Anaerobic Biodegradation of Blends Based on Polyvinyl Alcohol

The presented work deals with blends composed of polyvinyl alcohol (PVA) and biopolymers (protein hydrolysate, starch, lignin). PVA does not belong to biologically inert plastics but its degradation rate (particularly under anaerobic conditions) is low. A potential solution to the issue problem lies in preparation of blends with readily degradable substrates. We studied degradation of blow-molded films made of commercial PVA and mentioned biopolymers in an aqueous anaerobic environment employing inoculation with digested activated sludge from the municipal wastewater treatment plant. Films prepared in the first experimental series were to be used for comparing biodegradation of blends modified with native or plasticized starch; in this case effect of plasticization was not proved. The degree of PVA degradation after modification with native or plasticized starch increases in a striking and practically same manner already at a starch level as low as approximately 5 wt.%. Films of the second experimental series were prepared as additionally modified with protein hydrolysate and lignin. Only lignin-modified samples exhibited a somewhat lower degree of biodegradation but regarding the measure of lignin present in blend this circumstance is not essential. Level of biodegradation with all discussed films differed only slightly—within range of experimental error.     

Role of Crosslinker on the Biodegradation Behavior of Starch/Polyvinylalcohol Blend Films

The effect of crosslinkers on the biodegradation behavior of starch/polyvinyl alcohol (PVA) blend films was investigated by weight loss study, Scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). Starch/PVA films were prepared by solution casting method and 5 weight% of four different crosslinking agents like epichlorohydrin, formaldehyde, zinc oxide and borax were used in four different sets to crosslink the films. These crosslinked starch/PVA films were biodegraded in compost. Weight loss study showed that crosslinking retarded the biodegradation of the films in the first 15?days, but after that, there was a significant increase in weight loss. The DSC analysis revealed that the consumption of starch and consequent rearrangement of the PVA molecules were distinctly different in the crosslinked films due to the effect of different crosslinking agents.     

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.     

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.     

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.     

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.     

Characterization of Biodegradable Composite Films Prepared from Blends of Poly(Vinyl Alcohol), Cornstarch,and Lignocellulosic Fiber

Several composite blends of poly(vinyl alcohol) (PVA) and lignocellulosic fibers were prepared and characterized. Cohesive and flexible cast films were obtained by blending lignocellulosic fibers derived from orange waste and PVA with or without cornstarch. Films were evaluated for their thermal stability, water permeability and biodegradation properties. Thermogravimetric analysis (TGA) indicated the suitability of formulations for melt processing, and for application as mulch films in fields at much higher temperatures. Composite films were permeable to water, but at the same time able to maintain consistency and composition upon drying. Chemical crosslinking of starch, fiber and PVA, all hydroxyl functionalized polymers, by hexamethoxymethylmelamine (HMMM) improved water resistance in films. Films generally biodegraded within 30 days in soil, achieving between 50–80% mineralization. Both starch and lignocellulosic fiber degraded much more rapidly than PVA. Interestingly, addition of fiber to formulations enhanced the PVA degradation.     

Characterization of Urea Encapsulated by Biodegradable Starch-PVA-Glycerol

The influence of the blending ratio of biodegradable starch/polyvinyl alcohol (PVA)/glycerol in encapsulating urea has been investigated. It is found that water absorption capacity increased approximately 135 % as the amounts of starch, PVA and glycerol in the composite film increase. Therefore, the swell ability of the composite film is increased and the urea is released from the composite film in the wet environment. The FTIR shows that the urea had been encapsulated successfully in the composite films. Moreover, the soil burial biodegradation results indicated that the biodegradability of the starch/PVA/glycerol/urea composite film strongly depended on the PVA proportion in the composite film matrix. The DSC results show that the higher the amount of PVA in the composite film, the less change of the melting enthalpy value. The crystalline region of PVA remains after biodegradation.     

Biodegradability of Starch Based Self-Supporting Antimicrobial Film and Its Effect on Soil Quality

Alarming environmental pollution from petroleum based non-biodegradable disposable packaging films has generated concern for development of alternatives from natural polymers such as starch. In the present work, the biodegradability of a self-supporting film made from starch and polyvinyl alcohol (PVA) (starch:PVA?=?9:1 as the polymer) together with glutaraldehyde as crosslinker and sodium propionate (SP) as antimicrobial was investigated by soil burial method. The changes in soil composition namely pH, organic carbon, available and total nitrogen, and water holding capacity as a result of biodegradation were also estimated. The film underwent ≈?90% biodegradation within a period of 28 days, with simultaneous increase in soil nutrients. Moreover, the pH remained in the accepted limit for plant growth. Thus, antimicrobial in the film did not hamper its biodegradation, rather disposal of the film in soil might facilitate plant growth.     

