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Int.J.Curr.Microbiol.App.Sci (2019) 8(3): 2311-2321

International Journal of Current and Applied Sciences ISSN: 2319-7706 Volume 8 Number 03 (2019) Journal homepage: http://www.ijcmas.com

Review Article https://doi.org/10.20546/ijcmas.2019.803.274

Bioplastics for Packaging: A Review

Rukhsana Rahman*, Monika Sood, Neeraj Gupta, Julie D. Bandral, Fozia Hameed and Shafia Ashraf

Division of and Technology, S. K. University of Agricultural Sciences and Technology of Jammu, Chatha - 180 009, J & K, India

*Corresponding author

ABSTRACT

In the past years, various studies have been done on biodegradable materials to replace petroleum based plastics for application. For this purpose, biopolymers are considered the most favorable material because of their biodegradable nature and long

properties like resistance to chemical or enzymatic reactions. Keeping in view the K e yw or ds non-renewable nature and waste disposal problem of petroleum based plastics; newer

Petrochemical concept of use of came into existence. Bioplastics are derived from renewable plastics, Bioplastics, resources i.e. produced from agro/food sources, materials such as , cellulose, Biodegradable etc. used for packaging materials and which are considered safe to be used in food packaging, Blend, applications. Bioplastics made from renewable sources are compostable or degradable by

Recyclable, the enzymatic action of micro-organisms and gets hydrolysed into CO2, CH4, inorganic Renewable compounds or biomass. The beneficial uses of bio-origin materials obtained from resources, microbial fermentations, starch and cellulose has led to their immense innovative uses in

Agricultural food packaging in the last few years. The biodegradable packaging materials are highly byproducts, Biopolymers, beneficial in one time use or short-duration packaging requirements. The main function of nanofillers biodegradables like any other packaging material is to protect the contents from surrounding and maintain its throughout the storage life. They are widely used to Article Info pack low shelf life products, like fresh fruits and vegetables, and high shelf life products, like pasta and chips, which does not require very high and/or barrier Accepted: properties. To increase the mechanical properties, and water barrier properties, the 20 February 2019 Available Online: bioplastics can be blended easily with other biopolymer as well as nanofillers. The 10 March 2019 dependency on limited petroleum resources has been reduced with the developments in the bio-based packaging. Thus, the bioplastics serve as an eco-friendly substitute for the use of non-renewable and non- based packaging materials and the study of recyclable and biodegradable is fascinating and developing area in packaging science.

Introduction and preservation of all types of and is prevalent by petroleum-derived plastics. Food packaging is a prerequisite element in Petrochemical-based plastics such as the , concerns with protection polyvinylchloride (PVC), (PP),

