pubs.acs.

org/engineeringau Review

Durable Polylactic Acid (PLA)-Based Sustainable Engineered Blends

and Biocomposites: Recent Developments, Challenges, and
Opportunities
Neelima Tripathi, Manjusri Misra,* and Amar K. Mohanty*

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ABSTRACT: The paper comprehensively reviews durable polylactic

acid (PLA)-based engineered blends and biocomposites supporting a
Downloaded via 201.243.244.195 on January 14, 2022 at 22:51:33 (UTC).

low carbon economy. The traditional fossil fuel derived non-

renewable durable plastics that cannot be circumvented have
spawned increased environmental concerns because of the con-
tinuous rise of their carbon footprint during processing and disposal.
It is anticipated that the production of biodegradable and
nonbiodegradable (durable) plastics from the year 2020 to 2025
will rise ∼47% and ∼21%, respectively. The carbon footprint can be
reduced in durable (nonrenewable) plastics by decreasing or
replacing the “fossil carbon” content with “renewable carbon”
content. The replacement will enable us to attain a sustainable
environment, a low carbon footprint, energy security, and effective
resource management. Thus, PLA-based durable products need to be
developed with an enhanced service life that strikes a balance between environment-friendliness and product performance for
engineering high-performance applications. The recent progress for enhancing the durability of PLA-based products consisting of
hybrid nonrenewable and renewable carbon has been attained by incorporating synthetic plastics, synthetic fibers (glass and carbon),
natural fibers, and other biofillers (biocarbon). Further, the effects of additives such as initiators, nucleating agents, chain extenders,
compatibilizers, impact modifiers, and toughening agents to prepare such blends and composites have been discussed. This Review
further critically examines the advances centering on processability, heat resistance, flame retardancy, strength, and toughness. In
addition to that, current and prospective applications such as automotive, electronic, medical, textile, and housing of PLA-based
products are discussed. However, the challenges for tailoring durable PLA-based products that still need to be addressed, such as
improved processability, striking stiffness−toughness balance, enhanced heat resistance, and improved interfacial adhesion between
the polymer−polymer, polymer−filler, and hybrid polymer−filler in respective polymer blends, composites, and hybrid composites,
are summarized and analyzed in this Review. Hence, the opportunities for improvement to overcome the challenges lie ahead.
KEYWORDS: Renewable carbon, Compatibilization, Processing, Strength, Toughness, Heat resistance, Flame resistance, Durability,
Low carbon economy

1. INTRODUCTION such as marine pollution, land pollution, and air pollution that
Over the past 100 years, plastics and polymers have causes CO2 emission. The National Aeronautics and Space
progressively been used and are now ubiquitous and Administration (NASA) web site shows that the rise of CO2
indispensable1 as they are lightweight, inexpensive, readily from the year 2005 to 2021 has reached 10%.4 This linear
processable, and durable. However, due to the continuous economy driven by the burning of fossil fuels results in the
production of petroleum-based plastics and an unprecedented emission of greenhouse gases, and reckless depletion of natural
waste management crisis, it is expected that the amount of
plastic waste will increase to 850 million tons per annum by
2050.2 It is assessed that more than 150 million tons of plastic Received: June 13, 2021
debris is currently floating on the surface of the oceans.3 At Published: October 4, 2021
least 8 million tons of plastic waste is dumped into the ocean
each year, at a rate of approximately 1 garbage truck per
minute.3 Such vigorous plastic production leads to well-
established issues that are detrimental to the environment2
© 2021 The Authors. Published by
American Chemical Society https://doi.org/10.1021/acsengineeringau.1c00011
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ACS Engineering Au pubs.acs.org/engineeringau Review

Figure 1. Schematic representation of biobased plastics from “cradle to gate” for durable applications. (The figure has been drawn by the authors,
and the pictures in the figure have been taken from “3D Models” and “Icons” of Microsoft Office.)

resources drastically impairs the life of future generations.3 to gate” representation of the development of biobased durable
Thus, the consequences of the continuous rise of the carbon plastics is illustrated in Figure 1.
footprint into the atmosphere cannot be circumvented and is a Environmental impacts by CO2 emissions from petro-based
topic of grave concern. Hence, the addition of more CO2 to and biobased polymers is quantitatively represented in Figure
the atmosphere has spawned increased attention as it needs to 2a. The data show that the petroleum-based polymers
be diminished, and sustainable practices must be adopted to consisting of fossil or nonrenewable carbon parts in the
counter the effects. The concept of sustainability covers three durable product will contribute to more CO2 greenhouse gas
major points: (i) maximum utilization of renewable resources; emissions. So, if a part of the fossil carbon can be replaced with
(ii) the energy required by the system should be optimized, renewable carbon, the increasing carbon footprint can be
and minimum energy input suffices the purpose; (iii) the waste
generated from one process becomes the resource for another.5
The current plastic waste epidemic can be addressed via the
circular economy approach, as the closed-loop approach is
restorative and regenerative. Factors such as resource depletion
and environmental burden due to the linear model approach
have led to the discussions toward achieving a sustainable
society and conserving resources by the circular economy.6,7 In
the circular economy, the maximum value of the resources can
be extracted, retained, and kept in use to its maximum extent.8
However, the critical enabler of the circular economy is to
make materials for longevity9 or more durable or efficient,
preventing waste production.3 In the circular economy
approach, the product is retained within the economy,
maximizing its economic productivity at the end of each
service life. The approach promotes a reduction in material
input and minimizes waste generation, which helps in
diminishing the pressures on the environment.8
Thus, for achieving a sustainable circular economy, environ-
ment-friendly, sustainable, and durable products need to be
designed and developed without compromising performance.
Hence, the products having reduced fossil carbon consisting of
both conventional and biobased plastics need to be engineered
to partially curtail the dependency on petroleum resources,
mitigate climate change, and reduce material carbon foot-
print.10 The durable biobased product will keep the materials
in use, favoring low carbon and circular economy, as the
synthesized material will have low fossil carbon, low CO2
emission and at the end of its life can be recycled or
incinerated for producing energy. The introduction of
renewable carbon for reducing fossil carbon into products
should not significantly affect the properties, performance, and Figure 2. (a) Environmental impacts of petro-based and biobased
aging of the products and hence should last longer (durable) polymers41 (figure redrawn). (b) Schematic representation of the
and can be used for high-performance applications. The “cradle components involved in developing low carbon footprint.

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ACS Engineering Au pubs.acs.org/engineeringau
controlled or reduced throughout its life cycle.11 Spierling et
al.12 conducted a detailed calculation of the substitution
potential of petro-based plastics with biobased plastics and
determined global warming potential (GWP) impacts. Initially,
GWP was calculated based on the global demand of fossil
LDPE (low density polyethylene); further GWP for biobased
substitution was calculated for LDPE. GWP for biobased
substitution included bio-PE (bio-polyethylene), PHA/PHB
(poly(hydroxy alkanoate)/poly(hydroxy butyrate)), and starch
blends. It has also been deduced from the calculations that
241−316 million tons of CO2 equivalents can be saved by
bioplastics each year.13 Further, the use of renewable carbon in
durable plastics helps to curtail the dependency on petroleum
resources which can further translate to saving several barrels
of oil per year.10 In addition to that, it will be the attempt to
develop such products for attaining some specific targets such
as (1) reducing at a minimum of 20% environmental impacts;
(2) saving no less than 20 MJ of nonrenewable energy per
kilogram of polymer; (3) avoiding at least 1 kg of CO2 per
kilogram of polymer.14 The end-of-life strategy for such
durable products can be recycling15,16 or smokeless inciner-
ation. The energy recovered from the incineration process can
be used further for the production of heat or power.17
Yarahmadi et al.18 studied the durability issues of reprocessing
and recycling virgin PLA resin and compared it with PLA
blends consisting of fossil-based resins, such as polycarbonate
(PC) and high density polyethylene (HDPE). Post-consumer
recycling of virgin PLA and PLA blends was conducted after
accelerated aging (that corresponds to product usage for 1
year) succeeded by reprocessing. It was observed that the
PLA/HDPE blend and PLA/PC blend showed increased and
decreased elongation at break, respectively, after multiple
rounds of processing. Ngaowthong et al.19 observed an
increase in percentage crystallinity in PLA composites with
increasing recycling times and hence revealed reduced water
diffusivity. Beigbeder et al.20 concluded that the recycling of
PLA reinforced with flax fiber composites (composite preferred
to be used in indoor automotive applications) after end-of-life
showed the lowest environmental impacts when compared
with industrial composting.
In addition to that, PLA-based products can be subjected to
chemical recycling. Chemical recycling is a depolymerization
process using chemicals, usually solvents or acids.21 Further,
the depolymerized components can be repolymerized to form
valuable products. The chemical recycling of PLA was
conducted by using a clay catalyst (montmorillonite K10),22
aliphatic diamines (1,6-diaminehexane (DAH) and 1,2-
diamineethane (DAE)),23 an acetone−water solution,24 and
an ethanol−water solution.21 Further, PLA/PE blends were
chemically recycled by selective degradation. So, based on
different solubilities toward toluene, PLA/PE blends were
separated and PLA was depolymerized further using
montmorillonite K5.25 Further, to make the process econom-
ically viable and sustainable, microwave heating was also
applied.26 Furthermore, apart from incineration and recycling
(until the blends and composites can be used to develop usable
products), polymeric products should be avoided for land-
filling, as it is not a safe or sustainable option. Particularly for
industrially compostable materials, according to ASTM
D6400-19,27 any product consisting of more than 1% of
unknown organic constituents must pass the biodegradation/
compostability test. Zhao et al.28 studied the closed-loop
recycling of 3D printed PLA products. The life cycle
9 https://doi.org/10.1021/acsengineeringau.1c00011
Review
assessment (LCA) approach showed that recycling has lower
environmental burdens followed by incineration and landfills
have the highest environment burden.
Thus, efforts are being made to overcome the issue of an
increased carbon footprint into the atmosphere by replacing
even the part of the conventional (petroleum-based and
nonbiodegradable) polymers, for instance, poly(ethylene
terephthalate) (PET), PE, polypropylene (PP), and polystyr-
ene (PS), with biobased plastics such as starch, cellulose,
PHAs, and polylactic acid (PLA).13,29,30 Compared to fossil-
based plastics, PLA contributes to a zero-material carbon
footprint and lower CO2 emissions. In addition to that,
modified PLA can be easily processed by technologies such as
extrusion, injection molding, casting, thermoforming, com-
pounding, 3D printing, and fiber spinning. Furthermore, the
biobased carbon from PLA can be incorporated into durable
products. Hence, PLA properties need to be enhanced for a
wider range of high-performance applications.
Researchers have started tailoring products in such a way
that the fossil or nonrenewable carbon and renewable carbon
coexists. However, much work needs to be done to attain
durability for biobased products with enhanced properties for
high-performance applications. Reddy et al.31 reviewed the
status and opportunities of biobased plastics and bionano-
composites without focusing on the durability of PLA-based
blends and composites. Chang et al.32 reviewed biobased
composites only. The PLA-based blends and composites have
not been covered. Further, the advanced engineering
applications of durable PLA composites have not been
discussed. Nagarajan et al.33 discussed the perspectives on
high-performance partially renewable PLA-based materials for
durable (multiuse long-term) applications focusing only on
heat resistance and toughness. Hemath et al.34 reviewed the
effect of fillers in high-performance hybrid polymer-based
nanocomposites. Along with the mechanical properties,
research progress, specifically thermal, electrical, electro-
magnetic radiation shielding, viscoelastic, and creep properties,
was discussed and compared. However, PLA-based blends and
composites consisting of synthetic plastics, glass fibers (GF),
carbon fibers (CF), natural fibers, and biocarbon have not
been discussed elsewhere. Further, the effects of additives,
prospective applications of durable PLA blends and
composites, their key challenges, and future perspective have
not been discussed.
The focus of this Review is to discuss the recent research
work for the development of PLA-based blends and
composites having both “renewable carbon” and “fossil carbon”
for attaining properties like that of engineering plastics which
have the potential to be used in durable applications for
achieving the goals schematically represented in Figure 2b. The
focused aspects of PLA-based blends and composites
consisting of synthetic, nonbiodegradable additives and at
least one nonbiodegradable filler (in case of composites) that
showed significant improvement in thermal and mechanical
properties for durable applications are discussed. Comprehen-
sive literature on the topic is systematically organized based on
the strategies and approaches followed to resolve the
limitations of the materials. The latest advances in PLA-
based blends and composites, key challenges for tailoring the
blends and composites, and future perspectives have been
discussed. The synthesized durable PLA-based product usage
in numerous applications, namely, automotive, housing,
electronics, and textiles, are also discussed.
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2. FACTORS AFFECTING THE DURABILITY OF mobile phase (XMAP)). The increase or decrease in these
BIOPLASTICS: A POTENTIAL SUBSTITUTE OF parameters is shown in Figure 3a.44 Figure 3b shows the effect
ENGINEERING PLASTICS
Biopolymers have attracted significant attention for the
fabrication of products for engineering applications. However,
the service life of the biopolymers is a serious concern.
Bioplastics are susceptible to various environmental factors
such as temperature, humidity,32 oxidation, and pollutants.
These factors severely affect the service life of the products and
further exacerbate the degradation rate.35 Thus, the develop-
ment of environmentally sustainable and durable products with
a low carbon footprint is essentially needed.
For the development of these durable products, individual
polymers (renewable and nonrenewable) are combined with
reinforcing agents and additives to form blends and
biocomposites. These blends and composites possess the
combined properties or sometimes superior properties than
individual polymers. The quantity of each polymer can be
adjusted to achieve specific performance.36 It has been
observed that the effective approach for improving the
properties of plastics is by creating multicomponent blends37
or composites. The basic prerequisites for developing the
blends or composites for enhancing the durability of plastics
are as follows: excellent toughness of the material, 37
flexibility,37 high impact resistance or impact strength, ability
to crystallize, and high heat deflection temperature (HDT). As
for durable applications, significantly high mechanical strength,
temperature resistance and, the ability to withstand sudden
impact are desirable. Processing parameters on the impact
strength and HDT are the critical factors that decide the
commercialization of polymers for wide-scale applications.38
However, it was observed that the enhancement in toughness
usually reduces tensile strength and tensile modulus. The
composite having high storage modulus can be correlated with
the presence of a crystalline structure. In the crystalline region,
the polymers are aligned and have less mobility which results
in enhanced composite stiffness.38 The crystallinity has various
benefits on different products. Crystallinity in cutlery provides
Figure 3. (a) PLA stability and its effect on properties at humid
heat resistance and stiffness; it provides heat resistance in trays environments.44 (Adapted with permission from ref 44. Copyright
and cups; it provides barrier and chemical resistance in films; 2017 American Chemical Society.) (b) Change in Tm during PLA
and it provides higher strength39 and chemical resistance40 in aging in humid environments.44 (Reprinted with permission from ref
fibers. Thus, the preparation of blends and composites is an 44. Copyright 2017 American Chemical Society.) (c) Change in Xc
effective and economical means of developing materials with during PLA aging in humid environments.44 (Adapted with
required physical and mechanical properties. permission from ref 44. Copyright 2017 American Chemical Society.)
Thus, materials using biopolymers (made from renewable or
biological resources)31 or biobased (obtained partially or on Tm of PLA at different humidity environments with time.44
totally from biological resources)31 polymers need to be used Initially (until ∼40 days), a slight increase in Tm was detected
for the development of sustainable materials. One of the most with an increase in humidity because of the increase in PLA
promising biopolymers for achieving durability for sustainable crystallites thickness. The increase in crystallite thickness is
applications is PLA.42 PLA is a semicrystalline aliphatic favored by the increase in chain mobility during hydrolysis.
thermoplastic polyester37,43 having terminal hydroxyl and Further, at increased aging times, a decrease in Tm was
carboxyl groups. The largest producer of PLA that is situated observed due to the reduction in the thickness of lamellae
in the United States is NatureWorks. The other producers of (disordered crystals). Figure 3c shows the linear increase in Xc
PLA are Toyota, Mitsubishi, Shimadzu, Mitsui Chemicals, at different humidity environments with time.44 The increase
Purac, Futerro, and Biomer.31 in Xc during aging with the increase in humidity was observed
However, for durability applications, PLA has its limitations due to the hydrolysis-induced crystallization. However, this
due to its sensitivity to humidity. The parameters which are may impart plasticization.44
affected by the humidity in PLA are water sorption (H2O), dry The effect of weathering on PLA samples was observed
matter loss, molecular weights (number-average (M̅ n) and using X-ray diffraction (XRD) and rheological and morpho-
weight-average (M̅ w)), glass transition temperature (Tg), logical characterization. The PLA samples were placed in
melting temperature (Tm), percentage of crystallinity (Xc), accelerated weathering conditions and exposed to ultraviolet
amorphous region percentage (rigid fraction (XRAF), and (UV) radiation at a temperature of 40 °C and 60% relative
10 https://doi.org/10.1021/acsengineeringau.1c00011
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ACS Engineering Au pubs.acs.org/engineeringau
humidity for 600 h. The incident light intensity of the mercury
lamp was 39 mW cm−2 at the wavelength range from 200 to
700 nm. The XRD analysis of PLA samples after 600 h showed
strong diffraction crystalline peaks at 16.6° and 18.6°,
suggesting chain scission, which is predominantly degrading
amorphous regions; i.e., the amorphous region is more prone
to weathering. The XRD spectra of the PLA samples are shown
in Figure 4a. Figure 4b shows the effect of weathering on the
Figure 4. (a) XRD spectra showing weathering effect on PLA.45
(Reprinted with permission from ref 45. Copyright 2013 American
Chemical Society.) (b) Effect of weathering on G′.45 (Adapted with
permission from ref 45. Copyright 2013 American Chemical Society.)
(c) Scanning electron micrographs of PLA45 (i) before weathering
and (ii) after weathering. (Reprinted with permission from ref 45.
Copyright 2013 American Chemical Society.) (d) DSC thermogram
showing the weathering effect of PLA.46 (Copyright 2020, adapted
with permission from Elsevier, license number: 5121501060785.)
storage modulus (G′).45 The reduction in G′ after UV
exposure confirms the degradation of amorphous regions of
PLA.45 The surface morphology of weathered samples (Figure
4c) revealed milky patches on PLA samples, and small cracks
also developed on the surface.45 Differential scanning
calorimetry (DSC) analysis was also conducted to observe
the effect of heat on the weathered samples (Figure 4d).46 It
was observed that, after weathering, the cold crystallization
peak at 90 °C for PLA disappeared, suggesting the extinction
of amorphous regions.
From the above results, it can be inferred that virgin PLA is
susceptible to weathering and is not suitable for durable
applications. The durability of PLA can be enhanced by
modifying it with fillers or additives. Researchers have started
developing and are becoming more inclined toward innovating
11
Review
the PLA-based blends and composites for durable applications
for a sustainable environment, low carbon footprint, energy
security, and effective resource management. The data of
published research articles have been extracted from the Web
of Science (Figure 5). The keywords used to extract the data
Figure 5. Research publication trends for the related field (data
assessed from the Web of Science, July 2021).
from the Web of Science are “polylactic acid engineering
application”, “sustainable polylactic acid”, “polylactic acid in
durable application”, and “durable polylactic acid”. The
publications trend, based on the keywords, showed that
research on PLA for durable applications has started recently
and interest toward this area is increasing significantly.
3. PLA LIMITATIONS TOWARD ENGINEERING
APPLICATIONS
PLA has recently gained a lot of attention owing to its
renewable-resource-based origin,37 good biodegradability37 or
compostability,38 biocompatibility,37,38 and high mechanical
strength37,38 related to other biobased plastics; better
processability37 compared to poly(ethylene glycol) (PEG),
PHA, and poly(ε-caprolactone) (PCL);47 low energy con-
sumption (25−55% less than petroleum-based polymers),47
low CO2 emissions or low carbon footprint and end of life
standpoints.38
PLA has been considered a propitious substitute to
petroleum-based polymers because of its affordable perform-
ance and large-scale availability in the market.37 It has been
used to make an expansive range of products for various
applications such as biomedical,37 packaging, and other
commodity applications.38 However, the innate deficiencies
of PLA limit its use in engineering applications, and hence, it
has yet to attain a strong commercial standpoint.
Thus, it is critically needed to modify the properties of PLA
in such a way that it can compete with other commodity
polymers, particularly PP, polyethylene (PE), poly(vinyl
chloride) (PVC), or PET. A few of the limitations of PLA
are as follows:
(I) High stiffness.48,49
(II) Poor ductility.37
(III) Brittleness.37,48−51 To overcome the brittle nature of
PLA, plasticizer(s) such as PEG were added into the PLA.
However, it results in the loss of stiffness or decreased modulus
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Table 1. Critical Properties Comparison among Biobased and Petroleum-Based Polymers for Sustainable Applicationsa
tensile tensile
density strength modulus HDT (°C) (at 0.455 elongation at
polymer (g·cm−3) Tg (°C) Tm (°C) (MPa) (GPa) MPa load) break (%) refs
PLA 1.21−1.25 45−60 150−180 59 3.5 55 7 66, 67
poly(D-lactic acid) (PDLA) 1.25−1.27 50−60 175 50 3.45 10 68, 69
acrylonitrile butadiene styrene 1.04 115.5 42.5−44.8 1.45 82 23−25 70−72
(ABS)
polycaprolactone (PCL) 1.07−1.2 −65 to −60 56−65 4−785 0.21−0.44 42 20−1000 73−76
polyglycolide/poly(glycolic 1.50−1.71 35−45 220−233 60−99.7 6−7 66, 77
acid) (PGA)
poly(ethylene terephthalate) 1.37 67−81 260 70−177 1.7−3.5 80−115 230 78−80
(PET)
polypropylene (PP) 0.91 −20 175 31 1.5−2 60−105 100−1000 79, 81,
82
polystyrene (PS) 1.05 70−115 100−240 30−100 2.3−4.1 85−95 1−4 79
polyamide 6/Nylon6 (PA6) 1.13 56.34 222.29 82 2.9 138.1 14.5 83
poly(ethylene terephthalate 1.26−1.28 75 56 1 240 84, 85
glycol) (PETG)
a
The properties of the polymers given in the table are dependent on the polymer grades.

