Electrodeposition of Co–Cu alloy coatings from glycinate baths

The cathodic polarization, cathodic current efficiency of codeposition, composition and structure of Co–Cu alloy as a function of bath composition, current density and temperature were studied. Electrodeposition was carried out from solutions containing CuSO₄ · 5H₂O, CoSO₄ · 7H₂O, Na₂SO₄ and NH₂CH₂COOH. The cathodic current efficiency of codeposition (CCE) was high and it increased with increasing temperature and Cu²⁺ content in the bath, but it decreased with current density. The codeposition of Co–Cu alloys from these baths can be classified as regular. The Co content of the deposit increased with Co²⁺ content and current density and decreased with glycine concentration and temperature. The structure of the deposited alloys was characterized by anodic stripping and X-ray diffraction techniques. The data showed that the deposited alloys consisted of a single solid solution phase with a face-centred cubic (f.c.c.) structure.     

硫酸盐-柠檬酸盐体系锌锰合金电镀液稳定性的研究

锌锰合金镀液存在电流效率低,镀液稳定性差等缺点,选择硫酸盐－柠檬酸盐体系锌锰合金镀液,研究了阳极,二价锰离子以及连续作用等因素对镀液稳定性的影响,结果表明：采用不锈钢阳极和阴离子膜可提高镀液稳定性,防止二价被氧化,加入氢氧化可消除因补充锌锰离子而积累的硫酸根离子。     

Hydrothermal synthesis (200 °C) of Co–kaolinite and Al–Co–serpentine

In the systems CoO–Al₂O₃–SiO₂–H₂O and CoO–Al₂O₃–SiO₂–HCl–H₂O, at initial pH between 5.5 and 8.1 and temperature of 200 °C, kaolinite is unstable and the following phases form through a dissolution-precipitation process: a) kaolinite and Co-bearing kaolinite; b) Al–Co–serpentine; and c) poorly crystalline phases. Identification of the several phases was carried out from a combination of X-ray diffraction and transmission/analytical electron microscopy.Co–kaolinite shows variable morphologies: a) Platy lath-shaped particles with very low Co content; b) Spherical particles, with relatively constant Co contents (in the order of 0.10 apfu); c) Kaolinite stacks with very variable Co contents (up to 0.25 apfu). Analytical data indicate that the presence of Co(OH)₂ in the system favors the dissolution process as well as serpentine formation but it leads to the parallel formation of abundant poorly crystalline phases. The Co-content in kaolinite increased as a function of the Co(OH)₂/CoCl₂ ratio in the initial systems, and it is reflected by a parallel increase of the b-cell parameter of kaolinite. The average composition of the coexisting Al–Co–serpentine is: (Al_1.20Fe_0.11Co_1.27)(Si_1.64Al_0.36)O₅(OH,Cl)₂, with Cl contents in the order of 0.14 apfu.The assemblage Co–kaolinite + Al–Co–serpentine, which appears to be stable at 200 °C, has not been described in natural environments, probably because it requires unusual Al- and Co-rich chemical systems.     

Effects of boric acid on hydrogen evolution and internal stress in films deposited from a nickel sulfamate bath

The effects of boric acid additions on the pH close to the electrode surface, on the hydrogen evolution reaction and on the internal stress in the plated films were studied for the high speed electroplating of nickel from a nickel sulfamate bath at a current density close to the nickel ion limiting current density. The study was carried out at 50 °C and pH 4.0 using a 1.55 M nickel sulfamate plating bath containing boric acid at concentrations ranging from 0 to 0.81 mol L^–1. The variation of the internal strain in the plated nickel films was determined in situ using a resistance wire-type strain gauge fitted to the reverse side of the copper electrode substrate. The solution pH at a distance of 0.1 mm from the depositing nickel film was measured in situ using a miniature pH sensor assembly consisting of a thin wire-type antimony electrode and a Ag/AgCl/sat. KCl electrode housed in a thin Luggin capillary. The addition of boric acid was shown to effectively suppress the hydrogen evolution reaction at nickel electrodeposition rates (18.0 A dm^–2) close to the limiting current density (~20 A dm^–2). Consequently, the solution pH adjacent to the plating metal surface was maintained at a value close to that in the bulk solution and the development of high internal stresses in the deposited nickel films was avoided.     

