Preparation and Characterization of Blend Films of Poly(Vinyl Alcohol) and Sodium Alginate

Blend films of poly(vinyl alcohol) (PVA) and sodium alginate (NaAlg) were prepared by casting from aqueous solutions. This blend films were characterized by tensile strength test, Fourier transform infrared spectroscopy (FT‐IR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The miscibility in the blends of PVA and NaAlg was established on the basis of the thermal analysis results. DSC showed that the blends possessed single, composition‐dependent glass transition temperatures (T_gs), indicating that the blends are miscible. FT‐IR studies indicate that there is the intermolecular hydrogen bonding interactions, i.e. –OH…^?OOC– in PVA/NaAlg blends. The blend films also exhibited the higher thermal stability and their mechanical properties improved compared to those of homopolymers.     

Fabrication and characterization of poly(vinyl alcohol)/chitosan hydrogel thin films via UV irradiation

A series of poly(vinyl alcohol)/chitosan (PVA/CTS) hydrogel thin films were prepared via ultraviolet (UV) irradiation, with acrylic acid (AA) monomer added as a crosslinker without the addition of any other photo-initiator. The swelling behaviors, intermolecular chemical bonds, molecular structures, thermal behaviors, degrees of crystallinity, morphologies of the surfaces and internal structure, and their relationship to the AA content were characterized using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Poly(acrylic acid) (PAA) and its chemical crosslinks formed in hydrogel films via free-radical reactions were confirmed using FTIR and DSC analyses. The XRD patterns indicated that the degree of crystallinity of the hydrogel films decreased as the PAA content was increased. SEM micrographs showed that a uniform interconnected pore structure was formed through the entire hydrogel structure, and a gradient in the crosslinking density through the film thickness was observed to result from extended irradiation times. The swelling behaviors revealed that the formation of PAA and its crosslinking in the hydrogel thin films improved the pH stability and controlled the degree of swelling while retaining a high swelling rate. The successful formation of chemical crosslinking without any specific photo-initiator improves the natural characteristics of CTS and PVA and imparts the resulting PVA/CTS hydrogel thin films with properties that make them very promising in biomedical applications.     

Preparation and properties of calcium silicate hydrate-poly(vinyl alcohol) nanocomposite materials

Summary A series of calcium silicate hydrate (C-S-H)-polymer nanocomposite (C-S-HPN) materials were prepared by incorporating poly(vinyl alcohol) (PVA) into the inorganic layers of C-S-H during precipitation of quasicrystalline C-S-H from aqueous solution. The as synthesized C-S-HPN materials were characterized by Fourier-transform infrared photoacoustic (FTIRPAS) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy/energy dispersed spectroscopy (SEM/EDS), thermogravimetric analysis (TG), differential thermogravimetry (DTG) and differential scanning calorimetry (DSC). The XRD peaks of C-S-HPN materials suggest the intermediate organizations presenting both intercalation of PVA and exfoliation of C-S-H. The SEM micrographs of C-S-H, PVA and C-S-HPN materials with different PVA contents exhibit the significant differences in their morphologies. Effects of the material compositions on the thermal stability of a series of C-S-HPN materials along with PVA and C-S-H were studied by TG, DTG and DSC. Three significant decomposition temperature ranges were observed in the TG curves of all C-S-HPN materials.     

The synthesis and characteristic study of 6FDA-6FHP-NLO polyimide/SiO2 nanohybrid materials

Hybrid nanocomposite films of silica (SiO₂) in polyimide (PI) from 4,4^′-(hexafluoroisopropylidene) diphthalic arhydride (6FDA), 2,2-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FHP) and nonlinear optical (NLO) molecule have been successfully fabricated by an in situ sol-gel process. The silica content in the hybrid films was varied from 0 to 22.5 wt%. These nanocomposite films exhibit fair good optical transparency. Fourier transform infrared (FTIR) spectroscopy results confirm the formation of SiO₂ particles in PI matrix. Scanning electron microscope (SEM) images show that the SiO₂ phase is well dispersed in the polymer matrix. Their glass transition behavior and thermal stability were investigated by differential scanning calorimeter (DSC) and thermal gravimetric analysis (TG).     

