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Journal Pre-proof Starch-based biodegradable plastics: methods of production, challenges and future perspectives Larissa do Val Siqueira, Carla Ivonne La Fuente Arias, Bianca Chieregato Maniglia, Carmen Cecı́lia Tadini PII: S2214-7993(20)30110-7 DOI: https://doi.org/10.1016/j.cofs.2020.10.020 Reference: COFS 632 To appear in: Current Opinion in Food Science Please cite this article as: do Val Siqueira L, Arias CILF, Maniglia BC, Tadini CC, Starch-based biodegradable plastics: methods of production, challenges and future perspectives, Current Opinion in Food Science (2020), doi: https://doi.org/10.1016/j.cofs.2020.10.020 This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. 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Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2020 Published by Elsevier. https://doi.org/10.1016/j.cofs.2020.10.020 https://doi.org/10.1016/j.cofs.2020.10.020 1 Starch-based biodegradable plastics: methods of production, challenges and future perspectives Larissa do Val Siqueira1,2, Carla Ivonne La Fuente Arias3, Bianca Chieregato Maniglia3 and Carmen Cecília Tadini1,2* 1 Universidade de São Paulo, Escola Politécnica, Department of Chemical Engineering, Main Campus, São Paulo, SP, 05508-010, Brazil 2 Universidade de São Paulo, Food Research Center (FoRC/NAPAN), SP, Brazil 3 Universidade de São Paulo, School of Agriculture Luiz de Queiroz (ESALQ), Department of Agri-food Industry, Food and Nutrition (LAN), Piracicaba, SP, 13418-900, Brazil *Corresponding author: Tel: +55 11 30912258. Email: catadini@usp.br (C. C. Tadini) Graphical abstract Jo ur na l P re -p ro of 2 ABSTRACT Although packaging based on starch is already being commercialized, its properties still have some disadvantages concerning conventional plastics, such as poor barrier (vapor and oxygen) and mechanical properties. Improving them is a great challenge, to know its processability and commercialization better. Currently, there is one intense quest for developing starch-based biodegradable plastics at lab scale. There are also incentives for using biodegradable packaging among government policies, sustainability actions by industries, and changes in consumer behavior. We here discuss the methods of production of starch-based biodegradable plastics, the barriers to large production, and future perspectives. Our current opinion is that much research funding is needed to overcome the challenges to a large production of these materials. Keywords: biodegradable packaging, starch films, packaging production, large-scale barriers. Jo ur na l P re -p ro of 3 Introduction Ecofriendly polymers have gained great attention in the last few decades due to environmental concerns [1]. Starch is a biopolymer available in nature, and starch-based plastics are one of the end products which have been of great interest. Starch-based plastics can be applied to agricultural, medical and pharmaceutical purposes, and food packaging, for example [2]. Starch-based materials have shown great potential, especially when an increasing number of countries adopted regulations for banning disposable conventional plastics [3]. For example, in Spain, the commercialization of single-use items, such as straws, balloon sticks, and plastic cutlery is banned, as well as the use of microplastics in cosmetics and detergents (URL: https://elpais.com/sociedad/2020-06-02/el-gobierno-lanza-un-nuevo- impuesto-sobre-los-envases-plasticos-que-preve-recaudar-724-millones-de-euros.html). In Brazil, the states of Rio de Janeiro (Law Project nº 3794/2018) and São Paulo (Law Project nº 631/2018) already established regulations that prohibit the supply or sale of plastic straws in commercial establishments. It is well known that the main benefit of starch-based materials is the biodegradability due to faster degradation and reduced requirement of landfills, as compared to synthetic plastics [4]. Moreover, positive social-economic effects are expected involving the production of bio-based polymers, particularly related to their employment in the agricultural sector [5]. Besides, the starch source is extensively accessible, being corn, potato, and cassava starches produced on commercial-scale and the most explored starch sources for plastic production [5]. Currently, we can find some biodegradable materials based on starch with the “Biodegradable products institute (BPI)” (URL: https://www.bpiworld.org/) or “OK compost HOME” (URL: https://www.tuv-at.be/home/) certifications already being Jo ur na l P re -p ro of 4 commercialized in the packaging market. For example, Mater-bi® (Novamont, Italy), Bioflex® (FKuR Kunststoff GmbH, Germany), Biopac (Biopac Ltd (UK), Bio-solo (Indaco Manufacturing Ltd, Canada), Bioplast® (Biotec GmbH, Germany), Clean Green (Starch Tech Inc, MN (USA), Cornpol® (Japan Corn Starch, Japan), Eco-flow (National Starch & Chemical (USA), Ecoplast (Groen Granlaat, Netherlands), Vegemat® (Vegeplast S.A.S, France) and Solanyl® (Rodenburg Biopolymers, Netherlands). Although this type of plastic is already being commercialized, its production and the improvement of its final properties still represent a great challenge. Starch-based plastic has poor mechanical properties and, due to its hydrophilic character, it presents high water vapor permeability, which limits its applications [3]. To overcome this problem, different approaches have been studied, such as starch modification, reinforcement with nanomaterials, blend and multilayer strategies. Therefore, given the advantages and the disadvantages yet to be overcome of the starch- based plastics, methods of starch-based biodegradable plastics production are here described, highlighting selected works for each technology. Moreover, the barriers for scaling up, challenges and the future perspectives of this field are discussed. Methods of production In this section, we explore techniques for starch film production, focusing mainly on the challenges of each. The preparation of starch-based