CORROSION RESISTANCE OF NICKEL-CONTATHING ALLOYS TH PETROCHEMICAL EXVIROMMENTS Gaylord D. smith Ince Alloys Iaternational, inc. 3200 Riverside Drive Huntington, WY 25705 ABSTRACT Nunezous nickel-containing alloys possess a desirable combination of properties vital to long tern dependability within petrochemical ané refinery plants. Critical to many operations is the requirement for elevated tenparatire sulfidation resistance under either reducing or oxidizing environments. This paper surveys the role of materials, environmental factors, alloying elements and the formation of protective seales on'the performance of selected nickel-containing alleys. Keyaord: alloying, nickel-centa: ing alleys, scales, stainless steels, sulfidation xurRopucTION The literature defines sulfidation as the corrosive attack of a matal or alloy when exposed to a sulfur-bearing atmosphere at elevated temperature leading to the formation of metal suifide(s) corrosion products.“! Since virtually all physical sources of enercy (including their waste products) contain sulfur in various forms, the need for alloys registant to sulfidation is cbvicus. Sulfidation within the petrochexical and refining industry has been a matter of increasing concern in recent years as the demand for inproved, more efficient processes expand to maet ever changing patterns of available energy seurces and stricter end-product and plant emission specifications.) Sine sultidation resistance is ultimately related to protective scale formation, it is the purpose of this paper to exanine che role that scales pley in the process of sulfication and to gain some daqrec of insight into che contyibution chat typical alloying elements make to scale characteristics. Without a working knowledga of scale behavior, proper alley selection is difficult and improved alloy development efforts Will be hit of mise at best. Scns guidelines for koth alloy selection and development will be presented.G2NERAL CHARACTERISTICS OF SULPIDATION Sulfidation behavior of metals and alloys is vary similar to that of oxidaticn but with several notable differences. Perhaps the wost important of these differences ie the rate of reaction as compared to that of oxidation as shown in Figure 1." The rate Of sulfidation is commonly many Grdars of magnitude faster than oxidation and ERs sorrasion products much sore complex, thereby implying a degree of mechanistic benavior syen more difficult to unravel than thet asscciated with oxidation. Contrary Fa General oxidation rates which ars aneliorated by low suygen potentials, the rate of culfidation becomes increasingly more severe as the oxyyen partial pressure is reduced, Tneldeutiy, it is in these high sultur/low oxygen potential environments that enhanced Corrosion resistant alloye are needed. Unlike oxide ecales which have melting points higher than the melting temperature of the alloy on which they form, sulfiea scales have comparatively lower melting points than their base alloy, Figure 2 showe the influence of underlying nickel-iren-chremiun composition on the melting point of tha sulfide scale formed. Increasing iron and chromiun contents raise the melting point of the sulfide scale for any given nickel 16 Higher molting point scalae should be expacted to have lower self-diffusion rates at typical service temperatures, Tt ohould be mentioned that the self-diffusion coefficients for sulfides ara substantially greater than thone of their corresponding oxides. Whilo inforisation on oxidation mechanisms and oxidation products are relatively abundant, the paucity of fundamentel information on sulfidation rates and mechanisnd coupled with a scarcity of physicochemical properties of sulfides (tharmechonical data, diffusion rates, defect chondstey, ee.) has impeded an indepth understanding of sulfidation and frustrated a systematic, quantitative approach to alloy devalopnent for this service Before focussing on the performance of typical commercial nickel-containing alloys, the thermodynamic and physicochemical proparties of the sulfides of nickel and its common alloying elements warrant review. Table 1 liste some cf the acaic-forming pounds sf interest, their free energy cf formation and the partial pressure ob sulfur for H/MS equilifrium (where M represents the metal and/or ita cation), It would appear based on exaninaticn of the freo energy of formatien data that a Large nunber ef alleying elemento will preferentially react with sulfur avez the reaction ot nickel br iron te term a sulfide. Table 2 lists for these same compounds, the Pilling- Bedworth ratio, defect stricture type, malting point and, in come cages, the matal/ metal oulfide (u/s) eutectic neiting temperature. The Pilling-Bedwort! ratio ia a general guide that predicts a protective scale if the molecular volume of the sulfide is greater