Advanced Industrial and Engineering Polymer Research 3 (2020) 27e35

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Advanced Industrial and Engineering Polymer Research

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Biodegradable polymers and green-based antimicrobial packaging

materials: A mini-review
Yajie Zhong a, Patrick Godwin b, Yongcan Jin a, **, Huining Xiao b, *
a
Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China
b
Department of Chemical Engineering, University of New Brunswick, Fredericton E3B 5A3, Canada

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

Article history: Recently, the demands for biodegradable and renewable materials for packaging applications have
Received 21 August 2019 increased tremendously. This rise in demand is connected to the growing environmental concerns over
Received in revised form the extensive use of synthetic and non-biodegradable polymeric packaging, polyethylene in particular.
29 September 2019
The performance of biodegradable polymers is discussed in this review, with a particular focus on the
Accepted 4 November 2019
blends of starch and other polymers. Furthermore, in food packaging industry, microbial activities are of
great concern. Therefore, incorporation of antimicrobial agents or polymers to produce barrier-enhanced
Keywords:
or active packaging materials provides an attractive option for protecting food from microorganism
Biodegradable polymers
Packaging materials
development and spread. Additionally, the barrier, mechanical and other properties of biodegradable
Antimicrobial packaging polymers are discussed. Lastly, the existing and potential applications for bioactive coatings on antimi-
Starch crobial packaging materials are also addressed.
© 2019 Kingfa SCI. & TECH. CO., LTD. Production and Hosting by Elsevier B.V. on behalf of KeAi
Communications Co., Ltd. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction benefits for greenhouse gas balances and other environmental

Packaging waste, those from non-biodegradable polymers in
particular, has become a significant part of municipal solid waste,
resulting in increasing environmental concerns. Discarded pack-
aging material is also a very obvious source of litter, posing a major
waste management challenge. Among these materials, poly-
ethylene (PE) is the most commonly-used petroleum-based poly-
mer in packaging application [1,2]. It is extremely difficult for PE or
other types of petroleum-based polymers to be biodegraded after
disposing in land or coast, thus creating varying levels of contam-
ination. To address this problem, much attention has been paid to
developing the biodegradable polymers from renewable resources
in recent years [3e5], which is also driven by the global environ-
mental awareness. The degradation of biodegradable polymers
disposed in bioactive environments (e.g., landfills) is often induced
by microorganisms (e.g., bacteria, fungi) via enzymatic catalysis
processes. The polymer chains may also be broken down by non-
enzymatic processes like chemical hydrolysis. The end products
of biodegraded polymers typically include CO2, CH4, water, biomass
and other natural substances, which are relevant to potential
* Corresponding author.
** Corresponding author.
E-mail addresses: jinyongcan@njfu.edu.cn (Y. Jin), hxiao@unb.ca (H. Xiao).
impacts. The recyclable biological process of biodegradable poly-
mers is shown in Fig. 1. Biopolymers originate from various natural
resources, such as starch, cellulose, chitosan and proteins from
plant and animal origins. Those natural polymers are the attractive
alternatives for non-biodegradable and petroleum-based or syn-
thetic plastic packaging materials, owing to their green features.
Among various biopolymers, cellulose and starch are particularly
abundant. In conjunction with their renewable, inexpensive, envi-
ronmentally friendly, biodegradable, and biocompatible features,
those biopolymers have become increasingly popular [6,7].
As one of the unique packaging materials, antimicrobial pack-
aging is not only beneficial to the consumers but also to the food
and hygiene products. The innovative packaging is able to extend
the shelf life of products through deactivating or reducing the
growth of various bacteria or fungi which are harmful to human
health [8]. The development of biodegradable materials and
antimicrobial green-based materials for packaging is of importance
though the dilemma between biodegradable behavior and anti-
microbial activity should be addressed as well [9,10]. The review
presented herein highlights several types of biodegradable poly-
mers and green-based antimicrobial packaging materials; and
focuses on the characteristics of various biodegradable polymers.
Some recent advances and emerging technologies associated with

