A Comparison of Mechanical Properties of Natural Fiber Filled Biodegradable and Polyolefin Polymers I.

Taha Institute for Polymer Materials and Plastics Processing, Clausthal University of Technology, Agricolastrasse 6, D-38678 Clausthal-Zellerfeld, Germany, iman.taha@tuclausthal.de G. Ziegmann Institute for Polymer Materials and Plastics Processing, Clausthal University of Technology, Agricolastrasse 6, D-38678 Clausthal-Zellerfeld, Germany A great value is nowadays being given to light-weight structures and durable light-weight materials and composites. In this respect, fiber reinforced plastics (FRP) are given more importance and are becoming one of the most distinguishing material categories next to metals. This research provides some results of mechanical properties of natural fiber reinforced polyolefins (PP, PE) in comparison to some biodegradable polymers, combined without any bonding enhancements, such as bonding agents or surface modifications. It is for this reason that the composites in this study do not show significant improvement in the mechanical properties of polymers; however they can be used as reference values for the mere natural fiber reinforcement. A comparison of polyolefins and biodegradable polymers shows that some biodegradable polymers eventually provide higher mechanical properties, mainly depending on the initial properties of the neat material. Key Words: natural fibers flax hemp biodegradable polymers biocomposites This version was published on November 1, 2006 Journal of Composite Materials, Vol. 40, No. 21, 1933-1946 (2006) DOI: 10.1177/0021998306061304 Can. J. Microbiol. 41(13): 143153 (1995) | doi:10.1139/m95-181 | 1995 NRC Canada Degradation and applications of polyhydroxyalkanoates Helmut Brandi, Reinhard Bachofen, Jrg Mayer, and Erich Wintermantel Abstract: A series of tests is available to study the biodegradation of plastic materials under either laboratory or field conditions. Most of the standard methods have been published by the American Society for Testing and Materials. All of them describe techniques to investigate the biodegradation of plastics under laboratory conditions. Microbially formed polyhydroxyalkanoates (PHAs) have been marketed recently as biodegradable plastics. However, currently only a few articles made from PHAs (e.g., bottles) are commercially available. A series of microorganisms (prokaryotes as well as eukaryotes) has been characterized as being able to degrade PHAs. With one exception (Ilyobacter delafieldii), all of them were isolated from aerobic environments. So far, over 10 different extracellular PHA depolymerases have been purified and characterized.

Depolymerases that preferentially attack PHAs with monomer units other than 3hydroxybutyrate have been found only in Pseudomonas fluorescens and Pseudomonas lemoignei. Key words: poly(3-hydroxybutyrate), polyhydroxyalkanoates, biodegradation, industrial applications. Can. J. Microbiol. 41(13): 323328 (1995) | doi:10.1139/m95-204 | 1995 NRC Canada Blends containing poly(hydroxybutyrate-co-12%-hydroxyvalerate) and thermoplastic starch H. Verhoogt, N. St-Pierre, F. S. Truchon, B. A. Ramsay, B. D. Favis, and J. A. Ramsay Abstract: Poly(hydroxyalkanoates) form biodegradable composites when blended with starch granules but the mechanical properties are poor. Unlike starch granules, thermoplastic starch is a flexible material that can be reprocessed at elevated temperatures. Mixing thermoplastic starch with poly(hydroxybutyrate-co-12%-hydroxyvalerate) resulted in a true blend in which the starch phase was also deformed. Nevertheless, the blends were still brittle despite the presence of the flexible starch phase. Morphological studies showed that the shapes of the dispersed phases in these blends were irregular and that the sizes were large owing to a large difference in viscosity between the two phases in the melt and inadequate shear during processing. Thermal analysis of the blends and starting polymers showed no indication of any interaction between the two polymers. Even if there is no compatibility between the two phases, improved mechanical properties may be obtained by optimizing the blend morphology during processing. Key words: P(HB-co-12%-HV), thermoplastic starch, blends. Comparative Performance and Barrier Properties of Biodegradable Thermoplastics and Nanobiocomposites versus PET for Food Packaging Applications D. Cava Institute of Agrochemistry and Food Technology (IATA), CSIC, Apdo. Correos 73, Burjassot 46100, Spain E. Gimnez Department of Technology, Area of Materials, University Jaime I, Castellon, Nanobiomatters Ltd., CEEI, Av. Benjamin Franklin 12, 46980 Paterna (Valencia), Spain R. Gavara Institute of Agrochemistry and Food Technology (IATA), CSIC, Apdo. Correos 73, Burjassot 46100, Spain J. M. Lagaron

