Structure and Mechanical Properties of Chitosan/Poly(Vinyl Alcohol) Blend Films

Summary: The origins of the thermal and mechanical properties of chitosan and poly(vinyl alcohol) (PVA) with inter- and intra-hydrogen bonds were investigated systematically by using X-ray, DSC, positron annihilation and viscoelastic measurements. Based on their individual properties, the characteristics of the blend films were estimated in relation to their morphology and mechanical properties as a function of chitosan content. The characteristics of the blend films were also analyzed in terms of the deviation from a simple additive rule of chitosan and PVA content. These results suggested that the miscibility of chitosan and PVA could be ensured by entanglement of the amorphous chain segments of chitosan and PVA. Further detailed analysis revealed that the chitosan content on the film surface is higher than that of the admixture content of chitosan after elongation, although the chitosan and PVA chains were crystallized independently. The elongation could be achieved for the blend films whose PVA content was higher than 50% and the drawn blend films were transparent. Thus, it may be expected that sufficiently entangled meshes formed between chitosan and PVA amorphous chains within the film, the PVA content being higher than 50%, were maintained under the elongation process.     

甲壳素/聚氨酯共混物膜结构与性能的研究

采用共混的方法分别制备了丁羟型和聚醚型聚氨酯／甲壳素共混膜(HPCT和PPCT系列),研究了甲壳素加入量对共混膜力学性能、热稳定性、溶胀性和吸湿性的影响,讨论了共混物膜在不同环境条件下的降解性能。结果表明随着甲壳素含量的增加共混材料对水的亲和力和热稳定性提高,当甲壳素质量分数分别为0．15和0．10时HPCT系列和PPCT系列具有较佳的力学性能,HPCT和PPCT系列分别在pH=7．0和pH=4．7的环境中具有良好的降解性能。     

Electrical Properties Investigation in PA12/PANI Composites

Summary: Volume conducting PA-12 based composites powders were chemically prepared by in situ polymerization and aniline doping at room temperature. These kinds of polyamide / PANI composites were investigated regarding their electrical properties. Their ac and dc electrical properties measured in the frequency range of 10⁻²–10⁷ Hz are reported and the frequency dependence of electrical conductivity was investigated as a function of PANI concentration leading to the determination of the conductivity. The experimental conductivity was found to increase continuously with PANI content and explained by percolation theory with a relatively low percolation threshold of about 0.4 wt.%. The dielectric behavior of various PANI polymer composites has been characterized by the critical frequency ω_c (denoting the crossover from the dc plateau of the conductivity to its frequency dependent ac behaviour). Modelling the conductivity behavior versus volume fraction using Slupkowski approach has revealed that the considered parameters are not sufficient to describe the electrical conductivity behavior.     

聚吡咯薄膜的电特性

含有不同的链长的w-吡咯烷基二甲基氯硅烷作为粘合剂通过自组装（SAMs）吸附于二氧化硅表面,然后聚吡咯膜化学沉积于该粘合剂修饰的表面。化学沉积的聚吡咯膜的表面形貌用扫描电镜（SEM）及原子力显微镜（AFM）表征。除短链外不同链长的粘合剂对聚吡咯膜的厚度影响不大。聚吡咯膜的电特性用电流-电压表征。结果显示电流与粘合剂的链长无关。电特性表明载流子迁移率为1.4 ´ 10-4 cm2×V-1.s –1。     

三偏磷酸钠交联壳聚糖/聚乙烯醇共混膜的制备及其性能研究

将充分溶胀的壳聚糖/聚乙烯醇共混膜置于一定浓度的三偏磷酸钠溶液中进行交联反应制备出交联壳聚糖膜。用红外光谱(FTIR-ATR)、X-射线衍射(XRD)和扫描电镜(SEM)表征了膜的结构,并测试了其吸水率、力学性能、酶降解性能。结果表明,交联作用明显提高了膜的抗张强度和抗水性,并有效地降低了溶菌酶对其降解速率。     

High Substitution Synthesis of Carboxymethyl Chitosan for Properties Improvement of Carboxymethyl Chitosan Films Depending on Particle Sizes

