PHD Dissertation Draft - Fang Wang

MEASUREMENT OF VISCOEASTIC PROPERTIES
AT SMALL LENGTH SCALES FOR

HETEROGENEOUS AND NONLINEAR
MATERIALS

By

FANG WANG

Bachelor of Science
East China University of Science & Technology
Shanghai, China
2003

Master of Science
Zhejiang University
Hangzhou, China
2006

Submitted to the Faculty of the
Graduate College of the
Oklahoma State University
in Partial Fulfillment of
the Requirements for
the Degree of
DOCTOR OF PHILOSOPHY
February 2013
iii

ACKNOWLEGEMENTS

I would like to express my sincere appreciation to Dr. Hongbing Lu, Dr. Ranga Komanduri
and Dr. Raman P. Singh for their instructions on this research. I appreciate their intelligent and
inspiring guidance. I would like to thank Dr. Komanduri and Dr. Lu for their generous financial
support and for the opportunity for letting me work in the Polymer Mechanical Lab. Also, I am
grateful to Dr. Singh for being my adviser and committee chair. Finally, I would like to thank Dr.
D. A. Lucca, Dr. Kaan Kalkan and Dr. Yu Mao for serving on my committee.
I appreciate Dr. Sushen Tans help with AFM experiments, and Dr. Nitin Daphalapurkar and
Mr. Boshen Fus help with nanoindentation and finite-element simulations. I am also thankful for
Dr. Huiyang Luos help with technical suggestions on the bismaleimide resin experiments.
Finally, I am grateful to the other members in Dr. Komanduri and Dr. Lus research groups for
their constructive suggestions and discussions during my research.
I would like to acknowledge the financial support for my research work provided by AFOSR
through a DEPSCoR grant (FA9550-08-1-0328).

iv

ABSTRACT

In this dissertation, advances in linear and non-linear viscoelastic analysis and
experimentation have been employed to investigate the properties of materials using
nanoindentation. In the first study, a general linear-viscoelastic model was developed to measure
the properties of polydimethylsiloxane (PDMS) using a flat punch indenter. Subsequently, linear
viscoelastic nanoindentation was used to measure the youngs relaxation modulus of a locally-
heterogeneous thermally-aged bismaleimide resin using a Berkovich indenter. Nanoindentation
measurements were conducted on both surface and cross section of aged bismaleimide resin
specimens with different aging time at 200C and 300C respectively to extract the oxidation
effect of sample under high temperatures. Finally, nanoindentation measurements were made on
human tympanic membrane specimens with using a spherical nanoindenter tip in direct contact
with the collagen fiber layer. Linear viscoelastic analysis was conducted to extract the Youngs
relaxation modulus distributions.
The study also focused on the development of non-linear viscoelastic analysis of
indentation experiments. Despite the fact that the nanoindentation technique is well established
for the characterization of elasto-plastic materials, nanoindentation on viscoelastic materials is not
fully understood especially in nonlinear viscoelastic region. In the dissertation, a nonlinear
viscoelastic model was developed and implemented in Abaqus/Implicit Code to analyze the
nonlinear visceoelastic behavior of polyvinyl acetate (PVA) under nanoindentation.

v

TABLE OF CONTENTS

Chapter Page

I. INTRODUCTION ......................................................................................................1

II. THEORETICAL BACKGROUND ..........................................................................5

2.1 The elastic indentation problem .........................................................................5
2.2 Viscoelastic material modeling ........................................................................10
2.3 The viscoelastic indentation problem ..............................................................13

III. DETERMINATION OF LINEAR VISCOELASTIC FUNCTIONS USING
NANOINDENTATION .........................................................................................18

3.1 Flat punch nanoindentation of polydimethylsioxane (PDMS) ........................18
3.1.1 Theoretical prerequisites .........................................................................19
3.1.2 Experiments ............................................................................................23
3.1.3 Results .....................................................................................................24
3.1.4 Conclusions on flat punch nanoindentation ............................................27
3.2 Viscoelastic characterization of thermally aged bismaleimide resin ...............27
3.2.1 Theoretical background ..........................................................................30
3.2.2 Experiment ..............................................................................................31
3.2.3 Results and discussions ...........................................................................35
3.2.4 Conclusion of nanoindentation on bismaleimide resin ...........................49
3.3 Viscoelastic characterization of human tympanic membrane .........................50
3.3.1 Analysis method......................................................................................51
3.3.2 Nanoindentation experiments .................................................................52
3.3.3 Results discussion ...................................................................................56
3.3.4 Conclusion of nanoindentation on human eardrum ................................61
3.4 Conclusion of linear viscoelastic nanoindentation ..........................................61

IV. MEASUREMENT OF NONLINEAR VISCOELASTIC PROPERTIES OF
POLYVINYL ACETATE (PVAC) .............................................................................62
vi

Chapter Page

4.1 Introduction ......................................................................................................62
4.2 Nonlinear viscoelastic model ...........................................................................63
4.3 Nanoindentation measurement on PVAc .........................................................69
4.4 Simulation of nanoindentation on PVAc .........................................................69
4.5 Conclusion .......................................................................................................74

VI. CONCLUSIONS ...................................................................................................76

REFERENCES ............................................................................................................79

vii

LIST OF TABLES

Table Page

1. Youngs relaxation modulus (at 50s) determined from nanoindentation on cross-
sectional area of specimens aged at 200C ..................................................................44

2. Youngs relaxation modulus (at 50s) determined from nanoindentation on cross-
sectional area of specimens aged at 300C ..................................................................49

3. Transient creep parameters ...................................................................................73

viii

LIST OF FIGURES

Figure Page

2-1. A typical load-displacement curve of nanoindentation on aluminum .................9

2-2. Typical load-displacement data obtained from the nanoindentation of a
viscoelastic material. ....................................................................................................10

3-1. Schematic of flat punch indentation ..................................................................20

3-2. Nanoindentation results for ELASTOSIL RT 601 silicon rubber. (a) Load-
displacement curves from experiments. (b) Results of G(t) and fitting .......................25

3-3. Dynamic nanoindentation results for ELASTOSIL RT 601 silicon rubber. (a)
Amplitude of harmonic load. (b) Amplitude of harmonic displacement. (c) Phase
angle. (d) Storage and loss compliance........................................................................26

3-4. Section view of aged specimen with three oxidation phases defined. ...............29

3-5. Cutting set for obtaining the facture cross section ............................................32

3-6. AFM images of the cross section of BMI sample (a) sample height 2D image.
(b) sample height 3D image .........................................................................................33

3-7. Fractured cross section surface with 4 testing areas defined .............................34

3-8. The nanoindentation load-displacement curves for the edge area of cross-
section
of non-oxidized sample. (a) All test load-displacement curves from nanoindentation
experiment. (b) The load-displacement curve from experiment and fitting method. ..36

3-9. Youngs relaxation modulus measured from the fractured cross-section for an
un-oxidized sample ......................................................................................................37

3-10. Youngs relaxation modulus result measured from nanoindentation test on the
surface of the specimens aged at 200C (a). Youngs relaxation modulus measured at
different aging time. (b). Youngs relaxation modulus vs. aging time. .......................39

ix

3-11. Youngs relaxation modulus result measured from nanoindentation test for the
cross-section of the specimen aged 5.2 hours at 200C. (a). Youngs relaxation
modulus at different cross-sectional locations . (b). Youngs relaxation modulus (at
50 s) determined from nanoindentation on cross-sectional area. .................................40


cross-section of the specimen aged 523 hours at 200C. (a). Youngs relaxation



3-16. Image of the right TM (lateral view) ...............................................................54

3-17: Schematic diagram showing four quadrants of left ear TM (medial view). ....54

3-18. Schematic of through-thickness and in-plane nanoindentation tests setup .....55

3-19. Typical load-displacement curve of human TM from nanoindentation ..........56

3-20. Youngs relaxation modulus distribution illustrations of human tympanic
membrane .....................................................................................................................60

4-1. Nonlinear Burgers model .................................................................................63
x

Figure Page

4-2. Load-displacement curves from nanoindentation (0.05mN/s) ..........................68

4-3. FEA simulation model: Berkovich indenter using rigid shell element and 1/6
symmetric PVAc sample..............................................................................................70

4-4. Simulation result (a) 50s loading/unloading time.(b) 75s loading/unloading
time.(c) 100s loading/unloading time. (d) 125s loading/unloading time. ....................71

4-5. Simulation results. (a). Stress z (GPa) distribution after loading. (b). Stress z
(GPa) distribution after unloading. (c). Displacement (m) along z axis after
unloading. (d). Displacement (m) along z axis after unloading.................................72

1

CHAPTER I

INTRODUCTION

An awareness of viscoelastic behavior dates back at least to the late 18
th
century. Viscoelastic
behavior manifests itself in creep, which is continued deformation of a material under constant
load; and in stress relaxation, which is progressive reduction in stress of a material under constant
deformation. Thus, viscoelastic materials are said to exhibit time-dependent behavior. All
materials exhibit some viscoelastic response. Nonetheless, for polymers in particular, the
mechanical behavior is dominated by viscoelastic phenomena, which is most likely due to the
polymers complicated molecular adjustment under deformation. Since the invention of synthetic
polymers in last century, they have been increasingly used in structural and chemical
applications. Based on high specific strength, ease of fabrication and high corrosion resistance,
polymers are anticipated to find even greater application in medical, automotive, and aerospace
industries. For all such applications it becomes critical to understand the deformation and failure
of polymers in order to design and fabricate optimal components and structures.
Various methods have been developed to investigate the viscoelastic response of
materials. Nonetheless, techniques developed for bulk measurements are not readily applicable
for small volumes of time dependent materials, such as polymeric thin films, some biological
materials, and microelectronic packaging. In this case it becomes important to develop methods
that can be applied to measure viscoelastic properties at the nanometer or micrometer length-
scale. In this research the viscoelastic behavior of polymers was investigated by first developing a
2

general model to characterize the linear viscoelastic properties of materials using a flat-punch
indenter tip. Then, experimentation and analytical analysis was conducted to measure the linear
viscoelastic properties of heterogeneous materials with mechanical properties that vary spatially.
Finally, a procedure was developed to investigate the nonlinear viscoelastic properties of a
polymer by using a hybrid approach that combined experimentation with simulation.
Nanoindentation is an extension of conventional indentation technique to micron and
submicron scales. The early understanding of indentation problem is ascribed to Hertz (1896),
Hunter (1960), Boussinesq (1885), and Sneddon (1965). Hertz (1896) solved the problem of
elastic contact between two spheres. The Hertzian problem was investigated by Hunter (1960) for
viscoelastic materials. Boussineq (1885) derived the solution for stress and strain distribution of
concentrated force on half space of elastic materials. Sneddon (1965) generalized the relationship
between load and depth of indentation for elastic axisymmetric indentation problems. These
solutions laid the foundation for extracting mechanical properties (including viscoelastic
parameters) from nanoindentation data.
With the increasing application of very small structures, such as MEMs (Mirco-
Electronic-Mechanical Systems) thin films deposited on substrates, the indentation technique was
developed to provide an approach for measuring properties at micron and sub-micron scales.
Oliver, Hucthings and Pethica (1986) proposed a method to determine the hardness by calculating
the contact area using the depth of impression obtained after indentation load was removed.
Doerner and Nix (1991) and Oliver and Pharr (1991, 1992) later refined the method to determine
the contact area through indenter shape calibration. Using the contact area at maximum load and
by considering Sneddons solution for an elastic indentation problem, they developed methods to
measure elastic modulus and hardness. In their improved methods, the contact area was measured
at submicron resolution without the necessity to optically image the impression. Thus their
3

methods greatly facilitated the application of nanoindentation test techniques to elastic-plastic
materials.
Typically, indenters used for nanoindentation are made of diamond because of its high
hardness and elastic modulus. This allows the indenter to be treated as rigid, especially for the
indentation of metals and polymers. There are various shapes of nanoindenter tips, like
Berkovich, cube-corner, flat punch, spherical, etc. The Berkovich triangular pyramidal indenter is
most used tip for measuring mechanical properties such as hardness and elastic modulus because
a three-sided pyramid is more easily ground to a sharp point than say a four-sided pyramid such
as the Vickers indenter. Another three-sided pyramidal indenter, the cube corner indenter, which
is much sharper with a 35.26 center line to face angle, usually used to estimate the fracture
toughness at relatively small scales since it can produce much higher stresses and strains in the
vicinity of the contact and reduce the cracking threshold. The spherical indenter initiates elastic
contact and then causes elastic-plastic contact at higher loads. It is particularly suitable for
measuring soft materials. The flat punch indenter is usually used when the contact area between
the indenter and sample needs to be constant. In this investigation, different indenter tips and
analysis methods were used to determine the mechanical properties of viscoelastic materials.
The dissertation is organized into five chapters. The first two chapters provide the
introduction and background. The following three chapters are the descriptions of developed
viscoelastic functions measurement methods at nano scale. The last chapter is summarizes the
result of this research and provides conclusions.
Chapter III is focused on linear viscoelastic characterization. First, a flat punch indenter
was used to measure the viscoelastic properties under quasi-static and dynamic loading
conditions. Formulae were derived for the determination for viscoelastic properties in both time
and frequency domains based on viscoelastic contact mechanics analysis of nanoindentation
4

using a flat punch indenter. The contribution of this work is the development of a general linear
viscoelastic analysis. Subsequently, nanoindentation using a Berkovich tip was conducted on
heterogeneous materials. This included the determination of the relaxation modulus of a
thermally aged bismaleimide resin and the out-of-plane relaxation modulus of the human
tympanic membrane. In chapter IV, a nonlinear viscoelastic model was developed based on the
Burgers model and it was implemented in Abaqus/Standard Code to analyze the nonlinear
viscoelastic behavior of PVAc under nanoindentation.
5

CHAPTER II

THEORETICAL BACKGROUND

This chapter presents an overview of the nanoindentation technique and discusses models for
viscoelastic analysis of indentation data.
2.1 The Elastic Indentation Problem
Hertz derived the solution for the contact of two elastic bodies in 1881 based on the linear theory
of elasticity. For an elastic problem of contact between a spherical indenter and a half-space, he
derived the pressure (the normal stress) in the contact regime as,
2 2
0
) 1 (
4
r r
v R
p
=
t

,
0
0 r r < < (2-1)
where is shear modulus, v the Poissons ratio, R the radius of the spherical indenter, and r
0
is
the contact radius. Integrating over the contact area yields the force applied for indentation,
6

dr r r r
v R
P
r
}

=
0
0
2 2
0
2
) 1 (
4
t
t

, (2-2)
which leads to,

3
0
) 1 ( 3
8
r
R v
P
=

. (2-3)
According to Hunter (1960), for a rigid spherical indenter, if h<<R,
Rh r =
2
0
, (2-4)
where, h is the displacement of the indenter tip.
From the relationship between loading and displacement for spherical indentation is:
2
3
) 1 ( 3
8
h
v
R
P
=

. (2-5)
Sneddon (1965) extended the Hertzian solution for the contact mechanics problem of frictionless,
axisymmetric rigid indenter of arbitrary shape.
The indentation depth, h, is given in terms of the shape function f, as

}

'
=
1
0
2
1
) (
dx
x
x f
h (2-6)
and the load-geometry relationship is,

}

'
=
1
0
2
2
1
) (
1
4
dx
x
x f x a
P
v
(2-7)
where, x=r/a, and are the shear modulus and Poissons ratio of the half-space respectively.
7

