Starch- polyvinyl alcohol crosslinked film— performance and biodegradation

Starch-PVOH cast films were prepared with and without crosslinking agent (hexamethoxymethylmelamine) in the absence of plasticizer. Moisture absorption in films without crosslinking agent at a low relative humidity was similar to that of PVOH and increased as the relative humidity increased. Films with crosslinking agent showed moisture absorption linearly proportional to the relative humidity. Significant improvement in resistance to water disintegration for crosslinked starch-PVOH films was observed. While the tensile strength decreased with increased relative humidity, crosslinking significantly improved the tensile strength. Increased PVOH content improved elongation of films even when the relative humidity was 80% or higher. Biodegradation studies revealed that the degradation rate was negatively correlated with the PVOH content in films and crosslinking generated more converged degradation curves. Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may also be suitable.     

阴离子对Fenton氧化降解聚乙烯醇的影响

研究了亚铁盐中NO3-、SO42-、Cl-、Br-等阴离子对Fenton氧化降解高浓度聚乙烯醇(PVA)效果的影响。实验结果表明:酸性条件下具有氧化性的阴离子NO3-或能被氧化形成具有氧化性物质的离子Cl-、Br-对Fenton氧化降解PVA有协同促进作用,且氧化性越强越容易促使PVA大分子链断裂;含NO3-、Cl-、Br-和SO42-的Fenton氧化降解PVA,COD去除率分别为70.05%、70.60%、72.40%和87.90%。采用COD去除率相差不大、产物分子量较小的硝酸亚铁、氯化亚铁、溴化亚铁中的一种作为Fenton试剂催化降解PVA较适宜。     

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.     

Processing and mechanical properties of biodegradable Poly(hydroxybutyrate-co-valerate)-starch compositions

Poly(hydroxybutyrate-co-valerate) (PHBV) is a completely biodegradable thermoplastic polyester produced by microbial fermentation. The current market price of PHBV is significantly higher than that of commodity plastics such as polyethylene and polystyrene. It is therefore desirable to develop low-cost PHBV based materials to improve market opportunities for PHBV. We have produced low-cost environmentally compatible materials by blending PHBV with granular starch and environmentally benign CaCO₃. Such materials can be used for specific applications where product biodegradability is a key factor and where certain mechanical properties can be compromised at the expense of lower cost. The inclusion of granular starch (25 wt%) and CaCO₃ (10 wt%) in a PHBV matrix (8% HV, 5% plasticizer) reduces the cost by approximately 40% and has a tensile strength of 16 MPa and flexural modulus of 2.0 Gpa, while the unfilled PHBV/plasticizer matrix has a tensile strength of 27 MPa and a flexural modulus of 1.6 GPa.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.The mention of firm names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over other firms or similar products not mentioned.     

Pressure- volume- temperature relationships of soy protein isolate/starch plastic

The use of pressure-volume-temperature (PVT) studies in processing of a biodegradable plastic composition made from soy protein isolate and corn starch is described. The ability of PVT measurements to predict the combined effects of pressure, volume, and temperature effects is demonstrated. The results show that the PVT relations of the plastic can be predicted by using a regression analysis similar to the Tait equations of state. A change in slope of the PVT curves was observed at around 80‡C, which is ascribed to the glass-transition process of the plastic. Evidence of onset of thermal degradation of the plastic was observed at ca. 160‡C under 0 to 200 MPa isobaric pressure. This thermal degradation precluded determination of the crystal melting point of the plastic.     

