Carbohydrate Polymers 77 (2009) 576–582

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Preparation, characterization and properties of binary and ternary blends with

thermoplastic starch, poly(lactic acid) and poly(butylene adipate-co-terephthalate)
Jie Ren a,b,*, Hongye Fu a, Tianbin Ren a,b, Weizhong Yuan a,b
a
Institute of Nano- and Bio-Polymeric Materials, School of Materials Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092, China
b
Key Laboratory of Advanced Civil Engineering Materials, Ministry of Education, School of Materials Science and Engineering, Tongji University,
1239 Siping Road, Shanghai 200092, China

a r t i c l e i n f o a b s t r a c t

Article history: Binary and ternary blends of thermoplastic starch (TPS), poly(lactic acid) (PLA) and poly(butylene adipate-
Received 6 November 2008 co-terephthalate) (PBAT) were prepared using a one-step extrusion process. The concentration of TPS in
Received in revised form 11 January 2009 both binary and ternary blends was fixed at 50 wt%, with the rest being PLA and PBAT. A compatibilizer
Accepted 26 January 2009
with anhydride functional groups was used to improve the interfacial affinity between TPS and the
Available online 6 February 2009
synthetic polyesters. The addition of a small amount of compatibilizer greatly increased the mechanical
properties of the blends. Mechanical properties of the blends exhibited a dramatic improvement in
Keywords:
elongation at break with increasing PBAT content. Compared to the non-compatibilized blends, the
Thermoplastic starch
Poly(lactic acid)
morphology analysis of the blends showed that most of the TPS particles were melting and were well
Poly(butylene adipate-co-terephthalate) dispersed in the polyester matrix for the compatibilized blends. The water absorption data of the non-
Ternary blends compatibilized blends increased more significantly than the compatibilized blends when PBAT content
increased.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction (Tang, Alavi, & Herald, 2008b) are two of the most widely used
plasticizers. The role of plasticizers is to destructurize granular
As people’s growing concern for environmental protection, bio- starch by breaking hydrogen bonds between the starch macromol-
degradable materials have attracted considerable attention as ecules, accompanying with a partial depolymerization of starch
interesting sustainable plastics. Starch is a naturally occurring bio- backbone. Chemical modification of starch such as esterification
polymer that can be extracted from many crops including corn, (Raquez et al., 2008) is the other well known methods to get TPS.
wheat, rice, potato and so on (Tester & Karkalas, 2002). As an inex- Acetylated starch that can be obtained through changing part of
pensive and renewable source, it has been used as filler (Chandra & the hydroxyl groups into acetyl groups has been extensively stud-
Rustgi, 1997; Griffin, 1977; Tang, Zou, Xiong, & Tang, 2008a) for ied over the last two decades (Reinisch, Radics, & Roatsch, 1995;
environmentally friendly plastics for about three decades. How- Wang & Wang, 2002). Although various methods have been tried
ever, native starch has to be modified in order to be melt-processed to modify native starch in the last few years, it is still difficult to
as a thermoplastic because the melting temperature (Tm) of pure completely overcome its moisture absorption nature and poor
dry starch is close to 220–240 °C and the onset temperature of mechanical properties of the final products.
starch degradation is around 220 °C (Sarazin, Li, Orts, & Favis, Polymer blending is an important way to obtain new materials
2008; Souza & Andrade, 2002; Stepto, 2003). that can meet different needs. Blending of TPS with other polymers
In order to obtain thermal plastic starch (TPS), both physically represents an important route to overcome the limitations of TPS.
and chemically methods of modification of starch have been Poly(lactic acid) (PLA), which is a hydrophobic and semicrystalline
widely studied. Physical modification of starch can be prepared polyester, is a renewable material that can be utilized by microbes
by extrusion using various plasticizers (Da Roz, Carvalho, Gandini, within 30–40 days (Hakkarainen, Karlsson, & Albertsson, 2000;
& Curvelo, 2006; Forssell, Mikkila, Suortti, Seppala, & Poutanen, Itavaara, Karjomaa, & Selin, 2002). Its good physical properties
1996; Graaf, Karman, & Janssen, 2003; Ma, Yu, & Wan, 2006). and commercial availability make it very attractive, not only as a
Water (Teixeira, Da Roz, Carvalho, & Curvelo, 2007) and glycerol substitute of non-biodegradable polymers for commodity applica-
tions, but also for specific applications in medicine and in agricul-
tural areas. The main limitation of PLA is its high price which
* Corresponding author. Address: Institute of Nano- and Bio-Polymeric Materials,
caused by its complicated production process. Blending of PLA with
School of Materials Science and Engineering, Tongji University, 1239 Siping Road,
Shanghai 200092, China. Tel.: +86 21 65989238; fax: +86 21 65989238. TPS is a good way to balance the cost-effective issue and get a new
E-mail address: [email protected] (J. Ren). material that has good performances. However, previous studies