than unity. However, high ratica may indicate a tendency for aduerent scales to develop stresses leading to spallation. The nickel-nickel sulfide eutectic malting point of 645°C and the iron-iron sulfide eutectic melting point of 98°C poce & potentially limiting condition for alloys containing these elements. Corrosion rates gan increase dramatically when a liquid phase exists either within tha scale or at tha Scale/alloy interface. Tablo ? compares the self-diffusion cocfficienss for the fides ond oxides of cobalt,nickel, iron, chromium and aluminum. Of key importance, is the fact that selr-ditrusicn thrcugh aluminum sulfide is orders of magnitude less than that through the sulfides of cobalt, nickel, iron and chromium. Tucnspert Gharacterieticos deveud on the defect tipo and’ since mast sulfides are. non- steichiometric, the way is paved for active inward and outward diffusion machaniene. Marker studies by Stafford and Wanpton show that cations are mobile in CeS incicating scale growth at the scele/environment interface.” additionally, they found Crs, being a *n* type semiconductor, allows inward sulfur diffusien via anion defects ‘in the sulfide lattice, Missing thus far is any corralation of thermodynamic or physicochemical properties with actual perfomance data. Tha complexity of the interaction of these properties over time in any given environment makee it highly unlikely that any attempt in this direction will prove completely successful. Rather {he approach being taken here is to settle on limited variations of the test cordit ions and attempt to expinin performance differences on ehangee in composition. These chances in compositicn cre defined by che list of commerical alicys presented in Table 4. Frequent retreat to literature citations will supplement the empirical resulte. HENEROGEN-NDROGEN SULFIDE BASE ATMOSPHERES Practically speaking, most reducing atuespheres containing HS in the pstrechenical industry eleo contain varying amounts of H:, CO, CO, and W,.'The effect SE hydrogen is to potentially reduce the scale, thereby creating a porous structure which parite both rapid inward and outward diffusion, Varying ancunts of GO and CO, Will aler the carbon activity and oxygen potential and thersby affecting tha rate and type of scale formation. Corrosion data obtained by Xu, et al., for alloy S00R in such an environment is presented here." The room temperature (RT) composition of the gas 24/2mixture by volunc ic 27.68 fy, 0-12 HS, 20-88 Co, 20.48 CO., bal. N;. Gas aquilibriue at 850°C ds Fa = 1.5 x 10 Pa, Py = #.3 x 10" Pa and =, = 0-03. Figuxe 3 prosante the thermodynamic phas® stability diagran for clenental nickel, iron and chromium ae B50ee and pinpoints the locatioa in the diagran of the test a:masphess deacribad above, Figure 4 shows the rate of mass change of alley S00K in this test envirouest, An increasing rate of corrosion ie scan te begin in 3Sn. At the completion ot the so test, large nodules were observed on the specimens. Whe ncdule frer areas of the sale were composed of a Cr,0, subscale capped with a layer of (¢z,Fa,Ma) sulfides, The cutee layer sulfides form dus to the outward migration of cations from che substrate reacting with 1,6. The composition of the nodules varies with time and is shown schenatically in Figure 5. Inivielly ¢xs is formed principally over grain boundaries. While over the inverior surtaces ot the grains and dom some grain and twin boundaries, the M3 reacts to form complex (Cr,Fo,Mn)oulfides. Over tine, nickel diffuses through the porous gulfide nodules and forms a layer of liquid Ni,S, (>645°C) on top of the acdulec and in any cracks with the neditles that are exposed to the ourface. By the time of the completion of the 96h test, a Fes layer is observed above the Ni,S, suggesting the prasence of complex diffusion kinetics and continually varying equilibria within the nodules over timo. Any liquid Mi,¢, that forms within the scale or substrate is likely extruded te an open surface due to the larger volume ot the liquid sulfide. The rapid «diffusion rate of iron results in thie element ultimataly dovoloping FeS us the outer most layer of wach nodule, Corrosion data for ¥j-H,S environments are presented e@lsmuhere in this paper howing the effect of ineraasing tenperature at several levels of is trom 0.5 to 6.0%, Hydrogen sulfide corrosion rates can be ameliorated in mixed oxidant envixonnents where corrosion products other than sulfide scales can possibly farm. Data for such, an environment is given in Table 5. The inlet composition is Hy, 45#¢o,, 1.0tH¢ and tha gaqullibrium Py = 1.5 2 10~ Pa, PL, 2 0.56 « Pa and a, = 0.0099 at aaécc. sezuciny of these 1000 hour tect data shows = number of potential benefits to be derived trom alloy composition. in the stainless steels (30¢ and 110), higher chromium lavals