Solution Manual for

Nanoengineering of Structural, Functional

and Smart Materials
Prepared by
Han Gi Chae, Rahul Jain, Tetsuya Uchida, Beom-Jin Yoon, Satish Kumar
Joseph H. Koo, Louis A. Pilato
Gregory M. Odegard
Samit Roy
Vesselin Yamakov, Dawn R. Phillips, Erik Saether, Edward H. Glaessgen
Xudong Wang, Zhong Lin Wang
Virginia A. Davis, Matteo Pasquali
Debasish Banerjee, Jingyu Lao, Zhifeng Ren
Hassan Mahfuz
Kin-Tak Lau
Cindy K. Waters, Sergey Yarmolenko, Jagannathan Sankar, Sudhir Neralla, Ajit D. Kelkar
Mannur Sundaresan
M. Buongiorno Nardelli, S.M. Nakhmanson, V. Meunier
Peng He, Donglu Shi
Dong Qian
Ashutosh Tiwari and J. Narayan
Ying Chen and Jim S. Williams
Vesselin N. Shanov
Yun YeoHeung, Mark J. Schulz

December 30, 2006

This solution manual is for use by instructors and practicing engineers and scientists.

Copyright CRC Press

Contact Person:
Mark J. Schulz
University Of Cincinnati
Department of Mechanical Engineering
Smart Materials Nanotechnology Lab
598 Rhodes Hall, Cincinnati, OH 45221-0072
Phone: (513) 556-4132, Fax: (513) 556-3390; Email: Mark.J.Schulz@uc.edu
http://www.min.uc.edu/~mschulz/smartlab/smartlab.html
 List of Contributors to the Solution Manual
BeomJin Yoon, Han Gi Chae, Rahul Jain, and Satish Kumar
Georgia Institute of Technology
School of Polymer, Textile and Fiber
Engineering
801 Ferst Drive, NW MRDC-1, Atlanta,
GA 303320295
Satish Kumar (and Tetsuya Uchida), satish.kumar@ptfe.gatech.edu
Rahul Jain, rahuljain@gatech.edu
Han Gi Chae, HanGi.Chae@gatech.edu
BeomJin Yoon, gth770p@mail.gatech.edu

Joseph H. Koo and L.A. Pilato

University of Texas at Austin,
Department of Mechanical
Engineering-C2200, Austin, TX
787120292
KAI, Inc., 6402 Needham Lane, Austin,
TX 78739
jkoo@mail.utexas.edu

Gregory M. Odegard
Department of Mechanical
EngineeringEngineering Mechanics
Michigan Technological University
1400 Townsend Drive
Houghton, MI 499311295
gmodegar@mtu.edu

Samit Roy, K. Vengadassalam, Farzana Hussain, and Hongbing Lu

William D. Jordan Professor
Aerospace Engineering and Mechanics
209 Hardaway, Box 870280
University of Alabama
Tuscaloosa, AL 35487-0280
samit roy, rsamit@ceat.okstate.edu

V. Yamakov
National Institute for Aerospace,
Hampton, VA 23666
D.R. Phillips
Lockheed Martin Space Operations,
Hampton, VA 23681
E. Saether and E.H. Glaessgen
Analytical and Computational Methods
Branch
NASA Langley Research Center,
Hampton, VA 23681
e.h.glaessgen@larc.nasa.gov

Xudong Wang and Zhong Lin Wang

School of Materials Science and
Engineering
Georgia Institute of Technology,

2
Atlanta, GA 303320245
Xudong Wang , gtg600c@mail.gatech.edu
Zhong Lin Wang, zhong.wang@mse.gatech.edu

Virginia A. Davis and Matteo Pasquali

Rice University, Department of
Chemical Engineering, MS 362
Center for Nanoscale Science and
Technology, 6100 Main Street,
Houston, TX 77005
Matteo Pasquali, mp@rice.edu
Virginia Davis, davisva@auburn.edu

D. Banerjee, J.Y. Lao, and Z.F. Ren

Department of Physics, Boston College,
Chestnut Hill, MA 02467
Debasish Banerjee
1841 Shirley Lane, Apt# B4
Ann Arbor, MI 48105
banerjde@bc.edu
Zhifeng Ren, renzh@bc.edu

Hassan Mahfuz
Department of Ocean Engineering
Florida Atlantic University
777 Glades Road
Bldg. 36 - Room 179
Boca Raton, FL 33431
hmahfuz@oe.fau.edu

Kin-tak Lau
Department of Mechanical
Engineering, The Hong Kong
Polytechnic University, Hung Hom,
Kowloon, Hong Kong
mmktlau@polyu.edu.hk
Jagannathan Sankar
North Caroline A&T State University,
Department of Mechanical
Engineering, Greensboro, NC 27411
sankar@ncat.edu
David Hui
Department of Mechanical
Engineering, University of New
Orleans, New Orleans, LA 70148
DHui@uno.edu

Cindy K. Waters, Sergey Yarmolenko, Jagannathan Sankar, Sudhir Neralla, and Ajit D. Kelkar
Center for Advanced Materials and
Smart Structures, Department of
Mechanical Engineering,
North Carolina A&T State University,
Greensboro, NC 27411
Cindy Waters, PhD
Adjunct Associate Professor-Research Scientist
Department of Mechanical and Chemical Eng.

3
Center for Advanced Materials and Smart Structures
625 McNair Hall
NCA&T State University, Greensboro, NC 27411
kwaters@ncat.edu
Kelkar, kelkar@ncat.edu
sergey@ncat.edu
sudhirneralla@hotmail.com

Mannur J. Sundaresan
Dept. of Chemical and Mechanical
Engineering, North Carolina A&T State
University, Greensboro, NC 27411
mannur@ncat.edu

M. Buongiorno Nardelli
Department of Physics, North Carolina
State University, Raleigh, NC 27695
Center for Computational Sciences
(CCS) and Computer Science and
Mathematics Division,
Oak Ridge National Laboratory, Oak
Ridge, TN 37830
S.M. Nakhmanson
Department of Physics, North Carolina
State University, Raleigh, NC 27695
V. Meunier
Center for Computational Sciences
(CCS) and Computer Science and
Mathematics Division,
Oak Ridge National Laboratory, Oak
Ridge, TN 37830
Marco Buongiorno Nardelli, mbnardelli@ncsu.edu
Serge Nakhmanson, nakhmans@physics.rutgers.edu

Peng He and Donglu Shi

Department of Chemical and Materials
Engineering, Nanoparticle Coating
Laboratory
University of Cincinnati, Cincinnati,
OH 45221
shid@email.uc.edu
hepg@email.uc.edu

Dong Qian
Department of Mechanical, Industrial and Nuclear Engineering
University of Cincinnati, PO Box 210072
Cincinnati, OH 45221-0072, USA
Dong.Qian@uc.edu

Ashutosh Tiwari and J. Narayan

Department of Materials Science
& Engineering,
North Carolina State University
Raleigh, NC 276957916
J Narayan, j_narayan@ncsu.edu
Prof. Ashutosh Tiwari

4
Dept of Materials Science & Engineering
University of Utah
122 S. Central Campus Drive
Room#317
Salt Lake City, UT-84112
Assistant Professor
MATERIAL SCIENCE AND ENGINEER
CIVIL & MATERIALS ENGINEERING
122 S CENTRAL CAMPUS DR RM 304
tiwari@eng.utah.edu

Ying Chen and Jim S. Williams

Department of Electronic Material
Engineering, Research School of
Physical Sciences and Engineering, The
Australian National University,
Canberra, ACT 0200, Australia.
Ying Chen, ying.chen@anu.edu.au

Vesselin N. Shanov
Department of Chemical and Materials
Engineering, Department of
Mechanical Engineering
Smart Structures Bio-Nanotechnology
Laboratory, University of Cincinnati
Cincinnati, OH 452210072
vesselin.shanov@uc.edu

Yun Yeo-Heung, Mark J. Schulz

University Of Cincinnati
Department of Mechanical Engineering
Smart Materials Nanotechnology Lab
598 Rhodes Hall, Cincinnati, OH 45221-0072
yunyg@email.uc.edu
Mark.J.Schulz@uc.edu

5
FOREWORD
This manual contains solutions to the chapter wise problems in Nanoengineering of Structural,
Functional and Smart Materials. The problems for Chapters 1 and 12 were not included at the
end of the chapters in the book due to time constraints in publishing the book. However, the
problems and solutions for Chapters 1 and 12 are included in the solution manual.
This manual is a comprehensive solution set for nanotechnology problems. The solutions were
prepared by the chapter authors or other volunteers. The solutions are based on the current state
of knowledge in the field. As the field of nanotechnology matures, some solutions and
approaches may be replaced by better solutions and approaches. In fact, it is hoped that this book
can serve as a reference for the current state of the art and to allow researcher to improve upon
existing technology. Improvements in materials processing are especially needed in areas such as
dispersing nanotubes, spinning fibers, electrical properties, control of synthesis, and on. We hope
that you find the nanoengineering book and the accompanying solution manual useful. We
appreciate any comments to improve the book and solution manual. Some suggestions on using
the book to teach nanotechnology are given below.

Use of the Solution Manual. The solution manual is meant for use by instructors that are using
Nanoengineering of Structural, Functional and Smart Materials for teaching, and for other
professionals such as engineers and scientists who would use the solutions for reference. There
are not many books that have nanotechnology problems and solutions. It is hoped that this 100
page solution manual will be a helpful starting point to develop many more problems sets that
can provide and test understanding of nanotechnology concepts. The authors should especially
be thanked for contributing chapters with the problems and solutions. Some of the chapter
problem sets are very detailed (e.g. Chpts. 2, 5, 12, 16) and provide a great resource for quickly
learning the basics of these subject areas of nanotechnology. Reading the chapters and studying
the solutions can save a tremendous amount of work that would be required to survey the
literature to provide an equivalent understanding of the subject.

Teaching Nanoengineering. Teaching nanoengineering is a little different than teaching other

subjects because nano is new and changing quickly, and often the instructor is learning along
with the students. This makes it necessary for the instructor to continuously update the course
material from interdisciplinary sources. Therefore, searching the web for technical papers and for
presentations posted at the different university laboratories and government agencies is necessary
to stay current in most areas of research.

Resources for Teaching and Research in Nanotechnology. Besides Nanoengineering of

Structural, Functional and Smart Materials, there are several books that may be used for
teaching nanotechnology at different levels. Some of these books and web sites with useful
information are listed below. New books in the area of nanotechnology are also coming out
every month.
1. Nanoscale Science and Technology, Robert Kelsall (Editor), Ian W. Hamley (Editor), Mark
Geoghegan (Editor), ISBN: 0470850868
2. Introduction to Nanoscale Science and Technology, Massimiliano Di Ventra, Stephane Evoy,
James R. Heflin, ISBN: 1402077203
3. Biomechanics at Micro- and Nanoscale Levels, Vol. 1, Hiroshi Wada (Editor), ISBN:
981256098X

6
4. Biofunctionalization of Nanomaterials, Kumar Challa (Editor), ISBN: 3527313818
5. Nanofabrication Towards Biomedical Applications: Techniques, Tools, Applications, and
Impact, Josef Hormes (Editor), Kumar Challa S. S. R. (Editor), Carola Leuschner (Editor),
ISBN: 3527311157
6. Nanotechnology: Basic Science and Emerging Technologies, Michael Wilson, ISBN 1-
58488-339-1.
7. Engines of Creation: The Coming Era of Nanotechnology, Eric Drexler, ISBN 0-385-19973-
2.
8. CD-ROM, 2005 Guide to Nanomedicine Technology, ISBN 1-59248-435-2, from Amazon.
Com and other book sellers.

Interdisciplinary Teaching. Since nanoengineering is so broad of an area, introductory courses

are often cooperatively taught, or guest lecturers are invited to teach certain topics of the course.
Nanotechnology courses are available at most of the universities of the authors in this book.
Readers are encouraged to visit the web sites of the different universities to see current course
listings. As an example, at the Univ. of Cincinnati (UC) a new two course undergraduate
sequence in nanotechnology was started in 2006. The course contains a lecture and a laboratory
component. Both components are team taught by faculty members from the departments of:
Chemical and Materials Engineering, Electrical and Computer Engineering, Physics, Chemistry,
and Philosophy. Seven different faculty members in total teach the course and there is generous
support of teaching assistants provided by the University. More information on the
nanotechnology courses at the university can be found at:
(http://www.eng.uc.edu/ucnanoinstitute/). Nano courses (8) available at UC as of 2007 are:
INTRODUCTION TO NANOSCALE SCIENCE & TECHNOLOGY. Catalog 20 ENFD 278.
3 Credits. Fundamental concepts and applications of nanoscale science and technology (can
be audited by graduate students) .
EXPERIMENTAL NANOSCALE SCIENCE & TECHNOLOGY. Catalog 20 ENFD 279. 3
Credits. The laboratory course comprises four two-week experiments including carbon
nanotube synthesis, nanotube sensor fabrication and characterization, quantum dot
characterization, and gold nanoparticle fabrication and characterization (can be audited by
graduate students)
NANOMATERIALS SCIENCE/BIOMEDICAL APPLICATIONS I. Catalog 20 MTEN 610,
winter quarter. 3 credits. To introduce various basic concepts of current nanomaterials and
nanotechnology, such as nano- structures, new nanomaterials (nanotubes and nano-wires),
synthesis methods, and physical properties.
NANOMATERIALS SCIENCE/BIOMEDICAL APPLICATIONS II. Catalog TBD, spring
quarter. 3 credits. Continuation of Nanomaterials I.
NANOTECHNOLOGY OCCUPATIONAL AND ENVIRONMENTAL HEALTH &
SAFETY. 20 INDS 691/TBD; Topics cover the impact of nanotechnology on occupational
and environmental health and safety with respect to the promotion and protection of
individual safety and health along the life cycle of nano-based products (i.e., material
handling, manufacturing process, etc.)
NANOTECHNOLOGY OCCUPATIONAL AND ENVIRONMENTAL HEALTH &
SAFETY. Continuation of first course.
INTRODUCTION TO NANOELECTRONICS; 20 ECES 628. Emerging technologies in
nanofabrication and nanoscale electronic devices. Nanolithography, nanometer 3D

7
 MOSFETs, carbon nanotubes, spintronics, nanoscale and single electron transistors, quantum
dots and computing, molecular electronics.
NANO-STRUCTURED POWDERS: SYNTHESIS STRUCTURE AND APPLICATIONS;
20 MTSC 641. This class is intended to give an overview of the syntheses, industrial
production, characterization and applications of nano-structured ceramic, organics and hybrid
powders. These materials are used for a wide range of applications including use as catalysis
chemical sensors etc.

Problems and Solutions for all chapters of the book

The problems and solutions for all 24 chapters in the book are contained in this manual. In some
of the problems the solution may be open to debate, or the problem may be open-ended and have
more than one solution. For many solutions, reference to the open literature is given. Also, the
authors in some cases did not have time to answer all questions in detail. It should be noted that
references numbers, figure numbers, and equation numbers in the solution manual are
independent for each question. Comments and corrections to the solution set are invited and
appreciated. It is hoped that readers of the book may provide more details to the solutions and
answer some of the questions that were not answered except by providing references. An
updated solution manual might be provided if significant contributions are provided by readers.

8
 Table of Contents
(Problems and solutions are by the chapter authors unless otherwise noted.)

1.1 Solutions for Chapter 1- Introduction to Nanoengineering by John F. Maguire and David B.
Mast (Problems and solutions by Mark Schulz)

PART 1 Synthesis of Nanoscale Materials

1.2 Solutions for Chapter 2- Design of Nanostructured Materials by Debasish Banerjee, Jingyu
Lao, and Zhifeng Ren

1.3 Solutions for Chapter 3- Carbon Nanotubes and Bismuth Nanowires by Mildred S.
Dresselhaus, Ado Jorio, and Oded Rabin (Solutions by Mark Schulz)

1.4 Solutions for Chapter 4-Nanobelts and Nanowires of Functional Oxides by Xudong Wang
and Zhong Lin Wang

1.5 Solutions for Chapter 5- Advances in Chemical Vapor Deposition of Carbon Nanotubes by
Vesselin N. Shanov, Atul Miskin, Sachin Jain, Peng He, and Mark J. Schulz (Solutions by
Vesselin N. Shanov)

1.6 Solutions for Chapter 6- Self-Assembled Au Nanodots in a ZnO Matrix: A Novel Way to
Enhance Electrical and Optical Characteristics of ZnO Films by Ashutosh Tiwari and Jagdish
Narayan

1.7 Solutions for Chapter 7- Synthesis of Boron Nitride Nanotubes Using a Ball-Milling and
Annealing Method by Ying Chen and Jim S. Williams

PART 2 Manufacturing Using Nanoscale Materials

1.8 Solutions for Chapter 8- Plasma Deposition of Ultra-Thin Functional Films on Nanoscale
Materials by Peng He and Donglu Shi

1.9 Solutions for Chapter 9- Structural Nanocomposites by Hassan Mahfuz

1.10 Solutions for Chapter 10- Synthesis and Characterization of Metal-Ceramic Thin-Film
Nanocomposites with Improved Mechanical Properties by Dhananjay Kumar, Jagannathan
Sankar, and Jagdish Narayan (Solutions by Vesselin N. Shanov)

1.11 Solutions for Chapter 11- Macroscopic Fibers of Single-Walled Carbon Nanotubes by
Virginia A. Davis and Matteo Pasquali

1.12 Solutions for Chapter 12- Carbon Nanofiber and Carbon Nanotube/Polymer Composite
Fibers and Films by Han Gi Chae, Tetsuya Uchida, and Satish Kumar

9
1.13 Solutions for Chapter 13- Surface Patterning Using Self-Assembled Monolayers: A Bottom-
Up Approach to the Fabrication of Microdevices by Lakshmi Supriya and Richard O. Claus
(Solutions by Mark Schulz)

1.14 Solutions for Chapter 14- Enhancement of the Mechanical Strength of Polymer-Based
Composites Using Carbon Nanotubes by Kin-Tak Lau, Jagannathan Sankar, and David Hui

1.15 Solutions for Chapter 15- Nanoscale Intelligent Materials and Structures by Yun Yeo-Heung,
Inpil Kang, Sachin Jain, Atul Miskin, Suhasini Narasimhadevara, Goutham Kirikera, Vishal
Shinde, Sri Laxmi Pammi, Saurabh Datta, Peng He, Douglas Hurd, Mark J. Schulz, Vesselin N.
Shanov, Donglu Shi, F.J. Boerio, and Mannur J. Sundaresan (Solutions by Yun YeoHeung)

1.16 Solutions for Chapter 16- Thermal Properties and Microstructures of Polymer
Nanostructured Materials by Joseph H. Koo and Louis A. Pilato

1.17 Solutions for Chapter 17- Manufacturing, Mechanical Characterization, and Modeling of a
Pultruded Thermoplastic Nanocomposite by Samit Roy, Kalivarathan Vengadassalam, Farzana
Hussain, and Hongbing Lu

PART 3 Modeling of Nanoscale and Nanostructured Materials

1.18 Solutions for Chapter 18- Nanomechanics by Young W. Kwon (Solutions by Dong Qian)

1.19 Solutions for Chapter 19- Continuum and Atomistic Modeling of Thin Films Subjected to
Nanoindentation by J. David Schall, Donald W. Brenner, Ajit D. Kelkar, and Rahul Gupta
(Solutions by Mark Schulz)

1.20 Solutions for Chapter 20- Synthesis, Optimization, and Characterization of AlN/TiN Thin
Film Heterostructures by Cindy K. Waters, Sergey Yarmolenko, Jagannathan Sankar, Sudhir
Neralla, and Ajit D. Kelkar

1.21 Solutions for Chapter 21- Polarization in Nanotubes and Nanotubular Structures by Marco
Buongiorno Nardelli, Serge M. Nakhmanson, and Vincent Meunier

1.22 Solutions for Chapter 22- Multiscale Modeling of Stress Localization and Fracture in
Nanocrystalline Metallic Materials by Vesselin Yamakov, Dawn R. Phillips, Erik Saether, and
Edward H. Glaessgen

1.23 Solutions for Chapter 23- Modeling of Carbon Nanotube/Polymer Composites by Gregory
M. Odegard

1.24 Solutions for Chapter 24- Introduction to Nanoscale, Microscale, and Macroscale Heat
Transport: Characterization and Bridging of Space and Time Scales by Christianne V.D.R.
Anderson and Kumar K. Tamma (Solutions by Mark Schulz)

10
1.1 Solutions for Chapter 1
Introduction to Nanoengineering by John F. Maguire and David B.
Mast (Problems and solutions by Mark Schulz.)

1. Compare and contrast the NST revolution with other scientific and technical revolutions
in history. What can we learn from history to guide the NST revolution?

Other revolutions in history from different perspectives include the mechanistic revolution
(Copernicus/Galileo/Newton), biological evolution (Darwin/Mendel/Watson-Crick),
atomic/quantum physics (Bohr/Einstein/Schroedinger/), information and microelectronics
(Turing/Wiener/Kilby-Noyce), the industrial revolution, nuclear fission, space exploration, the
transistor, electronic computer, genetics, and others. Lessons from history may suggest some
oversight of the development of NST is needed including to explore potential harmful uses of
nanotechnology and how society can adapt to nanotechnology through education and planed
coordinated nanoindustrialization. Part of this question and response is from notes by Dr. John
Bickle, Professor and Head of the Department of Philosophy and Professor in the Neuroscience
Graduate Program at the University of Cincinnati [1].

2. What are some of the societal and ethical implications of NST?

There are many perspectives on the positive and negative societal and ethical implications of
NST. As an example, the Foresight Institute [2] has articulated six critical challenges that
humanity faces which can be addressed by nanotechnology. Their Weekly News Digest presents
news items, research breakthroughs, and events citing current research and applications
providing the stepping stones to solutions to these challenges. The challenges are listed below.

(1) Meeting global energy needs with clean solutions. Providing abundant energy globally will
solve many other problems (such as clean water) and reduce global conflict. To be effective,
nanotechnology energy solutions need to be scalable and cost effective. Solar cells based on
nanotechnology to replace fossil fuels may be one solution.

(2) Providing abundant clean water globally. Nanofiltration, remediation and other advances in
near-term nanotech are helping to solve one of the biggest challenges of the 21st century.

(3) Increasing the health and longevity of human life. Nanotechnology is producing sensors to
detect disease such as cancer early, nanoparticles to deliver drugs to more effectively treat
disease, and nanoparticles that provide alternative therapies to heal disease.

(4) Maximizing the productivity of agriculture. Nanotechnology may increase food production
while reducing the harmful environmental effects of agriculture.

(5) Making powerful information technology available everywhere. More efficient computers
and communication systems may be possible through development of nanoscale materials which

11
may supplement silicon in electronics. To overcome the problem of defects that occur when
manufacturing nanoscale materials, nanomaterial design errors might be incorporated in the
process rather than trying to fix them.

(6) Enabling the development of space. Strong and light materials are critical for space
exploration. Carbon nanotube research may create stronger fibers than conventional macro-scale
fibers.

Societal and ethical implications of NST will be particularly important in the area of
nanomedicine. One organization in which these implications may be considered is the American
Academy of Nanomedicine (AANM). The AANM [3] is a fast growing professional, academic
and medical society dedicated to advancing research in nanomedicine. Goals of the academy
include providing a forum for scientific investigation, communicating new findings and
encouraging collaboration among the diverse disciplines represented in Nanomedicine [3].
Annual scientific meetings of the AANM include presentations on basic and clinical
investigations by scientists, engineers, molecular biologists, cell biologists, immunologists,
chemists, mathematicians, subspecialty trainees, and other health care professionals.
The National Science Foundation (NSF) [4] and the National Institutes of Health (NIH) [5]
also have programs to investigate the societal and ethical implications of NST. Information is
available on the web sites for these organizations.

References.
1. UC Institute for Nanoscale Science and Technology, http://www.eng.uc.edu/ucnanoinstitute/
2. Foresight Institute, http://www.foresight.org/
3. American Academy of Nanomedicine, http://www.aananomed.org/
4. National Science Foundation, NSF, http://www.nsf.gov/
5. National Institutes of Health, NIH, http://www.nih.gov/

12
 PART 1

Synthesis of Nanoscale Materials

13
1.2 Solutions for Chapter 2
Design of Nanostructured Materials by Debasish Banerjee, Jingyu
Lao, and Zhifeng Ren

1. What are the key advantages of the bottom-up approach compared to the top-down
approach in nanoscale fabrication?

There are two ways or methodologies to create nano-scale materials. The first one is called the
top-down approach. In this approach the basic idea is to take a large object and disintegrate it
into smaller components. This method of creating smaller objects is often adopted in the
electronics industry. With the increasing demand for fast computing devices, a large number of
electronic components need to be fabricated in a small volume. That is why electrical engineers
are creating smaller and smaller components. The other approach is so called the bottom-up
method. The main idea is to create things by manipulating atoms or molecules to create small
objects.
The development of micro-electronics has reached a point now where it is expected to be
limited in fast computing capabilities by certain fundamental issues of its conventional top-
down approach for fabrication. Besides the approaching fundamental limitation in reducing size,
the micro-fabrication techniques are expensive in general. Significant advancement towards
production and precise control over the morphology and microstructure of various nano-scale
materials opens up a brand new bottom-up approach to nano-scale devices through self-
assembly, which is cost-effective as well as versatile. Several research groups have demonstrated
prototype fundamental electronic devices, such as, field effect transistor (FET), bipolar junction
transistors, p-n junctions, resonant tunneling diode [1], etc. using nanowires, in addition to
numerous nanotube based devices [2]. This approach becomes particularly powerful when the
ease and control offered by the self-assembly is combined with the electronic, magnetic or
photonic properties with inorganic components [3]. Furthermore, the self-assembly approach to
nano-engineering has enormous potential to provide high density fabrication capabilities and
flexibility to choose a desired material for device functionality, at the same time, enhance the
controllability and tuning capacity of the material properties by downsizing, powered by
quantum confinement effects [4].

