NN ter ey TosContents Introduction ...2...4..sseeeeses 1 Elevated- Temperature Characteristics of Engineering Materials 3 ‘Mechanical Properties at Elevated Temperatures. . B Corrosion at Elevated Temperatures, ol Industrial Applications of Heat-Resistant Materials. 61 Properties of Ferrous Heat-Resistant Alloys......+++ Elevated-Temperature Mechanical Properties of Carbon and Alloy Steels . 89 Elevated-Temperature Mechanical Properties of Stainless Steels... 123 Elevated-Temperature Corrosion Properties of Carbon and Alloy Steels. 146 Elevated-Temperature Corrosion Properties of Stainless Steels .. 2 ea 159 Alloy Cast Irons... 179 High-Alloy Cast Steels = 200 Properties of Superalloys -......... - 219 Metallurgy, Processing, and Properties of Superalloys .... 22 Directionally Solidified and Single-Crystal ‘Superalloys 255 Powder Metallurgy Superalloys. 2m Effect of Heat Treating on Superalloy Properties Elevated-Temperature Corrosion Properties of ‘Superalloys ‘Microstructural Degradation of Superalloys Protective Coatings for Superalloys Properties of Nonferrous Heat-Resistant Materials... Titanium and Titanium Alloys Refractory Metals and Alloys 1.7 Nickel-Chromium and Nickel Theis: Structural Intermetallies . Structural Ceramics Carbon-Carbon Composites Special Topics ..... Assessment and Use of Creep-Rupture Data ‘Thermal and Thermomechanical Fatigue Structural Alloys Elevated-‘Temperature Crack Growth of Structural Alloys: Creep-Fatigue Interaction Design for Elevated-Temperature Applications Design for Oxidation Resistance Index .. 331 335 345, 347 361 383, 389) als 429 M4 454 486 499 518. 534 549Introduction eae Temperature Characteristics of Engineering Materials . : af Mechanical Properties at Elevated Temperatures 3 31 Corrosion at Elevated Temperatures... sees Industrial Applications of Heat-Resistant Materials - Be -67Elevated-Temperature Characteristics of Engineering Materials HIGH-TEMPERATURE ALLOYS broadly refer vo materials that provide strength, enviton- ‘mental resistance, and stability within dhe 260 0 1200 °C (500 to 2200 °F) temperature range ‘They have generally been used in the presence of combustion from heat sources such as turbine engines reciprocating engines, power plants, fu races, and pollution control equipment. In order to retain strenglh under these conditions, it is imperative that their microstructures remain sta- ble at high operating temperatures During the last few decades, a beter under standing of alloying effects, advances in meling technology, and the development of controlled thermomechanical processing have led (0 new and improved high-temperature alloys. Most such alloys have suicient amounts of chromium (with without additions of aluminum oF sil- con) to form ehomia (Cr20»), alumina (AlzO3), andlor silien (SiO) protective oxide scales, hich provide resistance t environmental degra- dation, However, oxides cannot protect against failure by ereep, mechanical or thermal fatigue, thermal shoek, or embrittlement, In actual serv ice, failure of a componenmateral is typically caused by a combination of two oF more atack ‘modes, which synergistically accelerate depada- This anicle briefly reviews the elevated-tem perature characteristics of various engincered ‘materials. Although emphasis has been placed on the most commonly employed-—most notably ‘hromiunalloyed steels and superalloys—low- density metals (tanium-aluminum-,and magne: sum-base alloys), refractory: meta alloys, in- ‘ermetalles, ceramics, and carbon-carbon composites are also discussed, The high-em- perature property data presented are comparative, the intent being to provide the reader with an understanding of alloy group rankings (se, for ‘example, Fig. 1 1 5). More detailed informa- tiontdata on specific alloys can be found in the ‘many ctedaricles found throughout this Volume. Cast Irons and Steels Heat-resistant cast irons are basically alloys ‘of iroa, carbon, and silicon having high-tempera- {ure properties markedly improved by the ad tion of certain alloying clement, singly or in ‘combination, principally chromium, nickel, mo- Iybdenum, aluminum, and silicon in excess of 3%, Silicon and chromium increase resistance heavy scaling by forming a light surface oxide thats impervious to oxidizing atmospheres. Bout elements reduce the toughness and thermal shock resistance of the metal. Although nickel does not appreciably afect oxidation resistance, it in- creases strength and toughness at elevated tem- peraures by promoting an austenitic structure that is signifcandy stronger than ferric sire tures above 540 °C (1000 °F), Molybdenum in ‘reaseshigh-lemperature strength in both feeiic and austenitic iron alloys. Aluminum additions fare Very potent in raising the equilivium tem- perature (Ax) and in redueing both growth and scaling, but they adversely affect mechanical propertics at room temperature. Alloy east irons that have successfully been used for low-siress elevated temperature applica- tions include ‘© High-silicon rons (40 6% i), with o without ‘molybdenum additions (0.2 to 2.54), used at temperatures up to 900 °C (1680 °F) ‘+ Austenitic nicke-alloyed irons (18 to 344% Ni With 0.5 o 5.5% Cr, used at temperatures up to 815 °C (1500 °F) ‘© High-ctromium white irons (12 w 399%), used at Lemperatures up to 1040 °C (1.900 "F) Applications for these alloys include eyliner liners, ‘exfust manifolds, valve guides, gas turbine hous ings, ubocharger housings, nozzle rings, water ‘pump bois, and piston rings in aluminum pistons. More dete information on heat-resistant ions can be found inthe article “High-Alloy Cast Irons” inthis Volume, Carbon steel, the most widely used stl, is suitable where corrosion or oxidations relatively mld. It is used for applications in condensers, heat exchangers, boilers, superhestrs, and sis. The widespread usage reflects its 1 cost, generally good service perfor 00d weldabilty. The basic low-carbon grade ‘contains nominally 0.15% C and is used in vari- ‘ous tubing applicitions, Medivm-carbon grades ‘contain 0.35% C (max) with manganese contents ranging from 0.30 to 1.06%. These grades are used for ting, pipe, forgings, and castings. For low-stross applications plain earbon steels cam he used at temperatures 42S °C (800 °F ‘Temperatures up to about $40 °C. (1000 °F) ean bbe withstood for only short periods. Figures 110 5 compare the clevated-temperature properties of carbon steels with tase of other alloy systems. Carbon-molybdenum steels contain 0.50% Mo with a carbon content of about 0.20%. These steels are used in the same kind of equipment as carbon stel, but they can be more highly stressed ‘because the molybdenum addition increases shorttime tensile strength and reduces the creep rate for a given stress and temperature. If graphi- tization under service conditions is probable, the maximum service temperature fr exrbon-molyb- ‘denumn steels is about 450 °C (850 °F) Chromium-Molybdenum Steels. Creep-r sistant low-alloy steels usually contain 0.510 19% ‘Mo for enhanced ercep strength along with chro- ‘miu contents between 0.5 and 9% for improved corrosion resistance, rupture ductility, and ress- tance aginst graphitization. Small additions of carbide formers such as vanadium, niobium, and titanium may also he added for precipitation strengthening and/or grain refinement. The ef fects of alloy elements on transformation harden ing and weldabiity are, of couse, additional fac- ‘The three general types of ereep-resistant low alloy stels are © Plain chromium-molybdenum steels include the 1Cr-0,5Mo and 1.2SCr-0.5Mo alloys used at emperatures up to 310°C (85D °F); 2.25Cr- Mo steel, the most widely employed grade, used at temperatures up to SRO °C (1075 °F): S5C¥-0.5Mo steel used at temperatures up to 620 °C (1150 °F); and the 7Cr-0.SMo and 9Ce-1Mo alloys, used a temperatures. up to 650 °C (120 The chromivon-molybdenum-vanadivun steels provide higher creep strengths and are used in pplications where allowable design stresses ‘may require deformations less than 1% over the Tile of components operating at tempers tures up to 540 °C (1000 °F). The most com4// Introduction ston composition contains 19 