聚（ε-己内酯）泡沫塑料制备与性能研究

随着人们环保意识的普遍提高，可生物降解材料已经成为了世界范围的研究热点。开展可生物降解高分子泡沫塑料的结构与性能的研究，对以可生物降解的高分子泡沫塑料替代不能生物降解的泡沫塑料，遏制白色污染，保护生态环境，具有重要的科学价值和社会意义。本工作选用聚（ε-己内醋）（PCL）为原料，通过辐射方法引发PCL交联，提高其熔体粘度和强度；以AC为发泡剂，制备PCL泡沫材料：添加无机纳米粒子-碳酸钙，进一步提高PCL的发泡倍率。研究辐射剂量、凝胶含量、分子量、AC发泡剂含量、碳酸钙含量等因素对制备泡沫塑料的影响，优化组合，获得PCL泡沫材料。主要研究结果如下：1．采用辐照交联的方法实现了PCL的交联，凝胶含量最高可达到41％；2．交联后的PCL热稳定性略有下降，结晶性能基本没有变化。但是，抗张性能变化很大，弹性模量提高（260MPa-430MPa），断裂伸长率下降（1500％-30％）。由此推测，提高了PCL的熔体强度；3．制备出了PCL泡沫塑料，发泡倍率可控制在2-12范围内。其中，发泡倍率与发泡剂含量、PCL分子量关系密切。当辐照计量大于5Mrad后，辐照计量对发泡倍率影响不大，但是，对泡孔的结构影响很大，即辐照剂量大，得到的泡孔直径小；4．体系中添加CoCO_3使得PCL的发泡倍率进一步提高，最高可达到15倍，并且使泡孔数量增加，体积减小。添加30wt％碳酸钙，PCL泡沫塑料的孔径为147μm，单位体积泡孔数为29.6*10~8cell/cm~3，壁厚4.48μm。

