Biodegradable Polymers Concepts and Applications Editors Margarita del Rosario Salazar Sánchez Departamento de Ciencias Agroindustriales Facultad de Ingenierías y Tecnológicas Universidad Popular del Cesar Cesar, Colombia José Fernando Solanilla Duque Departamento de Agroindustria Facultad de Ciencias Agrarias Universidad del Cauca Popayán, Colombia Aidé Sáenz Galindo Facultad de Ciencias Química Universidad Autónoma de Coahuila Saltillo, México Raúl Rodríguez Herrera Universidad Autónoma de Coahuila Saltillo, México A SCIENCE PUBLISHERS BOOK Cover illustration reproduced by kind courtesy of Margarita del Rosario Salazar Sánchez. First edition published 2023 by CRC Press 6000 Broken Sound Parkway NW, Suite 300, Boca Raton, FL 33487-2742 and by CRC Press 4 Park Square, Milton Park, Abingdon, Oxon, OX14 4RN © 2023 Margarita del Rosario Salazar Sánchez, José Fernando Solanilla Duque, Aidé Sáenz Galindo and Raúl Rodríguez Herrera CRC Press is an imprint of Taylor & Francis Group, LLC Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, access www.copyright.com or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. For works that are not available on CCC please contact [email protected] Trademark notice: Product or corporate names may be trademarks or registered trademarks and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging‑in‑Publication Data (applied for) ISBN: 978-1-032-13714-8 (hbk) ISBN: 978-1-032-13715-5 (pbk) ISBN: 978-1-003-23053-3 (ebk) DOI: 10.1201/9781003230533 Typeset in Times New Roman by Radiant Productions Preface As a consequence of the negative impact of synthetic polymers on the environment, not only for the present generation but also for future generations, the need has arisen to develop biodegradable polymers that not only meet most of the quality standards for the manufacture of products but also have a degradation period much shorter than that of synthetic polymers. This book appears as a collaborative project between different institutions of higher education and research in order to bring together the different topics related to the production, application and final destination of biodegradable polymers, and their impact on modern life and on future generations. The book of biodegradable polymer science reveals the basic concepts of biodegradable polymer science, describing the techniques, standards and analysis to be performed to characterize biodegradable polymeric materials, highlighting that it is important to further develop and/or innovate processes considering the environment. Pointing to this, this book focuses on the engineering of biopolymers in food processing and explores the processing technology associated with biopolymer applications. The difference between a normal book on biodegradable polymers and the present book is that in our version, there are some very interesting chapters that are framed on the rheological and structural analysis, in addition to the applications in different areas of knowledge such as: health, agriculture and technology. The present book will be useful for the biodegradable polymer’s industry because it covers from films to composites, as well as in academia and research including framing processes of analysis and technology which could be used to improve biodegradable polymer production, where the reader will find different tools to become familiar with biopolymers analysis and implementation of these analyses. The contribution of this book would complement the themes developed by a reference book on biodegradable polymer bases because this book refers to treatment topics among which are Compounding and Additives, Powdering, Chemical Treatment, Surface Treatment, Adhesive Compositions, Biopolymer Engineering in Food Processing and Biodegradation, other product developments from these biopolymers are also covered. All applications are shown from a sustainability and sustainability approach, it is important to highlight that biodegradability has a great burden when it involves substituting, modifying and/or designing existing processes in harmful and polluting processes. The book concludes with a reflection on the development of biodegradable polymers in different areas of knowledge and trends. Contents Preface iii Introduction vi 