Institute of Agrochemistry and Food Technology (IATA), CSIC, Apdo. Correos 73, Burjassot 46100, Nanobiomatters Ltd., CEEI, Av. Benjamin Franklin 12, 46980 Paterna (Valencia), Spain, lagaron@iata.csic.es This article reports on preliminary studies of several comparative packaging properties between polyethylene terephthalate (PET) packaging films and biodegradable biopolymers such as polycarpolactone (PCL), polylacticacid (PLA), amorphous PLA (aPLA), and polyhydroxyalcanoates copolymer with 8 mol% valeriate (PHBV) and of some nanobiocomposites, in terms of thermal and retorting resistance (thermal humid processes) and oxygen, water vapor, aroma, and solvent barrier by means of time-resolved synchrotron radiation, FT-IR and direct permeation methods. This work suggests that while PHBV can easily withstand retorting and shows excellent water and aroma (limonene and linalool) barriers compared with PET, its solvent resistance (toluene and ethanol) and oxygen barrier properties are poorer. First, trials with compression molded food contact complying nanobiocomposites of PCL and aPLA show enhanced oxygen barrier but are not sufficient, as yet, to outperform high-oxygen-barrier grades of PET film. Key Words: biodegradable nanobiocomposites PCL PLA PHBV PET packaging films oxygen permeability WVTR diffusion ethanol toluene limonene linalool FT-IR DSC Journal of Plastic Film and Sheeting, Vol. 22, No. 4, 265-274 (2006) DOI: 10.1177/8756087906071354 Foaming of Synthetic and Natural Biodegradable Polymers Carlo Marrazzo Ernesto Di Maio Department of Materials and Production Engineering, University of Naples, Federico II, Piazzale Tecchio 80, 80125 Naples, Italy Salvatore Iannace Institute of Composite and Biomedical Materials, National Research Council, Piazzale E. Fermi 1, 80055 Portici (Na), Italy; iannace@unina.it Biodegradable polymers, both synthetic and natural, often show poor foamability, in terms of the ability to form a fine-celled structure and to retain it. In fact, foams with high density and/or non uniform morphology are generally obtained with these materials. Poor rheological properties, poor solubility and inadequate diffusivity of the ordinary foaming agents, and insufficient setting mechanisms (e.g., crystallization kinetics), are the possible reasons. In this work different approaches, tuned to the different materials, have been investigated to improve the foamability of biodegradable materials, such as polyesters, polysaccharides, vegetal and animal proteins. This comprehensive analysis allows one to gain a wide and clear picture of the relevance and efficiency of the available strategies: process optimization, macromolecular design, choice of blowing agent, and use of additives. Key Words: foams biodegradable material nanocomposites

Journal of Cellular Plastics, Vol. 43, No. 2, 123-133 (2007) DOI: 10.1177/0021955X06073214 Polymer Journal Vol. 30 (1998) , No. 11 pp874-878 Compatibility and Crystallization Studies on Poly (phenyl acetylene)/Polycaprolactone Blend Hsin-Lung Chen2), Der-Jang Liaw1), Been-Yang Liaw1), Chu-Lun Shih1) and JangShiang Tsai1) 1) Department of Chemical Engineering, National Taiwan University of Science and Technology 2) Department of Chemical Engineering, National Tsing Hua University ABSTRACT: The compatibility and crystallization behavior of poly(phenyl acetylene) (PPA)/polycaprolactone (PCL) blends were investigated. PPA and PCL were partially miscible in the melt. PCL composition in the PCL-rich phase was calculated from the observed glass transition temperature with the consideration of the perturbation of amorphous phase composition by the crystallization of PCL. PCL composition in PCLrich phase ranged from ca. 91 wt% to 94 wt%. The melting point of PCL was depressed upon blending. The isothermal crystallization kinetics of the blends was analyzed by Avrami equation. The crystallization rate decreased with increasing PPA composition in the PCL-rich phase. The crystal fold surface free energy e of ca. 90 erg cm2 was obtained from Lauritzen-Hoffman analysis considering regime II kinetics. Fold surface free energy was found to increase slightly with PPA composition. KEY WORDS Poly(phenyl acetylene)/ Polycaprolactone/ Blend/ Compatibility/ Crystallization Polymer Journal Vol. 33 (2001) , No. 4 pp336-343 Study on Thermal and Mechanical Properties of Biodegradable Blends of Poly(caprolactone) and Lignin Jianchun Li1), Yong He1) and Yoshio Inoue1) 1) Department of Biomolecular Engineering, Tokyo Institute of Technology ABSTRACT: The phase structure and physical property were investigated for blends of poly(-caprolactone) (PCL) and lignin, both of which were biodegradable polymers. The blend was prepared by mechanical mixing and solution casting. The thermal analysis (DSC and DMTA) indicated there was no detectable evidence that PCL/lignin blends prepared by mechanical mixing was miscible obviously. But it was found the obvious shift of glass transition temperature Tg of the blends prepared by solution casting. This was the strong evidence to support the fact that these two polymers were at least partially miscible. According to the results of FT-IR, no obvious changes in the shape and peak position of

carbonyl absorption caused by formation of hydrogen bond between PCL carbonyl and lignin phenol hydroxyl groups were observed due to the fact that the number of phenol groups in lignin molecule is too small to induce detectable changes of carbonyl absorption. With increasing the lignin content in the blends, the position of O-H stretching band obviously shifted from 3397 to 3412 cm1. This shift to lower frequency was characteristic for intermolecular hydrogen bonding. Studying the mechanical property of the blends, we found that the maximum strength, elongation at maximum strength and elongation at break decreased but Youngs modulus increased with the increasing content of lignin. Within the lignin content of 25%, the material had good mechanical property. It was also found that the samples prepared by solution casting had better mechanical properties because of the higher dispersity. The result suggested that to blend PCL with lignin could contribute to increase Youngs modulus and reduce the production cost of PCL materials. KEY WORDS Poly(-caprolactone)/ Lignin/ Biodegradable Polymer/ Polymer Blends/ Hydrogen Bond/ Miscibility Polymer Journal Vol. 34 (2002) , No. 3 pp203 Preparation and Properties of Poly(l-lactide)-block-poly(trimethylenecarbonate) as Biodegradable Thermoplastic Elastomer Ji-Heung Kim1) and Ju Hee Lee1) 1) Department of Chemical Engineering, Polymer Technology Institute, Sungkyunkwan University ABSTRACT: Biodegradable ABA triblock copolymers of l-lactide and trimethylene carbonate with given compositions were prepared and chain-extended to produce high molecular weight polymer. The polymers were semicrystalline, and exhibited well microphase-segregated morphology with one crystalline poly(l-lactide) (PLLA) and the other soft and amorphous poly(trimethylene carbonate) (PTMC) block segments. The polymers could be cast into flexible and tough film, reversibly stretchable with elongation up to about 300%. This material may provide a novel thermoplastic elastomer possessing desirable properties including biodegradability, biocompatibility and good mechanical properties including two-phase morphology. Also a preliminary result on the hydrolytic degradation behavior was discussed. KEY WORDS Poly(l-lactide) (PLLA)/ Poly(trimethylene carbonate) (PTMC)/ Block Copolymer/ Biodegradable/ Thermoplastic Elastomer Polymer Journal Vol. 36 (2004) , No. 9 pp695-704 Morphology and Biodegradability of Poly(-caprolactone)/Poly(vinyl alcohol) Block Copolymers Jin Zhou1), Yoshiro Nishimura1), Akinori Takasu1), Yoshihito Inai1) and Tadamichi Hirabayashi1)