of elasticity, which is one of the desirable properties for
structural applications. A few researchers incorporated nano-
clay into the PLA, which very well gets dispersed due to the
hydrogen bonding formation linking the carbonyl group of
PLA and ammonium group of clay into the polymer without
the addition of compatibilizers and results in the formation of
PLA nanocomposites.52 It has been observed for plasticized
PLA/MMT (montmorillonite) nanocomposites that it results
in at least maintaining toughness compared to other filled
polymeric systems. The brittle nature of PLA nanocomposite
was overcome by the addition of toughener into the materials.
(IV) Low impact strength.38,48 The low impact strength of
PLA is commonly linked with the brittle nature of PLA that
results in the incapability of polymeric chains to mobilize
relative to each other and consequently the inability to absorb
energy.53 The impact strength of neat PLA was observed as
∼20 J m−1.38
(V) Low deformation at break or elongation at break.48
Zhang et al.37 observed the elongation at break for PLA (Ingeo
3251D) around 4%. The ductility of the PLA was enhanced by
adding renewable elastomers ethylene methyl acrylate-glycidyl
methacrylate (EMA-GMA) and poly(ether-block-amide) elas-
tomeric copolymer (PEBA). However, the addition of
elastomers leads to a reduction in tensile strength and
modulus. In a PLA/EMA-GMA/PEBA ternary blend, an
increase in elongation at break was observed with an increase
in EMA-GMA (Elvaloy) content. The PLA/EMA-GMA/
PEBA of 70:20:10 wt % showed 72.7% elongation at break,
which is 20 times higher when compared with that of neat
PLA.
(VI) Low thermal resistance.51,54−56 Based on the PLA
molecule architecture, molecular weight, and degree of
crystallinity, the glass transition temperature ranges from 50
to 65 °C. It shows melting temperatures in the range of 150−
180 °C.31
(VII) Slow crystallization rate.38,54,56 PLA is a semicrystal-
line material which in XRD analysis showed a broad hollow or
peak ascribed to a weak reflection peak at 2θ = 16.8.38 The
crystallinity of the polymer is related to the stiffness. The
crystallinity can be improved either by the use of nucleating
agents without disturbing the inherent crystal structure or by
inducing stress during polymer processing.38,40 PLA also has
intrinsic flammability, which impedes its use in automobiles,
12
electrical appliances, and construction applications because of
the potential fire threat.57
(VIII) Moisture sensitivity of PLA during processing.
Generally, the moisture-induced degradation during processing
can be prevented by overnight drying of the polymer
precursors (having melting temperatures above 80 °C) at
∼75−80 °C in an oven or vacuum oven and is conducted to
remove unbound moisture. The dried precursors having a
moisture sensitivity of less than 1% are further processed. In
addition to that, the other method to reduce the moisture
sensitivity of PLA before processing is the modification,
functionalization, or grafting of PLA to make PLA hydro-
phobic. However, this process may change the properties of
PLA and will not be a cost-effective process. Further, additives
such as initiators, nucleating agents, and chain extenders58 have
been added to reduce moisture sensitivity and hydrolytic
instability in PLA-based products; this has been observed with
silane cross-linking,59 carbodiimide,60 silicon carbide,61 nano-
clays, graphene nanoplatelets, and antihydrolysis agents.58
(IX) Even though PLA has the ability to be processed, it still
has processing instability49,51 and a narrow processing
window.29
(X) Low HDT.38 The HDT value of PLA is around 55 °C.38
One of the efficacious and demonstrated approaches to
enhance the ability of PLA to crystallize and effective
enhancement of HDT is achieved by increasing the mold
temperature and using an organic nucleating agent.38 The
toughness of PLA, which is lower than those of polycarbonate
(PC) and PET, limits its use in structural applications.62,63 It is
also generally noticed that the magnitude of toughness is
inversely proportionate to that of strength and stiffness.64 The
low elongation at break and brittleness of PLA have been
overcome by researchers by the addition of plasticizers.48
Recently, PLA nanocomposites have gained attention as
researchers continue enhancing the inherent properties, such
as thermal and mechanical, of PLA. Nonetheless, the toughness
of PLA is jeopardized, which leads to a significant decrease in
ductility. The brittleness, poor toughness, and low HDT are
the main bottlenecks that hamper the performance of PLA for
durable applications. Effective improvements in stiffness, HDT,
and chemical resistance in PLA can be achieved by increasing
its total percent crystallinity.38 These inherent deficiencies in
PLA are the target areas that need improvement so that PLA
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ACS Engineering Au
Figure 6. Explored research on various polymers, reinforcing agents, and additives to fabricate PLA-based materials for durable applications.
can be used in engineering applications by achieving durability.
The characteristic parameters of PLA are compared with other
polymers in Table 1.
4. PLA-BASED BLENDS AND COMPOSITES
The pristine biobased polymers are usually expensive and have
poor performance. However, superior performance can be
attained if the bioplastics, having fossil and renewable carbon,
can be synergistically tailored for preparing the blends and
composites.65 Consequently, these cannot be used as it is, and
hence a balance between performance and cost needs to be
maintained while blending the polymers as blending
thermodynamics does not succor the blending process and is
not an easy feat.
One of the promising approaches for attaining durability is
by formulating PLA blends or synthesizing PLA composites
because of the distinctive properties and cost competitive-
ness33 of PLA. Hence, work needs to be done to fabricate PLA-
based blends or composites for enhancing their durability.
However, preparing a good miscible blend or composite of
PLA with other polymers is a challenging task that should not
hamper the toughness of the PLA. It also has to be considered
that the synthesized PLA blend or composite should not
impair the environmentally friendly characteristics.
Thus, the selection of precursors is a decisive factor that
needs careful attention for modifying PLA. Some noteworthy
results for PLA-based blends or composites have been reported
pubs.acs.org/engineeringau Review
and are elucidated in this section. Figure 6 illustrates various
polymer and additive combinations for the preparation of PLA-
based blends and provides composites explored so far for
enhancing their properties.
The PLA-based blends or composites that were prepared are
as follows: PLA-cellulose,86 PLA-silk,87 PLA-poly(glycerol
succinate-co-maleate)(PGSMA),88 PLA-PC,89 PLA-poly-
(trimethylene terephthalate) (PTT),90 PLA-CF,91 PLA-wheat
straw,92 PLA-nanoclay,93 PLA-soy straw,94 PLA-kenaf fiber,95
PLA-PCL,96 PLA-chitosan,97 PLA-soy protein isolate (SPI),98
PLA-talc,99 PLA-flax,100 PLA-starch,101 PLA-sisal fiber,102
PLA-hydroxyapatite,103 PLA-LDPE,104 PLA-HDPE,105 PLA-
ABS, 106 PLA-PP, 107 PLA-poly(butylene terephthalate)
(PBT),108 PLA-PET,109 PLA-nylon,110 PLA-polysaccharide
gum,111 PLA-PEG,112 and PLA-poly(amide elastomer)
(PAE).113
The additives used were Luperox (2,5-bis(tert-butyl
peroxy)-2,5-dimethylhexane),88 trichloromethyl terminated
PLA (PLA-Cl), LAK-301,38 magnesium oxysulfate,38 precipi-
tated calcium carbonate,38 poly(ethylene-n-butylene acrylate-
glycidyl methacrylate) (EBA-GMA),89,114−116 EMA-GMA
(Elvaloy),37,90 acryl copolymer (Biostrength 99),64 ethylene
butyl acrylate-maleic anhydride (EBA-MaH),114 ethylene
methyl acrylate-glycidyl methacrylate (EMA-MaH),114 epoxi-
dized microfibrillated cellulose (MFC-EPI), where EPI
represents epichlorohydrin,117 maleic anhydride-graf t-polypro-
pylene (MA-g-PP),118 L-lysine ethyl ester diisocyanate
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Figure 7. Molecular structure of additives used for the development of PLA-based durable products: (a) (i) dicumyl peroxide (DCP);124 (a) (ii)
trimethylolpropane triacrylate (TMPTA);125 (b) (i) Joncryl ADR 4368;116 (b) (ii) CESA Extend;128 (c) Biomax Strong;128 (d) Elvaloy PTW;116
(e) Lotader 3410;130 and (f) LAK-301.131 (Molecular structures have been drawn using ChemDraw.)
(LDI),119 hydrogenated dimer acid (HDA),119 poly(styrene-
acrylic-co-glycidyl methacrylate) (SA-GMA),116 N,N-dimethyl-
stearylamine (DMSA),120 stannous octanoate (Sn(Oct)2),121
dibutyltin dilaurate,122 Grubbs first generation ruthenium
metathesis catalyst,123 and poly(L-lactic acid)-block-poly-
(methyl methacrylate) (PLLA-b-PMMA).121
Thus, various types and quantities of additives were used to
formulate blends and composites that crucially determine the
desired properties of polymers for durable applications. The
additives can be classified as initiator, catalyst, synthesized
copolymer, nucleating agent, chain extender, compatibilizer,
impact modifier, and toughening agent. The general molecular
structures of some commonly used additives are shown in
Figure 7.
(a, i) initiator dicumyl peroxide (DCP);124
(a, ii) initiator trimethylolpropane triacrylate (TMPTA);125
(b, i) chain extender Joncryl ADR 4368 is poly(styrene-
acrylic-co-glycidyl methacrylate) (SA-GMA);116
(b, ii) chain extender CESA Extend is an epoxidized styrene-
acrylic copolymer,126,127 where R1−R5 represent H,
CH3, a higher alkyl group, or their combinations, while
R6 is an alkyl group, and the subscripts i−k are between
1 and 20.128
(c) impact modifier Biomax Strong128 includes ethylene−
acrylate copolymers;129
(d) toughening agent Elvaloy PTW is an EBA-GMA;116
(e) compatibilizer Lotader 3410 consists of maleic anhy-
dride and epoxy reactive groups;130
(f) nucleating agent LAK-301 is an aromatic sulfonate.131
Compatibilizers enhance stability by creating interactions
and diminishing the interfacial tension between two or more
pubs.acs.org/engineeringau Review
immiscible polymers or between polymer(s) and filler(s). In
reactive compatibilization, compatibilizers with reactive groups
facilitate compatibilization between PLA, petroleum-based
polymers, and fillers by reacting the end groups of PLA with
functional groups of petroleum-based polymers and fillers to
form ionic, covalent, or hydrogen bonds. In some cases, the
thermoplastic elastomer or rubbery copolymer particle size
reduction takes place upon the addition of compatibilizers.
Thus, the incompatibility between the matrix and dispersed
phase can be made compatible by using a compatibilizer. The
compatibilizer results in a small uniformly distributed particle
size. To achieve the super toughening effect, the particle size
should be optimum as a smaller particle size may not efficiently
absorb energy from external sources.
Initiators are added to the incompatible system to trigger the
reaction process. The initiator breaks into radicals, converting
monomers into radicals. The monomer radicals further react
with other monomers or polymers, and the process keeps on
propagating the chain to form bigger radicals. The chain is
terminated when the product radical reacts with other radicals
and polymerization product is obtained. In cationic or anionic
polymerization, the initiator is termed electrophile and
nucleophile, respectively.
Cross-linkers are one of the additives that are used to
augment tensile strength, impact resistance, and corrosion
resistance. However, cross-linked polymers face difficulties in
recycling. In addition to that, it is challenging to cross-link low
functionality macromolecules in a controlled manner. Hence,
high reactive sites are generated by energy-intensive
processes.132
The oligomer or masterbatch is usually synthesized by
reacting the monomers of the immiscible polymers. The
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synthesized copolymer or masterbatch is further added to the
immiscible polymers. The masterbatch consisting of various
functional groups can react to the immiscible polymers during
processing, enhancing the miscibility between the immiscible
polymers.
Nucleating agents create nucleating sites that can signifi-
cantly promote crystallization rate or crystallinity of PLA that
can significantly improve HDT or heat resistance of PLA.
Stereocomplex PLA also works as a nucleating agent. However,
special care should be taken for developing crystalline regions
in polymers because the crystallites can act as stress
concentrators and the material may break easily.
Chain extenders affect the thermal and mechanical proper-
ties by reacting with the functional groups of the polymers and
connecting the polymers’ chains. As the length of the
macromolecule increases, the degree of entanglement and
molar mass increases which increases viscosity and melt
temperature. A chain extender such as Joncryl has shown its
effectiveness in enhancing the percentage of elongation and
ductility. Chain extenders can also act as compatibilizers.
Impact modifiers are added to enhance toughness in PLA.
The addition results in improved impact strength and
elongation at break. However, impact modifiers reduce the
ability of PLA to crystallize and recrystallize.133 Wang et al.134
and Zhao et al.135 discussed the strategies to enhance the
toughness of PLA and PLA-based blends, respectively.
Catalysts have the capability to promote the interfacial
reaction between incompatible polymer blends. However,
mixed results have been achieved. The promising method of
improving reactive compatibilization can be conducted by
interfacial localized catalysis.136
4.1. PLA-Based Blends
4.1.1. PLA/PTT Blends. PTT is an aromatic polyester
synthesized by the condensation reaction of trimethylene
terephthalate and 1,3-propanediol. It is usually used in textile
industries owing to its high elastic property and recoverability.
The 1,3-propanediol part of PTT has also been derived from a
renewable resource such as starch.137
Kultravut et al.138 synthesized a toughened PLA/PTT blend
using a reactive compatibilizer (poly(ethylene-co-glycidyl
methacrylate) (PEGMA)). The PLA/PTT/PEGMA blend
was prepared initially by melt mixing PTT with PEGMA, and
then PLA was added. Since PEGMA does not preferentially
mix with PTT, it was added first with the compatibilizer in the
two-step blending process. PLA/PTT/PEGMA blend showed
a craze formation on the annealed elongated area, which
signifies toughening of the blend.
Nagarajan et al.90 reactively compatibilized PLA and PTT
using the EMA-GMA terpolymer. EMA-GMA was used as a
reactive terpolymer having epoxy functional groups. PLA and
PTT blends have shown good miscibility as a single Tg was
obtained for the composition. Joncryl ADR 4368, a chain
extender with a multiepoxy group, was also added to PLA/
PTT blends to impart melt stability to the polyesters and
facilitate compatibilization. During compatibilization, the
epoxy group of EMA-GMA reacted with the carboxyl and
hydroxy groups of PLA and PTT, forming a graft copolymer.
In the continuous PTT matrix phase, the PLA phase was
dispersed as domains forming a two-phase morphology. The
optimized formulation had 85% [PTT 70%:PLA 30%]/15%
terpolymer and chain extender (0.5 phr) processed at 200 rpm
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screw speed. It was concluded that the terpolymer significantly
affected tensile strength.
4.1.2. PLA/ABS Blends. ABS consists of polybutadiene
and styrene-acrylonitrile which determine toughness and
strength (tensile and flexural), respectively.139 ABS is
extensively used for automotive applications, especially for
interior parts of automobiles, because of its exceptionally good
impact strength.139 PLA and ABS can be made compatible by
adding compatibilizers such as maleic anhydride grafted
styrene-acrylonitrile copolymer, ethylene-propylene rubber,
and polycarbonate and epoxy terminated polyethylene.139
Jo et al.139 obtained enhanced mechanical strength (tensile
and impact, 40 MPa and 80 J·m−1, respectively) by the
addition of grafted ABS (G-ABS) and grafted styrene-
acrylonitrile grafted glycidyl methacrylate copolymer (SAN-
GMA) in a 50:50 blend of ABS and PLA.
Chaikeaw et al.140 initially synthesized ABS-g-PMAA in the
presence of an initiator (potassium persulfate) at 65 °C for 4 h.
Further, ABS-g-PMAA was reacted with PLA to form PLA-g-
ABS. PLA-g-ABS was further melt blended with PLA to form
PLA/PLA-g-ABS blends. A substantial rise in percent of
elongation (75%) was observed on blending of 20 wt % PLA-g-
ABS in PLA. In addition to that, it was perceived that PLA/
PLA-g-ABS behaved as an efficient impact modifier as the
impact strength of PLA/PLA-g-ABS30 wt % was shown to be
7.9 kg-cm·cm−1·cm−2.
Yu et al.141 prepared a PLA/ABS alloy by using a filler
(barium sulfate, BaSO4), compatibilizer (styrene-maleic
anhydride copolymer, SMA), and antioxidant for the housing
of loudspeakers. The injection molded PLA/ABS samples of
50:50 ratio resulted in a tensile strength and flexural modulus
of 55.4 MPa and 2.86 GPa, respectively.
Rigoussen et al.106 followed two approaches for compatibi-
lizing immiscible PLA and ABS. The compatibilization was
conducted by using a liquid phenolic compound (cardanol).
However, it showed reactivity toward ABS rather than PLA.
Hence, two approaches were followed. In the first approach, an
enhancement in elongation at break and impact strength of
PLA/ABS was attained by the reaction of epoxidized cardanol
unsaturations with PLA and the phenolic group of cardanol
with ABS. The cardanol consisting of the epoxy group
increased the reactivity toward PLA. In another approach, a
mixture of raw and epoxidized cardanol was reacted with either
PLA or ABS. It was observed that the 50:50 blend of PLA and
ABS following the second approach resulted in an impact
strength and elongation at break of 7.8 kJ·m−2 and 82.9%,
respectively.
Vadori et al.53 studied the influence of additives on PLA and
ABS blends synthesized by reactive extrusion and injection
molding. The additives were added to improve the
compatibility between the polymers PLA and ABS. ABS
(melt flow index (MFI) = 0.90 g/10 min at 3.8 kg, 240 °C)
with a high butadiene content or high rubber content was
added as a toughening agent. PLA and ABS are immiscible as-
is, and hence, compatibilizer needs to be added. Acryl
copolymer (Biostrength99) and Joncryl ADR 4368 were
added as a processability enhancer for PLA53 and chain
extender, respectively, enhancing the compatibility between
PLA and ABS. The amount of acrylic copolymer was limited to
0−5 wt %, and the chain extender was limited to 0−2 wt %.
The molecular weight of the blend was increased using the
chain extender, while the chain mobility was increased by the
acrylic copolymer. The barrel temperature was set at 240 °C,
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Table 2. Mechanical Properties of PLA-Based Blends and Composites for Durable Applications
tensile tensile elongation flexural flexural impact
PLA strength modulus at break strength modulus strength HDT (°C) (at
grade other components (MPa) (GPa) (%) (MPa) (GPa) (J·m−1) 0.455 MPa load) ref
Ingeo ethylenemethyl acrylate-glycidyl
3251D methacrylate (EMA-GMA)
terpolymer ∼45 ∼1.9 72.7 ∼500 37
poly(ether-b-amide) elastomeric
copolymer (PEBA)
Ingeo EMA-GMA
3001D
PEBA
∼32 ∼2.8 ∼55 ∼2.7 ∼80 90 38
aromatic sulfonate derivative
(LAK-301)
miscanthus fibers
Ingeo PTT (Mw: 56 300 g·mol−1)
3001D
EMA-GMA (MFI: 6 g/10 min) 44.2 2.0 60 122.9 90
Joncryl ADR 4368
Ingeo ABS (Magnum 1150 EM)
3052D
acrylic copolymer (Biostrength 900) 60 2.78 35 320 53
Joncryl ADR 4368
Ingeo PC
3251D
EBA-GMA (Elvaloy PTW) ∼47 ∼2.85 ∼90 ∼90 ∼2.8 715 130 42
Joncryl ADR 4368C
Ingeo PP
3251D
PHBV ∼31 ∼2.9 ∼2.5 ∼59 ∼2.8 ∼20 117 36
miscanthus biocarbon
Ingeo PC
3251D
chopped glass fiber strands ∼80 ∼3.7 ∼125 ∼3.9 ∼136 ∼145 89
EBA-GMA (Elvaloy PTW)
Joncryl ADR 4368C
Ingeo Hytrel RS 40F3 NC010
3001D ∼40 ∼2.3 ∼52 ∼55 ∼2.22 nonbreak 114
EMA-GMA (Lotader AX 8900)
Ingeo pinewood fibers
4043D 71 5.4 174
epoxy system (PBG + DICY)

