Preparation and Properties of Poly（vinyl alcohol）/Chitosan Blend Bio-nanocomposites Reinforced by Cellulose Nanocrystals

The aim of this paper is to report the effect of the addition of cellulose nanocrystals（CNCs） on the mechanical, thermal and barrier properties of poly（vinyl alcohol）/chitosan（PVA/Cs） bio-nanocomposites films prepared through the solvent casting process. The characterizations of PVA/Cs/CNCs films were carried out in terms of X-ray diffraction（XRD）, transmission electron microscopy（TEM）, scanning electron microscopy（SEM）, thermogravimetric analysis（TGA and DTG）, oxygen transmission rate（OTR）, and tensile tests. TEM and SEM results showed that at low loading levels, CNCs were dispersed homogenously in the PVA/Cs matrix. The tensile strength and modulus in films increased from 55.1 MPa to 98.4 MPa and from 395 MPa to 690 MPa respectively, when CNCs content went from 0 wt% to 1.0 wt%. The thermal stability and oxygen barrier properties of PVA/Cs matrix were best enhanced at 1.0 wt% of CNCs loading. The enhanced properties attained by incorporating CNCs can be beneficial in various applications.     

Preparation and characterization of corn starch/soy protein biocomposite film reinforced with graphene and graphene oxide nanoplatelets

Corn starch (CS) and soy protein isolate (SPI), as inexpensive, abundant, and biodegradable materials, can chemically interact well with each other to produce biofilms. However, to overcome some of their physical and mechanical limitations, it is preferred to use their composite form, employing reinforcing materials. In this study, initially, graphene (G) and graphene oxide (GO) were synthesized by a green method. Then, to enhance the polymer blend final properties, the effects of adding G and GO in the range of 0.5 to 2 wt% on physical and mechanical properties of starch/protein blend were investigated. The results showed that the presence of 0.5‐wt% G and 2‐wt% GO significantly increased the modulus of starch/protein film from 252 to 578 and 449 MPa, respectively. In addition, the thermal stability of CS/SPI/GO (2 wt%) composite film was 50°C to 60°C more than that of the pure starch/protein film. On the other hand, G‐reinforced composite films tended to decline water diffusion compared with the pure polymer film. In addition, the composite film with 2‐wt% GO content had the lowest oxygen permeation rate (3.48 cm³ μm/m²d kpa) among the other composite films.     

聚乙烯醇/单宁共混膜的制备及其抗菌性能

采用溶液共混浇膜法制备了不同单宁含量的聚乙烯醇/单宁共混膜材料,利用扫描电镜(SEM)、广角X-射线衍射(WAXD)及示差扫描量热分析(DSC)对共混膜的结构进行了表征.结果表明,单宁和聚乙烯醇具有良好的相容性,聚乙烯醇的结晶能力及熔点均随单宁的加入量增大而稍降低.少量戊二醛的轻度交联作用使单宁在共混膜中非常稳定,在水中浸泡24 h后也仅有不到1.8%的单宁(相对膜中单宁总质量)渗出.接触法抗菌试验表明,所制备的共混膜对大肠杆菌(E.coli,CMCC 44103)、金黄色葡萄球菌(S.aureus,ATCC6538)和表皮葡萄球菌(S.epidermidis,ATCC 12228)都具有良好的抗菌能力,且随着单宁含量的升高而增强.     

Effect of pullulan/poly(vinyl alcohol) blend system on the montmorillonite structure with property characterization of electrospun pullulan/poly(vinyl alcohol)/montmorillonite nanofibers

Nanofibers of the composite of pullulan (PULL), poly(vinyl alcohol) (PVA), and montmorillonite clay (MMT) were prepared using electrospinning method in aqueous solutions. Pullulan is an interesting natural polymer for many of its merits and good properties. Because of biocompatibility and non-toxicity of PVA, it could be used in numerous fields. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR), X-ray diffraction (XRD), and thermal gravimetric analysis (TGA) were done to characterize the PULL/PVA/MMT nanofibers morphology and properties. XRD patterns and FTIR data demonstrated that there were good interactions between PULL and PVA caused by possibly hydrogen bonds. Moreover, XRD data and TEM images indicated that intercalated and exfoliated MMT nanoplatelets can be obtained within the PULL/PVA/MMT nanofibers depending on the PULL/PVA blend ratios. Furthermore, the thermal stability and mechanical property (tensile strength) of PULL/PVA/MMT nanofibers could be enhanced more by exfoliated MMT nanoplatelets than intercalated structures of that nanoplatelets.     

