Thermal Conductivity of Reinforced Composites for Electrical Applications

Peter Zweifel and Sian F. Fennessey

ABB Switzerland Ltd. Corporate Research 5405 Baden-Dttwil, Switzerland sian.fennessey@ch.abb.com

Abstract- Thermal conductivity and resistance at interfaces plays a major role in the heat transfer through a material. The potential advantages and uses of submicron and micron sized fillers for thermal management in reinforced composites used in electrical insulation applications are investigated. The affect of filler material, size, concentration, and aspect ratio on the processing, thermal, mechanical, and electrical properties of reinforced epoxy laminates is determined. The affect of submicron filler on the matrix and fiber reinforced composite modulus and flexural strength is determined. The dielectric dissipation factor tangent and the permittivity r of the composite are measured; a significant increase in tangent is not desirable. Improvement in thermal properties of the resultant composite material with minimal change in the dielectric properties is reached.

II.

EXPERIMENTAL

I. INTRODUCTION Hollow composite insulators are used in circuit breakers, bushings, instrument transformers and cable terminations; ABB currently provides hollow composite insulators in the voltage range of 72kV-800kV and in lengths up to 10m. The glass reinforced epoxy tube is designed with respect to mechanical properties and heat produced during operation and current interruption; in gas insulated circuit breakers, the tube must also withstand decomposed SF6 [1]. Silicone rubber is often used as an external insulation on the composite tube; the thermal conductivity silicone rubber used in power devices is typically in the range of 0.21 W/mK to 0.57 W/mK, while that of a bisphenol-A based epoxy is approximately 0.2W/mK on average. Submicron and micron sized ceramic fillers are examined for the enhancement of the thermal conductivity of glass reinforced epoxy composites; composites with high thermal conductivity are beneficial in electrical applications requiring good heat dissipation through the housing and insulation. Fillers may be used to enhance the thermal conductivity of a material, although mechanical and processing properties of the material may be affected (depending upon the type, size, shape, and dispersion of the filler material) [2]. In the present study boron nitride (BN), silicon carbide (SiC), and diamond are examined.

A. Materials CY225/HY925 epoxy resin system is used as received from Huntsman Advanced Materials; CY225 is a diluted bisphenol A (average molecular weight of <700) and HY925 is a preaccelerated methyltetrahydrophthalic anhydride (MTPHA) curing agent. A masterbatch of 40 wt% BN and 40 wt% silicon carbide (SiC) with an average particle size of 500nm dispersed in a bisphenol A epoxy is supplied by Nanosperse, USA.; the masterbatch is diluted with CY225 and cured with HY925. Boron nitride (BN) powder (NX1) and platelets (HCPL) are supplied from Momentive Performance Materials, DE; NX1 has a mean particle size of 700 nm and HCPL is between 9-12 m according to the supplier. Boron nitride particles are dispersed in CY225 and cured with HY 925. Diamond filler with a particle size range of 0-0.5 m and 3-6 m supplied by Qiming, CN is studied in EPH 845/ EPH 05389 resin system from Hexion AG filled with silica flour from Quarzwerke. EPH 845 is a mixture of bisphenol F and bisphenol A, and EPH 05389 is an accelerated MTPHA curing agent. B. Sample Preparation Filler is combined with the resin system and cured at 140 C for 8 hours. E-glass woven fabric (390 g/m2) is used as received from Ster Swiss Composite, CH; a twill 1/7 weave pattern is used in all experiments. Laminates are prepared by resin transfer molding (RTM); 30 vol% glass laminates are produced. C. Characterization The glass transition temperature Tg is measured using a Perkin Elmer DSC 7 with a heating rate of 10 C/min; baseline subtraction is used. Viscosity is measured with a CVOR Bohlin rheometer by parallel plate (40 mm diameter) with a gap distance of 500 m and a constant shear rate of 10 s-1; viscosity is measured over a temperature range of 3090 C at a heating rate of 3 C/min. Thermal conductivity is measured with an Anter Model 2022 thermal conductivity meter according to ASTM E1530 in the temperature range

