Electrodeposition of corrosion resistant zinc alloy coatings

With the increase use of de-icing salts on roads for safety, the need for improved corrosion resistance of the traditional galvanized automobile bodies has never been greater. In the present work, Zn alloy coatings (Zn-Ni and Zn-Co) were studied as an alternative to pure Zn coatings. The production of these deposits involved formulation of various acidic (pH of about 5.5) chloride based solutions. These showed anomalous deposition, that is, alloys were deposited much more easily than expected from the noble behaviour of Ni and Co metals. Coating compositions ranging from 0 to about 37% Ni and 20% Co were obtained. The chemical composition of the coatings depended very much on the electrolytes nature and operating conditions. The Ni content of deposits increased with increase in Ni bath concentration, temperature, pH and solution agitation but decreased considerably with increase in current density. The throwing power of the Zn-Ni solution deteriorated as Ni metal bath concentration increased. The Co content of deposits also increased with increase in Co bath concentration and temperature, and decreased with increase in current density. However, the addition of commercial organic additives to Zn-Co plating solutions suppressed considerably the amount of Co in the coatings. The Co content of deposits plated from Zincrolyte solution was found to be more sensitive to variation in current density than in the case of deposits plated from the alkaline Canning solution. The chromating procedures were carried out using laboratory formulated solution and commercially available ones. The deposit surface state was of great significance in influencing the formulation of conversion coatings. Bright and smooth deposits acquired an iridescent colour when treated with the laboratory formulated solution. However, the dull deposits acquired a brownish appearance. The correlation between the electrochemical test results and the neutral salt spray in marine environment was good. Non-chromated Zn-Ni coatings containing about 11-14% Ni increased in corrosion resistance compared to pure Zn. Non-chromated Zn-Co deposits of composition 4-8% were required to show a significant improvement in corrosion resistance Corrosion resistance was improved considerably by conversion coating. However, the type of conversion coating was very important. Samples treated in a laboratory solution performed badly compared to those treated in commercial solutions. Zn alloy coatings were superior to pure Zn, the Schloetter sample (13.8% Ni) had the lowest corrosion rate, followed by the Canning sample (1.0% Co) and then Zincrolyte (0.3% Co).Neither the chromium content of the conversion films nor the chromium state was found to have an effect on corrosion performance of the coatings.

Fracture toughness of a series of high chromium abrasion resistant alloys

The fracture properties of a series of alloys containing 15% chromium and 0.8 to 3.4% carbon are investigated using strain fracture toughness testing techniques. The object of the work is to apply a quantitative method of measuring toughness to abrasion resistant materials, which have previously been assessed on an empirical basis; and to examine the relationship between microstructure and K10 in an attempt to improve the toughness of inherently brittle materials. A review of the relevant literature includes discussion of the background to the alloy series under investigation, a survey of the development of fracture mechanics and the emergence of K10 as a toughness parameter. Metallurgical variables such as composition, heat treatment, grain size, and hot working are ???? to relate microstructure to toughness, and fractographic evidence is used to substantiate the findings. The results are applied to a model correlating ductile fracture with plastic strain instability, and the nucleation of voids. Strain induced martensite formation in austenitic structures is analysed in terms of the plastic energy dissipation mechanisms operating at the crack tip. Emphasis is placed on the lower carbon alloys in the series, and a composition put forward to optimise wear resistance and toughness. The properties of established competitive materials are compared to the proposed alloy on a toughness and cost basis.

Corrosion mechanisms of duplex stainless steels in the petrochemical industry

The recent search for new sources of hydrocarbons has led to production from very severe environments which can contain considerable amounts of carbon dioxide, hydrogen sulphide, and chloride ions, combined with temperatures which can exceed 100°C. Oil and gas production from such wells requires highly corrosion-resistant materials. The traditional solution of using carbon steel with additional protection is generally inadequate in these very-aggressive environments. Duplex stainless steels (DSS) are attractive candidates because of their high strength, good general corrosion resistance, excellent resistance to chloride-induced stress corrosion cracking, and good weldability. Although duplex stainless steels have a very good reputation in both subsea and topsides pipework, it is recognized that the tolerance of these materials to variations in microstructure and chemical composition are still not fully understood. The object of this paper is to review the corrosion behaviour of duplex stainless steels in the petrochemical industry, with particular emphasis on microstructures and the effect of changes in chemical composition.