无定形1，2－聚丁二烯的分子链结构和分子链的相互作用

聚合物的结构决定了它的分子链的运动，分子链的运动又可表征聚合物的结构，而且聚合物的宏观性质又受到它的微观运动的影响。因此有目的地开发各种聚合物材料，充分利用其独特的性质，都离不开研究它的微观运动。这就是结构－性能－运动的关系。1，2－聚丁二烯作为一种弹性体，近十几年研究得较多，主要局限在它的链节结构（1，2－链节）与其物理机械性能的关系方面，其目的是为了弥补顺丁橡胶的不足。对于1，2－链节与其分子链的微观运动则研究得较少。然而这方面的研究对于1，2－聚丁二烯弹性体的开发和应用无疑是有益的。研究1，2－聚丁二烯的链节结构与其分子链的相互作用，首先需要选择适当的表征分子链的各种相互作用的参数。聚合物分子链的长程运动，可分为分子链内旋转运动和分子链间相互作用。其中分子链间相互作用通常用聚合物的内聚能密度表示，分子链内旋转运动决定分子链的柔顺性，而它们二者共同影响聚合物的玻璃化温度。因此实验中首先测定1，2－聚丁二烯的玻璃化温度和内聚能密度，从研究1，2－链节与1，2－聚丁二烯分子链的忌的相互作用和分子链间的相互作用着手。实验需要的1，2－聚丁二烯样品部分是用丁基锂制备的，也有别人提供的钼体系和铁体系的样品。样品的1，2－链节含量从8％至90％。主要用线膨胀法（还有DSC法及扭摆法）测定了1，2－聚丁二烯的玻璃化温度。不仅发现了1，2－聚丁二烯的玻璃化温度随1，2－链节增多而提高，而且得到了它们在玻璃化转变时的体积膨胀系数。这个系数对于后面研究分子链柔顺性是有用的。聚合物的内聚能密度是其溶解度参数的平方。实验选用特性粘数法测定1，2－聚丁二烯的溶解度参数，其中关键在于选择适当的溶剂。这方面失败的教训是由于所用的溶剂在化学结构和极性上与聚合物的相差甚大。由于这种限制，测定1，2－聚丁二烯的溶解度参数时，难以找到化学结构和极性合适且溶解度参数又相当的纯溶剂。因此按照溶解度参数理论，配制了不同溶解度参数的环已焓一甲苯混合溶剂，代替部分纯溶剂。测定结果表明，1，2－链节含量为16％的样品，其溶解度参数为8.6（[卡／立方厘米]~(1/2)），其余含量较高的样品，都是8.5（[卡/立方厘米]~(1/2)）。用混合溶剂测定聚合物的溶解度参数还是第一资，其可靠性取决于混合溶剂的溶解度参数的准确性。根据溶解度参数理论，我们提出克分子体积相近，且无特殊的相互作用的二元混合溶剂的溶解度参数，等于它们各自的溶解度参数按体积分数的加合。环已烷和甲苯的克分子体积分别为108.7和106.8立方厘米，它们的溶解度参数的极性分量S_极 → 0，再假定混合时没有吸热效应，它们二者按体积分数加合的溶解度参数可以定量使用。用时还从三个方面进行了验证，(1)用克分子体积相差较大(分别为147.4和89.4立方厘米)的正庚焓－苯混合溶剂作为反证；(2)根据特性粘数理论，用Matsuo方程；(3)由三元(溶剂1－溶剂2－聚合物)体系的Flory-Huggins相互作用参数等，它们都证实了上面提出的混合溶剂测定1,2－聚丁二烯溶解度参数的条件。根据前面的实验结果发现，1，2－链节与1，2－聚丁二烯的玻璃化温度有关，与其内聚能密度基本无关。建么1，2－链节必定与其分子链柔顺性有关。为了更准确地说明1，2－链节对1，2－聚丁二烯分子链柔顺性的影响，需要选择表征分子链柔顺性的参数。聚合物的分子链中相互作用的直观表现是它的分子链柔顺性，而分子链的柔顺性起因于它的链状分子和分子链的内旋转运动。因此我们选用分子链内旋转的参数（内旋转势垒和内旋转异构化能）表征1，2－聚丁二烯分子链的柔顺性。目前文献报道的计算分子链内旋转异构化能的方法，大多数是根据Gibbs-DiMarzio的玻璃化转变理论。这些方法一般都比较复杂。我们提出从聚合物发生玻璃化转变时的温度和体积膨胀系数，计算分子链内旋转异构化能的简便方法。这个方法的基本出发点是认为聚合物发生玻璃化转变时的自由体积，对不同结构的聚合物并非常数，其原因在于玻璃化转变时的聚合物体积膨胀系数部分地来自于分子链构象变化的贡献。分子链内旋转引起构象变化时，分子链的内旋转异构化能也相应地变化。因此玻璃化转变时，分子链的构象变化既对聚合物的体积膨胀系数有影响，又与分子链内旋转异构化能有联系，那么此时的聚合物的体积膨胀系数，与单个分子链的内旋转异构化能必然有某种联系。若用Δα·Tg（Δα是随态和玻璃态的体积膨胀系数）表示玻璃化温度Tg下，单个分子链处于能量状态∈的几率，Ng表示相同温度下，分子链中处于相同能量状态中的柔顺链分数，按照统计力学原理得到∈=-K·TgLn((Δα·Tg)/(1-Δα·Tg))。(1)

Laterally Electrostatically Driven Poly 3C-SiC Folded-Beam Resonant Microstructures

Micromachined comb-drive electrostatic resonators with folded-cantilever beams were designed and fabricated. A combination of Rayleigh＇s method and finite-element analysis was used to calculate the resonant frequency drift as we adjusted the device geometry and material parameters. Three micromachined lateral resonant resonators with different beam widths were fabricated. Their resonant frequencies were experimentally measured to be 64.5,147.2, and 255.5kHz, respectively, which are in good agreement with the simulated resonant frequency. It is shown that an improved frequency performance could be obtained on the poly 3C-SiC based device structural material systems with high Young＇s modulus.

