Application - of - Biodegradable - Polymers - in PKG
Application - of - Biodegradable - Polymers - in PKG
https://doi.org/10.1007/s41783-018-0049-y
REVIEW PAPER
Abstract
For last 50 years plastics are widely used for manufacturing of packaging materials because of their performance and ease in
production. With the advent of food processing industries there is a great demand for petroleum based packaging materials
for food applications. However, increased use of plastics has created serious ecological problems to the environment because
of their resistance to biodegradation. Biopolymers can be used as a solution to the problems posed by plastics as they easily
degrade in the environment and also mimic the properties of conventional polymers. Biopolymers can be classified into three
categories according to their origins of production. These are polymers extracted from biomass, synthesized from bio-derived
monomers and produced from microorganisms. There are different film formation methods for biopolymers like solution
casting method, melt mix method, electro spinning method, thermo pressing and casting, extrusion blown film method. The
quality of polymers can be expressed as different properties like physical, thermal, mechanical and barrier properties. This
review highlights the different kinds of biodegradable polymers, their characteristics with special emphasis on their market
potential for food packaging applications. The review revels that presently starch based, PLA, PHA and different blends
have been manufactured by industries, film properties compared with petrochemical based polymer for MAP and other food
packaging applications. Since information on biopolymers is widely scattered over many sources and are very scarce com-
pared to the conventional polymers, this article intends to give an overview of the state of the art on biodegradable polymer
packages for food applications.
Keywords Biopolymer · Film properties · Film production · Packaging · Food industry · MAP
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[3, 10]. India produces about 5.6 million tons plastic waste plastics were 63.7% and 36.3%, respectively. Majority of
every year. The environmental impact caused by excessive biodegradable plastics are made up of PLA (polylactic acid)
quantity of non-degradable waste materials is necessitating (10.9%), biodegradable polyesters (10.8%), biodegradable
research and efforts to develop new alternate materials that starch blends (9.4%) and PHAs (polyhydroxyalkanoates)
can be manufactured with the utilization of environmentally (3.6%). In bioplastics production, Asia contributes 63.1%,
friendly raw materials [3, 11, 12]. In recent years, bioplastics North America 13.5%, Europe 13.0% and South America
have emerged as an alternative to curb the menace caused 10.0%. Mostly biodegradable bioplastics are used for flexible
by the plastics. The European Bioplastics Organization state packaging and non-degradable bioplastics are used for rigid
that a plastic material is defined as a bioplastic if it is either packaging. The future of bioplastics focuses on the market
biobased, biodegradable, or features both properties. The for compostable, semi-durable and durable bio plastics used
need of replacement for the petroleum based plastic with bio in consumer and industrial applications [18]. Biodegrada-
based polymers is impartial because producing conventional ble polymers can be used for modified atmospheric storage
plastics consumes 65% more energy, unsustainable (due to (MAP) of fruits and vegetables instead of conventional poly-
environmental problems) and emits 30–80% higher green- mers. In MAP it is often desirable to generate an atmosphere
house gases than bioplastics [13, 14]. Biodegradable poly- low in O2 and/or high in CO2 to influence the metabolism of
mers are produced from renewable sources, are complete the product being packaged and the activity of decay-causing
biodegradable and mimic the properties of conventional organisms to increase storability and/or shelf life. In addition
polymers like polyethylene (PE), polypropylene (PP), poly- to atmosphere modification, MAP vastly improves moisture
ethylene terephthalate (PET), etc. [15]. Thus, biopolymers in retention, which can have a greater influence on preserving
the form of packaging materials are key innovations that can quality than O2 and CO2 levels [19–30]. Figure 1 represents
help in reducing the environmental impact of plastic produc- the global scenario of bioplastics application in different sec-
tion and can have high value generation potential from the tors at present and a future estimation [18].
agriculture feed stocks [16].