978-1-4244-6300-8/10/$26.00 2010 IEEE

of 40 C to 100 C. Flexural properties are measured with a Zwick Roell tensile machine according to EN ISO 178 for the particle filled composite and EN ISO 14125 for the fiber reinforced composite. The relative permittivity r and the dielectric dissipation factor tan are measured between 1106 Hz between 40 C and 140 C (at 20 C steps) using a Novocontrol spectrometer according to CEI IEC 250. Particle distribution is observed by scanning electron microscopy with a Vega XMU SEM from Tescan USA Inc.; energy dispersive x-ray spectroscopy (EDX) is used to confirm the presence of filler in fiber reinforced composites. Polished samples are coated with gold or carbon prior to observation. III. RESULTS

use of h-BN with an approximate particle size of 500 nm. An improvement in particle dispersion had been expected in the h-BN (500 nm) masterbatch, although large agglomerates are observed (Fig. 1). B. Boron nitride and fiber reinforced composites Fiber reinforced composites are prepared by resin transfer molding (RTM); laminates with 30 vol% E-glass fiber are prepared. Viscosity limitations affect the maximum filler weight percent impregnated into the glass fabric; typically the viscosity of the filled system is increased to a greater extent as the particle size of the filler is decreased (increase in available surface area). Although as the filler particle size is decreased, the visible signs of filtering during impregnation are decreased. Energy dispersive x-ray spectroscopy (EDX) confirms that BN NX1 particles, with a mean particle size of 700 nm, are impregnated between the individual fibers of the tow; BN NX1 particles are observed to be dispersed throughout the matrix of the reinforced laminate (Fig. 2). However, BN HCPL platelets, with a mean particle size of 9-12 m, do not impregnate the fiber tows although they appear well dispersed in the matrix between the fabric sheets (Fig. 3). It is expected that better impregnation of the filler particles into the fiber tows or bundles is obtained as the particle size is decreased; good

A. Boron nitride Hexagonal crystalline boron nitride (h-BN) particles are combined with the bisphenol A epoxy resin system and characterized; results are summarized in Table I. The glass transition temperature Tg of the neat epoxy T g decreases from 124.5 C to a minimum of 120.5 C with the addition of h-BN as a function of weight percent filler, regardless of particle size. As expected the viscosity of the system is increased with the addition of filler as a function of particle size and shape. The viscosity of the epoxy is increased from 0.094 Pas to 5.58 Pas and 0.499 Pas with 20 wt% BN NX1 (700 nm) and BN HCPL (9-12 m) at 65 C, respectivley. The thermal conductivity of the epoxy matrix is increased as the weight percent of h-BN is increased, regardless of particle size or shape [3] (Table I); the thermal conductivity of solid h-BN is between 40 W/mK and 120 W/mK. The affect of the filler shape on the increase of thermal conductivity is not clearly demonstrated due to the difference in examined fillers average particle size. The modulus E of the matrix is increased with the addition of hBN as a function of weight percent filler, while the maximum strength max tends to decrease; the nanocomposite is stiffer than the reference. The relative permittivity r increases with the addition of h-BN; the dissipation loss factor tan increases significantly with the
TABLE I

Fig. 1. Scanning electron micrograph of 27 wt% h-BN with an average particle size of 500 nm dispersed in bisphenol A epoxy

THERMAL CONDUCTIVITY, MECHANICAL AND DIELECTRIC PROPERITES OF THE REFERENCE BISPHENOL A EPOXY RESIN SYSTEM WITH THE ADDITION OF BORON NITRIDE AS A FUNCTION OF PARTICLE SIZE, SHAPE, AND WEIGHT PERCENT FILLER