Effect of diethanolamine and triethanolamine on the properties of electroplated Zn–Ni alloy coatings from acid bath

In the present work, zinc–nickel alloy coatings have been produced under direct current conditions from an acid bath with different concentrations of diethanolamine (DEA) and triethanolamine (TEA). The produced coatings were analysed through chronopotentiometry, microhardness, X‐ray diffraction and MEB techniques. The compositional analysis of the films showed that the Zn–Ni electrodeposition is anomalous for all the systems. Ethanolamines augmented the anomalous behaviour. The hindering in the Ni (II) reduction will be more effective due to complexation of Ni (II) catalyst with ethanolamines. Electrochemical and structure analysis of deposits indicated the presence of γ and highly Zn‐enriched phases. The presence of these additives resulted also in coatings with finer grains. The behaviour of modified Zn–Ni alloy coatings in corrosion solution of 3% NaCl was investigated through potentiodynamic polarisation and electrochemical impedance spectroscopy. It was found that the obtained Zn–Ni/3 mM TEA alloy exhibited better corrosion resistance compared to pure Zn–Ni alloy electrodeposited at similar conditions. © 2012 Canadian Society for Chemical Engineering     

含铵盐的硫酸盐三价铬镀铬液中硼酸的测定

制定了测定含铵盐的硫酸盐三价铬镀铬液中硼酸的方法。用柠檬酸钠掩蔽三价铬离子和镍杂质,用甘露醇与硼酸反应生成较强的配合酸。以变色pH范围为6.8～8.4的酚红作为指示剂,用氢氧化钠标准溶液滴定配合酸,避免了硫酸铵对测定硼酸的影响。测定结果的相对平均偏差为0.28%,回收率为99.34%～100.46%。     

硼酸凝固浴对MF-PVA纤维结构与性能的影响

以三聚氰胺(M)、甲醛(F)、聚乙烯醇(PVA)水溶液为原料反应制得纺丝原液,经湿法纺丝得到三聚氰胺甲醛-聚乙烯醇(MF-PVA)纤维。研究了在凝固浴中加入硼酸对MF-PVA纤维结构及性能的影响。采用凯氏定氮法、扫描电子显微镜、单纤电子强力仪和极限氧指数(LOI)仪表征了纺丝过程氮流失率、纤维形貌结构、力学性能以及阻燃性能。结果表明:在凝固浴中加入硼酸可以有效地控制MF树脂的溶出,随着硼酸添加量的增加,纤维的氮流失率明显降低,断裂强度增加,断裂伸长率减小,LOI提高。当添加硼酸的质量分数为7%时,纤维的氮流失率只有14.64%,其LOI达到40%,但纤维表面变得粗糙。     

Glucose hydrogenation on Co–B amorphous alloy catalysts and the promoting effect of metal additives

Two kinds of ultrafine Co–B amorphous alloy catalysts, denoted as P‐1 Co–B and P‐2W Co–B, were prepared by chemical reduction with borohydride in aqueous or 50% (v/v) ethanol/water solution, respectively. In comparison with the corresponding Co‐based crystalline catalysts and Ni‐based catalysts, these catalysts exhibited higher activity during the liquid phase glucose hydrogenation, possibly due to the unique amorphous characteristics and the lower d‐band electron density, which was favorable for hydrogen dissociative chemisorption. Addition of Cr‐, Mo‐ or W‐promoters could further increase the conversion of Co–B amorphous catalyst, which was mainly attributed to the dispersion effect of promoters and the adsorption and polarization of carbonyl groups by these promoters. The different effects of W‐ from Cr‐ and Mo‐promoters on the conversion were observed and are discussed. © 2001 Society of Chemical Industry     

采用钠硼解石生产硼酸的工艺研究

由青海大柴旦钠硼解石矿中提取硼酸，找出了最佳工艺条件，即：矿粒细度〈1．7mm，反应温度80～90℃，反应液酸度（pH）2～3，结晶温度20～25℃，反应液中硼酸质量分数15％～16％，蒸发过程镁离子质量分数〈4％，渣带失（以三氧化二硼计）质量分数〈2％。在此条件下对其工艺技术的稳定性、可靠性及适应性进行了研究。结果表明，硼的总收率达85％以上，利用本地资源生产硼酸，投资少，见效快。     

