ABSTRACT: Smallangle light scattering was used to measure the time evolution of the structure factor
S(k,t)at various times t after quenching polystyrenecyclohexane (PSCH) solutions to a temperature below
the spinodal temperature. Qualitatively, we observe the usual features of spinodal decomposition kinetics.
The initial part of the phaseseparation process shows an exponential increase in intensity. An analysis in
terms of the linear CahnHilliard theory was made to determine the extrapolated growth rate at zero time
and hence the initial diffusion constant. By comparing the initial growth rates for two different molecular
weights of PS, we find evidence of Zimm dynamics in these dilute solutions. The characteristic domain size
shows power law growth with an exponent ranging between 0.4 and 0.5. However, the growth of intensity
at the maximum of the structure factor does not exhibit any extensive region of power law growth; Le., the
exponent varies with time. The later stages of the structure factor data appear to collapse when rescaled
with appropriate units of length and time. From a detailed analysis of the kdependenceof the scaled structure
factor, we present some possible explanations of the interesting morphology occurring in the intermediate
stages. Our results are discussed in terms of current theory and compared with the results seen in polymer
blends and simple liquid mixtures.
800.88
,/
" ,m 338.68
=/' , 66.19
0 0.5 1 1.5 2 2.5
k (10' cm')
310
+ 0.7s
  1.21
, 1
0 1  .iL .
~ ~ .   ..1
~
0.OlCr , , , r o . o
0 1000 2000 3000 0 2 4
~
a t different times after the sample 2 was quenched to depth, decreasing k and increasing M. Following the
303.85 K. At earlier times the composition fluctuations approach used by several groups for polymer blends,3J+6
are too small to be measured. The ring initially appears we use the linear CahnHilliard model to determine the
a t large k, and with time the peak of the ring shifts into initial growth rate, i.e., R ( k ) a t t = 0. Strictly speaking,
smaller k and the intensity of the ring grows. The peak this linear theory is valid only when t h e growth is
position, k,, continues to shift in until it overlaps with the exponential and the position of the scattering maximum
forward beam and then cannot be detected. Note that the is unchanged in time (or slowly varying if one includes the
background scattering, Z,(k,t = 0), has been subtracted, thermalnoise term due to Cook). The latter condition is
and to correct for effects of multiple scattering, the clearly not true for our data. However, the linear model
scattered intensity is normalized by t h e transmitted may still be a good approximation for the initial growth
intensity, Figure 2b shows mainly the early stages of rate, R ( k ) ,a t low k's, since (i) the effects of the Cook term
the same data. Not,e that, although the peak is shifting are small when k  k, is large and (ii) the nonlinear terms
in, on the high k end the curves for different times appear that are responsible for the change of k, with time arise
to be approaching a common intersection point. Such a from a coupling of fluctuations of different sizes and are
behavior is one of the characteristic features of the linear thus likely to be more important in the vicinity of k, where
CHC model. the magnitude of the fluctuations are much larger than
Figure 2c shows intensity as a function o f t a t selected those at Ikl<< lkml. Thus, such an analysis could be useful
values of k for the same data as in Figure 2a. We note a in estimating the characteristic length and time scale in
very rapid rise of intensity a t early times followed by a the system. According to the linear CahnHilliard theory,
slower growth a t later times. For each of the k values the the scattered intensity is given as
intensity reaches its maximum value at some time and then
decreases, which is consistent with latestage coarsening
phenomena.21 Also the time a t which this maximum is where
reached is larger for smaller k's (i.e., larger size) as expected
for the growth of phaseseparating domains. T o investigate
further the rapid increase in the intensity a t very early (4)
times, we have plotted a part of the same data versus k2t
in Figure 2d. The initial growth appears to be exponential, Decrease of the initial slope, R ( k ) / k 2 ,with increasing k2
suggesting that the CHC model may be applicable at very is clearly seen in Figure 2d. From semilog plots of scattered
early stages. However, the peak position appears to be intensity versus kzt (cf. Figure 2d), we get R ( k ) / k 2= D[1
shifting in from the very first measurement (cf. Figure 2b).  k 2 / 2 k m 2 ( 0 ) ] . I n order t o d e t e r m i n e D from t h i s
