表面增强拉曼光谱研究高分子共混物薄膜相结构

采用拉曼光谱法研究了由聚苯乙烯(PS)/聚甲基丙烯酸甲酯(PMMA)的四氢呋喃(THF)溶液在玻璃基板上旋转涂膜得到的共混物薄膜。应用显微共焦拉曼光谱,根据PS在1604,1585cm-1处苯环的伸缩振动峰和PMMA在1728cm-1处羰基的伸缩振动峰,可以确定薄膜(厚度约为800nm)表面海岛状相结构的组分分布信息。另外,还对210℃下PS/PMMA(30/70)共混物薄膜退火过程中表面的变化进行了分析。采用表面增强拉曼散射效应对高聚物的增强作用得到了薄膜(厚度约为400nm)的Raman光谱,并且成功地对其组成进行了分析。     

掺三异丙氧基稀土的聚甲基丙烯酸甲酯的结构与性能

掺三异丙氧基稀土的聚甲基丙烯酸甲酯的结构与性能;掺杂     

Biological Activity of an Injectable Biphasic Calcium Phosphate/PMMA Bone Cement for Induced Osteogensis in Rabbit Model

Polymethylmethacrylate (PMMA) bone cement is widely used in repair of vertebral fracture because of its good biomechanical properties and fast curing. However, the bioinertness of PMMA cement may cause interfacial loosening, fatigue, fracture, and ultimate failure. In this study, biphasic calcium phosphate (BCP) is introduced into PMMA cement to prepare an injectable composite bone cement (BCP_x/PMMA) and the content of BCP is optimized to achieve appropriate rate of absorption that matches the bone regeneration. The compressive strength of BCP_x/PMMA bone cement is found to comply with the International Standardization Organization standard 5833, and can promote biomineralization as well as adhesion, proliferation, and osteogenic differentiation of Sprague‐Dawley rat bone marrow mesenchymal stem cells in vitro. Furthermore, in vivo test performed on a rabbit radius defect model demonstrates that the presence of BCP can significantly improve the osteogenic efficacy of PMMA cement. Therefore, it is anticipated that BCP_x/PMMA bone cement, as a promising injectable biomaterial, is of great potential in bone tissue regeneration.     

Antifungal and Surface Properties of Chitosan-Salts Modified PMMA Denture Base Material

Chitosan (CS) and its derivatives show antimicrobial properties. This is of interest in preventing and treating denture stomatitis, which can be caused by fungi. Therefore, the aim of this study was the development of a novel antifungal denture base material by modifying polymethyl methacrylate (PMMA) with CS-salt and characterizing its antifungal and surface properties in vitro. For this purpose, the antifungal effect of chitosan-hydrochloride (CS-HCl) or chitosan-glutamate (CS-G) as solutions in different concentrations was determined. To obtain modified PMMA resin specimens, the CS-salts were added to the PMMA before polymerization. The roughness of these specimens was measured by contact profilometry. For the evaluation of the antifungal properties of the CS-salt modified resins, a C. albicans biofilm assay on the specimens was performed. As solutions, both the CS-G and CS-HCl-salt had an antifungal effect and inhibited C. albicans growth in a dose-dependent manner. In contrast, CS-salt modified PMMA resins showed no significant reduced C. albicans biofilm formation. Furthermore, the addition of CS-salts to PMMA significantly increased the surface roughness of the specimens. This study shows that despite the antifungal effect of CS-salts in solution, a modification of PMMA resin with these CS-salts does not improve the antifungal properties of PMMA denture base material.     

有机玻璃力学性能的研究现状

有机玻璃作为飞机风挡与舱盖的主要材料,对其力学性能研究尤为重要。综述了国内外学者对有机玻璃力学性能的研究现状：在理论方面,总结了目前对有机玻璃的黏弹性、非弹性、屈服应力与模量——温度关系等本构模型的成果;在实验方面,阐述了近年以准静态、动态及断裂实验为主的研究;在模拟方面,举例说明在分子模拟和有限元模拟中的应用。最后指出了有机玻璃在力学研究方面的发展方向。     

Interferenzoptische Untersuchungen zur Bruchausbreitung unter Wechsellast in PMMA

Zusammenfassung In einem amorphen, transparenten Thermoplasten wurde an einem unter Ermüdungsbelastung sich ausbreitenden Riß das Verhalten des Craze an der Rißspitze untersucht. Dazu wurde eine spezielle Apparatur gebaut, mit der an Miniatur-CT-Proben Ermüdungsbelastungen bis zu 30 N bei Frequenzen bis zu 250 Hz aufgebracht werden können. Der besondere experimentelle Aufbau erlaubt die gleichzeitige Messung der Bruchgeschwindigkeit, der jeweils an der Probe wirkenden Last und des mikroskopischen Interferenzstreifensystems des Craze für jeden beliebigen Zeitpunkt eines Belastungszyklusses.An hochmolekularem PMMA wurden Bruchzähigkeit und Craze-Länge als Funktionen von Bruchgeschwindigkeit und Rißfortschrittsrate in einem weiten Frequenzbereich gemessen.Mit Hilfe des Dugdale-Modells, das die Craze-Zone an der Rißspitze beschreibt, konnte eine neue, charakteristische Materialeigenschaft abgeleitet werden: die Lebensdauer (Zahl der Belastungszyklen) einer Fibrille im Craze als Funktion der lokal am Craze wirkenden Spannung.

