1

Thermally Conductive Polymer-Based Composites for Electronic Packaging Applications

AHMED MAHMOUD

A thesis submitted in partial fulfillment of the requirements for the degree of BACHELOR OF APPLIED SCIENCE

SUPERVISOR: DR. HANI E. NAGUIB Department of Mechanical and Industrial Engineering

Abstract
The objective of this thesis was to develop an electrically-insulative material with a high thermal conductivity for electronic packaging applications. A heat-transfer analysis study found that a thermal conductivity of at least 10 W/m.K would be required in order to provide a viable alternative to the current electronic packaging and heat sink assembly. To that end, a composite comprising a poly(p-phenylene sulphide) matrix and Boron Nitride filler was investigated. The choice of matrix was predicated upon the need to use a resin which has a low melt viscosity and excellent affinity with the filler to ensure that air gaps within the composite are minimized, while the choice of filler was based upon the favourable thermomechanical properties of Boron Nitride, as well as encouraging previous research. Initial thermal conductivity testing as well as SEM analysis using four different grades of Boron Nitride singled out one polymorph PTX60 for further study; due to its spherical shape, it allowed for maximization of filler-packing throughout the matrix, thereby increasing the likelihood of filler-filler contact and reducing the percolation threshold. At 7.8 W/m.K, however, the highest obtained thermal conductivity was well below the goal of the thesis, as well as theoretically-predicted values. It was conjectured that this was due to high interfacial resistance resulting from incompatibility between the Boron Nitride and the matrix. This issue was addressed by surface-treating PTX60 with a coupling agent, which was shown in SEM images to enhance the adhesion of Boron Nitride to the matrix, thereby reducing phonon scattering at interfacial barriers and lattice defects, and bringing the percolation threshold within reach. The final result was a 13% improvement in thermal conductivity, achieving a very remarkable value of 8.8 W/m.K using 74 wt% Boron Nitride in a poly(p-phenylene sulphide) matrix. Methods to increase this value to the desired 10 W/m.K, including use of multi-modal Boron Nitride filler and a novel epoxy matrix, are explored at the end of the report.

Table of Contents
I II
Introduction............................................................................................................................... 1 1.1 Heat Transfer Analysis.............................................................................................................. 2 Literature Review...................................................................................................................... 5 2.1 Polymer Research..................................................................................................................... 5 2.2 Boron Nitride Research ............................................................................................................ 6 2.3 Percolation Theory and Previous Research on Fillers .............................................................. 7

III

Phase One: Preliminary Research using Single-Phase and Hybrid Fillers .................................... 8 3.1 Methodology .......................................................................................................................... 10 3.2 Results .................................................................................................................................... 13 3.2.1 Single-Phase Composite Results ............................................................................ 13 3.2.2 Hybrid-Filler Composite Results ............................................................................. 16 3.3 SEM Analysis .......................................................................................................................... 18 3.2.1 Methodology .......................................................................................................... 18 3.3.2 SEM Micrograph Results ........................................................................................ 19 3.3.2.1 Single-Phase Composite Micrographs ................................................... 19 3.3.2.2 Hybrid-Filler Composite Micrographs ................................................... 21 3.4 Compression Molding Pressure Analysis ............................................................................... 24

IV

Phase 2: Coupling Agents ........................................................................................................ 28 4.1 Background Research ............................................................................................................. 28 4.2 Methodology .......................................................................................................................... 30 4.3 Thermogravimetric Analysis (TGA)......................................................................................... 31 4.3.1 Methodology .......................................................................................................... 31 4.3.2 Results .................................................................................................................... 32 4.3.2.1 Calibration .............................................................................................. 32 4.3.2.2 PTX60 vs. PT110 ..................................................................................... 32 4.4 Design of Experiments ........................................................................................................... 36 4.5 Thermal Conductivity Results................................................................................................. 40 4.6 SEM Analysis .......................................................................................................................... 43

Future Research Directions ...................................................................................................... 46 5.1 Multi-Modal hBN Fillers ......................................................................................................... 46 5.2 Ishida Method ........................................................................................................................ 47 5.2 Multifunctional Fillers ............................................................................................................ 48

VI

Conclusion.............................................................................................................................. 49

Introduction

As electronic devices are made smaller and more powerful, they generate more heat in a smaller volume of space, and so the need arises to develop optimum heat dissipation solutions. Heat sinks are used to transfer the heat generated by the processor or chipset to the surrounding air; these heat sinks are traditionally made out of a metal,
Figure 1: An Aluminum heat sink and fan

usually Aluminum, fabricated into a multi-fin arrangement to maximize heat dissipation. However, Aluminum has a high electrical conductivity, which prompts the need for micro-processor packaging solutions to prevent the heat sink from short-circuiting the processor. [1] These packages are usually made of a copolymer, such as epoxy, which has a high electrical resistivity and excellent processability, but also a low thermal conductivity in the range of 0.1 to 0.5 W/m.K which reduces the overall effective heat dissipation of the heat sink. [2] To address this problem, researchers have experimented with composites which could exhibit both a high thermal conductivity and a low dielectric constant, the aim being to develop a material which would perform the function of a heat sink, while forgoing the need for electronic packaging. They started by embedding ceramic fillers, such as alumina (Al2O3) [3], silica (SiO2) [4], aluminum nitride (AlN) [5][6][7], and boron nitride (BN),[8][9][10] in a polymer matrix. Among these materials, hexagonal BN (hBN) showed the greatest potential due to its high thermal conductivity (up to 400 W/mk) and relatively low dielectric constant, compared with SiC, Al2O3, and AlN, which suffer from high reactivity with moisture and a poor affinity with resin. Further, hBN exhibits excellent resistance to oxidation and chemical corrosion. [11] For the matrix, a wide array polymers have been explored by researchers to varying success. Two polymers in particular have proven to be good candidates: poly(p-phenylene sulfide) (PPS) and Low-Density Polyethylene (LDPE). Both exhibit similar thermal

properties but have slightly varying mechanical properties owing to differences in molecular weight and degrees of cross-linking. [12] Though they are not as good as epoxies in terms of affinity to BN, they are the best thermoplastic choices available since they are easily processable. The thermal conductivity of the polymer-filler composite can be maximized by minimizing thermal barrier resistance along the heat flow path and forming a thermal conductive network in the composites. Once a conductive network is formed by the filler, the composite shows percolation behaviour, i.e., the thermal conductivity increases steeply. The objective of this thesis was to expand on current research on thermallyconductive polymers in order to develop prototypes a composite with a ceramic filler, in order to achieve a high thermal conductivity but low electrical conductivity.

1.1

Heat Transfer Analysis TAmbient

Rconvection

Heat transfer across the heat sink can be modeled by a series of heat resistors between the processor and ambient air representing: 1. The epoxy packaging which has a thermal conductivity of ~0.3 W/m.K [13] 2. The thin layer of thermal compound used to promote heat conductivity from the processor; a typical silverbased thermal compound has a thermal conductivity of approximately 5 W/m.K 3. The Aluminum heat sink, the thermal conductivity of which is 237 W/m.K 4. Heat convection from the heatsink

For this analysis, the following assumptions are made: The thickness of the epoxy packaging is 1 mm and that of the thermal compound is 0.5 mm The height of the heat sink is 10 cm The processor has the same dimensions as an Intel LGA775 socket processor: 0.6 in x 0.6 in [14] Heat loss is by simple convection only, and therefore the heat transfer coefficient is given by = where: h = heat transfer coefficient, W/(m2K) q = heat flow in input or lost heat flow , W A = heat transfer surface area, m2 T = difference in temperature between the solid surface and surrounding fluid area, which is A study by Rebay et al found that the heat transfer coefficient for a typical commercial heat sink is roughly 49W/m2K. [15] This factor is a function of the geometry of the heat sink and not the material from which it is made. Therefore, calculating the effective heat resistivity across a commercial heat sink, we get: = + + , + =
=

1 + + +

0.001 0.0005 0.1 1 + + + 0.35 (2.3 10 ) 5 (2.3 10 ) 237 (2.3 10 ) 49 (2.3 10 )

= 103.4

If we are to replace the current arrangement with just a single heat sink that incorporates the electronic packaging, only two resistivies exist: one due to the composite heatsink and the other due to convection. Therefore: = 1 +

where Lcomposite is the height of the heat sink which, as stated above, is 10 cm.

