1116 Full Paper

Summary: The phase-morphology inversion in two blend

systems of polystyrene/poly(methyl methacrylate) (PS/
PMMA) and polystyrene/poly(e-caprolactone) (PS/PCL)
has been studied after their thin films were prepared on glass
substrates by spin-coating from a co-solvent tetrahydrofuran
(THF). Phase-contrast microscopy (PCM), scanning-
electron microscopy (SEM) equipped with energy dispersive
X-ray spectroscopy (EDS), and atomic force microscopy
(AFM) were used to obtain information on the morphology of
the thin films during heat treatment. It was found that the
PMMA-rich and PCL-rich phases are always continuous
after annealing in either of the PS/PMMA and PS/PCL blend
thin films, even though the PMMA and PCL are minor com-
ponents in the blends. This should result from the better
wetting abilities of PMMA and PCL on a glass substrate than
PS in the blends. The effect of the viscosity in the evolution of
the phase structure was also investigated by changing the
molecular weight of PS in the PS/PCL blend thin films.
Further more, it is found that the phase-separation process
and the wetting phenomenon of the blends on the glass
substrate can be strongly suppressed after adding PS-block-
PMMA diblock copolymer to the PS/PMMA blend system as
a compatibilizer.
Scheme of the longitudinal section of the evolution of the
phase structure of a PS:PMMA (70:30 w:w) blend film.

Inversion of Phase Morphology in Polymer-Blend Thin

Films on Glass Substrates
Qi Zong, Zhi Li, Xuming Xie*
Advanced Materials Laboratory, Department of Chemical Engineering, Tsinghua University, Beijing, 100084, China
Fax: þ86-10-62770304; E-mail: xxm-dce@mail.tsinghua.edu.cn

Received: December 11, 2003; Revised: March 12, 2004; Accepted: March 24, 2004; DOI: 10.1002/macp.200300235
Keywords: phase inversion; poly(methyl methacrylate); polystyrene; thin films; wetting ability

Introduction influenced the phase-separation process. More recently,

There has been much interest in the investigation of the
surface structure of multicomponent polymer systems and
phase structures in polymer-blend thin films.[1–11] It has
been revealed that near interfacial boundaries, surface ef-
fects and substrate dependence may lead to physical pro-
perties that significantly differ from those in the bulk.[12–20]
In 1981 Reich and Cohen[21] reported on the study of the
phase separation of polymer blends in thin films. By light
scattering from thin films of polystyrene/poly(vinyl methyl
ether) PS/PVME, the authors showed that both the boun-
daries and specific polymer-surface interactions strongly
employing atomic force microscopy (AFM), Krausch and
co-workers[22] studied the three-dimensional information
of the domain morphology in polystyrene/poly(methyl
methacrylate) (PS/PMMA) thin films on three different
substrates. In our previous work, studying the interface-
induced coarsening process in polymer blends and the study
of the phase inversion of PS/PMMA thin films on different
substrates, it was found that the substrate plays an important
role in governing the structure and properties of polymer
films.[23–25] Xie and co-workers[26] observed the surface
morphology development of PS/PMMA-blend thin film in
the presence of supercritical carbon dioxide (SCCO2).

