Properties of the crosslinked plasticized biodegradable poly(vinyl alcohol)/rambutan skin waste flour blends

Poly(vinyl alcohol) (PVOH)/rambutan skin waste flour (RWF) crosslinked films were successfully prepared by solution casting with glutaraldehyde (GLU) and hexamethylenetetramine (HMTA) and without crosslinker in the presence of glycerol as a plasticizer. The properties of cast films were evaluated by tensile testing, water absorption, and degradation behavior at different weight ratios of PVOH and RWF. The tensile results show that the PVOH/RWF films crosslinked with HMTA exhibited a slight improvement in the tensile strength and Young's modulus but a lower elongation at break than that of GLU-crosslinked films; this was attributed to the better crosslinking effect of HMTA, as shown by the Fourier transform infrared results. The HMTA-crosslinked film showed a lower water absorption and water vapor transmission rate as compared to the GLU-crosslinked and noncrosslinked films. A natural weathering test revealed that the addition of 1.5 wt % GLU and HMTA did not significantly affect the reduction in tensile properties, but the biodegradability test showed that the weight loss of noncrosslinked films was higher than those of the GLU- and HMTA-crosslinked films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and Properties of Biodegradable Polymer Film Based on Polyvinyl Alcohol and Tropical Fruit Waste Flour

In this study, two different types of tropical fruit waste flour, rambutan waste flour (RWF) and banana waste flour (BWF), were blended with polyvinyl alcohol (PVOH) by solution casting method. The structure of the blend film was characterised by Fourier Transform Infrared Spectroscopy. The tensile strength and elongation at break of tropical fruit waste flour-filled polyvinyl alcohol were lower, but the tensile modulus was higher, than that of PVOH film. At a similar blend ratio, the tensile properties of the PVOH/RWF film were higher than the PVOH/BWF film, but the PVOH/BWF film showed higher water uptake than PVOH/RWF film.     

Crosslinked glutinous rice starch filled polyvinyl alcohol films

The influence of glutinous rice starch (GRS) content and sodium hexametaphosphate (SHMP) in polyvinyl alcohol (PVOH) films were studied. The increase of GRS content (0–40 wt%) reduced the tensile strength (from 14.3 to 4.3 MPa) and elongation at break (from 183 to 52.5) of PVOH/GRS films. Nevertheless, the modulus of elasticity of PVOH/GRS films increased with GRS content, from 20.3 to 132.83 MPa. SHMP was used as a crosslinking agent, which improved more than 30% of tensile strength and modulus of elasticity of PVOH/GRS films. However, the elongation at break reduced after crosslinking process of the films. The crosslinked film showed better interaction between GRS and PVOH, as demonstrated by scanning electron microscopy. Conversely, the crosslinked films exhibited a lower swelling degree, but a higher gel content compared to uncrosslinked films. J. VINYL ADDIT. TECHNOL., 25:359–365, 2019. © 2019 Society of Plastics Engineers     

Improvement of polyvinyl alcohol/casein blend film properties by adding cellulose nanocrystals

This study aims to prepare and examine the properties of poly(vinyl alcohol)/casein (PVA/CAS) based films reinforced with cellulose nanocrystals (NC), which can be presented as an alternative to petroleum-based polymer packaging materials. PVA/CAS and 0.5–1–3–5 wt% NC containing PVA/CAS biocomposite films were prepared by solution casting method. Afterward, the 1NC film, which exhibited the best mechanical properties, was crosslinked with various amounts of glyoxal. Structural, morphological (polarized optical microscope), mechanical (tensile), thermal (differential scanning calorimetry, thermogravimetric analysis), contact angle, and water vapor transmission rate (WVTR) properties of the samples were investigated. The 1NC film exhibited the highest tensile strength (TS) and elongation values in PVA/CAS/NC films, and its mechanical properties decreased due to agglomeration with increasing NC amount. As expected, crosslinking improved the TS. The thermal stability of the PVA/CAS film was generally improved with the addition of NC and crosslinking. The high WVTR value of the PVA/CAS film decreased with the addition of NC and the 1NC film presented the lowest value. Thanks to the complex structure formed as a result of crosslinking and the reduced free volume, the WVTR of the 1NC film has reduced. The results showed that PVA/CAS-based films with good mechanical properties and water vapor barrier are promising as packaging materials.     