1) Department of Environmental Technology and Urban Planning, Graduate School of Engineering, Nagoya Institute of Technology ABSTRACT: Poly(-caprolactone)-block-poly(vinyl alcohol) (PCL-b-PVA) copolymers were prepared by using a bifunctional initiator 4-(2-hydroxyethoxy)-benzaldehyde (4HEBA), which could respond to both ring-opening polymerization and aldol-type group transfer polymerization. Morphological changes along with block length ratios were observed with differential scanning calorimeter and polarized optical microscope. Increment of PVA block influenced the crystallizing manner of PCL block. Biodegradability of PCL-b-PVA copolymers, two homopolymers (PCL and PVA), and PCL/PVA blend was evaluated from biochemical oxygen demand (BOD) in the presence of activated sludge. Under the conditions in this study, the biodegradation behavior of PCL-b-PVA copolymer was influenced by shape of sample. Increment of the PVA block in PCL-b-PVA copolymers slowed down biodegradation rates. When the content of PVA block in the block copolymer increased to more than 25 mol %, the biodegradation of PCL moiety was effectively inhibited even after much longer exposure time. KEY WORDS Poly(-caprolactone)-block-Poly(vinyl alcohol) (PCL-b-PVA)/ Polarized Optical Microscope/ Differential Scanning Calorimeter/ Morphology/ Biodegradability/ Biochemical Oxygen Demand (BOD) Polymer Journal Vol. 38 (2006) , No. 11 pp1137-1145 Thermal and Mechanical Characterization of Electrospun Blends of Poly(lactic acid) and Poly(glycolic acid) Lisa I. Ramdhanie1), Steven R. Aubuchon2), Eugene D. Boland1), Danielle C. Knapp1), Catherine P. Barnes1), David G. Simpson3), Gary E. Wnek4) and Gary L. Bowlin1) 1) Department of Biomedical Engineering, Virginia Commonwealth University 2) TA Instruments-Waters LLC 3) Department of Anatomy and Neurobiology, Virginia Commonwealth University 4) Department of Chemical Engineering, Case Western Reserve University ABSTRACT: Poly(lactic acid) (PLA) and poly(glycolic acid) (PGA) have long been popular polymers in the development of tissue engineering scaffolds due to their biocompatibility, bioabsorbability, and good tensile strength. Electrospinning is an attractive approach for the production of non-woven, nano- to micron-scale fibrous tissue engineering scaffolds of complex geometries. In this study, we characterize electrospun blends of PLA and PGA via scanning electron microscopy, tensile testing, differential scanning calorimetry, and phase contrast microscopy to gain a better understanding of these blended structures for potential use in biomedical applications. KEY WORDS Poly(glycolic acid)/ Poly(lactic acid)/ Electrospinning/ Differential Scanning Calorimetry/ Polymer Blend Polymer Journal Vol. 39 (2007) , No. 12 pp1337-1344

Study on Properties of Polymer Blends from Polypropylene with Polycaprolactone and Their Biodegradability I Made Arcana1), Bunbun Bundjali1), Iyan Yudistira1), Budiati Jariah1) and Lenggana Sukria1) 1) Physical and Inorganic Chemistry Research Groups, Faculty of Mathematic and Natural Sciences, Institut Teknologi Bandung ABSTRACT: The main problem in preparation of polymer blends is compatibility between polymers mixtures with different properties. This paper describes properties of polymer blends prepared from modified polypropylene (PP) and poly--caprolactone (PCL). The preparation of these polymer blends involves modification of PP by oxidation with hydrogen peroxide. A part of the polymer blends consisting oxidized PP and PCL was compatible polymer blends, and the highest compatible polymer blends was obtained in the PP/PCL ratio of 70/30 (% w/w) with low crystallinity. The mechanical properties of polymer blends decreased with increasing of PCL proportion in the polymer blends. Enzymatic degradability of PP-PCL polymer blends were lower than that of PCL, and increased slowly with increasing of PCL content in the polymer blends. The use of oxidized PP in preparation of polymers blends with PCL effectively improves the degradability of the polymer blends due to the increase of compatibility of each component in polymer blends. Furthermore, biodegradation process might occur through hydrolysis of PCL and compatible parts of polymer blends to result in hydroxyl and carboxylate functional groups in the end of polymer chain. KEY WORDS Polypropylene/ Poly--caprolactone/ Polymer Blends/ Compatibility/ Biodegradation Processability and Properties of Biodegradable Plastics Made from Agricultural Biopolymers J. U. Otaigbe Department of Materials Science and Engineering, Iowa State University of Science and Technology, 3053 Gilman Hall, Ames, IA 50011 H. Goel Department of Materials Science and Engineering, Iowa State University of Science and Technology, 3053 Gilman Hall, Ames, IA 50011 T. Babcock Department of Materials Science and Engineering, Iowa State University of Science and Technology, 3053 Gilman Hall, Ames, IA 50011 J. Jane Department of Food Science and Human Nutrition, Iowa State University of Science and Technology, Ames, IA 50011 The use of synthetic and natural biodegradable plastics has been severely limited due to their strong sensitivity to processing conditions such as temperature. The object of our research is to develop novel biodegradable thermoplastic compositions and processing methods for making plastic articles reproducibly from soy protein isolate and corn starch. This paper discusses viable biodegradable soy protein-starch plastic that can be extruded and injection molded into articles of various shapes and sizes. The thermal and mechanical properties of the plastic indicate that it may be useful in many applications where the plastic must biodegrade in an environmentally-benign manner after service. Blending the biodegradable soy protein plastic with novel polyphosphate fillers greatly reduced its