Biodegradation by Composting of Surface Modified Starch and PVA Blended Films

Several starch/PVA/glycerol polymer blends were prepared by a solution casting technique and examined for biodegradation by composting over 45 days. Within this time frame, the starch and glycerol components were fully degraded, leaving the PVA component essentially intact. The lowest PVA content film (20%) was selected as a polymer with enough PVA to impart important physical characteristics, but also enough starch to be considered biodegradable. The film characteristics were further improved by surface modification with chitosan. This modification did not interfere with the biodegradation of the starch component. Furthermore, there was slight evidence that PVA biodegradation had been initiated in composted, surface modified starch/PVA blends.     

Non-isothermal Crystallization Behaviors of Polyvinyl alcohol/Hydroxyethyl Cellulose Blend Films

In this work, polyvinyl alcohol/hydroxyethyl cellulose (PVA/HEC) blend films were fabricated by solution casting and the crystalline morphology as well as non-isothermal crystallization kinetics of the blends was investigated detailedly with polarized optical microscopy, X-ray diffraction and differential scanning calorimetry. With fixed cooling rate, the crystallization time for PVA/HEC was less than that for neat PVA. The crystallization peak temperature of PVA/HEC decreased first and then increased with the increase of HEC. With higher cooling rate, the crystallinity and crystallization time decreased. It worth noting that large spherocrystal with a size of 35 μm was observed by polarized optical microscopy for PVA/HEC blends for the first time.     

Utilization of Waste Lignin and Hydrolysate From Chromium Tanned Waste in Blends of Hot-Melt Extruded PVA-Starch

The demand for biodegradable plastic material is increasing worldwide. However, the cost remains high in comparison with common forms of plastic. Requirements comprise low cost, good UV-stability and mechanical properties, as well as solubility and water uptake lead to the preparation of multi-component polymer blends based on polyvinyl alcohol and starch in combination with waste products that are hard to utilize—waste lignin and hydrolysate extracted from chromium tanned waste. Surprisingly the addition of such waste products into PVA gives rise to blends with better biodegradability than commercial PVA in an aquatic aerobic environment with non-adapted activated sludge. These blends also exhibited greater solubility in the water and UV stability than commercial PVA. Tests on the processing properties of the blends (melt flow index, tensile strength and elongation at break of the films) as well as their mechanical properties showed that materials based on these blends might be applied in agriculture (for example as the systems for controlled-release pesticide or fertilizer) and, somewhat, in the packaging sector.     

Properties of Poly(Vinyl Alcohol)/Chitosan Nanocomposite Films Reinforced with Oil Palm Empty Fruit Bunch Amorphous Lignocellulose Nanofibers

The objective of this study was to investigate the properties of poly(vinyl alcohol)/chitosan nanocomposite films reinforced with different concentration of amorphous LCNFs. The properties analyzed were morphological, physical, chemical, thermal, biological, and mechanical characteristics. Oil palm empty fruit bunch LCNFs obtained from multi-mechanical stages were more dominated by amorphous region than crystalline part. Varied film thickness, swelling degree, and transparency of PVA/chitosan nanocomposite films reinforced with amorphous part were produced. Aggregated LCNFs, which reinforced PVA/chitosan polymer blends, resulted in irregular, rough, and uneven external surfaces as well as protrusions. Based on XRD analysis, there were two or three imperative peaks that indicated the presence of crystalline states. The increase in LCNFs concentration above 0.5% to PVA/chitosan polymer blends led to the decrease in crystallinity index of the films. A noticeable alteration of FTIR spectra, which included wavenumber and intensity, was obviously observed along with the inclusion of amorphous LCNFs. That indicated that a good miscibility between amorphous LCNFs and PVA/chitosan polymer blend generated chemical interaction of those polymers during physical blending. Reinforcement of PVA/chitosan polymer blends with amorphous LCNFs influenced the changes of T_g (glass transition temperature), T_m (melting point temperature), and T_max (maximum degradation temperature). Three thermal phases of PVA/chitosan/LCNFs nanocomposite films were also observed, including absorbed moisture evaporation, PVA and chitosan polymer backbone structural degradation and LCNFs pyrolysis, and by-products degradation of these polymers. The addition of LCNFs 0.5% had the highest tensile strength and the addition of LCNFs above 0.5% decreased the strength. The incorporation of OPEFB LCNFs did not show anti-microbial and anti-fungal properties of the films. The addition of amorphous LCNFs 0.5% into PVA/chitosan polymer blends resulted in regular and smooth external surfaces, enhanced tensile strength, increased crystallinity index, and enhanced thermal stability of the films.     

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.     