films can be classified into wet and dry processes [6]. The wet process is more applied to lab-scale mainly because it is considerably time-consuming, whilst the dry process can be useful in an industrial setting [7]. The major processes for starch-based film production are casting (wet process), molding and extrusion (dry processes). Jo ur na l P re -p ro of 5 Figure 1 shows the number of papers found in the Web of Science database for each method from 2015 to 2020. The terms used in the research were: TS=((Casting AND starch) AND (*film* OR *sheet* OR *blend* OR *composite*) ) AND AB=(Casting AND Starch), for casting; TS=((Molding AND starch) AND (*film* OR *sheet* OR *blend* OR *composite*) ) AND AB=(Molding AND Starch) NOT AB=(3D OR “food extrusion” OR “pet food” OR print* OR dough OR cereal* OR bread* OR noodle*) NOT AK=(3D OR “food extrusion” OR “pet food” OR print* OR dough OR cereal* OR bread* OR noodle*), for molding; TS=((Extrusion AND starch) AND (*film* OR *sheet* OR *blend* OR *composite*) ) AND AB=(Extrusion AND Starch) NOT AB=(3D OR "food extrusion" OR "pet food" OR print* OR dough OR cereal* OR bread* OR noodle*) NOT AK=(3D OR "food extrusion" OR "pet food" OR print* OR dough OR cereal* OR bread* OR noodle*), for extrusion. Figure. 1. The number of papers (from 2015 to 2020) found in the Web of Science database for the following methods of starch-packagingproduction: casting, molding or extrusion. Jo ur na l P re -p ro of 6 We noted a superior number of publications on casting when compared with the other methods, which has increased over the years. In the period, there was a 22 % and 40 % increase for extrusion and molding, respectively, while casting increased by 100 %. This information suggests that many kinds of research in this field of starch-based plastic are still in their initial stage of verifying the formulation using the casting technique, which is a fundamental step. Also revealed is an urge for studying the extrusion and molding processes, for appropriately exploring the flexibility and the variety offered in parameter setting. This understanding is important to enable the next stage of the research in this field, aiming at large-scale production. The obstacles of scaling-up will be explored in the subsequent section. We also compiled the number of patents involving the methods of starch-based production in the Derwent Innovation Index through the Web of Science database for the same period (2015 to 2020), using the terms: (“starch” AND “packag*”) AND (“casting” OR “extrusion” OR “molding”) AND (“film” OR “plastic” OR “blend” OR “sheet” OR “composite”). We found a total of 61 patents indexed using the casting technology, while for extrusion, there were 63 and 101 for molding. These data convey interesting information showing that despite the higher number of publications using the lab-scale method, patents are significantly filled by large-scale technologies that facilitate technology transfers from the academy to the industry. Solvent casting Most studies involving the development of starch-based films use laboratory-scale methods since they are useful to evaluate the polymer capacity to form filmogenic matrices and their properties; however, they represent a high processing cost, due to the limited capacity of production and the difficulty in expanding to an industrial scale [8]. Jo ur na l P re -p ro of 7 One lab-method commonly used is solvent‐ casting. This method involves solubilization, casting, and drying steps. Firstly, the starch is gelatinized, forming a solution; some additives can be added to the process in this step. The casting technique consists in pouring the filmogenic solution onto plates (Teflon plates, Petri dishes, or acrylic plates), wherein the film thickness is controlled based on the mass of the film-forming solution that will not be lost during drying. Finally, the drying step can be conducted at room temperature or at a controlled temperature (30 to 40) °C, with drying times varying generally between (6 to 48) h, and under relative controlled humidity (30 – 85) %. The drying step is the most time-consuming [9], which is a point that hinders the process of scaling-up. Another point is that the films produced by this technique have a limitation of (25 to 30) cm (width or length) [10]. Also, in the literature, Ochoa-Yepes et al. [11] compared the properties of starch films produced by solvent casting in industrial-scale process (extrusion/thermo-compression). The authors observed that the casting method resulted in films with lower mechanical resistance, greater moisture content, water vapor permeability, water solubility, and hydrophilicity than films elaborated by extrusion/thermo-compression. We found a rare work involving the production of films based on cassava starch and pectin using a continuous laminating system KTF-S-B (Mathis, Germany) [12]. The film-forming solution was deposited on a polyester conveyor that takes the solution to a crack that promotes spreading in a uniform layer with controlled thickness. The conveyor then transports the material through drying sectors along the way. Although it brings the possibility of a continuous process, this technique shows some deficiencies when applied on a pilot-scale. For example, the filmogenic formulations must have adequate viscosity, sufficient to spread, but not so liquid that it can spill from the polyester surface, and the Jo ur na l P re -p ro of 8 step drying has to be efficient enough to dry while the material is transported on the conveyor. Because of the limitations presented by solvent casting, our current opinion is that much effort must be made by researchers to apply other methods that can be easily scaled-up. Tape-casting The tape-casting method is similar to that of solvent-casting; however, the support whereby the film-forming solution spreads allows drying control by conducting heat, circulating hot air (heat convection), and/or infrared. This process occurs through the movement of a conveyor tape (continuous process) or