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Int.J.Curr.Microbiol.App.Sci (2019) 8(3): 2311-2321 terephthalate (PET), naturally occurring organisms, such as polyethylene (PE), polyamide (PA) and , , or fungi (Sorrentino et al., polystyrene (PS) have been progressively 2007), and can be used as fertilizer or humus used as packaging materials because their when composted (Siracusa et al., 2008). good mechanical performance such as tear and tensile strength, good barrier to carbon Currently, bioplastics represent about one dioxide, oxygen, anhydride and aroma percent of the about 320 million tonnes of compound, and heat sealability and because plastic produced annually. According to the their huge availability at relatively low cost European Bioplastics in cooperation with the (Siracusa et al., 2008). Increased use of research institute nova-Institute, global petroleum based plastics has both bioplastics production capacity is set to environmental and health hazards. It also increase from around 2.05 million tonnes in affects the health of workers who are related 2017 to approximately 2.44 million tonnes in with cleaning or maintaining the processing 2022 (European , 2017). equipments which led to serious ecological problems due to their total non- Although bioplastics are considered to biodegradability (Jayasekar et al., 2005). develop eco- friendly food packaging materials, they also have some limitations Due to the increasing environmental concerns such as poor mechanical and barrier created by excessive plastic accumulation, properties and high production cost. But their interest has shifted towards the development mechanical and barrier properties can be of such packaging materials that not only improved by blending two or more improve performance but are also easy to biopolymers and high production cost recycle and reuse i.e., “bio-plastics”. drawback can be managed by utilizing the According to the European Bioplastics low cost of renewable resources such as organization, bioplastics can be defined as agricultural wastes (Jain and Tiwari, 2015). plastics based on renewable resources (bio- Several active components or additives like based) or as plastics which are biodegradable , color, , nutrients, and/or compostable polymers. Bioplastics are etc. can be incorporated for increasing their derived from different renewable sources such performance (Clarinval and Halleux, 2005). as vegetable oil, corn starch, starch, fibres obtained from pineapple, jute, hemp, The study of recyclable and biodegradable henequen leaves and banana stemsand also plastic is an interesting and emerging area in from used plastic and other packaging science but massive research is using (Siracusa et al., 2008; required for improving their performance, Sudesh and Iwata, 2008). mechanical, thermal, and physical characteristics, and commercial use, which Biodegradable polymers are polymers that are might be possible in a few years. capable of undergoing into CO2, CH4, H2O, and inorganic compounds Classification of bioplastics under suitable conditions of , moisture, and oxygen or biomass through Various classification systems based on predominantly the enzymatic action of different criteria’s have been proposed to microorganisms (Song et al., 2009). Thus the classify these bioplastics, as they can be biodegradable packaging materials are those derived from a large number of renewable that undergo the process of degradation by sources and it is difficult to restrict them in a

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Int.J.Curr.Microbiol.App.Sci (2019) 8(3): 2311-2321 single class. However, one classification availability, and biodegradability. Starch system based on their origin (Fig. 1) divides having poor resistance to moisture and their these bioplastics into three major poor mechanical property restricts their use. categories/types. Therefore to improve these properties starch is blended with various biopolymers and Natural polymers or polymers derived from certain additives (Yadav et al., 2018). biomass. Synthetic polymers or polymers chemically Cellulose synthesized from renewable sources. Microbial polymers or polymers derived from Cellulose is the most abundant natural microorganisms. and is derived by a delignification from wood pulp or cotton linters. Cellulose is Natural polymers or polymers derived very difficult to use in packaging because it is from biomass hydrophilic and crystalline in nature possessing poor mechanical properties in its The natural polymers are derived from raw form. Therefore, it must be treated with animal, marine, and agricultural sources, chemicals like NaOH, H2SO4, CS2, etc. to which include the polysaccharides, such as produce having excellent starch, cellulose, , gums etc., mechanical characteristics (Majid et al., like plant derived proteins (zein, gluten, soy, 2018). Cellulose derivatives can be produced etc.) and animal extracted proteins (casein, by derivatization of cellulose from the collagen, , etc.) and including solvated state, via esterification or cross linked triglycerides. By nature most of etherification of hydroxyl group. Cellulose these polymers are hydrophilic and crystalline derivative forms are used for films or edible in nature, which create several problems : Hydroxypropyl cellulose, while processing in moist food packaging. hydroxypropyl methylcellulose, However they have excellent gas barrier Carboxymethyl cellulose or Methyl cellulose properties which make them acceptable for (Majid et al., 2018). Incorporation of their utilization in food packaging (Averous hydrophobic compounds is one method for and Pollet, 2012). increasing the moisture barrier, such as fatty acids into the cellulose ether matrix to Starch develop a composite film (Morillon et al., 2002). Starch is the most abundant commonly used renewable raw material and easy Chitosan or chitin biodegradable natural resource. It is obtained from seeds, corn, wheat, rice, potato, sweet Chitosan or chitin, is the second abundant potato, and cassava (Whistler and BeMiller, polysaccharide resource after cellulose found 2007). Starch is usually used as a in nature. It naturally appears in the thermoplastic and constitutes a substitute for exoskeleton of arthropods and in the cell polystyrene (PS). It is plasticized through walls of and fungi. It is produced destructuration in presence of specific commercially by chemical extraction amounts of water or plasticizers (glycerol, processes from prawns and crabs wastes. ) and heat and then it is extruded. Chitosan is obtained from deacetylation of Starch is an attractive material for packaging chitin, and different factors (e.g. alkali applications because of its relatively low cost, concentration, incubation time, ratio chitin to

