Rheological Behavior for Polymer Melts and Concentrated Solutions——Part Ⅶ: A Quantitative Verification for the Molecular Theory of Non-linear Viscoelasticity with Entanglement Constraints in Polymer Melts

Based on the molecular theory of non-linear viscoelasticity with constrained entanglements in polymer melts, the material functions in simple shear flow were formulated, the theoretical relations between. eta((gamma) over dot), psi (10)((gamma) over dot) and shear rate ((gamma) over dot), and topologically constrained dimension number n ' and a were derived. Linear viscoelastic parameters (eta (0) and G(N)(0)) and topologically constrained dimension number (n ' a and <(<upsilon>)over bar>) as a function of the primary molecular weight (M-n), molecular weight between entanglements (M-C) and the entanglement sites sequence distribution in polymer chain were determined. A new method for determination of viscoelastic parameters (eta (0), psi (10), G(N)(0) and J(e)(0)), topologically constrained dimension number (n ', a and v) and molecular weight (M-n, M-c and M-e) from the shear flow measurements was proposed. It was used to determine those parameters and structures of HDPE, making a good agreement between these values and those obtained by other methods. The agreement affords a quantitative verification for the molecular theory of nonlinear viscoelasticity with constrained entanglement in polymer melts.

Rheological Behaviour for Polymer Melts and Concentrated Solutions Part Ⅰ:A New Multiple Reptation Model to Predict the Nonlinear Visco-elasticity with Nagai Chain Constraints in Entangled Polymer Melts

An approach of stochastically statistical mechanics and a unified molecular theory of nonlinear viscoelasticity with constraints of Nagai chain entanglement for polymer melts have been proposed. A multimode model structure for a single polymer chain with n tail segments and N reversible entanglement sites on the test polymer chain is developed. Based on the above model structure and the mechanism of molecular flow by the dynamical reorganization of entanglement sites, the probability distribution function of the end-to-end vectr for a single polymer chain at entangled state and the viscoelastic free energy of deformation for polymer melts are calculated by using the method of the stochastically statistical mechanics. The four types of stress-strain relation and the memory function are derived from this thery. The above theoretical relations are verified by the experimentaf data for various polymer melts. These relations are found to be in good agreement with the experimental results

Rheological Behaviour for Polymer Melts and Concentrated SolutionsPart Ⅱ: Material Function with Nagai Chain Constraints and Determination of Their Parameters from Flow Curves

An integral constitutive equation and a set of material functions for describing the strain history of polymer melts were formulated in terms of the Cauchy-Green and Finger tensors. A simple memory function and the dependence of ηo and τt on M3.4 were derived from the theory of non-linear viscoelasticity with constraints of entanglements for polymer melts and substituted into the Oldroye-Walters-Fredickson constitutive equation. An integral constitutive equation for polymer melts was consequently obtained. Some material functions of the constitutive equation related to certain 'test flow' are examined as follows : (1) simple steady shear flow; (2) steady elongation flow; (3) small-amplitude oscillatory shear flow; (4) stress growth upon the inception of steady shear elongation flow; (5) stress relaxation (modulus and compllance). These theoretical relations for simple steady shear flow were compared with experimental data from our laboratory and references for various polymer melts and concentrated solutions. A good agreement between the theory and experiment was achieved.

MODELING THE CHAIN CONFORMATION OF POLYMER MELTS IN CONTRACTION FLOW

A constitutive model of quasi-Newtonian fluid based on the type of flow is used in abrupt planar contraction now.The numerical results from finite element analysis are consistent with experimental data for stress patterns and velocityprofiles in the flow field. The chain conformations of polymer melts are then investigated in such a planar contraction byusing the phenomenological model with internal parameters proposed by the author. That is, the shape and orientation ofpolymer chain coils are predicted and discussed in different flow regions of the contraction flow field that possess simpleshear flow, extensional flow, vortical flow, and mixed flow respectively.

