DOI: 10.

1007/s10967-007-0715-y

Journal of Radioanalytical and Nuclear Chemistry, Vol. 273, No.1 (2007) 8590

Corrosion study of heat exchanger tubes in pressurized water cooled nuclear reactors by conversion electron Mssbauer spectroscopy
Z. Homonnay,1 P. . Szilgyi,1 E. Kuzmann,2 K. Varga,3 Z. Nmeth,3 A. Szab,3 K. Rad,3 J. Schunk,4 P. Tilky,4 G. Patek4
1 Department 2 MTA-ELTE

of Nuclear Chemistry, Etvs Lornd University, Budapest, Hungary Research Group for Nuclear Methods in Structural Chemistry, Hungarian Academy of Sciences, Etvs Lornd University, Budapest, Hungary 3 Department of Radiochemistry, University of Veszprm, Veszprm, Hungary 4 Paks Nuclear Power Plant, Paks, Hungary (Received June 30, 2006)

57Fe-conversion electron Mssbauer spectroscopy (CEMS) a sensitive tool to analyze the phase composition of corrosion products on the surface of stainless steel was applied to study real specimens from the Paks Nuclear Power Plant, Hungary. The primary circuit side of the heat exchanger tubes was studied on selected samples cut out from the steam generators during regular maintenance. Mostly Cr- and Ni-substituted magnetite, amorphous Fe-oxides/oxyhydroxides as well as the signal of bulk austenitic steel of the tubes were detected. The level of Cr- and Nisubstitution in the magnetite phase could be estimated from the Mssbauer spectra. It is suggested that CrNi substitution occurs simultaneously so that the inverse spinel structure of magnetite is preserved up to a certain limit which appears to be roughly at [Fe3+]tet[Fe2+1/4Ni2+3/4Fe3+1/4Cr3+3/4]octO4. Further decrease of the iron content of this phase results in the formation of nickel chromite of regular spinel structure, with very low Fe content. This transformation may be responsible for the hybrid structure of the protective oxide layer, being substantially accelerated by previously performed, factory developed and proposed AP-CITROX decontamination cycles.

Introduction Nuclear energy production tends to return into the focus of interest because of the constantly increasing energy need of the world and the green house effect problems of the strongest competitor oil or gas based power plants. In addition to the construction of new nuclear power plants, lifetime extension of the existing ones is the most cost effective investment in the energy business. However, feasibility and safety issues become very important at this point, and corrosion of the construction materials should be carefully investigated before decision on a potential life-cycle prolongation of a reactor. Corrosion products in the primary circuit of water cooled nuclear reactors have been investigated using CEMS and other methods by several groups.14 CEMS (57Fe-conversion electron Mssbauer spectroscopy) is a sensitive tool to analyze the phase composition of corrosion products on the surface of stainless steel,5 giving information mostly from the outhermost 300 nm layer due to the penetration range of conversion electrons. It is well known that the main corrosion product on stainless steel in wet environment under chemically reductive conditions is magnetite (Fe3O4).5,6 Magnetite has an inverse spinel structure: it has Fe3+ ions on the tetrahedral (A) sites and Fe3+ and Fe2+ ions in equal population on the octahedral (B) sites of the ideal unit cell. Iron ions may be easily substituted by other metal ions (Cr3+, Ni2+, Co2+) if the respective elements are present in the steel. Since octahedral sites are crystallographically equal in the unit cell, the Mssbauer
02365731/USD 20.00 2007 Akadmiai Kiad, Budapest

spectrum of magnetite contains only two sextets. One represents the tetrahedral Fe3+ with isomer shift typical to high spin Fe3+ with an internal magnetic hyperfine field B = 49.1 T, while the other sextet has an isomer shift between those characteristic of Fe3+ and Fe2+ with hyperfine field B = 45.3 T).7 The averaged valence state at site B is due to fast electron hopping between Fe2+ and Fe3+ at the octahedral sites. ROSENBERG and FRANKE8 have systematically studied the effect of substitutional disorder on the iron valence states of Fe3xMexO4-like systems (Me=Ni, Co, Cr) using Mssbauer spectroscopy. They have concluded that substitution of Ni2+ or Co2+ into the Fe(B) sites lead to the appearence of sextets with hyperfine fields 47.0, 49.6 and 51.7 T besides the averaged Fe(B) line, so the mixed valency state will acquire more Fe3+ character. For Cr3+ substitution the Fe(B) site became more Fe2+ in character since the spectrum contained three more Lorentzian sextets, besides the Fe(B) magnetite one, with hyperfine fields of 38.2, 41.7 and 44.0 T. This shows that analysis of the Mssbauer spectrum of magnetite formed on the surface of stainless steel can help estimate the substitution level in the spinel structure. Recently, we have reported corrosion study of stainless steel tubes from the steam generators of the Paks Nuclear Power Plant using various analytical methods, and concluded that the protective oxide layer on the primary curcuit side of the tubes has a hybrid structure with substantial mobilty.6,911 We report here, a more detailed CEMS analysis of selected samples in order to find out if the substitution level of magnetite on the surface and the mobility of the protective oxide layer
Akadmiai Kiad, Budapest Springer, Dordrecht

