Development and Characterization

of NanocompositeMaterials

Dr. Fazal Ahmad KhalidPro-Rector

GIK Institute of Engineering Science and TechnologyTopi, NWFP

Khalid@giki.edu.pk

International Scientific Spring 2010NCP, QAU

CNT Reinforced

Molecular Level Mixing

Nanotechnology Growth

S. Milunovich, J. Roy. United States Technology Strategy. Merrill Lynch. 4 Sept. 2001

Info Bio

Nano

Milestone1959 R. Feynman Delivers “ Plenty of Room at the Bottom”

1974 First Molecular Electronic Device Patented

1974 Taniguchi used the term Nanotechnology

1981 Scanning Tunneling Microscopic (STM)

1985 Buckball C60 discovered

1986 Atomic Force Microscopy (AFM) Invented

1987 First single-electron transistor created

1991 Carbon Nanotubes Discovered

2000 US Launches National Nanotechnology Initiative

~ 2000 Years Ago – Sulfide nanocrystals used by Greeks and Romans to dye hair~ 1000 Years Ago (Middle Ages) – Gold nanoparticles of different sizes used to produce different colors in stained glass windows

History

What is Nanoscale

1.27 × 107 m 0.22 m 0.7 × 10-9 m

Fullerenes C60

12,756 Km 22 cm 0.7 nm

10 millions times smaller

1 billion times smaller

Exciting new science and technology for the 21st century

Human hair ~ 80 μm

© Deb Newberry 2002,2003,2004,2005,2006,2007

Macro – Micro - Nano

Macro or Conventional MachinesBuild and assemble

(m - mm)MicromachinesBuild in place

(0.1 mm - 0.1 µm)

NanosystemsBrought together by forces at the atomiclevel

(100- 1 nm)

Nanotechnology: Key component of converging technologies

Materials &Chemistry

Molecular Electronics NEMS

MechanicallyStrong Material

Quantum Devices

MolecularEngineeringAtom-

Molecular

Manipulation

Miniaturization of Semiconductor Devices Molecular EngineeringAtom Molecular Manipulation DNA-Protein Manipulation

Expectation of new technology domain and new market

Carbon Nanotube

Fuel Cell

NanobioDevices

Lifescience

DNA

Protein

Manipulation

Sem

icond

ucto

r

min

iatu

rizat

ion

Mechanics

ElectronicsNew applicationsNew materialsNew systems & devices

NanomaterialsZero-Dimensional

Nanoparticles (oxides, metals, semiconductors and fullerenes

One-DimensionalNanowires, Nanorods and Nanotubes

Two-DimensionalThin films (multilayers, monolayer, self-assembled and mesoporous

Three-DimensionalNanocomposites, nanograined, micro- and mesoporous and organic-inorganic hybrids

Synthesis andPhysical Fabrication

Si/Ge

Si

Nanomaterials Size-Dependent Properties

Chemical Properties – reactivity, catalysis

Surface area to volume ratio

- Surface energy ⇑ – high reactivity- Al nanoparticles – energetic materials

Nanoscale melting temperature

- Nanocrystal – surface energy ⇑ – melting temp ↓- CdSe (3 nm) nanocrystal melts @ 700 K (1678 K)

Thermal Properties - melting temperature

Wang,et al, FIU

NanomaterialsSize-Dependent Properties

Mechanical Properties – strength, adhesion andcapillary force

Optical Properties – absorption and scattering of light

Electrical Properties – tunneling current

Magnetic Properties – superparamagnetic effect

Nanofluidic properties

New Properties promise new applications

Properties of Bulk Nanostructured Materials

BenefitsStrengthToughnessFormability

LimitationsManufacturing small things big?Structural stability

ODS Alloys and Nanocomposites

Goa, University of California

Increasing Copper Strength

• Plastic deformation of copper introduces work-hardening (copper gets stronger) and reduces the grain size

• Hall-Petch relation predicts materials get stronger as grain size decreases:

σy = σ0 + KHPd-1/2

(Yield strength is inversely proportional to grain size)

Material Yield Strength

Cold Worked Copper 393 MPa

400 nm Copper 443 MPa

100 nm Nanograin Copper 900 MPa

10 nm Nanograin Copper 2.9 GPa

Arzt, MPI Stuttgart

Problems in Nanotechnology

Create

Manipulate

Analyze

Small objects 1 – 100 nm in at least one

dimension

Nanomanufacturing - Requirements

Nanomanufacturing/ nanofabrication technology should:be capable of producing componentswith nanometer precisionbe able to create systems from these componentsbe able to produce many systemssimultaneouslybe able to structure in three dimensionsbe cost-effective

Mimicking the naturePlants are made from cellsCells use molecules (clusters of atoms) from the air, soil and water