The effect of frequency and microstructure on corrosion fatigue crack propagation in high strength aluminium alloys

Fatigue crack growth in high strength aluminium alloy 7150 commercial plate material has been studied in both laboratory air and acidified aqueous salt solution. The aggressive aqueous environment enhanced fatigue crack growth rates by up to an order in magnitude compared to laboratory air. The enhancement in fatigue crack growth rate was accompanied by evidence of embrittlement in the crack path, involving both brittle intergranular and transgranular failure modes. Both the enhancement of fatigue crack growth rates and the extent of intergranular growth modes are dependent on cyclic frequency which, along with the absence of a similar frequency effect in a spray-formed version of the material with a significantly different grain structure, supports a mechanism of grain boundary hydrogen diffusion for intergranular corrosion fatigue crack growth. The convergence of corrosion fatigue crack growth rates at high ΔK in both spray-formed and conventional plate materials coincides with the operation of identical transgranular corrosion fatigue modes dependent on strain-controlled hydrogen diffusion ahead of the crack tip. © 1997 Acta Metallurgica Inc.

The creep behaviour of pressure diecast zinc-aluminium based alloys

The creep behaviour of three pressure diecast commercial zinc-aluminium based alloys: Mazak 3, corresponding to BS 1004A, and the new alloys ZA.8 and ZA.27 with a series of alloys with compositions ranging from 0% to 30% aluminium was investigated. The total creep elongation of commercial alloys was shown to be well correlated using an empirical equation. Based on this a parametrical relationship was derived which allowed the total creep extension to be related to the applied stress, the temperature and the time of test, so that a quantitative assessment of creep of the alloys could be made under different conditions. Deviation from the normal creep kinetics occurred in alloys ZA.8 and ZA.27 at very low stresses, 150°C, due to structural coarsening combined with partial transformation of ε -phase into T' phase. The extent of primary creep was found to increase with aluminium content, but secondary creep rates decreased in the order Mazak 3, ZA.8 and ZA.27. Thus, based on the above equation, ZA.8 was found to have a substantially better total creep resistance than ZA.27, which in turn was marginally better than Mazak 3 for strains higher than 0.5%, but inferior for smaller strains, due to its higher primary creep extension. The superior creep resistance of ZA.8 was found to be due to the presence of strictly-orientated, thin plate-like precipitates of ε(CuZn4) phase in the zinc matrix of the eutectic and the lamellarly decomposed β phase, in which the precipitation morphology and orientation of ε in the zinc matrix was determined. Over broad ranges of temperature and stresses, the stress exponents and activation energies for creep were found to be consistent with some proposed creep rate mechanisms; i.e. viscous glide for Mazak 3, dislocation climb over second phase particles for ZA.8 and dislocation climb for ZA.27, controlled by diffusion in the zinc-rich phase. The morphology of aluminium and copper-rich precipitates formed from the solid solution of zinc was clearly revealed. The former were found to further increase the creep rate of inherently low creep resistant zinc, but the latter contributed significantly to the creep resistance. Excess copper in the composition, however, was not beneficial in improving the creep resistance. Decomposition of β in copper-containing alloys was found to be through a metastable Zn-Al phase which is strongly stabilised by copper, and the final products of the decomposition had a profound effect on the creep strength of the alloys. The poor creep resistance of alloy ZA.27 was due to the presence of particulate products derived from decomposed β-phase and a large volume of fine, equiaxed products of continuously decomposed α-dendrites.