Thus, unlike the CahnHilliard prediction the growth is information, one needs an estimate of k m ( 0 ) . According
not observed a t a constant wavenumber. As is well to CHC theory as discussed by Binder,12the relationship
known, the thermalnoise Cook term causes the peak to between k,(O), the correlation length, E, and the radius
slowly shift in right from the beginning. However, the of gyration, R,, is given by
magnitude of the shift seen in these data is too large to 1 1 1
be simply accounted for by the effects of thermal noise. k,(O) = y k, = y  (5)
Our results imply that since the kinetics in the polymer d 2 d25
solution is faster as compared to polymer blends, nonlin Here 0 < k C kc represents the region of wavevectors where
ear terms are important right from the early stages. Similar growth rate is positive, which means t h e fluctuations
results were reported by Wiltzius et aL6 on the kinetics become amplified rather than decay. As described in
of a blend of protonated and deuterated polybutadiene. Binder, h, = l/t, where 5 is the concentration correlation
In their measurements? although the very first data show length below T,. According to t h e Ising model, 6 =
some evidence for nonlinear effects, they found that an to(T,/ T  l)2/3. The prefactor to is the amplitude of the
analysis of the initial growth rate, R ( k ) ,was consistent with correlation length, which is different for measurements
the CHC model. above T, versus below T,. According to renormalization
In the following sections we analyze our data in three group calculationsz4to, the amplitude of the correlation
different time regimes, corresponding t o t h e early, length measured in the twophase region, is related to the
intermediate, and late stages of the phaseseparation correlation length measured in the onephase region, EO+,
p r o c e s ~ . ~InJ ~the early stages of spinodal decomposition, via to = 0.524to+.
the time evolution of the concentration fluctuation, 6c, is In order to determine to+, we have used the relationship
predicted by the linear CahnHilliard theory to grow between correlation length and the radius of gyration in
exponentially and the wavelength of the dominant mode a dilute polymer solution, Eo+ = R g / d 3 . T o determine R,,
is either constant or slowly growing if one allows for the we note t h a t CH is a 8 solvent for PS. For PS a t a
thermal fluctuations as introduced by Cook.9 In the temperature below 8 the polymer chain would be collapsed.
intermediate stage both the wavelength of the dominant T h u s we also have t o t a k e i n t o consideration t h e
mode of fluctuations k , and amplitude of the fluctuations temperature dependence of the radius of gyration, R,(T),
6c grow with time. In the late stage, the amplitude of the below the 8 temperature (8= 308.4 K for PS in CH).
concentration fluctuations 6c reaches the equilibrium value According t o t h e prediction of t h e coilglobule
of the concentration difference of the two coexisting phases, for T < 8 is given by
t r a n ~ i t i o nR, ~, ~
but the wavelength grows in a selfsimilar manner.536 It
should be noted that the transitions between these three 8  T 113
stages are not necessarily sharply defined. R,(T) = ( 7 )
N'I6 R,(8)
Early Time Behavior. As seen in Figure 2d the initial Here N , the monomers in the polymer chain, is equal to
growth of the scattered intensity appears to be exponential Mw/104 for PS. The value of R, a t the 8 temperature is
for very early times ( t I 100 s). This behavior is seen for given by R g ( 8 )= a W i 2 , ( a = 2.75 AZ6for PS). Taking
both samples a t all the different quenches. The time up everything into consideration, R,(T,) = 110.5A for sample
to which this occurs increases with decreasing quench 1 and R g ( T , )= 346.5 A for sample 2. Using this estimate,
Macromolecules, Vol. 24, No. I , 1991 Spinodal Decomposition in a Polymer Solution 293
Table I
Results of the Linear CahnHilliard Analysis for Samples 1
and 2 for Different Quench Depths, A!P
AT, K D X 10'0, cm* s1 k,(O) X lo4,cm1 70, s a 6
Sample 1
0.45 3.83 2.79 3.35 0.49 1.1
0.55 4.66 3.19 2.11 0.47 1.0
0.65 5.35 3.56 1.47 0.51 1.0
0.75 5.73 3.92 1.14 0.43 1.2
0.95 7.84 4.59 0.61 0.53 1.2
Sample 2
0.25 0.87 0.59 330.2 0.59 b
0.40 1.86 0.81 81.94 0.59 1.0
0.75 3.78 1.23 17.48 0.54 1.0
1.25 6.12 1.73 5.46 0.47 1.0
The exponent a was determined as the best effective fit to each
of the data sets shown in Figure 3. The exponent 6 is only defined
over a very limited range of times and thus represents an asymptotic
*
value. No region of power law growth could be identified.

