Effect of Thermal Aging on Impact Strength

Acrylonitrile-Butadiene-Styrene (ABS) Terpolymer

MICHAEL D. WOLKOWICZ and SATISH K. GAGGAR
Borg-Warner Corporation
Technical Centre
Washington, West Virginia 26181

A high speed puncture impact apparatus was used to mea-

sure impact loss in thermally aged ABS (acrylonitrile-
butadiene-styrene) as a function of time and temperature. Im-
pact energy values decreased to a low level and degraded
surface layer thickness increased as a function of aging time at
three aging temperatures. Systematic removal of surface layers
from thermally aged samples progressively increased impact
energy values to control levels. Infrared spectroscopy, differ-
ential scanning calorimetry and molecular weight data indicate
that degradation occurs in the rubber, graft and rigid phases at
different times during the thermal aging period. Microscopy
results show a critical degraded layer thickness which causes
brittle failure of the entire sample.

INTRODUCTION speed tester at a crosshead speed ofabout 1,OOO in./min.

hermal and photo degradation of rubber modified
T p o lymers has been studied by a number of investiga-
tors (1-6).On exposure to heat, rubber-modified poly-
mers suffer a significant drop in impact. strength. It is
generally agreed that degradation affects only the sur-
face layer and the thickness of this degraded surface
layer depends on both the time and temperature of
exposure to heat. Since the interior of the exposed sam-
ple usually remains unaffected, a routine pendulum
type of notched impact test generally does not yield
significant differences in the impact values of thermally
aged and unaged samples. Falling dart type of impact
tests although suitable for such studies, suffer due tolack
of sensitivity and the large amount of samples required
for testing purposes. In the present study a high speed
puncture test was selected to measure impact loss in
thermally aged ABS (acrylonitrile-butadiene-styrene)as
a function of time and temperature of exposure to heat.
Degradation of the rubber, graft and rigid phases was
studied using spectrophotometric, calorimetric,
chromatographic and microscopic techniques.
EXPERIMENTAL PROCEDURE
Thermal Aging
A high impact grade ABS was selected for oven aging
at various temperatures. Samples cut from an extruded
sheet (0.125 in. thick) were placed in an air circulating
oven at the required temperatures. At the end of the
required exposure period, samples were removed from
the oven and allowed to cool at room temperature.
Impact 'Testing
Test specimens of dimensions 1.25 x 1.25 in. were
cut from the aged sheet samples for puncture impact
testing. The impact testing was performed on a high
The puncture test employed a pneumatically driven
crosshead driving a steel rod with a % in. diameter
hemispherical end. The specimens were positioned
such that the punch hit the samples on the unaged side
thus causing failure on the aged surface. The total cross-
head movement was controlled so that it could b e '
stopped at desired depths of punch penetration in the
specimen. Since it was only desired to study the impact
characteristic of a thin surface layer, examination of the
specimen surface was done at each depth of penetration.
The punch penetration depth at which cracks first ap-
peared on the surface was determined and the puncture
energy value was calculated from the load deflection
curve obtained for that sample. The puncture impact
energy value obtained is the area under load-deflection
curve normalized with respect to thickness of the speci-
men. A minimum of four specimens were tested to
obtain puncture impact values. Figure 1 shows the ex-
perimental arrangement for the puncture test.
To determine the degraded layer thickness at various
times of exposure to a particular temperature, thin sur-
face layers were carefully scraped off from the surface
using a microtome knife. Each layer removed was esti-
mated to be approximately 0.01 mm based on the
amount of material removed from a given surface area of
aged sheet sample. The layers removed from the sample
were used to generate analytical information on rigid,
graft and rubber phases. Impact data was generated for
samples after removal of successive layers.
Molecular Weight Analysis
Each layer of material (weighing about 2 mg) removed
from the aged sheet sample was dissolved in acetone and
the solubles were separated from the insolubles using a
Beckman J-21C centrifuge. The soluble portion was

