A Sensitive Electrochemical Impedance Spectroscopy Method for Detection of Polyimide Degradation by Microorganisms

An electrochemical impedance spectroscopy (EIS) technique was evaluated for monitoring microbial degradation of electronic packaging polyimides. The microbial inoculum was a mixed culture of fungi isolated previously from deteriorated polyimides. The active fungal consortium comprised Aspergillus versicolor, Cladosporium cladosporioides, and a Chaetomium species. After inoculation, fungal growth on the polyimides resulted in distinctive EIS spectra indicative of polymer insulation failure, which directly related to polymer integrity. Degradation appeared to occur in a number of steps and two distinctive stages in the decline of film resistance were observed in the inoculated EIS cells within the 2 and 10 weeks after inoculation. The early stage of resistance decrease may be related to the ingress of water molecules and ionic species into the polymeric materials, whereas the second stage probably resulted from partial degradation of the polymers by fungal growth on the polymer film. The relationship between changes of impedance spectra and microbial degradation of the polymer was further supported by scanning electron microscopy (SEM) observations of fungi growing on the surface of the inoculated polyimides. Our data indicate that the EIS can be used in detection of early degradation of resistant polymers and polyimides that are susceptible to biodeterioration.     

Synthesis and Properties of Biodegradable Poly(vinyl alcohol)/Organo-nanoclay Bionanocomposites

Biodegradable nanocomposites comprising of biodegradable polymers and bioactive organically modified layered silicates commonly reveal extremely enhanced mechanical and various other properties when compared to those of virgin polymers. This work was undertaken with a view to preparation of polymer bionanocomposites consisting of biodegradable poly(vinyl alcohol) (PVA) and organo-nanoclay. Cloisite Na⁺ and ammonium salt of l-isoleucine amino acid was used for the preparation of the novel chiral organo-nanoclay via an intercalation reaction in an aqueous solution. PVA/organo-nanoclay bionanocomposites of various compositions were created through the solution intercalation method by ultrasound-assisted technique. The resulting novel materials were characterized by X-ray diffraction and Fourier transform infrared spectroscopy techniques. Thermogravimetric analysis (TGA) and UV/vis spectroscopy were applied to test the properties of PVA bionanocomposites. TGA indicate that the thermal stability is enhanced distinctly, without a sacrifice in optical clarity. The improvement of thermal properties was attributed to the homogeneous and good dispersion of organo-nanoclay in polymeric matrix and the strong hydrogen bonding between O?CH groups of PVA and the oxygen atoms of silicate layers or carbonyl group as well as OH group of intercalated amino acid. The morphology of the organo-nanoclay and PVA bionanocomposites was examined by scanning electron microscopy and transmission electron microscopy techniques. Uniform distribution of clay due to intimate interaction between clay and polymer appears to be the cause for improved properties.     

An overview of methods for biodegradability testing of biopolymers and packaging materials

This paper gives an overview of the methods used at the Technical Research Centre of Finland (VTT) for the biodegradability testing of solid polymers and packaging materials. Biodegradability of each polymer included in the packaging material should be separately tested. Aquatic aerobic and anaerobic tests and, in specific cases, enzymatic tests are used for screening purposes. The application of aquatic aerobic tests—an automated Sturm test (OECD 301B; ASTM D5209) and a VTT headspace test as well as an anaerobic test (ASTM D5210)—is discussed. Three composting tests and their applications are summarized. These tests are regarded as important because they can be used to simulate the biodegradability under real-life conditions. Several tests are needed to determine the fate of the polymer under real conditions and to study its biodegradability in different environments. The time needed for complete biodegradation of polymers in nature is impossible to predict with laboratory tests and should be studiedin vivo.According to the lecture given in Sweden at the Royal Institute of Technology, at a workshop on polymers from renewable resources and their degradation, November 10–11, 1994.     

