MATERIALS SCIENCE & ENGINEERING

ELSEVIER Materials Science and Engineering A197 (1995) 237-249

Prediction of creep rupture of unidirectional carbon fiber reinforced polymer composite

J. Raghavan*, M. Meshii
Department of Materials Science and Engineering, Robert R. McCormick School of Engineering and Applied Science, Northwestern University, Evanston, IL 60208, USA

Received 5 August 1994

Abstract

A creep model, which was used successfully in a previous paper to model the creep of cross-linked epoxy resin as well as unidirectional carbon fiber reinforced epoxy composite, is used along with a fracture criterion to predict creep rupture at temperatures ranging from near Tg to far below Tg when the epoxy matrix of the composite is in the glassy state. This model, whose parameters have been measured by separate experiments, enables the separation of the part of the work stored from the part dissipated. A critical energy is proposed as the fracture criterion. Using the model, the time-dependent increase in stored elastic energy is calculated. Fracture occurs when the stored elastic energy equals the critical energy. The implication of temperature-dependent fracture mode in creep rupture prediction is discussed in terms of the temperature dependence of the critical energy.
Keywords: Polymer composite; Creep rupture; Prediction model; Critical energy fracture criterion

1. Introduction

The fact that the creep rupture of polymer composite is dependent on the viscoelastic properties of the matrix is evident from the study by Miyano et al. [1], in which the fracture strength of the polymer composite and the pure epoxy matrix showed similar dependence, on temperature and strain rate, spanning both glassy and rubbery regions. The high-performance polymer composites currently in use and development have service temperatures far below the glass transition temperature (Tg), when the matrix is in the glassy state. Even at these temperatures polymer composites exhibit timedependent degradation of strength and modulus. But the experimental quantification of this degradation at these temperatures is time-consuming, so that it is often necessary to resort to extrapolation of data from accelerated tests at high temperatures. F o r reliable extrapolation of data, a model with accurate creep rupture predictive capability in a wide range of accelerted test

* Present address: Center for Composite Materials, Newark, DE 19716, USA 0921-5093/95/$9.50 1995 - - Elsevier Science S.A. All rights reserved SSD1 0921-5093(94)09730-5

conditions, and with validity over the entire extrapolation range of temperature and stress, is crucial. The creep rupture models proposed in the past were based on the rate process theory of fracture [2-4], fracture mechanics principles [5,6] and probabilistic fracture [7]. Though the fracture mechanics approach is very promising, a simple power law used in this to model the creep of the composite is only an approximation with limitations on the time period for which a single constant power law exponent can be used. Moreover the t i m e - t e m p e r a t u r e - s t r e s s superposition principles used in extrapolation of experimental data from test temperature to another temperature is not valid for the thermo-rheologically complex high-performance polymer composites [8]. Other models rely on extensive testing, to establish a functional relationship between model parameters and testing conditions, for extrapolation of data. Moreover, considering the various degrees of orientation of fibers for a given application, experimental cost and time would be prohibitive while using simple empirical models. Based on the review, it can be concluded that a satisfactory standardized procedure, to extrapolate experimental data accurately and reliably from accelerated test conditions near Tg to service

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conditions far below Tg, needs to be developed. In order to understand the creep rupture process better and to derive a model for accurate extrapolation of test results from accelerated test conditions to service conditions, the present authors have adopted an approach wherein the creep rupture of composites is considered to be termination of creep. Hence an accurate model to simulate creep of composites and a fracture criterion to predict creep rupture are essential. Mathematically simple creep models reported thus far in the literature [4,9-11], based on mechanical analogs (stretched exponential), the t i m e - t e m p e r a t u r e stress-superposition principle (TTSSP) and power law, have been successful in modeling creep of a variety of polymers in limited experimental conditions. However, they are not considered by the present authors, for two reasons. These are empirical approaches incorporating no material parameters. Any change in material parameters cannot be readily translated into a change in long-term durability without extensive testing. The second reason is the assumption in these models that the shape of the creep compliance-time curve remains the same: i.e. the shape of the relaxation spectrum remains the same, in the range of extrapolation. This is not true for matrices of polymer composites in use today [8]. Accordingly, thermal activation theory, which was shown [12] to model successfully the creep of epoxy resin and unidirectional carbon fiber reinforced composite in a limited strain rate range, has been modified [8] and incorporated into a three-element model to predict creep reliably over a wide range of temperature, stress and time. The objective of this paper is to establish a fracture criterion for creep rupture and to use this to predict creep rupture of polymer composites by extending the above creep model. At temperatures below Tg, if sufficient time is allowed, a glass-to-rubber transition of the glassy polymer matrix of the composite will occur, provided the specimen does not break. Depending on the stress level, temperature and activation energy for creep, the polymer matrix will be in either a glassy state or a rubbery state at the time of fracture. Considering this, a reliable creep rupture prediction model should be able to predict creep rupture in both glassy and rubbery regions. This requires a failure criterion common to both rubbery and glassy regions as well as knowledge of fracture modes in the entire time period of extrapolation. The majority of previous studies [13-16] on epoxies, similar to the matrix of the polymer composite used in this study, were focused on fracture below Tg in the glassy region. The fracture mechanics studies of precracked epoxy specimens under mode I loading, in the glassy region, revealed that the fracture energy (Gic) varied with temperature and strain rate. Hence the stress and strain at fracture also varied. In addition, Gic

