Journal of Polymers and the Environment

https://doi.org/10.1007/s10924-020-01874-w

ORIGINAL PAPER

Biodegradable Polymer Blends Based on Thermoplastic Starch

Vesna Ocelić Bulatović1   · Vilko Mandić2 · Dajana Kučić Grgić2 · Antonio Ivančić1

© Springer Science+Business Media, LLC, part of Springer Nature 2020

Abstract
This work considered the utilisation of environmentally friendly biodegradable materials instead of conventional polymeric
materials, in order to prevent further environmental endangerment by accumulation of non-biodegradable materials. Ther-
moplastic starch (TPS) is an exemplary environmentally friendly biodegradable material. Blending TPS with other biode-
gradable polymers such as biodegradable polyesters; polylactic acid (PLA) and polycaprolactone (PCL), was recognised as
a successful strategy to provide a renewable, fully biodegradable and cost-effective materials. Namely, PLA, PCL and TPS
polymeric materials individually show some shortcomings, which can be surpassed by blending. Using economically viable
procedure, one can produce multicomponent polymeric materials complying with functional performance requirements
while achieving complete biodegradation. Accordingly, PLA/PCL/TPS ternary blends with compositional variations were
prepared and investigated in terms of structural, morphologic, mechanical, thermal, physicochemical (water absorption,
contact angle) and processing properties in order to discuss and elucidate optimal performance of the overall material. In
summary, this study could lead to a better understanding of performance behind different blends and ensure producing and
using a new generation of biodegradable plastics that will not burden our environment.

Keywords  Biodegradable materials · Thermoplastic starch · Polylactic acid · Polycaprolactone

Introduction reducing carbon dioxide emissions [1, 2]. Biopolymers are

Nowadays, an increasing environmental awareness of the
public and stakeholders finally allowed a shift of the focus
of the scientific community towards the development of bio-
degradable materials from renewable sources with the aim
of completely replacing conventional non-biodegradable
materials in many applications. Namely, the predominate
approach to use petroleum-based plastic packaging that end-
up in landfills where recycling is difficult or restricted needs
to be reduced. Recently, the plastics industry displayed an
interest in finding alternative sources of raw materials. Many
natural materials were considered [1], however polymers
produced from natural renewable raw materials, i.e. biopol-
ymers, turned out to be particularly interesting. Namely,
biopolymers can successfully substitute for fossil sourced
polymers and therefore can contribute to the environment by
* Vesna Ocelić Bulatović
vocelicbu@simet.hr
1
University of Zagreb Faculty of Metallurgy, Sisak, Croatia
2
University of Zagreb Faculty of Chemical Engineering
and Technology, Zagreb, Croatia
abundant and economically favourable. Despite the increas-
ing use of biopolymers and increased production capacity,
the environmental impact on behalf of biopolymer advanta-
geous properties is still not fully utilised. Some drawbacks
of biopolymers still hinder them to meet the market expecta-
tions [3]. Biopolymers are still quite expensive compared to
conventional fossil fuel based polymers. Consequently, mod-
ifying the biopolymer materials to yield the desired perfor-
mance is currently the hot topic in the scientific community.
Unlike demanding development of new polymer materials
or polymerization pathways, blending is a relatively inex-
pensive and fast answer on how to adjust the plastic product
properties. Namely, modification by means of blending of
selected bio-based and/or biodegradable materials offers the
ability to adjust properties over a wide range while comply-
ing with low carbon footprint legislative constrains.
Poly (lactic acid) (PLA) is a thermoplastic material that
belongs to the group of biodegradable polyesters. PLA high-
lights repose on its extreme stiffness, tensile strength and
gas permeability as well as other outstanding mechanical
properties in line with the properties of synthetic polymers,
perfectly allowing packaging applications. On the other