https://doi.org/10.1016/j.aiepr.2019.11.002
2542-5048/© 2019 Kingfa SCI. & TECH. CO., LTD. Production and Hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd. This is an open access article under the
CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
28 Y. Zhong et al. / Advanced Industrial and Engineering Polymer Research 3 (2020) 27e35
Fig. 1. Cyclic biological process of biodegradable polymers.
the packaging application of biodegradable polymers are also
discussed.
2. Biodegradable polymers
2.1. Definition and classification of biodegradable polymers
Biopolymers can be used to substitute non-biodegradable plas-
tics to reduce the environmental impact and petro-dependence. As
alternative bio-packaging materials, biopolymers allow the pack-
aging materials to be biodegradable or compostable completely.
Biodegradation of biopolymers involves the hydrolytic or enzymatic
cleavage of bonds in the polymer. Biodegradation is often defined as
an event which occurs via the action of enzymes and/or chemical
decomposition associated with living organisms (bacteria, fungi,
etc.). It is worth noting that the other processes like photo-
degradation, oxidation and hydrolysis may also have impact on the
structure and chains of polymers prior to or during biodegradation.
Biodegradable polymers may be classified into different types
according to their synthesis processes and sources, which are out-
lined in Fig. 2 [11,12]. They are directly obtained from biomass
(proteins and polysaccharides), synthetic biopolymers from biomass
(poly(lactic acid) (PLA)) or petrochemicals (e.g., (polycaprolactone)
(PCL), poly(glycolic acid) (PGA), poly(butylene succinate-co-adipate)
(PBSA)) or those obtained by microbial fermentation (e.g., poly
(hydroxyalkanoates) (PHA), poly(hydroxybutyrate) (PHB)).
2.2. Properties and drawbacks of biodegradable polymers
There are several types of biodegradable polymers in the market
at the moment. The structures of selected biodegradable polymers
are shown in Fig. 3. The characteristics of each polymer is detailed
as follows.
2.2.1. Starch
One of the most abundant and renewable polysaccharides in
plants is starch [13]. Native starch consists of two types of glucose
polymers, namely amylose and amylopectin. While amylose is a
chain of D-glucose unit that is connected together by a-1,-4 bonds,
the amylopectin contains short chains of a-1,-4 linked D-glucose
units that are branched by a-1,-6 bonds. Although starch is a
biodegradable polymer that can be manufactured in large quanti-
ties at relatively low cost, handled easily and form film products
with low oxygen permeability, the major challenge with native
starch is that, it is brittle and hydrophilic. These limit its various
applications such as its use for the manufacturing of plastic bags
and food packaging [14]. To enhance its flexibility and improve the
easiness for processing or plasticizing starch, various plasticizers
(glycerol, glycol, sorbitol) are employed to convert the starch into
thermoplastic starch (TPS) via the application of heat and shear
over extrusion processes [15,16].
2.2.2. PLA
PLA is a biodegradable polyester obtained from lactic acid dur-
ing the fermentation of renewable crops such as sugar beets and
corn. This polyester has attracted attention because it is readily
available and cheap. Lactic acid is usually synthesized from either
bacterial fermentation or from synthesis of petrochemicals. PLA is
prepared from the condensation polymerization of D- or L-lactic
acid or from the ring-opening polymerization of lactide monomer
from lactic acid. The PLA with low molecular weight is manufac-
tured by the direct polycondensation of lactic acid. On the other
 Y. Zhong et al. / Advanced Industrial and Engineering Polymer Research 3 (2020) 27e35 29

Fig. 2. Representative biodegradable polymers based on two resources.

