Viscoelastic Properties of

Ac ryIo nitriIe - Butadie ne- Styre ne (AB S) PoIy mers

in the Molten State
MARIE-PIERRE BERTIN, GERARD MARIN, and
JEAN-PIERRE MONTFORT
LPMI-UPPA,Avenue d e lUniversit6, 64000 Puu, France
G. E. Plastics ABS-S.A., B.P. 1
60134 Villers-St-Skpulcre,France

The viscoelastic behavior of acrylonitrile-butadiene-styrene(ABS) terpolymers is

studied in the molten state. First, the behavior of the styrene-acrylonitrile (SAN)
matrix is determined. Then, the effect of the degree of grafting on AI3S rheological
properties is emphasized. A critical degree of grafting (DGc), corresponding to a
minimum of the viscoelastic functions in the low frequency region, is determined.
It defines a critical thickness of the grafted layer, and is related to the conforma-
tion of the grafted chains at the surface of the rubber particle. The DGc affects the
morphology of the ABS and also affects the appearance of a secondary plateau at
low frequencies. The effects of the rubber particles, of the grafted chains, and of
the morphology on the appearance of the secondary plateau at low frequencies are
clearly dissociated.

INTRODUCTION thermore, for ABS materials, Y . Aoki ( 11) put forward

igh impact resistance, good dimensional stabil-
H ity, and good processability have made acryle
nitrile-butadiene-styreneterpolymers (ABS) the ma-
terial of choice in many engineering thermoplastic
applications for more than thirty years, particularly
in the automotive industry and in electric household
appliances. Specific processability properties are of-
ten required by customers. Rheological studies of the
visoelastic behavior of ABS in the molten state are
related to the fundamental principles which govern
processability. riBS polymers belong to the family of
rubber-modified polymeric materials: they consist of
a poldstyrene-co-acrylonitrile)(SAN) matrix rein-
forced with SAN grafted polybutadiene (PB) particles.
Many studies of the steady-state viscosity in the
molten state on these types of materials may be
found in the literature (1-7). but this parameter p r e
vides limited information concerning heterogeneous
systems. More recent studies of their viscoelastic
properties have been made by means of oscillatory
deformations over a large frequency range, thus al-
lowing the description of the relaxation time spec-
trum of the samples, in order to give information
about the effect of the complex structure of such
materials (8- 13). These studies enhance a solid-like
behavior of the material in the low frequency region.
This particular behavior is called the secondary
plateau phenomenon as it is manifested by a nearly
constant value of the storage shear modulus. Fur-
the existence of a minimum of the complex shear
modulus at low frequencies, as a function of the
grafted SAN-polybutadiene mass ratio (degree of
grafting). The degree of grafting corresponding to this
minimum is called the critical degree of grafting, DGc.
The characterization and understanding of these two
phenomena, viz. the secondary plateau and the criti-
cal degree of grafting, are the core of this paper.
The viscoelastic behavior of the SAN matrix is first
characterized. Then, the effects of the various struc-
tural parameters (particle size, matrix molecular
weight, matrix composition, polybutadiene content)
upon the rheological properties of the ABS are em-
phasized. A morphological study of the internal struc-
ture of the ABS is of great help in explaining the
critical degree of grafting and the secondary plateau
appearance. The mean features of the viscoelastic
behavior are discussed in the last part.
MATERIALS
The SAN matrix and the SAN grafted polybutadiene
particles were synthesized separately and then me-
chanically mixed in a Brabender Plastograph at 170C
for 10 min.
The polybutadiene spheres are crosslinked and
well-defined in size, and the particle sizes were deter-
mined by transmission electron microscopy (Photo 1 ) .
The particles show a spherical shape, are nearly
monodisperse and have a regular distribution in

1394 POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, Vol. 35, No. 77
 Viscoelastic Properties of Al3S Polymers

over 20 min. The samples were placed in an oven at

50C until use to avoid any water absorption.
The characteristics of the SAN and ABS samples
used in this study are listed in Tables I to 4 . The AN
content of the SAN samples (Table 1 ) varies from 25
to 35% and their average molecular weights ( M w )
from 76000 to 228000. ABS 1 to 11 presented in
Table 2, are made of a blend of the same SAN 2
matrix with different SAN grafted polybutadiene sam-

Table 1. Characteristic Parametersof SAN 1-6.

