On the Solvent Stress-Cracking of

Polycarbonate
G. W. MILLER,* S. A. D. VISSER and A. S. MORECROFT*

Mobay Chemical Company

Pittsburgh, Penmylvania
The stress-cracking of polycarbonate by a gaseous or liquid
agent results from the diffusion of this agent into the polymer.
The low molecular weight polymer fractions and the chain ends
within the bulk of the polymer become more ordered during
the diffusion and swelling process by their partial solubility in
the crazing agent, causing crystallization. The creation of interfaces at areas of order-disorder causes high shearing forces
at this boundary and voids within the bulk of the polymer.
These voids are then propagated as crazes or cracks at stresses
much lower than the tensile strength of the polymer. Therefore,
a stress-cracking agent need not diffuse rapidly, but must be
an effective environment for swelling and/or crystallization.
Data from diffusion, density, thermal and molecular analyses
are presented to support this mechanism.

INTRODUCTION

common disadvantage of most polymers is their

susceptibility to crazing or cracking under the
influence of a tensile stress in some environment,
whether natural or artificial, and the rates are dependent on a great number of parameters, particularly molecular weight, chemical nature of the polymer, and environment. Bisphenol-A polycarbonate, a
polyester conceived and developed by H. Schnell
( l ) , has been found to exhibit this common phenomenon of stress-cracking ( 2 ) , the condition wherein polymeric material mechanically fails under stress
at a level lower than the normal tensile strength of
the polymer. Stress-crazing can be distinguished
from stress-cracking in that the former contains polymer within the developed flaw, whereas the latter
is void of this material.
Numerous investigators ( 3-8) have demonstrated
that considerations such as increasing the average
molecular weight, decreasing crystallinity, shock
cooling, decreasing molding stresses, and branching
may contribute to an increase in stress-cracking resistance, and other distinct causes for stress-cracking
have also been postulated (9-13).
Karasz and Kambour (14) have reported that the
diffusion of acetone into polycarbonate is Fickian,
and the opacity developed within the polymer was
suggested to be a consequence of an increase in
crystallinity with accompanying microscopic voids.
Present address: Owens-Illinois, Inc., Toledo, Ohio.
Deceased.

POLYMER ENGINEERING AND SCIENCE, MARCH, 1971, Vol. 11, No. 2

Stuart (15) has observed near crystalline order in

so-called glassy polycarbonate, and these ordered
areas were found to be 8OOA in size. The size of
these ordered areas increased with annealing below
150C. Small crystallites have been postulated as
responsible for the high modulus in the rubbery
region ( 16).
Carr, Geil and Baer (17) have shown that glassy
polycarbonate contains nodules in the surface of
about 125.A in size. These nodules enlarge even when
annealing below 150C, and their rate of growth is
accelerated at temperatures of 150C or more.
Lamellae readily form from these nodules near

150C.
It is the purpose of this report to examine the behavior of the stress cracking solvent in its manner
of permeation, effect on swelling and crystallization,
and mechanical failure at low stress levels for the
postulate of a mechanism by which solvent-induced
stress cracking occurs in Bisphenol-A polycarbonate.

EXPERIMENTAL
Materials
Polycarbonate samples used in this study were
equivalent grades of Merlonl, Lexan and Makrolon
polycarbonates, representing the three major manufacturers of this resin. Injection molded pieces in the
form of discs (0.125 in. thickness x 2.00 in. diam1 Registered

trademark of Mobay Chemical Co., Pittsburgh, Pa.

73

G . W. Miller, S . A. D . Visser and A. S. Morecroft

eter) or typical tensile specimens (ASTM D638)

were used in this study. The discs were used for the
bulk of the study on diffusion rates and thermal
analyses. Single specimens were used in each of the
diffusion measurements, and the solvents used herein
were freshly distilled through 20 in. X 1 in. columns
packed with glass rings or saddles. The molecular
weight characteristics of the materials used in this
study are given in Table 1.
Table 1. Molecular Characteristics of Samples
Sample
A
B

C
Dd

E
a

b
c

M,

x 103

X 103

MJMn

Ida

vnib

Densityc

36.5
38.6
36.0
48.0
27.7

20.0
17.0
20.4
19.6
13.9

1.83
2.27
1.76
2.45
1.99

0.61
0.63
0.60
0.66
0.46

1.40
1.53
1.05
3.0
1.15

1.1933
1.1866
1.1958
1.1884
1.1929

Mn

In CHrClr; dl/g.
Shear Rate, 72 sc-1; Poise x 10-1; 300%
g/cc.
This sample is Slightly branched.

