Materials 14 03565 v2

materials
Article
A Comparative Study of Thermal Aging Effect on the Properties
of Silicone-Based and Silicone-Free Thermal Gap
Filler Materials
A S M Raufur Chowdhury 1, * , Monjur Morshed Rabby 1,2 , Mehzabeen Kabir 1 , Partha Pratim Das 1,2 ,
Rabin Bhandari 1 , Rassel Raihan 1,2 and Dereje Agonafer 1
1 Department of Mechanical and Aerospace Engineering, University of Texas at Arlington, Arlington,

TX 76019, USA; monjurmorshed.rabby@mavs.uta.edu (M.M.R.); mehzabeenbinte.kabir@mavs.uta.edu (M.K.);
parthapratim.das@mavs.uta.edu (P.P.D.); rabin.bhandari@mavs.uta.edu (R.B.);
mdrassel.raihan@uta.edu (R.R.); agonafer@uta.edu (D.A.)
2 Institute of Predictive Performance and Methodologies, University of Texas at Arlington Research Institute,
Fort Worth, TX 76118, USA
* Correspondence: raufur.chowdhury@uta.edu
Abstract: Thermal conductive gap filler materials are used as thermal interface materials (TIMs)
in electronic devices due their numerous advantages, such as higher thermal conductivity, ease
of use, and conformity. Silicone is a class of synthetic materials based on a polymeric siloxane
backbone which is widely used in thermal gap filler materials. In electronic packages, silicone-

based thermal gap filler materials are widely used in industries, whereas silicone-free thermal gap
Citation: Chowdhury, ASMR.;
filler materials are emerging as new alternatives for numerous electronics applications. Certainly,
Rabby, M.M.; Kabir, M.; Das, P.P.; characterization of these TIMs is of immense importance since it plays a critical role in heat dissipation
Bhandari, R.; Raihan, R.; Agonafer, D. and long-term reliability of the electronic packages. Insubstantial studies on the effects of various
A Comparative Study of Thermal chemical compounds on the properties of silicone-based and silicone-free TIMs has led to this
Aging Effect on the Properties of study, which focuses on the effect of thermal aging on the mechanical, thermal, and dielectric
Silicone-Based and Silicone-Free properties of silicone-based and silicone-free TIMs and the chemical compounds that cause the
Thermal Gap Filler Materials. changes in properties of these materials. Characterization techniques such as dynamic mechanical
Materials 2021, 14, 3565. https:// analysis (DMA), thermomechanical analysis (TMA), differential scanning calorimetry (DSC), Fourier
doi.org/10.3390/ma14133565
transform infrared spectroscopy (FTIR), and broadband dielectric spectroscopy (BbDS) are used to
study the mechanical, thermal, and dielectric characteristics of these TIMs, which will guide towards
Academic Editors: Jie Sun and
a better understanding of the applicability and reliability of these TIMs. The experiments demonstrate
Alexander A. Lebedev
that upon thermal aging at 125 ◦ C, the silicone-free TIM becomes hard, while silicone-based TIM
Received: 17 April 2021
remains viscoelastic, which indicates its wide applicability to higher temperature applications for a
Accepted: 23 June 2021 long time. Though silicone-based TIM displays better mechanical and thermal properties at elevated
Published: 25 June 2021 temperatures, dielectric properties indicate low conductivity for silicone-free TIM, which makes it a
better candidate for silicone-sensitive applications where higher electric insulation is desired.
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in Keywords: thermal gap filler material; dynamic mechanical analysis; thermomechanical analysis; differ-
published maps and institutional affil- ential scanning calorimetry; Fourier transform infrared spectroscopy; broadband dielectric spectroscopy
iations.
1. Introduction
Copyright: © 2021 by the authors. Thermal interface material plays a significant role in the electronic packages to enhance
Licensee MDPI, Basel, Switzerland. the heat transfer between contact surfaces. Due to miniaturization, heat dissipation from
This article is an open access article the electronic devices has become one of the limiting factors in device performance and
distributed under the terms and reliability. For the optimum performance and better reliability of a device, it is important
conditions of the Creative Commons to dissipate heat efficiently from the device during its normal operation. When two
Attribution (CC BY) license (https://
mating parts are attached in an electronic device, voids can be formed in between these
creativecommons.org/licenses/by/
two mating surfaces. Generally, these voids are filled with air, which increases thermal
4.0/).
Materials 2021, 14, 3565. https://doi.org/10.3390/ma14133565 https://www.mdpi.com/journal/materials

having good thermal contact between the mating parts. Thermal
(TIMs) are essential for good contact between the adjacent surfaces a
thermal contact resistance. Thermal gap fillers are used to fill voids bet
Materials 2021, 14, 3565 such as silicon die and heat sinks, and it is important to study 2 of 20the the
this material. The elevated temperature in the electronic devices has

properties, reliability, and the thermal performance of the thermal
contact resistance. Heat dissipating devices cannot dissipate heat efficiently without having
(TIMs).
good thermal From a lifecycle
contact between theviewpoint, the long-term
mating parts. Thermal reliability
interface materials (TIMs)of arethe the
essential (TIMs)
terials for good contact between the for
is a concern adjacent
thesurfaces
industryand minimizing
[1]. Thethepackage
thermal contactin which
resistance. Thermal gap fillers are used to fill voids between mating parts such as silicon
the environment
die and itisisimportant
heat sinks, and it subjected to,the
to study and the properties
thermal nature of its material.
of this serviceThe all influ
reliability of TIMs.
elevated temperature in theAs a result,
electronic in two
devices has anentirely
impact on thedifferent
properties, devices,
reliability, the sa
and the thermal performance of the thermal interface materials (TIMs). From a lifecycle
plied, and in one of the devices it will fail prematurely while in the ot
viewpoint, the long-term reliability of the thermal interface materials (TIMs) is a concern for
efficiency [2].The
the industry [1]. Different
package in types
which a ofTIMthermal
is mounted, interface materials
the environment (TIMs) are
it is subjected
to, and the nature of its service all influence the long-term reliability of TIMs. As a result,
try, such as thermal greases, phase change materials (PCM), elastomer
in two entirely different devices, the same TIM can be applied, and in one of the devices
filler materials,
it will fail prematurelythermal
while in thepads,
otherand
it willepoxies [3]. An[2].electronic
increase efficiency Different types package
of w
thermal interface
spreader (IHS)materials
and heat(TIMs) sink
are used
is inshown
the industry, such as thermal
in Figure 1. Thegreases,
schematicphase dem
change materials (PCM), elastomer pads, thermal gap filler materials, thermal pads, and
1epoxies
is placed
[3]. Anin between
electronic silicon
package die andheat
with integrated IHS, and TIM
spreader 2 isheat
(IHS) and placed
sink is in betw
sink
shownto minimize
in Figure thermal
1. The schematic resistance.
demonstrates In general,
that TIM 1 is placed inpolymer-based
between silicon die TIMs
and IHS, and TIM 2 is placed in between IHS and heat sink to minimize thermal resistance.
TIMs are used for the TIM 1 interface.
In general, polymer-based TIMs and solder-based TIMs are used for the TIM 1 interface.
Schematic
Figure 1. 1.
Figure of electronic
Schematic package withpackage
of electronic heat sink and IHS.heat sink and IHS.
with
Polymer-based TIMs are primarily comprised of elastomeric resin and thermally
conductive fillers [4]. Elastomers
Polymer-based TIMsareare special polymerscomprised
primarily that have both of high viscosity and resin
elastomeric
elasticity. Depending on the effectiveness and application, a specific TIM is chosen for
ductive fillers
a device. TIMs [4].
used Elastomers
between high-power aredevices
specialand polymers
heat sink need that
to behave both high
electrically
ticity. Depending
insulating, and at the same ontime,
the these
effectiveness
TIMs need toand application,
have high a specific
thermal conductivity to TIM
provide efficient thermal performance [3]. For electronic devices, thermally conductive
vice. TIMs used between high-power devices and heat sink need to be
and electrically insulating polymer matrix composites are used to acquire optimum per-
ing, andand
formance atreliability
the same time, these
of electronic devices.TIMs need
There are to have
different highpossess
fillers which thermal the cond
aforementioned properties, such as aluminum nitride, silicon carbide, and alumina [5]. The
efficient thermal performance [3]. For electronic devices, thermally co
dielectric constant of materials has a significant impact on device performance. Materials
trically insulating
with low dielectric polymer
constant reduce thematrix composites
signal delay and enhancearedeviceused to acquire
performance [3]. opti
and Silicone-based
reliability of TIMs are broadly
electronic used in electronic
devices. There are devices. Siliconefillers
different is a class of
which pos
synthetic material based on a polymeric siloxane backbone containing silicon, and oxygen
tioned properties,
atoms attached suchatoms.
to the silicon as aluminum nitride,
It is categorized silicon fluids,
as elastomers, carbide, and alum
or resins
tric constant
depending on theof materials
range has aSilicone
of crosslinking. significant
resins areimpact on device
highly crosslinked performan
structures,
and at room temperature they can be either liquid or solid. Silicone provides chemical
low dielectric constant reduce the signal delay and enhance device per
and thermal stability, low glass transition temperature, and low viscosity and near-zero
surfaceSilicone-based TIMs arethermal
shear viscosity [6]. Silicone-free broadly used
interface in electronic
materials are emergingdevices.
as a new Silico
choice of thermal interface materials for industries for the silicone-sensitive devices in
thetic material based on a polymeric siloxane backbone containing s
many applications, such as optical, medical, and sensor devices, preventing manufacturers
atoms
from usingattached to the
silicone-based silicon
materials [7]. atoms. It is categorized as elastomers, f
pending on the range of crosslinking. Silicone resins are highly crosslin
at room temperature they can be either liquid or solid. Silicone prov
thermal stability, low glass transition temperature, and low viscosity
face shear viscosity [6]. Silicone-free thermal interface materials are e
Materials 2021, 14, 3565 3 of 20
Characterization of the properties of thermal interface materials is primarily impor-