hand, high molecular weight PLA is produced from the ring-
opening polymerization and it exhibits better mechanical proper-
ties [17]. Moreover, the high molecular weight PLA has also been
generated via the azeotropic condensation polymerization of lactic
acid [18].
PLA has been widely accepted as biodegradable polymer for
packaging materials owing to its stiffness, transparency, process-
ability and biocompatibility. When compared with other bio-
polymers such as PHA, PEG and PCL, PLA exhibits a better thermal
processability, which allows for the various processing methods of
PLA such as injection molding, blow filming, cast filming, fiber
spinning, thermoforming, etc. [19]. Furthermore, PLA presents a
medium level of water and oxygen permeability that is comparable
to that of polystyrene [20,21]. However, PLA has a low resistance to
oxygen permeation, and it is also brittle with less than 10% elon-
gation at break. These properties limit its applications that require
plastic deformation at higher stress levels. To address this chal-
lenge, blending PLA with highly exfoliated clay in conjunction with
thermoplastic starch has proven to satisfactorily produce materials
with improved mechanical strength [22]. The bending of PLA with
PHB by melt blending has been considered to be a facile way to
improve the properties of PLA. When PLA was blended with PHB,

Fig. 3. Structures of selected biodegradable polymers.

30 Y. Zhong et al. / Advanced Industrial and Engineering Polymer Research 3 (2020) 27e35
there was an improved oxygen barrier, water resistant and
mechanical properties of the polymer as compared with pure PLA.
This demonstrated a valuable option for food packaging application
[23].
2.2.3. PCL
PCL is a thermoplastic biodegradable polyester with good
thermal processability, low melting point and low viscosity. It is
synthesized by the polymerization of ε-caprolactone. Because of
the weak barrier properties and poor mechanical properties of PCL
which are attributed to its low melting point, PCL application as a
biodegradable polymer in the packaging industry is limited. To
increase the scope of its applications, PCL is usually blended with
other polymers (e.g., cellulose propionate, polylactic acid, and
cellulose acetate butyrate) to improve stress crack resistance,
dyeability and adhesion [24].
2.2.4. PHA/PHB
Another promising material applied in packaging, medical and
agriculture sector is PHA, which is a polyester of various hydrox-
yalkanoates that is synthesized from microbial fermentation. PHAs
are non-toxic and crystalline thermoplastic elastomers with lower
melting point. They are biocompatible with good UV resistance,
physical and chemical properties. These properties depend on the
PHA monomer compositions. PHAs application is constrained due
to its poor mechanical properties, incompatibility with conven-
tional thermal processing techniques, as well as their susceptibility
to thermal degradation [25].
PHB is the most common representative of PHA with a high
degree of crystallinity. It has been equally considered for short-
term food packaging applications [26]. It has the advantage of
biodegradability by the action of PHA hydrolases and PHA depo-
lymerases forming (R)- and (S)-hydroxybutyrates and nontoxic
compounds under aerobic and anaerobic conditions [27]. PHB with
crystallinity up to 70%, exhibits remarkable mechanical properties
like polyethylene. Furthermore, PHB is suitable for food packaging
applications owing to its lamellar structure which contributes to its
superior aroma barrier properties with water vapor permeability.
PHB has a comparable melting point temperature with PLA, and
thus allows for the blending of both polymers in their melted state.
However, the poor mechanical performance and melt processing
behavior of PHB, i.e., high brittleness, low thermal stability and
difficult processing, along with insufficient barrier properties, limit
its widespread use [28]. Many attempts are being made to improve
its properties for packaging application [29,30]. Plasticized PLA-
PHB blends incorporated with catechin were prepared by melt
blending. PHB-added materials improved the mechanical proper-
ties of the plasticized PLA-PHB blends, which showed potential as
biobased active packaging for fatty food [31].
3. Starch/polymer blends
Biodegradable polymers have the potential to ameliorate the
problems of non-biodegradable plastic waste pollution. However,
the majority of biodegradable plastics are not commonly used since
they are quite expensive and the range of the material selection
suitable for various end-use products is limited. For biodegradable
polymers to have wider industrial applications, it is important to
minimize its cost by blending them with renewable feedstock.
A natural biopolymer synthesized from renewable resources is
starch. Since starch is inexpensive, readily available and totally
biodegradable, there has been growing interest in synthesizing
starch-based products. Blending biodegradable plastics with TPS
appears to be the most promising approach to minimize the cost of
biodegradable polymers.
Starch, in particular, is water sensitive and its film properties are
heavily dependent on the moisture content, exhibiting relatively
