C Journal of

Carbon Research

Review
Towards Controlled Degradation of Poly(lactic) Acid in
Technical Applications
Stefanie Teixeira, Katarzyna Morawa Eblagon * , Filipa Miranda, M. Fernando R. Pereira
and José Luis Figueiredo

Laboratory of Separation and Reaction Engineering-Laboratory of Catalysis and Materials (LSRE-LCM),

Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal;
[email protected] (S.T.); [email protected] (F.M.); [email protected] (M.F.R.P.);
[email protected] (J.L.F.)
* Correspondence: [email protected]

Abstract: Environmental issues urge for the substitution of petrochemical-based raw materials with
more environmentally friendly sources. The biggest advantages of PLA over non-biodegradable
plastics are that it can be produced from natural sources (e.g., corn or sugarcane), and at the end of
its lifetime it can be returned to the soil by being composted with microorganisms. PLA can easily
substitute petroleum-based plastics in a wide range of applications in many commodity products,
such as disposable tableware, packaging, films, and agricultural twines, partially contributing to
limiting plastic waste accumulation. Unfortunately, the complete replacement of fossil fuel-based
plastics such as polyethylene (PE) or poly(ethylene terephthalate) (PET) by PLA is hindered by its
higher cost, and, more importantly, slower degradation as compared to other degradable polymers.
Thus, to make PLA more commercially attractive, ways to accelerate its degradation are actively





 sought. Many good reviews deal with PLA production, applications, and degradation but only in
Citation: Teixeira, S.; Eblagon, K.M.;
the medical or pharmaceutical field. In this respect, the present review will focus on controlled
Miranda, F.; R. Pereira, M.F.; PLA degradation and biodegradation in technical applications. The work will include the main
Figueiredo, J.L. Towards Controlled degradation mechanisms of PLA, such as its biodegradation in water, soil, and compost, in addition
Degradation of Poly(lactic) Acid in to thermal- and photo-degradation. The topic is of particular interest to academia and industry,
Technical Applications. C 2021, 7, 42. mainly because the wider application of PLA is mostly dependent on discovering effective ways of
https://doi.org/10.3390/c7020042 accelerating its biodegradation rate at the end of its service life without compromising its properties.

Academic Editors: Keywords: PLA; biodegradation; hydrolysis; soil immersion; composting; control of biodegradation;
Jean-François Morin and Patrizia Savi PLA composites

Received: 24 February 2021

Accepted: 19 April 2021
Published: 30 April 2021
1. Introduction
Publisher’s Note: MDPI stays neutral
Many reviews deal with the technology and degradation of PLA, mostly in a plethora
with regard to jurisdictional claims in
of medical applications, including tissue engineering, implants, skin and tendon healing,
published maps and institutional affil- and medical tools and equipment [1–5]. However, reviews dealing with the technical
iations. applications of PLA are very scarce. The present review’s objective is to show the current
progress in the controlled degradation of PLA in commodity applications, where it can
substitute in the future the non-degradable poly(ethylene terephthalate) (PET), polystyrene
(PS), polypropylene (PP) and others.
Copyright: © 2021 by the authors.
With an approximate production of 140 million tons per year, synthetic polymers
Licensee MDPI, Basel, Switzerland.
have become an indispensable part of our life [6]. Intense use of petrochemical-based
This article is an open access article
polymers for more than 70 years has resulted in many environmental issues concerning
distributed under the terms and non-degradable waste accumulated in the landfills and, sadly, in the oceans. The well-
conditions of the Creative Commons known “great Pacific garbage patch,” which is mainly composed of plastics (an estimated
Attribution (CC BY) license (https:// 80,000 tones) covering over 1.6 million square kilometers, is shocking evidence of the size
creativecommons.org/licenses/by/ of the global problem with plastic waste management. The improper disposal of plastic
4.0/). materials can endanger living organisms’ health and life. Thus, with the ever-increasing

C 2021, 7, 42. https://doi.org/10.3390/c7020042 https://www.mdpi.com/journal/carbon

C 2021, 7, 42 2 of 43

use of plastics, significant funding worldwide is directed towards either improving the
disposal of petrochemical-based polymers or substituting them with more environmentally
benign materials, e.g., produced from biomass. Additionally, alternative bio-resources
for plastic production can help decrease the depletion rate of fossil fuels, minimize the
political conflicts around the world, and lessen climate changes connected with emissions
of greenhouse gasses [7].
Notably, bio-based polymers can replace petrochemical plastics in various sectors
and provide new and sometimes improved combinations of properties. Unfortunately,
biodegradable plastic represents only a small-scale market compared with conventional
petrochemical materials [6]. Globally, bioplastics account for less than 1% of the 181 million
metric tons of synthetic plastics the world produces each year [8]. Lately, research and
development on biodegradable plastics have been mainly driven by the restrictions in
the total “carbon footprint,” particularly in applications such as packaging, automotive,
electrical, and electronics industries [9].
PLA is a biodegradable plastic produced from natural resources, such as starch (mainly
harvested from corn), combining ecological advantages with reasonable mechanical prop-
erties. One of the crucial advantages of PLA is that it requires up to 55% less energy to be
produced than petroleum-based polymers, and estimations have shown that this could be
further reduced to less than 10% in the near future [10]. Further, at the end of its service
life, it can be degraded to CO2 and biomass in the environment [11], allowing a reduction
in landfill volumes. The lifecycle of PLA demonstrates that PLA is a sustainable alternative
to olefins, because it is produced from natural resources, such as starch (mainly harvested
from corn), and at the end of its service life it can be degraded to CO2 and biomass in the
environment [11], thus serving as so-called carbon sink. Biodegradability in conjunction
with selected disposal systems of PLA such as composting and anaerobic digestion offers
an end-of-life solution to completely remove the plastic substrate from the environment
and to close the carbon cycle.
Disposable products that would benefit from the advantage of PLA biodegradability
should be disposed of alongside organic waste (e.g., PLA twines together with the green
residues) in industrial composting facilities, without the need for separation. In some
European countries, e.g., the Netherlands, lower surcharges are placed on biodegradable
and compostable waste disposal compared to mixed waste [12]. However, PLA is mostly
resistant to attack by microorganisms in soil or sewage under ambient conditions, and in
fact, it is less susceptible to degradation than other aliphatic biodegradable polymers such
as poly(ε-caprolactone) (PCL) in the natural environment [8]. The slow degradation of
PLA in the environment limits its application. Thus, both industry and academy have a
tremendous interest in searching for new ways of increasing the degradation rate of PLA
and its derivatives. However, improving the PLA’s biodegradability is a big challenge to
overcome, mainly because it should not compromise the material’s mechanical properties
during their service lifetime [13].
Thus, the review will focus on PLA applications in food packaging, textile, and agricul-
tural industries, excluding drug delivery and medical uses of PLA and its decomposition
in vivo. Firstly, PLA’s general characteristics that directly influence its degradation will be
briefly discussed in Section 4, Properties of PLA, followed by its main degradation paths,
along with a description of the factors that influence these processes (Section 5, Degrada-
tion of PLA). The mechanism of PLA hydrolytic degradation and biodegradation will be
described in more detail in Section 5.1, Hydrolytic Degradation, including enzymatic and
microbial degradation in compost (Section 5.4, Microbial Degradation, and Section 6.1,
Composting Conditions). Finally, an overview of some selected methods for controlling
the PLA’s biodegradation in technical applications will be presented (Section 7, Control
and Improvement of PLA Degradation).
C 2021, 7, 42 3 of 43

2. Properties of Lactic Acid and Lactides

The monomeric unit of PLA is lactic acid with the formula CH3 –CH(OH)–COOH,
chemically known as 2-hydroxy-propionic acid. Lactic acid is chiral and has two stereoiso-
mers (i.e., L-(+)-lactic acid or S-lactic acid and D-(−)-lactic acid or (R)-lactic acid), as shown
in Figure 1 [14]. As the result of these stereoisomers, three different PLA materials can be
expected, depending on the substrate material, such as poly(L-lactide) (PLLA), poly(D-
lactide) (PDLA), or a racemic mixture called poly(D,L-lactide) or PDLLA. Most commercial
PLA consists of copolymers of PLLA and PDLLA [15].

Figure 1. Chemical structure of lactic acid stereoisomers: L-(+)-lactic acid is also known as (S)-lactic
acid and D-(−)-Lactic acid, also known as (R)-lactic acid, adapted from [4].

All the stereoisomers above occur naturally as the products of microorganism activity
(bacterial systems). However, the most commonly observed forms are L-type lactic acid or
a racemic mixture (mainly 50% L and 50% D) [16]. Additionally, the L-form constitutes the
main fraction of PLA derived from natural resources [15] (such as biomass), and it is also
the only form of lactic acid produced by humans and other mammals, which has led to the
wide application of PLA in the biomedical industry [17].
The optical properties of PLA are essential for packaging applications, where clarity is
desirable [18].
In general, the polymer’s physical and mechanical properties, which may be tailored
to fit the specific requirements of the application, are mainly determined by its stereochem-
istry [19]. The degree of crystallinity of PLA depends on the type and composition of the
stereoisomers of lactic acid monomers and the polymer’s thermal history. Control of the
physical properties and biodegradability of PLA can be achieved by the racemization of
D- and L-isomers [20]. Thus, when the amount of D-(−)-lactic acid is higher than 6%, the
resulting PLA can be amorphous; when it is lower than 6%, it is considered semicrystalline.
The degree of crystallization of PLA affects its melting temperature (Tm), glass tran-
sition temperature (Tg), and its mechanical properties, including elastic modulus and
mechanical strength. Moreover, as the percentage of the D-isomer increases, both the Tm
and Tg decrease. High crystallinity PLA might be desirable for durable products with long-
term performance in the automotive and electronic industries due to improved thermal and
chemical resistance. On the other hand, the presence of many amorphous domains, which
increase the degradation rate of PLA, is highly beneficial for disposable products [4,20–22].

3. Methods of PLA Production

Currently, NatureWorks LLC Northford, USA, is the world leader in lactic polymer
technology and markets. The company off-set their non-renewable carbon emissions by
buying wind energy certificates and thus claim carbon neutrality for their PLA (marketed
under the trade names Natureworks™ or Ingeo™).
C 2021, 7, 42 4 of 43

Corn-derived PLA presents a competitive advantage versus petroleum-based plastics

due to significantly diminished greenhouse gas emissions (approximately 30–55%) [23] and
price independence from oil fluctuations. Over the past ten years, NatureWorks LLC has
developed patent-protected technologies for lactic acid-based products for a wide range of
specific applications such as extrusion and thermoforming, injection molding, films, foams
and 3 D printing. Recently, one of their patented lactic acid products was used to produce
reusable N95 protection masks against Covid 19 [24]. Nevertheless, from an economic
point of view, bioplastics continue to be more expensive than traditional petroleum-derived
plastics due to their less efficient production [25,26]
Nowadays, PLA production accounts for over 39% of the total lactic acid demand
worldwide. Moreover, 70% of the total worldwide production of lactic acid is carried out by
microbial fermentation [27], using enzymatic hydrolysates from starch [28]. The high cost
of pure carbon and nitrogen sources commonly employed for lactic acid production with
Lactobacillus or Lactococcus has motivated several studies using food wastes. Numerous
candidates have been explored, including sugarcane molasses [29], paper sludge [30],
waste paper [31], apple pomace [32], among others.
Fermentation techniques produce the desired stereoisomer, optically pure D (−) or
L (+) lactic acid, or a racemic mixture. The majority of the commercially produced lactic
acid uses modified strains of genus Lactobacilli [33]. The type of bacteria used governs the
type of stereoisomers obtained and the yield of lactic acid produced in the process. The
most technically and economically feasible alternative method of lactic acid production is
chemical synthesis using the lactonitrile route and applying acetaldehyde derived from
petroleum resources [28]. However, this method is expensive, and it can only produce
a racemic mixture of the lactic acid isomers [34]. As a result, approximately 90% of the
total lactic acid produced worldwide is made by bacterial fermentation, and only the small
remaining portion is produced synthetically by the hydrolysis of lactonitrile [28].
PLA of variable molecular weights can be produced from lactic acid. However, mostly
the high Mw PLA has commercial value in the fiber, textile, plasticulture, and packaging
industries [4].
The synthesis of PLA can be divided into chemical and biological polymerization.
Within chemical polymerization, there are three methods, (i) direct polycondensation (DP)
of lactic acid (ii) azeotropic condensation polymerization (iii) ring-opening polymerization
(ROP) of the cyclic dimer of lactic acid called l lactide [4,21,35].
The main steps of the direct condensation polymerization process involve: (i) removal
of free water, (ii) oligomer polycondensation, and (iii) melt polycondensation of high Mw
PLA [4,18,36]. A detailed description of the condensation polymerization method can be
found in [33].
On the other hand, azeotropic condensation polymerization (ACP) and ROP are
two methods for directly synthesizing PLA with high Mw. The former method (i.e.,
ACP) is similar to DP per se; the main difference lies in the use of the solvent in ACP to
reduce the systems’ viscosity at high degrees of conversion [37]. Moreover, ACP produces
high molecular weight polymer without chain extenders or adjuvants (unlike DP). The
general steps of DP and ROP are shown in Figure 2. The main difference between these
methods is that ROP involves an intermediate called lactide in the first step, which will be
discussed later. Due to the existence of different preparation methods, two names can be
interchangeably used to describe PLA, namely: poly(L-lactide) denotes the origin of the
polymer from the cyclic monomer, or poly(L-lactic acid) to indicate the repeating acid unit
in the polymer backbone, respectively. Thus, polymers obtained by polycondensation are
usually referred to as poly(lactic acid) and those prepared from lactide as polylactides. In
the present work, both types are abbreviated as PLA for simplification.
C 2021, 7, 42 5 of 43

Figure 2. Available routes to obtain PLA, ring-opening polymerization (ROP), and direct polymerization (DP). Polylactide
is a synonym for poly(lactic)acid (PLA), and the names can be used interchangeably.

ACP was first reported by Mitsui Toatsu Chemicals, Inc. Singapore [38]. It involves
continuous removal of condensation water by azeotropic distillation and consists of the
following steps: (i) distillation of lactic acid under vacuum; (ii) addition of catalyst and
diphenyl ether and oligomer polycondensation; (iii) polycondensation of melt to obtain
high Mw PLA while refluxing the solvent with additional drying using 3-A molecular
sieves (iv) isolation or precipitation of PLA [4,21,33]. It should be noted that the PLA
produced by ACP is very likely to contain traces of the catalysts used during its synthesis,
which may, later on, lead to unwanted side reactions or even PLA degradation. Thus,
additional steps of PLA purification procedures have to be carried out after the synthesis,
such as precipitation of the catalyst followed by filtering in the presence of, e.g., sulfuric
acid. Tin catalysts can be deactivated by the addition of phosphoric acid [38].
ROP is the industrially most preferred method of obtaining high-Mw polylactic acid
and copolymers of lactide and glycolide. The method is based on the original Cargill-Dow
patented process [8,18,33,37,39] and allows obtaining high Mw PLA with narrow molecular
weight distribution. ROP can be carried out in the melt, in solution, or suspension, and a cat-
alyst is usually required to start the polymerization process [40]. The primary intermediate
of ROP, lactide, is a cyclic lactic acid dimer formed in the first step of the reaction (conden-
sation polymerization), while the condensation water is removed via evaporation during
oligomerization. All enantiomers of lactic acid (i.e., L-lactic acid, D-lactic acid, or mixtures
thereof) can be polymerized to low Mw PLA (prepolymer PLA), which is subsequently
depolymerized by thermal unzipping reaction to form lactide [40]. Three stereoisomers of
lactide can be produced, namely: L-lactide, D-lactide, and Meso-Lactide [9,34], as shown
in Figure 3, which can result in three stereochemical forms of PLA, namely: PLLA, PDLLA
and PDLA [41].
It is noted that several excellent reviews are dealing with ROP of lactide to obtain
PLA, where details about this synthesis method can be found [11,39,42].
C 2021, 7, 42 6 of 43

Figure 3. The stereoisomers of lactic acid and the resulting lactides, together with their optical activity
adapted from [9].

4. Properties of PLA
4.1. Thermophysical Properties and Crystallinity
The thermophysical properties and crystallinity of PLA have a direct influence on
its degradation. The thermophysical properties of PLA depend on molar mass, thermal
history, and purity of the polymer sample The influence of these features on the thermal
behavior of PLA has been a subject of many published works; thus, here, only general
trends that are strongly connected with the degradation of PLA will be pointed out, which
involve heat capacity, thermal transition, and crystallization of PLA. Interested readers can
find more detailed information about these properties elsewhere [16,43–49].
Polymers prepared from meso- or racemic-lactide are amorphous, as mentioned
before, but by applying stereoselective catalysts, PLA having tacticity high enough for
crystallization can be obtained [20]. The crystallization rate of PLLA is unusually high at
temperatures between 100 and 118 ◦ C [50]. PLA can crystalize in three structural forms:
α, β, and γ, which differ in the helix conformation and symmetries [50,51]. The PLA’s
crystallinity can be increased with nucleating agents in injection-molding and extrusion [52].
In this way, the α form mentioned above is produced. Alternatively, the β form of PLA
develops upon mechanical stretching of the more stable α form from solution-spinning
processes conducted at high temperatures or high hot-drawing ratios (i.e., stress-induced
crystallization) [50,52,53].
Moreover, crystallization of PLA for applications requiring high thermal stability
can be initiated by annealing PLA at temperatures higher than Tg but below its melting
point [15]. It should be pointed out that the rate of crystallization of PLA is much slower
than other thermoplastics, limiting its use in high-performance applications. The rate of
crystallization influences the PLA degradation rate, thermal resistance, optical, mechanical,
and barrier properties.
Typically, Tm, Tg, and crystallinity of PLA decrease with decreasing content of L-
isomer. However, it also depends on the Mw of the polymer. Oligomers with a minor
number of lactyl units show a Tg directly dependent on Mw [20,54]. The Tg of PLA directly
impacts the material’s processability and service temperature.
In comparison to other thermoplastics, PLA has a relatively high Tg and low Tm.
Metastable states of high molecular weight amorphous polylactides, based on the reports
C 2021, 7, 42 7 of 43

of Auras et al. [55], are shown in Figure 4. As follows, below the so-called transition
temperature of −45 ◦ C, PLA is entirely brittle. Between temperatures of −45 and 58 ◦ C,
amorphous polylactide undergoes physical ageing and behaves similarly to glass, capable
of creep until it is cooled to its transition temperature [15]. In this range of temperatures,
PLA can show ductile or even brittle fracture [55]. As the temperature increases above
Tg (~58 ◦ C), PLA becomes rubbery. At temperatures below Tg, no large-scale molecular
motion is feasible inside the polymer chains, and the material is hard, which explains its
behavior. On the other hand, if the temperature increases above Tg, some motion can occur,
and the material becomes softer [16].

Figure 4. Metastable phases of high Mw amorphous PLA adapted from [55].

Thus, PLA with a low Tg is not suitable for storing hot liquid, as with the increased
temperature, the material would soften and would easily deform [9]. With further increase
of the temperature, in the range of 110–150 ◦ C, PLA changes its phase from rubbery solid
to viscous liquid, and this transformation depends mainly on the Mw of the specimen
and the applied shear stress [55]. As shown in Figure 4, at temperatures above 215 ◦ C,
PLA undergoes decomposition. Overall, the properties of amorphous PLA depend on the
difference between its Tg and the temperature at which it is stored and used.
For semicrystalline PLA, both Tg and Tm are critical for predicting the polymer´s
behavior. For amorphous PLA, the Tg is one of its most essential parameters since dra-
matic polymer chain mobility changes occur at and above this temperature. As a result,
amorphous plastics, such as PLA containing a mixture of D and L-lactides, perform best at
T < Tg, but elastomers must be used above the brittle point [18]. Moreover, it should also
be mentioned that the Tg of PLA depends on its optical purity and, to a large extent, on the
particular sample’s thermal history.
Concerning the Tm, it is usually influenced by the level of crystallinity of the poly-
mer [52]. Pure poly(D-Iactide) or poly(L-lactide) equilibrium crystalline melting tempera-
ture can be as high as 207 ◦ C. However, the lower temperature of around 180 ◦ C is typically
measured in practice due to small and imperfect crystallites, slight racemization, and impu-
rities usually present in the materials. The Tm = 180 ◦ C can be decreased down to 130 ◦ C
by adding meso lactide, depending on the amount incorporated into the polymer [15].
As obtained, lower crystalline melting points allow lower melt-processing temperatures
of the final polymer, expand the process window, decrease lactide formation and reduce
degradation [52].
Blending of PLLA and PDLA can form a stereocomplex with an equilibrium crystalline
melting point as high as 230 ◦ C, which is considerably higher than the Tm of the pure
polymers. This increase in Tm is due to the side-by-side packing of stereo complexes,
forming a compact, and ordered structure [56,57]. The mentioned Tm of enantiomerically
pure semicrystalline PLA is higher than 130 ◦ C, which is typical for amorphous meso-
C 2021, 7, 42 8 of 43

lactide [20,21,54,58]. Precisely, for engineering applications, which demand high thermal
stability, the general tendency is to use a PLA matrix with extremely low D-isomer content,
which can exhibit higher Tm and degree of crystallinity. Moreover, Tm of PLA depends
strongly on its molar mass. For example, PLA with Mn of 2000 displays a 60 ◦ C lower Tm
than that of PLA with Mw close to 20,000 [58].

