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Security Technology Sector First year progress report Author – Kshitij Aditeya Singh Organisation – Institute of Nanotechnology May, 2009

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Security Technology Sector

First year progress report

Author – Kshitij Aditeya Singh

Organisation – Institute of Nanotechnology

May, 2009

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Executive Summary

A European Strategy on Security was adopted in 2003. The European Security and Defence

policy as a part of the common Foreign and Security policy has deployed 20 missions in response

to incidents. The use of various policy instruments in European Union (EU) has contributed to

security of society, improving equality, human rights and good governance. The policy and

missions adopted by the EU are linked to the United Nations objectives in security. The European

Security Strategy aims to address the security challenges such as proliferation of weapons of

mass destruction, terrorism and organised crime, energy security, cyber security, climate change,

securing industrial supply chains and trade routes, and responding to natural disasters.

The rapidly changing dynamics of present times and forces in a globally integrated world are a

reflection of the numerous challenges facing societies in protecting civilians and civilian

infrastructure. Recent acts of aggression in London and Madrid bombings have revealed the

weaknesses of security provisions in civilian zones. Risk and threats that have multiple

dimensions need to be addressed for maintaining harmony and peace. The disruptions in civil

society may arise from natural elements or divisive human forces. Technology can act as an

enabler in assisting agencies in operational situations, where limitation of time and unknown

quantity of risk presents itself. Technology research and development can enhance capabilities in

supporting security missions for maintaining peace and harmony in society.

Methodology

The European Security Research Advisory Board (ESRAB) had produced a strategic framework

for structuring research on technology and non-technological aspects. In a multidisciplinary

approach to research aligned with strategic missions, capability development and systems

development has been identified of prime importance. The technical research in ESRAB was

grouped based on capability development, system development and system of system

demonstration. These research areas were focused on addressing mission specific needs or

multi-mission needs. The mission areas identified under ESRAB were border security, protection

against terrorism and organised crime, critical infrastructure protection, and restoring security in

case of crisis. A cross mission analysis was conducted as a part of the scope. The capability

enhancement was focused into the following functional groups: detection, identification and

authentication; situational awareness and assessment including surveillance; risk assessment,

modelling and impact reduction; positioning and localisation; command and control; intervention;

doctrine and operations; incident response; information management; communication; training

exercise.

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Figure E.1 – Nanotechnology as an enabler of capabilities for Security Missions (Source:

ESRAB)

Nanotechnology research and development can enhance security capabilities that enable critical

security missions. An illustration of a capabilities enhancement by nanotechnology research is

shown in figure E.1. The segmentation of nanotechnology applications for security was done

based on enhancement of capabilities and missions identified in ESRAB. The mission specific

capabilities enhancements are largely categorized into existing, new and advanced.

The segmentation of the security technology sector was done into four sub-sectors: ‘detection’,

‘protection’, ‘incident support’, and ‘anti-counterfeiting, authentication and positioning’. The

detection sub-sector is further divided into technology segments for ‘chemical’, ‘biological’,

‘radiological and nuclear’, ‘explosive’ (CBRNE) weapons and ‘narcotics’ detection. The research

and development observations in the protection sub-sector is further done by technology

segments defined as ‘protection of civilians and civilian security agencies’, ‘ equipment and

infrastructure protection’, and ‘condition monitoring of civilian zones and infrastructure’. The

research and development observations in incident support segment have been done based on

nanotechnologies relevant to ‘decontamination’, ‘forensic’ and ‘neutralising CBRNE effect’. The

final segment has nanotechnologies research and development analysed based on ‘anti-

counterfeiting, authentication and positioning and localisation’ (AAPL). A definition of the each of

the technology segments is available from each of the sub-sector report. A visual representation

of the segmentation of capabilities can be seen in Figure E.2 below.

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Figure E.2 – Segmentation of capabilities in Security Technology Sector

The observations in each of the technology segments from the literature review were classified

into the technology readiness level. These were defined into 6 levels representing research

(fundamental and applied), development (prototype and field trails) and application (niche and

mass deployment). Gaps in implementation and further research needs have been identified for

the above technology segments that relate to specific missions. The technology segment

observations have also taken interaction with aspects of commercialisation, environment health

and safety issues, ethical, societal and regulatory aspects into consideration. The expert

engagement process through surveys, interviews and workshops were used to validate the

findings and refine the course of future work. Observations from workshop discussion were

recorded and synthesized through a group of observers along with the moderator.

The methodology is limited in not being able to present an exhaustive view of all technology

research and developments taking place across the world. Among other methodology challenges

are balancing the width of technology monitoring and analysis, balancing knowledge

representation in profile of experts engage and improving the comparative assessment between

world regions taking national language publications into consideration.

Segmentation

Detection

Protection

Chemical

AAPL

Incident Response

Anticounterfeiting Authentication

Decontamination Forensics

Infrastructure and equipment

Personal Protection

Positioning and Localisation

Neutralising CBRNE effect

Biological Radiological / Nuclear

Narcotics Explosive

Condition monitoring

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Detection

The growing threat from terror related activities to civilian security presents a significant challenge

to policymakers and security agencies. The observations in the detection segment have been

made with a view to assist civilian agencies and policymakers in identifying technology

developments of materials and devices between 1-100 nm that may prove to be useful in

safeguarding civilians by detecting substance posing a significant threat. The approach taken for

detection has been that of identifying development that enable devices or instruments used in

detection of different species. The risk agents have been defined in the initial part, where

chemical biological, radiological dispersive devices, nuclear and explosives (CBRNE) weapons

are the main focus of the detection sub-sector. The observations also address nanotechnology

developments in detecting narcotics. The scientific species have then been related to specific

enabling nanoscale technologies and devices integrating them. The observations are intended to

provide an overview of the current state of the art and the development trajectory.

The detection of chemical weapons by identification of chemical species can be accomplished by

a range of sensing methods, and instruments. The nanotechnology development mentioned in

the observations for chemical weapons detection are electronic noses, conductive polymers, field

effect transistors, piezoelectric sensors, field effect transistors, piezoelectric sensors, surface

acoustic wave sensors, flexural plate wave sensors, sensor arrays, optical fibres, cantilever

mechanism, chemiresistive action, chemicapacitive sensing and spectroscopic methods.

Nanotechnology research and development for explosive detection has been observed. These

observations are based on electrochemical sensing, mass based detection, optical sensing,

biosensors, Terahertz detection, photoluminescence, cataluminescence, nanosensors, and

nanowires based methods for explosive detection. The methods for detecting biological toxins are

based on molecular recognition, self assembled bilayers, biosensors, metallic nanowires,

Terahertz waves. Detection of radioisotopes based on methods based on sensor networks,

radiation portal monitoring equipment, cantilever based detection, mass spectrometry, nuclear

resonance fluorescence, electronic neutron dosimeter and neutron imaging camera has been

mentioned. The role of radiation detection material, nanocomposites, and nanomaterials for

detectors has been observed. Narcotics detection based on membranes, portable detection

systems, mass spectrometry, and Raman scattering has been observed.

The nanotechnologies for various detection methods have been observed to be in different

stages from applied research, to prototypes and developments that are undergoing field trials.

The pace of technological developments is variable for the different detection methodologies

used. Demand for specific additional research and desired functionality for detection has been

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further elaborated. Each technology segment identifies the drivers and barriers for research

affecting the development of detection. The main drivers for detection research were considered

as technological and social impact, while the main barriers were considered to be inadequate

finance availability and insufficient technology transfer from Universities. Essential functionalities

have been outlined, application specific trends and needs identified. Deployment of detection

technologies, future development and factors affecting uptake and penetration has also been

reported for the above mentioned detection methods. A relative comparison of regional

competencies of Europe, North America and Asia has also been reported qualitative. A number of

qualitative suggestions such as collaborative research, tax exemptions, technology transition and

fund allocation for improvement of capabilities have also been mentioned in the technology

segment.

The outcomes of the workshop on an integrated platform for CBRNE detection enabled by

nanotechnology held in Dusseldorf were that technology was not sufficiently advanced to achieve

a single platform for CBRNE detection. It was recommended that an integrated modular system

that focuses on chemical, biological and explosive detection as one unit and radiological-nuclear

detection as another unit may be a better approach. It was agreed that systems integration for

CBRNE detection was a major challenge. Suggestion were made regarding producing a

statement of requirements taking nanotechnology into consideration. Accuracy and reliability of

measurement was considered to be the most important characteristics. Reproducibility of

measurements and operating life of sensors were considered poor for a modular system. A need

for greater understanding in the sensing mechanism through fundamental research was

emphasised. The first application of integrated platform was expected to be transportation hubs.

The demand for development and uptake of technology would be driven by the state as agreed in

the expert engagement process.

While there are a number of developments going on at present for detection of different threat

agents, there are a number of challenges that need to be overcome. Some of the challenges that

need to be overcome are integration of a large number of sensors, high sensitivity and specific

detection of toxins. The detection method observed present one advantage over another method

due to a range of causal factors. A number of complimentary approaches are in practice, though

integration of detection of multiple species on a single platform remains an ongoing challenge.

Incident Support The incident support function in civilian security serves to provide relief to victims of an attack or a

crime directed unknowingly or with intent against them. The responses and measures are through

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medical aid offered to victims and neutralisation of CBRNE effects. Incident support function also

aims to neutralise and decontaminate the environment, civilian infrastructure and vital utilities

such as water supply. Forensic analysis of evidence at crime scenes is also a vital part of this

function. It aims to establish the causal link in a crime or terrorist act. Nanotechnology research

and development enhancing capabilities of Incident Support have been observed.

The neutralisation of effects of chemical and biological attack on civilian population has been

observed. Prophylactic antidotes for neurotoxic organosphosphorus compounds have been

mentioned. Diagnosis and pharmaceutical countermeasures such as vaccines, sera and

medicine have been observed as neutralisation means. A number of delivery methods of

antidotes based on nanoparticles for targeted delivery, antidote carrying capacity and release has

been observed for a range of methods. Improved diagnostics based on quantum dots, nano-

enabled biosensors, molecular imaging and lab on a chip has been mentioned for incident

support functions. The neutralisation of radiological and nuclear effects using nanosized magnetic

sorbent, zircon, nanostructured sodium silcotitanate and super adsorbent polymer gels have been

mentioned for environmental remediation of radio nucleotides. The use of mass spectrometry in

determining environmental contamination has been reported. Biodegradable nanospeheres have

been observed for removing toxins from blood stream of victims. The incident response through

provision of medical aid for victims of explosions has been observed. Self assembled peptides

forming nanofibrous barriers in stopping bleeding of victims has been mentioned. Research and

development in nano-scale innovation is expected to enhance capabilities in surgery for victims of

explosion. Bone and dental implants enabled by titanium dioxide have been reported. Nanophase

materials, ceramic nanoparticles, nanocomposites and nanotubes have been reported to have

applications in implants. The application of nanofibres in tissue engineering, magnetic

nanoparticles as coatings on stents, carbon nanotubes based regeneration of neurons,

biodegradable polymer scaffolds, and nanowires in implants are expected to benefit medical aid

provided to explosion victims. The use of nanoscale silver and nanofibrous membranes provide

benefits in wound care dressing.

Research and development at a nanoscale enabling capabilities in forensic analysis and criminal

investigation has been observed in literature. The detection of latent fingerprints evidence and

establishing an association with a crime remains of utmost importance in serving justice. The use

of optical, physical, and chemical techniques has been observed for fingerprint detection. The use

of quantum dots, nanocomposites, metal nanoparticles of gold and silver, metal oxide

nanoparticles of titanium and zinc, nanoparticles metal sulphide of cadmium and zinc have been

observed. The use of microscopy and spectroscopy methods have been observed in the analysis

of forged documents, hand writing, fingerprints, damaged electronic devices, gun shot residue,

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and firearm identification. Biosensors have also been reported to have forensic applications. DNA

identification has an important role in forensics with a number of developments that have been

reported. Methods such as geno-magnetic nanocapture, single molecule spectroscopy,

electrochemical sensors and lab-on- a- chip developments have been observed.

Decontamination of the environment and infrastructure are essential incident support function

following a contamination event. A number of nanoscale materials are being researched for

decontamination applications. Nanosized metal halogen adducts nanocrystals of magnesium

oxide, photocatalytic titanium dioxide coatings, silica coated nanoparticles, and nanocrystalline

zeolites have been observed. Photocatalytic nanowires have been mentioned for breaking down

environmental toxins in the air. Silica xerogels for removing toxic gases, nanoporous keratin

fibres for removing heavy metals, nanofibrous membrane for removing particulates in liquids have

been mentioned as remediation measures. Nanoporous membranes for removing pores from air,

nanoceramic membranes decontamination of mercury, and use of nanocrystalline silver in filters

for decontamination of water has been observed as research development.

The state of research and development for neutralising effects of CBRNE, Forensics, and

Decontamination range from applied research, protyping, field trials and deployed for use. The

vast majority of observations are in the applied research state while some have reached field

trials. Further demand for research has been reported along with the current situation in Europe

through the framework projects. The drivers and barriers for research in incident support have

been reported. The drivers for research were considered to be technological and societal impact.

The main barriers were considered as availability of finance and intellectual property conflict.

Important functionality requirements, expected development course and factors affecting the

uptake of applications have also been observed from the expert engagement process. The most

attractive and growth markets in the above mentioned applications were also indicated in the

process. North America effort in the sub-sector was considered to be better than other world

region for research, development and commercialisation for decontamination. In forensics, an

area considered to be of limited research, EU was considered to at par with other world regions.

For neutralising CBRNE effects, North American and EU research were considered to be at par.

The potential toxicity of nanoparticles was identified as a concern requiring greater research and

validation.

Protection

Nanotechnology research and development to provide protection to civilians, civilian agencies

and infrastructure has been observed in the literature. The protection function is served by shields

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made out of nano-scale materials. The materials provide shielding against chemical, biological,

radionucliotides, ballistic projectiles, sharp objects and electromagnetic interference. The

protection of equipment and infrastructure threat agents physical, natural and electronic has been

observed. The rapid proliferation of asymmetric threats has made it necessary not only to protect

but also to continually monitor the condition of the environment within civilian zones and that of

infrastructure. The information and communication integration with active monitoring is

considered important for prevention and mitigation of the impact from threat agents.

Protective barrier suits functionalised with nanoscale material has been observed to act as a

barrier against chemical and biological species. Nanoparticles of magnesium oxide in a

nanocomposite membrane have been observed for enhancing protection capabilities. Nanofibres

of polymer have been reported to enhance protection functionalities against CBRNE agents.

Nanocomposite for body armour application, multilayer polymer thin films have been incorporated

into body suits for neutralising chemical and biological agents have been reported. The use of

dendrimers and electro-rheological fluids has also been mentioned for body suit applications.

Research has demonstrated the effective use of carbon nanotubes as barrier to ballistic

projectiles. Yarns of multiwalled carbon nanotubes have been observed to have excellent

reversible damping from projectile impact making it suitable for protective vests.

Protection of infrastructure from ballistic impact and shock waves enabled by nanoscale material

has been observed in literature. The use of metal foams, nanometre sized precipitates, ceramic

composites have been observed to have infrastructure and equipment protection applications.

Vertically aligned carbon nanotubes have been shown to demonstrate super compressible foam

like behaviour, acting as energy absorbing surfaces for protection against ballistic projectiles and

earthquakes. Inorganic fullerenes of tungsten and molybdenum sulphide have been mentioned to

have excellent mechanical and shock resistance behaviour making them suitable for protection

against ballistic impact. Protection of infrastructure against fire is possible from the benefits

offered by nanoscale materials. Nanoscale layered double hydroxide, nanocomposites of silicon

dioxide, nanocomposites of polymer-organoclay, nanocomposites of layered silicates, buckyball

nanocomposites and bucky paper have been observed to have fire resistance properties suitable

for protection applications.

Electromagnetic interference (EMI) presents a significant threat to the highly integrated

information and communication networks. A number of research developments have been

reported for potential application in EMI shielding. Intrinsically conductive polymers have been

observed to be suitable for shielding applications. Nanoscale materials such as nanocrystalline

silver coated ceneospheres, lamellar nanocomposites based on polymers such as polyaniline

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have been observed to be suitable for shielding application due to high conductivity. Organo-

clays and polyaniline nanocomposites have been observed to have high conductivities and good

mechanical properties. Carbon nanotubes and carbon nanofibres in polymer matrix have also

shown to have excellent shielding characteristics. Vapour grown carbon nanofibres have been

studied for their shielding effectiveness. Multiwalled carbon nanotubes and single walled carbon

nanotubes are being researched for shielding applications against a wide range of frequencies

from the electromagnetic spectrum. Silver colloid nanoparticles in protective thin films and

nanoparticles of nickel and iron alloys in expanded graphite have been observed to be in an

applied research stage. Nanoscale zinc oxide, carbon nano onions and detonation nano diamond

composites are being researched as candidate materials for EMI shielding applications. EMI

shielding using materials such as carbon matrix composites with self assembled interconnected

carbon nanoribbon network have been researched for low frequency portable electronics

applications. Carbon nanotubes and shape memory alloys have also been mentioned for

shielding effectiveness.

Capabilities in condition monitoring of infrastructure and civilian zone environment can be

enhanced through sensor networks. Nanotechnology research in sensing, information

processing, communication and data transfer, storage and providing power can benefit the

development of sensor networks and sensory nodes. A number of sensing mechanism based on

nanoscale material and phenomena have been observed in the ‘Detection’ segment for CBRNE

based on physical, chemical, optical, mechanical and electronic changes. Advancements in

carbon nanotubes based transistors have been observed that may enhance capabilities

processing capabilities of sensor networks. Carbon nanotubes and nanowires have been

reported to have applications in communication and data transmission applications. Nanotube

based antennas have been reported for communication. A range of nanooptoelectronic

components are expected to add value to sensor networks. Advancements in storage are

expected to benefits sensor network through the developments in IBM’s millipede technology,

carbon nanotubes based NRAM, molecular memory, ferroelectric RAM, magnetic RAM, and

phase change bridge RAM. Research in nanocrystalline materials and nanotubes for applications

in electrodes are expected to enhance the characteristics of batteries. The use of carbon

nanotubes in supercapacitors is being researched which may have potential applications for

sensory nodes. The application of solar cells in power harvesting for sensory nodes is also being

investigated. The application of quantum dots, carbon nanotubes, polycrystalline thin films, single

crystalline thin films, organic and polymer solar cells has been observed to be under research

and development. Power harvesting from mechanical vibrations using cantilever and nanowires is

also being researched.

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The outcomes of a workshop on nanotechnologies enabling sensor networks for detection of

CBRNE held in Dusseldorf, was that sensor networks would be valuable for trend monitoring and

pattern recognition across cities and in local areas. The greatest value addition from

nanotechnology to sensor nodes would be at the sensing layer. While integration of multi-channel

sensors was not accomplished, novel sensors could be easily integrated with commercial off the

shelf components to produce such a network. The market would be created by the state and

consideration should be given to dual use for improving commercial attractiveness.

The vast majority of technological capabilities mentioned in the segment are in the applied

research stage with many integration challenges to be fulfilled before the technology becomes a

mainstream application for the protection of civilian and civilian infrastructure. The expert

engagement process identified the main drivers for research in the protection sub-sector were

considered to be technological and safety of citizens. The main barriers were considered to be

availability of finance and intellectual property related conflicts. Important functionalities for each

of the technology segments were identified and the applications trends noted. Relative

comparison of research, EU was considered better for personnel protection while US had better

instruments for commercialisation and technology transfer. Qualitative suggestions for improving

research and development efficiency were mentioned as tax benefits, introducing

commercialisation performance metric for academics, and promotion of scientific security

enterprise.

Anti-counterfeiting, Authentication, Positioning and Localisation Anti-counterfeiting, authentication, positioning and localisation research and development is

expected to prevent crime by reducing theft of goods, property and identity. Nanotechnology

developments in anti-counterfeiting are expected to improve brand protection by reduction in

counterfeiting of technological goods and products. Authentication related nanotechnology

research and developments are expected to enhance border security and protection against

identity theft. Research enabled by nano-materials is expected to enhance positioning and

localisation capabilities. The enhanced positioning capabilities are expected to improve the

security of industrial supply chains from theft.

Research in nano-enabled materials, methods and devices has been observed for anti-

counterfeiting applications. Nanocomposites of silicates, zeolites and luminescent nanoparticles

in photopolymerisable nanocomposites have been researched as recording material for

holographic security patterns. Laser surface authentication used to map the surface roughness is

under field trials as a potential anti-counterfeiting technology. The physically unclonable function

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developed by Philips and magnetic fingerprinting technology based on distributing micro-nano

scale magnets in non magnetic medium has been observed to offer potential advantages. Three

dimensional polymer patterns on a nanoscale, metallic sub-micron rods of gold, silver and

platinum, and quantum dots have been observed as nano barcodes for enhancing anti-

counterfeiting features. Surface enhanced Raman scattering tags are being developed as

potential solutions for anti-counterfeiting. The processing and integration of organic nanofibres,

and research into multilayered nanostructures, for bank notes has been observed. Nanoclusters

of metal atoms in thin films have been researched for using optical effects in anti-counterfeiting

applications. Nanomaterials are being researched and patented for applications in anti-

counterfeiting. Nanoscale titanium dioxide and zinc oxide are being developed for application in

bank notes, birth certificates and drivers licenses. Single and multiwalled carbon nanotubes have

been demonstrated as security marks. Diffractive structures for anti-counterfeiting verification

have been developed in quantum dots and metallic nanoparticles. The use of gold nanoparticles

as composites in security paper has also been observed. The state of research and development

for anti-counterfeiting technologies range from fundamental research, applied research,

prototype, field trials to commercialised.

Authentication of identify, information and communication play a vital role in preventing crime.

Nanomaterials are expected to enable identity verification. Polymer nanocomposites have been

observed to have application in security labelling of features such as fingerprints, photograph and

signature. Quantum dot doped polymer opal composites have been developed for application as

fingerprinting sensors. Optical fluorescent fibres have been developed as anti-counterfeiting

technology. Quantum cryptography research is expected to enhance the safety and security of

information and communication exchange. The state of enabling nanotechnologies for

authentication ranges from fundamental research to field trials.

Radio frequency identification tags are expected to enhance the positioning and localisation of

industrial goods by providing enhanced security for the industrial supply chain. Nanotechnology

research and development can enhance the performance of RFID components. Conductor

patterns based on organic insulated copper and silver nanoparticles have been experimentally

demonstrated. Carbon nanotubes antennas have been researched and developed for RFID

application. Printed RFID antennas produced from silver nanoparticles ink and nanowires have

been observed. Position and Localisation have been observed to be at the applied research

stage.

The main drivers for research in AAPL were considered to be technological, economic gain,

social impact and regional policy. Brand theft, product theft and forgery were other specific drivers

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for research in AAPL sub-sector. The main barriers for AAPL were regarded as lack of

supporting government policies, access to equipment and infrastructure and lack of technology

transfer. Failure to integrate during field trials was regarded as a development barrier. Important

functionalities for applications were identified and trends mentioned for the technology segment.

Timelines for technology adoption were qualitatively presented for the research and development

mentioned above. Laser surface authentication and nanocluster identification were considered

closest to application, while others like holographic features were already present as applications

in the market. Qualitatively research trends were mentioned to be towards intelligent materials

and packaging.

Comparative World wide and EU situation: Publications and Patents

The world wide activity in security was compared using a publication database MERIT and

methodology developed within the Observatory Nano project. The comparison of countries

conducting security research revealed in the period from 1998 – 2007, USA (44,885) was leading

the publication in applications, followed by Peoples Republic of China (26,505) and Japan

(18,312). Other top 10 world leading countries for publications in security were Germany

(16,577), France (10,784), United Kingdom (9,488), South Korea (7,194), Italy (6,466), India

(5,762), and Spain (5,050). Worlds top ten Institutions publishing security research are Chinese

Academy of Science (6,692), Russian Academy of Science (2,502), CNRS (1969), University of

Tokyo (1,811), Osaka University (1,552), University of Science and Technology China, Tohoku

(1,538), Tsing Hua University (1,437), Nanjing University (1,384), and CNR (1,349). A more

detailed view of the research institutions and world wide countries is available from the

publication report.

Within Europe security research is led by Germany followed by France, United Kingdom, Italy,

and Spain. The remaining top 10 countries in Europe for security research are Switzerland

(3,330), Netherlands (3,038), Sweden (2,859), Poland (2,484), and Belgium (1,964). Institutions

in Europe leading publications in security research, in a European journal, during the period of

1998-2007 were CNRS (1,966), CNR (1,329), CSIC (1,322), University of Cambridge (1,135),

Russian Academy of Science (925), University of Paris (834), ETH (752), University of Oxford

(730), and Polish Academy of Science (723). Research collaboration leading to joint publications

between EU researchers and other world regions were also observed. The collaborating regions

with highest number of joint publication records were noted to be USA (6,420), Russia (1,826),

Japan (1,610) and Peoples Republic of China (1,288). Other leading top 10 collaboration

researchers for security were observed to be from Canada (842), India (656), Israel (572),

Australia (563), Brazil (515), and Ukraine (427). A number of European framework projects have

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been observed for each technology segment which are actively pursuing security research and

development. These have been mentioned in the technology segment observations.

The patent analysis was based on the European Patent Office ‘World wide patent statistical

database’. It was mentioned that 5944 patent documents resulted from the classification and

keyword search. A more detailed view on the methodology used is available from the patent

report. The leading country in the world was considered to be ‘United States’ with 48% of the

patents assigned, followed by ‘Japan’ with 18% and ‘Germany’ with 12% in third place. The

combined output for European Union was mentioned to be 26% of the total security related patent

documents. The correlation search in the International Patent Classification system revealed the

main areas of patenting to be ‘measuring electric and magnetic variables’, ‘measuring chemical

and physical properties’, ‘information storage’, ‘biochemistry, enzymeology and microbiology’, and

‘semi-conductor devices’.

Numerous challenges exist for security applications of nanotechnology. The development of

capabilities enabling missions identified in the ESRAB will require overcoming the scientific and

technological barriers. In addition each of the enabling nanotechnologies will have to demonstrate

performance benefits at minimal costs in order for them to become mass applications. Integration

of nanotechnology applications in existing systems to provide enhanced operational capabilities

will be one of the biggest challenges to be overcome. The realisation of the potential offered by

nanotechnologies for civilian security is expected to increase the safety and security of European

citizens and also of other world regions. Future work of the ‘Security Technology’ sector is

expected to take into consideration outcomes and recommendations of the European Security

Research and Innovation Forum.

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Table of Contents

Executive Summary..................................................................................................................... - 2 -

Table of Contents ...................................................................................................................... - 15 -

Foreword.................................................................................................................................... - 19 -

Acknowledgements ................................................................................................................... - 21 -

1. Detection................................................................................................................................ - 25 -

1.1.1 Title – Chemical................................................................................................................ - 25 -

1.1.2 Definition of Technology segment .................................................................................... - 25 -

1.1.3 Short Description .............................................................................................................. - 26 -

1.1.4. State of Research and Development .............................................................................. - 31 -

1.1.5 Additional demand for research ....................................................................................... - 33 -

1.1.6 Applications and Perspectives.......................................................................................... - 34 -

1.1.7 Current Situation within EU .............................................................................................. - 39 -

1.2.1 Title – Biological ............................................................................................................... - 41 -

1.2.2 Definition........................................................................................................................... - 41 -

1.2.3 Short Description .............................................................................................................. - 41 -

1.2.4 State of Research and Development ............................................................................... - 46 -

1.2.5 Additional demand for research ....................................................................................... - 47 -

1.2.6 Applications and Perspectives.......................................................................................... - 48 -

1.2.7 Current Situation within EU .............................................................................................. - 53 -

1.3.1 Title - Radiological and Nuclear........................................................................................ - 55 -

1.3.2 Definition of Technology Segment ................................................................................... - 55 -

1.3.3 Short Description .............................................................................................................. - 55 -

1.3.4 State of Research and Development ............................................................................... - 60 -

1.3.5 Additional demand for research ....................................................................................... - 61 -

1.3.6. Applications and Perspectives ........................................................................................ - 61 -

1.3.7 Current Situation within EU .............................................................................................. - 65 -

1.4.1 Title – Explosives.............................................................................................................. - 67 -

1.4.2 Definition of Technology Segment ................................................................................... - 67 -

1.4.3 Short Description .............................................................................................................. - 68 -

1.4.4 State of Research and Development ............................................................................... - 75 -

1.4.5 Additional demand for research ....................................................................................... - 76 -

1.4.6 Applications and Perspectives.......................................................................................... - 77 -

1.4.7 Current Situation within EU .............................................................................................. - 82 -

1.5.1 Title - Narcotics................................................................................................................. - 84 -

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1.5.2 Definition of Technology Segment ................................................................................... - 84 -

1.5.3 Short Description .............................................................................................................. - 84 -

1.5.4 State of Research and Development ............................................................................... - 85 -

1.5.5 Additional demand for research ....................................................................................... - 86 -

1.5.6 Applications and Perspectives.......................................................................................... - 86 -

1.5.7 Current Situation within EU .............................................................................................. - 88 -

2. Incident Support .................................................................................................................... - 90 -

2.1.1 Title – Neutralising CBRNE effect .................................................................................... - 90 -

2.1.2 Definition of Technology Segment ................................................................................... - 90 -

2.1.3 Short Description .............................................................................................................. - 90 -

2.1.3.1 Response to Chemical and Biological threats attack ........................................... - 90 -

2.1.3.2 Response to Radiological and Nuclear weapons attack ...................................... - 93 -

2.1.3.3 Response to Explosive Incident............................................................................ - 94 -

2.1.4 State of Research and Development ............................................................................... - 95 -

2.1.5 Additional demand for research ....................................................................................... - 99 -

2.1.6 Applications and Perspectives........................................................................................ - 101 -

2.1.7 Current Situation within EU ............................................................................................ - 103 -

2.2.1 Title – Decontamination.................................................................................................. - 104 -

2.2.2 Definition of Technology Segment ................................................................................. - 104 -

2.2.3 Short Description ............................................................................................................ - 104 -

2.2.4 State of Research and Development ............................................................................. - 107 -

2.2.5 Additional demand for research ..................................................................................... - 109 -

2.2.6. Applications and Perspectives ...................................................................................... - 109 -

2.2.7 Current Situation within EU ............................................................................................ - 111 -

2.3.1 Title - Forensics .............................................................................................................. - 112 -

2.3.2 Definition of Technology Segment ................................................................................. - 112 -

2.3.3 Short Description ............................................................................................................ - 112 -

2.3.3.1 Metal Nanoparticles in Forensics........................................................................ - 114 -

2.3.3.2 Metal oxide nanoparticles in fingerprint detection .............................................. - 116 -

2.3.3.3 Metal sulfide nanoparticles in fingerprinting detection........................................ - 116 -

2.3.3.4 Microscopy and Spectroscopy............................................................................ - 117 -

2.3.3.5 Biosensors .......................................................................................................... - 118 -

2.3.3.6 Role of DNA in forensics..................................................................................... - 119 -

2.3.4 State of Research and Development ............................................................................. - 122 -

2.3.5. Additional demand for research .................................................................................... - 123 -

2.3.6 Applications and Perspectives........................................................................................ - 124 -

2.3.7 Current Situation within EU ............................................................................................ - 126 -

- 17 -

3. Protection............................................................................................................................. - 127 -

3.1.1 Title - Personnel ............................................................................................................. - 127 -

3.1.2 Definition of Technology Segment ................................................................................. - 127 -

3.1.3 Short Description ............................................................................................................ - 127 -

3.1.4 State of Research and Development ............................................................................. - 129 -

3.1.5 Additional demand for research ..................................................................................... - 130 -

3.1.6 Applications and Perspectives........................................................................................ - 131 -

3.1.7 Current Situation within EU ............................................................................................ - 133 -

3.2.1 Title – Infrastructure and Equipment .............................................................................. - 134 -

3.2.2 Definition of Technology Segment ................................................................................. - 134 -

3.2.3 Short Description ............................................................................................................ - 134 -

3.2.3.1 Reinforcement of structures................................................................................ - 134 -

3.2.3.2 Protection against fire ......................................................................................... - 135 -

3.2.3.3 Electromagnetic shielding of information and communication equipment ......... - 136 -

3.2.4. State of Research and Development ............................................................................ - 139 -

3.2.5 Additional demand for research ..................................................................................... - 142 -

3.2.6 Applications and Perspectives........................................................................................ - 142 -

3.2.7. Current Situation within EU ........................................................................................... - 143 -

3.3.1 Title – Condition Monitoring............................................................................................ - 144 -

3.3.2 Definition of Technology Segment ................................................................................. - 144 -

3.3.3 Short Description ............................................................................................................ - 144 -

3.3.4 State of Research and Development ............................................................................. - 148 -

3.3.5 Additional demand for research ..................................................................................... - 150 -

3.3.6 Applications and Perspectives........................................................................................ - 151 -

3.3.7 Current Situation within EU ............................................................................................ - 153 -

4. Anti-counterfeiting, Authentication, Positioning and Localisation........................................ - 156 -

4.1.1 Title – Anticounterfeiting ................................................................................................. - 156 -

4.1.2 Definition of Technology Segment ................................................................................. - 156 -

4.1.3 Short Description ............................................................................................................ - 156 -

4.1.4 State of Research and Development ............................................................................. - 162 -

4.1.5 Additional demand for research ..................................................................................... - 164 -

4.1.6 Applications and Perspectives........................................................................................ - 164 -

4.1.7 Current Situation within EU ............................................................................................ - 165 -

4.2.1 Title - Authentication....................................................................................................... - 166 -

4.2.2 Definition of Technology Segment ................................................................................. - 166 -

4.2.3 Short Description ............................................................................................................ - 166 -

4.2.4 State of Research and Development ............................................................................. - 168 -

- 18 -

4.2.5 Additional demand for research ..................................................................................... - 169 -

4.2.6 Applications and Perspectives........................................................................................ - 169 -

4.2.7 Current Situation within EU ............................................................................................ - 170 -

4.3.1 Title – Positioning and Localisation ................................................................................ - 171 -

4.3.2 Definition of Technology Segment ................................................................................. - 171 -

4.3.3 Short Description ............................................................................................................ - 171 -

4.3.4 State of Research and Development ............................................................................. - 172 -

4.3.5 Additional demand for research ..................................................................................... - 173 -

4.3.6 Applications and Perspective ......................................................................................... - 173 -

4.3.7 Current Situation within EU ............................................................................................ - 174 -

References and Literature ....................................................................................................... - 175 -

- 19 -

Foreword The report has been written with the view to provide policy makers with analysis on the state of

research and development for security applications of nanotechnology. Due to the nature of the

fundamental science and engineering underlying the applications, the observations have

relevance to several sectors. For instance security applications have overlap with ‘Chemistry and

Materials’, ‘Energy’, ‘Information Communication Technology’, ‘Health, Medicine and

Nanobiology’, ‘Environment’ and ‘Textiles’.

The security applications were related to enabling capabilities and missions based on the

Strategic Research Agenda recommended by the European Security Research Advisory Board

(ESRAB). Though ESRAB does not exist formally anymore, the research agenda has relevance

to security. The technology segmentation has been based on applications that are relevant to

‘Civilian Security’ or also known as ‘Homeland Security’ in other world regions. The observations

for civilian sector have been reported for four sub-sectors, namely detection, incident support,

protection, and anti-counterfeiting, authentication, positioning and localisation (AAPL). There has

been relatively greater focus on detection and incident support sub-sectors. The state of research

and development are not exhaustive but aim to provide a representation of activities that have

relevance to security.

