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.     

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 Chemically Modified Starch (RS4)/PVA Blend Films: Part 2

Biodegradable films were successfully prepared by using cornstarch (CS), chemically modified starch (RS4), polyvinyl alcohol (PVA), glycerol (GL), and citric acid (CA). The physical properties and biodegradability of the films using CS, RS4, and additives were investigated. The results of the investigation revealed that the RS4-added film was better than the CS-added film in tensile strength (TS), elongation at break (%E), swelling behavior (SB) and solubility (S). Especially, the RS4/PVA blend film with CA as an additive showed physical properties superior to other films. Furthermore, when the film was dried at low temperature, the properties of the films clearly improved because the hydrogen bonding was activated at low temperature. The biodegradation of films was carried out using the enzymatic, microbiological and soil burial test. The enzyme used in this study was amyloglucosidase (AMG), α-amylase (α-AM) and β-amylase (β-AM). At the enzymatic degradation test, the GL-added films had an approximately 60% degradation, while the CA-added films were degraded about 25%. The low degradation value on CA-added film is attributed to low pH of film added CA that deactivated the enzymatic reaction. The microbiological degradation teat was performed by using Bacillus subtilis and Aspergillus niger.     

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.     

Physical Properties of Chemically Modified Starch(RS4)/PVA Blend Films—Part 1

In this paper, we report on the physical properties of films that have been synthesized by using native corn starch (NS) and chemically modified starch (RS4). NS or RS4/PVA blend films were synthesized by using the mixing process and the casting method. Glycerol (GL), sorbitol (SO), and citric acid (CA) were used as additives. The chemically modified starch (RS4) was synthesized by using sodium trimetaphosphate (STMP) and sodium tripolyphosphate (STPP) as a crosslinker. Then, the RS4 thus synthesized was confirmed by using the pancreatin-gravimetric method, swelling power and an X-ray diffractometer (XRD). Tensile strength (TS), elongation (%E), swelling behavior (SB), and solubility (S) of the films were measured. The result of the measurements indicated the RS4-added film was better than the NS-added film. Especially, the RS4/PVA blend film with CA as an additive showed the physical properties superior to other films.     

Preparation and Thermo-Mechanical Characterization of Chitosan Loaded Methylcellulose-Based Biodegradable Films: Effects of Gamma Radiation

Chitosan (0.1–1%, w/w), dissolved in 2% acetic acid solution, was added into 1% methylcellulose (MC)-based formulation containing 0.5% vegetable oil, 0.25% glycerol and 0.025% Tween^?80. Films were prepared by casting. Puncture strength (PS), puncture deformation (PD), viscoelasticity coefficient and water vapour permeability (WVP) of the films were measured. The PS value of 312 N/mm was observed for MC-based films containing 0.25% chitosan. Values of PD, viscoelasticity coefficient and WVP of these films were 5.0 mm, 44.1%, and 6.0 g mm/m² day kPa, respectively. The MC-based films containing 0.25% chitosan were also exposed to gamma radiation (0.5–50 kGy). The PS of the treated films decreased significantly from 312 at 0 kGy to 201 N/mm when treated at a dose of 50 kGy. However, WVP values were not affected by increasing irradiation the dose used. The Fourier Transform Infrared spectroscopy supported the molecular interactions due to addition of chitosan in MC-based films. Thermo gravimetric analysis and differential scanning calorimetric experiments showed that thermal properties of the films were significantly improved by chitosan loading. Surface topography of the films was studied by scanning electron microscopy and found rougher due to chitosan addition.     

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.     

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.     

Preparation and Characterization of Gamma Irradiated Sugar Containing Starch/Poly (Vinyl Alcohol)-Based Blend Films

Blends based on different ratios of starch (35–20%) and plasticizer (sugar; 0–15%) keeping the amount of poly(vinyl alcohol) (PVA) constant, were prepared in the form of thin films by casting solutions. The effects of gamma-irradiation on thermal, mechanical, and morphological properties were investigated. The studies of mechanical properties showed improved tensile strength (TS) (9.61 MPa) and elongation at break (EB) (409%) of the starch-PVA-sugar blend film containing 10% sugar. The mechanical testing of the irradiated film (irradiated at 200 Krad radiation dose) showed higher TS but lower EB than that of the non-radiated film. FTIR spectroscopy studies supported the molecular interactions among starch, PVA, and sugar in the blend films, that was improved by irradiation. Thermal properties of the film were also improved due to irradiation and confirmed by thermo-mechanical analysis (TMA), differential thermo-gravimetric analysis (DTG), differential thermal analysis (DTA), and thermo-gravimetric analysis (TGA). Surface of the films were examined by scanning electron microscope (SEM) image that supported the evidence of crosslinking obtained after gamma irradiation on the film. The water up-take and degradation test in soil of the film were also evaluated. In this study, sugar acted as a good plasticizing agent in starch/PVA blend films, which was significantly improved by gamma radiation and the prepared starch-PVA-sugar blend film could be used as biodegradable packaging materials.     