For a spherical indenter, the indenter shape function becomes
2 2 2
1 1
) ( x a R R x f z = =
where, R
1
is the radius of indenter tip. Consider this relation and combining Eqns. (2-6) and (2-7)
leads to Eqn. (2-5).
For conical indenter, the load-displacement equation is

2
) 1 (
cot 4
h
v
P
=
t
o
(2-8)
It is noted that above equations are limited to a rigid indenter, with an elastic modulus that could
be regarded as infinite. For the case of a deformable indenter indenting into a half-space, the
reduced modulus was introduced (Fischer-Cripps, 1999). For conical indention, the loading-depth
equation is then,
2
cot 8
h
E
P
r
t
o
= , (2-9)
where, E
r

is reduced modulus, which is expressed as,
i
i
r
E
v
E
v
E
2
2
1 1 1
+
= , (2-10)
where, v and v
i
are the Poissons ratios of the sample material and the indenter, respectively, and
E, E
i
are the Youngs moduli of the sample material and the indenter, respectively.
In indentation problem, the contact area between indenter and sample material is needed to
extract properties, such as elastic modulus and some other properties. Doerner and Nix (1986)
found a linear relationship between contact stiffness and square root of projected contact area.
King (1987) also found the same relationship through finite element simulation. Consider
spherical indentation as an example. Differentiating Eqn. (2-5) with respect to h leads to
8

h
v
R
dh
dp
S
= =
1
4
, (2-11)
The slope of the curve,
dh
dp
, upon unloading is indicative of the stiffness S of the contact.
Consider Rh r =
2
0
, we have
) 1 (
2
2
v
E A
dh
dp
S
= =
t
. (2-12)
Pharr et al. (1992) demonstrated that above equation is the general relationship between contact
stiffness, contact area and modulus for all kinds of axisymmetric rigid indenters. Based on the
above equation, Oliver and Pharr (1992) proposed an improved method to measure Youngs
modulus and hardness. In their method, the load-displacement curve at initial unloading is fitted
with a power law equation. The power law equation is used to calculate the stiffness S. The
contact area, which is a function of the contact radius, is then determined by relating contact
radius h
c
to the indentation displacement h, based on Sneddons solution to axisymmetric
indentation problem. The contact area, taken as function of contact depth after indenter shape
calibration, has such form as follows,

8 / 1
4
4 / 1
3
2 / 1
2 1
2
0 c c c c c
h a h a h a h a h a A + + + + = (2-13)
The Youngs modulus is then calculated through Eqn. (2-10) after the contact area and contact
stiffness are known. The method documented by Oliver and Pharr is regarded as the standard
technique to measure elastic properties, and has been frequently quoted in nanoindentation. In
this research, some part of this method will also be applied when dealing with indentation on
viscoelastic materials.
9

Conventional indentation tests deal primarily with relatively large deformations. The
hardness of a material is obtained by the maximum indentation force divided by the projected
area of final impression measured optically after the load is removed (Pethica et al., 1983). In a
typical nanoindentation test, the size of the residual impression is often a few microns and this
makes it very difficult to obtain a direct measurement using optical techniques. Thus, in
nanoindentation testing, the depth of penetration beneath the specimen surface is measured as the
load is applied to the indenter. The known geometry of the indenter then allows the size of the
area of contact to be determined.
During a typical nanoindentation test, the force and displacement are recorded as the
indenter tip is pressed into the test materials surface with a prescribed loading and unloading
profile. Figure. 2-1 shows a typical of nanoindentation load-displacement data for aluminum.
Such data can be analyzed easily using the Oliver-Pharr approach. On the other hand, the load-
displacement data obtained during nanoindentation testing on a viscoelastic material typically
exhibits a negative unloading curve, as shown in Figure. 2-2.. This is due to time-dependent
behavior (creep), and makes difficult to apply the elastic solution. In this case, it is necessary to
develop a viscoelastic solution to the indentation problem.

10

Figure. 2-1 A typical load-displacement curve of nanoindentation on aluminum

Figure.2-2 Typical load-displacement data obtained from the nanoindentation of a
viscoelastic material. This data was obtained for nanoindentation on polyvinyl acetate (PVAc).
The negative slope at unloading is indicated by a red line.
Despite the fact that nanoindentation technique for measurements of some properties,
such as Youngs modulus and hardness for elastic-plastic materials has been well established and
used widely, nanoindentation on viscoelastic materials is not fully understood even in the regime
of linear viscoelasticity. For nanoindentation on viscoelastic materials in the regime of linear
viscoelasticity, the viscoelastic properties in both time domain and frequency domain are often of
interest. In this report, methods are presented to measure viscoelastic functions in both time and
frequency domains for time-dependent materials using nanoindentation.
2.2 Viscoelastic Material Modeling
Solutions to linearly viscoelastic contact mechanics problems have been derived in the
past. Lee and Radok (1960) derived the analytical solution to the viscoelastic contact problem
involving a spherical indenter. In recent years, some results have been reported on the indentation
11

of viscoelastic materials. Shimizu et al. (1999), Sakai and Shimizu (2001) investigated the
viscoelastic response of soda lime silica glass through pyramidal indentation at glass transition
temperature. Cheng et al. (2000) measured the relaxation modulus using a flat-ended cylindrical
punch for a polymer that was described by a three-element model. Vanlandingham et al. (2005)
measured the relaxation modulus under step displacement and the creep compliance using step
loading. They also investigated the applicability of linear viscoelasticity in nanoindentation on
polymers. Cheng and Cheng (2005) derived an expression for the unloading stiffness of a linearly
viscoelastic solid under nanoindentation. These investigations are useful under their respective
situations but are far from complete. Cheng and Chengs work is limited to the measurements of
creep functions of a very limited class of viscoelastic materials and relies on a closed form
solution of the load-displacement relation for a standard linear solid. In Vanlandinghams work,
the difference of relaxation modulus values between the rheometry measurements and indentation
measurements is quite large which indicate the analytical model used may not fully represent the
real situation. Moreover, due to the nonlinearities in material behavior and contact mechanics in
nanoindentation, the linear viscoelastic models used in those research works cannot accurately
characterize the mechanical behavior of time-dependent materials.
For the measurement of viscoelastic properties in the frequency domain using
nanoindentation, Loubet et al. (1995) proposed a method based on analogy between indention
under cyclic loading and the uniaxial location counterpart. Nevertheless, there was no rigorous
analysis to support the proposed approach. To use nanoindentation to find the viscoelastic
properties of a general viscoelastic material in linear regime, consensus methods need to be
developed, which is the objective of this work. Huang et al. (2005) derived an analytical method
based on the LeeRadok (1960) approach to compute the complex creep compliance for
nanoindentation of a linear viscoelastic material using a spherical tip. The oscillatory load of
dynamic nanoindentation experiment was formed by superimposing a harmonic oscillation upon
12

a quasi-static carrier load. Based on Huangs method, this thesis will derive the linear viscoelastic
functions in frequency domain for nanoindentation with flat punch indenter.
In order to develop general linear or non-linear viscoelastic approaches for analysis of
indentation data, it is first necessary to understand the basis of viscoelastic modeling. The classic
approach has been to derive viscoelastic constitutive models through the use of mechanical
analogs. These approaches have led to the Maxwell fluid (Maxwell, 1867), Kelvin-Voight solid
(Thomson, 1898), and the three-parameter solid (Zener, 1948).
The classical mechanical analog approach can be extended to develop generalized
viscoelastic constitutive models using convolution integrals based on Boltzman superposition
principle, which takes stress (strain) prehistory into consideration. For example, the linearly
viscoelastic constitutive law is given as,
,
,
, o
, c d
d
d
t D t
t
kl
ijkl ij
}

=
) (
) ( ) ( (2-14)
where
ijkl
D are components of creep tensor,
ij
c and
kl
o are shear strains and shear stresses,
respectively. For isotropic materials, the deviatoric stress- strain relations are
,
,
,
, d
d
dS
t J t e
t
ij
ij
}

=
) (
) (
2
1
) ( , (2-15)
and ,
,
,
, d
d
de
t t S
t
ij
ij
}

=
) (
) ( 2 ) ( , (2-16)
where J and are creep compliance and relaxation modulus, respectively.
If time is defined as positive, one has
13

,
,
,
, d
d
dS
t J S t J t e
t
ij
ij ij ij
}
+ =
+
0
) (
) (
2
1
) 0 ( ) (
2
1
) ( (2-17)
and ,
,
,
, d
d
de
t e t t S
t
ij
ij ij
}

+
+ =
) (
) ( 2 ) 0 ( ) ( 2 ) ( . (2-18)

2.3 The Viscoelastic Indentation Problem
In elastic problems, the mode of control (displacement- or load-control) is irrelevant and
the relationships between stress and strain are independent of applied loading conditions. On the
other hand, viscoelastic materials exhibit time-dependent, and thus path-dependent, behavior,
including instantaneous elasticity, delayed elasticity, and viscous flow. The contact stresses and
strains are highly localized close to the contact area, and their magnitude decrease rapidly with
distance from the point of contact making the deformation field inhomogeneous. With this
complexity of the stress and strain distributions under the indenter, it is not practical to solve a
viscoelastic indentation problem directly based on the constitutive equations. One approach to
solve the viscoelastic indentation problem would be to remove the time variable in the governing
equations and in the boundary conditions by employing the Laplace transformation with respect
to time (Lee, 1955). The viscoelastic problem then reduces to an elastic problem called an
associated elastic problem. However, such a method is valid only when the boundary conditions
can be prescribed. For nanoindentation of viscoelastic materials, both the traction boundary and
displacement boundary are changing with time as the contact between the indenter and the
material changes with time. It is not possible to predict explicitly the history of both traction
boundary and displacement boundary. Therefore direct application of the correspondence
principle is not appropriate for solving the viscoelastic indention problem. Lee and Radok (1960)
later proposed an approach applicable for viscoelastic contact problems with moving boundary
14

conditions. They showed that the Hertzian contact problem in viscoelasticity could be solved by
replacing the elastic constants in elastic problem with integral operators under condition of non-
decreasing contact area, such that the corresponding viscoelastic problem could be expressed in
hereditary form. Using the Hertzian solution to elastic indentation problem and assuming that the
viscoelastic material is incompressible, the load-displacement relation follows for a spherical
indenter,
) (
3
8
) (
2
1
2 / 3
0
t h R d
d
dP
t J
t
=
}
t
t
t . (2-19)
In this research, Lee and Radoks hereditary operator based on elastic indentation solution is
applied to develop a consensus method to measure the viscoelastic properties of polymers. In this
section, a method to measure local surface creep compliance for linearly viscoelastic materials is
presented.
As introduced before, the load-displacement relationship for spherical indentation
problem, i.e., Hertz problem is:
2
3
) 1 ( 3
8
h
R
P
v
= , (2-20)
where is shear modulus, v is the Poissons ratio, R is the radius of the spherical indenter, and r
0

is the contact radius. Applying Lee and Radoks method, one obtains,
v
d
d
dP
t J
R
t h
t
}

(
=
) (
) (
8
) 1 ( 3
) (
2 / 3
, (2-21)
Under a constant rate loading history, ) ( ) (
0
t tH v t P = , with
0
v being loading rate, Eqn. (2-20)
becomes
15

v
d J
R
v
t h
t
}
=
0
0 2 / 3
) (
8
) 1 ( 3
) ( , (2-22)
where
0
v is loading rate. Differentiation of Eqn. (2-21) with respect to time yields

dt
dh
v
t h R
t J
0
) 1 (
) ( 4
) (
v
= . (2-23)
Similarly, Sneddons solution for the elastic conical indentation problem, in terms of load-
displacement relationship, is

2
) 1 (
cot 4
h
v
P
=
t
o
(2-24)
where is the angle between the cone generator and the substrate plane. Again, applying Lee and
Radoks method to Eqn. (2-24) leads to:

o
v t
d
d
dP
t J t h
t
}

(
=
) (
) (
cot 4
) 1 (
) (
2
(2-25)
Under a constant rate loading, ) ( ) (
0
t tH v t P = , with ) (t H being Heaviside function, Eqn. (2-25)
becomes

dt
t dh
v
t h
t J
) (
tan ) 1 (
) ( 8
) (
0
o v t
= (2-26)
Eqn. (2-31) and Eqn. (2-35) are used in this research for the computation of creep compliance in
terms of derivative of displacement with respect to time under constant rate loading. Due to the
fact that data from for displacement nanoindentation experiments are usually scattered, the
derivative of displacement with respect to time based on experimental data can induce some
error, even if the related curve is fitted. An alternative approach is proposed next.
16

The general representation of the creep function based on the generalized Kelvin model is given
as,
) 1 ( ) (
1
0
=
+ =
N
i
t
i
i
e J J t J , (2-27)
where
N
J J J , , ,
1 0
are compliance numbers, and
N
, , ,
2 1
are retardation times.
For the Berkovich indenter, substituting Eqn. (2-27) into Eqn. (2-25) we obtain,

=
=
+
=
N
i
t
i i
N
i
i
i
e J t J J v
ctg

t h
1 1
0 0
2
)] 1 ( ) [(
4
) 1 (
) ( . (2-28)
Considering t v t P
0
) ( = , Eqn.(2-28) can be rewritten as,

=
=
+
=
N
i
v
t P
i i
N
i
i
i
e v J t P J J
ctg

t h
1
) (
0
1
0
2
)] 1 )( ( ) ( ) [(
4
) 1 (
) (
0
. (2-29)
If we fit Eqn. (2-29) into the experimentally measured load-displacement curve using the
least square correlation, we can find a set of best-fit parameters
N
J J J , , ,
1 0
and
N
, , ,
2 1
.
We can then substitute these constants to Eqn. (2-27) to determine the creep function when the
Berkovich indenter is used for nanoindentation.
The same method for data reduction to determine J(t) can be applied to a spherical
indenter. For a spherical indenter, substitution of Eqn. (2-24) into Eqn. (2-22) leads to,

=
=
+
=
N
i
t
i i
N
i
i
i
e J t J J
R
v
t h
1 1
0
0 2 / 3
)] 1 ( ) [(
8
) 1 ( 3
) ( , (2-30)
Since
t v t P
0
) ( =
, Eqn. (2-30) can be rewritten as,
17

=
=
+
=
N
i
v
t P
i i
N
i
i
i
e v J t P J J
R
t h
1
) (
0
1
0
2 / 3
)] 1 )( ( ) ( ) [(
8
) 1 ( 3
) (
0
. (2-31)
Similar to the approach employed for a conical indenter, we can fit Eqn. (2-31) to the
experimentally measured load-displacement curve to find a set of the best-fit parameters
N
J J J , , ,
1 0
and
N
, , ,
2 1
. Finally, we can then substitute these parameters into Eqn. (2-27)
to determine the creep function when a spherical indenter is used in nanoindentation.
It is noted that applicability of the hereditary integral operator provided by Lee and
Radok (1960) as shown in Eqns. (2-22) and (2-25) is based on the condition that contact area
between indenter and samples non-decreasing with time. It should also be pointed out that in
Eqns. (2-22) and (2-25) the Poissons ratio is assumed to be constant.
Once J(t) is obtained, other viscoelastic functions, such as the uniaxial relaxation
modulus E(t), can be determined. For example, the creep function in shear, J(t), can be converted
to E(t) through the following relation
t d t J E
t
) 1 ( 2 ) ( ) (
0
v t t t + =
}
. (2-32)

