Oe ee eet crear fas) te cee ie tte ett BRC.CORP 37-74.F 175 cu Definition of the Problew 33._OXIDATION Normal surface oxidation involves progressive reaction of a given motal eurface with oxidizing gacee, ueuslly at elevated temperatures. Catastrophic oxidation may involve metal ignition or very high corrosion rates from contact with molten salt (fuel ash) or oxide films, in the presence of alloying elements like V, Mo, or Pb. For an example of the latter form of catastrophic corrosion, see Section 43 on Vanadium Pentoxide (V20s) Corrosion. Ignition describes oxidation in ite accelerated version, vhere the rate of heat generation from oxidation exceeds the rate of heat dissipation, causing @ catastopnic rise in temperature, Internal oxidation 1s a phenomenon involving preferential oxidation of one or more alloying components below the surface of the metal instead of at the metal/scale interface. The effect of internal onidation 4e uoually embrittlement. Discussion of the Probl Carbon steel is seldom used in furnaces if metal temperatures are above 535°C (995°), because of excessive scaling rates. Higher temperatures Tequire alloys containing chromium, which provides a tightly adherent oxide film that retards the oxidation process. The amount of chromium required to supply practical scaling protection increases with temperature. Some improvenent in oxidation resistance is noted vhen only small anounts of chromium are added. The effect is more pronounced at the 4 to 6% chromium level. For instance, 5 Cr-1/2 Mo steel is considered an acceptable material for up to 650°C (1202°F) service. Progressive increases in chromium to 9 to 12% raise the temperature Linde eo 705* and 760°C (1301° and 1400°P), reopeetively, while with 14 to 10% chromium, the recommended limit 1s 760° and 815°C (1400° and 1499°F), respectively. At 27% chromium, the limit is extended to 1095%C (2003*F). If cyclic temperature conditions prevail, additions of nickel are necessary to reduce the differential in thermal expansion between the oxide and the base metal. This correspondingly reduces the stress at the scale- etal interface and thus reduces scaling (see Figure 33-1). — Silicon and aluminum are other steel additives which increase exidetion resteteuces They wut be eupluyed iu gual quantities, however, in order to not affect adversely the mechanical properties of the material. Frpertenre indinates the Following limteing temperatures for several chromium containing steels, for operation without excessive scaling in clean oxidizing gas atmospheres:176 BRC-CORP 37-74.F Maximum Temperature, °C For Scaling Resistance Carbon Steet 365 (1049°P) 1/2% Mo Steel 565 (1049°F) 1% Cr 1/2% Mo Steel 595 (1103°F) 21/42 Cr 1% Mo Steel, 693 (1173°F) 5% Cr 1/2% Mo Steel 650 (1202°F) 7% Cr 1/2% Mo Steel 680 (1256°F) 9% Cr - 12 Mo Steal 708 (1301°P) 12% Gr Steel 760 (1400°F) 17% Cr Steel 815 (1499°F) 16% Cr - 14% Ni-2% Mo Steel 870 (1598°F) 18% Cr -" 8% Ni Steel 870 (1598°F) 18% Cr- 10% Ni- 2% Mo Steel 870 (1598°F) 27% Cr Steel 1100 (2012°F) 25% Cr- 20% Ni Steet 1150 (2102°F) Figure 33-2 indicates temperatures of oxidation resistance at which the alloys can he used continuouely without exccosive pxidatiou. Wowever, fur this chart as well as the preceeding table, these limits serve only to make a Preliminary selection of high temperature alloys. Several factors can then affect the final selection in such a manner that the marimm temperature Limte for the alloy would be adjusted upward or dovnvard. These factors could include: intermittent exposure, instead of continuous; cycling conditions; contaminated gaseous atmospheres; mechanical properties; and expected life of the part. The chart of Figure 33-3 compares the corrosion rates of steels in air, with those encountered in ofl heaters at the same temperature. However, elements such as sulfur, vanadium, and sodium in the fuel can change the nature of the metal oxidation, sometimes increasing it to several inches per vear. under very adverse randitane (e.g. 4m the precence ef molten fuel ach) + ‘An example of oxidation on the outside of a furnace tube, created by elevated metal temperatures, resulting from coke buildup on the inns surface is shown on Figure 33-4. As indicated in the table, ordinary el is adequate to resist oxidation over a large part of the temperature range ordinarily encountered in oil and chenical processing. For those services where the Limit for steel 1s exceeded, a wide range of intermediate and highly