聚合物熔体界面扩散理论与研究方法

本文结合与聚合物加工过程密切相关的界面扩散问题,从动力学和热力学两方面综述了与聚合物界面互扩散相关的基础理论.结合在聚合物界面扩散方面的研究进展,系统介绍了聚合物熔体界面扩散的常用研究方法.对其中的流变学方法的原理及进展作了重点论述,该方法不仅可以有效表征聚合物熔体界面扩散的动力学过程,进一步从分子动力学角度发展并完善聚合物扩散理论,而且对于聚合物加工成型过程的界面结构设计和性能优化起到关键的指导作用.本文最后提出了聚合物熔体界面扩散研究中存在的问题并对其前景进行了展望.     

多孔离子交换树脂内Eu3+离子的分步扩散

用同位素交换法研究了Eu³⁺离子在D72和D751树脂内的扩散过程.应用分步孔道扩散方程将粒内有效扩散系数D_e分解为孔道扩散系数D_p和固相扩散系数D_g,表明该方程可用于描述多孔树脂内的动力学过程.实验表明,D_e、D_p、D_g均随反应温度的升高而增大.计算了实验条件下的Eu³⁺的自扩散活化能;D72树脂的D_p和D_g对温度的响应比D751树脂大,其D_e、D_p、D_g值亦均大于D751树脂;Eu³⁺在溶液中的自扩散系数D_s＞D_p,说明离子在树脂孔道内的自扩散不能完全等同于其在溶液中的自扩散.     

胸腺五肽在NH-1树脂上的离子交换过程研究

研究了胸腺五肽(TP5)在NH-1树脂上的离子交换过程.结果表明,在pH 2.O的条件下,其等温吸附过程符合Langmuir等温吸附方程,最大吸附量为221.07mg/g wet resin;静态吸附动力学的研究结果显示,NH-1树脂对TP5的吸附过程主要受颗粒扩散控制影响,TP5的颗粒内扩散系数为4.50×10-9cm2/s;对比Nernst-Planck与Fick动力学模型,可用Fick动力学模型来描述TP5在NH-1树脂内的颗粒扩散行为,其有效扩散系数为5.58×10-9cm2/s;采用固定床吸附数学模型,对TP5离子交换柱行为进行模拟,该数学模型考虑了颗粒扩散、轴向返混、非线性平衡以及液膜扩散.结果显示,模拟数据与实验结果具有较好的符合.     

离子交换树脂吸附胞嘧啶核苷三磷酸的动力学和热力学研究

根据CTP在离子交换树脂上的吸附容量和分离因数的大小,确定Duolite A-30树脂适合CTP与CDP及CMP之间的分离.CTP在Duolite A-30树脂上的吸附动力学和热力学研究表明,在283.15～303.15K之间,CTP的质量浓度在7.5g/L以上时,Duolite A-30树脂对CTP的吸附主要受颗粒扩散的控制,其有效扩散系数为D=3.47×10-7cm2/s,溶液的质量浓度≤1.0g/L时,CTP与Duolitc A-30树脂之间的交换速率主要受液膜控制,其液膜扩散系数为Kf=4.112×10-4/s.热力学参数Eα=9.008kJ/mol,△H=5.17kJ/mol·K,△S283.15K=80.28J/mol·K.     

氧在甲基丙烯酸辛酯-乙烯基咪唑共聚物/钴卟啉复合膜中的溶解和扩散过程

讨论了氧在甲基丙烯酸辛酯 乙烯基咪唑共聚物 钴卟啉复合膜中的溶解和扩散过程,用二元输送模型分析了间α,α,α,α-四(邻三甲基乙酰胺苯基)钴卟啉(CoP)作为氧载体的复合膜氧输送性能.研究发现,固定在聚合物中的CoP与氧可逆地络合和解络合,其络合平衡常数K为14mol- 1 L ,根据吸附实验结果计算出氧在基体聚合物中的物理溶解度系数kD 为4 4×10 - 5cm3(STP)cm- 3Pa- 1 .聚合物 载体复合膜除了物理渗透外,氧还可通过与载体的络合和解络合而扩散,从而促进氧的输送.氧通过载体的扩散系数(DC)和通过基体聚合物的物理扩散系数(DD)的比值为0 0 8.     