a scraper blade (batch process). An advantage of this technique is that it allows controlling the thickness through an adjustable blade at the bottom of the device where the solution is spread [13]. The thickness of the films generally varies between 20 μm and 1 mm. Besides, tape-casting allows producing multi-layer films by repeating the steps upon the film. Tape-casting is a method that requires a film-forming solution with shear thinning behavior with adequate apparent viscosity values to ensure adequate flow conditions and to concurrently prevent unwanted flow and sedimentation [13]. Works involving the use of tape-casting are scarce. From 2015 to 2020, we found four articles in the Web of Science database being two of them [13,14] by the same research group (Department of Chemical and Food Engineering – UFSC, Brazil). Although this technique allows the continuous process, a disadvantage of exploiting it is not being used by conventional plastic companies, which makes technology transfer difficult. Jo ur na l P re -p ro of 9 Compression-molding The compression-molding process consists of heating a thermoset resin under pressure and in a closed mold cavity; the resin liquefies and flows, taking the shape of the mold after cooling and, therefore, solidifying [15]. This method is low-cost when compared with others, such as injection molding, and it is suitable for a large number of materials production [15]. Moreover, little material is lost during the molding process, an advantage when working with expensive compounds. In recent years, this technology has been widely explored to produce bilayer films. This strategy allows combining two individual polymers in a single structure through bilayer association leading to better performance of the monolayers, in which at least one monolayer is produced with starch. Injection molding The injection molding technique consists in injecting a paste into a mold, with many control variables, such as powder granulation, paste temperature, filling rate, and mold temperature [16]. This method is widely used in polymer processing due to the ability to produce a high volume of complex plastic articles at low costs [16]. However, in the literature, most of the studies using this technology to produce biodegradable films relate the use of proteins, e.g. albumen, soy, pea, and rice protein, as biopolymers. Few studies report the use of starches and, in most of them, the starch is used as part of a blend. For example, a blend of starch and a copolymer of ethylene and vinyl alcohol; and a blend of native tapioca starch and polyethylene used as the binder of 316 L stainless steel powder [17,18]. Other studies reported the use of this technology combined with others, for example, extrusion [19]. Jo ur na l P re -p ro of 10 Extrusion Extrusion is a continuous and dynamic process that can be defined as a material in a solid or semi-liquid state that enters a fixed barrel and is transported until it exits the barrel, going through a die which shapes the material [20]. The transport is generally made by rotating screws. Inside the barrel, this materialundergoes several unit operations, such as mixing, heat exchange, melting, shear, and pressure drop. This thermomechanical treatment results in physical and chemical transformations in the material [21,22], generating changes in their properties [20]. In the shaping section, the material goes from liquid to solid-state, due to the change in pressure [21,23], resulting in the desired product. Extrusion is a major process for the polymer industry [21]; it is a flexible process and there are many extruder designs. The screws in an extruder are segmented, which means the screw can be assembled with different screw elements, depending on the process need, making possible a large range of configurations [21]. Among the possible designs, the ones that are most suited and used for starch-based plastics production will be described in detail. Single-screw extrusion The single-screw extrusion is used in the polymer industry, snacks, cereals, and oil separation process [21]. In a single-screw extruder, the barrel envelopes one rotating screw that can be assembled in a monobloc, with one type of screw elements in it, or in a modular assembly, with different screw elements. The latter configuration enables different sections in the extruder, namely feed, compression, metering and shaping section [21], making the process more effective. Jo ur na l P re -p ro of 11 Single-screw extrusion is a low-cost, easy to scale-up process, yet it is suited for simple compounds that do not require much flexibility of the process since it has less efficient mixing, conveying and heat transfer compared to twin-screw extrusion [21,22]. Twin-screw extrusion The twin-screw extruder design shows important advantages when compared to single- screw extrusion. The two screws can be co-rotating or counter-rotating, intermeshing, or with separate meshes. However, the most efficient design is the twin-screw co-rotating intermeshing extruder. Twin-screw extruders have only modular assembly [21] and there are more screw elements for this design. For example, kneading discs, which help to mix and to melt the material, can only be used in this design. Also, there are elements to increase residence time and to generate a compression in the material [24]. The advantages of the twin-screw extruder are the accuracy to meet each demand in the process since it has more flexibility for the assembly of the screws; efficient mixing and conveying; low-cost process; easy to scale-up [20,25]. In extrusion, this design is the most explored for starch-based plastic research, once it enables setting specific parameters depending on the process needs [21]. Reactive extrusion Reactive extrusion is a continuous operation that can occur in a single or twin-screw configuration. In this method, the extruder is used as a chemical reactor [26]. It is widely applied to the polymer industry, to chemically modify virgin or blended polymers. It