low mechanical resistance. Moreover, due to the high melting point
and lower thermal decomposition temperature of starch, it has
poor thermal processability [32]. To make starch suitable for tar-
geted applications, it is necessary to blend starch with other poly-
mers. The properties of polymers can be altered or modified by
blending [33,34]. Blends of starch with polymers which have
enhanced water resistant and good mechanical properties as
packaging materials are not only biodegradable but also econom-
ical. These starch-based thermoplastic materials blending with
polymers such as polyolefins, PHA, PLA and PCL, have received
wider industrial applications ranging from film blowing, extrusion
applications, blow moulding, injection moulding and foaming [35].
3.1. Blends of starch and polyolefins as compostable packaging
Prior to developing completely biodegradable packaging, starch
has been blended with polyolefins, low-density polyethylene
(LDPE) and linear low-density polyethylene (LLDPE) in particular, to
produce compostable (though not 100% biodegradable) and envi-
ronmentally friendly materials for packaging application [36].
Blending or compounding is often conducted in a twin-screw
extruder followed by either cast filming or blown filming process.
To ensure the compatibility between PE and TPS, a compatibilizer,
e.g., PE grafted with maleic anhydride, is often needed, particularly
at relatively high content of TPS (>20 wt %). In the presence of the
compatibilizer, TPS could be well dispersed in PE matrix. The re-
sults from DSC analysis also indicated that starch had strong impact
on crystallization of PE. The packaging materials with desired
mechanical properties required less amount of TPS (approximately
15 wt% TPS); however, to achieve highly compostable materials, a
higher amount of starch (up to 60 wt%) is required. The balance
between the mechanical properties and biodegradability remains a
challenge [37]. TPS can easily be blended with high density poly-
ethylene (HDPE) using deep eutectic solvents (DES) as modifiers,
which could increase the ductility of compounds [38]. It is worth
noting that EDS often acts as a lubricant rather than a plasticizer.
As a further extension of compostable starch/polyolefin blends,
polypropylene (PP) was compounded with starch using a single
screw extruder and molded via injection molding, leading to the
compostable materials for various applications such as disposable
dishes and folk etc. The blends of PP and starch with better
performance were prepared with a twin-screw extruder in the
presence of various compatibilizers. The mechanical and thermal
properties of resulting starch/PP blends were improved with the
addition of compatibilizers, owing to the improved dispersion of
starch in PP matrix and the enhanced adhesion between PP and
starch [39].
Reactive extrusion with catalysts was employed to generate
cross-linking reactions within polymer blends, resulting in films
with improved properties that are adequate as packaging materials.
Blends of starch (native and oxidized corn starch) and polystyrene
(PS) containing glycerol as a plasticizer were prepared by reactive
extrusion in a twin-screw extruder using zinc octanoate (Zn(Oct)2)
as a catalyst, followed by compression molding. The results showed
that the catalyst used in the reactive extrusion promoted the cross-
linking between PS and starch, especially oxidized starch since the
oxidative modification process of the starch could potentially
activate the catalyst [40]. Impact, thermal and biodegradation
properties of high impact polystyrene (HIPS)/corn starch blends
prepared via melt extrusion with glycerol as a plasticizer were
evaluated. Results indicated that the properties of the blends were
dependent on the amount of starch and glycerol; and the
 Y. Zhong et al. / Advanced Industrial and Engineering Polymer Research 3 (2020) 27e35
as-prepared blends exhibited fast degradation during the soil burial
test [41].
3.2. Compounding starch with biodegradable polyester and PLA for
biodegradable films
3.2.1. Compounding starch with biodegradable polyester
(PCL and PHB)
Blending starch with PCL even at a low PCL content is an
effective approach to tackle the issues related to the weakness of
pure starch materials, such as high moisture sensitivity, low resil-
ience, and high shrinkage [42]. Compounding with PCL, the
dimensional stability and the impact resistance of native starch are
significantly enhanced. The content of the plasticizer and compo-
sition of the blend vary the mechanical properties and glass tran-
sition temperature of TPS/PCL [43]. TPS/PLA and TPS/PCL blends are
similar in both the compatibility and the role of components.
Introducing fiber and nano-clay to PCL/starch blends can reinforce
the blends further. Furthermore, this also improves the other
properties of the blends such as degradation rate, hydrolytic
stability, and compatibilization between starch and PCL [44].
Blending of starch with PHB was also investigated in an attempt
to overcome PHB limitations and exploit inherent properties of
starch [45]. PHB/EVA/starch blends with fine dispersion of
starch were prepared with in-situ compatibilization in the presence
of maleic anhydride (MA) and benzoyl peroxide (BPO) as
