Electrodeposition of Copper in Presence of Carbohydrates

The rates of electrodeposition of copper plates were determined by measuring cathodic limiting current in the absence and in the presence of carbohydrates (glucose, fructose, mannose, sucrose, lactose, and maltose). It is found that the rate of electrodeposition decreases in the presence of organic additives by an amount ranging from 1.89% to 35.85%, and depending on the types of additives and its concentrations. Our investigation of adsorption isotherm indicates that the inhibition fits both the Langmuir adsorption isotherm and Flory-Huggins adsorption isotherm; we found that the rate of electrodeposition decreases by increasing height and increasing CuSO₄ concentrations. Thermodynamic parameters are given and show that electrodeposition process is diffusion controlled. The rate of deposition and its equations are represented:

• Sh = 0.099Re^0.715 Sc^0.33 for glucose with average deviation: ±0.158%

• Sh = 0.097Re^0.715 Sc^0.33 for fructose with average deviation: ±0.058%

• Sh = 0.099Re^0.715 Sc^0.33 for mannose with average deviation: ±0.108%

• Sh = 0.098Re^0.713 Sc^0.33 for sucrose with average deviation: ±0.003%

• Sh = 0.099Re^0.714 Sc^0.33 for lactose with average deviation: ±0.018%

• Sh = 0.099Re^0.713 Sc^0.33 for maltose with average deviation: ±0.097%.

     

Limiting Current of Copper Electrodeposition from a Copper Sulfate Solution under Conditions of Natural Convection: The Space Charge Effect

Copper electrodeposition from a copper sulfate solution under conditions of natural convection is analyzed theoretically and examined experimentally. The space charge, which forms in the near-cathode layer, is shown to affect the limiting current density and to change its concentration dependence.     

Electroplating of Steel in the Presence of 5,6-Dihydropyrimidine-2-(1H)-thione, 2-Methylthiopyrimidine-4-(1H)-one, 2-Thiopyrimidine-4-(1H)-ones,and 2,4-Pyrimidine(1H,3H)-dione Derivatives as Organic Additives

The electrode processes on steel in acidified CuSO₄ were finding to depend on the organic additives as well as their concentrations. They also depend on the type of the anode and temperature. The activation energy proves that the reaction is diffusion controlled. The percentage of inhibition for all solutions ranged from 6.9% to 44.7% and depended on the type of the cathode and the concentration of the additive. The order of inhibition efficiency of steel cathode is: compound 4 > compound 5 > compound 3 > compound 2 > compound 6 > compound 1. The overall mass transfer correlation proves that the electroplating reaction is natural convection, which is in accordance with our previous studies.     

2种有机添加剂对锡电沉积的影响

2种有机添加剂对锡电沉积的影响;有机添加剂;电沉积;循环伏安;交流阻抗     

玻碳电极上铜电沉积初期行为研究

运用循环伏安和计时安培法研究酸性镀铜溶液中硫酸和 2_巯基苯骈咪唑对铜电沉积初期行为的影响 .实验表明铜的电沉积经历了晶核形成过程 ,其电结晶按瞬时成核三维生长方式进行 ,硫酸对铜的电沉积具有加速作用 ,而 2_巯基苯骈咪唑对铜的电沉积起阻化作用 ,两者均不改变铜的电结晶机理     

Effect of Solvents on the Corrosion Inhibition of Copper by 1,2,3-Benzotriazole

Electromotive force (E) measurements have been made at 303.15 K on the cell, Cu _x Hg/CuCl₂ (m) in solvent S′ [S′=W or FD or DMF each containing 15 ppm of 1,2,3-benzotriazole (BTA)] /AgCl/Ag (where W, FD and DMF represent the solvents water, formamide and N,N-dimethylformamide, respectively). The Emf data have been compared with the corresponding data under the same conditions in pure W, FD and DMF; the Emf values change from negative to very positive in the presence of BTA in these solutions and suggest the possibility that the presence of BTA in W, FD and DMF helps to bind copper ions with solvent molecules through formation of new complex structures of the film formed on the metal surface. We have suggested the probable mechanism of formation of a protective film through complex formation. The higher Emf values in the presence of BTA indicate strong ion-solvent interactions and the order of interactions was found to be as: FD≥DMF>W. Further iterative procedures were employed to evaluate K ₁,K ₂ (dissociation constants), α ₁,α ₂ (degrees of dissociation), γ _± (mean activity coefficient) and E ^o (standard cell potential) making use of the measured E values. The standard molar Gibbs energy of transfer, ΔG _tr^o, of CuCl₂ from the pure S to S′ were calculated using the computed standard cell potentials. The calculated ΔG _tr^o values were found to be negative which was indicative of strong ion-solvent interactions and reasonably supported the trend of ion-solvent interactions. From these studies we concluded that BTA acts as a better corrosion inhibitor towards copper in FD and DMF than water.     

