Nanotechnology

& Polymer Nanocomposites Where are We Now

Molecular Nanotechnology
An Overview
Richard Feynmans talk in 1959, entitled There's Plenty of Room at the Bottom. K Eric Drexlers 1986 book Engines of Creation: The Coming Era of Nanotechnology.

Top Down Approach IC, MEMS, etc. Bottom Up Approach Molecular Machine, Ribosome, DNA, Cell Membrane, etc.

Molecular Nanotechnology

The next big thing is really SMALL

Molecular Nanotechnology

No Cook and Look

Obstacles:
Stickiness, Brownian motion, surface to volume ratio, Force of Electromagnetism, Van de Waals forces, Quantum mechanical tunneling

Design

About Complexity
Small Change in the Force Field or the Boundary Condition of the Interacting Molecules could Result in Completely Different Results.

Self-Assembly: Reversible processes in which preexisting parts or disordered components of a preexisting system form structures of patterns.

Self-assembly of gold-polymer nanorods results in a curved structure. Chad Mirkin, Northwestern University

Irreducible Complexity
"a single system which is composed of several interacting parts that contribute to the basic function, and where the removal of any one of the parts causes the system to effectively cease functioning". (Michael Behe, Molecular Machines: Experimental
Support for the Design Inference)

Solution:
Molecular Interaction Data Base Computer Simulation: Molecular Dynamics Simulation

Molecular Dynamic Simulation

Schematic of the polymer layered silicate nanocomposite (PLSN) morphologies: (a) intercalated and (b) exfoliated.

(a) Molecular Dynamics simulation "snapshot" of a silicate-surfactantpolystyrene nanocomposite. (b) The corresponding number density of carbon atoms as a function of distance.

D.B. Zax, D.-K. Yang, R.A. Santos, H. Hegemann, E.P. Giannelis and E. Manias. J. Chem. Phys., 112 , 2945, (2000).

Polymer Nanocomposites (PNC)

Applications
Heat-resistant materials Light weight and high strength structural materials Electrical package, conductive polymers. Barrier Properties Corrosion resistant, coating or structure Electro-magnetic field shielding Selective photo sensitivity, coatings, etc
It is estimated that widespread use of PNCs by car manufacturers could save over 1.5 billion liters of gasoline annually and reduce CO2 emissions by nearly 10 billion pounds!

Polymer Nanocomposies
Popular Nano-reinforcements
Carbon Nanotube, Bukcyball

Clay

POSS

Graphite

Building Blocks of the Nano Age

Other Synthetic Materials

Cellulose

Polymer Nanocomposies
Surface Modification, Dispersion

Ion exchange for clays

Addition reaction on CNTs (fullerenes) Acidification, fluorination, etc. in order to attach different functional groups onto nano reinforcement surface to improve dispersion as well as reactivity with the matrix structure morphology change & tailoring of interface

Focus : Carbon Nanotube Functionalization

Azomethine Ylides M. Prato, A. Hirsch et al., 2001
DMF, 130 oC 120 h R1NHCH2C(=O)OH + R2CH=O - H2O , CO 2 S R1 SWNTs W R2 N N H2C CH _ + T N R1 R2 x

Nitrenes A. Hirsch et al., 2001, 2003

160 oC ODCB - N2

R1 = - CH2(C H2)6CH3, - CH2CH2OCH2CH2O CH2CH2OCH3

ROC(=O)N3 + SWNT

SWNT [>NC(=O)OR] x

R2 = H,

O CH3,

R = tert-Butyl, Ethyl, oligoether groups

Aryl Diazonium Salts, J. Tour et al., 2001

R SWNTs, -1 V CH3CN + Bu 4N BF 4 SWNT R x ODCB / CH3CN, 2:1 65 oC NH2 SWNTs (CH3)2CHCH 2CH2ONO R

Fluorination J. L. Margrave et al., 1998

F2/H2 SWNTs heat [F]x-SWNTs

N2 BF 4

Acyl Peroxides V.N.Khabashesku et al., 2002

heat SWNTs + RC(=O)OO(=O)CR - CO2 [R]x-SWNTs

R = tert-Butyl, halogen, COOH, 2, COOH, CO2CH3 etc. NO

R = C11H23, C6H5, CH2CH2COOH

Polymer Nanocomposies
Network Formation
Controlling Factors Properties of the Matrix Properties of the Nano-reinforcement Interface Properties of the Nanocomposites Interaction between Reinforcement and Matrix during Loading (Thermal, Mechanical, Electronical, etc.)

POSS

Carbon Nanotubes

Conflicting Property Reports

Conflicts Result from Differences in
Matrix Polymer Repeating Unit Relative Mobility of Nano-reinforcement Compared with Matrix Degree of Crosslinking Polymerization Mechanism

Nano-reinforcement
Surface Treatment Degree of Dispersion etc.