Sample Mw AN% IP
SAN 1 76,500 29.9 1.77
SAN 2 93,900 30.1 1.8
SAN 3 112,500 29.9 1.56
SAN 4 87,100 24.7 1.5
SAN 5 68,100 34.3 1.6
SAN 6 227,800 27 3.1

Table 2. Characteristic Parametersof ABS 1-11

- PB ratio = 15%
-Matrix = SAN 2
-Graft SIAN =70130.
Sample D (nm) DG%
ABS 1 200 29
ABS 2 200 42.5
ABS 3 200 63
ABS 4 200 ao
ABS 5 420 33
Photo 1: ABS ABS 6 420 48
ABS 7 420 63.5
ABS 9 200-420 29-33
ABS 10 200-420 42.5-48
ABS 11 200-420 63-63.5

(x30 000)
Photo 1 . ABS. Table 3. Characteristic Parameters of ABS B-l
- PB ratio = 15%
-D=200 nm
space. The degree of crosslinking was determined by -Graft SIAN = 70130.
measuring the gel ratio, prior to reaction of the rub- Sample D (nm) DG % Ref. SAN
ber with the styrene/acrylonitrile monomers. The gel
ratio is defined as follows: the PB sample of weight P1 ABS B 200 42.5 1
ABS C 200 63 1
is put into toluene for 24 h at room temperature in ABS D 200 29 4
order to dissolve the free chains. I t is then placed into ABS E 200 42.5 4
an oven at 45C to evaporate the solvent. When the ABS F 200 63 4
weight remains constant, it is measured (P2) and ABS H 200 42.5 5
ABS I 200 63 5
corresponds to the weight of the crosslinked chains.
The gel ratio is equal to P2/P1. The value of the gel
ratio was different for the two particle sizes as fol- Table 4. Characteristic Parametersof ABS Gl-G9
lows: - Matrix = SAN 2
-D=200 nm
-D = 200 nm Gel Ratio = 93% -GraftS/AN=70/30.
-D = 420 nm Gel Ratio = 88% Sample PB% DG%
The polybutadiene (PB)/styrene (S)/acrylonitrile (AN) ABS G1 5 29
ratio of both the grafted rubber and the SAN matrix ABS G2 5 42.5
was measured by ETIR prior to mixing. The molecular ABS G3 5 63
weight M w and the polydispersity index Ip were de- ABS G4 15 29
ABS G5 15 42.5
termined by GPC. ABS G6 15 63
The sample preparation was as follows. The pow- ABS G7 25 29
ders were first dried at 150C under vacuum for one ABS G8 25 42.5
hour. They were then compression molded at 200C ABS G9 25 63

POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 7995, Vol. 35, No. 17 1395
 Marie-PierreBertin, Gkrard Marin, and Jean-PierreMontfort
ples (the graft has the same S/AN ratio than the
matrix), in order to get a constant polybutadiene
content of 15%. The SAN degree of grafting ( D G )
defined by
weight of grafted SAN
DG = weight of PB
varies from 29 to 80%, for two particle sizes, 200 and
420 nm, and for bimodal ABS (ABS containing two
different sizes of particles). The degree of grafting is
determined by measuring the weight of PB and the
weight of SAN grafted. The weight of PB is measured
prior to the reaction with the styrene/acrylonitrile
monomers. The weight of SAN grafted is determined
by substracting the initial weight of PB from the SAN
grafted PB. The SAN grafted PB is weighed after the
following operations: it is put into acetone for 16 h at
room temperature to extract the non-grafted SAN
(free SAN) from the grafted layer. The acetone is evap
orated under vacuum at 60C for 12 h. Then, the
powder of SAN grafted polybutadiene is dried in a n
oven at 60T, and weighed.
ABS B to I in Table 3 are made of a blend of the
same SAN grafted polybutadiene a s the one used for
ABS 1-4with various SAN samples (the S/AN ratio of
the grafted and of the matrix are possibly different).
The PB content is 15%.the particle size 200 nm, and
the degree of grafting vanes from 29 to 63%.ABS G 1
to G9 in Table 4 , are made of blends of the same SAN
grafted PB as for ABS 1-4 and ABS B-I with the
matrix SAN 2, in order to get a PB ratio of 5, 15, and
25%. The particle size is 200 nm and the degree of
grafting varies from 29 to 63%. To summarize the
table presentation: Table 1 presents the SAN samples
which allows the determination of the SAN viscoelas
tic behavior: Table 2 corresponds to ABS with various
degrees of grafting for two different sizes of particles
and for bimodal ABS; Table 3 presents ABS samples
with different matrix: ABS samples in Table 4 have
their degrees of grafting varying for three different
rubber contents.
EXPERIMENTAL
The viscoelastic measurements were performed
with a n Instron 3250 rotary Rheometer, in a parallel
plates geometry in dynamic mode. The plate radius is
1 cm. The shear and loss moduli were measured in
the frequency range from 10 to 100 Hz and in the
~
temperature range from 150 to 210C. In order to
limit aging effects of the ABS, the plates and the
sample were placed in a n oven under nitrogen gas
and therefore the ABS viscoelastic modulus did not
vary during the course of the experiments. A linear
viscoelastic response to a 5% strain amplitude was
observed in the whole frequency range.
RESULTS
Viscoelastic Behavior of the SAN Matrix
The SAN material is a statistical copolymer in this
S / A N ratio range. The value of the glass transition
1396 POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, VOl. 35, NO. 17
temperature is 106C.The viscoelastic moduli G' and
G ( w ) measured at 150, 170, 190, and 210C were
superimposed into a master curve at 170Caccording
to the time-temperature superposition principle. The
coefficients Cp and C: and f o , determined with the
W.L.F. (14) equation (Eq 1) are given in Table 5.
To = 170C
The viscoelastic behavior of the SAN matrix was char-
acterized. The effects of molecular weight and AN
content on the viscoelastic functions are respectively
shown in Figs. 1a and b and 2a and b. Slopes of 2
and 1 respectively observed for log G' us. log w and
l o g G us. logo were found. This modulus depen-
dence on frequency is usual for homopolymers: linear
for G and squared for G'. SAN 6 is a n exception,
probably due to its high polydispersity index (3.1).
which broadens and shifts the terminal zone to lower
frequencies. Furthermore, a n increase in molecular
weight shifts the terminal region to lower frequencies,
which means that the viscosity is increasing with
molecular weight (Fig. I ) . The low frequency zone
behavior is not influenced by variations in the S/AN
ratio of the materials, though a n increase in the AN
content from 25 to 35% slightly increases the plateau
modulus value. The AN variation from 25 to 35% is
not broad enough to allow conclusions concerning its
influence upon the viscoelastic behavior of the SAN.
Thus SAN behaves like a homopolymer with a nar-
row molecular weight distribution, explained by its
statistical copolymer structure (at this S/AN ratio
range) (15).
Viscoelastic Behavior of the ABS
The ABS polymer is a two-phase material and each
phase has a distinct glass transition: the SAN phase,
with a glass transition temperature of 106"C,and the
PB phase, with a glass transition temperature of
- 84C.In the temperature range of this study (150to
210C).ABS master curves and SAN master curves
are superimposed (when SAN molar mass is the
same), except in the terminal zone of the relaxation
Table 5. Effect of the ABS Characteristic Parameters
on C:, Cg, and f,.
Sample T%("C) c: (2 f0
SAN 22.8 7.4 147 0.06
ABS 1-11 60 5.4 110 0.08
ABS G1-G3 52 5.9 118 0.075
ABS G4-G6 60 5.4 110 0.08
ABD G7-G9 65 5.1 105 0.085
ABS B-I 65 5.1 105 0.085
 ViscoelasticProperties of Al3S Polymers
1 log G ' ( w 1
(b)
Fg. l a and b. Master curves of SAN samples at 170C.
Efects of the molecular weight. All units related to G' and G"
are Pa.
spectrum ( R g s . 3 to 6). This observation suggests
that the SAN behavior predominates over the ABS
behavior except at low frequencies where another
phenomenon appears. Therefore the AI3S behaves as
a homogeneous polymer at high frequencies and the
time-temperature superposition principle can be a p
plied in this region. The viscoelastic moduli measured
at 150, 170, 190, and 210C were superimposed into
a master curve at 170C.The coefficients Cp and C i
and fo determined with the W.L.F. equation are re-
ported in Table 5 for all samples.
The ABS values of Cp and Cg and fo are different
from those of the SAN matrix. The free volume frac-
tion increases with polybutadiene content, in agree-
ment with Casale et al (10). The free volume fraction
is also slightly increased when the matrix and graft
S/AN ratio are different (AI3S 1 to 11 compared with
ABS B to I). Other parameters, like the degree of
grafting, molecular weight, percent AN of the matrix,
or particle size do not have any effect on the free
volume (i.e. temperature dependence).
The most peculiar ABS viscoelastic behavior is
located in the lower frequency region where a sec-
POLYMER ENGlNEERlNG AND SCIENCE, MID-SEPTEMBER 1995, VOl. 35,
f l o g G'Cwl
SANl AN-30%
SAN4 AN=25%
* SANJ AN-35%
-3 -2 -1 I 2 3 log I w x a , )
(b)
Fig. 2a and b. Master curves of SAN samples at 170C.
Effects of the S/AN composition.
ondary elastic plateau appears: G' is higher than G ,
therefore the ABS exhibits a more elastic than vis-
cous behavior. This solid-like behavior at low frequen-
cies, which usually appears for heterogeneous sys-
tems, is not yet completely explained and several
theories have been presented (8, 16, 17). This will be
discussed later.
The ABS viscoelastic behavior in the low frequency
region strongly depends on the degree of grafting of
the rubber particles. Aoki's (1 1) experiments on ABS
samples showed that when varying the degree of
grafting of the rubber particles, the viscoelastic func-
tions exhibit a minimum at a degree of grafting that
he calls the Critical Degree of Grafting ( DGc). The aim
of this work is to better describe and understand this
Critical Degree of Grafting. Thus, several parameters
were varied and their effects upon DGc studied. G'
and G" were measured at a given low frequency in
the terminal zone ( w . a, = 10 rad/s) and plotted us.
~
the degree of grafting for different situations.
In the following paragraphs, the minimum of G'
and G is observed for the same degree of grafting,
but the modulus variations are higher for G' than for
G . Thus, only the curves obtained from G' are pre-
sented.
NO. 17 1397
 Marie-Pierre Bertin, Gkrard Marin, and Jean-Pierre Montfort

