AISI 304, 314, 321, and Incoloy 800H have been subjected to several pretreatments: polishing, milling, grinding, and cold drawing. In the temperature range 800–1400 K, cold work improves the oxidation resistance of AISI 304 and 321 slightly, but has a relatively small negative effect on the oxidation resistance of AISI 314 and Incoloy 800H. Milling results in an enlargement of the surface area with a factor 2.5

Fransen, T.

Gellings, P.J.

Langevoort, J.C.

English

University of Twente Research Information

Oxidation of Metals, VoL 21, Nos. 5/6, 1984 On the Influence of Cold Work on the Oxidation Behavior of Some Austenitic Stainless Steels: High Temperature Oxidation J. C. Langevoort,* T. Fransen,* and P. J. Gellings* Received December 14, 1983 AISI  304, 314, 321, and Incoloy 800H have been subjected to several pretreat- ments: polishing, milling, grinding, and cold drawing. In the temperature range 800-1400 K, cold work improves the oxidation resistance of AIS1304 and 321 slightly, but has a relatively small negative effect on the oxidation resistance o fAISI314 and Incoloy 80OH. Milling results in an enlargement of the surface area with a factor 2.5. KEY WORDS: oxidation; stainless steel; cold work. INTRODUCTION The influence of the surface condition on the high temperature oxidation resistance of metals and alloys has been the subject of  various investigations in the past. It is reported by Allan and Dean t that cold work results in a better corrosion resistance in CO2 atmospheres at temperatures in the range 923-1023 K. The temperature at which deformation is taking place is also assumed to play an important role. Cigada et al. 2 showed that specimens of  AISI 304 deformed at liquid nitrogen temperature were less resistant to SCC (stress corrosion cracking) than undeformed ones, whereas deforma- tion at room temperature resulted in a better resistance to SCC. Leistikow 3 found that cold work had a beneficial influence on the corrosion of  Incoloy 800H below 1073 K and a negative effect above that temperature. Stevens 4 * Twente University of Technology, Department of Chemical Technology, P.O. Box 217, 7500 AE Enschede, The Netherlands. 271 0030-770X/84/0600-0271503.50/0 9 1984 Plenum Publishing Corporation 272 Langevoort, Fransen, and Gellings observed that annealed specimens showed a better oxidation resistance than cold worked ones. Langevoort et aL 5 reported an increase in oxidation resistance of AISI 304 and 321 in the temperature range 800-1000 K, but a decrease in oxidation resistance of Incoloy 800H after cold work. Stokkers et  aL 6 observed an increase in oxidation rate after ion bombardment of stainless steel AISI 314. In this paper, the results of the oxidation measurements of several stainless steels are discussed in terms of defect structures introduced in the bulk by milling, rolling, grinding, and polishing. It is shown, however, that cold work has only a relatively small influence. EXPERIMENTAL PROCEDURE All specimens were annealed at 1350 K, water quenched, heated at 1230 K for 1 hr, and finally water quenched again. This last heat treatment was only necessary for AISI 321 and Incoloy 800H in order to prevent sensitization at temperatures in the range 870-1070 K. However, for reasons of uniformity, all samples were treated the same way. The final pretreatments used in this work were milling, electropolishing, grinding, cold rolling, and cold drawing. Except for the milled samples, all specimens were ground (220-800 grit SiC paper and polished on 1 ~m diamond powder followed by 0.05/xm A1203 powder). Samples were milled following standard pro- cedures. All samples were ultrasonically cleaned with hexane and with ethanol for 1 hr. Oxidation tests were performed in a Stanton balance and a Cahn RG electrobalance (sensitivity 0.1 and 5 x 10 .3 mg, respectively). The oxidized specimens were examined by