Oxidation and crystallisation of amorphous alloys
Amorphous alloys have a range of desirable ferromagnetic, electrical, mechanical and chemical properties. For instance, the application of Fe-based soft ferromagnetic amorphous alloys as transformer core materials can cut the transformer core losses to about 1/4, with considerable energy saving. However, during manufacture, heat treatment and in service, amorphous alloys may need to be exposed to moderately high temperatures for a period of time, with possible degradation caused by oxidation and crystallisation. There has been almost no previous study of oxidation behaviour and the relationship between oxidation and crystallisation in amorphous alloys. Eight important amorphous alloys and an industrial crystalline silicon steel have been studied in the present work; amorphous Fe78Si9Bl3, Fe40Ni40B20, Fe40Ni40P14B6, Co58NilOFe5SillB16, Fe32Ni36Crl4P12B6, Co66Fe4NilSil5B14, Co76Fe2Mn4Si6B12 and Ni78Si8B14, and crystalline Fe94Si6. A combination of thermogravimetry, optical and electron microscopy, electron probe microanalysis, X-ray diffractometry and differential scanning calorimetry has been used to investigate the oxidation and crystallisation kinetics, oxide structure and composition, oxidation and crystallisation mechanisms and the effect of crystallisation on the oxidation behaviour. The results show that the oxidation resistance at 350 C in air increases in the order Fe40Ni40- P14B6 < Fe94Si6 < Co66Fe4NilSil5B14 < Co58NilOFe5SillB16 < Co76MnFe2- Si6B12 < Fe40Ni40B20 < Si78Si9B13 < Ni78Si8B14 < Fe32Ni36Crl4P12B6. Most of the amorphous alloys obey a parabolic oxidation rate law, but the oxidation kinetics, oxide growth mechanism and resulting oxide structure change sharply when crystallisation takes place in the amorphous alloys. Amorphous Fe78Si9B13 and Fe40Ni40B20 have better oxidation resistance than the corresponding crystalline alloys, while amorphous Fe40Ni40P14B6 and Co58NilOFe5Sil1B16 have poorer oxidation resistance than the crystalline counterparts. Most of the crystalline alloys also obey a parabolic oxidation rate law, except for the crystalline Co based alloys and Fe40Ni40B20, which obey a logarithmic rate law. In most cases, the amorphous and crystalline alloys oxidise to form a fine-scale multiphase oxide scale, except for amorphous Fe40Ni40P14B6, which oxidises to form a whisker-like thick layer of Fe203- In general, ion diffusion through fast transport paths such as grain boundaries and dislocations is the rate controlling process for oxide growth. Different oxidation kinetics and oxide growth mechanisms in amorphous and crystalline alloys of the same composition are caused by micro-chemical segregation of the alloying elements during crystallisation.