Measurement of Tensile Stress Levels

The ultimate tensile strength in various solvent
media were measured on the Instron testing machine
by constructing a reservoir of solvent about the midsection of the tensile specimen and filling the reservoir, immediately prior to pulling the tensile specimen at 2.0 in./min. The reservoir was made by taping a polyethylene bag about the center of the tensile
specimen.
Tensile-Sorption Behavior
Tensile specimens were immersed in the designated
liquid, taken out, weighed, and immediately pulled
on the Instron testing machine to assess the decrease
in strength with sorption.
Diffusion Measurements

DuPont TMA, Model 940, used in the penetration

mode. The samples were obtained by peeling the
crazed surface from polycarbonate specimens and
completely removing all solvent at llOC/l mm Hg
for seven days before thermal analysis.
Molecular Weight Measurements
This information was taken from the measurements
on a Gel Permeation Chromatograph, calibrated with
polycarbonate and polystyrene fractions. Melt viscosity measurements were made on an Instron Capillary Rheometer at 300C and at a shear rate of 72
sec-'.

RESULTS
Tensile Behavior
An examination of the tensile behavior of polycarbonate in various stress-cracking media showed that
the ultimate tensile strength was dependent upon the
concentration of cracking reagent in the medium, and
the cracks appeared in the reservoir of liquid. (All
of the samples failed catastrophically when pulled on
the Instron tester but at different stress levels.)
Figure 1 shows the curve for the ultimate tensile
strength versus the concentration of carbon tetrachloride on immediate contact. The curve formed by
the squares is that of a branched polycarbonate,
whereas the other curve (circles) is that of a linear
polycarbonate. The increased tensile strength of thc
branched polycarbonate is probably due to the higher
molecular weight of the branched polymer. This sigmoidal curve was reproducible for many lots and
molecular weights of polycarbonate, shifting to
higher tensile strengths with increasing molecular
weights, when the CC1, concentration is greater than
SOY, in isopropanol.
9c

Polycarbonate discs were immersed in the desired

media at 25C for given periods of time. At a desired time, the disc was removed, blotted dry and
weighed. Single specimens in individual containers
were used for each time determination. Movement
of the opaque transition zone was measured by means
of a microscopic reticule and millimeter rule.
Density Determination
After drying the polycarbonate for seven days at
100"C/1 mm, the densities of various specimens were
measured by a flotation method ( 18), that of titrating
glycerine with distilled water until pieces of the
specimen neither rose nor sank. The density was
read from a predetermined calibration curve.
Differential Thermal Analyses
Thermal measurements were carried out on a
DuPont Differential Thermal Analyzer, Model 900.
Thermomechanical determinations were made on a
74

?m

go

80

70

60

I
50

I
b0

50

ZO

10

I
C

c c 4 , $ IN MTXRlRE

Fig. I. Tensile strength in CCl*/isopropanol mixtures.

Figure 2 shows the increase in tensile strength of

polycarbonate in 70/30 carbon tetrachloride/isopropanol with increasing molecular weight. This behavior
might be expected from the fact that others (3, 9
10) have shown that polycarbonate's ability to stresscraze is an inverse function of its molecular weight.
Isopropanol does not craze polycarbonate. An examination of the sorption or time-dependent tensile
POLYMER ENGINEERING AND SCIENCE, MARCH, 1971, Vol. 1 1 , No. 2

effccts of the stress-cracking agent reveals that the

tensile strength is proportional to the amount of
stress-cracking liquid sorbed ( Fig. 3 ) .

rates of benzene and toluene are proportional on

qiven samples, but there does not appear to be a
Lorrelation with weight-average molecular weight
or density.
Table 3 shows the diffusion coefficients and equilibrium sorption for polycarbonate, Sample A, in
Table 2. Diffusion Behavior of Liquid Mixtures
into Polycarbonatea

x 10-8,

50%
benzene
isopropanol

Sample
I

A
B
D
E

cm2lsec
50%
toluene
isopropanol

Density,
gicc

36.5
38.6
48.0
27.7

16.6
13.6

6.6
5.0
10.6
9.1

x 103

M,

1.1933
1.1866
1.1884
1.1929

Table 3. Diffusion Coefficients for Liquids into

Sample A Polycarbonate
Solvent

D )( 10-7, cmzlsec

Q,, %

6.3
13.8
0.019

27.5
48.0
72.0

Acetone
Toluene
Carbon Tetrachloride

Fig. 3. Sorption lis. tensile strength of polycarbonate in toluene (50): isopropanol (50).

