Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
copying and redistribution of the article or any adaptations for non-commercial purposes.
Perspective
pubs.acs.org/journal/ascecg
■ INTRODUCTION
The past is prologue for durable bioplastics; the quest for
emissions and end of life options, PLA is superior to many
petroleum based polymers.1 PLA already serves as an
materials with properties similar to those of engineering plastics alternative to certain petroleum based plastics in commercial
but derived from renewable resources is becoming a reality in applications. It is available in the market at a price on a par with
the 21st century. Although several biobased engineering plastics that of common plastics like polypropylene. Market demand for
are already available in the market, the idea here is to take PLA has grown dramatically over the past decade, with much of
advantage of the cost competiveness and unique properties of it being in the packaging industry.2 PLA was initially promoted
polylactic acid (PLA). The past decade has seen a remarkable for single use packaging applications, given the key benefit of
surge of research interest in developing PLA based blends and short life cycle due to its compostable nature. The application
composites for durable applications in automotive, electronics areas for PLA are widening with usage in durable structural
and semistructural parts. The diversity of the approaches, and parts generating particular high demand. According to
the specialty additives and toughening agents has increased our European trade association for the bioplastics industry, the
knowledge on controlling the performance of PLA for long- global production of durable bioplastics is forecasted to increase
term durable product applications. This perspective provides a by 535% from 2014 to 2019.3
critical review of the literature in the field of super toughened, Besides property enhancement with suitable additives, when
heat resistant PLA blends and biocomposites followed by the final formulations are intended for compostable applica-
recommendations for future work. tions, the materials should satisfy the compostability standards
while retaining its compostability. Industries are therefore depends on many extrinsic (notch, temperature, loading mode,
seeing a major shift in the marketplace from “compostability” to specimen geometry, fracture behavior) and intrinsic (phase
“renewability”. However, being compostable and being renew- morphology, chain structure and entanglements) variables. The
able are not dependent or in conflict with each other, each has responsiveness of a particular polymer to be rubber toughened
its own advantages. Preference for “renewable carbon” instead is also said to depend on entanglement density (νe) and
of “fossil carbon” stems from the very realization of our need to characteristic chain ratio (C∞); these two will decide the
reduce nonrenewable resource consumption, and greenhouse fracture behavior of crazing and yielding.15 See Wu’s work15 for
gas (GHG) emissions. The Kyoto Protocol was the first critical detailed understanding of these concepts.
step taken toward a truly sustainable future; it mandates Toughening mechanisms including shear yielding, multiple
emission cuts for industrialized nations. Ratified by 145 nations crazing and a combination of both have been reported for
around the world, the protocol entered into force in February toughened PLA blends.9 According to toughening theo-
2005.4 At the 10 year mark, United Nation Framework ries,15−19 stress concentration due to the presence of spherical
Convention on Climate Change (UNFCCC) announced those rubbery particles is the first step to complex toughening
countries who took on the targets of the protocol have process. Multiple crazing occurs when the stress required for
collectively reduced the emissions over 20% as opposed to the craze initiation is less than the yield stress. In this situation,
aimed target of 5%.5 A successor climate change agreement maximum triaxial stress concentrations at the dispersed
approved in Paris COP21 Conference, December 2015, has set particles initiate crazes. Craze termination is the next natural
a goal to keep the world under 1.5 °C temperature rise.6 A step in this mechanism through the formation of small multiple
Japanese government directive says by 2020, 20 wt % of all crazes leading to crack propagation. New surfaces generated
plastics used in Japan must be derived from renewable during the creation of multiple crazes consume more energy
resource.7 Leadership in Energy and Environmental Design than a small number of large crazes. Shear yielding occurs when
(LEED) certifications, carbon tax and other local regulations the stress required for craze initiation is greater than yield
are also driving the demand for durable biopolymers. stress. Toughening by this mechanism is usually achieved by
Current research around the world on PLA modification and hydrostatic tension in the dispersed particles acting as shear
application is focused on producing high performance partially band initiators. When the yield stress and craze initiation stress
renewable materials that can compete with conventional are comparable or when there are interactions between the
plastics. However, much like other synthetic plastics, PLA has shear bands and crazes formed in the matrix, the combination
its own inherent weakness that prevents it from being widely of shear yielding and multiple crazing becomes the predom-
adopted for durable applications, in particular its low toughness inant mechanism. Cavitation is another important precursor
and heat resistance. PLA has a very slow crystallization rate, phenomenon to any toughening mechanism. Two types of
whereas a high level of crystallinity is desirable in finished cavitation have been observed in PLA toughened with a
products as it dictates most of the mechanical and thermal rubbery phase: (i) internal cavitation, which occurs when the
properties. The toughness and ductility of PLA have been interfacial bonding is strong between the rubber domains and
improved with multiple strategies including plasticization, matrix; (ii) debonding cavitation, which occurs when there is
copolymerization, and melt blending with different tough poor interfacial bonding strength. To prevent the localization of
polymers, rubbers and thermoplastic elastomers. Research strain, cavities formed either in the rubber particle (internal) or
progress in toughening PLA based on these strategies can be the matrix (debonding) alters the triaxial stress state and favors
found in several recent review articles.8−14 However, none of the formation of shear bands ultimately leading to shear
these articles have articulated the efforts taken toward achieving yielding of the matrix. Combination of internal and debonding
a PLA based material with improved short-term heat resistance. cavitation is also a possible mechanism.
This perspective summarizes the most recent developments in The particle size, shape and distribution of toughening agent
achieving super toughened and heat resistant PLA blends and can be tailored to reduce substantially the amount of impact
composites. Exhaustive literature available on these topics are modifiers or elastomers required for a desired toughness.
organized based on the strategies and approaches taken to Multicomponent blends containing reactive copolymers are
resolve the material problems. Various factors governing the therefore being developed to tune the phase morphology in
toughness and heat resistance of the blends and composites are interesting ways and obtain blends with moderate stiffness and
also discussed.
■
sufficient toughness by employing techniques like in situ
reactive compatibilization and dynamic vulcanization. These
SUPER TOUGHENED BLENDS: CURRENT TREND processes increase interfacial strength by promoting chemical
SEEKING TOUGHER PLA reactions between blending components establishing strong
Toughness: Definitions and Mechanisms. Toughness is bridge for transmission of stresses. Resulting PLA blends with
a complicated property; it is defined in terms of “impact drastic improvement in impact toughness are being referred to
strength/toughness”, the ability to absorb sudden impact as “super toughened” PLA. This term was first known to be
energy without breaking and “tensile toughness”, the ability used by Wu15 for convenience to denote arbitrarily blends
to absorb energy while being pulled apart or stretched. having notched impact strength higher than 10 ft/lb or ∼530 J/
Emphasis is on the ability to absorb energy before fracture. A m (energy lost per unit width, North American standard),
good combination of strength and ductility is the key to which is approximately equal to 53 kJ/m2 (energy lost per unit
toughness. PLA is a brittle polymer with low crack initiation cross-sectional area, European standard) depending on the
energy (measured by unnotched impact test) and low crack dimension of the sample. Research work specifically focused on
propagation energy (measured by notched impact test); it fails achieving super toughened PLA blends (impact strength
by crazing. Although it may be relatively easy to improve the beyond 35 kJ/m2) is reviewed in this section. They are
ductility (elongation at break), it is much more challenging to categorized according to the type of reactive toughening
increase the impact toughness of PLA. Impact toughness polymers and techniques used. This is followed by recom-
2900 DOI: 10.1021/acssuschemeng.6b00321
ACS Sustainable Chem. Eng. 2016, 4, 2899−2916
ACS Sustainable Chemistry & Engineering Perspective
mendations for future work. Range of impact properties thus far weight PLA containing 20% EGMA was found to have a drastic
obtained in super toughened PLA blends are summarized in effect on elongation,21 as the value went up from 26% to
Table 1. Most of the articles in this section were focused on >200%. However, a super toughened PLA blend with 72 kJ/m2
achieving super toughness and have not investigated the effect of impact strength was achieved only after annealing the
on crystallinity or heat resistance. processed samples at 90 °C for 2.5 h. Another parameter
Reactive Compatibilization with Functional Mono- appearing to have a significant effect on the resulting
mers. Successful application of a reactive compatibilization toughening is GMA grafting content. Polyethylene octene
technique has provided enormous opportunities to compatibi- (POE), a metallocene catalyzed thermoplastic polyolefin
lize otherwise immiscible and incompatible blends. Reactive elastomer grafted with different percentages of GMA (1.8 and
compatibilization is therefore seen as a powerful technique to 0.8%), was used to toughen PLA.22,23 To achieve an impact
enhance effectively the compatibility of PLA with other tough strength of 55 kJ/m2, 45 wt % of POE-g-GMA (1.8%) had to be
polymers. Melt blending PLA with other suitable polymers in blended with PLA,22 whereas in another study,23 20 wt % of
the presence of a reactive monomer forms a graft copolymer at POE-g-GMA (0.8%) was sufficient to attain super toughness of
the interphase, decreases the interfacial tension of the over 80 kJ/m2. These super toughened blend systems were
immiscible polymer components and promotes interfacial proved to be efficient in absorbing external energy through a
adhesion. A finer phase morphology developed in the blends combination of crazing and shear yielding mechanisms.
facilitates stress transfer between the two phases, thereby Poly(ether-block-amide), PEBA, a commercial class of thermo-
improving the properties of the blends. Maleic anhydride, plastic copolyester elastomer from Arkema, is seen as an
glycidyl methacrylate, isocyanate and epoxy are some of the efficient impact modifier for brittle polymers as it is highly
widely investigated reactive monomers proving to be successful resistant to sudden impact even at very low temperatures (−40
in compatibilizing the blends of PLA with other bio- and °C). In spite of such favorable properties,24 30 wt % PEBA was
petroleum based polymers. In the work of Harada et al.,20 0.5% required to improve the impact strength of PLA to 60 kJ/m2.
lysine triisocyanate (LTI) was found to increase the impact Zhang et al.25 used EMAGMA as a reactive interfacial
strength of PLA/PBS (90/10) blend from 18 kJ/m2 to 50−70 compatibilizer for blends of PLA/PEBA and achieved impact
kJ/m2. These improvements were attributed to effective strength up to 500 J/m, while maintaining tensile strength at 50
interfacial reactions accomplished between the isocyante MPa (Figure 1). Performance improvements in these ternary
functionalities of LTI and carboxyl, hydroxyl end groups of
the blending polymers.
Glycidyl methacrylate (GMA) is one of the versatile
functional monomers tailored to meet a variety of applications.
