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SPRINGER BRIEFS IN MATERIALS
Ronald L. Poveda
Nikhil Gupta
Carbon Nanofiber
Reinforced
Polymer
Composites
123
SpringerBriefs in Materials
More information about this series at http://www.springer.com/series/10111
Ronald L. Poveda · Nikhil Gupta
Carbon Nanofiber
Reinforced Polymer
Composites
13
Ronald L. Poveda Nikhil Gupta
Department of Mechanical Department of Mechanical
and Aerospace Engineering and Aerospace Engineering
Polytechnic School of Engineering Polytechnic School of Engineering
New York University New York University
Brooklyn, NY Brooklyn, NY
USA USA
ISSN 2192-1091 ISSN 2192-1105 (electronic)

SpringerBriefs in Materials
ISBN 978-3-319-23786-2 ISBN 978-3-319-23787-9 (eBook)
DOI 10.1007/978-3-319-23787-9
Library of Congress Control Number: 2015948858
Springer Cham Heidelberg New York Dordrecht London

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Preface
Unprecedented growth in the applications of composite materials has been

observed in the past 10 years. Many commercial aircraft and passenger cars are
now using composite materials. High cost of raw materials, intense labor depend-
ence, and property variations from batch to batch were some of the factors against
composite materials in their initial years of development, which are now slowly
being overcome to enable many mainstream applications. As a variety of fiber
and particle reinforced polymer matrix composites find applications in bulk quan-
tities, the quest for improved next generation composites continues. Composites
with nanoscale reinforcement, commonly referred to as nanocomposites, are now
a major focus area in academic and industrial research laboratories.
Carbon nanofibers (CNFs) are one-dimensional nanoscale fibers that have
outstanding mechanical, thermal, and electrical properties. CNFs have been

considered for use in several specialty and commercial applications, including
those in the aerospace, automobile, and marine industries. CNFs can be useful in
enhancing and tailoring the properties of polymer matrix composites without a
significant increase in bulk composite density. Such a consideration is critical for
weight-saving structural applications.
The physical properties of polymer composites can be enhanced to a great
extent through designed dispersion of CNFs. Such effects correspond to the struc-
ture and innate properties of CNFs, as well as how the composite is fabricated and
processed. The structure of CNFs can vary depending on the fabrication method,
thus resulting in varied strength and stiffness properties. Further processing such
as additional heat and chemical treatment can result in further fiber structure and
surface tailorability, which can lead to improved polymer composite performance
when incorporated. Inclusion of CNFs has also demonstrated unique fracture fail-
ure mechanisms under various loading modes, as well as a range of loading rates.
From the vast body of literature on CNFs and their composite materials, it is
possible to miss some contributions in the references. We have primarily covered
the information available in journal publications. Conference publications and
theses/dissertations are referred only if some critical information not available in
peer-reviewed journals was taken from them. The field continues to evolve at a
v
vi Preface
rapid pace. We hope that this brief book will provide a starting point for interested
readers to gain a basic understanding about the major material parameters and
mechanical properties of CNFs and their nanocomposites. Readers can use the
cited references for detailed information.
Brooklyn, NY, USA Ronald L. Poveda

Nikhil Gupta
Acknowledgments
The authors wish to thank a number of people who contributed to the research
related to CNF reinforced polymer composites in their group over the past decade.
These individuals include Dr. Vasanth C. Shunmugasamy, Dr. Dinesh Pinisetty,
Dr. Dung D. Luong, Dr. Gabriele Tagliavia, Dr. Michele Colloca, Sriniket Achar,
Dennis John, Gleb Dorogokupets, Andres Donoso, Matthew Moore, Matthew
Labella, and Steven E. Zeltmann. Diligent work by these current and past p ostdocs
and students resulted in several publications that became the basis for developing
this book. Assistance in manuscript editing by Dr. Christopher Thajudeen is
appreciated.
Parts of this work were supported by the Office of Naval Research grant
N00014-10-1-0988, Army Research Laboratory cooperative agreement
W911NF-11-2-0096, and National Science Foundation grant IIA-1445686. The
views and conclusions contained in this book are those of the authors and should
not be interpreted as presenting the official policies or position, either expressed or
implied, of the ONR, ARL, NSF, or the U.S. Government unless so designated by
other authorized documents.
vii
Contents
1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Polymer Matrix Composites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.1 Classification of Composite Materials. . . . . . . . . . . . . . . . . . 4
1.1.2 Hybrid and Multiscale Composites . . . . . . . . . . . . . . . . . . . . 7
1.2 Introduction to CNF/Epoxy Composites. . . . . . . . . . . . . . . . . . . . . . 8
1.3 Organization of the Present Book . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2 Carbon Nanofibers: Structure and Fabrication. . . . . . . . . . . . . . . . . . . 11

2.1 Structure and Fabrication. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.1.1 Vapor Grown CNFs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.1.2 Electrospun CNFs (ECNFs). . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.1.3 Comparison of VGCNFs and ECNFs. . . . . . . . . . . . . . . . . . . 15
2.2 Measured Mechanical Properties of CNFs. . . . . . . . . . . . . . . . . . . . . 16
2.3 CNF Surface Enhancement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.4 Modeling of Mechanical Properties of CNF . . . . . . . . . . . . . . . . . . . 21
2.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3 Mechanical Properties of CNF/Polymer Composites . . . . . . . . . . . . . . 27

3.1 Literature Review. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.2 Tensile Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.3 Compressive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3.4 Flexural Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.5 Other Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.6 Common Analytical Models for Experimental Validation. . . . . . . . . 38
3.7 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
ix
x Contents
4 Environmental Effects on CNF/Polymer Composites. . . . . . . . . . . . . . 43

4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.2 Studies on Moisture Effects on Polymers
and Fiber Reinforced Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
4.3 Investigations on CNF/Polymer Composites. . . . . . . . . . . . . . . . . . . 47
4.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
5 Thermal Expansion of CNF/Polymer Composites. . . . . . . . . . . . . . . . . 53

5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
5.2 Thermomechanical Analysis Methods. . . . . . . . . . . . . . . . . . . . . . . . 54
5.3 Experimental and Analytical CTE Investigations . . . . . . . . . . . . . . . 55
5.3.1 Experimental Results. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
5.3.2 Analytical Modeling CTE of CNF/Epoxy Composites. . . . . 58
5.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
6 Dynamic Mechanical Analysis of CNF/Polymer Composites. . . . . . . . 63

6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
6.2 Dynamic Mechanical Analyses of CNF/Polymer Composites. . . . . . 64
6.3 Results and Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
6.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
7 Electrical Properties of CNF/Polymer Composites. . . . . . . . . . . . . . . . 71

7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
7.2 Electrical Impedance Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
7.3 Results and Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
7.4 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
8 CNF Reinforced Multiscale Composites. . . . . . . . . . . . . . . . . . . . . . . . . 77

8.1 Composites with Three or More Phases. . . . . . . . . . . . . . . . . . . . . . . 78
8.2 Mechanical Properties of Multiscale Composites . . . . . . . . . . . . . . . 79
8.2.1 Additional Reinforcement and Fillers . . . . . . . . . . . . . . . . . . 79
8.2.2 Compressive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
8.2.3 Flexural Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
8.2.4 Interlaminar Shear Strength and Fracture Toughness . . . . . . 89
8.2.5 Dynamic Mechanical Analysis. . . . . . . . . . . . . . . . . . . . . . . . 91
8.3 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Chapter 1
Introduction
Abstract The benefit of achieving multifuctionality has been a strong driving

force behind increasing interest in lightweight polymer matrix nanocomposites.
Versatile, lightweight structural designs can be developed through tailoring the
mechanical, thermal, and electrical properties of polymer matrix composites,
especially those utilized in the aerospace, marine, and automobile industries.
Utilization of novel reinforcement materials such as carbon-based nanostructures
in an effort to enhance a composite’s properties has proven to be useful for a pleth-
ora of structures with strict design requirements. This chapter intends to provide
an opening review on polymer matrix composites, especially those reinforced with
carbon microfibers and carbon nanofibers (CNFs). Some of the recent applications
of carbon microfiber reinforced composites in modern automobiles are shown.
However, the desire to fabricate composites with further improved properties and
performance has led to exploration of CNFs as a new reinforcement. Cost and
weight-saving remain crucial factors that determine industrial viability of CNFs.
Through the use of reinforcement such as CNFs, resultant composites have been
shown to exhibit enhanced properties such as strength, thermal stability, and ther-
mal and electrical conductivities, all with negligible variation in the density.
Keywords Composite materials · Nanocomposites · Carbon nanofiber ·

Reinforcement · Fiber · Particle
Polymer matrix composite (PMC) materials have been the materials of choice for
a plethora of industrial and commercial applications due to ease in fabrication and
reinforcement dispersion, better chemical resistance, higher toughness, and lower
weight compared to metals, ceramics, and their composites [1–3]. Fabrication
of PMCs is more cost-effective than the fabrication of ceramic and metal matrix
composites because polymers can be processed at lower temperatures. Micro and
nanoscale fibers in PMCs are expected to bridge cracks and improve strength and
energy absorption under tensile and flexural loading conditions. Numerical studies
have shown that the orientation of fibrous reinforcement significantly affects
© The Author(s) 2016 1

R.L. Poveda and N. Gupta, Carbon Nanofiber Reinforced Polymer Composites,
SpringerBriefs in Materials, DOI 10.1007/978-3-319-23787-9_1
2 1 Introduction
the stress distribution in the composite. Interesting results can be obtained when
particles and fibers are simultaneously present in the composite and the location of
maximum stress can be tailored to be either in the fibers or in the particles [4].
In particulate composites, the discontinuous structure of reinforcement makes
the tensile properties very sensitive to the properties of the matrix material.
Experimental studies have shown brittle tensile behavior of epoxy and vinyl ester
matrix composites. It is also observed that the failure under flexural loading condi-
tions usually starts from the tensile side of the specimens and the flexural proper-
ties are closely related to the tensile response of the epoxy and vinyl ester matrix
composites. Micro and nanoscale reinforcements, such as glass microfibers, nano-
clay, and carbon nanofibers (CNFs), have been incorporated in polymer resins that
are used in fabricating particulate composites to also improve their tensile proper-
ties [5, 6].
In the past decade, the use of PMCs has increased rapidly due to an interest
in reducing the weight of structures in all modes of transportation. Increasing
demand for lightweight materials has led to the development of composite materi-
als parts for several non-load-bearing and load-bearing components. It is estimated
in market studies that the composite materials market is growing globally with a
growth rate of 6 % for the past several years and this rate will continue in the near
future.
A vast variety of PMCs are now available commercially. A large number
of standard text and reference books are available for various types of compos-
ite materials. The available texts range from fundamental aspects of composites
design to advanced mechanics methods for composites analysis [7–9]. A typical
classification of PMCs is discussed in the next section. However, the ever-increas-
ing variety in composite materials can go beyond these traditional categories.
1.1 Polymer Matrix Composites
PMCs are materials that contain fillers or reinforcement phases in a continuous

polymer matrix. A wide variety of PMCs is now available for industrial applica-
tions. Among the available PMC types, fiber and fabric reinforced laminates, par-
ticle reinforced composites, and sandwich structures are now available. PMC parts
are now used in many high performance and production cars. The current state of
the art in applications of PMCs in the automotive sector is captured in the example
presented below. This example covers a high-end performance car that is very sen-
sitive to weight reduction in order to maximize performance.
Some of the parts made of carbon fiber reinforced composites used in a lim-
ited production run high-end Maserati Granturismo MC Centennial are shown in
Figs. 1.1 and 1.2. Some of the large size parts made with main consideration of
weight saving are shown in Fig. 1.1. Examples shown in this figure include the
complete front hood and the seat frames. Many other cars have now used seat
frames of similar carbon fiber reinforced composite construction. In addition,
1.1 Polymer Matrix Composites 3
Fig. 1.1 a Front hood, b front seat frame, c door inserts and d rear spoiler. All images were
taken at the 2015 NY International Auto Show
components such as door inserts can benefit from the impact resistance and energy
absorption capability of carbon fabric laminates. Another large size part is the rear
spoiler, which is also carbon fabric reinforced composite construction. These large
size functional components made of composites are encouraging because early
adoption by limited production run cars will slowly percolate to a wider range
of automobiles as the industry gains confidence in the long-term performance of
composites. In addition, increase in adoption of such components will bring their
cost down, further accelerating the applications.
The Maserati Granturismo MC Centennial also has several small components
made of composites. While every gram of weight saved is useful, many of these
components, shown in Fig. 1.2, appear to be selected from a style and aesthet-
ics perspective. The examples included in Fig. 1.2 represent the front dashboard
trim, rear view mirror casing, exterior door handle, and steering wheel mounted
paddle shifters. Clear finish laminates with carbon fabric texture look attractive
and visibly place the use of high-end carbon composite materials, which is appeal-
ing. Among these components, the rear view mirror casing application seems to be
4 1 Introduction
Fig. 1.2 a Dashboard trim, b rear view mirror case, c exterior door handle and d steering wheel
mounted pedal shifters. All images were taken at the 2015 NY International Auto Show
gaining traction very fast in the industry as several production models of other cars
have also adopted it for the 2016 model year.
Although the range of available PMCs is difficult to define in one clear set of
classifications, an illustration of the variety of composites is presented in Fig. 1.3.
It can be observed in the figure that numerous classes of composites can be devel-
oped and a variety of keywords are required to properly define a given composite
material. Fiber length, spatial orientation, and diameter are important parameters
for fiber reinforced composites. Particle reinforced composites also have several
classes based on the particle shape, porosity configuration, and distribution. There
are many examples such as multiphase composites containing more than one type
of reinforcement, which cannot be covered within one category. This classification
can be expanded to add more information as per the requirement.
1.1.1 Classification of Composite Materials
A few classes of PMCs commonly referred to in the published literature are briefly
discussed below to define their most important characteristics.
Sandwich Bulk Solid

Laminates Structure Mixture
Ceramic
In-situ
(Aluminides,
Precipitates
Carbides,
(chemical
etc.)
Composite reactions)
Structure
Polymer Composite Fibrous

Composite
(Thermoplastic/
Thermoset) Matrix
Composites Reinforcement
(Continuous/
Discontinuous)
Particles
Metal
(Solid/Hollow)
(Pure/Alloys)
Fig. 1.3 Classification of composite materials
• Fiber reinforced composites

Fiber reinforced composites have been extensively studied. The interest in these
composites is mainly because of their very high strength and modulus in the direc-
tion of fibers. There are several possible reinforcing configurations for fibers, some
of which are identified below:
– Continuous fiber reinforced composites
○ Aligned unidirectional fiber reinforced composites
○ Aligned bi- or multidirectional fiber reinforced composites
○ Random fiber reinforced composites
– Fabric reinforced laminates

○ Plain weave fabric reinforced composites
○ Triaxial weave fabric reinforced composites
○ 3D weave fabric reinforced composites
– Discontinuous fiber reinforced composites

○ Microfiber reinforced composites
○ Nanofiber reinforced composites
The examples for each category are listed only for illustrative purposes. A large
number of other subcategories can be identified depending on the fiber or fabric
type. Several large-scale applications of fiber reinforced composites are now avail-
able, which include the fuselage section of the Boeing 787 Dreamliner airplane.
The high mechanical properties of these composites are advantageous in keeping
the structural weight low, which is useful in weight sensitive applications such
6 1 Introduction
as aircraft and spacecraft structures. Consumer products such as laptops and cell
phone cases, suitcases, and furniture are also examples where fiber reinforced
composites are finding applications.
• Particle reinforced composites
The interest in particle reinforced composites has been growing in recent years.
One of the main advantages of these composites is their low raw material cost and
lower processing cost compared to fiber reinforced composites. In addition, parti-
cle reinforced composites can have isotropic properties if the particle size is small
enough compared to that of the component dimensions. Particle reinforced com-
posites can be divided into the following categories:
– Solid particle reinforced composites
– Hollow particle reinforced composites
Hollow particle filled composites are gaining new applications because of their
low density, high compressive energy absorption capability, and large failure
strain. In both solid and hollow particle filled composites, industrial waste mate-
rials have been used as fillers or reinforcements. For example, hollow and solid
ceramic particles found in fly ash are beneficial as fillers. Glass, alumina, silica,
and silicon carbide are among other materials that are widely used as reinforcing
particles. All these materials are available as solid and hollow particles in a wide
range of sizes from nanoscale to macroscale.
• Nanocomposites
Nanocomposites are defined as composite materials that are reinforced with a
phase that has at least one dimension smaller than 100 nm. Although these com-
posites can form subcategories in particle and fiber reinforced composites,
the main reason to classify them separately is that the mechanisms of interac-
tion between the reinforcement and matrix are different at the nanoscale and
lead to significantly higher properties than those expected by scaling laws.
Nanocomposites can be divided into the following subcategories:
– Nanofiber reinforced composites
– Nanotube reinforced composites
– Nanoplatelet reinforced composites
– Nanoparticle reinforced composites
Carbon-based nanomaterials have been widely studied as reinforcements. Their
most common examples are carbon nanotubes (CNTs) and graphene for nanotubes
and platelets, respectively. An overview and structure of some of the carbon-based
nanomaterials is shown in Fig. 1.4 [10].
Nanotubes of boron nitride, silicon nitride, zinc oxide, and many other materi-
als have been synthesized. Among platelet reinforced composites, nanoclay is an
example of a widely used filler. Low cost and abundant availability of high quality
nanoclay favors its use as fillers. The possibility of creating functional compos-
ites with only a small volume fraction of nanotube or nanoplatelet reinforcement
is very attractive. Among the functionalities that have been explored or envisioned
Fig. 1.4 An overview of carbon-based nanomaterials widely used in composite materials [10]
are the possibilities of using nanotubes for energy storage, self-healing, and shape
morphing. CNTs and graphene have also been used to synthesize conducting or
semiconducting composites using insulating matrix materials.
Nanoparticles of a large number of materials, for example alumina, silicon car-
bide, boron nitride, diamond, and carbon, have been used for synthesizing nano-
composites. Lower cost of dispersing nanoparticles compared to other types of
nanoreinforcements is in their favor.
The recent literature shows some very interesting possibilities with CNF rein-
forcement of polymers. Lower cost of these fibers compared to CNTs yet high
level of mechanical properties and electrical and thermal conductivity benefit
many applications where cost is of concern. Nanofibers of zinc oxide, alumina,
silica, and many other ceramics are now available.
1.1.2 Hybrid and Multiscale Composites
In hybrid composites, reinforcements of two different morphologies may be incor-

porated to obtain benefits specific to both reinforcement types. For example, both
solid and hollow particles may be dispersed in a composite. In another possible
8 1 Introduction
Fig. 1.5 Scanning electron
micrograph of a hybrid
composite containing glass
hollow particle and short
glass fiber reinforcements in
epoxy matrix
case, which is shown in Fig. 1.5, glass hollow particles and glass fibers are used
together as reinforcement in a composite. In this case glass hollow particle filler is
used for lightweight and high stiffness under compression. However, tensile prop-
erties of such composites (called syntactic foams) can be poor, which are improved
by simultaneous fiber reinforcement. Such clear objectives achieved by a combina-
tion of reinforcements is an important aspect of the tailoring of the composites.
In many cases a composite can be classified into more than one category. For
example, fuzzy fiber reinforced composites have CNFs grown on microfibers,
which are used as reinforcement [11–14]. Such composites can be complex exam-
ples of multiscale reinforcement. There are numerous other studies available on
composites where fibers or particles of different length scales are used together to
benefit from the strengthening mechanisms offered by them [15–17]. In other type
of composites, CNT and fiber reinforced laminates have been fabricated [18–20].
It is known that laminates have high mechanical properties in the fiber directions
but their through-the-thickness properties can be poor. CNT impregnation of resins
has shown to improve the mechanical properties of laminates.
1.2 Introduction to CNF/Epoxy Composites
The high level of interest in CNFs has led to a vast amount of literature investi-
gating their physical structure as well as their mechanical, thermal, and electrical
properties. Understanding the structure and properties of individual CNFs is criti-
cal to understanding their effects on the properties of composites. Development
of synthesis methods that can provide large quantities of high quality CNFs at
low cost is also a priority area. Dispersion of long aspect ratio CNFs in polymers
remains a significant challenge. Surface treatments have tried to address the CNF
dispersion issues. In addition, several processing methods are available now for
1.2 Introduction to CNF/Epoxy Composites 9
CNF reinforced composites. Various chapters of this book are devoted to these
aspects, including synthesis and properties of CNFs and synthesis and properties
of CNF reinforced composites.
1.3 Organization of the Present Book
The main focus of this book is CNF reinforced polymer matrix composites. In
some cases multiphase composites containing CNF in the presence of an addi-
tional reinforcement phase are studied. Chapter 2 is devoted to CNF fabrication
methods and characterization studies, Chap. 3 is focused on the mechanical prop-
erties of CNF reinforced composites and Chap. 4 is focused on environmental
effect of CNF reinforced composites. Chapter 5 deals with thermal properties of
CNF/epoxy composites. The discussion on temperature-dependent properties con-
tinues in Chap. 6, which is focused on dynamic mechanical analysis of a wide
range of temperatures and frequencies. Electrical properties are covered in
Chap. 7. Multiscale composites containing CNF reinforcement along with at least
one more phase are discussed in Chap. 8.
References
1. Al-Saleh, M. H., & Sundararaj, U. (2009). A review of vapor grown carbon nanofiber/polymer
conductive composites. Carbon, 47(1), 2–22.
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10 1 Introduction
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(2014). Low temperature growth of carbon nanotubes on carbon fibre to create a highly net-
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characterization of piezoresistivity in fuzzy fiber reinforced polymer composites. International
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2009–2015.
Chapter 2
Carbon Nanofibers: Structure
and Fabrication
Abstract In this chapter, vapor-grown and electrospun carbon nanofibers (CNFs)

are emphasized. Fabrication processes and surface modification methods for
CNFs are presented. Microstructure of CNFs is discussed based on the reported
observations in various studies. CNFs have a complex structure compared to the
structure of carbon nanotubes. The orientation of carbon layers in CNFs affects
their mechanical properties. Experimental analyses and resulting trends are dis-
cussed from various published works, such as studies that investigate the tensile
and flexural properties of individual CNFs. The range of measured properties is
rather wide, which is likely due to the difference in the structure of the fibers that
were tested and the presence of defects. Molecular dynamic simulation results on
single nanofibers are also presented to understand their potential of reinforcing
composites.
Keywords Carbon · Nanofibers · Nanotube · Vapor-grown · Electrospinning ·
Polyacrilonitrile · Molecular dynamics
The potential of using carbon-based nanofibers as reinforcement has been recog-

nized since the 1980s for both vapor-grown [1] and polyacrilonitrile (PAN)-based
[2] carbon fibers, among other fiber types. Obtaining control over the fiber prop-
erties through manipulation of process parameters was of great interest during
earlier studies. A similar trend was observed with the development of CNFs. The
research continued with measuring the properties of single CNFs and then with
synthesis and characterization of CNF reinforced composites. Modeling and simu-
lation studies were useful in understanding the nature of CNFs and in understand-
ing the potential benefits of using such nanofibers in composites. Comprehensive
literature reviews highlighting the mechanical properties of CNF-reinforced poly-
mer composites have been previously published [3–6]. These reviews can be of
great help in developing the background of CNF reinforced composites.