tant since it plays a vital role in the thermal dissipation and the lifecycle of the of the
electronic packages. Goel et al. identified that there is a need for developing new tech-
niques of mobile device application since existing methods such an ASTM D5470 testing
do not include the operating conditions for mobile devices. They analyzed the end-of-life
performance of thermal grease and phase change materials [8]. Fabris et al. found that
performance of the commercial TIM degrades with the addition of large quantities of
carbon nanotubes (CNTs), while on the other hand, at higher pressure, CNT and silicone
oil mixtures showed improved performance [9]. Thermal conductive gap filler materials
should possess good thermal conductivity, high-temperature stability, and elasticity at
low temperatures. However, mechanical properties, for example dynamic modulus, creep,
and stress relaxation, have an impact on the long-time reliability of the thermal interface
materials (TIMs). The characterization of the beginning of life performance of TIMs is not
sufficient since performance can degrade with usage [8]. Roy et al. used isothermal aging
and thermal cycling to determine the lifecycle and performance degradation of low melting
alloys (LMA). They discovered that low melting alloys (LMA) can withstand 2700 h of
thermal aging at 130 ◦ C and 1400 cycles between −40 and 80 ◦ C without considerable per-
formance degradation [10]. Misrak et al. studied the mechanical properties of commercially
available, thermally conductive gap filler materials. They performed a high-temperature
storage test at 125 ◦ C for 720 h to determine the change in mechanical properties of the
TIMs [11]. Isothermal ageing or bake tests, also referred to as high-temperature thermal
storage tests, are designed to simulate high temperatures experienced by the TIMs [12].
Due et al. mentioned that there is lack of understanding about the mechanism that causes
TIM failure as there are not enough studies on the basic physics of TIM degradation [2].
Additionally, moisture present in the air can affect the modulus, strength, and damping
properties of polymers [13]. Due to the scarcity in understanding the behavior of TIMs
in the packages under different circumstances, the impact of chemical compounds on the
properties of the TIMs is still an ongoing research effort.
This study focuses on the effect of thermal aging on silicone-based and silicone-free
thermal gap filler materials and the effect of different chemical compounds on the silicone-
based and silicone-free thermal gap filler materials. In this study, isothermal aging is
performed at 125 ◦ C for 2000 h for both the thermal gap filler materials to investigate the
thermal aging effect on the gap filler materials. Properties such as storage modulus, loss
modulus, complex modulus, thermal expansion, and dielectric properties of thermal gap
filler materials are analyzed, and the causes of the change in the properties are investigated
to better understand how TIMs’ characteristics change with thermal aging. Established
characterization techniques, e.g., dynamic mechanical analysis (DMA), thermomechanical
analysis (TMA), differential scanning calorimetry (DSC), Fourier transform infrared spec-
troscopy (FTIR), and broadband dielectric spectroscopy (BbDS), are used in this study to
analyze the material state of the TIMs. Finally, it can be concluded that the core purpose
of this analysis relies on the change of mechanical, thermal, and dielectric properties of
silicone-based and silicone-free TIMs after thermal aging. Additionally, the physics behind
those changes are explained by different characterization techniques applied in this study.
2. Materials and Methods

2.1. Materials
This research characterizes commercially available silicone-based and silicone-free
thermal gap filler materials. Throughout this article, silicone-based and silicone-free TIMs
are referred to as TIM A and TIM B, respectively. Steel plates, Teflon boards, double sided
adhesive tape, spacers, and clamps were used to prepare TIM samples. Teflon sheets were
adhered to one side of two steel plates with double sided adhesive tape. TIM samples were
dispensed on one of the plates’ Teflon board, and spacers were mounted on both sides of
the plates. The other steel plate was affixed to the end. Teflon was used to prevent gap filler
materials from adhering to the steel plates. Pressure was applied using clamps on both
Materials 2021, 14, x FOR PEER REVIEW 4 of 2
Materials 2021, 14, 3565 4 of 20

sides of the plates. The other steel plate was affixed to the end. Teflon was used to preven
gap filler materials from adhering to the steel plates. Pressure was applied using clamps
on both sides of the plates and the TIMs were cured for 24 h at room temperature (~25 °C)
sides
TIM B ofsamples
the plateswere
and the TIMs were
prepared cured
using the for
same24 h at room temperature
procedure. (~25 ◦in
The schematic C).Figure
TIM B 2 shows
samples were prepared using the same procedure. The schematic in Figure 2 shows TIM
TIM sample preparation assembly to obtain the required dimension of the sample. Iso
sample preparation assembly to obtain the required dimension of the sample. Isothermal
thermal
aging aging
at 125 at 125 °C (high-temperature
◦ C (high-temperature storage life, Condition
storage life, JESD22-A103E, JESD22-A103E, Condition A) was
A) was performed
performed
for 2000 h forfor 2000
TIM h for
A and TIM
TIM B toAanalyze
and TIM B to analyze
changes changes
in properties inTIMs.
of the properties
An ECof the TIMs
127
Temperature Test Chamber was used to perform the thermal aging of TIMs. In this study,of TIMs
An EC 127 Temperature Test Chamber was used to perform the thermal aging
In this
for bothstudy, for the
the TIMs, both the TIMs,
samples thenot
that are samples that areare
thermal-aged not thermal-aged
referred are referred
to as preaged, and to as
after thermal
preaged, andaging,
afterthe samples
thermal are referred
aging, to as thermal-aged.
the samples are referred to as thermal-aged.
Figure2.2.Schematic
Figure Schematicof of
TIMTIM sample
sample preparation
preparation assembly.
assembly.
2.2. Methods
2.2. Methods
2.2.1. Dynamic Mechanical Analysis (DMA)
2.2.1.Mechanical
Dynamic properties
Mechanical
of Analysis
a polymer(DMA)
can be measured using the dynamic mechanical
Mechanical
analysis properties
(DMA) technique of a polymer
applying variablecan be or
stress measured usingatthe
strain applied dynamic
range mechanica
over time.
It is a technique which provides a relationship between temperature and
analysis (DMA) technique applying variable stress or strain applied at range over time. I the mechanical
properties
is a techniqueof a sample
whichrelated to vibration
provides load (or strain)
a relationship between of a material [14]. Itand
temperature consists
the of a
mechanica
force generator which applies a sinusoidal force on the sample though the
properties of a sample related to vibration load (or strain) of a material [14]. It consists o probe and its
deformation is detected by a LVDT detector. The schematic of the dynamic mechanical
a force generator which applies a sinusoidal force on the sample though the probe and its
analyzer is shown in Figure 3. The relation between applied stress and measured strain
deformation
is considered to is calculate
detectedviscoelastic
by a LVDT detector.ofThe
properties schematic
a material. Sinceofmost
the dynamic
polymers mechanica
are
analyzer is shown in Figure 3. The relation between applied
viscoelastic materials, they have both elastic and viscous components. DMA measures stress and measured the strain is
consideredcharacteristics,
viscoelastic to calculate viscoelastic properties
such as storage modulus of(Ea ),material.
0 Since(E”),
loss modulus most polymers
loss tangent are vis
coelastic
(Tanδ), andmaterials, they have
their dependency both elastic
on frequency andand viscous components.
temperature. Storage modulus DMA measures the
is defined
as the stored characteristics,
viscoelastic energy and loss modulus is defined
such as storage as energy
modulus lostloss
(E′), in the form of (E″),
modulus heat. loss
The tangen
relations
(Tanδ), and between
their complex
dependencymodulus, storage modulus,
on frequency and loss modulus
and temperature. Storageare shown in
modulus is defined
Equations (1) and (2) [11,15]. Equation (3) [11,15] shows the relation of
as the stored energy and loss modulus is defined as energy lost in the form of heat. The loss tangent with
storage and loss modulus.
relations between complex modulus, storage modulus, and loss modulus are shown in
Equations (1) and (2) [11,15]. Equation (3) [11,15] shows the relation of loss tangent
E∗ = E0 + iE00 (1)
with
storage and loss modulus. q
| E∗ | = E0 2 + E00 2 (2)
𝐸 ∗ = 𝐸 ′ + 𝑖𝐸 ′′ (1
E00
Tanδ = 0 (3)
∗ E√ (2
|𝐸 | = 𝐸′2 + 𝐸′′2
𝐸′′
𝑇𝑎𝑛𝛿 = (3
𝐸′
For dynamic mechanical analysis of the thermal gap filler materials, DMA 7100 was
used. Several modes such as tension, compression, shear, and dual cantilever bending
modes are available in DMA 7100, and depending on the sample shape and desired mod
ulus, a suitable mode needs to be selected. By using different attachments, E″, E′, and Tanδ
can be measured for different materials. The storage and loss modulus are measured fo
silicone-based and silicone-free thermal gap filler materials using the dynamic mechanica
analyzer. In this analysis, tensile attachment was used. For each TIM, at least four tests are
even when a small force amplitude is applied, resulting in the set strain amplitude being
exceeded [14]. TIM A was the softer material of the two TIMs, and for this material, thicker
samples were prepared to have the geometric factor with the range of the DMA. The prop-
erties were measured from 20 to 170 °C, at a 2 °C/min heating rate, for 0.5, 1, 2, 5, and 10
Materials 2021, 14, 3565 Hz frequencies. For this study, minimum force of 50 mN and force gain of 1.5 were used,5 of 20
and properties of the TIMs were analyzed at 1 Hz dynamic frequency [4].
Figure 3. Schematic of dynamic mechanical analyzer (tension mode) [16].
2.2.2.For dynamic mechanical