A great number of PLA super toughening studies report use of
GMA in one or other forms to facilitate compatibility by
reacting with functional end groups of PLA. Effectiveness of
GMA in improving the toughness of PLA is explored mainly
through these three routes: (i) addition of GMA monomers or
copolymers such as ethylene glycidyl methacrylate (EGMA),
ethylene methyl acrylate glycidyl methacrylate (EMAGMA)
and ethylene butyl acrylate glycidyl methacrylate (EBAGMA),
(ii) addition of tough polymers grafted with GMA to facilitate
compatibility between the blending components (two-step
process of grafting followed by reactive compatibilization) and
(iii) addition of tough thermoplastic elastomers in combination
with GMA copolymers in one-step reactive extrusion. Factors
Figure 1. Components, morphology and impact strength of
drastically affecting the toughening behavior of PLA blends supertoughened PLA blends. [Reprinted with permission from ACS
containing GMA are the reactive extrusion screw rpm and Applied Materials and Interfaces, Vol. 6, K. Zhang, V. Nagarajan, M.
residence time, which in turn affects important morphological Misra, A. K. Mohanty. Supertoughened renewable PLA multiphase
aspects such as dispersed phase size and interparticle distance. blends system: Phase morphology and performance, 12436−12448,
Increasing the screw rpm from 30 to 200 in low molecular Copyright 2014, American Chemical Society.]
blends were attributed to their unique morphology of partial however a challenge in simple binary blends of PLA with such
encapsulation of PEBA by EMAGMA in PLA matrix. Interfacial polymers.31−33 Researchers have looked into core−shell acrylic
cavitation and good adhesion between phases resulted in copolymers such as methyl methacrylate−butadiene styrene,
massive shear yielding of PLA matrix. acrylonitrile−butadiene styrene and methyl methacrylate−butyl
Vachon et al.26 used EMAGMA and poly(maleic anhydride- acrylate copolymers to super toughen PLA.34−40 The rubbery
alt-octadecene) (PMAOD) to compatibilize PLA and thermo- core provides impact resistance whereas the glassy shell imparts
plastic poly(ether ester) elastomer, PEE. A sharp transition in rigidity. Outer shell can be designed specifically to be
impact strength values to 650 J/m was noticed in PLA ternary compatible with the PLA matrix. Core−shell composition,
blends containing 12% of PEE and 12% of EMAGMA, with particle diameter and its distribution, grafting percentage and
EMAGMA being more efficient compared to PMAOD. cross-linking degree are all important factors to achieve the
Recently, Zhou et al.27 investigated the effect of adding GMA necessary toughening and they have all been investigated in
grafted PEBA (PEBA-g-GMA) as an impact modifier for PLA detail in PLA matrix. Acrylic impact modifiers (ACRs)
and thermoplastic starch acetate (TPSA). This work showed a containing different ratios of methyl methacrylate, MMA
notched Izod impact strength of ∼60 kJ/m2 could be achieved (hard/shell monomer) and butyl acrylate, BA (soft/core
for PLA/TPSA/PEBA-g-GMA (70/15/15) blend. A TPSA monomer) were used to super toughen PLA.36,37 Impact
esterification degree of 0.04% was needed to improve the strength and elongation at break gradually increased with
compatibility between TPSA and PLA/PEBA-g-GMA. Proper- increase in the amount of soft monomer in the ACR. In PLA/
ties of polymers are influenced to a greater extent by the length ACR (90/10) containing BA/MMA in the ratio of 90/10, the
of the macromolecule. When the macromolecular chain is unnotched impact strength was significantly increased to 68 kJ/
longer, the molar mass and entanglement degree is higher, m2 compared to 17 kJ/m2 for neat PLA. Tensile and flexural
which increases the melt temperature and viscosity. Adding a properties were not drastically reduced as the ACR content was
chain extender (CE) to PLA increases the molar mass of PLA only 10%.36 As the concentration of MMA hard shell monomer
by connecting the short and long polymer chains via a reactive increased, the impact strength initially increased and then
functional end groups present in the CE. When a multifunc- decreased, signifying the presence of a critical concentration of
tional epoxy based chain extender, Joncryl was used for in situ MMA. The highest notched Izod impact strength of 77.1 kJ/m2
reactive compatibilization of PLA and poly(butylene succinate- was achieved when the ACR core−shell ratio was optimized at
co-adipate), PBSA, the alteration of blend structure from linear 79.2/20.8 for the 80/20 PLA/ACR blend.37 With increase in
to long branched chains enhanced the impact strength of PLA/ BA content, the interactions between ACR and PLA were
PBSA (60/40) blend28,29 as shown in Figure 2. postulated to get stronger and the interface between these
phases was indistinct. Internal and debonding cavities in the
ACR domains induced crazes and shear bands in the PLA
making the matrix around the ACR particles to deform easily to
achieve shear yielding as shown in the schematic,36 Figure 3.
The particle size of the PBSA dispersed phase was reduced Figure 3. A simple schematic of a possible mechanism by which ACR
by 74% with the addition of 0.6% Joncryl, and further reduction toughens PLA. [Adapted from BioResources, Vol. 9, X. Song, Y. Chen,
was noticed with increase in Joncryl content owing to effective Y. Xu, C. Wang. Study of tough blends of polylactide and acrylic
compatibilization. Dong et al.30 have also reported Joncryl is impact modifier, 1939−1952, 2014.]
effective in increasing the ductility and percentage elongation of
PLA/PBAT blends, to a maximum of 500%. As previous Poly(ether glycol) methyl ether acrylate, abbreviated as
studies29 have established the presence of induction time for AcrylPEG, has been most effective in imparting super
reactivity of Joncryl, the effect of increasing the temperature to toughness to PLA thus far. Two different approaches were
increase the reactivity of Joncryl could be an interesting aspect investigated by Kfoury et al.:38 (i) polymerization of AcrylPEG
of future investigations. to poly(AcrylPEG) using free radical initiator, Luperox and (ii)
Acrylic Copolymers and Core−Shell Impact Modifiers. direct one step reactive extrusion with PLA, where in situ
Acrylic polymers such as poly(methyl methacrylate), PMMA, grafting of AcrylPEG onto PLA backbone was achieved.
and poly(butyl acrylate), PBA, have been found to be partially Substantial improvement of notched Izod impact strength to
miscible with PLA; therefore, they have been used to toughen 102 kJ/m2 was achieved for PLA with 20 wt % AcrylPEG, and
PLA.31,32 Achieving significant increase in impact strength is 35 kJ/m2 for PLA with poly(AcrylPEG). Commercial non-
2902 DOI: 10.1021/acssuschemeng.6b00321
ACS Sustainable Chem. Eng. 2016, 4, 2899−2916
ACS Sustainable Chemistry & Engineering Perspective
Figure 5. Morphology of the PLA/EVA50 (80/20) blends after impact testing: (a) initial impact bars, (b) optical images, and TEM images of (c)
undeformed part, (d−d″) the stress whitening zone at different magnifications. [Reprinted from European Polymer Journal, Vol. 48, P. Ma, D. G.
Hristoca-Bogaerds, J. G. P. Goossens, A. B. Spoelstra, Y. Zhang, P. J. Lemstra. Toughening of poly(lactic acid) by ethylene-co-vinyl acetate copolymer
with different vinyl acetate contents, 146−154, Copyright 2012, with permission from Elsevier, License number: 3794310181202.]
island morphology of PLLA/TPU to a unique network-like the inability of the second phase to act as stress concentrator
structure. High levels of crystallinity in these blends were does not favor multiple crazing or shear yielding resulting in
achieved by injecting the samples into a preheated mold at 130 blends with only moderate toughness. Similarly, low toughness
°C and postannealing. This resulted in PLLA/TPU/PDLA was reported for PLA with in situ formed PU containing non-
(70/15/15) blends with remarkable improvement in impact cross-linked product that acted as a plasticizer.63 In the case of
strength up to 63.2 kJ/m2. Ethylene-co-vinyl acetate (EVA) PLA/EVA blends, toughness improvements were marginal
with different vinyl contents and ethylene acrylic elastomer because of the formation of homogeneous morphology below
(EAE) has also been found to impart super toughness to PLA 20 wt % EVA.65
at 20 wt %.65,66 Formation of shear bands initiated by the Toughness improvement is also the highest at an optimum
internal cavitation of EVA resulted in shear yielding type of rubber particle size. When the dispersed phase is incompatible
fracture behavior in the blend, no crazing or interfacial with the matrix, it would exist as spherical particles to reduce
debonding occurred. As a consequence of numerous internal surface tension. If the components in the blend have good
cavitations, stress whitening was noticed on a macroscopic scale compatibility, uniform dispersion of the rubbery toughening
as shown in the Figure 5. agent with relatively small particle size can be expected. With an
deformation mechanism. For brittle polymers in general super observations reporting very small particle size but no substantial
toughening is predicted to occur at an optimum νe of 0.1 toughening effect do not follow this theory on L and Lc.
mmol/cc, as massive crazing and yielding of the matrix occurs Further studies are needed to establish any possible relation-
at this level of νe.16 Depending on composition, PLA is ships.
predicted to have νe in the range of 0.12−0.14 mmol/cc.57,67
Using Wu’s relationship16 between optimum rubber particle
size, do and νe,
■ HEAT RESISTANCE: CRITICAL ASPECT
CONFERRING DURABILITY
log d o = 1.19 − 14.1ve (1)
Heat resistance can be defined as the ability of a material to
maintain properties of interest at a desired level at the
the do for PLA can be calculated to be in the range of 0.16−0.31 maximum service temperature for a prolonged period of time.
μm. On the basis of theoretical investigations, this range can be Having a certain level of heat resistance is one of the principal
expected to be the guiding value of particle size in future PLA criteria for material selection. The heat resistance of PLA
work aiming at achieving successful super toughening effect. depends on its level of crystallinity and crystallization behavior.
However, if the dispersed rubber phase contains rigid The crystallization model suggests the chain segments of
subinclusions as in the case of core−shell or salami-like semicrystalline PLA coexist in three different forms: (i)
morphology in ternary blends, the inclusion phase can anchor crystalline fraction, (ii) rigid amorphous fraction (RAF) and
the load bearing fibrils to the matrix, which can effectively (iii) mobile amorphous fraction (MAF).70 Crystalline fraction
reduce premature cavitation. Therefore, in an alternative view, is where the chain segments are all in ordered crystalline state.
particle size range required to achieve optimum toughness also Random long molecular chains of amorphous fraction coexist
depends on other factors such as strain rate, morphology of the with the crystalline chains.70,71 When a polymer approaches its
dispersed particles, rubber content and the rubber shear glass transition temperature, Tg, molecular chains of the
modulus. crystalline region are unlikely to move due to strong
Unfortunately, PLA super toughening studies have not intermolecular interactions, but chains of the amorphous
delved into the effect of particle size distribution. Bimodal phase move freely. Within the amorphous region, there are
particle size distribution was observed when P[CL-co-VA] with some chain segments that are rigid, consequently hindering free
high molar mass was used to toughen PLA samples prepared by movement of the entire long chain. This fraction is referred to
compression molding.59 Although a super toughening effect as rigid amorphous fraction (RAF). The remaining long
was not achieved, compression molded samples containing molecular chains in the amorphous region are known as
P[CL-co-VA] in bimodal particle size distribution attained MAF.70−72 PLA with very low degree of crystallinity has a great
higher impact strength compared to their injection molded proportion of its chains in the MAF, which has high mobility
counterparts. Such improvements in compression molded near its Tg and therefore exhibits very low heat resistance, with
samples were thought to be because of the relatively larger distortion temperatures often occurring close to its Tg. When
size of the microdomains in them compared to the morphology the crystallization of PLA is facilitated with external aids such as
of injection molded samples. The authors did not provide nucleating agents, the proportion of the crystalline and rigid
further explanation behind this experimental observation. amorphous fraction is increased, which impedes chain mobility
Smaller particles can toughen the localized shear bands formed and resists heat induced distortions, resulting in enhanced heat
in between the large particles.68 This makes the crack tip region resistance.71,72 A schematic of the CF, RAF and MAF is shown
sustain higher fracture load by maintaining a higher critical in the graphical abstract.