12 2 Carbon Nanofibers: Structure and Fabrication
2.1 Structure and Fabrication
CNFs have been classified as linear, sp2-based (one double bond, with two s ingle
bond) discontinuous filaments, where the aspect ratio is greater than 100 [7].
Transmission electron microscopy (TEM) revealed that the layers of graphitic
planes of most CNFs are generally not aligned along the axis of the fiber.
Nanoscale filaments such as CNFs have even been classified in previous works as
follows, depending on the angle of the graphene layers that compose the filament
[8]:
• Stacked (graphene layers stacked perpendicular to the fiber axis)
• Herringbone/Cup-stacked (graphene layers stacked at an angle between parallel
and perpendicular to the fiber axis).
These layering arrangements are possible, due to the growth mechanism of the
CNF that depends on the geometric facets of a metallic catalyst particle and the
gaseous carbon feedstock (hydrocarbon or CO gas) that is introduced during CNF
processing. Such general classifications leave further room for additional catego-
ries of carbon-based nanoscale fibers; however, the discussion will be limited to
the more common types known henceforth as vapor-grown CNFs (VGCNFs) and
electrospun CNFs (ECNFs). The inherent structure of CNFs is usually dependent
on the production processes employed, as described in the following sections for
both VGCNFs and ECNFs.
2.1.1 Vapor Grown CNFs
The structure of VGCNFs resembles graphene layers helically folded along the
axis of the fiber, providing a hollow core. The graphitic layers are folded at an
angle to the fiber axis, giving the appearance of cups that are layered, or “stacked”
one on top of the other along an axis, as shown in the simplified diagrams of
Fig. 2.1 [6, 9]. Such a “cup-stacked” structure distinguishes them from CNTs,
which have the appearance of a single cylinder or multiple concentric cylinders
made of graphene layers oriented parallel to the CNT axis. An available TEM
image demonstrates unfurling of a graphene layer in a CNF, as shown in Fig. 2.2
[10], thereby providing direct visual evidence and confirming the continuity of the
stacked layers in the form of helical folding. The hollow core graphitic inner layer
and a turbostratic carbon outer layer structure are further shown in high resolution
TEM images in Fig. 2.3. The current literature has attempted to develop a prac-
tical definition of CNFs by stating that carbon-based nanofibrous structures with
nonzero angles with respect to the fiber axis are to be deemed as CNFs [8, 11, 12].
The structure and properties of VGCNFs are influenced by their fabrica-
tion process. The processes that are used for CNF production have been around
since the 1970s for producing other materials and have been adapted for CNF
2.1 Structure and Fabrication 13
Fig. 2.1 a 3D CAD rendering of cup-stacked graphene layers in a single CNF, and b Simplified
schematic of stacked-cup carbon nanofiber helical structure with inset in (b) showing TEM image
of inclined orientation of grapheme planes along the side of structure with respect to nanofiber
axis. Image taken with permission from [9]
production in the recent years [1, 6, 8]. Chemical vapor deposition (CVD) is
among the most common processes used for producing VGCNFs. Transition metal
catalytic particles such as iron, nickel, cobalt, and copper are utilized in conjunc-
tion with a carbon supply, such as carbon monoxide or a hydrocarbon gas, at
temperatures ranging from 500 to 1200 °C in the CVD process [13]. The size of
the catalyst particle determines the size of the graphitic structure of CNFs [14].
Several models have been proposed to explain the growth of the graphitic struc-
ture through the use of metal catalysts [15, 16]. The size of the catalyst parti-
cles is usually in the range 10–100 nm, which determines the outer diameter of
the CNFs produced [8, 16]. The angle at which the “cups” are oriented strongly
affects the properties of CNFs [8, 17, 18]. A faceted catalyst particle may allow
for the formation of angled layers where graphitic platelets are deposited at an
angle leading to growth of CNFs. A simple schematic illustration of this process
is shown in Fig. 2.4a. In contrast, a spherical catalyst particle results in graphitic
layers which are parallel to the growth axis, allowing for the formation of single-
walled or multi-walled CNTs [7, 8]. Experimental analyses on CNFs denoting the
effect of varying cone angles are not yet available. However, atomistic simulations
have revealed that the fiber stiffness and failure mode are a function of cone angle,
Fig. 2.2 TEM image of the unfurling of one end of a VGCNF. The continuity of the fiber
explained the electrical conductivity of the nanofibers in previous studies. Image taken with
permission from [10]
Fig. 2.3 a TEM images of a single VGCNF with a hollow core, inner graphitic layers, and outer
turbostratic carbon layers. b Higher magnification TEM micrograph of hollow core structure
surrounded by carbon layers
which can vary within a rather large range (38.9°–112.9°) [18]. Advances in CVD-
based methods, such as plasma-enhanced CVD, allow for use of glow discharge
plasma for production of carbon nanostructures at considerably lower tempera-
tures (T ≥ 650 °C) than traditional CVD methods [12].
2.1 Structure and Fabrication 15
2.1.2 Electrospun CNFs (ECNFs)
An alternate route to the production of CNFs is through electrospinning [19]. The

electrospinning process is schematically illustrated in Fig. 2.4b. A fine tip needle
syringe is used in this sol–gel process. High voltage is applied to the droplet at the
tip of the needle, which causes the solution to spurt out from the needle to a target.
When the surface tension is high enough for the solution to prevent breaking into a
fine droplet, a fibrous structure is developed and collected at the target. Polymeric
precursors used in this process have included PAN, cellulose, and pitch, where
PAN is the most desirable and most often used due to its higher carbon yield and
strength [7, 20], as well as its ease of fabrication and mass-production [19, 21].
A heterogeneous “skin-core” structure is observed in ECNF in Fig. 2.5, where
the carbon layers are oriented radially along the fiber skin, but a randomized gran-
ular structure is observed along the axis of the fiber core [22]. It is proposed that
the skin–core structure is formed because of shear forces exerted on the fiber due
to the variation in inner and outer fiber temperatures encountered during the elec-
trospinning process [23].
2.1.3 Comparison of VGCNFs and ECNFs
The CVD process generally tends to yield ultra-high modulus CNFs [7, 24].
However, a significant amount of catalyst residue, relatively lower product yield,
and use of expensive equipment are the limitations of the CVD process [19].
Compared to the “bottom-up” method of production employed by CVD, elec-
trospinning takes advantage of its “top-down” manufacturing process, which
facilitates production, assemblage, and alignment [21]. The CVD process pro-
duces fibers that are difficult to align without the use of magnetophoretic or
(a) (b)
Primary Oblique Turbostratic
T=~1100
Graphene Layers Carbon
Layers
Gaseous Carbon
Supply
(CO or
Hydrocarbon Gas) Hollow
Core
Metallic
Catalyst
Particle
Substrate
Fig. 2.4 a Schematic of chemical vapor deposition (CVD) process with illustration of CNF lay-
ering, and b Schematic of electrospinning of PAN fibers, which is typically followed by stabiliza-
tion and carbonization to create CNFs. Image taken with permission from [19]
Fig. 2.5 TEM micrographs of broken edges of carbonized ECNFs with a loosened outermost

layer, and b several sheath layers can be observed at the edge. Images taken with permission
from [22]
electrophoretic methods, as well as mechanical methods such as screw extrusion

[25–27]. Both methods of CNF production are continuously refined to efficiently
produce higher CNF yields for mass production.
Due to the heterogeneity of the skin–core structure of ECNFs, the cup-stacked
structure of VGCNFs offers distinct advantages with respect to mechanical proper-
ties. However, the crystallinity of the ECNF structure can be manipulated through
further high-temperature carbonization, thus prompting enhancements in mechani-
cal strength. The strength and modulus values of both types of CNFs are discussed
in detail in the following section.
2.2 Measured Mechanical Properties of CNFs
Direct measurements of mechanical properties were conducted on individual

CNFs [4, 22, 24, 28–31]. Analytical predictions and finite element simulations
require such values for validation and to analyze associated data trends and mech-
anisms of composite reinforcement using CNFs [6, 17, 18, 32–35]. Table 2.1 lists
experimental measurements of strength and modulus of CNFs. The mechani-
cal properties of both VGCNF and ECNF are found to be functions of process-
ing methods, fiber diameter, and type of loading used for mechanical analysis. The
tensile strength of VGCNFs was measured through the use of a micromanipula-
tor that is viewed under a high-speed camera and a scanning electron microscope,
shown in Fig. 2.6 [24]. Later studies involving graphitized ECNF bundles derived
from PAN tested tensile strength using computer controlled mechanical testers,
2.2 Measured Mechanical Properties of CNFs 17
Table 2.1 Experimentally measured strength and modulus values of CNFs

Author Processa Diameter Loading Strength Modulus
(nm) type (GPa) (GPa)
Endo et al. [24] VG 300–1000 Tensile 1.25–3 100–300
Ozkan et al. [28] VGb 150 Tensile 2.35–2.9 180–245
Lawrence et al. [36] VG 115–470 Bending n/a 6–207
Zhou et al. [21] Eb 300 Tensile 0.597–0.969 n/a
Arshad et al. [20] E 150–500 Tensile 1.86–3.52 80–191
Zussman et al. [22] E 50–250 Bending 0.55–0.71 53.5–75.3
aVG: vapor grown, E: electrospun
bIncludes functionalized/graphitized CNF
Fig. 2.6 Schematic of micromanipulator setup utilized for tensile tests on VGCNFs. Image

taken with permission from [24]
where it was found that the use of phosphoric acid enhanced the strength of
graphitized ECNF by 62.3 % [21]. Ordered, graphitic, ribbon-like structures were
also induced in the ECNF through sufficient graphitization at 2200 °C in vacuum
in addition to phosphoric acid content to manipulate the tensile strength [21].
Bending experiments provided consistent results through the use of the
mechanical resonance method, which entailed clamping a PAN-based nanofiber
to the cantilever tip of an AFM and driving it to its fundamental resonance by a
piezoelectric actuator [22], as shown in Fig. 2.7a. Using a modulus-frequency rela-
tionship from classical linear elasticity, the modulus can be obtained by [22]

βn2 d E
fn = 2 (2.1)
2π L 16ρ
where E is the Young’s modulus, which in this case is termed as the effective
bending modulus, due to the fiber measurement method utilized. βn is the eigen-
value obtained from the characteristic equation cosh(βn ) cos(βn ) = −1, and d, L,
and ρ represent diameter, length, and density of the fiber, respectively. Three-point
bend tests on VGCNFs have also been implemented using AFM probes, with plat-
inum pads used as additional constraints, thus yielding CNF modulus values as
high as 207 GPa [36]. In such studies, it was observed that the midspan deflection
δ of the individual CNF varied linearly with the applied force F, which is con-
sistent with classical beam theory. Therefore, the elastic modulus can be obtained
from the AFM cantilever setup through [36]
192EI
F= δ (2.2)
L3
where E, I, and L are the elastic modulus, second moment of the cross-sectional
area, and the span of the beam, respectively. The range of bending modulus values
for ECNFs is observed to be generally smaller than the range of values obtained
from testing vapor-grown fibers, where the bending modulus of VGCNF can vary
by one to two orders of magnitude [36].
Platinum constraints were later utilized in a microelectromechanical system-
based (MEMS) experimental setup to observe the strength, modulus, and fracture
characteristics of individual VGCNFs [28]. An example of a MEMS-based tensile
test setup can be observed in Fig. 2.7b. Experimental studies on PAN-based CNFs
observed tensile strength of CNFs as a function of carbonization temperature
using MEMS-based loading setups [20]. The results derived from such MEMS-
based experimental setups showed some of the highest measured tensile strength
values for either VGCNFs or ECNFs listed in Table 2.1. However, the disparity of
values in Table 2.1 remains highly dependent on the process method, fiber diam-
eter, loading type, and possibly the structure of CNF. For example, it is shown in
Table 2.1 that typical PAN-derived ECNFs attain mechanical properties lower than
that of VGCNF, which is likely due to the differences between the VGCNF and the
ECNF structure. It is observed in earlier studies that the discontinuous granular
core morphology observed for the skin–core structure of ECNF offers a limited
Fig. 2.7 a A single ECNF constrained between a tungsten wire (left) and an AFM tip (right)
[22]. b A MEMS-based tensile measurement platform utilizing platinum blocks to constrain a
single VGCNF. Images taken with permission from [28]
2.2 Measured Mechanical Properties of CNFs 19
Fig. 2.8 a TEM image of ECNF carbonized at 1400 °C and b close-up TEM image of carbon
crystallites abundant in the ECNF structure. Images taken with permission from [20]
range of mechanical strength at processing temperatures of up to 1100 °C [21].

However, further research on carbonization effects due to higher temperature pro-
cessing has allowed for increased strength in ECNF, where non-carbon elements
are removed from the ECNF structure, and the appearance of carbon crystallites
allowed for increased densification and strengthening of individual fibers as shown
in Fig. 2.8. With such processing capabilities, the mechanical properties of ECNF
can be made comparable to VGCNF. The tensile strength and modulus values are
compared with respect to treated temperatures in Fig. 2.9. It can be observed that
the tensile strength of ECNFs at 1400 °C is 21.3 % higher than the maximum
value of average tensile strength of VGCNFs obtained in [28]. However, large
portions of the standard deviations recorded from the studies coincide with each
other, resulting in mechanical property data that is comparable to both types of
CNFs.
An inverse relationship is noted between the fiber diameter and the modulus
in Table 2.1, which may be due to the significance of shear deformation as the
aspect ratio changes [37]. Other size effects are also likely, given that CNFs with
larger dimensions have a higher chance of containing flaws and defects adversely
affecting their strength [12]. Such size effects are found to be prevalent for stud-
ies analyzing both ECNFs [23] and VGCNFs [28], as evidenced by the range of
values in Table 2.1. Additionally, the aforementioned studies that obtained strength
and modulus measurements using MEMS-based devices are comparable in terms
of tensile strength ranges. However, the modulus was measured to be as low as
180 GPa for VGCNFs [28], whereas modulus values obtained from testing PAN-
derived CNFs were as low as 80 GPa [20]. Additionally, within the set of modulus
values of ECNFs shown in Table 2.1, the bending modulus is up to one order of
magnitude lower than the values obtained from tensile testing of PAN-based CNF.
(a) 6 ECNF (Arshad, 2011) (b) 350 ECNF (Arshad, 2011)
Elastic modulus (GPa)

VGCNF (Ozkan, 2010) 300 VGCNF (Ozkan, 2010)
Tensile strength (GPa)
5
250
4
200
3
150
2
100
1 50
0 0
0 1000 2000 3000 0 1000 2000 3000
Treated temperature ( C) Treated temperature ( C)
Fig. 2.9 Comparison graphs of a tensile strength and b elastic modulus with respect to treatment
temperature of ECNF and VGCNF (data derived from [20, 28])
2.3 CNF Surface Enhancement
Efficient utilization of CNFs within composites is required for realizing their

potential as reinforcement. Considerations of the CNF aspect ratio [38, 39], proper
CNF dispersion within various matrices [40, 41], and rate of mechanical load-
ing of composites containing CNFs [35, 42] have been explored extensively in
an effort to identify factors for variation in composite mechanical performance.
However, enhancement of CNF itself can also play an important role in the
improvement of mechanical properties of the composite. Enhancements through
fiber functionalization and graphitization have allowed for improvements in
mechanical properties of VGCNF [28] and ECNF [21], respectively, as denoted
in Table 2.1. Additives incorporated in the precursor during fabrication, such as
phosphoric acid, have proven to be useful in enhancing the strength of PAN-based
CNFs by facilitating the formation of graphitic structures within the CNFs [21],
where such ordered graphitic structures have allowed for crystallinity and mechan-
ical property improvements.
Functionalized CNFs can allow for the formation of chemical bonds and
improve compatibility with polymer matrices [43–47]. For experimental inclusion
in composites, CNFs have been treated with acid-based chemical reagents [47].
Functionalization is more common for VGCNFs compared to ECNFs, although acid-
based chemicals such as heteropolyacids have been incorporated into PAN matrices
during ECNF production to enhance fiber morphology and physicochemical proper-
ties [48]. Molecular dynamics simulations have captured the effect of pristine [47]
and functionalized [50] CNFs on the crosslink density around the nanofiber within
a vinyl ester polymeric resin. It was shown that an interphase region with a lower
crosslink density forms around a pristine CNF, where different chemical concentra-
tions near the surface of functionalized CNF form a stiffer interphase region with a
higher crosslink density [49, 50]. Such results can be u seful to further modify the
properties of multiscale composites through improved fiber–matrix interactions [50].
2.3 CNF Surface Enhancement 21
Adhesion between the functionalized VGCNF surface and a polymer matrix

has been improved through the chemical grafting of a polymer on the fiber surface
[43, 51]. In situ intercalated polymerization is the primary mechanism through
which a polymer layer can be introduced on a functionalized CNF surface, where
polymerization occurs inside of a composite on a functionalized surface in the
presence of filler. Therefore, such materials have been dubbed in situ polymer
nanocomposites, a topic which has been discussed in the published literature [52].
However, the quantity of the chemical that is grafted onto CNF and ultimately
introduced into the solid multiscale composite is often difficult to parameterize in
terms of composite constituent percentage through direct measurement and pre-
determination of composite material design. Such assessments become crucial in
determining the effect of variation of weight or volume percentage of chemical
additive on the mechanical properties of the individual CNF and the composite.
Thus, for the purposes of this review, in situ composites developed through func-
tionalization of CNF will only be given general mention. Such studies on CNF
enhancement can lead to mechanical property and dispersion improvements while
reducing the amount of CNF reinforcement necessary, thus facilitating composite
fabrication, CNF dispersion, and ultimately reducing cost.
2.4 Modeling of Mechanical Properties of CNF
Before direct experimental measurements were conducted, iterative back-calcu-

