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  • Nanoscale Trends, Opportunities and Emerging Markets

    Christopher C. Ibeh

    Pittsburg State University (PSU), Pittsburg, KS 66762

    Abstract

    Nanotechnology has attained the status of currency but is predominantly an emerging and trendy technology. This is desirable as it is poised for growth and sustainability. At the 2010 Nanotechnology Entrepreneurship Forum, there was a consensus among the guest speakers and panelists for the need to move beyond the Forbes.Com top ten nanotechnology products to achieving its true potential in the aerospace, naval and homeland security infrastructure development. In order to achieve this potential that is currently estimated at 20 Billion ($1,085 Billion in 2015) Dollars, the challenges posed by nanotechnology need to be addressed and leveraged. A concerted approach of research and education at Pittsburg State University is leveraging the opportunities at the nanoscale. Introduction

    Background There is a school of thought that contends that nanotechnology is not really new despite the 1991 invention of carbon nanoubes (CNTs) that is attributed to Iijima and NEC, Japan1-2. Recent molecular structure studies have found carbon nanotubes (CNTs) and carbon nanowires3-8 in a sample of a 17th century sword made from Damascus steel. The Damascus steel were first made in the 8th century and last manufactured in the 18th century. Sabers and swords made from the Damascus steel had extraordinary strength, extremely sharp cutting edge and the characteristic wavy damask banding pattern. These characteristics of the Damascus steel sabers and swords posed challenges to the Crusaders of those times. The contention is that the sabres and swords [Figure 1] forged from Damascus steel may have

    Figure 1: The Sabres and Swords made from Damascus Steel (circa 1700s and prior) [Courtesy: Alexander Dietsch, NatureNews, November 15, 2006] gotten their strength from nanoscale structures in Wootz steel that contains iron ores from India and Sri Lanka9-13. The Indian iron ores contain transition metal impurities that could have facilitated and catalyzed the formation of the nanotubes (CNTs) from burning wood and

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    leaves during the high temperature, annealing and forging manufacturing process of the Damascus steel. Asbestos is another case in point in the nanotechnology timeline. It is a known carcinogen and a discontinued material in most industries14-16. Asbestos is a naturally occurring silicate mineral with long, thin fibrous crystals; the rupture or damaging of asbestos releases fibrous asbestos particles into the air. Susceptibility to asbestos and the development of cancerous conditions such as mesothelioma (malignant lung cancer), asbestosis (non-cancerous, pneumoconiosis), etc arise from exposure to airborne fibrous asbestos particles. Figure 2 shows two of the many types of asbestos. The typical dimensions of asbestos are 3.0 - 20.0 m length and 0.01m thickness (10*10-9 m). In 1989 US Environmental Protection Agency (EPA), banned the commercial manufacture, importation, processing and distribution of most asbestos-containing products. The original 1989 EPA ban was vacated and remanded by the 1991 U.S. Fifth Circuit Court of Appeals but the upgraded EPA ban remains in effect under

    A B C Figure 2: Some of the Many Different Forms of Asbestos [Courtesy: US Geological Survey] A = Serpentine Asbestos [(Mg,Fe)3Si2O5(OH)4, Magnesium/Iron Silicate Hydroxide)] B = Tremolite Asbestos; C = Presence of Asbestos in the Lung. the 1999 Clean Air Act and the Toxic Substances Control Act (TSCA). Asbestos manufacturing has been discontinued in the US since 2002, and importation has decreased from 2530 tons in 2005 to 715 tons in 2009. The nano-size dimension of asbestos implies that it is a nanomaterial; this highlights the need for safety that is of paramount importance in nanotechnology. In addition, the diminished but continued usage of asbestos in the US despite the EPA rule on it suggests a realization of its efficacy and indispensability in certain formulations and applications. Nanotechnology is generically defined as the creation, processing, characterization, and utilization of materials, devices, and systems with dimensions less than 100 nanometers. A nanometer is one billionth of a meter or 10-9 m. Nanoscale-sized systems exhibit novel and enhanced physical, mechanical, chemical and biological properties/functions. Figure 3 is an FE-SEM micrograph of a sparse network of isolated individual Single Wall Carbon Nanotubes (SWCNT), prepared by CVD with cobalt nanoparticles as catalyst and alcohol as the carbon source and grown on silicon/silica chips 17-19. Figure 3A shows the nanoscale size of CNTs; CNTs are 50,000 to 70,000 times smaller than a typical hair strand.

