An Investigation into the Role of Capping on Second Harmonic Generation from Nonlinear Organic Polymer and Guest-Host Thin Films by In-Situ Poling

In attempts to fabricate thermally stable second-order nonlinear polymer thin films, we have investigated the second harmonic generation (SHG) from both nonlinear polymer and guest-host thin films. We have also investigated the role of capping on the SHG, temporal stability and relaxation of dipole alignment. Corona poling techniques were employed to orient the dopants into the noncentrosymmetric structure required to obtain the SHG. The effect of capping with a polymeric encapsulant below the glass transition temperature of the polymers on the unpoled and corona poled thin films was studied. Capping of the nonlinear polymer and guest host thin films have resulted in high SHG with good temporal stability. SHG signal falls drastically during the first 8 days after poling while no further significant decay in SHG signal was observed after about 33 days. Our investigations have identified the characteristics required for a good encapsulant on a non-con-ductive surface.

THE ESTIMATION OF ORDERING DEGREE OF CORONA-POLED NONLINEAR OPTICAL POLYMER FILMS

The investigation of electrochromic effect of corona-poled nonlinear optical polymer films is an effective method for the estimation of poling level and the selection of poling conditions. The poling electric field E_p and orientational order parameter Φ, which are the important parameters to predict d_(33) of poled films, can be calculated by a simple operation from the number of red shift of charge transfer absorption band. The calculated results are in good agreement with the experimental data.

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

Nonlinear Multiple Model Predictive Control of Solution Polymerization of Methyl Methacrylate

A sequential linearized model based predictive controller is designed using the DMC algorithm to control the temperature of a batch MMA polymerization process. Using the mechanistic model of the polymerization, a parametric transfer function is derived to relate the reactor temperature to the power of the heaters. Then, a multiple model predictive control approach is taken in to track a desired temperature trajectory.The coefficients of the multiple transfer functions are calculated along the selected temperature trajectory by sequential linearization and the model is validated experimentally. The controller performance is studied on a small scale batch reactor.

A MICROMECHANICAL ANALYSIS OF THE NONLINEAR ELASTIC AND VISCOELASTIC CONSTITUTIVE RELATION OF A POLYMER FILLED WITH RIGID PARTICLES

Micromechanical theory is applied to study the nonlinear elastic and viscoelastic constitutive relations of polymeric matrix filled with high rigidity solid particles. It is shown that Eshelby's method can be extended to the case of nonlinear matrix and Eshelby's tensor still exists provided that Poisson's ratio of the nonlinear matrix assumes constant value in deforming process and the rigidity of elastic filling particles is much higher than that of the matrix. A new method for averaging process is proposed to overcome the difficulty that occured in applying the ordinary equivalent inclusion method or the seff-consistant method to nonlinear matrices. A rather simple constitutive equation is obtained finally and the strengthening effect of solid particles to composites is investigated.

基于自抗扰控制技术的PVC反应温度控制

聚氯乙烯(Polyvinyl chloride,PVC)是当前世界上应用最广泛的合成材料之一。聚氯乙烯生产的关键是聚合反应过程,PVC聚合反应温度控制精度直接影响产品质量。由于PVC聚合反应过程具有大时滞及时变非线性的特点,传统的PID控制精度通常难以满足生产需要。研究了自抗扰控制技术在PVC反应温度控制中的应用,通过和IMC-PID的控制仿真对比,验证了自抗扰控制技术适应工况变化的能力。针对实际的PVC生产过程,在DCS上进行了自抗扰控制器组态,并应用于实际PVC生产过程。实际控制结果证实了自抗扰控制技术应用于PVC反应温度控制的可行性和有效性。

STUDY ON THE POLING PROPERTIES OF NONLINEAR OPTICAL ACTIVE DERIVATIVE OF POLY (p-HYDROXYSTYRENE):(PS)O-DCV

In this paper, the poling properties of (PS)O-DCV, a derivative of poly (p-hydroxystyrene ), was reported. The investigations showed that the thermochromism correction, which was neglected in the literatures, should be considered in the measurements of order parameter of poled films with electrochromism technique Here, another linear optical method, IR and polarized IR spectra for characterizing of poled films was suggested first time. The bulk second nonlinear optical coefficient d_(33) of poled films could be estimated by measured order parameter semi-qualitatively.