lation and semi-empirical estimations, as well as analytical predictions and finite
element simulations, were employed to obtain predictions for values of modulus
of CNFs [6, 17, 18, 33, 34]. Such methods allowed using predicted properties of
CNFs in estimating the properties of CNF reinforced nanocomposites before the
actual experimental measurements on single CNFs were possible [32, 35]. For
the majority of simulation studies performed on individual CNFs, the cup-stacked
structure of VGCNFs is most commonly utilized, as opposed to the more hetero-
geneous and randomized structure found in ECNFs.
It has been previously proposed that the graphitic cone angle and layer align-
ment directly influence the mechanical properties of individual CNFs [6]. Initial
attempts at developing analytical solutions have demonstrated that variation in
the CNF length and cup tilting angles with respect to the fiber axis can affect the
Young’s modulus [17]. This was determined through the derivation of an analyti-
cal relationship between the Young’s modulus of a single-shell nanocone (YCONE)
within a VGCNF and a single-walled CNT (YSWCNT), as follows:
2
YCONE = YSWCNT cos4 θ 1 − γ|| sin2 θ (2.3)
where γ|| is the Poisson’s ratio along the graphene plane and θ is the tilting angle of the
graphene plane with respect to the cone axis. Since a single CNF can be comprised of
N shells of nanocones, the total strain energy E of a single CNF is defined as [17]:
(a) (b)
(R1 -R2) = 25 nm
(R1 -R2) = 50 nm
(R1 -R2) = 100 nm
Fig. 2.10 a Schematic denoting CNF geometric parameters. b Plot demonstrating relationship
between the geometric parameters and Young’s modulus of single CNFs, where θ is the tilting
angle, L is the nanofiber length, and R1 and R2 are the outer and inner radii of the CNF, respec-
tively. Images taken with permission from [17]
N N=1
1 i,i+1
E = AL Y ε2 = i
Eshell + EVDW (2.4)
2
i=1 i=1
where Y, A, L, and ε are the Young’s modulus, cross-sectional area, fiber length,
and fiber strain, respectively. The first summation term takes into account the
strain energy of all shells, where the strain energy of the ith shell is denoted as
i
Eshell. The second summation term takes into account the total strain energy con-
tribution of the van der Waals (VDW) forces acting between each shell, where the
i,i+1
VDW strain energy acting between shells I and i + 1 is denoted as EVDW . Using
Eq. 2.4, the Young’s modulus of a CNF composed of N shells can be derived so
that the relationship between the Young’s modulus and parameters, such as the
cone tilting angle and nanofiber length, can be assessed as shown in Fig. 2.10a.
Asymptotic trends are observed in Fig. 2.10b for the modulus with respect to these
two parameters. Low tilting angles, low nanofiber lengths, and larger differences
between the inner and outer radii of CNF allow for higher modulus. Such expres-
sions and trends derived in [17] were validated with molecular dynamic (MD)
simulations utilizing single-shell, four-shell, and seven-shell CNF nanocones.
Computer models have expanded on the structure of helical nanostructures such
as CNF [53], where consideration of carbon atomic bonds mapped as a hexago-
nal structure can potentially show accurate visual demonstrations of CNF growth
and facilitate calculation of physical properties. Recent MD simulations on cup-
stacked CNFs have further explored the role of the cone angle [18]. Figure 2.11
shows that maximum strength is achieved when the cone angles in a CNF are
close to being parallel to the fiber axis, such as in a CNT, where failure modes
are shown to vary with cone angle in Fig. 2.11a–d. A tensile strength minimum
is also observed at a critical cone angle in Fig. 2.11e, thereby demonstrating
competition between van der Waals forces and strengthening mechanisms from
2.4 Modeling of Mechanical Properties of CNF 23
Fig. 2.11 MD simulations
of a SWCNT, and CNF
models with cones at b 19.2°,
c 83.6°, and d 180°. e Log-
scale relationship between
tensile strength and cone
angle. Images taken with
permission from [18]
thermal-induced surface bonds [18, 34]. However, it must be noted that direct
experimental studies on the effect of the cone angle on the mechanical properties
of single CNFs are scarce at present.
2.5 Summary
Vapor-grown and electrospun CNFs are discussed in this chapter. The manufac-
turing processes for both types of CNFs are discussed. VGCNFs usually have a
helically folded or stacked-cup geometry, whereas ECNFs have a core–shell
structure. The difference in their structure reflects in the difference in their prop-
erties. Studies are now available that have tested single CNFs for mechanical
properties, usually under tensile and bending loading. The experimentally meas-
ured strength is found to be in the range 550 MPa–3.5 GPa. A similarly large
scatter is observed in the modulus values, which vary from 53 to 300 GPa under
tensile loading. Surface modification can help in making CNFs compatible with
the matrix polymer. MD simulations have been used extensively to estimate the
properties of CNFs and also to understand the deformation mechanisms and trends
in m
echanical properties with respect to parameters such as cone angle and fiber
diameter. Such studies have been very useful in providing insight into CNFs
because of a lack of direct observations at that scale.
References
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Chapter 3
Mechanical Properties of CNF/Polymer
Composites
Abstract This chapter discusses the effect of composition of CNF reinforced

nanocomposites on their mechanical properties measured under tensile, compres-
sive, and flexural loading. The structure of the CNFs plays an important role in
determining the reinforcement efficiency. In most cases, random CNF dispersed
nancomposites have been studied. Thermoplastic resin, thermosetting resin, and
elastomer matrix nanocomposites have been studied. Polypropylene is the most
common thermoplastic resin that is reinforced with CNFs. Among thermosets,
epoxy and vinyl ester resin matrix nanocomposites are studied. The strength and
stiffness improve, depending on the volume fractions of CNF dispersed within
several different polymer matrices. It is noted that compared to the mechani-
cal properties of single CNFs reported in Chap. 2, the level of enhancement of
mechanical properties of nanocomposites is only moderate. The bending of long
aspect ratio fibers and stacked-cup structures are potential reasons for this out-
come. Nevertheless, combined with other properties, such as electrical and ther-
mal conductivity increase in otherwise insulating resins, the moderately enhanced
nanocomposites can develop new applications.
Keywords Carbon nanofiber · Nanocomposites · Dispersion · Mechanical property ·

Flexural properties · Viscoelastic properties
3.1 Literature Review
The potential of using carbon based fibers in developing high performance

composite materials has been recognized for a long time [1]. Carbon microfiber-
based polymer matrix laminates have been widely studied and used in numerous
structural applications. The ever-increasing demand for higher performance fib-
ers and composites has resulted in continuous improvement in the properties of
microfibers and also of development of carbon nanofibers and nanotubes. Fibers of
different length or diameter scales are sometimes combined into novel structures

28 3 Mechanical Properties of CNF/Polymer Composites
to develop new composite materials. It has been shown that the strength and stiff-
ness of vapor-grown carbon fibers decrease with increasing diameter, due to the
increased likelihood of flaws within higher volumes. The diameter of fabricated
vapor-grown fibers is attributed to the rate of carbon deposition [1]. Through com-
parisons drawn between VGCNFs, PAN fibers, and pitch fiber, VGCNFs offer
superior tensile strength and modulus. To allow for optimal performance, as well
as ease of fabrication and design, VGCNFs are often utilized in random dispersion
within composites, where reinforcement at the nanoscale allows for retention of
the homogeneity and isotropy in bulk composite materials.
Experimental studies conducted on the mechanical properties of CNF/polymer
composites are summarized in tabular form, where Table 3.1 covers thermoplas-
tic matrix composites [2–12], Table 3.2 covers thermosetting matrix composites
[13–24], and Table 3.3 covers elastomer matrix composites [25–27]. The tabular
form allows for a quick comparison of various studies and their reported results.
Subsequent sections of this chapter will discuss some of the results and observa-
tions reported in these studies.
3.2 Tensile Properties
Thermosetting polymer matrices that have been prominent in tensile stud-

ies include vinyl ester, epoxy, and polyimides such as polyetherimide (PEI).
Thermoplastic polymers such as polypropylene and polycarbonate have also been
utilized. Studies denoting random dispersion of VGCNFs in polycarbonate matrix
showed increase in the tensile strength (8–22 % with respect to neat polycarbon-
ate) and in the tensile modulus (53–72 % with respect to neat polycarbonate) [7].
Such increases are considered marginal for nanoreinforcements, especially given
the 20 wt% CNF in the composite. On the contrary, the impact resistance, which
is an important attribute in thermoplastics such as polycarbonate, was severely
diminished with the addition of CNFs. The presence of aromatic hydrocarbons on
the fiber surfaces is likely the reason for the inefficiency of the CNF reinforcement
and degradation of impact properties.
These initial results obtained from polymer composites containing CNFs laden
with aromatic hydrocarbons on the surface promoted development of processes
such as pyrolytic stripping during CNF processing. The pyrolytically stripped
VGCNFs have been useful in several studies. Increase in the tensile properties due
to such alterations has been considerable, especially given that such increase has
been achieved at relatively lower CNF loadings (below 20 wt%). Kuriger et al.
achieved a near-threefold increase in the tensile modulus and a 20 % increase in
the ultimate tensile strength in CNF/polypropylene composites, with 11 vol%
(approximately 20 wt%) CNF [3]. Although composites with higher CNF con-
tent were analyzed in the study, the efficiency of CNF reinforcement decreased at
higher CNF content due to poor wetting of the fiber surfaces and increase in void
entrapment.
3.2 Tensile Properties 29
Table 3.1 Available studies on bulk CNF thermoplastic polymer composites

Reference Composite type Testing conditions Results
Carneiro et al. Matrix: Polycarbonate Tensile test Tensile strength
[7] CNF: 20 wt% of change = −8 to
VGCNF 22 %, tensile modulus
change = 53–72 %, with
respect to neat polymer
Kumar et al. Matrix: Polypropylene Compression test Compressive modulus and
[8] CNF: 5 wt% CNF strength of polypropylene
composite with 5 wt%
CNF increased by 50 and
100 %, respectively, with
respect to neat matrix
Kuriger et al. Matrix: Pro-Fax Tensile test 20 % increase in ultimate
[3] 6301 polypropylene (4 mm/min) tensile strength with
composite 11 vol% CNFs, tensile
CNF: aligned Pyrograf modulus nearly tripled
PR-21-PS (1–11 vol%) with the same CNF
and PR-19-HT content
(9–23 vol%) VGCNFs
Brandl et al. Matrix: Polypropylene Tensile test Tensile strength and
[5] CNF: 5 wt% VGCNF modulus increased by 18.5
with added functional and 49.2 %, respectively,
groups on fibers with addition of 5 wt%
CNF
Choi et al. [9] Matrix: NOVAREX Micro-indentation Composite hardness
7020A polycarbonate test and Young’s modu-
CNF: Showa Denko lus increased by ~56
Japan VGCF carbon and ~105 %, respectively,
nanofibers, content rang- with addition of 25 wt%
ing from 0 to 25 wt% CNF
Howe et al. Matrix: Montel Pro-Fax Tensile test Tensile strength range:
[10] 6301 polypropylene (1 mm/min) 20–50 MPa, tensile modu-
matrix lus range: 1.5–2.5 GPa.
CNF: Pyrograf PR-19 Neat polypropylene tensile
VGCNF content rang- strength and modulus aver-
ing from 3 to 12 vol%. ages around 30 MPa and
CNF heat treated with 1.25 GPa, respectively
temperatures between
1000 and 3000 °C
Hasan et al. Matrix: Polypropylene Tensile test 154.5 % increase in tensile
[2] CNF: 0.5 wt% aligned modulus, 69.5 % increase
Pyrograf PR-24 VGCNF in yield strength at 0.5
wt% CNF
Ingram et al. Matrix: ChemPoint Tensile test (strain At strain rate of 0.02/min,
[4] polypropylene rate range: 0.02/min enhancement of 154 %
CNF: 0.5 wt% Pyrograf to 2/min) in tensile modulus and
PR-24 VGCNF 69.5 % in ultimate
tensile strength observed,
compared to neat
polypropylene
(continued)
Table 3.1 (continued)
Larin et al. Matrix: Isotactic Tensile test Tensile modulus and
[11] polypropylene strength increased by
CNF: 1 wt% graphitized maximum of 46 and 14 %,
VGCNF respectively, with addition
of 1 wt% CNF, variation
dependent on mixture
drawing method
Teng et al. Matrix: Polylactide Flexural (3-point) Flexural strength and
[12] thermoplastic polymer bend test modulus increased by 7.0
CNF: Showa Denko and 35.4 %, respectively,
Japan VGCF carbon with addition of 7 wt%
nanofibers (polylactide PLA-functionalized CNF
functionalized), content
ranging from 0 to
18.5 wt%
Kumar et al. Matrix: Polyetherimide Tensile test Tensile strength
[6] (PEI) range = 40.6–56.4 MPa,
CNF: 1–3 wt% CNF tensile modulus
range = 3.74–4.51 GPa
depending on content and
treatment
Table 3.2 Available studies on bulk CNF-thermoset composites

Patton et al. [15] Matrix: EPON 830 Flexural (3-point) Flexural strength
epoxy resin and low bend test range = 70.9–146.4 MPa,
viscosity epoxy resin flexural modulus
from Clearstream range = 2.29–8.74 GPa
Products, Inc. depending on content and
CNF:3.3–49.5 vol% fabrication
CNF
Sun et al. [16] Matrix: EPON 862 Tensile test Tensile strength range:
epoxy resin 68.7–74.4 MPa, tensile
CNF: Pyrograf III modulus range: 1.04–1.29
CNF content ranging GPa, toughness range:
from 0 to 2 wt% 244.5–610.2 MJ/m3
Wang et al. [13] Matrix: EPON 862 Tensile test Functionalized CNF/epoxy
epoxy composites show modulus
CNF: Pyrograf III and strength retention,
PR-19-HT CNF modulus and strength
content ranging increase by a maximum
from 0 to 10 wt%, of 15 and 6 %, respectively
both functionalized
with epoxy and
non-functionalized
(continued)
Ahn et al. [14] Matrix: EPON 828 Tensile test Tensile modulus increased by
epoxy resin matrix (1 mm/min) 260 % at 12.8 wt% function-
CNF: functionalized alized CNF. Tensile strength
Pyrograf III VGCNF increased by 136 % at 6.4
content ranging from wt% CNF. Values compared
0 to 12.8 wt% to neat epoxy resin
Xu et al. [17] Matrix: EPON 826 Flexural (3-point) Flexural strength and
and 828 epoxy resin bend test modulus increased by 28.2 %
CNF: graphitic Tensile test and 5.4 %, respectively;
carbon nanofiber Fracture tough- tensile strength and modulus
content ranging from ness test increased by 15.2 % and
0 to 10 wt% 27.7 %, respectively;
toughness increased
by 9.8 % with CNFs
Xu et al. [18] Matrix: Vinyl ester Flexural (3-point) Variation in flexural modulus
CNF: Pyrograf III bend test is negligible, flexural strength
CNF loadings rang- decreased by 49.5 % with
ing from 0 to 25 wt% respect to neat vinyl ester
VGCNF
Choi et al. [19] Matrix: Epikote 825 Tensile test Maximum tensile strength
Bisphenol A epoxy (1 mm/min) and Young’s modulus
resin achieved at 5 wt% CNF,
CNF: Showa Denko tensile strength range:
Japan VGCNF, 0–20 20–75 MPa, tensile modulus
wt% range: 5.5–10.5 GPa
Gauthier et al. [20] Matrix: Two series Tensile test Tensile modulus: increased
made of Araldite by a maximum of 35 and
LY-556 (Bisphenol 200 % for epoxy and SBR
A) epoxy resin composites at 7 wt% CNF
and styrene-buta- with respect to neat matrices.
diene (SBR) latex Tensile strength of epoxy
elastomer composite increased by
CNF: 0–10 wt% 65 % but for SBR composite
CNF decreased by 55 % at 7 wt%
CNF with respect to neat
matrices
Zhou et al. [21] Matrix: SC-15 epoxy Tensile test Tensile strength
resin range = 63.96–68.98 MPa,
CNF: 1–3 wt% CNF tensile modulus
range = 2.87–3.32 GPa
Bal [22] Matrix: Araldite Flexural (3-point) Flexural modulus range:
LY-556 (Bisphenol bend test 2249-2694 MPa depending
A) epoxy on content and processing.
CNF: 0.5-1 wt%
CNF
(continued)
Colloca et al. [23] Matrix: D.E.R. 332 Tensile test Tensile modulus and
epoxy resin Nanoindentation hardness of 1 wt% CNF
CNF: Pyrograf III test composite are 3.87 GPa, and
PR-19 XT-PS CNF 214 MPa, respectively,
content at 1 wt% specific modulus decreases
by 23.8 % with addition of
CNF. Modulus measured
through nanoindentation
is 28 % lower than that
measured through tensile test
Bafekrpour et al. Matrix: Hexion Tensile test Tensile strength remains
[24] Specialty Chemicals Flexural (3-point) relatively unchanged in
phenolic resin matrix bend test monolithic composites
CNF: Nanostructured with CNF content variation
and Amorphous (strength ranges between 21
Materials, Inc. and 24 MPa), similar results
graphitized CNFs were observe for flexural
with content ranging strength. Tensile modulus
from 0-16 wt% increased from 2.63 GPa
for neat resin to 4.49 GPa
for composite containing
16 wt% CNF. No general
trend in flexural modulus was
observed for composites
Table 3.3 Available studies on bulk CNF-elastomer composites

Mapkar et al. Matrix: Gelest Inc. Tensile test Highest values of tensile
[25] poly(dimethylsiloxane) (0.5 mm/min) strength and modulus are
elastomer observed in composites
CNF: Pyrograf PR-24 containing 30–40 wt%
pristine and oxidized functionalized CNF. Strength
VGCNFs with additional and modulus increased
grafted surface by maximum of 300 and
functionalization, 1900 %, respectively,
0–50 wt% compared to neat matrix
Raza et al. Matrix: Rubbery epoxy Compression test Compressive modulus and
[26] (RE) strength increased by factors
CNF: Pyrograf III of 3 and 5, respectively, at
VGCNF, 0–40 wt% 40 wt% CNF compared to
neat matrix
Raza et al. Matrix: Sylgard 184 Compression test Compressive strength and
[27] Silicone elastomer modulus increases by max of
CNF: Pyrograf III PS 89.8 % (at 12 wt% CNF) and
and HT grade VGCNF, 68.9 % (at 15 wt% CNF),
0–15 wt% respectively
Alignment of CNFs along a specific direction has demonstrated considerable

improvement in tensile strength and modulus along the direction of alignment.
Hasan et al. demonstrated increases of 154 % and 69.5 % in the tensile modu-
lus and strength of CNF/polypropylene composite filaments with only 0.5 wt%
VGCNFs that were aligned through single-screw extrusion [2]. Due to improve-
ments in composite processing and CNF surface treatment over time as evidenced
in Table 3.1, it can be seen that the reinforcing efficiency of CNFs within polymer
composites has steadily increased.
It is found that graphitization by high temperature treatment alters the crystallin-
ity of the CNF structure, which in turn affects its mechanical properties. Studies uti-
lizing graphitic CNFs within polymer composites have demonstrated increases in the
tensile strength and modulus, with CNF content as low as 1 wt% [11]. The issues of
poor surface wetting and void entrapment have been partly addressed through the
use of chemical functionalization of the CNF surface, which can eliminate interfa-
cial incompatibility and improve fiber adhesion to the polymer matrix. The applica-
tion of functional chemical groups on the CNF surface has allowed for higher CNF
loadings. The use of a poly(dimethylsiloxane) (PDMS) elastomer matrix compos-
ite with functionalized CNF allowed for a tensile strength and modulus increase of
300 and 1900 %, respectively [25]. Such high values of tensile strength and mod-
ulus were attained with composites containing between 30 and 40 wt% CNF. The
enhanced surface chemistry of functionalized CNFs allowed for improved distribu-
tion of CNFs within the elastomer composite, as shown in Fig. 3.1 [25].
Fig. 3.1 SEM micrographs of 30 wt% PDMS nanocomposite produced with a pristine CNFs,

b oxidized CNFs, c aminopropyl (NH2) terminated functionalized CNFs, and d carbinol (COH)
terminated functionalized CNFs [25]
3.3 Compressive Properties
Effect of reinforcement on the compressive properties is expected to be limited

because of the high aspect ratio of fibers. Hence, compression studies on CNF/
polymer composites are scarce as shown in Table 3.1. However, if randomly dis-
tributed throughout the composite, the fibers that are oriented in the transverse
direction can restrict lateral expansion, thus indirectly providing resistance to
longitudinal compression. Studies on CNF/polypropylene composites have dem-
onstrated 50 and 100 % improvement of compressive modulus and strength,
respectively, with the addition of 5 wt% CNFs. Uniform random dispersion of
CNFs within the composite was observed through scanning electron microscopy.
The mechanism of restricting lateral expansion to improve the compressive prop-
erties is effectively deployed in elastomeric matrix composites reinforced with
CNFs.
Elastomers demonstrate high thermal stability, excellent dielectric properties,
and low curing temperature, which are useful in many applications. However, their
large elastic deformation, high coefficient of thermal expansion, and low compres-
sive modulus are major limitations. Experimental studies on silicone elastomers
reinforced with 0–15 wt% VGCNFs have improved the compressive strength and
modulus by a maximum of 89.8 and 68.9 %, respectively [27]. Due to the pres-
ence of CNFs, the resulting composite can be used for applications requiring high
electrical and thermal conductivity. Thermal interface pads and electrostatic dis-
sipation materials can be developed at lower cost with CNFs than with CNTs.
Improved processing techniques using rubbery epoxy and VGCNFs have also
been shown to produce composites suitable for electronic packaging applications,
where the compressive modulus and strength as well as thermal conductivity have
been shown to increase significantly [26]. Dispersion of CNFs in such composites
has been shown to drastically improve with three-roll mixing, as demonstrated in
Fig. 3.2. High shear generated between the rolls is used to disperse CNFs in the
matrix. The thin layer of the processed composite slurry is scraped from the third
Fig. 3.2 Schematic of
a three-roll mill utilized
to fabricate elastomeric
composites with CNFs [26]
3.3 Compressive Properties 35
roll and recirculated in the system as many times as necessary to obtain the desired
level of dispersion. Among the drawbacks of this processing method are that
(a) the high shear force can break CNFs and reduce their aspect ratio and
(b) entangled CNFs may not be separated in this method. Nevertheless, this
method is successful in fabricating CNF/polymer composites and has been widely
used.
3.4 Flexural Properties
Flexural loading is essentially a combination of tensile and compressive loading,

where fracture is generally initiated on the tensile side in brittle materials. As dis-
cussed in the previous sections on the tensile and compressive properties, uniform
dispersion of CNFs can offer multiple benefits. Earlier studies demonstrated a
wide range of strength (70.9 – 146.4 MPa) for CNF/epoxy composites containing
3.3–49.5 vol% CNFs. The flexural modulus for the composites in the same study
is shown to vary between 2.3 and 8.7 GPa, thus demonstrating the tailorability of
the composite through CNF variation. Despite the potential benefits in altering the
flexural properties, higher CNF content does not generally correlate to increased
strength and stiffness. Flexural analyses conducted using vinyl ester resin and up
to 25 wt% VGCNFs have shown negligible variation in flexural modulus as well
as decrease in flexural strength by up to 49 % [18]. As established in earlier sec-
tions, higher CNF content can lead to poor fiber surface wetting and high void
presence, which can adversely affect mechanical performance.
Dispersion strategies and fabrication techniques such as altered curing con-
ditions have allowed for improvements in the flexural properties of CNF rein-
forced epoxy composites. The addition of up to 1 wt% CNFs, coupled with
refrigerated curing of composites, has allowed for a flexural modulus increase
of approximately 97 % compared to neat epoxy cured at room temperature [22].
Refrigeration curing is shown to prevent CNF aggregates during curing, thus
resulting in improved properties. As implemented in several of the tensile analyses
discussed in the previous section, CNF surfaces were functionalized for improved
matrix adhesion. In one study, polylactide (PLA) was grafted onto the CNF sur-
face and then dispersed within a PLA matrix, resulting in a flexural modulus and
strength increase of 35.4 and 7.03 %, respectively, when compared to neat PLA
[12]. The flexural property increases, coupled with significant increases in the
impact strength within the same study, were achieved with only 7 wt% functional-
ized CNF. Surface functionalization of VGCNFs, as performed in the study using
PLA, involve grafting functional chemical groups onto the surface in such a way
that interfacial compatibility between the CNF and matrix (PLA) is achieved.
A schematic highlighting some of the steps in the CNF functionalization and
PLA/VGCNF composite fabrication process is shown in Fig. 3.3 [12].
Fig. 3.3 Schematic of CNF functionalization through use of PLA and fabrication of PLA/VGCNF