Physical Characterization of Biodegradable Films Based on Chitosan,Polyvinyl Alcohol and <Emphasis Type="Italic">Opuntia</Emphasis> Mucilage

This study aimed to develop and characterize biodegradable films containing mucilage, chitosan and polyvinyl alcohol (PVA) in different concentrations. The films were prepared by casting on glass plates using glycerol as plasticizer. Mechanical properties, water vapor and oxygen barrier, as well as the interaction with water, were measured. The compatibility of the film-forming components and the uniformity of the films were determined by zeta potential and SEM, respectively. The glycerol and mucilage allowed obtaining more hydrophilic films. The barrier properties of the films made from 100 % chitosan were similar to composed films containing PVA up to 40 %. The results of this study suggest that the interaction between chitosan and mucilage could increase water vapor permeability. The films prepared from either 100 % chitosan or PVA showed a more hydrophobic behavior as compared to the composed films. The films were homogenous since no boundary or separation of components was observed, indicating a good compatibility of the components in the films.     

Effect of the Incorporation of Lysozyme on the Properties of Jackfruit Starch Films

Jackfruit starch based biodegradable films containing lysozyme were characterized for their antimicrobial activity, thickness, solubility, water vapor permeability and mechanical properties. The biodegradable films had good appearance and antimicrobial activity against Micrococcus lysodeikticus. The thickness of the biodegradable films were not affected by the variation in pH, but the addition of lysozyme increased the thickness, the thickest films being those with the highest lysozyme concentrations. The variation in pH of the filmogenic solutions affected the solubility of the biodegradable films, water solubility being greatest at pH 7.0 and with the highest lysozyme concentration. The permeability of the biodegradable films was increased by incorporating lysozyme. The lysozyme concentration and pH variation caused changes in the mechanical properties. The addition of 8% lysozyme increased the tensile strength and Young’s modulus for all the pH values studied. With respect to the release of antimicrobial activity, the diffusion of lysozyme was shown to follow Fickian transport mechanism.     

Novel Biodegradable Cast Film from Cherry Tree Gum,Development, Modification and Characterization

The feasibility of sweet cherry gum as a bio-based film-forming material and effect of hydrogen peroxide as a chemical modifier investigated. The influence of film compositions (gum, glycerol) and hydrogen peroxide on the physical properties of films, including solubility in water, permeability to water vapor (WVP), mechanical properties, and transparency, thermal and microstructural properties evaluated. The results showed that WVP and thickness increased by gum and glycerol concentration, but significantly decreased by hydrogen peroxide. As expected, elongation-at-break and solubility, increased at higher concentration of glycerol but the tensile strength decreased at the same condition. The film transparency was influenced by the dry weight content and was improved by higher concentrations of hydrogen peroxide. The partial degradation of polymer chain by hydrogen peroxide was observed by FTIR analysis.     

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.     

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.     

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.     

Active Bio-composite Sodium Alginate/Maltodextrin Packaging Films for Food Containing Azolla pinnata Leaves Extract as Natural Antioxidant

The aim of the current work was to produce sodium alginate (SA) maltodextrins (MD) based functional films incorporated with phenolic extract of Azolla pinnata leaves fern (AF) by solution molding technique. AF with different concentrations (0.8, 1.2 and 1.6% w/w) were integrated inside SA.MD films. The resulted films were characterized to investigate the surface structure by scanning electron microscope (SEM), thermal disposal by (DSC), crystallization by X-ray diffraction (XRD), potential interaction by (FT-IR) and some mechanical properties. The SEM micrographs indicated that the higher concentration (1.6%) of AF extract caused development of wrinkles on the surface of films. And as a result, there were a significant decrease of elongation at break (EB) and tensile strength properties of films to 55.01 and 58.42%, respectively. By continues addition of AF extract to SA.MD films, the film thickness increased from 0.124 to 0.181 mm, the scavenging and antimicrobial properties were enhanced by the attendance of ferulic acid, rutin, thiamine, tamarixetin, astragalin, quercetin, chlorogenic acid and epicatechin inside extracts. Furthermore, the films solubility, swelling degree and water vapor permeability were decreased to 13.08%, 26.41% and 1.662?×?10^??10 g H₂O/m s p.a. The resulted films could be utilized as composite packaging material for different food applications.

     

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.     

Polyvinyl Alcohol (PVA)/Starch Bioactive Packaging Film Enriched with Antioxidants from Spent Coffee Ground and Citric Acid

The bioactive packaging polyvinyl alcohol (PVA)/starch films were prepared by incorporating combined antioxidant agents i.e. extracted spent coffee ground (ex-SCG) and citric acid. Effect of citric acid content on chemical compatibility, releasing of antioxidant, antibacterial activities, and physical and mechanical properties of PVA/starch incorporated ex-SCG (PSt-E) films was studied. The results of ATR-FTIR spectra showed that antioxidant agents of ex-SCG can penetrate into the film and the ester bond of blended films by citric acid was also observed. The presence of ex-SCG increased efficiency of antioxidant release and antimicrobial activity. The PSt-E film incorporated 30 wt% citric acid showed minimum inhibitory concentration against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). The incorporation of ex-SCG and citric acid into film showed a synergistic effect on antibacterial activity. The water resistance and kinetic moisture sorption improved with incorporation of citric acid. The tensile strength and biodegradability of samples were in range of 5.63–7.44 MPa and 65.28–86.64%, respectively. Based on this study, PSt-E film incorporated 30 wt% citric acid can be applied as novel food packaging materials.     

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。     

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.