4.2. Miscibility with Other Polymers

New PLA-based products (composites, nanocomposites, tailored formulations, etc.)
with improved characteristics and performance are always under research and develop-
ment. Reducing the cost of the material by blending PLA with other polymers is also
crucial since the cost of PLA is roughly twice to three times the cost of oil-based plastics.
On the other hand, employing copolymerization, blending, or additives to PLA is one way
to control its degradation by influencing its mechanical and thermal properties. Thus, we
will briefly discuss the most commonly found blends of PLA.
Lactic acid can be polymerized with other monomers, hydrophilic macromonomers
(e.g., PEG), or other monomers with functional groups (such as amino and carboxylic
groups) [18]. For example, the copolymerization of lactide with another lactone-type
monomer such as polyglycolide results in poly-lactic-glycolic acid (PLGA), which has
lower crystallinity and melting point than PLA [59].
Polyethylene glycol (PEG) is an excellent plasticizer for PLA and can significantly
enhance its elongation at break [60]. Moreover, PLA is very often mixed with starch in the
presence of glycerin due to economic reasons and to improve the mechanical properties of
PLA (e.g., increase toughness) by changing the concentration of starch in the composite [61].
Another study reported the improvement of tensile strength and elongation after blending
PLA with starch particles. The enhancement of the properties mentioned above depends
on the starch granules’ average particle size—the improvement declined when the granules
were greater than 45 µm [15].
Several PLA blends with other polymers have been studied over the past years,
including: poly(4-vinyl phenol) [20,62–64], poly(vinyl acetate) [20,62,65,66], poly(vinyl
chloride) [20,67], poly(ethylene) [20,68], poly(ethylene oxide) and copolymers [20,62,69,70],
poly(ethylene glycol) [20,62,71], poly(ethylene-co-vinyl acetate) [20,62,72], poly(cis-1,4-
isoprene)s [20,73], poly(ε-CBZ-L-lysine) [20,74], polyacrylates [20,75–77], poly(butylene
succinate) [20,48,62,78], hydrolytically degradable rubbers [20,79], silicates [20,80], glycol-
ide [20,62,81,82], and polyhydroxyalkanoates [20,62,83,84].
In general, to improve the targeted property, phase separation during blending should
be avoided. On the other hand, immiscible blends produce a rubber toughening ef-
fect on PLA that could benefit some applications [20,62]. Under normal conditions, a
compatibilizer (i.e., catalyst or a coupling agent) must make the polymers miscible with
PLA [20,62,85].

5. Degradation of PLA
According to the European Union standard, a biodegradable material should be
converted in more than 90% into CO2 , water, and minerals by biological processes within
six months. More generally, the European norm for biodegradable plastics (CEN/TR
159325) states that the characteristics of biopolymers and bioplastics can be used to describe:
• Biogenic or biobased plastic, originating from renewable sources;
• Biodegradable plastics, in terms of their functionality;
• Biocompatible plastics, in medical applications only.
The term biodegradation is often used to refer to the degradation of PLA occurring
in biological environments. The process is based on microorganisms (bacteria, fungi, and
algae) using a polymer material as a source of energy for their life [86].
PLA is a biodegradable commodity plastic that needs to be stable during the service
life but quickly degrade when it enters the waste stream, should the recycling be not
C 2021, 7, 42 9 of 43

feasible. Initially, PLA biodegradation occurs on the PLA surface and ultimately spreads
inside the PLA matrix to facilitate the material’s total degradation.
PLA can undergo hydrolytic, thermal, oxidative, bacterial, enzymatic degradation
and photodegradation [87]. However, most of the studies published were focused on
enzymatic degradation [88–90] or hydrolytic stability of PLA [41,91,92]. These mechanisms
are essential for reducing PLA to CO2 , water and biomass material in the context of
increasing environmental issues with plastic waste disposal.
Degradation of any polymer produces changes in its mechanical, optical, or electrical
characteristics through crazing, cracking, erosion, discoloration, or phase separation [93].
It can take place via (a) scission of the leading chains, (b) scission of the side chains, or (c)
scission of the intersectional chains [41]. It should be noted that all of the PLA degradation
mechanisms usually involve the ester bonds’ scission. Depending on the type of factor
inducing the degradation process, we can divide the degradation of PLA into non- biotic
processes (i.e., hydrolysis, thermal degradation, oxidation, photolysis) and biotic processes
(i.e., digestion by microorganisms) [4,21]. Out of the processes mentioned earlier, abiotic
hydrolysis isa rate-limiting step in the biodegradation of PLA [94].
Regarding the hydrolytic stability of PLA, one of the significant challenges that the
PLA users have to face is its tendency to undergo degradation during processing from the
molten state. The degradation is accelerated if the material is not correctly dried. Thus the
PLA substrate has to be carefully dried beforehand, accordingly to the indications from
the supplier.
The rates of thermal (isothermal at 220 ◦ C), biological, and photo-degradation (under
ultraviolet (UV) light) of PLA with 4 mol% D were compared by monitoring the mass
decrease of the polymer samples. The study concluded that the primary step under all
of the conditions studied was a random chain excision, and the degradation rate of PLA
specimens followed the progression: thermal > photo > biological. Overall, the degradation
in the soil was found to be the slowest of the three processes considered. After the same
degradation time, photodegraded specimens showed about half the molar mass of soil-
degraded samples [95].
The degradation of PLA depends not only on the characteristics of the specimen
(i.e., degree of crystallinity, molecular weight, sample morphology, its molecular and
supramolecular structures, etc.) but also on the conditions of the surrounding environment,
including the presence of water and moisture, temperature, acidity conditions, presence of
oxygen, or type and activity of microorganisms [96]. For example, water or moisture are
essential in the degradation environment for the microorganisms to grow and reproduce.
Additionally, the increase in water amount maximizes the rate of hydrolytic degradation
of PLA. Thus, it can be expected that the overall biodegradation of PLA will be faster in
moisture-rich environments than in dry conditions [96].
In general, the rate of PLA degradation is mainly determined by polymer reactivity
with water and catalysts (if present) [55]. Temperature is another critical factor affecting
the degradation of PLA. In general, the hydrolysis rate and the microbial activity increase
monotonically with temperature. However, at too high temperatures, microorganisms’
activity can drastically decrease or stop altogether.
Another environmental factor influencing the degradation of PLA is exposure to UV
light. It was found that UV light decreases the physical integrity of PLA, increases its
brittleness, stress at break, and average Mw [21]. The photodegradation and other modes
of PLA degradation will be described in more detail in the following paragraphs.
Last but not least, the degradability of PLA depends on macromolecular architecture.
Thus, branched structures display faster degradation rates than the corresponding linear
ones [97,98].

5.1. Hydrolytic Degradation

An in-depth understanding of the hydrolysis process of PLA is imperative to control
the degradation properties of most of the PLA products at the end of their lifetime. During
C 2021, 7, 42 10 of 43

hydrolysis, the main chain’s ester groups are cleaved until the polymer is completely
converted into soluble oligomers and monomers [4,20,21,99]. The ester bonds of PLA
fragment into carboxylic acid and alcohol by chemical hydrolysis due to hydrion (see
Equation (1)). However, in the absence of any catalyst, the hydrolysis of PLA consumes
plenty of energy and time [41,87].
The degradation of PLA in water can be described as a non-enzymatic chain scission
followed by a chain-end, which causes a decrease in the Mw of PLA [4,20,21].

−COO + H2 O → −COOH + OH (1)

Hydrolysis can take place not only in water but also in alcohol [100], alcoholic solu-
tions, such as water-ethanol mixtures [101], or acetonitrile solutions [99]. Conversely, it has
been found that PLA will plasticize and crystallize in the presence of other organic solvents,
which swell the polymer matrix, increasing chain mobility and rapid solvent-induced
crystallization [8,102].
The hydrolysis of PLA is a self-catalyzed reaction since the carboxylic acid end groups
of PLA and their oligomers can catalyze the breakage of ester linkages. The chain’s scission
during hydrolysis releases H+ acid groups. The acid is retained in the material or the
reaction medium, resulting in a decrease in the pH and acceleration of the hydrolysis
rate [87]. The pKa of PLA’s carboxylic acid end group and its oligomers is lower (~3) than
most carboxylic acid groups (4.5–5), leading to a faster rate of degradation (autocatalysis).
As it can be expected, the hydrolysis of the amorphous PLA chains is always easier
than that of crystalline ones because water diffuses readily into the less organized amor-
phous regions. Thus, hydrolysis tends to start in these regions and later propagates with
a decreased rate into the sample’s crystalline parts [8,21,103]. As a result, the hydrolytic
degradation of PLA causes a substantial increase in the specimen’s crystallinity and reduces
its physical and mechanical properties [104].
Chen et al. studied molecular ordering of amorphous PLLA during hydrolysis in
alkaline media at temperatures in the range of 40–60 ◦ C [105]. The authors found that
at temperatures of 40–50 ◦ C, a locally ordered structure was created, and many α-form
crystallites were induced when the temperature reached 60 ◦ C. Subsequently, the amount
of ordered structure increased gradually with the time of hydrolytic degradation.
It should be mentioned that the hydrolytic degradation of PLA in medical applications
is not the focus of the present review. Interested readers can find information on this subject
in various excellent articles and reviews [106–108].

5.1.1. Hydrolysis Mechanism

In general, the hydrolytic degradation of a polymer results from the interplay between
chemical hydrolysis and diffusion of water and oligomers [2]. From the point of view of or-
ganic chemistry, the reaction is a bimolecular nucleophilic substitution (shown in Figure 5),
and it can be catalyzed by either acids or bases [109]. Interestingly, the mechanism and
kinetics of the hydrolytic degradation of PLA are governed by the pH of the sample’s
environment. In particular, at neutral or basic pH, the hydrolytic degradation occurs pref-
erentially through backbiting reactions, although a minor contribution of random scission
hydrolysis was observed [91]. On the other hand, hydrolytic degradation of D, L-lactic
acid oligomers in basic media showed random ester cleavage to be the primary mecha-
nism [110], which is controlled by the rate constant, the amount of absorbed water, the
diffusion coefficient of the chain fragments and finally by the solubility of the degradation
products: lactic acid and lactide [7,99,110].
C 2021, 7, 42 11 of 43

Figure 5. Scheme of nucleophilic substitution reaction, adapted from [109].

Tsuji and Ikaida reported that alkaline conditions are different from the others. The
formed oligomeric acids are dissociated into RCOO− and hence must have high hy-
drophilicity to diffuse into the outer solution in contrast to the non-dissociated oligomers
RCOOH formed in the neutral environment [104]. On the other hand, at acidic pH, it was
shown that the hydrolysis of PLA proceeds through a preferential scission of the polymer
end-groups, or so-called “unzipping”.
The kinetic constant of the scission of the terminal groups of PLA was reported to be
10 times higher than that of the internal esters [111].
The mechanism shown in Figure 5 seems to be relatively straightforward. However,
due to the long-chain structures and condensed states of polymers such as PLA, the detailed
steps of the PLA hydrolysis are far more challenging. For example, polymer bonds at the
end of the chain can have different reactivity from those situated in other sites, as well as
the reactivity of the crystal domain being different from its amorphous counterpart.
During hydrolysis, different diffusion-transport phenomena of water, ions, and PLA
degradation products occur. These phenomena can lead to several changes in the reaction
mechanism. For example, in larger PLA specimens, the carboxylic acid groups concentrate
inside the polymer due to the restricted diffusion of the chain ends. Thus, a pH gradient
develops because the polymer’s surface is kept at a neutral pH, which slows down the
degradation of the polymer matrix surface compared to the centre. The surface layer
only gives up when a critical osmotic pressure builds up inside the matrix due to the
accumulation of degradation products [109] .
The hydrolysis of PLA is a third-order kinetic reaction, as initially proposed by
Pitt et al. [112] in their study of the degradation of similar polyester material, poly(-
caprolactone). They reported that the hydrolysis rate of PLA depends on the concentration
of the polymer bonds, the quantity of adsorbed water, and the concentration of acidic
hydrolysis products, as well as on diffusion rate and coefficient of chain fragments within
the polymer, but interestingly, not on the amount of H+ itself [87,109]. This theory predicted
a linear relationship between the logarithm of the polymer molecular weight with degrada-
tion time, but it did not consider the transport phenomena during polymer degradation.
Schliecker et al. reported that the degradation constant decreases with increasing
Mw of PLA sample [110]. Lyu et al. [109] reported that the hydrolysis rate displayed a
slow-to-fast transition at a particular Mw. This transition was not affected by the mass
loss and water uptake of samples or the changes in the media’s pH values. Thus, it was
speculated that this transition was due to the slow diffusion of the polymer chain ends.
The authors found that the concentration of the chain ends has to reach a specific critical
value, at which the hydrolysis starts to be promoted by the carboxylic acid chain ends.
Other works point out that the kinetics of chain scission of PLA indicates an autocatalytic
process. The carboxylic acid end groups generated by ester hydrolysis contribute to the
process acidity and participate in the transition state [99] .
The corresponding rate equation for hydrolytic degradation is given in Equation (2),
where [H2 O], [E], and [COOH] are concentrations of water, ester (reactant), and carboxyl
end groups [99,112–115].

d[COOH ] d[COOH ]
= k[ H2 O][COOH ][ E] = k[ H2 O][COOH ][ E] (2)
dt dt
C 2021, 7, 42 12 of 43

According to this equation, the term “self-catalysis” can be defined as taking place
when the acid group (catalyst) concentration increases and, simultaneously, the ester
(reactant) concentration decreases in 1:1 mole proportion.
Pseudo-first-order kinetics is a good approximation for hydrolysis catalyzed by a
strong external acid but is not entirely suitable for self-catalyzed hydrolysis. Thus, a model
was proposed (see Equation (3)) considering partial dissociation effects and half-order
dependence on a carboxylic acid group. This model fitted the experimental data well
except for the data set extrema [92,99,114].

d[ E] 1
= k0[ E]([COOH ]Ka ) 2 (3)
dt
In general, the hydrolysis of PLA can be described with four subsequent steps: (i) water
sorption, (ii) reduction of mechanical properties, (iii) reduction of Mw and (iv) complete
loss of weight of the material [115,116]. During the process, a loss in strength and modulus
is observed due to the plasticizing effect of water and the drop in Mw of the polymer.

5.1.2. Erosion
It should be mentioned that hydrolysis is only an initial step of a multistep process in
which the polymer eventually degrades. In this context, the whole process from the polymer
hydrolysis to its complete “disappearance” into the environment is called erosion [117,118].
Two types of erosion have been classified according to the way of degradation. These
processes are: surface erosion (heterogeneous) or bulk erosion (homogenous) [87,96,117].
For example, hydrolysis occurs heterogeneously because it proceeds faster in bulk than on
the surface [92,117]. Furthermore, it was reported that heterogeneous erosion is faster than
its homogenous counterpart [7].
Surface erosion happens when the hydrolysis rate is higher than the water diffusion
into the material’s bulk [87]. The surface eroding polymers lose mass only in the wa-
ter/polymer interface. In this case, the sample’s shape remains the same, but its volume
decreases with time [117,118]. On the other hand, bulk erosion is when the hydrolysis
occurs throughout the entire sample, and during the process, water diffuses rapidly into
the polymer structure, and as a consequence, mass loss within the bulk of the sample is
observed [118]. Since the bulk erosion is not confined to the surface, the polymer sample
size usually remains constant for a substantial amount of time. It should be also men-
tioned that it is generally assumed that the degradation of PLA becomes a bulk process
above Tg. At temperatures below Tg, degradation of the polymer matrix is restricted to its
surface [3,119].
According to the literature, polymers that contain less reactive functional groups,
such as PLA, were reported to be predominantly bulk eroding materials [120]. Tsuji and
Ikada studied the degradation of PLLA films in alkaline solutions and reported that the
degradation proceeded through surface erosion mechanism [104]. On the other hand, some
authors believe that the type of erosion taking place mainly depends on the formation
velocity of diffusing oligomers [121]. It is generally accepted that PLA degradation is
heterogeneous (bulk erosion), which is assigned to an internal autocatalytic effect of the
carboxyl end group. During the infiltration of the material with water, the hydrolysis
develops from the inside of the polymer towards its surface, causing sudden and rapid
loss of strength and structural integrity [115,117].
A significant advance in this field was achieved by Burkersroda et al. [122], who have
developed a theoretical model that allows predicting the erosion mechanism of water-
insoluble biodegradable polymers. Following this model, all of the polymers can undergo
bulk or surface erosion, and the type of the mechanism depends on the diffusivity of water
inside the matrix, the degradation rate of the polymer’s functional groups, and the matrix
dimensions. Accordingly, the erosion mechanism is defined by the critical dimension of
the device to be degraded. It is defined by the thickness normal to the reaction surface
(abbreviated Lcritical = 7.4 cm in PLA). Thus, surface erosion happens when the thickness
C 2021, 7, 42 13 of 43

of the matrix is larger than Lcritical ; if the dimensions are smaller than Lcritical , bulk erosion
prevails [115,122].
On the other hand, Lyu and co-workers found that the erosion rate and the erosion
front width (defined as a product of induction time and the erosion rate) can be expressed
as simple functions of the rate of polymer bond hydrolysis, water diffusivity, and solubility,
and other experimentally defined parameters [118]. Considering this theory, the type
of erosion that the sample undergoes can be predicted considering the ratio of the front
width to the polymer specimen’s thickness. Moreover, the authors’ modelling work allows
predicting the type and rate of erosion for a given sample. These results allow better
understanding and control of the degradation of PLA.

5.1.3. Factors Affecting Hydrolytic Degradation of PLA

The most important factors that influence the hydrolysis rate of PLA are tempera-
ture, pH, relative humidity (RH), Mw of the sample and its crystallinity, chain stereo-
configuration, and the chemistry of the solvent. The rate of hydrolysis increases with
temperature as the chain scission is accelerated. For example, the abiotic hydrolysis rates
differ considerably in the range of temperatures from 20 to 60 ◦ C [109]. Furthermore,
it should be noted that the dielectric constant of liquid water decreases with increasing
temperature leading to the improved affinity of water for the polymer and acceleration of
the hydrolysis [123]. Most of the studies on the influence of the temperature on the PLA’s
hydrolysis were conducted at temperatures that were either higher or lower than Tg or Tm
of PLA, and they all suggested Arrhenius-dependent kinetics with activation energies in
the order of 40–100 kJ/mol [55].
In contrast, Lyu et al. studied hydrolysis of PLA in the range of temperatures from
37–90 ◦ C, which included the Tg of PLA (55 ◦ C), and they showed an essential complica-
tion in the general understanding of biodegradation of PLA. The authors found that the
molecular weight data at various temperatures could not fit the existing equations describ-
ing polymer degradation. Moreover, the data points at 37 ◦ C did not fit the Arrhenius
equation. It appeared that the lack of mobility of the –COOH chain ends in the early stages
of biodegradation was not adequately accounted for in the existing theories. However, the
authors found that the degradation kinetic constant followed a Vogel–Tamman–Fulcher
(VTF) temperature dependence [109].
On the other hand, Han and Pan [124] developed a polymer degradation model
which accounted for the interplay between the autocatalytic hydrolysis reaction, oligomer
diffusion, and degradation-induced crystallization. Later, this model was further improved
and simplified by Han and co-workers [125]. Another study reported that the rate of
PLA degradation is higher above Tg because polymer chains become more flexible at this
temperature, which increases the adsorption of water, accelerating both hydrolysis and
microbial attachment [21].
Concerning the influence of the solvent chemistry on the hydrolytic degradation of
PLA films, the rate of the process was found to be higher in 50% solutions of ethanol in
water than in 95% ethanol or pure water [101]. It was explained by the fact that ethanol
molecules diffused more efficiently inside the polymer matrix.
Furthermore, Coszach et al., in their patent [126], reported that when alkyl lactates
are used as a solvent for hydrolysis of PLA to lactic acid, they significantly aided PLA
dissolution and added supplementary benefit of removing other polymers. Hydrolysis of
PLA in alkyl lactates was achieved with or without NaOH at 80−180 ◦ C and pressures of
up to 10 bar.
The effect of pH on the hydrolytic degradation of PLA has been studied in a few
works. It is known that the hydrolysis of polyesters is slowest in pH 4 solutions. The study
of lactic acid degradation showed that on increasing pH values from 1 to 10, the observed
rate constant values first decreased and reached a minimum at pH of about 4, and then
increased for higher pH values [127]. Notably, the increase mentioned above is about 4
orders of magnitude. It can be explained taking into consideration that the pKa of lactic
C 2021, 7, 42 14 of 43

acid is 3.84, which means that in solutions with pH > 4, lactic acid will be present mainly in
a dissociated form, thereby accelerating hydrolysis. Alternatively, in solutions with pH < 4,
lactic acid at the chain ends exists in an associated acid form, which increases the rate
of hydrolysis via auto-acceleration. In agreement with these results, Göpferich reported
that a fast rate of hydrolytic degradation of PLA could be realized at low and high pH
conditions [117], which confirmed that both acids and bases could catalyze hydrolysis.
Conversely, the degradation rates of solid polylactide samples were reported to be
almost the same for pH values of 0, 4, and 7. It was explained by the fact that the ions
(H+ and OH− ) from the solutions have very low solubility in polymers, so they cannot
effectively catalyze the degradation of solid polymer samples [128].
Another study reported higher hydrolytic degradability of poly(D, L-lactic acid) in
strongly basic conditions than in strongly acidic conditions, but very low degradability in
moderate acidic, basic and neutral conditions [129]. Interestingly, in a buffered pH media,
the auto-acceleration of PLA’s hydrolysis was found to be suppressed at neutral and low
pH [109,117].
Concerning the influence of the RH, it was reported that the rate of hydrolysis of PLA
increases with a high RH (>60%) due to faster absorption of water molecules [4,21,99].
Another study focusing on hydrolytic degradation of PLA films revealed that the state
of water (i.e., liquid vs. vapor) has an interesting influence on the hydrolysis rate. It was
found that prolonged storage of PLA specimens (2 months) in water or 100% RH conditions
was slightly faster than in the liquid water conditions [130].
It was reported that the higher degree of crystallinity and higher dispersity of PLA
decrease the degradation rate. As mentioned before, the incorporation of D-units in the PLA
material perturbs the crystallization process and thereby reduces the degree of crystallinity
of the sample. Thus, increasing the amount of D-units in the PLA specimen lowers the
regularity of the material and increases the water diffusion rate, leading to the acceleration
of the hydrolysis. Moreover, hydrolytic degradation was also enhanced by a higher molar
mass distribution of PLA [131].
The hydrolytic degradation of PLA products can be tailored to broaden its applications
by adopting the following methods: (i) incorporation of hydrophilicity into the surface of
the polymer, (ii) addition of hydrophilic fillers or polymers, (iii) incorporation of proteinase,
which facilitates hydrolytic attack, (iv) introduction of chain extenders [132], (v) decrease
of activation energy of hydrolysis [127]. Some of these approaches will be discussed in
more detail in the following paragraphs.