Then the required k for the composite is: = 1 ( )

0.1 1 (103.4 )(2.3 10 ) 49 (2.3 10 ) = 29.6 .

This figure approximates the thermal conductivity required by the composite which would result in the same dissipative power as the current Aluminum heatsink arrangement. However, due to time constraints, the target keff for this thesis is set to for 10 W/m.K, which is a more realistic expectation.

II

Literature Review

There exists a substantial body of literature on attempts to develop thermally-conductive composites for enhanced electronic packaging applications. This section summarizes the research that has been done on the topic in the run-up of to experimental prototyping.

2.1

Polymer Research

Most studies were carried out using a polymer or epoxy for the matrix, the reason being that they are affordable, easily processed and have a low dielectric constant [16]. However, almost all polymers have very poor thermal conductivities due to their semicrystalline nature; specifically, in a spherulitic polymer, the chains fold into highly ordered crystalline lamellae, but are separated by amorphous regions that disrupt phonon heat transport (by scattering), therefore resulting in poor thermal conductivity. [17] Therefore, it becomes important to choose a polymer which has a low viscosity so that it is easily processed, has a high tendency to crystallize to promote thermal conductivity, a high service temperature to withstand the heat generated by the processor, and most importantly, it must allow for excellent filler dispersion. Research indicates that two particular polymers: poly(p-phenylene sulfide) (PPS), Liquid Crystal Polymer (LCP), and polyethylene (PE) are excellent candidates based on these criteria. [18][19] Whereas PPS is chosen for its outstanding mechanical properties, high thermal stability, and good solvent resistance, LCP and PE are equally as qualified for our application; though they have slightly lower thermal conductivity than PPS, they can be stretched and aligned to produce a high uni-directional thermal conductivity. A recently-published and criticallyacclaimed study by Shen el al. reported achieving thermal conductivities as high as 104 W/mK using high-quality ultra-drawn polyethylene nanofibres. The high thermal conductivity achieved is attributed to the restructuring of the polymer chains by stretching, which improves the fibre quality toward an ideal single crystalline fibre.[20] The methods used to achieve these results, however, are expensive and time consuming, so the focus for now will be on embedding filler materials within a PPS matrix to the desired thermal conduction network.

2.2

Boron Nitride Research

Boron nitride exists in several allotropic forms; most commonly, it assumes one of two structures: hexagonal (hBN, similar to graphite), and cubic (cBN, similar to diamond). The hexagonal form is extremely soft and has a layered structure, where Van der Waals forces hold sheets of covalently bonded boron and nitrogen atoms together.

As a consequence of the layered structure, hBN crystals are anisotropic. This anisotropy is clearly seen in the thermal conductivity: The in-plane thermal conductivity [for hBN] has been measured to be more than 300 W/mK, and is attributed to good conduction of phonons through boron nitride bonds, whereas the through-plane conductivity has been measured to be
Figure 2: Hexagonal Boron Nitride Crystal Structure

only about 3 W/mK, a significant difference, most likely due to poor phonon transfer across layers.[29]

Numerous studies have been carried out that confirm the ability of Boron Nitride to show percolation in a polymer matrix, thereby resulting in a high thermal conductivity composite. One such study by Sato et al was able to achieve a thermal conductivity of 7 W/mK. Using a polyimide matrix embedded with 60% hBN.[30] On the other hand, Yung et al were able to achieve 20 W/mK using multimodal (hybrid) fillers of
Figure 3: Yung et als results for thermal conductivity of BN resins with various filler contents.

hBN and cBN.[31] Their results are shown in figure 3 on the right. Much higher values for composite thermal conductivity have been obtained in other studies, one of which is briefly touched on in section V.

2.3

Percolation Theory and Previous Research on Fillers

Previous studies indicate that embedding highly-conductive ceramic filler particles in the polymer matrix is the most widely used method to develop a composite with high thermal conductivity. The process which governs the enhancement in thermal conductivity is called Percolation, which is a phenomenon in which the highly conducting filler particles form at least one continuous low-resistance chain connecting the opposite faces of the matrix. Percolation theory predicts that the thermal conductivity of the composites increases according to a scaling law with increasing concentration of the high thermal conductivity constituent after percolation. However, when the characteristic size of the particles in the nanocomposites is comparable to or smaller than the phonon mean free path, the phonon scattering at interfaces between two materials can introduce significant thermal resistance in the highly conductive phonon pathway. Such interfacial thermal resistance can reduce the thermal conductivity of the nanoparticle composites. The thermal conductivity of the random composites thus deviates significantly from the predictions of the percolation theory. [21][22] In early studies on the topic, oxide fillers such as alumina (Al2O3) and silica (SiO2) were used due to their affordability and processability in mixing procedures. However, they have always yielded poor results inasmuch as the thermal conductivities of the oxide filler composites were at most 13 W/mK. [23] Subsequent research focused on nitride ceramics, particularly Aluminum Nitride (AlN) and Boron Nitride (BN), which are now considered the best qualified fillers for thermally-conductive polymers. [24][25] Both exhibit very high thermal conductivities, as evident in table 1, are affordable, and they disperse well in polymers.
Table 1: Thermal Properties for Various Materials [26][27] Density CTE Specific Heat (g/cc) [ppm/K] [J/kg-K] @ 25C 2.25 1.20 794 3.26 4.10 734 3.98 7.1 798 2.20 0.5 689 5.64 0 [28] 523

Material Boron Nitride Aluminum Nitride Aluminum Oxide Silica Zinc Oxide

Thermal Conductivity [W/mK] 300+ 260 30 1.4 54

III

Phase One: Preliminary Research using Single-Phase And Dual Hybrid Fillers
Based on the findings in the last section, it was decided to go forward with PPS and

Boron Nitride as the baseline constituents of the composite. This was primarily due to their favourable properties as postulated by previous research. In line with that strategy, the aim of this research phase is to gain an understanding of how different amounts and types (polymorphs) of Boron Nitride embedded in a PPS matrix would affect the thermal conductivity of the composite by conducting a battery of tests using as many different compositions as possible. Two different parameters known to affect thermal conductivity are going to be explored in this section 1. Type of Boron Nitride: Four different polymorphs of hexagonal Boron Nitride comprising different shapes and sizes were decided are going to be used in order to compare their performance1. SEM images, along with physical properties, of these polymorphs can be seen in the figure 4 below.

Figure 4: SEM micrographs of the polymorphs of Boron Nitride which will be tested in this thesis

Obtained from Momentive Performance Materials, Inc.

2. Amount of Boron Nitride in a thermal conductivity sample: Based on previous research, we know that the higher the Boron Nitride content in the composite, the high the thermal conductivity. However, there is both a theoretical and practical limit as to how much Boron Nitride one can embed in a composite.

