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.     

Eco-Synthesis of PVA/Chitosan Hydrogels for Biomedical Application

A drug delivery system based on physically cross-linked poly vinyl alcohol (PVA)/chitosan blend hydrogels for the release of sparfloxacin antibiotic as a model for drugs was described. Eco-synthesis in current work is based on synthesizing a hydrogel without using chemical crosslinking agents like in the conventional method. In addition all materials are used are non- toxic, safe, non-carcinogenic and can be accepted by the human body without danger. The swelling behavior was tested to be dependent on pH as temperature as well as time and number of freezing thawing cycles. The physical properties of the hydrogels, such as swelling percent, dissolution percent, gel fraction and mechanical properties was assessed. The antimicrobial activity of hydrogels having different compositions was evaluated for both gram positive and gram negative bacteria. Furthermore, the release of antibiotic from hydrogels prepared using the freeze—thawed process was studied. Results obtained disclose that the swelling percent of the hydrogels is pH- dependent and increases by increasing the chitosan percent and decreases with increasing the time and number of freezing cycle. With respect to the antimicrobial activity of the prepared hydrogels, display a positive effect for both gram positive and gram negative bacteria. Freeze-thawed hydrogels could serve as drug delivery system to release sparfloxacin in acidic medium. Indeed, the release percent of sparfloxacin relies on both pH and temperature.     

Preparation and Properties of Chitosan–PVA Fibers Produced by Wet Spinning

Chitosan fibers were prepared by wet spinning in three stages. Initially, a polymer solution of chitosan and polyvinyl alcohol (PVA) was solidified in a mixture of potassium hydroxide and ethanol. The polymers were then crosslinked with sodium tripolyphosphate (TPP) or glutaraldehyde, and finally dried in methanol or acetone. The effect of these conditions was evaluated based on scanning electron microscopy images, water-holding capacity, and swelling and mechanical properties. The miscibility of the mixture was evaluated using Fourier Transform Infrared spectroscopy and differential scanning calorimetry. The results obtained showed that chitosan fibers containing 45% (v/v) PVA and crosslinked using TPP have properties similar to those of commercial sutures prepared using other biomaterials.     

Preparation and Characterization of Three Different Derivatized Potato Starches

The use of native starch as a thermoplastic polymer is limited by its fragility and high water absorption. Due to the presence of several hydroxyl groups in its structure, water acts as a natural plasticizer of starch, modifying its properties. It is necessary to chemically modify starch molecules by replacing hydroxyl groups with other functional groups to reduce water absorption. Chemical modification of starch granules also alters its swelling and gelatinization behavior. In this contribution we describe the chemical modification of starch and its influence on its hydrophilicity and heat resistance. Acetic acid, maleic anhydride and octanoyl chloride were used as derivatizing reagents. The effectiveness of the treatments was evaluated by means of infrared spectroscopy. Different tests were conducted in order to evaluate the influence of the different chemical modifications on starch structure and properties. Results showed that the treatments effectively reduced starch moisture susceptibility, while substantially altering other properties such as amylose content, swelling power, solubility, and heat resistance. Finally, films were prepared from native and derivatized starch and their surface polarity was evaluated.     

Fabrication and Characterization of Biodegradable Composite Films Made of Using Poly(caprolactone) Reinforced with Chitosan

Chitosan was dissolved in 2?% aqueous acetic acid solution and the films were prepared by solution casting. Values of tensile strength (TS), tensile modulus (TM), elongation at break (Eb?%) and water vapor permeability (WVP) of the chitosan films were found to be 30?MPa, 450?MPa, 8?% and 4.7?g?mm/m²?day?kPa, respectively. Poly(caprolactone) (PCL) films were prepared from its granules by compression molding and the values of TS, TM, Eb and WVP were 14?MPa, 220?MPa, 70?% and 1.54?g?mm/m²?day?kPa, respectively. PCL was reinforced with chitosan films, and composite films were prepared by compression molding. Amount of chitosan in the composite films varied from 10 to 50?% (w/w). It was found that with the incorporation of chitosan films in PCL, both the values of TS and TM of composite films increased significantly. The highest mechanical properties were found at 50?% (w/w) of chitosan content. The Oxygen transmission rate (OTR) of composite film was found to decrease significantly than PCL films. Thermal properties of the composite were also improved as compared to PCL. The water uptake test of the composite also showed promising results with a good stability of composite films. The interface of the composite was investigated by scanning electron microscopy and showed good interfacial adhesion between PCL and chitosan films.     

