[acs symposium series] high-temperature properties and applications of polymeric materials volume...

Chapter 2

Thermophysical Properties of Epoxy and Phenolic Composites

R. E. Taylor1 and R. H. Bogaard2

lThermophysical Properties Research Laboratory, School of Mechanical Engineering and 2CINDAS, Institute for Interdisciplinary Engineering

Studies, Purdue University, 2595 Yeager Road, West Lafayette, IN 47906

The thermophysical properties (specific heat, thermal conductivity, thermal diffusivity and thermal expansion) of epoxy and phenolic composites are examined. The most common measurement techniques are briefly discussed. Both original and representative literature data are presented to illustrate observed behavior.

When the thermophysical properties for epoxies and phenolics are compared to those for other materials such as metals and ceramics, i t is generally found that the epoxies and phenolics have much lower conductivities and larger specific heats and expansions. It is also noted that the environment and temperature effects on the properties of the epoxies and polymers are much more pronounced than for other material classes. This is due to the molecular structure of these materials and their relatively low melting or degradation temperatures. On a temperature scale normalized to the "melting" temperatures, these materials are used at much higher temperature ratios than other materials. In effect, the situation is comparable to continual use of iron alloys at temperature above 800° C.

The sensitivity of the thermophysical properties of epoxy and phenolics to environmental conditions is shown, for example, by thermal expansion testing. When samples of these materials are placed in a dilatometer and dry gas introduced, the samples often shrink even though the temperature is held constant This is due to removal of moisture. This phenomena is not usually observed for metals or ceramics.

0097-6156/95/0603-0022$12.00/0 © 1995 American Chemical Society

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In High-Temperature Properties and Applications of Polymeric Materials; Tant, M., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1995.

2. TAYLOR & BOGAARD Thermophysical Properties of Composites 23

The large difference in the thermophysical properties of polymers compared to those for metal or ceramic reinforcements, combined with the softness of polymers and their easy fabricability, makes i t possible to make composites with a wide range of propertiea

Thermophysical Properties of Composites: Original Data

Specific Heat. Currently, most specific heat measurements are made using differential scanning calorimetry (DSC), as defined by A S T M E1269-94. Usually sapphire is the reference standard. The standard and sample are subjected to the same heat flux as a blank, and the differential powers required to heat the sample and standard at the same rate are determined using a digital data acquisition system. From the masses of the sapphire standard and sample, the differential power, and the known specific heat of sapphire, the specific heat of the sample is computed. Other test methods, such as adiabatic calorimetry (1) or drop calorimetry (2\ are much more labor intensive and less convenient (3X Also the accuracy of DSC techniques has increased markedly in recent years and is comparable to al l but the most accurate techniques.

The specific heats of polymers are larger than those of other materials due to the low atomic number of the constituents and to molecular bending and rotation. According to the DuLong-Petit Law, the specific heat is 6 calories per mole, so atoms of low atomic weight have large specific heats. While it is not possible to calculate the specific heat of a polymer from first principals (as it is to a certain extent for metals), the Rule of Mixtures is generally valid, so it is possible to calculate the specific heat of a polymer composite from the specific heats of the polymer and the reinforcements. Directionality is not a factor. The Rule of Mixtures for specific heat is expressed as:

C = hvfif, + K . p . C j (1)

where ρ is the density, V is the volume fraction, C is specific heat and the subscripts f and m denote fiber and matrix properties, respectively. The composite density ρ is itself predicted from the Rule of Mixtures:

ρ = y fit+ K«p» ( 2 )

Figure 1 compares the specific heats of two graphite fiber reinforced P E E K materials. The volume percent of fibers (62%) was the same for both samples, but one was unidirectionally reinforced, while the other was quasi-isotropic The specific heat values are within a few percent

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HIGH-TEMPERATURE PROPERTIES AND APPLICATIONS OF POLYMERS

0 Γ • I . I • I • I , I • I • I I ι I ι I ι -200 -100 0 100 200 300 400

Temperature (°C)

Figure 1. Specific Heat of Graphite/Thermoplastic (62 Vol % P75 i n P E E K ) with Quasi-Isotropic and Zero C T E Layups.