stress level. If this critical stress level generates greater triaxial Heat resistance is often quantified by the detection of a
stress ahead of the crack tip, it causes higher degree of softening point under a certain load. The two most commonly
cavitation in the larger particles; consequently, the adjacent adopted techniques measure: heat deflection or distortion
matrix undergoes shear yielding before fracture.68 Optimum temperature (HDT) and Vicat softening temperature (VST).
size and biomodal distribution would be necessary to achieve HDT is defined as the temperature at which a specimen
synergistic super toughening. There is great scope for deflects 250 μm, under a specified load and thickness at a
interesting future work on examining the effects of such heating rate of 2 °C per min.72 The two common loads used
biomodal particle size distribution. One way to achieve such are 0.46 MPa (66 psi) and 1.8 MPa (264 psi). VST is defined as
distribution in PLA matrix would be to use small fine rubber the temperature at which the specimen is penetrated to a depth
particles in combination with large coarse particles. Synergistic of 1 mm by a flat-ended needle with a 1 mm2 cross-sectional
toughening with a combination of 1−2 and 70 μm rubber area.72 Common loads are 10 and 50N with heating rates of
particles from recycled tires has been observed in epoxy resin.69 either 50 or 120 °C per hour depending on the standards
Another factor to consider for efficient rubber toughening is followed.73,74 It is generally understood VST is the temperature
the average interparticle distance, L. According to toughening at which a material loses its form-stability and HDT is the
theories,18 L should be below a value, Lc, in order for the temperature at which material loses its load bearing capacity.
rubbery particles to effectively initiate plastic deformation in the However, the difference in assessing the softening point by
surrounding matrix, despite L being directly related to rubber HDT or VST is mainly a matter of defining the “end point”.74
particle size and content. In PLA toughened with POE-g- VST values are usually higher than the HDT values, and the
GMA,23 when the rubber content and particle size were difference is quite modest in the case of PLA, which shows
increased, interparticle distance was reduced. The critical value, HDT of ca. 55 °C and VST of 65 °C. Various techniques and
Lc for effective toughening of the blend was found to be 0.5 methods have been explored to improve the crystallinity and
μm.23 However, there is no unique agreement between heat resistance of PLA. This section reviews the state-of-the art
researchers whether Lc is more important than content and technologies for improving the heat resistance of PLA by (i)
size. If so, the ultimate goal of manipulating the content and addition of nucleating agents and stereocomplex; (ii) adopting
size will be to drive the L below the Lc. On the other hand, different processing strategies; (iii) blending with heat resistant
2905 DOI: 10.1021/acssuschemeng.6b00321
ACS Sustainable Chem. Eng. 2016, 4, 2899−2916
ACS Sustainable Chemistry & Engineering Perspective
polymers; and (iv) fabrication of biocomposites with natural adopted to achieve substantial improvements (results are in
fibers and nanoreinforcements. A summary of PLA blends with Table 2). In spite of the successful enhancement of the
improved HDT/VST is presented in Table 2. crystallization rate of PLA through the addition of nucleating
agents, obtaining injection molded articles of PLA with high
Table 2. PLA Blends with Improved Heat Resistance: crystallinity remains difficult with a fast mold cooling rate.
Summary of Results Nucleated PLA molded in room temperature molds with fast
cooling (>100 °C/min) does not show substantial improve-
PLA blends with improved heat softening point from HDT ment in HDT. Therefore, the effect of performing annealing
resistance and VST reference
postprocessing on the mechanical and thermal properties, and
nucleating agents, stereocomplex the fracture behavior of PLA has been studied. The crystallinity
TMC-328 (0.6%) 134.3 °C (VST, 10N) 72 of PLA has been found to increase consistently through
OMBH (1%) 124 °C (HDT, 0.45 MPa) 84 annealing in most of the studies and the increase lead to an
EBH/talc mixture (1%) 110 °C (HDT, 0.45 MPa) 84 improvement in its heat resistance and overall mechanical
PLLA/PDLA (50/50) blend 150 °C (HDT, 0.45 MPa) 103 performance. Park et al.90 and Nascimento et al.91 performed
PLLA/hPLLA (95/5) no deformation at 70 °C, 105 annealing of PLA under various conditions to obtain micro-
50 g for 5 min
processing strategies
structures with different spherulite sizes and densities. The heat
PLA/1% EBH, 10 min 93 °C (HDT, load not 77
resistance of PLA was markedly improved when its crystallinity
annealing at 105 °C mentioned) was increased by annealing. PLA with 1% EBH molded at room
PLA with NA annealing at 80 HDT, 0.45 MPa temperature and then annealed for 1, 2, 4, 10 and 20 min at 105
°C for 15 min °C showed increasing HDT with increasing annealing time. A
PLA/2% EBS 70 °C 92 sharp step change in HDT was noticed when the crystallinity
PLA/2% talc 77 °C went 25%, indicating a threshold for crystallinity content.77
PLA/talc/PEG (80/10/10) VST, 10N However, annealing adds a postprocessing step, which may not
23 °C epoxy mold 123.6 °C 95 be economical or industrially feasible.
90 °C steel mold 117.9 °C As an alternative to annealing, researchers84,92,93 have looked
blending PLA with heat resistant at increasing the mold temperature during the injection
polymers and nanofillers
molding process. This technique can be called as an in-mold
PLA/POM (60/40) and (50/ ∼72 and 135 °C (HDT, 99
50) 0.45 MPa) annealing process, where the cooling time is increased to
PLA/PHBV/PBS (30/60/ 72.2 and 87.5 °C (HDT, 100 facilitate effective demolding of the samples. Harris and Lee92
10) and (10/60/30) 0.45 MPa) increased the injection mold temperature to 110 °C and were
PLA/organically modified 112 °C (HDT, 0.98 MPa) 108 successful in obtaining PLA molded articles with high
MMT (93/7) percentage of crystallinity and high HDT. However, the
PLA/ OMSFM (96/4) and 92 and 117 °C (HDT, 109 problem with this step is molding cycle time of ∼2 min is
(90/10) 0.98 MPa)
PLA/5% DCPD capsules 78.05 °C (HDT, load not 110 required due to higher cooling time; demolding of the
mentioned) processed components would be difficult with short cooling
cycle. Li and Huneault93 also observed similar effect of mold
Nucleating Agents and Processing Strategies. Nucleat- temperature on crystallinity as shown in Figure 6. At mold
ing agents can effectively promote crystallization by providing
nucleation sites around which the polymer chains can
crystallize. Shorter crystallization half time achieved with the
addition of nucleating agents can help to increase the
crystallinity and shorten the molding cycle time. Nucleating
agents for PLA include, but are not limited to, talc,75,76 N,N′-
ethylene bis-stearamide (EBS),77 carbon nanotubes,78 metal
salts of phenylphosphonic acid,79 multiamide and hydrazide
compounds,80−85 barium sulfate,86 titanium dioxide,86 calcium
carbonate (CaCO3),86 nano-CaCO387 and orotic acid.88
Numerous investigations have been conducted on improving
crystallization of PLA with the help of nucleating agents.
However, only a handful of them corelate the increase in
crystallinity due to nucleation to increase in heat resistance
measured through HDT/VST. Recently, TMC-328, a commer-
cial heterogeneous multiamide nucleating agent, has been
found to enhance greatly the heat resistance of PLA at a very
small concentration (0.2%).72 Benoylhydrazide (BH) com-
pounds, in particular octamethylenedicarboxylic dibenzoylhy-
drazide (OMBH) and decamethylenedicarboxylic dibenzoylhy-
drazide (DMBH), are known to impart enhancement in the Figure 6. Effect of molding temperatures on crystallinity (Xc)
crystallization of PLA.84,89 The nucleation ability (Tc and ΔHc) developed for PLA with 5% acetyl triethyl citrate (ATC) and 1% talc.
of OMBH was found to be higher than that of DMBH, and [Reprinted from Polymer, Vol. 48, H. Li, M. A. Huneualt. Effect of
ethylenebis (12-hydroxystearylamide), EBH/talc mixture at 1 nucleation and plasticization on the crystallization of poly(lactic acid),
wt % loading in PLA.84 In addition to using hydrazide 6855−6866, Copyright 2007, with permission from Elsevier, License
nucleating agent, a high molding temperature of 110 °C was number: 3794330203855.]
temperatures below 50 °C, low crystallinity level was observed, (4032D, Ingeo NatureWorks) and hPLLA helped to keep
and crystallinity reached maximum level at 80 °C mold hPLLA crystallites unmelted at the processing temperature of
temperature with a combination of 5% plasticizer and 1% talc. 170 °C. Presence of 5% hPLLA accelerated PLLA crystal-
In most of the above reviewed works,72,77,84,89 addition of lization at a remarkable rate compared to PLA containing the
nucleating agent in combination with annealing or high same amount of talc and SC PDLA. PLLAs, with and without
temperature molding was helpful in increasing the mechanical
talc and PDLA, were noticed to deform in less than 2 min when
properties. Increase in crystallinity increased the tensile and
flexural modulus. In some cases, increased number of spherulite placed in an oven at 70 °C for 5 min under a constant load of
structures with low spherulite size was believed to consume 50 g, whereas PLLA with hPLLA crystallites showed no visible
more energy and thus increase the impact strength of PLA deformation for 5 min, HDT/VST needs to be measured for
samples containing nucleating agents. any practical comparisons. This work, however, has contributed
On the contrary, Vadori et al.94 have showed increasing the to new ways of tailoring the crystallization of PLLA without
mold temperature of PLA decreases the impact toughness and involving any post processing techniques and more importantly
percentage elongation of high impact PLA. Unique approach of without compromising the biodegradable nature of the
using epoxy based PolyJet mold instead of steel mold for polymer.
conventional injection molding to produce PLA parts with high Incorporation of nanoparticles into PLA is a relatively new
crystallinity has been proposed to offer promising results strategy that researchers are exploring to improve the heat
(Table 2).95 Because of low thermal conductivity of epoxy
resistance of PLA. Although addition of 2 wt % talc to PLA
based PolyJet mold, PLA parts containing nucleating agents
produced from this mold had a significantly higher level of resulted in 3 °C HDT improvement,106 addition of 8 wt %
crystallinity, thermal and mechanical properties compared to montmorillonite (MMT) to PLA increased its HDT by 28
PLA samples molded from steel molds. When PLA is injected °C.107 Layered silicate nanocomposites offer desired improve-
into 23 °C steel mold, it is cooled below its Tg in 15 s due to ment in HDT only when the silicate layers of the clay are
high thermal conductivity of the steel mold, whereas, in PolyJet intercalated, stacked and well distributed in PLA matrix.108,109
mold, PLA material stays above Tg for around 66 s, allowing the Organomodified montmorillonite (OMMT) containing tri-
material to crystallize. As a result, VST of PLA molded in 23 °C methyl octadecyl ammonium cation at 7 wt % increased the
PolyJet mold increased to 118−124 °C compared to VST of HDT of PLA to ∼112 °C,109 10 wt % of organically modified
60−65 °C for PLA samples obtained from 23 °C steel mold. synthetic fluorine mica (OMSFM) increased the HDT of PLA
Use of such PolyJet molds show promise in achieving higher
to ∼117 °C,108 under a deflection load of 0.98 MPa.
