铝合金作为阴极在锌电积过程中的电化学行为

选取商业纯铝、防锈铝、锻铝和超硬铝作为锌电积阴极,在ZnSO_4-H_2SO_4体系中通过电化学测试及中试试验研究4种阴极的电化学行为,同时利用扫描电镜(SEM)观察铝合金上电积锌初期形核,X射线衍射(XRD)分析沉积锌结晶取向。研究结果表明:500 A·m~(-2)电流密度下铝及其合金的析出电位(E)和交换电流密度(i0)分别为:E纯铝=-1.541 V,i0=6.33×10-11A·cm~(-2);E防锈铝=-1.545 V,i0=7.74×10~(-8)A·cm~(-2);E锻铝=-1.55 V,i0=1.01×10~(-7)A·cm~(-2);E超硬铝=-1.496 V,i0=6.07×10-3A·cm~(-2)。合金元素的添加会增加初期形核位置、促进成核速率;形核速率的提高,在一定程度上抑制了卤族元素对阴极的腐蚀;长时间沉积后,锌片结晶取向没有发生变化。锻铝和超硬铝易发生烧板和鼓泡,电流效率低,分别只有79.16%和84.54%;纯铝电流效率达到88.04%,且沉积锌平整、光滑,但阴极板容易被卤族元素腐蚀;防锈铝沉积锌质量与纯铝相差不大,电流效率为86.88%,但对卤族元素腐蚀抑制作用明显。     

锌电积过程中锰元素对铝阴极的电化学行为影响

传统湿法炼锌工艺采用纯铝板作为阴极,但随着锌精矿品位的降低,电解液中杂质离子含量增大,造成阴极腐蚀消耗增加.本文以铝锰合金为研究对象,研究锰作为添加元素,与铝形成良好铝锰合金阴极材料的电化学行为,进一步提高铝阴极的耐蚀性和电催化活性.采用交流阻抗、阴极极化曲线、恒电流极化曲线、塔菲尔曲线等分析方法,探讨不同Mn元素含量对铝锰合金在40℃恒温条件,Zn2+ 65 g·L-1和H₂SO₄ 150 g·L-1溶液中电化学行为的影响.研究结果表明:相比纯铝电极,添加Mn元素的铝锰合金电极的耐蚀性普遍提高,腐蚀电流均减小;随着Mn含量的增加,腐蚀电流逐步降低,腐蚀电位与Mn含量增加无明显变化规律;当Mn质量分数为1.5%时腐蚀电流达最低(1.11 mA·cm-2),腐蚀电位最小(-1.0954 V);零电势下,表观电流密度i₀受Mn元素的添加影响显著,i₀随Mn含量增加呈现出先增大后减小的趋势,在Mn质量分数1.5%时达到最大值3.7462×10-16 mA·cm-2,远大于纯铝电极4.8027×10-33 mA·cm-2,整体变化幅度明显,电极的电催化活性得到提高;不同电流密度下的析氢过电位和纯铝电极的整体接近,电化学过程均为电化学传质步骤控制.综合考虑电极材料的耐蚀性和电催化活性,含Mn质量分数1.5%的铝锰合金可作为理想的电积锌阴极使用.      

某些杂质对锌电解沉积的影响

前言溶液中金属杂质的影响,有很多研究者研究过了。众所周知,熔液中的少量杂质会降低电流效率。在采用酸性水溶液电积次贵金属的过程中,在阴极上发生主金属与氢析出的争先反应,这种现象与具有很高氢超电压的锌电积相似。而且,电积锌的重新溶解(系锌电极腐蚀),与锌的溶解过程有关。锌在酸性介质中的腐蚀速度取决于阴极的微量的氢超电压。因     

含氯离子环境下锌铝伪合金涂层的耐蚀性及电化学特性

采用盐雾试验和电化学阻抗谱测试技术研究了纯锌和锌铝伪合金涂层在含氯离子环境中的腐蚀行为和电化学特性,通过扫描电镜、X射线物相分析等手段研究了原始涂层及腐蚀后的表面形貌和腐蚀产物的相结构,并对两种涂层的腐蚀机理进行了初步的探讨.随着盐雾时间的增加,纯锌涂层表面逐渐生成疏松多孔的胞状腐蚀产物层,主要腐蚀产物为Zn₅(OH)₈Cl₂H₂O、ZnO和Zn₅(CO₃)₂(OH)₆,盐雾试验达到768 h后腐蚀产物层局部区域发生龟裂.锌铝伪合金涂层表面生成致密的腐蚀产物层,主要为Zn₅(OH)₈Cl₂H₂O、Zn_0.71Al_0.29(OH)₂(CO₃)_0.145·xH₂O及ZnAl₂O₄.电化学阻抗谱测试结果表明:随着盐雾时间的延长,两种涂层的电荷转移电阻均逐渐增大,但锌铝伪合金涂层的阻抗要明显大于纯锌涂层,表现出了更好的耐蚀性.      

