Documente Academic
Documente Profesional
Documente Cultură
entitled
by
Gregory J. Tilton
Composite materials are being more frequently used in a wide variety of indus-
tries. Their high strength to weight ratio makes them a desirable material in many
the composite’s thermal expansion, materials that have negative coefficients of ther-
mal expansion are used as a filler material. Zirconium tungstate (ZrW2 O8 ) is a metal
oxide which exhibits thermal behaviors not seen in most other materials. When sub-
to most other materials which show an increase in volume. This makes ZrW2 O8 an
pleted, this research looked at the finite element modeling of these composite materials
models were created using COMSOL Multiphysics with basic geometries for both the
matrix and filler. The results from these tests showed that the filler geometry had
little effect on the expansion results and volume fraction was the most important fac-
tor. To further test this, more complex models were created using three-dimensional
iii
geometries with the same volume fractions. These results confirmed the findings of
the two-dimensional tests by showing similar expansion. These results were then com-
pared to published experimental data where it was found that all the models showed
less expansion than the physical experiments of the same volume fraction.
The difference between the finite element analysis (FEA) and experimental results
was attributed to the interaction between the filler and matrix materials. In the mod-
els, the bond between the two was considered perfect, with no voids or separation,
leading to the filler material having more effect on the overall properties of the com-
posite. In real-world testing, this perfect bond would be nearly impossible to achieve.
To build on this idea and gain a better understanding of how the experimental test-
ing compared to the FEA, models with no bond between the filler and matrix were
created. Using the results from these models, as well as the models with a perfect
bond, an upper and lower bound of expansion were able to be created. All published
experimental data looked at was contained within these FEA-created bounds. This
showed that while some bond was likely made between the filler and matrix materials,
iv
Table of Contents
Abstract iii
Table of Contents v
List of Figures ix
1 Introduction 1
2 Literature Review 9
v
2.2 Experimental Research of ZrW2 O8 Composites . . . . . . . . . . . . . 11
3 Modeling Approach 17
Lower Bounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
5.1 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
References 59
A MATLAB Codes 67
A.1 MATLAB Code for Creating Random Coordinates for Spherical Inclu-
sions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
vi
A.2 MATLAB Codes for Creating a Mapped Mesh and Randomly Assign-
vii
List of Tables
viii
List of Figures
2-4 Chart comparing different mathematical models for predicting the CTE
of composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3-4 A screen-shot of the MBT showing changes made to the default solver . 22
3-8 Three-dimensional model with seven percent filler volume made of one
cylinder. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3-9 Three-dimensional model with seven percent filler volume made of nine
cylinders. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
ix
3-10 Three-dimensional model with seven percent filler volume made of twenty-
five cylinders. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3-11 Three-dimensional model with seven percent filler volume made of ten
spheres. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3-12 Three-dimensional model with seven percent filler volume made of fifty
spheres. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3-14 COMSOL results settings for determining the change in volume of the
models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4-2 Total displacement plots for two-dimensional models with seven percent
filler volume. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4-3 Total displacement plots for two-dimensional models with nineteen per-
4-6 A graph showing volume fraction versus relative expansion from the two-
dimensional data. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
4-7 Total displacement plot for 3-D model with one cylindrical filler particle. 43
4-8 Total displacement plot for 3-D model with nine cylindrical filler particles. 44
4-9 Total displacement plot for 3-D model with twenty-five cylindrical filler
particles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4-10 Total displacement plot for 3-D model with ten spherical filler particles. 46
4-11 Total displacement plot for 3-D model with fifty spherical filler particles. 46
4-12 Total displacement plot for 3-D model made with a mapped mesh of cube-
shaped particles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
x
4-13 Bar graph comparing the three-dimensional models studied. . . . . . . . 48
4-15 Graph showing the upper and lower bounds of expansion created by FEA
4-16 Graph showing the upper and lower bounds of expansion created by FEA
4-17 Graph showing the upper and lower bounds of expansion created by FEA
4-18 Graph showing the upper and lower bounds of expansion created by FEA
5-1 Geometry showing a possible way to model the interface between the
xi
List of Abbreviations
E . . . . . . . . . . . . . . . . . . . . . . Modulus of Elasticity
xii
List of Symbols
T . . . . . . . . temperature
∆T . . . . . . change in temperature
K . . . . . . . Kelvin, unit of temperature
xiii
Chapter 1
Introduction
temperature. This property can often create problems for engineers who must account
for this change in volume in their designs. While a majority of solids do not undergo
significant changes for their given operating temperatures, certain cases exist where
a large increase in volume is observed (e.g. [1–4]). This often leads to less than ideal
One way to combat the high thermal expansion in polymers is through the use
and expand given a temperature increase. Certain materials undergo thermal con-
traction, or, negative thermal expansion, and shrink when subjected to an increase
in temperature (Fig. 1-1). While none of these materials contain the properties to
completely replace polymers, they can be used to form a composite material that will
1
(a) Positive CTE (b) Negative CTE
Figure 1-1: Comparison between the effects of a positive and a negative CTE
when subjected to an increase in temperature.
results have shown that it is an effective way to reduce thermal expansion (e.g. [5–
8]). This research focuses on the finite element modeling of them in the hopes of
being able to correctly model the properties of these composites as well as gain a
better understanding of how the matrix and filler interact. With this understanding,
new experimental procedures could be developed to obtain better results and further
The objective of this work was to determine an accurate way to model composite
problems in finite element modeling (FEM) because they contain a filler material
that exhibits negative thermal expansion while the matrix material exhibits positive
the composite leading to imperfect bonds and separation between the two materials.
It is also likely that voids are created between the two materials during the production
2
of these composites. In a typical finite element model, the bond between the two
materials is modeled as a perfect connection with no separation and the voids are not
taken into consideration. This leads to inaccurate results that over-predict the effects
To conduct this study, the FEM software package COMSOL Multiphysics was
used. Different approaches to modeling the composite’s internal geometry were looked
at and a better understanding of the interface region between the two materials was
was not only to develop a way to closely match the experimental results, but also to
do so using the simplest model. This was to ensure that the results of this study were
not only beneficial to those running computers with multiple processors and large
quantities of RAM.
This thesis looks at the finite element analysis (FEA) of thermal expansion in
for the reader to better understand this work, a basic overview of the principals
used to conduct this research will be given. Topics covered will include composite
are combined. Their use has become more prevalent over the past few decades due to
the ability to obtain desirable properties that would not be achievable through the use
3
b b
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b b b b
b
b b b
b
b b b b
b b b
b b
b b
b b b b b
b b b
b b b
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b b b b b
b b
b b
b
b b
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b b b b b
b
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b b b b
bb b b
b
b b b b b
b b
b b
b b b
b b b b
b b b b
b b b b
b b b
Figure 1-2: Three cross-sections showing different ways filler material can
be included in a composite. Each has its own advantages and
disadvantages.
matrix and filler. The matrix is the material that holds the composite together. It
can be made up of a polymer, metal, or ceramic material and is usually chosen for
its ductility, toughness, or electrical insulation property (e.g. [9–11]). The filler is the
material that is mixed into the matrix to form the composite. It is held in place by
the matrix and used to improve certain properties of the matrix material in order to
posite’s volume fraction is the ratio of one constituent’s volume divided by the entire
composite’s volume. For a two-part composite, the volume of the filler material is
usually referenced. For instance, a composite consisting of two materials and a volume
fraction of 25% would contain one-quarter filler material and three-quarters matrix
material.
Filler material in composite materials can be included in various forms. (Fig. 1-2)
These can range from tiny, nanoscopic particles to long, fibrous strands. In many
cases, the way the filler is included can affect the final properties of the composite.