1. Biodegradation of Polymers 1 Sarai Agustín Salazar, Sabu Abdulhameed and Margarita del Rosario Salazar Sánchez 2. Use of Renewable Source in Biodegradable Polymer 13 J.J. Cedillo‑Portillo, J.D. Flores‑Valdes, W.Y. Villastrigo‑López, D.W. González‑Martínez, A.O. Castañeda‑Facio, S.C. Esparza‑Gonzalez, R.I. Narro‑Céspedes and A. Sáenz‑ Galindo 3. Plastics Technology 32 Marlene Lariza Andrade‑Guel, Alma Berenice Jasso‑Salcedo, Diana Iris Medellín‑Banda, Marco Antonio De Jesus‑Tellez and Christian Javier Cabello‑Alvarado 4. Analysis and Testing of Biopolymers 55 María C. García‑Castañeda, Kassandra T. Ávila‑Alvarez, Marco A. García‑Lobato, Anna Ilyina and Rodolfo Ramos‑González 5. Structure and Morphology of Biodegradable Polymers 64 Felipe Avalos Belmontes, Francisco J. González, Mónica Esmeralda Contreras Camacho, Aidé Sáenz‑Galindo and Rodrigo Ortega Toro 6. Rheology Properties of Biodegradable Polymers 80 Juan Pablo Castañeda Niño, José Herminsul Mina Hernandez, Heidi Andrea Fonseca Florido, Leticia Melo López, Margarita del Rosario Salazar Sánchez and Jose Fernando Solanilla Duque 7. Structural Analysis of Polymers and Composite Materials 99 Juan Pablo Castañeda Niño, José Herminsul Mina Hernandez, Alex Valadez González and Jose Fernando Solanilla Duque 8. Films 112 Karla C. Córdova‑Cisneros, Paola F. Vera‑García, Karina G. Espinosa‑Cavazos, Omar A. Martínez‑Anguiano, Aidé Sáenz‑Galindo and Adali O. Castañeda‑Facio 9. Composites and Novel Applications in the Biomedical Field 129 Claudia Gabriela Cuellar Gaona, Rosa Idalia Narro Céspedes, Ricardo Reyna, Martínez, Víctor Adán Cepeda Tovar, Karina Reyes Acosta and Aidé Sáenz Galindo 10. Green Materials in the Packaging: Biodegradable Foams 148 Sindhu Thalappan Manikkoth, Deepthi Panoth, Kunnambeth M. Thulasi, Fabeena Jahan, Anjali Paravannoor and Baiju Kizhakkekilikoodayil Vijayan 11. Biodegradable Foams: Processes and Applications 160 Lorena Farías‑Cepeda, Lucero Rosales Marines, Anilú Rubio Rios, Victor A. Cepeda Tovar, Karina Y. Reyes Acosta and Bertha T. Pérez‑Martínez Contents v 12. Thermo-Shrinkable Biodegradable Polymers 177 Reyes‑Acosta Yadira Karina, Farias‑Cepeda Lorena, Rubio‑Ríos Anilú, Rosales‑Morales Lucero, Reyna‑Martínez Ricardo, Alonso‑Montemayor Francisco Javier and Cepeda‑Tovar Víctor Adán 13. Applications of Biodegradable Polymers in Food Industry 189 Jose Fernando Solanilla‑Duque, Diego Fernando Roa‑Acosta, Luis Daniel Daza, Darwin Carranza‑Saavedra, Henry Alexander Váquiro, Juan Pablo Quintero‑Cerón, Maria Julia Spotti and Carlos Carrara 14. Health Applications of Biodegradable Polymers 207 Sandra Cecilia Esparza González, Aide Saenz Galindo, Raúl Rodriguez Herrera, Claudia Magdalena López Badillo, Lissethe Palomo‑Ligas, Isai Medina Fernandez and Victor de Jesús Suarez Valencia 15. Natural Polymers: Applications in the Health Field 218 Carneiro‑da‑Cunha, M. G., Granja, R. C. B., Souza, A. A., Melo, E. C. C., Oliveira, W. F. and Correia, M. T. S. 16. Bioplastics: Challenges and Opportunities 229 Lily Marcela Palacios, Germán Antonio Arboleda Muñoz, Héctor Samuel Villada Castillo and Hugo Portela Guarín 17. Tendencies and Applications in Biodegradable Polymers 243 Lucía F. Cano Salazar, Denis A. Cabrera Munguía, Tirso E. Flores Guía, Jesús A. Claudio Rizo, Martín Caldera Villalobos and Nayvi Y. Nava Cruz 18. Tendencies in Development of Biodegradable Polymers 260 Lluvia Itzel López‑López 19. Assessment of Biodegradability in Polymers: Mechanisms and Analytical Methods 272 Francisco J. González, Francisco J. Rivera‑Gálvez, Felipe Avalos Belmontes and Mario Hoyos 20. Biodegradable Packaging: Colombian Coffee Industry 289 Germán Antonio Arboleda Muñoz, Lily Marcela Palacios, Hugo Portela Guarín and Héctor Samuel Villada Castillo 21. Agriculture Applications of Biodegradable Polymers 300 Rocio Yaneli Aguirre‑Loredo, Lluvia de Abril Alexandra Soriano Melgar, Luis Valencia, Gonzalo Ramírez García and Alma Berenice Jasso‑Salcedo 22. Insight on Polymeric Hydrogel Networks: A Sustainable Tool for the Isolation 320 of Enzymes and Bioremediation Bárbara Bosio, Paola Camiscia, Guillermo Picó and Nadia Woitovich Valetti Index 337 Editors Biography 339 Introduction Zainul Akmar Zakaria,1 Siti Hajjar Che Man,1 Rocio Castillo‑Godina2 and Raul