Crystallization kinetics of poly(ether ether ketone) (PEEK) from its metastable melt

After isothermal crystallization of the amorphous poly(ether ether ketone), double endothermic behaviour can be found through differential scanning calorimetry experiments. During the heating scan of semicrystalline PEEK, a metastable melt, which comes from the melt of the thinner lamellar crystal populations, can be obtained between these two endotherms. The metastable melt can recrystallize immediately just above the lower melting temperature and form slightly thicker lamellae than the original ones. The thickness and the perfection depend upon the crystallization time and the crystallization temperature. By comparing the TEM morphological observations of the samples before and after partial melting, it can be shown that lamellar crystals, having different thermodynamic stability, form during isothermal crystallization. After partial melting, only the type of lamellar crystal exhibiting the higher thermodynamic stability remains. Wide angle X-ray diffraction measurements shows a slightly change in the crystallinity of the samples before and after the partial melting. Small angle X-ray scattering results exhibit a change in the long period of the lamellar crystals before and after the partial melting process. The crystallization kinetics of the metastable melt can be determined by means of differential scanning calorimetry. The kinetic analysis showed that the isothermal crystallization of the metastable PEEK melt proceeds with an Avrami exponent of n = 1.0 similar to 1.4, reflecting that probably one-dimensional or an irregular line growth of the crystal occurred between the existing main lamellae with heterogeneous nucleation. (C) 1998 Elsevier Science Ltd. All rights reserved.

Isothermal melt and cold crystallization kinetics of poly(aryl ether ether ketone ketone) (PEEKK)

Isothermal melt and cold crystallization kinetics of PEEKK have been investigated by differential scanning calorimetry in two temperature regions. During the primary crystallization process, the relative crystallinity develops with a time dependence described by the Avrami equation, with exponent n = 2 for both melt and cold crystallization. The activation energies are -544.5 and 466.7 kJ/mol for crystallization from the melt and amorphous glassy state, respectively. The equilibrium melting point T-m(o) is estimated to be 371 degrees C by using the Hoffman-Weeks approach. The lateral and end surface free energies derived from the Lauritzen-Hoffman spherulitic growth rate equation are sigma=10 erg/cm(2) and sigma(e) = 60 erg/cm(2), respectively. The work of chain folding q is determined as 3.98 kcal/mol. These observed crystallization kinetic characteristics of PEEKK are compared with those of PEEK. (C) 1997 Elsevier Science Ltd.

Thermal analysis of ethylene propylene copolymer-grafted-acrylic acid

The thermal properties of ethylene propylene copolymer-grafted-acrylic acid (EP-g-AA) were investigated by using differential scanning calorimetry (DSC). Compared with the ethylene propylene copolymer (EP), the peak values of the melting temperature (T-m) of the propylene sequences in the grafted EP changed a little, the crystallization temperature (T-c) increased about 8-12 degrees C, and the melting enthalpy (Delta H-m) increased about 4-6 J/g. The isothermal crystallization kinetics of grafted and ungrafted samples was carried out by DSC. Within the scope of the researched crystallization temperature, the Avrami exponent (n) of the ungrafted sample was 1.6-1.8, and that of grafted samples were all above 2, which indicated that the grafted monomer could become the crystal nuclei for the crystallization of propylene sequence. With increasing grafted monomer content, the crystallization rate of propylene sequence in grafted EP increased; it might be the result of rapid nucleation rate and crystal growth rate.

Crystallization behavior of a novel poly(aryl ether ketone): PEDEKmK

Isothermal melt and cold crystallization kinetics of PEDEKmK linked by meta-phenyl and biphenyl were investigated by differential scanning calorimetry in two temperature regions. Avrami analysis is used to describe the primary stages of the melt and cold crystallization, with exponent n = 2 and n = 4, respectively. The activation energies are -118 kJ/mol and 510 kJ/mol for crystallization from the melt and the glassy states, respectively. The equilibrium melting point T-m(0) is estimated to be 309 degrees C by using the Hoffman-Weeks approach, which compares favorably with determination from the Thomson-Gibbs method. The lateral and end surface free energies derived from the Lauritzen-Hoffman spherulitic growth rate equation are sigma = 8.45 erg/cm(2) and sigma(e) = 45.17 erg/cm(2), respectively. The work of chain folding q is determined as 3.06 kcal/mol. These observed crystallization characteristics of PEDEKmK are compared with those of the other members of poly(aryl ether ketone) family. (C) 1997 John Wiley & Sons, Inc.

Thermal analysis of ethylene-propylene copolymer-grafted-glycidyl methacrylate

The thermal properties of ethylene-propylene copolymer grafted with glycidyl methacrylate (EP-g-GMA) were investigated by using differential scanning calorimetry (DSC). Compared to the plain ethylene-propylene copolymer (EP), peak values of melting temperature (T-m) of the propylene sequences in the grafted EP changed a little, crystallization temperature (T-c) increased about 8-12 degrees C, and melting enthalpy (Delta H-m) increased about 4-6 J/g. The isothermal and nonisothermal crystallization kinetics of grafted and ungrafted samples was carried out by DSC. Within the scope of the researched crystallization temperature, the Avrami exponent (n) of ungrafted sample is 1.6-1.8, and those of grafted samples are all above 2. The crystallization rates of propylene sequence in EP-g-GMA were faster than that in the plain EP and increased with increasing of grafted monomer content. It might be attributed to the results of rapid nucleation rate. (C) 1996 John Wiley & Sons, Inc.