Zimm dynamics (D Mw4.5and TO M W 9than with 
weights is 12, these results are in better agreement with
of the peak maximum and I, the intensity at the maxi
mum. T h e exponents a and @ obey the hyperscaling
relation P = 3a for latestage growth in three dimensions.'
either Rouse or reptation dynamics.27 The validity of The linear analysis of the initial growth rate provides
Zimm dynamics for dilute solutions has been well us with an estimate of the characteristic length and time
established from dynamic lightscattering measurements scales. Using these values, we plot the peak position, k,
of the selfdiffusion coefficients in dilute solution^.^^ It (in units of k,(O)), and the intensity at the maximum, I,,
is i m p o r t a n t t o note t h a t our observation of Zimm as a function of the reduced time T = t / T g , for the different
dynamics is obtained from the twophase region and the quenches for both the samples (Figures 3 and 4). As shown
D values correspond to the collective diffusion constant. in Table I, cy ranges from 0.4 to 0.5. Unlike the work with

The diffusion constant decreases as T approaches T,
scaling as D ( T , This result is in good agreement
polymer blends, we never observed a value of a = l / 3 ,
suggesting that hydrodynamic effects are important a t all
of the Ising

with the result obtained from measurements done aboue
the critical point,14D ( T  Ts)0.77,
which gives D 
and with the prediction
(T Ts)0J37.
stages of the spinodal decomposition process in the dilute
solution case. Several different droplet growth and
coarsening mechanisms predict a value of a = 1/3. For
Our analysis shows that the linear CahnHilliard model example, the evaporationcondensation mechanism of Lif
works reasonably for the extrapolated initial growth rate shitz and S l y o z ~ v the
, ~ ~droplet coalescence growth
in the polymer solution case, in spite of the fact that the mechanism of Binder and S t a ~ f f e rand , ~ ~the coarsening
position of the maximum in the structure factor is changing of solid interfaces all predict a = l/3. Values of a > '13
from the earliest observation. The effects of including the are obtained if one includes hydrodynamic effects.32 The
thermal noise as done by Cookg and nonlinear terms as model of Siggia,33 where convective flow with hydro
done in the LagerBaronMiller modeP will be discussed dynamic interactions are dominant, gives a = 1.
in a future paper. According to the dynamic scaling hypothesis, the late
Intermediate and LateStage Growth. As mentioned stage data plotted in reduced units should be independent
earlier, in the intermediate stage t h e concentration of the quench depth. We observe only a partial collapse
294 La1 and B a n d Macromolecules, Vol. 24, No. I , 1991

\
'i
4
earlier times than at later times. This may be happening
because the initial concentration of the solution is in the
dilute regime where hydrodynamic interactions are not
0 24.8
A 14.2
screened out and the polymer dynamics is described by
$ 1
I 24.1 Zimm model. However, as phaseseparation proceeds most
x 24.0 of the polymer molecules are in the concentrated or semi
X 0 2¶.&
dilute regions where hydrodynamic screening is quite
effective. Thus with increasing time, hydrodynamic effects
X
become less important, in stark contrast to the situation
with binary fluids where hydrodynamic effects become
more important in the late stages. If this argument is
correct, then a should be close to 1/3 at earlier times in
the spinodal decomposition of concentrated polymer
solutions as compared to that of a dilute solution of the
same molecular weight. Preliminary results on a high
concentration solution of PSCH tend t o support this.