The observations have been primarily made from research and development that aim to produce

a device or enable instruments that address a specific security need. Where deemed necessary

observations have also been made from areas of complimentary research to complete the overall

picture. The sections of the technology segments reports are based on a standard template

created for the Observatory Nano project in the formative stages. The standard template aims to

bring scientific and technology information about an application area within the larger scope of the

project.

The technology segment reports were written as stand alone reports and have been reviewed by

experts as stand alone chapters. Whilst information about other aspects such as markets, health,

environmental and societal issues have been mentioned in various places, these have been

covered in greater detail in other work packages of the project. Some of the information related to

other aspects has been included in the perspectives on applications.

- 20 -

Specific additional demand for research has been mentioned for a majority of the technology

segment, while some segments give a more general view. The current state within Europe has

been represented through research and development project activity in the framework

programmes. A national review of the various security programmes has not been conducted,

instead an EU-wide view has been provided to reflect the activities. The information is

supplemented by both publication and patent analysis to give a relative comparison of activity

world wide.

The analysis has been supplemented by perspectives on the applications by experts from various

areas. The names of these experts involved in the survey, interview and workshop have been

recognised in the acknowledgement section. The validation of the technology segment report was

reviewers for accuracy and representation of the subject.

The limitation of the analysis has been mentioned in the methodology. All effort has been made to

ensure the scientific validity and factual accuracy of observations recorded in the document.

Further work is due to take the recommendations and outcomes of European Security Research

and Innovation Forum into consideration, which is the successor body to ESRAB and builds on its

work with a long term vision for security research and innovation.

K. Singh

May 2009

- 21 -

Acknowledgements

The author would like to express his gratitude to the following experts who have reviewed the

different security technology segment reports and validated the observations before publication.

Name Organisation and Affiliation

1 Professor Anja

Boisen Technical University of Denmark

2 Dr. Sanjay Patel Seacoast Science Inc., U.S.A.

3 Professor Dr.

Helmut Bachmayer

Biosafety and Biosecurity Consultant, Former ESRAB

member, Austria

4 Professor Nikolas

A. Chaniotakis University of Crete, Greece

5 Professor Seamus

Higson Cranfield University, U.K.

6 Valerio Pagnotta CENG, Italy

7 Dr. Richard Kouzes Pacific Northwest National Laboratory, U.S.A.

8 Professor Steve

Haswell University of Hull, U.K.

9 Professor Anthony

Turner Cranfield University, U.K.

10 Dr. Andy Becue School of Criminal Sciences / Institut de Police Scientifique /

University of Lausanne, Switzerland

11 Dr. Kenneth J.

Klabunde Kansas State University, U.S.A.

12 Professor Sarah C.

Larsen University of Iowa, U.S.A.

13 Dr. Rutledge Ellis-

Behnke

Massachusetts Institute of Technology

and University of Hong Kong

14 Dr. J.-L. Wojkiewicz CEM- Ecole des Mines, France

- 22 -

15 Professor L. C.

Zhang University of Sydney, Australia

16 Dr. Y.Q. Zhu University of Nottingham, U.K.

17 Dr Leonid

Goldenberg Fraunhofer IAP, Germany

18 Prof. Dr.

T.Schalkhammer

Attophotonics Biosciences GmbH

and University of Vienna, Austria

19 Dr. T.Trindade University of Aveiro, Portugal

20 Dr. V. Sridhar Chonnam National University, Gwangju. South Korea

21 Dr. Edward A.

McKigney Los Alamos National Laboratory, U.S.A.

The author would also like to express his gratitude to the following experts for their input to the

Security technology sector by making their informed opinions available through survey

questionnaire, interviews and the Observatory Nano workshop. The output from these has been

presented in the applications and perspective section of the report.

Name Organisation/ Affiliation

1 Heloisa Mariath Senior Scientific Advisor, Austria

2 Dr. Elena Lacatus Polytechnic University of Bucharest

3 Dr. Sanjay Patel Seacoast Science Inc., U.S.A.

4 Dr. Jeong-O Lee Korea research institute of chemical technology, South

Korea

5 Dr. Andy Becue School of Criminal Sciences / Institut de Police

Scientifique / University of Lausanne, Switzerland

6 Dr. D. Ravi Shankaran Kyushu University, Japan

7 Keith Crandell Arch Venture, U.S.A.

8 Neil Wright C-Tech Innovation Ltd, U.S.A.

- 23 -

9 Dr. Patrick Gardner Western Carolina University, U.S.A.

10 Dr. Richard Kouzes Pacific Northwest National Laboratory, U.S.A.

11 Professor Anthony

Turner Cranfield University, U.K.

12 Prof. Dr.

T.Schalkhammer

Attophotonics Biosciences GmbH

and University of Vienna, Austria

13 Richard Palmer d30, U.K.

14 Dr. Daniel Crespy EMPA, Switzerland

15 Dr. Stan S. Swallow Intelligent Textiles Limited, U.K.

16 Dr. Christian Mittermayr Lambda GmbH, Austria

17 Professor Nikolas A.

Chaniotakis University of Crete, Greece

18 Dr. Edward A. McKigney Los Alamos National Laboratory, U.S.A.

19 Professor Dr. Helmut

Bachmayer

Biosafety and Biosecurity Consultant, Former ESRAB

member, Austria

20 Valerio Pagnotta CENG, Italy

21 Dr. Frank Schäfer Fraunhofer EMI, Germany

22 Dr. Gerhard Holl Bundeswehr, Germany

23 Dr Juergen Altmann University of Dortmund, Germany

24 Dr Michael Decker ITAS, FZK Karlsruhe, Germany

25 Professor Jim Darwent University of Liverpool, U.K.

26 Dr. Volkhard Beyer Fraunhofer Center Nanoelektronische Technologien

(CNT), Germany

27 Dr. Daping Chu University of Cambridge, U.K.

28 Dr Mostafa Analoui Livingston Group/Charlesson Pharmaceuticals, U.S.A.

29 Dr Donald Bruce EdinEthics, U.K.

- 24 -

30 Professor Seamus

Higson Cranfield University, U.K.

31 Dr Tony Munter VTT Technical Research Centre of Finland

32 Professor Dr. Cees

Gooijer VU University of Amsterdam, Netherlands

33 Dr. T.Trindade University of Aveiro, Portugal

34 Dr. Rutledge Ellis-

Behnke

Massachusetts Institute of Technology

and University of Hong Kong

The author would also like to thanks Tom Crawley and Laura Juvonen from Spinverse, and Ineke

Malsch from MTV for the contribution made in recording observations during the Security

workshops held in Dusseldorf at the annual symposium. The author would also like to express his

gratitude to all the Observatory consortium partners for the engagement and Mark Morrison for

his encouragement throughout the process.

- 25 -

1. Detection

1.1.1 Title – Chemical

Detection of Chemical Weapons and Industrial Toxins

Keywords: nerve agent, blister agent, electronic nose, nanosensors, chemiresistors,

chemicapacitors, conductive polymers, piezoelectric, sensor array, nanomaterials, spectroscopy,

field effect transistors, optical fibres

1.1.2 Definition of Technology segment

The prevention of development, production, stockpiling, and use of chemical weapons was

formed in 1992 by the Organisation for Prohibition of Chemical Weapons. Sarin gas was used in

Matsumoto in 1994 and in the Tokyo subway in 1995 [1]. Civilian security is also threatened by

malpractices in industry and accidents that lead to release of toxic industrial chemicals.

Organisation for Prohibition of chemical weapons has classified chemical weapons into three

categories - schedule 1, 2, and 3. Schedule 1 chemicals (nerve agents) have very limited

industrial uses. Schedule 2 chemicals (example are Amiton, PFIB, dimethyl methylphosphonate

precursor to sarin) have limited legitimate use on small scale. Schedule 3 chemicals (examples

are chloropicrin, hydrogen cyanide and phosgene) are those which have large scale uses. The

schedules limit the use of chemicals as identified in the conventions [2].

Table CW. 1 – A complied list of most harmful and common chemical warfare agents and

industrial toxic agents [2,3]

Category of Toxin Name

Nerve agent Tabun, Sarin, Soman, Cyclosarin, VX, Novichok agents

Choking agents Chloropiricn, chlorine, phosgene, diphosgene

Blister agent Sulphur mustard, Nitrogen mustard, Lewsite, Phosgene oxime (CX)

Cytotoxic proteins Ricin, Abrin

Industrial toxic agents

Phosogene , Hydrogen cyanide, Nitrous oxide, Carbon monoxide,

Hydrogen Chloride, Methyl isocynate, Mercury, Lead, Benzene

hexachloride, 1,3,5 trichlorobeneze , Dichloromethane, Chloroform

- 26 -

1.1.3 Short Description

Electronic Nose - Artificial noses also known as electronic noses are used to sense the

presence of toxic gases and bio agents, and convey its presence by means of an electrical signal.

These artificial or electronic noses are also used in detecting explosives. A number of

physiochemical approaches are used in sensing, for example measurement of changes in

conductivity for metals oxides and polymers, for piezoelectric materials changes in frequency are

measured and fluorescent optical fibers changes in colour are measured. Nanosensors based on

the human olfactory system have been studied in the United States for molecular recognition of

species, pre-processing of the neural signal and transduction of the signal. Sensors based on the

electrochemical are either conductance based or potentiometric (field effect transistor). Mass

change based piezoelectric sensors are quartz crystal microbalance and for surface acoustic

wave devices. Optical sensors are mainly either fluorescent based optical fibers or colorimetric

[4].

Conductance sensors are based on a metal oxide or a conducting polymer where binding of a

compound causes a change in the resistance between two metal contacts. The main material

used for metal oxide sensors are tin, zinc, titanium, tungsten, and iridium. These could be doped

with palladium or platinum. A gas sensor array the size of a thumb nail size can sense industrial

gases that maybe potentially toxic gases such as ammonia, formaldehyde and carbon monoxide

based on oxides of tin and tungsten. Sensor layer thickness can range from 2-20nm [5].

Nanoscale tin oxide based sensors and its variations, with grain size of 8 nm, have effectively

demonstrated the recognition of combustible gases such as propane, butane, LPG within their

explosion limits [6].

Conductive Polymer - Conductive polymers used as sensors use a polymer to connect two

electrodes. The polymer acts as the active sensing agent, the sensitivity of the sensor is higher

than metal oxide sensors. The main shortcomings of these types of sensors are the complexity of

fabrication and reproducibility of sensing function between batches [4,7]. The active sensor

element is used to detect volatile organic compounds. Polymers such as polypyrole, polyaniline,

polythiophene, and polyacetate are used due to their high sensitive to vapour and gases.

Nanometre sized carbon black has also been used to make polystyrene conductive for sensing

application [8]. Carbon black composite sensing arrays have been used to detect explosives and

chemical warfare agent such as sarin and soman [9].

- 27 -

Field effect transistors - Field effect transistors used as potentiometeric sensors have been

demonstrated in detecting gases by making the gates sensitive to gases. A volatile organic

compound produces a reaction in the sensing layer, which causes the physical property of the

gate to change, thereby changing the threshold voltage and thus the channel conductivity. Noble

metal catalysts such as platinum, palladium and iridium have been coated on metal oxide FET

[10]. Nose on a chip concept of sensors arrays of polymer gated FET’s is used for sensing

different odours. The sensing element is combined with a signal processing component, which is

used to detect the presence of a gas, identified by a train of spikes in the frequency [11]. Methods

such as statistical pattern recognition, neural networks, chemometrics, machine learning, and

biological cybernetics has been used to process electronic nose data [12].

Piezoelectric sensors - Piezoelectric devices working as an electronic nose work on the basis of

measuring a change in mass. Piezoelectric crystals vibrate under the influence of an applied

voltage, the mass of which determines the resonant frequency. Quartz crystal microbalance

(QCM) and surface acoustic wave device are used as electronic noses [7]. QCM is used in

explosive detection, wherein the adsorption of a gas molecule on the surface of polymer changes

the resonant frequency. Quartz crystal microbalance with immobilised nanoscaled ZSM-5 zeolite

film has been developed as a sensor for nerve agent. A minimum concentration of 1 part per

million (ppm) was detected using the stimulant dimethylmethylphosphonate [13].

Surface Acoustic Wave sensors - Surface acoustic wave sensors are based on acoustic waves

travelling on the surface of transducers. Adsorption of a gas molecule causes a change in the

mass thereby causing a change in the frequency or phase shift. The advantage with these

sensors is that they are easy to fabricate, while their drawback is that they are temperature

sensitive, the noise in the signal increases with decreasing size [14]. IBM has demonstrated

cantilever based sensors, in ambient air to detect ethenes, alcohols, natural flavours and water

vapour using optical methods [15]. Microsensor systems Inc a leading producers of SAW sensors

have demonstrated the nerve gas agents and blister gas agents, with a sensitivity of 0.04 ppm in

20 seconds and 0.01 ppm in 120 seconds respectively [16]. Polymer coatings such as

polysiloxane films that allow diffusion of chemical agents into the bulk of the film for optimal mass

loading. These have been used both for SAW and QCM sensors [17,18]. Thin film piezoelectric

acoustic sensor works on the basis of change in thickness of the gas sorption layer on the

substrate. These sensors can detect chemical and biological threats with a sensitivity of 100 ppm

[19,20].

Flexural plate wave sensors - Flexural plate wave sensors are similar to SAW and QCM

sensors detect an agent based on mass absorbed on a coating deposited on the sensor. It is

- 28 -

known to have one of the highest levels of detection sensitivity being in the range of parts per

trillion (ppt) [21]. Chemical vapour detection and biosensor array based on flexural plate wave

sensor has been demonstrated. A siloxane polymer coating 50nm thick is applied on the surface

for the detection of specific chemical agents. A sensitivity of 10 ppm was demonstrated in the

experimental study [22].

Sensor Arrays - Sensor arrays have been integrated with support vector machines for detecting

organophosphate based nerve agents. Support vector machines serve the purpose of data

extraction, pre-processing and classification of chemical biological agent [23]. MEMS based

sensor arrays have been used to detect nerve agents such as tabun and sarin, with a sensitivity

of 4 and 26 parts per billion (ppb) respectively. Blister agents such as sulphur mustard were

detected with a sensitivity of 16 ppb. Oxides of tin and titanium were deposited as nanostructured

thin films which act as the sensing element. These sensor arrays have demonstrated stability,

high signal to noise ratio to the relevant chemical warfare agent [24].

Optical fibres - Optical fibres have been used in sensing application. The fibre is turned into a

sensor by coating the end with sensing materials or by removing the cladding and coating it with

the sensing material. The sensing material used is primarily polymers containing chemically

active fluorescent dyes. The presence of a target agent causes a change in the polarity of the dye

which further leads to a change in the wavelength [12]. These optical fibres have been used to

detect explosives such as TNT at a sensitivity of 10-15 ppb, which is comparable to 1 ppb

sensitivity of a dog’s nose for the same agent. The sensitivity achieved was for a closed chamber

however, field trials were not as successful in demonstrating the same result [25].

Cantilevers - Microcantilevers are similar in appearance to diving boards, and are machined from

silicon or other materials. The length of these can vary from 100-200 microns and the thickness

between 0.3 - 1 microns. Microcantilevers offer sensitivity at least an order of magnitude higher

than QCM and SAW based sensors for chemical agents sensing [3]. Piezo resistive micro

cantilever based sensors have been demonstrated to have excellent detection capabilities for

chemical and explosive vapour detection. The cantilevers are coated with 4nm Ti film, 20nm gold

layer and 4-mercaptobenzoic acid self assembled monolayer. Detection of dimethyl

methylphosphonate (DMMP), a stimulant for the nerve agents was demonstrated with parts per

trillion detection capability within 10 seconds of exposure [26].

Chemiresistors - Chemiresistors are sensors that monitor a change in the resistance

continuously with exposure to vapours. Carbon nanotubes have been used for organic vapour

sensing. Single walled carbon nanotubes with diameter of 15-30 nm have been demonstrated as

- 29 -

effective sensors for nerve gas agents Sarin and Soman. A network of films 1-2 microns thick on

a polyethylene terephthalate (PET) substrate can detect traces of chemical agent vapours with a

sensitivity of 25 ppm. Strong sensors responses were obtained that were not affected by

environmental conditions such as air quality and humidity does not interfere significantly [27].

Single strand DNA along with single walled carbon nanotubes field effect transistors have been

used to detect chemical warfare agents. These sensors have show high sensitivity and stability

up to 50 cycles of operation [28]. Detection of V type nerve agent has been experimentally

demonstrated using carbon nanotubes. The detection is based on enzyme catalyzed hydrolysis of

nerve agents and amperometric detection of thiol containing hydrolysis product that is performed

at the carbon nanotube modified screen printed electrode. The sensitivity demonstrated for such

sensors is 258 ppb [29].

Chemicapacitive sensor - A chemicapacitive sensor is a capacitor that has selectively

absorbing materials such as a polymer, as a dielectric. Volatile organic compounds are absorbed

into dielectric, changing the permittivity leading to an increase or decrease in the capacitance.

Polymer dielectrics are a type of chemicapacitive sensor that are used for detecting chemical

warfare agents. These demonstrate a sensitivity of detection of 100 ppm for toxic industrial

solvents and 1 ppm for chemical warfare agent as well as explosives [30]. Chemicapacitive

sensors for toxic industrial chemicals have demonstrated a sensitivity of 0.0006 – 720 ppm for

analyte such as carbyl for the lower limit and carbon disulphide for the higher limit [31].

Spectroscopic Methods - Nerve gas agents such as sarin, soman, tabun, and VX, along with

blister agents such as mustard gas, and lewisite were compared for their detection using

techniques such as gas detection tube, flame photometric detector, ion mobility spectrometer,

surface acoustic wave detector, photo ionisation detector, Fourier- transform infrared

spectroscopy, gas chromatography – mass spectrometry for chemical warfare agents. Similar

comparative study for biological warfare agents such as flow cytometry, bioluminescence

detection, lateral flow immunoassay. Figure 1 below demonstrates the shortcomings of each of

these techniques for onsite detection, according to the volatility and molecular weight. Some

techniques proved to be suitable in detection of certain analytes while others resulted in false

positives or a slow response to the nerve agent [32].

- 30 -

Figure CW.1 – Performance of onsite chemical and biological threat detection [32]

In another study chemical warfare agents were comparatively detected by different analytical

techniques such as gas chromatography–infrared detection–mass spectral detection (GC–IR–

MS); liquid chromatography–mass spectrometry (LC–MS); nuclear magnetic resonance (NMR)

using the nuclei H, C and P; and gas chromatography–atomic emission detection (GC–AED). It

was observed in the study that each of the technique gave good identification of some of the

components such as amines, phosphorous, or sulphur. Each of these techniques also missed out

on several major components [33]. Separation and detection of organophosphorus type nerve

agents by gas chromatography with inductively coupled plasma mass spectrometry has been

demonstrated, less than 5 picogram sensitivity to river water and soil contamination [34].

Techniques such as laser photo-acoustic spectroscopy have demonstrated a detection of sarin

with a sensitivity of 1.2 ppb, and with extremely low false positives of less than 1 in 1,000,000 in

the presence of other trace gases [35]. Micro-X Ray fluorescence has unique capabilities suited

to high throughput screening of combinatorial libraries of chemical warfare agents. High

throughput screening of nerve agents such as VX has been demonstrated in nanogram

quantities. These could be coupled with other spectroscopic techniques such as Raman and IR to

give additional information [36]. Contamination of portable water with nerve agent Sarin can have

serious consequences such as bronchospasm and even death under conditions if enough

- 31 -

quantity is consumed. Diffuse reflectance infrared spectrum investigation, using nanoparticulate

magnesium oxide as a preconcentration medium produced a sensitivity of 98 ppb for Sarin

detection in water [37].

Laser induced breakdown spectroscopy has been used as a versatile sensory platform for

detecting chemical agents, biological agents such as anthrax and improvised explosive devices.

This sensory platform can be couple with robotic platforms for toxic environments and with fiber

optics. The LIBS technique has demonstrated effectively to distinguish chemical agents

especially in the soil [38]. Phosphorus containing nerve agent stimulant detection with LIBS has

been demonstrated at a range of 20 meters [39].

Nanomaterials - Nanocomposites of tin oxide and indium oxide have been demonstrated as

excellent material for semiconductor gas sensors for toxic industrial gases. Addition of additives is

shown to have enhanced sensitivity and selectivity performance significantly [40]. Toxic and

explosive industrial gas such as methane, butane, propane, liquefied petroleum gas, and carbon

monooxide have been detected by nanostructured tin oxide sensors. The sensor arrays

demonstrated have a detection capability of less than 100 parts per million [6]. Tin, Niobium and

Vanadium Oxide thin films have been developed for the detection of nerve gas agents Sarin. For

agglomerates of the size of 40 nm, a sensitivity of 70 ppb was demonstrated. The stability of such

thin films for gas sensing applications is being further researched [41].

Challenges of chemical sensing – Integration of large number of sensors in a limited area,

providing high sensitivity, and selectivity of the toxin. Another challenge is the environmental

conditions, whereby it is much easier to measure parameter in a laboratory condition as opposed

to ambient air or in water [4]. Shortcomings of conductive polymers are that surface morphology

is not predictable, therefore the surface conductivity and the sensing function are not reproducible

between batches, and more importantly it sensitivity to water vapour [4, 7]. There is no one

device that meets the need of onsite detection of both chemical and warfare agents for onsite

detection [32]. Shortcomings of chemical agents sensors are that no polymer coating for sensors

can display complete selectivity to all possible interferents [22]. The costs of using mass

spectrometry, gas chromatography, ion mobility spectrometry are expensive and not as easy to

use as electronic noses [26].

1.1.4. State of Research and Development

- 32 -

The sections give an overview of the technology development in relation to a specific technology.

Fundamental Research is defined for this purpose as research with no particular goals of

commercialisation. Applied Research is defined as research conducted in academia and industry

directed towards a specific purpose and application. Prototype has been defined as Applied

Research or Fundamental Research that has found a potential market application. Technologies

that are in the field trial state are defined as those that are in the process of commercialisation,

and are being tested. Deployed nanotechnologies are those that have found an early stage

market. Mass Market has been defined as those technologies that have been adopted by large

population and are attractive high growth markets. The technologies have been mentioned are

those mentioned in the literature review for chemical detection. The scale of readiness mentioned

ranges from fundamental research to mass market. The spread of research and development for

a particular method indicates different applications, threat agents and devices that are being

developed. A validation of their status is necessary from the economic and other technology

sectors perspective. Table CW.2 gives an overview of all chemical weapon detection

technologies enabled by nanomaterials.

Table CW. 2 – Comparative Research and Development Status for chemical weapons detection

Fundame

ntal

Research

Applied

Researc

h

Prototyp

e

Field Trials / Pilot

plant ( Pre-

commercialisatio

n)

Deployed

(Commercial

ised)

Mass

Market

Conducti

ve

polymers

Field

effect

transistor

s

Piezoelec

tric

Surface

acoustic

wave

Flexural

plate

- 33 -

wave

Sensor

arrays

Optical

fibres

Cantileve

rs

Chemires

istors

Chemica

pacitors

Spectros

c-opic

methods

Nanomat

erials for

detection

1.1.5 Additional demand for research

Specific research needs were mentioned in the literature relating to different detection aspects

are as follows:

SWCNT based sensors for detection of nerve gas agents have to be optimised for their

performance. Performance optimisation is needed for tenability, stability, detection limit

and elimination of false positives [27].

No onsite detection equipment for capsaicin, lacrymating ingredient in pepper spray, and

snake toxins is available. Further research is required in detection methods for these

toxins [32].

LIBS – further research is needed in reducing the number of false positives and

negatives. Research is also needed in refining the model to include a range of materials

and selection of detection limits [39].

Research on properties of paper and its scanning through the postal system has also

been suggested to protect civilians from biological or chemical attack [42].

- 34 -

1.1.6 Applications and Perspectives

In the expert engagement process for the technology segment, the following perspectives were

observed:

• Funding research and development for detection of CBRNE and Narcotics was

considered very important for society and economy of Europe.

• The most important drivers for research and development of ‘detection of CBRNE and

Narcotics’ were considered technological and social impact. The technological drivers

relate to cost, performance, efficiency and absence of solutions. Other secondary drivers

were indicated as competitive advantage in conflict situations, safety, productivity gains

and regional security policy.

• The main drivers for R&D of ‘chemical detection’ were mentioned to be ‘cost of sensors,

devices and instrumentation’, ‘sensitivity’, ‘time for detection’, ‘life time of operation’ and

accuracy of detection’. Other secondary drivers were identified as ‘size of detectors’,

‘mobility of detection unit’ and ‘integration of detection platform’.

• The main barriers to research and development of ‘detection of CBRNE and Narcotics’

were mentioned as ‘availability of finance to early stage companies’ and ‘inadequate

technology transfer from Universities’. Secondary barriers indicated were ‘intellectual

property conflicts’, ‘lack of tax incentives’ and ‘lack of supportive government policy’.

• Qualitative responses indicated to meet the challenges of ‘availability of finance’, EU

needs to consider dual commercial use of security technology as the market was

relatively smaller than US. While trends in US are towards government driven technology

that is validated, EU grants are inadequate for proving technology. It was suggested that

government validation of systems was necessary as laboratory systems not scaled for

field use.

• The main barriers to R&D of ‘chemical detection’ were indicated as ‘inadequate research

funding’, ‘lack of skilled personnel availability’ and ‘lack of reproducible results’. Other

secondary barriers were mentioned to be ‘poor detection limit’, ‘failure in integrating

devices’, ‘robustness of field trials’ and ‘limited target acquisition’.

- 35 -

• The most important functionality for detection were indicated as ‘sensitivity of specie

being detected’, ‘reproducibility of accurate results’, ‘retaining functionality in wide

operating conditions’, and ‘long operating life with minimum maintenance’. ‘Collection and

sampling’ and ‘specificity’ were considered other very important functional requirement.

• Other secondary desirable functionalities were indicated as ‘stability of detection’,

‘multifunctionality’, ‘signal transduction’, ‘minimal sample preparation’, ‘integration of

detector into monitoring unit’ and ‘low cost’. ‘Reversibility’ was considered relatively less

important functionality.

• The application trends were mentioned as:

- The charecteristics of a detector application are mission and scenario dependent.

- Development of portable and sensitive detection devices. There is a present lack

of portable instruments with good sensing characteristics. Trend is towards

miniaturising chemical sensors.

- Application development trend directed toward broad based technologies

primarily for transportation hubs.

- Development of nanostructured functional materials and interfaces for high

performance detection of chemical agents.

- Systems integration is a gap in technology development for detection.

- Low false positives and low false negatives are the most important application

requirement.

- Response time was entirely application dependent. While in border situation 2-3

seconds response time is ideal, several seconds at the port, it should be within

milliseconds in crowded locations.

- Functionalities such as detection limit are dependent on application and scenario

where ppm might be adequate.

- 36 -

- Operational constraints were identified as environmental changes such as

temperature, humidity and large number of interferants. Mobility of detection

device, and calibration for temperature and humidity were mentioned as

constraints.

- Other operational constraints were mentioned to be calibration of measurement,

skills and interpretation needed from operator. The need for simpler interfaces

that are tailored for operation setting was mentioned specially for less qualified

operators.

- Processing constraints were identified as lack of basic understanding to control

nanomaterials in a precise manner.

- Improving cost effectiveness by controlled large scale production and improve

laboratory infrastructure for mass scale production.

- Long development life cycles for applications are characterised by delivering

scientific results, establishing performance and establishing cost effective

performance of detection technologies.

• The sensing methods for chemical detection that are presently deployed are

chemicapacitive, chemiresistors, surface acoustic wave, sensor arrays, optical fibres,

mass based, and spectroscopy based detection.

• Methods for chemical detection that are expected to be deployed in the next 5 years are

nanomaterials based detectors, conductive polymers, field effect transistors, and

piezoelectric sensors. Certain types of sensor arrays and specific optical fibres are also

expected to be in the market in 5 years.

• Application issues for surface acoustic wave sensors were mentioned to be sensitivity

and functionalisation. Development barriers for sensor arrays were mentioned as

availability of diverse sensors at the required selectivity and sensitivity. Limitations of

spectroscopy as a practical field technique were also mentioned. Reproducibility,

selectivity and pattern recognition were development challenges for a majority of sensors.

The factors determining the uptake of conductive polymers were mentioned as

reproducibility, stability, durability and selectivity. For field effect transistors it was

- 37 -

mentioned as robustness, selectivity and sensitivity. Important factors in uptake of piezo -

electric sensors were mentioned to be robustness and stability.

• Methods for chemical detection that are expected to take over 10 years to be deployed

were mentioned to be cantilevers.

• The very attractive and relatively higher growth markets were expected to be sensor

arrays, biosensors, surface acoustic wave, flexural plate wave, chemiresistors and

nanomaterials for detectors.

• The moderately attractive growth markets were expected to be field effect transistors,

piezoelectric transistors, optical fibres and cantilever based detection.

• North America was considered relatively better than Europe which was considered better

than Asia for fundamental and applied research, industrial technology development and

commercialisation. While Asia was considered better for cost effectiveness for

technology, EU was considered better for governmental policy for innovation. Qualitative

responses mentioned that EU research was complimentary to US for chemical detection.

It was mentioned that Europe had existing sensor deployment relatively better than other

world regions, it lacked research and development for future leadership.

• Qualitative suggestions on improvement of capabilities were :

- collaborative research between security agencies, academia and industry

- encouraging tax exemptions

- basic research to understand nanomaterials better

- technology transition from science to implemented demonstrators is gap that

needs to be addressed

- creation of multinational, multidisciplinary fund for development

- creating a centre for standardised testing for different sensors

- 38 -

The theme of integrated platform for detection of chemical, biological, explosive, radiological

and nuclear threats was conducted at Dusseldorf in March 2009. The following outcome and

recommendations resulted from the discussion:

• Technology was not sufficiently advanced to achieve single platform detection.

• An integrated modular system that focuses on Chemical, Biological and Explosive as

one unit and Radiological-Nuclear detection as a separate module is a better

approach.

• One of the main weaknesses for CBRNE detection was considered to be systems

integration. It was suggested that a statement of requirements to be produced taking

nanotechnology into consideration.

• Accuracy and reliability of measurement was considered to be most important

characteristic. Reproducibility of measurements and operating life of sensor were

considered to be poor for modular systems of detection.

• The cost of false positives are very high, therefore operational definition should be

developed on a case by case basis for a modular system.

• The need for greater fundamental research in understanding the sensing mechanism

was emphasised.

• It was recommended that communication between materials and sensing community

be improved in order to create mutual awareness of technical breakthroughs.

• The first area of application is expected to be transportation hub for such a modular

system.

• Technology penetration and application driven by state for CBRNE detection.

• It was recommended that sensor requirements for the EU are critically examined.

- 39 -

1.1.7 Current Situation within EU

NANOS4 was a research and technology development project which was completed last year.

The objective of the project was the development of metal oxide gas sensing system based on

mesoscopic sensor. The thin film sensors were to be developed using lithography techniques, for

applications in transport safety, monitoring environmental variables. TERAEYE is another

framework project that aims to develop an innovative range of inspecting passive range of

systems based on Terahertz wave detection. The two dimensional array of detectors are

expected to detect harmful explosive, biological, and chemical agents at airports, railways hubs

and civilian zones.

The following framework 7 projects have been funded by the European Commission in the

Security theme that are relevant to biological threats detection:

• CBRNE related testing and certification facilities - a networking strategy to strengthen

cooperation and knowledge exchange within Europe (CREATIF) was initiated early in

2009. The project aims to create a network of product testing facilities for CBRNE

detection [43].

• Integrated mobile security kit (IMSK) was initiated in 2008. The objective of the project is

to combine technology solutions from Detection of CBRNE, area surveillance, and check

point control for additional sensitive security locations. The sensor data is expected to be

integrated with communication and data module to a command centre [44].

The following Preparatory Action for Security Research Funded projects were funded by the

European Commission and are relevant to chemical detection:

• European Security: High level study on threats responses and relevant technologies

(ESSTRT). The support action project has provided a comprehensive overview of

necessary responses to security challenges. These include technologies for detecting

chemical weapons and hazardous materials at airports and travel hubs [45].

• The active terahertz imaging for security (TERASEC) project, that aims to develop

terahertz detection. The detection of threats, explosives, pathogens and chemicals in

person, luggage or post were the focus of the project. The Terahertz imaging systems

were developed and evaluated in the 24 month period [46].

- 40 -

• Hazardous Material Localisation and Person Tracking (HAMLeT) project demonstrated

an indoor security system using sensors to give real time decision information. This was

done by classifying, tracking and localising potential threats. Chemical sensors were

used for detection of hazardous materials such as explosives [47].

• On-line monitoring of drinking water for public security from deliberate or accidental

contamination (WATERSAFE) project aimed to use nanotechnologies in sensing and

detoxification to protect drinking water systems for potential terrorist attacks or accidental

spillage [48].

- 41 -

1.2.1 Title – Biological

Detection of Biological threats

Keywords: anthrax, ricin, virus, bacteria, toxin, nucleic acid, biomolecular, immuno-detection,

biosensors, nanowires, nanotubes, terahertz, optical methods

1.2.2 Definition

Biological threats have been defined as those viruses, bacteria and toxins which deliberately

spread can cause serious harm to humans, animals and plants. 23 bacteria, 43 viruses and 14

toxins have been reported by security agencies as threats. Table BW.1 provides a list of some of

these biological threats [49].

Table BW.1 – List of commonly cited harmful biological agents

Name of biological agent

1 botulinium toxin

2 shiga toxin

3 diptheria toxin

4

anthrax - Bacillus

anthracis (anthrax)

5 ricin

6 ovalbumin

7

Staphylococcal Enterotoxin B

(SEB)

8 Yersinia pestis (plague)

9 Variola major (smallpox)

1.2.3 Short Description

Detection of biological threats, which could be used against citizens and agricultural produce,

involves the recognition of bacteria, viruses and toxins. The identification methods based on

- 42 -

nucleic acid and immuno-based methods are used in detecting has been mentioned in the

literature. These have also been used in food testing, clinical and environmental applications [50].

