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Cryogenics 35 (1995) 713-716 0 1995 Elsevier Science Limited Printed in Great Britain. All rights reserved INIl-2275/95/$10.

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Thermal properties of polymer/particle composites at low temperatures


M. Jiickel
Dresden University Dresden, Germany of Technology, Institute of Low Temperature Physics, D-01062

With different models, the thermal conductivity of composite materials is calculated on the basis of the thermal conductivity of the matrix and filler, of the volume fraction and shape of the fillers and with consideration of the thermal boundary resistance in the temperature range below 20 K. Measurements of the thermal conductivity and specific heat of epoxy resins with different fillers (needle-shape Ag, HTSC powders) in the temperature range 2-80 K are presented. Comparison of the measured and calculated thermal conductivity of these composites shows that above 20 K, the thermal conductivity is determined to a high degree, by the shape of the fillers. Keywords: thermal conductivity; particle composites; specific heat; epoxy resins

A significant advantage of polymers in low-temperature technology is the possibility of modifying the polymers with fibres or powders, and thus, of modifying the mechanical or thermal properties. In this paper, the influence of fillers in polymers on the thermal properties, especially the thermal conductivity in the low-temperature range, is discussed. A large number of theoretical works have dealt with different models of calculating the properties.

Specific

heat

For the calculation of the specific heat of polymeric composites (cc) with fibre or powder reinforcement (cF) in a matrix (c,), the simple linear equation generally agrees well with experimental data (denoted by subscripts C, F and M, respectively):
cc = ( 1 -fic&+ +fc,

(1)

where f is the volume fraction of the reinforcement. For the glass-fibre reinforcement in epoxy resins, the specific heat, which is calculated from the specific heats of glass fibre and epoxy resin, is only 10 to 20% higher than the measured specific heat of the compound (Figure I ). The reason is that the specific heat is a bulk effect of the solids. The deviation between the measured specific heat of the composites and the specific heat calculated by Equation (1) shows that filler particles or fibres interact with the surrounding polymer layer and that they are able to modify the properties of the bulk material. This interaction modifies the intrinsic energy of the matrix, and, therefore, changes the specific heat. This has been shown in an earlier

Figure 1 Specific heat of glass-fibre composite as a function of temperature: (----) pure epoxy resin; (*) glass fibre; (0) glass-fibre composite; (-_) calculated specific heat by Equation (1)

paper, in which the specific heat of epoxy-resin/particle


composites decreases with increasing peratures above 40 K. filler content at tem-

Thermal materials

conductivity

of particle-composite

For the calculation of the effective conductivity of a composite (h,) it is necessary to know the conductivities of the

Cryogenics

1995 Volume

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Thermal properties

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M. JBckel tration f of the filler. As an example, with Ag or steel spheric fillers, one obtains nearly the same thermal conductivity for the two compounds. Below 20 K the boundary resistance increases with decreasing diameter of the filler particles, and with that, the thermal conductivity of the compound decreases. With embedment of very small particles in the matrix in this temperature range, one obtains solids with very low thermal conductivity7,. For a compound system consisting of a continuous phase with a discontinuous phase as particles of various shapes in either regular or irregular assays, Hamilton and Crosser give for the thermal conductivity:
&=A, A,+(n-

filler and matrix (h,, A,,,,), the volume fraction of the filler ,J the size and shape of the inclusion, and the arrangement of fillers in the matrix. Most real composites have irregular arrangements and nonhomogeneous sizes. Nevertheless, simple models often give useful equations for the calculation of the thermal conductivity of composite materials2,. For many models, thermal-conductivity calculations are based on the assumptions that the properties of the matrix are not altered by any interaction between filler and matrix and that the heat transfer between filler and matrix is ideal. The supposition of an ideal transfer of heat is fulfilled when there is perfect adhesion between the different phases, and the wavelength of the propagated phonons is very small compared with the microscopic irregularities of the filler surfaces or the filler diameter. This is realized for temperatures above 20 K. For temperatures T < lo-20 K, the thermal boundary resistance at the interface between matrix and filler becomes increasingly important owing to the different acoustic impedances of the two materials. The acoustic impedance (p.u) is the product of the ultrasonic velocity v and density p of the material. This boundary resistance (or Kaptiza resistance) increases strongly with decreasing temperature (R, - T). A commonly used model for the calculation of the thermal conductivity of composite materials containing dispersed spheric inclusions is that of Meredith and Tobias. They considered the case of a cubic array of uniform-size spheres and analysed the effect in the neighbourhood of a sphere by 248 of its close neighbours of the thermal stream. The final equation for the effective thermal conductivity of this arrangement is h = h A - 2f + 0.409.B.f c MA +f+ 0.409.Blf3 - 2.1 33C.f3 - 0.906C~f03

l)A,-(n-

1~(A,$4-A~) (4)

