CNT Manufacturing Study Products · CNT Manufacturing, NSF 11/3/06 Objectives of Panel Study of CNT...

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CNT Manufacturing, NSF 11/3/06 Carbon Nanotube Manufacturing 2006: Introduction and Overview Peter C. Eklund CarboLex, Inc., & Dept’s of Physics and Mat. Sci. Engineering Penn State University CNT Manufacturing, NSF 11/3/06 CNT Manufacturing Study Products North American Workshop Baseline Report Final Workshop on Panel’s Assessment Final Assessment of International CNT Manufacturing and Applications Disseminated by web and hardcopy 1

Transcript of CNT Manufacturing Study Products · CNT Manufacturing, NSF 11/3/06 Objectives of Panel Study of CNT...

Page 1: CNT Manufacturing Study Products · CNT Manufacturing, NSF 11/3/06 Objectives of Panel Study of CNT Manufacturing in North America and Asia – Clarify research opportunities and

CNT Manufacturing, NSF 11/3/06

Carbon Nanotube Manufacturing 2006:

Introduction and Overview

Peter C. Eklund

CarboLex, Inc.,&

Dept’s of Physics and Mat. Sci. EngineeringPenn State University

CNT Manufacturing, NSF 11/3/06

CNT Manufacturing Study Products

– North American Workshop Baseline Report– Final Workshop on Panel’s Assessment– Final Assessment of International CNT Manufacturing and

Applications• Disseminated by web and hardcopy

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Page 2: CNT Manufacturing Study Products · CNT Manufacturing, NSF 11/3/06 Objectives of Panel Study of CNT Manufacturing in North America and Asia – Clarify research opportunities and

CNT Manufacturing, NSF 11/3/06

Objectives of Panel Study of CNT Manufacturing in North America and Asia

– Clarify research opportunities and needs for promoting progress in the field generally

– Identify opportunities for international collaboration and mechanisms for achieving success

– Evaluate the position of foreign research programs relative to those in the U.S.

– Indicate where successes have been made and obstacles identified

– Provide government decision-makers and the research community with data to move CNTs into the marketplace

CNT Manufacturing, NSF 11/3/06

WTEC CNT Panel Members

• Peter Eklund*, Panel Chair,Physics & Mat Sci Eng’ingPenn State University

• Apparao Rao*, Physics, Clemson University• Pulickel Ajayan*, Material Sci & Engineering, RPI• Bhabendra Pradhan*, Columbian Chemical• Andrew Rinzler^, Physics, Univ of Florida• Jing Kong^, John Hart^, Electrical Engineering, MIT• Robert Blackmon^, Harper International, Inc

Site Visits, Workshop Area: *Japan , ^Korea, China

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Page 3: CNT Manufacturing Study Products · CNT Manufacturing, NSF 11/3/06 Objectives of Panel Study of CNT Manufacturing in North America and Asia – Clarify research opportunities and

CNT Manufacturing, NSF 11/3/06

CNT Mfg & Applic’s Panel Activities

• Organizational/Planning Meeting (NSF)• North American Baseline Workshop (NSF)• Asian Tour-Site Visits

– Japan– Korea– PR China

• Final Symposium/ Panel Findings and Recommendations (NSF)

• Final Report (published WTEC Website; HardCopy-Springer)

Team 2

Team 1

CNT Manufacturing, NSF 11/3/06

Asian Site Visits• South Korea

– Samsung– Yonsei University – Iljin Nanotech– Seoul National University

• PR China – Chinese Academy of Sciences – Peking University– Tsinghua University– National Center for Nanoscience and Engineering

• Japan– NanoCarbon Technologies (NCT) Ltd.– Shinshu University– Showa Denko K.K.– Riken National Laboratory– AIST Lab (Tsukuba)– NEC Lab (Tsukuba)– Chiba University – University of Tokyo

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Page 4: CNT Manufacturing Study Products · CNT Manufacturing, NSF 11/3/06 Objectives of Panel Study of CNT Manufacturing in North America and Asia – Clarify research opportunities and

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Outline• Introduction to Carbon Nanotube (CNT) Structure,

Properties • Production of Single-Walled Tubes (SWCNTs) and

Multi-Walled Tubes (MWCNTs)• Purity Issues

– Large Batches of CNTs-what’s in there besides the tubes?– What Simple Characterization Tools tell us about SWCNTs and