alloyed steels is available. Tn certain alloy systems, one or more components which form more stable oxides than the base metal may oxidize preferentially below the external surface of the metal. This is called internal oxidation because the oxidation takes place within the metal matrix, rather than at its surface. "Green rot" is a term for one type of internal oxidation, which is used descriptively in referring to the greenish looking fracture surfaces it produces in certain Cr/Ni and Ur/Ni/Fe alloys when the component fails. ‘The mechanism involves the oxidation of chromium carbides that have precipitated due to exposure of the metal to carburizing compounds. The result of this type of internal oxidation 49 serious embrittlement uf the alloy. & Prcccccvcccccccceé BRC-CORP 37-74.F "7 Hethods of Checking for the Frobiew Scaling from surface oxidation may be monitored by visual inspection, radfography, or dimensinnal measurement. Na methade of determining the extent of internal oxidation are currently known. Methods of Eliminating the Problem Proper alloy choice, proper burner design for furnace tubes, and avoidance of unnecessary temperature excursions or fluctuations are methods of controlling metal oxidation to an acceptable level. Pitfalls Failure of heater tubes 1s often due to temporary flane impingement. This type of failure cannot be helped effectively by a different choice of materials. but rather through proper heater and burner design and clone control of firing techniques. Certain impurities in the fuél ‘of oil-fired furnaces vastly decrease the temperature limite established for scaling resistance of alloys. For many alloys, high temperature metallurgical phase chang tion’ or maximum temperature limite rather than si (see Section 15), sigma phase formation in austenitic steels (see Section 35), and graphitization of carbon steele Section 21).178 BRC-CORP 37-74.F 75 Ni - 16 cr 78 Ni - 20 cr 80 Ni - 20 cr 18 cr 2G 7BNi-14cr Type 310 (20Ni- 25 cr) -10 ~~ Type 330 25 Ni - 20cr 8 Type 309, (4 Ni- 23.60 Change in Weight, % -50 Type 347 (8 Ni 18 cr) 14.Ni-19.Cr ‘Type 204 (@Ni- 18.cr ° 200 400 00 ‘800 1000 Hours of 18-5 Cycles Figure 33-4 Effect of Nickel Content on Ait Oxidation of Alloy Each cycle consists of 15 minutes ar 2A2°C (1800"F) followed by a § minute air cooling oe wr) TYe BRC-CORP 37-74.F v9 ToT 7-7 Carbon Steel emer Estimated Value ‘Armeo Aluminized Type 1 Tone 410 Type 405 Type 409 Type 430 Types 302/304 Type 321 Type 316 Type 347 Armen 21-6-8 Type 442 Type 2028 Carpenter Alloy 20 Cb-3 Armen 22-13-6 ‘Armeo 20-45-6 Type 446 USS 18-18-2 Type 309 Type 310 Incoloy 800 Inconel 625 {ncone} 600 Incone! 001 Has Hoy X Rolled Alloy RA 933 Rolled Alloy RA 330 ‘Armeo 188R cee |e | ee ea ee |e |e 800 1000 1200 1400-«1600-«1800— «2000 2200°F 4267 59778 6489 760 BN. RP 1naRa_tonAATC ‘Temperature Figure 332 Approximate Maximum Temperatures for Continuous Air Oxi Resistance of High Temperature Alloys180 BRCCORP 37-74. WWo.> vays at 620°C (1200°F) W190 Days at 650°C (1200°F) 8.3 Daya at 700°C (1300°F) 61 Days at 730° (1350°F) 7s Days at 815°C (1500"F) B78 Daye at 775°C (14257) T TF ‘Wrought Materiat A Wrought Material [Furnace Gases from] 23cr-12N 22 cr ~ 12 Wt Low-Suiter Past 18 Cr -8NI-Cb it cr 18Cr-aNt 13 ce Wer scr 1309 at > Cr ~ 0.5 Mo ier 4.75 Cr = 0.5 Mo 10 Cr -0.5 Mo 3 cr-0.$ Mo =1.5 st 5Cr-0.5 Mo 1.5 Cr -0.5 Mo 316 2 Gr = 0.5 Mo Finin Carton Stee! 64 1.5 Cr ~0.75 st 1.25 Cr - 0,5 Mo Plain Carhon Ste 29Cr- 9M T T 24 Cr 2 ML caves 24 Cr = S6 Ni = Ben 29Cr-9 Nt 16 Cr 36 Ni 24Cr-12 NL 10Cr~0.5 AL 16 Cr ~ 36 Nt 3¢r-13Ni-6Cu Plain Carbon Stee! 1742 ° 025 0,500.75 Gieaoae Tanwe by Sonling, Lose Wy Sealing, tn, per yr ‘a. per yr (Lett) Spectmens heated in uncontaminated sir in an electric laboratory furnace, (Right) Specimens exposed to sulfur-bearing gesce in typlcel refinery crude-oll, heaters burning low-sulfur fuel off oF gas and high-sulfur crude for the times indleated in each instance, Wie Daye ws crete (100¢r) O36 Days at 730°C (1350°F ) G36 Daye at 815°C (1500°F) from Relatively High-Sulfur Fue ‘Type 310 Stainles ‘Type 317 Stainie 5 Cr -0.8 Mo 2.25 Cr 1 Mo iain Carton Steet ° 0.25 0.80 Loss by Scaling, tn. per vr Figure 33.3 Comparison of Metal Lossas Due to Scaling for Several Wrought and Cost Mate eo *BRC-CORP 37-74.F tat Oxide Layers ° Steel Figure 334 Section from Steel Pipe Severely Oxidized and Bulged on Surface Facing Firebox Magnification: 1X. 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