An alternative explanation is that in the case of the
polymer solution the mobility is a strong function of
polymer concentration and changes with time as the phase
separation proceeds. Thus the characteristic time scale
itself varies during the phaseseparation process, becoming
longer as the phase separation proceeds. A t present no
theoretical model deals with the case where the mobility
and characteristic time scale are themselves time depend
ent.
Figure 4. Maximum scattered intensity, I,, obtained at various Parts a and b of Figure 4 show a loglog plot of intensity
quench temperatures as function of time in reduced units. (a) at the peak Im/If versus reduced time 7 for samples 1 and
The data for sample 1 showing rapid initial growth followed by 2. For both samples 1 and 2 we observe the slope /3 to be
a region of slower growth. It is clear that no extensive power law

growth regime can be identified; however, there appears to be a
transition at late stages to power law growth with @ 1. The
time at which this transition to latestage growth occurs depends
continuouslychanging, approaching an asymptotic behavior
with a slope p close to 1 (7 > 60 and 6, for samples 1 and
2 , respectively). The initial growth is more rapid, being
on quench depth occurring earlier in reduced time for deeper exponential instead of power law, suggesting that at early
quenches. (b) The same analysis for sample 2 suggests that most times the dominant contribution to the amplitude of the
of the data are in the early and intermediate stages. An
asymptotic power law growth with /3 = 1 (see text) can be seen. fluctuations is from the linear terms even though the
The line of slope 1 is drawn to guide the eye. growth of wavelength, k m , of the dominant mode of
fluctuations is influenced by the nonlinear terms. Since
of the data (Figure 31, suggesting that most of it lies in the width of the coexistence curve is broader for deeper
the intermediate stage of the phaseseparation process. An quenches, the equilibrium value of the amplitude of the
examination of parts a and b of Figure 3 shows that the concentration fluctuations, 6c, reached in the late time
transition from the intermediate to the late stage depends should increase with increasing quench depth. This is well
on quench depth, the deeper quenches showing more of borne out by our data for sample 1 as seen in the increase
the late stages, since the process happens on a faster real of the asymptotic value of Im/If with quench depth. For
time scale for T further away from T,. sample 2 this is not seen, again indicating that most of the
In the late stages of spinodal decomposition in a critical measured data are in the intermediate stage where the
sample of polymer blends, an exponent of a l / 3 has been amplitude has not yet reached the equilibrium value.
observed5v6whereas in the intermediate stages the exponent During the late stages where no further concentration
was found to be dependent on the quench depth. We changes occur in the demixed phases, scaling theory
observe similar behavior for the lower molecular weight predicts /3 = 3a. The time range explored in our data never
solution, with a becoming independent of quench depth seems to quite approach this as seen in Table I. This
for 7 > 100. An additional difference is that, for 7 < 100 further corroborates our conclusion that most of our
(Le., in the intermediate stage), a > l / 3 , in contrast to the measured data fell in the intermediate region. It was not
results with polymer blends where it is less than l / 3 .
Similar results are seen in the higher molecular weight possible to extend the measurements to later times because
sample. T o rule out experimental artifacts, we used our the peak position had become so low as to be obscured by
apparatus under identical optical conditions to measure the transmitted beam. It should also be pointed out that
spinodal decomposition in the isobutyric acidwater system intensity measurements are susceptible t o greater
where the peak positions are in the same range as those inaccuracy than measurements of the peak position since
in our samples. For a critical quench close to T,, we found small effects of multiple scattering and background
that N was l / 3 , in agreement with the results of Wong and subtraction can still occur even though we have tried to
Knobler.21 minimize these effects as discussed earlier.
Having ruled out experimental artifacts, we suggest two Dynamic Scaling of the Structure Factor. A t late
possible explanations for this somewhat intriguing times, according to the dynamic scaling hypothesis,' the
observation of a larger value of (Y at earlier times. Since structure factor S ( k , t ) can be written in terms of a time
Macromolecules, Vol. 24, No. I , 1991 Spinodal Decomposition in a Polymer Solution 295
: t
p 4.0 8.0
(c)
3.0 0.0
n

0
c c
.