metallography, SEM/EDAX measurements, and X-ray diffraction. The chemical composition of stainless steels used are listed in Table I. Samples of AISI 314 were electropolished in an electrolyte of 80% methanol and 20% H 2 5 0 4  (SV, current density 0.5 A/cm2). Milling was carried out under continuous cooling, with a Clarckson groove cutter (q5 = 12 mm), at 175 r/rain, a rate of feed of 0.05 mm/min, and a conveyor screw of 216 nm/min. Table I. Chemical Composition of Stainless Steelss Used Steel Cr Ni Ti Mn Si C S Fe AISI 304 17.39 8.88 1.27 0.70 0.044 0.017 bal. 321 17.45 10.13 0.40 1.55 0.52 0.048 0.003 bal. 314 24.22 19.30 1.29 2.10 0.06 0.005 bal. Incoloy 800H 19.90 31.70 0.42 0.72 0.49 0.080 0.080 bal. Influence of Cold Work on the Oxidation Behavior of Some Austenitic Stainless Steels 273 The increase of  the surface area by grinding, milling, etc., was deter- mined by measuring the amount  of  adsorbed carbon-14 labeled species. Specimens were immersed for 0.5 hr either in an aqueous solution of hexadecyl- l -Cln-tr imethylammonium bromide (HMAB 13) or in a solution of C~4-stearic acid in nitrobenzene, followed by washing for 5 min in fresh solvent. For comparison,  a worked sample was always immersed in a radioactive solution together with a electropolished one. The samples were counted under  a Geiger-Mfiller  detector tube. For further details, see refs. 13 and 14. RESULTS Oxidation Kinetics In Fig. 1 the experimental  results are shown for the different stainless steels used. Even at high temperatures,  AISI  321 oxidizes more slowly than AISI  304 and both show a decreasing weight gain with increasing cold work (elongation). After 5 -10hr  of  oxidation, however, the oxidation rate is almost the same for all deformations (elongation) applied. In Fig. l(c) the difference in oxidation behavior for electropolished and milled samples (without surface correction) of  AISI  314 is shown for two temperatures (1318 and 1468 K). At both temperatures milled samples oxidize faster than ~J r~ ~'7 E ! U i z ! 0 "1~0 2~0 3~0 4'0 50 TIP1E Eh3 (a) Fig. 1 (a) Typical oxidation curves for AISI 304 and AISI 321 at T =  1420 K: +, 9.4% elongation; *, 20% elongation; # ,  milled AISI 304; x, AISI 321 20% elongation. (b) Typical oxidation curves for Incoloy 800H at T= 1420 K: *, 6% elongation; +, 10% elongation; circles, 20% elonga- tion; x, milled. (c) Typical oxidation curves for AISI 314: O, electropol- ished, T= 1318 K; +, electropolished, T= 1468 K; filled circles, milled, T= 1318 K; • milled, T= 1468 K. 274 Langevoort, Fransen, and Gellings n 04 E O 0] E~. z (E (_5 I (w- I (_5 W O 0 j f  o b 1~0 2'0 3~0 4~0 5'0 T I M E  [ h i  (b) n 04 E O [D S~_ z (IZ (5 I t~ W o- 0 f 1 '0 2 '0 :3 0 -4LO 5 0 TIME [h] (c) Fig. 1. Continued. electropolished ones. Incoloy 800H shows an increasing weight gain with increasing cold work (elongation). The oxidation curves of milled AISI 304 and Incoloy 800H at various temperatures are plotted in Figs. 2(a) and (b), respectively. After several hours of oxidation, all samples followed the parabolic rate law Influence of Cold Work on the Oxidation Behavior of Some Austenltic Stainless Steels 275 I"-3 QD- (N E (3 ED u.J Z (E (D T Ld 0 .---<m--- Y I I I + I -l- a 1'o Jo 3'o 20 s'o TIME [hi (a) Cxl E U 0~ i-J Z u Q5 [ ,-~- k- -l- (D Ld 0 110 210 30 40 ~0  TIME [h] (b) Fig. 2. (a) Milled AISI 304 at different temperatures: +, 1040~ x, 1100~ *, 1150~ (b) Milled Incoloy 800H at different temperatures: *, 1035~ O, 1100~ filled circles, 1 !50~ The dependence of the parabolic rate constant, Kp, on the temperature is given by the Arrhenius equation 1 Kp = Ko exp - ~  In Fig. 3, log K v is plotted versus the inverse of the temperature for AISI 304 and Incoloy 800H, respectively. Table II gives some parabolic rate constants and activation energies. 