18

Empa Report 2004

AFMFEG-SEMFEG-TEMFIB

50 µm

Carbon Nanotube

200 nm D. Zhou and L.A. Giannuzzi, UCF

Carbon Nanotubes Grown From FIB Prepared Seeds

Holes Drilled by FIB andFilled with Iron as Catalyst

Gold particles on carbon

20

Intelprocessors with features measuring 65 nanometers

20 nanometer transistor

Atomic structure

Gate oxide less than 3 atomic layers thick

Important for:Power efficient computingCommunication products

New Developments in Processing and CharacterizationApplications

in biomaterials

Hip Joints - replacements Heart valvesKnee Joints - replacements Stents

Biomaterials: A material intended to interface with biological systems to evaluate, treat, augment, or replace any tissue, organ or function of the body

Williams D. F. The Williams Dictionary of biomaterials 1999,Liverpool (UK): Liverpool University Press 42

Applications

in crystalline Diamond MEMS

Diamond coating surface morphology: (111)-diamond film (left) and (100)-diamond coating (right).

Diamond gears. Diamond accelerometer.Courtesy: J. Lou, W. Milne et al (Cambridge University)

Applications

Cleaning Up the Environment

Field demonstration that iron nanoparticles can remove up to 96% of a major contaminant – trichloroethylene – from groundwater at an industrial site From W. Zhang, Lehigh UniversityFrom W. Zhang, Lehigh University

Applications

Large Increase in Lighting EfficiencyLarge Increase in Lighting Efficiency

Lauren Rohwer Lauren Rohwer displays the two displays the two solidsolid--state lightstate light--emitting devices emitting devices using quantum dots using quantum dots her team at her team at

Sandia National Labs Sandia National Labs has developed. has developed.

•• Dept. of Energy estimates that ~20% of energy Dept. of Energy estimates that ~20% of energy used in U.S. is for illumination used in U.S. is for illumination

•• Nanotechnology quantum dot phosphors hold Nanotechnology quantum dot phosphors hold promise of more economical white light LED promise of more economical white light LED lightinglighting

•• LEDLED--based lighting could cut the electricity used based lighting could cut the electricity used for illumination by as much as 50 percent by for illumination by as much as 50 percent by 2025; 2X more efficient than fluorescent2025; 2X more efficient than fluorescent

The Cook Nuclear Plant The Cook Nuclear Plant

Capacity ~2 gigawatts

Cutting electricity for lighting in half would result in energy savings roughly equivalent to the annual energy production of 50 nuclear reactors

Applications

Nanocomposite Materials

Engineering

Energy

Transport Auto- and LocomotivesNaval & Aircrafts

Sports

SpaceDefense

Bridges StructuresBuildings

MMCsPMCsCMCs

NanoComposites – engineering, multifunctional coatings, biomedical and devices

26

Pictures from http://www.space.com/businesstechnology/technology/space_elevator_020327-1.html

The Space Elevator

CNTs Reinforcement

Materials Diameter(µm)

Strength(G Pa)

Young’sModulus

(G Pa)

Thermal conductivity

(W/m K)

Density(g/cc)

Boron 140 3.3~4.0 370~400 100~200 2.3~2.5

SiC 15~145 2.9~4.0 210~400 70~110 2.5~3.5

Al2O3 20 1.5 380 30 3.9

Carbon fiber 7~13 2.1~5.0 240~500 250~600 1.7~2.1

Aramid fiber 12 3.0~3.6 70~180 0.3 1.4

Carbon Nanotubes 0.01~0.04 20~50 600~1200 1800~6600 1.6

ASM handbook 21, (1987) 579 P. J. F. Harris, Int; mat; Reviews 49, (2004) 31

CNTs – excellent properties, new applications 3D wafers

Source: The Fredonia Group, “Nanomaterials Demand in Composites, 2010”, © 2006

Significant Market OpportunityNational Science Foundation forecasts $1 trillion worth of nanotechnology-enabled products on the market by 2015

$1.4 billion Federal Research and Development Investment in 2008

2005 2010 2015

$273 Million $740 Million $3.8 Billion

Nanocomposites Advantage: Stronger, Lighter, Less Expensive Game Changing

Traditional

Innovative

CONVENTIONAL COMPOSITEHigh strength BrittleLower weight

NANOCOMPOSITEHigh strength Not BrittleLowest weight

METAL ALLOYSHigh strength High weight

CNTs composites in sports industry

Babolat’s Tennis Rackets [Babolat Inc.]