A,+(n-

l)hM+flA,-hF)

In this equation, n depends on the shape of the particles and upon the ratio of the conductivities of the two phases. Equation (4) can be used with n as an empirical constant (shape factor) that must be determined experimentally for mixtures containing particles of arbitrary shapes. The shape factor n corresponds to the sphericity rC, (defined as the ratio of the surface area of the inclusion to that of a sphere of equal volume): 1 -?V 1

(2)

2+k l-k with A = __

;B=---

6 + 3k 4 + 3k

;c=

3 - 3k -+;

k=$

This model has been found to be in a reasonable agreement with experiments at temperatures above 20 K4,. Chen et al. developed the following mode16, which incorporates boundary resistance for spherical inclusions at high concentrations by a simple extension of the work of Meredith and Tobias2. h = h A*-2f-0.41 B*f 13-2. 13C*f c M A*+f+0.41B*j=0.91 C*f3 with A*=_. 2+k+2kr l-k+kr c* = 3-3k+9kr 4+3k+l2kr B = k=F;
M

With Equation (4), it was possible to describe successfully the thermal conductivity of a compound of high-temperature superconductor (HTSC) particles (YBa,Cu,O,,,) in epoxy resin for temperatures above 20 K with n = 8 (Figure 2). Since the particles do not diverge much from the spherical shape, this shape factor is possible only if the porosity of the HTSC particles is taken into consideration, which clearly can be seen in REM pictures of the particles. If in Equation (4) the boundary resistance through a series arrangement of the heat resistances of filler and boundary area is taken into consideration, then 1 2R, h;;=7+A, 1

(6)

With this A;, one obtains from Equation (3) t

(4):

6-3k+24kr 4-k+ I6kr r-h,%

where d is the diameter of the filler and Rg, the boundary resistance. For a compound of spherical Cu fillers (diameter 5.5 or 50 pm) in epoxy resin, Equation (3) is in reasonable agreement with experiments between 2 and 300 K6. If the relative thermal conductivity &J.Jh, 2 102, then the thermal conductivity of the compound depends only on the concen-

,,

I 10 T/K loo

Figure 2 Thermal conductivity of pure Epilox T 20-20 (0) with HTSC-powder-filled Epilox T 20-20 and pure HTSC (0) as a function of temperature. Filler content: (A) 31%; (x) 20%; (0) 9%

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M. JBckel n

(7)

Equation (7) is also valid for temperatures below 20 K. With Equation (7), it was possible to describe successfully the phonon part of the thermal conductivity of a particle compound of Ag needles in epoxy resin (Epotek 3 1D) for temperatures between 0.1 and 80 K with 12= 55 (Figure 3). The composite investigated here is a single-compound epoxy that is filled with an estimated 17 ~01% Ag needles. The REM picture shows that the Ag needles are 10 to 30 pm long and 1 to 3 pm thick. The shape factor was determined from measurements of the thermal conductivity about 30 K. In this temperature range, the electronic contribution to the thermal conductivity amounts to only 20 to 25%. The electronic contribution is estimated from the Wiedemann-Franz law. Clearly, the thermal conductivity by electrons dominates in the composite below -0.5 K. For comparison, the thermal conductivity of epoxy resin with 56.9% Ag spheres (48 pm) by de Araujo and Rosenberg5 is shown in Figure 3. Though the composite with needleshape fillers includes only 17% Ag, its thermal conductivity between 20 and 80 K is about three to four times higher than that of the composite with Ag spheres. Here is experimental evidence of the large influence of filler shape on the thermal conductivity of composites. If the ratio of thermal conductivities A,,,/A, 5 lo*, then Equation (4) can be reduced to A =A l+(n-1)f c M 1 -.f