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CO2), which not only increase the shelf-life of the prod- moist food products. However, their excellent gas barrier
uct, but also add functionality in terms of convenience and properties make them suitable for their utilization in food
attractiveness to the consumers [32, 33]. The only problem packaging industry [36, 37, 40, 42–45].
with synthetic polymers is their resistance to degradation Group 2 Thesis includes polymeric materials which are
in the environment [34, 35]. According to ASTM stand- synthesized by a classical polymerization procedure such as
ards D-5488-94d, biodegradable is defined as capable of aliphatic aromatic copolymers, aliphatic polyesters, poly-
undergoing decomposition into carbon dioxide, methane, lactide, aliphatic copolymer (CPLA), using renewable bio-
water, inorganic compounds and biomass. With increased based monomers such as poly (lactic acid) and oil-based
awareness on sustainability, the packaging industries around monomers like poly-caprolactones. A good example of
the globe are looking for biopolymers as the replacement polymer produced by classical chemical synthesis using
of synthetic polymer. Biopolymers may be defined as the renewable bio-based monomers is polylactic acid (PLA), a
polymers that are biodegradable by the enzymatic action biopolyester polymerized from lactic acid monomers. The
of microbes. In last two decades, a lot of research has been monomers themselves may be produced via fermentation of
done on biopolymers for food packaging applications [36, various carbohydrate feed stocks. PLA may be plasticized
38]. with its monomers or, alternatively, oligomeric lactic acid.
Based on the researches biopolymer based packaging PLA can be formed into blown film, injected mold objects
materials may be divided into three main groups based on and coating. Therefore, all together explaining why PLA is
their origin and production (Fig. 2) [36, 39–41]. the first novel bio-based material produced at commercial
Group 1 Thesis constitutes polymers which are directly scale [36, 37, 40, 42–45].
extracted or removed from biomass. Certain polysaccha- Group 3 Polymers which are produced by microorgan-
rides such as starch, cellulose, and proteins (like casein and isms or genetically modified bacteria constitute this group.
gluten) constitute represent this category. All these are, by Till date, this group of bio-based polymers consists mainly
nature, hydrophilic and somewhat crystalline and create of the polyhydroxy-alkanoates, but developments with bac-
problems while processing. Besides, Further, their perfor- terial cellulose and other polysaccharides are also in pro-
mances are also poor especially in relation to packaging of gress. [39, 40, 42–45].
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Starch Based Biopolymers mechanical properties and facilitate the effective incorpo-
ration of bioactive ingredients and other functions such as
Starches are low cost polysaccharides, abundantly available tampering resistance, a barrier from oxygen, water vapor
and one of the cheapest groups of biodegradable polymers. and dust, etc. In non-food packaging polymer of keratin,
It is also known hydrocolloid biopolymer. It is composed casein, zein, gelatin and soy-protein, etc., could play a cru-
of amylose (poly-α-1, 4-D-glucopyranoside), a linear and cial role in the development of various commercial products
crystalline polymer and amylopectin (poly-α-1, 4-D-glu- like shopping bags, mulch film, flushable sanitary product,
copyranoside and α-1, 6-D-glucopyranoside), a branched etc. Blends of protein with non-protein, natural molecules
and amorphous polymer. The amylose and amylopectin such as chitosan, cellulose, and with synthetic polymer like
contents of starch ranges from about 10–20% and 80–90%, polypropylene, polyethylene, polyvinyl chloride, etc., were
respectively, depending on the source [47]. Amylose is prepared to improve the plastic properties of protein-based
soluble in water and forms a helical structure [44]. Various polymer which are suitable for food and non-food packag-
kinds of starches like potato, cassava, rice, corn, and tapioca ing [63].
are used for the preparation of biopolymers [48–50]. Starch
is usually used as a thermoplastic. It is plasticized through
destructuration in presence of specific amounts of water Polylactic Acid (PLA)
or plasticizers and heat and then it is extruded. So thermo-
plastic starch has high sensitivity to humidity. Starches are PLA is one of the biopolymer that has gained lot of atten-
poor resistance to moisture and their mechanical property tion in recent years because of its economic and commer-
restricts their uses. To improve these properties starches are cial viability during processing [62, 64]. Poly (lactic acid)
blended with various biopolymers and certain additives. (PLA) belongs to the family of aliphatic polyesters made
The list of research carried out on starch-based biopolymers up from alpha-hydroxyacids, including polyglycolic acid
is given in Table 1. or polymandelic [63–66]. The polylactic acid (PLA) is
obtained from the controlled depolymerization of the lac-
tic acid monomer obtained from the fermentation of sugar
Protein Based Biopolymers feedstock, corn, etc., which are readily biodegradable [65,
67]. PLA is a sustainable alternative to petrochemical-
Many of the proteins like gelatin, keratin, and casein con- derived products, since the lactides are produced by the
sisting very interesting features of polymers such as flex- microbial fermentation of agricultural byproducts, mainly
ural, shear strength, tensile modulus, as well as exceptional the carbohydrate rich substances [66, 68]. The yield of lac-
material properties including toughness, strength and elas- tic acid from different microorganisms and different sources
ticity. Thus, these proteins are also useful for the creation is shown in Table 2. PLA is becoming a growing alternative
of new biodegradable polymer for various commercial as a green food packaging material because it was found
applications. Protein-based biodegradable polymers they that in many circumstances its performance was better than
have an expanding range of potential applications in for- synthetic plastic materials [17].