聚乙烯醇/纳米纤维素复合膜的渗透汽化性能及结构表征

将聚乙烯醇/纳米纤维素(PVA/NCC)复合膜应用于乙醇-水混合溶液的渗透汽化脱水过程,探讨了纳米纤维素对膜的溶胀性能、机械性能和渗透汽化性能的影响; 利用原子力显微镜(AFM)探测了纳米纤维素的形貌特征; 采用傅里叶变换红外光谱仪(FTIR)、扫描电镜(SEM)、差示扫描量热仪(DSC)和热重分析仪(TGA)对膜结构...     

Kinetic study of the thermal decomposition of poly(vinyl alcohol)/kraft lignin derivative 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 (Hg lamp, 96 h) and analyzed by thermogravimetry (TG) in inert and oxidative atmosphere. Typical multi-step decomposition profiles were obtained. The apparent activation energy (E_a) of the thermal degradation of the samples was computed by the Vyazovkin method. The KLD degradation presented only small intervals of decomposition degree with constant E_a values. PVA and blends showed intervals of up to 50% in decomposition degree with nearly constant E_a, and smaller intervals in which E_a varies drastically. The influences of samples irradiation and of surrounding gas in TG analysis on E_a are also shown.     

丝素褐藻糖胶共混膜的结构与热性能

丝素是蚕丝的主要成分，是人类最早应用的天然蛋白质之一，作为性能优良的天然纤维一直用于纺织行业．近年来，丝素膜由于具有良好的透气透氧性和较少的炎症反应，尤其是对活体组织具有良好的生物相容性的特点，在生物工程和生物医学领域得到广泛地研究，被用作酶的固定化材料和哺乳动物细胞培养的基质、体外组织工程支架和抗凝血材料等．     

Thermal characterization of bacterial cellulose–phosphate composite membranes

Cellulose–phosphate composite membranes have been prepared from bacterial cellulose membranes (BC) and sodium polyphosphate solution. The structure and thermal behavior of the new composites were evaluated by X-ray diffraction (XRD), ³¹P-nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetry (TG) and thermomechanical analysis (TMA). From XRD analyses the Iα and Iβ cellulose crystalline phases were identified together with crystalline sodium phosphate that covers the cellulose microfibrils as revealed by SEM. ³¹P NMR spectra show peaks assigned to Q⁰ and Q¹ phosphate structures to be compared to the Q² units that characterize the precursor polyphosphate. Glass transition temperature, T _g, obtained from TMA curves and thermal stability obtained from TG and DSC measurements, were observed to be dependent on the phosphate content.     

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 properties of water‐soluble chitosan and polyvinyl alcohol blend films as potential bone tissue engineering matrix

The blend film was prepared by casting solutions of water‐soluble hydroxyethyacryl‐chitosan (HEA‐CS) and polyvinyl alcohol (PVA) and cross‐linked by glutaraldehyde. The structure and properties of the blend films were estimated by wide‐angle X‐ray diffraction (WXRD), contact angle measurements with water, and scanning electron microscopy (SEM). The tensile properties of the blend films were investigated and the tensile strength (TS) and the elongation increased with the increased amount of PVA. The thermal stability (thermogravimetric (TG) and derivative thermogravimetric (DTG)) was evaluated and HEA‐CS was more thermally‐stable than that of PVA. The water swelling properties analysis indicated that HEA‐CS in the blends promoted the water absorption owing to its porous structure and the antimicrobial ability of the blend films was retained. Indirect cytotoxicity assessment of the blend films with human bone sarcoma cell (SW1353) indicated that the biomaterials were non‐toxic and did not release substances harmful to living cells. Copyright © 2009 John Wiley & Sons, Ltd.     

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.     

