K.E. García

New analysis of the Mössbauer spectra of akaganeite

The Mossbauer spectra of akaganeite have always been interpreted considering both the tetragonal structure and the chlorine content. However, very recently it has been suggested that the crystallographic structure is not tetragonal but monoclinic, thus another interpretation for the Mossbauer spectra is required. For this purpose, we have prepared and characterized by several techniques synthetic akaganeite. Our results suggest that the two crystallographic sites required by the monoclinic symmetry are not distinguishable in the paramagnetic state as previously assumed, but they are only discernible in the low temperature magnetic region. At room temperature the spectrum is fitted with two doublets whose origin is related to the chlorine content, i.e. one Fe site assigned to Fe3+ ions located close to chloride ions and the other Fe site to those located close to chloride vacancy sites. The low temperature spectra can be adequately fitted with four sextets, whose hyperfine parameters must be subjected to some constraints. The origin of these components is related to the two different crystallographic sites and to the chlorine content. In-field Mossbauer spectrometry at low temperature suggests that the magnetic structure behaves as a system which consists of two asperimagnetic-like structures antiferromagnetically coupled, and not as a collinear antiferromagnet as usually assumed.

Mossbauer characterization of rust obtained in an accelerated corrosion test

We have performed drying-humectation cyclical processes (CEBELCOR) on eight A36 low carbon steel coupons in NaCl solutions containing 1×10−2 M and 1×10−1 M concentrations. The main purpose of these experiments is to contribute to the understanding of the conditions for akaganeite formation. Additionally, and with the idea to perform a complete characterization of the rust, this work also considers the formation of other iron oxide phases. The corrosion products were characterized by Mössbauer spectroscopy and X-ray diffraction techniques. Gravimetric analysis demonstrates that the coupons presented high corrosion rates. Magnetite/maghemite was common in the rust stuck to the steel surface, whereas akaganeite was present only in traces. In the rust collected from the solutions, i.e., the rust that goes away from the metal surface easily, a magnetite/maghemite was not present and akaganeite showed up in larger quantities. These results support the idea that high concentrations of Cl− ions are required for the akaganeite formation. We concluded that akaganeite is not easily bonded to the rust layer; this may lead to the formation of a less protective rust layer and to higher corrosion rates.