water sensitivity, allowing new uses in moist and load-bearing environments where the unfilled biodegradable plastic is not useable. Key Words: polymer processing biodegradable plastic water-resistant biodegradable plastic composite soy protein plastic polyphosphate glasses Journal of Elastomers and Plastics, Vol. 31, No. 1, 56-71 (1999) DOI: 10.1177/009524439903100104 Advance in Polymer Technology Journal Volume 10 Issue 1, Pages 23 - 30 Published Online: 10 Mar 2003 Biodegradable plastics: A review Jan-Chan Huang *, Aditya S. Shetty, Ming-Song Wang Plastics Engineering Department, University of Lowell, Lowell, Massachusetts 01854 *Correspondence to Jan-Chan Huang, Plastics Engineering Department, University of Lowell, Lowell, Massachusetts 01854 Abstract In this paper, the approach of biodegradation to reduce the environmental impact of plastic wastes is reviewed. The mechanism of biodegradation and the processing and applications of these materials are also discussed in relation to the structural characters of their molecules. The synthetic biodegradable materials such as starch based biodegradable materials are compared with naturally occurring biodegradable materials such as poly(hydroxy butyrate) (PHB) in terms of their applications, processing difficulty, and degradation mechanism. The future trends of these materials are anticipated. Macromolecular Materials and Engineering Volume 216 Issue 1, Pages 21 35 Published Online: 12 Mar 2003 The biodegradation of polymers: Recent results C. David, C. De Kesel, F. Lefebvre, M. Weiland Universit Libre de Bruxelles, Campus Plaine, C.P. 206/1, Bd du Triomphe, 1050 Bruxelles (Belgium) Paper presented at the 15th Annual International Conference on Advances in the Stabilization and Degradation of Polymers in Luzern (Switzerland), June 2-4, 1993. Abstract After a general introduction including definition of biodegradability, the recent literature is briefly summarized. The results obtained in our laboratory for various polymers in three different composting units are then presented. They demonstrate that there is an urgent need for a quantitative method to characterize polymer biodegradation. For that purpose, a manometric method which allows the measurement of the oxygen consumed by the growing microorganisms has been developed. It has been tested with various inocula of increasing complexity: one Streptomyces sp., a mixture of three Streptomyces (badius, setonii and viridosporus), a compost extract or sewer sludge, growing in the presence of low molecular weight molecules as sole carbon source. Its performances and limitations are discussed. It is then applied to various polymer systems: polyesters and their constituent units, autoxidized polyethylene (APE) and its model compounds, polyvinyl

alcohol (PVAl), starch and cellulose. The biodegradability of these polymers is characterized and their potential use as biodegradable materials for packaging, sanitary and agricultural uses is discussed. Electrical Engineering in Japan Volume 168 Issue 2, Pages 1 - 10 Published Online: 9 Apr 2009 Partial discharge degradation of several biodegradable polymers Norikazu Fuse 1, Shinjiro Fujita 1, Naoshi Hirai 1, Toshikatsu Tanaka 1, Masahiro Kozako 2, Masanori Kohtoh 3, Shigemitsu Okabe 3, Yoshimichi Ohki 1 1Waseda University, Japan 2Kyusyu Institute of Technology, Japan 3Tokyo Electric Power Company, Japan Funded by: Partly supported by The Electric Power Research Consortium. Keywords electrical insulation biodegradable polymer partial discharge surface degradation dielectric aging Abstract Partial discharge (PD) resistance was examined by applying a constant voltage to four different biodegradable polymers - poly-L-lactic acid (PLLA), polyethylene terephthalate succinate (PETS), poly -caprolactone butylene succinate (PCL-BS), and polybutylene succinate (PBS) - and the results were compared with those of low-density polyethylene (LDPE) and crosslinked low-density polyethylene (XLPE). The PD resistance is determined by the erosion depth and the surface roughness caused by PDs, and is ranked as LDPEXLPE>PLLAPETS>PBS>PCL-BS. This means that the sample with a lower permittivity has better PD resistance. Furthermore, examination of the sample surfaces by a polarization microscope and a laser confocal microscope reveals that the PD resistance of crystalline regions with spherulites is higher than that of amorphous regions. Therefore, good PD resistance can be achieved by the sample with a high crystallinity and a low permittivity. 2009 Wiley Periodicals, Inc. Electr Eng Jpn, 168(2): 1-10, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/eej.20807 Journal of Applied Biomaterials See Also: Journal of Biomedical Materials Research Part B: Applied Biomaterials Volume 1 Issue 1, Pages 57 - 78 Published Online: 30 Aug 2004 Mechanical properties of biodegradable polymers and composites proposed for internal fixation of bone Ph. D. A. U. Daniels 1 *, Melissa K. O. Chang 1, Kirk P. Andriano 1, Jorge Heller 2 1Division of Orthopedic Surgery, University of Utah School of Medicine and Department of Bioengineering, University of Utah College of Engineering, Salt Lake City, Utah 2Biomedical Polymers Program, SRI International, Menlo Park, California *Correspondence to A. U. Daniels, Division of Orthopedic Surgery, University of Utah School of Medicne, 50 North Medical Drive, Salt Lake City, UT 84132