铝（Ⅲ）—桑色素—含氧有机溶剂荧光体系的研究

本文系统研究了醇、酮等7种含氧有机溶剂对铝-桑色素络合物荧光反应的溶剂化效应。研究发现,上述有机溶剂对荧光体系均有增敏作用,以乙醇的效果最佳,使络合物的荧光强度增加6倍多。据此,本文建立了测定微量铝的高灵敏度荧光分析方法,线性范围为0～1.0μg/10ml,检测限为1.6×10~(-9)g/ml。用所建立的方法对化学试剂中的微量杂质铝进行了测定,结果令人满意。并对有机溶剂化效应的机理作了探讨。     

烟酸对酸性硫酸盐体系铜电沉积的影响

对溶液A: 0.8 mol•L－1硫酸铜,0.6 mol•L－1硫酸,5.0×10－5 mol•L－1氯离子,1.0×10－4 mol•L－1聚乙二醇的溶液,溶液B:在溶液A中加入2.0×10－2 mol•L－1烟酸,pH为0.5,运用循环伏安和计时安培法研究玻碳电极上铜的电沉积行为.结果表明,铜的电沉积过程经历了晶核形成过程,其电结晶按瞬时成核和三维生长方式进行.烟酸的加入对铜的电沉积具有阻化作用,但不改变铜的电结晶机理.沉积层的X射线衍射表明Cu为面心立方结构,在烟酸存在下沉积层出现(220)高择优取向,这可能是烟酸在Cu(220)晶面上发生强烈吸附作用的结果.     

Corrosion of Copper in Presence of Acetic Acid Derivatives

The anodic corrosion of copper in presence of acetic acid derivatives were determined by measuring the limiting current. It is found that the rate of corrosion increased by decreasing H₃PO₄ concentration and electrode height. The experimental results showed that the inhibition efficiency increased with increasing concentration of the investigated compounds at a fixed temperature, but decreases with increasing temperature. Values of activation energy indicate that the reaction is diffusion controlled. The isotherm Langmuir, Temkin, and Flory Huggins are applied. The values of free energy of adsorption (ΔG_ads) obtained indicate the spontaneous adsorption of the inhibitor. The overall mass transfer correlations under the present conditions have been obtained using dimensional analysis method. The results agreed with the previous studies of mass transfer to rotating cylinder in turbulent flow.At the end of the corrosion process the morphology of the specimens after experiment is monitored using scanning electron microscope (SEM). SEM examination of the copper surface revealed that these compounds inhibited copper from corrosion by adsorption on its surface to form protective film. The presence of these organic compounds adsorbed on the electrode surface was confirmed by SEM investigations.     

基于铜纳米簇的硝酸根微传感器的研究

基于循环伏安扫描(CV)的电化学沉积方法制备出多孔性纳米簇状结构铜膜,结合采用微机电系统(Micro electro mechanical systems,MEMS)技术制备的微电极芯片,研制出用于NO3-检测的安培型微传感器。考察该微传感器对NO3-的响应性能,在6.25~300mmol/L浓度范围内,灵敏度为0.0526mA/(mmol/L),线性度99.93%;在300~3500mmol/L浓度范围内,灵敏度为0.0353mA/(mmol/L),线性度99.18%。与文献报道相比,该传感器表现出更高的灵敏度。考察水体中常见的NO2-,Cl-,HPO42-/PO43-,SO42-,HCO3-/CO23-,Na+和K+等离子对该传感器的干扰性能,传感器表现出较好的抗干扰性能。采用该微传感器对实际水样进行测试,测试结果与具有权威资质的测试公司的测试结果之间具有一定的相关性。实验结果表明,采用循环伏安沉积方法在微电极表面制备的纳米簇状结构的铜敏感膜,比表面积大,催化活性高,对NO3-表现出了很好的敏感特性和选择性,适用于对微量NO3-的检测。     

气相色谱法测定托吡酯中有机溶剂残留量

用填充柱FID-GC外标法在线检测托毗酯中4种有机溶剂残留量，通过线性、准确度、精密度、专属性、最低检测限等试验，证明此方法分离度高、灵敏、准确、简便，能满足检测要求．     

亚甲基二膦酸为配位体的无氰碱性镀铜

提出一种以亚甲基二膦酸(MDPA, H₄L)为主配位剂的无氰镀铜体系. 采用pH 电位滴定法分别测定MDPA的四级解离常数和MDPA-Cu(II)的稳定常数, 并比较MDPA-Cu(II)和羟基乙叉二膦酸(HEDPA)-Cu(II)的循环伏安曲线和阴极极化曲线. 结果表明: MDPA各级解离常数为, pK₁=1.86, pK₂=2.65, pK₃=6.81, pK₄=9.04;MDPA与Cu²⁺形成分级配合物的稳定常数为, pK_ML=10.65, pK_ML2 = 5.59, pK_ML3 = 2.50; 随着pH升高, 形成的配合物依次为, Cu(H₃L)₂、[Cu(H₃L)(H₂L)]-和[Cu(H₂L)₂]^2-; 当pH在7-10 时, MDPA较HEDPA更易与Cu²⁺配位. 当pH=9 时, MDPA碱性镀铜体系阴极主要发生的是[Cu(H₃L)(H₂L)]^-和[Cu(H₂L)₂]^2-还原生成铜的过程; 在10 °C,MDPA体系的铜配位化合物还原生成铜的电位比HEDPA体系负移, 扩散速度更快.     