A RHEOLOGICAL MODEL FOR POLYMER MELTS WITH INTERNAL STRUCTURE IN FLOW FIELDS

Conceptually, an imagined conformation ellipsoid is supposed to represent the shape of a polymer chain for polymer melts in flow fields and to be equivalent to the volume element in a mathematical sense in continuum mechanics. A power law dependence of shear modulus of polymer melts on detC, referred to as envelope volume, is proposed. Based on those assumptions and the non-linear relation of shear modulus, a phenomenological viscoelastic model is derived. The model is tested in simple shear flow, simple elongational flow, oscillatory shear flow, and relaxation process after flow suddenly stopped. The results show that the model works well to predict the change of internal structure and viscoelastic performance of polymer melts in flow fields.

Analyses of Dynamic Rheological Behavior of Polymer Melt Based on Novel Experimental Equipment and Procedures

By introducing a vibrating force field into the extrusion process of polymer melt, an experimental equipment of constant velocity type dynamic rheometer of capillary (CVDRC) was designed. A set of experimental procedures was established, by which the dynamic rheological parameters of polymer can be acquired, and a set of data management methods to undergo time-domain or frequency-domain analysis was set up for dynamic rheological data of polymer melt. Meantime, the characterization formula of polymer melt's rheological behavior in a vibrating force field was set up. The instantaneous value of capillary entry pressure, capillary volume flow rate and their phase difference were measured and analyzed, and the melt apparent viscosity, which describes the rheological behavior of polymer melt in a vibrating force field, was obtained.

Statics,Dynamics and Linear Viscoelasticity from Dissipative Particle Dynamics Simulation of Entangled Linear Polymer Melts

Dissipative particle dynamics(DPD)with bond uncrossability shows a great potential in studying entangled polymers,however relatively little is known of applicability range of entangled DPD model to be use as a model for ideal chains and properly describe the full dynamics of entangled melts.Therefore,we perform a comprehensive study on structure,dynamics and linear viscoelasticity of a typical DPD entangled model system,semiflexible linear polymer melt.These polymers obey Flory's ideality hypothesis in chain dimensions,but their local structure exhibits nonideal behavior due to weak correlated hole effect.Both monomer motion and viscoelasticity relaxation reproduce the full pictures as predicted by reptation theory.The stronger chain length dependent diffusion coefficient and relaxation time as well as dynamic moduli are in close agreement with predictions of modern tube model that accounts for additional relaxation mechanisms besides chain reptation.However,an anomalous sub-diffusive center of mass motion is observed both before and after the intermediate reptation regime and the cross-correlation between chains is not negligible even these polymers obey stress-optical law,indicating limitations of the reptation theory.Hence semiflexible linear entangled DPD model can correctly describe statics and dynamics of entangled polymer melts.

Shear and extensional rheology of entangled polymer melts: Similarities and differences

This work extends our previous understanding concerning the nonlinear responses of entangled polymer solutions and melts to large external deformation in both simple shear and uniaxial extension. Many similarities have recently been identified for both step strain and startup continuous deformation, including elastic yielding, i.e., chain disentanglement after cessation of shear or extension, and emergence of a yield point during startup deformation that involves a deformation rate in excess of the dominant molecular relaxation rate. At a sufficiently high constant Hencky rate, uniaxial extension of an entangled melt is known to produce window-glass-like rupture. The present study provides evidence against the speculation that chain entanglements tie up into "dead knots" in constant-rate extension because of the exponentially growing chain stretching with time. In particular, it is shown that even Instron-style tensile stretching, i.e., extending a specimen by applying a constant velocity on both ends, results in rupture. Yet, in the same rate range, the same entangled melt only yields in simple shear, and the resulting shear banding is clearly not a characteristic of rupture. Thus, we conclude that chain entanglements respond to simple shear in the manner of yielding whereas uniaxial extension is rather effective in causing some entanglements to lock up, making it impossible for the entanglement network to yield at high rates.