levels of crystallinity for PLA at room temperature molding
conditions. Dicyclopentadiene (DCPD) filled urea formaldehyde micro-
Blending with Heat Resistant Polymers, Stereo- capsules added to arrest the crack propagation and promote
complexation, and Use of Nanofillers. Blending PLA self-healing in PLA was observed to act as a nucleating agent.110
with heat resistant engineering polymers such as polycarbon- Formation of stable cocontinuous morphologies of heat
ate,96 poly(acrylonitrile−butadiene−styrene),97 nylon,98 poly- resistant polymer with the aid of well intercalated nanoparticle
oxymethylene99 can improve the HDT of PLA when there is is a recently explored promising strategy to increase the
good compatibility between the blending polymers. Biodegrad- crystallinity. PLA phase interpenetrated with a continuous
able ternary blends of PLA, PHBV and PBS with balanced framework of nylon (30 wt %) and 3 phr OMMT showed
stiffness and toughness attained HDT of ∼72 °C with 30 wt % resistance to temperature up to ∼160 °C (Figure 7); however,
PLA in the blend.100 Polyoxymethylene, POM, has a high HDT
the HDT at 0.25 mm was the same as that of neat PLA.98
of 160 °C and it crystallizes fast with 70−80% crystallinity
content.99 Nonetheless, having POM as a dispersed phase in
PLA did not help in improving the HDT; to achieve desired
improvements in HDT, POM should be the major phase in the
blend as significant improvements were observed with phase
inversion, beyond 40%.99 Two different monomers, D-lactide
and L-lactide, exist due to chirality of PLA. Homopolymers of D-
and L-lactide (PDLA and PLLA) have faster crystallization and
higher melting points compared to common PLA, which has a
small percentage of D-lactide with atactic stereoregularity in a
majority of L-lactide. A stereocomplex of two polymers with
same structure but different configuration has a melting
temperature between 190 and 230 °C. Stereocomplex (SC)
PLA can work as a nucleating agent promoting the formation of
ordered structures. Various mixtures of PLLA and PDLA have Figure 7. (a) Sample deflection recorded during creep tests for the
been investigated101−104 and 50−50 blend with stereocomplex sample PLA (squares), PA11 (diamonds), PLA70 (circles) and
crystalline structure improved the HDT to 150 °C. Never- PLA70-C3 (triangles). The pictures show the samples PLA70 (b)
and PLA70-C3 (c) at the end of the test, which is after the
theless, the high cost of PDLA is a bottleneck to stereo-
temperature had reached ≈160 °C. [Reprinted from Macromolecular
complexation due to difficulty in production of D-lactide and Materials and Engineering, Vol. 299, A. Nuzzo, S. Coiai, S. C.
hence PDLA. In a recent publication, Yin et al.105 used high Carroccio, N. Dintcheva, C. Gambarotti, G. Flippone. Heat resistant
melting point PLLA homocrystallites (hPLLA) as a nucleating fully biobased nanocomposite blends based on poly(lactic acid), 31−
agent to improve the thermomechanical properties of PLA. 40, Copyright 2013, with permission from Elsevier, License number:
About a 20 °C difference in melting point between PLA 3794371367676.]
■
ability to bind active groups of the polymer.127 Chemical
interactions formed between hydroxyl, silanyl and alkoxy
PLA BIOCOMPOSITES: THE QUEST CONTINUES groups increased the impact strength of the PLA−PBAT
FOR HIGH PERFORMANCE biocomposites by 22%.127 By treating ramie fiber with silane
A biocomposite is a multiphase system, where plant-derived coupling agent (KH550) for in situ polymerized PLLA−PCL
fiber or mineral/synthetic filler is dispersed in the biopolymer matrix, tensile and impact strength increased from 12.14 MPa,
matrix; either the matrix or the reinforcement phase is 30.0 J/m to 23.45 MPa, and 88.9 J/m, respectively.128
biobased.118,119 Toughened PLA biocomposites have a far Incorporation of Cordenka fiber at 25 wt % has been shown
greater potential for minimizing the limitations of PLA, hence to triple the impact strength of PLA without any tough
major research efforts are being taken to develop and component being present; however, more research is needed
commercialize them. Numerous research works have been toward the effect of this fiber on HDT.129 Although addition of
conducted in the field of PLA composites; however, most of the 5 wt % lignin resulted in toughness improvement in PLLA130
works report only marginal improvements in impact strength from 8.2 to 12.5 kJ/m2, addition of 5 wt % of lignin-g-rubber-g-
and HDT.120−125 The scope of this section has been limited to PDLA to PLLA exhibited a 7-fold enhancement in toughness
reviewing the research progress in injection molded PLA (from stress−strain curves) compared with neat PLLA. This
2908 DOI: 10.1021/acssuschemeng.6b00321
ACS Sustainable Chem. Eng. 2016, 4, 2899−2916
ACS Sustainable Chemistry & Engineering Perspective
improvement is significant considering the copolymer contains Stiffness and HDT of the PLA were improved with the
only 3.8 wt % of rubber.131 In the case of PLA/pine wood floor addition of newspaper fibers/talc hybrid with drastic reduction
composites, notched Charpy impact strength was found to to impact strength.153,154 HDT of the PP−PLA composites
increase gradually with increase in addition of wood floor and could be increased to 120 °C with 30% Oat hull but in a major
further increment in impact strength was achieved by phase of PP, with a drastic reduction in impact strength.155
toughening the PLA matrix with styrene−butadiene−styrene Incorporating 30 wt % agricultural residues like soy stalk, corn
(SBS) block copolymer.132 Use of reactive impact modifiers can stalk, wheat straw and their hybrids in PLA matrix did not
form ductile interface between PLA and fiber, thus increasing provide a desired increase in HDT. Only the modulus of the
the resultant properties. With this hypothesis, ethylene acrylate composites increased while impact strength remained essen-
copolymer (Biomax) was used as an impact modifier (IM) for tially the same as virgin or neat PLA.156 In such cases, addition
PLA/kenaf fiber (KF) composites.133 Impact strength and of fibers alone would not be sufficient to increase the HDT, a
elongation at break increased, but only at a high loading level of combinatorial approach of adding fibers, and use of high mold
40 wt % coupled with substantial reduction in tensile strength temperature could be beneficial.
and modulus. Liu et al.134 compared the toughening effect of By taking super toughened PLA blend developed based on
three different reactive elastomers: polyoxyethylene grafted PEBA and EMAGMA 25 as the matrix material, such
with maleic anhydride (POE-g-MAH), ethylene−propylene− combination of approaches have proved to be successful in
diene rubber grafted with maleic anhydride (EPDM-g-MAH) achieving concurrent improvement in impact strength and
and ethylene−acrylate−glycidyl methacrylate copolymer HDT of PLA biocomposites.157 Although the impact strength
(EAGMA) on PLA/basalt fiber composites. EAGMA at 20 reduced as expected with addition of 10 wt % miscanthus, it
wt % imparted the most toughening effect by recording a value was still considerably higher than the neat PLA matrix,
of 33.7 KJ/m2 for unnotched charpy impact strength.134 Other exhibiting 120 J/m (Figure 9). A high mold temperature of
mineral fillers such as barium sulfate135 and calcium
sulfate136,137 have also been reported to increase the toughness
of the PLA composites. PLA based nanocomposites prepared
by incorporation of nanofillers such as cellulose nanofibers and
nanowhikers,138 nanocalcium carbonate,139−141 nano- and
mesoporous silica,142−145 halloysite nanotubes,146,147 nano-
clay147−150 and titanium oxide nanoparticles151 exhibited
good improvement in toughness, mechanical and barrier
properties. However, none of these studies have reported the
heat resistance of the developed materials. Although the
hybridization of PLA with impact modifier and nanoparticle
can offer a toughened composite material, challenges exist in
achieving good level of dispersion and distribution of the
nanoparticles, its compatibility with the matrix and ease of
processing.
On the flip side, a considerable number of research Figure 9. Impact strength and HDT of PLA biocomposites with and
investigations have shown the heat resistance of injection without nucleating agent (NA) molded at different mold temperatures
and injection cycle times. PLA blend/MS (90/10) at (A) 30 °C, 30 s;
molded PLA biocomposites to increase with fiber/filler
(B) 110 °C, 60 s. PLA blend/MS/NA (89/10/1) at (C) 30 °C, 30 s;
incorporation in spite of affecting impact strength negatively. (D) 60 °C, 60 s; (E) 90 °C, 60 s; (F) 110 °C, 60 s; (G) 120 °C, 60 s.
Crushed Kenaf fiber152 has been reported to significantly [Reprinted with permission from ACS Applied Materials and
increase the HDT of injection molded PLA composites when Interfaces, Vol. 7, V. Nagarajan, K. Zhang, M. Misra, A. K. Mohanty.
added beyond 10 wt %, as shown in Figure 8. Overcoming the Fundamental Challenges in Improving the Impact
Strength and Crystallinity of PLA Biocomposites: Influence of
Nucleating Agent and Mold Temperature, 11203−11214, Copyright
2015, American Chemical Society.]
Table 4. Commercial Toughened and/or Heat Resistant PLA Formulations for Durable End Use Applications
tensile
HDT at 0.45 MPa strength
company grade impact strength (°C) (MPa) comment reference
RTP Co. RTP 2099 X Series 694−854 J/m 96−124 48−52 PLA−PC blends 111
(notched Izod)
43−187 J/m 91−160 38−114 PLA with glass fibers or talc
(notched Izod)
PolyOne reSound FR 620 J/m (notched 112 PLA−engineering plastic blend 112, 158
Corporation Izod)
Kingfa Sci & Tech Ecopond AFR-97 55 kJ/m2 (notched 84 (1.82 MPa) 52 PLA−PC and PLA−ABS blends, >40% 113
Co., Ltd. Izod) biobased
UGM ABS Ltd. ECO PELLET LA Series 12−27 kJ/m2 78−92 48−58 PLA−PC and PLA−ABS blends 114
(notched Charpy)
Interfacial deTerra XP698 880 J/m (notched 38 PLA blend, compostable, >85% 159
Solutions Charpy) biobased
Teknor Apex Terraloy 3D-40040 Series 267 J/m (unnotched 75 PLA blend, extrusion filament for use in 160
Company Inc. Izod) 3D printers
Corbion Carbion Purac 5−23 kJ/m2 (notched 85−120 30−45 PLLA/PDLA blends with and without 161
(development grades) Charpy) talc
Sukano Polymers Sukano Bioloy 003, 004 60−70 kJ/m2 50−90 35−50 PLA blend, compostable (EN13432), 162
NC001 (unnotched 35−97% biobased
Charpy)
Toray Industries ECODEAR V751X53, 21−24 kJ/m2 81 49−52 PLA blend 163
Inc. V751X52 (notched Charpy)
Unitika Ltd. Terramac TE 7000, 7307, 2.0−4.0 kJ/m2 110−140 50−70 compostable (ISO 14855) 164
7300, 8210, 8300 (notched Charpy)
NatureWorks Ingeo 3100HP, 3260HP 16−32 J/m (notched 149−151 63−65 PLA with nucleating agent, mold 165
LLC Izod) temperature of 120 °C
Supla Co., Ltd. SUPLA 135 150 PLA blend (90% PLA) 166
SK Chemicals Ecoplan-Dura 40 J/m (notched 100 42 compostable, 80−100% biobased 167
Izod)
FKuR Plastics Bio-Flex F 6513 3 kJ/m2 (notched 68−130 32 PLA blend, HDT of up to 130 °C by 168
Charpy) appropriate processing
NaturePlast PLI 013, PLE 013, high 89 kJ/m2 (unnotched 123−133 injection and extrusion grades 169
temperature Charpy)
Barlog Plastics KEBACOMP FE 120204 5 kJ/m2 (notched 100 compostable (ISO 13432) 170
Izod)
EcolBiotech EcolGreen EGP Series 382−477 J/m 62−72 31.7−45.5 nanocomposite with 12 different 171
Co.,Ltd. (unnotched Izod) additives, compostable
GEHR Plastics ECOGEHR PLA-L 59.8 kJ/m2 (notched 58.4 (VST) 49.5 PLA blend with lignin and fatty acid, 172
Izod) compostable, >80% biobased
WinGram Ecoplant HRS heat resistance up compostable (ISO 14855) 173
Industrial Co to 120 °C
Ltd.