13
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hand, the limitations of PLA are found in low degradation
rate, relatively high cost and high inherent brittleness [1,
4], which prevent broader applications. Addressing the brit-
tleness problem of PLA would broaden its applicability,
justifying the focus of recent investigations. Blending PLA
with flexible polymers such as poly-ε-caprolactone (PCL),
poly-buthylene succinate (PBS), and poly-butylene succi-
nate adipate (PBSA) was investigated to clarify the extent
of upgrades of flexibility and elongation strain at break [1,
5–8]. PCL was shown to be a good candidate to address the
shortcomings of PLA.
Poly-ε-caprolactone (PCL) is highly flexible biopolymer
with extremely high elongation at breakage and low ten-
sile strength [9]. PCL structure resembles combination of
ordered crystalline domains and non-ordered domains con-
sequently allowing rigid-rubbery properties; such configura-
tion has been widely acknowledged for improving elasticity.
PCL is a hydrophobic semi-crystalline polymer with broad
applicability with good solubility in organic solvents, low
melting point and exceptional blending compatibility [9,
10]. Binary PLA/PCL blends offer advancements in terms
of physical properties and biodegradability. Amorphous
PLA, having high degradation rate, allows tensile strength
improvement, whereas crystalline-rubbery PCL allows
toughness improvement but has much lower degradation
rate [11–13]. Broader packaging applicability is hindered
by their inherently high price, where starch was introduced
as low-cost natural biopolymer.
Native starch, one of the most abundant and widespread
natural food sources, is a main component of many plants
such as corn, potato, rice, cassava, etc. Starch shows bio-
degradability, low density, nonabrasive nature, but cost-
efficiency is the main reason promoting starch as one of
the most attractive environmentally friendly biopolymer
[14–16]. Hence, it is often used to produce blends with
non-biodegradable polymers and, more recently, with bio-
degradable materials. Starch is not thermoplastic material.
Native starch generally exists in a granular state due to the
inherent hydrogen bond between adjacent molecules. The
transformation of starch into bioplastics for all applications
requires starch gelatinization i.e. the disruption of granules
by applying mechanical shear stresses and heat in the pres-
ence of suitable plasticizers, usually glycerol and water,
under specific conditions. Thereof, thermoplastic starch
(TPS) biopolymer is produced [17, 18]. TPS also shows
some disadvantages that restrict its wider applications, such
as dominant hydrophilic character, high degradation rate and
poor mechanical properties, particularly under wet condi-
tions [19]. The best way to overcome these drawbacks is
to blend TPS with other biodegradable polymers. As men-
tioned before, blending polymers is a simple, rapid and
cheap method suitable for achieving combinations of prop-
erties that are generally unattainable by a single polymeric
13
Journal of Polymers and the Environment
material. Thus, blending TPS with biodegradable polyesters
may be an excellent way to provide a renewable, fully bio-
degradable and cost-effective material.
Previous studies have shown that blending PCL and TPS
increases PCL biodegradation rate. Low degradation rate of
PLA may be increased by blending with other biodegradable
polymers that have higher degradation rates. Natural starch
can be a good blending candidate for enhancing the biodeg-
radability of PLA and PCL due to its low cost, abundance
and availability from various botanical resources [19, 20].
Although the success of binary blends has been docu-
mented, recently, industrial and academic research is con-
cerned with the study and development of multicomponent
polymer blends consisting of three or more components [21].
Namely, broader range of useful properties may be achieved
if a successful balance of the constituents is provided. By
combining different materials with complementary proper-
ties, multicomponent polymeric materials may allow novel
high-performance materials with synergistic performance
[22].
However, very little attention has been devoted to the
research of multicomponent polymer blends from biopoly-
mers. Compatible properties among PLA, PCL and TPS sug-
gest biodegradable blends with good performance can be
obtained, such as appropriate processing and melt strength,
strength and toughness balance and required thermal proper-
ties. PLA and PCL were used as a matrix and TPS was added
to accelerate biodegradation as well as to reduce the rela-
tive cost. Thereof, morphology, crystallinity, surface tension,
mechanical and thermal properties as well as water absorp-
tion tests of binary and ternary blends were investigated and
discussed. For that purpose, blends with different binary
(PLA/PCL) and ternary composition (PLA/PCL/TPS) were
prepared using Brabender kneader blending followed by a
hydraulic press process. The aim of this work is to show how
the development of multicomponent biodegradable polymer
blends (ternary PLA/PCL/TPS blends) prepared by simple
melt blending can support viable packaging materials.
Materials and Methods
Materials
The native wheat starch used was Srpanjka made up of 23%
amylose and 77% amylopectin obtained from Agricultural
Institute, Osijek, Croatia. Glycerol was supplied by Gram
Mol, Zagreb, Croatia. Polylactide (PLA) pellets were sup-
plied by Nature Works LLC, USA (Ingeo™ Biopolymer,
4043D). PLA melting point is in the 145–160 °C range
with a glass transition temperature (­ Tg) between 50–70 °C
with density of 1.24  g  cm −3 at 25  °C, and molecular
weight around 110.000 g mol−1. Polycaprolactone (PCL)
Journal of Polymers and the Environment
pellets were supplied by Sigma-Aldrich, Germany (Poly-
caprolactone 440,744-500G). It exhibits an average Mn of
70.000–90.000 g mol−1 by GPC, Mw/Mn < 2, and density
1.145 g cm−3 at 25 °C. According to our research the melting
point of PCL is located at 58.6 °C whereas the glass transi-
tion temperature of PCL is at − 62.8 °C [23].
Preparation of Binary and Ternary Blends
The TPS was prepared by a melt extrusion process with
glycerol as a plasticizer. The ratio of plasticizer to wheat
starch was 30:100 (w/w). The TPS were extruded in a
laboratory scale Brabender single-screw extruder (Model
19/20DN; Germany; screw ratio L/D = 1:1 and die 4 mm)
with a screw speed of 40 rpm and dosing speed of 15 rpm.
The temperature profile of the extruder barrel from the feed
zone to the die was 100, 100 and 130 °C. The extruded
samples were air-dried overnight and then conditioned in a
sealed polyethylene bags at room temperature to maintain
stable moisture content.
Briefly, the binary PCL/PLA and ternary PCL/PLA/TPS
blends were blended for 6 min using a Brabender kneading
chamber at 170 °C with a rotor speed of 50 rpm. Firstly, the
binary PCL/PLA blends were blended and then TPS was
blended with them in a constant weight composition of 30
wt. %. The mass ratios of PCL to PLA were s 100/0, 70/30,
50/50, 30/70 and 0/100. PCLx/PLAy was used as the symbol
for the PCL/PLA blend, where x and y indicated mass per-
centages of PCL and PLA, respectively. The preparation of
binary PCLx/PLAy blends was followed by the preparation
of ternary blends where binary blends were selected as the
polymeric matrix (PCLx/PLAy/TPS).
Subsequently, after homogenization, the blends were
compression moulded at 25 bar and 180 °C for 5 min using
a laboratory hydraulic press machine Fontune, Holland.
Also, the neat PLA and PCL were subjected to the mixing
treatment in order to have the same thermal regime as the
blends. Scheme 1 displays an illustration of the preparation
Scheme 1  Illustration of the preparation of biodegradable ternary PLA/PCL/TPS blends
of biodegradable PLA/PCL/TPS ternary blends with their
chemical structures.
Methods
The melt flow index, MFI, of the polymers, binary and
ternary blends was determined using an apparatus (Zwick
4100, Germany) with a capillary die of 8 mm length and
2 mm diameter. Seven grams of each sample was loaded into
the barrel of the apparatus and then heated to the specified
temperature of 190 °C. A driving weight of 2.16 kg for the
material was applied to the plunger and the molten sample
was forced through a die. The extrudates were collected and
weighed and MFI values were calculated in g (10 min)−1.
The morphology of the blends was observed from the
cross-sections of cryogenically fractured surfaces of the
moulded bars by Vega EasyProbe 3 scanning electron
microscope (Tescan, Brno, Czech Republic), SEM, with an
accelerating voltage of 15 kV. The samples were cooled in
liquid nitrogen then fractured into specimens which were
separately mounted on a stub using a conductive tape and
sputtered with gold prior to fractographic examination.
The contact angle measurements were performed on a
contact angle goniometer, DataPhysics OCA 20 Instrument
GmbH. The measurements were carried out at a tempera-
ture of 23 °C ± 0.2 °C and a relative humidity of 60% with
a volume drop of 2 μL with a stabilization period of 10 s,
using an injection system. The drop shapes were geometri-
cally determined from Laplace–Young fitting integrated
into the software (SCA20, version 2.01). The average val-
ues of at least five drops of the same samples at difference
places were taken and the standard deviation was less than
2% for all samples. The contact angle of each sample was
measured using three different liquids (water, formamide
and diiodomethane). Distilled water, ­H2O, (twice distilled
λ = 1.33 µL cm−1) and formamide, ­CH3NO, (p.a. 99.5%,
Fluka) were used as polar solvents, while diiodomethane,
­CH2I2, (p.a. 99%, Aldrich) was used as non-polar solvent,
respectively. The literature values of their surface energies
13