Extruded Cornstarch-Glycerol-Polyvinyl Alcohol Blends: Mechanical Properties, Morphology, and Biodegradability

Elongation properties of extruded cornstarch were improved by blending with glycerol. Further blending of starch-glycerol with polyvinyl alcohol (PVOH) resulted in significant improvements in both tensile strength (TS) and elongation at break. Samples of starch-glycerol without PVOH equilibrated at 50% relative humidity had a TS of 1.8 MPa and elongation of 113%, whereas those containing PVOH had a TS and elongation of 4 MPa and 150%, respectively. Dynamic mechanical analysis (DMA) of starch-glycerol-PVOH blends showed that decreases in glass transition temperatures (T _g values) were proportional to glycerol content. Scanning electron microscopy (SEM) of fractured surfaces revealed numerous cracks in starch-glycerol (80:20) samples. Cracks were absent in starch-glycerol (70:30) samples. In both blends, many starch granules were exposed at the surface. No exposed starch granules were visible in blends with added PVOH. Starch-glycerol samples incubated in compost lost up to 70% of their dry weight within 22 days. Addition of PVOH lowered both the rate and extent of biodegradation.     

Biodegradable corn starch loose- fill. I. The effect of the extrusion temperature on the physical properties of loose-fill

Extrusion with an intermeshing corotating twin-screw extruder with a limited amount of water caused structural changes in corn starch. The structural changes resulted in a transformation-from a semicrystalline to an amorphous state and the development of orientation of molecular chains in the amorphous region during extrusion. These structural changes, in turn, caused an increase in theT _g, tensile strength, and resilience of the extruded corn starch. Our experimental results showed that the tensile properties and resilience of the expanded corn starch extruded at 240‡C were the best: tensile strength, 1.7 kPa; tensile modulus, 40.4 kPa; and resilience, 57.2%. Extrusion produced an expanded corn starch suitable for protective loose-fill.     

Synthesis of a block copolymer of poly(3-hydroxybutyrate) and poly(ethylene glycol) and its application to biodegradable polymer blends

A block copolymer {P[(R,S)-HB-b-EG]} of atactic poly[(R,S)-3-hydroxybutyrate] {P[(R,S)-HB]} and poly(ethylene glycol) (PEG) was prepared by the ring-opening polymerization of -butyrolactone in the presence of a macroinitiator (PEG/ZnEt₂/H₂O) which had been produced by the reaction of ,-dihydroxy PEG ( _n=3000) with ZnEt₂/H₂O (1/0.6) catalyst. The block copolymer ( _n=10,500, _w/ _n=1.2) was an A-B-A triblock copolymer comprising atactic P[(R,S)-HB] (A) and PEG (B) segments. The miscibility, physical properties, and biodegradability of binary blends of microbial poly[(R)-3-hydroxybutyrate] {P[(R)-HB]} with the block copolymer P[(R,S)-HB-b-EG] has been studied. The glass-transition temperature (T _g) data showed that the P[(R)-HB]/P[(R,S)-HB-b-EG] blend was miscible in the amorphous state. The P[(R)-HB] film became flexible and tough by means of blending with P[(R,S)-HB-b-EG] block copolymer. The enzymatic degradation of blend films was carried out at 37°C and pH 7.4 in a 0.1M phosphate solution of an extracellular PHB depolymerase fromAlcaligenes faecalis. The enzymatic degradation took place solely on the surface of the blend films.     

Starch, Poly(lactic acid), and Poly(vinyl alcohol) Blends

Research on biodegradable materials has been stimulated due to concern regarding the persistence of plastic wastes. Blending starch with poly(lactic acid) (PLA) is one of the most promising efforts because starch is an abundant and cheap biopolymer and PLA is biodegradable with good mechanical properties. Poly(vinyl alcohol) (PVOH) contains unhydrolytic residual groups of poly(vinyl acetate) and also has good compatibility with starch. It was added to a starch and PLA blend (50:50, w/w) to enhance compatibility and improve mechanical properties. PVOH (M_W 6,000) at 10%, 20%, 30%, 40%, 50% (by weight) based on the total weight of starch and PLA, and 30% PVOH at various molecular weights (M_W 6,000, 25,000, 78,000, and 125,000 dalton) were added to starch/PLA blends. PVOH interacted with starch. At proportions greater than 30%, PVOH form a continuous phase with starch. Tensile strength of the starch/PLA blends increased as PVOH concentration increased up to 40% and decreased as PVOH molecular weight increased. The increasing molecular weight of PVOH slightly affected water absorption, but increasing PVOH concentration to 40% or 50% increased water absorption. Effects of moisture content on the starch/PLA/PVOH blend also were explored. The blend containing gelatinized starch had higher tensile strength. However, gelatinized starch also resulted in increased water absorption.     

