K. KHOSRAVI-DARANI and D. Z. BUCCI, Application of Poly(hydroxyalkanoate)…, Chem. Biochem. Eng. Q., 29 (2) 275–285 (2015) 275 Application of Poly(hydroxyalkanoate) In Food Packaging: Improvements by Nanotechnology K. Khosravi-Darania and D. Z. Buccib,* aResearch Department of Food Technology, National Nutrition and Food Technology Research Institute, Faculty of Nutrition Sciences and Food Technology, Shahid Beheshti University of Medical Sciences, P.O.Box: 19395–4741, Tehran, Iran doi: 10.15255/CABEQ.2014.2260 bUniversidade Regional de Blumenau, Departamento de Engenharia Review de Produção e Design, Rua São Paulo 3250, Received: August 22, 2014 CEP 89030–000 Blumenau, SC, Brazil Accepted: June 2, 2015 The environmental impact of plastic usage is of critical concern and too great to repair. A shift toward biodegradable food packaging is one option. The aim of this review paper is the study of the potential of biodegradable materials for food packaging. The main characteristics in relation to food usage can be narrowed down to mass transfer (gas and water vapor), thermal and mechanical properties. Among several kinds of biodegrad- able polymers, poly(hydroxyalkanoate) is one of the favorable candidates for food pack- aging due to its physical and mechanical properties, biodegradability, with low permea- bility for O2, H2O and CO2 without residues of catalysts and water solubility. The main focus of this article is to address poly(hydroxyalkanoate) as a potential candidate for food packaging. The need of applying biobased polymers in food packaging is presented in the introduction of this study. We also describe the most common biopolymers provid- ing a brief overview of classification and application. This is followed by an outline of biopolymer production and a main section in which the properties of poly(hydroxybutyr- ate)-based nanocomposites of greatest relevance to food packaging are discussed. Fur- thermore, several approaches for improvement of poly(hydroxybutyrate) properties are described and the role of nanotechnology to improve its mechanical properties is present- ed. Finally, the article concludes with a summary as well as some possible future trends. Key words: poly(hydroxybutyrate), poly(hydroxyalkanoate), food packaging, properties, modifica- tions, nanoparticles Introduction mental impacts are three main issues which should been identified in the concern of food packaging2. Food packaging is a main step of the food The production of plastics is one of the largest man- chain, the purpose of which is mechanical support, ufacturing industries in the world. The aims of the transition, extension of shelf life, and preservation recycling plants are reduction of the amount of of food. Petrochemical-based polymers have long plastic created each year, and their reuse. However, been vital materials in food packaging due to sever- recycled materials can be used for food packaging al reasons, including their mechanical properties, only if they meet specific government standards. easy processing, and cost. The common food-pack- Such limitation leads to a cost- and time-consuming aging polymers are polyethylene (PE) (cooking oil, process. Despite a great amount of different recy- milk and water containers), polyethylene terephthal- cling programs, in some places there is still no co- ate (PET) (applied in food, beverage, and other liq- hesive recycling program3,4. uid containers); polyvinylchloride (PVC) and poly- The food industry spends approximately less propylene (PP) (yogurt, spice ice tea, and margarine), than hundred billion dollars a year on food process- polystyrene (PS) (eggs and mushroom), and poly- ing5. Less than one tenth of the total food cost is amide (PA) (flexible packaging of perishable food, spent on packaging and processing. At present, food 1 such as meat and cheese) . The cost, migration of and beverage packaging comprises about one half toxic ingredients into food matrix, and the environ- of food packaging in the United States. Innovation * Corresponding author: Doris Zwicker Bucci; Tel: +55 (47) 3221 6068; in food and beverage packaging is increased with Fax: +55 (47) 3221 6000; email: [email protected] the aim of reducing food preparation time and use 276 K. KHOSRAVI-DARANI and D. Z. BUCCI, Application of Poly(hydroxyalkanoate)…, Chem. Biochem. Eng. Q., 29 (2) 275–285 (2015) of animal protein, as well as enhancing bioconver- droxyalkanoates (PHA), poly(lactic acid) (PLA), sion of materials, and industrial processing5. and polycaprolactones (PCL), which arise from re- The packaging materials include fillers, plasti- newable resources, present processability with con- cizers and stabilizers. Fillers tend to maintain barri- ventional plastics machinery. er and mechanical properties, while