References:
1. a) X. F. Daun, Y. Huang, Y. Cui, J. F. Wang, and C. M. Lieber, Nature 409, 66, 2001,
b) Y.Huang, X.Daun, Y.Cui, L.J.Lauhon, K.H.Kim, C.M.Lieber, Science 294,1313,2001
c) D.H.Cobden, Nature 409,32, 2001 (d) G.Y.Tseng, J.C.Ellenbogen, Science 294,1293, 2001.

2. R.H.Baughman,A.A.Zakhidov, W.A.de Heer, Science 297, 787, 2002

3. a) C.T.Black, C.B. Murray, R.L. Sandstrom, S. Sun, Science 290, 1131, 2000, (b) T.Thurn-
Albrecht, Science 290, 2126-2129, 2000. (c) C. Sanchez, B. Lebeau, Mater. Res. Soc. Bull. 26,
377, 2001.

4. a) B.B.Li , D.P. Yu, S.L.Zhang,Phys Rev. B, 59,1645,1999, b) S.Q.Feng , D.P.Yu, H.Z.Zhang,

14
Z.G. Bai, Y.Ding J. Crys. Growth 209, 513, 2000; c) A.M. Rao, E.Richter, S.Bandow, B.Chase,
P.C. Eklund, K.A.Williams, S.Fang,K.R, Subbaswamy,M. Menon M, A.Thess, R.E.Smalley, G.
Dresselhaus, M.S.Dresselhaus, Science 275, 187, 1997

2. Discuss the strategies one can adopt to grow nanostructures out of their bulk form.

The answer to this question is best explained in this publication; "One-dimensional

nanostructures: synthesis, characterization and applications", Y. Xia, P. Yang, Y. Sun, Y. Wu, B.
Mayers, B. Gates, Y. Yin, F. Kim, H. Yan, Adv. Mater. 15, 353, 2003.

3. Discuss the vapor phase epitaxy approach for nanostructure growth.

Vapor phase epitaxy is the general method to grow nanostructures of all solid materials. In
principle any bulk material can be converted to its one-dimensional nanostructure form in this
approach. The vapor phase epitaxy approach employs vapor transport and condensation to grow
nanostructure. First, we thermally evaporate either a mixed source or two different sources and
then direct the vapor molecule towards the substrate, which is at a lower temperature. The vapor
condenses on a suitable substrate, such as graphite foil sapphire, to form the nanostructures. At
the end of the process, a fine powder is found deposited on the substrate facing the vapor stream.
In the early twenties Volmer and others grew the first mercury nanofibers of 20nm diameter
and 1mm length condensing mercury vapor on glass[1], later on, in the mid-fifties, a series of
studies were conducted by Sears and others to explain one dimensional growth through a general
growth mechanism based on axial screw dislocation [2],which basically explains the growth
kinetics. It has been accepted now that the supersaturation process during growth is the key to
get various shapes and morphology of nanostructures. The vapor-liquid- solid (VLS) approach is
the most popular process to grow one dimensional nanowires, and was proposed by Wagner and
Ellis in 1964. The VLS approach involves the absorption of the source material from the gas
phase into a liquid droplet of a catalyst [3] and from a liquid alloy. The liquid alloy clusters serve
as a preferential site for absorption and supersaturation of reactant and thus breaking the
symmetry to form one-dimensional nanowires. One dimensional growth occurs as long as the
catalyst remains liquid. The most important issue with this approach is to find the perfect catalyst
for a particular material, which coexists as a liquid at a eutectic temperature. Observation of the
catalyst particles at the end of the nanostructures is generally considered as a proof of VLS
growth. In the last few years researchers have synthesized semiconducting oxide nanowires of
ZnO [4, 5, 6], In2O3 [7], SiO2, Ga2O3 [8] etc.; nanobelts of ZnO, SnO2, In2O3, CdO, PbO [9] etc.
using the vapor phase epitaxy approach. Recently, Lee and co-workers produced semiconducting
Si nanowires with relatively high yields with the oxide assisted growth (OAG) mechanism, a
claimed fundamentally different approach to grow nanostructures than the VLS method [10]. In
oxide assisted growth, metal catalyst is not needed; semi-liquid sub-oxides (which has a lower
melting point than oxides) droplet act as a catalyst for the preferential growth sites. Suggested
Reading: Chemistry and Physics in One Dimension: Synthesis and Properties of Nanowires and
Nanotubes J. Hu, T. W. Odom, C. M. Lieber, Acc. Chem. Res., 32, 435, 1999.

1. M.Volmer, I.Estermann, Z.Phys, 7,13,1921

15
2. a) G.W.Sears, Acta Metall. 3,367,1955, b) G.W.Sears, Acta Metall. 1,427,1953
3. J. Hu, T. W. Odom, and C. M. Lieber, Acc. Chem. Res. 32, 435, 1999
4. a) P.Yang, H.Yan, S.Mao,R.Russo, J.Johnson, R.Saykally, N.Morris, J.Pham, R.He, H.J.Choi,
Adv. Funct. Mater.12(5), 2002, b) Y. C. Kong, D. P. Yu, B. Zhang, W. Fang, S. Q. Feng,
Appl. Phys. Lett. 78, 4, 2001
5. S. H. Jo, J. Y. Lao, and Z. F. Ren , R. A. Farrer, T. Baldacchini, J. T. Fourkas, Appl.Phys.Lett.
83, 4821, 2003
6. D. Banerjee, J. Y. Lao, D. Z. Wang, J. Y. Huang,Z. F. Ren , D. Steeves, B. Kimball, M.
Sennett , Appl. Phys. Lett. Appl. Phys. Lett. 83, 2061, 2003
7. C.H.Liang, G.W.Meng, Y.Lei, F.Phillipp, L.D.Zhang, Adv. Mater.13,1330,2001
8. a) Z.L.Wang, R.P.Gao, J.L.Gole, J.D.Stout, Adv. Mater, 12,1938, 2000, b) C.H.liang,
G.W.Meng, G.Z.Wang, Y.W. Wang, L.D.Zhang, S.Y.Zhang Appl.Phys.Lett. 78,3202, 2001
9. a) Z.WPan, Z.R.Dai, Z.L.Wang, Science 291,1947, 2001, b)Z.W.Pan,Z.R. Dai,Z.L.Wang,
Appl. Phys. Lett. 80,309, 2002. c)Z.R. Dai, Z.W.Pan, Z.L.Wang, Solid State Commun. 118, 351,
2001
10. R.-Q.Zhang, Y.Lifshitz, S.T.Lee, Adv. Mater. 15, 635, 2003.

4. How does the vapor-solid-liquid (VLS) growth mechanism of nanostructures work?

What are its advantages? What is the key difference between VLS and OAG (oxide-
assisted growth)?

1D nanowires are the most commonly used form of nanostructures. We will focus on ZnO
nanowires. Even though there are some reports on solution based methods, most of the research
on nanowires has been focused on vapor phase growth techniques [1]. Among the vapor phase
methods [2], metal organic chemical vapor deposition (MOCVD), chemical vapor deposition
(CVD), physical vapor deposition (PVD), and thermal evaporation have shown a unique
usefulness in growing ZnO nanostructures. A simple vapor phase techniques developed recently
is known as thermal evaporation and condensation. In this method, the material is first heated to
produce a vapor, which is then transferred to the lower temperature zone of a closed furnace with
a controlled atmosphere, to solidify to form quasi 1D nanocrystals. In this approach, ZnO
nanostructures follow two basic growth mechanisms; (a) the vapor liquid solid (VLS) method,
and (b) the vapor solid (VS) method or also called oxide assisted growth (OAG).
The Vapor solid liquid (VLS) approach. As shown in Fig.1, this mechanism was first proposed
for the growth of single crystal silicon whiskers, 100 nm to hundreds of microns in diameter, in
1964 by Wagner and Ellis [3].

16
 Semi liquid Au
Au droplet particle

ZnO
nanowires

Zn/Au
Alloy Substrate
Zn vapor

Fig 1. Schematic diagram of VLS growth mechanism.

This method involves the absorption of the source material from the gas phase into a liquid
droplet of a catalyst (gold, in this case) [1] to form a liquid alloy. The liquid alloy clusters serve
as a preferential site for absorption and supersaturation of reactant and thus break the symmetry
to form 1D nanowires. 1D growth occurs as long as the catalyst remains liquid. The most
important issue with this approach is to find the perfect catalyst for a particular material, which
coexists as a liquid at a eutectic temperature. Observation of the catalyst particles at the end of
the nanostructures is generally considered to be proof of VLS growth. The main advantage of
this approach is that nanowires can be grown on selective sites.
ZnO
nanowires
Semi-liquid
ZnOx
Zn or substrate
ZnOx
droplet
Zn vapor

Fig. 2. Schematic diagram of the OAG growth mechanism.

Oxide Assisted Growth (OAG). As shown in Fig 2, ZnO nanowires can grow without the
presence of any catalyst. Zn and Zn sub-oxides (ZnOx where x<1) droplets produced during the
vapor phase reaction have low melting temperatures (approximately 419 C) for both Zn and
ZnOx. At the low temperature site (lower than 907 C, i.e., the boiling point of Zn) the Zn-sub-
oxide vapor produced condenses in the low temperature zone and act as ideal nuclei of ZnO
nanowires [4]. Suggested reading: Oxide assisted growth of semiconductor nanowires R.-
Q.Zhang, Y.Lifshitz, S.T.Lee, Adv. Mater. 15(7-8), 635, 2003.

References:
1. J. Hu, T. W. Odom, C. M. Lieber, Acc. Chem. Res. 32, 435, 1999.

17
2. G. C. Yi, C. Wang, W. I. Park , Semicond. Sci. Technol. 20, S22, 2005.
3. R. S. Wagner, W. C. Ellis, Appl. Phys. Lett. 4, 89, 1964.
4. B.D. Yao, Y.F. Chan, N. Wang, Appl. Phys. Lett. 81, 4, 2002.

5. What are the strategies for growing nanostructures in complex hierarchical form?
Explain and give examples.

We have discussed the usefulness of ordering nanostructures in relatively complex forms in the
text. In the past few years, the research community in nano-scale science has earned a reasonable
success in growing and functionalizing one dimensional nanostructure, but not many reports
have come out for hierarchical 3D structures, because of its complex mechanism and difficulty in
controlling the processes. One simple approach to grow multi-dimensional nanostructures is first
growing nanowires by the VLS method and then switching the synthesis condition to grow
different materials on the surface by chemical vapor deposition (CVD). Lauhon and co-workers
demonstrated the synthesis of Si/Ge and Ge/Si coaxial nanowires [1] and have shown that the
outer shell can be formed epitaxially on the outer core. Wang and others generated a mixture of
coaxial and biaxial SiC-SiOx nanowires via a catalyst-free high temperature reaction of
amorphous silica and graphite mixture [2]. A few years back, Zhu and co-workers synthesized
some 3D flower-like nanostructures consisting of SiOx fibers radially attached to a single
catalytic particle, using a solid-solid and gas-solid reaction. In the same method they also
synthesized a MgO fishbone or fern-like type fractal nanostructure assembly [3]. Several other
nontrivial 3D structures such as Bi2S3 skeletons [4] and SnO [5] nano-ribbon networks have also
been demonstrated. Recently, Yang and others showed ZnO nanocrystals with exotic shapes like
a tetrapod, tripod, nano-comb etc, by thermal evaporation of a mixture of ZnO and graphite [6].
In a similar way, Wang and co-workes produced nanocombs and nanowindmills of wurtzite ZnS
[7].
The general method for synthesizing these nanostructures is similar to that described in our
recent reports. [8] The source, a mixture of the required oxides and graphite powder was inserted
into the sealed end of a small quartz tube. The substrate was placed at the open end of the quartz
tube and then the open end was covered with graphite foil. Then the entire assembly was placed
in the ceramic tube of a tube furnace which was evacuated using a rotary pump. The vacuum in
the ceramic tube was kept at a pressure of approximately 0.52.5 Torr of air. The source
temperature was then raised to about 9501050 C and held for 1530 min at a pressure of 0.5
1.5 Torr. After cooling, ZnO nanostructures were present either on the substrate or on the
covering graphite foils. Growth condition dependant microstructures are listed in table 1.
Details of growth of each hierarchical structure are described in section 2.2.3.4-2.2.5 also in this
publication: J. Y. Lao, J. Y. Huang, D. Z. Wang, Z. F. Ren, "Hierarchical Oxide Nanostructures",
J. of Materials Chemistry 14, 770 - 773 (2004).

18
References.
1. L.J.Lauhan, M.S.Gudiksen, D.Wang, C.M.Leiber, Nature,420,57,2002
2. Z.L.Wang, Z.R.Dai, Z.G.Bai, R.P.Gao, J.L.Gole, Appl.Phys.Lett., 77, 3349,2000.
3. Y.Q.Zhu, W.K.Hsu, W.Z.Zhou, M.Terrones, H.W.Kroto, D.R.M.walton, Chem. Phys.Lett.
347,337,2001.
4. D.Wang, M.Shao, D.Yu, W.Yu, Y.Qian, J. Crys. Growth, 254,487, 2003.
5. Z.L.Wang, Z.Pan, Adv. Mater. 14(15), 2002.
6. H.Yun, R.He, J.Pham, P.Yang, Adv. Mater. 15(5),402,2003.
7. C.Ma, D.Moore, J.Li, Z.L.Wang, Adv. Mater. 15 (3), 228, 2003.
8. J.Y.Lao, J.G.Wen, Z.F.Ren, Nano Lett., 2 (11), 1287, 2002 ; a)J.Y.Lao, J.Y.Huang,
D.Z.Wang and Z.F.Ren, Nanolett., 3 (2), 235,2003 b) J.G.Wen, J.Y.Lao, D.Z.Wang,
T.M.Kyaw, Y.L.Foo, Z.F.Ren, Chem. Phys. Lett. 372,717-722, 2003

6. Why is ZnO superior to other oxide semiconductors for shortwave lasing applications?
What are the advantages of ZnO in its nanostructure over its bulk form?

The interest in developing a short wavelength semiconductor laser was initiated by the
realization of room temperature green-blue diode lasers structure with ZnSe and InxGa1-xN as
active layers. Some reports of using ZnO thin film and particles lead to believe in the possibility
of room temperature UV lasing from 1 D system. Usually for wide band gap semiconductors a
high carrier concentration is required in order to reach an optical gain that is high enough for
lasing action in an electron-hole plasma process. Such a conventional system requires a high
lasing threshold. On the other hand, excitonic recombination in semiconductors is a more
efficient radiative process and can accommodate low threshold stimulated emission. To achieve
such a system of efficient excitonic lasing at room temperature, the exciton binding energy of the
material media must be larger than the thermal energy at room temperature (26 meV). To that
end, compared to the other wide bandgap semiconductors such as ZnSe (22 meV) and GaN (25
meV), ZnO is a more promising candidate having an excitonic biding energy of 60 meV.
An exciton is bound state of an electron and a hole, or a Coulomb correlated electron/hole
pair, in an insulator or semiconductor. When a photon excites an electron from the valence band
in a semiconductor, the hole created in the conduction band is attracted by the Coulomb force.
The exciton results from the binding of the electron with its hole; as a result, the exciton has less
energy than the unbound electron and hole. The wave function of the bound state is hydrogen
atom-like. However, the binding energy is much smaller and the size much bigger than a
hydrogen atom because of the effects of screening and the effective mass of the constituents in

19
the material.

Conduction Band (empty)

Photon

Valance band (full)

Conduction Band
Negatively charged

Coulomb
attraction

Positively charged
Fig. 3. Energy diagram of exciton formation. A photon enters a semiconductor, exciting an
electron from the valence band into the conduction band. The missing electron in the valence
band leaves a hole behind, of opposite electric charge, to which it is attracted by the Coulomb
force. The exciton results from the binding of the electron with its hole; as a result, the exciton
has slightly less energy than the unbound electron and hole.

Fig. 4. Left figure shows free (Wannier) exciton. Radius >>a. This is typical for semiconductors.
Right figure shows tightly-bound (Frenkel) exciton. Radius ~a. This is typical for ionic crystals
and organic molecular crystals.

Excitons can be treated in two limiting cases, which depend on the properties of the material in
question. In semiconductors, the dielectric constant is generally large, and as a result, screening

20
tends to reduce the Coulomb interaction between electrons and holes. The result is a Mott-
Wannier exciton, which has a radius much larger than the lattice spacing. As a result, the effect
of the lattice potential can be incorporated into the effective masses of the electron and hole, and
because of the lower masses and the screened Coulomb interaction, the binding energy is usually
much less than a hydrogen atom, typically on the order of 0.1 eV. This type of exciton was
named for Sir Nevill Francis Mott and Gregory Wannier. Due to small binding energy, such
excitons move freely through crystals, which is typical for semiconductors. In insulators,
excitons tend to be much smaller, of the same order as the unit cell. Due to the large binding
energy, it is localized on one lattice site. This kind of electron-hole pair is called a Frenkel
exciton, named after J. Frenkel.
The existence of exciton states may be inferred from the absorption of light associated with
their excitation. Typically, excitons are observed just below the band gap. Alternatively, an
exciton may be thought of as the excited state of an atom or ion, the excitation wandering from
one cell of the lattice to another. An exciton can bind with other excitons to form a bi-exciton,
analogous to a hydrogen molecule. If a large density of excitons is created in a material, they can
interact with one another to form an electron-hole liquid. It was found recently that in
semiconductors, excitonic recombination is an efficient radiative process and can accommodate
low threshold stimulated emission.
The basic elements of a semiconductor laser include an active gain medium that provides
optical gain by stimulated emission, and an optical resonant cavity that confines the photons to
create positive optical feedback, as shown in Fig. 5.The electron and hole in the semi-conducting
medium is excited to non-equilibrium energy levels by optically or electrically pumped energy.
If the resulting gain is sufficient to overcome the losses of the optical cavity that provides the
necessary feedback of the radiation, lasing oscillation can be established at a well-established
threshold.

Gain medium

Cavity mirror

Fig. 5. The basic elements of a semiconductor laser: Optical gain medium and cavity mirror.

Lets discuss the various kinds of resonant cavities developed over the years to achieve effective
semiconductor lasers. Fig. 6(a) shows a conventional edge-emitting in-plane optical cavity with a
cleaved facet mirror. The main disadvantage of this design is the presence of a multimode
operating region, by which the spontaneous emission of the active gain material is distributed
over a large number of non-lasing modes. To overcome the problem of multimode operation,
over a few decades, various innovative designs have been explored. Fig. 6(b) shows a vertical
cavity surface-emitting laser, which is one of the first optical cavities made in the order of
wavelength of light.

21
 Fig. 6. Design of various kinds of design optical cavities developed over the years.(a)
Conventional edge-emitting laser having long optical cavity (always > 100m) results in
multimode operation, (b) Design of a vertical cavity surface-emitting laser consisted of
epitaxially grown distributed Bragg reflectors acts a 1-D photonic crystal. (c) Micro-disk laser
uses the high refractive index material to facilitate total internal reflection of light. (d) Vertically
aligned semiconductor nanowire nanolaser. Drawing curtsey Prof. S.S. Mao, UC Berkeley.

The distributed Bragg (DBR) mirrors are designed as photonic crystals, consisting of a dielectric
medium patterned into a regular structure with a length scale on the order of the optical
wavelength. A defect in a photonic crystal will lead to a localized photon state within the band
gap which serves as a laser cavity with a small mode volume and where the multimode operation
was excluded. Fig. 6(c) shows a micro-disk type laser where a high refractive index disk was
used to facilitate a total internal reflection of light similar to the reflection of sound waves along
a curved inner surface. These cavities exhibit higher quality factors, leading to the enhancement
of the spontaneous emission. Fig. 6(d) shows a vertically aligned semiconductor nanowire
nanolaser, where photon confinement in one-dimensional nano-scale cavities has been achieved.
Crystalline nanorods have a length on the order of light wavelength, and the two facets work as
natural mirrors to form optical cavities. As mentioned earlier, ZnO, because of its high exciton
binding energy (60 meV), can achieve an efficient excitonic laser action at room temperature
(thermal energy at room temperature is 26 meV). A lower threshold is further achieved by low-
dimensional semiconductor nanostructures in which quantum size effects yield a substantial
density of states at the band edges and enhance radiative recombination due to carrier
confinement. Suggested reading: M. Huang, S. Mao, H. Feick, H. Yan, Y. Wu, H. Kind, E.
Weber, R. Russo, P. Yang, Science, 292, 1897 (2001).

7. Discuss applications of ZnO and In2O3 in various fields.

Zinc Oxide (ZnO). ZnO has a unique combination of high values of band gap energy, cohesion
and exciton stability. The very high exciton binding energy (60meV) gives it a very high
potential for room temperature light emission. This also gives ZnO a strong resistance to high
temperature electronic degradation during operation (e.g. laser diodes).

22
 Table 2. Comparison of compound semiconductor properties.
Lattice Band Exciton Dielectric
Material Crystal parameters gap Binding constant
structure (nm) energy energy (0)
A c (eV) (meV)
ZnO Wurzite 0.329 0.52 3.37 60 4.6
ZnS Wurzite 0.382 3.80 30 5.1
ZnSe Zinc 0.626 2.70 20 5.8
GaAs blende 0.566 1.43 4.2 10.9
GaN Zinc 0.565 3.39 21
blende 0.319
Wurzite 0.518

ZnO is the hardest of the II-VI family of semiconductors. Table 2 compares the key properties of
ZnO with other compound semiconductors. These properties have been explored to fabricate
ZnO based devices in various fields. Applications of various properties of ZnO have been
summarized in the list below:
1. High piezoelectric property. (e33 = 1.2 C/m2, among highest of all semiconductors) [1].
2. High thermal conductivity of 50.4 W/mK (compared with 46.0 for GaAs). [2], [3]
3. Largest exciton binding energy of II-VI & III-V semiconductors, 60 meV = excitonic
stimulated light emission up to 550 K. [4].
4. High radiation damage threshold (up to 1 MeV, 4 x 1016 electrons/cm-2; higher than GaN or
GaAs) [4].
5. Drift mobility saturates at higher fields; higher values than GaN = attractive for high
frequency devices. For room temperature, drift velocities higher than 3 X 107 cm/s at fields
near 250 kV/cm. [5]
6. Very low dark current UV detectors with maximum spectral response at 350nm. [6]

In2O3 (Indium Oxide). Indium oxide is used in batteries, transparent thin film infra-red
reflectors. It is also commonly doped with tin oxide (SnO2) to make indium tin oxide (ITO),
which is used in transparent thin conductive thin films, which are used in various different types
of displays, energy efficient windows and photovoltaics.

References.
1. A.Dalcorso, M. Posternak, R. Resta, A. Baldereschi, Phys. Rev. B 50, 10715, 1994.
2. C.M. Barrado, E. R. Leite , P. R. Bueno , E. Longo, J. A. Varela, Mat. Sci. and Eng.
A,371, 377, 2004.
3. S.Capinski, H. J. Maris, Physica B: Cond. Mat., 219, 699, 1996.
4. D.C. Look, Mat. Sci. and Eng. B 80, 383, 2001.
5. J.D. Albrecht, P. P. Ruden, S. Limpijumnong, W. R. L. Lambrecht, K. F. Brennan, J
of Appl. Phys., 86, 6864, 1999.
6. T.H. Moon, M. C. Jeong, W. Lee, J. M. Myoung, J of Crys. Growth, 265, 34, 2004.

8. What are the various techniques of producing nanostructures? Explain the vapor

23
transport and condensation technique. What are the useful characterization techniques for
nanostructures?

This question is mostly answered in questions 2 and 4. A literature survey could be done to
provide recent results.

24
1.3 Solutions for Chapter 3
Carbon Nanotubes and Bismuth Nanowires by Mildred S.
Dresselhaus, Ado Jorio, and Oded Rabin (Solutions by Mark
Schulz)

1. Based on the cutting lines concept, explain why for an (n,m) single-wall carbon nanotube
(SWNT) the nanotube is a large bandgap semiconductor, when n m is not a multiple of
three, with the band gap increasing as the diameter decreases (1/dt dependence), while the
nanotube shows metallic behavior (at room temperature) for n m = 3j ( j = integer).
Compare the electronic density of states near the Fermi level for semiconducting and
metallic SWNTs and for a 2-D graphene sheet.