Brush plating of bearing alloys on aluminium alloy shells

The turbocharging of diesel engines has led to increase in temperature, load and corrosive attack of plain bearings. To meet these requirements, overlay plated aluminium alloys are now preferred. Currently, lead-tin alloys are deposited using a zincate layer and nickel strike, as intermediate stages in the process. The nickel has undesirable seizure characteristics and the zincate can given rise to corrosion problems. Consequently, brush plating allows the possible elimination of these stages and a decrease in process together with greater automation. The effect of mode application, on the formation of zincate films, using film growth weight measurements, potential-time studies, peel adhesion testing and Scanning Electron Microscopy was studied, for both SIC and AS15 aluminium alloys. The direct plating of aluminium was also successfully achieved. The results obtained indicate that generally, although lower adhesion resulted when a brush technique was used, satisfactory adhesion for fatigue testing was achieved. Both lead-tin and tin-cobalt overlays were examined and a study of the parameters governing brush plating were carried out using various electrolytes. An experimentally developed small scale rig, was used to produce overlay plated bearings that were fatigue tested until failure. The bearings were then examined and an analysis of the failure mechanisms undertaken. The results indicated that both alloy systems are of the regular codeposition type. Tin-cobalt overlays were superior to conventional lead-tin overlays and remained in good condition, although the lining (substrate) failed. Brush plated lead-tin was unsatisfactory. Sufficient understanding has now been gained, to enable a larger scale automated plant to be produced. This will allow a further study of the technique to be carried out, on equipment that more closely resembles that of a full scale production process.

Electrodeposition on aluminium and its alloys

Aluminium alloys S1C, NS4, HE9, LM25 and the 'difficult' zinc containing U.S. specification alloy used for automobile bumpers (X-7046), have been successfully electroplated using pretreatments which utilized either conventional immersion, elevated temperature or electrolytic modified alloy zincate (M.A.Z.) deposits. Satisfactory adhesion in excess of 7•5 KN m -I was only achieved on X-7046 using an electrolytic M.A.Z. pretreatment. The limitations of simple zincate solutions were demonstrated. Growth of deposits ~as monitored using a weight loss technique and the morphology of the various deposits studied using scanning electron microscopy. The characteristics of a specific alloy and processing sequence selected had a significant influence on the growth and morphology of the N.A.Z. deposi t. These all affected subsequent adhesion of electrodeposited nickel. The advantages of double-dip sequences were confirmed. Superior adhesion was associated with a uniform, thin, fine grained M.A.Z. deposit which exhibited rapid and complete surface coverage of the aluminium alloy. The presence of this preferred type deposit did not guarantee adhesion because a certain degree of etching was essential. For a satisfactory combination of alloy and M.A.Z. pretreatment, there was a specific optimum film weight per unit area which resulted in maximum adhesion. An ideal film weight of 0•06 :!: 0•01 mg cm-2was determined for S1C. Different film weights were required for the other alloys due to variations in surface topography caused by pretreatment. S1C was the easiest alloy on which to achieve high bond strength. Peel adhesion was not directly related to tensile strength of the alloy. The highest adhesion value was obtained on S1C which had the lowest strength of the alloys studied. The characteristics of the failure surfaces after peeling depended on alloy type, adhesion level and pretreatment employed. Plated aluminium alloys exhibited excellent corrosion resistance when appropriately pretreated. The M.A.Z. layer was not preferentially attacked. There was a threshold value of adhesion below which corrosion performance ~a8 poor. Alloy type, pretreatment and coating system influenced corrosion performance. Microporous chromium gave better corrosion protection than decorative chromium.

Application of wear resistant coatings by the brush plating technique

The development of cobalt molybdenum and cobalt tungsten brush plating electrolytes is described. Their optimum compositions and operating conditions for commercial applications have been determined. The effects of composition, pH, applied voltage, stylus speed and pressure upon deposit composition and efficiency have been investigated. Transmission and Scanning Electron Microscopy have been employed to study the cobalt alloy deposits produced. Evaluation of the wear resistant properties of the cobalt alloys developed in this work was carried out in the laboratory using a pin and disc technique and a simulated hot forging test, and by industrial trials involving the "on site" plating of hot forging dies and cold pressing tools. It was concluded that the electrolytes developed in tl1is work enabled cobalt alloys containing 6% Mo or 8% W to be deposited at 17-20V. Brush plated cobalt deposits possessed a mixed CPU and FCC crystallographic structure at room temperature. The application of 13µm of either of the cobalt alloys resulted in improved wear performance in both pin and disc and simulated hot forging tests. The results of the industrial trials indicated that by the use of these alloys, the life of hot forging dies may be increased by 20-100%. A commercial forging organisation is using electrolytes developed in this work to coat dies prior to forging nimonic alloys. Reductions in forging temperature and improved forging qualities have been reported. Cold pressing tools coated with the alloys showed a reduced tendency to "pick-up" and scoring of the pressed panels. Reports of a reduced need for lubrication of panels before pressing have also been received.