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1394 POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, Vol. 35, No. 77
Viscoelastic Properties of Al3S Polymers
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
(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 temperature is 106C.The viscoelastic moduli G' and
matrix), in order to get a constant polybutadiene G ( w ) measured at 150, 170, 190, and 210C were
content of 15%. The SAN degree of grafting ( D G ) superimposed into a master curve at 170Caccording
defined by to the time-temperature superposition principle. The
weight of grafted SAN coefficients Cp and C: and f o , determined with the
W.L.F. (14) equation (Eq 1) are given in Table 5.
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 To = 170C
following operations: it is put into acetone for 16 h at The viscoelastic behavior of the SAN matrix was char-
room temperature to extract the non-grafted SAN acterized. The effects of molecular weight and AN
(free SAN) from the grafted layer. The acetone is evap content on the viscoelastic functions are respectively
orated under vacuum at 60C for 12 h. Then, the shown in Figs. 1a and b and 2a and b. Slopes of 2
powder of SAN grafted polybutadiene is dried in a n and 1 respectively observed for log G' us. log w and
oven at 60T, and weighed. l o g G us. logo were found. This modulus depen-
ABS B to I in Table 3 are made of a blend of the dence on frequency is usual for homopolymers: linear
same SAN grafted polybutadiene a s the one used for for G and squared for G'. SAN 6 is a n exception,
ABS 1-4with various SAN samples (the S/AN ratio of probably due to its high polydispersity index (3.1).
the grafted and of the matrix are possibly different). which broadens and shifts the terminal zone to lower
The PB content is 15%.the particle size 200 nm, and frequencies. Furthermore, a n increase in molecular
the degree of grafting vanes from 29 to 63%.ABS G 1 weight shifts the terminal region to lower frequencies,
to G9 in Table 4 , are made of blends of the same SAN which means that the viscosity is increasing with
grafted PB as for ABS 1-4 and ABS B-I with the molecular weight (Fig. I ) . The low frequency zone
matrix SAN 2, in order to get a PB ratio of 5, 15, and behavior is not influenced by variations in the S/AN
25%. The particle size is 200 nm and the degree of ratio of the materials, though a n increase in the AN
grafting varies from 29 to 63%. To summarize the content from 25 to 35% slightly increases the plateau
table presentation: Table 1 presents the SAN samples modulus value. The AN variation from 25 to 35% is
which allows the determination of the SAN viscoelas not broad enough to allow conclusions concerning its
tic behavior: Table 2 corresponds to ABS with various influence upon the viscoelastic behavior of the SAN.
degrees of grafting for two different sizes of particles Thus SAN behaves like a homopolymer with a nar-
and for bimodal ABS; Table 3 presents ABS samples row molecular weight distribution, explained by its
with different matrix: ABS samples in Table 4 have statistical copolymer structure (at this S/AN ratio
their degrees of grafting varying for three different range) (15).
rubber contents.
Viscoelastic Behavior of the ABS
EXPERIMENTAL
The ABS polymer is a two-phase material and each
The viscoelastic measurements were performed phase has a distinct glass transition: the SAN phase,
with a n Instron 3250 rotary Rheometer, in a parallel with a glass transition temperature of 106"C,and the
plates geometry in dynamic mode. The plate radius is PB phase, with a glass transition temperature of
1 cm. The shear and loss moduli were measured in - 84C.In the temperature range of this study (150to
the frequency range from 10 to 100 Hz and in the
~
1396 POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, VOl. 35, NO. 17
ViscoelasticProperties of Al3S Polymers
SANl AN-30%
SAN4 AN=25%
* SANJ AN-35%
-3 -2 -1 I 2 3 log I w x a , )
(b) (b)
Fg. l a and b. Master curves of SAN samples at 170C. Fig. 2a and b. Master curves of SAN samples at 170C.
