在位分散聚合聚甲基丙烯酸甲酯/二氧化硅纳米复合材料研究

应用在位分散聚合方法制备了分散相粒径介于１３０ｎｍ左右的聚甲基丙烯酸甲酯／二氧化硅ＰＭＭＡ／ＳｉＯ２纳米复合材料，并利用ＳＥＭ，ＤＭＡ，ＴＧＡ等手段研究了该体系的性能．结果表明，经表面处理的ＳｉＯ２无机填料在复合材料基体中分散均匀，界面粘结好．ＳｉＯ２填充粒子的用量对基体的热稳定性，动态力学行为，光学行为以及拉伸强度，弹性模量，断裂伸长率等力学性能都有较大影响     

氟化γ-Al2O3表面酸性的NMR和FTIR表征

用红外光谱和核磁共振技术研究了氟化作用对γ-Al2O3的表面酸性（酸中心类型、强度及数量）的影响。吡啶和二甲基吡啶在氟化γ-Al2O3（F／γ-Al2O3）表面上吸－脱附的IR光谱和三甲基膦在F／γ-Al2O3表面上吸附的^31P MAS NMR结果表明，F／γ-Al2O3表面上既存在Lewis酸位又存在Broensted酸位。L酸的总量随氟含量的增加而减少。但其强度随之增加，且同时产生几种新的L酸位。B酸的数量和强度在样品含氟量为2％－3％间存在极大值。研究还表明，三甲基膦是一种测量F／γ-Al2O3表面酸性的灵敏的NMR探针分子，^31P MAS NMR和红外光谱的测试结果基本一致。同时，对氟化过程中酸位形成和变化机理进行了探讨。     

Preparation of flame retardant polyamide 6 composite with melamine cyanurate nanoparticles in situ formed in extrusion process

This paper is focused on in situ preparation of melamine cyanurate (MCA) nanoparticles from reaction of melamine (MEL) and cyanuric acid (CA) and their flame retardant polyamide 6 (PA6) composite in the extrusion process through a novel reactive processing method. Fourier transform infrared (FT-IR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) were utilized to characterize the in situ formed MCA nanoparticles and their blends with PA6. Introduction of pentaerythritol (LTP) and water-bound plasticizer dioctyl phthalate (DPT) into the extrusion reaction system greatly inhibits the evaporation of water required for melamine and cyanuric acid reaction at high temperature (higher than 180 °C), laying a foundation for successful in situ preparation of MCA through reactive processing. XRD and FT-IR measurements indicate that under the effect of pentaerythritol, dioctyl phthalate and water, melamine really reacts with cyanuric acid to in situ form MCA in extrusion process. The reaction degree is close to 100%. A very important finding through SEM is that the in situ formed MCA particles, which were found to have aspect ratio of about 7.5, radial size in the range of 70-300 nm (mostly 70-90 nm) and crystallite size of less than 22 nm, are uniformly dispersed in the matrix PA6 at nanoscale. The in situ formed MCA nanoparticles greatly improve the flame retardancy and the mechanical properties of flame-retarded PA6 materials, and the introduced plasticizer dioctyl phthalate also ameliorates the related impact property. The obtained flame-retarded PA6 materials have good comprehensive performance with flame retardancy UL-94 V-0 rating at 1.6 and 3.2 mm thickness, tensile strength 48.0 MPa, elongation at break 106.3% and Izod notched impact strength 8.92 kJ/m². Compared with flame-retarded PA6 material with in situ formed MCA, the one prepared through conventional blending of PA6 with commercial MCA product has improved tensile strength but deteriorated impact strength and flame retardancy.     

Structure of thiocyanate adlayers on Rh(111): an in situ STM study

In situ scanning tunneling microscopy (STM) was used to examine the structure of thiocyanate adlayers specifically adsorbed on Rh(111) in solutions of potassium hydroxide and perchloric acid, both containing potassium thiocyanate (KSCN). An atomically flat terrace-step structure was consistently observed on Rh(111) surfaces prepared by the flame-annealing-quenching method. The Rh(111)-(1 × 1) atomic structure was discerned on the atomically flat terrace even in the alkaline solution. High-resolution STM images disclosed two different structures of the SCN⁻ adlayers, () and (2 × 2), in the alkaline and the acidic media, respectively. In each structure, an individual adsorbed SCN⁻ ion appeared as a single spot with a constant corrugation height in STM images, suggesting that SCN⁻ ions adsorbed predominantly with their S-ends at particular bonding sites on Rh(111). The difference in the adlayer structure in the two solutions can be attributed to the interaction between adsorbed SCN⁻ and coadsorbed K⁺ in the alkaline solution, and is different from that between adsorbed SCN⁻ and H⁺ in the acidic solution. Received: 26 February 1997 / Accepted: 3 March 1997     