are beneficial without defining the contribution of the increased nickel content. High nickel austonitics (alleys B00H, 320, Ds and 803) also benefit trom increasing chromium but not from increasing silicon. Nickel-pase alloya can parfarm catistactoxily with sduquate chromium levels end/or @ combination of chromius aad yetria (Hh 75a and 758), Where yttria io believed te improve scale adnesion and partially block inward and vutward grain boundary diffusion. Outstanding sulfidation vesistaace is achieved with. 4 combination of iron, chromium, aluminum and yetria (MA 956), Mass change data for eight nickel-containing alloys in If,-6tH,S as a function of increasing tonperature are given in Figures 6, 7 and 8. the general ranking of performance does e Cure despite the ainost five-fold inerease in hase change tor most of the alloys. Since negativa mags change values reflect loss of sound metal through scale foxmation and epsilation, the mass gain data of alloys 617 and 625 suguest more optimal scale behavior, i.e, parabolic sullfidation rates coupled with @ high degree of scale adhesion capable of resisting scale growth and therm lly induesd ctrocscs which cause opallation. Fluctuating mass change curves reflect spallation tendencies, very evident for the 304 and 321 stainless stecls and alleys £25 and 601. The increasing rates cf mace lose for all the alloys, except alloys 617 and 625, predict the eventual sccurance of complete failure by brakaway carrasicn- SULFUR DIOXIDZ-oxYGEN BASE ATMOSPRERES An S0,-0, containing atuespberes, the stable phases for nickel and izon are often Eheixy sulfates.(*H! thie layer of thin sulfate is generally nonprotective and senducive for high corrosion rates. Luthra and Worvell Found that this scale oftea contains a network of sulfides which provide = rapid diffusion pach for cations. ™ Chromiun-bearing alloys will add Cr,0, plus CxS to tne scale, altering corrosion rates fevorebly. Using the sulfidation resistance and scale-forming tendencies of alloy $00H as @ reference, the influence of alloy elenents jas found in other conuercially established alloys) were examined. Xu, ot al,, using an atucosphere of 2 parts §0, and i part 0; (at RT) examined scale formation on alloy S00E at 750°C." ‘Tha total Pressure in their furnace was 2.03 x 10° Pa veculting in an equilibrium atmosphere with Pa = 2.33 x 104 Pa and Py = 1.9 x 10% pa at 750°C. Pigure 9 presents the thermodynamic phase stability diagran for alencntal nickel, iron and chromium at 750°C 24/3gud shows the location in the Giagram ot this test atmosphere. The rete of mass change during the first 75h ie shown in Figure 10. Lack of a amccth rete of increase dn mass gain ic attributed to scale spallatioa beginning as carly as about 10 houre into the test, Following exposure, x-ray diffraction studies (XRD) reveal that the ecale contains Cr,0,, ecr.0,, FeS, Wi,S, and (Mi,Fs),(s0,),. Cx,0, conetitutes the bulk cf the subscale. Guall fragments of €rj0;, remnants of the initially tormed scale, can also be found near the cuter layer of Fecr.0,. eS and Ni,S; nodules exist theougheut the seale but no evidence of the Ni/Ni,S, eutectic is ebesrved. Inward sulfur micration which penctrated czacks in the Cr,0, subscale diffused down grain and twin boundaries forming Crs. The general morphology of the scale at the duration of the tost ia depicted in Figure lic, while the progressive eteps in the development of thio scale axe shown in Figures lls and 11k. Initially, simultansous oxidation of Fed, NiO and Cr,0, occurs 4s shown in Figure Ja, The reaction ef Feo with Cr,0, then results in a surface layer of FeCr,0, as shown in Figure Lib. “Reaction of these oxides with So, from tha tast atmosphere results in surface nodules vith a thin outer layer of nickel and izon sulfates, The sulfates have reacted with the outward diffusing nickel and iron to form an oxida and sulfide as shown below: SNL + 2NiSO, = ENE + Ni,S, a 10Fs 4 Po,(80,), = 3F 4,0, + ares Also depicted in Figure lib is a crack reflecting this tendency of Cr,0, scalos to erack on iron-base substrates. Cracking and cpallation of ¢r,0, scales’ on iron-chromium alloys has been studied by Salisbury and Birks for various atmcapheres.!” These cracks allow $0, direct access to tha aubstrate ultinately forming nickel and iron sulfides which can undercut the iniriel layer of Gr,0, and lead to further cracking and seale spallation, Development of the subscale of Cz,0, is not completely protective because of thin tendency to develop cracks CxS stringers form within the substrate, perhaps by the dissociation of Ni,S, or eS leading to a sufficiently high partial preasaura of sulfur to form Crs. Ingress of 80, through the porous sulfides of the scale, alao cculd be a mechanian by which the pertial pressure of oulfur iy increased through an oxidation