离子交换膜法合成2,2′-二氯氢化偶氮苯

应用离子交换膜法电解邻氯硝基苯合成2,2′-二氯氢化偶氮苯.讨论了电极活化条件、电流密度、电解液温度等因素对电解还原反应的影响.结果表明:在反应温度t=80℃,阴极、阳极电解液分别为10%和30%(by m ass)的NaOH溶液,电流密度4.2A/dm2条件下电解,电流效率最高,可达73%,收率为83%.     

电流密度对锌电积用Pb-Ag平板阳极电化学行为的影响(英文)

研究了在不同电流密度下进行长时间极化后Pb-Ag(0.8%(质量分数,w))平板阳极的阳极电位、腐蚀率及阳极钝化膜.同时,也研究了该阳极在ZnSO4-MnSO4-H2SO4电解液中的阴极电流效率和阴极锌品质.阳极钝化膜的表面形貌用扫描电镜(SEM)进行观测.实验结果表明,不管电解液中是否存在Mn2+,电流密度对阳极和阴极的电化学行为都产生了显著的影响.随着电流密度的升高,阳极电位、腐蚀率、阴极电流效率和阳极泥生成量也增加,而阴极锌中的Pb含量则减少.当电流密度从500A·m-2降到200A·m-2时,阳极在ZnSO4-MnSO4-H2SO4电解液中的稳定电位和腐蚀率分别减少64mV和40%.此外,在比较低的电流密度下,阳极电位更容易稳定,阳极表面生成的钝化膜更加致密并与基体结合牢固,这些都有利于降低阳极腐蚀率.为了降低阳极电位、减小阳极腐蚀率及阳极泥生成量并提高阴极电流效率和阳极锌品质,锌电积的理想工作条件是较低的阳极电流密度和较高的阴极电流密度.     

NaCl对离子液体中电解精炼铝的影响

研究了添加NaCl对BMIC-AlCl3离子液体电导率及电解精炼铝的影响,分析了阴极电流效率、电流密度的变化,并通过扫描电镜和能谱分析研究了沉积层的形貌及成分。结果表明,添加NaCl可以提高电解液的电导率,阴极电流效率也可提高至82%～96%,但电流密度则有所降低;添加NaCl还可以改善电解精炼铝的沉积质量,使晶粒尺寸...     

电解条件对电化学法制备FeO42-的影响

以铁丝网作阳极,应用电解氧化法制备FeO42-溶液,并合成固体K2FeO4.研究电解条件(如搅拌、超声、静置、温度、电流密度等)对该制备过程电流效率的影响规律.结果表明:以14 mol/L NaOH作电解液,于30℃、10 mA.cm-2及搅拌作用下电解,可获得较高的电流效率.     

低浓度NaCl溶液Ti/Pt阳极电解制备活性氯

以Ti板阴极、Ti/Pt阳极组成无隔膜电解装置,电解低浓度NaCl溶液制得活性氯.研究电解时间、电流密度、氯离子浓度、溶液pH值对活性氯浓度及电流效率的影响.结果表明:电解时间增加,活性氯浓度增加,而电流效率逐渐降低;初始阶段活性氯浓度增加较快,近1 h活性氯浓度趋于稳定;增加氯化钠浓度可提高活性氯浓度和改善电流效率;微酸性电解液有利于提高活性氯浓度.电解过程中,溶液电导率不断降低,pH值变化范围在1之内.     

稀土贮氢合金电极在乙醛酸电解制备中的应用

研究了以AB5型稀土贮氢合金作催化还原电极恒电位电解草酸制备乙醛酸,合金表面处理和电极活化可提高电解产率和电流效率.确定了最佳电解工艺条件:电流密度120mA·dm-2,电解液温度30℃,草酸浓度1.0mol·L-1,此时电流效率为86%,电解产率为88%.随着电解次数的增加,由于贮氢合金膨胀粉化及表面被电解产物覆盖,电流效率和乙醛酸产率均呈下降趋势,在电解过程中即时分离电解产物有利于提高电流效率和乙醛酸产率.     