When fibrous filler is used and the fibers are specifically oriented, the composite will
exhibit anisotropic behavior. This means the composite will behave differently de-
4
pending on the direction of the load relative to the orientation of the fibers. However,
those same fibers could be randomly oriented within the matrix and the composite
would exhibit isotropic behavior. This means the composite would exhibit the same
properties regardless of the loading direction. This paper looks at randomly oriented,
However, some materials will exhibit thermal contraction, or negative thermal ex-
change [6]. The materials that exhibit this behavior typically only do so over a small
zirconium tungstate is a material that is being heavily researched due to its negative
(CTE), α, in its cubic phase of −9 × 10−6 K −1 [6]. Table 1.3.2 lists various materials
5
Figure 1-3: Structure of ZrW2 O8 [6].
along with their CTE for comparison. The NTE behavior of ZrW2 O8 is seen from 2 to
350K and can be attributed to its internal structure [6]. When ZrW2 O8 is subjected to
a positive temperature change, its rigid internal particles rotate, bringing them closer
together, decreasing the overall volume. Figure 1-3 shows the internal structure of
ZrW2 O8 that allows this. The NTE behavior can also be seen in other materials with
similar particle structure, however none have been found to occur over as wide of a
model to describe the behavior of a system. More often than not, this model will
find an exact solution to the system. In FEA, this system is broken down into small
6
solution to the system to be obtained.
Today, FEA is a very common technique used among engineers. It allows for com-
of these models are used to verify experimental results, which leads to fewer exper-
iments needing to be run, which leads to saving time and money. In this research,
solve thermal expansion problems. The results from the FEA were then compared to
The remaining chapters of this thesis will provide a detailed overview of the sim-
ulation approach taken to model ZrW2 O8 composites as well as how the simulations
of previous research in this area. It covers experimental research that has been done
on NTE composites, specifically those that deal with ZrW2 O8 /polymer composites.
It also reviews previous work in the mathematical and finite element modeling of
composite materials.
Chapter 3 covers the approach taken to model ZrW2 O8 composites in this research.
A detailed explanation of the 2-D and 3-D models are covered as well as the different
ways the filler material’s geometry was looked at. Details of the set-up and input
Chapter 4 contains the numerical results to the models as well as discussion about
the results. In this chapter, results from the FEA are compared to similar experi-
Finally, Chapter 5 includes the conclusions drawn from this research. It sum-
marizes the results from the modeling and published experimental data as well as
7
provides reasoning to the results. It also outlines possible future work, providing
goals and theoretical background to move forward with the research. The appendices
provided at the end of the document contain the computer codes used to develop
8
Chapter 2
Literature Review
Research in the areas of negative thermal expansion (NTE) and composite ma-
terials has been on the rise over the last two decades. Researchers are interested in
applications [5, 7, 8, 21, 22]. This chapter will review previous research involving NTE
perature, and it is assumed that pressure is held constant. For most materials, the
9
bc
rs bc rs
rs
rs
bc
bc bc bc bc bc bc
bc
rs
rs
rs bc rs
bc
Figure 2-1: Diagram showing thermal contraction in oxides. Circles repre-
sent oxygen and squares represent cations. As temperature is
increased, the movement of the oxygen atoms causes the cations
to become closer together. Therefore, the overall volume de-
creases [24].
ever, in some materials, the value of the CTE is negative in at least one direction and
The study of NTE materials has been ongoing for roughly twenty years. Early
researchers found that there were several oxide systems that exhibited the behavior
[23–30]. In this research, however, it was found that the materials only exhibited
NTE behavior over a small, high temperature range. In addition, the contraction
of the material was usually small and anisotropic. From there, researchers sought
to determine the source of the NTE behavior in these materials. It was found that
the excited oxygen atoms linked to other elements were the cause [24]. The linkages
start linear, but then thermally bend when temperature is increased (Fig. 2-1). This
thermal bending causes a decrease in length between atoms which leads to a decrease
One particular material that gained the attention of researchers of negative ther-
mal expansion was zirconium tungstate (ZrW2 O8 ). This material is a ternary oxide
first discovered by Graham et al. in 1959 [31]. In 1967, the phase relations of the oxide
were reported by Chang et al. [32]. This aided in the discovery of its NTE behavior
10
in 1996 by Sleight et al. [14]. This research shows that the NTE behavior exists from
its cubic symmetry, the NTE properties are isotropic over its entire stability range.
Similar NTE behavior was also found by Sleight et al. for HfW2 O8 , but the cost to
produce it is much higher [21]. These findings have led to ZrW2 O8 become a highly
Production of ZrW2 O8 is somewhat challenging and has been carried out in differ-
ent ways [8, 15, 33–36]. For use in composites, small particles of ZrW2 O8 of uniform
size are desirable. This keeps particles from settling during the formation of the com-
also been created to further improve homogeneity as well as mechanical strength [7].
The knowledge of zirconium tungstate’s NTE behavior led to its use as filler in
composite materials. The use of polymers as the matrix material allows for a wide
range of applications with low cost and ease of production [37]. The addition of
filler materials within the polymer allows for fine tuning of the material properties
by combining the favorable properties of the polymer with favorable properties from
a filler material [38–42]. Incorporating ZrW2 O8 into matrix materials has allowed
researchers to reduce the overall CTE of the composite [5,8,13,21,22]. This is desirable
due to polymers’ usually high CTE, reducing their usefulness in certain applications
[43–45]. Figure 2-2 shows an example of this research conducted by Tani et al. where
ZrW2 O8 was added to a phenolic resin matrix. As the volume fraction of ZrW2 O8 is
Researchers are now beginning to look into the interface between the filler and
the matrix [7, 46–49]. This is especially important in composites with ZrW2 O8 as a
11
Figure 2-2: Chart showing the effect of ZrW2 O8 on a phenolic resin ma-
trix during a temperature increase. As the volume fraction of
ZrW2 O8 increases, the overall expansion of the composite de-
creases [5].
filler because of the opposing forces created during a positive temperature change.
Because of this, the interface between the two materials is subjected to high stress.
When the stress becomes too high and the two materials separate, the effect of the
filler material is reduced. Researchers are currently trying different surface treatments
to the ZrW2 O8 to improve the bond between the filler and matrix [7]. Improvement
to this interface region allows the ZrW2 O8 to further reduce the composite’s CTE.
of Composites
Several mathematical models have been developed to predict the overall CTE
12
Figure 2-3: Figure displaying the opposing forces in a ZrW2 O8 composite.
The gray area represents the ZrW2 O8 filler and the white area
represents the matrix material. The dotted line is the interface
between the two materials where high stresses would be seen
when subjected to a temperature increase.
complex equations that account for material stiffness and matrix/filler interaction.
This interaction can greatly affect the resulting CTE of the composite which allows
these models to give more accurate results [5]. A chart comparing results from each
The simplest of the mathematical models is called the Rule of Mixtures (ROM)
[53]. The ROM is a linear average of the matrix’s and filler’s CTE based on volume
αc = vf αf + (1 − vf )αm (2.2)
where αc , αf , and αm are the coefficients of thermal expansion of the composite, filler,
and matrix, respectfully and vf is the volume fraction of the filler. The ROM model
does not account for any relationship between the filler and matrix and also does not
account for the stiffness of either material. It assumes a uniform stress distribution
Another mathematical model for predicting the CTE of a composite is called the
13
Turner model [50]. This model builds upon the ROM and incorporates each materials
vf Kf αf + (1 − vf )Km αm
αc = (2.3)
vf Kf + (1 − vf )Km
where Kf and Km represent the filler and matrix bulk moduli, respectively. αc , αf ,
αm , and vf are the same as from the ROM. One will notice that if Kf is equal to Km ,
The last model to be covered is called the Schapery model [51]. This model
consists of two equations that develop an upper and lower bound for the effective CTE
of composites. Schapery used energy principles to develop this model that works for
isotropic and anisotropic composites and also is independent of filler geometry. The
Schapery model also uses a model for elastic modulus developed by Hashin-Shtrikman
(H-S) [54] within the CTE equations. The upper bound is expressed as
where the superscript u and l refer to the upper and lower bounds and Kcu andKcl
are calculated from the H-S model using the equations below.