Thermomechanical analysis
Analysis of the thermal gap filler materials, DMA 7100 was
(TMA)
used. Several modes such as tension, compression, shear, and dual cantilever bending
In thermomechanical analysis, deformation of a sample is measured under non-os-
modes are available in DMA 7100, and depending on the sample shape and desired
cillating stress with respect to temperature or time [17]. The thermomechanical analyzer0
modulus, a suitable mode needs to be selected. By using different attachments, E”, E ,
was used to measure the coefficient of thermal expansion (CTE) and glass transition tem-
and Tanδ can be measured for different materials. The storage and loss modulus are
perature (Tg) of the materials. In this technique, materials are characterized by measuring
measured for silicone-based and silicone-free thermal gap filler materials using the dynamic
the deformation of material with respect to temperature. The schematic of the thermome-
mechanical analyzer. In this analysis, tensile attachment was used. For each TIM, at least
chanical analyzer is shown in Figure 4. It consists of a furnace to heat or cool the sample
four tests are performed for dynamic mechanical analysis. To perform the analysis, both
and the force is applied on the sample by a force generator through the probe. The defor-
preaged and thermal-aged TIM A and TIM B samples’ lengths were ~30 mm, and widths
mation of the sample is measured by the LVDT detector, and the results are used to com-
were 6 to 9 mm. The thickness of preaged TIM A samples was ~2.7 mm, and the thickness
pute CTE and Tg of the samples. A compression probe or a tensile attachment is used for
of thermal-aged TIM A and TIM B samples was ~1 mm in this study. When the geometry
the analysis.
factor is veryTMAlarge,is the
alsosample
capablecannot
of measuring modulus
be extended, for thininand
resulting soft samples,
a small how-
measurement
ever, in this analysis, it is used to measure the thermal expansion behavior
amount. On the other hand, if the geometry factor is too small, the sample deformationof the thermal
gap fillerismaterials.
amount large even when a small force amplitude is applied, resulting in the set strain
amplitude being exceeded [14]. TIM A was the softer material of the two TIMs, and for
this material, thicker samples were prepared to have the geometric factor with the range of
the DMA. The properties were measured from 20 to 170 ◦ C, at a 2 ◦ C/min heating rate, for
0.5, 1, 2, 5, and 10 Hz frequencies. For this study, minimum force of 50 mN and force gain
of 1.5 were used, and properties of the TIMs were analyzed at 1 Hz dynamic frequency [4].
2.2.2. Thermomechanical Analysis (TMA)

In thermomechanical analysis, deformation of a sample is measured under non-
oscillating stress with respect to temperature or time [17]. The thermomechanical analyzer
was used to measure the coefficient of thermal expansion (CTE) and glass transition temper-
ature (Tg ) of the materials. In this technique, materials are characterized by measuring the
deformation of material with respect to temperature. The schematic of the thermomechani-
cal analyzer is shown in Figure 4. It consists of a furnace to heat or cool the sample and the
force is applied on the sample by a force generator through the probe. The deformation
of the sample is measured by the LVDT detector, and the results are used to compute
CTE and Tg of the samples. A compression probe or a tensile attachment is used for the
analysis. TMA is also capable of measuring modulus for thin and soft samples, however,
in this analysis, it is used to measure the thermal expansion behavior of the thermal gap
filler materials.
erials 2021, 14, x FOR PEER REVIEW
Materials 2021, 14, 3565 6 of 20
Figure 4. Schematic of the thermomechanical analyzer (TMA) [17].

Figure 4. Schematic of the thermomechanical analyzer (TMA) [17].
The thermomechanical analyzer TMA/SS6000 was used to perform the thermome-
chanical analysis of the thermal gap filler materials. Thermal expansion with the change of
Thewasthermomechanical
temperature measured for both the TIMs analyzer TMA/SS6000
using the thermomechanical was
analyzer. TIMused
A to
and TIM B specimens,
chanical analysis with dimensions of height and
of the thermal gap width of ~7materials.
filler mm and thickness of ~1
Thermal ex
mm, were placed on top of the quartz stage. For this analysis, a compression probe was
of temperature
used was measured
for measuring the thermal expansion of the for both
thermal gapthe
fillerTIMs using
materials. the ther
To ensure
contact between the sample and the probe throughout the analysis, a load of 10 mN was
TIM A and TIM B specimens, with dimensions of height and w
applied on the sample. The measurements of TIMs were performed from 25 to 130 ◦ C at a
ness rate
heating of of~13 ◦mm,
C/min were placed
to understand on top
the thermal of thebehavior.
expansion quartz stage.hold
Isothermal For this
was performed to bring the sample to the desired temperature. Each measurement was
probe was used for measuring the thermal expansion of the the
performed at least three times. The tip of the probe and the quartz stage were cleaned with
To ensure
ethanol after eachcontact
experiment between
to remove thethe sample and the probe throughout
residual.
mNDifferential
2.2.3. was applied on the sample.
Scanning Calorimetry (DSC) The measurements of TIMs we
130Observing
°C at thermal
a heating rateis aof
transitions 3 °C/min
major to understand
aspect of characterizing electronicthe thermal
materials
to study thermal stability. Differential scanning calorimetry measures the difference in the
thermal hold was performed to bring the sample to the desired
quantity of heat required for increasing the temperature of the sample and reference with
urement
respect was performed
to temperature. attheleast
It can also analyze three
amount of heattimes.
absorbed orThe tip during
released of the pro
these transitions. The thermal properties of the polymer and the decomposition behavior
were
were cleaned
studied with ethanol
using differential after each
scanning calorimetry. It alsoexperiment to remove
detects the transitions of melts, the r
glass transitions, phase changes, and curing [18]. In a heat flux DSC system, the sample
and reference are heated at an equal rate from a single heat source. Temperature difference
2.2.3.
(dt) Differential
between Scanning
the pans was recorded Calorimetry
and converted (DSC) (∆P). This power
to a power difference
difference provides the difference in heat flow (dH ) [19].
Observing thermal transitions is a major aspect of character
to study thermal stability.∆PDifferential = dH/dt scanning calorimetry (4) meas
quantity
Using DSC, oftheheat
heat required for isincreasing
flow in a sample measured, which theis temperature of the sa
attributed to how the
material absorbs or generates energy at the molecular level when heat is applied. Dur-
respect to temperature. It can also analyze the amount of heat abs
ing heating, molecules inside the material start vibrating, however, they also rotate and
these transitions.
translate, then the heat flowThe thermal
becomes higher. Atproperties of the
the glass transition polymer
region, and the
the material
starts shifting its state from rigid to more flexible, which in turn increases the heat flow [20].
were studied using differential scanning calorimetry. It also d
Thus, heat flow indicates changes in structure. Equation (5) is used to calculate the heat
melts, glass transitions, phase changes, and curing [18]. In a he
sample and reference are heated at an equal rate from a single h
difference (dt) between the pans was recorded and converted to
This power difference provides the difference in heat flow (𝑑𝐻)
Materials 2021, 14, 3565 7 of 20
flow, where heat flow is dH/dt, heat capacity is Cp , heating rate is β, and the mass of the
sample is M [21–23].
dH
= Cp × β × M (5)
dt
Discovery DSC 25 was used to analyze the thermal properties of the gap filler materials.
A Tzero aluminum pan and a ramp from 40 ◦ C temperature to 450 ◦ C at a heating rate
of 5 ◦ C/min were used to investigate changes of thermal properties that occurred in this
temperature range.
2.2.4. Fourier Transform Infrared Spectroscopy (FTIR)

FTIR is a prominent technique to measure infrared emission and absorption spectra of
materials. One of the most important advantages of the FTIR technique is that virtually
all the compounds display their absorption/emissions in the IR spectral region, which
can be quantitatively and qualitatively analyzed based on their properties [24]. Organic
and inorganic materials can be analyzed using FTIR spectroscopy [11]. A Thermo Nicolet
6700 FTIR Spectrometer was used for evaluating the molecular properties in the thermal
gap filler materials. For every sample, 32 scans were collected. The spectra were collected
for a wavelength of 4000 to 650 cm−1 . Using this spectrometer, spectra can be collected at
multiple IR spectral ranges.
2.2.5. Broadband Dielectric Spectroscopy (BbDS)

