Thesis (M.S.)--University of Texas at El Paso, 2009. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.

The aim of this research proj ect was to produce compositionally modulated zincnickel and zinc-nickel-manganese coatings usi ng a single bath process by variation of the applied electroplating current density. These could then be considered as possible replacements for electroplated cadmium. Zinc-nickel electrodeposits from both a simple bath and one containing the complexant tris(hydroxymethyl)methylamine (TRIS) were produced using either bath or by selective electroplating onto mild steel, 2014-T6 aluminium and 2000 series aluminium alloy connector shells. Zinc-nickelmanganese coatings were electroplated onto mild steel, using both DC and pulse electroplating from sulphate based baths containing either the complexant TRIS or sodium citrate. The coatings and the various electrodeposition processes were evaluated by thickness measurements, cun'ent efficiency calculations, composition detennination using energy dispersive X-ray anal ys is and SEM to examine the morphology. Corrosion characteristics were investigated by neutral salt fog exposure, alternate immersion, atmospheric trials, and electrochemical immersion tests including potential monitoring, galvanic and polarisation measurements. Other properties such as microhardness and surface electrical conductivity were also investigated. Compositionally modulated zinc-nickel and ziJlc-nickel-manganese were successfully deposited from single baths with nickel contents ranging from 5-20% Ni and manganese contents varying from 0-12% Mn. Current efficiency measurements showed the efficiency to be low especially for the zinc-nickel-manganese coatings, which exhibited a distinct morphology when electroplated from the citrate bath. Corrosion testing indicated that both coatings had a lower corrosion resistance than cadmium especially in accelerated tests, with a reduction in corrosion resistance being seen as the nickel content was increased; due to a decrease in density of the electroplate. This, and increasing through-thickness porosity promoted ennoblement of zinc-nickel and zinc-nickel-manganese leading to the coatings becoming nonsacri ficial to the substrate in accelerated tests. Zinc-nickel-manganese showed less white rust than zinc-nickel and exhibited lligher micro-hardness than zinc, cadmium and zinc-nickel. Electrical measurements indicated that both coatings were sufficiently conductive to meet the surface conductivity requirements for use on electrical connector shells.

Zinc and its alloys are among the most widely utilised metallic coatings for the sacrificial protection of steel. Although excellent in this mode of protection, these coatings are often less durable when subjected to environments of combined wear and corrosion due to their intrinsic relative softness and ductility. A possible and fast growing way of improving the durability of these coating is by the codeposition of inert particles into the zinc and zinc-alloy matrix. The main aim of this research was therefore to improve the durability of zinc and zinc-nickel coatings by the incorporation of inert particles via electrolytic codeposition methods. The first five chapters of this thesis comprise literature review on the electrodeposition of zinc, its alloys and composite electrodeposition in general. A major part of which was dedicated to the review of various conventional methods and parameters such as current density, agitation, temperature, solution composition, bath additives and pH usually investigated in electrodeposition. The experimental work was principally based on DC electrodeposition and was aimed at understanding the deposition behaviour of zinc and zinc-nickel electrodeposition baths, conditions which influence them and solution compatibility to the introduction of silica particles. A systematic study on the deposition behaviour of both zinc/silica and zinc-nickel/silica composite baths was carried out with particular interest on the rate of particle incorporation and the influence of particles on zinc-nickel alloy deposition. The complimentary codeposition behaviour of the nickel and silica particles was observed. The influence of bath additives such as N,N Dimethyldodecylamine (NND) and sodium nitrate on the rate of silica incorporation was also studied. Both additives were found to improve the rate of particle incorporation for the zinc/silica. The morphologies and compositions of the coatings were analysed with the use of SEM and FEGSEM. Corrosion performance studies were carried out in a neutral salt spray chamber and linear polarisation resistance methods used to determine barrier corrosion properties of the coatings. Anodic polarisation studies were also carried out. The results show an improvement in the corrosion performance of these coatings with the addition of silica particles Reciprocating wear tests were used to determine the wear behaviour of the coatings in terms of weight loss. Improvement in wear resistance was not observed in the zinc/silica coatings probably due to the high content of silica in the coatings. Lower silica contents may be required for the desired improvements. However, there were obvious improvements in the wear behaviour of the zinc-nickel/silica coatings due to the presence of the silica particles.