Fractal roughness characterization of super-ground Mn-Zn ferrite single crystals

The surface of superground Mn-Zn ferrite single crystal may be identified as a self-affine fractal in the stochastic sense. The rms roughness increased as a power of the scale from 10(2) nm to 10(6) nm with the roughness exponent alpha = 0.17 +/- 0.04, and 0.11 +/- 0.06, for grinding feed rate of 15 and 10 mu m/rev, respectively. The scaling behavior coincided with the theory prediction well used for growing self-affine surfaces in the interested region for magnetic heads performance. The rms roughnesses increased with increase in the feed rate, implying that the feed rate is a crucial grinding parameter affecting the supersmooth surface roughness in the machining process.

Crystallization behaviour of poly(ether ether ketone)/poly(ether sulfone) block copolymer

The crystallization and melting behaviours of a multiblock copolymer comprising poly(ether ether ketone) (PEEK) and poly(ether sulfone) (PES) blocks whose number average molecular weights <((M)over bar (n)'s)> were 10 000 and 2900, respectively, were studied. The effect of thermal history on crystallization was investigated by wide-angle X-ray diffraction measurement. A differential scanning calorimeter was used to detect the thermal transitions and to monitor the energy evolved during the isothermal crystallization process from the melt. The results suggest that the crystallization of the copolymer becomes more difficult as compared with that of pure PEEK. The equilibrium melting point of the copolymer was found to be 357 degrees C, about 30 degrees C lower than that of pure PEEK. During the isothermal crystallization, relative crystallinity increased with crystallization time, following an Avrami equation with exponent n approximate to 2. The fold surface free energy for the copolymer crystallized from the melt was calculated to be 73 erg cm(-2), about 24 erg cm(-2) higher than that of pure PEEK. Copyright (C) 1996 Elsevier Science Ltd.

KINETICS OF NONISOTHERMAL PHASE-TRANSITION OF POLY(ESTER-IMIDE)

Based on Jeziorny theory, the kinetics of phase transition of poly(ester-imide) has been determined under non-isothermal condition by using differential scanning calorimetry (DSC). Avrami exponent n, kinetic parameters G(c) and rate constant Z(c) were derived and discussed.

A STUDY OF MODE-I DELAMINATION RESISTANCE OF A THERMOPLASTIC COMPOSITE

This paper describes the mode I delamination behaviour of a unidirectional carbon-fibre/poly(phenylene ether ketone)(PEK-C) composite. Tests have been performed on double cantilever beam (DCB) specimens. Several data reduction schemes are used to obtain the critical strain energy release rate, G(IC), and the results are compared. It is shown that when using a DCB test to determine the fracture toughness, corrections must be employed. The experimental methods have been described for ascertaining the correction terms, and the results are consistent after modification. Some of the authors' results are different from those of other authors, particularly the negative correction term for crack length, the larger exponent (n > 3) in the relationship C = Ra(n), and decrements of flexural modulus with the crack growth when using the simple beam theory to predict the bending behaviour of DCB specimens. The possible reasons are discussed.

Self-organized Criticality Model for Ocean Internal Waves

In this paper, we present a simple spring-block model for ocean internal waves based on the self-organized criticality (SOC). The oscillations of the water blocks in the model display power-law behavior with an exponent of -2 in the frequency domain, which is similar to the current and sea water temperature spectra in the actual ocean and the universal Garrett and Munk deep ocean internal wave model [Geophysical Fluid Dynamics 2(1972) 225; J. Geophys. REs. 80 (1975) 291]. The influence of the ratio of the driving force to the spring coefficient to SOC behaviors in the model is also discussed.

Dielectric response of spherically anisotropic graded piezoelectric composites

A graded piezoelectric composite consisting of a spherically anisotropic graded piezoelectric inclusion imbedded in an infinite nonpiezoelectric matrix, with the physical properties of the graded spherical inclusion having a power-law profile with respect to the radial variable r, is studied theoretically. Under an external uniform electric field, the electric displacement field and the elastic stress tensor field of this spherically anisotropic graded piezoelectric composite are derived exactly by means of displacement separation technique, based on the governing equations in the dilute limit. A piezoelectric response mechanism, in which the effective piezoelectric response vanishes along the z direction (or x,y directions), is revealed in this kind of graded piezoelectric composites. Furthermore, it is found that the effective dielectric constant decreases (or increases) with the volume fraction p of the inclusions if the exponent parameter k of the grading profile is larger (or smaller) than a critical value. (C) 2007 American Institute of Physics.

