Hyperfine Interactions 57 (1990) 2023-2028

2023

CEMS STUDY OF OXIDE LAYERS FORMED ON STAINLESS STEEL (SUS304 A N D SUS316) Kiyoshi N O M U R A and Yusuke U J I H I R A Faculty of Engineering, The University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo 113, Japan

Stainless steel (SUS304 and SUS316) was chemically treated and heated at various temperatures, and the oxide films formed on the surface were analyzed by conversion electron Mrssbauer spectrometry (CEMS). Three magnetic components of iron species were detected in the top oxide layers of stainless steels heated below 600 ~ and the fine particles of iron oxides were initially produced in the inner oxide layers of the samples heated at temperatures higher than 700 ~ C. Only paramagnetic iron species were detected in the oxide layers of the stainless steels prepared by chemical treatment.

1. Introduction It is known that the heat treatment and chemical oxidation of stainless steel at certain conditions improve corrosion resistance of the substrate by forming the colored films. Colored stainless steel of type SUS304 becomes golden at 400 o C, orange at 5 0 0 ~ red to purple at 6 0 0 ~ purple at 700 ~ and blue above 7 0 0 ~ [1]. X-ray photoelectron spectrometric studies on the colored films on stainless steel treated chemically were reported by Ansell et al. [2]. We reported recently that oxide film on stainless steel works as a p H sensor [3]. Stewart et al. [4] applied C E M S to the analysis of the oxide layer on the enriched S7Fe thin foil of stainless steel (type SUS310), which was oxidized at high temperatures ( > 700~ and reported the formation of a-Fe203 in the chromium depleted layer. But few M r s s b a u e r spectrometric studies have been carried out on the formation of oxide films on stainless steel which was oxidized at low temperature ( < 700 o C) and by chemical procedure.

2. Experimental section
Sheets of austenic stainless steel (type SUS304 and SUS316) were degreased in acetone, and heated in air for 1 hour at 400, 500, 600, 700, and 800 o C. SUS316 contains 3% M o in addition to similar constituent of SUS304, which is composed of 18% Cr, 8% Ni, and Fe balance. The other oxide films were also prepared by immersing stainless steels in the mixture of 2.5 m o l / d m 3 chromic acid and 5.0 9 J.C. Baltzer A.G. Scientific Publishing Company

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K. Nomura et al. / CEMS of oxide layers on steel

m o l / d m 3 sulfuric acid at 70~ 800 MBq of the 5VCo(Rh) source and a gas flow counter [5] were used. Care was taken to prevent samples from electrical charging during the measurement by contacting the substrate to the counter wall. Some data were fit to the sum of Lorentzian.

3. Results and discussion

3.1. OXIDATION IN DRY AIR Oxide films on SUS304: The thickness of oxide films on SUS304 heated for 1 hour increased from 20 nm to 50 nm with the elevation of heating temperature up to 700 ~ C. Iron content in the oxide layer was far less than that in the bulk, but magnetically split peaks were clearly observed in the samples heated below 600 ~ C. The magnetic hyperfine field of iron compounds produced in the oxide films increased with the increase of heating temperature, whereas the intensity of internal magnetic hyperfine field did not always increase in accordance with the temperature. CEM spectrum of a sample heated at 500 ~ was measured at room and dry ice temperatures as shown in fig. 1. Three iron species [isomer shift ( I . S . ) = 0 . 3 7 m m / s , quadrupole splitting (Q.S.)=0.02 m m / s , and hyperfine field (Hm) = 53 T; I.S. = 0.5 r a m / s , Q.S. = 0.2 m m / s , Hin = 30T, and I.S. = 0.2 m m / s and Hin = 31 T] were observed. The species with largest Hin was attributed to a-Fe203 and the remaining two species to a poorly crystalline spinel compound such as (Ni, Fe)O(Cr, Fe)203. Only paramagnetic peaks (I.S. = 0.2 m m / s , Q.S = 0.6 m m / s ) were observed at room temperature in samples heated above 700~ and broad sextet [I.S. = 0 . 0 3 r a m / s , Q.S. = 0 . 8 6 m m / s , and average Hin = 30 T] and doublet [I.S. = 0 . 2 7 m m / s , Q.S. = 0 . 8 6 m m / s ] at dry ice temperature as shown in fig. 2. The doublet observed at room temperature was considered due to superparamagnetism of fine iron oxide beneath the chromium oxide layer. It may also be mixed with chromium, nickel and iron to form (Fe, Cr)203 and NiO (Fe, Cr)203 at the initial oxidation stage, a-Fe203 was produced though the decomposition of the intermediate mixed c o m p o u n d s by a long heating duration. It is considered that the growth of ~-Fe20 ~ in the chromium oxide layer destroyed the smoothened top oxide layers. Oxide films on SUS316: CEM spectra of SUS316 heated at various temperatures for 1 hour are shown in fig. 3. Three iron species, which had hyperfine fields of 28, 34, and 53 T, were found in the sample heated at 4 0 0 ~ These are considered to be due to F e ( I I I ) / F e ( I I ) pairs in octahedral sites and Fe(III) in tetrahedral sites of spinel compounds such as (Fe, Ni)O(Fe, Cr)203, and Fe(III) in columdum structure of o~-Fe203 and (Fe, Cr)203. Schematic changes of oxide films on SUS316 as a function of heating temperature were similar to those of SUS304. However, more iron remained at the outermost surface on SUS316 than on SUS304 heated under 600 ~ Superparamagnetic doublet also was observed