This study investigated the effect of chitosan particle sizes on the properties of carboxymethyl chitosan (CMCh) powders and films. Chitosan powders with different particle sizes (75, 125, 250, 450 and 850 µm) were used to synthesize the CMCh powders. The yield, degree of substitution (DS), and water solubility of the CMCh powders were then determined. The CMCh films prepared with CMCh based on chitosan with different particle sizes were fabricated by a solution casting technique. The water solubility, mechanical properties, and water vapor transmission rate (WVTR) of the CMCh films were measured. As the chitosan particle size decreased, the yield, DS, and water solubility of the synthesized CMCh powders increased. The increase in water solubility was due to an increase in the polarity of the CMCh powder, from a higher conversion of chitosan into CMCh. In addition, the higher conversion of chitosan was also related to a higher surface area in the substitution reaction provided by chitosan powder with a smaller particle size. As the particle size of chitosan decreased, the tensile strength, elongation at break, and WVTR of the CMCh films increased. This study demonstrated that a greater improvement in water solubility of the CMCh powders and films can be achieved by using chitosan powder with a smaller size.     

甲壳素/甲壳胺的聚集态结构及性能

制备了不同脱乙酰度的甲壳素,并对脱酰化反应进行了研究,找出了适合不同脱酰度甲壳素的溶剂,探讨了制样温度与甲壳胺膜的结晶形态和力学性能之间的关系,比较了甲壳素、甲壳胺及不同来源甲壳素的结晶形态.     

Effect of Carbon Dots Concentration on Electrical and Optical Properties of Their Composites with a Conducting Polymer

CQD/PEDOT:PSS composites were prepared via the hydrothermal method from glucose carbon quantum dots (CQDs) and an aqueous solution of PEDOT:PSS conducting polymer and their electrical and optical properties were investigated. The morphology and structure of these samples were investigated by AFM, SEM, EDX, and EBSD. It was found that the CQDs and CQD/PEDOT:PSS composites had a globular structure with globule sizes of ~50–300 nm depending on the concentration of PEDOT:PSS in these composites. The temperature dependence of the resistivity was obtained for the CQD/PEDOT:PSS (3%, 5%, 50%) composites, which had a weak activation character. The charge transport mechanism was discussed. The dependence of the resistivity on the storage time of the CQD/PEDOT:PSS (3%, 5%, 50%) composites and pure PEDOT:PSS was obtained. It was noted that mixing CQDs with PEDOT:PSS allowed us to obtain better electrical and optical properties than pure CQDs. CQD/PEDOT:PSS (3%, 5%, 50%) composites are more conductive composites than pure CQDs, and the absorbance spectra of CQD/PEDOT:PSS composites are a synergistic effect of interaction between CQDs and PEDOT:PSS. We also note the better stability of the CQD/PEDOT:PSS (50%) composite than the pure PEDOT:PSS film. CQD/PEDOT:PSS (50%) composite is promising for use as stable hole transport layers in devices of flexible organic electronics.     

PMMA/定向碳纳米管复合材料导电与导热性能的研究

Methyl Methacrylate(MMA) has been filled in the apertures of aligned carbon nanotubes(ACNTs). Then PMMA/ACNTs composites have been synthesized by in-situ polymerization. The SEM results show that carbon nanotubes are well dispersed and directionally arranged in the composites. The electrical conductivities of the parallel direction (parallel with ACNTs) and perpendicular direction (perpendicular with ACNTs) of composites were respectively tested to be 15 S·cm^-1 and 4 S·cm^-1, so the composites were conductivity anisotropic. Compared with PMMA, the thermal stable temperature of composites in air was improved by 100 ℃,and the thermal conductivity of composites was 13.64 times of PMMA.     

胶原-壳聚糖共混膜的微观结构

胶原-壳聚糖共混膜的微观结构;胶原;壳聚糖;共混膜;原子力显微镜(AFM)     

Electrical Properties of Sol-Gel Processed Hybrid Films

We report on the electrical properties of a hybrid organic/inorganic material synthesized by a sol-gel technique. Spin-coated films with sputtered Nb electrodes in a sandwich-type geometry were studied by a.c. measurements. The aging of the films affected the resistance of the samples. Electrochemical impedance spectroscopy (EIS) measurements were performed in a test chamber at different relative humidity (RH) values to evaluate the aging mechanism.     