0144-8617/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbpol.2009.01.024
 J. Ren et al. / Carbohydrate Polymers 77 (2009) 576–582 577

have shown that TPS/PLA blend have rather poor mechanical prop- TPS was prepared by a high speed mixer (SHR-10A, 2880 r/min,
erties due to the poor interfacial affinity of starch and PLA (Ke & Zhong-Yun machinery Co., Ltd., China) in the following propor-
Sun, 2000; Kim, Chin, Yoon, Kim, & Jung, 1998; Ren, Liu, & Ren, tions: 80 wt% of starch and 20 wt% of glycerol. The mixing time
2007; Wang, Yu, Chang, & Ma, 2008). Thus, compatibility is the vi- was kept at 20 min and the temperature of the mixer was kept
tal problem that has to be dealt with when blending hydrophilic at 120 °C. TPS/polyester binary and ternary blends were prepared
starch granules and hydrophobic PLA together. In order to increase by melt mixing TPS, PLA and PBAT using a twin-screw extruder
the interfacial adhesion between TPS and PLA, polymers having (F: 27 mm, L/D: 40, LEISTRITZ: Germany). The compositions of
functional groups capable of interacting with the hydroxyl groups the blends are shown in Table 1. Before extrusion, PLA and PBAT
on starch are desirable. Huneault and Li (2007) found that MAh- pellets were dried under vacuum at 60 °C for 12 h, respectively.
grafted PLA/starch blend showed much finer dispersed phase and The extrusion temperature was independently controlled at eight
exhibited a dramatic improvement in ductility than pure PLA/ zones along the extruder barrel and a strand die to achieve a tem-
starch blend. Wu (2005) found that acrylic acid grafted PLA and perature profile in the range of 155–175 °C. The screw speed was
starch composite had much better mechanical and thermal proper- set at 80 rpm and feed rate was 30 g/min.
ties than PLA/starch blend. Bhattacharya et al. prepared starch/syn- Injection moulding was accomplished in a JN55E injection
thetic polymer blends by injection moulding and studied the effect moulding machine (Ning Bo Zhen Xiong Machinery Co., Ltd., Chi-
of processing parameters on blends physical properties (Ramku- na). Test specimens for tensile testing were obtained according to
mar, Vaidya, Bhattacharya, & Hakkarainen, 1996), evaluation of GB1040-79 (China). The binary and ternary blends follow the fol-
mechanical properties (Ramkumar, Bhattacharya, & Vaidya, lowing processing conditions: barrel temperature 170 °C, mould
1997), effect of amylopectin on amylose ratio in starch (Mani & temperature 30 °C, back pressure 4 MPa, and injection pressure
Bhattachazya, 1998a), thermal and morphological properties (Mani 12 MPa. All samples were conditioned at room temperature at
& Bhattachazya, 1998b). Their research showed that maleated syn- 50% relative humidity for at least 2 weeks before testing.
thetic polymers such as SMA, EPMA and EVAMA are effective com-
patibilizers for starch/synthetic polymer blends. 2.3. Mechanical properties
Sarazin et al. (2008) studied binary and ternary blends with PLA,
polycaprolactone (PCL) and TPS, it was found that the addition of All the mechanical property measurements were performed at
PCL greatly increased the ductility of PLA/TPS blends. So blending room temperature on injection moulded blends. Both tensile and
PLA/TPS binary blend with another flexible polymer could be a use- flexural properties were measured on a tensile testing machine
ful way to obtain a new kind of materials with excellent integrated (DXLL-5000, Shanghai D&G Instruments Co., Ltd., China) according
performances. Poly(butylene adipate-co-terephthalate) (PBAT) is a to GB1040-79 (China). A crosshead speed of 5 mm/min was used.
flexible copolyester which can fully degrade within a few weeks At least five specimens were used for each blend condition.
with the aid of naturally occurring enzymes. PLA/PBAT blends were
studied by Jiang, Wolcott, and Zhang (2006). The blends showed 2.4. Blend morphology and image analysis (SEM analysis)
decreased tensile strength and modulus, however, elongation and
toughness dramatically increased. The failure mode changed from Impact samples were gold coated and observed under a Hitachi
brittle fracture of the neat PLA to ductile fracture of the blends. In S-2360 N scanning electron microscope (SEM).
this respect, PBAT could be considered as a good candidate for the
toughening of rigid polymers such as TPS/PLA binary blend. 2.5. Melt flow index (MI)
Here, TPS/PLA/PBAT binary and ternary blends were prepared
via a one-step melt-processing. Then, the morphology and proper- MI measurements of various blends were obtained using a
ties of both compatibilized and non-compatibilized blends were model MI-1 plastometer (Tanhor, RZY-400, China). The test was
investigated. To keep the study manageable the TPS content of carried out according to GB/T 3682-2000 (China).
the blend was fixed at 50% by weight, the remaining being the syn-
thetic polymers PLA and PBAT which were varied in different ra- 2.6. Vicat softening temperature (VST)
tios. One anhydride functionalized polymer which has very high
content of maleic anhydride was used as compatibilizer, and for A Vicat softening temperature testing machine (SWB-300C/D,
the compatibilized blends its content was fixed at 1 wt% of the Si-Yu-Da Co., Ltd., China) was used to measure the VST of the
blends. blends. Test specimens for VST testing were obtained according
to GB1633-79 (China).