18

CHAPTER III

DETERMINATION OF LINEAR VISCOELASTIC FUNCTIONS USING
NANOINDENTATION
The nanoindentation technique for measurements of some properties, such as Youngs modulus
and hardness for elasto-plastic materials has been well established. Nonetheless, nanoindentation
of viscoelastic materials is not fully understood even in the regime of linear viscoelasticity. In this
chapter, linear viscoelastic analysis was conducted on three different materials using three
different nanoindenter tips: Flat punch nanoindentation on Polydimethylsiloxane (PDMS),
Berkovich nanoindentation on thermally aged bismaleimide resin and spherical nanoindentation
on human tympanic membrane. The objective was to develop and apply a robust scheme for
linear-viscoelastic analysis and explore the indentation of heterogeneous viscoelastic materials.
3.1. Flat Punch Nanoindentation of Polydimethylsiloxane (PDMS)
Polydimethylsiloxane (PDMS) is a widely used silicon-based organic polymer, and is
particularly known for its unusual rheological (or flow) properties. Its applications range from
contact lenses and medical devices to elastomers. It is also found in shampoos (dimethicone
makes hair shiny and slippery), caulking, lubricating oils and heat resistant tiles. PDMS is
optically clear, and is generally considered to be inert, non-toxic and non-flammable. It is
occasionally called dimethicone and is one of several types of silicone oil (polymerized siloxane).
To measure its mechanical properties, it is not easy to develop full contact in the beginning of the
experiment (Cheng, 2005) and it is challenging to make standard specimen shape for mechanical
properties testing. In this case, nanoindentation is applied and flat punch indenter tip is used for
measuring the viscoelastic properties of PDMS samples. The use of a flat punch indenter tip
19

alleviates the issues associated with the development of improper contact at the start of the
indentation experiment.
In recent years, several efforts have been made to investigate viscoelastic
nanoindentation. Oyen (2001) reported phenomenological models for the sharp viscoelastic
indentation. Lu, et al. (2003) developed methods to measure creep compliance of polymers using
Berkovich and spherical indenters. Huang, et al.(2005) developed a method to determine
viscoelastic properties in frequency domain using a spherical indenter; they also presented
methods to measure Youngs relaxation modulus using Berkovich and spherical indenters.
Cheng, et al. (2005) investigated creep and relaxation behavior under a constant rate
loading/displacement history using flat punch indenter on viscoelastic materials described by a
three-element viscoelastic model. However, for an arbitrary linearly viscoelastic material, the
phenomenological model could not be necessarily described by a three-element model. Thus a
more general model is needed to characterize the viscoelastic behavior in flat punch indentation.
In this study, methods are given to measure linear viscoelastic functions in both time and
frequency domains, such as shear relaxation modulus, creep compliance, complex compliance,
etc., using a flat punch indenter tip. This analysis uses an arbitrarily general (multi-parameters)
linear viscoelastic model.
3.1.1 Theoretical prerequisites
The equations for determination of viscoelastic functions in both time and frequency
domains are derived in this section. As a circular flat punch indenter penetrates into a half space
composed of a homogeneous, isotropic and linearly elastic material, as shown in Figure. 3-1, the
indentation load is proportional to the indentation displacement, and is described as,
20

h
GR
P
v
=
1
4
(3-1)
where P is the indentation load, h the displacement, G the shear modulus, R the radius of
cylindrical indenter, and v the Poissons ratio.
2R
h

Figure. 3-1 Schematic of flat punch indentation
The solution to the problem of a flat punch indenter indenting into a linearly viscoelastic
material can be obtained based on the solution to the corresponding elastic indentation problem.
The contact area between the indenter and workpiece is constant and equal to R t 2 during
viscoelastic indentation, in other words, the contact area is non-decreasing. Therefore, the
Correspondence Principle can be applied to derive the relation between indentation load and
displacement. Using the Correspondence Principle, the indentation load-displacement relation can
be written as

v
d
d
dh
t
R
P
t
}

=
0
) (
) (
1
4
(3-2)
for the case when the Poissons ratio is a constant. Also, here ) (t is the relaxation modulus in
shear. Under constant rate displacement history,
t V t H t h
0
) ( ) ( = (3-3)
21

where H(t) is the Heaviside function and
0
V the loading rate, Eqn. (3-2) can be simplified into
}

=
t
d t
RV
P
0
0
) (
1
4

v
. (3-4)
Differentiation of Eqn. (3-4) leads to
) (
) (
4
1
) (
t dh
t dP
R
t
v

= . (3-5)
Since the load-displacement data from nanoindentation tests generally shows scatters,
which would induce error in measuring ) (t , the relaxation modulus can be more accurately
determined using a curve fitting method.
A linearly viscoelastic material can be represented by the generalized Maxwell model,
+ =
N
i
t
i
i
e t
1
) (
t
, (3-6)
where
and
i
are relaxation numbers, and
i
t the relaxation times. Substituting Eqn. (3-6)
into Eqn. (3-4) one has,
(
(
|
|
.
|
\
|
+
=

=
N
i
t
i
i
i
e
t
t Rh
t P
1
1
1
) ( 4
) (
t
t

v
. (3-7)
The load-displacement relation described in Eqn. (3-7) can be used to fit the load-
displacement data from nanoindentation tests, which will result in the best fit parameters of
,
i
and
i
t . Subsequently, the relaxation modulus in shear can be determined as per Eqn. (2-6).

With the relaxation modulus determined, one could in principle extract the creep
compliance by conversion. However, the conversion between properties related to relaxation and
creep is an intrinsically ill-pose problem. Therefore an independent test is needed to determine
the creep compliance. Eqn. (3-2) can also be written as
22

v
d
d
dP
t J
R
h
t
}

=
0
) (
) (
4
1
. (3-8)
Using a derivation similar to that for the relaxation modulus, one can derive equations for
the determination of creep compliance under constant rate loading history by replacing Eqn. (3-5)
with
dP
dh R
t J
) 1 (
4
) (
v
= , (3-9)
and replacing Eqn. (3-6) with the generalized Kelvin model,
) 1 ( ) (
1
0
=
+ =
N
i
t
i
i
e J J t J
t
, (3-10)
where
and
i
are creep numbers, and
i
t the retardation times, and also replacing Eqn. (3-7)
with
(
(
|
|
.
|
\
|
+ +
=

=
N
i
t
i
i
e
t t
J J
R
t P
t h
1
0
1 1
1
4
) ( ) 1 (
) (
t
v
. (3-11)

In the frequency domain, an oscillatory indentation loading needs to be applied to
measure the viscoelastic functions. The oscillatory load can be formed by superimposing a
harmonic oscillation upon a quasi-static carrier load, such as a constant rate load or a pseudo step
load. When a constant rate loading is used as the carrier load, the dynamic load can be written as
) sin( ) ( ) (
0
t P t tH V t P
p
e A + = . (3-12)
where
p
V is the loading rate and
0
P A is the amplitude of harmonic load. With the substitution of
Eqn. (3-12) into Eqn. (3-8) one has
e e
v

v
d t J P
R
d t J
R
V
h
t t
p
) cos( ) (
4
) 1 (
) (
4
) 1 (
0
0
0
} }
A
= . (3-13)
Simplification of Eqn. (3-13) leads to
23

. ) sin( ) ( sin ) cos( ) ( cos
4
) 1 (
) (
4
) 1 (
0 0
0
0
(
+ A
=
} } }
t t t
p
d J t d J t P
R
d t J
R
V
h e e e e
v

v
(3-14)
Since
}
=
0
) sin( ) ( ) ( ' e e d J J and
}
=
0
) cos( ) ( ) ( " e e d J J , considering the
steady state of viscoelastic elastic response which is equivalent to t , Eqn. (3-14) can be
written as
| |. ) ( ' sin ) ( " cos
4
) 1 (
) (
4
) 1 (
0
0
e e e e
v

v
tJ tJ P
R
d t J
R
V
h
t
p
+ A
=
}
(3-15)
On the other hand, the output of displacement from nanoindentation using flat punch can
be obtained from nanoindenter output in the form of
| e | e | e sin ) cos( cos ) sin( ) ( ) sin( ) ( ) (
0 0 0 0 0
t h t h t h t h t h t h A A + = A + = . (3-16)
Comparing Eqn. (3-16) with Eqn. (3-15) leads to

v
d t J
R
V
t h
t
p
}

=
0
0
) (
4
) 1 (
) ( (3-17)
which is the same as Eqn. (3-8), and
, cos
1
4
) ( '
0
0
|
v
e
P
h R
J
A
A
= |
v
e sin
1
4
) ( "
0
0
P
h R
J
A
A
= . (3-18)
Eqn. (3-18) can be used to determine the storage and loss compliance from such data as
the amplitude of both harmonic load and harmonic displacement, as well as phase angle from
nanoindentation.
3.1.2. Experiments
An MTS Nano Indenter XP system was used in nanoindentation tests to acquire load-
displacement data. The nanoindenter can reach a maximum indentation depth of 500 m and a
24

maximum load of 500 mN. The displacement resolution is 0.2 nm and the load resolution is 50
nN. The flat punch indenter made of diamond has a radius of 5m, as shown in Fig.3-1.
The materials used in these tests were a commercially available polydimethylsiloxane
(PDMS-ELASTOSIL RT 601 silicon rubber, Wacker Company). The silicon rubber specimen
was annealed at 100 C for 8 hours and was cooled down slowly to room temperature at a rate of
approximately 5 C /hr. Samples were then stored in an enclosed desiccator with approximately
50% relative humidity produced by placing a saturated salt solution in this enclosed environment.
The specimens were subsequently mounted on aluminum holders. All specimens had an ageing
time of nearly 75 hours to achieve uniform moisture absorption. The humidity in the room was
maintained at ~ 50% by the use of a humidifier and a dehumidifier in combination.
Nanoindentation tests on silicon rubber specimens were performed in air at room
temperature (23 C) and at 50% relative humidity. Each test was started after the drift rate of the
indenter tip had dropped below a set value (typically0.05 nm/s) to ensure that a thermal
equilibrium condition for the specimen and nanoindenter system had been reached. After the
indenter tip had made contact with the specimen surface, a quasi-static or dynamic load was
applied, and experimental data such as indentation load and depth (or harmonic load and
displacement) were recorded simultaneously at a sampling rate of five data points per second.
3.1.3. Results
The results from nanoindentation will be described in this section for PDMS
(ELASTOSIL RT 601 silicon rubber). The experimental load-displacement data were fitted into
Eqn. (3-11), and the fitted curves are also plotted in Fig. 3-2. The fitted load-displacement curve
of loading portion was plotted in Fig. 3-2(a). We can see it can fit very well with the load-
displacement curve obtained from the nanoindentation experiment. Fig. 3-2(b) provided the shear
relaxation modulus value obtained from curve fitting method as well as differentiation method.
25

The results are quite similar from these two methods. Since the load-displacement data from
nanoindentation tests often shows scatters, which would cause errors in measuring the relaxation
modulus, the curve fitting method would be more suitable in the analysis. It is seen that Eqn. (3-
11) can describe the nanoindentation data very well. The measured shear relaxation modulus of
PDMS is around 4.4 MPa. The reported PDMS elastic modulus is from 2 MPa-5MPa depending
on the degree of crosslinking.

(a) Load-displacement curves from experiments (b) Results of G(t) and fitting
Figure 3-2. Nanoindentation results for ELASTOSIL RT 601 silicon rubber
Displacement (nm)
L
o
a
d
(
m
N
)
0 500 1000 1500
0
0.05
0.1
0.15
0.2
0.25
Fitting
Differentiation
Time (s)
S
h
e
a
r
r
e
l
a
x
a
t
i
o
n
m
o
d
u
l
u
s
(
M
P
a
)
0 20 40 60
0
1
2
3
4
5
6
Fitting
Differentiation Fitting
Experiment
26

(a) Amplitude of harmonic load (b) Amplitude of harmonic displacement

(c) Phase angle (d) Storage and loss compliance
Figure. 3-3 Dynamic nanoindentation results for ELASTOSIL RT 601 silicon rubber
Figure 3-3 gives the plot of harmonic load amplitude, harmonic displacement amplitude,
phase angle and the results of storage and loss compliance. In experiments, the nanoindenter
modulates the amplitude of harmonic force (Fig. 3-3(a)) to produce the set target in harmonic
displacement (Fig. 3-3(b)). After the indenter tip had made contact with the surface of test sample,
Time (s)
H
a
r
m
o
n
i
c
L
o
a
d
(
u
N
)
0 100 200 300 400
0
20
40
60
80
100
Time (s)
H
a
r
m
o
n
i
c
D
i
s
p
l
a
c
e
m
e
n
t
(
n
m
)
0 100 200 300 400
0
1
2
3
4
5
6
7
Time (s)
P
h
a
s
e
A
n
g
l
e
(
d
e
g
r
e
e
)
0 100 200 300 400
0
5
10
15
20
Time (s)
C
o
m
p
l
e
x
C
o
m
p
l
i
a
n
c
e
(
1
/
G
P
a
)
0 100 200 300 400
0
1
2
3
4
5
6
Loss Compliance
Storage Compliance
27

the indentation load, depth, harmonic load amplitude, harmonic displacement amplitude, and out-
of-phase angle between the harmonic load and the displacement were recorded simultaneously at
a sampling rate of five data points per second. As Fig. 3-3 (a) shows, the steady value of
harmonic load reaches at 82.5 N. Fig. 3-3(b) shows the harmonic displacement which reaches
steady at 4.5-5 nm in response to the harmonic load. The out-of-phase angle between
harmonic load and harmonic displacement is shown in Fig. 3-3(c).After the harmonic
response had reached a steady state, data were used to determine the complex compliance of
the material. Figure 3-3(d) was plotted from calculation. The storage compliance is1.80.51/GPa
and the loss compliance is 0.2 0.03 1/GPa.
3.1.4. Conclusions on flat punch nanoindentation
In this work, generalized methods are presented to measure linear viscoelastic functions
in both time domain and frequency domain using a plat punch indenter. The methods are proved
to be applicable to heterogeneous materials where homogeneity is assumed locally. PDMS
material was used for method validation. Based on the solution for a linearly viscoelastic half
space subjected to the indentation of an indenter, formulas are derived to compute creep
compliance functions and complex compliance functions for general linearly viscoelastic
materials using flat punch indenter.
In time domain, formulas were derived based on Lee-Radok approach while the creep
compliance equation was realized by applying the generalized Kelvin model. The relaxation
modulus/creep compliance functions of PDMS are measured under constant rate
displacement/loading history. In frequency domain, following the Hertzian solutions for
indentation in linear elasticity and the consideration of the Lee-Radok approach for a moving
boundary problem in linear viscoelasticity, formulas for the components of the complex
compliance function in the frequency-domain have been derived based on the load-displacement
28

