International Journal of Biological Macromolecules 109 (2018) 99–113

Contents lists available at ScienceDirect

International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac

Review

Fully biodegradable Poly(lactic acid)/Starch blends: A review of

toughening strategies
J. Justin Koh a,b , Xiwen Zhang b , Chaobin He a,c,∗
a
Department of Materials Science and Engineering, National University of Singapore, 9 Engineering Drive 1, 117576, Singapore
b
Singapore Institute of Manufacturing Technology, Agency for Science, Technology and Research (A*STAR), 73 Nanyang Drive, 637662, Singapore
c
Institute of Materials Research and Engineering, Agency for Science, Technology and Research (A*STAR), 2 Fusionopolis Way, Innovis #08-03, 138634,
Singapore

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

Article history: Polylactic acid (PLA) and Starch are both bio-based biodegradable polymers that have properties that
Received 1 November 2017 are complementary to each other. PLA/starch blend exploits the good mechanical property of PLA and
Received in revised form the low cost of Starch. However, PLA/Starch blend is intrinsically brittle. This paper reviews the current
27 November 2017
state of arts in toughening of PLA/Starch blend, which are categorized as: Additive Plasticization, Mixture
Accepted 7 December 2017
Softening, Elastomer Toughening and Interphase Compatibilization. These strategies are not mutually
Available online 14 December 2017
exclusive and can be applied jointly in a single blend, opening up a wide range of toughening tech-
niques that can be employed in PLA/Starch blend. Even though significant progress has been made in
Keywords:
Poly(lactic acid)
this area, there is still much room for research, in order to achieve easy to process, fully bio-based and
Starch completely biodegradable PLA/Starch blends that have mechanical properties suitable for a wide range
Sustainability of applications.
Biodegradable © 2017 Published by Elsevier B.V.
Bio-based
Toughening
Compatibilization

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
2. Toughening strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
2.1. Additive plasticization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
2.1.1. Plasticization of starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
2.1.2. Plasticization of PLA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
2.2. Mixture softening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
2.2.1. Ductile immiscible component . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
2.2.2. Ductile miscible component . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
2.3. Elastomer toughening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2.3.1. Elastomer compatible to PLA and starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2.3.2. Elastomer compatible to PLA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2.3.3. Elastomer compatible to starch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2.4. Interphase compatibilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2.4.1. Chemical crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
2.4.2. Amphiphilic bridging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
2.4.3. Componential modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
2.4.4. Interfacial transitioning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107

∗ Corresponding author.
E-mail address: [email protected] (C. He).

https://doi.org/10.1016/j.ijbiomac.2017.12.048
0141-8130/© 2017 Published by Elsevier B.V.
100 J.J. Koh et al. / International Journal of Biological Macromolecules 109 (2018) 99–113

3. Disscussion section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110

3.1. Combination of strategies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .110
3.2. Preserving the novelty . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111

1. Introduction lopectin in Starch varies from different Starch sources, which can
result in slightly different physical properties of the material.
The increasing global population and increasing consumption . Starch and PLA are also different in their interaction character-
has resulted in increasing environmental pollution and waste accu- istics, Starch is hydrophilic while PLA is hydrophobic. This means
mulation. Plastic waste now poses a major challenge not only to our that Starch-based materials are susceptible to water. However, the
environment, but also to the marine ecosystem. These problems Starch component can be shielded from contact with water if the
are predominantly contributed by plastics employed in short-term dispersed Starch phase is embedded within the hydrophobic PLA
applications such as packaging and disposable products. A large matrix in the PLA/Starch blend. Moreover, it would be sponta-
portion of these issues can be resolved by employing biodegrad- neous for the hydrophobic (less polar) polyester to form the outer
able materials, and hence they are receiving considerable attention layer in order to lower the surface tension of the material, hence,
in recent years. improving the water resistance aspect of the blend [5–7]. More
Among the biodegradable materials, polylactic acid (PLA), also importantly, the thermodynamically incompatible hydrophobic
known as polylactide, is one of the most promising polymers. PLA PLA and hydrophilic Starch components results in phase separa-
is an aliphatic polyester that is capable of breaking down into tion and poor interfacial adhesion between the phases. As such,
smaller molecular weight species and subsequently into carbon mechanical stress cannot be properly distributed from the PLA
dioxide, water and small organic molecules through hydrolysis matrix to the dispersed Starch phase, creating defects in the system
in the presence of certain microorganisms distributed in the soil that results in decreased strength, ductility, and ultimately tough-
environment [1]. Besides being biodegradable, PLA is also bio- ness of the binary blend. In fact, PLA/Starch blend results in weaker
based (bio-derived), hence renewable. Its monomers, lactic acids, and even more brittle material than that of the pure PLA.
are obtained from the fermentation of carbohydrates by bacteria Unfortunately, many of the short-term applications such as
of the genus Lactobacillus [2]. This further supports the environ- packaging and disposable tableware, are primarily structural
mental aspect of PLA as a sustainable alternative. The conventional applications that require the material to possess some form of
method of synthesizing high molecular weight PLA starts from mechanical robustness. For example, for the case of most packaging
lactic acids, to intermediate oligomeric lactic acid and lactides, applications, such as food packaging, certain amount of ductil-
and eventually high molecular weight PLA [3]. Firstly, lactic acids ity is required so that the material can withstand the storage
undergo condensation polymerization into low molecular weight and distribution process without failing catastrophically. Therefore,
oligomeric lactic acids. Subsequently, depolymerisation of the low toughening of PLA/Starch blends by increasing its ductility without
molecular weight PLA into lactides and eventually the ring-opening sacrificing too much of its strength is crucial for PLA/Starch blend
polymerization of lactides into high molecular weight PLA. Due to be employed in a wide range of short-term applications.
to a chiral centre, lactic acids exists in two enantiomeric forms, In the recent decades, many researchers have come up with
L-(+)-lactic acid and D-(−)-lactic acid, allowing the formation of different methods to toughen the PLA/Starch polymer blend
L-lactide, D-lactide and DL-lactide (meso-lactide). This in turn pro- to achieve balanced mechanical properties suitable for a wide
vides the freedom to adjust the tacticity of PLA from isotactic PLLA range of short-term applications. In this paper, key strategies
and PDLA, to syndiotactic and atactic PDLLA. Chart 1 illustrates employed in the toughening of the polymer blend will be reviewed,
the various chemical structures of the stereoisomers of lactic acid, organised and discussed. These strategies can be categorised
lactide and PLA. Another interesting feature of the PLA’s struc- into 4 main categories: Additive Plasticization, Mixture Soft-
ture is the ability to form PLLA and PDLA stereocomplex [4]. This ening, Elastomer Toughening and Interphase Compatibilization;
stereocomplex has higher inter-chain interactions due to uncon- and 11 sub-categories: Plasticization of Starch, Plasticization of
ventional hydrogen bonding resulting in better thermal stability PLA, Ductile Immiscible Component, Ductile Miscible Component,
and mechanical properties. These tacticity variations allow the tun- Elastomer Compatible to PLA and Starch, Elastomer Compatible
ing of PLA’s microstructure and hence its physical properties. In to PLA, Elastomer Compatible to Starch, Chemical Crosslinking,
general, PLA possess outstanding mechanical properties. Its stiff- Amphiphilic Bridging, Componential Modification and Interfacial
ness and strength are comparable to conventional petroleum-based Transitioning. Lastly, the complication of the combinations of
synthetic polymers such as polyethylene terephthalate (PET) and these strategies will also be examined. This paper focuses on the
polystyrene (PS), making PLA a promising PLA/Starch binary blend where PLA is the matrix and Starch as the
However, PLA has its shortcomings. Firstly, it has a higher dispersed phase.
cost of production as compared to those petroleum-derived, non-
biodegradable counterparts. Secondly, PLA is inherently brittle 2. Toughening strategies
despite its tuneable tacticity, microstructure and mechanical prop-
erties. These drawbacks have impeded PLA’s path to be employed 2.1. Additive plasticization
in a wide range of short-term applications
In order for PLA to be a more attractive replacement to conven- Plasticization is a common technique to increase the flexibil-
tional petroleum-based polymers, it can be blended with another ity of the polymers as well as to improve their processability.
component that is much more economical. Starch appears to be to As a result of increased flexibility, the toughness of the mate-
an appealing choice because of its low cost. Furthermore, Starch is rial can be increased. However, the increase in flexibility through
completely biodegradable [2] and renewable from annual harvest. plasticization strategy usually come with the price of decrease
The composition of Starch comprises of amylose and amylopectin in strength due to the reduction in polymer inter-chain interac-
which are made up of glucose units. The ratio of amylose and amy- tion. Nevertheless, this allow mechanical properties to be tunable
 J.J. Koh et al. / International Journal of Biological Macromolecules 109 (2018) 99–113 101

