Preparation and Characterization of Magnetically Aligned Carbon Nanotube Buckypaper and ...

178 Pages·2015·4.57 MB·English

by  Ravi Shankar Kadambala

Florida State University Libraries
Electronic Theses, Treatises and Dissertations The Graduate School
2003
Preparation and Characterization of
Magnetically Aligned Carbon Nanotube
Buckypaper and Composite
Kadambala Ravi Shankar
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THE FLORIDA STATE UNIVERSITY
COLLEGE OF ENGINEERING

PREPARATION AND CHARACTERIZATION OF
MAGNETICALLY ALIGNED CARBON NANOTUBE
BUCKYPAPER AND COMPOSITE

By
KADAMBALA RAVI SHANKAR

A Thesis submitted to the
Department of Industrial Engineering
in partial fulfillment of the
requirements for the degree of
Master of Science

Degree Awarded:
Fall Semester, 2003
The members of the Committee approve the thesis of Kadambala Ravi Shankar defended
on November 10, 2003

Zhiyong Liang
Professor Directing Thesis

Ben Wang
Committee Member

Chuck Zhang
Committee Member

Approved:

Ben Wang, Chair, Department of Industrial Engineering

Ching-Jen Chen, Dean, FAMU-FSU College of Engineering

The Office of Graduate Studies has verified and approved the above named committee
members

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ACKNOWLEDGEMENTS

I would like to express my sincere gratitude and thanks to Dr. Zhiyong Liang, for
his extensive support through out the program and his guidance as both advisor and
friend. I would also like to thank my committee members, Dr. Ben Wang and Dr. Chuck
Zhang for their suggestions and assistance during the preparation of this thesis. A sincere
appreciation goes to all my co-workers of Florida Advanced Center for Composite
Technologies (FAC2T) especially Philippe Gonnet, Michael Wang, Kevin Barefield,
Maria Roquer and Yu-Hsuan Liao for their help and meaningful contribution to this
thesis. Finally, I would like to thank my parents, my sister and my friends for their
encouragement and support throughout my life and education.
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TABLE OF CONTENTS

