Applied Surface Science 238 (2004) 6472

Domain size effects on the thermal properties of

PS/PMMA blends
Glaura Goulart Silvaa,*, Patrcia Mara de Freitas Rochaa,
Patrcia Santiago de Oliveiraa, Bernardo Ruegger Almeida Nevesb
a

Departamento de Qumica, Universidade Federal de Minas Gerais, Caixa Postal 702, Belo Horizonte MG 31270-901, Brazil
b
Departamento de Fsica, Universidade Federal de Minas Gerais, Caixa Postal 702, Belo Horizonte MG 31270-901, Brazil
Available online 21 August 2004

Abstract
Polystyrene/poly(methylmethacrylate) blends (PS/PMMA) are phase-separated materials and remain so even at elevated
temperatures. Blends of PS/PMMA with 40:60, 50:50 and 60:40 wt.% ratio were prepared with PS showing glass transition (Tg)
at 64 8C and PMMA at Tg 119 8C. The constituents were mixed using three different methods: melt-mixing, casting from
solution and spin-casting. The thermal properties of the blends were studied using thermogravimetry (TG) and temperature
modulated differential scanning calorimetry (TMDSC). Insights into the morphology of phases were obtained by atomic force
microscopy (AFM) using intermittent contact mode. The melt-mixing blends have domain sizes larger than a micron and the
casting and spin-casting materials are submicron phase-separated. AFM indicated the co-continuous phase arrangement of spincasting samples at 140 8C. TMDSC showed an increase of interfacial content along with a decrease in the difference between the
glass transitions of the phase-separated materials when the preparation varies from melt-mixed to casting.
# 2004 Elsevier B.V. All rights reserved.
PACS: 68.35.-p; 68.55.-a; 68.60.Dv
Keywords: Immiscible polymer blend; Thermal properties; Spin-casting deposition; Demixing; AFM

1. Introduction
Polymer blends play an important role in the technological field since they allowed improvements in
material characteristics by combining selected properties of the original polymers [1,2]. Most polymeric
blends are multiphase systems and, therefore, their
properties largely depend on their morphologies.

Corresponding author. Tel.: 55 31 3499 5768;

fax: 55 31 3499 5700.
E-mail address: glaura@qui.ufmg.br (G.G. Silva).

The model blend of polystyrene (PS) and poly(methylmethacrylate) (PMMA) has been well characterized in previous studies [38]. Melt-mixing, casting
and spin-casting blends of PS/PMMA were studied by
varying several experimental parameters in the preparation of samples. Besides molar masses and distribution, temperature of melt, solvent and substrate
for casting are critical choices which can lead to
different results in similar studies and, thus, much
debate in the literature [8].
We are proposing in this work to study the PS/
PMMA system using a recent development of DSC
named TMDSC (temperature modulated DSC) and

0169-4332/$ see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2004.05.211

G.G. Silva et al. / Applied Surface Science 238 (2004) 6472

atomic force microscopy (AFM). Glass transitions of

the phase-separated blends prepared by melt-mixing
and casting were studied and further related with the
phase contrast images obtained for spin-casting samples at two different temperatures: before and after the
thermal events.
DSC studies are vital in polymer blend research [9].
According to Kammer et al. [10], the typical domain
size sensitivity of conventional DSC to phase-separated polymeric materials is approximately 50 nm.
Temperature modulated DSC (TMDSC), first introduced by Reading [11], has proved to be able to
address the problem of overlapping transitions associated to nanometric phases [1217]. In a TMDSC
experiment, a sinusoidal modulation of temperature is
superimposed to a linear temperature ramp with time.
The TMDSC response explored was the in-phase
heat capacity (Cp) which displays a sigmoidal change
from glassy to liquid-like values at a temperature that
is referred as a dynamic glass transition temperature [18]. The derivative differential of Cp with respect
to the temperature is a Gaussian function. Its maxima
and width were interpreted as the glass transition
parameters associated to different phases or interphases of the heterogeneous material [19].