Thermal Conductivity, (W/mK) Reference: CY 225/ HY925 27 wt% BN (500nm) 7.7 wt% BN NX1 (700nm) 14.3 wt% BN NX1 20 wt% BN NX1 20 wt% BN HCPL (9-12m) 0.19 0.7 0.27 0.38 0.45 0.54

Flexural Modulus, E (GPa) 3040 5680 3140 3670 4070 5070

Maximum strength, max (MPa) 110 84 120 120 100 85

Relative Permittivity, r* 3.5 3.8 3.6 3.6 3.7 3.7

Dissipation loss factor, tan * 0.0029 0.0047 0.0030 0.0029 0.0029 0.0025
*40 C, 50 Hz

Fig. 2. Scanning electron micrograph (SEM) of (A) 10 wt% BN NX1 dispersed between the individual fibers of a tow and the EDX spectrum (B) of an area of the matrix between the fibers. (B) shows the presence of boron (B) and nitrogen (N) from the filler, carbon (C) and oxygen (O) from the epoxy, calcium (Ca) and silicon (Si) from the glass fibers and gold (Au) from sputter coating

500nm are characterized in a bisphenol A epoxy resin system; the thermal conductivity of solid SiC is between 25 W/mK and 100 W/mK. The particles appear well dispersed within the resin, although large agglomerates are observed (Fig. 4). The viscosity of the mixture is acceptable for RTM, but no laminates are prepared due to significant shrinkage and cracking upon curing for large sample sizes. The cause of the shrinkage is not presently clear; small sample sizes could be prepared and used for thermal conductivity measurements. The thermal conductivity of the matrix is increased by 68 % with the addition of 27 wt% SiC in comparison to the reference (Table III). The relative permittivity r and the dissipation loss factor tan increase significantly with the use of SiC as expected since SiC is a semiconductive material. D. Diamond Diamond submicron and micron filler is examined in a silica filled epoxy resin system to avoid sedimentation of the diamond. The silica is the main source of the increase in thermal conductivity of the reference system. The use of diamond filler leads to a further increase of the thermal conductivity of the composite and a surprising decrease in the relative permittivity r and dissipation loss factor tan in comparison to the reference (Table IV). Micron size diamond particles increase the thermal conductivity to a greater extent than submicron particles at the same weight percent due to more direct particle contacts of the high thermal conductivity filler. Laminates are not produced from the described diamond fillers due to sedimentation and expected processing difficulties.

Fig. 3. Scanning electron micrograph (SEM) of (A) 21.7 wt% BN HCPL platelets dispersed between the fiber tows of the glass fabric and (B) of the platelets impregnating the matrix surrounding outer fibers of the tow or bundle. Platelets are not found between the individual fibers of the tow.

impregnation is desirable. In addition to increasing the overall thermal conductivity of the composite, ceramic filler is used to reduce the thermal mismatch between the glass fiber and the epoxy; the typical themal conductivity of glass used in power devices is between 0.8 W/mK and 1.2W/mK [5]. The overall thermal conductivity of a bisphenol A epoxy with 30 vol% E-glass laminate is increased by 44 % with the addition of 10 wt% BN NX1 (700nm) and by 85% with 18 wt% BN (500 nm) (Table II). The flexural modulus, E, of the resultant fiber reinforced composite is decreased with the use of the BN masterbatch. C. Silicon carbide Silicon carbide (SiC) particles with an average diameter of
TABLE II
THERMAL CONDUCTIVITY AND MECHANICAL PROPERTIES OF FIBER REINFORCED NANOCOMPOSITES AS A FUNCTION OF h-BN PARTICLE SIZE, SHAPE AND WEIGHT PERCENT; 30vol% E-GLASS FABRIC WITH TWILL1/7 IS USED IN ALL COMPOSITES

Thermal Conductivity, (W/mK) Reference: CY 225/ HY925/ E-glass 18 wt% BN (500nm) 10 wt% BN NX1 (700 nm) 21.7 wt% BN HCPL (9-12 m) 0.27 0.5 0.39 0.59

