Electrolytic Metallic Coatings for Carbon Fibers

This paper concerns electrolytic metallic coatings for carbon fibers and the related processes. Plating bath design, electrolyte selection and other aspects were investigated. Experimental results especially in copper electroplating show that the uniformity of metallic coatings on carbon fibers can be improved by the modification of plating bath and the selection of electrolytes. Thus continuous and uniform metallic coatings can be obtained on carbon fibers, even if the cross section of carbon fibers has irregular shape. Polarization tests on different copper baths was performed. Electrodeposition of other metallic layers such as nickel, cobalt, and copper/tin duplex layer was also introduced. A process of two or more than two plating steps in which different electrolytes may be used for same metal deposition was proposed to expedite the coating procedure     

Kinetics of Ni-Mo electrodeposition from Ni-rich citrate baths

The kinetics of Ni-Mo alloy electrodeposition on steel substrates from an aqueous citrate-ammonia complex baths has been investigated by means of steady-state polarisation measurements in a system with a rotating disc electrode (RDE). Partial current densities for discharge of Ni(II) and Mo(VI) ions and hydrogen evolution as a function of molybdate concentration in the bath, cathode potentials and the rate of mass transport were determined. It has been shown that - under all investigated conditions - Ni-Mo alloy deposition is more favourable than pure nickel and the cathodic process is strongly influenced by the Mo(VI) content in the solution. The Ni(II) electroreduction rate initially increases, as the cathode potential shifts towards more negative values and the concentration of molybdate grows in the solution. However, for the highest examined MoO₄^2 − content, a considerable decrease in the rate of the process is subsequently observed at certain limit potentials, the values of which depend on molybdate concentration and hydrodynamic conditions. This effect, related to the formation of intermediate molybdenum oxides (characterised by very low overvoltage for hydrogen evolution), becomes less pronounced when the RDE rotation speed is increased. Hydrogen evolution is strongly associated with molybdenum deposition. An increase of the molybdate ions concentration in the bath, as well as an increase in the rate of mass transport, leads to an increase in Mo content in deposits and to the reduction of current efficiency. The Ni-Mo coatings electrodeposited from the designed bath (with the current efficiency of about 70%) containing about 30 wt.% Mo, are characterised by a shiny-grey appearance and good adhesion to the steel substrate. They are characterised by column growth and amorphous microstructure with randomly distributed nanocrystallites of the MoNi₄ intermetallic phase.     

Corrosion resistance of multilayer coatings of nanolayered Cr/Ni electrodeposited from Cr(III)-Ni(II) bath

In this study the corrosion resistance of chromium and nickel single layers and multilayer coatings of nanolayered Cr/Ni, electrodeposited from Cr(III)-Ni(II) baths on low carbon steel substrates, has been studied. The coatings were electrodeposited from a bath using pulse current and modulated agitation. The total thickness of single layer and multilayer coatings was fixed at 5 μm and multilayer coatings with different modulation wavelengths and Cr to Ni thickness ratio were electrodeposited. Corrosion behavior of coatings was then studied by using potentiodynamic polarization test and electrochemical impedance spectroscopy in 0.1 M H₂SO₄. The results showed that Cr and Ni single layers had low corrosion resistance due to the presence of surface cracks and pores, respectively. On the other hand, optimized 20 nm Cr/50 nm Ni multilayer deposition significantly improved corrosion resistance.     

Phosphate conversion coatings on steel

A mechanism for the formation of crystalline phosphate conversion coatings on steel is proposed from the results of this investigation. X-ray diffraction results identify the crystal types formed from both Zn and Mn phosphating baths. The effect of process parameters, such as metal surface finish and soluble iron content of the phosphate bath, on crystal size and surface layering are discussed. Differential thermal analysis shows the water of crystallization of the phosphate precipitates to be driven off at about 325° C with corresponding contraction and fracture of the surface crystal. Corrosion data was determined and correlated with the crystal morphology. Scanning electron micrographs were taken of the various crystal systems produced to confirm conclusions drawn from the data collected.     

