Adsorption/Desorption of Polyvinyl Alcohol on Solid Substrates and Relevant Biodegradation

The rates and extents of absorption and desorption of polyvinyl alcohol (PVA) samples on different solid substrates comprising montmorillonite, quartz sand, and farm soil, as well as humic acid mixture are reported. The uptake of PVA by the substrates was analyzed as a function of PVA hydrolysis (72–98%), molecular weight, and molecular weight distribution. Higher adsorption was detected on montmorillonite followed by farm soil, whereas the quartz sand did not display any specific adsorption affinity for the PVA. An increase in the hydrolysis degree of PVA increased the adsorption rate and extent whereas this feature was reversed by an increase in PVA molecular weight. The desorption of PVA samples from the different substrates was performed both under various pH conditions and in the presence of concentrated HF that was used to dissolve the silicon derivatives present in the substrates. Biodegradation experiments carried out in liquid cultures of PVA adsorbed on montmorillonite showed that the mineralization of the adsorbed PVA was much lower than that detected for the nonadsorbed PVA. This investigation suggests that irreversible adsorption of PVA on the clay component occurs in soil, thus substantially inhibiting PVA biodegradation.     

Influence of Technological Process on Biodegradation of PVA/Waxy Starch Blends in an Aerobic and Anaerobic Environment

Improving biodegradability of PVA/starch blends is a reality already documented by a number of works. Admittedly, mechanical properties of products (for example, tensile strength) are somewhat worse, but suitable composition optimizing or chemical modifying of starch may eliminate the problem to a large degree. This work is an attempt to find another potential effect influencing biodegradability, that of technological procedure for producing films from these blends on an extruder. The procedure with a so-called pre-extrusion step (two-stage) and dry-blend (single-stage) produced blends of slightest differences in achieved biodegradability (virtually within limits of experimental error) in aerobic (76 vs. 79%) as well as anaerobic breakdown (48 vs. 52%). Conversely, morphological analysis exhibited superior homogeneity of films prepared by the two-stage process; their tensile strength was also higher.     

Anaerobic Biodegradation of Polyvinyl Alcohol Modified by Extracellular Polysaccharides

This work focused on anaerobic biodegradation of blends composed of glycerol-plasticized polyvinyl alcohol (PVA) and biopolymer (starch, gellan, xanthan) in an aqueous environment, after inoculation with digested activated sludge from a municipal wastewater treatment plant. Glycerol degradability is comparable to degradability of used modifying agents. Modifying agents added in the 20–40 wt% range proportionally increased biodegradation degree (D_t) calculated from balance of transformed carbon in the system. Biodegradation degree of polysaccharides and glycerol attained 95% and over. For PVA it was only 6.5% (in breakdown times up to 500 h). Content of polysaccharides favorably affects biodegradation degree of polyvinyl alcohol blends, but at the expense of reduced mechanical properties of resultant products.     

Effect of Cross-Linking Waste Protein with Diepoxides on its Biodegradation under Anaerobic Conditions

Biodegradability testing was performed in an aqueous environment under anaerobic conditions after inoculation with digested sludge from municipal wastewater treatment plant. In cross-linking with 1,2:3,4-diepoxybutane in limits 0.8–9.1% weight, biodegradability degree decreased from 76.8 to 62.2%; when 1,2:7,8 diepoxyoctane in quantities 1.1–13.2% weight was used, biodegradability degree dropped more prominently – from 72.3 to 22.8%. There is obviously a direct connection between growing cross-link degree (assessed by so-called fixation index) and decreasing readiness to biodegradation, apparently owing to build-up of a network forming an obstacle to access of micro-organisms and enzymes.     