LIST OF TABLES…………………………………………………………………… vii
LIST OF FIGURES………………………………………………………………….. ix
ABSTRACT…………………………………………………………………………. xvi
MOTIVATION AND OBJECTIVES………………………………………………... 1
1.1 Introduction…………………………………………………………………... 1
1.2 Motivation…………………………………………………………….……... 2
1.3 Technical Challenges of Nanotube Based Nanocomposites..……………….. 4
1.4 Research Objectives 6
LITERATURE REVIEW…………………………………………………….……… 7
2.1 Self-Organized Ribbons of Aligned Carbon Nanotubes……………………. 7
2.2 A Simple Spinning Process to make Nanotubes Fibers…………………….. 9
2.3 Aligned Carbon Nanotubes Arrays Formed by Cutting a Polymer Resin- 11
Nanotube Composite………………………………………………………...
2.4 Direct Synthesis of Long Single-Walled Carbon Nanotube Strands………… 13
2.5 In-plane-Aligned Membranes of Carbon Nanotubes……………………….. 14
2.6 Synthesis of Large Arrays of Well-Aligned Carbon Nanotubes on Glass…... 18
2.7 Conclusion…………………………………………………………………… 20
MAGNATICALLY ALIGNED NANOTUBE BUCKYPAPERS…………………. 21
3.1 Buckypapers ………………………………………………………………… 21
3.1.1 SWNT suspension…………………………………………………….. 21
3.1.2 Filtration…………………………..………………………………….... 24
3.2 Magnetically Aligned Buckypaper………………………………………….. 27
3.2.1 Experimental Set-up..………………………………………………….. 27
3.2.2 Experiment………………………..………………………………….... 28
3.2.3 Cylindrical Filter Design………………………………………………. 31
3.2.3.1 Design…………………………………………………………. 31
3.2.3.2 Parts……………………………………………………………. 32
3.2.3.3 Filter assembly and membrane attachment……………………. 33
CLEANING ALIGNED NANOTUBE BUCKYPAPERS…..…….…….………….. 38
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4.1 Cleaning Procedure for the Buckypaper using Isopropyl Alcohol…………... 38
4.2 Testing Procedure for Cleaning the Buckypaper using Infrared Spectroscopy 38
4.2.1 Principle…………………………….……………………………….…. 39
4.2.2 Sample Preparation using the KBr Pellet Method…….….……………. 39
4.2.3 Experimental Procedure…………………………….………………….. 40
4.2.4 Result and Analysis……………………………………...…………….. 40
ALIGNED NANOTUBE BUCKYPAPER COMPOSITES….……………….…….. 48
5.1 Resin infusion system…………………………………………………...…… 48
5.1.1 Diluting Resin…………..………………………………………...….… 49
5.1.2 Infusion Resin…………………………………………...……………... 50
5.1.3 Vacuuming Buckypaper……………………………………………….. 50
5.1.4 Mold assembling………………………………………………….….… 51
5.1.5 Hot pressing………………………………………………………...….. 52
5.1.6 De-molding…………………………………………………………...... 53
CHARACTERIZATION OF RANDOM AND ALIGNED NANOTUBE
53
BUCKYPAPERS….………………………………………………………………….
6.1 Preliminary Analysis……………………………………………………….... 53
6.2 Atomic Force Microscopy (AFM) Analysis…………………………………. 54
6.3 Scanning Electron Microscope (SEM) Analysis…………………………….. 55
6.4 Permeability Measurement…………………………………...……………… 58
6.5 Summary 60
THEORETICAL CALCULATIONS FOR RANDOM AND ALIGNED
61
NANOTUBE BUCKYPAPER COMPOSITES…………….…………………….….
7.1 Critical Length of Nanotube/Epoxy Composite…………………………...… 62
7.2 Composite Modulus of Nanotube/Epoxy Composite……………………...… 63
7.3 Composite Modulus of a Standard Short-Fiber Composite………………….. 65
7.4 Assumptions to Calculate the Composite Modulus of Random and Aligned
Discontinuous Nanotubes/Epoxy………...………………………………...… 66
7.5 Composite Modulus of Random and Aligned Discontinuous
Nanotubes/Epoxy…………………………………………………………….. 67
7.6 Composite Modulus of Random and Aligned Discontinuous Nanotube
Ropes/Epoxy………………………………………………………….…….... 72
7.7 Summary…………………………………………………………………...… 79
CHARACTERIZATION OF RANDOM AND ALIGNED BUCKYPAPER
79
COMPOSITES….………………………………………………………………….
8.1 Scanning Electron Microscope (SEM) Analysis...………………………… 80
8.1.1 Random Buckypaper Composite…………………………………….. 80
8.1.2 Aligned Buckypaper Composite……………………………………... 82
8.2 Dynamic Mechanical Analysis………………………………..…………… 85
8.2.1 Random Buckypaper Composite…………………………………….. 85
8.2.2 Aligned Buckypaper Composite……………………………………... 87
8.3 Summary 87
RESISTIVITY ANALYSIS OF RANDOM AND ALIGNED BUCKYPAPERS 92
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AND COMPOSITES………………………………………………………………....
9.1 Method……………………………………………...……………………...… 93
9.2 Experimental Set-up………………………………………..……………...… 94
9.3 Experiment……………………………………………………………..…….. 97
9.4 Results………..…………………………………………….………………… 98
9.4.1 Resistivity Analysis for Reference Sample………………………...….. 98
9.4.2 Resistivity Analysis for Aligned Buckypaper…………………………. 99
9.4.2.1 Influence of SWNT suspension concentration………………… 102
9.4.2.2 Influence of magnetic field strength…………………………… 105
9.4.2.3 Influence of the type of surfactant on resistivity of the
buckypaper…………………………………………………….. 109
9.4.2.4 Influence of the sonication time……………………………….. 112
9.4.3 Comparison of Experimental Results………………………………….. 114
9.5 Summary 116
CONCLUSION………………………………………………………………………. 115

APPENDIX A Results of Magnet Time from 5/21/03 to 5/30/03……………….….. 119
APPENDIX B SEM Images of Aligned Buckypapers………...….…..…………….. 121
APPENDIX C DMA Analysis for Random and Aligned Buckypaper Composites… 125
APPENDIX D Resistivity Data for Random and Aligned Buckypapers…………... 127
APPENDIX E Slope of Voltage vs. Current for Aligned Buckypapers……………. 138
APPENDIX F Resistivity Measurements of Random and Aligned Buckypaper
152
Composites…………………………………………………………..
REFERENCES……………………………………………………………………… 154
BIOGRAPHICAL SKETCH………………………………………………………… 158