the screw speed was set at 100 rpm, and the mixing time was
kept at 2 min. The experimentally determined optimized blend
formulation (PLA 50%:ABS 48%:acrylic copolymer 1.5%:
chain extender 0.5%) showed 600% enhancement in impact
strength. Further, the authors used statistical optimization to
determine the optimized blend (PLA 50%:ABS 45.2%:acrylic
copolymer 3.59%: chain extender 1.21%). According to the
model, the optimized formulation can yield an increase of 11%,
1000%, greater than 7%, and over 600% for tensile strength,
elongation at break, tensile modulus, and impact strength,
respectively. The results showed a balance between strength,
stiffness, and toughness. The work concluded that the
synthesized blend has impact strength and elongation at
break values comparable with those of commercially available
ABS, while the tensile strength and modulus increased
significantly.64 ABS is extensively used in automotive and
electronic applications considering its relatively low cost and
tailorable properties.53 The blend of various compositions was
prepared by the group, noting the MFI and HDT values.142
4.1.3. PLA/PC Blends. PC is an engineering plastic
consisting of a bisphenol A moiety and carbonate moiety
and has high impact resistance,143 high thermal stability,143,144
and high Tg144 compared to PLA. Bisphenol A imparts stiffness
16
to the molecule because of the aromatic rings; however, it also
restricts its crystallization ability. PLA (an aliphatic polyester)
and PC (an aromatic polyester)145 blends can be used in
computers, mobile phones, and automotive parts.143 However,
the low adhesion146 and high surface tension between PLA and
PC results in incompatibility between the polymers.143 Thus,
compatibilization is conducted to stabilize the blends, resulting
in fine dispersion due to reduced interfacial tension and
coalescence. Hence, interfacial adhesion between the phases
can be improved.147 Lee et al.147 used three compatibilizers,
namely, poly(ethylene-co-octene) rubber-maleic anhydride
(EOR-MAH), poly(styrene-g-acrylonitrile)-maleic anhydride
(SAN-g-MAH), and poly(ethylene-co-glycidyl methacrylate)
(EGMA) for PLA/PC blends. In addition, chain extenders
(low molecular weight compounds) were also added to
enhance the compatibility between the polymers in the blends.
The chain extenders rapidly reacted with the end group of
macromolecules, leading to the coupling of polymers.148
Phuong et al.146 prepared cellulose microfiber-based PLA/
PC blends and further synthesized ecocomposites. Along with
Bisphenol A PC, an interchange catalyst consisting of triacetin
and tetrabutylammonium tetraphenylborate (TBATPB) was
used. The tensile strength and Young’s modulus of the
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microcellulose reinforced (PLA/PC/Catalyst) composites
obtained were 68 MPa and 4.2 GPa, respectively.
Hedayati et al. 144 studied the effect of cobalt(II)
acetylacetonate (Co) as a transesterification catalyst and
dicumyl peroxide (DCP) as a radical initiator, which was
used to enhance the grafting between the components PLA,
PC, bisphenol A, and nanosilica. PC was added to enhance the
toughness of the blend as the addition of inorganic
nanoparticles can create defects in the PLA matrix. It was
observed that the PLA/PC/silica/Co composite showed a
substantial increase in elongation at break (57%), which
occurred due to the presence of low molecular weight
copolymers. However, the tensile strength and Young’s
modulus remained unaffected.
Yuryev et al.42 utilized PC for high heat resistance and
toughness for enhancing the characteristic properties of the
PLA by preparing the PLA and PC blend. However, this was a
challenging task as significant decomposition of PLA can be
observed at the processing temperature of PC, which is around
260−270 °C. PLA/PC blends without compatibilizers typically
had low elasticity and low HDT and were intrinsically brittle.
In the work of Yuryev et al., PLA/PC blends were prepared by
using EBA-GMA ethylene terpolymer or ElvaloyPTW. Another
additive used was Joncryl ADR 4368C, which was used as a
chain extender and for mitigating thermal degradation in PLA
and PC. The highly reactive epoxy groups present in Joncryl
ADR 4368C have the capability to form a bond with carboxylic
groups present in PLA and hence result in a high molecular
weight polymer. The additive Joncryl ADR 4368C has partial
miscibility, while EBA-GMA is immiscible in PLA. The
composition of the optimized blend PLA:PC:EBA-GMA was
32:62:6 wt % with a chain extender of 0.3 phr. The achieved
mechanical values are shown inTable 2.
Yuryev et al.89 developed a high impact strength and high
heat resistance blend using PLA, PC, and GF. In this work,
linear and branching PCs were also processed and compared in
PLA/GF blends. The low compatibility between PLA and PC
was enhanced by the addition of a compatibilizer. Impact
modification was done by adding poly(ethylene-n-butylene
acrylate glycidyl methacrylate) (EBA-GMA) ethylene terpol-
ymer. Joncryl ADR 4368C, an epoxy-based chain extender, was
also added. The mechanical properties data of the PLA/
branched PC/GF blend at 50 rpm screw speed is shown in
Table 2. It was inferred that the impact modification occurred
because of the impact modifier phase accumulated in the
brittle phase of the blend. Excellent elongation and good
impact strength were achieved in the PLA/PC blend upon
adding only 7.5 phr GF loading. The PLA/PC/GF composite
enhanced heat resistance to greater than 145 °C.
4.1.4. PLA/Nylon Blends. Scarce information is available
in nylon/PLA binary blends and their compatibilization.
Neppalli et al.149 ameliorated the mechanical properties of
the PLA by incorporating electrospun nylon 6 fibers. In the
first step, nylon fibers were made by electrospinning. Further,
the fiber mats were placed between PLA sheets and
compression molded at 180 °C. At this temperature, PLA
was melted and formed a continuous phase by filling the voids.
The modulus of the nylon fiber reinforced PLA composite
obtained was 3-fold greater than that of PLA.
Gug and Sobkowicz150 enhanced the compatibility between
PLA and polyamide11 using a catalyst. The catalyst (p-
toluenesulfonic acid (TsOH)) compatibilized the polymers via
an ester-amide exchange reaction in reactive extrusion. The
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optimum amount of TsOH was found to be around 0.5 wt %,
beyond which (>2 wt %) depolymerization occurred and,
hence, blend properties deteriorated. The blend under an
optimized catalyst concentration resulted in 50% enhancement
in elongation at break. The authors deduced that the optimized
process could potentially reduce the complexity and processing
time.
Liu et al.119 developed fully biobased PLA blends having
super toughness. The work utilizes LDI and HDA as
toughening monomers. LDI and HDA were derived from a
sugar-based monomer and plant oil, respectively. LDI and
HDA were in situ polymerized to obtain hydrogenated dimer
acid flexible biopolyamide (c-HDAPA). The fully biobased
PLA blends showed excellent toughness (impact strength was
>1200 J·m−1) and exceptional melt flowability. The elongation
at break obtained was greater than 400%. Figure 8a illustrates
the effect of HDAPA concentration in the matrix.
Figure 8. (a) Effect of HDAPA on compatibilization and cross-
linking.119 (Reprinted with permission from ref 119. Copyright 2019
American Chemical Society.) (b) Schematic representation of the
effect of elastomer-graf t-PLA on a matrix.120 (Reprinted with
permission from ref 120. Copyright 2019 American Chemical
Society.) (c) Digital images of samples after Izod impact strength
and mechanical data of samples: (A) neat PLA, (B) PLA/ECO, (C) 5
wt % PLLA-b-PMMA in PLA/ECO (80:20) blend, and (D) 20 wt %
PLLA-b-PMMA in PLA/ECO (80:20) blend.121 (Adapted with
permission from ref 121. Copyright 2020 American Chemical
Society.)
A few researchers worked on nylon-based ternary blends.
Anstey et al.118 investigated the performance of nylon 6, PLA,
and PP, and compatibilized the blend with PP-g-MA. The
incorporation of PLA resulted in increased stiffness and tensile
and flexural strengths. However, the focus of the work was to
enhance the polyolefin-polyamide blend properties through the
blending method.118 The same group performed rheological
and morphological analyses and concluded that PLA acted as a
flow enhancer in the ternary blends and improved process-
ability.151
4.1.5. PLA/PET Blends. The significant difference between
the processing temperature of PET (∼260−300 °C) and the
melting temperature of PLA (∼160−180 °C) limits the
blending of the two polymers.116,152 Torres-Huerta et al.153
worked on accessing the miscibility of the PET/PLA blends.
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The blends showed weak interactions, suggesting electrostatic
interaction and hydrogen bridges between the components.153
McLauchlin et al.152 studied the effect of PLA (0.5−20%)
inclusion in PET. The work was conducted to check the
impact on the mechanical and thermal behavior of PLA in
recycled PET (rPET) process streams. The polymers were
coprocessed at a short residence time (4 s) in an injection
molding machine. No additive was used in the process to
enhance the compatibility between the two polymers. A drastic
reduction in mechanical strength was observed when more
than 2% of PLA was added to PET. The behavior was ascribed
due to the increased number and size of PLA microscopic
beads.
You et al.116 compatibilized PLA/PET blends using epoxide
compatibilizers. EBA-GMA and SA-GMA were used as a
toughening agent and chain extender, respectively. The
carboxylic and hydroxyl groups of PLA reacted with the
epoxy group on EBA-GMA. Further, SA-GMA (Joncryl)
resulted in the reduction of thermal degradation of PLA in the
blend. PLA degradation was restricted by the epoxide reaction.
However, it was observed that adding two compatibilizers does
not significantly enhance the properties. Instead, EBA-GMA
formed micelles and showed poor adhesion with the PLA
phase. Furthermore, the addition of only SA-GMA acted as a
compatibilizer and chain extender simultaneously. The
addition of the toughening agent resulted in 292% enhance-
ment in impact strength; however, the modulus was reduced to
25%.
4.1.6. PLA/Polyolefin Blends. Polyolefins such as PP,
LDPE, and linear low density polyethylene (LLDPE) have also
been used to fabricate PLA blends for improving PLA
properties. Hamad et al.154 synthesized PLA/LDPE blends
without using any compatibilizer and showed incompatibility
between the two polymers.
Chen et al.155 worked on enhancing the processability and
mechanical strength of PLA. In this work, paraffin wax (PW)
was mixed with PLA to improve the ductility and fluidity of the
matrix. However, the melting temperature of PLA was ∼55 °C,
which is much lower than that of PLA, and thus caused
processing difficulties. The immiscibility of PW and PLA was
improved by adding LLDPE to the PLA/PW blend. PLA/PW/
LLDPE was prepared by melt compounding extrusion and
subcritical gas-assisted processing (SGAP) using nitrogen gas.
Further, injection molding was done to prepare mechanical test
samples. It was concluded from the results that LLDPE
improved the thermal stability of the PLA/PW blends. Further,
LLDPE and PW in the PLA matrix acted as nucleating agents.
In addition to that, SGAP yielded a better dispersion
morphology and better mechanical properties than melt
compounding extrusion.
Harris et al.156 mixed PLA, HDPE, and PE-g-MaH and then
melt blended the blend. A high stability of PLA toward
degradation was observed when HDPE was mixed with PLA.
Wen-Dong et al.157 worked on preparing PLA/PP blends
using the initiator trimethylolpropane triacrylate (TMPTA).
The reactive extrusion was induced in the presence of
ultraviolet radiation. The activated vinyl groups in TMPTA
were used as grafting sites in the reactive compatibilization
process. The tertiary carbon in PLA and activated terminal
radicals in PP generated due to chain scission of PP molecules
readily take part in grafting.
Casamento et al.158 observed the compatibilization effect of
PLA/LDPE blends by using two natural surfactants. The ratio
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of surfactants Tween 80/Span 80 (72:28 wt %) was
characterized by hydrophilic−lipophilic ratios. Rheological
and morphological studies of PLA/LDPE (70/30 wt %)
revealed that the addition of surfactants (Tween 80/Span 80)
improved the storage modulus. A remarkable decrease in
LDPE particle size in the PLA matrix was also detected.
4.1.7. PLA/Elastomer Blends. Zhang et al.37 synthesized
multiphase ternary blends of PLA for enhancing toughness
through reactive melt blending. In this system, EMA-GMA
terpolymer and a renewable PEBA were blended with PLA.
Renewable PEBA was synthesized with the combination of
biosourced polyol with castor oil comprising aliphatic
polyamide, polyether, and diacid as a hard block, a soft
block, and a joint for two blocks, respectively. PEBA has the
tendency to significantly enhance the toughness and flexibility
of PLA. However, immiscibility and poor interfacial adhesion
of PEBA with PLA limit its use as a toughener of PLA. EMA-
GMA was used as a functionalized copolymer containing epoxy
groups, which tends to react with functional groups (hydroxyl
or carboxyl) of PLA molecules. It acted as a reactive
compatibilizer and toughening agent for PLA. That is, the
PLA and EMA-GMA binary blend has good interfacial
adhesion and good compatibility between the phases. The
PLA/EMA-GMA/PEBA blend of 70:20:10 composition
displayed an improvement in miscibility that resulted from
the reaction between GMA and the end functional groups of
PEBA and PLA. The dominant morphology showed a ‘multiple
stacked structure’ with partial encapsulation or stack formation
of minor phases. In this morphology, two dispersed polymers,
small PEBA particles (poor interfacial adhesion) stuck on large
EMA-GMA particles (good interfacial adhesion), were
detected in the PLA matrix for PLA/EMA-GMA/PEBA of
70:20:10 composition. The HDT of the developed samples
remained the same as that of neat PLA. The impact strength
achieved for this supertoughened ternary PLA system
(PLA:EMA-GMA:PEBA (70:20:10 wt %)) was ∼500 J·m−1.
An exceptional synergistic effect of the phases contributed to
the exceptional toughness of the blend.
Nagarajan et al.114 investigated the effect of thermoplastic
copolyester elastomer (TPCE) on improving the toughness of
PLA. In this work, TPCE (HytrelRS 40F3 NC010) was used,
which contained no less than 50% biobased ingredients.
Adding Hytrel (30 wt %) in PLA leads to a 6-fold
enhancement in impact strength (234 J·m−1). Reactive
compatibilizers EBA-GMA (ElvaloyPTW), EMA-GMA (Lo-
tader AX 8900)), EBA-MaH (Lotader 3410), and EMA-MaH
(Lotader 3410) were added individually with PLA and Hytrel
to prepare the blends. The blend ratio for PLA/Hytrel/
compatibilizer was 70:10:20. The nonbreak impact behavior
was noticed for the PLA/Hytrel/EMA-GMA blend; the data is
shown inTable 2. Massive shear yielding and larger stress
whitening were observed for this blend supported super-
toughening effect.
Deng et al.120 developed an elastomer-g-PLA copolymer
which resulted in achieving high-performance stereo complex
(SC)-PLA/elastomer blends, as the SC blends impart strength
and durability.159 EMA-GMA in the presence of catalyst was
reacted with the hydroxyl group of poly(L-lactide) (PLLA) and
poly( D-lactide) (PDLA) to obtain a graft copolymer.
Interestingly, the graft copolymer compatibilized and improved
the melt stability of the stereocomplex matrix. The graft
copolymer also worked as an interfacial enhancer, i.e.,
strengthened the blend interface and improved toughening
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efficiency. The effect of a catalyst on the graft copolymer and
matrix is illustrated in Figure 8b. The values of Vicat softening
temperature and notched Izod impact toughness achieved were
201 °C and 65 kJ·m−2, respectively.
Jiang et al. 121 prepared PLA and renewable poly-
(epichlorohydrin-co-ethylene oxide) (ECO) elastomer blends,
which were compatibilized by the synthesized PLLA-b-PMMA.
The synthesized block copolymer increased the interfacial
adhesion between PLA and ECO. Sample 5 wt % A181M690
represents 5 wt % PLLA-b-PMMA in PLA/ECO (80:20
blend) which shows a degree of polymerization of 181 for
PLLA and 690 for PMMA. The results showed that the
elongation at break achieved was more than 260% and impact
strength was 63 kJ·m−2 and nonbroken behavior was observed,
as shown in Figure 8c. The digital images after tensile tests
show necking and stress whitening, indicating ductile behavior.
The change in morphology from sea-island structure to
tricontinuous was observed upon the addition of the block
copolymer because of compatibilization.
4.2. PLA-Based Biocomposites
Composites are the heterogeneous combination of two or
more constituents comprising the matrix, fillers, compatibil-
izers, and reinforcements. The sizes and shapes of the fillers
and reinforcements also govern the properties of the
composites. Wertz et al.123 worked on improving the HDT
and self-healing properties for durable applications. The
microcapsules in the PLA composite released self-healing
additives to the fracture regions and improved thermal
tolerance and served as nucleating agents. The PLA films
were prepared by incorporating dicyclopentadiene (DCPD);
further, a Grubbs first-generation ruthenium metathesis
catalyst was added. The optimized composition showed 38
± 3% fracture recovery toughness. Relative to virgin PLA, the
increase in HDT and degree of crystallinity achieved was ∼21
°C and ∼11%, respectively. In addition to that, PLA
biocomposites consisting of fibers160−162 (synthetic/natural)
and biofillers (biocarbon) have been developed for enhancing
the performance.
4.2.1. PLA/Synthetic Fiber-Based Biocomposites.
4.2.1.1. PLA/Carbon Fiber Biocomposites. Carbon fibers
(CF) are lightweight and strong materials that have use in
bicycle frames, automobiles, and aeronautics.91 Chen et al.91
prepared PLA/CF biocomposites. The analyses revealed
recycled CF and PLA reinforcement as shown by enhanced
tensile strength and modulus data. It was observed that, with
the addition of 30% fiber loading, flexural modulus and
strength increased to 400 and 53%, respectively. It was inferred
that the enhancement in modulus was due to the restricted
polymer chain movement caused by the filler. In addition to
that, fibers assisted in dissipating forces and resulted in
enhanced strength.
Hazer et al.143 studied PLA/PC-based composites reinforced
with CF. A tensile strength of 114 MPa was achieved for the
PLA/PC/CF (50:50:30) composite.143 Hazer et al.163 also
worked on studying the effect of flame retardants on the
mechanical strength of PLA/PC composites reinforced with
GF. The flame retardants used in the work are ammonium
polyphosphate (APP) and triphenyl phosphate (TPP). The
tensile strength obtained for PLA/PC/CF (50:50:30) was 110
MPa, which was approximately 90% more than that of the
PLA/PC blend. However, the decrease in the strength was
obtained upon addition of the flame retardants.
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A high-performance PLA composite was printed using chiral
CF. The chiral samples showed enhancement in strength,
tensile modulus, and energy absorption at the break. A 2-fold
augmentation was attained for absorbed energy. It was inferred
that the high strength achieved was due to the fiber filler. This
research has the potential for fabricating high strength auxetic
metamaterials.164
4.2.1.2. PLA/Glass Fiber Biocomposites. Glass fibers (GFs)
have been preferred over CF due to their lower cost. In
addition to that, GFs impart great mechanical properties and
required heat resistance.128 Yuryev et al.89 developed PLA/PC
biocomposites consisted of GF composites. EBA-GMA was
added as an impact modifier. The heat resistance of the PLA/
PC blend reached 145 °C upon the addition of GF to make it a
biocomposite. In addition to that, superior mechanical
properties were obtained. Enhancement in flexural strength
and modulus was observed at low shear processing even at low
GF loading. The flexural strength and modulus obtained at 50
rpm screw speed and 5 phr GF loading were 126 and 3912
MPa, respectively. The competitive weight-to-strength ratio
and relatively low density made the biocomposite suitable for
the electronic and automotive industries. The composites were
prepared by compounding and injection molding.
PLA/continuous GF (CGF)-based composites were also
prepared using a 3D printer and a fused filament fabrication
technique. CGF was used as a reinforcing phase. It was found
that optimal printing speed resulted in various high quality
geometric shape composites.165 Akindoyo et al.128 synthesized
PLA/GF composites and noted the effect of an impact
modifier (BiomaxStrong) and chain extender (CESA-extend)
in the composite. The enhancement in impact strength,
crystallinity, and flexural modulus was 63%, 58%, and 66%,
respectively. The group further worked on developing high
load bearing composites for orthopedic applications. Surface-
modified hydroxyapatite (HA) was added to prepare a PLA/
HA/GF composite. A chain extender and impact modifier were
not added. However, PLA and HA compatibility was enhanced
by modifying HA with a phosphate modifier. The addition of
HA improved bonding and facilitated dispersion. Heteroge-
neous nucleation in the PLA matrix was also induced. The
composite possessed an enhanced tensile modulus and flexural
modulus, namely, 86% and 82%, respectively. When compared
with PLA, the PLA/HA/GF composite showed a 1273 MPa
increase in the storage modulus.166
Wang et al.167 added silane-modified GF to PLA by twin-
screw compounding. The increased thermal, mechanical, and
foaming ability of PLA was achieved. The addition of 20 wt %
modified GF showed improved rigidity and strength around 2-
fold, and impact toughness was more than 3-fold greater than
that of PLA. It was inferred that the enhanced mechanical
property was due to the anchoring effect of GF and chemical
bond formation between PLA and GF. HDT also increased
upon adding GF to PLA. However, the MFI of PLA was
reduced.
4.2.2. PLA/Synthetic Plastic/Natural Fiber-Based Bio-
composites. Biocomposites composed of renewable or
nonrenewable polymer matrices and natural fibers/biofibers
have the capability to be used in building products and
automotive applications.168,169 Reinforcing natural fibers can
be categorized as wood fibers and nonwood fibers. The
nonwood fibers can further be classified as grass, seed/fruit,
leaf, bast, and straw fibers.169 Fibers such as flax, jute, hemp,
kenaf, sisal, ramie, abaca, bagasse, and coir have been explored
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as reinforcing agents. Natural fibers, when used as fillers in
composites, for the same weight in GF composites, can show
25−30% more strength.169 Biofibers have gained attention
over traditional fibers170 such as GF and CF due to availability,
economics, adequate specific strength, good thermal proper-
ties, improved toughness, low density, enhanced energy
recovery, and reduced skin and respiratory irritation. However,
a critical challenge for biofibers in composites is their low
reactivity because of their hydrophilic nature. The hydro-
philicity of biofibers results in a reduction of their compatibility
with the hydrophobic polymer matrix.171 Thus, the mod-
ification of fibers to make them more reactive can be done by
corona treatment, plasma treatment, alkaline treatment, silane
treatment, enzyme treatment, acetylation, and maleated
coupling.172 The biofibers also possess low processing
temperatures with respect to GF or CF.171 Composites
consisting of natural fibers such as sisal, hemp, bamboo, coir,
jute, and kenaf have the potential to be used in structural parts
and low-cost housing.173 PLA biocomposites have been
prepared using various fibers such as kenaf, bamboo, coir,
flax, cellulose, and jute fibers.172
Zhao et al.174 used pinewood fibers as reinforcing materials
for enhancing PLA strength. However, the pine fibers create
discontinuities and have less interfacial adhesion with PLA.
The improvement in interfacial adhesion between the matrix
and reinforcing agent was conducted by modifying the fibers
with epoxy. The epoxy resins possess adhesiveness, heat
resistance, and chemical resistance which can bridge the gap
between the matrix and filler. In addition to that, it enhances
the compatibility between the hydrophobic polymer matrices
and hydrophilic natural fibers. The epoxy system was a two-
component system formed by reacting poly(bisphenol A-co-
epichlorohydrin) glycidyl end-capped (PBG) and dicyandia-
mide (DICY). DICY used in the system was a hardener, a
curing agent that was used for the development of a cross-
linked network that resulted in desirable thermal and
mechanical properties. The epoxy-modified pinewood fibers
were synthesized by the reaction between PBG and DICY on
fibers. The epoxy solution was impregnated on the fibers.
Further, PLA and epoxy-modified fibers were shear mixed. The
hollow fibers allowed the epoxy to penetrate them and
mechanically interlock, which enhanced layer adhesion.
Nagarajan et al.38 successfully developed PLA-based
biocomposites, synthesized by combining a supertoughened
PLA ternary system, nucleating agents, and natural fibers, with
improved HDT and impact strength through reactive extrusion
followed by injection molding. Miscanthus fibers, a perennial
grass, were added in a supertoughened ternary blend of
PLA:EMA-GMA:PEBA (70:20:10) due to its availability at
low cost. Among (i) the potassium salt of 5-dimethyl
sulfoisothalate (LAK-301), (ii) magnesium oxysulfate (HPR-
803i), and (iii) precipitated calcium carbonate (Specialty
Minerals Inc.) nucleating agents, LAK showed the fastest rate
of crystallization and reduced the free energy barrier for
nucleation. An aromatic sulfonate derivative nucleating agent
(LAK-301) of 1 wt % was added, which exhibited a dramatic
reduction in crystallinity. The presence of nucleating sites in
virgin PLA supports the initializing crystallization process,
which shortens molding cycle times. LAK is an organic
nucleating agent, which favored chemical nucleation by chain
scission in polyesters. The process further creates ionic chain
ends and then ionic clusters which work as nuclei. The
addition of fibers also aids crystallinity by increasing stiffness,
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increasing heat resistance, and decreasing the cost of the
composite by reducing the use of an expensive matrix. As
compared to neat PLA, biocomposites revealed a 4-fold
enhancement in impact strength and HDT reached 85 °C.
Optical microscopy was conducted at 120 °C and revealed that
the samples not containing LAKshowed large spherulite sizes
formed at a relatively slow rate compared to samples having
LAK. Samples having LAK showed densely packed spherulites
which formed at a faster rate. It was also concluded that LAK
reduces the interfacial free energy barrier for nucleation
efficiently and thus a significant increase in crystallization rate
occurred.
Oat hull fibers have also been used with PLA/PP for the
preparation of reinforced biocomposites. The reinforcement
was conducted by the addition of a compatibilizer, namely, A-
C ethylene propylene maleic anhydride copolymer. Oat hull
fiber imparted the nucleation effect in the biocomposite. The
enhancement in tensile and flexural strength in the
biocomposite was 40% and 46%, respectively.175
4.2.3. PLA/Synthetic Plastic/Biofiller-Based Biocom-
posites. 4.2.3.1. PLA/Biocarbon-Based Biocomposites. Bio-
carbon or biochar is achieved by thermochemical conversion
or pyrolyzing forestry or agricultural waste in an oxygen-
limited environment. The biological origin of carbon is
biocarbon, unlike carbon black which is obtained from
petroleum-based oil or natural gas. Biocarbon (a carbon
sequestration source: 50−80% carbon content based on the
source) has gained attention due to its chemical and thermal
stability, relatively greater hydrophobicity than that of natural
fibers, low environmental impact, cost-effectiveness, large
surface area, and electrical properties.176 In addition to that,
it has a wide processing window, unlike natural fibers where
degradation occurs at temperature more than 200 °C.
Biocarbon imparts strength and stiffness when used as a
reinforcing agent to the matrix. The desired yield, pore
volumes, and surface area can be achieved by varying pyrolysis
temperature. Arrigo et al.176 worked on synthesizing PLA/
biocarbon biocomposites by solvent casting and melt mixing
processing routes. Biocarbon was prepared by pyrolyzing waste
brewed ground coffee. Biocarbon has the potential to be used
in electronic casings and automotive interior parts.
Snowdon et al.36 synthesized PLA/PP/poly-
(hydroxybutyrate-co-hydroxyvalerate) (PHBV) with a pyro-
lyzed miscanthus biocarbon filler. PHBV has been added to
PLA and PP, as PHBV has surface tension analogous to the
“polar PLA” and “nonpolar PP” immiscible portions.
Biocarbon was selected because of its reinforcing capacity,
lower density, availability, less cost, and environmentally
friendly characteristics. The data are shown in Table 2.
Snowdon et al.177 compared the influence of biocarbon and
talc on extrinsic properties of PLA biocomposites for durable
applications. Superior flammability resistance was attained by
the biocomposite consisting of biocarbon. Abrasion tests
showed limited frictional wear in the synthesized PLA/
biocarbon-based durable composites.
4.3. PLA-Based Bionanocomposites
Nanofillers (having at least one dimension 100 nm) have also
been incorporated in PLA for developing products for durable
applications. The nanofillers can broadly be classified into four
types: (i) zero-dimensional; (ii) one-dimensional, namely,
carbon nanotubes; (iii) two-dimensional, namely, clay; (iii)
three-dimensional, namely, polyhedral oligomeric silsesquiox-
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anes (POSSs).178 The nanocomposite materials have the
potential to reduce the weight of the products. The PLA
nanocomposites have been prepared by using montmorillon-
ite,179 graphene nanoplatelets,180 layered silicate, halloysite
nanotube, sepiolite, carbon nanotubes, silver nanoparticles, and
zinc and titanium oxide nanoparticles.181
One of the challenges of working with nanofillers is
dispersion in the matrix. Functionalization of nanoparticles
controls dispersion and distribution. Fu et al.182 functionalized
graphene nanoparticles and added an elastomer modifier
containing an epoxy group that improved interfacial adhesion
between graphene and PLA.
Zhao et al.183 developed high performance microcellular
polymer foams by preparing prefoamed pellets by supercritical
fluid (SCF) extrusion foaming. The injection molded PLA/
clay nanocomposites were developed by enhancing diffusion,
which was achieved by the plasticizing effect of SCF. Further,
another driving force for enhancing intercalation and
dispersion clay nanofiller was achieved by changing the
phase from supercritical to gaseous state in polymer melts.
A PLA/nanosilica/epoxidized soybean oil (ESO) nano-
composite showed enhanced toughness. The elongation at
break of PLA/nanosilica/ESO increased ∼42% with respect to
PLA/nanosilica.184
Chen et al.185 synthesized a nanocomposite using PLA,
thermoplastic polyurethane (TPU), and graphene oxide (GO).
The fused deposition modeling (FDM) 3D printing of
nanocomposites has the potential to be used in biocompatible
materials. The addition of TPU and GO in PLA enhanced
mechanical properties. The addition of GO also resulted in
achieving thermal stability by degradation temperature increase
by 90 °C. Furthermore, the addition of GO increased
compression and tensile modulus by 167% and 75.5%,
respectively.
The poor ultraviolet (UV) stability of PLA restricts its use
under atmospheric conditions. Zhang et al.186 added TiO2
nanoparticles for the UV-shielding effect. For maintaining the
stability of nanoparticles in the polymer matrix, TiO2-
polydopamine (PDA) hybrid nanoparticles were developed.
The hybrid nanoparticles in the PLA matrix showed out-
standing UV-shielding performance without forfeiting trans-
parency. Increased strength and toughness were observed by
adding 0.2 wt % nanoparticles. The developed high-perform-
ance PLA products contain TiO2-PDA hybrid nanoparticles.
Such developed products can be used in longer service life
applications.
5. ADVANCES IN PLA-BASED BLENDS AND
COMPOSITES
5.1. Processability
The processing technique significantly affects the properties of
PLA composites.187,188 The factors that substantially influence
the crystallinity and mechanical properties of PLA are
annealing condition, degree of crystallinity, and crystallite
orientation.189 The highest melting point crystals are produced
when the samples are annealed close to the melting point.
Higher melting crystals and more perfect crystals are produced
when annealing is done for extended times.189 Kultravut et
al.138 studied the effect of annealing in a PLA/PTT blend in
the presence of a reactive compatibilizer and observed that the
hydrolytic instability or degradation was controlled. Thermal
annealing above Tg resulted in the fabrication of a polylactide/
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ethylene−acrylic EGMA terpolymer elastomer with an impact
strength of 94 kJ·m−2 that is 52 times more than that of
polylactide. It was inferred that the enhancement occurred
because of the decrease in Tg of the elastomeric particles in the
blend, which is related to the negative pressure effects which
were imposed on the particles during the quenching and
further thermal annealing process.190
Cooling times and removability of the samples from the
mold affect the overall production cost and efficiency. As the
exceeding times and deformation in the samples defeat the
purpose of making cost-effective materials and processes.
Nagarajan et al.38 used LAK as a nucleating agent which
inhibits sample warping during removal from the mold, and the
cooling times do not exceed 60 s.
Nagarajan et al.90 also observed that the high screw speed
during processing results in coalescence suppression in the
blend which further reduces the particle size of the dispersed
phase. These uniformly distributed smaller particles further
result in a reduced interparticle distance. The decrease in
interparticle distance of the dispersed phase in the blends is
considered the main reason for increased impact toughness.
Yuryev et al.42 studied the impact of processing temperature
on a PLA/PC blend. The increase in toughness was observed
by increasing the temperature. The use of a chain extender at
270 °C led to the highest toughness values. The conventional
processing temperature of PLA is in the range of 180−220 °C,
and hence, the incorporation of a chain extender during PLA
processing will prevent the degradation process. Accordingly,
the process has to be maneuvered in such a way that, at
increased processing temperature, which results in reduced
induction time, compatibilization and reaction rate can be
accelerated without hampering the PLA chains.
Wang et al.109 prepared a superthermal insulated PLA/PET
foam by high pressure microcellular injection molding
(HPMIM) without using any compatibilizer as an additive.
The PET nanofibril reinforcement created high-performance
foams. Initially, PLA and PET pellets were put in a twin screw-
extruder. The extruded sample generally shows sea-island
microstructure, where less sample dispersed as an island and
more content sample forms sea morphology. The extruded
PLA/PET composite fibers were drawn by melt spinning and
then stretched which converted the spherical PET domains
into nanofibers. The fibrils were further cut by pelletizers, and
the pellets were inserted in the foam injection molding. Along
with the composite particles, gas was also inserted into the
injection molding machine. Finally, the mold-opening foam
injection molding (MOFIM) technology resulted in the foam
structure. The foam was prepared by applying 20 MPa, and
after holding for some time the mold was instantly opened for
triggering secondary foaming. The exceptional thermally
insulating material was obtained due to the large expansion
ratios created during processing. Further, the PLA/PET foam
showed a 7-fold enhancement in Izod impact strength.
Tan et al.191 worked on fabricating polymer−polymer
composites in which the polymeric microfibrils were well
distributed in the polymer matrix. The morphology was
obtained when the blend polymers have wide processing
temperature and melting temperature differences. The fibers
were made by the polymer having a high melting temperature,
and the matrix was prepared by the polymer having a low
processing temperature. Tan et al.191 prepared the highly
oriented microfibrils, which were developed in situ to replace
the spherical stiffer polymer morphology. The steps involved in
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ACS Engineering Au
manufacturing microfibrillar composites are blending (com-
pounding), fibrillization or drawing (stretching), and isotrop-
ization. The presence of polymer fibers (as the reinforcing
material) in the polymer matrix has the potential to improve
the mechanical properties of the incompatible polymer
(LDPE)-polymer (PET) blends. Figure 9 shows the presence
Figure 9. Polarized optical micrographs of the films consisting of PET
fibers: (a) 0.5% fiber loading and (b) >1% fiber loading.192
(Copyright 2019. Reproduced with permission from John Wiley &
Sons, license number: 5124000602586.)
of fibers in polymer films. Pon Kumar et al.192 observed
agglomeration as shown in Figure 9b with the increase in
loading. However, reducing the agglomeration of those fibers is
a challenging task.
Kulkarni et al.193 worked on enhancing the melt strength of
PLA for improving its melt processability. The researchers
synthesized star telechelic PLA ionomers that showed a
dramatic increase in elasticity. Telechelic ionomers consist of
ions in which ions are present at the end of the polymeric
chains. It was demonstrated that the incorporation of ionic
groups in high molecular weight PLA makes it more amenable
to processing applications. Huang et al.194 improved the
rheological and mechanical properties by electron-induced
reactive processing (EIReP) for improving interfacial energy
between immiscible polymer phases without using any
compatibilizers. It was observed that the chemical free
approach increased the elasticity and melt strength of PLA
pubs.acs.org/engineeringau Review
blends. Further, enhanced crystallinity in PLA and PLA blends
was also observed. It was speculated that the increased
crystallization could be due to the partial heterogeneous
nucleation effect triggered by in situ long-chain branches
present in blends.
Further, researchers worked on widening the processing
window of PLA. Chen et al.195 prepared a long-chain branched
PLA structure. The structure was prepared by premixing
trimethylolpropane triacrylate with PLA pellets. The reactive
extrusion of the mixture was carried out, and the sample during
the melt extrusion process was irradiated with UV to control
chain scission. The UV-induced reactive extrusion process was
conducted without using any peroxide initiator and processed
at high temperature.196 Liu et al.197 enhanced the processing
window by more than 40 °C. The nonwoven core−sheath PLA
fibers were developed by hot-pressing. The sheath was
developed from PLA consisting of 10 mol % D-lactide
(PLA90), and the core was developed from poly(L-lactide).
Yan et al.198 introduced stereocomplex crystallites for
enhancing melt strength and widening the processing window
of PLA.
5.2. Strength and Toughness
Generally, the mechanical properties of the composites are
guided by the adhesion between the reinforcement (dis-
continuous) and matrix (continuous) phase. The tensile
strength can be enhanced by adding synthetic fibers (such as
carbon-based or glass) or natural fibers (jute, kenaf, hemp,
sisal, or flax). It was observed that fibers having a larger length
to diameter ratio in the PLA matrix could carry the load in
composites. Apart from fibers, the mechanical properties can
be enhanced by adding inorganic fillers of micro- and
nanosizes such as talc, HA, and mica. Clay platelets have
also been used to impart impermeability or barriers to water
and gases. In addition to that, they extend the diffusion path or
create a tortuous path for small molecules.199
Further, immiscible PLA/PEBA binary blends showed a
slight improvement in impact strength. This partial improve-
ment was observed because of the large size dispersed phases
and weak interfacial adhesion. On the contrary, PLA/EMA-
GMA showed a remarkable enhancement in elongation and
impact strength, signifying better compatibility of the EMA-
GMA modifier with PLA. The stiffness of PEBA significantly
affected toughness and flexibility for the 70:10:20 wt %
composition of PLA/EMA-GMA/PEBA. In addition to that,
changing PEBA grades of different stiffness does not affect the
impact strength for the formulation. A distinct “multiple
stacked structure” morphology for the renewable elastomer-
based PLA blend was observed, in which the minor phases
EMA-GMA and PEBA were partially encapsulated, and
showed enhanced toughness. It was believed that the reason
for the significant toughening effect was the synergistic effect of
interfacial adhesion, interfacial cavitation, and shear yielding.
The shift in the Tg value of the ternary blend showed improved
miscibility between the components because of the reaction
between the terminal functional PLA and PEBA groups and
GMA group. Consequently, EMA-GMA in the ternary blend
acts as a reactive compatibilizer and effective toughening
agent.37
5.3. Heat Resistance
Heat resistance determines the ability of a material that can
retain its desired properties for a longer duration at maximum
service temperature. The crystallinity and crystalline nature of
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PLA govern its heat resistance. Increased heat resistance of