Effect of Attapulgite Clay on Biodegradability and Tensile Properties of Polyvinyl Alcohol/Corn Starch Blend Film

Polyvinyl alcohol (PVOH) with corn starch (CS) at 70/30 weight percent ratio were prepared by a solution casting method with the addition of attapulgite at a range of 0.0–1.0 grams. The aim of this study is to investigate the effect of attapulgite on biodegradability and tensile properties of PVOH/CS matrix. All the results were compared with the control sample (PVOH/CS). The presence of attapulgite had hindered the degradation process in enzymatic, soil, and compost burial. The water sorption content increased with increasing immersion time. The highest tensile strength and elongation at break were shown by the PVOH/CS with 0.2 g of attapulgite content.     

Eco-friendly coupling agent-treated kenaf/linear low-density polyethylene/poly (vinyl alcohol) composites

Untreated kenaf (KNF) and eco-friendly coupling agent (EFCA)-treated kenaf were used as filler to prepare natural fiber-reinforced polymer composites (NFPCs) using linear low-density polyethylene (LLDPE) and poly(vinyl alcohol) (PVOH) as polymer matrices. The composites containing various loadings of untreated and EFCA-treated KNF (0, 10, 20, and 40 phr) were melt-blended in an internal mixer. The effect of treatment on the behavior of processing torque, mechanical properties, morphology, functional groups, water absorption, and thermal stability of KNF/LLDPE/PVOH composites were investigated. The results revealed that EFCA-treated KNF composites exhibited higher equilibrium torque, indicating that the viscosity of molten composites increased in the presence of EFCA. The tensile strength and tensile modulus of KNF/LLDPE/PVOH composites were improved with the addition of EFCA-treated KNF attributed to the enhancement of the interfacial adhesion between KNF and LLDPE/PVOH matrices, as confirmed by field-emission scanning electron microscopy. Fourier transform infrared spectroscopy indicated the presence of ester bond in EFCA-treated KNF composites. Furthermore, EFCA-treated KNF composites possessed a lower water absorption and greater thermal stability as compared to untreated KNF composites. Therefore, EFCA could be suggested as an effective coupling agent to enhance the performance of KNF/LLDPE/PVOH composites.     

FTIR-ATR studies of the sorption and diffusion of acetone:water mixtures in poly(vinyl alcohol)-clay nanocomposites

The simultaneous ingress of acetone and water into dried PVOH-clay nanocomposites containing 2.5 wt% or 5 wt% of well dispersed Na-Cloisite, using FTIR-ATR, has been compared with that into pure PVOH films. The rate at which water and acetone moved through the PVOH films is significantly reduced (i) at high acetone concentrations and (ii) when clay is incorporated in the PVOH film. For example, it takes 9 min and 17 min for water and acetone, respectively, to saturate a 25 ± 5 μm PVOH film containing 2.5 wt% of well dispersed clay when the acetone:water ratio is 90:10 v/v compared with ca. 1 min for a pure PVOH film when the acetone:water ratio is 70:30 v/v. The presence of significant quantities of water in the PVOH (nanocomposite) films was necessary before acetone began to permeate the film. The acetone entering the evanescent field was always highly hydrated even if the water content of the reservoir in contact with the film was low. There was no substantial evidence that the presence of clay altered the way in which the PVOH interacted with the acetone:water mixtures. The clay only acted to increase the tortuosity of the path through the film to the ATR prism.     