zeaction with the elements: of the substrate freeing the sulfur fron the 0, Comparison of the development of the actual scale can be made with the thermodynamic phase-stability diagrans for chromium, nickel and iren at the sane tenperature in Figure $. Fouilibriun between the scale and tne environment only partially explains the chain of complex events occurring daring sul fidatien/aesdation- Corrosion kinetics and the rates of cation and anion diffusion also play major roles in scale formation, Mass change data for a number of comercial alloys with varying nickel and chromium contents are presented in Table 6 for exposure in aiz-Z¥S0,-54H.0 for 1000 hours at 700°C, 850°C and 1000°C. The low mse changa data reflect tho ability of oxidation products to retard eulfidation. Only 304 stainless steel failed to maintain a positive rate of mass change. ‘THE ROLE OF ALLOYING ELEMENTS IN SULEIDATION RESISTANCE Given the fact that most eulfuy-containing atnessheres axe dictated by process conditions, process modification to increase an alloy’s acceptability is usually not an option. Consequently, the corrosion engineer must turn to alternative alloys to gain satisfactory corrosion resistances. interest now is the imoact that various alloys and ¢lloying siements make on sulfidaticn resistance ever that of our reference material, alloy 800E The conpositicn of che elloys of interest for this comparative study are listed in Table ¢. Mass change data for these slloys fer beth typical reducing and cxidicing sulfidation environments are presented in thiz paper. Based on chase data end reported L explain the contribution that various elements Literature, an effort hes been mace ©: make to scale characteristics and sulfidation vosicsance- EPPECT OF CHROMIUM ,Huswee reported the parabolic retes of sultieation for pure chromium (K, = 8.0 X 10" Fens), iren-208 chronium (K, = 9.8 x 10% genet) and that of nickel-208 s2ar4chromium Uk = 8.8 x 10% gions“) at 1000°C in a 1.0 % 10° Pa atmosphere of culfur, thereby suggesting that incrassins ckroniun content in ivon- and aickel-base alleys 16 likely to be beneficial." this is born cut in Tables 6 ane 7 by comparing 364 stainless steel cata with that of 310 stainless ctesl for keth oxidising and reducing sulfidation environments. Wancock examined ths affect of increasing chronius content in nickel-chromiun alloys in both 100% $0, and HS envirenments and found a similar benefit for increasing chromium levels as shown in Figure 12." "while chromium has a high affinity for sulfur and its sulfide has 2 high melting paint, the attack of chyomium by euléar ia minimal once a CrS scale is formed. It appears that diffusivity rates through nickel chromium sulfide scales can be reduced even further. Wancock found that tha corrosion rate in 80, vas not as severe as that in HS. This atmosphere apparontly forms a very goherent inner scale of Gr,0, with an outer layer of Wijs; and occasionally an intermediate layer of Crs. ‘he presence of an outer NisS, layer suggests as least some mobility of cations through cxs- The parabolic rate constants for a series of nickel-chromium alloys in 1008 sulfur vapors based cn the research of Mrowec, ct al., aa a function of temperature are presented in Figure 13.'! uetallography shows that the scalas on these alloys consist datgely of Gr with an outer layer cf Mi,S,, the thickness of the scala dacreacing vith decreasing temperature and increasing chroniun content. Strafford and Hampton confirwod thie using warker studies and themmcelestric power measuresents and concluded Crs is: an vn’ type (metal excess) compound. Tntarestly, Hancock haa reparted that the activity of chromium in nickel-chromium alleys at 750°-1000°C increases markedly between 18 and 35tchromium py weight and then renains essentialy constant at higher chromium levels." This suggests that corrosien rates may not improve oignificant ly with increne: oudum beyond 356, an observation not completely verified in Figures 12 or 13. ERFECT oF ALUMDONC Aluminum scales offer the promise of b inhibiting aulfidetion corzesion for a number of reasons, Its large negative standard y of formation of AS, (-546 kJ mol at RT), low rate of reaction and large molecular volume (Pilling-Bedwsrth vatio of 2.6) suggest that Alyy should be a favorable sulfide scale fox conferring excellent gulfidation resistance to an alloy. Strafford ana Naniford found « ten-fold reduction in the rate of sulfidation of iron-8% aluminum versus iron in 100% sulfur vapere at 500°C, 600°C and 700°C!” ‘They found the iron-5% aluminum alloy developed an inner scale of Als; and an outer scale of Fes. However, at hicher exposure temperatures (800°C to 1000°C), ionic diffusion through tha AL,S, layer becane rapid owing to the high exposure temperature relative co the melting point of Al), (1275°C) and the potentially protective effect of the ALS, ia lost. g potentially very effective in Mrowec, ot al., combined 5% aluninum to iron elloys containing 18-25% chromium and noted an order Of magnitude reduction in the teraary alley as contrasted to the binary iron-chronium alloy in ambient prescure gulfur vaper at 900°C to 1o00eC.