Diffusion and Relaxation Dynamics of Supercooled Polymer Melts

The dynamic properties of polymer melts are investigated in the range of normal liquid regime to the supercooled liquid regime. The polymer is modeled as a coarse-grained bead-spring model with chain length ranging from 5 to 160. The mean squared displacement and non-Gaussian parameter are used to describe the self diffusion of polymer beads. We find slow dynamics with decreasing temperature and increasing chain length. The time evolution of non-Gaussian parameters shows two peaks （or one peak one shoulder） in the a-relaxation time, τa, regime and sub-diffusion time regime, respectively, where the first primary peak indicates the dynamic heterogeneity stemmed from the motion of beads, and the secondary peak is the result of correlated motion along a polymer chain. Moreover, the relaxation of polymer beads shows clear two-step decay in supercooled melts and the dynamics shows growing heterogeneity with decreasing temperature. As chain length is increased, a peak of the dynamic susceptibility occurs, and the peak height, x＊4, increases and then reaches a plateau. The curves of the height of the first peak of a2, a2＊, versus τa and the curves of x＊4 versus τa follow two master curves for different chain lengths. Our results indicate the similarity of dynamic heterogeneity dominated by the motion of single bead even the chain length is different. It is interesting to find that the Stokes-Einstein （SE） relation between ra and diffusion coefficient D, D-rq 1, is highly length-scale dependent. The SE relation breaks down in both normal melts regime and supercooled regime at large magnitude of wave vectors, attributed to the non-Brownian motion arising from the chain connectivity and growing heterogeneity due to supercooling. However, the SE relation is reconstructed when the probing length scale is large （at small magnitude of wave vectors）. Our results show a hierarchical physical picture of the supercooled polymeric dynamics.

Developing Soft Sensors for Polymer Melt Index in an Industrial Polymerization Process Using Deep Belief Networks

This paper presents developing soft sensors for polymer melt index in an industrial polymerization process by using deep belief network(DBN).The important quality variable melt index of polypropylene is hard to measure in industrial processes.Lack of online measurement instruments becomes a problem in polymer quality control.One effective solution is to use soft sensors to estimate the quality variables from process data.In recent years,deep learning has achieved many successful applications in image classification and speech recognition.DBN as one novel technique has strong generalization capability to model complex dynamic processes due to its deep architecture.It can meet the demand of modelling accuracy when applied to actual processes.Compared to the conventional neural networks,the training of DBN contains a supervised training phase and an unsupervised training phase.To mine the valuable information from process data,DBN can be trained by the process data without existing labels in an unsupervised training phase to improve the performance of estimation.Selection of DBN structure is investigated in the paper.The modelling results achieved by DBN and feedforward neural networks are compared in this paper.It is shown that the DBN models give very accurate estimations of the polymer melt index.

Ultravilolet-radiation-induced graft polymerization of acrylamide onto the melt-blown polypropylene filter element by dynamic method

By dynamic method under UV irradiation, commercial melt-blown polypropylene （PPMB） filter element was modified with acrylamide （AAm） using benzophenone （BP） as initiator. Attenuated total reflection-Fourier transform infrared spectroscopy and scanning electron microscope verified that polyacrylamide chain was grafted on the fiber surface of PPMB filter element. Elemental content analysis with energy dispersive X-ray of fibers revealed that the polymerization content in the inner part of filter element was relatively higher than that in the outer. Degree of grafting changed with initiator concentration, monomer concentration, reaction temperature and reached 2.6% at the reaction condition： CBp=0.06 mol/L, CAAm=2.0 mol/L, irradiation time： 80 min, temperature： 60℃. Relative water flux altered with the hydrophilicity and pore size of filter element. In the antifouling test, the modified filter gave greater flux recovery （approximately 70%） after filtration of the water extract of Liuweidihuang, suggesting that the fouling layer was more easily reversible due to the hydrophilic nature of the modified filter.

聚丁二酸丁二醇酯熔融缩聚增黏特性

为解决生物可降解聚丁二酸丁二醇酯(PBS)长期正常储存过程中易发生降解而导致分子量下降的难题,通过熔融缩聚增黏方法实现了PBS分子量的提升。研究了反应温度、反应时间、初始特性黏度以及熔体膜厚等对PBS特性黏度、分子量、热性能和流变性能的影响。结果表明:PBS分子量随熔融缩聚增黏温度升高而升高;220℃反应60min,PBS特性黏度即可从1.049dL/g升至2.072dL/g;PBS初始黏度越低其增黏速率越高;而PBS的熔体膜厚与其增黏反应速率呈反比;PBS特性黏度的升高导致结晶困难,进而使其熔点下降。流变测试结果表明随着特性黏度升高,PBS熔体强度与热稳定性均提升,能满足重新加工和使用的需求,通过熔融再聚合方法可有效解决PBS因降解而无法满足其后续加工和使用需求的难题。