Effect of Cell-to-matrix Ratio in Polyvinyl Alcohol Immobilized Pure and Mixed Cultures on Atrazine Degradation

Atrazine biodegradation by immobilized pure and mixed cultures was examined. A pure atrazine-degrading culture, Agrobacterium radiobacter J14a (J14a), and a mixed culture (MC), isolated from an atrazine-contaminated crop field, were immobilized using phosphorylated-polyvinyl alcohol (PPVA). An existing cell immobilization procedure was modified to enhance PPVA matrix stability. The results showed that the matrices remained mechanically and chemically stable after shaking with glass beads over 15 days under various salt solutions and pH values. The immobilization process had a slight effect on cell viability. With the aid of scanning electron microscopy, a suitable microstructure of PPVA matrices for cell entrapment was observed. There were two porous layers of spherical gel matrices, the outside having an encapsulation property and the inside containing numerous pores for bacteria to occupy. J14a and MC were immobilized at three cell-to-matrix ratios of 3.5, 6.7, and 20 mg dry cells/mL matrix. The atrazine biodegradation tests were conducted in an aerobic batch system, which was inoculated with cells at 2,000 mg/L. The tests were also conducted using free (non-immobilized) J14a and MC for comparative purpose. The cell-to-matrix ratio of 3.5 mg/mL provided the highest atrazine removal efficiency of 40–50% in 120 h for both J14a and MC. The free cell systems, for both cultures, presented much lower atrazine removal efficiencies compared to the immobilized cell systems at the same level of inoculation.     

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.     

Biodegradability of Poly (lactic acid), Preparation and Characterization of PLA/Gum Arabic Blends

In this study, the biodegradation of PLA films using microorganisms from Lake Bogoria (Kenya) were investigated. The biodegradation tests done using certain strains of thermophilic bacteria showed faster biodegradation rates and demonstrated temperature dependency. The biodegradation of the PLA films was studied using Gel Permeation Chromatography (GPC) and light microscopy. The biodegradation of PLA was demonstrated by decrease in molecular weight. The preparation and characterization of PLA/Gum Arabic blends were also investigated using DSC, TGA, TMA and NMR. In summary, the results obtained in this research show that PLA films undergo fast biodegradation using thermophiles isolated from Lake Bogoria. The PLA/GA blends studies show it is possible to prepare films of varying hydrophobic–hydrophilic properties for various applications.     

Moisture Sorption Characteristics of Microbially Produced Polysaccharide and Polyvinyl Alcohol Blends

Moisture sorption characteristics of microbial polysaccharide (Ps.C101) from Pseudomonas caryophilli and polyvinyl alcohol (PVA) blends have been carried out at 27°C for water activity from 0.1 to 0.9. The sorption data was used to fit six different sorption isotherm models proposed in literature. The model constants were determined by linear fitting of the sorption equations. The ranges of applicability of water activity for isotherm models reported in this paper lie in between 0.1 and 0.4 for Brunaur–Emmet–Teller (BET) model (monolayer), and in between 0.2 and 0.9 for other models. The value of the coefficient of determination (R² = 0.97 ± 0.02) confirms the applicability of the equations studied.     

Fenton法氧化降解聚乙烯醇的机制

为深入了解Fenton法氧化降解聚乙烯醇（PVA）的机制,通过考察反应过程中COD、BOD5、总有机碳及pH等随反应时间的变化,研究了聚乙烯醇Fenton氧化降解过程的特点,结果表明,当PVA被Fenton试剂氧化时,可生成大量CO2,同时生成酸性中间产物。进一步分析认为,当Fenton试剂中H2O2不足景时PVA氧化的中间产物以醛为主,而当H2O2足量时醛会被继续氧化生成有机酸,最终COD去除率达到80％。     

Effects of Modified Starch and Different Molecular Weight Polyvinyl Alcohols on Biodegradable Characteristics of Polyvinyl Alcohol/Starch Blends