I log G ' f w l

I log G'iwi

D = 2 0 0 nm

.
x ABSI
AS S 2
-
BIMODAL
ABS9
ABSIO
+ ABS3
* ABSII
ABS4

21 I I I I I I I I )
-3 -2 -I 0 I 2 3 log f W XOJ

6 - J

5-

D= 200nm
4-
x ABSI
ABS2
+ ABS3
3-
ABS4

2
-3
I I
-2
I
-I
I
0
I
I
I
2
I
3
I
log l w x a l J
*
2 & -3 -2 -I 0 2 3 log fW XOJ

(b) (b)
Fg. 3a and b. Master curves of ABS samples at 170C. Fig. 4a and b. Master curves of ABS samples at 170C.
Effects of the degree of grafting for D = 200 nm. Effects of the degree of graftingfor bimodal ABS.

curve log G' us. the DG show similar shape for M w =

Particle size influence
.,
The particle size influence on the Critical Degree of
Grafting (DGc) was studied on ABS 1-7 samples
(Table 2). The elastic modulus, measured at 0'a, =
lop2 rad/s for the two different particle sizes, D =
200 and 420 nm, is reported a s a function of the
degree of grafting (Fig. 7). The DGc was measured at
the minimum of G' and found to be:
- D = 20P nm DGc = 40 to 45%
- D = 420 nm DGc = 20%, assuming that the vis-
coelastic moduli behave the same for 420 and
200 nm particle size, and thus shifting the curve
along the X-axis.
Aoki (1 1) found DGc E 45% for ABS with 170 nm
rubber particle size, which is consistent with our
value.
Matrix characteristics influence
Storage moduli measured at w . a t = rad/s are
plotted us. the degree of grafting for samples with
different matrix molecular weights (Fig. 9 ) and com-
positions (Fig. 10). Molecular Weight Influence: the
76,500 and for Mw = 93,900 (Fig.9). However, more
values are necessary to determine the DGc, and thus
no conclusion can be drawn concerning the molecu-
lar weight effect on the DGc. A modulus decrease
between the curves corresponding to Mw = 93,900
and M w = 76,500 is observed and attributed to the
effect of the matrix molecular weight on the viscoelas
tic behavior of the ABS.
Composition Influence: the curve log G' us. DG for
75/25 S/AN matrix composition exhibits a minimum
at about 40% degree of grafting (Fig. 1 0 ) but other
values are necessary to allow the DGc determination
for the 70/30 and 65/35. However, the DGc is equiv-
alent for ABS 1-4 with a 70/30 matrix composition
(Fig.7) and for ABS D-F with a 75/25 matrix compe
sition; therefore the S/AN ratio 75/25 and 70/30
has no influence on the DGc.
The modulus variations observed when the matrix
S/AN ratio differs from that of the graft (65/35 com-
pared to 70/30) have not been explained. Masuda (9)
showed that a small deviation between the matrix
and the grafted composition results in a large in-
crease of G', which is observed for the 75/25 curve
compared to the 70/30 one.

