Stress-strain analysis of oriented polyethylene

L. E. Govaert* Centre for Polymers and Composites, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands and C. W. M. Bastiaansen Centre for Polymers and Composites, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands; and DSM Research, Geleen, The Netherlands and P. J. R. Leblans Agfa-Gevaert, Antwerp, Belgium ( Received 24 December 1991 )
The time-dependentdeformation behaviour of a commercialgrade of high-performancepolyethylenefibres (Dyneema SK66), was studied using static and dynamic mechanical testing. A mathematical model is proposed, where the total deformation of the fibre is regarded as being composed of a stress-linear delayed elastic component and a non-linear plastic flow contribution. The thermo-rheological characteristics of the delayed elastic contribution are obtained using dynamic mechanical thermal analysis. The non-linear plastic flow component is characterized separately using long-term creep experiments. Model predictions of stress relaxation and tensile experiments are in good agreement with the experimental data.
(Keywords: polyethylene; fibres; creep; stress relaxation; dynamic behaviour; modelling)

INTRODUCTION High-performance polyethylene fibres, with tenacities of 3-4 GPa and moduli of 100-150 GPa, are nowadays commercially produced by solution spinning and subsequent drawing of ultra-high-molecular-weight polyethylene (UHMW-PE) (M w > 103 kg mol-1) 1 - 6 . The high work to break and the viscoelastic character of these fibres render them eminently suitable for applications where high impact resistance and vibrational damping is required 7-9. One of the major drawbacks, however, is the pronounced time dependence of the mechanical properties of these fibres (creep, stress relaxation). In exploring new applications for UHMWPE fibres, the ability to predict the time-dependent behaviour of the fibres in various loading conditions is of great significance, The long-term mechanical behaviour of melt-spun/ drawn high-density polyethylene (HDPE) fibres has been studied extensively by Wilding and Ward 1-~4. They distinguished two separate contributions to the deformation: (a) a linear viscoelastic recoverable component, further referred to as the delayed elastic component ; and (b) a non-linear irrecoverable flow component, further referred to as the plastic flow component 1. Moreover, they showed~'~ t that the plastic flow contribution to the deformation is consistent with two temperature-activated Eyring dashpots acting in parallel. The linear delayed elastic deformation was incorporated into the model by addition of linear springs in series with the dashpots, *To whomcorrespondenceshould be addressed 0032-3861/93/030534-07 1993 Butterworth-HeinemannLtd.

which made it possible to predict, to some extent, creep 11 and stress relaxation behaviour 12't5. However, for accurate description of the deformation behaviour over a wide range of stress and temperature, this model requires several sets of parameters, each covering a limited area ~5. Moreover, since the model only contains two relaxation times, it will inevitably poorly represent the dynamic behaviour of the material (vibrational damping). In previous work 16 the delayed elastic behaviour of UHMW-PE fibres in creep, stress relaxation and tensile experiments was modelled using the classical theory of linear viscoelasticity~7. However, as the non-linear plastic flow contribution to the deformation was neglected in this approach, the validity of the model is restricted to small deformations and/or short loading times. In the present investigation, a mathematical model is presented that incorporates both the linear delayed elastic and the non-linear plastic flow contributions to the deformation. The model is based on the assumption that both components are additive and act independently. To investigate the validity of the stress-strain relation, a commercial grade of high-performance polyethylene fibre (Dyneema SK66) is fully characterized. The stress and temperature dependences of the plastic flow component are obtained by determining plateau creep rates from long-term creep experiments. The linear delayed elastic component is evaluated using dynamic mechanical experiments. It should be noted that the quantitative characteristic functions obtained in this study are specifically for the

534

POLYMER, 1993, Volume 34, Number 3

Stress-strain analysis of oriented PE: L. E. Govaert et al.