光亮镀镍液中硼酸和氯化镍的连续滴定

介绍一种光亮镀镍液中硼酸和氯化镍的测定方法。采用732型阳离子交换树脂分离镍及其它阳离子后,分别用氢氧化钠和硼酸银滴定硼酸和氯离子,分析结果表明,本方法简便快速、准确度高。     

The elastic property of polyvinyl alcohol gel with boric acid as a crosslinking agent

The elastomers of polyvinyl alcohol gel were made from the polyvinyl alcohol polymer, with boric acid added as a crosslinking agent, in the mixed solvent of dimethyl sulfoxide and water. From the experimental results, the viscosity of polyvinyl alcohol solution is found to increase not only with an increment of boric acid content, but also with the temperature in the range of 70°C ∼ 100°C, although the viscosity is decreased in the range of 30°C ∼ 70°C. Moreover, the molecular mass between junctions of polyvinyl alcohol gel is calculated from the rubber elastic theory and found to be decreased with the increment of boric acid content. We also evaluated the values of Young's modulus of polyvinyl alcohol gel, E, E*, and the elastic parameters C₁ and C₂ of the Mooney‐Rivlin equation, according to Hook's law and theory of rubber elasticity. Based on these, the polyvinyl alcohol gel behaves as a good rubberlike elastic property. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3046–3052, 1999     

Investigation of Co–B–S system as anode material for secondary alkaline battery

A series of novel Co–S–B systems were prepared by simple chemical reduction method as the anode material for secondary alkaline batteries. The prepared samples were investigated by inductivity coupled plasma optical emission spectrum (ICP), Brunauer–Emmetr–Teller (BET) method, scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray energy dispersive spectroscopy (EDS) and charge–discharge method. It was found that the BET surface area of Co–S–B system increases and its particle size decreases with increasing the sulfur content. Sulfur incorporation suppresses initial capacity fading of Co–B compound due to irreversible dissolution of boron, and Co–S–B electrodes show enhanced electrochemical capacity and excellent cycle performance. The discharge capacity of Co_75.4B₁₇S_7.6 reaches 513.6 mAh/g at a moderate current density of 100 mA/g and 470 mAh/g after 60 cycles, which is about 1.5 times that of conventional AB₅-type alloy. A proper mechanism was proposed to explain the electrochemical reaction process of Co–S–B electrode.     

W-promoted Co–Mo–K/γ–Al2O3 catalysts for water–gas shift reaction

The effects of incorporating tungsten into the traditional Co–Mo–K/γ–Al₂O₃ catalysts on the catalytic performances for water–gas shift reaction were investigated. Activity tests showed that W-promoted Co–Mo–K/γ–Al₂O₃ catalysts exhibited higher activity than W-free Co–Mo–K/γ–Al₂O₃ catalyst. Raman and H₂-TPR studies indicated that part of the octahedrally coordinated Mo–O species on Co–Mo–K catalysts transformed into tetrahedrally coordinated Mo–O species in the presence of W promoter.     

离子交换法从卤水中提取硼酸

中国很多的盐湖卤水中都富含大量的硼矿资源，从中提取硼酸的方法也有很多，如：酸化结晶法、沉淀法、萃取法、离子交换法等，其中离子交换法被认为是这些方法中最有前途的方法之一。综述了采用离子交换法从含硼盐湖卤水中提取硼酸的工艺原理和影响因素，列出了几种常用的提硼树脂，介绍了应用离子交换法从卤水中提取硼酸的现状。     

Properties and microstructure of nickel electrodeposited from a sulfamate bath containing ammonium ions

A 70 m thick Ni layer was electrodeposited from a sulfamate bath containing various amounts of ammonium ions onto a copper plate. The detailed microstructure of the Ni deposits was characterized using a plane-view and cross-sectional transmission electron microscopy (TEM). The textures of the Ni deposits were also determined using conventional X-ray diffraction. Experimental results indicated that ammonium ions suppressed the lateral growth of Ni deposits and favoured out growth, thus leading to the growth of [1 1 0] and [3 1 0] oriented deposits. A structural refinement effect was observed after ammonium ions were added to the sulfamate bath. Ammonium ions also increased the internal stress and hardness of the deposits. A general Hall–Petch relationship was observed for the dependence of deposit hardness on the average grain size of the Ni deposits. The adsorption of atomic hydrogen and the polar NH₃ molecule explains the effect of ammonium ions on the electrocrystallization of Ni.     