is an important process for biomaterials, which often need to undergo a reaction - cross-link reaction, for example - to attain the desired property, mainly reinforcement, or that need a catalyst for the reaction to take place. Jo ur na l P re -p ro of 12 There are many advantages in using an extruder despite a traditional reactor. As the reaction medium is the melt, solvents are not necessary; an extruder is a proper equipment for materials with high viscosity, being able to continuously transport it; there is a large range of process conditions; it is a low-cost process that offers energy saving. Conversely, there are some disadvantages, since the extruder can only perform short residence-time reactions; if the reaction is extremely exothermic, it can be difficult to control the temperature in the medium [21,27]. Co-extrusion The co-extrusion process consists of two or more polymer materials being extruded together. This process arose due to the demand of the packaging industries for properties not achieved by a single polymer, although they could be served by a combination of polymers [28]. For example, Mazerolles et al. [29] obtained blends based on low-density polyethylene (LDPE) with thermoplastic potato and corn starch, more transparent and with greater oxygen barrier (~ 20 times) than the films based on pure LDPE. Using co-extrusion allows producing a plastic film with distinct layers without requiring intermediate steps, differently from the lamination process, required for producing plastic films isolated, which are later adhered together [30]. Co-extrusion can be used for both blown and cast films. Blown-extrusion The blown-extrusion technique is the most used for producing plastic films [7]. Its greatest application occurs due to its advantages, such as simple production equipment, low-cost, adjustable film size, and continuous production. Moreover, this technique is versatile and capable of making single-layer or multilayer films with a variety of film thicknesses and widths. Jo ur na l P re -p ro of 13 Blown-films, also known as tubular films, are produced by an extrusion process with a circle-shaped extrusion die, with air pressure used to further expand the film. After the film is expanded to the desired dimensions, it is cooled to promote the solidification of the material [31]. The use of this technique for producing films using starch (TPS) is still a challenge given the difficulty in blowing film due to the insufficient toughness of the melted TPS [32]. Hence, most of the studies involving the use of blown extrusion for elaborating starch- based films use a mixture of TPS with other polymers to adjust the rheological properties and to improve processability by this technique [32,33]. Table 1 shows some selected works involving the different methods of starch-based film production and their major findings considering scale-up, lower cost, lower time- consumption, and new technologies to improve the film properties. Barriers vs solutions to large-scale production Many factors could be pointed out as likely to obstruct the scaling-up process of biodegradable films based on starch. Some of them are listed below. The first point is that biodegradable films are characterized by poorer mechanical and water barrier properties than those made from conventional petroleum-derived polymers. The addition of other components to act as a reinforcement filler has been evaluated [47,48]. In recent years, studies focusing on reinforcing biodegradable materials with nanomaterials have been investigated, yet most of these studies have been performed on a laboratory scale. The effect of chemical interactions, lack of evidence of biodegradability, fear of toxicological and health effects of these nanomaterials should be evaluated [4]. Moreover, legal aspects must be established, such as the nanomaterial used in one country may not be permitted in another, making the commercialization of these materials difficult [4]. Jo ur na l P re -p ro of 14 Another strategy to improve the mechanical and barrier properties has been developed by blending starch-based with conventional petroleum-derived polymers. However, these blends may not be biodegradable; the advantages of using a biodegradable polysaccharide are thus lost [48]. Another approach to improve these properties (mechanical and barrier) is the multilayers strategy, in which it is possible to take advantage of the individual characteristic of the monolayer films. However, this strategy, requires long production time, high energy consumption, increasing cost due to the two processes requirement. Therefore, this alternative is less interesting despite providing good barrier properties [4]. The film production method most explored in academic works is casting. It is difficult to scale-up because it requires evaporation of a significant amount of water,which is a high energy-consumption process and unsuitable for scaling-up to industrial production. Long drying times prevent accurate thickness standardization [4], which is also related to the formation of water vapor bubbles within the biocomposite structure [47]. Extrusion and molding methods show large-scale capacity. However, the difficulty in further exploring the use of these methods of production for starch-based films must be their high equipment cost. Also, for the plastic companies that already have this equipment, the production of starch-based films is more laborious, expensive, and results in materials with properties not as good as conventional ones. Another point that does not favor the large-scale production of starch-based plastics is the need for a special composting system to ensure proper processing or recycling of biodegradable plastic packaging when discarded. If they are not properly disposed of, being mixed with common plastics, for example, they can be contaminated and can no longer be used. Another very polemic fact is the use of croplands to produce natural materials to create biodegradable plastics instead of using them to