Chitosan/Hydrophilic Plasticizer-Based Films: Preparation,Physicochemical and Antimicrobial Properties

The addition of plasticizers to biopolymer films is a good method for improving their physicochemical properties. The aim of this study was to evaluate the effect of chitosan (CHI) blended with two hydrophilic plasticizers glycerol (GLY) and sorbitol (SOR), at two concentrations (20 and 40 wt%) on their mechanical, thermal, barrier, structural, morphological and antimicrobial properties. The chitosan was prepared through the alkaline deacetylation of chitin obtained from fermented lactic from shrimp heads. The obtained chitosan had a degree of deacetylation (DA) of 84 ± 2.7 and a molecular weight of 136 kDa, which indicated that a good film had formed. The films composed of CHI and GLY (20 wt%) exhibited the best mechanical properties compared to the neat chitosan film. The percentage of elongation at break increase to over 700 % in the films that contained 40 % GLY, and these films also exhibited the highest values for the water vapor transmission rate (WVTR) of 79.6 ± 1.9 g m² h^?1 and a yellow color (b _o  = 17.9 ± 2.0) compared to the neat chitosan films (b _o  = 8.8 ± 0.8). For the structural properties, the Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analyses revealed an interaction in the acetamide group and changes in the crystallinity of plasticized films. The scanning electron micrographs revealed that all formulations of the chitosan films were smooth, and that they did not contain aggregations, pores or microphase separation. The thermal analysis using differential scanning calorimetry (DSC) revealed a glass transition temperature (Tg) of 130 °C for neat chitosan film, but the addition of SOR or GLY elicited a decrease in the temperature of the peak (120 °C). In addition, the antimicrobial activity of the chitosan films was evaluated against Listeria monocytogenes, and reached a reduction of 2 log after 24 h. The plasticizer concentration of 20 % GLY is sufficient for obtaining flexible chitosan films with good mechanical properties, and it could serve as an alternative as a packaging material to reduce environmental problems associated with synthetic packaging films.     

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.     

An Overview on the Mechanical Behaviour of Biodegradable Agricultural Films

The mechanical behavior of various types of biodegradable materials depends, mainly, on their chemical composition and the application conditions. Various additives are added into the bioblends to improve their properties, which sometimes even reach the levels of the conventional plastics. It is well known that the environmental conditions during production, storage, and usage of these materials influence their mechanical properties. Ageing during the useful lifetime also causes great losses in the elongation. In the present paper, the overall mechanical behavior of biodegradable films, which may be considered suitable for agricultural applications, but also of partially biodegradable films, is reviewed and analyzed. Selected critical mechanical properties of films before their exposure to biodegradation are investigated and compared against those of conventional agricultural films.     

Structure and Property of Porous Polyvinylalcohol Hydrogels for Microorganism Immobilization

The porous polyvinylalcohol (PVA) hydrogel was prepared by chemical crosslinking in the saturated boric acid solution with sodium bicarbonate (SBC) as porogen. It was found that addition of SBC decreased the mechanical strength of the gel beads, while the gel permeability was improved. The equilibrium swelling rate and the swelling rate constant k of gel beads increased significantly by addition of SBC. Most of water in PVA hydrogel was in the form of free water and freezing bound water. With increasing SBC content, the total water content of the gel increased, in which the free water content increased remarkably, due to the formation of a large number of pores, and in the meantime, n values, characterizing the mole content of non-freezing bound water, were also improved greatly, indicating of the enhancement of the interaction between PVA molecules and water molecules. SEM observation showed that by adding SBC, many pores formed on the surface and inside gels, which provided channels for microbial metabolites. Microorganism could be successfully entrapped in the porous PVA beads, and addition of SBC made COD removal rate of the gel beads increase significantly.     

A Study of Physicomechanical and Morphological Properties of Starch/Poly(vinylalcohol) Based Films

Starch/Poly(vinylalcohol) blends in two different ratios (60:40 and 50:50) were prepared with glycerol as a plasticizer. Films were cast by a solution casting method. One set of films were filled with 10 wt% of unmodified bentonite clay and another set of films were crosslinked with epichlorohydrin in an alkaline medium. The prepared film samples were subjected to X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), mechanical characterization and scanning electron microscope (SEM). Significant changes in the tensile properties were observed depending on the different chemical constituents of the films. The presence of clay and crosslinking with epichlorohydrin were both found to have considerable effect on the morphology and mechanical property of the films. The SEM investigations, XRD analysis and FTIR studies revealed the interaction between the various chemical components 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.     