5.2. Thermal Degradation

One of the main disadvantages of PLA is its limited thermal stability, especially at
temperatures above 190 ◦ C [58]. It is mainly because the ester groups of PLA responsible
for polymer degradation are also thermally unstable [133]. Thus, the thermal degradation
of PLA usually is enhanced by moisture, oxygen, metal catalysts, or mechanical forces [134].
Depending on the combination of external forces, the degradation of PLA under elevated
temperatures can be purely thermal, thermo-oxidative (degradation due to temperature
and the presence of oxygen in the atmosphere), or thermo-mechanical (degradation due to
temperature and mechanical stress) [135].
In general, structural changes in the PLA start to be visible at Tg when the mobility
and the volume of the polymeric chains are modified [136]. Thermal degradation of
PLA is associated with the hydrolysis initiated by moisture during processing and is
influenced by several factors such as initial Mw, the amount of residual water, and traces
of polymerization catalysts (if present).
Under an inert atmosphere, thermoplastic polymers’ thermal degradation occurs at
Tm when the polymer is transformed from a solid into a viscous liquid. In the case of PLA,
it depends on the Mw of the sample and occurs at temperatures from 159–178 ◦ C [136].
Several studies have addressed the complex mechanism of the thermal degradation
of PLA. Zou et al. interpreted the thermal degradation kinetics of PLA in multi-step
C 2021, 7, 42 15 of 43

degradation mechanisms [137]. Some of the most commonly-reported PLA degradation

mechanisms can be observed in Figure 6.
McNeal and Leiper [103] reported that thermal degradation occurs predominantly by
random chain scissions through non-radical reactions along the PLA backbone. Dynamic
oscillatory measurements showed that the extent of these phenomena could be increased by
raising the temperature, extending time, or applying mechanical stress [135]. Additionally,
some radical reactions can be present at temperatures above 270 ◦ C.
Kopinke and Mackenzie [138,139] reported transesterification and non-radical reac-
tions to be the major mechanisms of PLA0 s pyrolysis, apart from non-selective radical
reactions observed at temperatures above 300 ◦ C. The authors found that intramolecular
transesterification gives rise to cyclic oligomers.
Due to acrylic acid found in the reaction products, cis-elimination (shown in Figure 6)
was also suggested as another reaction pathway [103]. The ester interchange has lower
energy of activation than the cis-elimination. Therefore, the ratio between these reactions
shifts towards the cis-elimination at more elevated temperatures. Apart from acrylic acid,
other products of cis-elimination include oligomers with open-chain structure and carboxyl
groups. O-phthalic acid or 1,4-butanediol can also be produced if the reaction starts in the
nonactivated C-H bonds [139,140].
Apart from the mechanisms discussed above, Jamshidi and co-workers [58] found
others such as: thermohydrolysis, depolymerization, and cyclic oligomerization. These
mechanisms can lead to the appearance of a wide range of products, such as lactide and
cyclic oligomeric units, CO, CO2 , acetaldehyde, and methyl ketone, which might further
degrade into methane and butanedione [103,137,139].
According to Kopinke [139], acetaldehyde formation above 270 ◦ C increased with
temperature, whereas McNeal and Leiper [103] observed that the maximum concentration
of acetaldehyde was around 230 ◦ C and decreased at higher temperatures. It was due to
acetaldehyde degradation involving chain reactions to CH4 and CO by-products.

Figure 6. Thermodegradation PLA mechanisms adapted from [4,141].

C 2021, 7, 42 16 of 43

At elevated temperatures (230–440 ◦ C) and in a closed system, the dominant reaction

pathway of the isothermal degradation of PLA was found to be a non-radical, backbiting
ester interchange reaction involving the OH chain ends. It should be pointed out that the
type of products from the backbiting reaction depends on the point in the backbone of the
PLA where the reaction occurred. The products include lactide, oligomers, acetaldehyde,
and CO [103,139]. Moreover, when the temperature was raised above 270 ◦ C, the homolysis
of the polymer backbone was additionally observed to give other minor side products [103].
Zou studied thermal degradation of PLA in nitrogen and reported that the reaction
initiated at ≈275 ◦ C and complete decomposition of the sample was obtained at ≈420 ◦ C
with the evolution of the following products: cyclic oligomers, lactide, acetaldehyde, carbon
monoxide, and carbon dioxide. The products were attributed to the hydroxyl end-initiated
ester interchange process and chain homolysis [137].
Carrasco and co-workers [142] studied the thermal decomposition of processed and
raw PLA specimens and determined the activation energy (Ea) to be 280 ± 5 kJ/mol for
the former and 318 kJ/mol for the latter sample. They demonstrated that there was only
one first-order reaction for the entire conversion range.
In comparison, a detailed study of the isothermal degradation of PLA in the tempera-
ture range of 240–270 ◦ C was accomplished by McNeill and Leiper. They also showed a
first-order kinetic evaluation of isothermal measurements of PLA volatilization. Moreover,
a considerably low value of Ea = 119 kJ/mol was obtained in their study. It was attributed
to the feasibility of transition state formation under the reaction conditions [103]. Other
studies reported Ea of thermal degradation of PLA changing irregularly in a range of
70–270 kJ/mol as the degradation progresses [143,144]. It was also found that the value of
Ea tends to increase at higher conversions of PLA, due to more complex kinetics [139].
The onset of thermal degradation of PLA is strongly affected by several factors, includ-
ing residual polymerizing catalyst (residual metals), Mw of PLA, and moisture [145,146].
For example, the effect of these residual catalysts on the thermal decomposition of PLA was
studied by Cam and Mauruci [147], and their experimental results enable the comparison
of the influence of different metal impurities on PLLA thermal stability, which follows a
decreasing order: Fe > Al > Zn > Sn. Among these metals, the Sn catalyst is of particular
importance because only Sn 2-ethylhexanoate (Sn(Oct)2 ) is approved by the Food and Drug
Administration (FDA) as a catalyst for food contact applications [144]. The authors found
that the presence of Sn, Zn, Al, and Fe in trace amounts (i.e., 0–15,000 ppm) in purified
PLLA accelerated the inter-and intra-molecular transesterification reactions as well as the
backbiting reaction (as shown in Figure 6 at higher temperatures (i.e., T > 240 ◦ C).
Figure 7 shows the changes in the decomposition temperature vs impurity concentra-
tion measured by Cam and Marucci [147]. The authors showed that the decomposition of
PLLA was accelerated even with a very low level of impurities below 2000 ppm. It was
also concluded that transition metals (e.g., Fe) have a high capacity to coordinate ester
groups and, as a result, accelerate depolymerization and transesterification reactions [147].
Several techniques showed that the thermal decomposition of PLA samples containing
a higher amount of residual Zn compounds in the matrix can occur via intermolecular
transesterification and selective unzipping depolymerization [4,144,148].
Cam and Maurucci [147] concluded that Sn- and Zn-initiators could give rise to
interchange and depolymerization at high temperatures, but more modestly than Al
and Fe since they are known as the most selective catalysts for the polymerization of
lactide (as it was mentioned before); thus they are less efficient in thermodegradation of
PLA [147,149,150].
C 2021, 7, 42 17 of 43

Figure 7. Effect of residual catalyst presence on PLA thermal degradation [147]. Reproduced with
permission from Elsevier, 2021.

On the other hand, Jamshidi et al. [58] described an accelerating effect of Sn(Oct)2
(5 wt %) on the PLLA pyrolysis. They presented thermogravimetric analysis (TG) under
isothermal conditions, which showed that the Sn-containing sample exhibited a linear
weight loss curve with time, in contrast to the pure PLLA, which showed a sigmoid curve.
These observations suggested a change in the weight loss behavior from a random process
to a zero-order reaction induced by the addition of an Sn atom.
Regarding the influence of Mw of PLA on its thermal degradation, Cam and Marucci [147]
reported that the lower the Mw of the PLA oligomer, the lower the decomposition tem-
perature. It was attributed to the fact that the specimens with lower Mw have a higher
concentration of hydroxylic groups, which trigger the degradation of PLA. Once a specific
Mw is reached (around 140,000 g/mol), the amount of terminal hydroxyl groups becomes
negligible compared to the ester repeating units within the polymer chain, and the influence
of Mw on the thermal degradation temperature becomes smaller [147].
The influence of moisture or hydrolyzed monomers or oligomers on the thermal stabil-
ity of PLA is far lesser than that of residual metals. For example, Cam and Maurucci [147]
reported that a sample containing 1 wt % of monomers decomposed at a temperature
slightly lower than that of the PLA (1–2 ◦ C), whereas the PLA samples containing the same
amount of metals (10,000 ppm of Sn, Zn, Al, Fe) decomposed respectively at 50, 60, 70 and
110 ◦ C lower than that of the pure polymer [147].
There are many ways to control the thermal stability of PLA. For example, end
protection of the hydroxyl group has been considered a possible method, and some reports
have been published dealing with the application of an acetyl group [4,148]. Acetylation of
PLA end groups by 2 h refluxing with acetic anhydride was found to increase the thermal
stability of PLA by 26 ◦ C [139].
Besides, some chain extenders can be used, such as, e.g., polycarbodiimide (PCDI)
and tris (nonyl phenyl) phosphite (TNPP) or Joncryl® , to increase the initial thermal de-
composition temperature of PLA. These extenders increase the PLA’s stability by reducing
active sites on the chain end per mass by producing longer polymer chains [4].
Stabilizers can also be added to diminish the impact of shear and temperature during
the processing of PLA. Furthermore, the molecular mass of these stabilizers is an important
parameter affecting the thermostabilization of PLA [151].
Oliveira et al. reported that the B900 stabilizer (i.e., a mixture of Irganox 1076, a pri-
mary stabilizer, and Irgafos 168, a secondary antioxidant) acts directly on the deactivation
of free radicals and hydroperoxide decomposition [134].
C 2021, 7, 42 18 of 43

On the other hand, in heterogeneous systems, such as PLLA/alkali earth metal ox-
ides, such as CaO or MgO, the oxides lower the degradation temperature range of PLLA
and completely suppress the production of oligomers except for lactides [144]. Moreover,
Kopinke et al. reported that blends of PLA with poly(methylmethacrylate) (PMMA) as
a source of radicals accelerate the decomposition of PLA, whereas the PMMA is stabi-
lized [139].
Concerning the thermo-oxidative degradation of PLA (i.e., in the presence of oxygen),
the process induces a chain scission mechanism of alkoxyl radicals (alkyl- and acyl-oxygen),
thus leading to the formation of new free radicals that can cause chain scission and forma-
tion of oxidation product degradations (mainly ester and carbonyl groups) [135].
According to Cameron and Kerr [152], during thermal oxidation in air, the initial
change in Mw of a polymer is due to the scission of bonds at various weak links that
might be present/or created during heating. Another work reported that the thermo-
oxidative degradation of PLA at the average processing temperature (around 200 ◦ C)
follows a random chain scission mechanism causing a significant molecular degradation
and leading to the formation of various degradation products (e.g., linear hydroxyl, ester,
and carbonyl groups, etc.) [139]. It is all reflected in a dramatic change of the molecular
structure, resulting in a decrease in the material’s melt viscosity and elasticity. In addition,
the Mw changes of PLA during thermo-oxidative degradation cause a decrease in Tg
according to the Fox–Flory theory and an increase in the degree of crystallinity due to a
chemicrystallization process [153]. Importantly, the processing equipment can be damaged
by the formation of the volatile lactide [134,135].
Concerning kinetics of thermal degradation of PLA in air, only a few assessments of
Ea, kinetic parameters, and reaction order can be found in the literature [133,154,155]. TG
studies of PLA degradation in the air suggested that the degradation kinetics follows the
Avrami–Erofeev equation for solid-gas equilibria, which indicates that the decomposition
of PLA is due to the growth and nucleation of decomposition sites in the solid [156].
Gupta and Deshmukh studied PLA degradation in the air using TG and reported a
first-order reaction with Ea = 92–126 kJ/mol [133,155]. The authors also discussed the dif-
ference between degradation of PLA in air and nitrogen. The derivative thermogravimetric
(DTA) curve in air exhibited two exotherm peaks and two endotherm peaks compared to
two endotherm peaks in the nitrogen atmosphere. The peaks obtained in air were assigned
to thermal decomposition (310 ◦ C) and oxidative degradation (321 ◦ C and 351 ◦ C). On
the other hand, the peaks obtained in nitrogen were identified as a phase change (140 ◦ C),
volatilization of low boiling point products (240 ◦ C), and thermal cracking (310 ◦ C) [133].
Liu et al. [154] compared the kinetics of PDLA thermal decomposition in air and nitrogen
and concluded that the process in both atmospheres had two or three stages, each with
different Ea. The authors applied the Arrhenius equation and calculated an Ea of 130 and
87.9 kJ/mol for the first and second stages of PDLLA in air, and 142 and 138 kJ/mol for
the first and second stages of PDLLA in nitrogen, respectively. They concluded that the
atmosphere had little effect on the degradation in stage one. However, in stage two, oxygen
had a clear promoting effect on the thermodegradation, which resulted in a substantial
drop in the value of Ea. Babanalbandi et al. [143] also compared the degradation of PLA
under nitrogen and air over the temperature range 180–280 ◦ C and obtained Ea values for
isothermal weight loss rate between 71.1 and 105 kJ/mol depending on the conversion
of PLA.
Finally, the degradation of PLA under vacuum was reported to take place at ap-
preciable rates at T ≥ 230 ◦ C, and the products observed included oligomers, lactide,
acetaldehyde, and carbon monoxide. At T = 277 ◦ C, CO2 appeared as an additional prod-
uct, whereas at T ≥ 320 ◦ C, methylketene became one of the major products. Small amounts
of methane were additionally recorded at higher temperatures [103].
Concerning the thermo-mechanical degradation, Amorin et al. [151] studied the
extrusion of PLA. They reported that the two types of degradation reactions could occur
during the process, radical and nonradical. The authors also reported that the presence
C 2021, 7, 42 19 of 43

of the additives could prevent the decrease in Mw of PLA when exposed to melting
temperature and shearing. However, nonradical reactions suppressed this stabilizing effect
during the exposition of PLA to higher temperatures and shear.
Other authors reported that a high level of stress applied to PLA at elevated tempera-
tures produces a decrease in the carbon-oxygen bonding energy in PLA and, consequently,
favors the chain scission. Moreover, radical reactions typically observed during oxidative
degradation of PLA are more likely to occur in the presence of a high level of stress apart
from oxygen [135].

5.3. Photodegradation
In several applications, such as, e.g., PLA twines in greenhouses, the polymer is
exposed to ultraviolet (UV) radiation, leading to discoloration or even brittle fracture caused
by photodegradation [4,41]. The photodegradation of polymer materials is particularly
accelerated outdoors due to the strong intensity of sunlight (around 245 nm [156]), which
includes invisible lower wavelength and higher energy UV radiation [157].
The main mechanism of photodegradation of polymers is the so-called “Norrish
type photocleavage”, typical for aliphatic polyesters having carbonyl groups, like PLA or
PCL [158]. Primarily, photodegradation mechanisms are initiated by the transformation of
the polymer via photoionization (Norrish Type I) and followed by polymer chain scission
(Norrish Type II) [87]. It is known that the carbonyl group (i.e., C=O) absorbs UV radiation
around 220–280 nm due to n-π* electron transition and that this energy can cause chemical
reactions [4,157]. Even though the extinction coefficient for PLA at 280 nm is very low (less
than 100 L/(mol cm)), photodegradation of PLA products certainly takes place during
exposure. Since the excited state of the C=O group of PLA via n-π* presents antibonding
and biradical characteristics, the photoexcitation of C=O can result in α and β cleavage,
atom abstraction, radical addition or electron abstraction or transfer. These excited states
of PLA are shown in Figure 8.

Figure 8. Excited states of PLA molecule adapted from [159] (a) the excited state of the C=O group
via n-pi* transition exhibits an antibonding and biradical property, (b) photoexcitation of C=O tends
to cause some chemical reactions, such as bond cleavage or (c) radical addition, electron abstraction
or electron transfer.

Jeon and Kim reported that UV irradiation enhances PLA degradation due to making
PLA sheets more hydrophilic after exposure, which results in easier absorption of water by
the polymer structures [156]. In turn, the chemical hydrolysis causes chain cleavage within
the PLA polymer, forming oligomers and monomers, which can be later biodegraded by
microorganisms [21].
C 2021, 7, 42 20 of 43

UV irradiation also affects the tensile strength of PLA, reduces polymer integrity,
and finally turns it into a white brittle solid that is difficult to be digested by microorgan-
isms [156]. Some authors claimed that faster degradation of PLA takes place with more
prolonged exposure to UV lights [95]. Other effects of UV irradiation on PLA include
changes in Mw of the polymer, decreased stress, and strain at break [4,160]. McNeil and
Leiper [103] studied the photodegradation of PLA under vacuum in a photolysis cell at
30 ◦ C for 72 h. Based on the volatile reaction products analysis, they suggested that PLA
decomposition by UV light happens at the O-C bond in the ester linkage. The proposed
mechanism of the reaction is shown in Figure 9 [103,157]. The proposed mechanism is very
similar to that of thermal degradation.

Figure 9. Mc Neil and Leiper mechanism adapted from [157].

Ikada studied photodegradation of PLA and reported a rapid (1 h) decrease of Mw of

PLA, attributed to a random main chain scission in the chemical bonds by absorption of
a photon[158]. The main chain scission occurred via the Norrish II type photo-cleavage
(shown in Figure 10). In addition, the studies comparing the photodegradation of PLA
with that of PCL showed that the chemical structure of the two sequential groups adjacent
to the ester oxygen has a decisive impact on the photodegradation mechanism [157,160]

Figure 10. Scheme of photodegradation via Norish II mechanism adapted from [4].

Tsuji et al. [160] studied PCL and PLA’s photodegradation behavior and suggested
bulk erosion as the main mechanism. Bulk erosion observed in all samples studied indi-
cated that UV penetrated the specimens with no significant reduction in their intensity,
irrespective of the chemical structure and the crystallinity of biodegradable polyesters. The
authors also concluded that although PLLA chains are photodegradable, even in the crys-
talline regions, however, their photodegradability is lower than in the amorphous regions.
As a result, the anhydride groups are formed, and the crystallization rate is decreased [4].
This is in contrast to hydrolytic degradation, where the chain cleavage occurs only in the
amorphous regions [160].
Janokar et al. [161] studied the effect of UV radiation wavelength within a range of
232–500 nm by irradiating the PLA films directly in atmospheric conditions or through a
Pyrex container (not optically transparent at wavelengths below 300 nm). They concluded
that the adsorption of photons by C=O and other relevant groups occurred at wavelengths
between 200 and 300 nm, resulting in the samples’ photodegradation. Furthermore, the
PLA Mw was less affected when the irradiated films were enclosed in a Pyrex container.
Based on their results, two different mechanisms of PLA photodegradation were proposed.
As schematically shown in Figure 11, mechanism A involves a photolysis reaction leading
to the breakage of the backbone C-O bond. On the other hand, mechanism B is based
on photo-oxidation of PLA, leading to the formation of a hydroperoxide derivative and
its subsequent degradation to compounds containing a carboxylic acid and di-ketone
end groups.
C 2021, 7, 42 21 of 43

Figure 11. Basic mechanisms proposed to predict the degradation products of PLA adapted from [161].

