Journal Pre-proofs

Silicone-based alumina composites synthesized through in situ polymerization

for high thermal conductivity and thermal stability

Yi Liu, Zhenxing Chen, Yuqiu Shen, Yong Zhou, Dan Wang, Zuomin Lei,
Wenchao Feng, Zhongyu Min

PII: S0167-577X(19)31634-9
DOI: https://doi.org/10.1016/j.matlet.2019.127002
Reference: MLBLUE 127002

To appear in: Materials Letters

Received Date: 27 August 2019

Revised Date: 24 October 2019
Accepted Date: 11 November 2019

Please cite this article as: Y. Liu, Z. Chen, Y. Shen, Y. Zhou, D. Wang, Z. Lei, W. Feng, Z. Min, Silicone-based
alumina composites synthesized through in situ polymerization for high thermal conductivity and thermal stability,
Materials Letters (2019), doi: https://doi.org/10.1016/j.matlet.2019.127002

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Silicone-based alumina composites synthesized through in situ polymerization for high thermal

conductivity and thermal stability

Yi Liu1, Zhenxing Chen1,2,3,*, Yuqiu Shen1,*, Yong Zhou1, Dan Wang1, Zuomin Lei1, Wenchao Feng1,

Zhongyu Min1
1 School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai, 519082, P. R.

China
2 School of Materials Science and Engineering, Baise University, Baise 533000, P. R. China
3The Key Laboratory of Low-Carbon Chemistry & Energy Conservation of Guangdong Province,

510275, P.R. China

* Corresponding author: Tel: +86 13430309839; E-mail:2764927916@qq.com; shenyuqiu8@163.com

Abstract

Silicone-based alumina composites for high thermal conductivity and thermal stability were

fabricated through in-situ polymerization, in which silanol groups were formed by a hydrolysis reaction

with methyltriethoxysilane (MTES), dimethyldiethoxysilane (DMDES) and phenyltrimethoxysilane

(PhTMS). Then, the silanol groups were polymerized in situ on the surface of alumina powders, which

greatly improved the wettability and dispersity of the hybrid alumina powders in the matrix. When the

hybrid alumina powder loading was 80 vol%, the silicone-based alumina composites presented a

thermal conductivity of 2.92 W m-1 K-1, which was 15.3 times higher than that of the pure silicone resin.

Furthermore, the silicone-based alumina composites showed a high thermal stability with a weight loss

of less than 2.2 % at 400 °C.

Keywords: polymeric composites; in situ polymerization; thermal conductivity; thermal properties

1. Introduction

Polymer composite materials have attracted a great deal of attention in heat dissipation applications

due to their excellent electrical insulation, low thermal expansion and high modulus [1-3]. As one of

the typical polymeric materials, silicone resin has received widespread attention for its resistance to

oxidative degradation, low toxicity, excellent electrical insulation, high chemical stability and thermal
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stability [4, 5]. However, its thermal conductivity is too low to meet the heat-dissipating requirement of

modern electronic materials [6]. To improve the thermal conductivity of the silicone-based composites,

many kinds of thermal conductive fillers have been added such as BN [7], Al2O3 [8], ZnO [9], AlN [10]

and Al2O3/BN [11], and graphene oxide-hexagonal boron nitride (RGO-hBN) [12]. To form effective

thermally conductive pathways, the fillers should be modified to a hydrophobic core-shell structure so

as to reduce the interfacial resistance between the matrix and fillers [13]. The silane coupling agents

have been widely applied to modify a the filler surface [14]. However, large interfacial resistance still

exists in the core-shell structures because of the steric hindrance effect of the surface modifier.

In this work, the thermal conductivity of composites was improved via in situ polymerization.

Spherical Al2O3 was chosen as the thermal conductive filler due to its thermal conductivity (30-40 W

m-1 K-1), electric insulation, chemical stability and low cost. The silanol fabricated by a hydrolysis of

methyl methyltriethoxysilane (MTES), dimethyl diethoxysilane (DMDES) and phenyltrimethoxysilane

(PhTMS), was directly mixed with the spherical Al2O3 powder to polymerize in situ on the surface of

the spherical Al2O3 powder. Because of the negligible steric hindrance of silanol, the thermal

conductivity of the as-prepared silicone-based alumina composites could be greatly improved.