fibre investigated (SK66) and cannot be applied directly to predict the deformation behaviour of any solutionspun fibre. Similar to melt-spun fibres 1'11'14, the mechanical behaviour of solution-spun ultra-drawn polyethylene is strongly influenced by parameters such as molecularweight, molecular-weightdistribution, draw ratio and, additionally, polymer concentration in solution L4,18-25. The present investigation is directed to develop a profound mathematical analogue that is capable of predicting the actual deformation behaviour of oriented polyethylene fibres in any loading condition. As such, it provides a new methodology to analyse the effect of processing parameters and intrinsic polymer characteristics on the general performance of oriented polyethylene fibres. Also, the analysis of the deformation behaviour, as presented here, supplies a profound basis for a better understanding of the molecular processes underlying the deformation of oriented polyethylene26. To examine the development of irrecoverable deformation during creep, fibre samples were loaded at 500 MPa at a temperature of 70C. For each sample the loading time was varied, and the irrecoverable deformation was measured using the cardboard end tabs as a reference. To exclude any recoverable contribution to the deformation, each sample was allowed to recover at a temperature of 70C for a period exceeding 10 times the loading time. RESULTS

EXPERIMENTAL All experiments in this study have been performed on solution-spun, ultra-drawn UHMW-PE fibres Dyneema SK66, supplied by DSM-HPF as a multi-filament yarn of 1600 denier. The modulus and strength of the fibres were 85 GPa and 3 GPa respectively, Dynamic experiments were performed in uniaxial extension in the frequency range from 0.2 to 3 Hz, at temperatures from - 2 0 to 105C. The equipment used for the experiments was a Polymer Laboratories DMTA MK 2. By splitting the multi-filament yarn, samples were prepared with a cross-sectional area of 0.01 mm 2 and a length of 20 mm. To prevent excessive creep of the fibres during the experiment as a result of the static load applied, a relatively low static stress level of 150 MPa was chosen. Further restriction of creep was achieved by reducing the static load at higher temperatures by means of the reduced force option that is available on the apparatus. All scans were performed at least five times and the results were subsequently averaged, resulting in a relative accuracy of 5% for the dynamic modulus Ed and tan ~. Stress relaxation, creep and constant-strain-rate experiments up to 10 - 3 S-1 were performed on a Frank 81565 tensile tested equipped with an extensmeter and a thermostatically controlled oven. Additional tensile experiments with high strain rates (up to 10 s - l ) were performed on a Zwick Rel servo-hydraulic tensile tester equipped with a thermostatically controlled oven. In all cases the fibre samples had a length of 255 mm. To improve clamping, the fibre ends were provided with cardboard tabs glued together with an epoxy resin. The stress relaxation experiments, with loading times not exceeding 150 h, were performed at strains of 0.5-2.5% and temperatures of 30-70C. Creep experiments, with loading times not exceeding 50 h, were performed in dead-weight loading at loads of 200-1500
M Pa and temperatures of 30 90C. Plateau creep rates

General deformation behaviour In Figure 1 the creep compliance D(t) = e(t)/ao of the SK66 fibre is presented as a function of time for various temperatures and stresses. The creep curves at 30C can be regarded as representative of the general creep behaviour. Two important observations can be made : at short loading times the deformation behaviour is nearly stress-linear; while at long loading times the onset to a steady rate of creep is found (observed as an upswing of the curves in the double logarithmic representation of Figure 1), which is strongly stressdependent. The deformation behaviour observed may be regarded as being typical for oriented polyethylene, since similar observations were made on moderately oriented, melt-spun HDPE fibres by Wilding and Ward, who suggested a phenomenological model consisting of a linear delayed elastic component and a non-linear plastic flow component ~. This phenomenological interpretation is clarified in Figure 2, where the creep deformation of the SK66 fibre (70C, 500 MPa) is decomposed into its recoverable and irrecoverable components. The irrecoverable deforma-

0.1 -~ ~'5 ~ o = .~ ~ o i

/o
~~#~5ooc / j( ~ " ~

Qc /

..,," -"-' '- . /

.J

0.01

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

were determined from the creep data employing the method suggested by Sherby and Dorn 27. Additional information on the stress dependence of the plateau creep rate at high temperatures was obtained by determining yield stresses from constant-strain-rate experiments at 70 and 90C.

102

10 3

10 4

105

T i m e Is] Figure 1 Creepcomplianceof UHMW-PE yarn (SK66) at various temperature loads: 250 MPa (), 400 MPa (), 500 MPa (), and 750 MPa (V) and 1 GPa (A)

P O L Y M E R , 1993, V o l u m e 34, N u m b e r 3

535

Stress-strain analysis of oriented PE: L. E. Govaert et al.

