AN INVESTIGATION INTO THE CORROSION BEHAVOUR OF A COMMERCIAL TYPE SUPERFERRITIC STAINLESS STEEL CONTAINING SMALL AMOUNTS OF RUTHENIUM AND

SILVER
A. VAN BENNEKOM, P.M. HUNG AND J.H. POTGIETER* SCHOOL OF PROCESS AND MATERIALS ENGINEERING UNIVERSITY OF THE WITWATERSRAND JOHANNESBURG, SOUTH AFRICA *DEPT. OF CHEMISTRY AND PHYSICS TECHNIKON PRETORIA, SOUTH AFRICA
1. INTRODUCTION It is well known that small additions of PGMs (platinum group metals) to ferritic stainless steels can significantly increase the corrosion resistance of such alloys in reducing acid media (1-12). Tomashov and Chernova (1,2) showed that the addition of PGMs had a marked beneficial effect on the passivation of Fe-Cr-Pd alloys containing varying concentrations of chromium, especially at chromium concentrations greater than 25%. The optimal effect of the Pd occurred at a chromium concentration of 40%. The PGM addition results in a lowering of the hydrogen over-potential, and sometimes also an inhibition of anodic dissolution. This technique to increase the corrosion resistance is known as cathodic modification and its mechanism (13) has been described in detail in the literature. The effect of the bulk concentration of the PGM on the spontaneous passivation of stainless steels has been confirmed by Higginson et al (3) for the Fe-40%Cr-Ru alloy system. Work by Potgieter and van Bennekom (14) has indicated that the corrosion behaviour of two different stainless steels with 40% Cr and 30%Cr is very similar in 10%H2SO4, both with and without varying ruthenium additions. Streicher (7,8) assessed the effect of various PGM additions as well as Ni on the corrosion resistance of an Fe-28%Cr-4%Mo alloy in 10% boiling sulphuric acid. On the basis of his results, a commercial alloy Fe-29%Cr-4%Mo-2%Ni (AL29-4-2) was developed. Recently Scheers et al (12) described the corrosion performance of Fe-29%Cr-4%Mo-2%Ni alloys with various ruthenium additions in pure phosphoric acid and phosphoric acid containing impurities. The good corrosion resistance of these alloys resulted in a patent application for the material in South Africa and other countries (15). The purpose of this paper is to investigate the corrosion behaviour of the Fe-29%Cr-4%Mo-2%Ni alloys with various small additions of ruthenium and silver in sulphuric acid solutions. Silver was included in the investigation because it can also modify the superferric stainless steel cathodically and it costs about one tenth the price of an equal weight of ruthenium.

2. EXPERIMENTAL The alloys were melted in a vacuum induction furnace and rectangular ingots were produced. Each ingot was then hot-rolled at 1100oC through a number of passes to a plate with a final thickness of between 3-6mm. The plates were annealed at 1050oC for 1 hour before they were water-quenched. The chemical compositions of the alloys used in the investigation are summarised in Table 1.
Target Fe-29%Cr-4%Mo-2%Ni-0%Ru Fe-29%Cr-4%Mo-2%Ni-0.05%Ru Fe-29%Cr-4%Mo-2%Ni-0.10%Ru Fe-29%Cr-4%Mo-2%Ni-0.20%Ru Fe-29%Cr-4%Mo-1%Ni-1%Cu-0.20%Ru Cr 28.4 28.1 28.9 28.5 28.7 Ni 2.23 2.31 2.25 2.21 1.10 Mo 4.13 4.02 4.00 4.09 3.93 Ru 0 0.05 0.12 0.21 0.22 Ag Fe-29%Cr-4%Mo-2%Ni-0%Ag Fe-29%Cr-4%Mo-2%Ni-0.5%Ag Fe-29%Cr-4%Mo-2%Ni-1.0%Ag 28.7 29.1 29.4 2.66 2.60 2.49 4.25 4.34 3.86 0.088 0.41 0.85 0.03 0.02 0.02 0.020 0.015 0.012 0.004 0.003 0.004 Cu 0.02 0.02 0.02 0.02 1.0 C 0.020 0.012 0.005 0.006 0.017 N 0.004 0.002 0.003 0.003 0.003