relation for linearly viscoelastic materials under harmonic loading. Loss compliance and storage
compliance are measured using harmonic load, harmonic displacement and out-of-phase angle
from flat punch nanoindentation; the dynamic loading is realized by superimposing a harmonic
load on a quasi-static load.
3.2. Viscoelastic Characterization of Thermally Aged Bismaleimide Resin
Polymer matrix composites (PMCs) have found increasing applications in extreme
environments such as components in aircraft near the engine, through exhaust gas area, or in
pump components. For PMCs such as carbon fiber reinforced bismaleimide resin composites,
exposed to high temperature environments, the thermal effect on the mechanical properties during
the service period is critical. Creep, thermal oxidation and cracking are considered as three major
degradation mechanisms caused by high temperature exposure, oxidative attack, moisture
absorption and other factors during thermal aging process. The oxidative layer growth depends on
exposed surface and fibermatrix interface. Matrix cracking provides more available surface and
oxygen penetration paths for oxidative reaction. Thus the oxidation occurs from the surface
towards inward region and the PMCs subjected to thermal oxidation in general presented three
different zones, namely oxidized zone, active zone and unoxidized zone (Figure3-4). Also, the
differences of oxidation rates of bismaleimides and added agents could cause phase separation
too.
Nelson (1983) first reported the anisotropic oxidative response of PMCs when he noticed
that the oxidation process is sensitive to the surface area. Physical aging effect on PMCs was
discussed by Sullivan (1990), McKenna (1992) etc. The high-temperature aging behaviors of
several neat polymer resins and their composites has been studied by Bowles (1992), Tsuji
(1998), Abdeljaoued (1999) etc. Colin (2000) et al. proposed the kinetic model of thermal
oxidation of PMR-15 PMCs. Schoeppner et al. (2007) reported the methods used for processing
the optical micrographs of aging responses. Pochiraju et al. (2008) presented a combined thermo-
29

chemo-mechanics model of resin oxidation. The presented models may predict the change of
mechanical properties of PMCs after thermal oxidation process. However, as the degradation
process is very complicated, including chemical reactions, mechanical structure changes, the
appearance of shrinkage and cracks etc., the models cannot obtain accurate mechanical properties
results. Thus, a more direct experimental method is needed to be established to determine the
mechanical properties of the oxidized, active and unoxidized layer of PMCs samples. As the
thicknesses of these layers are thin and conventional tensile tests cannot be conducted. In this
chapter, nanoindentation is conducted to measure the mechanical properties of different layers of
aged bismaleimides composite.
Lu, et al. developed a method to measure the creep compliance of polymers under ramp
and step loading history using berkovich and spherical indenter. This method is applicable for
general linearly viscoelastic materials and is used in this chapter to obtain Youngs relaxation
modulus.

Figure 3-4. Section view of aged specimen with three oxidation phases defined.
The PMCs material being tested here is carbon fiber reinforced bismaleimides resin
composite. The matrix resin is CYCOM 5250-4 bismaleimide, a high temperature resin with glass
transition temperature of 300 C as reported in manufacturers specifications. It has continuous
service temperature up to 204 C and can be used as the matrix for carbon or glass fiber
reinforced composites. CYCOM-5250-4 is used in primary aircraft structures, including engine
Oxidized zone
Active zone
Unoxidized
zone
30

nacelles, fuselage skin and stiffeners, wing and stabilizer spars and skins, and other critical load-
bearing components. To evaluate the mechanical properties in oxidized layers, nanoindentation
was made on both surface and cross sectional area of the bismaleimide resin specimens at
different aging times.
3.2.1. Theoretical background
In this section, we provide some equations used for the measurement of linear
viscoelastic properties from the load and displacement data under nanoindentation. A Berkovich
indenter is used as an axisymmetric rigid conical indenter. For indentation into an elastic half-
space, Sneddon has derived the load-displacement relationship given as
P
G
h
4
tan ) 1 (
2
o v t
= , (3-19)
where P is the indentation load, h is the indentation depth, is the angle between the cone
generator and the substrate plane,v is the Poissons ratio, and G is the shear modulus.
For the indentation to a linearly viscoelastic material, the solution cannot be derived from
the correspondence principle directly, as the contact area between the indenter and the half space
changes with time. To resolve this problem, Lee and Radok proposed a hereditary integral
operator to determine the time-dependent stresses and deformations under condition of non-
decreasing contact area between the indenter and the test material. Following this theory, Eqn. (3-
19) can be revised to the following form for a linearly viscoelastic material when a constant rate
loading history is applied.
2
0
(1 ) tan ( )
( ) ( )
4
t
dP
h t J t d
d
t v o

(
=
(

}
, (3-20)
where ) (t J is the shear creep compliance in shear at time t. As
0
( ) P t p t = , and
0
p is the loading
rate, differentiation of Eqn. (3-20) gives
31

0
8 ( )
( )
(1 ) tan
h dh t
J t
p dt t v o
=
, (3-21)
Eqn. (3-21) provides a direct differentiation method to determine the shear creep compliance in
shear.
However, the data from displacement nanoindentation experiments are usually scattered,
and the derivative of displacement with respect of time based on experimental data will produce
error. In this case, we applied an alternative approach to determine the creep compliance which is
based on the curve fitting approach consider a generalized Kelvin model for the shear creep
compliance
+ =
N
i
t
i
i
e J J t J
1
/
0
) 1 ( ) (
t
, (3-22)
where
0
J ,
i
J are compliance coefficients,
i
t retardation times.
When
0
( ) P t p t = , substituting Eqn. (3-22) into (3-20) leads to
0
( )
2
0 0
1 1
1
( ) (1 ) tan [( ) ( ) ( )(1 )]
4
i
P t
N N
p
i i i
i i
h t J J P t J p e
t
t v o t

= =
= +

. (3-23)
Using the least squares correlation to the nanoindentation load-displacement curve into
Eqn. (3-23), all parameters,
0
J ,
i
J (i=1, , N) and
i
t can be obtained. The creep compliance
can then be determined from the Eqn. (3-22). Subsequently the relaxation modulus E(t) can be
obtained from creep compliance, using
t d t J E
t
) 1 ( 2 ) ( ) (
0
v t t t + =
} (3-24)
when the Poissons ratio

v is constant.
3.2.2. Experiment
32

. The CYCOM-5250-4 resin composite was cut into 7.5mm3mm3mm pieces and then
washed with soap and rinsed with distilled water for a minimum of five minutes. The specimens
were then dried with paper towels and placed in a vacuum desiccator for at least 48 hrs. To
prevent from direct contact with metal parts of the oven, the specimens were placed on glass fiber
cloth which was burned off at 500 C for one hour to avoid contamination. The oven temperature
was brought up to intended temperature (200C and 300C respectively) and the specimens were
placed into the oven for a certain time. Then the samples were cooled down slowly to room
temperature at a cooling rate of approximately 5C/hr and then stored in the vacuum desiccater
for nearly 72hrs before the nanoindentation experiment.
Nanoindentation was conducted on both surface and cross section. To avoid cutting and
polish heat effect, we use a special method to get the smooth surface of the cross section of the
specimens for nanoindentation. The smooth cross section was obtained by fracture by suddenly
hammering a razor blade into the resin sample as shown in Figure 3-5. The razor blade was
washed and wiped clean with paper towel before each use. The razor blade was placed straight in
the slot on the sample. The AFM scanning images of a 2 m2 m area of the cross section of
BMI sample are showing in figure 3-6. The RMS value of the image area is 2.1 nm. The
fractured, uncutting edge was smooth for nanoindentation.

33

Figure.3-5 Cutting set for obtaining the facture cross section

(a)
Razor blade
Sample
34

(b)
Figure. 3-6 AFM images of the cross section of BMI sample (a) sample height 2D image(b)
sample height 3D image
Nanoindentation tests on both surface and cross section region were conducted and
viscoelastic analysis is conducted to extract the Youngs relaxation modulus. For nanoindentation
on cross section, the change of Youngs relaxation modulus for samples at short aging time (e.g.
32min) at 200C are not detectable, so that the nanoindentation results have not shown here. To
understand the effects of the aging temperature and aging time effect, we considered six aging
conditions: the specimens aged for 5.2 hours, 52.3 hours, and 523 hours at 200C and 300C
respectively. Nanoindentation on un-aged sample was also conducted for reference. The entire
cross sectional region for an aging sample can be divided into three zones: the oxidized zone,
reacting zone and un-oxidized zone. To represent different zones of degradation, four regions on
the cross section were selected starting from the edge to the center as shown in Figure 3-7.
35

Figure.3-7 Fractured cross section surface with 4 testing areas defined.
Nanoindentation was conducted on an MTS Nano Indenter XP System equipped with a
diamond berkovich indenter tip. The resolutions of the machine for load and displacement are 50
nN and 0.01 nm, respectively. The Berkovich indenter tip was modeled as an axisymmetric
conical indenter with a half-cone angle of 70.2. The nanoindentation was conducted in the air at
room temperature (23C) under a relative humidity about 50%. Three to five load-displacement
curves were recorded at each zone and the results are reproducible. There were at least 50 m
spaces between each test location. In all nanoindentation measurements, a loading rate of 0.1
mN/s was used, and the maximum load reached was 5mN. The typical maximum displacement
was around 800 nm. The measured indenter tip drift rate was within 0.02 nm/s within a total
nanoindentation time of 50 s in each measurement. As a result, the error induced by drift is
negligible.
3.2.3. Results and discussions
36

The aging status of resin depends on both aging temperature and aging time. Here we are
going to discuss the effect of these two aging conditions on the measured Youngs relaxation
modulus value.
Figure 3-8 (a) shows all load-displacement experiment curves for the near edge region of
un-aged sample. (b) Shows the fitted load-displacement curve together with the measured curve
from one of the nanoindentation tests.

(a) (b)
Figure 3-8. The nanoindentation load-displacement curves for the edge area of cross-section of
non-oxidized sample. (a) All test load-displacement curves from nanoindentation experiment. (b)
The load-displacement curve from experiment and fitting method.
The measured Youngs relaxation moduli for the four defined testing areas of un-
oxidized sample are illustrated in Figure 3-9. We found the modulus value of the interior region is
about 5% lower than the edge region. The BMI (bismaleimide resin) cure reactions are
incomplete after standard composite fabrication and further cure can occur in the 25-177C
37

service environment temperature range which will induce shrinkage stresses. Here we suppose
the un-oxidized sample is mainly affected by physical aging that would cause the shrinkage and
the modulus increase at edge region.

Figure 3-9. Youngs relaxation modulus measured from the fractured cross-section for an un-
oxidized sample
The BMI (bismaleimide) resins are sensitive to physical aging when it is below the glass
transition temperature Tg and the physical aging will be faster when it closes to Tg. So when we
increased the temperature to 200C and put the specimens into the oven, the physical aging effect
will be more obvious. However, when thermal oxidation occurs, the physical aging contribution
is so small compare to it and can be neglect. Figure 3-10 illustrates the Youngs relaxation
modulus from the nanoindentation test on the surface of bismaleimide resin sample for different
aging time. The surface indentation displacement is limited within 1m. Thus we can assume the
38

detected region is totally exposed to oxidizing environment and the measured result can reflect
the resin surface property change during aging. The curve indicate the modulus steadily increase
within 1 hour aging time and get the ultimate value at 32mins. As we mentioned above, the
further cure induces shrinkage during this period. Then the modulus reduces because of the
relaxation of shrinkage stress together with the oxidation growth. As a sudden modulus reduction
appears in the figure at 52.3 hours aging time, we may predict a serious damage occurs caused by
combined influence of thermal oxidation, moisture absorption, matrix cracking, and
microstructure changes.

(a)
39

Figure 3-10. Youngs relaxation modulus result measured from nanoindentation test on the
surface of the specimens aged at 200C (a). Youngs relaxation modulus measured at different
aging time. (b). Youngs relaxation modulus vs. aging time.
Microstructure studies have shown that oxidation of high-temperature polymers is mostly
a surface phenomenon (Nam and Seferis, 1992). An oxidation reaction in the interior relies on
mass-transport process, including diffusion of oxygen inward and subsequent diffusion of
reaction products. No obvious change for the modulus value on the cross section of resin sample
has been found at short aging time and we assume the oxidation still remains on the surface
during this period. The measured Youngs relaxation modulus on the cross section of 5.2 hours,
52.3 hours, and 523 hours aging time samples are illustrated in the Figure 3-11, Figure 3-12 and
Figure 3-13 respectively. Un-aged specimen data also presented for reference. Measured Youngs
relaxation modulus values at time t=50s on the cross section at 200C are presented in table1.
40

(a)

(b)
1.5
2
2.5
3
3.5
4
4.5
0 0.5 1 1.5 2
Y
o
u
n
g
'
s

R
e
l
a
x
a
t
i
o
n

M
o
d
u
l
u
s

(
G
P
a
)

Distance From Edge (mm)
41

Figure 3-11. Youngs relaxation modulus result measured from nanoindentation test for the cross-
section of the specimen aged 5.2 hours at 200C. (a). Youngs relaxation modulus at different
cross-sectional locations . (b). Youngs relaxation modulus (at 50 s) determined from
nanoindentation on cross-sectional area.

(a)
42

(b)
1.5
2
2.5
3
3.5
4
4.5
0 0.5 1 1.5 2
Y
o
u
n
g
'
s

R
e
l
a
x
a
t
i
o
n

M
o
d
u
l
u
s

(
G
P
a
)

43

(a)

(b)
1.5
2
2.5
3
3.5
4
4.5
0 0.5 1 1.5 2
Y
o
u
n
g
'
s

R
e
l
a
x
a
t
i
o
n

M
o
d
u
l
u
s

(
G
P
a
)

44

section of the specimen aged 523 hours at 200C. (a). Youngs relaxation modulus at different

Table 1. Youngs relaxation modulus (at 50s) determined from nanoindentation on cross-sectional
area of specimens aged at 200C.

un-oxidized
sample modulus
(GPa)
200C aged sample modulus (GPa)
5.2hrs 52.3hrs 523hrs
Edge Area 3.920.01 2.280.18 2.320.08 2.270.38
0.3mm-0.7mm Area 3.970.06 3.030.01 2.710.03 2.470.06
0.7mm-1.2mm Area 3.910.04 2.920.05 2.870.04 2.530.06
1.2mm-1.7mm Area 3.720.04 3.590.08 2.880.03 2.790.15

Different from the un-oxidized sample, all the aged sample experiment results show the
modulus of edge region is lower than the core region due to the oxidative degradation. The
modulus measured at four locations all decreased obviously during the aging process. For the
outer near edge region, the modulus decreased about 40% after aging 5.2 hours at 200C while
the modulus for the inner core region decreased only 3.5%. For 52.3 hours aging time sample, the
modulus for the outer region remains unchanged which indicate a stable status approached and
the reaction was completed under the same aging condition, but the modulus for the inner region
45

keep decreasing for about 22.6%. And for 523 hours aging time sample, the interior modulus
decreased even more and close to the edge value. We can predict for longer aging time at 200C,
the measured Youngs relaxation modulus for the whole area would approach a constant value.
The degradation penetration is due to the microcracking resulting from the differences in thermal
expansion of longitudinal and transverse directions. Such kind of microcracking would make
more surfaces available for oxidation reaction and more paths for oxygen and moisture diffusion.
Cure was incomplete due to the glass-state diffusion restrictions at 250C, so when
temperature was brought to 300C, principal further cure occurs that can be diffusion controlled
by further dehydration followed by complex dissociation of the resultant ether linkages to from
stiffer carbon linkages. This dissociation and recombination process would form a stiffer, more
molecularly open crosslinked network. The Youngs relaxation modulus for the cross section of
5.2hrs and 52.3 hrs aging time bismaleimide resin samples at 300C are demonstrated in Figure
3-14 and Figure 3-15 respectively. Measured Youngs relaxation modulus values at time t=50s on
the cross section at 300C are presented in table 2.
46

