Tailoring of Transition Metal Silicides as Protective Thin Films on Austenitic Stainless Steel

Doctoral thesis, 2011

The objective of this study is to make use of transition metal silicides in a novel way as protective thin films on engineering metals. It can then be possible to take advantage of the potentially good corrosion resistance of metal silicides while compensating for their brittle nature by the ductile bulk material. Transition metal silicide thin films based on the systems of Ti-Si, Cr-Si, Fe-Si, Ni-Si were fabricated by means of ion-beam co-sputter deposition on 304 stainless steel substrates, with or without subsequent annealing treatment. Thin film characterisation was done by means of X-ray photoelectron and X-ray diffraction analysis. For the films in crystalline form after annealing, the silicides were well-characterised by means of both techniques. The co-sputtered films showed short-range ordered structures, but the possible silicide phases could be depicted from the core-level XPS spectra of the transition metal peaks defined by the crystalline forms. Except for the Cr-Si system, the phase formation sequence during annealing processes was possible to predict by means of Pretorius’ effective heat of formation (EHF) model provided that the initial thin film compositions were determined. The corrosion properties of the as-deposited silicide films and the uncoated stainless steel specimens were assessed by means of polarisation measurements in dilute hydrochloric (HCl) and sulphuric (H2SO4) acid solutions. All silicide-coated specimens showed lower current densities along the measured potentials than the uncoated steel, suggesting their lower reactivity. Among the silicide films, the Ti-Si and Ni-Si based films showed the best corrosion properties and Si content above 60 at.% for all films facilitated high integrity Si-oxide layer development, whereby corrosion properties improved. Further studies conducted on the Ni-Si system showed that composition is a more important design factor than structure. When considering their tribological properties, Rockwell-C adhesion tests and reciprocating sliding wear tests proved the silicide films to be well-adhering on the substrates and to show lower specific wear rate (10e-13 m3/Nm) than that (10e-12 m3/Nm) of the uncoated steel. It is supposed that transition metal silicides can act as protective thin films on stainless steel as well as any other engineering materials as far as good adhesion is guaranteed.