PLA can be achieved by adding heat resistant polymers or
reinforcing agents or by adding nucleating agents. It has been
observed that a well dispersed nanoclay can act as a super heat
insulator.199 Hashima et al.200 developed a PLA alloy having
supertoughness and excellent heat resistance. The alloy
consists of PLA, PC, hydrogenated styrene−butadiene-styrene
block copolymer (SEBS), and poly(ethylene-co-glycidyl
methacrylate) (EGMA). EGMA acts as a reactive compatibil-
izer, and SEBS was used to dilate the PLA-PC matrix to
enhance local segmental motions. In some of the samples, zinc
phenylphosphonate was incorporated as a nucleating agent. PC
was added to elevate the HDT as it has a high glass transition
temperature (∼140 °C). The HDTs observed for the injection
mold samples as cold (40 °C) and hot (80 °C) were 88.6 and
94.5 °C, respectively.200 Scientists at the University of Akron
modified PLA in such a way that it can contain boiling liquids
without shrinking, turning opaque, or degrading.201
5.4. Flame Resistance
The flammability of PLA limits its use in practical applications
such as automotive materials, electronic appliances, and
textiles. PLA is inherently flammable with a low limited
oxygen index (LOI) of only 19 vol % and tends to drip upon
being ignited, extremely restricting its applications in the fields
where excellent flame-retardancy performance is required.202
Hence, it is highly imperative to develop PLA so that it meets Figure 10. (a) Mechanism of FR on PLA composite.212 (Copyright
the industrial requirements. The materials that have been 2018. Reproduced with permission from Elsevier, license number:
developed for enhancing the flame resistance of PLA are as 5124001163913.) (b) Mechanism of FR on PLA/DM-H compo-
follows: APP,104,203,204 mixture of cyclic phosphonate esters site.213 (Reprinted with permission from ref 213. Copyright 2020
(Afflamit PE),205 melamine resin microencapsulated ammo- American Chemical Society.) (c) (i) Digital images showing dripping
of the samples and (ii) mechanism of intumescent FR in PLA.214
nium polyphosphate,206 phosphorus and nitrogen grafted
(Adapted with permission from ref 214. Copyright 2019 American
lignin,207 charring agent containing benzene and triazine Chemical Society.)
joined with APP,208 lanthanum oxide effect on APP,209
sepiolite grafted with 9,10-dihydro-9-oxy-10-phosphaphenan-
threne-10-oxide (DOPO),210 biocarbon,177 biobased poly-
phosphonate obtained by reacting phenylphosphonic dichlor- endowing the antidripping attribute in the condensed phase.
ide (PPDC), caged bicyclic phosphorus, and plant-derived The dark brown color of the sample illustrates the charring
diphenolic acid (DPA).211 effect in the sample containing FR in Figure 10c,i. The A-A
The flame retardant (FR) mechanism is shown in Figure released nonflammable gases in the gas phase. The FR (15%)
10a. Char formation takes place in the matrix when the sample in PLA showed an increase of LOI from 20% (neat PLA) to
is exposed to the flame. The formation of the char restricts heat 30.5%, and the UL rating was V-0. The mechanism of the
and oxygen transfer inside the substance and decreases the sample is shown in Figure 10c,ii.214
amount of smoke particles and flammable gases. The FR acts Zhang et al.57 synthesized bioderived FR, forming a core−
as a barrier, and additionally, the char layer increases the shell structure. The FR consists of chitosan, alginate, and APP.
stability. In the gas phase, the FR generates the PO• radical, APP illustrated high flame retardant effectiveness in PLA.
resulting in quenching of OH• and H• radicals which further However, dissatisfying flame retardant effectiveness was
reduces combustible volatiles evaporation.212 demonstrated. Chitosan and alginate have positive and
Feng et al.213 synthesized FR in a one-pot method without negative charges, respectively. Consequently, facile fabrication
using any solvent and catalyst. The FR polyphosphoramide of the flame retardant was accomplished, resulting in a core−
(DM-H) was obtained by reacting 1,6-hexanediamine (HAD) shell morphology. Initially, chitosan was coated on APP which
and DMMP under high pressure and temperature conditions. was further coated with alginate. The process was repeated to
The inclusion of DM-H (2 wt %) in PLA has achieved a 29.7% make up to three bilayers (chitosan and alginate) and was
LOI value and V-0 rating without much affecting the tensile further named as APP-at-chitosan-at-alginate-3BL (where, 3BL
strength of PLA. Figure 10b illustrates the FR mechanism.213 It represents three chitosan and alginate bilayers) which was melt
can be seen from the literature that flame retardancy has also blended in the PLA matrix. The PLA consisting of 10 wt %
been developed by functionalizing phosphorus nitrogen-based APP-at-chitosan-at-alginate-3BL showed a maximum LOI
compounds that have been reacted with epoxy groups. value (30.6%). The sample in the vertical burning test showed
Jin et al.214 developed an intumescent FR (A-A) and melt a UL94 V-0 rating. This was achieved due to the exceptional
blended it with PLA. The FR was prepared by reacting p- char-forming capacity of APP-at-chitosan-at-alginate. An
aminobenzenesulfonic acid and APP by ion exchange. A increase in impact strength (∼23%) was achieved on the
significant reduction in dripping was observed, for PLA having addition of 10 wt % APP-at-chitosan-at-alginate-3BL in PLA.
developed FR, because of the rapid formation of char residues Enhancement in toughness (elongation at break 21% and
23 https://doi.org/10.1021/acsengineeringau.1c00011
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notched impact strength 35%) was also achieved which has the
significant potential for industrial applications.
Feng et al.213 developed a polyphosphoramide (DM-H) FR
for PLA. The sustainable approach for synthesizing eco-benign
FR was a one-pot method, and the preparation does not
involve any solvent or catalyst. The polycondensation between
dimethyl methylphosphonate (DMMP) and 1,6-hexanedi-
amine was conducted for the synthesis of the FR (DM-H).
The results showed a balance between flame retardancy and
mechanical properties. A limited quantity of DM-H (only 2 wt
%) enabled PLA to achieve 29.7% LOI, and during vertical
burning tests it achieved a V-0 rating. Tensile strength merely
reduced from 62.1 MPa for bulk PLA to 59.7 MPa.
Zhao et al.215 synthesized a superefficient flame retardant for
PLA without affecting the tensile properties. Phenylphos-
phonic dichloride (PPDCL) was reacted with allylamine (AA)
in the presence of triethylamine (TEA) to form N,N′-diallyl-p-
phenylphosphonicdiamide (P-AA). P-AA was melt com-
pounded with PLA to form a superefficient flame retardant
PLA. Merely 0.5 wt % loading of P-AA showed an increase in
its LOI value from 20.5 to 28.4. Samples 0.5 and 1 wt % passed
a UL 94 V-0 rating at 3.2 mm and 1.6 mm thickness,
respectively.
Feng et al.202 fabricated a FR system having cellulose
nanofibers grafted with a phosphorus−nitrogen-based polymer.
PLA consisting of a 10 wt % synthesized FR system attained a
rating of V-0 (industrial flame retardancy requirement) flame
resistance in vertical burning tests. In addition to that, an
enhancement in mechanical properties was achieved. To
develop the FR system, chemical grafting of cellulose nanofiber
(CNF) was conducted with epoxy chloropropane. The product
was further reacted with polyethylenimine and consequently
with diethyl phosphite. The fabricated system showed a 24%
increment in tensile strength and a 12% increase in elastic
modulus.
Zhang et al.57 performed repeated self-assembly of chitosan
and alginic acid on APP to form a bioderived core−shell FR.
The 10 wt % FR in PLA sample showed a 30.6% LOI value
and achieved a V-0 rating. Such a result was obtained due to
the char formation capability of the FR. Impact strength
increased by ∼23% that probably resulted from interfacial
hydrogen-bonding interaction.
6. PROSPECTIVE APPLICATIONS OF DURABLE
PLA-BASED BLENDS
6.1. Automobiles
The criteria for selecting plastics to use in automobiles are
durability, stiffness, elasticity, flexibility, corrosion resistance,
heat resistance, UV resistance, processability, weight or density,
plastic cost, and production cost.216 Plastics commonly used in
automobiles are PP in bumpers and fuel systems; polyamide in
electrical components; polyurethane (PU) and poly(methyl
methacrylate) (PMMA) in lighting; polycarbonate (PC) in
dashboards and bumpers; and acrylate butadiene styrene for
exterior and interior trims.216 Aircraft interiors require
dimensional stability, mechanical strength, light weight, and
low smoke release in case of fire. Fuselages, wings, and major
interior assemblies of aircraft have been increasingly
manufactured from composites, namely, carbon-fiber rein-
forced polyether−ether−ketone (CF-PEEK).217 PLA-based
Röchling Automotive’s filter box and interior trim have also
been developed. Zheng et al.218 introduced a closed-cell
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polymethacrylimide (Rohacell-31) polymer foam and devel-
oped a concept for crashworthy subfloor design. The polymer
foam is an exceptionally lightweight material that can absorb
energy by undergoing deformation.218 However, a study was
conducted for determining space debris (material) density
distribution; among different materials, the amount of plastic
debris cannot be ignored.219 To overcome this problem, the
panels for aircraft interiors can be made of renewable PLA
blends or composites with flame retardants. Vidal et al.220
conducted a life cycle assessment of aircraft interior panels.
Four sustainable panels such as geopolymer-based, PP,
linseed-oil-based, and PLA were investigated. Marx et al.221
prepared a potential leading material for aircraft by infusing a
hydrophobic two-part aromatic epoxy resin in a stainless steel
composite metal foam (SS-CMF). The surface properties of
the epoxy coupons were improved by adding an aminopropyl-
terminated siloxane. The epoxy resin filled the micro- and
macropores of the foam which created a density similar to that
of aluminum. It was concluded from the results that the resin-
infused metal composite has the potential to provide greater
wear resistance, extended operational lifetime, lower wett-
ability, and excellent durability.221 PLA (specifically the L-
isomer) has the potential to be used in automobiles as (i) it is
relatively less expensive; (ii) it has commercial availability
compared to other bioplastics; (iii) it has easy processability as
it can be prepared by film-forming, sheet extrusion,
thermoforming, injection molding, blow molding, and 3D
printing techniques. Thus, intricate shapes and complex
geometries can be prepared that can be used as automotive
parts.216 An electrically powered car “Noah” was manufactured
where its chassis and all bodywork were prepared using
Luminy PLA and natural flax fiber. The car was claimed to be
100% circular and sustainable. PLA grade Luminy was supplied
by Total Carbion that ensured significant heat resistance and
durability.222
6.2. Medical
PLA is biocompatible with the human body. That is, it rarely
shows foreign body response and thus can be used for
biomedical applications. Its degraded products inside the body
are metabolized intracellularly or can be excreted in the breath
and urine. 223 PLA has been explored in biomedical
applications in the field of orthopedics (bone regeneration,
screws, meniscus repair, spinal cord injury regeneration),
cardiology (stent, chest wall reconstruction), dentistry (tissue
regeneration, space fillers), plastic surgery (suture, skin graft,
dermal fillers, reconstructive surgery), general surgery (hernia
mesh), gynecology (stress incontinence mesh), radiology
(theranostic imaging), and oncology (drug delivery, nano-
particles, and intracranial delivery).224
Figure 11a shows scaffolds prepared using a polylactide/
calcium carbonate composite prepared by selective laser
sintering (SLS).225 Figure 11b,i shows a molar tooth model,
and Figure 11b,ii shows a 3D printed molar tooth, which was
prepared from a PLA composite. Biocompatibility and
adaptability are the reason for PLA-based composite use in
dentistry-based applications. Nano-HA was added and was
homogeneously dispersed in the PLA matrix and showed
increased mechanical properties.226 Figure 11c shows 3D
printed drug impregnated orthopedic PLA (i) plates and (ii)
pins.227 Figure 11d shows PLA/iron oxide composite bone
screws that were (i) injection molded and (ii) 3D printed and
implanted into white rabbit femoral condyles with enhanced
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Figure 11. Medical applications. (a) PLA composite cranial implant
demonstrators.225 (Open access.) (b) (i) Molar tooth model226 and
(ii) PLA-based 3D printed tooth. (Copyright 2017, adapted with
permission from John Wiley and Sons; license number:
5124020527281.) (c) PLA 3D printed orthopedic227 (i) plates and
(ii) pins. (Open access.) (d) PLLA/iron oxide screws:228 (i) injection
molded and (ii) 3D printed. (Open access.)
osteogenic capability.228 Further, the mechanical strength and
durability of PLA-based products has attracted attention for
clinical applications.66 Further, a cost-effective PLA filament
was used to prepare Army/Navy surgical retractors. The
properties possessed by the retractor are the strength to retract
tissues and tolerance for repeated sterilization.229 The use of
disposable products is gaining attention in the modern medical
field. These nonwoven products such as surgical gowns,
hospital bed covers, and surgery drape sheets are used in
patient and operating rooms.
6.3. Textile
M+N Textiles launched the sunscreen fabric REVOLUTION
made from Ingeo PLA yarn. The fabric has flame retardant
properties.230 Avinc et al.205 worked on PLA fabric perform-
ance when liquid repellent, flame retardant, and softer finishes
were added. The flame retardant properties of the PLA fabrics
were found to be durable for 50 washing cycles.205 The
concept for 4D printed PLA/nylon fabrics, which possess
shape memory properties when exposed to temperature, was
also developed.231 Win Yang Textile Co., Ltd. manufactures
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and exports PLA webbing that is suitable for pet collars,
harnesses, and straps.232 Felfil developed 3D printed clothes,
particularly using nylon and PLA. Naturepedic developed a
pillow consisting of an outer fabric made of cotton and batting
made from PLA. PLA was introduced because of its moisture
wicking properties and resilience. The PLA high-performance
fiber offered fluffiness in the pillows.233
6.4. Electronics
The global demand for electronic devices is increasing
drastically, generating enormous waste and creating serious
environmental issues. As a result, durable electronic products
prepared using renewable bioplastics are essentially needed.
The use of bioplastics in such electronic devices will positively
impact the environment and carbon footprint. For conven-
tional refrigerator and freezer cabinet door liners, it has been
observed that, over time, the cabinets lose thermal resistance.
The loss of thermal resistance occurs due to the diffusion of air
pockets into the foam along with the diffusion of low thermal
conductive gases out of the foam. This diffusion process results
in the use of more energy. The problem can be addressed by
applying the liner on the exterior part of the foam insulation
which can restrict the diffusion and can potentially save energy.
The refrigerator and freezer cabinet door liner was developed
using Ingeo PLA, which can be applied to the foam insulation,
as shown in Figure 12a. The thermal resistivity of the door
Figure 12. Electronics applications. (a) PLA-based refrigerator-freezer
cabinet door liner.234 (Copyright 2019, adapted with permission from
Elsevier, license number: 5124021312326.) (b) OFETs array
fabricated on PLA.235 (Copyright 2015, adapted with permission
from Elsevier, license number: 5124030294324). (c) 3D printed PLA-
based ring and disc-shaped electrodes.236 (Reprinted with permission
from ref 236. Copyright 2018 American Chemical Society.)
liners over the years was determined by simulation, and it was
observed that the developed PLA liners could save 7.3−12.5%
of energy over 15 years.234
Organic field-effect transistors (OFETs) were developed
using PLA as the substrate and gate dielectric, as shown in
Figure 12b. The developed product showed good dielectric
properties.235 Graphene/PLA electrodes were developed and
printed using a fused deposition modeling printer for
electrochemical sensing (Figure 12c). The developed product
showed enhanced electroactivity.236
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Figure 13. Challenges and strategies for the development of PLA-based blends and composites.
6.5. Housing
Alpar architectural products are made from deTera biobased
materials, prepared using NatureWorks Ingeo, having least
possible environmental impact. The products are sheet wall
protection,237 corner guards,237 handrails, and crash rails.
Gantri and colorFabb codeveloped PLA blends for lighting
products. The opaque lamps are safe for electronic use and
possess better thermal resistance than traditional PLA.238 LG
Hausys developed ZEA series wallpapers and floorings by
utilizing fibers and PLA (Ingeo) for achieving durable and
thermal resistant properties.230,239 ZEA wallpapers were
prepared by LG Hausys using PLA (Ingeo) layer,230 and
Treleonideveloped Provito floor pads.
7. KEY CHALLENGES OF TAILORED PLA FOR
ATTAINING DURABILITY
Researchers are working toward developing durable PLA-based
blends and composites for achieving the specific goals as
discussed in the Introduction. It has also been observed a
material with increased sustainability, including GHG emission
reduction over engineering plastics, can be developed by
incorporating renewable materials by blending it with
engineering plastics. A few of the challenges for attaining
PLA-based durable blends and composites and the strategies
for improving those properties are summarized in Figure 13.
However, the key challenges faced so far for attaining
durability in PLA-based blends and composites are as follows:
• Simultaneously achieving the critical characteristics such
as impact strength, toughness, heat resistance, flame
resistance, and improved processability so that high-
performance, durable PLA blends or composites can be
attained, which can match the performance of currently
available engineering plastics. Primarily, striking a
balance between toughness and stiffness.90 However,
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significant improvement in both properties, HDT and
impact strength, has been achieved.38
• Achieving good interfacial adhesion in the blends
between components is one of the challenging issues
that also needs to be addressed as it directly affects
mechanical properties.114
• The immiscibility between the polymers has also been
overcome by adding a masterbatch prepared by reacting
the monomers of the individual immiscible polymers.
The addition of a masterbatch enhances the miscibility
of the polymers containing the masterbatch because the
functional groups present in the masterbatch can easily
attach to their respective polymers during processing.
However, enhancing the miscibility between the
incompatible polymers using a masterbatch (prepared
by multiple processing and energy-intensive process)
may not be favorable for industrial-scale production.
Thus, the development of feasible and cost-effective
production should also be taken into consideration for
the preparation of durable polymers on a large scale for
various applications, such as automotive, textile, housing,
electronic, and medical, and is a taxing task.
• Tough materials are blended with PLA to prevail over
the inherent brittleness of PLA. However, PLA has a
high mechanical strength which is usually sacrificed by
the addition of tough materials to outplay its
brittleness.117
• To develop sustainable products for durable applica-
tions, a selection of sustainable additives should be made
so that if they leech out they should not adversely affect
living creatures and the environment.
• Unreacted additives in the product should not hamper
the properties of the polymers in the long run.
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Figure 14. Life cycle stages of durable PLA-based products.
8. LIFE CYCLE ASSESSMENT OF PLA-BASED
PRODUCTS
The life cycle assessment (LCA) is a tool for evaluating the
environmental impact of a process or a product life cycle. The
purposes of the LCA are (i) to compare alternative products,
processes, or services; (ii) to compare alternative life cycles for
a particular product or service; (iii) and to identify the parts of
the life cycle where the improvements can be made.
LCA has also been used to evaluate the environmental
performance of renewable products, including PLA-based
products. Usually, a product’s cradle-o-gate analysis consists
of raw materials extraction, transportation, product develop-
ment (manufacturing), and packaging. On the other hand,
cradle-to-grave analysis includes product distribution, use, and
finally end of life. Figure 14 represents an overview of the steps
involved in the life cycle of durable PLA-based products. The
initial step in the life cycle of PLA-based durable products is to
extract raw materials consisting of renewable carbon and
nonrenewable carbon, additives, and reinforcing agents.
Further, the raw materials are transported to the industry/
development center for product development for high-
performance applications. Thereafter, the developed products
are distributed and used by the consumers. As described in the
Introduction, the end-of-life options of PLA-based durable
products are recycling (mechanical or chemical), incineration,
or landfilling. The used products can be recycled and can enter
the stream at the product development stage. The incinerated
solid waste can further go to landfills. However, landfilling can
be avoided to its possible extent, and other end-of-life options
such as smokeless incineration and recycling can be preferred.
Haylock et al.240 conducted a LCA analysis and compared
the effect of inorganic fillers (glass fibers and talc) and organic
fillers (rice husks, wood, flax, and hemp). Based on the
assumptions, it was inferred that landfilling of PLA composites
consisting of glass fillers is highly undesirable toward the
environment and has a significant economic impact. In
addition to that, when recycled, PLA composites consisting
of organic fillers have the least damaging impact on the
environment.
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Rezvani Ghomi et al.241 determined that the conversion of
PLA is the most energy-intensive process, as during conversion
more than 50% of CO2 (2.8 kg CO2 per kg PLA) is released in
its life cycle. However, the conversion of PLA can be optimized
to further reduce the carbon footprint of PLA.
Roy et al.242 evaluated the life cycle environmental impact
(cradle-to-grave) of biocarbon derived from Miscanthus fibers
as a reinforcing agent in the PP matrix for lightweight
automotive parts. It was observed that the global warming
potential (GWP) of the biocarbon in the PP matrix of an
automotive component (441 cm 3 ) was 11.08 kg CO 2
equivalent, which was lesser than the conventional reinforcing
agent such as talc that showed GWP 12.53 kg CO2 equivalent.
However, Yates and Barlow243 concluded that even though
most studies found biopolymers to be better than petroleum-
based polymers, it has to be taken into consideration that the
biopolymers technology is at an immature stage. Hence, it is
required that the current immature stage of biopolymers has to
be taken into consideration for future improvements and
optimization. Thus, it is difficult to predict the environmental
friendliness of biopolymers and petroleum-based polymers at
this stage.
Furthermore, Walker and Rothman244 compared seven
fossil-based polymers and seven biobased polymers for various
impact categories. It was observed that conclusively declaring
any polymer to have the most negligible environmental impact
was not possible. The variation in the results was observed due
to the methodological differences between studies. Hence, it
was proposed that Product Environmental Footprint (PEF)
standards should be adopted for homogenizing methods.
Qiang et al.245 compared the environmental impact load of
untoughened PLA-based wood plastic composites (PLA/
WPCs) with the styrene−butadiene−styrene (SBS) toughened
PLA/WPCs. The SBS toughened PLA/WPCs displayed a
reduced environmental impact load index with untoughened
PLA/WPCs. The calculation was conducted without consid-
ering the pollution data of SBS due to the nonavailability of
emission data. Based on the environmental impact load (EIL)
values, it was observed that the nonrenewable part (SBS) in
the renewable part (PLA/WPCs) resulted in a reduction in
environmental impact load.
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Hence, the detailed LCA study of PLA-based durable
products will help identify the hot spots where the most
significant improvement can be made to improve the
environmental performance and determine if we can improve
the sustainability of PLA-based durable products compared to
the conventional products.
9. PLA-BASED BLENDS AND COMPOSITES
DURABILITY: FUTURE PERSPECTIVE
The need for bioplastics in the global market is increasing
significantly, and the outlook for bioplastics is promising. It has
been predicted that, over the next 5 years, the global market
will grow by 36%. The expected growth for the years 2021−
2025 is shown in Figure 15. The investments for production in
the United States, Europe, and China will continue the growth
of PLA. The data confirms that it will be explored for various
applications that also require durability.
Figure 15. (a) Global production capacities of bioplastics. Color
representation: green represents biodegradable, yellow represents
biobased/nonbiodegradable.246 (Redrawn from data in ref 246;
accessed the web site “European Bioplastics” in August 2021.) (b)
Biobased and durable bioplastics production.247 (Redrawn from the
data in ref 247; accessed the web site “European Bioplastics” in
August 2021.)
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The global market demand for PLA doubles in 3−4 years
and, hence, results in the starting of new plants such as Total-
Corbion, China Oil and Foodstuffs Corporation (COFCO),
and SuPLA, and many more are under construction to meet
the demand and supply gaps. PLA plants that have been under
construction are BBCA Galactic of ∼40 000 tons capacity and
Hisun of 30 000−50 000 tons production capacity.81
Marked improvements in mechanical strength, crystallinity,
and thermal stability simultaneously for various applications is
the scope of future work. Chain extenders, such as epoxides,
anhydrides, isocyanates, acid chlorides, thiirane, and oxazoline,
have been used to improve the crystallinity and mechanical
properties of PLA. The use of chain extenders is an
economically feasible process, as much smaller amounts are
used in the melts. However, the unreacted nonbiodegradable
chain extending agents in the final product can be
minimized.189 The minimized use of additives such as catalysts
and chain extenders can be done during processing, as these
additives can result in undesired degradation and unreprodu-
cible or uncontrolled hydrolysis rates.189 Additives having
similar processing temperatures as PLA and PLA blends or
composites can be selected. Uniform perfect crystallites or
crystals in the blends or composites can be achieved by
precisely controlling processing temperature and mechanical
properties.189
In addition to that, low temperature−high pressure
processing of incompatible polymer−polymer blends can be
explored. In the system, one of the polymers with a high
melting point can be used as reinforcing material in the form of
fibers, and other polymers having low processing temperature
can be used as a matrix for enhanced mechanical properties.
However, this processing method needs thorough investigation
and optimization.
Researchers are gaining attention to the development and
use of compatibilizers with two or more incompatible phases,
such as Janus materials or hydrophilic−lipophilic surfactant
blends. When added into the immiscible polymer blends, these
compatibilizers choose the surface of the polymers immiscible
with each other and can reinforce the surface compatible with
them. In this way, all the phases of a compatibilizer may create
strong bonds with all the blend components and can result in
improved mechanical properties. Although, Janus materials
have already been used in biological or medical fields.
However, these compatibilizers have the potential to be
explored in this direction also.248 Hence, PLA-based blends or
composites need to be developed cost-effectively from techno-
economic and circularity perspectives for durable applications.
10. CONCLUDING REMARKS AND OUTLOOK
PLA is proving its worth and potential over other bioplastics in
the pursuit of developing biobased durable products having
sustainability, a low carbon footprint, and cost competitiveness.
Future innovations are required to corroborate that the
developed materials will not only be economically sustainable
but also will be sourced, produced, utilized, and repurposed
such that they can address the needs of current and future
generations. Material scientists have shown diverse approaches
in developing PLA-based blends and composites for achieving
durability using suitable additives. The perspective on the
subject and studies conducted have bestowed knowledge on
the approaches, strategies, and understanding on the subject.
It has been observed that the crystallinity, molecular weight,
and mechanical properties of PLA are interdependent, which
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have to be controlled for durable applications. An unprece- Biographies