filling the poly- PCL is a biodegradable thermoplastic polyester mer with cheap materials reduces the cost. synthesized by chemical conversion of crude oil. Plasticizers are applied to strengthen flexibility, This biopolymer has good water, oil, solvent, and ductility, and toughness of polymers while at the chlorine resistance, with a low melting point, glass 6 same time reducing hardness and stiffness . Also, transition temperature, and low viscosity, and pro- stabilizers are incorporated into the matrix to inhib- cessable using conventional melt blending technol- it deterioration of mechanical properties due to UV 13 7 ogies . PCL is being investigated for its use in bio- light and oxygenation . medical utensils, pharmaceutical controlled release There are still many concerns about food pack- systems, and in biodegradable packaging13. PLA is aging materials and their possible interactions with L 8 a thermoplastic biopolyester produced from -lactic food, especially when food plastics are reused . acid, which is usually produced from the fermenta- Also, there are some issues about environmental tion of corn starch, and can be biodegraded by some problems due to slow degradation of polymers bacteria (e.g. Alcaligenes faecalis) and fungi. Cur- and the importance of consumption of renewable rently, PLA is the most commercially used biopoly- sources. Therefore, there is a growing interest worldwide to replace plastics with biodegradable ester in food packaging applications commercial- 9 ized in cups, containers and films for short shelf-life plastics, particularly in packaging applications . The 12 use of biodegradable plastics and resources are seen products . Incorporation of plasticizers for reduc- as one of the many strategies to minimize the envi- tion of stiffness leads to a decrease in oxygen barri- ronmental impact of petroleum-based plastics. Plas- er and transparency. PLA, when compared to PET tic recycling is not often economically viable as and polyolefins, presents easy processability14, there are problems of contamination of the food availability in the market and transparency15, as packaging10. well as printability16, biodegradability in compost17, but low thermal resistance, excessive rigidity, and high permeable properties. Conversely, the use of Biopolymer-based food packaging PLA films for food packaging has been strongly limited due to poor mechanical and barrier proper- Bio-based polymers can be categorized in three ties18. Moreover, for large-scale industrial produc- groups: tion of PLA must guarantee adequate thermal stabil- 1. Polymers extracted directly from biomass e.g. ity or low thermal degradation during processing proteins (whey, casein, collagen, soy), lipids (tri- and use19. glycerides), and polysaccharides (cellulose, starch, Thus, melt blending PLA with another bio- chitin gums) polymer may cause improvement of some cha- 2. Polymers synthesized from bio-derived mono- racteristics, cost, and easy processing technolo- mers e.g. polylactides gy11. Both PLA and PHB have a similar melting 3. Polymers produced by natural or genetically temperature. Therefore, melt blending for inser- modified organisms e.g. microalgal and bacterial tion of a highly crystalline poly (hydroxybutyrate) cellulose and other inclusion bodies, e.g. poly(hy- (PHB) to the PLA bulk has been considered as droxylalkanoate) an easy way to moderate properties and enhance Naturally occurring substances are partly or PLA crystallinity20,21. About PLA, a great industri- completely biodegradable, which may prove useful al interest is the enhancement of its thermal and 11 for food packaging . However, biodegradable poly- barrier properties while maintaining its inherently mers are expensive and exhibit poor mechanical 12 good properties e.g. transparency and biodegrad- properties . ability. Recently, a novel combination of PLA-PHB Biodegradable polymers blends and functionalized CNCs for food packaging in food packaging have been reported. This investigation indicates that this combination offers a new view for their indus- Biodegradable materials show some promising trial usage as short-term food packaging12. There characteristics for many applications e.g. packag- are some effective solutions for mechanical prob- ing, and the medical sector. Specifically, thermo- lems, but some problems exist for barrier and ther- plastic biodegradable polymers, such as polyhy- mal properties11,12,22–26. K. KHOSRAVI-DARANI and D. Z. BUCCI, Application of Poly(hydroxyalkanoate)…, Chem. Biochem. Eng. Q., 29 (2) 275–285 (2015) 277 PHA Bucci et al. 2005, investigated the use of PHB in food packaging, comparing it to PP9. The deforma- PHAs are biopolymers which accumulate as a tion value of PHB was about 50 % lower than that carbon/energy or reducing