2. Experimental method

2.1. Preparation of silanol and silicone/Al2O3 composites

Taking their synergistic effect into account, 10 μm and 0.5 μm of Al2O3 powders (purchased from

Yaan Bestry Performance Materials Corporation, Sichuan Province, China) were mixed to form hybrid

fillers at a mass ratio of 7:3.

MTES, PhTMS, DMDES, H2O and HNO3 (dilute solution) were mixed with a molar ratio of

DMDES:PhTMS:MTES:H2O:HNO3 = 1:0.7:1.3:11:0.0005, in which PhTMS was used as a resin

modifier to enhance the thermal stability; in addition, its π-π conjugated structure had a positive effect

on the thermal conductivity [15]. The mixture was stirred at 60 °C for 1.5 h to obtain the silanol

groups.

Next, the hybrid Al2O3 powders were added into the silanol mixture at a certain proportion and

stirred for 30 min at room temperature so that the powders could be uniformly dispersed and reacted
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with silanol to form a compact shell. Finally, the slurry was concentrated at 80 °C in a high-speed

mixer for 20 min and vacuum defoamed for 5 min.

2.2. Characterization

Fourier transform infrared spectroscopy (FTIR, PerkinElmer Spectrum Two, America) was used to

characterize the chemical bonding configuration of the silanol groups and the composite. The

morphology of the composites was characterized by a scanning electron microscope (SEM, JEOL JSM

6510, Japan). X-ray diffraction (XRD, PANalytical B.V, Empyrean, Netherlands) was used to observe

the crystal transformation of composites. Thermogravimetric analysis (TGA, Netzsch TG209F1 libra,

Germany) was used to investigate the thermal properties of composites. A thermal conductivity test

was carried out using a TPS model with a 2# kapton sensor (DZDR-S, China). To fabricate specimens

for the thermal conductivity tests, a concentrated slurry was poured into a square PTFE template (4 mm

×4 mm ×3 mm). After heating at 60 °C for 1 h and 100 °C for 2 h, the specimens were then hot

compressed at 10 MPa.

3. Results and discussion

3.1. Silanol-modified hybrid Al2O3 powders

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Fig.1. (a) FTIR spectra of silanol, Al2O3 and silanol-modified Al2O3 powders; (b) surface

modification mechanism of Al2O3 powders; and (c) XRD results of silicone, Al2O3 and an 80 vol%

silicone/Al2O3 composites

The FTIR spectra of silanol, Al2O3 powders and modified Al2O3 powders are shown in Fig. 1a. The

pristine Al2O3 has no obvious absorbance between 4000 and 1000 cm-1. However, the modified Al2O3

powders exhibit an absorption peak at 2967 cm−1, which presents the stretching vibration of C-H. The

modified Al2O3 has an important absorbance peaks at 1134 and 1091 cm-1, which relates to the Si-O-Si

and Si-OR asymmetric modes. The absorbance peak at 1270 cm-1 corresponds to the stretching

vibrations of Si-CH3, indicating a successful surface treatment of the Al2O3 particles with silanol. The

broad absorption band at approximately around 3337 cm−1 indicates that many more hydroxyl groups

attach to the surface of Al2O3 powders. It is inferred that the -OH on the surface of Al2O3 powders can

react with the -OH in the silanol chain [16]. Surface modification mechanism of Al2O3 powders can be

explained through Fig. 1b. Compared to the XRD patterns of silicone and Al2O3, the composites

exhibited no obvious phase changes after curing at 160 °C (Fig. 1c).

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Fig.2.(a) Morphology of silanol-modified Al2O3 composites; (b-d) Cross-sectional morphology of

silicone/Al2O3 composites (b-d, 1000x magnification): b. 60 vol%, c. 70 vol%, d. 80 vol%.