Calculation of carbon balances for evaluation of the biodegradability of polymers

Establishing carbon balances has been proven to be an applicable and powerful tool in testing biodegradability of polymers. In controlled degradation tests at a 4-L scale with the model polymer poly(-hydroxybutyrate) (PHB), it was shown that the degree of degradation could not be determined with satisfactory accuracy from CO₂ release alone. Instead, the course of degradation was characterized by means of establishing carbon balances for the degradation of PHB withAcidovorax facilis and a mixed culture derived from compost. Different analytical methods for determining the different carbon fractions were adapted to the particular test conditions and compared. Quantitative determination of biomass and residual polymer were the main problems in establishing carbon balances. Amounts of biomass derived from protein measurements depend strongly on assumptions of the protein content of the biomass. Selective oxidation of biomass with hypochlorite was used as alternative, but here problems arose from insoluble metabolic products. Determination of soluble components with the method of chemical oxygen demand (COD) also includes empirical assumptions but seems acceptable if the dissolved carbon fraction is in the range of some 10% total carbon. Results confirm both analytical assays and theoretical approaches, in ending up at values very close to 100%, within an acceptable standard deviation range under test conditions comparable to standard test practice.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.     

The Properties of PLA/Oxidized Soybean Oil Polymer Blends

Novel polymer blends based on completely renewable polymers were reported. Polymer blends based on polylactic acid (PLA) and oxidized and hydroxylated soya bean oil polymers were prepared. Plasticization and mechanical strength effect of the soya bean oil polymers on the PLA were observed. Fracture surface analysis of the polymer blends was carried out by using scanning electron microscopy. The PLA blends showed more amorphous morphologies compared to pure PLA. The blends had better elongation at break in view of the stress–strain measurement. Blend of PLA with the hydroxylated polymeric soya bean oil indicated the slightly antibacterial properties.     

Measurement of the biodegradation of starch-based materials by enzymatic methods and composting

The aim of this study was to evaluate the suitability of in vitro enzymatic methods for assaying the biodegradability of new starch-based biopolymers. The materials studied included commercial starch-based materials and thermoplastic starch films prepared by extrusion from glycerol and native potato starch, native barley starch, or crosslinked amylomaize starch. Enzymatic hydrolysis was performed using excessBacillus licheniformis -amylase andAspergillus niger glucoamylase at 37°C and 80°C. The degree of degradation was determined by measuring the dissolved carbohydrates and the weight loss of the samples. Biodegradation was also determined by incubating the samples in a compost environment and measuring the weight loss after composting. The results indicated that the enzymatic method is a rapid means of obtaining preliminary information about the biodegradability of starch-based materials. Other methods are needed to investigate more accurately the extent of biodegradability, especially in the case of complex materials in which starch is blended with other polymers.     

Biodegradability of a Selected Range of Polymers and Polymer Blends and Standard Methods for Assessment of Biodegradation

Synthetic polymers are important to the packaging industry but their use raises aesthetic and environmental concerns, particularly with regard to solid waste accumulation problems and the threat to wildlife. Some concerns are addressed by attention to problems associated with source reduction, incineration, recycling and landfill. Others are addressed by the development of new biodegradable polymers either alone or in blends. Materials used for biodegradable polymers include various forms of starch and products derived from it, biopolyesters and some synthetic polymers. Starch is rapidly metabolised and is an excellent base material for polymer blends or for infill of more environmentally inert polymers where it is metabolised to leave less residual polymer on biodegradation. This should help to improve the environmental impact of waste disposal. A number of standard methods have been developed to estimate the extent of biodegradability of polymers under various conditions and with a variety of organisms. They tend to be used mainly in the countries where they were developed but there is much overlap between the standards of different countries and wide scope for development of consistent and international standards.     

A respirometric method to measure mineralization of polymeric materials in a matured compost environment

A respirometric method was developed to measure the mineralization of polymeric materials in a matured compost environment. For the purpose of evaluating the method, results obtained for the mineralization of glucose and cellulose are presented. The matured compost, in addition to supplied nutrients, micronutrients, and an inoculum, serves as the matrix which supports the microbial activity. Recovery of the substrate carbon in the form of carbon dioxide from the glucose and cellulose added to test vessels was 68 and 70%, respectively. A statistical evaluation of the results obtained on substrate mineralization was carried out and showed acceptable reproducibility between replicate test vessels and test runs. The testing protocol developed has the following important characteristics: (1) the test reactors are maintained at 53 °C at a high solids loading (60% moisture), which has certain characteristics that are similar to a thermophilic compost environment; (2) the test matrix providing microbial activity is derived from readily available organic materials to facilitate reproducibility of the method in different laboratories; (3) the equipment required to perform this test is relatively inexpensive; and (4) the information obtained on polymer mineralization is vital to the study and development of biodegradable polymeric materials.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