The common biodegradable properties of polymer make them an excellent pair for blending, and the water solubility of polyvinyl alcohol (PVA) makes it easy to mix evenly with the starch. In this study, PVAs with different molecular weights were blended with various compositions of cross-linked starch (CLS) to explore the effects of molecular weight of PVA on the biodegradable characteristics of the PVA/starch blends. Comparing the biodegradability of all the various PVA/starch blends, a PVA was singled out from the PVA/starch blends of higher biodegradability. Further, the chosen PVA was then blended with the acid-modified starch (AMS) to systematically investigate the effects of the modified processing of starch on the biodegradable characteristics of the PVA/starch blends. Differential scanning calorimetry (DSC) analysis of PVA and PVA/starch specimens reveal that the T_m values of PVA/starch specimens reduce gradually as their CLS or AMS contents increase. After the CLS is blended in PVAs of different molecular weights, the tensile strength (??_f) and elongation at break (??_f) values of (P₁₀₀S₀)G₂₀M₁ specimen increase and simultaneously reduce, respectively, as their molecular weights of PVA increase from about 80,000 (PVA_BF-17) to 120,000 (PVA_BF-26). The ??_f and ??_f values of the PVA/modified-starch blends decrease with an increase in the modified starch contents. The ??_f values of the PVA/AMS specimens decrease with an increase in the concentrations of hydrochloric acid. Comparing the ??_f values of the PVA/CLS specimens with those of the PVA/AMS specimens, the ??_f values of the PVA/CLS specimens are better than those of the PVA/AMS specimens. On the contrary, the ??_f values of the PVA/AMS specimens are better than those of the PVA/CLS specimens. According to the biodegradability of all the PVA/starch blends, PVA with higher molecular weights displays higher biodegradability. The biodegradability of the PVA/modified-starch blends increase as the modified starch contents of the PVA/modified-starch blends increase. As evidenced by the results of the biodegradability test, the biodegradability of the PVA/modified-starch blends, therein PVA is blended with 1N AMS, shows better biodegradability. The result of bio-reaction kinetics experiment can evaluate the decomposition tendency of the PVA/starch blends up to any biodegradable rate under ambient environment. Using the kinetic model of the first order reaction, it is estimated that 16.20?years and 12.47?years will be needed for the PVA_BF-17/starch blends, containing 20 and 40% of CLS respectively, to be degraded up to 70% under ambient environment. In addition, it is 1.68?years for the PVA_BF-26 blends with the 40% 2N AMS under decomposition environment while it is 1.94?years for the 40% 1N AMS. Overall, the decomposition potential of PVA/AMS specimens is better than PVA/CLS specimens. Furthermore, the 1N(26P₆₀AS₄₀)₁₀₀G₂₀M₁ specimen is coincidence the biodegradable material criteria of Environmental Protection Administration (EPA) of Taiwan.     

Effect of Cross-Linking Waste Protein with Dialdehydes on Its Biodegradation Under Anaerobic Conditions

Most native polymers used in processing and application technologies are admittedly disposable from the environment in a biologic manner, but products possess low mechanical strength. One of the paths to increasing this attribute (if feasible) is their cross-linking, which may, however, affect their readiness to biodegradation. In the presented work this condition was observed on the example of waste protein (Hykol B) cross-linking by means of glutardialdehyde and glyoxal. Degree and course of cross-linking were determined through impedance spectroscopy. The objective of this work also was to obtain data for constructing a sensor capable of following the cross-linking course in real time, for potential industrial application of Hykol in continuous production. Impedance spectroscopy proved to be applicable even to this kind of material marked by considerable water content and exhibiting relatively high electric conductivity; so far it had been used only for materials of low conductivity. An aqueous environment inoculated with digested anaerobic sludge from a municipal wastewater treatment plant was selected for modeling anaerobic conditions. The relation was studied between cross-linking degree given by content of cross-linking agent (determined by impedance spectroscopy) and biodegradation degree under anaerobic conditions. It was confirmed that network density as given by quantity of added agent not only reduced breakdown degree but also slowed the course of the process. This fact is particularly obvious with cross-linking by means of glyoxal; network density is thus dependent on type of employed substance, which affect type and structure of created network. That not merely forms an obstacle during polymer swelling and dissolution but also prevents access of bacteria to source of metabolized organic carbon.     

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.     