Rodriguez‑Herrera2 Biopolymers are produced by living organisms and should be differentiated for its term synthetic biodegradable polymers. The monomer units of most biopolymers usually consist of recurring molecules of either nuclei acid of nucleotides (deoxyribonucleic acid, DNA and ribonucleic acid, RNA), amino acid proteins (collagen, gelatin, gluten) or saccharides derived from sugars such as cellulose, chitosan, chitin (Samrot et al., 2020). Increasing depletion of petroleum-based resources to produce various types of polymers as well as its associated non-biodegradability features, has become the major driving force in the continuous development in the area of biopolymers production, processing and applications. Biopolymer offers an interesting and viable solution for this problem based on its biodegradability features. Notably, some weaknesses such as high cost, limited rate of production and poor mechanical properties have been identified as focus for further investigation in this area. Biopolymers are comprehensively segregated into two principle groups namely biodegradable and non-biodegradable (Rai et al., 2021). They can also be classified as elastomers, thermosets and thermoplastics according to their physical and chemical changes when stressed in different thermal conditions (George et al., 2020). Other researchers have classified biopolymers according to its various forms of either composites, blends or laminates. Some examples for commercially-produced biopolymers include polyesters (polyhydroxybutyrate, PHB) and (polybutylene succinate, PBS), bio-polyolefins, Bio-PE (polyethylene), bio-polyamides, Bio-PA (homopolyamides - Bio-PA 6, Bio-PA 11) and biopolyurethanes, Bio-PUR. Biopolymers have been established and gained significant interest in various applications such as biomedical, nanomaterials, food industry as well as water treatment. The ability of this polymer to be tailored with other materials to suit certain properties made them more attractive and feasible. In biomedical applications (Moohan et al., 2020), biopolymers such as starch, cellulose, chitosan, polylactic acid (PLA) (Ghalia and Dahman, 2017) and Poly (Glycolide Acid) (PGA) have been extensively used for tissue engineering, pharmaceutical carriers and medical devices. These polymers are known for their advantageous features that include cytocompatibility and the ability to degrade in the body without releasing harmful substances. Tyler et al. (2019) reviewed the applications of PLA and its copolymers as nanoparticle drug carriers, such as liposomes, polymeric nanoparticles, dendrimers and micelles. The ability of PLA to be moldable, allowing its applications to take on numerous shapes, i.e., scaffolds, sutures, micelle, etc., to suit such applications. Other than PLA, biopolymers such as gelatin and hydroxyapatite (HA) has been long used as artificial scaffolds, due to their compatibility to the natural bone tissue (Hajinasab et al., 2018; Szcześ et al., 2017). Despite 1 School of Chemical and Energy Engineering, Faculty of Engineering, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia. 2 Autonomous University of Coahuila, School of Chemistry, Blvd. V. Carranza and J. Cardenas s/n, Col. Republica Ote. Saltillo Coahuila 25280. México. * Corresponding author: [email protected] Introduction vii their advantages, there are several limitations that restrict their use for these particular applications due to the lack of mechanical strength. To date numerous studies have been reported to improve the issue with the property’s instability of this biopolymers (Hamad et al., 2015; Reddy et al., 2015). Recently, biopolymers are preferred to be used in food packaging coating to replace the traditional non-degradable materials such as polypropylene, polyethylene, etc. The demand for higher shelf life as well as better packaging quality have led to the increased interest in this area. Biopolymers such as starch, polyhydroxyalkanoates (PHA), polyhydroxybutyrates (PHB), PLA and so on, are among the commercially viable materials in food packaging, which can be processed via conventional equipment. Barrier properties is an extremely important characteristic especially for biobased food packaging materials. Biopolymers are known as hydrophilic