Broadband dielectric spectroscopy is the analysis of interaction of the electromagnetic
waves with matter. It has become a very prominent method to determine the dielectric
properties of materials. Using this technique, dielectric properties of a material can be
measured with reference to frequency and temperature. This technique provides informa-
tion about molecular dynamics, dielectric constant, and dielectric loss of different polymer
materials [25]. Morphological heterogeneity, the interactions of structural and electrical
properties between the particles, and the shape as well as the orientation of the combining
phases are several different factors that can change the dielectric spectra of a heterogeneous
material.
To perform dielectric studies, a parallel plate arrangement was created by placing the
sample between the electrode blocks connected to the analyzer of the NOVOCONTROLTM
unit. Uniform contact of electrodes with the sample was ensured by clamping the blocks
and the impedance, and capacitance was measured as function of frequency with high
precision. A schematic of dielectric properties’ measurement setup is shown in Figure 5.
The conductive plates in the electrode and the TIM placed in between the conductive plates
are shown in Figure 6. In this study, a 1-volt AC current was applied and a frequency of
10−1 to 106 Hz was used for dielectric response analysis. The measured permittivity of the
sample is given by:
C∗
ε r ∗ (ω ) = ε0r + jε r 00 = (6)
C0
A
C0 = ε 0 (7)
d
where εr * is complex permittivity, and εr 0 and εr ” represent real and imaginary parts
of measured εr *. The permittivity of the free space is presented by ε 0 F m−1 and the

capacitance of the free space is presented by C0 (F) [26].

Materials
Materials 2021,
Materials2021, 14,
14,x3565
2021,14, xFOR
FORPEER
PEERREVIEW
REVIEW 888of
of 20
of20
20
Figure
Figure5.
5.Principle
Principleof
ofdielectric
dielectricmeasurement
measurement [26].
[26].
Figure
Figure6.
6.(a)
(a)Conductive
Conductiveplates
plateson
onthe
theelectrode,
electrode, (b)
(b) TIM
TIM placed
placed in
inbetween
in betweenthe
between theelectrodes.
the electrodes.
electrodes.
3.
3. Resultsand
3.Results
Results andDiscussion
and Discussion
Discussion
3.1. Dynamic Modulus
3.1.
3.1.Dynamic
DynamicModulusModulus
In general, gap filler materials are viscoelastic in nature and have rubber-like proper-
In
In general, gap
general, gap filler
filler materials
materials are are viscoelastic
viscoelastic in in nature
nature and and have
have rubber-like
rubber-like prop-prop-
ties. Dynamic mechanical analysis was used to confirm their viscoelastic nature. At glass
erties.
erties.Dynamic
Dynamicmechanical
mechanicalanalysis analysiswas wasusedusedto toconfirm
confirmtheir theirviscoelastic
viscoelasticnature.
nature.At Atglass
glass
transition temperature (Tg ), polymeric material shows state changes. Decreasing the tem-
transition
transition temperature
temperature (T
(Tgg),
), polymeric
polymeric material
material shows
shows state
state changes.
changes. Decreasing
Decreasing the
the tem-
tem-
perature of a polymer below Tg leads the material to a brittle state, like a glass, whereas
perature
perature of
of aa polymer
polymer below
below TTgg leads
leads the
the material
material to
to aa brittle
brittle state,
state, like
like aa glass,
glass, whereas
whereas
above the Tg , the material state is more like a rubber [27]. Therefore, elastomer should
above
above the the Tgg,, the
the material state
state isis more like a rubber [27].
[27]. Therefore, elastomer should
behave likeTrubber material
at room temperature moreas like
the aglass
rubbertransition Therefore,
temperature elastomer should
is very low for
behave
behave like
like rubber
rubber at
at room
room temperature
temperature as
as the
the glass
glass transition
transition temperature
temperature is
isvery
very low
low for
for
elastomer [28]. For this reason, compared to the other polymers, elastomers exhibit a de-
elastomer
elastomer [28].
[28]. For
For this
this reason,
reason, compared
compared to
to the
the other
other polymers,
polymers, elastomers
elastomers exhibit
exhibit aade-
de-
creased modulus of elasticity and higher strain at break. In this study, dynamic mechanical
creased
creasedmodulus
analysis modulus
(DMA) was of
ofelasticity
elasticity
performed and
andforhigher
higher
preagedstrainandat
strain break.
break.In
atthermal-aged Inthis study,
thisTIMstudy, dynamic
A and TIM Bmechani-
dynamic mechani-
samples.
cal
Measurements of 1 Hz were used to compare the properties of the TIM A and TIMBB
cal analysis
analysis (DMA)
(DMA) was
was performed
performed for
for preaged
preaged and
and thermal-aged
thermal-aged TIM
TIM AA and
and TIM
TIM Bsam-
sam-
sam-
ples. Measurements
ples. TIM
ples. Measurements
A preaged of of 1 Hz
1 Hz were
samples were used
wereused to compare
to compare
challenging the properties
the properties
to mount on the DMA of the
of the TIM A and
TIM attachment
tensile TIM
A and TIM
Bfixture
Bsamples.
samples.dueTIMTIM A
to theApreaged
softnesssamples
preaged samples were
werechallenging
of the sample, challenging
while on the to
tomount
mounthand,
other on
onthe DMA
theTIMDMA A tensile
tensileattach-
attach-
thermal-aged
ment
ment fixture
fixture due
due to
to the
the softness
softness of
of the
the sample,
sample, while
while onon
samples were easier to mount on the DMA tensile fixture as they are not as soft as the the
the other
other hand,
hand, TIM
TIM AA thermal-
thermal-
aged
aged samples
preaged samples
samples.were
were easier
easier to
Stiffness toofmount
TIM Bon
mount on the
the DMA
preaged DMAand tensile
tensile fixture
thermal-agedfixture as as they
they are
samples are
was not
not as
as soft
higher soft
thanas
as
Materials 2021, 14, 3565 9 of 20
the preaged samples. Stiffness of TIM B preaged and thermal-aged samples was higher
than TIM A thermal-aged samples, and both TIM B preaged and thermal-aged samples
were easier to mount on the fixture. Tests were performed in the range of 25 to 170 °C.
TIM A thermal-aged samples, and both
The normalized TIM
storage andBloss
preaged
modulus andof TIM thermal-aged samples were
A preaged and thermal-aged ma-
easier to mount on theterials Tests were performed in the range of 25 to 170 ◦ C.
is shown in Figure 7. Storage modulus is used to define the elastic properties
fixture. of a
polymeric material. When the temperature increased, both TIM A and TIM B were found
The normalized storage
to lose theirand lossto modulus
ability store energy.of TIMtheAenergy
When preagedstorageand thermal-aged
capacity of the materials ma-
terials is shown in Figure 7. Storage
decreases modulus
with increasing is used
temperature, to define the
the intermolecular bondelastic properties
of the materials weakens, of a
and the stiffness of the materials decreases. It has been observed that the complex modu-
polymeric material. When the temperature increased, both TIM A and TIM B were found
lus of silicone-based thermal gap filler material normally decreases with heating. As pre-
to lose their ability toviously
storestated,
energy. polymerWhenchain the energy
scission occurredstorage capacity
during heating of A.
for TIM the materials
Since during
decreases with increasing
thermaltemperature,
aging the samples thewere
intermolecular
held at 125 °C forbond
2000 h,ofthethe materials
polymer chain has weakens,
enough
and the stiffness of thetime to move and the polymer chain motion continues, resulting in entanglement among
materials decreases. It has been observed that the complex modulus
some polymer chains [29]. As a result, thermal-aged TIM A has a higher complex modulus
of silicone-based thermal
thangap filler
preaged TIM material normally
A. Loss modulus decreases
describes the viscouswith heating.
properties As previously
of a polymeric-based
stated, polymer chainmaterial
scission andoccurred
it represents during
how muchheating for TIM from
energy is dissipating A. Since during
the material thermal
[30]. The loss
modulus of TIM A preaged◦ C for and thermal-aged materials (Figure 7) decreases as tempera-
aging the samples were held at 125 2000 h, the polymer
ture increases, because less force is required for deformation.
chain has enough time to
move and the polymer chain motion continues, resulting in entanglement
Dynamic modulus, also referred to as complex modulus, is calculated from storage among some
polymer chains [29]. and As loss
a result,
modulusthermal-aged
using Equation (2).TIM A has
The change a higher
in complex complex
modulus modulus
with temperature
of preaged and thermal-aged TIM A samples with the change of temperature is shown in
than preaged TIM A. Loss modulus describes the viscous properties of a polymeric-based
Figure 8. The complex modulus of TIM A preaged and thermal-aged results are normal-
material and it represents how much
ized against the value energy is dissipating
of the thermal-aged TIM Afrom the
at 25 °C. Thematerial [30]. The
complex modulus of TIMloss
modulus of TIM A preagedA is increased when it is thermal-aged
and thermal-aged at 125 (Figure
materials °C. From 50 7)todecreases
170 °C, thereasis about a 65.3%
temperature
decrease in complex modulus for the TIM A preaged sample, and there is about a 58.9%
increases, because lessdecrease
force is required for deformation.
in complex modulus for the TIM A thermal-aged samples.
TIM A preaged TIM A thermal-aged at 125 °C