showed a single value when the crack growth was stable, and when the crack growth was by unstable stick-slip mode, a value for initiation (Glc i) as well as a value of crack arrest (Gic a) were obtained. In most studies, G~ci increased with increase in temperature and decrease in strain rate, while an opposite dependence on temperature and strain rate was exhibited by G~c and Glc a. In the temperature range of interest to this study, where primary ~ transition is predominant, the epoxies showed stick-slip crack growth mode, and the Gic values were not single valued. Lemay and Kelley [15] observed a square-root dependence of Gic a on molecular weight between cross links and supported the prediction of a limiting fracture toughness, i.e. fracture energy in the glassy region, by Kramer and Hart [17]. These results suggest that there may be a limiting fracture energy in the glassy region which can be used to predict the safe limit of stress below which time-dependent creep rupture of the composite will never occur. However, Aliyu and Daniel [18] reported a decrease in single-valued Gic with decrease in strain rate at room temperature in AS4/3501-6 composite. Similar variation of both Gic and Guc with temperature was observed by Russell and Street [19] in AS4/3501-6 composite. In the temperature range of their investigation, only the transition is predominant [8]. These studies suggest that for the composite used in the present study, which is also AS4/3501-6, testing in the glassy region would yield temperature- and strain-rate-dependent fracture energies. These results suggest that a unique fracture criterion may not be realistic for creep rupture prediction in the glassy region. While fracture studies on epoxy above Tg are limited, extensive studies have been carried out on elastomers. Lemay and Kelley [15] studied the fracture of epoxies at temperatures above Tg. They observed GIC to decrease with increase in temperature to a constant value at temperatures 65 80 degrees above Tg. They also found this constant G~c to show a square-root dependence on molecular weight between cross links, similar to the dependence of Gic a below Tg in the glassy region. Based on these results they concluded that the fracture process, whether above or below Tg, depended on a similar creep rupture mechanism. Since cross-linked epoxy can be considered as weak elastomers, more information about fracture behavior above Tg can be obtained from previous studies on elastomers. Fracture mechanics studies [20-22] on elastomers, at temperatures which were normally above Tg, had shown that Gjc decreased with increase in temperature or decrease in strain rate to a constant value. This temperature- and strain-rate-independent constant value was first related theoretically by Lake and Thomas [23] to the energy required to break polymer chains lying across the path of the crack, in vulcanized

J. Raghavan, M. Meshii / Materials Science and Engineer&g A 197 (1995) 237 249

239

rubber. Mueller and Knauss [24], by swelling an elastomer, measured an intrinsic fracture energy which was strain-rate- and temperature-independent. They related the total tear energy obtained by constant strain rate tests to this intrinsic energy using time-dependent compliance. A similar relation was developed independently by Andrews [25] based on his generalized fracture mechanics theory. From the above review, the following can be inferred in general about time-dependent polymer composite fracture in regions above and below Tg: (a) there are no unique stress or strain limits to define the fracture; (b) these exists a temperature- and strainrate-independent constant fracture energy; and (c) the total fracture energy calculated from the area under the stress strain curve, obtained in a constant strain rate test, is dependent on strain rate and temperature and would approach the constant fracture energy value as the temperature increases or as the strain rate decreases. If the temperature and strain rate dependence of the total fracture energy is due to viscous creep alone, then, using the creep model [8] already developed for simulating the creep of composites, the energy dissipated by viscous creep can be evaluated at any applied creep stress. Subtracting this from the work done by the applied creep stress on the composite specimen, the stored energy with time can be evaluated until it reaches the constant fracture energy when the specimen fractures. Then, this constant fracture energy would be a unique fracture criterion in such viscoelastic materials that exhibit energy dissipation by creep only. But this constancy in fracture energy implies that fracture mode should be the same in the entire prediction range of temperature and strain rate, which may or may not be valid. Hence the fracture criterion used in this study is "the macroscopic fracture of the unidirectional composite occurs when the stored elastic energy equals a critical energy for fracture". Combining this fracture criterion with the creep model [8], the creep rupture model for unidirectional polymer composites has been formulated, predicting the creep rupture of polymer composite under the constant load condition. The simplest fracture criterion of constant critical energy is independent of temperature and strain rate. This condition is met when the creep rupture occurs at high temperatures above Tg when the matrix is in a rubbery state and at very low strain rates at temperatures below Tg. The fracture surface corresponding to this fracture condition is relatively smooth. On the other hand, in the lower-temperature region or at relatively high strain rates, the fracture surface becomes increasingly rough with decreasing temperature or increasing strain rate. This results in variation of critical energy with temperature and strain rate.

~a

VIO
Ho, V

Fig. 1. Schematic of the model used to predict the creep and creep rupture of the polymer composite.

2. Creep rupture model

When a polymer is stressed, its free energy is momentarily raised. This is then dissipated gradually when the polymer segments reorient to a lower free energy state. The rate of this process depends on temperature, stress as well as the cooperative motion of the molecular neighbors [26,27]. Hence an amorphous cross-linked polymer matrix of a polymer composite behaves like a brittle solid at temperatures far below the glass transition temperature (Tg) due to the very high viscous resistance to chain segmental motion. With increase in temperature, this viscous resistance is more frequently overcome and the polymer becomes progressively softer and at temperatures above Tg, it approaches a state where the viscous resistance to the chain segmental motion is easily overcome. Such a material can be easily visualized using a three-element model, as shown in Fig. 1. Such a model was first used by Eyring and Halsey [28] to model the constant strain rate behavior of textile fibers, and since then several combinations of such mechanical analogs have been used by several investigators to empirically fit the experimental creep data. However, the modified thermal activation theory used in the analysis of creep differentiates the present approach from earlier ones. Moreover, in contrast to previous approaches where the model parameters were obtained by fitting the experimental data to the theoretical model, the important model parameters in the present approach have been measured by independent experiments and used to verify the consistency and validity of the model over a wide range of extrapolation conditions. With increase in temperature, the viscous resistance in the material is overcome by the thermally

240
t i i i i i i

J. Raghavan, M. Meshii / Materials Science and Engineering A 197 (1995) 2 3 7 - 2 4 9

iii

7 ,", o.