Table BW.2 – A selection of detection of commonly known bacterial pathogens as cited in the

journal paper [50]

Biorecognition molecules Target Type of assay

Estimated time of assay (h)

Sensitivity (no. of targets)

Specificity

Nuclei

c acid

pst gene probes

and primers

Yersinia

pestis

5% nuclease

fluorogenic assay

2.5 h 3–30

cells

Very

high

Heat stable toxin

gene (ST-gene)

E. coli PCR-ELISA; color

amplified PCR

(CAPS)

3.5 h 270 cfu High

Genomic DNA;

Escherichia coli

E. coli

and

lambda

phage ,

Lambda phage

Molecular combing,

scanning force

microscopy

2 h 103 cells High

Universal and

specific 16s

rRNA primers

B.

subtilis,

Y. pestis

and E.

coli

Multiplex PCR

followed by gel

electrophoresis

3 h ND (5 ml

of soil)

High

Immun

o-

assay

s

Fluorescently

labeled MAb

Salmonel

la

typhimuri

um

Flow cytometry 40 min 103

cells:ml of

milk &

egg

High

Fluorescently

labeled PAb to

0157 antigen E. coli

0157:H7

Antibody-direct

Epifluorescent filter

technique

(Ab-DEFT)

3 h 104–105

cfu:g

feces

High

- 43 -

Table BW.3 – A selection of recognition techniques for detection of pathogenic viruses as cited in

a journal paper [50]

Biorecognition molecules Target Type of assay

Estimated time of assay (h)

Sensitivity (no. of targets)

Specificity

Nucleic

acid

Biotinylated

primers for gag gene and

internal

standard

control

HIV-1

RNA:DN

A

QC-PCR followed by

amplicon capture,

probe hybridization

and

Luminometry

4h 100 Very

high

quantit

ative

Biotinylated

primers for pol

gene

HIV-1

RNA

PCR followed by

amplicon capture and

colorimetry

3 h 20 virions Very

high

Primers for

immediate

early genes

Active

human

cytomeg

alovirus

(hCMV)

In situ PCR followed

by in situ colorimetry

4 h 100 High

Primers for

immediate

early genes

hCMV Nested PCR followed

by gel

electrophoresis

4 h 5 virions High

Primers and

biotinylated

probes

Hepatitis

C virus

(HCV)

PCR based,

digoxigenin labled

amplicons are

captured by

biotinylated probes 3 h

10–100

virions

Very

high

Digioxigenin

labeled

riboprobe

targeting non-

coding

sequence

Enterovir

uses

Dot blot hybridization

and

chemiluminescent

detection 2.5 h

104–105

TCID High

Digioxigenin Polioviru Dot blot hybridization 2.5 h 103–104 High

- 44 -

labeled Vp1

probe

ses

serotyop

es

and

chemiluminescent

detection

TCID

Immun

o-

assays

Fluorescein

labeled human

recombinant

Fab (rFab)

Cells

infected

with

herpes

simplex

virus

(HSV)

Indirect

immunofluorescence

2.5 h ND High

Fluorescein

labeled murine

monoclonal Ab

to HSV

Cells

infected

with HSV

Direct

immunofluorescence

2 h

indirect

ND (less

than

High

Latex bound

antibody to

Cytomeg

alovirus

(CMV)

Latex agglutination,

visual assay

10 min 1012 High

IgM antibody to

CMV

Enzyme immuno

assay

10 min 106 High

Antibody

HAV

Immuno electron

microscopy

8 h 104–105

virions/ml

Moder

ate

Radio labeled

antibody HAV Radioimmunoassay

2 h 105–106

virions/ml

Moder

ate

Self assembled bilayers of Cu2+/L-cysteine have been coated on gold surfaces are used to

detect biological agents in microcantilever sensors. Dimethyl methyl phosphonate was used as a

sarin nerve gas stimulant in these tests [51].

Label free biosensors also known as optical biosensors are based on direct measurements of a

change taking place during a biochemical reaction on the surface of a transducer [52]. Ricin has

been detected using optical biosensors within 30 minutes to a detection limit of 10ng/ml. The

advantages optical biosensors offer is rapid screening and multi-analyte detection. The main

disadvantage for these sensors is the reduced sensitivity for the rapid screening assays [53].

- 45 -

Portable fibre optic biosensors have been demonstrated in the detection of Staphylococcal

Enterotoxin B. These biosensors have been demonstrated in the compact, light weight portable

identification system. The multi-channel identification system is based on simultaneous

fluorescence immunoassays on the surface of polystyrene fibre optic probes [54].

NASA has demonstrated the nanotechnology based biosensors that can be used to detect

pathogens such as anthrax. These sensors are based on carbon nanofibres and the licensed

technology is being commercialised by Early Warning Inc. Electrical signals are measured in

these sensors to identify the presence of a pathogen. These sensors are equipped with

microfludics as well that provides the advantage of field testing, allowing detection within 30

minutes [55].

Aptamers are functional RNA oligonucleotides that are used for sensing biologicial agents. These

are also DNA based. Aptamers based biosensors have been reported to be good for security

applications. Aptamers based biosensors are relatively immature, in relation to immunoassays,

due to the limited availability of aptamers and knowledge of surface immobilization [56]. Single

walled carbon nanotubes based field effect transistors, has been demonstrated to monitor

aptamers – protein affinity binding processes. These offer an advantage over immunological

assays due to their small size in monitoring protein- protein interactions [57].

Array Biosensors have been used to detect targets such as staphylococcal enterotoxin B (SEB),

ricin toxin, cholera toxin, mouse IgG and Bacillus globigii (anthrax spore simulant). Prototype for

monitoring postal sorting machines was demonstrated to be successful. The array biosensors

provide the advantage of being specific and non-destructive [58].

Inhibition of enzyme acetylcholinesterase has been the basis of detecting organophosphate

compounds due to high specificity and selectivity. The development of single thiocholine enzyme

based biosensor has been reported in the literature using screen printed carbon electrodes doped

with cobalt phthalocyanine. The sensors were observed to be fabricated using

electropolymerisation and ablation with ultrasound. Detection limits in the order of 1 * 10-17M were

experimentally reported for dichlorvos, parathion and azinphos. In a separate experiment the

same detection limit was reported for paraoxon. The biosensors were reported to have

application in environmental monitoring [59,60].

Biosensors based on acetylcholinesterase functionalised carbon nanotubes have been

demonstrated in detecting organophosphorus compounds. These sensors have shown excellent

- 46 -

limits of detection (0.145 ppb), good precision, electrode to electrode stability, and reproducibility

[61].

Metallic nanowires striped with gold, silver and nickel nanoparticles in a suspended format have

been used to identify biological warfare agents such as anthrax, smallpox, ricin and botulinum.

Each nanowire relating to a particular antibody detects a pathogen. The made advantage offered

by this method of detection is the ability to have up to 100 different striped nanowires which

reduce analysis time significant for multiple analytes [62].

Kane et al. have demonstrated the use of peptide bound carbon nanotubes in detecting toxins

such as anthrax, and deactivating the anthrax toxin by using invisible and near infrared light.

Carbon nanotubes coatings maybe applied as a thin coating on a range on surfaces [63]. SERS

enhancements have been used to detect microorganisms using colloidal metal suspension [64].

Terahertz imaging has been demonstrated for anthrax stimulant bacillus cereus in postal

envelopes [65]. The need for research in detection methods of biological threats was driven by

the anthrax spores distribution through the postal services in the United States. Laser induced

breakdown spectroscopy (LIBS) is a technique that uses light induced from a laser induced

microplasma to determine the composition of the sample, based on elemental and molecular

emission intensity. The main advantages of this technique are high sensitivity, selectivity and

minimal sample preparation. LIBS have been demonstrated to have been effectively used in the

detection of bacillus subtilis and ovalbumin. Experimental research has established the

effectiveness of this method with few false positive or false negatives [66].

1.2.4 State of Research and Development

The sections give an overview of the technology development in relation to a specific technology.

Fundamental Research is defined for this purpose as research with no particular goals of

commercialisation. Applied Research is defined as research conducted in academia and industry

directed towards a specific purpose and application. Prototype has been defined as Applied

Research or Fundamental Research that has found a potential market application. Technologies

that are in the field trial state are defined as those that are in the process of commercialisation,

and are being tested. Deployed nanotechnologies are those that have found an early stage

market. Mass Market has been defined as those technologies that have been adopted by large

population and are attractive high growth markets. The scale of readiness mentioned ranges from

fundamental research to mass market. The spread of development across the readiness level is

- 47 -

an indication of various detection methods, research and development effort for different threat

agents using varied biological means. A validation of their status is necessary from the economic

and other technology sectors perspective. The table BW.4 below gives an overview of technology

developments in relation to specific enabling technologies for biological threats detection.

Table BW.4 – Comparative Research and Development Status for category of biological threats

detection

Fundame

ntal

Research

Applied

Researc

h

Prototy

pe

Field Trials / Pilot

plant ( Pre-

commercialisatio

n)

Deployed

(Commercial

ised)

Mass

Market

Nucleic

Acid

based

Sensing

Immunoa

ssay

sensing

Optical

biosenso

rs

Nanowire

Nanotub

e

Spectros

copy

1.2.5 Additional demand for research

Specific research needs were mentioned in the literature relating to different detection aspects as

follows:

Leveraging telecommunications in sensing of biological warfare agents has been

identified as an applied research need. Linking of sensors, detectors and inspection

systems into a communication and management network similar to air traffic control has

been suggested [49].

- 48 -

Research on properties of paper and its scanning through the postal system has also

been suggested to protect civilians from biological or chemical attack [67].

1.2.6 Applications and Perspectives

In the expert engagement process for the technology segment, the following perspectives were

observed:

• Funding research and development for detection of CBRNE and Narcotics was

considered very important for society and economy of Europe.

• The most important drivers for research and development of ‘detection of CBRNE and

Narcotics’ were considered technological and social impact. The technological drivers

relate to cost, performance, efficiency and absence of solutions. Other secondary drivers

were indicated as competitive advantage in conflict situations, safety, productivity gains

and regional security policy.

• The main drivers for R&D of ‘biological detection’ were mentioned to be ‘cost of sensors,

devices and instrumentation’, ‘sensitivity’, ‘time for detection’, ‘size of detectors’, ‘mobility

of detection unit’, and ‘accuracy of detection’. Other secondary drivers were identified as

‘integration of detection platform’, and ‘life time of operation’

• The main barriers to research and development of ‘detection of CBRNE and Narcotics’

were mentioned as ‘availability of finance to early stage companies’ and ‘inadequate

technology transfer from Universities’. Secondary barriers indicated were ‘intellectual

property conflicts’, ‘lack of tax incentives’ and ‘lack of supportive government policy’.

• Qualitative responses indicated to meet the challenges of ‘availability of finance’, EU

needs to consider dual commercial use of security technology as the market was

relatively smaller than US. While trends in US are towards government driven technology

that is validated, EU grants are inadequate for proving technology. It was suggested that

government validation of systems was necessary as laboratory systems not scaled for

field use.

- 49 -

• The main barriers to R&D of ‘biological detection’ were indicated as ‘inadequate research

funding’, ‘lack of reproducible results’, ‘failure in integrating devices’ and ‘poor detection

limit’. Other secondary barriers were mentioned to be ‘inadequate skilled personnel’, ‘lack

of equipment and testing facility’ and ‘robustness of field trials’.

• ‘Collection and sampling’, ‘integration of detector into monitoring unit’, ‘continuous

operation’ and ‘specificity’ were considered important functional requirement. Other

important functionality for detection were indicated as ‘sensitivity of specie being

detected’, ‘reproducibility of accurate results’, ‘retaining functionality in wide operating

conditions’, and ‘long operating life with minimum maintenance’.

• Other secondary desirable functionalities for detection were indicated as ‘stability of

detection material’, ‘reversibility’, ‘multifunctionality’, ‘signal transduction’, ‘minimal sample

preparation’, and ‘low cost’. ‘Reversibility’ was considered relatively less important

functionality.

• The application trends were mentioned as:

- The charecteristics of a detector application are mission and scenario dependent.

- Development of portable and sensitive detection devices. There is a present lack

of portable instruments with good sensing characteristics. Trend is towards

miniaturising biological sensor systems.

- Application development trend directed toward broad based technologies

primarily for transportation hubs.

- Development of nanostructured functional materials and interfaces for high

performance detection of biological agents.

- Systems integration is a gap in technology development for biological detection.

Along with system issues, performance issues for sensors were also mentioned.

- Low false positives and low false negatives are the most important application

requirement.

- 50 -

- Qualitative responses mentioned that getting the sample into the device,

concentrating and analysing is a development challenge.

- In-situ forensics application demand has been mentioned.

- Lack of data sharing from field trials has been mentioned as a constraint for

example by water companies.

- Operational constraints were identified as environmental changes such as

temperature, humidity and large number of interferants. Mobility of detection

device, and calibration for temperature and humidity were mentioned as

constraints.

- Other operational constraints were mentioned to be calibration of measurement,

skills and interpretation needed from operator.

- Processing constraints were identified as lack of basic understanding to control

nanomaterials in a precise manner.

- Improving cost effectiveness by controlled large scale production and improve

laboratory infrastructure for mass scale production.

- Long development life cycles for applications are characterised by delivering

scientific results, establishing performance and establishing cost effective

performance of detection technologies.

- Nanotoxicology was considered an important issue therefore development of

appropriate risk assessment methods is necessary.

• The sensing methods for biological detection that are presently deployed are nucleic

acid, immunoassays, optical biosensors and spectroscopy.

• Methods for biological detection that are expected to be deployed between 5 - 10 years

are nanowires, and nanotubes based sensors.

• Development challenges for immunoassays were mentioned to be field practicability,

durability of sensing surface, sample handling and cost. For nanotubes sensors,

- 51 -

economical production of nanotubes was considered to a development issue to be

addressed. Other development issues and critical factors for nanotubes and nanowires

sensors were mentioned to be reproducibility, sensitivity, selectivity and pattern

recognition. For spectroscopic techniques, miniaturising the system was considered to be

the most challenging aspect.

• The very attractive and relatively higher growth market for biological detection was

expected to be nucleic acid based and optical biosensors.

• The moderately attractive future growth markets for biological detection were expected to

be immunoassays and nanowires.

• North America was considered relatively better than Europe which was considered better

than Asia for fundamental and applied research, industrial technology development and

commercialisation for the Detection sub-sector. While Asia was considered better for cost

effectiveness for technology, EU was considered better for governmental policy for

innovation.

• Qualitative responses indicated that US was considered to be far advanced than Europe

in Biological detection. Korea, Taiwan, Japan and Singapore were conducting

considerable research. Notable advances have been made in China. Research funding

was mentioned to be dispersed and effort was ill directed. US was considered good for

commercialisation but increasingly Asia is becoming better. It was mentioned that Europe

had existing sensor deployment relatively better than other world regions, it lacked

research and development for future leadership.

• Qualitative suggestions on improvement of capabilities were suggested as:

- collaborative research between security agencies, academia and industry

- encouraging tax exemptions

- basic research to understand nanomaterials better

- greater need for biochemical basic and applied research

- 52 -

- technology transition from science to implemented demonstrators is gap that needs to

be addressed.

- creation of thematic networks to improve coordination of research and development

activity

- development of novel solution for sample collection and identification of a wide range of

threats

- creation of multinational, multidisciplinary fund for development

- creating a centre for standardised testing for different sensors

The theme of integrated platform for detection of chemical, biological, explosive, radiological

and nuclear threats was conducted at Dusseldorf in March 2009. The following outcome and

recommendations resulted from the discussion:

• Technology was not sufficiently advanced to achieve single platform detection.

• An integrated modular system that focuses on Chemical, Biological and Explosive as

one unit and Radiological-Nuclear detection as a separate module is a better

approach.

• One of the main weaknesses for CBRNE detection was considered to be systems

integration. It was suggested that a statement of requirements to be produced taking

nanotechnology into consideration.

• Accuracy and reliability of measurement was considered to be most important

characteristic. Reproducibility of measurements and operating life of sensor were

considered to be poor for modular systems of detection.

• The cost of false positives are very high, therefore operational definition should be

developed on a case by case basis for a modular system.

• The need for greater fundamental research in understanding the sensing mechanism

was emphasised.

- 53 -

• It was recommended that communication between materials and sensing community

be improved in order to create mutual awareness of technical breakthroughs.

• The first area of application is expected to be transportation hub for such a modular

system.

• Technology penetration and application driven by state for CBRNE detection.

• It was recommended the technology readiness level for biological agents should be

assessed on a case by case basis for the specific threat agent and medium of

propagation.

• It was recommended that sensor requirements for the EU are critically examined.

1.2.7 Current Situation within EU

TERAEYE is another framework project that aims to develop an innovative range of inspecting

passive range of systems based on Terahertz wave detection. The two dimensional array of

detectors are expected to detect harmful explosive, biological, and chemical agents at airports,

railways hubs and civilian zones. DINAMICS is a framework 6 project that aims to develop an

integrated cost-effective nano-biological sensor for detection of bioterrorist activities. The project

is developing a lab on a chip device that will detect pathogens in the water supply.

The following framework 7 projects have been funded by the European Commission in the

Security theme that are relevant to biological threats detection:

• CBRNE related testing and certification facilities - a networking strategy to strengthen

cooperation and knowledge exchange within Europe (CREATIF) was initiated early in

2009. The project aims to create a network of product testing facilities for CBRNE

detection [43].

• Integrated mobile security kit (IMSK) was initiated in 2008. The objective of the project is

to combine technology solutions from Detection of CBRNE, area surveillance, and check

point control for additional sensitive security locations. The sensor data is expected to be

integrated with communication and data module to a command centre [44].

- 54 -

The following completed Preparatory Action for Security Research projects, were funded by the

European Commission and are relevant to biological detection:

• European Security: High level study on threats responses and relevant technologies

(ESSTRT). The support action project has provided a comprehensive overview of

necessary responses to security challenges. These include technologies for detecting

biological threats and hazardous materials at airports and travel hubs [45].

• The active terahertz imaging for security (TERASEC) project, that aims to develop

terahertz detection. The detection of threats, explosives, pathogens and chemicals in

person, luggage or post were the focus of the project. The Terahertz imaging systems

were developed and evaluated in the 24 month period [46].

• Assessment of the quantity, identity, viability, origin and dispersion of airborne micro-

organisms for application in crisis management tools (AEROBATICS) project aimed to

develop a sensing system for biological threats detection. The project aimed to quantify

the origin of micro-organism, analyse the micro-organism, and develop predictive model

tools [68].

• Bioterrorism resilience, research, reaction-supporting activity promoting co-operation to

assess the bio threat and organise a collective and comprehensive response for EU

society and citizens bio security (BIO3R) project aims at improving preparedness for

bioterrorism. It aimed to identify operational requirements, countermeasures against

biological attack (detection and therapeutic) and resilience, ethical and legal issues [69].

• Biological Optical Detection (BODE) project aimed to address the necessities of

developing a reliable and accurate detection tool for biological threats for stand-off

applications using LIDAR. The project identified functional and operational requirements,

proposed specifications, and produced a demonstrator [70].

• On-line monitoring of drinking water for public security from deliberate or accidental

contamination (WATERSAFE) project aimed to use nanotechnologies in sensing and

detoxification to protect drinking water systems for potential terrorist attacks or accidental

spillage [48].

- 55 -

1.3.1 Title - Radiological and Nuclear

Detection of Radiological and nuclear weapons

Keywords: alpha particles, beta rays, gamma rays, high energy photons, high energy electrons,

radiation monitoring, plastic scintillators, pure crystal scintillators, solid state devices, nuclear

resonance fluorescence, nanophosphor, nanocomposite

1.3.2 Definition of Technology Segment

Nuclear weapons and radiological dispersal devices illegitimately smuggled across the European

borders present a significant threat to civilian population. Radiological dispersal devices (also

know as ‘dirty bombs’) are capable of dispersing highly radioactive particles over large densely

populated areas. Alpha particles (equivalent of a helium nucleus), beta rays (high energy

electrons) and gamma rays (high energy photons) are detected by devices to warn of the

presence of a nuclear weapon or radiological dispersive device [71].

1.3.3 Short Description

International smuggling of weapons grade nuclear material presents a significant security

challenge. Between 1993 and 2004, the International Atomic Energy Agency has reported 18

incidents that related to smuggling of weapons grade nuclear materials. The proliferation of

nuclear weapons can take place through the borders at ports, airports, road passengers and

through the postal system. A tactical or improvised nuclear weapon would be small enough to be

transported in modular containers. It was reported that 25 kilograms of highly enriched uranium or

4 kilograms of plutonium-239 would be adequate for a nuclear explosive device. A significant

challenge is presented by dirty bombs, which would present a significant challenge to health of

civilians. Americum-241, californium-252, cesium–137, cobalt-60, iridium–192, and strontium-90

are radioactive species that could possibly be used for a dirty bomb. The radioactive isotopes

californium-252 and americium–241, are used in the oil industry and smoke detectors

respectively, therefore are easy to obtain for a dirty bomb [72]. Weapon grade plutonium and

highly enriched uranium can also be used for radiological dispersal devices. Radiological

dispersal devices can thus contain a variety of radioactive species that emit gamma rays,

neutrons and/or bremsstrahlung radiation.

- 56 -

Radiation monitoring is largely done by detecting gamma rays emitted by radioactive materials.

The gamma rays cover a spectrum of energies. Gamma rays passing through matter deposit a

part of their energy resulting in electrons that can be detected. One method of detection of

photons in a detector is a process called scintillation. Plastic scintillators, pure crystal scintillators,

and solid state devices are used for detecting gamma radiation. The drawback of plastic

scintillators is the low energy absorption due to the low density of the material. As a result the

instruments using such detectors cannot identify the radioactive material accurately. Pure crystal

scintillators and solid state devices are relatively better at absorbing all the energy of gamma rays

due to their higher density and atomic number. Radioactive isotopes such as strontium-90 emit

beta rays, which when shielded produce bremsstrahlung radiation which can be detected by the

same methods as gamma rays. Weapon grade plutonium and highly enriched uranium are

relatively less radioactive with respect to gamma ray emission in comparison to other isotopes,

therefore making them more difficult to detect. Neutrons are also emitted by weapon grade

plutonium, often making detection easier due to the low natural background from cosmic

radiation. The neutron detectors function by detection of protons released from nuclei struck by

neutrons, of fission daughters or by measuring gamma rays, electrons and other charged

particles. Uranium isotopes emit alpha particles and gamma rays, and not as many neutrons [72].

A number of strategic tools are used in the detection of radiation such as radiation portal

monitoring equipment, personal radiation detectors, hand held detectors and x-rays systems for

imaging of shielding. Radiation detection systems can be passive or active. Passive systems for

detection of radiation include radiation portal monitoring equipment, mobile systems, hand held,

backpack and belt monitoring systems, all of which have been deployed. Mobile x-ray and fixed

systems have been used for penetration of cargo containers for suspected cargo. Plutonium and

a few other radioactive materials emit neutron and tus neutrons are of particular interest in

detection applications at border crossing [73].

Radiation portal monitoring equipment has been deployed for border crossing and port

application in detection of illicit nuclear material. Detectors of gamma rays based on

polyvinyltoluene (PVT) and thallium doped crystalline sodium iodide have been demonstrated and

deployed. For passive screening of gamma rays, the energy range of interest for detection was

between 20 keV to 3 MeV [74]. A comparison of radiation portal monitoring equipment for border

security was done using gamma ray and neutron detectors. A comparison of polyvinyltoluene and

thallium doped crystalline sodium iodide for vehicle based radiation portal monitoring has also

been evaluated in the literature. The spectral capability of NaI(Tl) is superior to PVT for isotopic

identification, though the cost of NaI(Tl) has been reported to be much higher than PVT. A range

of environmental and operational factors determine the suitability of a detector in different

- 57 -

operating scenarios. Each detector type offers some advantages for various operating conditions

of portal monitoring systems [75].

Energy based alarm algorithms with enhanced sensitivity over gross counting have been

implemented for radiation portal monitoring equipment. The energy information obtained from

plastic scintillators can be used to distinguish between naturally occurring radioactive material

and special nuclear material. The energy based algorithm was considered to be a much desired

improvement in detection over gross count algorithms. One of the main limitations of radioaction

portal monitoring systems is the presence of naturally occurring radioactive isotopes that can

present a significant operational challenge [73,76].

Nuclear weapons detection in transportation cargo has been demonstrated with a range of

techniques, including both passive and active detection. The photo-fission of neutron emission

induced by gamma rays forms the basis of one active detection approach. The technique and its

effectiveness has been demonstrated for radioactive material in simulated shipping containers

and air-cargo [77]. Detection of nuclear weapons in cargo has been demonstrated using a pulsed

beam of neutrons, that produce fission events and detection of their fissionable material is done

from the beta delayed neutron emission or beta delayed high-energy gamma radiation. This is

another of the several active interrogation detection methods, and has been demonstrated for

simulated shipping cargo [78].

Nuclear Resonance fluorescence, another potential active interrogation technique, has been

demonstrated in the detection of isotopes of uranium in a laboratory. The basis of the method is a

unique signal that is relevant to each nuclei. The technique combined with effective algorithms

has been demonstrated in the laboratory as a possible method that may be applicable to

detection of material in sea containers, truck containers, trucks and other vehicles [79].

Monitoring of radioactive xenon in air has been used to detect nuclear weapons explosions as

part of the worldwide network of the Comprehensive Test Ban Treaty verification effort. A

prototype single phoswich detector has been used to detect beta particles and gamma rays from

radioxenon isotopes [80].High resolution inductively coupled plasma mass spectrometry and

accelerator mass spectrometry have been demonstrated in detecting ultra low level of uranium

isotopes in marine environments. The uranium isotope signature provides valuable information on

origin of uranium. The method has useful applications in monitoring radioactivity in depleted

uranium environments and undeclared nuclear activity or movement of nuclear material [81].

- 58 -

Detection of radioisotopes using a distributed sensor network, as opposed to central fixed

systems, has been proposed and developed. These distributed sensor network, coupled with a

monitoring portal has been demonstrated. The sensor array consisted of sodium iodide

scintillators that were connected to a platform for processing of gamma counts. The performance

of the array was reported to be higher than that of a single detector, though that is a controversial

claim. The advantage of this proof of concept is that it may be inexpensive, further research is

aimed at increasing sensitivity and developing an integrated platform for chemical and biological

threats [71].

The use of various detectors for radioactive species has been mentioned earlier. A system for

simultaneous detection of radiation species such as x-rays, gamma rays, neutrons and minimum

ionising particles has been observed in the literature. The sensitivity of the scintillators in the

research was achieved using nano-sized particles, dopants and extruded plastic material. Three

different type of detectors have been described, which identify specie of radiation. Nano-sized

particles of lithium have been used in neutron detectors. The wavelength shifting fibre absorbs

scintillator light at a wavelength and re-emitting it at a higher wavelength to better match the

photodetector used [82].

The use of nanoscale materials for detection of radiation is expected to overcome single crystal

based detectors limitations such as size and cooling requirements to very low temperatures.

Nanophosphor has been mentioned as a candidate material for scintillators and detectors.

Cerium doped lanthanum halides (less than 10nm in diameter) have also been mentioned as

suitable candidates for scintillators nanocomposites. Due to their brightness and short decay

lifetime they are very effective in gamma ray detection. Scaling up of the synthesis of cerium

lanthanum fluoride to kilogram quantities remains a further research challenge that remains to be

addressed [83].

Enhanced optical properties of nanocomposites made of existing scintillator materials have been

reported in the literature. The nanocomposites offer enhanced light output, decreased costs and

scalability have been demonstrated at the proof of principle stage. Cerium doped lanthanum

fluoride has been synthesized nanoparticles having a size of 25 -100nm, have shown a three

times increase in light intensity as compared to bulk material used for scintillation. Further

research in the area was identified as synthesis of nanophosphors as scintillators and their

fabrication as nanocomposites. Measurement of absolute light yield and linearity of the

nanocomposite were mentioned as challenges for characterization [84].

- 59 -

Solid state semiconductor detectors offer advantages over gas filled detectors and scintillator

detectors due to excellent energy resolution and higher efficiency. High purity germanium

detectors are the gold standard for gamma ray detection but require cryogenic temperatures. A

number of semiconductors have been suggested for application such as cadmium zinc telluride

(CZT), cadmium telluride, gallium arsenide, indium phosphide, mercury iodide and thallium

bromide. CZT offer advantages due to its wide band gap, high resistivity and commercial

availability. The higher resistivity is a desirable characteristic as it decreases noise level thus

improving the resolution of detection. A synthesis process for producing nanowire arrays of CZT

has been mentioned in the literature for detecting gamma ray radiation. In the process CZT was

electrodeposited on a titanium dioxide nanotubular template. Stacks of CZTs with very high

resistivity were fabricated and connected. It was experimentally demonstrated that the flow in the

current increased when exposed to a radiation source. The potential of nanowires being used as

a radiation detector at room temperature was at a much lower bias applied in relation to bulk

material detectors. Very high sensitivity to radiation was experimentally demonstrated [85].

Other recent methods have been mentioned in the literature such as the Neutron Imaging

Camera for detection of weapon grade plutonium at borders. The camera is based on three

dimensional image tracker developed initially for applications in gamma ray astrophysics. The

working principle is based on measuring the energy and position in three dimensions of the

charged particles moving through the camera medium. The application was successful

demonstrated to identify radiation at stand-off distances and in the presence of other background

emissions [86]. An Electronic Neutron Dosimeter has been mentioned in the literature for

detecting radiation. It uses scintillators on a pair of photomultiplier tube minimizing the power

consumption and increasing operational times. The dosimeter has been prototyped with results

exceeding electronic neutron dosimeter standards [87].

Microcantilevers were reported to detect an alpha particle as it impinges on an electrically

insulated metallic surface by undergoing a deflection of a few nanometres. The particle is

detected by a shift in the resonance frequency due to electrostatic forces. A single alpha particle

can be detected using this method, however other conventional methods have been shown to

have higher sensitivity as compared to these detectors [88].

One of the main challenges of detecting these threat radioactive materials is the shielding using

lead and other dense materials for gamma rays, and hydrogenous materials for neutrons. An

additional challenge is interference from medical isotopes and other slightly radioactive, but

relatively innocuous materials such as smoke detectors, fertilizers, television sets, abrasives and

glazed ceramics. The approach of using X-ray scanners has been used in the United States, for

any shielding that may be used to hide radiological weapons. Other methods such as active

- 60 -

interrogations using gamma ray and neutrons have also been reported. As mentioned above,

these induce fission in uranium and plutonium, resulting in gamma rays and neutrons that are

detected [72].

1.3.4 State of Research and Development

The sections give an overview of the technology development in relation to a specific technology.

Fundamental Research is defined for this purpose as research with no particular goals of

commercialisation. Applied Research is defined as research conducted in academia and industry

directed towards a specific purpose and application. Prototype has been defined as Applied

Research or Fundamental Research that has found a potential market application. Technologies

that are in the field trial state are defined as those that are in the process of commercialisation,

and are being tested. Deployed nanotechnologies are those that have found an early stage

market. Mass Market has been defined as those technologies that have been adopted by large

population and are attractive high growth markets. The technologies have been mentioned are

those mentioned in the literature review for nuclear and radiological weapons detection. The

scale of readiness mentioned ranges from fundamental research to mass market. The range of

activity indicates various methods and materials being used at different stages of readiness. The

table RNW.1 below gives an overview of enabling technologies for detection of radiological

disperse device and nuclear weapons in relation to their development status.

Table RNW.1 - Technology and its Development Status for radiological disperse devices and

nuclear weapons detection

Fundame

ntal

Research

Applied

Researc

h

Prototy

pe

Field Trials / Pilot

plant ( Pre-

commercialisatio

n)

Deployed

(Commercial

ised)

Mass

Market

Radiation

portal

monitorin

g

Sensor

Array

Spectro

metric

- 61 -

method

Nuclear

Resonan

ce

fluroesce

nce

Nanomat

eri-al

based

Detector

s

1.3.5 Additional demand for research

Specific research needs were mentioned in the literature relating to different detection aspects

are as follows:

Materials research needs for CBRNE sensors has been identified as developing sensors

with the ability to detect and warn. Sensor capabilities to allow functionality at stand off

distances in order to protect personnel in conflict situations. Enhanced understanding of

the energetic behaviour of weapons and its packaging modes has been suggested.

Enhanced and portable imaging techniques have been identified as a research need for

civilian areas with high shipping container traffic. Integration of imaging and detection

techniques with mass transportation has also been mentioned [89].

1.3.6. Applications and Perspectives

In the expert engagement process for the technology segment, the following perspectives were

observed:

• Funding research and development for detection of CBRNE and Narcotics was

considered very important for society and economy of Europe.

• The most important drivers for research and development of ‘detection of CBRNE and

Narcotics’ were considered technological and social impact. The technological drivers

relate to cost, performance, efficiency and absence of solutions. Other secondary drivers

- 62 -

were indicated as operational advantage in conflict situations, safety, productivity gains

and regional security policy.

• The main drivers for R&D of ‘radiological and nuclear detection’ were mentioned to be

‘mobility of detection unit’, ‘cost of sensors, devices and instruments’, and ‘accuracy of

detection’. Other secondary drivers were ‘time for detection’, ‘integration of detection

platform’, and ‘life time of operation’

• The main barriers to research and development of ‘detection of CBRNE and Narcotics’

were mentioned as ‘availability of finance to early stage companies’ and ‘inadequate

technology transfer from Universities’. Secondary barriers indicated were ‘intellectual

property conflicts’, ‘lack of tax incentives’ and ‘lack of supportive government policy’.

• Qualitative responses indicated to meet the challenges of ‘availability of finance’, EU

needs to consider dual commercial use of security technology as the market was

relatively smaller than US. While trends in US are towards government driven technology

that is validated, EU grants are inadequate for proving technology. It was suggested that

government validation of systems was necessary as laboratory systems not scaled for

field use.

• The main barriers to R&D of ‘radiological and nuclear detection’ were indicated as

‘lack of equipment and testing facility’, and ‘limited supporting policies’. Other secondary

barriers were indicated as ‘lack of reproducible results’, ‘failure in integrating devices’

and ‘robustness of field trials’.

• Qualitative responses suggested the different approach towards funding research in

radiological and nuclear weapons from different agencies. Short term 2-3 year view was

detrimental to research efforts.

• The desirable characteristic of a radiological nuclear detector was mentioned

inexpensive, excellent energy resolution, thermally stable, physically robust, and usable

for a long operating life.

• The application trends were mentioned as:

- Radiological and nuclear detectors are physically large. Physical miniaturisation

is not possible therefore improved material performance is being investigated.

- 63 -

- Increased energy analysis for radiation detection has led to higher costs. The

direction of research is towards extracting more information from less expensive

technological solution.

- Response time was entirely application dependent. While in border situation 2-3

seconds response time is ideal, longer at trading ports, it should be within

milliseconds in crowded locations.

- Operational factors important in radiological- nuclear detection are time, distance

and shielding. Time of detection is for seconds, and distance is based on

packages and physical sizes of vehicles. Shielding is considered to be the main

factor for planning against different scenarios.

- Results from technique such as Nuclear Resonance fluorescence were

considered poor for laboratory condition. In real situations with shielding they

may not produce predictable results like those from active induced fission by

neutrons or gamma rays.

- One of the main application problems was considered to be absence of an

accelerator which can address the lack of tunable, variable energy, continuous

source of gamma rays with the right energy. The present sources are pulsed thus

resulting signal to noise ratio are not feasible for application of technique.

- CeF3 material was mentioned to have been developed as proof of principle. The

limitation for CeF3 was reiterated to result from the low light output. It was

mentioned that scale up to 500 gram/batch synthesis of CeF3 had been

achieved.

- There are limitations in understanding of the production process.

- All detector materials show limitations and advantages over each other.

- Application areas where nanomaterials can add value would be nanoparticle

inclusion in plastic for plastic scintillators.

- Nano-additives could play a role in gamma radiation detectors

- 64 -

- Nanotechnology could enhance light detection system for photo tube detection

and gas detectors.

• The sensing methods for radiation and nuclear weapons detection that are presently

deployed are radiation portal monitoring and spectroscopy.

• Methods for radiological and nuclear detection that are expected to be deployed after at

least 5 years of development are sensor arrays for radiation detection and nanomaterials

based detectors.

• The factors determining uptake of radiation detection technology are physical size, price,

robustness, resolution. Response time, count rate (some scintillators are slower than

others), and relationship to material properties.

• The moderately attractive future growth markets for explosives detection were expected

to be radiation portal monitoring, sensor arrays for radiation and spectroscopy methods.

• Investment in technology and evaluation of product markets is important for radiation

detection. One company holding sole monopoly in a market through patents is

counterproductive for development in security.

• Basic research for radiation detection was perceived to be better in Europe than North

America, mainly concentrated in Universities. National laboratories in US were focused

on technology development and transfer for radiation detection. Europe was considered

particularly weak for technology transfer.

The theme of integrated platform for detection of chemical, biological, explosive, radiological

and nuclear threats was conducted at Dusseldorf in March 2009. The following outcome and

recommendations resulted from the discussion:

• Technology was not sufficiently advanced to achieve single platform detection.

• An integrated modular system that focuses on Chemical, Biological and Explosive as

one unit and Radiological-Nuclear detection as a separate module is a better

approach.

- 65 -

• One of the main weaknesses for CBRNE detection was considered to be systems

integration. It was suggested that a statement of requirements to be produced taking

nanotechnology into consideration.