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Int.J.Curr.Microbiol.App.Sci (2019) 8(3): 2311-2321 alkali, temperature and chitin source) can or for thermoplastic applications is currently affect its properties (Thakur et al., 2016). being carried out due to its low cast and Chitosan forms films without the addition of abundance (Otles and Otles, 2004). additives, exhibits good and oxygen permeability, as well as excellent Soy proteins are commercially available as mechanical properties and soy flour, soy concentrate and soy isolate. Soy properties which reduces the oxidation protein isolate (SPI) may be used to prepare process and is beneficial for increasing the edible and biodegradable packaging films. shelf life and quality of food products (Gemili The films obtained from SPI exhibit excessive et al., 2009). friability, so their performance is limited. In order to improve them, they must be modified Proteins by the addition of a plasticizer, such as glycerol (Kokoszka et al., 2010). Proteins are complex structures made up of amino acids and can be obtained from plant The cheapest protein, keratin extracted from (wheat gluten, corn, zein, etc.) and waste streams such as hair, nails and feathers. animal (casein, whey, keratin, gelatin, etc.) Keratin the most difficult protein to process sources. They are highly desirable to modify due to its structure and a high content of the required characteristics of packaging cysteine groups (Shukla, 1992). On the other materials due to the presence of unique side hand, whey proteins, byproducts from the chain in their structure. Due to the renewable industry, are widely employed as nature, biodegradability and their excellent edible films and coatings. gas barrier properties proteins and protein based materials find their use in many Several components like fatty acids, industrial applications. But they are adversely natural waxes, resins, and vegetable oils are affected by their hydrophilic nature like generally incorporated in the films to provide starch-based polymers. Therefore, they need hydrophobicity so that moisture barrier to be blended with other polymers or must be properties can be improved. chemically or microbiologically modified (Majid et al., 2018). Synthetic polymers or bioplastics chemically synthesized from renewable Casein is a -derived protein, when sources processed with suitable plasticizers at temperature of 80-100 0C, form materials with They are produced from classical chemical mechanical performance varying from stiff synthesis from biobased monomers. In this and brittle to flexible and tough performance. category, polylactic acid (PLA) is one of the Casein films have an opaque appearance. most commercially available and exploited Irrespective of its relatively high price, it is bioplastics. used today for labeling because of its excellent properties. Polylatic acid (PLA)

Gluten plastics exhibit high gloss and show PLA one of the most promising and good moisture resistance under certain biodegradable made from renewable conditions. They do not dissolve in water, but resources such as corn, beets, and absorb some water on immersion. Research potato starch for commercial use as a on the use of gluten in edible films, , substitute for high density polyethylene