I 10

IO

IO2 hr 1 h,

I 103

Figure 4 Thermal conductivity (relative) of the compound as a function of the relative thermal conductivity of fillers for f= 0.2 with shape factor n as parameter by Equation (4)

(8)

Figure 5 .Thermal conductivity (relative) of the compound as a function of filler factor f and for Ad&., > IO2 with n as parameter by Equation (8)

Here, the thermal conductivity of the composite is dependent only on the shape factor 12and the filler concentration J The large influence of the shape of the fillers is also shown in Figures 4 and 5, where the ratio AJAM in Equations (4) and (8) is represented with n as a parameter. A large AJA,,, ratio is obtained only with large shape factors n; this means the shape of the filler must strongly diverge from the spherical shape (e.g. needle shape). From Figure

4 it can be seen that for nearly spherical fillers (n < lo), the thermal conductivity of the filler does not influence the thermal conductivity of the composite when Aflh,,, > lo*.

Conclusions
For many technical applications, the specific heat of polymeric particle composites can be calculated with simple linear equations, which are in sufficient agreement with experimental data. The equation by Hamilton and Crosser3 and experimental measurements (Figure 3) have shown that the shape of the particles can influence the thermal conductivity of a composite quite strongly if the conductivity of the filler material is much greater (say, >lOO times) than that of the matrix for temperatures above 20 K. For spherical particles (n < 10) with AdA,,,, 2 lo*, one can increase the thermal conductivity of the composite to not more than fivefold the thermal conductivity of the matrix (Figure 5). In contrast, one can increase the thermal conductivity much higher for composites containing nonspherical particles (e.g. needles with n > 20). If the boundary resistance between filler and matrix is known, one can also calculate the thermal conductivity for a composite at temperatures below 20 K with the modified Equation (7).

10'

1:
2 IO0
E
.-z

10-I

10;

10: Figure3 Thermal conductivity of a Ag-filled epoxy as a function of temperature: (0) Ag needleApotek 31 (17%); (0) Ag powder (25%) by Reynolds and AndersonlO; f-.-.-_) electronic contribution of Ag; (....) pure epoxy resin; (-1 calculated curve by equation (7) with electronic contribution; * Ag spherical powders (56.9%) by de Araujo and Rosenbergs

Cryogenics

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Thermal properties

of polymer/particle

composites:

M. JBckel
6 I Chan, F.C., Choy, C.L. and Young, K. A theory of the thermal conductivity of composite materials J Phvs D (1976) 9 S7l-586 Jgickel, M. Untersuchungen thermischer Eigenschaften van Polymeren und Polymerverbunden im Hinblick auf ihre Einsetzbarkeit im Tieftemperaturbereich Phys. Postdoctoral Thesis TU Dresden ( 1985) Claude& G., Disdier, F. and Locatelli, M. in Nonmetallic Materials and Composites at Low Temperatures I (Eds Clark, A.F., Reed, R.P. and Hartwig, C.) Plenum Press, New York ( 1978) I3 I Backmann, F. Untersuchung der thermischen Eigenschaften van Epoxidharz-Hochtemperatursupraleiter-Verbundproben im Temperaturbereich van 2 K bis 100 K Phys Dissertation TU Dresden (1988) Reynolds, C.L. Jr and Anderson, A.C. Thermal conductivity of an electrically conducting epoxy below 3 K Rev Sci lnstrum (1977) 48 1715

References
Jiickel, M. and Scheibner, W. Boundary layer induced modification of thermal and mechanical properties of epoxy resin composites C~~genics ( 1991) 31 269-272 Meredith, R.E. and Tobias, S.W. Resistance to potential flow through a cubical array of spheres J Appl Phys ( 1960) 31 I270- 1273 Hamilton, R.L. and Crosser, O.K. Thermal conductivity of heterogeneous two-component systems Ind Eng Chem Fundam (1962) 1 187-191 Garrett, K.W. and Rosenberg, H.M. The thermal conductivity of epoxy-resin/powder composite materials J Phys D (1974) 7 1247I258 de Araujo, F.F.T. and Rosenberg, H.M. The thermal conductivity of epoxy-resin/metal-powder composite materials from 1.7 to 300 K J Phvs D ( 1976) 9 665-675

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