............. ........... . . . . . . . . . . . . contribution, since at long loading times this component dominates and can be measured directly. At high temperatures, additional information on the stress dependence of the plastic flow contribution can be obtained in deriving yield stresses from constant-strainrate experiments 14. The stress dependence of the plateau creep rate, as measured on the SK66 fibres in both creep and constant-strain-rate experiments, is presented for various temperatures in Figure 3. Two important observations can be made : (i) The stress dependence of the plateau creep rate can be represented by a power-law relation in the stress region from 200 to 2000 MPa at all temperatures. (ii) The power-law slope appears to be independent of temperature. Apparently, the stress and temperature dependences of the plastic flow rate are independent of each other, which leads to:
~pl(O', T) = apl(T)Cff m (1)

Total

~-~_~fo ~
"-'

o~ / - - 0~

/~ zx//~ ~~- ....

~ ~ .... *

"7" = 102

=-----I
ra /
Irrecove

Recoverable/

r~

/ ~ _ U n i t slope )z

10-3 102

, /, .......

.........
10 4

103 T i m e Is]

Figure 2 Creep deformation at 70C and a load of 500 MPa (A), decomposed into its recoverable, delayed elastic ( ) and irrecoverable,

plastic flow (I-q) components. Experimental data on irrecoverable deformationare also represented (*) tion is observed to increase proportionally with the elapsed loading time or, more specifically, to develop at a constant rate in time. At long loading times this plastic flow component dominates the creep behaviour of the fibres, and a constant rate of creep is found. This constant rate of creep is generally referred to as the plateau creep rate, which, as can be observed in Figure 1, is evidently strongly stress- and temperature-dependent. Since the plastic flow contribution to the creep deformation increases proportionally with the loading time, the delayed elastic component will dominate the deformation behaviour of the fibre at short loading times. Of course, the time region where the stress-linear delayed elastic behaviour dominates (see Figure 1) will be determined by the value of the plastic flow rate at a given temperature and stress. In previous work 16 it was shown that the classical theory of linear viscoelasticity can be applied to the stress-linear (short-time) behaviour of the fibres and can be used to correlate stress relaxation, creep and constant-strain-rate experiments. The applicability of this linear viscoelastic stress-strain relation, however, is obviously restricted to a limited time region. To obtain a unified model that combines the contributions of both the delayed elastic and the plastic components, and, as such, will have a larger range of application, it is assumed that (a) both components act in series with each other, (b) the delayed elastic contribution is not influenced by the plastic flow contribution, and (c) the plastic flow rate is uniquely determined by stress and temperature.

where C = 4.6 x 10 -16 MPa -ms -1 (reference temperature 70C) and m = 3.7, and the temperature dependence of the plastic flow rate ~p~is represented by the shift factor up1(T). This temperature dependence is analysed in Figure 4, where the Arrhenius plots of the plastic flow rate at stresses of 200-1000 MPa are constructed. It is evident that the irrecoverable creep can be approximated by a single temperature-activated process with an activation energy of 28 kcal mol- 1 (118 kJ mol-1) over the entire region of stress and temperature experimentally covered. Consequently, the temperature shift factor ap~(T) can

10 .3 90 oc

10-4 -.~ ~ ~ ~ c~ a" = ~ ~ ~

10 .5 30 oc 10-6 ,, " 10-7 A 200

.i,I-

"

Characterization of the irrecoverable deformation."

plateau creep rates

1000 Stress [MPa]

Evidently, long-term creep experiments a r e preeminently suitable to characterize the plastic flow

Figure 3 Stress dependence of the plateau creep rate at temperatures of 30C ( + ) , 40C (A), 50C (O), 60C (I-q), 70C ( ~ ) and 90C (<>). The symbols (V) and ( * ) represent data obtained by

constant-strain-rate experiments

536

POLYMER, 1993, Volume 34, Number 3

_.-

-4 ~ ~ ~
"

Stress-strain analysis of oriented PE: L. E. Govaert et al.