produce food. The options would Jo ur na l P re -p ro of 15 thus be to explore starches from agro-industrial residues, or unusual starch sources, or even starch sources with high availability. Finally, another fact that reduces the interest in large-scale production of starch-based films is that their properties can be compromised over time. For example, the properties of the films must be stable to protect the contained food. However, starch-edible films generally suffer aging. Few studies in the literature explore aging [4], which also hinders the scaling- up process. Despite the many points presented here that reflect the difficulty in producing starch-based plastics on a large-scale, we should reflect on two main factors: starch is a renewable source and starch-based plastics are biodegradable; they can thus help to solve the problems of petroleum depletion and accumulation of waste in the environment. Future perspectives In addition to all the scientific development to obtain biodegradable packaging, the environmental problem of plastic accumulation also relies on international and national government policies. For example, there are current policies for reducing the release of plastics in wastewater treatment plants [49], consumer education and awareness policies [50], besides improvements in the management of plastics life cycle [51]. Moreover, some public agencies have established control policies, including restrictions on advertisements, regulation of consumption, taxes and fees applicable to discourage the use of plastic, and banning single-use products [51–53]. Allied to that, companies have implemented voluntary actions known as corporate social responsibility (CSR) to perform sustainably in environmental spheres [51]. Thus, synergy is necessary among the policies created by governments, voluntary initiatives by industries, and changes in consumer behavior. Conclusion Jo ur na l P re -p ro of 16 We have seen that elaborating starch-based biodegradable plastics is a complex and more difficult process than the traditional petroleum-based polymers. Therefore, the modifications in the traditional processing techniques and the evaluation of processing conditions have been explored to overcome the challenges presented in polymer starch processing. The major methods of starch-based biodegradable plastics production were described in this study. Even though most of the studies in this field explore the lab-scale methods, the time-consuming drying step makes it uninteresting. Moreover, to streamline the process between the development of a material until it reaches the consumer, large-scale processing methods should be further explored, such as extrusion, injection molding, compression molding, and blowing. However, these techniques present their challenges, such as high equipment costs. Furthermore, governments need to establish a special composting system to ensure the proper discard of these materials. So far, the achievements in this area have contributed to a better understanding of the ability of starch to produce biodegradable polymers and the challenges involved in this field. However, the future of bio-based plastic production depends on a joint effort of academia, industries and governments. Declaration of interests The authors declare that they have no known competing for financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgments The authors acknowledge the State of São Paulo Research Foundation (FAPESP) for grants 2017/05307-8 and 2019/21700-7 and the National Council for Scientific and Technological Development (CNPq, Brazil) for grants 429043/2018-0 and 306414/2017-1. We would like Jo ur na l P re -p ro of 17 to thank the Food Research Center – FoRC for the financial support under FAPESP grant 2013/07914-8. References 1. Abdullah ZW, Dong Y: Recent advances and perspectives on starch nanocomposites for packaging applications . J Mater Sci 2018, 53:15319–15339. 2. Lumdubwong N: Applications of starch-based films in food packaging. In Reference Module in Food Science. . Elsevier; 2019. 3. Din MI, Ghaffar T, Najeeb J, Hussain Z, Khalid R, Zahid H: Potential perspectives of biodegradable plastics for food packaging application-review of properties and recent developments. Food Addit Contam Part A 2020, 37:665–680. 4*. Jeya Jeevahan J, Chandrasekaran M, Venkatesan SP, Sriram V, Britto Joseph G, Mageshwaran G, Durairaj RB: Scaling up difficulties and commercial aspects of edible films for food packaging: a review. Trends Food Sci Technol 2020, 100:210–222. This article reviews the research progress, confronting problems and research opportunities ahead for the industrial scaling up and commercial success for edible films in food packaging. 5. Spierling S, Knüpffer E, Behnsen H, Mudersbach M, Krieg H, Springer S, Albrecht S, Herrmann C, Endres H-J: Bio-based plastics - A review of environmental, social and economic impact assessments. J Clean Prod 2018, 185:476–491. 6. Zhong Y, Li Y, Liang W, Liu L, Li S, Xue J, Guo D: Comparison of gelatinization method, starch concentration, and plasticizer on physical properties of high- amylose starch films . J Food Process Eng 2018, 41:e12645. Jo ur na l P re -p ro of 18 7. Liu W, Wang Z, Liu J, Dai B, Hu S, Hong R, Xie H, Li Z, Chen Y, Zeng G: Preparation, reinforcement and properties of thermoplastic starch film by film blowing. Food Hydrocoll 2020, 108:106006. 8. Madhumitha G, Fowsiya J, Mohana Roopan S, Thakur VK: Recent advances in starch–clay nanocomposites . Int J Polym Anal Charact 2018, 23:331–345. 9. Siemann U: Solvent cast technology – a versatile tool for thin film production. In Scattering Methods and the Properties of Polymer Materials. . Springer Berlin Heidelberg; 2005:1–14. 10. de Moraes JO, Scheibe AS, Sereno A, Laurindo JB: Scale-up of the production of cassava starch based films using tape-casting. J Food Eng 2013, 119:800–808. 