6
5 4

,~

3
0

!
~ . a . . a ~.a ~ .j ~ j ~ml ~ml e -a ~ml e -a . . a . . a e.a ~-a R.a ~-a . . a e.a ~tml ~ 1 ~ ~tml ~ 1 ~ 1 ~tml,

The chain segmental motion in the polymer matrix of the composite, which results in macroscopic creep strain, is modeled, by the thermal activation theory, to be a rate process of overcoming an energy barrier. The macroscopic creep strain is measured when the transition from state 1 to state 2 occurs, overcoming the energy barrier of magnitude Go separating the two states. At a given temperature, the creep rate of the composite due to such transition is related to the effective stress by the thermal activation theory [29]: ~v = eo e x p L - - ~ )
f Ho\ . /Va*\ slnhL~- )

(la)

where eo is the pre-exponential factor given by ~o = 2N~ Ae ~ e x p ( ~ ) (lb)

10-3 100 103 106 109 1012 1015 1018 1021 1024 Time : s Fig. 2. Predicted compliance curve, for the composite, at 433 K at a creep stress of 29.56 MPa. The curve beyond a reasonable time period of 109 S is shown to point out that the composite compliance would reach a plateau if failure did not interfere during this time period. activated chain segmental motion and is represented by the box in series with the viscous resistive element. This thermally activated chain segmental motion has already been modeled [12] in a limited strain range, using a simple activation theory. Upon application of a constant creep stress cra, o" i is the stress in the element with modulus ER and referred to as internal stress. This internal stress, at any given macroscopic strain, is defined by ER. o-* is the stress in the element with modulus Ev and referred to as the effective stress. During creep, due to thermally activated chain segmental motion, the macroscopic strain increases. The internal stress increases and effective stress decreases. The resulting time-dependent creep compliance is shown in Fig. 2. From Fig. 1, it can be inferred that the creep compliance saturates when the creep rate decreases to zero, i.e. when the effective stress decreases to zero. Then this saturation compliance, as shown in Fig. 2, is equal to the inverse of ER. When there is no creep in the composite, i.e. zero creep rate, then the strain response of the composite is in phase with the applied stress. In other words, the composite's response is elastic. This condition is achieved in the dynamic mechanical thermal analysis (DMTA) test, when the storage modulus decreases to a constant value at temperatures above Tg and when the matrix of the composite is in a rubbery state. Hence, E R is termed the rubbery modulus. Its magnitude is given by the plateau value of the storage modulus above Tg, measured using D M T A tests. The viscous modulus Ev, which is the magnitude of the modulus drop across the glass transition and has been measured by the D M T A test [29].

Here, the free energy, Go, is written in terms of Ho and So. Ho is the activation energy at zero effective stress for the transition process and can be experimentally obtained using the D M T A test [8]. S O is the entropy of activation and is assumed to be constant in the temperature range (295-433 K) of investigation, T is the test temperature, k is Boltzmann's constant and V is the stress coefficient. This is referred to as the activation volume since its unit is the same as that of volume. This can be experimentally determined using a differential strain rate or constant strain rate test [8]. In metals, this volume has been shown to be the volume defined by the product of the Burgers vector and the area swept by a dislocation segment while overcoming an energy barrier. However, no such clear definition exists for polymers. N~ is the number of flow units, i.e. the number of polymer chain segmental units in state 1, available for transition. The total number of flow units N, available in both state 1 and state 2, is given by N = N1 + N2 (2)

where N2 is the number of flow units in state 2. N remains constant since the total population of flow units cannot change. A~ is the average strain increment per transition and h is Planck's constant. As creep progresses, the internal stress increases and the effective stress decreases, maintaining the relation
(7" a =

~ri(t) + o-*(t)

(3)

where t is the creep time. Accordingly the creep rate decreases with increase in time. A simple activation theory, represented by Eq. (1), has been successful only in a limited strain rate/time range due to the assumption that the number of flow units (N~) available for transition and average strain increment per transition remain constant during the entire creep period. But in reality, the number of flow units available for transitions and the average strain increment per transition, in amorphous polymers, may

J. Raghavan, M. Meshii / Materials Science and Engineering A197 (1995) 237-249

241

vary with stress and strain rate/time at a given temperature. Due to this, previous investigators were unable to use a single activation process to model the entire creep curve, and they used a spectrum of activation processes, i.e. a spectrum of retardation time, to model the entire strain rate/time range. An earlier attempt [10] including a change in N1 with creep rate, assuming a constant average strain increment per transition, was not successful in simulating the actual creep behavior with a single activation energy. The present authors have demonstrated [8] that a single activation process with a single activation energy can model successfully the creep of a polymer composite [AS4/3501-6] and its epoxy matrix by assuming that both N~ and average strain increment per transition change with strain rate during creep. The number of flow units N~ at any strain rate is written as N1 = Nl -- n (4)

available for transition at a given strain rate and effective stress. This is assumed to be constant in the entire range of strain rate and effective stress and is substituted for N1 in Eq. (lb). Referring to Fig. 1, during creep, in addition to viscous strain rate as per Eq. (7), there will also be an elastic strain rate due to the time-dependent change in elastic strain in the element with modulus Ev. The total creep rate, measured macroscopically in the creep experiment, is written as Dr = ~e + iV where tv is given by Eq. (7) and Dr = ~ and te = 1 do-dt* (8a)

Using Eqs. (3), (7) and (8), the total creep rate, measured macroscopically during creep experiments, is derived as Dr=4~ o-* In exp - ~ smh ~ (9a) where to = 2 1~ ~ ER fl exp (~--2)AN1 Xo (9b)

where N~ is the magnitude of N1 at the instant of application of creep stress aa. n is the total change in N~ from the start of creep to a certain stage of creep. Corresponding to this change, there would be an increase in macroscopic creep strain and a decrease in effective stress. Assuming a Weibull distribution [29] in n, the effective stress remaining in the material, after a change in N~ by n, is given by o-~ = exp --

(5)

