Fractals, Vol. 6, No.

3 (1998) 285–292
c World Scientific Publishing Company

MORPHOLOGY OF POLYMER-SALT
COMPLEX FILMS CROSSOVER FROM
FRACTAL TO COMPACT AGGREGATION

ANINDA JIBAN BHATTACHARYYA∗ , S. BANERJEE† ,

T. R. MIDDYA and S. TARAFDAR
Condensed Matter Physics Research Center, Department of Physics,
Jadavpur University, Calcutta-700032, India
† Indian Association for the Cultivation of Science,

Calcutta-700032

Received April 6, 1998; Accepted June 23, 1998

Abstract
In this paper we present a study of the variation of morphology of polyethylene oxide (PEO)
films complexed with ammonium perchlorate (NH4 ClO4 ) formed by evaporating a methanolic
solution. Films with salt concentration x = 0 − 0.35 (x is the weight fraction of salt) were
prepared for the morphology study. The wide variety of structures obtained were systemat-
ically studied by photographs and polarizing microscopy. Some preliminary studies of x-ray
diffraction, differential scanning calorimetry and variable temperature polarizing microscopy
have also been done to identify the various phases present in the films.

1. INTRODUCTION 0.10–0.15) to large compact spherulite (x = 0.18–

We have prepared polyethylene oxide (PEO) films
complexed with ammonium perchlorate (NH4 ClO4 )
formed by evaporating a methanolic solution. A
rich diversity of structures is found on varying the
salt concentration (x). The morphology varies from
pure PEO spherulites at x = 0, through macro-
scopic diffusion limited aggregates (DLA) (x ∼
∗
E-mail: aninda@juphys.ernet.in
0.35). Here x is the fraction of salt by weight.
For higher x, the salt remains uncomplexed and
can be seen as separate crystals on the film. We
present a series of photographs and micrographs
which clearly show the transition. To identify
the species present in the film, preliminary stud-
ies of variable temperature polarizing microscopy

