柞蚕丝素蛋白的凝胶化行为（摘要）

柞蚕丝素蛋白与细胞具有特异性相互作用,作为生物医用材料具有潜在的研究和开发前景.凝胶是组织再生支架的重要材料形态之一,而迄今国内外尚无对柞蚕丝素蛋白凝胶化行为的系统性研究报道.本文研究了环境温度、pH值、柞蚕丝素溶液的浓度以及K^＋、Ca^2＋的浓度对再生柞蚕丝素蛋白的凝胶化速率的影响,研究了溶胶-凝胶转变过程中柞蚕丝素蛋白构象的变化.     

溶胶-凝胶法制备有机/无机杂化材料工艺及其应用

介绍了溶胶–凝胶法制备有机/无机杂化材料的原理和基本过程,杂化材料的制备方法及对材料性能的影响,概述了杂化材料在结构材料、光学材料及其它材料中的应用研究。     

P123重水溶液的物理凝胶化及凝胶结构

利用 1H NMR方法, 研究了高浓度的P123(PEO20PPO70PEO20)在重水溶液中的溶胶-凝胶转变过程. 升高温度使得体系发生溶胶-凝胶转变, 进一步升高温度, 体系发生凝胶-溶胶转变. 通过对不同质子基团的谱线宽度和化学位移偏移的分析, 同时结合流变学频率扫描和同步辐射(SR)研究, 发现质量分数为30%的P123的重水溶液在凝胶化过程中, 结构经历了由立方相(cubic)-六角柱状相(hcp)-层状相(lamellar)的转变过程, 其中立方相为面心立方(fcc)和六角密堆积球状相(hcps)的混合相. 高温时从凝胶到溶胶的转变主要体现为P123形成富集区与水发生相分离的过程.     

溶胶-凝胶法合成聚甲基丙烯酸甲酯/二氧化钛杂化聚合物材料

由共聚合在PMMA聚合物链段上引入了－Si(OR)₃功能团,通过溶胶－凝胶过程合成了PMMA/TiO₂杂化聚合物材料.溶剂抽提结果表明有化学键存在的杂化材料体系中凝胶的含量很高.通过FTIR测试对材料结构进行了分析,由TGA、DSC测试分析了杂化材料体系中无机组份的含量对材料性能的影响.     

乙二胺对溶胶-凝胶法合成La0.65Sr0.35MnO3的影响

利用溶胶-凝胶工艺制备了钙钛矿结构的亚锰酸盐化合物(La0.65Sr0.35MnO3),通过XRD和SEM研究了乙二胺和氨水对溶胶-凝胶工艺的影响.结果发现,当体系pH值调梧到8.0附近时,添加乙二胺有利于溶胶-凝胶的形成,而添加氨水的样品中有部分沉淀产生,不能很好地凝胶化.热处理后,添加乙二胺的样品形成的产物颗粒细小均匀,而添加氨水的样品出现了比较严重的团聚现象.分析表明:乙二胺在溶胶.凝胶形成过程中起着桥接、交联和螫合的作用,桥接和交联有利于凝胶化过程的发生和稳定,螯合作用有利于金属离子均匀分散在凝胶的三维网络结构中,从而减少后期热处理过程中的团聚.     

溶胶凝胶模板法制备SiO2:Sm3+纳米阵列材料

采用溶胶凝胶模板法制备了不同Sm3+掺量的SiO2:Sm3+纳米阵列材料,通过SEM、EDS、FTIR等对材料的形貌和结构进行测试表征.FTIR分析表明Sm3+进入SiO2网络结构形成了Si-O-Sm键.SEM、EDS分析显示Sm3+掺量的增大促使阵列由纳米管向纳米线的转变.此外,腐蚀清洗等后处理工艺对保持纳米阵列的形貌至关重要.最后,讨论了溶胶凝胶模板法制备SiO2;Sm3+纳米阵列的机理.     