Here X is used for convenience in defining the distribution in n, and it represents a specific value of n. o-* is the effective stress, in the material, at the instant of application of the load. Xo represents the total change in N 1 when the effective stress in the material reduces to o-*/e, fl is the Weibull shape parameter. Using Eqs. (4) and (5), the average strain increment per transition is computed [29] to be + Ev fl X o o o * ,I --lnt~,o,) /o-,\-]l A e - ERER~-~---v ] - lip (6)

Eq. (9) is the analytical form of the creep model. Using this modified creep rate Eq. (9), it has been shown that a single activation process with a single activation energy can accurately model and predict the creep of AS4/3501-6 composite and its matrix resin [8]. Using Eqs. (3), (8) and (9), the rate of change of effective stress can be written as
do'* = t" [- *

d, o<o{-[l'Q)}}
o-*

fro-*\ sinht )
where to' = eoER

(lOa)
(10b)

Using this expression for the average strain increment per transition, Eq. (1) is modified as [8]

[ln(5)l)l 1
sinht-~- ) where e=2ER ~+ EE R vE v fl exp(~)ANIxo (7b) (7a)

Due to the cooperative nature of the polymer chain segmental motion, it is likely that only a certain number of flow units in state 1, i.e. AN~ out of N~, is

The effective stress and the effective stress rate in the material decrease with time. At a given effective stress, the effective stress rate is evaluated using Eq. (10), provided all the model parameters are known. From the values of effective stress and corresponding effective stress rate, the time at the effective stress rate is numerically evaluated [29]. The steps in the numerical procedure are as follows: (1) At time t = 0, the effective stress in the material is a*. (2) Let the effective stress decrease by Ao-* to a new value o-* in a time interval At. (3) The effective stress rate corresponding to the new effective stress value is calculated using Eq. (10).

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J. Raghavan, M. Meshii / Materials Science and Engineering A 197 (1995) 237-249

Assuming this effective stress rate to be constant during the current time step (At), from the values of effective stress rate and Aa*, the magnitude of the time interval At is determined. (4) This is added to the time before taking the time step, i.e. t = 0 , to give the new time t l = 0 + A t corresponding to the effective stress o-*. (5) Steps (2)-(4) are repeated until the desired time is reached. This numerical procedure results in the values of effective stress as a function of time. Using Eq. (3), internal stress ~ri(t) as a function of time is calculated. The elastic stored energy in the composite is the sum of the elastic energy stored in resistive elements with moduli Ev and ER. The elastic energy stored in both the elements at a time t is calculated using the following expressions: Wv(t) - - 2Ev
[~*(t)] 2

and

[~i(t)] 2
Wk(t) -

2E~

(11)

Stored elastic energy at time t is given by

W(t) = WR(t)+

Wv(t)

(12)

According to the fracture criterion chosen for this study, fracture occurs when
W(t

= tf) = Wc

(13)

where Wc is the critical energy for fracture of the composite. Due to variations in internal and effective stresses caused by creep, the stored energy gradually increases with time. Using Eqs. (11), (12) and the numerical procedure discussed above, the time-dependent increase in stored elastic energy is calculated. The time at which this stored elastic energy equals the critical energy is taken to be the fracture time. The above approach, integrating the creep model and a critical energy fracture criterion, is referred in this report as the creep rupture model.

tester. The stresses were chosen such that the rupture time spanned from few a minutes to 11 days. The creep tests were performed at 295 K, 373 K, 403 K and 433 K. The creep rupture tests were performed at 403 K and 433 K. Typical loading time was 13-15 s. Constant strain rate tensile tests at a strain rate of 1 0 - 4 S - l w e r e performed using a Sintec 20/G screwdriven tester to measure the total fracture energy (given by the area under the stress-strain curves) in the temperature range 295-558 K. Resistance strain gages were used for measuring strain except at 558 K, where an extensometer with 1 in gage length was used. Since the matrix resin started degrading chemically at temperatures near Tg, the test result for 558 K (Tg + 40) was simulated by boiling the specimen in distilled water for 8 6 h to bring down the Tg to 4 0 3 K [30], and the specimen was tested immediately in an oven maintained at 443 K. Humidity was maintained high inside the oven to prevent any moisture desorption while heating the specimen to 443 K and testing. It was ascertained that the matrix of the composite reached the rubbery state, due to boiling in water, by comparing the modulus of composite obtained by this test with the modulus obtained in the D M T A test [29] at 558 K. No macroscopic yielding was observed in the temperature range of testing. Fractographic analysis of the composite specimens, fractured in constant strain rate tests, was done using a Hitachi 560 scanning electron microscope at 15 kV. The fracture surfaces were gold plated to 150-200 A for better SEM imaging.

4. Results
The effective and internal stresses at any macroscopic strain were defined using the moduli ER and Ev. The values of these moduli were measured experimentally and their temperature dependence was determined as follows. The rubbery modulus (ER) of the composite, obtained from the D M T A test [29], was defined at a temperature of 558 K. Since the rubbery modulus is proportional to temperature, its magnitude at any temperature was calculated by multiplying the measured magnitude at 558 K by the ratio of temperatures. The instantaneous modulus [Eo] was defined to be the modulus measured in D M T A tests at a frequency of 50 Hz. Its dependence on temperature was deduced from D M T A results. By subtracting the ER from Eo the magnitude of Ev was calculated at a given temperature. The values of Eo, ER and Ev for the composite are tabulated in Table 1. The activation volume was determined using constant strain rate tests [8]. a* at any applied creep stress was calculated from the product of applied stress and the ratio of Ev to Eo. Using these values and Eq. (9), the experimental creep rate results were numerically fitted to obtain the values of the