Efects of the molecular weight. All units related to G' and G" Effects of the S/AN composition.
are Pa.
ondary elastic plateau appears: G' is higher than G ,
therefore the ABS exhibits a more elastic than vis-
spectrum ( R g s . 3 to 6). This observation suggests cous behavior. This solid-like behavior at low frequen-
that the SAN behavior predominates over the ABS cies, which usually appears for heterogeneous sys-
behavior except at low frequencies where another tems, is not yet completely explained and several
phenomenon appears. Therefore the AI3S behaves as theories have been presented (8, 16, 17). This will be
a homogeneous polymer at high frequencies and the discussed later.
time-temperature superposition principle can be a p The ABS viscoelastic behavior in the low frequency
plied in this region. The viscoelastic moduli measured region strongly depends on the degree of grafting of
at 150, 170, 190, and 210C were superimposed into the rubber particles. Aoki's (1 1) experiments on ABS
a master curve at 170C.The coefficients Cp and C i samples showed that when varying the degree of
and fo determined with the W.L.F. equation are re- grafting of the rubber particles, the viscoelastic func-
ported in Table 5 for all samples. tions exhibit a minimum at a degree of grafting that
The ABS values of Cp and Cg and fo are different he calls the Critical Degree of Grafting ( DGc). The aim
from those of the SAN matrix. The free volume frac- of this work is to better describe and understand this
tion increases with polybutadiene content, in agree- Critical Degree of Grafting. Thus, several parameters
ment with Casale et al (10). The free volume fraction were varied and their effects upon DGc studied. G'
is also slightly increased when the matrix and graft and G" were measured at a given low frequency in
S/AN ratio are different (AI3S 1 to 11 compared with the terminal zone ( w . a, = 10 rad/s) and plotted us.
~
ABS B to I). Other parameters, like the degree of the degree of grafting for different situations.
grafting, molecular weight, percent AN of the matrix, In the following paragraphs, the minimum of G'
or particle size do not have any effect on the free and G is observed for the same degree of grafting,
volume (i.e. temperature dependence). but the modulus variations are higher for G' than for
The most peculiar ABS viscoelastic behavior is G . Thus, only the curves obtained from G' are pre-
located in the lower frequency region where a sec- sented.
POLYMER ENGlNEERlNG AND SCIENCE, MID-SEPTEMBER 1995, VOl. 35, 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.
1398 POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, VOl. 35, NO. 77
ViscoelasticProperties of ABS Polymers
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)
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.
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.)
ciently covered and tend to agglomerate. The rubber formed while the overgrafted particles (Photo 5) still
is not compatible with the matrix and the rubber retain their spherical shape. TEM photos of the same
particles attract each other. sheared ABS, non-quenched, do not show any defor-
Photos 4 and 5 correspond to sheared samples. The mation of the rubber particles which have the same
undergrafted particles (Photo 4) are strongly de- 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 tively. The particles dispersion is better for ABS hav-
not correspond to an equilibrium state. The deforma- ing DG = 43%than for ABS having DG = 29%. due to
tion related to the rigidity of the rubber particle and the attraction forces between the undergrafted parti-
to its surface tension, both change with the degree of cles. Furthermore, the small, undergrafted particles
grafting. Above DGc, the particle surface might be shown in Photo 6 do not get deformed during shear-
well-covered with SAN and when the material is sub- ing, contrary to the undergrafted small particles of
jected to shear, the graft SAN, entangled with the the monomodal sample of Photo 4. The presence of
matrix, does not move and therefore the rubber parti- the large well-grafted rubber particles prevents the
cles, to which the other end of the graft chains are deformation of the small undergrafted particles (the
attached, cannot move either and do not deform. large particles possibly provide more rigidity to
Photos of samples at the DGc show the same mor- the matrix which avoids the smaller particles defor-
phology as those above DGc. Thus the particle stabil- mation).
ity under shear depends on the degree of grafting.
The rubber particles which would not be sufficiently DISCUSSION
covered get deformed and tend to agglomerate. The Critical Degree of Grafting
less the particles are grafted, the worse the disper-
The effect of various parameters on the critical
sion. When the particles are well-grafted, they are
degree of grafting can be summarized as follows:
more stable and are better dispersed.