Novel malonate-type copolymers containing vinyl alcohol blocks as biodegradable segments and their builder performance in detergent formulations

Poly[(disodium methylene malonate)-co-(vinyl alcohol)] [P(DSMM-VA)] and poly[(disodium ethoxymethylene malonate)-co-(vinyl alcohol)] [P(DSEMM-VA)] containing a poly(vinyl alcohol) (PVA) block as a biodegradable segment were prepared and their biodegradability and functionality were evaluated and compared with those of the corresponding fumarate and maleate copolymers. It was found that the 1,1-dicarboxylate-type copolymers, P(DSMM-VA) and P(DSEMM-VA), showed better biodegradability than the corresponding 1,2-dicarboxylate-type copolymers, P(DSF-VA) and P(DSM-VA). This improved biodegradability of P(DSMM-VA) and P(DSEMM-VA) is probably attributable to their more expanded polymer chain in aqueous solution, which will be more accessible to the degrading enzymes. The minimum chain length of the PVA-block, which acts as a biodegradable segment in the polymer chain, is estimated to be 2–3 and 3–4 monomer units for P(DSMM-VA) and P(DSEMM-VA), respectively. On the other hand, the minimum PVA block is about 5 and 7 monomer units for the fumarate and maleate copolymers, respectively. It was confirmed that P(DSMM-VA) showed excellent builder performance compared to the corresponding fumarate copolymer.Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.     

Processing and characterization of a new biodegradable composite made of a PHB/V matrix and regenerated cellulosic fibers

In this study, a biodegradable composite consisting of a degradable continuous cellulosic fiber and a degradable polymer matrix—poly(3-hydroxybutyrate)-co-poly(3-hydroxyvalerate (PHB/V with 19% HV)—was developed. The composite was processed by impregnating the cellulosic fibers on-line withPHB/V powder in a fluidization chamber. The impregnated roving was then filament wound on a plate and hot-pressed. The resulting unidirectional composite plates were mechanically tested and optically characterized by SEM. The fiber content was 9.9 ±0.9 vol% by volumetric determination. The fiber content predicted by the rule of mixture for unidirectional composites was 13.8 ±1.4 vol%. Optical characterization showed that the fiber distribution was homogeneous and a satisfactory wetting of the fibers by the matrix was achieved. Using a blower to remove excess matrix powder during processing increased the fiber content to 26.5 ±3.3 vol % (volumetric) or 30.0 ±0.4 vol% (rule of mixture). The tensile strength of the composite parallel to the fiber direction was 128 ±12 MPa (10 vol% fiber) up to 278 ±48 MPa (26.5 vol% fiber), compared to 20 MPa for the PHB/V matrix. The Young’s modulus was 5.8 ±0.5 GPa (10 vol% fiber) and reached 11.4 ±0.14 GPa (26.5 vol% fiber), versus 1 GPa for the matrix.     

Progress in the genetic manipulation of crops aimed at changing starch structure and increasing starch accumulation

The starch content and its composition have important consequences for the yield of the harvested crop and the materials extracted from it. The functional properties of the foods or other processed materials derived from these crops are also affected by the structure and composition of the starch. Recently, genetic engineering has been used to produce plants with an elevated starch content, achieved by transforming the plant with a mutated bacterial gene coding for an ADPglucose pyrophosphorylase that is active in the presence of metabolites which inhibit the plant enzyme. Besides the practical implications of these results, this experiment provided direct evidence for the regulatory role of the ADPglucose pyrophosphorylase in starch synthesis. Other bacterial enzymes, such as glycogen synthase and branching enzyme, could be introduced in order to modify starch structure. However, a more elegant (but longer-term) approach would be to learn enough about the structure-function relationships of the plant enzymes so that the product of their action could be changed. To achieve this objective, much more will have to be learned about the enzymes involved in the biosynthesis of starch than is presently known. Here, the basic properties of starch and the current research approaches to understanding its biosynthesis are described, together with a perspective of how genetic manipulation of starch structure may be achieved.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.     

