553

Macromol. Mater. Eng. 2002, 287, 553558

Full Paper: Biodegradable thermoplastic starch (TPS)/

clay hybrids were prepared by melt intercalation. Three
organically modified montmorillonite (MMT) with different ammonium cations and one unmodified Na+ MMT
(Cloisite Na+) were used. Cloisite Na+ showed the best
dispersion in the TPS matrix. It was observed that the
TPS/Cloisite Na+ hybrid showed an intercalation of TPS
in the silicate layer due to the matching of the surface
polarity and interactions of the Cloisite Na+ and the TPS,
which gives higher tensile strength and better barrier
properties to water vapor as compared to the other TPS/
organoclay hybrids as well as the pristine TPS. It was
found that the dynamic mechanical properties of the TPS/
clay hybrids were also affected by the polar interactions.

Preparation and Properties of Biodegradable

Thermoplastic Starch/Clay Hybrids
Dedicated to Prof. Won-Jei Cho on the occasion of his retirement

Hwan-Man Park,1 Xiucuo Li,2 Chang-Zhu Jin,3 Chan-Young Park,3 Won-Jei Cho,1 Chang-Sik Ha* 1
1

Dept. of Polymer Science and Engineering, Pusan National University, Pusan 609-735, Korea
Fax: +82-51-514-4331; E-mail: csha@pnu.edu
2
School of Chemical Engineering, Hebei University of Technology, Tianjin 300130, P.R. China
3
Dept. of Polymer Science and Engineering, Pukyung National University, Pusan 608-739, Korea

Keywords: biodegradable; clay; hybrid; nanocomposites; thermoplastic starch;

Introduction
Starch is known to be completely biodegradable in soil
and water and to be one of the effective packing materials
because it is a cheap resource material and has very fast
biodegradability.[1] Starch promotes the biodegradability
of a non-biodegradable plastic and starch also can be
used together with fully biodegradable synthetic plastics,[2, 3] producing biodegradable blends of low costs. The
starch remains in granular form in the plastic matrix and
thus may act as a filler.
One major problem with granular starch composites is
their limited processibility, due to the big particle sizes
(5100 lm). Therefore, it is difficult to make blown thin
Macromol. Mater. Eng. 2002, 287, No. 8

films for package applications. For this reason, thermoplastic starch (TPS) has been developed by gelatinizing
starch with 610% moisture with heat and pressure.[4, 5]
Poor water resistance and low strength are limiting factors, however, for the use of materials manufactured only
from TPS, and hence it is often blended with other polymers. For instance, it was found that the ductility of the
gelatinized starch plasticized with approximately 15
wt.-% glycerol and 10 wt.-% water was improved by adding poly[ethylene-co-(vinyl alcohol)] (44 mol-% ethylene) (EVOH).[6] If the mechanical properties of the TPS
can be further improved by the addition of a small quantity of an environmentally benign material, this polymer

i 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1438-7492/2002/08080553$17.50+.50/0

554

H.-M. Park, X. Li, C.-Z. Jin, C.-Y. Park, W.-J. Cho, C.-S. Ha

will find applications in more special or severe circumstances.

Organic-inorganic hybrids have attracted great interests
since they exhibit unexpected hybrid properties synergistically derived from the two components.[1, 7 9] Melt intercalating polymers into the layered silicates of clay has
been proven to be an excellent technique to prepare polymer-layered silicate (PLS) hybrids.[9 15] With only a few
percent of clay, PLS exhibit greatly improved mechanical, thermal and barrier properties compared with the
pristine polymers.[16] The essential raw material for a
nanoclay is montmorillonite (MMT), 2-to-1 layered
smectite clay with platelet structure.[9 11] MMT clays
have been traditionally modified through a cationic ion
substitution reaction with surface sodium ions.[12]
More importantly, clay is environmentally friendly,
naturally abundant and economic. In order to realize the
combination of the biodegradability of cheap TPS and the
high strength and stability of the clay, TPS/clay hybrids
were prepared through a melt intercalation method in the
present work. So far there are no reports on the preparation of biodegradable PLS hybrids except poly(e-caprolactone)/clay hybrids.[17, 18] Furthermore, to the best of our
knowledge, this is the first report to deal with the blends
of thermoplastic starch and clay.
The objective of our research is to prepare the biodegradable blends of TPS and clay, and to investigate the
influence of the nanostructure on the properties of TPS/
clay hybrids. The hybrids were characterized by X-ray
diffraction (XRD) and transmission electron microscopy
(TEM). Tensile, dynamic mechanical, thermal and barrier
properties of the hybrids are discussed.