弱酸强碱两性树脂解吸动力学的研究

本文采用浅床解吸法对离子在弱酸强碱两性树脂相内的扩散进行了研究．结果表明：阳离子所带电荷越多．其粒内扩散系数就越小，阴离子体积越大．电荷多．则粒内扩散系数也越小。     

两性树脂解吸动力学的研究──温度对扩散系数的影响

本文采用浅床法对阳离子在弱酸强碱两性树脂相内的扩散速度进行了研究。发现温度升高 ,其粒内扩散系数增大 ,离子价态越高 ,扩散过程的活化能就越大 ,表明温度的改变对高价阳离子的扩散速度的影响更显著     

离子交换法纯化重组类人胶原蛋白Ⅱ的吸附动力学研究

为了确定重组类人胶原蛋白Ⅱ(Recombinant human-like collagen,RHLC Ⅱ)在CM52树脂上的动力学行为,考察温度、初始浓度等因素的影响,分别采用简单线性推动力模型(液膜扩散控制时)和均相扩散模型(颗粒扩散控制时)研究RHLC Ⅱ在不同工艺条件下的反应速率,确定离子交换过程的速率控制步骤,并计算模型参数.结果表明,(1)速率控制机理受转速和料液初始浓度的影响,在转速和料液初始浓度较低时,为液膜扩散控制(Film Diffusion Control,FDC);反之,则为颗粒扩散控制(Particle Diffusion Control,PDC);(2)以简单线性推动力模型拟合液膜扩散控制时的动力学数据,其线性关系良好,模型准确度较高;对于颗粒扩散控制的吸附,则以均相扩散模型拟合,求出有效扩散系数,模型较好地描述了CM52对RHLC Ⅱ的PDC吸附.(3)对于FDC,温度越高,溶液浓度越大,搅拌转速越高,外扩散速度常数越大,吸附越快;对于PDC,温度升高,有效扩散系数增大,吸附加快,料液浓度对有效扩散系数的影响不显著.     

EDTA溶液中稀土离子在大孔树脂内的扩散

本文研究了EDTA溶液中稀土在大孔树脂内的扩散,用同位素交换法测定了ce,Tb、Yb的有效粒内自扩散系数(D_e)。D_e值受外部溶液浓度的影响。应用Kataoka双分散大孔扩散方程将D_e值分解为孔道扩散系数D_p和固相扩散系数D_g,表明该方程可用于描述大孔树脂的动力学过程。D_e随树脂粒度增大而增加,D_p远大于D_e,D_g接近于D_e,固相扩散是控制离子在大孔树脂扩散速率的决定步骤。     

大孔树脂吸附苯和甲苯的平衡及动力学研究

研究并比较了四种大孔吸附树脂对正庆烷中低浓度苯、甲苯的吸附平衡及动力学。Langmuir方程能够良好地描述吸附等温线,由单组分吸附平衡得到的参数;可以很好地预测双组分吸附平衡。动力学研究表明,内扩散过程是决速步,并估算出粒内扩散系数。     

Molecular dynamics simulations of nanocomposites based on poly(epsilon-caprolactone) grafted on montmorillonite clay

Intercalated and exfoliated models of polymer nanocomposites based on poly(epsilon-caprolactone) and functionalized montmorillonite clay are studied by means of molecular dynamics simulations. Intercalated and exfoliated models are considered for probing the structural characteristics of the corresponding nanocomposites prepared by melt intercalation and in situ polymerization, respectively. In the exfoliated system, the organization of the polymer chains onto the clay surface is examined in terms of the density profiles and the order parameter function. A layered structure can clearly be seen to form near the surface with density maxima higher than in amorphous poly(epsilon-caprolactone). This can be viewed as an increase in effective particle thickness, which can contribute to the outstanding gas barrier properties of the exfoliated nanocomposites. The comparison of the structures and energetics of the intercalated model with those of a nanocomposite model based on a nonfunctionalized clay indicates nearly similar characteristics. Nevertheless, the slight differences observed for the interfacial polymer density and clay- and surfactant-polymer binding energies can account for the differences in rheological measurements. The results also suggest that the difference in morphology obtained for the nanocomposites prepared by the two synthetic approaches can be ascribed to both a difference in interfacial polymer density and the formation of bridging polymer chain structures that hinder the exfoliation process.     