POLYMER ENGINEERINGAND SCIENCE, JUNE. 1981, Vol. 21, No. 9 57 1

 Michael D . Wolkowicz and Satish K . Gaggar

faces were then examined using an optical microscope to

determine the thickness of the degraded surface layer as
a function of thermal aging time and temperature.
RESULTS
Figure 2 shows puncture impact values as afunction of
aging time at an oven temperature of 190°C. The results
indicate that at 30 min of aging time, the sample has lost
more than 90 percent of its initial impact value. Beyond
1h of aging time, the impact values decreased to a very
low (almost constant) level. All samples after 30 min of
aging time showed a complete brittle failure on the
surface. Samples aged at 15, 20, and 25 min showed a
ductile failure although the impact energy values de-
creased by about 30 percent even at 15 min of aging
time. Figure 3 shows optical micrographs of fracture
surfaces obtained by driving the punch clear through the
specimens. It is clear that as the aging time is increased,
the thickness of degraded layer increases. Figure 4
shows the plots of degraded surface layer thickness as a
function of aging time at 3 aging temperatures. The
critical thickness of the degraded surface layer where
surface failure mode changes from ductile to brittle fail-
ure at room temperature is estimated to be about 0.02

Fig. I. Puncture impact apparatus.

dried in a vacuum oven at 130°Cfor 1h then dissolved in

MEK and used for analysis in a Water's Model 200 Gel
Permeation Chromatograph for determination of the
number average molecular weight and molecular weight
profile.
IR Studies
The grafted rubber phase (insoluble portion in
acetone) of each layer of material removed was swollen
in toluene and then pressed into thin films (1-2 mil thick)
at 175°C and dried in a vacuum oven at room tempera-
ture for 24 h. Infrared spectra of these films were then
obtained using a Perkin-Elmer 727B Infrared Spec-
trophotometer. Absorbance values of several functional
groups were calculated as a function of both the thermal
aging time and the layers of material removed from the
aged samples.
Differential Scanning Calorimetric Studies
DSC studies were carried out to determine the effect
of thermal aging on the glass transition of the rubber
phase. A DuPont 900 Differential Thermal Analyzer was
used over a temperature range of - 120 to 23°C at a scan
rate of 10°C per min.
Microscopic Studies
Thermally aged samples were impacted so as to drive
the punch clear through the specimen thus exposing a
cross-section of the fractured sample. The fracture sur- Fig. 3. Effect of thermal aging on surface degradation at 190°C.

572 POLYMER ENGINEERING AND SCIENCE, JUNE, 1981, Vol. 21, No. 9
 Effect of Thermal Aging on Impact Strength of Acylonitrile-Butadiene-Styrene (ABS) Terpolymer

quired to reduce the puncture impact values toless than

215%
21s a 232%
Fig. 4 . Degraded surface layer thickness us oven aging time at
190,215 and 230°C.
mm at each temperature of aging. The bulkfailure mode
of samples was also determined for samples aged at
190°C and the observations are listed in TubEe 1. These
results indicate that the bulk failure mode of sample
remains ductile up to a degradation depth of about 0.07
mm indicating that surface cracks formed during impact
testing can not propagate through the sample thickness
in a brittle manner. When the degraded layer thickness
reached a value of about 0.2 mm, the sample shattered
in acomplete glasslike failure mode. Removal of 0.2 mm
surface layer from the sample aged for 89 h at 190°C
restored the ductile failure of the sample. These results
indicate that there is a critical layer thickness (between
0.07 mm and 0.2 mm) at which brittle cracks formed on
the surface can traverse in a brittle manner through the
bulk of the sample. It is expected that critical layer
thickness will vary as test rate and test temperatures are
changed. Table 2 lists the time required for surface
embrittlement at various oven aging temperatures. The
surface embrittlement time is the oven aging time re-
10 percent of the initial impact value of unaged sample.
As expected the time to embrittlement is lowered sig-
nificantly as oven aging temperature is increased. An
activation energy plot of aging time vs 1/T (where T is
absolute temperature) gives an apparent activation
energy value of about 19.8k cal/mol which is in reason-
able agreement with the reported value of activation
energy for degradation process in ABS (5).
Figure 5 shows the plots of impact energy values as a
function of surface layers removed systematically from
the samples aged at 190°C. These results clearly indicate
that impact energy values progressively increase as sur-
face layers are removed from the samples aged for vari-
ous times at 190°C.
Table 3 lists the rigid molecular weight (MJ deter-
mined for each layer of material removed from the aged
samples and the corresponding puncture impact values.
The samples aged for 30 min did not show any significant
changes in rigid molecular weight. As the aging time
increases, there is a significant drop in rigid molecular
weight indicating that chain scission takes place in the
matrix phase. Molecular weight data and corresponding
puncture impact values show some inconsistencies
which are due to experimental scatter and the variations
in the thickness of the layers removed.
Figure 6 shows the infrared data indicating the prog-
ress of degradation of the rubber phase in the surface
layer as a function of aging time. Absorbance values for