Diffusion Measurements
Figure 4 shows the initial diffusion rates at 25C
for 50% mixtures of isopropanol (V/V) with benzene, toluene, acetone, xylene, and carbon tetrachloride into Merlon polycarbonate. The initial diffusion
rates appear Fickian. The distinct difference in rates
between CCl, and other stress-crazing solvents is
noteworthy. The fact that the lines for acetone, xylene
and toluene do not appear to emanate from the origin
could be due to the initial wetting characteristics of
each for polycarbonate. Carbon tetrachloride and
benzene do pass through the origin.
The approximate solution to Ficks diffusion law
for short times was used in the calculation of the
diffusion coefficients for various lots of polycarbonate
in 50% toluene and SO/o benzene (Table 2 ) ,

I
where Qsis the amount sorbed per weight of sample,
Qe is the equilibrium sorption, L the thickness of the
sample, D the diffusion constant, and t the time of
diffusion (19). The data indicate that the sorption
POLYMER ENGlNEERlNG AND SCIENCE, MARCH, 1971, Vol. I J , No. 2

.-

CARBON TETRACHLORIDE

0
0

10

a,
MINUTES
Fig. 4. Sorption of 50% mixtures with isopropanol b y Merlon polycarbonate.
75

various solvents. Though carbon tetrachloride is

very slow to diffuse into polycarbonate, its equilibrium sorption is much higher than any other solvent
in this study; this result is similar to the sorption of
n-propano1 by polyvinyl acetate ( 2 0 ) .
Figure 5 shows the equilibrium sorption ( Q e ) and
the diffusion coefficients ( 0 )of various mixtures of
toluene and isopropanol for polycarbonate. The sorption isotherm in Fig. 5 is typical of a material whose
surface is somewhat porous, and the pores fill with
solvent before diffusion begins. The diffusion curve
illustrates the semi-logarithmic relationship between
D and the concentration of stress-cracking solvent.
A compilation of sorption curves of toluene into
polycarbonate at various concentrations is illustrated
in Fig. 6. The curves show the time-to-equilibrium
sorption for given concentrations. Figure 7 shows the
Fickian behavior for the diffusion of carbon tetrachloride into polycarbonate, indicating the greater
amount of time necessary for equilibrium sorption
with apparent Fickian diffusion over several days.
Scveral samples which had been exposed to varying concentrations of stress-cracking agents in isopropano1 were analyzed by gas chromatographic
techniques, and the results showed that only the
stress-cracking agent was sorbed. The diffusion and
concurrent molecular ordering ( crystallization)

Fig. 5. Diffusion behavior of polycarbonate at ucrrious tolrime concentrations in isopropanol.

caused the polycarbonate to become opaque, and the

development of the width of the opaque portion was
a linear function of the square root of time, the rate
of development being governed by the concentrations of stress-cracking solvent. The movement of the
opaque transition zone and the change in total thickness or swelling of the polycarbonate were also a
function of the concentration of the stress-cracking
solvent used, as shown in Fig. 8. Hence, the stress-

(LiEb,

IT1

Fig. 6. Sorption rates of polycarbmte at various concentrations of toluene in isopropml.

