Ethylene Polymerization over Supported Titanium-Magnesium Catalysts: Heterogeneity of Active Centers and Effect of Catalyst Composition on the Molecular Mass Distribution of Polymer

New experimental approach was used for analysis of molecular weight distribution (MWD) of polymers produced over titanium-magnesium catalysts (TMC). Polymers were fractionated on to fractions with narrow MWD (polydispersity (PD) values Mw/Mn ≤ 2). Then some of these fractions were combined to get the minimal quantity of fractions with PD values close to 2 (Flory components). It was found that three fractions corresponding to three groups of active centers are sufficient for proper fitting experimental MWD curve for PE obtained over TMC with different Ti content and with different hydrogen concentration in polymerization.     

Determination of the Mode of Free Radical Termination from Pulsed Laser Polymerization Experiments

The molecular‐weight distribution (MWD), obtained by pulsed laser polymerization (PLP) at the high termination rate limit has been considered for investigating termination kinetics. The proposed methodology takes into account both the composite model for termination and the chain‐length dependencies of propagation for short‐chain and long‐chain radicals. Power‐law expressions are used to represent propagation and termination of long‐chain radicals (where k and k represent the maximum “virtual” rate coefficients for monomeric radicals, and α and β capture the chain‐length dependencies for propagation and termination), with the combined value of (β − α) evaluated from the MWD, after correcting for the influence of the kinetics of short‐chain radicals. A novel method is also developed for determining the mode of termination, δ, from MWDs produced by PLP at the high termination rate limit. Simulations for methyl methacrylate (MMA) polymerization at 25 °C confirm that the method can be applied robustly in the presence of complicating factors such as chain transfer to monomer and SEC broadening. The analysis of an experimental MWD obtained for MMA polymerization at 25 °C results in estimates of 0.14 ± 0.03 for (β − α) and 0.75 ± 0.04 for δ.

     

Monte Carlo Simulation of Controlled/Living Radical Polymerization in Emulsified Systems

A new MC simulation method is proposed for the controlled/living radical polymerization in a dispersed medium, assuming an ideal miniemulsion system. This tool is used to consider the effects of particle size on the polymerization rates and the molecular weight distributions. For NMP, the polymerization kinetics are basically governed by two conflicting factors, (i) the confined space effect that promotes the coupling reaction between a radical and a trapping agent and (ii) the isolation effect of radicals into different particles that suppresses the overall frequency of bimolecular termination. For RAFT polymerization, a significant rate enhancement by reducing the particle size could be observed only for the systems with fast fragmentation of adduct radicals.

     

Hartmann共振管及超音速雾化喷嘴流场的数值模拟

采用基于Roe解法的有限体积法,对Hartmann共振管中的气体流场进行了数值模拟,研究了当喷嘴轴线处存在针型激励器的情况下流场的振动情况,数值计算的结果与理论和相关的实验结果符合得较好．计算结果表明移除或引入激励器,将会使Hartmann共振管的共振模式发生转换．通过对超音速雾化喷嘴流场的数值模拟,研究了其中Hartmann共振腔和二级共振腔共同作用下的振动现象以及各物理参数对振动的影响,并对喷嘴中气流从亚音速向超音速的转变机理进行了研究．     

PECVD低温制备微晶硅薄膜的研究

实验采用等离子体增强化学气相沉积(PECVD)法在玻璃衬底上制备了微晶硅薄膜.研究了氢稀释比、衬底温度、射频功率等因素对薄膜晶化的影响,得出在一定范围内随着衬底温度的升高、射频功率和氢稀释比的增大,薄膜的晶化率得到提高;但进一步提高沉积温度、射频功率反而会使薄膜晶化效果变差,并对晶化硅薄膜低温生长的机理进行了初步的探讨.     

新生儿脑部光学参数的无损检测

生物组织的光学参数与组织中各种生化、生理以及病理过程密切相关。利用频域近红外光谱技术,使用一个140 MHz的射频振荡源对不同波长的半导体激光管进行调制,通过精确测量距离光源一定距离处光子密度波的相位延迟和幅度衰减,并借助于一个光学参数已知的校准模型,实现了对23个新生儿头部组织光学参数的定量测量。并且根据两个波长(788和832 nm)下的吸收系数的测量结果进一步得到了新生儿脑部组织的生理学参数。实验结果表明,这种便携式的频域近红外光谱系统可以有效地获取新生儿头部的光学和生理学参数。     

含氟聚酰亚胺1,3-BPA-6FDA-DR1的合成及其热光性能

用1,3-双(3-氨基苯氧基)苯(1,3-BPA)、4,4′-(六氟异丙基)-苯二酸酐(6FDA)和分散红1(DR1)合成了含氟聚酰亚胺,采用示差扫描量热(DSC)、热失重分析(TGA)和紫外、红外吸收光谱等测试技术对该聚酰亚胺的热稳定性和结构进行了表征。结果显示,该聚酰亚胺的玻璃化转变温度(Tg)和在5%的质量损失温度分别为238和287℃,表明具有较好的热稳定性。不同浓度的材料在自然光下的热光系数(dn/dT)值为(-2.31～-3.04)×10-4/℃,体积热膨胀系数变化率(dβ/dT)为(2.56～4.32)×10-7/℃;一定浓度的材料在436nm单波长光照射下的热光系数(dn/dT)值为-3.08×10-4/℃,体热膨胀系数变化率(dβ/dT)为4.72×10-7/℃,表明该聚合物在低驱动功率的新型数字热光开关、光通信器件等领域具有潜在的应用前景。     

Cascadic Multigrid for Finite Volume Methods for Elliptic Problems

In this paper, some effective cascadic multigrid methods are proposed for solving the large scale symmetric or nonsymmetric algebraic systems arising from the finite volume methods for second order elliptic problems. It is shown that these algorithms are optimal in both accuracy and computational complexity. Numerical experiments are reported to support our theory.     

摄动有限体积法重构近似高精度的意义

研讨有限体积(FV)方法重构近似高精度的作用问题.FV方法中积分近似采用中点规则为二阶精度时,重构近似高精度(精度高于二阶)的意义和作用是一个有争议的问题.利用数值摄动技术[1,2]构造了标量输运方程的积分近似为二阶精度、重构近似为任意阶精度的迎风型和中心型摄动有限体积(PFV)格式.迎风PFV格式无条件满足对流有界准则(CBC),中心型PFV格式为正型格式,两者均不会产生数值振荡解.利用PFV格式求解模型方程的数值结果表明:与一阶迎风和二阶中心格式相比,PFV格式精度高、对解的间断分辨率高、稳定性好、雷诺数的适用范围大,数值地"证实"重构近似高精度和PFV格式的实际意义和好处.     

甘氨酸、L-丙氨酸和L-丝氨酸在尿素水溶液中的体积性质

蛋白质的折叠与解折叠、稳定性、变性行为和酶的活性等都受到环境中其它各种物质影响.作为蛋白质模型分子,氨基酸在混合溶液中的热力学研究近年来引起了广泛重视.尿素在生物体系中的独特地位主要表现在:它是水结构的破坏者,同时又是许多球状蛋白的变性剂.然而,尿素对球状蛋白的变性作用尚未达成共识.