I
T
n
\
n

:
X
T = 297.1 K
Y
Y
0
2.0 T = 296.8 K Y
0
4.0
Y
I
I r 233363
*E T 105316 cDE
Y Y
1.0 2.0
0.0
0 1 2
k/k,
4
0.0 L 1 2
k/k,
3 4
a
r
p 26.0 p 16.0
I;:$
20.0
0 CI
c ,40.0
T \
.
16.0
Y T = 296.8 K
.
n
Y
T = 297.1 K

Y
Y
0
10.0
Y
I
Y
0
r 233348
*DE ",E6.0
Y
6.0
0.0 1I 2I
.? 3 0.0 4
I
;
I
2 3 1
k/k, k/k,
Figure 5. Scaled scattering functions for sample 1. (a) Early and intermediatestage data (7 < 316) for a deep quench Tq= 296.8
K, showing no collapse. (b) For the same quench as in (a) the data collapse for 7 > 331, which is indicative of late time scaling regime.
Also plotted are the theoretical scaling functions of Furukawa for offcriticaland critical quenches, identified as F4 and F6, respectively
(see text for definition). (c) Data for the shallow quench, Tq = 297.1 K plotted using eq 7 with d = 3. (d) The same data as in (c)
plotted with d = 2 in eq 7.
independent scaling function, F ( k / k m ( t ) ) teristic length scale lead to most of the data falling in the
intermediate time scale for shallow quenches. Similar
kmdS(k,t)= F ( k / k , ( t ) ) (7) results were observed for the higher molecular weight
where d is the spatial dimension of the system. Since the sample 2, where true latestage behavior could never be
scattered intensity is proportional to the structure factor, detected.
the applicability of this scaling can be tested by plotting We tried an empirical approach to examine the question
km3Z,(k,t)/Zf versus k / k m for different times. Figure 5 of whether any alternative form of scaling exists in the
shows the results of such an analysis for sample 1 for two intermediate region. We found that if we allowed d in eq
different quench temperatures. For the case of a deep 7 to vary with the quench depth and the time regime, then
quench, Tq= 296.8 K, we find that at early times ( T < 316) it was possible t o scale t h e d a t a in the intermediate
the data do not collapse (Figure 5a) whereas at late times regime.34 Figure 5d shows that for Tq = 297.1 K the data
( T > 331) the data collapse, indicating that dynamic scaling collapse with d = 2.0. Similar results were obtained for
is satisfied at later stages but not in the intermediate stages. the intermediatestage data at other temperatures and also
For a shallow quench Tq= 297.1 K, the data do not collapse for the higher molecular weight sample. The value of d
for even the latest times a t which measurements could be ranged between 1.7 and 2.5.
made. These results are consistent with the interpretation Since the term (k,)d in the dynamic scaling equation
given earlier, that the slower time scale and larger charac (eq 7) arises from the dependence of the structure factor
296 La1 and Bansil Macromolecules, Vol. 24, No. 1, 1991
,
10 J
(d
analysis for polymer blends by several authors gives values
of y = 4, with y = 6 observed in two case^.^^^^ The values
T =203.8 K of y obtained by us would suggest that, in the case of deep
/ T 331 197 quenches, where late stages of spinodal decomposition are
reached, the clusters are isolated and have a smooth
interface, which gives the characteristic Porod scattering.%
Since this sample was almost critical, we should have
obtained y = 6 according to the Furukawa theory. As
oE 1 discussed in the recent review by Binder,12disagreements
with the Furukawa theory also show up in other experi
ments6 and in computer simulations where also one obtains
y = 4 instead of 6 for critical quenches. For the shallow
quench case where the laste measurements are in the
O . l t 77
o.olc~  ,
0.1
, , , , , ,
klk,
1
,
P 10
effective power law and clearly suggests that a further study
over bigger k ranges might be very useful.