reactive agents. EVA/starch/MA/BPO/glycerol mixture was pre-
compounded, prior to being blended with PHB. It was found that
although the tensile strength of the blends increased with the in-
crease of MA content up to 0.09%, further increasing MA lowered
the strength because of the changes associated with the size of
starch particles, phase morphology and EVA domains. Furthermore,
the co-continuous morphology led to an increase in elongation at
break, thus giving a rise in toughness of the blends. The improved
impact strength is attributed to the enhanced affinity between
EVA-g-starch and PHB, compared to PHB/starch blends [46].
3.2.2. Compounding starch with PLA
Blending starch with PLA in adequate proportions in the pres-
ence of compatibilizers could lead to high-performance films that
can meet the packaging requirements [18,47]. The combination of
starch and PLA allows the blends or multilayer films to better suit
the requirements for packaging application due to their comple-
mentary characteristics. Earlier research on PLA/starch blends
focused on minimizing the cost while still maintaining biode-
gradability. Recently, much attention has been paid to strength-
ening PLA/starch blends. Plasticizing PLA/starch blends tends to
improve the compatibility, which has been regarded as a promising
means to enhance the toughness of the blends. Bilayer films of
amorphous PLA and starch were prepared by compression
moulding of TPS films and casting PLA layers with or without cin-
namaldehyde. Both tensile strength and water vapor barrier of
bilayer films were improved compared to the net starch films.
Moreover, the high transparency was well maintained while the
oxygen barrier was similar to that of starch-alone films [48].
4. Antimicrobial-modified biodegradable packaging
Antimicrobial packaging plays an important role in food pack-
aging, which could extend the shelf life and assure the preservation
of food. Antimicrobial packaging can be prepared by incorporating
bioactive agents directly into the packaging compounds, by coating
bioactive agents onto the surface of the packaging, or by film-
forming using antimicrobial polymers [49]. Starch and starch de-
rivatives, PHB and PLA have many features compatible with many
31
antimicrobial agents for packaging. They have been scrutinized for
both pathogenic and spoilage microorganisms in biomedical and
food applications at different testing conditions. The active films
prepared by solvent casting demonstrated the release of antimi-
crobial agents and efficacy against target microorganisms [50,51].
4.1. Starch-based antimicrobial packaging materials
A number of antimicrobial agents and starch are compatible; and
resulting starch films demonstrated the abilities to deactivate many
species of pathogens [52,53]. Among various antimicrobial peptides,
nisin or pediocin has been incorporated into the starch-halloysite
nanocomposite films via a casting method for food preservation.
As-prepared films not only possessed the improved thermal stabil-
ity, mechanical strength and water barrier properties, but also
showed high antimicrobial activity against L. monocytogenes and
C. perfringens [54]. The effectiveness of antimicrobial packaging
materials often depends on the amount of antimicrobial agents
loaded in the polymer matrix and the optimal amount released over
time. The performance of the film is usually governed by the
formulation protocol and materials used. However, the amount of
disinfectants incorporated into a polymer or starch matrix should be
properly controlled either for a particular application or minimizing
the negative impact on environments. It was reported that the starch
containing propolis improved antimicrobial efficacy against various
pathogens even at very low dosages [55]. Antimicrobial agents
extracted from natural sources, such as essential oils (EO), also
showed the desired antimicrobial activity with no harmful effect on
food, which has been employed for food packaging [56]. Similar
systems based on TPS/layered silicates bionanocomposites contain-
ing EO for food packaging were also reported [57,58]. The release
profile of antimicrobial agents in the composites is often controlled
by formulation variables or the interaction among the components
in the composite [58].
Through melt-blending of antimicrobial thermoplastic starch
(ATPS) with LLDPE, antimicrobial packaging film has been pre-
pared. Polyhexamethylene guanidine hydrochloride used as the
antimicrobial agent was blended with starch. The derived LLDPE/
ATPS films demonstrated an excellent antimicrobial activity against
Escherichia coli (E.coli) [59]. Furthermore, the antimicrobial prop-
erty and biodegradation behavior of novel antimicrobial biode-
gradable poly(butylene adipate-co-terephthalate) (PBAT)/TPS films
before and after a three-month soil burial test have been studied.
Results demonstrated that both starch and PBAT were biodegrad-
able and TPS showed excellent growth inhibition against E. coli
during the biodegradable test [60].
Since antimicrobial-modified starch renders itself more hydro-
philic, the enhancing of the compatibility between the modified
starch and PBAT is essential [61]. Fig. 4 illustrates the role of com-
