一种研究Aa型缩聚反应体系的新方法

应用统计力学基本原理, 从两种不同角度构造了Aa型缩聚反应的正则配分函数, 得到了体系的平衡自由能以及质量作用定律的解析表达式, 提出了获得数量分布函数的两种新方法. 进一步基于数量分布函数的不变性, 给出临界点后溶胶相和凝胶相的平衡自由能, 证明溶胶-凝胶相变是一类几何相变, 而非热力学相变.     

高分子凝胶的体积相变

本文概要地介绍了高分子凝胶体积相变的基础理论,较系统地综述了近10年来利用温度、pH值、光、电、生化反应等控制体积相变研究的进展,对有关的应用也作了简单的介绍.     

含引发机制A_2 十A_a型缩聚反应的溶胶-凝胶分配理论

讨论了含引发机制的A_2+A_a型缩聚反应体系,给出了该体系溶胶-凝胶分配公式,凝胶化条件,数量分布函数,并证明了数量分布函数的不变性质.     

溶胶-凝胶法制备二氧化钛溶胶

以钛酸丁脂为前驱体,乙醇为溶剂,采用溶胶-凝胶法制备了二氧化钛(TiO2)溶胶.最佳制备条件为:钛酸丁脂29 mmol,n(水):n(钛酸丁脂)=5:1,n(乙醇):n(钛酸丁脂)=15:1,pH 3～4,聚乙烯醇2 mL,于室温剧烈搅拌下缓慢加料制得透明度较好,可长时间放置,粘度适于涂膜的TiO2溶胶.     

溶胶-凝胶法制备氧化铝光学薄膜

氧化铝薄膜性能优异,具有较高的介电常数、高热导率、抗辐照能力强、抗碱离子渗透能力强以及在很宽的波长范围内透明等性能。因此,氧化铝薄膜广泛地应用于微电子器件、电致发光器件、光波导器件以及抗腐蚀涂层等众多领域[1]。特别是氧化铝光学薄膜具有高的抗激光损伤阈值[2],用     

溶胶—凝胶法合成稀土铁氧体过程中的相变与形成机制

利用元素相态分析,X射线衍射分析和红外光谱分析等多种测试技术对溶胶－凝胶法合成稀土六方铁氧体过程中的相态变化进行剖析,并对掺加La后稀土铁氧体的形成机制初步探讨。干凝胶在焙烧过程中,由金属柠檬酸配合物发生碳酸铁,Fe2O3与铁酸钡,六方铁氧体和γ-Fe2O3等相变反应,La3＋晶格位置的同时,通过缺陷结构发生电荷转移,使Fe^3 还原成Fe^2 ,从而达到电荷平衡。     

聚电解质凝胶的结构与体积相变

N,N-二甲基丙烯酰胺分别与2-丙烯酰胺-2-甲基丙磺酸或丙烯酸钠经自由基共聚,合成了聚电解质凝胶DS50和DA50,交联剂为N,N’-亚甲基双丙烯酰胺。比较了DS50与DA50在不同pH值的缓冲溶液和不同组成的水-丙酮混合溶液中的溶胀特性,并观察到两种凝胶在水-丙酮混合溶液中都会发生体积相变,在上述两类溶液中DS50的溶胀比都比DA50大。测定了未溶胀的DS50的动态贮能模量G′和损耗模量G″,发现G′不随应变和角频率变化,讨论了平衡剪切模量Ge与凝胶中分子链密度的关系。同时还发现,将DS50在纯水中溶胀平衡时的有关实验数据代入Flory的凝胶状态方程并不能得到合理的相互作用参数值。     

溶胶-凝胶法制备Bi-Pb-Sr-Ca-Cu-O微粉

以金属醋酸盐为原料,用溶胶-凝胶技术制备了Bi-Pb-Sr-Ca-Cu-O微粉,并用TG、DTA、IR、XRD和TEM等手段对Bi_1.85Pb_0.35Sr_1.9Ca₂Cu_3.1O_y粉末的热分解和晶化行为以及粉末粒度进行了分析测试,并用此微粉制备出以2223相为主要物相、零电阻为105K的高温陶瓷超导体。     