Table 1. Chemical composition of alloys used in the investigation 2.1. Immersion tests Specimens of nominal dimensions 30 mm x 40 x 5 mm were cut from each plate. They were polished to a 120 grit finish on SiC paper, rinsed in distilled water and degreased with iso-propanol. After weighing and measuring their dimensions, the coupons were placed in open glass cradles and immersed in sulphuric acid solutions of varying concentrations at boiling point. The period of exposure depended on the corrosion rates experienced, but varied from 30 min in cases where active corrosion occurred to 48 hours for alloys that passivated in the acid solutions. The coupons were then removed, cleaned mechanically with a nylon brush and rinsed with distilled water and isopropanol before their mass loss was determined. The mass loss results were converted to corrosion rates (mm/year), and the results from these tests are summarised in Table 2. Table 2: Corrosion rates (mm/a) of the various Fe-29%Cr-4%Mo-Ni-Ru alloys in boiling H2SO4
Alloy 10 Fe-29%Cr-4%Mo-2%Ni-0%Ru Fe-29%Cr-4%Mo-2%Ni-0.05%Ru Fe-29%Cr-4%Mo-2%Ni-0.10%Ru Fe-29%Cr-4%Mo-2%Ni-0.20%Ru Fe-29%Cr-4%Mo-1%Ni-1%Cu-0.20%Ru Fe-28%Cr-4%Mo-0.2%Ru Fe-29%Cr-3%Mo-14%Ni-0.2%Ru Fe-29%Cr-4%Mo-2%Ni-0.1%Ag Fe-29%Cr-4%Mo-2%Ni-0.5%Ag Fe-29%Cr-4%Mo-2%Ni-1.0%Ag 0.0083 0.0012 0.0008 0.0006 0.0152 0.2300 0.000
(8) (17)

[H2SO4] (%) 20 1.733 0.0205 0.0031 0.0027 0.0518 3.719 1.560 0.4726 30 1.884 1.044 0.4219 0.0645 0.0892 40 4687 4099 12.93 3550 -

0.0227 0.0333 0.1183

2.2. Electrochemical measurements An insulated copper wire was spot welded to the back of a sample of approximately 1.5cm x 0.30.5cm before it was mounted in fibre-glass resin. Each sample was then ground to a 600 grit finish, in accordance with the ASTM-G59 standard (16). The metal surfaces to be exposed were degreased ultrasonically in iso-propanol and the edges of each specimen masked off with a commercial glue to prevent crevice corrosion. The sample was masked off in such a way that the remaining area was approximately square or rectangular and as large as possible, which allowed the exposed area to be measured as accurately as possible prior to testing. A standard glass cell was used with platinum wires acting as counter-electrodes and a Haber-Luggin capillary forming the junction with a saturated calomel electrode (SCE). High purity argon was bubbled through the test solution for one hour prior to testing and throughout the duration of the test to ensure that the solution remained de-aerated. Prior to initiation of the scans, all samples were polarised at 700mV for 10 minutes to remove any oxide layer from the surface. Potentiodynamic scans were then conducted on a Princeton 273 potentiostat, starting immediately after polarisation at 250mV and using a scan rate of 0.1 mV/sec. The scans were terminated at 1600 mV. All potential values reported were with respect to SCE. The temperature was maintained at 50o2oC in a water bath, while scans were carried out in 50% sulphuric acid, 50% sulphuric acid + 250 mg/l chloride and 50% sulphuric acid + 1500 mg/l chloride solutions. Three scans were performed for each alloy and the average of these results were calculated. These results are summarised in Tables 3-5. No IR compensation was used, since all the solutions were highly conducting. Standard commercial software (Model 342C) was employed to calculate important electrochemical parameters as well as corrosion rates via the linear polarisation method.
Alloy Fe-29%Cr-4%Mo-2%Ni-0.%Ru Fe-29%Cr-4%Mo-2%Ni-0.05%Ru Fe-29%Cr-4%Mo-2%Ni-0.10%Ru Fe-29%Cr-4%Mo-2%Ni-0.20%Ru Fe-29%Cr-4%Mo-1%Ni-1%Cu-0.20%Ru Fe-29%Cr-4%Mo-2%Ni-0%Ag Fe-29%Cr-4%Mo-2%Ni-0.5%Ag Fe-29%Cr-4%Mo-2%Ni-1.0%Ag Ecorr (mV) -387 -372 -350 -312 -212 -376 -384 -389 Icorr (A/cm 2) 7500 10 861 8663 5525 1382 8069 6775 5584 CR(mm/a) 86.7 125.5 99.3 63.9 16.0 93.3 78.3 64.5