are [24]: ­H2O: γp = 51.0  mJ  m−2 and γd = 21.8  mJ  m−2;
­CH3NO: γp = 19.0 mJ m−2 and γd = 39.0 mJ m−2; ­CH2I2:
γp = 0.0 mJ m−2 and γd = 50.8 mJ m−2.
The X-ray diffraction, XRD, was conducted using Shi-
madzu diffractometer XRD 6000 with CuKα radiation at
acceleration voltage of 40 kV and current of 30 mA. Data
were collected between 2–70°2θ in a step scan mode with a
step 0.02°2θ and counting time of 0.6 s. The degree of crys-
tallinity ­(Xc %) was estimated on a behalf of integral areas
of crystalline and amorphous contribution (Pseudo-Voight
fit) upon baseline correction (polynomial fit).
Thermal gravimetric analysis, TGA, of the blends was
evaluated using thermogravimetric analyser TGA Q500
(TA Instruments, New Castle, USA). Samples of approxi-
mately 10 mg were heated from 25 to 600 °C at a constant
heating rate of 10 °C min–1 under a nitrogen atmosphere
(60 ml min–1). The initial degradation temperature ­(T5%) was
calculated at 5% mass loss, while temperatures at the maxi-
mum degradation rate (­ Tmax) for each stage were determined
from the first derivatives of the TGA curves (DTG).
Water absorption, WA, of samples was determined
by preparing 2 × 2 square inch thin film specimens using
hydraulic press, Fontune, Holland, followed by hot press
process for 4 min at 160 °C and 500 kPa and finally dried
overnight in a desiccator. The specimens were weighed every
24 h for the next 8 days (192 h). Firstly, the specimens were
removed from water then blotted dry with paper, weighted
and returned to the distilled water again (23 °C, 100% RH).
WA of each specimen was calculated as follows (1):
m1 − m0
WA = (1)
m0
where m1 is the weight of the specimen at the specific time
interval and m0 is the initial dry weight of the specimen.
Tensile test of the blends was performed using a univer-
sal testing machine, Zwick 147670Z100/SN5A according
to standard ISO 527. Tests were performed at ambient tem-
perature (23 °C) and a cross-head speed of 50 mm min−1
to determine the tensile strength, elongation at break and
elastic modulus. In all mechanical tests, the reported data
are the mean and standard deviation from at least 5 measure-
ments. All samples were conditioned for 72 h at 23 °C with
a relative humidity of 50%.
Results and Discussion
Melt Flow Index
The melt flow index (MFI) is widely accepted parameter
that reposes on molecular weight and viscosity values of
the tested materials to describe the uniformity of the flow
13
Journal of Polymers and the Environment
rate of thermoplastic materials. Interfacial characteristics as
a consequence of developed microstructural and structural
parameters consequently influence the flow ability of poly-
mer blends, so knowing MFI of a blend indirectly points out
to dispersion and interaction between the polymers. It should
be noted that MFI provides only a very crude approxima-
tion. Still, obtaining MFI is heavily utilised in industry for a
quality control purpose before subjecting polymers to further
machine processing [25]. Here, the MFI value of the ther-
moplastic starch could not be determined, pointing out to a
polymer that is not suitable for machine processing due to
blockage occurrence. Processing inability was stressed out
as one of the disadvantages of starches. MFI values were
obtained for PCL and PLA. From the Fig. 1 it is obvious that
the MFI values of PLA are much lower than those of PCL,
which may be due to higher molecular weight. MFI values
suggest that the incorporation of PCL in PLA significantly
simplifies the processing of PLA/PCL blend due to molten
PCL properties.
The MFI values of PLA/TPS and PCL/TPS binary blends
indicate a uniform distribution of starch in PCL and PLA
based matrices. The increase of MFI value indicates that
the viscosity of the blend is lower than thermoplastic starch
value. This is due to homogeneous blending of the wheat
starch that has irregularly shaped particles, which increases
the space between molecules and therefore diminishes the
strength of intermolecular forces between polymer coils.
Possibility the blending process enhanced the formation
of particle-matric interaction, causing the blend to become
smoother and hence increase the mobility. It is evident that
MFI decreases with the content of thermoplastic starch in
binary and ternary blends, which is explained with increas-
ing viscosity of the blends, higher molecular weight and
higher elasticity, all consequently diminishing the polymer
Fig. 1  Melt flow index for investigated samples
Journal of Polymers and the Environment

flow ability [25, 26]. On the other hand, the addition of PCL Table 2  Interfacial tension of Polymer pairs Interfacial
and PLA to thermoplastic starch increases the thermoplastic the polymer pairs tension
starch MFI value. Such behaviour is particularly interesting, (m N m−1)
as thermal processing of starch-based polymers is known to PLA/PCL 8.7
be demanding. However, with the decrease of PCL viscos- PLA/TPS 1.5
ity, PCL/TPS blend turns out to have higher MFI value than PCL/TPS 15.5
PLA/TPS blend.

Interfacial Properties
The properties of polymer blend depend on composition and
structure of individual components and also on interfacial
interactions between polymers [1, 7, 17]. Measurements of
contact angle are widely used for the evaluation of material
surface characteristics, such as wettability, hydrophilicity
and surface energy. Thus, interfacial tension plays an impor-
tant role in the control of the hierarchal morphology of ter-
nary blends. The miscibility of components into blends can
be predicted by surface free energy calculations using vari-
ous models and theories. Surface free energy characteristics
of examined materials were investigated via contact angle
measurements with different test liquids having specified
values of surface free energy. The contact angles of indi-
vidual biodegradable materials (PLA, PCL, TPS) with water,
formamide and diiodomethane are listed in Table 2. Surface
tensions of the samples were calculated using a model of
harmonic average from the measured contact angles (θ) and
the values of the interfacial tension were calculated by the
equation of Wu (Eq. (2)) [27]:
( d d p p
) requires knowing of the interfacial tensions for all binary
𝛾1 𝛾2 𝛾1 𝛾 2
𝛾12 = 𝛾1 + 𝛾2 − 4 d + p (2)
𝛾1 + 𝛾2d 𝛾1 + 𝛾2
p
where θ is the contact angle, γ is the surface tension, γd is the
dispersion component and γp is the polar component. γ12 is
the interfacial tension between materials 1 and 2, γ1 and γ2
are the surface tensions of the two contacting components
in the blends. The values of calculated parameters are given
in Table 1.
It is known that lower contact angle with water is char-
acteristic for materials with higher surface wettability and
hydrophilicity. Respectively, PCL surface shows good wetta-
bility and hydrophilicity. The comparison of average contact
angle values with water (PLA = 68.0°, PCL = 99.7° and
TPS = 55.6°) confirms that the PCL surface was the most
hydrophobic with the highest contact angle value with water.
PLA shows a slightly lower contact angle value than PCL,
indicating a slightly less pronounced hydrophobic character
of PLA. On the contrary, low value of contact angle between
water and TPS surface is a consequence of polarity, i.e. pro-
nounced hydrophilic nature of TPS. The highest value of
polar component is observed for TPS; the lowest for PCL,
whereas dispersive component is in very narrow interval
from 22.8 to 24.7 m N m−1 for these polymers. The low
value of polar component as of PCL indicates nonpolar PCL
surface, i.e. possibility of establishing interaction at inter-
phase mainly by dispersive forces.
Therefore, it is expected that the presence of TPS in
binary blends will change the surface wettability and
hydrophilicity due to the strong intermolecular hydrogen
bonding at the film surface which causes surface polarity
of biopolymer films. Monitoring the development of mor-
phology with respect to theoretical spreading coefficients
blends; PLA/PCL, PLA/TPS and PCL/TPS (Table 2).
Understanding the mechanisms behind strong surface
adhesion development in binary blends can indicate which
interface could exhibit stronger adhesion in ternary sys-
tems. The highest value of interfacial tension is obtained
for PCL/TPS blends (γ PCL/TPS  = 15.5  mN  m −1 ) and it
indicates the lowest interaction extent between these two
polymers, i.e. poor miscibility of PCL and TPS polymers.
On the contrary, the lowest value of interfacial tension is
for PLA/TPS polymers, which indicates good adhesion
between PLA and TPS polymers (γPCL/TPS = 1.5 mN m−1)
and confirms better interactions are established between

Table 1  Contact angle and Sample Contact angle (°) Surface tension (m N m−1)
surface tension of the polymers
Water Formamide Diiodomethane Total (γ) Dispersion com- Polar
ponent (γd) compo-
nent (γp)