Flexural Modulus,E (GPa) 15100 14700 16000 18200

Maximum strength, max (MPa) 350 360 360 390

*40C, 50Hz

Fig. 4. Scanning electron micrograph of 27 wt% SiC with an average particle size of 500 nm dispersed in bisphenol A epoxy TABLE III
THERMAL CONDUCTIVITY AND DIELECTRIC PROPERTIES OF THE REFERENCE BISPHENOL A EPOXY RESIN SYSTEM WITH THE ADDITION OF SILICON CARBIDE

Reference: CY 225/ HY925 27 wt% SiC (500nm)

Thermal Conductivity, (W/mK) 0.19 0.32

Relative Permittivity, r* 3.5 6.2

Dissipation loss factor, tan * 0.0029 0.027

*40 C, 50 Hz

TABLE IV
THERMAL CONDUCTIVITY AND DIELECTRIC PROPERTIES OF THE SILICA FILLED REFERENCE EPOXY RESIN WITH THE ADDITION OF DIAMOND AS A FUNCTION OF PARTICLE SIZE

Reference: EPR 845/EPH 05389/ 65 wt% Silica 7.92 wt% Diamond (00.5m) 7.92 wt% Diamond (36m)

Thermal Conductivity, (W/mK) 0.77 0.85 0.92

Relative Permittivity, r* 4.7 4.6 4.5

Dissipation loss factor, tan * 0.034 0.028 0.026

*40C, 50Hz

may be used to enhance the thermal conductivity of composite parts, although the increase in electrical permittivity of the composite is too great for electrical insulation applications. Diamond is an ideal filler for electrical insulation; diamond enhances the thermal conductivity and slightly reduces the electrical permittivity of the epoxy resin. Due to the high density of diamond, it could not be used in the RTM epoxy resin system in this study and was not a candidate for impregnation by RTM. Ongoing work associated with this study includes the evaluation of the electrical breakdown strength of the fiber reinforced epoxy composites with filler by short and long term testing. ACKNOWLEDGMENT The authors would like to thank M. Schneider and W. Gerig for their support and advice regarding RTM, D. Zegarac for dielectric measurements, and C. Lang for EDX analysis. REFERENCES
[1] [2] [3] [4] Remote Plant Plays Key Role in ABB Insulator Business, INMR Quarterly Review, vol. 13, pp. 54, 2005. Schadler LS. Polymer-based and polymer-filled nanocomposites. In: AjayanPM, Schadler LS, Braun PV, editors. Nanocomposites science and technology. p.77, 2003. Han, Z.; Wood, J.W.; Herman, H.; Zhang, C.; G.C. Stevens Thermal Properties of Composites Filled with Different Fillers, IEEE International Symposium on Electrical Insulation, pp. 497, 2008. Brtsch, R.; Lutz, A.; Liptak, G.; R. Schuler New High Voltage Insulation with Increased Thermal Conductivity, IEEE Electrical Manufacturing and Coil Winding Conference, pp. 323, 1993

IV.

CONCLUSIONS

Efficient cooling and heat transfer is an important topic for a wide range of electrical products in medium and high voltage applications. Particularly as products are expanded to allow for higher energy (or power density) applications and at the same time product sizes are reduced, consideration of thermal management through engineering design and materials choice is of increasing importance. The use of submicron ceramic fillers for the enhancement of the thermal conductivity in glass reinforced composite parts is proposed. Particle dispersion, size, and material type are shown to affect the thermal conductivity and processing, mechanical, and electrical properties of the matrix and the fiber reinforced composite. Boron nitride particles with a diameter of 500 nm and less exhibit good impregnation; composite insulation with thermal conductivity of up to 0.6 W/mK can be achieved with the addition of boron nitride (regardless of particle size or shape). Silicon carbide