Please perform a literature survey to answer this question. Also consider:

1. Philip Kim, Teri W. Odom, Jin-Lin Huang, and Charles M. Lieber, Electronic Density of
States of Atomically Resolved Single-Walled Carbon Nanotubes: Van Hove Singularities
and End States; PHYSICAL REVIEW LETTERS, VOLUME 82, NUMBER 6, 8
FEBRUARY 1999.
2. Su Chang-Rong and Li Jia-Ming, Novel Bismuth Nanotubes, 2002 Chinese Phys. Lett. 19
1785-1787.

2. How are single-wall carbon nanotubes formed in the laboratory? Which mechanism for
SWNT growth (catalytic root growth or tip growth) is most probable for the synthesis of
very long (~cm) tubes? What are the major challenges that need to be addressed in
advancing carbon nanotube synthesis?

To answer this question, please read the paper below, survey the literature, and then draw some
conclusions about the questions.
1. Kenji Hata, Don N. Futaba, Kohei Mizuno, Tatsunori Namai, Motoo Yumura, Sumio Iijima,
Water-Assisted Highly Efficient Synthesis of Impurity-Free Single-Walled Carbon
Nanotubes, Science 19 November 2004: Vol. 306. no. 5700, pp. 1362 1364.

3. List the common methods for nanotube characterization, and their advantages and
limitations. What is it that each characterization method probes and why is it important to
gain this information?

There are many methods to characterize the morphology and the chemistry of nanotubes, but not
one or a few methods that can do it all. Consider high resolution transmission electron
microscopy (HRTEM), environmental scanning electron microscopy (ESEM), energy dispersive
spectroscopy (EDS), x-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis
(TGA), atomic force microscopy (AFM), Raman spectroscopy, time of flight secondary ion mass
spectroscopy (TOF-SIMS), and other methods. Also see Chapt. 5.

25
4. Why is Raman spectroscopy a particularly valuable tool for the study and
characterization of carbon nanotube systems? What are its advantages and limitations?

Raman spectroscopy can show the relative amounts of graphitic (G peak) and amorphous or
disorder (D peak) of carbon. However, when using Raman spectroscopy with multi-wall carbon
nanotubes a large D peak typically occurs. This may be due to the number of shells and is not
fully explained yet. Refer to books and papers on Raman spectroscopy for further details and
also Chapter 5 in the nanoengineering book.

5. Using the tight binding model, find an expression for the electronic energy levels of an
armchair nanotube. Make an explicit application of your expression to a (10,10) nanotube.

Look at these sites for several papers:

1. http://www.stat.phys.titech.ac.jp/ando/treport/tp2001_j.htm
2. http://flux.aps.org/meetings/YR04/MAR04/baps/abs/S8950.html
3. J.W. Mintmire, C.T. White, First-principles band structures of armchair nanotubes, Applied
Physics A: Materials Science & Processing, 65-69, 2004.

6. For very small-diameter nanotubes, at what diameter does the tube curvature impose
sp3 bonding rather than sp2 bonding. Explain in what sense we can consider this cross-over
point to indicate that the graphitic nanotube becomes a nanodiamond.

Please review these references to answer the question.

1. UNUSUAL PROPERTIES AND STRUCTURE OF CARBON NANOTUBES, M.S.
Dresselhaus, G. Dresselhaus, A. Jorio, Annual Review of Materials Research, August 2004,
Vol. 34, Pages 247-278.
2. SCIENCE AND TECHNOLOGY OF THE TWENTY-FIRST CENTURY: Synthesis,
Properties, and Applications of Carbon Nanotubes, Mauricio Terrones, Annual Review of
Materials Research, August 2003, Vol. 33, Pages 419-501.
3. Dragan Stojkovic, Peihong Zhang, and Vincent H. Crespi; Smallest Nanotube: Breaking the
Symmetry of sp3 Bonds in Tubular Geometries; Phys. Rev. Lett. 87, 125502 (2001).

7. Find the electronic energy levels for a free electron nanowire with a square cross section
(a2) and a length 10a. At what temperature would you expect quantum confinement effects
to become important at room temperature?

A nanowire is a wire of diameter of the order of a nanometer [1]. At this scale, quantum
mechanical effects are important and nanowires are also known as quantum wires. There are
many different types of nanowires that can be used to create extremely small electrical circuits.
Please review the literature to answer this question. Suggested references to start are below.

References

26
1. Wikipedia encyclopedia, http://en.wikipedia.org/wiki/Nanowire
2. The Quantum Hall Effect: K. v. Klitzing, G. Dorda, and M. Pepper; Phys. Rev. Lett. 45, 494-
497 (1980).
3. Y.-M. Lin, O. Rabin, S.B. Cronin, J.Y. Ying, and M.S. Dresselhaus, Appl. Phys. Lett. 81,
2403 (2002).
4. K. Nielsch, R.B. Wehrspohn, J. Barthel, U. Gosele, S.F. Fischer, and H. Kronmuller, Appl.
Phys. Lett. 79, 1360 (2001).
5. L.D. Hicks and M.S. Dresselhaus, Phys. Rev. B 47, 12 727 (1993).
6. L.D. Hicks and M.S. Dresselhaus, Phys. Rev. B 47, 16 631 (1993).
7. Y.-M. Lin, X. Sun, and M.S. Dresselhaus, Phys. Rev. B 62, 4610 (2000).

8. Find the electronic energy levels of a silicon nanowire of diameter dw with its wire axis
along (100) and then repeat for its wire axis along (111). Use the effective mass
approximation and effective mass tensor components for 3-D Si. Explain how to find the
effective mass that governs transport along the nanowire axis and how to find the threshold
for optical transitions.

Reading Chapter 3 and reference to the literature including the references below can be used to
answer this question.
1. http://web.mit.edu/physics/facultyandstaff/faculty/millie_dresselhaus.html
2. Nanowires and nanotubes, Materials Science and Engineering: C, Volume 23, Issues 1-2, 15
January 2003, Pages 129-140, M. S. Dresselhaus, Y. M. Lin, O. Rabin, A. Jorio, A. G.
Souza Filho, M. A. Pimenta, R. Saito, G. Samsonidze and G. Dresselhaus.

9. Assume that the carriers of a nanowire of diameter dw have an effective mass of 0.1m0 in
the plane of the nanowire and 0.05m0 along the nanowire axis. At what magnetic field
value would the electron scattering rate for carriers in a nanowire of diameter dw decrease
rapidly for a magnetic field parallel to the nanowire axis? Repeat for the case of a magnetic
field perpendicular to the wire axis.

Use the chapter information and supplementary references below to answer this question.
1. Xavier Batlle et al, Finite-size effects in fine particles: magnetic and transport properties,
2002 J. Phys. D: Appl. Phys. 35, R15-R42.
2. A. S. Alexandrov1 and V. V. Kabanov, Magnetic quantum oscillations in nanowires, PACS
numbers: 72.15.Gd,75.75.+a, 73.63.Nm, 73.63.b, arXiv:cond-mat/0504321 v2 3 June, 2005.

10. Consider a silicon nanowire to be the same as in Problem 7. At what magnetic field
along the nanowire axis is the spacing of the Landau levels (magnetic energy levels) equal
to the subband spacing? Explain why carrier localization is expected as the nanowire cross-
sectional area becomes very small.

Please use the chapter information and the excellent references below to answer this question.

27
1. M. S. Dresselhaus, Y. M. Lin, O. Rabin, A. Jorio, A. G. Souza Filho, M. A. Pimenta, R. Saito,
G. Samsonidze and G. Dresselhaus, Nanowires and nanotubes, Materials Science and
Engineering: C Volume 23, Issues 1-2 , 15 January 2003, Pages 129-140.
2. Jiangtao Hu, Teri Wang Odom, And Charles M. Lieber, Chemistry and Physics in One
Dimension: Synthesis And Properties of Nanowires and Nanotubes, Acc. Chem. Res. 1999,
32, 435-445.

28
1.4 Solutions for Chapter 4
Nanobelts and Nanowires of Functional Oxides by Xudong Wang
and Zhong Lin Wang

1. How can a nanobelt structure be defined? What are the differences between nanowires,
nanorods, and nanobelts?

The nanobelt morphology can be defined as a single-crystal one-dimensional (1D) nanostructure

that has a rectangular cross-section and well defined side surfaces. The nanowire is a fairly
general terminology in defining 1D nanostructure. Any solid 1D nanostructure can be called as
nanowire. It could be single crystalline, poly crystalline or amorphous. A nanowire generally
grows along a specific axial direction, whereas their side surfaces may not be well-defined. The
cross-section of a nanowire could be round, hexagonal or a polyhedron according to the
crystallography of the material. The length of a nanowire varies from a few hundred nanometers
to microns or even millimeters and its thickness is always negligibly small compared to its length.
A nanorod can be defined as a short nanowire of length in the range from tens to hundreds of
nanometers, which is NOT negligible comparing to its length. A nanobelt can be considered as a
single-crystal nanowire with rectangular cross-section.

2. List at least five methods to synthesize 1-D nanostructures. What are the basic
procedures for the thermal evaporation technique? What are the advantages and
disadvantages of the thermal evaporation technique? How can the disadvantages be
overcome?

Methods to synthesize 1D nanostructures: thermal evaporation, laser ablation, template-assisted

growth, arc discharge, lithography, sol-gel method, metal-organic chemical vapor deposition
(MOCVD), etc. Basic procedures for the thermal evaporation technique (based on single-zone
horizontal tube furnace):
1. Load the tube with source materials and substrate.
2. Pump down the system to around 10-2 Torr to remove air inside the tube.
3. Turn on the furnace to heat the tube to the reaction temperature at a specific heating
rate.
4. Introduce an inert carrying gas, such as argon or nitrogen, into the system at a
constant flow rate to bring the pressure in the tube back to 200-500 Torr (different
pressures are required by different source materials and final deposited
nanostructures).
5. Hold the reaction temperature and pressure for a certain period of time to vaporize the
source material and achieve a reasonable amount of deposition.

Advantages of thermal evaporation technique: Simple experimental setup; low-cost process;

versatile technique that is able to make different morphologies from a variety of materials.

29
Disadvantages of thermal evaporation technique: High temperature required; lack of precise
control over the source vapor concentration.

One possible solution of this disadvantage is mixing the source materials with carbon powder,
which is so-called carbon-thermal evaporation, which can reduce the vaporization temperature
and achieve moderate vapor concentration.

3. Describe how 1-D nanostructures form through a vapor-liquid-solid (VLS) process. How
does a metal catalyst affect the final morphologies of 1-D nanostructures in a VLS process?

A thin layer of metal or pre-synthesized metal nanoparticles are deposited onto a substrate and
used as catalyst. As the furnace temperature is increased, the source material will be vaporized
(Vapor phase) and transported by the carrier gas to the substrate region. Upon the introduction of
the source vapor, the metal catalyst forms liquid alloy droplets once the deposition temperature
rises above the eutectic temperature of the metal and source material (Liquid Phase). With the
constant incoming source vapor, the percentage of source component in the droplet increases and
ultimately supersaturates. Then, a new solid phase is precipitated out at the substrate-liquid
interface and forms wire- or belt-like nanostructures. The 1D nanostructure will keep growing as
long as the temperature is kept above the eutectic point and the supply of source vapor is
adequate.
Generally, the metal catalyst determines the size of the nanowires. For the growth of ZnO
nanobelts, crystalline orientation of the Sn catalyst particle can determine the growth direction
and the side surfaces of the nanobelts.

4. Describe the mechanism of the formation of the porous ZnO 1-D nanostructure.

This mesoporous ZnO nanowires is a unique 1D nanostructure that not only exhibits a very high
surface-to-volume ratio, but also retains the crystallized structure so that their electronic and
optical properties are preserved. The formation of the mesoporous nanowire is due to the
appearance of the Zn2SiO4 out-layer. In a high temperature region, ZnO nanowires can re-
decompose into Zn vapor and O2, which could happen at the local substrate temperature of ~ 600
C. In the meantime, Si-O vapor sublimated from the silicon substrate can be quickly deposited
on the nanowire surface and diffuse into the ZnO lattice, resulting in the formation of a new
phase Zn2SiO4. The newly formed Zn2SiO4 layer tends to have an epitaxial relationship with the
ZnO in order to reduce the interface lattice mismatch. On the other hand, the lattice mismatch
between (0001)ZnO and (001)Zn2SiO4 is 14%, and between (0110)ZnO and 4(010)Zn2SiO4 is 9%,
Zn2SiO4 tends to form textured islands on the surface of ZnO, but they cannot form a continuous
single-crystal film due to large mismatch, resulting in the growth of epitaxial Zn2SiO4 islands on
the ZnO surface. The newly formed Zn2SiO4 is more stable than ZnO at the local growth
temperature. Therefore, there are open areas on the ZnO surface that are not covered by the
Zn2SiO4 network; an evaporation of Zn-O from the open areas forms the pores in the volume of
the nanowire. The sublimation of ZnO and growth of Zn2SiO4 proceed simultaneously and
finally end with a high-porosity ZnO nanostructure.

30
5. What are the three main steps for fabricating the patterned and aligned ZnO nanorods?

The synthesis process involves three main steps: First, a two-dimensional, large-area and highly
ordered monolayer of sub-micron polystyrene (PS) spheres was self-assembled on a single
crystal Al2O3 (sapphire) substrate. Second, the self-assembled arrays of PS spheres were used to
pattern the gold catalyst. For this process, gold particles were either sputtered or thermally
evaporated onto the self-assembled monolayer structure; as a result, a honeycomb-like hexagonal
gold pattern and a highly ordered hexagonal array of gold spots were obtained respectively.
Finally, using a carbon-thermal evaporation method, aligned ZnO nanorods were obtained
through a VLS process. Following the patterned gold catalyst, the aligned ZnO nanorods exhibit
a hexagonal arrangement on the sapphire substrate.

6. List the possible applications of nanobelts. What are the advantages of using a nanobelt
as an SPM cantilever?

Owing to their well-controlled crystal structures and the morphology-induced unique chemical,
physical and electrical properties, semiconducting nanobelts could be applied in a broad area,
including nano SPM/AFM cantilevers, solid state sensors, transducers, FETs, resonators and
more.
Based on the application requirements, an ideal SPM/AFM cantilever would be a robust 1D
belt-like structure that is small and rigid. Upon the discovery of semiconducting oxide nanobelts,
it is found that the nanobelts could be ideal candidates for cantilever applications. Structurally,
most of the nanobelts are single crystals and dislocation free, which provide them excellent
mechanical properties with both high elastic modulus and high mechanical flexibility.
Geometrically, nanobelts can be made about 1000 times smaller than the conventional used
cantilever, thus the sensitivity of the cantilevers can be greatly increased. Furthermore, there are
feasible methods to manipulate the nanobelts so as to realize the cantilever applications, such as
using AFM tip to pick, cut, and locate the nanobelts.

31
1.5 Solutions for Chapter 5
Advances in Chemical Vapor Deposition of Carbon Nanotubes by
Vesselin N. Shanov, Atul Miskin, Sachin Jain, Peng He, and Mark J.
Schulz (Solutions by Vesselin Shanov)

1. List the important benefits of the CVD approach as compared to other preparation
techniques for synthesis of CNT.

Currently there are three principal techniques to produce high quality SWCNT, laser
ablation, electric arc discharge, and Chemical Vapor Deposition (CVD). Laser ablation and arc-
discharge are modified Physical Vapor Deposition (PVD) techniques and involve the
condensation of hot gaseous carbon atoms generated from the evaporation of solid carbon.
However, the equipment requirements and the large amount of energy consumed by these
methods make them mostly suitable for laboratory research. Both the laser ablation and arc
discharge techniques are limited in the volume of sample they can produce in comparison to the
size of the carbon source. In addition, more impurities accompany the nanotubes in the form of
amorphous carbon and catalyst particles because of the high temperature nature of the heat
source. Since the growth is difficult to control, the final product consists mostly of MWNT with
poor alignment.
Chemical Vapor Deposition has become the most important commercial approach for
manufacturing carbon nanotubes. CVD is known as irreversible deposition of a solid from a gas
or a mixture of gases through a heterogeneous chemical reaction. This reaction takes place at the
interface of gas-solid substrate, and depending on the deposition conditions, the growth process
can be controlled either by diffusion or by surface kinetics. CVD is the preferred technique for
fabrication of thin layers of metals, insulators and semiconductors on different substrates. This
method can be easily scaled up to industrial production. CVD is a continuous process and
currently is the best-known technique for high yield, and low impurity production of CNT at
moderate temperatures. It offers better growth control because of the equilibrium nature of the
chemical reactions involved. In addition, CVD has the capability to control the size, shape and
alignment of the nanotubes through a carefully designed patterning of the catalysts on the
substrates surface. A typical schematic illustrating CVD reactor for growing CNT is shown in
Figure 1. The precursor in the drawing is ethylene. The bubbler provides water vapor carried by
argon gas into the reactor. Water serves as oxidizing agent helping to remove the amorphous
carbon from the surface of the catalyst particle. In addition, hydrogen and argon are added to the
gas mixture for better control of the carbon concentration in the gas phase. A sample holder
accommodates the substrate with patterned catalysts on its surface. The reactor is heated by a
resistance furnace and the gas phase is monitored via a quadupole mass spectrometer.

32
 T
C2H4(g) C(s) + 2H2(g)
H2
Figure 1. Schematic of a CVD reactor for carbon nanotube growth.

2. Perform a literature search on CVD growth of CNT and reveal any new advances that
have been made relative to the information provided in this chapter.

The reader is encouraged to use Internet search engines with key words such as: CVD,
CNT, CNT catalyst, CNT characterization, and CNT application. It is expected that a lot of new
publications related to the search area will appear. The next step can be to narrow the search by
using more specific key words in order to select papers of particular interest.

3. List the catalysts, the substrates, and the carbon precursors used for synthesis of CNT by
CVD.

Transition metals such as Fe, Co, and Ni are frequently used as catalysts. In addition to
these catalysts, other metals such as: Sc, Ti, V, Cr, Mn, Y, Zr, Nb, Mo, Hf, Ta, W, Re or a
combination of them are also included into the family of catalysts for CNT growth. In some
cases the catalyst is introduced as a vapor in the CNT growth zone. This is known as the floating
catalyst approach, which provides nano-size particles of the metal catalyst. A typical floating
catalyst compound, which has been studied extensively, is ferrocene. The reaction takes place at
about 1,100 C depending on the stability of the hydrocarbon. The metal catalyst can stay on top
of the CNT forming a cap encapsulating the CNT. In some cases, it remains at the bottom of the
CNT, which promotes a bamboo-shaped morphology. The growth mechanism postulates that
carbon atoms from the gas phase are transported through the melted carbon-catalyst solution to
the growth surface of the CNT. This process is based on the Vapor-Liquid-Solid (VLS)
mechanism. The selection and preparation of the substrate and catalyst are important aspects
affecting the nanotube yield, and the ability to purify the product of the synthesis.

Frequently used substrates are ceramic particles such as magnesium oxide (MgO),
aluminum oxide (Al2O2) and in some cases mixed with SiO2 to form hybrid materials for bulk
synthesis. Silicon, glass, ceramic or metal wafers are frequently used for surface synthesis.

33
 CVD of CNT uses carbon precursor gases such as methane, ethylene, acetylene, benzene,
carbon monoxide or ethanol. The process usually involves high temperature decomposition of
hydrocarbons in hydrogen over the catalyst, which is pre-deposited on the solid substrate.

4. Describe the difference between the bulk synthesis and surface synthesis in terms of yield
and alignment of CVD-grown carbon nanotubes.

The CVD synthesis of CNT can be divided into two major groups: bulk synthesis and
surface synthesis on flat substrates. The first group is based on ceramic particulate substrates
described above. Catalysts of pure metals or alloys are deposited on the ceramics, which provide
support and structural stability at elevated temperatures. High surface area catalysts with a
porous structure of the supported ceramics are desirable for high yield of CNT grown by CVD.
Alumina-supported Fe-Mo is a frequently used substrate/catalyst combination for synthesis of
SWCNT.

Surface synthesis of SWNT requires flat substrates such as polished or porous Si wafers,
patterned with metal catalysts by various lithographic techniques. An advantage of this technique
is that the final CNT product is much cleaner than the one grown by bulk synthesis. In addition,
the surface synthesis provides better control of the diameter and the alignment of the carbon
nanotubes, which makes it attractive for device fabrication. The size and the pattern of the metal-
catalyst islands on the Si substrate predetermine their orientation, geometric dimensions and
selective growth. Figure 2 shows multilayered Si substrate patterned with Fe particle, which are
uniformly distributed on the substrates surface. Each catalyst cluster is about 40 nm large and
promotes growth of one multiwall CNT with diameter of about 20 nm.

Figure 2. AFM images of iron clusters on Si/SiO2/Al2O3 multi-layered substrate prepared for
CVD of CNT arrays.

The use of bulk or surface approach affects the morphology of the CNT synthesized on
ceramic particles or on flat substrates patterned with catalyst. This is illustrated in Figure 3 which
reveals spaghetti type CNT synthesized on MgO particles and aligned CNT arrays grown on Si
substrates patterned with Fe nanoclusters (as shown in Figure 2).

34
 (a) (b) (c)

(d)

Figure 3. SEM images of CNT grown on ceramic particles and or Si substrates: (a) bulk
synthesis of spaghetti type CNT on powdered MgO substrate coated with Fe catalyst; (b) 50
m CNT array grown on patterned with Fe nanoclusters Si; (c) 0.7cm long CNT array grown on
Si in collaboration with CVD Equip. Inc. by an UC optimized process; Large area of CNT arrays
grown at UC with a novel catalyst and CVD process.

5. List the impurities of as-grown CNT and describe the purification procedures for their
removal.

As deposited CNT are frequently contaminated with metal catalysts, ceramic particles,
amorphous carbon, and graphitic nanoparticles. Purification of the as-grown CNT is a complex
procedure. The first step of purification includes removal of the impurities by wet chemical

35
oxidation. Acids such as hydrochloric and nitric acid are frequently used for this purpose.
Additional steps include decanting, centrifugation or filtration, followed by rinsing in de-ionized
water. Gas or vapor phase oxidation is also used for deeper refinement. Finally, gentle treatment
in an ultrasonic bath helps to continuously break up agglomerated nanotubes. These approaches
are frequently combined to achieve more comprehensive purification and a higher CNT yield.

Most of the purification efforts are based on wet-chemical treatment. This approach
offers large scale processing. The involvement of strong acids causes a lot of defects on the
nanotubes. The followed procedures such as: filtering and drying after chemical etching
substantially lowers the yield. Figure 4 shows an acid reflux system used at UC which enables
fast purification of CNT and carbon nanofibers (CNF). An appropriate amount of H2SO4, HCl,
and HNO3 is mixed with CNT or CNF. A hot plate is used to heat the suspension up to 110 C.
The evaporated acids condense and return to the initial vessel with the CNT suspension. The
reflux system reduces the acid losses, thus maintaining their concentration, which helps to
shorten the purification time.

Figure 4. UC reflux system for CNT purification.

Along with wet purification UC is exploring dry plasma purification. This method is clean,
efficient, can be done at low-temperatures and offers minimum loss during the treatment. Plasma
etching for removal of amorphous carbon that poisons the catalyst or to etch out the remaining
catalysts has been tested using water-plasma with or without additional hydrogen. However, a
prolonged plasma processing may damage the graphitic structure of the nanotubes. There are
several reactors reported in the literature for plasma processing of nanostructured particles:
vibrating bed reactor, fluidized bed reactor and rotary drum reactor. The one used at UC (Diener
Electronic, PICO Model) includes a cylindrical tumbler and is shown in Figure 5.

36
 Fig. 5. UC plasma system for CNT purification.

Another simple approach for dry purification of carbon nanostructured materials is high
temperature oxidation (325-425C) in air. It is important to note that when using this technique
the metal catalyst should be removed first by wet oxidation. The last step is required, since in the
presence of oxygen the metal particles catalyze low temperature oxidation of the CNT, which
decreases the yield dramatically.

Measuring the CNT contaminant can be done by thermo gravimetric analysis (TGA).
Burning the CNT sample in air up to 1,000 C removes all the carbonaceous material and the
metal catalysts in the original sample convert to oxides. Purity evaluation of the CNT is not a
simple procedure. The metal catalyst weight in as-grown CNT is about 30 %. Thermo
Gravimetric analysis (TGA) is frequently used to measure material weight loss or gain as a
function of temperature. This type of analysis provides information related to phase changes,
oxidation or chemical reactions that result in weight loss of gain. TGA is one of many method
used to characterize the purity of carbon nanotubes. Amorphous carbon burns in air at a lower
temperature than graphitic carbon. Therefore if high amounts of amorphous or other non-
crystalline carbon are present, appreciable weight loss should occur below 400C. After this
initial weight loss, a second weight change should occur when the graphitic carbon comprising
the CNT walls oxidizes and converts to CO2. Figure 6 shows TGA of CNT array synthesized
and purified at UC. The graph indicates high purity due to little weight loss in air below 400C,
which corresponds to loss of amorphous carbon.