Experimental Part
Materials
Four kinds of MMT were purchased from Southern Clay
Co.; three kinds of organically-modified MMT (organoclays)
(Cloisite 30B, Cloisite 10A, and Cloisite 6A) and one natural
Na+ MMT (Closite Na+). The ammonium cations of the organoclays are. respectively. methyl tallow bis(2-hydroxyethyl)
for the Cloisite 30B, dimethyl benzyl hydrogenated-tallow
ammonium for the Cloisite 10A, and dimethyl, dihydroge-

nated tallow, quaternary ammonium chloride for the Cloisite

6A. Table 1 summarizes the related structure information of
the clays used in this work.
The TPS was prepared using potato starch (PS: Katayama
Co.) glycerol (95%, Junsei Chemical Co., Ltd), and water in
the Haake Rheocord 600 system equipped with a mixer. The
TPS was prepared using a two-step procedure. The premixture containing native potato starch/water/glycerol (5/2/3 by
wt. ratio) was retained for 1 h to let plasticizers (water and
glycerol) to swell the granular starch molecules. These
swelled mixtures were transferred to the Haake mixer and
the starch was gelatinized at 110 8C for 25 min at 100 rpm of
roller speed. The temperature and torque were monitored
during the processing. After processing, the TPS were cooled
and cut to small particles in order to be premixed with clay
powders easily. The TPS prepared in this work was identified using X-ray diffraction (XRD) and a scanning electron
microscopy (SEM: JEOL 35CF).
Preparation of TPS/Clay Hybrids
TPS and clays were dried under vacuum at 80 8C for at least
24 h before use. TPS was mixed with clays in a Haake Rheocoder 600 roller mixer for 20 min. The contents of clays
were fixed at 5 wt.-%. The rotor speed was 50 rpm and the
temperature was set at 110 8C. The mixed product was injection molded using a Mini-MAX molder (Custom Scientific
Instruments, Inc., CS-183 MMX) to get dog-bone shaped
specimens for characterization and property measurements.
The blends after preparation were placed in tightly sealed
polyethylene bags to prevent any moisture absorption.
Characterization
XRD studies of the samples were carried out using a Rigaku
D/max 2200H X-ray diffractometer(40 kV, 50 mA) equipped
with Cu Ka radiation (k = 0.154 nm) and a curved graphite
crystal monochromator at a scanning rate of 0.5 8/min. TEM
images were taken from cryogenically microtomed ultrathin
sections using a Hitachi H-800 TEM, operated at an acceleration voltage of 100 kV.
Properties
Tensile properties of the hybrids were measured using a Universal Testing Machine (Hounsfield UL25) at room temperature. The crosshead speed was 10 mm/min. All measurements were performed for five replicates of dog-bone shaped

Table 1. Structure information of different kinds of clays. T = tallow (L65% C18, L30% C16, L5% C14), HT = hydrogenated
tallow, anion = chloride.
Clay a)
Cloisite Na+
Cloisite 6A
Closite 10A
Cloisite 30B
a)

Ammonium cation

XRD peak position 2h

degree

Basal spacing 001

nm

none
(CH3)2 (HT)2N+
(CH3)2(HT)(CH2C6H5)N+
(CH3)(T)(CH2CH2OH)2N+

7.85
2.49, 4.72
4.52
4.73

1.17
3.57
2.00
1.88

The surface hydrophobicity of Cloisite clays: 6A AA 10A A 30B A Na+.