The theoretical limit can be easily determined by calculating the maximum theoretical atomic packing factor (APF) of Boron Nitride spheres in the PPS matrix:

16 ( 3 ) = = = = 0.74 16 2
This then tells us that the composition at which the Boron Nitride particles are closest packed in the PPS matrix is 74 wt%. At this composition, however, the sample is speculated to be too brittle to be viable. Therefore, an additional composition 33 wt% Boron Nitride will be tested in order to establish a meaningful relationship between Boron Nitride content and Thermal Conductivity. In addition to the above tests, we will explore the effect of using hybrid-filler composites, containing 2 or more polymorphs of Boron Nitride, on thermal conductivity. The purpose behind these tests is to attempt to maximize the thermal conductivity by combining the positive effects of various shapes and sizes of Boron Nitride in the same matrix. We will then conclude the section by analyzing a number of SEM micrographs of a representative number of compositions in order to examine the morphologies of the prototyped samples.

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3.1

Methodology

For the thermal conductivity tests, a 2 cm diameter disc-shaped prototype is used. The steps involved in making the fabricating this sample are as follows: 1. The constituents for the desired composition are weighed using a digital scale then mixed thoroughly in a glass container. 2. The mixture is then placed in a compounder which melts the constituents and then, using a pair of screws, extrudes the mixture into a long strand [32]. The purpose of this process is to ensure that the filler particulates are properly distributed and well dispersed within the polymer matrix

3. The strands are then inserted in a freeze mill which pelletizes them into a finelyground thoroughly dispersed powder. This is done by cooling the sample using liquid nitrogen to make it sufficiently brittle and then hammering it into a powder; the process is carried over three 2-minute cycles in order to give the hammer and sample time to cool down before continuing to grind it down. The end result is a thoroughly-mixed powder consisting of the polymer and filler(s) 4. The powder samples are then inserted in the mold and are compacted at room temperature under 2000 psi to ensure that the powder solidifies in the mold before moving on to the next sample. Otherwise, the power might be blown away as the other samples are added.

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5.

Finally, when all samples are compacted, they are molded at 310C and 2000 psi for 15 minutes. The mold is then quenched in ice-cold water and the discs are removed.

Two molds may be used which produce different sized samples: one is used for thermal conductivity analysis, and is 1 cm in diameter and 2 cm thick. The other is used for SEM inspection, and is the same diameter but only 1 cm thick in order to be easily shattered during SEM preparation. If the composition of the sample is over 45% BN or 20% CNT, the compounder is unable to process the blend since it becomes too viscous, and it would therefore have to be dry-blended directly using the compression molder. This entails weighing out and mixing the samples in a glass container by shaking the container by hand to ensure the constituents are well dispersed compacting them individually in the mold, and then finally compressing them at 310C, 2000 psi.

This method produces samples in which the filler is poorly dispersed in the polymer since the compounding and freeze milling steps are forgone. The final step is to then measure the thermal conductivity of the samples using a custombuilt analyzer which conforms to ASTM standard E-1255-04[33]. This is carried out by placing the test specimen under load between two steel bars having the same diameter as the specimen. A heater at the top of the test stack is then turned on and a temperature gradient is established across the stack; heat losses are minimized by

12

use of a thick insulation layer as well as a longitudinal guard having approximately the same temperature gradient. At equilibr equilibrium, , the thermal conductivity is derived from the measured temperature gradients in the respective specimens and the thermal conductivity of the reference materials by using the following equation:

. .( + ) 2

where,
Zi are positions measured from the top of the column and given by figure 5 Ti are temperatures at Zi kM is the thermal conductivity of the met metal reference bars This calculation is carried out through software which monitors the temperatures across the gradient using 9 thermocouples.

Guard Heater Section

Metal or ceramic guard shell at Tg

Figure 5: Schematic of the thermal conductivity analyze showing the comparative comparative-guarded guarded longitudinal heat flow system

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3.2

Results

In line with the introductory discussion, 13 samples with different compositions were prepared and tested for thermal conductivity. Six of those samples were single-phase composites, meaning they contained only one polymorph of Boron Nitirde, while the other four were hybrid (dual) composites, comprising two different polymorphs of Boron Nitride, dispersed in a PPS matrix.

3.2.1 Single-Phase Composite Results

The purpose of the single-phase tests was two-fold: 1. To understand how different polymorphs of Boron Nitride affect the thermal conductivity of BN-PPS composites: This is accomplished by testing 4 different samples each containing the same concentration (33 wt%) of Boron Nitride but with different polymorphs 2. To determine how much thermal conductivity increases with increasing Boron Nitride concentration in the composite (from 33 wt% to 74 wt%)

Chart 1: Thermal Conductivity Results For Different Polymorphs of Boron Nitride

9 8 Thermal Conductivity (W/m.K) 7 6 5 33 wt% Boron Nitride 4 74 wt% Boron Nitride 3 2 1 0 Pure PPS PTX25 PTX60 PT371 PT110

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Looking at the chart 1 on the previous page, we observe that, for 33 wt% Boron Nitride composites, three of the polymorphs, PTX25, PTX60 AND PT371, have an identical effect on thermal conductivity, raising it only slightly above that of neat PPS. PT110, on the other hand, performs relatively poorly, falling almost 30% short of the thermal conductivities attained by the other polymorphs. This may be due to the fact that the PT110 platelets are pulverized, or otherwise flattened across the width of the sample, during compression molding, therefore diminshing the thermal network which forms across the matrix and resulting in a breakdown of percolation. In fact, this is true of all the other polymorphs, though to a lesser extent than in the case of PT110. Using a modified version of the Maxwell-Garnett formula:

we can estimate that the theoretical thermal conductivity of a composite consisting of 33 wt% Boron Nitride within a PPS matrix to be 44 W/m.K, which is well above any of the obtained results[46]. Generally speaking, this discrepancy between theoretical and experimental thermal conductivities is due to a high thermal resistance at the interfacial boundaries between PPS and the Boron Nitride particulates due to the inherent incompatibility of the two compounds. This issue can be resolved using coupling agents, which will be addressed in section III. Another reason for the deviation of results from theoretical predictions is due to the imperfect dispersion of Boron Nitride in the PPS matrix. Since the only method used to mix the two
Figure 6: Schematic showing (a) theoretical, (b) (likely) actual packing of BN particulate fillers in PPS matrix

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components is manual shaking, there is usually an uneven distribution of matrix and filler powders during compression molding. As a result, filler particulates tend to clump together into clusters throughout the matrix with regions of pure PPS in between, rather than percolating by arranging into a proper close-packed geometry as can be seen in figure 6 on the previous page.

Referring back to chart 1 on page 13, we observe that increasing the Boron Nitride content of the samples vastly improved their thermal conductivity. At 7.8 W/m.K, PTX60 achieves the highest thermal conductivity attained so far, edging out PT371 by about 0.4 W/m.K. The reason for this slight discrepenacy relates to differences in the microstructures of the PTX60 and PT371 composites which will be explored in detail the next section using SEM micrographs. Since 74 wt% Boron Niride implies that most of the sample is ceramic in nature, prototypes which were fabricated at this composition very brittle and difficult to handle. In fact, all samples containing 74 wt% PTX25 and PT110 fractured either during molding or drilling, and so were rendered un-testable (see figure 7a).
Figure 7a: Cracked 74 wt% PTX25 sample

Though the value achieved for 74 wt% PTX60 is encouraging, it is not recommended to develop a material with such a high content of ceramic since it would be very difficult to machine into a multi-fin heatsink. In addition, it will be liable to fail due to fatigue early on in its lifecycle as unstable cracks would propagate very quickly after initiating at sites of stress concentration, such as at the corners of the fins.