Effect of thermo-mechanical cycles on the physico-chemical properties of poly(lactic acid)

Polylactic acid (PLA) has now become an economically viable commodity plastic in many industries. This raises the question of recyclability of industrial production waste and some packaging wastes as well. The evolution of rheological and mechanical properties of polymer with the number of recycling cycles up to seven was investigated. For PLA, only the tensile modulus remains constant with the thermo-mechanical cycles. In contrast, stress and strain at break, rheological factors and the modulus and hardness probed by nanoindentation decrease for PLA. This dramatic effect is ascribed to a large decrease in the molecular weight due to several different complex degradation processes which are discussed. The effect of two stabilizers is also assessed.     

端羟基聚丁二烯/增塑剂共混物相容性的分子动力学模拟

固体推进剂和炸药的力学性能在很大程度上依赖于配方中高分子粘结剂与增塑剂的相容性. 本文对相容和非相容两种体系进行了分子动力学(MD)模拟, 以考察分子模拟方法的实用性. 为预测固体推进剂中端羟基聚丁二烯(HTPB)与增塑剂癸二酸二辛酯(DOS)、硝化甘油(NG)的相容性, 采用MD模拟方法在COMPASS力场下, 对HTPB、DOS、NG和共混物HTPB/DOS、HTPB/NG的密度、内聚能密度及溶度参数等进行了模拟计算. 通过比较溶度参数差值(△δ)的大小、分子间径向分布函数和模拟前后体系密度变化情况均可以预测HTPB/DOS属于相容体系,而HTPB/NG属于不相容体系, 与实验结果一致. 径向分布函数分析同时揭示了HTPB/增塑剂组分之间的相互作用及本质. 本文的模拟方法可以作为预测聚合物与增塑剂相容性的有利工具, 也可以为固体推进剂和炸药的配方设计提供理论指导.     

Molecular dynamics simulation of solvent-polymer interdiffusion: Fickian diffusion

The interdiffusion of a solvent into a polymer melt has been studied using large scale molecular dynamics and Monte Carlo simulation techniques. The solvent concentration profile and weight gain by the polymer have been measured as a function of time. The weight gain is found to scale as t(1/2), which is expected for Fickian diffusion. The concentration profiles are fit very well assuming Fick's second law with a constant diffusivity. The diffusivity found from fitting Fick's second law is found to be independent of time and equal to the self-diffusion constant in the dilute solvent limit. We separately calculated the diffusivity as a function of concentration using the Darken equation and found that the diffusivity is essentially constant for the concentration range relevant for interdiffusion.     

动态流变法在聚合物/聚合物界面分子链扩散研究中的应用

聚合物/聚合物界面的分子链扩散问题在塑料注塑、焊接、共混等领域普遍存在.动态流变法是研究聚合物/聚合物界面分子链扩散的一种有力手段,这种方法对于界面间分子链扩散的监测非常灵敏.本文简述了用动态流变法研究聚合物/聚合物界面扩散的原理、实验方法以及优点,着重讨论了采用该方法研究初始界面分子链末端分布对扩散机理的影响、对称聚合物/聚合物界面分子链扩散的量化,非对称聚合物/聚合物界面的相互扩散,分子量多分散性对聚合物/聚合物界面扩散的影响,聚合物/聚合物界面间的流动和扩散耦合以及近年来动态流变法在化学反应型聚合物/聚合物界面的应用进展.     

Interdiffusion of solvent into glassy polymer films: a molecular dynamics study

Large scale molecular dynamics and grand canonical Monte Carlo simulation techniques are used to study the behavior of the interdiffusion of a solvent into an entangled polymer matrix as the state of the polymer changes from a melt to a glass. The weight gain by the polymer increases with time t as t(1/2) in agreement with Fickian diffusion for all cases studied, although the diffusivity is found to be strongly concentration dependent especially as one approaches the glass transition temperature of the polymer. The diffusivity as a function of solvent concentration determined using the one-dimensional Fick's model of the diffusion equation is compared to the diffusivity calculated using the Darken equation from simulations of equilibrated solvent-polymer solutions. The diffusivity calculated using these two different approaches are in good agreement. The behavior of the diffusivity strongly depends on the state of the polymer and is related to the shape of the solvent concentration profile.     