nanocomposites. Further details and an interpretation of the figure legend can be found in [12]
3.5 Other Mechanical Properties
Localized plasticity, as well as failure mechanisms, can also be altered with the
presence of CNFs within polymer composites. Few indentation test reports exist
for CNF/polymer composites, since it is often assumed that due to the decrease
in homogeneity of nanocomposites at smaller dimensional scales, microindenta-
tion or nanoindentation may not produce results that are representative of the bulk
nanocomposite properties. Nevertheless, improvements can still be observed with
addition of CNFs [28]. Polycarbonate composites reinforced with up to 25 wt%
CNFs have demonstrated an increase in the composite hardness and the modulus
by approximately 56 and 105 %, respectively, compared to neat polycarbonate [9].
Nanoindentation analyses have been carried out on epoxy composites containing
1 wt% VGCNFs, where the hardness was measured to reach a value of 217 MPa
[23]. The tensile modulus that was measured through tensile analysis in the same
study was measured to be 28 % lower than the modulus measured through nanoin-
dentation. Given the size of the indenter, the nanocomposite structure can be
influenced by the dispersion of the CNFs, since large standard deviations for the
nanoindentation results were found. However, such results can be considered to be
3.5 Other Mechanical Properties 37
Fig. 3.4 Images of the nanoindentation markes on the surface of CNF/epoxy composite

obtained through scanning probe microscopy at (a) lower and (b) higher magnification. c Surface
topography of an indented region can be observed in (c) [23]
Fig. 3.5 Large-diameter
CNF protruding from the
surface of a crack in a
specimen stressed to
25 MPa [30]
an upper bound, due to indenter insensitivity to property-degrading voids along the

composite surface. Scanning probe microscopy images of the indentation on the
CNF/epoxy surface are shown in Fig. 3.4 [23].
Failure mechanisms for CNF/polymer nanocomposites have been of interest,
given that the fracture energy can increase due to fiber crack bridging. Large CNF-
matrix interfacial area is also expected to provide an increase in fracture energy if
the interfacial strength is strong. Earlier studies denote modest gains in the frac-
ture toughness with addition of up to 10 wt% graphitic CNFs [17]. Randomized
CNFs within epoxy matrix composites have demonstrated high interfacial shear
strengths, especially after surface functionalization of CNFs [29]. Parameters
such as the Mode I fracture toughness (GIC) of CNF/epoxy composites have
been evaluated and shown to increase by 144 % with addition of only 1 wt%
CNFs, compared to neat epoxy [30]. Crack bridging within the nanocomposite
can be observed through detailed microscopy of the fracture surface in the form
of a nanofiber protruding from the surface of a crack, as shown in Fig. 3.5 [30].
Presence of such CNFs indicates fiber pull-out and rupture.
3.6 Common Analytical Models for Experimental

Validation
Theoretical models can provide the capability to predict the properties of composite
materials and identify compositions that may be beneficial for a given application.
Assumptions are often made to derive simpler and tractable models. Taking appro-
priate assumptions is very important in order to make sure that the prediction accu-
racy is not compromised and the model is representative of the material structure. In
general, many of the simple micromechanics-based models assume that [31]
• The composite is homogeneous and orthotropic on the macroscopic level;
• The composite is linearly elastic, initially stress-free, and defect-free;
• Perfect bonding is observed at all interfaces, with no transitional region between
both phases and there is no interfacial slip.
Specific assumptions are also made for the matrix and the reinforcing fibers that
constitute the composite, which include
• The matrix is homogeneous, linearly elastic, and isotropic;
• The fibers are homogeneous, isotropic or orthotropic, and linearly elastic;
• The fiber cross-section is assumed to be circular, and fiber length is assumed to
be infinitely long in the axial direction;
• The fibers are evenly spaced and perfectly aligned.
One of the most common models, used as a first measure for property prediction
and validation, is the rule of mixtures:
Ec = Em φm + Ef φf (3.1)
φm = 1 − φf (3.2)
where E and φ represent elastic modulus and volume fraction, respectively.
Subscripts c, m, and f represent composite, matrix, and CNFs, respectively.
Homogeneity and isotropy are assumed over a small range of volumetric strains;
however, the fibers are assumed to be unidirectional. Such a model serves as a
weighted mean, as well as an upper bound, for composite property predictions.
Another model often utilized is the Cox model, where properties such as the
composite elastic modulus can be estimated as a function of fiber volume fraction
and aspect ratio [32]

Ec = Em φm + ηf Ef nφf (3.3)
tanh β
ηf = 1 − (3.4)
β
3.6 Common Analytical Models for Experimental Validation 39

l Em
β=

(3.5)

d π

(1 + ν)Ef ln 4φf
where n is a constant related to the orientation of the fibers (n = 1/6 for randomly
oriented fibers in 3-D, as opposed to n = 1 for aligned fibers), ηf is the filler effi-
ciency factor, l is the average fiber length, d is the fiber diameter, and ν is the fiber
Poisson’s ratio. The Cox model is considered to be an extension of the paral-
lel model derived from the rule of mixtures, such that the fibers are taken to be
much shorter than the bulk composite specimens tested. The filler aspect ratio is
also taken into account through use of a filler efficiency factor. These assumptions
are in contrast to the infinite fiber continuity assumed in the rule of mixtures, thus
resulting in more accurate predictions. The Cox model for prediction of the com-
posite modulus is very sensitive to fiber aspect ratio as shown in Fig. 3.6 [32].
Complexity is further added to predictive models by taking into account the
longitudinal and transverse properties of the reinforcement. The Halpin–Tsai
model is one such model that has often been modified in order to take random
distribution into account [33]. Properties such as the elastic modulus (Ec), shear
modulus (Gc), and Poisson’s ratio (νc) of the composite have been predicted using
the following expressions:

3 5
Ec = Em EL + ET (3.6)
8 8

1 2
Gc = Em EL + ET (3.7)
8 8
Ec
νc = −1 (3.8)
2Gc
where the terms EL and ET represent the longitudinal and transverse elastic modu-
lus, respectively, and each can be calculated using the Halpin–Tsai equations as
follows:
1 + 2ζ ηL φf
EL = (3.9)
1 − ηL φf
1 + 2ηT φf
ET = (3.10)
1 − ηT φf
Fig. 3.6 Cox model
predictions for the elastic
modulus of VGCNF/polymer
composites [32]
where the terms ηL and ηT are expressed as

E
α Emf − 1
ηL = E (3.11)
α Emf + 2ζ

Ef
α Em −1
ηT =
Ef
(3.12)
α Em +2
The terms α and ζ represent the orientation factor and aspect ratio, respectively. In use
of both models, studies have shown good agreement with experimental data, where
the Halpin–Tsai model has been shown to fit data well with 5 % variation [33].
3.7 Summary
The available literature on CNF/polymer composites is rich. Despite the very

high strength and modulus measured on single CNFs, composite materials rein-
forced with CNFs show a lower than expected improvement in mechanical prop-
erties. In many studies up to 10 wt% CNFs are added and improvements in the
range of 50–200 % are observed in either strength or modulus or both. However,
given the properties of single CNFs, such a level of improvement is much less than
expected. Some of the factors responsible for this deficiency are the surface prop-
erties of CNFs leading to less than perfect CNF-matrix interfacial bonding, defects
present in the CNF structure, and random distribution of CNFs. Uniform disper-
sion of CNFs in the matrix and complete wetting are the focus issues in the pro-
cessing method development. High shear forces are capable of dispersing CNFs
3.7 Summary 41
but damage to CNFs leading to shorter effective lengths is a concern. Theoretical

models are available that can estimate the properties of nanocomposites based on
the distribution of CNFs in the material. Most existing investigations are based
on the tensile properties of CNF reinforced nanocomposites for thermosetting
and thermoplastic resin matrix composites. Elastomeric matrix nanocompos-
ites are also found studied for compressive properties. Overall, it is expected that
improved understanding of the mechanical and surface properties of individual
CNFs will help in improving the quality of nanocomposites and will help in gain-
ing the level of performance that is expected based on the theoretical values.
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Chapter 4
Environmental Effects on CNF/Polymer
Composites
Abstract A crucial factor that affects all composite materials exposed to typical
service conditions is environmental degradation. It has been shown that over time
the combination of moisture and fluctuating temperatures degrades the structure
of polymeric composites through chemical and morphological degradation mecha-
nisms. Experimental investigations have not only demonstrated degradation of the
polymeric matrix but also of the CNF–matrix interface due to surface morphol-
ogy variation caused by weathering. This chapter aims to focus on the moisture
effects on the structure and mechanical properties of CNF/polymer composites in
an effort to offer insight into the mechanisms of degradation and failure under load
after moisture exposure. However, information on this aspect of CNF/polymer
composites is in the nascent stage and extensive future work is required.
Keywords Carbon nanofiber · Nanocomposite · Moisture · Ultraviolet radiation ·

Degradation
4.1 Introduction
As discussed in Chap. 3, CNFs are used as reinforcements in polymer matrix

composites (PMCs) for improvement in their strength and modulus [1–4].

Small quantities of CNFs can significantly alter the properties of PMCs, without
adversely affecting the density [5, 6]. Evaluation of the environmental performance
of polymer matrix composites is important for marine and aerospace applications
[7, 8]. These structures are exposed to severe moisture and temperature conditions
[9, 10]. The adoption of PMCs for such applications can be accelerated by deter-
mining the effect of environmental conditions on their properties and designing
composites that can retain their properties for a longer time in harsh environments.
During service, a composite component may be in contact with gases such
as moisture in the form of environmental humidity or oil fumes or with liquids
such as saltwater, freshwater, or lubricants. Depending on the type and level of
exposure as well as the time exposed, the magnitude of the degrading effects on

44 4 Environmental Effects on CNF/Polymer Composites
exposed composites can vary significantly. Periodic weight measurement of the

specimens is usually carried out to quantify the level of moisture absorption over
time. However, given the variety in the possible combinations of moisture and
temperature conditions, it is usually difficult to directly compare the results from
different studies or generalize the conclusions. For example, the conditions to
which a composite may be exposed to moisture may include freeze–thaw, different
levels of humidity; room or high temperature immersion in water; use of seawater,
saltwater, freshwater, or deionized water; moisture exposure-dying cycles; among
others. It has been widely accepted that environmental testing should be conducted
based on the anticipated actual service conditions of the component, which results
in such a wide variety of test conditions in the available literature on PMCs. Apart
from common elements such as periodic weight gain measurements and exten-
sive microscopy of the exposed material, residual mechanical properties are often
measured to determine the extent of damage in the material.
4.2 Studies on Moisture Effects on Polymers and Fiber

Reinforced Composites
Studies of the environmental effects on the physical properties of CNF/polymer

composites are scarce. Insights into the environmental effects of such composites,
however, can be obtained from the analyses performed on the constituent mate-
rials. The environmental behavior of neat polymers is of great interest in under-
standing the behavior of CNF/polymer composites.
Moisture effects on polymer materials, particularly epoxy resins, have been
investigated since the 1970s [11, 12]. The earlier studies have observed consider-
able swelling of cured epoxy resin with moisture uptake and exposure to higher
temperatures resulted in hygrothermal expansion of the polymer. It should be
noted that the terms “swelling” typically refers to the volumetric expansion attrib-
uted to moisture exposure, which may be at different temperatures. The swelling
can result in residual stress buildup at the filler–matrix interface due to the mis-
match of material properties [13, 14]. Hence, the strength and chemical nature
of the interfacial bonding is extremely important for moisture and temperature
effects. The effects can be complex. For example, the volumetric expansion of
polymer material is usually greater compared to that of the fiber. The swelling can
lead to compressive stresses on the fiber. Excessive force can result in fiber frac-
ture if the mismatch in the swelling of fiber and matrix is too large. Microscopy of
exposed specimens can detect such possibilities.
The moisture uptake profiles with respect to time are used for calcula-
tion of diffusion rate of moisture in polymer [11]. The diffusion coefficient, D,
is a parameter of evaluation in such experimental analyses involving moisture
absorption and diffusion through polymers and other porous materials. The dif-
fusion occurring in a material can be classified as Fickian [15], if (a) the moisture
4.2 Studies on Moisture Effects on Polymers and Fiber-Reinforced Composites 45
absorption graph shows an initially linear behavior with the square root of
exposure time, (b) glass transition temperature (Tg) of the material is higher than
the test temperature, and (c) the overall water uptake is low. To assess the diffusiv-
ity D, Fick’s law for a semi-infinite plate is stated as [11, 16]
2 2
h M(t3 ) − M(t2 )
D=π √ √ (4.1)
4M(t4 ) t3 − t2
where M is the moisture content of the immersed specimen, defined as

w(t) − w0
M(t) = (4.2)
w0
where w(t) is the specimen weight as a function of immersion time and w0 is the
initial dry weight. The parameter h is the specimen thickness, and times t2 and t3
are selected within the initial linear region of the moisture uptake graphs. M(t4) is
the saturation concentration of moisture in the composite achieved at saturation
time t4. It is crucial that CNF/epoxy composites exposed to moisture show satura-
tion, allowing for measurement of the saturation concentration and subsequently
the diffusivity D for various CNF loadings.
In previous studies on carbon fiber laminates, it is shown that the tensile
strength is directly dependent on the level of moisture that the composites are
exposed to, despite differences in moisture and temperature exposure methods
[17]. Mechanical properties of carbon-fiber epoxy composites have been shown
to degrade more severely in seawater than in demineralized water under long-term
moisture conditions and Tg is also shown to decrease after moisture absorption
[18]. The effect of moisture induced degradation on high strain rate compressive
of impact properties of carbon fiber reinforced laminates has been of great interest
at different strain rates [19]. Select studies on laminates may sometimes be coun-
terintuitive, where moisture is shown to alleviate the impact-induced damages in
carbon fiber reinforced epoxy laminates [20]. SEM images in such a study have
shown notable retention of the microstructure morphology and integrity, where
no visible voids or cavities were found when comparing laminates under varying
hygrothermal conditions, as seen in Fig. 4.1 [20].
The hygroscopic behavior of epoxies used in carbon fiber laminates has been
established, where there are typically three sorption modes at room temperature [15]:
1. Moisture uptake in the polymer network;
2. Moisture absorption on surfaces of the free volume elements; and
3. Hydrogen bonding between water and polymer groups that are hydrophilic.
Despite the scarcity of moisture analyses on CNF/polymer composites, it can
be inferred that the potential effect of moisture on the fiber–matrix interface
is significant, given such sorption mechanisms. Further insight into moisture
diffusion within fibrous composites is obtained through finite element simulations,
which have demonstrated the effect of fiber geometry on the diffusion of moisture
Fig. 4.1 SEM images comparing carbon fiber laminates from a control group with no exposure
to temperature and moisture, b cyclically hygrothermally conditioned group, and c isothermally
conditioned group [20]
throughout the reinforced composites [21]. Parameters such as the fiber spacing,
fiber content, and adjacent fiber angles with respect to the moisture flow direction
are shown to influence the moisture diffusion profile and the saturation rate. A dia-
gram of these parameters is shown in Fig. 4.2 [21]. The saturation rate of the rein-
forced composite in the simulation can be mitigated considerably with a decrease
in filament spacing, particularly after 40 % saturation. However, the trend reverses
when the fiber angle with respect to the moisture flow direction increases. A com-
parison between both angles can be seen in Fig. 4.3 [21].
In the same study, the effect of fiber clusters was also modeled since they are
common in fiber reinforced composites. Moisture saturation over time was simu-
lated with variation of cluster geometries. It is observed that moisture saturation is
inhibited more with select cluster geometries, as shown in Fig. 4.4 [21]. Complete
saturation, shown in red, can easily be achieved with dense clusters containing
high fiber content, whereas saturation is noticeably slowed down with barrier lay-
ers of select geometries. Such results demonstrate that fiber placement, as opposed
to fiber density, is critical in the determination of the moisture diffusion character-
istics of composites. This concept also extends the possibility for cluster design in
order to achieve controlled diffusion in fiber reinforced composites.
4.3 Investigations on CNF/Polymer Composites 47
Fig. 4.2 Illustration of fiber neighborhood parameters, where θ represents the fiber angle with
respect to moisture front flow direction, N represents number of adjacent neighborhood fibers,
d represents the distance between fiber centers, and R represents the radius of the fiber [21]
Fig. 4.3 Percentage of saturated resin at neighborhood fiber angles of a 90° and b 150° with
respect to the flow direction [21]
4.3 Investigations on CNF/Polymer Composites
Studies on the effect of environmental exposure of CNF/polymer composites have

demonstrated retention in the mechanical and thermal properties with addition of
CNFs [22, 23]. A comparison between CNF and CNT reinforced epoxy compos-
ites shown in Fig. 4.5 illustrates considerable differences in water uptake amounts,
as well as common trends pertaining to water uptake variation with respect to
Fig. 4.4 Snapshots of moisture profiles for different clusters [21]
Fig. 4.5 Water uptake of epoxy resin with a CNF/epoxy composites and b CNT/epoxy

composites [22]
nanofiller content [22]. The samples used in the study made use of an environmen-
tal chamber at 55 °C and 95 % relative humidity for 60 days.
Water uptake generally decreases with dispersion of as little as 0.25 wt% CNF
and 0.1 wt% CNT, resulting in a 20–30 % decrease in the calculated diffusion
4.3 Investigations on CNF/Polymer Composites 49
coefficient D with respect to neat epoxy [22]. However, the decrease in water
uptake is mitigated when 1 wt% CNF or 0.25 wt% CNT is added to their respec-
tive composites. This is likely due to the presence of agglomerates at sufficiently
high weight fractions, which result in poor distribution of nanofillers and the pos-
sible presence of voids for water to diffuse in the composites. It should also be
noted that despite the addition of 0.75 wt% CNF, the difference between the water
uptake values of 0.25 and 1 wt% CNF/epoxy composites is not significant, where
most values hover around 1.4 % weight gain within the plateau region in Fig. 4.5a.
In contrast, with addition of only 0.15 wt% CNT, the water uptake for 0.25 and
0.1 wt% CNT-epoxy composites is around 1.5 and 1.25 %, respectively, for most
values around the plateau region in Fig. 4.5b. This discrepancy between the water
uptake variation of CNF and CNT reinforced composites may be due to the size
difference between CNFs and CNTs, providing different surface area for the
same concentration levels. It is also proposed that strong chemical interfaces were
formed between the epoxy matrix and the functionalized CNTs used in the study,
which caused the difference in water uptake between CNF and CNT composites.
However, effects that are not yet studied such as chirality of CNTs and the effect
of CNF structure that contains turbostratic graphite may also be contributors.
In the same study, increases in the Young’s modulus (21.7 %) and tensile
strength (23.1 %) are observed in dry epoxy composites containing 0.25 wt%
CNFs, with respect to the neat epoxy properties. However, the increases are mit-
igated with additional CNFs due to poor dispersion of CNFs at higher loading.
Despite the variation in modulus and strength with respect to CNF content, reten-
tion of such properties is observed with increased aging time. For composites
containing 0.25 wt% CNFs, the Young’s modulus of neat epoxy becomes higher
(2.68 GPa) than that of the CNF/epoxy composite (2.57 GPa) after 60 days of
aging. However, at 1 wt% CNF loading, the modulus of the composite remains
considerably higher than neat epoxy throughout the entire period of environmental
exposure. It is proposed that the bound water initially degrades the epoxy matrix,
resulting in a drop in the mechanical properties. However, with longer aging times,
the bound water induces multiple chemical connections, promoting an increase in
secondary crosslinking within the hygrophilic groups of the epoxy matrix, result-
ing in property rebound and retention. Later studies concur with the phenomenon
of property retention by CNF/epoxy composites with moisture exposure, where
the compressive modulus was found to increase by nearly 100 % with 1 wt% CNF
at room temperature after exposure for 6 months [23]. The strength of the same
wet CNF/epoxy composites decreased by 28 % with respect to the dry composites.
Competing mechanisms due to polymer matrix swelling may be invoked, where
changes in matrix surface morphology with moisture exposure can dislodge indi-
vidual CNFs from the matrix, causing a loss in strength. However, swelling may
also cause increased traction of the matrix on the CNFs, thereby improving load
transfer between fiber and matrix and ultimately increasing resistance to compres-
sive load.
Thermophysical properties of CNF/epoxy composites are also affected by
moisture exposure. The glass transition temperature Tg of CNF/epoxy composites
was found to be higher than that of neat epoxy at nearly all levels of moisture
uptake [22]. It is proposed that the steric hindrance of additional rigid elements
of longer length, such as added CNFs within the epoxy matrix, hinders epoxy
network movement, resulting in higher Tg. The storage modulus of CNF/epoxy
composites was found to be higher (2.6–2.7 GPa) than that of neat epoxy (about
2.5 GPa) due to the high stiffness of CNFs.
Retention of viscoelastic properties after moisture exposure is not limited
to CNF/epoxy composites. Reinforced polyester composites containing 1 wt%
CNFs have been aged for 1343 h. The results show that CNFs are more effective
in retarding diffusion through the composite compared to glass fibers [24]. With
moisture exposure, CNFs inhibited storage modulus degradation and caused vari-
ation in Tg that was dependent on the composite constituency. Furthermore, reten-
tion of the viscoelastic properties was such that the CNF/polyester composites
recuperated over 90 % of the maximum storage modulus and maintained moderate
Tg upon re-drying.
4.4 Summary
Extensive literature is available on degradation of various thermosetting and ther-

moplastic polymers due to water uptake at different temperatures. In comparison
to the polymers, CNFs have shown to improve the level of mechanical and thermal
property retention after environmental exposure. Moisture diffusion is known to
cause swelling in the resin, which exerts compressive forces on the reinforcement.
It is also observed that the fiber–matrix interfaces are preferentially attacked by
the moisture and surface treated fibers can be more effective in mitigating the det-
rimental effects. Research on the effects of long-term thermal cycling and ultravio-
let radiation are also important aspects of environmental exposure; studies under
such conditions can also give more insight into possible performance and degrada-
tion issues of nanocomposites. A limited number of available studies necessitates
further detailed investigations of this aspect of CNF/polymer composites.
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Chapter 5
Thermal Expansion of CNF/Polymer
Composites
Abstract Improved dimensional stability of composites is desired in applications

where they are exposed to varying temperature conditions. Polymers inherently
have a high coefficient of thermal expansion (CTE), which complicates their inclu-
sion in structural designs exposed to temperature extremes. However, through low-
CTE reinforcements dispersed in a polymeric matrix, the CTE of the composite
can be lowered to a degree suitable for use in service. This chapter aims at summa-
rizing the studies that analyze the effect of vapor-grown carbon nanofibers (CNFs)
on the thermal expansion behavior of polymer matrix composites. CNFs typically
have a significantly lower CTE than epoxy resins and other widely used polymer
matrices, which result in composites with increased dimensional stability as the
dispersed CNF content is increased. The use of nanofibers has resulted in the abil-
ity to tailor the thermal expansion of the composite over a wide range. Schapery’s
model is used to estimate the upper and lower bounds on the CTE of CNF/epoxy
nanocomposites. The experimental results are found to be within the bounds.
Keywords Carbon nanofiber · Coefficient of thermal expansion · Thermal

properties · Nanocomposite · Nanofiber dispersion
5.1 Introduction
Dimensional stability is a critical parameter in selecting materials for applica-

tions that are exposed to temperature variations [1, 2]. The ability to tailor both the
mechanical and thermal properties is an asset for composites. Some applications,
such as substrates for space mirrors, strive for materials with low or zero coef-
ficient of thermal expansion (CTE), while other applications, such as sandwich
skins or cores used in aircraft structures, desire composites with a tailored CTE
value to match with that of the adjacent components [3]. Thermal stresses can be
minimized at interfaces by matching the CTE of adjacent materials. Therefore,
understanding the trends observed in the CTE of composites with respect to the
properties and proportions of the constituent materials is desired.