37
 120

Percent of Starting Mass (%)

100

80

60

40

20

0
0 100 200 300 400 500 600 700 800 900 1000
Temperature (C)

Figure 6. TGA of CNT array, synthesized and purified at UC. Starting mass of the CNT
is 3.371g

Measuring the carbonaceous purity is a much more difficult procedure. Most of the
qualitative and quantitative techniques have been based on spectroscopy. The ideal technique has
to distinguish between graphitic and amorphous carbon phases in the CNT. A very promising
approach for this is solution-phase near infrared (NIR) spectroscopy. In addition, Micro-Raman
spectroscopy can point defects in the graphitic structure of CNT along with presence of
amorphous carbon. In carbon-based materials, typically two main first order peaks are present.
One is the D peak, observed around 1300 cm-1 (for excitation with He-Ne laser) or at 1350 cm-1
when using an Ar ion laser. The D peak is related to the presence of defects. The other one is the
G peak at about 1580 cm-1, which is associated with the in-plane vibrations of the graphene sheet.
In addition to the G line, the appearance of a side peak at about 1540 cm-1 indicates the existence
of single-wall nanotubes with different diameters. Ratios of the D peak to the G peak have been
used as an indicator of the amount of disorder within nanotubes. A small ID/IG ratio, typically in
the range of 0.1- 0.2, indicates that the defect level in the atomic carbon structure is low, which
suggests reasonable crystalline quality.

6. Search the literature for new purification techniques that can decrease the loss of CNT
during the removal of the impurities.

Please perform an internet search using key words such as: CNT purification, CNT
plasma purification, CNT oxidation, will reveal new documents related to purification of carbon
nanotubes. Further refined search can narrow the number of the publications until the new
information is obtained.

38
7. List the characterization techniques used for determination of CNT diameter. Comment
on the limitations and advantages of each technique.

Carbon nanotubes are extremely small objects and their characterization requires
sophisticated instruments. Their dimensions can be easily revealed using Scanning Electron
Microscopes with high resolution such as Field Emission Environmental SEM, which does not
need preparation of the samples using conductive coating. Another advanced approach showing
the diameter of CNT is Atomic Force Microscopy (AFM), which provides the opportunity to
study features and properties that are not available with other techniques. High Resolution
Transmission Electron Microscopy (HRTEM) is the most powerful instrument that reveals the
diameters of the single wall and multiwall CNT, the number of walls, and the distance between
the walls. Figure 7 displays HRTEM of CNT synthesized at UC. The internal structure of the
nanotubes and their dimensions are clearly displayed.

(a) (b)
2 walls

20 walls

10 nm scale bar 5 nm scale bar

Figure 7. High Resolution TEM images of CNT synthesized at UC: (a) MWCNT with
15-20 nm outer diameter and 7 nm inner diameter; (b) Double wall CNT found with about 5 nm
diameter

Micro-Raman Spectroscopy is frequently employed to study the diameter of the carbon

nanotubes. The high-resolution spectrum obtained in the low-frequency domain shows several
components within the range of 100250 cm-1. Prominent low energy peaks around 191 and 216
cm-1 are the breathing modes of nanotubes vibrating along the radial direction, and can be clearly
revealed using a He-Ne laser. The spectrum in the low frequency domain reflects the SWCNT
diameters and can be used to evaluate it. In general, the frequency increases with decreasing tube
diameter (d). These bands are due to Ag symmetry mode. The frequency of these modes is
known to be inversely proportional to the diameter of the SWCNT. Based on the equation (cm-
1
) = 223.75/d (nm), the diameter of the SWCNT can be determined. The calculated (d) values
reflect a distribution in the diameters of the CNT.

8. Describe the characterization techniques for studying the morphology and the structure
of carbon nanotubes.

39
 Scanning Electron Microscopy (SEM) is a perfect technique to reveal the orientation of
the CNT and to distinguish between spaghetti type and aligned CNT arrays. In addition, it can
focus on fine features related to the CNT morphology as it is shown in Figure 8.

(a) (b)

Figure 8. Side view of a MWCNT array synthesized at UC at different SEM magnifications: (a)
low magnification at the bottom and high magnification at the top; (b) at high magnification. For
long array, CNT grow in strands with each strand having ~20 individual MWCNT or small
bundles that tend to wave or entangle each other.

Transmission Electron Microscopy (TEM) is widely used for morphological studies. Its power
is fully revealed when it comes to observation of the internal structure of the CNT, as shown in
Figure 7.

The resolution of the new generations Atomic Force Microscopes (AFM) is dramatically
improved lately. This allows observation of the overall morphology of CNT with unprecedented
details.

40
1.6 Solutions for Chapter 6
Self-Assembled Au Nanodots in a ZnO Matrix: A Novel Way to
Enhance Electrical and Optical Characteristics of ZnO Films by
Ashutosh Tiwari and Jagdish Narayan

1. Describe and discuss surface plasmon resonance.

At an interface between two transparent media of different refractive index (glass and water),
light coming from the side of higher refractive index is partly reflected and partly refracted.
Above a certain critical angle of incidence, no light is refracted across the interface, and total
internal reflection is observed. While incident light is totally reflected the electromagnetic field
component penetrates a short (tens of nanometers) distance into a medium of a lower refractive
index creating an exponentially detenuating evanescent wave. If the interface between the media
is coated with a thin layer of metal (gold), and light is monochromatic and p-polarized, the
intensity of the reflected light is reduced at a specific incident angle producing a sharp shadow
(called surface plasmon resonance) due to the resonance energy transfer between the evanescent
wave and surface plasmons. The resonance conditions are influenced by the material adsorbed
onto the thin metal film. A satisfactory linear relationship is found between resonance energy
and mass concentration of biochemically relevant molecules such as proteins, sugars and DNA.
The SPR signal which is expressed in resonance units is therefore a measure of mass
concentration at the sensor chip surface. This means that the analyte and ligand association and
dissociation can be observed and ultimately rate constants as well as equilibrium constants can
be calculated.

2. What are the values of band gap and exciton binding energies for ZnO? Compare these
numbers with corresponding values for GaN.

ZnO: Bandgap : 3.34eV (300K), Exciton binding energy: 60mev.

GaN: Bandgap: 3.39eV (300K), Exciton Binding energy: 25mev

41
1.7 Solutions for Chapter 7
Synthesis of Boron Nitride Nanotubes Using a Ball-Milling and
Annealing Method by Ying Chen and Jim S. Williams

1. What are the structural differences between C and BN nanotubes?

Although BN nanotubes have the same nanosized tubular structure as C nanotubes, there are two
main differences between their structures. (1) Different nanotube tips. A single-wall C nanotube
can be capped by a half-fullerene molecule (C60) consisting of 6-membered hexagons and 5-
membered pentagons, and thus multiwalled C nanotubes often have cone-shape tips, while many
BN nanotubes have flat tips, which are formed based on 4-membered squares instead of 5-
membered pentagons. (2) Different chiralities. The dominant BN nanotube structures are so-
called zig-zag tubes. The arm-chair and chiral tubes are less likely, possibly due to the special
tip configurations. On the other hand, C nanotubes with zig-zag, arm-chair and chiral structures
are all particularly abundant.

2. Why do BN nanotubes have flat tips instead of cone-shaped tips?

Theoretical investigation reveals that 5-membered pentagons in BN would require energetically

unfavorable B-B or N-N bonds that destabilize the structure. 4 membered squares have only B-
N bonds.

3. What are the different properties of BN nanotubes compared with C nanotubes?

BN nanotubes are stable insulating materials with a uniform electronic band gap of about 5.5 eV,
which does not depend on size and chirality of nanotubes as in the C nanotube case. BN
nanotubes have a much stronger resistance to oxidation at high temperatures than C nanotubes. C
nanotubes readily oxidize in air at a temperature above 400oC starting from the tips and defects
on the outer layers. They burn completely at 700oC when sufficient oxygen is supplied. BN
nanotubes normally start to oxidize in air above 800oC.

4. What is the role of the high-energy ball milling in the milling-annealing process?

The milling process has an essential role in nanotube formation during subsequent annealing,
which appears to be associated with the creation of suitable nucleation sites for nanotube growth.
The milling and annealing processes actually correspond to separate nucleation and growth
processes, respectively, i.e.:
Ball milling -> nucleation, and
Annealing -> growth.

42
5. Is HEBM the same as conventional ball milling?

The HEBM is fundamentally different from conventional ball milling. The impact energy of
HEBM is typically 1000 times higher than conventional ball milling energy. The particle
fracturing and size reduction in the conventional ball milling is only the first stage of HEBM. A
longer milling time is thus required for HEBM. In addition to the milling intensity, milling
atmosphere and temperature controls of HEBM are crucial to create a desired structural change
or chemical reaction.

6. What are the possible applications of BN nanotubes based on their special properties?

BN nanotubes are more thermally stable and chemically inert compared with CNTs, which lead
to many high temperature applications including energy storage, composite materials, radiation
protection and field emission. The stable electronic property makes it as ideal material in device
applications.

43
 PART 2

Manufacturing Using Nanoscale Materials

44
1.8 Solutions for Chapter 8
Plasma Deposition of Ultra-Thin Functional Films on Nanoscale
Materials by Peng He and Donglu Shi

1. Briefly explain what plasma polymerization processing is and what the important
parameters for this processing are.

Plasma polymerization is a procedure in which gaseous monomers, stimulated through a plasma

zone, condense on freely selectable substrates as highly cross-linked layers. The monomer
molecules in the plasma for the most part become excited into reactive particles, with only
partially preserved chemical structures of the output gases in the product. The monomer will
deposit to form branched and highly cross-linked structures. The most important parameters
include: pressure, working gas-flow, input power, monomer type, loading, and time.

2. Compared with other functionalization methods for carbon nanotubes, what are the
advantages of using plasma processing?

The advantages of using the plasma technique to functionalize CNT are the following: (a) A
wide range of precursor choices; (b) Highly adherent to a variety of substrates; (c) The process is
solvent free; (d) Thin films can be easily produced with thickness from several nanometers to
1m; (e) Through careful control of the polymerization parameters, it is possible to tailor the
films with specific chemical functionality, thickness, and other chemical and physical properties.

3. A company has some amorphous carbon substrates. In order to modify the surface,
plasma polymerization processing is suggested. In order to get better adhesion between the
coating and substrates, which condition will you will try to use for this processing: (a) high
power, low flow ratio, or (b) low power, high flow ratio? If the substrate is polystyrene,
which condition you will use for this case? (Assume that the monomer used here is styrene,
and that other processing parameters are the same.)

When the substrate is amorphous carbon, better adhesion can be obtained by applying high
power and a low flow ratio. The reason is that under this condition the deposited film has a
higher cross-link density and the C/H ratio will increase which will provide a similar chemical
structure like the amorphous carbon. The similar structure will provide better adhesion between
the substrate and coating. When the substrate is changed from amorphous carbon to PS, the
conditions will be totally opposite to the conditions used for the amorphous carbon case. It will
help to retain the styrene structure which is the critical issue for improvement of adhesion

4. A company wants to coat a glass substrate with poly-pyrrole to make the surface
ionically conductive. If the regular plasma polymerization processing is used, could we
achieve this objective? How could you modify the plasma processing to achieve the

45
objective?

During the plasma polymerization process, the chemical structure of the monomer or input gas
cannot be preserved. In other words, plasma poly-pyrrole will have a different chemical structure
compared with regular poly-pyrrole. But for the conductivity property, large bonding will be
the critical issue. The plasma poly-pyrrole will no longer contain large bonging for electron
movement. Thus it will lose the conductivity property. In order to solve this problem, usually
there are two ways: (1) a monomer doped with I2, or (2) using pulsed plasma polymerization
which will dramatically improve the conductivity.

5. What are the advantages and limitations of plasma polymerization processing?

The advantage of plasma polymerization was mentioned in problem 2. The limitation for plasma
polymerization is that during plasma processing, the chemical structure of the monomer will be
destroyed. Any property strongly related to the monomer chemical structure will disappear and
cannot be preserved.

6. List as many parameters as you can think of that control the plasma processing. Explain
what effect you think each parameter would have on the coating of nanoparticles. For
example, faster or more vigorous stirring of the nanoparticles may expose the particle to
the plasma longer and make the coating thicker and more uniform and prevent clumping
of particles.

There are several important parameters for plasma processing:

(a) pressure or gas flow ratio, Increasing this parameter will increase the monomer amount for a
large loading case.
(b) power, which can be used to control the dissociation ratio of the monomer.
(3) monomer type, which determines the chemical structure of final coating
(4) time, which determines the thickness of coating
(5) loading, which is an important parameter for thickness control also.

46
1.9 Solutions for Chapter 9
Structural Nanocomposites by Hassan Mahfuz

1. Explain different methods that are commonly used in mixing nanosized particles into
polymers.

There are three methods which are quite frequently used for mixing nanoparticles with
polymer. The methods are: a) Ultrasonic Mixing, b) Magnetic Stirring, and c) the Sol Gel
Method.
a) Ultrasonic Mixing: Acoustic cavitations are one of the efficient ways to disperse
nanoparticles into the virgin materials. In this case, the application of alternating acoustic
pressure above the cavitations threshold creates numerous cavities in the liquid. Some of
these cavities oscillate at a frequency of the applied field (usually 18 kHz) while the gas
content inside these cavities remain constant. However, some other cavities grow intensely
under tensile stresses while yet another portion of these cavities which are not completely
filled with gas, start to collapse under the compression stresses of the sound wave. In the
latter case, the collapsing cavity generates tiny particles of "debris" and the energy of the
collapsed one is transformed into pressure pulses. It is noteworthy that the formation of the
"debris" further facilitates the development of cavitation. It is assumed that acoustic
cavitations in liquids develop according to a chain reaction. Therefore, individual cavities on
real nuclei are developing so rapidly that within a few microseconds an active cavitations
region is created close to the source of the ultrasound probe. The development of cavitation
processes in the ultrasonically processed melt creates favorable conditions for the
intensification of various physio-chemical processes. Acoustic cavitations accelerate heat and
mass transfer processes such as diffusion, wetting, dissolution, dispersion and emulsification.

b) Magnetic Stirring: A magnetic stirrer consists of a small bar magnet (or stir bar), which is
normally wrapped in plastics and a stand or plate containing a rotating magnet or stationary
electromagnets creating a rotating magnetic field. Often, the plate can also be heated. During
operation of a typical magnetic stirrer, the bar magnet (flea) is placed in a vessel containing a
liquid to be stirred. The vessel is set on top of the stand, where the rapidly rotating magnetic
field causes the bar magnet to rotate. It uses a magnetic coupling between an outer magnet
assembly driven by a motor, and an inner magnet assembly separated by a drive tube. As the
outer magnet assembly rotates, the torque is magnetically transferred through the stationary
drive tube to the inner magnets attached to the drive shaft.

c) Sol Gel Method: Sol Gel processing involves generation of colloidal suspensions (Sols)
which are subsequently converted to viscous gels and then to solid materials. A sol is a
dispersion of colloidal particles suspended within a fluid matrix. Colloids are suspension of
particles of dimension between 1 nm to 1 micron. The formation of colloidal particles is best
understood by calculation of the sedimentation rates assuming that particles are spherical so
that Stokes law may be applied by equating gravitational and frictional factors. This
controlled method has many advantages, which led to its historical use before the underlying
scientific principles were understood. In recent years, the method has been employed to the
production of a wide variety of advanced materials including nanocomposites.

47
2. Discuss the effects of micron- and nanosized SiC fillers in an epoxy matrix on the
thermal properties of the nanocomposites.

Effects of micron and nanosized particles on the thermal properties of epoxy or any other
polymer matrices are quite evident. The main effect comes from particle dimension. If the
particle size is small, more number of atoms will be at the surface of the particle. This means
that if the particle can be dispersed properly in the matrix, the interaction between the particle
and the polymer will be much more intense. In addition, it can also be shown that if the
diameter of the particle decreases, the specific surface area of the particle increases in the
reverse order. For example, the specific surface area (m2/g) for a 10 nm dia particle is 1000
times larger than that of a 10 micron diameter particle. This enormous increase in surface
area gives rise to a huge interphase zones (IZ) between the particle and the polymer. At these
interphase zones, polymer chain structures, chemistry and kinetics are different. In other
words, IZ introduces a perturbed layer in which the polymer has properties different than the
bulk. Since IZ is very large, the bulk of the polymer will be just next to an IZ. That means,
the bulk of the polymer will now behave differently under any thermal or mechanical load.
Presence of nanosize particles within the polymer will also play another role in controlling
the molecular mobility of the chain in the free space. This affects the glass transition
temperature directly. We do not expect these interactions with micron size particles.

3. Discuss the effects of micron- and nanosized SiC fillers in an epoxy matrix on the
mechanical properties of the nanocomposites.

The effect of nanoparticle inclusion on mechanical properties can be explained from the
micromechanical theories that a certain average perturbed strain is introduced into the matrix
due to the presence of inclusions, and that the perturbed strain correspond to an average
perturbed stress. This concept equally applies to micron size particles. What is different with
the nanosize particle is that the nanoscale interaction induces a morphological change in the
polymer which directly affects the mechanical properties. For example, if the degree of cure
is faster at the initial stage of cure, it might induce partial crystallinity in the polymer which
will directly translate into changes in mechanical properties. In addition, if the nanosize
particles can be dispersed uniformly, they will sit comfortably within the polymer chain as
those dimensions are all in the nanometer range. In other words, embedded nanoparticles
wrapped around by polymer chains would serve as a tethering or an anchoring mechanism
during the application of an external load, especially in the uncoiling phase. Due to nanoscale
interaction, the bonding strength between particle and the polymer is expected to be higher
than one would expect with micron size particles. Enhancing bonding strength will have a
direct influence on the strength of the nanocomposite.

4. Discuss the advantages and disadvantages of nanosized SiC fillers on the fatigue
performance of polymeric composites.

48
Fatigue performance in a composite is usually controlled by the formation of crack, and its
subsequent propagation. In nanocomposites, because of the morphological changes in the
polymer, the polymer becomes stronger and as such the initiation of damage or a crack is
usually delayed. Once the crack is initiated, the presence of a large interface would act as
energy absorbing mechanism during the cyclic loading. Particles may also serve as a pinning
mechanism to arrest the advancing crack, leading to a better fatigue performance. The
disadvantage of nanoparticle inclusion is that if a laminated composite is made it will have
reduced interlaminar strength and delamination fracture toughness properties. This is true
with regular laminated or sandwich composites. These properties become important
especially during the later part of the fatigue life.

49
1.10 Solutions for Chapter 10
Synthesis and Characterization of Metal-Ceramic Thin-Film
Nanocomposites with Improved Mechanical Properties by
Dhananjay Kumar, Jagannathan Sankar, and Jagdish Narayan
(Solutions by Vesselin N. Shanov)

1. Describe the role of the pulsed laser deposition method in the fabrication of thin-film
nanocomposite materials.

The conventional approach in the fabrication of the thin-film nanocomposite materials is based
on multistep processing and includes techniques such as sol-gel, thermal evaporation, sputtering,
molecular beam epitaxy, ion implantation, etc. A sequential post- treatment is also required to
form the final composition and structure. Pulsed Laser Deposition (PLD) offers many advantages
in preparing multi-component composite films. A multiple target PLD permits independent
control of synthesis of nanocrystals and the embedding matrix. In addition, this technique allows
stoichiometric thin-film deposition of complex compounds. The laser ablation of the targets
causes a plume generation that evaporates energetic ions, which participate in formation of dense
and well-adhered films with good adhesion and superior mechanical properties. PLD is an
excellent approach for fabrication of composite coatings consisting of metallic nanocrystals
embedded in an insulator host.

2. Discuss the mechanism for the improvement in ceramic thin films by the addition of
nanodimensional metal particles.

Scanning Transmission Electron Microscopy (STEM) studies show that the metal nanoparticles
(Ni) are crystalline and the ceramic (alumina) matrix is amorphous. The amorphous phase of the
matrix provides high structural flexibility in order to accommodate the coherency strain without
forming dangling bonds and voids, which stabilizes the nanostructure and reduces the grain
boundary sliding. According to the Koehler concept of multilayers, under applied stress, a
dislocation that that would form in a soft metal layer will move to the metal-ceramic interface.
The elastic strain in the second ceramic layer with the higher elastic modulus will cause a
repulsive force that will prevent the dislocation from crossing that interface. The metal-ceramic
nanocompsite films are considered multilayered structures. A closer look reveals that they
consist of a continuous ceramic layer and a discontinuous metal film, and such a structure is
stronger than expected from the rule of mixtures. The improvement in hardness and Youngs
modulus of such nanocomposites is related to the evolution of the microstructure that efficiently
manages the dislocation and microcrack propagation due to grain boundary hardening.

3. Explain how the mechanical properties of hard materials such as alumina can be
improved by the addition of soft materials such as nickel or iron.

50
The experimental data obtained from Ni-Al2O3 and Fe-Al2O3 thin film composites prepared by
PLD reveal that the hardness of pure alumina is less than the hardness of the nanocomposite and
it can be manipulated by the metal particle size and concentration. This effect is related to
embedding of metal nanocrystals that promote the evolution of a microstructure, which
suppresses the dislocation motion and microcrack growth. The restriction in grain boundary
movement comes from the grain boundary hardening due to formation a layered two-phase
structure consisted of soft metal nanoclusters imbedded in an amorphous ceramic matrix.

51
1.11 Solutions for Chapter 11
Macroscopic Fibers of Single-Walled Carbon Nanotubes by Virginia
A. Davis and Matteo Pasquali

1. Describe a potential application for nanotube fibers. What properties would be

required? What kind of nanotubes would you use? Which of the fiber production methods
described in this section would you use? (At this stage, assume that cost is not an issue.)

There are numerous potential answers to this question; the answers to the various parts of the
question should be self-consistent. For example, one potential application is electrical wire for
conducting electricity long distances from a supply source such as a large solar array in a remote
area to the cities where it is needed. In this case, the best type of nanotubes would be those that
provide the most efficient electrical conduction, namely armchair metallic SWNTs all with the
same diameter. Using a mixture of metallic and semiconducting nanotubes would reduce the
electrical conductivity and using nanotubes of different diameter would reduce packing
efficiency creating voids and defects in the wire. One possible production method is continuous
growth of a specific nanotube followed by solution spinning or the continuous winding of the
SWNTs into a large fiber.

2. How does the polydispersity in chirality, length, and diameter of SWNTs affect the
different fiber spinning processes? How does this polydispersity affect fiber properties?

For solution spinning as well as the other processes polydispersity in chirality and diameter
results in reduced packing efficiency. This can be visualized in a 2D case by pushing coins or a
table together to try to pack them into a regular array. If the coins are all dimes (or all another
type) they will close pack. However, if the coins are randomly placed nickels, dimes and quarters
a regular array can not be achieved. Diameter polydispersity (which also implies chirality
polydispersity) therefore results in defects in voids in the fiber and a reduction in properties.
Chirality polydispersity also can have a marked impact on properties, particularly electrical
properties; a mixture of semiconducting and metallic nanotubes in a single fiber is rarely
desirable. Length polydispersity can also affect packing. Length polydispersity implies
polydispersity in the length to diameter ratio which has a marked impact on liquid crystalline
phase transitions as well as the rheological behavior of spinning solutions or melts.

3. What are the biggest challenges in producing nanotube polymer composite fibers? How
do these differ from the challenges in producing neat SWNT fibers?

For both composite and pure SWNT fibers materials availability is an issue as of the date of
publication, but this is being overcome. The two main challenges for SWNT composite fibers are
first dispersing the SWNTs in the polymer and then avoiding phase separation of the SWNT
from the polymer during all subsequent steps of production and use. For neat SWNT fibers,
initial SWNT dispersion is also a critical issue, but in subsequent steps the goal is controlled

52
removal of the solute from the dispersion.

53
1.12 Solutions for Chapter 12
Carbon Nanofiber and Carbon Nanotube/Polymer Composite
Fibers and Films by Han Gi Chae, Tetsuya Uchida, and Satish
Kumar (Solutions by Han Gi Chae, BeomJin Yoon, Rahul Jain,
Tetsuya Uchida, Satish Kumar)

1. List the densities, tensile strength, and modulus values for the following: (a) Diamond,
(b) graphite, (c) Carbon fiber, (d) Vapor grown carbon nanofiber (VGCNF), (e)
MWNT, (f) DWNT, (g) SWNT. Provide reference for each value you quote.

The properties for various carbon materials are tabulated in the following Table.