Macromol. Chem. Phys. 2004, 205, 1116–1124 DOI: 10.1002/macp.200300235 ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Inversion of Phase Morphology in Polymer-Blend Thin Films on Glass Substrates
A stable surface structure, in which the PS-rich phase was
elevated by the PMMA-rich phase, was formed after
annealed in SCCO2. This can be explained by the different
aggregations of the PS and PMMA in the two interfaces: air-
polymer and substrate-polymer.
In many practical applications, polymer films are pre-
pared by the method of spin-coating. The resulting phase-
separated morphology resulting from sudden extraction of a
solvent may be far from the thermodynamic equilibrium.
This film formation process involves the interplay of a
series of processes, which include solvent evaporation,
phase separation, gelation, wetting, solvent diffusion, vitri-
fication, and so on. Affrossman et al.[27] and Tanaka[28]
investigated the domain morphology of an immiscible
binary polymer blend, spin-coated from toluene solution,
with AFM. They found a remarkable topographical struc-
ture that accompanied the formation of lateral domains.
More recently, Bradley and co-workers[29–31] examined
the surfaces of PS and PMMA blend films with different
compositions on a mica substrate by the techniques of X-
ray photoelectron spectroscopy (XPS), AFM, and
frictional-force microscopy (FFM). They found that surface
enrichment of PMMA existed in all compositions,
and when the concentration of PMMA in the casting
solution was less than that of PS a pitted morphology was
formed.
The study of wetting phenomena on polymer surfaces
and interfaces is also a rapidly maturing subject since the
quantitative studies of surface segregation at the end of
1980s.[32] Ade and co-workers[33] analyzed the thin films of
PS and PMMA on silicon substrate by AFM, total electron
yield (TEY), partial electron yield (PEY), and near-edge X-
ray absorption fine structure (NEXAFS) spectroscopy, in
order to show that the slightly lower surface energy of PS
compared to that of PMMA is insufficient for the PS to
segregate to the surface and form a wetting layer. Instead,
PS and PMMA are phase-separated on the surface. This is in
contrast to the experiments[29] that implied an equivalent PS
wetting layer of about 5–10 nm was forming during
annealing. More recently, Kang et al.,[34] using both optical
microscopy (OM) and AFM, investigated the kinetics of the
dewetting and the layer inversion in enthalpically inverted
poly(vinyl pyrrolidone)/polystyrene (PVP/PS) bilayer
films on a silicon wafer during annealing.
The morphology of formations is full of varieties for
polymer-blend thin films. The objective of this study is to
obtain a better understanding of the phase evolution
observed in the polymer-blend thin films. In this paper,
phase-contrast microscopy (PCM), scanning-electron
microscopy (SEM) equipped with energy dispersive X-
ray spectroscopy (EDS), and AFM are used to characterize
the morphology of the thin films during annealing. Mean-
while, the effects of viscosity and compatibilizer content on
the morphological evolution process are both investigated
from both a dynamic and thermodynamic aspect.
Macromol. Chem. Phys. 2004, 205, 1116–1124 www.mcp-journal.de
1117
Experimental Part
Materials
The PS samples used in this work were obtained from Beijing
Yanshan Petrochemical Co. Ltd. (M w ¼ 219 648, M w:M n ¼
2.56, [Z] ¼ 85 g
mL1) and Acros Organics (M w ¼ 281 100,
M w:M n ¼ 3.44, [Z] ¼ 107 g
mL1) respectively. PMMA was
obtained from Asahi Co. (M w ¼ 136 600, M w:M n ¼ 1.56).
poly (e-caprolactone) (PCL) was purchased from Wako Pure
Chemical Industries, Ltd. (M w ¼ 48 500, M w:M n ¼ 1.20).
Glass transition temperatures of the PS samples and PMMA,
measured by differential scanning calorimetry, were 98, 101,
and 118 8C, respectively. The glass transition temperature of
PCL was ca. 60 8C.[35] The diblock copolymer of PS-block-
PMMA was kindly offered by Mr. K.-H. Chang (Dept. of
Chemical Eng. & Materials Sci., University of Minnesota). It
has a weight-averaged molecular weight of 160 000 and a PS
weight fraction 50%. The solvent for spin-coating (tetrahy-
drofuran, THF) was analytical grade.
Film Preparation
Each PS/PMMA (PS/PCL) mixture was solution-blended in
the THF solvent. Polymer-blend films were prepared by the
spin-coating technique from PS/PMMA or PS/PCL solutions
(typically 2% (w:v)) at room temperature. The diblock co-
polymer, used as a compatibilizer, was well dissolved in THF
(typically 2% (w:v)) and then added into the PS/PMMA
solution. The compatibilizer weight fractions were varied in
the range (1 to 9%) in the PS/PMMA blends. The blend film
thickness was controlled by varying the rotation speed and