1 − vf
Kcu = Kf + 1 3vf (2.6)
Km −Kf
+ 3Kf +4Gf
vf
Kcl = Km + 3(1−vf )
(2.7)
1
Kf −Km
+ 3Km +4Gm
In the Schapery and H-S equations, all variables are the same as in the previous
14
Figure 2-4: Chart comparing different mathematical models for predicting
the CTE of composites. All calculations were done for a com-
posite with a polymer matrix and ZrW2 O8 filler.
two models and Gm and Gf represent the shear moduli of the matrix and filler,
respectively. A chart comparing the results of the three models can be seen in Figure
2-4.
posites
tions that are difficult or impossible to solve analytically [55]. The finite element
15
method takes a given geometry and breaks it down into smaller parts (elements)
and uses a system of algebraic equations to describe the relationship at the points
(nodes) connecting the elements [6]. This allows the original differential equations to
be simplified into a system of algebraic equations that can be quickly solved using a
FEA allows researchers to test ideas and theories without having to purchase
materials and produce samples. It can also be used to verify experimental results. In
the study of thermal expansion in composites, FEA is a tool that can give an idea of
the effect certain filler materials will have on the overall composite and what volume
Research in the area of FEA of particulate composites has been mostly limited
to composites with positive CTEs for both the filler and matrix [56–61]. In these
studies, the effect of particle size, shape, and distribution within the FEA model have
date, little research on the FEA of composites with negative CTE fillers has been
completed. One study in the area looked at the FEA of closely packed tetrahedra
ZrW2 O8 at 60% volume loading in a copper matrix [62]. This study used FEA to
calculate the thermal mismatch stresses within the composite and found that they
geometry, and packing fraction influenced the overall expansion and thermal stress in
composites with ZrW2 O8 filler and either copper or ziconium oxide matrix [6]. Here
researchers concluded that the thermal stresses are larger when the amount of filler
is larger and that it is advantageous to use matrix and filler materials with similar
magnitudes of CTE. The research of this thesis built upon these works and studied
16
Chapter 3
Modeling Approach
polymer based composites with zirconium tungstate as a filler material. The FEA
was completed with the software package COMSOL Multiphysics version 4.0 using the
structural mechanics module. This software allowed for two and three-dimensional
models to be created with different numbers of filler particles and different filler
modeling including the materials used and their properties, the various geometries
of the 2-D and 3-D models, the setup for COMSOL, and how the solutions to the
The materials studied in this research were polymer based composites with the
negative thermal expansion material ZrW2 O8 as a filler. Two different polymer matrix
materials were looked at in order to compare the results from the FEA to experimental
results published by Tani et al. [5] and Sharma et al. [7] The experiments conducted
by Tani and Sharma were on ZrW2 O8 composites using phenolic resin (PR) and poly-
imide (PI) as the matrix materials, respectively. To run FEA of thermal expansion
17
on these composites, four material properties are required for each material. These
are Young’s modulus (E), Poisson’s Ratio (ν), density (ρ), and coefficient of thermal
expansion (α). Then, in order to calculate the CTE using the mathematical models
discussed in section 2.3, the materials’ bulk moduli (K) and shear moduli (G) must
also be known. All of the materials used are listed in table 3.1 with each of their
required properties.
Table 3.1: Materials used in FEA models and their required properties
kg −6
Material E(GP a) ν ρ( m3) α( 10K ) K(GP a) G(GP a)
ZrW2 O8 88.3 0.33 5090 -9.0 74.5 33.9
PI 2.2 0.35 1430 64.2 2.4 0.8
PR 3.5 0.37 1370 45.6 4.5 1.3
This research was conducted using the finite element software COMSOL Mul-
tiphysics version 4.0. This software was used to create two and three-dimensional
models, simulate a change in temperature applied to the models, and analyze the ef-
fects of the temperature change on the models’ dimensions. This section will overview
When first opening COMSOL multiphysics, a window similar to the one in figure
3-1 is seen. When starting a new model, this is where options such as space dimension,
physics, and type of study are selected. For this research, both 2-D and 3-D models
were used, so one of those two options was chosen first. Next, COMSOL prompts
users to choose which physics modules they would like to use. COMSOL is capable of
running multiple physics modules on one model, however, for this research, only the
solid mechanics module under the structural mechanics section was needed. Lastly,
18
Figure 3-1: Opening window seen when COMSOL is first launched. This
research used both 2-D and 3-D modeling, the solid mechan-
ics module under structural mechanics physics, and a stationary
study.
COMSOL needs to know what type of study will be run, which in this case was
stationary.
After inputing the initial settings, the model is ready to be created. At this
point, the geometries of the matrix and filler are drawn. Details about the different
geometries studied and how they were created can be seen in sections 3.3 and 3.4.
Once the geometry of the model is made, the matrix and filler material properties
need to be assigned. To do this, two materials were created for each model under the
material branch of the model builder tree (MBT). (Fig. 3-2) Then, the properties
listed in Table 3.1 were input to the appropriate matrix or filler material.
The next step was to apply boundary conditions to the model. This is done under
the solid mechanics branch of the MBT. For all models, roller supports were used as
the only boundary conditions. The rollers were added to the x = 0, y = 0, and z = 0
19
Figure 3-2: An example of what the model builder tree in COMSOL looked
like for the finite element models created for this research.
surfaces (or just the x and y if the model was 2-D) to allow for thermal expansion
in the positive directions similar to what is seen in Figure 1-1(a). After applying
the boundary conditions, the loads were applied to the models. While there were no
external forces applied in any of the simulations, the loading was applied through a
change in temperature. To do this, the thermal expansion option was added to the
model under the linear elastic material model branch of the MBT. Once added, this
option allowed for two temperatures to be defined. The first was the strain reference
temperature, Tref , which was the initial temperature of the model. Then, the user
defined temperature, T , was the final temperature. Subtracting Tref from T allowed
for the change in temperature, ∆T , to be calculated. For all models, ∆T was positive
After the boundary conditions and loads were applied, the model was ready to be
meshed. Meshing in FEA is where the geometry of the model is broken down into
20
Figure 3-3: An example of a two-dimensional, free triangular mesh in COM-
SOL set at the ‘finer’ size setting.
smaller pieces, called elements, which are connected by nodes. Each element is then
meshing models, it is generally understood that a finer mesh (more elements) will give
a more accurate solution. However, a finer mesh will also require more time for the
balance between computation time and an acceptable level of accuracy. A mesh was
created in COMSOL by right-clicking on the mesh branch of the MBT and selecting
free triangular for 2-D models and free tetrahedral for 3-D models. Then, the size
of the mesh was set to the ‘finer’ setting. This gave an initial starting point for the
mesh which could then be adjusted either finer or courser based on the time it took
to solve the problem. An example of a two-dimensional mesh set to the ‘finer’ setting
The last step in setting up COMSOL for this research was to adjust the default
21
Figure 3-4: A screen-shot of the MBT showing the changes made to the de-
fault solver. Changes were made under the ‘Advanced’, ‘Iterative
1’, and ‘Multigrid 1’ branches to achieve faster solution times
with no effect to the accuracy of the results.
solver settings. This allowed for the solutions to be found in a slightly faster time
while having no negative effects on the accuracy of the solution. To do this, the study
branch of the MBT was right-clicked on and ‘show default solver’ was selected. Once
all the drop-down menus are expanded, various options are available to change on
the solver. For the models run in this research, the first change was made under the
‘Advanced’ branch which was found under ‘Stationary Solver 1’. Here the matrix
symmetry was changed from automatic to symmetric. The next change was made
on the ‘Iterative 1’ branch. Here the solver was changed from GMRES to conjugate
gradients. The last change was made under the ‘Multigrid 1’ branch where the solver
setting was changed from a geometric to an algebraic multigrid. The branches these
22
3.3 Modeling to Compare Geometry
The first portion of this research looked to compare the FEA results of polymer/ZrW2 O8
composites with the same volume fraction but different geometries. The goal was to
determine if varying the geometry of the model had a significant effect on the results.
filler geometries and numbers. Details of the geometries modeled and compared can
The initial modeling completed for this research was done using two-dimensional
models. These models were created using the same materials and volume fractions
and then subjected to the same temperature change. The goal was to compare these
models to see the effect different filler geometries and number of inclusions has on the
change. The first model created was a completely isotropic polymer to use as a
on the ‘Geometry’ branch of the MBT and selecting the ‘Square’ option. The material
properties of phenolic resin were applied to the square geometry and the model was
subjected to a 70K temperature increase. The geometry was meshed and the study
was run using the settings described in Section 3.2. After running the control model,
were added to the polymer square. This portion of the research looked to compare
the effects of changing the shape and number of these inclusions. To do this, three
sets of models differing only by volume fraction were created. Each set consisted of
eight models with different filler geometry that equated to the same amount of matrix
23
and filler materials. The three volume fractions modeled were 7%, 19%, and 37%.