Potassium Release Kinetics and Water Retention of Controlled-Release Fertilizers Based on Chitosan Hydrogels

Controlled release fertilizer (CRF) hydrogels were prepared from poly(vinyl alcohol), poly(vinyl alcohol)/chitosan and chitosan using glutaraldehyde as a crosslinker. Intermolecular interactions of the CRF hydrogels were elucidated using FTIR. Water absorbency characteristics of the CRF hydrogels were also studied. It was found that the CRF hydrogels exhibited the equilibrium swelling ratio (SR) in the range 70–300%. The water retention of soil containing the CRF hydrogels was also examined. It was found that the CRF hydrogels increased the water retention of the soil. After 30 days, soil containing the PVA-, PVA/CS- and CS-hydrogels showed the water retention capacities of 25%, 10% and 4%, respectively. While the soil without the CRF hydrogel had already given off most of the water. The release behavior of potassium from the CRF hydrogels, both in deionized water and in soil, was investigated. In soil, the potassium release mechanism from the PVA- and PVA/CS-hydrogels were non-Fickian diffusion. On the other hand, the CS hydrogel showed, n value that was close to 1.0 corresponding to case II transport. In deionized water, all the CRF hydrogels showed small values of release exponent (n < 0.5) indicating a quasi-Fickian diffusion mechanism.     

Synthesis of Polymeric Matrices for Adsorption and Purification of Endoglucanase

Chitosan (CHS), chitosan–Eudragit® EPO (CHS–EPO) and chitosan beads partially cross-linked with glutaraldehyde (CHS–GLUT) were obtained in order to improve the adsorption selectivity of endoglucanase from a fungal culture obtained under SSF by Aspergillus niger using soybean harvest residues as support. The matrices synthetized were characterized in terms of physical and chemical changes. Fourier-transformed infrared spectroscopy with attenuated total reflectance device (FTIR-ATR) was employed to verify the chemical changes on the CHS matrix after the synthesis of CHS–GLUT and CHS–EPO. Scanning electron microscopy (SEM) was performed to compare the surface morphology of the polymeric beads. Two variables, purification factor and yield percentage of the adsorption process, were analyzed using a bifactorial ANOVA considering the matrix–time first order interaction. SEM results exhibited greater surface roughness in the CHS–GLUT and CHS–EPO matrices which may enhance endoglucanase adsorption. FTIR-ATR results confirmed an effective chemical modification of the CHS matrix after crosslinking with GLUT and corroborated the efficiency of the synthesis of the CHS–EPO matrix by the presence of chemical groups of the EPO polymer. An endoglucanase purification factor close to 9 was achieved with the CHS–GLUT matrix and a yield percentage of 60% was obtained with the CHS–EPO matrix. Bifactorial ANOVA results showed the matrix–time interaction to be significant for both variables. The CHS–GLUT matrix with low crosslinking times and the novel CHS–EPO matrix could be included in the bioseparation stage of endoglucanase using a simple and a low-cost method such as batch adsorption.     

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.     

Novative Biomaterials Based on Chitosan and Poly(ε-Caprolactone): Elaboration of Porous Structures

The swelling capability of chitosan was explored in order to use water both, as volatile plasticizer and as pore-forming agent. Chitosan powder was swelled in acidic aqueous solution and melt blended with poly(ε-caprolactone) (PCL). After stabilization at 57% RH and 25 °C, samples suffered a water mass loss of around 30 wt% without dimensions variation. Despite the low miscibility of these biopolymers, quite homogeneous dispersion of chitosan within the polyester matrix was obtained. Some interactions between both biopolymers could be observed. To obtain chitosan phase with a thermoplastic-like behaviour, the plasticization effect was also studied by the addition of 25 wt% glycerol as non volatile plasticizer. The equilibrium moisture content of samples increased with the incorporation of glycerol due to its hydrophilic nature. Morphology, thermal and mechanical properties of the blends were determined after stabilization. The preparation of rich PCL blends allowed the formation of macroporous structures since samples were not contracted after water loss and stabilization. These biomaterials with such a porous structure could be used for biomedical applications.     

Sisal/Carbon Fibre Reinforced Hybrid Composites: Tensile, Flexural and Chemical Resistance Properties

The variation of mechanical properties such as tensile and flexural properties of randomly oriented unsaturated polyester based sisal/carbon fibre reinforced hybrid composites with different fibre weight ratios have been studied. The chemical resistance test of these hybrid composites to various solvents, acids and alkalies were studied. The effect of NaOH treatment of sisal fibres on the tensile, flexural and chemical resistance properties of these sisal/carbon hybrid composites has also been studied. The hybrid composites showed an increase in tensile and flexural properties with increase in the carbon fibre loading. The tensile properties and flexural properties of these hybrid composites have been found to be higher than that of the matrix. Significant improvement in tensile properties and flexural properties of the sisal/carbon hybrid composites has been observed by alkali treatment. The chemical resistance test results showed that these untreated and alkali treated hybrid composites are résistance to all chemicals except carbon tetra chloride. Hand lay-up technique was used for making the composites and tests are carried out by using ASTM methods.     