276 Langevoort, Fransen, and Gellings Table II. Parabolic Rate Constants and Activation Energies Material Pretreatment T(~ Kp (mg2/cm 4 s) E (kJ/mol) AISI 304 milled 1.3 x 10 -73 ] 1.6 x 10-12 ~ 900 6.0 x 10 -1~ ) polished 3.0 x 10 -13 ) 1.2 x 10-1~ 6.0 x 10 -1~ ( 500 4.0x lO-X~ Incoloy 800H 320 Grit 5.2 x 10 lO \ 1.8 x 10 -9 J 370 20% elongation 1.6 x 10 -13 ] 4.5 • 10-12~ 280 1.0 x 10 -11 ) milled 4.8 • 10 -12] 7.0 x 10-12~ 9.0x 10_12 [ 115 1.SxlO-11J 20% elongation 5.0 X 10 -14 ] 2.5• 13~ 170 9.0 x 10 -13 ) 6.0xlO -14" 2.0 x 10 -13 2.0 x 10 -12 1.3 • 10 -~3 3.3 • 10 -14" 4.3 x 10 13 23 x 10 -12 7,7 x 10 -12 5% elongation cold rolled 1070 1100 1150 880 950 1090 1100 1070 1190 900 1000 1100 977 1035 1100 1150 8OO 9OO 1000 8OO 9OO 1000 1100 8OO 9OO 1000 1100 199 193 Morphology and Analysis All spec imens  had  a dark b rown  to b lack color  af ter  the ox ida t ion  exper iments .  The scale was porous  and was always found  to consist  o f  two layers,  except  for  the mi l led  specimens.  F igure  4 shows S E M  pictures  with E D A X  line scans o f  a cross-sect ion o f  A I S I  321. Even  at h igh tempera tures ,  grain growth  only occur red  in the bulk  o f  the sample ,  but  in the layer direct ly be low the surface ( <~ 10/xm),  no grain growth was found.  X- ray  diffract ion showed  a-FeaO3 and an oxide  o f  the fo rm (Ni,  MnFe)  (MnFe)204  or (FeCr)3Og with a cubic  structure and a cell cons tant  o f  0.841 nm to be the main  const i tuents  o f  the outer  oxide  layers. The  inner  oxide  layer  consis ted of  a cubic  c h r o m i u m  oxide  with a spinel l ike structure and a cell constant  o f  0.836 nm. Figure  5 shows a typical  cross-sect ion of  Influence of Cold Work on the Oxidation Behavior of Some Austenitic Stainless Steels 277 % k - I  (3 O~ _J '~ o "t3.6 o " L _ I  (3 O~ c "t38 \\ 0;.7 0~.8 o~.g IO00/T EK 1 (a) 110 I I 0.7 o:8 o:9 1.o IO00/T EK ] (b) Fig. 3. (a) Log[Kp] vs 103/T for AISI 304: filled circles, milled; +, coarse grained (+320 grit); O, coarse grained; x, 20% elongation. (b) Log[Kp] vs 103/T for Incoloy 800H: *, milled; +, 20% elongation; O, 5% elongation; x, cold rolled. the scale on a mi l l ed  sample .  This consists  on ly  o f  c h r o m i u m  oxide ,  with some i s lands  o f  i ron  oxide .  This was obse rved  on all mi l l ed  samples  ox id ized  be low 1373 K. A b o v e  this t e m p e r a t u r e  these  i ron- r ich  oxides  fo rm a con- t inuous  l aye r  on top  o f  the  c h r o m i u m  ox ide  layer.  This change  in ox ida t i on  can a lso  be seen in the  weight  gain  versus t ime curves o f  Fig. 2(a).  Fig. 4. SEM pictures of a cross-section of AISI 321 with (a) Cr line scan and (b) Fe and Ni line scans. g~ ga, Influence of Cold Work on the Oxidation Behavior of Some Austenitic Stainless Steels 279 r o Fig. 5. Typical cross-section of a milled sample (oxidized below 1373 K). ~n QtQ O ga Influence of Cold Work on the Oxidation Behavior of  Some Austenitic Stainless Steels 281 Determination of the Surface Area Specific rates and rate constants (i.e., per unit of surface area) can of course only be determined if the real specimen surface areas are well known. Techniques utilizing the adsorption of carbon-14 or tritium labeled polar organic compounds such as HMAB and stearic acid have made possible determinations of the specific surface area of  nonporous materials and flat surfaces. 