Abstract The mechanical properties of biodegradable polymers and composites proposed for use in internal fixation (in place of stainless steel) are crucial to the performance of devices made from them for support of healing bone. To assess the reported range of properties and degradation rates. we searched and reviewed papers and abstracts published in English from 1980 through 1988. Mechanical property data were found for poly(lactic acid), poly (glycolic acid), poly(-caprolactone), polydioxanone, poly(ortho ester), poly(ethylene oxide), and/or their copolymers. Reports of composites based on several of these materials, reinforced with nondegradable and degradable fibers, were also found. The largest group of studies involved poly(lactic acid). Mechanical test methods varied widely, and studies of the degradation of mechanical properties were performed under a variety of conditions, mostly in vitro rather than in vivo. Compared to annealed stainless steel, unreinforced biodegradable polymers were initially up to 36% as strong in tension and 54% in bending, but only about 3% as stiff in either test mode. With fiber reinforcement, reported highest initial strengths exceeded that of stainless steel. Stiffness reached 62% of stainless steel wiht nondegradable carbon fibers, 15% with degradable inorganic fibers, but only 5% with degradable polymeric fibers. The slowest-degrading unreinforced biodegradable polymers were poly(L-lactic acid) and poly(ortho ester). Biodegradable composites with carbon or inorganic fibers generally lost strength rapidly, with a slower loss of stiffness, suggesting the difficulty of fiber-matrix coupling in these system. The strength of composites reinforced wiht (lower modulus) degradable polymeric fibers decreased more slowly. Low implant stiffness might be expected to allow too much bone motion for satisfactory healing. However, unreinforced or degradable polymeric fiber reinforced materials have been used successfully clinically. The key has been careful selection of applications, plus use of designs and fixation methods distinctly different from those appropriate for stainless steel devices. Journal of Applied Polymer Science Volume 91 Issue 2, Pages 833 - 840 Published Online: 18 Nov 2003 In situ fiber-reinforced composites from blends containing polypropylene and polycaprolactone Takeshi Semba 1 *, Kazuo Kitagawa 1, Satoshi Endo 2, Kazunori Maeda 2, Hiroyuki Hamada 3 1Department of Applied Chemistry, Kyoto Municipal Institute for Industrial Research, 17 Chudoji Minami-machi, Shimogyo-ku, Kyoto 600-8813, Japan 2Technology and Development Department, Hexa Chemical Company, Ltd., 153 Yokomakura-Nishi, Higashi-Osaka-City 578-0956, Japan 3Division of Advanced Fibro-science, Kyoto Institute of Technology, Goshokaido-cho, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan email: Takeshi Semba (sentake@city.kyoto.jp) *Correspondence to Takeshi Semba, Department of Applied Chemistry, Kyoto Municipal Institute for Industrial Research, 17 Chudoji Minami-machi, Shimogyo-ku, Kyoto 6008813, Japan Keywords blends shear immiscibility stress morphology

Abstract Our study was focused on the presupposition that morphology control in immiscible polymer blend could give rise to reinforcement in composites. To investigate the effects of shear and elongational flow in polymer processing, observation of the mechanical properties and the morphology of the polypropylene/polycaprolactone (PP/PCL) blend system was performed. PP/PCL sheets were fabricated by means of a single-screw extruder equipped with a slit-type die to which high shear and elongational stresses were applied. For the sake of comparison, a second series of composites of identical composition was compression molded with a hot-press machine that transmits lower shear and elongational stresses. The results indicate that the extruded sheets have better mechanical properties than those of the compression-molded sheets, a result attributed to the generation of in situ dispersed long fiber minor phases and cocontinuous phases in the extruded composites. The differences in the crystallization behavior of the fibrous and spherically shaped components were indicated clearly by DSC curves. A PP crystalline peak indicative of in situ PP fiber formation is conspicuous around 980 cm-1 (PP crystalline band) in the FTIR spectrum. 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 833-840, 2004 Journal of Chemical Technology & Biotechnology Volume 82 Issue 3, Pages 233 - 247 Published Online: 7 Mar 2007 Polyhydroxyalkanoates: biodegradable polymers with a range of applications S. Philip, T. Keshavarz, I. Roy * School of Biosciences, University of Westminster, London, UK email: I. Roy (royi@wmin.ac.uk) *Correspondence to I. Roy, Department of Molecular and Applied Biosciences, School of Biosciences, University of Westminster, 115 New Cavendish Street, London W1W 6UW, UK Keywords polyhydroxyalkanoates applications biodegradable polymers Abstract Increased and accelerated global economic activities over the past century have led to interlinked problems that require urgent attention. The current patterns of production and consumption have raised serious concerns. In this context, greater emphasis has been put on the concept of sustainable economic systems that rely on technologies based on and supporting renewable sources of energy and materials. Average UK households produce around 3.2 million tonnes of packaging waste annually whereas 150 million tonnes of packaging waste is generated annually by industries in the UK. Hence, the development of biologically derived biodegradable polymers is one important element of the new economic development. Key among the biodegradable biopolymers is a class known as polyhydroxyalkanoates. Polyhydroxyalkanoates (PHAs) are a family of polyhydroxyesters of 3-, 4-, 5- and 6-hydroxyalkanoic acids, produced by a variety of bacterial species under nutrient-limiting conditions with excess carbon. These water-insoluble storage polymers are biodegradable, exhibit thermoplastic properties and can be produced from renewable carbon sources. Thus, there has been considerable interest in the commercial exploitation of these biodegradable polyesters. In this review various applications of polyhydroxyalkanoates are discussed, covering areas such as medicine, agriculture, tissue engineering, nanocomposites, polymer blends and chiral synthesis. Overall this review