Z. HOMONNAY et al.: CORROSION STUDY OF HEAT EXCHANGER TUBES

may be correlated. Possible relation with previous AP-CITROX6,12 decontamination cycles is also proposed. Experimental The experiments have been performed on numerous (>25) austenitic stainless steel tube specimens (type: 08X18H10T (GOST 5632-61) outer diameter: 16 mm, average wall thickness: 1.6 mm) originating from different steam generators of the Paks Nuclear Power Plant. In addition to CEMS, the samples have been studied by several methods including voltammetry, XPS, SEM-EDX and XRD and such results have been published elsewhere.6,912 The 1.52 cm long tube pieces were cut into two halves along their axes and then flattened gently so that they could be mounted to the CEMS detector. Visible damage was not observed on the surface, or if was, it was painted with an organic paint which completely absorbed conversion electrons and thus prevented false detection of deeper oxide layers or bulk steel. The CEMS spectra were recorded at room temperature with a conventional Mssbauer spectrometer (Wissel) in constant acceleration mode. The conversion electrons were detected with a constantflow type proportional counter specially designed for CEMS technique (Ranger). The counter gas was a mixture of 96% He and 4% methane. A 57Co(Rh) source of 500 MBq provided the -rays. Calibration was done by measuring an -Fe foil in transmission mode, which is the reference of the isomer shifts published in this work. Computer analyisis of the spectra was carried out by using Msswinn 3.0. Lorentzian line shape and common linewidth (within one spectrum) were assumed in all cases. Results and discussion The CEMS results on the specimens cut out from the steam generators resulted in various types of spectra which may be classified in two characteristic groups. In the first group of samples, the Mssbauer spectra were composed mostly of a doublet and a singlet in addition to a very minor sextet if any. Four of such spectra are shown in Fig. 1 as examples. The ramarkable feature of these spectra is the marked presence of the singlet, which is assigned to the bulk steel, and the absence of magnetite, a typical corrosion product of stainless steel in reductive primary coolant. The small sextet sometimes observed may be assigned to magnetite only tentatively because it cannot be resolved to two subsextets due to low intensity. The high intensity of the singlet is difficult to understand because the thickness of the oxide layer on the surface was found to be sometimes more than 86

12 m, and thus conversion electrons from bulk steel should not be able to reach the detector if the corroded surface has a layered structure. Since possible mircocracks on the surface due to shaping of the specimen may account only for a minor part of this signal; it was concluded earlier6,911 that the oxide layer has a hybrid structure: a relatively thick layer composed of a more or less random mixture of grains of iron depleted magnetite (spinel ferrite or chromite), amorphous Fe(OH)3 and steel. The doublet is assigned to amorphous Fe(OH)3 (and/or FeO(OH)), and is present in various amounts in every sample. The second typical group of samples showed Mssbauer spectra with large fraction of magnetite (Fig. 2). However, regular magnetite has a somewhat different Mssbauer spectrum as shown in Fig. 3. The sextet with smaller hyperfine field and averaged Fe2+/Fe3+ character has an intensity twice as high as that of the other because there are two octahedral sites for each tetrahedral site in the unit cell of spinel (Fig. 4). (Differences in Mssbauer-Lamb factors which causes some deviation from the 2 :1 ratio are normally neglected.) In our measurements, although the Mssbauer parameters of the sextets show no noticeable difference from those of pure magnetite, the relative intensities are very different: the intensity of the sextet assigned to site B is anomalously low (Table 1). This shows that the population of Fe at site B decreased, which must be due to substitution of Fe by the most abundant alloying elements of the steel: Cr and Ni. Chromium is expected to show up in the form of Cr3+ ions in a corrosion process, and since the crystal field stabilization energy for Cr3+ in octahedral field is 224.5 kJ/mol in contrast to the tetrahedral field where it is only 66.9 kJ/mol,13 chromium will be substituted solely for Fe3+ at site B. The analogous figures for Ni2+, expected corrosion product of nickel, are 122.1 kJ/mol and 35.9 kJ/mol, respectively, thus nickel will also substitute at site B, however, for Fe2+. As mentioned earlier, ROSENBERG and FRANKE8 found new sextets in the Mssbauer spectrum of magnetite when either Cr or Ni were single substituting elements. Both were found to substitute at site B. That is reasonable since by single substitution, the electron hopping between Fe2+ and Fe3+ becomes unbalanced. We have found no new sextets, only the ratio of sextet A and sextet B changed. Taking into account the site preference of Ni2+ and Cr3+, one can logically conclude that this system (i.e., Cr-Ni steel) offers a unique opportunity for simultaneous substitution of Cr3+ and Ni2+ at site B in the inverse spinel structure of magnetite formed during the corrosion of stainless steel, and this can explain the Mssbauer spectra.