mation of food and non-food packaging, and as biomate- PLA is usually obtained from polycondensation of D-
rials like reconstructive surgery, tissue engineering, etc. or L-lactic acid or from ring opening polymerization of
Therefore, the protein-based polymer can be used for the lactide, a cyclic dimer of lactic acid [36, 44, 45, 68, 70].
polymer reinforcement. The mechanical properties of pro- Properties that make PLA a good food packaging material
tein polymer can be further enhanced by blending them are their high molecular weight, water solubility resistance,
with other protein and/or non-protein molecules. Blending good process ability, i.e., easy to process by thermoform-
technology gives us an opportunity to develop next gen- ing and biodegradability [36, 37, 44, 68, 70]. PLA has the
eration biodegradable polymer/plastics which can replace tensile strength modulus, flavor and odor barrier of poly-
the conventional plastics from the market. In food packag- ethylene and PET or flexible PVC; the temperature stability
ing industries films made by protein polymers (like Milk and process ability of polystyrene; and the printability and
proteins, Whey protein, Gelatin, Wheat gluten, Corn, Zein, grease resistance of polyethylene. PLA can be processed by
Soy protein, Egg white, etc.) are used as an edible film so several approaches which include injection molding, sheet
that they can consume along with the food. Plant proteins extrusion, blow molding, thermoforming and film forming.
from soybean, wheat, and corn are readily available and Processed PLA comes in the form of films, containers and
films from these proteins have been investigated exten- coatings for paper and paper boards. PLA can be further
sively. The employment of protein-based film concepts to recycled by chemical conversion back to lactic acid and
edible packaging materials promises to improve barrier and then re-polymerized. Although PLA seems to be potential
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Table 1 The list of researches has been carried out on starch based biopolymers
Type of starch blend Film formation method Methodology Film characterization Observation Reference
Starch blended with chitosan and Solution casting method Starch concentration was varied FTRI, SEM The film made from starch (3%) [50, 51]
gelatin and concentration of chitosan blended with chitosan (2%) and
was kept constant gelatin (2%) resulted highest
density and low moisture uptake.
It exhibited smooth surface
with no visible pores and less
agglomerates
Wheat starch based antimicrobial Solution casting method The film was developed and the FTIR, XRD, SEM Antimicrobial films were pro- [51, 52]
films incorporated with lauric inhibition of spoilage and/or duced by incorporating chitosan
acid and chitosan pathogenic microorganisms was and lauric acid; it exhibited a
studied. The antimicrobial effect growth inhibition for B. subtilis
was tested on B. subtilis and but it is not effective for E. coli
E. coli
Corn starch blend with PVOH Solution casting method PVOH/Starch based polymers SEM The biodegradability of films [52, 53]
were developed and biodeg- made from corn starch was
radability, tensile tests was high in soil and compost and by
conducted. The biodegradability enzymes also
was studied by using differ-
ent methods like enzymatic
absorbency in water and acidic
solution, soil burial and compost
tests. The structure of the film
was characterized
Thermoplastic starch and chitosan Melt mix method The film was prepared and the SEM, FTRI Incorporation of chitosan resulted [53, 54]
effect of chitosan modification in increase of tensile strength
on the material was studied (up to 85%)
PVA/oxidized starch (OS) fibers Electrospinning technique PVA/OS fibers were developed SEM, FTIR, XRD and DSC The average diameter of fibers was [54, 55]
with electro spinning technique lowered by changing the solu-
at a applied voltage of 11 kV and tion concentration and weight
tip to collector distance of 12 cm ratio (PVA/OS). The fibers were
irregular and interspersed with
shuttle shape bead at the weight
ratio (PVA/OS) below 1:3
Biodegradable films from cassava Thermopressing and casting Starch was gelatinized which was – The films obtained by gelatini- [55, 56]
followed by thermopressing and zation were transparent and
solubilization of cassava starch resistant to traction. The starch
acetate in organic solvents, fol- acetate films were also transpar-