1398 POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, VOl. 35, NO. 77
 ViscoelasticProperties of ABS Polymers

loq G ' I W I !log G'IW)

6 -

5-

5 % PB 4-
* 29% GI
43% G 2
63% G3 3-

2
-3 -2 -1 0 2 3 log i w x a , ) -3 -2 -1 0 2 3 log (WXO,)

(a) (a)

I log G"1w) log G " l w )

5% PB 2 5 % PB
*
8 29% GI
43% G2
63% G 3
.
m
29% G 7
43% G 8
63% G 9

2 I I I I I 1 1 I c 1 I I I I I --
-3 -2 -I 0 ' 2 3 log ( W X O , ) -3 -2 -I 0 I 2 3 log I W X O J

(b) (b)
Fg. 5a and b. Master curves of ABS samples at 170C. Fg. 6a and b. Master curves of ABS samples at 170C.
Effects of the degree of grafting at 5% PB. Eflects of the degree of grafting at 25% PB.

Polybutadiene content injluence Morphology

The polybutadiene content varies from 5, 15 to 25%
for ABS G1 to G9 (Table 4). G' and G" at 0 -at=
rad/s were plotted us. the degree of grafting (Figs.
1 l a and b). At the low polybutadiene content of 5%,
the ABS behaves as the unmodified SAN matrix. At
15 and 25% rubber content, the DGc is v',sible and
its value is independent of rubber content.
Bimodal ABS
Bimodal ABS contains two different sizes of rubber
particles. They are commonly used for their good
impact properties. The bimodal ABS materials inves-
tigated in this study, ABS 9- 1 1, described in Table 2,
are made of a 50/50 weight blend of 200 and 420 nm
diameter particles. Their storage modulus, measured
at w . a , = rad/s, is plotted us. the average de-
gree of grafting in Fig. 8 and exhibit a minimum at
45% degree of grafting. This value is equivalent to the
DGc of the monomodal ABS with 200 nm particles.
Furthermore, below DGc, the bimodal AI3S behavior
in the low frequency region is dominated by the
smallest particle size.
The vlscoelastic properties of the ABS are strongly
affected by the degree of grafting, which might have
an effect on the grafted particle morphology. The mor-
phology of the samples was therefore investigated.
The internal structure of the ABS was studied by
transmission electron microscopy. The polybutadiene
particles were first stained with osmium tetraoxide
(OsO,) in order to a) harden the particles and b)
enhance the contrast between the PB and SAN
phases. Samples of both undergrafted (below DGc)
and overgrafted (above DGc) ABS. were studied, both
in the initial state and after shearing for 2 h at 210"C,
w = 10 rad/s. The sheared samples were quenched in
liquid nitrogen in order to examine the particle mor-
phology during the experiments.
In the initial state (Photos 2 and 3 ) . there is a
slight difference in morphology between undergrafted
particles and overgrafted particles. The particle dis-
persion in the SAN matrix is slightly less homoge-
neous in the case of the undergrafted particles and
some contacts between them are observable. At low
graft density, the PB particles might not be suffi-

POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, VOl. 35, NO. 17 1399
 - -

wa,=10-2rad/s w a,=10-2rad/s
To=170'C I T,=170'C I

T G (7.)
(a)
Ftg. 7a and b. Particle sue effect on the DGc.

bimodal
r W"
bimodal

w a , = IO-'rod/s w o,=IO-'rad/r
T o = 170'C
I To = 170'C 1
50 I 50 I
T G (Y.) TG ( X I
(a) (b)
Fg.8a and b. DGc f o r bimodal ABS.

I
I
7
\

L/
M,. 93900

M,.76500
"-1 / M,-76500

w a , = IO-'rad/s
T o = 170'C
I w a , = IO-'rod/s
TO=170'C
I
I 0 50 I
T G (7.)

Fig. 9a and b. Molecular weight effect on the DGc.

ciently covered and tend to agglomerate. The rubber
is not compatible with the matrix and the rubber
particles attract each other.
Photos 4 and 5 correspond to sheared samples. The
undergrafted particles (Photo 4) are strongly de-
formed while the overgrafted particles (Photo 5) still
retain their spherical shape. TEM photos of the same
sheared ABS, non-quenched, do not show any defor-
mation of the rubber particles which have the same
morphology as in the initial state. Therefore the parti-

1400 POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, Vol. 35, No. 17
 Viscoelastic Properties of ABS Polymers
41 1

75/25

70/30

b 65/35
-0 3 '

w a,= IO-'rod/s

2
0
To=170'C
50
1 1
100
2
0
To= 170'C
50
I
I
TG (Ye) TG ( X )
(a) (b)
Rs. 1 Oa and b. Compositioneffect on the DGc.