硫酸盐三价铬镀液中次磷酸钠浓度对不锈钢阳极电化学溶出的抑制作用

为了进一步完善以316不锈钢为阳极的硫酸盐三价铬镀铬新工艺,考察了镀液中次磷酸钠等对316不锈钢阳极电化学溶出的抑制作用.利用Hull槽试验、能量射散谱(EDS)和扫描电子显微镜(SEM)研究了次磷酸钠浓度对镀层外观、组分和表面形貌的影响.结果表明,次磷酸钠可以有效地抑制316不锈钢阳极的电化学溶出:当其浓度为0.02...     

Corrosion behaviour in concrete of three differently galvanized steel bars

The increasing use of galvanized steel reinforcements in concrete structures submitted to aggressive environments induces research into innovative zinc coatings with higher corrosion resistance. In this work, several cylindrical concrete specimens were manufactured with two cements of different alkalinity and reinforced with different hot-dip galvanized bars obtained from the “traditional” Zn–Pb bath and from two “modified baths”: Zn–Ni–Bi and Zn–Ni–Sn–Bi. The corrosion rate and corrosion potential of the bars were monitored during the air curing period and during wet–dry exposure both in tap water and in a 5% sodium chloride solution. The results showed that the coatings obtained from Zn–Ni–Sn–Bi bath have the highest corrosion rates, when the aggressiveness of the concrete matrix is determined mainly by its alkalinity. On the contrary, when the corrosion process is determined mainly by the penetration of chlorides (concrete manufactured with cement having a low alkali content) Zn–Ni–Sn–Bi was attacked only when the chloride concentration at the concrete cover depth reached the threshold of 4.02% (by weight of cement), which is higher than those necessary for the attack of the other coatings studied (1.36% for Zn–Ni–Bi, 1.73% for Zn–Pb).     

Physico-mechanical properties of nickel electrodeposited from nickel acetate–amide baths

Abstract

Electrodeposition of nickel from nickel acetate dissolved separately in formamide (FA), N-methylformamide (NMF), and N,N-dimethylformamide (DMF) was carried out. The effects of current density, temperature, boric acid addition, and basis metal were studied. To obtain satisfactory deposits, higher current densities were required using the NMF bath, while FA and DMF baths gave good results at lower current densities. For all types of bath the optimum temperature range for the production of hard deposits was 50–60°C. A higher concentration of boric acid was required to enhance the buffering action for the FA bath, less for the NMF bath, and least for the DMF bath. The DMF and NMF baths also resulted in nickel deposits of high hardness. Scanning electron microscopy revealed a definite change in microstructure when the copper basis metal was replaced by brass which produced fine grains and thereafter by a copper-deposited copper substrate which produced large grains. Reduced cracking was found in the electrodeposited nickel and refinement in grain size occurred when the amide hydrogen of formamide was respectively replaced by one or two methyl groups.

MST/1011     

Production and characterization of boride layers on AISI D2 tool steel

AISI D2 is the most commonly used cold-work tool steel of its grade. It offers high hardenability, low distortion after quenching, high resistance to softening and good wear resistance. The use of appropriate hard coatings on this steel can further improve its wear resistance. Boronizing is a surface treatment of Boron diffusion into the substrate. In this work boride layers were formed on AISI D2 steel using borax baths containing iron-titanium and aluminium, at 800 °C and 1000 °C during 4 h. The borided treated steel was characterized by optical microscopy, Vickers microhardness, X-ray diffraction (XRD) and glow discharge optical spectroscopy (GDOS) to verify the effect of the bath compositions and treatment temperatures in the layer formation. Depending on the bath composition, Fe₂B or FeB was the predominant phase in the boride layers. The layers exhibited “saw-tooth” morphology at the substrate interface; layer thicknesses varied from 60 to 120 μm, and hardness in the range of 1596-1744 HV were obtained.     