Chart 1. Conventional synthesis of high molecular weight PLA (top). Stereoisomers of lactic acid, lactide and PLA (bottom).

by manipulating the polymer/plasticizer ratio. The additive plas- urea [22–24], ethanolamine [22] formamide [23,24] and acetamide
ticization strategy for the PLA/Starch blend can be targeted at the [24] can form stronger hydrogen bond with Starch as compared to
dispersed starch phase, PLA continuous phase or both. those hydroxyl-groups-containing molecules. The stronger hydro-
gen bond between the plasticizer and Starch serves to supress the
2.1.1. Plasticization of starch retrogradation process, and hence improving material stability.
The primary purpose of plasticizing Starch is to improve the However, as mentioned previously, the poor interfacial adhe-
processability of Starch for the blend. For pure dry Starch, which sion between Starch and PLA hinders the stress transfer between
are semi-crystalline, thermal degradation occurs before the melting the matrix and the dispersed phase. Therefore, the effect of plasti-
[8]. This is largely due to the strong intra- and inter-chain hydro- cizing Starch on the toughness of the PLA/Starch is limited without
gen bonds by the hydroxyl groups of the glucose units [9]. With proper compatibilization between the two phases [25,26]. How-
the presence of plasticizer, heat and mechanical shear, intermolec- ever, if Starch has been sufficiently plasticized, it can induce
ular hydrogen bonds between Starch molecules can be weakened, elastomer toughening effect (see 2.3.3. Elastomer Compatible to
while hydrogen bonds can be formed between the plasticizer and Starch) or even improve interphase compatibility through interfa-
the Starch molecules. This process is known as gelatinisation, which cial transitioning (see 2.4.4. Interfacial Transitioning). Indeed, with
transforms Starch into a more amorphous material, resulting in suitable interphase compatibilization, a brittle-to-ductile transi-
the depression of melting temperature (Tm ) and glass transition tion can be observed from the PLA/Starch blend if the Starch is
temperature (Tg ) such that Starch can be process by conventional sufficiently plasticized, in other words, when plasticizer content
methods such as moulding and extrusion. This depression of Tm exceeds a critical threshold [25,26].
and Tg by plasticizer can be attributed to the translational entropic
effect. The level of gelatinisation and hence the Tm and Tg of the 2.1.2. Plasticization of PLA
Thermoplastic Starch (TPS) is dependent on the amount and type The plasticization strategy can be employed on the PLA matrix.
of plasticizer used. Chart 3 illustrates the chemical structures of molecules that has
Chart 2 shows the chemical structure of various small molecules plasticizing effect on PLA. Many small molecule esters such as
that have been successfully used to plasticize Starch. Water can triethyl citrate [25,27,28], tributyl citrate [27,29–31], acetyl tri-
act as a plasticizer for starch but is not preferred due to its ethyl citrate [27,31], acetyl tributyl citrate (Tributyl O-acetylcitrate)
volatility [8,10–14]. Various less volatile polyols such as glycerol [27,31,32], Diethyl adipate [31], dioctyl adipate (Bis(2-ethylhexyl)
[8,11,13–18], xylitol [11], sorbitol [13,15,19,20], ethylene glycol adipate (DEHA))[32,33], diisodecyl adipate [31], glycerin triacetate
[19], propylene glycol [19], diethylene glycol [19] has successfully (triacetin) [30,32,34], cardanol acetate [35], diethyl bishydrox-
been used to plasticize Starch. Many other bio-derived plasticizers ymethyl malonate [29], glyceryl tribenzoate [34], dipropylene
such as glucose [9,11], fructose [14], sucrose [14] and citric acid [18] glycol dibenzoate [34] has successfully been used to plasticized
has been reported to be able to plasticize Starch as well. Amongst PLA and consequently increase its ductility and toughness. Small
these hydroxyl groups-containing molecules, glycerol remains as building blocks of PLA, such as lactides [36] and oligomeric lactic
the most conventional small molecule plasticizer for Starch. How- acid [25], are also known to be effective plasticizers of PLA. Glucose
ever, these small molecules plasticizer tends to migrate during monoester and partial fatty acid ester had been explored but their
aging, leading to recrystallization (retrogradation) of Starch, caus- effect on PLA’s toughness is limited [36].
ing the embrittlement of TPS [5,18]. To tackle this issue, Ma and Similarly, PLA plasticized by small molecules also face aging
co-workers discovered that a series of amides and amines, such as issues. The low molecular mass of these plasticizers facilitated their
102 J.J. Koh et al. / International Journal of Biological Macromolecules 109 (2018) 99–113