Table 1. Failure Modes of Samples Oven Aged at 190°C

Surface failure Bulk failure

mode and mode and
impact value impact value
( Ib4n.) ('bp)
Aging Degraded layer Failure Impact Failure Impact
the- thiEkness(mm) mode value mode value

0 0 Ductile 890 Ductile 890

15 min. 0.002 Ductile 580 Ductile 580
20 min. 0.005 Ductile 500 Ductile - NUMBER OF LAYERS REMWED
25 min. 0.010 Ductile 220 Ductile - Fig. 5 . Puncture impact vs number of layers removed.
30 min. 0.019 Brittle 70 Ductile 450
45 min. 0.038 Brittle 30 Ductile -
1 hr. 0.048 Brittle <30 Ductile 400
2 hr. 0.062 Brittle <30 Ductile 400
3 hr. 0.069 Brittle <30 Ductile 400
89 hr. 0.25 Brittle <30 Brittle <30

Table 2. Surface Embrittlement at Various Oven

Temperatures

Temperature Time for surface c

"C O K Embrlttlement (min) Failure mode

165 438 120 Brittle TIME0

190 463 30 Brittle I, 4 PB-/-I,2-PB
~~*-ia-iTm Vi-Carbmyl ~~--Hydronyl
215 422 10 Brittle
232 505 5 Brittle Fig. 6 . Relation between functional group absorbance in ABS
surface layer on thermal aging at 190°C.

POLYMER ENGINEERING AND SCIENCE, JUNE, 1 9 8 1 . Vol. 21, No. 9 573

 Michael D. Wolkowicz and Satish K . Gaggar

Table 3. Molecular Weight Analysis of Rigid Phase for Each Layw

-
Mnand Impact
Aging Ib.-in. Layer removed
time In. 1 2 3 4 5 6 7 8 9
-
0 M" 50,000
-
Impact 890
15 rnin Mn 48,000
-
Impact 580
30 min Mn 46,000 42,500
-
Impact 70 480
l h Mn 32,500 27,000 25,000 38,000
-
Impact 20 400 350 475
2h Mn 19,000 22,000 19,000 23,000 25,000 - -
-
Impact 18 18 33 180 100 250 -
3h M" 19,000 17,500 20,500 19,000 20,5Oo -
Impact 18 18 19 19 19 340

the trans-1,4 PB (967 cm-') and, 1,2-PB vinyl (910cm-l)
rubber unsaturation sites show a sigmoidal decrease
with thermal aging time. After 2 h of aging time absor-
bance values for these groups are about 10 to 20 percent
of their original values. Likewise absorbance units for
carbonyl (1710 cm-') and hydroxyl (3500 cm-l)
functionalities which are products of oxidation reactions
show a corresponding increase with aging time.
Figure 7 shows the relationships between the absor-
bancies of the above mentioned functional groups and
the layers of material removed from sample thermally
aged at 190°C for 1h. As can be seen absorbance values
of the trans and vinyl rubber unsaturation increase sig-
Fig. 7. Functiorial group absorbance vs layers of ABS removed
from sample thermally aged at 190°C for 60 min.
nificantly as the depth of penetration beneath the sam-
ple surface increases. At the 5th layer or roughly 0.05
mm penetration, the vinyl and trans rubber absorbance
values are approximately 90 percent of the control val-
ues. Also, the absorbance values for the carbonyl and
hydroxyl degradation products significantly decrease as
penetration depth increases.
Figure 8 shows the infrared absorbance of the nitrile
stretch at 2250 cm-' in the grafted rubber phase as a
function of oven aging time at 190°C and layers of mate-
rial removed from a sample oven aged at 190°C for I h.
There is a sharp initial decrease in the absorbance of the
nitrile band during the first 30 min of aging time and
then the absorbance values level off to nearly constant
value. This suggests that grafted material is being re-
moved from the rubber phase as the oven aging time
increases. It is not certain whether the grafted material
is undergoing random chain scission or if it is being
selectively cleaved at the graft site on the rubber phase.
It is likely however that the graft site is chemically more
active and attack would preferentially occur there.
Again the nitrile absorbance increases when penetration
depth increases as indicated on Fig. 8.
Figure 9 plots the results of the T, analysis for the
grafted rubber phase using differential scanning
calorimetry. As shown in Fig. 9 the most significant
change in glass transition of the rubber in the surface
layer occurs after 45 min of aging time at 190°C. The
expected decrease of the rubber T , as a function of