Teijin Ltd. Biofront grade J20, J201, highly heat stereocomplex PLA melting point of 210 174
L201 resistant °C
of green chemistry, sustainability and engineering are being blends. Recent explorations have revealed that a unique
integrated in the R&D to achieve a good balance of product network-like or cocontinuous morphology unevenly distributed
performance and environmental friendliness. Extensive research in the matrix to exhibits much better super toughening
effort has been devoted to developing PLA blends and compared to the common sea-island morphology containing
biocomposites with desirable morphology and crystallinity for well dispersed spherical elastomer particles in a polymer matrix.
durable applications. However, achieving feasible and econom- The network-like distribution of the elastomer particles can
ical manufacturing processes for mass production of such facilitate the percolation of the stress field as the plastic
materials has been quite a challenge. Enhancing matrix deformation of the matrix around them at lower content.
crystallization has been reported to be an effective strategy Adding inorganic nanoparticles with strong self-networking
toward creating heat resistant PLA blends. Both thermal capability in polymer melts has been shown to assist in the
annealing and nucleating agent induced matrix crystallization transition of morphology from immiscible sea-island structure
could significantly enhance heat resistance of the blends, while to the network-like, cocontinuous structure.
maintaining or further increasing the toughening efficiency. Approach of adding nucleating agents and natural fiber in
However, increasing matrix crystallinity alone cannot guarantee combination with a high molding temperature to a super
toughness improvement in most cases because suitable toughened PLA blend has resulted in composites with
morphology must be obtained for PLA matrix to undergo concurrent improvements in both the impact strength and
plastic deformation. Specifically, optimum elastomer content, HDT. Epoxy based mold with low thermal conductivity has
particle size and interparticle distance are identified to be the demonstrated significant advantages over conventional steel
most important deciding factors for toughening PLA. Reactive molds. Future work is needed to shed light on the effect of
compatibilization along with dynamic vulcanization techniques applying an intense shear flow field through oscillation shear
have been shown to tailor successfully the morphology of the injection molding (OSIM) to trigger dramatic enhancement of
2910 DOI: 10.1021/acssuschemeng.6b00321
ACS Sustainable Chem. Eng. 2016, 4, 2899−2916
ACS Sustainable Chemistry & Engineering Perspective
■ AUTHOR INFORMATION
Corresponding Author
including the “Andrew Chase Forest Product Award” from the
American Institute of Chemical Engineers and most recently the
“Lifetime Achievement Award”, from the BioEnvironmental Polymer
Society (BEPS) in the year 2015. Dr. Mohanty holds the Alexander
*A. K. Mohanty. E-mail address: mohanty@uoguelph.ca. Tel.:
von Humboldt Fellowship at the Technical University, Berlin. His
+1-519-824-4120 ext. 56664. Fax: +1-519-763-8933
ResearchGate score is 44.43, higher than 97.5% of the 7 million
Notes ResearchGate members. His research impact resulted in 16 962
The authors declare no competing financial interest. citations with h-index of 62 (Google Scholar, as of April 2016).
■
poly(butylene succinate) blend composites by using isocyanate as a
reactive processing agent. J. Appl. Polym. Sci. 2007, 106 (3), 1813−
ACKNOWLEDGMENTS 1820.
(21) Oyama, H. T. Super-tough poly(lactic acid) materials: Reactive
We gratefully acknowledge the financial support from (1) the
blending with ethylene copolymer. Polymer 2009, 50 (3), 747−751.
Ontario Ministry of Agriculture, Food, and Rural Affairs (22) Su, Z.; Li, Q.; Liu, Y.; Hu, G.; Wu, C. Compatibility and phase
(OMAFRA)- University of Guelph Bioeconomy-Industrial structure of binary blends of poly(lactic acid) and glycidyl
Uses Theme (Project # 200425); (2) the Ontario Ministry of methacrylate grafted poly(ethylene octane). Eur. Polym. J. 2009, 45
Economic Development and Innovation (MEDI), Ontario (8), 2428−2433.
Research Fund, Research Excellence Round 4 program (ORF- (23) Feng, Y.; Hu, Y.; Yin, J.; Zhao, G.; Jiang, W. High impact
RE04) (Project # 050231 and 050289); and (3) the Natural poly(lactic acid)/poly(ethylene octene) blends prepared by reactive
Sciences and Engineering Research Council (NSERC) Canada blending. Polym. Eng. Sci. 2013, 53 (2), 389−396.
Discovery Grants (Project # 400322) and Networks of Centres (24) Han, L.; Han, C.; Dong, L. Morphology and properties of the
of Excellence (NCE) AUTO21 Program (Project # 460372). biosourced poly(lactic acid)/poly(ethylene oxide-b-amide-12) blends.
■
Polym. Compos. 2013, 34 (1), 122−130.
(25) Zhang, K.; Nagarajan, V.; Misra, M.; Mohanty, A. K.
REFERENCES Supertoughened Renewable PLA Reactive Multiphase Blends System:
(1) Drumright, R. E.; Gruber, P. R.; Henton, D. E. Polylactic acid Phase Morphology and Performance. ACS Appl. Mater. Interfaces 2014,
technology. Adv. Mater. 2000, 12 (23), 1841−1846. 6 (15), 12436−12448.
(2) Auras, R.; Harte, B.; Selke, S. An overview of polylactides as (26) Vachon, A.; Pépin, K.; Béland, O.; Monfette, W. G.; Rochette,
packaging materials. Macromol. Biosci. 2004, 4 (9), 835−864. A.; Vuillaume, P. Y. Thermal, Mechanical and Morphological
(3) Bioplastics facts and figures. http://docs.european-bioplastics. Properties of Binary and Ternary PLA Blends Containing a Poly(ether
org/2016/publications/EUBP_facts_and_figures.pdf (accessed Janu- ester) Elastomer. J. Biobased Mater. Bioenergy 2015, 9 (2), 205−217.
ary 2016). (27) Zhou, L.; Zhao, G.; Feng, Y.; Yin, J.; Jiang, W. Toughening
(4) Kyoto Protocol. http://unfccc.int/kyoto_protocol/items/2830. polylactide with polyether-block-amide and thermoplastic starch
php (accessed December 30, 2016). acetate: Influence of starch esterification degree. Carbohydr. Polym.
(5) As Kyoto Protocol turns 10, UN says ‘first critical step’ must 2015, 127 (2015), 79−85.
trigger new 2015 emissions-curbing deal. http://www.un.org/apps/ (28) Ojijo, V.; Ray, S. S.; Sadiku, R. Toughening of biodegradable
news/story.asp?NewsID=50099#.Vw-FMtL2Y3E (accessed December polylactide/poly(butylene succinate-co-adipate) blends via in situ
30, 2015). reactive compatibilization. ACS Appl. Mater. Interfaces 2013, 5 (10),
(6) United Nations conference on climate change. http://www. 4266−4276.
cop21.gouv.fr/en/ (accessed December 30, 2015). (29) Ojijo, V.; Ray, S. S. Super toughened biodegradable polylactide
(7) Kuzuhara, Y. Biomass Nippon StrategyWhy “Biomass Nippon” blends with non-linear copolymer interfacial architecture obtained via
now? Biomass Bioenergy 2005, 29 (5), 331−335. facile in-situ reactive compatibilization. Polymer 2015, 80, 1−17.
(30) Dong, W.; Zou, B.; Yan, Y.; Ma, P.; Chen, M. Effect of Chain- (49) Chen, Y.; Yuan, D.; Xu, C. Dynamically vulcanized biobased
Extenders on the Properties and Hydrolytic Degradation Behavior of polylactide/natural rubber blend material with continuous cross-linked
the Poly(lactide)/Poly(butylene adipate-co-terephthalate) Blends. Int. rubber phase. ACS Appl. Mater. Interfaces 2014, 6 (6), 3811−3816.
J. Mol. Sci. 2013, 14 (10), 20189−20203. (50) Wang, Y.; Chen, K.; Xu, C.; Chen, Y. Supertoughened Biobased
(31) Meng, B.; Deng, J.; Liu, Q.; Wu, Z.; Yang, W. Transparent and Poly(lactic acid)−Epoxidized Natural Rubber Thermoplastic Vulcan-
ductile poly(lactic acid)/poly(butyl acrylate) (PBA) blends: structure izates: Fabrication, Co-continuous Phase Structure, Interfacial in Situ
and properties. Eur. Polym. J. 2012, 48 (1), 127−135. Compatibilization, and Toughening Mechanism. J. Phys. Chem. B
(32) Zhang, G.; Zhang, J.; Wang, S.; Shen, D. Miscibility and phase 2015, 119 (36), 12138−12146.
structure of binary blends of polylactide and poly(methyl meth- (51) Yuan, D.; Xu, C.; Chen, Z.; Chen, Y. Crosslinked bicontinuous
acrylate). J. Polym. Sci., Part B: Polym. Phys. 2003, 41 (1), 23−30. biobased polylactide/natural rubber materials: Super toughness,“net-
(33) Ye, S.; Ting Lin, T.; Weei Tjiu, W.; Kwan Wong, P.; He, C. like”-structure of NR phase and excellent interfacial adhesion. Polym.
Rubber toughening of poly(lactic acid): Effect of stereocomplex Test. 2014, 38, 73−80.
formation at the rubber-matrix interface. J. Appl. Polym. Sci. 2013, 128 (52) Yuan, D.; Chen, Z.; Xu, C.; Chen, K.; Chen, Y. Fully Biobased
(4), 2541−2547. Shape Memory Material Based on Novel Cocontinuous Structure in
(34) Zhang, H.; Liu, N.; Ran, X.; Han, C.; Han, L.; Zhuang, Y.; Dong, Poly(Lactic Acid)/Natural Rubber TPVs Fabricated via Peroxide-
L. Toughening of polylactide by melt blending with methyl Induced Dynamic Vulcanization and in Situ Interfacial Compatibiliza-
methacrylate−butadiene−styrene copolymer. J. Appl. Polym. Sci. tion. ACS Sustainable Chem. Eng. 2015, 3 (11), 2856−2865.