11**. Ochoa-Yepes O, Di Giogio L, Goyanes S, Mauri A, Famá L: Influence of process (extrusion/thermo-compression, casting) and lentil protein content on physicochemical properties of starch films . Carbohydr Polym 2019, 208:221–231. This article compares the properties of starch films produced by solvent casting in relation to industrial-scale process (extrusion/thermo-compression). 12. Mendes JF, Norcino LB, Martins HHA, Manrich A, Otoni CG, Carvalho EEN, Piccoli RH, Oliveira JE, Pinheiro ACM, Mattoso LHC: Correlating emulsion characteristics with the properties of active starch films loaded with lemongrass essential oil. FoodHydrocoll 2020, 100:105428. 13. de Moraes JO, Scheibe AS, Augusto B, Carciofi M, Laurindo JB: Conductive drying of starch-fiber films prepared by tape casting: Drying rates and film properties . LWT - Food Sci Technol 2015, 64:356–366. 14*. de Moraes JO, Laurindo JB: Properties of starch–cellulose fiber films produced by tape casting coupled with infrared radiation. Dry Technol 2018, 36:830–840. Jo ur na l P re -p ro of 19 This article compares three different drying procedures for the drying of starch– cellulose films in a tape-casting process: conduction drying, infrared drying, and conduction-infrared drying 15. Tatara RA: Compression molding. In Applied Plastics Engineering Handbook. . Elsevier Inc.; 2017:291–320. 16. Marçal RLSB: Biomaterials produced by injection molding. In Reference Module in Materials Science and Materials Engineering . . Elsevier; 2016. 17. Mano J., Reis R.: Viscoelastic monitoring of starch-based biomaterials in simulated physiological conditions . Mater Sci Eng A 2004, 370:321–325. 18. Abolhasani H, Muhamad N: A new starch-based binder for metal injection molding. J Mater Process Technol 2010, 210:961–968. 19. Yin P, Dong X, Zhou W, Zha D, Xu J, Guo B, Li P: A novel method to produce sustainable biocomposites based on thermoplastic corn-starch reinforced by polyvinyl alcohol fibers . RSC Adv 2020, 10:23632–23643. 20. Emin MA, Schuchmann HP: A mechanistic approach to analyze extrusion processing of biopolymers by numerical, rheological, and optical methods . Trends Food Sci Technol 2017, 60:88–95. 21. Bouvier J-M, Campanella OH: Extrusion processing technology. Hoboken: Wiley 2014, doi:10.1002/9781118541685. 22. Kazemzadeh M: Introduction to extrusion technology. CRC Press; 2012. 23. Della Valle G, Berzin F, Vergnes B: Modeling of twin screw extrusion process for food products design and process optimization. Adv food Extrus Technol 2011, doi:10.1201/b11286-14. 24. da Silva AS, Sobral Teixeira RS, Oliveira R de, Santana V, de Barros R da RO, Jo ur na l P re -p ro of 20 Antonieta M, da Silva Bo EP: Sugarcane and woody biomass pretreatments for ethanol production. In Sustainable Degradation of Lignocellulosic Biomass - Techniques, Applications and Commercialization. . InTech; 2013. 25. Emin MA, Schuchmann HP: Analysis of the dispersive mixing efficiency in a twin-screw extrusion processing of starch based matrix . J Food Eng 2013, 115:132–143. 26**. Formela K, Zedler Ł, Hejna A, Tercjak A: Reactive extrusion of bio-based polymer blends and composites – Current trends and future developments. 2018, 12:24–57. This article explains the reactive extrusion process through a literature review, discussing the advances, advantages and limitations of the method and the use of starch blends 27. Vergnes B, Berzin F: Modelling of flow and chemistry in twin screw extruders . Plast Rubber Compos 2004, 33:409–415. 28. Wang G, Chen F: Development of bamboo fiber-based composites. In Advanced high strength natural fibre composites in construction. . Elsevier; 2017:235–255. 29. Mazerolles T, Heuzey M-C, Soliman M, Martens H, Kleppinger R, Huneault MA: Development of multilayer barrier films of thermoplastic starch and low- density polyethylene . J Polym Res 2020, 27:44. 30. Selke SEM, Hernandez RJ: Packaging: polymers in flexible packaging. Reference Module in Materials Science and Materials Engineering: Elsevier; 2019. 31. McKeen LW: 3 - Production of films, containers, and membranes . In Plastics Design Library. Edited by McKeen LWBT-PP of P and E (Third E. William Andrew Publishing; 2012:39–58. Jo ur na l P re -p ro of 21 32. Huntrakul K, Yoksan R, Sane A, Harnkarnsujarit N: Effects of pea protein on properties of cassava starch edible films produced by blown-film extrusion for oil packaging. Food Packag Shelf Life 2020, 24:100480. 33. Gao W, Liu P, Li X, Qiu L, Hou H, Cui B: The co-plasticization effects of glycerol and small molecular sugars on starch-based nanocomposite films prepared by extrusion blowing. Int J Biol Macromol 2019, 133:1175–1181. 34. La Fuente CIA, Castanha N, Maniglia BC, Tadini CC, Augusto PED: Biodegradable films produced from ozone -modified potato starch. J Packag Technol Res 2020, 4:3–11. 35. Maniglia BC, Tessaro L, Ramos AP, Tapia-Blácido DR: Which plasticizer is suitable for films based on babassu starch isolated by different methods? Food Hydrocoll 2019, 89:143–152. 36. Menzel C, González-Martínez C, Chiralt A, Vilaplana F: Antioxidant starch films containing sunflower hull extracts . Carbohydr Polym 2019, 214:142–151. 37. Requena R, Vargas M, Chiralt A: Obtaining antimicrobial bilayer starch and polyester-blend films with carvacrol. Food Hydrocoll 2018, 83:118–133. 38. Valencia-Sullca C, Vargas M, Atarés L, Chiralt A: Thermoplastic cassava starch- chitosan bilayer films containing essential oils . Food Hydrocoll 2018, 75:107– 115. 39. Lenz DM, Tedesco DM, Camani PH, dos Santos Rosa D: Multiple reprocessing cycles of corn ctarch-based biocomposites reinforced with curauá Fiber. J Polym Environ 2018, 26:3005–3016. 40. Zarski A, Bajer K, Raszkowska-Kaczor A, Rogacz D, Zarska S, Kapusniak J: From high oleic vegetable oils to hydrophobic starch derivatives: II. Physicochemical, Jo ur na l P re -p ro of 22 processing and environmental properties . Carbohydr Polym 2020, 243:116499. 41. Fitch-Vargas PR, Camacho-Hernández IL, Martínez-Bustos F, Islas-Rubio AR, Carrillo-Cañedo KI, Calderón-Castro A, Jacobo-Valenzuela N, Carrillo-López A, Delgado-Nieblas CI, Aguilar-Palazuelos E: Mechanical, physical and microstructural properties of acetylated starch-based biocomposites reinforced with acetylated sugarcane fiber. Carbohydr Polym 2019, 219:378–386. 