Physico-chemical properties of lignin–alginate based films in the presence of different plasticizers

A lignin–alginate blended film was prepared in the presence of three different plasticizers, viz. glycerol, epichlorohydrin (EPC) and poly(ethylene glycol) (PEG) and the effect of each plasticizer was studied on physico-chemical properties of the blended film. Lignin extracted from Acacia wood by alkali extraction process was blended with alginate to obtain lignin–alginate film in the presence of different plasticizers. A film plasticized with glycerol displayed higher solubility and swelling percentage as compared to EPC and PEG plasticized films. The highest tensile strength was observed for film plasticized with PEG, and none of the plasticizers made any significant change on the bursting strength of the film. Incorporation of lignin considerably improved the light barrier properties of the films. Fourier transform infrared spectroscopy study of films suggested the existence of hydrogen bonding between lignin–alginate in the presence of plasticizers. In addition, EPC plasticized film displayed highest thermal stability, as confirmed by thermogravimetric analysis. Further studies demonstrated that plasticizers significantly affected the physico-chemical properties of the blended films. In conclusion, lignin–alginate film plasticized with EPC presented better physico-mechanical and light barrier properties which could be used in packaging and coating applications.     

Improvement of Physicochemical Properties of Rubber Blends Between Nonirradiated and Irradiated Rubber Latexes by Radiation Vulcanization

Abstract

Nonirradiated natural rubber latex (NRL) and irradiated (12 kGy) rubber latex were blended in ratios of 100:0, 85:15, 65:35, 50:50, 35:65, 15:85, and 0:100 (v/v) to improve properties of the rubber latex. The blends were irradiated using different irradiation doses (0–20 kGy) in the presence of a radiation vulcanization accelerator (RVA), normal butyl acrylate (n-BA). The physicochemical properties of the nonirradiated latex, irradiated latex, and blend films were determined after leaching with distilled water. It was observed that the tensile strengths of the blend films increases with an increase in the content of the irradiated proportion and radiation doses. The composition of the blends and the doses of radiation were optimized. The maximum tensile strength (31.41 MPa) was found for the 50:50 composition of the blend with a 5 kGy radiation dose. The 100:0 blends, when irradiated, give the highest tensile strength (27.69 MPa) with 12 kGy but a 15:85 nonirradiated blend gives the tensile strength of 26.18 MPa.     

Cellulose/chitin films blended in NaOH/urea aqueous solution

Regenerated cellulose/chitin blend films (RCCH) were satisfactorily prepared in 6 wt % NaOH/4 wt % urea aqueous solution by coagulating with 5 wt % CaCl₂ aqueous solution then treating with 1 wt % HCl. The structure, miscibility, and mechanical properties of the RCCH films were investigated by infrared, scanning electron microscopy, ultraviolet spectroscopies, X‐ray diffraction, tensile test, and differential scanning analysis. The results indicated that the blends were miscible when the content of chitin was lower than 40 wt %. Moreover, the RCCH blend film achieved the maximum tensile strength in both dry and wet states of 89.1 and 43.7 MPa, respectively, indicating that the tensile strength and water resistivity of the RCCH film containing 10–20 wt % chitin was slightly higher than that of the RC film unblended with chitin. Structural analysis indicated that strong interaction occurred between cellulose and chitin molecules caused by intermolecular hydrogen bonding. Compared to the mechanical properties of chitin film, those of the blend films containing 10–50 wt % chitin were significantly improved. This work provided a novel way to obtain directly chitin material blended in the aqueous solution. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1679–1683, 2002     

Structure and mechanical properties of soy protein materials plasticized by Thiodiglycol