A similar mechanism of photodegradation was proposed by Bocchini et al. [162]. They

suggested that the photodegradation of PLA proceeds with the usual radical mechanism
beginning with the abstraction of a tertiary hydrogen atom from a PLA chain and the
formation of a radical. Then this radical reacts with oxygen to form peroxide and subse-
quently hydroperoxide. The authors proposed that the most probable β-scission leads to
the formation of anhydride groups.
Concerning factors affecting the photodegradation of PLA, Copinet et al. simulta-
neously studied the effect of UV, temperature, and humidity. They concluded that with
increased RH and temperature, there is a faster decrease of the degree of crystallinity, Tg,
and Mw apart from increased hydrolysis rate at the ester linkage. It was suggested that
the increased rate of hydrolytic degradation of PLA could be the result of an accelerated
autocatalytic process upon UV treatment (as described in the hydrolytic degradation para-
graph). Moreover, the UV irradiation, together with elevated temperature and higher RH,
caused a significant reduction in the polyester’s mechanical properties and accelerated its
degradation. In general, increased exposure time is expected to induce faster polyester
degradation [4,95]. However, Jeon and Kim [156] proved that the biodegradability of PLA
was enhanced as UV irradiation was increased to 8 h and then decreased with a further
increase in UV irradiation.
C 2021, 7, 42 22 of 43

There is not much information about the chirality effect on photodegradation of PLA.
However, as photodegradation starts at the monomer’s functional group, it would be
expected that D and L isomers should have the same mechanism of decomposition. The
chirality effects should be related to crystalline effects because the isomer ratio influences
the polymer crystallinity, as mentioned earlier in this review.
In addition to UV radiation, PLA can be exposed to X-ray or gamma-rays, which are
more intense than UV. The degradation mechanism of PLA is different under these two
types of radiation, which may lead to unselective ionization of molecules by interactions
with cloud electrons. The produced electrons are kinetically active to trigger subsequent
ionization. Intermediate products are formed due to side reactions as homolytic cleavage,
ionic scission, electron transition, and energy transition [141].
The effect of gamma and e-beam radiation on PLA has been recently studied by
Benyathiar et al. [163]. The authors reported a decline in the average Mw number of
PLA after exposure to both types of radiation. Moreover, the authors reported a decrease
in Tg and Tm upon ionizing irradiation. Mechanical properties such as tensile strength,
elongation at break, and elastic modulus also deteriorated [4,160,161].
Another study analyzed the effect of gamma-irradiation on PLA crystallinity in two
different atmospheres (air and vacuum) under constant radiation dose and rate. Tg and Tm
were found to be independent of the atmosphere and dose parameters, but the crystallinity
and the enthalpy decreased considerably in the air. On the other hand, the reaction yield of
damaged units was higher in vacuum [141,164].
Birkinshaw et al. [165] studied the influence of gamma-irradiation in molded poly-(D,
L-lactide) and observed changes in mechanical properties. The reduction in Mw made the
sample brittle due to the random chain scission of the polymer. Increasing the doses of the
radiation resulted in more substantial embrittlement.
The PLA integrity was also affected by electron beam irradiation. It was reported that
pre-treating of PLA by electron beam irradiation increased PLA brittleness and decreased
molecular weight during compost degradation compared to non-irradiated samples [166].
Interestingly, PLA properties such as low wettability and poor thermal resistance
above Tg can be upgraded using irradiation. It was reported that wettability and biocom-
patibility could be improved by ionized beam irradiation [141,167], UV/ozone irradia-
tion [141,168], or by oxygen radio frequency glow discharge [141,169]. Since intermolecular
interactions among polymer chains make the polymer more thermally resistant, a stan-
dard method is to induce cross-links in the polymer matrix by photoirradiation [141,170].
Moreover, reconstructing the PLA surface with hydrophilic molecules is also possible by
UV-induced graft polymerization [141,171].

5.4. Microbial Degradation

As mentioned before, composting involving microbial activity (e.g., actinomycetes,
bacteria or fungus) is a desirable method for environmentally friendly plastic waste man-
agement if recycling of the polymer is not feasible. The digestion of PLA by microorganisms
can only occur after successfully breaking the ester bonds in chemical hydrolysis to obtain
low Mw oligomers, CO2 , CH4, and carboxylic acid [4,21,87]. Thus, random non-enzymatic
chain scission of the ester groups occurs, leading to a reduction in molecular weight.
Embrittlement of the polymers generally happens in this step, reducing their molecular
weight [55]. Importantly, PLA is more resistant to microbial attacks in the environment than
other synthetic polymers [172]. When mineralization is not complete, biotransformation
occurs, creating organic and inorganic metabolites or transformation products. Mechanical
degradation can also occur through meso- and micro-faunal activities, such as earthworms,
that fragment polymer waste and incorporate it in the mineral soil [98].
Enzymatic mechanisms can be divided into two categories: enzymatic oxidation (by
aerobic microorganisms only) and enzymatic hydrolysis (by either aerobic or anaerobic
microbes) [96]. Microorganisms present in the soil begin to digest the lower molecular
weight lactic acid oligomers, producing CO2 and water, only when the average Mw of the
C 2021, 7, 42 23 of 43

PLA specimen reaches approximately 10,000 g/mol [52]. The mechanism of enzymatic
degradation is shown in Figure 12.

Figure 12. Mechanism of enzymatic biodegradation of plastics under aerobic conditions, adapted from [173].

Different microorganisms can digest the products of hydrolytic degradation of PLA,

which can be classified as actinomycetes, bacteria, and fungus [174]. Environmental factors
such as humidity, temperature, pH, salinity, the presence or absence of oxygen, and the
supply of different nutrients have important effects on the microbial activity in PLA
degradation [8]. Different authors considered the influence of some of the parameters
mentioned above. The optimum temperature for digestion of PLA oligomers for the same
microorganism in a specific strain can vary depending on the sample’s environment.
Following Bikiaris [89], the majority of polyesters are degraded by enzymes called
lipases. These enzymes usually are too large to penetrate inside the polymeric material,
and as such, they are only active after conformational changes have taken place. In
addition, due to the low solubility of PLA in water and the large size of its molecule,
the microorganisms are unable to transport the polymeric matter directly into the cells,
where the biochemical reactions take place. As a result, the microbes first release the
enzymes (called depolymerase) that work outside the cells until generating water-soluble
compounds, which can be transported inside the cells and digested in the appropriate
metabolic pathway [173]. Typically, inducers such as gelatin, elastin, silk fibroin, and some
amino acids and peptides are needed to stimulate the process [41,87]. This mechanism
the supply of different nutrients have important effects on the microbial activity in PLA
degradation [8]. Different authors considered the influence of some of the parameters
mentioned above. The optimum temperature for digestion of PLA oligomers for the same
microorganism in a specific strain can vary depending on the sample’s environment.
Microbes that can degrade PLA belong mostly to actinomycetes, a family of antibiotic-
producing filamentous bacteria commonly found in soil. Most of the PLA degrading
actinobacteria are Pseudonocardiaceae, and other families include Micromonosporaceae, Strep-
tomycetaceae, Streptosporangiaceae, and Thermomonosporaceae, etc. [175]. Apart from actino-
mycetes, the PLA-degrading bacteria include Bacillus brevis, Pseudomonas, Stenotrophomonas,
Laceyella sacchari, Nonomuraea, Thermoactinomyces vulgalis, and Bordetella petrii [175]. Addi-
tionally, thermophiles from the thermophilic genus Bacillus were reported to play a leading
C 2021, 7, 42 24 of 43

role in fermentation [174]. Further, there were reports of PLA oligomers (molecular weight
~1000) degradation by Fusarium moniliforme and Penicillium roqueforti and the degradation
of PLA by Amycolatopsis sp. [6].
Concerning the fungal degradation of PLLA, the process occurs at the chain-ends of
PLA. The microorganisms consume the monomer in the chain’s extremity, which leads to
depolymerization of PLLA [172]. The most commonly reported fungi that can assimilate
DL-lactic acid belong to the following types: Fusarium Moniliforme, Penicillium roqueforti,
Tritirachium album, Aspergillus fumigatus, and Thermomyces laniginosa, and partially soluble
racemic oligomers [172,176]. These microorganisms can colonize even extreme environ-
ments, where their ability to produce enzymes (e.g., lactases, hydrolases, esterases, and
dehydrogenases) allows them to degrade many chemical compounds with different func-
tional groups, including polyesters [177]. Moreover, it was found that the temperature
is the predominant parameter governing the fungal degradation of PLLA in soil and
compost [172].
The selection of the most commonly studied microorganisms for biodegradation
of PLA, together with the secreted enzymes and the optimum temperatures for PLA
degradation, are gathered in Table 1. As shown in Table 1, the key enzymes that play an
important role in the depolymerization of PLA are carboxylesterase, cutinases, lipases,
and serine proteases. Proteinase K was also reported to degrade neat PLA films and PLA
composites, and the rate of the degradation of the former being faster [178]. Besides,
enzymatic degradation of low molecular weight PLA (molecular weight ~2000) has been
shown using esterase-type enzymes such as Rhizopus delemer lipase [6].

Table 1. Microorganisms and enzymes degrading PLA with the temperature of the mineralization process [41].

Microorganism Representative Species Enzyme Temperature of Digestion (◦ C)

Amycolotopsis strain K104-1 55–60
Amycolotopsis strain 41 37–45
Actinomycetes Protease
Amycolotopsis strain orientalis 30
Actinomadura strain T16-1 70
Bacillus smithii strain PL21 60
Alcanivorax borkumenesis ABO2449 Esterase 30–37
Rhodopseudomonas palustris RPA1511 55–60
Bacteria
Paenibacillus amylolyticus strain TB-13 50
Alcaligenes sp. Lipase 55
Pseudomonas tamsuii TKU015 60
Tritirachium album ATCC 22563 Protease 37
Fungus
Cryptococcus sp. strain S-2 Cutinase 37

Serine protease usually follows a two-step reaction of hydrolysis. In the first step, PLA
substrate binds to the surface of serine protease at the active site. The following second
step involves the cleavage of peptide-like bonds in PLA through catalytic amino acids with
water [179]. Enzymatic involvement can produce pores and fragmentation, making more
polymer regions accessible to the enzymes [55] The activity of the enzymes depolymerizing
the PLA depends on the following factors: pH values, temperatures, chain stereochemistry,
and material crystallinity [87].
As mentioned earlier, PLA is resistant to microbial attack compared to other biodegrad-
able polymers [41,180]. Thus, pretreatments of PLA waste, such as gamma-irradiation
(described before) or mechanical grinding, help disorganize the macromolecular aggregate
structures of the material and increase enzymatic rate degradation.
Single culture, co-culture, and the microbial consortium have been studied to optimize
the best biodegradable conditions. It was reported that PLA degradation efficiency could
be enhanced using the simultaneous PLA degradation and dialysis method. The maximum
conversion efficiency of 89% was achieved after incubation for 72 h under optimized
C 2021, 7, 42 25 of 43

conditions [175]. Moreover, modern molecular biological techniques provide a powerful

tool to explore the diversity of PLA degrading microorganisms in the environment. These
techniques involve analyzing nucleic acids extracted directly from the environments, thus
avoiding the limitations of the culture-dependent approach [94].

6. Degradation of PLA in Different Environments

6.1. Composting Conditions
In horticulture, PLA has already substituted partially conventional PP as material
for twines supporting greenhouse crops such as tomatoes and peppers, mainly due to
the increasing need for sustainable cultivation and environmentally friendly and cheaper
waste processing. The cost of removing and disposing of PP twines into landfills is high,
and disposal facilities are not always available. Conventional plastics such as PP are not
biodegradable and thus add a sorting step into the composting process. On the contrary,
compostable polymers, such as PLA, can be decomposed by biological activity with no
visible and toxic residues [21,181]. For example, The Elite Bio Twine from Lankhorst
Euronete Portugal, produced using PLA, can degrade in industrial compost in 5 to 8 weeks
into an unrecognizable, hummus-like substance. If there are remains of string left in the
soil after the composting phase, they break down without leaving behind toxins in contrast
to the PP twines that have to be separated from the green waste before composting.
The composting process is used as a versatile approach to treat biodegradable solid
waste [119]. A mixed microbial population carries out composting in a moist, warm, aerobic
environment under controlled conditions [86]. As compared to sorting and reprocessing
for recycling, composting is a less energy-demanding process, although it requires more
energy than landfilling [119].
Plastic material can be considered compostable if it is biodegradable and can undergo
degradation by biological processes during composting at a rate similar to other known
compostable materials. It should be underlined that not all biodegradable materials are
compostable [96]. In general, PLA can be expected to decompose entirely into CO2 and
water in an adequate and controlled composting environment in less than 90 days [8].
The PLA degradation under composting conditions involves two-steps. The first step
is hydrolysis (abiotic process), followed by micro-organisms digestion to end-products
(biotic process). In this sense, the first step’s mechanism is very similar to that previously
described for hydrolytic degradation of PLA; however, composting also involves digestion
of soluble oligomers by bacteria and evolution of CO2 along with water as final products.
The last step might be under aerobic or anaerobic conditions. In particular, abiotic hydroly-
sis was suggested as the primary depolymerization mechanism and the rate-controlling
step of PLA biodegradation in compost [94,95]. The described two-step mechanism is a
unique characteristic of biodegradable polymers [21].
When it comes to composting conditions, they are organically rich with a large diver-
sity of microbial populations, as listed in Table 1. During composting, it is necessary to
consider that both; biotic and abiotic factors coexist in the same space. The complex process
of degradation in compost involves the following intermediate phenomena: (i) water ad-
sorption, (ii) ester bond cleavage and formation of oligomer fragments, (iii) solubilization
of oligomer fragments, and finally (iv) diffusion of soluble oligomers by bacteria in terms
of CO2 evolution [173,182]
The composting starts with the abiotic process, chemical hydrolysis, and occurs in the
presence of water at temperatures higher than 50 ◦ C. The biotic process follows hydrolysis
and happens in the presence of microorganisms (listed in Table 1) responsible for decom-
posing the polymer to the final products. As mentioned before, these products include
CO2 , water, and biomass under aerobic process conditions, while methane, hydrocarbons,
and biomass are generated under anaerobic conditions [21].
The elevated temperature, high moisture content, and abundance of microorganisms
in compost are the most suitable environment for the biodegradation of PLA. However, the
disintegration of PLA under composting conditions made by microorganisms starts when
C 2021, 7, 42 26 of 43

the polymer’s molecular weight reaches about 10.000–20.000 g/mol [96]. Importantly, this
natural process of degradation requires the availability of carbon, nitrogen, water, and
oxygen. Nitrogen is necessary for microorganisms to build their cell structures, and they
use carbon as a source of energy. The ideal composting conditions are with a carbon-to-
nitrogen ratio (C:N) of 30:1. These conditions are ideal for the reproduction of thermophilic
microorganisms [96].
Moreover, composting biodegradable plastics with other organic compostable ma-
terials, namely yard, food, and agricultural waste, can create much-needed carbon-rich
compost for soil enrichment [182]. In turn, the temperature and the type of compost used
affect chain mobility, which plays an essential role in PLA biodegradation [183].
In general, a maximum of 10% PLA should be used in compost piles [55]. PLA levels
higher than 30% (w/w) in pre-composted yard waste were reported to decrease pH due to
disintegration of the polymer to lactic acid, which suppresses the microbial growth and
slows down the overall decomposition [182].
The aerobic reaction observed in the composting process with the aid of microbial
metabolism can be described as follows [184].
FRESH ORGANIC WASTE + O2 = STABILIZED ORGANIC MATERIAL + CO2 + H2 O + HEAT
The composting process starts with a mesophilic phase (temperatures between 10 and
45 ◦ C), where microorganisms break-down PLA into simple molecules. A thermophilic
phase follows this step, which takes place at temperatures optimum for microbial activity
(between 45 and 70 ◦ C) [185]. Subsequently, the cooling phase starts, which continues
until the compost achieves the ambient temperature and hummus-like end-products are
observed. Degradation occurs at a slower rate and continues until all the utilizable carbon
is converted to carbon dioxide, and the humification coincides with the degradation of the
organic matter [119,184]. The general scheme of PLA bottle degradation under composting
conditions is represented in Figure 13.

Figure 13. General steps involved in biodegradation of a PLA bottle under composting conditions.
C 2021, 7, 42 27 of 43

Gattin [186] classified the PLA degradation in composting media to be more efficient
than in inert solid media but slower than in liquid media. Other researchers reported that
complete PLA degradation takes about one year in the soil, whereas it takes 60 to 100 days
in a compost environment [176].
A different study carried out by Saadi and collaborators [172] compared the purely
fungal degradation of PLA to the natural biodegradation (bacteria and fungi together).
The obtained results indicated that the kinetics of PLLA mineralization were faster under
natural biodegradation, attributed to a synergy between bacteria and fungi and the diversity
of enzymes released in the medium. The authors reported a decrease of Tg from 60.8 to
43.8 ◦ C and Tm from 165 to 142 ◦ C during the 70 days of the degradation test. The decrease
in Tm can indicate that degradation occurred not only in the amorphous phase of PLLA
samples but also in the crystalline regions.
Comparisons between laboratory set compost and field exposure (soil in the banana-
growing farm) degradation of PLA films were made by Ho and collaborators [187]. The
results indicated that PLA plastic films lost their mechanical properties faster when exposed
to natural conditions than during simulated compost exposure in the laboratory. They
also confirmed that the degradation of PLA was enhanced at higher temperatures and
relative humidity.
Husárová et al. reported the influence of Mw on the biodegradation of PLLA sam-
ples under composting conditions [94]. They found that with the increasing Mw of the
polymer, the biodegradation rate decreased, and initial retardation was discernible in
parallel. Further, the addition of a limited amount of low Mw PLA did not accelerate the
biodegradation of high Mw PLA, suggesting that the process is not limited to the number
of specific degraders and the induction of specific enzymes.
Kale et al. [119] compared the degradation of three types of commercial packaging
made of poly (LD-lactide) (PLA) under compost and ambient conditions. The samples
were subjected to composting for 30 days, and the degradation of the physical properties
was monitored. PLA packages made of 96% L-lactide exhibited lower degradation than
PLA packages made of 94% L-lactide, mainly due to the former’s higher crystallinity.
Further, the authors reported that the degradation rate changed with the initial crystallinity.
Other factors that significantly influenced the PLA degradation in compost were: L-lactide
content of the samples, temperature, relative humidity, and pH of the compost pile. They
also reported that PLA trays and deli containers’ degradation time in a commercial facility
was not more than 30 days.
As a result, any factors described before, which allow controlling the PLA matrix’s
hydrolytic degradation, will ultimately allow tuning the decomposition of PLA in com-
post. Thus, similarly to the hydrolytic degradation, the rate of degradation of PLA in
compost can be affected by different properties of the polymer material, including first and
higher-order structures (e.g., Mw, optical purity, crystallinity, Tg, and Tm) as well as the
environment conditions (humidity, temperature, pH and the enzymes or microorganisms
present) [21,181]. A study by Karamanlioglu and Robson [188] suggested that sterilization
of soil or compost decreased the PLA decomposition rate by tested fungal strains, which has
proven that soil micro-biota directly or indirectly stimulates the biodegradation process.

6.2. Soils
PLA degradation in soils is complex and much slower than in compost due to the lat-
ter’s higher moisture content and temperature range, which increases the PLA hydrolysis
and the assimilation of PLA by thermophilic microorganisms [181,182]. The appropriate
PLA-degrading microorganisms and the optimal environmental conditions, e.g., pH, hu-
midity, temperature, oxygen, are compulsory for the successful biodegradation of PLA
in the environment [41]. The soil’s geographic location could also impact the rate of PLA
degradation [21].
For example, a 20 month PLA soil burial trial caused 20% and 75% degradation of
PLA100 (crystalline PLA) and PLA75 (amorphous PLA), respectively [21]. Calmon et al. [189]
C 2021, 7, 42 28 of 43

compared the degradation in soil burial of PLA, PCL, cellophane, polyethylene (PE), and
polyhydrobutyrate by burying the samples in four different areas of France for two years.
Surprisingly at the end of the experiments, the authors found a PLA sample with significant
degradation signs, whereas the PCL specimen was entirely degraded. As was expected,
no degradation was observed in PE. Similar studies were done by Karamanlioglu and
collaborators [188,190], who also demonstrated minimal PLA degradation at ambient
temperatures. In their study, PLA coupons were buried in soil or compost at 25 ◦ C and
showed minimal changes after one year. A further study done by these authors, let to the
isolation of several fungi from the PLA’s surface; however, the sample showed no signs
of degradation.
Saadi et al. [172] studied the degradation of PLLA in sterilized and inoculated soil at
30 ◦ C and reported a low rate of fungal degradation of only 8% after 220 days incubation. In
another study, the soil burial for a year (T = 0–22 ◦ C) was reported not to affect the physical
properties of PLA test bars [191]. Therefore, while compostable, PLA cannot be regarded
as hydrolyzable or entirely biodegradable under normal environmental conditions. Similar
results were obtained by Kolstad and collaborators [192] who studied the behavior of Ingeo
PLA in landfills and performed two tests: (i) under accelerated landfill conditions, at 21 ◦ C,
up to 390 days; and (ii) anaerobic digestion test under optimal and significantly accelerated
conditions at 35 ◦ C for 170 days. The tests had accelerated the biological degradation
sufficiently to be equivalent to approximately a century of a “typical” landfill. The tests
were used to evaluate the methane generation potential of PLA under these conditions.
None of the PLA samples exhibited a statistically significant generation of biogas in the
first test, and no signs of PLA degradation were observed. In the second test, at 35 ◦ C, the
amorphous PLA sample degraded, with a biogas contribution suggesting approximately
36% degradation. The authors concluded that semicrystalline PLA (typical of >96 wt %
of resin used to manufacture products), under anaerobic conditions of a landfill under
ambient conditions, does not release a significant amount of methane, and there is no
available population of organisms to degrade high molecular weight PLA directly under
anaerobic conditions. The obtained results confirmed that semicrystalline PLA samples
at ambient temperature would require many decades to hydrolyze to the point where
microbes begin to consume the oligomers.
Rudnik and Briassoulis [193] carried out experimental studies on the biodegradation
of fibres and films of PLA and poly(hydroxyalkanoates) (PHA) under natural conditions
(in soil) and in the laboratory -simulated soil burial for seven months. The results showed
that under both testing conditions, PLA needed much more time and higher temperatures
(at least 58 ◦ C) to show any signs of degradation compared to PHA. In fact, the PLA
degradation at temperatures below the Tg occurs slowly because of polymer molecules’
inactivity to change from a glass-like state to a rubber-like state [192,194]. Furthermore,
Rudnik and Briassoulis reported that PLA fibers degraded more slowly than PLA films,
which was related to the higher crystallinity of the former. After seven months of burial
in the simulated laboratory soil, the PLA films became brittle and creased but were not
disintegrated in contrast to PHA films, which took only one month to biodegrade.
When PLA degrades in soil, its physical, mechanical, and chemical properties change.
Commonly, transparent PLA samples become opaque after soil burial degradation [193,194].
Santonja-Blasco and co-workers [195] studied commercial PLA degradation in soil burial
for 15 days, monitoring the samples with thermal techniques. The results showed that
the cold crystallization temperature decreased with degradation time, while the related
enthalpy of crystallization increased. The degradation of PLA in soil affected the PLA
chain reorganization, leading to an increase in the polylactide chains’ free volume in the
amorphous phase that favorably affected the bulk properties.
Weng and collaborators [196] studied the degradation of PLA samples buried 40 cm
deep under the soil surface for four months and reported a decrease in organic carbon
contents in the degraded samples while the oxygen atom contents increased. The authors
also reported a slight decrease in Tm of the degraded samples.
C 2021, 7, 42 29 of 43

The degradation of elongation at break, tensile strength at break, and Young modulus
of PLA after 50 days of soil burial degradation was reported by Vasile et al. [194]. These
authors studied the influence of chitosan (CS) on soil burial degradation of plasticized
PLA bio-composites sheets obtained by melt processing. Samples were buried in natural
active soils (with known water retention) and sterile soils under aseptic conditions. The
rate of degradation of the bio-composites was higher compared to the neat PLA sample.
The chitosan was found to favor the degradation process, which was demonstrated by
increasing weight loss with increasing CS content. Moreover, the mass losses were higher
in active soil than those found in sterile soil. The authors concluded that the yeasts,
molds, and total aerobic mesophiles present in the active soil promoted the bio-composite
biodegradation process.
Another group studied methods for accelerating the degradation of commercial bever-
age cups produced using PLA granules 2003D (Ingeo™ , Natureworks LLC, Northford, CT,
USA) in soil burial. The PLA cups were cut into sheets and buried in soil containing vari-
ous sources of bacteria and fungi, including cow-manure, green yard-waste, wastewater
sludges from dairy, etc. UV light was used to reduce the Mw of the samples. Interestingly,
the PLA cups degraded entirely after 15 days of burial in the soil with dairy wastewater
sludge, having a high total nitrogen content under thermophilic conditions. In comparison,
the neat PLA cups (not UV radiated) were found to be more challenging to degrade [180].