As a final comparison of the latestage structure factor
with the Furukawa prediction, Figure 5b shows t h e
predicted functional form F ( x ) = 3x2/(2 + x6) and 4x2/
(3 + x8), for offcritical and critical quenches, respectively
Figure 6. The asymptotic behavior of the scaled structure factor (x = k/k,). These are identified as F4 and F6, respec
F ( k / k , ) for sample 1. (a) For a deep quench, Tq= 296.8 K, the tively, in the figure. A comparison of the predicted
same data as in Figure 6b shown on a loglog plot. Note that function with the measured scaled structure factor shows
the slope y = 2 for k/k, < 1 and equals 4 for k / k m > 1. (b) good agreement for k / k m < 1and a clear disparity for high
For a shallow quench, Tq= 297.1 K, the data of Figure 6d shown
on a loglog plot. Note that y = 2.1 for k / k m < 1 but equals values of k/km. In this region, even though the asymptotic
3.5 for k/km > 1. Note also that, although the collapse of the behavior is given by the exponent y = 4, the actual function
data for different times occurs only with d = 2.0, the asymptotic does not match. The mismatch is most pronounced in the
power law behavior in k has the same exponent irrespective of vicinity of k/k, E 2, suggesting that perhaps there is a
the value of d in eq 7, because the factor kmdbecomes an additive secondary peak in this region. Recent experiments6 and
constant in a loglog plot. theoretical models38 have suggested the existence of a
second peak at k/k, = 2. This is also supported by the
on the volume of the scatterer, our result may be indicative work of Chakrabarti e t al.,37 who obtained the time
of scattering from “rough” domains in the intermediate evolution of the structure factor by numerically integrating
stages, possibly arising from the very diffuse and relatively the spinodal decomposition equations for polymer blends
large interface that exists in the intermediate stages as based on the FloryHugginsde Gennes freeenergy
compared to the late stages. The k dependence of the functional a n d found no agreement with either of
structure factor is also suggestive of scattering from a Furukawa’s functional forms.
diffuse interface as discussed below.
According to Furukawa,%the asymptotic scaled structure Conclusions
factor, F(k/k,), scales as (k/k,)?, where y = 2 for for
k / k m < 1 and y = 4 or 6 for k / k m > 1. The value of y = To summarize, we have measured the spinodal decom
4 implies the existence of isolated phaseseparated clusters position kinetics in polystyrenecyclohexane solutions of
and is expected for offcritical quenches whereas y = 6 two different molecular weights for several different quench
implies a percolating structure and is expected for critical temperatures. As expected, the kinetics is slower for the
quenches. It is perhaps interesting to see if any effective high molecular weight sample. While most of t h e
power law behavior can be discerned from the structure measurements accessible by smallangle light scattering
factor data obtained here. Since the range of 12space fall in the intermediate to late stages, the earliest data show
accessible in these measurements is limited, we recognize some features that are indicative of a linear CHC model.
t h a t t h e conclusions of such a n analysis are a t best Although the contribution of nonlinear terms is probably
indicative of effective exponents. However, such analysis inportant from the beginning, it is perhaps reasonable to
has often been done in polymer blends over approximately analyze the initial growth rate in terms of the linear theory.
similar ranges of k. Thus we attempt similar analysis of Such an analysis was used to determine the initial diffusion
our data but caution against taking the exponents too constant, and the molecular weight dependence shows that
literally. the dynamics is consistent with the predictions of the Zimm
As shown in parts and and b of Figure 6 for the low model.
molecular weight sample, the exponent y = 2 for k / k m Intermediate and latestage growth appear t o be
1 is obtained for both deep and shallow quenches. described by power law relations. The exponents become
However, for k / k m > 1, the exponent y = 4 for deep independent of quench depth only in the late stages, and
quenches and y 1: 3.5 for shallow quenches. Similar this could only be reached for the lower molecular weight
Macromolecules, Vol. 24, No. 1, 1991 Spinodal Decomposition in a Polymer Solution 297
sample for deep quenches. The characteristic time scale Phys. 1986,85,6773. For a recent review, see: Hashimoto, T.