Density Tensile Tensile

(g/cm3) Strength (GPa) Modulus (GPa)
3.52 > 90 > 900
Diamond1-4
2.26 21 ~ 1000
Graphite4-6
1.7 ~ 2.2 4~7 150 ~ 950
Carbon Fiber7
1.9 ~ 2.1 3 ~ 20 50 ~ 775
VGCNF8~11
1.8 ~ 2.0 11 ~ 63 1060
MWNT12~15
1.5 23 ~ 63 ~ 1000
DWNT15~17

SWNT15, 18~19 1.3 37 640

1. Mykolajewycz, R.; Kalnajs, J.; Smakula, A. J. Appl. Phys. 1964, 35, 1773.
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and Applications. Noyes Publications 1993; p. 51, 62, 250, 272.
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6. Deborah D. L. Chung, Carbon Fiber Composites, 1994, Butterworth-Heinemann.
7. Minus, M.L., Kumar, S. JOM 2005, 57, 52.
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11. Uchida T, Anderson DP, Minus ML, Kumar S. Morphology and modulus of vapor grown

54
 carbon nano fibers. Journal of Materials Science 2006, 41, 5851.
12. Yu, M.F.; Lourie, O.; Dyer, M.J.; Moloni, K.; Kelly, T.F.; Ruoff, R.S. Science 2000, 287,
637.
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of Various Types of Carbon Nanotubes in Polyacrylonitrile Fiber. Polymer 2005;46:10925-
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17. http://www.tmcnanotech.com/tmcnanotech/dwnt.html
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19. Dresselhaus, M. S.; Dresselhaus, G; Avouris,Ph.Carbon nanotubes- synthesis properties, and
applications, 2000, Springer

2. The following SWNTs were reported in a recent HipCO batch (Nano Letters, Vol. 5, No.
1, P. 163~168, 2005, see Fig. 5): (8,3), (6,5), (7,5),(10,2), (9,4), (8,4), (7,6), (12,1), (8,6), (11,3),
(10,5), (10,3), (9,5), (8,7), (11,1)
(a) Calculate the diameter and chiral angle of each tube.
The diameter of SWNT can be calculated by following equation:
3
d= (acc )n 2 + nm + m 2 .

where, d: diameter of SWNT; ac-c: carbon-carbon bond length (0.1421 nm); and n & m: index of
SWNT (from (n,m)).
The chiral angle () of SWNT is given by following equation:
3m
= tan 1 ( ).
m + 2n
The results based on the above equations are given in Table 1.

(b) Classify these tubes as (i) arm-chair, (ii) zig-zag, or chiral.

For (n,m) SWNTs, arm-chair is the case if n=m, zig-zag type is the case if m=0, and the others
are chiral. In the given data, there are no arm-chair or zig-zag tubes: all of them are chiral
nanotubes.

(c) Which of these tubes are metallic?

If n-m is an integer multiple of 3, it is a metallic SWNT. However, the given SWNTs dont
satisfy the condition. Consequently, all of them are semi-conducting CNTs.

Table 1. SWNT Diameter, Chiral Angle (), Tube Chirality, and Conducting Behavior.
n m n-m Diameter Chirality Conducting
(nm) () Behavior

55
 8 3 5 0.77 15.3 chiral semiconducting
6 5 1 0.75 27.0 chiral semiconducting
7 5 2 0.82 24.5 chiral semiconducting
10 2 8 0.87 8.9 chiral semiconducting
9 4 5 0.90 17.5 chiral semiconducting
8 4 4 0.83 19.1 chiral semiconducting
7 6 1 0.88 27.5 chiral semiconducting
12 1 11 0.98 4.0 chiral semiconducting
8 6 2 0.95 25.3 chiral semiconducting
11 3 8 1.00 11.7 chiral semiconducting
10 5 5 1.04 19.1 chiral semiconducting
10 3 7 0.92 12.7 chiral semiconducting
9 5 4 0.96 20.6 chiral semiconducting
8 7 1 1.02 27.8 chiral semiconducting
11 1 10 0.90 4.3 chiral semiconducting

3. What is the typical spacing between planes in a MWNT?

The interlayer spacing of MWNTs is ~0.34 nm, and this value is larger than single crystal
graphite, 0.335 nm 1. Actually, the interlayer spacing of MWNTs varies in the range of 0.34 ~
0.39 nm2,3.
1. Saito, Y; Yoshikawa, T.; Bandow, S.; Tomita, M.; Hayashi, T. Phys. Rev. B 1993, 48, 1907.
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M.S. J. Phys. Chem. Solids 1997, 58, 1707.
3. Kiang, C.H.; Endo, M.; Ajayan, P.M.; Dresselhaus, G.; Dresselhaus, M.S. Phys. Rev. Lett.
1998, 81, 1869.

4. What is molecular weight of a SWNT of 1 nm diameter and 10 m length?

The total number of C-atoms comprised in a nanotube can be calculated from a periodic cell,
which if repeated will generate the whole C-nanotube structure. Such a unit cell is shown in
Figure 1, which contains a particular number of C-atoms in a particular area (8 C-atoms in
3x1.42x2x2.46 2 area).

56
 2 C atoms for 3ac-c

3 x 1.42
8 C atoms

2ac-c
2 x 2.46
a2
ac-c = 1.42 a1

a1 = a2 = a = 3aC C = 2.46
Figure 1. A representation of C-nanotube surface showing bond length, various length vectors,
and a representative unit cell.

For a nanotube with 1 nm diameter and 10 m length, the total surface area can be calculated as
shown in equation 3.
o
S A = d t h = 1 nm 10 m = 3141600 A 2 (3)

Therefore, the total number of C-atoms can be calculated as shown in equation 4.

o
8
total # C atoms = 3141600 A 2 o
1199130 (4)
3 1.42 2 2.46 A 2

Hence, the molecular weight (MW) of the given tube can be calculated as shown in equation 5.
MW = 1199130 12.011 14402747 g.mol 1 1.44 10 7 g.mol 1 (5)

5. What evidence exists in the literature prior to 1991, which suggested the existence of the
carbon nanotube?

Please see references below.

1. Monthioux M, Kuznetsov VL. Who should be given the credit for the discovery of carbon
nanotubes? Carbon 2006, 44, 1621-3
2. Boehm HP. The first observation of carbon nanotubes. Carbon 1997;35:5814.
3. Iijima S, Ichihashi T. Single-shell carbon nanotubes of 1-nm diameter. Nature 1993;363:603
5.
4. Bethune DS, Kiang CH, De Vries MS, Gorman G, Savoy R, Vazquez J, et al. Cobalt
catalysed growth of carbon nanotubes with singleatomic-layer walls. Nature 1993;363:6057.
5. Oberlin A, Endo M, Koyama T. Filamentous growth of carbon through benzene
decomposition. J Cryst Growth 1976;32:33549.

57
6. Tersoff J, Ruoff RS. Structural properties of a carbon-nanotube crystal. Phys Rev Lett
1994;73:6769.
7. Iijima S. Helical microtubules of graphite carbon. Nature 1991;354:568.
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1957;2:131.
9. Hughes TV, Chambers CR. US Patent 405480;1889.
10. Schutzenberger P, Schutzenberger L. Sur quelques faits relatifs a`lhistoire du carbone. C R
Acad Sci Paris 1890;111:7748.
11. Pelabon C, Pelabon H. Sur une variete de carbone filamenteux. C R Acad Sci Paris
1903;137:7068.
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nanotubes from vapor-grown carbon fibers. Carbon 1995;33:87381.
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razlozenii okisi ugleroda na zeleznomkontakte. Zurn Fisic Chim 1952;26:8895.
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15. Boehm HP. Carbon from carbon monoxide disproportionation on nickel and iron catalysts:
morphological studies and possible growth mechanisms. Carbon 1973;11:58390.
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cobalt and chromium catalyzed decomposition of acetylene. J Catal 1973;30:8695.
17. Baker R.T.K. et. al. Nucelation and growth of carbon deposits from the nickel catalyzed
decomposition of acetylene J. Catal. 1972, 26, 51.
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211.
19. Nielsen J.P. et. al. Mechanism of carbon formation on nickel-containg catalysts J. Catal.
1977, 48, 155.
20. Tibbetts G.G. Why are carbon filaments tubular J. Cryst. Growth, 1984, 66, 632.
21. Alstrup I. J. A new model explaing carbon filament growth on nickel, iron and Ni-Cu alloy
catalysts Catal., 1988, 108, 241.
22. Baker R.T.K. Catalytic growth of carbon filaments Carbon, 1989, 27, 315.
23. Bianchini E.C et. al. Kinetic implications of mechanisms proposed for catalytic carbon
filament growth, J. Catal., 1989, 117, 455.
24. Sacco A. et. al. Carbon deposition and filament growth on Fe, Co, and Ni foils using CH4-
H2-H2O-CO-CO2 gas mixture, J. Catal., 1989, 119, 322.
25. Lobo L.S. et. al. Kinetics of catalytic carbon formation on steel surfaces from light
hydrocarbons Catal. Today, 1990, 7, 247.
26. Safvi et. al. The dependence of catalytic carbon filament growth kinetics upon gas phase
carbon activity Carbon, 1991, 29, 1245.
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Carbon 1974;12:111-41.
29. Wiles PG, Abrahamson J. Carbon Fibre Layers on Arc Electrodes-I: Their Properties and
Cool-Down Behaviour. Carbon 1978;16:341-9.
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Anodes. 14th Biennial Conference on Carbon June 25-29, 1979; Penn. State Univ.,
University Park, Penn., USA. 254-5. (republished in Carbon 1999;37(11): 1873-4.

58
6. How does the process for producing vapor grown carbon fibers differ from the process
of making MWNTs using hydrocarbon gas and a catalyst? In other words, why one process
can yield 100 nm diameter fiber with graphite planes oriented at a certain angle (typically
15 degrees) to the nano fiber axis, while the other process can result in 10 nm diameter tube,
where graphite planes are axially aligned.

Please see references below.

1. Teo KBK, Singh C, Chhowalla M, Milne WI. Catalytic Synthesis of Carbon Nanotubes and
Nanofibers. In: Encyclopedia of Nanoscience and Nanotechnology (ed. by H.S. Nalwa)
2003; X:1-22.
2. Laurent, C.; Flahaut, E; Peigney, A.; Rousset, A New J. Chem. 1998, 1229
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1998, 73, 3845
4. Tibbetts GG. Why are Carbon Filaments Tubular? Journal of Crystal Growth 1984, 66(3),
632-8
5. Tibbetts GG. Lengths of Carbon Fibers Grown From Iron Catalyst Particles in Natural Gas.
Journal of Crystal Growth 1985, 73(3), 431-8
6. Baker, R.T.K.; Harris, P.S. The formation of filamentous carbon in Chemistry and physics
of carbon, 1978, 14, 84

7. In the gas phase process, what factors dictate the formation of SWNTs and DWNTs. In
other words, if in one batch you only want to produce SWNTs and in another batch only
DWNTs, which factors/parameter you will control/change, and why?

Please see references below.

1. Sugai T, Yoshida H, Shimada T, Okazaki T, Shinohara H. New Synthesis of High-Quality
Double-Walled Carbon Nanotubes by High-Temperature Pulsed Arc Discharge. Nano Letters
2003;3(6):769-73.
2. Saito Y, Nakahira T, Uemura S. Growth Conditions of Double-Walled Carbon Nanotubes in
Arc Discharge. Journal of Physical Chemistry B 2003;107:931-4.
3. Cumings J, Mickelson W, Zettl A. Simplified Synthesis of Double-Wall Carbon Nanotubes.
Solid State Communications 2003;126:359-62.
4. Lyu, S. C.; Liu, B. C.; Lee, S. H.; Park, C. Y.; Kang, H. K.; Yang, C. W.; Lee, C. J. Large-
Scale Synthesis of High-Quality Double-Walled Carbon Nanotubes by Catalytic
Decomposition of n-Hexane. J. Phys. Chem. B, 2004, 108, 2192.
5. Lyu, S. C.; Liu B. C.; Kang, H. K.; Yang, C. W., Park, C. Y.; Lee, C. J. High-Quality
Double-Walled Carbon Nanotubes Produced by Catalytic Decomposition of Benzene. Chem.
Mater., 2003, 15, 3951.
6. Liu, B. C.; Lyu, S. C.; Lee, T. J.; Choi, S. K.; Eum, S. J.; Yang, C. W.; Park, C. Y.; Lee, C. J.
Synthesis of Single- and Double-Walled Carbon Nanotubes by Catalytic Decomposition of
Methane. Chem. Phys. Lett., 2003, 373, 475.
7. Xie, S.; Song, Li; Ci, L.; Zhou, Z.; Dou, X.; Zhou, W.; Wang, G.; Sun, L. Controllable
Preparation and Properties of Single-/Double-Walled Carbon Nanotubes. Sci. Tech. Adv.
Mater., 2005, 6, 725.

59
8. Describe the nucleation and growth process for SWNT synthesis in the gas phase or
HiPCO process.

Please see references below.

1. Nikolaev P, Bronikowski MJ, Bradley RK, Rohmund F, Colbert DT, Smith KA, Smalley RE.
Gas-Phase Catalytic Growth of Single-Walled Carbon Nanotubes from Carbon Monoxide.
Chemical Physics Letters 1999;313:91-7.
2. Bronikowski M, Willis PA, Colbert DT, Smith KA, Smalley RE. Gas-phase production of
carbon single-walled nanotubes from carbon monoxide via the HiPco process: A parametric
study. Journal of Vacuum Science and Technology 2001;19(4):1800-5.
3. Dai H, Rinzler AG, Nikolaev P, Thess A, Colbert DT, Smalley RE. Single-Wall Nanotubes
Produced by Metal-Catalyzed Disproportionation of Carbon Monoxide. Chemical Physics
Letters 1996;260:471-5.
4. Scott CD, Smalley RE. Effects of Carbonyl Bond, Metal Cluster Dissociation, and
Evaporation Rates on Predictions of Nanotube Production in High-Pressure Carbon
Monoxide. Journal of Nanoscience and Nanotechnology 2003;3(1/2):75-9.
5. Smalley et al. Gas Phase Nucleation and Growth of Single-Wall Carbon Nanotubes from
High Pressure CO. US Patent 6761870 B1 July 2004.

9. Before Ziegler-Natta catalysts only atactic polypropylene could be synthesized, which

was not very useful. Ziegler-Natta catalysts led to isotactic polypropylene, resulting in its
rapid commercialization. Are we, now likely to come up with a catalyst that can produce
SWNT of a specific type (e.g. zig-zag, arm-chair, or chiral). If so, which approach(es) is/are
likely to succeed? Why?

This is an open ended question with no definite answer as of 2006.

10. Come up with a nanotube (SWNT, DWNT, or MWNT) reactor design to produce
continuous tubes, rather than the short length typically 1 to 100 m tubes currently
produced.

This is an open ended question with no definite answer as of 2006.

11. Come up with a method to produce 100% pure undamaged un-functionalized SWNT,
DWNT, or MWNT. The ultimate product should contain no catalyst, no carbonaceous or
other impurity, and no tube functionalization.

Please see references below.

1. Jung SH, Kim MR, Jeong SH, Lee OJ, Lee KH, Suh JH, Park CK. High-Yield Synthesis of
Multi-Walled Carbon Nanotubes by Arc Discharge in Liquid Nitrogen. Applied Physics A
2003;76:285-6.

60
2. Olk CH. Method for Making Carbon Nanotubes. US Patent 5753088 1998.
3. Zhao X, Ohkohchi M, Wang M, Iijima S, Ichihashi T, Ando Y. Preparation of High-Grade
Carbon Nanotubes by Hydrogen Arc Discharge. Carbon 1997; 35(6):775-81.
4. Merchan WM, Saveliev A, Kennedy LA, Fridman A. Formation of Carbon Nanotubes in
Counter-Flow, Oxy-Methane Diffusion Flames without Catalysts. Chemical Physics Letters
2002;354:20-4.
5. Singh, Charanjeet et. al., Carbon 2003, 41, P. 359.
6. Zhu, Lingbo et. al., Nano Lett. 2005, 5, P. 2641.

12. Stress coefficient of the Raman G and G bands for the nanotubes were reported to be
8.7 cm-1/GPa and 23 cm-1/GPa, respectively. How are these stress coefficients
determined? How valid are these numbers?

The position of G and G band in a Raman spectrum depend on factors such as, stress [1-14],
temperature [15-16], charge etc. Please see references [1-16] below.
1. Zhao Q, Frogley MD, Wagner HD. Direction-Sensitive Strain-Mapping with Carbon
Nanotube Sensors. Composites Science and Technology 2002; 62:147-50.
2. Frogley MD, Ravich D, Wagner HD. Mechanical Properties of Carbon Nanoparticle-
Reinforced Elastomers. Composites Science and Technology 2003; 63:1647-54.
3. Cooper CA, Young RJ. Investigation of Structure/Property Relationships in Particulate
Composites Through the Use of Raman Spectroscopy. Journal of Raman Spectroscopy
1999;30:929-38.
4. Cooper CA, Young RJ, Halsall M. Investigation into the Deformation of Carbon Nanotubes
and Their Composites Through the Use of Raman Spectroscopy. Composites: Part A
2001;32:401-11.
5. Venkateswaran UD, Rao AM, Richter E, Menon M, Rinzler A, Smalley RE, Eklund PC.
Probing the Single-Wall Carbon Nanotube Bundle: Raman Scattering Under High Pressure.
Physical Review B 1999;59(16):10928-34.
6. Lourie O, Wagner HD. Evaluation of Youngs Modulus of Carbon Nanotubes by Micro-
Raman Spectroscopy. Journal of Materials Research 1998;13(9):2418-22.
7. Loa I. Raman Spectroscopy on Carbon Nanotubes at High Pressure. Journal of Raman
Spectroscopy 2003;34:611-27.
8. Venkateswaran UD, Gosselin ME, Postek B, Masica DL, Chen G, Gupta R, Eklund PC.
Radial and Tangential Vibrational Modes of HiPCO-Derived Carbon Nanotubes under
Pressure. Physica Status Solidi (b) 2003:235(2):364-8.
9. Peters, M.J.; McNeil, L.E. ; Lu, J.P. ; Kahn, D. Phys. Rev. B 2000, 61, 5939
10. Venkateswaran, U.D.; Brandsen, E.A.; Schlecht, U.; Rao, A.M.; Richter, E.; Loa, I.; Syassen,
K.; Eklund, P.C.; Phys. Stat. Sol. B 2001, 223, 225
11. Thomsen, C.; Reich, S; Jantoljak, H.; Loa, I.; Syassen, K.; Burghard, M.; Duesberg, G.S.;
Roth, S.; Appl. Phys. A 1999; 69, 309
12. Rols, S.; Goncharenko, I.N.; Almairac, R.; Sauvajol, J.L.; Mirebeau, I.; Phys. Rev. B 2004,
64, 153401
13. Venkateswaran, U.D.; Brandsen, E.A.; Katakowski, M.E.; Harutyunyan, A.; Chen, G.; Loper,
A.L.; Eklund, P.C.; Phys Rev B 2002, 65, 054102

61
14. Zhang X, Liu T, Sreekumar TV, Kumar S, Moore VC, Hauge RH, Smalley RE. Poly(vinyl
alcohol)/SWNT Composite Film. Nano Letters 2003, 3, 1285-1288.
15. Li HD, Yue KT, Lian ZL, Zhan Y, Zhou LX, Zhang SL, Shi SJ, Gu ZN, Liu BB, Yang RS,
Yang HB, Zou GT, Zhang Y, Iijima S. Temperature Dependence of The Raman Spectra of
Single-Wall Carbon Nanotubes. Applied Physics Letters 2000;76(15):2053-6
16. Raravikar NR, Keblinski P, Rao AM, Dresselhaus MS, Schadler LS, Ajayan PM.
Temperature Dependence of Radial Breathing Mode Raman Frequency of Single-Walled
Carbon Nanotubes. Physical Review B 2002;66:235424 1-9.

13. (a) In a polymer-A /nanotube composite, when macroscopic stress was 100 MPa, the
Raman G band shifted by 20 cm-1. Assuming that the stress coefficient in Question #
(12) is correct, what was the stress on the nanotube? Why does macroscopic stress
differ from the Raman calculated stress on the nanotube? (b) In a polymer-B/nanotube
composite, when the macroscopic stress was 100 MPa, there was no shift in the Raman
G band. Qualitatively compare the polymer/nanotube interfacial strength in the two
cases (polymer-A/nanotube vs polymer-B/nanotube). Can the G Raman shift be used to
quantify the interfacial strength of the polymer/nanotube composite? If so, how?

(a) Assuming the G-band stress coefficient of 23 cm-1/GPa is correct; Macroscopic Stress =
100 MPa. The Raman calculated stress on nanotube from G-band shift = 20/23 = 870
MPa. The fact that there is higher stress on the nanotube than on the bulk sample,
suggests that the stress is not homogenous through the sample.
(b) There is no load transfer to the nanotube in sample B. This suggests that interfacial
strength in sample B is negligible or very low, while sample A exhibits good interfacial
strength. Measurement of interfacial strength: One should be able to conduct the
equivalent of a single filament pullout test using AFM in conjunction with Raman
spectroscopy to determine the interfacial strength.

References:
1. Ajayan, P. M.; Schadler, L.S.; Giannaris, C.; Rubio, A. Adv Mater 2000, 12, 750
2. Wood, J.R.; Zhao, Q.; Wagner, H.D. Composites A 2001, 32, 391
3. Zhang X, Liu T, Sreekumar TV, Kumar S, Moore VC, Hauge RH, Smalley RE. Poly(vinyl
alcohol)/SWNT Composite Film. Nano Letters 2003, 3, 1285-1288.

14. Why is fluorescence not observed in metallic tubes? (Science, vol. 298, pp.2361-2366,
2002; Science, vol. 297, pp. 593-596, 2002)

Please see references below.

1. http://hyperphysics.phy-astr.gsu.edu/hbase/solids/band.html#c5
2. http://micro.magnet.fsu.edu/primer/lightandcolor/fluorointroduction.html
3. OConnell MJ, Bachilo SM, Huffman CB, Moore VC, Strano MS, Haroz EH, Rialon KL,
Boul PJ, Noon WH, Kittrell C, Ma J, Hauge RH, Weisman RB, Smalley RE. Band Gap
Fluorescence from Individual Single-Walled Carbon Nanotubes. Science 2002;297:593-6.

62
4. Bachilo SM, Strano MS, Kittrell C, Ma J, Hauge RH, Smalley RE, Weisman RB. Structure-
Assigned Optical Spectra of Single-Walled Carbon Nanotubes. Science
2002;298(5602):2361-6.
5. Hertel T, Moos G. Electron-Phonon Interaction in Single-Wall Carbon Nanotubes: A Time-
Domain Study. Physical Review Letters 2000;84(21):5002-5.
6. Lauret JS, Voisin C, Cassabois G, Delalande C, Roussignol P, Jost O, Capes L. Ultrafast
Carrier Dynamics in Single-Wall Carbon Nanotubes. Physical Review Letters 2003;90(5):
057404 1-4.
7. Reich S, Thomsen C, Maultzsch J. Carbon Nanotubes: Basic Concepts and Physical
Properties. Wiley-VCH, Weinheim 2004:80-3
8. Huang L, Pedrosa HN, Krauss TD. Ultrafast Ground-State Recovery of Single-Walled
Carbon Nanotubes. Physical Review Letters 2004;93:017403 1-4.

15. Why is NaDDBS (SDBS) a much better surfactant than SDS for nanotubes? (Nano
letters, vol. 3, pp. 1379-1382, 2003)

Please see references below.

1. Moore VC, Strano MS, Haroz EH, Hauge RH, Smalley RE. Individually Suspended Single-
Walled Carbon Nanotubes in Various Surfactants. Nano Letters 2003;3(10):1379-82.
2. Islam MF, Rojas E, Bergey DM, Johnson AT, Yodh AG. High Weight Fraction Surfactant
Solubilization of Single-Wall Carbon Nanotubes in Water. Nano Letters 2003;3(2):269-73.

16. The SWNT optical spectra generally report E11, E22, and M11. Why is M22 not reported
or observed?

The M22 (E >3.53 eV, <351 nm) van Hove transition is out of the range of the optical spectra.

Please see references below.

1. OConnell MJ, Bachilo SM, Huffman CB, Moore VC, Strano MS, Haroz EH, Rialon KL,
Boul PJ, Noon WH, Kittrell C, Ma J, Hauge RH, Weisman RB, Smalley RE. Band Gap
Fluorescence from Individual Single-Walled Carbon Nanotubes. Science 2002;297:593-6.
2. Bachilo SM, Strano MS, Kittrell C, Ma J, Hauge RH, Smalley RE, Weisman RB. Structure-
Assigned Optical Spectra of Single-Walled Carbon Nanotubes. Science
2002;298(5602):2361-6.
3. Itkis, M.E.; Niyogi, S.; Meng, M.E.; Hamon, M.A.; Hu, H.; Haddon, R.C. Nano Lett 2002, 2,
155
4. Streetman, B.G.; Banerjee S. Solid state electronic devices, Prentice Hall 2000
5. Dresselhaus, M.S.; Dresselhaus, A.; Jorio A.; Filho A.G.S.; Saito R. Carbon 2002, 40, 2043

17. A number of ionic compounds (both organic and inorganic) have been used to
dissolve/disperse nanotubes. How do these ionic compounds assist in
dissolving/dispersing nanotubes?

63
Please see reference below.
1. Penicaud, A.; Poulin P.; Derre, A.; Anglaret, E.; Petit .P, J Am Chem Soc 2005, 127, 8
2. Bo Yu, Feng Zhou, Gang Liu, Yongmin Liang, Wilhelm T. S. Huck and Weimin Liu. The
Electrolyte Switchable Solubility of Multi-Walled Carbon Nanotube/Ionic Liquid
(MWCNT/IL) Hybrids. Chem. Commun. 2006, 2356

18. Why are dichlorobenzene, chloroform, and dimethyl formamide good solvents for
nanotubes? Suggest a solvent, with an appropriate explanation, for dispersing
nanotubes in the following polymers: nylon 6, nylon 66, PET, and polystyrene.

