离子液体电沉积CuInxGa1-xSe2薄膜

采用循环伏安法(CV)对离子液体Reline中三元CuCl₂+InCl₃+SeCl₄体系和四元CuCl₂+InCl₃+GaCl₃+SeCl₄体系的电化学行为进行了研究。研究表明,In³⁺并入三元CIS(Cu-In-Se)薄膜体系和Ga³⁺并入四元CIGS(Cu-In-Ga-Se)薄膜体系均有两种途径：一是发生共沉积,二是直接还原。利用电感耦合等离子体发射光谱(ICP)和扫描电镜(SEM)对沉积电势、镀液温度和主盐浓度对CIGS薄膜组成、镀层表面形貌的影响进行了测试,结果表明通过工艺参数的选择可以控制Ga/(Ga+In)和CIGS薄膜组成并得到化学计量比为Cu_1.00In_0.78Ga_0.27Se_2.13的薄膜。     

酒石酸铅锆的制备、表征及其燃烧催化作用

以酒石酸、硝酸氧锆和硝酸铅为原料,合成出了双金属盐酒石酸铅锆,采用有机元素分析、X射线荧光光谱和FTIR对其进行了表征。在程序升温条件下,利用TG/DTG、DSC、固相原位反应池/FTIR联用技术,研究了酒石酸铅锆的热行为和热分解机理,描述了酒石酸铅锆的热分解过程,分析得出其最终分解产物为ZrO2、PbO和C。利用螺压工艺制备了含酒石酸铅锆的推进剂样品,研究了酒石酸铅锆对双基系推进剂燃烧性能的影响,分析了其燃烧催化作用。结果表明,酒石酸铅锆对双基系推进剂的燃烧具有良好的催化作用,是一种高效的燃烧催化剂;酒石酸铅锆热分解的最终产物PbO是催化燃烧的主要活性物质,推进剂燃烧过程中形成了氧化铅-铅循环催化体系,而锆和碳则起辅助催化的作用。     

间氨基水杨酸修饰超高交联吸附树脂对酚类化合物的吸附行为

合成间氨基水杨酸修饰的超高交联吸附树脂LZ-01,比较LZ-01树脂与NJ-8树脂对对甲基苯酚和对硝基苯酚的吸附能力,研究LZ-01树脂在不同温度(288K,313K,318K)下吸附水溶液中对甲基苯酚和对硝基苯酚的静态吸附热力学和动力学行为。结果表明,由于LZ-01树脂具有更大的比表面积、更多的微孔且含有氨基、羟基和羧基等基团,使其对对甲基苯酚和对硝基苯酚的吸附量明显高于NJ-8树脂。Freundlich方程对等温吸附数据能够很好地拟合,吸附焓变绝对值小于40kJ/mol,表明吸附是焓驱动的物理吸附过程。LZ-01树脂对对甲基苯酚和对硝基苯酚吸附动力学均符合准一级动力学方程,吸附速率随温度升高而增大,颗粒内扩散是该吸附过程的速控步骤。     

Solution Crystallization Behavior of Linear and Star-shaped Poly(ethylene glycol)-b-Poly(ε-caprolactone) Block Copolymers简

Lamellar crystals of diblock, triblock and four-arm poly（ethylene glycol）-b-poly（ε-caprolactone） （PEG-b-PCL） crystalline-crystalline copolymers were successfully obtained from their solution. Morphology and structure of lamellar crystals of crystalline-crystalline copotymers were investigated using tapping-mode atomic force microscopy （AFM） and selected area electron diffraction （SAED）. All of these samples showed the truncated-lozenge multilayer basal shapes with central screw dislocation or central stack, which were all obtained simultaneously from the oil bath. The diffraction pattern of PEG block lamellar crystal is attributed to the （120） diffracting planes and the pattern of PCL block lamellar crystal is attributed to the （1 I0） diffracting planes and （200） diffracting planes according to the SAED results. Four （110） crystal growth planes and two （200） crystal growth planes are discovered for the PCL blocks, but the （120） crystal growth planes of PEG blocks are hided in the figure of AFM. The crystalline structure of the four-arm copolymers （FA） is more disorder and confused than that of the diblock （DI） copolymer and the striated fold surface structures of lamellar crystals of four-arm copolymers （FA） are smoother than these of linear analogues, owing to the confused crystallization of blocks caused by the mutual restriction of blocks and the hindrance of the dendritic cores. In addition, the aspect ratio of FA is greater than that of the others. It is hypothesized that there are two reasons for the change of aspect ratios. First, the （200） diffracting planes of PCL crystals grew slowly compared to their （110） diffracting planes because of difference in the energy barrier. Secondly, edge dislocations on the （200） diffracting planes are also responsible for the variation of the aspect ratio. Consequently, the crystalline defects are augmented by the competing blocks crystallized simultaneously and the hindrance of the dendritic cores.     