2. Experimental
Atactic PMMA (nominal Mw 120 000, GPC-Mw
100 000 [5]) and PS ( nominal Mw 200 000 and
Mw 4000), were used as obtained (Sigma Aldrich).
A PS with binodal distribution in mass was used since
this polymer presents Tg 64 8C which is out of the
range of the PMMA-Tg 120 8C. The molar mass of
PS was checked by Size Exclusion Chromatography
using LC-10AD Shimadzu model with two columns
GPC-805 and 804 (Shimadzu) and tetrahydrofurane
plus an Utraviolet SPD-10AV (Shimadzu) detector.
The binodal molar mass distribution was confirmed
and the molar mass values obtained were Mw
103 000 and 1200 with [Mw/Mn] approximately 2.5
for both mass ranges.
Melt-mixing was performed using a Haake Rheocord 90 at 180 8C over a 10-min period at 40 rpm. The
compositions prepared for both melt-mixing and casting blends of PS/PMMA were 40 at 60 wt.% of
PMMA. The casting samples were obtained by co-

65

dissolution in chloroform of PS and PMMA followed

by casting into Petri dishes and drying of residual
solvent.
Spin-casting samples were prepared by co-dissolution in chloroform. Aliquots of 200 mL of 1 wt.%
solutions were spin casted under ambient conditions
onto glass and cleaved mica substrates, which were
rotated at approximately 2000 rpm.
Thermogravimetric analysis were performed using
samples of about 10 mg packed in alumina crucibles.
The experiments were carried out using a DTA-TGA
TA Instruments model SDT 2960 analyzer. A heating
rate of 10 8C min1 from room temperature to 600 8C
and a nitrogen atmosphere with a 110 mL min1 outflow were used.
TMDSC analysis were accomplished on a TA
Instruments model DSC 2920 Modulated using the
following procedure: (a) heating stage of 10 8C min1
up to 180 8C, (b) isotherm for 5 min, (c) quenching
(inside the DSC cell) with rate of approximately
40 8C min1 down to 20 8C, (d) modulation (amplitude of 1 8C, period of 60 s) applied during a 20 8C
isotherm for 5 min and then (e) a 3 8C/min heating
stage up to 180 8C under modulation. Samples
(5 mg) were loaded in aluminum crucibles and were
kept under a helium atmosphere with an outflow of
30 mL min1. The first heating stage and the 180 8C
isotherm aimed both annealing of the polymer and
drying of volatile residues.
The AFM images were obtained with a Nanoscope
IV MultiMode from Veeco Instruments operating in
intermittent contact (Tapping) mode using standard Si
probes. Phase contrast images were acquired simultaneously with topographic images by monitoring, with
a lock-in, the phase lag between the oscillation driver
and the actual response of the cantilever. A high
temperature heater accessory enabled the in situ
AFM investigation of the thermal behavior of samples
within a range from room temperature up to 250 8C.

3. Results and discussion

The thermogravimetric (TG) curves for PS, PMMA
and blends are showed in Fig. 1. PMMA presents two
stages of decomposition and PS is a more stable matrix
which shows degradation in a single stage. For meltmixing blends, an intermediate behavior between the

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G.G. Silva et al. / Applied Surface Science 238 (2004) 6472

Fig. 1. Thermogravimetric curves for PS, PMMA, and blends

prepared by melt-mixing and casting.

pure polymers was observed. On the other hand,

casting samples were found to have a very different
behavior: no free solvent was lost before 100 8C and a
weight loss of 18% was observed over the range 100
200 8C for both blends. This weight loss is attributed
to the solvent trapped in the glass structure which was
freed after the glass transition of the PMMA since Tg
of PS was surpassed at 64 8C.
The mainly TG results are presented in Table 1. For
easy of comparison, the first weight loss observed for
casting samples was not added in Table 1. Therefore,
the two decomposition stages in Table 1 are related to
the polymeric matrix. It should be noted that the
second stage of polymer decompositions of the casting
blends occurred at a temperature of maximum rate of
degradation (Td2 I) which was lower than for the
melt-mixing blends.
The results of TMDSC are presented in Figs. 2
and 3. Fig. 2 shows the heat flow curves which are
similar to the results that we can obtain from a
conventional DSC measurement. These curves were
recorded after a first thermal treatment at 180 8C for
5 min and, therefore, there is no influence of residual
solvent. The behavior of heat flow curves evidences
the difficulty to quote Tg values for the immiscible
blends PS/PMMA, specially in the case of casting
preparation. For this reason we turned to the signal of
in-phase with modulation heat capacity obtained
from MTDSC procedure. The derivative of Cp with
temperature (dCp/dT) as a function of temperature is
shown in Fig. 3 for all samples. In Fig. 3 the Gaussian