For each volume fraction, eight different models were simulated. These consisted of
four different filler arrangements with two different filler geometries. The two filler
geometries used were square and circular and the four different filler arrangements
nine inclusions, and twenty-five inclusions. All the variations of the filler created a
matrix of twenty-four models to be simulated for this section. Figures 3-5, 3-6, and
3-7 show all of the models simulated for the two-dimensional portion of the study.
To create the models in COMSOL, the geometry of the filler was added to the
control model of pure polymer. This was done through the use of the ‘Square’ or
‘Circle’ option under the ‘Geometry’ branch of the MBT. The size of the square or
circular inclusions depended on the volume fraction and number of filler particles. To
quickly determine these sizes, equations 3.1 and 3.2 were used for square and circular
inclusions, respectively.
nx2sq
r
n(Af ) n[(lf )(wf )] n[(xsq )(xsq )] vf
vf = = = = → xsq = (3.1)
Ac (lc )(wc ) (1)(1) 1 n
πd2 2 2
r
n(Af ) n( 4cir ) n(πrcir ) nπrcir vf
vf = = = = → rcir = (3.2)
Ac (lc )(wc ) (1)(1) 1 nπ
In Equation 3.1, vf is the volume fraction and n is the number of square inclusions
within the composite. Af is the area of one inclusion, which is equal to the length
times the width of the square (lc and wc ) which are both equal and called xsq . Ac
is the area of the entire composite, which is equal to the length times the width of
the model (lc and wc ). Both of these values are equal to one meter making the area
one square meter. Equation 3.2 is for circular inclusions and all the variables are the
same as in equation 3.1 except for rcir which is the radius of one inclusion.
Once the size of the filler particles was determined, the ‘Array’ tool under ‘Trans-
24
Figure 3-5: Geometry of two-dimensional models with 7% percent filler vol-
ume. Each grid division represents 0.5 m and all models have an
initial total volume of 1 m2 .
Figure 3-6: Geometry of two-dimensional models with 19% percent filler vol-
ume. Each grid division represents 0.5 m and all models have an
initial total volume of 1 m2 .
25
Figure 3-7: Geometry of two-dimensional models with 37% percent filler vol-
ume. Each grid division represents 0.5 m and all models have an
initial total volume of 1 m2 .
forms’ was used on models with more than one inclusion to create a symmetric pattern
centered within the polymer square. After the full geometry of the filler was created,
the ‘Difference’ tool under ‘Boolean Operations’ was used to subtract the filler ge-
ometry from the matrix. When doing this, the ‘Keep input objects’ box was checked
so that the filler’s geometry was not deleted after the operation. However, because
that option was selected, the original matrix square needed to be removed using the
‘Delete Entities’ tool. This left two domains within the model. One being the matrix
with voids, and the other being the filler inclusions. Material properties were then
added to both domains with the matrix and filler consisting of phenolic resin and
with boundary conditions, mesh settings, and solver settings as described in section
26
3.3.2 Three-Dimensional Models
Three-dimensional models were also tested and compared to the results of the
two-dimensional models. A similar matrix of tests was created that varied the shape
of the filler as well as the number of inclusions. The only volume fraction tested
was 7% due to the computation time required to run a simulation. While only one
volume fraction was tested, results were still conclusive and able to be compared to
The exterior dimensions of the three-dimensional models were based off of the
samples tested by Tani et al. [5] with a length of 20 mm, a width of 4 mm, and a
height of 4 mm. Filler was added to the block in the shape of either cylinders, spheres,
tall cylinders with radii depending on the number of inclusions. Equation 3.3 was
used to determine these radii and is similar to the equations used in two-dimensional
modeling. The geometry of these models can be seen in Figures 3-8, 3-9, and 3-10.
πd2 hcyl 2 2
r
n(Vf ) n( cyl4 ) n(πrcyl (20)) nπrcyl 16vf
vf = = = = → rcyl = (3.3)
Vc (lc )(wc )(hc ) (4)(4)(20) 16 nπ
was used to determine the radius of the spheres based on the volume fraction and
number of particles. Models were made using ten and fifty spherical inclusions located
randomly within the matrix. To generate the random coordinates, a MATLAB code
was used. This code ensured that the correct number of inclusions were used and
that the spheres did not overlap or break the surface of the matrix. This code can
be seen in Appendix A. Because the location of the spherical inclusions was random
within the matrix, the results of the simulation differed slightly with each run. To
account for this, five different simulations were run and the results were averaged to
27
Figure 3-8: Three-dimensional model with seven percent filler volume made
of one cylinder. The initial volume of the model is 320 mm2 .
Figure 3-9: Three-dimensional model with seven percent filler volume made
of nine cylinders. The initial volume of the model is 320 mm2 .
28
Figure 3-10: Three-dimensional model with seven percent filler volume made
of twenty-five cylinders. The initial volume of the model is
320 mm2 .
obtain the data point for each specific case. The geometry of these models can be
n( 34 πrsph n( 43 πrsph
3 3 3
r
n(Vf ) ) ) nπrsph 3 240vf
vf = = = = → rsph = (3.4)
Vc (lc )(wc )(hc ) (4)(4)(20) 240 nπ
The last style of three-dimensional model studied was quite different than the
previous two. This model used MATLAB and COMSOL together to create a model
with a specific mesh and then randomly assigned either matrix or filler material
properties to individual elements until the desired volume fraction was achieved. To
do this, five MATLAB files were created, all of which can be seen in Appendix A.
The first of these codes defined the size of the mapped mesh (a grid pattern mesh
consisting of a certain number of blocks) as well as the volume fraction and then
randomly assigned each block as either matrix or filler material. This code output
29
Figure 3-11: Three-dimensional model with seven percent filler volume made
of ten spheres. The initial volume of the model is 320 mm2 .
Figure 3-12: Three-dimensional model with seven percent filler volume made
of fifty spheres. The initial volume of the model is 320 mm2 .
30
the coordinates of the elements to become filler material which was then used by the
other four codes to assign material properties. Each required material property (E,
nu, rho, and alpha) has a MATLAB code that looked at the coordinates generated by
the first code and then assigned the correct values for that specific material property
to each particular element. Once the codes for each material property were written,
the m-files needed to be placed in the COMSOL root folder so they could be found
To use these MATLAB files within COMSOL, a few settings needed to be changed
from previous models. Firstly, the codes needed to be defined within COMSOL so that
they could be found when needed. To do this, a MATLAB function was added under
the ‘Global Definitions’ branch of the MBT. Here, each MATLAB file that defined a
material property was added to the list and the variables it used were defined. Next,
the geometry of the models was created. This was, simply, a solid, 20 mm by 4 mm
by 4 mm bar with roller supports on three sides. The only load applied to this bar
this bar, no values were input under the ‘Material’ branch of the MBT. Instead, one
material was added and the names of MATLAB files defined above were input into
the ‘value’ fields, telling COMSOL to look to the results of the MATLAB code to
find the material property. The last step to create these models was to create the
mesh. For these tests, a mapped, grid-pattern, mesh was used. It was important that
the mesh defined within COMSOL matched the grid that was input in the MATLAB
codes. For this research, a mapped mesh of ten blocks, by ten blocks, by fifty blocks
was used. To create this within COMSOL, the first step was to add a mapped mesh
under the ‘Mesh 1’ branch of the MBT. Then, the x = 0, y = 0, and z = 0 faces
were added to the selection box. The next step was to define the size of the mesh
by adding the ‘Size’ option under the ‘Mapped 1’ branch of the MBT. Here, the
‘custom’ option was selected and the maximum element size was set to 0.0004 m to
31
produce the desired 10 by 10 by 50 element mesh. The last step in the creation of
the mesh was to add the ‘Swept’ option under ‘Mesh 1’ to convert the face mesh to a
three-dimensional mesh of the whole block. Once all the proper options were applied
to the mesh, the build button was pressed and COMSOL output that 5, 000 elements
were created. Figure 3-13 shows what this mesh looked like within COMSOL.