285
286 A. J. Bhattacharyya et al.
(VTPM), x-ray diffraction (XRD) and differential
scanning calorimetry (DSC) studies have also been
done.
Recently, a number of studies have been reported
where crossover from fractal to non-fractal1,2 struc-
tures has been observed on varying different pa-
rameters. Biological systems3 – 5 such as bacteria
colonies of proteus mirabilis5 with varying concen-
trations of agar and nutrient show such a behavior.
An aggregation of potassium dichromate in gelatin6
with different gelatin concentration is another inter-
esting case.
Fractal growth7,8 and compact spherulite
formation9 in polymer ionic salt complexes have
also been reported. These materials are ion con-
ducting and may be used commercially10,11 as solid
electrolytes.
In the present work, we report a more systematic
and detailed study of the morphology variation in
PEO-salt complexes. Our objective is to find out
the composition most suitable for use as a poly-
mer electrolyte, but we find that the morphology
variation itself makes a fascinating study. This a
preliminary report to be followed by more detailed
measurements of crystallinity and ionic conductiv-
ity in films having different morphology.
2. PREPARATION OF THE
FILMS
For the morphology study, we prepared both pure
PEO (B.D.H., England; M.W. = 600000) and PEO
complexed with NH4 ClO4 (Fluka, 99.5% pure) by
solution casting technique by dissolving in methanol
(hplc grade) as solvent. s gms. of NH4 ClO4 and
(1-s) gms. of PEO was taken in a 100 ml flat bot-
tomed beaker. s (and hence x) was varied from
0 to 0.35. 25 ml of methanol was added and the
solution was stirred for 6 hours at room tempera-
ture (26◦ C). The solution was then transferred to
a polypropylene petri dish (diameter = 7.5 cm) and
left for slow evaporation approximately for a day
(relative humidity range: 90%–50%). After this it
was transferred to a vacuum dessicator and vacuum
dried at ∼ 10−3 Torr, for over a week (i.e. the dry-
ing process takes ∼ 10 days). The above method
produced good quality films of polymer-complexes
with no cracks for the salt concentration range x =
(0.10–0.35) gms. For x < 0.10 cracks appeared in
the films during vacuum drying. In order to obtain
better films in the range x < 0.10, the drying con-
ditions were changed. The solution was left in the
petri dish for slow evaporation for 5 days to a week.
After this the films were transferred to the vacuum
dessicator for vacuum drying. Good quality films
with no cracks were produced after 1–2 days of vac-
uum drying. The modified preparation conditions
used for x < 0.1 were also tried out for x > 0.1.
Results for x > 0.1 using the modified preparation
conditions were similar to the ones obtained with
the previous method. However, we opted for the
method (i.e. for x > 0.1) which produced faster
drying of the films.
For each concentration three sets of samples were
prepared for reproducibility. The thickness of the
films was approximately 150 µm. All the films were
stored in a vacuum dessicator.
3. STUDY OF MORPHOLOGY
OF THE FILMS AND
DISCUSSION
We have observed the detailed structure of the films
through a polarizing microscope (Leitz Ortholux
2). However, much of the morphology is visible
to the naked eye and has been photographed un-
der low magnification. XRD (Philips PW170, PC-
APD diffraction software), DSC (Perkin Elmer DSC
2) under Nitrogen gas flow and VTPM (with hot
stage-Mettler FP 82 HT and an exposure meter-
Wild MPS 46/52, Photoautomat) studies were done
to identify the species present in the films and to
estimate the crystallinity. The ionic conductivity
depends on two competing factors — the concen-
tration of charge carriers which increases with x
and the amorphous fraction which appears to de-
crease with x. Conductivity measurements are in
progress. Since the films are ∼ 150 µm thick, we
treat them as quasi two-dimensional in the follow-
ing discussions. A summary of the characteristics
observed for different x are given in Table 1.
3.1 Low x Regime
Figure 1 is a micrograph showing the spherulites
of the pure PEO. In preliminary DSC studies a
single endotherm corresponding to the melting of
pure PEO was observed at x = 0. It is seen
that the crystallinity (area under the curve) of
pure PEO spherulites decreases as x is increased.
Figures 2(a) and 2(b) show the DLA pattern ob-
tained for x = 0.10 and x = 0.12. The fractal
 Morphology of Polymer-Salt Complex Films . . . 287

Table 1 Variation of morphology with different salt fraction

Concn. of NH4 ClO4 (x) Morphology Average Spherulite/Tree Size

0 (Pure PEO) Small Spherulites 360 µm

00
0.04 200 µm
00
0.08 150 µm
0.10 Large Trees + microscopic spherulites 1.3 cm
00
0.12 0.214 cm
00
0.15 0.15 cm
0.18 Large Polygonal Spherulites 0.242 cm
0.20 Largest Polygonal Spherulites 2.0 cm
0.22 Polygonal Spherulites 1.4 cm
00
0.25 0.9 cm
0.27 Small sized Spherulites 0.7 cm
0.30 Small amounts of salts
0.32 remain unreacted, Polygonal Spherulites 250–350 µm
0.35 in the background

Fig. 1 Micrograph of pure PEO film showing spherulites of size ∼ 360 µm [Scale = 300 µm; Magnification: × 50].