13'14 Both compounds were used following the method described above. This method was found to provide complete monomolecular layers. The influence of  cold work per se (i.e., without surface area enlarge- ment) was determined by means of experiments with samples that underwent a deformation of 90% by cold rolling, followed by electropolishing. The adsorption capacity of these specimens proved to be the same as that of samples which had been electropolished, but not cold rolled. This resulted in the conclusion that working itself does not influence the specific adsorp- tion. However, the surface area may undergo an important change due to working procedures other than cold rolling. The milled coupons, for in- stance, have a surface area about twice to triple that of the electropolished ones. Comparable results were found for samples ground with 320 grit SiC papers. It has been reported that such specimens are characterized by a roughness factor of about 2.5. Hence, these samples show in fact a specific resistance toward oxidation which is better than that of electropolished ones (see Figs. 1 and 2). DISCUSSION Both AIS1304 and 321 show a decreasing oxidation rate with increasing cold work, while AISI 314 and Incoloy 800H show an increasing oxidation rate with increasing cold work. But as can be seen from Figs. 1-5, cold work has only a small influence on the oxidation. Cold work has a beneficial effect on the oxidation resistance of AISI 304 and 321, but in contrast with Leistikow, 3 no beneficial effect has been seen on the oxidation resistance of Incoloy 800H, even at lower temperatures 770-800 K. 6 There are many theories for explaining the effects of pretreatment on the oxidation behavior of stainless steels. Cigada et  aL 2 correlate the SCC resistance reduction to an increase in concentration of internal microstresses, generated by a reciprocal reordering of  a '  and 7 phases. Allan and Dean l ascribe the effect to the creation of one or more zones of differing structures and the formation of  more grain boundaries as a result of recrystallization. This results in a faster diffusion of chromium just below the surface, thus yielding faster formation of a protective chromium oxide layer. 282 Langevoort, Fransen, and Gellings Langevoort e t  al. 5 explained their results from optical microscopic measurements of AISI 304 at temperatures of 770-970 K with the formation of an a '  martensite structure within the austenite matrix. This martensite structure was found to exhibit a high rate of diffusion for chromium, 7 which will lead to a very fast initial and a very slow subsequent oxidation, due to a protective Cr203 oxide layer. Even at the high temperatures used (1000- 1400 K), where it is expected that the importance of easy diffusion paths will be diminished, elongation still has a beneficial effect on the oxidation resistance of AISI 304 and 321. However, the effects measured are only small at the temperatures and times used in this investigation. Caplan and Cohen 8 showed that below a temperature of 840 K, cold worked Fe oxidizes faster than annealed Fe, while at temperatures above 920 K, cold work has no effect on tl~ oxidation rate. They proposed that, at low temperatures, the oxide formed on cold worked Fe had a finer grain size than the oxide formed on annealed specimens and that the cold worked metal provided sufficient cation vacancy sinks to suppress cavity nucleation. At high tem- peratures, however, the results are explained by the formation of a highly defective FeO oxide, where lattice diffusion would not be much slower than grain boundary diffusion. Caplan and Sproule 9 reported that in the oxidation of chromium, compressive stresses, within the oxide, may play an important role. These compressive stresses are caused by cations diffusing outwards and anions inwards along grain boundaries in the oxide layer, resulting in a wrinkling of the oxide layer. Ledjeff e t  aL l~ attribute the increase in oxidation rate of a 25/20 stainless steel to a grain growth mechanism, which prevents the formation of a protective scale of Cr203 and which promotes the formation of an iron oxide scale. This is, however, in contrast with our findings, where in the surface layer (thickness-~ 100/xm), no grain growth was observed. Pearce and Wild 11 found an increased Ti concentration (up to 23%) in the oxide of Incoloy 800H after 2000rain of oxidation. Although (in our