dented strategy needs to be developed to simultaneously
enhance both the exclusive attributes, namely, strength and
toughness, because usually toughness is achieved at the cost of
stiffness and strength. The research conducted on enhancing
the durability of PLA shows that impact modifiers, nucleating
agents, and compatibilizers play a vital role in lowering the
technological barrier to achieve durable PLA for desired
applications. The interfacial adhesion between components
needs to be enhanced for achieving supermechanical proper-
ties, which result in durable PLA. The two inherent factors
which affect the tensile strength of blends are phase structure
and adhesion at the interface.
The durable PLA-based blends and composites open up
possibilities for a broad range of high-performance applications
in automotive, biomedical, electrical appliance, textile, and
housing applications. The development of durable PLA blends
and composites is the panacea to resolve the impediments in
acclimatizing PLA for various commercial applications. Bio-
plastics prepared from PLA, which can be used for durable
applications, have tremendous potential to become the
centerpiece of the market. Hence, facile yet highly effective
methods need to be explored for attaining circularity and
sustainability.
Neelima Tripathi is currently working as a Postdoctoral Fellow in
Bioproducts Discovery & Development Centre (BDDC) at the
University of Guelph, ON, Canada. She received her Ph.D. from the
Department of Chemical Engineering, Indian Institute of Technology
Guwahati, India. She was awarded with a SERB-National Postdoctoral
Fellowship and has worked at the Indian Institute of Technology
Kanpur, India. She also worked as an adhoc faculty for a year in the
Department of Chemical Engineering at the National Institute of
Technology Warangal, India. She received the Gandhian Young
Technological Innovation (GYTI) Award, 6th National Awards (one
as a winner and one as a runner-up) for Technology Innovation
2015−16 by Petrochemicals, Ministry of Chemicals & Fertilizers,
Department of Chemicals & Petrochemicals, Government of India.
She is the associate member of The Institution of Engineers (India);
and life member of Indian Institute of Chemical Engineers (IIChE),
Paint And Coating Technologists’ Association (PACT), and Oil
Technologists’ Association of India (OTAI). Her main research
interests include biopolymers, polymer bionanocomposites, pack-
aging, adhesives, edible films and coatings.