间接电氧化2-丁酮制备α-羟基缩酮的研究

在板框式循环电解槽中,以KOH为电解质,KI为催化剂,石墨电极分别为阳极和阴极,研究电化学间接氧化2-丁酮合成乙偶姻中间体α-羟基缩酮,讨论电流密度、极板间电解液流速、电解液中2-丁酮浓度、电解温度以及通电量等电解条件对中间体收率和电流效率的影响,经优选工艺条件为：电流密度40 mA·cm^-2,流速6.4 cm·s^-1,2-丁酮浓度1.75 mol·L^-1,电解温度30℃,通电量为1.5 F·moL^-1时,中间体收率可达78.9%,电流效率40.1%. 循环伏安测试结果表明,电解时碘离子在阳极氧化生成碘单质,甲醇在阴极还原生成甲氧基负离子,原料2-丁酮与电解产物反应,并最终生成乙偶姻中间体.     

电化学氧化苯酚合成对苯醌的研究

在H型阳离子交换膜电解槽中,以H₂SO₄电解质、阳极和阴极铅电极,研究苯酚电解氧化合成对苯醌. 讨论电流密度、电解质浓度、电解液中对苯醌浓度和萃取剂等电解条件对对苯醌收率和电流效率的影响. 经优选工艺条件为：电流密度4 A·dm^-2,H₂SO₄电解质浓度1 mol·L^-1,氯仿萃取剂. 通入3.2 Ah电量,对苯醌收率可达68%,电流效率为24.7%. 而在萃取剂存在下,对苯醌收率可提高至73%,电流效率为26%. 实验结果表明氯仿萃取剂可循环套用.     

二氧化铅膜电极用于电解合成苯醌的研究

:本文研究了一种新型的电极———PbO2 膜电极用于以苯酚为原料电解合成苯醌的反应 ,讨论了电解液的酸度、电流密度和苯酚浓度对电流效率的影响。结果表明 ,对于高浓度的苯酚溶液 ,在酸性条件下、保持适中的电流密度能获得较高的电流效率     

电解四甲基碳酸氢铵制备四甲基氢氧化铵

以四甲基碳酸氢铵为原料,钛基二氧化钌为阳极,不锈钢为阴极,在H型电解槽中恒电流密度电解合成四甲基氢氧化铵,主要考察了合成工艺中离子交换膜种类、原料浓度、电解温度和电流密度对电流效率的影响。研究结果表明,当采用旭化成F4403D为阳离子交换膜,在四甲基碳酸氢铵浓度为1.41mol·L-1,电解液温度40℃～60℃,电流密度792A.m-2的条件下,电流效率可达83.5%。     

(NaPO3)6对AZ91D镁合金微弧氧化陶瓷层电化学腐蚀特性的影响

在Na2SiO3-KOH电解液体系中添加一定量的(NaPO3)6, 利用微弧氧化(MAO)技术在AZ91D 镁合金表面制备了原位生长的陶瓷层. 采用动电位极化和电化学阻抗谱(EIS)技术研究了添加(NaPO3)6前后, 制备的陶瓷层在3.5%(w) NaCl溶液中的室温电化学行为. 结果表明, 添加(NaPO3)6后, 陶瓷层的自腐蚀电位显著上升, 自腐蚀电流密度明显减小. 这主要是由于(NaPO3)6增加了反应过程中基体镁合金表面的“氧空位”和溶液中PO3-4的含量, 促使元素Mg在金属/膜层(M/F)界面上快速形成相应氧化物, 从而增加了陶瓷层的厚度和致密性. 根据电化学反应体系和陶瓷层的特殊结构, 建立了合理的等效电路, 并结合EIS 数据, 分析了添加(NaPO3)6提高陶瓷层耐电化学腐蚀性能的机理.     

Electropolishing of titanium alloy under hydrodynamic mode

Titanium (Ti) alloys are widely used in aerospace industry due to the low density and high corrosion resistance. However, machining and polishing remain great challenges because of the hardness and chemical stability. With a home-made electrochemical machining workstation, cyclic voltammetry is performed at a wide potential range of [0 V, 20 V] to record the details of passivation and depassivation processes under a hydrodynamic mode. The results show that the thickness of viscous layer formed on the alloy surface plays a crucial effect on the electropolishing quality. The technical parameters, including the mechanical motion rate, polishing time and electrode gap, are optimized to achieve a surface roughness less than 1.9 nm, which shows a prospective application in the electrochemical machining of Ti and it alloys.     