nature is quite evident and the Hausdorff dimen-
sion for Fig. 2(a) measured by box-counting tech-
nique applied to the digitized images gives a value
∼ 1.8, for the length scales (0.4–11.4)mm, which is
typical of DLA. XRD studies show no characteris-
tic lines of pure salt in this regime. We may con-
jecture that small particles of the PEO-NH4 ClO4
complex, which are very sparsely distributed at
this value of x, aggregate through a diffusion lim-
ited random walk process to give the DLA struc-
ture, and the background consists of spherulites
of pure PEO. Increasing x produces more nucleat-
ing islands (formed by immobile clusters of several
crystallites). This results in smaller trees which
288 A. J. Bhattacharyya et al.
(a)
Fig. 2 Photographs of DLA pattern obtained for PEO-NH4 ClO4 for (a) x = 0.10 [Scale = 1 cm ; Magnification: × 4.5]
(b) x = 0.12 [Scale = 1 cm ; Magnification: × 3.3].
Fig. 3 Micrographs(cross polarizer) of a branch of a tree
obtained for PEO-NH4 ClO4 for x = 0.10 [Scale = 300 µm;
Magnification: × 50].
(b)
are more closely spaced [Fig. 2(b)]. At this x value
the trees cover the whole sample, the “mass” of each
tree is M (r) ∼ r 1.8 , r being the average radius.
A rough estimate of the diffusion coefficient of
the polymer solution is obtained from the drying
time τ (10 day) as
hr2 i
D= .
4τ
This gives D ∼ 10−8 cm2 sec−1 with r = 0.20 cm,
the radius of the trees for x = 0.12. The viscos-
ity and hence D changes with drying, so this is an
average value.
Under the polarizing microscope, the branches of
the tree appear quite thick, and their outlines are
clearly seen in Fig. 3. For the small length scales
of the order of the thickness of a branch the trees
are not mass fractal, but the surface fractal dimen-
sion of the boundary (calculated manually by the
 Morphology of Polymer-Salt Complex Films . . . 289

divider step method) is ∼ 1.5. The micrograph also
reveals circular spherulites probably of pure PEO
in the background region of the trees. These are of
microscopic (∼ 0.01 mm) dimensions and cannot be
seen in low magnification Fig. 2(a).
On slightly increasing x from 0.15 to 0.18 [see
Figs. 2(b) and 4(b)], the morphology changes dras-
tically from the trees with M (r) ∼ r 1.8 to compact
spherulites with M (r) ∼ r 2 .
3.2 Intermediate x Regime
Figures 4(a) and 4(b) show two photographs of the
same sample (x = 0.18) at different times. In
Fig. 4(a), the film is not yet dry and the circu-
lar spherulites are separated. In Fig. 4(b), they
cover the whole sample, and the circular spherulites
crowd to form polygons when the neighbors touch.
The size of the spherulites in Figs. 4(a) and 4(b)
are equal, which shows that the original spherulites

(a) (b)
Fig. 4 Photographs of PEO-NH4 ClO4 for x = 0.18 taken at different times (a) Undried and (b) Dried [Scale = 1 cm;
Magnification × 2.2].

(a) (b)
Fig. 5 Photographs of PEO-NH4 ClO4 at different concentrations showing the change in the size of the polygons (a) x = 0.22
(Avg. size ∼ 1.4 cm) and (b) x = 0.25 (Avg. size ∼ 0.9 cm ) [Scale = 1 cm; Magnification: × 2.2].
290 A. J. Bhattacharyya et al.
Fig. 6 Micrograph of PEO-NH4 ClO4 for x = 0.20 shows
the Maltese cross pattern.8 [Scale = 300 µm; Magnifica-
tion: × 50].
Fig. 8 Micrograph of PEO-NH4 ClO4 for x = 0.35 shows undissolved salt crystallites with the spherulites in the background.
[Scale = 300 µm; Magnification: × 50].
stopped growing and new nucleation centers ap-
peared in the gaps.
As x is increased further the polygons reach a
maximum linear size of ∼ 2 cm at x = 0.20, and
then grow smaller [Figs. 5(a) and 5(b)]. Prelimi-
nary XRD and DSC studies show that the polygonal
spherulites are highly amorphous. Under crossed
polarizers they show a Maltese cross pattern12 at
Fig. 7 Micrograph of PEO-NH4 ClO4 for x = 0.20 shows
different texture at the boundaries of three regions. [Scale =
300 µm; Magnification: × 50].
the center (Fig. 6) and a directional texture is
clearly visible (Fig. 7) at the boundary between ad-
jacent polygons.
As x is increased from 0.27 to 0.30 the polygons
grow smaller in size, but the film appears smooth
and uniform throughout this range. The average
linear size of the polygonal spherulites are given in
Table 1.