LDPE/EVA/graphene nanocomposites with enhanced mechanical and gas permeability properties

In the present work, graphene oxide (GO) and reduced graphene oxide (RGO) were incorporated at low‐density polyethylene (LDPE)/ethylene vinyl acetate (EVA) copolymer blend using solution casting method. Monolayer GO with 1‐nm thickness and good transparency was synthesized using the well‐known Hummers's method. Fourier transform infrared and X‐ray photoelectron spectroscopy data exhibited efficient reduction of GO with almost high C/O ratio of RGO. Scanning electron microscopy showed the well distribution of GO and RGO within LDPE/EVA polymer matrix. The integrating effects of GO and RGO on mechanical and gas permeability of prepared films were examined. Young's modulus of nanocomposites are improved 65% and 92% by adding 7 wt% of GO and RGO, respectively. The tensile measurements showed that maximum tensile strength emerged in 3 wt% of loading for RGO and 5 wt% for GO. The measured oxygen and carbon dioxide permeability represented noticeably the attenuation of gas permeability in composite films compared with pristine LDPE/EVA blend. Copyright © 2015 John Wiley & Sons, Ltd.     

Structure and compatibility of poly(vinyl alcohol)-silk fibroin (PVA/SA) blend films

The structure and compatibility of poly(vinyl alcohol)-silk fibroin (PVA/SF) blend films were analyzed by differential scanning calorimetry (DSC), thermomechanical (TMA) and thermogravimetric (TGA) analysis, x-ray diffractometry, and scanning (SEM) and transmission (TEM) electron microscopy. DSC curves of PVA/SF blend films showed a major endothermic peak at 220°C, along with a peak at 280°C. These endotherms were assigned to the thermal decomposition of the ordered PVA elements and to the thermal degradation of silk fibroin, respectively. The PVA/SF blends behaved in a manner intermediate to the pure components, as suggested by both contraction expansion and sample weight retention properties recorded by TMA and TGA measurements. The IR absorption spectra of the blends were identified as purely a composite of the absorption bands characteristic of both PVA and SF pure polymers. The X-ray diffraction patterns of PVA/SF blends showed overlapping spacing due to PVA and SF. A dispersed phase formed by spherical particles of 3–7 μm diameter was observed by SEM and TEM. All these findings suggest that PVA and SF are incompatible. © 1994 John Wiley & Sons, Inc.     

Preparation and characterization of polyvinyl alcohol/β‐cyclodextrin/GO‐Ag nanocomposite with improved antibacterial and strength properties

In this work, new hydrogel films based on polyvinyl alcohol (PVA) and β‐cyclodextrin (β‐CD) were prepared with the aim of studying their ability as an antibacterial and drug carrier system. Gallic acid (GA) was used as an antibacterial drug which was encapsulated into the β‐CD cavity, and finally, β‐CD inclusion complex (GA/βCD‐IC) was prepared. On the other hand, silver nanoparticles (AgNPs) were synthesized on the graphene oxide (GO) surface (GO‐Ag), and the obtained GO‐Ag was used to enhance the antibacterial properties and mechanical strength of their films. FT‐IR and DSC analysis approved the formation of cross‐linking with glutaraldehyde between the PVA and β‐CD. Hydrogel films were characterized using XRD and SEM. The disc diffusion method showed the antibacterial activity for the films containing GO‐Ag and GA. Due to the good strength, elasticity, WVP, and swelling ability, PVA/GA/βCD‐IC/GO‐Ag can be proposed as a potential antibacterial drug delivery system.     

Spectroscopic and Discharge Studies on Graphene Oxide Doped PVA/PVP Blend Nanocomposite Polymer Films

Graphene oxide (GO) nanoparticles were synthesized by modified Hummers method. The synthesized GO nanoparticles were incorporated in polyvinyl alcohol/polyvinyl pyrrolidone (PVA/PVP) blend polymers for the preparation of nanocomposite polymer films by solution cast technique. Different characterizations such as XRD, UV–Vis and FTIR were carried-out on to the prepared nanocomposite polymer films. The thermal analysis of the films was studied by DSC. The morphology of PVA/PVP:GO polymer films confirms GO was exfoliated within the PVA/PVP matrix and also reveals the heterogeneous phase of nanocomposite polymer electrolyte systems. From the conductivity studies the highest conductivity of PVA/PVP: GO (0.45: 0.3) was found to be 8.05 × 10^–4 S/cm at room temperature. Solid state battery has been fabricated with the configuration of Mg⁺/(PVA/PVP:GO)/(I₂ + C + electrolyte) and its cell parameters were calculated for a constant load of 100 kΩ.     