Cr, 1% Mo, ad 025% ¥ + Modified chromiummolybdenum sees co tin varios micralloying elements sch 35 nau, niobium, anim, and boron and dre ose for thick section components in hy- dogen-containing environmen. Depening on the pad, these movfied pads can be {ed at femperatres up o 455 0 G00 °C (850 wnii0 Chromium-molybdenum steels are widely sed for pressure vessels and piping inthe oi and ‘industries and in fossil uel and nuclear power plants. Product forms include forgings, wing, pipe, castings, nd pate. Figures 3 and 5 compare Sng MP the propertics of chromium-molybdemam steels with those of other alloy systems. Detailed infor- mation on the compositions and properties of these steels, which are covered by various ASTM. specifications, can be found in the anicle “Ble- Vated-Temperature Mechanical Properties of (Carbo and Alloy Stels” inthis Volume. ‘Chromium hot-work die steels types H10 0 H19) have good resistance to thermal softening (high hot hardness) up to $40-°C (1000 “F) be- cause of their medium chromium content (5%) land the addition of earbide-forming, clements such as molybdenum, tungsten, and vanadium, ‘An increase in silicon content (up to 1,208) im- proves oxidation resistance at temperatures up 800 °C (1475°F). Stainless Steels and Superalloys ‘When the severity ofthe service environments precludes the use of cast ions, carbon steels, or Jow-alloy steels, more highly alloyed materials such a stainless steels and superalloys must be considered. As shown in Fig. 6, some wrought superalloys—pantcularly hose’ based on the austenitic Fe Ni-Cr system—evolved from stain Tess steel technology. In fact, some stainless steels are also considered iron-base superalloys. Examples include A-286 (UNS 565286). a pre- cipitation-hardening austenitic stainless steel, and 19-9-DL (UNS $63198), a solid-solution- srengthened austenitic stainless stl Fig.1 Tenerew (7). Source Rol 3 Shortie highsemeraure yc tenth for varios materi The broken property sek ines nica at ceramic enh values re Compressive, nt seo ak Thome dsb bed ner Sle eles oo emcee ae esElevated-Temperature Chat Testtampeatve, °C acteristics of Engineering Materials / 5 or 71 1316 1998 al * rT = ~ m 1901 ta ta i Tea ie vant, 1 soa er 5% Cr otwork: 1655 coon copa + = 13 2 | sermon ot sao tt 5 Saat F woh: fro F i en ita hy, : F woh 7 wi Bon Neste se rt i oe |s2 5 Tan gre el do eer ‘aluminum plate ol mt rey - — |, ee Testtomperaire,-F Fig. 2 erortemoertue onthe unseen steht varus mals and alloys Souee Res Generally, however, stainless stels ean be df= Terentiated by thei lower alloying content. For ‘example, compare the analysis of type 308 stain- Jess with Waspaloy alloy (UNS NO7001), a pre- cipitationhardening.nickel-base_high-tempera- ‘urealloy. Type 304 includes carbon, manganese, silicon, chromium, and nickel. Waspaloy alloy, ‘in addition to these elements, includes molybde- ‘num, cobalt titanium, aluminum, zirconiue, and boron, These additional elements in the right combination give Waspaloy alloy its consider- able stength and corosion resistance al tempera- tures of up 1 $70 °C (1600 °F), Stainless Steels (Ref 7, 8) Stainless steels for elevated temperature ap ‘ations include ferrite, martensitic, preciptation- hardening, and austenitic grades, Next co the 80- penlloys, the stainless steels provide the best ‘combination of high-temperature corrosion rsis- {ance and high-temperature mechanical strength (of any alley group. More detailed information on stainless steols can be found in the articles “Ble- vated-Temperature Mechanical Propenies of Stainless Steels" and_ “Blevated-Temperatre Corrosion Propenies of Stainless Steels” in this Volume, resistance up 1 815 °C (1500 °F). Where ele- vated-temperaure srength is a requirement, the tase ofthis composition is limited because ofits relatively low creep strength. Although itis duc between about 400 and 590°C (750 and 1100 “F), this stool will be brite when iti cooled to ambient temperature afer prolonged heating in ‘this range (sigma-phase embritlement). The bit teness may be eliminated by reheating 1 about 760 °C (1400 °F), The 27% Cr stainless steel type 446, which has relavely low elevated-tem- perature strength, is used between 870 and 109 °C (1600 and 2060 F) in spplications where the ‘most severe oxidation is encountered. Its also Stubjet to the same embviting phenomena as {ype 430 steel, The major application of type 446 stool is in such items as furnace parts, soot Blow fs, and thermocouple protection tubes, where stresses are relatively low The martensitic stainless steels most com- monly used for elevated-temperatureapplica- tions ae the so-called “Super 12 Chrome” steels ‘hat contain molybdenum (up t 3%) andor tung- sten (up to 3.5%) for greater strength at elevated lemperatutes. Other elements, such as vanadium, niobium, and nitrogen, may also be added in small amounts for additional strengthening. The 129% Cr martensities withthe aforementioned al- lying additions ean be used at temperatures up 0 650 °C (1200 °F), but they provide only mod- 12% GrM stots 1% CeMOV sees Carbon rmaganese sets _ Castrickehbase alls ‘The ferrtic grades, which have good resis- tance to oxidation at elevated temperature, are not ‘known for theie mechanieal strength at high cer iar ae — \ Magnesiom or perature Instead, these alloys are primarily used in corosion-resistant applications. Another lim- ‘Aucive ‘Sates iting fctor for high-chromium feritic stainless steels is sigma phase embeltlement duo to high: temperture exposure. Two examples of ferrite stainless stels are given below. ‘The 17% Cr stainless sce, type 430, is used in spplications that require oxidation and corrosion oo ——~8O Temperate, “6 a0 Fig. 3 srestoproduceupue intent or varius os Source: Re6 / Introduction erate strength above $40 °C: (1000 °F. Straight {unalloyed) martensitic grades can only be wsed al temperatures up to 400 °C (750 °F), Property data for martensitic stainless stels are given in 3005, “The austenitic stainless steels are essentially alloys of iron, chromium, and nickel. These stecls asaclassare the strongest steels for service above about 540 °C (1000 °F), Property data for the Austenitic grades ar piven in Fig.2to 5. Some of the more commonly employed alloys are dis cussed below. “Type 304 s the most common grade of austen tic etvomium-nickel steels, which a a group are used for handling many comosive materials oF resisting severe oxidation. Type 304 steel has excellent resistance to corrosion and oxidation, thas high croop strength, and is frequently used a {emperatures up to 815 °C (1500 °F), Type 304 steel is being used successfully and economically in high-temperature service in such applications as high-pressure steam pipes and boiler tubes, ‘giant superhoates, and oil-tefinery and process industry equipment "Types 321 and 347 stainless stools are similar to type 304 except that Gtanium and niobium, respectively, have been added wo these steels. The titanium and aiobium additions combine wi carbon and minimize invergranular corrosion that ‘may oecur in certain media after welding. How= ‘ver, the use of niobium (or titanium) does not ‘ensure complete immunity to sensitization and subsoquent intergranular attack when the stecl is ‘exposed for long times in the sensitization range ‘of 425 10 815 °C (800 to 1500 *F). However, types 321 and 347 stainless steels are widely used for service inthis temperature range. “Type 316 stainless sce, which contains mo- |ybdenum, s used for high-strength service up (0 about 815 °C (1500 °F), and it will resist oxida tion up to about 900 °C (1650 °F). However, above this temperature, in still ar the molybde~ ¢_| coe\ : 7 BTL mom a ad come i & 766 ee on ‘num ll form an oxide that will volatilize and result in rapid oxidation ofthe ste, For service above about $70 °C (1600 °F), types 309 and 310 stainless stecls, which contain bout 23 0 25% Ce, are used. These stels have the best high-temperature strength ofthe austeni- tic stainless scl at these temperatures, und be- cause of their chromium content, they can be ‘sed in applications where extreme corrosion or oxidation i encountered. “The highest service