三元络合碱性电沉积锌镍合金的抗腐蚀性能研究

采用四乙烯五胺(TEPA)、酒石酸钾钠和三乙醇胺(TEA)三元混合物作为镍离子络合剂配制碱性锌镍合金镀液,在低碳钢基材上电沉积制备锌镍合金镀层。利用电化学工作站测试了镀层在3.5%NaCl溶液中的极化曲线和电化学阻抗谱,考察不同电沉积条件参数(电流密度和镍离子相对含量)对锌镍合金镀层的腐蚀电化学行为的影响。结果表明:当镀液的镍含量在较宽范围内(n(Ni 2+)/n(Ni 2++Zn2+)=15%～30%)变化时,所得镀层对基体都有很好的防护作用;当电流密度为2～3A/dm2时得到的镀层抗腐蚀能力最强,而当电流密度过低和过高时都会使镀层的耐蚀性有所降低。     

碱性体系电镀锌镍合金工艺中配位剂对镀层的影响

锌镍合金是目前最理想的代镉镀层,而碱性锌镍合金电镀体系则以其分散能力强、成本低等优点受到关注.以三乙醇胺或三乙烯四胺作为配位剂研究了锌镍合金的碱性电镀工艺,采用赫尔槽试验、重量及分光光度测定等方法讨论了镀液组成、配位剂添加量、电流密度、温度等因素对镀层外观及镀层镍含量的影响.结果表明:镀液中[Ni2 ]/[Zn2 ]浓度比、配位剂用量等对镀液稳定性、镀层质量及镍含量有较大的影响;在较宽的电流密度范围内获得光亮耐蚀合金镀层的最优工艺参数为[Ni2 ]/[Zn2 ]浓度比0.29,三乙醇胺或三乙烯四胺的最佳添加量50 mL/L(或30 mL/L),镀液温度30～60 ℃;锌镍合金镀层在5%NaCl溶液中的腐蚀行为表明,含镍量为13%的锌镍合金镀层的耐蚀性明显优于纯锌镀层.     

碱性锌镍合金电镀中NiSO_4·6H_2O浓度对镀层的影响

过去,就碱性锌镍合金电镀液中镍离子含量对镀层镍含量、形貌及耐蚀性的影响研究不够。考察了镀液中NiSO4.6H2O浓度对碱性锌镍合金镀层质量的影响,利用扫描电镜(SEM)、能谱仪和塔菲尔曲线分析了镀层的镍含量、形貌和性能。结果表明:锌镍合金镀层中镍含量随镀液中NiSO4.6H2O浓度的增加而增大,当NiSO4.6H2O低于8 g/L时,镀层镍含量低,晶粒粗大,不光亮;高于8 g/L时镀层镍含量较高,晶粒粗大、出现瘤状物,镀层会出现开裂现象;浓度为8 g/L时效果最好,镀层镍含量为12.56%,镀层平整、致密、光亮,具有良好的耐蚀性能。     

以三乙醇胺为辅助配位剂碱性电沉积锌镍合金的电化学行为

碱性镀液中镍离子的配位剂对镀层影响很大,目前对其多种配位剂共同使用的研究较少。研究了以四乙烯五胺为镍离子的主配位剂,三乙醇胺(TEA)为镍离子辅助配位剂的锌镍合金碱性电沉积体系,在不同三乙醇胺含量和电流密度下在Q235低碳钢表面电沉积锌镍合金的电化学过程。结果表明:随着镀液中三乙醇胺含量增加,电流效率和沉积速率下降,溶液电阻、电荷传递电阻和电感先增加后降低,在n(TEA)∶n(Ni2+)=2.0时阴极极化最大;增加阴极电流密度使镀液的沉积电位变负,阴极极化增大,同时使电荷传递电阻和电感变小;该碱性电沉积锌镍合金的过程受电化学步骤和扩散步骤混合控制。     

光度法测定锌镍合金镀液中的锌镍离子含量

1　前　言研究表明 ,锌镍合金的耐蚀性与镀层含镍量有关 ,镀液中锌镍含量的变化显著影响镀层的含镍量。为了控制镀层含镍量 ,就要保持镀液中锌镍含量的稳定 ,从而必须快速、准确地测定镀液中锌镍含量。本实验采用光度法与滴定法相结合 ,很好地解决了这一问题。实验中用ＥＤＴＡ作为络合剂 ,Ｚｎ2 + 、ＥＤＴＡ及ＺｎＹ2 -在可见光区均无吸收 ,ＮｉＹ2 -、Ｎｉ2 + 的最大吸收波长分别为 60 0、680ｎｍ ,在 60 0ｎｍ处可以直接通过比色法测得镍含量。实验中先将Ｚｎ2 + 、Ｎｉ2 + 完全络合 ,并保持ＥＤＴＡ过量 ,由于在 60 0ｎｍ处 ,ＮｉＹ2 -…     