3.3 Higher x Regime
For salt fractions higher than 0.30, excess salt re-
mains uncomplexed and can be seen as separate
crystals on the film (Fig. 8), with spherulites still
seen in the background. This is also confirmed by
VTPM where at 68◦ C only the grains of salt remain
and the other phases have melted.
Table 1 summarizes the characteristics of the
films obtained for varying x.
4. CONCLUSION
The films prepared consist of the following phases
in varying proportions — pure PEO, PEO-salt com-
plex and uncomplexed NH4 ClO4 , which may be in
amorphous or crystalline form. A quantitative anal-
ysis of the relative amount of the phases in these
films is not yet complete. XRD, DSC and conduc-
tivity studies are in progress, and are expected to
shed more light on this problem.
We may, however, offer a qualitative explanation
of the observations.
In the low x regime, the salt forms complexes
in the form of isolated crystallites, which diffuse
through the viscous solution by a random walk.
Two crystallites, on meeting, stick together.
After a certain number has aggregated, immobile
islands are formed which act as nucleation centers.
The islands grow in the form of DLA, as more and
more crystallites reach them. Preliminary XRD re-
sults indicate that the region with trees are more
crystalline than the regions without trees. Infra
red study (Perkin Elmer, 597) of regions having the
tree growth and others having no growth were done.
Spectra of both exhibit the same absorption bands.
As we restricted our study to optical microscopy
and photography at present we have not been able
to quantify the amount of pure PEO and NH4 ClO4
present in the cluster.
As the salt concentration increases the number
of nucleation centers per unit area increases, so
the trees become smaller and more closely spaced
[Fig. 2(b)].
At a certain x, the salt-complex crystallites
become so dense that the aggregation process
is no longer diffusion limited and the compact
aggregation starts. This is the crossover region
(x = 0.18).
The regimes x < 0.10 and 0.18 < x < 0.27
both exhibit spherulites of macroscopic size but
the appearance of the spherulites is quite differ-
Morphology of Polymer-Salt Complex Films . . . 291
ent for the two cases, as shown by Fig. 1 and
Fig. 5(a). The pure PEO forms small (∼ 0.5 mm) ir-
regular spherulites with somewhat rounded bound-
aries, but Fig. 5(a) shows clear polygons with sharp
straight edges of large size (∼ 1 cm). As Fig. 4(a)
shows, these are initially circular. Spherulites con-
tain crystalline as well as amorphous fraction and
preliminary DSC and XRD results shows that the
pure PEO spherulites are more crystalline than the
polygonal ones.
The fact that uniform films are obtained through-
out the range x = 0.18 to 0.27 indicates that com-
plexes can form at different [EO]/[NH+ 4 ] (where EO
is the monomer unit) ratios which correspond to
x = 0.18 (12:1) and x = 0.27 (7:1) respectively.
The conductivity of the films depends on the salt
concentration — directly through the charge car-
rier density and indirectly through the crystallinity,
which is also a function of x. In polymer electrolytes
the amorphous fraction is mainly responsible for
conductivity.
We are at present investigating the effect of the
varied morphology on other properties and plan to
report this later.
ACKNOWLEDGEMENTS
The authors are grateful to COSIST for provid-
ing a grant to the Dept. of Physics, J.U. for the
polarizing microscope. The authors are also very
grateful to the following persons: Dr. P. Nandi
(Physics Dept., J.U.) and Dr. Ruma Basu (Physics
Dept., Jogomaya Devi College) for their active co-
operation in the usage of the microscope, Prof. D.
Chakraborty (IACS) for help in Hausdorff dimen-
sion measurements, Prof. R. G. Bhattacharyya and
Rabindranath Pradhan (Chemistry Dept., J.U.)
for IR measurements, Prof. N. Roy Chowdhury
(Chemistry Dept., IACS) for DSC measurements,
Mr. S. N. Dutta (SINP) for XRD, Mr. Joydeep Roy
for the photographs and Prof. A. N. Basu for stim-
ulating discussions. Finally, AJB thanks the UGC
for a Senior Research Fellowship.
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