investigation) S!' and some Ti enrichment in the oxide was found, the concentrations never exceeded a few percent. Without surface correction, milling seems to have a negative effect on the oxidation resistance, but if the surface enlargement, due to milling, is taken into account, millil~g has a slight beneficial effect on the oxidation resistance. However, after~ 100 hr oxidation time, this surface enlargement has largely gone, so its beneficial effect on the oxidation resistance in the long run is doubtful. It is ~therefore proposed that the conclusion of Allan and Dean ~ that industrial treatments improve the oxidation resistance is too optimistic; however, it may be concluded that industrial treatments do no harm to the oxidation resistance of stainless steels. Influence of  Cold Work on the Oxidation Behavior of  Some Austenitic Stainless Steels 283 C O N C L U S I O N S  Due  to cold work an a ' -mar tens i te  structure is fo rmed within the austenite matrix o f  A I S I  304 and 321. In this martensite structure, the diffusivity o f  ch romium is much larger than in the austenite structure, and as a consequence,  the initial oxidat ion o f  cold worked 304/321 is faster until a good  protective Cr203 oxide has been formed.  This scale becomes  more dense and adhesive with increasing cold work. Inco loy  800H and AIS1 314, however,  are more  stable austenite stainless steels, and they do not show t ransformat ion  o f  their structures into martensites as a result o f  cold work. Due  to cold work,  the concent ra t ion  o f  defects in the metal is increased, and this will cause the presence o f  an increased amount  o f  defects in the oxide layer. These defects create easy diffusion paths, resulting in a faster oxidation.  Therefore,  the oxidat ion resistance o f  Inco loy  800H decreases with increasing deformation.  Cold  work has an influence on the oxidat ion resistance, but  this is only very small. In  this investigation AISI  321 was observed to be oxidized more  slowly than AISI  304. This p robab ly  due to the t i tanium content  o f  AISI  321. However ,  a separate t i tanium oxide layer was not  observed,  and only small amounts  o f  t i tanium oxide were found  within the oxide layer. So the role o f  Ti in the high temperature  oxidat ion remains unclear.  A C K N O W L E D G M E N T S  We thank Z. Kolar  o f  the "Interuniversi ta i r  Reactor  Inst i tuut"  Delft  and M. A. de Jongh  for their experimental  contr ibut ions and helpful discussions. R E F E R E N C E S  1. S. J. Allan and M. J. Dean, in Behaviour of High Temperature Alloys in Aggressive Environments I. Kirmann et aL, eds., Proc. Int. Conf. Petten (The Metals Society, London, 1979), p. 139. 2. A. Cigada, N. Mazza, P. Pedeferri, G. Salvago, D. Sinigaglia, and G. Zanni, Corr. Sei. 22, 559 (1982). 3. S. Leistikow, in ref. 1, p. 197. 4. R. Stevens, Oxid. Met. 13, 71 (1979). 5. J. C. Langevoort, T. Fransen, and P. J. Gellings, Werkstoffe und Korrosion 34, 500-504 (1983). 6. G. J. Stokkers, A. van Silfhout, G. A. Bootsma, T. Fransen, and P. J. Gellings, Corr. Sci. 23, 195 (1983). 7. S. Pednekar and S. Smialowska, Corrosion 36(10), 56-577 (1980). 8. D. Caplan and M. Cohen, Corr. Sci. 6, 321 (1966). 284 Langevoort, Fransen, and Gellings 9. D. Caplan and G. I. Sproule, Oxid. Met. 9, 459 (1975). 10. K. Ledjeff, A. Rahmel, and M. Schorr, Oxid. Met. 15, 485 (1981). 11. R. J. Pearce and R. K. Wild, J. Nucl. Mat. 91, 156-170 (1980). 12. T. Fransen, M. A. de Jongh, and P. J. Gellings, in Proc. 8th I C M C  Mainz (1981), p. 730. 13. J. Kivel, F. C. Albers, D. A. Olsen, and R. E. Johnson, J. Phys. Chem. 67, 1235 (1963). 14. C. O. Timrnons, J. Colloid Interface Sci. 43, 1 (1973). 

On the influence of cold work on the oxidation behavior of some austenitic stainless steels: High temperature oxidation

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