隔膜对双电层电容器和混合型电池-超级电容器的电化学性能的影响

隔膜是双电层电容器和混合型电池-超级电容器等电化学储能器件的重要组成元件.本文采用1 mol?L-1四乙基四氟硼酸铵的丙烯碳酸酯电解液制备了基于活性炭的扣式双电层电容器,并采用1 mol?L-1六氟磷酸锂锂离子电解液制备了(LiNi0.5Co0.2Mn0.3O2+活性炭)/石墨体系的混合型电池-超级电容器.研究了不同类型隔膜的物理化学性能,以及其对双电层电容器和混合型电池-超级电容器的电化学性能的影响.四种隔膜分别是无纺布聚丙烯毡、多孔聚丙烯薄膜、Al2O3涂层的聚丙烯薄膜和纤维素纸隔膜.进行了表面形貌、差示扫描量热、电解液吸液量和表观接触角测试表征.电化学测试表明,采用纤维素隔膜的双电层电容器具有最高的比电容和更优的倍率性能,电容器的自放电性能差别不大.而对于混合型电池-超级电容器,采用聚丙烯薄膜和无纺布聚丙烯毡隔膜器件的比容量比其它器件约高20%,且采用纤维素隔膜的器件自放电率最高.     

低温热分析标准物质的研制

研制了两种0~100℃热分析标准物质,分别为金属镓和水杨酸苯酯标准物质。研制的标准物质具有良好的均匀性和稳定性,采用与NIST,LGC相应标准物质比较的方法定值。NIST为SRM 2234镓,其定值采用288.6~314.35 K范围内的绝热热量计测得温度及热量值;LGC用绝热法为水杨酸苯酯的熔化温度和熔化热定值,两种方法都可以直接溯源至SI单位。对定值结果的不确定度进行了分析和评定。镓和水杨酸苯酯标准物质的熔化温度分别为(29.77±0.20)℃(k=2),(41.81±0.34)℃(k=2);熔化热分别为(80.52±0.48)J/g(k=2),(88.94±0.62)J/g(k=2)。研制的两种标准物质满足国家标准物质的技术要求,申报已获批准。     

二异丁腈肼溶液中氮的选择性测定

二异丁腈肼分子结构中含有连氮(-N-N-)和氰基氮(-CN),每一个分子中有4个N原子,其结构式见图1。油溶性偶氮引发剂偶氮二异丁腈是重要的化工原料,广泛用于高分子的研究和生产,可作为氯乙烯、乙酸乙烯和丙烯腈等单体聚合引发剂,也可用作聚氯乙烯、聚烯烃、聚氨酯、聚乙烯醇、丙烯腈与丁二烯、苯乙烯共聚物等的发泡剂。此外,也可用于其它有机合成。偶氮二异丁腈由氯气氧化二异丁腈肼而制得,这开发了偶氮二异丁腈生产的新工艺,达到清     

Rapid,simple and selective determination of 2,4-dinitrophenol by molecularly imprinted spin column extraction coupled with fluorescence detection

A rapid, simple and selective method based on molecularly imprinted, spin column extraction coupled with fluorescence detection was successfully established for the determination of 2,4-dinitrophenol in serum samples. The 2,4-dinitrophenol imprinted polymers exhibited highly selective recognition for the template molecule and the maximum adsorption capacity was 138.9 mg/g. The results indicated that when water is used as the loading solution, only 2,4-dinitrophenol could be adsorbed on the spin column without the remaining structural analogs（2-nitrophenol, 4-nitrophenol and phenol）. After eluting with acetonitrile/acetic acid（9/1, v/v）, 2,4-dinitrophenol in serum samples could be determined by using the fluorescence spectrometer, based on the fluorescence enhancement of fluorescein by the template molecule. Under the optimal conditions, the spiked recovery ranged from 95.8% to 103.4% and the detection limit was 1 nmol/L. The results confirmed the reliability and practicality of the protocol and revealed a good perspective of this method for biological sample analysis.     

Synthesis,characterization, thermal stability and antibacterial activity of coumarin based methacrylate copolymers

Monomer of 7-methacryloyloxy-4-methylcoumarin(MAOMC) was synthesized and characterized by FTIR, 1H-NMR and 13C-NMR spectroscopy. Copolymers of MAOMC with butoxyethylmethacrylate(BOEMA) at different feed compositions were prepared by free radical solution polymerization at(70 ± 1) °C in ethylmethylketone(EMK) using benzyl peroxide(BPO) as an initiator. The copolymers were characterized by FTIR and 1H-NMR spectroscopy. Thermogravimetric analysis(TGA) and differential scanning calorimetry(DSC) of the copolymers showed moderate thermal stability and higher Tg values. Gel permeation chromatography(GPC) was used to find out the molecular weights of the different copolymers. Antibacterial activities of the copolymers were also investigated against the selected pathogenic bacteria's. The antibacterial activity of the copolymer increases as the MAOMC content increases in the copolymer. This shows that coumarin moiety plays a very important role in the antibacterial activity.     