54 5 Thermal Expansion of CNF/Polymer Composites
Polymer composites can exhibit improved thermal stability when reinforced

with phases that are stable at high temperatures and have low CTE [4], such as
carbon-based nanomaterials [5–7]. By replacing a fraction of the matrix polymer
with inclusions such as carbon nanofibers (CNFs) or CNTs, a composite with
enhanced dimensional stability can be fabricated [8–10]. With increasing focus on
more cost-effective reinforcements, use of CNFs for this purpose is explored, as
summarized in this chapter.
Current applications demand materials with high mechanical properties cou-
pled with low density. In addition, materials with tailored CTE can be extremely
useful in aircraft structures where large variations in stresses can occur during
their routine service conditions. Several studies have even assessed the CTE value
of CNF-reinforced multiscale composites containing both fibers and particles [1,
8, 10]. It has been observed in such studies that the addition of CNFs decreases the
CTE of particle or fiber reinforced composites. Such studies performed on mul-
tiphase composites fill a critical gap by studying a variety of composites to build
a comprehensive understanding of their respective thermal expansion behavior of
these composites. However, in the presence of second phase particles along with
CNFs, it is difficult to isolate and understand the effect of each constituent on the
CTE of the composite; therefore, such studies are not covered at this point.
5.2 Thermomechanical Analysis Methods
Experimental analyses on the CTE of fiber reinforced polymer composites have

been performed using various equipment and methods. One of the classic methods
of measuring CTE is through the use of a dilatometer. In this instrument, the differ-
ence in expansion between a rod made of the desired material and a standard silica
push rod of the same dimensions is compared [11]. A type of dilatometer is shown
in Fig. 5.1, which can measure the CTE with accuracy of ±0.1 × 10−6/°K [12].
Some investigations have conducted CTE measurements using linear strain
gages applied on the specimen surface [1, 8]. However, there are limitations in
Fig. 5.1 An image of a DI.24 ADAMEL LHOMARGY dilatometer [12]

5.2 Thermo-Mechanical Analysis Methods 55
Fig. 5.2 Schematic of TMA experimental setup
bonding the strain gages to certain materials, especially with operation at high
temperatures. Recently published experimental studies have used thermomechani-
cal analyzers (TMAs) for CTE measurement below the glass transition tempera-
ture of the matrix resin [13]. A schematic of the TMA setup is shown in Fig. 5.2. A
glass expansion probe is typically utilized in conjunction with a thermocouple in
order to measure the specimen expansion and temperature variation, respectively.
It is recommended that the specimens are preheated in an oven for 2 h at tem-
peratures below the glass transition temperature of the polymer matrix to remove
any surface moisture prior to the test. The glass expansion probe is positioned on
top of the specimen to measure the initial length and the expansion of the speci-
men under thermal loading with respect to temperature. The temperature ramp
rate depends on the thermal conductivity of the material and has been maintained
between 1 and 10 °C/min in previous studies [14]. Conducting materials can be
ramped at higher rates because of temperature homogenization throughout the
cross section in shorter time durations.
The CTE value is calculated from the slope of the resulting temperature-ther-
mal strain curve. It should be noted that the CTE may be a function of tempera-
ture. In some materials different slopes can be identified in different temperature
ranges. In such cases, the CTE values is presented with the appropriate measure-
ment temperature range.
5.3 Experimental and Analytical CTE Investigations
5.3.1 Experimental Results
The hollow core structure of vapor grown CNFs can be observed in Fig. 5.3a.
Previous work focused on characterizing CNFs (summarized in Chap. 2) has
shown that CNFs comprise a series of truncated cones (or cups) stacked vertically
Fig. 5.3 a Transmission electron micrograph of cup-stacked nanofibers showing their hollow
core structure (TEM image courtesy Drs. Deepam Maurya and Shashank Priya, Virginia Tech)
and b schematic representation of cup-stack structure
to provide a fibrous structure [15–18], as schematically illustrated in Fig. 5.3b.

Experimental evidence has shown that the structure may be composed of a long
narrow graphene ribbon helically folded in the form of a hollow tube [15]. A
small unit of this kind of structure would also resemble stacked cups, as shown
in Fig. 5.3b. The interaction between various layers of cup-stacks determines the
properties of CNFs [17, 19].
In typical nanocomposite specimens, CNFs are randomly dispersed as observed in
Fig. 5.4. It is important to characterize the microstructure of such composites, in order
to ensure that the nanofibers are wetted with the resin and are uniformly dispersed in
the composite microstructure. Bulk material properties such as CTE are affected by
the fiber–matrix interfacial strength and CNF distribution in the composite.
The theoretically predicted and the experimentally measured densities for such
nanocomposites, in addition to their respective CTE values, are listed in Table 5.1
Fig. 5.4 Scanning electron
micrograph of a composite
containing 10 wt% of CNFs
randomly dispersed in epoxy
resin matrix
5.3 Experimental and Analytical CTE Investigations 57
Table 5.1 Density and CTE values for CNF/epoxy composites at various CNF weight percent-
ages [20]
Composite type (wt%) Density (kg/m3) Experimental CTE
Measured Theoretical (×10−6/°C)
CNF/epoxy 1 1168.8 1164.7 68.0 ± 3.1
CNF/epoxy 2 1212.2 1169.5 67.0 ± 3.7
CNF/epoxy 5 1198.8 1184.0 60.1 ± 4.6
CNF/epoxy 10 1227.6 1209.0 57.8 ± 3.2
Fig. 5.5 Typical raw data 5 Neat epoxy

graphs of CNF/epoxy 1 wt.% CNF
composites with various 2 wt.% CNF
weight percentages of CNFs 4
5 wt.% CNF
Thermal strain, 10-3
10 wt.% CNF
3
0
30 50 70 90
Temperature, C
for a select study [20]. In most cases, the rule of mixtures density prediction and
experimentally measured densities are within 5 % of each other, which illustrates
that the matrix void entrapment during composite fabrication is small. A represent-
ative set of thermal strain graphs from the same study is shown in Fig. 5.5, where
data for one specimen of each composite is plotted for direct comparison of trends.
The slope of the thermal strain graph is defined as the CTE. The figure shows that
the CTE is dependent on the weight percentage of CNF. The measured CTE val-
ues for these composites are presented in Table 5.1 [20]. As the CNF content is
increased from 1 to 10 wt%, the thermal stability of the CNF/epoxy composites is
increased, with a maximum of 11.6 % CTE reduction at 10 wt% of CNF.
The CTE of neat epoxy resin is measured to be 65.4 × 10−6/°C. The CNF/
epoxy composites show a monotonically decreasing trend from 68 × 10−6 to
57.8 × 10−6/°C as the CNF content is increased from 1 to 10 wt%. The differ-
ence between the CTE values of neat resin and composites containing 0, 1, and
2 wt% CNFs is statistically insignificant, but composites containing higher CNF
content provide the indication of the trend. These measurements show that the
dimensional stability of composites increases with CNF content. CNFs have a
Fig. 5.6 Possible thermal
expansion effects in carbon Longitudinal
nanofibers [20] expansion
Cup
sliding
Transverse
expansion
cup-stacked structure with a hollow core, where individual cups may expand in
diameter and length. In addition, the cups may also slide with respect to each other
along the fiber length as the cup diameter increases with temperature, as schemati-
cally represented in Fig. 5.6. The expansion of cup diameter would allow them to
become more compactly packed, providing lower CTE of the CNFs and the result-
ing nanocomposites.
The effects of CNF on the CTE of other polymeric composites have also been
quantified and assessed in detail in other experimental investigations. In addition
to epoxy resin, polymeric matrices such as polypropylene, rubbery epoxy, and sili-
cone elastomers have been utilized for fabricating CNF-reinforced nanocompos-
ites. Phenolic resin composites containing up to 16 wt% CNF have been shown to
reduce the CTE by about 17 % with respect to neat resin [21]. EPON 800-series
epoxy resins have been utilized in several experimental analyses of CNF/epoxy
composites, where the CTE in one study has been reduced by as much as 11 %
with volume fractions ranging between 0.5, 1, and 2 wt% CNF [8].
5.3.2 Analytical Modeling CTE of CNF/Epoxy Composites
Theoretical micromechanics models have been developed for prediction of CTE

values and elastic constants of fiber-reinforced composites. The assumptions,
advantages, and disadvantages of several analytical models that predict the CTE
with respect to fiber volume fraction, fiber orientation, and elastic constants of
fiber and matrix have been extensively published [22]. Some models that are not
necessarily closed-form have been published with comparisons to experimental or
5.3 Experimental and Analytical CTE Investigations 59
numerical data, including comparisons to finite element models [23] and Monte
Carlo simulations [24]. General assumptions that are made in the models for eval-
uation of CTE include [22]:
• Temperature is uniform throughout the material and remains uniform during
temperature increase.
• The material properties of the constituents do not vary with temperature.
In addition to the rule of mixtures, which is a simplified estimate utilized in a
large number of experimental studies, several other models are available to obtain
more accurate predictions of the CTE of fiber-reinforced composites. Some of
these models can be adapted to CNF/polymer composites. Experimental results on
CNF/epoxy composites are compared with the Schapery’s bounds calculated for
CTE of unidirectional fiber composites [22, 25]. The bounded range of CTE can
be obtained as the longitudinal (αls) and transverse (αts) CTE predictions of the
model as [26]
αm φm Em + αf φf Ef
αls =
φm Em + φf Ef (5.1)

αts = 1 + νf αf φf + (1 + νm )αm φm − αls νf φf + νm φm (5.2)
where E, ν, φ, and α refer to Young’s modulus, Poisson’s ratio, volume fraction,
and CTE, respectively. Subscripts m and f refer to matrix and CNF, respectively.
The values for CNFs are obtained from theoretical studies because direct experi-
mental measurements are not yet readily available. It also becomes useful to
apply the longitudinal and transverse CTE predictions as upper and lower bounds,
respectively, because CNFs are usually randomly dispersed in actual composites.
To obtain analytical predictions in previous studies [20], the values assigned to
CNFs include Ef = 300 GPa [1, 27] and αf = 4 × 10−6/°C [27, 28]. CTE of the
neat epoxy resin was experimentally measured to be 65.1 × 10−6/°C. The elastic
modulus of the neat epoxy was measured under quasi-static compression and was
found to be Em = 1511 MPa [29]. Schapery’s upper and lower bounds for one set
of CNF/epoxy composites are plotted in Fig. 5.7, along with experimental results
on CNF/epoxy composites performed in the same study [20]. The experimental
results are within the bounds. Note that the input values of Ef and αf are obtained
from theoretical and simulation studies, which may affect the prediction accuracy.
The experimental data in Fig. 5.7 can be approximated as a linear trend by
α = −1.18ψ + 68.54 (5.3)
where α and ψ are the CTE of the composite and weight fraction of CNFs, respec-
tively. Since the upper bound (αls) corresponds to the fibers in the direction of
loading and the lower bound (αts) refers to all the fibers being oriented perpen-
dicular to the loading direction, the effectiveness of the reinforcement is calculated
as a parameter τ by comparing the experimental values with theoretical results as
α = τ αls + (1 − τ )αts (5.4)
Fig. 5.7 Schapery’s bounds 100

for CNF/epoxy composites
are plotted along with 80
corresponding experimental
CTE, × 10-6/°C
results
60
Experimental
40
Schapery Longitudinal
Schapery Transverse
20
0
0 5 10
wt.% CNF
The best matching is obtained between the theoretical and experimental results at
τ = 0.27 by curve fitting. This illustrates that due to the randomness of CNF in the
composite, their reinforcing efficiency is only 27 %. Several other parameters such
as CNF aspect ratio, entanglement, and curviness due to their large aspect ratio
may also affect the results.
5.4 Summary
There are several applications where the CTE of composite materials is an impor-
tant consideration. Substrates for electronic components and adhesives are exam-
ples where matching the CTE of two materials is very important to avoid failure
in the component due to thermal cycling. The ability of CNFs to tailor the CTE
of composites and provide very low CTE composites is very useful. Experimental
results are available that have used up to 10 wt% CNFs in epoxy resin and found
that the CTE of composites can be reduced by about 15 % at this reinforcement
level compared to the neat matrix resin. Schapery’s model is used for estimat-
ing the CTE of the composite. However, the model is used to find the lower and
upper bounds for certain level of CNF reinforcement. Comparison shows that
the experimental results are within the two theoretical bounds. In addition, due to
the random dispersion of CNFs in the composite, the reinforcing efficiency in the
measurement direction is about 27 %. The cup-stacked structure of CNFs helps
in obtaining low CTE because the lateral expansion of cups can make them more
compact and reduce the overall length of the fiber which results in the observed
CTE reduction of the composite.
References 61
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27. Wei, C. Y., & Srivastava, D. (2004). Nanomechanics of carbon nanofibers: Structural and
elastic properties. Applied Physics Letters, 85(12), 2208–2210.
28. Natsuki, T., Ni, Q.-Q., & Wu, S.-H. (2008). Temperature dependence of electrical resistivity
in carbon nanofiber/unsaturated polyester nanocomposites. Polymer Engineering & Science,
48(7), 1345–1350.
29. Gupta, N., Woldesenbet, E., & Mensah, P. (2004). Compression properties of syntac-
tic foams: Effect of cenosphere radius ratio and specimen aspect ratio. Composites Part A
Chapter 6
Dynamic Mechanical Analysis
of CNF/Polymer Composites
Abstract The viscoelastic properties of carbon nanofiber (CNF) reinforced

polymer matrix composites are examined in this chapter. Temperature-dependent
variations in the properties from subzero to above glass transition temperature (Tg)
is studied. Different compositions of CNF/polymer composites are evaluated for
parameters such as storage modulus, loss modulus, and damping parameter using
a dynamic mechanical analyzer. The maximum use temperature and Tg of such
composites are also determined. The ability to tailor the properties by means of
CNFs and improve the stability of reinforced polymer composites at high temper-
atures is important for aerospace applications that handle mechanical load under
thermal extremes.
Keywords Carbon nanofiber · Dynamic mechanical analysis · Storage modulus ·

Loss modulus · Glass transition temperature · Damping
6.1 Introduction
Applications of composite materials that require a high degree of stability under

combined mechanical and thermal loads include airplane and automotive com-
ponents [1]. Use of lightweight composites in transportation structures can save
weight and fuel. Many of the existing and potential structural applications require
materials with a high degree of dimensional stability and retention of mechanical
properties at high temperatures. Therefore, evaluation of high temperature elastic
and viscoelastic properties is necessary for composites used in these applications.
Thermal properties such as low coefficient of thermal expansion (CTE) and high
thermal conductivity of CNFs are helpful in developing multifunctional compos-
ites [2, 3]. Among other properties of interest is the ability of the material to store
and dissipate energy at various service temperatures.
Dynamic mechanical analysis (DMA) is a widely used technique in which load
is applied to a specimen at various frequencies. The specimen configuration can

64 6 Dynamic Mechanical Analysis of CNF/Polymer Composites
be cantilever, double cantilever, flexural, or tensile among the possibilities. As the

loading and unloading continues, a phase lag develops between the applied load
and observed deformation, depending on the elastic and viscoelastic properties
of the material. The stored and dissipated energies can provide storage and loss
modulus values, respectively. This kind of testing is usually conducted in conjunc-
tion with temperature or frequency ramping. A large number of studies on DMA
have maintained a constant frequency of 1 Hz and ramped the temperature. In this
case, a rapid decrease in the storage modulus is observed around the glass transi-
tion temperature Tg. The ratio of loss to the storage modulus is termed as damping
parameter Tan δ. The loss modulus-temperature plot can be used to also determine
Tg. In addition, the storage modulus-temperature plot can be used to determine the
maximum use temperature (Tmax), a temperature beyond which a rapid loss in the
storage modulus is observed.
In addition to temperature sweep, testing can also be conducted at a constant
temperature, while the frequency is varied. The dependence of storage and loss
modulus on frequency can be important for aircraft structures, which undergo
vibrations over a wide range of frequencies during their service life. The time-tem-
perature superposition principle can be used with a data set obtained on a limited
range of temperatures and frequencies to estimate the storage and loss moduli over
a wide range of temperatures and frequencies. The information on various param-
eters should be extracted at temperatures and loading frequencies that are relevant
to an application.
6.2 Dynamic Mechanical Analyses of CNF/Polymer