活性污泥的固定化及其性能研究

用改进聚乙烯醇-硼酸法将活性污泥制成固定化颗粒,考察了改进聚乙烯醇-硼酸法的最佳条件及固定化颗粒的性能。实验结果表明：改进聚乙烯醇-硼酸法的最佳条件为聚乙烯醇质量分数6．5％、包泥比（包埋剂与活性污泥质量比）1．2：1、二氧化硅质量分数1．5％、活性炭质量分数0．3％、海藻酸钠质量分数0．6％;用最佳条件下制得的固定化颗粒处理模拟化工废水,连续运行15d后的COD去除率达90％以上,且固定化颗粒耐冲击负荷和pH变化能力强;固定化颗粒对模拟化工废水的COD去除速率随进水COD的变化曲线类似于米氏方程所描述的反应初速度随底物浓度的变化规律。     

Thermodynamic and Diffusion Properties of Biodegradable Systems Based on Starch and Cellulose Derivatives

The interval sorption and diffusion of water vapor were studied for two systems: methylcellulose (MC)/starch and carboxymethylcellulose (CMC)/starch. The diffusion coefficient of water vapor and the Gibbs free energy of swelling of these blends in water were estimated. The Gibbs free energy of mixing starch with the cellulose derivatives was determined using the thermodynamic cycle. CMC/starch was shown to be more compatible than MC/starch. Biodegradation of these systems in the water–soil environment was measured and found to increase with the concentration of starch in its blends with cellulose derivatives.     

Toxicity screening of biodegradable polymers. I. Selection and evaluation of cell culture test methods

A screening test method for potential toxicity of biodegradable plastics on humans and the environment was selected and evaluated with samples of cellulose acetate, Bionolle, polyhydroxybutyrate-co-valerate (Biopol), and polycaprolactone (Tone polymer). Among the standardin vitro tests using animal cell cultures for the evaluation of biomedical materials, the test by direct contact and the test with extract were examined. Qualitative and quantitative determinations of the cell viability and morphology indicate that the test with extracts can be easily performed, providing reproducible and comparable results for all materials. Using the cell culture test with the extract of sterile samples, an estimation of the toxicity of a new polymeric material can be obtained within a few weeks.     

The relationship between blend miscibility and biodegradation of cellulose acetate and poly(ethylene Succmate) blends

The miscibility of cellulose acetate (CA; degree of substitution = 2.5) and poly(ethylene succinate) (PES) has been investigated using a variety of thermal techniques and by solid-state carbon13 NMR spectroscopy. The blends containing greater than ca. 70% CA were found to be miscible. In the case of blends containing less than ca. 70% CA, a combination of thermal and NMR analyses suggests that these blends are not fully miscible on a 2.5- to 5-nm scale. On the scale which can be probed by dynamic mechanical thermal analysis (15 nm), the low-percentage CA blends exhibit “significant local concentration fluctuations≓. Investigation of the biodegradation of the blend components and of the blends revealed that PES degraded relatively rapidly and that CA degraded slowly. The blends degraded at a rate essentially identical to that of CA. Miscibility (75% CA blend) or crystallization of PES (30% CA blend) had no significant effect. These data suggest that a significant mode of degradation ófPES during composting involves chemical hydrolysis of the polymer followed by biological assimilation of monomers. Degradation of the blends is initiated in the amorphous phase. Because CA is a significant component of the amorphous phase, a small amount of CA significantly impacts the biodegradation rates of the blends.     