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3.2.2 Hybrid Filler Composite Results

As was pointed out in the previous section, one of the two main reasons behind the discrepancy between empirical predictions of thermal conductivity and experimental results is due to the coalescence of the Boron Nitride particulates in the matrix during compression molding, leaving vast regions of poorly-conductive PPS across the composite. To address that issue, dual-phase PTX60:PTX25 hybrid fillers were attempted, predicated on the understanding that PTX25 spheres are small enough to fit in the interstitial sites between the larger PTX60 spheres, thereby achieving an ordered arrangement of filler particulates in the matrix and forming the desired thermal conductivity network. At 33 wt% Boron Nitride, three different samples with different ratios of PTX60 to PTX25 were prototyped and tested in order to determine the optimal proportion in the sample which would ensure the highest thermal conductivity; these ratios are 2:1, 3:1 and 4:1 PTX60:PTX25. Looking at the results in chart 2 above, we notice that there is a weak, though positive correlation between the ratio of PTX60:PTX25 and thermal conductivity. Based on these results, we can hypothesize that PTX60 has a better thermal conductivity in Boron Nitride-PPS composites than PTX25 since, in samples containing identical amounts of boron nitride but with different ratios of PTX60 and PTX25, increasing the proportion of PTX60 in the sample resulted in an increase in thermal conductivity of the composite.
Thermal Conductivity (W/m.K)

Chart 2: Thermal Conductivity Results For Hybrid-Filler BN Composites

6 5 4 3 2 1 0 2:1 PTX60 : PTX25 3:1 PTX60 : PTX25 4:1 PTX60 : PTX25 15:1 PTX60 : PT110

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We also conclude that the assumption made regarding better percolation was not fulfilled since there is almost no improvement in thermal conductivity using hybrid fillers than one-phase fillers, both of which achieve ~2 W/m.K at 33 wt% Boron Nitride, which is well below our target of 10 W/m.K. The underlying reasons for this, and as to why PTX60 performs better than PTX25 will be explained using SEM micrographs in the next section In addition to the PTX60:PTX25 hybrid-filler composites, one sample containing 74% PTX60 and 5% PT110 a 15:1 ratio of PTX60:PT110 was tested. This was based upon the assumption that the crushing of PT110 platelets during compression molding may serve to disperse them throughout the matrix, thereby connecting together the PTX60 particulates in the matrix; this then forms an interconnected network of highlyconductive Boron Nitride particulates throughout the matrix, leading to a high thermal conductivity. The result, however, indicates that this is not the case; at 5.6 W/m.K, the thermal conductivity of the hybrid-filler sample is 40% less than the 74 wt% PTX60 sample, which suggests that PT110 particulates have a detrimental effect on thermal conductivity. Likely this is due to the high incompatibility between the PT110 platelets and PPS, leading to a high thermal resistance at the interfacial boundaries. As was mentioned earlier, this problem may be addressed by treating the Boron Nitride with a compatibilizing agent to improve its bonding to the matrix. However, in the case of PT110, even if surface treatment is carried out, the platlets will still tend to line up across the width of the specimen, therefore providing asymmetric thermal conductivity in the composite. A 15:1 PTX60:PTX25 sample was also prototyped, but due to excessive brittleness, it shattered during extraction from the mold.

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3.3

SEM Analysis

The Scanning Electron Microscope (SEM) is a powerful tool which can provide us with a valuable insight into the microstructure of the prototypes , giving information about dispersion, morphology, percolation and integrity of the sample. Faults such as cracks or air pockets, which elevate thermal resistivity within the composite, can also be identified on the micrographs.

3.3.1 Methodology
Two methods were used to obtain SEM samples for analysis: The first was to compression-mold a thin disc specially made for SEM analysis (see figure 7b); the second was to cut slots into thermal conductivity samples using a band saw after they were tested using
Figure 7b: 74 wt% PT371 SEM sample

the thermal conductivity analyzer. After that, the following steps are carried out [34]: 1. The sample is dipped in liquid nitrogen for about one minute then, using a pair to tongs, snapped in order to expose a clean fracture surface with good topology for analysis. 2. Next, the sample is mount sample onto stub using glue 3. The surface is then polished with SiC sandpaper in order to enhance grain boundaries 4. The metallic stub is covered with Carbon Black in order to insulate it so that it doesnt interfere with the electron beam 5. The sample is then sputter-coated with a 7.5 30 nm gold platinum layer at ~ 10 Pa in order to impart electrical conductivity to the fractured surface. This results in a higher rate of secondary and backscattered electron emissions which would yield a higher resolution image. If the sample is not properly coated, the samples accumulate charge when scanned by the electron beam, which can cause beam

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deflection and increased emissions of secondary electrons which cause scanning faults and other image artifacts. 6. Finally, the samples are placed under the microscope, analyzed, and photographed

3.3.2

SEM Micrograph Results

As with before, analysis was carried out on both single-phase and hybrid-filler composites. All samples were imaged at 50x, 500x and 1000x magnifications in order to provide a cascade of morphology, from a macro overview to a high-resolution insight into the grain structures of the composite constituents.

3.3.2.1

Single-Phase Composite Micrographs

SEM analysis was carried out on composites consisting of 74 wt% PTX25, PTX60 and PT371, as well as 33 wt% PTX60 and PT371 in a PPS matrix. The purpose behind analyzing these compositions is to show us how different polymorphs of Boron Nitride disperse within the PPS matrix, how well they retain their shape after compression molding, and to confirm the hypotheses postulated in section 3.2.2 regarding the thermal conductivity results obtained for these compositions. SEM micrographs of the aforementioned compositions can be seen in the following two pages.

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Figure 8: 74% PTX25 in PPS matrix at 50X, 500X and 1000X respectively

Figure 9: 74% PTX60 in PPS matrix at 50X, 500X and 1000X respectively

Figure 10: 74% PT371 in PPS matrix at 50X, 500X and 1000X respectively

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Figure 11: 33% PTX60 in PPS matrix at 500X

Figure 12: 33% PT371 in PPS matrix at 500X

Figures 8, 9 and 11 show the Boron Nitride PTX25 and PTX60 spheres have largely disintegrated during compression molding, resulting in a breakdown of their thermomechanical properties. This breadown occurs when Boron Nitride sheets slip past one another as they are compressed under a high pressure, thereby deforming the hexagonal structure of the Boron Nitride crystal. This results in steep changes in its crystallographic directions, resulting in phonon scattering both within the Boron Nitride crystals and at the interfacial barrier between Boron Nitride and PPS [31]. This scattering is the root cause of the poor thermal conductivities obtained in the previous section. Therefore, the next section (3.4) will attempt to address the issue of Boron Nitride pulverization during compression molding by adjusting the process conditions Figures 10 and 12 shows a similar pattern with the PT371 agglomerates broken down into small flakes randomly dispersed throughout the matrix; these flakes are not only poorly conductive relative to their intact counterparts, but they are also spaced apart in the matrix, and therefore not forming a proper 3D thermal conductivity network.

3.3.2.2

Hybrid-Filler Composite Micrographs

As with the single phase samples, SEM analysis was conducted for two compositions, 15:1 PTX60: PT110 (74% PTX60, 4% PT110), and 15:1 PTX60:PTX25, which can be seen in figures 13 and 14 on the next page.

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Figure 13: 74% PTX60 + 5% PT110 in PPS matrix micrographs at 50X, 500X and 1000X respectively

Figure 14: 74% PTX60 + 5% PTX25 in PPS matrix micrographs at 50X, 500X and 1000X respectively

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In both samples, it is clear that, despite good dispersion, there is severe breakdown of the Boron Nitride particulates in the matrix. This is due to the fact the matrix is inundated with copious amounts of Boron Nitride (79 wt% in total), which results in their immediate pulverization as they press up against each other during compression molding. This is particularly apparent in figure 14, where it can be seen that both polymorphs of Boron Nitride have completely broken down. On the other hand the sample in figure 13 shows that some particulates retained their integrity during compression molding. Nevertheless, the disintegration of was so extensive, that we cannot consider either composition viable.