Zinc-nickel ?-phase silicate and copper-nickel silicate corrosion resistant coatings have been prepared via electrochemical methods to improve currently available corrosion resistant materials in the oil and gas industry. A layered silicate, montmorillonite, has been incorporated into the coatings for increased corrosion protection. For the zinc nickel silicate coatings, optimal plating conditions were determined to be a working pH range of 9.3 -9.5 with a borate based electrolyte solution, resulting in more uniform deposits and better corrosion protection of the basis metal as compared to acidic conditions. Quality, strongly adhering deposits were obtained quickly with strong, even overall coverage of the metal substrate. The corrosion current of the zinc-nickel-silicate coating is Icorr = 3.33E-6 for a borate based bath as compared to a zinc-nickel bath without silicate incorporation (Icorr = 3.52E-5). Step potential and direct potential methods were examined, showing a morphological advantage to step potential deposition. The effect of borate addition was examined in relation to zinc, nickel and zinc-nickel alloy deposition. Borate was found to affect the onset of hydrogen evolution and was examined for absorption onto the electrode surface. For copper-nickel silicate coatings, optimal conditions were determined to be a citrate based electrolytic bath, with pH = 6. The solutions were stable over time and strong adhering, compact particle deposits were obtained. The corrosion current of the copper-nickel-silicate coatings is Icorr = 3.86E-6 (copper-nickel coatings without silicate, Icorr = 1.78E-4). The large decrease in the corrosion current as the silicate is incorporated into the coating demonstrates the increase in corrosion resistance of the coatings with the incorporation of silicates.

The optimal conditions for deposition of zinc-nickel alloys onto stainless steel discs in alkaline solutions have been examined. In the past cadmium has been used because it shows good corrosion protection, but other methods are being examined due to the high toxicity and environmental threats posed by its use. Zinc has been found to provide good corrosion resistance, but the corrosion resistance is greatly increased when alloyed with nickel. The concentration of nickel in the deposit has long been a debated issue, but for basic solutions a nickel concentration of 8-15% appears optimal. However, deposition of zinc-nickel alloys from acidic solutions has average nickel concentrations of 12-15%. Alkaline conditions give a more uniform deposition layer, or better metal distribution, thereby a better corrosion resistance. Although TEA (triethanolamine) is most commonly used to complex the metals in solution, in this work I examined TEA along with other complexing agents. Although alkaline solutions have been examined, most research has been done in pH ≥ 12 solutions. However, there has been some work performed in the pH 9.3-9.5 range. This work examines different ligands in a pH 9.3-9.4 range. Direct potential plating and pulse potential plating methods are examined for optimal platings. The deposits were examined and characterized by XRD.

<p>At present the automotive industry is due to an EU directive, replacing hexavalent chrome on vehicles. This is an extensive job as hexavalent chrome is used all over the vehicle and to large extent on fasteners (screws, nuts, rivets etc.). Chrome (VI) is used as a passivating layer on mainly zinc-iron. When replacing the hexavalent chrome with a chrome (VI) free product, the passivating properties are reduced. One of the alternatives is to replace the zinc-iron coating with a zinc-nickel coating. This coating shows great promise from the corrosion resistance point of view. Zinc-nickel is a cathodically protecting coating, and will in principle dissolve to protect the substrate from corrosion. It is therefore important to understand how, and at what rates nickel is released from zinc-nickel coatings when exposed to a chloride-rich automotive environment. The potential environmental impact of nickel needs to be evaluated before Scania can introduce this alternative as corrosion protection. Tests by Scania have previously shown that contact allergy is not an issue for zinc-nickel coatings with Cr (III) passivation.</p><p>Nickel release rates corresponding to 0,12 mg m^-2yr^-1 for zinc-15 % nickel coatings at a pH of 4,2 were determined from an accelerated corrosion test. Based on these values, less than 1 kg of nickel per year would be released from the Scania rolling stock if Scania were to introduce zinc-nickel coatings preferably on fasteners. This value is low compared to other sources of nickel release. In order to evaluate the toxicity of the released nickel, information about the chemical speciation, i.e. chemical forms, is needed.</p><p>Total or dissolved metal are not good predictors of ecotoxicity of metals. Chemical speciation and bioavailability must be incorporated in toxicity testing. Total or dissolved metal may be used as a worst case approximation.</p>

At present the automotive industry is due to an EU directive, replacing hexavalent chrome on vehicles. This is an extensive job as hexavalent chrome is used all over the vehicle and to large extent on fasteners (screws, nuts, rivets etc.). Chrome (VI) is used as a passivating layer on mainly zinc-iron. When replacing the hexavalent chrome with a chrome (VI) free product, the passivating properties are reduced. One of the alternatives is to replace the zinc-iron coating with a zinc-nickel coating. This coating shows great promise from the corrosion resistance point of view. Zinc-nickel is a cathodically protecting coating, and will in principle dissolve to protect the substrate from corrosion. It is therefore important to understand how, and at what rates nickel is released from zinc-nickel coatings when exposed to a chloride-rich automotive environment. The potential environmental impact of nickel needs to be evaluated before Scania can introduce this alternative as corrosion protection. Tests by Scania have previously shown that contact allergy is not an issue for zinc-nickel coatings with Cr (III) passivation. Nickel release rates corresponding to 0,12 mg m-2yr-1 for zinc-15 % nickel coatings at a pH of 4,2 were determined from an accelerated corrosion test. Based on these values, less than 1 kg of nickel per year would be released from the Scania rolling stock if Scania were to introduce zinc-nickel coatings preferably on fasteners. This value is low compared to other sources of nickel release. In order to evaluate the toxicity of the released nickel, information about the chemical speciation, i.e. chemical forms, is needed. Total or dissolved metal are not good predictors of ecotoxicity of metals. Chemical speciation and bioavailability must be incorporated in toxicity testing. Total or dissolved metal may be used as a worst case approximation.