Aa1Dd1-Aa2Dd2型氢键体系的网络结构参数

利用溶胶-凝胶分配理论对氢键溶液的模型体系进行研究, 给出了体系的凝胶化条件以及凝胶点后氢键网络中各类结构参数的计算方案, 并进行了相应的数值计算. 结果表明, 当两类质子受体基团的活性不同时, 质子受体基团的竞争作用对网络结构有一定影响. 这为控制氢键网络结构特征提供了可能的理论线索.     

_(a_1)_(d_1)-A_(a_2)D_(d_2)型氢键体系的网络结构参数

利用溶胶-凝胶分配理论对氢键溶液的模型体系进行研究,给出了体系的凝胶化条件以及凝胶点后氢键网络中各类结构参数的计算方案,并进行了相应的数值计算.结果表明,当两类质子受体基团的活性不同时,质子受体基团的竞争作用对网络结构有一定影响.这为控制氢键网络结构特征提供了可能的理论线索.     

溶胶—凝胶法合成聚甲基丙烯酸甲酯／二氧化钛杂化聚合物材料

由共聚合在ＰＭＭＡ聚合物链段上引入了一－Ｓｉ（ＯＲ）３为功能团，通过溶胶－凝胶过程合成了ＰＭＭＡ／ＴｉＯ２杂化聚合物材料，溶剂抽提结构表明有化学键存在的杂化材料体系中凝胶的含量很高，通过ＦＴＩＲ测试材料结构进行了分析，由ＴＧＡ，ＤＳＣ测试分析了杂化材料体系中无机组份的含量材料性能的影响。     

酶凝干酪素物理凝胶化过程的有限元模拟

以酶凝干酪素的凝胶化过程为对象,利用有限元方法数值分析了在凝胶化过程中温度场的空间分布和时间演变规律.在此基础上,基于一阶的凝胶化动力学方程,数值模拟了凝胶体系的复剪切模量场,进而分析了材料配方、体系尺寸与冷却方案对复剪切模量场的影响规律.模拟结果表明,由于热阻的差异,体系表面的冷却速率大于内部,表面首先发生凝胶化;而由于预凝胶化阶段的平均冷却速率决定了无穷复剪切模量的值,最终体系内部的复剪切模量超过表面的.     

Sol-Gel Transition and Equilibrium Shear Modulus of Poly(vinyl chloride) and Plasticizers

The elasticity of poly(vinyl chloride) gels with molecular weight distribution (M_w/M_n), of 2.16 have been studied in the region beyond their gel points. Dynamic storage modulus G′, and equilibrium gel shear modulus of elasticity G_e, at low frequencies (ω) have specific developments as a function of polymer concentrations c, and plasticizers. The scaling elasticity from G_e = kε^z equation holds at different PVC plasticizer gels. The scaling exponent z, and constant k. ε is defined as the relative distance, ε = (|c − c_g|)/c_g, the calculated z = 2.45 ± 0.15. Furthermore, this analysis provides constant k with certain informations about the dependency of gel elasticity on the kind of plasticizer. Near the sol-gel transition temperature T, G_e decreases rapidly with increasing temperature. The normalized moduli G_eM/cRT, of the gels at different temperature, and/or c were dependent on the relative distance from the gelation point ε, and PVC and plasticizers concentration respectively. These results suggested mesh size of gel network near the gelation point for PVC with bis(2-ethylhexyl) phthalate (DOP) or di-n-butyl sebacate (DBS) plasticizers that has been newly reported.     

EFFECT OF PLASTICIZER ON THE MICROSTRUCTURE OF PS/PVC BLENDS

In this work, controlling of the particle size of PVC in PS/PVC blends was studied. Itis shown that viscosity ratio and particle size can be changed by adding a third composition,such as plasticizers, and the distribution of the third composition in two phases plays avery important role in controlling viscosity ratio and particle size. When DOP was used asthe plasticizer of PVC in PS/PVC blends, the particle size of PVC could not be reduceddue to the transference of DOP into PS phase. When polycaprolactone (PCL) was usedas the plasticizer of PVC in the same blends, the particle size of PVC could be descreasedobviously because PCL does not migrate to PS phase.     