骨胶对长周期锌电积能耗及阴极质量的影响

采用实际生产电解槽的1∶1 000规模,控制阴极电流密度450 A/m2,电积液温度37~40℃,电积液中的Zn2+浓度53~58 g/L,硫酸浓度170~180 g/L,连续电积48 h,研究了骨胶对长周期锌电积的直流电单耗、电流效率和阴极锌表面质量的影响。结果表明,吨锌骨胶加入量控制在0.1~0.3 kg,可以使48 h锌电积的槽电压保持在2.99~3.05 V,吨锌直流电单耗2 820~2 860 kW.h,而电流效率均高于90%,所产阴极锌表面光滑致密;吨锌骨胶加入量超过0.3 kg将使锌电积的直流电单耗显著升高、电流效率明显降低,且所产阴极锌表面粗糙、生长大量突瘤、颜色暗沉。     

真空光源—空心阴极灯在分析卤族元素中的应用

水中过量的氯离子会造成对金属和合金管道、容器的严重腐蚀,因此,水中氯离子浓度的分析,具有重要意义.通常见到的有关卤族元素的分析报告,绝大多数是化学法和离子选择电极法.到目前为止,国内还未见到采用光谱法直接分析卤族元素的公开报导.直接测定卤族元素,长期以来都好象是光谱分析的“禁区”.空心阴极光源应用于光谱分析,是解决卤族元素直接分析的有效手段.目前,国内对空心阴极光源的研究和应用,已     

杂散电流对接地材料在陕北土壤模拟溶液中腐蚀行为影响

采用自行设计的杂散电流模拟装置,测试了距离杂散电流源不同距离的纯锌、纯铜和锌/铜耦接结构在陕北土壤模拟溶液中的电位和腐蚀电流,并结合电化学阻抗谱对接地材料腐蚀行为进行分析.研究发现接地材料纯锌表面存在明显的由阴极区向阳极区的过渡,阳极区的试样腐蚀严重;纯铜表面发生电化学反应的阻抗明显高于纯锌,在存在杂散电流的介质中具有更好的耐蚀性;锌作为牺牲阳极与纯铜接地材料耦接后,会使纯铜表面电位整体负移,原来位于杂散电流流出区域的纯铜也进入阴极区受到保护.      

Fe-TiB2/Al2O3复合阴极的电解性能及元素迁移行为

以氧化铝溶胶为黏结剂、金属Fe为烧结助剂, 采用冷压-烧结制备出铝电解用Fe-TiB₂/Al₂O₃复合阴极材料, 利用20A电解试验研究其电解性能; 利用能谱仪(EDS) 对电解试验前后的复合阴极材料进行了成分物相分析, 研究电解过程中各种元素迁移行为.研究结果表明: 金属Fe作为烧结助剂在烧结过程中能有效的填充骨料之间的空隙, 使该复合阴极材料的烧结致密度显著提高; 20 A电解试验过程电压稳定, 电流效率93. 2%, 原铝中铝元素质量分数为99. 47%, 杂质元素质量分数为0. 53%.在电解试验后, 铝液能有效润湿阴极表面, 表明Fe-TiB₂/Al₂O₃复合阴极材料具有较理想的可润湿性; 从复合阴极电解后的能谱分析可知, 在电解过程中, 碱金属主要是通过液态电解质渗透进入阴极材料中, 随后又逐渐渗透进入黏结剂相中, 并在骨料之间氧化铝溶胶和金属烧结助剂均未能充分填充的空隙进行富集. K元素较Na元素对黏结相的渗透力更强; 与此同时, 阴极表面生成的Al通过复合材料的空隙进入阴极内部, 而Fe金属会利用材料内部的空隙反向扩散至铝液层中.在试验中, 阴极表面的铝液层的稳定存在是该阴极高效稳定运行的基础.      

