Journal of Cleaner Production 258 (2020) 120536

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Journal of Cleaner Production

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

Review

Prospects of biopolymer technology as an alternative option for non-

degradable plastics and sustainable management of plastic wastes
Ehsanul Kabir a, 1, Rajnish Kaur b, 1, Jechan Lee c, 1, Ki-Hyun Kim d, *, Eilhann E. Kwon e, **
a
Department of Farm Power and Machinery, Bangladesh Agricultural University, Mymensingh, 2202, Bangladesh
b
Department of Physics, Panjab University, Sector 14, Chandigarh, 160014, India
c
Department of Environmental and Safety Engineering, Ajou University, Suwon, 16499, Republic of Korea
d
Department of Civil and Environmental Engineering, Hanyang University, Seoul, 04763, Republic of Korea
e
Department of Environment and Energy, Sejong University, Seoul, 05006, Republic of Korea

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

Article history: As of yet, disposal platforms for synthetic polymers have not matured in an environmentally benign
Received 12 October 2019 manner. Consequently, their wastes tend to remain as sources of pollution that chronically release
Received in revised form hazardous substances. In a strategical sense, biopolymers synthesized from natural (plant/animal or
28 December 2019
microbial) sources are thus recognized as an attractive and alternative option to replace synthetic
Accepted 10 February 2020
polymers in various respects, as demonstrated from their Life Cycle Assessment (LCA). It is found that
Available online 13 February 2020
some biopolymers (e.g., polylactic acid (PLA)) are naturally biodegradable, whereas others (e.g., ones
Handling editor: Kathleen Aviso derived from bioethanol) are not. In light of such limitations, new and innovative ideas and findings have
been proposed to seek for the sustainable use of biopolymers. In this review, the prospects of biopolymer
Keywords: technology were emphasized to address the issues associated with non-degradability of plastics. In this
Biopolymers respect, essential strategies were also discussed further for biopolymers as an alternative option for non-
Plastics degradable plastics to help establish sustainable management plan for plastic wastes based on standards,
Biodegradability certifications, and labeling of biopolymers.
Emerging contaminant
© 2020 Elsevier Ltd. All rights reserved.
Sustainability
LCA

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Classification and properties of biopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Degradation mechanisms of biopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.1. Hydrolysis of biopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2. Microbial degradation of biopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.3. Photodegradation of biopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4. Drawbacks of biopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5. Environmental impacts of using biopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.1. Thermoplastic starch (TPS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5.2. Polyhydroxyalkanoates (PHAs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5.3. Polylactic acid (PLA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
5.4. Polybutylene succinate (PBS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
6. The role of biopolymers for sustainable development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

* Corresponding author.
** Corresponding author.
E-mail addresses: kkim61@hanyang.ac.kr (K.-H. Kim), ekwon74@sejong.ac.kr
(E.E. Kwon).
1
These authors are co-first authors because they contributed equally to this
work.

https://doi.org/10.1016/j.jclepro.2020.120536
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 E. Kabir et al. / Journal of Cleaner Production 258 (2020) 120536

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

1. Introduction specifications, e.g., in terms of physicochemical properties and

mechanical functionalities comparable to conventional plastics
To date, synthetic plastics have been employed preferably in (e.g., flexibility, brittleness, and rigidity) (Elsawy et al., 2017). In line
various fields of applications due to their superior physico- with such expectation, the use of biopolymers has been proven to
chemical properties (e.g., availability, flexibility, durability, and have great potential for the conservation of natural ecosystems and
light weight) and economic viabilities (e.g., relative to conventional for the prevention of continued ecological destruction (Hall and
materials like wood, fabric, and metals) (Rendo
n-Villalobos et al., Geoghegan, 2018). In these respects, LCA of biopolymers becomes
2016). As most polymers are derived from petroleum, they tend an essential tool for evaluating their long-term environmental
to be resistant to biodegradation (Mercado et al., 2017). Low impacts. In this review, current knowledge on the fundamental
biodegradability is one of the key factors contributing to the aspects of biopolymers was discussed to describe their classifica-
deterioration of ecological conditions if they are disposed of inap- tion, drawbacks, and degradation mechanisms. Finally, strategies
propriately (simply incinerated or dumped into landfills). From are summarized to help effectively replace conventional plastics
1950 to 2015, 8300 Mt of synthetic polymers were produced, with easily degradable products (related to standards, certifica-
roughly half of which (3900 Mt) were produced in the past 13 years tions, and labeling of biopolymers) for sustainable development.
(Fig. 1) (Geyer et al., 2017). Further, 4900 Mt of them were landfilled Standards, certifications, and labeling are regulatory tools to
or dumped into the natural environment (Geyer et al., 2017). support the establishment of a sustainable economy for bio-
A reliable disposal platform for polymeric wastes has not been polymers. Establishment of such criteria is essential for creation of
fully realized despite their short lifetime and potential hazards biopolymer markets, both for the generation of benefits of the
(Fig. 2). Hence, over the past 65 years (1950e2015), 800 and 600 Mt products and for overcoming uncertainties or doubts about their
of polymeric wastes are reported to have been incinerated and reliability. Standards are highly useful in that the existing regula-
recycled, respectively. Although thermal treatment is the only way tory system can adapt technological innovations in the highly un-
to fully break down conventional polymeric wastes, their inciner- certain biopolymer market (Blind et al., 2017). The International
ation leads to the release of toxic pollutants including dioxins, fu- Organization for Standardization (ISO) defines a standard as “a
rans, and polychlorinated biphenyls (PCBs) (Verma et al., 2016). document that provides requirements, specifications, guidelines, or
Hence, in order to mitigate the aforementioned negative environ- characteristics that can be used consistently to ensure that materials,
mental impacts, there have been increased efforts to develop products, processes and services are fit for their purpose”. The Euro-
biodegradable polymers (biopolymers) that can be produced from pean Committee for Standardization (CEN) offered a standardized
diverse natural feedstocks such as vegetables (e.g., starch, zein, program for bio-based products, as mandated by EU M/429, for the
cellulose, and pectin), animals and dairy products (e.g., chitosan, creation of TC 411 (Technical Committee 411) in 2011 (EU, 2015). TC
whey protein, gelatin, and casein), and fermentation products (e.g., 411 covers horizontal aspects such as determination of bio-based
polyhydroxybutyrate and polyhydroxyvalerate) (Vieira et al., 2011). content, application of LCA, a consistent terminology, and guid-
The utilization of a natural feedstock for the production of bio- ance on using existing standards. TC 249 with the EU M/249 is
polymers can be a desirable innovation, if such products show tasked with developing standards for biopolymers. TC 19, TC 276,
enhanced biodegradability while meeting the technical and TC 411 are responsible for the creation of standards for bio-

