J O U R N A L OF M A T E R I A L S S C I E N C E 24 (1989) 649 657

Temperature dependence of the mechanical

properties of EPDM rubber-polyethylene blends
filled with aluminium hydrate particles
Part 2 Static mechanical behaviour

M. T. C H A N L I A U - B L A N O T , M. N A R D I N , J. B. D O N N E T , E. P A P I R E R
Centre de Recherches sur /a Physico-Chimie des Surfaces Sofides,
24, A venue du Pr#sident Kennedy, 68200 Mu/house, France
G. R O C H E , P. L A U R E N S O N
Soci#t# Anonyme de T~l#communications - C~blerie de Riom, Route de Mar#chat, BP 153,
63203 Riom Cedex, France
G. R O S S I G N O L
Soci#t# Industrielle de Liaisons E/ectriques, Rue de Varennes Prolong#e, 77130 Montereau,
France

In this second part of the study concerning the characterization of new flame-retardant
materials, special attention has been paid to a ductile-brittle transition which occurs at about
70 ~C. In order to evidence the causes of this unexpected phenomenon of brittleness, all the
tensile mechanical properties (tensile strength, strain at break and modulus of elasticity) of
filled and unfilled EPDM-polyethylene blends are systematically studied in relation to thermal
conditions. Examination of the fracture facies of broken samples, at different temperatures,
clearly points out this transition. It is shown that the presence of a rubber phase within the
matrix is solely responsible for this type of behaviour. The fracture energy of the blends, as a
function of filler volume fraction and temperature, is also determined. Finally, a very simple
test on folded samples, allowing a precise determination of the critical temperature at which
the ductile-brittle transition occurs, is developed.

1. I n t r o d u c t i o n appears on increasing the temperature of a deformed

In a previous paper [1], the properties of new non-
halogen flame-retardant materials were determined as
a function of the temperature. These materials are
constituted by an E P D M rubber-polyethylene blend
filled with a large amount of aluminium hydrate par-
ticles. Firstly, the morphological aspects of these
blends and the distribution of the filler particles in the
matrix were studied. It was shown that the filler par-
ticles, totally coated by the E P D M phase, were very
well dispersed in the blend. Secondly, the thermal
characteristics of the pure polymers, analysed by dif-
ferential scanning calorimetry (DSC), were not or
only slightly affected when they were mixed together
or filled with aluminium hydrate flakes. Finally, a
dynamic mechanical study of unfilled and filled blends
showed that classical models describe well the influence
of the filler volume fraction on storage and loss moduli.
The second part of this study deals with the static
mechanical behaviour of these materials in relation to
the temperature. In fact, it was noticed by observation
of their fracture surfaces that, surprisingly, filled
blends presented a ductile-brittle transition around
70 ~ The aim of the present paper is to find an
explanation of the phenomenon of brittleness which
0 0 2 2 - 2 4 6 1 / 8 9 $03.00 + .12 9 1989 Chapman and Hall Ltd.
sample. Consequently, all the tensile mechanical
properties (tensile strength, strain at break and
Young's modulus) of the blends are systematically
studied in relation to thermal conditions. The fracture
energy, as a function of filler volume fraction and
temperature, is also determined. Fracture facies of
broken samples, at different temperatures, are observed
by electron microscopy. Finally, a simple test allowing
a precise measurement of the critical temperature at
which the brittleness occurs is developed.
Actually, the purpose of all these experiments is to
find out which constituent of the filled blends is
responsible for the initially unexpected phenomenon
of fragilization by temperature increase of the stressed
polymer blends.
2. Experimental procedure
2.1. Materials
Thermoplastic polymeric phases of the blends, com-
prising unmodified low-density polyethylene (PE) and
silane-modified polyethylene (SMPE), were used in the
same conditions as previously described [1]. In addition
to the EPDM elastomer fully characterized in the
previous paper and now denoted EPDM-1, two other
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TAB L E I Melting temperature Tf and degree of crystallinity C
of the elastomers

Polymer Tr (~ AH (Jg 1) C (%) f l

EPDM-1 50.3 21.8 8.1
EPDM-2 - 0 0
EPDM-3 48. l 10,6 3.9
EPR 54.1 49.4 18.3

types of EPDM rubber (EPDM-2 and EPDM-3)