新型碱性锌镍合金电镀工艺

正0前言在恶劣的工况条件下,汽车、船舶、机械、电子等设备的镀锌层已不能满足高耐蚀性能的要求,锌镍合金镀层作为锌系合金层具有优异的综合性能,其应用范围也越来越广。锌镍合金镀层可从多种溶液中获取,对于非铸铁件,碱性锌酸盐体系是首选。在强碱性溶液中,适当的配位剂可以使镍离子稳定存在,并参与电极反应,从而得到镍含量相对稳定的锌镍合金镀层。但是,现有的锌镍合金电镀工艺存在镀层镍含量稳定性差、钝化处理难度大、添加剂种类过多、镀液维护难     

弱酸性无铵锌镍合金电镀工艺的研究

研究了一种无铵弱酸性锌镍合金电镀工艺,并深入探讨了镀液的成分及工艺条件对镀层含镍量的影响,得到了镀层为γ相Ni5Zn21与δ相Ni3Zn22、且含镍量为13%的全光亮锌镍合金镀层,确定了电镀工艺规范.该镀层具有极好的耐高温性能及优良的耐腐蚀性.     

锌-镍合金溶液（碱性）中锌、镍、氢氧化钠的分析方法

研究表明,锌-镍合金的耐蚀性与镀层含镍量有关,镀液中锌镍含量的变化显著影响镀层的含镍量。为了控制镀层含镍量,就要保持镀液中锌镍含量的稳定,从而,必须快速、准确地测定镀液中锌镍含量。本方法采用光度法与滴定法相结合,很好的解决了这一问题。锌的测定方法,在氨性溶液中,用抗坏血酸还原三价铁离子,再加入氰化物掩蔽Fe^2＋、Zn^2＋、Ni^2＋、Cu^2＋等离子,以铬黑T为指示剂用EDTA进行滴定。氢氧化钠的测定,用中和滴定法完成,以酚酞为指示剂用盐酸滴定。镍是用比色分析法,在碱性溶液中,当有氧化剂存在时,利用镍与丁二酮肟不产生沉淀而形成酒红色可溶性络合物的特性,借此进行比色测定,用酒石酸络合铁等杂质。     

锌镍合金电镀工艺研究

通过正交试验方法,采用新的添加剂和配位剂实现了锌镍合金电镀,优选出了新的锌镍合金电沉积工艺和镀液配方.通过GDA-750型辉光放电光谱仪、HitachiS-570型扫描电镜等分析手段,研究了不同电镀工艺参数对镀层中镍含量、镀层厚度和镀层外观的影响规律.采用了电化学试验法研究了镍含量变化对镀层的耐腐蚀性的影响.结果表明:通过此新型的镀液配方和工艺条件,可获得含镍9%～13%、具有良好外观和耐蚀性好的锌镍合金镀层.随着电流密度的增加,镀层中镍含量先减小后增加;随着温度和pH值的增加,镀层中镍含量在不断增加;镀层的自腐蚀电位随着镍含量的增加,呈现先变正后变负的趋势,镍的含量为12%～13%时,合金的自腐蚀电位最正.     

有机多膦酸盐电镀锌镍合金的研究

研究了用有机多膦酸盐（HEDP）作络合剂,ZNP作添加剂电镀光亮锌镍合金,探讨了络合剂、氯化物含量、[Zn^2＋]/[Ni^2＋]比、阳极电流密度、温度、辅助络合剂对合金中镍含量的影响,测定了合金镀层中物相组成及镀液稳定性,通过筛选得出最佳最镀光亮锌镍合金的镀液组成及工艺条件,并讨论了锌镍合金的异常共沉积机理。     

改性沸石对电镀废水中Pb2+、Zn2+、Ni2+的吸附

将天然沸石进行处理制备出多孔质改性沸石颗粒。在静态条件下，研究了改性沸石颗粒对重金属离子Pb^2 ,Zn^2 ,Ni^2 的吸附效果及条件，含Pb^2 ,Zn^2 ,Ni^2 的电镀废水经改性沸石颗粒吸附后，废水中Pb^2 ,Zn^2 ,Ni^2 的含量低于国家排放标准。     