Chart 2. Chemical structures of plasticizers for Starch.

Chart 3. Chemical structures of plasticizers for PLA.

 J.J. Koh et al. / International Journal of Biological Macromolecules 109 (2018) 99–113 103

migration ability from their original position after processing [30], a co-continuous phase with PLA. This is because at the processing
which will hasten the cold crystallization process of PLA leading to temperature, the viscosity of PBS is significantly lower than that of
the embrittlement of the PLA, which facilitates the dispersed PBS to deform and coalesce into
material [29]. One possible solution to impede migration of plas- continuous fibres [46,47]. This phenomenon has been reported in
ticizers is to increase their molecular weight hence reduce their other polymer blends with huge disparity in viscosity as well [48].
mobility. Some large molecules such as polyethylene glycol (PEG) Beyond 42 wt%, phase inversion takes place and PLA becomes the
[25,36–40], polypropylene glycol (PPG) [25,41], block copolymer of dispersed phase in PBS matrix.
PEG and PPG (Pluronic) [42], as well as polymeric adipate [33] have Despite being immiscible, the good interfacial adhesion
been employed successfully as plasticizers for PLA. Efforts have also between the PLA and PBS phase results in reasonably accurate pre-
been made to polymerize small molecules plasticizers of PLA, such dictions of the PLA/PBS mechanical properties using mixture rules.
as oligomeric tributyl citrate [29] and oligomeric diethyl bishydrox- Young’s modulus of the blend fall between the upper and lower
ymethyl malonate [29], to increase their molecular weight. bound of the mixture rules. However, tensile strength is slightly
The increase in molecular weight of the plasticizers comes lower than lower bound of the mixture rules; an indication that
at a price of compatibility and functionality. As a result of the interfacial adhesion is not ideal. Nonetheless, it is quite close
increased molecular weight, the miscibility [39,42,43] and effi- to the lower bound of the theoretical value, suggesting reasonable
ciency [25,29,39] of the PLA plasticizer may decrease. For example, compatibility.
in the case of PEG, phase separation occurs at a lower plasticizer Indeed, given the reasonable compatibility between PLA and
content for higher molecular weight PEG [39]. In addition, larger PBS, high elongation at break ∼270-340%, is also obtained when
molecular weight plasticizer is less effective, which can be gauged the co-continuous phase is formed. In addition, scanning electron
from the smaller magnitude of Tg depression of PLA at the same micrograph of the fracture surface with this composition range
plasticizer content [25,29,39]. (8.4–42 wt% PBS) showed drawn tiny fibrils; another indication of
This phenomenon can be easily predicted by the Flory-Fox ductility. Zhong and coworkers [49] employed this strategy on the
equation and Fox equation. According to the Flory-Fox equation, PLA/Starch blend to form the PLA/Starch/PBS ternary blend and has
the increased molecular weight of the plasticizer will lead to an successfully increased the ductility of the material by increasing
increase in its own Tg . With the increase in Tg of the plasticizer, the and decreasing the PBS and PLA content respectively, trading off
Tg final polymer blend (plasticized PLA) will be higher, as described some strength and stiffness.
by the Fox equation. Hence higher molecular weight molecules are Another example of a complementary polymer is Polycaprolac-
less effective plasticizers. tone (PCL), whose Tm and Tg is about 60 ◦ C and −60 ◦ C respectively
Indeed, the effectiveness of the plasticizer seems to compete [50,51], is also a ductile material at ambient temperature. PCL is
with stability of the material through molecular weight alteration. employed in a similar fashion as PBS due to its complementary
However, Ljungberg and Wesslén [29] reported that by introduc- properties to PLA/Starch blends. It is known that PLA and PCL
ing an amide group into the oligomeric diethyl bishydroxymethyl are immiscible and hence, a much smaller proportion of PCL in
malonate, hydrogen bonding can form between the plasticizer and the PLA/PCL blend will form a dispersed PCL phase in PLA matrix
PLA. This increase in intermolecular interaction decrease the plasti- [50,52]. Unmodified PLA/PCL blends have shown improved the duc-
cizers’ migration and cold crystallization rates without decreasing tility and toughness as compared to neat PLA [50], However, after
the compatibility and functionality of the plasticizer. compatibilization, PLA/PCL blend of showed better mechanical
Nevertheless, by trading some strength for flexibility through properties that are closer to that predicted by the rules of mixture
plasticization of PLA, impact strength of the PLA/Starch blend can be [50,52–55], an indication that interfacial adhesion of the unmodi-
greatly enhanced; even higher than that of neat PLA [37,41]. It can fied PLA/PCL blend is non-ideal but reasonable. Nonetheless, even
be seen that employing plasticization strategy on the PLA matrix is without PLA and PCL compatibilization, Sarazin and co-workers
a more effective method to toughen the PLA/Starch polymer blend reported improved ductility and toughness of PLA/Starch blend by
compared to plasticizing the dispersed Starch phase, as mechanical incorporating PCL [51]. However, this improvement in toughness
stress rest mainly on the PLA matrix for the uncompatibilized blend. may be partially contributed by another a compatibilizing mecha-
nism between the three components, which will be elaborated in
2.2. Mixture softening 2.4.4. Interfacial Transitioning sub- section.

