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Effect on the Elastic Modulus of High-Density Polyethylene

of Differing Thermal Treatments

Department of Materials Engineering, Monash University, Clayton, Victoria 31 68, Australia


The effect of different thermal treatments on the elastic modulus of high-density polyeth-
ylene has been studied in order to determine which of the parameters defining the polymer
morphology has the major effect on the modulus. After examination of the effects of crys-
tallinity, spherulite size, and lamellar thickness, it is concluded that it is the spherulite
size which plays the dominant role in controlling the magnitude of the modulus. 0 1995
John Wiley & Sons, Inc.

INTRODUCTION Effect of Thermal Treatment on Polyethylene
T h e heat treatment which is applied during pro-
cessing is one of the main factors which affects the The crystallinity, spherulite size, and lamella thick-
mechanical properties of polymer end products. ness are all significantly dependent upon the applied
Since polymers differ from metals or ceramics in thermal treatment. Experiments have therefore been
that the elastic modulus may vary with its mor- carried out to determine the extent to which crys-
phology, this article is primarily concerned with the tallization temperature, crystallization time, and
dependence of the modulus on the heat treatment. cooling rates affect these aspects of the morphology
The physical significance of the modulus in terms and, hence, the elastic modulus of high-density
of molecular movements is still unresolved, and, in polyethylene.
any case, it is strongly dependent upon the time scale A change in the crystallization temperature af-
of the experiment. In this article, the modulus will fects not only the rate of crystallization but also the
be taken as the ratio of applied stress t o measured size of spherulites which are formed. T h e critical
strain a t a time scale of approximately 0.1 s. T h e nucleus dimensions for growth decrease with in-
physical significance of the quantity will be discussed creasing undercooling for a given surface free energy.
in a later article.' At small undercooling, the critical size required for
Experiments have been carried out t o develop a n the formation of the equilibrium nucleus is relatively
understanding of the relationship between the mi- large and few spherulites develop. At large under-
crostructures of high-density polyethylene developed cooling, the critical size required for the equilibrium
by different thermal treatments and the mechanical nucleus is much smaller, and many spherulites de-
properties of the polymers which result from these velop.*~~
microstructures. T h e ultimate aim is t o develop a n The crystallization time will affect the overall
understanding which will enable polymer engineers crystallinity. T h e subsequent or secondary crystal-
t o control the mechanical properties of the end lization is normally accompanied by a n increase in
products, by changing the microstructure through the density of spherulites with time. Since the sec-
thermal or other treatment. ondary crystallization takes place a t temperatures
higher than the initial crystallization temperature,
* To whom t o address correspondence a t Department of this is also responsible for increased lamellae thick-
Manufacturing Systems Engineering, RMIT, Bundoora, Victoria n e s ~ .Similarly,
~.~ increasing the holding time a t the
3083, Australia
Journal of Applied Polymer Science, Vol. 58, 2429-2432 (1995)
crystallization temperature increases the lamella
0 1995 John Wiley & Sons, Inc. CCC 0021-8995/95/132429-04 thicknem6z7

Introducing different cooling rates to the polymer so that following the group number the first four
is equivalent to introducing different undercooling digits refer to the crystallization time and the last
and, hence, different crystallization temperatures? three digits refer t o the crystallization temperature.
In industrial practice, the effect is t o introduce dif-
ferent spherulite dimensions.
Crystallinity and Morphology Determination
Crystallinity of the samples was determined by den-
EXPERIMENTAL sity and by DSC. The densities were determined by
using a density gradient column. The enthalpies of
The polymer used was high-density polyethylene fusion were determined from the melting endo-
supplied in powder form without additives by therms obtained with a Perkin-Elmer DSC2B a t a
Hoechst and designated GA7260 ( M , = 97,900 and heating rate of 10 K/min. T h e enthalpies of fusion
M,, = 10,000). Samples were compression-molded were converted to degrees of crystallinity by taking
a t 180°C in a n induction-heated platen press and, 69 cal/g as the enthalpy of fusion of the perfect
subsequently, a number of different treatments were polyethylene crystal."*"
applied to these samples. A small-angle light-scattering method was used
In the first group of samples, different cooling to measure the spherulitic dimension of the polymer
rates were applied to the molten polymer in order samples. The sample which had been cut into a 10
to induce different morphologies. Slow cooling was pm section using a sledge microtome was placed be-
achieved by leaving the polymer melt in the platen tween a microscope slide and a coverslip. When a
press a t the maximum pressure t o air cool i t to room monochromatic laser beam wavelength of 632.8 nm
temperature. Samples made from this type of plaque was passed through the system, a four-leaf H , SALS
were termed "air-cooled ( AC ) " samples. Fast cool- pattern was obtained for samples which had a well-
ing was achieved by plunging the complete mold as- defined spherulitic structure." A photoelectric cell
sembly containing the molten polymer into the ice- was used to scan the H , SALS pattern in order to
water mixture. Samples made from this type of locate the maximum intensity. The scattering angle
plaque were termed "water-quenched ( WQ) " sam- 8, the angle between the main beam and the scattered
ples. light a t maximum intensity, and the wavelength of
In a second series of experiments, instead of slow the laser beam were used to calculate the average
or fast cooling, the polymer was crystallized in a spherulite radius R.
second platen press which had been preset t o the The lamella thickness was measured by DSC.
desired temperature. After holding the polymer a t These measurements were based on the fact that
different crystallization temperatures for 150 min lamellae with small dimensions melt a t lower tem-
a t atmospheric pressure, it was plunged into the ice- peratures and the melting temperature increases
water mixture. The crystallization temperature was with increasing lamellar thickness. If it is assumed
varied between 100 and 129°C with the idea of con- that a t a given temperature for a melting sample of
trolling the lamellar thickness. After the initial heat polymer the rate of heat input is proportional to the
treatment a t 18OoC,the polymer was held in a platen fraction of lamellae whose thickness is given by the
press a t specified crystallization temperatures for Thomson formula, then the distribution of lamellae
150 min. As the crystallization temperature ap- thickness can be obtained directly from the DSC
proached lOO"C, the change in lamellar thickness melting curve.13 A heating rate of 10-20 K/min was
due to variation in the crystallization temperature suggested t o be the most appropriate heating rate
levels off, and for a crystallization temperature for semicrystalline polymers on the basis of opti-
higher than 125"C, the time required for complete mizing the relation of the recrystallization and re-
crystallization increases d r a ~ t i c a l l y .Therefore,
~ organization rate of the polymer to the DSC scan-
crystallization temperatures lower than 100°C and ning rate.'*
higher than 129°C were not applied. The elastic moduli of samples cut into a 6.4 X 45.7
In the last group of samples, for a given crystal- mm dimension from 0.5 mm-thick molded plaques
lization temperature, different crystallization times were measured on a Rheometrics solids analyser
were applied. After the initial treatment a t 18OoC, (RSAII) a t two different temperatures of T = 28
the plaques were held at T,= 125 or 120°C in a and 48°C. All tests were done using a dual cantilever
platen press under atmospheric pressure for 150,240, bending fixture. T h e sample extension a t elevated
600, 1500, 2400, and 6000 min and then plunged temperatures was compensated by the spring-loaded
into the ice-water mixture. Samples are designated clamps in the fixture. T h e elastic modulus was re-