Ultrafine Amorphous Co–Fe–B Catalysts for the Hydrolysis of NaBH4 Solution to Generate Hydrogen for PEMFC

For hydrogen generation from alkaline sodium borohydride (NaBH₄) solution, Co–Fe–B catalysts with different Co/(Co + Fe) molar ratios (χ_Co) were prepared by the chemical reduction of CoCl₂ and FeCl₃ ethanol solution with KBH₄ solution. The X‐ray diffraction (XRD) and scanning electron microscopy (SEM) analyses revealed that the as‐prepared Co–Fe–B catalysts were in amorphous form and ultrafine. The hydrogen generation measurements showed that as‐prepared Co–B and Co–Fe–B catalysts exhibited excellent catalytic activity. Co–Fe–B with the Co/(Co + Fe) molar ratio (χ_Co) of 0.85 was the best. Its maximum hydrogen generation rate at 298 K was 4,310 mL min^–1 g^–1, while the Co–B was 2,773 mL min^–1 g^–1. The enhanced activity could be attributed to large active surface area, electron transfer from B and Fe to active Co sites, and improvement in the dispersion of Co–B with Fe₂O₃. The activation energy of Co–Fe–B catalyst with the molar ratio χ_Co = 0.85 was decreased to 29.09 kJ mol^–1 as compared to 30.85 kJ mol^–1 obtained with Co–B.     

大柴旦柱硼镁石矿酸法制硼酸工艺优化研究

针对大柴旦柱硼镁石矿特点．对酸法制硼酸进行了工艺优化研究。通过试验,缩短了酸化反应时间,提高了反应收率,达到了优化工艺的目的。该工艺已在实际生产中应用。     

从硼镁矿硫酸分解液中分级结晶硼酸和水镁矾

目前在中国用硫酸分解硼镁矿直接制取硼酸（一步法）的B2O3收率不高。对硼酸母液的利用方法主要有将硼酸母液蒸浓后冷却制硼镁肥；蒸浓冷却至室温再用浮选法或重选法进行分离；加入MgCl2做盐析剂等方案，但都存在一定的问题。经分析25，100℃H3BO3-MgSO4-H2O体系相图，确定了从硼镁矿的硫酸分解液中分级结晶硼酸和水镁矾的生产工艺，并指出可以采用冷却式Oslo结晶器结晶硼酸以获得大粒晶体；用蒸发式Oslo结晶器结晶可以获得大粒水镁矾晶体，并可确保水镁矾离心机安全运转.     

西藏硼镁矿制取硼酸联产碳酸镁工艺研究

提出了西藏硼镁矿综合利用的新工艺,即用硫酸铵复分解法分解西藏硼镁矿制取硼酸和碳酸镁。考察了反应温度、反应时间、硫酸铵的初始浓度、硫酸铵的用量比等工艺条件对硼浸出率的影响。较佳工艺条件为：反应温度100 ℃、反应时间2~2.5 h、硫酸铵的初始浓度为9%~11%（质量分数）、硫酸铵的用量为理论量的110%。在此工艺条件下,硼酸的收率可达95%,碳酸镁的收率可达90%以上。该工艺充分利用了西藏硼镁矿的硼、镁资源,提高了硼的收率。     

Voltammetric and morphological characterization of zinc electrodeposition from acid electrolytes containing boric–polyalcohol complexes

The influence of sorbitol or glycerol polyalcohols on the electrodeposition of zinc and on morphology of the zinc film is discussed. The deposition current efficiency, in the potential range −1.30 V to −2.50 V, was ∼90% in all baths. Increasing the sorbitol concentration in the bath shifted the deposition to more negative potentials, ∼50 mV, and decreased the current density (j _p ) of the zinc deposition significantly. On the other hand, adding glycerol did not significantly affect either j or the deposition potential of zinc. Scanning electron microscopy (SEM) showed that either sorbitol or glycerol lead to the formation of granular deposits. The best zinc morphology was obtained with 0.52 M sorbitol or glycerol in the plating bath. The presence of sorbitol or glycerol in the plating bath was beneficial, since the resulting zinc deposits were compact and without holes.