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(HDPE) and low density polyethylene propylene chloride. These polymers, alone or (LDPE), polystyrene (PS) and polyethylene in combination with starch or synthetic plastic terephthalate (PET). It is obtained by give excellent packaging films (Tharanathan, conversion of corn, or other 2003). Among more than 100 PHAs sources, into dextrose, followed by composites, PHB is the most common type of fermentation into lactic acid. Through direct PHA, coming from the polymerization of 3- polycondensation of lactic acid monomers or hydroxybutyrate monomer with properties through ring-opening polymerization of similar to PP but stiffer and brittle. It degrades lactide, PLA pellets are obtained. The under both aerobic and anaerobic conditions processing possibilities of this transparent forming CO2 and H2O. Besides being material are very vast, ranging from injection insoluble to water, PHB is optically active and over cast film and has good barrier properties toward gas extrusion to and (Castilho et al., 2009). The PHAs have (Rasal et al., 2010) potential as an alternative for many conventional polymers, since they possess PLA is becoming an advancing alternative as similar chemical and physical properties. a green food packaging material because it PHAs also exhibit printability, and was found that in many circumstances its odor barrier, heat sealability, grease and oil performance was better than synthetic plastic resistance, temperature stability, and are easy materials (Auras, 2005). PLA comes in the to dye which improve its applications in the form of films, thermo-formed cups and trays, food industry (Tripathi et al., 2015). containers and coatings for and paper boards etc. The utilization of several microbial polysaccharides, such as xanthan, pullulan, Microbial polymers or polymers derived curdlan, etc., as a packaging film is a novel from microorganisms. concept and needs biotechnological techniques. This class includes the polymers that are synthesized from the microbial fermentation Pullulan is produced by yeast like of polysaccharides. It is a quite recent and Aureobasidium pullulans from substrates innovative field that has immense potential in containing which are linear, water- industry. This category includes the polymers, soluble and exopolysaccharide (EPS). It is such as polyhydroxyalkanoates (PHA), PHB, employed for packaging in several industries etc., and microbial polysaccharides like like food, , and cosmetics. Pullulan pullulan, curdlan and xanthan. based films are edible, homogeneous, transparent, printable, heat sealable, flexible Polyhydroxyalkanoates (PHAs) and good barrier to oxygen and are tasteless, odorless, nontoxic, and biodegradable in The polyhydroxyalkanoates (PHAs) are nature. Pullulan membranes inhibit fungal biodegradable, thermoplastic, biocompatible growth thus making them suitable for food and thermo stable having melting temperature applications particularly (Freitas et al., 2014). of about 180 0C. These polymers are produced in nature via bacterial fermentation Curdlan, the bacterial polysaccharide, is of plant-derived feedstocks such as sugars or produced from Agrobacterium biobar and lipids and then harvested by using solvents Agrobacterium tumefaciens and is mainly such as chloroform, methylene chloride or used as a gelling agent in the food industry

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Int.J.Curr.Microbiol.App.Sci (2019) 8(3): 2311-2321 but has enormous potential in the temperature is a very slow mechanism as development of packaging films, which is yet compared to hydrobiodegradation. The to be discovered. On the other hand, Xanthan oxobiodegradation of carboxylic acid (– is produced by the aerobic fermentation of COOH) results in alcohol, aldehyde and Xanthomonas campestris using sucrose or ketone molecules, which are degradable using glucose as its major carbon source and is low molar mass generated during the highly viscous, water soluble and nontoxic in peroxidation that is initiated either by light or nature. Not much data is available about the heat. This is the main reason the hydrocarbon potential of xanthan in the packaging sector. polymers lose their mechanical properties. This may be due to the high cost of After this, bioassimilation starts by the fungal production. However, acerola when wrapped or bacteria, giving rise to CO2 and with xanthan exhibited reduced biomass that finally produce humus. weight loss, respiration thus maintaining the Generally synthetic polymers contain color and enhancing the shelf life (Quoc et antioxidants and stabilizers are added to al., 2015). inhibit the oxidation of polymers during process and to increase the Mechanism of biodegradation shelf-life of materials and to improve the performance also (Scott and Wiles, 2001). Biodegradation means degradation, disintegration, or loss of mechanical attributes Improving the properties of bioplastics of packaging materials using microorganisms and is preceded by hydrolysis followed by The bioplastics are associated with several oxidation. The rate of biodegradation depends major drawbacks limiting their use in the on temperature (varying from 50 to 700C), industry. Thermal instability, brittleness, low humidity and kind and amount of melt strength, high and oxygen microorganisms. In industrial composting permeability, and poor heat sealability etc bioplastics are converted into water, CO2 and hinder the commercial use of bioplastics as biomass, in about 6-12 weeks (Siracusa et al., food packaging (Jamshidian et al., 2010). 2008). The degradation can be aerobic or Therefore, great efforts are being taken to anaerobic in nature resulting in the formation improve the functionality of biopolymers, or sludge in the former and such as methane and hydrogen (biogas) and in the latter. Natural biopolymers like starch, Coating cellulose, etc. are hydrophilic and swellable in nature in contrast to the polyolefins that are Coating consists of covering of biopolymer used in central packaging material and are using an additional thin film of another hydrophobic in nature, exhibiting high material. Several bio-based and non-biobased resistance toward hydrolysis, peroxidation, materials can be used as coating. and biodegradability. Prooxidants must be incorporated in polyolefins to initiate the For example, PLA can be layered using PCL- oxobiodegradation in them. The Si/SiOx, PEO-Si/SiOx (polyethylene oxide), oxobiodegradation mechanism is followed in or PLA-Si/SiOx, which improves the barrier the biodegradation of synthetic and natural properties of PLA which makes the PLA polymers; however, standard biodegradation films suitable for packaging material (Iotti et require the instant mineralization measure. al., 2009). Further, oxobiodegradation at room