limits for oxidation rexis- tance of stainless stels is achieved by the highly alloyed type 380 grade, This alloy, which con- tains 1994 Cr, 25% Ni, and 1.0% Si, is suitable for ‘continuous service at temperatures as high as 1150 °C (2100 *8. tation-hardening stainless steels have the highest room-temperature strengths of all the stainless steels, They fill an important gap between the chromium-tree 18% Ni maraging steels and the 124% Cr quenched and tempered Imartensiic grades. One grade, the austenitic A~ 286, has moderate suengih and long-term service ‘capability up 10620 °C (1130. Valve steels are austenitic ntrogen-suength- ‘ened sleels that have boon used extensively in Automotiveiateral combustion engine valve ap plications. Examples of such alloys include 21 2N Q2ICr, Ma, 2Ni+ Np, 21-4N (21Cr. 9M, 4Ni-+N), 21-12N QICK, T2Ni, 1.25 Mn+ N), ‘and 23-8N (21Cr, BNi, 3.5Mn +N). The nitrogen feontents in these alloys range from 0.20 to (0.508%, These engine valve grades arc used at temperatutes up 10 760 °C (1400 *F), but they provide fainty low strength atthe upper end of thie temperature capability, Cast heat-resistant alloys are primarily used in applications where service temperatures ex- ceed 650 °C (1200 *F) and may reach extremes as high as 1315 °C (2400 °F), Many of the cast heat-resistant alloys are compositionally related fo the wrought stainless stcls and co the cast cortosion-resstant alloys, The major difference S ‘guys 1900 «7 ‘rapt. som 208790000 —Te00 1860 FOO Temes K Fig. 4. maximansenice tener rows rep estan materials, Source: Res between these materials is ther carbon content. fons, carbon in the cast heat-sesistant alloys falls i a range from 0.3 t0 (0.6%, compared with the 0.01 10 0.25% C that is ronmally associated with the wrought and cast ‘corrosion-resistant grades. "The standard cast heat-resistant grades have high ereep strength and generally good oxidation resistance, show better carburization behavior than the corresponding srought alloy, and are tvailable in product forms such as tubes, retorts, snd hangers at relatively low cost forthe alloy Content, Detailed information on the composi: tions and properties of cast heat-resistant alloys cean be found in the article "High-Alloy Cast ‘Steels inthis Volume, Cast duplex nickel-chromium alloys near he fevicetie composition (about 50% CA) develop ‘compact chroma scales rapidly and show excep: tional esistace to oxidation and fucl ash corro- sion. Small niobium additions, as in IN-657,im- prove creep suength, Such duplex alloys are Seseribod in the anicle “Nickel-Chromiom and NickcI-Thori Alloys" inthis Volume. Superalloys Superalloys are nickel, iron-nickel, and co ballbase alloys generally used at temperatures above about 540 °C (1000 °F). As shown in Fig 6, the iron-nickel-base superalloys are an exten- sion of stainless stel technology and generally ‘are wrought, whereas cobalt- and nickel-base su- peralloys may be wrought or east, depending on the application/composition involved. Appropri- ‘te compositions of all superalloy base metals ean be forged, rolled 10 sheet, or otherwise formed into a varew of shapes. The more highly alloyed compositions nocmally are processed as Castings, Properties can be eontrolled by adjust ‘mens in composition and by processing (includ- ing heat treatment), ancl excellent elevated-tem- perature strengths are available in finished Products, Figures | o 5 illatate the excellent lovated- temperature characteristics of superal loys. As indicated in Fig. 5, no othe alloy system ‘nas u better combination of high-temperature cor- rosion resistance and stress-rupture. strength ‘Some superalloys, parculanly nickel-base cast ing alloys, ean be used at temperamnes that are approximately 854 of their incipient melting ‘point. Such alloys exhibit oustanding creep and Sress-ruplure properties at temperatures in ex ‘ess of 1040 °C (1900 °F). The oxidation tess {ance of most superalloys is excellent at moderate temperatures—about 870 °C (1600 °F) and be: Jw. Some alloys can be used at temperatures up to 1200 °C (2200 °F). Coatings ean further e hance high-temperature conrosion resistance. ‘More detailed information regarding the compo- sitions, propertics, and processing of superalloys anbe found in the Sections "Properties of Super- alloys" and "Special Topics” in this Volume. Superalloy Development. Nickel-base su peralloys were created at approximately the tara Df the century with the addition of 20 wi% Cr in fn 80 w(% Ni alloy for clectrical heating ele-‘ments Inthe late 1920s, small amounts of alu ‘num and lanium were added to the SONi-20Cr alloy, witha significant gain in creep strength at ‘levated temperatures. I soon bocame apparent that iron and cobalt alloys could be more effec: tively strengthened by solid-solution additions, while nickel alloys could be strengthened by coherent phase, Concurrent with these ai- tions, the carbon present in the alloys was ides fied as having a strengthening effect when com- bined with other alloying elements wo form MgC and MaxC carbides, Other grain-boundary form= fe, such as horon and zireonium, were added to polycrystalline materials to hold the material to Tn the early development time period (about 1926), Heracus Vacuurnsehinelze A.G. received patent for a nickel-chromium alloy that con- lained up wo 15 wide W and 12 wt Mo, thereby introducing the refractory metals into superalloy compositions. The purpose of adding refractory mets was to increase the high-temperature strength of the nicke-base alloy. By the 19305 there were two iron-base “heat-resisting alloys ‘containing cither tungsten or molybdenum addi- tion, and the use ofthese two metals was widely sccepted in cobal-base alloys. Inthe early 1950s, alloys containing about $ wt% Mo were intro- Aaucod inthe United States. The commercial ex ploitation of moly ena additions took place in 1955, A cast alloy containing 2 wt% Nb was available in the late 1950s In the early 1960s, tungsten and tantalum were widely accepted for alloying in nickel-base alloys. The demonstration of the effectiveness of rhenium additions in rickel-hase alloys ocurred in the lte 1960s, ‘Some highly alloyed nickel-base castings have {otal refractory metal contents exceeding 20 wt. Finally, also in the late 1960s, hafnium additions were found to stabilize and strengthen grain- boundary structures, Figure 7 chars the develop ‘ment of superalloys from 1940 wo the 1990s, ‘Superalioy Systems. loys can be divided into three types: ron-nickel- nickel, and cobalt-base. Each ofthese is briefly reviewed below. ‘The most important class of iron-nickel-base superalloys includes alloys that ar strengthened hy itermetallic compound precpitaion in a face-centered cubie (fee) matrix. The most com- mon precipitate is’ typiied by A-286, V-57, oF Tncoloy 901, but some alloys precipitate gamma double prime ¢Y”), typified by Inconel 718, Other iron-nekel-base superalloys consist of modified stainless stels primarily strengthened by solid= foluion hardening, Alloys in this last category vary from 19-9DL. (18-8 stainless with slight ‘hromium and nickel adjustments, adltional so Tution hardeners and higher carbon) 10 Incoloy 00H (215% Cr, high nickel, and small additions of Gtanium and sluminum). The ron-nickel-base superalloys are used inthe wrought condition, "The mos important class of nickel-basesuper- alloys i that strengthened by intermetallic monly referred to as light metas, include magne- sium, aluminum-, and ttanium-base alloys Magnesium alloys have the Jowest densities (1.8 g/cm’) of any structural alloy, Magnesium alloys fr elevated temperature applications ust ally contain thorium (up to 3 wt‘). The magne sium-thoriumztconium cast alloys HK3A 7960 1970 ‘Year nocd (Mg3.3TH-0.7Z9 and HZIZA_ OMg-33TH 2.1Z0-0.722) are intended primarily for use at temperatures of 200 °C (400 “F) and higher. At 260 °C (500 °F) and slightly higher, HZ32A is ‘equal to or better than HK3IA in short-time and Tong-time creep strength at all extensions. The HKGIA alloy has higher tensile, yield and short- time creep strengths up 0 370°C (700 °F). ‘Another cast alloy, QH21A (Mg-2.5Ag-1.OTh- 0.722), retains 