shows that polyhydroxyalkanoates are a promising class of new emerging biopolymers. Copyright 2007 Society of Chemical Industry Macromolecular BioscienceVolume 8 Issue 1, Pages 14 - 24 Published Online: 11 Sep 2007 Biodegradation of Aliphatic and Aromatic Polycarbonates Trishul Artham, Mukesh Doble * Department of Biotechnology, Indian Institute of Technology Madras, Chennai 600036, India email: Mukesh Doble (mukeshd@iitm.ac.in) *Correspondence to Mukesh Doble, Department of Biotechnology, Indian Institute of Technology Madras, Chennai 600036, India. Fax: +91 44 22574102 Keywords biodegradable lipases polycarbonates pretreatment Abstract Polycarbonate is one of the most widely used engineering plastics because of its superior physical, chemical, and mechanical properties. Understanding the biodegradation of this polymer is of great importance to answer the increasing problems in waste management of this polymer. Aliphatic polycarbonates are known to biodegrade either through the action of pure enzymes or by bacterial whole cells. Very little information is available that deals with the biodegradation of aromatic polycarbonates. Biodegradation is governed by different factors that include polymer characteristics, type of organism, and nature of pretreatment. The polymer characteristics such as its mobility, tacticity, crystallinity, molecular weight, the type of functional groups and substituents present in its structure, and plasticizers or additives added to the polymer all play an important role in its degradation. The carbonate bond in aliphatic polycarbonates is facile and hence this polymer is easily biodegradable. On the other hand, bisphenol A polycarbonate contains benzene rings and quaternary carbon atoms which form bulky and stiff chains that enhance rigidity. Even though this polycarbonate is amorphous in nature because of considerable free volume, it is non-biodegradable since the carbonate bond is inaccessible to enzymes because of the presence of bulky phenyl groups on either side. In order to facilitate the biodegradation of polymers few pretreatment techniques which include photo-oxidation, irradiation, or use of chemicals have been tested. Addition of biosurfactants to improve the interaction between the polymer and the microorganisms, and blending with natural or synthetic polymers that degrade easily, can also enhance the biodegradation. Macromolecular Materials and Engineering Volume 276-277 Issue 1, Pages 1 - 24 Published Online: 24 May 2000 Biofibres, biodegradable polymers and biocomposites: An overview A. K. Mohanty, M. Misra, G. Hinrichsen * Technical University of Berlin, Institute of Nonmetallic Materials, Polymer Physics, Englische Str. 20, D-10587 Berlin, Germany *Correspondence to G. Hinrichsen, Technical University of Berlin, Institute of Nonmetallic Materials, Polymer Physics, Englische Str. 20, D-10587 Berlin, Germany

Abstract Recently the critical discussion about the preservation of natural resources and recycling has led to the renewed interest concerning biomaterials with the focus on renewable raw materials. Because of increasing environmental consciousness and demands of legislative authorities, use and removal of traditional composite structures, usually made of glass, carbon or aramid fibers being reinforced with epoxy, unsaturated polyester, or phenolics, are considered critically. Recent advances in natural fiber development, genetic engineering and composite science offer significant opportunities for improved materials from renewable resources with enhanced support for global sustainability. The important feature of composite materials is that they can be designed and tailored to meet different requirements. Since natural fibers are cheap and biodegradable, the biodegradable composites from biofibers and biodegradable polymers will render a contribution in the 21st century due to serious environmental problem. Biodegradable polymers have offered scientists a possible solution to waste-disposal problems associated with traditional petroleum-derived plastics. For scientists the real challenge lies in finding applications which would consume sufficiently large quantities of these materials to lead price reduction, allowing biodegradable polymers to compete economically in the market. Today's much better performance of traditional plastics are the outcome of continued R&D efforts of last several years; however the existing biodegradable polymers came to public only few years back. Prices of biodegradable polymers can be reduced on mass scale production; and such mass scale production will be feasible through constant R&D efforts of scientists to improve the performance of biodegradable plastics. Manufacture of biodegradable composites from such biodegradable plastics will enhance the demand of such materials. The structural aspects and properties of several biofibers and biodegradable polymers, recent developments of different biodegradable polymers and biocomposites are discussed in this review article. Collaborative R&D efforts among material scientists and engineers as well as intensive co-operation and co-ordination among industries, research institutions and government are essential to find various commercial applications of biocomposites even beyond to our imagination. Packaging Technology and Science Volume 20 Issue 1, Pages 49 - 70 Published Online: 24 Aug 2006 Comparison of the degradability of poly(lactide) packages in composting and ambient exposure conditions Gaurav Kale, Rafael Auras *, Sher Paul Singh School of Packaging, Michigan State University, East Lansing, MI-48823-1223, USA email: Rafael Auras (aurasraf@msu.edu) *Correspondence to Rafael Auras, 140 Packaging Building, School of Packaging, Michigan State University, East Lansing, MI 48823-1223, USA Keywords biopolymers compostability degradation GPC, hydrolysis poly(lactide) Abstract The adoption of biodegradable polymeric materials is increasing in food and consumer goods packaging applications, due to concerns about the disposal of petroleum-based polymers and the increasing cost of petroleum-based polymer resins. Currently, poly(lactide) (PLA) polymers are the biggest commercially available bio-based polymeric packaging materials. As the main motivation for adopting biopolymers is environmental, there is a need to address the degradability and environmental performance of