PLA 68.0 72.5 65.2 38.1 22.8 15.4

PCL 99.7 83.1 70.8 27.0 24.2 2.8
TPS 55.6 55.4 63.8 47.4 24.7 22.7

13

those phases. The value of interfacial tension for PCL/PLA
pairs is between afore mentioned values (8.7 m N m−1).
Other approach to theoretical prediction of morphology
development in ternary blends reposes on Harkin’s spread-
ing coefficients [28]. The advantage of this approach is that
the knowledge of the interfacial properties is sufficient for
prediction of the morphology development. Based on the
calculated interfacial tension data, it is possible to predict
the morphology of multiphase polymers [28, 29]. Using
the values of the interfacial tensions given in Table 2, it is
possible to calculate the set of three spreading coefficient
for a PLA/PCL/TPS blends as follows:
( )
λPLA/PCL/TPS = γPLA/TPS − γPLA/PCL + γPLA/TPS = −26.8
(3)
λPCL/PLA/TPS = γPCL/TPS − γPLA/PCL + γPLA/TPS = 5.5 (4)
( )
( )
λPLA/TPS/PCL = γPLA/PCL − γPLA/TPS + γPLA/TPS = −9.2
(5)
where λPLA/PCL/TPS are the interface tensions between poly-
mers. γPLA/TPS is the interfacial tension between PLA and
TPS phases, γPCL/TPS is the interfacial tension between
PCL and TPS phases and γPLA/PCL is the interfacial ten-
sion between PLA and PCL phases. A positive λPLA/PCL/TPS
indicates the tendency of component PCL to spontaneously
spread at the interface of components PLA and TPS, which
is considered as the complete wetting regime. However,
when all the three coefficients are negative, partial wetting
is predicted at triple-phase contact where all phases meet,
since the spreading does not occur. A negative but close to
zero spreading coefficient suggests a weak partial wetting
driving force, whereas the negative spreading coefficient
implies a strong driving force towards partial wetting. Two
wetting regimes are defined based on the spreading coef-
ficient; complete wetting and partial wetting. For positive
spreading coefficients, the liquid drop completely spreads
and forms a thin-film on the substrate to minimize the sur-
face energy. However, the liquid drop does not spread, rather
forms a spherical cap with an equilibrium contact angle on
the substrate when the spreading coefficient is negative [29].
In our case, the results of interfacial tension indicate
that in PLA/PCL/TPS ternary blends, the interfacial ten-
sion of PCL/TPS is much greater than that of PLA/PCL,
whereas the interfacial tension of PLA/TPS is lower than
tension of PLA/PCL. A multicomponent polymer system
will usually develop a morphology having lowest free
energy; therefore in this system TPS phase is most likely
encapsulated by PLA phase in PCL matrix. Figure 2 illus-
trates possible phase morphologies for PLA/PCL/TPS
polymer blends and their relations of the spreading coef-
ficients according Fu et al. [30].
13
Journal of Polymers and the Environment
Fig. 2  Possible phase morphologies for a PLA/PCL/TPS polymer
blend, and their relations of the spreading coefficients [28, 30]
Structural Characterization of the Blends, XRD
Analysis
All blends were analysed by means of X-ray diffraction,
where the constituent phases and blends were shown sepa-
rately (Figs. 3 and 4). The constituents were identified;
yet the ICDD diffraction assignation is not meaningful for
compounds having low structural order. For PCL, several
characteristic peaks could be easily observed, as this com-
pound displays semi-crystalline behaviour. Afterwards,
this will be used to discuss the degree of crystallinity.
The crystallite sizes of PCL remain similar for all blending
conditions. On the contrary, PLA is predominately amor-
phous, whereas only single characteristic low intensity
broad peak may be identified. For native wheat starch,
semi-crystalline behaviour is visible as several characteris-
tic peaks arise. Starch thermoplastic derivative, biodegrad-
able polymeric TPS material resembles semi-crystalline
to almost amorphous behaviour, with possible occurrence
of one or more characteristic peaks. PCL shows the char-
acteristic crystalline pattern (Fig. 3) with peaks at about
21.5, 21.8, 23.7 and 36.1°2θ attributed to the (110), (111),
(200) and (213) reflections, respectively [31–33]. PLA is
characterized by one weak peak centred at about 17°2θ
within broad amorphous hump centred at about 20°2θ,
which consequently does not allow monitoring of possible
structural transitions [34, 35]. TPS shows characteristic
peak at about 20°2θ (Fig. 3), attributed to the processing-
induced crystallinity of polyols molecule. Polyols, i.e.
glycerol also shows considerable influence at the TPS
structural parameters. Commonly, starch is plasticized by
adding an appropriate amount of plasticizer, where a mate-
rial flexibility is increased by reduction of intramolecu-
lar hydrogen bonding, and thereof allows intermolecular
spacing along polymer chains. Thereby we can expect an
increase of molecular mobility and a decrease of crystal-
linity [12, 36, 37]. These single-phase characteristics were
used to identify and discuss the behaviour of the blends.
The behaviour of PCL in blends with PLA is consistent
with the content of the sole constituents (Fig. 3a). Blending
Journal of Polymers and the Environment

Fig. 3  a XRD diffractograms

of the binary PCL/PLA and
b XRD diffractograms of the
ternary PCL/PLA/TPS blends

Fig. 4  a Overlap of the XRD

diffraction patterns of the PCL/
PLA binary blends, where com-
positional changes reflecting
in quantitative changes may be
observed and b overlap of the
XRD diffraction patterns of the
PCL/PLA/TPS ternary blends

biodegradable and ductile PCL with PLA should allow novel
materials showing upgrades in already good mechanical
properties of PLA yet with retained biodegradability on
behalf of PCL [38, 39]. The blending may be hindered by
thermodynamic immiscibility of PLA and PCL. To enhance
the miscibility, among other techniques, the addition/incor-
poration of a third component such as small molecule should
reduce the size of the dispersed phase and thereby improve
toughness and elongation at break of the overall blend. From
the available literature, the mechanisms of the ternary blends