Biopolymers Based Green Composites: Mechanical, Thermal and Physico-chemical Characterization

Natural cellulosic fibers are one of the smartest materials for use as reinforcement in polymers possessing a number of applications. Keeping in mind the immense advantages of the natural fibers, in present work synthesis of natural cellulosic fibers reinforced polymer composites through compression molding technique have been reported. Scanning Electron microscopy (SEM), Thermo gravimetric/Differential thermal/Derivative Thermogravimetry (TGA/DTA/DTG), absorption in different solvents, moisture absorbance, water uptake and chemical resistance measurements were used as characterization techniques for evaluating the different behaviour of cellulosic natural fibers reinforced polymer composites. Effect of fiber loading on mechanical properties like tensile strength, flexural strength, compressive strength and wear resistances has also been determined. Reinforcing of the polymer matrix with natural fibers was done in the form of short fiber. Present work indicates that green composites can be successfully fabricated with useful mechanical properties. These composites may be used in secondary structural applications in automotive, housing etc.     

Selective separation of virgin and post-consumer polymers (PET and PVC) by flotation method

More and more polymer wastes are generated by industry and householders today. Recycling is an important process to reduce the amount of waste resulting from human activities. Currently, recycling technologies use relatively homogeneous polymers because hand-sorting waste is costly. Many promising technologies are being investigated for separating mixed thermoplastics, but they are still uneconomical and unreliable. At present, most waste polymers cause serious environmental problems. Burning polymers for recycling is not practiced since poisonous gases are released during the burning process. Particularly, polyvinyl chloride (PVC) materials among waste polymers generate hazardous HCl gas, dioxins containing Cl, etc., which lead to air pollution and shorten the life of the incinerator. In addition, they make other polymers difficult to recycle.Both polyethylene terephthalate (PET) and PVC have densities of 1.30–1.35 g/cm³ and cannot be separated using conventional gravity separation techniques. For this reason, polymer recycling needs new techniques. Among these techniques, froth flotation, which is also used in mineral processing, can be useful because of its low cost and simplicity.The main objective of this research is to recycle PET and PVC selectively from post-consumer polymer wastes and virgin polymers by using froth flotation. According to the results, all PVC particles were floated with 98.8% efficiency in virgin polymer separation while PET particles were obtained with 99.7% purity and 57.0% efficiency in post-consumer polymer separation.     

Poly(aspartic acid): Synthesis, biodegradation, and current applications

Poly(aspartic acid) is a biodegradable, water-soluble polymer that is valuable in numerous industrial applications. A variety of synthetic methods can be utilized to prepare poly(aspartic acid) and related polymeric materials with a range of tailored physical and chemical characteristics. This review of current investigative and patent literature describes methods of synthesis, biodegradative studies, and important current and potential applications of both poly(aspartic acid) homopolymers and copolymers.     

Reinforcement of Yeast Biomass Films with Bacterial Cellulose and Rice Husk Cellulose Nanofibres

Journal of Polymers and the Environment - In the last decades, cellulose nanoparticles have been widely used to reinforce polymeric materials due to their strength and their wide availability in...     