Describing the component dynamics in miscible polymer blends: towards a fully predictive model

We have recently proposed [D. Cangialosi et al., J. Chem. Phys. 123, 144908 (2005)] an extension of the Adam-Gibbs [J. Chem. Phys. 43, 139 (1965)] theory, combined with the concept of self-concentration, to describe the temperature dependence of the relaxation time for the component segmental dynamics in miscible polymer blends. Thus, we were able to obtain the dynamics of each component in the blend starting from the knowledge of the dynamic and thermodynamic data of the pure polymers, with a single fitting parameter (alpha) which had to be obtained from the fitting of the experimental data. In the present work we demonstrate that this model is also suitable to describe the polymer segmental dynamics in concentrated polymer solutions. From this result we have developed a new route for determining the value of the alpha parameter associated with any given polymer. Once this value is known for the two components of a possible polymer blend, our model for polymer blends dynamics becomes fully predictive.     

An ultrasonic method to study the interdiffusion phenomenon between two polydimethylsiloxanes

We present an original method that allows the monitoring of the interdiffusion process between two miscible polymers. This acoustical method is nondestructive, and does not need any chain marking. It is based on the variations of the angular reflection coefficient R(θ) measured at fixed frequency, caused by the ultrasonic parameters modifications in the interphase during the diffusion process. We applied it to the interdiffusion between two polydimethylsiloxanes A and B of very different molecular weights. The evolution of R(θ) was also computed using successively the slow and the fast theories of diffusion, after calculation of the concentration profiles. The adjustment of the theoretical reflection spectra given by the slow theory on the experimental spectra allowed us to find the value the interdiffusion coefficient D₀, which is characteristic of the system. This value is very near the value determined from the molecular dynamics laws (Rouse, reptation, Stokes-Einstein). But in the studied time domain, the fast theory accounts for the experimental results as well as the slow theory. Finally, we discuss the precision of the method and the means to improve it.     

“Volume‐Preserving” Conformational Rheological Models for Multi‐Component Miscible Polymer Blends Using the GENERIC Formalism

A family of conformational rheological models for multi‐component miscible polymer blends is developed using a modified form of the Poisson bracket formulation. Two conformation tensors called c ₁ and c ₂ are introduced to show the orientation of the first and the second components of a blend, respectively. The mobility tensor and the energy function for each blend component are expressed in terms of these conformation tensors. The interaction effects are also included by energy expressions. The predictions of this family of “volume‐preserving” models are illustrated for a Hookean‐type energy function and several expressions of the modified mobility tensors. The results are illustrated for material functions in transient (start‐up and relaxation) and steady shear flows. The predictions are compared with experimental data taken from the literature for a miscible polymer blend. Study of the model sensitivity to its parameter shows that model predictions can cover a wide range of rheological behavior generally observed for multi‐component miscible polymer blends in steady and transient shear flows.

Experimental data and model predictions for steady shear viscosity for HDPE/LDPE blends.     

Model experiments for the interfacial reaction between polymers during reactive polymer blending

Bilayer film Fourier transform infrared (FTIR) model experiments are designed to provide a well-defined interface for study which can be probed by infrared spectroscopy during the interdiffusion and reaction of two reactive polymers. This provides a model experiment to determine the kinetics and extent of reaction between functionalized polymers during reactive polymer blending. This type of experiment provides data on the reaction at a stagnant interface which is necessary for the analysis of the interface while it is simultaneously undergoing deformation. It is also useful as a screening or preliminary experiment on reactive blending systems in that the extent of reaction may be followed for different systems at different temperatures. Experiments reported here trace the reaction of a styrene–maleic anhydride copolymer with two different amine terminated polymers. Results are obtained for the interdiffusion and reaction of a styrene-maleic anhydride copolymer with two amine terminated polymers: a butadiene-acrylonitrile copolymer and Nylon 11. The kinetics from these experiments include contributions due to both interdiffusion and chemical reaction. The chemical reaction kinetics may be isolated from the diffusion kinetics by performing experiments on well-mixed systems which are prepared by casting films of the polymer mixtures from a mutual solvent. © 1994 John Wiley & Sons, Inc.