materials with inadequate moisture resistance. Thus, various improvements have been reported to enhance the barrier properties as well as the mechanical properties. The development of coatings from natural polymers for food packaging have received significant interest to overcome the issue. Various polysaccharides and protein-based compounds have been investigated for food packaging coating which shown good grease, good affinity to the packaging substrate as well as a positive effect on mechanical properties (Nechita et al., 2020). Chemical and physical crosslinking such as grafting and coating have been reported to improve the compatibility of the coating and substrate (Reddy et al., 2015). The incorporation of nanofillers into biopolymers matrices not only to enhance the mechanical and barrier properties but also to impart other attractive properties such as antimicrobial agent and biosensor (Othman, 2014; Qamar et al., 2020). Preparation of nanomaterials derived from cellulose (CNs) have recently gained significant interest, due to their excellent inherent and physical properties. In addition, CNs may serve as an inexpensive, renewable and biodegradable in comparison to its counterpart carbon nanotubes (CNTs). It was reported that CNs exhibited a greater axial elastic modulus than Kevlar and its mechanical properties are within the range of other reinforcement materials. The presence of reactive surface of –OH side groups in the structure of CNs enables the grafting of chemical species to achieve surface functionalization which allows the tailoring of particle surface chemistry to facilitate self-assembly (Moon et al., 2011). To date, the potential of CNs have been recognized in various fields, i.e., paper and packaging, automotive, medical, construction, personal care, textile industries as well as waste water treatment (Carpenter et al., 2015; Mohan et al., 2020; Tayeb et al., 2018). In other applications, biopolymers have been incorporated in the fabrication of lithium-ion battery separators due to the excellent properties particularly low cost, high thermal stability, excellent mechanical properties, non-toxic, light-weight and excellent wettability to the electrolyte (Xu et al., 2014; Zhang et al., 2019). Whereas in biosensor application, biopolymer is a great material to be used as it can act as good immobilization matrix for entrapping biorecognition units such as enzymes, whole cells and others and provide good adhesion of the composite to electrode for carrying out sensing measurements. Next the most important facts of the book chapters will be mentioned. In Chapter 3 on the science of biodegradable polymers, it is emphasized that synthetic polymers in general meet many needs of the human population, which is why they are materials of mass consumption, however, characteristics such as: high resistance to corrosion, water and bacterial decomposition makes them difficult to eliminate, and consequently, a serious environmental problem that lasts for years (Valero-Valdivieso et al., 2013). On the other hand, there has been a demand for products that replace petroleum-derived plastics with alternatives based on renewable resources and above all biodegradable. This focuses an approach of multiple scientific disciplines and the so-called science of biodegradable polymers arises. Biodegradable polymers are those that have the ability to decompose in the presence of enzymes produced by microorganisms such as: bacteria, fungi and algae. It is necessary to differentiate between degradable, which refers to decomposition due to chemical or physical changes, while biodegradable is due to degradation by biological mechanisms (Niaounakis, 2013; Karamanliouglu et al., 2017). viii Biodegradable Polymers: Concepts and Applications The latest trends in polymer production include the use of renewable sources (Chapter 4) instead of traditional polymers based on fossil sources, responsible for CO emissions into the atmosphere 2 and which also generate non-biodegradable waste, taking years for its decomposition, which therefore represents an environmental problem (Peplow, 2016; Llevot et al., 2016). Biodegradable polymers can be produced by biological systems (microorganisms, plants and animals) or they can