76

POLYMER ENGINEERING AND SCIENCE, MARCH, 7977, Vol. 7 1 ,

No. 2

On the Solvent Stress-Cracking of Polycurbonute

(Trn)l/2, D*Ys

Fig. 7. Rate

of sorption of CC& b y polycarbonatc.

cracking solvent caused both swelling and crystallization during the diffusion process. After the polycarbonate had reached its equilibrium sorption level
with carbon tetrachloride, drying to completely desorb the polymer or organic liquid was carried out
to produce a specimen of polycarbonate which was
crystallized to the greatest extent with the solvents
included in this study. The specimen would not sorb
any measurable amount of any stress-crazing liquid
in five days.
Figure 8 shows that the formation of the opaque
crystalline-clear amorphous boundary during the diffusion of the stress-crazing solvent is proportional to
the root of time, similar to the rate of sorption. The

varying concentrations of toluene in isopropanol are

identified by the numeral on the rate plot, eg, 40
means 40% toluene and 60% isopropanol ( V/V ) .
During the diffusion of the toluene, the polycarbonate becDmes opaque and swells. The degree of
swelling is shown as the change in thickness with
the square root of time. The change in opacity when
plotted as a function of the thickness of the residual
clear section with the square root of time is linear.
If the opacity were due only to swelling, then the
rate of development of the opaque section (or decrease of clear section) would be the same as that
of the total increase in thickness. Since the swelling
and opacity develop at different rates, and since the
density of the opaque section increases with time,
it is likely that volume shrinkage or crystallization
accompany the development of the opaque section.
This is easily measurable after long periods of time
of immersion. It can be seen from Fig. 8 that after
one week's immersion ( 10,OOO minutes) in SO/SO
toluene/isopropanol, the opaque section is still developing, and there is no significant change in thickness. The density data from TabZe 4 illustrate an increase after one week's immersion. Hence, the swelling during sorption is accompanied by crystallization.
N

Density Changes
In Table 4 are listed the densities and relative
viscosities of polycarbonate subjected to various carbon tetrachloride and toluene treatments. For immersion times of one day, the density of polycar-

)O

Fig. 8. Movement of transition zone.

POLYMER ENGINEERING AND SCIENCE, MARCH, 1971, Vol. 11, No. 2

77

G.W. bliller, S . A. D.Vkser and A. S,. Morecroft

Table 4. Densities and Relative Viscosities of
Solvent-Immersed Polycarbonatea
Lot
Number

SampleA

Solvent

None
100%
100%
50%
100%
100%
50%

SampleC

cc14
cc14

None
50% CC14-lsopropanol
100% Toluene
50% T d uene-lsopropa no1

a
c

Density,
glcc

1.346
1.363
1.374
1.358
1.358
1.345

1.1961
1.1965
1.2300h
1.1953
1.2008
1.2049~
1.2062

1.306
1.345
1.347
1.336
1.326

1.1988
1.2012
1.1996
1.2146
1.2083

1.380
1.383
1.401
1.371
1.375

1.1945
1.1942
1.1927
1.2067
1.2041

CCI4-lsopropanol
Toluene
Toluene
To1uene-lsopropa no1

100% cc14

SampleD

Re1 Viscosity

None

100% cc14
50% CCl&opropanol
100% Toluene
50% To1uene-lsopropa no1

immersed 24 hr and dried at 100C/l mm for one week.

Immersed in CClr for two months.
Immersed one week and dried at l O P C / l mm for one week.

Table 5. Extraction of Polycarbonate with Stress

Crazing Solvents

% Low
Polycarbonate

Sample A

Sample B

% Extracted

Ends

Solvent

RT

Reflux

(RT)

Benzene
Toluene
Xylene
Acetone
Methyl lsobutyl
Ketone
Carbon Tetrachloride
Benzene
Toluene
Xylene
Acetone
Methyl lsobutyl
Ketone
Carbon Tetra-