溶胶-凝胶硫离子传感器的研制及应用

报道了溶胶 凝胶硫离子传感器的制备方法及其在硫离子检测中的应用。采用循环伏安法(CV)对传感器修饰过程进行了表征,对其电化学过程的可行性及其响应机理进行了探讨。传感器在6.0×10-7～1.0mol L范围内符合Nernst方程式,线性相关系数r=0.9991,方法的检出限为2.0×10-7mol L。于4℃干态保存4周,响应信号基本不变,已用于环境水样的分析。     

多标度分形热力学及其相变

用与热力学和统计物理相类比的方法,对多重分形引入了熵、自由能函数。这些函数对多重分形的几何特性给出了充分的描述。同时按照热力学相变理论刻画了多重分形谱函数的非解析性及相变。     

Ba1－xSrxTiO3的Sol-gel法制备与结构相变研究

采用sol-gel法制备了钛酸锶钡(Ba1－xSrxTiO3)．用XRD、DSC、Raman等表征技术研究了Ba1－xSrxTiO3的晶体结构和相变行为.结果表明,随着锶含量的增加,晶胞体积逐渐减小,c/a趋近于1,相变温度降低,相变热减少,相变弥散性增强,且存在热滞现象.Raman光谱发生有趣变化,当x=0.30时,室温下发生结构相变, Ba1－xSrxTiO3以立方相为主要存在相,相变具有有序-无序特征.     

溶剂效应与海藻酸钠溶液溶胶-凝胶相转移

以溶质、溶剂间的协同作用作为高分子电解质体系的凝胶化条件，以松软粒子结构（Blob）间的三维修滤过程作为体系的凝胶化模型，从而将高分子电解质体系的凝胶化分为松软粒子的形成和渗滤过程．结合不同浓度海藻酸钠溶液的Ca2＋离子深加体系的凝胶化，分析了高分子电解质溶胶-凝胶相转移的实质，得到了体系相对粘度的临界指数k＝0．90～0．97和相转移的临界点fc与聚合物浓度间的幂次关系fc～c-0.65，明确了临界点附近相对粘度的幂次公式ηrel∝（fc-f）-k的适用范围．     

Sol-gel Transition of Methylcellulose Solution in the Coexistence of Hexadecyltrimethylammonium Bromide and Sodium Chloride

The sol-gel transition of methylcellulose (MC) solution in the presence of NaCl and hexade-cyltrimethylammonium bromide (HTAB), together with MC/NaCl solution in the presence of HTAB and MC/HATB solution in the presence of NaCl, was investigated by the rheolog-ical measurements. It has been found that the sol-gel transition temperature of MC solution decreases linearly with the concentration of NaCl in solution but increases linearly with the concentration of HTAB in solution, respectively. However, the sol-gel transition temperature of MC/NaCl solution in the presence of HTAB keeps the same value, independent of theconcentration of HTAB in solution. On the other hand, the sol-gel transition temperature of MC/HTAB solution decreases linearly with the concentration of NaCl in solution. The experimental results suggest that, for MC/NaCl solution in the presence of HTAB, the salt-induced spherical micelles of HTAB should have formed in bulk solution. For MC solution in the absence of NaCl, no spherical micelles have been formed in bulk solution, though the concentration of HTAB in our experiment is almost one order of magnitude higher than the critical micelle concentration of HTAB in polymer-free solution. In fact, due to adsorption of HTAB on MC chains, the realconcentration of HTAB in bulk solution, is much less than the apparent concentration of HTAB dissolved in MC solution.     

用荧光光谱跟踪钙-海藻酸水溶液的Sol-gel转变

为了克服传统方法在测定凝胶化点的同时, 作用力对物理交联点的破坏和对大分子链运动的干扰, 探索和建立不施加应力的凝胶化点测定方法, 采用荧光光谱跟踪了异硫氰酸荧光黄(FITC)标记海藻酸与钙离子在水溶液中螯合的物理凝胶化. 随着凝胶化的进行, 荧光相对强度和各向异性比在凝胶化时间曲线的80 min时出现了明显的转折点, 与Winter方法得到的凝胶化点(80 min)完全一致. 因此可以利用FITC标记的荧光发射相对强度及各向异性比来决定钙-海藻酸体系凝胶化点.     