Table I Effect of Morphology-Crystallinity on Elastic Modulus for AC and
WQ Samples

Spherulite Size Lamellar Thickness Crystallinity Elastic Modulus
Group I (wn) (A) by DSC (%) (GPa)

AC 19.0 155.4 74.9 4.1
WQ 10.5 128.1 66.7 3.1

corded a t a static strain sweep mode a t a strain of talline and amorphous phases but also the fraction
0.1%. of interfacial material between crystalline and
amorphous phases.15
This analysis of Raman spectrum was used by
RESULTS AND DISCUSSION Glotin and Mandelkern in a study of the morpho-
logical structure of the polyethylene and the differ-
To examine the dependence of elastic modulus on ence between crystallinity determination by density
morphology-crystallinity, the different microstruc- and DSC methods.16 They concluded that the degree
tures produced by various heat treatment have t o of crystallinity determined from density measure-
be analyzed. A difference in crystallinity values was ments is equal to the sum of the crystalline and in-
found between the density and the enthalpy of fusion terfacial contents obtained from the Raman anal-
(DSC) methods. The authors claim that as the ysis, while enthalpy of fusion measurements yields
crystallinity of the polymer increases amorphous values equal to the crystalline content. Therefore,
chains-between the crystallites, particularly in the the difference between crystallinities measured by
interfacial region-become more and more oriented density and enthalpy of fusion is actually equal to
and go into a n ordered state, increasing the overall a n interfacial contribution. T h e difference in crys-
density of the polymer. Crystallinity calculations tallinities measured in this investigation also sup-
based on density ignore the increase in the amor- ports the proposition of a n interfacial contribution.
phous density and refer to a constant amorphous It is found that, as the crystallinity increases, the
density, consequently resulting in a discrepancy be- difference between crystallinity values obtained by
tween the crystallinity values measured by a density density and crystallinity methods decreases. De-
method and by a DSC method. These differences creasing divergence between the two methods of
can also be explained by a comparative analysis of crystallinity determinations with increasing crys-
the Raman spectrum together with the degree of tallinity is consistent with the fact t h a t the differ-
crystallinity results obtained by the two methods. ence between the two methods of crystallinity de-
Strobl and Hagedorn described a way of obtaining termination is due to the effect of a noncrystalline-
the level of crystallinity in semicrystalline polyeth- interfacial region.
ylene from a n analysis of the Raman spectrum. Table I shows the measured elastic modulus and
Their analysis of the Raman spectrum not only pro- morphology-crystallinity results for the samples
vides a means of determining the fraction of crys- subjected t o markedly different cooling rates. The

Table I1 Effect of Morphology-Crystallinity on Elastic Modulus at Constant
Time Duration but at Different Crystallization Temperatures

Spherulite Size Lamellar Thickness Crystallinity Elastic Modulus
Group I1 (clrn) (A) by DSC (%) (GPa)

0.150.100 11.3 132.0 65.0 3.207
0.150.105 11.9 129.0 68.6 3.417
0.150.110 13.3 136.6 68.9 3.438
0.150.115 16.6 145.0 70.9 3.482
0.150.120 20.4 162.7 72.1 3.541
0.150.125 185.7 72.3 3.655
0.150.127 189.8 73.4 4.358
0.150.129 200.6 69.6 3.911

Table I11 Effect of Morphology-Crystallinity on Elastic Modulus of Various
Crystallization Time at a Constant Crystallization Temperature of 120°C

Spherulite Size Lamellar Thickness Crystallinity Elastic Modulus
Group I11 (w) (4 by DSC (%) (GPa)

0150.120 20.4 162.7 72.1 3.54
0240.120 19.9 163.7 72.9 3.55
0600.120 19.8 169.8 74.2 3.63
1500.120 20.4 178.7 75.1 3.57
2400.120 19.9 174.2 76.0 3.68
6000.120 20.2 180.1 75.8 3.59

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- -
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morphological units in determining the measured Received November 18, I994
elastic modulus. Accepted June 5, 1995