Table 1
Thermal results for pure polymers and blends PS/PMMA
System

TG

TMDSC dCp/dT
a

PS
PMMA
Blend 40 wt.%
Blend 60 wt.%
Blend 40 wt.%
Blend 60 wt.%
a

PMMA,
PMMA,
PMMA,
PMMA,

melt-mixing
melt-mixing
casting
casting

Td1 I (8C)

Weight
loss1 (%)

279b
293
292
287
290

33
13
12
9
16

Td2 I (8C)

Weight
loss2 (%)

Tg1 (8C)

422
387
418
411
398
379

98
66
87
88
73
66

64
53
62
51
69

Tg2 (8C)

119
102
103
87
96

Td(I): temperature of maximum rate of degradation. Subscript number (1 or 2) corresponds to the order of appearance of the thermal
event.
b
The accuracy in all temperature data were typical of thermal analysis: 1 8C.

G.G. Silva et al. / Applied Surface Science 238 (2004) 6472

67

Fig. 2. Heat Flow curves from TMDSC measurements for PS, PMMA, and blends prepared by melt-mixing and casting.

lines used to fit the curves are also exhibited. Table 1

shows the Tg results quoted from the center of the
Gaussian lines used for the adjustment of dCp/dT
curves.
Several interesting features can be pointed out from
results of glass transitions obtained from the line shape
analysis. In order to better discuss these results, the
complete set of Gaussian fitting data is presented in
Table 2. The linewidths used to fit the Tg of the pure
polymers were 13 and 11 8C, for PMMA and PS

respectively, which is acceptable for a homogeneous

material. The binodal distribution of the PS mass has
no effect on its Tg. The Tg1 values for blends of both
preparations in the concentration of 40 wt.% of
PMMA show a surprising decrease in relation of
the pure PS.
The DTg (Tg2  Tg1 ) values for melt-mixing and
casting blends show a decrease in relation to the
difference in Tg for the pure polymers. This decrease
is more significant in the case of casting blends. It

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G.G. Silva et al. / Applied Surface Science 238 (2004) 6472

Fig. 3. dCp/dT curves from TMDSC measurements for PS, PMMA, and blends prepared by melt-mixing and casting.

G.G. Silva et al. / Applied Surface Science 238 (2004) 6472

69

Table 2
Results of line shape analysis by sum of Gaussian lines for pure
polymers and blends PS/PMMA
Tg1
A1
(8C)

System
PMMA
PS
Blend 40 wt.%
melt-mixing
Blend 60 wt.%
melt-mixing
Blend 40 wt.%
casting
Blend 60 wt.%
casting

W1 Tg2
A2
(8C) (8C)

W2
(8C)

PMMA,

64
53

0.35 11
0.18 13

119

102

0.24 13

0.11 19

PMMA,

62

0.20 23

103

0.20 22

PMMA,

51

0.12 24

87

0.17 20

PMMA,

69

0.20 32

96

0.13 14

W: linewidth at half height; A: area.