be synthesized from biological raw materials (for example, corn, sugar, starch, etc.), also known as bio-based (Gómez and Yory, 2018). In general, the production of these biopolymers includes synthetic polymers obtained from renewable resources, such as: polylactic acid (PLA); biopolymers produced by microorganisms such as polyhydroxyalkanoate (PHA) and natural biopolymers such as starch or proteins (Rudin and Choi, 2013). Biodegradable polymers can be classified as follows: • Polymers extracted or removed directly from biomass: polysaccharides such as starch and cellulose. Proteins like casein, keratin and collagen. • Polymers produced by classical chemical synthesis using biological monomers from renewable sources. • Polymers produced by microorganisms, native or genetically modified producing bacteria. In Chapter 5, the authors focus on plastics technology, specifically those of biological origin: PHAs and polylactic acid (PLA). PHAs are also called “double green polymers.” PLA is a natural monomer produced by fermentative ways from elements rich in sugars, cellulose and starch. Bioplastics have physicochemical and thermoplastic properties equal to those of polymers made from oil, but once deposited under favorable conditions, they biodegrade (Díaz del Castillo, 2012). Polymerization is the process in which small molecules of a single unit (monomers) or of a few units (oligomers) are chemically united to create bigger molecules, in which the atoms are strongly linked by a covalent bond (Díaz del Castillo, 2012). Currently, enzymatic polymerization represents a great approach to functionalizing polymers and biopolymers and preventing the generation of waste through the use of catalytic processes with high selectivity, as well as preventing or limiting the use of dangerous organic reagents (Peponi et al., 2015). The technological methods of manufacturing plastics are determined by their rheological properties and will depend on whether the material in question is thermoplastic or thermoset. Some of these methods are: injection molding, blow molding, rotational molding, blow processing methods, calendaring, casting, coatings, extrusion, film techniques, foam forming, lamination and low-pressure molding, filling techniques, plasticizers and other additives, an example of the latter such as antioxidants and colorants (Billmeyer, 2020). Polymers obtained from both oil and renewable natural resources need to be analyzed using different methodologies, which are discussed in Chapter 6, within these techniques are: Analytical methods in which the process used in polymers is not different from the techniques used in low molecular weight organic compounds. The physical analysis of polymers consists of different techniques: mass spectrometry and gas chromatography, infrared spectroscopy, in which the emission and absorption spectra of the molecules are determined, X-ray diffraction analysis, nuclear magnetic resonance spectroscopy and electrical spin, thermal analysis, which includes experimental methods of calorimetry, differential thermal analysis, microscopy and physical tests that include mechanical properties, fatigue tests, thermal properties, optical properties, electrical properties and chemical properties (Billmeyer, 2020). The structure of polymers is covered in Chapter 7, which depends on the shape of the chains. Based on the structure, polymers can be classified as linear, branched or cross-linked (López-Carrasquero, 2004). Linear polymers are those in which the monomeric units are linked side by side in a single direction. Under certain conditions or with certain types of monomers, polymers with another type of architecture can be obtained which are characterized by having branches that are generated from the main chain, this characteristic has significant effects on many physical properties Introduction ix of the polymer, for example, in decreasing crystallinity. Branched polymers cannot easily fit into a crystal lattice as linear polymers do. On the other hand, branched polymers are much less soluble than their linear counterparts and cross-linked polymers are insoluble materials. Crosslinking can occur during the polymerization process or later through various chemical reactions. Crosslinking is