The gist of this strategy is to tune the mechanical properties

of the PLA/Starch blend by incorporating a 3rd component that
possess complementary properties such as ductility and flexibility. 2.2.2. Ductile miscible component
This additional component should be compatible to PLA in order to Atactic Polyhydroxybutyrate (a-PHB), a type of Polyhydrox-
impart ductility to the matrix, which can either miscible or immis- yalkanoate (PHA), is an amorphous polymer that has a Tg of about
cible with PLA. This section will illustrate this strategy using 3 0 ◦ C, and hence behaves like an elastomer at ambient tempera-
different biodegradable polyesters, namely, Polybutylene succinate ture [56]. It can be synthesized via ring-opening polymerization
(PBS), Polycaprolactone (PCL) and Atactic Polyhydroxybutyrate (a- of racemic ␤-butyrolactone using KOH/18-crown-6 complex as the
PHB). initiator [57].
Focarete and co-workers [56,58] reported that a-PHB is fully
2.2.1. Ductile immiscible component miscible with PDLLA and PLLA over a full range of compositions.
One successful example of this strategy is the addition of Poly- However, Ohkoshi et al. [59] suggest that the miscibility between
butylene succinate (PBS). PBS is a semi-crystalline polymer that PLA and a-PHB is dependent on their molecular weight. Low molec-
has a melting temperature (Tm ) of about 114 ◦ C and glass transi- ular weight a-PHB (Mw = 9 400) is miscible with PLLA (Mw = 680
tion temperature (Tg ) of about −32 ◦ C [45]. Therefore, it is a ductile 000) up to 50 wt% a-PHB content, whereas high molecular weight
material at ambient temperature and can achieve elongation at a-PHB (Mw = 140 000) is immiscible with PLLA. Nonetheless, this
break of >300% depending on molecular weight [45]. strategy has allow 50/50 wt% of PDLLA/a-PHB blend to achieve the
The morphology and mechanical properties of PLA/PBS blend elongation at break of >300%. Therefore, a mixture of PLA/a-PHB
has been documented by Deng and Thomas [46]. At a much lower can serve as a more ductile matrix to the blend with Starch instead
mass fraction of PBS, between 8.4 wt% to 42 wt%, PBS is able to form of pure PLA. Unfortunately, to the best knowledge of the authors of
104 J.J. Koh et al. / International Journal of Biological Macromolecules 109 (2018) 99–113

