梳状聚合物电解质的力学松弛时间

以苯乙烯 /马来酸酐共聚物为骨架 ,聚乙二醇单甲醚为侧链合成了 3种不同侧链长度的梳状高分子聚合物 ,制成了锂盐络合物薄膜 .动态力学性能研究结果表明 ,本体系是主链刚性、侧链较柔软的梳状接枝聚合物 .应用时间温度等效原理 ,选择Tα 作为参考温度 ,建立了主曲线 ,得到了移动因子图和等自由体积图 .Williams、Landel和Ferry(WLF)经验方程的两个参数C1、C2 随着盐浓度增加而增大 .若T0 =50℃作为参考温度 ,平均松弛时间lgτc 与锂盐浓度C呈线性关系 .随着侧链分子量增加 ,主曲线向高频率移动 ;平均松弛时间lgτn 与侧链分子量的关系也是线性的 ;另外随着盐的不同 ,主曲线也会产生移动 ,表明盐种类对松弛时间产生影响 .     

密封橡胶材料的压力-体积-温度关系的研究

制备了3种密封胶材料——丁苯橡胶、丁腈橡胶及丁腈/氯化丁基混合橡胶材料,利用压力-体积-温度(P-V-T)高压膨胀计对样品进行测试,得到了比容Vsp随着温度T和压力P变化的关系;采用Tait方程研究了P-V-T性能,并计算出Tait方程中相应的参数.结果表明,Tait方程计算所得的P-V-T理论关系与实验结果一致,具有较好的规律性;b3、b4均为常数,即B为常数;Tait方程计算所得值与实验值的平均残差均小于0.02,吻合度较好;因此Tait方程可以较好地描述3种密封橡胶体系的P-V-T关系,并且为定量研究密封橡胶材料的P-V-T关系提供理论基础.同时,根据Tait方程所得的参数,计算了3种橡胶材料的热膨胀系数α和等温压缩系数β,研究了3种橡胶材料的α和β随着压力、温度的变化规律,结果表明3种材料中丁苯橡胶的尺寸稳定性最好,而丁腈/氯化丁基复合橡胶的尺寸稳定性较差并且其α随着压力的变化有较大的改变.准确地描述了3种密封橡胶材料的α和β随压力、温度的变化.     

受限状态聚合物熔体的分子动力学模拟

用粗粒化的分子动力学(MD)模拟方法从分子层次研究了受限于粗糙壁内的聚合物熔体的动力学性质. 结果表明, 对于链长较短的受限聚合物熔体体系, 随着膜厚的增加, 体系内部高分子链的松弛时间逐渐减少; 然而对于链长较长的受限体系, 聚合物链的松弛时间随着膜厚的增加先减少后增加. 推测这种由于链长的变化所引起的动力学性质的差异源自受限熔体内聚合物链聚集状态的改变, 并且通过考察交叠参数对这种改变进行了分析. 结果表明, 在膜厚增加的过程中, 决定受限状态高分子长链松弛机理的因素逐渐从受限效应转变成为链间的缠结效应.     

苯乙烯基形状记忆聚合物热力学行为的有限元分析

对苯乙烯基形状记忆聚合物进行了拉伸实验研究,测定了该材料在25℃、30℃、40℃和50℃时的弹性模量和屈服极限.根据实验结果,建立了苯乙烯基形状记忆聚合物的材料参数方程,描述了苯乙烯基形状记忆聚合物在玻璃体转化过程中,材料参数和温度的关系.在假设形状记忆聚合物为各向同性材料的基础上,将Tobushi等建立的热力学本构方程从一维扩展到三维.基于有限元分析软件ABAQUS的二次开发功能,针对上述本构方程和材料参数方程,编写了可供ABAQUS调用的UMAT函数,并对苯乙烯基形状记忆聚合物实现形状记忆效应的高温变形、应力冻结和形状恢复等热力学过程,进行了有限元数值模拟分析.     