Optical and Electrical Properties of Polyimide Thin Films Grown by Vapor Deposition Polymerization

Using pyromellitic dianhydride (PMDA) and 4,4’ diaminodiphenyl ether (ODA) as monomer materials, polyimide thin films have been prepared onto glass substrate by vapor deposition polymerization under a vacuum of 2.666×10 -3 Pa and thermal curing of polyamic acid film in a vacuum at temperature of 150～200 ℃ for 60 min. In this process, the polymerization can be carried out through controlling the stoichiometric ratio, heating time and deposition ratio of the two monomers. The composition, the structure and properties of the polyimide films are investigated with IR spectrum, XRD, and SEM methods. The results show that the polyimide films by vapor deposition polymerization have good electrical properties and thermal stability. Therefore, the vapor deposition polymerization process is considered as a possible method of polymerization for other polymers.

Optical and Electrical Properties of Polyimide Thin Films Doped-Cu-phthalocyanine Polymerized by Vapor Phase Deposition

Using Cu-phthalocyanine（CuPc）,4,4’-diaminodiphenyl ether and pyromellitic dianhydride as monomer materials, polyimide（PI） thin films doped-CuPc have been prepared onto glass substrate by vapor phase co-deposition polymerization under a vacuum of 2×10-3Pa and thermal curing of polyamic acid film in at temperature of 150-200℃ for 60min. In this process, the polymerization can be carried out through controlling the stoichiometric ratio, heating time and deposition rates of the three monomers. IR spectrum identifies the designed chemical structure of the polymer. The absorption of polyimide doped-CuPc is very intense in vis-range and near-infrared by UV-Vis spectrum. And, the PI films doped-CuPc polymerized by vapor phase deposition have uniformity, fine thermal stability and good nonlinear optical properties, and the third-order optical nonlinear susceptibility χ（3） with degenerate four-wave mixing can be 1.984×10-9ESU.

Synthesis of End Functional Polymers via Atom Transfer Radical Polymerization in Immobilized Catalytic System

Cross-linked polystyrene with azo-crown ether functional side chain (PSt-1, 10-dicarbonyl-3,6,9-trizaoeylcode-cane) was prepared under microwave irradiation and the structure was characterized through FT-IR and element analysis. The functionalized cross-linked polystyrene (cross-link degree, 3.5%) combining with immobilized catalyst system (CuBr and ethylα-bromo-isobutyrate) can catalyze atom transfer radical polymerization of Styrene. Neat polymer products can be obtained then. Complex of La and the polymer end group (EBiB) was synthesized. The third order nonlinear optical property of the polymer-La complex was investigated and the structure was also characterized by FT-IR and XPS.

Enhanced Constitutive Theories for Classical Thermoviscoelastic Polymeric Fluids

This paper presents ordered rate nonlinear constitutive theories for thermoviscoelastic fluids based on Classical Continuum Mechanics (CCM). We refer to these fluids as classical thermoviscoelastic polymeric fluids. The conservation and balance laws of CCM constitute the core of the mathematical model. Constitutive theories for the Cauchy stress tensor are derived using the conjugate pair in the entropy inequality, additional desired physics, and the representation theorem. The constitutive theories for the Cauchy stress tensor consider convected time derivatives of Green’s strain tensor or the Almansi strain tensor up to order n and the convected time derivatives of the Cauchy stress tensor up to order m. The resulting constitutive theories of order (m, n) are based on integrity and are valid for dilute as well as dense polymeric, compressible, and incompressible fluids with variable material coefficients. It is shown that Maxwell, Oldroyd-B, and Giesekus constitutive models can be described by a single constitutive theory. It is well established that the currently used Maxwell and Oldroyd-B models predict zero normal stress perpendicular to the flow direction. It is shown that this deficiency is a consequence of not retaining certain generators and invariants from the integrity (complete basis) in the constitutive theory and can be corrected by including additional generators and invariants in the constitutive theory. Similar improvements are also suggested for the Giesekus constitutive model. Model problem studies are presented for BVPs consisting of fully developed flow between parallel plates and lid-driven cavities utilizing the new constitutive theories for Maxwell, Oldroyd-B, and Giesekus fluids. Results are compared with those obtained from using currently used constitutive theories for the three polymeric fluids.

基于非线性聚合的多类型指标综合评估方法

针对多类型指标综合评估问题,将实数型、区间数型和模糊数型指标相结合,构建评估指标体系。采用区间数特征向量法和信息熵权法确定指标权重,并针对3种不同类型的指标分别定义了评分方法。引入非线性聚合理论,建立了基于非线性聚合的多类型指标综合评估指标体系。最后,以某型军事指挥信息系统的指挥控制能力评估为例,进行了实例运算,验证了该模型与方法的合理性和有效性。

酚醛树脂聚合反应过程的模糊控制

针对酚醛树脂在间歇式反应釜内的聚合反应过程具有非线性、时变的特点,通过总结生产现场的操作经验,用模糊条件语句构成相应的模糊控制规则,提出了一种可以工程实现的模糊控制模型,经模型仿真说明,这类模糊控制器是可行的,并易于工程实现。