( Alloy MA 956, as reported in Table 5, «: ities the ability of this combination of soale formers to markedly enhance sult. BEFECT OF KICKEL Tk is generally conesded that increasing nickel levels are detrimental to high Semperature sulfidetion resistence primarily ‘because of the relatively low melting polit of the nickel/nickel suifide eutectic (645¢C). Sines nickel aantrisutes strength, foughness and thornsi stability te an alley, it iz within the petrochemical industry's best interest to define the operating Limits oz nickel-containing alleys as a function Sf gach environmental condition. For one such anvirennant, #,-1,54H,6 at 720°C (Py = 10% Fa and Pj = 1 x 10! Pa), the effect of uickel content !s examined as it is modified by cther slloying elements (principally chromium, aluminum, ilicoa and the refractory elements) Tne Gata of Table 7 chow that sulfidation resistence is less Gegendent cn nickel content then on the scale-forming churacteriscies of the alloy. Modest aluminum acaitions (elloy 702 as compared to alloy 600), high iron contents and chronium levels greater than 15% (alley 300E as compared to alloy 600) are all effective in conveying sulfidetion resistance to nickel-conteining alloys in the Yeducing conditions of this test anvironnent. The resulte of Table # convey a cimilar theme for the lewor temperature, longer duration tests in #,-9.58 and 2.0 HAS.) Over Ehe temperature range 260°C to 260°C, increasing nickel contents between if and 35¢ have little influence on corrosion rates in reducing #,8 atmospheres. Interestingly, 9245the best results under these test conditions are fer the highest nickel-containing Alloy (alloy 671). EEVECT OF REFRACTORY AND RARE EARTH ELEMENTS Strafford and Hampton experimented with alloying elemante of differing valence and lonic racii to impede cation mobility through the scale chat forms on pure chromium in en atmosphere of P, = 0.107 Pa at ipo0°C.) Tncveasing amounts of tantalum (to 58), edzconium (to 58), yctriun (te 3.5%) and nolypdenum (to 108) did produce a Bighificant decrease in’ sulfidation. he parabolic rata constants for theca binary alloys ac a function of time at 1000°C in E,-209I,5 is presented in Table 9. ‘These glements were found to enrich tha inner region of the CrS scale but fail to devalep an impervious layer. These elewents appear to be nora cffoctive in nickal-baco alloys than they axe in iron-base alloys. Compare alleys 625 and 6L7 with alloy 601 (all approximately 22% chromium) in Figures §, 7 and 8 and Table 7. Strafford and Rampton have conciuded that minor additions of’ the reactive eloments, such a9, tantalum, sirconium and yttriun have @ beneficial effect in retarding sulfidation hy improving scale adhesion and by inhibiting cation mobility. Alloys MA 754, MA 758 and MA OS6 in Table 5 attest to the contribation of ¥,0, te suifidation resistance. EEFECT OP STLICOW Norton and Eneeshaw examined the effect of silicon additions to a cast 35% Nickel, 254 chromium, 1.18 manganese, 0.8% niobium, bal. Fe alloy oa tha rate of suifidation in 0.2% 1,6 (10 Pa) and 6.6% E35 (10~ Pa) atmospherce both at Py = 107 Pa and 600°C. They concluded that silicon additions up to 1-6# afforded no‘obvious protectien over that of the gilicon-free composition. Apparently internal oxidation of the vilicon precluded active participation of silicon within the scale. Hosier and Harris in an atmosphere of H,-1.5tH,S at 720°C (ses Table 7) algo found ho chvicus banefit of silicon additiens te alloys B3 and 330 over alloy 800."" ‘They observed that silicon and nickel combined to form a diffusion barrier at the seale/substrate interface of slicy DS which thay concluded vetarded inward diffusion pf sulfur. Tho scale itealf appeared netaliic in The above findings are consistent with chove of Table 5 in a H,-45t CO,-1.04H,3 atmosphere at 820°C where again tha two silicon-containing alleys (alleye DS and 330) showed greater mage change values than alley 800. EPPECT OP OTHER ELEMENTS Birks states that if nickel contains manganeee at an activity of 0.01 or graatar, Mns will foam at the scale/eubctrate interface when the pertial pressure of sulfur exceeds shout 107 fe. Hallstedt, et al., studied the effact or increasing manganese gantenks to 8.7% in alloy 80) on mixed dxidant sulfidation rates betwoon 700eC and 200% in crucible teste conteining CaSO, and carbon and in pure NaSO, crucible tests between 806°C and 1o00¢c. They concludac that manganese diffused throughout the oxide scale resulting