evaluated by scratching through the polymer film down to the
substrate using stiff AFM cantilevers and a high loading
force.[36] The average film thickness was about 350 nm.
Observation and Analysis
OLYMPUS BH-2 phase-contrast microscopy was used to
observe the evolution of the phase morphology of the thin
films. Sample annealing was carried out on a heating stage (the
annealing temperatures were 220 and 190 8C for the PS/
PMMA and the PS/PCL thin films, respectively). Once remo-
ved from the heating stage, samples were quenched to room
temperature. In addition, the films were sputtered with alumi-
num to a thickness of 10 nm under vacuum in order to enhance
the electrical conductivity of the film, and JSM-6301F
scanning electron microscopy (SEM) equipped with EDS
was used to observe the surface morphology of the films and
analyze the surface composition. The surface morphology of
the PS/PMMA blend films was also investigated on the basis of
AFM observation. Tapping mode AFM imaging was per-
formed on a Digital Instruments Multimode AFM controlled
by Nanoscope III at room temperature. The AFM cantilever
used was microfabricated from silicon and its spring constant
and resonant frequency was 17.5 Nm1 and 210 kHz, respec-
tively. Image analysis was performed using commercial DI
software. Cyclohexane is a good solvent only for the PS
component and does not dissolve PMMA. The surface of the
ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1118
sample was also immersed in cyclohexane for 10 min to
remove the PS at the sample surface.
Results and Discussion
Substrate Dependence of the Evolution
of Phase Morphology
The phase-separation process of the PS/PMMA (70:30 w:w)
mixture, which was spin-coated onto a glass substrate to
form a thin film of about 350 nm thickness, was observed at
220 8C by PCM. Figure 1 shows the morphological evolu-
tion of the blend.
Before annealing, no structure was observed in the film,
implying the blend film is quite homogeneous after solution
blending (Figure 1a). In the spin-coating method, since
solvent molecules were evaporated fairly fast from the
solution before attainment of an equilibrium and a thermo-
dynamically stable state of the mixture system, no macro-
scopic domains were observed at the initial stage.
Macroscopic domains were detected after annealing the
blend above the glass transition temperature for 4 min
(Figure 1b), which is the result of the immiscibility of the
two polymers. For films annealed for 24 min (Figure 1c),
PCM observations show the appearance of the well-defined
sea/island-like phase-separated structure in the polymer-
blend thin film. As the annealing time increased, the island
domains became larger and larger and a bi-continuous
Figure 1. Phase contrast microscopic images for the PS/PMMA (70:30 w:w) blend film on glass
substrate annealed at 220 8C. The annealing times are (a) 0 min, (b) 4 min, (c) 24 min, (d) 29 min,
(e) 37 min, and (f) 135 min.
Macromol. Chem. Phys. 2004, 205, 1116–1124 www.mcp-journal.de
Q. Zong, Z. Li, X. Xie
structure was formed (Figure 1d). After this critical state,
the isolated domains in the early stage inverted to
continuous-phase-like domains while the incipient contin-
uous phase changed into island-like domains. Finally,
during the final stage the newly formed isolated domains
coarsened with time to take the shape of a sphere (Figure 1f)
which minimizes the interfacial free energy, as is usual.
In order to understand the mechanism of the above phase-
inversion phenomenon on glass substrate, we should first
define the compositions of the domains and the matrixes in
the morphological evolution as shown in Figure 1.
SEM combined with EDS was used to analyze the
surface compositions of the films at different annealing
stages. Figure 2a is the SEM micrograph of the phase struc-
ture corresponding to Figure 1b by PCM, which represents
the early stage of annealing. Figure 2b is the spectra of the
elementary analysis along the line in Figure 2a from the top
down. Carbon and oxygen spectra were obtained simulta-
neously. Except for hydrogen, PMMA contains the ele-
ments of oxygen and carbon, whereas PS only has the
element of carbon. Hence, the domains that are rich in
PMMA will show peaks in the oxygen spectrum while the
domains that are rich in PS show peaks in the carbon
spectrum. Both from the micrograph (Figure 2a) and the
spectra (Figure 2b), we could define that at the early stage of
annealing, the PMMA-rich phase is the dispersed phase,
which has peaks in the oxygen spectrum, and the PS-rich
phase is the continuous phase, which has peaks in the
ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Inversion of Phase Morphology in Polymer-Blend Thin Films on Glass Substrates 1119