this review paper, there are no studies done on PLA/Starch/a-PHB has been sufficiently plasticized by small molecule plasticizers, its
ternary blend [56] Tg can depressed to a level below ambient temperature making it
rubbery, as described by the Fox equation.
2.3. Elastomer toughening Many researchers have also suggested the formation of a
glycerol-rich ␤-TPS phase on the outer region of the dispersed
Elastomer toughening has been a common strategy used for Starch phase above a certain plasticizer content [51,60,67–72]. This
toughening of brittle polymers. Classical examples of elastomer phenomenon can be explained by the Harkins spreading theory
toughened engineering plastics are high impact polystyrene (HIPS) [72–74], that describes the morphology of a blend when two differ-
and the copolymer of acrylonitrile butadiene styrene (ABS). Phase ent immiscible polymers are dispersed within a third. The Harkins’s
separation usually occurs, leading to the formation of rubbery dis- equation is as follows:
persed phase embedded within the brittle polymer matrix. The
dispersed rubbery phase can act as the location of plastic defor-
31 = 12 − 32 − 13
mation, as well as craze or cavitation initiating centres. These
mechanisms serves to absorb energy upon stress, resulting in the
toughening of the material. There are several factors that affects Where 31 is the spreading coefficient for situation when com-
the final result of elastomer toughening. Firstly, it depends on the ponent 1 is the core being encapsulated by component 3, while
mechanical properties of the elastomer such as elasticity, ductility, component 2 is the matrix. 31 must be positive in order for this
strength etc. Secondly, it also depends on the concentration of the situation to be true.  is the interfacial tension of the respective
rubbery phase. Lastly, it also depends on the interaction between components pair. The following equation (2) is Harkins’ equation
the rubber phase and the matrix phase, which will determine the for the case where for the case where starch-rich ␣-TPS phase being
miscibility and dispersion of the rubber phase in the matrix, as well encapsulated by plasticizer-rich ␤-TPS phase:
as the interfacial adhesion between them.
Nonetheless, it is difficult to find a compatible elastomer for a
ˇ/˛ = ˛/PLA − ˇ/PLA − ˛/ˇ (2)
given matrix, let alone in the case of two different phases: PLA and
Starch. Therefore, in order to elastomer-toughen the PLA/Starch
blend, one would have 3 options: 1) Use an elastomer that is com- Where  ␣/PLA is known to be large [75], which can also be esti-
patible to PLA. 2) Use an elastomer that is compatible to Starch or mated from the poor interfacial adhesion that led to the poor
3) Use an elastomer that is compatible to PLA and Starch. mechanical properties.  ˇ/PLA can be assumed to much smaller than
 ␣/PLA due to entropic effects, given that Starch (macromolecules)
2.3.1. Elastomer compatible to PLA and starch has a much larger molecular weight than that of the plasticizer
Polyethylene octene (POE) elastomer has been successfully used (small molecules e.g. glycerol) [76]. Lastly,  ␣/ˇ can also be esti-
to toughened PLA/Starch blend by Shi and co-workers [60]. How- mated as very small since Starch and glycerol are largely miscible
ever, POE is neither compatible to PLA nor Starch given its non-polar components. Hence, a plasticizer-rich ␤-TPS phase encapsulating
characteristic. In the study, POE was compatibilized with both PLA a starch-rich ␣-TPS phase being dispersed in the PLA matrix illus-
and Starch via grafting of glycidyl methacrylate (GMA) onto POE trated in Fig. 1. is formed.
(POE-g-GMA or GPOE). GMA can react with both terminal car- The strongest evidence of this model is the appearance of two
boxyl and hydroxyl groups of PLA and Starch respectively (see 2.4.1. relaxation temperature of the TPS phase in DMA analyses, which
Chemical Crosslinking). has been assigned to as the Tg of the ␣-TPS phase and ␤-TPS phase
With a fixed 20 wt% of TPS and varying proportion of PLA/GPOE, respectively [51,77]. This plasticizer-rich ␤-TPS phase naturally has
the ductility of the PLA/GPOE/TPS blend peak at ∼400% elongation a much lower Tg than ␣-TPS phase given the higher plasticizer con-
at break impact strength of ∼11.5 kJ/m2 [60] with 15 wt% of GPOE. tent. With 24 wt% of glycerol in the TPS, Tg of ␤-TPS phase can
The subsequent decline in ductility and impact toughness can be reach ∼ −45 to − 47 ◦ C [51]. Nevertheless, it has been reported that
attributed to excess elastomer in the blend. This phenomenon is both ␣- and ␤-TPS Tg can be depressed to under ambient tem-
common in elastomer-toughening material [61,62]. One possible perature though sufficient plasticization, forming a fully rubbery
reason is that the high concentration of the elastomer leading to dispersed phase [51].
a high concentration of craze nucleation centres. Hence, crazes However, Müller et al. [78] suggest that the plasticizer-rich
impinge on one another resulting in the failure of the material phase encapsulating the starch-rich phase lack substantial evi-
before the crazes can be fully developed, causing the decrease in dence. They propose that the ␤ relaxation temperature was due
ductility and toughness of the material. to the movement of the smaller structural units in the within the
Starch molecules. Indeed, it is difficult to characterize this thin
2.3.2. Elastomer compatible to PLA layer, or to come up with substantial evidence on the thickness
As for the PLA matrix, many different elastomers has been of the layer [72], hence, more studies are required to prove the
used to successfully toughen PLA, such as polyolefin elastomer glycerol-rich model.
[63], polyamide elastomers [64], poly(ether-block-amide) [65], Despite the controversial model, TPS can perform the role of
Poly(n-butyl acrylate) (PBA) elastomer [66] and Poly(lactide- elastomers in PLA matrix when sufficiently plasticized, i.e. Tg of ␣-
random-caprolactone) [62]. In order to compatibilize these TPS phase is depressed to under ambient temperature. The effect
elastomers with PLA, they are usually copolymerized (block or of elastomeric TPS can be observed from the increase in ductility as
graft) with PLA or chemically bonded to PLA matrix through reac- TPS increases in various studies [26,60]. This is followed by a subse-
tive coupling agents. These techniques should also be applicable to quent decline in ductility observed when TPS content is in excess,
toughen the PLA matrix of the PLA/Starch blend as well. similar to the case of usual elastomer toughening cases. However,
its effect are limited due to poor interfacial adhesion with the PLA
2.3.3. Elastomer compatible to starch matrix. With proper compatibilization, the elastomeric TPS can aid
No deliberate attempt was made to toughen PLA/Starch blend by to improve the ductility of the PLA/TPS blend tremendously even
elastomer toughening the Starch phase as mechanical stress cannot when used at large amount. Indeed, Huneault and Li [26] observes
be properly distributed to the dispersed Starch phase due to poor a brittle-to-ductile transition of the compatibilized PLA/TPS blend
interfacial adhesion between PLA and Starch. However, if Starch when plasticizer content exceed a critical threshold.
 J.J. Koh et al. / International Journal of Biological Macromolecules 109 (2018) 99–113 105

Fig. 1. Schematic morphology of TPS with a phase separation of plasticizer-rich ␤-TPS phase and Starch-rich ␣-TPS phase. a) ␣-phase remains glassy for TPS with lesser
plasticizer content. b) ␣-phase becomes rubbery for TPS with higher plasticizer content.

