环己烷在聚乙烯和聚异丁烯中无限稀释扩散系数 的测定

采用填充柱的反相气相色谱方法,基于Hadj-Romdhane-Danner色谱过程的数学模型,在323.2～363.2K温度范围内测定了环己烷在聚异丁烯和聚乙烯膜中的无限稀释扩散系数。从实验数据可以看出,环己烷更容易在PIB中发生扩散。对实测扩散数据进行了自由体积理论关联,结果表明,采用空穴自由体积替代Vrentas-Duda自由体积理论方程中自由体积项的修正方程能很好地描述溶剂分子扩散系数随温度的变化关系。     

痕量氯代甲烷在聚异丁烯中的扩散系数研究

采用填充柱反相气相色谱 ,基于 Hadj- Romdhane和 Danner所提出的扩散分子在色谱柱中扩散模型 ,分别测定了不同温度下痕量的三种氯代甲烷溶剂 :二氯甲烷、三氯甲烷和四氯甲烷在聚异丁烯膜 ( PIB)中的扩散系数。实验结果表明溶剂分子在聚异丁烯中的扩散系数与体系温度和溶剂的分子大小有关。在相同温度下 ,溶剂分子睦菠 ,扩散系数越大 ;温度越高 ,扩散系数越大。同时对所测数据用 Vrentas- Duda自由体积扩散系数方程进行了探讨 ,发现对于 PIB/ CCl4 体系 ,采用预测型 Vrentas- Duda方程计算所得不同温度下的值与实验数据相符 ,而对于PIB/ CHCl3体系计算偏差较大 ,该偏差产生于预测方程中忽略了能量效应。     

四臂星形聚苯乙烯在良溶剂和0溶剂中分子扩散的光子相关光谱的研究

用光子相关光谱研究了四臂星形聚苯乙烯在良溶剂(四氢呋喃THF)和θ溶剂(环己烷CH)中扩散系数与溶剂的浓度和温度的依赖关系。用累积量方法分析光子相关数据给出了多分散样品的Z均扩散系数。在θ溶剂中,高于或低于θ温度时,聚合物在溶液中的分子扩散分别表现出具有在良溶剂与不良溶剂中的行为。外推浓度至零,得到无限稀时不同温度的分子扩散系数,借助Stokes-Einstein方程,给出了聚合物的流体力学半径。通过InD对I/T作图,得到了星形聚苯乙烯在THF与CH中的扩散活化能。     

苯乙烯—二乙烯基苯共聚超微球在溶液中的扩散行为

用光子相关光谱测定了苯乙烯-二乙烯基苯(St-DVB)共聚超微粒在良溶剂(甲苯)与θ溶剂(环己烷)中不同温度下的分子扩散系数,与流体力学方程结合给出了该微粒在无限稀时的等效流体力学半径。微粒分子扩散与温度的关系符合Arrhenius方程。不同温度的测试结果表明,St-DVB共聚超微粒的微交联网络结构使其分子形态不易改变。在θ溶剂中,T<θ时,微粒发生聚集,表现出大分子的协同扩散;T>θ时,在较高浓度,扩散系数偏离与浓度的线性关系。流体力学作用和热运动决定了微粒分子的扩散行为。     

溶剂在高分子中的扩散系数-Vrentas-Duda模型及其发展

自由体积理论是描述高分子材料中低分子量溶剂扩散现象的有效工具,以此为基础的Vrentas-Duda模型中多数参数不需要扩散实验测量,可以通过分子性质独立确定,对渗透物的扩散行为具有可预测性。综述了Vrentas-Duda自由体积理论的发展和修正情况,分析其对建立预测型溶剂扩散系数模型的贡献,为从分子基团水平上探索溶剂扩散现象奠定基础。     

氧气在聚丙烯内吸附和扩散的分子模拟

采用巨正则Monte Carlo和分子动力学模拟相结合的方法研究了氧气在不同聚合度的聚丙烯内的吸附和扩散. 模拟结果表明, 随聚丙烯聚合度的增加, 聚丙烯对氧气的吸附量逐渐增加, 而氧气在聚丙烯内的扩散系数减小; 当聚合度增大到一定程度时, 吸附量和扩散系数都趋于一稳定值. 随温度的升高, 氧气在聚丙烯内的吸附量减少, 而扩散系数增大. 本文还应用自由体积理论探讨了氧气在聚合物内扩散的机理, 发现氧气在聚丙烯内以空穴形式存在的自由体积之间扩散, 即氧气先在一个空穴内不停振动, 然后通过聚丙烯链段运动形成的通道跳跃到下一个空穴来完成扩散. 结果表明, 较高聚合度的聚合物材料在常温及低温下使用对于其在食品包装材料中的应用是有利的, 这为食品包装材料行业相关产品的应用开发提供了一定的指导和依据.     