Electrospinning of nylon-6,6 solutions into nanofibers: Rheology and morphology relationships

The relationship between the rheological properties of nylon-6,6 solutions and the morphology of their electrospun nanofibers was established. The viscosity of nylon-6,6 in formic acid(90%) was measured in the concentration range of 5 wt%-25 wt% using a programmable viscometer. Electrospinning of nylon-6,6 solutions was carried out under controlled parameters. The chemical structure, morphology and thermal properties of the obtained nanofibers were investigated using Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM) and differential scanning calorimetry(DSC), respectively. Entanglement concentration(ce) was found to be 15 wt% and a power law relationship between specific viscosity and solution concentration was observed with exponents of 2.0 and 3.3 for semi-dilute unentangled(c ce) and semi-dilute entangled(c ce) regimes, respectively. The diameter and uniformity of the nanofibers were found to be dependent on the viscosity. Moreover, the average diameter of electrospun nanofibers was found to be dependent on zero shear rate viscosity and normalized concentration(c/ce) in a power law relationship with exponents of 0.298 and 0.816, respectively. For nylon-6,6 solutions, the entanglement concentration(ce = 15 wt%) provides the threshold viscosity required for the formation of a stable polymeric jet during electrospinning and producing uniform beadless fibers. For concentrations less than ce, beaded fibers with some irregularities are formed. DSC analysis showed an increase in crystallinity of all electrospun samples compared to original polymer. Furthermore, Based on FTIR spectroscopy, α phase is dominant in electrospun nanofibers and minor amount of β and γ phases is also available.     

Microstructure characterization of short-chain branching polyethylene with differential scanning calorimetry and successive selfnucleation/annealing thermal fractionation

A series of the copolymers of ethylene with 1-hexene(M1–M9) synthesized by metallocene catalyst Et[Ind]2ZrCl2/MAO was studied by differential scanning calorimetry and successive self-nucleation and annealing(SSA) thermal fractionation. The distribution of methylene sequence length(MSL) in the different copolymers was determined using the SSA method. The comonomer contents of samples M4 and M5 are 2.04 mol% and 2.78 mol%, respectively. Both M4 and M5 have low comonomer content and their MSL distribution profiles exhibit a monotonous increase trend with their MSL. The longest MSL of M5 is 167, and its corresponding molar percent is 43.95%, which is higher than that of M4. Moreover, the melting temperature(Tm) of M5 is also higher than that of M4. The comonomer contents of samples M7, M8, and M9 are 8.73 mol%, 14.18 mol% and 15.05 mol%, respectively. M7, M8, and M9 have high comonomer contents, and their MSL distribution profiles display unimodality. M7 has a lower peak value of 33 and a narrow MSL distribution, resulting in a Tm lower than that of M8 and M9. The MSL and its distribution are also key points that influence the melting behavior of copolymers. Sometimes, MSL and its distribution of copolymers have a greater impact on it than the total comonomer contents, which is different from traditional views.     

差示扫描量热法测定比沙可啶的纯度

建立差示扫描量热法测定比沙可啶原料药样品纯度的方法。考察了炉体气氛、升温速率、称样量3个因素对差示扫描量热法测定结果的影响,确定差示扫描量热法最佳实验条件:升温速率为2.0 K/min,称样量为2.0~4.0 mg,炉内气体为静态空气。差示扫描量热法测定比沙可啶样品纯度为99.86%,测定结果的相对标准偏差为0.02%(n=6),差示扫描量热法测定比沙可啶样品纯度值与HPLC测定结果具有良好的一致性。该方法可以快速、准确地测定比沙可啶化学纯度,为比沙可啶纯度测定提供了一种新的分析方法。     

三维立方准晶椭球夹杂的Eshelby张量

准晶体颗粒复合智能材料具有优异的物化性能和应用前景。不同于传统的各向同性材料,三维立方准晶体材料包含声子场,相位子场,及声子-相位子耦合场。为更好地研究准晶体颗粒夹杂问题,揭示准晶体材料夹杂问题的物理现象,本文利用本征应变公式和柯西留数定理,考虑椭球体夹杂,获得了三维立方准晶材料夹杂问题的Eshelby张量,并给出了统一的表达式。进而,当三维立方准晶夹杂形状为球形、棒状、扁平状和带状时,获得了封闭形式的三维立方准晶Eshelby张量表达式。同时,给出了椭球体长径比变化时Eshelby张量的变化规律,这对研究准晶体颗粒夹杂问题具有重要的理论意义。     

基于涡量矩理论的绕振荡水翼涡动力学分析

文章采用标准k-ω SST湍流模型和动网格技术, 实现了绕俯仰振荡NACA66水翼非定常流动结构与水动力特性的数值模拟, 并基于有限域涡量矩理论定量表征了局部旋涡结构对水翼动力特性的影响. 研究结果表明: 在水翼升程阶段, 当攻角较小时, 层流向湍流的转捩点由水翼尾缘向前缘移动; 在较大攻角时, 顺时针尾缘涡?TEV在水翼吸力面上生成并向前缘发展, 同时与吸力面上的顺时针前缘涡?LEV融合发展为附着在整个吸力面上的新前缘涡?LEV, 新的?LEV与逆时针尾缘涡+TEV相互作用直至完全脱落, 直接导致了水翼的动力失速, 在回程阶段, 绕振荡水翼的流场结构逐渐由湍流转变为层流. 基于有限域涡量矩理论的定量分析发现, 有限域内附着的?LEV和?TEV提供正升力, 当?LEV发展覆盖整个吸力面时对升力的贡献最大, 占总升力近50%, 而+TEV提供负升力. 同时发现, 有限域内各旋涡内部的不同区域提供的升力有正有负; 而逸出有限域的旋涡内部不同区域提供的升力方向均保持一致, 其中顺时针涡提供正升力, 而逆时针涡提供负升力. 在失速阶段, 域外旋涡整体对升力贡献较小且存在小幅波动, 体现了流动的非定常性.