2.4. Interphase compatibilization such as lysine diisocyanates (LDI) [95] and hexamethylene diiso-
cyanates (HDI) [42,95].
Compatibilization strategies are techniques that sought to The key difference between DI as compared to previously
increase the interfacial adhesion between the PLA and Starch phase, discussed coupling agents is that it has two functional groups (iso-
such that defects can be reduced and mechanical stress can be cyanate groups) that can react directly with PLA or Starch, therefore,
properly transferred from the matrix to the dispersed phase. From additional grafting process is not required. The isocyanate group
literature, compatibilization strategies can be classified into four can react with the hydroxyl group of Starch or carboxyl terminal
categories: 1) chemical crosslinking 2) amphiphilic bridging 3) group of PLA to form urethane linkages. Indeed, the reaction can
componential modification and 4) interfacial transitioning. also results in PLA-crosslinked-PLA or Starch-crosslinked-Starch
that does not aid in compatibilization of PLA and Starch. Nonethe-
less, the crosslinking mechanism between PLA and Starch (or TPS)
2.4.1. Chemical crosslinking via DI is illustrated in Scheme 3.
Chemical crosslinking is the most commonly employed strategy
to compatibilize PLA and starch, which uses a coupling agent to 2.4.2. Amphiphilic bridging
chemically bond PLA and starch molecules together Another way to compatibilize hydrophobic PLA and hydrophilic
Maleic Anhydride (MA) has been widely used as compatibilizer Starch is to include some amphiphilic molecules to act as physi-
for binary immiscible polymer blends [79–84]. Peroxide initiators cal bridges at the interface of the two incompatible components.
such as BPO or L101 are used for hydrogen abstraction of PLA This bridging molecule should constitute two different segments;
chains to generate radicals, which lead to either recombination one compatible to PLA and one compatible to Starch. The mecha-
with another PLA radical that results in a crosslink between PLA nism is illustrated using a di-block amphiphilic copolymer in Fig. 2,
chains or grafting of MA onto PLA [26,85–87]. If the latter is true, the however, this strategy is not just restricted to amphiphilic block
second step is the reaction between the anhydride group and the copolymers
hydroxyl group of Starch (amylose or amylopectin), which results Unquestionably, one of the polymers that are compatible with
in the opening of the five-member ring and the formation of ester any polymer is itself. Therefore, copolymers of PLA and Starch,
linkages [79]. In addition, if TPS is used instead of native starch, the namely, PLA grafted Starch (PLA-g-Starch) or Starch grafted PLA
anhydride group can also react with the hydroxyl group of Starch’s (Starch-g-PLA) is definitely a suitable and favoured candidate to
plasticizer (e.g. glycerol) [26,85]. It is also possible that the anhy- carry out this compatibilization strategy.
dride group reacts with the terminal carboxyl group of PLA, which Starch-g-PLA can be synthesized via polymerization of PLA onto
will not aid in compatibilization between PLA and Starch. Nonethe- Starch, using the hydroxyl groups as the initiator instead of the
less, the crosslinking mechanism between PLA and Starch (or TPS) usual alcohol [96,97]. One key challenge of this synthesis method
that provides the compatibilization effect is illustrated in Scheme 1. is the removal water content from the hydrophilic Starch, as poly-
The advantages of MA includes its low toxicity and that it does not merization of PLA is known to be sensitive to water.
homopolymerize under normal melt grafting conditions. On the other hand, Starch can also be grafted onto PLA. Woot-
Acrylic Acid (AA) can be used as a coupling agent in similar fash- thikanokkhan et al. reversed the chemical crosslinking procedure
ion [88], which is also illustrated in Scheme 1 in brackets. Instead of to produce PLA-g-TPS by reversing the MA crosslinking process
having a highly reactive anhydride group, the carboxylic acid of AA described in the 2.4.1. Chemical Crosslinking sub-section [98]; TPS
is proposed to undergo condensation reaction with hydroxyl group is first maleated with MA before being grafted onto TPS using per-
of Starch at 190 ◦ C. oxide initiators to generate PLA radical. In this case, plasticizer (e.g.
Similar to MA and AA, the grafting of Glycidyl Methacrylate glycerol) might be grafted onto PLA as well, which also act as the
(GMA) [89] onto PLA can be done via radical generation by per- amphiphilic can bridge in PLA/Starch blends.
oxides like BPO. The difference between MA and GMA is that GMA Similarly, Amylose, the linear minor component in Starch, can
is known to be able to homopolymerize [90]. Regardless of its abil- also be use as the hydrophilic component in the amphiphilic bridge.
ity to homopolymerize, the reactive epoxide group can react with PLA is also polymerize on Amylose using its hydroxyl group as the
the hydroxyl groups of Starch or the plasticizer to form ether link- initiator [93,99].
ages. Similar to the MA case, the epoxide can also react with the Ke and Sun [100] suggested that the copolymer of Polyvinyl
terminal carboxyl group of PLA, which does not contribute to com- acetate (PVA) and Polyvinyl alcohol (PVOH) can act as the phys-
patibilization efforts [60,91]. The crosslinking mechanism between ical amphiphilic bridge to compatibilize PLA and Starch. Due to
PLA and Starch (or TPS) via GMA is illustrated in Scheme 2. vinyl alcohol’s instability, PVOH is usually synthesized through
The effects of using various Diisocyanates (DI) to crosslink PLA hydrolysis of the PVA ester bonds. Therefore, partial or incomplete
and Starch molecules have been explored by many researchers. hydrolysis can result in the formation of PVA-PVOH random copoly-
They include aromatic diisocyanates such as toluene diisocyanates mer (PVA-r-PVOH). PVA has been reported to be miscible with PLA
(TDI) [42], phenylene diisocyanates (PDI) [92] and methylene in previous studies [100]. Likewise, studies have shown that PVOH
diphenyl diisocyanates (MDI) [28,42,93,94], as well as aliphatic one and Starch blends demonstrate partial miscibility and compatibil-
106 J.J. Koh et al. / International Journal of Biological Macromolecules 109 (2018) 99–113

Scheme 1. Chemical reaction of the PLA-Starch (TPS) crosslinking process using MA (AA) as the coupling agent.

ity due to formation of intermolecular hydrogen bonding between lizing PLA/Starch blend that resulted in increased impact strength
the two polymers [101–104]. depending on the degree of substitution of the hydroxyl groups
with acetyl groups. This improved compatibility can be largely be
attributed the formation of ester side group on Starch that has
2.4.3. Componential modification
better affinity with PLA, a polyester.
Another way to compatibilize two incompatible components is
A series of plant oil derivatives, namely soybean oil [106], cas-
to modify the components such that the modified component has
tor oil [107], tung oil [108] and cardanol [109] were also grafted
a better affinity with the other. In the case of PLA/Starch blend, this
onto Starch molecules via various coupling agents, such as MA
strategy is usually applied on Starch such that it becomes compat-
and DI mentioned in the 2.4.1. Chemical Crosslinking sub-section.
ible to PLA. Firstly, Starch is usually the minor component as PLA’s
These plants oils are generally hydrophobic [109] and indeed, the
superior mechanical properties are preferred in the final material as
final blends show improved mechanical properties. However, more
the matrix. Hence, it is more economical to modify Starch than PLA.
studies are required to show the decrease in interfacial energy
Secondly, Starch’s hydrophilicity is one of its greatest Achilles’ heel
between PLA and the modified Starch that leads to an increased
that hindered its application prospect. This drawback jeopardizes
interfacial adhesion.
the material’s structural integrity under moist or wet conditions.
Besides acetylation and grafting of plant oil derivatives, PEG has
Therefore, to preserve a certain level of water resistance in the
also been grafted onto Starch [40]. As mentioned previously (see
final material, Starch is usually modified into a more hydrophobic
2.1.1. Plasticization of PLA), PEG has a partial miscibility with PLA
component rather than the reverse modification on PLA. In order
and can act as a plasticizer for PLA. Even though PEG is a generally
to modify Starch into a more compatible component to PLA, the
known as a hydrophilic polymer because of its solubility in water,
hydroxyl groups of Starch can be substituted with hydrophobic
it has occasional hydrophobic behaviour as well [110]. In the study,
groups instead.
PEG was first reacted with MA to form dicarboxylic acid. The car-
A classic example of this is acetylation, which has been com-
boxyl groups can then react with the hydroxyl group of Starch to
monly performed on cellulose to increase its hydrophobicity,
complete the grafting. The chemical reaction and proposed mor-
forming cellulose acetate. Similarly, as a polysaccharide, Starch
phology is illustrated in Scheme 5. An increased impact strength
can undergo acetylation to form Starch acetate as well. Starch
of 2.37 kJ/m2 (more than 3 x of unmodified PLA/Starch blend) was
acetate can be synthesized via hydroxyls’ reaction with acetic anhy-
achieved with 20 wt% of Starch-g-PEG in the blend. Elongation for
drides [91,105], as illustrated in Scheme 4. Indeed, Zhou et al. [91]
reported that acetylation has proved to be effective in compatibi-
 J.J. Koh et al. / International Journal of Biological Macromolecules 109 (2018) 99–113 107