Fig. 1. Global production, use, and fate of polymer resins, synthetic fibers, and additives (1950e2015; in million metric tons) (Geyer et al., 2017).
 E. Kabir et al. / Journal of Cleaner Production 258 (2020) 120536
Fig. 2. Product lifetime distributions for the eight industrial sectors using or producing polymers are plotted as log-normal probability distribution functions (Geyer et al., 2017).
lubricants, bio-surfactants, and bio-solvents, respectively. A recent
review was well organized to offer an overview of the work
accomplished by CEN (Ladu and Blind, 2017).
Certification schemes ensure that a product conforms to certain
standards. Most certification schemes were developed for biofuels
and then adapted for bio-based materials like biopolymers. ASTM
D-6866 provides a procedure for quantifying the amount of carbon
in a product to help assess bio-based content in the product.
Recently, the European bio-based content certification scheme was
also developed based on EN 16785e1, enabling independent eval-
uation of claims about bio-based contents (C, H, O, and N) (Ladu and
Blind, 2017). Biodegradability of biopolymers would be certified
based on European standards. A certification process is supposed to
generate a label to guarantee the compliance of products with
sustainability requirements. Labels provide information about
features and characteristics of products. In Europe, no label is yet
used to identify bio-based products (e.g., biopolymers). Given that
labels for biopolymers need to cover a wide range of chemicals and
materials, it would be a challenging task to make labels for bio-
polymers. In this review, the utility of biopolymers has been
described as an alternative option for the proper management of
non-degradable plastics based on sustainable strategies.
2. Classification and properties of biopolymers
Biopolymers are produced from carbon-neutral resources
composed largely of bio-polymers such as carbohydrates and pro-
teins, which impart enhanced biodegradability relative to synthetic
polymers. In general, polymers are generated by repeating a
building block, namely a monomer, consisting of carbon (C), oxygen
(O), hydrogen (H), and nitrogen (N) (Vilela et al., 2014). The
physico-chemical properties of polymers (e.g., stiffness, resilience,
conductivity of heat and electricity, resistance to corrosion, trans-
parency, color, etc.) are determined by the types of monomer, de-
gree of polymerization, and bonding pattern/order. Biodegradable
polymers are classified into five categories depending on their
fabrication methods and sources: (i) from plants (e.g., starch, cel-
lulose, zein, pectin, and lipid); (ii) from animals and dairy products
(e.g., casein, whey protein, gelatin, chitosan, and lipid); (iii) from
fermenting products or by-products (e.g., polyhydroxybutyrate
(PHB) and polyhydroxyalkanoates (PHA)); (iv) from chemical syn-
thesis of naturally derived substances (e.g., polylactic acid (PLA));
and (v) from chemical synthesis of fossil resources (e.g., poly-
caprolactones (PCL) and polyesteramides (PEA)) (Fig. 3) (Vieira
et al., 2011). The properties of various biopolymers are summa-
rized in Table 1.
Starch-based biopolymers are widely used due to the abun-
dance of their raw materials and the ease of processing with
existing methods (e.g., synthesis through film extraction and in-
jection moulding) (Oniszczuk et al., 2015). Biopolymers from
3
starch, soy protein, gelatin, casein, etc. are suitable for food coating,
food packaging, and many other related applications due to their
harmlessness (Baharuddin et al., 2014). In recent years, consider-
able efforts have hence been put on biopolymer packaging to in-
crease the shelf-life and nutritional value of food products (Stefani
et al., 2016).
The global biopolymer market is fragmented according to
products, applications, and regions based on price and quality. Due
to stringent regulations and public demand for using biopolymers
to abate the negative environmental impacts from synthetic poly-
mers, the European Union (EU) is the highest consumer of bio-
polymers in the global market. Steady growth of the biopolymer
market is expected in the Asia-Pacific region due to increasing
environmental concerns and global pressure to curb pollution.
Various types of biopolymer are commercially available, including
PLA, PHA, polyethylene furanoate (PEF), thermoplastic starch (TPS),
and biodegradable polyesters (Kreyenschulte et al., 2014). Among
them, PLA is one of the most common biopolymers. It can be made
from lactic acid through fermentation of dextrose (C6H12O6)
derived from carbohydrate-rich crops (e.g., potato, tapioca, corn,
maize, wheat, and rice) (Mallegni et al., 2018). The same (or
different) types of monomers can be joined together in various
forms via different types of microbial fermentation to generate
biodegradable materials such as PLAs, polyglycolides (PGAs), and
polycaprolactones (Kalia, 2015).
PEF from vegetable-derived fructose is considered to be one of
the most promising biopolymers as it offers enhanced resistance to
mechanical and thermal stress (Isikgor et al., 2015). Specifically, PEF
exhibits improved thermal and mechanical properties relative to
polyethylene terephthalate (PET) (the most common thermoplastic
polymer), including a higher transition temperature (when a ma-
terial changes from one crystal state to another) (Tg) (85
C vs.
76
C), lower melting temperature (211
C vs. 247
C), and 1.6 times
higher Young’s modulus (Isikgor et al., 2015). (Young’s modulus is a
measure of elasticity, and is equal to the ratio of the stress acting on
a substance to the strain produced.)
Moreover, 2,5-furandicarboxylic acid (FDCA) monomer
(C6H4O5) from fructose presents new opportunities to make an
extensive variety of polymers like poly(ethylene 2,5-
furandicarboxylate) (PEF), poly(propylene 2,5-furandicarboxylate)
(PPF), and poly(butylene 2,5-furandicarboxylate) (PBF) that provide
an effective CO2 barrier with higher glass transition temperature
(~87
C) (Wang et al., 2017). These products (i.e., PEF, PPF, and PBF)
can be used as chemical building blocks in diverse industries
including bottling, textiles, food packaging, carpeting, electronics,
and automotives, due to their lower CO2, O2 and H2O permeability
(Wang et al., 2017). However, biopolymers tend to suffer from the
lack of mechanical/chemical resistance. In an effort to overcome
such limitation, natural plasticizers and nanoparticles have been
added (Sanyang et al., 2015). The use of polymer blends is also
4 E. Kabir et al. / Journal of Cleaner Production 258 (2020) 120536
Biopolymer sources
Microorganis
Plants Animals
ms
Polyhydroxya
Starches Casein
lkanoates
Polyhydroxyb
Celluloses Whey protein
utyrate
Pectins Gelatin
Chitosan
Zein
Lipid
Fig. 3. Types of raw feedstocks required for biopolymer synthesis.
another promising alternative for improving biopolymer properties
by limiting repulsive forces inside the biopolymers chains
(Sadasivuni et al., 2019). The photo-degradation (e.g., photolysis,
photo-oxidation) process of the biopolymers is accounted for by UV
radiation (e.g., UVA (315e400 nm) and UVB (295e315 nm)),
whereas their thermal degradation/oxidation by visible radiation
(400e700 nm) and infrared radiation (760e2500 nm) (Siracusa,
2019). As a result of such degradation processes, alterations of
boipolymers can take place in terms of physical and optical prop-
erties, molecular weight, ductility, color, etc.
Currently, the biopolymer market share is less than 1% of the
global polymer industry demand (European Bioplastics, 2017).
However, the global biopolymer market is expected to grow rapidly
to meet government regulations and consumer demand for safe,
eco-friendly packing materials for food items around the world
(Babu et al., 2013). The market of biopolymers is influenced by the
rising demand in the packaging end-use industry (both rigid and
flexible), environmental legislations, government policies, while
growing interests on bio-based content are increasing the demand
for biopolymers. The market dimension of biopolymers was USD
6.95 billion in 2018 and is estimated to hit USD 14.92 billion by
2023, at a compound annual growth rate (CAGR) of 16.5% (GLOBE
NEWSWIRE, 2019). Now the biopolymer producers are increasing
their production capabilities as the leading industries of modern
services (e.g., Samsung and Apple) have decided to use biopolymers
in their products and packaging. Furthermore, increasing rate of
beverage consumption and government policies are driving the
market demand for bio-PET bottle around the globe. However, high
price is one of the vital restraining factors of biopolymers industry.
Hence, shortage of necessary supply chain network at the capacity
locations is another challenge in the market. Furthermore, various
raw materials are being tested for the optimal production of bio-
polymers, as the present technology is still in the nascent stage of
development.
3. Degradation mechanisms of biopolymers
Degradation of biopolymers is receiving significant attention
with respect to solid waste accretion (i.e., growth or increase by the
gradual accumulation of additional layers or matter). Many efforts
have been made to transform degradable biomaterials into mono-
mers and/or carbon (C), oxygen (O), hydrogen (H), and nitrogen (N)
Chemical synthetization Chemical synthetization
(natural origin ) (fossil resources )
Polylactic
Polycaprolactones
acid
Polyesteramides
without any environmental side effects. Thus, it is important to
understand the diverse degradation mechanisms of biopolymers.
Extensive evaluations of the degradation of these materials have
been conducted to address environmental problems such as pollu-
tion, accumulation in landfills, and aggregation of persistent organic
pollutants. Degradation is a process by which polymers are frag-
mented into smaller molecules or elements. Note that not all bio-
polymers are biodegradable. The presence of hydroxyl group makes
biopolymers hydrophilic, which expedites the reaction kinetics for
hydrolysis by absorbing water. The degradation process of bio-
polymers depends on the origin of the polymer and its chemical/
physical properties (e.g., chemical structure, surface area, crystal-
linity, hydrophobicity/hydrophilicity, molecular weight, etc.). Recent
advances in degradation of biopolymers are reviewed in this section.
3.1. Hydrolysis of biopolymers
Hydrolysis is regarded as the major degradation mechanism of
biopolymers. Hydrolytic biodegradation of polymers involves hy-
drolytic bond cleavage to form water soluble byproducts that can
dissolve in an aqueous environment, giving rise to polymer
degradation. Degradation of biopolymers via hydrolysis enhances
hydrophilicity via hydrolytic bond cleavage (Machmudah et al.,
2017). Hydrolysis is initiated from the inside out, turning the
polymer into a porous matrix with little dimensional change. On
the other hand, surface erosion causes mass loss to progress from
the outer surface toward the center while maintaining the me-
chanical and structural integrity of the polymer. In general, hy-
drolysis of biopolymers involves bond dissociations of the
polymeric backbone in the presence of water, in which dissociated
molecules turn into water soluble monomeric acids via two path-
ways (bulk and surface erosion). In bulk erosion, water molecules
diffuse quickly into the amorphous sites, causing a rapid loss of
strength and structural properties of the biopolymer. In surface
erosion, materials begin to degrade at the exterior surface, while
the interior material is degraded last (Burkersroda et al., 2002). In
addition, hydrolysis occurs by breaking larger compounds like
polymers into smaller components, turning the polymer into a
porous matrix with little dimensional change (Bagheri et al., 2017).
A graphical presentation of the bulk and surface erosion processes
is provided in Fig. 4. Surface erosion occurs by hydrolyzing the
outer surface first, whereas bulk erosion hydrolyses the entire