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    The US National Nanotechnology Initiative has identified four major generations of nanotechnology development: passive nanostructures, active nanostructures, nanosystems and molecular nanosystems. Passive nanostructures, circa 2000, include dispersed and contact

    A B

    Figure 3: A. Carbon Nanotube Network Compared to a Hair Strand (Dark Gray) [Courtesy: Jirka Cech, http://www.jirkacech.com/blog/]; B. Atomic Force Microscope Image of ECSA Nanosensor [Courtesy: CNCMM-PSU].

    nanostructures such as aerosols and colloids, and nanostructures-based products such as nanoparticles reinforced composites, etc. Active nanostructures, circa 2005, include bioactive, targeted drugs and biodevices, and physico-chemically active nanostructures such as actuators, amplifiers, 3D transistors and adaptive structures. Nanosystems, circa 2010, include hierarchical/hybrid architectures, controlled assembling, 3D networking, robotics, etc. The fourth generation, molecular nanosystems, circa 2015 2020, includes molecular and sub-atomic designed devices20-22, etc.

    The objectives of this paper are to discuss: the current trends, challenges, opportunities and emerging markets of nanotechnology. The current trends in nanotechnology are highlighted via the relevant literature approach. The different types of nanomaterials are explored, and their associated challenges including safety are specified; the mechanisms for overcoming these challenges are proposed. The nanotechnology research and education at Pittsburg State University and partner institutions are utilized to illustrate some of the emerging opportunities and markets at the nanoscale.

    Relevant Literature: Current State of the Nanotechnology Industry

    In 2007, there were more than 370 nanotechnology companies23. Of these, 78 were nanoparticles companies; the complete demographics include: fabrication equipment (50), inspection/analysis (49), carbon nanotubes (46), semiconductors (21), sensors (21), coatings (17), batteries (12), solar cells (12), displays (12), and others (85). Figure 4 shows the market share of the projected $1085 Billion nanotechnology industry by segments; materials, electronics and pharmaceuticals are ranked numbers 1, 2 and 3 at 31%, 28% and 17% respectively. It is important to note that nanotechnology is also slated to play a role in sustainability. Figure 5 indicates that the projected growth of nanotechnology depicted by Figure 4 is in line with the nanotechnology hype index, and impacts every segment of society.

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    Figure 4: 2005 2015 Market Share of the Nanotechnology Industry [Courtesy: NSF]

    The Nanotechnology Hype Index [Data: Lux Corp.]

    0

    0.5

    1

    1.5

    2

    2.5

    3

    1 2 3 4 5 6 7

    Years: 1=1995; 4=1998; 7=2001

    Num

    ber

    of A

    rtic

    les C

    itin

    g

    Nanote

    chnolo

    gy

    Years: 1=1995 & 7 =

    2001

    Figure 5: The Nanotechnology Hype Index [Courtesy: Lux Corporation ] Josh Wolfe, Forbes/Wolfe Nanotech Report, January 12, 2005, Forbes.Com Top Ten

    Nanoproducts

    Forbes.com Top Ten Nanotech Products include24 a fullerene-based golf driver by Tokyo-based Maruman & Co that out-classes the conventional titanium-based 366c golf driver in bending stiffness, hardness, resilience and flight distance (15 extra yards); a nano-based golf ball by Buffalo, NY-based NanoDynamics Inc. that has the capability for flight path correction as it is able to absorb and channel the energy from the driver head; washable

    Potential Impact of Nanotechnology - Market Share

    Materials

    31%

    Electronics

    28%

    Pharmaceuticals

    17%

    Chemical

    Manufacture

    9%

    Aerospace

    6%

    Sustainability

    4%

    Enhanced

    HealthCare

    3%

    Tools

    2%

    Materials

    Electronics

    Pharmaceuticals

    Chemical Manufacture

    Aerospace

    Sustainability

    Enhanced HealthCare

    Tools

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    mattress; nanosilver dressing for burn wounds that cleans and disinfects in one step; aerogel footwarmer; 3M dental adhesive, etc.