Thiodiglycol (TDG) is a relatively nontoxic compound from organic wastes. By using TDG as a plasticizer with weights from 2.5 to 40%, we prepared soy protein isolate (SPI) films by a compression‐molding technique at 140°C and 15 MPa. The TDG‐plasticized films (SPI–TDG films) were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, dynamic mechanical thermal analysis, thermogravimetric analysis, optical transmittance, and water uptake experiments. The SPI–TDG film plasticized with 25% TDG exhibited good mechanical properties, such as a tensile strength and modulus of 20.3 and 582 MPa, respectively, whereas the SPI–glycerol film with 25% glycerol had a tensile strength and modulus of 16.2 and 436 MPa, respectively. The results from the thermogravimetric analysis and water uptake experiments indicated that the thermal stability and water resistance of the TDG‐plasticized SPI materials were higher than that of the glycerol‐plasticized one. The improvements in the mechanical properties, water resistance, and thermal stability of the SPI–TDG films could be attributed to the strong intermolecular hydrogen bonding between soy protein and TDG and the presence of fewer hydroxyl groups in TDG, as compared structurally with glycerol. This study provided a new plasticizer for the preparation of soy protein materials. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Studies on the properties of poly(vinyl alcohol) film plasticized by urea/ethanolamine mixture

This study investigated the effects of urea/ethanolamine mixture (UE) on the crystallinity, thermal, and mechanical properties of poly(vinyl alcohol) (PVA) films. PVA films were prepared from solutions containing PVA, urea, ethanolamine, and water by casting and evaporating at 50°C for 12 h. The plasticization efficiency of UE was compared with that of glycerol (GL), the conventional plasticizer for PVA. The properties of PVA films plasticized by UE and GL, abbreviated to UE-plasticized PVA film and GL-plasticized PVA film, respectively, were investigated by Fourier-transform infrared spectroscopy, X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and mechanical testing. It was proved that UE could form more stable hydrogen bonding with the hydroxyl group of PVA molecule and was more effective in breaking the hydrogen bonds between the hydroxyl groups. Thus, the crystallinity of UE-plasticized PVA films was lower than that of GL-plasticized PVA films. The melting temperatures of UE-plasticized PVA films were lower than those of GL-plasticized PVA films. It was found that UE-plasticized PVA film showed a higher degradation temperature compared with GL-plasticized PVA film. The degree of swelling of UE-plasticized PVA film was higher than that of GL-plasticized PVA film but solubility (S) of UE-plasticized PVA film was lower in aqueous solution. Furthermore, UE-plasticized PVA films show lower tensile strength and higher elongation at break (E) than those of GL-plasticized PVA films. The tensile strength, E, and Young's modulus of PVA film containing 30% UE mixture reached 50.78 MPa, 591.19% and 76.9 MPa, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

豌豆淀粉/聚乳酸双层膜的制备与性能表征

采用溶液流延法以豌豆淀粉（PS）和聚乳酸（PLA）为原料制备了豌豆淀粉/聚乳酸（PS/PLA）双层薄膜。通过对双层薄膜的吸水性、溶解性、水蒸气透过性、拉伸性能、表面形貌等进行测试,研究了薄膜的力学性能、疏水性能以及水蒸气阻隔性能。结果表明：随着双层膜中聚乳酸层的比例增加,双层薄膜的吸水性、溶解性和水蒸气透过性逐渐降低,拉伸强度和拉伸模量逐渐增加,断裂伸长率逐渐下降,表明水蒸气阻隔效果明显,增加了膜的韧性,降低了膜的强度。当PLA和PS的质量比为50：50时,PS/PLA双层膜的拉伸强度为（13.47±0.75）MPa,拉伸模量为（0.848±0.002）GPa;断裂伸长率为（16.11±0.16）%,水蒸气透过系数为0.27×10^-10 g·cm/（cm²·s·Pa）。     

Comparison of mechanical and degradation properties of EG and EGDMA grafted gelatin films