Table 1
Summary of basic properties of various biopolymers.
Order Name
1 Polyhydroxybutyrate
(PHB)
2 Polycaprolactones (PCL)
3 Polyhydroxyalkanoates
(PHAs)
4 Polylactic acid (PLA)
5 Polyethylene 2,5-
furandicarboxylate(PEF)
Fig. 4. Hydrolysis degradation process of biopolymers: (a) Bulk Erosion and (b) Surface
Erosion.
E. Kabir et al. / Journal of Cleaner Production 258 (2020) 120536 5
Chemical structure Melting Glass Tensile Application
temperature(Tm) transition strength(MPa)
(
C) temperature
(Tg) (
C)
170e180 2e5 40 Medical applications
60 60 16 Medical applications, drug
delivery device
170e180 5 43 Packaging material, medical
and pharmaceutical
applications
150e160 60e65 16 Medical implants (e.g., anchors,
screws, plates, pins, rods),
packaging material, membrane
gas separation and
pervaporation (PV)
211 85 25 Packaging material
biopolymer, thereby resulting in the hydrolytic degradation of the
surface and core of the biopolymer. Various factors (including pH,
temperature, hydrophobicity, morphology, crystallinity, and
porosity) affect the degree of hydrolysis. Polyanhydrides and
aliphatic polyesters can be degraded in 182 days in the presence of
water (Ho €glund et al., 2012).
Researchers have studied the effects of thermal treatment of
biopolymers at temperatures from 20 to 50
C to identify the
combined effects of temperature and kinetics on the hydrolysis of
biopolymers. While investigating the degradation kinetics of PLA
and Mg/PLA composite, the impacts of immersion temperature (25,
37, and 50
C) and pressure were examined. This examination
demonstrated that there are well-characterized connections be-
tween the bending strength of the samples and the PLA atomic
weight amid submersion, which are independent of the degrada-
tion temperature and external compression stress. Results of these
investigations could contribute to a numerical model of the re-
lationships among bending strength, PLA molecular weight, im-
mersion time and temperature (Li et al., 2017).
6 E. Kabir et al. / Journal of Cleaner Production 258 (2020) 120536
Poly(lactic) acid (PLA) has excellent physico-chemical properties
such as high mechanical strength, high Young’s modulus, biode-
gradability, biocompatibility, bio-absorbability, transparency, and
low toxicity. Nevertheless, PLA exhibits fast reaction kinetics for
hydrolysis because the oligomeric structure of PLA is water soluble
(Gupta et al., 2007).
As the ester groups are hydrolytically degraded, the molecular
weight decreases, as dissolvable low-molecular-weight oligomers
and monomers are released. The kinetic model for hydrolysis in-
dicates that the ester bond separation rate is time-dependent.
During hydrolytic degradation, ester bonds in PLA are seldom hy-
drolyzed by water atoms, which results in carboxylic and hydroxyl
end gatherings. It was observed that the reaction rate for hydrolysis
can be expedited by providing additional energy. Specifically, the
reaction rate for hydrolysis was higher at 60
C and pH 7.4 than at
37
C and pH 3.7 (Li et al., 2017) Hydrolytic degradation of PLA
begins after only two days.
High temperature and humidity expedite the reaction kinetics
for hydrolysis of PLA. Cadori et al. reported the reaction kinetics for
hydrolysis of PLA at pH of 2 under varied hydrolytic temperatures
from 40 to 120
C (Codari et al., 2012). The evolution of PLA olig-
omers (different chain lengths and chirality) as a function of hy-
drolytic time was monitored and quantified using HPLC. To do so,
the reaction kinetics for hydrolysis of PLA were evaluated at a range
of temperatures as a function of the formation of hydrolytic prod-
ucts. Based on the developed kinetic model, the activation energies
of two PLA oligomers with different chain lengths and chirality
were estimated to be 73 and 58 kJ mol1.
Tsuji et al. degraded PLA at 37
C and pH of 7.4. Introduction of
alcohols during ring-opening polymerization of lactides results in
the formation of linear and star-shaped (branching) structures. The
effects of branching architecture and crystallinity on hydrolytic
degradation and crystalline morphology changes were examined in
detail. The rate of debasement was likewise evaluated based on a
decline in atomic weight, which was higher for crystalline samples
than for amorphous samples. The glass transition and cold crys-
tallization temperatures of originally amorphous and crystalline
samples demonstrated changes comparable to those recorded for
one-armed PLA. Overall, it was observed that molecular weight,
which is used to quantify the degradation rate, decreases during
this process. The degradation rate was significantly lower with
higher branching architecture as well as a high number of hydroxyl
groups per unit mass (Tsuji and Hayashi, 2015).
As degradation of PLA is known to occur in the presence of
water, the effects of organic solvents also were studied. Swelling of
the polymer matrix expands chain mobility and induces crystalli-
zation. For instance, Franco et al. found that solvents expedite
crystallization and hydrolytic degradation in water-ethanol solu-
tions. They saturated PLA films in pure water, water: ethanol
(50:50) and water: ethanol (5:95) for three months and compared
the change in molecular weight, water sorption, sorption of
ethanol, and lactic acid release under the three different experi-
mental conditions. Immersion of PLA in 50% ethanol resulted in a
faster hydrolysis rate than in 95% ethanol or in pure water. The
results were confirmed by NMR spectroscopy, which showed that
PLA experienced solvent-induced crystallization. The overall
degradation process was associated with changes in mechanical
and thermal properties, molecular weight and morphology of the
polymers (In ~ iguez-Franco et al., 2016).
Accelerated hydrolytic degradation of PLA was reported in
polymer/clay nanocomposites. In a study of hydrolytic degradation
of PLA by Di et al., the molecular weight and the pH of the medium
were monitored for PLA degradation. The introduction of clay helps
water diffusion, which further enhances the degradation rate. After
observing for six weeks, they concluded that clay-filled PLA
degraded 3e4 times more than neat polylactide (Di et al., 2005).
Lizundia et al. (2016) proposed the use of nanomaterials such as
zinc oxide (ZnO) to enhance the eco-friendly disposal of polymers.
A poly(L-lactide) (PLLA)/ZnO composite with a pore diameter of
125e250 mm and porosities of up to 90% was prepared. PLLA/ZnO
nanocomposites with homogeneously distributed nanoparticles
were subjected to thermal and hydrolytic degradation processes to
explore the catalytic effect. The FTIR results demonstrated an in-
crease in carboxylic acid groups, which was proportional to ZnO
loading due to lattice oxygen vacancies in ZnO. These findings
suggest that progress in eco-friendly disposal of polymeric waste
can be achieved through the use of natural materials as catalysts
(Lizundia et al., 2016). As degradation of PLA is already known in
the presence of water, the effect of organic solvent was also studied.
In detail, the polymer matrix was swelled, increasing chain
mobility and inducing solvent-induced crystallization. For instance,
Franco et al. elucidated concurrent solvent expedites crystallization
and hydrolytic degradation in water-ethanol solutions. The PLA
films were immersed in water, water: ethanol (50:50) and water:
ethanol (5:95) for three months. Franco et al. compared change in
molecular weight, water sorption, sorption of ethanol, and lactic
acid release under three different experimental conditions. The
immersion of PLA in 50% ethanol showed the faster hydrolysis rate
than in 95% ethanol and pure water). The studies were confirmed
by NMR spectroscopy showing that PLA experienced solvent-
induced crystallization. The hydrolysis of PLA was associated with
the fact that during exposure there is a release of lactic acid, which
is a low molecular weight, water-soluble oligomers and monomers.
The hydrolysis of bio-based poly(butylene succinate-co-fur-
andicarboxylate) and poly(butylene adipate-co-furandicarbox-
ylate) copolyesters were studied at 25
C with a phosphate-
buffered saline (PBS) solution of pH 7.0 (Peng et al., 2017). The
authors reported the hydrolysis kinetics for a period of 22 weeks.
The dependence of biopolymer hydrolysis on temperature was
correlated with weight reduction and the viscosity-averaged mo-
lecular weight decrement using X-Ray Diffraction and AFM analysis
in a study by Bonartsev et al. A key point from these studies is that
the problem of biodegradation in semicrystalline biopolymers re-
mains unresolved. As biodegradable polymers are viewed as an
important solution to ecological issues created by plastic waste, the
kinetics of their degradation process was estimated through
various models. Hydrolytic degradation of polylactic acid (PLA) and
its composites was estimated by Bonartsev et al. (2012). Poly(3-
hydroxybutyrate) (PHB) is a standout amongst the most essential
biopolyesters from the group of polyhydroxyalkanoates, which are
created by microorganisms from renewable resources. Amorphous
PHB films were degraded in aqueous media at various pH values
(13.0, 12.5, 12.0 and 7.0) by Polyak et al. Degradation studies were
done over different degradation periods (7, 14, 21 and 28 days). The
outcomes demonstrated that degradation occurs in the interior of
the samples and not on their surface because degradation does not
happen randomly, but rather with higher frequency toward the end
of the chains. The rate of degradation increased with increasing pH
values (Polya
k et al., 2017). Table 2 summarizes factors affecting the
hydrolysis of biopolymers, as discussed in this subsection.
3.2. Microbial degradation of biopolymers
Degradation of biopolymers can be triggered by microbiota (e.g.,
fungi and bacteria) and/or other factors (e.g., hydrolysis, photolysis,
mechanical, and/or thermal stress) (Pathak and Navneet, 2017).
Microbial degradation alters the strength and color of polymeric
material under controlled conditions of aerobic and anaerobic
surroundings. During this process, microorganisms convert the
insoluble biopolymer into a soluble biopolymer. These compounds
 E. Kabir et al. / Journal of Cleaner Production 258 (2020) 120536
Table 2
Hydrolysis of biopolymers.
Order Biopolymer
1 Polyanhydrides and aliphatic polyesters
2 Poly(DL-lactide)
3 Polylactic acid
4 4-armed poly(L-lactide)s at 37
C and pH 7.4
5 Polylactic acid
6 Polylactic acid
7 Poly(L-lactide)
8 Poly(butylene succinate-cofurandicarboxylate) and poly(butylene adipate-co-
furandicarboxylate) copolyesters
9 Poly(3-hydroxybutyrate) (PHB)
Fig. 5. Microbial degradation of biopolymers.
are used by microorganisms in their microbial growth metabo-
lisms. This explains the degradation of biopolymers in the presence
of microbes showing the by-products of degradation, as shown in
Fig. 5.
The microbial degradation process involves excretion of extra-
cellular enzymes that depolymerize the biopolymers. As extracel-
lular enzymes are secreted outside the cell membrane, they allow
microbes to derive energy and nutrients from polymers and cata-
lyze the cycling of organic matter. During the depolymerization
step, the biopolymer is decreased to a size that is water soluble and
ready to be transported through the cell wall. After this it can be
mineralized through microbial metabolic pathways, which involves
chemical transformation and turnover of naturally occurring bio-
polymers (Pathak and Navneet, 2017). Fragments of the bio-
polymers (depolymerization) are consumed as carbon substrates,
which form various products such as CO2, CH4, NH3, SO2, H2, water,
salts, and minerals (Emadian et al., 2017). In general, degradation
rate is faster under aerobic conditions than under anaerobic con-
ditions. Microbes such as Fusarium verticillioides, Penicillium
roquefort, Amycolatopsis sp., Bacillus brevis, and Rhizopus delemar
have been identified as responsible for the biodegradation of PLA
(Kawai, 2010).
The biodegradation of diverse plastics (such as traditional/bio-
based plastics and natural fiber composites (i.e., poly-
hydroxyalkanoate plastics, starch-based plastics, and materials
made up of compost)) was investigated (Go
mez and Michel, 2013).
These authors determined the extent of biodegradation by esti-
mating the amount of carbon mineralized from these materials
during incubation using scanning electron microscopy (SEM). Their
7
Factors affecting the rate of Hydrolysis conditions
degradation
Dimensions of the polymer 182 days in the presence of
water
Temperature and pH conditions 60
C at pH 7.4
Temperature and pH conditions 40 to 120
C
Temperature and pH conditions 37
C at pH 7.4
Clay nanocomposites 25 and 37
C
Concurrent solvents ethanol and 40
C
water
ZnO NPs e
PBS buffer solution 25
C at pH 7.0
pH dependence pH value of 13.0, 12.5, 12.0
and 7.0
investigations demonstrated that following 660-day-long stretches
of soil incubation, mineralization occurred for poly-
hydroxyalkanoate plastics, starch-based plastics and for materials
produced using manure (Go
mez and Michel, 2013).
Microcantilever sensors were used for rapid assessment of
enzyme-based degradation reactions (Bose et al., 2015). Bose et al.
degraded amorphous poly(D, Lactide) (PDLLA) and estimated the
reverberation frequencies of polymer-covered microcantilevers
during debasement. This type of analysis provides a fast measure-
ment of the biodegradation rate of PDLLA using a minute amount of
sample. When the cantilever is covered with polymer, the reso-
nance frequency decreases from 33.3 kHz to 30.1 kHz because of
the expansion of mass on one side of the cantilever. When the
cantilever is drenched in a proteinase K compound solution, the
amount of polymer on the cantilever surface declines because of
the beginning of degradation and the frequency begins to increase
until the point when it approaches the initial resonance frequency
of the blank cantilever. Meanwhile, Masmoudi et al. (2016) worked
on novel biodegradable packaging materials produced from vegetal
biomass such as starch and PLA reinforced with cellulose. The
plasticized starch demonstrated a rapid biodegradation process, in
contrast to the PLA/cellulose fibers. These new materials were
proposed for sustainable development and waste reduction, as al-
ternatives to non-degradable plastic materials. In this way, low cost,
safe, high value biopolymers for food packaging have been pro-
duced by reinforcing starch and PLA using natural fibers.
Moon et al. also estimated microbial degradation of PLA with
anaerobic bacteria from sewage sludge, and the biodegradability
was evaluated using the specific gas generation rate. During the
8 E. Kabir et al. / Journal of Cleaner Production 258 (2020) 120536