Controlled/living free‐radical copolymerization of 4‐(azidocarbonyl) phenyl methacrylate with methyl acrylate under 60Co γ‐ray irradiation

A new vinyl acyl azide monomer, 4‐(azidocarbonyl) phenyl methacrylate, has been synthesized and characterized by NMR and FTIR spectroscopy. The thermal stability of the new monomer has been investigated with FTIR and thermal gravimetry/differential thermal analysis (TG/DTA), and the monomer has been demonstrated to be stable below 50 °C in the solid state. The copolymerizations of the new monomer with methyl acrylate have been carried out at room temperature under ⁶⁰Co γ‐ray irradiation in the presence of benzyl 1H‐imidazole‐1‐carbodithioate. The results show that the polymerizations bear all the characteristics of controlled/living free‐radical polymerizations, such as the molecular weight increasing linearly with the monomer conversion, the molecular weight distribution being narrow (<1.20), and a linear relationship existing between ln([M]₀/[M]) and the polymerization time. The data from ¹H NMR and FTIR confirm that no change in the acyl azide groups has occurred in the polymerization process and that acyl azide copolymers have been obtained. The thermal stability of the polymers has also been investigated with TG/DTA and FTIR. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2609–2616, 2007     

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.     

Thermal properties and degradability of poly(propylene carbonate)/poly(β-hydroxybutyrate-co-β-hydroxyvalerate) (PPC/PHBV) blends

Poly(propylene carbonate)/poly(β-hydroxybutyrate-co-β-hydroxyvalerate) (PPC/PHBV) blends were prepared via the solution casting method at different proportions. Their thermal characteristics were studied by means of differential scanning calorimetry (DSC) and thermogravimetry (TG). The degradability of the blends was investigated in soil suspension cultivation and in vitro degradation testing. The changes of structure and molecular weight for blends were also studied by ¹H nuclear magnetic resonance spectroscopy (¹H NMR), scanning electron microscopy (SEM) and gel permeation chromatography (GPC) before and after degradation. Although the PPC/PHBV blends were immiscible, the addition of PHBV could improve the thermal stability of PPC. PHBV was degraded mainly by the action of microbial enzymes in the soil suspension, which biodegraded it more rapidly than PPC in a natural environment. PPC was degraded mainly by chemical hydrolysis and random hydrolytic scission of chains in the PBS solution in vitro, and degradation of PPC was more rapid than that of PHBV in a simulated physiological environment.     

Emulsion copolymerization of fluorinated acrylate in the presence of a polymerizable emulsifier

An emulsifier-free fluorinated polyarcylate emulsion was synthesized by a seed emulsion polymerization method from methyl methacrylate (MMA), butyl acrylate (BA) and hexafluorobutyl methacrylate (HFMA) in the presence of a polymerizable emulsifier—ammonium allyloxtmethylate nonylphenol ethoxylates sulfate (DNS-86). Influences of the DNS-86 level on electrolyte stability of the emulsifier-free emulsion were discussed. In addition, the emulsion and the films were characterized by Fourier transformed infrared (FT-IR) spectrometry, nuclear magnetic resonance (¹H NMR) spectrometry, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), thermogravimetry (TG), and contact angle (CA) analysis, respectively. The FT-IR spectra and ¹H NMR spectrum showed that HFMA was effectively involved in the emulsion copolymerization and monomers formed the fluorine-containing acrylate copolymer. The resulted emulsion particles had a core–shell structure and a narrow particle size distribution. XPS and CA analysis revealed that a gradient concentration of fluorine existed along the depth profile of the fluorine-containing emulsion film. One side of the film was richer in fluorine and more hydrophobic than the other side. The film formed from the fluorine-containing emulsion showed higher thermal stability than that of the fluorine-free emulsion.     

Thermal degradation of a reactive flame retardant based on cyclotriphosphazene and its blend with DGEBA epoxy resin

Hexaglycidyl cyclotriphosphazene (HGCP) was synthesized, and characterized by FTIR, ³¹P, ¹H, and ¹³C-NMR. This compound was used as a reactive flame retardant to blend with commercial epoxy resin DGEBA (Diglycidyl ether of bisphenol A). Its effect on the DGEBA decomposition pathways was characterized by studying both gas and solid phases produced during thermogravimetric analysis (TGA). The gases evolved during TGA in air were studied by means of thermogravimetry coupled with Fourier transform infrared spectroscopy (TG–FTIR), while the solid residues were analysed by FTIR and scanning electron microscopy (SEM). The results showed that HGCP presents a good dispersion in DGEBA, and the blend thermoset with 4,4′-methylene-dianiline (MDA) curing agent leads to a significant improvement of the thermal stability at elevated temperature with higher char yields compared with pure DGEBA thermoset with the same curing agent. Improvement has also been observed in the fire behaviour of blend sample.     