used to impart good elastic properties in some elastomers, as well as to provide rigidity and dimensional stability to some materials called thermoplastics. Biopolymers have macromolecules (proteins, carbohydrates, etc.), that generate dispersions that have certain rheological behaviors (Zambrano-Herrera, 2020). Rheology studies the fundamental and practical knowledge of the deformation or flow of matter (Hernández, 2014). Based on the above, Chapter 8 discusses the rheological properties of biopolymers. This branch of physics allows the characterization of flow patterns during processing, which facilitates handling and operating conditions, in addition to the properties of the final product (Zambrano-Herrera, 2020). One of the most common forms of bioplastics is in the form of thin sheets obtained from blowing films. In this procedure, a thin-walled tube is extruded and then expanded by increasing the internal pressure of the tube (Mendoza and Velilla, 2011). In Chapter 9, the authors report the research on thin films and mixtures to obtain biodegradable polymers. In this regard, starch is widely used, given its availability and low cost. Starch is used as a thermoplastic in the production of biodegradable plastics (Funke, 1998). During its production, it must be mixed with a plasticizer and undergo a de-structuring procedure to be processed by injection, blow molding and extrusion (Thuwall, 2006). In Chapter 10, the authors deal with composites which are composite materials that are characterized by exceeding the properties of the materials if they were used individually and by possessing specific properties and characteristics. These materials are made up of two phases; a continuous one called matrix and another dispersed called reinforcement. The reinforcement provides the mechanical properties to the composite material and the matrix provides thermal and environmental resistance. The matrix and the reinforcement are separated by the interface. Composite materials are classified according to their structural components: fibrous, laminated and particulate (Lubin, 2013). In the gradual interest of finding biodegradable materials to replace EPS expanded polystyrene foam, different studies have focused on developing starch foams, which have been industrially obtained by extrusion, although these biodegradable foams have properties similar to polystyrene materials. Some studies have been carried out to improve its mechanical properties by adding cellulose (Motloung et al., 2019), chitosan, sugar cane fibers (Debiagi et al., 2011), Yucca flour, corn fiber (Sumardiono et al., 2021), bioplastic from banana peel (Castillo et al., 2015) and other biodegradable polymers. This topic on biodegradable foams is addressed in the Chapter 11. Many of the alternatives seek to take advantage of agricultural residues to obtain a sustainable and biodegradable product in order to reduce the consumption of non-renewable sources in the coming years. The variation of different external factors, especially temperature, cause changes in the shape of polymers during their processing. Thus, heat-shrinkable polymers result from different heat stimuli and therefore changes in their shape in Chapter 12 describes the advantages and disadvantages of this kind of polymers. Currently, some studies focus on replacing synthetic materials with flexible films from biodegradable sources (Montilla et al., 2016; Montilla and Joaquí, 2016), because of the multiple applications that heat-shrinkable biodegradable polymers have. These heat-shrinkable polymers have application in many fields: packaging (Khankrua et al., 2019), medical devices, drug administration, intravenous needles (Xiao et al., 2019), electronic devices, digital storage media (Cui et al., 2017), etc. Some of the fundamental characteristics of polymers to be used in medicine, is that they must be biocompatible, that its mechanical properties are suitable for use, that they are excretable and non-toxic for the recipient and that they can be sterilized (Labeaga, 2018). Based on these antecedents in Chapter 14 the health applications of biodegradable polymers are discussed. The most common application of biopolymers in surgeries is for development of absorbable sutures, some examples