Gelation/fusion behavior of PVC plastisol with a cyclodextrin derivative and an anti-migration plasticizer in flexible PVC

We successfully evaluated the effects of 2,3,6-per-O-benzoyl-β-cyclodextrin (Bz-β-CD) on the rheological properties of PVC plastisols and the migration behavior of plasticizer from flexible PVC. Two types of plasticizer, di-isononyl phthalate (DINP) and diisononyl cyclohex-4-ene-1,2-dicarboxylate (Neocizer), along with Bz-β-CD as a migration inhibitor were mechanically mixed into an emulsion grade PVC resin to prepare plastisols. The presence of Bz-β-CD was expected to facilitate formation of stable complexes with DINP or Neocizer in the flexible PVC. It was necessary to determine whether changes in the processing conditions of the PVC plastisol were needed for use in this application. To this end, the viscoelastic properties of the plastisols, including the elastic modulus, G′, and the viscous modulus, G″, were continuously monitored as a function of temperature during the gelation and fusion processes using rheological analysis techniques. The results showed that complete gelation was slightly delayed and both moduli (G′ and G″) decreased upon addition of Bz-β-CD to the PVC matrix. FE-SEM images yielded insight into the gelation and fusion processes. The curing conditions and physical properties of the flexible PVCs containing Bz-β-CD were optimized, and the influence of Bz-β-CD on the migration of the plasticizers and the stability of the flexible PVC was studied. The results showed that Bz-β-CD reduced migration of DINP and Neocizer from the flexible PVC by almost 40% and 25%, respectively, thereby favorably restricting migration within the flexible PVC.     

Network formation by epoxidised soybean oil in plastisol poly(vinyl chloride)

Epoxidised soybean oil, ESBO, is a well known additive used in plasticized poly(vinyl chloride) (PVC) since it functions both as plasticizer and as stabilizer. This paper describes what happens to the material when ESBO is used as primary plasticizer in plastisol- and in suspension PVC without any additional stabilizer. When 50 ph ESBO was added to 100 ph plastisol PVC and then aged in a Werner Mathis oven at 180 °C for various lengths of time, the E-modulus increased with ageing time due the formation of a crosslinked network induced by a polymerization reaction of the epoxy groups in the ESBO. The network and the PVC were analyzed by NMR which showed that reaction between PVC and ESBO had occurred, and that the network consisted primarily of ESBO. The same experiment performed with suspension PVC instead of plastisol PVC did not result in any crosslinking of the ESBO. The ring opening of the epoxy which starts the polymerization of ESBO is most likely catalyzed by an additive used in the polymerization of plastisol PVC.     

High-temperature pyrolysis of poly(vinyl chloride): Gas chromatographic-mass spectrometric analysis of the pyrolysis products from PVC resin and plastisols

A pyrolysis–gas chromatographic–mass spectrometric technique for analyzing the pyrolysis products from polymers in an inert atmosphere is described. Initial studies encompassing the pyrolysis of poly(vinyl chloride) homopolymer and a series of PVC plastisols (based on o-phthalate esters) have provided a complete qualitative and semi-quantitative analysis of the pyrolysis products from these materials. PVC resin yields a series of aliphatic and aromatic hydrocarbons when pyrolyzed at 600°C; the amount of aromatic products is greater than the amount of aliphatic products. Benzene is the major organic degradation product. A typical PVC plastisol [PVC/o-dioctyl phthalate (100/60)] yields, upon pyrolysis, products that are characteristic of both the PVC matrix and the phthalate plasticizer. The pyrolysis products from the plasticizer dilute those from the PVC portion of the plastisol and are, in turn, the major degradation products. There are no degradation products resulting from an interaction of the PVC with the plastisol. The pyrograms resulting from pyrolysis of the various plastisols of PVC can be used for purposes of “fingerprinting.” Identification of the major peaks in a typical plastisol pyrogram provides information leading to a precise identification of the plasticizer. The pyrolysis data from this study were related to a special case of flammability and toxicity.     