---

Summary For a propagating crack under cyclic loading conditions the behaviour of the craze at the crack tip in an amorphous transparent polymer has been investigated. A special apparatus has been built to apply a cyclic load up to 30 N at a frequency up to 250 Hz on the cracked sample. The experimental set-up allows the simultaneous measurement of the crack speed, the instantaneous load on the sample and the microscopic interference pattern of the craze at any moment of the cycle.Fracture toughness and craze length as functions of crack speed and fatigue crack growth rate have been measured on PMMA in a wide frequency range.By means of the Dugdale model describing the craze shape at the crack tip, a particular material property could be derived: the lifetime (number of loading cycles) of a fibril in the craze as a function of the local stress applied on the craze.

     

Construction of Two-Dimensional Waveguides in Insulating Optical Materials by Means of Ion Beam Implantation for Photonic Applications: Fabrication Methods and Research Progress

Ion beam implantation has been used not only to modify some properties of the bulk materials but also to construct waveguide structures in many optical substrates by accurate control the refractive index in selected regions. This paper reviews the recent development of ion beam implantations on fabrication of two-dimensional (2D) optical waveguides, i.e., in cases of channel or ridge configurations, in diverse insulating optical materials by giving detailed fabrication methods and research progress obtained to date. Future prospects of practical applications in photonics are also discussed briefly. Another aim of this work is to show the challenging task of this field, that is, to create practical 2D waveguide devices applicable in any existing insulating optical materials.     

Effect on structural relaxation of the poly(methyl‐methacrylate) copolymers chain flexibility

The structural relaxation of poly(methyl‐methacrylate) (PMMA)‐based copolymers with different chain flexibility has been studied by DSC with the classical procedure of the isothermal and dynamical approach. Modified PMMA with different chain flexibility have been prepared by free radical polymerization in solution using a mixture of monomers containing 10 mol % of alkyl methacrylate (i.e., ethyl, buthyl, and hexyl methacrylate). The molecular characteristics of all the prepared copolymers have been performed by a multiangle laser light scattering (MALS) photometer on‐line to a size exclusion chromatography (SEC) system (SEC‐MALS) after and before the thermal treatments, NMR (¹H and ¹³C) and MALDI‐TOF mass spectrometry. A comparison of the apparent relaxation rate (R_H) was appraised from the enthalpy loss by annealing the different samples at the same level of undercooling (T_a = T_g ? 18 °C). It was found an increase of R_H increasing the chain flexibility in the copolymers. Dynamical tests, performed at different cooling rates, have been used to estimate the apparent activation energy of the relaxation process. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 596–607, 2009     

Synthesis and kinetic analysis of DPE controlled radical polymerization of MMA

The 1,1‐diphenylethene (DPE) controlled radical polymerization of methyl methacrylate was performed at 80 °C by using AIBN as an initiator and DPE as a control agent. It was found that the molecular weight of polymer remained constant with monomer conversion throughout the polymerization regardless of the amounts of DPE and initiator in formulation. To understand the result of constant molecular weight of living polymers in DPE controlled radical polymerization, a living kinetic model was established in this research to evaluate all the rate constants involved in the DPE mechanism. The rate constant k₂, corresponding to the reactivation reaction of the DPE capped dormant chains, was found to be very small at 80 °C (1 × 10^?5 s^?1), that accounted for the result of constant molecular weight of polymers throughout the polymerization, analogous to a traditional free radical polymerization system that polymer chains were terminated by chain transfer. The polydispersity index (PDI) of living polymers was well controlled <1.5. The low PDI of obtained living polymers was due to the fact that the rate of growing chains capped by DPE was comparable with the rate of propagation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

Preparation of porous PMMA/Na–montmorillonite cation-exchange membranes for cationic dye adsorption

Porous PMMA/Na⁺–montmorillonite (MMT) cation-exchange membranes were successfully prepared by entrapment method in this study. One approach (simple mixing) was to mix commercial PMMA polymer with Na⁺–MMT clays in solvent for membrane preparation (Membrane A). The other approach (emulsion polymerization) was to synthesize the PMMA/Na⁺–MMT polymer composite via emulsion polymerization first, followed by membrane casting (Membrane B for Kunipia F clays and Membrane C for PK-802 clays). Membrane morphology and properties were characterized. The thermogravimetric analysis (TGA) verified the near complete incorporation of feed Na⁺–MMT clays in the PMMA/Na⁺–MMT composite membranes, while X-ray diffractograms (WXRD) exhibited the slightly enlarged interlayer spacing of Na⁺–MMT. The range of cation-exchange capacity (CEC) was 9–32 μequiv./47 mm disc. For batch cationic dye adsorption, the best performance was achieved by Membrane B with feed Na⁺–MMT/MMA (M/P) ratio (w/w) = 0.5 and Membrane C with feed M/P = 0.6, where about 95% Methyl violet adsorption was attained in 2 h. The optimal desorption solution was 1 M KSCN in 80% methanol and its related dye desorption efficiency was 92%. In the flow process using one piece of 47 mm disc of Membrane B (M/P = 0.5), dye solution was recirculated for 6 h and ≥85% dye could be removed. Higher than 94% of dye was desorbed at 1 or 4 mL/min, and the membrane regenerability was proved by successfully performing three consecutive cycles.