excitation atlow static stress levels. Inthese conditions /~ 0.Z0GPa

the dynamic stress signal will not be influenced by the irrecoverable deformation process, since, even at high temperatures, the development of irrecoverable strain during a dynamic cycle is negligible. On the other hand, however, the static load applied should not be too high, since excessive irrecoverable deformation (equivalent to post-drawing) leads to an increase of the modulus of the fibres z6. The experimental data are shown in Figures 5 and 6, where the values of the dynamic modulus Ed (Figure 5) and tan 6 (Figure 6) are plotted versus the angular frequency for various temperatures. As expected, the dynamic modulus decreases with decreasing frequency at a fixed temperature, as well as with increasing temperature at a fixed frequency. The isotherms of tan 6, on the other hand, increase gradually with decreasing frequency for temperatures up to 70C, reach their maximum and subsequently decrease with decreasing frequency at higher temperatures. This maximum in tan 6 is generally ascribed to the a-relation process 28, and is in accordance with observations of Roy et al. 29 and Matsuo et al. 3 for solution-cast, ultra-drawn UHMWPE films, as well as with results of Gibson et al. for melt-spun HDPE fibres 31. Master curves of E a and tan 6 could be constructed by horizontal shifting of adjacent curves. With a relative accuracy of 5%, the same horizontal shift factor superimposes the tan 6 curves as well as the dynamic modulus curves. The master curves for E d and tan 6, at a reference temperature of 30C, are presented in Figure 7. The shift factors aro (T) used to construct both curves and those derived from stress relaxation experiments are plotted logarithmically against 1/T in Figure 8. It is clear that the data in Figure 8 cannot be represented by a single thermally activated Arrhenius process. The observed temperature dependence of the

'~
_~ - 5 ~
0~ _\

~
~\

~ .~\\
" " ~ ~

~7 0.30GPa 0.50GPa

~a -6 ~ =
"~ -7 ~

"\ ~-\ ~
z~ .

~.~ ~
~

0.50

Ol.OOGPa

.~ 2.70 290 3.1o 3.30

Reciprocal temperature [103K"]

Figure4 Arrhenius oftheplateaucreeprateat variousstresses plots

12 5 -10 C -20 10C o
20 C A+~fA O _

O~
~

~
V~ V

30oc

~-""-""/V /

~' ~ = "~ o -~ =~

100

40 C

50oc 0o oc 75 7ooc 80oc 90 oc 50 95 oc ~o5,,c

/ / o - ~ V/V / / o/~ //a~n

oja/
~ v/v / J r / v~v~ *J* / * / ~ *----*-f ~,,~f~""--" ,,~"/ a~a ~ A~ ~ -a- - -/ - - ~ / U ~o a o / ~ +~+

lit

ill

0.3

1 10 Angular Frequency [s']

~ 0.1

~6ooc

Figure5 Dynamic modulus of SK66 vs. angular frequency at temperatureSbe expressedfrOmas :-20 to 105C ~"7~

~ ~ ~ " ~ W''~ ~

nooc 405 cC

ap,(T) = exp

To

(2)

~ [.., ~"~.... ~ ~ _ +'-...~_ ~ a ~ .~ 0.005 .............. 0.5 1 10

2ooc tc o oc ~-~-10c -2o o c

where U = Arrhenius activation energy ( 118 kJ mol- 1), R = gas constant (8.314 J mo1-1 K - l ) , T = absolute temperature (K) and TO = reference temperature (343 K, 70C)" Although caution should be exercised in using extrapolations far outside the region experimentally covered, the experimental data available justify application of the temperature shift in the temperature range from 30 to 90C.
Recoverable deformation: thermo-rheologieal behaviour An efficient method to isolate the linear viscoelastic contribution experimentally is by dynamic strain

0.01

Angular Frequency [s']

Figure6 Tan 6 of SK66vs. angularfrequencyat temperaturesfrom
-2o to 105c

POLYMER, 1993, Volume 34, Number 3 537

Stress-strain analysis of oriented PE." L. E. Govaert et al.

,~ 10

100 ~

.,.