6.3. Aquatic Environment

As described before, degradation of PLA in aquatic environment occurs through
hydrolysis, which increases with the presence of high moisture in the environment. The
aquatic environment conditions are very stringent for the microorganisms because the
polymer becomes the sole carbon and energy source, and there are no co-substrates and
vitamins, apart from inorganic nitrogen source and the elements essential for microbial
growth. Thus, only some microbes capable of growing under harsh conditions can survive.
Similar to the degradation of PLA in soil, PLA degradation in the aquatic environment
takes a long time at ambient conditions (T = 25 and 37 ◦ C), but it accelerates under
thermophilic conditions (T = 55 ◦ C). The apparent effect of elevated temperatures suggests
that the polymer’s chain needs to be hydrolyzed before the microorganisms can act, which
is similar to the PLA degradation in soil or compost. The fastest mineralization of PLA in
the aerobic aquatic headspace test was reported at 60 ◦ C, reaching 90% within 120 days. On
the contrary, the anaerobic biodegradation of PLA under the same conditions was faster
than aerobic one, and 60% mineralization of PLA was reached at 52 ◦ C in just 40 days [197].
Musiol and collaborators [198] incubated PLA strips in the water at 70 ◦ C for 70 days.
The authors observed that the initially transparent samples became opaque after three days
of incubation due to an increase in crystallinity degree during the degradation process.
The disintegration of the samples was observed after 7 days of incubation. The authors
observed bimodal mass distribution for the PLA samples incubated for 7 and 14 days,
whereas the sample incubated for 21 days had a single peak distribution on the Gel
Permeation Chromatography (GPC) chromatograms. This observation was due to the
autocatalytic effect of hydrolysis degradation, whereas at a later stage of degradation,
lactic acid and its dimer diffuse out of the samples’ interior, and the effect of autocatalytic
degradation disappears after 21 days.
Deroine and collaborators [199] studied the degradation of PLA samples in seawater
and distilled water for six months. Under both experimental conditions, PLA ageing was
favored by increased temperatures. The Ea was lower in distilled water than in seawater.
The degradation of PLA in distilled water at 50 ◦ C was strongly accelerated, and the
sample became considerably brittle only after one month of immersion. Furthermore, the
immersion of samples at 40 and 50 ◦ C in distilled water for six months resulted in an
increase in melting enthalpy and degree of crystallinity. A significant reduction of the stress
at break of PLA samples was observed in both environments after six months at 40 ◦ C;
however, it was more pronounced in distilled water (85% versus 70% in seawater). The
C 2021, 7, 42 30 of 43

lesser deterioration of PLA properties in seawater than in distilled water was attributed to
the difference in water absorption. The accelerated aging tests in seawater and distilled
water showed that the nature of the aqueous medium significantly affects the polymer
properties. It was concluded that the degradation of PLA is faster in distilled water,
probably due to the role of mineral salts, which facilitate the diffusion of seawater within
the polymer and a lower pH of distilled water (≈6 against ≈8 for seawater), which can
promote hydrolytic degradation.
Accelerated ageing of PLLA in seawater for three months revealed a decrease of
almost 50% in molecular weight at 40 ◦ C. Further, the elastic modulus was not affected
by ageing, but the tensile strength significantly decreased. Furthermore, the failure strain
increased with ageing at 20 ◦ C but decreased at 40 ◦ C [200].
Tsuji and Suzuyoshi [201] compared the degradation of PLA in static seawater in
the laboratory and dynamic natural seawater [202]. In the natural seawater, mechanical
stresses and strains (from waves and tides) are always loaded on the specimens together
with UV radiation. These effects significantly accelerate the biodegradation of PLA. After
one week of immersion in the dynamic seawater and 10 weeks in static seawater, there was
no significant degradation by marine microbes. Moreover, an induction period of three
weeks was observed in dynamic seawater, with a 65% weight loss obtained in 5 weeks.
In contrast, PLLA specimens appeared to be biodegradation-resistant in the static
seawater as no significant weight loss or weight distribution changes were recorded up to
ten weeks of immersion [201]. Moreover, the tensile strength of PLLA films in the natural
dynamic seawater was lower than that in the controlled static seawater when compared at
the same degradation time. The authors reported no UV irradiation influence on the chain
cleavage in PLLA films during (bio)degradation in the natural dynamic seawater [202].

7. Control and Improvement of PLA Biodegradation

It is clear that PLA, although hydrolyzable, is very resistant to degradation under
environmental conditions. In this sense, nanocomposites or blends represent an excellent
solution to modify the initial characteristics of PLA. For example, the use of some of the
nanoparticles, as “nanoreinforcements” of PLA, not only affects its mechanical properties
but also dramatically influences its biodegradation behavior. Several different materials
have been added to PLA, which can accelerate its decomposition, for example, clays, zinc
oxide, TiO2 , metal oxides, or natural polymers, such as chitosan. The development of PLA-
based nanocomposites often involves a trade-off between the composites’ performance and
their degradability at the end of their service life. This section will give a short overview of
the most important works concerning the biodegradability of PLA.
Controlling the hydrolytic degradability of PLA is of great importance because, as
mentioned before, hydrolysis is an obligatory step in PLA biodegradation in natural
environments. Numerous studies have been undertaken to elucidate the effects of various
features on the process. Hydrolysis of PLA composites containing nanoparticles is a
complex phenomenon depending on the degradation temperature and pH, nature and
dispersion of filler, type of bonding between components, dispersion of the nanofiller, and
polymer crystallinity [203]. In comparison, the biodegradation rate of PLA composite in
the compost or soil is more complicated. The composting process additionally depends
on the environmental conditions (e.g., type of microbial population and nutrient supply)
to which the material is subjected [204]. It is worth mentioning that since the biological
contact in the compost or soil occurs at the material–environment interface, the exposed
surface properties play the most crucial role. For example, a rough surface with a high
number of polar hydrophilic functional groups is much more prone to biodegradation than
a smooth, hydrophobic one.
Ho et al. [205] reported a faster degradation rate of PLA under composting conditions
after incorporating bamboo charcoal particles. The effect was attributed to better adsorption
of water by the composite materials than neat PLA, which resulted in a higher rate of the
C 2021, 7, 42 31 of 43

hydrolysis reaction. The authors pointed out that the composites’ higher degradation rates
can be due to their lower crystallinity than a neat PLA.
Luzi and collaborators [178] showed that films based on PLA reinforced with cellulose
nanocrystals were disintegrated in less than 14 days in compost conditions. The accelerating
effect of the cellulose nanocrystals was assigned to the hydrophilicity of the surfactant
used during the synthesis of the biopolymer. Additionally, several micro-holes in the
composites’ structure improved the kinetics of the biocomposites’ degradation and aided
water absorption. The developed material was proposed for application in food packaging
with low environmental impact.
The addition of cellulose nanocrystals modified with a commercial surfactant im-
proved the disintegration of PLA in composting conditions. The results were attributed
to the hydrophilicity of the surfactant [178]. Enzymatic degradation of PLA was also
accelerated in PLA reinforced with cellulose nanocrystals [206].
Biodegradation of the polyblends of PLA, PCL, and microcrystalline cellulose (MCC)
was studied and compared with neat PLA and neat PCL. The blends with a higher con-
centration of PCL and MCC in the PLA matrix showed higher carbon mineralization
percentages than the blends having low PCL and MCC components. The blend composi-
tion and filler concentration played a crucial role in the biodegradation behaviour of these
composite materials [183].
Balaguer et al. [207] evaluated the influence of the addition of layered silicate, cal-
cium carbonate nanoparticles, and nano silicon oxide to PLA films on the nanocomposites’
compostability. Results showed that films completely disintegrated into visually indistin-
guishable residues after 6–7 weeks of incubation in a composting environment. Further,
biodegradation was higher in all the biocomposites than that of plain PLA after 130 days in
composting, and the addition of calcium carbonate and clay obtained the most significant
improvements. Furthermore, all the samples showed the typical PLA biodegradation pat-
tern, which consists of an initial lag phase corresponding to hydrolysis of the ester bonds
by extracellular hydrolytic enzymes and the subsequent biodegradation of the generated
monomers and oligomers. The corresponding lag phase ranged from 9 days for the film
PLA with clay to 17 days for the blank film and the film PLA with SiO2 . The shortest lag
phase was attributed to the high hydrophilicity of the nanoclay, which enhances the amount
of water absorbed in the polymer matrix and thus prompts the hydrolytic degradation
processes. Another study reported similar results on the addition of montmorillonite, or
hectorite, and smectite-type layered silicates into the PLA matrix. The authors reported
that these nanofillers increased the PLA matrix’s hydrophilicity and thus increased the
polymer’s hydrolysis rate. Further, the clay particles’ morphology was found to influ-
ence water diffusion in the material, and a lower diffusion coefficient was found with the
nanofillers’ pellets-like morphology [208]. Moreover, organically modified layered silicates
such as mica or montmorillonite increased the enzymatic degradation of clay reinforced
PLA/PBSA blends [88].
Fukushima et al. [209] studied PLA nanocomposites with the addition of organically
modified montmorillonites. The degradation of nanocomposites was faster than that of
neat PLA. The accelerated degradation was attributed to hydroxyl groups in the clays,
which catalyzed the PLA matrix’s hydrolysis. Other studies underlined the importance
of hydroxyl groups of the surfactants in clay-PLA composites, which improve the distri-
bution of the clay in the polymer and promote adsorption and diffusion of water in the
composites [182,209]. Another study dealing with PLA–clay nanocomposites reported that
montmorillonite or fluorohectorite and sepiolite resulted in increased crystallinity of the
nanocomposite compared to neat PLA. The hydrolysis of the samples in the phosphorous
buffer solution at 58 ◦ C showed no significant effect of clays on the degradation trend
of PLA. The nanocomposites degraded similarly to the neat PLA, which was related to
the easy access of water molecules to the bulk material, minimizing the effect of polymer
crystallinity, clay nature, and aspect ratio on the polymer degradation [203].
C 2021, 7, 42 32 of 43

A rational choice of the nanofiller’s chemical nature allows tuning both the degra-
dation rate of PLA and its structure. Neppalli et al. [210] prepared nanocomposites of
PLA with perkalite (anionic clay) and montmorillonite (cationic clay) and studied the
relationship between the presence of clay, the crystallization behavior of the matrix, and
the degradation rate of the nanocomposite. Perkalite induced higher crystallinity, a faster
crystallization rate, and also a modification of the crystallization mechanism. Moreover,
when perkalite was used, the lamellar framework of PLA was preserved. On the contrary,
the cationic clay inflicted a disruption of the order of the lamellar stacks in PLA, causing
less homogenous dispersion of the filler in the PLA matrix. After 125 days of immersion in
a phosphate buffer solution at pH 7.4, PLA showed a negligible mass loss. On the other
hand, PLA with cationic clays lost about 10% initial mass, whereas the sample containing
perkalite showed degradation of 40%. Accelerated degradation of the PLA-perkalite com-
posite was due to a high volume of the polymer matrix in contact with the nanoclay edges
due to the excellent dispersion of perkalite in the PLA matrix. As a result, the water attack
was more straightforward, and the rate of hydrolysis was accelerated compared to PLA-
montmorillonite or neat PLA.
The degradation mechanism and kinetics of PLA nanocomposite films containing
various commercially available native or organo-modified montmorillonites were studied
under composting conditions in the process’s thermophilic phase and during abiotic hy-
drolysis. Biodegradation of PLA was enhanced in the presence of nanoclays, in accordance
with other reports. In particular, the lag phase at the beginning of the process was shortened
in the clays’ presence compared to neat PLA. The lag phase typical for biodegrading high
molecular weight PLA [94] was discernible for all samples at the beginning of the process,
but it was more pronounced for neat PLA. The authors also determined that the critical
molecular weight for the hydrolysis of PLA is higher than the critical molecular weight
for the onset of its mineralization, which confirmed that PLA chains must be shortened
beyond the solubility limit before being assimilated by microorganisms [211].
Similarly to clays, the presence of graphene oxide (GO) in the PLA matrix also im-
proves the material’s hydrophilicity. Duan et al. [212] carried out the hydrolytic degradation
of PLLA-GO nanocomposites in three different environments, including alkaline, acidic
and neutral solutions. The results demonstrated that the hydrolytic degradation of PLLA
was greatly accelerated by adding GO in all media. Moreover, the acceleration effect
was proportional to the amount of GO added. Furthermore, the hydrolytic degradation
mechanism of the PLLA matrix was not affected by the presence of GO in the matrix.
Lizundia et al., studied the influence of ZnO on the thermal and hydrolytic degradation
of PLLA. PLLA nanocomposites with five wt % ZnO nanoparticles were prepared involving
solvent-precipitation method followed by compression molding. The thermal degradation
tests were carried out in TG by heating the material to 500 ◦ C. The results showed that
ZnO nanoparticles catalyzed nanocomposites’ thermodegradation process, and the onset
temperature was lowered by 100 ◦ C. The catalytic activity of ZnO was also apparent in
hydrolytic degradation tests, where nanocomposites with higher concentrations of ZnO
underwent physical disintegration to a more considerable extent than neat PLLA. The
analysis using the wide-angle X-ray diffraction technique revealed that the amounts of
oxygen vacancies initially present in the ZnO lattice in nanocomposites were reduced
upon degradation. The authors postulated that thermal and hydrolytic degradation of
PLLA-ZnO nanocomposites were both initiated on ZnO surfaces. The accelerated thermal
degradation of PLLA in the presence of ZnO nanoparticles was also reported by other
authors [213–215]. The addition of ZnO or TiO2 has led to a significantly decreased
activation energy for PLA pyrolysis and a substantially higher decomposition rate constant.
The catalytic effect of ZnO was found to be more considerable than TiO2 [215].
On the other hand, TiO2 nanoparticles have been investigated in recent years because
of their photocatalytic ability to decompose various organic chemicals, including PLA [216].
UV irradiation results in an electron (e− ) in the TiO2 nanoparticles being removed into
the conduction band, leaving a positive hole (h+ ) in the valence band, which produces
C 2021, 7, 42 33 of 43

active oxygen species. These species subsequently aid in the degradation of the polymer
matrix. By adding photodegradability to PLA, its degradability can be efficiently promoted
under any conditions, as was already mentioned. Studies indicated that the degradation
efficiency of a PLA was improved by incorporating TiO2 nanoparticles [217].
Luo and coworkers [218] studied the biodegradability of PLA/TiO2 composites with
different contents of TiO2 from 0.5 to 15.0 wt %. The biodegradation tests carried out under
controlled composting conditions for three months indicated a considerable degradation of
PLA/TiO2 composite compared to that of PLA. The degradation was evidenced by deep
cracks and large voids on PLA/TiO2 composites’ surface due to the hydrolysis of PLA
and microorganisms’ activity. Additionally, larger amounts of TiO2 in the PLA matrix
accelerated the initial phase of degradation and enhanced the amount of CO2 generated at
the end of incubation periods.
Another group reported that the presence of TiO2 increased the rate of hydrolytic
degradation of PLA in a phosphate buffer solution of pH 7.4 at 37 ◦ C [219]. The change
in surface morphology of PLA-TiO2 nanocomposites after hydrolysis revealed that the
degradation process was initiated at the PLA matrix and nanofillers interface. The water
absorption and degradation rate of PLA-TiO2 were affected by nanofillers’ dispersion in
the polymer matrix.
The catalytic effect of alkali earth metal oxides such as CaO and MgO on the thermal
degradation of PLLA was previously reported by Fan et al. [220]. Metal oxides, especially
MgO, suppressed oligomers’ production other than lactides and limited the racemization of
lactide during thermal degradation of PLLA. At temperatures lower than 270 ◦ C, the pyrol-
ysis of PLLA/MgO (5 wt %) composite occurred smoothly via unzipping depolymerization
mechanism and resulted in selective production of L-lactide.
PLA is often blended with starch to increase biodegradability and reduce costs. Lv and
collaborators [221] studied the biodegradation behavior of PLA blended with starch and
wood flour in soil. They reported that starch provided a biological fuel for the growth of
microorganisms in the soil, which accelerated the composite’s degradation rate. Moreover,
in the simulated soil, the growth of microorganisms was increased with the occurrence of
glucose provided by thermoplastic starch (TPS), which was found to significantly accelerate
the degradation of PLA and PLA/TPS blends [222].
Petinakis and collaborators [223] reported that both starch and wood-flour accelerated
the thermal decomposition of PLA, and the former exhibited a relatively more substantial
effect than the latter. The decomposition temperature of PLA was decreased by about 40 ◦ C
when the filler content reached 40%. Compared to wood-flour, the lower decomposition
temperature of starch resulted in a lower decomposition temperature of PLA in the blends
with starch. Concerning the impact of starch on biodegradation under composting condi-
tions, it was observed that nanocomposites containing less than 40% of starch took a longer
time to degrade due to the aforementioned lag phase. On the contrary, the degradation of
blend PLA 60%–starch 40% initiated disintegration immediately under controlled compost
conditions and achieved 80% biodegradation after 80 days in the compost. Furthermore,
the improved compatibility between PLA and esterified starch enhanced the rate and
degree of degradation of starch-PLA composites [224].
Plastic composites with natural fiber reinforcements result in lightweight structures
having high stiffness and tailored properties for specific applications, thereby saving weight
and reducing energy needs [225]. Aerobic biodegradation of PLA-TPS with 30% natural
fiber was studied under controlled composting conditions. The degradation rate was
influenced chiefly by starch, whereas the fibers showed only a marginal effect. Biofilm was
observed on biodegraded materials due to bacterial and fungal fixation and growth [226].
Enhancement in the PLA’s degradation in a laboratory-scale simulated composting
facility was found with the addition of natural biomass such as untreated soy and wheat
straw [225]. Both nanocomposites showed similar rates of degradation irrespective of
the type of biomass used. Compared to that of the neat PLA, the improved degradation
C 2021, 7, 42 34 of 43

rate was due to the presence of readily degradable natural substrate and reduced average
molecular weight of the PLA.
Shinoda et al. [227] melt-blended PLA with a small amount of poly(aspartic acid-co-
lactide) (PAL) or poly(sodium aspartate-co-lactide) (PALNa) and obtained homogeneous
press films. They studied the degradation of these blends in compost and the soil. The
results suggested that PAL and PALNa are useful additives for accelerating the hydrolysis
of PLA. Interestingly, PAL did not accelerate the hydrolysis rate of PLA unless it came
into contact with water. It was explained by the amphiphilic nature of the PAL, which
would be hydrophilic in water and hydrophobic in air. Conversely, the PLA/PALNa blend
degraded relatively quickly under the same ambient conditions. PALNa is water-soluble
and relatively hydrophilic; its hygroscopic nature accelerated the rate of PLA hydrolysis.
The strength of the blend films decreased faster than that of the pure PLA film under
controlled composting conditions at 58 ◦ C, with a water content of 60%.
The hydrolytic degradation of PLA can be controlled by improving the hydrophilicity
of the polymer surface. The hydrolytic degradation of PLA grafted with acrylic acid (AA)
at 37 ◦ C was significantly accelerated compared with the neat PLA. Low molar mass
compounds migrated from surface-grafted PLA after seven days of tests compared to
133 days for nongrafted PLA. Besides, the degradation product pattern of surface-grafted
PLA showed significant variation as a function of hydrolysis time with the evolution of
short and long AA-grafted lactic acid (LA) oligomers apart from plain lactic acid oligomers.
The authors underlined the necessity to consider the degradation product patterns parallel
with developing new PLA materials [228].
The biodegradation of PLA can be accelerated by treating the material with specific
fungal strains (Aspergillus Niger, Chaetomium globosum, Paecilomyces variotti, Penicillium
pinophilium and Trichoderma viride) to improve the kinetics of the process [172].
Finally, Pattanasuttichonlakul et al. [180] proposed the UV irradiation of PLA followed
by burying in a soil mixture of bacteria from dairy wastewater sludge as an efficient method
for accelerating the degradation of PLA waste.