Z. HOMONNAY et al.: CORROSION STUDY OF HEAT EXCHANGER TUBES

Fig. 1. Examples of CEMS spectra indicating hardly any (or no) magnetite on the corroded surface of stainless steel tubes from the steam generators of Paks NPP

Fig. 2. Examples of CEMS spectra indicating large amount of magnetite on the corroded surface of stainless steel tubes from the steam generators of Paks NPP

87

Z. HOMONNAY et al.: CORROSION STUDY OF HEAT EXCHANGER TUBES

Fig. 3. Simulated Mssbauer spectrum (CEMS) of pure magnetite at room temperature, showing two sextets assigned to terahedral (site A, dashed line) and octahedral (site B, solid line) lattice positions

Table 1. Mssbauer parameters of the sextets of Ni- and Cr-substituted magnetite in selected samples; : isomer shift relative to -Fe, B: magnetic field (induction), I: relative spectral area in the Mssbauer spectrum Spectrum A B C D , mm/s 0.38 0.36 0.34 0.35 Sextet A B, T 49.9 49.6 50.0 50.4 I, % 59.9 59.7 43.2 30.6 , mm/s 0.69 0.69 0.63 0.71 Sextet B B, T 46.4 46.1 46.2 46.3 IB/IA I, % 25.4 31.7 21.1 25.6 0.424 0.532 0.488 0.833

Fig. 4. The unit cell of the (inverse) spinel structure for magnetite. Tetrahedral sites (A) are highlighted by indicating Fe3+-O bonds. Octahedral sites (B) contain Fe3+ and Fe2+ with equal populations

Now the question arises how far this simultaneous substitution may proceed. Recording more than 25 spectra on various samples, it is remarkable that in the magnetite rich ones, the relative fraction of sextet B is never observed to diminish below a certain limit, namely, about 4050% of sextet A (Table 1). This may indicate a substitution limit at a composition of roughly [Fe3+]tet[Fe2+1/4Ni2+3/4Fe3+1/4Cr3+3/4]octO4. In the other group of samples the intensity of magnetite (?) seems to drop rather suddenly, and the two sextet description appears to be invalid. To explain these findings, the following picture can be proposed. Since we have several examples where the Mssbauer spectra do not show any magnetically split in Fe-containing phase while the thickness of the protective oxide layer is found to be more than 1 m, the spinel phase covering the surface must be composed of mainly nickel chromite, NiCr2O4 (not detectable by Mssbauer spectroscopy). Nickel chromite has the normal spinel structure,14,15 thus Ni2+ is at site A and Cr3+ is at site B. This structural difference explains why a continuous transition from the inverse spinel Cr/Ni substituted magnetite to normal spinel Ni-chromite is not possible. A smooth internal transformation would involve

88

Z. HOMONNAY et al.: CORROSION STUDY OF HEAT EXCHANGER TUBES

exchange of A site Fe3+ ions with B site Ni2+ ions by diffusion jumps: Fe3+A(Fe2+, Ni2+)B(Cr3+, Fe3+)BO4 Ni2+A(Fe2+, Fe3+)B(Cr3+, Fe3+)BO4, followed by further chromium substitution: Ni2+A(Fe2+, Fe3+)B(Cr3+, Fe3+)BO4
Cr 3 Fe
3

As can be seen in Fig. 5 by the example of three characteristic samples, when the Cr- and Niconcentration increases in the surface oxide layer, the amount of magnetite detectable by CEMS decreases down to even zero. Therefore, the absence of the signal of magnetite in the CEMS spectra can serve as an indication of a quite thick oxide layer composed of normal spinels of high Ni- and Cr-concentration.

Ni2+A(Fe2+, Cr3+)B(Cr3+, Fe3+)BO4, which (the first step) is against the site preference of Ni2+. Therefore, one has to assume that the transformation should occur by dissolution of the inverse spinel type substituted magnetite followed by nucleation and growth of the normal spinel nickel chromite. This can result in a sudden change in the composition of the spinel. Note that since chromium has a very strong preference for the octahedral sites (B), Fe3+ cannot substitute for it easily in nickel chromite. Fe2+ has also preference for the octahedral sites (Fe3+ has no preference at all due to its highly symmetric 3d5 valence shell configuration), thus noticeable substitution for Ni2+ at the tetrahedral site A is not expected either. The obvious result is low solubility of iron in nickel chromite. This explains why we found sextets of very small intensity in many cases, and now these sextets must be assigned to Fe impurity in nickel chromite rather than to magnetite with very low iron content. The formation of Ni-ferrite and Fe-chromite may also be considered; both phases are normal spinels. The high Ni- and Cr-content of the corrosion layer on the steel was verified by EDX measurements.9