An Integratable Distributed Bragg Reflector Laser by Low-Energy Ion Implantation Induced Quantum Well Intermixing

An integratable distributed Bragg reflector laser is fabricated by low-energy ion implantation induced quantum well intermixing. A 4.6nm quasi-continuous wavelength tuning range is achieved by controlling phase current and grating current simultaneously,and side mode suppression ratio maintains over 30dB throughout the tuning range except a few mode jump points.

O2在FeSi（100）表面的初始吸附研究

于2010-11-23批量导入

Design of spectrometer based on volume phase grating for near infrared range

In order to design and fabricate a spectrometer for the infrared range widely used in the different applications, Volume Phase Grating (VPG) with. low Polarization Dependence Loss (PDL) and high efficiency has been adopted as the dispersion element. VPG is constructed by coating an optical substrate with a thin film of dichromated. gelatin and exposing the film to two mutually coherent laser beams to form index modulation. The diffraction efficiency for a VPG is governed by Bragg effects. The depth (d) and index modulation contrast of the grating structure control the efficiency at which the light is diffracted when the Bragg condition is satisfied. Gradient index lens with high performance and low aberration are used as collimating system instead of standard lens. The spot diagrams and MTF curve of the collimating lens are shown in the paper. The receive system is InCaAs photodiode (PD) array including 512 pixels with 25 mum pitch. The spectrum resolution of the spectrometer reaches to 0.2nm and wavelength accuracy is 40pm.

Photoluminescence characteristics of GaAs/AlGaAs quantum dot arrays fabricated by dry and dry-wet etching

GaAs/AlGaAs quantum dot arrays with different dot sizes made by different fabrication processes were studied in this work. In comparison with the reference quantum well, photoluminescence (PL) spectra from the samples at low temperature have demonstrated that PL peak positions shift to higher energy side due to quantization confinement effects and the blue-shift increases with decreasing dot size, PL linewidths are broadened and intensities are much reduced. It is also found that wet chemical etching after reactive ion etching can improve optical properties of the quantum dot arrays.

Transport properties through quantum dot in a vertical electric field

The transport properties through a quantum dot are calculated using the recursion method. The results show that the electric fields can move the conductive peaks along the high- and low-energies. The electric field changes the intensity of conductance slightly. Our theoretical results should be useful for researching and making low-dimensional semiconductor optoelectronic devices. (C) 2002 Elsevier Science B.V. All rights reserved.

Energy band and acceptor binding energy of GaN and AlxGa1-xN

The hole effective-mass Hamiltonian for the semiconductors of wurtzite structure is established, and the effective-mass parameters of GaN and AlxGa1-xN are given. Besides the asymmetry in the z and x, y directions, the linear term of the momentum operator in the Hamiltonian is essential in determining the valence band structure, which is different from that of the zinc-blende structure. The binding energies of acceptor states are calculated by solving strictly the effective-mass equations. The binding energies of donor and acceptor for wurtzite GaN are 20 and 131, 97 meV, respectively, which are inconsistent with the recent experimental results. It is proposed that there are two kinds of acceptors in wurtzite GaN. One kind is the general acceptor such as C, substituting N, which satisfies the effective-mass theory, and the other includes Mg, Zn, Cd etc., the binding energy of which deviates from that given by the effective-mass theory. Experimentally, wurtzite GaN was grown by the MBE method, and the PL spectra were measured. Three main peaks are assigned to the DA transitions from the two kinds of acceptor. Some of the transitions were identified as coming from the cubic phase of GaN, which appears randomly within the predominantly hexagonal material. The binding energy of acceptor in ALN is about 239, 158 meV, that in AlxGa1-xN alloys (x approximate to 0.2) is 147, 111 meV, close to that in GaN. (C) 2000 Published by Elsevier Science S.A. All rights reserved.