Soil Biodegradation of PHBV/Peach Palm Particles Biocomposites

There is great interest in developing eco-friendly green biocomposites from plant-derived natural fibers and crop-derived bioplastics attributable to their renewable resource-based origin and biodegradable nature. Fully biodegradable composites, made from both biodegradable polymeric matrices and natural fibers, should be advantageous in some applications, such as one way packaging. Polyhydroxyalkanoates (PHAs) are naturally occurring biodegradable polymers produced from a wide range of microorganisms, with poly(3-hydroxybutyrate) P(3HB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) being important examples of PHAs. In this work, biocomposites of PHBV consisting of a PHBV matrix incorporating peach palm particles (PPp), [i.e., 100/0, 90/10, 80/20 and 75/25 (%w/w) PHBV/PPp] were processed by injection molding at 160 °C. The effect of PPp loading on the thermal and the mechanical properties, as well as on the morphological behavior of the PHBV/PPp biocomposites was investigated. Soil biodegradation tests were carried out by burying specimen beakers containing aged soil and kept under controlled temperature and humidity in accordance with ASTM G160-98. Degradation of the biocomposites was evaluated by visual analysis, scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) following test exposures of up to 5 months. The addition of PPp reduced the maximum strength and the elongation at break of the biocomposites. On the other hand, the Young’s modulus improved with the PPp content. Micrographs of the fracture surfaces following tensile strength testing revealed a large distance between the PHBV matrix and PPp particles although a low interaction is expected. Where measured, these distances tended increase as the PPp content of the biocomposites increased. Soil biodegradation tests indicated that the biocomposites degraded faster than the neat polymer due to the presence of cavities that resulted from introduction of the PPp and that degradation increased with increasing PPp content. These voids allowed for enhanced water adsorption and greater internal access to the soil-borne degrader microorganisms.     

Instrumental Physical Analysis of Microwaved Glycerol Citrate Foams

Solid glycerol citrate polyester polymeric foams generated by microwave heating were further cured in a conventional oven at 100?°C for 0, 6, 24, 48, or 72?h and their physical properties were tested. Curing glycerol citrate polyesters resulted in decreased moisture content (MC), altered color, increased hydrated polymer weight loss (HWL), and increased polymer oven weight loss (OWL). Polyester polymer samples were evaluated for firmness and springiness employing a texture analyzer (Model TA/TX2i). Oven curing increased polymer firmness and springiness. For example, firmness and springiness in 48?h cured samples increased 202 and 143%, respectively, when compared to uncured controls. High correlations were found comparing OWL, MC, HWL, firmness, and springiness. Compression molded samples obtained from ground cured and non-cured polymers were evaluated for tensile strength, elongation and Young??s modulus using the Instron universal test machine (Model 4201). Curing promoted higher tensile strengths and elongation but did not affect Young??s modulus values. High correlations were found between springiness, firmness, tensile strength, and elongation. The texture analyzer was shown to have merit in the preliminary evaluation of the glycerol citrate polyester polymers.     

Degradation of Polycaprolactone Modified with TPS or CaCO3 in Biotic/Abiotic Seawater

This paper is an investigation of the polymer degradation process in two types of seawater (with and without microorganisms) sourced from the Baltic Sea. The chosen polymeric materials were polycaprolactone modified with either thermoplastic starch (PCL/TPS?>?85%) or calcium carbonate (60% PCL/40% CaCO₃) compared directly against unmodified polycaprolactone. All samples were incubated for 28?weeks in seawater with and without microorganisms under laboratory conditions and analysed before and after the degradation process. Weight loss analysis, microscopic observations of polymer surfaces and tensile strength tests were used to determine the progress of polymer degradation. The experimental results obtained indicated, that in each of the experiments, degradation of tested polymeric samples occured. The process was more effective in seawater with microorganisms compared against systems without added microorganisms. The experiment in seawater demonstrated that modification of PCL with calcium carbonate did not encourage the degradation process; and in some circumstances inhibited it.     

Life Cycle Assessment of Polysaccharide Materials: A Review

Apart from conventional uses of polysaccharide materials, such as food, clothing, paper packaging and construction, new polysaccharide products and materials have been developed. This paper reviews life cycle assessment (LCA) studies in order to gain insight of the environmental profiles of polysaccharide products (e.g. viscose or natural fibre polymer composites) in comparison with their conventional counterparts (e.g. cotton or petrochemical polymers). The application areas covered are textiles, engineering materials and packing. It is found that for each stage of the life cycle (production, use phase and waste management) polysaccharide-based end products show better environmental profiles than their conventional counterparts in terms of non-renewable energy use (NREU) and greenhouse gas (GHG) emissions. Cotton is an exception, with high environmental impacts that are related to the use of fertilisers, herbicides, pesticides and high water consumption. The available literature for man-made cellulose fibres shows that they allow to reduce NREU and GHG emissions in the fibre production phase. No study has been found for the fabric production and the use phase of man-made cellulose textiles.