"7'
c~

10-2

20 -7

10 -~ 1 3 5

-5

-3

-1

Log Angular Frequency [s -1]

Figure 7 Master curves of the dynamic modulus ( A ) and tan 6 ( + ) of SK66 vs. the logarithm of the angular frequency for a reference temperature of 30C. The full curves represent the fit obtained with the continuous relaxation-time spectrum of F i g u r e 9

shift factor is generally interpreted in terms of combined contributions of at least two temperature-activated (crystalline) relaxation processes ~1 and ~2, for isotropic 32-34 as well as for oriented polyethylene 29'3. Of course, the contribution of two separate relaxation processes, possessing different activation energies, would lead to a thermo-rheologically complex behaviour, which implies that short-term experiments at high temperatures cannot easily be translated to long-term behaviour at low temperatures 32. However, in Figure 8 a similarity is observed in the temperature dependence of the dynamic data, measured from 0.2 to 5 Hz (short relaxation times), and stress relaxation data, measured from 100 to 10000 s (long relaxation times). This similarity suggests that the material behaviour is thermo-rheologically simple, which is more indicative of a single molecular process. The molecular origin of this deformation process has been studied extensively and is discussed in another paper 26. With respect to the present investigation, the observed similarity in the temperature dependences of short and long relaxation times indicates that the time-temperature superposition principle does apply over the entire frequency/temperature range. This implies that the constructed master curve (Figure 7) can be considered to represent the actual fibre behaviour at 30C. The shift factors ade(T), presented in Figure 8, will be used to translate the fibre behaviour to other temperatures. In order to obtain a mathematical stress-strain relation for the viscoelastic contribution, the classical theory of linear viscoelasticity is applied1 v. In this theory the stress is related to viscoelastic strain rate by the Boltzmann superposition integral'

5
o

o o
o

"C ~ ~ [.., "~

0
o

# o
O

o ,.-1

-5

o o 0
o

-10 c~ , , , , . . . . 2.50 3.00

, .... 3.50

4.00

1 / T [ 1 0 3 K "l]
Figure 8 Arrhenius plot of the horizontal shift factor aae(T), for a reference temperature of 30C: ( O ) shift factor as derived from the dynamic quantities; ( , ) shift factor as derived from stress relaxation

experiments the linear region in case equation (3) is valid for simple extensional deformations only, and cannot be translated directly to other deformation modes. To specify a stress-strain relation enabling description of the viscoelastic behaviour of U H M W - P E fibres over the entire region covered, a continuous relaxation-time spectrum for the stress relaxation modulus E ( t ) (ref. 17)

E(t - - t ' ) g d e ( t ' ) d t ' (3) ~ where a is the extensional stress, E is the relaxation modulus and ~ae is the strain rate acting on the delayed elastic component. It must be emphasized that in our
-

a(t) =

538

POLYMER, 1993, Volume 34, Number 3

Stress-strain analysis of oriented PE: L. E. Govaert et al.

10' / / / ~ for the plastic flow deformation, a stress-total strain relation is obtained by introduction of equation (6) into equation (4), which leads to"

/
a_ ~.~ 10 / f

a(t, T) =

-/~ ~ /

where E(t, T) is defined in equation (4) and ~pl(a, T) in equation ( 1 ).

fo

E(t -

t,

T)[~,o,

F, p l ( O ,

T)] dr'

(7)

Model verification
10' .
10 10"

EquilibriumModulus : 33 GPa . 10 103 106 109 ~, [sl .

Figure 9

The continuous relaxation-time spectrum H(z) of SK66 for

a referencetemperature of 30C is introduced (isothermal conditions): foo E ( t, T) = E~ +

-oo

( -t_~ din z H (z) exp \ ade ( T ) z J

(4) The lower and upper bounds of the integral are in practice restricted to finite values. An equilibrium modulus E~ is introduced to account for the reversible character of the viscoelastic contribution to the deformation, The procedure used to derive the relaxation-time spectrum H(z) is based on an approximate relation, suggested by Booij and Palmen 35, between the relaxation-time spectrum, the dynamic modulus and the loss angle 6. The procedure is described in detail in ref. 36. Since it proved to be difficult to find a spectrum that gave accurate predictions of both tan 6 and E d, the spectrum was constructed primarily for the prediction of the dynamic modulus. The distribution of relaxation times H(z) obtained by this procedure is presented in Figure 9, whereas a value of 33 GPa was derived for the equilibrium modulus E~, which represents the contribution of relaxation times over 109s. The predictions of the master curves of E d and 6, using the spectrum of Figure 9, are presented in Figure 7. The spectrum H (z) introduced in equations (3) and (4) leads to a stress-strain relation for the delayed elastic component that is applicable over a large frequency/time scale.