(a) (b)
Figure 7. Storage modulus (E′) and loss modulus (E″), (a) TIM A preaged, and (b) (E″) TIM A thermal-aged at 125 °C.
Figure 7. Storage modulus (E0 ) and loss modulus (E”), (a) TIM A preaged, and (b) (E”) TIM A
thermal-aged at 125 ◦ C.
Dynamic modulus, also referred to as complex modulus, is calculated from storage

and loss modulus using Equation (2). The change in complex modulus with temperature
of preaged and thermal-aged TIM A samples with the change of temperature is shown in
Figure 8. The complex modulus of TIM A preaged and thermal-aged results are normalized
against the value of the thermal-aged TIM A at 25 ◦ C. The complex modulus of TIM A
is increased when it is thermal-aged at 125 ◦ C. From 50 to 170 ◦ C, there is about a 65.3%
decrease in complex modulus for the TIM A preaged sample, and there is about a 58.9%
decrease in complex modulus for the TIM A thermal-aged samples.
The normalized storage and loss modulus of TIM B preaged and thermal-aged materi-
als are shown in Figure 9. In Figure 9a, for TIM B preaged samples, the value of storage
modulus and loss modulus decreases with the increase of temperature, however, after 115
◦ C temperature, the storage modulus and loss modulus increase as the material becomes
stiffer. The reason behind the increase in stiffness of preaged TIM B is explained in the
thermal properties section (Section 3.3).
Normalized Complex Modulus (
1 TIM A thermal aged at 125°C
0.8
0.6
Materials 2021, 14, 3565 10 of 20
0.4
0.2
1.2
TIM A preaged
Normalized Complex Modulus (E*)

0
0 20 40 60 TIM A
80thermal
100aged120 140
at 125°C 160 180
1 Temperature (°C)
Figure 8. Complex modulus of TIM A.
0.8
The normalized storage and loss modulus of TIM B preaged and thermal-aged mate-
rials are shown in Figure 9. In Figure 9a, for TIM B preaged samples, the value of storage
0.6 modulus and loss modulus decreases with the increase of temperature, however, after 115
°C temperature, the storage modulus and loss modulus increase as the material becomes
0.4
The complex modulus of TIM B preaged results and TIM B thermal-aged results is
0.2
normalized against the thermal-aged TIM B value at 25 °C. Figure 10 shows the complex
modulus of TIM B before aging and TIM B after thermal aging, respectively. The complex
modulus of preaged TIM B is lower than thermal-aged TIM B. For preaged TIM B, the
0
complex modulus decreased until 115 °C, and there was about a 16% decrease in complex
0 20 modulus
40 from 6050 to 115
80 °C, while
100 after120 140 160 180
115 °C, the modulus started to increase rapidly
Temperature (°C)
with the increase of temperature. From Figure 10, it can be seen that the complex modulus
of TIM B was much higher when it was thermal-aged at 125 °C. After thermal aging, the
Figure 8. Complex modulus
Figure 8. Complex modulus of TIMTIM
A. A.
TIM B of
sample became hard, and the Vickers hardness of the sample was 59.6 HV, meas-
ured using a LECO LM300AT Microhardness Tester.
The normalized storage and loss modulus of TIM B preaged and thermal-aged mate-
rials are shown in Figure 9. In Figure 9a, for TIM B preaged samples, the value of storage
modulus and loss modulus decreases with the increase of temperature, however, after 115
°C temperature, the storage modulus and loss modulus increase as the material becomes
The complex modulus of TIM B preaged results and TIM B thermal-aged results is
normalized against the thermal-aged TIM B value at 25 °C. Figure 10 shows the complex
TIM B preaged TIM B thermal-aged at 125 °C
complex modulus decreased until 115 °C, and there was about a 16% decrease in complex
(a) (b)
modulus from 50 to 115 °C, while after 115 °C, the modulus started to increase rapidly
Figure 9. Storage modulus (E′)0and loss modulus (E″), (a) TIM B preaged, and (b) TIM B thermal-aged at 125 °C.
with the
Figure 9. increase of temperature.
Storage modulus (E ) andFrom Figure 10,(E”),
loss modulus it can
(a)be seen
TIM that the complex
B preaged, and (b) TIMmodulus
B thermal-aged
of 125
at TIM◦ C.
B was much higher when it was thermal-aged at 125 °C. After thermal aging, the
TIM B sample became hard, and the Vickers hardness of the sample was 59.6 HV, meas-
ured The
usingcomplex
a LECO LM300AT
modulusMicrohardness
of TIM B preaged Tester.results and TIM B thermal-aged results is
normalized against the thermal-aged TIM B value at 25 ◦ C. Figure 10 shows the complex
complex modulus decreased until 115 ◦ C, and there was about a 16% decrease in complex
modulus from 50 to 115 ◦ C, while after 115 ◦ C, the modulus started to increase rapidly
with the increase of temperature. From Figure 10, it can be seen that the complex modulus
of TIM B was much higher when it was thermal-aged at 125 ◦ C. After thermal aging, the
TIM B sample became hard, and the Vickers hardness of the sample was 59.6 HV, measured
using a LECO LM300AT Microhardness Tester.
TIM B preaged TIM B thermal-aged at 125 °C

(a) (b)
Figure 9. Storage modulus (E′) and loss modulus (E″), (a) TIM B preaged, and (b) TIM B thermal-aged at 125 °C.
(a) (b)
Figure 10. Complex modulus, (a) TIM B preaged, and (b) TIM B thermal-aged at 125 °C.
Figure 10. Complex modulus, (a) TIM B preaged, and (b) TIM B thermal-aged at 125 ◦ C.
3.2. Thermal Expansion
To understand the thermal expansion behavior of the TIMs, the change in relative
length of the sample was calculated with the change of temperature using the thermome-
chanical analyzer (TMA) from 25 to 130 °C. The change in relative length with tempera-
ture for preaged TIM A samples has been found to be greater than the ones thermal-aged
at 125° (Figure 11). Preaged TIM A has a total thermal expansion of 4.84% from 50 to 130
Materials 2021, 14, 3565
(a) (b) 11 of 20
Figure 10. Complex modulus, (a) TIM B preaged, and (b) TIM B thermal-aged at 125 °C.

To understand the thermal expansion behavior of the TIMs, the change in relative
lengthToofunderstand
the samplethe
wasthermal expansion
calculated with thebehavior
change ofoftemperature
the TIMs, the change
using in relative
the thermome-
length of the sample was calculated with the change of temperature using the thermome-
chanical analyzer (TMA) from 25 to 130◦ °C. The change in relative length with tempera-
chanical analyzer (TMA) from 25 to 130 C. The change in relative length with temperature
ture for preaged TIM A samples has been found to be greater than the ones thermal-aged
for preaged TIM A samples has been found to be greater than the ones thermal-aged at
at 125° (Figure 11). Preaged TIM A has a total thermal expansion of 4.84% from 50 to 130
125◦ (Figure 11). Preaged TIM A has a total thermal expansion of 4.84% from 50 to 130 ◦ C,
°C, whereas thermal-aged TIM A has a total thermal expansion of 3.42%.
whereas thermal-aged TIM A has a total thermal expansion of 3.42%.
1.08
TIM A preaged
1.07
TIM A thermal aged at 125°C
1.06
Relative Length
1.05
1.04
1.03
1.02
1.01
1
0 20 40 60 80 100 120 140
Temperature (°C)
Figure 11. Change in relative length with temperature of TIM A.
The change
The change in in relative
relativelength
lengthwith
withthe
thechange
changeofoftemperature
temperatureforfor TIM
TIM B is
B is shown
shown in
in Figure 12. In the case of TIM B, the changes in relative length with temperature
Figure 12. In the case of TIM B, the changes in relative length with temperature for preaged for
preaged and thermal-aged
and thermal-aged (at 125 °C) 125 ◦ C) have
(atsamples samples have
been been observed
observed to besimilar.
to be almost almostBesides,
similar.
Materials 2021, 14, x FOR PEER REVIEW
Besides, thermal expansion from 50 to 130 ◦ C for preaged TIM B was about 1.68% and 12 of 20
for
thermal expansion from 50 to 130 °C for preaged TIM B was about 1.68% and for thermal-
thermal-aged
aged TIM B, itTIM
wasB, it was
about about 1.62%.
1.62%.
1.08
1.07 TIM B preaged
1.06 TIM B thermal aged at 125°C