Conclusions On the basis of our results we conclude that the protecting oxide layer formed on the surface of the stainless steel tubes in the steam generators of the nuclear reactors has various compositions depending on the operation time and decontamination history. We find that Fe depletion from the surface layer (Fe is the most soluble metal components of steel in the primary coolant) causes transformation of the originally inverse spinel magnetite with low Ni- or Cr-substitution level mostly into the normal spinel Ni-chromite by a dissolution-nucleation process. During this transformation, part of iron may precipitate in the form of amorphous Fe(OH)3 and/or of FeO(OH). This mechanism can explain the hybrid structure of the protective oxide layer which is undesirable for good corrosion resistance. As discussed in our previus papers,911 the surface decontamination by properly performed nonregenerative version of the AP-CITROX procedure (developed by Russian steam generator manufacturer) can initiate (or/and accelerate) the above described undesired transformation process, and the resultant oxide layer may become mobile which can be responsible for delivering large amount of corrosion products to the reactor core.

References
1. J. LIPKA, J. BLAZEK, D. MAJERSKY, M. MIGLIERINI, M. SEBERINI, J. CIRAK, I. TTH, R. GRNE, Hyperfine Interact., 57 (1990) 1969. 2. V. SLUGE , J. LIPKA, I. TTH, J. HA K, M. LEHOTA, I. SMIEKO, Czechoslovak J. Phys., 51 (2005) 909. 3. Z. HOMONNAY, A. VRTES, E. KUZMANN, K. VARGA, P. BARADLAI, G. HIRSCHBERG, J. SCHUNK, P. TILKY, J. Radional. Nucl. Chem., 246 (2000) 131. 4. Z. HOMONNAY, E. KUZMANN, K. VARGA, J. DOBRNSZKY, A. VRTES, P. BARADLAI, G. HIRSCHBERG, J. SCHUNK, P. TILKY, Hyperfine Interact., 139 (2002) 215. 5. Y. UJIHIRA, K. NOMURA, Analyses of corrosion products of steels by conversion electron Mssbauer spectrometry, Research Signpost, Trivandrum, India, 1996.

Fig. 5. Correlation between the Cr-content (first column), Ni-content (second column) measured by EDX, and the magnetite content (third column) measured by CEMS in the protective surface oxide layer of corroded stainless steel tubes. (Note that percentage values ontained from EDX and CEMS have quite different meanings, but it does not effect the observed tendencies)

89

Z. HOMONNAY et al.: CORROSION STUDY OF HEAT EXCHANGER TUBES

6. K. VARGA, The role of interfacial phenomena in the contamination and decontamination of nuclear reactors, in: Radiotracer Studies of Interfaces, Vol. 3, G. HORNYI (Ed.), Interface Science and Technology, Elsevier B.V., Amsterdam, 2004, p. 313. 7. N. N. GRRENWOOD, T. C. GIBB, Mssbauer Spectroscopy, Chapman and Hall Ltd., London, 1971. 8. M. ROSENBERG, H. FRANKE, Philos. Mag., B42 (1980) 419. 9. A. SZAB, K. VARGA, Z. NMETH, K. RAD, D. ORAVETZ, K. . MAK, Z. HOMONNAY, E. KUZMANN, P. TILKY, J. SCHUNK, G. PATEK, Corros. Sci., (in press). 10. K. VARGA, Z. NMETH, A. SZAB, K. RAD, D. ORAVETZ, J. SCHUNK, P. TILKY, F. K RSI, J. Nucl. Mater., 348 (2006) 181.

11. Z. HOMONNAY , E. KUZMANN , K. VARGA, Z. NMETH, A. SZAB, K. RAD, K. . MAK, L. KVR, D. VARGA, J. TTH, J. SCHUNK, P. TILKY, G. PATEK, J. Nucl. Mater., 348 (2006) 191. 12. K. VARGA, P. BARADLAI, G. HIRSCHBERG, Z. NMETH, D. ORAVETZ, J. SCHUNK, P. TILKY, Electrochim. Acta, 46 (2001) 3783. 13. A. R. WEST, Basic Solid State Chemistry, John Wiley and Sons, Chichester, New York, Weinheim, Brisbane, Singapore, Toronto, 1999, p. 108. 14. F. C. ROMEIJN, Philips Res. Rep., 8 (1953) 304. 15. S. KLEMME, J. C. VAN MILTENBURG, Phys. Chem. Miner., 29 (2002) 663.

90