In order to evaluate the validity of the stress-strain relation, the stress build-up at different constant strain rates and the stress relaxation after different steps in strain were calculated and compared with experimental data. For model predictions, the stress strain relation, equation (7), was incorporated in a computer program that was specially written for this purpose. The loading time was divided into small time increments, and the deformation rate of the plastic flow contribution was assumed to be constant over an increment. The magnitude of the plastic deformation rate was accordingly recalculated for the next increment. The time steps chosen were sufficiently small to eliminate any influence of the discretization on the calculation results. Constant-strain-rate experiments were performed at 30 and 70C, at strain rates of 10 -4 to 10 s-1. Figure 10 compares the experimental results with numerical predictions, and shows that the model based on series connection of delayed elastic and plastic flow components leads to accurate predictions over the complete range of strain rates. Model predictions of stress relaxation at various strains are compared with experimental data in Figure 11, at temperatures of 30, 50 and 70C, respectively. At

2000

- - ~ v/ ,7/f" v/

v/
1500 ,--, ~ ~ "~ / /v/ v/ 7/ 1000 ~ .~ _a_ o_--~-z e~ v/ 7o c

Unified modelling
To obtain a unified stress-strain relation that covers the total deformation of U H M W - P E fibres, the delayed elastic and the plastic flow components are regarded to act in series. This leads to the following decomposition of the total strain Cto of the fibre : t
/;tot = gde "q- /~pl (5)

~
r~ / 500 /~
i,~'

"' ~" d
~/o /,6' ~'

where %~ and Spl a r e the contributions to the total strain of the delayed elastic and the plastic flow processes, respectively. The time derivative of equation (5) reads : ~d~(a, T) = eto, - ~p,(a, T) (6)

l 0 0. O0

' 0.02 Strain

0.04

[-]

Since the series connection represented by equation (5) implies that the stress responsible for the delayed elastic deformation is the same as the stress responsible

Figure l0 Constant-strain-rateexperiments at various temperatures

and strain rates of 10-'ts -~ ( O ) , 10-3s -1 (~7) and 10s -~ ( O ) ,

compared with model predictions (curves)

POLYMER, 1993, Volume 34, Number 3

539

Stress-strain analysis of oriented PE: L. E. Govaert et al.

100 REFERENCES 1 ~ 3 0 C ~_~-ZZ.2~.7~_ "~ 1~ (,~ ~ ~~ "" "'"~A-'"?~'-z~.v 50 C ~.~..,. D',.~, ,~ ~O..... "~h"-... E3"E3.< ) ~ ' O . \ ~ " ~ . " ~.,,
,.~ O

2 3 4 5 6 7

~"-.~
"~,, "~o ~ .

E3.,.i3\ \ "o. \ "iB,

"

8 9 10 11 12 13 14

~ "~

. ~'~A70C \. ~ ~. ~. ~. "~\

10
50

.... '
100

........

'
1000

, ,

15 16 17 18 19 20 21 22

Time

[s]

Figure 11 Stressrelaxation experiments at various temperatures and strain levels of 0.5% (+), 1.0% (O), 1.5% (A), 2% (O) and 2.5% ([S]), in comparison with model predictions (curves)

low strains, where the viscoelastic contribution is dominant, the predicted modulus is higher than experimentally observed, the deviation being within 10%.
This inaccuracy indicates that the delayed elastic

23 24 25 26 27 28 29 30

component is also intrinsically non-linear. At a higher

strain, where the plastic flow c o n t r i b u t i o n becomes

dominant, the accuracy of the predictions increases significantly.

CONCLUSIONS
A unified model for the c o m b i n e d c o n t r i b u t i o n of the

31 32 33 34 35 36

delayed elastic and plastic flow components was obtained by considering the two processes to act in series.
E v a l u a t i o n of the model in stress relaxation and

constant-strain-rate experiments (up to impact rate)

shows that the deviations between calculated a n d measured stresses are within 10%. Therefore, it can be concluded that the proposed model gives a n accurate

representation of the actual deformation behaviour of

oriented polyethylene fibres.