Scheme 2. Chemical reaction of the PLA-Starch (TPS) crosslinking process using GMA as the coupling agent.

Fig. 2. Schematic morphology of amphiphilic bridging using amphiphilic di-block copolymer as an example.

that blend was also increased to ∼190%, while tensile strength This method of modifying Starch consists of 4 main steps in
remains at a reasonable ∼32.2 MPa. Scheme 6: 1) Formation of admicelle on the Starch surface 2)
Instead of chemically substituting the hydroxyl groups of Starch Adsolubilization of MMA (monomers) within the admicelle 3) Poly-
with a PLA-compatible side group, surface coating of a compati- merization of the monomers and 4) Removal of the top layer
ble substance on the surface of Starch particles may work as well. surfactant to expose coated PMMA.
Hemvichian et al. [111] employed the admicellar technique to coat Indeed, the surface modified Starch demonstrated increased
a thin film of Polymethyl methacrylate (PMMA) onto Starch par- hydrophobicity from contact angle tests. Mechanical properties of
ticles. Having an ester group as a side group, hydrophobic PMMA the blends of PLA and modified Starch were studied with up to
has previously demonstrated good compatibility with PLA. In an 30 wt% of modified Starch. All the blends demonstrated higher ten-
earlier study, the same admicellar polymerization technique has sile strength and ductility than PLA blends with unmodified Starch,
been used to coat PMMA onto graphene nanosheets to improve the signifying improved compatibility between components.
interfacial adhesion between the graphene filler and the PLA matrix
[111].
108 J.J. Koh et al. / International Journal of Biological Macromolecules 109 (2018) 99–113

Scheme 3. Chemical reactions of the PLA-Starch (TPS) crosslinking process using DI as the coupling agent.

Scheme 4. Acetylation of Starch using Acetic Anhydride.

Scheme 5. Chemical reaction for the synthesis of Starch-g-PEG and the proposed morphology of PLA/Starch-g-PEG blend. Adapted from [40].
 J.J. Koh et al. / International Journal of Biological Macromolecules 109 (2018) 99–113 109

Scheme 6. Process of surface modifying Starch with a thin PMMA coat using admicellar polymerization technique. Adapted from [111].

Fig. 3. Schematic morphology of Interfacial Transitioning mechanism.

2.4.4. Interfacial transitioning One possible example of the transitioning phase is the PCL. Pre-
Another technique that is not usually applied in deliberate vious studies have shown that PCL has rather good compatibility
attempt to improve the compatibility of the PLA/Starch blend is with Starch [112]. In addition, PCL is also more compatible to PLA
to provide a transitioning phase in between PLA phase and Starch than Starch, from interfacial energy estimations [53,75] and micro-
phase. This transitioning phase should have better compatibility scopic characterization [113]. More importantly, blends of PLA and
and interfacial adhesion to both the PLA and Starch phase as com- PCL have demonstrated some form of compatibility through the
pared to the compatibility between PLA and Starch phases. In order mechanical properties of their blends (see 2.2.1. Ductile Immiscible
for this strategy to work, the sum of interfacial tension between PLA Component). For example, Finotti and co-workers [50] reported an
and the transitioning phase (␥PLA/trans ), and the interfacial tension increase in elongation at break to ∼10% with 5 wt% of PCL and elon-
between the transition phase and Starch (␥trans/Starch ), should be gation at break of up to 30% with 20 wt% of PCL in PLA/PCL binary
smaller than the interfacial tension of PLA and Starch (␥PLA/Starch ). blends. This mechanical synergy indicates some form of compati-
Then according to Harkins’ theory (see 2.3.3. Elastomer Compatible bility and interfacial adhesion between PLA and PCL. However, as
to Starch), a spontaneous mechanism will occur in order to lower mentioned previously (see 2.2.1. Ductile Immiscible Component)
the free energy of the system, resulting in the transitioning phase interfacial adhesion of the unmodified PLA/PCL blend is less than
encapsulating the Starch phase as illustrated in Fig. 3. ideal [50,53] but nonetheless, it is still better than PLA/Starch.
110 J.J. Koh et al. / International Journal of Biological Macromolecules 109 (2018) 99–113