1.36
0.88
0.67
0.66

0.65

51.8
96.0
85.6
100.0

0.33

0.98

100.0

0.37

0.61

100.0

1.58
0.95
0.87

16.20

chloride

Sample C

Benzene
Toluene
Xylene

Acetone
Methyl lsobutyl
Ketone
Carbon Tetrachloride

Sample D

Benzene
Toluene
Xylene
Acetone
Methyl lsobutyl
Ketone
Carbon Tetra-

chloride

78

11.80

0.74

57.5
100.0
87.6
100.0

1.13

100.0

0.73

100.0

1.35
0.61
0.39

0.53

68.4
100.0
89.9
100.0

0.75

100.0

0.36

100.0

1.65
1.00
0.71

10.60

9.60

0.72

94.2
97.9
100.0

1.06

100.0

0.62

100.0

bonate rose rather sharply when immersed in toluene,

whereas the density in carbon tetrachloride changed
little. This is due to the slow diffusion of the carbon
tetrachloride into the polycarbonate, whereas the
toluene diffuses at a much greater rate. The changes
in relative viscosity, particularly by toluene, reflect
the extraction of low molecular weight polymer from
the carbonate. This is further borne out in Table 5
where the percent of material extracted is listed for
various solvents for four lots of polycarbonate. Increases in polymer density are usually associated with
molecular ordering or crystallinity, and the changes,
in the absence of x-ray data, verify the crystallization
by the stress-cracking solvent. An x-ray analysis on
the acetone-treated polycarbonate showed it to be
14% crystalline (21).
At room temperature ( R T ) , benzene extracts the
most low molecular weight polymer, followed by
toluene, xylene, ketones, and carbon tetrachloride in
that order. Refluxing the polycarbonate in the solvent
naturally increases the rate, and consequently the
amount of low ends extracted is far greater, as depicted in the samples in Table 5. Benzene extracts
both high and low molecular weight polymer, even
at room temperature.
Figure 9 shows the gel permeation chromatograph
diagrams for the low molecular weight fractions that
were extracted by the stress-cracking solvents. In
the case of carbon tetrachloride and xylene, only
low molecular weight components were extracted.
However, with benzene, the final distribution represents an overlap of both high and low molecular
weight fractions. The elution of extracted polycarbonate at a higher elution volume is due to the presence of only low molecular weight polycarbonate in
the carbon tetrachloride and xylene extracts. The
original polycarbonate maximum occurring at an elution volume of 85-90 mI is typical for a sample of
hl, = 38,000 and
= 19,000.
Table 6 shows the effects of refluxing polycarbonate in a stress-crazing solvent for five hours. The
aromatic solvents extract both high and low molecular weight polymer, whereas the ketones and carbon
tetrachloride extract only low molecular weight polymer. The molecular weight distribution is narrow for
the extracted material, and the relative viscosity of
the recovered material changes little from the original. However, there is a definite change in melt viscosity which is due to crystallization. There is no apparent reason why some crystallization should affect
the melt viscosity from the original 'amorphous'
sample. The degradation of the carbon tetrachloride
extract is puzzling.

a,,

Thermal Analyses
Polycarbonate normally exhibits an endotherm by
DTA at about 150C; however, as stress-cracking
takes place and as it becomes crystalline, an endotherm due to molecular ordering results at a higher
temperature. In the case of immersion of a film in
carbon tetrachloride for sixteen hours at 25"C, a very
POLYMER ENGINEERING AND SCIENCE, MARCH, 1971, Voi. 11, No. 2

On the Solvent Stress-Cracking of Polycarboriate

Table 6. Effect of Solvent Extraction on Molecular Weight of Sample A Polycarbonate
EXTRACT

RECOVERED MATERIAL
Melt Viscosity

37,900
36,700
3,030
46,700
2,540
33,100
1.600
1,920

None
Benzene
Toluene
Xylene
Acetone
Methyl lsobutyl Ketone
Carbon Tetrachloride

18,900
15,400
1,900
31,000
1,650
23,700
1,260
1,460
1,350
1,530

1,680

2,090

sharp peak is observed, indicating a high degree of

molecular ordering, whereas with sixteen hours' immersion at 25C in toluene or acetone, a broad endot h e m occurs, indicating varying degrees of ordering
within the polymer ( F i g . 10).The very sharp endo-

130

I 125

I
120

I
115

110

105

2.00
2.38
1.60
1.50
1.54
1.40
1.27
1.32
1.24
1.36

1.40
1.01

1.357

1.01

1.344

0.72

1.358
1.340
1.352

1.06
0.86
Degraded

therm for the material crystallized in carbon tetrachloride is typical of the slow crystallization processes
that occur from the slow diffusion of carbon tetrachloride in polycarbonate and the concurrent higher degree of molecular ordering.

130 125

'1

ELUTION VOLUME, ML.

1.346
1.355

120

110

115

ELUTION VOLUME, ML.

80

60

t l l l l J
130 125 120 115 110 105 100 95 90

I
85

t
80

ELUTION VOLUME, ML.

ORIGINAL
0

I
115

I
1
1
110 105 100

1
95

11
90 85

1
80

ELUTION VOLUME, ML.

Fig. 9. GPC diagrams of extracted polycarbonate.