After creating the mesh the models were ready to be run. The solver was set-
up the same way as all previous models which is shown in Figure 3-4. As with the
spherical three-dimensional models, five separate models were run and the results
The models created in the previous section were based off the experiments of
Tani et at. [5] where expansion data was collected for phenolic resin/ZrW2 O8 com-
posites. After running the simulations it was found that the FEA models tended to
32
over-predict the negative CTE effect of the ZrW2 O8 filler material. More detailed
results can be seen in the next chapter, but this section will describe the modeling
techniques that were used to gain a better understanding of the interface between the
two materials.
It was assumed that the difference between the experimental data and the FEA
models could be attributed to the bond between the matrix and filler materials. In
the FEA models, this was created as a perfect bond with no voids or separation. In
the goal of this modeling was to establish the upper and lower bounds of the data by
creating a model with a perfect bond between the filler and matrix as well as a model
The model used for the perfect bond case was already created for the previous
section and the results could be carried over. It was decided to use the geometry of
the model that showed the most expansion of all the two or three-dimensional models.
This way, when the bond between the matrix and filler was removed, it would show
the most expansion and better represent the worst-case scenario. However, choosing
a different geometry would make little difference as all the models showed similar
results.
The next step was to create a model with no bond between the filler and matrix.
To do this, the filler particles of the model were completely removed, leaving empty
voids within the matrix. By doing this, the effect of the filler was removed from the
model, which gave the same effect as if there was no bond between the two materials.
Therefore, these models would show much more expansion than the models with a
Using the modeling techniques just described, FEA was completed to compare to
the experiments of Tani et al. and Sharma et al. To compare to the Tani experiments,
models contained the properties of phenolic resin and zirconium tungstate at volume
33
fractions of 7%, 19%, and 37%. To compare to the Sharma experiments, models
5%, 10%, and 15%. The results of these models as well as how they compare to the
The final step to the modeling conducted in this research was to evaluate the
models. This consisted of simply determining the final total volume after the 70 K
After a model finished its study, COMSOL displays a surface plot of total dis-
placement and puts the user in the ‘Results’ section of the MBT. The first step was
to adjust the plot to show the deformation of the model. To do this, under ‘2D
Plot Group 1’, ‘Surface 1’ is right-clicked on and ‘Deformation’ is selected. The plot
should now show a scaled, deformation plot that extents past the black lines of the
original shape. The next step was to have COMSOL calculate the change in volume
of the model. To do this, the ‘Derived Values’ section was right-clicked on and either
integration, all domains were selected and the expression was set to ‘solid.evol’ to
integrate over the volumetric strain. With those settings chosen, the equals button
was selected and COMSOL then output a value for volumetric strain in the results
table. This value represented the change in volume of the model. Therefore, know-
ing the initial volume of the model (1 m2 for 2-D, and 320 mm2 for 3-D), the final
volume of the model was calculated by adding the value of volumetric strain to the
initial volume. From there, the relative expansion was calculated using Equation 3.5
34
to allow for direct comparison between the 2-D and 3-D models. Comparisons were
also made between these results and the mathematical models discussed earlier. The
Vf inal
RelativeExpansion = −1 (3.5)
Vinitial
Figure 3-14: COMSOL results settings for determining the change in volume
of the models.
35
Chapter 4
The models described in Chapter 3 were run and evaluated as described in Section
3.5. The results of these models will be given and discussed in this chapter. First,
the two-dimensional models will be looked at, followed by the three-dimensional ones.
Then, the models will be compared to published experimental results and modifica-
tions will be made to create an upper and lower bound for expansion. Finally, the
results will be compared to the mathematical models described in Section 2.3 to de-
termine which model the data most closely followed and how the upper and lower
bounds compare.
The two-dimensional models detailed in Section 3.3.1 were run and evaluated as
described in Section 3.5. The results of these tests will be discussed in this section.
The first model run was a one-meter by one-meter square made up of only phenolic
resin; the matrix material. This model was created to determine the baseline of
expansion for the pure polymer and to better understand the effects of adding the
filler material. The total displacement plot for this model can be seen in Figure 4-1
36
Figure 4-1: Total displacement plot for a two-dimensional, pure polymer
model. This model represents the baseline of all future models
and has an even, linear growth in the positive x and y directions.
It was subjected to a temperature change of 70 K and the scale
factor of the displacement is 200.
When looking at the displacement plot, take note of its linear shape and even
displacement in both the positive x and y directions. It should be noted that the plot
has a scale factor on the displacement of 200. This allows the changes in shape to be
more easily seen and will be used on all 2-D plots. After using COMSOL to determine
the change in area, Equation 3.5 was used to calculate the relative expansion using
the initial and final areas in place of the volumes. This was found to be 0.292%.
Next, the two-dimensional models containing 7% filler material were run. These
models were all created in the same COMSOL file and run at the same time, but
analysed individually. The total displacement plot for these models can be seen
in Figure 4-2 and the expansion data can been seen graphically in Figure 4-5 and
numerically in Table 4.1. When looking at the total displacement plot, the effects of
the ZrW2 O8 can be seen, but only slightly, and the displacement of all eight models
37
appears to be similar. This was confirmed by calculating the relative expansion for
each model and plotting the results. The graph in Figure 4-5 shows that there was
little deviation in the expansion of the eight models suggesting that filler shape and
arrangement have little effect on the overall expansion. The average value of relative
expansion for the 7% models was 0.252% with a standard deviation of 0.0010%.
This equates to a 0.070% reduction in relative expansion when compared to the pure
polymer model.
Figure 4-2: Total displacement plots for two-dimensional models with seven
percent filler volume. The average relative expansion of the mod-
els was 0.252% meaning an average reduction in expansion of
0.070% was seen when compared to the pure polymer model.
Next, the models with 19% filler were run. Like the 7% models, these were all
created in the same COMSOL file and run and the same time, but analysed separately.
The total displacement plot for these models can be seen in Figure 4-3. In these plots,
the filler material’s effect is more noticeable, especially in the models with only one
particle where the expansion is not as evenly distributed as the models with multiple
inclusions. Despite these differences, the relative expansion of the models were all
38
similar with an average value of 0.187% and a standard deviation of 0.0024%. This
gives an average reduction of expansion of 0.135% when compared to the pure polymer
model. This data can be seen graphically in figure 4-5 and numerically in Table 4.1.
Figure 4-3: Total displacement plots for two-dimensional models with nine-
teen percent filler volume. The effects of the ZrW2 O8 filler can
be seen in the shape of the displaced plots and an average re-
duction in expansion of 0.135% was calculated when compared
to the pure polymer model.
The last set of two-dimensional models run were those containing 37% filler. These
models were run the same way as those with 7% and 19% and the total displacement
plot can be seen in Figure 4-4. The negative effect of the filler material is very
noticeable in these plots with the expanded shape appearing only slightly larger than
the original geometry, even with the scale factor of 200. These models also gave the
largest variation in relative expansion with an average value of 0.096% and a standard
deviation of 0.0026%. This can be seen graphically in Figure 4-5 and numerically in
Table 4.1. The 37% filler reduced the expansion of the polymer by 0.226%.