Effects of Alkali Treatment on the Properties of Short Flax Fiber–Poly(Lactic Acid) Eco-Composites

In this study, the influence of alkali (NaOH) treatment on the mechanical, thermal and morphological properties of eco-composites of short flax fiber/poly(lactic acid) (PLA) was investigated. SEM analysis conducted on alkali treated flax fibers showed that the packed structure of the fibrils was deformed by the removal non-cellulosic materials. The fibrils were separated from each other and the surface roughness of the alkali treated flax fibers was improved. The mechanical tests indicated that the modulus of the untreated fiber/PLA composites was higher than that of PLA; on the other hand the modulus of alkali treated flax fiber/PLA was lower than PLA. Thermal properties of the PLA in the treated flax fiber composites were also affected. T_g values of treated flax fiber composites were lowered by nearly 10 °C for 10% NaOH treatment and 15 °C for 30% NaOH treatment. A bimodal melting behavior was observed for treated fiber composites different than both of neat PLA and untreated fiber composites. Furthermore, wide angle X-ray diffraction analysis showed that the crystalline structure of cellulose of flax fibers changed from cellulose-I structure to cellulose-II.     

Tensile,Flexural and Chemical Resistance Properties of Sisal Fibre Reinforced Polymer Composites: Effect of Fibre Surface Treatment

In this study, effect of fibre surface treatment on tensile, flexural and chemical resistance properties were studied for sisal fibre reinforced composites. Natural ligno cellulosic sisal fibre reinforced composites were prepared by different surface treatments by hand lay-up method. Fibre surface treatments were carried out to produce good interface between the fibre and the matrix to improve the mechanical properties. Fibre surface treatments were done by boiled the sisal fibres in different % of NaOH and treated the fibres in different % of NaOH, treated in acetic acid and methanol. Unsaturated polyester resin was used as the matrix for preparing the composites. For comparison, these properties for untreated sisal fibre reinforced composites were also studied. From the results it was observed that 18% aqueous NaOH boiled sisal fibre reinforced composites have higher tensile, flexural properties than other composites. Untreated sisal fibre composites show lower properties than treated composites. Chemical resistance properties indicate that all sisal fibre reinforced composites are resistance to all chemicals except carbon tetra chloride. The tests are carried out as per the ASTM standards.     

Biodegradable Blends with Potential Use in Packaging: A Comparison of PLA/Chitosan and PLA/Cellulose Acetate Films

Poly(lactic acid) (PLA) is a biodegradable polymer that exhibits high elastic modulus, high mechanical strength, and feasible processability. However, high cost and fragility hinder the application of PLA in food packaging. Therefore, this study aimed to develop flexible PLA/acetate and PLA/chitosan films with improved thermal and mechanical properties without the addition of a plasticizer and additive to yield extruder compositions with melt temperatures above those of acetate and chitosan. PLA blends with 10, 20, and 30 wt% of chitosan or cellulose acetate were processed in a twin-screw extruder, and grain pellets were then pressed to form films. PLA/acetate films showed an increase of 30 °C in initial degradation temperature and an increase of 3.9 % in elongation at break. On the other hand, PLA/chitosan films showed improvements in mechanical properties as an increase of 4.7 % in elongation at break. PLA/chitosan film which presented the greatest increase in elongation at break proved to be the best candidate for application in packaging.     

Development of Regenerated Cellulose/Citric Acid Films with Ionic Liquids

Nowadays, the importance of green and biodegradable plastics as viable substitutes for non-degradable petroleum-based materials is felt more than ever. Regenerated cellulose (RC) as a potential candidate suffers from poor processability and inferior properties, limiting its wide applications. In this study, it is demonstrated that citric acid (CA) enhances physical, mechanical, and thermal properties of RC films, due to RC-citric acid compatibility. 1-ethyl-3-methylimidazolium chloride (EMIMCl) as a green ionic liquid was employed for the processing of RC. The optimum properties in terms of thermal stability, mechanical strength, contact angle, water uptake, and oxygen permeability were achieved at 10 wt% of CA. However, further incorporation of CA adversely affected the film properties. This behaviour was explained by the crosslinking and plasticizing effects of CA. Furthermore, in vitro cytotoxicity test demonstrated that RC/CA films are cytocompatible, suggesting the potential advantage of using these biopolymeric films for biomaterial and biological applications.