Relative Length
1.05
1.04
1.03
1.02
1.01
1
0 20 40 60 80 100 120 140
Temperature (°C)
Figure 12.
Figure 12. Change
Change in
in relative
relative length
length with
with temperature
temperature of
ofTIM
TIMB.
B.
From
From Figures 11 and 12, itit can
can be
beconcluded
concludedthat
thatthe
thethermal
thermalexpansion
expansionofofTIM
TIMAAis
is significantly
significantly higher
higher than
than TIM
TIM B for
B for thethe preaged
preaged samples.
samples. ForFor both
both thethe TIMs,
TIMs, thermal
thermal ex-
pansion was higher compared to that of copper, aluminum, or other underfill materials
[4]. Thermal expansion of preaged TIM A was higher than thermal-aged TIM A, which
can be correlated to dynamic mechanical analysis (DMA) results. Similarly, thermal ex-
pansion of TIM B decreased after thermal aging, which can also be correlated to the dy-
Materials 2021, 14, 3565 12 of 20
expansion was higher compared to that of copper, aluminum, or other underfill mate-
rials [4]. Thermal expansion of preaged TIM A was higher than thermal-aged TIM A,
which can be correlated to dynamic mechanical analysis (DMA) results. Similarly, thermal
expansion of TIM B decreased after thermal aging, which can also be correlated to the
dynamic mechanical analysis (DMA) results.
3.3. Thermal Properties

In this study, thermal stability of two types of gap filler material, TIM A and TIM
B, have been analyzed before and after thermal aging. Thermal interface materials are
mostly elastomeric material and show significant physical property changes when exposed
to heat. These changes in properties can have significant impacts on characteristics and
lifecycle of the elastomeric materials [31–33]. Gap filler material (elastomeric material) has
a glass transition temperature far below room temperature, and can be thought of as a
single large molecule of macroscopic scale [34]. When the temperature drops, elastomers
become harder and less flexible, and they lose their rubber-like properties entirely when
the temperature reaches the glass transition temperature. On the other hand, at high
temperatures near or above the service temperature limit, some irreversible chemical
changes occur in elastomers. At this temperature, the polymer backbone may be subject
to either chain scission, causing the elastomeric part to become softer, or the polymer
molecules may undergo a crosslinking process, resulting in the material being more rigid,
which in turn alters their thermal stability [34,35].
From the DSC thermograph (Figure 13), it has been found that there is a sudden drop
in heat flow for TIM A at 225 ◦ C, which indicates oxidative degradation with subsequent
polymer chain scission. During thermal aging of the elastomeric material, depending on the
microstructure of the elastomer, degradation will cause either hardening or softening. For
example, polybutadiene generally undergoes oxidative hardening, while on the other hand,
polyisoprene softens as it is exposed to heat and oxygen [29]. According to the literature,
pendent bulky side groups in polymer chains create steric hinderance, which causes a
radical recombination reaction, which is difficult to occur. Therefore, these polymers
undergo strain softening because of the chain scission [31–33,36]. A representation of
oxidative softening—chain scission is shown in Figure 14. For this reason, preaged TIM
A shows softening during heating. Similar degradation has been observed in a DSC
thermograph for thermal-aged TIM A.
However, TIM B material showed hardening when this material was exposed to heat.
At 220 ◦ C (Figure 15), TIM B showed similar transition because of the thermal degradation.
However, an exothermic peak (because of reaction heat) has been observed in the DSC
thermograph above 360 ◦ C, which indicates the occurrence of a crosslinking reaction. The
crosslinking will cause the elastomeric part to become hard. The crosslinking reaction
occurs due to free radicals produced by heat. For this reason, after thermal aging, TIM B
showed brittle-like behavior.
When the DSC experiment was performed for thermal-aged TIM B material with the
same conditions, it was found that thermal ageing does not change the degradation tem-
perature, however, a reduction in exothermic peak area (reaction heat) has been observed
because most of the polymer chains were already crosslinked and there was less energy
left for further reactions.
At 220 °C (Figure 15), TIM B showed similar transition because of the thermal degrada-
When the
tion. However, an DSC experiment
exothermic was performed
peak (because for thermal-aged
of reaction heat) has been observed TIMinB thema
same
DSC conditions,
thermograph it was
above found
360 °C, that
which thermal
indicates ageing does
the occurrence not changereaction.
of a crosslinking the deg
Materials 2021, 14, 3565
perature,
The however,
crosslinking a reduction
will cause in exothermic
the elastomeric peak
part to become area
hard. The(reaction heat)
crosslinking has
reaction
13 of 20
occurs
becausedue most
to freeof
radicals producedchains
the polymer by heat.were
For this reason,crosslinked
already after thermal and
aging, TIM B
there w
When the DSC experiment was performed for thermal-aged TIM B material with the
same conditions, it was found that thermal ageing does not change the degradation tem-
perature, however, a reduction in exothermic peak area (reaction heat) has been observed
because most of the polymer chains were already crosslinked and there was less energy
Figure
Figure 13. Normalizedheat
13. Normalized heat flow
flow vs.vs. temperature
temperature of TIM
of TIM A. A.
Figure 13. Normalized heat flow vs. temperature of TIM A.
Figure 14. A representation of oxidative softening-chain scission [33].


Materials 2021,14,
Materials2021, 14,3565
x FOR PEER REVIEW 14
14of
of20
20
Figure 15.
Figure 15. Normalized
Normalized heat
heat flow
flow vs.
vs. temperature
temperature of
of TIM
TIM B.
B.
3.4.
3.4. FTIR
FTIR Spectra
Spectra
FTIR ◦ C are shown in
FTIR spectra of TIM
spectra of TIMAApreaged
preagedand andTIM
TIMA A thermal-aged
thermal-aged at 125
at 125 °C are shown in Fig-
Figure
ure 16. 16.
TIMTIM A preaged
A preaged material
material showed
showed an intense
an intense peakpeak at a 1258
at a 1258 cm−1 wavelength,
cm−1 wavelength, which
which indicates
indicates the the presence
presence of of silicon
silicon organic
organic compounds
compounds with with
a a methyl
methyl group.
group. Around
Around 1260
1260−1 cm−1 , methyl groups attached to silicon atoms produced a distinctive deformation ab-
cm , methyl groups attached to silicon atoms produced a distinctive deformation absorp- −1 .
sorption [37]. The asymmetrical deformation was weaker and occurred around 1400 cm
tion [37]. The asymmetrical deformation was weaker and occurred around 1400 cm−1. As
As the material was thermal-aged, a certain decrease in the intensity at this wavelength
the material was thermal-aged, a certain decrease in the intensity at this wavelength was
was found, which indicates that polymer chain scissions occurred during thermal aging.
found, which indicates that polymer chain scissions occurred during thermal aging. The
The peak at the 2962−1cm−1 wavelength was analyzed, and it shows that the CH3 and CH2
peak at the 2962 cm wavelength was analyzed, and it shows that the CH3 and CH2 bonds
bonds decrease with thermal aging, which is a clear indication of polymer chain scission.
decrease with thermal aging, which is a clear indication of polymer chain scission. The
−1 wavelengths,
The TIM A preaged sample also showed peaks at 3520 and 3438 cm which
TIM A preaged sample also showed peaks at 3520 and 3438 cm−1 wavelengths, which de-
define −OH bond (carboxylic acid) and −OH stretching vibration. In the thermal-aged
fine −OH bond (carboxylic acid) and −OH stretching vibration. In the thermal-aged sam-
sample, the intensity of the −OH bond decreased, which indicates that the −OH bond was
ple, the intensity of the −OH bond decreased, which indicates that the −OH bond was
broken at elevated temperature and free oxygen caused thermal oxidation.
broken at elevated temperature and free oxygen caused thermal oxidation.
Materials 2021, 14, 3565
Materials 2021, 14, x FOR PEER REVIEW
15 of 20
15 of 20
(a) (b)
Figure
Figure 16.16.
(a)(a) FTIRspectra
FTIR spectraofofTIM
TIMAApreaged,
preaged, and
and (b)
(b) FTIR
FTIR spectra
spectraof
ofTIM
TIMAAthermal-aged
thermal-agedatat
125 °C.◦ C.
125
FTIRanalysis
FTIR analysis was
was performed
performed for
forpreaged
preagedTIM TIMBBand andthermal-aged
thermal-aged TIM
TIM B. B.
The FTIR
The FTIR
spectra of TIM B preaged and TIM B thermal-aged at 125 °C ◦ are
spectra of TIM B preaged and TIM B thermal-aged at 125 C are presented in Figure 17. presented in Figure 17.
Fromthe
From theFTIR
FTIR data,
data, ititwas
wasobserved
observed that there
that is no
there is peak
no peakat 1258 cm−1,cm
at 1258 so −
it1indicates that
, so it indicates
it is silicone-free TIM. It was found that CH and CH bonds increase
that it is silicone-free TIM. It was found that CH3 and CH2 bonds increase with thermal
3 2 with thermal aging
at theat2921
aging cm−1 cm
the 2921 −1 wavelength,
wavelength, which which
indicates polymer
indicates chain crosslinking.
polymer The FTIR
chain crosslinking. Thealso
FTIR
showed the presence of -OH and C=O functional groups
also showed the presence of -OH and C=O functional groups at the wavenumbers at the wavenumbers 3452 and
3452
1710
and cm−1cm
1710 , respectively. The C=O
−1 , respectively. The stretching vibration
C=O stretching generally
vibration occurred
generally at the 1711
occurred cm1711
at the
−1
wavelength
− 1 [38]. There was a good possibility that the sample went
cm wavelength [38]. There was a good possibility that the sample went through thermal through thermal oxi-
dation during
oxidation duringthermal
thermalaging, and and
aging, during thermal
during aging,aging,
thermal C=O bondsC=O degraded, and moreand
bonds degraded,
hydrogen bonds formed. At peak 965 cm −1, for preaged material, there was presence of a
− 1
more hydrogen bonds formed. At peak 965 cm , for preaged material, there was presence
ofcarbon–carbon
a carbon–carbon double
doublebond. With
bond. the the
With thermal
thermalaging,
aging,we we
found thatthat
found thethe
density of the
density of the
carbon–carbon double bond decreases. The decrease in the carbon–carbon double bond
carbon–carbon double bond decreases. The decrease in the carbon–carbon double bond
indicates that more crosslinking occurred. From FTIR results, it was confirmed that the
TIM A is a silicone-based material, however, TIM B is a silicone-free elastomer.
3.5. Dielectric Properties