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of those predicted from the Rule of Mixtures. The peaks in the specific heat curve are due to a transition in the P E E K

It should be emphasized that the Rule of Mixtures applies to true specific heat, Le. that quantity of heat required to raise one gram of material one degree C. Reported specific heat values are usually apparent specific heats which include energy which changes the material: desorption of moisture, phase changes, energetics of decomposition, etc. In determining specific heat, thoroughly dried samples should be used; otherwise the results depend upon the relative humidity. Also there must be no cutting oil, fingerprints, or other contaminants present. The heat required to remove those contaminants is significant compared to the heat required to raise one gram one degree. Therefore the presence of such contaminants introduces significant errors into the measurements. The small sample mass magnifies the problem. Thermal Conductivity/Thermal Diffusivity. Thermal conductivity (K) values may be calculated from the results of steady state measurements or from the results of transient measurements. Both methods are indirect. Thermal conductivity is a derived quantity and cannot be measured directly. Transient techniques are often used (4) because of their relative ease, speed and the fact that they can reveal important information concerning the microstructure of the samples (5) However, the measurement of the properties of heterogeneous materials by transient techniques requires a great deal of expertise. This is particularly true in the case of fiber-reinforced composites where the fibers act as "super-highways" for heat flow (6) Actually, a similar problem exists for steady- state determinations, since the experimenter assumes that the heat flux is uniform or that the surface temperatures are uniform - neither of which is correct. The laser flash diffusivity technique has been established as an A S T M standard ( A S T M E1461-9) and its application to a l l types of heterogeneous materials has been investigated (6X

In the flash method, the front face of a small disc-shaped sample is subjected to a submillisecond laser burst, and the resulting rear face temperature rise is recorded and analyzed. A computer controls the experiment, collects the data, calculates the results, corrects for heat losses and compares the raw data with the theoretical model.

Conductivity values for material with continuous fiber reinforcements can be approximated (7,8) by the following equations

• For longitudinal conductivity,

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ZeroCTE [±30,0 4] s

Figure 2. Figure Layup Configurations.

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(3)

(4)

where Κ is thermal conductivity and x, y and ζ refer to direction. In the case of unidirectional fibers, Eq. (3) is very satisfactory,

and Eq. (4) is approximately correct. The conductivity values of multilayer composites can be calculated from ply values (7X

A thorough study of thermal conductivity, thermal expansion and specific heat of three continuous fiber-reinforced composites using three layups and keeping the fiber volume percent constant at 62% was performed by T P R L (NASA Report, CR-187472, Aug., 1990) (SX The three composite systems were graphite epoxy [P75/ERLX 1962], Pitch-fiber based graphite/thermoplastic [P75/PEEK], and a pan-fiber based carbon/thermoplastic [AS4/PES1 The layups were quasi-isotropic [0,45,90,-45^ and near-zero C T E [30,-30,0^ (Table I and Figure 2). Some measurements were also made on unidirectional composites.

The conductivity values for the P75 /PEEK samples are plotted in Figure 3. The Z-direction values are the same and are quite small. The conductivity of the zero C T E layup in the X-direction is quite large, while that for the Y direction is much less, but still considerably larger than those for the Ζ direction In the case of the quasi-isotropic layup, the conductivity values in the X - and Y - directions are nearly equal to each other and are midway between the corresponding values for the zero C T E layup.

Thermal conductivity values at 100° C for the three continuous fiber-reinforced composites are summarized in Table I. The Z-direction values are a l l small, as expected. The conductivity values for both P75 graphite composites are nearly equal in corresponding in-plane directions, demonstrating that the fiber controls the values, and not the matrix. The conductivity values for the in-plane directions in the AS4 composite are much smaller than those for both P75 composites, in line with the previous comment. Both the lack of quasi-isotropic response in [0,45,90,-45^ and low longitudinal conductivity in [30,-30,0^ suggest the presence of disbonds or microcracks in the carbon-reinforced composite (8).