13

formation are not completely clear, especially in the case
of TPS addition. The PCL/PLA/TPS blend is prepared to
allow better mechanical properties, especially rubbery elas-
tic properties [40]. The addition of TPS should not decrease
the abovementioned performance. Given their compatible
properties, we believe that the polymers could be blended
more successfully. Here we address these aspects only to
observe minimal, but unneglectable changes on behalf of
diffraction data. Basically, the increase in the content of the
predominately amorphous PLA within the semi-crystalline
PCL decreases overall peak, i.e. signal intensity proportion-
ally to the ratio of the constituents. The distribution of the
polymeric domains, i.e. the level of the structural organiza-
tion of the semi-crystalline PCL blends is barely affected.
The PCL/PLA in blends with TPS follows the behaviour of
the PCL/PLA blends (Fig. 3b). Namely, from the structural
point of view, the addition of TPS only slightly interferes
with the mechanisms of the ternary blend formation as well
as with the structural level of ordering. First, the change in
overall XRD signal is a proportional function of the relative
constituents’ contribution. Overlap of the XRD diffracto-
grams of PCL/PLA binary blends and PCL/PLA/TPS ter-
nary blends allowed observation of critical differences in
the blend formation between the two blends (Fig. 4a). While
the correct calculation of the crystallite size from diffraction
signal is not possible for polymeric materials, the correlation
of the PCL diffraction peaks at least reveals the size of the
PCL crystallites remains barely unchanged for samples with
and without TPS.
Diffraction peaks observed for PCL at 21.3 and 23.6°2θ,
attributed to the (111) and (211) crystal planes indices [33],
remain in the blended specimens. Regarding peak shifting,
in the PCL/PLA/TPS blends, all major PCL peaks; (110),
(111) and (200) plane reflections, remain constant 2θ posi-
tions, suggesting stable lattice of PCL. Some authors sug-
gest PCL crystal lattice extension or contraction may indi-
cate good PCL-TPS interaction, which is not the case here
[31]. Another way of structural changes, such as hindered
crystallization on behalf phase separation, points out to lim-
ited homogeneity between TPS and PCL and insignificant
improvement of PCL-TPS interaction. Also, the differences
on behalf of TPS addition are limited only to minor peaks
that may occur also due to starch derivatives (TPS) degra-
dation. Namely, TPS is prone to water adsorption. Obvi-
ously, PCL/PLA will reduce the overall blend susceptibility
to water adsorption, as the constituents are known for good
permeability with slow hydrolysis [41, 42]. The addition
of TPS will show only trace changes of water based deg-
radation. Finally, in Fig. 4b the XRD diffractograms of the
PCL/PLA binary blends and PCL/PLA/TPS ternary blends
are shown where compositional changes reflecting in quan-
titative changes may be better observed. The quantitative
13
Journal of Polymers and the Environment
features in general follow the relative compositional ratios
of the constituents.
Again, critical information obtained from the XRD data
is the observation of influence on the structure through
the degree of crystallinity. The addition of TPS into PLA/
PCL blends suggests miscibility improvement was limited.
Namely, the decrease of PCL relative crystallinity values
(hindered crystallization) in the PCL-based blends points
out to phase separation process in ternary blends (Table 3).
Blend Morphology
The fracture surfaces of pure thermoplastic starch, polycap-
rolactone and polylactide, as well as prepared binary and
ternary polymer blends, examined by a scanning electron
microscopy (SEM) are shown in Figs. 5–7. Before SEM
analysis, surfaces were sputtered with gold to ensure the
conductivity of the samples. Figure 5a shows a SEM micro-
graphs of native wheat starch before plasticization where
granular microstructure is visible. Granules are more or
less isotropic with broad size distribution and significant
agglomeration. The texture of the granules is pore and crack
free, surface roughness is low, edges are smooth and blunt.
During the plasticization process, granular morphology
went through a transformation yielding homogeneous poly-
meric film. The degradation of hydrogen bonding between
the starch molecules occurred synchronously with the for-
mation of the hydrogen bonds between the plasticizer and
starch molecules, whereas thermoplastic starch was obtained
(Fig. 5b). Therefore, SEM microphotograph of TPS (Fig. 5b)
shows uniform texture and morphology, with no unreacted
starch residuals. The absence of wheat starch granular resid-
uals suggests that the plasticization process was complete.
It can be concluded that the conditions for obtaining TPS
were well selected to transform granular wheat starch into
homogeneous TPS over plasticization process (Fig. 5b).
SEM micrograph of fracture surface of the pure PLA
(Fig. 6a) shows flat and smooth surface, corresponding to
low energy dissipation from crack initiation to propagation.
This corresponds to typical fracture surface of brittle mate-
rial with low roughness and absence of plastic deformation,
Table 3  Crystallinity of the PCL in the binary PCL/PLA and in the
ternary PCL/PLA/TPS blends
Composition Crystallinity Composition Crystallinity
PCL 33.7 PCL/TPS 22.7
PCL70/PLA30/ 22.2 PCL70/PLA30/ 17.1
TPS TPS
PCL50/PLA50 15.7 PCL50/PLA50/ 13.7
TPS
PCL30/PLA70 11.9 PCL30/PLA70/ 8.8
TPS
Journal of Polymers and the Environment

Fig. 5  SEM micrographs of: a

native wheat starch, b thermo-
plastic starch

Fig. 6  SEM micrographs of: a

PLA, b PCL, c PLA/TPS and d
PCL/TPS

which is correlated with the properties of PLA [5, 7, 11].
Meanwhile, SEM micrograph of the PCL (Fig. 6b), where
certain degree of structural order is observed, shows no
traces of no brittle fracture, indicating that a certain degree
of material elasticity is present. This is also obvious from
high elongation at breaking point. In addition, presence of
elongated fibril features, that can be observed from SEM
micrograph (Fig.  6b) points out to ductile deformation
behaviour of PCL.
The addition of thermoplastic starch to PLA and PCL
clearly shows the completely different morphology, as
shown in Fig. 6c, d. Comparing the SEM micrographs of

13

Fig. 7  SEM micrographs of binary a PCL70/PLA30, b PCL50/PLA50, c PCL30/PLA70, and ternary, d PCL70/PLA30/TPS, e PCL50/PLA50/
TPS, and f) PCL30/PLA70/TPS blends
binary PLA/TPS and PCL/TPS blends, a better miscibility
is observed in PLA/TPS blend (Fig. 6c). SEM micrograph of
the PCL/TPS (Fig. 6d) blend shows a higher accumulation of
TPS on the fracture surface, which is easier to squeeze out
when breaking, which indicates poor penetration of thermo-
plastic starch into the PCL matrix and the absence of interac-
tions that would contribute to better miscibility of PCL and
TPS. The formation of agglomeration-prone TPS flakes can
be clearly observed, which were mechanically induced to
form blocks and accumulate. Since PCL is a highly hydro-
phobic biopolymer and TPS is highly hydrophilic, the result
is a strong phase separation resembling to two-phase mor-
phology of the PCL/TPS blend.
Binary PCL/PLA blends (Fig. 7a, c, e) exhibit rough sur-
face and bimodal morphology, characterized by the exist-
ence of various voids and growth of fibril structures with
the increase of PCL content. This indicated poor adhesion
between PCL and PLA phases and high interfacial tension,
which can result in poor functional properties of such PCL/
PLA blends. There is also a clear, sharp interface between
PCL and PLA, which indicates poor penetration of either
PCL or PLA, which is a consequence of the poor adhesion
at the interface. This leads to limitations in stress trans-
fer through the system which could result in diminished
13
Journal of Polymers and the Environment
mechanical properties of such blends. Due to unsatisfying
transfer of stress from the matrix to the dispersed particles
and vice versa, cracks at the interface could occur. Further-
more, with the increase of PCL content in PCL/PLA blends,
the fibril microstructure of PCL is more pronounced, while
in contrast, with higher PLA content SEM micrographs
show isotropic morphology.
SEM micrographs of ternary PCL/PLA/TPS blends
(Fig. 7b, d, f) show that TPS addition results in poor adhe-
sion at the phase interface and the presence of micropores
and cracks in the polymer matrix. By adding TPS to the
PCL/PLA blends (PCL/PLA/TPS), miscibility or compat-
ibility of TPS was not improved. In contrast, the accumula-
tions of extruded starch and consequently residual cavities
are observed after extrusion of starch on the fracture surface.
The best morphology was achieved with a PLA content of
70 wt. %, or with purely PLA matrix (Fig. 7f). Majority of
starch granules are well covered by the PLA matrix, and
surface fracture probably occurred because of PLA matrix.
It is also possible to notice some degree of material elastic-
ity, on behalf of PCL presence in the PCL70/PLA30/TPS
blend (Fig. 7b).
Journal of Polymers and the Environment