2. Experimental

2.1. Materials
Table 1
The following materials were obtained from commercial suppli- Compositions of various TPS/polyester blends.
ers and used as received. The corn starch was supplied by Ju-Neng- Samples TPS PLA PBAT Compatibilizer
Jing Corn Co., Ltd. (Shandong, China). Poly(lactic acid) (PLA,
nc-PBAT0 50 50 – –
Mw = 180,000, Mw/Mn = 1.7, L/D isomer ratio is 96:4, Tg = 58, nc-PBAT10 50 40 10 –
Tm = 155 °C) was supplied by Tong-Jie-Liang Biomaterial Co., Ltd. nc-PBAT20 50 30 20 –
(China). Poly(butylene adipate-co-terephthalate) (PBAT, Tg = 29 °C, nc-PBAT30 50 20 30 –
Tm = 110–115 °C, Ecoflex F BX 7011) was supplied by BASF. nc-PBAT40 50 10 40 –
nc-PBAT50 50 – 50 –
c-PBAT0 50 50 – 1
2.2. Processing c-PBAT10 50 40 10 1
c-PBAT20 50 30 20 1
TPS can be obtained by processing granular starch at low water c-PBAT30 50 20 30 1
c-PBAT40 50 10 40 1
or other plasticizer content using thermal and mechanical forces
c-PBAT50 50 – 50 1
(Myllarinen, Partanen, Seppala, & Forssell, 2002). In this paper,
578 J. Ren et al. / Carbohydrate Polymers 77 (2009) 576–582

2.7. Dynamic mechanical analysis (DMA) non-compatibilized blends. The reaction of the anhydride groups
from the compatibilizer with the hydroxyl groups from the TPS
Dynamic mechanical properties were determined as a function granules formed ester linkages (Fig. 2). Therefore, the core of the
of temperature using a DMA testing machine (Q800, TA Instru- hydrophilic TPS granules was wrapped by the hydrophobic shell
ments) in three-point bending mode. The sample size was formed by the compatibilizer which has better compatibility with
60  10  3.9 mm, prepared by hot compression moulding with PLA and PBAT. So compatibilized blends have better interfacial
3 MPa at 160 °C for 3 min using a Flat Sulfuration Machine. The test adhesion between the blend components, thus resulting in a rela-
was carried out in a single cantilever bending mode at a frequency tively compact phase structure and an increase in flexural strength
of 3.33 Hz and a strain of 2 N, corresponding to a maximum dis- and flexural modulus.
placement amplitude of 30 lm. The range of temperature was
from 30 to 120 °C. The standard heating rate was 3.0 °C/min. 3.2. Morphology