2 high yield strength up 10 300 °C (570°). This alloy is relatively expensive due to its silver content, Rare carth (RE) additions also contribute 10 improved clevatod-temperature performance. Al loys WES4 (Mg-S2¥-3.0RE-0.722) and WEA3 (Mg-4.0Y34RE-0720) have high tensile strengths and yield strengths, and they exhibit 200d properties at temperatures up to 300°C (570 °F) and 250 °C (480°), respectively. The WES4 alloy retains it properties thigh temperature for po 1000h, whereas WEA3 retains its properties at high temperature in excess of 5000 h. ‘Thorium-alloyed wrought alloys are also used at elevated temperatures, Alloy HMBIA (Mg- 3.0Th-1.2MMn), produced in extruded forms, i of ‘moderate strength. Ii suitable for use in appli- calions requiring good strength and creep reis- {ance at temperatures inthe range of 150 vo 425 C00 10 800 *F. Alloy HM2IA (Mg-2.0Th06Mtn), produced a Foogings, is useful a temperatures up to 370 0 ro Taos Teepetatue cab of superalloy wth apposite yer af ntaducian. DS, retonaly soli SC singles PIM, powder mela; ODS, oxdediiperon 425 °C (70010 800 °F) for applications in which good creep resistance is needed HKSIA and HM21A alloys, produced in sheet and plate forms, ae suitable for use at tempera ‘ures up to 315’ and 345 °C (600 and 650 °F, respectively. However, HM21A has superior strength and creep resistance, as shown in the following table: sb 205°C (40°F) apis BRSIA a 60 Anse 0-7 KIA Ey 40 Ae318-C (60° wis KA, ‘Additonal data on magnesium alloys ae given in Fig. 1 w 3. As these daa indicate, th elevated temperature performance of magnesium alloys is comparable to that of some aluminum alloys. “Most other alloy systems, however, have superior high-temperature properties, ‘Alyminum alloys have higher densities (-2.8 ‘om’ and higher room-temperature strengths than magnesium alloys, Some cast aluminum al-ig. 8 Tove svete of aluminum alloys 24004, BB 240°17 and 2420-1371 astnctionsof Joys are used in applications at moderately cle~ vated temperatures e. pistons in intemal com- 25M). As shown in Fig. 8, his Sucngth temperatures as high 2 °F, Some oer cast aluminum alloys canbe used a lighly higher temperatures (175 °C, of 350 . The Tex seis of wrought age-hardenable al loys that ar based onthe AL-Zn-Mg.Cu system develop the highest room-temperature tensile propertis of any aluminum alloys produced fom Conventionally east ingots However, te strength ‘of these alloys declines rapidly if they are ex- pesed 10 clvated temperature (Fig. 9), de mainly Yo coarsening of the fine precipitates on ‘hich he alloys depend for thei strength Alloys Of the 2x series, such 36 2014 and 2024, per. form beer above these temperatures but ae not normally used for elevate-temperatue applica tons. Sirength at temperatures above about 100 19 200 °C-(200 to 400 °F is improved mainly by toldsolaion stengthening or second-phase fardenng. Another approach o improve the ele- vaiodtemperatue performance ofsluminum al loys as hen the use of rai solidification teh ogy 10 produce powders containing. high {persatiaions of elements sucha iro chro ‘nu dat fase slowly in solid aluminum. In this regard, several experimental materials based on he Abfo-Ce, ALFe-V-Si and ALCTZr ss tems are now avaiable hat have promising creep -operies upto 380 °C 650 °F) (Ret 10). Adi- Tena ta. on alumina alloys are given in Fig Twos. Titanium alloys provide an oustapding com- ‘bination of low density (-4.5 gfem’) and high stengih (vp to 1100 MPa, oF 160 Kel yield strength), Alloys have been developed that have ‘ef strength an resist oxidation at tempera tures as high as $95 °C (1100 °F). The improved tcevled temperature characteristics of thse al- loys, combined with thet high stengtho- ‘sight ratios, make them an atractive altemaive Elevated-Temperature Characteristics of Engineering Materials / 9 Tempers, gt 02m a sm a “(| am * Le oa Taw ne 1 i Bo a at Fig. 9 Yalusof 0.2% yell ses aluminum lost BO Crecpourfo 1000 hat tomperstasbxtwees oanaas0e to nickel-base superalloys for certain gas turbine alloys for elevated-tem perature applications are near-alpha alloys based fon the TAL-Sn-Zr system. portant alloying clements are molybdenum, silicon, and niobi Molybdenum enhances hardenability. and e hhances shor-ime high-temperature suength or improves strength at lower temperatures. Minor silicon additions improve creep stength, while riobium is added primarily for oxidation resis- tance a elevated temperate. Examples of these rnear-alpha alloys are Ti-1100 (Ti-6AL-2.75S0- 42r-Q.4Mo-0.ASSi) and IMI-834 (T1-5.SAL-4Sn- 421-0 3Mo-INb.O.SSi), Specific yield strengths density corected) of titanium- and niekel-base alloys are compared in Fig. 10. Additional data are shown in Fig. 1,2, and As these dataclearly show, titanium alloys have far greater clevated- temperature strength than do plain earbon steels and low-density aluminum- and magnesium a loys. More detailed information can be found in the article “Titanium and Titanium Alloys” inthis Volume, Refractory Metal Alloys Refractory metals include tungsten, molybde- rum, niobium, tantalum, and rhenium. These ‘metals and thei alloys have meliing points in ‘excess of 2200 °C (4000 °F), which is substan- tially higher than those of stainless steels or s- peralloys. As indicated in Fig. | to 5, the ereep szength of some refractory metas (tungsten and niobium) exceeds that of superalloys. These ae, however, a number of deficiencies of refractory ‘mecals and alloys that have precluded their being ville alternatives 10 superalloys in gas turbine engine applications: the open body-centered cu bic structure (precluding high creep resistance relative to the melting poin), lack of low-tem- perature dutiity inthe Via metals (tungsten and molybdenum), severe lack of oxidation resis: tance forall, and significantly higher density than superalloys forall except niobium. Detaled in formation on the processing and properties of these materials, as well as efforts made to over- come some of the aforementioned deficiencies (eg, coatings 1 prevent catastrophic oxidation) ‘canbe found in the article “Refractory Metals and Alloys” inthis Volume. Structural intermetallics ‘The search for new high-temperature structural ‘materials has stimulated much imerest in ordered intermetallics. Recent interest has been focused fn nickel aluminides based on NisAl and Nil, iron aluminides based on FeAl and FeAl, and titanium aluminides hased on TisAl and TiAL “These aluminides possess many attributes that make them airactive for high-temperature struc- tural applications. They eontain enough alumi- ‘num to form, in oxidizing environments, thin films of aluminide oxides that often are compact and protective. They have low densities, rela tively high melting poims, and good high-tem- perature strength properties ‘Nickel, iron, and titanium alurninides, like other ordered intermetallics, exhibit brite frac- ture and low ductility at ambient temperatures, Poor fracture resistance and limited fabicability restrict the use of aluminides as engineering ma- terials in most cases. Nevertheless, these materi- als appear the most likely to replace superalloys in high-performance applications. brief review ofthese materials is given below. More detailed information ean be found inthe article “Structural Inuermetallies” in this Volume. kel Aluminides. The nickel aluminide based on NiAl has a melting point of 1638 °C (2980 °F), compared with a solidus temperature (6f about 1300 °C 2370 °F) for most superalloys. [iA has excellent cyclc-oxidation resistance 10 1300 °C (2370 °F), low density, and, through minor alloy edditions, can provide erep strength to that of superalloys. While it has good in single-crystal form, its polycrystalline ‘ductility must be improved significantly, which provides a challenge to alloy developers ‘Considerable research also has been conducted ‘on the NisAl compound, which has a lower melt ing point than NiAI but sill offers strength and density advantages over curent superalloys. Bo- ‘on additions significantly enkance ductility over ‘4 wide temperature range up to its melting point [NisAL ingots produced using conventional elec: ‘uoslag remelt ESR) and vacuum induction melt- ‘ng (VIM) techniques be-have superpastcally ‘when thermomechanically worked at low strain rates, such as those associated with isothermal forging ‘Advantages claimed for “ductlized” nickel sluminides over conventional nickel-base super- alloys include: © Lower densities due to the higher aluminum content ofthe aluminides ‘© Much simpler chemical compositions than ‘many superalloys Single-phase structure ‘Strength derived from their ordered structure, ‘ot from precipitates of second phases; thus, no special heat weatments, such as aging, ae required10 / Introduction © Yiold strengths that increase with inereasing temperatures (as high as 650 w 750 °C, or 1200 w 1380 °F) 1 Very good oxidation resistance to 1100 °C (010) due to their high aluminum content 4 Potcatial lower cost than many superalloys ‘when full-scale production is achieved While as-cast properties of nickel aluminides suggest possible use in applications such as hot forming dies, turbochargers, permanent mold, and advanced pistons, relatively litle research has been performed 10 date on the suitability of ‘producing nicks! aluminides by investment cast- ing Tron and titanium aluminides, unlike the nickol- aluminum compounds, Jo not offer the same creep strength at very high temperatures ‘They do, however, have unique specific (density corrected) properties that should ensure their use ff some rotating components. FeAL, for example, has good strength to 700 °C (1290 °F), while its high melting point (1340 °C, or 2444 °F) and 00d oxidation resistance may well lead tits use ‘8 amatix material in metal-matrix composites Both TisAl and TiAl have good specific strength at temperatures to 1100 °C (2010 °F However, compared with superalloys. they each ‘have limitations, such as inferior oxidation esis- tance (TixAl) and ductility CTiAI—areas requir- ing further development ‘Nonmetallic Materials Polymer-Matrix Composites. Generally, polymers o polymer-matrx composites are not ‘Considered hea-esistant materials. Most organic ‘polymers soften or melt below 205 °C (400 °F). ‘As a result, most polymeric materials are used at ‘or just above ambient temperature (ess than 100 5C, of 212 °F), Polymer-matrix composites are tractive, however, because they provide major Weight and durability advantages. They have spe cific stiffness and strength values of not less than twice that of metallic structures. They also have similar advantages in fatigue strength "The most successful high-temperuture poly ‘meric material developed to date is a polyimide resin reinforced with graphite fibers. Graphite-r- inforced polyimide composites have been te ported tobe suitable for use in air at 288 °C (S50 TP) for at least 5000 h, At 316-°C (600 "P, the useful life ofthese composites is inthe range of 1200 to 1400 h. More detailed information on polymer-matrix composites ean be found in Vol- ‘ume 1, Composites, ofthe Engineered Materials Handbook published by ASM Intemational. Ceramics, both in monolithic and composite forms, offer the prospect of useful hea resistance, possibly to temperatures near 1680 °C (3000 °F), ‘coupled with lo density and in some cases ex: collet oxidation and corrosion resistance. Unfor= tunately, these ceramics also are brite, prone 10 thermal shock, and less thermally conductive than heat-resistant metals, leading to severe dei ciencis under tensile loading. These are inherent properties determined by the nature ofthe intra Tener ao? 10 300 500 0 ooo 100 = ne 0 neaaes Tressel | Dena conected 02% ye tess, MPa Densty cm === Dene coecten = oe sess, Seaesicent Nketzase soy consiy _| 5 L 0 a 100 200 0 wo Eo Temeerave, Fig. 10. spec kisah or vars titers base and eicha base alloys omic bonds, Mechanical properties also are SiC, produced by chemical vapor infiltration and highly variable, depending sensitively on prepa- ‘ation technique, impurities, and surface ish in Ceramies the process basically determines the properties, Processing of ceramies is also quite costly, Nevertheless, the toughness and thermal shock resistance of silicon nite (SisN) and its ability to form protective SiO> layers makes ita ‘candidate for turbine or diesel applications. Sil ‘con carbide (SiC) has similar properties, Other applications include heat exchangers, recupera- tors, and furnace components ‘Oxides, such as alumina (AIj0s) and ziror (207), ate also used for high-temperature appl ‘cations. Zirconia has been in service as a thermal barrier coating in airraft combustors on superal- loys for many years. However, the oxide~ype ‘ceramics tend to be less desirable mechanically than are carbide-nitide ceramics, although they ‘are very table in oxidizing atmospheres. ‘Ceramic-matix composites also show great potential. A wide variety ofweinforcing materials ‘maces, and corresponding processing methods have been studied. The most suecessfulfiberre- inforced composites have been produced by hot pressing, chemical vapor infiltration, or directed fetal oxidation, a process that uses accelerated ‘Oxidation reactions of molten metals to grow ce ramic matrices around preplaced filler o tein- forcement malerial peeforms. Much of the work has been on lass and glass-ceramic matrices reinforced with carbon fibers. Other fiber-tein- forced ceramic composites include SiC fibers in deposition, SiC-fiperreinforeed AloOs, and z= ‘conium carbide composites reinforced with zit ‘cnium diborid, produced by directed metal ox dation. Multiditcetionally reinforced ceramics have also been produced, such as silica reinforced With A105 or fused quartz "The excellent high-temperature strength, oxi- dation existance, and thermal shock resistance of 'SiaNs has led to the development of SiCy-tein- otced SNe. The major phase, SisNa, offers ‘many favorable properties, and the SiC whiskers provide significant improvement in fracture oughness. Whisker reinforced SiN is aTeading ‘candidate material for hot-section ceramic-en- zine components. More detailed information on nonrcinforced and reinforced cerumic materials ‘ean be found in the atte “Strctural Ceramis” inthis Volume. ‘Carbon-Carbon Composites. ‘The highest temperature expability of any material considered for high-temperature use is exhibited by carbon- carbon composites, graphite fibers ina carbon- [raphite malix. Carbon-carbon composites are now ised for one-time service in rocket-nozzle and missile exit core structures and in turbine aircraft brake shoes; SiC-coated carbon-carbon parts are being used as the nose cap and heating ‘edges ofthe space shut. Because carbon fibers tend 10 increase in strength with increasing temperature, carbon- carbon composites retain their tensile strength at fextteme temperntures, Carhon-carbon compos-Hevated-Temperature Characteristics af Engineering Materials / 11 10,000 10,000 109 § zg & 2 ‘0 — | stoners 10 - o ou 1 ve “00 1000 awe coat vue Fig. 11. Ser led ate cou prey actor sah ole poe envelope lise atte senha acre me ites provide unmatched specific stfiness and steength at temperatures from 1200 to 2200 °C (2192 vo 3992 °F). AL temperatures below 1000 °C (1832 °F), carbon-carbon composites exhibit specific strength equivalent to that of the most advanced superalloys. As a result oftheir earbon constituents and weakly bonded reinforced ma trix, eabon carbon composites also have supe For thermal shock, toughness, ablation, and high- speed friction properties. Another oustanding feature isthe low density (~1.6 g/em') of erbon- carbon composites. ‘Because carbon-carbon is not stable in oni ing environments at temperatures above about Sie regi Stor deta Source el 425 °C (800 °P, coatings are essential. Reftac- tory carbides such as SiC are applied by various processes, ‘The selection and performance of ‘coatings is the Focus ofthe article “Carbon-Car- bon Composites" in this Volume. Cost Considerations roma compottive standpoint, alloy selection must he based on expected costoffectiveness. ‘The best choice is usually the lowest-cost mat: rial able to meet design criteria. However, a higher-cost material offering greater reliability ‘may be justified for certain components in a sys- tem thats critical