气相沉积法制备聚酰亚胺薄膜的光、电特性研究

以均苯四甲酸二酐 (PMDA)和二氨基二苯醚 (ODA)为单体原料 ,研究了在 3× 10 - 3Pa真空度下 ,通过控制双源单体的加入摩尔计量、加热时间和其沉积速率 ,在玻璃衬底上合成了聚酰亚胺的预聚体聚酰胺酸 ,再经 15 0～ 2 0 0℃真空加热亚胺化 1h后得到了成膜性良好的均匀聚酰亚胺薄膜。通过红外吸收、X射线衍射和扫描电镜等方法对样品的组织结构和特性进行了研究和探讨。结果表明 。

非线性光学材料及其分子设计和聚集态设计述评

在介绍非线性光学材料的类别的同时，以“电荷转移”理论为依据，对二阶非线性光学材料和三阶非线性光学材料的分子结构与性能的关系以及分子设计原则作了评述，并比较了有机晶体、金属有机和高分子材料各自的非线性光学性质及结构特点．讨论了二阶非线性光学材料的聚集态设计．

1，12-二（2-吡啶基）-1，3，5，7，9，11-十二-六炔的合成与性质研究

本文中我们合成了一种新颖的乙炔衍生物，1，12-二（2-吡啶基）-1，3，5，7，9，11-十二-六炔（7），并利用红外光谱（IR），紫外光谱（UV），核磁（NMR），质谱（MS）对其结构进行了鉴定。在对其性质研究研究中，采用红外光谱（IR）和紫外光谱（UV）对7的拓扑固相聚合性质进行了初步的探讨。实验结果表明，化合物7在加热和紫外光照射条件下能够发生固相聚合得到结构复杂的聚合物，这是由于其结构未能符合进行典型规则的1，2-聚合或者1，4-聚合的结构条件的原因。

基于LMBP神经网络的聚合反应预测控制

研究基于LMBP神经网络算法的预测控制策略在苯乙烯本体聚合反应产物组分控制领域的应用。利用神经网络对非线性系统的逼近能力,把预测控制推广到聚合反应过程质量指标控制这一非线性系统中。仿真结果证明,基于神经网络算法的预测控制策略达到了较好的控制质量。

气相沉积法制备聚酰亚胺薄膜的光、电特性研究

以均苯四甲酸酐（ＰＭＤＡ）和二氨基二苯醚（ＯＤＡ）为单体原料，研究了在２×１０－５Ｔｏｒｒ真空度下，通过控制双源单体的加入摩尔计量、加热时间和其沉积速率，在玻璃衬底上合成了聚酰亚胺的预聚体聚酰胺酸，再经１５０～２００℃真空加热亚胺化，１小时后得到了成膜性良好的均匀聚酰亚胺薄膜。通过红外吸收、ｘ射线衍射、扫描电镜等方法对样品的组织结构和特性进行了研究和探讨。结果表明，气相沉积法制备的聚酰亚胺薄膜具有良好的电学特性和热稳定性，不失为聚合物合成的可能途径之一。

非线性状态空间预测控制在聚丙烯装置中的应用

为解决实际装置Spheripol-II液相双环管聚丙烯反应器工艺瓶颈和控制难点,从丙烯聚合反应动力学出发,根据物料平衡和能量平衡原理建立了反应器动态数学模型,采用基于状态空间模型非线性预测控制策略,开发了由"DCS控制层"和"上位机控制层"构成的先进控制系统。结合DCS逻辑切换安全保护方法,该系统可灵活投用与切除,保障了双环管反应器控制问题的安全性。该控制器成功应用于国内某石化企业聚丙烯装置,有效地减少了双环管反应器反应温度和反应密度等关键参数的工艺波动,实现了熔体流动速率等产品质量指标的闭环控制,产品质量稳定提升,关键运行参数在投用先进控制系统后标准偏差减少了25%以上。

2-甲基-8-（9，9-二丁基芴）-3，5，7-三炔-2-辛醇的合成和性质研究

合成了一种新颖的乙炔衍生物，2-甲基-8-（9，9-二丁基芴）-3，5，7-三炔-2-辛醇（6a），并利用红外光谱（IR），紫外光谱（Uv），核磁（NMR），质谱（MS）等对其结构进行了表征。利用红外光谱（IR）和紫外光谱（Uv）对其拓扑固相聚合性质进行了研究。实验结果表明，这些化合物在加热和紫外光照射条件下都能够发生固相聚合，但得到的是结构复杂的聚合物。