42*. Ghanbari A, Tabarsa T, Ashori A, Shakeri A, Mashkour M: Preparation and characterization of thermoplastic starch and cellulose nanofibers as green nanocomposites: Extrusion processing. Int J Biol Macromol 2018, 112:442–447. This article presents the method to prepare thermoplastic starch and to incorporate CNFs as reinforcers for the produced films. Also, it shows the analysis of films to verify their properties. 43*. Vedove TMARD, Maniglia BC, Tadini CC: Production of sustainable smart packaging based on cassava starch and anthocyanin by an extrusion process . J Food Eng 2021, 289:110274. This article presents a large-scale production (twin extrusion process) of smart packaging using cassava starch and anthocyanin. Also, the smart action of the packaging was investigated. 44. Herniou-Julien C, Mendieta JR, Gutiérrez TJ: Characterization of biodegradable/non-compostable films made from cellulose acetate/corn starch blends processed under reactive extrusion conditions . Food Hydrocoll 2019, 89:67–79. 45. Simões BM, Cagnin C, Yamashita F, Olivato JB, Garcia PS, de Oliveira SM, Eiras Grossmann MV: Citric acid as crosslinking agent in starch/xanthan gum Jo ur na l P re -p ro of 23 hydrogels produced by extrusion and thermopressing . LWT 2020, 125:108950. 46. Pattanayaiying R, Sane A, Photjanataree P, Cutter CN: Thermoplastic starch/polybutylene adipate terephthalate film coated with gelatin containing nisin Z and lauric arginate for control of foodborne pathogens associated with chilled and frozen seafood. Int J Food Microbiol 2019, 290:59–67. 47. Otoni CG, Lodi BD, Lorevice M V., Leitão RC, Ferreira MD, Moura MR de, Mattoso LHC: Optimized and scaled-up production of cellulose-reinforced biodegradable composite films made up of carrot processing waste . Ind Crops Prod 2018, 121:66–72. 48**. Jiang T, Duan Q, Zhu J, Liu H, Yu L: Starch-based biodegradable materials: challenges and opportunities . Adv Ind Eng Polym Res 2020, 3:8–18. This paper reviews the recent development of starch-based materials, including both fundamentaland application researches. 49. Raubenheimer K, McIlgorm A: Can the basel and stockholm conventions provide a global framework to reduce the impact of marine plastic litter? Mar Policy 2018, 96:285–290. 50. Schneider DR, Arne M Ragossnig: Recycling and incineration, contradiction or coexistence? Waste Manag Res 2015, 33:693–695. 51. Ashrafi M, Adams M, Walker TR, Magnan G: ‘How corporate social responsibility can be integrated into corporate sustainability: a theoretical review of their relationships.’ Int J Sustain Dev World Ecol 2018, 25:672–682. 52. Watkins E, Schweitzer J-P, Leinala E, Börkey P: Policy approaches to incentivise sustainable plastic design. 2019, doi:10.1787/233ac351-en. 53. Prata JC, Silva ALP, da Costa JP, Mouneyrac C, Walker TR, Duarte AC, Rocha- Jo ur na l P re -p ro of 24 Santos T: Solutions and integrated strategies for the control and mitigation of plastic and microplastic pollution. Int J Environ Res Public Health 2019, 16:2411. Jo ur na l P re -p ro of 25 Figure caption Fig. 1. The number of papers (from 2015 to 2020) found in the Web of Science database for the following methods of starch-packaging production: casting, molding or extrusion. Jo ur na l P re -p ro of 26 Table 1. Selected papers involving different methods of starch-based biodegradable plastics. Starch-based biodegradable plastic developments Major findings Refs. Solvent casting Films based on potato starch were modified by ozone technology. The starch treated for 30 min with ozone resulted in more rigid, less flexible, less hydrophilic, and more transparent films than native starch ones. [34] The effect of the interaction of babassu starches (starch extraction by methods: steeping in acid medium - AS in alkaline medium - KS and neutral medium - WS) with plasticizers (sorbitol, glycerol, urea, or glucose) on the film properties was evaluated. The type of plasticizer did not affect the color or the antioxidant activity, but it affected the opacity, the chemical composition, and the structure of the film. Films with KS and AS starches and plasticized with glycerol and urea were more hydrophilic and more permeable to water vapor, less opaque, less mechanically resistant and less crystalline. Films with WS starch showed this behavior when sorbitol or glucose was used as a plasticizer. [35] Tape-casting The effect of the suspension thickness (starch and fiber) and the temperature on the conductive drying rate and the film properties were evaluated. Both parameters influenced the drying rate and film properties. Furthermore, it was observed that to obtain films with satisfactory properties, a maximum 60 °C temperature of drying is necessary, and thickness between (3 and 4) mm. It was possible to dry the films elaborated by tape-casting in 2.3 h (a much shorter time than that observed in conventional casting processes). [13] Jo ur na l P re -p ro of 27 Cassava starch–cellulose films using a tape-casting method were produced using three different drying procedures: conduction, conduction-infrared, and infrared drying. The methods of infrared or conduction-infrared drying were faster (~1 h) than conduction drying. The films dried using infrared and conduction-infrared showed similar tensile strength, hygroscopicity, and glass transition temperature. [14] Compression molding A blend with potato starch incorporated with phenolic compounds extracted from sunflower hulls was prepared. The films showed good thermal stability with the potential use of potato starch to produce 100 % renewable and recyclable material, which can be easily produced at a low cost. [36] Bilayer films are widely studied and produced by compressing molding. In many of these studies, one monolayer is cassava starch combined with polyester blends incorporating carvacrol, chitosan containing essential oil or poly (lactic) acid PLA. In general, all of these studies