in a manganase rich spinal which greatly retarded invard sulfur penetration while similtaneously reacting with any sulfur which did peactrate the scale by forming mms just beneath the scale. A high chromium flux ta the scale/substrace interface is thereby maintained thus postponing the initiation of braakaway corzesion gniguchi rouna that minor additions of titanium and zirconium have a distinct beneficial affact in reducing epa authors have studied titaniun edd Toy 800 end found marked xeductions in the rate of sulfidation in various environments and have proposed different nodele to explain their observations." ng conditions. “Several BFPECT OP TIME AT SRMPERATURE Mass change data can be misleading if an alley is subject to unpredictable breakaway corrosion. Rllays subjected to sulfidation envienments are prone to failure by this mechsnism, sepscially if its cule tends toward spatlation due to induced thermal stresses ox cyclic concitions or if the scale possesses high porosity that allows inward sulfur migration to internally tie up the scale forming elemente. Table 19 lists © number of elloys seeuly resistant to breakaway corrasion in H,-45t00,-1¥E,5 at 620°C. Alloys of the 500 sezies with their high iron and chromium contents rosie? breakaway corroeion vather well. It appsare that silicon additions (alloys DS and 330) do not initiate breakaway corrosion resistance put their higher mass change values for equivalent times suggest that in the long run, silicon is not as preferred a scale 24/6former ao higher levels of chromium, such as, that contained in alley 803. The oxide Gispersion strengthened alleys, MA’ S85 and 758, posmess low mass change rates and zesist bremkaway corrosicn apzarently duc to effective scale revention and low diffusivity values sesulting fron the dispersoid content and adequate chromium contents. FUIURS ALLOY EFFORTS A number of synergistic improvements in performance have been reported in this paper, all of which can be traced ultimately to altered scale characteristics stemning fron alloy modification. Tt certainly appears pessinle that for any giver exvirommontal condition operating between precisely defined limite that an alloy could be tallorad to mect specific end-use conditions. ‘To accomplish what is required now, corrosion specialists need a otter fundamental underctanding o£ these synergiseie Phenomena. However, even while this effort iy underway, these corrosion specialists should strive to nore accurately cefine the operating limits of current alloys and be ina position to suggost the best current alloy or alley family for any particular service conditions. Especially needed are long term (one year or more)’ sulfication data upon which plant construction congiderations could be hasod concLusroNs 1. Sulfidation of nickel-containing alloys differs from oxidation in the rates ef weaction, melting points of the scales and reaction products, diffusivity rates through the various scales and the effect of the oxygen potential. The general level of technical understanding is alse lower for sulfidation. 2. The kinetics of reaction in reducing culfidation atmospheres are generally nore rapid than those in oxidizing sulfidation environments. 3. Increasing levels of chromium, aluminum, izon, refractory and rare earth eloments ameliorate sulfidation rates at any given nickel content for both oxidizing and reducing sulfidation environments. 4. Increasing tenperetuses or time-at-temperature require that scale integrity be upgraded through more enlightened use of scale forming elemente to achiove Satisiactory corrosion performance. REFERENCES 3. Kp M. Strafford end P. K, Uatts, Materials Science and Technology §, (1985): p. 2, BB, Backensto, R. D. Drew and C. C. Stapleford, Corrosion 12 (1956): p. 22 3. BL W, Neumainer and Cc. M. Schillmollex, Petroleum 29, (1957) p. 385. 4. G. Sorell and W. 2 Hoyt, Collection and Correlatien of High Temperature lydrogen Sulphide Coazvsion Dele (Houston, TX: National Asscciation of Corrosion Engineers, 1979). 5. W. L. Lomand A. F. Williams, Substitute Natural Gas - Manufacture and Properties (London: Applied Science Publishers, 1974) - 6 8. Mrowec, oxidation of metals 44, 1/2(1995): p. 177 7 RLM, Strafford and A. F. Hampton, Journal ef Materials Science 8, (1953): p. 8. H. Mu, M. G. Hocking and P, . Sidky, Oxidation of Metals 41, 1/2(1894): p. al. 9. ©. B. Alcock, M. G. Hocking and S. Zador, Corrosion Science 9, 2(1969): p. 111. 10. K. B. billenud, 8. Haflen and P. ¥ Lis. feted, Oxidation of Uetale 21, 2/4 (1994): Be Ll. H. Mu, M. G. Hocking and P. S. Sidky, Oxidation of Metale 29, $/6(1993}1 p. 371. 12. KL, Luthra and W. L. Worrell, Metallurcical Traneactions A 10, 5(1979)+ p. 621. searBe 1a. as. a6. a7. aa. as. 20. a. 23. 24. as. 26. 