CHARACTERIZATION OF POLY(VINYL ALCOHOL)-KONJAC GLUCOMANNAN BLEND FILMS

This article deals with the characterization of blend films obtained by mixing poly(vinyl alcohol) (PVA) and konjac glucomannan (KGM) in aqueous solution. The DTA curves of PVA/KGM blend films showed overlapping of the main thermal transitions characteristic of the individual polymers. The exothermic peak at 312°C, which resulted from the thermal degradation of the KGM, shifted slightly to a higher temperature at low PVA content (≤20 wt%). The weight-retention properties of the blend films indicated that thermal stability of the blend films were better than pure KGM film at PVA content below 20 wt%. The crystallinities, tensile strength, and elongation at break of the films increased with the PVA content, and reached the maximum values at 20 wt% PVA, then decreased. Changes in the carbonyl stretching band of KGM and hydroxyl stretching regions of KGM and PVA were detected by FTIR analysis. Those are attributable to the existence of a certain degree of inteaction between KGM and PVA, and resulted from intermolecular hydrogen bonds. Phase separation phenomena were observed by examining the surface of the blend films by SEM.     

Effects of Electron Beam Irradiation on the Structural Properties of PVA/PAM/CMC Ternary Polymer Blends

Ternary miscible blends based on various ratios of poly(vinyl alcohol) (PVA), poly(acrylamide) (PAM) and carboxymethyl cellulose (CMC) were prepared by solution casting in the form of thin films. The structure‐property behavior of the ternary PVA/PAM/CMC blends, before and after they had been exposed to various doses of electron beam irradiation, was investigated by FT‐IR spectroscopy, SEM, XRD and stress‐strain curves. The visual observation showed that the cast films of the individual polymers PVA, PAM, and CMC and their blends over a wide range of composition are clear and transparent indicating the miscibility of PVA/PAM/CMC ternary blends. The FT‐IR analysis of pure polymers or their ternary blends before or after electron beam irradiation proved the formation of hydrogen bonding. In addition, it was found that the intensity of the different absorption bands depends on the ratio of PAM and CMC in the ternary blend. The XRD patterns showed that the peak position for the ternary blends decreases with increasing the ratio of CMC in the blend. However, the peak position for the ternary blend based on equal ratios of pure polymers was not affected by blending and was found in the same position as in the XRD pattern of pure PVA. The SEM micrographs give support to the visual observation indicating the complete miscibility of PVA/PAM/CMC ternary blends. The improvement in morphology leads to improvement in the tensile mechanical properties of the ternary polymer blends.     

Nanocrystalline cellulose acetate (NCCA)/graphene oxide (GO) nanocomposites with enhanced mechanical properties and barrier against water vapor

Highly flexible nanocomposite films of nanocrystalline cellulose acetate (NCCA) and graphene oxide (GO) were synthesized by combining NCCA and GO sheets in a well-controlled manner. By adjusting the GO content, various NCCA/GO nanocomposites with 0.3–1 wt% GO were obtained. Films of these nanocomposites were prepared using the solvent casting method. Microscopic and X-ray diffraction (XRD) measurements demonstrated that the GO nanosheets were uniformly dispersed in the NCCA matrix. Mechanical properties of the composite films were also studied. The best GO composition of the samples tested was 0.8 wt%, giving tensile strength of 157.49 MPa, which represents a 61.92 % enhancement compared with NCCA. On the other hand, the composite films showed improved barrier properties against water vapor. This simple process for preparation of NCCA/GO films is attractive for potential development of high-performance films for electrical and electrochemical applications.     

纤维素/甲壳素共混膜的结构表征与抗凝血性能

以 6wt %NaOH 4wt%尿素为纤维素的新溶剂 ,采用溶液共混法制备出纤维素 甲壳素共混膜 ,为甲壳素在碱性溶液中制膜提供了新的方法 .红外光谱、X 射线衍射、扫描电镜和力学性能、抗凝血性能测试结果表明 ,共混膜中甲壳素含量低于 4 0wt%时 ,纤维素与甲壳素分子间具有良好的相容性 ;在纤维素中引入适量甲壳素可提高共混膜的抗张强度 ,共混膜的干、湿态抗张强度在甲壳素含量 10wt%时最大 ,其值分别为 89 1MPa和 4 3 7MPa ,比纯态纤维素膜的干、湿态抗张强度分别提高了 6 7%和 11 5 % ;甲壳素的引入可明显降低血小板在共混膜表面的粘附、凝聚与变性 ,增大共混膜的抗凝血参数 ,甲壳素含量达到 5 0wt%时 ,该共混膜具有良好的抗凝血性能     

