Acid etching as a surface pre-treatment step for PVD coatings on high strength steels

Abstract

Coating deposition by Physical Vapour Deposition (PVD) on high strength steels is an important research project at TATA Steel - IJmuiden. The research is aimed at replacing the conventional hot-dip galvanisation process to obtain a defect-free coating without affecting their well-engineered properties. However, the annealing treatment of the steel, performed to obtain these properties, affects the coating adhesion properties. This is a result of the selective oxidation process, which forms external oxides of alloying elements at the surface. Therefore, a pre-treatment process is required to remove these surface oxides from the steel strips before they are coated. Plasma sputtering is currently being
used for the pre-treatment to remove any contaminants and surface oxides from the steel. To obtain a good coating adhesion, a relatively large amount of surface oxides needs to be removed by sputtering. Also, the removed material is known to contaminate the vacuum chamber in the PVD deposition line, for which frequent maintenance of the chamber might be necessary. Thus, an additional
surface pre-treatment step was investigated in this study to reduce the sputtering process inside the vacuum as much as possible. In the present work, the effect of both direct current electrolytic alkaline cleaning and sulphuric acid etching on the surface of DP800 steel was investigated. Two different baths were considered for this purpose; a 27 g/L NaOH bath with some additive at 60°C and a 50 g/L H2SO4 bath at 25°C and 50°C. A current density of 1.5 A/dm2 was applied during the electrolytic cleaning for which both cathodic and anodic polarisation methods were investigated. Also, a range of acid etching times (10s to 120s) was investigated for the given concentration and temperatures of the acid bath to study its effect on the surface. The effect of adding a corrosion inhibitor into the acid bath on the rest of the coating deposition process was also investigated. Various surface characterisation techniques and wettability tests were performed to study the changes in morphology and composition of the surface and their effect on the coating adhesion properties of the treated samples. Finally, coating adhesion tests were performed after zinc deposition to investigate the adhesion performance of the steel after the pre-treatment steps. Initial surface analysis during electrolytic alkaline cleaning showed that the anodic polarisation was more effective than cathodic polarisation of the sample, as the latter tends to reduce the surface wettability by additional deposits of iron fines over the surface. A subsequent acid etching provided a reduction in the minimum required sputter intensity to obtain a good adhesion from 2300 kJ/m2 to about 800 kJ/m2. A further reduction was achieved to a sputter intensity of only 214 kJ/m2 after retarding the effects of surface reoxidation by vacuum sealing the samples. Acid etching at 25°C provided bad coating adhesion at lower etching times, attributed to the partial dissolution of surface oxides and absence of an initial grain roughening. Good coating adhesion was either obtained at higher etching times or by increasing the temperature of the acid bath to 50°C. Addition of a corrosion inhibitor was considered impractical as high sputter intensities (> 321 kJ/m2) was required to remove the adsorbed inhibitor molecules from the surface. Thus, a reduction in the required sputter intensity was achieved by more than a factor of 10 after acid etching, only if the effects of surface reoxidation during the transfer time between acid etching and entering the PVD installation can be minimized.