Table 3
Microbial degradation of bioplastics.

Order Biopolymer Type of microbe Factors affecting the rate of degradation

1 Polyhydroxyalkanoate plastics, starch-based plastics e Soil incubation

2 Poly (D, Lactide) Proteinase K enzyme e
3 PLA Bacillus strains Cellulose fibers
4 PLA Anaerobic bacteria from sewage sludge pH of 7.0
5 Starch-glycerol based films Yerba mate extract Ambient conditions
6 Polyhydroxyalkanoate (PHAs) Bacillus subtilis e

the photodegradation process (Guillet et al., 1968). The most

effective UV wavelength range for photodegradation of bio-
polymers is 250e340 nm (Yousif and Haddad, 2013). A basic
schematic of the photodegradation process is presented in Fig. 6. To
expedite photolysis activity associated with light wavelengths from
200 to 700 nm, photo-sensitive additives (e.g., TiO2 and ZnO) are
Fig. 6. Photolysis mechanism of biopolymers. added to the polymer. For example, the presence of TiO2 nano-
particles during the photodegradation process was enhanced in
poly(butylene succinate)/titanium dioxide (PBS/TiO2) (Heitmann
degradation of PLA with anaerobic digester sludge, the degree of
et al., 2016). The degradation efficiency was enhanced due to
biodegradation was assessed by examining both gas generation and
unique structural and interfacial interactions between the nano-
by-product development. The degradation occurs at the interface of
composites of nanoparticles and PBS matrix. Due to the high sur-
the polymer exposed to the solution and bacteria. The particular
face area of TiO2 (460 m2 g1), the maximum loading of the
CO2 and CH4 production rates were estimated in light of the total
polymer material can be achieved, while the PBS matrix ensures the
surface area to measure the biodegradability of PLA. The results
dispersion of these particles in the matrix structure (Buasri et al.,
successfully demonstrated a fast biodegradation process that can
2013). The incorporation of NPs increases the crystallinity of the
be controlled to produce ecological polymer materials (Moon et al.,
composite and slightly strengthens the interfacial interactions be-
2016).
tween cavities in the structure. Degradation studies were also done
Researchers also studied biodegradable and edible cassava starch-
by using various nanomaterials as photocatalysts in the presence of
glycerol-based films using different concentrations of yerba mate
UV radiation, as explained in this section. The nanostructured
extract (Jaramillo et al., 2016). The studies revealed the plasticizing
niobium oxyhydroxide (NbO2OH) was dispersed over poly (3-
impact of yerba mate extract as an antioxidant when it was integrated
hydroxybutyrate) (PHB) biopolymer at mass fractions of 1, 2, 3
into the matrix. Thermal degradation and biodegradability of the
and 5 wt% and heated at 55
C for 4 h. The results suggested that
obtained biofilms were analyzed by using various characterization
composite formation modifies the bandgap value (2.53e3 eV),
tools. Kanmani et al. (2016) investigated enzymatic degradation of
which further improves the photocatalysis process (Heitmann
polyhydroxyalkanoates (PHAs), which are a critical class of biode-
et al., 2016). Table 4 summarizes the photodegradation of bio-
gradable polymers, using lipase from Bacillus subtilis. The enzymatic
polymers, as discussed in this subsection.
degradation of PHAs showed a decrease in molecular weight. More-
Photolysis also can be expedited in the presence of combined
over, scanning electron micrographs revealed a change in polymer
mechanical stresses such as shear stress, tension, and compression.
surface morphology. The chromatography studies indicated a 21.3%
Powerful shearing stress mechanically tears the polymer, resulting
molecular weight decrease and a 28.3% weight loss. From TGA studies,
in the formation of fragments with low molecular weight
the degraded sample showed a 45.82% weight loss between 30 and
(21e70 wt % of the polymer). Poly(ester-urethane) films based on
930
C. The melting temperature (Tm) of the polymer also decreased
poly[(R)-3-hydroxybutyrate] and poly(ε-caprolactone) blocks also
from 126.22 to 118.18
C, as demonstrated by various scanning calo-
were degraded photo-catalytically by Saad et al. (2010) and changes
rimetry studies. These lipase-catalyzed chain scission responses can
in molecular weight associated with variations in UV irradiation
be utilized to grow low-molecular-weight functional biopolymers for
were observed. It was noticed that, photolysis of examined tests i.e.
sustained drug release in pharmaceutical applications. Table 3 sum-
some synthesized poly(ester-urethane)s based on PHB and PCL
marizes the microbial degradation of biopolymers, as discussed in this
hinders preceding biodegradation increases its degree of degra-
subsection.
dation. The studies were performed using viscosity measurements
coupled to differential scanning calorimetry (DSC), which was able
3.3. Photodegradation of biopolymers to explain about crystalline phase. For biodegradation, the film
samples were placed on trays and covered with a standard soil
Ultraviolet (UV) rays, which are electromagnetic radiation with mixture preserved at a moisture level of 22e26%, at pH of 7.5e8.5
wavelengths ranging from 10 to 400 nm, play a critical role during and temperature of 25e30
C. The films were observed after

Table 4
Photodegradation of biopolymers.

Order Biopolymer Factors affecting the rate of degradation Photodegradation conditions

