Synthesis of hybrid nanocomposites based on new triazeno copolymers and montmorillonite used for detecting metal ions

The modern synthesis of novel functional materials with improved properties includes that of hybrid nanocomposites composed of inorganic nanoparticles and organic derivatives, where controlling the molecular structure at atomic and macroscopic dimensions is a key factor, with a major effect on performance. An extension of this approach to the field of nanocomposites containing photopolymers with triazene groups attached on a methacrylic backbone could be of great interest in the future development of chemosensors and photoresists, among others. Photopolymer/clay nanocomposites were prepared by in situ free radical copolymerization of 1‐(phenyl)‐3‐(2‐methacryloyloxyethylcarbamoyloxyethyl)‐3‐methyltriazene‐1 or 1‐(p‐methoxyphenyl)‐3‐(2‐methacryloyloxyethylcarbamoyloxyethyl)‐3‐methyltriazene‐1 and vinyl acetate or styrene in solution and in the presence of 3 and 5 wt% of organically modified montmorillonite. The characterization of the nanocomposites and pure copolymers was achieved through ¹H NMR and Fourier transform infrared spectroscopy, gel permeation chromatography, thermogravimetric analysis, X‐ray diffraction, atomic force microscopy and fluorescence analysis. The morphologies and properties of the nanocomposites are dependent on the nature of the triazene, on the co‐monomer structure and on the organoclay content. Also, the fluorescence response of these nanocomposites towards certain metal ions (Fe³⁺, Cu²⁺, Hg²⁺, Ni²⁺) in dimethylformamide solution was investigated. The effect of uranyl ions on the fluorescence intensity of the nanocomposites in solution or as films could be exploited in the development of ‘turn‐off’ or ‘turn‐on’ chemosensors for this type of analyte. Triazeno copolymer/organophilic montmorillonite nanocomposites with exfoliated (not completely exfoliated) or exfoliated and intercalated structures exhibit distinct characteristics concerning their fluorescence behaviour, a higher sensing ability towards certain target compounds (Fe³⁺, UO₂²⁺) being evidenced for those incorporating 3 wt% organoclay in solution and as films. Copyright © 2010 Society of Chemical Industry     

An experimental and theoretical study of the carbazole to carbazole intramolecular energy transfer in N‐vinylcarbazole/vinyl tert‐butyl‐benzoate copolymers of different molar compositions

Fluorescence depolarization and quenching measurements of N‐vinyl carbazole/vinyl tert‐butyl‐benzoate copolymers in dilute solution of several fluid solvents and in a rigid poly(methyl methacrylate) matrix were performed to study the effect of copolymer composition on the intramolecular energy transfer (IET) between carbazole groups (Cz) along the polymer chain. IET efficiency, as the amount of Cz? Cz intramolecular excimer formation, monotonically increases with Cz content up to a number average sequence length of carbazole of ca 12 (Cz molar content ≥ 90%). After this value, IET efficiency remains almost constant. Molecular dynamics simulations on isotactic and syndiotactic copolymer fragments of several monomer compositions were used for obtaining different parameters related to the efficiency for the IET process between Cz units along the polymer chain. Copyright © 2011 Society of Chemical Industry     

淬火工件/介质边界换热条件研究

在试验的基础上，开发了淬火工件／介质边界换热条件程序，该程序通过反算法计算边界换热系数．利用该程序与ＡＢＡＱＵＳ非线性有限元程序对淬火过程温度场进行数值模拟，模拟结果与实测值比较，误差在１０％以内．     

复合场效应淬火试验研究

本文提出了复合场效应淬火工艺原理和流场一超声复合场效应淬火技术,并进行了试验研究,结果表明:该项技术可显著改善介质的淬火冷却特性。提高工件的淬硬性、淬透性;减少淬火应力与变形。为淬火技术指出了新的方向。     

淬火过程流动与传递现象数值模拟

根据淬火过程中多相流动与传热的特点,提出了简化模型。基于两相流体动力学及流固耦合传热建立了流动与传热方程。推导出了计算模型并结合大型软件Fluent进行了用户子程序（UDF）设计,利用此方法对影响流动与沸腾传热的几个因素进行了数值研究,数值计算结果与理论分析吻合。最后对金属铝块的淬火过程进行了计算,计算得到的金属表面测点温度随时间变化历程与文献中实验数据误差在15%以下,表明计算方法可行并且把握了物理过程的本质。     