was slower and the characteristic length scale bigger for In Phase Transitions; Gordon and Breach Science Publishers
Inc.: New York, 1988; Vol. 12, pp 42119.
both shallow quenches and higher molecular weights. As (6) Wiltzius, P.; Bates, F. S.; Heffner, W. R. Phys. Ref. Lett. 1988,
a consequence, it was not possible to measure the scattering 60,1538. Bates,F. S.; Wiltzius, P.J. Chem. Phys. 1989,91,3258.
in truly late stages in these cases. (7) Nose, T. In SpaceTime Organization in Macromolecular Fluids;
The latestage structure factor could be scaled into a Tanaka, F., Doi, M., Ohta, T., Eds.; SpringerVerlag: New York,
universal timeindependent form in agreement with the Berlin, and Heidelberg, 1989; Vol. 51, p 40. Earlier work is
reviewed in: Nose, T. Phase Transitions 1987,8, 245.
predictions of the dynamic scaling hypothesis. However, (8) Cahn, J. W.; Hilliard, J. H. J . Chem. Phys. 1958, 28, 258.
in the intermediate stages such a collapse of the data could (9) Cook, H. E. Acta Metall. 1970, 18, 297.
only be obtained by modifying t h e dynamic scaling (10) de Gennes, P.G. J. Chem. Phys. 1980, 72, 4756.
equation to allow the dimension d to vary with quench (11) Pincus, P. J . Chem. Plys. 1981, 75, 1996.
(12) Binder, K. J. Chem. Phys. 1983,79,6385. For a recent review,
depth and time. Although this is clearly an empirical see: Binder, K. In Materials Science and Technology: Phase
procedure, we tentatively suggest that this may be related Transformation in Materials; Haasen, P., Ed.; VCH Verlags
to the structure of the interface in the intermediate stages. gesellschaft: Weinheim, Germany, 1990; Vol. 5, p 1.
The asymptotic behavior of the scaled structure factor was (13) Van Aarsten, J. J.; Smolders, C. A. Eur. Polym. J . 1970,6,1105.
(14) Kuwahara, N.; Fenby, D. V.; Tamsky, M.; Chu, B. J. Chem. Phys.
also found to be anomalous in the intermediate stages. The 1971,55, 1140.
results are suggestive of a diffuse interface in this time (15) Nakata, M.; Kuwahara, N.; Kaneko, M. J. Chem. Phys. 1975,
range. 62, 4278.
A detailed comparison with the predictions of the (16) Kojima, J.; Kuwahara, N.; Kaneko, M. J. Chem. Phys. 1975,63,
333.
Furukawa model was made. The results showed that the (17) Nakata, M.; Dobashi, T.; Kuwahara, N.; Kaneko, M. Phys. Reo.
s t r u c t u r e factor scales according t o t h e Furukawa A. 1978, 18,2603.
prediction for k < k m but that for k > k, the exponent y (18) des Cloizeaux, J.; Jannink, G. Les Polymeres en solution: leur
= 4 even though we considered a critical quench. The Modelisation et leur Structure, Les editions de physique, 1987.
actual functional form proposed by Furukawa agrees on (19) Perzynski, R.; Delsanti, M.; Adam, M. J . Phys. 1987, 48, 115.
(20) Goldburg, W. W. In Scattering Techniques Applied to Su
the low k side but is quite inadequate on the high k side. pramolecular and Nonequilibrium Systems; Chen, S. H., Chu,
Some evidence for a second peak a t k l k m N 2 can be seen B., Nossal, R., Eds.; Plenum Press: New York, 1980; and
in the data. references therein.
In conclusion, we note that while some of the results (21) Wong, N. C.; Knobler, C. M. J. Chem. Phys. 1978,69, 725.