MWCNTs

• Nanotube Applications• Executive Summary of WTEC Study on CNT

Manufacturing

CNT Manufacturing, NSF 11/3/06

Carbon: The Wonder Element

DWCNTSWCNTConesFullerenes C2n DiamondGraphite

Before 1985

Properties of Carbon combined in SWCNTs: high electron mobility, high thermal conductivity, high strength, low mass density

New NanoCarbons

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Page 5: CNT Manufacturing Study Products · CNT Manufacturing, NSF 11/3/06 Objectives of Panel Study of CNT Manufacturing in North America and Asia – Clarify research opportunities and

CNT Manufacturing, NSF 11/3/06

]2

3[tan 1

nmm

How to make Carbon NanotubesCarbon Nanotubes from Graphene

•Armchair: (n, n)

= 30

•Chiral: (n, m) (n m)

0 < < 30

•Zigzag: (n, 0)

= 0

21223 nmnmad cct

Courtesy of T. Hertel

CNT Manufacturing, NSF 11/3/06

(12,0)

“Zigzag” (n,0)

(7,7)

“Armchair” (n,n)

(9,5)

“Chiral” (n,m)

The Perfect Carbon Nanotube

(n,n): all metallic ; (n,m): 2/3 semiconducting 1/3 metallic

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Page 6: CNT Manufacturing Study Products · CNT Manufacturing, NSF 11/3/06 Objectives of Panel Study of CNT Manufacturing in North America and Asia – Clarify research opportunities and

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E22

E11

Energy gap (Eii) vs tube diameter (d)

E11

Eii ~ 1/d

H. Kataura, et al., Synthetic Metals 103, 2555 (1999).

Electronic States

CNT Manufacturing, NSF 11/3/06

Characterizational Probes for CNT Quality

• Bulk Powders– SEM– Sheet Resistance (Ohms per square)– Gravimetric response to oxidation (TGA)– Raman Scattering/Photoluminescence (Chirality Maps)– Optical Absorption

• Single tube– High Resoultion TEM– Resonant Raman Scattering – 4-probe Electrical Resistivity, Back-gated FET

transconductance; thermal conductivity– Young’s Modulus

We need standards for nanotube quality!! NIST,NASA

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Page 7: CNT Manufacturing Study Products · CNT Manufacturing, NSF 11/3/06 Objectives of Panel Study of CNT Manufacturing in North America and Asia – Clarify research opportunities and

CNT Manufacturing, NSF 11/3/06

CNT Growth

•Growth by high temperature interaction of carbon vapor or hydrocarbon feedstock with nanoparticles containing Fe,Ni,Co + X

•Lingering arguments over the details of the growth model

•Growth Model needed if monodisperse (n,m) material are ever to be made

CNT Manufacturing, NSF 11/3/06

Growth: Small vs. Large Catalyst Particles

dia~ 4-20 nm

bundles of SWNTs

Multi-Walled Nanotubes (MWNTs)

dia > 30 nmdia < 4 nm

individual SWNT

Endo et al.Smalley et al.

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Growth Methods for SWCNTs

• Chemical Vapor Deposition – Batch process; highest purity,low T--more wall defects,

long tubes, best control of diameter distribution

• Arc Discharge and Plasma– Batch process, larger scale production, high-T—less wall

defects, lower purity, shorter tubes

• Pulsed Laser Vaporization– Batch process, low production (except FEL), high T- less

wall defects

CNT Manufacturing, NSF 11/3/06

“The automatic ARC”

SWNT Research Chamber at CarboLex-Broomall(PA) facility SWNT Research Chamber at CarboLex-Broomall(PA) facility

www.CarboLex.com

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Page 9: CNT Manufacturing Study Products · CNT Manufacturing, NSF 11/3/06 Objectives of Panel Study of CNT Manufacturing in North America and Asia – Clarify research opportunities and

CNT Manufacturing, NSF 11/3/06 Hata, et. al, SCIENCE, 306, 1362-1364 (2005)

CVD Approach: H2O-Assisted “Super Growth”

CNT Manufacturing, NSF 11/3/06

Large Batches of SCWNTs:(What’s in there?)