Preparation and Properties of Biodegradable Thermoplastic Starch/Clay Hybrids

specimens and averaged. Water vapor permeability (WVP)

of a film was determined gravimetrically at 24 l 2 8C using
the ASTM E96-93 method, and the WVP values were calculated using the WVP Correction Method described by Gennadios, et al.[19] Two specimens of 1.7 cm diameter discs
were cut from each preconditioned film. Dynamic mechanical analysis (DMA) was performed with a Rheovibron DDV25F (Orientec co.) in the tension mode with the following
parameters: frequency = 1 Hz; scan rate = 4 8C/min; temperature range = 150 8C to 130 8C. Samples were prepared
by injection molding using a mini-max molder and dried at
100 8C in the chamber for 15 min to remove any residual
bulk water before the measurements.

Results and Discussion

Figure 2. XRD patterns of Cloisite 30B (a) and the TPS/Cloisite 30B hybrid (b).

Dispersion of Clays in a TPS Matrix

To prepare TPS/clay hybrids, four kinds of natural and
organically modified clays were selected to mix with the
TPS in the Haake Rheocorder mixer. Figure 1 through 4
show the XRD patterns of the hybrids with clay contents
of 5 wt.-%. It can be seen that the dispersion states of
clays in the TPS matrix depends on the type of the clay
used.
Figure 1 shows the XRD patterns of the Cloisite Na+
(a), TPS (b), and the TPS/Cloisite Na+ hybrid (c). The
hybrid shows an intensive peak at 2H = 4.96 8 with a
weak peak of TPS at ca. 9.8 8, while the Cloisite Na+
exhibits a single peak at 7.85 8. It should be also noted
from Figure 1b that TPS exhibits broad featureless peaks
in the range of around 312 8 due to the amorphous character of TPS.[18, 20] The appearance of the new peak at
4.96 8 (d spacing = 1.78 nm) with diminishing the original
peak of the clay at 2H = ca. 7.85 8 (d spacing = 1.17 nm)
indicates the intercalation of TPS in the gallery of the silicate layer of the Cloisite Na+.
In Figure 2, the TPS/Cloisite 30B hybrid shows a weak
peak at 2H = 4.3 8, while the Cloisite 30B exhibits an
intensive single peak at 4.73 8, indicating hardly to say
the formation of the intercalated hybrids. Also in the case

Figure 3. XRD patterns of Cloisite 10A (a) and the TPS/Cloisite 10A hybrid (b).

Figure 4. XRD patterns of Cloisite 6A (a) and the TPS/Cloisite

6A hybrid (b).

Figure 1. XRD patterns of Cloisite Na+ (a), TPS (b), and the
TPS/Cloisite Na+ hybrid (c).

of the TPS/Cloisite 10A hybrid, the original peaks of the

Cloisite 10A (at ca. 4.52 8) remain in the hybrids, indicating that little or no intercalation has occurred. (Figure 3).
For the TPS/Cloisite 6A hybrid, only a weak peak at
2.85 8 with the amorphous featureless pattern of the TPS
was observed, while the original peaks of the Cloisite 6A
were not shown at 2.49 8 and 4.72 8, as shown in Figure 4.
The result implies that the hybrid system exhibits almost

555

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H.-M. Park, X. Li, C.-Z. Jin, C.-Y. Park, W.-J. Cho, C.-S. Ha

the silicate layer, and the ammonium cations located in the

gap of the silicate layers. Due to the strong polar interactions between a small amount of polar hydroxyl group of
water in the TPS chain and the silicate layer of the inorganic Cloisite Na+, the TPS chains can intercalate into the
interlayer of the Cloisite Na+. On the other hand, the Cloisite 6A and the Cloisite 10A are too hydrophobic and do
not match with the polarity of TPS, and discourage TPS
intercalation. The Cloisite 30B was also rendered hydrophobic, but was less than that of the Cloisite 6A and the
Cloisite 10A. Furthermore, due to the existence of hydroxyethyl groups, the methyl tallow bis(2-hydroxyethyl)
ammonium cation in the Cloisite 30B interlayer has polar
interactions with TPS, favoring the intercalation of TPS
chains and the formation of TPS/Cloisite 30B hybrids.
However, the introduction of these polar hydroxyethyl
groups also enhances the interaction of the ammonium
cation with the silicate surface. As a result, replacement of
the surface contacts by TPS chains will be less favorable,
impeding the extensive intercalation.
It may be argued here that any component (starch, glycerol, and water if remaining) may escape from the TPS
matrix and swell the clay, which favors the intercalation
of the TPS chains in the case of TPS based hybrids. Since
the TPS/Cloisite 30B, TPS/Cloisite 6A, and TPS/Cloisite
10A hybrids except the TPS/Cloisite Na+ hybrid did not
exhibit any intercalation behavior, however, the possibility of the swelling of clays by any of the parent component residues must be negligible, if any.

