Hot Water Aging of Polycarbonate

M. NARKIS
Chemical Engineering
Technion City
Haqa 32000, Zsrael
L. NICOLAIS and A. APICELLA
Chemical Engineering
University of Napoli
Naples 80125, Italy
and
J. P. BELL
ZMS, University of Connecticut
Storrs, CT 06268

Internal cracking and microvoids are shown to form during

room temperature storage of polycarbonate samples that have
previously been exposed to boiling water. These microcracks
or microvoids are actually disc-shaped pockets filled with wa-
ter. This formation occurs due to the creation of water super-
saturation conditions by cooling water-saturated specimens
from 100°C to room temperature. As a result, water phase-
separation, clustering, and microvoiding result and lead to
deterioration of the mechanical properties. Visual healing of
the microcracks is also sometimes observed at room tempera-
ture, especially under a dry atmosphere.Water from the water-
filled pockets diffuses through the polycarbonate matrix to the
external dry environment; the very thin emptied pockets then
close and visually heal. This paper provides experimental data
for the microvoiding process and clarifies the special mecha-
nism of cracking/healing in polycarbonate samples.

INTRODUCTION utilized in direct contact with hot water and PC

olycarbonate (PC) is a well-known polymer, es-
P pecially for its superior ductility and outstand-
ing impact-resistance behavior (1,2). The solubility
of water in PC increases from about 0.3 percent at
room temperature to 0.6 percent at 100°C. How-
ever, these relatively low concentrations of water
have significant and even dramatic effects on the
polymer’s mechanical performance (3-7). Hot wa-
ter causes gradual chemical degradation of the pol-
ymer; its long-term use in water having a tempera-
ture above approximately 60°C is not recom-
mended (8). Special PC grades having improved
hydrolytic resistance have been developed and are
available commercially. The water effect on PC may
be even more dramatic if wet PC samples experi-
ence thermal cycling (7). For example, upon rapid
cooling of water saturated PC samples, supersatu-
ration conditions are imposed, leading to the for-
mation of water clusters. Voids and cracks may
appear from the stresses associated with cluster
formation, resulting in a brittle, useless polymer
rather than the initially highly ductile material.
The ductile-brittle transition in PC polymers as-
sociated with hot-water treatment has been studied
by only a few authors, although PC articles are
parts are also steam-sterilized (3-7). The effect of
a given hot-water-treatment procedure will depend
upon the specific PC sample tested, its molecular
weight, additives present in the polymer and their
levels, and the processing method and cooling pro-
gram.
The objective of the present paper is to demon-
strate and explain the formation of some unique
defects in PC samples after exposure to boiling
water and storage at room temperature under var-
ious conditions.
EXPERIMENTAL
ASTM tensile dogbone specimens and flexural
bars, both 3.0 mm thick, were prepared by use of
an injection-molding machine (Ankenverke, Ger-
many). All injection-molded specimens were pro-
duced from Lexan 143 (General Electric Corp.).
Some preliminary studies on injection-molded Mer-
lon PC grade M-40 (Mobay) were terminated in an
early stage after observing a similar response to hot-
water treatment of these Merlon and Lexan mate-
rials. Some studies were also carried out on com-
pression-molded samples of Lexan 143 and on a
commercially extruded PC sheet. Samples were

POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1984, V d . 24, NO. 3 211

 M. Narkis
exposed to boiling water for periods from one to
eight days, and then were removed arid stored at
room temperature either in a desiccator or in dis-
tilled water. The specimens were frequently in-
spected visually, and photographed. They were
tested in tension using an Iiistron machine (Instron
Engineering Co.) at a crosshead speed of 1 cm/min.
Liquid water sorption kinetics were determined
by weighing samples as a function of water immer-
sion time. Differential scanning calorimetry studies
of the water-conditioned and desiccated samples
were performed by using a Perkin Elmer DSC-2
calorimeter at 2O"C/miii.
RESULTS AND DISCUSSION
The equilibrium solubility of water in PC in-
creases from 0.3 percent at room temperature to
0.6 percent at 100°C (7, 8). Thus water supersatu-
ration conditions are imposed upon PC samples
removed from boiling water and cooled to room
temperature. Owing to the slow diffusion of water
molecules from the thick polycarbonate specimens,
the excess dissolved molecules will form small water
pockets by phase-separation and clustering.
The rate of growth of these water pockets de-
pends largely upon the PC mechanical properties,
since significant mechanical deformations are tak-
ing place during their expansion. The mechanical
properties of PC exposed to boiling water are
known to change, and usually to deteriorate, with
time due to chemical hydrolytic processes leading
to degradation of the molecular weight (6). PC
samples containing water, whether in a dissolved
state or in clusters, will tend to desorb their water
to the environment (atmospheric air, dry air, or
even water if the PC is supersaturated) as long as a
positive driving force in the environment direction
prevails. This water desorption mechanism will
sometimes cause visual disappearance of the water
pockets; they gradually close during their water-
emptying process due to their geometrical two-
dimensional nature (7).
All these facts can be combined to explain the
observation of microcrack formation in PC samples
(samples which were previously boiled in water) at
room temperature, followed by a partial to com-
plete healing process of these microcracks (actually
water-filled pockets), as evidenced by their visual
disappearance. The visual healing process, how-
ever, does not necessarily mean restoration of me-
chanical properties.
The phenomenon of supersaturation conditions
causing phase-separation of water molecules, clus-
tering, and microvoid formation can also be applied
to other polymeric systems. Such systems are char-
acterized by a significant difference of their equi-
librium water-solubility values at the hot and cold
temperatures. The number and size of the water
pockets and their growth kinetics will change from
polymer to polymer depending on the level of the
imposed degree of supersaturation and on the me-
chanical and structural properties of the specific
polymer. They will also change for a given polymer
depending on its specific formulation (presence of
212 POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1964, Vol. 24, No. 3
various additives, hydrolytic stabilizers, etc.) and
molecular weight. A good example of another very
different polymer in which tiny voids can be de-
tected due to clustering of water molecules is per-
oxide-crosslinked polyethylene. Since crosslinked
polyethylene is used as an insulation layer for high-
voltage cables, its continuity and uniformity are
very important. The occurrence of microvoids i n
crosslinked polyethylene layers may lead to pre-
mature failure of the insulation by the well-known
"treeing" phenomenon (9, 10). High-temperature,
high-pressure steam ovens are utilized to crosslink
the crosslinkable polyethylene layer, followed by
water cooling. Water supersaturation conditions are
thus created in the crosslinked layer by this heat-
ing/cooling combination leading to clustering and
formation of tiny voids, detectable by microscopy.
A new technology, which uses dry nitrogen for the
curing and cooling steps, has recently been devel-
oped with the objective of eliminating conditions
for formation of the microvoids (11).
An injection-molded PC bar exposed to boiling
water for 8 days is shown in Fig. 1 . Parts (a) and (b)
of this boiled sample were immersed in water at
room temperature for an additional 10 days, and
part (a) was then placed in an air oven at 100°C for
16 hours. The water-filled pockets, usually having
disc shapes, are clearly seen in part (b). In fact,
when the continuous PC matrix becomes saturated
with water (saturation corresponding to direct con-
tact with water at room temperature) during the
room temperature water immersion step, the driv-
ing force for water to diffuse from the pockets to
the surrounding water becomes zero. At this stage,