Thermogravimetric Analysis
In order to evaluate thermal stability, thermogravimetric
(TG) analyses of constituents PCL, PLA, TPS, their binary
and ternary blends were performed in inert (nitrogen)
atmosphere. Initial decomposition temperature, T ­ 5%, final
decomposition temperature, ­Tf, maximum decomposition
temperature, ­Tmax, with associated mass loss ratio, Δm,
decomposition temperature interval, ΔT, and char residue
at 600 °C, R
­ 600 °C, were determined from TG and derivative
TG (DTG) curves (Table 4). Initial decomposition tempera-
ture depends on blend composition and indicates in thermal
stability of the blends. Figure 8 shows the TG and DTG
curves of constituent polymers as well as binary PCL/TPS
and PLA/TPS blends, respectively. Whereas thermal stabil-
ity of PCL is not high due to low melting and glass transition
temperatures, PCL shows highest thermal stability among
biodegradable polymers used in this study [8, 10, 23, 43].
Figure 8 shows that thermally induced changes for PCL
start at 364.3 °C, which is higher than 322.6 °C observed
for PLA. PCL is the most stable polymer with the onset of
thermal decomposition at a temperature of 364.3 °C with a
maximum degradation rate at 408.1 °C and completion of
degradation at 441.8 °C. Degradation of PCL occurs in a sin-
gle stage thermal interval about 22 °C wider in comparison
with PLA and TPS (Fig. 8b).
According to the Persenaire et al. the thermal degrada-
tion mechanisms of PCL is characterised by two stages that
occur simultaneously [44]. In the first stage of degradation,
cis-elimination occurs, i.e., the bursting of polyester chains
via the reaction of pyrolysis of esters, with the release of
­CO2, ­H2O and the formation of acidic carboxyl groups. In
the second stage of degradation, specific breakage of the
chain-end occurs, resulting in caprolactone (cyclic mono-
mer) due to the depolymerization process. However, the
initial blocking of the chain-end hydroxyl groups may not
completely prevent the occurrence of specific bursting of the
chain end. It is therefore suggested the two processes occur
simultaneously. On the other hand, from the obtained PLA
curves (Fig. 8b) it can be seen that the thermal degradation

Table 4  Results of thermal properties

Sample T5% (°C) T1max (°C) ∆m1 (%) T2max (°C) ∆m2 (%) T3max (°C) ∆m3 (%) Tf (°C) ∆T (°C) R600°C (%)

PCL 364.3 – – – – 408.1 99.0 441.8 77.5 0.00

PLA 322.6 – – 367.6 98.3 – – 377.6 55.0 0.87
TPS 279.3 318.4 65.9 – – – – 338.1 58.8 10.08
PCL/TPS 291.6 314.3 18.9 – – 406.1 70.9 429.8 138.2 2.41
PLA/TPS 221.2 243.4 17.0 327.4 70.0 – – 341.7 120.5 5.56
PCL30/PLA70 325.9 – – 365.2 75.4 398.2 23.2 418.3 92.4 0.19
PCL30/PLA70/TPS 296.5 318.6 27.5 329.7 34.1 372.1 24.9 402.4 105.9 4.37
PCL50/PLA50 318.8 – – 355.1 44.3 408.0 53.3 422.0 103.2 1.09
PCL50/PLA50/TPS 294.5 311.2 25.0 356.3 29.5 401.8 36.4 424.1 129.6 2.90
PCL70/PLA30 333.4 – – 360.5 15.1 455.7 82.7 477.1 143.7 2.30
PCL70/PLA30/TPS 291.2 310.9 18.3 354.2 20.4 401.8 50.7 420.7 129.5 3.05

Fig. 8  TGA (a) and DTG (b) curves of PCL, PLA, TPS and binary PCL/TPS and PLA/TPS blends

13

of PLA also occurs in a single stage, in a relatively narrow
temperature interval of about 55 °C. The onset of PLA deg-
radation is at 322.6 °C, with a maximum degradation rate
at 367.6 °C, with a mass loss of 93.3% attributable to the
cleavage of the PLA end macromolecules. Literature sug-
gests that thermal decomposition of PLA occurs via com-
plex mechanism which prevents simple obtaining of activa-
tion parameters [45, 46]. Namely, there are many factors
that affect the thermal stability of polylactide, among other
moisture, hydrolysed monomers and oligomers, molecular
weight and residual metals [47]. The thermal degradation of
PLA begins with the hydrolysis of water that has been left
behind during processing, followed by a depolymerization,
random degradation of the main chain, followed by intra-
molecular and intermolecular transesterification [48]. Then,
the starch chains begins to degrade at about 230 °C mainly
due to dehydration of hydroxyl groups and the subsequent
formation of unsaturated and aliphatic low molecular weight
carbon species [15].
Unlike single degradation stage of PCL and PLA, the
thermoplastic starch degradation occurs in two stages. The
TGA curve of TPS (Fig. 8a) shows mass loss up to 250 °C
associated with the evaporation of water, glycerol and other
volatile compounds which are present in TPS due to its
extreme hydrophilic character. Evaporation is followed by
thermal decomposition of the polysaccharide, i.e. starch
between 250 and 350 °C with a maximum decomposition
rate at temperature of 318.4 °C. The thermal decomposition
of starch is primarily related to the breakage of strong bonds,
such as glycosidic bonds. The process of thermal dehydra-
tion follows, with gaseous CO, ­CO2, ­H2O, aldehydes, alco-
hols, acids, aliphatic and furan fragments as decomposition
products [15]. The possible starch degradation mechanism
according to Worzakowska is shown in Fig. 9 [16]. TPS
shows the onset of degradation at lower temperature than
PCL and PLA polymers, indicating its low thermal stability.
From the TGA/DTG results it can be seen that the addi-
tion of TPS lowers the degradation onset temperature, reduc-
ing the thermal stability of each polymer. The addition of
TPS to PCL resulted in a decrease of ­T5% from 364.3 °C to
291.6 °C while the thermal stability of PLA is reduced by
100 °C (Table 4). Furthermore, the maximum degradation
Fig. 9  Thermal decomposition of TPS [16]
13
Journal of Polymers and the Environment
rate temperature of PCL ­(T1max) and TPS ­(T2max) remain
unchanged, indicating that PCL and TPS are immiscible
(Table 4). The addition of thermoplastic starch to polylac-
tide significantly decreases the temperatures of maximum
degradation rate, which indicates a certain degree of interac-
tions are present, i.e. a certain degree of miscibility, which
corroborates well with SEM microphotographs (Fig. 2b).
Accordingly, the thermal behaviour of the PLA/PCL blend
was found to be intermediate to those of constituent poly-
mers (Table 4). The thermal decomposition of the PLA/PCL
blends occurs in two stages. The first stage is between 300
and 370 °C, dominated by thermal decomposition of the
PLA since its degradation onset is found at a lower tem-
perature, while the second stage of decomposition in the
range of 370–440 °C relates to the thermal decomposition
of PCL as a more thermally stable component in the blend
(Fig. 10). The TGA and DTG curves clearly show all the
stages of thermal degradation for PLA and PCL are shifted
to higher temperatures, due to the increase of PCL content
in the blend. The exception is observed for a blend with 50
wt. % of polycaprolactone added, where the decomposition
onset temperature is slightly lower compared to the pure
PLA. For ternary blends, the addition of TPS to the PCL/
PLA blends decreases the onset temperature of degradation
up to about 30 °C (due to the lower thermal stability of the
TPS). The extent of mass loss in the temperature range from
30 to 300 °C relative to the composition of the blends was
also compared. A similar influence of TPS on the thermal
stability of blends has been obtained by other researchers [4,
17, 19, 49]. The initial mass loss up to 70 °C is attributed
to the evaporation of water, and other volatile compounds
present in TPS due to its pronounced hydrophilic character
is barely noticeable in PCL/PLA/TPS blends, indicating that
small amount of water is adsorbed within their structure.
The TGA and DTG thermal decomposition curves of PCL/
PLA/TPS blends show three stages of thermal decomposi-
tion (Fig. 10). The first stage is related to the degradation of
TPS as the least stable component in blends and the second
stage is related to thermal degradation of PLA. The last stage
of thermal degradation is attributed to the degradation of
PCL in PCL/PLA/TPS blends because of its highest thermal
stability. The results confirm the TPS phase addition reduces
Journal of Polymers and the Environment
Fig. 10  TGA (a) and DTG (b) curves of binary PCL/PLA and ternary PCL/PLA/TPS blends
the thermal stability of the blends. The weight percentage
of char residues for all samples is presented in Table 4. It
can be observed that TPS contributed to generating a higher
amount of residue due to the char residues of the neat TPS
(10.08%). It may be because the starch is a carbohydrate,
which yields high charred products. Whereas the neat PCL
presented completely degradation without char residues, the
neat PLA piece resulted in very low char content of approxi-
mately 0.87%. By adding the TPS, this value increased up to
2.41% and 5.56% in the binary PCL/TPS, PLA/TPS blends,
respectively. The binary PCL/PLA blends presented inter-
mediate char residue. This result can be related to additives
incorporated into the biopolymers by the manufacturer. As
expected, ash content increased in ternary blends due to the
TPS presence.
Fig. 11  Water absorption versus immersion time for a PCL, PLA, PLA/TPS, PCL/TPS and b binary PCL/PLA and ternary PCL/PLA/TPS
blends
Water Absorption
The water absorption (WA) behaviour of the constituent
polymers, their binary and ternary blends as a function of
water immersion time is presented in Fig. 11. As aforemen-
tioned, one of the major disadvantages of TPS is its ten-
dency for water absorption. The hydroxyl groups in starch
form a hydrogen bond with water, so any improvement in
water sensitivity is significant for many practical applica-
tions of starch-based materials [50]. On the other hand;
polycaprolactone and polylactide have a pronounced hydro-
phobic character and high resistance to water. Comparing
the results of water absorption behaviour for PCL and PLA
(at a plateau point 0.8%), more pronounced hydrophobic
character is shown by polycaprolactone (at a plateau point
0.2%) (Fig. 11a).
Therefore, water absorption was investigated on behalf
of a difference in water affinity of TPS (hydrophilic) to PCL
13