Synthesis,characterization and optical properties of graphene oxide–polystyrene nanocomposites

The synthesis of graphene oxide (GO)–polystyrene (PS) Pickering emulsions, as environment‐friendly nanostructures suitable for novel applications, has received significant attention in recent years. In this work, the synthesis and characterization of GO–PS nanocomposites through seeded emulsion polymerization and the selective light reflection properties of dry films have been reported. Amphiphilic molecule sulfonated 3‐pentadecyl phenol was used as a co‐surfactant to stabilize GO dispersions during the emulsion polymerization process. The particle size of the dispersions as measured by dynamic light scattering decreases from 540 nm, for PS without any GO, to 88 nm with 1 wt% GO content. Scanning electron microscopy studies show a uniform size distribution of the composite particles prepared with GO. The dried films show a structural color that varies with the GO content. The self‐assembly behavior of the dried film was further studied using reflectance spectroscopy, which shows a red shift of the reflectance maximum from 440 to 538 nm as the GO loading was increased from 0.2 to 0.5 wt%, respectively, indicating a different microstructure. X‐ray diffraction, transmission electron microscopy (TEM) and atomic force microscopy (AFM) were used to study the morphology and structure of the composite particles on drying. The AFM study confirms the non‐spherical shape of the particles. Thermogravimetric analysis shows improved thermal decomposition characteristics of the nanocomposite films. Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation and Characterization of Poly Vinyl Alcohol/Poly Vinyl Pyrrolidone/Clay Based Nanocomposite by Gamma Irradiation

A series of PVA/PVP/clay nanocomposite were prepared by gamma irradiation with different clay contents of (0.15, 0.3, 1, 1.5, 3 and 5 wt%). The gelation content and swelling behavior were investigated. The morphology and structure of PVA/PVP/clay nanocomposite and dispersion of the clay nanoparticles in the polymeric matrix were examined by infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The introduction of clay into polymeric matrix was investigated by X-ray diffraction pattern (XRD) and Transmission electron microscope (TEM). It is observed that, the increase of the clay content causes a decrease in the swelling percent. The thermal stability studies confirmed that the introduction of clay lead to an increase in the thermal stability. The TEM results showed that the clay nanoparticles are interchelated or exfoliated in the polymeric matrix. Some desirable characteristics such as relatively good swelling and excellent barrier capability against microbe penetration suggested that PVA/PVP/clay nanocomposite can be a good candidate as a wound dressing.     

Thermal and photochemical stability of poly(vinyl alcohol)/modified lignin blends

A kraft lignin derivative (KLD) obtained by reaction with p-aminobenzoic acid/phthalic anhydride was blended with poly(vinyl alcohol) (PVA) by solution casting from DMSO. PVA and PVA/KLD films were exposed to ultraviolet radiation (24, 48, and 96 h) and analyzed by thermogravimetry (TG), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), hydrogen nuclear magnetic resonance (¹H NMR) spectroscopy, and scanning electron microscopy (SEM). PVA films show a loss of thermal stability due to irradiation. PVA/KLD reveals greater thermal stability than PVA and an increase in thermal stability after irradiation. These results suggest that the incorporation of KLD into PVA provides a gain in thermal and photochemical stability. FTIR, ¹H NMR, DSC, and TG results obtained for the blends suggest that intermolecular interactions between PVA and KLD chains are present. SEM micrographs revealed blend miscibility for a KLD blend content of up to 15 wt%, as observed at magnification of 1000 times.     

Hybrid polypyrrole/copper/graphene oxide nanocomposite films synthesized via potentiostatic deposition with enhanced photovoltaic properties

Novel ternary nanocomposites films of Polypyrrole/copper/graphene oxide (PPy/Cu/GO) showed enhanced optical and electronic properties. In this study, PPy/Cu/GO films were synthesized with different GO load (0.0, 0.4, 0.6, and 0.8 wt%) using electrochemical deposition technique. The structural, optical and electrical properties of the composites were evaluated using X-Ray Diffraction (XRD) spectroscopy, UV–visible spectroscopy, Scanning electron microscopy (SEM), Energy dispersive X-ray spectroscopy (EDX), and four-point probe methods. XRD results reveal that the GO was completely intercalated and dispersed uniformly in the nanocomposites. The results also revealed that the nanocomposite films are crystalline in nature, with distinct peaks corresponding to indexed miller indices. UV-visible analysis revealed that all of the nanocomposites showed good UV absorbance which was significant in the UV–Vis region of ≈450 nm. The energy band gap decreased with increase in GO load and was found within 3.46 to 2.25 eV, across the range of GO load which fall within the range of energy band gap for photovoltaic applications. The SEM results revealed that the nanocomposite films showed unevenly shaped structures with porous surface which increases with increasing GO loading, while the EDX result revealed the presence of carbon, oxygen nitrogen and copper as fundamental elements deposited. The nanocomposites' four-point probe analysis revealed slight increase in conductivity with low GO content. The incorporation of Cu and GO nanoparticles in PPy matrix provides a better balance and thus improved the photovoltaic properties of PPy/Cu/GO making them suitable for photovoltaic applications.     