Table 3. Some electrochemical parameters derived from the polarisation responses of the various alloys in 50% H2SO4 at 50oC
Alloy Fe-29%Cr-4%Mo-2%Ni-0%Ru Fe-29%Cr-4%Mo-2%Ni-0.05%Ru Fe-29%Cr-4%Mo-2%Ni-0.10%Ru Fe-29%Cr-4%Mo-2%Ni-0.20%Ru Fe-29%Cr-4%Mo-1%Ni-1%Cu-0.20%Ru Fe-29%Cr-4%Mo-2%Ni-0%Ag Fe-29%Cr-4%Mo-2%Ni-0.5%Ag Fe-29%Cr-4%Mo-2%Ni-1.0%Ag Ecorr (mV) -363 -365 -361 -349 -345 -358 -352 -359 Icorr (A/cm 2) 2438 7730 5278 5476 2740 7711 9933 5367 CR(mm/a) 28.2 89.3 61.0 63.3 31.7 89.1 114.8 62.0

Table 4. Some electrochemical parameters derived from the polarisation responses of the various alloys in 50% H2SO4 + 250mg/l Cl- at 50oC

Alloy Fe-29%Cr-4%Mo-2%Ni-0%Ru Fe-29%Cr-4%Mo-2%Ni-0.05%Ru Fe-29%Cr-4%Mo-2%Ni-0.10%Ru Fe-29%Cr-4%Mo-2%Ni-0.20%Ru Fe-29%Cr-4%Mo-1%Ni-1%Cu-0.20%Ru Fe-29%Cr-4%Mo-2%Ni-0.1%Ag Fe-29%Cr-4%Mo-2%Ni-0.5%Ag Fe-29%Cr-4%Mo-2%Ni-1.0%Ag

Ecorr (mV) -335 -359 -360 -320 -314 -336 -351 -358

Icorr (A/cm 2) 1139 2643 3402 1254 1312 2765 4078 2286

CR(mm/a) 13.2 30.6 39.3 14.5 15.2 32.0 47.1 26.4

Table 5.

Some electrochemical parameters derived from the polarisation responses of the various alloys in 50% H2SO4 + 1500mg/l Cl- at 50oC

3. RESULTS AND DISCUSSION 3.1. Immersion tests: The values summarised in Table 2 clearly illustrate the beneficial effects of the Ru and Ag additions on improving the corrosion resistance of the various alloys, especially with increasing aggressiveness of the corroding solution. In the group of alloys containing ruthenium additions, the increase in Ru concentration always results in a decrease in the corrosion rate in the various sulphuric acid solutions. This decrease varies between one to three orders of magnitude for the alloy containing 0.2% Ru as compared to the base alloy without any PGM addition, and is normally two orders of magnitude in most solutions. In the two alloys both containing 0.2% Ru, the one with the higher nickel concentration is significantly more corrosion resistant in all the sulphuric acid solutions up to 40% than the one containing copper also. All the alloys containing ruthenium additions, as well as the base alloy, display low corrosion rates in sulphuric acid solutions up to 30%. Only upon exposure to 40% sulphuric acid at boiling point does the alloys seem to undergo active corrosion with corresponding high corrosion rates. Compared to a similar type of alloy with no nickel addition, the currently investigated alloys all display a lower corrosion rate, even the base alloy without any ruthenium. This confirms results obtained previously by Streicher (8). However, compared to an alloy of similar composition (17), but which has a much higher nickel content, the alloys in the current investigation display a higher corrosion rate. Similar trends to the ones described so far were also observed in the alloys containing silver additions instead of ruthenium. The beneficial effect of an increasing silver concentration in the alloy is especially evident in the 20% H2SO4 solution. In this particular solution the alloy containing the lowest silver concentration starts to display active corrosion, while the one with the highest silver content still passivates in a boiling 20% H2SO4 solution with a correspondingly low corrosion rate. However, none of the alloys containing silver had as good corrosion resistance in the sulphuric acid solutions as the group containing ruthenium additions. In some cases the corrosion resistance of the alloys containing silver were comparable in magnitude to that of the basic alloy without any noble metal additions and mostly are at least two orders of magnitude higher than that of the alloys containing various ruthenium concentrations. The results obtained from the immersion tests illustrate the suitability of the Ru containing alloys in sulphuric acid environments and supports previously reported work by McEwan et al (18).