3. Experimental details
The fracture model presented above is applied in this study to model the creep rupture of carbon fiber reinforced epoxy [AS4/3501-6 [90116] with fibers oriented perpendicular to the loading axis. The fiber volume fraction was 62%. The specimens of size 165 mm in length, 12.7 mm in width and 2 mm in thickness were cut from panels laminated (16 plies) in house using a diamond saw, wet ground using silicon carbide papers, polished with 1 gm diamond paste, rinsed and dried. Then, they were bonded with 38.1 mm long low-carbon steel tabs using an aerospace adhesive (AF 191) supplied by the 3M Company. Resistance strain gages were used for strain measurements. The creep and creep rupture tests were performed using an ATS 2320 creep

J. Raghavan, M. Meshii / Materials Science and Engineering A 197 (1995) 237-249

Table 1 Moduli from D M T A tests [8]. Specimen: AS4/3501-6 [90]16 composite T (K) Instantaneous modulus, E o (GPa) 14.0 13.2 12.9 12.6 Rubbery modulus, ER (MPa) 967 1220 1321 1410 Viscous modulus, Ev (GPa) 13.00 11.98 11.60 11.20

243

20 "7 ---18 16 14

295 373 403 433

~
oo

Table 2 Activation energy. Specimen: AS4/3501-6 [90It 6 composite Creep stress (MPa) 15 29.68 Model fit (kJ mol i) 491 492 Experimental (kJ mo1-1) 494

o 10 r..) ~
o

8 6
10 -3 10 -1

101

103 Time : s

105

107

109

Table 3 Model parameters. Specimen: AS4/350-6 [90116 composite T (K) -at -at fl at 15 M P a fl at 29.68 MPa

Fig. 3. Comparison of experimental compliance with the predicted compliance values, for the composite, at different temperatures. The creep stress is 31.02 M P a at 295 K, 29.68 M P a at 373 K and 403 K and 29.56 M P a at 433 K.

(fiT)

(fiT)

15 M P a

29.68 M P a

(s 1)
295 373 403 433 6.43 9.6 9.0 3.96 x 1020 1021 l02 1020

(s-t)
7.14 8.75 7.52 6.21 x x x 1027 1027 1027 1027 0.048 0.082 0.072 0.084 0.067 0.113 0.126 0.135

pre-exponential factor (e'o), activation energy (Ho) and the Weibull shape parameter ft. The activation energy determined by the numerical fit to two stresses is tabulated in Table 2 along with the experimental value obtained from D M T A tests. The numerical fit values compare well with the experimental value measured by the D M T A test, thus demonstrating the consistency of this model. An activation energy of 494 kJ mol-1, thus obtained, was used for the creep and creep rupture prediction results reported here. The numerical fit values for the pre-exponential factor and fl are tabulated in Table 3. The fl values tend to decrease with decrease in stress at a given temperature. But no analytical form for its dependence on stress could be arrived at this time, since the experimental results were limited to a few stress levels. Hence an average value was used in the creep rupture prediction values presented in this report. The values were 0.058 at 2 9 5 K , 0.098 at 3 7 3 K , 0.100 at 4 0 3 K and 0.110 at 433 K. F r o m Table 3, it can be inferred that the preexponential factor is nearly constant at an applied stress in the entire temperature of creep testing. However, it increases with increasing applied stress. An

exponential function [29] was chosen to fit the variation of pre-exponential factor, given in Table 3, with applied stress and was used in the creep rupture prediction. Using these model parameters and Eq. (9), the creep strain and compliance were simulated by the numerical procedure [29], up to 30 years, and are plotted in Fig. 3 along with the experimental values. In Fig. 2, predicted values at 433 K are plotted beyond 30 years to show that the sample would ultimately creep to a saturation level, if it did not fracture at that applied stress.
5 i tttl,lq i itHtl] i tHiiiq
r

,,H,,q

, ,r,mq

, H,,,|[

I ,~,,,,q

I ,,Imq

, Hrntq

i HIIHI

T
I I

AS4 / 3 5 0 1 - 6
o

[90116

50

T i

45

295 K 373 K 403 K 433K

.,,m

40

<
35

oA o

30

,,,,.-, ,,.,,., ,,,,,,,1 ,,,,,,,1 ,,,,,,,, ,,,,,,., ,,,,,,.~ ,,,,,,,1 ,,,,,,~ ,,,, 10 "1 101 103 105 107 109 Fracture Time : s

Fig. 4. Experimental creep rupture results for the composite at different temperatures.

244

J. Raghavan, M. Meshii Materials Science and Engineering A197 (1995) 237-249

110 100 "O 90 *~ e~ 80

70

.l_l

i i i

i i i

~ i

AS4 / 3501-6 [90116

60
"5 [..

50
4 0

. . . .

. . . .

. . . .

. . . .

250

300

350

400

450

500

550

600

Temperature-K
Fig. 5. Total fracture energy for the composite measured, by constant strain rate testing, at a strain rate of 10 4s i.

In Fig. 4 the creep rupture results at 403 and 433 K are plotted along with the results of constant strain rate tests at 295 and 373 K. The creep rupture time for the composite increased with decrease in applied stress. Also, the applied stress, for a given lifetime, decreased with increasing temperature. The reduction in strength at 403 and 433 K, over a period of 3 days, is approximately 10%. From the slopes of the data plotted in Fig. 4, the rate of strength reduction at 433 K appears to be greater than that at 403 K. At 295 and 373 K, the range of strain rates available for the constant strain rate tests was too limited to determine the stress-fracture time trend. Therefore, an average value is indicated with higher and lower limits at each temperature. These creep rupture results will be discussed, along with the predicted curves, in the next section. The total fracture energy obtained from constant strain rate tests at different temperatures is plotted in Fig. 5 as a function of temperature. The total fracture energy decreased from an average value of 91.7 kJ m - 3 at 295 K to a value of 43.9 kJ m - 3 at 558 K. It can be inferred from tan ~ (which is an approximate measure of ratio of dissipated energy to stored energy) values for the composite, obtained from D M T A tests [31], that the energy dissipated by viscous deformation at 295 and 558 K is negligible. But the dissipated energy increases with temperature at intermediate temperatures approaching a maximum value at Tg (518 K), and it contributes to the total fracture energy plotted in Fig. 5. Hence the total fracture energy in Fig. 5 includes both stored elastic energy and dissipated energy. This dissipated energy was excluded from the total fracture energy to obtain the temperature-dependent critical en-