biodegradable packages. The aim of this study was to investigate and compare the degradation of two commercially available biodegradable packages made of PLA under real compost conditions and under ambient exposure, using visual inspection, gel permeation chromatography, differential scanning calorimetry and thermal gravimetric analysis. A novel technique to study and track the degradability of these packages under real compost conditions was used. Both packages were subjected to composting and ambient exposure conditions for 30 days, and the degradation of the physical properties was measured at 1, 2, 4, 6, 9, 15 and 30 days. PLA bottles made of 96% l-lactide exhibited lower degradation than PLA delicatessen (deli) containers made of 94% l-lactide, mainly due to their highly ordered structure and, therefore, their higher crystallinity. The degradation rate changed as the initial crystallinity and the l-lactide content of the packages varied. Temperature, relative humidity and pH of the compost pile played an important role in the rate of degradation of the packages. First-order degradation kinetics and linear degradation trends were observed for both packages subjected to composting conditions. Copyright 2006 John Wiley & Sons, Ltd. Polymer Engineering and Science Published Online: 8 Apr 2004 Volume 38 Issue 8, Pages 1251 - 1253

Biodegradable polymers and environmental interaction Sigbritt Karlsson *, Ann-christine Albertsson Department of Polymer Technology, The Royal Institute of Technology (KTH), S-100 44 Stockholm, Sweden *Correspondence to Sigbritt Karlsson, Department of Polymer Technology The Royal Institute of Technology (KTH) S-100 44 Stockholm, Sweden Abstract Biodegradable polymers are by definition those that degrade as a result of the action of microorganisms and/or enzymes. The rate of this biodegradation may vary from hours to years depending on the molecular architecture of the polymer in question. Biopolymers like lignin take years to degrade while many proteins and polysaccharides degrade within hours to days. The same is true for the synthetic biodegradable polymers where polyethylene is sometimes regarded as inert to biodegradation while polyanhydrides are rapidly biodegradable. The influence of structure, morphology, and surface area on the biodegradability are discussed, with polyesters and degradable polyethylene (with prooxidant and/or biodegradable additives) as examples. The rate of biodegradation is controllable by choosing the appropriate molecular architecture. In addition to this the environmental interaction of these polymers should be determined. The degradation product pattern of biodegradable polymers should be compatible with the natural degradation mechanisms (i.e., catabolisms). Polymer International Volume 47 Issue 2, Pages 89 - 144 Published Online: 26 Mar 1999 A review of biodegradable polymers: uses, current developments in the synthesis and characterization of biodegradable polyesters, blends of biodegradable polymers and recent advances in biodegradation studies Wendy Amass *, Allan Amass, Brian Tighe

Speciality Polymer Research Group, CEAC, Aston University, Aston Triangle, Birmingham B4 7ET, UK Keywords biodegradation; biodegradable polyesters; packaging; synthesis; characterization; blends Abstract This review considers the uses of biodegradable polymers in terms of their relevance within current plastic waste management of packaging materials, biomedical applications and other uses; research papers and patents are catalogued. The chemical synthesis of polyesters and the microbial production of poly(hydroxyalkanoate)s, including recent publications in these areas, are covered and methods of characterization and structural analysis are outlined. Current research into two- and three-component blends is reviewed as a method of reducing overall costs and modifying both properties and biodegradation rates of materials. Finally, there is a summary of degradation processes. Both abiotic and biotic reactions are discussed, together with the development of biodegradation test methods, particularly with respect to composting. 1998 Society of Chemical Industry Polymers for Advanced Technologies Volume 15 Issue 6, Pages 340 - 345 Published Online: 19 May 2004 Mechanical, thermal and morphological properties of poly(-caprolactone)/zein blends E. Corradini 1, L. H. C. Mattoso 2, C. G. F. Guedes 3, D. S. Rosa 3 * 1Cincia e Engenharia de Materiais, USP, CEP 13560-970, So Carlos, SP, Brazil 2EMBRAPA Instrumentao Agropecuria, CNPDIA/EMBRAPA, CP 741, CEP 13560970, So Carlos, SP, Brazil 3Laboratrio de Polmeros Biodegradveis e Solues Ambientais, Programa de PsGraduao Stricto Sensu em Engenharia e Cincia dos Materiais (PPG-ECM), Universidade So Francisco, Rua Alexandre Rodrigues Barbosa, no 45, Centro, CEP 13251-900, Itatiba, SP, Brazil email: D. S. Rosa (derval.rosa@saofrancisco.edu.br) *Correspondence to D. S. Rosa, Laboratrio de Polmeros Biodegradveis e Solues Ambientais, Programa de Ps-Graduao Stricto Sensu em Engenharia e Cincia dos Materiais (PPG-ECM), Universidade So Francisco, Rua Alexandre Rodrigues Barbosa, no 45, Centro, CEP 13251-900, Itatiba, SP, Brazil. Funded by: FAPESP; Grant Number: 99/10716-4, 99/06373-4 CNPq; Grant Number: processes 303500/2002-6, 477942/2003-2 Departamento de Engenharia de Materiais of UFSCar, Universidade So Francisco Union Chemical Carbide Ltd. Keywords poly(-caprolactone) zein mechanical properties blends thermal properties Abstract Blends of poly(-caprolactone) (PCL) with zein (PCL/zein) in different proportions (100/0, 75/25, 50/50, 25/75 and 0/100 wt% containing 5 wt% glycerol) were compared based on their mechanical properties (tensile strength, elongation at break, and Young's modulus), and on their thermal properties, the latter determined by thermogravimetric analysis