2.8. Water absorption The morphology of the blends has been performed by SEM and
Table 2 shows the starch granules distributing in the polymer ma-
The moulded samples (size: 10  10  4 mm) were immersed trix. Large starch phase domains could be found for the non-com-
in water at room temperature. The samples were then removed patibilized blends. The TPS phase that formed from agglomerated
at specific intervals, gently blotted with tissue paper to remove starch granules, was partially plasticized, and could not totally
the excess water on the surface, and the weight recorded. This pro- flow as a thermoplastic. While after compatibilized, the starch
cess was repeated at several time intervals. The water absorption granules were mostly melted and formed a continuous phase with
ratio was calculated by the formula below: synthetic polymer matrix. Therefore, the non-compatibilized
blends showed poor mechanical properties compared to those of
Mx  Mo
v¼  100% ð1Þ compatibilized ones as described earlier. These results confirm that
Mo
the anhydride functionalized polymer acted as compatibilizer and
Mx indicates the weight of the samples in the X day; Mo indi- increases the interfacial adhesion between the blend components
cates the initial weight of the samples; v indicates the water and thereby produces a finer and more uniform morphology,
absorption ratio. hence, resulting in significantly improvement of mechanical prop-
erties. Better distributions of starch granules could be seen when
3. Results and discussion PBAT content increased.

3.1. Mechanical properties 3.3. Melt flow index

The tensile strength and elongation at break of TPS/polyester Melt flow index (MI) is an assessment of average molecular
samples are shown in Fig. 1a. When a small amount of compatibi- mass and is an inverse measure of the melt viscosity. In other
lizer was added to the blend, increases in both tensile strength and words, the higher a MI, the more flows of polymer under test con-
elongation at break were observed over the whole composition ditions. Knowing the MI of a polymer is vital to anticipating and
range. These increases could be ascribed to the poor interfacial controlling its processing. Generally, higher MI polymers could
adhesion between TPS and polyesters being improved after the be used in blow moulding, and lower MI polymers could be used
compatibilizer was added. in injection moulding or extrusion processes. Fig. 3 shows the MI
For the non-compatibilized blends, there was a decrease in the values for various blends under a certain condition. The MI values
tensile strength of the blends with increasing PBAT content. The for non-compatibilized and compatibilized blends both increased
tensile strength decreased slowly with PBAT content increasing (from 0.94 to 2.63 and 1.56 to 9.26 g/10 min, respectively) with
from 0 to 20 wt%, but it decreased sharply at a PBAT level between PBAT content. The compatibilized blends had much higher MI val-
20 and 30 wt%, where the tensile strength of the blend decreased ues than the non-compatilized blends. The difference could be
by about 30% (from 12.22 to 7.60 MPa) compared to the strength attributed to the better interfacial interaction between synthetic
of the nc-PBAT0 blend (17.99 MPa). The decreasing rate of the ten- polymer and starch since the anhydride groups of the compatibiliz-
sile strength slowed down again when PBAT content increased to er could react with the hydroxyl groups of starch to form ester
more than 30 wt%. This could be ascribed to the main phase chang- bonds between these components, thus increased the melt flow
ing from TPS/PLA (comparatively rigid) to TPS/PBAT (compara- properties of the blends.
tively flexible) at PBAT content between 20 and 30wt%. For the
compatibilized blends, as PBAT content increased, the tensile 3.4. Thermal properties of blends
strength of the blends first decreased, and then increased (with
the inflexion at 30 wt% PBAT content). This might be caused by The storage modulus (G0 ), loss modulus (G00 ) and loss factor
the phase separation of PLA and PBAT. As PBAT content increased, (tand) of TPS/polyester are showed in Fig. 4. Storage modulus is a
the elongation at break of blends increased. At higher concentra- measure of the energy stored and recovered in a cyclic deformation
tions of PBAT (>30 wt%) the increase was dramatic; the elongation whereas the loss modulus is a measure of the energy dissipated.
at break increased by many times compared to the elongation of Tand is the ratio of the energy lost to the energy stored in a cyclic
the nc-PBAT0 blend (1.28%). This behaviour occurred in both com- deformation. DMA studies revealed that all binary and ternary
patibilized and non-compatibilized blends. blends had a decreasing G0 over the glass transition temperature
The flexural strength and flexural modulus of TPS/polyester of PLA from 40 to 60 °C. The decrease in G0 suggested that the
samples are shown in Fig. 1b. It can be seen from Fig. 1b that both material was becoming less elastic or conversely more perma-
flexural strength and flexural modulus of TPS/polyester blends nently deformable. As PBAT content increased, the value of G0 of
were decreased gradually with increasing PBAT content. This is be- the blends decreased (Fig. 4a), which indicated that the blends
cause PBAT is flexible polyester, as its content increasing the with less PBAT content were more elastic than those with more
blends became much softer, thus resulting in a decrease in flexural PBAT content. It was noticed that these results were similar to
strength and flexural modulus. The compatibilized blends showed those of tensile strength, percentage elongation, flexural strength
higher flexural strength and flexural modulus comparing to the and flexural modulus results (Figs. 1 and 2). The storage modulus
 J. Ren et al. / Carbohydrate Polymers 77 (2009) 576–582 579

Fig. 1. Mechanical properties of TPS/polyester blends as a function of PBAT content, (a) Tensile strength and elongation at break; (b) Flexural strength and flexural modulus.