and/or expensive to shut down {for maintenance, Knowledge of alloy capabilities can be helpful in making a wise decision. "Figure I provides an overview of the costs of various materials. The relative cost is calculate by dividing the cost per kilogram ofthe material in question by the cost per kilogram of low car: bon (mild) ste reinforcing rod (rebar). Materials offering the greatest strength per unit cost ie {oward the upper left commer. Included here would be steels and aluminum alloys. As alloying in- ‘reases in stecls, costs go up. Hence, stainless steels containing chromium (an expensive alloy-12 / Introduction ing clement are much more costly. Further alloy- ing to produce superalloys results in even higher costs. Superalloys with high cobalt or refractory metal conten are very expensive ‘Some materials are expensive because of high processing costs. An example here would be the ‘ngingering ceramics shown in Fig. 11. The costs of the principal staring materials (silicon, eat ‘bon, and nitrogen ae relatively low, but the cost of engineering ceramics is significantly increased bby raw material preparation (mixing, milling, tc), forming and fabrication (ot pressing or hot isostatic pressing), thermal processing (sinter ng), and finishing (grinding, polishing, and in: spection). REFERENCES. 1. ME, Ashby, Materials Selection in Mechanical Design, Pergamon Press, 1992, p 24-55 2, MIE Ashby, Materials and Process Selection Chars, Pergamon Press, 1992, p 1-57 3. FU. Clauss, Engineer's Guide io HighTem- perature Materials, Addison-Wesley Publish {ng Co, 1969, p2 4. GA. Webster and RA. Ainsworth, High Tem perature Component Life Assessment, Chap- ‘man & Hal, 1994, p 13 5. A, Weronski and'T- Hejwowski, Thermal Fa feu of Metal, Mace Deir, In 1991, P 6, Superailoys I, C-Sims, NS, Slo, and W.C. Hagel, Ed, John Wiley & Sons, 1987, 15 7. “Steels for Elevated Temperature Service” United States Stel Corp, 1974 8 KP. Rofrbach, Trends in High-Temperature Alloys, Ad. Mater. Proc, Vol 148 (No.4), Cet 1995, p 37-40 9, WJ. Molloy, Investment-Cast Superalloys —A Good Investment, Ad. Mater. roe, Vol 138 (No.4), Oct 1990, p 23-30 10, UR. Pickens, High-Strength Aluminum PM. Alloys, Properties and Selection: Nonferrous Alls and Special Purpose Materials, Vol 2, ‘ASM Handbook, ASM Intemational, 1990, p 200-215Mechanical Properties at Elevated Tem peratures MECHANICAL PROPERTIES of interest for clevated-temperature applications include shor- lime clevated-temperature tensile properties, creep and stress-rupture, low-cycle and high-cy- ‘le Tatigue, thermal and thermomechanical f2- tigue, combinations of creep and fatigue (creep fatigue imeraction), and hot hardness. Each of these wil be described inthis tile with empha sis placed on the underlying principles associated With creep and stress-rupture properties. Mone ) >, > 0) 8) Huh rer sure rep, whet ty > >> Cs al Properties at Elevated Temperatures / 15 equations involving temperature and stress. An interrupted creep test provides much the sume data as & ereop-rupture experiment within the impose strain-time limitations. Direction of Loading. Most crcep-rupture tests of metallic materials are conducted in uniaxial tension. Although this method is suitable for ductile metals, compressive testing is more appropriate for brite, flawsersitive materials, In compression, cracks perpendicular to the ap~ pli stress do not propagate as they would in fension; thus, a better measure of the inberent plastic properties of a britle material can be ob- tained. Ta general, loading direction has lite influence ‘on many creep propentes—for example, steady- sate ereep rte in detile materials (Ref 6). How- ‘ever, even in these materials, the onset of third- Stage creep and fracture is usually delayed in ‘compression compared to tension. This delay is ‘duc 40 the minimized effect of microstructural ‘aws and the inability wo form a “neck-like” me- ‘chanical instability. Foe brite materials, the di- ference in behavior between tension and com pression can bo extreme, primarily due tthe Fesponse to flaws, Consequently, care must be ‘exercised when using compressive creep proper= ties of a brite material vo estimate tensile behav- “Test specimens for uniaxial tsi eeep-rup- te tests are the same as those used in short-term tensile tests, Solid round bars with threaded oF ‘wpered rip ends or thin sheet specimens with pin and clevis grip ends are typical (refer co ASTM Standard 8). However, many other types and sizes of specimens have been used successfully ‘where the choive of goometry was dictated by the Available materials, For example, small threaded round bars with a 12 mm (0.47 in) overall ength and a 1.52 mm (0.06 in.) diameter by 5 mm (0.2 in) long reduced section have been usedto meas- ‘ure transverse stress-rupture properties of a 13 ‘mm (0.51 in) diameter directionally solidified eutectic alloy bar (Ref 7). pty Sian fm oy ie 4 lorstess. Lowe16 / Introduction In the case of uniaxial compression testing, specimen design can be simple small-diameter right cylinders or parallelepipods with length-to- ‘diameter ratios ranging from approximately 210 44 Larger ratios end to enhance clastic buckling and smaller ratios magnify the effects of friction ‘between the test specimen and the load-transmit- ting member. These specimen geometries are wel suited for creep testing when only a smal ‘mount of material i available, or when the ‘eral is difficult to machine Environment. The optimum conditions for a creep-rupure tet are those in which the speci ‘men is influenced only by the applied stress anc temperature. This rarely occurs, particularly at clevated temperatures, and these conditions do not exist for real structures and equipment oper- ating under ereep conditions. For example, tur- bine blades are continuously exposed 0 hot, re active gases that cause corrosion and oxidation, Reactions between the fest environment and material vary greatly, ranging from no visible ‘effect wo large-scale atack, For example, creep: rupture testing of aluminum, ion-chromium-al num, nicke|-chromium, and nickel-base super joys “at elevated tomperatures in air can ‘generally be accomplished without problems, be- ‘ase these materials frm thin, stable, protective Oxide films. This is not the case for refractory ‘metals (molybdenum, niobium, tantalum, and tungsten) and their alloys, due 10 their strong reaction with oxygen, which leads to the formar tion of porous, nonprotective, and in some cases volatile oxides. Environmental effecis such as ‘Typical ta ndtbecype eeniomter or elevate owes macrins shoul eet spect Fig. 5 sbtampertue ciep tein. Gersometr i clamped Io LWT, real wares 0 7 L Nowhea dap = Dd ][P O> 108 we (0424 nd] [Noh aapan — a al" re [EE seorminaan a . win pts ot are) =m fe ¢ frastan atin | NUT Se ite 5 om eae) f ee a i i a of 38) sense i |e +8 “| i Racteeondt | dm ” Fig. 6 Theeprelyesonoth ecsin ss pom me.) Nahi 189 ea the 30% (1200-7 and alcool Mixed bar ad wor 4% 1 750° 400 "fe Notes weakening teed 24 5t630°C, and a cooked ayes a8 heated st 11S0~C 2400"F coke, Sb eat seg at 985 (1950 ter que, ‘oxidation and corrosion reduce the load-bearing cross-sectional area and can also facilitate the formation and growth of cracks. Reactions are also possible in inert atmos- pheres (such as vacuum) and in reducing gas environments. Elevated temperature esting. in ‘vacuum can result in the loss of volatile alloying elements and subsequent loss of strength. Expo- ‘ure to reducing gases can result in the absorption of interstitial atoms (carbon, hydrogen, and nitro Ren), which may increase strength, but also in dave bitlenes. ‘A “perfect” environment does not exist forall ‘reep rupture testing, The appropriate choice de- ‘pends on the materia, its intended use, and the Available environmental protection methods. If creep mechanisms ae beng determined, then the stmosphere should be as inert, or nonreactive, as ‘possible, However, ithe material isto be used in fan unprotected state in a reactive atmosphere, then creep-rupture testing should reflect these coneltions. CCreep-rupture data from inert aumosphere tests cannot be used for design