The internal morphology of bimodal ABS samples, 0 DGc decreases when the rubber particle size in-
bimodal ABS with DG = 29% (undergrafted small creases:
particles and overgrafted large particles) and bimodal 0 DGc is independent of the polybutadiene content;
ABS with DG = 43% (small and large particles at and DGc is unchanged when the matrix AN ratio varies
above DGc) can be seen in Photos 6 and 7, respec- from 25 to 30%.
POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, Vol. 35, No. 17 1401
Marie-PierreBertin, Gkrard Marin, and Jean-PierreMontfort
1402 POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, Vol. 35, No. 17
Viscoelastic Properties of ABS Polymers
(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 mo , monomeric molecular weight = 90 g
calculated for the ABS for which the grafting degree
is critical (at uJ,are reported in Table 6. The data of Then, the radius of gyration and the critical thick-
densities are pPR= 0.97 g/cm3; pps = 1.06 g/cm3; ness have similar values. Thus, the assumptions con-
pAN = 1.17 g/cm3. The SAN density is calculated ac- cerning the SAN grafted conformation at the rubber
cording to the S/AN ratio. The main result is that the surface might be correct and can be summarized as:
critical thickness does not vary with any of the con-
sidered characteristics (particle size, matrix molecu- 0 when the degree of grafting is below the DGc, the
lar weight, S/AN composition, polybutadiene con- mushroom conformation is observed, and the
tent), although the grafts are supposed to be the particle surface is not well-covered.
same in all of our ABS materials. Therefore a direct 0 when degree of grafting is at DGc, the thickness of
correlation exists between DG and the grafts confor- the graft layer is equivalent to the value of two
mation. radius of gyration, the particles are just well-
Let us now calculate the value of the radius of covered.
(x 20 000)
Photo 6. ABS 9 - DG = 29% - sheared Uor 2 h at 210C. times is also a possible origin. The experimental re-
w = 10 rad/s).
sults presented here show that there may be several
causes for the formation of the secondary plateau:
Two different cases need to be considered:
when the degree of grafting is above the DGc, the
chains may stretch and exhibit the brush confor- 1) Case 1: the degree of grafting is equal to or greater
mation. The particles are well-covered and the than DGc
thickness of the graft layer might increase with the
degree of grafting. In this case the rubber particles are well-covered and
well-dispersed. The grafted molecules have the brush
Therefore, the correlation between the degree of graft- conformation and the thickness of the grafted layer
ing and the chains conformation a t the surface ex- increases with the degree of grafting. The elastic mod-
plains the strong dependence of the ABS viscoelastic ulus G is minimum at DGc, and above DGc, G
properties. Furthermore, the degree of grafting has increases with the degree of grafting.
an effect on the grafted morphology, thus affecting The level of the secondary plateau depends on the
the viscoelastic properties even further. The following volume fraction of dispersed phase (grafted PB) and
section describes a possible explanation of the ABS on the grafted layer thickness, i.e., the length of the
viscoelastic properties at low frequencies. grafted chains. The dependence on the volume frac-
tion of the dispersed phase can be explained by the
Secondary Plateau
formation of a pseudo-network, in which the nodules
The secondary plateau appearance is not yet totally are the rubber particles. The second effect, the length
explained. I t has been attibuted to the existence of of the grafted chains, can be explained by the brush
long relaxation times, of which several origins can be conformation of the graft at the sphere surface.
considered. Palieme (16) attributes the secondary Milner (20)showed that a n increase in length of the
plateau to the particle shape relaxation. The exis- grafted molecules does increase the elastic compe
tence of a network structure creating long relaxation nent.
1404 POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, VO/. 35, NO. 17
Viscoelastic Properties of ABS Polymers
POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, VOl. 35, NO. 17 1405
Marie-PierreBertin, Ghrard Marin, and Jean-PierreMontfort
second plateau. The grafted layer plays a more com- n = Number of grafted particles in the
1406 POLYMER ENGINEERING AND SCIENCE, MID-SEPTEMBER 1995, Vol. 35, No. 17