and PLA (hydrophobic). It is obvious that water absorption
of blends will increase if TPS is added. Namely, that water
absorption of the polymer blends depends on the weight
fraction of TPS, weight fraction of hydrophobic polymer,
the thermodynamic interaction energy between TPS and the
hydrophobic polymer, and their respective diffusion coeffi-
cients [51]. The measuring of the water absorption for con-
stituent TPS was not possible in eight days because during
the first day the TPS was saturated and broke down, which
confirmed its strong hydrophilic character. After 48 h, TPS
turned into a paste that could not be removed from water
in order to measure weight. Placing the TPS in a high rela-
tive humidity environment further reduced the strength of
the samples to the point where they were no longer able to
remain coherent. Therefore, the WA value for TPS was cal-
culated based on the results during the first day and equals to
104.9%. In addition, the plasticizer itself contributes to this
extremely high WA value of thermoplastic starch. A plasti-
cizer is necessary for processing starch into a thermoplas-
tic material. Adding plasticizer has an impact on essential
material properties such as water resistance, glass transition
temperature, and mechanical properties. Although glycerol
is proven as the most common plasticizer for plasticizing
starch, due to the high amount of end hydroxyl groups, it
pronounces the water sensitivity even more. We confirmed
the thermoplastic starch is highly hydrophilic.
As expected, the TPS sample shows the highest water
absorption due to its hygroscopic nature [8, 14, 17], whereas,
the hydrophobic PCL and PLA samples showed the low-
est water absorption (Fig. 11). The water absorption in the
binary TPS samples, increased linearly as a function of time
in the first 100 h (4 days). Finally, a plateau was observed,
indicating that water absorption had reached equilibrium
plateau. As reported previously for similar systems, the
absorption is fast for shorter periods (t < 100 h) and slows
down for extended reaction periods reaching an equilibrium
plateau. The equilibrium swelling, or maximum relative
water uptake, or water uptake at equilibrium, corresponds
to the plateau value observed at 100 h (4 days).
Furthermore, the incorporation of PCL and PLA can dra-
matically decrease the water absorption of TPS and reduce
the water sensitivity of the PCL/TPS (4.0%) and PLA/
TPS (2.5%) blends due to their hydrophobic characteristic
(Fig. 11). Figure 11 shows that water absorption of PLA/
TPS blends are slightly lower than those of the correspond-
ing PCL/TPS blend. This can be explained by a finer disper-
sion of TPS phase in the PLA matrix due to its lower melt
viscosity, which leaves less free hydroxyl groups for water
binding. Additionally, the dense and homogenous micro-
structure can hinder the diffusion of water molecules in the
PLA/TPS blends.
Ternary blends with thermoplastic starch show a sharp
increase of water absorption at the beginning and then
13
Journal of Polymers and the Environment
remain constant for about 4 days. Maximum water absorp-
tion was 6.3% for ternary blends with higher content of PCL
(PCL70/PLA30/TPS) (Fig. 11). Water absorption of this
blend is typical for Fickian type of diffusion behaviour. In
Fick’s law, the concentration gradient is the driving force for
diffusion and amount of the component diffused in a func-
tion of time. Generally, water absorption process follows
the prediction of Fick’s law as the mass of water absorbed
increases linearly with square root of time until equilibrium
plateau is reached.
The hydrophobic character of PCL and PLA causes
reduction of water adsorption for ternary blends and thereof
reduce their equilibrium water content. Likewise, when the
ratio of PCL or PLA in the blends increased, their water sol-
ubility decreased, as shown in Fig. 11. The results confirm
the expected changes in the water affinity of the blends when
the ratio of PCL or PLA increased, which is an advantage of
these ternary materials.
For water absorption, it can also be noticed that an
increase in PLA content reduces the plateau equilibrium
value; despite its slightly less hydrophobic character com-
pared to PCL. This behaviour can be explained by the better
miscibility of TPS and PLA and the absence of cavities as
potential water retention sites.
Observing the results of WA for binary PCL/PLA blends,
regardless of their mutual composition, changes in water
adsorption are not specific. This result is expected due to
both components having highly hydrophobic character.
The absorption of excessive water weakens the TPS
properties. Thereof it is critically important to diminish the
property of starch plastics to absorb water. The pronounced
absorption of starch reposes on ability of water molecule to
easily diffuse through the starch network which also strongly
interacts with water molecules. Adding hydrophobic materi-
als significantly reduces water absorption in concordance
with the theory for a polymer blend that predicts the dif-
fusion coefficient and water absorption of a hydrophilic
polymer will be reduced when blended with a hydrophobic
polymer.
Mechanical Properties
Maintaining the quality of mechanical properties is greatly
important because the material must be able to display stable
performance under various loads. From the law of blends
for miscible polymers, the expected properties of the blend
are near to the sum of properties of the constituents. For
immiscible polymers, mechanical properties are markedly
impaired. Results of mechanical properties: tensile strength,
elongation at break and elastic modulus of pure polymers,
binary and ternary PLA/PCL/TPS blends were evaluated
from stress–strain curves and the results are shown graphi-
cally in Fig. 12.
Journal of Polymers and the Environment
From the results of the mechanical properties shown in
Fig. 12, the PLA is highly fragile with a very low elonga-
tion at break values of 5.3%. Very low elongation at break,
medium-to-high tensile strength of 45.3 N mm−2 and the
elastic modulus of ~ 1020.0 N mm−2 are responsible for PLA
high brittleness. High strength, rigidity and low elongation
at break of polylactide, nominate PLA as biopolymer appro-
priate for loading applications, such as fixing orthopaedic
accessories [52, 53]. On the other hand, PCL exhibits very
ductile behaviour, extensive elongation at break, capable to
undergo large deformations. It shows relatively low elastic
modulus of 261.4 N mm−2, which limits its application for
materials with high rigidity requirements (Fig. 12). Ther-
moplastic starch exhibits extremely poor mechanical prop-
erties compared to PCL and PLA, very low tensile strength
of 4.1 N mm−2, low elastic modulus of 91.6 N mm−2, and
elongation at break 22.3%. TPS can be described as a highly
fragile polymeric material, i.e. material with strong hydro-
philic character and poor mechanical properties, which
hinders its widespread use. Still, the elongation at break of
Fig. 12  Mechanical properties of binary PCL/PLA and ternary PCL/PLA/TPS blends a tensile strength, b elongation at break and c elastic
modulus
thermoplastic starch is about 5 times higher compared to
pure PLA. The disadvantages of TPS can be mitigated by
various modifications and by blending with polymers that
have strong hydrophobic character. The blending produces
materials with low water sensitivity, high strength, and envi-
able thermal stability with pronounced biodegradable prop-
erties. Based on the obtained mechanical properties of each
polymer (Fig. 12), it is expected that blending TPS with
biodegradable polymer, either PCL and PLA will improve
the tensile strength and elongation at break of TPS, whereas
reduce the elastic modulus, which will result in an improve-
ment of the poor mechanical properties of thermoplastic
starch. The mechanical properties of the pure polymers
obtained in this study corroborate well with the literature
values [5, 11, 20, 46, 54]. Some observed deviations were
not pinpointed, namely mechanical properties depend on
morphology, molecular weight of the polymer, degree of
crystallinity, plasticizer content in thermoplastic starch, its
composition as well as the source of the starch.
13