POLYMER ENGINEERING A N D SCIENCE, MARCH, 1971, Yo/. 11, No. 2

79

G.W. Miller, S . A. D.Visser and A. S . Morecroft

cck

\.., -t>u

300"c

200

ORIGIN

I
I

C6H5CH3

Fig. 10. DTA endotherms

AT

of

mazed polycarbonate.

Figure 11 shows the curves obtained from the thermomechanical analyses of these polycarbonate samples. The thermomechanical analyzer (TMA) in the
penetration mode measures a property analogous to
that from a Vicat softening measurement. However,
it is much more sensitive, and it can be seen from
Fig. 10 that the beginning of the DTA melting
endothexm of the carbon tetrachloride-treated polycarbonate is superimposable with changes in the
TMA curve. The expansion occurring near 75C has
been shown to be a consequence of crystaUizing the
polymer, and its magnitude and temperature increase
with annealing times (22). The toluene-treated sample, because of its broad degree of molecular ordering, begins to soften at about 190C. This agrees with
the beginning of the melting endotherm in the DTA
diagram.

DISCUSSION
Normal stress-crazing by liquids usually results in
rapid and catastrophic failure. Most of the common
tests of this phenomenon involve the measurement
of: ( a ) stress at which the specimen breaks (constant
strain); ( b ) the time to break at a desired stress
level (constant stress). The values shown in Fig. 1
demonstrate the maximum stress levels tolerable for
polycarbonate in the indicated medium. Isopropanol
does not craze polycarbonate. Since stress-crazing is
a rapid response to a stress in a given medium, it was
necessary to slow down the phenomenon by dilution
of the crazing agent and decreasing the stress level in
order to study the effects of the solvent on the bulk
polymer. Hence, molded discs, which appeared to
exhibit the least amount of molded-in stress (except
at the edges) and whose ratio of width to thickness
was 16:1, were used for the diffusion experiments.
Molded pieces with areas of high stress concentration
sorbed the stress-cracking agents more rapidly than
80

the discs, and bars which were put under some flexural stress sorbed the solvent even more rapidly.
Increasing the molecular weight will decrease the
susceptibility to stress-cracking since it will decrease
the rate of diffusion, swelling and the amount of low
molecular weight polymer available for extraction by
the stress-cracking solvent. The solubility of low
molecular weight polymer in all of the crazing agents
as well as the partial solubility of high molecular
weight polymer in a few preferred stress-cracking
solvents is evidenced by the GPC data in Fig. 9. The
sorption isotherm ( F i g . 5 ) is particular to h a t of a
porous surface, which may be characteristic of that
described by Stuart (15) and Carr, et a1 (17). This
partial solubility of the chain ends of the polymer in
the crazing medium, small as it may be, as well as
the manner of sorption, could indicate a preferred
swelling and extraction of polymer from areas which
may be more amorphous than the nodules on the
polycarbonate surface. These nodules have been
shown to be precursors to areas of definite crystalline
order (17). There should be some small density difference between these areas of differing molecular
order, but with available techniques it would be difficult to measure. This preferential sorption of organic
solvent and consequent swelling is the initiation step
for void formation. Crystallization is then a consequence of the increase in chain mobility from swelling and partial solubility of the polymer in the crazing agent.
The development of crystallinity in the polymer
with even short sorption times by the cracking solvent
is supported by a number of pieces of evidence in
this study.
1. The change in total thickness versus the decrease in the thickness of uncrazed polymer ( F i g . 8)
illustrates that the total swelling of the disc is not
equivalent to the increase in the swollen layer depth.
Hence some of the swollen layer must have shrunk
or crystallized during the sorption of the crazing
agent. A combined effect of swelling and crystallization caused the voids whose refractive indexes are

100

150

200C

Fig. 11. TMA diagrams of crazed polycarbonate.