Effect of Ionizing Radiation on the Morphological,Thermal and Mechanical Properties of Polyvinyl Alcohol/Polyethylene Glycol Blends

Blends of water—soluble polymers based on Poly vinyl alcohol (PVA) and Polyethylene glycol (PEG) have been prepared by the solution casting technique. The effect of various doses of γ-radiation on the structural properties of PVA/PEG polymer blends with all its compositions has been investigated. From the visual observation of all the blend compositions, it was found that, the best compatibility of the blend is up to 40% PVA/60%PEG. The structure–Property behavior of all the prepared blends before and after γ-irradiation was investigated by IR Spectroscopy, thermogravimetric analysis (TGA), mechanical properties and Scanning electron microscope (SEM). The gel content and the swelling behavior of the PVA/PEG blends were investigated. It was found that the gel content increases with increasing irradiation dose and PVA concentration in the blend. Swelling percent increased as the composition of PEG increased in the blend. The results obtained by FTIR analysis and SEM confirm the existence of possible interaction between PVA and PEG homopolymers. TGA of PVA/PEG blend, before and after γ-irradiation, showed that the unirradiated and irradiated PVA/PEG blends are more stable against thermal decomposition than pure PVA. Improvement in tensile mechanical properties of PVA/PEG blends was occurred.     

Evaluation of the Biodegradability of Polyvinyl Alcohol/Starch Blends: A Methodological Comparison of Environmentally Friendly Materials

Polyvinyl alcohol (PVA) and starch are both biodegradable polymers. These two polymers can be prepared as biodegradable plastics that are emerging as one of the environmental friendly materials available now. In this study, after reacting with sodium trimetaphosphate (STMP), modified corn starch was blended with PVA in different ratios by a barbender. Test samples were prepared for mechanical and thermal properties measurements. The surface roughness and morphology of fractured surface of the samples were observed by an atomic force microscopy (AFM) and scanning electron microscope (SEM) measurements. Aqueous degradation by enzyme, water absorption and biodegradability behavior were evaluated for the degradability. The biodegradability of these materials was followed by bio-reactivity kinetics models. Results showed that the addition of modified starch could enhance its water uptake. With an addition of 20 wt% of modified starch, the blend had a maximum weight loss during enzymatic degradation. It was found that the degradability was enhanced with the addition of the starch. Analyzing the results of the biodegradability based on the kinetic models, the growth rate of the microorganism was found to be increasing with the increase of the content of starch in the PVA/starch blends in the first order reaction fashion. In our biodegradability analysis, i.e., based on the China national standards (CNS) 14432 regulations, we estimated the decomposition behavior based on the mentioned first order reaction. We found that the PVA/starch blends would take 32.47, 16.20 and 12.47 years to degrade by 70% as their starch content 0, 20 and 40 wt%, respectively.     

Modeling Biodegradation of Nonylphenol

Nonylphenol is the primary breakdown product of nonylphenol ethoxylates, a certain class of nonionic surfactants. Nonylphenol has been found to be toxic to aquatic organisms and has been suspected of being harmful to humans due to its xenoestrogenic properties. Although there are known releases of nonylphenol to the environment, there is a lack of data describing the extent of biodegradation. This study thus focuses on much needed information on the biodegradation kinetics of nonylphenol. Oxygen uptake, cell growth and nonylphenol removal data were collected using batch reactors in an electrolytic respirometer. Nonylphenol removal, cell growth and substrate removal rates were modeled by the Monod, Haldane, Aiba, Webb, and Yano equations. The differential equations were solved by numerical integration to simulate cell growth, substrate removal, and oxygen uptake as a function of time. All models provided similar results with the Haldane model providing the best fit. The values of the kinetic parameters and the activation energy for nonylphenol were determined. These values can be used for predicting fate and transport of nonylphenol in the environment. The validity of applying each model to the biodegradation of nonylphenol was analyzed by computing the R ² values of each equation.     