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3.4 Compression Molding Pressure Analysis

As was mentioned in the last section, Boron Nitride particulates undergo extensive damage due to the high pressure (2,000 psi) sustained during compression molding. This prompts us to attempt to understand how we can address this issue; particularly, how varying this pressure may produce better percolation. Pressure plays a huge role in determining the final morphology of compression-molded samples. In the case of ceramic-polymer composites, there are two dimensions to the effect of pressure: 1. On the polymer matrix: The effect of molding pressure on the thermomechanical properties of mouldable polymers has been extensively studied and is widely understood. One paper by Parasnis and Ramini summarized this effect very well; by conducting compression molding runs on samples compressed at different pressures, they found that the stiffness and crystallinity of the molded polymer increased as the pressure is increased. Past a certain pressure, these characteristics decline rapidly, thereby diminishing the thermo-mechanical integrity of the molded samples. That is to say, they found that there is a narrow pressure band in which the crystallinity and stiffness of the polymer are maximized. For thermal conductivity of ceramic-polymer composites, achieving crystallinity is not crucial, but it may improve the obtained results due to the fact that neatly-crystallized polymer speherulites tend to conduct heat better than amorphous polymers with randomly-distributed strands.[43] 2. On the ceramic filler: As noted previously, damage sustained by the Boron Nitride particles can result in a breakdown of their thermomechanical properties, rendering them far less conductive than they would be if they were intact. In order to understand how different moulding pressures affect the above mentioned parameters, prototypes consisting of 33 wt% PTX60 in PPS were compression molded at 4 different pressures 500, 1000, 1500 and 2000 psi and analyzed using SEM.

25

Figure 15: 33% PTX60 in PPS matrix compression-molded at 500 psi 50X

Figure 16: 33% PTX60 in PPS matrix compression-molded at 1,000 psi 50X

Figure 17: 33% PTX60 in PPS matrix compression-molded at 1,500 psi 50X

Figure 18: 33% PTX60 in PPS matrix compression-molded at 2,000 psi 50X

26

Figure 19: 33% PTX60 in PPS matrix compression-molded at 500 psi 500X

Figure 20: 33% PTX60 in PPS matrix compression-molded at 1,000 psi 500X

Figure 21: 33% PTX60 in PPS matrix compression-molded at 1,500 psi 500X

Figure 22: 33% PTX60 in PPS matrix compression-molded at 2,00 psi 500X

27

Two sets of images were taken of the samples compressed at the 4 pressures, one at 5ox magnification to give a macroscopic view of the morphology of the samples (figures 15 through 18), and the other at 500x magnification to provide information on Boron Nitride integrity after compression molding (figures 19 through 22). The following observations are made: At low pressures, large microvoids, cracks and air pockets form throughout the cross-section of the sample. These are and are a result of insufficient pressure during compression molding, and are extremely detrimental to the thermal conductivity of the final composite since the air in these gaps has a high thermal resistivity. Therefore, we conclude that higher pressure yields a higher thermal conductivity based on the 50x magnification micrographs. On the other hand, looking at figures 19 through 22, we notice that, as pressure increases, there is a more pronounced breakdown of boron nitride particulates, leading to loss of percolation and therefore diminishing the thermal conductivity of the composite. Based on that observation, we conclude that the lower the pressure, the better the percolation, and therefore the better the thermal conductivity. To strike a balance between these contradictory observations, we would have to pick one of the two middle pressures 1000 psi or 1500 psi. From a qualitative standpoint, it would seem that the 1000 psi treatment is better since it produces fewer microvoids, while at the same time preserving the integrity of the Boron Nitride sphere better than at 1,500 psi. Therefore, it was decided from this point onward to apply a 1,000 psi compression molding pressure to all thermal conductivity prototypes.

28

IV

Phase Two: Coupling Agents

For a given filler concentration, there are three methods to increase the thermal conductivity of the composite. They are (i) maximizing conductive paths, (ii) minimizing thermal resistance in each conductive path [35], and (iii) decreasing the thermal contact resistance at the fillermatrix interface. In this section, we will focus on the third method, attempting so with the use of a coupling agent (also known as compatibilizer).

The value of the third method stems from the tendency for gaps or other flaws to occur at the fillermatrix interface due to the insufficient affinity between filler and matrix. Such interfacial flaws cause a high thermal resistance at the interface, thus reducing the thermal conductivity of the composite [36, 37]. This thesis will attempt to use surface treatment of the filler to improve the affinity between filler and matrix, thereby significantly increasing the thermal conductivity of the composite. In particular, this thesis will focus on using silane coupling agents for surface treatment. Silane acts as a bridge to connect the ceramic filler and the polymer matrix together, because it has two different chemical structures at the two ends of the molecule. One end is chemically reactive with the polymer; the other end is chemically reactive with the surface of the ceramic filler [37].

4.1

Background Research

Several studies have been conducted which used a variety of silane coupling agents. For example, Yung and Yue [37] describe using a coupling agent KBM-430 to treat a polymorph of hexagonal Boron Nitride not different from PTX60. In surface-treating the Boron Nitride with the coupling agent, they first mixed the filler and the coupling agent of 1 wt% of filler weight in a small amount of isopropyl alcohol at 80C for 2 h. Next, they carried out vacuum drying to remove the solvent at 85C for 24 h, exposing the filler to ambient air for 4 h. Finally, they heat treated the filler at 100/120C for 4 h. The treated fillers were then stored in vacuum dryer.

29

Next, they embedded the treated Boron Nitride in an epoxy matrix and conducted thermal conductivity measurements.
Figure 23: Graph showing the strong correlation between use of coupling agents and thermal conductivity. Note that an increase in the amount of coupling agent does not necessarily imply an increase in matrix-filler adhesion. In fact, it may have a detrimental effect as is the case here [37]

In their results, they noted that increasing the concentration of the

coupling agent increased the thermal conductivity up until 1%, which they found to be the optimal concentration of coupling agent. Further increasing the coupling agent, they found, led to a thick coating on the BN filler, which eventually become thermal barrier causing the thermal conductivity to decrease. This is evident in figure 23 above, which summarizes the results of their experiments.

The value of this study is that it provides a starting point for this section of the thesis. An initial investigation found that KBM-430 may be difficult to procure, so a similar silane agent, 3-aminopropyltriethoxysilane (SCA100), was obtained from Struktol.

Other coupling agents used by other researchers were also explored, such as Styrylethyl trimethoxysilane (KH-560) [38] and [Methoxy(polyethyleneoxy) propyl]trimethoxysilane [35] but they were both deemed unsuitable for this thesis as they could not sustain the operating conditions under which the prototypes are produced. Therefore, the focus of this section of the thesis will be solely on using SCA1100 as a surface treatment coupling agent.

Finally, in addition to PPS, LDPE will be explored as a matrix polymer in future experiments when using treated Boron Nitride. This is in accordance with research

30

conducted by Harrison et al, which found a high affinity between silane-treated BN and LDPE [10].