3.2. Electrochemical investigations: Since all the potentiodynamic scans display characteristic stainless steel in sulphuric acid behaviour with active to passive transition upon polarisation, no potentiodynamic curves are shown and only characteristic electrochemical parameters obtained from them are summarised and discussed. The corrosion potentials for the alloys investigated in various solutions are graphically represented in Figures 1 to 3. Due to the aggressiveness of the solutions, all the potentials display fairly electronegative values and no spontaneous passivation occurred. In all the solutions investigated, it was clear that especially the 0.2% Ru additions displaced the corrosion potentials towards more electropositive values. This phenomenon is best illustrated and most pronounced in the sulphuric acid solutions without chloride additions. In all the solutions investigated the alloy with the copper addition displayed the least electronegative corrosion potential. In very aggressive corrosion conditions the additional copper alloying is therefore distinctly beneficial. The alloys containing silver had similar corrosion potentials to the basic alloy and the ones containing 0.05% Ru and 0.10% Ru. No displacement of the corrosion potential to less electronegative values was observed for any of the alloys containing silver. If anything, the presence of silver seems to be more detrimental than beneficial.
Alloy (base: 29% Fe, 4% Mo, 2% Ni) 0% 0.05% 0.10% 0.2% Ru -200 E corr/mV -250 -300 -350 -400 1% Ni, 1% Cu, 0.2% Ru 0% 0.50% 1% Ag

Figure 1. Corrosion potentials of various Fe-29%Cr-4%Mo-2%Ni alloys containing noble metal additions in H2SO4 An examination of the summarised corrosion current densities and the corrosion rate values calculated from them in Tables 3 to 5 support the trends observed in the corrosion potentials. In all the solutions to which the alloys were exposed, an insufficient amount of Ru (<0.2%) led to an increase in corrosion rate. This can be ascribed to the increased efficiency of the cathodic hydrogen evolution reaction and is in agreement with similar results reported previously in literature (9). The same phenomenon is observed in the alloys containing silver additions. In both groups it is only in the 50% H2SO4 solution without any chloride additions that the highest concentrations of the noble metal additions increase the corrosion resistance to higher levels than that observed in the base alloy. This result is interesting since it could mean that the silver alloyed steels are not as corrosion resistant as they could be if the silver addition was greater than 0.85%. Unfortunately, increasing the silver addition further will have a negative influence on the cost of the steels and as such there

would be no present justification for replacing ruthenium additions with silver. Since the possibility exists that increased silver alloying could improve the corrosion properties of these stainless steels, and since corrosion is purely a surface phenomenon, research is underway to silver plate some stainless steel components and then to thermally diffuse the silver into the steel structure by simple heat treatment processes. Once again the copper addition in the Ru containing alloy group caused a significant increase in the corrosion resistance compared to the base alloy. The ruthenium additions to the basic steel seem to be more effective in increasing the corrosion resistance than the silver additions. This confirms the mass loss results obtained in the investigation. The similarity in corrosion rates between the sulphuric acid solution and the solutions containing chloride implies good pitting resistance in all these alloys, an observation that is supported by previous work of Streicher (8).

