Post Processing #1 Dispersion, Functionalization and CNT Blends

Bhabendra Pradhan Columbian Chemicals Company

November 3rd, 2006

WTEC Workshop

Outline
Background Dispersion Post-processing (Heat treatment and
functionalization) Observations

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Functions and Applications of Carbon Nanotubes

Courtsey: M.Endo

Agglomeration of Carbon Nanomaterials is a problem

50 nm

Carbon Black

Single-walled carbon nanotubes

Multi-walled carbon nanotubes

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Dispersion science is the solution

Dispersion
- Wetting - De-agglomeration - Stabilizing interactions
van der Waals Interaction Electrostatic Interaction Steric Interaction

Rheology Substrate Interaction

Influence of Carbon Nanomaterials Properties on De-agglomeration

Aspect Ratio - dispersing higher aspect ratio materials is easier due to
reduced interaction between agglomerates. They build viscosity, thus more shear which aids in dispersion.

Nanotubes/Matrix Compatibility - an improvement in wettability is

usually accompanied by an improvement in dispersibility. The wettability dispersibility. improvement brought about by adding functionalization to the carbon in carbon some systems usually enhances dispersibility. dispersibility.

Physical Form single nanotubes are easier to disperse than bundled

or entangled nanotubes.

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Poor vs. Good Dispersion/Polyurethane (PU)

In Solution
5 nm

5 nm

In PU

5 nm

HRTEM

Courtesy:Zyvex

Purification and Suspension of CoMoCAT Nanotube

SWNT gel Patent Pending Freeze-dried pure material Dry Oxidation at 250 C

HF to remove silica support

Courtesy:Daniel E. Resasco

University of Oklahoma

Stable suspension in Surfactant solution

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General Surface Activity for NanoCarbons

Property describing the interaction of a carbon
nanomaterial surface with its surroundings In polymers, surface activity can be defined as the ability of a carbon surface to chemically bind polymer

Both of the above points are applicable for carbon nanotubes (single or multi wall)

Continuous MWCNT Manufacturing (Japan)

Carrier Gas

Base Resin

Raw Material

Reactor No.1 High Temperature Furnace No.2 High Temperature Furnace

Master-batch Production

Features (Based on ENDOs Method) Floating Catalyst Chemical Vapor Deposition Two-stage high temperature treatment (i. oxidative, ii. inert) Production rate: kilograms/hour High purity; 99.5wt% carbon Tune structure via growth and post-processing conditions

Products

Courtesy: Nano Carbon technologies Co., Ltd

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Microstructure of MWCNT
(a)
Average diameter 40 to 90 nm 10 mm Linear and long (aspect ratio > 100)

10 mm

After dispersion in toluene

(b)

200 nm

Courtesy: Nano Carbon technologies Co., Ltd

Plastics/MWNT Compound for ASD/ESD

FEATURES High conductivity with low loading Improving the resin physical property Smooth and uniform surface Minimal increase of viscosity Extremely low of particle sloughing Uniform conductivity Minimal shrinkage during molding

MWNT

MWNT dispersed in toluene

MWNT dispersion in plastics (PC/MWNT5%)

Courtesy: Nano Carbon technologies Co., Ltd

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Functionalization
Two distinct bonds:
van der Waals Covalent/Customizable

Binding applicable to CNMs

(SWNTs, MWNTs, CNFs)

Functionality may be
customized
Functionalization technology

Dispersion Adhesion Other Courtesy:Zyvex

Single-walled Nanotubes/ Epoxy Composites

Sidewall amine functionalization of nanotubes using peroxide
O
SWNT

O
.

+ HOCCH2CH2

||

CH2CH2C-OH

||

||

O H 2 CH CH2 C

A new curing agent

OH H 2 CH CH2 C N H 2 CH CH2 C OH N

OH H 2 HC CH2 C

H 2 HC CH2 C OH OH H 2 HC CH2 C N H 2 HC CH2 C OH N

OH C H 2 CH CH2 H 2 CH CH2 C OH

Nanotubes become integral to the epoxy. The epoxy is (reformulated).

Fully Integrated Nanotube Composite

Courtesy: Enrique V. Barrera, Rice University, Houston, TX

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SWNTs-Epoxy composites for EMI

0.1 0.01 1E-3 1E-4

0 -1 -2 -3 log (
-2 0 2

(S/cm) Conductivity

1E-5 1E-6 1E-7 1E-8 1E-9 1E-10 1E-11 1E-12 1E-13

-4 -5 -6 -7 -0.5 0.0 0.5 1.0 1.5 2.0 2.5 log((p-pc)/pc)

4 6 8 10 12 14 16

wt % SWNT p

Percolation pc=0.062%

SWNTs homogenously dispersed

Y. Chen and P.C. Eklund, NanoLett, 2006, 1141

Functionalized SWNTs for Chem/Bio Sensors

Ferrocene-SWNTs Hybrid for Electrochemical H2O2 Measurement Much enhanced H2O2 detection for many bio/medical applications

Y. Chen et al.,Chem. Phy. Lett., 2006, 420, 416-420

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Zyvex processing leads to products

Zyvex

Courtesy: Zyvex

MWCNT applied in sporting goods

Courtesy: Endo, Shinshu University

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Observations
Progress in Dispersion of Carbon Nanotubes - MWCNTs for sporting goods, ESD & EMI applications (North America, Japan and China) - SWCNTs for ESD, EMI and bio-application (North America, Japan and China) More work needed on dispersion, functionalization and blend of single walled carbon nanotubes (SWNTs) to capitalize the full potentials of these unique carbon nanomaterials. More work needed to scale up purification of SWCNTs.

Summary Post Synthesis Processing #1. Dispersion, Functionalization and Blends (Objectives/Results)
Objective: Clarify research opportunities and needs for promoting progress in the field generally
More work needed on large scale purification, dispersion, functionalization and blending of single walled carbon nanotubes (SWCNTs)

Objective: Evaluate the position of foreign research programs relative to those in the U.S.
US leading in the understanding of dispersion and functionalization of single walled carbon nanotubes Japan is far ahead in large scale processing of MWNTs

Objective: Indicate where successes have been made and obstacles identified
Successes: MWNT purification, dispersion and blending Obstacles: SWNT, post growth purification, functionalization, dispersion and blending

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