8. Conclusions
Society’s primary challenges nowadays include environmental problems, increased
pollution, plastic waste management issues, and consumer demands for environmentally
friendly options. The use of biodegradable plastics is a way to solve the disposal problem
of plastics in landfills and a valid alternative to replacing conventional polymers. Poly(l-
lactide) (PLLA), which can be prepared from renewable resources, has been believed to
be an ideal alternative to petroleum-based polymers due to its excellent comprehensive
performance and biodegradable ability. Its performance characteristics, such as stiffness,
strength, and gas permeability, are comparable with conventional petroleum-based plas-
tics. PLA exhibits high strength, stiffness, biocompatibility, thermo-plasticity, and good
processability. On the other side, the main drawbacks of PLA include its low toughness,
high cost, and unacceptably slow degradation rate.
In general, PLA is more resistant to degradation under environmental conditions than
other aliphatic biodegradable polymers. Thus, although compostable, PLA is not a readily
degradable biopolymer.
Hydrolytic degradation is a critical first step in the biodegradation of PLLA. It can be
affected by many features of the material itself (crystallinity, molecular weight etc.) and
the media’s conditions (temperature, time, pH, etc.). Moreover, humidity, time, type of
microorganisms, presence of oxygen and the supply of essential nutrients, population, and
action potential of enzyme activity, etc. are some additional factors that should be taken into
account if the PLA is meant to be degraded in compost at the end of its service life. A vast
body of literature on PLA degradation in soil and compost suggested that the degradation
behavior was a complex phenomenon, and the degradation rate of PLA is strongly affected
by temperature. The primary condition to obtain substantial biodegradation of PLA is a
temperature higher than the glass transition temperature of PLA.
C 2021, 7, 42 35 of 43

When attempting to control the degradation of PLA, fine-tuning is needed to bal-

ance the necessity of maintaining suitable material properties during the entire service
life in environmental conditions and the need for rapid degradation when the material
becomes a waste. The degradation of PLA can be controlled by (i) addition of catalysts or
organically modified nanoparticles; (ii) modifications by blending PLA with other easily
degradable natural polymers such as chitosan, cellulose, or starch; (iii) combining with or-
ganic modifiers, or chain extenders, among others. The most common nanofillers favoring
biodegradation of PLA are ZnO, clays, alkali earth metal oxides.
For the near future, new strategies are needed for the selective depolymerization of
bioplastics such as PLA either to their constituent monomers or other useful intermediates
that could be used as resources for other chemical processes. New strategies should be
developed to recapture and reutilize plastic materials at the end of their useful life since
their persistence in the environment causes pollution of the lands and oceans. New ways
should be sought to decrease PLA production cost, improve its toughness, and boost its
biodegradation behavior to make it more commercially attractive.
Although recycling could be more energetically feasible than composting for PLA
products, composting seems to be more practical, as it does not require sorting and cleaning.
Furthermore, compostable food packaging materials or agricultural products could trigger
plastic waste diversion from landfills into composting facilities. Work should be done to
make compostable materials compatible with the circular economy as immediate value is
lost from the life-cycle.

Author Contributions: S.T., Conceptualization, Investigation, Writing—Original Draft; K.M.E., Con-

ceptualization, Methodology, Validation, Investigation, Writing—Original Draft, Writing—Review
and Editing; F.M., Investigation, Writing—Original Draft; M.F.R.P. Writing—Review and Editing,
Funding Acquisition; J.L.F., Conceptualization, Writing—Review and Editing, Funding acquisition;
S.T. and K.M.E. contributed equally to this work. All authors have read and agreed to the published
version of the manuscript.
Funding: This research was funded Base Funding—UIDB/50020/2020 of the Associate Laboratory
LSRE-LCM—funded by national funds through FCT/MCTES (PIDDAC). K.M.E. acknowledges FCT
funding under DL57/2016 Transitory Norm Programme.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Informed consent was obtained from all subjects involved in the study.
Acknowledgments: This work was financially supported by Base Funding—UIDB/50020/2020 of
the Associate Laboratory LSRE-LCM—funded by national funds through FCT/MCTES (PIDDAC).
K.M.E. acknowledges FCT funding under DL57/2016 Transitory Norm Programme.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Alexis, F. Factors affecting the degradation and drug-release mechanism of poly(lactic acid) and poly[(lactic acid)-co-(glycolic
acid)]. Polym. Int. 2004, 54, 36–46. [CrossRef]
2. Araújo, A.; Oliveira, M.; Oliveira, R.; Botelho, G.; Machado, A.V. Biodegradation assessment of PLA and its nanocomposites.
Environ. Sci. Pollut. Res. 2013, 21, 9477–9486. [CrossRef]
3. Aso, Y.; Yoshioka, S.; Liwanpo, A.; Terao, T. Effect of temperature on mechanisms of drug release and matrix degradation of
poly(d,l-lactide) microspheres. J. Control. Release 1994, 31, 33–39. [CrossRef]
4. Castro-Aguirre, E.; Iñiguez-Franco, F.; Samsudin, H.; Fang, X.; Auras, R. Poly(lactic acid)—Mass production, processing, industrial
applications, and end of life. Adv. Drug Deliv. Rev. 2016, 107, 333–366. [CrossRef]
5. Jamshidian, M.; Tehrany, E.A.; Imran, M.; Jacquot, M.; Desobry, S. Poly-Lactic Acid: Production, Applications, Nanocomposites,
and Release Studies. Compr. Rev. Food Sci. Food Saf. 2010, 9, 552–571. [CrossRef]
6. Shah, A.A.; Hasan, F.; Hameed, A.; Ahmed, S. Biological degradation of plastics: A comprehensive review. Biotechnol. Adv. 2008,
26, 246–265. [CrossRef]
7. Elsawy, M.A.; Kim, K.-H.; Park, J.-W.; Deep, A. Hydrolytic degradation of polylactic acid (PLA) and its composites. Renew.
Sustain. Energy Rev. 2017, 79, 1346–1352. [CrossRef]
C 2021, 7, 42 36 of 43

8. Nampoothiri, K.M.; Nair, N.R.; John, R.P. An overview of the recent developments in polylactide (PLA) research. Bioresour.
Technol. 2010, 101, 8493–8501. [CrossRef]
9. Murariu, M.; Dubois, P. PLA composites: From production to properties. Adv. Drug Deliv. Rev. 2016, 107, 17–46. [CrossRef]
10. Vink, E.T.; Rábago, K.R.; Glassner, D.A.; Gruber, P.R. Applications of life cycle assessment to NatureWorks™ polylactide (PLA)
production. Polym. Degrad. Stab. 2003, 80, 403–419. [CrossRef]
11. Platel, R.H.; Hodgson, L.M.; Williams, C.K. Biocompatible Initiators for Lactide Polymerization. Polym. Rev. 2008, 48, 11–63.
[CrossRef]
12. Malinconico, M. Soil Degradable Bioplastics for a Sustainable Modern Agriculture; Springer: New York, NY, USA, 2017.
13. Wan, L.; Zhang, Y. Jointly modified mechanical properties and accelerated hydrolytic degradation of PLA by interface reinforce-
ment of PLA-WF. J. Mech. Behav. Biomed. Mater. 2018, 88, 223–230. [CrossRef]
14. Mehta, R.; Kumar, V.; Bhunia, H.; Upadhyay, S.N. Synthesis of Poly(Lactic Acid): A Review. J. Macromol. Sci. Part C 2005, 45,
325–349. [CrossRef]
15. Lim, L.-T.; Auras, R.; Rubino, M. Processing technologies for poly(lactic acid). Prog. Polym. Sci. 2008, 33, 820–852. [CrossRef]
16. Sin, L.T.; Rahmat, A.R.; Rahman, W.A.W.A. (Eds.) 3-Thermal Properties of Poly(lactic Acid). In Polylactic Acid; William Andrew
Publishing: Oxford, UK, 2013; pp. 109–141.
17. Fambri, L.; Migliaresi, C.; Kesenci, K.; Pişkin, E. Biodegradable Polymers. In Integrated Biomaterials Science; J.B. Metzler: Stuttgart,
Germany, 2005; pp. 119–187.
18. Farah, S.; Anderson, D.G.; Langer, R. Physical and mechanical properties of PLA, and their functions in widespread applications—
A comprehensive review. Adv. Drug Deliv. Rev. 2016, 107, 367–392. [CrossRef]
19. Gupta, B.; Revagade, N.; Hilborn, J. Poly(lactic acid) fiber: An overview. Prog. Polym. Sci. 2007, 32, 455–482. [CrossRef]
20. Södergård, A.; Stolt, M. Properties of lactic acid based polymers and their correlation with composition. Prog. Polym. Sci. 2002, 27,
1123–1163. [CrossRef]
21. Karamanlioglu, M.; Preziosi, R.; Robson, G.D. Abiotic and biotic environmental degradation of the bioplastic polymer poly(lactic
acid): A review. Polym. Degrad. Stab. 2017, 137, 122–130. [CrossRef]
22. Bergsma, J.E.; de Bruijn, W.C.; Rozema, F.R.; Bos, R.R.M.; Boering, G. Late degradation tissue response to poly(l-lactide) bone
plates and screws. Biomaterials 1995, 16, 25–31. [CrossRef]
23. Available online: https://www.pressreleasefinder.com/NatureWorks/NWPR005/en/ (accessed on 22 December 2020).
24. Available online: https://www.natureworksllc.com/News-and-Events/Press-Releases/2020 (accessed on 12 November 2020).
25. Momani, B. Assessment of the Impacts of Bioplastics: Energy Usage, Fossil Fuel Usage, Pollution, Health Effects, Effects on the
Food Supply, and Economic Effects Compared to Petroleum Based Plastics. Available online: https://core.ac.uk/download/pdf/
212988946.pdf (accessed on 28 November 2020).
26. Momani, B. Assessment of the Impacts of Bioplastics: Energy Usage, Fossil Fuel Usage, Pollution, Health Effects, Effects on the Food Supply,
and Economic Effects Compared to Petroleum Based Plastics; An Interactive Qualifying Project Report; Worcester Polytechnic Institute:
Worcester, MA, USA, 2009.
27. Zhang, Y.; Luo, H.; Kong, L.; Zhao, X.; Miao, G.; Zhu, L.; Li, S.; Sun, Y. Highly efficient production of lactic acid from xylose using
Sn-beta catalysts. Green Chem. 2020, 22, 7333–7336. [CrossRef]
28. Komesu, A.; Oliveira, J.A.R.d.; Martins, L.H.d.S.; Wolf Maciel, M.R.; Maciel Filho, R. Lactic Acid Production to Purification: A
Review. BioResources 2017, 12, 20. [CrossRef]
29. Sun, Y.; Xu, Z.; Zheng, Y.; Zhou, J.; Xiu, Z. Efficient production of lactic acid from sugarcane molasses by a newly microbial
consortium CEE-DL15. Process. Biochem. 2019, 81, 132–138. [CrossRef]
30. Budhavaram, N.K.; Fan, Z. Production of lactic acid from paper sludge using acid-tolerant, thermophilic Bacillus coagulan strains.
Bioresour. Technol. 2009, 100, 5966–5972. [CrossRef]
31. Schmidt, S.; Padukone, N. Production of lactic acid from wastepaper as a cellulosic feedstock. J. Ind. Microbiol. Biotechnol. 1997,
18, 10–14. [CrossRef]
32. Gullón, B.; Yáñez, R.; Alonso, J.L.; Parajó, J. l-Lactic acid production from apple pomace by sequential hydrolysis and fermentation.
Bioresour. Technol. 2008, 99, 308–319. [CrossRef]
33. Garlotta, D. A Literature Review of Poly(Lactic Acid). J. Polym. Environ. 2001, 9, 63–84. [CrossRef]
34. Rasal, R.M.; Janorkar, A.V.; Hirt, D.E. Poly(lactic acid) modifications. Prog. Polym. Sci. 2010, 35, 338–356. [CrossRef]
35. Sin, L.T.; Rahmat, A.R.; Rahman, W.A.W.A. Synthesis and Production of Poly(lactic Acid). In Polylactic Acid; Elsevier BV:
Amsterdam, The Netherlands, 2013; pp. 71–107.
36. Drumright, R.E.; Gruber, P.R.; Henton, D.E. Polylactic Acid Technology. Adv. Mater. 2000, 12, 1841–1846. [CrossRef]
37. Botvin, V.; Karaseva, S.; Salikova, D.; Dusselier, M. Syntheses and chemical transformations of glycolide and lactide as monomers
for biodegradable polymers. Polym. Degrad. Stab. 2021, 183, 109427. [CrossRef]
38. Hartmann, M.H. High Molecular Weight Polylactic Acid Polymers. In Biopolymers from Renewable Resources; Kaplan, D.L., Ed.;
Springer: Berlin/Heidelberg, Germany, 1998; pp. 367–411.
39. Dechy-Cabaret, O.; Martin-Vaca, B.; Bourissou, D. Controlled Ring-Opening Polymerization of Lactide and Glycolide. Chem. Rev.
2004, 104, 6147–6176. [CrossRef]
40. Bendix, D. Chemical synthesis of polylactide and its copolymers for medical applications. Polym. Degrad. Stab. 1998, 59, 129–135.
[CrossRef]
C 2021, 7, 42 37 of 43

41. Qi, X.; Ren, Y.; Wang, X. New advances in the biodegradation of Poly(lactic) acid. Int. Biodeterior. Biodegradation 2017, 117, 215–223.
[CrossRef]
42. Metkar, S.; Sathe, V.; Rahman, I.; Idage, B.; Idage, S. Ring opening polymerization of lactide: Kinetics and modeling. Chem. Eng.
Commun. 2019, 206, 1159–1167. [CrossRef]
43. Huang, J.; Lisowski, M.S.; Runt, J.; Hall, E.S.; Kean, R.T.; Buehler, N.; Lin, J.S. Crystallization and Microstructure of Poly(l-lactide-
co-meso-lactide) Copolymers. Macromolecules 1998, 31, 2593–2599. [CrossRef]
44. Vasanthakumari, R.; Pennings, A. Crystallization kinetics of poly(l-lactic acid). Polymer 1983, 24, 175–178. [CrossRef]
45. Marega, C.; Marigo, A.; Noto, V.; Zannetti, R.; Martorana, A.; Paganetto, G. Structure and crystallization kinetics of poly(L-Lactic
Acid). Die Makromolekulare Chemie 1992, 193, 1599–1606. [CrossRef]
46. Mazzullo, S.; Paganetto, G.; Celli, A. Regime III crystallization in poly-(l-lactic) acid. Solidif. Process. Polym. 2007, 34, 32–34.
[CrossRef]
47. Kolstad, J.J. Crystallization kinetics of poly(L-lactide-co-meso-lactide). J. Appl. Polym. Sci. 1996, 62, 1079–1091. [CrossRef]
48. Zell, M.T.; Padden, B.E.; Paterick, A.J.; Hillmyer, M.A.; Kean, R.T.; Thakur, K.A.M.; Munson, E.J. Direct Observation of Stereodefect
Sites in Semicrystalline Poly(lactide) Using 13C Solid-State NMR. J. Am. Chem. Soc. 1998, 120, 12672–12673. [CrossRef]
49. Baratian, S.; Hall, E.S.; Lin, J.S.; Xu, R.; Runt, J. Crystallization and Solid-State Structure of Random Polylactide Copolymers:
Poly(l-lactide-co-d-lactide)s. Macromolecules 2001, 34, 4857–4864. [CrossRef]
50. Di Lorenzo, M.L. Crystallization behavior of poly(l-lactic acid). Eur. Polym. J. 2005, 41, 569–575. [CrossRef]
51. Lopes, M.S.; Jardini, A.; Filho, R.M. Poly (Lactic Acid) Production for Tissue Engineering Applications. Procedia Eng. 2012, 42,
1402–1413. [CrossRef]
52. Lunt, J. Large-scale production, properties and commercial applications of polylactic acid polymers. Polym. Degrad. Stab. 1998, 59,
145–152. [CrossRef]
53. Eling, B.; Gogolewski, S.; Pennings, A. Biodegradable materials of poly(l-lactic acid): 1. Melt-spun and solution-spun fibres.
Polymer 1982, 23, 1587–1593. [CrossRef]
54. Available online: https://www.hitachi-hightech.com/file/global/pdf/products/science/appli/ana/thermal/application_TA_
081e.pdf (accessed on 13 December 2020).
55. Auras, R.; Harte, B.; Selke, S. An Overview of Polylactides as Packaging Materials. Macromol. Biosci. 2004, 4, 835–864. [CrossRef]
56. Tsuji, H. Poly(lactide) Stereocomplexes: Formation, Structure, Properties, Degradation, and Applications. Macromol. Biosci. 2005,
5, 569–597. [CrossRef]
57. Tsuji, H.; Horii, F.; Hyon, S.H.; Ikada, Y. Stereocomplex formation between enantiomeric poly(lactic acid)s. 2. Stereocomplex
formation in concentrated solutions. Macromolecules 1991, 24, 2719–2724. [CrossRef]
58. Jamshidi, K.; Hyon, S.-H.; Ikada, Y. Thermal characterization of polylactides. Polymer 1988, 29, 2229–2234. [CrossRef]
59. Cheng, Y.; Deng, S.; Chen, P.; Ruan, R. Polylactic acid (PLA) synthesis and modifications: A review. Front. Chem. China 2009, 4,
259–264. [CrossRef]
60. Gui, Z.; Xu, Y.; Gao, Y.; Lu, C.; Cheng, S. Novel polyethylene glycol-based polyester-toughened polylactide. Mater. Lett. 2012, 71,
63–65. [CrossRef]
61. Yu, M.; Zheng, Y.; Tian, J. Study on the biodegradability of modified starch/polylactic acid (PLA) composite materials. RSC Adv.
2020, 10, 26298–26307. [CrossRef]
62. Meaurio, E.; Hernandez-Montero, N.; Zuza, E.; Sarasua, J.R. Miscible Blends Based on Biodegradable Polymers. In Characterization
of Polymer Blends: Miscibility, Morphology and Interfaces; Thomas, S., Grohens, Y., Jyotishkumar, P., Eds.; Wiley-VCH Verlag GmbH
& Co. KGaA: Weinheim, Germany, 2015; pp. 7–86.
63. Zhang, L.; Goh, S.; Lee, S. Miscibility and crystallization behaviour of poly(l-lactide)/poly(p-vinylphenol) blends. Polymer 1998,
39, 4841–4847. [CrossRef]
64. Chen, H.-L.; Liu, H.-H.; Lin, J.S. Microstructure of Semicrystalline Poly(l-lactide)/Poly(4-vinylphenol) Blends Evaluated from
SAXS Absolute Intensity Measurement. Macromolecules 2000, 33, 4856–4860. [CrossRef]
65. Pitt, G.; Cha, Y.; Shah, S.; Zhu, K. Blends of PVA and PGLA: Control of the permeability and degradability of hydrogels by
blending. J. Control. Release 1992, 19, 189–199. [CrossRef]
66. Gajria, A.M.; Davé, V.; Gross, R.A.; McCarthy, S.P. Miscibility and biodegradability of blends of poly(lactic acid) and poly(vinyl
acetate). Polymer 1996, 37, 437–444. [CrossRef]
67. Riedl, B.; Prud’Homme, R.E. Thermodynamic study of poly(vinyl chloride)/polyester blends by inverse-phase gas chromatogra-
phy at 120 ◦ C. J. Polym. Sci. Part B Polym. Phys. 1986, 24, 2565–2582. [CrossRef]
68. Wang, Y.; Hillmyer, M.A. Polyethylene-poly(L-lactide) diblock copolymers: Synthesis and compatibilization of poly(L-
lactide)/polyethylene blends. J. Polym. Sci. Part A Polym. Chem. 2001, 39, 2755–2766. [CrossRef]
69. Nakafuku, C.; Sakoda, M. Melting and Crystallization of Poly(L-lactic acid) and Poly(ethylene oxide) Binary Mixture. Polym. J.
1993, 25, 909–917. [CrossRef]
70. Park, T.G.; Cohen, S.; Langer, R. Poly(L-lactic acid)/Pluronic blends: Characterization of phase separation behavior, degradation,
and morphology and use as protein-releasing matrixes. Macromolecules 1992, 25, 116–122. [CrossRef]
71. Yang, J.-M.; Chen, H.-L.; You, J.-W.; Hwang, J.C. Miscibility and Crystallization of Poly(L-lactide)/Poly(ethylene glycol) and
Poly(L-lactide)/Poly(ε-caprolactone) Blends. Polym. J. 1997, 29, 657. [CrossRef]
C 2021, 7, 42 38 of 43