一种确定煤基吸附剂内各扩散系数的简易方法

多孔介质内的扩散有分子扩散和表面扩散两种。在吸附温度较高时 ,表面扩散可忽略 ,而在温度较低的吸附过程中 ,两种扩散均须考虑。Ｓｃｈｎｅｉｄｅｒ和Ｓｍｉｔｈ[1 ] 曾用色谱法探讨了一种计算扩散系数的方法。他们认为等温吸附呈线性变化 ,引入了曲折系数 ,计算出分子扩散系数 (下称气相扩散系数 ) ,表面扩散系数 (下称吸附相扩散系数 )则由综合扩散系数减去分子扩散系数得到。文献 [2 ]则认为吸附过程非线性变化 ,服从Ｆｒｕｎｄｌｉｃｈ方程或Ｌａｎｇｍｕｉｒ方程。从质量平衡方程得出相对吸附量方程 ,再求出各扩散系数。前一种方法将…     

苯与DOP在LDPE与PEMA基体中无限稀释扩散系数的测定及研究

用逆流气相色谱法测定了苯、邻苯二甲酸二辛酯(DOP)在293～373K间在低密度聚乙烯(LDPE)、聚甲基丙烯酸乙酯(PEMA)基体中的无限稀释扩散系数,拟合了扩散系数与温度倒数的对数线性关系,并求得扩散活化能,发现它在玻璃化温度附近出现转折,且两者之间存在0．6倍关系。通过检验Vrentas-Duda自由体积扩散模型,发现在小分子无相变情况下该模型比较准确。     

线性柱色谱分离过程的递推方程

依据非平衡热力学分离理论中的局域平衡假设和流体力学的Lagrangian描述方 法，首次提出了线性柱色谱分离过程中溶质带迁移和扩散的状态递推方程，克服了 以经典动力学为基础的塔板理论不能准确预测时变控制条件下溶质扩散的局限性。 反相色谱梯度洗脱的实验数据支持递推方程的理论预测，与基于塔板理论的预测方 法比较，状态递推方程法更具优越性。状态递推方程还为采用动态优化控制柱分离 过程奠定了基础。     

小分子在高分子膜中无限稀释扩散系数的测定

随着高分子材料研究和应用的日益广泛,小分子在高分子中迁移规律的研究显示出其重要的理论和现实意义．小分子在高分子中的扩散系数是衡量其在高分子中迁移速率的一个重要物理量,其测定方法有多种,其中反相气相色谱法具有简便、迅速的特点且能适用于无限稀的浓度范围,反相气相色谱法早期所采用的模型是VanDeemter方程’‘·”,但此模型往往受柱子条件限制,且得出的扩散系数由于包含了小分子在气相中的扩散而其值偏大．最近R0mdhane和＂anner”‘提出了新的数学模型来描述填充柱的色谱过程,并采用矩分析法处理色谱流出峰,修正了流…     

A nuclear magnetic resonance study of toluene-polyisobutylene solutions. 2. Vrentas-Duda theory

The self-diffusion coefficients of toluene in polyisobutylene have been analyzed using the Vrentas-Duda free volume diffusion model. The diffusion coefficients were determined at different temperatures and concentrations, using the pulsed field gradient nuclear magnetic resonance technique. The data were satisfactorily described by the model and the size of the polymer jumping unit was extracted. Comparisons were made with the Fujita free volume theory and the Fujita free volume parameters were extracted from the Vrentas-Duda free volume parameters. From the diffusion data that now available, it can be concluded that for most polymers the jumping unit is about 1.5 times the polymer monomer molecular weight. The activation energy of the toluene diffusion in polyisobutylene is compared with the activation energies of other penetrants in the same polymer. The diffusion data presented in this work show that the energy per mole required to overcome the attractive forces which constrain a diffusing species to its neighbors should be considered to be zero, in order to be able to extract the free volume parameters (from viscosity and diffusion data) with an acceptable uncertainty. ©1995 John Wiley & Sons, Inc.     