Figure 2. (a) SEM micrograph of the phase structure corresponding to Figure 1b. (b) Spectra of the
elementary analysis along the line in Figure 2a from the top down. The upper is the C spectrum and the
lower is the O spectrum. The scan range is 22.4 mm.

carbon spectrum. However, at the late stage, the SEM
micrograph (Figure 3a) of the phase structure correspond-
ing to Figure 1f (determined by PCM) and the correspond-
ing spectra (Figure 3b) shows that the PS-rich phase
becomes the dispersed phase and the PMMA-rich phase is
the continuous phase. These results obviously show that the
phenomena observed by PCM, as shown in Figure 1, is real.
Phase inversion occurred during annealing of PS/PMMA
(70:30 w:w) films on glass substrates.
The spectra shown in Figure 2 and 3 can be investigated
further. The spectroscopic line in Figure 2 shows that in
some regions of the film the contents of both oxygen and
carbon are very high, however, there is no such situation
occurring in Figure 3. This phenomenon is related to the
phase separation process, that is, after a long annealing
time, phase separation becomes much more complete than
that in the early stages.
The phase inversion observed by PCM revealed that
during annealing on a glass substrate, the continuous do-
mains of the PS-rich phase invert to a dispersed phase, and
the island-like domains of the PMMA-rich phase turn into a
continuous phase. However, it should be noted that the
PMMA is the minor component in the blend.
The works by Shih,[37] Sundararaj et al,[38] and Scott and
co-workers[39] found that when the minor component be-
came a viscoelastic fluid much faster than the major
component, an intermediate morphology consisting of the
major component suspended in a continuous matrix of the
molten minor component resulted. With further processing
(purely shear flow or complex flow), the major component
eventually reached the viscoelastic fluid stage and a phase
inversion occurred. However, phase inversion did not occur
under no-flow conditions.
In this study, the case is not the same as for the phase
inversion observed by the works about melt blending
mentioned above. There are two questions arising: How can
the minor component be continuous? and what caused the
minor component to become continuous? In order to help
answer these, the surface morphology change of the blend
films during phase evolution was monitored. Hence, AFM
combined with selective etching of the blend sample
surface by solvent was used to obtain three-dimensional
information on the domain morphologies on the surfaces of
PS/PMMA (70:30 w:w) thin films during annealing.
Figure 4 shows the changes of the surface morphology of
a PS/PMMA (70:30 w:w) blend film at the early stage of

Figure 3. (a) SEM micrograph of the phase structure corresponding to Figure 1f. (b) Spectra of the
elementary analysis along the line in Figure 3a from left to right. The upper is the C spectrum and the
lower is the O spectrum. The scan range is 39.6 mm.