    Figure 6: NanoDynamics Nano-based Golf Ball that has flight path correction. Subhasish Mitra, Philip H. S. Wong, Nanotechnology-Carbon Nanotube (CNT)

    Electronics, Stanford Nanofabrication Lab25-26

    This research effort epitomizes some of the best practices in nanoelectronics as it leverages fundamental research in CNT science into useful nano-chip technology for high speed computing based on quarter-size CNT chips. CNTs are highly electrically conductive, and their small, nanometer size allows for wafer scale, smaller circuits than the conventional silicon circuits. In this, CNT instead of silicon is grown on quartz wafer facilitated by catalyst nanoparticles at 900 oC for 17 hours. This growth process is carried out at optimal conditions of density, length and uniformity to marginalize the problem of misalignment that plagues nanoelectronic manufacturing and logic gate design. 100-nm gold is evaporated on the grown CNT to embed the CNT in gold. A special tape that looses its adhesiveness at 120 oC is applied over the gold-CNT wafer. The tape is removed to lift the gold and CNT; the tape with gold and CNT is applied to a new substrate. The gold is chemically dissolved away. Standard lithography and photoresist techniques are applied to the system for pattern printing. CNT logic gates design is a challenge due to CNT misalignment. Logic gates are used to produce circuits and circuits give systems. Eric K. Drexler, Nanorex Inc., Molecular Machinery Gallery,27-28

    A B C Figure 7: K. Eric Drexlers 4th Generation Molecular Designs of Gear s and Bearing . A. The MarkIII(k), a nanoscale planetary gear; B. The SRG-III Gear - the third parallel-shaft speed reducer gear; C. Small Bearing. Animated videos of fourth generation molecular designs of gears and bearings by Eric Drexler are available on the websites of References 27 28. The MarkIII(k) is a nanoscale planetary

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    gear design; it couples an input shaft via a sun gear to an output shaft through a set of planet gears. The planet gears roll between the sun gear and a ring gear on the inner surface of a casing. This animation was implemented with QuteMol29 by reading PDB files from a NanoEngineer-1 molecular dynamics simulation. A section of the casing atoms is hidden to expose the internal gearing assembly. QuteMol is an open source (GPL), interactive, high quality molecular visualization system. QuteMol exploits the current OpenGL shaders GPU capabilities to provide innovative visual effects. QuteMol visualization techniques enhance clarity and understanding of the 3D shape and structure of large molecules especially complex proteins. The SRG-III is the third parallel-shaft speed reducer gear; it is the first molecular gear train ever designed. The SRG-III has 15,342 atoms, and is the second largest nanomechanical device modeled in atomic detail. The Small Bearing was also modeled and simulated via the NanoEngineer-1 software. Peter Lillehei, "Quantifiable Assessment of SWNT Dispersion in Polymer Composites,"

    Nanotechnology Entrepreneurship Forum, April 23, 2010.30-32

    Figure 8: A. NASA Subsonic Fixed Wing Program; (B). NASA Sample #1; (C). NASA Sample #5 A NASA nanoscale initiative sponsored by the Subsonic Fixed Wing program focuses on the development and characterization of lightweight and multifunctional nanomaterials that will enable cost-effective, aerospace cargo transportation [Figure 8a]. In addition to lightweight, other desirable attributes in this application include radiation protection, electrical conductivity for lightening strike protection, actuation, thermal conductivity, sensing, health monitoring, self healing, energy generation, energy storage, etc. This effort emphasizes the fundamental understanding of the underlying science33-34 of how the bulk properties are influenced by such nano-attributes as dispersion, aspect ratio, interfacial phenomena, structure (primary, secondary and tertiary), purity, defects, etc. Transition of nanotechnology to aerospace and aircraft applications will be facilitated via such factors as technology readiness, verifiable distribution and orientation of nanoparticles, quality assurance and quality control tools and methodologies, certification plan, and the need for industry-academia-government collaboration. This NASA effort has resulted in the development of new tools that enable the generation and collection of relevant and useful data. The Poly-transparent imaging, one of the newly developed analysis tools, enables one to see through the polymer as if it is clear and transparent, and to truly observe the nanotube network deep within the sample. The contrast mechanism is currently not well understood but it allows the quantitative

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    representation of nanomaterials dispersion. Figure 8 depicts the quantitative distinction between the ordinarily mixed sample of 8B and the in-situ polymerized and sonicated sample of 8C. The study employs the use of Minkowski functionals, volume (), surface (s) and connectivity () to validate experimental data. The dispersion of nanoparticles is one of the challenges of nanotechnology, and a key element in achieving the potential of nanotechnology. Fujitso Corp., SemiConducting Leading Edge Technologies, Novel Carbon Nanotube-

    Graphene 3D Composites, Nanotech 2009

    This joint project between Fujitso Corporation and SemiConducting Leading Edge Technologies35 leverages the 2D graphene planar structure and the 1-D CNT cylindrical structure to produce a 3D Composite that conducts electricity in all directions.. The 2-D graphene conducts electricity in the h...