A model for predicting solvent self-diffusion coefficients in nonglassy polymer/solvent solutions

Cohen-Turnbull diffusion theory is used to develop a model for predicting solvent self-diffusion coefficients D₁ in nonglassy polymer/solvent solutions. Polymer molecules are envisioned as hindering solvent mobility by reducing the average free volume per unit mass in the system and through the lower mobility of polymer segments relative to solvent molecules. The concentration dependence of D₁ predicted by the model is in reasonable agreement with data for the solvents heptane, hexadecane, benzene, cyclohexane, and decalin in polyisobutylene (PIB), and for toluene in polystyrene, poly(methyl mothacrylate), and PIB. Although none of the data is for high concentrations of polymer (volume fractions ?≥0.9) it is anticipated the model will be less representative in this regime where the assumptions in its development are unsure. The model also demonstrates the correct temperature and concentration dependence of the apparent activation energy for diffusion. The only experimental data needed to use the model are the viscosity and critical volume of the pure solvent, and the specific volume of both the solvent and mixture. No binary transport data are required.     

Experimental free volume aspects of the polymer rheology as obtained by positron annihilation lifetime spectroscopy

The ortho‐positronium (o‐Ps) annihilation parameters, i.e. the mean o‐Ps lifetime, τ₃, and the o‐Ps relative intensity, I₃, in cis‐1,4‐polybutadiene (cis‐1,4‐PBD) and polyisobutylene (PIB) over a wide temperature range including the glass‐liquid transition have been measured by means of positron annihilation lifetime Spectroscopy (PALS). From them the free volume microstructural characteristics, i.e. the mean free volume hole size, V_h, and the free volume hole fraction, f_h, have been determined via a semiempirical quantum‐mechanical model of o‐Ps in a spherical hole or a phenomenological model of volumetric and free volume hole properties, respectively. Consequently, the literature rheological data for both the above‐mentioned polymers have been related to the free volume hole fractions via the WLF‐Doolittle type equation. It has been found that i) in the case of PIB this equation holds over 130K above the glass transition temperature T_g and ii) in the case of cis‐PBD the WLF‐Doolitle equation is valid in the temperature range over 60K above 1.3T_g, but below 1.3T_g down to T_g the modified WLF‐Doolittle‐Macedo‐Litovitz equation with the additional activation‐energy term describes the shift factor data better.     

Electrochemical properties of polyethylene membrane modified with carboxylic acid group

Two cation-exchange membranes modified with the carboxylic acid group for battery separator were prepared by radiation-induced grafting of acrylic acid (AA) and methacrylic acid (MA) onto a polyethylene (PE) film. The surface area, thickness, volume, water uptake, ion-exchange capacity, specific electric resistance, and electrolyte flux were evaluated after PE film was grafted with AA and MA. It was found that KOH diffusion flux of AA-grafted PE membrane and MA-grafted PE membrane increased with an increase in the degree of grafting. AA-grafted PE membrane had a higher diffusion flux than MA-grafted PE membrane. Electrical resistance of two cation-exchange membranes modified with AA and MA decreased rapidly with an increase in the degree of grafting.     

A diffusion model of the pervaporation separation of ethylene glycol-water mixtures through crosslinked poly(vinyl alcohol) membrane

The pervaporation separation of ethylene glycol-water mixtures was carried out over the full range of compositions at temperatures varying from 60 to 80°C, using chemically crosslinked PVA dense membrane which had been developed in our laboratory. A new thermodynamic diffusion coefficient equation is derived based on the modified Vigne equation. Combining Lee-Thodos equations, Wilke-Chang equations, Vrentas-Duda's free volume theory, diffusion equations and swelling equilibrium equations, the permeation fluxes of individual components in ethylene glycol-water mixture through crosslinked poly(vinyl alcohol) (PVA) dense membrane have been calculated and showed to be in agreement with the experimental values.     