"1 -Tg OF SURFACE LAYER VS, AGING TIME AT 190%

OF LAYER REMOVED AFTER AGING I HR. AT 190%
n****-"-Tg
10-
0.

J
15
. . 45 . 75. v
106
d

TIME (minutes)
I 2 3
LAYERS REMWED
4 5 -90
-lo&.
0
. I 1 . . .
10 20 30 40 5 0 60 TlME(min1
I 2 3 4 5 6 LAYERSREMOVED
Fig. 8. Relationship between grafted C 4 absorbance and
thermal aging time at 190°C and layers of ABS removed after Fig. 9. Dependence of rubbcr T , on thermal aging time at 190°C
thermal aging 1 h at 190°C. and layers of ABS removed after thermal aging 1 h at 190°C.

574 POLYMER ENGINEERING AND SCIENCE, JUNE, 1981, Vol. 21, No. 9
 Effect of Thermal Aging on Zmpact Strength of Acylonitrile-Butadine-Styrene (ABS) Terpolyrner
penetration depth beneath the surface of the sample
aged 60 min at 190°C is also shown in Fig. 9.
DISCUSSION
The results presented above on rubber, graft and rigid
phases clearly indicate that each phase plays a role in the
degradation process of ABS type polymers. The surface
embrittlement at 30 min of oven aging time at 190°C
apparently occurs without a significant change in rigid
molecular weight as shown by GPC analysis or extensive
rubber phase degradation as indicated by the relatively
unchanged glass transition temperature. This indicates
that the embrittlement is possibly due to cleavage of the
grafted portion from the rubber phase. The surface layer
behaves as having ungrafted rubber particles which is
known to have avery brittle behavior. This conclusion is
supported by the drastic decrease in nitrile absorbance
in the grafted rubber phase after 30 min of thermal aging
time. At this point the nitrile absorbance has decreased
to 25 percent of its original value whereas the trans-1,4
PB unsaturation is still at 70 percent of the control value.
After 1 h of aging time rubber phase degradation and
molecular scission in the rigid phase take place causing
further reduction in puncture impact values. The results
also indicate that since the rigid molecular weight is
decreased significantly after some time the material
would have very low impact values even if the rubber
and graft phase were left intact.
POLYMER ENGINEERING AND SCIENCE, JUNE, 1981, Yo/. 21, No. 9
CONCLUSIONS
The results obtained in this study indicate that the
high speed puncture test is a sensitive test to charac-
terize the surface degradation phenomenon in ABS type
polymers in terms of studying surface embrittlement.
The thickness of the degraded surface layer has been
established as a function of oven aging time and temper-
ature and it seems that there may exist acritical degrada-
tion layer thickness which causes brittle failure of the
entire sample. Infrared, DSC and molecular weight data
show that degradation occurs in rubber, graft and rigid
phases and it is indicated that the initial surface embrit-
tlement takes place due to graft phase separation. Re-
moval of surface layers is shown to eliminate the surface
brittle behavior of oven aged samples.
ACKNOWLEDGMENTS
Authors wish to thank Borg-Warner Chemicals for
allowing this work to be published. Experimental help
from Mr. J. R. Wilson and helpful discussions with Dr.
D. Kulich are appreciated.
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4. Michael G. Wyzgoski, Polym. Eng. Sci., 16, 265 (1976).
5. J. ShimadaandK. Kubuki,/.Appl. Polym. Sci., 12,655(1968).
6. P. G. Kelleher, D. J. Boyle, and B. D. Gesner, J . Appl. Polym.
Sci., 11, 1731 (1967).
575