改进的扩散自由体积模型及其在凝胶和固定化细胞中的应用(Ⅰ)模型的建立

利用扩散自由体积模型,通过一定的线性假定将凝胶及固定化细胞中的自由体积与各主要影响因素相联系,得到了能表达诸因素对有效扩散系数影响的改进的扩散自由体积模型.其特点是不仅能反映凝胶总单体浓度、交联度及扩散分子大小的影响,而且可以反映温度及细胞浓度对有效扩散系数的影响.     

改进的扩散自由体积模型及其在凝胶和固定化细胞中的应用(Ⅱ)实验数据的关联

应用本文(I)报建立起来的改进的扩散自由体积模型,对聚丙烯酰胺凝胶及其固定化酵母细胞中葡萄糖和(或)乙醇的有效扩散系数与凝胶的单体浓度、交联度、温度和细胞浓度分别进行关联,定性解释和定量关联都令人满意,说明了该模型的适用性.     

改进的扩散自由体积模型及其在凝胶和固定化细胞中的应用(Ⅱ)实验数据的关联

应用本文(I)报建立起来的改进的扩散自由体积模型,对聚丙烯酰胺凝胶及其固定化酵母细胞中葡萄糖和(或)乙醇的有效扩散系数与凝胶的单体浓度、交联度、温度和细胞浓度分别进行关联,定性解释和定量关联都令人满意,说明了该模型的适用性.     

聚丙烯酰胺凝胶及其固定化细胞扩散性能的研究

应用自行设计的扩散池,以稳态操作方式测定了聚丙烯酰胺凝胶单体浓度、交联度、聚合温度、扩散温度、组分浓度、酵母细胞浓度等对葡萄糖和/或乙醇在聚丙烯酰胺凝胶及其固定化细胞中有效扩散系数的影响。并得到了有效扩散系数与各因素间的关联式。     

用Simha-Somcynsky状态方程改进高分子中溶剂扩散系数模型

将Simha-Somcynsky状态方程和Vrentas-Duda的自由体积理论模型相结合，提出改进的高分子中溶剂扩散系数模型.改进的模型利用状态方程和WLF理论定义的自由体积分数确定扩散过程的有效自由体积，避免原模型中繁琐的黏弹性实验测定.对苯、甲苯、乙苯、氯仿在聚苯乙烯、聚异丁烯和聚醋酸乙烯酯中的扩散系数的计算结果表明，改进模型的预测值与实验值取得较好一致，且自扩散系数的预测精度比原模型高.同时，改进的模型能够反映压力对扩散系数的影响.溶剂扩散系数随外界压强增加而减小，当溶剂浓度较低时，压强的影响非常显著，扩散系数可相差几个数量级.随着溶剂浓度升高，扩散系数接近常压时的扩散系数，压强影响可以忽略.     

用状态方程改进的高聚物中溶剂扩散系数预测模型

将Simha-Somcynsky状态方程引入Vrentas-Duda自由体积理论模型,提出改进的高聚物-溶剂体系扩散系数模型,计算常压下橡胶态高聚物中有机溶剂扩散系数对浓度和温度的依存关系.利用高聚物结构单元的范德华体积导出高聚物自由体积分数表达式,通过Simha-Somcynsky方程求取高聚物体积以及对溶剂分子扩散有效的自由体积,避免原模型中繁琐的高聚物粘弹性实验测定和回归高聚物自由体积参数,提高了自由体积理论的预测能力.使用改进的模型预测了苯、甲苯、乙苯和三氯甲烷在聚苯乙烯、聚异丁烯和聚醋酸乙烯酯中的自扩散系数和互扩散系数,计算结果表明改进的自由体积模型具有较高的预测精度.     

自由基聚合/扩散动力学模型与仿真

基于自由体积和反应动力学理论,考虑了非稳态过程“笼蔽效应”对引发效率的影响,大分子自由基质心扩散、链段重排扩散、反应扩散对速率常数的影响,聚合物系体积变化对浓度的影响,松弛效应对于自由体积的影响.建立了自由基聚合动力学模型,并就苯乙烯本体聚合作了仿真验证.     

非离子型凝胶球在水中的溶胀行为

以过硫酸铵和N,N,N',N',-四甲基乙二胺氧化-还原体系引发丙烯酰胺聚合,制备球状非离子型水凝胶.利用带刻度的显微镜记录了凝胶球在水中的溶胀扩散过程,采用Tanaka-Fillmore凝胶溶胀动力学模型进行数学处理,得到凝胶网络扩散系数.在此基础上,进一步考察了交联剂、引发剂、单体浓度对凝胶网络扩散系数的影响,结果表明:随着交联剂用量的提高,扩散系数先变小后增大;增加引发剂﹑单体浓度,扩散系数均增大.对凝胶网络扩散系数-温度理论模型进行修正,更加符合实验结果,可用于凝胶网络扩散系数的预测.     

非电解质溶液扩散系数的理论研究评述

许多过程都涉及扩散控制的传质,相应的扩散速率计算对过程工程的精确量化具有重要意义.本文简述了扩散速率的理论表述模型,并着重介绍了非电解质溶液内扩散系数的理论分析计算途径.分子动力学模拟正处于发展中,并用于估算自扩散系数,但进入实用化阶段尚需时日,唯象模型仍为最重要的理论计算手段.作为最常用的方法,由无限稀释浓度下的扩散系数以及合适的插值方法可计算特定浓度下的扩散系数;自由体积理论是半经验性模型,可以计算自扩散系数,并借助混合规则计算相互扩散系数;最后,对扩散系数的理论研究作了展望.     