Macromol. Chem. Phys. 2004, 205, 1116–1124 www.mcp-journal.de ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1120
annealing. The AFM topography (Figure 4a) of the film
before annealing showed a granular surface. In order to
determine the component of the granules in Figure 4a, the
surface of the sample was immersed in cyclohexane for
10 min to remove the PS at the sample surface. Cyclohexane
is a good solvent only for the PS component and does not
dissolve PMMA. The AFM topographic image (Figure 4b)
was then taken to reveal the surface structure of the
remaining PMMA phase. It was found that the granular
surface was unchanged but only the height of the granules
increased. It implies that the granules and the matrix regions
in Figure 4a were composed of the PMMA and the PS
phases, respectively. However, after annealing the blend
sample at 220 8C for 5 min, the surface morphology of
the incipient granules changed to a pitted morphology
(Figure 4c). The annealed sample was also analyzed by the
same procedure of etching treatment as above. The AFM
image is shown in Figure 4d. The annealed surface, after
dissolving the PS, still exhibited granular structures.
However, the height of the granules decreased. Therefore,
we know that in Figure 4c the component in the pits is the
PMMA-rich phase and the continuous phase being etched is
the PS-rich phase.
Before annealing, the dispersed phase (PMMA-rich
phase) was higher than the continuous phase (PS-rich
Figure 4. Two-dimensional AFM images of the surface morphologies of PS/PMMA(70:30 w:w)
blend film on glass substrate annealed at 220 8C for (a) 0 min, (c) 5 min, (b) and (d) after etching
treatment with cyclohexane of (a) and (c), respectively.
Macromol. Chem. Phys. 2004, 205, 1116–1124 www.mcp-journal.de
Q. Zong, Z. Li, X. Xie
phase) in the surface of PS/PMMA (70:30 w:w) thin films.
However, after annealing for about 5 min, the granular
structure rapidly inverted to the pitted structure. It can be
explained as follows. The initial surface morphology for-
med in the rapid solvent evaporation process is a conse-
quence of the different solubility of the two polymers in the
common solvent. The PS-rich phase, which has a better
solubility in THF, solidified later than the PMMA-rich
phase. Thus the PS-rich phase collapsed below the average
height of the PMMA layer.[22]
Figure 5 shows the changes of the surface morphology of
PS/PMMA (70:30 w:w) blend film at the later stage of anne-
aling. With an increase in annealing time, the protruding
domains gradually coarsen as shown in Figure 5a–5c. The
surface morphologies (Figure 5d–5f) of the annealed
samples after etching treatment did not change much,
although the heights of the granules decreased more or less.
This is evidence that the protruding domains in the AFM
topographic image (Figure 5a–5c) are the PS-rich phase
and the matrix phase is the PMMA-rich phase. After an
annealing time of 12 min (Figure 5a), the continuous PS
phase formed separate domains and later it exhibited
spherical PS drops that protruded from the PMMA matrix
(Figure 5b–5c). This corresponds to the results observed by
PCM.
ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Inversion of Phase Morphology in Polymer-Blend Thin Films on Glass Substrates 1121

Figure 5. Three-dimensional AFM images of the surface morphologies of PS/PMMA(70:30 w:w) blend
film on glass substrate annealed at 220 8C for (a) 12 min, (b) 22 min, (c) 130 min, (d), (e), and (f) after
etching treatment with cyclohexane of (a), (b), and (c), respectively. Z ranges are all 800 nm for each graph.