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LIST OF TABLES

2.1. Comparison of magnetic susceptibilities ……………………………………… 15

3.1. Facilities and materials for the experimental setup of NBP preparation………. 26

3.2. Various experiments performed in the NHMFL under 15~25 T magnetic fields 30

3.3.The various aligned alignment experiments performed in the NHMFL………... 35

3.4. Various alignment experiments performed in the NHMFL……………………. 36

4.1. Vibrational frequencies for molecules…………………………………………. 41

5.1. Facilities and materials for the experimental setup of composite processing….. 48

6.1. Permeability data for random and aligned buckypaper………………………… 59

7.1. Composite modulus of random discontinuous and aligned discontinuous
carbon fibers with respect to increase in fiber weight content…………………. 66

7.2. Composite modulus of random discontinuous and aligned discontinuous
SWNTs with respect to increase in nanotube weight content…………………... 68

7.3. Composite modulus of random discontinuous and aligned discontinuous
SWNTs with respect to increase in aspect ratio………………………………... 70

7.4. Composite modulus of random discontinuous and aligned discontinuous
SWNT ropes with respect to increase in aspect ratio…………………………... 73

7.5. Composite modulus of random discontinuous and aligned discontinuous
SWNT ropes with respect to increase in fiber weight content..………………… 75

7.6. Composite modulus of random discontinuous and aligned discontinuous
SWNT ropes with respect to increase in diameter of the nanotube rope……….. 77

8.1. Storage modulus of random and aligned buckypaper composites……………... 85

vii
9.1. List of equipments for resistivity measurements………………………………. 95

9.2. Resistivity of copper film samples…………………………………………….. 98

9.3. Resistivity and anisotropy of sample A-4-18………………………………….. 99

9.4. Anisotropy and resistivity of various sample based on the concentration
of the SWNT suspension……………………………………………………….. 103

9.5. Resistivity of various samples based on the magnetic field strength………….. 106

9.6. Resistivity of various samples based on the type of surfactant and
sonication time……………………………………………………………….… 109

9.7. Comparison of experimental results…………………………………………... 115

A. Results of magnet time from 5/21/03 to 5/30/03………………………………. 119

C. Resistivity data for random and aligned buckypaper………………………….. 125

D. DMA analysis for random and aligned buckypaper composites……………… 127

F. Resistivity measurements of random and aligned buckypaper and composites 152
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LIST OF FIGURES

2.1. Photographs of beakers and schematic diagrams showing the growth direction
of the nanotube ribbons. (a) Perpendicular to and (b) parallel to the bottom of
the beaker…………………………………………………………………..…… 8

2.2. SEM images of a ribbon that consists of aligned carbon nanotubes.
(a) Cross section of the nanotube ribbon.(b) Bent ribbons…………………….. 9

2.3. Schematic drawing of the experimental set-up used to make nanotubes ribbons 10

2.4. Optical micrographs of a nanotube ribbon observed between crossed vertical
and horizontal polarizers……………………………………………………….. 10

2.5. Low-magnification TEM image from a slice 950 nm thick) with a distribution
of nanotubes.…………………………………………………………………… 12

2.6 (a) low-magnification TEM image from a pure nanotube sample in a 80 mm
thick film. (b) and (C) images at higher magnification showing local areas of
films with perfectly parallel and separated nanotube arrays…………………. 12

2.7. Optical image showing a human hair and two as-grown SWNT strands…….. 13

2.8. (a) Low-magnification SEM image of a long SWNT strand.(b) High-resolution
SEM of an array of SWNT ropes peeled from the strand. (c) HRTEM image of
a top view of a SWNT rope……………………………………………………. 14

2.9. Transmitted light signal (mv) as a function of magnetic field………………… 16

2.10. Peak-to-peak modulation amplitude, as a fraction of average transmittance,
vs. field for unmodified SWNTs (circles)………………………………….… 17

2.11. In-plane-aligned assembly of SWNTs……………………………………….. 18

2.12. (a) SEM micrograph of carbon nanotubes aligned perpendicular to the
substrate over large areas; (b) Enlarged view of (a) along the peeled edge
showing diameter, length, straightness,and uniformity in height, diameter,
and site density………………………………………………………………. 19

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