Pressure and temperature dependence of the gas‐transport properties of dense poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] membranes

The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH₄ > N₂ > O₂ > CO₂. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO₂ decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO₂‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004     

采用空心阴极放电等离子体化学气相沉积方法制备a-CH薄膜

 研究了不同衬底-阴极距离、直流电压和H₂流量对a-CH薄膜沉积速率的影响。结果表明：衬底-阴极距离必须大于0.5cm，随着该距离的增加，薄膜的沉积速率减少；直流电压达550V时沉积速率最大；随着H2含量的增加，CH₄含量相对减少，沉积速率随之降低。用AFM观察了以该方法制得的448.4nm CH薄膜的表面形貌，表面粗糙度约为10nm。最后测出了不同条件下CH薄膜的UV-VIS谱，由此可以计算得到薄膜的禁带宽度及折射率。     

紫外波段CH2I2分子的光解离动力学研究

利用离子速度成像方法,研究CH2I2分子在277—305nm范围内若干波长处的光解离动力学.通过同一束激光经(2+1)共振多光子电离(REMPI)过程探测光解碎片I(2P32)和I(2P12),得到了不同激发波长处的离子速度分布图像,从而获得CH2I2光解产物的能量分配和角分布.实验发现,碎片CH2I自由基有很高的内能激发,约占总可资用能的80%,该能量分配可以较好地用冲击模型来解释.实验还发现,产物I(2P32)和I(2P12)具有很不相同的平动能分布,结合所得到的碎片能量分配和角分布,我们对碎片I(2P32)和I(2P12)生成机理进行了分析,指出CH2I2分子电子激发态的绝热和非绝热解离决定了碎片的平动能分布. 关键词： CH2I2 离子速度成像 绝热和非绝热解离     

热丝加热电流对CH薄膜沉积速率和表面形貌的影响

 热丝辅助裂解法是结合气相沉积制备聚对二甲苯薄膜和热丝化学气相沉积而形成的一种制-CH薄膜的新方法。热丝辅助裂解法的最大特点就是在保持低衬底温度情况下可以获得高沉积速率，而热丝加热电流对薄膜沉积速率和薄膜表面形貌具有重要影响。研究表明，热丝加热电流越大，薄膜沉积速率越高，在加热电流9A时，薄膜沉积速率可达0.002mm/min，同时薄膜表面粗糙度随之增加，薄膜表面也开始出现其它元素污染，因此，一般热丝加热电流选择为7A附近。     

Synthesis and characterization of isotopically enriched methylmercury (CH3201Hg+)

A simple procedure for the synthesis of an important standard, isotopically enriched methylmercury, which is not commercially available, has been established successfully. The isotopically enriched standard synthesized is utilized in conventional isotope dilution mass spectrometry (IDMS), as well as in speciated IDMS (SIDMS), for determination of the true concentration of methylmercury in environmental samples. The CH₃²⁰¹Hg⁺ standard has been synthesized from commercially available ²⁰¹HgO and tetramethyltin. The synthesis time required is 1 h at 60°C. The product is highly pure, yielding more than 90% as ²⁰¹Hg in CH₃²⁰¹Hg⁺. Hazardous dimethylmercury does not occur during this synthesis procedure. The product synthesized was analyzed using high‐performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (ICP‐MS) and ICP‐MS alone in order to determine its concentration, isotopic composition and purity. The stability of the product was also evaluated for over 6 months and found to be stable at 4°C in the dark. The isotopically enriched methylmercury synthesized can be used in SIDMS and IDMS analyses as a standard. Copyright © 2003 John Wiley & Sons, Ltd.     

CH分子束的强度与CH4/He混合配比的关系及CH(A2△)振转温度的计算

为了获得CH分子束及其相关特性,以氦气为载气,利用直流脉冲放电技术产生了CH分子束.实验记录了放电时间相对于脉冲分子束不同延时CH光谱信号强度的变化,放电相对延时为460μs左右获得最大的信号强度.研究了在保持CH4/He总气压3 atm和放电电压-4 kV不变的条件下CH分子束强度与不同配比的关系,建立了理论模型,对实验数据进行了理论拟合,拟合曲线与实验结果符合较好,配比为1%(甲烷与氦的气压比为1:99)左右能够维持较稳定的放电现象和较强的放电强度而获得较强的CH自由基束流.在这一配比下对CH(A2△-X2П)(0,0)带发射光谱进行探测和分析,获得CH(A2△)转动温度和振动温度分别为2455 K和4575 K,并估计此时每个脉冲中大约包含1013～1014个CH自由基.     

自由基CH(X2Π,a4Σ-)的光谱数据从头算研究

用分子轨道从头算方法,对CH自由基的基态(X2Π)和低激发态(a4Σ-)的光谱数据进行了计算.计算结果表明,在基态CH(X2Π)时,在QCISD(T)/6-311G (3df,3pd)水平上,计算所得的键长R=0.1120981nm,偶极矩μ＝1.5891 Debye,ν＝2845.43cm-1均与实验值相吻合,在B3PW91/6-311G (3df,3pd)理论水平上,计算的基态能量为-38.496143 Hartree,误差仅为0.22%;对低激发态CH(a4Σ-),使用含时的密度泛函方法(TDDFT)和大基组6-311 G(3df,3pd)计算所得的R=0.1094nm,垂直跃迁能量为0.926eV,均与实验结果有较好的吻合.     

CH分子束的强度与CH_4/He混合配比的关系及CH(A~2Δ)振转温度的计算

为了获得CH分子束及其相关特性,以氦气为载气,利用直流脉冲放电技术产生了CH分子束。实验记录了放电时间相对于脉冲分子束不同延时CH光谱信号强度的变化,放电相对延时为460μs左右获得最大的信号强度。研究了在保持CH4/He总气压3 atm和放电电压-4 kV不变的条件下CH分子束强度与不同配比的关系,建立了理论模型,对实验数据进行了理论拟合,拟合曲线与实验结果符合较好,配比为1%(甲烷与氦的气压比为1∶99)左右能够维持较稳定的放电现象和较强的放电强度而获得较强的CH自由基束流。在这一配比下对CH(A2Δ-X2Π)(0,0)带发射光谱进行探测和分析,获得CH(A2Δ)转动温度和振动温度分别为2455 K和4575 K,并估计此时每个脉冲中大约包含1013~1014个CH自由基。     

Reaction Mechanism Investigation Using Vibrational Mode Analysis for the Multichannel Reaction of CH_3O+CO

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