Figure 5. TEM images of TPS/clay hybrids of different kinds

of clay. a) TPS95/Cloisite Na+, b) TPS95/Cloisite 6A, c) TPS95/
Cloisite 10A, d) TPS95/Cloisite 30B.

neither intercalation of TPS nor partial exfoliation of the

Cloisite 6A in the TPS matrix.
To further confirm the above results, TEM micrographs
are presented in Figure 5. The TEM images of the TPS/
Cloisite Na+ hybrid exhibit multilayer nanostructure with
alternating polymeric and inorganic silicate layers (Figure
5a), whereas the TEM images of the TPS/Cloisite 30B
hybrid showed almost no intercalated hybrid morphologies with expanded layer gaps (Figure 5d). The TEM
results correspond well with the XRD patterns. The TEM
images of the TPS/Cloisite 6A hybrid (Figure 5b) and the
TPS/Cloisite 10A hybrid (Figure 5c) did not show the
layered nanostructures of the organoclays but instead
large particle agglomerates, indicating the lack of compatibility between TPS and the organoclays. Comparison
of Figure 4 and Figure 5b indicates that the TPS/Cloisite
6A hybrid exhibits neither intercalated nor exfoliated
nanostructure.
The nanostructure of the polymer/clay hybrids depends
on the compatibility and interaction among the polymer,

Properties
Table 2 gives the tensile properties of various TPS/Clay
hybrids containing 5 wt.-% of clays. It is obvious that the
TPS/Cloisite Na+ hybrid and the TPS/Cloisite 30B hybrid
exhibit higher tensile strength and elongation at break
due to the partial nanocomposite formation compared to
two other hybrid systems. It is noteworthy that the tensile
strength and elongation at break of the TPS/Cloisite Na+
hybrid increased by ca. 30 and 20%, respectively, as compared to the pristine TPS. The increase of the hybrid elongation at break may be due to stress-concentration sites
which lead to shear banding and/or craze initiation, which
has been observed sometimes in immiscible blends.[21]
Table 2. Tensile properties of TPS/clay hybrids of 5 wt.-%
clay contents.
Clay type
Cloisite Na+
Cloisite 30B
Cloisite 10A
Cloisite 6A
Blank (0%)

Tensile strength
MPa

Elongation at break
%

3.32
2.80
2.14
2.51
2.61

57.2
44.5
34.9
38.0
47.0

Preparation and Properties of Biodegradable Thermoplastic Starch/Clay Hybrids

Figure 6. Water vapor permeability behavior of TPS/clay

hybrids of different kinds of clays at 24 8C.

Owing to our interest in developing polymeric materials with improved barrier properties, we have studied the
permeability of water in TPS hybrid films (thickness is
ca. 110 lm). Water vapor permeability (WVP) of hybrid
films with different kinds of clays was examined at a
vapor pressure difference of 0/54% RH (i. e. 0 to 54%
RH) across the film. Figure 6 shows the plots of the
amount of WVP of the hybrid films as a function of time.
Under steady state conditions, the increase in weight with
time corresponds to the amount of water diffusing
through the hybrid films. Comparing WVP of the TPS/
clay hybrids, all the hybrid films showed lower WVP
than that of the pristine TPS due to the barrier properties
of the clay, and the TPS/Cloisite 10A hybrid film showed
higher WVP than the other hybrid systems. The high
hydrophilicity of TPS favorable to the adsorption of water
molecules could also contribute to the increase in the
WVP of the films. Generally, water vapor transmission
through a hydrophilic film depends on both diffusivity
and solubility of water molecules in the film matrix.[22]
The result of Figure 6, therefore, may be attributed to
the fact that an increase in the spacing between the starch
polymer chains (because of bad dispersion as already
shown in the TEM micrograph) due to some aggregation
of Cloisite 10A particles, may promote water vapor diffusivity through the film and hence accelerate the water
vapor transmission. It should also be noted that the TPS/
Cloisite Na+ hybrid showed the lowest WVP, meaning
the best barrier property, among all the hybrids. This
enhanced barrier characteristics of the TPS/Cloisite Na+
hybrid result from the better-ordered intercalated structure of the hybrid that had high aspect ratio nano-layers
of Cloisite Na+ clay in the hybrid.
DMA analysis has been performed to track the temperature dependence of storage modulus and tan d behaviors of the TPS/clay hybrids. Figure 7 shows the temperature dependence of storage modulus (E 9) of various TPS/
clay hybrids. It is seen that the moduli of the TPS/Cloisite
Na+ hybrid are higher than those of the pristine TPS over
broad temperature ranges from around 70 to 70 8C,