AFM observation of the PS/PMMA (70:30 w:w) thin also minimizes the interfacial free energy, as shown in
films shows that the evolution of surface morphology can be Figure 6b–6c. Finally, the PS-rich island domains are
divided into two stages. At the early stage of annealing, transformed into spheres, as shown in Figure 6d. It was
there was a substrate preferential aggregation of the clearly illustrated that near the glass substrate there was a
PMMA-rich phase and a surface segregation of the PS-
rich phase, which induced the granular surface morphology
to rapidly inverted into a pitted morphology. At the late
stage, it was mainly a dewetting process of the PS-rich
phase on a PMMA-rich layer. Because PMMA has better
wetting ability on a glass substrate than PS, there is a
tendency for the minor component of PMMA to spread on
the glass substrate to form a continuous phase, and for the
major component of PS to form a dispersed phase through
dewetting after long annealing times.
With the help of the results obtained from SEM/EDS
analyses and AFM observations, in general, the inversion of
the phase structure followed by PCM can be explained as
shown in Figure 6. Before annealing, as shown in Figure 6a,
the blend film was almost homogeneous under PCM
observations because of the fairly rapid evaporation of
solvent in the spin-coating method. But there are small
domains of PMMA protruding from the film because of the
different solubility of the two polymers in the common
solvent.[22] Annealing the blend film above the glass
transition temperature for a short time, results in the
PMMA-rich domains going down to the polymer/substrate
interface and spread on it (because of the better wetting Figure 6. Scheme of the longitudinal section of the evolution of
ability of PMMA on a glass substrate than PS) while the PS- the phase structure of PS:PMMA ¼ 70:30 w:w blend film at
rich phase segregates on the PMMA-rich layer, which 220 8C on glass substrate.

Macromol. Chem. Phys. 2004, 205, 1116–1124 www.mcp-journal.de ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1122 Q. Zong, Z. Li, X. Xie

Figure 7. Phase-contrast microscopic images for the phase morphologies of PS/PCL (70:30 w:w)
blend film on glass substrate annealed at 190 8C. Here the M w of PS is 219 648, [Z] ¼ 85 g
mL1. The
annealing times are (a) 0 min, (b) 6 min, (c) 15 min, (d) 22 min, (e) 30 min, and (f) 165 min.

PMMA-rich layer spreading on it, while PS-rich domains phase. Finally, as shown in Figure 7e–7f, the blend film
took the shape of spheres on top to minimize the interfacial attained the structure that was similar to the scheme put
free energy. forward in Figure 6. Because of its good wetting ability, the
During the investigation of the morphological evolution minor component of PCL wetted the glass substrate and
of the PS/PMMA thin films on glass substrates, it was found formed a PCL layer under the PS domains.
that the minor component in the blend system could become
a continuous phase, despite of the polymer blend ratios. The
Influence of Compatibilizer on Phase Inversion
component in the blend, which has a good wetting ability to
the substrate, determined the composition of the continuous The influence of viscosity is mainly on the dynamics of the
phase and the dispersed phase. Therefore, the glass sub- phase inversion, further more, the compatibilizer, which has
strate played an important role in the phase-inversion effects on both the thermodynamics and dynamics of phase
process of the PS/PMMA (70:30 w:w) blend films. In order inversion, was investigated by the means of PCM observa-
to confirm this conclusion, which was put forward from the tions to gain some insight into its influence on the phase
observations of the PS/PMMA blend films, the same experi-
ment in another incompatible blend system of PS/PCL was
also made. Figure 7 depicts the phase-evolution process that
Table 1. Time needed for the different stages in the PS/PMMA
was observed for PS:PCL ¼ 70:30 w:w thin films on glass (70:30 w:w) system with different compatibilizer concentrations
substrates at 190 8C. There was a similar process followed and annealing at 220 8C.
by PCM. At the early stage of annealing (Figure 7a–7b), the
continuous phase and the dispersed phase of the blend film Content Time
were mainly determined by the composition ratio, that is, % min
when the PCL was the minor component, it became the
dispersed phase, and the major component of PS was First stage Second stage Third stage
the continuous phase. However, with further annealing
(Figure 7c–7d), PCL rapidly spread on the glass substrate to 0 0–4 4–29 29 onwards
1 0–4 4–42 42 onwards
minimize the interfacial free energy between the polymer 4 0–10 10–155 155 onwards
film and the glass substrate. At the same time, the PS phase 6 0–10 10– –
was dewetted and protruding from the PCL continuous 9 0–20 20– –

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 Inversion of Phase Morphology in Polymer-Blend Thin Films on Glass Substrates 1123

Figure 8. Phase-contrast microscopic images of the phase structure evolution of PS:PMMA ¼