• Accuracy and reliability of measurement was considered to be most important

characteristic. Reproducibility of measurements and operating life of sensor were

considered to be poor for modular systems of detection.

• The cost of false positives are very high, therefore operational definition should be

developed on a case by case basis for a modular system.

• The need for greater fundamental research in understanding the sensing mechanism

was emphasised.

• It was recommended that communication between materials and sensing community

be improved in order to create mutual awareness of technical breakthroughs.

• The first area of application is expected to be transportation hub for such a modular

system.

• Technology penetration and application driven by state regulation for CBRNE

detection.

1.3.7 Current Situation within EU

The following Preparatory Action for Security Research Funded projects were funded by the

European Commission and are relevant to radiation and nuclear detection:

• European Security: High level study on threats responses and relevant technologies

(ESSTRT). The support action project has provided a comprehensive overview of

necessary responses to security challenges. These include technologies for detecting

nuclear weapons and radiological disperse devices at airports and travel hubs. The

project also investigated technologies that could develop smart containers, and border

security against weapons [45].

• CBRNE related testing and certification facilities - a networking strategy to strengthen

cooperation and knowledge exchange within Europe (CREATIF) was initiated early in

- 66 -

2009. The project aims to create a network of product testing facilities for CBRNE

detection [43].

The following framework 7 projects funded under the security theme by the European

Commission have relevance to the radiological-nuclear detection.

• Cooperation across Europe for Cd(Zn)Te based security instruments (COCAE) project

initiated in 2008 is focused on spectroscopic measurements for detecting radioactivity

using Cd(Zn)Te crystals [90].

• Integrated mobile security kit (IMSK) was initiated in 2008. The objective of the project is

to combine technology solutions from Detection of CBRNE, area surveillance, and check

point control for additional sensitive security locations. The sensor data is expected to be

integrated with communication and data module to a command centre [44].

- 67 -

1.4.1 Title – Explosives

Detection of Explosives

Keywords: explosive, TNT, DNT, Semtax, RDX, Nitroglycerin, electrochemical, mass sensor, fibre

optics, photoluminescence, spectroscopy, terahertz, SERS, biosensors, nanosensors, nanowires,

nanotubes

1.4.2 Definition of Technology Segment

Detection of explosives in cargo, luggage, mail, vehicles, aircrafts and on personnel presents a

significant challenge for civilian security. Three main means of detection are in deployment or in

advanced stages of development. The first method relies on detecting traces quantities of volatile

compounds of explosives, in vapour form or deposits on surfaces. The second method used is

penetrating radiation that interacts with an explosive element producing a characteristic signal on

the detector. The third method used combines one or more methods as platforms for detection. In

this approach one detection technique compensates for the weakness of another [91].

More than a 100 explosive categories have been identified in the literature. Table EW.1 provides

a list of explosives that are commonly used. The explosive characteristics used to identify the

explosive are geometry, material density, elemental composition and vapour detection. The

properties used for identifying explosives and drugs have been mentioned in the literature. For

explosives the constituents in general has moderate carbon, high to moderate nitrogen, very high

to high oxygen and very high density [92].

Table EW.1 - List of common used explosives and their chemical formula [91]

Explosive Name/contents

Standard TNT 2,4,6-Trinitrotoluene

RDX

1,3,5-Trinitro-1,3,5-

triazacyclohexane

PETN Pentaerythritol tetra nitrate

NG Nitroglycerin (glycerol trinitrate)

- 68 -

EGDN Ethylene glycol dinitrate

Improvised ANFO Ammonium nitrate + fuel oil

Urea nitrate Urea nitrate

TATP Triacetone triperoxide

Plastic C-4 C-4 RDX + plasticizer

Semtex

Semtex RDX + PETN +

plasticizer

Detasheet Detasheet PETN + plasticizer

1.4.3 Short Description

There are a number of methods used to detect trace vapour such as ion-mobility spectrometry,

mass spectrometry and electronic noses. Probing radiation techniques include X-ray techniques,

millimetre wave imaging, terahertz technology, neutron gamma ray techniques, and nuclear

quadrapole resonance. The third method uses two or more technology solutions in a

complimentary way [91]. Techniques such as X- rays, gamma rays, millimetre imaging have been

used for detecting explosives and weapons [92]. Based on the type of measurement obtained,

explosive sensors are largely categorised into – electrochemical, mass, optical sensors and

biosensors [93].

Electrochemical sensors - Electrochemical sensors convey changes in the environment through

changes in current, when chemicals interact with the electrodes. Three main types of

electrochemical sensors are in use namely, potentiometric, amperometric, and conductometric.

Such sensors can be used for the detection of TNT in marine environments [94]. Detection of

explosives has also been demonstrated with amperometric bioelectrochemical sensors [95].

These sensors have limited sensitivity, and need mobile electrolytes [93]. Nanocomposites of

metal nanoparticles with carbon nanotubes solubilised in Nafion have been demonstrated for the

detection of TNT and other nitroaromatic explosives [96]. Glassy carbon electrodes containing

copper nanoparticles and single walled carbon nanotubes have shown a reproducible detection

limit of 1 ppb. Glass carbon electrode modified by single walled carbon nanotubes has been

demonstrated to detect TNT [97].

Mass based sensors - Mass based sensors generally adsorb, chemicals on to the surface and

the change in mass is detected by the device. The detection of the explosive is done by a

- 69 -

travelling acoustic wave or by bending of the surface. Polymer films are used in fabrication SAW

sensors that are used for detecting explosives and explosive devices [98]. Sorbent coatings for

SAW sensors have demonstrated a DNT detection limit of less than 100 parts per trillion [99].

Fibre optic based sensors - Fibre optical sensors have been used for detecting explosives.

They rely on changes in frequency, or intensity of electromagnetic radiation for detection of

explosives [93]. Explosives such as DNT and DNB have been detected at low ppb level within

seconds using optical sensors that rely on changes in fluorescence properties [100]. Optic fibre

based explosive detection is based on defect free zeolite film, utilises a change in sensor

reflectivity on exposure. Such sensors have not demonstrated selectivity and sensing time is

about 200 seconds [101].

A number of spectrophotometric methods are used for detecting explosives such as absorption

based detection, photoluminescence based detection, fluorescence based detection, laser

induced breakdown spectroscopy and terahertz based detection [93]. Absorption based detection

based on the change in colour, has been demonstrated to detect nitrous explosives and explosive

related compounds. This method has demonstrated a detection limit of 0.2 ng for DNT [102 ].

Nanosized molybdenum hydrogen bronze react with TATP to change colour from dark blue to

yellow. The colour change property can be used both for titration neutralisation and for detection

of explosives [103].

Photoluminescence based detection - Photoluminescence based detection, is based on

monitoring the photoluminescence of a nanocrystalline porous silicon film that is exposed to an

analyte in flowing air stream. Nitro aromatic compound explosives have been detected using this

method [104]. Fluorescence based detection of explosives relies on quenching of fluorescence

when a target molecule is acquired. The advantage of this technique is the ability to detect from a

distance. Fluorescent sensory material spread over the suspected area is detected, which is

illuminated with fluorescent light identifying the explosive in question. Nitro aromatic explosives

have been detected with electron rich polymer semiconductors [105]. Fluorescence quenching

method using pyrene as fluorophore is applied for the detection of RDX, HMX, TNT, nitromethane

and ammonium nitrate [106]. Quantum dots of cadmium selnide with zinc sulphide shell have

been used to detect TNT [107]. Fluorescent nanofibrous membranes prepared by electro-

spinning have demonstrated very high sensitivity to trace vapours of TNT. Highly porous

structures of these nanofibres have been reported to provide it high sensitivity to analytes with

detection limit of 10 parts per billion [108]. Nanofibrous membranes have been reported to act as

both chemiresistor sensors and fluorescence quenched sensors. These sensors based on

- 70 -

conductive polymer nanotubes have uses in detection of explosive, biological and chemical

agents [109].

Spectroscopic methods - Explosives have been detected using techniques such as laser

induced breakdown spectroscopy. The explosive is detected by means of laser that is used to

create plasma over the explosive surface. High pulsed lasers have been demonstrated to create

plasma that is detected using an optical probe to determine the explosive material composition.

Detection of TNT on brass and molybdenum substrates and RDX on molybdenum substrates has

been demonstrated [110]. Nuclear Resonance fluorescence has been demonstrated in detection

of explosives using the signatures of carbon, hydrogen and oxygen of the elements. The

experimentally demonstrated technique offers advantages such as short detection times and high

probability of detection [111].

Terahertz detection –Terahertz explosive sensors are based on differential absorption. A

sample region is illuminated with two frequencies, chosen for a specific explosive, and to

maximise the contrast between presence and absence of an explosive. This technique has been

demonstrated as a detection tool for explosive and also identifying specifically the unique

terahertz spectral fingerprints of TNT, TDX, HMX, and Semtax [93]. Carbon nanotubes based

antennas for THz detection have been mentioned in the literature [112]. Potassium ions

interaction with carbon nanotubes have shown to induce a strong dielectric response. The binding

event causes the carbon nanotubes to vibrate at 0.4Tz. This effect has potentially applications as

a THz detector operating at room temperature [113].

Terahertz sensing for explosives detection at airports is being developed. A product demonstrator

in a portable unit with data processing has been produced [114]. Improvements in growth, design,

and characterisation of low temperature grown gallium arsenide photomixers has enabled its use

for sensing applications. An important component of these photomixers is nanoparticulates that

reduce the charge carrier lifetime to sub-picosecond therefore allowing optical mixing to terahertz

range. This approach is limited in the power output and device reliability [115]. This technique has

been demonstrated in detecting bombs and explosives in envelopes, clothes, luggage and soil

[116]. Terahertz method has been demonstrated to detect RDX and RDX related explosive when

are covered by opaque material [117]. One of the main challenges and limitations in Terahertz in

stand off detection has been reported to be environmental conditions and barrier materials as

picosecond pulsed measurement cannot be accurately measured. Quantum dot based detectors

have been claimed to be the detector of choice for terahertz detection. Multiband tunnelling

quantum dots infrared photo detectors, with nanometre dimensions, have been produced using

molecular beam epitaxy for security applications [118]. The design and characteristic of a indium

- 71 -

aluminium arsenide and gallium arsenide quantum dot which respond to terahertz radiation has

been mentioned in the literature [119].

Surface enhanced Raman scattering - Surface enhanced Raman scattering has been used to

detect vapours of explosives. Raman systems for detecting explosives such as RDX, TNT, and

PETN have been demonstrated at a distance of 50 metres and over [120]. Large enhancements

of Raman signals, using noble metal nanoparticles and nanostructures have been observed for

adsorbed molecules. Electrochemically roughened gold and silver substrates have been

demonstrated as a field SERS sensor to detect vapour signatures of TNT [121]. Enhancement of

TNT Raman signal on non-noble metal materials is being researched [122]. SERS enhancement

has been demonstrated for the detection of TNT using colloidal silver suspension. High sensitivity

was demonstrated in the experimental research with detection of limit at 10-15g for DNT and 10-

19g for TNT [123].

Cataluminescence - Cataluminescence is the emission of light during the catalytic oxidation of a

molecule on the surface of a solid state catalyst [124]. A sensor array based on

cataluminescence, using strontium, barium and aluminium carbonates as catalysts have been

demonstrated for explosive gas mixtures [125].

Biosensors - Biosensors are devices that integrate a biological element on a solid state surface,

enabling interaction with an analyte and signal transduction. Biological elements such as

peptides, enzymes, receptors, single strand DNA [93]. Detection of TNT and DNT has been

demonstrated using proteins immobilised on electrodes [126]. Immunoassays use antibodies as

recognition elements in biosensors. Electrochemiluminescent immunoassays have been

developed for TNT detection in which enzyme labelled antibodies are bound to paramagnetic

beads on the electrode surface are used. TNT has been detected with this method in 80s to a

sensitivity of 31 ppb [127]. Development and comparison of two immunoassays for detection of

TNT has been based on competitive inhibition [128].

Nanosensors - Nanosensors have been mentioned to be one of the most effective platforms for

detection of explosives. The most important characteristics of a trace explosive sensor are

sensitivity, selectivity, reversibility and real time operation. A number of sensing elements and

platforms have been mentioned for nanosensors platform such as micro-nano structures,

quantum dots, nanowires, nanotubes and nanobelts [129].

Selectivity to sensors is provided by coatings such as self assembled monolayers, polymers,

metal oxides and single stranded DNA. Important factors for consideration are response time and

- 72 -

recovery. Self assembled monolayers of 4 mercaptobenzoic acid are good for explosive vapour

detection [130]. 6-Mercaptonicotinic acid monolayer has been reported to produce good results

with TNT detection [131]. Molecular imprinted polymers for the detection of TNT have also been

developed and demonstrated [132].

Nanomechanical sensors have been considered an ideal platform for detection of explosives.

Molecular adsorption of vapour on the surface of the cantilever, results in bending of cantilever

structure, which is used to detect the presence of explosives. Piezoresistive cantilever deflection

leads to a change in the resistance which is measured. Beams coated with 4-MBA have been

demonstrated to detect TNT explosive vapours [133]. Nanoporus coatings tend to produce

micrometer responses in the presence of vapour phase TNT and DNT. A detection limit of 520

ppt was demonstrated [134].

A number of different approaches have been considered such as thermally induced

decomposition, have demonstrated a sensitivity of 40 picogram [135]. Another approach used is

photo thermal deflection spectroscopy, where a bimaterial cantilever demonstrates high

sensitivity to temperature changes. The bending of the cantilever results from absorbing the IR

energy on the surface of the explosive molecule [136]. Amplifying fluorescence polymers have

been successfully used in detection explosives. The adsorption of the explosive molecule on the

surface of the polymer leads to a change in the fluorescence characteristic. AFP’s with TNT

adsorbed on the surface continuously fluorescence under the ultraviolet light source. Sensors

based on thin films of AFP have been commercialised by Nomadics [137,138].

Cantilever based sensors have been used in detecting explosives by identifying compounds

trinitrotoluene (TNT), 2,4 dinitrotoluene (DNT); pentaerythritol tetranitrate (PETN), and

hexahydro-1,3,5-triazine (RDX). TNT is a commonly used explosive and DNT remains a by

product of TNT. PETN and RDX are high end explosives used for sabotaging aircrafts. The

detection of the explosive vapours was demonstrated. The sensitivity of microcantilevers in

detecting such explosives is approximately 14 part per trillion within 20 seconds. Active detection

of explosive vapours was allowed to deposit on a piezoresistive microcantilever which has been

detected using optical signals such as laser scattering [139,140,141].

Nanowires - Nanowires also provide an effective platform for sensing explosives. Interdigitated

electrode capacitors modified with single walled carbon nanotube has been demonstrated to

detect chemical vapours with high sensitivity. The change in capacitance is used to detect the

molecules and its class [142].

- 73 -

Table EW.2– Comparative assessment of the sensor performance used for detection of

explosives, as cited in review paper [93]

Sensor Type Field of application Explosive detected Detection limit

Electrochemical Soil samples RDX 0.12 ppm

Electrochemical Marine water TNT 25 ppb

Electrochemical Forensic laboratory DNB and TNT, 60 ppb for both

Electrochemical

Soil extract and

ground water

RDX, TNT, 2,4-

DNT, 2,3-DNT,

2,4-DNT

RDX 0.2 ppm, TNT 0.11

ppm, 2,4-DNT 0.15 ppm,

2,6-DNT 0.16 ppm, 2,3-

DNT-0.15 ppm

SAW Laboratory samples 2,4-DNT

SAW Laboratory samples DNT 92 ppt

SAW Laboratory samples 2,4-DNT, TNT

Micro cantilever

For detection of

explosive vapors PETN and RDX

A low femtogram (10−15

g)

Micro cantilever TNT 520 ppt

Optical

Field test (soil

samples) DNT 120 ppb

Optical (fiber optic

based)

Ground water and

soil extracts TNT and RDX 0.1 ppm

Optical

(photoluminescence

based) Air and sea water TNT, Picric acid

4 ppb for TNT vapor in air,

1.5 ppt for TNT in sea

water,

6 ppb for picric acid in sea

water

Optical (fluorescence

based) Laboratory samples

TNB, TNT, DNB,

tetryl, and

2,4-DNT

1 ppm for all these

explosives

Optical (fluorescence based)

TATP and

HMTD

2×10−6 mol L−1 for both

TATP and HMTD

Optical (fluorescence

based) Water samples DNP 1.0×10−6 mol L−1

- 74 -

Optical (LIBS) DNT

NB 40 ppb for DNT and

17–24 ppb for

nitrobenzene

Optical fiber (biosensor) Ground water TNT and RDX

0.05 ppb for both RDX and

TNT

Electrochemical

(biosensor) Laboratory samples TNT 31 ppb

Optical (immunosensor) Artificial sea water TNT 0.05 ppb

Electrochemical

(immunosensor)

Environmental

samples and clinical

assay TNT 1 ppt

Optical

(fluoroimmunoassay)

Soil and water

samples TNT

Optical (immunosensor) Laboratory samples TNT and RDX

450 fmol for TNT, 1 ppb for

RDX

Optical (immunosensor) Seawater TNT 250 ppt

Electrochemical

(immunosensor) Seawater TNT

2.5 ppb in saline buffer

and

25 ppb in seawater

Optical (SPR based

immunosensor)

On-site detection of

landmines TNP 10 ppt

Optical (SPR based

Immunosensor) Laboratory samples TNT 6 ppt

A combination of different sensor platforms and different optical modes has been suggested as

an optimal method for successfully detecting explosive trace vapours. Mass, stress and thermal

signals of TNT vapours measured by cantilevers are independent of one another and could

provide pattern recognition. Increased selectivity and sensitivity could also be achieved by

combining platforms in a single sensing unit that could measure different physical and chemical

properties. An example of such a combination would be SWCNT and cantilever. A SWCNT could

measure the electrical polarisation of explosive molecule adsorbed on its surface by change in

capacitance. The cantilever would determine the mass and stress measurements of the same

explosive molecule [129].

- 75 -

1.4.4 State of Research and Development

The sections give an overview of the technology development in relation to a specific technology.

Fundamental Research is defined for this purpose as research with no particular goals of

commercialisation. Applied Research is defined as research conducted in academia and industry

directed towards a specific purpose and application. Prototype has been defined as Applied

Research or Fundamental Research that has found a potential market application. Technologies

that are in the field trial state are defined as those that are in the process of commercialisation,

and are being tested. Deployed nanotechnologies are those that have found an early stage

market. Mass Market has been defined as those technologies that have been adopted by large

population and are attractive high growth markets. The technologies have been mentioned are

those mentioned in the literature review for chemical, biological, explosive, nuclear, radiological,

and narcotics detection. The scale of readiness mentioned ranges from fundamental research to

mass market. The span of activities for a particular sensing method represents the different

applications, nanomaterials used and threat agents detected. A validation of their status is

necessary from the economic and other technology sectors perspective. The table EW.3 below

gives an overview of the technology development in relation to enabling nanotechnologies for

explosives detection.

Table EW.3 - Technology and its Development Status for category of explosive weapons

detection

Fundamen

tal

Research

Applied

Research

Prototy

pe

Field Trials /

Pilot plant (

Pre-

commercialisati

on)

Deployed

(Commerciali

sed)

Mass

Market

Electroc-

hemical

Mass

based

Fibre

optic

Photolumi

ne-

scence

- 76 -

Spectrosc

opic

methods

Terahertz

detection

Surface

enhanced

Raman

scattering

Catalumin

isc-ence

Biosensor

s

Nanomec

ha-nical

sensors

Nanowire

s

1.4.5 Additional demand for research

Specific research needs were mentioned in the literature relating to different detection aspects

are as follows:

• Explosives detection in civilian zone can be done best with sensors that can be deployed

in mass number are miniature in size, selective and sensitive for detection, inexpensive

and can be mass produced [129].

• Low vapour pressure of the explosive molecules present a challenge in detection for

collection within an acceptable detection time. The concentration of a potential explosive

molecule decreases as source from the distance increases. Very low concentration of the

molecule being detected provides false positives. Research is needed in nanosensors for

trace explosives to integrate the sensing element, with vapour collection and pre-

concentration functionality [129].

• Research specific to microcantilever detection capabilities – detection of trace amounts of

multiple analytes from researching vapour concentration, controlling experimental

conditions, providing a wide variety of coatings for sufficient signal variation [130].

- 77 -

• Speed of detecting is a challenge for chemical, biological and radiological exposure. This

is essential for providing a response in the event of a nerve gas attack. Detection times of

seconds to minutes could not only limit the inhaled quantity but also the following

prophylactic action [130].

1.4.6 Applications and Perspectives

In the expert engagement process for the technology segment, the following perspectives were

observed:

• Funding research and development for detection of CBRNE and Narcotics was

considered very important for society and economy of Europe.

• The most important drivers for research and development of ‘detection of CBRNE and

Narcotics’ were considered technological and social impact. The technological drivers

relate to cost, performance, efficiency and absence of solutions. Other secondary drivers

were indicated as competitive advantage in conflict situations, safety, productivity gains

and regional security policy.

• The main drivers for R&D of ‘explosive detection’ were mentioned to be ‘cost of sensors,

devices and instrumentation’, ‘size of detectors’, ‘mobility of detection unit’, ‘life time of

operation’ and ‘accuracy of detection’. Other secondary drivers were identified as

‘integration of detection platform’, ‘sensitivity’, and ‘time for detection’.

• The main barriers to research and development of ‘detection of CBRNE and Narcotics’

were mentioned as ‘availability of finance to early stage companies’ and ‘inadequate

technology transfer from Universities’. Secondary barriers indicated were ‘intellectual

property conflicts’, ‘lack of tax incentives’ and ‘lack of supportive government policy’.

• Qualitative responses indicated to meet the challenges of ‘availability of finance’, EU

needs to consider dual commercial use of security technology as the market was

relatively smaller than US. While trends in US are towards government driven technology

that is validated, EU grants are inadequate for proving technology. It was suggested that

government validation of systems was necessary as laboratory systems not scaled for

field use.

- 78 -

• The main barriers to R&D of ‘explosive detection’ were indicated as ‘inadequate research

funding’, ‘lack of skilled personnel availability’ and ‘lack of reproducible results’. Other

secondary barriers were mentioned to be ‘poor detection limit’, ‘failure in integrating

devices’, ‘robustness of field trials’ and ‘inadequate skilled personnel’.

• The most important functionality for detection were indicated as ‘sensitivity of specie

being detected’, ‘reproducibility of accurate results’, ‘retaining functionality in wide

operating conditions’, and ‘long operating life with minimum maintenance’. ‘Collection and

sampling’ and ‘specificity’ were considered other very important functional requirement.

• Other secondary desirable functionalities for detection were indicated as ‘stability of

detection material’, ‘multifunctionality’, ‘signal transduction’, ‘minimal sample preparation’,

‘integration of detector into monitoring unit’ and ‘low cost’. ‘Reversibility’ was considered a

relatively less important functionality.

• The application trends were mentioned as:

- The charecteristics of a detector application are mission and scenario dependent.

- Development of portable and sensitive detection devices. There is a present lack

of portable instruments with good sensing characteristics.

- Application development trend directed toward broad based technologies

primarily for transportation hubs.

- Development of nanostructured functional materials and interfaces for high

performance detection of chemical agents.

- Systems integration is a gap in technology development for detection.

- Low false positives and low false negatives are the most important application

requirement.

- Response time was entirely application dependent. While in border situation 2-3

seconds response time is ideal, longer at trading ports, it should be within

milliseconds in crowded locations.

- 79 -

- Operational constraints were identified as environmental changes such as

temperature, humidity and large number of interferants. Mobility of detection

device, and calibration for temperature and humidity were mentioned as

constraints.

- Other operational constraints were mentioned to be calibration of measurement,

skills and interpretation needed from operator.

- Processing constraints were identified as lack of basic understanding to control

nanomaterials in a precise manner.

- Improving cost effectiveness by controlled large scale production and improve

laboratory infrastructure for mass scale production.

- Long development life cycles for applications are characterised by delivering

scientific results, establishing performance and establishing cost effective

performance of detection technologies.

• The deployment of detection methods for explosives was perceived to be:

sensing methods presently deployed are electrochemical, optical fibres,

mass based and spectroscopy based detection.

methods for deployment after 5 years of development are terahertz and

surface enhanced raman scattering.

methods expected to take over 10 years to be deployed were mentioned

to be nanowires, nanomechanical sensors, cataluminescence, and

biosensors.

• Development challenges for biosensors were mentioned to be reliability, long operating

life. Cost, sample handling, selectivity and robustness are factors which would determine

the uptake of biosensors. For terahertz the development challenge was considered to be

cost effectiveness. SERS and spectroscopy had limitations due be being laboratory

based methods. Cost and power are other issues to be addressed for spectroscopy.

Nanomechanical research challenge was mentioned to be interfacing between

- 80 -

mechanical and sensing function. Sensitivity, selectivity, reproducibility and pattern

recognition are factor which would determine the uptake of nanowires and

nanomechanical.

• The very attractive and relatively higher growth market for explosive detection was

perceived to be terahertz.

• The moderately attractive growth markets for explosives detection were expected to be

electrochemical, biosensors, mass based, surface enhanced raman scattering, optical

fibres, spectroscopy based detection and nanowires.

• North America was considered relatively better than Europe which was considered better

than Asia for fundamental and applied research, industrial technology development and

commercialisation for the Detection sub-sector. While Asia was considered better for cost

effectiveness for technology, EU was considered better for governmental policy for

innovation. Qualitative responses mentioned that EU research was complimentary to US

for explosive detection. It was mentioned that Europe had existing sensor deployment

relatively better than other world regions, it lacked research and development for future

leadership.

• Qualitative suggestions on improvement of capabilities were:

collaborative research between security agencies, academia and

industry

encouraging tax exemptions and basic research to understand

nanomaterials better.

technology transition from science to implemented demonstrators is gap

that needs to be addressed.

creation of multinational, multidisciplinary fund for development

creating a centre for standardised testing for different sensors

- 81 -

The theme of integrated platform for detection of chemical, biological, explosive, radiological

and nuclear threats was conducted at Dusseldorf in March 2009. The following outcome and

recommendations resulted from the discussion:

• Technology was not sufficiently advanced to achieve single platform detection.

• An integrated modular system that focuses on Chemical, Biological and Explosive as

one unit and Radiological-Nuclear detection as a separate module is a better

approach.

• One of the main weaknesses for CBRNE detection was considered to be systems

integration. It was suggested that a statement of requirements to be produced taking

nanotechnology into consideration.

• Accuracy and reliability of measurement was considered to be most important

characteristic. Reproducibility of measurements and operating life of sensor were

considered to be poor for modular systems of detection.

• The cost of false positives are very high, therefore operational definition should be

developed on a case by case basis for a modular system.

• The need for greater fundamental research in understanding the sensing mechanism

was emphasised.

• It was recommended that communication between materials and sensing community

be improved in order to create mutual awareness of technical breakthroughs.

• The first area of application is expected to be transportation hub for such a modular

system.

• Technology penetration and application driven by state for CBRNE detection.

• It was recommended that sensor requirements for the EU are critically examined.

- 82 -

1.4.7 Current Situation within EU

TERAEYE is another framework project that aims to develop an innovative range of inspecting

passive range of systems based on Terahertz wave detection. The two dimensional array of

detectors are expected to detect harmful explosive, biological, and chemical agents at airports,

railways hubs and civilian zones.

The following framework 7 projects have been funded by the European Commission in the

Security theme that are relevant to explosives detection:

• Optical technologies for the identification of explosives (OPTIX) project was initiated in

2008 to develop a system for stand-off detection of explosives based on LIBS, RAMAN

and IR [143].

• Localisation of threat substances in urban society (LOTUS) project was initiated in early

2009. The LOTUS project aims to create a system to detect the preparation of explosives

and drugs during preparation and production of a terrorist plot. This will be demonstrated

by detection using sensors and global infrastructure for positioning and networking [144].

• Underwater coastal sea surveyor (UNCOSS) project was initiated in 2008, aims to protect

the naval infrastructure against underwater improvised explosive devices. The objective

is to provide a non-destructive tool for the evaluation of underwater objects based on

neutron sensors [145].

• CBRNE related testing and certification facilities - a networking strategy to strengthen

cooperation and knowledge exchange within Europe (CREATIF) was initiated early in

2009. The project aims to create a network of product testing facilities for CBRNE

detection [43].

• Integrated mobile security kit (IMSK) was initiated in 2008. The objective of the project is

to combine technology solutions from Detection of CBRNE, area surveillance, and check

point control for additional sensitive security locations. The sensor data is expected to be

integrated with communication and data module to a command centre [44].

The following Preparatory Action for Security Research Funded projects were funded by the

European Commission and are relevant to explosives detection:

- 83 -

• European Security: High level study on threats responses and relevant technologies

(ESSTRT). The support action project has provided a comprehensive overview of

necessary responses to security challenges. These include technologies for detecting

weapons and hazardous materials at airports and travel hubs [45].

• The active terahertz imaging for security (TERASEC) project, that aims to develop

terahertz detection. The detection of threats, explosives, pathogens and chemicals in

person, luggage or post were the focus of the project. The Terahertz imaging systems

were developed and evaluated in the 24 month period [46].

• Secure Container Data Device Standardisation (SECCONDD) project aims to initiate

standardisation of technical interface between secure container or vehicle and a data

reader at a port or border crossing. The project is expected to identify any potential

threats from terrorist activity or insertion of contraband goods [146].

• Transport Infrastructures Protection System (TIPS) project aimed to address security of

mainline, subway and metro systems of European cities. The project addressed

technological solutions for safety of passengers against explosives along with the

communication infrastructure [147].

• Hazardous Material Localisation and Person Tracking (HAMLeT) project demonstrated

an indoor security system using sensors to give real time decision information. This was

done by classifying, tracking and localising potential threats. Chemical sensors were

used for detection of hazardous materials such as explosives [47].

• Integrated system for on-line trace explosives detection in solid and vapour state

(ISOTREX) project addresses trace explosive detection of high energy material. The

project investigated and development an instrument for particle and vapour detection for

airports, customers and central post-offices. The instrument was based on Laser Induced

Breakdown Spectroscopy and IR absorption methods [148 ].

- 84 -

1.5.1 Title - Narcotics

Detection of Narcotics

Keywords: cocaine, heroine, fentanyl, drugs, narcotics, spectrometry, SERS, gamma rays,

neutron analysis

1.5.2 Definition of Technology Segment

The international narcotics control board has produced a list of narcotics drugs under

international control that is included in Schedule I, II and IV. The exhaustive list also provides the

chemical formula and its chemical content of chemical substances considered illegal and under

international control. It also provides a list of those narcotic drugs that are exempt under some

provisions [149]. The segment covers detection of chemicals such as heroine, cocaine and

fentanyl.

1.5.3 Short Description

Fentanyl has been reported to be 40 times more potent than heroine and has been used as a

narcotic. Ion selective membrane electrodes have been reported as sensors for Fentanyl.

Polyvinyl chloride based membranes have been applied with negligible interference from other

chemicals to detect fentanyl citrate in injections [150].

A sea portable drug detection system can enable detecting threats such as drugs, explosives,

nuclear weapons and chemical weapons behind hidden compartments of maritime vessels has

been mentioned in the literature. Detection of gamma ray signature of chemicals in narcotics has

been demonstrated for maritime vessels using thermal neutron analysis and fast neutron

analysis. This is based on characteristic gamma rays generated by elements such as hydrogen,

nitrogen and chlorine capturing thermal neutrons. The man portable detection system has been

demonstrated for Heroin hydrochloride, Cocaine hydrochloride, Heroin, and Cocaine [151].

Commercially available ion mass spectrometry has been reported to have applications in

detection of drugs. Ions are produced through atmospheric pressure ionisation are pulsed

through an electric field to a collector, during which the time of flight is measured. The

advantages offered by this technique are its portability, selectivity, high sensitivity (parts per

- 85 -

billion) and low cost. The detector could potentially be used as a stand alone sensor or as an

online system [152].

Surface enhanced Raman scattering offers very high sensitivity to detection of drugs and

narcotics molecules. Physiological fluids such as blood, urine and saliva have been used in

analysis of narcotics [153]. Research in identification of cocaine, heroin, amphetamines, 1, 4-

benzodiazepines and various metabolites of the drugs has been conducted using SERS with high

performance liquid chromatography [154]. SERS has been combined with electrophoresis and

flow injection analysis to quantitatively analyse cyanide levels [155,156].

1.5.4 State of Research and Development

The section gives an overview of the technology development in relation to a specific technology.

Fundamental Research is defined for this purpose as research with no particular goals of

commercialisation. Applied Research is defined as research conducted in academia and industry

directed towards a specific purpose and application. Prototype has been defined as Applied

Research or Fundamental Research that has found a potential market application. Technologies

that are in the field trial state are defined as those that are in the process of commercialisation,

and are being tested. Deployed nanotechnologies are those that have found an early stage

market. Mass Market has been defined as those technologies that have been adopted by large

population and are attractive high growth markets. The technologies have been mentioned are

those mentioned in the literature review for narcotics detection. The scale of readiness mentioned

ranges from fundamental research to mass market. A validation of their status is necessary from

the economic and other technology sectors perspective. The enabling technologies for the

detection of narcotics, in relation to its development status have been mentioned in table N.1

below.

Table N.1 - Comparative Research and Development Status for narcotics detection

Fundame

ntal

Research

Applied

Researc

h

Prototy

pe

Field Trials / Pilot

plant ( Pre-

commercialisatio

n)

Deployed

(Commercial

ised)

Mass

Market

- 86 -

Membran

es

Thermal

neutron

analysis

Fast

neutron

analysis

Spectro

metric

methods

SERS

1.5.5 Additional demand for research

Additional demand for research was mentioned in further development of SERS based detection

of narcotics during the engagement process. Research directed towards quantitative aspects of

SERS and their improvement were considered desirable [157].

1.5.6 Applications and Perspectives

In the expert engagement process for the technology segment, the following perspectives were

observed:

• Funding research and development for detection of CBRNE and Narcotics was

considered very important for society and economy of Europe.

• The most important drivers for research and development of ‘detection of CBRNE and

Narcotics’ were considered technological and social impact. The technological drivers

relate to cost, performance, efficiency and absence of solutions. Other secondary drivers

were indicated as competitive advantage in conflict situations, safety, productivity gains

and regional security policy.

• The main drivers for R&D of ‘Narcotics detection’ were mentioned to be ‘cost of sensors,

devices and instrumentation’, ‘size of detectors’, and ‘sensitivity of detection’. Other

- 87 -

secondary drivers were mentioned as ‘mobility of detection unit’, ‘time of detection’, ‘life

time of operation’ and ‘accuracy of detection’.

• The main barriers to research and development of ‘detection of CBRNE and Narcotics’

were mentioned as ‘availability of finance to early stage companies’ and ‘inadequate

technology transfer from Universities’. Secondary barriers indicated were ‘access to

equipments, infrastructure and manufacturing facility’ and ‘intellectual property conflicts’.

Other barriers also mentioned were ‘lack of skilled personnel availability’, ‘lack of tax

incentives’ and ‘lack of supportive government policy’.

• Qualitative responses indicated to meet the challenges of ‘availability of finance’, EU

needs to consider dual commercial use of security technology as the market was

relatively smaller than US. While trends in US are towards government driven technology

that is validated, EU grants are inadequate for proving technology. It was suggested that

government validation of systems was necessary as laboratory systems not scaled for

field use.

• The main barriers to R&D of ‘Narcotics detection’ were indicated as ‘inadequate research

funding’, ‘failure in integrating devices’ and ‘lack of reproducible results’. Other secondary

barrier was mentioned to be ‘poor detection limit’.