Figure 7. Typical storage modulus behavior of TPS/clay

hybrids of different kinds of clays.

Figure 8.
of clays.

Tan d behavior of TPS/clay hybrids of different kinds

while the moduli of the TPS/Cloisite 30B, TPS/Cloisite

10A, and TPS/Cloisite 6A hybrids are lower than those of
the TPS. Even though the TPS/Cloisite 30B hybrid shows
higher storage modulus than the other two hybrids (TPS/
Cloisite 10A and TPS/Cloisite 6A) due to the intercalated
structure, the storage modulus of the hybrid is lower than
that of the TPS because of bad dispersion or lack of compatibility between the TPS and the organoclays. The
shifts of the relaxations to lower temperatures may also
indicate that the matrix has been plasticized, since the
Cloisite 6A, 30B, and 10A are prepared with an excess of
surfactants, which may diffuse into the matrix.
In Figure 8, the relaxation processes associated with
the glass transition of the amorphous phase of TPS could
be clearly determined. The relaxation temperatures can
be taken at the maximum of the respective tand peaks in
Figure 8. The TPS shows two transition peaks at around
7.0 8C and 64 8C due to the a-relaxation of starch (Ta)
and the b-relaxation (Tb) of glycerol, respectively.[23]
When 5 wt.-% of Cloisite Na+ was added to TPS (Figure 8b), the temperatures of the two peaks were shifted
toward higher temperatures (64 to 53 8C and 7 to 12 8C,
respectively) indicating that the silica layered clay in the
hybrids do strongly influence the chain mobility of the
TPS matrix. On the other hand, for both the hybrids of

557

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H.-M. Park, X. Li, C.-Z. Jin, C.-Y. Park, W.-J. Cho, C.-S. Ha

Cloisite 10A, and 6A (Figure 8d, e), the two relaxation

temperatures were decreased by ca. 10 8C compared to
the pure TPS. This may be due to poor interaction or
strong repulsion between the hydrophilic TPS and the
hydrophobic organoclays. In this sense, the TPS/Cloisite
6A hybrid showed the largest shift toward lower temperature for both of the two transition temperatures.
Comparison of Figure 7 and 8 indicates that the
dynamic mechanical properties of the TPS/clay hybrids
are strongly affected by the surface polarity and the interactions of the clays and the polymers in question. The
higher storage modulus and the larger shift in the relaxation temperatures of the TPS/Cloisite Na+ hybrid in comparison to other hybrids is clearly attributed to the matching of the surface polarity and interactions of the Cloisite
Na+ and the TPS. It should be again noted that the compatibility and optimum interactions between polymer
matrix, organic modifiers (if any) and the silicate layer
surface itself are crucial to the property improvement as
well as the formation of intercalated PLS hybrids.

Conclusions
Novel biodegradable thermoplastic starch (TPS)/clay
hybrids were prepared through a melt intercalation
method. Three kinds of organoclays, Cloisite 30B, 10A,
and 6A with different ammonium cations, and one unmodified Cloisite Na+ MMT were chosen in the hybrid preparation. Cloisite Na+ MMT showed the best dispersion
in the nanostructure of the TPS hybrids. The dispersion of
the organically modified MMT in the TPS matrix
depended on the hydrophilicity of the organoclays and
especially the polar interaction between the silicate layers
and the TPS. The strong interaction between the TPS and
the Cloisite Na+ leads to higher tensile properties and
lower water vapor permeability than the pristine TPS.
The results also showed that adding only 5 wt.-% of the
clay to the TPS matrix is favorable to improve the tensile
strength and the barrier property of TPS.
For the TPS/Cloisite Na+ hybrid, the storage modulus
was higher than any other TPS containing hybrid systems
as well as the pristine TPS in the temperature ranges
above ca. 20 8C. The TPS showed two transition peaks
at around 7.0 8C and 64 8C due to the glass transitions of
starch and glycerol, respectively. The tan d data of the
hybrids showed that the two transition peaks around
64 8C and 7.0 8C of the TPS were shifted towards higher
temperatures due to the matching of the surface polarity
and interactions of the Cloisite Na+ and the TPS.