purposes when the ‘material ill be exposed to conditions of severe ‘oxidation. However, if environmental protection ‘methods, such as exidation- oF corrosion resis- tant coatings, aze available, then testing in inert ‘gas is acceptable, and the resulting data can be used for design I reactions occur between the test environment ‘andthe specimen, the resultant ereep-ruptute data Will not reflect the tre creep properties of the ‘material, Rather, the measured data ae indicative ‘fa complex interaction between ereep and envi- ronmental atack, where the effects of environ rental attack become more important in long term exposure. Strain Measurement. Care must be taken to ‘ensure that the measured deformation occurs ‘only in the gage section, Thus, measurements ‘based on the relative motion of pars of the grip ping system sbove and below the test specimen fare generally inaccurate, because the site of de- formation i unknown, Extensometry systems are currently available that attach directly to the specimen (shoulders, special ridges machined on the reduced section, or the gage section itself) and transmit the relative motion ofthe top and bottom ofthe gage section via tubes and rods toa sensing device such as linear variable differential trans- former. Figure 5 illustrates such a system. These systems are quite accurate and stable over long periods of time ‘Other methods of direct strain measurement cxist and, under certain circumstances, ae sul- able. At low temperatures, strain gages can be directly bonded to the gage section and can be used (0 follow deformation over the range of, extension for which the stain gage is valid. For specimens that will undergo reasonable deforms- tions (€ > 1.0%, the distance between two gage ‘marks can be optically racked with acathetome- {eras a function of time. While the location of strain is known, use of this technique is operator dependent and is generally limited to tests of less than 8h or greater than 100 hin duration in orderom we Mechanical Properties at Elevated Temperatures / 17 ‘Table 1 Effect ofa notch on rupture time of Waspaloy ‘Sapo oeaniara 80°CAI075 "Pola harTEOC ‘140 Prarcoed Shen te essa 180°C(1975°P a cone san spa BH8 °C es {US50-Pra cob ap Ita Tea" oa ‘Soon eat he 1]-C(U975"P aeons sa ha 670°C ma "e001 CAIN, aco shentea ta ht 105) °C (LSP) cok st Ia 9O°C 9 os {Usb Parc aged Toho 1) °CCD'P) (apo ee conta 1505 Testing tempor, Fig. 7 Noone srry ao songs a 7 eerie rpm times or inconel 730. to permit sufficient readings to properly define the erep curve Notched-Specimen Testing Notched specimens are used principally as a ‘qualitative alloy election too! for comparing the filly of materials for components that may contain deliberate or accidental stress concentra ‘ions. The rupture life of notched specimens is an indication ofthe ability of a material to deform locally without cracking under muliaxial streses, Because this behavior is typical of su- penlloys, the majority of notched-specimen test- Ings performed on superalloys "The most common practice ist use a circum feretial 60° V-notch in round specimens, with a ‘eros-setional area atthe base ofthe notch one~ half that ofthe unnotched section. However, size and shape of test specimens should be based on requirements necessary for obtaining. repre sentative samples of the material being investi- sted Ina notch test, the material being tested most severely is the small volume at the root of the hotch. Therefore, surface effects and residual ‘stresses ean be very influential. The notch radius rst be carefully machined or ground, because it ‘cam have a pronounced effect on test results. The ‘oot rads is generally 0.13 mm (0,005 in) or less and should be measured using an optical ‘comparator or other equally accurate means. Size effects, stress-concentration factors introduced by novches, notch preparation, grain size, and hardness are all Known to afect notch-tupture lite ‘Noteh-rupture properties ean be objained by using individual notched and unnotched speci- mens, or by using a specimen with a combined noiched and unnotched tst section. The ratio of rupture strength of notched specimens to that of lunnotched specimens varies with notch shape and acuity, specimen size, rupture life (and there- fore suress level), testing temperature, and eat treatment and processing history, “To avoid introducing large experimental et- rors, notched and unnotched specimens must be ‘machined from adjacent sections of the same picoe of material, andthe gage sections must be ‘machined to very accurate dimensions. For the combination specimen, the diameter ofthe un- notched section and the diameter a the root ofthe fotch should be the same within +0025 mm (40.001 in). Notch sensitivity in creep cupture is influ- enced by various factors, including material and test conditions. The presence of notch may increase life, decrease life, or have no effect. ‘When the presence of a notch increases life over ‘the entire rango of rupture time, as shown in Fig. ‘64a, the alloy is said to be nowh strengthened: that i, the notched specimen can_withstand higher nominal stresses than the unnotched speci- men, Conversely, when the notch-raptare strength is consistently below tbe unnotched-rup- ture strength, a in Fig, 6c), the alloy is said to be T 000 rupture stenath YH ® Fig.8 ® iit ch dmersionson tess concentaton and nothurute renga.) Varisonofstes-concentaen facto with rl of minor to major diameter ad wit ato ‘Stout ras rma arc ot thd bar ses intranet range Variation of sc-rupure erg ato for 1000 re wit oo of aus © ivr siamese Cave str 12-30 ae heed 3 hatao0 C1650" an ai cooked Cra ste, ASTM No. 2;haress 15 HV; unotches pre dct, A et temperate, Sto" 1000" Cove 6 fr Retaclaly 2c quenched on 101850 Perched 20 at 15°C (1500 7 and coo reat 20h at 650 °C (1200-7 and icles Ooh th SC nea coo andl scbeue) 208.680 ans cook. Cranage ASTMN, 708: ards, 390 HV: unnoiched ptr duit, 7 teat temperate EOC Cane alo Retoraoy oe qverched om 1175 50°F read 2h =1013 °C a iceoked eheated 208 31 730°C (1 380°P and a cooled: andl whee 20 hateso-C and icook tiie ASTM No.2 chariness 32549 anolhed pte dati, 10st temperate, 60 C. Curved ior Reacts 26.0 quenched om 380 2ilsn stncnted 41 hat 730°C and ok cola nly head 20h a4 60 AC ane a cocked aaa, ASTM fo 8; ares, 975 HW ante pte dui, Fest epee 650°C18 / Introduction meet” wag” one | EE a , pot att & 3 Este | - da? 1 | BSoobe i ea Fig.9 Fugue renga futon of ie or nach and unnoiche aso ieee ain Sie was hate to N55" i130" and water qed eee 700°C G400°F) eld 12 icone. Waspaoy ws eat 180°C 1975", hl nt score raed io G40 (138 eld +h, ada coud and rallye fetal 60°C 40°F hel 6h, andr cock Salerro tes wre poducrdbycadrekusgihe S816 1,2 ‘he Wasploy 1.2 by cldaling a 24°C 737) andthe est resting Dare pects was 12.7 m0. ‘smc oh wae 89 mm (95), okie wan mt Oo and mechan was Dalat ‘urgoste of ts rm wo ote: ‘oich sensitive, or notch weakens. Many inves tigators have defined a notch sensitive condition as one for which the notch strength ratio is below iy. However, this ratio is unreliable and can vary acconding to class of alloy and rupture time Certain alloys and test conditions show notch strengthening at igh nominal stresses (short rup- ture times) and notch weakening at lower nomi- nal stresses (longer rupture times), withthe result that the stress-rupmure curve for notched speci: mens crosses the euve for uanotched specimens ‘as nominal stress is reduced. Figure 6(b) shows that Haynes $8 becomes notch sensitive under high nominal stresses in a rupare time of about 2 ‘Wand that the material Becomes notch strength- ‘ened agai at lower nominal stesses at a rupture time of approximately 400 h. This same phe- ‘nomenon has been observed in many superalloys and i illustrated in a different manner in Fig. 7. ‘The “notch ductility tough” varies with alloy composition. For example, A-286 is otch sensi- tive at 540 °C (1000 °F), whereas Incone! X-750, is notch sensitive at 680 °C (1200 °F). A given alloy may show notch weakening at some tem- peratures and notch strengthening at others, Gen erally, notch sensitivity appears 10 increase as temperature is