Resistivity－temperature characteristics of sol gel YBa2Cu3Oy samples synthesized in flowing oxygen atmosphere

The relationship of resistivity versus synthesizing temperature of sol gel YBa_2Cu_3O_y samples was studied when prepared under flowing oxygen conditions. A set of high-temperature ρ－T curves was obtained for the whole process. After the sample finished the test measuring, its resistivity was ρ_{300}=9.83×10^{-3 }Ω·cm at room temperature. The ρ－T curve also showed that the orthorhombic－tetragonal phase transformation of sol-gel YBa_2Cu_3O_y sample occurred at 581℃ for the sample in the rising temperature process, but at 613℃ in the cooling process, lower than that of the samples made by using the conventional powder metallurgy methods.     

Synthesis and characterization of oxidized cellulose

Samples of oxidized cellulose (OC) with various carboxyl contents and degrees of crystallinity were obtained by the oxidation of native and mercerized cellulose with a solution of nitrogen(IV) oxide in CCl₄. A detailed characterization of these OC samples was performed. The effect of oxidation conditions (concentration of N₂O₄ in the solution and oxidation time) and starting cellulose material on OC characteristics (carboxyl, carbonyl and nitrogen content, degree of crystallinity and polymerization, surface area and swelling, and acidic properties) was investigated. Reactivity in the oxidation process was higher in mercerized cellulose than in native cellulose. The action of dilute solutions (10–15%) of N₂O₄ did not affect the degree of crystallinity of cellulose samples. Under these conditions, the oxidation took place mainly in amorphous regions and on the surface of crystallites. Oxidation in a concentrated (40%) N₂O₄ solution led to the destruction of crystallites, which increased the surface area and swelling of cellulose in water. The surface area and the swelling of OC samples increased with a decrease in the index of crystallinity. The acidic properties of OC were shown to increase with an increase of swelling in water. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4785–4791, 2004     

Novel UV‐induced photografting process for preparing poly(tetrafluoroethylene)‐based proton‐conducting membranes

A novel process comprising the UV‐induced photografting of styrene into poly(tetrafluoroethylene) (PTFE) films and subsequent sulfonation has been developed for preparing proton‐conducting membranes. Although under UV irradiation the initial radicals were mainly generated on the surface of the PTFE films by the action of photosensitizers such as xanthone and benzoyl peroxide, the graft chains were readily propagated into the PTFE films. The sulfonation of the grafted films was performed in a chlorosulfonic acid solution. Fourier transform infrared and scanning electron microscopy were used to characterize the grafted and sulfonated membranes. With a view to use in fuel cells, the proton conductivity, water uptake, and mechanical properties of the prepared membranes were measured. Even through the degree of grafting was lower than 10%, the proton conductivity in the thickness direction of the newly prepared membranes could reach a value similar to that of a Nafion membrane. In comparison with γ‐ray radiation grafting, UV‐induced photografting is very simple and safe and is less damaging to the membranes because significant degradation of the PTFE main chains can be avoided. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2624–2637, 2007     

Depth profile analysis of polyimide film treated by potassium hydroxide

The structural change in the depth direction of a polyimide (UPILEX‐S) film treated in alkaline solution, which was a representative surface treatment used to form a seed layer for plating and to improve the adhesive strength, was analyzed by means of micro Fourier transform infrared attenuated total reflection (FTIR‐ATR) line analysis with gradient shaving preparation. The polyimide film was treated with KOH. The imide ring opened through the alkaline treatment, and the amide structure and carboxylic acid salt were formed. The attainment depth of this structural change was almost proportional to the treatment time, and it reached about 8 μm after a 30‐min treatment. The degree of structural change through the alkaline treatment was almost constant after it reached a considerably degraded stage, and the chemically changed region penetrated into the inner part of the film from the surface. An intermediate layer before the final degraded stage appeared in the treated layer, and its thickness increased with the treatment time. The region that was changed chemically by the alkaline treatment progressed to the inner part simultaneously and continuously as the treatment time increased. The combined use of gradient shaving preparation and micro FTIR‐ATR line analysis was found to be extremely effective for the depth profiling of organic materials. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2071–2078, 2003     

单壁碳纳米管的SERS研究

本文通过改进实验方法,将单壁碳纳米管的乙醇溶液与金胶混合并制作成固体薄膜,使单壁碳纳米管夹裹在金纳米粒子之间,保证了吸附的紧密性,获得了高质量的单壁碳纳米管SERS光谱。不但观测到文献中报道的径向呼吸振动模(RBM)和C-C正切拉伸模(GM)的增强,还在1100-1500cm-1区域观测到一组新峰,其峰形完整并有相当的强度。这些峰在现有的文献中几乎没有报导。文章对这组新峰的出现进行了初步的分析。     