Composites
A comprehensive literature survey of dynamic mechanical properties of CNF/

polymer composites is presented in Table 6.1 [4–11]. The CNF content (Φf) is
found to vary in the range 0–25 wt% in nanocomposites characterized in these
studies. Certain studies expose composites to fixed temperatures near ambient
[10], whereas others analyze composite behavior from subzero to high tempera-
tures [8]. Most studies have conducted testing at a fixed frequency of 1 Hz [9,
11, 12] or 10 Hz [4, 13]. Results from the studies have shown variations in Tg
depending on the CNF content [4, 11–13], where Tg has been shown to decrease
by as much as 30 °C with 25 wt% CNF content [5]. The storage and loss mod-
uli of the composites vary significantly with CNF content. The storage and loss
moduli are found to change by as much as 250 and 46.7 %, respectively, with
graphitized CNF [10].
Table 6.1 Available studies on the dynamic mechanical properties of CNF reinforced polymer composites
Reference Composite typea Testing conditionsb Results
Xu et al. 2004 [5] Derakane 411-45 vinyl ester matrix; DMTA analysis in dual-level bending Tg decreases by up to 30.6 % w.r.t. neat vinyl
Pyrograf III VGCNF; Φf = 0–25 wt% mode; T = 30–200 °C; ω = 1 and 10 Hz ester at 25 wt% CNF loading
Finegan et al. 2003 Polypropylene matrix; Applied DMTA analysis, double cantilever bend- Increase in damping with increasing CNF
[10] Science, Inc. VGCNF; Φf = 0–15 ing mode; T = 21 °C; ω = 1 Hz content. Storage modulus increases by factor of
vol.% 2.5 and loss factor decreases by 46.7 %, w.r.t.
neat matrix
Choi et al. 2005 [6] Epikote 825 epoxy resin; Showa DMA analysis in stretching mode; Tg increased by 26 °C with addition of 20 wt%
Denko Japan VGCF; Φf = 0–20 wt% T = RT–200 °C; temperature scanning CNF with low viscosity epoxy composite,
rate of 5 °C/min; ω = 10 Hz storage modulus generally increases with
addition of CNFs
Choi et al. 2005 [4] NOVAREX 7020A polycarbon- DMTA analysis (loading mode unspeci- Addition of CNFs significantly increased stor-
ate; Showa Denko Japan VGCNF; fied); T = RT–200 °C at rate of 5 °C/min; age modulus below Tg, and Tg change is negli-
Φf = 0–25 wt% ω = 10 Hz gible (Tg = 160 °C) with varying CNF content
Yang et al. 2007 HXM-50100 High-density polyethyl- DMA analysis in tensile mode; Addition of 20 wt% CNF results in max
[9] ene; Pyrograf III CNF; Φf = 20 wt% T = RT–130 °C; ramp at rate of 3 °C/min; increase of 82 % in storage modulus, slightly
ω = 1 Hz higher damping than neat polyethylene
Zhou et al. 2007 SC-15 epoxy resin; Applied Science, DMA analysis in three-point bending Storage modulus and Tg increased by 65 % and
[7] Inc. CNF; Φf = 1–3 wt% mode; T = RT–160 °C; ω = 1 Hz 6 °C, respectively, with addition of 3 wt% CNF
Sun et al. 2011 EPON 862 epoxy; Pyrograf III CNF; DMA analysis in three-point bending Variation in Tg with addition of CNFs, storage
6.2 Dynamic Mechanical Analyses of CNF/Polymer Composites
[11] Φf = 0–2 wt% mode; T = 25–200 °C; at temperature modulus increases by 18 and 70 % below and
scanning rate of 3 °C/min; ω = 1 Hz above Tg, respectively, with addition of 1 wt%
CNF
Jang et al. 2011 [8] EPON 862 epoxy; Nano Amorphus DMA analysis (loading mode unspeci- Increase in storage modulus at 3 wt% CNF
Materials Inc. graphitized CNFs; fied); T = −50–130 °C; ω = 1 Hz over given temperature range, 10 % increase in
Φf = 3 wt% storage modulus at room temperature, 31.3 %
increase in loss modulus at room temperature
f
aΦ = fiber content
bT = temperature and ω = frequency
65
6.3 Results and Discussion
The storage and loss modulus results for a representative epoxy nanocomposite
specimen containing 2 wt% CNF are shown in Fig. 6.1. The curves can be divided
into four regions as shown in the figure:
(I) The subzero region, where the storage modulus decreases linearly with
temperature;
(II) The linear region above subzero temperatures until the start of glass transi-
tion region, where the storage modulus decreases linearly with temperature
but at a lower rate than that in Region I;
(III) The glass transition region where the material consistency changes from
elastic to viscous, and the storage modulus drastically decreases; and
(IV) The flow region where the material generally exhibits viscous behavior and
exhibits low values for both storage and loss moduli.
The maximum use temperature is identified as the intersection of tangents drawn
in Regions II and III. The temperature corresponding to the peak in the loss modu-
lus curve is defined as Tg. The damping parameter, Tan δ, is defined as the ratio
of the loss modulus over the storage modulus, and is indicative of the damping
capacity of the composite. The material stability increases with a decrease in the
area under the Tan δ curve [13]. The variation in storage modulus, loss modu-
lus, and Tan δ for CNF/epoxy composites is shown in Fig. 6.2. Results for the
neat epoxy resin are also included in these graphs for comparison. These graphs
are used to determine several quantities of interest listed in Table 6.2 through
Table 6.5 and the trends are discussed below.
The storage and loss moduli of CNF/epoxy composites at representative tem-
peratures in the subzero range (T = −50 °C), at room temperature (T = 30 °C),
(a) (b)
8000 500
I II III IV I II III IV
Storage modulus (MPa)
Loss modulus (MPa)
400
6000 Glass transition
temperature
300
4000
200
Maximum use
2000 temperature
100
N10 N10
0 0
-100 -50 0 50 100 150 200 -100 -50 0 50 100 150 200
Temperature ( C) Temperature ( C)
Fig. 6.1 Sample graphs indicating locations of four characteristic regions for evaluation of vis-
coelastic properties with respect to temperature. The maximum use and glass transition tempera-
ture can be found as shown in a from storage modulus and b from loss modulus, respectively
6.3 Results and Discussion 67
(a) (b)
8000 Neat epoxy 500 Neat epoxy
N1 N1
Storage modulus (MPa)
Loss modulus (MPa)

N2 400 N2
6000 N5 N5
N10 N10
300
4000
200
2000
100
0 0
-100 -50 0 50 100 150 200 -100 -50 0 50 100 150 200
Temperature ( C) Temperature ( C)
(c) 0.8 Neat epoxy

0.7 N1
N2
0.6 N5
0.5 N10
Tan
0.4
0.3
0.2
0.1
0
-100 -50 0 50 100 150 200
Temperature ( C)
Fig. 6.2 Comparison graphs of a storage modulus, b loss modulus, and c damping parameter

Tan δ of CNF/epoxy composites. The nomenclature of composites include N for nanocomposites,
followed by the weight fraction of CNFs
Table 6.2 Storage modulus values of CNF/epoxy composites at selected representative

temperatures
Material type Storage modulus (MPa)
T = −50 °C T = 30 °C T = 175 °C
Neat epoxy 4635.0 ± 105.4 3311.1 ± 66.9 22.4 ± 2.5
N1 4402.0 ± 128.8 3157.5 ± 117.5 83.0 ± 27.9
N2 4867.8 ± 130.9 3207.9 ± 263.2 83.6 ± 5.5
N5 4731.1 ± 177.5 3285.7 ± 131.8 95.8 ± 4.7
N10 5001.0 ± 68.2 3793.1 ± 52.2 112.0 ± 3.2
and in the flow region (T = 175 °C) are listed in Table 6.2. The N10 composite
attains the highest storage modulus at all temperatures; at −50, 30, and 175 °C,
the values are 7.9, 14.6, and 400 % higher than those for neat epoxy at the respec-
tive temperatures. The N10 composites demonstrate significantly higher storage
modulus values in Region IV with respect to neat epoxy, which is likely due to
bonding between CNF and resin molecules leading to increased viscosity of the
CNF reinforced resin. For the loss modulus values presented in Table 6.3, the N2
Table 6.3 Loss modulus Material type Loss modulus (MPa)

values of CNF/epoxy
T = −50 °C T = 30 °C T = 175 °C
composites at selected
representative temperatures Neat epoxy 246.7 ± 7.9 57.6 ± 2.3 0.2 ± 0.3
N1 218.3 ± 8.5 70.6 ± 15.0 2.9 ± 1.8
N2 265.1 ± 30.2 67.8 ± 7.9 4.0 ± 0.5
N5 250.5 ± 8.2 61.4 ± 4.0 2.5 ± 0.2
N10 239.7 ± 4.2 64.4 ± 2.9 1.4 ± 0.8
composite attains the highest value at −50 °C, whereas the N1 composite attains
the highest value at 30 °C. Such CNF/epoxy composites attain loss modulus val-
ues that are 7.5 and 22.6 % higher than neat epoxy at −50 and 30 °C, respectively.
However, there is no significant difference between the loss moduli for all com-
positions in the subzero range or at room temperature. At 175 °C the loss moduli
of all nanocomposites is significantly higher than that of the neat resin. Although
micrographs show uniform dispersion of CNFs in the composites, the higher loss
modulus for N2 composites may indicate that the dispersion of this composition
is the best. Higher CNF content may lead to entanglements that may not be com-
pletely dispersed. The results show that incorporation of CNFs increased the stor-
age and loss moduli of epoxy resin. The cup-stacked structure of CNFs can help
in increasing the elastic energy absorption because the graphene layers in CNFs
have some freedom to fold and unfold under the applied stresses. The expansion of
CNFs in the transverse direction can lead to further increases in the elastic energy
absorption in CNFs. Significant mismatch in the coefficient of thermal expansion
of CNFs and epoxy resin may lead to interfacial degradation and increase friction
between CNFs and the epoxy resin matrix, which can result in increased energy
loss. At high temperatures, transverse expansion of CNFs can result in shorten-
ing of their length, which will provide compressive stresses at the CNF/epoxy
interface and result in the increased viscosity of the mixture. Such mechanism can
account for the significantly high loss modulus of CNF/epoxy composites at high
temperatures compared to the neat epoxy.
Table 6.4 presents the Tan δ values at room temperature as well as at the peak
of the curves shown in Fig. 6.2c. CNF/epoxy composites have higher Tan δ at
room temperature but lower peak Tan δ compared to the neat resin. In general, no
significant difference is observed in the peak Tan δ values of CNF/epoxy compos-
ites. The temperature at which Tan δ attains a maximum also varies within a small
range and showed maximum value for N2 at 143.8 °C. The loss modulus and
Tan δ show indication of a β-relaxation peak in the subzero temperature range in
Regions I. Experimental measurements at lower temperatures may further reveal
the peak.The maximum use temperatures (Tmax) and Tg are listed in Table 6.5. It
can be observed that N2 composite attains both the highest Tmax and Tg, which are
measured to be 9.1 and 8.6 % higher than neat epoxy, respectively. The Tmax and
Tg for the N1 composite are measured to be 2.9 and 1.1 % lower than neat epoxy,
respectively. The Tmax and Tg for the N10 composite are 6.4 and 4.4 % lower than
neat epoxy, respectively.
6.4 Summary 69
Table 6.4 Tan δ values of CNF/epoxy composites at room temperature and the maximum value
Material type Tan δ
30 °C (×10−3) Maximum (×10−3) Temperature at maximum value
(°C)
Neat epoxy 17.4 ± 0.7 681.4 ± 10.6 124.6 ± 0.8
N1 21.8 ± 4.1 513.4 ± 42.9 131.6 ± 9.0
N2 21.1 ± 1.4 545.6 ± 16.4 143.8 ± 1.1
N5 18.7 ± 1.0 487.6 ± 8.9 132.8 ± 1.0
N10 17.0 ± 0.6 502.5 ± 9.8 121.3 ± 0.2
Table 6.5 Average values Material type Maximum use temperature (°C) Tg(°C)

for maximum use and glass
Neat epoxy 104.9 ± 1.5 116.2 ± 1.1
transition temperatures of
CNF/epoxy composites N1 101.9 ± 3.0 114.9 ± 6.2
N2 114.4 ± 3.1 126.2 ± 3.1
N5 105.8 ± 1.8 118.2 ± 0.9
N10 98.2 ± 0.7 111.1 ± 0.5
6.4 Summary
Viscoelastic properties of composite materials are important in modern transpor-

tation structures. Incorporation of CNF reinforcement can remarkably change the
ability of the material to store or dissipate energy when the load is applied at vari-
ous frequencies. It is also known that temperature can also change the material
behavior remarkably. One of the parameters that affect the viscoelastic proper-
ties of CNF/epoxy composites is the very low coefficient of thermal expansion of
CNFs, which can cause interfacial stresses during testing. The results show that
the storage and loss moduli are found to change by as much as 250 and 46.7 %,
respectively, with graphitized CNF. The composite containing 10 wt% CNFs
attains the highest storage modulus at all temperatures; at −50, 30, and 175 °C,
the values are 7.9, 14.6, and 400 % higher than those for neat epoxy at the respec-
tive temperatures. The results indicate that the dispersion of fibers has a remark-
able impact on the properties of the composite.
References
1. Thipse, S. S., Schoenitz, M., & Dreizin, E. L. (2002). Morphology and composition of the fly
ash particles produced in incineration of municipal solid waste. Fuel Processing Technology,
75(3), 173–184.
3. Yang, S., Taha-Tijerina, J., Serrato-Diaz, V., Hernandez, K., & Lozano, K. (2007). Dynamic
mechanical and thermal analysis of aligned vapor grown carbon nanofiber reinforced
polyethylene. Composites Part B Engineering, 38(2), 228–235.
4. Choi, Y. K., Sugimoto, K. I., Song, S. M., & Endo, M. (2005). Mechanical and thermal
properties of vapor-grown carbon nanofiber and polycarbonate composite sheets. Materials
Letters, 59(27), 3514–3520.
5. Xu, J., Donohoe, J. P., & Pittman, C. U, Jr. (2004). Preparation, electrical and mechanical
properties of vapor grown carbon fiber (VGCF)/vinyl ester composites. Composites Part A
6. Choi, Y.-K., Sugimoto, K.-I., Song, S.-M., Gotoh, Y., Ohkoshi, Y., & Endo, M. (2005).
Mechanical and physical properties of epoxy composites reinforced by vapor grown carbon
7. Zhou, Y., Akanda, S. R., Jeelani, S., & Lacy, T. E. (2007). Nonlinear constitutive equation
for vapor-grown carbon nanofiber-reinforced SC-15 epoxy at different strain rate. Materials
42(1), 98–103.
9. Yang, S., Taha-Tijerina, J., Serrato-Diaz, V., Hernandez, K., & Lozano, K. (2007). Dynamic
mechanical and thermal analysis of aligned vapor grown carbon nanofiber reinforced poly-
ethylene. Composites Part B Engineering, 38(2), 228–235.
10. Finegan, I. C., Tibbetts, G. G., & Gibson, R. F. (2003). Modeling and characteriza-
tion of damping in carbon nanofiber/polypropylene composites. Composites Science and
Technology, 63(11), 1629–1635.
11. Sun, L.-H., Ounaies, Z., Gao, X.-L., Whalen, C. A., & Yang, Z.-G. (2011). Preparation,
characterization, and modeling of carbon nanofiber/epoxy nanocomposites. Journal of
Nanomaterials, Article ID 307589, 8 p.
12. Zhou, Y., Pervin, F., & Jeelani, S. (2007). Effect vapor grown carbon nanofiber on thermal
and mechanical properties of epoxy. Journal of Materials Science, 42(17), 7544–7553.
13. Shunmugasamy, V., Pinisetty, D., & Gupta, N. (2013). Viscoelastic properties of hollow glass
particle filled vinyl ester matrix syntactic foams: effect of temperature and loading frequency.
Journal of Materials Science, 48(4), 1685–1701.
Chapter 7
Electrical Properties of CNF/Polymer
Composites
Abstract The electrical properties of carbon nanofiber (CNF) reinforced epoxy

matrix nanocomposites are summarized in this chapter. The effect of CNF weight
fraction on the conductivity, impedance, and dielectric constant is considered. The
results show that the impedance decreases and the dielectric constant increases
with increasing CNF content in the composites. Nanocomposites containing
10 wt% CNFs showed significantly higher dielectric constant because of the pres-
ence of a continuous network of CNFs in the composite. The resistance, capaci-
tance, and dielectric constants of the neat resin are found to be lower at the test
frequency of 105 Hz compared to the values measured at 1 Hz. The dielectric con-
stant of CNF/epoxy composites increases monotonically from 12.4 to 16.1 with
increasing CNF content from 1 to 10 wt%.
Keywords Carbon nanofiber · Nanocomposite · Electric properties · Dielectric

constant · Impedance · Permeability
7.1 Introduction
The electrical and thermal conductivity of CNFs can be used in conjunction with
the mechanical properties to develop multifunctionality in composite materials.
High mechanical properties [1], low coefficient of thermal expansion [2, 3], and
high electrical conductivity [4–8] are achieved in CNF reinforced composites. This
chapter is focused on studying the electrical properties of CNF reinforced epoxy
matrix composites.
7.2 Electrical Impedance Analysis
The electrical impedance was measured using a CH Instruments 700D (Austin,

TX) electrochemical potentiostat. Specimens were placed between gold elec-
trodes in order to measure the impedance and dielectric constant with respect to

72 7 Electrical Properties of CNF/Polymer Composites
frequency in the range 10−2–106 Hz with applied AC wave amplitude of 500 mV.

The impedance, denoted as Z , was obtained using the measurement of the electri-
cal resistance R and the capacitive reactance Xc as [9]

|Z| = R2 + Xc2 (7.1)
Both the resistance and the reactance, which represent the real and imaginary parts
of the impedance, respectively, can also be utilized to calculate the phase angle φ

−1 Xc
φ = tan (7.2)
R
The capacitance C is calculated by

1
C= (7.3)
2π f Xc
where f is the frequency. Finally, the dielectric constant is calculated as
Ct
ε= (7.4)
ε0 A
where t is the specimen thickness, A is the area, and ε0 is the permittivity of free
space. The value of ε0 is taken as 8.854 × 10−12 F/m.
7.3 Results and Discussion
It is known that epoxy resins exhibit a capacitive behavior. The neat epoxy resin
analyzed in this study shows a similar behavior and the phase angle is measured to
be around −87°. Impedance and dielectric constants with respect to frequency for
neat resin and CNF/epoxy composites are presented in Figs. 7.1 and 7.2, respec-
tively. The specimen nomenclature in these figures includes “N” representing CNF
reinforced nanocomposite and the numbers represent the weight fraction of CNF
in the composite. The log–log plot shows a linear relationship between impedance
and frequency as observed in Fig. 7.1 for neat resin and also for the nanocompos-
ites. The impedance of CNF/epoxy composites is lower than that of neat resin in
the tested range of frequencies. An opposite trend is observed for the dielectric
constants, as shown in Fig. 7.2. All CNF/epoxy composites demonstrate higher
dielectric constants over the entire frequency spectrum with respect to neat epoxy.
CNF/epoxy composites are shown to be less sensitive to field variations at higher
frequencies. The decrease in permittivity with increasing frequency has been
observed for CNF reinforced polyethylene composites in previous studies [10].
7.3 Results and Discussion 73
Fig. 7.1 Comparison of
impedance variation with
respect to frequency for
CNF/epoxy composites.
The results include the neat
epoxy matrix and composites
containing 1, 2, 5, and
10 wt% CNFs
Fig. 7.2 Comparison of 102
Neat epoxy
dielectric constant variation N1
with respect to frequency N2
for CNF/epoxy composites. N5
The results include the neat N10
epoxy matrix and composites
containing 1, 2, 5, and
10 wt% CNFs 101
100
100 101 102 103 104 105
Frequency (Hz)
The measured electrical properties of CNF/epoxy composites are presented in

Tables 7.1 and 7.2 at two representative frequencies of 1 and 105 Hz, respectively.
It is observed that at 1 Hz, the resistance and reactance of the composite decrease
as the CNF content is increased from 1 to 2 wt%. Further increase in the CNF con-
tent increases the resistance and reactance of the composite. An opposite trend is
observed in the capacitance and N2 composite shows the minimum value. The low
capacitance of the N2 composite leads to high dielectric constant compared to the
neat resin and other CNF/epoxy composites. This composite was also observed to
have high viscoelastic properties, which was attributed to its superior dispersion of
CNFs compared to other compositions.
The phase angle for composites containing 1, 5, and 10 wt% CNFs varies
within a narrow range of −76.3 to −77.5° and is close to the value of −78.2°
observed for the neat resin. The resistance, capacitance, and dielectric constants
of the neat resin are found to be lower at the test frequency of 105 Hz compared to
the values measured at 1 Hz. At this frequency, all the electric properties of CNF/
74 7 Electrical Properties of CNF/Polymer Composites
Table 7.1 Electrical properties of CNF/epoxy composites at 1 Hz

Composite Resistance Capacitance Reactance Phase angle Dielectric
type (Ω × 108) (F × 10−11) (Ω × 108) (°) constant (ε)
Epoxy 26.8 1.4 −114.8 −78.2 6.3
N1 9.4 4.2 −41.0 −76.6 19.9
N2 7.3 50.3 −4.1 −27.2 222.8
N5 7.7 5.2 −31.0 −76.3 26.4
N10 7.7 5.1 −34.7 −77.5 26.6
Table 7.2 Electrical properties of CNF/epoxy composites at 105 Hz

Composite Resistance Capacitance Reactance Phase angle Dielectric
type (Ω × 103) (F × 10−11) (Ω × 103) (°) constant (ε)
Epoxy 4.6 1.1 −151.1 −88.3 4.8
N1 2.2 2.6 −64.8 −88.0 12.4
N2 2.8 3.1 −51.5 −86.9 13.8
N5 1.9 3.1 −52.0 −87.9 15.8
N10 1.6 3.1 −56.5 −88.4 16.1
epoxy composites are found to vary within only a narrow range with respect to the
CNF content. The phase angle is found to be about 10° higher at 105 Hz frequency
compared to 1 Hz. Table 7.2 shows that the dielectric constant increases mono-
tonically from 12.4 to 16.1 with increasing CNF content from 1 to 10 wt%. These
results will be useful in understanding the trends observed in the electrical proper-
ties of CNF/syntactic foams.
7.4 Summary
The conducting nature of CNFs can provide conductive properties to CNF/epoxy

composites at sufficiently high CNF content. In the experimental studies, it is
observed that the resistance, capacitance, and dielectric constant of the neat resin
are lower at the test frequency of 105 Hz compared to the values measured at 1 Hz.
The dielectric constant of CNF/epoxy composites increases monotonically from
12.4 to 16.1 with increasing CNF content from 1 to 10 wt%. The resistance and
reactance of CNF/epoxy composites decrease as the CNFs content is increased
from 1 to 2 wt%. Further increase in the CNF content increases the resistance and
reactance. An opposite trend is observed in the capacitance and composite contain-
ing 2 wt% CNFs shows the minimum value. Tailoring of electrical properties of
materials through CNF content is useful in electronic packaging, electronic sub-
strate, and electromagnetic interference shielding applications.
References 75
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nanocomposite: Processing behavior, microstructure and electrical properties. Materials and
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Chapter 8
CNF Reinforced Multiscale Composites
Abstract Given the advantages of utilizing CNFs in polymers for improvement

in mechanical properties, current research has progressed to the reinforcement of
composites with three or more phases in order to elicit specified composite prop-
erty enhancements and support tailorability and multifunctionality within com-
posite systems. Since there are several possible categories in which to classify
such composites, the following sections will focus on two types of composites
that have been prominent in the literature: (1) particle reinforced composites with
CNFs and (2) continuous fiber composite laminates with CNFs. In this chapter, the
processing methods used to enhance the mechanical properties of the composite
are discussed first, and then the studies involving composites containing polymer
matrices, CNFs, and additional phases are reviewed.
Keywords Syntactic foam · Hollow particle · Nanoscale reinforcement ·