ergy that was used in the creep rupture prediction. This procedure is discussed in the next section. The mode of fracture changed with temperature. Fig. 6 shows the fracture surfaces of epoxy resin fractured, by constant strain rate tests, at a strain rate of 10 - 4 S-l and at various temperatures ranging from 295 to 552 K. The series of photographs at a low manification show the changes in fracture mode most graphically. The changes were not so clearly revealed on the fracture surface of the composite due to the interference of the carbon fibers. The fracture surfaces shown in Fig. 6 consist of the fracture initiation region followed by a smooth region leading to steps or a river-like pattern. The steps are followed by a coarser stacked lamellar structure. It is apparent in these fractographs that with increase in temperature, the fracture surface morphology gradually becomes smoother. A similar trend appears to exist with decrease in strain rate, but the magnitude was much smaller due to the limited strain rate range investigated. Generally, the coarser lamellar structure gradually disappears and steps gradually decrease in size and number with increase in temperature and decrease in strain rate. A similar trend, in change of fracture mode, in the composite is indirectly manifested as a variation in total fracture energy with temperature, as shown in Fig. 5.

5. Discussion

The partition of applied stress into internal and effective stresses has proved essential in prediction of both creep and creep rupture of composites. The model predicts creep curves which fit the experimental creep results well in the range of temperatures investigated. The excellent agreement between the activation energy obtained by numerical fitting of experimental creep curves using Eq. (9) and the experimental activation energy obtained from the D M T A test demonstrates the consistency of the model. It has been demonstrated [31], by measuring the activation energies for composites with different fiber orientations and epoxy matrices, that the reinforcing fibers do not alter the creep mechanism (i.e. same activation energy) but alter its creep behavior by increasing the internal stress in the epoxy. This is manifested as an increase in glass transition (c~ transition) by approximately 6 degrees from 512 to 518 K. Though the c~ transition is predominant in the temperature range (295-558 K) of this study, at temperatures lower than 295 K, where the fl transition is predominant in the matrix, a decrease in transition temperature by 7 degrees from 209 to 202 K, without any change in activation energy, was observed. This also confirms that reinforcing fibers do not alter the creep mechanism. The Weibull shape parameter fl, which determines the shape of the strain rate-effective

J. Raghavan, M. Meshii / Materials Science and Engineering A 197 (1995) 237-249

245

stress curve, is found to decrease with temperature. Hence the shape of the compliance-time curve also changes with temperature. This observation corroborates the concerns expressed in the introduction section that a simple superposition principle used in the past is not applicable to composite materials, particularly the one used in the present study.

In the creep rupture model, the rupture criterion is defined by Eq. (13): i.e. creep rupture occurs when the stored elastic energy reaches the critical energy, W~. This critical energy can be regarded as constant in the simplest case, i.e. independent of temperature and strain rate. The tan 6 value at 558 K, obtained for the composite using the D M T A test, was almost zero,

(a)

(b)

....

. . . . . . . . . . . .

< ~ i

~i~7

(c)

(d) Fig. 6 (a-d)

246

J. Raghavan, M. Meshii / Materials Science and Engineering A 197 (1995) 237-249

40

i ,,rm~

i Imll~

i 11111~

, i,im~

, iiiml

I ilmrq

I Ilmlg

I I,,ul~

i inaq

I ,mill

35
o

i--

r~

30 AS4 / 25 - .....
I iiLlil~ t lllill~ i lilli~

.o <

3501-6

[90116

Experimental @ 433 K Constant Critical Energy Critical Energy

I iliiii~ i lillli~ I I lilflil I lilill~ i ilHli~ l llilld I lii

10-1

101

103

105

107

109

Fracture Time : s
Fig. 7. Predicted and experimental creep rupture results for the composite at 433 K.

(e)
Fig. 6 (continued). Fractography of 3501-6 epoxy resin fractured, by constant strain rate testing, at a strain rate of 10 - 4 s - l . (a) 295 K, Erracmre = 152 kJ m -3. (b) 373 K. (c) 433 K, Efract~r~ = 508 kJ m -3. (d) 463 K, Efracture = 586 kJ m -3. (e) 552 K, i.e. Tg Jr- 40, Ef~...... = 122 kJ m -3.

45

i ilnm I

i illul

, ,rain I

i illn~

I IIIII1~

I tinny]

i i ltu,l~

, i i)lll I

I IIInl

~ 111111.

AS4 / 3501-6 [90116 40

suggesting that the energy dissipated by creep was nearly zero. Hence the total fracture energy of 43.9 kJ m -3 obtained at 558 K was considered to be the stored energy at fracture. Then, as per the fracture criterion discussed in Section 2, this stored energy at fracture would give an experimental measure of the value for the critical energy at 558 K. Lemay and Kelley [15] observed the fracture energy (Gic) of epoxies to reach a constant value at temperatures 60-80 degrees above Tg, when the matrix was in the rubbery state. Similar saturation in fracture energy at temperatures above Tg, independent of strain rate, was observed by many investigators [23,24] in elastomers. In this study, constant strain rate tests at strain rates differing by an order of magnitude, performed on pure resin and composite with fibers oriented at 10 to the loading axis, yielded the same fracture energy within a scatter of 15%. Hence the critical energy of 43.9 kJ m - 3 w a s considered to be the strain-rate- and temperature-independent constant critical energy and was used in the creep rupture prediction. However, verification of this constancy, at temperatures greater than 558 K and at strain rates differing by more than an order of magnitude, could not be performed due to experimental difficulties. The solid lines in Figs. 7 - 1 0 represent the predicted creep rupture curves for the composite, over a period of 30 years, using a constant critical energy of 43.9 k J m 3, Eq. (10) and model parameters whose

" 35

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I
-

..a,.....