PMCs degrade at high temperatures, permanently altering their conductivities. A knowledge of this degradation is important in applications in which these materials are used as heat shields. In a

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28 HIGH-TEMPERATURE PROPERTIES AND APPLICATIONS OF POLYMERS

ο Z3 "D C Ο Ο CO ε ο

1.000 0.900 0.800 0.700

0.600 h 0.500 0.400 0.300

0.200 0.100

I ι I • I ι l ' I ι I ' I ' I ' I ' I ' I • I '

P75/1962[±30,0 4] s

• Χ Δ Υ ΟΖ

Ρ75/1962 [0,±45, 90]c

• Χ s

AY • Ζ

—Ç ι I ι 0 ι ι ι Ο -200 -100 0 100 200

Temperature (°C) 300 400

Figure 3. Thermal Conductivity in the X , Y and Ζ Directions of Graphite/Thermoplastic (62 Vol % P75 in P E E K ) with Zero C T E and Quasi-isotropic Layups.

0.020

? 0.018

400 600 Temperature (°C)

1000

Figure 4. Thermal Conductivity of Carbon-Reinforced Phenolic in the Ply Direction Pre-Heat Treated to Various Temperatures (200, 300, 400, 500, 600, 700 and 800 ° C). Reprinted with permission from Reference 9. Copyright 1989 Plenum Publishing.

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proprietary study of a carbon fiber reinforced phenolic composite, conductivity values were determined for samples which had previously been heated for twenty minutes to various temperatures between 200 and 800° C by the manufacturer prior to shipment to the measurement facility (9). The conductivity values for the across-ply direction for many different degradation states are given in Figure 4. By plotting the values measured at the soak temperature (Figure 4), the conductivity of the composite as a function of temperature for twenty minute exposures can be deduced (Figure 5). Alternately, because thin samples are essentially exposed on all surfaces and each diffusivity experiment can be performed rapidly, it is possible to determine changes in conductivity for the composite as it degrades by simply holding the sample temperature constant and measuring diffusivity as a function of time.

Table I. Thermal Conductivity (W/cmK) at 100°C Material Κ

X K 2

P75/1962 [0]8 1.05 0.012 0.012 P75/1962 $,±45,90], 0.50 0.48 0.015 P75/1962 [±30,0^ 0.97 0.098 0.015

P75/PEEK $,±45,90], 0.46 0.58 0.015 P75/PEEK [±30,0,], 0.85 0.082 0.018

AS4/PES [0,±45,90]6 0.029 0.050 0.005 AS4/PES [±30,0,], 0.029 0.007 0.002

Thermal Expansion. Expansion studies can be performed relatively quickly and inexpensively using push-rod dilatometers (ASTM E228). However, the sensitivities of push-rods are not adequate to accurately measure the small changes seen in the small temperature ranges involved. Thus push rod-dilatometers are useful for establishing the overall behaviors of continuous-reinforced polymer composites. Precise measurements should be taken using laser interferometric dilatometry. Contractions can be observed on graphite/polymer samples as the chamber they are in is evacuated or purged with dry gas. These length changes, due to moisture disorption, can be appreciable. In the fiber direction of continuously-reinforced fiber composites, changes can be equal to the dimensional changes caused by the usual temperature cycles investigated. Thus, the sample should be evacuated for several hours before beginning a test.

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0.020

§ 0.008 S 0.006 I 0.004 β 0.002

200 400 600 Temperature (°C)

800 1000

Figure 5. Thermal Conductivity Values at the Pre-Heat Temperature for Carbon-Reinforced Phenolics in the Warp, Ply, Fill and Involute Conf igur ations.