Carbon fiber · Carbon nanotube · Nanoclay · Glass fiber · Fracture toughness ·
Density-fracture toughness relation
Composites containing microparticles or microfibers are often optimized based on

well-developed theoretical models. In such composites, additional enhancement
in mechanical properties or generation of new properties such as thermal conduc-
tivity can be achieved through reinforcing the matrix resin with nanoscale fillers.
The nanofillers can occupy the spaces between microfillers and provide enhance-
ment in the properties of the matrix resin. Such approaches have been explored in
carbon nanofiber (CNF) reinforced nanocomposites with the addition of a second
phase filler or reinforcement.
Microfibers can be dispersed relatively easily in polymeric resins using stir
mixing methods, but nanoscale fillers require a more rigorous mixing routine.
Mechanical mixing using high shear impellers, shear mixing using three-roll
mills, and ultrasonic mixing using sonicators have been widely used to disperse
nanoscale materials in polymeric resins [1, 2]. Incorporation of nanoscale fillers
increases the viscosity of the resin [3], which can make it difficult to mix high

78 8 CNF Reinforced Multiscale Composites
volume fractions of nanoparticles or the second phase reinforcements. Long aspect

ratio nanostructures are preferred for enhancement in mechanical properties of
composites but the dispersion of such materials becomes difficult due to entangle-
ment, which is difficult to solve only by mechanical or shear mixing [4].
8.1 Composites with Three or More Phases
A vast variety of multiphase composites have been studied in the available litera-
ture. A few representative examples are discussed here, which present the spread
in the properties that can be obtained in such composites.
In one set of composites, the nanoscale reinforcements used include nan-
oclay and CNFs. The effect of nanoclay (1–5 wt%) was studied on glass
hollow particle/PEEKMOH toughened epoxy matrix composites. The hollow par-
ticle filled composites are called syntactic foams. The fracture toughness of epoxy
matrix syntactic foams is found to increase by 26 % through the addition of 5 wt%
nanoclay [5]. PEEKMOH toughened epoxy matrix syntactic foams were found to
have up to a 46 % improvement in fracture toughness at 5 wt% nanoclay addition.
The improvement in the fracture toughness due to PEEKMOH, is attributed to the
phase separation of the PEEKMOH domains in the epoxy matrix [5].
The effect of CNFs was studied on carbon hollow particle/phenolic resin syn-
tactic foams. An increase of 37 % in fracture toughness is observed with addition
of 1.5 vol% of CNFs, in comparison to the plain syntactic foam. Both fiber pullout
and crack bowing mechanisms were observed as the failure mechanisms in rein-
forced and plain syntactic foams, respectively.
These two examples establish the usefulness of the second phase reinforcement
in the composites. The use of hollow particles in high volume fraction is desired
in syntactic foams to keep the material density low. However, at high particle vol-
ume fraction, the mechanical properties such as strength are usually low, which
can benefit from the presence of CNFs. Use of CNFs in small volume fraction
helps in keeping the density low for the composite, while improving the mechani-
cal properties.
The effect of fiber length on the fracture toughness of phenolic hollow parti-
cle filled syntactic foams was studied [6]. To perform this analysis, the volume
fraction of hollow particles was kept constant at 30 %. For all the fiber lengths
tested (3, 4.5 and 10 mm), the fracture toughness increased with increasing fibers
content and a maximum increase of 95 % was observed for 10 mm length fiber at
3 wt%, with respect to plain syntactic foam. The effect of fiber materials such as
glass and carbon fibers on the fracture toughness of syntactic foams was studied
[7]. Carbon fibers were found to have a significantly stronger effect on the fracture
toughness than glass fibers. Addition of 0.9 vol% of carbon fibers was found to
improve the fracture toughness by 35 % compared to the plain syntactic foams.
Fiber pullout, particle matrix debonding, and particle failure were observed as the
8.1 Composites with Three or More Phases 79
failure mechanisms. In addition, fiber reinforcements created step-like structures

during the failure process, which helped in enhancing the fracture toughness due
to the high surface area of such structures.
The effect of nanoscale (nanoclay) and microscale reinforcements (short car-
bon fiber) on the fracture toughness of phenolic hollow particle filled epoxy matrix
syntactic foams was studied [6]. The study was performed keeping the volume
fraction of hollow particles constant at 30 % and varying the nanoclay content
from 0 to 2 wt% and the carbon fiber content from 1 to 3 wt%. A 42 % increase
in the fracture toughness was observed with addition of 1 wt% nanoclay in com-
parison to plain syntactic foam. With further increase in the nanoclay content, a
decrease in the fracture toughness was observed, owing to the agglomeration of the
nanoclay layers. The energy release rate was found to have a maximum increase of
104 % at 1 wt% of the nanoclay reinforcement, compared to plain syntactic foam.
The SCF reinforced syntactic foams showed an increasing fracture toughness and
energy release rate with an increasing weight fraction of carbon fibers. A maxi-
mum increase of about 109 % in the fracture toughness is observed at 3 wt% of
fiber addition. The study also observed that microscale reinforcement was more
effective than nanoscale reinforcement (nanoclay), under similar weight fractions.
8.2 Mechanical Properties of Multiscale Composites
8.2.1 Additional Reinforcement and Fillers
In combination with CNFs, several types of microscale reinforcements with a

large range of aspect ratios have been utilized within polymer composites [8].
A variety of microscale particulates with low aspect ratios such as silicon diox-
ide (SiO2) particles [9, 10], and hollow microspheres made of glass [11–15] and
carbon [16] have been dispersed within polymer matrices, in addition to various
weight percentage of CNF. The current studies that have analyzed such multiscale
composite systems are listed in Table 8.1. The results obtained in these studies are
also listed in the table, along with the details of the material system and the test
method. Most of these studies are focused on hollow particle filled composites
reinforced with CNFs.
E-glass [17–21] and carbon [22–34] fabrics have been utilized in conjunction
with CNFs in multiscale composite laminates. Polymer resins reinforced with
E-glass have been used in aerospace, marine, and automobile applications [19].
E-glass is also resistant to moisture degradation [35]. A list of available studies on
CNF/E-glass composite laminates is compiled in Table 8.2. The main results of
these studies are also summarized in the table.
The high stiffness and strength-to-weight ratio of carbon fibers provide bene-
fits for laminates in both aerospace and automobile structures [36–38]. However,
delamination of carbon fiber laminates is the primary mode of failure documented
Table 8.1 Available studies on bulk CNF/particle polymer composites
80

Colloca et al. [12] Matrix: D.E.R. 332 epoxy resin • Tensile test Maximum change in tensile modulus and
Particles: 3 M sodalime borosilicate glass • Nanoindentation test strength is 13.0 % decrease and 46.6 %
microballoons increase, respectively, with 1 wt% CNF
CNF: Pyrograf III PR-19 XT-PS; 1 wt% addition; variation of tensile and indenta-
tion test lower than 20 % compared to
theoretical
Dimchev et al. Matrix: D.E.R. 332 epoxy resin • Tensile test (0.5 mm/min) Tensile modulus and strength increase by
[13] Particles: 3M sodalime borosilicate glass • Compression test (1 mm/min) maximum of 20 % and 50 %, respectively;
microballoons CNF: Pyrograf III PR-19 compressive modulus decreases by
XT-PS; t 0.25 wt% maximum of 30 %, compressive strength
remains nearly the same
Poveda et al. [11] Matrix: D.E.R. 332 epoxy resin • Compression test (1 mm/min and high With respect to neat resin, compressive
Particles: 3 M sodalime borosilicate glass strain rates at ~ 103/s) strength and modulus increase by 7.3 % and
microballoons 15.5 %, respectively; compressive strength
CNF: Pyrograf III PR-19 XT-PS; 0–10 and modulus at high strain rates increase
wt% by factor of 3.4 and 3, respectively, when
compared to quasi-static values
Poveda et al. [14] Matrix: D.E.R. 332 epoxy resin • Compression test (1 mm/min and high Most compositions absorb between
Particles: 3 M sodalime borosilicate glass strain rates at ~ 103/s); effect of 6-month 0.75 and 2 wt% moisture depending
microballoons water immersion on compressive on microballoon content; compressive
CNF: Pyrograf III PR-19 XT-PS; 0–1 wt% properties assessed modulus is generally retained, but maxi-
mum strength decrease of 30 % observed
with respect to dry specimens
Zhang et al. [16] Matrix: Phenolic resin • Compression test (0.5 mm/min) Compressive strength variation is
Particles: hollow carbon microspheres • Flexural test (0.01/min) negligible, flexural strength and fracture
(HCMs) • Fracture toughness test (5 mm/min) toughness increases by 196 % and 37 %,
CNF: Pyrograf III; 0–2 vol% with addition of 1.5 vol% CNF
(continued)
8 CNF Reinforced Multiscale Composites
Uddin et al. [10] Matrix: SC 79 Bisphenol A epoxy resin • Flexural (3-point) test (1 mm/min) Flexural modulus and strength increased by
Particles: Nanopox silica nanoparticles 30 % and 45 %, respectively, with 8.5 wt%
CNF: Pyrograf III; 1.5 wt% silica and 1.5 wt% CNF
Zhang et al. [8] Matrix: Polypropylene • Flexural (4-point) test Flexural strength ranged from 39.5 to
Particle(s): pine wood flour and maleated 56.9 MPa, and flexural modulus ranged
polypropylene (MAPP) from 2448 to 4706 MPa, depending on
CNF: Pyrograf III PR-19-PS; 1 wt% composition
Poveda et al. [15] Matrix: D.E.R. 332 epoxy resin • Dynamic mechanical analysis, single Storage modulus lower than neat resin for
Particles: 3 M sodalime borosilicate glass cantilever mode all compositions, loss modulus increases
microballoons (T = −75 to 200 °C, ω = 1 Hz) by maximum of 25.3 %; Maximum use
CNF: Pyrograf III PR-19 XT-PS; 0–2 wt% temperature and Tg increase by maximum
of 27.1 % and 25.0 %, respectively, with
respect to neat epoxy
Jang et al. [9] Matrix: EPON 862 epoxy resin • Dynamic mechanical analysis (T = −50 Loss modulus increases by 37.9 % and
Particles: JUNSEI SiO2 particles; 0–9 to 130 °C, ω = 1 Hz) CTE decreases by 15 % with 3 wt% of both
wt% • CTE analysis using linear strain gages CNFs and SiO2, percentages with respect
CNF: Nano Amorphous Materials with K-type thermocouple (T = ambient to neat resin
graphitized; 3 wt% to 65 °C)
81
Table 8.2 Available studies on CNF/E-glass reinforced polymer composite laminates

Green et al. [18] Matrix: EPON 815 • Flexural (3-point) Flexural strength/
epoxy resin test (1.5 mm/min) modulus = 393 MPa/21
Fiber: E-glass weave • Short-beam shear GPa at 0.1 wt% CNF,
stacked into 12–16 test 404 MPa/22 GPa at
layers • Thermo-mechanical 1 wt% CNF; storage
CNF: surface- analysis (10 °C/min) modulus increased by
modified Pyrograf III • Dynamic mechani- 17 % and 4.5 % at 0.1
PR-19 HT, 0.1–1 wt% cal analysis and 1 wt% CNF respec-
(ω = 1 Hz, 5 °C/ tively, Tg increase by 25 °C
min) with respect to neat FRC
Hossain et al. Matrix: B-440 • Compression test Flexural strength and
[19] premium Polyester (1.27 mm/min) modulus increased
resin • Flexural (3-point) by 49 % and 31 %,
Fiber: plain weave test (2.0 mm/min) respectively; compres-
E-glass fiber sive strength and modulus
CNF: Pyrograf PR-24, increased by 43 % and
0–0.4 wt% 60 %, respectively, with
addition of 0.2 wt% CNF
Sadeghian et al. Matrix: unsaturated • Fracture toughness 100 % improvement in GIC
[20] polyester (Mode I) over neat resin laminate
Fiber: E-glass fiber
preform
CNF: Pyrograf III,
0–1 wt%
Zhu et al. [17] Matrix: EPON 8132 • Fracture toughness 30–57 % improvement in
epoxy resin (Mode I and II) fracture toughness/delami-
Fiber: S2-glass fibers nation resistance over neat
CNF: Pyrograf III resin laminate with 0.5
PR-24 HT, 0.5 wt% wt% CNF
Hossain et al. Matrix: B-440 pre- • Dynamic Up to 49.5 % improvement
[21] mium Polyester resin mechanical analysis in storage modulus,
Fiber: plain weave (T = 30 to 175 °C, up to 2.7 °C (2.3 %)
E-glass fiber ω = 1 Hz, 5 °C/min) improvement in Tg, and
CNF: Pyrograf PR-24, • Thermo-mechanical 30 % improvement in
0–0.4 wt% analysis (5 °C/min) ILSS, all with addition of
• Short-beam shear 0.2 wt% CNF
test
in several studies [32, 39]. To increase the delamination strength and fracture
toughness, CNFs have been introduced into the laminate system in one of three
ways:
• CNFs are pre-mixed into the polymeric resin, and then introduced between the
layers of carbon fiber [22, 30];
• CNFs are grown in bunches in order to form CNF mats or interlayers, in an
effort to introduce higher weight fractions of CNFs into laminates with ease [27,
28, 32, 40];
8.2 Mechanical Properties of Multiscale Composites 83
• CNFs are grown on carbon fibers through electrophoretic deposition and/or

chemical additives [26, 37].
Research investigations that have evaluated such processing methods with respect
to carbon fiber laminate mechanical properties are summarized in Table 8.3, where
inclusion of CNFs is shown to increase the interlaminar shear strength and fracture
toughness under different loading modes.
8.2.2 Compressive Properties
It seems unlikely that fibers would provide a major benefit to the compressive
properties of composites, given the high aspect ratio of fiber that would be sus-
ceptible to buckling under compressive load. However, with random homogeneous
dispersion of CNFs in a matrix, the lateral expansion of a composite under axial
loading can be restricted, thus prompting enhancement in the compressive strength
and modulus of the composite. Enhancements in the compressive properties with
CNF inclusion have been shown with several experimental studies on two-phase
composites [41], particularly those involving elastomeric matrices under compres-
sion [42, 43]. In polymer matrix composites tested under compression, CNFs are
found to bridge cracks and retard the crack growth reate. In such cases the CNFs
fracture under tensile mode, which has been previously studied and reported [44].
Hollow particle-filled composites such as syntactic foams are used in appli-
cations involving hydrostatic compressive loading, particularly for buoyant
marine structures and submersibles [45]. An SEM image of syntactic foam can
be observed in Fig. 8.1a. Since syntactic foams are designed to be lightweight by
keeping high volume fraction of hollow particles, nanoscale reinforcements such
as CNFs can be utilized for further property enhancement by modification of the
matrix resin. CNFs have been randomly dispersed within syntactic foams, as shown
in Fig. 8.1b, to elicit enhancements in the mechanical and thermal properties of the
resulting bulk composite. The quasi-static compressive strength of CNF reinforced
syntactic foams shows a large spread ranging from 40 MPa to around 120 MPa as
shown in Fig. 8.2a [13, 16, 44]. Negligible enhancement of compressive strength
was observed in syntactic foam containing hollow carbon microspheres [16]. Other
studies that analyzed the compressive properties of syntactic foam demonstrated
increases in the compressive strength of the overall composite with a combina-
tion of glass microballoons and CNFs [11]. The same type of three-phase syntac-
tic foam was also analyzed for its residual compressive properties after moisture
exposure and absorption for a period of 6 months, and a noticeable decrease in the
compressive strength can be observed in Fig. 8.2a [14]. A maximum weight gain of
7 % was observed in the worst performing composite in this study.
A limited amount of compressive analyses have been performed on CNF
reinforced composite laminates that include three or more phases [19, 26].
Determination of the in-plane strength of composite laminates is common;
Table 8.3 Available studies on CNF/carbon fiber reinforced polymer composite laminates
84

Rana et al. [24] Matrix: Bisphenol A epoxy resin • Tensile test (5 mm/min) Young’s modulus and tensile strength increased
Fiber: carbon fabric with satin weave pattern by 65 % and 36 %, respectively, with addition
CNF: Pyrograf III PR-24 functionalzed; of 0.1 wt% functionalized CNFs
0.1 wt%
Hu et al. [25] Matrix: jER 806 epoxy resin (Japan) • Tensile test Tensile modulus at 6 wt% CNF increased by
Fiber: TORAY T700S PAN-based carbon • Fracture toughness (Mode I) 36 %, tensile strength at 4 wt% CNF increased
fiber by 23.1 %, with respect to plain CF-epoxy
CNF: Showa Denko Co.; 0–6 wt% laminates; GIC decreases monotonically with
CNF increase
Palmeri et al. [22] Matrix: High-viscosity tetrafunctional • Tensile test ILSS and tensile modulus change by +22 %,
resin with and without reinforcing triblock • Short-beam shear test and −7 %, respectively, 20 % increase in
polymer • Fracture toughness (Mode I) toughness, and slight degradation of Tg
Fiber: PAN-based carbon fibers • DMTA analysis (T = 30 to 320 °C, observed with addition of CNFs
CNF: 0–2 wt% ω = 1 Hz, 3 °C/min)
Bortz et al. [30] Matrix: Resoltech 1800/1805 epoxy resin • Tensile test Tensile stiffness and strength increased by
Fiber: Hexcel PAN-based carbon fiber • Flexure test 5 % and 8 %, flexural modulus and strength
CNF: 1 wt% • Short-beam shear test both increased by ~ 10 %, fracture toughness
• Dynamic mechanical analysis increased by 35 %, negligible effect on Tg,
(single-frequency temperature ramp) with addition of 1 wt% CNF
Rodriguez et al. Matrix: EPON 862 epoxy resin • Compression test ILSS and compressive strength increased by
[26] Fiber: PAN-based IM7 6 K carbon fiber • Short-beam shear test 12.4 % and 12.6 %, respectively, with addition
layers of 0.67–1 wt% functionalized CNF
CNF: Pyrograf PR-24 XT-PS functional-
ized; 0.67–1 wt%
Chen et al. [28] Matrix: SC-15A epoxy resin • Flexural (3-point) test ILSS increased with addition of CNF mats
Fiber: woven T300 carbon fibers • Short-beam shear test by 221.1 %, flexural strength and modulus
CNF: PAN microfibers (SAF 3 K fibers) increased by 23.5 % and 105.0 %, respectively,
electrospun into carbon nanofiber mats of all with respect to plain CF-epoxy laminates
14 wt% content
8 CNF Reinforced Multiscale Composites
(continued)
Chen et al. [27] Matrix: SC-15A epoxy resin • Flexural (3-point) test ILSS increased with addition of CNF mats
Fiber: woven T300 carbon fibers • Short-beam shear test by 86.2 %, flexural strength and modulus
CNF: PAN microfibers (SAF 3 K fibers) increased by 11 % and 9 %, respectively, all
electrospun into carbon nanofiber mats of w.r.t. plain CF-epoxy laminates
14 wt% content
Li et al. [29] Matrix: epoxy resin • Flexural (3-point) test Flexure strength and modulus increased by
Fiber: TORAY T700S PAN-based carbon • Fracture toughness (Mode I) 8.6 % and 10.1 %; GIC increased by 95.4 %,
fiber all with respect to plain CF-epoxy laminates
CNF: Showa Denko Co.; 12.7 wt%
Khan et al. [31] Matrix: Huntsman LY 1564/Aradure 1571 • Fracture toughness (Mode II) 104 % increase in GIIC and 31 % increase in
epoxy • Short-beam shear test ILSS, with addition of CNF buckypaper to
Fiber: Pyrofil TR30S carbon fiber • End notched flexure test CFRP laminate
CNF: buckypaper interleaves made of 10
wt% CNFs (Hodogaya Chemical Co.)
Arai et al. [33] Matrix: DENATOOL XNR6809 epoxy • Fracture toughness (Mode I, static at With the addition of CNF interlayers, GIC
resin 0.5 mm/min and fatigue at 5 Hz) increases by maximum of 20 %

Fiber: TORAY C06347B carbon fiber
CNF: Showa Denko K.K., 7–13 vol%
Koissin et al. [34] Matrix: epoxy resin • Fracture toughness (Mode I) 100 % improvement in GIC (fracture tough-
Fiber: carbon fabric ness/delamination resistance) over neat resin
CNF: grafted carbon nanofibers, 1–11 laminate
wt%
Arai et al. [32] Matrix: epoxy resin • Fracture toughness (Mode I and II) At high CNF area density (20 g/m2), 50 %
Fiber: vapor grown carbon fiber • Hardness test max improvement in GIC, GIIC increased by
CNF: Showa Denko K.K., 7–13 vol% factor of 2–3, with respect to plain CF-epoxy
laminates
85
Fig. 8.1 SEM image of VGCNF reinforced syntactic foam (a) at low magnification showing glass
microballoons and (b) at high magnification showing 10 wt% CNFs dispersed in the matrix resin
(a) (b)
150 Dimchev, 2010 450
Compressive strength (MPa)
Poveda, 2013
Compressive strength (MPa)
Poveda, 2013 (Moisture Abs.) 375