.~

30

25

Experimental @ 403 K I Constant Critical Energy - - Critical Energy

L illll "i I IH,,,d i Himil i Imll 'I , llluul , imall I I,I

20

I IIIIII 'i

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i NH,,ll

10-1

101

103

l0 s

107

109

Fracture Time : s
Fig. 8. Predicted and experimental creep rupture results for the composite at 403 K.

values are given in the previous section. It can be inferred from these figures that the predictions based on the constant critical energy underestimate the creep rupture life, except at longer lifetime at 433 K. The trend, however, is clear that deviation of experimental results, represented by the legends, from predicted lifetime becomes smaller as temperature and creep lifetime increase. Hence the constant critical criterion is useful in predicting very long creep life of the composite used in this study, particularly at elevated temperatures. The underestimation of creep life at temperatures lower

J. Raghavan, M. Meshii / Materials Science and Engineering A197 (1995) 237 249

247

50 45 40
,o

115111~

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35
--.2

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.....
Hiiid i ilnlml I IIInd

Experimental @ 373 K Constant Critical Energy Critical Energy

i iiiHid i itllud i illuml I Hmn[ I iIiind i iiil,d i iiin~l

101

103

105

107

109

Fracture Time : s
Fig. 9. Predicted and experimental creep rupture results for the composite at 373 K.

55 50

i,n,,~

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10-1

101

103

105

107

109

Fracture Time : s
Fig. 10. Predicted and experimental creep rupture results for the composite at 295 K.

than 433 K is due to the assumption in the constant critical energy criterion that the fracture mode does not change with temperature and strain rate. However, as shown in the preceding section, the fracture mode changes substantially with temperature in the epoxy matrix used in the present study. While the fracture at 552 K is characterized by a relatively smooth fracture surface (Fig. 6(e)), the fracture at 295 K is characterized by a rough surface (Fig. 6(a)). This change in fracture mode appears to occur continuously from 552 to 295 K. The fracture surface consists of a

fracture initiation region followed by a smooth region leading to steps [32] or a river-like pattern. The steps are followed by coarser stacked lamellar structure. Robertson and Mindroiu [32] explained these features, using a crack front fingering hypothesis and subsequent interaction of crack fingers due to local stress variation and local rotation of principal stress axis. Bascom et al. [33] suggested a role of plastic deformation in the formation of stacked lamellae. It is apparent from these fractographs (Fig. 6) that, with increase in temperature, the mechanisms that result in a stacked lamellar structure with localized plastic deformation are gradually suppressed, and the additional energy associated with such mechanisms also decreases. Hence this temperature dependence of the fracture mode suggests that critical energy (Wc) also depends on temperature, and that it decreases with increasing temperature, saturating at a temperature above the glass transition temperature (Tg). This is supported by the study of Cantwell and RoulinMoloney [34]. They related the fracture surface morphology and the stored elastic energy at the instant of fracture of epoxy resin and particulate-reinforced epoxy composite, and observed a gradual increase in smoothness of fracture surface with decrease in stored elastic energy. Similar morphological features were observed, in this study, in carbon fiber reinforced epoxy composite [AS4/3501-6], but the trend is not clearly visible due to the complexity of the fracture surface. This trend can be indirectly observed from the variation in total fracture energy with temperature as shown in Fig. 5. As per the creep rupture criterion discussed in Section 2, the stored elastic energy at fracture would give an experimental measure of the critical energy. The critical energy and its dependence on temperature was derived from constant strain rate results, since the three-element mechanical system had been shown to model the constant strain rate as well as constant stress behavior [28]. Stored elastic energy at fracture was calculated as follows. Using the fracture strain and ER, the internal stress was calculated. Subtracting this from fracture stress, the effective stress was calculated. Using Eqs. (11) and (12), the stored elastic energy was obtained. The average values of critical energy thus calculated at different temperatures are plotted in Fig. 11. The variation of critical energy with temperature in Fig. 11 is significant, indicating that the constant critical energy becomes a poor approximation, particularly at higher strain rates and in the low temperature range. An empirical method was employed to include this temperature dependence in the creep rupture predictions. Using an apparent activation energy determined from the experimental creep rupture data at 403 and 433 K, the critical energy values plotted in Fig. 11 were recalculated to obtain critical values as a function of strain rates at different constant temperatures. A power

248

J. Raghavan, M. Meshii Materials" Science and Engineering A 197 (1995) 237-249

90

80

AS4 / 3 5 0 1 - 6 [90116

]
70 60

50

40

250

, , , , , i . . . . ~. . . . I t i 300 350 400 450

l l l l L l l L l l l

500

550

600

Temperature : K Fig. 11. Critical energy plotted as a function of temperature, for the composite. 110 ,.v,v,~,,v,~,.v,~,,v-v,~,,v,v,~,,~,,v,v,~,,v,v,~,.v,v,~,,~,,v,~,,~ AS4 / 3501-6 [90116 1 100 - 295 K -- -- - 373 K / -- - 403 K J ]90=~.. 80 ......... 433K / ,