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Chitosan can be employed as a biobased Blending coating for polymers that possess poor gas barrier properties. It can be an efficient and Blending of two or more biopolymers shows economic technique to improve the great significance. When we blend materials, performance of polymer. The application of compatibility becomes a major challenge. The coating improves the barrier properties, such compatibility for immiscible polymers can be as oxygen permeability and water vapor, increased by introducing a reactive functional grease or oil resistance, and to a little extent, group, chemical modification, or the mechanical properties (elasticity). etherification.

Table.1 Applications of bioplastics in food packaging

Packaging applications Biopolymer Company References Starch based Milk chocolates Cornstarch trays Cadbury Schweppes food Group, Highlights in Bioplastics, Marksand Spencer Website European Organic tomatoes Corn-based packaging Iper bioplastics (Italy), Coop Italia Cellulose Kiwi Biobased trays wrapped Wal-Mart Blakistone and Sand with cellulose film (2007) Potato chips Metalized cellulose film Boulder Canyon Organic pasta Cellulose based Birkel packaging Sweets Metalized cellulose film Quality street, Highlights in Bioplastics, Thornton Website European bioplastics Polylactic acid (PLA) Beverages PLA Cups Mosburger (Japan) Sudesh and Iwata (2008) Fresh PLA Bowls McDonald’s Haugaard et al., (2003) Coffee and Cardboard cups coated KLM Jager (2010) with PLA Fresh cut fruits and Rigid PLA trays and Asda (retailer) Koide and Shi (2007) vegetables, bakery packs Jager (2010) goods, salads Yoghurt PLA Stonyfield (Danone) Haugaard et al., (2001), Jager (2010) Organic fruit and PLA packaging Mont Blanc Primeurs vegetables Pasta PLA packaging Biorigin Highlights in bioplastics Herbs PLA packaging Asda (retailer) Source: Reproduced from Peelman et al., (2013).

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Fig.1 Classification of bioplastic polymers based on origin (Weber et al., 2002)

Biopolymer cellulose can be incorporated to (continuous phase) is desired to modify the the bio-based polymer mainly to improve the bioplolymer, which can be achieved through Young’s modulus and tensile strength and to polymerization, melt intercalation, and decrease the water vapor transmission rate. solvent intercalation. , mainly The PLA would be beneficial in reducing the nanoclays (montmorillonite and kaolinite), are film brittleness by incorporation of starch, preferred to enhance the properties of bio- glycerol, or other degradable polyester based polymers (Peelman et al., 2013). (Cabedo et al., 2006). Physical/chemical modification Nanotechnology Another technique used for improving the Nanotechnology is defined as the creation and performance of bioplastics is by chemical development of structures with at least one and/or physical modification. Such kinds of dimension in the nanometer length scale (10-9 modification provide a beneficial effect on the m) and these structures are called nano barrier and mechanical properties in addition composites which could exhibit modifications to enhancing the compatibility among or create novel properties to the materials. polymers. Generally starch is modified to improve the hydrophobicity, making them A good interaction between the nanofiller compatible with other hydrophobic materials. (discontinuous phase) and polymer matrix Starch films reduces their water vapor