■ AUTHOR INFORMATION
Corresponding Authors
Amar K. Mohanty − Bioproducts Discovery and Development
Centre, Department of Plant Agriculture, Crop Science
Building and School of Engineering, Thornborough Building,
University of Guelph, Guelph N1G 2W1 Ontario, Canada;
orcid.org/0000-0002-1079-2481; Email: mohanty@
uoguelph.ca
Manjusri Misra − Bioproducts Discovery and Development
Centre, Department of Plant Agriculture, Crop Science
Building and School of Engineering, Thornborough Building,
University of Guelph, Guelph N1G 2W1 Ontario, Canada;
orcid.org/0000-0003-2179-7699; Email: mmisra@
uoguelph.ca Manjusri Misra is a professor and Tier 1 Canada Research Chair
(CRC) in Sustainable Biocomposites in the School of Engineering
Author
and holds a joint appointment in the Department of Plant Agriculture
Neelima Tripathi − Bioproducts Discovery and Development at the University of Guelph. As well, she is the Research Program
Centre, Department of Plant Agriculture, Crop Science Director of the Bioeconomy Panel for the Ontario Agri-Food
Building, University of Guelph, Guelph N1G 2W1 Ontario, Innovation Alliance, a program between the Ontario Ministry of
Canada Agriculture and Rural Affairs (OMAFRA) and the University of
Complete contact information is available at: Guelph. Dr. Misra completed her Bachelor’s, Master’s, and PhD at
https://pubs.acs.org/10.1021/acsengineeringau.1c00011 Utkal University in India focusing in chemistry with a specialization in
polymers and natural fibers. Dr. Misra’s current research focuses
Notes primarily on novel biobased composites and nanocomposites from
agricultural, forestry and recycled resources for the sustainable
The authors declare no competing financial interest. bioeconomy moving towards Circular Economy. She has authored