Thin films of gelatin were prepared from gelatin granules in aqueous medium by casting and its mechanical properties like tensile strength (TS), tensile modulus (TM), and elongation at break (Eb %) were studied. Gelatin films were procured with two types of monomers such as 5% ethylene glycol (EG) and 5% ethylene glycol dimethacrylate (EGDMA) to increase the mechanical properties. Five percent of monomer solutions were prepared in MeOH along with 2% photoinitiator; Irgacure-651. Soaking time and UV radiation intensities were optimized with the extent of polymer loading (PL) and the mechanical properties of the cured films. Comparing the properties of EG and EGDMA treated gelatin film, EG showed the best performance. The EG-cured gelatin film with 5?min soaking time showed the highest tensile strength (58.6?MPa) and elongation at break (11.2%). The water uptake was determined for raw film (500.1%), EG grafted gelatin film (375.3%), and EGDMA grafted film (412.9%). The degradation properties in water and soil were determined for the raw and cured gelatin films. It was observed that the raw film degrades more than that of the treated films.     

Preparation of gelatin-based films modified with nanocrystalline cellulose

Gelatin is a natural biological macromolecule derived from the collagen in the connective tissue of the skin, bone and other tissues. It has been widely used in medicine, food and industrial production and other fields for easy molding, excellent compatibility and biodegradability. However, physical and chemical disadvantages impede its further application, seriously. Therefore, modification of the gelatin films becomes more and more important. In this study, the gelatin/nanocrystalline cellulose (NCC) composite films were prepared by casting method with 4% glycerol as plasticizer. The effect of NCC on the properties of the composite films was investigated by the characterization of its morphology and mechanical, thermal, and optical properties and water adsorption. The results showed that mechanical, thermal stability and water absorption properties of the gelatin/NCC composite film were obviously improved. The composite films showed the highest tensile strength (13.56?±?0.25 MPa) when the mass concentration of NCC was 0.6%. Adding NCC to gelatin benefited the thermal stability of composite films. The gelatin/NCC composite film of 0.4% NCC had the highest melting transition temperature (138.9 °C). The composite films exhibited the lower water absorption (271.1%) when mass concentration of NCC was 1.0%. Thus, these results indicated that NCC could affect the properties of gelatin-based composite films, and showed it has potential for application in food packing.     

Preparation and characterization of starch-based composite films reinforced by apricot and walnut shells

Starch-based biodegradable films were prepared by using solution-casting method and reinforced by agricultural residues [apricot and walnut shell (APS and WNS) powder]. The powder of both shells was added in different ratios (0, 2.5, 5, 7.5, and 10%) to investigate the microstructures and performances (mechanical and thermal properties) of the starch-based film. Different techniques such as impact, tensile testing, scanning electron microscope, optical microscope (OM), X-ray diffraction (XRD), water vapor transmission rate (WVTR), and dynamic mechanical analysis were applied to study the thermomechanical and barrier properties of the composite films. Results showed that the incorporation of both shells significantly improved the WVTR and mechanical properties of starch-based films. The shells powder was significantly increased the Young's modulus and tensile strength of the starch-based films. Both OM and SEM results showed reasonably good compatibility between starch and reinforced shells. OM and XRD indicated that the APS and WNS not only retained their crystalline structure in the film but they also strengthened the peak intensity of the film. This phenomenon can be used to explain the mechanism of mechanical reinforcement. Since all the components used in the preparation of the films are food grade ingredients, it is expected that the films developed in this work will be used for food packaging applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47978.     

Films of chitosan and N‐carboxymethylchitosan. Part II: effect of plasticizers on their physiochemical properties