lowed by casting ent but breakable. The use of
these starch acetate films in
paper impregnation improved
the mechanical properties of the
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paper
Table 1 (continued)
Type of starch blend Film formation method Methodology Film characterization Observation Reference
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LDPE/sago starch Twin screw extruder blown film Low density polyethylene (LDPE)/ Fourier transform infrared (FTIR) The presence of high starch [56, 57]
method sago starch compounds with var- contents had an adverse effect on
ious sago starch contents were the tensile properties of LDPE/
prepared by twin screw extru- tapioca starch blends. High con-
sion with the addition of maleic tent of starch increased the rate
anhydride grafted polyethylene of biodegradability of LDPE/
as compatibilizer. Palm cooking tapioca starch films
oil was used as processing aid
Rice starch/flour Casting Films from rice starch and rice SEM analysis Preparing edible films from rice [57, 58]
flour were prepared by cast- flour is a new alternative for
ing, with glycerol or sorbitol as using this raw material, which
plasticizer is sometimes much cheaper than
commercial starches
Rice starch/polyvinyl alcohol Casting Different blends were made SEM, FTIR Films made up of rice starch and [58, 59]
(PVA) varying the concentration of rice PVA with a ratio of 2:8 showed
starch and PVA. Tensile strength highest TS. 10% sugar was
(TS) and elongation at break added with highest TS giving
(Eb) of the prepared films were four composition of Starch/
studied PVA blend to increase TS and
Eb. Films made up of rice starch
and PVA and sugar with a ratio
of 1:8:1 showed highest TS and
Eb and the recorded value was
14.96 MPa and 637% respec-
tively
Film produced from hydroxy- Casting method Biodegradable films were prepared Characterized for film tensile The increase in the starch concen- [59, 60]
propylated one of each of tuni, from the solutions containing strength, elongation, solubility, tration resulted in an increase
molatandihursago starch with different amounts of starch (3, 4 water vapor transmission rate in film tensile strength, but the
propylene oxide and 5%, w/v) by heating at 70 °C (WVTR) and oxygen perme- elongation, solubility, WVTR
for 30 min and glycerol (0.5%, ability (OP) and OP decreased. The films
[60, 61]
[61, 62]
food products, it exhibits certain limitations in unmodified
form, viz. it is more brittle and degrades easily at substantial
temperature rise. The list of patents on starch and PLA based
compatibilizers to improve
PLA/starch blend
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WO 2013042083 A1 Biodegradable films obtained from cassava starch and their manufacture process [69, 71]
EP 2712889 A1 Starch-based biodegradable material [70, 72]
US 8188185 B2 Biodegradable packaging film made from TPS/PLA blend [71, 73]
US 8133558 B2 Poly lactic acid blown film and method of manufacturing [72, 73]
US 20110135912 A1 Biodegradable packaging materials with enhanced oxygen barrier performance [73, 74]
US 8263197 B2 Poly lactic acid shrink films and methods of casting same [74, 76]
US 6987138 B2 Biodegradable poly lactide resin composition [75, 77]
diameters of 0.2–0.7 μm and are surrounded by a membrane Application of Biofilm for MA Packaging
coat composed of lipid and protein about 2 nm thick and can
be isolated as native granules or by solvent and enzymatic Modified atmosphere packaging is food preservation tech-
extraction [83–86]. niques in which the O2 concentration is reduced and CO2
concentration is increased to reduce the overall metabolic
processes, there by extend the shelf life of the commodities.
Pathways for Synthesis of Biopolymers It is an economical and simple technique for extending the
shelf life with preserving quality of fruits and vegetables.
Renewable sources like agriculture feed stocks (starches) Researchers have successfully used petroleum based film for
act as a precursor for the synthesis of various biopolymers enhancing the storage life of various commodities [24–27].
through enzymes and microbial fermentation. A schematic In this study some relevant research work carried out on
flow chart for the synthesis of biopolymers is shown in modified atmosphere packaging of fruits and vegetables
Fig. 3. using biodegradable polymers are listed and presented in
Table 6.