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more than 750 publications, including 412 peer-reviewed journal
papers, 21 book chapters, and 53 patents. She was the editor or co-
editor of 4 books in the area of biocomposites and nanocomposites.
She is a Fellow of the Royal Society of Chemistry (UK), the American
Institute of Chemical Engineers (AIChE), and the Society of Plastic
Engineers (SPE). Dr. Misra has received many awards including the
Synergy Award for Innovation from Natural Sciences and Engineering
Research Council of Canada (NSERC); the Andrew Chase Forest
Products Division Award from the American Institute of Chemical
Engineers and the Lifetime Achievement Award from the BioEnvir-
onmental Polymer Society (BEPS). In 2020, she was selected as one
of Canada’s Most Powerful Women: Top 100 Award Winner in the
Manulife Science and Technology category from the Women
Executive Network.
Cluster Program (Project No. 054712); (iii) the Ontario
Ministry of Agriculture, Food and Rural Affairs (OMAFRA)/
University of Guelph − Bioeconomy for Industrial Uses
Research Program (Project Nos. 030251, 030332 and
030485); (iv) the Natural Sciences and Engineering Research
Council of Canada (NSERC), Canada Research Chair (CRC)
program Project No. 460788; and (v) the NSERC, Canada
Discovery Grants (Project No. 401111) in carrying out this
study. This research was also benefited from the facility
funding to the Bioproducts Discovery and Development
Centre (BDDC) lab by FedDev Ontario; Ontario Ministry
of Agriculture, Food, and Rural affairs (OMAFRA); Canada
Foundation for Innovation (CFI); Federal Post- Secondary
Institutions Strategic Investment Fund (SIF); and matching
funds from the province of Ontario, Bank of Montreal (BMO)
and numerous University of Guelph’s Alumni.