Les travaux présentés dans ce mémoire ont pour but d’approfondir la compréhension des mécanismes d’élaboration de revêtements électrolytiques de zinc-nickel obtenus à partir d’électrolytes alcalins. Les dépôts de zinc-nickel contenant entre 12% et 16%de nickel, connus pour leur performances anti-corrosion, nécessitent l’utilisation d’agents complexants afin de d’obtenir des formes solubles et réductibles du nickel dans un électrolyte à base de zincates à haut pH. Une étude des mécanismes de complexation a permis d’améliorer la compréhension du rôle respectif des agents complexants et de leurs interactions sur la stabilité des mélanges, ainsi que sur la morphologie de la structure cristalline des revêtements obtenus. Les phases cristallines d’alliages de zinc-nickel électro déposés,contenant entre 1% et 20% de nickel ont été quantifiés par déconvolution de courbes d’oxydation potentio dynamique et par DRX. Cette approche donne accès à une cartographie précise des phases d’alliages obtenus en fonction de la teneur en nickel du dépôt. La stabilité thermique des différentes phases à également pu être évaluée et quantifiée par cette méthode. La formulation des électrolytes ainsi que les paramètres des procédés peuvent modifier les cinétiques de germination des revêtements. Une étude fondamentale des mécanismes de germination par chrono ampérométrie couplée à des méthodes d’identification paramétrique a permis de quantifier l’évolution de certains paramètres de germination d’éléments simples en fonction du potentiel d’électrodéposition. L’étude de la germination d’alliage a mis en évidence que des réactions de décomplexation d’espèces modifient les cinétiques de nucléation, sans permettre d’aboutir à un modèle descriptif complet. / The present work aims to deepen the understanding of the mechanisms of zinc-nickelelectrodeposition in alkaline baths. Zinc-nickel deposits containing between 12% and 16%nickel known for their anti-corrosion performance. Complexing agents are required toobtain soluble and reactive nickel forms, and to stabilize the electrolytes. A study ofthe complexing mechanisms has improved the understanding of their respective role andbehavior, and their influence on the stability and the morphology and crystalline structureof the coatings obtained. The crystalline phases of electroplated zinc-nickel alloys in therange from 1% to 20% nickel content were quantified by deconvolution of potentiodynamicoxidation curves and XRD. This approach has led to a precise mapping of the alloyphases obtained as a function of the nickel content. The thermal stability of the differentphases has also been evaluated and quantified by this method. The formulation of theelectrolytes and the process parameters may modify the kinetics of coating germination. Afundamental study of the mechanisms of germination by chronoamperometry coupled witha parametric identification allows the quantification of parameter evolution in relation tonucleation phenomenon of simple elements. The study of alloy germination has shownthat decomplexing reactions are able to modify nucleation kinetics, without achieving acomplete comprehensive modeling.

Corrosion can cause devastating damage to materials, and to protect materials from corrosion is crucial, especially in the aeronautical industry. An electroplated Zinc-Nickel coating provides excellent corrosion protection of steel. Electroplating of ZnNi is a sensitive process which needs frequent and fast feedback controls and adjustments of the process electrolyte. A common process control for electroplating processes is the Hull cell test, which is investigated in this study. The Hull cell test is a lab scaled electroplating unit, which spans a wide range of current densities. It is crucial to establish the relation between process parameters in the Hull cell and the resulting coating characteristics in order to implement it as a process control. The purpose of this study is to establish these relations for the ZnNi electroplating process, and evaluate if the Hull cell test is a suitable process control for this process. How the process parameters; current density, temperature, metal ion concentration, and carbonate contaminations affect the coating characteristics; visual appearance, thickness, composition, surface structure, and phase content has been established. Influence on the coatings were mainly seen at current densities higher and lower than the ones used in production. This demonstrates the strength of the Hull cell test for early detection of process deviations. Coating thickness and composition was measured with X-ray fluorescence. However, the composition values for thin coatings were discovered to be inaccurate, which was avoided by increasing the plating time. Once addressed, the Hull cell test is suitable as a process control for the electroplating process of ZnNi.