POLYMER ENGINEERING AND SCIENCE, MARCH, 1971, Vol. 11, No. 2

On the Solvent Stress-Cracking of Polycarbonute

variant, producing the scatter of light or developed

opacity of the swollen layer.
2. The change in the DTA response of the polycarbonate as the stress-crazing agent is sorbed is illustrative of the increase in molecular order normally
associated with the thermal crystallization of the
polymer. Carr, et a1 (17) have shown by electron
microscopy that the small nodules in the surface of
polycarbonate enlarge on heating at 150C and
higher. The increase in the temperature at which the
endotherm occurs (Fig. 10) as well as the sharpness
of the peaks by CC1, immersion evidences the high
degree of crystallinity in the sample. The slow sorption of CCl, apparently provides a preferred crystallization. The higher temperature peaks in the DTA
caused by acetone and toluene apparently have a
heterogeneous dispersion of crystallites.
3. The change in the penetration temperature ( F i g .
11) and the shape of the TMA curves illustrate the
transformation of the original polymer to one which
has a higher mechanical deformation temperature on
treatment with the crazing agent. This mechanical
property change is normally illustrated by increasing
the crystallinity in polyethylene, polypropylene and
other polymer systems. Nielsen (23) has also shown
that crystallization of polycarbonate raises the temperature of the major mechanical loss from 150 to
about 220C.
4. The increase in density of the polycarbonate on
treatment with the solvents in this study adds another
piece of evidence for an increase in molecular order
(Table 4 ) .
These data support the manner of sorption, swelling, and solubilization of low molecular weight polymer, even for short times. Crystallization definitely
occurs, and the extent of change in molecular order
at the moment of contact of the liquid with the polymer is not easily quantified. However, high shearing
planes can be generated at interfaces where density
inhomogeneities exist, and cracks may propagate
from these points.
In measuring the effect of crystallinity on the stresscracking of polyethylene, the constant strain test indicates that higher density polymer decreases the
resistance to stress-crazing, whereas with the constant stress test, higher densities increase the resistance to stress-cracking (24). The two apparently
opposite behaviors may be resolved by considering
that the stress-crazing solvent is not sorbed by highly
crystalline polymer, but it is sorbed by polymers
which are predominantly amorphous. The constant
stress test requires a tensile stress equivalent to or
greater than the tensile strength of the crystalline
polymer when there is no diffusion. Hence the greater
the crystallinity (constant stress), the less chance for
diffusion and further crystallization. On the other
hand, the results obtained by the constant strain test
are apparently explained by the faster rate of diffusion as the induced stress increases, causing crystallization and void propagation for failure.
Plasticization also is known to increase stressPOLYMER ENGINEERING AND SCIENCE, MARCH, 1971, Vol. 11, No. 2

cracking in polyethylene terephthalate ( 8 ) . Here

again, the plasticizer acts as a crystallizing environment, causing voids and propagation of cracks similar to the mechanism of this study. Irradiation is
known to improve solvent stress-cracking (21); this
is attributable to branching or crosslinking which inhibit molecular ordering brought about by solvents.
Nylon is known to stress-crack in contact with water
( W ) ,and this behavior can be readily explained by
the type of mechanism demonstrated in this study.
Hence it would appear that the diffusion of the stresscracking agent holds the key to illustrating the modc
of crystallization for cracks developing at stress levels
less than those of the tensile strength of the polymer.

CONCLUSIONS
The data contained in this study may be interpreted to show that the stress-cracking of polycarbonate proceeds by diffusion of the solvent into the bulk
of the polymer. As diffusion takes place, swelling and
crystallization occur, and the slight solubility of the
polymer in the cracking agent mobilizes the polymer
chains to form regions of varying order. The ordering
of the polymer chains creates shearing forces and
voids at the ordered-disordered interface. Failure
under stress is then due to the propagation of these
surface flaws or voids. Hence, under conditions where
organic agents produce stresses by solvent crystallization, the resistance to stress-cracking is markedly reduced. The slower rate of diffusion of carbon tetrachloride causes more orderly areas to be formed than
with the rapid diffusion of aromatic and ketone solvents, allowing the polycarbonate to fail more catastrophically in the former solvent. The cracks always
emanate from the surface of the specimen.
ACKNOWLEDGMENTS
We ( G . W. Miller, S. A. D. Visser) dedicate this
work to our former colleague, A. S. Morecroft, who
was the major contributor at Mobay Chemical Company to the conclusions gathered during this and
other studies on the whole realm of polycarbonate
behavior.
The authors are grateful to Mobay Chemical Company for permission to publish this work. We would
like to acknowledge the helpful discussions of Professor F. Eirich, J. H. Saunders, s. Steingiser and G. F.
Bauman, and the assistance of V. L. Busick, D. H.
Cotton, K. S. Booth and W. C. Richards in performing the experimental work.
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