Properties of cerium-zirconium mixed oxides partially substituted by neodymium: Comparison with Zr-Ce-Pr-O ternary oxides

CeO₂ doped with praseodymium, neodymium and/or zirconium atoms were prepared by coprecipitation and by the sol-gel method. Structural properties were investigated by in situ XRD and Raman spectroscopy while oxygen storage capacity (OSC) was measured by transient CO oxidation. All the compounds, except pure Nd₂O₃, have a fluorite-type structure as well as a Raman band at 560 cm⁻¹ characteristic of the oxygen vacancies involving non-stoichiometric oxides. The lattice parameter under hydrogen, being dependent on the temperature, revealed two reduction mechanisms: one at a low temperature at the surface and another at a high temperature in the bulk. Ce-Nd binary oxides show a strong tendency towards crystallite aggregation, which reduces accessibility to gases and OSC properties. Zirconium improves the thermal resistance to sintering of both Ce-Nd and Ce-Pr oxides. The Zr-Ce-Pr-O followed by Zr-Ce-Nd-O compounds displaying high oxygen mobility at a low temperature, appear to be very promising for practical applications such as OSC materials.     

L—氨基酸氧化酶电极的制作及电极特性的研究

报道了一种新的Ｌ－氨基酸氧化酶电极，这种酶电极系由氨气敏电极和以氨基化玻璃布为载体的酶膜所组成；研究了固定化条件对酶膜活性的影响以及底物浓度、温度和ｐＨ对电极响应特性的影响。该电极在６．０×１０＾－５～４．０×１０＾－３ｍｏｌ／Ｌ的底物浓度范围内呈良好的线性关系，检测下限为５．０×１０＾－５ｍｏｌ／Ｌ。在最宜条件下，酶电极具有良好的稳定性。     

担载液相催化剂的研究——Ⅳ.催化剂的原位红外光谱表征

本文利用原位红外光谱方法对铑基担载液相催化剂(SLPC)在接近于实际反应条件下进行了表征。结果表明,新鲜催化剂上,铑膦络合物主要以二聚物的形式存在,如Rh_2(CO)_2(PPh_3)_4而在合成气或反应气氛中,催化剂铑膦络合物以单核络合物HRh(CO)_2(PPh_3)_2的形式存在。文中还对SLPC在CO,H_2,C_2-H_4,空气和HCl中处理时铑络合物种的变化进行了原位观察。实验结果表明,SLPC上活性铑络合物与对应的均相过程完全一致,进一步证实了SLPC催化在微观上就是一个均相催化过程。     

PHEMA hydrogels obtained by a novel low-heat curing procedure with a potential for in situ preparation

In this work, we report on poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogels obtained by a low heat curing reaction. These materials are suitable for in situ preparation and therefore endowed with a potential for several biomedical applications. The novel procedure adopted involves as the first step the synthesis of a soluble oligomeric PHEMA precursor containing polymerizable functions as side substituents. As the second step, the precursor is dissolved in equal amounts of 2-hydroxyethyl methacrylate (HEMA) and water, to form a viscous but still injectable syrup. A low temperature water soluble initiator is then added. The curing reaction starts promptly and is completed within few minutes. During the entire process the internal temperature never rises above 40 degrees C. Preliminary mechanical characterizations performed on the hydrogels in their water-swollen state and diffusion tests in absorption/desorption experiments clearly indicated that on all respects the novel hydrogels are comparable with conventional PHEMA hydrogels obtained according to literature from HEMA in the presence of divinyl crosslinkers. However, the much shorter curing time combined with the far lower curing temperature endow the new hydrogels with a higher potential in view of specific surgical requirements, and particularly for in situ preparation.     

PREPARATION OF POLY（METHYL METHACRYLATE）/LAYERED DOUBLE HYDROXIDES NANOCOMPOSITES via in situ SOLUTION POLYMERIZATION

An exfoliated layered double hydroxides/poly(methyl methacrylate)(LDHs/PMMA)nanocomposite was prepared by in situ solution polymerization of methyl methacrylate(MMA)in the presence of 4-vinylbenzenesulfonate intercalated LDHs(MgAl-VBS LDHs).MgAl-VBS LDHs was prepared by the ion exchange method,and the structure and composition of the MgA1-VBS LDHs were determined by X-ray diffraction(XRD),infrared spectroscopy and elemental analysis.XRD and transmission electron microscopy(TEM)were employed to examine the structure of LDHs/PMMA nanocomposite.It was indicated that the LDHs layers were well exfoliated and dispersed in the PMMA matrix.The grafting of PMMA onto LDHs was confirmed by the extraction result and the weight fraction of grafted PMMA increased as the weight fraction of LDHs in the nanocomposites increased.