4'
w a , = lo-' rad/s
T o = 17O'C To=170'C

I
b b
-3-
-
0

u 25%

15%
I
21 I
II 20
* I
* 5%

0 50 100 50 I
TG (Ye) TG (%I
(a) (b)
1 1.a and b. Polybutadiene content effect on the DGc.
fk~

cle deformation during shearing experiments does
not correspond to an equilibrium state. The deforma-
tion related to the rigidity of the rubber particle and
to its surface tension, both change with the degree of
grafting. Above DGc, the particle surface might be
well-covered with SAN and when the material is sub-
jected to shear, the graft SAN, entangled with the
matrix, does not move and therefore the rubber parti-
cles, to which the other end of the graft chains are
attached, cannot move either and do not deform.
Photos of samples at the DGc show the same mor-
phology as those above DGc. Thus the particle stabil-
ity under shear depends on the degree of grafting.
The rubber particles which would not be sufficiently
covered get deformed and tend to agglomerate. The
less the particles are grafted, the worse the disper-
sion. When the particles are well-grafted, they are
more stable and are better dispersed.
The internal morphology of bimodal ABS samples,
bimodal ABS with DG = 29% (undergrafted small
particles and overgrafted large particles) and bimodal
ABS with DG = 43% (small and large particles at and
above DGc) can be seen in Photos 6 and 7, respec-
tively. The particles dispersion is better for ABS hav-
ing DG = 43%than for ABS having DG = 29%. due to
the attraction forces between the undergrafted parti-
cles. Furthermore, the small, undergrafted particles
shown in Photo 6 do not get deformed during shear-
ing, contrary to the undergrafted small particles of
the monomodal sample of Photo 4. The presence of
the large well-grafted rubber particles prevents the
deformation of the small undergrafted particles (the
large particles possibly provide more rigidity to
the matrix which avoids the smaller particles defor-
mation).
DISCUSSION
Critical Degree of Grafting
The effect of various parameters on the critical
degree of grafting can be summarized as follows:
0 DGc decreases when the rubber particle size in-
creases:
0 DGc is independent of the polybutadiene content;
DGc is unchanged when the matrix AN ratio varies
from 25 to 30%.

POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, Vol. 35, No. 17 1401
 Marie-PierreBertin, Gkrard Marin, and Jean-PierreMontfort
Photo 2 :ABS 1 - GD = 29%
(x40000)
Photo 2. Al3S 1 ~ DG = 29% - initial state.
The dependence of the DGc with particle size is ex-
plained by a lower surface area for larger particles,
which therefore requires less grafting on a weight
basis. The degree of grafting can be related to the
density of graft points at the surface of the rubber
particle. Therefore the critical degree of grafting corre-
sponds to a critical density of graft points, 0,. A
correlation with the theory of De Gennes (18) about
conformation of polymers attached to a surface can
help u s to understand the dependence of the vis-
coelastic behavior of the polymer with the degree of
grafting ( HLJ. 12).
when the density of graft points is below uC,each
graft chain occupies a half-sphere which do not
overlap each other. This is the mushroom confor-
mation.
when the density of graft points is at u,,each graft
chain occupies a sphere with a radius equivalent to
the radius of gyration.
when the density of graft points is above uc,the
graft chains are stretched and the chains of the
1402 POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, Vol. 35, No. 17
Photo 3 : ABS 3 - GD = 63%
Photo 3. ABS 3 - DG = 63%- initial state.
matrix are expelled from the SAN graft layer. This is
the brush conformation.
At v,, each grafted chain occupies the volume of a
sphere with a radius equivalent to the value of two
radii of gyration. Thus, assuming a core-shell struc-
ture of the rubber particle surrounded by the graft
SAN, the thickness of the graft layer around the
particle might be equivalent to the value of two radii
of gyration. The average value of this thickness can
be determined, assuming the shell only is composed
of the graft chains. Taking into account the penetra-
tion of the free SAN chains within the SAN graft layer
would provide the real value of the thickness, but an
estimation is enough.
The layer thickness T of the shell can be calculated
from the radius R and the number n of grafted
particles in the considered volume in the following
way:
volume (grafted sphere) - volume (sphere)
= volume (grafted)
P PR
volume (grafted) = volume (PB) . -. DG
PSAN
 Viscoelastic Properties of ABS Polymers

Photo 4 : ABS 1 - GD = 29% Photo 5 : ABS3 - GD = 63%

Photo 5. ABS 3 - DG = 63% - sheared Cfor 2 h at 21 0C
w = 10 rad/s).