Fig. 2. Formation of TPS and compatibilizer and the reaction between them.
580 J. Ren et al. / Carbohydrate Polymers 77 (2009) 576–582

Table 2
SEM micrographs of various TPS/polyester blends.

Samples SEM image (magnification = 2000, Scale bar = 20 lm)

Non-compatibilized blends Compatibilized blends
TPS/PLA 50/50

TPS/PLA/PBAT 50/40/10

TPS/PLA/PBAT 50/20/30

TPS/PBAT 50/50

and the loss modulus correlated positively to the tensile strength,

G00 (Fig. 4b) and tand (Fig. 4c) both showed a slight decrease with
percentage elongation, flexural strength and flexural modulus
increasing PBAT content.
respectively.
Vicat softening temperature (VST) is the temperature at
In DMA studies a peak in G00 and tand are usually used as indi-
which a flat-ended needle penetrates the specimen to the
cators of glass transition. The Tg of PLA measured by the peak of
 J. Ren et al. / Carbohydrate Polymers 77 (2009) 576–582 581

Fig. 3. Melt flow index curves of TPS/polyester blends, as a function of PBAT Fig. 6. Water absorption of non-compatibilized and compatibilized blends.
content.

depth of 1 mm under a specific load. The temperature reflects

the point of softening to be expected when a material is used
in an elevated temperature application. VST was tested for
both binary and ternary blends with or without compatibilizer.
It can be seen in Fig. 5 that as PBAT content increased, the va-
lue of VST increases gradually. It is because PBAT has higher
VST than PLA. Comparing to the non-compatilized blends, the
VST of the compatilized blends were about 10 °C higher. This
is probably because the addition of the compatibilizer in-
creased the interfacial adhesion of the blends, thus caused a
higher value of VST.

3.5. Water absorption of blends

The hydroxyl groups in starch can form a hydrogen bond

with water, so it is important to study the water absorption
properties of blends contenting starch. The water absorption
characteristics of non-compatibilized and compatibilized blends
are shown in Fig. 6. For all the non-compatilized blends, the
time taken to reach the equilibrium water content is about
Fig. 4. DMA thermograms of TPS/polyester blends: (a) storage modulus, (b) loss
10 days, which did not change very much as PBAT content in-
modulus, (c) loss factor.
creased. The equilibrium water content increased from 16% to
20% as the PBAT content increased from 0% to 50%. This trend
is similar to that observed for starch/PBAT blends reported by
John and Bhattacharya (1999) before. PBAT has lower crystallin-
ity than PLA and this would account for the higher water
absorption of blends with higher PBAT content. For the compa-
tilized blends, there is a comparatively slow uptake of water
and the equilibrium absorption value is also lower than non-
compatilized blends.

4. Conclusion

Biodegradable binary and ternary blends of TPS, PLA and

PBAT give excellent properties when small amount of compati-
bilizer (an anhydride functionalized polyester) is added. For the
TPS/PLA and TPS/PBAT binary blends the tensile strength in-
creased about 30% and 100% each after compatibilized. The
elongation is drastically increased as the percentage of PBAT
is increased; this is particularly true of the compatibilized blend
where at 50% PBAT content the value of the elongation reached
22.04%. The anhydride functionalized polyester reduces the size
Fig. 5. VST of blends with various PBAT content. of the dispersed phase, thus enhancing the interaction between
582 J. Ren et al. / Carbohydrate Polymers 77 (2009) 576–582

the two phases between TPS and polyesters. Better properties Kim, S. H., Chin, I., Yoon, J., Kim, S. H., & Jung, J. (1998). Mechanical properties of
biodegradable blends of poly(L-lactic acid) and starch. Korea Polymer Journal,
could also be found for the compatibilized blends in the results
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uptake of the blends is lower and the time required to reach behaviour of amylose and amylopectin films. Carbohydrate Polymers, 50(4),
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