A simple chemical method for preparation of hydroxyapatite coatings on Ti6Al4V substrate

A novel, simple and economical chemical bath method for deposition of calcium hydroxyapatite coating has been developed. The coatings were prepared from EDTA solutions in alkaline media on Ti6Al4V substrates. The method is based on thermal dissociation of the Ca(EDTA)^2- complex at 65–95 °C. Two chemical baths with and without presence of Na⁺ and Cl^- were used for the deposition. The Rutherford back scattering study shows that the coating material from bath which contained sodium and chlorine ions have their presence in the coated material. The bath which has been prepared with potassium substituting sodium and nitrate substituting chlorine produced coatings with better stoichiometry, with Ca/P=1,67. The X-ray analysis revealed that the calcium hydroxyapatite coatings have preferred crystal orientation in the 002 direction. © 2001 Kluwer Academic Publishers     

Effect of polytetrafluoroethylene content on electrochemical anticorrosion behaviors of electroless deposited Ni-P and Ni-P-polytetrafluoroethylene coatings in seawater

The Ni-P and Ni-P-polytetrafluoroethylene (PTFE) coatings with various PTFE contents were electroless deposited on carbon steel and characterized through X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy. The microstructural morphologies of the coatings significantly varied with the PTFE content. As a result, the electrochemical anticorrosion capabilities were seriously decreased with the increase of the PTFE content. The coating with a trace PTFE (PTFE emulsion concentration of 0.2 mL/L in the plating bath) possessed excellent anticorrosion both in sterilized and unsterilized seawater which has been attributed to the absence of nano pores blocked by the incorporated trace PTFE nano particles.     

Morphological and structural characterisation of electrodeposited Zn–Mn alloys from acidic chloride bath

Zn–Mn coatings were electrodeposited on steel substrate from an acidic chloride bath containing a commercial additive used in zinc plating. The effects of deposition parameters such as stirring, applied current density or potential and temperature on the coating composition, microstructure and crystallography were investigated. It was found that this additive permits to obtain dense, compact and thick Zn–Mn coatings. The morphology is quite particular, displaying hexagonal pyramids whatever the manganese content of the coating. This morphology is associated with the main phase found in the coatings that is the HCP -Zn–Mn. The manganese content reaches a maximum value of 20 wt.% corresponding to a monophasic coating. Stirring of the solution has no influence on the composition of the coatings but induces essentially an improvement of the surface appearance as brightness increases and roughness decreases. The increase of the temperature also leads to an enhancement of the surface appearance but induces a decrease of the manganese content.     

Analysis of coating layer formedon steel strips during aluminising by hot dipping in Al-Si baths

Abstract

Aluminising of low carbon (0.19 wt-%C) steel was carried out using AI-0, 4, 8, and 12 wt-%Si melts. Different dipping times and melt superheat were used. In all cases, a coating layer was formed which is composed of an intermetallic layer and an aluminium top coat layer. The thickness of the intermetallic layer increased with bath temperature, especially in pure aluminium baths, and decreased with increasing silicon content. Addition of more than 8 wt-%Si to the bath had no detectable effect on the thickness. This thickness X increased with time following the parabolic relationship X =KTⁿ, where the growth rate constant K decreased with silicon content. Energy dispersive X-ray analysis revealed that the intermetallic layer is composed of a thick layer of AI₅Fe₂ followed by a much thinner one of Al₃Fe on the aluminium side. In the case of a silicon containing bath, different Al_xFe_ySi_z compounds were identified. The kinetics of the reaction between solid steel and liquid aluminium were studied. In AI-Si baths, the growth rate of the intermetallic layer was lower and its dissolution rate higher compared with a pure aluminium bath. Separation of parts of the layer was also found. Iron loss from the steel strip, especially in the case of AI-Si baths, was partly used in the formation of both the measured and the dissolved layer and partly dissolved in the melt. The growth rate of the layerwas evaluated and the activation energy was found to be 138.46 and 106.65 kJ mol^-1, for pure aluminium and Al-8Si baths respectively.     