锌铋合金电极在溶胶电解液中的电化学行为

锌电极的自腐蚀速率, 持续放电下的阳极溶解速率和电极钝化的难易程度是碱性电池性能的重要电化学参数. 本文应用线性极化、恒流放电等电化学实验方法研究了电解液中添加Carbopol树脂以及电极中添加Bi对锌电极电化学行为的影响. 并应用金相显微镜和环境扫描电子显微镜(ESEM)对锌电极和锌铋合金电极浸蚀及放电后的形貌进行了表征. 结果表明: 电解液中添加适量的Carbopol树脂可明显提高电极的极化电阻, 显著降低电极的自腐蚀速率; 阳极的溶解电位出现不同程度的正移, 阳极过电位显著增大且大电流密度放电时较明显促进电极钝化. 锌电极中添加一定量的Bi对改善电极表面氧化物膜的沉积形貌和电极表面固液界面的传质条件, 减小电极的自腐蚀速率, 抑制电极自腐蚀等方面具有显著作用.     

酸性AlCl3-BMIC离子液体中的铝阳极溶解

采用线性扫描伏安法研究了Lewis 酸性AlCl₃-BMIC (BMIC: 1-butyl-3-methylimidazolium chloride)离子液体中铝电极的溶解. 铝电极在阳极极化时出现了钝化现象, 钝化是由于在铝电极表面形成了固体AlCl₃钝化膜造成的. 铝的电化学溶解过程可以依次分为三个区: 电化学控制区、过渡区和钝化区. 在电化学控制区, 铝的电化学溶解速率随着电位的正移而逐渐增加; 在过渡区, 由于电极表面AlCl₄^-和Al₂Cl₇^-浓度发生改变而析出固体AlCl₃使得铝电化学溶解速率随着电位的正移而逐渐减小; 当钝化膜形成之后, 铝的电化学溶解速率不再随着电位的正移而发生改变, 铝溶解进入钝化区. 增加搅拌、升高温度、降低离子液体AlCl₃摩尔分数都可以增加铝溶解阳极极限电流密度.     

Studies on the influence of various experimental conditions on electrochemical generation of ferrate(VI) in NaOH-KOH mixed electrolyte

Ferrate(VI) was prepared by electrooxidation in diaphragm electrolyzer with iron wire gauze as anode and NaOH-KOH mixed solution as electrolyte. The influences of various experimental conditions, such as the volume ratio of NaOH-KOH mixed electrolyte, temperature, current density, passivation of iron anode were investigated on ferrate current efficiency. Due to the low solubility of K₂FeO₄ in concentrated alkaline solution and the passivation of iron wire gauze anode, a highest current efficiency over 90% was obtained at 45°C and at a current density of 5 mA cm⁻² in mixed electrolyte with the volume ratio of NaOH: KOH equal to 6: 4. The result is superior to using NaOH and KOH as electrolyte respectively. In addition, polarization curves, scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) were employed to further study the effects of synthesis conditions on ferrate(VI) in theory. Published in Russian in Elektrokhimiya, 2009, Vol. 45, No. 7, pp. 853–857. The article is published in the original.     

The effect of anode surface area on nanoporous oxide formation during anodizing of low purity aluminum (AA1050 alloy)

Porous anodic alumina layers were obtained by a simple two-step anodization of low purity aluminum (99.5 % Al, AA1050 alloy) in a 0.3 M oxalic acid electrolyte at 45 V and 20 °C. The effect of anode surface area on structural features of nanoporous oxide and process of oxide formation was investigated. An ordered structure composed of nanostripes or nanopores was formed on the Al surface during electrochemical polishing in a mixture of perchloric acid and ethanol. This nanopattern is then replicated during the anodic oxide formation. It was found that the pore diameter, interpore distance, and porosity increase slightly with increasing surface area of the aluminum sample exposed to the anodizing electrolyte. On the other hand, a slight decrease in pore density and cell wall thickness was observed with increasing surface area of the sample. The detailed inspection of current density vs. time curves was also performed. The obtained results revealed that the higher surface area of the anode, the local current density minimum, was reached faster during first step of anodization and the increase in current density corresponding to the pore rearrangement process was observed earlier. Finally, a dense array of Pd nanowires (～90 nm in diameter) was synthesized by simple electrodeposition of metal inside the channels of through-hole nanoporous anodic alumina templates with relatively large surface areas (4 cm²).     