(Vistalon, from Essochem) and ethylene;propylene-
rubber (EPR) were also employed. Their thermal
properties (melting temperature Tr, melting enthalpy
AH and degree of crystallinity C) determined by DSC
[1] and their ethylene content are gathered in Table I.
All three kinds of EPDM rubber contain 5-ethyl-
idene-2-norbornene as diene monomer.
Two types of filler were used: on the one hand, the
well-characterized aluminium hydrate flakes of the
previous study and, on the other hand, a thermal
carbon black (Sterling MT, Cabot, USA) with a density
of 2 g c m -3 and a specific surface area equal to
8.5m2g -~. Thus, the influence of the nature of the
filler on the mechanical behaviour of filled blends can
be then determined.
The unfilled and filled blends were made under the
same experimental conditions as previously described.
In each case, and independently of the nature of the
constituents, the composition of the blends was always,
by weight, 60% of elastomer phase and 40% of
thermoplastic polymeric phase (40% PE or 20%
PE + 20% SMPE). The volume fraction 4~ of alu-
minium hydrate particles varied from 0 to 0.45, while
that of carbon black was constant and equal to 0.50.
Figure 1 Unfolded and folded ISO I/2 samples dimensions in
millimetres).
made concerning the experimental value of t, since in
our case notches have been made on the two sides of
our samples.
To study the phenomenon of brittleness of filled
blends in the temperature range 60 to 80 ~ C, a very
simple test was specially developed. Samples (ISO 1/2)
were folded as shown in Fig. 1 and put in the environ-
mental chamber. The temperature inside this chamber
was then gradually increased from 20 to 120~ with
an increasing rate of I~ min-I and under constant
nitrogen gas flow. The behaviour of each sample was
continuously followed and recorded by means of a
video system provided with a timer. Consequently,
one was able to measure precisely at which critical
temperature 0c failure of the folded samples occurred.
Three samples in each case were tested by this method.
Finally, fracture surface micrographs of filled blends
were obtained by scanning electron microscopy (SEM)
using a Jeol JEM 100 B.

2.2. M e a s u r e m e n t s 3. Results and discussion

To study the static mechanical behaviour of our unfilled The values of tensile strength at, strain at failure er and
and filled blends, stress-strain curves were obtained modulus of elasticity E (at 0.2% strain) of unfilled and
on an Instron 1195 H tensile testing machine, at a filled blends ( E P D M - I - P E or PE-SMPE) are gathered
constant crosshead speed of 10 mm min ~. The testing in Tables II and III. The scatter of the results is equal
machine was equipped with an environmental chamber
enabling the temperature to be varied from room T A B L E ]I Tensile strength, strain at failure and Young's
temperature to about 100~ The elongation was modulus of unfilled and filled EPDM-1-PE blends at different
measured by an optical extensometer. Each sample, temperatures
with the standard ISO 1/2 shape, was held in the T Temperature (~
chamber for 30 min before testing in order to reach 20 40 6O 8O 100
thermal equilibrium at the chosen temperature. Tensile
Tensilestrength, a t ( M P a )
strength (at), strain at failure (er) and Young's modulus
0 > 11.0 >2.3 >1.5 1.2 0.5
(E) at 0.2% strain were then measured on five samples 0.17 > 14.6 >2.9 >2.0 1.3 0.6
for each system. 0.29 8.8 >4.3 1.9 1.1 0.6
Measurements of fracture energy were also carried 0.38 6.2 >3.7 2.3 1.5 0.8
out with the same mechanical and thermal conditions 0.45 6.8 4.3 2.9 1.6 1.1
using a "trouser tear" test, described elsewhere [2]. Strain at Nilure, e r ( % )
The tear test pieces consisted of rectangular strips, 0 > 800 - - 83 31
about 2 mm thick, partially precut with a razor blade 0.17 > 800 -- -- 138 45
0.29 737 -- 126 63 40
on each side along a central line so that only about 0.38 663 -- 79 26 35
0.6 mm of the thickness remained to be torn through. 0.45 76 50 15 9 16
The fracture energy G was calculated from the tear
Young's modulus, E ( M P a )
force F by the equation 0 0.9 0.8 0.6 0.4 0.2
2F 0.17 1.3 0.8 0.3 0.2 0.1
G - 0.29 2.0 0.9 0.6 0.3 0.1
t 0.38 4.3 2.4 1.1 0.7 0.3
where t is the width of the tear path. No correction is 0.45 4.6 2.6 1.4 0.8 0.5

650