包埋紫草细胞的海藻酸钙凝胶扩散性能

用非稳态法测定了充分搅拌条件下在未包埋紫草细胞和包埋紫草细胞的海藻酸钙凝胶珠粒体系内蔗糖溶液浓度的瞬间变化情况。结果表明，海藻酸钠浓度、氯化钙浓度和紫草细胞包埋量对蔗糖扩散有明显影响，有效扩散系数Ｄｅ随着海藻酸钠浓度、氯化钙浓度和紫草细胞包埋量的提高而下降．     

Mathematical modelling of protein diffusion in microcapsules: A comparison with experimental results

The objective of this study was to develop a general diffusion model for describing mass transport phenomena and membrane diffusivities in alginate—polylysine (PLL) microcapsules. Good agreement between calculated and experimental protein concentration profiles was obtained based on a microcapsule model, consisting of a capsule membrane containing a partially impermeable alginate gel core with a decreasing gel pore size towards the centre of the capsule. The apparent size of the impermeable gel core and the capsule membrane permeability were directly dependent on the size of the diffusing protein and the alginate-PLL reaction time. The presence of this impermeable core may hinder the commercial and clinical use of these microcapsules in cell culture engineering and cell transplantation by affecting cell viability.     

Modeling of Fouling in Three Ultrafiltration Cell Configurations: Swirl,Plane and Axial Annular

Membrane fouling is a complex phenomenon induced by various chemical or physical factors. Several models can be used in order to predict flux. In this paper, models extracted from the literature are compared with experimental data collected in our laboratory during ultrafiltration of bentonite suspensions for three different cell designs (a classical plane unit and two annular units, one fitted with a tangential inlet inducing a swirling decaying flow, the other generating a pseudo axial flow). Mass transfer coefficients are measured by means of an electrochemical method for the two axial cell designs and are further included in the gel model predicting the limiting ultrafiltration flux. In ultrafiltration, the particles retained by the membrane will accumulate in the immediate vicinity of its surface to form a layer of higher particle concentration involved in the gel model. This concentration is also determined experimentally. Nevertheless, the gel model is not able to predict the permeation flux during ultrafiltration of bentonite suspensions in different cell designs. A modification of the erosion model, which takes into account the cell configuration, is also presented.     

Compression-Permeability Properties of Compressed Bed of Superabsorbent Hydrogel Particles

The average pore size of the gel network of a superabsorbent hydrogel particle was evaluated based on the data of the permeation rate of water through the compressed bed of gels obtained with the use of a compression-permeability cell (C-P cell). The pore size evaluated based on the Happel's cell model using the C-P cell data was compared with that obtained from the Kozeny-Carman equation in which the Kozeny constant k was assumed to be 5.0. It was clarified that the use of k = 5.0 in Kozeny-Carman equation underestimated the pore size compared to the calculations using the Happel's cell model. Moreover, the effect of bound water in the gel was clarified.     

Compression-Permeability Properties of Compressed Bed of Superabsorbent Hydrogel Particles

The average pore size of the gel network of a superabsorbent hydrogel particle was evaluated based on the data of the permeation rate of water through the compressed bed of gels obtained with the use of a compression-permeability cell (C-P cell). The pore size evaluated based on the Happel's cell model using the C-P cell data was compared with that obtained from the Kozeny-Carman equation in which the Kozeny constant k was assumed to be 5.0. It was clarified that the use of k = 5.0 in Kozeny-Carman equation underestimated the pore size compared to the calculations using the Happel's cell model. Moreover, the effect of bound water in the gel was clarified.     

A kinetic study on calcium alginate bead formation

Ca-Alginate-Gel is one of the most widely used carriers for cell entrapment. Since gel formation can take place under mild conditions, entrapment in this matrix is very suitable for immobilization of viable cells and it has found most extensive application. Despite of the extended use there have been no kinetic data related to gel formation of alginate with calcium ion. In the present work the kinetic study was accomplished to more fully elucidate the transient structure transformations involved in the gel formation using stirinking-core model. The proposed kinetic model may be successfully extended to account for the transient behavior and complete gelling time as well as some useful information of the gelling conditions in the process of Ca-Alginate-Gel.     

Swelling effect of a polymer electrolyte membrane on the development of a semi-empirical cell voltage model

We developed a new cell voltage model which depends on the current density response of the proton exchange membrane fuel cell (PEMFC). The proposed model focuses on the conductivity of a PEMFC fuel cell. The model for conductivity of a polymer electrolyte membrane, Nafion, uses the thermodynamic function to represent water activity. We observed membrane conductivity by monitoring the chemical potential of the swelling of the hydrogel. The swelling equilibrium of the ionized hydrogel is governed by the free energy of mixing, the free energy of elasticity, and the concentration of counterions with fixed charges on the gel network. A cell voltage equation with reasonable boundary conditions, including the swelling effect, which plays a major role in determining the cell voltage of a PEMFC, was newly developed.     

Modelling of phenol biodegradation by Candida tropicalis immobilised in alginate gel beads

Phenol‐degrading yeast Candida tropicalis were immobilised in alginate gel beads and photographed by scanning electron microscopy. Batch phenol biodegradation experiments were done in shaking flasks under varying conditions such as initial phenol concentrations and bead loadings. A mathematical model was proposed to simulate the batch phenol biodegradation process in the immobilised system, which took into account the internal and external mass transfer resistances of phenol and oxygen and the double‐substrate phenol–oxygen intrinsic kinetics. The validation of this model was done by the comparison between the model simulations and the experimental measurements of phenol concentration profiles in the main liquid phase. Moreover, the time and radius courses of phenol, oxygen, and cell concentration profiles within the alginate gel beads were reasonably predicted by the proposed model.