三种添加剂对纳米晶锌镀层电沉积行为及结构的影响

运用极化曲线、XRD和SEM研究了三种有机添加剂对酸性硫酸盐溶液中锌电沉积行为以及纳米晶锌镀层结构的影响.结果表明,十六烷基三甲基溴化铵(CTAB)、4-苯基-3-丁烯-2-酮(BA)和聚乙二醇(PEG)三种添加剂之间具有较强的协同作用,采用三者组成的混合添加剂可制备出光亮致密的纳米晶锌镀层.镀层晶粒细化的主要原因在于混合添加剂可有效提高锌的沉积过电位,使锌沉积过程中的晶核形成速率增大.     

基于氯化胆碱离子液体的铜电沉积研究（英文）

采用恒电流和恒电位方法,基于含有氯化铜溶液的乙二醇-氯化胆碱或硫脲-氯化胆碱离子液体,室温下在钢阴极上进行了铜的电沉积. 利用扫描电子显微镜和X-射线衍射技术研究了各种实验条件对电沉积的影响以及沉积层的形貌. 结果表明,室温下施加不超过-0.45 V的沉积电位和不超过-4.0 A·m^-2的沉积电流密度,可以同时从氯化胆碱基乙二醇和硫脲离子液体中沉积得到非常光滑、有光泽、致密且具有良好结合力、色泽鲜艳的铜金属涂层. 铜的电沉积阴极电流效率约为97%.     

有机溶剂对ICP—AES分析性能影响的研究

研究了有机溶剂对电感耦合等离子体－原子发射光谱（ＩＣＰ－ＡＥＳ）分析性能的影响。ＭｏｎｔｅＣａｒｏｌ模拟结果和实验结果表明，只要选择合适的操作参数，有机溶剂直接引入ＩＣＰ不仅不会影响ＩＣＰ的稳定性，还会提高某些元素的灵敏度，从而提高了ＩＣＰ－ＡＥＳ的分析性能。     

气相色谱法测定核苷类药物中的有机溶剂残留量

用HP-5毛细管气相色谱柱、FID检测器,以二甲亚砜为溶剂进行外标法定量测定药物合成产物中的有机溶剂残留量.乙腈、乙酸乙酯的线性范围分别为0.787~15.700μg(R2=0.9994)、0.180~4.510 mg(R2=0.9991),回收率测试结果满足分析测试的要求,最低检测限分别为3.9、0.40 mg/mL.本方法简单、准确、灵敏高,重现性好,适用于核苷类药物中有机溶剂残留量的测定.     

高效液相色谱中用于梯度洗脱的有机溶剂的纯度测试

在反相高效液相色谱中,空白梯度基线的漂移和杂质峰,可能由含水溶剂和有机溶剂中杂质所引起的。当含水溶剂通过预柱在线净化后,根据空白梯度色谱图可测试有机溶剂的纯度。按照此法,对国产不同等级的乙腈和甲醇进行了测试,指明这些试剂用于梯度洗脱的可能性。     

Gel Chromatography of Metal Acetylacetonates in Organic Solvents

Abstract

Tris (acetylacetonato)cobalt(III) and tris(acetylacetonato)-chromium(III) have been eluted by gel chromatography through styrene-divinylbenzene copolymer gel using an organic solvent as an eluent. Elution counts of these chelates in these solvents reflect some mutual interactions between metal chelate, gel and solvent. When benzene or chloroform was used as an eluent, sieving effect seems to be dominant for the separation of these chelates. Discussions were done in relation to solubility parameters of the solvent, the complex and the gel.     

有机溶剂性质及其水含量对酶催化合成含D－氨基酸残基的二肽衍生物的影响

有机溶剂性质及其水含量对酶催化合成保护的寡肽及其衍生物有显著影响。系 统地研究了有机溶剂性质及在不同有机溶剂中水含量对α－胰凝乳蛋白酶催化合成 含D－氨基酸残基的二肽衍生物产率的影响。用α－胰凝乳蛋白酶、枯草杆菌蛋白 酶和嗜热杆菌蛋白酶在有机溶剂中催化合成了一系列保护的二肽及其衍生物，并研 究了水含量对反应产率的影响，得到了十分有意义的结果。