The expansion curves for continuous fiber-reinforced composites usually exhibit considerable hysteresis and residual strain. Generally, these are reduced after several cycles. A thorough study of the length changes experienced by the P75/1962, P75/PEEK and AS4/PES samples has been made. Length changes were measured between -150 and +150° F before and after 10,000 cycles over the same temperature range. The length changes for the non-cycled samples all show large hysteresis and residual changes. These were significantly smaller in magnitude in the extensively cycled samples. This was indicative of the reduced residual strain levels in the laminate. The fabrication residual strains near the reinforcement/matrix interface are partially relieved due to microcracking and microplastic flow in the matrix. Because of the reduced hysteresis, the average CTE obtained by the slope of a line joining thermal strain values at extreme temperatures (-150° F and 150°F) were consistent with the average CTE in the heat (RT-150°F) cool (150°F--150°F), and heat (-150°F-RT) segments. Also, the average CTE values for each composite were close to the predicted values.

The predicted values were calculated from the Rule of Mixtures relations (8X

• Continuous Fiber Reinforced Longitudinal Thermal Expansion Coefficient:

CTEX = VfiffTEf, + VJ!mCTEm (5)

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• Transverse Thermal Expansion Coefficient:

CTEy = CTEZ = CTE,

where Ε is the modulus and ν is Poisson ratio. The results before and following 10000 cycles are summarized in

Table IL

Table Π. Thermal Expansion Results Material CTEX

initial CTEx

cycled CTEx

predicted CTE y

initial CTE" cycled

P75/1962[0]8 -0.69 -0.60 P75/1962[0,±45,90]s -0.45 -0.59 -0.34 -0.14 -0.40 P75/1962[±30,04]s -1.02 -1.0 5.83 2.9

P75/PEEK[0,±45,90]s -0.28 -0.25 -0.30 0.04 -0.20 P75/PEEK[±30,04]S -0.39 -0.80 -1.01 10.17 7.6

AS4/PES[0,±45,90]S 1.08 -0.65 1.38 -0.29 AS4/PES[±30,0J8 -0.66 -0.37 12.6 10.7

Thermophysical Properties for Composites: Literature Data

A data base activity on properties of polymer matrix composites has been underway at CINDAS for some time. Literature data for thermophysical and mechanical properties are compiled, analyzed, and evaluated for entry into the data base. Particular attention is given to factors such as material description (name, composition, reinforcement structure), processing, specimen description (dimensions, orientation), test method (standards, parameters), and material conditioning (moisture effects, aging). In the subsections that immediately follow, several representative sets of data from the database are displayed and discussed. Thermal Conductivity. Several sets of literature data for thermal conductivity of unidirectional laminates along with a typical epoxy and a pitch-based graphite fiber are shown in Figure 6. The heat flow direction is in all cases along the fiber. Fiber-volume contents are in the range 59-65%. The logarithmic scale accommodates the large range in magnitude of the thermal conductivity observed when comparing an epoxy (10X S-glass/epoxy (11\ aramid/epoxy (12X HMS carbon/2002 epoxy (13X GY80 carbon/Code 69 epoxy (MX and a P100 graphite fiber (15), with the increase amounting to a factor of 1000 at room temperature.

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Increased thermal conductivity is associated with increasing order and bond strength at the atomic level, and, for carbon fibers, with increased graphite platelet content in the fiber microstructure. Thermal Expansion. Some published results for thermal expansion of unidirectional carbon/epoxy laminates along with matrix resin and fiber are shown in Figure 7. The data show that the expansion of a unidirectional laminate in the fiber direction (16) is quite similar to the fiber itself (17). On the other hand, for the transverse laminate direction the laminate expansion (18) is midway between the resin alone (18) and the transverse (radial) expansion of the fiber alone (19)

The absorption of moisture by epoxy polymers is widely known to cause swelling of the material. The complication this creates for thermal expansion is demonstrated in Figure 8 by data reported for unidirectional AS/3501-6 carbon/epoxy in the matrix dominant direction (18) along with the 3501-6 epoxy alone (18). The effect of moisture is

Temperature, Κ

Figure 6. Thermal Conductivity of Various Materials (Literature Data: Unidirectional Composites, Polymer, Fiber).