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Int.J.Curr.Microbiol.App.Sci (2019) 8(3): 2311-2321 transmission rate by the addition of citric acid Future trend because carboxyl (–COOH) groups react with the hydroxyl (–OH) groups present in starch Comprehensive research is needed to improve and thus decrease the free OH groups. Also, the barrier properties and to maintain the food there is inhibition of recrystallization and integrity. Further, research and development retrogradation due to the formation of strong in the biodegradable polymers is the need of hydrogen bonds. Further, the addition of citric the hour because of human responsibility acid, a cross-linking agent improves the towards environment. That is the main driving mechanical properties of starch force implementing the tremendous potential (Ghanbarzadeh et al., 2011). Gelatinized of biopolymers in future. starch, when heated with lithium chloride (LiCl) in the presence of some organic References solvent, becomes water resistant and flexible also (Fang et al., 2005). Auras, R., Singh, S. P., and Singh., J.J. (2005). Evaluation of oriented poly Applications of bioplastics in food (lactide) polymers vs. existing PET and packaging oriented PS for fresh food service containers. Packaging Technology and Among the extensively used bio-based Science. 18:207-216. plastics, PLA is widely used. Moreover, the Averous, L. and Pollet, E. (2012). bioplastics nowadays have found applications Environmental Silicate Nano- for both short-shelf life products like fresh Biocomposites. Springer, London fruits and vegetables and long shelf life Heidelberg, New York Dordrecht, products, like potato chips and pasta. An Blakistone, B., and Sand, C.K. (2007). Using overview of applications of bioplastics in Technologies to food packaging is listed in table 1. Respond to Consumer, Retailer, and Industry Needs. International In conclusion, nowadays biodegradable Smoked Seafood Conference packaging materials are mostly used, which Proceedings, 75-79. do not need high oxygen and water vapor Cabedo, L., Feijoo, J. L., Villanueva, M.P., barrier properties. The biopolymers also show Lagaron, J.M., and Gimenez, E., (2006). some constraints about the performance, such Optimization of biodegradable as mechanical, barrier properties and cost, nanocomposites based on a PLA/PCL which can be improved by novel strategies, blends for food packaging applications. such as, blending, chemical or physical Macromolecular Symposia 233, 191– modifications, coatings or using nano 197. techniques. Incorporation of nanoparticles is Castilho, L.R., Mitchell, D.A. and Freire, better way to improve the performance of D.M.G. (2009). Production of biobased films. In the food industry, these are polyhydroxyalkanoates (PHAs) from used as carry , plates and cutlery, film to waste materials and by-products by pack short shelf-life food products, loose film submerged and solid-state fermentation. in transport, etc. Thus, it can be concluded Biores. Technol. 100, 5996_6009. that bioplastics have great potential in food Clarinval, A. M., and Halleux, J. (2005). packaging applications and also do not harm Classification of biodegradable the environment by breaking down into the polymers. In: Smith, R.(Ed.), organic matter. Biodegradable Polymers for Industrial

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How to cite this article:

Rukhsana Rahman, Monika Sood, Neeraj Gupta, Julie D. Bandral, Fozia Hameed and Shafia Ashraf. 2019. Bioplastics for Food Packaging: A Review. Int.J.Curr.Microbiol.App.Sci. 8(03): 2311-2321. doi: https://doi.org/10.20546/ijcmas.2019.803.274

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