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Fig. 3 Schematic flowchart for synthesis of different biopolymer from starches [1]
Plantic (Plantic Technologies, USA) Ingeo (Nature Works, USA) Ecovio® (Nature Works, USA)
Solanyl (Rodenburg Biopolymers, Japan) PURAC (PURAC Co., Thailand) Bio-Flex® (BASF, Germany)
Bioplast (Biotec, USA) BIOFRONT (Teijin, Japan) Plantic (Plantic Co., USA)
Biopar (Biop, Germany) HiSun (Revoda, Canada) Biolice (Limagrain, France)
Mater Bi (Novamont, USA) Pyramid (Tate and Lyle, Denmark) Compole (Japan corn starch, Japan)
PET Bio-PET Bottles for carbonated PS/PP PLA/Blends of PLA/ Clear films for fruits and
beverages Bio-PET vegetables
PP Bio-PP Cups for yogurt PS/PP PLA/PHB Coffee capsule/pouches
PET, PP, PS Bio-PP, PLA Trays PS PBAT Shrink films
PE, PP PLA blends Caps PE Bio-PE Stretch films
PET, PS Cellulose, starch blends Cutlery PE, PP, PS Blends of PLA/PHA/ Shopping/waste bags
PBAT
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Table 6 Showing researches on biodegradable films used in MAP of fruits and vegetables
Commodity Biodegradable Observation References
material
Sweet cherries PLA This study investigated the changes in quality of sweet cherries during MAP (1 °C) with poly- [85, 87]
ethylene (25 μm thickness; O2 TR 8000 cm3 m−2 day−1 atm−1) and biodegradable films, film
1 (25 μm thickness; O2 TR 3000 cm3 m−2 day−1 atm−1) and film 2 (25 μm thickness O2 TR
900 cm3 m−2 day−1 atm−1)
More CO2 concentration was observed in film 1 (6.9%) after 15 days of storage
There was no change in TSS during the storage period of control fruit but a slight increment
was observed in storage under MAP condition (for both films 1 and 2)
It was concluded that film 2 had higher permeability to CO2 and barrier to O2 and it resulted
good quality of fruits in terms of color, acidity and firmness
Fresh fruits and PLA The excess WVTR due to perforation as a function of the water vapor permeability of the film [86, 88]
vegetables was estimated. The combined effect of perforation and permeability of the film on the syn-
thesis of the equilibrium modified atmosphere packaging (EMAP) was also investigated
The effect of the perforation was lower for the PLA and the starch based films, which are
hydrophilic. In the case of cellophane, which was less permeable to water, the effect of the
hole was similar to the OPP film, although its WVTR was 10 times higher
Plum Tomato PLA and poly- Plum tomato (cultivar Iride) was packaged in three different plastic films, a commercially [87, 89]
olefin films available polyolefinic film and two biodegradable films, and stored at market conditions
(15 °C and 75% RH)
Results showed that the use of packaging films with high barrier properties speeded up the
quality decay kinetics of the investigated produce
The biodegradable films with an appropriate permeability coefficient could be advantageously
used to prevent contamination from both microorganisms and insects, without reducing the
shelf life of the produce
Mushrooms PVC film, The effect of different packaging films (paper, PVC, paper coated with wheat gluten) on quality [88, 90]
(Agaricusbispo- Paper, paper of mushrooms during the storage (20 °C and 80% relative humidity) was investigated
rus L.) coated with It was observed that mushroom stored in wheat gluten coated paper offered more shelf life
wheat gluten (3 days) and it retained the product color, texture and unbroken veils as compared to that
stored in PVC film and the shelf life in PVC film was limited to 1 day
This shelf life extension of mushroom was attributed to storage at medium CO2 (9.5 kPa) and
low O2 (2.5 kPa) partial pressure, without condensation
Cabbage toma- Laminate of The effect of temperature (10–25 °C) on gas permeability coefficients (O2, CO2 and N2) of [89, 91]
toes, sweet corn chitosan – biodegradable laminates was evaluated
and blueberries cellulose and This study reveals that gas permeability coefficients increased with increasing temperature
polycaprol- The biodegradable laminate was found suitable as a packaging material for storage of fresh
actone produce
Banana Biofex The effects of biodegradable MAP and LDPE conventional packaging on quality of banana [90, 92]
were studied
This storage was conducted at a temperature of 20 °C and 80% RH for eight days
Small weight loss was observed in banana stored in biodegradable MAP (1.8%) as compared to
conventional MAP (3%) and control sample (6.5%) after eight days of storage