70

40 I N K Ili~ li~I 1 1 1 1 " lu ll~ II"A IdIlilI 1 1 1 1 1 ~ II1~ II'J L-J l U l ~ I1~ I"JI I I 1 ~ IlK Ili~ ] IdIdI1~ I~I1~ ll~ 10-2710-2410-2110"1S10-1510-12 10-9 10"6 103 1 Shifted Strain Rate : s 1 Fig. 12. Critical energy plotted as a function of strain rate, for the composite, at four temperatures. law was found to fit well the dependence of critical energy on strain rate. Due to the empirical nature of the power law, this relation is employed only in the interpolation for critical energy values. The critical energy values thus derived are plotted in Fig. 12, as a function of strain rate, for four temperatures. The creep rupture results, predicted using this strain rate and temperature dependent critical fracture energy, are shown by broken lines in Figs. 7-10. This empirical approach, to include the temperature and strain rate dependence of fracture energy, appears to be successful,

as the broken lines agree well with the experimental observations. The intersection of the broken line with the solid line indicates the demarcation point beyond which the constant critical energy criterion predicts the creep rupture life accurately. An earlier study [13] used the activation energy, determined from dynamic mechanical test data, to obtain the master curve for fracture energy (G~c), measured in mode I tests, as a function of strain rate at a constant temperature. A similar approach was examined in the present study. The creep activation energy of 494 kJ m - 3 was used to obtain the strain rate dependence of critical energy. The values obtained for the creep rupture life were not in good agreement with the experimental results. Since the rate-controlling process involved in creep and that in creep rupture are expected to be different, it is not surprising to find two different activation energies. It is clearly seen that even at room temperature (224 below Tg) considerable time-dependent reduction in strength occurs in polymer composites. Over a period of 25 years, the reduction in strength is calculated to be approximately 10% at 295 K, 20% at 373 K, 21% at 403 K and 24% at 433 K respectively. The simulated curve based on the temperature-dependent critical energy approaches and merges with the simulated curve based on the constant critical energy over a period of time. The estimated time when the curves merge is 5 105s at 433 K, 3 107s at 403 K, 8.7 101s at 373 K and 1.84 1022 S at 295 K. Beyond this time, the fracture is predicted by the constant critical energy. These results suggest that a critical energy for fracture can be used as a fracture criterion for the entire prediction range. However, this critical energy would vary with temperature and strain rate due to the variation of fracture mode. A constant energy criterion was used previously by Bruller [35] to predict well the linear viscoelastic limit in P M M A based on a modified Reiner-Weissenberg's theory for the strength of materials. Heil et al. [36] used such a concept to predict creep rupture of composites. But in both methods the stored energy was calculated from the experimental time-dependent compliance, modeled using a collocation scheme and arbitrarily choosing an average relaxation time per decade of creep time. The validity of such a fracture criterion over a wide range of temperature and time was not looked into. The conventional creep rupture models for composites rely on extrapolation, based on mathematical formulae that fit the limited experimental data. It can be realized from the present study that a simple mathematical fit is valid only over a limited range for materials that exhibit change in the shape of the applied stress creep rupture time curve with time and temperature. It has been shown in the present study that a simple creep rupture model, combining a creep model with a

J. Raghavan, M. Meshii / Materials Science and Engineering A 197 (1995) 237 249

249

critical energy fracture criterion, can be a p p l i e d to a h e t e r o g e n e o u s m a t e r i a l like c o m p o s i t e a n d yet a reliable s i m u l a t i o n o f creep a n d creep r u p t u r e c a n be a t t a i n e d in a wide stress a n d t e m p e r a t u r e r a n g e p r o v i d e d all the m o d e l p a r a m e t e r s are a p p r o p r i a t e l y m e a s u r e d a n d a n a lyzed. By a n a l y z i n g the s i m u l a t e d results, e x p e r i m e n t a l d a t a a n d f r a c t o g r a p h s , the influence o f fracture m o d e on p r e d i c t i o n o f creep r u p t u r e o f e p o x y c o m p o s i t e has been delineated. T h e suitability o f the present m o d e l a n d fracture criterion to p r e d i c t l o n g - t e r m r u p t u r e o f p o l y m e r c o m p o s i t e s is s u p p o r t e d by e x p e r i m e n t a l results. In a d d i t i o n , the m o d e l p a r a m e t e r s have h e l p e d in identifying the creep m e c h a n i s m [8] as well as in delineating the effect o f reinforcing fibers on the creep b e h a v i o r o f m a t r i x resin, which will be very useful during composite material development.

6. Conclusions
A simple creep r u p t u r e m o d e l has been d e v e l o p e d to p r e d i c t creep r u p t u r e o f u n i d i r e c t i o n a l c a r b o n fiber r e i n f o r c e d e p o x y c o m p o s i t e in a wide r a n g e o f r u p t u r e times a n d t e m p e r a t u r e s . A critical energy has been used as the creep r u p t u r e criterion. This critical energy has been f o u n d to be d e p e n d e n t o n t e m p e r t u r e a n d strain rate due to c h a n g e in fracture m o d e with t e m p e r a t u r e a n d strain rate. A c o n s t a n t value for critical energy has been f o u n d to be suitable for p r e d i c t i n g creep r u p t u r e at very l o n g times b e y o n d the e x p e r i m e n t a l time wind o w , for the c o m p o s i t e used in this study, especially at elevated t e m p e r a t u r e s . T h e c o n s t a n t critical energy has also led to p r e d i c t i o n o f a p r o o f stress b e l o w which t i m e - d e p e n d e n t fracture will never occur.

Acknowledgments
This w o r k was s p o n s o r e d b y the Officie o f N a v a l R e s e a r c h u n d e r c o n t r a c t N00014-89-J-3048. T h e aut h o r s w o u l d like to t h a n k Dr. Peter T h o r n l e y , Dr. Jeff M e y e r a n d Dr. D a n n F e n g o f A m o c o C h e m i c a l C o m p a n y , N a p e r v i l l e , I L for their help in D M T A testing. Also, the a u t h o r s w o u l d like to a c k n o w l e d g e the help o f Prof. I . M . D a n i e l for a l l o w i n g us to use his l a b o r a t o r y facilities, a n d the excellent technical assistance o f Mr. M. Seniw, Mr. A. Bilyk a n d R. K r a m e r at N o r t h w e s t ern University.

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