锌电积节能系统评价与技术研究

湿法炼锌电积单元是一个复杂的控制过程和体系,本文利用专家评议法（Delphi）对电积体系的能源利用情况进行了详细的分析和论述,根据生产情况,找出了影响节能的措施和方法.实践表明这些成果有较好的生产指导性,能带来可观的经济效益.锌电积电流效率由改进前的84.7％提高到87.6％;锌电积直流电单耗由改进前的3 250 kWh/t片降为3 196 kWh/t片,每吨锌片节能54 kWh.     

镀液温度对脉冲电沉积Ni-Sn-Mn合金镀层影响

为了提高低碳钢在海洋环境下的耐蚀性,采用脉冲电沉积法在Q235钢表面制备了Ni-Sn-Mn合金镀层。利用辉光放电光谱仪(GDS)、扫描电子显微镜(SEM)、Tafel极化曲线和电化学阻抗谱(EIS)考察了镀液温度对镀层元素含量、表面形貌、沉积速率、阴极电流效率和耐蚀性的影响。结果表明:随镀液温度的升高,镀层Ni和Sn含量先降低后提高,Mn含量先增加后减少;沉积速率和阴极电流效率提高,镀层耐蚀性先增强后减弱。镀液温度为30℃时,所制备的Ni-Sn-Mn镀层均匀致密,在3.5%NaCl电解液中具有最正的自腐蚀电位(-0.374 V),最低的自腐蚀电流密度(4.266×10-8A·cm-2)和最大的电荷转移电阻(7 459Ω·cm~2),耐蚀性性最好。     

可溶性镁合金的制备及其性能

针对传统可溶性压裂球材质存在的缺点,采用铸造法制备性能优异的可溶性镁合金,系统研究了铝含量对可溶性镁合金组织、溶解性能及力学性能的影响.结果表明:可溶性镁合金组织由α-Mg和β-Mg₁₇Al₁₂相组成,随着铝含量的增多,组织中β-Mg₁₇Al₁₂相数量增多,呈连续网状分布于α相晶界处,并且α晶粒也变得粗大.可溶性镁合金在氯化钾（KCl）溶液中可自行溶解,且随KCl浓度的升高,溶解速率变大,在质量分数为3%的KCl中溶解性能最佳.随着铝含量的增加,可溶性镁合金的溶解速率变大,室温下溶解速率最高可达7.42 mg·h-1·cm-2.溶解产物粒度分析结果显示,中值粒径D₅₀为38.691 μm,溶解产物物相为Mg₁₇Al₁₂和Mg （OH）₂.可溶性镁合金的抗压强度最高可达430 MPa,变形量为3.0%时试样断裂,随着铝含量的增加,可溶性镁合金的塑性降低.      

In situ observations of crystalline oxide formation during aluminum and aluminum alloy oxidation

Anin situ morphological study of the oxidation of electron transparent specimens of aluminum and aluminum alloys containing zinc and magnesium has been carried out in the temperature range 400 to 520°C using the hot stage of a 1 MeV transmission electron microscope. The structure and morphology of the crystalline oxide produced in each alloy has been carefully examined by selected area electron diffraction and stereomicroscopy. In pure aluminum, oxidation takes place after a temperature dependent induction period, by the nucleation of crystalline γ-Al₂O₃ at the amorphous oxide/metal interface. This process is delayed by additions of zinc which modify the structure of the oxide. In alloys containing magnesium, oxidation takes place by the rapid nucleation and growth of MgAl₂O₄ or MgO, with a secondary form of magnesia developing from the reduction of the amorphous γ-Al₂O₃ surface layer.

     

Electrolytic Deposition and Diffusion of Lithium onto Magnesium-9 Wt Pct Yttrium Bulk Alloy in Low-Temperature Molten Salt of Lithium Chloride and Potassium Chloride

The electrolytic deposition and diffusion of lithium onto bulk magnesium-9 wt pct yttrium alloy cathode in molten salt of 47 wt pct lithium chloride and 53 wt pct potassium chloride at 693 K were investigated. Results show that magnesium-yttrium-lithium ternary alloys are formed on the surface of the cathodes, and a penetration depth of 642 μm is acquired after 2 hours of electrolysis at the cathodic current density of 0.06 A·cm⁻². The diffusion of lithium results in a great amount of precipitates in the lithium containing layer. These precipitates are the compound of Mg₄₁Y₅, which arrange along the grain boundaries and hinder the diffusion of lithium, and solid solution of yttrium in magnesium. The grain boundaries and the twins of the magnesium-9 wt pct yttrium substrate also have negative effects on the diffusion of lithium.     