真空灭弧室设置不同屏蔽罩的均压作用

本文阐述了均压屏蔽罩在高电压真空灭弧室中的应用及其重要性,介绍了各种不同屏蔽罩在高电压真空灭弧室内所起的均压作用,触头开距与屏蔽罩之间的配合以及触头和屏蔽罩形状的分析。     

65Mn钢的CCT曲线及圆锯片淬火工艺

利用Formarstor一Digital全自动相变测定仪对我国现行圆锯片用钢65Mn的连续冷却转变曲线(CCT)进行了测定,研究了不同连续冷却速度下得到的组织,为合理制订圆锯片的淬火工艺提供了依据,得出了最佳淬火工艺曲线。     

Leaf Age-Dependent Photoprotective and Antioxidative Response Mechanisms to Paraquat-Induced Oxidative Stress in Arabidopsis thaliana

Exposure of Arabidopsis thaliana young and mature leaves to the herbicide paraquat (Pq) resulted in a localized increase of hydrogen peroxide (H₂O₂) in the leaf veins and the neighboring mesophyll cells, but this increase was not similar in the two leaf types. Increased H₂O₂ production was concomitant with closed reaction centers (q_P). Thirty min after Pq exposure despite the induction of the photoprotective mechanism of non-photochemical quenching (NPQ) in mature leaves, H₂O₂ production was lower in young leaves mainly due to the higher increase activity of ascorbate peroxidase (APX). Later, 60 min after Pq exposure, the total antioxidant capacity of young leaves was not sufficient to scavenge the excess reactive oxygen species (ROS) that were formed, and thus, a higher H₂O₂ accumulation in young leaves occurred. The energy allocation of absorbed light in photosystem II (PSII) suggests the existence of a differential photoprotective regulatory mechanism in the two leaf types to the time-course Pq exposure accompanied by differential antioxidant protection mechanisms. It is concluded that tolerance to Pq-induced oxidative stress is related to the redox state of quinone A (Q_A).     

Mechanism and microstructural evolution of combustion synthesis of ZrB2–Al2O3 composite powders

Mechanism of combustion synthesis (CS) of ZrB₂–Al₂O₃ composite powders was systematically analyzed by a combustion front quenching method (CFQM). The microstructural evolution during the CS process was investigated by field-emission scanning electron microscopy (FESEM) equipped with energy dispersive X-ray spectrometer (EDS). The combustion temperature and wave velocity were measured by the data acquisition system. Moreover, the phase constituents of the final product were examined by X-ray diffraction (XRD). The thermal behaviors of the stoichiometic powders under the thermal exposure were characterized using differential scanning calorimetry (DSC) and thermogravimetric (TG). The results showed that the combustion reaction started from the melting of the B₂O₃ and Al particles, which was followed by the formation of ZrO₂–B₂O₃–Al solution. The ignition temperature of this system was determined to be around 800 °C. B and Al₂O₃ were then precipitated from the solution. As the CS reaction proceeded, Zr and Al₂O₃ were produced by the reaction between ZrO₂ particles and Al and precipitated from the solution. ZrB₂ could then be formed by the direct reaction between Zr and B. Finally, the ZrB₂–Al₂O₃ composite powders were obtained. Furthermore, a model corresponding to the dissolution–precipitation mechanism was proposed.     

槲皮素-罗丹明6G荧光猝灭体系研究

以Stern-Volmer方程和罗丹明6G吸收光谱研究了槲皮素-罗丹明6G荧光猝灭体系。结果表明,槲皮素、罗丹明6G间发生静态猝灭,生成稳定复合物,二者的结合常数和结合点数为k1=2.63×106L·mol-1,n1=1.14;k2=7.42×105L·mol-1,n2=1.07。槲皮素的质量浓度在0.01～0.2μg·mL-1和0.2～5.0μg·mL-1范围内与F0/F成正比,检出限为5.9ng·mL-1,加标回收率为91.7%～104%,方法可用于槲皮素含量测定。