To compare the results of the 2-D models, the graph seen in Figure 4-5 was
39
Figure 4-4: Total displacement plots for 2-D models with 37% percent filler
volume. These models had the largest variance in expansion with
an average value of 0.096% and a standard deviation of 0.0026%.
The 37% filler reduced the expansion of the polymer by 0.226%.
created. This graph shows that the addition of the ZrW2 O8 reduced the expansion of
all models when compared to the pure polymer model, represented by the horizontal,
orange line. It also compares the different arrangements of filler particles tested for
each volume fraction. It was found that at each volume fraction, the arrangement
or shape of the filler particles was not an important factor in the overall expansion.
This can be seen by each volume fraction producing very similar expansion data for
all models tested. Knowing this, the expansion data was averaged and plotted versus
volume fraction, as shown in Figure 4-6. A linear best-fit line was added to these
data points and fit very well with an R2 value of 0.98. This means that as more
If this prediction is projected past the data of the models, a composite exhibiting
no expansion over the tested temperature range would require a volume fraction of
approximately 52%.
40
Table 4.1: Numerical results from the two-dimensional modeling. This data
shows that the filler geometry of 2-D models has little effect on
the expansion results with low standard deviations calculated for
each volume fraction. This is represented graphically in Figure
4-5.
Volume Filler Num. of Final A Relative Avg Std
Fraction Shape Inclusions (m2 ) Exp. Exp. Dev.
0% NA 0 1.00322 0.322% 0.322% NA
7% Sq 0.25 1.00252 0.252%
7% Sq 1 1.00251 0.251%
7% Sq 9 1.00251 0.251%
7% Sq 25 1.00251 0.251% 0.252% 0.0010%
7% Cir 0.25 1.00253 0.253%
7% Cir 1 1.00253 0.253%
7% Cir 9 1.00253 0.253%
7% Cir 25 1.00253 0.253%
19% Sq 0.25 1.00186 0.212%
19% Sq 1 1.00183 0.210%
19% Sq 9 1.00184 0.210%
19% Sq 25 1.00184 0.210% 0.187% 0.0024%
19% Cir 0.25 1.00189 0.214%
19% Cir 1 1.00189 0.214%
19% Cir 9 1.00188 0.214%
19% Cir 25 1.00188 0.214%
37% Sq 0.25 1.00095 0.095%
37% Sq 1 1.00094 0.094%
37% Sq 9 1.00094 0.094%
37% Sq 25 1.00094 0.094% 0.096% 0.0026%
37% Cir 0.25 1.00100 0.100%
37% Cir 1 1.00099 0.099%
37% Cir 9 1.00098 0.098%
37% Cir 25 1.00097 0.097%
41
Figure 4-5: Bar graph comparing all of the two-dimensional models studied.
The orange line at the top represents the expansion of the pure
polymer model. It can be seen that all models reduced the expan-
sion of the polymer and that each volume fraction gave similar
results for all filler arrangements.
Figure 4-6: This is a plot of volume fraction versus relative expansion cre-
ated from the averaged data of the two-dimensional models. A
best-fit line was added to show the linearity of the data and also
projects that a volume fraction of approximately 52% will pro-
duce a composite with no expansion.
42
4.2 Three-Dimensional Models
models were looked at. The goal was to see if modeling in three-dimensions affected
the outcome of the results in a significant manner. To do this, various models were
created at a volume fraction of 7% and compared to each other, as well as the results
from the two-dimensional testing. The models were based off the experiments of Tani
temperature increase.
The first model run had a filler geometry of one cylinder running through the
center of the bar. This model’s total displacement plot can be seen in Figure 4-
7. When looking at the plot, it is apparent that there was an even displacement
throughout the bar, mostly in the y and z directions. The long, cylindrical filler
prevented the bar from expanding in the x direction. The relative expansion of this
Figure 4-7: Total displacement plot for 3-D model with one cylindrical filler
particle. Expansion is seen mainly in the y and z directions with
little growth along the x axis.
43
For the next model, an array of nine cylinders was used for the filler geometry.
Like the model created with one cylinder, this one also showed even growth in the y
and z directions with the cylinders preventing much expansion in the x direction. This
can be seen in Figure 4-8. The relative expansion was calculated to be 0.256%. The
model shown in Figure 4-9 with twenty-five cylinders, again, showed similar behavior.
Figure 4-8: Total displacement plot for 3-D model with nine cylindrical filler
particles. Expansion is similar to the model with one cylindrical
particle.
For the next 3-D models, the filler was made up of spherical particles. One model
was made with ten inclusions and another with fifty. The total displacement plots
of these models can be seen in Figures 4-10 and 4-11, respectively. When looking
at these plots, the first thing noticed is that they are drastically different than the
ones of the models with cylindrical filler geometry (the displacement scale is kept the
same for all models). The plots for the spherical models show large displacement in
the x direction while the plots for the cylindrical models showed very little change
in that direction. This would lead one to believe that the expansion of the spherical
44
Figure 4-9: Total displacement plot for 3-D model with twenty-five cylindri-
cal filler particles. Little difference was seen between the three
models with cylindrical-shaped filler.
models is significantly greater than the expansion of the cylindrical models, however,
this is not the case. The relative expansion of the ten sphere model was found to be
0.265% and the fifty sphere model was 0.258% (both values obtained by averaging
five models’ results) showing that they exhibited a similar change in volume as the
cylindrical models. This meant that the spherical particles allowed the models to
expand primarily in the x direction while the cylindrical models prevented this growth,
The last three-dimensional model created used a mapped mesh to create cube-
shaped elements. Matlab was then used to randomly select enough elements to give
the composite the desired 7% filler material and the rest were given matrix material
properties. The total displacement plot of this model can be seen in Figure 4-12
where it can be seen that it expanded similarly to the spherical models with large
displacement in the x direction. The relative expansion, found by averaging five runs,
45
Figure 4-10: Total displacement plot for 3-D model with ten spherical filler
particles. The shape of the filler allows this model to expand
primarily in the x direction, which is different from the models
with cylindrical filler. However, the final volumes did not differ
significantly.
Figure 4-11: Total displacement plot for 3-D model with fifty spherical filler
particles. This model behaved similarly to the model with ten
spheres and produced a similar final volume.
46
Figure 4-12: Total displacement plot for 3-D model made with a mapped
mesh of cube-shaped particles. This model used Matlab to ran-
domly assign material properties to the mesh and contained the
smallest particles tested. The results were most similar to the
spherical models.
In Table 4.2, all of the numerical data from the three-dimensional models can be
seen. Looking at the relative expansion and standard deviation for all the models
shows that little changes were seen when the filler geometry was changed, which
agrees with the results from the two-dimensional modeling. This trend can be seen
results were added as the last column. This shows that the three-dimensional models
models exhibited slightly more growth than the two-dimensional models, but not
models was also higher than the two-dimensional ones, but no pattern to explain this
was seen.
47
Table 4.2: Numerical results from the three-dimensional modeling. This data
shows that the filler geometry of 3-D models has little effect on
the overall expansion of the model. The standard deviation of the
data is low and follows the trend seen in the 2-D modeling. This
data is represented graphically in Figure 4-13.
48
4.3 Comparisons to Experimental Data and De-
When looking at the results of the two and three-dimensional models evaluated
for the previous sections, it can be seen that all models of the same volume fraction
produced similar expansion results. While the consistency of the results is a plus, how
the results of the experiments of Tani et al. [5] were looked at as the same materials
were used. Figure 4-14 compares the results of the 7% models with the experimental
data of Tani. The two models chosen for the graph were the 7% models that showed
the highest and lowest expansion. The model that showed the least expansion was
the two-dimensional model with nine square-shaped filler particles. The model that
showed the most expansion was the three-dimensional model with twenty-five cylin-
drical filler particles. Looking at the plot shows that even the model with the most
expansion is considerably less than the experimental data published by Tani. This
means that all the FEA models over-predicted the effect of the ZrW2 O8 filler material
and reduced the expansion more than what is seen in physical experiments.