2012, 125 (S2), E550−E561. (53) Liu, G.; He, Y.; Zeng, J.; Li, Q.; Wang, Y. Fully biobased and
(35) Sun, S.; Zhang, M.; Zhang, H.; Zhang, X. Polylactide toughening supertough polylactide-based thermoplastic vulcanizates fabricated by
with epoxy-functionalized grafted acrylonitrile−butadiene−styrene peroxide-induced dynamic vulcanization and interfacial compatibiliza-
particles. J. Appl. Polym. Sci. 2011, 122 (5), 2992−2999. tion. Biomacromolecules 2014, 15 (11), 4260−4271.
(36) Song, X.; Chen, Y.; Xu, Y.; Wang, C. Study on Tough Blends of (54) Kang, H.; Hu, X.; Li, M.; Zhang, L.; Wu, Y.; Ning, N.; Tian, M.
Polylactide and Acrylic Impact Modifier. BioResources 2014, 9 (2), Novel biobased thermoplastic elastomer consisting of synthetic
1939−1952. polyester elastomer and polylactide by in situ dynamical crosslinking
(37) Li, W.; Zhang, Y.; Wu, D.; Li, Z.; Zhang, H.; Dong, L.; Sun, S.;
method. RSC Adv. 2015, 5 (30), 23498−23507.
Deng, Y.; Zhang, H. The Effect of Core−Shell Ratio of Acrylic Impact (55) Ma, P.; Xu, P.; Liu, W.; Zhai, Y.; Dong, W.; Zhang, Y.; Chen, M.
Modifier on Toughening PLA. Adv. Polym. Technol. 2015, DOI: Bio-based poly(lactide)/ethylene-co-vinyl acetate thermoplastic vul-
10.1002/adv.21632.
canizates by dynamic crosslinking: structure vs. property. RSC Adv.
(38) Kfoury, G.; Raquez, J.; Hassouna, F.; Leclère, P.; Toniazzo, V.;
2015, 5 (21), 15962−15968.
Ruch, D.; Dubois, P. Toughening of poly(lactide) using polyethylene
(56) Zhao, Q.; Ding, Y.; Yang, B.; Ning, N.; Fu, Q. Highly efficient
glycol methyl ether acrylate: Reactive versus physical blending. Polym.
toughening effect of ultrafine full-vulcanized powdered rubber on
Eng. Sci. 2015, 55 (6), 1408−1419.
poly(lactic acid) (PLA). Polym. Test. 2013, 32 (2), 299−305.
(39) Ge, X.; George, S.; Law, S.; Sain, M. Mechanical properties and
(57) Joziasse, C.; Topp, M.; Veenstra, H.; Grijpma, D.; Pennings, A.
morphology of polylactide composites with acrylic impact modifier. J.
Supertough poly(lactide) s. Polym. Bull. 1994, 33 (5), 599−605.
Macromol. Sci., Part B: Phys. 2011, 50 (11), 2070−2083.
(58) Odent, J.; Leclère, P.; Raquez, J.; Dubois, P. Toughening of
(40) Liang, H.; Hao, Y.; Bian, J.; Zhang, H.; Dong, L.; Zhang, H.
polylactide by tailoring phase-morphology with P [CL-co-LA] random
Assessment of miscibility, crystallization behaviors, and toughening
mechanism of polylactide/acrylate copolymer blends. Polym. Eng. Sci. copolyesters as biodegradable impact modifiers. Eur. Polym. J. 2013, 49
2015, 55 (2), 386−396. (4), 914−922.
(41) Taib, R.; Ghaleb, Z.; Mohd Ishak, Z. Thermal, mechanical, and (59) Odent, J.; Raquez, J.; Duquesne, E.; Dubois, P. Random
morphological properties of polylactic acid toughened with an impact aliphatic copolyesters as new biodegradable impact modifiers for
modifier. J. Appl. Polym. Sci. 2012, 123 (5), 2715−2725. polylactide materials. Eur. Polym. J. 2012, 48 (2), 331−340.
(42) Liu, H.; Chen, F.; Liu, B.; Estep, G.; Zhang, J. Super toughened (60) Odent, J.; Habibi, Y.; Raquez, J.; Dubois, P. Ultra-tough
poly(lactic acid) ternary blends by simultaneous dynamic vulcanization polylactide-based materials synergistically designed in the presence of
and interfacial compatibilization. Macromolecules 2010, 43 (14), 6058− rubbery ε-caprolactone-based copolyester and silica nanoparticles.
6066. Compos. Sci. Technol. 2013, 84, 86−91.
(43) Liu, H.; Song, W.; Chen, F.; Guo, L.; Zhang, J. Interaction of (61) Li, X.; Kang, H.; Shen, J.; Zhang, L.; Nishi, T.; Ito, K.; Zhao, C.;
microstructure and interfacial adhesion on impact performance of Coates, P. Highly toughened polylactide with novel sliding graft
polylactide (PLA) ternary blends. Macromolecules 2011, 44 (6), 1513− copolymer by in situ reactive compatibilization, crosslinking and chain
1522. extension. Polymer 2014, 55 (16), 4313−4323.
(44) Liu, H.; Guo, L.; Guo, X.; Zhang, J. Effects of reactive blending (62) Li, Y.; Shimizu, H. Toughening of polylactide by melt blending
temperature on impact toughness of poly(lactic acid) ternary blends. with a biodegradable poly(ether) urethane elastomer. Macromol. Biosci.
Polymer 2012, 53 (2), 272−276. 2007, 7 (7), 921−928.
(45) Liu, H.; Guo, X.; Song, W.; Zhang, J. Effects of metal ion type (63) Liu, G.; He, Y.; Zeng, J.; Xu, Y.; Wang, Y. In situ formed
on ionomer-assisted reactive toughening of poly(lactic acid). Ind. Eng. crosslinked polyurethane toughened polylactide. Polym. Chem. 2014, 5
Chem. Res. 2013, 52 (13), 4787−4793. (7), 2530−2539.
(46) Song, W.; Liu, H.; Chen, F.; Zhang, J. Effects of ionomer (64) Liu, Z.; Luo, Y.; Bai, H.; Zhang, Q.; Fu, Q. Remarkably
characteristics on reactions and properties of poly(lactic acid) ternary enhanced impact toughness and heat resistance of poly(L-lactide)/
blends prepared by reactive blending. Polymer 2012, 53 (12), 2476− thermoplastic polyurethane blends by constructing stereocomplex
2484. crystallites in the matrix. ACS Sustainable Chem. Eng. 2016, 4 (1),
(47) Lu, X.; Wei, X.; Huang, J.; Yang, L.; Zhang, G.; He, G.; Wang, 111−120.
M.; Qu, J. Supertoughened Poly(lactic acid)/Polyurethane Blend (65) Ma, P.; Hristova-Bogaerds, D.; Goossens, J.; Spoelstra, A.;
Material by in Situ Reactive Interfacial Compatibilization via Dynamic Zhang, Y.; Lemstra, P. Toughening of poly(lactic acid) by ethylene-co-
Vulcanization. Ind. Eng. Chem. Res. 2014, 53 (44), 17386−17393. vinyl acetate copolymer with different vinyl acetate contents. Eur.
(48) Fang, H.; Jiang, F.; Wu, Q.; Ding, Y.; Wang, Z. Supertough Polym. J. 2012, 48 (1), 146−154.
Polylactide Materials Prepared through In Situ Reactive Blending with (66) Likittanaprasong, N.; Seadan, M.; Suttiruengwong, S. Impact
PEG-Based Diacrylate Monomer. ACS Appl. Mater. Interfaces 2014, 6 property enhancement of poly(lactic acid) with different flexible
(16), 13552−13563. copolymers. IOP Conf. Ser.: Mater. Sci. Eng. 2015, 87, 012069.
(67) Schindler, A.; Harper, D. Polylactide. II. Viscosity−molecular (88) Qiu, Z.; Li, Z. Effect of orotic acid on the crystallization kinetics
weight relationships and unperturbed chain dimensions. J. Polym. Sci., and morphology of biodegradable poly(L-lactide) as an efficient
Polym. Chem. Ed. 1979, 17 (8), 2593−2599. nucleating agent. Ind. Eng. Chem. Res. 2011, 50 (21), 12299−12303.
(68) Chen, T. K.; Jan, Y. H. Fracture mechanism of toughened epoxy (89) Kawamoto, N.; Sakai, A.; Horikoshi, T.; Urushihara, T.; Tobita,
resin with bimodal rubber-particle size distribution. J. Mater. Sci. 1992, E. Nucleating agent for poly(L-lactic acid)An optimization of
27, 111−121. chemical structure of hydrazide compound for advanced nucleation
(69) Bagheri, R.; Williams, M.; Pearson, R. Use of surface modified ability. J. Appl. Polym. Sci. 2007, 103 (1), 198−203.
recycled rubber particles for toughening of epoxy polymers. Polym. (90) Park, S. D.; Todo, M.; Arakawa, K.; Koganemaru, M. Effect of
Eng. Sci. 1997, 37 (2), 245−251. crystallinity and loading-rate on mode I fracture behavior of poly(lactic
(70) Ma, Q.; Georgiev, G.; Cebe, P. Constraints in semicrystalline acid). Polymer 2006, 47 (4), 1357−1363.
polymers: Using quasi-isothermal analysis to investigate the mecha- (91) Nascimento, L.; Gamez-Perez, J.; Santana, O.; Velasco, J. I.;
nisms of formation and loss of the rigid amorphous fraction. Polymer Maspoch, M. L.; Franco-Urquiza, E. Effect of the recycling and
2011, 52 (20), 4562−4570. annealing on the mechanical and fracture properties of poly(lactic
(71) Arnoult, M.; Dargent, E.; Mano, J. Mobile amorphous phase acid). J. Polym. Environ. 2010, 18 (4), 654−660.
fragility in semi-crystalline polymers: Comparison of PET and PLLA. (92) Harris, A. M.; Lee, E. C. Improving mechanical performance of
injection molded PLA by controlling crystallinity. J. Appl. Polym. Sci.
Polymer 2007, 48 (4), 1012−1019.
2008, 107 (4), 2246−2255.
(72) Wang, L.; Wang, Y.; Huang, Z.; Weng, Y. Heat resistance,
(93) Li, H.; Huneault, M. A. Effect of nucleation and plasticization on
crystallization behavior, and mechanical properties of polylactide/
the crystallization of poly(lactic acid). Polymer 2007, 48 (23), 6855−
nucleating agent composites. Mater. Eng. 2015, 66, 7−15. 6866.
(73) Biron, M. Thermoplastics and thermoplastic composites; Elsevier: (94) Vadori, R.; Mohanty, A. K.; Misra, M. The Effect of Mold
Amsterdam, 2012. Temperature on the Performance of Injection Molded Poly(lactic
(74) Brydson, J. A. Plastic Materials, 7 ed.; Butterworth-Heinemann: acid)-Based Bioplastic. Macromol. Mater. Eng. 2013, 298 (9), 981−990.
Oxford, 2000. (95) Tábi, T.; Kovács, N.; Sajó, I.; Czigány, T.; Hajba, S.; Kovács, J.
(75) Yu, F.; Liu, T.; Zhao, X.; Yu, X.; Lu, A.; Wang, J. Effects of talc Comparison of thermal, mechanical and thermomechanical properties
on the mechanical and thermal properties of polylactide. J. Appl. Polym. of poly(lactic acid) injection-molded into epoxy-based Rapid
Sci. 2012, 125 (S2), E99−E109. Prototyped (PolyJet) and conventional steel mold. J. Therm. Anal.