• The most important functionality for detection were indicated as ‘sensitivity of specie

being detected’, ‘reproducibility of accurate results’, ‘retaining functionality in wide

operating conditions’, and ‘long operating life with minimum maintenance’.

• Other secondary desirable functionalities for detection were indicated as ‘stability of

detection material’, ‘reversibility’, ‘multifunctionality’, ‘signal transduction’, ‘minimal sample

preparation’, ‘integration of detector into monitoring unit’ and ‘low cost’.

• The application trends were mentioned as:

- Development of portable and sensitive detection devices. There is a present lack

of portable instruments with good sensing characteristics.

- Operational constraints were identified as environmental changes such as

temperature, humidity and large number of interferants. Mobility of detection

- 88 -

device, and calibration for temperature and humidity were mentioned as

constraints.

- Combining SERS detection and identification of narcotics with a separation

technique to address issues in reproducibility, retention of functionality and long

life. In a separation coupled system, the problems associated with SERS are

expected to be overcome.

- Other operational constraints were mentioned to be calibration of measurement,

skills and interpretation needed from operator.

• The sensing method for narcotics detection that is presently deployed is spectrometric

methods and bioassays for narcotics detection. Spectroscopy methods market was

considered to a moderate growth market. Miniaturisation of spectroscopic methods was

considered a development needs for enhanced application. Factors that would determine

uptake of the technology are size, cost and sample preparation.

• Method for narcotics detection that is expected to be deployed in the next 5 years is

surface enhanced raman scattering. The SERS detection market was consider a

moderate future growth market.

• Method for narcotics detection that is expected to take over 10 years to be deployed was

indicated to be based on membranes for detection.

• North America was considered relatively better than Europe which was considered better

than Asia for fundamental and applied research, industrial technology development and

commercialisation for the Detection sub-sector. While Asia was considered better for cost

effectiveness for technology, EU was considered better for governmental policy for

innovation.

1.5.7 Current Situation within EU

The following framework 7 project has been funded by the European Commission in the Security

theme that is relevant to narcotics:

- 89 -

• Localisation of threat substances in urban society (LOTUS) project was initiated in early

2009. The LOTUS project aims to create a system to detect the preparation of explosives

and drugs during preparation and production of a terrorist plot. This will be demonstrated

by detection using sensors and global infrastructure for positioning and networking [144].

- 90 -

2. Incident Support

2.1.1 Title – Neutralising CBRNE effect

Neutralising CBRNE effect

Keywords: neutralising, CBRNE effect, prophylaxis, antidote, organophosphorous compounds,

spectrometry, vaccines, sera, antinfectious medicine, drug delivery, diagnostics, nanoparticles,

biosensors, radionucleotides, polymer gels, biodegradable nanospheres, nanofiber, surgery,

implant, nanomaterials, nanocomposites

2.1.2 Definition of Technology Segment

The sub-segment addresses nanotechnology developments that deal with responding to an

attack on civilian population. The nanotechnology developments covered in this sector are related

to response measures in the event of a chemical, biological, radiological, nuclear and explosive

attack in civilian zones. The technology developments considered are those that relate to

responsiveness of medical action and removing contaminating species from the environment.

2.1.3 Short Description

The neutralisation of CBRNE effect has been further divided into response to chemical and

biological effects, response to radiological and nuclear weapons attack and response to explosive

events. In the event of a CBRNE attack in civilian zones, guidelines and emergency responses

for environment, medical and administrative are well laid out.

2.1.3.1 Response to Chemical and Biological threats attack

Organophosphorous compounds are neurotoxic and have been used as chemical warfare

agents. This section presents the response to a chemical and biological attack on civilian

population. The severity and rapidity of the effect of the chemical warfare agents, limits the use of

administering therapeutic antidotes. A typical antidote is acetylcholine receptor for atropine. A

model has been developed using which the exact amount dose of human butyrylcholinesterase

enzyme is required for prophylaxis against a specified dose of the organophosphate. The

- 91 -

mathematical model was built upon experimental data that was derived from in-vitro methods of

AChE and butyrylcholinestrase inhibition and calculation of biomolecular rates. The first part of

the model predicts the exponential decay of the administered butyrylcholinestrase. The second

part is a mass action model which looks at interaction of organophosphate, butyrylcholinestrase

and a neural surrogate for AChE. The limitation of the approach is the lack of validation of use of

such a prophylaxis in a disaster situation, and immunological reaction that may arise from

repeated use of the enzyme on the individual. One of the goals would be the prevention of long

term consequences of nerve agent exposure [158].

Response of engineered human skin to sulphur mustard has been studied and reported in

literature. The investigation was focused on establishing the dose and time relationship of tissue.

This was done by characterising response by morphology, apoptosis, ultrastructural, inflammation

and basement membrane alteration. The findings are expected to help in understanding the

damage mechanisms and development of enhanced countermeasures [159]. Immunochemical

analysis of chemical warfare agents adducts such as sulphur mustard, lewisite and nerve agent

with DNA and proteins have been reported. Mass spectrometry based methods have been

observed for diagnosis and dosimetry for exposure, health survelliance and forensic purposes

[160]. The mass use of prophylactic antibiotics and gas masks has been mentioned in the

literature in the event of a chemical or biological threat attack. The release of toxic materials is

managed by hazardous materials control system as laid out by the United Nations guidelines

[161]. A Delphi study was conducted in United Kingdom, to produce consensus statements, for

response and planning of biological incidents. Aspects covered were identification of risks,

personal protective equipment, contamination, transmission of infection, and accessing device

[162].

The process of dealing with chemical and biological threats has been identified in the literature.

Six measures of alerting, detection and diagnosis, availability of pharmaceutical countermeasures

such as vaccines, sera and antinfectious medicine, medical management of victims, training and

information, and research and development has been mentioned in the literature. Passive and

active immunotherapy and immunoprevention has been mentioned. The use of nanoparticles as

vehicles for antibiotics has been demonstrated against salmonella in mice. Challenges for future

development have been mentioned as protecting and selectively delivering peptides and proteins

avoiding adverse reaction to the immune system [163].

Delivery of antidotes - A number of drug delivery methods enabled by nanotechnology are

under development that may have potential applications for vaccines, anti-infective medicine,

antibiotics, and anti-inflammatory drugs. The pace and specific nature of medical response is

- 92 -

essential in addressing victims of potential attacks. Nanoparticle based drug delivery improves

the stability, targeted delivery, increases the drug carrying capability and releasing for a range of

drugs. They also provide the ability to carry both hydrophilic and hydrophobic molecules. Polymer

based therapeutics have been mentioned to have applications in antibiotics delivery. Polymer

therapeutics includes polymer drugs, polymer drug conjugates, polymer protein conjugates and

polymer micelles. Nanogels based drug vehicles have also mentioned. Nanoparticles of albumin,

chitosan and lectin are currently being used for drug delivery. Lipids based solid, nanostructured

carriers and drug conjugates are being researched. Nanoemulsions based delivery of drugs to

tumours has been reported in the literature. Experimental research on colloidal nanoparticles of

gold for delivery in a number of conditions has been mentioned. Ceramic nanoparticles

processed using the Sol-Gel techniques have been used for delivering drugs to tumour cells.

Gold nanoparticles coated on silica also provide a delivery platform. Apatamer based drug

delivery is advantageous due to high affinity and high specivity. A number of nanoparticle and

aptamer conjugates are being researched. Drug delivery based on liposomes has been reported

for a number of biological and pharmaceutical compounds such as antibiotics, antioxidants,

vitamins, haemoglobin, ATP and genetic material. Niosomes have been reported to be

advantageous for gene delivery. Polymer and phospholipid micelles are being researched for

certain delivery options. Dendrimers are being used to release anti-cancerous drugs. These are

also known to be effective against bacterial and viral infections. Carbon nanomaterials such as

nanotubes and nanohorns are being considered and researched as delivery vehicle for improving

specivity. This has been achieved by either functionalising the molecule on the surface or by

means or encapsulating it in the nanotubes. Other materials and structures such as nanoscale

sponges, nanoscale diamonds and thin films are also being researched for drug delivery. More

details in use of these approaches and methods can be obtained from the ‘Drug delivery’ report in

the ‘Health, Medicine and Nanobio’ technology sector of the Observatory Nano project.

Diagnostics - Theranostics is the field that combines drug delivery and diagnostics. Iron oxide

magnetic nanoparticles offer promising applications in targeted drug delivery. Quantum dots and

carbon nanotubes based sensors have been reported as the most promising nanomaterials for

diagnostic applications. Sensing applications are based on the recognition of proteins, DNA, RNA

and viruses. Nano-enabled biosensors offer the potential of identifying up to a hundred viruses in

parallel processing. Field effect transistors based on carbon nanotubes in a hand held device has

shown to detect asthama. Carbon nanofibres integrated into micro-fluidic devices have been

mentioned to detect micro organisms and toxins known to cause water based illnesses. A number

of other methods like immunosensors, enzymatic and viral sensors can be used in medical

diagnostic of biological species. Non-invasive molecular imaging using Magnetic Resonance

Imaging, Computer Tomography, Positron Emission Tomography, and Ultra Sonography.

- 93 -

Nanoparticles are used as contrasting agents such as fluorescent probes. Quantum dots

applications have been mentioned in the literature to have wide ranging application from

contrasting agents to fluorescence applications in DNA arrays and immunofluorescence arrays.

Gold, silica and magnetic nanoparticles have also been reported in the literature to have

diagnostic applications. Lab on a chip has potential applications in diagnostics due to its rapid,

highly sensitive and high throughput characteristics. Other technologies with relevant applications

to diagnostics are Nanopore, Lab in a cell, capillary electrophoresis and microscopy related

advances. A more detailed view on the applications is available from ‘Diagnostics’ report in

‘Health, Medicine and Nanobio’ technology sector of the Observatory Nano project. Anti-body

based diagnostic was mentioned for small pox and other agents, where pathogen is known. The

advantage of the method is that it is fast with a turn around time of 10 – 15 minutes. The

drawback of this is anti-body for each pathogen is needed. Chip readouts like those of Affymetrix

can be done for 100 pathogens however the turn around time is slow up to 4-8 hours [164] .

2.1.3.2 Response to Radiological and Nuclear weapons attack

Nano-sized magnetic absorbents have been mentioned in the literature to be effective at

treatment of low level radioactive material. Hexacyanoferrates have been mentioned in the

literature for their cesium sorption properties. The preparation of magnetite hexacynoferrate

composite has been done through wet dispersion, with in-situ precipitation synthesising coating

on magnetite. A particle distribution of between 8-30nm was achieved using this synthesis route

[165].

Zircon and more complex ceramics pyrochlore, perovskite, and zirconolite have been proposed

as forms to safely encapsulate plutonium from civilian reactors. Experimental studies have been

conducted to study the irradiation damage, at a nanometre scale, caused by radioactive material

in host ceramic matrix [166]. Remediation of nuclear waste and its safety has been mentioned in

literatures as one of the most serious problems facing nuclear installations. The waste containing

cesium and strontium ions have been dealt with using very targeted inorganic ion exchangers.

The application of nanostructured sodium silicotitanate, for selective removal of cesium ions and

sodium titanate for removal of strontium ions has been reported in the literature. Hydrothermal

methods of processing and ion exchange mechanism have been observed [167].

Determination of environmental contamination by radionucleotides such as plutonium, uranium

and americium require accurate analysis. Alpha spectrometry and inductively coupled plasma

mass spectrometry has been reported in the literature as methods for environmental monitoring,

nuclear safeguards and nuclear forensics for radionucleoides in picogram quantities [168].

- 94 -

Inductively coupled plasma mass spectrometry has been reported in the literature for the

detection of plutonium isotopes, and strontium in ground water supply. The limits of detection

reported were in femtograms per ml for the radionucleotides [169].

Super adsorbent polymer gels have been reportedly developed as a response measure in the

event of a radiological attack in civilian zones. The application would be done by means of a

spraying device in the form of an aqueous suspension. The action of the foam takes place by

absorbing the radioactive particles into the polymer structure, where they bind to the

nanoparticles contained in the gel. A vacuum device is then used to remove the gel. Arragone

National Laboratory in the United States has conducted field trials and removed 98% of

radioactive elements from cement and 80% from building facades [170].

Biodegradable nanospheres have been reported in the literature for removing toxins resulting

from a radiological and nuclear weapons attack. Poly (D, L-lactide) nanospehere 100 – 5000nm

in diameter and are injected into the blood stream of the victim. The magnetic iron oxide is coated

with polyethylene glycol to prevent white blood cell attack. The nanoparticles are further coated

with proteins that are specific to the toxin. This method offers advantages over existing methods

due to the width of toxins it can address and the short time interval they can detoxify blood.

Conventional techniques in relation to filtration of blood and can be time consuming. This method

for detoxifying is also to be used in treating victims of a chemical or biological attack. The

theoretical and preliminary experimental data has been presented in the literature [171].

2.1.3.3 Response to Explosive Incident

The application of self assembly peptide in establishing a nanofiber barrier has been reported in

the literature. This functions by means of incorporating into tissue and forming an extra cellular

matrix. The method has been experimentally demonstrated in stopping bleeding without causing

any secondary damage in spinal column, brain, femoral artery, liver and skin. The advantage

offered in traumatic situation such as response to explosive events is the ability to stop bleeding

without use of pressure, cauterization, vasoconstriction, coagulation, or cross-linked adhesives.

This method for stopping bleeding is also not toxic and does not cause any immune reactions

[172].

Explosives incident can result in bleeding and damage to the human body. Nanotechnology

advances in surgery and wound dressing are expected to provide enhanced capabilities in

attending to emergency victims of such incidents. A number of such developments have been

reported in the surgery. Bone and dental damage resulting from explosions can be addressed by

- 95 -

bone implants using nanophase materials along with polymers that are used to create an extra

cellular matrix. Nanoscale coating of titanium dioxide are used to improve mesenchymal cell

growth have been reported in the literature. Protein immobilisation on titanium implant and

nanocrystalline diamonds in implants has also been reported to improve bioactivity. Implants

enabled by ceramic nanoparticles are being developed for hip and knee replacements. Zirconia

nanoparticles enabling such implant provide enhanced mechanical resistance and longer life.

Nanocomposites formed from hydroxyapatite nanocrystals and collagen nanofibres have been

mentioned as scaffolding material for bone surgery. Nanostructured titanium has been reported to

improve bone adhesion and strength. Titanium nanotubes have been proposed as coatings for

implantable devices.

Research and development of nanoscale material enabling implants is expected to enhance

capabilities in attending victims of explosion attacks. Nanoscale calcium phosphates have been

mentioned for applications as dental implant. Cartilage implants made from anodised titanium

with nanopores and carbon nanotubes have been reported in the literature. Nanofibre scaffolds

have been mentioned for application in bladder replacements. Polydioxanone developed as

nanofibres have been mentioned for application in tissue engineering for vascular grafts. The use

of magnetic nanoparticles as coating on the surface of stents in blood vessels has been reported

in the literature. Regeneration of neurons using carbon nanotubes fibres has been reported in the

literature, where the nanotubes act like conducting electrodes. Biodegradable polymer scaffolds

for nerve regeneration have been reported to be successfully acting as extra cellular matrix for

neuron growth. Nanowires with high surface area have reported applications in neural implants.

Nanowires have also been suggested as retinal implants, and experimental studies have been

conducted to investigate their potential neuron-nanowire interface. Nanoscale silver has been

used for its antimicrobial properties during surgery in wound care dressing. Nanofibre membranes

have been reported to have applications in wound care dressings. A more detailed assessment of

implants and wound dressing can be obtained from ‘Surgery and Implants’ assessment in the

‘Health, Medicine and Nanobio’ technology sector of the Observatory Nano project.

2.1.4 State of Research and Development

This section provides a comparative assessment of research and development status of enabling

nanotechnologies. Fundamental Research is defined for this purpose as research with no

particular goals of commercialisation. Applied Research is defined as research conducted in

academia and industry directed towards a specific purpose and application. Prototype has been

defined as Applied Research or Fundamental Research that has found a potential market

- 96 -

application. Technologies that are in the field trial state are defined as those that are in the

process of commercialisation, and are being tested. Deployed nanotechnologies are those that

have found an early stage market. Mass Market has been defined as those technologies that

have been adopted by large population and are attractive high growth markets. The Response to

a CBRNE event has been presented as a comparative assessment of technology readiness

levels in Table NA.1, NA. 2 and NA.3. The technology readiness level details for medical

responses can be validated and obtained from the Health, Medicine and Nanobio Technology

Sector.

Table NA.1 – Comparative assessment of Research and Development for Neutralising chemical

biological attack

Fundame

ntal

Research

Applied

Researc

h

Prototyp

e

Field Trials /

Pilot plant ( Pre-

commercialisatio

n)

Deployed

(Commerci

alised)

Mass

Market

Vaccines

Prophylat

ic

antibiotic

s

Anti-

infectious

medicine

Drug

delivery

based on

nanoparti

cles

Nano

enabled

diagnosti

cs

A comparative assessment of research and development status of enabling nanotechnologies for

radiological and nuclear attack can be seen from Table NA.2 below.

- 97 -

Table NA. 2 – Comparative assessment of Research and Development status of incident

response to radiological and nuclear attack

Fundamen

tal

Research

Applied

Research

Prototyp

e

Field Trials / Pilot

plant ( Pre-

commercialisation)

Deployed

(Commerciali

sed)

Mass

Market

Nanosized

magnetic

sorbent

Nanostruc

tured

sodium

titanate

Spectrom

etry

technique

s

Super

adsorbent

polymer

gel

Biodegrad

able

nanospher

es

A comparative assessment of research and development status for nanotechnologies enabling a

response to an explosive attack can be seen from Table NA.3 below.

Table NA. 3 – Comparative assessment of Research and Development Status for explosive

attack response

Fundame

ntal

Research

Applied

Researc

h

Prototyp

e

Field Trials / Pilot

plant ( Pre-

commercialisation

)

Deployed

(Commerciali

sed)

Mass

Market

Self

assemblin

- 98 -

g peptide

on

nanofibre

Nano

titanium

dioxide

coating

for

implants

Titanium

nanotube

s coatings

for

implants

Nanocom

posites

for bone

surgery

Nanoscal

e

phosphat

e for

dental

implant

Nanofibre

s for

vascular

grafts

CNT for

neurogen

eration

surgery

Nanowire

s for

implant

Nanofibre

membran

e for

wound

dressing

- 99 -

2.1.5 Additional demand for research

Additional research needs for diagnostics and nanotechnology that would be beneficial for

neutralising CBRNE response as observed in the ‘Health, Medicine and Nanobio’ sector of

Observatory were mentioned as:

• Diagnostic equipment functionality in high noise situations in accidents and emergencies.

• Improving flow characteristics in nanofluidic channels, and development of coatings for

reduction of clogging.

• Improving the stability of quantum dots used in diagnostics and imaging.

• Further research on toxicity of nanomaterials used in diagnostics and imaging.

• Better (small) animal models, and adapted imaging techniques for these models, for the

development of new in vivo techniques and more accurate probe development [173].

Additional demand for research in drug delivery that would be beneficial for Neutralising CBRNE

response, as observed in the ‘Health, Medicine and Nanobio’ sector of Observatory were as

follows:

• Fundamental research in improved understanding of the mechanisms associated with

nanostructure transport across cell membranes. Understanding is also needed in

interactions between these novel nanostructures and cells.

• Applied research is needed in self assembly of polymers for creation of novel structures

for application in drug encapsulation and delivery.

• Research on novel nanostructures and coatings that can deliver drugs in response to

changes in pH, temperature, and enzyme interaction.

• Fundamental research is needed on understanding the mechanism and method for

release of drugs from delivery vehicles.

• Design and development of drugs that enhance specificity and reduce toxic side effects.

• Applied research is needed in implantable drug delivery devices and nanosensors.

- 100 -

• Particles that resemble viruses for gene delivery [173].

• Further research in drug loading efficiency of nanostructures was mentioned.

• Research and development of biodegradable nanostructures.

• Further research in toxicity of nanomaterials being researched for drug delivery options.

The following research needs for drug delivery [164] were mentioned in the expert engagement

process:

• Companion equipment to help monitor the effectiveness of some of the nano

decontamination agents.

• Equipment that can be used to make smart materials more effective; remote tuning on

charging of materials to function in multiple environments, i.e., controlled electronic

assembly or disassembly.

• Encapsulation and removal of contaminants on skin, buildings and wildlife.

• Sample acquisition and preservation for future analysis and archival.

• Active indicators in smart materials to indicate type, level and extent of contamination on

materials for biological or radioactive chemicals

• Storage of blood and blood products for use in disaster

• Improved shelf life is needed for long-term blood storage before deployment. This can be

accomplished by nano materials for storage without the need to stabilize temperature,

thus no cold chain is needed.

Additional research needs for surgery and implants that would be beneficial for neutralising

CBRNE effect, as mentioned in the ‘Health, Medicine and Nanobio’ sector of Observatory were

mentioned as follows:

• Research on nanocomposites that are biocompatible and suitable for bone replacement.

- 101 -

• Research needs for modifying surface of implant for improving implant integration into the

body. Applied research on immobilising functionalising molecules on surface of implant

coatings.

• Research has been mentioned on novel polymers, polymer mixes, and self assembled

compounded for implant stability, compatibility and integration.

• Research on miniaturisation of implant devices and power sources for such devices has

been mentioned.

• For large extended deployments mobile manufacturing on demand for nano materials

that can be placed at site [164].

2.1.6 Applications and Perspectives

The expert engagement process identified the following for the technology segment:

• Funding research for the Incident Support Sub-sector was considered more important for

societal reasons than for the economy.

• The main drivers for research and development in Incident Support were considered to

be technological and social impact resulting from the technology. This was followed by

ethical, environment, health and safety drivers. The technological drivers are cost,

performance, efficiency and absence of technological solution.

• The main drivers for research and development in neutralising effect of CBRNE incident

was mentioned as severity of incident, risk posed by incident, impact of response and

time taken for response to take effect.

• Main barriers for research and development for Incident Support were identified as

availability of finance to early stage companies and intellectual property conflicts.

Secondary barriers mentioned were access to equipment and infrastructure, inadequate

technology transfer, and lack of supportive governmental policy.

- 102 -

• The main barriers for research and development for neutralising CBRNE response

segment were identified as inadequate research funding, robustness of field trials and

availability of countermeasures and antidotes.

• The most important functional requirements were identified as effectiveness of diagnosis

and reproducibility of results. The functionality following these was mentioned to be ease

of administering therapeutics and drugs, and monitoring condition of victims.

• The engineered skins used to study the effects of chemical agents were considered to

be a good model. The limitation in using engineered skin model is that they lack active

transport and an immune system. These limitations are likely to cause a miscalculation

of the rate of damage and the contribution of the immune system to respond.

• The response to threat agent needs to include an active material to either immobilize the

specific agent or cause it to be expelled from the skin, in some other form than a blister.

• Nano enabled surgical tools, drug delivery based on nanoparticles, and nano enabled

point of care diagnostic devices are expected to be on the market in 10 years. These

were identified as attractive future markets. More need for research in drug delivery was

mentioned.

• The attractive future markets were identified for self assembling peptides on nanofibres,

and super absorbent polymer gels.

• In relation to Asia and North America, fundamental and applied research was considered

to be at par for Incident Support.

• Potential toxicity of nanoparticles was mentioned as a concern with suitable

development of appropriate precautionary measures underlined.

- Particular health concerns and potential toxicity for coated silica particles used in

drug delivery were mentioned.

- Occupational exposure to crystalline silica can lead to silicosis, pulmonary

tuberculosis, and chronic obstructive pulmonary disease. Further information on

these aspects is available from the Health, Safety and Environment work

package of the Observatory NANO.

- 103 -

2.1.7 Current Situation within EU

The following framework 7 projects funded by the European Commission in the security theme

are relevant to neutralising CBRNE:

• Simulation of crisis management activity (SICMA) project initiated in 2008, in producing a

computer assisted decision making tool for Health Services Managers in response to

crisis scenario [174].

• Identifying the needs of medical first responder in disasters (NMFRDISASTER) project

coming to an end in 2009 aimed to identify the research needs of medical first

responders. This relates to the use of protective equipment used in chemical and

biological incidents [175].

The following Preparatory Action for Security Research Funded projects were funded by the

European Commission and are relevant to neutralising CBRNE:

• The Crisis simulation project (CRIMSON) aims to research, develop and validate using

virtual reality technologies to prepare security and first response organisations for urban

crisis management in terrorist attack, CBRN crisis or hostage situation [176].

• Treatment initiatives after radiological accidents (TIARA) project aimed to create a

European network of excellence for managing crisis after accidental or malevolent

dispersal of radionuclides. The project provides information and guidelines for treatment

post radiological exposure [177].

• Bioterrorism resilience, research, reaction-supporting activity promoting co-operation to

assess the bio threat and organise a collective and comprehensive response for EU

society and citizens bio security (BIO3R) project aims at improving preparedness for

bioterrorism. It aimed to identify operational requirements, countermeasures against

biological attack (detection and therapeutic) and resilience, ethical and legal issues [69].

- 104 -

2.2.1 Title – Decontamination

Decontamination post incident

Keywords: environment, toxins, water supply, air, infrastructure, nanocrystals, nanometal oxides,

zeolites, photocatalytic, xerogel, nanoporous membranes

2.2.2 Definition of Technology Segment

The sub-segment focus is related to decontamination of environment, infrastructure and civilian

zones affected by toxins, chemical, biological and radiological species. Nanotechnology

developments related to filtration of fluid medium primarily water supply and air has also been

covered in the sub-segment.

2.2.3 Short Description

Nanosized metal oxide halogen adducts have been reported in the literature for high surface

reactivity due to their unique surface morphology. These can be used against vegetative cells and

viruses. These adducts in three nanosized metal oxides of aluminium, titanium and cerium have

been mentioned for applications in decontamination and disinfection. A comparative analysis of

the three oxides produced varying degree of results. The macrocrystalline counterparts of the

same oxides did not produce a result [178].

Nanocrystals of magnesium oxide have been reported in the literature to absorb

organophosphorus compounds. The chemisorption has been demonstrated at room temperature.

The high surface area and high surface reactivity make this material suitable for decontamination

of chemical warfare agents. The advantage offered by nanocrystalline magnesium oxide over

activated charcoal is that it is much faster, and organophosphorus compounds are destructively

absorbed while in activated carbon they are only phsisorbed [179]. It has also been reported in

the literature that nanoscale powders of magnesium and calcium oxides possess antimicrobial

properties. These nanocrystalline forms carry active halogens. Vegetative cells of Escherichia

coli, Bacillus cereus, or Bacillus globigii were reported to be decontaminated within a few minutes

and spores of spores of Bacillus within several hours. These formulations also decontaminated

water carrying Escherichia coli, Bacillus cereus, or Bacillus globigii within minutes [180].

- 105 -

Nanoscale Corporation has been reported to be commercialising a chemical hazard system that

combines magnesium oxide and photocatalytic titanium dioxide nanoparticles. The system has

been demonstrated to neutralise 99.9% of nerve gas VX within 10 minutes [181].

Bacillus anthracis attacks and Escherichia coli contamination of produce has made it necessary

for the development of a decontamination method that does not rely on time consuming cell

culture development. Magnetic glyconanparticles have been considered advantageous due to the

pace, high acquisition of pathogens due high surface to volume ratio and due to its non-

destructive nature. The functionalization of silica coated nanoparticles, was done with triazole

linker in the experimental investigation. High capture and removal efficiency for bacteria were

demonstrated with the carbohydrate coated magnetic glyconanoparticles [182].

Nanocrystalline zeolite surfaces have been researched for the absorption, desorption and thermal

oxidation of mustard gas stimulant, 2-chloro-ethyl ethyl sulphide. The research compares the

nanocrystalline zeolites, ZSM-5 (Si/Al~20) and silicalite -1 (purely siliceous form) for

decontamination of chemical warfare agents. It was experimentally demonstrated that the ZSM-5

form was more reactive than the silicalite form due to a higher surface area. The absorption was

suggested to take place both on the external surface and on the internal. It was shown that

chemical agent was stored in a stable state in the zeolite until destruction [183].

Experimental research has been conducted to analyse the reaction of nanocrystalline NaY with

dimethyl methylphosphonate (DMMP), a nerve gas stimulant. Nanocrystalline NaY with a crystal

size of approximately 30nm were used investigate the adsorption and thermal reaction. The

reaction and products were studied with FTIR and solid state NMR spectroscopy. Successful

decomposition of the stimulant was demonstrated, and the reactivity per gram of the zeolite was

reported to be similar to other studies conducted on metal oxides such as magnesium, aluminium

and titanium [184 ].

The benefits of using titanium dioxide as a photo catalyst and for decontamination of environment

pollutant are that TiO2 is inexpensive, non-toxic and biocompatible [185,186]. The processing of

nano-sized titanium dioxide was reported in the literature to have been produced by sol-gel

processing at temperatures of less than 100 degree centigrade. The thin titanium dioxide film

constituted by a of particle size in the range of 3 -5 nm adhere strongly to the substrate and are

photoactive. The research reported high photo catalytic efficiency in decomposing the stimulant

methylene blue and heptane extracted bitumen fraction. The titanium dioxide while decomposing

environmental pollutant did not promote the degradation of fibres [187]. Nano titanium dioxide

particles loaded on to activated carbon fibres have been studied in the literature for air

- 106 -

purification. The experimental study examined the photo degradation efficiency of formaldehyde

gas. The research showed excellent decontamination effect, by the photo catalytic action of

titanium dioxide and absorption of activated carbon fibers. The research also investigated

parameter such as concentration of nano-titanium dioxide, ratio of nano-titanium dioxide to

activated carbon fibre, drying temperature and time [188]. Materials coated with doped photo

catalysts have been reported to degrade solute toxic substances such as chlorophenol and azo

dyes. They can also degrade harmful gases such as acetaldehyde, benzene, and carbon

monoxide in diffuse daylight within closed spaces [181].

Research and development in photocatalytic nanowires has been reported in the literature. Free

standing membranes produced from titanium dioxide nanowire have been grown through a

hydrothermal heating process. These membranes give a paper like appearance and are highly

chemically inert, robust and can be heated to high temperatures. These can be potentially also

used as a filtration membrane in gas masks allowing oxygen but blocking toxic gases. The

technology is waiting to be commercialised by the University of Arkansas researchers [181].

CoOx-doped silica xerogels with high surface area have been reported in the literature for

decontamination of acetaldehyde gas. The xerogel with maximum pore size of 3 nm show high

catalytic activity. Carbon dioxide and traces of methane are produced as a result of air oxidation

of acetaldehyde [189].

Nanoporous keratin fibers have been reported in the literature for removing heavy metal from

solution. Keratin fibres are considered suitable due to their stability over a wide range of pH,

toughness of the structure and high surface area. A multi-fold increase in metal uptake by the

nano-porous keratin fibres was reported on alkaline ultrasonic treatment. The resulted indicated

high uptake and reusability of keratin as a biosorbent [190].

The development of a fibrous membrane has been mentioned in the literature for removing

particulates from liquid. Polyvinylidene fluoride nanofibers were electrospun into membranes for

this application. The structural properties were related to membrane separation properties and its

performance. The membranes were reported to be successful in separating 90% of the

polystyrene particles from the solution. This application has potential applications in pre-treatment

to minimise fouling and contamination [191].

Permeable reactive barriers have been mentioned in the literature for the remediation of ground

water. Permeable reactive barriers development investigation presents methods that rely on

injection and deposition of nano sized iron sulphide particles. The chemical conditions necessary

- 107 -

for optimum performance were reported to be moderately alkaline to establish optimal coverage

of iron sulphide in sand [192].

Nanoporous membranes have been developed using stable nickel based super alloys by

researchers in Germany. The nanoporous mechanical membranes offer high structural integrity,

porosity of between 30-70%, thermal and electrical conductivity and weldability. Such membranes

are suitable for applications filtering bacterial spores and dust from respiratory air and gas

separation. These are advantageous as they can be thermally sterilized. Design and

development challenges need to be overcome for such membranes can be cost effectively used

with reproducible quality [181].

Nanoceramic membranes with a mesoporous sponge structure have been developed through self

assembly of monolayers. The nanosponge is produced from mesoporous silicon dioxide

ceramics. The average pore size of these ceramics is 6nm and is known to remove toxins from

water more effectively than activated carbon fibers. The pores are filled with the self assembly

layer. Mercury is decontaminated using mercapton molecules while chelating ligands have been

reported to remove chromates. The investigation conducted by Pacific National Laboratory

reported to have achieved 99.9% decontamination within 5 minutes. Potential application for the

technology has also been mentioned for radio nucleotides and for non-fluid medium [181].

Water borne pathogens are an important cause of infections [193]. The most commonly known

pathogens are Legionella pneumophila, Pseudomonas aeruginosa and moulds [194]. Point of use

filters have been mentioned in the literature as a means of providing pathogen free water [195,

196]. This is expected to reduce infections in transmission of pathogens through water used in

washing hands and rinsing wounds in emergency wards [197]. Filters with inner coatings of

nanocrystalline silver have been reported in the literature for decontamination of water. The

research on the functionality lifetime retention of the filtering efficiency of pathogens

recommended that filters should be changed every 4 weeks in high risk areas and every 8 weeks

in moderate risk areas [198].

2.2.4 State of Research and Development

This section provides a comparative assessment of research and development status of enabling

nanotechnologies. Fundamental Research is defined for this purpose as research with no

particular goals of commercialisation. Applied Research is defined as research conducted in

academia and industry directed towards a specific purpose and application. Prototype has been

- 108 -

defined as Applied Research or Fundamental Research that has found a potential market

application. Technologies that are in the field trial state are defined as those that are in the

process of commercialisation, and are being tested. Deployed nanotechnologies are those that

have found an early stage market. Mass Market has been defined as those technologies that

have been adopted by large population and are attractive high growth markets.

The comparative assessment of research and development status for decontamination

applications enabled by nanotechnology is shown in Table DE.1 below.

Table DE.1 – Comparative assessment of Research and Development status for

Decontamination applications

Fundame

ntal

Research

Applied

Researc

h

Prototyp

e

Field Trials / Pilot

plant ( Pre-

commercialisation

)

Deployed

(Commerciali

sed)

Mass

Market

Nanosize

d metal

oxide

Nanocryst

als of

magnesiu

m oxide

Magnetic

glyconan

oparticles

Nanocryst

alline

zeolites

Photo

catalytic

titanium

dioxide

Silica

Xerogel

Nanoporo

us keratin

fibres

Polyvinyld

- 109 -

ene

nanofibre

s

PRB Iron

Sulphide

Nanoporo

us

mechanic

al

membran

es

Nanocera

mic

membran

es

2.2.5 Additional demand for research

Further research need have been mentioned for technologies and capabilities in decontamination

of people, platforms and infrastructure following an incident [199]. Further research in

improvement of decontamination reactivity of NaY for chemical warfare agents was mentioned to

be investigating incorporation of reactive metal ion or oxide into the zeolite [184].

2.2.6. Applications and Perspectives

The expert engagement process resulted in the following perspectives for the technology

segment:

• Funding research for the ‘Incident Support’ Sub-sector was considered more important

for societal reasons than for the economy.

• The main drivers for research and development in ‘Incident Support’ were considered to

be technological and social impact resulting from the technology. This was followed by

ethical, environment, health and safety drivers. The technological drivers are cost,

performance, efficiency and absence of technological solution.

- 110 -

• The main drivers for research and development in ‘Decontamination’ post incident was

mentioned as decontamination effect on civilian zones and water supply, inexpensive

approach to response, impact of response and time taken for response to take effect.

• Main barriers for research and development for ‘Incident Support’ were identified as

availability of finance to early stage companies and intellectual property conflicts.

Secondary barriers mentioned were access to equipment and infrastructure, inadequate

technology transfer, and lack of supportive governmental policy.