Corrosion behavior of Mg,AZ31, and AZ91 alloys in dilute NaCl solutions

Corrosion behavior of extruded Mg, extruded AZ31 alloy, and cast AZ91 alloy was investigated by electrochemical measurements in dilute NaCl solutions. Corrosion products and passivation films were analyzed by X-ray diffraction and X-ray photoelectron spectroscopy. All specimens exhibit the corrosion and passivation zones in dilute NaCl solutions. The aluminum content and alloy microstructure influence the corrosion and passivation processes. AZ91 alloy shows the broadest passivation zone followed by AZ31 alloy and Mg. AZ91 alloy reveals a highest corrosion resistance, and preferential attack is located at the primary Mg phase. Its relatively fine β-phase (Mg₁₇Al₁₂) network and Al₂O₃/Al(OH)₃ compounds produced on the passivation film are the main factors which limit the corrosion progress as compared with AZ31 alloy and Mg. The thick passivation product on AZ31 alloy is the key factor which restricts the corrosion attack in dilute solutions.     

铝合金表面改性对有机涂层附着力的影响及腐蚀防护性能研究

利用电化学阻抗（EIS）、扫描微参比技术（SRET）、接触角、粗糙度、附着力、盐雾等测试方法,研究了铝合金阳极氧化与贻贝黏附蛋白（MAP）/CeO₂/硅烷γ-APS（MCA）表面复合修饰的腐蚀防护性能以及对改性聚氨酯涂层附着力和耐蚀性的影响。结果表明,MCA复合膜可抑制铝合金的腐蚀,并具有一定的自修复功能;阳极氧化和MCA表面复合修饰可为铝合金提供有效的早期腐蚀防护作用,且能提高铝合金表面粗糙度和润湿性,显著提升改性聚氨酯涂层在铝合金表面的附着力和耐蚀性,因而结合改性聚氨酯涂层和表面复合修饰可实现对铝合金长期有效的腐蚀防护。     

Properties of composite nickel-cobalt-aluminum oxide coating deposited from chloride electrolyte

Effect of the cathodic current density, pH value, electrolyte temperature, and concentration of aluminum oxide introduced into the electrolyte on the wear, microhardness, and internal stresses in nickel-cobalt-aluminum oxide composite electrolytic coatings was studied. It is shown that the coatings under consideration can be used instead of chromium coatings.     

Effect of Aluminum Alloy Surface Modification on Adhesion of the Modified Polyurethane Coating and Its Corrosion Protective Performance北大核心CSCD

The ordinary organic coatings on aluminum alloy usually encounter a problem of low adhesion to the substrate, which results in destruction and failure of the long-term protective performance of the anticorrosion systems. The surface modification of aluminum alloy is able to enhance the adhesion of organic coating on aluminum alloys, and to improve their protective performance. In this work, a combined surface modification of anodic oxidation and mussel adhesion protein/CeO2/3-aminopropyltriethoxysilane composite film (MCA) was developed on the aluminum alloy. The adhesion of modified polyurethane coated on the treated aluminum alloy and its corrosion protective performance were evaluated comprehensively by using contact angle, adhesion strength, electrochemical impedance spectroscopy (EIS), and scanning reference electrode technique (SRET). The measurements of EIS and SRET demonstrated that the MCA composite film on anodic oxidized Al possessed self-healing function and provided effective protection against early corrosion of aluminum alloy. The pull-off test showed that both anodic oxidation treatment and MCA composite film modification were able to increase the adhesion of modified polyurethane coating on aluminum alloy, and their combined action were supposed to remarkably enhance the adhesion strength up to 17.1 MPa. The reason for the improvement of adhesion was that the anodic oxidation treatment and MCA composite film modification could improve the surface roughness of aluminum alloy, and enhance the surface wettability and surface polarity, which is beneficent to enhance the bonding of the modified polyurethane coating to aluminum alloy surface. The EIS results showed that no any corrosion occurred for the modified polyurethane coating on the treated aluminum alloy during 65 d immersion in 3.5wt.% NaCl solution. The impedance value in low frequency range of the modified polyurethane coating always maintained at a high order of magnitude on the aluminum alloy treated by anodic oxidation and MCA composite film modification, showing an excellent protective performance of the coating system. The evaluation of Neutral Salt Spray (NSS) indicated that the modified polyurethane coating on the treated aluminum alloy owned superior corrosion protection performance, and the adhesion strength remained 13.1 MPa and no any corrosion was found at the scratch locations even after 1200 h of salt spray testing. It was concluded that combination of anodic oxidation and MCA composite film were capable of significantly improving the adhesion of modified polyurethane coating on aluminum alloy and providing long-term effective corrosion protection for aluminum alloy. © 2021 Authors. All rights reserved.