should be noted that the Gaussian lines used to fit the

Tgs for casting samples exhibited a large overlap (see
Fig. 3) and their width is generally larger than for the
melt-mixing ones. These results pointed the existence
of an amount of material in interphase in the case of
casting blends.
The surface morphology of the PS/PMMA blends
was investigated using AFM. Within our experimental
conditions, melt-mixing and casting blends did not
present an adequately smooth surface, showing large
topographic variations. Holes with depths of more
than 1 mm prevented a scanning procedure. The
inspection using optical microscopy of melt-mixing
and casting blends shows protrusions larger than 1 mm
diameter in melt-mixing samples and, in casting
blends, these regions are smaller than 1 mm.
The spin-casting is a technique which allows the
preparation of adequate surfaces for AFM. Phase
contrast images for a PS/PMMA spin-casting blend
of 50:50 composition are shown in Fig. 4. The
samples were heated in situ and AFM images, over
the range ambient 140 8C, were obtained. As indicated by TMDSC results, during acquisition of AFM
images at 140 8C, the whole process of glass transition
was already surpassed (see Fig. 3). The substrate
generally used was mica which allows a good heat
conduction.
There is no significant difference between images
from ambient up to 120 8C, therefore, Fig. 4 shows the
phase contrast images for ambient, 140 8C and after
10 min at 140 8C. Dark regions of nanometric size
appear at 140 8C in phase contrast images. PS has

Fig. 4. Phase contrast images for 50 wt.% of PMMA blend

prepared by spin-casting in mica: (a) at ambient temperature, (b) at
140 8C and (c) after 10 min at 140 8C.

lower surface energy than PMMA [3,8] but, as the

samples were not previous annealed to reach thermodynamic equilibrium, we can suppose that the polymer

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G.G. Silva et al. / Applied Surface Science 238 (2004) 6472

more soluble in chloroform will be surface enriched

[4]. Ton-That et al. [6] reported results of spin-cast PS/
PMMA on mica from chloroform solutions and from
XPS results concluded that the surface is extensively
PMMA enriched. These authors observed a pitted
morphology at ambient temperature which was not
present in our topographic images as shown in a higher
magnification of Fig. 4 exhibited in Fig. 5a. The region
magnified in Fig. 5 was a central one which is more
homogeneous in relation to the dark spots observed at
140 8C.

A better observation of the temperature effect in the

morphology of PS/PMMA blends was obtained in a
experiment using a glass slide substrate, which was
heated up to 160 8C. It should be noted that the
temperature sensor of the heating stage is placed
beneath the sample substrate and aside the heating
element. Thus, since glass is a poor thermal conductor,
a temperature gradient between sample and heating
element should be expected. Glass is also reported as a
substrate that introduces a destabilizing effect and a
selective adsorption of PS [20].

Fig. 5. Higher magnification of topographic (left) and phase contrast (right) images for 50 wt.% of PMMA blend prepared by spin-casting in
mica: (a) at ambient temperature and (b) after 10 min at 140 8C.

G.G. Silva et al. / Applied Surface Science 238 (2004) 6472

71

Fig. 6. Topographic and phase contrast images for 50 wt.% of PMMA blend prepared by spin-casting in glass at 160 8C.

Fig. 6 shows topographic and phase contrast

images for spin-casting from chloroform in glass substrate blends. These images show the characteristic
co-continuous submicrom demixing structure of
phases of PS/PMMA which has no correspondence
with the topographic features.

4. Conclusions
As the PS matrix used in this work presents a
lower Tg than was generally used by other authors
[3,4,9], the temperature of 140 8C (or 160 8C for
glass substrate) was enough to promote the demixing and exposing of phase-separated structures
seen in Fig. 6. The surface structures of cocontinuous nanometric arrangements are dominant
at spin-casting samples over the range of glass
transitions.
Thermogravimetric studies evidenced the presence of solvent occluded in the glass structure of
the casting films. This had an effect in the phase
behavior rearrangements when samples were heated
from ambient to 140 8C for AFM studies. The
TMDSC results were explored after first heating
up to 180 8C and annealing for 5 min which allowed
the determination of glass transitions for PS and
PMMA rich phases. A significant amount of interphase was observed in the casting blends, which can
be correlated with the structure of demixed phases
observed by spin-casting.

Acknowledgements
This work was supported by the Brazilian agencies
CNPq and FAPEMIG and the Nanosciences Institute/
MCT.

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