(22) Chu, B.; Schoenes, F. J.; Fisher, M. E. Phys. Ref. 1969,185,219.
obtained here for the polymer solution case are similar to (23) Pine, D. J. Reo. Sci. Znstrum. 1984, 55, 856.
those seen in blends, many differences can also be seen. (24) Guenoun, P.; Gastaud, R.; Perrot, F.; Beysens, D. Phys. Reo.
For the polymer solution most of the data accessible to A . 1987,36, 4876.
smallangle light scattering fall in the intermediate time (25) Park, I. H.; Wang, Q. W.; Chu, B. Macromolecules 1987,20,1965.
scale where there is no existing theoretical model. It is (26) Cotton, J. P.; Decker, D.; Benoit, H.; Farnoux, B.; Higgins, J.;
Jannink, G.; Ober, R.; Picot, C.; des Cloizeaux,J. Macromolecules
clear that a proper theoretical treatment, which takes into 1974, 7, 863.
account the effects of phasediagram asymmetry and (27) Doi, M.; Edwards, S. F. The Theory of Polymer Dynamics; Clar
concentrationdependent mobility of polymer solutions and endon Press: Oxford, 1986.
also includes nonlinear effects, is needed in order to get (28) Stanley, H. E. Introduction to Phase Transitions and Critical
Phenomena; Oxford University Press: Oxford, 1971.
a detailed quantitative agreement between theory and (29) Langer, J. S.; Baron, M.; Miller, H. D. Phys. Reo. A 1975, 11,
experiment. 1417.
(30) Lifshitz, I. M.; Slyozov, V. V. J. Phys. Chem. Solids 1961, 19,
Acknowledgment. We thank Profs. Bill Klein and Karl 35.
(31) Binder, K.; Stauffer, D. Phys. Reo. Lett. 1974, 33, 1006.
Ludwig of Boston University for many helpful discussions (32) Kawasaki, K. Prog. Theor. Phys. 1977,57, 826.
and acknowledge the technical assistance of Jeyandran (33) Siggia, E. D. Phys. Reo. A. 1979, 20, 595.
Abraham throughout the whole project. This research was (34) Bansil, R.; Lal, J. In Extended Abstracts: Fractal Aspects of
supported by a grant from the NSF. Materials: Disordered Systems; Weitz, D. A., Sanders, L. M.,
Mandelbrot, B. B., Eds.; Materials Research Society Pittsburgh,
PA, 1988; EA17, p 255. Lal, J.; Bansil, R. In Fractal Aspects
References and Notes of Materials 1989; Kaufman, J. H., Martin, J. E., Schmidt, P.
(1) Gunton, J. D.; San Miguel, M.; Sahni, P. S. In Phase Transitions W., Eds.; MRS: Pittsburgh, PA, 1989; EA20, p 11.
and Critical Phenomena; Domb, D., Lebowitz, J. L., Eds.; (35) Furukawa, H. Phys. A. 1984, 123,497.
Academic Press: London, 1983; Vol. 8, p 267. (36) Tomlins, P. E.; Higgins, J. S. J. Chem. Phys. 1989, 90,6691.
(2) Snvder. H. L.: Meakin. P. J. Chem. Phvs. 1983. 79. 5588. (37) Chakrabarti, A,; Toral, R.; Gunton, J. D.; Muthukumar, M. J.
(3) Sah, TI; Han,'C. C. J. Chem. Phys. 1988,88,2057. Okada, M.; Chem. Phys. 1990,92,6899.
Han, C. C. J. Chem. Phys. 1986,85,5317. (38) Ohta, T.; Nozaki, H. In SpaceTime Organization in Macro
(4) Nishi, T.; Wang, T. T.; Kwei, T. K. Macromolecules 1975, 8, molecular Fluids; Tanaka, F., Doi, M., Ohta, T., Eds.; Springer
now
LL 1 .
Verlag: New York, Berlin, and Heidelberg, 1989; Vol. 51, p 51.
(5) Hashimoto, T.; Itakura, M.; Hasegawa, H. J . Chem. Phys. 1986,
85,6118. Hashimoto, T.; Itakura, M.; Shimidzu, N. J . Chem. Registry No. PS,9003536.