用TMS—2型热机分析仪测量热释蠕变

对已经商品化的Perkin-Elmer TMS-2型热机分析仪进行改进,用来测量聚合物材料的热释蠕变行为。按照7SCr分步加载的程序,用弯曲法测量了-83～300℃温度范围内低密度聚乙烯的玻璃化转变松弛过程,并从TSCr谱上计算其相应的分子参数,实验结果与用扭转的TSCr方法所得结果相等,因此这是一种研究聚合物材料松弛行为的方便可行的技术。     

聚合物薄膜玻璃化转变及其分子松弛行为的研究进展

随着纳米技术的发展,受限聚合物的玻璃化转变以及分子松弛行为受到了高分子物理学家的关注.由于纳米尺度效应,高分子薄膜的玻璃化转变以及分子松弛行为偏离于本体,呈现出尺寸依赖性.研究聚合物薄膜的玻璃化转变及其相关分子松弛行为对聚合物纳米材料的结构设计,进一步理解聚合物玻璃化转变的物理本质具有重要意义.本文总结了近20年来聚合物薄膜玻璃化转变行为的研究成果,介绍了薄膜分子松弛行为偏离本体的主要物理机制、聚合物薄膜分子运动能力的深度分布特征以及薄膜分子松弛行为的相关理论模型,并对该领域研究进行了展望.     

基于黏弹模型的聚合物溶液相分离的三维数值模拟

利用GPU加速技术实现黏弹模型的三维数值模拟,系统研究了中等浓度聚合物溶液的分相形貌和相分离动力学.模拟结果表明本体应力的不对称是体系出现相反转的重要原因.与实验观察的聚合物溶液相反转的演化过程一致,首先聚合物富集相形成网络结构,然后聚合物网络收缩断网,最后变为离散的液滴相.本体松弛模量的增加,一方面会抑制相分离初期的浓度涨落,导致相反转发生时间延迟;另一方面在相分离后期有助于形成大的聚合物富集液滴相,加速相区增长.剪切松弛模量的增加只有助于聚合物富集相保持网络结构,并在剪切松弛模量较大的情况下,不规则相结构的缓慢松弛导致了剪切应力在相分离后期长期存在.     

樟脑分子印迹整体柱的制备及性能评价

利用原位聚合法制备了樟脑分子印迹整体柱作为液相色谱固定相,通过优化制备条件和色谱条件,得到了对模板分子有较高保留性能的整体柱。采用前沿色谱分析法测定柱容量,得到有效结合位点Bt=1.815×102mmol/g和解离常数Kd=9.064 mmol/mL。Van’t Hoff方程得到的热力学参数焓值和熵值,说明了聚合物对樟脑的吸附为熵增过程。等温吸附模型证明在该聚合物表面只存在一种结合位点。     

盐酸雷尼替丁分子模板聚合物的分子识别特性

采用分子印迹技术合成了对药物雷尼替丁有高度选择性的模板聚合物。通过Scatchard方程和紫外光谱分析研究了模板聚合物的结合特性。结果表明,其结合位点的解离常数为Kd=2.679×10-3mol/L。底物的选择性结合实验表明,其模板聚合物对盐酸雷尼替丁有较大的吸附性和高度的选择性及识别能力。     

一种研究聚合物非等温结晶动力学的方法

作者基于多年对聚合物结晶动力学方面研究的工作积累,联合Avrami方程和Ozawa方程,提出了一种研究聚合物非等温结晶动力学的新方法.该方法既克服了使用Ozawa方程所获得的数据点过少,常常出现非线性,不能获得可靠的动力学参数的缺点,又克服了使用经Jeziorny修正的Avrami方程所获得的表观Avrami指数无法准确预测非等温过程成核生长机理的缺点.该方法已成功用于多种聚合物体系,被国内外学者引用数百次,已成为研究聚合物非等温结晶动力学一种有效方法.     