72. Yoon, J.-S.; Oh, S.-H.; Kim, M.-N.; Chin, I.-J.; Kim, Y.-H. Thermal and mechanical properties of poly(l-lactic acid)–poly (ethylene-
co-vinyl acetate) blends1Dedicated to Professor Ick-Sam Noh on the occasion of his retirement from Inha University.1. Polymer
1999, 40, 2303–2312. [CrossRef]
73. Jin, H.-J.; Chin, I.-J.; Kim, M.-N.; Kim, S.-H.; Yoon, J.-S. Blending of poly(L-lactic acid) with poly(cis-1,4-isoprene). Eur. Polym. J.
2000, 36, 165–169. [CrossRef]
74. Mikos, A.G.; Thorsen, A.J.; Czerwonka, L.A.; Bao, Y.; Langer, R.; Winslow, D.N.; Vacanti, J.P. Preparation and characterization of
poly(l-lactic acid) foams. Polymer 1994, 35, 1068–1077. [CrossRef]
75. Avella, M.; Errico, M.; Immirzi, B.; Malinconico, M.; Martuscelli, E.; Paolillo, L.; Falcigno, L. Radical polymerization of poly(butyl
acrylate) in the presence of poly(L-lactic acid), 1. Synthesis, characterization and properties of blends. Angew. Makromol. Chem.
Appl. Macromol. Chem. Phys. 1997, 246, 49–63. [CrossRef]
76. Eguiburu, J.; Iruin, J.; Fernandez-Berridi, M.; Román, J.S. Blends of amorphous and crystalline polylactides with poly(methyl
methacrylate) and poly(methyl acrylate): A miscibility study. Polymer 1998, 39, 6891–6897. [CrossRef]
77. Avella, M.; Errico, M.E.; Immirzi, B.; Malinconico, M.; Falcigno, L.; Paolillo, L. Radical polymerization of methyl methacrylate in
the presence of biodegradable poly(L-lactic acid). Preparation of blends, chemical-physical characterization and morphology.
Macromol. Chem. Phys. 2000, 201, 1295–1302. [CrossRef]
78. Chen, G.-X.; Kim, H.-S.; Kim, E.-S.; Yoon, J.-S. Compatibilization-like effect of reactive organoclay on the poly(l-lactide)/poly
(butylene succinate) blends. Polymer 2005, 46, 11829–11836. [CrossRef]
79. Grijpma, D.W.; Van Hofslot, R.D.A.; Supèr, H.; Nijenhuis, A.J.; Pennings, A.J. Rubber toughening of poly(lactide) by blending and
block copolymerization. Polym. Eng. Sci. 1994, 34, 1674–1684. [CrossRef]
80. Ogata, N.; Jimenez, G.; Kawai, H.; Ogihara, T. Structure and thermal/mechanical properties of poly(l-lactide)-clay blend. J. Polym.
Sci. Part B Polym. Phys. 1997, 35, 389–396. [CrossRef]
81. Cha, Y.; Pitt, C. The biodegradability of polyester blends. Biomaterials 1990, 11, 108–112. [CrossRef]
82. Joziasse, C.; Veenstra, H.; Topp, M.; Grijpma, D.; Pennings, A. Rubber toughened linear and star-shaped poly(d,l-lactide-co-
glycolide): Synthesis, properties and in vitro degradation. Polymer 1998, 39, 467–474. [CrossRef]
83. Gérard, T.; Budtova, T. PLA-PHA blends: Morphology, thermal and mechanical properties. In Proceedings of the International
Conference on Biodegradable and Biobased Polymers—BIOPOL 2011, Strasbourg, France, 29–31 August 2011.
84. Amass, W.; Amass, A.; Tighe, B. A review of biodegradable polymers: Uses, current developments in the synthesis and
characterization of biodegradable polyesters, blends of biodegradable polymers and recent advances in biodegradation studies.
Polym. Int. 1999, 47, 89–144. [CrossRef]
85. Wang, L.; Ma, W.; Gross, R.; McCarthy, S. Reactive compatibilization of biodegradable blends of poly(lactic acid) and poly
(ε-caprolactone). Polym. Degrad. Stab. 1998, 59, 161–168. [CrossRef]
86. Nair, N.R.; Sekhar, V.C.; Nampoothiri, K.M.; Pandey, A. 32-Biodegradation of Biopolymers. In Current Developments in Biotechnol-
ogy and Bioengineering; Pandey, A., Negi, S., Soccol, C.R., Eds.; Elsevier: Amsterdam, The Netherlands, 2017; pp. 739–755.
87. Zaaba, N.F.; Jaafar, M. A review on degradation mechanisms of polylactic acid: Hydrolytic, photodegradative, microbial, and
enzymatic degradation. Polym. Eng. Sci. 2020, 60, 2061–2075. [CrossRef]
88. Malwela, T.; Ray, S.S. Enzymatic degradation behavior of nanoclay reinforced biodegradable PLA/PBSA blend composites. Int. J.
Biol. Macromol. 2015, 77, 131–142. [CrossRef]
89. Bikiaris, D.N. Nanocomposites of aliphatic polyesters: An overview of the effect of different nanofillers on enzymatic hydrolysis
and biodegradation of polyesters. Polym. Degrad. Stab. 2013, 98, 1908–1928. [CrossRef]
90. Huang, Q.; Hiyama, M.; Kabe, T.; Kimura, S.; Iwata, T. Enzymatic Self-Biodegradation of Poly(l-lactic acid) Films by Embedded
Heat-Treated and Immobilized Proteinase K. Biomacromolecules 2020, 21, 3301–3307. [CrossRef] [PubMed]
91. de Jong, S.; Arias, E.; Rijkers, D.; van Nostrum, C.; Bosch, J.K.-V.D.; Hennink, W. New insights into the hydrolytic degradation of
poly(lactic acid): Participation of the alcohol terminus. Polymer 2001, 42, 2795–2802. [CrossRef]
92. Engineer, C.; Parikh, J.; Raval, A. Review on hydrolytic degradation behavior of biodegradable polymers from controlled drug
delivery system. Trends. Biomater. Artif. Organs 2011, 25, 79–85.
93. Laycock, B.; Nikolić, M.; Colwell, J.M.; Gauthier, E.; Halley, P.; Bottle, S.; George, G. Lifetime prediction of biodegradable polymers.
Prog. Polym. Sci. 2017, 71, 144–189. [CrossRef]
94. Husárová, L.; Pekařová, S.; Stloukal, P.; Kucharzcyk, P.; Verney, V.; Commereuc, S.; Ramone, A.; Koutny, M. Identification of
important abiotic and biotic factors in the biodegradation of poly(l-lactic acid). Int. J. Biol. Macromol. 2014, 71, 155–162. [CrossRef]
[PubMed]
95. Blasco, L.S.; Ribes-Greus, A.; Alamo, R. Comparative thermal, biological and photodegradation kinetics of polylactide and effect
on crystallization rates. Polym. Degrad. Stab. 2013, 98, 771–784. [CrossRef]
96. Kale, G.; Kijchavengkul, T.; Auras, R.; Rubino, M.; Selke, S.E.; Singh, S.P. Compostability of Bioplastic Packaging Materials: An
Overview. Macromol. Biosci. 2007, 7, 255–277. [CrossRef]
97. Tasaka, F.; Miyazaki, H.; Ohya, A.Y.; Ouchi, T. Synthesis of Comb-Type Biodegradable Polylactide through Depsipeptide−Lactide
Copolymer Containing Serine Residues. Macromolecules 1999, 32, 6386–6389. [CrossRef]
98. Polman, E.M.; Gruter, G.-J.M.; Parsons, J.R.; Tietema, A. Comparison of the aerobic biodegradation of biopolymers and the
corresponding bioplastics: A review. Sci. Total Environ. 2021, 753, 141953. [CrossRef]
C 2021, 7, 42 39 of 43

99. Siparsky, G.L.; Voorhees, K.J.; Miao, F. Hydrolysis of Polylactic Acid (PLA) and Polycaprolactone (PCL) in Aqueous Acetonitrile
Solutions: Autocatalysis. J. Polym. Environ. 1998, 6, 31–41. [CrossRef]
100. Hirao, K.; Nakatsuchi, Y.; Ohara, H. Alcoholysis of Poly(l-lactic acid) under microwave irradiation. Polym. Degrad. Stab. 2010, 95,
925–928. [CrossRef]
101. Iñiguez-Franco, F.; Auras, R.; Burgess, G.; Holmes, D.; Fang, X.; Rubino, M.; Soto-Valdez, H. Concurrent solvent induced
crystallization and hydrolytic degradation of PLA by water-ethanol solutions. Polymer 2016, 99, 315–323. [CrossRef]
102. Sato, S.; Gondo, D.; Wada, T.; Kanehashi, S.; Nagai, K. Effects of various liquid organic solvents on solvent-induced crystallization
of amorphous poly(lactic acid) film. J. Appl. Polym. Sci. 2012, 129, 1607–1617. [CrossRef]
103. McNeill, I.; Leiper, H. Degradation studies of some polyesters and polycarbonates—2. Polylactide: Degradation under isothermal
conditions, thermal degradation mechanism and photolysis of the polymer. Polym. Degrad. Stab. 1985, 11, 309–326. [CrossRef]
104. Tsuji, H.; Ikada, Y. Properties and morphology of poly(L-lactide). II. hydrolysis in alkaline solution. J. Polym. Sci. Part A Polym.
Chem. 1998, 36, 59–66. [CrossRef]
105. Chen, H.-M.; Shen, Y.; Yang, J.-H.; Huang, T.; Zhang, N.; Wang, Y.; Zhou, Z.-W. Molecular ordering and α0 -form formation of
poly(l-lactide) during the hydrolytic degradation. Polymer 2013, 54, 6644–6653. [CrossRef]
106. Suuronen, R.; Pohjonen, T.; Hietanen, J.; Lindqvist, C. A 5-year in vitro and in vivo study of the biodegradation of polylactide
plates. J. Oral Maxillofac. Surg. 1998, 56, 604–614. [CrossRef]
107. da Silva, D.; Kaduri, M.; Poley, M.; Adir, O.; Krinsky, N.; Shainsky-Roitman, J.; Schroeder, A. Biocompatibility, biodegradation
and excretion of polylactic acid (PLA) in medical implants and theranostic systems. Chem. Eng. J. 2018, 340, 9–14. [CrossRef]
[PubMed]
108. Lewis, D.H. Biodegradable Polymers as Drug Delivery Systems. In Biomedical Polymers; Woodhead Publishing: Sawston,
UK, 2007.
109. Lyu, S.; Schley, J.; Loy, B.; Lind, D.; Hobot, C.; Sparer, R.; Untereker, D. Kinetics and Time−Temperature Equivalence of Polymer
Degradation. Biomacromolecules 2007, 8, 2301–2310. [CrossRef] [PubMed]
110. Schliecker, G.; Schmidt, C.; Fuchs, S.; Kissel, T. Characterization of a homologous series of d,l-lactic acid oligomers; a mechanistic
study on the degradation kinetics in vitro. Biomaterials 2003, 24, 3835–3844. [CrossRef]
111. Shih, C. Chain-end scission in acid catalyzed hydrolysis of poly (d,l-lactide) in solution. J. Control. Release 1995, 34, 9–15.
[CrossRef]
112. Pitt, C.G.; Chasalow, F.I.; Hibionada, Y.M.; Klimas, D.M.; Schindler, A. Aliphatic polyesters. I. The degradation of poly(-
caprolactone) in vivo. J. Appl. Polym. Sci. 1981, 26, 3779–3787. [CrossRef]
113. Li, S.M.; Garreau, H.; Vert, M. Structure-property relationships in the case of the degradation of massive poly(α-hydroxy acids) in
aqueous media. J. Mater. Sci. Mater. Med. 1990, 1, 131–139. [CrossRef]
114. Henton, D.; Gruber, P.; Lunt, J.; Randall, J. Polylactic Acid Technology. In Natural Fibers, Biopolymers, and Biocomposites; CRC Press:
Boca Raton, FL, USA, 2005.
115. Gajjar, C.R.; King, M.W. Resorbable Fiber-Forming Polymers for Biotextile Applications; Springer: New York, NY, USA, 2014.
116. Kronenthal, R.L. Biodegradable Polymers in Medicine and Surgery. In Polymers in Medicine and Surgery; Kronenthal, R.L., Oser, Z.,
Martin, E., Eds.; Springer: Boston, MA, USA, 1975; pp. 119–137.
117. Göpferich, A. Mechanisms of polymer degradation and erosion. Biomaterials 1996, 17, 103–114. [CrossRef]
118. Lyu, S.; Sparer, R.; Untereker, D. Analytical solutions to mathematical models of the surface and bulk erosion of solid polymers. J.
Polym. Sci. Part B Polym. Phys. 2005, 43, 383–397. [CrossRef]
119. Kale, G.; Auras, R.; Singh, S.P. Comparison of the degradability of poly(lactide) packages in composting and ambient exposure
conditions. Packag. Technol. Sci. 2007, 20, 49–70. [CrossRef]
120. Siepmann, J.; Göpferich, A. Mathematical modeling of bioerodible, polymeric drug delivery systems. Adv. Drug Deliv. Rev. 2001,
48, 229–247. [CrossRef]
121. Shah, S.; Cha, Y.; Pitt, C. Poly (glycolic acid-co-dl-lactic acid): Diffusion or degradation controlled drug delivery? J. Control.
Release 1992, 18, 261–270. [CrossRef]
122. von Burkersroda, F.; Schedl, L.; Göpferich, A. Why degradable polymers undergo surface erosion or bulk erosion. Biomaterials
2002, 23, 4221–4231. [CrossRef]
123. Goto, T.; Kishita, M.; Sun, Y.; Sako, T.; Okajima, I. Degradation of Polylactic Acid Using Sub-Critical Water for Compost. Polymer
2020, 12, 2434. [CrossRef] [PubMed]
124. Han, X.; Pan, J.; Buchanan, F.; Weir, N.; Farrar, D. Analysis of degradation data of poly(l-lactide–co-l,d-lactide) and poly(l-lactide)
obtained at elevated and physiological temperatures using mathematical models. Acta Biomater. 2010, 6, 3882–3889. [CrossRef]
125. Han, X.; Pan, J. A model for simultaneous crystallisation and biodegradation of biodegradable polymers. Biomaterials 2009, 30,
423–430. [CrossRef]
126. Coszach, P.; Bogaert, J.-C.; Willocq, J. Chemical Recycling of Pla by Hydrolysis; GALACTIC, S.A.: Milwaukee, WI, USA, 2012; p. 7.
127. Gorrasi, G.; Pantani, P. Hydrolysis and Biodegradation of Poly(lactic acid). In Synthesis, Structure and Properties of Poly(lactic acid);
Springer International Publishing: Cham, Switzerlands, 2017.
128. Lyu, S.; Untereker, D. Degradability of Polymers for Implantable Biomedical Devices. Int. J. Mol. Sci. 2009, 10, 4033–4065.
[CrossRef]
C 2021, 7, 42 40 of 43

129. Jung, J.H.; Ree, M.; Kim, H. Acid- and base-catalyzed hydrolyses of aliphatic polycarbonates and polyesters. Catal. Today 2006,
115, 283–287. [CrossRef]
130. Rocca-Smith, J.; Chau, N.; Champion, D.; Brachais, C.-H.; Marcuzzo, E.; Sensidoni, A.; Piasente, F.; Karbowiak, T.;
Debeaufort, F. Effect of the state of water and relative humidity on ageing of PLA films. Food Chem. 2017, 236, 109–119. [CrossRef]
[PubMed]
131. Höglund, A.; Odelius, K.; Albertsson, A.-C. Crucial Differences in the Hydrolytic Degradation between Industrial Polylactide
and Laboratory-Scale Poly(L-lactide). ACS Appl. Mater. Interfaces 2012, 4, 2788–2793. [CrossRef]
132. Limsukon, W.; Auras, R.; Selke, S. Hydrolytic degradation and lifetime prediction of poly(lactic acid) modified with a multifunc-
tional epoxy-based chain extender. Polym. Test. 2019, 80, 106108. [CrossRef]
133. Gupta, M.C.; Deshmukh, V.G. Thermal oxidative degradation of poly-lactic acid Part I. Colloid Polym. Sci. 1982, 260, 308–311.
[CrossRef]
134. Oliveira, M.; Santos, E.; Araújo, A.; Fechine, G.J.; Machado, A.V.; Botelho, G. The role of shear and stabilizer on PLA degradation.
Polym. Test. 2016, 51, 109–116. [CrossRef]
135. Cuadri, A.; Martín-Alfonso, J. Thermal, thermo-oxidative and thermomechanical degradation of PLA: A comparative study
based on rheological, chemical and thermal properties. Polym. Degrad. Stab. 2018, 150, 37–45. [CrossRef]
136. Lucas, N.; Bienaime, C.; Belloy, C.; Queneudec, M.; Silvestre, F.; Nava-Saucedo, J.-E. Polymer biodegradation: Mechanisms and
estimation techniques—A review. Chemosphere 2008, 73, 429–442. [CrossRef]
137. Zou, H.; Yi, C.; Wang, L.; Liu, H.; Xu, W. Thermal degradation of poly(lactic acid) measured by thermogravimetry coupled to
Fourier transform infrared spectroscopy. J. Therm. Anal. Calorim. 2009, 97, 929–935. [CrossRef]
138. Kopinke, F.-D.; Mackenzie, K. Mechanistic aspects of the thermal degradation of poly(lactic acid) and poly(β-hydroxybutyric
acid). J. Anal. Appl. Pyrolysis 1997, 40–41, 43–53. [CrossRef]
139. Kopinke, F.-D.; Remmler, M.; Mackenzie, K.; Möder, M.; Wachsen, O. Thermal decomposition of biodegradable polyesters—II.
Poly(lactic acid). Polym. Degrad. Stab. 1996, 53, 329–342. [CrossRef]
140. Kricheldorf, H.R.; Lüderwald, I. Strukturuntersuchung von polyestern durch direkten abbau im massenspektrometer, 3. Poly-β-
propiolacton, poly-β-pivalolacton und poly-δ-valerolacton. Die Makromol. Chem. 1978, 179, 421–427. [CrossRef]
141. Auras, R.; Lim, L.-T.; Selke, S.; Tsuji, H. Poly (lactic acid): Synthesis, Structures, Properties, Processing, and Applications; John Wiley &
Sons, Inc.: Hoboken, NJ, USA, 2010.
142. Carrasco, F.; Pagès, P.; Gámez-Pérez, J.; Santana, O.; Maspoch, M. Kinetics of the thermal decomposition of processed poly(lactic
acid). Polym. Degrad. Stab. 2010, 95, 2508–2514. [CrossRef]
143. Babanalbandi, A.; Hill, D.; O’Donnell, J.; Pomery, P.; Whittaker, A. An electron spin resonance study on γ-irradiated poly(l-lactic
acid) and poly(d,l-lactic acid). Polym. Degrad. Stab. 1995, 50, 297–304. [CrossRef]
144. Nishida, H. Thermal Degradation, Poly (lactic acid): Synthesis, Structures, Properties, Processing, and Applications; Auras, R.A.,
Lim, T.-K., Selke, S.E.M., Tsuji, H., Eds.; John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2010; pp. 401–412.
145. Meng, Q.; Heuzey, M.-C.; Carreau, P.J. Control of thermal degradation of polylactide/clay nanocomposites during melt processing
by chain extension reaction. Polym. Degrad. Stab. 2012, 97, 2010–2020. [CrossRef]
146. Najafi, N.; Heuzey, M.; Carreau, P.; Wood-Adams, P.M. Control of thermal degradation of polylactide (PLA)-clay nanocomposites
using chain extenders. Polym. Degrad. Stab. 2012, 97, 554–565. [CrossRef]
147. Cam, D.; Marucci, M. Influence of residual monomers and metals on poly (l-lactide) thermal stability. Polymer 1997, 38, 1879–1884.
[CrossRef]
148. Abe, H.; Takahashi, N.; Kim, K.J.; Mochizuki, M.; Doi, Y. Thermal Degradation Processes of End-Capped Poly(l-lactide)s in the
Presence and Absence of Residual Zinc Catalyst. Biomacromolecules 2004, 5, 1606–1614. [CrossRef]
149. Kricheldorf, H.R.; Serra, A. Polylactones. Polym. Bull. 1985, 14, 497–502. [CrossRef]
150. Nijenhuis, A.J.; Grijpma, D.W.; Pennings, A.J. Lewis acid catalyzed polymerization of L-lactide. Kinetics and mechanism of the
bulk polymerization. Macromolecules 1992, 25, 6419–6424. [CrossRef]
151. Amorin, N.S.Q.S.; Rosa, G.; Alves, J.F.; Gonçalves, S.P.C.; Franchetti, S.M.M.; Fechine, G.J.M. Study of thermodegradation and
thermostabilization of poly(lactide acid) using subsequent extrusion cycles. J. Appl. Polym. Sci. 2014, 131. [CrossRef]
152. Cameron, G.; Kerr, G. Thermal degradation of polystyrene—I. Chain scission at low temperatures. Eur. Polym. J. 1968, 4, 709–717.
[CrossRef]
153. Rasselet, D.; Ruellan, A.; Guinault, A.; Miquelard-Garnier, G.; Sollogoub, C.; Fayolle, B. Oxidative degradation of polylactide
(PLA) and its effects on physical and mechanical properties. Eur. Polym. J. 2014, 50, 109–116. [CrossRef]
154. Liu, X.; Zou, Y.; Li, W.; Cao, G.; Chen, W. Kinetics of thermo-oxidative and thermal degradation of poly(d,l-lactide) (PDLLA) at
processing temperature. Polym. Degrad. Stab. 2006, 91, 3259–3265. [CrossRef]
155. Gupta, M.C.; Deshmukh, V.G. Thermal oxidative degradation of poly-lactic acid part II. Colloid Polym. Sci. 1982, 260, 514–517.
[CrossRef]
156. Jeon, H.J.; Kim, M.N. Biodegradation of poly(l-lactide) (PLA) exposed to UV irradiation by a mesophilic bacterium. Int. Biodeterior.
Biodegrad. 2013, 85, 289–293. [CrossRef]
157. Wataru Sakai, N. Tsutsumi, Photodegradation and Radiation Degradation, Poly (lactic acid); John Wiley & Sons, Inc.: Hoboken, NJ,
USA, 2010; pp. 413–422.
C 2021, 7, 42 41 of 43

