Impact of H+ ion irradiation on Matrimid®. I. Evolution in chemical structure

Ion beam irradiation can be used to modify the structure and gas transport properties of glassy polymers. This is the first of two studies that focus on the impact of H⁺ ion irradiation on the structure and permeation properties of the polyimide Matrimid®. Specifically, the evolution in chemical structure after H⁺ irradiation over a range of fluences was analyzed using FTIR spectroscopy and dissolution studies. Although H⁺ ion irradiation at very low ion fluences induced little modification in the chemical structure, irradiation at relatively high ion fluences resulted in crosslinking of the irradiated films. The branched structure of the aliphatic methyl (CH₃) was the most sensitive to the H⁺ ion irradiation. The para‐disubstituted aromatic ring showed the strongest resistance toward ion irradiation and required fairly high doses to induce degradation. Two potential crosslinking mechanisms related to the degradation of the aliphatic methyl and the benzophenone carbonyl were presented. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2010–2019, 2003     

Effect of crosslinkers on the preparation and properties of ETFE‐based radiation‐grafted polymer electrolyte membranes

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2‐bis(p,p‐vinylphenyl)ethane (BVPE), and triallyl cyanurate (TAC) crosslinked poly(ethylene‐co‐tetrafluoroethylene) (ETFE)‐based radiation‐grafted membranes, which were prepared by radiation grafting of p‐methylstyrene onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity, and thermal/chemical stability of the resulting polymer electrolyte membranes were investigated in detail. Introducing crosslink structure into the radiation‐grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation‐grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation‐grafted membranes show significantly higher chemical stability characterized in the 3% H₂O₂ at 50°C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation‐grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4565–4574, 2006     

γ‐Irradiation effects on the thermal and structural characteristics of modified,grafted polypropylene

The effects of both the degree of grafting and γ irradiation on the thermal stability and structural characteristic of polypropylene‐graft‐polyvinylpyrrolidone and polypropylene‐graft‐polyvinylpyrrolidone modified with α‐cyano‐δ‐(2‐thienyl) crotononitrile were investigated. The employed techniques were thermogravimetric analysis, differential thermogravimetry, and X‐ray diffraction. The thermal stability of various polymeric substrates was investigated through the determination of the degradation temperature and activation energy of degradation. The effects of different parameters on the structural characteristics of different films were investigated through the determination of possible changes in the degree of ordering of the polymeric substrates. The results revealed that the thermal stability of the trunk polymer, grafted polymer, and polymer modified by α‐cyano‐δ‐(2‐thienyl) crotononitrile increased progressively with an increasing degree of grafting. The increase was, however, more pronounced for the sample undergoing the lowest degree of grafting. The activation energy of the thermal degradation process remained almost unchanged, and this indicated that the degradation processes of the different films followed almost the same mechanism. The γ irradiation at a dose of 60 kGy of the sulfur‐treated polymeric films [i.e., the polymeric films treated with α‐cyano‐δ‐(2‐thienyl) crotononitrile] reduced their thermal stability. This conclusion was reached by the consideration of the changes observed in the pre‐exponential factor of the Arrhenius equation due to different chemical and γ‐irradiation treatments. The degree of ordering, evidenced by X‐ray diffraction measurements of the trunk polymer, grafted polymer, and modified polymer, suffered a significant drop. This drop was much more pronounced for the sulfur‐containing polymeric materials. The observed drop in the degree of ordering of the polymeric substrates was taken as a measure of the structure collapse due to a certain treatment (degree of grafting and sulfur inclusion). The γ irradiation of the sulfur‐containing polymeric materials greatly increased their degree of ordering, which reached a value greater than that measured for the trunk polymer. Therefore, it was concluded that the thermal stability increased as the degree of ordering decreased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 506–515, 2006     

185nmUV降解水中4-CP、4-NP和RhB的研究

本文以对氯苯酚（4-cP）、对硝基苯酚（4-NP）和罗丹明B（RhB）为模型有机物（以4-CP和4-NP为小分子模型有机物，以RhB为大分子模型有机物），分别研究了185nmUV对水中这3种模型有机物的降解规律、性能和效果．研究结果表明，185nmUV直接对水中4-CP、4-NP和RhB有很好的降解效果．研究内容包括：185nmUV降解模型有机物的浓度、TOC（Totalorganic carbon）浓度、185nmUV降解模型有机物过程中溶液pH及电导率变化、以及降解模型有机物过程中产生的无机离子等几个方面．     

Preparation and characterization of a proton‐exchange membrane by the radiation grafting of styrene onto polytetrafluoroethylene films

Radiation‐induced simultaneous grafting of styrene onto polytetrafluoroethylene (PTFE) films and the subsequent sulfonation in the chlorosulfonic acid/dichloroethane were investigated. The effects of the main radiation grafting conditions, such as the type of solvents, irradiation dose, dose rate, the styrene concentrations, etc., on the degree of grafting (DOG) were studied. To elucidate the influence of both the grafting and sulfonation conditions on the properties of the PTFE‐g‐polystyrene‐sulfonic acid (PSSA) membranes, the sulfonation conditions, including the sulfonation temperature and the concentration of the ClSO₃H with respect to the DOG, were systematically evaluated. The grafted and sulfonated membranes were characterized by FTIR–ATR spectra, ion‐exchange capacity (IEC), water uptake, thickness measurement, etc. The as‐prepared PTFE‐g‐PSSA membranes in this work showed a good combination of a high IEC (0.85–2.75 meq g^?1), acceptable water uptake (8.86–56.9 wt %), low thickness, and volume expansion and/or contraction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1415–1428, 2006     

Molecular motions of non-crystalline poly(aryl ether-ether-ketone) PEEK and influence of elecron beam irradiation