Emission of Volatiles from Polymers — A New Approach for Understanding Polymer Degradation

Emission of low molar mass compounds from different polymeric materials was determined and the results from the volatile analysis were applied to predict the degree of degradation and long-term properties, to determine degradation rates and mechanisms, to differentiate between biotic and abiotic degradation and for quality control work. Solid-phase microextraction and solid-phase extraction together with GC-MS were applied to identify and quantify the low molar mass compounds. Volatiles were released and monitored at early stages of degradation before any matrix changes were observed by e.g. SEC, DSC and tensile testing. The analysis of volatiles can thus also be applied to detect small differences between polymeric materials and their susceptibility to degradation. The formation of certain degradation products correlated with the changes taking place in the polymer matrix, these indicator products could, thus, be analysed to rapidly predict the degree of degradation in the polymer matrix and further to predict the long-term properties and remaining lifetime of the product.     

Controlling the Behaviors of Biodegradable/Bioabsorbable Polymers with Cyclodextrins

The cyclic six, seven, and eight-membered oligosaccharides -, -, and -cyclodextrins (CDs) can serve as hosts for a variety of polymer guests to form crystalline inclusion compounds (ICs), wherein the guest polymers are included in the continuous narrow channels (0.5–1.0 nm in diameter) formed by the host CD stacks. Polymers included as guests in CD-ICs are highly extended and segregated from neighboring chains by the walls of the host CD bracelets. As a consequence, when polymer-CD-ICs are treated with solvents for CDs that are non-solvents for the included polymers or with amylase enzymes, the CDs are removed and the guest polymers are coalesced into bulk samples whose structures, morphologies, and even chain conformations are different from those achieved by consolidation from their randomly coiling, entangled solutions and melts. Often these CD-IC coalesced and consequently reorganized polymer samples exhibit properties that are distinct from their normally processed bulk samples. Here we describe the CD-IC processing of several biodegradable/bioabsorbable homopolymers, copolymers, and blends made from poly (L-lactic acid), poly (-caprolactone), and poly (-hydroxybutyrate)s, with special emphasis placed on their improved and controllable properties. For example, the phase segregation and consequent crystallinities of their normally incompatible homopolymer blends and their block copolymers may be controlled and thus improved. In addition, co-inclusion of small molecule guests, such as drugs or anti-bacterials, in their common CD-ICs, and subsequent coalescence, yields well-mixed blends of these biodegradable/bioabsorbable polymers and the small molecule co-guests, which may lead, for example, to the improved delivery of drugs.     

Ecotoxicity Evaluation of the Biodegradable Polymers PLA,PBAT and its Blends Using <Emphasis Type="Italic">Allium cepa</Emphasis> as Test Organism

Biodegradable polymers are considered a feasible option to minimize the environment impacts of high disposal of solid waste. Nevertheless, environmental safety of these materials is a few explored issue. In this context, this study evaluated ecotoxicological effects in soil of the biodegradable materials poly(lactic acid)-PLA, poly(butylene adipate co-terephthalate)-PBAT and their blends compatibilized with a chain extender. The tool used for this analysis was the bioassay with Allium cepa as test organism. The studied materials were not phytotoxic, cytotoxic, genotoxic nor mutagenic for meristematic cells of A. cepa.     

Report: recycling of flame-retarded plastics from waste electric and electronic equipment (WEEE).

Shredder residues produced in plants processing waste electric and electronic equipment are excluded from material recycling due to a variety of polymeric materials and the presence of brominated flame retardants (BFR), which might contain banned polybrominated diphenyl ethers or toxic polybrominated dioxins and furans (PBDD/F). Herein we present a technological approach to transfer a significant portion of the shredder residue into recycled polymers. The technological approach consists of a density-based enrichment of styrenics, which are subjected to a solvolysis process (CreaSolv process) in a second stage. This stage allows the elimination of non-target polymers and extraction of BFR and PBDD/F. Pilot processing of 11.5 and 50 kg shredder residues indicated a material yield of about 50% in the density stage and 70-80% in the CreaSolv process, and an effective removal of BFR additives. The recycled products were proved to comply with threshold values defined by the European directive on the restriction of hazardous substances (RoHS) and the German Chemikalienverbotsverordnung. Mechanical material properties exhibited high tensile and flexural modules as well as slight impact strength, which qualify the products for applications in new electronic equipment.