Experimental Equations of State for Some Organic Liquids Between 273 and 333 K and Up to 280 MPa

Abstract

Five non-linear and three polynomial isothermal equations of state for liquids have been tested for their performance in describing the data of the density and the isothermal compressibility of benzene and cyclohexane from 288 to 323 K up to the melting pressures, and of methanol and ethanol between 273 and 333 K up to 280 MPa. It is found that the best representation is given by an expansion in temperature and density and the second best by the Usual Tait equation. The coefficients of these two equations for the four organic liquids are obtained by fitting the experimental data by a least squares analysis.     

A novel method for static equation-of state-development: equation of state of a cross-linked poly(dimethylsiloxane) (PDMS) network to 10 GPa

Pressure-volume-temperature (PVT) equation-of-state (EOS) information for polymers and polymeric composites is valuable for predicting their response to extreme conditions. An obstacle in determining equations of state for polymeric materials is the lack of a simple, static experimental method for acquiring PVT data for solid networks and liquids at pressures greater than several kilobars. Here, we report a novel approach in determining static EOS for polymers using high-pressure diamond-anvil cells coupled with optical microscopy and image analysis. Results are presented for a cross-linked poly(dimethylsiloxane) polymer, Sylgard 184. Static isothermal results were fitted to empirical and semiempirical equations of state, including the Tait, Birch-Murnaghan, and Vinet forms. Static PV data were also converted to pseudoshock velocity-pseudoparticle velocity (U(s)-u(p)) for comparison to dynamic Hugoniot data. A linear Rankine-Hugoniot fit U(s)=s(T)u(p)+c(T) gives c(T)=1.572 km/s and s(T)=1.703. s(T) is related to the pressure derivative of the bulk modulus B(0) (') by s(T)=(B(0) (')+1)/4 and B(0) (')=5.8. A comparison of the static and shock data is given, along with an estimate of the Grüneisen parameter, and a discussion of the free volume content in the polymer network, and limitations of this novel method.     

Modeling high-pressure densities at wide temperature range with volume scaling: Cyclohexane + n-hexadecane mixtures

High-pressure density data for cyclohexane + n-hexadecane mixtures at a wide temperature range was modeled with several classical equations of state (EOS) and correlative models. A modification for softening the co-volume and another for a volume scaling of the Peng–Robinson EOS (VS-PR) were proposed. The VS-PR model is able to correlate the pure component experimental data employing only five adjustable parameters, with root-mean-square deviation (RMSD) between calculated and experimental densities essentially within the experimental error. This result is superior to widely used approaches, i.e., a six parameter Tait model and six parameter volume translations (temperature and pressure dependent) for Peng–Robinson and Patel–Teja EOS. The VS-PR model also represents well the isobaric thermal expansion and the isothermal compressibility coefficients of the pure cyclohexane, a small naphthenic substance as well as a long chain n-alkane hydrocarbon, n-hexadecane. When modeling the mixture data, the use of VS-PR model of pure components along with the Redlich–Kister expansion, truncated at the first term, the density was correlated within a RMSD only 60% greater than the experimental error. The proposed model is able to accurately represent all the tested mixture data with a relatively small number of parameters.     

Equation of state and related properties of light and heavy waters and their mixtures

In this paper we have shown that the p—V—T measurements for light and heavy water systems can be represented with sufficient accuracy by the logarithmic form of the two parameter Tait equation. One of the parameters, which is dimensionless, turns out to be the same for both types of water. We make the plausible assumption that even for their mixtures this parameter has the same value. The other parameter can then be determined from the limiting isothermal compressibility which is obtainable with great precision from the speed of sound measurements at normal pressure. The p—V—T data for the water mixtures can thus be generated by using the Tait equation. This simple equation is very useful in the determination of the values of those thermodynamic functions which are not easily accessible to direct experimental measurements at elevated pressures. Lastly the principle of corresponding states is shown to be applicable for the two water systems.     