网络控制系统稳定性的图理论

针对具有有界时延和数据包丢失的网络控制系统,提出了一种新的稳定性判据.基于Lyapunov方法和图论理论,给出非线性离散和连续网络控制系统渐近稳定的充分条件,获得保持这两类系统稳定的最大允许时延界,得到控制器设计方法.并且,利用区间矩阵的谱特征,给出网络控制系统区间稳定的充分条件.设计算法,获得比例积分反馈控制器增益.算例表明所提方法的有效性。

互联网上机器人的遥控理论与方法综述

给出了系统的研究模型,指出系统控制和设计必须考虑的3个关键问题:稳定性、透明性和时延处理.阐述了4个主要的稳定性分析方法:Lyapunov稳定性、输入输出稳定性、无源稳定性和基于事件的稳定性,总结了这些方法的优势和局限性.接着,给出了几种主要的控制策略,指出了现有控制方法的优缺点.最后,提出了进一步的主要研究方向.

仿射非线性系统的广义逐点最小范数控制

在Freeman的逐点最小范数控制器的基础上,提出了一种新的非线性控制器设计框架-广义逐点最小范数控制器,并证明了其连续性.通过一个引导函数,新的控制器可以和其他的控制器设计策略结合,从而大大提高了控制器设计的灵活性.另外,给出了新方法的两个应用:改善局部线性化控制器稳定域较小的缺陷;及和其它控制器设计方法结合,使之能够简单有效地处理具有输入约束的系统.

多移动机器人主—从编队控制研究

多机器人编队控制是多移动机器人自主协调控制领域中的关键技术。这篇论文在基于局部测量和局部控制的框架下，研究具有主—从跟踪结构的移动机器人编队系统的建模和控制问题。论文的主要研究内容可分为如下三个方面：针对一阶运动学和二阶运动学模型的编队控制器设计；将基于运动学的编队控制器与基于从机器人动力学的载体控制器相结合；将队形反馈信息融入主机器人的轨迹跟踪控制器，给出了主机器人的协调编队控制器的设计。具体内容可概括为如下几个方面：（1）以主—从机器人编队中从机器人的固联视觉传感器的观察角度出发，用视觉等效相对速度建立了主—从机器人编队系统的运动学模型。同时，在该模型中考虑了由视觉传感器时间延迟所导致的模型误差对编队系统的影响。在基于该运动学模型的编队控制器的设计过程中结合了基于从机器人载体的动力学的速度控制器。这种基于编队运动学和机器人本体动力学相结合的控制方法，避免了以往文献中速度跟踪响应无限快的假设。使得对编队控制系统的分析和设计更趋于实际。用Lyapunov稳定性理论证明了主—从机器人之间的编队跟踪误差和从机器人载体的速度跟踪误差都可以收敛到零--整体系统的渐进稳定性。（2）结合上述编队控制律，提出了一种编队系统中从机器人主动避障的方法，该方法能够令从机器人在避开动态障碍物的同时，与主机器人保持期望的相对距离或相对方位。这种方法的实质是由主机器人来引导从机器人的避障过程，主—从机器人之间通过相互协作来完成避障任务。这就使得从机器人即使在避障的过程中也能够与主机器人保持部分的协作。这样，当避障过程结束之后，主—从机器人之间可以迅速的恢复队形。（3）导出了一种新的基于相对运动学的主—从跟踪系统的二阶运动学模型。利用这个运动学模型，我们设计了一个由反馈线性化控制器和一个滑模控制器组成的复合控制器，来实现机器人主—从跟踪系统的控制。运用Lyapunov理论证明了所设计的队形控制器能够镇定包括内部动力学系统在内的整个主—从跟踪系统。同时，该控制器使得队形跟踪系统对主机器人的绝对加速度具有鲁棒性。此外，在前述控制器的基础上，我们设计了一个自适应队形控制器来处理主—从跟踪系统中存在的参数不确定性。（4）将上述基于二阶运动学的编队控制方法与从机器人的载体动力学控制系统相结合，给出了将编队运动学与载体动力学相结合的编队控制器设计方法。同时，针对载体动力学模型中含有参数不确定性的情况，设计了基于自适应控制方法的编队控制器。同时，利用Lyapunov理论给出了保证整体系统稳定性的条件。（5）基于主—从编队系统的二阶运动学模型，将队形反馈信息引入主机器人的轨迹跟踪控制器中，形成了主—从机器人协调编队的辅助控制律。该辅助控制律所对应的虚拟协调力通过主机器人的动力学系统形成了真实的协作控制力。该控制器与前一章中的从机器人的鲁棒编队跟踪控制器共同形成了主—从编队系统的协调控制器。应用Lyapunov理论给出了在主—从机器人分别采用协调编队控制器的作用下所形成的闭环系统的稳定性条件。进一步地，我们将主机器人的面向轨迹跟踪任务的协调控制器转换为面向路径跟踪任务的协调控制器。分别利用了基于MATLAB的仿真平台和实际的多移动机器人系统，验证了以上各方法的有效性。