固相聚合对萘环液晶聚芳酯结构与性能的影响

为解决液晶聚芳酯熔融缩聚反应后期由于反应温度和熔体黏度过高导致的降解交联副反应以及成形加工困难等问题,以6-羟基-2-萘甲酸(HNA)、2,6-萘二羧酸(NDA)、对苯二甲酸(TA)、4,4'-二羟基联苯(BP)为原料,采用原位一锅熔融聚合法制备了低分子量萘环热致液晶聚芳酯,并对其进行固相聚合。通过差示扫描量热仪、热重分析仪、偏光显微镜、X射线衍射和熔融指数仪对固相聚合后的液晶聚芳酯结构与性能进行了测试。结果表明,液晶聚芳酯的熔融温度和结晶度受聚合时间和温度的影响较大,呈现出先增加后降低的变化趋势,但并不会改变聚芳酯的晶体结构,同样属于正交晶型。此外,固相聚合在温度305℃下反应12 h,液晶聚芳酯热学和结晶性能得到明显改善;高于此时间和温度时聚芳酯的熔点开始降低,热降解反应开始进行,热稳定性和结晶性能下降。

生物基聚酰胺510弹性体的制备及表征

以生物基戊二胺和癸二酸为单体采用熔融缩聚制备全生物基聚酰胺510。以双端羧基的聚酰胺510作为硬段,聚乙二醇为软段,采用两步熔融缩聚法制备生物基聚酰胺510弹性体。采用核磁共振氢谱和傅里叶变换红外光谱表征聚酰胺510弹性体的化学结构;通过差示扫描量热仪和热重分析仪测试聚酰胺510弹性体的热性能;利用万能试验机测试力学性能。结果表明,聚酰胺510弹性体的熔点、结晶温度、起始热分解温度、最大分解速率温度分别为210,163,395,452℃,低于聚酰胺510的217,177,410,456℃;在热学性能表征中,与聚酰胺510相比,聚酰胺510弹性体具有宽的加工窗口;在力学性能上,聚酰胺510弹性体的拉伸强度为42.7 MPa,低于聚酰胺510的拉伸强度60.3 MPa,断裂伸长率为224%,高于聚酰胺510的172%,聚酰胺510弹性体的柔韧性要高于聚酰胺510;在流变性能分析中,聚酰胺510弹性体低于聚酰胺510的储能模量、损耗模量及复数黏度,这是因为聚乙二醇影响了聚酰胺510的晶型结构及晶型的完整性。

耐高温茂金属催化剂催化乙烯与降冰片烯共聚

合成了一种用于乙烯与降冰片烯高温溶液共聚合的高活性耐高温茂金属催化剂,研究了反应温度、茂金属催化剂浓度、n(Al)∶n(Zr)、降冰片烯浓度等对催化剂活性的影响,并对乙烯-降冰片烯共聚物进行了分析和表征,确定了制备乙烯-降冰片烯共聚物的高温溶液聚合工艺条件。结果表明:反应温度为140℃时,催化剂活性高达6.7×10^(6)g/(mol·h),催化剂寿命达到30 min以上。最佳聚合条件:反应温度为140℃,茂金属催化剂浓度为6×10^(-5)mol/L,乙烯压力为1 MPa,n(Al)∶n(Zr)为250,n(B)∶n(Zr)为1.1,反应时间为30 min;最佳聚合条件下共聚物中的降冰片烯插入率达34.44%(y),密度约为0.98 g/cm^(3),玻璃化转变温度为135.8℃。

A soft sensor for industrial melt index prediction based on evolutionary extreme learning machine

In propylene polymerization(PP) process, the melt index(MI) is one of the most important quality variables for determining different brands of products and different grades of product quality. Accurate prediction of MI is essential for efficient and professional monitoring and control of practical PP processes. This paper presents a novel soft sensor based on extreme learning machine(ELM) and modified gravitational search algorithm(MGSA) to estimate MI from real PP process variables, where the MGSA algorithm is developed to find the best parameters of input weights and hidden biases for ELM. As the comparative basis, the models of ELM, APSO-ELM and GSAELM are also developed respectively. Based on the data from a real PP production plant, a detailed comparison of the models is carried out. The research results show the accuracy and universality of the proposed model and it can be a powerful tool for online MI prediction.