(TGA) and dynamic mechanical thermal analysis (DMTA). The morphology of the materials was studied by scanning electron microscopy (SEM). Blends of PCL/zein showed reduced tensile strength and elongation at break, but increased Young's modulus compared to the pure polymers, in agreement with the DMTA and SEM results. These findings indicated that PCL and zein were incompatible. TGA showed that the thermal stability was enhanced by the addition of zein to PCL, whereas SEM showed a poor interfacial interaction between the polymers. Copyright 2004 John Wiley & Sons, Ltd. Starch Strke Volume 49 Issue 7-8, Pages 306 - 322 Published Online: 26 Oct 2006 Biodegradable Films Made from Low Density Polyethylene (LDPE), Ethylene Acrylic Acid (EAA), PolyCaprolactone (PCL) and Wheat Starch for Food Packaging Applications: Part 3 Dr. Ioannis Arvanitoyannis 1 *, Eleni Psomiadou 1, Professor Dr. Costas G. Biliaderis 1, Hiromasa Ogawa 2, Norioki Kawasaki 2, Atsuyoshi Nakayama 2 1Aristotle University, School of Agriculture, 540 06, Thessaloniki (Greece). Laboratory of Food Chemistry and Biochemistry 2Osaka National Research Institute AIST, 1-8-31 Midorigaoka, Ikeda, 563 Osaka (Japan) *Correspondence to Ioannis Arvanitoyannis, Aristotle University, School of Agriculture, 540 06, Thessaloniki (Greece). Laboratory of Food Chemistry and Biochemistry Funded by: Shared Cost European; Grant Number: ERB-FAIRCT 961085 Abstract The mechanical properties and gas/water permeabilities of extrudates of low density polyethylene (LDPE), wheat starch and ethylene acrylic acid (EAA) or polycaprolactone (PCL) were studied after their conditioning at various relative humidities. Satisfactory agreement was found between the experimental values, pertaining the mechanical properties, and estimates obtained by applying several semiempirical equations. The presence of starch contents (> 30%) or PCL had an adverse effect on the mechanical properties of LDPE/starch blends, whereas EAA acted as a compatibilizer by increasing the percentage elongation of the blends. Gas permeability and water vapour transmission rate increased proportionally to the starch/PCL content in the blend. Several theoretical and semiempirical calculation were also applied for gas permeability and possible interpretations were provided for the occasionally observed deviations between the experimental and the theoretical values. Starch Strke Volume 57 Issue 1, Pages 8 - 15 Published Online: 30 Dec 2004 Green Nanocomposites from Renewable Resources: Effect of Plasticizer on the Structure and Material Properties of Clay-filled Starch Jitendra Kumar Pandey, Raj Pal Singh * Polymer Chemistry Division, National Chemical Laboratory, Pune, India email: Raj Pal Singh (singh@poly.ncl.res.in)

*Correspondence to Raj Pal Singh, Polymer Chemistry Division National Chemical Laboratory, Pune-411008, India, Phone + Fax: +91-20-25893234 Keywords Nanocomposites Clay-filled starch WAXD Effect of plasticizer Abstract Nanocomposites of starch were prepared via different addition sequences of plasticizer and clay by the solution method. The extent of dispersion of the filler was evaluated by wide angle X-ray diffractometry (WAXD) in the resulting composites. Thermal stability, mechanical properties and water absorption studies were conducted to measure the material properties whereas FT-IR spectroscopy was used to study the microdomain structure of composites. The sequence of addition of components (starch /plasticizer (glycerol) / clay) had a significant effect on the nature of composites formed and accordingly properties were altered. Glycerol and starch both have the tendency to penetrate into the silicate layers but penetration of glycerol is favored owing to its smaller molecule size. The filler dispersion becomes highly heterogeneous and the product becomes more brittle when starch was plasticized before filling with clay due to the formation of a bulky structure resulting from electrostatic attractions between starch and plasticizer. It was concluded that best mechanical properties can be obtained if plasticizer is added after mixing of clay in the starch matrix. Starch Strke Volume 42 Issue 4, Pages 123 - 130 Published Online: 26 Oct 2006 The Role of Starch in Biodegradable Thermoplastic Materials Dr. habil. Harald Rper, Dr. Helmut Koch Cerestar Research & Development, Gruppo Ferruzzi. Havenstraat 84, B-1800 Vilvoorde (Belgium) Lecture given at: Eurocarb V (Prague, August 20-25, 1989). Symposium Biodegradation of Carbohydrate based Polymers, organized by Programmabureau Koolhydraten (PbK) (Amsterdam, November 13-14, 1989). Expert meeting Werkstoffe aus nachwachsenden Rohstoffen, organised by Hanns Seidel-Stiftung e. V. (Wilbad Kreuth, December 6-8, 1989). Abstract The increasing garbage mountain is more and more recognized as an ecological threat. Space for landfills is limited and additional incineration capacities require high capital investments and pose additional envrironmental problems. In the FRG from total annual 14 million t of household waste, 700,000 t are non-degradable plastic materials (polyolefines, polystyrene and polyvinylchloride), especially for packaging. Different strategies are being followed to reduce the 5% plastics in household waste: prevention, recycling, chemical valorization, thermic utilization (incineration) and use of degradable polymers. The latter are reviewed in detail: chemical modification of classical polymers into photo- and chemo-degradable materials, physical mixing of 6-20% granular starch with polyethylene or polypropylene, coprocessing of more than 50% disintegrated starch with hydrophilic polymers like polyacrylate or polyvinylalcohol to biodegradable films for agricultural mulch or carrying bags, thermoplastic extruded starch with plasticiser containing more than 90% starch for blister packaging and disposables for fast food and

finally biodegradable polyesters like poly-hydroxybutyric acid (PHB) and polylactic acid, produced by fermentation processes.