the structure of the water-saturated continuous PC
matrix containing water pockets stabilizes, and will
remain intact as long as the sample is surrounded
by water at room temperature. If the sample is then
placed i n an oven at 1OO"C, Fig. l a , an enhanced
water desorption process will take place by emp-
tying the water pockets by diffusion through the
continuous PC matrix to the hot air environment.
The final drying step eliminates most of the visible
water pockets, leaving a milky sample due to the
Fig. 1 . Injection-inolded PC sample after 8 days in boiling water
and 10 days in water at room temperature. Part (a) was then
dried i n un ouen at 100°C f o r 16 hours.
 Hot Water Aging of Polycarbonate
Fig. 2. Liquid water sorption behavior of PC sheets of different grade (full symbols refer to Leran 143) and thickness (circles refm to 1.0
nun and triangles to 3.0 mm)
extensive localized plastic deformation and crazing
that have taken place during the growth of the
pockets at room temperature.
Liquid water sorptions were performed at 100°C
on: (a) injection-molded sheets of 3.0 mm thickness
(Lexan 143), (b) compression-molded sheets of 1.0
mm thickness (Lexan 143), (c) commercially avail-
able extruded (or compression-molded) sheets of
1.0 mm thickness, and (d) same as (c) but of 3.0
mm thickness.
Weight gains are reported in Fig. 2 as a function
of the square root of the time, normalized for the
thickness, corresponding to ordinary Fickian diffu-
sion. The experimental points for the four types of
specimens appear on two curves, i.e., for thin and
thick samples. Both curves s b w a maximum for the
weight gain in the initial stage of the sorption fol-
lowed by a slow progressive weight loss. The fast
initial gain may reflect the diffusion into and satu-
ration in the PC by the water, while the second
stage could be associated with the polymer degra-
dation and counter-diffusion facilitated by the
sorbed water. The normalized time needed to reach
saturation appeared to be approximately the same
for both thin and thick samples. This observation
indicated that the water sorption is governed by
ordinary diffusion. The two curves normalized to
square root of the time over the thickness, however,
are not coincident after the maximum. The overall
behavior is, in fact, controlled by the slower of the
two processes which characterize the long-term
aging, namely, the chemical degradation and
POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1984, V d . 24, No. 3
counter-diffusion of the degraded species. The sec-
ond portions of the curves will superimpose if the
actual times of immersion are considered. This in-
dicates that the diffusion of the degraded species is
fast compared to the kinetics of the chemical deg-
radation. Moreover, although the sorption behavior
seems independent of the grade of the PC, the two
sorptions are characterized by easily observed, dis-
tinct, visual morphological changes. The immersion
of the injection-molding grade PC in water at
100°C induces the formation of a large number of
disc-shaped fractures after only 1.0 hour, but only
a few fractures are observed after one day for the
commercially available sheets (12).
Figure 3 shows DSC thermograms for a virgin PC
sample and for two other samples after boiling in
water for 8 and 37 days, respectively. The Tg of the
sample boiled for 8 days is very similar to the virgin
PC, but, after 37 days in boiling water, the Tg of
the sample dropped by approximately 12°C. Dur-
ing the water boiling step of PC, its molecular
weight distribution is modified by hydrolytic deg-
radative reactions and by a removal process,
through leaching, of low-molecular-weight species.
The observed Tg may thus reflect changes in aver-
age molecular weight occurring by the two oppos-
ing effects, namely, degradation and loss of low-
molecular-weight chains. Such molecular weight
changes obviously will not be detected by Tg mea-
surements if the polymer sample is still in its Tg
versus molecular-weight plateau region.
In Fig. 4 , the number and size of the disc-shaped
213
water pockets generated by different conditioning
histories are shown. The longer boiling time results
i n a higher nuclei density, thus the size of the water
pockets will be reduced. Figure 4b shows clearly
the initiation sites for the subsequent growth of the
discs. The loci for the initiation of the disc-shaped
water pockets are closely associated with various
types of imperfections existing in the sample, such
as microvoids arid foreign materials, and with frozen
orientation and residual stresses which are depend-
ent upon the processing method and cooling con-
dition$. The exact appearance of these two-dimen-
sional discs depends 011 the disc plane orientation
relative to the observation direction. The very thin
needlelike shapes shown in Fig. 4 aTe actually two-