K. Nomura et al. / C E M S of oxide layers on steel

2025

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in the room temperature CEM spectra of the samples heated at the higher temperature than 700 ~ C. There is not an inherent difference of oxide structures between SUS304 and SUS316, although the outermost oxide layer of SUS316 contained more iron species than that of SUS304 as well as m o l y b d e n u m oxide which was distributed in whole oxide layers of SUS316.
3.2. W E T OXIDATION OF STAINLESS STEELS

Stainless steels were treated in a mixed solution of 2.5 m o l / d m 3 C r O 3 and 5 m o l / d m 3 H2SO 4 for several tens of minutes. In the coloring region, chromium

2026

K. Nomura et aL / CEMS of oxide layers on steel

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and dry ice tcmpcraturc C E M spcctra of oxide films on S U S 3 0 4 stainless steel hcated for I hour at 900 o C.

was a little enriched, iron decreased slightly on the outmost oxide films and nickel existed uniformly in the oxide films. Small amounts of sulfur was detected in the top oxide layer. Only a doublet (I.S. = 0.4 m m / s , Q.S. = 1.0 m m / s at RT) appeared in the CEM spectra measured both at room and dry ice temperatures, This iron product was considered to be iron oxyhydroxide containing chromium and nickel. The intensity of the doublet decreased from 20% to 10% with the increase of the immersion time although the chemical state of iron in the oxide film did not change significantly. The oxide films on SUS316 treated in a chromate solution gave the same CEM spectra as those on SUS304. I.S. and Q.S. of the doublet

K. Nomura et al. / C E M S of oxide layers on steel

2027

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Fig. 3. CEM spectra of oxide films on SUS316 stainless steel heated at 400, 500, 600, 700, 800, and

900 ~C. tended to decrease with a temperature of chromate solution. More iron was included in oxide layers of SUS316 than those of SUS304. Molybdenum was present uniformly in the oxide layers of SUS316, although the intensity of fluorecent Mo X-ray tended to decrease with the increase of immersion time. These oxide layers of our samples treated in a chromate solution were different from oxide layers on stainless steel treated under a boiler condition [6].

4. Conclusion

Oxide films, formed on stainless steels by the thermal treating up to 700 ~ or chemical treatingin a chromate solution, showed various shiny colors. The former oxides gave magnetic hyperfine fields in the CEM spectra and the latter gave paramagnetic peaks. At least two iron oxides were observed on the top oxide films on stainless steels heated under 600~ whereas iron oxides could be produced in high dispersed form beneath the chromium rich oxide layers on stainless steel heated at higher temperatures than 700 ~ C. These iron states in the initial oxide films formed on SUS304 and SUS316 heated and chemically treated were clarified by CEMS measurements.

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K. Nomura et al. / C E M S of oxide layers on steel

References
[1] [2] [3] [4] [5] [6] R. Nemoto and K. Horioka, Iron & Steel 71 (1985) S1254. R.O. Ansell, T. Dickinson and A.F. Pover, Corrosion. Sci. 18 (1978) 249. K. Nomura and Y. Ujihira, Anal. Chem. 60 (1988) 2565. I. Stewart and M.J. Tricker, Corrosion. Sci. 26 (1986) 1041. K. Nomura and Y. Ujihira, Hyp. Int. 41 (1988) 681. J. Ensling, J. Fleish, R. Grimm, J. Gruber and P. Giitlich, Corrosion Sci. 18 (1978) 979.