A nuclear magnetic resonance study of dynamics in toluene-polyisobutylene solutions: 1. Penetrant diffusion and Fujita theory

The self-diffusion coefficients of toluene in polyisobutylene (PIB) solutions were determined using the pulsed field gradient nuclear magnetic resonance technique. The volume fraction of toluene in the polymer was varied from 0.045 up to 0.712 and the temperature was varied from 225 K up to 368 K. The concentration dependence of the data was interpreted using the Fujita free volume theory and the temperature dependence was interpreted with the WLF equation. These models describe separately the concentration and temperature dependencies of the toluene self-diffusion coefficients very well and the resulting free volume parameters are in good agreement with the ones extracted from the analysis of viscosity data on the same system. ©1995 John Wiley & Sons, Inc.     

Water diffusion in polyethylene modified by ion irradiation

Water diffusion in polyethylene (PE) modified by irradiation with 40keV Ar⁺ ions to fluences of 1 × l0¹² to 1 × l0¹⁵cm⁻² was studied. The diffusion experiments were performed in a temperature interval from 25 to 100 °C and for diffusion times of up to 3 h. The water incorporated was detected by infra-red spectroscopy, microgravimetry and by measuring contact angles. Maximum water uptake observed for the ion fluence of 1 × 10¹³cm⁻² may be connected with an increase in free volume fraction and oxidative processes in the PE surface layer modified by ion irradiation. For higher ion fluences, the available free volume is reduced owing to carbonization and crosslinking of the polymer and, accordingly, the water content decreases. The water incorporated in PE is mostly in the form of isolated molecules. At elevated temperature rediffusion of water is observed.     

A nuclear magnetic resonance study of toluene-polyisobutylene solutions. 3. Spin-lattice relaxation: Rotational and segmental motion

The spin-lattice relaxation times are determined for the methylene carbon of polyisobutylene (PIB), as well as for the ortho carbon of toluene in toluene-polyisobutylene solutions. The Hall-Helfand correlation function combined with restricted anisotropic rotational diffusion was used to treat the T₁ data of the methylene carbon of PIB. A simple exponential correlation function was used to describe the local motion of toluene in the solutions which falls in the extreme narrowing limit for the solutions studied. Both models described satisfactorily the temperature and field dependence of the spin-lattice relation times. From the temperature dependence of the correlation times for the polymer segmental motion, the free volume of the solution at each concentration is extracted and compared with the values obtained from previous studies of the translational motion of the toluene penetrant. The free volume values extracted from the T₁ data for the methylene carbon of PIB and the self-diffusion data for the toluene were found to be in substantial agreement. The interrelationship of the timescale of segmental motion of the polymer and the translational diffusion of the toluene was also examined and it was found that the two types of motion seem to be correlated in high polymer concentrated solutions. The toluene reorientational motion was found to be much faster than both the polymer segmental motion and the toluene translational diffusion leading to the conclusion that the toluene reorientational motion is uncoupled from these two motions. ©1995 John Wiley & Sons, Inc.     

Modified combinatorial factor in the hole theory

To describe the behavior of liquid state by hole theory, Flory's combinatorial factor used in the partition function of the hole theory is modified in a general form by assuming that unit segment of chain molecule can occupy more than one unit cell or lattice. From this combinatorial factor and free volume expression, a new equation of state is derived, and is used to calculate the PVT behaviors of 10 pure low molecular weight liquid systems. In addition, the PVT behavior of carbontetrachloride/cyclohexane binary system is calculated. Good agreements between the theory and experimental data are obtained.     

Analysis of solute diffusion in poly(vinyl alcohol) hydrogel membrane

Measurement of diffusion and partitioning of solutes having molecular weights ranging 180–66000 in PVA gel membranes with various crosslinking degree were carried out. With increasing solute size or decreasing number of average molecular weight between crosslinks of the membranes, both the solute permeability and partition coefficient decreased. In spite of similar solute sizes, the more hydrophilic solute ribonuclease showed higher permeability and partition coefficient than the less hydrophilic α-lactalbumin, probably due to interaction with the hydrophilic PVA. The solute diffusion through swollen gel membrane was analyzed by the equation based on free volume theory. In this analysis equation, the partition coefficient, which is defined as the ratio of solute concentration in gel membrane standardized by water volume in the membrane to that in bulk solution, was introduced as the probability of a diffusing species finding a mesh with a volume of at least the solute size. The efficiency of the proposed analysis equation was confirmed by the experimental results of the effects of solute size and water volume fraction in the membrane.