The dynamic mechanical relaxation of non-crystalline poly(aryl ether-ether-ketone) PEEK and the one irradiated with electron beam were studied. The three distinct γ, β, α′ relaxation maxima were observed in unirradiated PEEK from low to high temperature. It was revealed from the study on the irradiation effects that three different molecular processes are overlapped in γ relaxation peak, i.e., molecular motion of water bound to main chain (peak temperature; at ?100°C), local motion of main chain (at ?80°C), and local mode of the aligned and/or oriented moiety (at ?40°C). The β relaxation connected with the glass transition occurred at 150°C and it shifted to higher temperature by irradiation. The α′ relaxation which can be attributed to rearrangement of molecular chain due to crystallization was observed in unirradiated PEEK ～ 180°C and its magnitude decreased with the increase in irradiation dose. This effect indicates the formation of structures inhibiting crystallization such as crosslinking and/or short branching during irradiation. A new relaxation, β′, appeared in the temperature range of 40° to 100°C by irradiation and its magnitude increased with dose. This relaxation was attributed to rearrangement of molecular chain from loosened packing around chain ends, which were introduced into the non-crystalline region by chain scission under irradiation, to more rigid molecular packing, From these observations, we proposed that deterioration in mechanical properties of non-crystalline PEEK by high energy electron beam was brought about not only by chain scission but structural changes such as crosslinking and/or branching in the main chain.     

Preparation of rechargeable lithium batteries with poly(methyl methacrylate) based gel polymer electrolyte by <Emphasis Type="Italic">in situ</Emphasis>γ-ray irradiation-induced polymerization

An admixture of commercial liquid electrolyte (LB302, 1 M solution of LiPF₆ in 1:1 EC/DEC) and methyl methacrylate (MMA) was enclosed in CR2032 cells. The assembled cells were then -ray-irradiated using configurations of half cells and full cells. Through this in situ irradiation polymerization process, we obtained rechargeable lithium ion cells with poly(methyl methacrylate) (PMMA) based gel polymer electrolytes (GPE). Galvanostatic cycling, AC impedance spectroscopy, and cyclic voltammetry were employed to investigate the electrochemical properties of the cells and the gel polymer electrolyte. This PMMA-based gel polymer electrolyte was found to exhibit a high ionic conductivity (at least 10^–3 S cm^–1) at room temperature. Due to a significant increase in the charge transfer resistance between the GPE and the cathode, the cell impedance of a PMMA-based lithium ion cell is greater than that of a liquid-electrolyte-based cell. The discharge capacity of a LiNi_0.8Co_0.2O₂/GPE/graphite is approximately 145 mAh g^–1 for the first cycle and decreases to123 mAh g^–1 after 20 cycles. In addition, a large initial cell impedance (LICI) was observed in the irradiated positive half cell. In this paper, we propose a possible mechanism related to the detachment of the PMMA layer from the lithium electrode. This detachment of the PMMA layer from the lithium electrode has not been explicitly discussed previously.     

用太阳辐射转化法计算室外照度值

针对中国光气候数据资料不足、太阳辐射数据丰富以及资金有限的现状,在分析多种光气候数据采集方法的基础上,选用太阳辐射转化法获得光气候数据。引入发光功效的概念作为室外照度值和太阳辐射量转化的基本关系,并分析对比了已有的发光功效模型,运用天空晴朗指数,以重庆1991-1992年的实测数据为基础进行拟合,建立了总发光功效模型和散射发光功效模型。选用重庆1993年的实测数据对该模型进行了验证,得到了高于其他模型的计算精度。为了验证该模型在中国其他城市的适用性,对中国32个城市的年平均总照度值的计算值和实测值进行了对比,结果证明该转化模型能够满足采光设计的需要。运用这种方法只要输入某地某时刻的太阳辐射数据就可以计算出当地该时刻的室外总照度值和散射照度值,可以大大丰富中国各个城市的光气候数据。最后论文给出了该模型用于室外照度值计算的应用方法。     

M2高速钢强脉冲离子束表面改性及其耐磨耐蚀性

针对陶瓷梯度涂层性能优良,在大气氛围下等离子喷涂制备涂层会受到空气氧化这一情况,在可控气氛（Ar气）中采用等离子喷涂的方法制取了NiCrBSi/Al₂O₃的梯度涂层,并且与大气条件下制取的NiCrBSi/Al₂O₃的梯度涂层进行对比.借助扫描电子显微镜（SEM）、x 射线衍射仪（XRD）对涂层的组织分布、相结构进行分析.结果表明：在Ar气和大气中梯度涂层的组织内部都没有明显的界面,实现了组织的连续变化;在Ar气中制取的梯度涂层的组织更加致密,被氧化的程度更低,质量更好.     

紫外/臭氧复合杀灭水中细菌性能研究

为开发一种高效灭菌方法,研究了UV/O3的复合灭菌性能,对紫外辐射、臭氧和羟基自由基等在体系中的各自作用进行探讨,同时考察pH值、温度等对灭菌效果的影响.结果表明,UV/O3较单独紫外或臭氧灭菌时效果有所提高,在初始臭氧质量浓度为5.02mg·L-1,液面紫外辐射强度为6.5mW·cm-2,灭菌时间1.5～9.0s时,UV/O3对细菌总数灭菌率达3.6～6.4,单独紫外时为1.8～4.7,单独臭氧时仅为1.6～3.0.羟基自由基的产生是复合灭菌效果增加的主要原因.随紫外辐射强度和臭氧投加量的增加,复合灭菌作用得到提高.pH值在5.5～8.5变化时,UV/O3灭菌效果随原水pH值的增加略有提高.温度由10℃上升到27℃时,灭菌效果稍有下降.由此可见,UV/O3是一种高效可行的水体灭菌技术。