Fruits stored in conventional MAP and without packaging ripened faster compared to biode-
gradable MAP
The CO2 concentration in packaging head space was 12% in biodegradable MAP and 9.8% in
conventional MAP after 8 days of storage
Fruits stored in biodegradable packaging showed greater consumer acceptance
Green pepper PLA The effects of PLA based biodegradable packaging, LDPE film packaging and perforated [91, 93]
LDPE packaging on the microbial and physiochemical quality of green pepper were com-
pared. Study was conducted at 10 °C for 10 days
The levels of coliform bacteria were increased by less than 1log CFU/g (0.2 log CFU/g) in the
biodegradable film packaging, whereas it was 2.3 log CFU/g in LDPE film package, and less
than 1log CFU/g (0.9 log CFU/g) in the perforated LDPE film package, after 7 days storage
period
The weight loss values for green pepper at the end of 7 days period were 2.46 ± 0.6%,
0.38 ± 0.1%, and 1.59 ± 0.4% for PLA, LDPE, and perforated LDPE film packaging, respec-
tively
The O2 and CO2 concentrations at 7 days of storage were 11.6 ± 4% and 5.6 ± 2% for PLA film,
and 14.8 ± 3% and 2.3 ± 1% for LDPE film, respectively
Biodegradable PLA film can provide an alternative to the chemically replace LDPE film for
modified atmosphere package
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Table 6 (continued)
Commodity Biodegradable Observation References
material
Mango Chitosan The effects of chitosan based biodegradable film and LDPE film on quality of mango stored at [92, 94]
based film a temperature 27 ± 1 °C and 65% RH were studied
The mango fruits were kept in carton boxes and top surfaces covered with biodegradable film
(MAP1) and LDPE (MAP2) and were compared with control (samples kept as such)
MAP2 fruits showed lower weight loss (3.5%) compared to MAP1 (7.5%), which was attrib-
uted to reduction in transpiration of water vapor in LDPE films
On day 18, the CO2 and O2 levels were 21.50% and 5.21%, in MAP1 and 18.35% and 6.65% in
MAP2, respectively
The pH of the fruits was 4.06, but as the fruits ripened, the pH of control fruits increased to
6.73 on day 12, which was higher compared to MAP1 (5.04) and MAP2 (5.79) fruits
Fruit salad Cellulose In this study minimally processed apple and pear mixed salad samples were packed under [93, 95]
based MAP in PP containers and sealed by different polymers (BOPP PropafreshTM P2GAF,
Nature- Amcor Agrifresh film, Biodegradable NatureFlexTM NVS INNOVIA Film and VC999
FlexTM BioPack PLA film coated with a barrier of pure silicon oxide (SiOx)) and stored at
NVS INNO- 4.0 ± 0.5 °C up to 10 days
VIA Films The mass losses as evaporated water permeated through VC999 BioPack PLA lidding film was
and VC999 observed to be the highest (0.46%) compared to other materials
BioPack CO2 content in containers sealed by BOPP Propafresh™ P2GAF film, AmcorAgrifresh film,
PLA coated NatureFlexTM NVS INNOVIA Film pouch and VC999 BioPack PLA film achieved 18, 13,
with a bar- 15 and 9%, respectively. There was no increase in CO2 (1–3%) content for containers sealed
rier of pure with PP and this was maintained during storage period of 10 days
silicon oxide It was concluded that biodegradable films are good alternatives to conventional polymers for
(SiOx) packaging fruit salads
employed within food quality monitoring systems, such as humidity. Barrier properties are usually measured under
active and intelligent packaging systems. The technologies equilibrium moisture conditions with a controlled environ-
that are associated with smart and active biopolymers have ment [97, 98]. Oxygen, CO2 and water vapor are the main
the potential to drive the development of a new generation parameters studied in packaging applications. The change
of intelligent/active packaging systems that integrate food in product quality (weight loss, color change, change in pH
quality monitoring systems and microparticles in a manner and increase in microbial growth) occurs due to the move-
that extends the shelf life of food products and their nutri- ment of these gases and water vapor [45]. The properties of
tional value [96]. different biopolymers are listed in Table 7. The requirement
of oxygen and carbon dioxide gas composition for optimum
storage varies for different commodities. During the MAP of
Properties of Biopolymers food, the gas composition changes due to different biological
and chemical reactions, this results loss in product quality.