The addition of TPS to pure PCL and PLA polymers
results in a decrease of the elongation at break of the
PCL while the elongation at break of the PLA increases
(Fig. 12b). Due to the extreme fragility of PLA, the addition
of thermoplastic starch, due to the high content of plasti-
cizer (glycerol), contributes to the increase in the elonga-
tion at break. The tensile strength is the highest for PLA
and the lowest for TPS, while the effect of blending TPS
in PLA is manifested by the decrease of tensile strength
(Fig. 12a). Also, the elastic modulus is the highest for PLA,
and the lowest for TPS, while the addition of TPS results
in a decrease of the elastic modulus value for PLA while
slight increase for PCL (Fig. 12c). Mechanical properties of
samples with TPS corroborate well with the SEM micropho-
tographs, indicating their immiscibility. Researchers have
also shown that low adhesion between TPS and PCL occurs
due to poor interfacial interactions, which lead to a decrease
in mechanical properties [49, 55, 56]. The addition of PCL
to PLA is manifested by a decrease of tensile strength and
elastic modulus, while the elongation at break is increased
compared to pure PLA, indicating a positive influence of
the addition of PCL on elongation at break of PLA/PCL
due to its prominent flexibility (Fig. 12) [57, 58]. On the
other hand, the addition of PLA to PCL contributes to almost
tripling of PCL/PLA stiffness. Figure 12 shows that the
higher the proportion of PCL in PCL/PLA blends increases
the elongation at break. Due to the extreme elasticity of the
PLA, even a small increase of PLA-based blend stretching
is extremely important for its application. It can be seen that
the elongation at break of the PCL/PLA blend increases to
392.6%, which is a remarkable contribution, compared to
pure PLA (5.3%). The elastic modulus of PCL/PLA blends
reduces gradually by the increase of PCL content (Fig. 12c).
PCL/PLA blends show reduced brittleness due to the high
elongation at break value (Fig. 12b) [59–61].
The addition of TPS in PCL/PLA blends reduces tensile
strength, elongation at break and elastic modulus, impairing
mechanical properties. This occurs as physical incorporation
of the TPS into the PCL/PLA matrix of the blend weakens
the London forces between the bland constituents. Another
reason for such behaviour is found in low molecular mass
of TPS molecules, which can consequently withstand less
elongation at break compared to PLA and PCL.
Conclusions
This investigation focused on preparing multiphase bio-
degradable polymer materials by blending three promis-
ing biopolymers: polycaprolactone (PCL), polylactide
(PLA) and thermoplastic starch (TPS). The homogeneous
morphology of TPS without the presence of accumulated
starch granules has been achieved indicating successful
13
Journal of Polymers and the Environment
plasticization. Addition of TPS to PCL and PLA heavily
affected their morphology, in favourable manner for binary
PLA/TPS blend. Addition of TPS to PCL/PLA blends (PCL/
PLA/TPS) resulted in poor adhesion at the phase boundary
and the presence of micropores and cracks in the polymer
matrix, where the immiscibility of the blends was clearly
observed by the presence of two separated phases. The best
morphology was achieved with a PLA content of 70 wt. %,
i.e. where the polylactide is a matrix (PCL30/PLA70/TPS).
Polymeric constituents and blends were successfully
monitored using X-ray diffraction. From the structural
point of view, the addition of TPS slightly interferes with
the mechanisms of the ternary blend formation as well as
with the structural level of ordering. XRD allowed obser-
vation of influence on the structure through the degree of
crystallinity. Namely, the decrease of PCL relative crystal-
linity values (hindered crystallization) in the PCL-based
blends points out to phase separation process in ternary
blends. Results of TGA analysis indicate that the addition
of TPS decreases thermal stability of PCL/TPS and PLA/
TPS blends. In binary PCL/PLA blends, PCL contributes to
the reduction of the elongation at break and elastic modulus,
while increasing the tensile strength of PLA, on the other
hand, the PLA contributes to tropeling of the stiffness of the
PCL. The addition of TPS into PLA/PCL blends impairs the
mechanical properties of the individual components in the
binary blends, suggesting miscibility was limited.
Finally, ternary biodegradable blends show great poten-
tial as environmentally friendly materials primarily due to
significant cost reduction. Resolving waste accumulation is
an issue that may be resolved by application of these ternary
biodegradable blends for disposable material. The topic may
need further research, focusing on eluting adequate com-
patibilizer in order to achieve better adhesion of the blend
constituents as well as improving miscibility and therefore
obtaining better material properties.
Acknowledgements  This work was supported by projects PZS-2019-
02-1555 in Research Cooperability Program of the Croatian Science
Foundation funded by the European Union from the European Social
Fund under the Operational Programme Efficient Human Resources
2014-2020.
Author contributions  Conceptualization: [Vesna Ocelić Bulatović
and Dajana Kučić Grgić]; Methodology: [Vesna Ocelić Bulatović];
Formal analysis and investigation: [Vesna Ocelić Bulatović and Vilko
Mandić]; Writing—original draft preparation: [Vesna Ocelić Bulatović,
Vilko Mandić and Antonio Ivančić]; Writing—review and editing:
[Vesna Ocelić Bulatović and Vilko Mandić]; Resources: [Vesna
Ocelić Bulatović and Dajana Kučić Grgić]; Supervision: [Vesna Ocelić
Bulatović and Vilko Mandić].
Compliance with Ethical Standards 
Conflicts of Interest  The authors declare that they have no conflict of
interest.
Journal of Polymers and the Environment

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