(76) Tsuji, H.; Takai, H.; Fukuda, N.; Takikawa, H. Non-Isothermal Calorim. 2016, 123 (1), 349−361.
Crystallization Behavior of Poly(L-lactic acid) in the Presence of (96) Hashima, K.; Nishitsuji, S.; Inoue, T. Structure-properties of
Various Additives. Macromol. Mater. Eng. 2006, 291 (4), 325−335. super-tough PLA alloy with excellent heat resistance. Polymer 2010, 51
(77) Tang, Z.; Zhang, C.; Liu, X.; Zhu, J. The crystallization behavior (17), 3934−3939.
and mechanical properties of polylactic acid in the presence of a crystal (97) Vadori, R. Bio-Acrylonitrile Butadiene Styrene (ABS): Creating
nucleating agent. J. Appl. Polym. Sci. 2012, 125 (2), 1108−1115. a New Green Polymer through Melt Blending. MASc, University of
(78) Barrau, S.; Vanmansart, C.; Moreau, M.; Addad, A.; Stoclet, G.; Guelph, Guelph, ON, 2012.
Lefebvre, J.; Seguela, R. Crystallization behavior of carbon nanotube− (98) Nuzzo, A.; Coiai, S.; Carroccio, S. C.; Dintcheva, N. T.;
polylactide nanocomposites. Macromolecules 2011, 44 (16), 6496− Gambarotti, C.; Filippone, G. Heat-Resistant Fully Bio-Based
6502. Nanocomposite Blends Based on Poly(lactic acid). Macromol. Mater.
(79) Han, Q.; Wang, Y.; Shao, C.; Zheng, G.; Li, Q.; Shen, C. Eng. 2014, 299 (1), 31−40.
Nonisothermal crystallization kinetics of biodegradable poly(lactic (99) Guo, X.; Zhang, J.; Huang, J. Poly(lactic acid)/polyoxy-
acid)/zinc phenylphosphonate composites. J. Compos. Mater. 2014, 48 methylene blends: Morphology, crystallization, rheology, and thermal
(22), 2737−2746. mechanical properties. Polymer 2015, 69, 103−109.
(80) Bai, H.; Zhang, W.; Deng, H.; Zhang, Q.; Fu, Q. Control of (100) Zhang, K.; Mohanty, A. K.; Misra, M. Fully biodegradable and
crystal morphology in poly(L-lactide) by adding nucleating agent. biorenewable ternary blends from polylactide, poly(3-hydroxybutyrate-
Macromolecules 2011, 44 (6), 1233−1237. co-hydroxyvalerate) and poly(butylene succinate) with balanced
(81) Song, P.; Wei, Z.; Liang, J.; Chen, G.; Zhang, W. Crystallization properties. ACS Appl. Mater. Interfaces 2012, 4 (6), 3091−3101.
behavior and nucleation analysis of poly(l-lactic acid) with a (101) Anderson, K. S.; Hillmyer, M. A. Melt preparation and
multiamide nucleating agent. Polym. Eng. Sci. 2012, 52 (5), 1058− nucleation efficiency of polylactide stereocomplex crystallites. Polymer
1068. 2006, 47 (6), 2030−2035.
(82) Gui, Z.; Lu, C.; Cheng, S. Comparison of the effects of (102) Rahman, N.; Kawai, T.; Matsuba, G.; Nishida, K.; Kanaya, T.;
commercial nucleation agents on the crystallization and melting Watanabe, H.; Okamoto, H.; Kato, M.; Usuki, A.; Matsuda, M.;
Nakajima, K.; Honma, N. Effect of polylactide stereocomplex on the
behaviour of polylactide. Polym. Test. 2013, 32 (1), 15−21.
crystallization behavior of poly(L-lactic acid). Macromolecules 2009, 42
(83) Xu, T.; Wang, Y.; Han, Q.; He, D.; Li, Q.; Shen, C.
(13), 4739−4745.
Nonisothermal crystallization kinetics of poly(lactic acid) nucleated
(103) Laske, S.; Ziegler, W.; Kainer, M.; Wuerfel, J.; Holzer, C.
with a multiamide nucleating agent. J. Macromol. Sci., Part B: Phys. Enhancing the temperature stability of PLA by compounding
2014, 53 (10), 1680−1694. strategies. Polym. Eng. Sci. 2015, 55 (12), 2849−2858.
(84) Kawamoto, N.; Sakai, A.; Horikoshi, T.; Urushihara, T.; Tobita, (104) Bai, H.; Bai, D.; Xiu, H.; Liu, H.; Zhang, Q.; Wang, K.; Deng,
E. Physical and mechanical properties of poly(l-lactic acid) nucleated H.; Chen, F.; Fu, Q.; Chiu, F. Towards high-performance poly(l-
by dibenzoylhydrazide compound. J. Appl. Polym. Sci. 2007, 103 (1), lactide)/elastomer blends with tunable interfacial adhesion and matrix
244−250. crystallization via constructing stereocomplex crystallites at the
(85) Xu, T.; Zhang, A.; Zhao, Y.; Han, Z.; Xue, L. Crystallization interface. RSC Adv. 2014, 4 (90), 49374−49385.
kinetics and morphology of biodegradable poly(lactic acid) with a (105) Yin, H.; Wei, X.; Bao, R.; Dong, Q.; Liu, Z.; Yang, W.; Xie, B.;
hydrazide nucleating agent. Polym. Test. 2015, 45, 101−106. Yang, M. Enhancing Thermomechanical Properties and Heat
(86) Liao, R.; Yang, B.; Yu, W.; Zhou, C. Isothermal cold Distortion Resistance of Poly(L-lactide) with High Crystallinity
crystallization kinetics of polylactide/nucleating agents. J. Appl. under High Cooling Rate. ACS Sustainable Chem. Eng. 2015, 3 (4),
Polym. Sci. 2007, 104 (1), 310−317. 654−661.
(87) Liang, J.; Zhou, L.; Tang, C.; Tsui, C. Crystalline properties of (106) Yu, F.; Liu, T.; Zhao, X.; Yu, X.; Lu, A.; Wang, J. Effects of talc
poly(L-lactic acid) composites filled with nanometer calcium on the mechanical and thermal properties of polylactide. J. Appl. Polym.
carbonate. Composites, Part B 2013, 45 (1), 1646−1650. Sci. 2012, 125 (S2), E99−E109.
(107) Ray, S. S.; Yamada, K.; Okamoto, M.; Ueda, K. Biodegradable PBAT blend reinforced kenaf fiber. Iran. Polym. J. 2013, 22 (2), 101−
polylactide/montmorillonite nanocomposites. J. Nanosci. Nanotechnol. 108.
2003, 3 (6), 503−510. (128) Xu, H.; Wang, L.; Teng, C.; Yu, M. Biodegradable composites:
(108) Ray, S. S.; Yamada, K.; Okamoto, M.; Ogami, A.; Ueda, K. Ramie fibre reinforced PLLA-PCL composite prepared by in situ
New polylactide/layered silicate nanocomposites. 3. High-performance polymerization process. Polym. Bull. 2008, 61 (5), 663−670.
biodegradable materials. Chem. Mater. 2003, 15 (7), 1456−1465. (129) Ganster, J.; Fink, H.; Pinnow, M. High-tenacity man-made
(109) Ray, S. S.; Yamada, K.; Okamoto, M.; Ueda, K. New cellulose fibre reinforced thermoplastics−injection moulding com-
polylactide-layered silicate nanocomposites. 2. Concurrent improve- pounds with polypropylene and alternative matrices. Composites, Part
ments of material properties, biodegradability and melt rheology. A 2006, 37 (10), 1796−1804.
Polymer 2003, 44 (3), 857−866. (130) Mu, C.; Xue, L.; Zhu, J.; Jiang, M.; Zhou, Z. Mechanical and
(110) Wertz, J. T.; Mauldin, T. C.; Boday, D. J. Polylactic Acid with Thermal Properties of Toughened Poly(L-lactic) Acid and Lignin
Improved Heat Deflection Temperatures and Self-Healing Properties Blends. BioResources 2014, 9 (3), 5557−5566.
for Durable Goods Applications. ACS Appl. Mater. Interfaces 2014, 6 (131) Sun, Y.; Yang, L.; Lu, X.; He, C. Biodegradable and renewable
(21), 18511−18516. poly(lactide)−lignin composites: synthesis, interface and toughening
(111) Product Datasheets for Engineered Bioplastic Compounds - mechanism. J. Mater. Chem. A 2015, 3 (7), 3699−3709.
RTP Company. http://web.rtpcompany.com/info/data/bioplastics/ (132) Qiang, T.; Yu, D.; Gao, H.; Wang, Y. Polylactide-based wood
index.htm (accessed February, 2016). plastic composites toughened with SBS. Polym.-Plast. Technol. Eng.
(112) reSound biopolymer Compounds. http://www.polyone.com/ 2012, 51 (2), 193−198.
files/resources//reSound_Product_Bulletin.PDF (accessed February, (133) Taib, R. M.; Hassan, H.; Mohd Ishak, Z. Mechanical and
2016). morphological properties of polylactic acid/kenaf bast fiber composites
(113) Ecopond AFR97 PLA-PC Alloy. http://omnexus.specialchem. toughened with an impact modifier. Polym.-Plast. Technol. Eng. 2014,
com/product/t-kingfa-ecopond-afr-97-pla-pc-alloy (accessed February, 53 (2), 199−206.
2016). (134) Liu, T.; Yu, F.; Yu, X.; Zhao, X.; Lu, A.; Wang, J. Basalt fiber
(114) Physical properties of Eco Pellet. http://www.umgabs.co.jp/ reinforced and elastomer toughened polylactide composites: Mechan-
en/products/edt/16.pdf (accessed February, 2016). ical properties, rheology, crystallization, and morphology. J. Appl.
(115) Wang, Y.; Chiao, S.; Hung, T.; Yang, S. Improvement in Polym. Sci. 2012, 125 (2), 1292−1301.
toughness and heat resistance of poly(lactic acid)/polycarbonate blend (135) Yang, J.; Wang, C.; Shao, K.; Ding, G.; Tao, Y.; Zhu, J.
through twin-screw blending: Influence of compatibilizer type. J. Appl. Morphologies, mechanical properties and thermal stability of poly-
Polym. Sci. 2012, 125 (S2), E402−E412. (lactic acid) toughened by precipitated barium sulfate. Russ. J. Phys.
(116) Lin, L.; Deng, C.; Wang, Y. Improving the impact property and Chem. A 2015, 89 (11), 2092−2096.
heat-resistance of PLA/PC blends through coupling molecular chains (136) Murariu, M.; Ferreira, A.; Duquesne, E.; Bonnaud, L.; Dubois,
at the interface. Polym. Adv. Technol. 2015, 26 (10), 1247−1258.
P. Polylactide (PLA) and Highly Filled PLA-Calcium Sulfate
(117) Lin, L.; Deng, C.; Lin, G.; Wang, Y. Super toughened and high
Composites with Improved Impact Properties. Macromol. Symp.
heat-resistant PLA-based blends by enhancing interfacial bonding and
2008, 272, 1−12.
PLA phase crystallization. Ind. Eng. Chem. Res. 2015, 54 (21), 5643−
(137) Murariu, M.; Ferreira, A. D. S.; Pluta, M.; Bonnaud, L.;
5655.