While exactly matching experimental results was not a goal of this research, the
comparison in Figure 4-14 does give a better understanding of the FEA models. In the
models, the filler and matrix materials are considered to be perfectly bonded together
achieve. When a composite material is made, small air bubbles can get trapped be-
tween the two materials which leads to imperfect bonds. In composites with ZrW2 O8
filler material, this has larger consequences as the opposing forces created during a
temperature increase only accentuate these imperfections. This explains why the all
the FEA models showed less expansion than the experimental data. The perfect bond
between the filler and matrix gave the negative thermal expansion filler more effect,
49
Figure 4-14: Bar graph comparing the FEA models to experimental data.
The two models chosen represent the highest and lowest expan-
sion of all the 2-D and 3-D, 7% models. This shows that all
modeling produced results that showed less expansion that the
experiments of Tani et al.
Knowing that the bond between the filler and matrix is perfect in the FEA models,
it is considered to be the lower bound of possible expansion for the composite. This
means that in a physical experiment, a test specimen will not show less expansion than
this lower bound provided they are tested at the same volume fraction. The obvious
next step is to then determine the upper bound for the expansion. A specimen
would undergo the most expansion if the ZrW2 O8 filler was not connected to the
matrix material at all, or, in other words, the complete opposite of the previous FEA
models. To do this in FEA, models were created similarly to the previous models, but
the filler particles were deleted leaving voids within the matrix material. To reduce
the amount of modeling needed, the results from the previous two sections were used
to guide this section. Geometry for the models was chosen based on the previous
50
data where the model showing the most expansion was used. This ensured that the
upper bound represented the worst case scenario and the lower bound maintained
consistency. The model showing the most expansion was the three-dimensional model
with twenty-five cylindrical filler particles and the expansion data from it was used
for the lower bound. It was then modified to represent no bond between the matrix
and filler by deleting the twenty-five cylindrical filler particles, leaving twenty-five
cylindrical voids within the matrix. Volume fractions of 7%, 19%, and 37% were
Figure 4-15: Graph showing the upper and lower bounds of expansion cre-
ated by FEA models compared to Tani’s data. The data ob-
tained by Tani et al. falls between the upper and lower bounds
in blue and green, respectively, for all volume fractions.
In Figure 4-15, it can be seen that the experimental data obtained by Tani et
al. falls between the upper and lower bounds created by the finite element models
for all volume fractions. The experimental data also tends to be closer to the upper
bound, meaning that there was likely many voids and separation between the filler
51
and matrix within the specimens. To further validate the FEA upper and lower
bounds, the experiments of Sharma et al. [7] were also compared to the models. In
these experiments, ZrW2 O8 filler was added to a polyimide (PI) matrix material and
the effects on the CTE were looked at. Surface treatments were also done to the
ZrW2 O8 to improve the bond between the filler and matrix. The FEA models were
adjusted to account for the different matrix material properties and different volume
fractions of 5%, 10%, and 15%. The results can be seen in Figure 4-16.
Figure 4-16: Graph showing the upper and lower bounds of expansion cre-
ated by FEA models compared to Sharma’s data. Again, the
data falls within the bounds and follows a similar trend as the
Tani data.
Looking at the graph in Figure 4-16, it can be seen that the upper and lower
bounds created by the FEA models encased the results of Sharma’s experiments.
and without surface treatments to the ZrW2 O8 in attempt to improve the bond
between the two materials. In the graph, the unmodified tests are represented by
52
the red bar and labelled Sharma Exp. and the samples with surface modifications are
represented by the orange bar and labelled Sharma Exp. Mod. While little difference
was seen between the two experiments, the modified tests did show a slight reduction
in expansion for the 5% and 10% samples but exhibited an increase in expansion
in the 15% samples. Despite these differences, the upper and lower bounds still
remained above and below all the results and the data followed a similar trend to
Tani’s, tending to be closer to the upper FEA bound. This means that there is room
to improve the bond between the filler and matrix if less overall expansion is desired.
For a better understand of Sharma’s data and the effect of the surface treatments on
the expansion of the composites, please see item [7] in the references section.
The mathematical models discussed in Section 2.3 were developed to predict the
CTE of composite materials. These included the rule of mixtures, the Turner model,
and the Schapery upper and lower bounds and can be seen graphically in Figure 2-4.
Figures 4-17 and 4-18 show the same plot with the bounds created by the FEA for
Tani’s and Sharma’s data added. It can be seen that the line for the lower bound falls
between the Schapery limits. This makes sense as both of the experimental results
closely followed the Shapery upper limit and the FEA models showed that a lower
CTE was possible. The upper bound predicts the CTE to be higher than any of the
other models, climbing above the rule of mixtures and showing the greatest difference
between the lower bound at a 50% filler loading. This makes sense because with a high
filler volume fraction, there is more surface area that could or could not be bonded
to the matrix material leading to a better chance for variance in the results. After
50%, the difference starts to become smaller again as the filler becomes the dominant
material and less bond area is seen because of the reduction in matrix material.
53
Figure 4-17: Graph showing the upper and lower bounds of expansion cre-
ated by FEA models compared to Tani’s data.
Figure 4-18: Graph showing the upper and lower bounds of expansion cre-
ated by FEA models compared to Sharma’s data.
54
Chapter 5
5.1 Conclusions
The main goal of this research was to determine the effect of filler geometry on
was determined that the filler geometry had little effect on the expansion results of
the FEA. All two and three-dimensional models of the same volume fraction showed
their geometry. It should be noted, however, that all of the three-dimensional models
showed slightly more expansion than all of the two-dimensional models. This means
that the two-dimensional models gave the filler material more effect, slightly reducing
After determining the effect of filler geometry on the outcome of the models, the
results were compared to the experiments of Tani et al. where it was found that all the
models showed less expansion than the experimental data of the same volume fraction.
While the FEA results were close enough to rule out any errors in modeling, the
difference was significant and consistent enough that an explanation was required. It
55
was decided that the discrepancy was most likely caused by the interface between the
filler and matrix materials. In the FEA models, the bond between the two materials
composites, voids can be created and separation between the two materials can occur,
all of which lead to the filler material having less effect on the overall properties. This
meant that the modeling completed represented the best possible case for reducing
of the experimental results, the opposite case needed to be modeled where there was
no bond between the filler and matrix material. Together, the results of the models
with a perfect bond and the results of the models with no bond created a lower and
upper bound for the possible expansion of the polymer/ZrW2 O8 composite. These
bounds were verified using the experimental results of Tani and Sharma et al. where
their results fell within the bounds at all volume fractions. These results can be seen
in Section 4.3.
right direction. The experiments of Sharma et al. that look to improve the bond
between a polymer matrix and ZrW2 O8 filler are areas that need to be addressed
While, currently, the polymer/ZrW2 O8 composites created are able to reduce the
CTE of the polymer, this research has shown that further reduction could be seen
The work conducted for this paper also leaves an opportunity for future research.
To start, the findings of this research could be verified through the recreation of the
56
models alongside real world experiments. This would ensure full confidence in the
research having gathered both the experimental data as well as completing the finite
element analysis. While completing the modeling, more volume fractions could be
modeled to add more data points to the upper and lower bounds created as in Section
4.3. The data used to create the bounds in Figure 4-17 were based on only three data
points and a best-fit line. These could be better represented if more volume fractions
were modeled.