Alloy (base: 29% Fe, 4% Mo, 2% Ni) 0% 0.05% 0.10% 0.2% Ru -335 -340 E corr/mV -345 -350 -355 -360 -365 1% Ni 1% Cu 0.2% Ru 0% 0.50% 1% Ag

Figure 2. Corrosion potentials of various Fe-29%Cr-4%Mo-2%Ni alloys containing noble metal additions in H2SO4 + 250 mg/l Cl-

Alloy (base: 29% Fe, 4% Mo, 2% Ni) -290 -300 E corr/mV -310 -320 -330 -340 -350 -360 1% Ni 1% Cu 0.2% Ru 0% 0.05% 0.10% 0.2% Ru 0% 0.50% 1% Ag

Figure 3. Corrosion potentials of various Fe-29%Cr-4%Mo-2%Ni alloys containing noble metal additions in H2SO4 and 1500 mg/l Cl-

4. CONCLUSIONS The following conclusions can be drawn from this investigation: 1. Noble metal additions of ruthenium and silver can increase the corrosion resistance of Fe29%Cr-4%Mo-2%Ni-alloys. However, only at a 0.20% Ru level is this improvement really significant and worthwhile The substitution of half of the nickel with a similar amount of copper does change some of the electrochemical parameters, but does not seem to have a major beneficial or detrimental effect, except in severely aggressive conditions (40% H2 SO4 at boiling point), where the effect is decidedly detrimental. Silver additions, even in much larger concentrations than ruthenium, are not as effective as the latter to improve the corrosion resistance of the base alloy. Indications are that both the ruthenium and silver alloyed stainless steels are resistant against pitting corrosion.

2.

3.

4.

5. ACKNOWLEDGEMENTS The authors AvB and PMH gratefully acknowledge Minteks (Council of Mineral Technology) contribution to their research efforts in the area of cathodic modification of various stainless steels. 6. REFERENCES
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. N.D. Tomashov and G.P. Chernova, Prot. Met. (USSR)., 9, p.379 (1975) G.P. Chernova and N.D. Tomashov, Corrosion, 34, p.445 (1978) A. Higginson, R.C. Newman and R.P.M. Proctor, Corros. Sci., 29, p.1293 (1989) S.C. Tjong, Appl. Surf. Sci., 44, p.7 (1990) S.C. Tjong, Surf & Coat. Tech., 38, p.325 (1989) S.C. Tjong, Werkstoffe und Korrosion, 40, p.729 (1989) M.A. Streicher, Plat. Metals Rev., 21, p.51 (1977) M.A. Streicher, Corrosion, 30, p.77 (1974) G.J. Biefer, Can. Metall. Quart., 9, p.537 (1970) V.S. Agarwala and G.J. Biefer, Corrosion, 28, p.64 (1972) J.H. Potgieter and M.U. Kincer, S. Afr. J. Chem., 44, p.47 (1991) P.V. Scheers, J.J. McEwan and D. Knight, Corr. & Coat., p.4 (Oct. 1994) J.H. Potgieter, W. Skinner and A.M. Heyns, J. Appl. Electrochem, 20, p.711 (1990) J.H. Potgieter and A. van Bennekom, Can. Metall. Quart., 34, p.143 (1995) S.A. Patent Application, No. 93/8889. ASTM Standard G59, Annual Book of ASTM Standards, Vol. 03.02 (1988) J.H. Potgieter and H.C. Brookes, Corrosion, 51, p.312 (1995) J.J. McEwan, D. Knight and P.V. Scheers, Proc. XVth CMMI Conference, Johannesburg, S.A., SAIMM, Vol. 2, p.151 (1994)

Dr. Andre van Bennekom

I obtained my BSc degree in Physical Metallurgy from Wits University in 1989. Both my MSc (1990) and PhD (1995) degrees were obtained at Wits University and focused on various aspects of corrosion and stainless steel alloy development which led to the development of commercially produced low nickel Cr-Mn-N duplex stainless steels. I was awarded the SASOL medal (1995) and received a silver medal from the Southern African Corrosion Institute (1998) for this research. Apart from lecturing and research activities, I am involved in industrial consulting and have completed in excess of 150 failure and research reports, covering the fields of corrosion, failure investigations, stainless steels, alloy development and welding. To date 38 technical papers have been published and/or presented in both local and international journals. I am currently employed as senior lecturer at the University of the Witwatersrand where I am head of the Corrosion Research Group and co-ordinator of the European Welding Federation's Welding Engineers Course. I am also employed on a part time basis as a consultant to the Council of Scientific and Industrial Research (CSIR) where I am involved in a spectrum of research and consulting activities.