120
Zhang, 2013
300
90
225 Hossain, 2011
60
150 Rodriguez, 2011
30
75
0 0
0 2 4 6 8 10 0 0.2 0.4 0.6 0.8 1
CNF wt.% CNF wt.%
Fig. 8.2 Comparison of compressive strength values of (a) particulate composites [11, 13, 14,
16], and (b) continuous fiber composite laminates [19, 26]
however, even delamination due to out-of-plane compressive loading has been

known to occur, particularly after impact [39]. The two studies compared in
Fig. 8.2b show the effect of functionalized CNFs on the flexure properties of lami-
nates, as well as the advantage of utilizing carbon-based fibrous phases. The in-
plane compressive properties of multiphase laminates were analyzed [26], where
the CNFs were grown and functionalized on the carbon fiber layers through the
use of electrophoretic deposition. In addition to carbon fiber, woven E-glass was
used in combination with randomly dispersed CNFs within a polyester matrix in
order to observe the effects of the reinforcement on the flexure properties [19]. An
increase in the compressive strength with CNF content is observed in both studies.
However, a monotonic trend is observed for the carbon fiber/CNF composite lami-
nate, as opposed to the woven E-glass/CNF laminate, where there is a decrease in
strength beyond 0.2 wt% CNFs.
(a) (b)
150 1500
Zhang, 2009
Flexural strength (MPa)

Uddin, 2010
Flexural strength (MPa)
1200
Zhang, 2013
100
900
Green, 2009
Li, 2009
600
50 Bortz, 2011
Chen, 2011
300
Hossain, 2011
Chen, 2013
0 0
0 1 2 3 4 0 5 10 15
CNF wt.% CNF wt.%
Fig. 8.3 Comparison of flexural strength values of (a) bulk particulate composites [10, 16, 47],
and (b) continuous fiber composite laminates [18, 19, 27–29, 48]
8.2.3 Flexural Properties
Flexure analyses require consideration of the tensile and compressive properties

of all phases included in the composite. Primarily, fibrous phases with high aspect
ratios contribute to improving the tensile properties of the composite, whereas par-
ticulates such as nanoclay and glass microballoons are more capable of withstand-
ing compressive loads [6, 46]. Hence, several studies on the flexural properties of
three-phase composites including both types of reinforcing materials have been pub-
lished, as shown in Fig. 8.3 [10, 16, 47] [18, 19, 27–29, 48]. Considerable enhance-
ment of the flexural strength of the composite can be observed even with composites
containing 1 wt% or less CNFs. As in the compressive studies denoted previously,
a considerably wider range of CNF weight fractions are utilized, with some studies
experimenting on compositions containing up to 14 wt% CNFs [27, 28].
Variability in the flexural strength has been observed with respect to 0–4 wt%
CNFs [16], where the strength is recorded to be the highest at 3 wt% CNFs.
Higher weight fractions of CNFs have contributed to CNF agglomeration resulting
in the formation of microcracks, thus leading to a decrease in the flexural strength.
However, determination of the effect of CNFs on the flexural properties becomes
more complicated when analyzing composites containing up to four phases [8],
which included CNFs, wood flour, maleated polypropylene, and a polypropylene
matrix. Wood flour and polypropylene have been preferred composite phases for
applications requiring low-density composites with a low impact on the environ-
ment. Given the difficulty of adhesion of fibrous phases on thermoplastic compos-
ites such as polypropylene, it was observed that flexural strength enhancements
due to CNFs were negligible despite previous success using extrusion techniques
for better CNF dispersion [8, 49]. Consistency of fabrication and phase disper-
sion methods have also been examined in multiphase composites containing
Fig. 8.4 (a) Schematic of composite laminate with layers of CNF mats in between layers of car-
bon fiber fabric, and (b) SEM images of A. the carbon fiber mat, B. randomly-oriented CNF mat,
and interlaminar fracture surfaces of C. carbon fiber/epoxy laminate, and D. carbon fiber/CNF/
epoxy hybrid laminate. Images taken from Chen, 2011 [27]
CNFs [10]. Through use of sol–gel and sonication techniques for better disper-
sion of silica nanoparticles and CNFs, respectively, increasing trends in the flex-
ural strength of such composites have been achieved, as shown in Fig. 8.3. A 40 %
increase in the flexural strength is observed in the CNF/silica hybrid composite
with respect to neat epoxy [10].
Graphitized CNFs and ECNF mats have been utilized in flexural analysis of
CNF reinforced three-phase laminates [18, 19, 28–30]. With CNF content rang-
ing from 0 to 1 wt%, increases in the flexural strength by about 9 % and 17 %
have been observed in multiphase composites containing E-glass [18] and carbon
fiber [30], respectively, when comparing the same base composites without CNFs.
Similar studies involving CNFs and woven E-glass fibers have elicited an increase
in the flexural strength at certain weight fractions of CNFs; however, the changes
in flexural strength were not monotonic [19]. It was found in this study that 0.2
wt% CNFs at a sonication time of 90 min was optimal, resulting in an increase in
the flexural strength and modulus of 88 % and 16 %, respectively. Enhancement
of CNF distribution within composite laminates to improve flexural properties has
been explored with the implementation of ECNF mats, which provide the follow-
ing advantages [27, 28]:
• Such mats can easily be sandwiched between laminate layers, which increases
ease of fabrication and processing;
• Increases in weight due to the addition of CNF mats are negligible, given that
ECNF mats are very thin; and
• The distribution of CNFs is generally considered to be uniform, since the fibers
in the CNF mats have randomly in-plane orientation.
A schematic of the CNF mat-reinforced carbon fiber composite laminate, as well
as SEM images of the different layers of the laminate, can be observed in Fig. 8.4a
and b, respectively [27]. CNF weight fractions of about 14 wt% was achieved in
Fig. 8.5 Comparison of 200 Rodriguez, 2011 Chen, 2011

shear strength values of Palmeri, 2011 Bortz, 2011
continuous fiber composite Chen, 2013 Green, 2009
Shear strength (MPa)

Khan, 2012 Hossain, 2013
laminates [18, 21, 22, 26–28, 150
30, 31]
100
50
0
0 5 10 15
CNF wt.%
such multiphase composite laminate systems along with high flexural strengths,
as observed in Fig. 8.3b. In two studies using carbon fiber mats, a flexural strength
increase of 23 % was achieved through surface attachment of CNF mats onto car-
bon fiber fabrics [28], as opposed to a 11 % increase due to interlaminar applica-
tion of CNF mats in between carbon fabric [27]. All percentages are compared to
base composite laminates not containing CNFs.
8.2.4 Interlaminar Shear Strength and Fracture Toughness
Studies on multiphase laminates have shown a considerable spread in the interlam-

inar shear strength (ILSS) with respect to CNF wt%, with ILSS values reaching
nearly 135 MPa between 0 and 2 wt%. CNFs. The ILSS values recorded in this
study are higher than others recorded here for three-phase composite laminates,
as shown in Fig. 8.5 [18, 21, 22, 26–28, 30, 31]. Depending on the orientation of
the carbon fibers (unidirectional or quasi-isotropic), the ILSS was enhanced by a
maximum of 22 % with the addition of CNFs. Despite utilizing different continu-
ous fiber materials such as carbon [22] and E-glass [18], existing studies display
similar trends in ILSS, where a non-monotonic trend with increasing CNF con-
tent is observed. The introduction of voids and defects in the presence of CNFs,
particularly with viscosity increases during fabrication, can reduce the reinforce-
ment efficiency such that optimal composite strength is reached at a lower CNF
content. In some experimental studies, monotonic trends in the ILSS of mul-
tiphase composite laminates with increasing CNF content may be observed [26,
30]. However, such studies test composite laminates that contain a maximum of 1
wt% CNFs, which may not yield optimal ILSS and fully describe variations in the
ILSS data trends. Studies previously discussed on the introduction of CNF mats in
laminates demonstrate increases in the ILSS at higher CNF content (14 wt%) [27,
28], but experimental values at intermediate composition levels are not available.
Fig. 8.6 (a) Schematic of unfurling of carbon nanofibers at a crack interface, (b) a time

sequenced splaying of a CNF embedded in epoxy, (c) nanocomposites fracture surface dem-
onstrating segmented CNF after fiber rupture, and (d) fracture surface displaying CNFs with
exposed graphene sheets at fiber tips. Images taken from Palmeri, 2010 [51]
Therefore, the trend cannot be fully assessed for such composite laminates at vary-
ing CNF contents.
It is of interest to observe the fracture toughness enhancements obtained
through the inclusion of CNFs. The mechanism of crack bridging is presented
in Fig. 8.6, where unfolding of the CNF structure can provide large strain in the
material [50, 51]. Rupture of bonds within the CNF structure allows for hindrance
of crack propagation, thereby inducing slow and stable crack growth and enhanc-
ing the fracture toughness of the composite.
Results on mode I interlaminar fracture toughness (GIC) for three-phase com-
posite laminates are emphasized here, although other studies have investigated
mode II and mixed mode interlaminar failure of three-phase laminates [17, 32,
40]. Experimental investigations demonstrated a relatively significant increase in
GIC of glass fiber/polyester composites of approximately 82 % with the addition
of 1 wt% CNFs [20]. Similar results are obtained by Koissin [34] with carbon fiber
laminates toughened with CNF, where over 100 % improvement in the Mode I
fracture toughness was noted with the addition of 2.6 wt% of CNF. In contrast,
previous experimental analyses performed on multiphase carbon fiber laminates
denoted issues with CNF agglomeration with or without modifications using an
Fig. 8.7 Comparison of 1400 Sadeghian, 2006 Li, 2009

mode I fracture toughness Palmeri, 2011 Hu, 2012
Fracture toughness (J/m2)

values of continuous fiber 1200 Zhu, 2012 Koissin, 2013
composite laminates [17, 20,
1000
22, 25, 29, 34]
800
600
400
200
0
0 3 6 9 12 15
CNF wt.%
elastomeric tri-block copolymer [22]. As a result, negligible enhancement in the

Mode I fracture toughness of such composites is observed, as shown in Fig. 8.7
[17, 20, 22, 25, 29, 34]. CNFs have been grown on the carbon fiber fabric itself
[34], thus mitigating agglomeration issues and demonstrating significant enhance-
ment in the fracture toughness of the laminates.
8.2.5 Dynamic Mechanical Analysis
Dynamic mechanical analysis (DMA) can provide the viscoelastic properties of

polymeric composites. Parameters such as storage modulus (measure of the stored
elastic energy in a material) and loss modulus (measure of the energy loss from a
material) under cyclical load are measured with respect to temperature and load-
ing frequency. In addition, the maximum use temperature and glass transition tem-
perature (Tg) of the composites can also be determined from the same test results.
Only a few studies on the viscoelastic properties of bulk polymeric composites
containing three or more phases are available. A comparison of Tg between two dif-
ferent multiphase composite types are shown in Fig. 8.8a, where up to 3 wt% CNFs
are dispersed in the composites. The addition of CNFs generally increases the Tg
of the SiO2/epoxy composites up to a temperature of 94 °C, and the presence of
both CNFs and SiO2 particles increase the storage modulus by 18.6 % with respect
to the neat resin [9]. The viscoelastic properties of CNF reinforced syntactic foam
were also reported, showing variation in the storage and loss modulus, as well as
the maximum use and glass transition temperatures with respect to the CNF and
glass microballoon content [15]. With respect to neat epoxy, Tg of CNF reinforced
syntactic foam may increase by as much as 25 %. Introduction of hollow glass par-
ticles and CNFs into epoxy resin allows for a wider range of Tg values at various
CNF weight fractions as shown in Fig. 8.8a. With the addition of 0.1 wt% CNFs in
E-glass fiber reinforced epoxy composites, an increase of 32 % can be observed in
(a) (b)
300 300
Jang, 2011
250 250
Poveda, 2013
200 200
Tg ( C)
Tg ( C)
150 150
100 100
50 50 Green, 2009 Bortz, 2011

Palmeri, 2011 Hossain, 2013
0 0
0 1 2 3 0 0.5 1 1.5 2
CNF wt.% CNF wt.%
Fig. 8.8 Comparison of glass transition temperature values of (a) bulk particulate composites [9,
15], and (b) continuous fiber composite laminates [18, 21, 22, 30]
Tg [18]. Negligible variation in Tg is observed in other studies performed with gra-

phitized CNF [22, 30]. It must be noted that only CNF weight fractions of 2 wt%
and below were utilized in the study. It may be possible to elicit a notable change in
Tg with higher CNF content in the composite laminate. However, such changes are
dependent on the crystallinity of the polymer, which is a function of the polymer
matrix type as well as the reinforcement concentration [52].
8.3 Summary
Studies on three, four, or multiphase composite materials are available on a wide

variety of systems. The purpose of incorporating each reinforcement should be
very clear in studying such materials. For example, hollow particles are used for
lightweight and high compressive modulus but the tensile strength of such syn-
tactic foam composites may be low, which can be improved by incorporation of
CNFs and other nanosized reinforcements. Through the thickness properties
laminates are also improved by dispersing CNFs in the matrix resin that is used
in the laminate. Such examples show clear synergy in the nano- and microscale
reinforcements used in composites. Studies on multiphase composites are usually
limited to experimental investigations because of complexities in modeling such
systems. However, remarkable improvement in the properties of the composites is
observed due to the nanoscale reinforcement.
References 93
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Index
A E
Analytical modeling, 38, 58 Electrical impedance, 72
Electric properties, 73
Electrospinning, 15
C Electrospun CNFs (ECNFs), 15
Carbon, 1–3, 6, 7, 11–13, 15, 19, 22, 27, 45, Epoxy composites, 8
46, 54, 78–80, 83, 84, 86, 88–90 Experimental validation, 38
Carbon fiber, 2, 28, 45, 78, 79, 84–86, 88–90
Carbon nanofiber (CNF), 1, 2, 7–9, 11–13, 15,
16, 18–23, 27–30, 32–37, 40, 43, 45, F
47–49, 50, 53–60, 63–66, 68, 69, 71, Fiber, 1, 2, 4–6, 8, 11–15, 19–22, 27, 28, 34,
73, 74, 77–80, 82–84, 86–92 38, 39, 44, 45, 47, 54, 58, 59, 69, 78,
Carbon nanotube, 6–8, 11–13, 22, 23, 34, 83, 89, 91
47–49, 54 Fiber reinforced composites, 44
Classification of composite, 4 Flexural properties, 2, 11, 35, 87, 88
CNF fabrication, 9 Fracture toughness, 31, 37, 78–80, 82–84, 89,
CNF investigations, 47 90, 91
CNF structure, 16, 18, 19, 33, 40, 49, 90
CNF surface enhancement, 20
Coefficient of thermal expansion, 34, 53–60, G
63, 68, 69, 71 Glass fiber, 8, 50, 78, 82, 88, 90, 91
Composite materials, 2–6, 27, 38, 40, 43, 63, Glass transition temperature, 45, 49, 55, 63,
69, 92 64, 66, 69, 91, 92
Compressive properties, 34
CTE investigations, 55
H
Hollow particle, 6–8, 78, 79, 83, 92
D Hybrid composites, 7, 8, 88
Damping, 63–67
Degradation, 28, 43, 45, 50, 68, 79, 84
Density-fracture toughness relation, 77 I
Dielectric constant, 71–74 Impedance, 71–73
Dispersion, 1, 8, 21, 28, 34, 35, 48, 68, 69, Interlaminar shear strength, 89
78, 87
Dynamic mechanical analysis, 9, 63–65, 81,
82, 84, 91 L
Loss modulus, 63–68, 81, 91

SpringerBriefs in Materials, DOI 10.1007/978-3-319-23787-9
98 Index
M S
Mechanical properties, 7–9, 16, 19–21, 27, 28, Storage modulus, 50, 63–67, 69, 81, 82, 91
33, 36, 40, 45, 47, 49, 78, 79, 83 Syntactic foam, 8, 74, 78, 79, 83, 86, 91, 92
Moisture, 43–50, 55, 79, 80, 83
Moisture effects on polymers, 44
Molecular dynamics, 11, 20, 22, 23 T
More phases, 78 Tensile properties, 28, 83
Multiscale composites, 7, 77, 79 Thermal properties, 9, 47, 53, 63, 83
Thermomechanical analysis, 54
Three phases, 78, 83, 87–90
N
Nanoclay, 2, 6, 78, 79, 87
Nanocomposite, 1, 6, 21, 36, 37, 41, 56, 58, U
64, 67, 68, 72, 77, 90 Ultraviolet radiation, 50
Nanofiber, 7, 11, 14, 17, 20, 22, 37, 53, 56
Nanofiber dispersion, 8, 20, 34–36, 40, 49, 60,
73, 83 V
Nanoscale reinforcement, 78, 79, 92 Vapor grown CNFs (VGCNFs), 12–21, 28,
Nanotube, 6, 27 34–36, 40, 55, 86
VGCNFs and ECNFs comparison, 15
Viscoelastic properties, 50, 63, 64, 66, 69,
P 73, 91
Particle, 2, 4, 6, 13, 54, 78–80, 91
Permeability, 71
Polyacrilonitrile, 11
Polymer matrix composites, 2
R
Reinforcement, 1, 2, 4, 6–8, 11, 16, 21, 28, 34,
43, 53, 54, 59, 60, 78, 79, 89, 92

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SPRINGER BRIEFS IN MATERIALS

ISSN 2192-1091 ISSN 2192-1105 (electronic)

Library of Congress Control Number: 2015948858

Springer Cham Heidelberg New York Dordrecht London

Printed on acid-free paper

Springer International Publishing AG Switzerland is part of Springer Science+Business Media

Unprecedented growth in the applications of composite materials has been

Brooklyn, NY, USA Ronald L. Poveda

2 Carbon Nanofibers: Structure and Fabrication. . . . . . . . . . . . . . . . . . . 11

3 Mechanical Properties of CNF/Polymer Composites . . . . . . . . . . . . . . 27

4 Environmental Effects on CNF/Polymer Composites. . . . . . . . . . . . . . 43

5 Thermal Expansion of CNF/Polymer Composites. . . . . . . . . . . . . . . . . 53

6 Dynamic Mechanical Analysis of CNF/Polymer Composites. . . . . . . . 63

7 Electrical Properties of CNF/Polymer Composites. . . . . . . . . . . . . . . . 71

8 CNF Reinforced Multiscale Composites. . . . . . . . . . . . . . . . . . . . . . . . . 77

Abstract The benefit of achieving multifuctionality has been a strong d­riving

Keywords Composite materials · Nanocomposites · Carbon nanofiber ·

© The Author(s) 2016 1

1.1 Polymer Matrix Composites

PMCs are materials that contain fillers or reinforcement phases in a continuous

1.1.1 Classification of Composite Materials

Sandwich Bulk Solid

Polymer Composite Fibrous

Fig. 1.3 Classification of composite materials

• Fiber reinforced composites

○ Aligned bi- or multidirectional fiber reinforced composites

○ Random fiber reinforced composites

– Fabric reinforced laminates

○ Triaxial weave fabric reinforced composites

○ 3D weave fabric reinforced composites

– Discontinuous fiber reinforced composites

○ Nanofiber reinforced composites

Fig. 1.4 An overview of carbon-based nanomaterials widely used in composite materials [10]

1.1.2 Hybrid and Multiscale Composites

In hybrid composites, reinforcements of two different morphologies may be incor-

1.2 Introduction to CNF/Epoxy Composites

1.3 Organization of the Present Book

Abstract In this chapter, vapor-grown and electrospun carbon nanofibers (CNFs)

The potential of using carbon-based nanofibers as reinforcement has been recog-

© The Author(s) 2016 11

2.1 Structure and Fabrication

2.1.1 Vapor Grown CNFs

2.1.2 Electrospun CNFs (ECNFs)

An alternate route to the production of CNFs is through electrospinning [19]. The

2.1.3 Comparison of VGCNFs and ECNFs

Fig. 2.5 TEM micrographs of broken edges of carbonized ECNFs with a loosened outermost

electrophoretic methods, as well as mechanical methods such as screw extrusion

2.2 Measured Mechanical Properties of CNFs

Direct measurements of mechanical properties were conducted on individual

Table 2.1 Experimentally measured strength and modulus values of CNFs

Fig. 2.6 Schematic of micromanipulator setup utilized for tensile tests on VGCNFs. Image

range of mechanical strength at processing temperatures of up to 1100 °C [21].

(a) 6 ECNF (Arshad, 2011) (b) 350 ECNF (Arshad, 2011)

Elastic modulus (GPa)

2.3 CNF Surface Enhancement

Efficient utilization of CNFs within composites is required for realizing their

Adhesion between the functionalized VGCNF surface and a polymer matrix

2.4 Modeling of Mechanical Properties of CNF

Before direct experimental measurements were conducted, iterative back-calcu-

Abstract This chapter discusses the effect of composition of CNF reinforced

Keywords Carbon nanofiber · Nanocomposites · Dispersion · Mechanical property ·

The potential of using carbon based fibers in developing high performance

© The Author(s) 2016 27

Abstract The benefit of achieving multifuctionality has been a strong driving

1.1 Polymer Matrix Composites

1.1.1 Classification of Composite Materials

1.1.2 Hybrid and Multiscale Composites

1.2 Introduction to CNF/Epoxy Composites

1.3 Organization of the Present Book

2.1 Structure and Fabrication

2.1.1 Vapor Grown CNFs

2.1.2 Electrospun CNFs (ECNFs)

2.1.3 Comparison of VGCNFs and ECNFs

2.2 Measured Mechanical Properties of CNFs

2.3 CNF Surface Enhancement

2.4 Modeling of Mechanical Properties of CNF

3.5 Other Mechanical Properties

3.6 Common Analytical Models for Experimental

4.2 Studies on Moisture Effects on Polymers and Fiber

4.3 Investigations on CNF/Polymer Composites

5.2 Thermomechanical Analysis Methods

5.3 Experimental and Analytical CTE Investigations

5.3.2 Analytical Modeling CTE of CNF/Epoxy Composites

6.2 Dynamic Mechanical Analyses of CNF/Polymer

6.3 Results and Discussion

7.2 Electrical Impedance Analysis

7.3 Results and Discussion