The role of goethite in the formation of the protective corrosion layer on steels

The corrosion products formed on carbon and weathering steels exposed in marine, industrial and rural environments in the United States for 16 years have been investigated using Mossbauer spectroscopy, Raman spectrometry and chemical analysis. Mossbauer spectroscopy was used to measure the fraction of each oxide in the corrosion coatings and micro-Raman spectrometry was used to locate and map the oxides to 2 mu m spatial resolution. Mossbauer spectroscopy identified the corrosion products in the weathering steels as 75% goethite, 20% lepidocrocite and 5% maghemite. Raman analysis showed that the corrosion products generally formed as alternating layers containing different oxides. For the weathering steels the protective inner-layer closest to the steel substrate consisted of nano-sized goethite ranging in size from 5-30 nm and having a mean particle size of about 12 nm. The outer-layer close to the coating surface, consisted of lepidocrocite and goethite with the former oxide being most abundant. Electron probe micro-analysis measured significant chromium in the goethite close to the steel substrate. Comparison of the goethite in the corrosion products was made with synthetic chromium substituted goethite with nearly identical microstructural characteristics being recorded. It is concluded that chromium inclusions in the goethite are important for formation of a nano-phase oxide layer which may help protect the weathering steel from further corrosion.