ESR of Cu2+and Tl2+ in thallium borate glasses

The electron spin resonance (ESR) and optical absorption spectra of Cu²⁺ were measured in thallium borate glasses in order to investigate the effects of glass transition temperature,T _g, upon the responses of cupric ion in alkali borate glasses. The ESR of Tl²⁺ induced by-ray irradiation was also obtained. An abrupt increase in the covalency of in-plane Cu²⁺-O-bonding was observed in the Tl₂O system as well as in the Na₂O system in a similar B₂O₃ composition range althoughT _g for the Tl₂O glasses has little dependency on the composition compared with the Na₂O glasses. The trend in the variation of the S-character of the Tl²⁺ unpaired electron with composition agreed with that of the covalency of in-plane Cu²⁺-O-bonding. The structure of the anion group present in Tl₂O glasses was also examined by laser reman spectroscopy.     

胶团强化超滤中SDS胶团对Cd^2＋，Zn^2＋和Pb^2＋的竞争吸附

胶团强化超滤法是一种将表面活性剂技术和超滤技术结合的新型、高效的重金属废水治理方法.以十二烷基硫酸钠(SDS)为表面活性剂,对含单一镉、锌、铅溶质以及混合溶质体系进行了胶团强化超滤研究,考察了胶团对Cd2 ,Zn2 ,Pb2 的竞争吸附性能.研究发现,当溶液中多种二价重金属离子存在时,各离子之间存在与SDS胶团的竞争吸附,竞争能力为Pb2 ＞Zn2 ＞Cd2 ;Cd-Zn有明显的协同吸附效应,而Cd-Pb,Zn-Pb则表现为拮抗吸附.     

NpO 2 + -UO 2 2+ cation-cation interaction in NaCl-KCl-CsCl and LiCl-KCl-CsCl eutectic melts

Absorption spectra of the NpO ₂ ⁺ ion in UO ₂ ²⁺ -containing NaCl-KCl-CsCl (0.300:0.245:0.455) and LiCl-KCl-CsCl (0.575:0.165:0.260) eutectic melts in the region of the 5f-5f transitions, 700–2000 nm, were studied at 650 and 500°C, respectively. Processing of the spectra allowed the previously discovered phenomenon, cation-cation interaction of actinides in melts, to be interpreted for the first time in terms of the mass action law. It was shown that, at the concentrations of the interacting components studied (C _Np = 0.2 M and C _U = 0.1–2 M), a 1: 1 NpO ₂ ⁺ ·UO ₂ ²⁺ cation-cation complex is formed. Its concentration stability constant was estimated at 0.06(6) and 0.11 1 mol^?1 for the NaCl-KCl-CsCl and LiCl-KCl-CsCl systems, respectively.     

Phase Composition of the Products of Fe Oxidation in Fe + C + NaCl + H2O + O2 Exothermic Mixtures

Using thermodynamic analysis of the Fe–C–NaCl–H₂O–O₂ system and experimental studies (x-ray diffraction and Mössbauer spectroscopy) of exothermic mixtures containing Fe metal, activated carbon, water, and NaCl, we identified the state of Fe and determined the phase composition of the reaction products at different stages of oxidation with atmospheric oxygen. The calculation and experimental results are in reasonable agreement. Under the conditions of restricted access for air, the main oxidation product is magnetite, Fe₃O₄. Free access for air leads to the formation of hydrous ferric oxide, Fe₂O₃ · nH₂O. The most stable phase under the conditions of interest is goethite, Fe₂O₃ · H₂O (-FeOOH). Storage of incompletely oxidized samples away from air for 7–14 days leads to partial reduction of iron(III) oxide phases to Fe₃O₄ and -Fe.     

钠基膨润土对废水中Ni2+,Cu2+的吸附效果

为了提高膨润土吸附废水中Ni2+,Cu2+的效果,对其改性制备了钠基膨润土,考察了吸附时间、废水pH值以及Ni2+和Cu2+初始浓度对自制钠基膨润土吸附Ni2+,Cu2+效果的影响,分析了吸附等温线,并探讨了吸附机理。结果表明:钠基膨润土对Ni2+,Cu2+都有较好的吸附性能;初始阶段(前10 min)吸附很快,之后随时间延长吸附量提高甚微;pH值为6.2时,处理后的水质即可达国家排放标准;随着Ni2+,Cu2+初始浓度增加,去除率先增加后降低,而吸附量迅速增加,Ni2+和Cu2+初始浓度分别为25 mg/L和40 mg/L时,钠基膨润土对Ni2+,Cu2+的去除率均可达98.6%;钠基膨润土对Ni2+,Cu2+的吸附等温线符合Freundlich吸附等温式。     