Investigation on crosslinking behaviors of NBR/PVC filled with anhydrous copper sulfate particles by dynamic mechanical analysis

Crosslinking behaviors of acrylonitrile butadiene rubber (NBR)/poly (vinyl chloride) (PVC) alloy, filled with anhydrous copper sulfate (CuSO₄) particles, were investigated for the first time by dynamic mechanical analysis (DMA) under hetero and isothermal modes, respectively. In the heterothermal testing, (NBR/PVC)/CuSO₄ compound showed two marked increases in the storage modulus (E′), corresponding to coordination crosslinking of NBR-CuSO₄ and self-crosslinking of NBR and PVC respectively. During the isothermal testing, a dramatic increase in E′ was found at the initial stage while that of original NBR/PVC alloy was not detected. The marked increase in E′ of (NBR/PVC)/CuSO₄ compound was mainly due to the crosslinking induced by coordination between  CN and Cu²⁺. The increasing extent of E′ increased with the rise of CuSO₄ content, suggesting the formation of a greater number of crosslinks. Moreover, the activation energy (E_a) of crosslinking process was about 139 kJ/mol. In this work, fourier transform infrared spectrum (FT-IR) and equilibrium swelling method were also performed for the characterization of the compound. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 41–51, 2007     

现场拉曼光谱研究乙腈在金电极上的解离吸附行为

利用共焦显微拉曼系统、结合合适的电极表面粗糙方法研究了非水体系 0 1mol/LLiClO4 /CH3CN溶液中 ,乙腈分子在金表面的吸附和解离行为。结果表明非水体系中乙腈可在金表面发生还原反应 ,产物CN- 离子与电极表面作用形成的表面配合物可在较宽的电位区间吸附于电极表面。溶液中的微量水、激光照射以及电极电位均对该反应有较大的影响。通过拉曼谱图的比较得出乙腈分子解离出的CN- 在金电极表面比在银电极表面有更强的吸附作用。     

Influence of the network chain orientation on the fracture toughness of a mesogenic epoxy resin modified with CTBN

A biphenol‐type epoxy resin, which had a mesogenic group in the backbone moiety, was modified with carboxy‐terminated butadiene acrylonitrile copolymer (CTBN) as a reactive elastomer, and its fracture toughness was measured. With the addition of CTBN, the fracture toughness of the biphenol‐type epoxy resin significantly increased and became significantly higher than that of a bisphenol A‐type epoxy resin modified with CTBN. The network chain orientation in the cured biphenol‐type epoxy resin system was clearly observed during the fracture process with polarized microscopy Fourier transform infrared measurements, although such a phenomenon was not observed in the bisphenol A‐type epoxy resin system. The high toughness of the cured biphenol‐type system was clearly due to the consumption of the mechanical energy by a large deformation of the matrix resin due to the orientation of the network chains during the fracture process. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1198–1209, 2003     

Influence of relaxation effects on probabilities of the 2s2p35S2－2s22p2 3P1，2 intercombination transitions in NII

Transition probabilities of the 2s2p^3 {}^5S_2－2s^22p^2 {}^3P_{1,2} intercombination transitions in NII have been calculated by using a large-scale multiconfiguration Dirac－Fock method. In the calculation the most important effects of relativity, correlation, and relaxation are considered. From the calculated transition probabilities, the lifetime of the 2s2p^3 {}^5S_2 metastable state is derived. The result is in excellent agreement with the latest experimental result. In the meantime the influence of anomalously strong relaxation effects on probabilities of the 2s2p^3 {}^5S_2－2s^22p^2 {}^3P_{1,2} lines in NII have been found.     

CTAB对四-(4-N-甲基吡啶)卟啉SERS谱的影响

研究了阳离子表面活性剂十六烷基三甲基溴化铵 (CTAB)对四 ( 4 N 甲基吡啶 )卟啉 (H2 TMPyP)及其银配合物 (AgTMPyP)在Ag胶中的表面增强拉曼散射 (SERS)谱的影响 .SERS光谱表明 ,吸附于Ag胶粒的H2 TMPyP与衬底银原子结合形成AgTMPyP ,加入CTAB后 ,部分AgTMPyP表面络合物还原为H2 TMPyP .相似的去金属化反应也出现在AgTMPyP/Ag胶 /CTAB体系中 .CTAB的加入使SERS谱带强度明显增加 .AgTMPyP的去金属化被认为是由于CTAB的存在使Ag胶颗粒表面附近微环境发生改变