2, R. F. Saliskury ond M. Birks, Journal of the Iron and Stee! institute 209, 743871): p. 534. S$. Mrowec, Proceedings of Sth International Congress on Metallic Corrosion (London: Butterworths, 1981), p. 2110. P. Eancock, Proceedings of First International Congress on Hetal Corrosion (london: Butterworths, 1962), p. 193. 8. Mrowec, T. Werber and M. Zastamik, Corresion Scisnce 6, 211966); p. a7 K. M. Strafford and R. Maniford, oxidation of Metals 46,1(1969! pe 221, 8. Mrowec, S$. Techowic: T. Werkor and J. Podhoredecki, Corrosion Geience 7, 16(1967)+ "p. €S7, J. ©, Hosier and J. A. Harris, *Sulfidation Resistance of High Temperature Alloys Rooted in Reducing ond Oxidizing Atwospheres,* CORROSION/80, paper no. 167 (Houston, Tk: NACE International, 1980). 8. F. Chou, P. Lb. Daniel, A. J. Blasewicz and R. F. Dudek, (New York, Nv: The Metallurgical Society of AINE, 1988), p. 327. K. MN, Stratford and A. F. Hamilton, Journal ot Less Common Metals 25, 4(1971): ps 435. 3. F. Norton and o. A. Kneeshaw, High Temperature Alloys: Theix Exploitable Potential (London and New York, MY: Elsovie: Applied Science, 1987), p, 173. N. Birks, Wich Temperature Gas-Metal Reactions in Mixed Envirorments (Naw York, MY: The Metallurgical Society of Atm, 1973), p. 332 B. Walleteds, P Wilhelmson and S. sernhardeon, ‘Effect ef Manganese on the Hot Corrasion Resistance of Alloy 800,* Corrosion/86, paper no. 95 (Houston Tk. NACE Internationa), 1985). S, Taniguchi, T. Shibata, T. Wiida, Oxidation cf Metale 34, 3/4 (1990): p. 277. D. R. Holmes and J. Stringer, Materials to Supply the Energy Danand (Metals Park, OW: ASM International, 1861), p. 125. C. Wearney, Sr. and E, Natesan, Oxidation of Motals 17, 1/2(1982): p. 1. 524/85TABLE i ‘THERMODYNAMIC DATA POR TRE SULPIDES oF NrcKED AND ITO KEY ALLOYING ELEMENTS AT 720°C Pres Energy of Pextial Prossure ot Formation Sulfur for K/Ms Slement Sulfide (Ae%kr/mal 8.) Equilibrium (Py, Fa) al ALS, 284.3 3.4 x 10 TH Tis, 383.4 1.3 x lo ar 472.9 3.3 x 10% Nb 1.0 x 19 ta 2.4 2 10" or 5.3 x 10 Mo, Mos, 1.0 x 10" u ws, x 107 Fe Fes « co 20,55 Ni Nis a0 Tho gonoral reaction 10: 2(x/¥)M,, + Sy? (2/¥)My,S,- Ware @ and g xofer to volia and gas atates, respact ely. Stoichiometzios are often uncartain, lending to uncertainty ta Ac? values. TABLE 2 FEYSICOCHEMICAL PROPERTIES OY SULFIDES OF NICKEL RND I79 KEY ALTOYING ELEMENTS Pilling-Zedwerth —_vefact Melting Point IMS Rutect4e suitiae Ratio structure 2) Tomporature (°C) ALS, 2.60 n type 1098 - aaa n type 1999-2100 -- 1.81 n type 1549 oe -- a type _ = 2.42 n type 1000 - 2.80(crs) n/p type 1550 1350 3.84 notype 14s? ae 3 -- ct 2 aias 96a Coxe 2.37 1080 200 mus, 2.50 yee 736 eas, Steichiomotries eud ranges of stoichlometztes aro oftes uncertain. Commonly n or p type cefact structures are accounted for by matal excoss ox cation deficiont structures, parabolie seale growth occurring principally by cation or vacancy diffusion, the formation of Mes, (and possibly WS,) however davolvaz anion transport in anion deficient lattices.TABLE 3 SELP-DIPFUSION COBFPICIENTS OF CATIONS D, IN SOME METAL OXIDES AND SULFIDES Moasuramant Mengsrenant Sulfide Temperature Dyan?) oxide vemperature D,(onte*) eel (i) 60,8, 720 7.0 x 107 coo. 1000 1-9 x 104 nis 800 a4 x 20° NiO 1009 2.0 x 10% crs, 1000 1.9 x 107 cx,0, 1000 1.0 x 10% Pos 800 3.5 x 107 Peo B00 1.3 x 10% ALS; 500 Lo x 104? ALO: 2090 1.0 x 10% TABLE 4 NOMINAL comoszTZON OF COMMERSTAL ALLOYS LISTED IN TUES PAPER (Nominal Weight Forcont) Alloy URse Nicer ve Ma st a mt ° 304 ©3000-1019 2.0) 1.0" - 0.98 3a 32100 10a 1.0" - Sxic 0.08" 209 s3ogo0 1323 2.0° 1.0" - - 02 310 e31000 21H SL. ao 3 = 0.25" B00 woss00 322046 10 0.2 oa 0.03 soon oo NosslG ©=— 322d 5 1.0r 0.48 0.07 801, Nosgor 922s 1.07 - 1.2 0.10" 803 280087 ao 0.5 0.3 oa 0.07 330 Nog3300 25S - Lt - 2 0.08" bs asase 380 1g 2.3 = o.2' o.n0t eos* = woge2s aa 2228 - - - 1.0 0.05" en sla - = on 11 9.05 ey NORSIT. SD = on : oa 9.09 east Nose2s gz 0.15. oa" 0.03 Nogsol = 6233 0.2 o4 0.04 wossa0 632 2 02 9.01 mosso0 75g o3 0.3 0.3 0.08 - eo 16 2 - OL 05 9.05 se79S¢ - 2 7a € 5 : os 0.05 MATES NOT7SE 78d - - 7 0.8 0.05 ma 788% - 6 300d - - 03 0.8 0.05 * Maximum Others: * 3.0 Mo,2.0 Cu "5.5 Mo,12.0 co * 9.0 Mo,4.0 Nb ° 0.5 ¥,0; 10.6 Ys0; 524/10TABLE 5 MASS CHANGE DATA IN #,~45%C0,-2AH,S FOR SELECTED ALLOYS aT ESD DURATION OF 1009 HOURS 82000, Rey Comocitional Slenents Masa change Alley xt ce Fo crber (aaiem") 308 3 2 et = 4.28 at 24 as 52 - 0.62 00% 32 2 a5 _ Las 330 a6 19 4a 1.1 6 6.97 te 37 1 42 2.25 si 13.70 503 34 26 37 0.7 Si 4.as sn st 48 zs hei th 0.92 mn 936 20 74 0.20 m75¢ 78 20 Le 4.60 15a? 30 1.0 1.24 MASS cmNGE TABLE 6 DATA Tif AIR-2%60,-5%,0 FOR SELBCTED ALLOYS AT 700°C, B50%C, AND 1o02%¢, ‘TEST DURATION OF 1000 HOURS Ray Componitional enants Mass Change (mg/en?) Alley a cr Fo 700° a5oec 1000°¢ 304 10 ~ 68 = -43.10 -14.30 308 Fe] 23 ct 0.33 1ea5 220 a 5 si - o.38 200 33 21 46 6.28 ast 2.43 601 61 23 4 0.33 2.40 3.50 690 62 22 8 0.33 6.61 0.45 672 82 48 - - o.t0 2.40 52411SAREE 7 TSOTHERMIC COPROOTOH RATES OF ALLOYS WITH DNCAEASING NICKEL CONTENT AND VARIABLE AMOUNIS OF OTHER ELEMENTS IN E.