patibilizer along with a typical compatibilizer synthesized from the
copolymerization of styrene (St), maleic Anhydride (MAH) and
glycidyl Methacrylate (GMA). Among them, St chains lead to the
hydrophobic part of compatibilizer; whereas anhydride and gly-
cidyl groups are hydrophilic and enable the covalent bonding with
starch, thus further improving the compatibility between starch
and PBAT.
4.2. PHB-based antimicrobial packaging materials
The application of PHB is not limited to packaging materials.
PHB can be used in encapsulation of food supplements and as
carrier in nutrients delivery [62,63]. PHB films bearing various
antimicrobial agents demonstrated the high activity in inhibiting
the growth of microorganisms and the controllable release of dis-
infectants which kinetics can be described with Fickian diffusion
32 Y. Zhong et al. / Advanced Industrial and Engineering Polymer Research 3 (2020) 27e35
Fig. 4. Schematic of the linkages induced by compatibilizer and the chemical structure of ter-polymer as a compatibilizer.
model [62]. Various natural antimicrobial agents, including vanillin,
sophorolipid or eugenol, were incorporated in PHB-based bio-
materials at different dosages for active packaging materials. PHB
films containing vanillin and eugenol even in a small amount
(80 mg/g PHB) were found to be effective against different bacterial
species [64,65]. PHB/TPS active films with eugenol also exhibited
anti-mould or antifungal activity against Botrytis cinerea and anti-
oxidant activity [66]. However, the incorporation of these natural
antimicrobial agents in PHB frequently decreases the thermal sta-
bility and mechanical properties of the films [64].
Apart from natural antimicrobial agents, synthetic disinfectants
were also employed in PHB-based packaging materials. Nevertheless,
for food packaging application, the dosage of antimicrobial agents
should be well controlled [67]. PHB/PCL/organo-clay nanocomposites
containing nisin demonstrated good inhibiting effect against Lacto-
bacillus plantarum; and as a result, the shelf life of processed meat
packed with the nanocomposite film was extended [68]. Zinc oxide
(ZnO) nanoparticle is also an inorganic and cost-effective antimi-
crobial agent for food packaging. Growth of Gram-positive bacterium
(Staphylococcus aureus) was completely inhibited by plasma-treated
PHB film loaded with ZnO nanoparticles [69].
4.3. PLA-based antimicrobial packaging materials
The incorporation of antimicrobial agents in PLA matrix enabled
the agents to be released in a controllable manner, thus improving
their effectiveness against microorganisms [70e72]. Antimicrobial
agents incorporated in PLA coating layer create a hydrophilic sur-
face which prevents the microorganisms from adhesion on the
surface of films. In order to meet special requirements for
biomedical applications, different methods for the surface modifi-
cation of PLA were developed, e.g., the surface modification of PLA
with silver nanoparticles to create antimicrobial nanocomposite
films [70]. PLA/PBAT intercalated with organoclay bearing antimi-
crobial natural rosin acid via melt blending led to the
nanocomposites for green packaging application. Moreover,
PLA/PBAT nanocomposites containing rosin acid also exhibited
effective antimicrobial and anti-mold activities compared to pris-
tine PLA nanocomposites [73].
Biodegradable active films based on PLA blended with PHB were
also reported. This polymer was incorporated with carvacrol as
active agents and lactic acid oligomers (OLA) as plasticizers and
were extruded and fully characterized in their functional capacities
for antimicrobial active packaging. PLA/PHB active films exhibited a
good barrier to water vapor, while the resistance to oxygen diffu-
sion decreased as more of OLA and carvacrol were added.
Furthermore, the antimicrobial and antioxidant properties of the
proposed formulations improved with the presence of carvacrol
and even with enhanced inhibition capacity against Staphylococcus
aureus if compared to Escherichia coli at short and long incubation
times [74]. Binary and ternary PLA-based nanocomposites with
cellulose nanocrystals (CNC) and lignin nanoparticles (LNPs) were
prepared by reactive melt grafting. LNPs with antioxidant activity
incorporated in the films proved to be efficient in antimicrobial
activity against plant pathogens. Furthermore, the combination of
CNC and LNP created a synergistic effect on the antioxidation
activity of ternary PLA-based films [75].
5. Testing of polymer degradation
As previously mentioned, polymer biodegradation is a natural
complex phenomenon, which is difficult to be fully simulated in the
laboratory environment due to a number of parameters related to
the entire biogeochemical process. Therefore, the current situation
offers limited flexibility in methodologies for testing polymer
biodegradation. For instance, the research on microbial degrada-
tion only provides a small variety of fungal and bacterial species.
Finding the same environmental conditions is hardly possible. In
addition, the ideal experiment to trace the change of polymers is
time consuming, which may take months or even years. In order to
 Y. Zhong et al. / Advanced Industrial and Engineering Polymer Research 3 (2020) 27e35 33