Non-isothermal crystallization kinetics of Nylon 10T and Nylon 10T/1010 copolymers:Effect of sebacic acid as a third comonomer

Nylon 10 T and Nylon 10T/1010 samples were synthesized by direct melt polymerization. The non-isothermal crystallization kinetics of Nylon 10 T and Nylon 10T/1010 was investigated by means of differential scanning calorimetry(DSC). Jeziorny equation and Mo equation were applied to describe the non-isothermal crystallization kinetics of the Nylon 10 T and the Nylon 10T/1010. The activation energies for non-isothermal crystallization were obtained by Vyazovkin's method and Friedman's method, respectively. These results showed that Jeziorny equation and Mo equation well described the non-isothermal crystallization kinetics of the Nylon 10 T and the Nylon 10T/1010. It was found that the values of the activation energy for non-isothermal crystallization of the Nylon 10T/1010 were lower than those of the Nylon 10 T at a given temperature or relative crystallinity degree,which revealed that crystallization ability of the Nylon 10T/1010 was higher. The crystal morphology was observed by means of a polarized optical microscope(POM) and X-ray diffraction(XRD). It was found that the addition of sebacic acid comonomer not only did not change the crystal form of the Nylon 10 T, but also significantly increased the number and decreased the size of spherulites. Comparing with the Nylon 10 T, the crystallization rate was increased with the addition of the sebacic acid comonomer.

Isothermal Crystallization Kinetics of Nylon 10T and Nylon 10T/1010 Copolymers:Effect of Sebacic Acid as a Third Comonomer

Nylon 10T and nylon 10T/1010 samples were synthesized by direct melt polymerization.The isothermal crystallization kinetics of nylon 10T and nylon 10T/1010 was investigated by means of differential scanning calorimetry（DSC）.The crystallization kinetics under isothermal condition has been analyzed by the Avrami equation.It was found that the Avrami equation was well-suited to describe the isothermal crystallization kinetics,combined with the results of the Turnbull-Fisher equation.The values of Tm^0 and Kg were obtained by Hoffman-Weeks and Lauritzen-Hoffman equations,respectively.The activation energies for isothermal crystallization of nylon 10T and nylon 10T/1010 were determined using the Arrhenius equation and found to be-123.24 and-81.86 kJ·mol^（-1）,respectively,which reveals that the crystallization ability of nylon 10T/1010was lower than that of nylon 10T during the isothermal crystallization process.The crystal morphology was observed by means of polarized optical microscopy（POM）and X-ray diffraction（XRD）.It was found that the addition of sebacic acid comonomer did not change the crystal form of nylon 10T,but significantly increased the number and decreased the size of spherulites.

Study of Synthesis of Copoly (lactic acid/glycolic acid) by Direct Melt Polycondensation

A two steps direct copolymerisation process was developed. The first step is to produce oligomer and then the oligomer of lactic acid/glycolic acid (90/10) is polymerized with binary catalyst tin chloride dihydrate/p-toluenesulfonic acid. In this way, the direct synthesis of copoly (lactic acid/glycolic acid) without any organic solvent was investigated. The properties and structures of products were characterized by nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), X-ray diffraction and so on. The results show that comparatively high molecular weight copolymer of lactic acid and glycolic acid can be prepared by direct processing under appropriate technological conditions.

WHOLLY-AROMATIC THERMOTROPIC LIQUID CRYSTALLINE POLYMER AND ITS BLOCK COPOLYMER

A wholly-aromatic thermotropic liquid crystalline polymer (WATLCP) composed of p-hydroxybenzoic acid (HBA), 4,4'-dihydroxy bisphenyl (BP), terephthalic acid (TPA), m-phthalic acid (MPA) was synthesized. It was symbolized by BP-LCP. Using a similar method, a new copolymer BP-PSF was prepared. BP-PSF has a semi-flexible chain polysulfone and a rigid-rod chain like BP-LCP. By FT-IR, polarizing microscope and DSC technique, the structures and properties of BP-LCP and BP-PSF were studied.