An overview on the recent developments in reactive plasticizers in polymers

This review is about the reactive plasticizer. Plasticizers are small molecules with low molecular weight. These compounds typically have an esteric structure. The plasticizers reduce the glass transition temperature, and the viscosity of the polymer also enhances the flexibility and processability of polymer materials. The main problem of these additives is that, over time, they migrate from the polymeric matrix and exude to the surface of polymeric matrix. As a result, the physical and mechanical properties of the polymer are affected. Various strategies, such as increasing molecular weight of plasticizer, selection of oligomeric structure for plasticizer, and adding nanoparticles of minerals, have been investigated to reduce and eliminate migration. An approach that has recently been of great interest to researchers is the use of reactive plasticizers. In this approach, plasticizers covalently bond to the polymeric chains and prevent migration.     

Rheology of PVC Plastisol: Particle Size Distribution and Viscoelastic Properties

Plastisols of poly(vinyl chloride), PVC, are suspensions of fine particles in plasticizer with about 50% resin volume fraction. Typically, the gross particle size ranges from 15 to 0.2 &mgr;m and smaller, where the common practice of spray-drying these resins and subsequent grinding of larger particles dictate the size ranges including agglomerates as well as the primary particles. The plastisol is a pastelike liquid, which may be spread to coat substrates. The coated substrates are heated in an oven to gel and fuse the material for producing uniform, rubbery products. Because the first step of processing is spreading the plastisol on a substrate, rheology at room temperature is obviously important. The material is thixotropic under very low stress. The flow behavior is pseudoplastic and exhibits dilatancy and fracture at high shear rate. This work is concerned with the pseudoplastic behavior but the dynamic mechanical measurements are employed instead of the usual steady-state shear flow measurements. This is because the steady shear may break up agglomerates. The dynamic measurements with small strain-amplitude avoid the break-up of the agglomerates. This is important, because this work is concerned with the effects of the particle size distribution on the material behavior. The frequency dependence of both viscous and elastic behavior is recorded and presented with samples varying in particle size distribution. Copyright 2001 Academic Press.     

Performance evaluation of new plasticizers for stretch PVC films

Six stretch PVC films have been formulated to have Shore A hardness of approx. 80 and nominal thickness of 15 μm with the aim of evaluating the performance of plasticizers from renewable and non-renewable sources for stretch PVC films intended to be employed as packaging. The reference film was produced with DEHA and ESBO, while the other films were produced with conventional plasticizers (ATBC and Polyadipate), new plasticizers from renewable sources (Mixture of glycerin acetates and Acetic acid esters of mono- and diglycerides of fatty acids) or a plasticizer employed in toy and childcare applications (DEHT) as a third plasticizer. The films were evaluated as to their physical and mechanical properties (durometer hardness, tensile strength and elongation), IR spectroscopy and light transmission. The several plasticizers influenced the mechanical properties of the PVC films to different degrees. All films will probably show adequate performance when used in packaging applications. Nevertheless, the vegetable oil-based plasticizers showed better mechanical performance than the other plasticizers when compared to DEHA.     

Influence of plasticizer content on the transition of electromechanical behavior of PVC gel actuator

The actuation performance of plasticized poly(vinyl chloride) (PVC) gel actuators in an electric field depends on their chemical composition and electrical and mechanical properties. The influence of plasticizer (dibutyl adipate) content on electromechanical behavior of PVC gels was investigated by impedance spectroscopy and space charge measurement. By plasticizing the PVC, the dielectric constant and space charge density of PVC gel were drastically increased at 1:2 w/w ratio of PVC to plasticizer. To apply the results obtained from the impedance spectroscopy and space charge measurement, electrostatic adhesive forces generated between the PVC gel and the anode were measured. The electrostatic adhesive force at the anode was also dramatically increased at the same plasticizer content. All of the results indicated a transition of electromechanical behavior of PVC gel in the electric field, which was considered to originate from the orientation of polarized plasticizer molecules and dipole rotation of PVC chains. By using the electrostatic adhesive force of PVC gel derived from the electromechanical transition, a new electroactive actuator can be developed for novel applications.