• The main barriers for research and development for ‘Decontamination’ segment were

identified as inadequate research funding, inadequate availability of skilled personnel,

robustness of field trials, health effect of nanoparticles, and availability of

countermeasures.

• The most important functional requirements were mentioned as ‘time taken for

desorption’, and ‘high decontamination efficiency’. Other secondary functionality were

mentioned as ‘biocompatability’, ‘high uptake of toxin’, ‘destructive desorption’ and

‘functionality retention for filter applications’.

• Nanoscaled metal oxides, nanocrystalline zeolites, photo-catalytic titanium dioxide,

fibrous membranes, nanoceramic membranes, nanoscale coatings on filters are

expected to be in the market in the next 5 years. Optimization of nanostructures and

combination with other materials are factors that would determine the market uptake. For

nanoscale coatings, durability of coatings and optimization of retained pore size would

be the important factors for technological uptake.

• Nanoprous keratin fibres and nanoporous mechanical membranes are expected to take

up to 10 years. For mechanical membranes, factors such as avoidance of clogging,

compromise between activity and longevity would be important.

• Nanoscaled metal oxides, photo catalytic titanium dioxide, xerogels were considered to

be nanomaterials with very attractive and relatively higher growth future markets for

products.

• Nanocrytalline zeolites, nanoporus keratin fibres, nanomaterials for membranes and

coatings were considered moderately attractive growth market for future products.

- 111 -

• North American research, development and commercialisation efforts were considered

better than Europe which was considered better than Asia for the technology segment.

• Potential toxicity of nanoparticles was mentioned as a concern with suitable

development of appropriate precautionary measures underlined.

2.2.7 Current Situation within EU

Nanosecure project mentioned in the Detection sub-sector is also relevant to decontamination of

airborne substances. Detoxification of airborne borne substances is being researched in the

project. DINAMICS is an ongoing European Commission project, the aim of which is the

development of a lab on a chip device, for detection of pathogens in water supply. The project

has relevance to decontamination sub-segment in Incident Support. Research has been funded

in the EU through both national and pan-European projects to develop nanotechnologies for the

incident support functions.

The following Preparatory Action for Security Research Funded projects were funded by the

European Commission and are relevant to decontamination:

• The Crisis simulation project (CRIMSON) aims to research, develop and validate using

virtual reality technologies to prepare security and first response organisations for urban

crisis management in terrorist attack, CBRN crisis or hostage situation [176].

• On-line monitoring of drinking water for public security from deliberate or accidental

contamination (WATERSAFE) project aimed to use nanotechnologies in sensing and

detoxification to protect drinking water systems for potential terrorist attacks or accidental

spillage [48].

- 112 -

2.3.1 Title - Forensics

Forensics

Keywords: crime, fingerprint, finger mark, detection, identification, forgery, nanoparticles,

nanocomposites, metal oxide nanoparticles, metal sulphide nanoparticles, DNA, biosensors,

microscopy, spectroscopy, lab on a chip

2.3.2 Definition of Technology Segment

The sub-segment cover all enabling nanotechnologies that assist in criminal investigations and

identification of criminals and means used to commit the crime. The scope of the assessment has

been on materials and methods used in detecting fingerprints, forgeries, and weapons used in

committing crimes.

2.3.3 Short Description

Forensic investigation deal with scientific analysis of evidence left at a crime scene in order to

determine establish means used, time of crime and the person involved in the crime. A fingerprint

is considered as extremely vital evidence that establishes an association between a suspect and

a criminal act. There are three types of fingerprints are found at a crime scene - visible, indented

and latent. The first ones are those that are visible formed in blood, grease, oil or paint. Such

marks are generally easy to detect. Indented or plastic marks are produced when fingers are in

contact with malleable materials such as candle wax, putty or wet paint. Latent fingerprints are

the most common and challenging to detect as they are invisible. Optical, physical and chemical

techniques are used to detect latent fingerprints. Fingerprint detection can be done by means of a

number of techniques. Each technique offers an efficiency advantage relevant to the application.

The advantage of a technique depends on the type of surface where the fingermark is left,

whether it is porous, semi-porous or non-porous. It depends on the composition of the secretions,

whether they are eccrine or sebaceous. It also depends on the time for which the fingermark has

been left on the surface and whether or not the surface has been wet [200].

The visible fingerprints can be easily detected, photographed and documented. The latent

fingerprints are difficult to detect. Fingerprints are formed primarily from perspiration. A typical

fingerprint contains water, organic and inorganic chemicals such as amino-acids, salts, glucose,

- 113 -

peptides, salts, lactic acid, ammonia, riboflavin, and lipids, due to a mix between eccrine and

sebaceous secretions. The chemical residue hardens when the water evaporates, making it

possible to detect fingermarks years after their deposition [201]. Nanoparticles based detection

were recently developed to detect the residues of latent fingerprints and provide a good contrast

between the residue and the underlying substrate.

A number of methods have been used in detecting fingermarks. The method based on

photoluminscent detection of latent fingerprints has been mentioned. In this method quantum dots

are bound to fingerprint residues, following which they are illuminated with the appropriate

spectrum of light and the fingerprint is detected by fluorescence. Cadmium sulphide, cadmium

selenide or indium phosphide quantum dots with diameter less than 10 nm have been attached to

latent fingerprint using encapsulating agents such as fatty acids or amino acid components. The

excitation of the quantum dot is carried out using a laser of near ultra-violet wavelength [202].

Fluorescent nanoparticles for detecting latent fingerprints have been developed by the University

of Sunderland. They are processed as sol-gel particles in the presence of derivates of fluorescent

dye. Nanoparticles of cadmium sulphide and cadmium selenide showing intrinsic fluorescence

can also be used. The processed nanoparticles are spherical in shape with diameters ranging

between 30 - 500 nm. Fluorescent dyes of Texas red-labeled gelatin have been used in the

process of developing the nanoparticles. Hydrophobic molecules such as phosphatidylcholine

and phosphatidylethanolamine are coated on to the nanoparticles. Texas Redporcine

thyroglobulin conjugate embedded in sol-gel derived nanoparticles have been shown to bind

latent fingerprints [203]. Latent fingerprints have been visualized using hydrophobic silica based

particles in forensic analysis. Both nano scaled and micro scaled particles have been

synthesized, the nanoparticles being applied in an aqueous solution to fingerprints while

microparticles (aggregates of nanoparticles with an average diameter of 27 microns) are used as

dusting agents. The synthesis route described in the literature, mentions the production of colored

and fluorescent agents, also colored and magnetisable particles embedded in the agents. Carbon

black and titanium dioxide has been used as embedded particles [204].

The small size of nanoparticles enables the detection of fingerprint sub-structure with greater

detail and accuracy, in comparison with larger particles used in the traditional powdering on crime

scene. The technique is advantageous due to a better definition of fingerprints recorded from

crime scenes. The technique improves the sensitivity and consequently increases the chance to

detect very faint fingermarks, and by the same way increase the possibilities to find a link with

criminals or suspects. Lipid sensitive dyes have been used for imaging and documenting

- 114 -

fingerprints in a method and apparatus developed by Ciencia Inc. Exposure to light brings about

fluorescence when lipids are bound to the residue of a latent fingerprint [201].

The use of silicon dioxide based nanocomposites has been mentioned in the literature for the

latent fingerprint detection. The experimental study has demonstrated the fabrication of

sensitising ligands and silicon dioxide based xerogels. The highly fluorescent photo-stable

europium metal ions/sensitizer complex into the nanopores of the xerogels. The novel doped

xerogels were reported to detect unfumed fingerprints on surfaces such as metal foils, glass,

plastic, coloured paper, and organic materials. The advantages offered by the doped

nanomaterials are distinct fluorescent characteristics, quick prototyping, cost effective fabrication,

and nanoparticle surface customisation for tagging of fingerprints [205].

2.3.3.1 Metal Nanoparticles in Forensics

Multi-metal deposition (MMD) is a technique that can efficiently detect fingerprints on a wide

range of substrates, as well as old and fresh fingermarks, even if they have been wet [206]. It

consists in a two-step process in which gold nanoparticles are first deposited onto the secretions,

before being covered by silver through a chemical deposition performed in solution. Gold

nanoparticles have been reported in the literature as intermediaries, for latent fingerprint

detection. The MMD technique has further been modified to improve the operational limitations of

multiple immersion baths for gold nanoparticle. Successful demonstration of detection of

fingermarks was achieved using gold nanoparticles functionalized with molecular hosts bearing

organic dyes [207]. Another modification consisted in replacing the silver deposition step by a

second gold deposition, on the gold nanoparticles, leading to an alternative MMD formulation

which constitutes a serious alternative to the classical method [208]. Luminescent techniques are

considered beneficial due to high sensitivity and their ability to remove the colour of the

background material on which the fingerprint is formed. A modification of the original two step

process has been reported in the literature for fingerprint detection, in the first step colloidal gold

particles are deposited onto the fingerprint, and in the second step zinc oxide covers the gold

nanoparticles (instead of silver for the classical MMD). A luminescent fingermark is obtained due

to the in situ–formed zinc oxide nanoparticles. Luminescent nanoparticles offer advantages over

other deposition material such as silver or functionalised gold nanoparticles. Zinc oxide is used

due to its photo-luminescent capabilities, which when excited with UV luminescent (300-400nm)

in visible range (~ 580nm) due to defects in the structure [209].

- 115 -

Figure F.1 – Schematic diagram of the multimetal deposition process for fingerprint detection

[207]

Experimental studies have been performed on detection of latent fingerprints using lipophilic and

polycationic chitosan polymer. Gold nanoparticles treated with chitosan have been used to attach

it with lipids in the latent fingerprints. The research was mainly aimed at understanding the

mechanism of detecting latent fingerprints using gold nanoparticles. Two approaches were used,

in the first one, gold colloids were capped with chitosan. In the second approach fingerprints were

pre-treated with chitosan, which was followed by immersion in a gold colloidal solution, and

addition of mono sodium glutamate to agglomerate the gold nanoparticles. Reproducible results

could lead to its potential use in forensic detection of fingerprints [210].

The application of gold nanoparticles using lipophilic interactions between fatty acids of latent

fingerprints has been reported in the literature [211].Gold nanoparticles of size 1-3 nm, stabilized

with alkanethiol have been synthesized and characterized [212]. Gold nanoparticles

functionalized with anti-body of cotinine, have been demonstrated in detecting fingermarks as

well as giving information whether the person was a smoker or a non-smoker. This was done by

pipeting the nanoparticle-anti-cotinine conjugate onto the fingerprint, following which a fluorescent

agent was added and the fingerprint imaged. Lack of fluorescence would confirm absence of

cotinine and that the individual was non-smoker [213].

Gold and silver nanoparticles have been demonstrated to detect latent fingerprints on non-porous

surfaces. Interaction of the oleylamine gold nanoparticles with the fatty acids in the latent

fingerprints causes them to deposit on the surface. These were reported to be advantageous over

conventional powder as they produce sharper patterns and do not stain the background of the

non-porous material [214].

Other techniques such as gas chromatography, mass spectrometry, infrared spectro-microscopy

and micro-X-ray fluorescence have been used in analyzing the finger mark composition [215,

216, 217].

- 116 -

2.3.3.2 Metal oxide nanoparticles in fingerprint detection

Metal oxide nanoparticles have found applications as pigments or colorant, fluorescent agent and

as fingerprinting powder. Titanium dioxide particles with particle diameter of 21nm have been

reported in suspension for the detection of fingerprints on porous and non-porous surfaces [218].

Titanium dioxide nanoparticles in methanol provided good results for fingerprint detection in blood

on non-porous and semi-porous surfaces. The results of the research were reproducible for both

old and new fingerprints [219]. For fingerprint detection on dark adhesive surfaces, titanium

dioxide nanoparticles suspended in a surfactant solution has been mentioned as the most

optimum method [220]. The use of suspended titanium dioxide nanoparticles for developing latent

fingerprints on wet surfaces has been reported in the literature. According to the authors, the

quality of fingerprint detection mainly depends on the way the surface has been touched and the

time the contact with the surface lasted [221]. Research on a highly fluorescent dye was

conducted that is absorbed onto nanoparticles of titanium dioxide, for detection of latent

fingerprints on non-porous surfaces. The research produced better results than conventional

fluorescent powders, due to a better quality of latent fingerprint details and contrast produced by

the nanoparticles and the reduced background developed [222].

Nanostructured zinc oxide was demonstrated to produce fluorescent recognition of the latent

fingerprint marks on non porous surfaces such as glass, polyethylene and aluminum foil. The

latent fingerprints were visualized when ultraviolet light was directed towards the surface [218].

Europium offers a narrow emission band and long excited life’s in relation to organic fluorescent

that have short excited lifetimes and broad emission bands. This presents an advantage in

detecting fluorescence on difficult surfaces. Experimental research has demonstrated the use of

europium oxide nanoparticles that are functionalized with amines. The nanoparticles target

carboxylic acid constituent of the latent fingerprints, which are subsequently detected using

photoluminescence [223].

2.3.3.3 Metal sulfide nanoparticles in fingerprinting detection

Nanocrystals and nanocomposites of cadmium sulfide have been applied in detecting fingerprint

marks on soft drink and aluminum foil. The nanocrystals were capped with dioctyl sulfosuccinate

in heptane or hexane, which detected the fingermarks by intense luminescence under near

ultraviolet light. The disadvantage this presents is that unfumed prints on metal, glass and plastic

cannot be adequately developed [224]. Dendrimers with terminal amine groups have been

research as reagents for fluorescent cadmium sulphide–dendrimer nanocomposties. The amine

group reacts with carboxylic acids found in deposits of fingermarks. Luminescence showed the

- 117 -

presence of fingermarks on aluminium foil, polyethylene and paper. The disadvantage of the

process was reported to be long immersion time required for development on paper surfaces

[225]. CdS with carboxylate terminal functionalisation have been used for fingerprint detection [

226]. Zinc Sulfide capped cadmium selnide nanocrystals have been used in fingerprint detection.

These bind to the amino acid component of the fingerprint residue. Fluorescent CdSe/ZnS

stablised with octadecaneamine, have been used in detecting latent fingerprints on silicon wafers

and paper. The results on silicon wafer had detailed marks detection whilst on paper they were

not obtainable due to high background fluorescence [211]. One the main disadvantages of using

cadmium if the health risk posed by the material. One of the main risks posed along with the

toxicity is the half life in the human body which is reported to be nearly 30 years [227].

2.3.3.4 Microscopy and Spectroscopy

Forensic digital imaging spectrograph developed by MS Macrosystems is used in both large- and

micro-scale document examinations. Two-dimensional and three-dimensional imaging is used for

analysis in the digital imaging spectroscopy hardware. Forged documents examined by forensics

experts for establishing authenticity use this tool to objectively compare physical parameters.

Small differences between inks and papers can be identified by the application of spectral

imaging technology and advanced processing. It can also reveal any information that has been

removed. The advantages of this technique are the nondestructive evaluation of documents and

three dimensional high resolution color imaging [228]

Scanning Probe Microscopy (SPM) is useful for characterizing surfaces based on

topographical features and physical and chemical properties. It has been used for non-

destructive evaluation of forged documents and applications in micro-nanometre resolution of

latent fingerprints. Forensic Science applications of scanning probe microscopes (including

atomic force microscope) has been mentioned in the literature [229]. Fingerprints were detected

under air or liquid with no discernable difference using an AFM. Successful development of two

overlapping fingerprints was also demonstrated. Analysis of thin layer of pen ink on the surface of

a paper document was conducted. The profile of the line was observed to have an average height

of 200nm. Writing history on a sample can be verified using this information obtained from the

AFM. The main disadvantages of this technique are the long time taken for data acquisition and

small area of the scan. Analysis of single bits in electronic devices has also been performed using

Scanning Probe Microscopy. Recovery of raw data from damaged specimen has been

demonstrated by Forensic Science Services. Information was recovered from sim cards

recovered from the site of London bombings despite the strong vibrations from the shock waves

[230].

- 118 -

Scanning electron microscopes (SEM) play an important role in forensic examinations. Extremely

good depth of focus and high to low magnification of SEMs are considered useful for a range of

applications and materials. It has been used in gunshot analysis, firearm detection, identification

of gemstones and jewellery, examination of paint particles and fibres, handwriting and print

examination, counterfeit bank notes, trace comparisons, examination of non-conducting

materials, and high resolution surface imaging. SEM identifies the particles due to their high

contrast with the stub background in the analysis of specimen stubs obtained from gun shot

residues. Bullets fired from the same gun have been identified from the marks left from the barrel

and the firing pin, in test conducted to compare bullets. SEM provides an advantage over optical

microscopy due to their high depth of focus in such forensic examinations. In addition, the

backscattered electron detector in SEMs can enhance markings on the bullets and suppress the

detection of dust particles. The literature points towards an Electron microscopy investigation

conducted into metal nanoparticles of gun shot residues. The investigation determined the

method of formation of the nanoparticles and proposed a method for the synthesis. The additional

information obtained from synthesis is expected to assist in solving crime through forensic

examination [231]. Variable pressure scanning electron microscopy along with energy dispersive

X-ray has been successfully demonstrated as analytical tool in diagnosis of electrocution cases.

In an accidental death caused by electrocution by means of histological examination of the skin

and identifying titanium metallization [232].

Desorption electrospray ionization is a detection that is used in forensic examination of surfaces.

The advantage of the technique is that is can be used at distances up to 3m with no need for

sample preparation. The technique is also rapid, highly sensitive and selection. Trace amount of

a wide range of chemical can be detected in nanogram quantities such as drug formulations, illicit

drugs, organic salts, peptides and chemical warfare agents. In this process the analyte ions

generated by the interaction of charged particles and neutral molecules on the surface are

analysed by the mass spectrometer. This disadvantage of this technique it is constraints faced

when limited access to sample. It was shown in experimental studies that illicit drugs were

identified with high level of sensitivity and selection. The technique also showed a high

throughput rate for the samples [233].

2.3.3.5 Biosensors

Biosensors are used in forensics to solve crimes and identify perpetrators. Prostrate specific

antigen (PSA) has been used to confirm the presence of semen, and absence of sperm in sexual

assault cases. The use of PSA is forensic analysis has a different set of requirements than used

- 119 -

in clinical samples. The challenge for detection lies in detecting samples contaminated by other

bodily fluids, lack of the sample or the need to extract the sample from different fabrics.

Nanoparticles and nanostructures are used to enable the analyte detection [234]. Biobarcode

arrays have been mentioned, where magnetic particles coating is where the PSA to PSA anti-

bodies binding takes place. Nanoparticles probes coated with anti-body and strands of DNA

barcode are applied in bind to the immoblised PSA [235]. Surface enhanced Raman scattering

has been used for the detection of PSA in sandwich immunoassays to a concentration of 1 pg/ml.

Gold nanoparticle probes are attached to antibodies that are labeled with Raman dyes [236].

Nanostructure based assays have been regarded robust for PSA detection due to being label free

and inexpensive. Cantilever can be used for PSA detection in resonance response variation and

bending of the cantilever. An electrical measurement of changes in resonant frequency of

cantilever has been mentioned, when binding of PSA with its antibody takes place [237]. Anti

bodies coated on silicon nanowire field effect sensors have been reported in the literature, for

highly sensitive detection of PSA. The transduction of the signal in the nanowire takes place

when the PSA - antibody binding takes place on the surface of the nanowire [238].

2.3.3.6 Role of DNA in forensics

A need for developing cost effective, rapid and precise methodology for detecting DNA has been

mentioned in the literature. DNA based identification plays an important role in forensics. Gold

nanoparticle conjugates with DNA are fabricated via gel electrophoresis, are used for precise

identification of target DNA samples. The mean particle diameter of gold nanoparticles was

reported as 10 nm. The quantitative analysis was done to produce a linear correlation between

target DNA and conjugate groupings [239]. DNA extraction, quantitation, amplification and

separation can be performed on microfabricated devices. The analytical microchip has numerous

advantages such as fast processing times, reduced reagent used, sample handling and use.

Reduced sample handling leads to a reduction in contamination of the sample. The increase in

efficiency is attributed to reduced sample volumes that are in nanolitre range and high surface

area to volume. The low cost of these devices make them an ideal platform for DNA forensic

analysis. A review by Horseman et al. has looked at the different methods applied at each of the

stages in the analysis. Modular, single and integrated systems for sample analysis have been

reported to be in a development stage [240].

An identification method for analyzing molecules based on cantilevers has been developed by

Intel. The method is used in the identity verification of criminal investigations and for forensic

examination. It is also referred to as DNA testing. The method is based on the identification of

target molecules (also known as analyte) by the use of probe molecules that bind to the analyte.

- 120 -

A deflection in the cantilever takes place if a binding between probe and analyte takes place. The

cantilever is balanced using a magnetic force, and therefore the detection is based on this

counterbalancing force. Oligonucleotides-nucleic acid and protein/peptide antibodies have been

successfully demonstrated probe analyte combinations [241]. A method for detecting target

nucleic acid has been patented by Integrated Nanotechnologies. Oligonucleotide probes are

integrated are integrated into an electrical circuit in such a manner that they are not in contact

with each other. The complimentary target nucleic acid joining the two probes bridges the gap,

resulting in a flow of current through the probes [242].

A method for application in forensics has been developed for genomagnetic nanocapture

(GMNC). Magnetic nanoparticles are functionalised with molecular beacons in this method. The

method is advantageous as molecular beacons offer high sensitivity and selectivity along with

excellent separation capability of magnetic nanoparticles. The GMNC was fabricated using the

magnetic nanoparticle as carrier, which was coated which was then functionalised with a DNA

probe for recognition and collection. An illustration and an example is shown in the figure below.

The experimental investigation was performed using samples containing cancer cells, random

DNA and proteins. It was effectively used in separation, and collection of trace amounts of

DNA/mRNA strands with a single base difference. The efficiency was reported to be over 90%

DNA collection [243].

Figure F.2 – A). Schematic diagram of genomagnetic nanocapture, Representations are 1.

Magnetic nanoparticle, 2, silica layer, 3 Biotin-avidin linkage, 4 molecular beacon DNA probe B).

TEM image of a silica-coated magnetic nanoparticle with a diameter range of 28 nm [243]

- 121 -

DNA electrochemical sensors have application in forensics. The detection methodology used by

electrochemical sensors is fundamentally based on hybridisation. The advantages offered by

electrochemical sensors for forensic applications are they are cheap, simple, reliable, sensitive

and selective for genetic identification. A number of electrochemical methods have been reported

in the literature based on impedance of voltametry. Gold nanoparticle based electrochemical chip

for DNA identification has been reported [244]. Electrochemical assays based on tracer quantum

dots of ZnS, CdS, PbS, and CuS have also been reported [245]. The main disadvantage of

electrochemical DNA sensors is the need to label the and also in some instances providing lower

sensitivity. A metal sulphide (Cadmium or Lead) based detection of DNA provides attomolar

sensitivity of the targeted DNA [246].

Single molecule spectroscopy has been reported to have applications in forensic analysis. The

technique offers ultrahigh sensitivity to detect molecules hidden condensed matter. Single

molecule spectroscopy has been used for DNA fragment sizing in forensic applications.

Fluorescent tags incorporated by a species provide physical information such as size, surface

area, volume and reactivity. Distribution of fluorescent tags on a specie is identified by

measurement of fluorescent burst size of particles. Identification in forensics is done using

information that is provided by distribution size of fragments achieved by restriction digest of

DNA. This technique offers advantages over gel electrophoresis such as high sensitivity as

picogram mass is needed as opposed to nanograms, shorter time scale being in minutes as

opposed to hours, and the ability to work with super coiled DNA [247].

Lab-on-a chip is considered to be a very useful for forensics due to its high sensitivity, high

specificity and portability. Lab on a chip devices offer the potential of high performance analysis

of substances rapidly by conducting sample preparation, injection, sampling, mixing, chemical

reactions, product separation, detection and collection on the same chip. To ensure its

disposability, they are made out of polymer, glass or hybrids of polymer-glass and silicon-glass. A

number of factors have to be considered in the design namely miniaturization, integration of the

different functional elements and low cost of the commercial devices. The device is capable of

handling numerous biological samples such as DNA. The advantages offered by the technique

are the reduction in process steps and the ability to make a number of analytical measurements.

Picolitre volumes of oligonucliotides have been experimentally separated and analysed in glass

micro fluidic chip. Capillary electrophoresis on the microfluidic chip was demonstrated to shorten

the separation time by one order of magnitude in relation to traditional capillary electrophoresis

[248]. Lab on a chip can be used in a number of relevant applications including identifying DNA

profiles and explosives at the incident site. The quick results, reliability and sensitivity of capillary

electrophoresis based method offers significant advantages for explosives analysis. The pace of

- 122 -

information analysis can act as an effective decision making tool in conducting on site forensic

analysis by agencies [249].

2.3.4 State of Research and Development

This section provides a comparative assessment of research and development status of enabling

nanotechnologies. Fundamental Research is defined for this purpose as research with no

particular goals of commercialisation. Applied Research is defined as research conducted in

academia and industry directed towards a specific purpose and application. Prototype has been

defined as Applied Research or Fundamental Research that has found a potential market

application. Technologies that are in the field trial state are defined as those that are in the

process of commercialisation, and are being tested. Deployed nanotechnologies are those that

have found an early stage market. Mass Market has been defined as those technologies that

have been adopted by large population and are attractive high growth markets. A comparative

assessment of research and development of nanotechnologies enabling forensics is shown in

Table F.1 below. A validation of readiness level against other technology sector applications for

the method, material and device is necessary. The nanotechnologies are primarily focused on

evidence analysis mainly through investigation of fingerprints, documents, gun shot residue,

explosive residue and DNA.

Table F.1 – Comparative assessment of Research and Development status for nanotechnologies

in Forensics

Fundam

ental

Researc

h

Applied

Researc

h

Prototyp

e

Field Trials / Pilot

plant ( Pre-

commercialisation

)

Deployed Mass

Market

Nanoparticl

es for

fingermark

detection

Fluorescen

t particles

Nanocomp

osites for

latent

prints

- 123 -

Gold and

silver

nanoparticl

e

Titanium

dioxide

nanoparticl

es

Zinc oxide

nanoparticl

es

Nanocrysta

ls

Dendrimer

s

SPM for

document

analysis

SPM for

explosive

specimen

SPM for

fingerprints

Biosensors

in forensics

DNA in

forensics

Lab on a

chip

2.3.5. Additional demand for research

The following areas of specific research have been identified in the literature for incident support

functions:

- The role of doped nanocomposites in improving latent fingerprint detection has been

mentioned in the literature [205].

- 124 -

- Further research for multi-metal deposition process and detection of fingerprints using

photoluminescence has mentioned the improvement of zinc oxide deposition process by

avoiding thickening of the ridges. Further research is to be conducted on different

surfaces such as coloured and illustrated paper. This is expected to be extended to

banknotes, which present a significant challenge due to the complex printed patterns.

The technique is also to be proven for other non-porus surface and compared with other

methods such as cyanoacrylate fuming [209].

- Further research in gold nanoparticles capped with chitosan has been mentioned in the

literature. Research is required into the mechanism of enhancement, and optimisation of

treatment time to obtain improved results [210].

- Increases in sensitivity and variety of DNA target detection with electrochemical DNA

sensors based on metal sulphides have been mentioned in the literature [246].

- Improved technological capabilities for forensic identification of trace hazardous

substances has been mentioned [250].

2.3.6 Applications and Perspectives

The expert engagement process resulted in the following perspectives for the technology

segment:

• Funding research for the ‘Incident Support’ Sub-sector was considered more important

for societal reasons than for the economy.

• The main drivers for research and development in ‘Incident Support’ were considered to

be technological and social impact resulting from the technology. This was followed by

ethical, environment, health and safety drivers. The technological drivers are cost,

performance, efficiency and absence of technological solution.

• The main drivers for research and development in ‘Forensics’ was considered to be

‘severity of incident’, ‘accuracy of forensic examination’ and ‘inexpensive approach to

analysis’.

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• Main barriers for research and development for ‘Incident Support’ were identified as

availability of finance to early stage companies and intellectual property conflicts.

Secondary barriers mentioned were access to equipment and infrastructure, inadequate

technology transfer, and lack of supportive governmental policy.

• The main barriers for research and development for ‘Forensics’ was considered to be

‘inadequate research funding’ and ‘health effects of nanoparticles’.

• The most important functional requirements were mentioned as ‘limit of detection’, ‘High

sensitivity’, and ‘ease of prototyping’. Important functionalities were mentioned to be

‘fluorescent characteristics’, ‘time taken for data acquisition and signal processing’,

‘range of substrates’, ‘physical parameters for definition’, and ‘non-destructive analysis of

forensic documents’.

• It was mentioned that visible fingermarks can be of poor quality while latent fingermarks

of excellent quality once detected.

• A visible fingermarks can also be greatly enhanced with subsequent treatment for

example in the case with blood fingermarks.

• The formulation of multi-metal deposition photo-luminescent zinc oxide has application

limited to non-porous surface.

• The most widely currently used techniques were mentioned as are chemical ones

namely, 1, 2-Indanedione, DFO, ninhydrin (for porous surfaces), cyanoacrylate fuming

with dye (for non-porous surfaces), vacuum metal deposition, among many others.

• FTIR spectroscopy was also mentioned to be used for detecting fingermarks by chemical

imaging, as well as micro X-ray. These however were not used in routine processes.

• Metal nanoparticles, colloids for fingerprint detection and fluorescent dyes are presently

in the market. The nanomaterials were mentioned to be attractive growth market for

applications.

• Fluorescent nanoparticles and metal oxide nanoparticles are expected to be in the

market in the next 5 years. These nanomaterials were considered attractive growth

markets for future application.

- 126 -

• Quantum dots, metal sulphide nanoparticles and lab on a chip are expected to take up to

10 years to reach the market. These were also considered to be attractive growth

market for the future.

• Other qualitative issues identified were the need to reduced prices of nanomaterials for

forensic application, development of synthesis and functionalisation protocol, application

protocols for users, ability to apply forensic technique at the crime scene.

• Additional policy measures were suggested for long term R&D strategy and support for

University researchers creating start up companies. Other ideas suggested were

improving the efficiency of existing techniques using nanomaterials.

• Potential toxicity of nanoparticles was mentioned as a concern, specific concerns were

mentioned for cadmium based powders. Health and safety issues are expected to

become important especially for application at the crime scene.

• The field of forensics was mentioned to an area of limited research spread out across

world in national laboratories and Universities. EU was mentioned to be at par with North

America and Asia in forensics. The recent years have witnessed a growth in publications

from China for forensic applications.

• A notable qualitative interaction was mentioned to be the negative impact of that

patenting may have in forensics. The increased protection of research limits enabling

capabilities and thus prevents deterrence of crime. Increased sharing of research results

through laboratories to implementation by civilian agencies would have a beneficial

impact on society through reduction of crime.

2.3.7 Current Situation within EU

A 3-years project funded by the Swiss National Science Foundation has been mentioned in

forensics. The aim of the project is to develop new efficient fingermark detection techniques

based on functionalized and luminescent nanoparticles. The project is being implemented in the

context of fingermark detection by chemical methods. The project has commenced in 2009 and is

expected to go on till 2012 [251].

- 127 -

3. Protection

3.1.1 Title - Personnel

Protection of Personnel

Keyword: textiles, vests, protective gear, ballistic projectiles, nanoparticles, nanomaterials, fibres,

oxides, body armour, Kevlar, carbon nanotubes, fullerenes, dendrimers, polymer nanofibres,

shield

3.1.2 Definition of Technology Segment

The ‘Protection of Personnel’ sub-sector segment would cover the developments under textiles

and protection systems against chemical, biological, radiological, nuclear and explosives. The

sub-segment would also cover developments in protective clothing against knives, projectiles,

and firearms.

3.1.3 Short Description

Protective clothing is based on barrier suits that are either full barrier impermeable suits or

permeable adsorptive suits. Functionalised activated charcoal has been reported to been used for

adsorption. The main disadvantage of charcoal for protective applications is its heavy weight and

moisture retention in barrier suits [252]. DS2 is used in the United States as a decontamination

agent against nerve gas. The disadvantage of this solution is that it is highly toxic, very corrosive

and release toxic by products. These are also not active against biological agents. A number of

other agents have been developed for decontamination of nerve agents, blister agents and blood

agents. Chemical such as b-cylcodextrin (b-CD), o-iodosobenzoic acid (IBA), polyoxometalates,

peroxides, oximes, chloramines and metal nanoparticles have been mentioned to be suitable [

253 , 254, 255, 256, 257]

Nanoparticles of magnesium oxide were mentioned in the literature to have been mixed with a

range of polymer solutions to produce nanocomposite membranes. A relative experimental

comparison of paraoxon hydrolysis under ultraviolet light produced the best results from

polysulphone. A further relative comparison of charcoal with nanoparticles produced a 60%

- 128 -

hydrolysis result for magnesium oxide nanoparticles membranes. Magnesium oxide nanoparticles

were loaded up to 35% into the nanofiber, were demonstrated to be twice more reactive than

charcoal [258].

Nanofibres offer high specific area, low fibre diameter, potential to include active chemistry,

filtration, layer thinness and high permeability [259]. The nanofibres can be incorporated into

cloths which serve the purpose of enhanced protection against aerosol. The nanofibres also

serve as carriers of active functionality that can detoxify the warfare agent without adding extra

weight to the cloth. Functionalising the appropriate catalyst on the surface of the nanofiber has

been mentioned in the literature as a suitable approach to detoxification [260]. Polymer nanofibre

membrane was reported to have been produced using the electro spinning technique. These

nanofibres were reported to be functionalised with activated granular carbon as catalyst. The

catalyst provided good performance for paraoxon, an organophosphorus model for sarin, which

was used in the experimental study [261].

Protective gear for civilian security organisation forms an important part of protection in

hazardous situation they may find themselves in the line of duty. Protective equipment is

expected to provide light weight gear which will allow extreme mobility and high degree of

protection. Body armour composed of nanocomposites is expected to become routine. The use of

Kevlar in helmets is an example of such light weight protection. Body armour is also expected to

provide protection against any chemical and biological warfare agents used in civilian zones.

Multilayer polymer thin films have been mentioned for use in body suits that would neutralise the

effect of chemical or biological agents. The use of dendrimers has been mentioned for detoxifying

the effects of mustard gas. The use of electrorheological fluids which changes its rigidity in

response to an electric charge has been suggested for protection application. An electric charge

in such passed through the fluid in between layers of fabric arranged like a deck of cards could be

a potential solution [262].

Protective vest, shields, barriers, and explosion proof blankets against bullets, sharp objects and

explosive devices are necessary for the protection of civilian security agencies. Research in

Australia has examined the potential of using carbon nanotubes against ballistic impact. A

comparative study of bullet impact on carbon nanotubes with both ends fixed and one end fixed

was performed for different radii. The study was performed using a piece of diamond with varying

velocities at different positions on the nanotubes. The absorption efficiency was reported to high

for fixed ends nanotubes, and lowest middle point of the nanotubes [263]. Yarns of multiwalled

carbon nanotubes have been produced with yarn strength greater than 460 MPa. These have

shown to be as strong as existing bullet proof vest and with 48% reversible damping. These offer

- 129 -

high thermal, creep resistance, chemical resistance and a substantial increase in yarn strength on

incorporation into a polymer matrix [264].

3.1.4 State of Research and Development

This section provides a comparative assessment of research and development status of enabling

nanotechnologies for protection. Fundamental Research is defined for this purpose as research

with no particular goals of commercialisation. Applied Research is defined as research conducted

in academia and industry directed towards a specific purpose and application. Prototype has

been defined as Applied Research or Fundamental Research that has found a potential market

application. Technologies that are in the field trial state are defined as those that are in the

process of commercialisation, and are being tested. Deployed nanotechnologies are those that

have found an early stage market. Mass Market has been defined as those technologies that

have been adopted by large population and are attractive high growth markets. Table PP.1 below

provides an overview of the development for the protection of personnel.