钼酸钠对热镀锌钢板表面磷化膜电化学行为的影响

在磷化液中添加钼酸钠可改善和提高热镀锌钢板表面磷化膜的质量.运用极化和电化学阻抗的测试方法,研究了磷化液中加入钼酸钠对热镀锌钢板表面磷化膜在5%NaCl溶液中的电化学行为的影响.结果表明,在磷化液中加入钼酸钠可促进磷化膜生长,大大降低电化学体系的腐蚀电流密度,提高其极化电阻和电化学阻抗,改善膜层的耐蚀性能.最佳的钼酸钠用量为1.0g/L,膜层呈暗灰色,膜重为1.6g/m2,耐硫酸铜点蚀时间大于65 s.当钼酸钠用量为2.0g/L时,膜层的各项性能指标均下降.     

铜铁界面含氧层对镀层结合强度的影响

镀层与基体界面间含氧层的存在,影响电镀层与基体之间金属键的形成,进而影响镀层的结合强度.用氰化物和焦磷酸盐两种工艺在铁片上镀铜,对镀层进行恒电流极化,并以氩离子深度刻蚀和X射线光电子能谱相结合的方法进行检测.电沉积初始电位-时间曲线显示,两种镀铜工艺,结合强度好的出现了基体表面的还原活化电位平阶,结合强度差的焦酸盐镀铜未出现活化就发生了金属的电沉积,而且铜镀层与基体界面含氧量有增高的现象.铜镀层与铁基底界面间含氧层的存在是影响镀层结合强度的主要原因.通过控制金属电沉积初始电位可提高镀层的结合强度.     

Sol-gel法制备耐蚀涂层的技术及应用

Sol-gel法制备耐蚀涂层对提高基材的化学耐久性、防止氧化、控制腐蚀有显著的效果,有望完全替代传统材料表面腐蚀控制处理使用的毒性物质铬酸盐处理工艺,可以减轻对环境的污染,是一项可持续发展的表面处理技术.为了阐述该项技术的工艺方法及特点,综述了Sol-gel法制备技术在不同的金属基体--不锈钢、铝合金和铜合金表面中的应用现状和最新研究进展.分析了采用Sol-gel法制备耐蚀涂层可以有效地阻止腐蚀介质对基体金属材料的破坏,延长材料在实际应用环境中的使用寿命等方面的作用原理,从理论上对Sol-gel耐蚀涂层的形成机制和耐蚀机理进行了初步讨论,并对Sol-gel技术的应用前景作一简要展望.     

Chromium electroplating from trivalent chromium baths as an environmentally friendly alternative to hazardous hexavalent chromium baths: comparative study on advantages and disadvantages

In this communication, we present a generalization of our investigations concerning current state in the development of trivalent chromium baths as an environmentally friendly alternative to hazardous electroplating baths containing extremely toxic hexavalent chromium compounds. The main technological properties of sulfate trivalent chromium baths containing carbamide and formic acid as organic additives are described and compared to those typical of common Cr(VI) plating bath. It is shown that thick nanocrystalline chromium–carbon deposits may be obtained from the Cr(III) electrolytes under study, with some physicochemical and service properties of such coatings exceeding those of “usual” chromium deposits. The proposed trivalent chromium baths are distinguished by their high current efficiency and electrodeposition rate. The covering power of the Cr(III) baths is poorer than in case of hexavalent chromium baths; it may be improved by applying basic chromium sulfate (chrome tanning agent) instead of chromium sulfate as a source of Cr(III) ions in solution. There is no need to utilize toxic lead anodes in Cr(III) deposition processes. It is noted that a grave shortcoming of trivalent baths is their low conductivity in comparison with the hexavalent ones.     