4.2

Methodology

Treated Boron Nitride Treated Boron Nitride

50:50 water/ethanol solution

Coupling Agent

Boron Nitride Stir on hot plate Filter out treated boron nitride

The following steps are carried out in preparing a sample of Boron Nitride surface treated with SCA1100 coupling agent: 1. A 50:50 mixture of water an ethanol is prepared in a beaker 2. The desired amount of coupling agent is added to the water-ethanol mixture using a micropipette 3. The desired amount of Boron Nitride powder is added to the mixture of water, ethanol and coupling agent 4. The mixture is stirred at the required temperature on a magnetic stir plate 5. The stirred mixture is filtered, leaving behind treated Boron Nitride powder (i.e. Boron Nitride which has bonded to the coupling agent) 6. The Boron Nitride is dried on the hot plate overnight at 60C

31

4.3

Thermal Gravimetric Analysis

Thermogravimetric Analysis (TGA) is a type of test which measures weight changes in a material as a function of temperature (or time) under a controlled atmosphere. Its principal uses include measurement of a material's thermal stability and composition. For this thesis, TGA was carried out on treated and untreated samples of PTX60 and PT110 in order to compare the effect of surface treatment on both polymorphs, as well as to ensure that the coupling agent has adhered sufficiently to the Boron nitride particles.

4.3.1

Methodology

A TA Instruments Q-50 TG analyzer was used to conduct the TGA tests. The analyzer itself consists of a high-precision balance with a platinum pan loaded with 10-20mg of a powder of the composition to be tested. The sample is placed in a small electrically heated oven with a thermocouple to accurately measure the temperature. The atmosphere is then purged with Nitrogen in order prevent oxidation or other undesired reactions. Though the TGA machine can reach temperatures up to 1000C, a temperature of 800C was deemed sufficient for the testing. A ramp profile was picked, in which the furnace heats the sample gradually at 20C/minute until it reaches the 800C mark. After the data are logged, curve smoothing and other operations are then carried out by the software in order to identify the points of inflection and produce an accurate graph of percentage weight loss vs. temperature (or time).

32

4.3.2 Results 4.3.2.1 Calibration

As a proof-of-concept, LDPE was analyzed for weight loss by ramping the TGA up to 800C. Since LDPEs degradation temperature is only 120C, one would expect it to completely burn off during the test, which was confirmed as can be seen in figure 24 on the right. This test was carried out to ensure the TGA is properly calibrated.
Figure 24: TGA results for Pure LDPE

4.3.2.2

PTX60 vs. PT110

Next, treated and untreated samples of PTX60 were analyzed in order to compare weight loss results before and after surface treatment using 8 parts of SCA1100 coupling agent per 100 parts of PTX60.

Figure 25: TGA results for Untreated PTX60

Figure 26: TGA results for PTX60 treated with SCA100

33

The same was carried out for PT110 samples before and after treatment with SCA1100

Figure 27: TGA results for Untreated PT110

Figure 28: : TGA results for PT110 treated with SCA100

The fractional-loss results for treated and untreated BN upon heating to 800C are shown in chart 3 below. The amounts of volatile/decomposable material on the as-received, acetone and HNO3 treated BN particles were negligible (~0.1% weight loss), indicating that treatments involving acetone and acids did not result in a coating on the particle. On the other hand, the amounts of weight loss were much higher (averaging out around 0.82%) with treated PTX60 powder, indicating that the silane treatment resulted in a coating on the particle, which decomposed during heating. This is exactly what we are looking for in a coupling agent.

Chart 3: TGA results

0.20% Percentage Weight Change 0.00% PTX60 -0.20% -0.40% -0.60% -0.80% -1.00% PT110 Untreated

34

The results for PT110, however, were slightly more ambiguous, with two of the samples recording a weight gain and one recording a negligible loss. There are several reasons in existing literature which may explain this unexpected weight gain. The first is that one of the constituents in the sample may have oxidized during the experiment, leading to a chemical reaction, which forms a compound that increases the weight of the sample [44]. This, however, is unlikely since the furnace is purged with nitrogen gas for the duration of the run, which expels oxygen, thereby preventing any chemical reactions. Further, if oxidation was an issue with the TGA, we wouldve observed the same weight gain when testing the treated PTX60 samples. Another possible explanation for the weight gain is due to a phenomenon called baseline drift, in which the TGA machine becomes decalibrated over time due to changes in buoyancy of the purge gas as its density decreases with increasing temperature [45].
Figure 29: Baseline Drift in TGA

Regardless of the validity of this hypothesis is true, it was made clear from the TGA charts that there is no perceptible weight loss in any of the treated PT110 samples, indicating that SCA1100 failed to coat the PT110 platelets during the treatment process. This is likely due to an incompatibility between the functional groups on the coupling agent and the PT110 platelets.

35

By using SCA1100 solutions of three different concentrations, different amounts of coating resulted. The three amounts were: 3 parts of SCA1100 per 100 parts of Boron Nitride (3 pph for short), 8 pph (the recommended dosage per Struktol, the supplier of SCA1100), and 15 pph. These treatments were carried out for both PTX60 and PT110, and the results are plotted in chart 4 below.

Chart 4 : TGA Results for PTX60 vs. PT110 vs. Amount of Silane Used
0.40% 0.20% 0.00% 3 -0.20% -0.40% -0.60% -0.80% Amount of SCA1100 (parts of SCA1100 per hundred parts of Boron Nitride) 8 15 PTX60 PT110

As can be seen, the higher the silane concentration in the solution, the greater the weight loss, indicating an improved coating of the Boron Nitride. This was true for both PTX60 and PT110, though much more pronounced with the former. These results imply that PTX60 has good reactivity with SCA1100 as it bonds well to it, smoothing out its surface, thereby mitigating the interfacial thermal resistance that it forms with PPS when the two are compression molded into a composite. These results, however, do not imply that a higher amount of SCA1100 will ensure a higher thermal conductivity in the a composite containing treated PTX60. The next section addresses the issue of how to determine what the optimal amount of coupling agent should be, amongst other factors.

Weight Cahnge

36

4.4

Design of Experiments

Design of Experiments (DOE) is a systematic approach to investigating, understanding and optimizing system or process. It comprises a series of structured tests in which planned changes are made to the input variables in this case, changes in process conditions or amount of coupling agent, for example of a process. The effects of these changes on a pre-defined output in this case, thermal conductivity are then assessed using statistical software such as MATLAB. DOE is widely used in multivariate data analysis since it allows a judgement on the significance to the output of input variables acting alone, as well input variables acting in combination with one another. Traditional one-factor-at-a-time (OFAT) testing always carries the risk that the experimenter may find one input variable to have a significant effect on the output while failing to discover that changing another variable may alter the effect of the first (i.e. some kind of dependency or interaction). This is because the temptation is to stop the test when this first significant effect has been found. In order to reveal an interaction or dependency, 'one change at a time' testing relies on the experimenter carrying the tests in the appropriate direction. However, DOE plans for all possible dependencies in the first place, and then prescribes exactly what data are needed to assess them i.e. whether input variables change the response on their own, when combined, or not at all. In terms of resource the exact length and size of the experiment are set by the design (i.e. before testing begins). Three types of DOE exist which may be used in our experiments: 1) Full Factorial DOE, which accounts for all possible combinations of input variables, 2) Fractional Factorial DOE, which exploits the sparsity-of-effects principle to expose information about the most important features of the problem studied, while using a fraction of the effort of a full factorial design in terms of experimental runs and resources, and 3) the Taguchi Method, which is similar to the Fractional Factorial method, but relies on analysis of variance (ANVOA) to define the list of experiments needed to be run.