Please see references below. Second part of the question is open ended.
1. Lee, G.-W.; Kumar, S.K. J Phys Chem B 2005, 109, 17128
2. Liu J, Liu T, Kumar S. Effect of Solvent Solubility Parameter on SWNT Dispersion in
PMMA. Polymer 2005;46:3419-24.
3. Brandrup J, Immergut EH, Grulke EA, Abe A, Bloch DR. Solution Properties (In: Polymer
Handbook, 4th Edition, John Wiley & Sons) 2005:688-714
4. Weisman RB. Fluorescence Spectroscopy of Single-Walled Carbon Nanotubes (In: Applied
Physics of Carbon Nanotubes: Fundamentals of Theory, Optics and Transport Devices, Ed.
by Rotkin SV, Subramoney S). Springer-Verlag, Berlin Heidelberg 2005:183-202
5. Bahr JL, Mickelson ET, Bronikowski MJ, Smalley RE, Tour JM. Dissolution of Small
Diameter Single-Wall Carbon Nanotubes in Organic Solvents? Chemical Communications
2001;193-4.
6. Dumonteil S, Demortier A, Detriche S, Raes C, Fonseca A, Rhle M, Nagy JB. Dispersion of
Carbon Nanotubes Using Organic Solvents. Journal of Nanoscience and Nanotechnology
2006, 6(5), 1315-8
7. Bahr JL, Yang J, Kosynkin DV, Bronikowski MJ, Smalley RE, Tour JM. Functionalization
of Carbon Nanotubes by Electrochemical Reduction of Aryl Diazonium Salts: A Bucky
Paper Electrode. Journal of American Chemical Society 2001;123:6536-42.
8. Teruo Takahashi, Katsunori Tsunoda, Hirofumi Yajima and Tadahiro Ishii. Dispersion and
Purification of Single-Wall Carbon Nanotubes Using Carboxymethylcellulose. Japanese
Journal of Applied Physics 2004, 43(6A), 3636-9
9. Cohen RS, Roth EN, Baskaran E, Kalisman YL, Szleifer I, Rozen RY. Selective Dispersion
of Single-Walled Carbon Nanotubes in the Presence of Polymers: the Role of Molecular and
Colloidal Length Scales. Journal of the American Chemical Society 2004, 126(45), 14850-7
10. Ham HT, Choi YS, Chung IJ. An Explanation of Dispersion States of Single-Walled Carbon
Nanotubes in Solvents and Aqueous Surfactant Solutions Using Solubility Parameters.
Journal of Colloid and Interface Science 2005, 286 (1), 216-23

19. Why van Hove transitions are observed in the optical spectra in individual SWNTs but
not in SWNT bundles? Can the intensity of the van Hove transitions be related to the
SWNT bundle diameter? Provide a scientific justification for your answer.

Please see references below.

64
1. Weisman RB. Fluorescence Spectroscopy of Single-Walled Carbon Nanotubes (In: Applied
Physics of Carbon Nanotubes: Fundamentals of Theory, Optics and Transport Devices, Ed.
by Rotkin SV, Subramoney S). Springer-Verlag, Berlin Heidelberg 2005:183-202
2. OConnell MJ, Bachilo SM, Huffman CB, Moore VC, Strano MS, Haroz EH, Rialon KL,
Boul PJ, Noon WH, Kittrell C, Ma J, Hauge RH, Weisman RB, Smalley RE. Band Gap
Fluorescence from Individual Single-Walled Carbon Nanotubes. Science 2002;297:593-6.

20. Suggest a di- or tri-block copolymer that will solubilize nanotubes in water from
which you can draw a continuous fiber. Subsequently you should be able to heat-treat
the fiber for complete polymer burn out, leaving a 100% nanotube fiber.

This is an open ended question with no definite answer as of 2006.

21. How 267 cm-1 band can be used to monitor SWNT exfoliation? Is this specific to 785
nm excitation? Are there other excitation wavelengths that can be used to monitor
SWNT exfoliation? (J. Phys. Chem. B, vol. 108, pp. 6905-6909, 2004)

Please see references below.

1. Heller DA, Barone PW, Swanson JP, Mayrhofer RM, Strano MS. Using Raman
Spectroscopy to Elucidate the Aggregation State of Single-Walled Carbon Nanotubes. The
Journal of Physical Chemistry B 2004, 108(22), 6905-9
2. Achieving Individual-Nanotube Dispersion at High Loading in Single-Walled Carbon
Nanotube Composites. Advanced Materials 2005, 17(8), 980-4

22. Calculate E11 and E22 for the (5,5) and (5,4) tubes. Give the appropriate equation and
the reference.

23. Determine E11 and E22 for (10,10), (10,0), and (10,9) tubes. At what wavelengths (in
nm and in eV) you would expect van Hove transitions for these tubes?

Please consult the following references for the answer to questions 22 and 23.
1. Charlier JC, Lambin P. Electronic Structure of Carbon Nanotubes with Chiral Symmetry.
Physical Review B 1998;57(24):R15 037
2. Bachilo SM, Strano MS, Kittrell C, Ma J, Hauge RH, Smalley RE, Weisman RB. Structure-
Assigned Optical Spectra of Single-Walled Carbon Nanotubes. Science
2002;298(5602):2361-6.
3. Kataura H, Kumazawa H, Maniwa Y, Umezu I, Suzuki S, Ohtsuka Y, Achiba Y, Synth. Met.
1999;103:2555
4. Saito R, Dresselhaus G, Dresselhaus M, Physical properties of carbon nanotubes, Imperial
College Press (1998).
5. Saito R, Dresselhaus G, Dresselhaus M, Phys. Rev. 2000;B 61:2981
6. Charlier JC, Lambin P, Phys. Rev. B 1998;57:R15037

65
7. Bachilo SM, Strano MS, Kittrell C, Ma J, Hauge RH, Smalley RE, Weisman RB, Science
2002;298:2361

24. Can van Hove transitions be observed in (a) DWNTs and in (b) MWNTs?

Please see the following reference.

1. Brennan ME, Coleman JN, Drury A, Lahr B, Kobayashi T, Blau WJ. Nonlinear
Photoluminescence from van Hove Singularities in Multiwalled Carbon Nanotubes. Optics
Letters 2003;28(4):266-8

25. What experiment you would do to determine, if all the walls in a given MWNT have
the same chirality? Have such tubes been made. If so, how?

Please see references below.

1. Koziol K, Shaffer M, Windle A. Three-Dimensional Inter Order in Multiwalled Carbon
Nanotubes Grown by Chemical Vapor Deposition. Advanced Materials 2005;17(6):760-3.
2. Xu Z, Bai X, Wang ZL, Wang E. Multiwall Carbon Nanotubes Made of Monochirality
Graphite Shells. Journal of American Chemical Society 2006;128:1052-3.

26. (a) Thermogravimetric analysis (TGA) of a batch of HiPCO tubes shows 10 % weight
gain when heated from room temperature to 300 C in air. What information can you
obtain from this weight gain? This sample had a residue of 40 wt% when heated to
1000 C in air. Assuming that Fe(CO)5 was used as the catalyst, calculate the weight
percent of catalytic impurity in the sample in which the TGA study was conducted.
(b) Thermogravimetric analysis of a second batch of HiPCO tubes that had been pre-
oxidized in moist air at 240 C does not show a weight gain in TGA when heated from
room temperature to 300 C, but shows a residue of 40 wt% when heated to 1000 C
in air. What is the weight % catalytic impurity in this second batch and why there is
no weight gain in this case?

26(a): Since the TGA was conducted in the presence of air (which contains O2), weight gain is
due to the oxidation of metallic catalyst impurities. When heated up to 1000 C, the C-content
from tube became oxidized in the form of CO or CO2 (CNT burnout), and only oxides of metal
(being heavy and non-volatile) remained in the pan. Therefore, the 40% residue can be attributed
to the oxides of metal. Assuming that the metallic impurity (Fe) after oxidation gets converted to
Fe2O3, the weight fraction of original impurity (Fe) can be calculated to be ~ 28%.

26(b): The weight fraction of the original impurity (Fe) can be calculated to be ~25.4%.

27. Nanotubes are heralded as the strongest material that will ever be produced. Yet, the
tensile strength of nanotube macroscopic fibers and yarns produced to-date is below 3
GPa, while carbon and polymeric fibers with tensile strength as high as ~ 6 GPa have

66
 been commercialized. What is the maximum tensile strength that you can expect from
a carbon nanotube (SWNT, DWNT, MWNT etc) fiber/yarn? Describe three
approaches (one paragraph on each approach) that one should pursue to produce
high strength carbon nanotube fiber/yarn.

Please see reference below.

1. Li YL, Kinloch IA, Windle AH. Direct Spinning of Carbon Nanotube Fibers from Chemical
Vapor Deposition Synthesis. Science 2004;304(5668):276-8.
2. Miaudet P, Badaire S, Maugey M, Derre A, Pichot V, Launois P, Poulin P, Zakri C. Hot-
Drawing of Single and Multiwall Carbon Nanotube Fibers for High Toughness and
Alignment. Nano Letters 2005;5(11):2212-2215.
3. Ericson LM, Fan H, Peng H, Davis VA, Zhou W, Sulpizio J, Wang Y, Booker R, Vavro J,
Guthy C, Parra-Vasquez ANG, Kim MJ, Ramesh S, Saini RK, Kittrell C, Lavin G, Schmidt
H, Adams WW, Billups WE, Pasquali M, Hwang WF, Hauge, RH, Fischer JE, Smalley RE.
Macroscopic, Neat, Single-Walled Carbon Nanotube Fibers. Science 2004, 305 (5689),
1447-50
4. Zhang M, Atkinson KR, Baughman RH. Multifunctional Carbon Nanotube Yarns by
Downsizing an Ancient Technology. Science 2004, 306, 1358-61
5. Li YH, Wei J, Zhang X, Xu C, Wu D, Lu L, Wei B. Mechanical and electrical properties of
carbon nanotube ribbons. Chemical Physics Letters 2002;365:95100
6. Wei J, Jiang B, Wu D, Wei B. Large-Scale Synthesis of Long Double-Walled Carbon
Nanotubes. J. Phys. Chem. B 2004;108:8844-47
7. Li Y, Wang K, Wei J, Gu Z, Wang Z, Luo J, Wu D. Tensile properties of long aligned
double-walled carbon nanotube strands. Carbon 2005;43:315
8. Wei B, Vajtai R, Choi YY, Ajayan PM, Zhu H, Xu C, Wu D. Structural Characterizations of
Long Single-Walled Carbon Nanotube Strands. Nano Letters 2002;2(10):1105-1107
9. Kozlov ME, Capps RC, Sampson WM, Ebron VH, Ferraris JP, Baughman RH. Spinning
solid and hollow polymer-free carbon nanotube fibers. Advanced Materials 2005;17(5):614-
617
10. Steinmetz J, Glerup M, Paillet M, Bernier P, Holzinger M. Production of pure nanotube
fibers using a modified wet-spinning method. Carbon 2005;43:23972429
11. Zhu HW, Xu CL, Wu Dh, Wei BQ, Vajtai R, Ajayan PM. Direct Synthesis of Long Single-
Walled Carbon Nanotube Strands. Science 2002;296:884-6
12. Anglaret E, Righi A, Sauvajol JL, Bernier P, Vigolo B, Poulin P. Raman study of
orientational order in fibers of single wall carbon nanotubes. Physica B 2002;323:3843
13. Jiang K, Li Q, Fan S. Spinning continuous carbon nanotube yarns. Nature 2002;419:801
14. Yang QH, Bai S, Fournier T, Li F, Wang G, Cheng HM, Bai JB. Direct growth of
macroscopic fibers composed of large diameter SWNTs by CVD. Chemical Physics Letters
2003;370:274279

28. Tensile strength of a SWNT/DWNT buckypaper between 10 and 850 MPa has been
reported. What mechanism is responsible for improving buckypapers tensile
strength? Can one process a similar strength buckypaper from MWNTs?

Please see the references below.

67
1. Zhang X, Sreekumar TV, Liu T, Kumar S. Properties and Structure of Nitric Acid Oxidized
Single Wall Carbon Nanotube Films. Journal of Physical Chemistry B 2004;108:16435-40.
2. Wei J, Zhu H, Li Y, Chen B, Jia Y, Wang K, Wang Z, Liu W, Luo J, Zheng M, Wu D, Zhu Y,
Wei B. Ultrathin Single-Layered Membranes from Double-Walled Carbon Nanotubes
Advanced Materials 2006, 18(13), 1695-700.
3. Sreekumar TV, Liu T, Kumar S, Ericson LM, Hauge RH, Smalley RE. Single-Wall Carbon
Nanotube Films. Chemistry of Materials 2003;15:175-8

29. There are wide ranging values of the nanotube volume fraction at which electrical
percolation is obtained. Assuming that the nanotube aspect ratio for these samples is
comparable, what factors are responsible for the wide ranging values for the electrical
percolation?

Factors responsible for varying percolation: nanotube length, diameter, quality of dispersion,
nanotube exfoliation (i.e. single wall carbon nanotube bundle diameter etc), if nanotubes are
straight or curly, impurity are some of the factors responsible for varying percolation.

References:
1. Grunlan, J.C. et. al., Adv. Mater. 2004, 16, 150
2. Gojny FH, Wichmann MHG, Fiedler B, Kinloch IA, Bauhofer W, Windle AH, Schulte K.
Evaluation and Identification of Electrical and Thermal Conduction Mechanisms in Carbon
Nanotube/Epoxy Composites. Polymer 2006;47(6):2036-45
3. Sandler JKW, Kirk JE, Kinloch IA, Shaffer MSP, Windle AH. Ultra-Low Electrical
Percolation Threshold In Carbon-Nanotube-Epoxy Composites. Polymer 2003 ;44(19) :5893-
9
4. Moisala A, Li Q, Kinloch IA, Windle AH. Thermal and electrical conductivity of single- and
multi-walled carbon nanotube-epoxy composites. Composites Science and Technology
2006 ;66 (10) :1285-8
5. Martin CA, Sandler JKW, Shaffer MSP, Schwarz MK, Bauhofer W, Schulte K, Windle AH.
Formation of percolating networks in multi-wall carbon-nanotubeepoxy composites.
Composites Science and Technology 2004 ;64(15) :2309-16

30. It has been reported that the polymer/carbon nanotube composite exhibits higher
solvent resistance than the control polymer. What factors are responsible for the
enhanced solvent resistance?

Please see references below:

1. Sreekumar, T.V. et. al., Adv. Mater. 2004, 16, 58
2. Guo, H. et. al. Polymer 2005, 46, 3001
3. Potschke, P. et. al., Polymer 2002, 43, 3247
4. Chae, H. G. et. al., Polymer 2006, 47, 3494

68
1.13 Solutions for Chapter 13
Surface Patterning Using Self-Assembled Monolayers: A Bottom-Up
Approach to the Fabrication of Microdevices by Lakshmi Supriya
and Richard O. Claus (Solutions by Mark Schulz)

1. List the important trade-offs when considering bottom-up and top-down fabrication
technologies.

Top-Down. Technology used in microelectronic fabrication with about one billion electronic
components (gigabit electronic chips) on an area of 1 cm. The characteristic length of
components is about 100 nanometers.

Bottom-Up. This refers to the assembly of molecules and tiny solids starting from individual
atoms. Nanoscale components are assembled into larger complex units that have different types
of functionality.

1. National Institute of Materials Science, Japan; http://www.nims.go.jp/eng/about/research-

fields/field01.html.
2. O.G. Schmidt, Ch. Deneke, Y. Nakamura, R. Zapf-Gottwick, C. Mller, N. Y. Jin-Phillipp,
Advances in Solid State Physics, Nanotechnology - Bottom-up Meets Top-down, Springer
Berlin / Heidelberg, Volume 42/2002, ISSN 1617-5034.

2. Perform a literature search on the subject of patterning of substrates using self-

assembled monolayers and list any new advances in techniques that have been made
relative to the techniques cited in this chapter.

In the literature search, search by key words first and then add the current year to the search to
get the most recent results.

3. Think of some new possible applications for surface patterning using the SAM technique
and list potential benefits.

Searching the literature will bring up applications. For example, bio-photolithography is

promising new area.

1. Amit Kumar, Hans A. Biebuyck, and George M. Whitesides, Patterning Self -Assembled
Monolayers: Applications in Materials Science, Langmuir 1994,10, 1498-1511.
2. Mrksich M.; Whitesides G.M., Trends in Biotechnology, Patterning self-assembled
monolayers using microcontact printing: a new technology for biosensors? Volume
13, Number 6, June 1995, pp. 228-235(8), Elsevier Science.

69
3. Emmanuel. Delamarche, Bruno. Michel, Hans A. Biebuyck, Christoph Gerber, Golden
interfaces: The Surface of Self-Assembled Monolayers, Advanced Materials, Volume 8,
Issue 9, Pages 719 729, 29 Oct 2004.

70
1.14 Solutions for Chapter 14
Enhancement of the Mechanical Strength of Polymer-Based
Composites Using Carbon Nanotubes by Kin-Tak Lau, Jagannathan
Sankar, and David Hui
1. Which factors affect the mechanical, electrical, and thermal properties of
nanotube/polymer composites?

The amount and alignment of the nanotubes inside the composites would influence their
mechanical, thermal and electrical properties. Besides, the homogeneity (uniform dispersion of
the nanotubes) of the composites is the key to make strong and high conductive
nanotube/polymer composites.

2. What are the differences between the mechanical properties of singlewalled and multi-
walled carbon nanotubes? Do all inner layers of the nanotubes contribute to the strength of
the multi-walled nanotubes?

Since only a weak Van der interaction between inner layers of the multi-walled nanotubes, the
stress transfer from the outer-layer to inner layers is very weak, i.e. the outermost layer takes
most of the load while the inner layers would not. In such case, single-walled nanotubes may
become more effective as nano-reinforcements for composite materials. Other approaches are to
spin the nanotubes into fibers to provide improved strength.

3. Fabrication processes of nanotube/polymer composites are crucial factors that control

the integrity of the composites. Which parameters have to be controlled or studied in
making high-strength composites?

The homogeneity is an important factor that produces strong nanotube/polymer composites. The
control of sonication time and viscosity of the resin is important. However, the use of some
functionalized nanotubes may achieve non uniformly-dispersed composite materials.

4. Based on your own understanding, which type of nanotube (MWNT or SWNT) is better
to use to make nanotube/polymer composites?

In terms of stress transfer theory, single-walled nanotubes may better than multi-walled types.
However, the fabrication cost of the single-walled nanotubes is higher as compared with the cost
for the multi-walled type. Also, the length of the nanotube may be more important than the type.

71
1.15 Solutions for Chapter 15
Nanoscale Intelligent Materials and Structures by Yun Yeo-Heung,
Inpil Kang, Sachin Jain, Atul Miskin, Suhasini Narasimhadevara,
Goutham Kirikera, Vishal Shinde, Sri Laxmi Pammi, Saurabh
Datta, Peng He, Douglas Hurd, Mark J. Schulz, Vesselin N. Shanov,
Donglu Shi, F.J. Boerio, and Mannur J. Sundaresan (Solutions by
Yun YeoHeung)

1. In the chapters in this book, different types of nanoscale materials are discussed. These
include carbon nanotubes, boron nitride nanotubes, zinc oxide nanobelts, and bismuth
nanowires. What might be the advantages and disadvantages of building smart materials
using these different types of nanoscale materials?

The advantages of each material would depend on the applications. The mechanical, physical,
electrical, thermal, and other properties of each material should be tabulated and then the
material with the overall best properties can be selected. Answering this question depends on
completing the table in question 7.

2. Describe the principle of the Potentiostat/Galvanostat. Describe the saturated Calomel

reference electrode (SCE). You may go to the manufactures Websites for information on
electrochemistry.

A potentiostat is an instrument that controls the potential between a working electrode and a
reference electrode of a three-electrode cell (see fig 1 below) at a preset value. It applies current
whatever it needs to flow between the working and counter electrodes to keep the desired
potential. Current is the main variable to be measured while applying the constant potential in the
electrochemical cell.
A galvanostat is an electronic instrument that controls the current through an electrochemical
cell at a preset value, instead of potential. Therefore potential is main value to be measured using
the galvanostat. Both the potentiostat and galvanostat should not exceed the compliance limits of
voltage and current for the electronic device.

72
 Figure1. General electrochemical cell with three electrodes; pt counter electrode, reference
electrode, and working electrode.

A potentiostat/galvanostat requires an electrochemical cell with three electrodes. The main

purpose of the reference electrode is to measure working electrode potential. The most common
lab reference electrodes are the Saturated Calomel Electrode (SCE) and the Silver/Silver
Chloride (Ag/AgCl) electrodes. SCE have the redox process; Hg2Cl2 + 2e- <=> 2Hg + 2Cl- . The
SCE contains mercury covered by a layer of mercury (II) chloride (calomel) which is contact
with a saturated solution of potassium chloride. Generally, the junction to the electrolyte is made
by a porous Vycor frit.

3. What is a motor protein? Why are DNA and motor proteins possibly good actuators in
vivo? Can a biological smart machine be made?

Motor proteins can be defined by the role they play in a spindle assembly and their function in
chromosome movement during meiosis or mitosis. Three types of cytoplasmic moters-myosins,
dyneins, and kinesins (Fig. 2) are mainly studied. DNA is another technique to develop new
smart machine including several viral proteins.

Figure 2. Example of motor protein, from ref. [187] in book.

4. Define solid polymer electrolyte. What is the limitation of a solid polymer electrolyte in a

73
structural application? Propose ways to improve the mechanical properties of solid
polymer electrolytes.

A solid polymer electrolyte (SPE) is an ionically conducting polymer, generally classified as a

polymer electrolyte or polymer ionics. The SPE enables operation in a dry environment instead
of special media such as liquid electrolytes. The dry actuator is suitable for some replacement
applications in which existing smart materials are used.

5. Describe the sp2 hybridization in the CNT structure and the -bonds and -bonds.

When a carbon atom is attached to 3 groups it is involved in 3 s bonds, it requires 3 orbitals in

the hybrid set. This requires that it is sp2 hybridized as shown in Figure 3. The in-plane
Bond, referred to as the -bond is a strong covalent bond that strongly binds the atoms in the
plane. The remaining -bond is out of- plane (perpendicular to the plane) and much weaker than
the in-plane bond. This -bond is the main source for electrical conductivity.

Figure 3. C-C bonding structure to show sp2 hybridization and -bonds and -bonds.

6. A machine with the ability to prevent failure is a smart machine. A manufacturer wants
to develop a way to provide short-time emergency lubrication for the bearings in an
aircraft engine. This would allow the aircraft to operate long enough to safely land if the
normal bearing lubrication system fails. Think of a nanoscale material that could be a
lubricant. Design a system that automatically delivers this lubricant to the bearing for a
short time if the standard lubrication system fails.

This is an open-ended design problem with different possible solutions. One approach may be to
develop a carbon nanotube or buckyball dry lubricant that is held in a binder material like a
grease that is released into the bearing by a temperature rise. The dry nano-lubricant could
operate at high temperature and remain in the bearing longer than a liquid lubricant.

7. Search the literature for the properties of nanoscale materials and try to compute and fill
in the missing properties in Table 15.3.

This question requires literature searching and documentation of references. A table of values
when developed could be published for general benefit.

74
1.16 Solutions for Chapter 16
Thermal Properties and Microstructures of Polymer
Nanostructured Materials by Joseph H. Koo and Louis A. Pilato

1. What are the shortcomings of using wide-angle x-ray diffraction (WAXD) to determine
the degree of dispersion in polymer-clay nanocomposites? How can one compensate for the
shortcomings for this technique?

Wide-angle x-ray diffraction (WAXD) is the most commonly used technique to characterize
the degree of nanodisperions of MMT organoclay in a specific polymer. Wide-angle x-ray
diffraction measures the spacing between the ordered crystalline layers of the organoclay. By
using Braggs law: sin = n/2d where d is the spacing between atomic planes in the crystalline
space and is the x-ray wavelength. The intensity of the diffracted x-ray is measured as a
function of the diffraction angle 2 and the specimens orientation. This diffraction pattern is
used to identify the specimens crystalline phases and to measure its structural properties.
WAXD is nondestructive and does not require elaborate sample preparation which partly
explains the wide usage of this technique in materials characterization. Spacing change (increase
or decrease) information can be used to determine the type of polymer nanocomposite created,
such as:
Immiscible (no d-spacing change)
Decomposed/deintercalated (d-spacing decrease)
Intercalated (d-spacing increase)
Exfoliated (d-spacing outside of wide-angle x-ray diffraction, or so expansive and
disordered as to give a signal)

However, WAXD can be affected by many parameters:

Sampling (powder vs. solids, alignment of clay platelets)
Experimental parameters (slit width, count time, angle step rate)
Layered silicate order (disordered/amorphous materials exhibit no pattern by WAXD)
WAXD measures d-spacing, not overall (global) clay dispersion in the sample

To reveal the capability of a modern x-ray characterization of nanoparticles and the

fundamental of WAXD, the reader should refer to other sources.1 Figure 16.18 (note: these
figures are from Chapter 16) displays the WAXD data showing the intensity of various wt% (5,
10, and 15 wt%) of SCPs Cloisite 30B MMT organoclay dispersing in a resole phenolic
(Bordens SC-1008).2 The fact that no peaks were shown at diffraction angle around 2.5 for all
three wt% indicates that all three formulations were possibly in an exfoliated state. Figure 16.19,
Fig. 16.20, and Fig. 16.21 are TEM images of the 5 wt% Cloisite 30B in 95 wt% SC-1008 (Fig.
16.19), 10 wt% Cloisite 30B in 90 wt% SC-1008 (Fig. 16.20), and 15 wt% Cloisite 30B in 85
wt% SC-1008 (Fig. 16.21). In fact, the TEM images indicate intercalation and not exfoliation of
the nanoclay in the resin system. As a result, WAXD can be misleading, this technique is best to
compensate with TEM images.