(a)

(b)
1.5
2
2.5
3
3.5
4
4.5
0 0.5 1 1.5 2
Y
o
u
n
g
'
s

R
e
l
a
x
a
t
i
o
n

M
o
d
u
l
u
s

(
G
P
a
)

47

Figure 3-14 Youngs relaxation modulus result measured from nanoindentation test for the cross-

(a)
48

(b)

1.5
2
2.5
3
3.5
4
4.5
0 0.5 1 1.5 2
Y
o
u
n
g
'
s

R
e
l
a
x
a
t
i
o
n

M
o
d
u
l
u
s

(
G
P
a
)

49

Table 2. Youngs relaxation modulus (at 50s) determined from nanoindentation on cross-sectional
area of different specimens aged at 300C.

un-oxidized
sample modulus
(GPa)
300C aged sample modulus (GPa)
5.2hrs 52.3hrs 523hrs
Edge Area 3.920.01 2.990.06 2.030.12 0.120.004
0.3mm-0.7mm Area 3.970.06 3.240.04 2.090.12 0.260.016
0.7mm-1.2mm Area 3.910.04 3.560.28 2.850.10 1.160.013
1.2mm-1.7mm Area 3.720.04 3.610.05 2.870.09 1.860.03

After being aged at 300C for 5.2 hours, the Youngs relaxation modulus at edge region
decreased by about 24% while the modulus of the inner core region decreased by 3%. Compared
to same aging time result at 200C, the modulus values were elevated for all the testing regions
due to the cure reaction conducted above 250C. For 52.3 hours aging time sample, the modulus
of edge decreased by 48% and core modulus decreased by 23%. After 523 hours aging time at
300C, some damage was clearly observed on the sample. The Youngs modulus illustrated here
is the average measurement value from MTS software. The dramatic modulus loss indicates
material failure with oxidative degradation.
3.2.4. Conclusion of nanoindentation on bismaleimide resin
Nanoindentation measurements were conducted on both surface and cross section of aged
bismaleimide resin specimens with different aging time at 200C and 300C respectively. Linear
viscoelastic analysis was performed to extract the Youngs relaxation modulus from surface to
50

interior of aged bismaleimide sample. When the temperature is elevated to 200C, the further
cure induced shrinkage would increase the modulus. With longer aging time, the thermal
degradation became the dominate influence factor and caused the modulus to decrease
significantly. Such phenomenon is clearly demonstrated in surface Youngs relaxation modulus
measurement results. The Youngs relaxation modulus changes in four predetermined regions on
cross section indicate the mechanical properties of oxidized zone, active zone and unoxidized
zone and predict the oxidation propagation with aging time. As the principal further cure occurs
above 250C that can be diffusion controlled, the Youngs relaxation modulus of aged
bismaleimide resin at 300C appears higher than aged sample at 200C in short aging time, but it
reduce dramatically due to the degradation and serious damage appear at 523 hours aging time.
The experiment result, in general, tests the mechanical properties of bismaleimide resin, which is
a high temperature thermal-setting composite, under different aging conditions.
3.3. Viscoelastic characterization of human tympanic membrane
The eardrum, or tympanic membrane, separates the middle ear from the outer ear,
receives the sound waves collected by the outer ear, and transmits them to the middle ear. The
human middle ear, including tympanic membrane (or eardrum), three ossicular bones (i.e.,
malleus, incus and stapes), and suspensory ligaments (or muscle tendons), transfers the sound
from the external ear canal to cochlea (or inner ear). The tympanic membrane initiates this
acoustic-mechanical transmission by converting the acoustic wave (pressure wave) into vibrations
of the middle ear ossicular bones (Gan et al., 2004). The changes of structure and mechanical
properties of the TM in middle ear diseases, such as the TM retraction, middle ear infection, otitis
media with effusion, and perforation of the TM, can affect directly sound transmission and lead to
conductive hearing loss (Gan et al., 2006). For instance, the otitis media, one of the most
common diseases in pediatric population, causes TM edema or perforation and result in the
hearing loss. Hence, the effective implants and surgical treatments are necessary to improve or
51

recover the hearing loss. To solve this problem, it is quite important to understand the roles of the
individual components in ear, the hearing aid devices and surgical procedures in acoustic
transmission. To measure the mechanical properties over the entire eardrum can provide more
accurate parameters for simulation model.
Von Bksy in 1960 reported the elastic modulus of TM to be 0.02 GPa using beam
bending test. Kirikae also measured the elastic modulus of TM strip to be 0.04 GPa using a
longitudinal dynamic tension vibrator. Decraemer et al. performed uniaxial tensile tests on human
TM and documented Youngs modulus of 23 MPa at relatively high strain. Fay et al. reported 30-
90 or 100-400 MPa elastic modulus of TM through modeling correlation methods in 2005. Gang
et al. used viscoelastic analysis method to determine the Youngs relaxation modulus of human
TM to be 6-10 MPa from nanoindentation experiment.
This section described the measurement of Youngs relaxation modulus values using
nanoindentation on the whole human tympanic membrane (eardrum). Since eardrum is a
nonhomogeneous biomaterial, the nanoindentation experiments were conducted on the entire
region of it. As very small size biomaterials, the sample preparation and experimental procedure
of nanoindentation on ear drums are very difficult. The 10 m radius spherical nanoindenter tip
was used. The viscoelastic properties were analyzed using the method developed by Lu et al.
3.3.1 Analysis method
The load-displacement relationship for spherical indentation into elastic half space problem,
i.e., Hertz problem is:
2
3
) 1 ( 3
8
h
R
P
v
=
, (3-25)
where is shear modulus, v Poissons ratio, R the radius of the spherical indenter, and r0 contact
radius. Applying Lee and Radoks method, one has
52

v
d
d
dP
t J
R
t h
t
}

(
=
) (
) (
8
) 1 ( 3
) (
2 / 3
, (3-26)
Under a constant rate loading history,
) ( ) (
0
t tH v t P =
, with
0
v
being loading rate, Eqn. (3-26)
becomes

v
d J
R
v
t h
t
}
=
0
0 2 / 3
) (
8
) 1 ( 3
) (
, (3-27)
where
0
v
is loading rate.
However, the data from displacement nanoindentation experiments are usually scattered,
and the derivative of displacement with respect of time based on experimental data will produce
error some time. In this case, we applied an alternative approach to determine the creep
compliance which is based on the Kelvin model as Eqn. 3-22.
When
t v t P
0
) ( =
, substituting Eqn. (3-22) into (3-26) leads to

=
=
+
=
N
i
v
t P
i i
N
i
i
i
e v J t P J J
R
t h
1
) (
0
1
0
2 / 3
)] 1 )( ( ) ( ) [(
8
) 1 ( 3
) (
0
. (3-28)
Using the least square correlation to fit Eqn. (3-28) to the load-displacement curve from
nanoindentation, all parameters,
0
J
,
i
J
(i=1, , N) and
i
t
can be obtained. Substitute into Eqn.
(3-22), the creep compliance can be determined. And the relaxation modulus E(t) can be obtained
from creep compliance, using Eqn.3-24.

3.3.2 Nanoindentation experiments
The human TM is a soft tissue with small dimensions (approximately 60 m in thickness
and 8 mm in diameter), as a result, it is a challenge to use conventional techniques such as tensile
tests to determine the viscoelastic properties. With the successful development of nanoindentation
53

techniques for measurements of viscoelastic functions, it becomes possible to measure the
viscoelastic properties of human ear tissue using nanoindentation.
In this study, measurements were conducted on fresh human cadaver TM samples in out-
of-plane directions. . The TM samples were harvested from fresh-frozen human temporal bones
(cadaver ears) through the Willed Body Program at the University of Oklahoma Health Sciences
Center. The tympanic annulus was separated from the bony ear canal with malleus attached to the
TM. All the TM samples had their outer epidermal layer removed, so that the indenter tip came in
direct contact with the lamina propria layer made up of collagen fibers. However, separating the
mucosal layer was very difficult and could induce damage to the TM. Hence, we carried out the
nanoindentation testing without removing the mucosal layer. Figure 3-16 shows the lateral view
of a right ear TM sample. The TM was sectioned into four portions: anterior-superior, anterior-
inferior, posterior-superior, and posterior-inferior quadrants following the clinical sectioning
procedure (Figure. 3-17). As a nonhomogeneous material, the different portion of eardrum has
different properties. We made nanoindentation tests on all area of tympanic membrane and gave
the modulus distribution mapping figure.

54

Figure.3-16 Image of the right TM (lateral view)

Figure 3-17: Schematic diagram showing four quadrants of left ear TM (medial view).

Before experiments the TM samples were stored in a freezer at 40 C. The TM was
defrosted for approximately 20 minutes prior to sectioning using a scalpel. Figure.3.15 shows a
Posterior-
Superior
Umbo
Posterior-
Inferior Anterior-
Inferior
Anterior-
Superior
Manubrium
Section
lines
55

right TM which was cut into four parts. A TM sample was mounted on top of a flat aluminum
substrate. The mount was designed to allow nanoindentation tests of TM in both dry and wet
conditions. The medial side of the TM is rougher than the lateral side. Nanoindentation was made
on the lateral side in all nanoindentation measurements. In physiological condition, the medial
side is saturated with fluid so that it remains in wet condition. To emulate this condition, we
allowed the medial side of the TM sample in contact with the aluminum substrate. For TM to
remain in wet condition, the outer ring of the sample was kept in contact with the saline solution
(NaCl concentration of 0.9 %, pH 5.6) placed in a circular groove around the TM sample. In this
case, TM would seep in the water from the periphery. Figure.3-18 shows a schematic diagram for
sample mounting method for nanoindentation. During the nanoindentation experiments, several
tests were conducted within a batch, it was necessary to ensure that the meniscus stayed in
contact with the TM tissue despite the evaporation of saline solution. This was accomplished with
the use of relatively large saline-well in the fixture. We monitored the saline level to ensure that
the TM stayed in saline-soaked condition at the end of every test batch for each sample. During
the whole experimental process, the saline water was added continually to make sure the TM
sample was in wet condition.

Figure 3-18 Schematic of through-thickness and in-plane nanoindentation tests setup
Aluminum
substrate
TM (medial side
facing down)
Nanoindenter tip
(spherical tip with 10m
radius and 90 cone angle
after that
2.75 mm

25 mm

7 mm

45

0.9% Saline solution
(for saline-soaked TM
samples)
56

Figure 3-19. Typical load-displacement curve of human TM from nanoindentation
Seven human tympanic membranes were obtained and used for nanoindentation
experiments. Since TM is a cone-shape membrane, it would be difficult to do the experiments on
the whole piece. The eardrum sample was sectioned into four portions: the superior-posterior
portion, inferior-posterior portion, superior-anterior portion and inferior-anterior portion. The
nanoindentation experiments were carried out on each potion from outer perimeter toward inner
part along certain lines. For each quadrant, tests were conducted along three lines where 5~10
experiments were conducted along each line. Figure 3-19 shows the typical load-displacement
curve of human TM.
3.3.3 Results and Discussion
The TM quadrant could be considered as a transversely isotropic material with the
identical properties within its plane. It is noted that under the nanoindenter tip (10 m radius), the
indent impression would have a dimension on the order of 10 m, hence there are many collagen
fibers (~10 nm diameter) within the indent. Thus, for analysis, the continuum approximation can
be considered. The out-of-plane relaxation modulus can be considered as the local average value.
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
0 200 400 600 800 1000 1200 1400
L
o
a
d

(
m
N
)

Displacement (nm)
57

Figure 3-20 shows the Youngs relaxation modulus distribution mapping figures of all
seven eardrums. The Youngs relaxation modulus values of the eardrum material vary from 1.5
MPa to 66 MPa, most of which are around 10~30 MPa. There are no obvious differences from
the Youngs relaxation values of left and right or posterior and anterior eardrum. As the figure 3-
19 shows, the modulus distribution has a certain trend. At the perimeter of the eardrum, the
Youngs relaxation modulus is relatively smaller. As the tissue around the perimeter of the
eardrum is softer than the middle membrane, the result is reasonable. And the center portion also
has smaller Youngs modulus which may due to the thinner thickness of the membrane. We can
conclude that from perimeter to center, the Youngs relaxation modulus of the TM follow small-
large-small trend.

(a)
3
10.9
11
4.1
3.6
4.5
6
4.2
6.2
4
2.7
9.7
15.6
43
17.6
4.9
21.2
18.6
10.6
10.1
11.4
8.3
24.5
30.4
21.3
7.5
8.1
7.8
3.5
3.2
6.4
4.7
15
8.3
25.9
30.7
17
5.6
2.7
4.6
3.2
14.1
45.3
10.2
6.7
4.9
3.5 19.2
38.9 1.6 2.2
2.5
1.5
3.5
3.1
3.6
4.4
18.2
3.6
5.7
10.2
17.5
26.6
26.4
13.4
4
3.3
17.9
48.3
10.8
2.9
3.6
2.9
3
10.9
11
4.1
3.6
4.5
6
4.2
6.2
4
2.7
9.7
15.6
43
17.6
4.9
21.2
18.6
10.6
10.1
11.4
8.3
24.5
30.4
21.3
7.5
8.1
7.8
3.5
3.2
6.4
4.7
15
8.3
25.9
30.7
17
5.6
2.7
4.6
3.2
14.1
45.3
10.2
6.7
4.9
3.5 19.2
38.9 1.6 2.2
2.5
1.5
3.5
3.1
3.6
4.4
18.2
3.6
5.7
10.2
17.5
26.6
26.4
13.4
4
3.3
17.9
48.3
10.8
2.9
3.6
2.9
50
45
40
35
30
25
20
15
10
5
58

(b)

(c)
13.7
23.6
23.6
12.1
17.1
21.9
23.4
14.7
9.6
16.8
32.6
6
14.5
25.1
29.3
55.2
26
7.9
4.6
6.9
30.2
32.2
21.3
10.6
20.3
22.6
34.4
50.7
37.9
9.2
20.9
20.1
25.3
13
16.3
14.7
10.6
28.1
13.5
16.4
35.9
13.2
25.3
18
20.6
36.7
55.6
44.5
15
12.6
17.5
9.8
9.3
13
8.9
7
6.9
5.5
7.9
9.6
11.2
10.8
8.7
10
9.4
6.5
5.5
8.8
14.5
15.7
16.1
11.9
12.4
10.2
16.8
11.5
17.7
13.7
23.6
23.6
12.1
17.1
21.9
23.4
14.7
9.6
16.8
32.6
6
14.5
25.1
29.3
55.2
26
7.9
4.6
6.9
30.2
32.2
21.3
10.6
20.3
22.6
34.4
50.7
37.9
9.2
20.9
20.1
25.3
13
16.3
14.7
10.6
28.1
13.5
16.4
35.9
13.2
25.3
18
20.6
36.7
55.6
44.5
15
12.6
17.5
9.8
9.3
13
8.9
7
6.9
5.5
7.9
9.6
11.2
10.8
8.7
10
9.4
6.5
5.5
8.8
14.5
15.7
16.1
11.9
12.4
10.2
16.8
11.5
17.7
50
45
40
35
30
25
20
15
10
5
59