0,
U
U

I * I I 1
50 I00 150 200
T, O C
i f crack propagatiotl
Fig. 5 . Detnotrstrutiotr b y light inicrosco~~y
utrd shear band foriiiation originating fronr a disc-slruped crack.
F I ~3 DSC thennograins of ( a ) reference PC, (12) after 8 days Sunipl~'icus conditioned in boiling water and then rr~eclrutticully
i n boiling water, (c) after 37 days in boiling water All samples st riwetl.
u e r e dried in a desiccator before the DSC testing

Fig. 4. Disc-shaped cracks as seen in transmission light microscope: (a) sample boiled in waterfbr N days arid subsequently stored in water
at room temperature f o r 4 days, (I>) 5 days boiling and 1.5 days in water at room teniperature.

214 POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1984, Vol. 24, No. 3
 Hot Water Aging of Polycarbonate

dimensional discs whose plane coincides with the

observation direction. The disc-shaped cracks have
light-reflecting properties, and some of them will
appear and others disappear by tilting the speci-
men. In addition, the initiating nuclei and the re-
sulting water pockets are distributed randomly
throughout the specimen volume, leaving the outer
skin of the sample defect-free because of the rapid
removal of water from the skin to the environment.
Upon stressing of samples containing disc-shaped
cracks, the stresses will be concentrated, as shown
in Fig. 5.. Namely, shear bands are formed and
additional cracks originating from discs will de-
velop.
In Fig. 6 micrographs of polycarbonate virgin (a)
and conditioned for 3(b), S(c), and 8(d) days in
boiling water are reported. Samples were fractured
in tension shortly after the boiling water treatment.
Thus, visible microcraks formed by water clustering
due to supersaturation conditions were still missing.
The results indicate a ductile behavior, similar to
the one of the virgin material, for sample (b) and
progressively more brittle failure from (c) to (d).
The origin of the fracture is easily detected in a
localized microvoid. The overall fracture topogra-
phy seems to follow a recent failure scheme offered
by Morgan et ul. 1131, for a different system. This
failure scheme in tension includes processes asso- Fig. 7 . Fracture surfaces of injection-molded bars conditioned i n
ciated with craze formation and show crack growth boiling aater for 3 (a, c) and 8 (b, d ) days. Samples were then
through the fibril-filled crazes, resulting in rough storedfiw one week at room temperature in water (a, b) and in a
fracture regions. A smooth fracture topography is desiccator (c, d ) before testing.
then produced when the crack has progressed to
the vicinity of the craze tip and a slow crack growth,
with a small plastic deformation zone at the crack
tip, is taking place. Finally, a fast unstable crack
growth process occurs, resulting in rough fracture
surfaces.
The major effect of the water boiling treatment
is to reduce the PC molecular weight, thereby
gradually decreasing its ductile behavior. The long
fibrils, shown in Fig. 6a for the untreated sample,
gradually disappear and a penny-shaped cavity, in-
cluding the initiating microvoid site, appears (Fig.
6 4 . The reduced ductility is manifested also in the
fracture surfaces demonstrated in Fig. 7 (compare
71, with 7u, and 7d with 7c). The fracture surfaces
shown in Fig. 7 describe samples treated for 3 days
(7u and 7c) and 8 days (7b and 7 4 in boiling water
and subsequently conditioned for 7 days in water
(7u and 7b) and in a desiccator (7c and 7 4 both at
room temperature. As previously described, the
room temperature water storage step prevents the
healing process of the water-filled narrow discs ( 7 4
7b).The well-defined discs cannot be identified in
the fracture surfaces of samples stored in a desic-
cator. In the latter storage procedure, the water-
filled discs have lost their water to the dry environ-
ment, closed and healed.
The deterioration of the tensile properties with
time of treatment in boiling water is shown in Figs.
8 and 9. The ductile-brittle transition occurs after
approximately 4 to 6 days of conditioning in boiling
Fig. 6. Fracture surfaces of injection-molded bars: (a) reference, water as shown by the ultimate stress (Fig. 8) and
conditioned in boiling water for (b} 3, (c} 5 , and (d} 8 days. ultimate strain (Fig. 9).