70:30 w:w blend film on glass substrate at the temperature of 220 8C. Here the M w of PS is
219 648, [Z] ¼ 85 g
mL1 and the M w of the diblock polymer is 160 000. The annealing times are
(a) 0 min, (b) 20 min, (c) 3 h, and (d) 6 h.

inversion. Polymer-blend thin films with different compa-
tibilizer concentrations were prepared by spin-coating
and annealed at 220 8C. In order to compare the effects of
different compatibilizer concentration, the whole phase-
evolution process was divided into three stages. The first
stage was the primeval for annealing when there was no
obvious macroscopic phase separation under optical micro-
scopy. The appearance of small domains and their growth
was defined as the second stage. The third stage was the bi-
continuous structure transforming into a droplet pattern.
Table 1 showed the time needed for different stages to
occur for the PS/PMMA system with different contents of
compatibilizer. For the blend films containing 0, 1, and 4%
compatibilizer, the inversion of the phase morphology can
be observed at the annealing times of 29, 42, and 155 min,
respectively. However, if the addition of the compatibilizer
into the blend system was higher than 4%, the bi-continuous
pattern no longer appeared even after annealing for more
than 6 h at 220 8C. Figure 8 shows the micrographs of the
representative phase evolution for PS/PMMA (70:30 w:w)
with 9% diblock copolymer content. It was clearly indica-
ted that the addition of the diblock copolymer of PS-block-
PMMA into the PS and PMMA blends led to a significant
depression of the film separation.
Influence of Viscosity on Phase Inversion
The wetting process is mainly dominated by dynamics, so
changing the viscosity of the blend system can control the
wetting process during phase inversion. Here, the influence
of viscosity on phase inversion was investigated by chan-
ging the molecular weight of the PS component in contrast
to the PS ([Z] ¼ 85 g
mL1)/PCL blend films shown in
Figure 7. The phase evolution process of PS ([Z] ¼
107 g
mL1)/PCL (70:30 w:w) blend films on glass sub-
strates was observed by PCM at 190 8C. Compared with
Figure 7, it was found that the phase-evolution processes
were similar, but the velocity of the phase separation
obviously slowed down. The time needed for the complete
phase inversion was postponed from 20 to 90 min after
changing the molecular weight. The higher viscosity of PS
increased the viscosity of the blend system, which slowed
down the enrichment process of the PCL-rich phase on the
substrate.
Conclusion
During the investigation of the morphological evolution of
PS/PMMA and PS/PCL thin films on glass substrates, a
phase-inversion process was clearly observed and well
analyzed. It was found that the minor component in the
blend system could become a continuous phase because of
its better wettability on the glass substrate. There were three
main processes during the annealing of the samples: phase
separation, wetting, and dewetting processes. Among them,
the wetting process of the PMMA-rich phase on the glass
substrate played the most important role in the formation of
the final phase-separation morphology of the blend films.
By changing the viscosity of the PS it was found that
the phase-evolution process slowed down when the high-
molecular-weight PS was used, although the phase-
evolution courses were similar. The higher viscosity of
the PS increased the viscosity of the blend system, which
slowed down the process of the PCL-rich phase colliding
with, coalescing on, and enrichment on the substrate.
The addition of diblock copolymer of PS-block-PMMA
to the spin-coating polymer solutions of PS and PMMA led
to a significant depression of film separation on glass
substrates.
Acknowledgment: We are grateful to Yan Yunjie at the
Department of Materials Science and Engineering, Tsinghua
University, for his technical support on the SEM experiments. And
we gratefully acknowledge Professor Ling Yong and Wang Xiufeng
at the Department of Physics, Tsinghua University, for their
technical support and valuable discussions on the AFM
measurements. This project has been supported by a grant from the
National Natural Science Foundation of China (No.90103035,
No.20174022andNo.10334020),whichisgratefullyacknowledged.

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1124
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