The dielectric properties of the thermal interface materials (TIMs) have been measured
by broadband dielectric spectroscopy (BbDS). Using this characterization technique, the
complex permittivity value has been measured, which has a real and an imaginary part.
The real part expresses the capability of the materials to polarize in response to an applied
field [39]. The high dielectric constant value indicates the materials to be highly polarized
and the low dielectric constant indicates the materials to be insulating. It has been found
that the real permittivity values for both TIMs decreased with thermal aging (Figure 18).
This can be explained from the view of chemical change of the TIMs due to aging. From
FTIR data, it has been observed that polymer chain breaks and oxidation occur during
thermal aging. The wavenumber signals at 1000 to 1088 cm−1 occur due to asymmetric
(a)
vibrations of (Si-O-Si), and the corresponding peaks at 950(b) cm−1 are assigned to asymmetric
vibrations
Figure 17. (a) FTIR ofTIM
spectra of (Si-OH) [40]. and
B preaged, Due(b)
toFTIR
thermal aging,
spectra of TIMthe Si-O-Si bondatdensity
B thermal-aged 125 °C. reduced, which
may lower the polarizability. The signals at 3435 to 3456 cm−1 are attributed to the starching
3.5. Dielectric
modes Properties
of adsorbed water molecules.
From FTIR data,
The dielectric it was found
properties of thethat -OH bond
thermal density
interface decreased
materials (TIMs)with
haveaging;
been therefore,
meas-
the ionby
ured movement
broadbandalso decreased,
dielectric which in
spectroscopy turn increased
(BbDS). Using thisthe resistivity of technique,
characterization the material.
Moreover,
the complex thepermittivity
imaginary permittivity
value has been alsomeasured,
decreasedwhichfor both
has TIM
a realAand
andan TIM B samples
imaginary
with
part.thermal
The realaging (Figure 19).
part expresses The imaginary
the capability part indicates
of the materials the dielectric
to polarize in response losstoof
anthe
applied field
material. [39].
As the The high dielectric
polarization decreasesconstant
in thevalue indicates
sample, the materials
the dielectric to be highly
loss should also be
polarized [39].
decreased and the
Thelow dielectric
dielectric constant such
properties, indicates thedielectric
as the materialsrelaxation
to be insulating.
strength It (DRS),
has
beencalculated
were found that from
the real permittivity
real permittivityvalues for both
values TIMsthe
for both decreased
TIMs. with thermal
Dielectric aging
relaxation
(Figure 18).
strength (DRS)Thisis can
the be explainedbetween
difference from therealview of chemicalat
permittivity change
higheroffrequency
the TIMs due andtoreal
permittivity at lower frequency (static permittivity) [26]. DRS values of TIM A and TIM B
are shown in Figure 20.
wavelength [38]. There was a good possibility that the sample went through thermal oxi-
dation during thermal aging, and during thermal aging, C=O bonds degraded, and more
hydrogen bonds formed. At peak 965 cm−1, for preaged material, there was presence of a
carbon–carbon double bond. With the thermal aging, we found that the density of the
carbon–carbon double bond decreases. The decrease in the carbon–carbon double 16
Materials 2021, 14, x FOR PEER REVIEW bond
of 20
Materials 2021, 14, 3565 16 of 20
aging. From FTIR data, it has been observed that polymer chain breaks and oxidation oc-
cur during thermal aging. The wavenumber signals at 1000 to 1088 cm−1 occur due to
asymmetric vibrations of (Si-O-Si), and the corresponding peaks at 950 cm−1 are assigned
toaging. From FTIR data, it has been observed that polymer chain breaks and oxidation oc-
asymmetric vibrations of (Si-OH) [40]. Due to thermal aging, the Si-O-Si bond density
cur during thermal aging. The wavenumber signals at 1000 to 1088 cm−1 occur due to
reduced, which may lower the polarizability. The signals at 3435 to 3456 cm−1 are at-
asymmetric vibrations of (Si-O-Si), and the corresponding peaks at 950 cm−1 are assigned
tributed to the starching modes of adsorbed water molecules.
to asymmetric vibrations of (Si-OH) [40]. Due to thermal aging, the Si-O-Si bond density
From FTIR data, it was found that -OH bond density decreased with aging; therefore,
reduced, which may lower the polarizability. The signals at 3435 to 3456 cm−1 are at-
the ion
tributedmovement also decreased,
to the starching which in water
modes of adsorbed turn increased
molecules.the resistivity of the material.
Moreover, the imaginary permittivity also decreased
From FTIR data, it was found that -OH bond density fordecreased
both TIMwithA and TIM
aging; B samples
therefore,
with thermal aging (Figure 19). The imaginary part indicates the dielectric
the ion movement also decreased, which in turn increased the resistivity of the material. loss of the ma-
terial. As the polarization decreases in the sample, the dielectric loss
Moreover, the imaginary permittivity also decreased for both TIM A and TIM B samples should also be de-
creased [39]. The dielectric properties, such as the dielectric relaxation
with thermal aging (Figure 19). The imaginary part indicates the dielectric loss of the ma- strength (DRS),
(a)were calculated
terial. from real decreases
As the polarization permittivity values
in the sample, for the
both the TIMs.
dielectric
(b) loss Dielectric
should alsorelaxation
be de-
strength
creased (DRS)
[39]. Theis the difference
dielectric between
properties, real
such aspermittivity
the dielectricatrelaxation
higher frequency and real
strength (DRS),
Figure
Figure 17.17.
(a)(a) FTIR
FTIR spectracalculated
were
spectra ofofTIM
permittivity TIM Bpreaged,
preaged,
at Blower
from and
frequency
real
and (b)(static
FTIR spectra
permittivity
(b) FTIR of
ofTIM
permittivity)
values
spectra for B[26].
TIMboth Bthermal-aged
DRSTIMs.
the atDielectric
values
thermal-aged at125
of °C.
TIM
125 ◦ C.A and TIM B
relaxation
strength
are shown (DRS) is the
in Figure 20.difference between real permittivity at higher frequency and real
3.5. Dielectric Properties
permittivity at lower frequency (static permittivity) [26]. DRS values of TIM A and TIM B
areThe dielectric
shown properties
in Figure 20. of the thermal interface materials (TIMs) have been meas-
ured by broadband dielectric spectroscopy (BbDS). Using this characterization technique,
the complex permittivity value has been measured, which has a real and an imaginary
part. The real part expresses the capability of the materials to polarize in response to an
applied field [39]. The high dielectric constant value indicates the materials to be highly
polarized and the low dielectric constant indicates the materials to be insulating. It has
been found that the real permittivity values for both TIMs decreased with thermal aging
(Figure 18). This can be explained from the view of chemical change of the TIMs due to
(a) (b)
(a) Figure18.
18.Real
Realpermittivity
permittivity of
of TM
TM A
A and
and TIM (b)
Figure TIM B.
B.
Figure 18. Real permittivity of TM A and TIM B.
(a)(a) (b)
(b)
Figure 19. Imaginary
Figure permittivity of TIM
TIM Aand
and TIMB.B.
Figure 19. 19. Imaginarypermittivity
Imaginary permittivity of
of TIM A
A andTIM
TIM B.
From
FromFigure
Figure20,20, itit can
can be
be observed that for
observed that forboth
bothtypes
typesofofsamples,
samples,thethe
DRSDRS value
value
decreased with thermal aging, which indicates that electrical conductivity
decreased with thermal aging, which indicates that electrical conductivity decreases withdecreases with
the thermal aging and less polarization occurs inside the material. For the thermally
the thermal aging and less polarization occurs inside the material. For the thermally aged aged
sample
sampleofofTIMTIMB,B,polymer
polymer crosslinking degradedthe
crosslinking degraded thedielectric
dielectricproperty.
property.TheThe polymer
polymer
chain
chain isisnot
noteasily
easilypolarized
polarized due due to crosslinking
crosslinking or orbulky
bulkygroups
groupsinin
the chain.
the OnOn
chain. thethe
other
other
hand,for
hand, forthe
thethermally
thermallyaged aged sample
sample of TIM
TIM A,A,the
thematerial
materialswells
swellsand
andtakes
takesonon
moisture
moisture
Materials 2021, 14, 3565 17 of 20