37

For this thesis, it was determined that a Taguchi orthogonal-array DOE would be the most efficient; two such arrays were to be constructed, one for samples with an LDPE matrix, and the other for samples with a PPS matrix. The first step in detailing these arrays was to list all control factors known (or suspected) to have an effect on thermal conductivity of the resultant composite2: 1. Coupling Agent Treatment (stirring) Condition: Three stirring conditions would be studied: 10 minutes at room temperature, 20 minutes at 60C, and 20 minutes at 60C 2. Amount of Coupling Agent: Per the recommendation of the supplier of SCA1100, Struktol, three dosages of coupling agent would be attempted: 3 parts of SCA1100 per 100 parts of Boron Nitride (3 pph), 8 pph, and 15 pph. 3. Weight % of treated PTX60 in a thermal conductivity Sample: Six potential levels would be considered: 5%, 10%, 25%, 33.3%, 50% and 74%. This allows us to gauge the effect of coupling agents across a wide spectrum of different compositions. In summary, 3 control factors were identified: the first and second have three design levels, and the third has six design levels. If we were to run a full factorial DOE against all these factors, we would have to test 54 prototypes, which would be too expensive and too time-consuming. Therefore, using MINITAB, we determine we arrive at the following testing arrays: (1) An L9 DOE for samples consisting of a PPS matrix, and (b) An L12 DOE for samples with an LDPE matrix. These arrays allow us to minimize the number of experimental runs while still gaining information of how different control factors affect the thermal conductivity independently and collectively. A graphical summary of all the chosen experiments can be seen in figures 30 and 31 on the next two pages.

2 The type of coupling agent was also identified as a control factor during the literature review phase, however, since no coupling agents were found that can withstand the process conditions currently used in prototyping samples, only SCA1100 is considered.

38

LDPE matrix

Type of Coupling Agent

Coupling agent treatment condition

Amount of Coupling Agent

wt% of agent-treated PTX60 in a thermal conductivity sample

3 pph SCA 1100 + PTX60

33 wt%

74 wt%

50 wt%

33 wt% SCA 1100 + PTX60 at 60 for 10 minutes 8 pph SCA 1100 + PTX60 25 wt%

10 wt%

5 wt%

3-aminopropyltriethoxysilane (SCA1100)

15 pph SCA 1100 + PTX60

33 wt%

50% SCA 1100 + PTX60 at 60 for 20 minutes 8 pph SCA 1100 + PTX60 33 wt%

50% SCA 1100 mixed with PTX60 at room temperature for 10 minutes 8 pph SCA 1100 + PTX60 33 wt%

Styrylethyl trimethoxysilane

[Methoxy(polyethyleneoxy) propyl] trimethoxysilane

Figure 30: Summary of all compositions to be tested, using an LDPE matrix, as per a Taguchi L-27 DOE

39

Figure 31: Summary of all compositions to be tested, using a PPS matrix, as per a Taguchi L-27 DOE

Note the red cells in figure 30 on the previous page. These represent experimental runs which have failed since they were carried out using LDPE in pellet form. The samples produced using this method were extremely brittle as the LDPE pellets did not melt during the compounding, but rather got embedded within the PPS. Nevertheless, the information lost from the DOE due to the failure of these samples is not severe This is because there is an additional array (fig 31) which carries out similar tests, the results of which may, with caution, be extended to make conjectures about samples with an LDPE matrix. This is explored in the next section.

40

4.5

Thermal Conductivity Results

Chart 5: Thermal Conductivity Results: Treated vs. Untreated PTX60 in PPS matrix
10 9 Thermal Conductivity (W/m.K) 8 7 6 5 4 3 2 1 0 0% 10% 20% 30% 40% 50% 60% 70% 80%
Untreated PTX60 Treated with 8 pph SCA1100 Treated with 3 pph SCA1100 Treated with 15 pph SCA1100

wt% of PTX60 Boron Nitride

Chart 5 above summarizes the results of all experiments runs at the same treatment condition of 10 minute stirring at 60C for prototypes with a PPS matrix. Immediately, we notice that there is an almost linear relationship between Boron Nitride content and thermal conductivity, with the highest being 8.8 W/m.K at 74 wt% Boron Nitride very close to the desired goal of 10 W/m.K. This figure is 13% higher that the thermal conductivity obtained for untreated 74 wt% Boron Nitride, indicating the coupling agent has achieved its purpose of improving of the interface between matrix and particles, thereby minimizing fillermatrix thermal contact resistance. This improvement was also observed at the 33 wt% Boron Nitride
1.7 Thermal Conductivity (W/m.K) 2.9 2.7 2.5 2.3 2.1 1.9

41

composition, where the treated sample performed almost 40% better than its untreated counterpart. Next, we look at the effect of amount of coupling agent on thermal conductivity; this comparison was carried out on 33 wt% Boron Nitride prototypes, and the results of these tests are shown in the inset on chart 5.

Given that all three concentrations of SCA1100 yielded conductivities above that achieved with untreated PTX60, we conclude that all silane treatments were effective in increasing the thermal conductivity of the composite, though to varying degrees. As the amount of silane coating on the particles increased, the thermal conductivity was enhanced more, until the silane concentration reached 8 pph. Further increase of the silane concentration to 15 pph caused the thermal conductivity to decrease. Hence, silane 8 pph treatment was the most effective. This means that the coating resulting from the silane treatment must be sufficiently thick in order for the treatment to be fully effective. The coating serves as an interlayer at the fillermatrix interface, thereby improving the quality of the interface. However, if the coating is too thick, the interlayer will become less effective or even a thermal barrier, thereby decreasing the thermal conductivity.

42

Turning our attention to LDPE samples, we will now be able to understand the effect of treatment conditions on thermal conductivity, as well as compare the effectiveness of LDPE and PPS as matrices for our composites.

Chart 6: Thermal Conductivity Results: Different Treatment Conditions

4.5 Thermal Conductivity (W/m.K) 4 3.5 3 2.5 2 1.5 1 0.5 0 60 for 10 mins 60 for 20 mins LDPE 33% PTX60 22 for 10 mins 60 for 10 mins PPS 60 for 10 mins 60 for 20 mins LDPE 50% PTX60 22 for 10 mins 60 for 10 mins PPS

Looking at chart 6 above, we observe that the conditions under which PTX60 is treated have a minimal effect on thermal conductivity regardless of composition. That is to say, stirring PTX60 and SCA1100 at 60C for 20 minutes does not achieve any better a coating than does stirring them for 10 minutes at room temperature. Therefore, to save time and energy, it is recommended for future research to carry out the stirring at the latter condition. We can also observe from chart 6 that PPS is a marginally better matrix than LDPE as it manages to achieve, on average, an 8% higher thermal conductivity. This is likely due to the fact that the functional groups on SCA1100 bond better to PPS than they do with LDPE. Further, LDPE has less tendency to crystallize than PPS, therefore diminishing the thermal conductivity of the matrix in the final composite.

43

Referring back to Design of Experiments, notice how, using a Taguchi DOE, we were able to reduce the number of experiments by concluding from the LDPE results in chart 6 that the treatment conditions are inconsequential, therefore forgoing the need to test PPS samples at each process condition.

4.6

SEM Analysis

In order to study the effect of coupling agents on the morphology of the samples, four prototypes were sectioned for SEM analysis, of which two comprised on a PPS matrix embedded with: 1. 33 wt% PTX treated with 8 pph SCA1100 2. 33 wt% PTX treated with 8 pph SCA1100 And the other two comprised an LDPE matrix embedded with 3. 33 wt% PTX treated with 8 pph SCA1100 4. 53 wt% PTX treated with 8 pph SCA1100

44

(a)

(b)

Figure 32: SEM micrographs of a PPS matrix embedded with 33 wt% PTX60 (a) as-received, (b) treated with SCA1100 at 60C for 10 minutes. 500X magnification.