Electrical Properties of Transparent Doped Oxide Films

In the present study n-type and p-type transparent conductive TiO₂ films were prepared by using sol-gel method. The n-type TiO₂ films were obtained by using Ti(OC₃H ₇ ⁱ )₄ solutions co-doped with Ru and Ta. The films were uniform and transparent in all the conditions, and their crystalline phases were anatase when HCl or HNO₃ was used as a catalyst. The resistivity decreased with increasing Ta content and increased with increasing Ru content. Most of the films showed resistivity minima at a heat-treatment temperature of 700°C. The lowest resistivity of 10¹ 10² cm was attained. The p-type TiO₂ films were obtained by using Ti(OC₃H ₇ ⁱ )₄ solutions co-doped with Co and Nb (Sb). The films were also uniform and transparent when AcAc was used, while samples heat-treated at 800°C became opaque when HCl was added. Rutile single phase appeared when the films were heat-treated at 700°C. Logarithmic resistivity of films co-doped with Co and Nb was directly proportional to the reciprocal absolute temperature. On the other hand, the slopes for films co-doped with Co and Sb were different below and above 200°–220°C. The activation energy at the low-temperature region is as low as 0.17 eV, and the resistivity at room temperature is 10⁴ 10⁵ cm.     

Synthesis and properties of poly‐(2‐ethynylpyridinium bromide) having propargyl side chains

Poly‐(2‐ethynylpyridinum bromide) (PEPBP) having propargyl side chains was prepared by the direct polymerization of 2‐ethynylpyridine and propargyl bromide under mild reaction conditions without any initiator and catalysts. The polymerization proceeded well to give PEPBP with propargyl side chains in relatively high yields. Various spectral data for the polymer structure indicated that the conjugated polymer system having N‐propargylpyridinum substituent was formed. This ionic polymer was completely soluble in water, methanol, dimethylformamide, dimethyl sulfoxide, and N,N‐dimethylacetamide and well processable into thin homogeneous film. The photoluminescence intensity (λ_max = 760 nm) of this polymer increased as the temperature was increased. At 1 KHz and room temperature, this polymer has k′ = 2.9 and σ = 7.3 × 10^?10 (S/cm). © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3151–3158, 2001     

Theoretical and Predictive Modelling of Physical Properties of Polymers

The application of Boltzmann statistics to a complete distribution of molecular conformation energies of simplified homo‐ and copolymer models gives meaningful information about temperatures at which phase transitions take place in the bulk. We have calculated in the conformation statistical distribution (CSD) approximation Helmholtz free energy variation versus temperature δF = δU–TδS, where U and S are, respectively, the internal molecular energy and the Gibbs statistical entropy of the considered polymeric model. The deepest minima correspond to glass‐transition temperature (T_g) and melting temperature (T_m) of modelled polymers, while the remaining peaks are related to some other transitions, the existence of which is also experimentally proven. The adopted method is able to give T_g and T_m as a function of the molecular weight of polymers. Some indications can also be achieved about the instability of polymers. The same procedure has been applied to copolymers and blends and has given acceptable results for T_g and T_m as functions of the material microstructure and composition. Other thermal and mechanical properties, such as moduli, mobilities, chemical resistance to oxidation, physical tendency to miscibility, have been directly or indirectly estimated.     

Properties of Natural Rubber/Recycled Chloroprene Rubber Blend: Effects of Blend Ratio and Matrix

The present study investigated the effects of two types of natural rubber and different blend ratios on the cure, tensile properties and morphology of natural rubber/recycled chloroprene rubber blends. The blends of natural rubber/recycled chloroprene rubber were prepared by using laboratory two-roll mill. The result showed that the cure time prolonged with the addition of recycled chloroprene rubber (rCR). Comparability, natural rubber/recycled chloroprene rubber (SMR L/rCR) blendcured rapidly than epoxidized natural rubber/recycled chloroprene rubber (ENR 50/rCR) blend. The addition of rCRalso caused a decrement in the tensile strength and elongation at break for both rubber blends. The SMR L/rCR blendsshowed higher tensile strength and elongation at break compared to those of ENR 50/rCR blends at any blend ratios.     