Acknowledgement: The work was supported by the Center for

Integrated Molecular Systems, POSTECH, Korea and the Brain
Korea 21 Project in 2001.

Received: November 5, 2001

Revised: January 29, 2002
Accepted: January 30, 2002

[1] A. Ova, Y. Kurokawa, H. Yasuda, J. Mater. Sci. 2000, 35,

1045.
[2] G. W. Zhou, J. L. Willett, C. J. Carriere, Polym. Eng. Sci.
2001, 41, 1365.
[3] T. Y. Ke , X. Z. Sun, J. Appl. Polym. Sci. 2001, 81, 3069.
[4] E. R. George, T. M. Sullivan, E. H. Park, Polym. Eng. Sci.
1994, 34, 17.
[5] L. L. Zhang, X. M. Deng, S. J. Zhao, Z. T. Huang, Polym.
Int. 1997, 44, 104.
[6] C. D. Muzny, B. D. Butler, H. J. M. Hanley, F. Tsvetkov,
D. G. Peiffer, Mater. Lett. 1996, 28, 379.
[7] S. R. Lee, H. M. Park, H. Lim, T. Kang, X. Li, W. J. Cho,
C. S. Ha, Polymer 2002, 43, 2495.
[8] R. Gangopadhyay, A. De, Chem. Mater. 2000, 12, 608.
[9] N. Hasebawa, M. Kawasumi, M. Kato, A. Usuki, A.
Okada, J. Appl. Polym. Sci. 1998, 67, 87, and references
therein.
[10] A. K. Carrado, Appl. Clay Sci. 2000, 17, 1.
[11] A. Usuki, Y. Kojima, M. Kawasumi, A. Okada, Y.
Fukishima, T. Kurauchi, O. Kamicaito, J. Mater. Res.
1993, 8, 1179.
[12] R. Kirshnamoorti, R. A. Vaia, E. P. Ciannelis, Chem.
Mater. 1998, 8, 1728.
[13] P. C. Lebaron, Z. Wang, T. J. Pinnavaia, Appl. Clay Sci.
1999, 15, 11.
[14] X. Li, T. Kang, W. J. Cho, J. K. Lee, C. S. Ha, Macromol.
Rapid Comm. 2001, 22, 1310.
[15] M. Zanetti, S. Lomakin, G. Camino, Macromol. Mater.
Eng. 2000, 279, 1.
[16] G. Jimenez, N. Ogata, H. Kawai, T. Ogihara, J. Appl.
Polym. Sci. 1997, 64, 2211.
[17] P. B. Messersmith, E. P. Giannelis, J. Polym. Sci., Part A:
Polym. Chem. 1995, 33, 1047.
[18] M. Vikman, S. H. D. Hulleman, M. van der Zee, P. Myllarinen, H. Feil, J. Appl. Polym. Sci. 1998, 74, 2594.
[19] A. Gennadios, C. L. Weller, C. H. Gooding, J. Food Eng.
1994, 21, 395.
[20] J. J. G. Van Soest, K. Benes, D. de Wit, Polymer 1996, 37,
3543.
[21] S. J. Lee, S. K. Kwon, W. J. Cho, C. S. Ha, J. Appl. Polym.
Sci. 1999, 73, 1697.
[22] N. Gontard, S. Guilbert, Biopackaging; Food Packaging
and Preservation, Blackie Academic & Professional, London 1994.
[23] L. Averous, N. Fauconnier, L. Moro, C. Fringant, J. Appl.
Polym. Sci. 2000, 76, 1117.