石墨烯添加量对Ni基-石墨烯复合镀层性能的影响

为提高连铸结晶器的表面性能,以NiSO_4·6H_2O为主盐,用电镀的方法在炼钢连铸结晶器铜板上制备了Ni基-石墨烯复合镀层。利用场发射扫描电镜(FE-SEM)、能谱仪(EDS)、X射线衍射仪(XRD)、显微硬度计、摩擦磨损试验机等分析手段,研究了镀液中石墨烯浓度对复合镀层组织、成分、形貌、厚度、相结构、硬度及耐磨性的影响,分析了复合强化机理。结果表明:Ni基-石墨烯复合镀层中C含量随着石墨烯添加量的增加而增加,石墨烯在镀层表面及截面上的分布较均匀;镀层的平均摩擦系数随石墨烯添加量的增加而减小,显微硬度显著提高;当镀液中石墨烯浓度为120 mg/L时,镀层的平均显微硬度为1 142 HV_(1N),摩擦系数为0.548,耐磨性优于目前生产上的常规Ni-Co合金镀层,可以有效地保证铸坯质量和提高结晶器使用寿命。     

Zinc recovery and waste sludge minimization from chromium passivation baths

This work reports the feasibility of applying emulsion pertraction technology (EPT) aiming at zinc recovery and waste minimization in the zinc electroplating processes that include Cr (III) passivation. The assessment consists of firstly the lifetime extension of the passivation baths by selective removal of the tramp ions zinc and iron, and secondly, the recovery of zinc for further reuse. Spent passivation baths from a local industry were tested, being the major metallic content: Cr³⁺ 9000 mg L⁻¹, Zn²⁺ 12,000 mg L⁻¹, Fe³⁺ 100 mg L⁻¹. Working in a Liqui-Cel hollow fiber membrane contactor and using the extractant bis(2,4,4-trimethylpentyl) phosphinic acid, reduction of zinc and iron concentrations below 60 mg L⁻¹ and 2 mg L⁻¹, respectively were obtained, while trivalent chromium, the active metal that generates the passivation layer, was retained in the baths. Zinc was selectively transferred to an acidic stripping phase that in the experimental time reached a concentration of 157,000 mg L⁻¹. Zinc recovery by electrowinning from the acidic stripping phase without any pretreatment of the electrolyte solution provided a purity of 98.5%, matching the lower commercial zinc grade. As a result of the extension of the life time of the passivation bath, significant environmental advantages are derived such as minimization of the volume of hazardous wastes and savings in the consumption of raw materials.     

The influence of the electroplating parameters on the conditions of deposited nickel‐iron coatings

Several specific electroplating parameters are varied to develop a manufacturing process for nickel‐iron coatings with low residual stresses and favourable structures and hardness values. Here, the produced coating conditions on the surface are characterised according to alloy compositions, microstructures, residual stresses, texture and microhardness as well as the elastic indentation modulus. The manufacture of the coatings was carried out in a laboratory electroplating plant. The process parameters are: electroplating in electrolytic baths with and without saccharin as an additive, with different iron content as well as with various current parameters. The results show significant influences of saccharin, as a bath additive, and of the pulse frequency during the reverse current pulse procedure on the coating conditions. Supplementary investigations are scheduled for determining the distributions of the conditions through the coating thickness. Similarly, micromechanical tests are planned. Process parameters with optimal conditions can then be selected from the determined process‐condition property relation. This is to subsequently serve as the basis for improving the manufacture of micro gear‐wheels. The micro gear‐wheels are produced by electroforming using the direct LIGA process.     

电沉积工艺参数对Ni-TiN-CeO2二元纳米复合镀层中粒子复合量的影响

采用超声-脉冲电沉积法制备了Ni-TiN-CeO2二元纳米复合镀层,研究了工艺参数对镀层中CeO2及TiN粒子复合量的影响,并对镀层的表面形貌及成分进行了测试和分析。结果表明,超声-脉冲电沉积Ni-TiN-CeO2纳米复合镀层的最佳工艺参数为阴极电流密度4A/dm2,TiN粒子添加量15g/L,CeO2粒子添加量40g/L,正向脉冲占空比20%,超声波功率180W。在该工艺条件下,可获得CeO2质量分数为3.3%、TiN质量分数为4.4%的Ni-TiN-CeO2二元纳米复合镀层。同时,TiN与CeO2二元纳米粒子的加入,充分发挥了两种纳米粒子复合的协同效应,优化了粒子与基质金属的共沉积方式,大大改善了镀层质量。