1 Hyaluronic acid Modification with methacrylic anhydride and photopolymerized e

2 Poly(ester-urethane) films Soil burial pH range of 7.5e8.5 and temperature of 25e30
C (254 nm)
3 Chitosan Treatment With H2O2 254 nm
4 Poly(butylene succinate) Titanium dioxide e
5 Poly (3-hydroxybutyrate) (PHB) Niobium oxyhydroxide Heating at 55
C for 4 h
 E. Kabir et al. / Journal of Cleaner Production 258 (2020) 120536
various time intervals, after which they were washed with DI water
and dried. These co-polymers were treated under UV-irradiation
with a wavelength of 254 nm with different exposure times (3, 6,
and 9 h). Increased exposure time of irradiation was supported by
increment of the extent of the gel fraction and the reduce of the
characteristic viscosity of the soluble fraction of co-polymers.
The biodegradability of biopolymers when UV-illumination
under soil internment demonstrated that photolysis in air before
biodegradation expanded the debasement rate (Saad et al., 2010).
So, after using UV irradiation in the degradation process, the re-
searchers also started exploring the effects of adding catalyst ma-
terials to accelerate the rate of photolysis. Other studies included
the application of mechanical forces as well as heating treatments
to the biopolymer to increase the degradation rate. To reproduce
the mechanical reuse of the polymer, the initial step is a quickened
ageing process, which includes 40 h of photochemical degradation
under UVB lights. Additionally, the examples were exposed to
thermal degradation in a convection oven at 50
C for 20 days. After
ageing, samples were washed with NaOH and a surfactant solution.
Finally, the samples were reprocessed by extrusion and compres-
sion techniques (Beltr
an et al., 2017).
There was an attempt to degrade chitosan under UV radiation in
the presence of hydrogen peroxide (H2O2) (Wang et al., 2017). The
carbonyl groups were found in the chitosan oligomers via diffuse
reflectance spectroscopy (DRS) analysis. Moreover, exposure of
chitosan to ultraviolet light alone could also crop carbonyl groups
by the cleavage of the glycosidic bond. When the system was
exposed to UV light with a wavelength of 254 nm (where H2O2
absorbs), there is disassociation of the eOeOe peroxide bond fol-
lowed by the generation of hydroxyl radical (Eq. (1)).
H2O2 þ hʋ / 2 .OH.
These hydroxyl radicals can oxidize the glycosidic linkages of
biopolymer for its degradation. Thus, the overall process involves
disassociation of hydrogen peroxide and generation of hydroxyl
radicals, which enhances the reaction kinetics for the photolysis.
This synergetic effect of combined exposure to UV and hydrogen
peroxide associated with breaking of the glycosidic bond was
demonstrated by means of viscometry. The decay rates of the
Fig. 7. A list of the major factors influencing the natural degradation of biopolymer.
9
intrinsic viscosities, when measured as a function of reaction time
(30 vs. 180 min) in the presence of H2O2 and UV radiation, were 17.2
and 26.4%, respectively. As the cleavage of the CeOeC glycosidic
bond prompted chain scission, carbonyl groups were created after
30 min of irradiation. According to FTIR studies, the bands at 1602
and 599 cm1 become stronger. Further, the peak at 599 cm1 was
shifted to the higher wavenumbers. The shifting of NeH extending
vibration peak toward the lower wavenumbers is due to weakening
of intermolecular and intramolecular hydrogen bonds of chitosan.
This weakening of bonds and reduced crystallinity should be
accounted for by the degradation of chitosan. This type of analysis
facilitated a fast measurement of the biodegradation process.
All the major degradation pathways for biopolymers as
described above are affected by the physiochemical properties of
the materials (e.g., surface area, molecular weight, chemical
structure, crystallinity, modulus of elasticity, glass transition tem-
perature, and melting temperature of biopolymers). The type of
environmental processes (e.g., erosion, hydrolysis, photo-
degradation, and thermo oxidative degradation) and factors (such
as moisture, temperature, solar radiation, air movement and
pressure, precipitation, chemical and by micro and macro-
organisms) play a vital role in efficient degradation process. The
description of these different components is provided in Fig. 7.
Despite the significance of temperature in such respect, yet rela-
tively little is known about the thermal treatment of biopolymers at
low temperature regime (e.g., from 20 to 50
C) to induce or
stimulate their degradation (Peelman, 2015). To assess the degra-
dation kinetics of pure PLA and Mg/PLA composite, the effect of
various immersion temperature (25, 37, and 50
C) and compres-
sion stress were studied (Li et al., 2017). These authors tested the
effect of rising immersion temperature in an effort to shorten the
(1) experimental time. The results on this immersion temperature test
indicated that there are well-defined relationships between the
bending strength of the specimens and the PLA molecular weight
during immersion, which are independent of the degradation
temperature and/or external compression stress. The outcomes of
these studies were helpful in developing a numerical model to
elucidate the relationships between diverse variables (e.g., bending
strength, PLA molecular weight, activation energy, immersion time,
and temperature) (Li et al., 2017).
10 E. Kabir et al. / Journal of Cleaner Production 258 (2020) 120536
Fig. 8. Comparison of aerobic vs. anaerobic degradation of biopolymers in the pres-
ence of light, temperature, and water. Reprinted from (B
atori et al. 2018), Copyrights
2019, with permission from Elsevier.
Further, enormous efforts were put to assess the other factors
controlling the degradation of biopolymers such as the application
of mechanical forces as well as heating treatments to fasten the
degradation. To simulate the effect of mechanical recycling of the
polymer on its structure and properties, it was subjected to two
recycling processes. The first recycling process consisted of an
accelerated ageing and melt processing step, while the other
recycling process involved an accelerated ageing, washing, and a
second-melt processing step. This photochemical degradation
process involves exposure of biopolymer under UVB lamps for 40 h
(Beltra
n et al., 2017). Further, the samples were exposed to thermal
degradation in a convection oven at 50
C for 20 days. After ageing,
samples were washed with NaOH and a surfactant solution. Finally,
the samples were reprocessed by extrusion and compression
techniques (Beltr
an et al., 2017).
Mechanical recycling of PLA filled with cellulose fiber compos-
ites was investigated by compression moulding (Åkesson et al.,
2016). For this, a composite of 30 vol% PLA and 70 vol% cellulose
fibers were prepared. The recyclability studies were performed by
grinding the material and then using the recyclate as a filler for PLA.
After the formation of composite, they were characterized by ten-
sile tests, Charpy impact tests, DMTA, and SEM. The results showed
a better stability of the material due to reinforcing effect. The
biodegradation of PCL/gelatin and PCL/collagen nanofibers was also
studied based on electrospun from different solvent systems
(Dulnik et al., 2016). The biodegradation studies of PCL/gelatin and
PCL/collagen nanofibers were compared to assess the effect of
various solvents used in the process.
Further, the degradation of biopolymers is affected by chemical
processes (e.g., dissolution, oxidation, and hydrolysis). In this
respect, the factors such as reactivity of the material, level of
exposure, and the nature of the contaminants also play a vital role
(Ba
tori et al., 2018). The efficiency of these processes can also be
boosted by heat treatment. As biopolymers are long-chain mole-
cules, their degradation may proceed in a step by step process. First