Figure 32 shows SEM micrographs of the cross-section of Boron Nitride-PPS composites containing as-received BN particles (fig 32a) and silane-treated BN particles (fig 32b). Figure 32a shows cracks, bare particles, and holes caused by particle pull-out due to the poor interface between particles and matrix. Figure 32b shows fewer cracks, less bare particles and less holes, indicating the improvement of the interface. This is in line with the thermal conductivity results in section 4.5 which show that the treated Boron Nitride samples performed substantially better than their untreated counterparts.

Figure 33: 33 wt% surface-treated PTX60 in PPS matrix

Figure 34: 50 wt% surface-treated PTX60 in PPS matrix

Figures 33 and 34 above show PPS composite samples embedded with treated 33% (fig 33) and 50% (fig 34) PTX60 Boron Nitride. In both cases, we observe that the Boron Nitride particles have been coated with a layer of Silane. This improves the matrix-

45

filler bonding and reduces the steep interfacial directional changes which were previously resulting in severe phonon scattering leading to poor thermal conductivity.

Figure 35: 33 wt% surface-treated PTX60 in LDPE matrix

Figure 36: 50 wt% surface-treated PTX60 in LDPE matrix

Figures 35 show LDPE composite samples embedded with treated 33% (fig 35) and 50% (fig 36) PTX60 Boron Nitride. In those cases, we observe the same coating layer on the Boron Nitride particulates, but far less pronounced than in the PPS images, indicating that the preparation of the treated Boron Nitride was not as effective as it was in the previous cases. As such, it is recommended that these samples be retested using a new batch of PTX60 treated with 8 pph SCA1100. Finally, we note from figure 37, which shows a low magnification image of an LDPE-PTX60 composite that the composites consisting of an LDPE matrix produce an excellent finish with very few microvoids, gaps or imperfections as is the case with PPS matrix samples (see figures 15 through 18).
Figure 37: 33 wt% surface-treated PTX60 in LDPE matrix. Low magnification

46

Future Research Directions

It would seem that this research project has reached its limits, with the highest thermal conductivity still well short of predicted values being obtained at the maximum 74 wt% Boron Nitride (with coupling agent). However, expanding on the results obtained in this thesis, much work can be done in order to further close the gap between experimental values and theoretical predictions. This section outlines three such methods.

5.1

Multi-Modal hBN fillers

So far, the focus has been on using hexagonal Boron Nitride (hBN) embedded in PPS in order to produce a composite with appreciable thermal conductivity. Another form of Boron Nitride exists, however, which may be used in tandem with hBN to improve upon the current results: Cubic boron nitride (cBN), a diamond-like allotrope of Boron Nitride, exhibits excellent mechanical and thermal properties due to its microstructure. It is synthesized by heating powdered hBN to 1500C at a pressure in excess of 60 kbars. This process transforms the atomic structure from hexagonal to cubic, making the material hard and of high abrasivity. hBN and cBN are often referred to as modes of Boron Nitride. When compounded with a resin and compression molded, they are equally good in terms of thermal conductivity [25]. However, due to its hardness and abrasivity, cBN must be used with caution, and in small amounts, as it may damage the compression molding. In order to ensure the formation of a near-perfect conductive network throughout the composite, maximum packing of the Boron Nitride in the matrix must be carried out. To achieve a high packing density composites, several researchers have found the use of large size particles with multi- modal particle size distribution and low aspect ratio with smooth surface texture to be very most effective [9][25][31]. The theory behind the superiority of multi-modality relies on the idea of combined use of whiskers (hBN) and

47

particles(cBN) enhances the formation of a thermally conductive networks throughout the composite[29]. The large particle size, on the other hand, is desired to minimize the scattering of phonons due to the interfacial thermal barrier. Moreover, the use of large particle size tends to form fewer thermally resistant junctions of the polymer layers than the small particle size at the same filler content. Finally, the smooth surface texture ensures that there is good adhesion between the BN and resin.

5.2

Ishida Method

Perhaps one of the best and most encouraging papers written on the topic of thermallyconductive polymers is by Ishida and Rimdusit, who managed to obtain a thermal conductivity of 32.5 W/m.K by embedding 88 wt% hexagonal BN (grade HCJ48)3 in as-synthesized bisphenol-A-methylamine type polybenzoxazine. They note that the remarkably high value was obtained using the well-recognized concept of thermal management in composite materials by maximizing the formation of conductive networks while minimizing the thermal barrier resistance along the heat flow path. The concept was accomplished by using highly thermally conductive filler with a matrix resin which has low melt viscosity and good adhesion to the filler. In addition, a large particle size with multimodal particle size distribution was used. Boron nitride and polybenzoxazine have properties that meet all these requirements and thus exhibit a very high thermal conductivity value [...] Boron nitride-filled polybenzoxazine has many outstanding properties which makes it suitable for an application as a molding compound
Figure 38: Ishida and Rimdusit's results for BN-saturated polybenzoxazine

supplied by Advanced Ceramics, http://www.advceramics.com/

48

for the electronic packaging industry and other applications with high thermal conductivity. [9] 5.3

Multifunctional Fillers

As was pointed out in section 3.3, the likely reason why there is a large gap between the obtained and the expected thermal conductivity values is that, instead of agglomerating together in a close-packed arrangement to form a thermal conductive network, the BN filler particulates tend to cluster together in a random arrangement, thus leaving gaps in the conductive path.
Figure39: Diagram showing thermal conductive pathways in the matrix

These gaps may be bridged using carbon nanotubes (CNT), carbon fibres or graphene [40] as diagrammed in figure 39. One study, conducted by Agarwal et al using various compositions and orientations of carbon fiber and CNT fillers in a polycarbonate matrix concluded that composites containing hybrid mixtures of two fillers show higher thermal conductivity due to increased contacts between the microfibers that are promoted by the presence of the nanofibers, especially when microfibers are aligned. [41]

Other potential fillers include nano-scaled graphene platelets (NGPs), which can be obtained from American Elements [42] and carbon fibres, both of which exhibit excellent thermomechanical properties.

49

VI

Conclusion

A thermal conductivity of 8.8 W/m.K was obtained using composite consisting of 74 wt% Boron Nitride embedded in a poly(p-phenylene sulphide) matrix. This remarkably high value was obtained using the well-recognized concept of thermal management in composite materials by maximizing the formation of conductive networks while minimizing the thermal barrier resistance along the heat flow path. This was accomplished by (1) using a resin which has a low melt viscosity and excellent affinity with the filler to ensure that air gaps within the composite are minimized, (2) surface treating the filler with a coupling agent, which improved the adhesion of Boron Nitride to the matrix, thereby reducing phonon scattering at interfacial barriers and lattice defects and bringing the percolation threshold within reach, (2) utilizing an optimized compression molding pressure to preserve the thermomechanical integrity of Boron Nitride, and (3) exploiting the spherical shape of PTX60-grade Boron Nitride to maximize the packing of filler throughout the matrix, thereby increasing the likelihood of filler-filler contact, and reducing the percolation threshold. Though LDPE has shown far better affinity to Boron Nitride than PPS in SEM images, BNLDPE composites seem to have a high percolation threshold, and therefore would require the use of a different coupling agent, or Boron Nitride contents in excess of 50 wt% in order to achieve the desire goal of 10 W/m.K. However, a better-established method would be the use of epoxy resins such as polybenzoxazine, combined with multi-modal Boron Nitride filler, which, together, have shown potential to reach up to 32 W/m.K.

50

Acknowledgements: The author thanks Dr. Naguib for his continuous supervisory support and Dr. Leung for his superb mentoring, as well as Mr. Khan for his guidance and suggestions.

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