Novel platinum-containing initiators for ring-opening polymerizations

A novel class of platinum-based initiating systems for the ring-opening polymerization of a wide variety of heterocyclic compounds including epoxides, oxetanes, and 1,3,5-trioxane have been discovered. In addition to a platinum complex as a catalyst, a cocatalyst, consisting of a compound or polymer containing silicon-hydrogen bonds must also be present. This article reports on a preliminary survey of the scope and limitations of these new initiator systems. Particular emphasis in this article has been placed on the ring-opening polymerization of epoxides which have been studied in some detail and which proceed rapidly and exothermically at room temperature. A number of mechanistic studies have been conducted and the best current evidence suggests that polymerization proceeds by a cationic mechanism. Evidence is also presented which suggests that platinum metal colloids may function as the active initiating species.     

Metal complexation of crosslinked polyacrylamide-supported dithiocarbamates: Effect of the molecular character and extent of crosslinking on complexation

Dithiocarbamate functions were incorporated into different polyacrylamide matrices crosslinked with a flexible and hydrophilic crosslinking agent, tetraethyleneglycol diacrylate (TEGDA), and their complexation behaviours were investigated. Crosslinked polyacrylamides with varying extents of the tetrafunctional TEGDA crosslinks were prepared by free radical solution polymerization at 60°C using potassium persulphate as initiator in ethanol. The dithiocarbamate functionality was incorporated into these polyacrylamides by a two-step polymer-analogous reaction involving (i)trans-amidation with ethylenediamine and (ii) dithiocarbamylation of the aminopolyacrylamide with carbon disulphide and alkali. The complexations of dithiocarbamate with Cu(II), Ni(II), Zn(II), Co(II) and Hg(II) ions were followed under different conditions. The metal ion intake varied with the extent of the crosslinking agent and the observed trend in complexation is Hg(II) > Cu(II)> Zn(II)> Co(II)> Ni (II). The time-course of complexation, the possibility of recycling, swelling characteristics, and spectral and thermal analyses were carried out. The thermal stability increases upon complexation with metal ions.     

A density functional theory computational study of the role of ligand on the stability of CuI and CuII species associated with ATRP and SET‐LRP

Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with Cu^I and trigonal bipyramidal with axial halide complexes with [Cu^IIX]⁺ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [Cu^IIX]⁺ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [Cu^IIX]⁺ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007     

Analysis of Threshold Current and Wall-Plug Efficiency of Diode Lasers with Asymmetric Facet Reflectivity

Threshold current and differential quantum efficiency of broad contact lasers with asymmetric facet reflectivity are discussed with the purpose to reveal factors essential for optimisation of the wall-plug efficiency of such lasers. Lasers with low front facet reflectivity and short cavity often exhibit behaviour difficult to explain with a classical theory. More rigorous calculation performed in this work show that differential quantum efficiency is indeed less affected by a change of the front facet reflectivity or cavity length than predicted by such theory. These findings greatly simplify criteria for optimisation of the wall-plug efficiency of broad contact lasers with coated facets.     

Temperature Dependence of the Threshold Current and the Lasing Wavelength in 1.3-μm GalnNAs/GaAs Single Quantum Well Laser Diode

Temperature stability of the threshold current and the lasing wavelength is investigated in a 1.3-μm GaInNAs/ GaAs single quantum-well laser. The measured characteristic-temperature was 88 K. The small wavelength shift per change in temperature of 0.35 nm/°C was obtained, indicating the superior lasing-wavelength stability. Therefore, it is shown experimentally that GaInNAs is very promising material for the fabrication of light source with excellent high-temperature performance for optical fiber communications.     