the long polymeric chains are broken down to monomers by such
factors as temperature, water, and sunlight. Further, the biodegra-
dation can occur in two ways, aerobically and anaerobically.
Biodegradation can occur under aerobic conditions, where oxygen
is the electron acceptor. In contrast, under anaerobic conditions,
nitrate or sulfate can serve as the electron acceptor. As methane gas
is released during anaerobic degradation process, aerobic degra-
dation is a preferable process for degradation of biopolymers
(Fig. 8).
4. Drawbacks of biopolymers
Biodegradation of biopolymers in the natural environment takes
a long time, during which they are considered as pollutants. More
specifically, in a controlled composting environment, it may take
about three months for PLA to break down into its constituent
parts. In contrast, in the field, it may take 100 to 1000 years to
decompose a PLA bottle due to the absence of light and oxygen (Lu
et al., 2014). The breakdown process of biodegradable products
depends on temperature and humidity. At low temperature and
high humidity, the degradation process may not progress efficiently
(Popescu et al., 2017). As most commercial biopolymers are pro-
duced from starch, companies are choosing genetically modified
species for higher crop yields. Some scientists have voiced concerns
about whether genetically modified crops generate or increase al-
lergens, toxins, and anti-nutrients (Arcieri, 2016). Hence, as the
origins of biopolymers are more diversified than those of a com-
parable conventional plastic, they should be treated differently af-
ter use. For example, biopolymers should be treated in composting
facilities, although very few industrial-grade facilities are currently
available. Moreover, it is difficult to separate PLA from PET as the
available technology is costly and not commonly used. Further-
more, the recycling value of PET products decreases significantly if
they are contaminated with PLA (Qin et al., 2017). That is why many
recyclers are against the use of PLA until proper technology is
available to remove the PLA products completely.
The European Plastics Recyclers Association addressed that
biodegradable plastic bags may “have the potential to do more
harm to the environment than good.” (Mohapatra et al., 2017).
Although a small amount of metal is contained in some biode-
gradable products, high levels of lead and cobalt were detected in
one brand (Jones and McClements, 2010). This raises questions
regarding the toxicity of metal residues on these products. With the
growing demand, the expansion of cultivable land area is required
as the feed stock of the biopolymers will increase. This may have a
negative impact on the production of food, feed, and pasture. In
2017, around 0.82 million hectares of land were used globally for
the production of biopolymer feedstock, with the area projected to
be 1.03 million hectares by 2022 (IfBB, 2018). Another downside of
biopolymers is their high production cost. In addition, there are
quality issues for biopolymers when employed in real situations. In
comparison to petroleum-based plastics, biopolymers have low
physical, mechanical, and chemical resistance. Furthermore, the
brittleness and high permeability to water vapor and oxygen of
some bioplastics make them unsuitable for use in certain consumer
applications such as food packaging.
5. Environmental impacts of using biopolymers
The environmental impact resulting from the production and
use of biopolymers has always been an important factor to consider
in their development and production. Proper assessment of such
impacts requires a keen knowledge of the environmental impacts
of biopolymers relative to their petrochemical counterparts. To this
end, life cycle analysis (LCA) can be used to determine the envi-
ronmental impacts of a material and/or its production process
throughout its production, distribution, use, and disposal. It should,
however, be noted that LCA does not cover social, ethical, and
economic aspects. In this section, results from various LCA studies
 E. Kabir et al. / Journal of Cleaner Production 258 (2020) 120536 11

Table 5
Summary of representative LCA results for TPS, PHAs, PLA, and PBS.

Order Biopolymer Energy demand Greenhouse gas emissions Reference

1 TPS 649 MJ 25 kg CO2 eq. Dinkel et al. (1996)

2 PHAs 31.5 MJ/kg 0.28 kg CO2 eq./kg Kim & Dale (2005)
3 PLA ~480 MJ when distributed by 16-ton truck ~28 kg CO2 eq. when distributed by 16-ton truck Madival et al. (2009)
4 PBS 123.3 MJ/kg 5.5 kg CO2 eq./kg (at stoichiometric scale) Tecchio et al. (2016)

are presented and described for a number of commercially were two options for energy requirements: natural gas or bio-
important biopolymers (e.g., thermoplastic starch (TPS), poly- energy (corn stover used as fuel). A better GHG profile was acquired
hydroxyalkanoates (PHAs), polylactic acid (PLA), and polybutylene by the integrated process for PHA production with steam/electricity
succinate (PBS)). Table 5 summarizes the LCA results of the four generation (using bioenergy) than for conventional PE (natural
biopolymers. gas). On the other hand, the production of PHAs, if compared with
integrated steam/electricity generation by natural gas, was not
5.1. Thermoplastic starch (TPS) advantageous over petrochemical PE; its GHG profile was even
worse than that of PE.
TPS is produced by restructuration of starch with particular The energy needs for the production of PHB from different raw
quantities of plasticizers at specific extrusion conditions. TPS is materials (e.g., sugar beet, starch, fossil methane, and fossil meth-
used by itself (i.e., pure TPS) or as blends with petrochemical anol) through bacterial fermentation were compared to those of
polymers, depending on the type of application. An LCA was con- HDPE and PS (Heyde, 1998). The work concluded that the use of
ducted for TPS by comparing TPS with different petrochemical low- renewable feedstock requires the additional use of fossil resources.
density polyethylenes (LDPE) (Patel, 1999). In the study done by In addition, saving resources by employing renewable feedstock
Patel, it was expected that both TPS and LDPE are burned in can be achieved only if the whole process is optimized carefully. A
municipal solid waste incineration (MSWI) plants after their use. case study of PHAs derived from no-tillage corn was reported by
The results of the LCA were confined to energy and CO2 emissions. Kim and Dale (Kim and Dale, 2005). In this study, two systems (corn
According to the comparison between TPS and LDPE, TPS has a
savings potential of 55 GJ/t plastic (cradle-to-factory gate energy
use) relative to LDPE. In addition, the former can reduce CO2
emissions by 3.7 t CO2/t plastic compared to LDPE. Note that a
comparative LCA was carried out between TPS and LDPE films
(100 m2 and 150 mm) (Dinkel et al., 1996). The study assumed that
80% of the waste was incinerated, while 20% was landfilled in
Switzerland. The LCA results also showed that TPS film (25 kg CO2
eq.) has less impact on greenhouse gas (GHG) emissions than LDPE
film (67 kg CO2 eq.). Furthermore, TPS film (649 MJ) was estimated
to require less energy than LDPE film (1340 MJ).
An LCA study was reported for tires containing TPS fillers (Patel
et al., 2002). The biopolymeric filler-containing tires were reported
to have performance-related advantages (e.g., low weight,
improved wet skid performance, reduced rolling resistance, and
controlled stiffness). According to the LCA results, the use of
biopolymer in tires led to low CO2 emissions that are caused not
only by fuel savings due to low rolling resistance but also by the
reduction in cradle-to-factory gate emissions. For example, the
replacement of 20 and 50 wt % carbon black with TPS in tires helped
reduce CO2 emission by 3.53 and 9.52 g CO2/km, respectively,
which corresponds to reductions in the average CO2 emissions per
passenger car of 2 and 5%, respectively.