The cross-sectional morphology of the silicone/Al2O3 composites at an Al2O3 loading of 50 vol%

(Fig. 2) shows that no obvious voids exist on the interface of the Al2O3 powders and silicone resin,

indicating that the silanol group has a good compatibility with the Al2O3 powders, which is very

important for the thermal conductivity of the composites. With an increase in the Al2O3 volume fraction,

the voids in the composites gradually increase, which affects the thermal conductivity of the

composites (Fig. 2b-d).

3.2. The performance of silicone-based alumina composites

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Fig.3 (a)Thermal conductivity as a function of filler loading and (b) TGA curves of the various

silicone/Al2O3 composites.

The effect of hybrid Al2O3 loading on the thermal conductivity of the silicone/Al2O3 composites is

shown in Fig.3a. With the increase in the hybrid Al2O3 loading from 60 vol% to 80 vol%, the thermal

conductivity of silicone/Al2O3 composites improves from 1.67 W m-1 K-1 to 2.92 W m-1 K-1, which is 15

times higher than that of the pure silicone resin (0.19 W m-1 K-1). The negligible steric hindrance of the

silanol-modified Al2O3 powders could increase its connection with Al2O3 powders in order to form an

effective heat conducting pathway [17]. However, as the filler loading is further increased to 85 vol%,

the thermal conductivity drops to 2.43 W m-1 K-1, which could be attributed to the increase in the

number of voids.

Thermal stability is also important for polymer composites. The TGA curves of the silicone/Al2O3

composites are presented in Fig.3b. The onset decomposition temperature is approximately 200 °C.

The Al2O3 powder loadings are 50 vol%, 60 vol%, 65 vol%, 70 vol%, 75 vol% and 80 vol%, and the

weight losses of the composites are 0.48 %, 0.23 %, 0.63 %, 0.32 %, 0.75 % and 0.15 %, respectively.

As the temperature is increased to 400 °C, the weight losses of the composites are 1.45 %, 1.32 %, 1.92

%, 1.72 %, 2.21 % and 1.88 %, respectively, presenting a high thermal stability of the composites. The

weight loss of silicone composites is mainly due to the thermal degradation of the cured silicone

network. The increasing decomposition temperature could be attributed to the Al2O3 surface

modification that increased the binding force between the fillers and silicone; additionally, the fillers

improves the resistance to thermal degradation and hinders the diffusion of decomposition products

from the bulk polymer into the gas phase [18].

4. Conclusion

Silicone-based alumina composites were fabricated through in situ polymerization, in which the

silanol was fabricated by a hydrolysis reaction of MTES, DMDES and PhTMS, and then the hybrid

alumina powders were directly encapsulated with silanol groups in situ polymerization process. In the
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as-prepared silicone-based alumina composites, the Al2O3 powders were uniformly dispersed

throughout the matrix and showed good compatibility with silicone. When the hybrid Al2O3 loading

was 80 vol%, the composites presented a thermal conductivity of 2.92 W m-1 K-1, which was 15.3 times

higher than that of the pure silicone resin, and the composites exhibited a weight loss of 2.2 % when

the temperature was 400 °C. Therefore, the silicone/Al2O3 composites prepared by in situ

polymerization might have great potential for applications in high power density electronic devices.

Acknowledgements

This research was financially supported by the Fundamental Research Funds for the Central

Universities (Grant No. 17lgpy69), the Guangdong Natural Science Foundation (Grant No.

2018A030310331), the Foundation of the Key Laboratory of Low-Carbon Chemistry & Energy

Conservation of Guangdong Province, and the Guangxi Natural Science Foundation (Grant No.

2016GXNSFDA380024).

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We declare that we do not have any conflict of interest.

Highlights:

1. Silicone-based alumina composites were fabricated through in situ polymerization.

2. The wettability and dispersity of hybrid alumina powders in the matrix were improved.

3. Composites with high thermal conductivity and thermal stability were prepared.
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The authors have declared that no conflict of interest exists.

We declare that we do not have any commercial or associative interest that represents
a conflict of interest in connection with the work submitted.