Table 1
List of currently active ASTM standards sorted by category.

Category Standard

Aerobic atmosphere D6400e12 “Standard specification for labeling of plastics designed to be aerobically composted in municipal or industrial facilities”
D5338e11 “Standard test method for determining aerobic biodegradation of plastic materials under controlled composting conditions,
incorporating thermophilic temperatures”
D5988e12 “Standard test method for determining aerobic biodegradation of plastic materials in soil”
D6340e98(2007) “Standard test methods for determining aerobic biodegradation of radiolabeled plastic materials in an aqueous or compost
environment”
D6691e09 “Standard test method for determining aerobic biodegradation of plastic materials in the marine environment by a defined microbial
consortium or natural sea water inoculum”
Anaerobic D5210e92(2007) “Standard test method for determining the anaerobic biodegradation of plastic materials in the presence of municipal sewage
atmosphere sludge”
D5511e12 “Standard test method for determining anaerobic biodegradation of plastic materials under high-solids anaerobic-digestion conditions”
D5526e12 “Standard test method for determining anaerobic biodegradation of plastic materials under accelerated landfill conditions”
Other auxiliary D5929e96(2009) “Standard test method for determining biodegradability of materials exposed to municipal solid waste composting conditions by
standards compost respirometry”
D6691e09 “Standard test method for determining the stability of compost by measuring oxygen consumption”
D6954e04(2013) “Standard guide for exposing and testing plastics that degrade in the environment by a combination of oxidation and
biodegradation”