(d)

(e)
3.5
39.6
11.9
10.4
8.9
6.2
20.3
19.8
16.6
10.8
4.6
4.8
4
10.3
11.6
13.2
10.7
11.1
10.1
10.5
8.4
15.1
17.2
12.7
14
10.7
10.2
13.1
13.2
20.1
16.8
22.5
17.1
13.1
15.4
11.5
14
15.1
66
29.4
12.3
8.8
17.1
9.7
10.7
9.1
11.1
6.8
5
6.3
7.2
7
9.5
9.5
10.2
7.4
10.8
11.4
18.5
16.1
22.2 9 3.9
7
6.2
5.8
8.7
7.1
10.1
8.3
8.6
4.5
11.1
17.9
12.7
10.2
18.1
12.7
9.5
9.9
8.5
9
11.1
25.9
32.5
46.3
13.6
18.7
3.5
39.6
11.9
10.4
8.9
6.2
20.3
19.8
16.6
10.8
4.6
4.8
4
10.3
11.6
13.2
10.7
11.1
10.1
10.5
8.4
15.1
17.2
12.7
14
10.7
10.2
13.1
13.2
20.1
16.8
22.5
17.1
13.1
15.4
11.5
14
15.1
66
29.4
12.3
8.8
17.1
9.7
10.7
9.1
11.1
6.8
5
6.3
7.2
7
9.5
9.5
10.2
7.4
10.8
11.4
18.5
16.1
22.2 9 3.9
7
6.2
5.8
8.7
7.1
10.1
8.3
8.6
4.5
11.1
17.9
12.7
10.2
18.1
12.7
9.5
9.9
8.5
9
11.1
25.9
32.5
46.3
13.6
18.7
50
45
40
35
30
25
20
15
10
5
4.5
20.7
15.6
17.7
28.9
10.4
5.5
4.5
4.6
5.6
11.5
6.2
4.3
4.6
4.6
6.3
13.3
5.4
6.5
8.2
3.3
5.5
4.1
4.5
6
4.5
6.1
8.2
11.4
9.3
4
3.4
4.3
4.7
4.8
20.2
17
5.3
4.1
7.8
4.1
4.3
5.8
9.2
6.5
6.1
6
5.8
5.6
6
11.6
5.6
4.9
4.3
4.8
4.4
4.5
4.9
4
5.5
7.3
4.6
4.9
5
4.3
3.7
4.3
6.4
9.5
7.5
5.8
5.4
4.1
4.6
5.2
5.1
9.7
6.6
7
8.6
5
4.5
4.8
8
12.8
9.9
4.1
4.1
5
3.8
20.3
6.1
5.7
8.9
13.5
7.8
5.3
4.5
20.7
15.6
17.7
28.9
10.4
5.5
4.5
4.6
5.6
11.5
6.2
4.3
4.6
4.6
6.3
13.3
5.4
6.5
8.2
3.3
5.5
4.1
4.5
6
4.5
6.1
8.2
11.4
9.3
4
3.4
4.3
4.7
4.8
20.2
17
5.3
4.1
7.8
4.1
4.3
5.8
9.2
6.5
6.1
6
5.8
5.6
6
11.6
5.6
4.9
4.3
4.8
4.4
4.5
4.9
4
5.5
7.3
4.6
4.9
5
4.3
3.7
4.3
6.4
9.5
7.5
5.8
5.4
4.1
4.6
5.2
5.1
9.7
6.6
7
8.6
5
4.5
4.8
8
12.8
9.9
4.1
4.1
5
3.8
20.3
6.1
5.7
8.9
13.5
7.8
5.3
50
45
40
35
30
25
20
15
10
5
60

(f)

(g)
Figure 3-20. Youngs relaxation modulus distribution illustrations of human tympanic membrane
5.2
20.3
32.7
19.5
9.2
6.9
8.7
15.9
23.32
21.1
17.8
19.2
19.8
22.4
14.3
5.9
6.8
8.4
17.4
22.5
18.3
10.4
9.4
13.7
18.7
28.5
24.7
16.8
11.4
15.8
22.8
25.1
17.8
13.9
19.2
14.6
21.8
23.7
18.9
16.3
12.4
10.9
15.6
19.6
29.1
24.6
17.2
11.3
10.9
18.4
27.3
23.8
26.1
21.9
17.6
22.8
12.4 18.3 17.7 20.2 19.2 17.7
9.3
11.5
19.2
22.4
24.8
20.7
18.7
6.9
18.6
24.1
23.7
15.6
9.3
9.8
19.9
20.8
22.4
23.2
15.2
5.2
20.3
32.7
19.5
9.2
6.9
8.7
15.9
23.32
21.1
17.8
19.2
19.8
22.4
14.3
5.9
6.8
8.4
17.4
22.5
18.3
10.4
9.4
13.7
18.7
28.5
24.7
16.8
11.4
15.8
22.8
25.1
17.8
13.9
19.2
14.6
21.8
23.7
18.9
16.3
12.4
10.9
15.6
19.6
29.1
24.6
17.2
11.3
10.9
18.4
27.3
23.8
26.1
21.9
17.6
22.8
12.4 18.3 17.7 20.2 19.2 17.7
9.3
11.5
19.2
22.4
24.8
20.7
18.7
6.9
18.6
24.1
23.7
15.6
9.3
9.8
19.9
20.8
22.4
23.2
15.2
50
45
40
35
30
25
20
15
10
5
6.2
9.3
18.3
34.8
23.9
21.5
16.7
8.1
11.6
25.3
24.2
27.2
20.1
12.3
18.3
22.1
24.2
20.9
27.6
20.2
10.3
15.1
22.7
24.5
26.2
20.8
19.4
18.6
12.1
10.5
17.7
21.1
25.2
20.1
19.6
29.5
20.8
9.4
9.2
18.5
20.7
23.2
17.5
14.2
5.9
8.3
17.8
28.1
23.4
13.6
11.4
9.2
16.3
21.5
24.2
18.2
15.2 10.4
19.3
25.4
17.5
15.9
12.4 9.7
7.7
19.2
22.4
25.1
20
15.8
9.1
18.3
20.1
24.2
18.2
13.2
15.9
21.4
22.5
18.4
14.3
15.7
6.2
9.3
18.3
34.8
23.9
21.5
16.7
8.1
11.6
25.3
24.2
27.2
20.1
12.3
18.3
22.1
24.2
20.9
27.6
20.2
10.3
15.1
22.7
24.5
26.2
20.8
19.4
18.6
12.1
10.5
17.7
21.1
25.2
20.1
19.6
29.5
20.8
9.4
9.2
18.5
20.7
23.2
17.5
14.2
5.9
8.3
17.8
28.1
23.4
13.6
11.4
9.2
16.3
21.5
24.2
18.2
15.2 10.4
19.3
25.4
17.5
15.9
12.4 9.7
7.7
19.2
22.4
25.1
20
15.8
9.1
18.3
20.1
24.2
18.2
13.2
15.9
21.4
22.5
18.4
14.3
15.7
E (MPa)
50
45
40
35
30
25
20
15
10
5
61

3.3.4 Conclusion of nanoindentation on human eardrum
For measurement of the Youngs relaxation modulus in the through-thickness direction,
nanoindentations were made on TM specimen with spherical nanoindenter tip in direct contact
with the collagen fiber layer. At the steady-state, the out-of-plane Youngs relaxation modulus
varies from 1.5 MPa to 66 MPa, most of which are around 10~30 MPa over the TM surface,
showing a considerable variation of out-of-plane Youngs relaxation modulus with locations.
From Youngs relaxation modulus distribution mapping figures, it can be concluded that for
human eardrum, from perimeter to center, the Youngs modulus follow small-large-small trend.

3.4 Conclusions of linear viscoelastic nanoindentation
The linear viscoelastic analysis methods of nanoindentation with flat punch, Berkovich
and spherical nanoindenter tips are described in this chapter. For flat punch nanoindentation,
experiments were conducted under quasi-static and dynamic loading conditions. Formulae were
derived measuring for viscoelastic properties in both time and frequency domains. The linear
viscoelastic analysis methods used for Berkovich and spherical tip nanoindentation were based on
Lu et. al. developed in 2003. Both thermally aged bismaleimide resin and human tympanic
membrane are anisotropic (transversely isotropic) material. The nanoindentation experiments
were conducted at different locations to get the Youngs relaxation modulus values of the whole
sample area. For bismaleimide resin, the oxidization propagation was detected with different
aging time at 200C and 300C. The Youngs relaxation distribution mapping figure of the
human eardrums were illustrated through the experimental results analysis.
62

CHAPTER IV

MEASUREMENT OF VISCOELASTIC PROPERTIES OF POLYVINYL ACETATE (PVAC)

4.1 Introduction
Nanoindentation involves 3D stress state and nonlinearity. Information is only available on the
load and displacement, as well as possibly the indentation area, and the indenter profile.
Properties have to be calculated from this using valid analysis. Despite the fact that
nanoindentation technique for measurements of some properties of elastic-plastic materials has
been well established, nanoindentation on viscoelastic materials is not fully understood especially
in for nonlinear viscoelastic material behavior. Polymers with low glass transition temperature,
i.e. Polyvinyl acetate (PVAc) which has Tg=29C, often shows negative unloading slope, i.e., the
negative contact stiffness under nanoindentation which implies that unloading displacement still
increases even when the load decreases during unloading. This phenomenon could be caused by
high viscosity in the material, or induced by nonlinearly viscoelastic behavior. In this case, the
elastic solution is not applicable.
Under isothermal conditions, viscoelastic functions of the polymers can be obtained in
either the time or frequency domain. Knauss and Kenner (1980) used a torsi meter to measure
shear creep compliance of PVAc at different temperatures. Deng and Knauss (1996) obtained the
complex creep function in the frequency domain for PVAc. For measuring the local surface
properties of polymers, nanoindentation can be used. Lu et al. (2003) developed methods to
63

measure the creep compliance of solid polymers using either the Berkovich indenter or the
spherical indenter. The method applied here was to determine nonlinear viscoelastic properties of
PVAc by nanoindentation tests. Load-displacement curves were determined using
nanoindentation at different indentation depths. ABAQUS/Standard code with user defined
subroutine was used to analyze the nonlinear viscoelastic behavior of PVAc under
nanoindentation.
4.2 Nonlinear viscoelastic model
Three dimensional, nonlinear viscoelastic Burgers model for variable stress is expressed
as:
ij kk ij
e
ij
E E
o o
u
o
u
c
+
=
1
(4-1)
) ( ) (
2
t s t J C
ij
m
s
s
ij
s
= c
(4-2)
) ( ) (
1
2
t s t J
t
C
t
ij
m t t
ij
t
ij
t
c c
c c = +
(4-3)
The components of the total strain tensor are the summation of elastic, steady creep, and
transient creep components,
=
+ + = + + =
n
i
t
ij
s
ij
e
ij
t
ij
s
ij
e
ij ij
i
1
c c c c c c c
(4-4)
where
n
is the number of Voigt units as shown in Figure. 4-1.
Eqs. (4-2) and (4-3) can also be written in integral form:
64

}
' ' ' =
t
ij
m
s
s
ij
t d t s t J C
s
0
2
) ( ) ( c
(4-5)
Which can also be written as:

( ) ( ) t d t t t s t J t t
t
C
ij
t
m t t
ij
t
' ' ' ' =
}
c c
c
c exp ) ( ) ( exp
0
2
(4-6)

Figure. 4-1. Nonlinear Burgers model

A simple, stable integration operator for these equations is the central difference operator:
t
f
f
t t
A
A
=
A +
2
1
,
2
2
1
f
f f
t
t t
A
+ =
A +
(4-7)
65

where f is some function,
t
f
is its value at the beginning of the increment,
f A
is the
change in the function over the increment, and
t A
is the time increment.
Jacobian matrix
c
o
A c
A c
of the constitutive model, with
o A
being the stress increments
and
c A
being the strain increments, can be derived by applying this to the above rate-dependent
constitutive Eqs. (4-1)-(4-3).
Applying the central difference method to the elastic strain component as depicted in
Eqn. (6-1), yields
ij kk kk ij ij
e
ij
e
ij
E E
o o o
u
o o
u
c c )
2
1
( )
2
1
(
1
2
1
A + A +
+
= A +
(4-8)
The stress and strain vectors for 3-D problem as defined in Abaqus are
( )
xy zx yz zz yy xx
o o o o o o o
, , , , ,
=

( )
xy zx yz zz yy xx
c c c c c c c
, , , , ,
=

Therefore the elastic compliance matrix (
kl
e
ij
o
c
A c
A c
) can be written as
66

(
(
(
(
(
(
(
(
(
(
(
(
(
+
+
+

E
E
E
E
E E
E E E
u
u
u
u
u u
1
0
1
0 0
1
0 0 0
1
0 0 0
1
0 0 0
1
symmetric (4-9)
Similar procedure is applied to Eqn. (4-2) for steady creep component, gives
|
.
|
\
|
A +
A
+ =
A
A
ij ij
m
s
s
ij
s t s
t
t J C
t
s
2
1
) ( )
2
(
2
c
(4-10)
Assuming
)
2
1
( ) (
2 2
t t J t J A + ~
, gives
ij
m
s ij
m
s
s
s t J tC t s t J tC
s s
A A + A = A ) (
2
1
) ( ) (
2 2
c
(4-11)
) (
2
1
2
t J tC
s
s
m
s
ij
s
ij
A =
A c
A c c

For
ij kk ij ij
s o o o
3
1
=
, then
= A =
A c
A c
= A =
A c
A c
=
A c
A c
A c
A c
=
A c
A c
) ( ), (
2
1
) ( ), (
3
1
3
2
2
2
j i t J tC
s
j i t J tC
s s
s
s
s
m
s
ij
s
ij
m
s
ij
s
ij
ij
s
ij
ij
s
ij
ij
s
ij
c
c
o
c
o
c
(4-12)
67

The compliance matrix of steady creep (
kl
s
ij
o
c
A c
A c
) can be written as

(
(
(
(
(
(
(
(
(
(
(
(
(
A
2
1
0
2
1
0 0
2
1
0 0 0
3
1
0 0 0 0
3
1
0 0 0 0 0
3
1
) (
2
t J tC
s
m
s
symmetric (4-13)
Finally for the transient creep component as defined in Eqn. (4-3),
|
.
|
\
|
A +
A
+ =
|
.
|
\
|
A + +
A
A
ij ij
m t
ij ij
t
ij
s t s
t
t J
t
C
t t
t
2
1
) ( )
2
(
2
1 1
2
c c
c c
c

( )
ij
m
t
t
ij
m
t
t
s t J tC t t s t J tC
t t
t t
A A + A A
A +
= A ) ( 2 ) ( ) ( 2
2
1
2 2
c c
c
(4-14)
) (
2
2
t J C
t t
t
s
t
m
t
ij
t
ij
A +
A
=
A c
A c
c
c

The compliance matrix of transient creep (
kl
t
ij
o
c
A c
A c
) can be written as
68

(
(
(
(
(
(
(
(
(
(
A +
A
1
0 1
0 0 1
0 0 0
3
2
0 0 0 0
3
2
0 0 0 0 0
3
2
) (
2
2
t J C
t t
t
t
m
t
c
symmetric (4-15)
From Eqn. (4-4), total compliance is
kl
t
ij
kl
s
ij
kl
e
ij
kl
ij
o
c
o
c
o
c
o
c
A c
A c
+
A c
A c
+
A c
A c
=
A c
A c
(4-16)
By inverting the total compliance matrix, the system stiffness matrix (Jacobian matrix)
kl
ij
c
o
A c
A c
can be obtained from Eqn. (4-16).
It should be noted that the above Jacobian matrix takes into account of only the elastic
deformation and creep deformation induced by stress increment. It can be seen from Eqs. (4-10)
and (4-14), aforementioned creep strain is just a small part of the total steady and transient creep
strain. The rest of the creep strain is developed over the time period of the time increment and
controlled by stress status. An artificial stress increment is introduced to include this creep strain
into the system equation. This part of creep strain can be extracted from Eqs. (4-10) and (4-14) as
( )
t
ij
m
t ij
m
s
t t s t J tC
t t
t s t J tC
t s
c c
c
A A
A +
+ A = ' A 2 ) ( ) ( 2
2
1
) ( ) (
2 2
(4-17)
A stress increment
c o ' A = ' A C
is then added into the system equation to account for
the creep strain in Eqn. (4-12), with C being the Jacobian stiffness matrix calculated from Eqn.
(4-16).
69

4.3. Nanoindentation measurements on PVAc
An MTS Nano Indenter XP system was used for the nanoindentation measurements. This
indenter can reach a maximum indentation depth of 500 m and a maximum load of 500 mN. The
displacement and load resolutions are 0.2 nm and 50 nN, respectively. Berkovich indenter tip,
made of single crystal diamond, was used in this investigation. The nanoindentation tests were
conducted in the air at room temperature (23C) under a relative humidity about 50%. Figure 4-2
shows the load-displacement curves from nanoindentation with 0.05 mN/s loading/unloading rate
of different loading time.