POLYMER ENolNEERlNG AND SCIENCE, FEBRUARY, 1984, V d . 24, No. 3 215

 M . Narkis

The effects of time and environment (desiccator
or water) of conditioning at room temperature upon
strain at break are shown in Fig. 10. Samples boiled
for 8 days in water are shown to be very brittle and
their ultimate strain, immediately after the boiling
period, is already far below eY (yield strain of the
fresh PC samples). Samples treated for 3 days in
boiling water still retain a significant degree of
ductility (Fig. l o ) , however, their brittleness in-
creases during the subsequent room-temperature
conditioning step in water, as well as in the dry
desiccator environment. In fact, a ductile-brittle
transition occurs during the room-temperatrue con-
ditioning step by the formation of mechanical de-
fects whose concentration increases with time. The
ductility deterioration at room temperature is
shown to be faster for samples stored in water in
comparison with the ones stored in a desiccator, in
agreement with the visual observation and the frac-
ture topography evidence. One can conclude from
the gradual deterioration of ductility of the desic-
cator-stored specimens that visual healing of micro-
cracks does not necessarily mean restoration of

0 I
I
tin., hr.
Fig. 9. Tvnsile strain at break of injection molded specimens as
jiinction of immersion time in boiling water ( e y designates the
tensile yield strain of fresh PC samples).

t 0

A
doriccator

WRT

8 days BW

t
.001 I I 1 1 1 I 1 1 I 1 I
.I I 10 K)o
time,hr
Fig. 10. Effect of room temperature conditioning time in water (WRT) and in a desiccator on strain at break f o r samples boiled in water f o r
3 and 8 days (cy designates the tensile yield strain of fresh PC samples).

216 POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1984, Vol. 24, No. 3
 Hot Water Aging of Polycarbonate
mechanical properties, as stated earlier in this pa-
per.
Glass fiber-reinforced polycarbonate compounds
are often utilized to produce technical articles,
aimed to function in humid or wet conditions com-
bined with temperature cycling. The response of
such systems to various humidity/temperature-con-
ditions is even more complicated and will be the
subject of a future paper.
REFERENCES
1. D. G . Legrand,]. Appl. Polym. Sci., 13, 2129 (1969).
2. P. So and L. J. Broutman, Polym. Eng. Sci., 16,785 (1976).
3. S. P. Petrie, A. T.DiBenedetto, and J. Miltz, Polym. Eng.
Sci., 18, 1200 (1978).
POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1984, V d . 24, NO. 3
4. M. Yokouchi and Y. Kobayashi,]. Appl. Polym. Sci., 26,431
(1981).
5. E. Ito and Y. Kobayashi, 1. Appl. Polym. Sci., 22, 1143
(1978).
6. R. J. Gardner and J. R. Martin,]. Appl. Polym. Sci., 24,1269
(1979).
7. M. Narkis and J. P. Bell, 1. Appl. Polym. Sci., 27, 2809
(1982).
8. “Makrolon Polycarbonate,” Bayer Engineering Plastics KL-
46100 C. Edition 8, (1979).
9. S. Nunes, Ph.D. Thesis, University of Connecticut, 1983.
10. W. Heckmann and J. Schlag, Kunststofie, 72,96 (1982).
11. “Radiant Curing Process for Manufacturing HV and EHV
XLPE Cables,“ Maillefer INF 6E 3.77 RBR 2000, Switzer-
land
12. E. A. Joseph, D. R. Paul, and J. W. Barlow, Organic Coatings
and Appl. Polym. Sci., Proceedings, 47,272 (1982);l.Appl.
Polym. Sci.,27, 4807 (1982).
13. R. J. Morgan, E. T. Mones, and W. J. Steele, Polymer, 23,
295 (1982).
217