PVT properties of polyethylene copolymer melts

PVT properties of four polyethylene random copolymers (ethylene-propylene, ethylene-1-butene, ethylene-1-hexene, and ethylene-1-octene) and linear polyethylene were measured at temperatures from 313 to 493 K and pressures up to 200 MPa. Dependence of properties such as specific volume, thermal expansion coefficient, isothermal compressibility, and characteristic parameter of equations of state on the length of the polymer branched chains were examined. It was found that the length of the branched chain did not affect the thermal expansion coefficient and isothermal compressibility. The specific volume of copolymers having longer branched chains were slightly larger than those copolymers with short branched chains.     

Prediction of poly(oxymethylene) non-isothermal crystallization behaviour from isothermal data

The spherulite growth, nucleation-related,K _g, parameter values obtained from isothermal data (by DSC or optical microscopy) and two other adjustable parameters (the spherulite growth rate preexponential factor and the Avrami's or Tobin's exponent,n) have been used with Nakamura's and Tobin's modified non-isothermal equations to model the kinetics of polymer non-isothermal crystallization. Malkin's model was also tested, for comparison. It is shown that, for polymers that crystallize on cooling almost entirely at temperatures higher than the maximum growth rate temperature, this Tobin's-like non-isothermal model accurately describes the experimental behaviour with only 2 parameters.     

薄膜用聚丙烯树脂熔融态PVT行为的研究

利用PVT 10 0分析仪对 5种不同牌号的双向拉伸用聚丙烯 (BOPP)树脂的压力 体积 温度 (PVT)特性进行了测定 ,并利用Tait方程法得出BOPP熔体的热膨胀系数 (α)随温度和等温压缩系数 (β)随压力的变化关系 .研究结果表明 ,在相同条件下 ,牌号为S2 8C的BOPP熔体的热膨胀系数、等温压缩系数和结晶熔融温度分别低于其它牌号 ,因此 ,我们推断S2 8C在冷片形成过程中的体积形变较小 ,可避免由于收缩产生的模片表面缺陷 ,进而减少在后续双向拉伸过程中的破膜现象     

Temperature effects for isothermal polymer crystallization kinetics

We adopt the cluster size distribution model to investigate the effect of temperature on homogeneous nucleation and crystal growth for isothermal polymer crystallization. The model includes the temperature effects of interfacial energy, nucleation rate, growth and dissociation rate coefficients, and equilibrium solubility. The time dependencies of polymer concentration, number and size of crystals, and crystallinity (in Avrami plots) are presented for different temperatures. The denucleation (Ostwald ripening effect) is also investigated by comparing moment and numerical solutions of the population balance equations. Agreement between the model results and temperature-sensitive experimental measurements for different polymer systems required strong temperature dependence for the crystal-melt interfacial energy.     

Thermomechanical behavior of a polyphenylquinoxaline

Crosslinking of linear poly[2,2′-(1,4-phenylene)-6,6′-bis(3-phenylquinoxaline)] (PPQ) by isothermal heat exposure in the temperature range between 425 and 490°C was investigated by means of torsional braid analysis. The change in glass transition temperature due to isothermal exposure was used as a kinetic parameter. In order to determine the effect of molecular weight and type of polymer chain ends, three PPQ samples were prepared that differed only in molecular weight and polymer chain endgroups. The apparent activation energy of isothermal crosslinking was independent of molecular weight and chain endings. Its value of 60 kcal/mole is the same as that for the thermal degradation of PPQ (determined by isothermal weight loss measurements). The rates of change of T_g at a particular temperature, however, are a function of both molecular weight (at least for these polymers that do not have a sufficiently high molecular weight) and the type of polymer chain ends. It was observed that isothermally crosslinked PPQ gave a higher break point in the TGA curve and also an increased char yield at 800°C than the linear precursor.