BMC SLC01 Pro MachineTM [Modified from “PezCycling News - What's Cool In Pro Cycling”]

Nitro LiteTM Ice Hockey Sticks [Montreal Sports]

Baseball bats [Anaconda Sports]

“Thermal management is one of the key concerns in diverse fields such as Microelectronics and Space Technology”ExtreMat Project

New Materials with enhanced

thermal conductivity

Approach to transfer the attractive physical propertiesof CNTs and diamond to bulk engineering components

InterfaceLoad TransferHeat Transfer

Traditional AlloysCu-W

New Materials

Al-SiCAl-DiamondCu-Diamond

Cu-CNTs Part of the work on Carbon based NanoComposites

λu = λrVr + λm(1 – Vr)Rule of Mixture

DiamondDiamond

C60 C60 ““BuckminsterfullereneBuckminsterfullerene””

GraphiteGraphite SingleSingle--wall Carbon Nanotubewall Carbon Nanotube

Availability & decline in cost of synthetic diamond & CNTs

CNT-Cu based Nanocomposites

Production of Nanocomposites

Powder MetallurgyContamination & interfacial reactions

Mechanical alloyingContamination & damage

Compaction – HIP/Sintering

Liquid Metal Infiltration (Squeeze Casting)Gas Pressure InfiltrationMolecular Level Mixing

Production benefitsbut stability of nanophases

C. Zweben, Power Elect. Tech. Feb., 2006

Advanced Thermal Management

Materials

Semiconductors, microelectronicand optoelectronic devices

HEAT DISSIPATIONTHERMAL STRESSES

WARPING

Thermal Conductivity

First Generation:<200 W/m-K

Second Generation:<400 W/m-K

Third Generation:>400 W/m-K

Excellent thermophysical propsReducing cost

-Servers, notebook computers-Plasma display, PCBs-Optoelectronic packaging

Carbon NanotubesElectrical properties

Transistor,Wiring,FED

Metal Semiconductor

Metallic or Semiconducting conduction depending on chiralitiesAppearance of Quantum Effect due to 1-d structureHighly-Effective Electron Emission

Chemical:Adsorption, Storage, CatalystsChemical modification, Composites

Fuel cellsSensors

Mechanical: Super strong structure Due to C-C bonds Composite materials

Nanostructure made from multiple atoms

Strength and Thermal Conductivity

Challenges in

Processing of CNT Based Nanocomposites

Agglomeration - van der Waals forcesStability

Conventional Powder MetallurgyNo interfacial strengthNon uniform dispersionCNTs located on surface after mixingof metal/ceramic (no diffusion along/across powders)

No improvement in properties

In CNT-polymer matrixInterface is strong

Molecular Level Mixing

Mixing of CNT and powder in a solution involving molecular level mixingInteraction between the components atthe molecular level due to surface functionalization of CNTs CNTs – Cu Matrix (Better Load Transfer)Homogenous distribution of CNTs in

thematrix - solution based mixingAvoid damage to CNTs

New approach

CNT-Cu Based Nanocomposites

Functionalized CNTs + ethanol

Addition of Cu(CH3COO)2.H2O

Suspension of CNT/Salt Precursor

Drying process of mixture consistsof CNT/Salt Precursor

Calcination & Reduction

Sintering

Composite Samples

CNT dispersion

CNT/Cu composite powders

Dispersion

Mixing

Fabrication of nanocomposite powders

Consolidation of nanocomposite powders

Attachment of functional groupsto remove electrostaticrepulsive forces on CNTs

Attachment of Cu ions to functional groups on CNTs

Cu ions on CNTs oxidized to formpowder

Crystalline powder

CNT-Cu based Nanostructures

Morphology of MWCNTs, TEM images

SEM

CNT-Cu based Nanostructures

CNTs and Copper acetate monohydrate

mix

CNTs dispersion in ethanol

Drying (100 °C) and calcination (320 °C) of mix

Reduction of copper oxide

Uniaxial Cold compaction

Sintering @ 900 °C

Characterization

Synthesis

Interaction Between CNTs & Copper Acetate Monohydrate

CO2

C- H

O- H

C- O

Cu- O

Cu- N

Chemical bonding between CNTs and copper matrix enhances the load transfer efficiency from copper matrix to CNTs

The absorption at 630 cm-1 and 698 cm-1 was attributed to the presence Cu-O and Cu-N bonding

Which indicates the interaction between copper precursor and the functional group on the surface of carbon nanotubes

CNT/Cu based Nanostructures

SEM image showing morphology of synthesized Cu particles

SEM image of sintered compositeshowing stability of CNT in 5% sample

Schematic diagram showing CNT implanted on Cu particles

CNT

SEM image showing diffusionof CNTs in Cu nanoparticles

SEM image showing CNTs and Cu nanoparticles mix

New Developments in Nanotechnology

Progress on Processing and Characterization of CNT Based Nanocomposites

Application of New Approach - Molecular LevelMixing to achieve better interfacial propertiesand uniform dispersion of CNTs in copper matrix