The role of OH ions in the stabilization of F colour centres in LiF

Thermally Stimulated Depolarisation Current (TSDC) and optical methods are applied to a range of alkali-fluoride crystals in order to establish a model for the stable F ₂ ⁺ - like colour centres in LiF:OH^-. The experimental results for LiF:OH^- suggest that the OH^- defects are partially destroyed under ionising irradiation or during crystal growth. The low-temperature dielectric relaxation signals in LiF:OH^- and LiF:Mg²⁺,OH^- are attributed to highly interacting hydroxide ions and products of their destruction located in extended lattice defects. In LiF:OH^-, in contrast to other alkali halides, the results advocate for a defect-structure model, which considers a neutral defect (ND, probably O₂ or H₂) sited at the anion vacancy of the O^2--V _a ⁺ dipole and which possibly is the “nucleus” for the F ₂ ⁺ centre. The proposed F ₂ ⁺ (ND, O^-) model seems to better explain the dielectric results, compared to the older F ₂ ⁺ (O^2-) and F ₂ ⁺ (O^-) models. The estimate for the electric dipole moment derived from the experimental TSDC bands, gives a value for the F ₂ ⁺ - like centre in LiF:OH^- between those of the F ₂ ⁺ (O^-) and F ₂ ⁺ (O^2-) defects, in good agreement with the proposed F ₂ ⁺ (ND,O^-) model. The reduction of the activation energy barrier of the (re)orientation process of the Mg²⁺V _c ^- (OH^-) complexes in LiF:Mg²⁺,OH^-, and the low-temperature shift of their TSDC band, compared to the single Mg ₂ ⁺ V _c ^- peak in LiF:Mg²⁺, are tentatively ascribed to an increase in the crystal-lattice parameters owing to the presence of OH^- and/or products of its destruction. Received 31 August 2001 / Received in final form 30 March 2002 Published online 9 July 2002     

The energy exchange and the optimum length of the sample tube of opfirl

The energy exchange between the pumping laser and FIR signal in the optically pumped FIR laser (OPFIRL) system was studied. The iteration method has been used to calculate the power density of the pumping and FIR signals at any point along the optical axis of the sample tube. It was found that the power density of the FIR signal did not always increase along the length of the laser tube. There was a maximum FIR power density at the appropriate point in the sample tube. If the distance of maximum power point from the entrance of the OPFIRL tube was taken as the length of sample tube Z_opt, the maximum FIR laser output should be obtained. This was the optimum length of OPFIRL tube. The value of Z_opt was closely related to the parameter of OPFIRL such as the pumping power density, the pumping detuning and the frequency of the FIR laser. The energy-exchange and the maximum output of the fir laser were calculated under the ideal condition.     

基于界面跟踪方法的汽蚀模型和算法的有效性验证

针对两相附着汽蚀流动机理,基于界面跟踪方法发展了新的汽蚀模型和算法。所发展的汽蚀模型和算法不仅考虑了液相／气相界面处的压力差,而且考虑了耦合Reynolds-Averaged Navier-Stokes方程求解技术得到的流场压力梯度信息来迭代计算附着汽蚀形状。采用具有试验数据的半球形头部圆柱体汽蚀绕流作为算例来验证所提出的汽蚀模型和算法的有效性。采用不同的网格数和松弛因子数值验证了发展的汽蚀模型和算法的有效性。三种汽蚀数下的数值计算结果得到的压力系数分布与试验数据完全吻合。结果表明所提出的汽蚀模型和算法能够准确模拟出汽蚀发生点和汽蚀长度。     

韧性金属裂纹尖端损伤区内应变场测量——数字散斑相关法应用

本文用数字散斑相关方法测量了五种不同幂硬化指数韧性金属材料(铝和铜),双边裂纹尖端细观区域内应变场.对所得结果用韧性损伤模型进行了分析.在此法中以金属自然表面结构为散斑场,不同加载状态的散斑场进行比较,得到相对变形与应变.图象之间相关性 C 是变形参数或是位移及其导数的泛函.使其相关性 C 取最大值的试凑变形即为其真实变形场.这一方法在细观测量中应用得到满意的结果.     

Overview: The Potential of silanes for chromate replacement in metal finishing industries

Trialkoxysilanes (or silanes) have emerged as a very promising alternative for chromates in metal finishing industries. Compared to the conventional chromating processes, the major merits of silane-based surface treatments include: eco-compliance, easy-control processing, comparable corrosion protection of metals as well as paint adhesion to a variety of topcoats. In this overview paper, we report the recent status of silane studies including results of corrosion performance tests, the mechanism of corrosion protection of metals by silanes and the themal stabilities of silane films. We also address the new fields that we are beginning to explore such as nano-structured silane films, “self-healing” silane films, and “super-primers”.