75
2. What is the disadvantage of using transmission electron microscopy (TEM) to determine
the degree of nanoparticle dispersion in polymer nanocomposites? How can one
compensate for this technique?

One of the characteristics of polymer nanostructured materials is their extremely small

particle size of the added nanoparticle. Although some structural features can be revealed by x-
ray and neutron diffraction, direct imaging of individual nanoparticles is only possible using
transmission electron microscopy (TEM) and scanning probe microscopy. Transmission electron
microscopy is unique because it can provide a real space image on the atom distribution in the
nanocrystal and on its surface.3, 4 Todays TEM is a versatile tool that provides not only atomic
resolution lattice images, but also chemical information at a spatial resolution of 1 nm or better,
allowing direct identification of the chemistry of a single nanocrystal. With a finely focused
electron probe, the structural characteristics of a single nanoparticle can be fully characterized.
To reveal the capabilities of a modern TEM and the fundamentals of TEM and its applications in
characterization of nanophase materials, the reader should refer to other sources.3-5
TEM sample preparation is of utmost importance in obtaining a TEM with good resolution.
Figure 16.40 (note: we continue to use the figure numbers from Chapter 16) illustrates the
sequence of TEM sample preparation that the author has followed in his study.6 The basic
requirements are that the specimen has to be thin enough to be transparent to the electron beam,
must be clean, without much damage or contamination. There are several common methods for
TEM specimen preparation:
Ion-milling: for nearly all kinds of materials
Electropolishing: for conductive bulk materials
Crushing powders: the simplest way to prepare for TEM specimens, but microstructural
details may be lost

The bulk sample is first cut into thin slices about 0.6 mm thick. The thin sample slices are
then either core-drilled or punched to obtain a 3-mm-diameter disk with a thickness of ~ 60 m.
The disk is then dimpled until the thickness in the center reaches about 1020 m, and the
specimen is then ion-milled until it is penetrated.

Figure 16.40. TEM sample preparation process by ion-milling.

Transmission electron microscopy allows the observation of the overall organoclay dispersion in
the polymer nanocomposite sample. Clay dispersion and structure observed under the
microscope can determine the nature of a clay nanocomposite as follows:
Immiscible: usually large clay tactoids, undispersed clay particles
Intercalated: clay layers in ordered stacks can be observed

76
 Exfoliated: single clay layers can be observed

Global microscale dispersion, as well as nanoscale dispersion and structure, can be determined.
Transmission electron microscopy has several limitations and drawbacks, as follows:
In sampling, heterogeneous samples will give false results
Labor-intensive analysis, involving expensive analytical instruments
Cannot measure d-spacing of clay, therefore, cannot easily determine difference between
intercalated clay nanocomposite and well-dispersed, immiscible nanocomposite

Transmission electron microscopy measures overall characteristics of clay dispersion, such

as uniformity, tactoids or non-uniformity of the clay within the material. It is recommended that
TEM measurements should be combined with WAXD data for a thorough analysis of the
nanomaterial.

3. Discuss other types of techniques that one can use to study the morphology of these
polymer nanocomposites.

Energy-dispersive x-ray spectroscopy (EDS)

X-rays emitted from atoms are characteristics of the elements, and the intensity distribution of
the x-rays represents the thickness-projected atom densities in the specimen. This is known as
energy-dispersive x-ray spectroscopy (EDS) which has played an important role in microanalysis,
particularly for heavier elements. EDS is a key tool for identifying the chemical composition of
a specimen. A modern TEM is capable of producing a fine electron probe smaller than 2 nm,
allowing direct identification of the local composition of an individual element. Examples are
given in the authors publication.6 When POSS materials were incorporated into the cyanate
ester resin, EDS was used to demonstrate that a molecular dispersion was achieved by the PT-15
cyanate ester-Trisilanolphenyl-POSS nanocomposite. Figure 16.32 shows the TEM micrographs
of PT-15/SO1458 POSS in progressive magnification. EDS shows Si is dispersed very well in
the PT-15 resin system. Si counts were observed in the particle and matrix areas. Thus
molecular dispersion of POSS particle in the PT-15 CE resin is evident.

Small-Angle X-ray Scattering (SAXS)

Small-angle x-ray scattering (SAXS) is an analytical x-ray application technique for the
structural characterization of solid and fluid materials in the nanometer range. In SAXS
experiments, the sample is irradiated by a well-defined, monochromatic x-ray beam, as shown in
Fig. 16.41. When a nonhomogeneous medium, for example proteins in water, is irradiated,
structural information about the scattering particles can be derived from the intensity distribution
of the scattered beam at very low scattering angles.

77
 Figure 16.41. Schematic of a small-angle x-ray scattering (SAXS).

With SAXS it is possible to study both monodisperse and polydisperse systems. In the case of
monodisperse systems, one can determine size, shape, and internal structure of the particles. For
polydisperse systems, a size distribution can be calculated under the assumption that all particles
have the same shape. Small-angle x-ray scattering is applied to investigate structural details in
the 0.5 to 50 nm size range in materials such as:
Suspended nanopowders
Materials in life science and biotechnology (proteins, viruses, DNA complexes)
Polymer films and fibers
Catalyst surface per volume
Microemulsions
Liquid crystals

Small-angle x-ray scattering can provide the following information:

Lamella repeat distance
Radius of gyration
Particle size and shape
Large-scale structure and long-range order

Readers should refer to existing texts describing the SAXS techniques.7-9

4. What other types of nanoparticles can be used to enhance the thermal and mechanical
properties of polymer nanostructured materials? Explain and give examples.

There are other nanoparticles such as nanosilica, mutli-wall carbon nanotubes (MWNTs),
single-wall carbon nanotubes (SWNT), buckytubes (also known as small diameter carbon
nanotubes, SDNT), nano-silicon carbide (n-SiC) particles or whiskers, nano-aluminum oxide (n-
Al203), nano-titanium oxide (n-TiO2), and exfoliated graphite that have been used to form
polymer nanocomposites with enhanced material properties. These nanoparticles are briefly
discussed in the authors recent publications.10, 11
In most cases, polymer nanostructured materials exhibit multi-functionality. Several of the
functions of these materials are listed below:10
Thermal: increased thermal resistance, higher glass transient temperature (Tg) or heat
deflection temperature (HDT), reduced coefficient of thermal expansion (CTE)
Mechanical: increased modulus, strength, increased toughness/elongation (in some cases)

78
 Chemical: improved solvent resistance, improved moisture resistance
Electrical: improved thermal conductivity, lower resistivity (depends on the
nanoparticles)
Barrier: reduced oxygen, moisture transmission
Optical: clear, transparency provided in selective systems
Others: abrasion resistance, reduced shrinkage

In general, polymers can be classified into the three basic families of resins namely
thermoplastics, thermosets, and elastomers. An extensive review of thermoplastic-, thermoset-,
and elastomer-based nanocomposites can be found in the authors publication.10

5. Discuss the similarities and differences of different types of nanoparticles and give
examples.

Nanoparticles such as MMT nanoclay, carbon nanofibers (CNF), POSS, nanosilica, mutli-
wall carbon nanotubes (MWNT), single-wall carbon nanotubes (SWNT), buckytubes, nano-
silicon carbide (n-SiC) particles or whiskers, nano-aluminum oxide (n-Al203), nano-titanium
oxide (n-TiO2), and exfoliated graphite all have at least one-dimension is in nanoscale.10 In terms
of physical dimensions, MMT nanoclay and exfoliated graphite come in sheets and can be
exfoliated in single sheet. CNF, MWNT, buckytubes, SWNT, and n-SiC whiskers come in fiber
form. POSS, nanosilica, n-SiC particles, n-Al203, and n-TiO2 comes in particle form. They can
also be surface treated to be more compatible with the polymer matrix.
All the above mentioned nanoparticles except POSS are inert to the polymer matrix they will
act as nanofillers to enhance specific materials properties such as thermal, mechanical,
flammability. POSS molecules can chemically react with the polymer matrix and be molecular
dispersed in the polymer matrix (see examples listed in Chapter 16, pp. 432-435).

6. Discuss other thermal applications of polymer nanostructured materials in the literature.

Thermal management is another emerging area that polymer nanostructured materials can be
beneficial. Thermal management relates to problems that arise from heat dissipation, thermal
stresses (CTE, coefficient of thermal expansion) that occur in electronic components. Applied
Sciences Inc. has promoted carbon nanofiber (see Chapter 16, pp. 411-415) for electronic boards,
high power electronics, computers, and cooling devices.12-14 Carbon nanotubes are being
explored aggressively in similar areas.15, 16 Equally important and closely related to thermal
management is thermal protection systems (TPS) that safeguard polymer composite systems
through nanotechnology. Examples of these are nanomodifed composite rocket ablative
materials (see Chapter 16, pp. 423- 431)2 and nanomodified carbon-carbon composites (see
Chapter 16, pp. 431-439).17

7. How can one enhance the interfacial interaction and compatibility with different
nanoparticles in a specific polymer matrix?

79
 All the nanoparticles can be chemically surface treated to be compatible with a specific
polymer matrix. For example MMT organoclays are surface modified to allow complete
dispersibility and miscibility with different resin system for which they were designed to
improve. For example, Southern Clay Products Cloisite 30B is a natural MMT modified with a
quaternary ammonium salt. Specific chemical pretreatment modified MT2EtOH: methyl, tallow,
bis-2-hydroxyethyl, and quaternary ammonium) was used for the preparation of Cloisite 30B.
Cloisite 30B is very compatible with nylon 11 and 12 polymers.10
The use of Hanse Chemie Technolgy18-22 of macrosurface treated spherical nanosilica
allows the introduction of up to over 10 wt% nanosilica with minimal increase in viscosity in the
nanomodifed reactive resin system and sill provide multifunctionality to the resulting cured
resin system. Hanse Chemies (now known as Nanoresins) proprietary synthesis of silica
nanocomposites is shown in Figure 16.42. A silicate solution is transformed into silica sol using
the sol-gel method. The silicas were surface-treated to be compatible with selective polymer
matrices to form transparent polymer nanocomposites with low viscosity and no sedimentation.
Nanoresins are able to create homogeneous dispersions of amorphous silicon dioxide in standard,
chemically unchanged organic monomers, prepolymers, and oligomers using this technique. The
silica phase consists of discrete nanospheres (20 nm) with an extremely narrow size distribution.
Owing to agglomerate-free colloidal dispersion of the nanosilica particles, the nanocomposites
are highly transparent, with low viscosity, and they do not show sedimentation even with SiO2
loading up to 60 wt% as shown in Figure 16.43. This nanosilica serves as both performance
additive and filler.
Nanopox F 400 is a high performance, versatile, silica reinforced bisphenol A based epoxy
resin for the use in fiber composites.21 The silica phase consists of surface-modified synthetic
SiO2 nanospheres of very small size (average diameter of 20 nm) with a narrow particle size
distribution (maximum diameter 50 nm). Despite the high SiO2 content of 40 wt%, Nanopox F
400 has a comparatively low viscosity due to the agglomerate-free colloidal dispersion of the
nanoparticles in the resin. Nanopox F 520 is a high performance, versatile, silica reinforced
bisphenol F based epoxy resin for the use in electric and electronic applications.22

Figure 16.42. Nanoresins route to produce nanosilicas. (Courtesy of Hanse Chemie.)

80
 Figure 16.43. TEM micrograph showing Nanoresins homogenous dispersion of nanosilica in
polymer. (Courtesy of Hanse Chemie.)

REFERENCES
1. Wang, Z.L., (ed.), Characterization of Nanophase Materials, Wiley Vch, Weinheim,
Germany, 2000, pp. 13-36.
2. Koo, J.H., Stretz, H., Bray, A., Weispfenning, J., Luo, Z.P., and Wootan, W., Nanocomposite
rocket ablative materials: processing, microstructures, and performance, Paper AIAA-2004-
1996, AIAA, Reston, VA, 2004.
3. Wang, Z.L., (ed.), Characterization of Nanophase Materials, Wiley Vch, Weinheim,
Germany, 2000, pp. 37-80.
4. Buseck, P., Cowley, J.M., and Eyring, L., (eds.), High Resolution Transmission Electron
Microscopy and Associated Techniques, Oxford University Press, New York, 1988.
5. Yan, N., and Wang, Z.L. (eds.), Handbook of Microscopy for Nanotechnology, Kluwer
Academic Publishers, Boston, 2005.
6. Koo, J.H., Polymer Nanocomposites: Processing, Characterization, and Applications,
McGraw-Hill, New York, 2006, pp. 81-88.
7. Cao, G., Nanostructures and Nanomaterials: Synthesis, Properties & Applications, Imperial
College Press, London, 2004, pp. 329-390.
8. Guinier, A., and Gournet, G., Small-Angle Scattering of X-Ray, Wiley, New York, 1955.
9. Glatter, O., and Kratky, O., Small-Angle X-Ray Scattering, Academic Press, London, 1982.
10. Koo, J.H., Polymer Nanocomposites: Processing, Characterization, and Applications,
McGraw-Hill, New York, 2006, pp. 9-49, 51-59, 138-159.
11. Koo, J.H., Lao, S. et al., Cyanate ester-silicon carbide nanocomposites: processing and
characterization, Proceedings of SAMPE Technical Conference, SAMPE, Covina, CA, 2006.
12. Lake, M.L, Glasgow, D.G. et al., Carbon nanofiber polymer composites: electrical and
mechanical properties, Proceedings of SAMPE International Symposium, SAMPE, Covina,
CA, 2002.

81
13. Tibbetts, G.G. et al., Conductivity of thermoplastic composites compounded of glass fibers
and carbon nanofibers, Proceedings of SAMPE International Symposium, SAMPE, Covina,
CA, 2003.
14. Yan, S. et al., Thermal and electrical analysis of vapor grown carbon nanofiber
(VGCNF)/LCP composites, Proceedings of SAMPE International Symposium, SAMPE,
Covina, CA, 2003.
15. Biercuk, M.J. et al, Carbon nanotube composites for thermal management, Applied Physical
Letters, 80, (15), 2767 (2002).
16. Mayeaux, B. et al, Application of carbon nanotube components for thermal management,
NASA Johnson Space Center for 8th Foresight Conference on Molecular Nanotechnology,
2006.
17. Koo, J.H., Pilato, L., and Wissler, G., Polymer nanostructured materials for propulsion
systems, Paper AIAA-2005-3605, AIAA, Reston, VA, 2005.
18. Sprenger, S., and Pyrlik, M., Nanoparticles in composites and adhesive: synergy with
elastomer, Proceedings of 11th International Conference on Composites/Nano Engineering,
Hilton Head Island, SC, Aug. 2004.
19. Sprenger, S., Kinloch, A.J., Taylor, A.C., and Mohammed, R.D., Rubber-toughened GFRCs
optimized by nanoparticles, JEC Composites, No. 19, Aug.-Sept. 2005, pp. 73-76.
20. Sprenger, S., Kinloch, A.J., Taylor, A.C., Mohammed, R.D., and Eger, C., Rubber-toughened
FRCs optimized by nanoparticles, JEC Composites, No. 21, Dec. 2005, pp. 66-69.
21. Nanopox F 400 Technical data sheet, Hanse Chemie USA, Hilton Head Island, SC.
22. Nanopox F 500 Technical data sheet, Hanse Chemie USA, Hilton Head Island, SC.

82
1.17 Solutions for Chapter 17
Manufacturing, Mechanical Characterization, and Modeling of a
Pultruded Thermoplastic Nanocomposite by Samit Roy,
Kalivarathan Vengadassalam, Farzana Hussain, and Hongbing Lu

1. Describe in detail the difference between intercalation and exfoliation of nanoclay

platelets. Why are these stages important in the processing of high-quality nanoclay
composites?

Intercalation is the increase in interlayer or gallery spacing between the nanoclay platelets by the
process of surface modification of nanoclay. The process of intercalation would enable the
polymer molecules to penetrate into the galleries between the platelets. The most common
surfactant used in the surface modification of nanoclay to make it organophilic is octadecylamine
(ODA).

Exfoliation is the process wherein the organically modified (intercalated) clay platelets are
completely delaminated. This is brought about by the extensive penetration of the clay by
polymer molecules. Subsequent to exfoliation, the clay platelets are dispersed in the polymer
matrix by various dispersion techniques, such as mechanical shearing, sonication etc.

It is essential to appreciate the importance of these two stages for the processing of high quality
nanocomposites. The process of surface modification of nanoclay leads to intercalation of
nanoclay platelets, which is an essential step for the complete exfoliation of platelets. The
uniform distribution of clay platelets in the polymer matrix would result in the interaction of
nanofiller particle, i.e. nanoclay, and polymer to form constrained regions. Since each nanoclay
tactoid contains numerous individual platelets, even a low loading of nanoclay would result in
high concentration of constrained regions.

2. Explain why unidirectional fiber-reinforced composites are much weaker in compression

than in tension. What is the most frequently encountered failure mode in compression of
unidirectional composites?

The overall compressive strength of unidirectional fiber reinforced polymer composites is 50%
the tensile strength. This is due to the fact that under compressive load microbuckling of the
fibers occur well before compressive fracture. Further, manufacturing defects such as voids and
fiber misalignment add to the reduction in compressive strength.

The most frequently encountered failure mode in compression of unidirectional composites is

fiber microbuckling in the form of kink band formation due to the localized shearing of the
polymer composite (see Figure 17.1).

83
3. What are some of the limitations of using the modified Argon formula (Equation 17.1) to
predict compressive failure in a unidirectional fiber composite?

The limitations of using the modified Argon formula to predict compressive failure in a
unidirectional fiber composite is that it assumes zero kink band angle (=0), and it also assumes
an elastic-perfectly plastic matrix material.

4. What were the changes made to the modified Argon formula (Equation 17.1) by
Budiansky and Fleck (Equation 17.2)? Explain why.
The changes made to the modified Argon formula by Budiansky and Fleck is to include a (i) a
non-zero kink band angle, >0 and (ii) strain-hardening plasticity in the polymer matrix.

The primary failure mechanism for unidirectional fiber composites under axial compressive
loads is fiber microbuckling, where in the fibers experience concurrent kinking with a kinkband
angle greater than zero, as shown in Figure 17.1 and Figure 17.13. Further, most polymer resins
exhibit strain-hardening plasticity which is more accurately modeled using the Ramberg-Osgood
relation. Therefore, it is unrealistic to assume an elastic-perfectly plastic matrix material with
kink band angle equal to zero for pultruded unidirectional E-glass/PP specimens.

5. Make a list of all of the processing variables used in the thermoplastic pultrusion process.
Discuss the effects of ultrasonic vibrations at the consolidation die on the pultruded
composite.

The most important process parameters include the pre-former temperature profile and the
process pull speed. The pre-former (referred to as preheater in Figure 17.2) consists of three
temperature zones which would determine the rate of heating of the matrix material thus
influencing the viscosity of the thermoplastic resin attained during the residence time of pre-preg
tapes in the performer. The process pull speed for a fixed die length, depending on the sectional
thickness, determines the residence time of the material. After passing through the pre-former die
the composite passes through a consolidation die. Ultrasonic vibrations are directed into the
preheated pre-preg tapes by means of a wave guide. Pressure is applied within the die to
consolidate the preheated pre-preg tapes to the chosen profile.

The ultrasonic vibrations directed into the pre-heated pre-preg tapes help to stimulate the resin
flow by decreasing effective resin viscosity, thereby reducing the void content and the friction at
the composite/die interface, which, in turn, reduces pull force requirement.

6. Discuss in detail the effect of addition of nanoclay particles on the following composite
properties: a. Compressive strength; b. Compressive modulus; c. Matrix yield strain in
shear; d. Critical kinking strain.

The effect of addition of nanoclay particles on the listed composite properties is discussed below:

84
a) Compressive Strength: A considerable improvement of 33% in the normalized
compressive strength of pultruded unidirectional E-Glass/PP composites is observed with
only 1 weight % addition of nanoclay. Further, a steady improvement in with increase in
nanoclay loading up to 10 weight % is observed. A significant improvement of 122% in
normalized compressive strength, for 10 weight % nanoclay loading is recorded.
b) Compressive Modulus: A significant improvement of 62% in normalized compressive
modulus of pultruded unidirectional E-Glass/PP composites with 1 weight % nanoclay
addition is observed. A steady increase in normalized compressive modulus with increase
in nanoclay loading up to10 weight % is observed. A significant improvement of 110% in
compressive modulus with 10 weight % nanoclay addition is measured.
c) Matrix Yield Strain in Shear: An increase of 30% in normalized matrix yield strain in
shear is measured for 3 weight % nanoclay addition. A steady increase with further
nanoclay addition is observed. A significant increase of 88% in matrix yield strain in
shear, with 10 weight % nanoclay loading was observed.
d) Critical Kinking Strain: The predicted shear strain in kink band shows a progressive
increase from 3 weight % nanoclay loading in pultruded unidirectional E-glass/PP with
nanoclay addition. An approximately 17% increase in kink band strain is predicted with
10 weight % nanoclay loading. From Figure 17.17, it is evident that although the
compressive failure process for the E-Glass/PP composite is inelastic, the degree of
inelasticity decreases with the increase in nanoclay loading.

85
 PART 3

Modeling of Nanoscale and Nanostructured Materials

86
1.18 Solutions for Chapter 18
Nanomechanics by Young W. Kwon (Solutions by Dong Qian)

1. What is the difference between the ab initio simulation method and the classical
molecular dynamics method as applied to nanomechanics?

In general, ab initio methods are designed to solve the schrodinger equation, whereas the MD
approach is primarily focused on the dynamics of the atomic system governed by Newtons
equation of motion. The results generated by the ab initio method include the electronic structure,
the potential energy field, and atomic degrees of freedom. In classical MD, the interatomic
potential that governs the interactions among the atoms is mainly based on an empirical formula.
For nanomechanics simulation, ab initio methods are more expensive than MD in terms of the
number of atoms and time scale they can address.

2. Discuss briefly the embedded atom method.

The embedded atom method (EAM) is a semi-empirical interatomic potential model mainly
developed for metal systems. The model is based on the theory that each atom on the solid can
be viewed as an impurity embedded in a host comprising other atoms. Correspondingly, the total
energy of the system is contributed by; 1) The embedding energy of each atom; and 2) Short
range core-core repulsion between the nucleus pair. Since its inception in the early 80s, the
EAM has been successfully applied for simulations up to billions of atoms and a modified
version, called MEAM, has also been proposed.

3. Explain clearly how the atomic and finite element models are coupled together.
This is tied to a particular approach. In terms of spatial partition, there are two classes. The first
is called a handshake approach, in which the FEM models are refined to a resolution such that
the nodes coincide with the atoms. The second class is based on overlap schemes, i.e., FEM
mesh are prescribed everywhere, and atomic model is embedded in local region. In terms of
coupling in time, both synchronized and multi-stepping algorithms have been developed. In
general, this area is still an active.

4. How is fatigue analysis at the atomic level performed?

We are not aware of any good method for this. The major limitation is the time scale that can be
treated in atomic scale simulations. Please perform a literature survey to see if any new methods
have been developed.

5. What are the advantages of performing fatigue analysis at the atomic level as opposed to
conventional fatigue analysis?

The conventional analysis is mainly based on empirical fitting to the experiment at the

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continuum scale and gives little insight on the mechanisms. Correspondingly, there is a strong
interest in understanding what triggers fatigue failure at the material level. The use of atomic
scale simulation could shed light on how detailed mechanisms, such as dislocation, can be
directly tied to the development of the failure and the type of dynamic load that is involved.

6. Compare different atomic energy potentials in terms of their characteristics and

applications.

The potentials can be characterized by the type of interactions that are taken into account, which
typically include: bond length (two-body), angle bending (three-body), angle twist (four-body),
columbic (long-range), etc. The choice of specific interaction is dependent on the systems being
considered.

7. Construct the matrix equation of motion for a carbon nanotube with chiral vector (n, n)
or (2n, 0) where n is an integer.

In general, the matrix equation of motion for each atom can be given as;
W
mx&&i = f i ext + f i int and fi int =
xi
in which m is the atomic mass, x is the spatial coordinate, fi ext and f i int are the externally
applied force and the force due to interatomic potential in the i-th dimension. The spatial
coordinate is a function of the chiral vector.

8. Apply the central difference technique for time integration to the matrix equation of
motion derived in Problem 7.

The central difference scheme is also called the verlet algorithm in the computational solid
physics community, and it can be directly applied. This scheme is known as an explicit scheme
and has a critical time step beyond which the algorithm will not be stable. Detailed algorithm
implementation can be found in chapter 6 in ref (Belytschko, Liu et al. 2000).