-1.5%H,5 at 7309C, RST DORAPION OF $6 HOURS Key Compositional elements Corrosion nate Alley a cx Fo other (m/v) 304 10 19 6 - 31.2 aio an 2s Et - 18.0 200% 32 21 45 - 18.4 330 36 qs 44 1.2 si oad ns 3 18 42 2.25 Sh 19.2 a2s 42 22 28 3.0 Mo, 2.2 cu, 1.0 74 28.4 SL 48, ~ La i 24.9 sa 22 12.5 Co, 9.0 Mo, 1.0.8 35.8 61 23 ad a 2 9.0 Mo, 18.9 76 16 < 36.0 202 20 16 3.0 AL 17.9 TABLE 8 ISOTHERMAL CORROSION RATE OF ALLOYS WITH TNCREASTNG NICKEL AND VARIABLE auomuTS OF GHROMTIM TW H,-0.58,5 AT 2600C AND 370%C AGED ON TEST DURATION OF 3000 HOURS AND FOR W,-24H,S AT 480°C AFTER 4000 HOURS Key Coupowitional #lomsate Corzesion Rate (on/y} ar ML or Pa 2E0ee 370°C 4o0%c aan 30 1 38 0005 0.0083 0.30 308 2B B a 0.0905 0.0007 0.041 210 2 2 51 0.002 0.002 - 600 33 2 45 0.0005 0.0028 0.330 en SL 4 - 0.0003 0.0008 0.00 S242,FAMABOUIC RATE CONSTANTS OBSERVED DURING THE SULFIDATION OF CHROMIUM AND VARIOUS CF-BASED BINARIES AT 1O00SC IH H,-30e H_9 GAS MEETUNE Material Rate Constent, Ep (composition wt .%) dag? en mint) (8B Alloy) /[RpCr) cr 222.4 24.2 = cr-0.5ta 267.3 44.7 9.95 crate 259.4 49.3 0.92 crane, 204.3 0.72 rst 136.9 0.66 cx-Ler 248-5 0.88 cesar 240.0 0.85 Cr-1Ke 213.5 49.9 0.76 Cr-10M6) 192.1 st.4 068 er. 198.2 212.5 0.79 PRBLE 10 MONGEST TIME LABORATORY EXPOSURE OBSERVED WITHOUT EXPERIENCING “BREAKAWAY" PATLIAE ZN Hy -45AC0,-1.03E,8 NIMOSPEERE 27 92080. HASS CHANGE DATA FoR’ LAST REPORTED TIME Ts ALSO LISTED Time Without Initiating Maso Change Prioz Breakaway Broakaway Corroaion (mg/m) Anoy (nour) 200 14,976 3.21 330 1,536 11.56 bs 1.872 7.89 803 5,496 3.21 3,108 0.03 Ma 758 22,056 0.68 824/13°C 1200 1900 990 890 700 500 S00 to-# 3 Fe 7 § « 10°4 & Ni z 5 3 Co 2 5 6 2 S é 2 1974 5 — Ssuitiastion 8 === Oxidation G é 10° T + 6 8 1 061214 104/T, Kt FIGURE 1- Collective plot of the temperature dependence of the sulfidation and oxidation rates of some metals. '8 a a a <— Iron, % Nickel, 4 —> FIGURE 2- The melting point of the sulfide scales that Torm on Nickel-Iron-Chromium ternary alloys. saad4 850°C 4 C095 > (Nis , (liquid) T | ' co, Ni ' 2 * i 3 gg crs { 1 g i 4 ocr 1 : T te 23 19 15 a 7 Log Py, (Pa) FIQURE 3- Thermodynamic phase-stabilily diagrams for the pure motals Iron, Cobalt, Nickel and Chromium at 850 °C. The askerisk is the point of the 17.6% Hz, 0.1% Hp S, 20.8% CO, 20.1% CO, Bal. Nz atmosphere described in this paper,(0) 800K Welght Change (mg/cm?) a ° 20 40 60 ao = 100 Exposure Time- Hours FIGURE 4- Mass change of alloy 800H in 17.6% Hz, 0.1% H2S, 20.8% CO, 20.1% COs, Bal. Np atmosphere at 850°C. (*) 524/15a. CrS over grain boundarles, Cr, 0, elsewhere. c. Cracks form in (Cr, Fe, Mn) Ss. 1, Fe, Mn)S (Cr, Fe, Mn) Sv NiSoj+ FeS b. (Cr, Fe, Mn) § form bensath Nis: Uf 4. Mature nodule with Fes cap. FIGURE 5~ Schematic diagrams showing the nodule formation of alloy 800H in 17.6% Hy~ 0.1% H, 8, 20.8% CO, 20.1% COz, Bal. Nz. [ (I) = liquid] 20 825 - 7 ow 5 0+ o ee] ot g = 207 200 = 308 & 2 204 301 & = 404 321 eas -50 T T 7 7 T © 100 200 300 400 500 00 Exposure Time - Hours FIGURE 6- Mass change of ten alloys in H,- 62 H,S at 482°C, saaiteMass Change, (mg/cm?) ° 100 «©6200 ©4300 400 500 600 Exposure Time ~ Hours FIGURE 7- Mass change of ten alloys in H ,- 6% HS at 538 °C. 1004 -2005 Mass Change, (mg/cm 2) 200 300 400 500 600 Exposure Time — Hours ° 100 FIGURE 8- Mass change of ten alloys in H,~ 6% H, S at 593°C. S247Loa Ps, (Pa) & 1 Co, Ni, Fa Sulnhates, TT —T 40 -35 -30-25 -20~19 -1D-5 0 45 HO Log Pg, (Pa) FIGURE 9- Thermodynamic phase-stebility for the pure metals Chromium, Iron, Cobalt, and Nickel al 750 °C. The asterisk is the equilibrium point ofthe SO 3:0 (2:1) atmosphere described in this paper. Welght Change (mg/cm?) 0 20 40 60 80 Exposure Time- Hours FIGURE 10- Mass change of alloy 800H In the SO, - 0, [2:1] atmosphere at 750°C, (8) saata. Formation of oxides at Initial stage. Ni, Fe oxides and culphides So, r b. 80, penetrates Cr, 0, through cracks leading to NiyS> and Fes, 8 80, 80. 2 pe 2 cr. 02 SNioSs, Fes FIGURE 11- A schematic diagram tor the corrosion of alloy BOOH In S02~ 0 p(2s1) at 750 °C bofore the spalling ef Cr, 03 ‘outer scales, ©. Sulf des undercut Cr, 0, layer and Internal attaek occurs, 150 100 50 63 - 35, 50 - 50 Welght Loss (mg/em2) 50 100 150 200 250 300 Exposure Time- Hours FIGURE 12- Weight loss-time curves for Nickel- Chromium alloys in HS at 700 °C, 524/19Log Kp (g2cm-4 8-1) -1.0. °c 900 850800 750 700 650 600 560 509 1 SSE AS Si outss or \ SS Ck 220, cr “* Ni 42.8% Gr 63.0% Cr 82.0% Gr 0.9 10 ut 42 13 = X 10°K FIGURE 13- Dependence of sulphidation rate on temperature for Nickel-Chromium alloys in H, - 30% H,S. (16) 524/20