Characterization of various Eu2+ sites in Ca2SiO4:Eu2+ and Ba2SiO4:Eu2+ by high-pressure spectroscopy

Photoluminescence of Ba₂SiO₄ and Ca₂SiO₄ activated with Eu²⁺ was investigated at various temperatures (from 10 K to 300 K) and pressures (from ambient to 200 kbar). At ambient pressure and room temperature, under UV excitation both phosphors yielded a green emission band with maxima at 505 nm and 510 nm for Ba₂SiO₄ and Ca₂SiO₄, respectively. The energies of these bands depended on pressure; the pressure shifts were ?12:55 cm^?1/kbar for Ba₂SiO₄:Eu²⁺; and ?5:59 cm^?1/kbar for Ca₂SiO₄:Eu²⁺. In the case of Ca₂SiO₄:Eu²⁺, we observed additional broadband emission at lower energies with a maximum at 610 nm (orange band). The orange and green emission in Ca₂SiO₄:Eu²⁺ had different excitation spectra: the green band could be excited at wavelengths shorter than 470 nm, whereas the orange band — at wavelengths shorter than 520 nm. The pressure caused a red shift of orange emission of 7.83 cm^?1/kbar. The emission peaked at 510 nm was attributed to the 4f⁶5d→4f⁷(⁸S₇₌₂) transition of Eu²⁺ in the β — Ca₂SiO₄:Eu²⁺ phase, whereas the emission peaked at 610 nm — to the γ — Ca₂SiO₄:Eu²⁺ phase. The emission of Ba₂SiO₄:Eu²⁺ peaked at 505 nm was attributed to the 4f⁶5d→ 4f⁷(⁸S_7/2) transition of Eu²⁺ in the β — Ba₂SiO₄ phase.     

Electron paramagnetic resonance of Cu2+ and VO2+ ions in phosphate glasses

Electron spin resonance (ESR) spectra ofx(CuO · V₂O₅ (1 –x) (Na₂O · P₂O₅) andx(CuO · 2V₂O₅) (1 –x) (Na₂O · P₂O₅) glasses for 0 x 40 have been studied at the X-band and at 300 K. It is found that forx 5, both Cu²⁺ and VO²⁺ are present, mostly as isolated species. Forx 10, broad resonance lines atg = 2.1524 forx(CuO · V₂O₅) (1 –x) (Na₂O · P₂O₅) and atg = 2.1448 forx(CuO · 2V₂O₅) (1 –x) (Na₂O · P₂O₅) are observed which may be mainly due to dipole-dipole type interaction between transition metal (TM) ions. Spin Hamiltonian parameters of TM ions have been calculated. Optical spectra of the sodium phosphate glasses doped with single TM ions have also been studied. The theoretical optical basicity, A_th, of these doped glasses has been calculated. It is found that for VO²⁺ ionsg ,g and increase whileA ,P and g _|/g decrease with increase in A_th. However, no significant change is observed in the spin Hamiltonian parameters of Cu²⁺ with the change in A_th.     

First Observation of the Cation-Cation Interaction of Actinides in Melts: NpO2 +-UO2 2+ System

Study of the absorption spectra of the NpO ₂ ⁺ ion in a CsCl melt containing 2 M UO ₂ ²⁺ , as well as in K₂UO₂Cl₄ and Cs₂UO₂Cl₄ melts (T = 700°C), allowed the first detection of the cation-cation interaction of actinides in melts. In all the molten salts studied, the cation-cation interaction of NpO ₂ ⁺ and UO ₂ ²⁺ is manifested most clearly (via appearance of an additional band) in the ³ H ₅ ³ H ₄ magnetic-dipole transition of the 5f ² configuration of the NpO₂ ⁺ ion (D _4h symmetry) near 1.6 m: Along with a sharp peak of unbound neptunyl(V) at 1660 nm, there is an equally sharp peak at 1633 nm belonging to the cation-cation complex. The intensity ratio for the peaks at 1633 and 1660 nm increases in the series of melts (UO ₂ ²⁺ in CsCl) < K₂UO₂Cl₄ < Cs₂UO₂Cl₄ by two orders of magnitude.