Processing and Physical Properties of Plastics Made from Soy Protein Polyester Blends

Blending soy protein with polyesters using a polyvinyllactam as a compatibilizer successfully made soy protein-based plastics. The polyesters used to produce blends included polycaprolactone (PCL) and Biomax (a commercial biodegradable polyester). The blends were processed by compounding extrusion and injection molding. Blends containing soy protein/Biomax-poly(vinyl alcohol) had tensile strengths ranging from 16–22 MPa, with samples containing larger percentages of the synthetic polymer exhibiting greater strengths. Blends made from soy protein, Biomax, and PCL had tensile strengths ranging from 27–33 MPa. All the blends had high Young's moduli but demonstrated brittle characteristics as evident from their low elongations at break, ranging from 1.8–3.1%. Plastics made from soy protein/polyester blends exhibited low water absorption and had good stability under ambient conditions relative to the plastics made from soy protein alone. Blends made from soy protein flour produced plastics with the lowest water absorption.     

Thermal and Rheological Properties of Commercial-Grade Poly(Lactic Acid)s

Poly(lactic acid) is the subject of considerable commercial development by a variety of organizations around the world. In this work, the thermal and rheological properties of two commercial-grade poly(lactic acid)s (PLAs) are investigated. A comparison of the commercial samples to a series of well-defined linear and star architecture PLAs provides considerable insight into their flow properties. Such insights are valuable in deciding processing strategies for these newly emerging, commercially significant, biodegradable plastics. Both a branched and linear grade of PLA are investigated. The crystallization kinetics of the branched polymer are inferred to be faster than the linear analog. Longer relaxation times in the terminal region for the branched material compared to the linear material manifests itself as a higher zero shear rate viscosity. However, the branched material shear thins more strongly, resulting in a lower value of viscosity at high shear rates. Comparison of the linear viscoelastic spectra of the branched material with the spectra for star PLAs suggests that the branched architecture is characterized by a span molecular weight of approximately 63,000 g/mol. The present study conclusively demonstrates that a wide spectrum of flow properties are available through simple architectural modification of PLA, thus allowing the utilization of this important degradable thermoplastic in a variety of processing operations.     

Thermal and mechanical properties of poly(lactic Acid) and poly(ethylene/butylene Succinate) blends

In this study, blends of poly (lactic acid) (PLA) with poly(ethylene/butylene succinate) (Bionolle) have been investigated for their thermal and mechanical properties as a function of the concentration of Bionolle. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and tensile tests were used to characterize the blends. From the results of the DMA and DSC, it was found that this blend system was not miscible within the compositions studied. DSC results showed that adding Bionolle aids in crystallization of PLA. It was observed that increasing the Bionolle concentration led to a slight increase in the strain-at-break of the blends but a decrease in the Young’s modulus and ultimate tensile strength. Biaxially oriented films showed an increase in tensile strength, modulus, and strain-at-break.     

具有共轭结构的CDPVA/ZnO复合光催化剂的制备及其可见光催化性能

CDPVA是一种具有共轭多烯序列的聚乙烯醇(PVA)衍生物。通过低温热处理法制备了CDPVA/ZnO复合光催化剂。表征结果显示,PVA经低温热处理后形成了具有一定共轭结构的CDPVA并包覆于纳米ZnO颗粒表面,提高了光催化剂的可见光响应能力,有效促进了光生空穴和电子的分离。当PVA与纳米ZnO的质量比为1∶100时,CDPVA/ZnO的可见光催化活性最高;在催化剂投加量为0.5 g/L、初始罗丹明B质量浓度为4 mg/L、可见光照射50 min的条件下,罗丹明B降解率为97.51%,明显优于纯纳米ZnO;CDPVA/ZnO循环使用9次后仍保持较高的罗丹明B降解率,表明CDPVA的包覆有效抑制了纳米ZnO的光腐蚀,提高了光催化剂的稳定性。