• Many different chiralities (n,m) • Other carbon phases (e.g., amorph. carbon)• Growth catalyst (metals)• Wall defects (missing C-atoms)• Wall functional groups (-COOH)• Hetero-atoms (boron,nitrogen)

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Page 10: CNT Manufacturing Study Products · CNT Manufacturing, NSF 11/3/06 Objectives of Panel Study of CNT Manufacturing in North America and Asia – Clarify research opportunities and

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10 nm

d=1.35 nm

d=1.3 nm

HRTEM: SWNTs from the Jeff Lab FEL

P.C. Eklund, B. Holloway and M. Smith et al. , NanoLett. (2002)

CNT Manufacturing, NSF 11/3/06

Raman Scattering: One SWCNT

G.Chen and P.C. Eklund, unpublished

Radial mode ~ 1/dia

4 “G”-bands activated by cylindricalsymmetry

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CNT Manufacturing, NSF 11/3/06

Heating rate: 5 ˚C/min in dry air; Gas (air) flow rate: 100 cc/min; data courtesy of B. Pradhan

100

90

80

70

60

50

40

Wt l

oss (

%)

800600400200Temperature

8x10-3

6

4

2

0

-dM/dt

( C)

Gravimetric Analysis of Unpurified SWCNT Powder

Controlled Oxidation

2C+O2-> 2COdM/dTM(T)

Multishellcarbons

SWCNTs

Amorphous carbon

c.f., pub’s by P.C. Eklund, B. Pradhan et al.

CarboLex SWCNTs)

CNT Manufacturing, NSF 11/3/06

Do All SWCNT Applications Require the Same Purity Material?

• Of course not!! • High-level purification leads to

significant manufacturing costs• Selectively remove impurities that

affect product performance

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Page 12: CNT Manufacturing Study Products · CNT Manufacturing, NSF 11/3/06 Objectives of Panel Study of CNT Manufacturing in North America and Asia – Clarify research opportunities and

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SWCNT Purification and De-bundling Process

•We know how to do it

•It’s really now in the hands of chemical engineers to scale it up

Purification

De-bundling

c.f., pub’s by P.C. Eklund, B. Pradhan, C. Furtado, et al.

CNT Manufacturing, NSF 11/3/06

What’s bonded to the tube walls?

Carbon. Vol. 31, No.5, 721Angew. Chem.Int. Ed. 2002, 41, No.11

IR Spectroscopy is sensitive to functional groups on the SWCNT tube wall; Raman scattering is sensitive to wall defects, diameter and with difficulty (n,m)

c.f., pubs with Furtado, Kim, Eklund et al.

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Growth of MWCNTs

• CVD- “Endo” continuous process• Large scale production, tons per year• CNTs produced with wall defects and metal

impurities• High temperature treatment is last step in

production– Wall defects annelaed– Metal impurities vaporized and transported away

• Final product is high purity; low wall defects

CNT Manufacturing, NSF 11/3/06

What do Nanotubes do well?

Structural Composites

Tips for NanoProbes

FieldEmission

Transistors

ElectroMechanicalActuators

LogicGates

Battery Electrodes, Capacitors,EMI

GasStorage

Bulk Electronics

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Page 14: CNT Manufacturing Study Products · CNT Manufacturing, NSF 11/3/06 Objectives of Panel Study of CNT Manufacturing in North America and Asia – Clarify research opportunities and

CNT Manufacturing, NSF 11/3/06

Summary• Single-Walled Carbon Nanotubes (SWCNTs)

– still found difficult to make in large quantities and high purity

– high specific surface area- catalyst supports, gas storage– high electron mobility-single tube devices– High aspect ratio-sharp tips-FED devices– Percolating networks-touch screens, EMI shield, Solar panels

• Multiwalled Carbon Nanotubes (MWCNTs)– Now a high purity product @ tens of tons per year (Japan)– Electronic applications in bulk electronics

• Capacitors, SuperCapacitors, Batteries– Structural composites with plastics

• Sports equipment, Military?, Medical

CNT Manufacturing, NSF 11/3/06

CNT Race at a GlanceTOPIC

USA /North

America China Japan Korea

Bulk Growth MWCNT **** *** ***** * Bulk Growth SWCNT *** *** **** ** Structural Composites *** ? ***** ? Post Synthesis Processing *** * *** ** Conductive Composites EMI,touch screens, ink Emission Electronics

FED **** ? ? ***** Lighting ? ** ? ? X-Ray/Tubes ** ? ? ?

Electronic Devices **** * ** *** Battery ? ? ***** ? Capacitors ? ? ***** ? Industry/University Cooperative R&D ** **** ***** **** Targeted Government CNT R/D/M Funding * ? **** *** Government Funded University R&D (SWCNT) *** * *** ** Government Funded University R&D (MWCNT) ** ** ***** *

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