9. Apply Newmarks technique for time integration to the matrix equation of motion
derived in Problem 7.
The Newmarks method is also described in the reference. The Newmark method is an implicit
scheme, i.e., it involves iterative steps in which a matrix must be inverted to obtain a converged
solution. It is an unconditionally stable scheme, but the convergence can be an issue sometimes.

10. Determine the natural frequencies and mode shapes of the nanotubes discussed in
Problem 7 with appropriate assumptions of the length of the tube, end closures, and
constrained conditions.

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This is only possible in the linear region. If the interatomic potential is approximated as
harmonic, then the frequencies and mode shapes can be obtained by solving a standard
eigenvalue problem based on the equation given in problem 7. The results will be a function of
the length and boundary conditions.

11. Model paired dislocation pileups at a free surface and apply a cyclic load to reveal the
movements of the dislocations.

The proper dislocation pileup is sensitive to the prescribed defects and material systems. Helpful
references on mechanics of nanotubes are below.

References.
1. Belytschko, T., W. K. Liu, et al. (2000). Nonlinear Finite Elements for Continua and
Structures, John Wiley & Sons, LTD.
2. Liu, W. K., J. Sukky, et al. (2006). Computational nanomechanics of materials. Handbook of
theoretical and computational nanotechnology. M. Reith and W. Schommers, American
Scientific Publishers.
3. Qian, D., G. J. Wagner, et al. (2002). "Mechanics of carbon nanotubes." Applied Mechanics
Reviews 55(6): 495-533.

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1.19 Solutions for Chapter 19
Continuum and Atomistic Modeling of Thin Films Subjected to
Nanoindentation by J. David Schall, Donald W. Brenner, Ajit D.
Kelkar, and Rahul Gupta (Solutions by Mark Schulz)

1. Perform a linear finite element simulation of the nanoindentation problem described in

Section 19.1.1 using the same material properties and Berkovich indentor loading.
Generate the force deflection curve. Evaluate the effect of mesh size and perform a
convergence study.

This is a simulation problem suggested for a student project. A literature search could be done to
check if any similar work has been done.

2. Perform a nonlinear finite element simulation of the nanoindentation problem described

in Section 19.1.1 using the same material properties and Berkovich indentor loading.
(Include the effects of material and geometry nonlinearity.) Generate the force deflection
curve. Evaluate the effect of mesh size and perform convergence study. Compare the linear
and nonlinear analysis results.

This is a continuation of the simulation problem 1 suggested for a student project. Again, a
literature search could be done to check if any similar work has been done.

3. Explore the effect of thin film thickness on the nanoindentation results for thin film
thickness greater than 250 nM as well as lower than 250 nM.

Simulation results could be used to answer this question. The following references could also be
consulted:

1. M.Lichinchi, C.Lenardi, J.Haupt and R.Vitali, Simulation of Berkovich nanoindentation

experiments on thin films using finite element method, Thin Solid Films, Volume 312, Issues
1-2 , 14 January 1998, Pages 240-248.
2. Qiuming Wei, Jag Sankar, Ajay Kumar Sharma, Jay Narayan, Effect of Film Thickness on
the Nanoindentation Measurements of Hard Diamondlike Carbon Films Prepared by Pulsed
Laser Deposition, Fall 2000 MRS Meeting, Paper number: Q7.20.

4. Describe the basic differences between the continuum-based finite element approach and
the EAM-based molecular dynamics modeling approach for the nanoindentation problem.

The general approach to model nanoindentation is to use multi-scale models directly to couple a
region described with full atomistic detail to a surrounding region modeled using continuum

90
concepts and finite element methods. The following references provide reviews and a large
number of further references in the area of nano-mechanics.

1. Shengping Shen and S.N. Atluri, Computational Nano-mechanics and Multi-scale Simulation,
CMC, vol.1, no.1, pp.59-90, 2004 Tech Science Press.
2. W.A. Curtin1 and Ronald E Miller, Atomistic/continuum coupling in computational
materials science, IOP, 2003 Modelling Simul. Mater. Sci. Eng. 11 R33-R68.
3. Ting Zhu, Ju Lib, Krystyn J.Van Vliet, Shigenobu Ogataf, Sidney Yipb, Subra Suresha;
Predictive modeling of nanoindentation-induced homogeneous dislocation nucleation in
copper, Journal of the Mechanics and Physics of Solids, 52 (2004) 691 724.

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1.20 Solutions for Chapter 20
Synthesis, Optimization, and Characterization of AlN/TiN Thin
Film Heterostructures by Cindy K. Waters, Sergey Yarmolenko,
Jagannathan Sankar, Sudhir Neralla, and Ajit D. Kelkar

1. Compare the mechanical properties of thin film and bulk of the same material system.

Bulk Elastic Thin film Bulk hardness Thin film

modulus Elastic Hardness
Modulus
AlN 330 GPa 260-350 GPa 12 GPa 18-25 GPa
TiN 250GPa 350-450 GPa 21 GPa 20-40 GPa

Why are thin film properties different from the bulk?

Bonding and mechanical properties
surface atoms have no bonds to atoms above them
can get surface reconstructions
Electrons bounce off the surface as well as off other atoms
electrons travel 10's to 100's of ngstroms before scattering off an atom
if close to surface, may scatter sooner from surface
changes electrical properties in surface region
Chemistry can be different at surface
atoms from bulk may segregate to surface to minimize free energy
impurities from outside environment may be present

2. Describe the role of growth temperatures on the mechanical and the structural
properties of AlN and TiN heterostructures.

There are several steps in Film Formation including; nucleation, surface diffusion, island growth,
coalescence, and continued growth all of which are affected by thermal energy.
The temperature of the substrate has considerable effect on the early development and growth of
the thin film and therefore on the mechanical properties. A higher substrate temperature
increases the atoms energy and therefore their mobility. High temperatures favor rapid and
defect-free crystal growth whereas low temperature may result in disordered or even amorphous
film development. Section 20.5.4.1 discusses that when the temperature is such that a crystalline
film is created the grain size is also affected by the deposition temperature, greater grain growth
will not create the greatest hardness as displayed in Figures 20.36-20.39.

3. Discuss the limitations of nanoindentation technique in the measurement of hardness

and elastic moduli of thin films.

Equation 20.11 displays the relationship between load (P) and the indentor depth of displacement

92
h. The literature generally agrees that indentation with depths of less than 10-20% of the thin
film thickness are desired so that many of the well known limitations and artifacts including;
indentation substrate effects, size effects, tip rounding effects, and surface roughness, will not
occur. Section 20.3.2.4 covers the substrate effect, and 20.3.2.5 covers the Indentation pile-up.
Experimental equipment limitations pose problems in indentation because the equipment may
not pose adequate sensitivity to test at shallow indentation depths. It is likely that the substrate
will affect the final measurements. Pile-up after the indentation as shown in Figures 20.18-19 is a
factor that leads to uncertainty in the nanohardness calculations and must be recognized.

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1.21 Solutions for Chapter 21
Polarization in Nanotubes and Nanotubular Structures by Marco
Buongiorno Nardelli, Serge M. Nakhmanson, and Vincent Meunier

Consider a hypothetical one-dimensional periodic (infinite) system, with lattice constant R

and with a unit cell composed of four atoms numbered 1 to 4 and positioned relative to one
another, as depicted in the figure. At equilibrium the system is such that the net charge on
atoms 1, 2, 3, and 4 is equal to q, q, q, and q, respectively.

1. Assuming that the ionic polarization is given by the dipole moment in a unit cell per unit
volume, explain the apparent discrepancy between the values of the polarization computed
using different choices of supposedly equivalent unit cells A, B, C, and D defined on the
figure.

The ionic polarization P computed in unit cell is given by P = 1 q x

i unit cell
i i , where 1 is

the volume of the unit cell. We get:

PA = 1 [q 0 + ( q) a + ( q) b + q c ] = 1 q ( a b + c )
PB = 1 [( q) a + ( q) b + q c + q R ] = 1 q ( a b + c + R )
PC = 1 [( q) b + q c + q R + ( q) ( R + a )] = 1 q ( a b + c + 2 R )
PD = 1 [q c + q R + ( q) ( R + a ) + ( q) ( R + b)] = 1 q ( a b + c + 3R )
The total dipole moment is not a well defined absolute quantity, since it is defined, as shown in
this simple example, modulo one lattice constant. This uncertainty is formally equivalent to the
2 uncertainty in the Berry phase or to the arbitrariness in the choice of the phase of the Bloch
functions in a calculation based on the Wannier-Function formalism. The origin of this
uncertainty arises from the periodic nature of the system, since any vector, for instance the dipole
moment, is equivalent to any other vector differing by an arbitrary number of lattice vectors.

2. Supposing that the system is truncated into a finite system, find the optimal (in terms of
maximum polarization) way to cut the system, keeping the number of different atomic
species equal. Show that the charge surface actually plays a crucial role in defining the
magnitude of the polarization.

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For the sake of simplicity, lets find the optimal system containing just four atoms and suppose
that b = 2a , c = 3a , and R = 4a . From (1), the largest dipole moment will be found in the system
corresponding to unit cells B (positive) and D (negative), and the two other systems, by
symmetry, do not have a net dipole moment. Now, by simple inspection, one find that the dipole
moment per unit volume, i.e. the polarization, does not vary with the number of atoms added
between the four surface atoms, a fact that confirms that the polarization is merely determined by
the termination, or the charge surface.

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1.22 Solutions for Chapter 22
Multiscale Modeling of Stress Localization and Fracture in
Nanocrystalline Metallic Materials by Vesselin Yamakov, Dawn R.
Phillips, Erik Saether, and Edward H. Glaessgen

1. Identify the differences between sequential and simultaneous multiscale methods. What
are the advantages and disadvantages of each?

Even though the answer to this question is not fully discussed in the text, it brings forth an
important concept in multiscale modeling and is well addressed in the open literature. Sequential
multiscale methods directly join atomistic simulations and continuum field representations such
as finite element analyses enabling a scale-up of results to higher length scales. The benefit of
this approach is the direct linking of atomic and nodal degrees of freedom which allows
straightforward satisfaction of displacement and force continuity. A disadvantage is that special
computations must be performed at the boundary to avoid nonphysical "ghost forces", phonon
reflection, and dislocation pile-up at the atomic-continuum boundary. In comparison,
simultaneous multiscale methods consist of independent analyses performed at different length
scales in which the results of lower length scale calculations (e.g. atomistic simulations) are
homogenized or averaged and used to tune the analysis at the next higher length scale (e.g. finite
element analysis). The disadvantage is that a direct connection between domains is lost and care
must be placed on preserving mechanical conservation relations and total energy balance. This
approach, however, has the advantage of simplifying the analysis and permits a more direct
treatment of phonon and dislocation effects to be passed into the analysis of material behavior at
the next higher length scale.

2. Discuss the considerations related to determining the smallest length scale for which a
continuum model is applicable. Under what conditions do continuum mechanics
assumptions break down? List the sources of error associated with the application of
continuum mechanics constructs at very small length scales.

There is no absolute answer to this question; it depends on the nature of the material and the
mechanisms or responses being simulated. In general, the application of a continuum
representation breaks down at the length scales in which the response of individual atoms are
significant and is a function of the mechanism being simulated. While continuum assumptions
consider deformations as the relative motion of material points with an infinitesimal separation,
deformations at the atomic scale are governed by the motion of discrete atoms within a force
field. Many of the mechanisms of an atomic system can not be directly represented using
continuum mechanics constructs. For example, the multibody force interactions and shielding
effects in a discrete atomic system cannot be directly represented within an elastic continuum
wherein it is assumed that internal forces and deformations are communicated only between
adjacent particles with an infinitesimal separation. Even nonlocal continuum theories cannot
adequately simulate atomic processes because they also average the response over an assumed
volume. Another example is the existence of phonon dispersion, i.e., the dependence of the

96
phonon wave speed on the wavelength as the wavelength approaches the interatomic spacing.
The variable wave velocity cannot be modeled using continuum mechanics but instead requires a
lattice dynamics framework. The wave speed asymptotically approaches a constant value with
increasing wavelength which suggests a length scale at which continuum mechanics can be
applied. Also, quantum-mechanics effects become important at cryogenic temperatures and lead
to anomalies in the thermal conductivity and heat capacity which cannot be adequately
represented by a classical continuum mechanics theory. Finally, continuum plasticity also breaks
down at the atomic scale because the plastic deformation becomes discretely represented by
individual dislocations with a given Burgers vector on a distance no smaller than atomic lattice
spacing. Thus, the nature of the phenomena dictates the length scale at which effective field
properties can be used to successfully utilize a continuum modeling approach.

3. List several nonphysical artifacts that can be generated in modeling small molecular
dynamics systems.

The artifacts that can occur in modeling small molecular dynamic systems are mainly related to
the effects of boundary conditions on the system behavior. In general, boundaries create image
forces which create nonphysical interactions in the system. For example, periodic boundary
conditions, where the system repeats itself at the boundary, produce an infinite number of
periodic images of every perturbation in the system. Fixed boundary conditions, where the
boundary atoms are fixed at certain ideal positions, or free surface conditions, where the system
ends with a free surface, both create image forces of the existing defects in the structure, which
can alter its evolution during simulation. In other cases, such as modeling the physics of crack
propagation, stable far field strain/stress conditions are essential and artifacts may be generated
in modeling small atomic systems due to an incorrect strain/stress field at the crack tip caused by
perturbations due to the proximity of a boundary. It should be noted that techniques have been
developed to mitigate most of these nonphysical artifacts.

4. Discuss several deformation mechanisms that are explicitly modeled by molecular

dynamics analyses that can only be considered in an average sense in finite element
analyses.

Mechanisms that are modeled by molecular dynamic (MD) computational frameworks account
for the interactions within atomic systems and, therefore, represent material behavior at a
fundamental level. Some deformation mechanisms include:

i) Plasticity due to dislocation formation, propagation, interaction, and long-range

influences.
ii) Creep due to diffusion of atoms such as Coble Creep for the case of grain-boundary
diffusion, or Nabarro-Herring creep for the case of transgranular diffusion.
iii) Grain boundary sliding.
iv) Void formation, annihilation and coalescence.
v) Phonon generation and propagation.
vi) Simultaneous plastic and elastic deformation mechanisms at the same applied stress.

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Continuum finite element analyses can account for dynamic effects such as wave propagation,
anisotropic material properties, and nonlinear material behavior such as plasticity. However, the
primary difference from MD is that the domain constitutes an elastic continuum that is defined
by a field of infinitesimal material particles. Thus the discrete interactions of MD must be
represented in a finite element analysis through derived constitutive laws that describe aggregate
atomic behavior and relate element deformations with applied loads. For example, in continuum
analyses, grain boundary sliding and grain separation can be described by traction-displacement
laws that can approximate the atomistic system behavior for use in continuum mechanics
formulations to simulate the rotation and separation of boundaries between adjacent elastic
domains.

5. Why is a columnar microstructural configuration needed in molecular dynamics

analyses to properly correlate with a two-dimensional finite element analysis? In general,
what are some of the advantages and disadvantages of using a two-dimensional model in
these solution methods?

A columnar MD model minimizes the development of atomic mechanisms in the texture

direction and, thus, in specific cases (such as that discussed in Ch. 22) yields a system suitable
for comparison with a two-dimensional continuum approximation. Applying hydrostatic loading
to the atomic system results in a nonzero but constant state of in-plane strains which, in certain
cases, can be approximated using generalized plane strain finite elements. The main advantage of
two-dimensional models compared with three-dimensional models is their simplicity and their
ability to simulate larger in-plane system sizes. In the special hydrostatic load case and system
configuration discussed in Ch. 22, the two-dimensional model is capable of representing the
system response. However, this is not true for general loading cases or three-dimensional
configurations wherein slip systems, grain boundaries and other microstructural features with
dependencies in the texture direction contribute to the overall deformation of the crystal.

6. Discuss the qualitative relationship between the size of a grain and its dominant
deformation mechanism. Under what conditions is grain boundary sliding the dominant
deformation mechanism of a grain? Hint: perform a literature search on the Hall-petch
relationship to gain insight to this question.

It has been empirically established that as the grain size d decreases the material hardness H
increases. This phenomena is expressed by the well-known Hall-Petch relationship:
H d 0.5 .
The conventional explanation of this relationship is that with decreasing the grain size, the role
of grain-boundaries (GBs) as obstacles for dislocation flow is increasing, which results in
material hardening. The Hall-Petch relationship holds for a very large range of grain-sizes, from
the millimeter range down to 100 nm, and is considered almost a universal law. Recent
investigations, though, have shown that there is a deviation from this law for grain sizes smaller
than 100 nm (the range of nanocrystalline materials) and the hardening can be even reversed to
softening for d < 10 nm, a phenomenon called the Inverse Hall-Petch effect. Extensive

98
molecular-dynamics simulations, combined with experimental investigations, showed that the
reason for this anomaly is a change in the deformation mechanisms. While ductile materials of
grain size larger than 100 nm deform mainly through dislocation-governed mechanisms
(dislocation slip or creep), the mechanisms change to GB mediated deformation when grains
become too small to support significant dislocation activity. GB mediated mechanisms, like GB
sliding and GB diffusion (Cobble creep), lead to softening of the material with decreasing grain
size and increasing density of the GB network. GB assisted deformation twinning in ductile
nanocrystalline metals, even in those which do not experience twinning under normal conditions,
such as aluminum, was also found to play an important role as a deformation mechanism.

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1.23 Solutions for Chapter 23
Modeling of Carbon Nanotube/Polymer Composites by Gregory M.
Odegard

1. How does the use of carbon nanotubes as reinforcement in composite materials improve
the mechanical and electrical properties over those of the pure polymer resin?

Pure polymers typically have poor electrical conduction and have mechanical properties that are
inferior to those of other engineering materials, such as metals and ceramics. However, the
addition of carbon nanotubes into a pure polymer (under the right conditions of processing) has
the potential to dramatically improve the electrical conductivity, stiffness properties, and strength
properties of the original polymer. This is due to the atomic structure of nanotubes, in which the
carbon atoms are bonded in a manner that provides for the electrical and mechanical properties.
In general, it is expected that as more nanotubes are added to a polymer resin, the electrical
conductivity, stiffness, and strength of the resulting composite will increase.

2. In what ways do nanotubes offer advantages as polymer reinforcements over graphite

and glass fibers?

Nanotubes are orders-of-magnitude smaller than traditional graphite and glass fibers. Therefore,
for a given volume fraction of reinforcement in a composite material, the surface area available
for load transfer from the polymer to the reinforcement is much greater for nanotube
reinforcement than for fiber reinforcement. Furthermore, for certain types of nanotubes, the
density of reinforcement is smaller for nanotubes than for traditional fibers, making nanotube-
composite structures lighter than fiber-reinforced composite structures. This is particularly
important for the aerospace industry. Finally, because large fibers contain orders-of-magnitude
greater numbers of atoms than nanotubes, individual large fibers have a greater probability of
having defects that lead to fiber failure than do nanotubes. All other factors aside, this factor
leads to a statistically greater expected strength of nanotube-reinforced composites relative to the
strength of fiber-reinforced composites.

3. What information is lost when continuum mechanics-based models are used to describe
the behavior of an atomic structure?

When representing the discrete atomic structure with a continuum-based geometrical description,
all information regarding the atomic structure is lost. Even though the information regarding the
atomic interactions in the equivalent-continuum can be potentially captured, a purely-continuum
model will have no information regarding a discrete geometry. Some equivalent-continuum
models use finite element nodes at the locations of the atoms in the discrete structure. However,
the finite-element mesh is just a tool to describe the behavior of the equivalent-continuum in
general, regardless of the placement of nodes for a specific simulation.

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4. What limits do molecular modeling techniques (MD and ab initio simulations) have in
predicting behavior of heterogeneous materials?

Two major limitations exist. The first is the inability of molecular modeling techniques to
simulate the mechanical behavior of materials at time scales that are relevant for engineering
applications. While bulk material behavior is usually experimentally observed and designed for
time intervals on the order of seconds, minutes, hours, or days, molecular modeling simulates the
motions of atoms on the order of femto-, pico-, or nanoseconds. Some molecular models, such as
Monte Carlo simulations, have a simulation time that does not clearly correspond to any real
time scale. The second major limitation exists in the size of a molecular system that can be
simulated. In engineering applications, most materials are designed on the micrometer level and
above. However, molecular simulations performed on the majority of research-grade computers
can only simulate molecular systems with length scales in the nanometer range. Even though
techniques exist to approximate molecular interactions on larger scales, these approximations
loose details concerning the atomic interactions.

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1.24 Solutions for Chapter 24
Introduction to Nanoscale, Microscale, and Macroscale Heat
Transport: Characterization and Bridging of Space and Time Scales
by Christianne V.D.R. Anderson and Kumar K. Tamma (Solutions
by Mark Schulz).

1. Identify the various methods (classical and nonclassical) existing in the literature for the
prediction of thermal conductivity at scales ranging from nanoscale to macroscale regimes.

This chapter is important because it provides a treatment of heat conduction from the nanoscale
to the macroscale in one place. The problems for this chapter are open-ended and require quite a
bit of time to solve. A starting point to tackle the problems is to conduct a thorough review of the
current literature. The literature review will provide references on traditional approaches and also
help to uncover the latest approaches for example to develop multiscale methods suited for
modeling large scale applications on large computer platforms. Some suggestions for solving the
problems are given below. For a start on the literature survey, see:

1. Nano/microscale Heat Transfer by Zhuomin Zhang, McGraw-Hill, expected publication in

2007.
2. J. R. Lukes, A. R. Abramson, and J.-G. Weng, 2005, "Nanoscale Thermophysical
Phenomena from Molecular Dynamics Simulation: Recent Advances," in Annual Review of
Heat Transfer: In Memory of Chang-Lin Tien, Vol. 14, V. Prasad, Y. Jaluria, and G. Chen,
eds.,Begell House, Inc., New York, pp. 197-224.
3. G. Chen, A. Majumdar, and J. R. Lukes, 2005, "Chang-Lin Tien's Contributions to Micro and
Nanoscale Heat Transfer," in Annual Review of Heat Transfer, Vol. 14, V. Prasad, Y. Jaluria,
and G. Chen, eds., Begell House, Inc., New York,pp. 97-102.

2. Conduct a thorough literature review and point out the limitations cited in the literature
for the classical models. Verify these limitations using examples in the literature. Conduct
the same for nonclassical models.

See above references for a start.

3. Derive the C- and F-processes constitutive model and understand the notion of spanning
ballistic to diffusive limits and finite to infinite speeds of heat propagation. Since the
method is not computationally intensive, verify some numerical examples such as thin films,
superlattices, thermal contact conduction/resistance, and the like.

New heat transport models are described in [1,2]. The model in [2] is founded on an underlying
unified theory stemming from the physics of the Boltzmann transport equation. The model
simultaneously represents the slow C processes at low energies and the fast F processes at high
energies as heat carriers. The model also describes heat transport characteristics spanning both

102
spatial (characterizing ballistic to diffusive limits) and time scales (characterizing finite to infinite
heat propagation speeds).

1. Xiangmin Zhou, Kumar K. Tamma, Christianne V.D.R. Anderson, On a New C- and F-

Processes Heat Conduction Constitutive Model and the Associated Generalized Theory of
Thermoelasticity, http://citeseer.ist.psu.edu/440866.html.
2. Christianne V. D. R. Anderson and Kumar K. Tamma, Novel Heat Conduction Model for
Bridging Different Space and Time Scales, , Phys. Rev. Lett. 96, 184301 (2006).

4. Investigate methods that are not computationally intensive yet do not require fitting
parameters. For example, look into coupling the C- and F-processes model with variants
that are less cumbersome to molecular dynamics to circumvent potential limitations.

Start with above references.

5. Develop multiscale methods suited for modeling and simulation of large scale
applications on modern high-performance computing (HPC) platforms.

Simulation of microscale and nanoscale heat transfer has lead to the development of a variety of
models and numerical methods [1,2]. These models include direct simulation methods using
molecular dynamics, various models with different accuracy based on the Boltzmann transport
equation, and hyperbolic extensions of the classical Fourier heat conduction equation. Problems
involving conduction, convection, and radiation are typically solved using the heat transfer
modules in existing finite element codes [1]. The simulations are used extensively in systems
that involve heat generation and flow in any form. The physics that is modeled includes transient
conduction heat transfer, enclosure radiation, chemistry, phase change with moving surfaces,
coupling to fluid mechanics and solid mechanics codes, and problem sizes of several million
elements that are scalable to several thousand processors. Some references to investigate are
below.

1. http://www.comsol.com/
2. Jayathi Y. Murthy et al, International Journal for Multiscale Computational Engineering,
ISSN 1543-1649, 2005, Volume3, Review of Multiscale Simulation in Submicron Heat
Transfer.
3. http://www.algor.com/products/ALGNAS1755/default.asp
4. http://www.ugs.com/products/nx/docs/fs_nastran_basic.pdf
5. http://www.nenastran.com/newnoran/pdf/NEL1_v90.pdf
6. http://www.mscsoftware.com/products/msc_nastran.cfm?Q=396&Z=422

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