In general, these standards have been divided into three categories according to the applied atmosphere and purpose: (1) aerobic atmosphere, (2) anaerobic atmosphere and
(3) other auxiliary standards.

meet different requirements and situations, a series of techniques 6. Conclusions

have been performed in this area. One of the most important proofs
that polymer materials have been consumed by microorganisms is
the release of carbon dioxide. The examination of carbon dioxide is
appropriate for the scenario that the biodegradable polymer is the
only carbon source into the environment. Other low molecular
weight metabolites (e.g., alcohols, fatty acids, aldehydes, and
methane, etc.) can be assayed by gas chromatography with mass
spectrometry (GC-MS) [76]. The residual polymer and its oligomers
are often analyzed via gel permeation chromatography (GPC) to
monitor the changes of molecular weight (MW) and MW distri-
bution [77].
To determine whether certain polymeric materials are biode-
gradable or compostable, standard organizations, such as the
American Society for Testing and Materials (ASTM) as well as the
International Organization for Standardization (ISO), have pub-
lished a series of standards for biodegradability and compostability
in different exposure environments. Generally, these standards
describe definitions, testing guidelines, time frames, procedures,
conditions, limits and results interpretation. The standards are
concordant between countries, but there is no globally accepted
standard for each area at present [78,79].
As one of the well-received standard specifications for com-
postable materials, ASTM D6400 covers the requirements for
labelling biodegradable polymers as compostable in municipal and
industrial composting facilities. In order to claim a certain material
is compostable, it must meet requirements that include satisfactory
disintegration, biodegradation, terrestrial and aquatic safety in a
controlled laboratory scale composting test.
It is worth noting that biodegradability is an essential prereq-
uisite for compostability according to ASTM D6400. A material is
compostable must be biodegradable. However, the reverse is not
necessarily true. In other words, if a material can be labeled as
biodegradable in composting environments, it is able to be claimed
as compostable. On the other hand, a biodegradable material which
is able to degrade in a fixed time frame and environment but
different from specifications for composting would be termed
biodegradable instead of compostable [80].
Besides ASTM D6400, a number of other ASTM standards
involving the biodegradability and compostability of a polymeric
material have been introduced and updated during the last two
decades. Table 1 lists a modified standard category covering
different standards (as of 2014) [81e91].
Although biopolymers are environmentally-friendly and most
attractive packaging materials, there industrial applications are
limited because of some factors such as their oxygen/water vapor
barriers, thermal resistance and other mechanical properties
related with costs. Due to these limitations, synthetic polymers are
the most widely used materials for packaging. To address these
limitations and encourage the industrial applications of bio-
polymers for packaging materials, there is the need for further
research to effectively enhance their shelf-life, quality, nutritional
values and microbial resistance. Additionally, the barrier properties
need to be enhanced. Biodegradable polymers consisting of
starch/cellulose fibers are most likely to make a firm growth in
applications.
Several methods of enhancing the properties and performance
of antimicrobial packaging materials such as polymeric blending,
chemical and physical modifications, nanocomposites, have
demonstrated promising potential for various applications. Both
functional and technical limitations have also been barriers to the
development and applications of antimicrobial packaging materials
in the food industry. Some of these limitations include vapor and air
barriers, the low processability of bioplastics, the stability of anti-
microbial agents under processing conditions, toxicity as well as
the changes in mechanical properties of the packaging materials.
Therefore, further research work should be focused on filling the
void linking the antimicrobial actions to microbial growth kinetics
in the packed foods in both lab and industrial approaches. This
would contribute to the initial efforts on the development of an-
timicrobials packaging. The strategies for improving antimicrobial
performances like synergism, nanocomposites and blending would
be the core tools for improving antimicrobial packaging and avoid
some of the limitations in the course of action.
Declaration of Competing Interest
There is no conflict interest.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (31770623) and NSERC Canada.
34 Y. Zhong et al. / Advanced Industrial and Engineering Polymer Research 3 (2020) 27e35

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