A New Method to Study the Sol-gel Transition Process of Organic/Inorganic Hybrid Materials

The sol-gel transition process of PMMA/SiO2 hybrid materials was first studied by means of the dynamic torsional vibration method. The different stages of the transition can be described by the change of torque. The temperature-dependent measurement of the gel time（ tg ） gives the possibility to determine the apparent activation energy.（ Ea ） of this transition according to Flory＇s gelation theory. The non-equilibrium thermodynamic fluctuation theory was used to predict the transition behavior. The isothermal transition experiments on hybrid sols with different TEOS（tetraethyl orthosilicate） contents were carried out. The results show that the Ea of a hybrid sol is higher than that of a non- hybrid sol of a TEOS-water-ethanol system. The increasing of TEOS content in a hybrid sol has no obvious effect on the Ea value, but it can enhance the sol-gel .reaction rate.     

On the Contraction Factor of Star‐Branched Polymers with Flory‐Distributed Arms

More than fifty years ago, Zimm and Stockmayer calculated the average contraction factor of star‐branched polymers (stars) with uniformly distributed arms to be 6f/{(f + 1)(f + 2)}. Since then this contraction factor has also been used for stars with other arm distributions. In this paper we determine the (probability) density function of the contraction factor of stars with arms with a Flory (most probable) distribution and conclude that this function is equal to that for stars with uniformly distributed arms. Other arm distributions, however, lead to different contraction factor density functions. The moments of the contraction factor distribution were precisely determined with the aid of a recursion method. The stochastical behavior of the contraction factor of stars was applied to size‐exclusion chromatography (SEC) analysis and showed that upward correction of the crude SEC data is necessary to determine the proper molecular‐mass distribution of stars.     

Span‐Length Distributions of Star‐Branched Polymers

Many relations between the physical, rheological or mechanical properties of linear polymers and their molar mass are well known. For disperse polymers, parameters that express these relations are typically related to (a combination of) the moments of the molar‐mass distribution. Properties of branched, nonlinear polymers have been far more difficult to describe in the form of general relations. Monodisperse star polymers or regular stars, with a distinct number of arms and equal arm length, are the simplest member of the family of branched polymers and have served as model compounds in many studies. For these regular stars, the relation between zero shear viscosity and arm or span length has been determined. To establish equivalent relations for disperse star‐branched polymers, it is important to assess the span‐length distribution and its moments; these parameters can be calculated when the distribution of the molar mass of the arms of a star‐branched polymer is known, for instance, for a known polymerization mechanism.

Span‐length probability functions of star‐branched polycondensates with x_n = 100: f = 1 (•), f = 2 (○), f = 3 (▪), f = 5 (□), and f = 10 (+).     

Predicting MWD and Branching Distribution of Terminally Branched Polymers Undergoing Random Scission

A new semi‐analytical approach to model simultaneous chain scission and branching is described that assumes the separation of the scission and the branching problem. The required properties of the linear segments or primary polymers forming the branched architectures are found by a kinetic model. The general rules for the construction of branched architectures from populations of linear segments then lead to an analytical expression for the branching distribution and a semi‐analytical expression for the bivariate length/branching distribution. The method is applied to the scission of an initially branched polymer and subsequent terminal branching on scission points and activated terminal double bonds. Exact agreement is found with Monte Carlo sampling results.

     

Af+AB星型聚合体系的统计热力学

应用统计力学和热力学原理研究了 A_f+AB星型聚合体系的性质. 首先从两种不同的角度给出了与聚合反应相应的配分函数, 并据此得到反应体系的平衡自由能、质量作用定律及数量分布函数, 进而得到了体系的平衡状态方程和比热. 在此基础上, 以反应体系的回转半径为例研究了溶剂效应对星型高分子空间尺度的影响.