Alexandre, M.; Dubois, P. Polylactide (PLA)−CaSO4 composites
(118) Mohanty, A.; Misra, M.; Hinrichsen, G. Biofibres, biodegrad-
toughened with low molecular weight and polymeric ester-like
able polymers and biocomposites: an overview. Macromol. Mater. Eng.
2000, 276 (1), 1−24. plasticizers and related performances. Eur. Polym. J. 2008, 44 (11),
(119) Mohanty, A.; Misra, M.; Drzal, L. Sustainable bio-composites 3842−3852.
from renewable resources: opportunities and challenges in the green (138) Herrera, N.; Mathew, A. P.; Oksman, K. Plasticized polylactic
materials world. J. Polym. Environ. 2002, 10 (1−2), 19−26. acid/cellulose nanocomposites prepared using melt-extrusion and
(120) Baltazar-y-Jimenez, A.; Sain, M. Effect of bismaleimide reactive liquid feeding: mechanical, thermal and optical properties. Compos. Sci.
extrusion on the crystallinity and mechanical performance of Technol. 2015, 106, 149−155.
poly(lactic acid) green composites. J. Appl. Polym. Sci. 2012, 124 (139) Chow, W.; Leu, Y.; Mohd Ishak, Z. Effects of SEBS-g-MAH on
(4), 3013−3023. the properties of injection moulded poly(lactic acid)/nano-calcium
(121) Petinakis, E.; Yu, L.; Edward, G.; Dean, K.; Liu, H.; Scully, A. carbonate composites. eXPRESS Polym. Lett. 2012, 6 (6), 503−510.
D. Effect of matrix−particle interfacial adhesion on the mechanical (140) Chow, W. S.; Leu, Y. Y.; Ishak, Z. A. M. Mechanical, Thermal
properties of poly(lactic acid)/wood-flour micro-composites. J. Polym. and Morphological Properties of Injection Molded Poly(lactic acid)/
Environ. 2009, 17 (2), 83−94. Calcium Carbonate Nanocomposites. Period. Polytech., Mech. Eng.
(122) Xia, X.; Liu, W.; Zhou, L.; Liu, H.; He, S.; Zhu, C. Study on flax 2016, 60 (1), 15−20.
fiber toughened poly(lactic acid) composites. J. Appl. Polym. Sci. 2015, (141) Jiang, L.; Liu, B.; Zhang, J. Properties of poly(lactic acid)/
132, 42573. poly(butylene adipate-co-terephthalate)/nanoparticle ternary compo-
(123) Bledzki, A. K.; Jaszkiewicz, A.; Scherzer, D. Mechanical sites. Ind. Eng. Chem. Res. 2009, 48 (16), 7594−7602.
properties of PLA composites with man-made cellulose and abaca (142) Xiong, Z.; Dai, X.; Na, H.; Tang, Z.; Zhang, R.; Zhu, J. A
fibres. Composites, Part A 2009, 40 (4), 404−412. toughened PLA/Nanosilica composite obtained in the presence of
(124) Bledzki, A.; Franciszczak, P.; Meljon, A. High performance epoxidized soybean oil. J. Appl. Polym. Sci. 2015, 132, 41220.
hybrid PP and PLA biocomposites reinforced with short man-made (143) Odent, J.; Raquez, J.; Thomassin, J.; Gloaguen, J.; Lauro, F.;
cellulose fibres and softwood flour. Composites, Part A 2015, 74, 132− Jérôme, C.; Lefebvre, J.; Dubois, P. Mechanistic insights on nanosilica
139. self-networking inducing ultra-toughness of rubber-modified polylac-
(125) Ho, M.; Lau, K.; Wang, H.; Hui, D. Improvement on the tide-based materials. Nanocomposites 2015, 1 (3), 113−125.
properties of polylactic acid (PLA) using bamboo charcoal particles. (144) Wu, J.; Kuo, M.; Chen, C. Physical properties and
Composites, Part B 2015, 81, 14−25. crystallization behavior of poly(lactide)/poly(methyl methacrylate)/
(126) Nomai, J.; Jarapanyacheep, R.; Jarukumjorn, K. Mechanical, silica composites. J. Appl. Polym. Sci. 2015, 132, 42378.
Thermal, and Morphological Properties of Sawdust/Poly(lactic acid) (145) Liang, J.; Li, F. Mechanical properties of poly(l-lactic acid)
Composites: Effects of Alkali Treatment and Poly(butylene adipate- composites filled with mesoporous silica. Polym. Compos. 2015, DOI:
co-terephthalate) Content. Macromol. Symp. 2015, 354 (1), 244−250. 10.1002/pc.23674.
(127) Sis, A. L. M.; Ibrahim, N. A.; Yunus, W. Md Zin Wan Effect of (146) Yeniova Erpek, C. E.; Ozkoc, G.; Yilmazer, U. Effects of
(3-aminopropyl) trimethoxysilane on mechanical properties of PLA/ halloysite nanotubes on the performance of plasticized poly(lactic
acid)-based composites. Polym. Compos. 2015, DOI: 10.1002/ (166) SUPLA 135. http://www.supla-bioplastics.com/en/pro2_
pc.23511. detail.php?id=243&class_list=21&class_name=43 (accessed February,
(147) Murariu, M.; Dechief, A.; Ramy-Ratiarison, R.; Paint, Y.; 2016).
Raquez, J.; Dubois, P. Recent advances in production of poly(lactic (167) Ecoplan-Dura Datasheet. http://www.materialdatacenter.com/
acid) (PLA) nanocomposites: a versatile method to tune crystallization ms/en/Ecoplan/SK+Chemicals/Ecoplan+DURA/d2ef4d76/6784 (ac-
properties of PLA. Nanocomposites 2015, 1 (2), 71−82. cessed February, 2016).
(148) Ojijo, V.; Ray, S. S.; Sadiku, R. Effect of nanoclay loading on (168) Bio-Flex® F 6513 Technical datasheet. http://www.fkur.com/
the thermal and mechanical properties of biodegradable polylactide/ fileadmin/user_upload/Produkte/bioflex/F6513/TD_BIO-FLEX_F_
poly[(butylene succinate)-co-adipate] blend composites. ACS Appl. 6513_en.pdf (accessed February, 2016).
Mater. Interfaces 2012, 4 (5), 2395−2405. (169) NaturePlast materials and additives portfolio. http://www.
(149) Salehiyan, R.; Yussuf, A.; Hanani, N. F.; Hassan, A.; Akbari, A. natureplast.eu/images/pdf/en/Portfolio_Natureplast_eng.pdf (ac-
Polylactic acid/polycaprolactone nanocomposite Influence of mont- cessed February, 2016).
(170) KEBACOMP® FE 120204 Material datasheet. http://www.
morillonite and impact modifier on mechanical, thermal, and
materialdatacenter.com/ms/en/Kebacomp/
morphological properties. J. Elastomers Plast. 2015, 47 (1), 69−87. BARLOG+plastics+GmbH/KEBACOMP%C2%AE+FE+120204/
(150) Jandas, P.; Mohanty, S.; Nayak, S. Morphology and thermal ffa76a32/6569 (accessed February, 2016).
properties of renewable resource-based polymer blend nanocompo- (171) Ecolgreen Biopolymer. http://www.ecolgreen.com/eng/
sites influenced by a reactive compatibilizer. ACS Sustainable Chem. include/content.php?pageID=ID12052844672 (accessed February,
Eng. 2014, 2 (3), 377−386. 2016).
(151) Ostafinska, A.; Fortelny, I.; Nevoralova, M.; Hodan, J.; (172) ECOGEHR® PLA-L Technical datasheet. http://omnexus.
Kredatusova, J.; Slouf, M. Synergistic effects in mechanical properties specialchem.com/product/gehr-plastics-ecogehr-plal-polylactic-acid
of PLA/PCL blends with optimized composition, processing, and (accessed February, 2016).
morphology. RSC Adv. 2015, 5 (120), 98971−98982. (173) WinGram PLA Series. http://www.wingram.hk/index.php/
(152) Serizawa, S.; Inoue, K.; Iji, M. Kenaf-fiber-reinforced products/pla-series (accessed February, 2016).
poly(lactic acid) used for electronic products. J. Appl. Polym. Sci. (174) Highly heat resistant Bioplastic. http://www.teijin.com/rd/
2006, 100 (1), 618−624. technology/bioplastic/ (accessed February, 2016).
(153) Huda, M. S.; Drzal, L. T.; Misra, M.; Mohanty, A. K.; Williams, (175) ASTM Standard D6400-12. Standard specification for labeling
K.; Mielewski, D. F. A study on biocomposites from recycled of plastics designed to be aerobically composted in municipal or
newspaper fiber and poly(lactic acid). Ind. Eng. Chem. Res. 2005, 44 industrial facilities; ASTM International: West Conshohocken, PA,
(15), 5593−5601. 2012; http://www.astm.org/cgi-bin/resolver.cgi?D6400.
(154) Huda, M.; Drzal, L.; Mohanty, A.; Misra, M. The effect of
silane treated-and untreated-talc on the mechanical and physico-
mechanical properties of poly(lactic acid)/newspaper fibers/talc
hybrid composites. Composites, Part B 2007, 38 (3), 367−379.
(155) Reddy, J. P.; Misra, M.; Mohanty, A. Injection Moulded
Biocomposites from Oat Hull and Polypropylene/Polylactide Blend:
Fabrication and Performance Evaluation. Adv. Mech. Eng. 2013, 5,
761840.
(156) Nyambo, C.; Mohanty, A. K.; Misra, M. Polylactide-based
renewable green composites from agricultural residues and their
hybrids. Biomacromolecules 2010, 11 (6), 1654−1660.
(157) Nagarajan, V.; Zhang, K.; Misra, M.; Mohanty, A. K.
Overcoming the Fundamental Challenges in Improving the Impact
Strength and Crystallinity of PLA Biocomposites: Influence of
Nucleating Agent and Mold Temperature. ACS Appl. Mater. Interfaces
2015, 7 (21), 11203−11214.
(158) reSound FR Development. http://www.innovationtakesroot.
com/~/media/itr2012/2012/presentations/durables/05_non_
halogen-flame-retarded-resound_avakian_pdf (accessed February,
2016).
(159) deTerra® Biobased Polymers. http://www.
innovationtakesroot.com/~/media/ITR2012/2012/presentations/
emerging-markets/03_deTerra-Biobased-Polymers_Cernohous_pdf
(accessed February, 2016).
(160) Terraloy® 3D-40040 Series. http://omnexus.specialchem.
com/product/t-teknor-apex-terraloy-3d-40040-series (accessed Febru-
ary, 2016).
(161) High heat PLA: Unlocking Bioplastic potential for durable
applications. http://www.corbion.com/media/77166/corbion-purac-
pla-high-heat-themesheet.pdf (accessed Feb, 2016).
(162) Bioloy. http://www.jimshin.com/productshow.asp?b_classid=
121&yid=339 (accessed February, 2016).
(163) ECODEAR® PLA Resin. http://www.toray.jp/plastics/en/
ecodear/grade.html (accessed February, 2016).
(164) Unitika Terramac product list and grades. http://www.unitika.
co.jp/terramac/e/products/resin/list.html (accessed February, 2016).
(165) NatureWorks Technical Resources. http://www.
natureworksllc.com/Technical-Resources (accessed February, 2016).