Figure 4-2. Load-displacement curves from nanoindentation (0.05mN/s)
4.4. Simulation of nanoindentation on PVAc:
70

In this simulation work, a 3D rigid Berkovich indenter tip model using shell elements
was created. Because of symmetric geometry structure of indenter tip, only 1/6 of entire PVAc
sample is needed the simulation which takes shorter time to run than the entire model case. The
symmetric boundary conditions were applied on the PVAc sample to obtain the identical
boundary condition as entire model was used. The Berkovich indenter tip and PVAc part are
shown in the Figure 4.3. A user defined subroutine code for Abaqus/Standard was developed
based on the algorithm introduced in the section 2. To explore the nonlinear viscoelastic material
properties of PVAc, an inverse problem has been solved to obtain the parameters for the
nonlinear viscoelastic model as mentioned previously. Different parameters were used as input
for the material model to run the simulation, and output load-displacement curves were compared
with the experimental results. By adjusting the input parameters of material model, the
simulation output curves are able to agree with the experimental results for some certain
parameter values. These values were determined as the parameters for the nonlinear viscoelastic
model. After a reasonable agreement was reached, the same parameters were used in different
loading /unloading time cases were simulated as well to indicate the viscoelastic response of the
material model.

71

Figure. 4-3. FEA simulation model: Berkovich indenter using rigid shell element and 1/6
symmetric PVAc sample

Figure 4-4 illustrates the load-displacement curve comparison between simulation results
and experiment data at 50s, 75s, 100s and 125s loading/unloading times. All the simulation
curves agree well with the experimental results which show the capability of this nonlinear
viscoelastic model to describe the properties of PVAc. The input parameters obtained from
simulation which output the agreeable curves with experimental results were listed in Table 3.
while steady creep parameters ms=0.75. The stress and displacement distribution along the
loading direction from simulation are shown in Figure 4-5. It is worthy to note that the residual
stress and displacement still exist after unloading of the indenter tip. This is associated with the
viscoelastic response of material.
72

(a) (b)

(c) (d)
Figure 4-4. Simulation result (a) 50s loading/unloading time.(b) 75s loading/unloading time.(c)
100s loading/unloading time. (d) 125s loading/unloading time.

73

Table 3. Transient creep parameters
N=1 N=2 N=3 N=4 N=5 N=6 N=7 N=8
Ct 0.23 0.1 0.1 0.05 0.05 0.05 0.05 0.05
mt 0.1 0.15 0.15 0.25 0.3 0.3 0.3 0.3
T (s) 0.25 3 50 100 125 150 250 300

(a) (b)

(c) (d)
74

Figure 4-5. Simulation results. (a). Stress z (GPa) distribution after loading. (b). Stress z (GPa)
distribution after unloading. (c). Displacement (m) along z axis after unloading. (d).
Displacement (m) along z axis after unloading.
Figure 4-6 plotted the Youngs relaxation modulus value of PVAc at different strain
levels using the nonlinear viscoelastic model. The compression tests were applied for simulation.
Small strain level samples are stiffer than large strain level samples.

Figure 4-6. Youngs relaxation modulus value of PVAc at different strain levels
4.5. Conclusion
Nanoindentation load-displacement results of polymer with low glass transition
temperature, as PVAc, often shows negative unloading slope which may be induced by
nonlinearly viscoelastic behavior. However, the nonlinear viscoelastic properties measurement
methods with nanoindentation technique are very limited. Huang et al. (2007) discussed the linear
75

viscoelastic behavior of PVAc with nanoindentation and only the loading curve was used to
compare with the analytical data. In our work, the simulation results were compared with both
loading and unloading curves. The nonlinear viscoelastic Burgers model was implemented in
ABAQUS/Standard simulation with a user define subroutine to analyze nanoindentation
experimental results. Simulation results were compared to nanoindentation experiments with
reasonable agreement at different indentation depth. Results show that the model could possibly
simulate the indentation depths from 800 nm to 1500 nm.

76

CHAPTER VI

CONCLUSIONS
Nanoindentation technique provides an effective and convenient approach to measure mechanical
properties of very small amounts of materials. Despite nanoindentation has been widely used to
measure the mechanical properties of elastic-plastic materials, nanoindentation on viscoelastic
materials is far from completed especially in nonlinear viscoelastic region. This dissertation
presented the analyze methods of material viscoelastic properties not only in linear but also in
nonlinear region using nanoindentation technique at nano and micro scales with different kinds of
indenter tips. The nanoindentation experimental methods of heterogeneous materials were also
proposed.
The instrumented nanoindenter, widely accepted as a standard tool for characterization of
properties for very small amounts of materials, is used to extract the viscoelastic properties of
typical viscoelastic materials in the dissertation, namely, the linear viscoelastic properties in both
time and frequency domains of PDMS using flatpunch indenter tip, the Youngs relaxation
modulus of thermally aged bismaleimide resin with berkovich indenter tip and the out of plane
viscoelastic function for tympanic membrane with spherical indenter tip. Due to the nonlinearities
in material behavior and contact mechanics in nanoindentation, the linear viscoelastic models
used sometimes cannot accurately characterize the mechanical behavior of time-dependent
materials. Thus, a nonlinear viscoelastic model was proposed to characterize the nonlinear
viscoelastic functions of PVAc.
77

For flat punch nanoindentation, viscoelastic functions of polymer in both time and
frequency domains are measured. Equations are derived to measure the relaxation modulus/creep
compliance functions as well as loss and storage compliance. In time domain, formulas were
derived based on Lee-Radok approach while the creep compliance equation was realized by
applying the generalized Kelvin model. The relaxation modulus/creep compliance functions of
PDMS are measured under constant rate displacement/loading history. In frequency domain,
following the Hertzian solutions for indentation in linear elasticity and the consideration of the
Lee-Radok approach for a moving boundary problem in linear viscoelasticity, formulas for the
components of the complex compliance function in the frequency-domain have been derived
based on the load-displacement relation for linearly viscoelastic materials under harmonic loading.
Loss compliance and storage compliance are measured using harmonic load, harmonic
displacement and out-of-phase angle from flat punch nanoindentation.
Linear viscoelastic nanoindentation technique was used on heterogeneous materials as
thermally aged bismaleimide resin and human tympanic membrane to measure their mechanical
properties with berkovich and spherical indenter tips. Particular experimental techniques were
applied to extract the Youngs relaxation modulus values of different locations of those materials
samples. As a high temperature thermal-setting composite, bismaleimide resin under different
aging conditions were used in experiment. Linear viscoelastic analysis was performed to obtain
the Youngs relaxation modulus from surface to interior of aged bismaleimide sample. It is found
that the Youngs relaxation modulus of resin would first increase when the aging temperature
elevated that may cause by the further cure induced shrinkage. With longer aging time, the
thermal degradation became the dominate influence factor and caused the modulus to decrease
significantly. The Youngs relaxation modulus changes in four predetermined regions on cross
section indicate the mechanical properties of oxidized zone, active zone and unoxidized zone and
predict the oxidation propagation with aging time.
78

It is quite important to measure the mechanical properties over the entire eardrum which
would provide more accurate parameters for simulation models. As very small size biomaterials,
the sample preparation and experimental procedure of nanoindentation on ear drums are very
difficult. Nanoindentation was made on the out-of-plane TM to measure Youngs relaxation
modulus of human eardrum. To emulate the physiological condition, the TM was remained in wet
condition during the whole experiment procedure and the outer ring of the sample was kept in
contact with the saline solution. The distribution of Youngs relaxation modulus over the entire
eardrum area was determined. . This phenomenon could be caused by high viscosity in the
material, or induced by nonlinearly viscoelastic behavior
For polymer under nanoindentation, nonlinear viscoelastic effects are presented. Because
of the complexity of nonlinear viscoelastic models and the limitation of information from
nanoindentation experiments, there is almost no particular research on the nonlinear viscoelastic
properties measurement methods with nanoindentation technique. In this dissertation, the
nonlinear model was implemented in Abaqus/Standard code through a user defined subroutine to
analyze nanoindentation results on polyvinyl acetate (PVAc). The model parameters were
determined by solving an inverse problem to allow simulated load-displacement curves agree
with nanoindentation experimental data. Results show that the model is effective for the
indentation depths from 800 nm to 1500 nm.
In summary, experimental, analytical and computational researches were conducted to
extract the linear and nonlinear viscoelastic functions of nanoindentation on time-dependent
materials. The linear viscoelastic analysis was conducted for nanoindentation with the use of flat
punch, Berkovich as well as spherical indenter tips. A nonlinear viscoelastic model was
implemented for nanoindentation on PVAc.
79

REFERENCES

Oliver, W.C. and Pharr, G.M., An Improved technique for determining hardness and elastic
modulus using load and displacement sensing indentation experiments, Journal of Material
Research, 7, 1564-1583, 1992,.
Oyen-Tiesma, M., Toivola, Y.A., and Cook, R.F., Load-displacement behavior during sharp
indentation of viscous-elastic-plastic materials, in Fundamentals of Nanoindentation and
Nanotribology II, Baker, S.P., Corcoran, S., Moody, G.N.R. and Cook, R.F. (ed.), Warrendale,
PA, Q.5.1, 2001.
Lu, H., Wang, B., Ma, J., Huang, G. and Viswanathan, H., Measurement of creep compliance of
solid polymers by nanoindentation, Mechanics of Time-dependent Materials, 7, 189-207, 2003.
Huang, G., Wang, B. and Lu, H., Measurements of viscoelastic functions in frequency-domain
by nanoindentation, Mechanics of Time-Dependent Materials, 8, 345-364, 2004.
Huang, G., Lu, H., Measurement of Youngs relaxation modulus using nanoindentation,
Mechanics of Time-dependent Materials,10,229-243,2006.
Cheng, L., Xia, X., Yu, W., Scriven, L.E. and Gerberich, W.W., Flat-punch indentation of
viscoelastic material, Journal of Polymer Science: Part B: Polymer Physics, 38, 10-22, 2000.
Sneddon, I.N., The relation between load and penetration in the axisymmetric Boussinesq
problem for a punch of arbitrary profile, International Journal of Engineering and Science, 3, 45-
47, 1965.
Lee, E.H. and Radok J.R.M., The contact problem for viscoelastic bodies, Journal of Applied
Mechanics 27,438-444, 1960
Nikonov, A., Davies, A.R., Emri, I.: The determination of creep and relaxation functions from a
single experiment. Proceedings of 5th International Conference on Mechanics of Time Dependent
Materials, Japan, October, 2005.
Chung, K., Seferis, J. C., and Nam, J.-D.: Investigation of Thermal Degradation Behavior of
Polymeric Composites: Prediction of Thermal Cycling Effect from Isothermal Data. Composites,
31(9), 945957.
G.A. Schoeppner, G.P. Tandon and E.R. Ripberger: Anisotropic oxidation and weight loss in
PMR-15 composites. Composites Part A: Applied Science and Manufacturing. 38(3) (2007)
80

K.V. Pochiraju and G.P. Tandon, Modeling thermo-oxidative layer growth in high temperature
resins, J Eng Mater Technol 128 (2006), pp. 107116.
Product Information Sheet, CYTEC Industries
Morgan, R.J., Shin, E.E., Rosenberg, B. and Jurek, A.: Characterization of the cure reactions of
bismaleimide composite matrices. Polymer. 38, 639-646 (1997)
J. Decelle, N. Huet, V. Bellenger: Oxidation induced shrinkage for thermally aged epoxy
networks. Polymer Degradation and Stability. 81, 239248 (2003)
J.D. Nam and J.C. Seferis, Anisotropic thermo-oxidative stability of carbon fiber reinforced
polymeric composites. SAMPE Quarterly 24 (1992), pp. 1018.
Morgan, R.J., Shin, E.E. and Lincoln, J.E.: Thermal properties of high temperature polymer
matrix fibrous composites. Handbook of Thermal Analysis and Calorimetry.3, 491-517 (2002)
Lim, D.J., Structure and function of the tympanic membrane: A review, Acta oto-rhino-
laryngologica belgica, 49, 1995, 101115.
G. Von Bekesy, Experiments in Hearing. McGraw Hill, New York, 1960
Kochkin, S. MarkeTrak VII: Hearing Loss Population Tops 31 Million People, The Hearing
Review, Vol. 12(7) July 2005, pp. 16-29.
lim, D. J. human Tympanic membrane :an ultrastructural observation, acta. Otolaryngol
Lim 1995 structure and function of the ytympanic membrane: a review. Acta otorhino
laryngological belgica 49,101-115
Helmhotz, H., 1868. The mechanism of the ossicles of the ear and membrane tympani. Originally
published in pfluger archive fur physiologie. Vol. 1 Bonn, Germany Translated by Albert H.
Buck and Normand smith (1873). William and Wood Co., New York.
Cheng, T., Dai, C., Gan, R.Z., 2007 . Viscoelastic properties of Human Tympanic Membrane.
Ann. Biomed. Eng. 35 (2), 305-314
Decraemer, W.F., Maes, M.A., Vanhuyse, V.J.,1980 An elastic stress-strain relation for soft
biological tissues based on a structural model. J. Biomech. 13,463-468
Fay, J., Puria, S., Decraemer, W.F., Steele, C., 2005. Three approaches for estimating the elastic
modulus of the tympanic membrane. J. Biomech. 38, 1807-1815
Gaihede, M., Liao, D., Gregersen, H., 2007. In vivo areal modulus of elasticity estimation of the
human tympanic membrane system: Modeling of middle ear mechanical function in normal
young and aged ears. Phys. Med. Biol. 52, 803-814.
81