Thermal stability of the PBAT biofilms with cellulose nanostructures/essential oils for active packaging

The primary objective of this study is to evaluate the thermal stability of the active films with the cellulose nanostructure (CNS, 5?mass%) treated with encapsulated essential oils (EOs), eugenol and linalool. CNS untreated and treated were incorporated in the poly(butylene adipate-co-terephthalate) (PBAT) polymer matrix prepared by casting. In this study, all samples were characterized by FTIR, DRX, TG, DSC and SEM, elucidating the contribution of each component in the final films. CNS untreated and treated with EOs were characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis (TGA), confirming the interaction between these components. The active biofilms were analyzed by TGA and DSC analyses (differential scanning calorimetry), confirming that their thermal stability was maintained similar to the neat PBAT film, without loss of properties. The CI (crystallinity index, %) of the polymeric films was calculated from heat fusion (ΔH) values, indicating that the incorporation of the nanostructures into the PBAT matrix increases the crystallinity of the biofilms, from 11.5 (neat PBAT) to 13.8% (PBAT/CNS-E), acting as a nucleating agent in the polymeric matrix. The presence of the EOs did not decrease the CNS stability, as well of the biocomposite films. Moreover, the thermal analysis confirmed that the EO was well involved by the CNS, before and after the incorporation in the PBAT polymer, as observed in the SEM images.

     

A novel intumescent flame-retardant system containing metal chelates for polyvinyl alcohol

A novel flame retardant containing phosphorous-nitrogen structure, the ammonium salt of 2-hydroxyl-5,5-dimethyl-2,2-oxo-1,3,2-dioxapho sphorinane (PNOH), was synthesized and its structure was characterized by ¹H NMR and FTIR spectra. PNOH was used together with ammonium polyphosphate (APP) to prepare a novel intumescent flame retardant (IFR) for polyvinyl alcohol (PVA). When a few amounts (0.5%) of metal chelates were added, the flame retardancy of the IFR-PVA systems was significantly improved, having a high LOI value of 34.2 in a total IFR loading of 15 wt.%. In order to have an understanding of the resulting flame retardant effects, the thermal degradation behaviors of IFR-PVA systems were investigated by thermogravimetric analysis (TGA), and the morphology and structures of residues generated in different conditions were investigated by scanning electronic microscopy (SEM) and FTIR spectra. The results show that NiSAO can promote the thermal stability of the IFR-PVA; the residual char containing polyphosphoric or phosphoric acid is formed during the combustion; the formation of a continuous and dense char layer could inhibit the transmission of heat during contacting with flame and shows good flame retardancy.     

Design,synthesis, and characterisation of symmetrical bent-core liquid crystalline dimers with diacetylene spacer

Two new symmetrical bent-core liquid crystalline dimers (B-DA4 and B-DA12) bearing diacetylenes spacer and different terminal alkyl chains were successfully synthesised via Sonagashira coupling reaction. The molecular structures of these dimers were confirmed by ¹H nuclear magnetic resonance (NMR), Fourier transform-infrared spectroscopy (FT-IR), Raman spectroscopy, mass spectrometry, and elemental analysis. Their thermal stability and liquid crystalline properties were characterised by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), polarised light microscopy (PLM), and small-angle X-ray scattering (SAXS). Results showed that the diacetylene group may be thermal polymerised at about 260°C far from thermal decomposition. The dimers exhibited monotropic phase behaviour and typical layered-structure phase with long-range order on a length scale of about 6.3 nm was observed. The results mentioned above offer a promising opportunity to design polydiacetylene nanowires by thermal, UV irradiation, or scanning tunnelling microscope (STM) tip-induced polymerisation.