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Figure 7. Thermal Expansion of Carbon/Epoxy Laminates (Literature Data for Dry Conditions). D

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Figure 8. Thermal Expansion of Carbon/Epoxy Laminates (Literature Data for Wet/Dry Conditions). D

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to increase the plasticity of the matrix resin, lower the glass-transition temperature, and reduce its stiffness. Clearly, the moisture content of the material, which in the present case is wet (moisture saturated at room temperature) or dry (ambient condition), must be known i n order for the data to be meaningful.

L i te ra ture Ci ted.

(1) Kagan, D.N. in Compendium of Thermophysical Property Measurement Methods, Eds., K D . Maglic, A. Cezairliyan and V.E. Peletsky, Survey of Measurement Techniques, Plenum Publishing, NY, NY, 1984, Vol. 1, Chpt. 12, pp. 461-521. (2) Ditmars, D.A., in Compendium of Thermophysical Property Measurement Methods, Eds., K.D. Maglic, A. Cezairliyan and V.E. Peletsky, Survey of Measurement Techniques, Plenum Publishing, NY, NY, 1984, Vol 1, Chpt. 13, pp. 527-548. (3) Richardson, M.J., in Compendium of Thermophysical Property Measurement Methods, Eds., K.D. Maglic, A. Cezairliyan and V.E. Peletsky, Survey of Measurement Techniques, Plenum Publishing, NY, NY 1984, Vol. 1, Chpt 17, pp. 669-685. (4) Taylor, R.E., in Thermal Conductivity 19, Ed. D.W. Yarbrough, Plenum Publishing, NY, NY, 1988, pp. 403-412. (5) Taylor, R.E., Jortner, J. and Groot, H., Carbon, 1985, 23(1), pp. 215-222. (6) Taylor, Raymond, High Temp - High Press, 1983, 15, pp. 299-309. (7) Rawal, S.P„ Misra, M.S. and Wendt, R.G., Report NASA CR-187472, Composite Materials for Space Applications, Martin Marietta Astronautics Group, Denver, CO., Contract NASA1-18230, August, 1990. (8) Chawla, K.K., in Composite Materials, Science and Engineering, Eds. B. Ilschner and N.J. Grant, Spring-Verlag Publishing, NY, NY, 1987, Chpt 10.3, pp. 189-191. (9) Taylor, R.E., in Thermal Conductivity 20, Eds. D.P.H. Hasselman and J.R. Thomas, Jr., Plenum Publishing, NY, NY, 1989, pp. 93-101. (10) Rosenberg, H.M., in Nonmetallic Materials and Composites at Low Temperatures, Eds. G. Hartwig and D. Evans, Plenum Press, NY, NY, 1982, Vol. 2, pp. 311-325. (11) Hust, J.G., National Bureau of Standards Report NBSIR-84-3003, 1984. (12) (Bogaard, R.H., HTMIAC/CINDAS, unpublished evaluation of literature data, 1992).

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(13) Philpot, K.A. and Randolph, R.E., in Nonmetallic Materials and Composites at Low Temperatures, Eds. G. Hartwig and D. Evans, Plenum Press, NY, NY, 1982, pp. 311-325. (14) McIvor, S.D., et al, J. Mater. Sci., 1990, 25(7) pp. 3127-3132. (15) Heremans, J., Rahim, I., and Dresselhaus, M.S., Phys. Rev., 1985, 32, pp. 6742-6747. (16) Lauraitis, KN. and Sandorff, P.E., U.S. Air Force Report AFML-TR-79-4179, 1979, [AD-A085 167]. (17) Yasuda, E., et al., in 18th Biennial Conference on Carbon, Proceedings and Programs, American Carbon Society, pp. 30-31, 1987. (18) Cairns, D.S. and Adams, D.F., U.S. Army Report ARO-16370.5-MS, 1981, [AD-A109 131]. (19) Sheaffer, P.M., in 18th Biennial Conference on Carbon, Proceedings and Programs, American Carbon Society, pp. 20-21, 1987. RECEIVED April 4, 1995

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