Huang, G., Daphalapurkar, N.P., Gan, R.Z., Lu, H., 2008. A method for measuring linearly
viscoelastic propertises of human tympanic membrane using nanoindentation. ASME: J.
Biomech. Eng. 130,014501 1-7
Daphalapurkar, N.P., Dai, C.K., Gan, R.Z., Lu, H., 2008. Characterization of the linearly
viscoelastic behavior of human tympanic membrane by nanoindentation
Gan, R.Z., Feng, B. and Sun, Q. 2004. Three dimensional finite modeling of human ear for sound
transmission, Ann. Biomed. Eng., Vol 32, pp847-859
Gan, R.Z., Sun, Q., Feng, B and Wood, M.W. 2006 Acoustic-structural coupled finite element
analysis for sound transmission in human ear-pressure distributions, Med. Eng. Phys., Vol. 28,
pp.395-404
Wang, X., Cheng, T. and Gan, R.Z. 2007 Finite-element analysis of middle-ear pressure effects
on static and dynamic behavior of human ear, J. Acoust. Soc. Am., Vol. 122, pp 906-917
Eiber, A. and Schidhlen, W. 1996 Reconstruction of hearing by mechatronical devices, Robot,
Autonom Syst. Vol. 19, pp.199-204
Puria, S. 2003 Measurement of human middle ear forward and reverse acoustics: implications for
otoacoustic emissions, J. Acoust. Soc. Am., Vol. 113, pp2773-2789
Ferris, P. and Prendergast, P.J. 2000 Middle-ear dynamics before and after ossicular replacement
, J. Biomech., Vol. 33, pp.581-590
Kirikae, I. 1960 The structure and function of the middle ear, University of Tokyo Press, Tokyo
Fung, Y.C. 1993 biomechanics: Mechanical properties of Living Tissues, 2nd ed., spring New
York
Luo, H., Lu, H., Dai, C. and Gan, R.Z. (2009) A comparison of Youngs modulus for normal and
diseased human eardrum at high strain rates, Int. J. Experimental and Computational
Biomechanics, Vol. 1, No. 1, pp.1-22
G. Huang and H. Lu, Measurement of Youngs Relaxation Modulus Using Nanoindentation,
Mechanics of Time-Dependent Materials, 10, 229-243 (2006)
H. Lu, B. Wang, J. Ma, G. Huang and H. Viswanathan, Measurement of Creep Compliance of
Solid Polymers by Nanoindentation, Mechanics of Time-Dependent Materials, 7, 189-207
(2003)
Kuypers. L.C, Decraemer W F and Dirckx J J J 2006 Thickness distribution of fresh and
preserved human eardrums measured with confocal microscopy Otol. Neurotol. 27 256-64
Lee, W. H. and Radok, J. R. M. J. Appl. Mech. 1960, 27,438-444
Hertz, H.j. Reine Angew. Math. 1881, 92, 156-171
82

Giannakopoulos, A. E. J. appl. MEch. 2000, 67, 409-416
W.F Decraemer, M. A. Maes, V. J. Vanhuyse, An elastic Stress-strain Relation for Soft
Biological Tissues Based on a Structural Model. J. Biomech., Vol. 13 pp 463-468, 1980
M. H. Azarian, C. L. Bauer (1993), Tribology of thin-film media in both flying and sliding
modes, Wear, 168, 59-76.
Sanchez, I. C. Physics of Polymer Surfaces and Interfaces; Butterworth-Heinemann: Boston,
1992.
J. L. Keddie, R. A. L. Jones, and R.A Cory, Interface and Surface Effects on the Glass-
transition Temperature in Thin Polymer Films,Faraday Discuss. 98, 219 (1994).
W. E. Wallace, J. H. van Zanten, and W. Wu, Influence of an impenetrable interface on a
polymer glass-transition temperature, Phys. Rev.E 52, R3329 (1995).
J. H. van Zanten, W. E. Wallace, and W. Wu, Effect of strongly favorable substrate interactions
on the thermal properties of ultrathin polymer films, Phys. Rev.E 53, R2053 (1996).
D.E Packham Hand book of adhesion P524-525
J. G. Swadener, K. M. Liechti, A. L. de Lozanne (1999), The intrinsic toughness and adhesion
mechanism of a glass/epoxy interface, Journal of the Mechanics and Physics of Solids, 47, 223-
258.
J.E. Houston (2005) A Local Probe Analysis of the Rheology of a Solid-Liquid, Journal of
Polymer Science. Part B. Polymer Physics Edition.
J. H. Teichroeb and J. A. Forrest (2003), Direct Imaging of Nanoparticle Embedding to
ProbeViscoelasticity of Polymer Surfaces, Physical Review Letters, 91 016104-1-106104-4.
S. A. Hutcheson and G. B. McKenna (2005), Nanosphere Embedding into Polymer Surfaces: A
Viscoelastic Contact Mechanics Analysis, Physical Review Letters, 94, 076103-1 - 076103-4.
T. C. T. Ting (1968), Contact problems in the linear theory of viscoelasticity, Journal of
Applied Mechanics, 35, Transactions of ASME, 68, Series E, 248-254.
T. C. T. Ting (1966), The Contact Stresses Between a Rigid Indenter and a Viscoelastic Half-
Space, Journal of Applied Mechanics, 33, Transactions of ASME, 66, Series E, 438-444.
D. Tabor (1977), Surface Forces and Surface Interactions, Journal of Colloid and Interface
Science, 58, 2-13.
K. L. Johnson, K. Kendall, A. D. Roberts (1971), Surface Energy and the Contact of Elastic
Solids, Proceedings of the Royal Society of London, Series A, 324, 301313.
D. S. Rimai, L. P. Demejo and R. C. Bowen (1994), Mechanics of particle adhesion, Journal
Adhesion Science and Technology, 8, 1333-1355.
83

W. G. Knauss and V. H. Kenner (1980), On the Hygrothermomechanical Characterization of
Polyvinyl Acetate, J. Appl. Phys, 51(10), 5131-5136.
P. Silberzan and L. Leger, Spreading of High Molecular Weight Polymer Melts on High-Energy
Surfaces Macromolecules, 1992, 25, 1267.
C. Buenviaje, S. Ge, M. Rafailovich, J. Sokolov, J. M. Drake and R. M. Overney, Langmuir, 15
(1999) 3521.
Pethicai, J.B., Hutchings, R., Oliver, W.C., 1983. Hardness measurement at penetration
displacements as small as 20 nm. Philos. Mag. A. 48, 593-606. doi:
10.1080/01418618308234914.
Oliver, W.C., Hutchings, R., Pethica, J.B., 1986. Measurement of hardness at indentation
displacements as low as 20 nanometers. Microindentation Techniques in Materials Science and
Engineering, ASTM STP 889, American Society for Testing and Materials. Philadelphia, 90108.
Li, X., Bhushan, B., 2002. A review of nanoindentation continuous stiffness measurement
technique and its applications. Mater. Charact. 48, 11-36. doi:10.1016/S1044-5803(02)00192-4.
Pethica, J.B., Oliver, W.C., 1987. Tip surface interactions in STM and AFM. Phys. Scripta. T19,
A61-A66. doi : 10.1088/0031-8949/1987/T19A/010.
Doerner, M.F., Nix, W.D., 1986. A method for interpreting the data from depth-sensing
indentation instruments. J. Mater. Res. 1, 601-613. doi: 10.1557/JMR.1986.0601.
Oliver, W.C. and Pharr, G.M., 1992. An improved technique for determining hardness and elastic
modulus using load and displacement sensing indentation experiments. J. Mater. Res. 7, 1564-
1583. doi: 10.1557/JMR.1992.1564.
Dutta, A.K., Penumadu, D., 2007. Hardness and modulus of individual sand particles using
nanoindentation. Geotech. 173, 1-10. doi: 10.1061/40917(236)34.
Taylor, L.J., Papadopoulos, D.G., Dunn, P.J., Bentham, A.C., Mitchell, J.C., Snowden, M.J.,
2004. Mechanical characterisation of powders using nanoindentation. Powder Techn. 143, 179-
185. doi:10.1016/j.powtec.2004.04.012.
Buchheit, T.E., Vogler, T.J., 2010. Measurement of ceramic powders using instrumented
indentation and correlation with their dynamic response. Mech. Mater. 42, 599-614.
doi:10.1016/j.mechmat.2010.02.007.
Martin, B.E., Chen, W., Song, B., Akers, S.A., 2009. Moisture effects on the high strain-rate
behavior of sand. Mech. Mater. 41, 786-798. doi:10.1016/j.mechmat.2009.01.014.
Song, B., Chen,W., Luk, V., 2009. Impact compressive response of dry sand. Mech. Mater. 41,
777-785. doi:10.1016/j.mechmat.2009.01.003.
84

Proud, W.G., Chapman, D.J., Williamson, D.M., Tsembelis, K., Addiss, J., et al., 2007. The
dynamic compaction of sand and related porous systems. Shock Compression of Condensed
Matter, 955, 1403-1408. doi:10.1063/1.2832988.
Jillavenkatesa, A., Dapkunas, S.J., Lin-Sien, H.L., 2001. Particle Size Characterization, NIST
Special Publication 960-1 (http://www.nist.gov/public_affairs/practiceguides/SP960-1.pdf).
Papoulis, A., Pillai, S.U., 2002. Probability, Random Variables, and Stochastic Processes.
McGraw-Hill Education.
Weibull, W., 1951. A statistical distribution function of wide applicability. J. Appl. Mech.-Trans.
ASME 18 (3), 293-297.
National Institute of Standards and Technology, SEMATECH, 2006. e-Handbook of Statistical
Methods. (http://www.itl.nist.gov/div898/handbook/eda/section3/eda3668.htm).
Calderon, E., Gauthier, M., Decremps, F., Hamel, G., Syfosse, G., and Polina, A., 2007.
Complete determination of the elastic moduli of -quartz under hydrostatic pressure up to 1 GPa.
J. Phys.: Condens. Matter 19, 1-13. doi: 10.1088/0953-8984/19/43/436228.
Shield, R.T., 1955. On the plastic flow of metals under conditions of axial symmetry. Proc. R.
Soc. London A233, 267-287. doi: 10.1098/rspa.1955.0262.
Tabor, D., 1970. The hardness of solids. Rev. Phys. Technol. 1, 145-179. doi: 10.1088/0034-
6683/1/3/I01.
Johnson, K.L., 1970. The correlation of indentation experiments. J. Mech. Phys. Solids 18, 115-
126. doi:10.1016/0022-5096(70)90029-3.
Bhattacharya, A.K., Nix, W.D., 1988. Finite element simulation of indentation experiments. Intl.
J. Solids Struct. 24, 881-891. doi:10.1016/0020-7683(88)90039-X.
Bhattacharya, A.K., Nix, W.D., 1991. Finite element analysis of cone indentation. Int. J. Solids
Struct. 27, 1047-1058. doi:10.1016/0020-7683(91)90100-T.
Liu, Y., Wang, B., Yoshino, M., Roy, S., Lu, H., Komanduri, R., 2005. Combined numerical
simulation and nanoindentation for determining mechanical properties of single crystal copper at
mesoscale. J. Mech. Phys. Solids 53, 2718-2741. doi: doi:10.1016/j.jmps.2005.07.003.
Wang, H.F., Bangert, H., 1993. Three-dimensional finite element simulation of Vickers
indentation on coated systems. Mater. Sci. Eng. A163, 43-50. doi:10.1016/0921-5093(93)90576-
Z.
Sun, Y., Bell, T., Zheng, S., 1995. Finite element analysis of the critical ratio of coating thickness
to indentation depth for coating property measurements by nanoindentation. Thin Solid Films
258, 198-204. doi:10.1016/0040-6090(94)06357-5.
85

Lichinchi, M., Lenardi, C., Haupt, J., Vitali, R., 1998. Simulation of Berkovich nanoindentation
experiments on thin films using finite element method. Thin Solid Films 312, 240-248.
doi:10.1016/S0040-6090(97)00739-6.
Knapp, J.A., Follstaedt, D.M., Myers, S.M., Barbour, J.C., Friedmann, T.A., Ager, J.W.,
Monteiro, O.R., Brown, I.G., 1998. Finite-element modeling of nanoindentation for evaluating
mechanical properties of MEMS materials. Surface Coating Technol. 103-104, 268-75.
doi:10.1016/S0257-8972(98)00422-8.
Osgood, W.R., Ramberg, W., 1943. Description of stress-strain curves by three parameters,
NACA Technical Note 902, National Bureau of Standards, Washington, USA.
Bildhauer, M., Fuchs, M., 2007. Continuity properties of the stress tensor in the 3-dimensional
Ramberg/Osgood model. J. Appl. Anal. 13(2), 209-233.
ABAQUS version 6.8 documentation, 2008. Dassault Systmes, Providence, RI, USA.
Tabor, D., 1951. The hardness of metals, Oxford: Oxford University Press, UK.
Atkins, A.G., Tabor, D., 1965. Plastic indentation in metals with cones. J. Mech. Phys. Solids. 13,
149-164. doi:10.1016/0022-5096(65)90018-9.
Bolshakov, A., Pharr, G.M., 1998. Influence of pileup on the measurement of mechanical
properties by load and depth sensing indentation techniques. J. Mater. Res. 13(4), 1049-1058.
doi:10.1557/JMR.1998.0146.
Jayaraman, S., Hahn, G.T., Oliver, W.C., Rubin, C.A., Bastias, P.C., 1998. Determination of
monotonic stress-strain curve of hard materials from ultra-low-load indentation tests. Int. J. Solids
Structures 35, 365-381. doi:10.1016/S0020-7683(97)89371-7.
Cheng, Y., Li, Z., 2000. Hardness obtained from conical indentation with various cone angles. J.
Mater. Res. 15, 2830-2835. doi:10.1557/JMR.2000.0404.
Sakai, M., Akatsu, T., Numata, S., Matsuda, K., 2003. Linear strain hardening in elastic-plastic
indentation contact. J. Mater. Res. 18, 2087-2096. doi:10.1557/JMR.2003.0293.
Johnson, K.L., 1985. Contact mechanics. Cambridge University Press, Cambridge, UK.
Dao, M., Chollacoop, N., Van Vliet, K.J., Venkatesh, T.A., Suresh, S., 2001. Computational
modeling of the forward and reverse problems in instrumented sharp indentation. Acta. Mater. 49,
3899-3918. doi:10.1016/S1359-6454(01)00295-6.
Pharr, G.M., Harding, D.S., Oliver, W.C., 1993. Measurement of fracture toughness in thin films
and small volumes using nanoindentation method. Mechanical properties and deformation
behavior of materials having ultra-fine microstructures, edited by Nastasi, M., Parkin, D.M. and
Gleiter, H., Kluwer Academic Publishers, pp. 449-461.

PHD Dissertation Draft - Fang Wang

Enviado por

Dados do documento

Descrição original:

Título original

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

PHD Dissertation Draft - Fang Wang

Enviado por

Direitos autorais:

Formatos disponíveis

MEASUREMENT OF VISCOEASTIC PROPERTIES

AT SMALL LENGTH SCALES FOR

Você também pode gostar