158. Ikada, E. Photo- and Bio-degradable Polyesters. Photodegradation Behaviors of Aliphatic Polyesters. J. Photopolym. Sci. Technol.
1997, 10, 265–270. [CrossRef]
159. Tsuji, H.; Echizen, Y.; Saha, S.K.; Nishimura, Y. Photodegradation of Poly(L-lactic acid): Effects of Photosensitizer. Macromol.
Mater. Eng. 2005, 290, 1192–1203. [CrossRef]
160. Tsuji, H.; Echizen, Y.; Nishimura, Y. Photodegradation of biodegradable polyesters: A comprehensive study on poly(l-lactide)
and poly(ε-caprolactone). Polym. Degrad. Stab. 2006, 91, 1128–1137. [CrossRef]
161. Janorkar, A.V.; Metters, A.T.; Hirt, D.E. Degradation of poly(L-lactide) films under ultraviolet-induced photografting and
sterilization conditions. J. Appl. Polym. Sci. 2007, 106, 1042–1047. [CrossRef]
162. Bocchini, S.; Fukushima, K.; Di Blasio, A.; Fina, A.; Frache, A.; Geobaldo, F. Polylactic Acid and Polylactic Acid-Based Nanocom-
posite Photooxidation. Biomacromolecules 2010, 11, 2919–2926. [CrossRef]
163. Benyathiar, P.; Selke, S.E.; Harte, B.R.; Mishra, D.K. The Effect of Irradiation Sterilization on Poly(Lactic) Acid Films. J. Polym.
Environ. 2021, 29, 460–471. [CrossRef]
164. Kantoǧlu, Ö.; Güven, O. Radiation induced crystallinity damage in poly(L-lactic acid). Nucl. Instruments Methods Phys. Res. Sect.
B Beam Interactions Mater. Atoms 2002, 197, 259–264. [CrossRef]
165. Birkinshaw, C.; Buggy, M.; Henn, G.; Jones, E. Irradiation of poly-d,l-lactide. Polym. Degrad. Stab. 1992, 38, 249–253. [CrossRef]
166. Vargas, L.F.; Welt, B.A.; Pullammanappallil, P.; Teixeira, A.A.; Balaban, M.O.; Beatty, C.L. Effect of electron beam treatments on
degradation kinetics of polylactic acid (PLA) plastic waste under backyard composting conditions. Packag. Technol. Sci. 2009, 22,
97–106. [CrossRef]
167. Tsuji, H.; Sasaki, H.; Sato, H.; Gotoh, Y.; Ishikawa, J. Neuron attachment properties of carbon negative-ion implanted bioabsorbable
polymer of poly-lactic acid. Nuclear Instrum. Methods Phys. Res. Sect. B Beam Interact. Mater. Atoms 2002, 191, 815–819. [CrossRef]
168. Koo, G.-H.; Jang, J. Surface modification of poly(lactic acid) by UV/Ozone irradiation. Fibers Polym. 2008, 9, 674–678. [CrossRef]
169. Alves, C.M.; Yang, Y.; Marton, D.; Carnes, D.L.; Ong, J.L.; Sylvia, V.L.; Dean, D.D.; Reis, R.L.; Agrawal, C.M. Plasma surface
modification of poly(D,L-lactic acid) as a tool to enhance protein adsorption and the attachment of different cell types. J. Biomed.
Mater. Res. Part B Appl. Biomater. 2008, 87, 59–66. [CrossRef]
170. Nagasawa, N.; Kaneda, A.; Kanazawa, S.; Yagi, T.; Mitomo, H.; Yoshii, F.; Tamada, M. Application of poly(lactic acid) modified by
radiation crosslinking. Nuclear Instrum. Methods Phys. Res. Sect. B Beam Interact. Mater. Atoms. 2005, 236, 611–616. [CrossRef]
171. Ma, Z.; Gao, C.; Ji, J.; Shen, J. Protein immobilization on the surface of poly-L-lactic acid films for improvement of cellular
interactions. Eur. Polym. J. 2002, 38, 2279–2284. [CrossRef]
172. Saadi, Z.; Rasmont, A.; Cesar, G.; Bewa, H.; Benguigui, L. Fungal Degradation of Poly(l-lactide) in Soil and in Compost. J. Polym.
Environ. 2011, 20, 273–282. [CrossRef]
173. Machado, A.V.; Araújo, A.; Oliveira, M. Assessment of polymer-based nanocomposites biodegradability. In Biodegradable Polymers:
Advancement in Biodegradation Study and Applications; Chu, C.-C., Ed.; Nova Science Publishers: Hauppauge, NY, USA, 2015; p. 26.
174. Tomita, K.; Tsuji, H.; Nakajima, T.; Kikuchi, Y.; Ikarashi, K.; Ikeda, N. Degradation of poly(d-lactic acid) by a thermophile. Polym.
Degrad. Stab. 2003, 81, 167–171. [CrossRef]
175. Butbunchu, N.; Pathom-Aree, W. Actinobacteria as Promising Candidate for Polylactic Acid Type Bioplastic Degradation. Front.
Microbiol. 2019, 10, 2834. [CrossRef]
176. Sankhla, I.S.; Sharma, G.; Tak, A. Chapter 4—Fungal degradation of bioplastics: An overview. In New and Future Developments in
Microbial Biotechnology and Bioengineering; Singh, J., Gehlot, P., Eds.; Elsevier: Amsterdam, The Netherlands, 2020; pp. 35–47.
177. Maqbool, Z.; Hussain, S.; Imran, M.; Mahmood, F.; Shahzad, T.; Ahmed, Z.; Azeem, F.; Muzammil, S. Perspectives of using
fungi as bioresource for bioremediation of pesticides in the environment: A critical review. Environ. Sci. Pollut. Res. 2016, 23,
16904–16925. [CrossRef] [PubMed]
178. Luzi, F.; Fortunati, E.; Puglia, D.; Petrucci, R.; Kenny, J.; Torre, L. Study of disintegrability in compost and enzymatic degradation
of PLA and PLA nanocomposites reinforced with cellulose nanocrystals extracted from Posidonia Oceanica. Polym. Degrad. Stab.
2015, 121, 105–115. [CrossRef]
179. Hedstrom, L. Serine Protease Mechanism and Specificity. Chem. Rev. 2002, 102, 4501–4524. [CrossRef] [PubMed]
180. Pattanasuttichonlakul, W.; Sombatsompop, N.; Prapagdee, B. Accelerating biodegradation of PLA using microbial consortium
from dairy wastewater sludge combined with PLA-degrading bacterium. Int. Biodeterior. Biodegrad. 2018, 132, 74–83. [CrossRef]
181. Sangwan, P.; Wu, D.Y. New Insights into Polylactide Biodegradation from Molecular Ecological Techniques. Macromol. Biosci.
2008, 8, 304–315. [CrossRef]
182. Ghorpade, V.M.; Gennadios, A.; Hanna, M.A. Laboratory composting of extruded poly(lactic acid) sheets. Bioresour. Technol. 2001,
76, 57–61. [CrossRef]
183. Kalita, N.K.; Bhasney, S.M.; Mudenur, C.; Kalamdhad, A.; Katiyar, V. End-of-life evaluation and biodegradation of Poly(lactic
acid) (PLA)/Polycaprolactone (PCL)/Microcrystalline cellulose (MCC) polyblends under composting conditions. Chemosphere
2020, 247, 125875. [CrossRef]
184. Gajalakshmi, S.; Abbasi, S.A. Solid Waste Management by Composting: State of the Art. Crit. Rev. Environ. Sci. Technol. 2008, 38,
311–400. [CrossRef]
185. Cooperband, L.R. Composting: Art and Science of Organic Waste Conversion to a Valuable Soil Resource. Lab. Med. 2000, 31,
283–290. [CrossRef]
C 2021, 7, 42 42 of 43

186. Lv, S.; Liu, X.; Gu, J.; Jiang, Y.; Tan, H.; Zhang, Y. Microstructure analysis of polylactic acid-based composites during degradation
in soil. Int. Biodeterior. Biodegrad. 2017, 122, 53–60. [CrossRef]
187. Ho, K.-L.G.; Iii, A.L.P.; Gadea-Rivas, A.; Briceño, J.A.; Rojas, A. Degradation of Polylactic Acid (PLA) Plastic in Costa Rican Soil
and Iowa State University Compost Rows. J. Polym. Environ. 1999, 7, 173–177. [CrossRef]
188. Karamanlioglu, M.; Robson, G.D. The influence of biotic and abiotic factors on the rate of degradation of poly(lactic) acid (PLA)
coupons buried in compost and soil. Polym. Degrad. Stab. 2013, 98, 2063–2071. [CrossRef]
189. Calmon, A.; Guillaume, S.; Bellon-Maurel, V.; Feuilloley, P.; Silvestre, F. Evaluation of Material Biodegradability in Real Conditions–
Development of a Burial Test and an Analysis Methodology Based on Numerical Vision. J. Polym. Environ. 1999, 7, 157–166.
[CrossRef]
190. Karamanlioglu, M.; Houlden, A.; Robson, G.D. Isolation and characterisation of fungal communities associated with degradation
and growth on the surface of poly(lactic) acid (PLA) in soil and compost. Int. Biodeterior. Biodegrad. 2014, 95, 301–310. [CrossRef]
191. Shogren, R.; Doane, W.; Garlotta, D.; Lawton, J.; Willett, J. Biodegradation of starch/polylactic acid/poly(hydroxyester-ether)
composite bars in soil. Polym. Degrad. Stab. 2003, 79, 405–411. [CrossRef]
192. Kolstad, J.J.; Vink, E.T.; De Wilde, B.; Debeer, L. Assessment of anaerobic degradation of Ingeo™ polylactides under accelerated
landfill conditions. Polym. Degrad. Stab. 2012, 97, 1131–1141. [CrossRef]
193. Rudnik, E.; Briassoulis, D. Comparative Biodegradation in Soil Behaviour of two Biodegradable Polymers Based on Renewable
Resources. J. Polym. Environ. 2011, 19, 18–39. [CrossRef]
194. Vasile, C.; Pamfil, D.; Râpă, M.; Darie-Niţă, R.N.; Mitelut, A.C.; Popa, E.E.; Popescu, P.A.; Draghici, M.C.; Popa, M.E. Study of the
soil burial degradation of some PLA/CS biocomposites. Compos. Part B Eng. 2018, 142, 251–262. [CrossRef]
195. Santonja-Blasco, L.; Moriana, R.; Badía, J.; Ribes-Greus, A. Thermal analysis applied to the characterization of degradation in soil
of polylactide: I. Calorimetric and viscoelastic analyses. Polym. Degrad. Stab. 2010, 95, 2185–2191. [CrossRef]
196. Weng, Y.-X.; Jin, Y.-J.; Meng, Q.-Y.; Wang, L.; Zhang, M.; Wang, Y.-Z. Biodegradation behavior of poly(butylene adipate-co-
terephthalate) (PBAT), poly(lactic acid) (PLA), and their blend under soil conditions. Polym. Test. 2013, 32, 918–926. [CrossRef]
197. Itävaara, M.; Karjomaa, S.; Selin, J.-F. Biodegradation of polylactide in aerobic and anaerobic thermophilic conditions. Chemosphere
2002, 46, 879–885. [CrossRef]
198. Musioł, M.; Sikorska, W.; Adamus, G.; Janeczek, H.; Richert, J.; Malinowski, R.; Jiang, G.; Kowalczuk, M. Forensic engineering of
advanced polymeric materials. Part III—Biodegradation of thermoformed rigid PLA packaging under industrial composting
conditions. Waste Manag. 2016, 52, 69–76. [CrossRef]
199. Deroiné, M.; le Duigou, A.; Corre, Y.-M.; le Gac, P.-Y.; Davies, P.; César, G.; Bruzaud, S. Accelerated ageing of polylactide in
aqueous environments: Comparative study between distilled water and seawater. Polym. Degrad. Stab. 2014, 108, 319–329.
[CrossRef]
200. Le Duigou, A.; Davies, P.; Baley, C. Seawater ageing of flax/poly(lactic acid) biocomposites. Polym. Degrad. Stab. 2009, 94,
1151–1162. [CrossRef]
201. Tsuji, H.; Suzuyoshi, K. Environmental degradation of biodegradable polyesters 1. Poly(ε-caprolactone), poly[(R)-3-
hydroxybutyrate], and poly(L-lactide) films in controlled static seawater. Polym. Degrad. Stab. 2002, 75, 347–355. [CrossRef]
202. Tsuji, H.; Suzuyoshi, K. Environmental degradation of biodegradable polyesters 2. Poly(ε-caprolactone), poly[(R)-3-
hydroxybutyrate], and poly(L-lactide) films in natural dynamic seawater. Polym. Degrad. Stab. 2002, 75, 357–365. [CrossRef]
203. Fukushima, K.; Tabuani, D.; Dottori, M.; Armentano, I.; Kenny, J.; Camino, G. Effect of temperature and nanoparticle type on
hydrolytic degradation of poly(lactic acid) nanocomposites. Polym. Degrad. Stab. 2011, 96, 2120–2129. [CrossRef]
204. Brebu, M. Environmental Degradation of Plastic Composites with Natural Fillers—A Review. Polymer 2020, 12, 166. [CrossRef]
[PubMed]
205. Ho, M.-P.; Lau, K.-T.; Wang, H.; Hui, D. Improvement on the properties of polylactic acid (PLA) using bamboo charcoal particles.
Compos. Part B Eng. 2015, 81, 14–25. [CrossRef]
206. Hegyesi, N.; Zhang, Y.; Kohári, A.; Polyák, P.; Sui, X.; Pukánszky, B. Enzymatic degradation of PLA/cellulose nanocrystal
composites. Ind. Crops Prod. 2019, 141, 111799. [CrossRef]
207. Balaguer, M.P.; Aliaga, C.; Fito, C.; Hortal, M. Compostability assessment of nano-reinforced poly(lactic acid) films. Waste Manag.
2016, 48, 143–155. [CrossRef]
208. Ray, S.S.; Bousmina, M. Biodegradable polymers and their layered silicate nanocomposites: In greening the 21st century materials
world. Prog. Mater. Sci. 2005, 50, 962–1079. [CrossRef]
209. Fukushima, K.; Abbate, C.; Tabuani, D.; Gennari, M.; Camino, G. Biodegradation of poly(lactic acid) and its nanocomposites.
Polym. Degrad. Stab. 2009, 94, 1646–1655. [CrossRef]
210. Neppalli, R.; Causin, V.; Marega, C.; Modesti, M.; Adhikari, R.; Scholtyssek, S.; Ray, S.S.; Marigo, A. The effect of different clays
on the structure, morphology and degradation behavior of poly(lactic acid). Appl. Clay Sci. 2014, 87, 278–284. [CrossRef]
211. Stloukal, P.; Pekařová, S.; Kalendova, A.; Mattausch, H.; Laske, S.; Holzer, C.; Chitu, L.; Bodner, S.; Maier, G.; Slouf, M.; et al.
Kinetics and mechanism of the biodegradation of PLA/clay nanocomposites during thermophilic phase of composting process.
Waste Manag. 2015, 42, 31–40. [CrossRef] [PubMed]
212. Duan, J.; Xie, Y.-N.; Yang, J.-H.; Huang, T.; Zhang, N.; Wang, Y.; Zhang, J.-H. Graphene oxide induced hydrolytic degradation
behavior changes of poly(l-lactide) in different mediums. Polym. Test. 2016, 56, 220–228. [CrossRef]
C 2021, 7, 42 43 of 43

213. Anžlovar, A.; Kržan, A.; Žagar, E. Degradation of PLA/ZnO and PHBV/ZnO composites prepared by melt processing. Arab. J.
Chem. 2018, 11, 343–352. [CrossRef]
214. Sun, X.; Xue, B.; Yang, S.; Huo, K.; Liao, X.; Li, X.; Xie, L.; Qin, S.; Zheng, Q. Structural conversion of PLLA/ZnO composites
facilitated by interfacial crystallization to potential application in oil-water separation. Appl. Surface Sci. 2020, 517, 146135.
[CrossRef]
215. Wang, X.-J.; Huang, Z.; Wei, M.-Y.; Lu, T.; Nong, D.-D.; Zhao, J.-X.; Gao, X.-Y.; Teng, L.-J. Catalytic effect of nanosized ZnO
and TiO2 on thermal degradation of poly(lactic acid) and isoconversional kinetic analysis. Thermochim. Acta 2019, 672, 14–24.
[CrossRef]
216. Nakayama, N.; Hayashi, T. Preparation and characterization of poly(l-lactic acid)/TiO2 nanoparticle nanocomposite films with
high transparency and efficient photodegradability. Polym. Degrad. Stab. 2007, 92, 1255–1264. [CrossRef]
217. Kaseem, M.; Hamad, K.; Rehman, Z.U. Review of Recent Advances in Polylactic Acid/TiO2 Composites. Materials 2019, 12, 3659.
[CrossRef] [PubMed]
218. Luo, Y.; Lin, Z.; Guo, G. Biodegradation Assessment of Poly (Lactic Acid) Filled with Functionalized Titania Nanoparticles
(PLA/TiO2) under Compost Conditions. Nanoscale Res. Lett. 2019, 14, 1–10. [CrossRef]
219. Luo, Y.-B.; Wang, X.-L.; Wang, Y.-Z. Effect of TiO2 nanoparticles on the long-term hydrolytic degradation behavior of PLA. Polym.
Degrad. Stab. 2012, 97, 721–728. [CrossRef]
220. Fan, Y.; Nishida, H.; Mori, T.; Shirai, Y.; Endo, T. Thermal degradation of poly(l-lactide): Effect of alkali earth metal oxides for
selective l,l-lactide formation. Polymer 2004, 45, 1197–1205. [CrossRef]
221. Lv, S.; Zhang, Y.; Gu, J.; Tan, H. Biodegradation behavior and modelling of soil burial effect on degradation rate of PLA blended
with starch and wood flour. Colloids Surfaces B Biointerfaces 2017, 159, 800–808. [CrossRef] [PubMed]
222. Rodrigues, C.A.; Tofanello, A.; Nantes, I.L.; Rosa, D.S. Biological Oxidative Mechanisms for Degradation of Poly(lactic acid)
Blended with Thermoplastic Starch. ACS Sustain. Chem. Eng. 2015, 3, 2756–2766. [CrossRef]
223. Petinakis, E.; Liu, X.; Yu, L.; Way, C.; Sangwan, P.; Dean, K.; Bateman, S.; Edward, G. Biodegradation and thermal decomposition
of poly(lactic acid)-based materials reinforced by hydrophilic fillers. Polym. Degrad. Stab. 2010, 95, 1704–1707. [CrossRef]
224. Zuo, Y.F.; Gu, J.; Qiao, Z.; Tan, H.; Cao, J.; Zhang, Y. Effects of dry method esterification of starch on the degradation characteristics
of starch/polylactic acid composites. Int. J. Biol. Macromol. 2015, 72, 391–402. [CrossRef]
225. Pradhan, R.; Misra, M.; Erickson, L.; Mohanty, A. Compostability and biodegradation study of PLA–wheat straw and PLA–soy
straw based green composites in simulated composting bioreactor. Bioresour. Technol. 2010, 101, 8489–8491. [CrossRef] [PubMed]
226. Iovino, R.; Zullo, R.; Rao, M.; Cassar, L.; Gianfreda, L. Biodegradation of poly(lactic acid)/starch/coir biocomposites under
controlled composting conditions. Polym. Degrad. Stab. 2008, 93, 147–157. [CrossRef]
227. Shinoda, H.; Asou, Y.; Kashima, T.; Kato, T.; Tseng, Y.; Yagi, T. Amphiphilic biodegradable copolymer, poly(aspartic acid-co-
lactide): Acceleration of degradation rate and improvement of thermal stability for poly(lactic acid), poly(butylene succinate) and
poly(ε-caprolactone). Polym. Degrad. Stab. 2003, 80, 241–250. [CrossRef]
228. Höglund, A.; Hakkarainen, M.; Edlund, U.; Albertsson, A.-C. Surface Modification Changes the Degradation Process and
Degradation Product Pattern of Polylactide. Langmuir 2010, 26, 378–383. [CrossRef]