Chitosan (Ch) and N‐carboxymethylchitosan (N‐CMCh) films were prepared by the casting method at concentrations of 1% and 2% of polymer, with or without plasticizer: polyethylene glycol (PEG‐400) and glycerol (G), at 15% (w/w). The influence of composition on mechanical properties, water vapour transmission rate (WVTR), water saturation, and aqueous dissolution of the films was analysed. The thermal stability of the mixture (polymer:plasticizer, 1:1) was evaluated by thermogravimetric analysis (TGA). In general, all the properties were affected by the plasticizers. The plasticized films showed lower strength and a higher percentage of elongation (%E), in the following order: G > PEG‐400 > unplasticized film. The total WVTR increased with Ch concentration, with a different WVTR profile for Ch and N‐CMCh. While the PEG‐400 addition did not significantly modify the WVTR profile of films, the glycerol enhanced the transport of water vapour through both polymers. The plasticizer addition increased the time of water film saturation, in the following order: G > PEG‐400 > unplasticized film; this was more pronounced in the N‐CMCh films, probably due to the formation of hydrogen bonds. The solubility of the films was also affected by their composition. Copyright © 2006 Society of Chemical Industry     

Blended films containing polybutyrolactam and chitosan for potential wound dressing applications

In this study, polybutyrolactam (PBA) was synthesized, and the PBA/chitosan (CS) blended films were fabricated for wound dressings. The results showed that the surface roughness of the blended films decreased with the increasing ratios of CS. In addition, the tensile strength of the film with 50 wt % CS (NC50) was about 33.6 MPa and the highest compared with other films. The hydrophilicity of the blended films gradually decreased while the water vapor transmission rates (WVTRs) increased with the increase of CS content. Moreover, the blended films could be biodegradable in phosphate buffer saline. Both PBA and blended films were non‐toxic and good for L929 cells growth, showing good cytocompatibility. Furthermore, the NC50 was found to promote the cell proliferation better than other groups. It can be suggested that the NC50 combined the advantages of both PBA and CS well. Therefore, the NC50 with good cytocompatibility, mechanical properties, and WVTRs might be suitable for wound dressing applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46511.     

Alginate dialdehyde (AD)-crosslinked casein films: synthesis,characterization and water absorption behavior

In this work, for the first time, alginate dialdehyde (AD) has been used as a cross linker to prepare casein films. The films, synthesized, have been characterized by Fourier transform infrared spectroscopy, X-ray diffraction analysis and scanning electron microscopy and thermogravimetric analysis. The films were investigated for their water absorption capacity in the physiological fluid of pH 7.4 at 37 °C. The film samples (AD-X-CAS)₁₂, (AD-X-CAS)₂₄ and (AD-X-CAS)₃₆ demonstrated an equilibrium water absorption of 30.86, 26.15 and 11.93 g/g, respectively. Moreover, the swelling exponents for the films were in the range of 0.66–0.75, thus indicating non-Fickian water transport mechanism. The dynamic water uptake data were analysed by various kinetic models. The water vapour transmission rates (WVTR) for the three film samples were found to be 16587, 15900 and 14316 g/m²/day, respectively. The higher values of WVTR, obtained for all the three samples, indicated their suitability for high exudating wounds. The results of expansion study in 4% gelatin medium revealed that the three samples exhibited an almost 2.54, 2.09 and 1.90-fold increase in their diameter in 90, 75 and 60 min, respectively.     

Bio-based sustainable films from the Algerian Opuntia ficus-indica cladodes powder: Effect of plasticizer content

The present study investigated the fabrication and characterization of bio-based sustainable films composed of a terrestrial plant raw material, namely Opuntia ficus-indica (OFI) cladodes powder (CP) and a marine seaweed derivative, namely agar (A). The effect of glycerol concentration on the properties of the casted films was evaluated at four different contents, namely 30, 40, 50 and 60 wt%. The films present UV-blocking properties, as well as moderate mechanical performance, thermal stability, and water vapor transmission rate (WVTR). The results point to an increase in thickness, elongation at break, moisture content, water solubility, and WVTR with increasing glycerol content. On the contrary, Young's modulus, tensile strength, and water contact angle decreased as glycerol concentration increased. The best combination is obtained for the film with 30% glycerol, based on an intermediate compromise between physical, mechanical, thermal, and barrier properties. All these outcomes express the potentiality of the powder obtained from grinding the OFI cladodes as raw material to produce low-cost films for the development of sustainable packaging materials.