氧化石墨烯/聚吡咯插层复合材料的制备和电化学电容性能

以FeCl₃-甲基橙(MO)为模板, 通过化学原位聚合法成功制备出氧化石墨烯/聚吡咯(GO/PPy)插层复合材料. 采用X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱、扫描电镜(SEM)和透射电镜(TEM)等测试技术对复合材料进行物性表征. 此外, 利用循环伏安、恒电流充放电和交流阻抗测试方法对复合材料在两种不同水系电解液(1 mol·L^-1 Na₂SO₄和1 mol·L^-1 H₂SO₄)中的电化学性能进行了研究. 结果显示: 氧化石墨烯和聚吡咯表现出各自优势并发挥协同作用, 使得GO/PPy插层复合材料在中性和酸性电解液中都显示出可观的比电容. 电流密度为0.5 A·g^-1时, GO/PPy 插层复合材料在Na₂SO₄和H₂SO₄电解液中的比电容分别为449.1 和619.0 F·g^-1, 明显高于纯PPy的比电容. 经过800 次循环稳定性测试后, 两种不同电解液中, 复合材料初始容量的保持率分别为92%和62%. 其中酸性电解液体系中初始容量更大, 而中性溶液中具有更稳定的循环性能.     

Cornstarch/Poly(vinyl alcohol) Biocomposite Blend Films: Mechanical Properties,Thermal Behavior,Fire Retardancy,and Antibacterial Activity

In the present study, biocomposite films of starch/poly(vinyl alcohol) (St/PVA) reinforced with delignified Grewia optiva fiber and methyl methacrylate (MMA) grafted fibers were prepared using citric acid as a plasticizer and glutaraldehyde as the cross-linker. The biocomposite films were subjected to evaluation of mechanical properties, biodegradability, and antibacterial properties. The biocomposite films were characterized by using Fourier transform-infrared (FT-IR) spectrophotometry, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA/DTA/DTG). SEM showed good adhesion between St/PVA blend matrix and fibers. The antimicrobial activity of biocomposite films against pathogenic bacteria such as Staphylococcus aureus and Escherichia coli was also explored. The results confirmed that the biocomposite films may be used for food packaging.     

Preparation and properties of poly(vinyl alcohol)/exfoliated α-zirconium phosphate nanocomposite films

In this work, poly(vinylalcohol)(PVA)/exfoliated α-zirconium phosphate(e-α-ZrP) nanocomposites of various compositions were created by a solution casting method. The α-ZrP compound was synthesized by refluxing. The characteristic properties of the PVA/e-α-ZrP composite films were examined by thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM) and tensile tests. Tensile tests indicated that with the loading of e-α-ZrP, the tensile strength and the elongation at break were increased by 17.3% and 26.6% compared to neat PVA, respectively. It is noteworthy that optimum film properties were obtained with 0.8 wt% e-α-ZrP, and higher proportions of e-α-ZrP, may be related to the aggregation of e-α-ZrP particles and deterioration of the film properties. On the whole, the nanocomposite PVA/e-α-ZrP systems had mechanical and thermal properties which were superior to that of the neat polymer and its conventionally filled composites.     

壳聚糖/聚乙烯醇共混超细纤维的制备及紫外光交联研究

用静电纺丝法制备壳聚糖/聚乙烯醇的共混超细纤维,采用扫描电镜考察了纺丝液浓度、共混物配比、喷丝口内径对纤维形貌的影响.此外,为减少壳聚糖/聚乙烯醇纤维膜的溶胀变形,在上述体系中加入可光交联的单体二缩三乙二醇双甲基丙烯酸酯(TEGDMA)、引发剂2-羟基-2-甲基-1苯基丙酮(1173),对电纺纤维进行紫外光交联.结果表明,当壳聚糖与聚乙烯醇质量比为8:2的共混体系中加入占混合溶液质量分数4%的TEGDMA、0.12%的1173作为交联剂时,所得的无纺布纤维直径比较均一,平均约为200 nm,经光交联处理后其耐水性能得到提高.