(x40000)
Photo 4. ABS 1 - DG = 2970- sheared ($or 2 h at 210C. gyration. The radius of gyration ( 1 9) in a melt can be
w = I 0 rad/s). defined a s ( E q 3).
N1/2
R,= b.-
6 (3)
R, = 10 nm
Then
b , monomer length = 0.35 nm
T = R. [( +
1 DG. -
PSAN
ppB I l l 3 -
(2)

The values of the thickness T, of the grafted layer
calculated for the ABS for which the grafting degree
is critical (at uJ,are reported in Table 6. The data of
densities are pPR= 0.97 g/cm3; pps = 1.06 g/cm3;
pAN = 1.17 g/cm3. The SAN density is calculated ac-
cording to the S/AN ratio. The main result is that the
critical thickness does not vary with any of the con-
sidered characteristics (particle size, matrix molecu-
lar weight, S/AN composition, polybutadiene con-
tent), although the grafts are supposed to be the
same in all of our ABS materials. Therefore a direct
correlation exists between DG and the grafts confor-
mation.
Let us now calculate the value of the radius of
mo , monomeric molecular weight = 90 g
Then, the radius of gyration and the critical thick-
ness have similar values. Thus, the assumptions con-
cerning the SAN grafted conformation at the rubber
surface might be correct and can be summarized as:
0 when the degree of grafting is below the DGc, the
mushroom conformation is observed, and the
particle surface is not well-covered.
0 when degree of grafting is at DGc, the thickness of
the graft layer is equivalent to the value of two
radius of gyration, the particles are just well-
covered.

POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, V d . 35, No. 17 1403

 Mane-Pierre Bertin, Gerard Marin, and Jean-Pierre Montfort
Photo 6 : ABS 9 - GD = 29%
(x 20 000)
Photo 6. ABS 9 - DG = 29% - sheared Uor 2 h at 210C.
w = 10 rad/s).
when the degree of grafting is above the DGc, the
chains may stretch and exhibit the brush confor-
mation. The particles are well-covered and the
thickness of the graft layer might increase with the
degree of grafting.
Therefore, the correlation between the degree of graft-
ing and the chains conformation a t the surface ex-
plains the strong dependence of the ABS viscoelastic
properties. Furthermore, the degree of grafting has
an effect on the grafted morphology, thus affecting
the viscoelastic properties even further. The following
section describes a possible explanation of the ABS
viscoelastic properties at low frequencies.
Secondary Plateau
The secondary plateau appearance is not yet totally
explained. I t has been attibuted to the existence of
long relaxation times, of which several origins can be
considered. Palieme (16) attributes the secondary
plateau to the particle shape relaxation. The exis-
tence of a network structure creating long relaxation
1404 POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, VO/. 35, NO. 17
Photo 7 : ABS 10 : - GD =42.5%
Photo 7. ABS 10- DG= 42.5% - sheared Vor 2 h at 210C.
w = I 0 rad/s).
times is also a possible origin. The experimental re-
sults presented here show that there may be several
causes for the formation of the secondary plateau:
Two different cases need to be considered:
1) Case 1: the degree of grafting is equal to or greater
than DGc
In this case the rubber particles are well-covered and
well-dispersed. The grafted molecules have the brush
conformation and the thickness of the grafted layer
increases with the degree of grafting. The elastic mod-
ulus G is minimum at DGc, and above DGc, G
increases with the degree of grafting.
The level of the secondary plateau depends on the
volume fraction of dispersed phase (grafted PB) and
on the grafted layer thickness, i.e., the length of the
grafted chains. The dependence on the volume frac-
tion of the dispersed phase can be explained by the
formation of a pseudo-network, in which the nodules
are the rubber particles. The second effect, the length
of the grafted chains, can be explained by the brush
conformation of the graft at the sphere surface.
Milner (20)showed that a n increase in length of the
grafted molecules does increase the elastic compe
nent.
 Viscoelastic Properties of ABS Polymers