Smith,P., Lemstra, P. J., Kalb, B. and Pennings, A. J. Polym. Bull. 1979, 1,633 Smith, and Lemstra, P. J. Makromol. Chem. 1979,180,2983 P. Smith,P. and Lemstra, P. J. J. Mater. Sci. 1980, 15, 505 Smith, P.andLemstra, P.J. Colloid. Polym. Sci. 1980,258,891 Lemstra, J., van Aerle, N. A. J. M. and Bastiaansen,C. W. M. P. Polym. J. 1987, 19, 85 Lemstra,P. J., Kirschbaum, R., Ohta, T. and Yasuda, H. in 'Developments in Oroented Polymers-2' (Ed. I. M. Ward), Elsevier, London, 1987, p. 39 Peijs,A. A. J. M., Catsman, P., Govaert, L. E. and Lemstra, P. J. Composites 1990, 21,513 Peijs,A. A. J. M., Venderbosch, R. W. and Lemstra, P. J. Composites 1990, 21,522 Govaert, L. E., d'Hooghe, E. L. J. C. J. and Peijs, A. A. J. M. Composites 1991, 22, 113 Wilding, M. A. and Ward, I. M. Polymer 1978, 19, 969 Wilding, M. A. and Ward, I. M. Polymer 1981, 22, 870 Wilding, M. A. and Ward, I. M. J. Mater. Sci. 1984, 19, 629 Wilding, M. A. and Ward, I. M. Plast. Rubber Proc. Appl. 1981, 1, 167 Wilding, M. A. and Ward, I. M. J. Polym. Sci., Polym. Phys. Edn 1984, 22, 561 Sweeney, and Ward, I. M. J. Mater. Sci. 1990, 25, 697 J. Leblans, P. J. R., Bastiaansen, C. W. M. and Govaert, L. E. J. Polym. Sci., Polym. Phys. Edn 1989, 27, 1009 Ferry, J. D. 'Viscoelastic Properties of Polymers', Wiley, New York, 1980 Ward, I. M. Polym. Eng. Sci. 1984, 24, 724 Smith,P. and Lemstra, P. J. Polymer 1980, 21, 1341 Smith,P., Lemstra, P. J. and Booij, H. C. J. Polym. Sci., Polym. Phys. Edn 1981, 19, 877 Smith,P. and Lemstra, P. J. J. Polym. Sci., Polym. Phys. Edn 1980, 19, 1007 Smith,P. and Lemstra, P. J. J. Polym. Sei., Polym. Phys. Edn 1982, 20, 2229 Bastiaansen, C. W. M. PhD Thesis, Eindhoven University of Technology, 1991 Bastiaansen, C. W. M. Polymer 1992, 33, 1649 Bastiaansen, C. W. M. and Grooters, G. P. Polymer 1992, 33, 1653 Govaert, L. E. and Lemstra, P. J. Colloid. Polym. Sci. 1992, 270, 455 Govaert, L. E. PhD Thesis, Eindhoven University of Technology, 1990 Sherby, D. and Dorn, J. E. J. Mech. Phys. Solids 1958,6,145 O. Boyd,R. H. Polymer 1985, 26, 323 Roy, S. K., Kyu, T. and St John Manley, R. Macromolecules 1988, 21, 1741 Matsuo, M., Sawatari, C. and Ohhata, T. Macromolecules 1988, 21, 1317 Gibson, A. G., Davies, G. R. and Ward, I. M. Polymer 1978, 19, 683 Nakayasu, H., Markovitz, H. and Plazek, D. J. Trans. Soc. Rheol. 1961, 5, 261 RibesGreus, A. and Diaz Calleja, R. J. J. Appl. Polym. Sci. 1989,37,2549 Meier, D. J. (Ed.) 'Molecular Basis for Transitions and Relaxations', Midland Macromolcular Institute Monographs, No. 4, 1978 Booij,H. C. and Palmen, J. H. M. Rheol. Acta 1982, 21, 376 Scholtens, J. R. and Booij, H. G. in 'Elastomers and Rubber B. Elasticity' (Eds J. E. Marks and J. Hal), Am. Chem. Soc. Syrup. Set. 1982, 139, 517

540

POLYMER, 1993, Volume 34, Number 3