Zinc phosphating of 6061-Al alloy using REN as additive

Zinc phosphate coating formed on 6061-A1 alloy was studied with the help of electrochemical measurements, Fourier Transform Infrared （FTIR）, and Scanning Electron Microscopy （SEM）, after dipping it in phosphating solutions containing different concentrations of Rare Earth Nitrate （REN）. REN, which acted as an accelerator in the phosphating solution, could catalyze the surface reaction and accelerate the phosphating process. REN mainly enabled the P in the phosphate coating to exist in the form of PO4^3- and promoted the hydrolysis of phosphatic acid in a liquid layer at the cathodes. This resulted in the evolution of H2 at the cathodes, which increased the local pH value and in turn drove the precipitation of the phosphate coating. Additionally, REN was adsorbed on the surface of the aluminum substrates to form a gel during the phosphating process. These gel particles were good crystal seeds, which helped to form phosphate crystal nuclei and possess the function of a nucleation agent that could decrease the phosphate crystal size. The corrosion resistance of the formed zinc phosphate coatings was improved.     

Zinc phosphating of 6061-Al alloy using REN as additive

Zinc phosphate coating formed on 6061-Al alloy was studied with the help of electrochemical measurements, Fourier Transform Infrared (FTIR), and Scanning Electron Microscopy (SEM), after dipping it in phosphating solutions containing different concentrations of Rare Earth Nitrate (REN). REN, which acted as an accelerator in the phosphating solution, could catalyze the surface reaction and accelerate the phosphating process. REN mainly enabled the P in the phosphate coating to exist in the form of PO43- and promoted the hydrolysis of phosphatic acid in a liquid layer at the cathodes. This resulted in the evolution of H2 at the cathodes, which increased the local pH value and in turn drove the precipitation of the phosphate coating. Additionally, REN was adsorbed on the surface of the aluminum substrates to form a gel during the phosphating process. These gel particles were good crystal seeds, which helped to form phosphate crystal nuclei and possess the function of a nucleation agent that could decrease the phosphate crystal size. The corrosion resistance of the formed zinc phosphate coatings was improved.     

Analysis of Nugget Formation During Resistance Spot Welding on Dissimilar Metal Sheets of Aluminum and Magnesium Alloys

The nugget formation of resistance spot welding (RSW) on dissimilar material sheets of aluminum and magnesium alloys was studied, and the element distribution, microstructure, and microhardness distribution near the joint interface were analyzed. It was found that the staggered high regions at the contact interface of aluminum and magnesium alloy sheets, where the dissimilar metal melted together, tended to be the preferred nucleation regions of nugget. The main technical problem of RSW on dissimilar metal sheets of aluminum and magnesium alloys was the brittle-hard Al₁₂Mg₁₇ intermetallic compounds distributed in the nugget, with hardness much higher than either side of the base materials. Microcracks tended to generate at the interface of the nugget and base materials, which affected weld quality and strength.     

硼和稀土对铝阴极板耐腐蚀性能的影响

通过添加适量B和稀土元素制备6种成分的铝合金阴极板材料.采用模拟工业环境浸泡腐蚀实验、电化学阻抗谱实验等方法探究实验合金的耐腐蚀性能.结果表明,同时添加B和稀土元素能有效降低铝合金中铁杂质含量,合金中的含铁相由针片状转变为细小颗粒状;这种铝合金阴极板材料在模拟工业环境浸泡减重实验中减重最缓慢,电化学阻抗谱拟合结果中阻抗弧半径最大,具有较好的耐腐蚀性能.      

电解质过热度对铝电解槽物理场的影响

电解质的过热度与铝电解槽槽膛内形的形成有很大的关系，而且对铝电解槽的物理场也有很重要的影响。为此，以国内最具代表性的郑州龙祥铝业有限公司154kA侧部四点进电铝电解槽为研究对象，具体分析了电解质过热度对铝电解槽电场、磁场和流场的影响，研究发现电解质过热度对阴、阳极电流分布、铝液层电位差、铝液平均磁感应强度几乎无影响；但是随着电解质过热度的增加，铝液层电流密度减小，而铝液最大流谏和平均流速将有所增大。