[41]. Therefore, the thermally aged sample of TIM A shows a relatively higher DRS value
than the thermally aged sample of TIM B.
Figure 20.
Figure 20. Dielectric
Dielectric relaxation
relaxation strength
strength (DRS)
(DRS) of
of TIM
TIMAAand
andTIM
TIMB.
B.
From
From Figure
the overall20, itanalysis,
can be observed
the dynamic thatmodulus
for bothoftypes of samples,
thermally aged TIM the A DRS value
increased
decreased with thermal aging, which indicates that electrical
compared to the preaged TIM A, but remained viscoelastic, which corresponds to the conductivity decreases with
de-
the
creasethermal aging expansion
in thermal and less polarization occursand
of the materials inside
the the material.
reduction Fordielectric
in the the thermally aged
relaxation
sample
strengthof(DRS).TIM B, polymer crosslinking
Furthermore, after thermal degraded
aging, TIMthe dielectric
B samplesproperty.
became hard. The polymer
Thermal
chain
expansion and dielectric relaxation strength (DRS) of thermally aged TIM B wereOn
is not easily polarized due to crosslinking or bulky groups in the chain. the
lower
other hand, for the thermally aged sample of TIM A, the
than those of preaged TIM B, which corresponds to the increase of dynamic modulus. material swells and takes on
moisture [41]. Therefore, the thermally aged sample of TIM A
Finally, the objective of this study was to investigate the change of thermomechanical and shows a relatively higher
DRS valueproperties
dielectric than the thermally aged sample
of silicone-based of TIM B. TIMs with thermal aging. In addi-
and silicone-free
tion, the characterization techniques used inmodulus
From the overall analysis, the dynamic this study of helped
thermally aged TIM
to explain theAreasons
increased be-
compared to
hind those changes. the preaged TIM A, but remained viscoelastic, which corresponds to the
decrease in thermal expansion of the materials and the reduction in the dielectric relaxation
strength (DRS). Furthermore, after thermal aging, TIM B samples became hard. Thermal
4. Conclusions
expansion and dielectric relaxation strength (DRS) of thermally aged TIM B were lower
In this work, the impact of thermal aging on the properties of silicone-based and sil-
than those of preaged TIM B, which corresponds to the increase of dynamic modulus.
icone-free thermal gap filler materials has been analyzed, and the effect of the chemical
Finally, the objective of this study was to investigate the change of thermomechanical
compounds
and dielectric onproperties
the changeofinsilicone-based
mechanical, thermal, and dielectric
and silicone-free TIMs properties has been
with thermal aging.in-
vestigated. After thermal aging, the dynamic modulus of silicone-based
In addition, the characterization techniques used in this study helped to explain the reasons thermal gap filler
materials
behind increased,
those changes. but remained viscoelastic, while on the other hand, with thermal ag-
ing, the silicone-free thermal gap filler material became hard. In dynamic mechanical anal-
ysis,
4. with the increase of temperature, the dynamic modulus of preaged silicone-free ther-
Conclusions
mal gap filler
In this material
work, increased
the impact of rapidly
thermalafter
aging 115on°C.the
It was observed
properties of that TIM B becomes
silicone-based and
hard after thermal aging, which will have an impact on the
silicone-free thermal gap filler materials has been analyzed, and the effect of the performance and reliability
chemical of
the device. Inonelectronic
compounds the change devices, after long-term
in mechanical, exposure
thermal, to heat, silicone-free
and dielectric properties has TIMbeenwill
become hard, which can create cracks on the adjacent surfaces
investigated. After thermal aging, the dynamic modulus of silicone-based thermal gap of the device, which will
affectmaterials
filler the performance
increased,and butreliability
remained of the device.while
viscoelastic, Additionally,
on the other voids
hand,canwith
form as the
thermal
silicone-free TIM starts to become hard, which will have an
aging, the silicone-free thermal gap filler material became hard. In dynamic mechanicalimpact on the thermal perfor-
mance ofwith
analysis, the device. Thermal
the increase expansion is higher
of temperature, in silicone-based
the dynamic modulus ofthermal preagedgap fillers and
silicone-free
it increases
thermal gapwithfillertemperature, which corresponds
material increased rapidly after to 115 ◦
the dynamic
C. It was modulus
observed results
thatforTIM bothB
preaged and
becomes hardthermal-aged
after thermalsilicone-based
aging, whichthermalwill have gapanfiller
impactmaterials.
on theDue to higher ther-
performance and
mal expansion,
reliability there might
of the device. be pump-out
In electronic devices,issues
afterfor silicone-based
long-term exposure thermal
to heat,gap filler ma-
silicone-free
terials. This phenomenon needs to be considered when designing
TIM will become hard, which can create cracks on the adjacent surfaces of the device, an electronic package.
which
It is evident from the study that the silicone-based thermal
will affect the performance and reliability of the device. Additionally, voids can form gap filler material has shown as
better
the thermal and
silicone-free TIMmechanical properties
starts to become hard,atwhich
higherwill temperatures
have an impact than the silicone-free
on the thermal
performance of the device. Thermal expansion is higher in silicone-based thermal gap fillers
and it increases with temperature, which corresponds to the dynamic modulus results
for both preaged and thermal-aged silicone-based thermal gap filler materials. Due to
Materials 2021, 14, 3565 18 of 20
higher thermal expansion, there might be pump-out issues for silicone-based thermal gap
filler materials. This phenomenon needs to be considered when designing an electronic
package. It is evident from the study that the silicone-based thermal gap filler material has
shown better thermal and mechanical properties at higher temperatures than the silicone-
free thermal gap filler material. On the other hand, for the applications where electrical
insulation is the primary concern, low-k dielectric material such as silicone-free thermal gap
filler materials are a better choice of thermal interface material to enhance the performance
and reliability of those devices. For silicone-sensitive devices, silicone-free thermal interface
materials should be used. Using dielectric relaxation strength (DRS) value, TIMs with
required electrical conductivity can be chosen for electronic packages. Depending on
the application, the proper thermal interface material needs to be chosen. The results
found in this this study can be readily used to design more efficient and reliable electronic
packages. Numerical analysis can be performed using the results to find the performance
and reliability of the electronic devices designed with these TIMs. Methodologies used in
this study can be followed to characterize the mechanical, thermal, and dielectric properties
of different kinds of thermal interface materials.
Author Contributions: Conceptualization, A.S.M.R.C. and M.M.R.; Research planning, A.S.M.R.C.,

M.M.R. and M.K.; Experimental methodology, A.S.M.R.C. and M.M.R.; Experimental work: A.S.M.R.C.,
M.M.R., M.K. and R.B.; Software, A.S.M.R.C. and P.P.D.; Data analysis, A.S.M.R.C., M.M.R., M.K.
and P.P.D.; Investigation, A.S.M.R.C. and M.M.R.; Writing—original draft preparation, A.S.M.R.C.,
M.M.R. and M.K.; Writing—review and editing, P.P.D., R.B., R.R. and D.A.; Supervision, R.R. and
D.A. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The authors would like to acknowledge Electronics, MEMS, and Nanotechnol-
ogy Systems Packaging Center (EMNSPC) at the University of Texas at Arlington, and Institute
for Predictive Performance Methodologies (IPPM) at the University of Texas at Arlington Research
Institute (UTARI) for providing the opportunity and support for the research.
Conflicts of Interest: The authors declare no conflict of interest.
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materials

1 Department of Mechanical and Aerospace Engineering, University of Texas at Arlington, Arlington,

Materials 2021, 14, 3565. https://doi.org/10.3390/ma14133565 https://www.mdpi.com/journal/materials

this material. The elevated temperature in the electronic devices has

Characterization of the properties of thermal interface materials is primarily impor-

2. Materials and Methods

Materials 2021, 14, 3565 4 of 20

and properties of the TIMs were analyzed at 1 Hz dynamic frequency [4].

Figure 3. Schematic of dynamic mechanical analyzer (tension mode) [16].

2.2.2.For dynamic mechanical

2.2.2. Thermomechanical Analysis (TMA)

Figure 4. Schematic of the thermomechanical analyzer (TMA) [17].

2.2.4. Fourier Transform Infrared Spectroscopy (FTIR)

2.2.5. Broadband Dielectric Spectroscopy (BbDS)

capacitance of the free space is presented by C0 (F) [26].

Materials 2021, 14, 3565 9 of 20

TIM A preaged TIM A thermal-aged at 125 °C

Dynamic modulus, also referred to as complex modulus, is calculated from storage

Normalized Complex Modulus (E*)

TIM B preaged TIM B thermal-aged at 125 °C

3.2. Thermal Expansion

1.07 TIM B preaged

1.06 TIM B thermal aged at 125°C

3.3. Thermal Properties

Figure 14. A representation of oxidative softening-chain scission [33].

Figure 14. A representation of oxidative softening-chain scission [33].

3.5. Dielectric Properties

Materials 2021, 14, 3565 17 of 20

Author Contributions: Conceptualization, A.S.M.R.C. and M.M.R.; Research planning, A.S.M.R.C.,

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