The shelf life of any product in a packaging depends pri- The packaging material should have recommended level of
marily upon the barrier properties of the packaging mate- permeability to gases and water vapor to maintain equilib-
rial. Gas phase permeation through a nonporous material rium atmosphere and thus to extend the shelf life of product.
occurs through adsorption at the leading interface, diffusion If the oxygen permeability of film is high then the vapor
through the material, and desorption at the trailing inter- pressure of oxygen inside the package increases and it leads
face and is often measured with three parameters: trans- to oxidation as well as respiration (fruits and vegetables) of
mission rate, permeance, and permeability. Transmission the product. Water vapor barrier property of film is required
rate is the volume or weight of a permeant (e.g., oxygen for some products like bakery products, powders which
or moisture) passing through a film per unit surface area need to be stored at very low moisture [45]. The oxygen,
and time under equilibrium with testing conditions. Perme- carbon dioxide and water vapor barrier properties of a film
ance is the transmission rate divided by the partial pressure are quantified by the oxygen permeability coefficient (OPC),
difference of the permeant across the film. Permeability is carbon dioxide permeability coefficient (CO2 PC) and water
the permeance multiplied by the thickness. Barrier proper- vapor permeability coefficient (WVPC), respectively, which
ties are not only determined by the nature of a material, indicate the amount of O2 oxygen or CO2 or water vapor that
but also a function of temperature, pressure, and relative permeates per unit of area and time in a packaging material
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Journal of Packaging Technology and Research
1. Physical properties Density is a very important property because high density leads to high transportation cost and this
(i) Molecular weight also affects mechanical properties (Table 9)
(ii) Density
(iii) Molar volume
2. Transmission properties Most of the food materials require specific atmospheric conditions to extend the shelf life and to
(i) Oxygen transmission rate maintain quality during storage [19, 23] (Mangaraj and Goswami, 2009; Mangaraj et al. 2009)
(ii) CO2 transmission rate Most of the foods are oxidative in nature and respiration of fruits occurs at high levels of oxygen. It
(iii) Water vapor transmission rate leads to deterioration of quality so the packaging material should act as a barrier to the gases [23]
Gas barrier properties of packaging films depend upon the humidity [39]
The oxygen and carbon dioxide barrier is quantified by the oxygen permeability coefficient (OPC)
and carbon dioxide permeability coefficient (CO2 PC), respectively, which indicate the amount
of oxygen or CO2 that permeates per unit of area and time in a packaging material [kg m m−2 s−1
Pa−1] [45]
Most of the biopolymers are hydrophilic in nature so it leads to moderate water uptake when it is
exposed to water [39]
The water vapor barrier is quantified by the water vapor permeability coefficients (WVPC) which
indicate the amount of water vapor that permeates per unit of area and time in a packaging materi-
als [kg m m−2 s−1 Pa−1] [45]
Migration of water through the polymer can lead to a disturbance of the fiber/polymer interface,
reducing the overall strength of the composite [94, 99]
3. Thermal properties The glass transition temperature is the property of the amorphous region of the polymer, whereas the
(i) Melting temperature crystalline region is characterized by the melting point [37, 39]
(ii) Glass transition temperature Glass transition temperature depends upon molecular weight, intermolecular forces, and plasticizers
[39]
The polymers those are used for storage of foods at lower temperatures should have high glass transi-
tion temperature and those for which food materials are packed at high temperature should have
high melting point [94, 99]
4. Mechanical properties Polymers should have good mechanical properties to provide physical barrier from the forces during
(i) Strength handling and transportation [23]
(ii) % elongation break The mechanical properties of biobased polymers like modulus and stiffness are similar compared to
(iii) Toughness conventional polymers [94, 99]
(iv) Young’s modulus Mechanical properties of polymers depend up on the molecular mass [94, 99]
(v) Viscoelasticity
5. Biodegradation/Compostability This property is useful to create sustainable environment
The term biodegradation involves biological activity. Composting is a process in which the organic
matter is converted to CO2 and a soil-like material (humus) by activity of a mixed group of micro-
organisms [95, 100]
Biodegradation of biopolymers involves mainly three steps biodeterioration, biofragmentation and
assimilation [96, 101]
The degradation time of biopolymers is less compared to conventional polymers Table 11)
Biodegradation is affected by chemical structure, chemical chain, crystallinity, temperature, pH,
moisture content and oxygen content [97, 102]
[(kg m m−2 s−1 Pa−1]) [103]. Transmission properties of dif- Thermal properties of film also play important role dur-
ferent biopolymers and conventional polymers are listed in ing the selection of packaging material, because most of
Table 8 [34, 45]. the food products are stored at lower than the atmospheric
It is well- known that the polymer architecture plays an temperature. The selection of packaging material mainly
important role on the mechanical properties, and conse- depends upon the processing, packaging and storage tem-
quently on the process utilized to prepare the final product peratures. Thermal properties can be characterized as glass
(i.e., injection molding, sheet extrusion, blow molding, ther- transition temperature (Tg) and melting temperature (Tm);
moforming, and film forming). In addition, many packaging these can be calculated by differential scanning calorimeter
containers are commercially used below room temperature, (DSC). Thermal properties of different bio and conventional
so it is important to assess the mechanical performance polymers are listed in Table 10 [39, 94, 99].
under these conditions [17, 45]. The list of physical and The advantage of biodegradable polymers over petroleum
mechanical properties of different bio and conventional based polymers is its biodegradability. This can be quantified
polymers is shown in Table 9 [94, 99].