Table PP.1 – Comparative assessment of Research and Development status Protection of

Personnel

Fundame

ntal

Research

Applied

Researc

h

Prototyp

e

Field Trials / Pilot

plant ( Pre-

commercialisation

)

Deployed

(Commerciali

sed)

Mass

Market

Nanoparti

cles of

magnesiu

m oxide

Nanofibre

s

Polymer

thin films

for body

suits

Dendrime

rs

CNT for

ballistic

- 130 -

absorptio

n

3.1.5 Additional demand for research

The following additional demand for research has been mentioned in the literature:

Catalysts functionalised on nanofibres membrane provide a means for detoxifying

chemical warfare agents. Research has been mentioned in the literature to be conducted

for different catalysts for a range of chemical and biological agents that could be reduced

using protective wear. Further development work has also been mentioned in brining the

different nanofibre layers to form a woven textile media as a protective garment. Such a

protective garment is expected to offer additional comfort through exchange of moisture

in relation to charcoal impregnated suits [261].

Further development for magnesium oxide nanoparticle based nanofibre membranes to

degrade mustard agents and biological warfare agents has been mentioned in the

literature [258].

Bullet impact of carbon nanotubes under different loading conditions has been mentioned

as a research need for application such as bullet proof vests and explosion blankets

[263].

Further research and development has been mentioned for operational effectiveness and

capability of first responders for reducing injury and loss of life. Research areas include

protective clothing for first responders, monitoring performance and health, integrating

sensors and communication devices [199].

• Active decontamination materials to protect responders from threats [164] were

mentioned in the engagement process as:

- Chemical: Nano barrier materials that can be applied and do not require PPE

suits.

- 131 -

- Biological: Encapsulate to protect responders from contamination at the site of

attack and prevent spread.

- Radioactive: Barrier that can be applied to reduce or eliminate exposure of

responders and subsequent cleanup crews.

3.1.6 Applications and Perspectives

In the expert engagement process for the technology segment the following perspectives were

observed:

• Funding research and development for Protection sub-sector was considered important

both for the European society and the economy.

• The main drivers for R&D in ‘Protection’ sub-sector were considered to be technological,

and environmental, health and safety (EHS). The technological drivers are primarily

related to cost, performance, efficiency, and absence of solution. Secondary drivers were

related as productivity gains, and competitive advantage in conflict.

• The drivers for R&D in ‘Personnel Protection’ segment were considered to be ‘safety of

citizens and civilian agencies’, ‘protection against risk agents’, and ‘effectiveness of

countermeasures’.

• The main barriers for ‘Protection’ sub-sector were considered as ‘intellectual property

conflict’ and ‘availability of finance’ for start-ups. Other secondary barriers were

considered as lack of supportive government policies, lack of tax incentives, access to

infrastructure, and inadequate technology transfer.

• The barriers for R&D in ‘Personnel Protection’ segment were mentioned to be

‘inadequate skilled personnel’, ‘health effect of nanoparticles’, ‘lack of research funding’,

and ‘lack of integration of nanomaterials into products’.

• The most important functionality was mentioned to be ‘low weight of protective clothing’.

Other desirable functionalities were mentioned as ‘non-toxicity’ and ‘non-corrosiveness’,

‘ability to functionalise catalyst on fibre surface’ and ‘freedom of movement’ for the

protection solutions.

- 132 -

• The application trends for protective textiles was mentioned as follows:

- For first responder markets, the trend is towards personnel area networks and

integrating sensors into textiles. The technology readiness is relatively mature and

expected to be deployed in the market over the next 2-3 years.

- Demand for technology is driven by security agencies for textiles and protective

equipment. Anti-ballistic functionalities drive research and development for protective

gear.

- The first responder and dual application markets are fragmented. They are small and

deployment times are very long.

- Cost effectiveness can be improved by legislating functionality. This is also expected

to improve the fragmentation in the marketplace. Cost effectiveness was also

suggested to be improving scale up through partnerships in manufacturing.

- Operational constraints were mentioned to be speed of deployment and discreteness

of protective functionality.

- Product driven focus developing cost effective technological solutions was mentioned

as an important issue for processing and manufacturing. Emphasis was given on

technological solution that adds to the product benefits.

- Product acceptance in the market place was mentioned as to be considerably

challenging. As incumbent products are averse to change, generating opinion leaders

was considered to be vital.

- For some applications it is expected that commercialisation would be in other markets

and then followed by security.

- Nanofibres and carbon nanotubes based vests were considered to be very attractive

high growth potential markets.

• In relation to US for ‘personnel protection’ segment, EU was mentioned to be better at

fundamental and applied research. US was mentioned to be better at commercialisation,

- 133 -

technology transfer, routes to market, and ‘supporting mechanisms’. EU was mentioned

to be lack of resources for commercialisation and technology transfer. A notable trend

mentioned was the changes in the Asian market, particularly innovative chemistry

research being published from India.

• Other qualitative suggestion for changes were suggested as follows:

- improving tax benefits for R&D for security applications

- enhancing academic focus on commercialisation in EU

- introducing a commercialisation performance metric for academics contributing to

research ratings

- promoting scientific defense enterprise that promotes development and validation

of concept

- specification generation through collaboration with security enterprise as a non-

competitive activity

3.1.7 Current Situation within EU

The following framework 7 projects funded by the European Commission in the security theme

are relevant to personnel protection:

• Identifying the needs of medical first responder in disasters (NMFRDISASTER) project

coming to an end in 2009 aimed to identify the research needs of medical first

responders. This relates to the use of protective equipment used in chemical and

biological incidents [175].

• Advanced first response respiratory protection (FRESP) project was initiated in 2008. The

aim of the project is to develop nanoporous adsorbent for respiratory protection of first

responders. The research and development of protection would cover a wide range of

chemical toxic and biological agents [265].

- 134 -

3.2.1 Title – Infrastructure and Equipment

Infrastructure and Equipment Protection

Keywords: reinforcement, mechanical strength, EMI shielding, carbon nanotubes, inorganic

fullerenes, ceramic composites, nano- layered double hydroxide, nanoclays, buckypaper,

buckyball, conductive polymers, nanofibres, carbon nano onions, metal nanoparticles, fillers,

dielectrics

3.2.2 Definition of Technology Segment

The technology segment is expected to cover research and development in applications that are

related to reinforcement of structures, construction, areas of mechanical strength, and robustness

of protection. The section also covers nanotechnological development that would enable the

prevention against fire. Electromagnetic shielding of critical communication and information

infrastructure would be covered under the technology analysis in this segment.

3.2.3 Short Description

The technology analysis is further been done based on protection by reinforcement of structures,

protection against fire and electromagnetic shielding of information and communication

infrastructure. A short description of the developments is available from the subsequent sub-

sections.

3.2.3.1 Reinforcement of structures

Protection of critical infrastructure against explosions and natural disasters are of primary

important in order to retain organisational functions of civil society. Enhanced safety and security

of constructions through incorporation of nanomaterials can be achieved. Products such as safety

glasses, plating, concrete reinforcement, fire protection and self healing are additional security

features. Metal foams have been mentioned in the literature for protection against ballistic

projectiles. Aluminium foams sandwiched between steel plates have shown to have high

tolerance to shock waves [266]. Nanometre sized precipitates are reported to increase the

strength of steel alloys making them suitable for ballistic impact applications. The material

- 135 -

demonstrates very high strength, hardness, ductility, toughness and good corrosion resistance

[267]. Ceramic composites backed by metal layers have been used in ballistic armour

applications. Function grade material with nanoscale coating was used to enhance the weakness

at the interface of composite and metal. It was demonstrated to have enhanced ballistic

resistance [268].

Vertically aligned carbon nanotubes have been shown to have super compressible foam like

behaviour. These nanotubes fabricated through the chemical vapour deposition process show

very high compressive strength, recovery rate, sag factor and excellent breath ability. These have

foams have demonstrated greater compressibility and pressure resistance than polymer foams,

while offering chemical resistance similar to metal foams. The experimentally demonstrated

prototype is expected to be used in energy absorbing surfaces for earthquake and explosion

protection [269].

Inorganic fullerenes such as tungsten and molybdenum sulphide have been demonstrated to

have excellent antishock behaviour with the ability to handle upto 25GPa. The close cage

structure of inorganic fullerenes provides it very high mechanical strength and shock resistance

behaviour. The fullerenes when combined in a metal, alloys and polymers can be used in

applications for protection against explosive ballistic projectiles [270].

3.2.3.2 Protection against fire

Fire resistant coatings have been mentioned in the literature. Nanometer scale layered double

hydroxide (LDH) and nanoscaled titanium dioxide have been mentioned in the literature for fire

resistance coating. Experimental studies performed have investigated the effects of nano-LDH

and nano-titanium dioxide in improving fire resistance and anti aging properties of coatings. The

coatings were shown to have great improvements in properties though by addition of nano scale

additives [271]. The improvement of acrylic nanocomposites with nanoscale silicon dioxide has

also been studied in fire resistant properties of flame retardant coatings. The nanoscale silicon

dioxide enhances the anti-oxidation, char accumulation and char structure. The fire protection

properties of acrylic nanocomposites have been reported to be better than conventional acrylic

resin [272]. Acrylic nanocomposite coating containing nanoclays have been developed for fire

protective coatings. The influence of nanoclays on properties was studied using scanning

electron microscopy and fire tests. Nanocomposite coatings with 1.5% nanoclay have

demonstrated good fire resistance and aging [273].

- 136 -

A comparative study of fire resistance of polymer nanocomposites filled with organoclays,

polyhedral silsesquioxanes and carbon nanotubes has been mentioned in the literature. The

experimental study using TEM showed that good dispersion of fillers improve flame retarding

ability but failed in flammability tests. It was demonstrated that best results were obtained using a

combination of flame retardants and Nanofillers [274]. Polymer and layered silicate

nanocomposites have been experimentally studied, and shown that indefinite protection against

fire could not be achieved. A number of approaches were suggested for improving fire retardancy

like improving coupling of silicate layers in the char, incorporating additional additives as second

layers of defence, to improve the effectiveness [275].

Buckyball nanocomposites have been investigated for their flame retardant properties. Dispersion

of buckyballs in a polypropylene matrix was studies using TEM. The presence of C60

demonstrated to have a marked increase in the flame retardant properties of the

nanocomposites. The flame retardancy was found to increase with the increase in increasing

loading of the C60 in the polymer matrix. The mechanism of the buckyballs for trapping the free

radical has been proposed [276].

Buckypaper is another name for carbon nanotubes membrane, which is made up of tangled

carbon nanotubes ropes. The bucky paper was incorporated on the surface of polyhedral

oligomeric silsesquioxane and glass fibre composite to experimentally study the fire resistance.

The buckypaper was shown to have effectively reduced flammability for covering glass fibre

composites. The advantages offered by the buckypaper are its thermal stability and ability to act

as a barrier in reducing the degradation of products [277].

3.2.3.3 Electromagnetic shielding of information and communication equipment

Electromagnetic interference (EMI) is a well known problem for security electronic equipment. In

a highly integrated information and telecommunications networked society, electromagnetic

pulses or fields could be present a threat to the security of vital networks. Electromagnetic pulses

may have their origin in thermonuclear explosions or an electromagnetic bomb. A number of

different materials are under consideration and are being researched to protect devices and

networks from EMI.

Electromagnetic radiation is also a by product of the vast increase of 1-5 GHz consumer

electronic applications that interfere with large and critical systems. The need for protection from

EMI has thus become an essential functional need of critical electronic and communications

- 137 -

equipment. Literature has reported the most cost effective commercially available to be magnetic

fillers and dielectrics [ 278, 279]. Intrinsically conductive polymers have been considered as

protection against EMI due to their high conductivity, environmental stability and simple synthesis

methods [280]. Electromagnetic shielding properties of polyaniline and polyurethane

nanocomposites were optimised by modelling using a genetic algorithm and then experimentally

tested. EMI shielding obtained attenuation higher than 40 or 80dB based on application in the

microwave band [281]. Intrinsically conductive polymers are applied in form of thermoplastic

polymer thin films such as polyvinyl chloride and polystyrene [282]. The synthesis and

characterisation of nanocrystalline silver coated fly ash cenosphere particles are used in

producing conductive polymer composites for EMI shielding has been mentioned in the literature

[283].

In order to improve the performance and properties of intrinsically conductive polymers, lamellar

nanocomposites based on conductive polymers like polyaniline have been reported in the

literature. An investigation into the thermal, mechanical, electrical and microwave radiation

absorbing properties of conductive polymers have been studies. Nanocomposites of polyaniline

and organoclays doped with dodecylbenzenesulphonate have been experimentally studied. The

nanocomposites showed to have high conductivities and good mechanical properties for

conducting composites. These nanocomposites were shown to act effectively against radiation

between 8 -12 GHz. These could be potentially used in antistatic packaging layers as well [284].

EMI shielding has been experimentally demonstrated using nanocomposite comprising of carbon

nanotubes and carbon nanofibres in a polymer matrix. Carbon nanofibres of diameter 100-200nm

in diameter and 30-100 µm length, with carbon nanotubes with 10-20 nm diameter and 5 -20 µm

were used in the experimental research in a polystyrene matrix. A relative comparison of carbon

nanotubes composite, nanofiber based composite and the combination of the two materials was

done in experimental research. Electrical conductivity of the filler material, shape, size, and

distribution in the matrix determine the electromagnetic shielding of the device. EMI shielding

effectiveness for commercial applications has been mentioned in the literature as 20 dB. This was

successfully demonstrated by nanocomposites containing 10 wt% of carbon nanofibres and a

minimum of 1wt% carbon nanotubes. Other advantages offered by these nanocomposites are the

light weight, low cost and excellent mechanical properties [285]. Vapour grown carbon nanofibres

(VGCNF) in a polymer matrix have been investigated for their effectiveness in shielding and the

relationship with processing variables. The effect of frequency (8 -12.5 GHz) was related to

electrical characteristic like impedance. The research concluded that all VGCNF reinforced

composites can find applications in electromagnetic shielding applications [286].

- 138 -

The mechanical, electrical, thermal, and electromagnetic shielding properties of multiwalled

carbon nanotubes embedded in rubber sheets have been investigated. The amount and

alignment of nanotubes determined the shielding effectiveness. These nanotubes demonstrated

effective shielding for the range between several hundred MHz upto 1GHz. Due to shielding

effectiveness of above 60dB these are expected to be used in a number of industrial electrical

equipments [287]. Multiwalled carbon nanotubes have been demonstrated for their

electromagnetic shielding in liquid crystal polymers and melaine polymer matrix. The highest

shielding effectiveness at 60 dB experimentally demonstrated is suitable for industrial scale

applications. The higher aspect ratio carbon nanotubes demonstrated higher shielding

effectiveness and are considered suitable for use in conductive filler in plastic package [288].

Single walled carbon nanotubes in polymer matrix have been reported in the literature for EMI

shielding applications. The highest shielding effectiveness demonstrated was 49dB at 10MHz for

15 wt% SWCNT. A shielding effectiveness of between 15-20 dB was observed for 500MHz –1.5

GHz frequencies [289].

Sol-gel based coatings have been mentioned in the literature for electromagnetic wave shielding

coatings. These are composed of ultra fine metal particles in a silicon dioxide matrix. Silver colloid

particles 10 nm in diameter were used with TiOxNy-ATO particles to obtain a protective film. The

electromagnetic shielding effect depends on the surface conductivity which in turn is affected by

the electric conductivity of the material and structure of the particles. The experimental research

demonstrated that the surface conductivity of the film can be controlled by controlling the shape

of the nanoparticles [290]. Nanoparticles of nickel and iron alloys were mentioned in the literature

to be dispersed in expanded graphite for electromagnetic shielding applications. The alloy

nanoparticles showed high shielding effectiveness for low frequency. Expanded graphite is

electrically conductive, and shows good shielding effectiveness at high frequencies. The material

thus demonstrated high shielding effectiveness for a wide range of frequencies [291].

Electromagnetic wave absorption has been mentioned in the literature using nano tetrapleg zinc

oxide as absorbent and epoxy resin as binder in a coating. The nano tetrapleg zinc oxide

coatings were observed to have excellent absorption for wave band between 15 -18 GHz [292].

Carbon nano onions (average particle size of 4 -7 nm) and detonation nano diamond are

considered to be a candidate material for applications of electromagnetic shielding.

Nanocomposites of carbon nano onions have been experimentally shown to attenuate

electromagnetic shielding radiation for 12- 230 THz. It has also been mentioned that through

mixed use of carbon nanomaterials, further enhanced shielding can be achieve for a spectral

range of ultraviolet to terahertz and microwave [293].

- 139 -

Electromagnetic shielding in the low frequency range (30 kHz - 1.5GHz) has been experimentally

demonstrated using carbon matrix composites with self assembled interconnected carbon

nanoribbon network. These were fabricated using low cost natural materials such as rice husks

as source for carbonaceous sources and transition metals as catalysts. The composites with

carbon nanoribbons were show to have higher electromagnetic shielding value and higher

electrical conductivities, than composites without carbon nanoribbons. Low frequency shielding

has important applications for portable electronic devices that are used by civilian security

agencies [294].

Carbon nanotubes and shape memory alloy composites have been developed for

electromagnetic shielding applications. The shielding effectiveness of the composite was shown

to have a dependency on the content of the nanotubes and the thickness of the composites.

Three frequency bands 8-26.5 GHz (K band), 33-50 GHz (Q band) and 50-75 GHz (V band) were

used for the experimental studies, with the highest frequency demonstrating the highest shielding

efficiency [295].

3.2.4. State of Research and Development

This section provides a comparative assessment of research and development status of enabling

nanotechnologies for protection. Fundamental Research is defined for this purpose as research

with no particular goals of commercialisation. Applied Research is defined as research conducted

in academia and industry directed towards a specific purpose and application. Prototype has

been defined as Applied Research or Fundamental Research that has found a potential market

application. Technologies that are in the field trial state are defined as those that are in the

process of commercialisation, and are being tested. Deployed nanotechnologies are those that

have found an early stage market. Mass Market has been defined as those technologies that

have been adopted by large population and are attractive high growth markets. A comparative

assessment of research and development status of nanotechnology development for protection

application of infrastructure, information and communication equipment has been shown in Table

EIP.1 below.

Table EIP.1 – Protection of equipment and infrastructure

- 140 -

Fundame

ntal

Research

Applied

Researc

h

Prototy

pe

Field Trials / Pilot

plant ( Pre-

commercialisatio

n)

Deployed

(Commercial

ised)

Mass

Market

Metal

foams

Ceramic

composit

es for

armour

CNT in

compres

sible

foams

Inorganic

fullerene

s for

shock

protectio

n

Nanoscal

e LDH

for fire

protectio

n

Nanoscal

e

Titanium

dioxide

for fire

resistanc

e

coatings

Nanoscal

e silicon

- 141 -

dioxide

Nanoclay

nanocom

posites

Buckybal

l

Nanoco

mposites

for fire

protectio

n

CNT

Membran

e for fire

protectio

n

Magnetic

fillers

and

dielectric

s for EMI

Nanoco

mposites

for EMI

shielding

Carbon

nanotube

s for EMI

Carbon

Nanofibr

es for

EMI

Metal

Nanopart

icles for

shielding

- 142 -

Nanoco

mposites

of carbon

nano

onions

Carbon

nanoribb

on

network

for

shielding

CNT and

shape

memory

alloy

composit

e

3.2.5 Additional demand for research

The following additional demand for research was mentioned in the literature:

Further research for carbon composites with a carbon ribbon matrix for electromagnetic

shielding has mentioned optimisation by manipulating the nanostructures through

changing the experimental parameters such as sintering temperature and impregnation

of transition metal [294].

Research need has been mentioned in the development of design requirements and

additional physical protection measurements to counter threats against critical

infrastructure such as government building and transportation hubs [199].

3.2.6 Applications and Perspectives

In the expert engagement process for the technology segment the following perspectives were

observed:

- 143 -

• Funding research and development for Protection sub-sector was considered important

both for the European society and the economy.

• The main drivers for R&D in ‘Protection’ sub-sector were considered to be technological,

and environmental, health and safety (EHS). The technological drivers are primarily

related to cost, performance, efficiency, and absence of solution. Secondary drivers were

related to productivity gains, and competitive advantage in conflict.

• The drivers for R&D in ‘Equipment and Infrastructure Protection’ segment were

mentioned ‘protection against sabotaging agents’, ‘information networking reliability’ and

‘protection of information and communication infrastructure’.

• The main barriers for ‘Protection’ sub-sector were considered as ‘intellectual property

conflict’ and ‘availability of finance’ for start-ups. Other secondary barriers were

considered as lack of supportive government policies, lack of tax incentives, access to

infrastructure, and inadequate technology transfer.

• The barriers for R&D in ‘Equipment and Infrastructure Protection’ segment were

mentioned as ‘inadequate research funding’, and ‘lack of product integration’.

• The most important functionality were identified as ‘fire resistance’, ‘aging resistance’,

‘thermal stability’, ‘longevity of production’, ‘resistance to forced damage’, ‘weight of

structure’, ‘electromagnetic shielding effectiveness’, ‘range of frequencies shielded’ and

‘surface conductivity of shielding agent’. Secondary functionalities desirable were

mentioned as ‘barrier to degradation products’, ‘strength of structure’ and ‘wear and tear

resistance’.

3.2.7. Current Situation within EU

No specific EC framework projects associated with nanotechnology applications in equipment

and infrastructure projects were observed.

- 144 -

3.3.1 Title – Condition Monitoring

Condition monitoring of civilian zones and critical infrastructure

Keywords: sensor, sensory networks, civilian zones, monitoring, temperature, light, vibration,

sound, chemical species, trace vapours, radiation, sensing, processing, storage, memory,

communication, information transfer, carbon nanotubes, graphene, nanowires, interconnects,

transistors, power supply, semiconductors, quantum dots, energy, cantilever, solar, light

harvesting

3.3.2 Definition of Technology Segment

Sensory networks and nodes provide platform for continuous monitoring of physical and

environmental variables affecting important infrastructure in civilian zones. The section aims at

assessing nanotechnology development which would enhance protection capabilities through

continuously monitoring the condition of infrastructure and providing information about its status

or any disruption in activity.

3.3.3 Short Description

The advancements in wireless communications and integrated circuit have made the

development of sensory networks possible. A network of sensors to monitoring environmental

conditions and presence of threatening agents could be used in the protection of infrastructure.

These sensors could detect temperature, light, vibration, sound, chemical species, trace vapours

and radiation. The concept of a sensor web has been reported in the literature. This sensor web

has been proposed to comprise of three layers, sensing, communication and information. The

sensor web provides functional characteristics such as interoperability between platforms, low

cost, reliability, scale up, and high resolution. The multimodal information obtained from the earth

observatory system is expected to considerable enhance data processing capabilities for

accurate analysis and decision making [296].

A sensor node comprises of a sensing unit, a processing unit, a power unit and a transceiver unit.

The sensor unit further is comprised of the sensor and an analog to digital converter. The

processing unit serves the function of working with other units on assigned sensing tasks. The

transceiver unit serves the purpose of connecting the node to the network. The power unit

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supported by power scavengers such as solar cells serve the purpose of providing functioning

power to the sensor node. Networking of such sensor nodes is an important aspect of these

sensor nodes, has important implication for civilian security such as target imaging, instruction

detection in sensitive locations and surveillance by detecting ambient conditions or presence of

objects [297].

Figure CM. 1 – A schematic diagram of sensor node [298]

Sensing - The use of carbon nanotubes as a sensing element has been mentioned in literature.

A number of examples of such sensors are mentioned in the Detection section of civil security.

The use of electrical and mechanical properties has been made in creating the smallest ‘balance’

that by mounting a single particle at the end of carbon nanotubes. On application of an electrical

charge the carbon nanotubes vibrates like a spring and mass of the particle is calculated using

changes in the resonant vibration frequency [299]. This remains an example of physical sensing.

Nanobarcodes comprising of 50nm cross section cylindrical rods can be coated with analyte

specific entities, for detection of complex molecules such as DNA [ 300, 301]. Chemical sensors

based on carbon nanotubes have been demonstrated in the detection of NO2 or NH3 by

signalling a change in the electrical resistance of the carbon nanotubes [302]. Titania nanotubes

sensors have been reported in the literature to have been incorporated in a wireless sensor

network for the detection of hydrogen [303].

Processing - Carbon nanotubes based transistors are expected to become an important

component of the processing unit in sensor nodes. IBM has developed and successfully

demonstrated using multiwalled carbon nanotubes or single walled carbon nanotubes, as

channels for field effect transistors. The current flowing through the nanotubes can be changes by

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a factor of 100, 000 by changing the voltage [304]. NEC has reported developing a method of

positioning the CNT which allow electrons to flow 100 times fasters than silicon and reduce the

power consumption by a factor of 20 [305].

Communication and Data transmission – The transfer of information maybe obtained

Microwave amplifiers are used in wireless communication are expected to form an important part

of the transceiver unit. CNT cathode developed thin film fabrication techniques have

demonstrated stable current densities in excess of 100 mA/cm2, which is the current density

necessary for amplifiers [306]. Excellent RF properties of nanotubes and nanowires have been

successfully demonstrated to have been integrated with wireless communication. The advantage

of this approach of using carbon nanotubes as an antenna is that it can communicate with the

sensing unit without have to use interconnects fabricated using lithography [307, 308]. Another

advantage of the nanotubes antenna is that it can serve as an excellent impedance matching

circuit to receive signals. Optoelectronic communication of information can be achieved through

the use of nanooptoelectronics, diffractive optical elements, optoelectronic transducers and

photonic components. Opotoelectronic components are composed of quantum wells, quantum

dots, and photonic crystals. A more detailed view on the research and development in the

optoelectronic communication maybe obtained from the ICT Technology sector of the

Observatory Nano project.

Storage - The storage unit of such a sensory network is expected to benefit from the improved

storage capacity. The millipede technology demonstrated by IBM can hold up to a trillion bits per

square inch, 20 times more information than the most dense information storage available. The

millipede works by punching thousands of indentation using nanosharp tips, which represents

bits. Ultra fine tipped V shaped silicon cantilever produced by surface silicon micromachining. The

millipede technology is expected to pack 10-15 GB of data [309]. CNT based memories

developed by Nantero have reported a 10GB memory. The NRAM offers advantages such as

non-volatility, high speed and price of a dynamic memory is expected to be a better candidate

than other memories. The nanotubes are sprinkled on silicon wafer, where the nanotubes are

balanced on the ridges of silicon. A change in the electrical charge can swing the nanotubes in

one of two positions representing a zero or one state. Another advantage offered by this memory

is the low power consumption required to change the state due to the small size of the nanotubes

[310]. A number of memory storage technologies are being developed that may have a potential

application in sensory network such as Molecular memory, Ferroelectric RAM, Magnetic RAM,

Phase Change Bridge RAM. A more detailed view of these developments and other storage

developments can be obtained from the Memory sub-sector of ICT Technology Sector in the

Observatory Nano project.

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Power Supply - The supply of power to sensory nodes is of utmost importance for continuous

condition monitoring of critical infrastructure. The use of nanocrystalline material and nanotubes

has been mentioned in the literature to improve power density, lifetime, and power

charge/discharge rates of batteries. Nanotubes as a replacement in the graphite-lithium electrode

of portable batteries are expected to improve performance by increasing performance due to

higher surface area. Nanocrystalline materials have been mentioned as potential material for

separator plates due to the foam like structure which can hold more energy [311]. Other materials

are being considered are transition metal oxides of cobalt, zinc, iron and copper for electrodes in

lithium ion batteries. The surface electrochemical reactivity is improved by nanoparticles thereby

improving the performance of lithium ion batteries [312]. Experiments have reported a 600%

increase in reversible energy capacity. Material for cathode based on carbon nanotubes, titanium

dioxide, and vanadium oxide have been mentioned in the literature [181]. Super capacitors have

been suggested as power units for such the sensory node due to their high energy storage

density and high power density. Carbon nanotubes increase the surface area of the capacitors

exponentially and thus are an ideal candidate material. Low resistivity, high stability and narrow

distribution of mesoporous size also make carbon nanotubes ideal for super capacitors [313].

Solar cells based on quantum dots have been mentioned to be suitable material for energy

scavenging applications for sensory nodes. CdS quantum dots have been demonstrated to self

assemble on the surface of nanocrystalline titanium dioxide and light harvesting electrode has

been fabricated from P25 particles using a pressing method. The method was mentioned to have

caused some loss in performance of the CdS coating though it was considered to be a suitable

option for low cost manufacturing [314]. A number of materials are being considered and

developed in photovoltaic, such as silicon based, polycrystalline thin film (copper indium diselnide

and cadmium telluride), single crystalline thin film, dye sensitised thin film, organic and polymer

solar cells. A more detailed view on the developments is available from the technology sub-sector

of photovoltaics in Technology Sector Energy of the Observatory Nano project.

A number of other methods have been suggested in the literature based on solar power, thermal

gradients and fluid flow [315]. Mechanical vibrations have been harnessed through piezoelectric

for transforming vibrations to electrical energy. Lead zirconate titanate (PZT) has been reported in

the literature for harvesting energy from vibrations. A thin film lead zirconate titanate MEMS

device has been developed. The device resonates at specific frequencies of an external vibration

source. The cantilever has a PZT/Silicon nitride bimorph structure with a proof mass attached to

its end. The platinum/titanium electrode was reported to be patterned on top of a sol-gel coated

PZT thin film. A spiral design for the cantilever has been proposed and demonstrated for

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compactness, lower resonant frequency, and a minimum damping coefficient. The device was

shown to demonstrate a continuous supply of 1 µW of continuous power [316]. An array of zinc

oxide nanowires have been reported in the literature for harnessing energy from mechanical

vibrations. The nanowire array is placed below zig-zag metal electrode with a small gap. The

piezoelectric semi-conducting coupling converts mechanical energy to energy. The device has

shown to produce high power density in relation to other microgenerators [317]. A more detailed

view of the technology research and development of the power supply are available from the

‘Power’ sub sector of the ICT Technology Sector in Observatory Nano project.

Role of Sensor Networks in Emergency Response - The role of sensors in emergency

response has been reported in the literature. The protocol design, application development and

security model has been mentioned to address the resource limitations of sensor nodes and

network. Some of the problems the architecture named ‘Code Blue’ aims to address are

robustness of signals received from sensors and communicated to the device, routing of signal

data to multiple nodes, and prioritisation of critical data flow over communication networks.

Security of wireless communication is expected to be enabled by providing enough computational

power at nodes allowing them to use dynamic cryptography protocols. The ability to locate the

node and sensory devices play an important role. In the event of serious causalities being

brought in to medical facilities, the facilities are overwhelmed with decision making at demanding

times. Sensory networks can be used for patient triage and tracking, temporary storage of patient

information, simultaneous monitoring of physical variables and tracking first responders in

providing trauma care to victims [318].

3.3.4 State of Research and Development

A comparative assessment of technology readiness levels has been done in Table CW.1 below

for nanotechnologies enabling sensor nodes. The sensing layer and its various developments

have been covered and comparatively assessed in the ‘Detection’ sub sector. Other technological

developments for processing, storage, transmission, communication and data transmission, and

power supply have been mentioned.

Table CW. 1 – A comparative assessment of Research and Development status of enabling

nanotechnologies in Condition monitoring of infrastructure and civilian zone environment

- 149 -

Fundame

ntal

Research

Applied

Researc

h

Prototy

pe

Field Trials / Pilot

plant ( Pre-

commercialisatio

n)

Deployed

(Commercial

ised)

Mass

Market

CNT

based

transistor

s for

processi

ng

CNT

cathodes

CNT

antenna

Nano-

optoelect

ronics

Millipede

memory

CNT

based

memory

Molecula

r memory

Ferroelec

tric RAM

Magnetic

RAM

Phase

Change

bridge

RAM

Nanocrys

talline

materials

for

batteries

Nanotub

e for

electrode

s

- 150 -

Transitio

n metal

oxides

Super

capacitor

s

Quantum

dot solar

cells

Thin film

solar

cells for

sensory

nodes

Mechani

cal

vibration

s from

cantileve

rs for

power

supply

Nanowire

array for

harnessi

ng power

3.3.5 Additional demand for research

Research and development has been mentioned in the literature to develop,

functionalities of sensory nodes and sensors as follows [313] :

- Programmable sensors with multisensing functions

- Wireless sensors with mobility

- Sensors with devices responding to stimuli

- Sensors with long and short range communication capability

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- Database built into sensory nodes

- Reducing interference in the transmission unit of the sensory node

- Eliminating noise from unwanted atoms or molecules in the sensing unit through

improved design

- Multiple attribute sensing has been suggested as a desirable function.

- Integration of various different sensors in one platform has also been mentioned

as a further research need.

- Interoperability of the sensor network and between sensor networks making it

easy for sensors to communicate with each other has been proposed as a

research need

- Deployment of sensors in uncertain and hostile environments may lead to loss in

functionality. Further research has been proposed for sensors to provide

information about its failure.

- Integration of nanoelectronics with sensing element through electrical contacts

has been mentioned as a research challenge.

One of the main limitations of sensory nodes in sensory networks is the low

computational capability, power availability and bandwidth limitations. Further research is

needed in enhancing performance of sensor networks in responding to emergencies and

medical disasters. Further research is also needed in taking prototype sensors to

deployment in clinical settings [318].

3.3.6 Applications and Perspectives

In the expert engagement process for the technology segment the following perspectives were

observed:

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• Funding research and development for Protection sub-sector was considered important

both for the European society and the economy.

• The main drivers for R&D in ‘Protection’ sub-sector were considered to be technological,

and environmental, health and safety (EHS). The technological drivers are primarily

related to cost, performance, efficiency, and absence of solution. Secondary drivers were

related as productivity gains, and competitive advantage in conflict.

• The drivers for R&D in ‘Condition monitoring’ segment was mentioned as ‘information

networking reliability’ and ‘protection of information and communication infrastructure’.

• The main barriers for ‘Protection’ sub-sector were considered as ‘intellectual property

conflict’ and ‘availability of finance’ for start-ups. Other secondary barriers were

considered as lack of supportive government policies, lack of tax incentives, access to

infrastructure, and inadequate technology transfer.

• The barriers for R&D in ‘Equipment and Infrastructure Protection’ segment were

mentioned as ‘inadequate research funding’, ‘lack of equipment and testing facility’ and

‘lack of product integration’.

• The most important functionality were identified as to be ‘information processing’,

‘information storage’, ‘power supply consistency’, ‘memory non-volatility and high speed’,

‘lifetime of operation of filters’, ‘operational capability retention in wide ranging conditions’,

and ‘wireless connectivity of sensor nodes’.

• Other secondary functionalities of interest were identified as ‘sensor characteristics’,

‘current density in circuits’, ‘Long and short range communication’ and ‘minimum

maintenance’ and ‘low power consumption’.

The theme of enabling nanotechnologies for sensor networks enabling CBRNE detection was the

topic of discussion at the Observatory Nano Symposium held in Dusseldorf in April 2009. The

following outcomes and recommendations were observed:

• Sensor networks would be valuable for trend monitoring and pattern recognition, either

globally across the city or in small local areas.

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• Greatest value addition for sensor networks would be in sensing layer of the sensor

nodes. Other nanotechnology research and development in information processing and

communication, and for energy has different drivers. These could be incorporated in

future.

• Integration of multichannel sensor array has not been accomplished as yet.

• Novel sensors could potentially be integrated with commercial of the shelf component to

achieve such a sensor network.

• The market for civilian security application would be created by the state.