5.2. Polyhydroxyalkanoates (PHAs)

LCA studies showed that the total fossil energy requirements of

PHAs (e.g., polyhydroxybutyrate (PHB) and polyhydroxyvalerate
(PHV)) from cradle-to-factory gate can compete with high-density
polyethylene (HDPE), depending on the process of producing PHAs
(Gerngross and Slater, 2000). The minimum energy input for the
production of PHAs via fermentation was estimated to be higher
than that of polyethylene terephthalate (PET), but lower than that
of polystyrene (PS). However, the process energy requirements for
PHAs were estimated to be two to three times higher than those
needed for petrochemical polymers.
A detailed LCA study was conducted about a profile of GHGs that Fig. 9. Environmental impacts of biopolymer (PLA) vs. petrochemical polymer (PET
are potentially emitted from the production of PHAs derived from and PS). Reprinted from (Madival et al., 2009), Copyright 2009, with permission from
genetically modified corn (Kurdikar et al., 2000). In this study, there Elsevier.
12 E. Kabir et al. / Journal of Cleaner Production 258 (2020) 120536
grain vs. corn grain/corn stover) were investigated for producing
PHAs. The global warming impact of the former system was
1.6e4.1 kg CO2 eq./kg, whereas the latter system was 0.28
to 1.9 kg CO2 eq./kg. These values were dependent on associated
fermentation technologies. Overall, the PHA production process
using both corn grain and corn stover as the feedstock reduced
impacts on the environment, compared to that using corn grain as
the sole feedstock.
PHAs derived from whey were evaluated through LCA in terms
of sustainable process index (SPI) (Koller et al., 2013). The SPI
assessment was conducted to optimize ecological sustainability of
the process for archaebacterial production of PHAs from whey. It
was shown that the production of 1 kg PHA (at 300 L scale) inflicted
a higher ecological pressure (10,000 m2/kg polymer) than that of
equal amounts of petrochemical polymers (such as PE (~2000 m2/
kg polymer), polyethylene terephthalate (PET) (~2000 m2/kg
polymer), polypropylene (PP) (<2000 m2/kg polymer), and PS
(<2000 m2/kg polymer)). Accordingly, biopolymers derived from
renewable resources are not necessarily more environmentally
friendly than petrochemical polymers if produced without opti-
mization and process development.
5.3. Polylactic acid (PLA)
In 2003, an overview of applications of LCA was provided to
describe the production of NatureWorks™ PLA manufactured by
Cargill Dow (Vink et al., 2003). Based on their LCA results, total fossil
energy requirements of PLA were lower than those of petrochemical
polymers. Additional fossil energy savings were estimated by using
renewable fuel as an energy source for heat and power both by
integrating the energy required for the PLA unit with that required for
the lactic acid facility and by optimizing separation of the products.
There was also a comparative LCA of two diaper systems: (1) one
based on polyolefins (e.g., PP and PE); and (2) the other based on
PLA made from sugar beet, wheat, and maize (Hakala et al., 1997).
The two diaper systems had comparable environmental impacts for
most scenario parameters considered.
An LCA analysis for industrial production of PLA was carried out
in Thailand as a case study (Groot and Bore
n, 2010). The authors
concluded that biopolymers could offset environmental problems
associated with using petro-derived polymers (e.g., GHG emissions
and climate change). However, in order to further minimize the
environmental impacts of PLA, production procedures for lactic
acid need to be technologically improved (Groot and Bore
n, 2010).
Likewise, LCA of PLA clamshell containers was compared with that
of PET and PS clamshell containers (Madival et al., 2009). For the
clamshell containers, the transportation stage of the polymers and
containers was considered as one of the main environmental im-
pacts. PLA showed lower global warming emissions (~28 kg CO2 eq.
when distributed by 16-ton truck) than PET (~830 kg CO2 eq.) and
PS (~520 kg CO2 eq.). In addition, the use of non-renewable energy
was reduced by around 40% when the goods were transported by a
28-ton truck. Refer to Fig. 9 for a visualization of their results.
5.4. Polybutylene succinate (PBS)
The LCA was carried out to meaningfully evaluate the environ-
mental impact of PBS (Tecchio et al., 2016). The environmental
burden of PBS was compared to that of conventional PET at three
different production scales (i.e., pilot, industrial, and stoichio-
metric). For all three scales considered, the cumulative energy de-
mand (CED) of PBS was higher than that of PET. For instance, at
industrial scale, the CED of PBS (138.85 MJ/kg (PBS)) was lower than
that of PET (75.71 MJ/kg (PET)). It was evaluated that the produc-
tion of PBS emitted more quantities of greenhouse gases (such as
CO2, CH4, and N2O). The production of PBS at pilot scale, for
example, emitted 36.57 kg CO2 eq./kg (PBS), while the production
of PET emitted 23.98 kg CO2 eq./kg (PET). The results indicated that
environmental burdens for the production of PBS are higher than
those for PET. It was however recognized that the scaling up of the
PBS production process should lead to the reduction of CED and
GHG emissions (Tecchio et al., 2016). As such, the scale-up of PBS
production is beneficial to make its supply more environmentally
benign.
6. The role of biopolymers for sustainable development
Sustainable development can be defined as that “which meets
the needs of the present generation without compromising the ability
of future generations to provide their own needs” (Go
mez, 2014). If
one can manage natural resources properly, the economic and so-
cial goals of sustainable development are not difficult to achieve. To
meet these goals, it is important to maintain a list of issues (or
conditions) such as efficient use/consumption of resources, effec-
tive recycling, ecological mentality, development (or innovation) of
efficient technologies for renewable resources, ecosystem preser-
vation, and social participation (Izatul et al., 2012).
Concerns related to conventional polymers have been
increasing because of their non-renewability. Such polymers also
are known to be responsible for releasing carbon into the atmo-
sphere. The carbon footprint of plastic is around 6 kg CO2/kg plastic
throughout the life cycle (i.e., production to incineration) (Dormer
et al., 2013). Furthermore, the non-degradability of polymers cre-
ates environmental pollution that seriously affects ecosystems,
wild and marine life, and/or humans. As biopolymers are derived
from renewable sources, they can be considered as sustainable al-
ternatives for conventional plastics. Their neutral carbon lifecycle
also helps decrease the release of carbon dioxide into the atmo-
sphere, reducing the ‘human footprint’ on the environment. Bio-
polymers have low carbon footprint, with less cradle-to-plant-gate
greenhouse gas emissions than fossil fuel. As for example cradle-to-
plant-gate-greenhouse gas emissions of Polyamide 410, is nearly
zero (Ashby, 2016). As the amount of carbon dioxide generated
during its manufacture is offset by the amount of carbon dioxide
absorbed during the growth of its source castor bean plant. Ac-
cording to the Intergovernmental Panel on Climate Change (IPCC),
biopolymers could make significant contribution by removing up to
20 percent of the CO2 to limit global warming by 1.5
C (IPCC, 2018).
Apart from the known sources of biopolymers, scientists around
the world are researching, developing, and even in some cases
commercializing new products from a variety of renewable sources
and waste materials. Newlight Technology, USA collected concen-
trated methane and air from landfills, farms, and industrial sources
for use in the production of AirCarbon (Power Pallet, 2017). New-
light’s biocatalyst separates carbon and hydrogen from methane
and oxygen from air in the conversion reactor (Power Pallet, 2017).
The isolated carbon, hydrogen, and oxygen molecules are then
linked together to make a long chain thermopolymer known as
AirCarbon. AirCarbon is compatible with traditional polyethylene
so that it can be used in cast film, blown film, fiber spinning,
thermoforming, etc. (Power Pallet, 2017). Unorthodox raw mate-
rials from animal sources (e.g., wool (Conzatti et al., 2013), feathers
(Aranberri et al., 2017), silk (Alam et al., 2011), and horns (Kumar
et al., 2017)) also are used as fillers for polymers.
Poultry feathers consisting of keratin protein with several amino