Biodegradable Films Based on Blends of Gelatin and Poly (Vinyl Alcohol): Effect of PVA Type or Concentration on Some Physical Properties of Films

The aim of this work was to develop biodegradable films based on blends of gelatin and poly (vinyl alcohol) (PVA), without a plasticizer. Firstly, the effect of five types of PVA with different degree of hydrolysis (DH) on the physical properties of films elaborated with blends containing 23.1% PVA was studied. One PVA type was then chosen for the study of the effect of the PVA concentration on the mechanical properties, color, opacity, gloss, and water solubility of the films. The five types of PVA studied allowed for films with different characteristics, but with no direct relationship with the DH of the PVA. Therefore, the PVA Celvol^®418 with a DH = 91.8% was chosen for the second part, because they produced films with greater tensile strength. The PVA concentration affected all studied properties of films. These results could be explained by the results of the DSC and FTIR analyses, which showed that some interactions between the gelatin and the PVA occurred depending on the PVA concentration, affecting the crystallinity of the films.     

Influence of Polyol Plasticizers on the Properties of Polyvinyl Alcohol Films Fabricated by Melt Processing

In this work, high-alcoholysis polyvinyl alcohol (PVA) films were fabricated by melt processing and the plasticizing effect of compound polyol plasticizers on PVA were investigated with X-ray diffraction (XRD), differential scanning calorimetry (DSC), rheological measurements, mechanical tests etc. Hydrogen bonding interactions occurred between PVA and plasticizer. With the increase of plasticizer, the flowability of PVA was improved and reached the maximum value at the plasticizer of 20%. Glass transition temperature (T _g) and melting point (T _m) decreased with the increase of plasticizer content. For the heterogeneous nucleation effect of plasticizer, new polymorph of PVA formed. The viscosity was sensitive to the shear rates. The incorporation of plasticizers into PVA resulted in the increase of elongation at break and impact strength, as well as the decrease of tensile strength.     

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.     

Influence of pH and C/N Ratio on Poly(Vinyl Alcohol) Biodegradation in Mixed Bacterial Culture

Cultivation conditions affecting poly(vinyl alcohol) (PVA) degradation by a mixed bacterial culture of Bacillus sp. and Curtobacterium sp. were investigated. Bacterial strains used in this study were isolated from the watercourse and the sewage sludge of vinylonfibre mill by enrichments on PVA as the sole carbon source. The results showed that PVA was greatly degraded under the following conditions: 0.5% PVA as a substrate at the initial medium pH of 8 with 0.15% glucose and urea at C/U ratio 1.5:1 and 1% bacterial inoculum, at a temperature of 35 °C and a shaking speed of 110 rpm. The analysis of FTIR and ¹H NMR spectra before and after biodegradation indicate fission of the PVA molecular chain during the incubation.     

Baked Foams Based on Cassava Starch Coated with Polyvinyl Alcohol with a Higher Degree of Hydrolysis

The aims of this work were to produce trays based on cassava starch, coated with polyvinyl alcohol (PVA) with a higher degree of hydrolysis (98%), and to study the effects of the coating on the mechanical and water sorption properties of the trays. Two types of PVA were tested: SELVOL? 325 (degree of polymerization?=?1000–1500) and SELVOL? 107 (degree of polymerization?=?350–650). A decrease in the water absorption capacity of 50% was observed when the coated samples were compared with the control sample after 30 min of immersion in water. It was observed in both coated samples a reduction of the initial rate of water adsorption sorption and a decrease in hydrophilicity compared with the control sample. Tensile strength and elongation were increased with application of the coatings. The use of the two types of PVA resulted in materials with similar mechanical and water sorption properties.     

Properties of Starch/PVA Blend Films Containing Citric Acid as Additive

Starch/polyvinyl alcohol (PVA) blend films were prepared successfully by using starch, polyvinyl alcohol (PVA), glycerol (GL) sorbitol (SO) and citric acid (CA) for the mixing process. The influence of mixing time, additional materials and drying temperature of films on the properties of the films was investigated. With increase in mixing time, the tensile strength (TS), elongation (%E), degree of swelling (DS) and solubility (S) of the film were equilibrated. The equilibrium for TS, %E, DS and S value was 20.12 MPa, 36.98%, 2.4 and 0.19, respectively. The mixing time of equilibrium was 50 min. TS, %E, DS and S of starch/PVA blend film were examined adding glycerol (GL), sorbitol (SO) and citric acid (CA) as additives. At all measurement results, except for DS, the film adding CA was better than GL or SO because hydrogen bonding at the presence of CA with hydroxyl group and carboxyl group increased the inter/intramolecular interaction between starch, PVA and additives. Citric acid improves the properties of starch/PVA blend film compared to glycerol and sobitol. When the film was dried at low temperature, the properties of the films were clearly improved because the hydrogen bonding was activated at low temperature.