过渡金属氧化物对阻燃剂聚磷酸铵热分解的影响机制

过渡金属氧化物(MO)可以显著影响聚磷酸铵(APP)的热分解过程,进而改善APP复配膨胀阻燃聚合物材料的阻燃效率。将ZnO、Fe2O3、TiO2掺入到APP中,采用热失重分析(TGA)、X射线光电子能谱(XPS)和X射线衍射分析(XRD),考察了3种MO对APP热分解行为的影响,分析了相互作用过程中金属原子和磷原子化学结合状态的变化以及高温热分解产物的物相结构。TGA和XPS图谱分析结果表明,MO可降低APP的起始热分解温度,并催化APP释放NH3和H2O,而在热分解后期由于金属磷酸盐的形成可显著增加APP的高温残留量。3种MO催化APP热分解脱NH3和H2O的活性由大到小的顺序是:ZnO>Fe2O3>TiO2,而对APP凝聚相热分解P-O产物的交联能力从大到小的顺序为:Fe2O3>ZnO>TiO2。XRD结果显示,ZnO在高温下与APP反应生成了Zn(PO3)2晶体,而Fe2O3和TiO2与APP反应分别生成了Fe4(P2O7)3和TiP2O7晶体。     

基于CAR模型国内A股市场反应不足的实证分析

主要关注的主体异象为反应不足,在已有的HS模型基础上,对我国IPO改革背景下的证券市场投资策略进行了实证研究.实证过程中主要采用了市场调整模型计算累计超额收益率,并根据样本条件划分适当的形成期和检验期.在此基础上,以经典的"赢者组合"和"输者组合"方法对实证数据进行分析,最终发现A股市场中存在反应不足的金融异象.     

爆轰波对碰驱动平面锡飞层的动力学及动载行为特征研究

强冲击下的物质变形、破坏及诱发的轻重介质混合问题,是内爆压缩科学和工程应用领域的研究重点.本文针对爆轰波对碰条件下的复杂加载动力学过程及其动载破坏形态特征,开展数值模拟研究与极曲线理论分析.设计了爆轰波对碰驱动平面锡飞层的计算模型,获得了爆轰加载动力学过程及波系相互作用物理图像,分析了锡飞层对碰区自由表面速度历史的典型特征.给出了锡飞层中折射激波对碰发生马赫反射的临界条件,解读了三波结构的传播行为,阐明了对碰区内存在"一维正冲击"区域,一维区外存在单次斜冲击向两次斜冲击过渡的复杂加载动力学过程,提出了对碰区冲击动力学模型,揭示了影响对碰区动载行为特征的机理.数值模拟结果与极曲线理论分析结果相互印证,符合较好.本文的研究成果,将为深入理解和解读对碰区特殊的物质破坏及混合现象提供重要的理论支撑.     

拉曼光谱技术在聚合物研究中的应用进展

拉曼光谱可以提供分子的振动信息,对于聚合物分子链的构象和链间的相互作用非常敏感,能够提供聚合物固体、薄膜或溶液的物理化学特性信息,如聚合物的结构单元、空间构型、晶态结构、分子链的物理构象或分子链子链和侧基在界面间或在各向异性材料中的排列等链取向信息等。因此拉曼光谱作为一种原位无损检测技术,其衍生出的表面增强拉曼光谱技术(Surface-enhanced Raman Scattering,SERS)、变温拉曼光谱技术、共焦显微拉曼光谱技术(Confocal Raman Microscopy,CRM)、拉曼Mapping成像技术和共振拉曼散射技术(Resonance Raman scattering,RRS)等,广泛应用于物理、化学和生物医学等领域。本文从拉曼光谱的基本理论基础、拉曼光谱技术及其在聚合物研究中的最新应用进展等方面进行综述,以探索扩展拉曼光谱技术在高分子物理与化学领域中许多问题,如分子链的构象结构、分子链的结晶行为、分子链的扩散运动和共混体系相态结构变化等方面的应用。     

Effect of Nanoclay on the Phase Separation Behavior of Poly（methyl methacrylate）/Poly（vinyl acetate） Binary Polymer Blends

The effect of nanoclay on the phase-separation behavior of poly（methyl methacrylate）/poly（vinyl acetate）（PMMA/PVAc） blends has been mainly investigated by small-angle laser light scattering. It is found that the effect of clay on the thermodynamics and kinetics of phase-separation for PMMA/PVAc blends seems inconsistent. The kinetics phaseseparation rate decreases, while the thermodynamics parameters, cloud points Tc and delay time tD of isothermal phaseseparation also decrease, and the variation amplitude depends on the matrix composition. The affinity of clay to PMMA results in the composition difference between the border layer and the polymer matrix and further causes the concentration fluctuation at the early stage of phase separation to reduce Tc and tD. On the other hand, the decrease of phase-separation rate is caused by the mechanical barrier effect of clay on the macromolecular diffusion of blend matrix. Hence, such seemingly counterintuitive results on the thermodynamics and kinetics of phase-separation are attributed to different dominant factors.     

Self-assembly behavior of copolymers with super segregated structure containing fluorinated segments

Copolymers with super segregated structure of hydrophilic methoxy poly（ethylene glycol） （mPEG） and fluorophilic poly（1H,1H,2H,2H-perfluorodecyl acrylate） （PFA） were prepared. And just because of this super segregated structure which was resulted from the extremely strong incompatibility between the two blocks, several interesting self- assembly behaviors of the copolymers were displayed and studied under different conditions. Transmission electron microscope （TEM） showed that with the increase of PFA in the polymerization system, the incompatibility in this super segregated structure became stronger, and the self-assembly behavior changed from ball-like or rod-like to vesicles, and finally collapsed to sheet-like. The self-assembly behavior changed likewise when the initial concentration increased. And the interesting formation of these barrel-like and spindle-like vesicles was finally studied with different cooling speeds. It＇s finally found that with this super segregation structure, these new self-assembly morphology might be formed due to the extremely strong incompatibility between mPEG and PFA segments.