■
PLA
ABBREVIATIONS
Polylactic acid
NASA National Aeronautics and Space Adminis-
tration
GWP Global warming potential
LDPE Low density polyethylene
PE Polyethylene
PHA Poly(hydroxy alkanoate)
PHB Poly(hydroxy butyrate)
PC Polycarbonate
HDPE High density polyethylene
DAH 1,6-diaminehexane
Amar K. Mohanty is a Full Professor and OAC Distinguished DAE 1,2-diamineethane
Research Chair in Sustainable Biomaterials and is the Director of the ASTM American society for testing and materials
Bioproducts Discovery & Development Centre at the University of LCA Life cycle assessment
Guelph. He is a former Michigan State University professor and is an PET Poly(ethylene terephthalate)
international leader in the field of bioplastics, biocomposites, and PP Polypropylene
advanced biorefinery. His research focuses on engineering value- GF Glass fibers
added uses of biomass wastes and industrial coproducts from agro- CF Carbon fibers
food and biofuel industries. Circular economy, environmental HDT Heat deflection temperature
sustainability, waste plastic valorization, biodegradable plastics as M̅ n Number-average molecular weight
single-use plastic alternatives, biocarbon-based composites, and 3D M̅ w Weight-average molecular weight
printing of sustainable materials are other areas of his expertise. Prof. Tg Glass transition temperature
Mohanty is the Editor-in-Chief of Sustainable Composites, Tm Melting temperature
Composites Part C − Open Access (ELSEVIER). He has more Xc Percentage of crystallinity
than 800 publications to his credit, including 423 peer-reviewed XRAF Amorphous region percentage (rigid frac-
journal papers, 6 edited books, over 400 conference presentations, 25 tion)
book chapters, and 67 Patents awarded/applied (His Google Scholar XMAP Amorphous region percentage (mobile
citations exceed 41 000). Prof. Mohanty is a Fellow of the Royal phase)
Society of Canada, the American Institute of Chemical Engineers, the XRD X-ray diffraction
Royal Society of Chemistry (UK) and the Society of Plastic UV Ultraviolet
Engineers. Prof. Mohanty has received many awards, including the DSC Differential scanning calorimetry
JL White Innovation Award from the International Polymer PEG Poly(ethylene glycol)
Processing Society; Synergy Award for Innovation from Natural PCL Poly(ε-caprolactone)
Sciences and Engineering Research Council of Canada (NSERC); PE Polyethylene
Andrew Chase Forest Products Division Award from the American PVC Poly(vinyl chloride)
Institute of Chemical Engineers and Lifetime Achievement Award MMT Montmorillonite
from the BioEnvironmental Polymer Society (BEPS).

■
EMA-GMA Ethylene methyl acrylate-glycidyl methacry-
late
ACKNOWLEDGMENTS PEBA Poly(ether-block-amide) elastomeric copoly-
The authors are thankful for the financial support of (i) the mer
Ontario Research Fund, Research Excellence Program; Round PDLA Poly(D-lactic acid)
9 (ORF-RE09) Ontario Ministry of Economic Development, ABS Acrylonitrile butadiene styrene
Job Creation and Trade (Project Nos. 053970 and 054345); PCL Polycaprolactone
(ii) the Agriculture and Agri-Food Canada (AAFC) and PGA Polyglycolide/Poly(glycolic acid)
Competitive Green Technologies, Canada through AgSci PS Polystyrene
30 https://doi.org/10.1021/acsengineeringau.1c00011
ACS Eng. Au 2021, 1, 7−38
ACS Engineering Au pubs.acs.org/engineeringau Review

PA6 Polyamide 6/nylon6 HPMIM High pressure microcellular injection mold-

PETG Poly(ethylene terephthalate glycol) ing
PGSMA Poly(glycerol succinate-co-maleate) MOFIM Mold-opening foam injection molding
PTT Poly(trimethylene terephthalate) SEBS Styrene−butadiene-styrene block copolymer
SPI Soy protein isolate LOI Limited oxygen index
PBT Poly(butylene terephthalate) DOPO 9,10-dihydro-9-oxy-10-phosphaphenan-
PAE Poly(amide elastomer) threne-10-oxide
EBA-GMA Poly(ethylene-n-butylene acrylate-glycidyl PPDC Phenylphosphonic dichloride
methacrylate) DPA Diphenolic acid
EBA-MaH Ethylene butyl acrylate-maleic anhydride FR Flame retardant
EMA-MaH Ethylene methyl acrylate-glycidyl methacry- DM-H Polyphosphoramide
late HAD 1,6-hexanediamine
MFC Microfibrillated cellulose DMMP Dimethyl methylphosphonate
EPI Epichlorohydrin PPDCL Phenylphosphonic dichloride
MA-g-PP Maleic anhydride-graf t-polypropylene AA Allylamine
LDI L-Lysine ethyl ester diisocyanate TEA Triethylamine
HDA Hydrogenated dimer acid CNF Cellulose nanofiber
SA-GMA Poly(styrene-acrylic-co-glycidyl methacry- PU Polyurethane
late) PMMA Poly(methyl methacrylate)
DMSA N,N-Dimethylstearylamine CF-PEEK Carbon-fiber reinforced polyether−ether−
Sn(Oct)2 Stannous octanoate ketone
PLLA-b-PMMA Poly(L-lactic acid)-block-poly(methyl meth- SS-CMF Stainless steel composite metal foam
acrylate) SLS Selective laser sintering
DCP Dicumyl peroxide OFETs Organic field-effect transistors
TMPTA Trimethylolpropane triacrylate PEF Product environmental footprint
PEGMA Poly(ethylene-co-glycidyl methacrylate) WPCs Wood plastic composites
G-ABS Grafted ABS SBS Styrene−butadiene−styrene
SAN-GMA Styrene-acrylonitrile grafted glycidyl meth- EIL Environmental impact load
acrylate copolymer COFCO China Oil and Foodstuffs Corporation
PMAA Polymethacrylic acid
SMA
MFI
EOR-MAH
Styrene-maleic anhydride copolymer
Melt flow index
Poly(ethylene-co-octene) rubber-maleic an-
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