the creation of long relaxation times due to correlated

motions of the particles, and would explain the sec-
ondary plateau appearance.
When the degree of grafting decreases, the disper-
sion deteriorates even further and the bridging be-
comes more important, with both the agglomeration
and bridging phenomena contributing to the sec-
ondary plateau.
The particle deformation observed when under-
grafted can explain the non-superposition of the G
curves. In fact the particle deformation implies a n
increase of G (20-26).A temperature increase would
result in more particle deformation, thus increasing
the elastic modulus. According to Taylor (27).the
particle deformation can increase or decrease with
temperature, depending on the viscosity ratio and on
the surface tension, but experiments always show
a n increase in the particle deformation with tem-
perature, even when the theory proposes the
opposite result. The assumption of a particle defor-
mation increase with temperature can explain the
non-application of the time-temperature superposi-
tion principle at high temperatures. The good applica-
tion of the time-temperature superposition principle
for bimodal ABS 9, having small undergrafted parti-
cles, can be explained by the fact that these particles
Fig. 12. Grafted chain conformation at the particle surface, do not get deformed during shearing experiments
( a ) mushroom- the particle is ungrafted, ( b ) ( Photo 6).
mushroont- he particle is well-covered, (c) brush- the
particle is overgrafted. Figure 13 presents the elastic modulus (at w . a , =
lop2 rad/s) us. Qg (volume fraction of dispersed
phase) and summarizes the effects of the particle
Table 6. Dependence of the Critical Thickness Tc content and of the grafted layer on the secondary
With Particle Size, Matrix Molecular Weight, S/AN plateau formation at low frequencies. The more p r e
Ratio and PolybutadieneContent. nounced solidlike behavior is found when the rubber
content is the highest, and the degree of grafting the
lowest.
The intensity of the secondary plateau of the ABS
200 42 11.2
was found to depend on the following parameters:
93,900 70130 15
420 20 11.7
- PB particle content;
200 87,100 75/25 15 42 11.2
graft length;
5 - -
200 93,900 70/30 15 42 11.2
25 42 11.2

2)Case 2:the degree of grafting is lower than DGc 25% +PB

The rubber particles are not sufficiently covered and
are not as well dispersed in the matrix. They also get
deformed during shearing. Here, the secondary
plateau increases when the degree of grafting de-
creases. Furthermore, the time-temperature superpe
sition principle is not obeyed at T = 210C and low
frequencies, for several samples, viz., ABS 1, ABS G4,
and ABS G7.
The particles are not sufficiently covered and there-
fore there may be a n area on the surface of the PB 2 1
0 0.1 0.2 0.3 0.4 0.5
sphere that is devoid of grafted SAN, leading to ag-
glomeration and poor dispersion. A bridging phe- @g
nomenon may appear between the free PB and the Fig. 13. Particles and grafted chain effect on the elastic mod-
grafted SAN of another particle which would lead to ulus at low frequencies.

POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, VOl. 35, NO. 17 1405
 Marie-PierreBertin, Ghrard Marin, and Jean-PierreMontfort
particle dispersion;
particle shape
The PB particle content, the bad dispersion, and the
deformation of the particles increase the value of the
second plateau. The grafted layer plays a more com-
plex role, via the AE3S morphology.
CONCLUSION
The degree of grafting of the rubber particles affects
the viscoelastic behavior of ABS in the low frequency
region, where the phenomenon of the secondary
plateau appears. A critical degree of grafting, for which
the secondary plateau intensity is at a minimum, was
related to a critical thickness, Tc, of the grafted layer,
independent of particle diameter, polybutadiene con-
tent, and of acrylonitrile content of the matrix. Tc is
related to the radius of gyration R,, thus depending
on the graft length.
TWO different types of behavior, directly connected
to the conformation of the grafted molecules on the
particle surface, were noted. At a thickness of the
grafted layer below Tc, the particles are not suffi-
ciently covered, they attract each other and are de-
formed during shearing. At a thickness above Tc, they
are sufficiently covered and well-dispersed.
The intensity of the secondary plateau depends on
several factors: the grafted layer thickness (or the
particle covering), the particle content, and the inter-
nal structure of the AE3S (dispersion state of the
rubber particles, particles shape).
The observations and interpretations of this study
show the dominant role played by the coverage qual-
ity of the dispersed phase on the morphology and
therefore the viscoelastic behavior of multiple phase
materials such as reinforced polymers, blends of in-
compatible polymers or colloids.
ACKNO\RLEDGMENT
The authors are thankful to General Electric Plas-
tics for financial support and for supplying the mate-
rials and performing some chemical analysis and TEM
photographs.
NOMENCLATURE
a, = Ratio of relaxation times at two different
temperatures.
b = Monomer length.
B = Reciprocal of free volume expansion
coefficient.
Cp, C i = W.L.F. coefficients referred to To.
D = Particle diameter.
DG = Degree of grafting.
DGc = Critical degree of grafting.
1406 POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, Vol. 35, No. 17
fo = Free volume fraction at glass transition
temperature.
m0 = Molecular weight per monomer unit.
Mw = Weight average molecular weight.
n = Number of grafted particles in the
considered volume.
N = Monomers per chain.
R = Particle radius.
= Radius of gyration.
R,
T = Layer thickness.
Tc = Critical layer thickness.
T, = Vogel temperature.
TO = Reference temperature.
= Coefficients of thermal dilatation.
clr
w = Circular frequency.
P = Volume density.
= Critical density of graft points.
c
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Reuision receiued December, 1993