Table 1 as the plasticizer for PLA and Starch respectively, while PLA-g-TPS
Summary of the strategies for toughening PLA/Starch blend.
was used as the amphiphilic bridge.
Main Strategies Sub-Strategies However, some of these strategies can also contradict one
Additive Plasticization Plasticization of Starch another when applied simultaneously in a single blend. One
Plasticization of PLA common example is the competition for the limited hydroxyl
Mixture Softening Ductile Immiscible Component groups in Starch. For example, in a study conducted by Zhou [91],
Ductile Miscible Component the Chemical Crosslinking (GMA) mechanism competes with the
Elastomer Toughening Elastomer Compatible to PLA and Starch
Componential Modification (acetylation) mechanism for Starch’s
Elastomer Compatible to PLA
Elastomer Compatible to Starch hydroxyl group. This produces in a toughness peak at an esterifica-
Interphase Chemical Crosslinking tion degree of 0.04 given a fixed amount of GMA.
Compatibilization Amphiphilic Bridging In some toughening techniques, several strategies are being
Componential Modification
applied concurrently in a single operation. For example, the plas-
Interfacial Transitioning
ticization of Starch can lead to the formation of elastomeric
TPS that can provide elastomer toughening effect. In addition,
the formation of ␤-TPS phase layer also improves interphase
Indeed, studies have shown that ternary blends of PLA/PCL/TPS
compatibility through the interfacial transitioning mechanism
results in a better dispersion of the TPS phase as compared to
[26,51,60,67–72,76,78,7]. Similarly, the addition ductile PCL to
binary blends of PLA/TPS [51,113], indicating improved compati-
form a ternary PLA/PCL/Starch blend may provide toughening
bility within the blend. Furthermore, TPS phases are characterized
through mixture softening and interfacial transitioning strategy
to be located within the PCL phase, demonstrating the spontaneous
[50,51,53,75,112,113].
mechanism for the phases to lower their interfacial energy through
In contrast, some of the toughening techniques require sev-
morphological rearrangement to ultimately lower the free energy
eral strategies to work. One example is the Elastomer Toughening
of the entire system. More importantly, Sarazin et al. [51] reported
using Elastomer Compatible to PLA and Starch. Since it is difficult
an increase in ductility of the ternary blend with increasing PCL
to find an elastomer that is compatible to both PLA and Starch,
content, up to 10 wt%. The increase in ductility has also lead to the
compatibilization strategies are required to execute this technique.
increase in impact toughness, where PLA/PCL/TPS 40/10/50 blend
In the study by Shi, the elastomer is chemically crosslinked with
achieve an impact strength of ∼70 J/m (three times that of neat
both Starch and PLA, hence acting as a compatibilizer as well as
PLA).
an elastomeric toughening agent [60]. In another example, where
However, this transitioning layer is difficult to characterize.
the Componential Modification strategy that utilizes adimicellar
Furthermore, interfacial tension between the components may be
polymerization technique to coat a thin layer of PMMA onto Starch
affected by several factors such as impurities, plasticizer content,
particles’ surfaces, the surfactant act as an Amphiphilic Bridge
molecular weight and polydispersity [76]. Therefore, more inves-
compatibilizer between the Starch and PMMA [111]. Without this
tigation regarding the interfacial tension between PLA, PCL and
surfactant as the amphiphilic compatibilizer, the interfacial adhe-
Starch is required in order for PCL compatibilizing effect to be more
sion between hydrophobic PMMA and hydrophilic Starch will be
conclusive.
poorer, hindering stress transfer.
Similarly, the adequate plasticization of Starch that led to the
formation of the ␤-TPS phase (see 2.3.3. Elastomer Compatible to
Starch), serving as a transitioning phase to lower the interfacial
tension between PLA and Starch. Be it a glycerol-rich or smaller
3.2. Preserving the novelty
units of amylose and amylopectin [51,60,67–72,78,7], these smaller
molecules aggregate at the interface by expelling large chains
Many of the strategies mentioned in this review employed
to lower the interfacial tension through configurational entropic
non-bio-based or non-biodegradable substances. For example,
effects [76]. Indeed, Huneault and Li [26] reported decreasing TPS
non-biodegradable components such as PEG and PMMA, as well
disperse phase size with increasing content of plasticizer. Although
as non-bio-based components such as petrol-derived plasticizers,
they attributed this effect to the lower viscosity of the more plas-
PVA, PVOH, PCL, PBS and PEBA. Their inclusion diminishes the
ticized TPS [26], this morphology can also be seen as the result
novelty of the final material as a fully bio-based and completely
of lower interfacial tension between the matrix and the dispersed
biodegradable material.
phase. However, relying on the entropic effect alone, ␤-TPS phase
Furthermore, some of the techniques involve complicated and
may not be sufficient to compatiblize PLA/Starch, which can be
excessive processes. For example, the admicellar polymerization to
observed from their rather poor mechanical properties. There-
surface modify Starch and chemical synthesis of elastomer compat-
fore, additional interphase compatibilization may be required to
ible to both PLA and Starch can prove to be very tedious. One key
enhance the interfacial adhesion.
advantage of employing Starch in the blend is to utilize its econom-
ical aspect. However, these complicated and excessive processes
3. Disscussion section would reduce the commercialization aspect of the PLA/Starch blend
to compete with the commodity plastics.
3.1. Combination of strategies A good strategy should be economically viable. For example, if
a readily available material that have strong interactions with both
All the toughening strategies described in this review has been the PLA and Starch phase can be identified, then it can serve as the
summarised in Table 1. It is important to note that these strategies interphase compatibilizer either via amiphiphilic bridging or inter-
not mutually exclusive and are able to function jointly in a single facial transitioning. Hence, mere compounding is required, without
blend. the need for tedious chemical synthetic processes. In addition, if
In some of the studies, several strategies are applied collectively the identified compatibilizer is a ductile or elastomeric material,
on a single blend in search for the optimal mechanical properties. it can perform a second role of mixture softening or elastomer
For example, Wootthikanokkhan et al. [98] utilized Plasticization toughening for the blend. Otherwise, plasticizing Starch to form
of PLA, Plasticization of Starch and Amphiphilic Bridging strategies elastomeric TPS may be sufficient. Preferably, the identified com-
concurrently in their study. Glycerol acetate and glycerol was used patibilizing material is both bio-based and biodegradable. This will
 J.J. Koh et al. / International Journal of Biological Macromolecules 109 (2018) 99–113 111

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