acids can be used to produce biopolymer (Aranberri et al., 2017).
Such polymers can be used to make plastic plates and cups.
Biodegradable thermoplastic has been produced from bakery waste
(bread crust, stale bread, and sponge cake) by adding suitable ad-
ditives like natural antioxidants and plasticizers (EU BREAD4PLA
 E. Kabir et al. / Journal of Cleaner Production 258 (2020) 120536
project, 2015). Scientists from the National University of Singapore
(NUS), Singapore have developed a biodegradable packaging ma-
terial from grapefruit seed extract and chitosan that was demon-
strated to double the shelf life of bread relative to conventional oil-
based film packaging (NSUNews, 2016). Researchers from the US
Department of Agriculture successfully made plastic films from the
milk protein casein. Such film packages are considered to be 500
times better than conventional plastics at keeping oxygen away
from food (ACS, 2016).
Scientists from the French National Institute for Agricultural
Research were able to make biodegradable food trays from liquid
effluent of the dairy and oil industries and dry fractionation of
wheat straw (Europa, 2016). Several startup companies successfully
designed plastic products (e.g., edible tea bags, seasoning sachets,
food wrappers, water bottles, and cups) from seaweed (Khalil et al.,
2017). A research team from AINIA, Spain also successfully acquired
PHB from whey surplus used in the cheese industry as an alterna-
tive option for replacing conventional dairy product packaging
materials (Nielsen et al., 2017). However, sustainability of these
products depends on their acceptance or widespread use by soci-
ety. To accomplish such a goal, it is imperative to have strong so-
cietal commitment towards resource conservation and natural
preservation.
There are a number of distinctive advantages when using bio-
polymers over the non-degradable packaging materials. For
example, biopolymers can be built to offer a much clearer and
smoother surface, while there is less probability of imparting an
alternate taste to the item contained in conventional plastics
packaging (Chen, 2014). Nevertheless, biopolymers may have
higher water vapor permeability than the ordinary plastic. How-
ever, in some cases (like for freshly baked bread), the use of
biopolymer as packing media may let more steam or vapor diffused
out. Moreover, biopolymers can be employed in cosmetics pack-
aging too as it can feel softer and more tactile (Pilla, 2011). For such
application, it may offer less breakage, better lid adhesion, and
protection during shipping (Coles and Kirwan, 2011).
Although the genuine advantages of biopolymers are well-
known, there have been enormous efforts to upgrade their physi-
cochemical characteristics, especially with respect to barrier,
mechanical,and thermal properties. Likewise, the industrial fields
developed from polymer materials (such as packaging technolo-
gies) should also devise diverse effective methods to maximize
their applicabilities (e.g., with respect to marinating the oxygen,
moisture,and/or CO2 levels, quality,and health aspects of the
packaged foods). As such, the producers should keep in mind to
meet up the long distribution distances of their products with the
globalization of the markets (Farme, 2013).
Note that the current use of the biopolymers is mostly confined
to packaging industries. As biopolymers have the great potential to
reduce cost, energy, and materials for next generations, their po-
tential utility is expected to expand in diverse ventures in future
(e.g., electronics, food technology, nanotechnology, chemistry,
medicine, biotechnology, agriculture, and textile industry) (Mowafi,
2018). In this respect, biomedical application is recognized as one of
the most rapidly growing fields among others (e.g., therapeutic
devices, temporary implants, and three-dimensional scaffolds for
tissue engineering) (Song et al., 2018). Recently, a German chemical
company named Evonik has developed various biodegradable
polymer (medical) devices for sustainable drug release implants
(Song et al., 2018). Furthermore, some microbes were reported to
produce polymers naturally that can be used efficiently in dispos-
able items like sanitary products and diapers (Sinha, 2018). Two
Dutch scientists have developed a type of bioploymer from algae
which could be used in 3D printers (Skrabania, 2018). Lego com-
pany has also reported their plan to introduce sugarcane-derived
13
bioplastics for making trees, bushes, leaves, and other botanical
elements parts (Lego, 2018). Two toy companies, Bio-on and Italeri
also made proposals to introduce PHA-based toys to the market
(Bioplasticsnews, 2018). Due to the biocompatibility characteristics,
biopolymers have become a preferable choice in many membrane
applications (e.g., drug delivery, tissue engineering, hemodialysis,
and blood oxygenation) (Galiano et al., 2018). Further, the high
permeability and salt rejection nature of the biopolymers make
them suitable for reverse osmosis for water desalination (Lee et al.,
2011). Biopolymers based membrane can also be used for gas
separation, pervaporation, and water filtration (Galiano et al.,
2018). Biopolymers are using in cellulose fibers as electrode ma-
terials as well (Martin et al., 2013). Biopolymers were also applied
for the fabrication of dye sensitized solar cells, FTO/TiO2-dye/
CMKC/CMCE-NH4I þ I2/Pt (Rudhziah et al., 2015). Likewise, they
have also been used in flexible, biomolecule-based photo-
electrochemical cells (Suresh et al., 2016). Metal-based electrodes
have low skin-surface interface to cause discomfort to the patients.
The use of flexible conductive biopolymer nanocomposite
(CPC) has also been proposed as a fascinating and promising
alternative in biomedical applications. CPCs are made by struc-
turing a network of conductive nanofillers into an insulating
biopolymer matrix (Tematio et al., 2017). CPCs also bring new
prospects for replacing traditional materials in many energy-
related fields such as photo-voltaic application, electronic and
energy storage devices, transistors, electromagnetic interference
shielding materials, light emitting diodes, and more (Tematio
et al., 2017).
7. Conclusions
It is well known that petroleum-based synthetic polymers have
exerted numerous adverse environmental impacts, as most of them
end up being dumped at landfills and/or being delivered to oceans
and soils. Bridgeable polymers would be a suitable option to
overcome such pollution. Nevertheless, the use of biopolymers as
biofuels has drawn huge interest from researchers to explore this
relatively new field. Additionally, biopolymers can be applied
progressively in surgical and therapeutic applications as well as in
drug delivery tools, a conceivable application in nano-medicine.
The market for biopolymers is growing rapidly with increased
societal interest in environmental sustainability. However, the use
of degradable plastics over regular plastics still remains a conten-
tious issue because of the cost involved in their production. More
research efforts should be focused on producing biopolymers from
biomass feedstock more cost effectively. The biotechnology of mi-
croorganisms can play a crucial role in the generation of bio-
polymers to compete with current barriers. Nevertheless, the
generation of these biopolymers ought to comply with the goal of
increasing the sustainability of materials and processes throughout
the product’s lifetime, without competing with customary food
sources, while at the same time lessening long-term reliance on
non-renewable resources. Moreover, the feasibility of biopolymer
products at laboratory scale should be validated at pilot-scale prior
to real-world applications. At present, the high cost of biopolymer
products remains as the major limitations to gain competitiveness.
Continuous development in the technology and innovative efforts
may help reduce this cost barrier to make it a worthy option for the
industries. Apart from the commodity products, biopolymer has
great prospects to be applied toward various hi-tech fields such as
stem cell sector and photovoltaic application.
Acknowledgements
This study was supported by a grant from the National Research
14 E. Kabir et al. / Journal of Cleaner Production 258 (2020) 120536
Foundation of Korea (NRF) funded by the Ministry of Science, ICT &
Future Planning (No. 2016R1E1A1A01940995). Dr. Rajnish Kaur
acknowledges the SERB-DST, India (Ref No.: PDF/2016/001870) for
her research grant.
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