A Composting Study of Membrane-Like Polyvinyl Alcohol Based Resins and Nanocomposites

This study presents the effect of biodegradation, in a composting medium, on properties of membrane-like crosslinked and noncrosslinked polyvinyl alcohol (PVA) and nanocomposites. The composting was carried out for 120 days and the biodegradation of these materials was characterized using various techniques. The changes in the PVA resin and nanocomposite surface topography and microstructure during composting were also characterized. The results from the analyses suggest biodegradation of PVA based materials in compost medium was mainly by enzymes secreted by fungi. The results also indicate that the enzymes degraded the amorphous regions of the specimens first and that the PVA crystallinity played an important role in its biodegradation. The surface roughness of the specimens was seen to increase with composting time as the microbial colonies grew which in turn facilitated further microorganism growth. All specimens broke into small pieces between 90 and 120 days of composting as a result of deep biodegradation. Glyoxal and malonic acid crosslinking decreased the PVA biodegradation rate slightly. Addition of highly crystalline microfibrillated cellulose and naturally occurring halloysite nanotubes in PVA based nanocomposites also decreased the biodegradation rate. The three factors: PVA crystallinity, crosslinking and additives, may be utilized effectively to extend the life of these materials in real life applications.     

Mechanical Property and Biodegradability of Cast Films Prepared from Blends of Oppositely Charged Biopolymers

Biodegradable cast films of about 50 m thickness were fabricated by blending oppositely charged biopolymers such as anionic starch–chitosan, and cationic starch–pectin. The tensile strength and elongation at break (%) of films were evaluated as well as their capacity to degrade in compost. Films recovered from soil every 48 h showed consistent degradation (weight loss), diminution of the polymers characteristic peak absorbance in the carbohydrate fingerprint region of the FTIR, and changes in the surface morphology via scanning electron microscopy (SEM). Anionic starch–chitosan films had much superior tensile strength and elongation compared to cationic starch–pectin, suggesting that the ionic bonds formed between anionic-starch and positively charged groups in chitosan polymer were much more stable and stronger. Initially, both films lost about 36% weight within 96 h, which also correlated well with the loss in the characteristic absorption peaks in the region of the infrared spectrum typical of biopolymers. The total mineralization of films by microorganisms in compost soil was also measured using respirometric techniques. Though the rate of mineralization differed for two formulations, total mineralization (extent) for both films were achieved within 45 days.     

Electron Microscope Observation of Biodegradation of Polymers

Biodegradable polymers generally decompose in the various media in our environments. These environments contain soils, seawater, and activated sludge. If biodegradable materials waste is discarded, they decompose in these media. The biodegradation process of biodegradable polymers was investigated by scanning electron microscopy. Polycaprolactone, polybutylene succinate, and P(3HB-co-3HV) were tested. The shapes of holes on the decomposing surfaces are different according to the biodegradation media. Semispherical holes are observed on the surfaces of polybutylene succinate films degraded in activated sludge and cracks are observed on the surfaces of polycaprolactone films degraded in soil.     

Biodegradation and flushing of MBT wastes

Mechanical–biological treatment (MBT) processes are increasingly being adopted as a means of diverting biodegradable municipal waste (BMW) from landfill, for example to comply with the EU Landfill Directive. However, there is considerable uncertainty concerning the residual pollution potential of such wastes. This paper presents the results of laboratory experiments on two different MBT waste residues, carried out to investigate the remaining potential for the generation of greenhouse gases and the flushing of contaminants from these materials when landfilled. The potential for gas generation was found to be between 8% and 20% of that for raw MSW. Pretreatment of the waste reduced the potential for the release of organic carbon, ammoniacal nitrogen, and heavy metal contents into the leachate; and reduced the residual carbon remaining in the waste after final degradation from ～320 g/kg dry matter for raw MSW to between 183 and 195 g/kg dry matter for the MBT wastes.     

厌氧生物降解活性黑KN-B5

研究了在葡萄糖作为共代谢基质时活性黑KN-B5的降解效果。实验结果表明:当葡萄糖质量浓度为1 500m g/L时,活性黑KN-B5初始质量浓度为30m g/L的染料溶液厌氧生物降解24h和48h后的降解率分别达到77.5%和90.3%;活性黑KN-B5的厌氧降解符合一级动力学方程,其反应速率常数为0.043 6h-1,半衰期为15.9h;葡萄糖质量浓度的增大对提高活性黑KN-B5厌氧生物降解效果有利。紫外-可见光谱扫描结果表明,活性黑KN-B5的降解过程中生成了小分子芳香胺类化合物;扫描电子显微镜照片表明污泥中对活性黑KN-B5起降解作用的菌种主要是杆菌和球菌。