• Investment would be independent of technology domain and more sensitive to capability

enhancement.

• Emphasis on dual use application was suggested to improve commercial attractiveness.

• Life cycle analysis of the material and nanomaterial for scenario dependent applications

should be conducted on a case by case basis.

3.3.7 Current Situation within EU

AMICON is a European Network of Excellence that brings together players in the field of Radio

Frequency Micro-Electromechanical Systems and Radio Frequency Microsystems. The project

targets research, education and applications aspects. The project aims to merge MEMS

technologies with Information Communication technologies. PHOREMOST was an FP6 project

that aimed to create a network of excellence that will address near and long term needs of

photonic functional components enabled by nanotechnology. Both the projects have relevance to

the Condition Monitoring of Infrastructure in the protection segment of the Technology Sector.

The European Commission funded Mobi-Health project looked at communication technology for

providing a continuous monitoring of trauma patients outside hospital environments. The

framework 5 project aimed to create a third generation network for monitoring purposes was

expected to save lives, generate vital medical research data and reduce medical services costs.

The following framework 7 projects have been funded by the European Commission in the

Security theme that are relevant to condition monitoring:

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• Seamless communication for crisis management (SECRICOM) has been initiated in 2008

for the development for a reference security platform as an interoperable system on the

existing communication network [319].

• Security System for maritime infrastructure, ports and costal zones (SECTRONIC) project

initiated in 2008, focuses on critical maritime infrastructure namely, passenger and goods

transport, energy supply and port infrastructure [320].

• Novel intruder detection & authentication optical sensing technology (IDETECT 4ALL)

project initiated in 2008 focuses on the need for alerting technology for surveillance and

intruder detection for critical infrastructure [321].

• Autonomous maritime surveillance system (AMASS) project initiated in 2008 focuses on

security of critical maritime areas using active and passive sensors linked to a network.

The project addresses illegal immigration, drug and weapons trafficking [322].

• Suspicious and abnormal behaviour monitoring using a network of cameras & sensors for

situation awareness enhancement (SAMURAI) project was initiated in 2008. The project

aims to develop and integrate monitoring systems based on cameras and sensors for

critical infrastructure site [323].

• Localisation of threat substances in urban society (LOTUS) project was initiated in early

2009. The LOTUS project aims to create a system to detect the preparation of explosives

and drugs during preparation and production of a terrorist plot. This will be demonstrated

by detection using sensors and global infrastructure for positioning and networking [144].

• Integrated mobile security kit (IMSK) was initiated in 2008. The objective of the project is

to combine technology solutions from Detection of CBRNE, area surveillance, and check

point control for additional sensitive security locations. The sensor data is expected to be

integrated with communication and data module to a command centre [44].

The following Preparatory Action for Security Research Funded projects were funded by the

European Commission and are relevant to condition monitoring:

• Vital Infrastructure threats and assurance (VITA) project has delivered an assessment of

threats and protection of highly networked infrastructure. The initial assessment of threats

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and proof of concept demonstrator were achieved for critical infrastructure in the 18

month period [324].

• Highway to Security: Interoperability for situation awareness and crisis management

(HITS/ ISAC) project objective was to enable information analysis and fusion from

numerous sources across borders to detect and provide early warning for suspicious

activities such as communication and movement of goods. The focus of the 18 month

project was prevention, prediction, interoperability and information sharing [325].

• Mobile Autonomous Reactive Information system for urgency situations (MARIUS)

project aimed at developing a autonomous command post which can be deployed for

monitoring during and after a crisis. The system is expected to integrate information

processing from sensors and communication capabilities as a generic crisis management

solution [326].

• Protection of Air Transportation and Infrastructure (PATIN) project aimed to ensure the

protection of air transportation system and critical ground infrastructure and security

networks against terrorist attacks. The project addressed issues such as interoperability,

crisis management and optimisation of networks [327].

• Surveillance of Border Coastlines and Harbours (SOBCAH) project aimed to demonstrate

a real time, user friendly, high automated surveillance systems for ports and borders. The

demonstration would be based on the architectural solutions for most advanced sensors

and networks [328].

• Transport Infrastructures Protection System (TIPS) project aimed to address security of

mainline, subway and metro systems of European cities. The project addressed

technological solutions for safety of passengers against explosives along with the

communication infrastructure [147].

• Wireless Interoperability for Security (WINTSEC) project aimed to study the standardised

internetworking layer at the core network level. The objectives were to achieve

interoperability in public and governmental security domain [329].

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4. Anti-counterfeiting, Authentication, Positioning and Localisation

4.1.1 Title – Anticounterfeiting

Anti-counterfeiting

Keywords: brand theft, forgery, holographic features, nanocomposites, carbon nanotubes,

quantum dots, organic nanofibres, laser surface authentication, SERS, physically unclonable

function, nanobarcodes, diffractive nanostructure, nanocluster, nanomaterial, anti-counterfeiting

4.1.2 Definition of Technology Segment

The anti-counterfeiting sub-segment covers the methods, techniques, devices, structures and

nanomaterials that help in the protection of the supply chain of industrial and consumer goods.

The nanotechnology developments in this segment aim to address brand theft and prevention of

intellectual property theft.

4.1.3 Short Description

A number of anti-counterfeiting technologies are being developed to counter theft of brand and

intellectual property. This section will observe the technology developments addressing the

increasing problems. Nanotechnology methods such as holographic features, laser surface

authentication, physically unclonable functions, magnetic fingerprints, nanobarcodes, surface

enhanced Raman scattering have been mentioned. Nanomaterials such as carbon nanotubes,

quantum dots, organic nanofibres are being developed for anti-counterfeiting applications. The

development of nanostructure, nanoscale features and nanoscale clusters to enhance the

security of supply chains.

Holographic features - Holographic patterns provide security features both overt and covert to

bank notes and credit cards. Application of holography has also been suggested for art.

Nanozeolites have been used in photopolymerisable recording material for security application.

[330]. The addition of inorganic additives has improved the properties of holographic polymers

- 157 -

that can be used for new photonic applications. The working principle of holographic recording is

the photo-induced modulation of the refractive index. This results from the variation in material

composition and density from photopolymerisation of nanocomposite and diffusion of components

from exposure to interference patterns. Experimental research has demonstrated

nanocomposites consisting of acrylate polymers and organically capped inorganic nanoparticles

as a medium for holography. Nanoparticles of SiO2 ,TiO2 and ZrO2 were used in the study.

Phololuminiscent nanoparticles of non-oxide semiconductors cadmium sulphide and zinc selnide

were also used. The research had investigated the preparation, properties, holographic

performance, and the polymer-nanoparticle structure. The nanoparticles of SiO2 were observed

to be the most effective in producing low scattering and highly selective holograms [331].

Experimental research has demonstrated the possibility of using luminescent nanoparticles in

photopolymerisable composites for holographic security technology. Lanthanum phosphate, with

an average size of 7nm, doped with cerium and terbium has been used as nanoparticles. Two

dimensional gratings have been recorded in the nanocomposite. Photoluminescence of these

nanoparticles within homogenous polymer film has been measured under ultraviolet light

excitation. The advantage of the luminescent nanoparticles is that they provide an additional level

of security for the hologram [332]. Experimental synthesis of fluorescent ZrO2:Eu3+ nanoparticles

have been reported in the literature. These spherical nanoparticles 4nm in size can be easily

dissolved in organic solvent and can be used to produce holographic gratings [333]. Progress in

holographic imaging has demonstrated a 164nm resolution using a table top extreme ultraviolet

laser. The experimental research was demonstrated on a photo resist of PMMA 120 nm thick, the

image of which was digitised using an AFM. The results demonstrated an improvement by a

factor of two in the lateral resolution [334].

Laser surface authentication - In laser surface authentication a laser is used to examine the

map of the surface roughness of an object using diffused scattering of a focused laser. The

obtained code is thereafter stored in a database that can be accessed at a later date. The code of

surface roughness is similar to iris scans and fingerprints, the probability of two codes matching

was demonstrated to be 10-72 for paper and 10-20 for matt finished plastic cards and coated

cardboard paper [335]. The advantages of the Laser Surface Authentication technique is that

surface roughness of a surface cannot be replicated therefore a high level of security is offered to

products, as compared to holograms and watermarks. Other advantages offered by the technique

are robustness against wear and tear, low cost of hardware, 100% accuracy, highly unique

features, covertness of the feature, speed at which scanning takes place on a production line,

and the overall low cost due to absence of chips. One of the main disadvantages is that it cannot

be used on transparent and reflecting surfaces, and the acceptable alignment limit is 1mm [336].

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Ingenia Technologies is commercialising the solution for the substrates such as paper, plastic,

metals and ceramics. The solution is aimed for integration into product, packaging, and

transportation stages of 37 supply chains. The implementation of the technique is expected to

target the brand theft and the forgery market. The development challenges of the technology are

the scanning apparatus and the design of codes database [337].

Physically unclonable function (PUF) – The anti-counterfeiting technology is being developed

at Philips Research for applications in optical devices, integrated circuits and S-RAM devices.

PUF comprises of two components, a physical protection layer and a cryptic layer. The physical

layer has a unique fingerprint, similar to LSA, and serves to protect the digital signature. Due to

the physical and cryptic layer, the solution is tamper resistant as verification of both layers is

essential. The fingerprint is printed on the surface of the packaging or the product which can be

then verified. The benefits offered by the technology are its tamper resistant nature, covertness of

the feature, ease with which it can be evaluated and non-reproducibility. The PUF could

potentially be embedded in RFID tags with digital signatures, thereby making the features

physically unclonable. S-RAM PUFs are also being developed by Philips [338].

Magnetic fingerprinting – Magnetic fingerprints are being developed and commercialised by

Singular ID as tags for products for which illegal counterfeits are being produced. The unique

fingerprints are created by distributing micro to nanoscale magnets in a non-magnetic matrix

material. The specific process used to synthesize magnetic nanoparticles depends on the

application and specification of the tag. Porous materials such as aluminium oxide can be used

as the matrix material and nickel based magnetic material are deposited through the pore

structure. The electroplating process used creates a random pattern and a unique magnetic

signature [339]. The unique signatures are read using GMR head scanner to obtain information

which is stored into a database. The magnetic material can be embedded in materials such as

metal, plastics and glass. The covert security features provide additional security to products in

the pharmaceutical, medical, engineering component, and bank cards. The tags are being

produced for anti-counterfeiting and brand security for automotive, fashion and pharmaceutical

markets [340].

Nano barcodes- Three dimensional nanoscale data encryption key, similar to barcodes has been

proposed in a filed patent. It consists of three dimensional polymer patterns in tens of

nanometres, of poly (methylmethacrylate) on silicon substrates as tri-dimensional barcodes.

Cross-linking the polymer using ultraviolet light provides a high durability material. Nano-imprint

lithography is used to generate the pattern on the surface. A number of dimensional coding

arrangements have been suggested – two dimension, two and a half dimension, three

- 159 -

dimensions, three and a half dimension and four dimensional code. A high resolution charged

coupled device camera fitted with an infrared filter is used to detect the reflection from silicon

surface using a laser in the infra-red range. The advantage that nanometre scale features provide

are the difficultly of being identified and even more difficult to duplicate such features. The

application of these features can be with banknotes, security papers, art, jewellery and gem

stones [341].

NanobarcodesTM particle system is being developed and commercialised by Oxonica. These

barcodes consist of striped submicron scale metallic rods. The barcodes use the difference in

reflectivity of gold, silver and platinum. These codes are read through an optical microscope using

proprietary software. A combination of one thousand metallic rods can be used to generate a

trillion unique codes. These barcodes can be applied in distinct surfaces such as those present

in inks, adhesives, laminates, paper, packaging, and films. They also find application in textiles,

thread and glass [342].

Surface enhanced Raman scattering tags – The unique spectra generated by Raman

scattering of substances can be utilised as an identification tool. SERS tags developed by

Nanoplex technologies use the principles of Raman scattering for identification purposes. The

SERS tag consists of metal nanoparticles, SERS reporter and, eventually, a coating material like

silica. Gold and silver nanoparticles are mainly used in SERS tags. These find applications in

bank notes, paper, packing, clothing and pills. The advantages offered by the technique difficultly

in reproducing due to infinite combinations, covert security feature, non-toxic, and

multifunctionality. One of the main disadvantages of the technique is the weak signal from the tag

that can be improved using surface enhancement by adjusting the type of substrate [342].

Quantum dots as barcodes for identification – A method for identifying and locating products

using quantum dots has been patented. Quantum dots fluoresce and produce characteristic

emission based on their composition and size. In the patented method quantum dots of one or

more particle size distribution are utilised as barcodes. The intensity of the emission at a fixed

wavelength can be varied to produce a binary or higher coding scheme. Quantum dots of

semiconductors for group II-VI, III-V, and IV are suitable for the identification application.

Semiconductor materials such as ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, GaN, GaP, GaAs, GaSb,

InP, InAs, InSb, AlS, AlP, AlSb, PbS, PbSe, Ge and Si were considered to be suitable for

application as quantum dots. The security tag can be used for consumer items such precious

jewellery, vehicles, and confidential paper [343 ].

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Organic nanofibers - Organic nanofibers have been suggested for application in banknotes. Gas

phase synthesis of functionalised organic nanofibres from organic precursors has been

mentioned in a filed patent. These organic nanofibres have been reported to have novel optical

properties such as pre-determined fluorescence under UV excitation [ 344]. Gain and lasing of

self assembled nanofibres have been studied experimentally, which was shown to be dependent

on the structure of the fibres [345].

Nanostructures - Anti-counterfeiting patterns have been produced for banknotes by depositing

adapted multilayered nanostructures. These structures produce different effects when interacting

with light such as change of luminosity and change of color which are used in security

applications in bank notes and credit cards. Experimental studies were conducted on concave or

convex structures of insect wings to study the effect [346].

Nanoclusters - Nanoclusters are assemblies of atoms or molecules that are covalently or non-

covalently bonded with largest overall dimension in the nanoscale [347]. They have novel

physical and chemical properties, which can be used for security applications. Clusters of metals

deposited on a substrate at a nanometric distance (5-500nm), from a wave reflecting layer can

act as a nanoresonator. Sensors and devices are based on surface enhancement of light

absorption. This technique forms the basis of producing thin film for anti-counterfeiting

applications, which is based on characteristic colours and special optical effects. This has formed

the basis of commercial products through Brandsealing which uses the patented cluster

technology to produce optical coding. These spectroscopic properties of the optical code are

authenticated using a reader. This technology has been considered by the authors to enhance

the security feature of threads in bank notes and much better than holograms for authentication of

new currency [348].

Nano-coloured materials in combination with active and sensory color-changing nano-features

and interactive properties are one of the promising concepts of Attophotonic’s nanotechnology

applications. By using multiple reactive nano-layers and nano-structured surfaces the

Attophotonics® Biosciences GmbH creates a wide range of colours using resonant nanoclusters.

The layers are designed to specifically reflect some spectral sub-fraction whereas other

electromagnetic waves are absorbed efficiently. Based on the particular nanostructure the

surfaces shines and even sparkles in a well defined colour-pattern. The innovative products are

manifold reaching from novel smart surface materials for design to films, foils, pigmented inks and

printed labels visually indicating the identity, quality and status of packed products [349].

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Diffractive nanostructures - Diffractive structures are useful for application in anti-counterfeiting

and brand protection. Structures of parallel lines with spacing of over 100nm are made up of

material with high refraction index surrounded with low refraction index material. In order to

enhance the color effect, a layer of chromophores and fluorophors materials such as quantum

dots and metallic nanoparticles have been mentioned. The device is to be used in form of

transferable labels and tags for banknotes, credit cards, passports and brand protection

applications. These have been mentioned to be better than optical variable devices, optical

variable ink, diffractive optical image wave device [350]. Diffractive optics based devices enabled

by nanomaterials have been reported in a filed patent for application in authentication and

security. A number of materials such as epoxy, acrylate, polycarbonate, UV-curable sol-gel

material, silicon oxide, carbide, diamond, carbon, carbon derivative, magnesium fluoride, ZnO,

ZnS, and/or titanium oxide have been indicated for use in the diffractive layer. Nanoparticles with

a high refractive index have been used in polymer matrix. For the mirror layer, metallic

nanoparticles have been suggested for use within metallic alloys. The application of the diffractive

optic device has been suggested for banknotes, credit cards, passports and for brand protection

[351].

Inexpensive and an easy to manufacture security packaging material and paper based on micro-

nanostructure have been reported in a filed patent. The packaging carries the micro-

nanostructures act as diffractive optical elements. The micro-nanostructures are embossed on to

the surface. A laser beam diffracted from the structures is used to detect the security feature. The

application of this method has been suggested for consumer applications such as electronics

goods and medicine [352]. Experimental research has been shown to demonstrate layer by layer

self assembly of gold nanoparticles on cellulosic fibres, wood and bacterial cellulose as substrate.

Gold nanoparticles of 15-100nm in size could be modified by silica shells to enhance optical

properties of the nanocomposite. The development will have applications in the security paper

synthesis [353].

Verify First Technologies have filed a patent for security documents, have described two security

features on a printable substrate, one that is on the substrate and the other partially or completely

embedded in the first feature. The first security feature has nanostructures for trapping printing

matter for latent copy-void warning message. The second security feature is also nanostructured

configured for forming pixel pattern on digital document reproduction. Thermochromic ink is

partially arranged in the pattern of the first nanostructure. This technology is expected to act as

security features for bank cheques, stocks and bond certificates [354]. A prior art by the same

organisation has demonstrated nanopatterns with different nanostructures such as polygons,

circles, ovals, crosses, and alphanumeric characters [355].

- 162 -

Confocal type laser profile microscope, have been demonstrated in measuring the thickness of

films posted on passports [ 356]. Spectral information based on color of an object captured on to

a database has been described in a filed patent. The spatial analysis software along with the

apparatus is used to compare unique patterns [357].

Others Nanomaterials - Nanosized titanium dioxide and zinc oxide have been demonstrated as

ultraviolet blockers by the Canadian Bank note company, in enhancing security features of

documents such as birth-certificates, driver’s license, travel documents and bank notes. The

patent describes the method of producing a transparent window on a security document,

including a transparent ultraviolet blockers, and printing an invisible ultraviolet fluorescent ink.

The authentication of the document is done using ultraviolet wavelengths of light [358].

Single walled and multiwalled carbon nanotubes have been demonstrated in a security mark

comprising of multiple layers. The identification information is contained with the patterned layers

composed of conductive material. The conductive layer is made from carbon nanotubes with

diameter in the range of 0.5 nm - 15nm. Antimony Tin-Oxide has been alloyed with carbon

nanotubes to produce conductive layers. The conductive layer is patterned to form resistors by

printing with conductive ink. The code in the conductive layer is read by a reader which identifies

an object, based on its conductivity. The application has been envisaged in prevention of

counterfeiting of products and security cards [359].

4.1.4 State of Research and Development

This section provides a comparative assessment of research and development status of enabling

nanotechnologies. Fundamental Research is defined for this purpose as research with no

particular goals of commercialisation. Applied Research is defined as research conducted in

academia and industry directed towards a specific purpose and application. Prototype has been

defined as Applied Research or Fundamental Research that has found a potential market

application. Technologies that are in the field trial state are defined as those that are in the

process of commercialisation, and are being tested. Deployed nanotechnologies are those that

have found an early stage market. Mass Market has been defined as those technologies that

have been adopted by large population and are attractive high growth markets. The spread of

technology readiness indicates the research and development focusing on different materials and

application for a given technique. Table AC.1 below shows a comparative assessment for Anti-

Counterfeiting sub-segment.

- 163 -

Table AC.1: Anti – Counterfeiting Comparative Research and Development Status

Fundam

e-ntal

Researc

h

Applied

Research

Prototy

pe

Field Trials / Pilot

plant ( Pre-

commercialisatio

n)

Deployed

(Commerci

alised)

Mass

Market

Holographic

feature (

Nanocompos

ite)

Laser

Surface

Authenticatio

n

Physically

Unclonable

function

Magnetic

fingerprinting

Nanobarcod

es

SERS tag

Quantum

dots

Organic

Nanofibres

Nanostructur

es

Nanocluster

Nanomaterial

s

Diffractive

Nanostructur

es

- 164 -

4.1.5 Additional demand for research

Further materials and applications research for the anti-counterfeiting, authentication, positioning

and localisation have been mentioned as:

Research is needed in controlling and modulating the organic nanofibres self assembly

process for enhanced application performance in authentication [345].

4.1.6 Applications and Perspectives

The expert engagement process identified trend for anti-counterfeiting as:

• Main drivers for research and development are technological, economic gains, social

impact and regional policy Technological drivers are principally identified as cost,

performance, efficiency and absence of a solution.

• Brand Theft is considered important driver for R&D in anti-counterfeiting.

• Main barriers for research and development were identified as lack of supporting

governmental policies, access to equipment and infrastructure as well as inadequate

technology transfer.

• Failure to integrate during field trials was considered a development barrier. Limited

supporting policies were also considered as a barrier for technology segment.

• The technological segment represents an economic implication for society with a justice

related dimension to it as well.

• The attractive application research area was ‘Intelligent materials and packaging’.

Automated packaging for product identification along with back tracing combined with

sensory features was suggested.

• The most important functionalities were identified as ‘accuracy in identification’, ‘not

easily reproducible feature’, ‘multifunctionality of identification tag’, ‘portability of

identification unit’, ‘uniqueness’, ‘ease of integration’ and ‘long operating life’

- 165 -

• The holographic features for anti-counterfeiting applications are currently on the market.

• Laser Surface Authentication and Nanocluster based identification is expected to be in

the market in the next 5 years. Both the technology solutions were considered attractive

growth markets.

• Nanobarcodes, SERS tags and nanostructured security features are expected to appear

on the market in the next 10 years. Nanostructured security features were considered to

be very attractive higher growth markets in relation to Nanobarcodes and SERS tags.

• Other qualitative information suggested that there should be ‘greater emphasis on

creating company awareness of product security features’, ‘improving international laws

to dealing with fraud’ and ‘more emphasis on technological development than basic

research for authentication’.

• Based on the application, the potential toxicity of nanomaterials should be considered.

Cadmium compounds were mentioned to one of the most severely regulated materials.

4.1.7 Current Situation within EU

The following Preparatory Action for Security Research Funded projects were funded by the

European Commission and are relevant to explosives detection:

• Secure Container Data Device Standardisation (SECCONDD) project aims to initiate

standardisation of technical interface between secure container or vehicle and a data

reader at a port or border crossing. The project is expected to identify any potential

threats from terrorist activity or insertion of contraband goods [146].

- 166 -

4.2.1 Title - Authentication

Authentication

Keywords: authentication, biometric, fingerprint, retinal, nanocomposites, opal, nanostructured

material, polymer nanocomposites, opal, nanofibre, quantum cryptography

4.2.2 Definition of Technology Segment

The authentication technology segment would cover applications of nanotechnologies in

verification of individual identity using fingerprints, retinal, facial and hand features. The

technology segment would cover nanotechnology developments for identity verification and

security of information and communication.

4.2.3 Short Description

Research and development addressing the verification of identify and security of information and

communication has been observed in this section. The use of nanomaterials in identity

verification has been done demonstrated through its use in nanocomposites and protection of

information and communication through quantum cryptography.

Nanocomposites – Biometrics are viewed to be vital in identification of a person’s identity.

Biometrics encompasses recognition method for human fingerprinting, iris and retinal, facial and

hand features. Polymer nanocomposite material based on multi-dyes has been reported in

literature for application in security labelling. Polymer multiphase nanostructured materials have

been reported in the literature as a medium for recording biometric information. Fluorescent dyes

with non-overlapping absorption and emission spectra have been used to record information by

photo-bleaching of the dyes. Design, synthesis and fabrication of two different approaches – full

color and monochromatic spatial arrangement of three biometric features, photograph, fingerprint

and signature was demonstrated. The dyes used were anthracene, 4-amino-7-nitrobenzo-2-oxa-

1, 3-diazole (NBD) and Nile Blue. The size of the An labelled core was reported to be 450nm, dye

labelled layer as 15 nm and spacer layer as 160nm. Destructive readout using a low power laser

was used to examine the information recorded on to the nanostructured material. The advantage

of this approach is the longevity as the destructive readout can be used on a daily basis for 4

years of image being accessed [360, 361].

- 167 -

Opal based nanocomposites - Iridescence of stacked silica spheres known as natural opals is

caused by interference of light with lattice planes [362, 363]. An industrially scalable approach for

producing opals from polymer has been mentioned in the literature. Quantum dot doped polymers

opals have been created for security applications by compression moulding of flexible films.

Experimental research has demonstrated nanoparticulate carbon black in elastomeric opals

produces remarkable change in colour under compression loading [364].

Nanotechnology based platforms of P-Ink and Elast-Ink have been mentioned as commercially

viable options for authentication technology. Active color tuning of opal has been utilised in these

technology solutions. One solution reversibly shrinks or expands on removal or application of a

voltage to a metallopolymer opal. Opal embedded in a matrix of polyferrocencylsilane gel is

termed as P-Ink. The other solution is based on studying the reversible dimensional changes of

an elastomeric opal that change based on application or removal of a mechanical force.

Composite opal formed by combing opal with synthetic rubber, which when dissolved leaves a

network of voids in a rubbery matrix known as elastomeric inverse. Due to the highly porous

structure, and the color shift observed with increasing pressure can be utilised as a highly

fingerprinting sensor for use in forensics, biometric security and authentication [365].

Optical Fibres - Optical fluorescent fibers randomly arranged have been suggested as a solution

for anti-counterfeiting by Tracer Detection Technology Corporation. The fibers provide a

constantly moving a non-repeating target, making counterfeiting difficult. A unique algorithmically

generated code printed with the fibers, add to the security feature. The code optically read has

mentioned the possibility of generating a duplicate is 1 in 1015. The advantage this technique

offers over other is due to the difficultly in producing the same fluorescent dichroic fibers,

producing the same emission behaviour at the detector wavelength, fibers of same length and

shape. Other alternatives to fluorescent markers have been suggested as nanocrystalline

materials, carbon nanotubes, fullerenes, dendrimers, nano-intermediaries and nano-composites.

Fluorescent nanoparticles such as quantum dots, fluorescent polymer particles, silica coated

fluorescent polymer particles, dye loaded latex nanobeads, and iron oxide nanoparticles have

been mentioned. The application has been reported for pharmaceutical, designer and branded

clothing [366].

Quantum cryptography – Quantum cryptography is based on the quantum mechanics principles

of uncertainty and entanglement. Two known approaches are considered for quantum

cryptography. The first approach is that using polarisation of photons, where the polarised

photons representing bits of information. The vertical polarisation represents a zero state and

horizontal polarisation represents one state. The information which is encrypted as diagonal

- 168 -

polarisations is used as an encryption method. The second approach used is that of entangled

photons, where the entanglement property utilises to transfer cryptic information. In this method

both the sender and receiver get one photon from the entangled pair. Due to pairing of entangled

photons the measurements of polarisation of light provides the same output at both ends. The

measurements are added to give a string of zero’s and one’s to get the key [367]. The research

on quantum cryptography has been successfully demonstrated in transferring funds between the

Vienna City Hall and the Bank of Austria. Entangled photons have also been sent over a distance

of 100 km by researchers at Northwestern University [181].

4.2.4 State of Research and Development

This section provides a comparative assessment of research and development status of enabling

nanotechnologies. Fundamental Research is defined for this purpose as research with no

particular goals of commercialisation. Applied Research is defined as research conducted in

academia and industry directed towards a specific purpose and application. Prototype has been

defined as Applied Research or Fundamental Research that has found a potential market

application. Technologies that are in the field trial state are defined as those that are in the

process of commercialisation, and are being tested. Deployed nanotechnologies are those that

have found an early stage market. Mass Market has been defined as those technologies that

have been adopted by large population and are attractive high growth markets. The spread of

development indicates the different methods and materials being researched and developed of

the application. A comparative assessment of nanotechnologies enabling Authentication has

been shown in Table AU.1.

Table AU.1 – Authentication enabling nanotechnologies

Fundame

ntal

Research

Applied

Resear

ch

Prototyp

e

Field Trials / Pilot

plant ( Pre-

commercialisatio

n)

Deployed

(Commercial

ised)

Mass

Market

Nanocomp

-osites

Opal

based

Nanocomp

osties

- 169 -

Optical

fibres

Quantum

cryptograp

hy

4.2.5 Additional demand for research

The following additional demand for research was mentioned in the literature:

Applied research is needed to demonstrate material characteristic to hone color switching

times, wavelength tuning range and mechanical strength for opal based P-Ink and Elast-

Ink authentication solution. The applications have to be further supplemented by

demonstration as a scaled up pilot plant [365].

4.2.6 Applications and Perspectives

The expert engagement process identified trend for authentication as:

• Main drivers for research and development are technological, social impact and regional

policy. Technological drivers are principally identified as cost, performance, efficiency

and absence of a solution.

• Forgery is considered important driver for R&D in authentication.

• Main barriers for research and development were identified as lack of supporting

governmental policies, access to equipment and infrastructure as well as inadequate

technology transfer.

• Failure to integrate during field trials was considered a development barrier.

• Application trend is towards enhanced and secure identity documents as well as finger

print detection.

• The attractive application research area was ‘Intelligent materials and packaging’.

- 170 -

• The most important functionalities were identified as ‘accuracy in identification and

authentication’, ‘not easily reproducible feature’, ‘multifunctionality’, ‘uniqueness’, ‘ease

of integration’ and ‘long operating life’

• Nanostructured polymer films are expected to be on the authentication market in the

next 5 years. The market is expected to be attractive growth market.

• Other qualitative information suggested that there should be ‘more emphasis on

technological development than basic research for authentication’.

• The debate on privacy versus security is an important one for the authentication

technology segment.

4.2.7 Current Situation within EU

The following Preparatory Action for Security Research Funded projects were funded by the

European Commission and are relevant to authentication:

• European Security: High level study on threats responses and relevant technologies

(ESSTRT). The support action project has provided a comprehensive overview of

necessary responses to security challenges. The technology development is expected to

address personal identification through biometrics solutions for documentation by

improving false rejections and acceptance [45].

• Towards a network for testing and certification of biometric components and systems (

BioTesting Europe) project aimed to set up a European Network of testing and

certification for biometric components [368].

- 171 -

4.3.1 Title – Positioning and Localisation

Positioning and Localisation

Keywords: positioning, localisation, radio frequency identification, carbon nanotubes, nanowire,

supply chain

4.3.2 Definition of Technology Segment

The positioning and localisation segment would cover all enabling nanotechnologies that would

enhance capabilities in positioning and localising of goods and objects.

4.3.3 Short Description

Position and Location of industrial and consumer goods is vital in ensuring the security of supply

chains. Radio Frequency identification tags have been centre of focus of development. The use

of metal nanoparticles and carbon nanotubes has been observed for their functionality enhancing

capability.

Radio frequency Identification (RFID) - Radio frequency identification tags are being used for

surveillance and logistics applications. RFID work on identification of low frequency and high

frequency, it consist of readers, transponders, and host systems [369]. The fabrication of RFID

components such as capacitors, inductors, circuits and interconnects need low resistance

conductors. The literature points towards a novel process for producing low resistance

conductors patterns. These patterns are produced from solutions of organic-encapsulated silver

and copper nanoparticles that can be printed and annealed [370].

Carbon nanotubes are being researched as suitable antenna elements for RFID tags. The high

conductivity and length of nanotubes make them suitable for between 50 GHz and 1 THz wireless

communication. One of the major limitations and subject of study is the achieving wireless

communication of antenna with other nanometric components. Development of vertically aligned

CNT based switches for RF-MEMS has also been mentioned in the literature. While striction

remains a problem, CNT’s overcome these due to dramatically reduced surface area and

charging effects in dielectrics [371]. The use of carbon nanotubes in an inductively couple

antenna with RFID has been experimentally demonstrated [372].

- 172 -

RFID embedded in paper has been considered as one of the best organic substrates due to its

cheap processing, similar dielectric constant as air and its ability to embed nanoscale additives.

These can also be coupled with sensors and batteries as actives tags in multilayers for security

applications [373]. Method for producing silver nanoparticle (2-5nm prepared from toluene) based

inks and nanowires (75nm in diameter) have been reported in the literature. These are

considered suitable for applications such as printed RFID antennas [374].

4.3.4 State of Research and Development

This section provides a comparative assessment of research and development status of enabling

nanotechnologies. Fundamental Research is defined for this purpose as research with no

particular goals of commercialisation. Applied Research is defined as research conducted in

academia and industry directed towards a specific purpose and application. Prototype has been

defined as Applied Research or Fundamental Research that has found a potential market

application. Technologies that are in the field trial state are defined as those that are in the

process of commercialisation, and are being tested. Deployed nanotechnologies are those that

have found an early stage market. Mass Market has been defined as those technologies that

have been adopted by large population and are attractive high growth markets.

A comparative assessment of enabling nanotechnologies for positioning and localisation is shown

in Table PL.1 below.

Table PL.1 – Positioning and Localisation

Fundame

ntal

Research

Applied

Researc

h

Prototy

pe

Field Trials / Pilot

plant ( Pre-

commercialisatio

n)

Deployed

(Commercial

ised)

Mass

Market

RFID

enabled

by metal

nanoparti

cles

RFID

enabled

by CNT

- 173 -

4.3.5 Additional demand for research

The following additional demand for research was mentioned for positioning and localisation

applications:

Further research is need in transmission of microwave signals in nano-antennas and

nano-switches enabled by carbon nanotubes. New communication architecture has been

suggested in literature for secure communication. CNT based devices are suggested to

increase rate of data transfer on mobile phones, providing high efficiency, low cost and

miniaturised broadband capabilities. W-band based security systems, enabled by

nanoscale components, will improve evaluation and avoiding collision with obstacles in

aircraft paths in difficult weather conditions [371].

Further research for integration of carbon nanotubes into RFID tags has been mentioned

in the literature. Optimising layer by layer self assembly to optimise capacitance has been

indicated. Research has also been suggested in fabrication parameters with sensing

performance [372].

Tracking and tracing of substances and vehicles are considered to be important

capabilities. Research in developing capabilities for automated observation and

monitoring of substances and objects has been mentioned [199].

4.3.6 Applications and Perspective

The expert engagement process identified the following trends:

• Main drivers for research and development are technological, economic gains, social

impact and regional policy

• Theft is considered important driver for R&D in positioning and localisation.

• The technological segment represents an economic implication for society. RFID

technology presents a privacy related issue as well.

- 174 -

4.3.7 Current Situation within EU

SELECT NANO was a framework 6 project that aimed at the development of multifunctional

nanoparticles using a process of Sonoelectrochemistry. The network of excellence aimed to

synthesise, scale up and apply the nanoparticles for detecting and authenticating articles using

printing conductive labels and coding information based on the printed pattern. The PEARL

(privacy enhanced security architecture for RFID tags) project is aimed at developing tools and

methodologies for RFID systems, while preserving user privacy. The ongoing project aims at

modelling relevant privacy and security policy as well as developing protocol for RFID

environments. The project also looks at integration of RFID tags and developing back office

support system applications.

The following Preparatory Action for Security Research Funded projects were funded by the

European Commission and are relevant to positioning and localisation:

• Advanced space technologies to support security operations (ASTRO +) was a 15 month

project aimed at transverse technology analysis, definition with end user and

demonstration of mission concepts. The project demonstrated imagery intelligence

facility, communication and tracking of vehicles and security personnel [375].

• People real-time observation in buildings: Assessment of New Technologies (PROBANT)

in support of surveillance and intervention operations, project aims to develop, integrate

and validate technologies for crisis intervention and surveillance situations. The

technologies validated by PROBANT would be used by civilian agencies in threat

detection during hostage situations, kidnapping and hijacking to obtain images in real

time [376].

- 175 -

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