Figure 5-1: Geometry showing a possible way to model the interface between
the matrix and filler. The effect of the ZrW2 O8 could be reduced
by adjusting the size and properties of the red layer surrounding
the filler.
experimental results using FEA. The unmodified results of Sharma and Tani both
showed similar differences to the bounds created by the finite element models. This
means that if one could determine how to properly model the interface between the
two materials when standard composite production techniques are used, accurate
57
results could be seen using FEA. One way to do this could be to add a third domain
to the FEA models surrounding the filler particle as shown in Figure 5-1. This
would allow researchers to reduce the effect of the ZrW2 O8 by adjusting the material
properties and thickness given to this layer. If the correct size and properties are
found, it would provide researchers with a simple and repeatable process to predict
the CTE in these composites. It would also aid in the understanding of the interface
between the matrix and filler which could lead to improving their bond and further
58
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Appendix A
MATLAB Codes
clc
clear a l l
%Volume f r a c t i o n ( p e r c e n t )
Volumefraction = 7;
%Volume f r a c t i o n ( d e c i m a l )
vf = Volumefraction /100;
%Dimensions o f bar
l = 20;
w = 4;
67
h = 4;
Vbar = l ∗w∗h ;
%Numer o f s p h e r e s
q = 50;
%Radius o f s p h e r e s
r = ( ( 3 ∗ v f ∗( Vbar ) ) /(4∗ q∗ pi ) ) ˆ ( 1 / 3 ) ;
%Create i n i t i a l random c o o r d i n a t e s
%Create non−o v e r l a p p i n g c o o r d i n a t e s
m = 1;
t = 0;
while m < q
i f t >1e6
break
end
68
i f any (C1<4∗( r ˆ 2) )
t = t +1;
continue
end
m = m+1;
x1 = [ x1 ;Xm] ;
y1 = [ y1 ;Ym] ;
z1 = [ z1 ;Zm ] ;
end
%Output s p h e r e c o o r d i n a t e s
[ x1 y1 z1 ]
%P l o t
[ xs , ys , z s ] = sphere ( 3 0 ) ;
for n = 1 :m
EdgeColor ’ , ’ r ’ )
hold on
camlight ( ’ l e f t ’ )
material dull
end
axis e q u a l
xlim ( [ 0 w ] )
ylim ( [ 0 h ] )
zlim ( [ 0 l ] )
hold o f f
69
A.2 MATLAB Codes for Creating a Mapped Mesh
Mesh
clc
clear a l l
%S e t t h e s t a t e t o t h e c l o c k t o e n s u r e random
%Volume f r a c t i o n ( p e r c e n t ) ( a c t u a l w i l l be l o w e r )
Volumefraction = 7 . 2 3 ;
%Volume f r a c t i o n ( d e c i m a l )
vf = Volumefraction /100;
%Enter t h e d i m e n s i o n s o f t h e bar
xd = 4 ;
yd = 2 0 ;
zd = 4 ;
directions
70
xn = 1 0 ;
yn = 5 0 ;
zn = 1 0 ;
t o t a l e l e m e n t s = xn∗yn∗ zn ;
%C a l c u l a t e e l e m e n t s i z e
xe = xd/xn ;
ye = yd/yn ;
z e = zd / zn ;
N = c e i l ( v f ∗xn∗yn∗ zn ) ;
%Create i n i t i a l random c o o r d i n a t e s
x1 = c e i l ( xn . ∗ rand (N, 1 ) ) ;
y1 = c e i l ( yn . ∗ rand (N, 1 ) ) ;
z1 = c e i l ( zn . ∗ rand (N, 1 ) ) ;
%S h i f t p o i n t s t o m i d p o i n t o f e l e m e n t s
x1 = x1∗xe−xe / 2 ;
y1 = y1∗ye−ye / 2 ;
z1 = z1 ∗ ze−z e / 2 ;
A = [ x1 , y1 , z1 ] ;
SizeB = s i z e (B, 1 ) ;
71
SizeA = s i z e (A, 1 ) ;
%S e l e c t o n l y u n i q u e p o i n t s
x2 = B ( : , 1 ) ;
y2 = B ( : , 2 ) ;
z2 = B ( : , 3 ) ;
N2 = SizeB ;
%P l o t
s c a t t e r 3 ( x2 , y2 , z2 , 1 )
axis e q u a l
xlim ( [ 0 xd ] )
ylim ( [ 0 yd ] )
z l i m ( [ 0 zd ] )
%Save o u t p u t
save x2
save y2
save z2
save xe
save ye
save z e
save N
72
A.2.2 Code for Assigning CTE Properties
function Alpha = a l p h a d a t a e l e m e n t s ( x , y , z )
%I n p u t m a t r i x and f i l l e r p r o p e r t y v a l u e s
a l p h a m a t r i x = 1 5 . 2 4 e −6;
a l p h a f i l l e r = −9e −6;
%Load c o o r d i n a t e f i l e s
load ( ’ x2 . mat ’ ) ;
load ( ’ y2 . mat ’ ) ;
load ( ’ z2 . mat ’ ) ;
load ( ’ xe . mat ’ ) ;
load ( ’ ye . mat ’ ) ;
load ( ’ z e . mat ’ ) ;
[m, p ] = s i z e ( x ) ;
%A ssign p r o p e r t i e s t o each e l e m e n t
a l p h a l o g i c = f a l s e (m, p ) ;
for j = 1 : length ( x2 )
end
Alpha = a l p h a l o g i c ∗ a l p h a f i l l e r + ˜ a l p h a l o g i c ∗ a l p h a m a t r i x ;
73
A.2.3 Code for Assigning Elastic Modulus Properties
function E = e d a t a e l e m e n t s ( x , y , z )
%I n p u t m a t r i x and f i l l e r p r o p e r t y v a l u e s
e m a t r i x = 3 . 5 1 e9 ;
e f i l l e r = 8 8 . 3 e9 ;
%Load c o o r d i n a t e f i l e s
load ( ’ x2 . mat ’ ) ;
load ( ’ y2 . mat ’ ) ;
load ( ’ z2 . mat ’ ) ;
load ( ’ xe . mat ’ ) ;
load ( ’ ye . mat ’ ) ;
load ( ’ z e . mat ’ ) ;
[m, p ] = s i z e ( x ) ;
%A ssign p r o p e r t i e s t o each e l e m e n t
e l o g i c = f a l s e (m, p ) ;
for j = 1 : length ( x2 )
end
E = e l o g i c ∗ e f i l l e r + ˜ e l o g i c ∗ ematrix ;
74
A.2.4 Code for Assigning Poisson’s Ratio
function Nu = n u d a t a e l e m e n t s ( x , y , z )
%I n p u t m a t r i x and f i l l e r p r o p e r t y v a l u e s
numatrix = 0 . 3 7 ;
nufiller = 0.33;
%Load c o o r d i n a t e f i l e s
load ( ’ x2 . mat ’ ) ;
load ( ’ y2 . mat ’ ) ;
load ( ’ z2 . mat ’ ) ;
load ( ’ xe . mat ’ ) ;
load ( ’ ye . mat ’ ) ;
load ( ’ z e . mat ’ ) ;
[m, p ] = s i z e ( x ) ;
%A ssign p r o p e r t i e s t o each e l e m e n t
n u l o g i c = f a l s e (m, p ) ;
for j = 1 : length ( x2 )
end
Nu = n u l o g i c ∗ n u f i l l e r + ˜ n u l o g i c ∗ numatrix ;
75
A.2.5 Code for Assigning Density Properties
function Rho = r h o d a t a e l e m e n t s ( x , y , z )
%I n p u t m a t r i x and f i l l e r p r o p e r t y v a l u e s
rhomatrix = 1370;
r h o f i l l e r = 5090;
%Load c o o r d i n a t e f i l e s
load ( ’ x2 . mat ’ ) ;
load ( ’ y2 . mat ’ ) ;
load ( ’ z2 . mat ’ ) ;
load ( ’ xe . mat ’ ) ;
load ( ’ ye . mat ’ ) ;
load ( ’ z e . mat ’ ) ;
[m, p ] = s i z e ( x ) ;
%A ssign p r o p e r t i e s t o each e l e m e n t
r h o l o g i c = f a l s e (m, p ) ;
for j = 1 : length ( x2 )
end
Rho = r h o l o g i c ∗ r h o f i l l e r + ˜ r h o l o g i c ∗ r h o m a t r i x ;
76