Deconvolution
Simple Model System Experimental Condition Raw Materials Selection Molecular Dynamics

the Future

Properties Design Microscopic Morphology Control

Optimum Interface Design

Mechanosynthesis of Polymer Chains

MWCNT/Epoxy Nanocomposites

Structure Change Morphology Change Increased Mobility Thermal Mechanical Properties

Preparation of Nanocomposites
MWCNT (40-60nm,10 m)

A- CNT

PGE-CNT

EPON-CNT

Bulk Sample

Surface Treatment (Continued)

Pure-CNT

MWCNT/Epoxy Nanocomposites
A
A-CNT

Di-epoxy: Epon 828 Mono-epoxy: PGE

PGE-CNT

Epon-CNT

Auad, M. L. et al, J. J APPL POLYM SCI 66: (6) 1997

Solubility Change After Modification

Pure-CNT

A-CNT PGE-CNT EPON-CNT

Pure-CNT

A-CNT PGE-CNT EPON-CNT

Solubility change in water

Increasing solubility in THF

FTIR Spectrum of Treated CNTs

760 cm-1 Epoxy ring
12 Band

2920,2850 cm-1 C-H Stretch

1710 cm-1 Carboxylic group

1250 cm-1 Aromatic Ether

CNTs/ Epoxy Composites

Epoxy (EPON 828) Functionalized CNT dispersed in THF 1wt%

Solvent Evaporation

DMAP (initiator)
(-4dimethylamino)pyridine A-CNT 0.9wt%

Crosslinking Reaction

0.7wt% PGE-CNT

Nanocomposites
0.51wt%
Williams et al. Macromol. Mat. and Eng. 289, 315, 2004

Epoxy-CNT

Morphology: SEM
10 m 10 m

CNTs agglomerations

1wt% CNT
Matrix EPON 828
10 m 10 m

Pure-CNT
10 m

A-CNT

PGE-CNT

Epon-CNT

DMA Test @ 1wt% Treated CNTs

300

250

Epoxy A-CNT composite PGE-CNT composite EPON-CNT composite

Storage Modulus (MPa)

350

4000

Loss Modulus (MPa)

3000

200
40

Pure Epoxy A-CNT Epoxy PGE-CNT Epoxy EPON-CNT Epoxy

60

150

Temperature ( C)

100
Storage Modulus (MPa)

50

Pure Epoxy A-CNT Epoxy PGE-CNT Epoxy EPON-CNT Epoxy

1000

40

60

80

100

120

140

160
o

180

200

220

240

Temperature ( C)
0 140 160 180
o

Temperature ( C)

MD Simulation of SWCNT&EPON Mixture

1.6

Pair Corelation Function (cnt-cnt;o-cnt)

1.4

1.2

1.0

G ab (r)

0.8

0.6

0.4

0.2

0.0 0 2 4 6

Blue: 50-150 ps Red: 500-600 ps

8 10

r (Angstrom)

Amorphous unit cell, orthorhombic, (7,0) swCNTs dispersed in Epon828 600,000 steps (600ps), NVT ensemble (298K), 1.4 g/cc, 14.9V%, 69W%

What to simulate in MD?

Stress-Strain Curve/Elastic Constants
Pair Distribution Functions Tg

Diffusive Behavior
IR Spectrum & Radiation Scattering Function (X-Ray, Neutron) Concentration Profiles Temperature Profile Orientation Correlations

CONCLUSIONS

The mobility of the polymer chain & the mobility of the nano-fillers dominates the properties of nanocomposites.
Well dispersed nano-fillers would have a confinement effect for the matrix, which leads to the improvement of Tg. Different interfacial bonding would lead to varied improvement for the glass transition temperature.

Future Work

Exploring the toughening mechanism of CNT polymer nanocomposites, focus on thermal mechanical properties.

Single walled carbon nanotube reinforced shape memory PU.

Building a MD model for thermoset polymers reinforced with randomly oriented SWCNTs/ modified SWCNTs.

Thank You
Questions?

Molecular Dynamics Simulation

MD ABC
Ideal length and time scale Bridging the molecular level with REAL WORLD MATERIALS Materials Structure Characterization and Property Prediction

Molecular Dynamics Simulation

Initiation:
Definition of Simulation Cell {R (N,V,E)}
* Periodical Boundary Condition * Minimum Image Convention

Energy minimization (non crystalline) Assignment of initial velocity {v (N,V,E)}

Molecular Dynamics Simulation

Force Fields:

Non-bond <Van der Waals, Hydrogen Bond, and Coulomb Interaction>

Covalent Bond <Bond stretching, valence angle bending torsion>

The force on each atom is related to the partial derivative of potential energy over the position vector of the atom.

Force = Mass*Acceleration
We can derive the ensemble of {R} and {v} of the system after minute time step t Thus, we can numerically decide the trajectory of the system over time.

Molecular Dynamics Simulation

Equilibrium:
Allow sufficient number of time steps to be calculated so that the system reach equilibrium --- thermal dynamic data (such as Total Energy, Potential Energy, Cv) no longer change or oscillate around the equilibrium value. )

Data Collection:
The trajectory average of the structural or thermal dynamic property over time will be the simulated value.

Absorbance
0.1 0.2 0.3 0.01 0.02 0.03 0.04 -0.00 -0.0 0.000
CNT PGE-CNT EPON-CNT

Absorbance
0.015 0.020

Absorbance

0.005

0.010

Default Text

3500

3429.3

3000

2922.0 2850.3 2856.0

2924.8

2500

Wavenumbers (cm-1)

2360.2

2360.2

2000

1709.5 1633.0 1567.9

1500 1000

1709.5 1635.8 1553.7 1451.8 1379.9 1457.5 1379.9 1382.7 1635.8

1256.6 1182.9 1110.4 1030.1

1259.5

1103.7 1024.4

877.2 817.8 806.5