showed excellent results with the combination of both matrices with enhanced characteristics, taking advantage of the monolayer characteristics. [37,38] Injection Molding Biocomposites with corn starch and a vegetable curauá fiber were developed. It was observed that the fibers increased the hardness, tensile strength, and decreased the strain. Moreover, the weight loss in soil degradation tests reached around 10 g/100 g after 230 days, showing to be a potential biodegradable material. [39] Single-screw extrusion Potato starch was blended with an ester, a result of the reaction between starch and fatty acids obtained from oil hydrolysate with the purpose of reinforcement and hydrophobicity of the bioplastic. A pre-analysis was carried out to verify the thermal stability of the starch and oil binding. the films were obtained using glycerol as a plasticizer. Among the analyses carried out, biodegradability and phytotoxicity were verified. The results showed an improvement in mechanical properties, lower water absorption and an eco-friendly product. [40] Jo ur na l P re -p ro of 28 The authors developed a biocomposite using corn starch and sugarcane fiber for reinforcement. Aiming to improve the hydrophilicity, a commonly verified issue, this work proposed a prior chemical treatment for the starch and the fiber, acetylation. Different concentrations of fiber were used. After the analyses of the product, it was verified that the sugarcane fiber can be incorporated as a reinforcer with effective results. [41] Twin-screw extrusion The goal of the paper was to develop nanocomposites with thermoplastic corn starch (TPS) and cellulose nanofibrils (CNFs) as reinforcement, focusing on a scale-up of the process. After analyzing the product, a good CNF dispersion in the TPS was verified, along with lower water absorption, and an enhancement in mechanical properties. [42] A sustainable smart packaging (sheets) based on cassava starch and anthocyanin (a natural pH indicator) by a twin-screw extrusion process was developed. The effect of the anthocyanin concentration on the properties of the sheets was evaluated. Also, the smart sheets were tested as a pH indicator in packaging trials with beef and fish for 3 days. The authors observed that the addition of anthocyanin resulted in thicker sheets, less resistant at break, flexible, and less rigid than the control ones. Thermoplastic starch sheets incorporated with 20 mg anthocyanin/100 g showed the best behavior as a smart packing indicator of pH change in beef stored at 6 °C. [43] Reactive extrusion The authors developed a packaging material with food hydrocolloids by reactive extrusion to achieve cross-link reactions. Using corn starch, chromium octanoate as food catalyst, cellulose acetate as filler, and glycerol as a plasticizer, the films were obtained in a twin-screw extruder, varying the concentration of the food catalyst and the filler, to evaluate their effectiveness. The results suggested that the cross-link reaction occurred. Also, biodegradability was verified. [44] Jo ur na l P re -p ro of 29 Citric acid was used to achieve cross-link reactions. A hydrogel sheet was produced with cassava starch, and xanthan gum, using citric acid as an agent for cross-link reactions, glycerol as a plasticizer and sodium hypophosphite as a catalyst. Using a single-screw extruder, pellets and sheets were obtained. Finally, the sheets were placed in a hydraulic press to result in a cured hydrogel. Once the product was analyzed, it was observed that the cross-link reactions occurred, resulting in a film with better mechanical properties and lower water absorption. [45] Co-extrusion Multilayer films were developed by co-extrusion of low-density polyethylene (LDPE) and potato and corn thermoplastic starch (TPS). In this work, the authorsalso investigated the effect of adding natural and organo-modified clays in the TPS phase to investigate its effect on the mixture morphology, processability, and physical properties of the film. Natural clay improved the processing and quality of the film. The films formed by multilayer (LDPE and TPS) were more transparent, had a higher oxygen barrier (~ 20 times), and maintained the good mechanical properties of the films made only with LDPE. [29] The authors produced antimicrobial film by co-extrusion based on polybutylene adipate terephthalate (PBAT) and thermoplastic starch (TPS) with gelatin coating containing pure lauric arginate (LAE) or combined with nisin Z. The researches evaluated the antimicrobial activity of the films when packing shrimp in conditions of refrigeration or freezing for a long period. No films with antimicrobial activity were obtained when LAE was added directly to TPS/PBAT by co-extrusion. Thus, the option was for direct LAE coating on the TPS/PBAT film. Finally, the results from this study indicated that the films showed excellent inhibition against V. parahaemolyticus and S. Typhimurium in chilled or frozen seafood. [46] Jo ur na l P re -p ro of 30 Blown-extrusion Production of blown-extrusion films based on acetylated cassava starch (AS) and pea protein isolate (PI). The increase in PI caused a reduction of flexibility, light transmission and solubility, but increased crystallinity, protein aggregation, surface hydrophobicity, thermal stability, tensile strength, and barrier properties against water vapor, and oxygen of the films. [32] Production by blown-extrusion of starch-based nanocomposite films with different co-plasticizers (fructose, sucrose, glucose, and glycerol). The presence of sugars prevented the formation of interleaved structures reducing the relative crystallinity of the films, increasing the water vapor permeability, and reducing the resistance at the break and the glass transition temperature. The presence of sugars resulted in the fracturing and melting of starch granules. Sugars enhanced the flexibility of the films. Sucrose resulted in a better performance of the film than the other sugars (fructose or glucose). [33] Jo ur na l P re -p ro of