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Table 8 Permeability properties of different biopolymers along with Table 10 Thermal properties of different biopolymers along with
conventional polymers at 23 °C and 50% RH [39] conventional polymers [39, 94, 99]
S. No Type of material Oxygen per- Water vapor S. No. Type of material Glass transition Melting
meability transmission temperature (Tg) temperature
rate (Tm)
Table 9 Physical and S. No. Type of material Density (g/cm3) Tensile Tensile modu- Ultimate strain (%)
mechanical properties of strength (MPa) lus (GPa)
different biopolymers along
with conventional polymers 1. PLA 1.21–1.25 21–60 0.35–3.50 2.5–6
[94, 99]
2. L-PLA 1.24–1.30 15.5–150 2.70–1.14 3–10
3. DL-PLA 1.25–1.27 27.6–50 1–3.45 2–10
4. PGA 1.50–1.71 60–99.7 6–7 1.5–20
5. DL-PLA/PGA 1.30–1.40 41.4–55.2 1.00–4.34 2–10
6. PL-PLA/PGA 1.30 41.4–55.2 1.38–4.13 2.5–10
7. PCL 1.11–1.15 20.7–42 0.21–0.44 300–1000
8. PHB 1.18–1.26 40 3.50–4 5–8
9. LDPE 0.92–0.93 7.17 0.14–0.3 200–900
10. PA6 1.13 3 80 50–120
11. PET 1.29–1.40 3 50 50–300
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Table 11 Compostability of different bio and conventional polymers Methods for Manufacturing Biodegradable
S. No. Type of material Com- Films
postability
(months) Manufacturing of biopolymers is a multi-step process that
1. Polyester amides 3–6 requires proper skill and thorough understanding of behav-
2. md-PHA 0.8–3.2 ior of bio polymers during processing. Biopolymers can be
3. Aliphatic (co) polyester 1.1–4.3 processed into varieties of products (packaging films, lami-
4. Proteins 0–1.4 nated paper, films, trays, cups cutlery items) depending upon
5. Thermo plastic strachTPS 0–0.8 the processing route (cast films, blow molding, coextruded
6. Polylactide(L) 0.4–1.5 films). The fundamental step of processing of any biopoly-
7. Cellulose diacetate 3.9–6 mer involves melting the biopolymer mix followed by cast-
8. TPS blends 0–1.8 ing, extrusion, blow molding, depending upon the material
9. PHBV biopol 0–2 to be made. Different methods of processing of biodegrad-
10. Cellulose paper 1.4–3.5 able materials are listed in Table 12.
11. News paper 2.8–4.7
12. Alip./arom. copolyester 3.3–6
13. Wood 4–6 Biodegradation of Biopolymers
14. Polycarprolactone 0.5–1.3
During degradation, the polymer is first converted to its
monomers and then these monomers are mineralized. Bio-
degradation is governed by different factors that include
implementation of antimicrobial enzymes like lysozyme and
polymer characteristics, type of organism, and nature of
other biocatalysts in active packaging has also been explored
pre-treatment. The list of factors affecting the rate of bio-
[113]. Very recently, bacteriophages have been embedded
degradation of polymers is shown in Table 13. The polymer
into acetate cellulose films for use against Salmonella Typh-
characteristics such as its mobility, tacticity, crystallinity,
imurium [114]. Cinnamon oil-embedded polymer films have
molecular weight, the type of functional groups and sub-
also been recently produced at the pilot-scale to repel larger
stitutes present in its structure, and plasticizers or additives
pests and insect larvae [107]. Some other forms of antimi-
added to the polymer all play an important role in its deg-
crobial packaging will enhance quality and safety of food
radation [98, 99, 116, 117]. The reactions occurring during
products, like addition of sachets containing volatile antimi-
the biodegradation of polymers is shown below.
crobial agents into packages that are inherently antimicrobial
due to immobilization of ions and covalent linkages [115].
Table 12 Different methods for preparation of biodegradable films from biodegradable materials [36, 37, 39]
S. No. Method Information
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