Preparation and Properties of Chitosan/Konjac Glucomannan Blend Fibers

Chitosan and konjac glucomannan (KGM) blend fibers were prepared by spinning their solution through a viscose‐type spinneret into a coagulating bath containing aqueous sodium hydroxide and ethanol. The structure and properties of the blend fibers were studied with the aids of infrared spectra (IR), scanning electron micrography (SEM) and X‐ray diffraction (XRD). The structure analysis indicated that there were strong interaction and good miscibility between the chitosan and KGM molecule which resulted from intermolecular hydrogen bonds. Mechanical properties and water‐retention properties were measured. Through controlling blend conditions, blend fibers can obtain better mechanical properties than the pure chitosan fiber. The water‐retention values (WRV) of blend fibers increase as the amount of KGM is raised. The fibers treated with alcoholic solution of acetic acid have good antibacterial activity to Staphylococcus aureus.     

PANI-DBSA/PAN共混体系的相容性及导电性能

以三氯甲烷/二甲基亚砜为混合溶剂,采用溶液共混的方法制备PANI-DBSA/PAN导电薄膜.采用扫描电镜、差示扫描量热仪、红外光谱及广角X射线衍射分析研究了共混体系的相容性及相态结构.结果表明,PANI-DBSA在PAN基体中分布均匀,聚集尺寸为纳米级,其较均匀的分布及较小的聚集尺寸使其出现较低的逾渗阈值(低于4%);PANI-DBSA/PAN的共混体系只有一个玻璃化转变温度,居于纯PAN和PANI-DBSA之间,表明两者之间具有良好的相容性;FTIR分析证实PANI-DBSA与PAN之间存在氢键相互作用,氢键发生在PANI-DBSA的氨基与PAN共聚物中的羰基之间,这两种聚合物之间的氢键相互作用是导致PANI-DBSA与PAN之间良好相容性的内因.     

Structural and Electrical Properties of Iron-Containing Aluminosilicate Gel-Derived Pellets

Aluminosilicate pellets containing 10 mol% of Fe₂O₃, prepared by the sol-gel method, have been investigated. Electrical conductivity, dielectric constant, X-ray diffraction, scanning electron microscopy and electron paramagnetic resonance have been used to characterize the evolution of the samples with the heat-treatment temperature and atmospheric conditions. Results show that iron is present in the air heat-treated samples as Fe³⁺, goethite and hematite particles. Metallic iron and magnetite were identified in the samples heat-treated under reducing conditions. The d.c. conductivity decreases with increasing heat-treatment temperature of the samples indicating a variation, with the temperature, of the electrical free charges. However, in the case of the dielectric constant the samples heat-treated in air and under reducing conditions do not present the same behaviour. This variation was related with the microstructural evolution of the samples.     

纤维素/壳聚糖共混透明膜的制备及阻隔抗菌性能研究

利用壳聚糖溶液包覆法制备了具有高气体阻隔性及抗菌性的透明纤维素膜,其扫描电镜照片证明壳聚糖厚度在1.31 ～4.07 μm之间.通过红外光谱、紫外光谱、热重分析仪、电子万能试验机和接触角测试仪对纤维素/壳聚糖共混膜的结构和性能进行了详细研究,结果表明由于壳聚糖和纤维素之间具有一定的氢键相互作用,使得纤维素/壳聚糖共混膜较好地保持了纯纤维素膜的机械强度,其拉伸强度都大于110 MPa.此外,壳聚糖的包覆对纤维素膜的透明性没有影响,它在600 ～ 800 nm处的透光率仍维持在80％左右,并且提高了纤维素膜的疏水性,其水接触角从纤维素膜的70°提高到了100°.利用气体渗透仪进一步研究了纤维素/壳聚糖共混膜的氧气阻隔性,结果表明该膜具有很好的氧气阻隔性,其氧气渗透系数甚至低于市场上理想的氧气阻隔材料乙烯-乙烯醇共聚物(EVA).金黄色葡萄球菌抗菌测试表明,通过壳聚糖包覆法改性纤维素能够明显提高纤维素膜的抗菌性.