reduced. ‘Changes in heat treatment of some alloys may alter noich sensitivity significantly. For example, single low-temperature aging of some alloys may produce very low rupture ductilities, because the Structure is not sufliciendy stabilized. Conse~ quently exposure of such materials for prolonged rupture times will further reduce rupture ductility ‘because of continued precipitation of particles ‘that enhance notch sensitivity. On the other hand, ‘multiple aging usually stabilizes the structure and ‘thus fduces notch sensitivity Notch configuration can have a profound ef fact on test results, particularly in noich-sensitive alloys. Most studies on notch configuration pre sent results in terms of the elastic stress concen: twaton factor. The design criterion Lor the weak- ening effect of notches at normal. and low temperatures is that of complete elasticity. The design stess is the yield stress divided by the ‘able 2 Comparison of creep-rupture strengths for notched and unnotched specimens of sate rd “penne Tied Ra a 75 Too 7) a 10 as ste) oo 0 0 ee) 7 0 20 o is 3 as is to % 3s y veo, 0 ig i (aCe. 6" V0 =9 Sen Sim. = 6-4 025i). = 25 OO A, =A by Teese 6D clastic stess-conventration factor K; (Pig. 8a). ‘The valuc of the peak axial (design) stress de- ‘pends on the configuration ofthe notch. There is no simple relationship fr the effect of oiches a elevated esmperatures. The metallsreie ‘aleflects that influence the behavior of notched ‘material are complex and include composition, fabrication history, and heat eatment. Effects of Several eat treaiments on rupture time of \Waspaloy are shown in Table 1 For ductile metals, the ratio of rupture strength of notched specimens to that of unnotched speci ‘mens usualy increases to some maximum as the stress-concenration factor is inereased. For very Insensitive alloys, there may be litle further change. Metals that are more notch sensitive may ‘undergo a reduction in rao as the notch sharp- ress (siress-eoncentration factor) is increased beyond the maximum and may show notch weakening for even sharper notches. Very hotch-sensitve allays may undergo litle oF 90 ‘notch stzengthening, even for very blunt notches (low suess-concentraion factor) and may un ergo progressive weakening as notch sharpness Relationships between notch configuration and the rato of rupture stengths of notched and un- notched specimens are shown in Fig, 8(b). ln cure |, for an alloy with an unnotehed ropture ductility of 40F%, the noweh-strengthening factor ‘decreases as the notch is decreased in sharpness (Ginerease in aio r/d). In curve 2, foranalloy with ‘unnotched rupture ductility of 7%, the notch- strength Tactor increases with increasing notch sharpness, reaches a peak, and then drops 10 8 rotch-strength reduction factor of less than unity For an alloy with a sill lower unnotched rupture ductility of 3% (curve 4), the noteh-strengthfac- (or is only slightly greater than unity for large radi of curvature and becomes less than unity. It ‘continues 10 decrease as the notches heeome sharper. Effect of Grain Size and Other Variables. The effets of grain size on notched and un notched rupture strength are shown in Fig. 9, The coarse grain sizes (ASTM =I t0 +2) were ob- tained by reheating bars in which smal strains had been introduced by cold reducing them 1 10 1256, Notches had a strengthening effect on both $-816 and Waspaloy when tested at 815 °C (1500°F). There was no measured effect of grain size on either the notched or unnoiched speci ‘mens of $-816. On the other hand, the eoarse- rained Waspaloy specimens showed a longer rupture time at the same rupture sess for both notched and unnotched specimens “The ruptute time for Discaloy at 650 °C (1200 "B) increases with increasing hardness up 10 about 290 HY for notched specimens (Ky = 3.9) and up to 330 HV for unnotched specimens, as shown in Fig, 10, Ductlty, as measured by elon- ‘zation values for unnotched bars, decreases with increasing hardness "The peak in rupture time at 650 °C (1200 °F) ccomesponds to a rupture elongation of 5%. The continual reduction in rupture elongation with {increasing hardness indicates thatthe alloy exhib-its time-dependent notch sensitivity. Notched burs exhibit a strengthening effect a lower hard nesses and higher duetilities; for specimens of higher hardness and lower ductility, rapid notch, weakening is apparent. For this pariculr alloy at this temperature, 9% rupture clongation indicates the point at which no notch strengthening or weakening occurs; this points also indicated by the crossover ofthe two ‘carves in Fig. 10 at about 318 HV. For other alloys, his crossover may cecur at mpture duc- lilies a5 low as 3% oF as high as 25%, Alloys ‘with lower rupture ductiliies are more notch sen= sitive ‘The effects of notches on rupture life of tree ‘creases with increased notch severity atthe lower test temperatures. Ths effect is particulary evi- enced in Waspaloy. At 650 and 730 °C (1200 and 1350 °F) and fora noel radius of 0.13 rom (4008 in), the ally is highly norch sensitive, but shows notch strengthening a these same test tem peratures at a blunter notch radius of 2.5 mm (0.10in), ‘ThweKfect of the rains at the root of the notch is minimal for Inconel 751 at 730 °C (1350 °F), in that the material is notch sensitive under a I Properties at Elevated Temperatures /19 conditions of notch severity at prolonged rupture times. The material does show slight notch strengthening, but only withthe larger radi and very short nupkure times. Thus, the larger rai ‘compensate for notch sensitivity in Waspaloy, but notin Inconel 751 a 730 °C (1350°F) tthe highes tes temperature—815 °C (1500 *E)—Waspaloy was notch strengthened und all ‘conditions af notah saverity. Tha nate radive did ‘ot have any effect on alloy $-816, as evidenced bby notch strengthening a all notch severities and superalloys are shown in Fig. 11. Nimonic 80A, a Numbers incSeate reduction Sle, moet Tot (rmelylacone! X30), a = fl Waly show ans dos of ach - _ Sensivisy. Nimonic SOA shows a now 0 na » Stengteting eect at 630 °C 1200 °F) bu Sear ORY nocceam-n ‘notch weakened in about 100 h at 705 °C (1300 490) 161.5 mer (0.080 in| Xv sh _ 2 "Thandinaout 40 mat 760°C 1400" Sacer) ans aod Gs ; imonic BOA Becomes notch sengthend at 7 a8 - 815°C C1S00°F), which lasts that alloy 70: ator ae da exhib anotch iy tough berwoen 705 ad ei 40°C (190 and 1400). Using 0.1 : fe (0.005 im) as the standard notch radius, 5 lamon 00a 0 11200 HP 7 Waspaloy and nconel 731 bth exhibited notch Seen sles Wakcingal the lower ts eoperanes 650 ad "+ peat 330°C (1200and 1350°P) anda tengo a * ingath higher test empratures 815 ans 870°C Fc Urnre (150 and 1600" « te Sirdar tet on Inconel X50 with pire duels of 10% reduction inaea at 730 wm & |" (1350"F and 24% 815°C 500" Indicated = if noth scagthening at bo peraires, These ‘ul sppon be Servant meas ith he Hip pte docliis nder he ial est core : Aitons willbe les notch sensitive in long expo pean eat ts pee tines tha anes with owned pte . 5 : heii. Alloy 816 furterllustates it ad xin tai ay es very iphone Goce 3 tea meach teat tampered os nt shove Ns Spot wach wealcaing uy es tomperiere Wasi = ae ots Sista) if The cvs for the alloys with varius notch ai] 2 98mm 9020} — radii show that, in general, notch sensitivity in- 2 28mm (0.100 nd | Numbers indicate) alent cates. eapotey, none 731 a0 * ae a |_| | 5 E > “——— | de 2 oy S| a 0 5 a — : , a ) = ee ~ » 22 os aoe Hordes. Hv : L ° Fig. 10 Yostione nt 50°C 120° = ; 7 ° e e natalensis. Op sybol na cave notches est 33 sod Symbols iste Soave Numbers adjacent opines etal elo one forthe oe. Fig. 11 etacwotmicheson tne i ofthe siperatloys20 / Introduction {est temperatures, However, high rupture ductili- ‘Ges enhanced notch strengthening Data Presentations Generally, all creep and stress-uprure data are analyzed in terms of three variables: time, stess, ‘nd temperature. Other factors are also important, particularly when an understanding of the proce ess(es) in control of deformation is desired. How- ‘ever, fora straightforward presentation and rep= resentation of most experimental data these thee Variables are sufficient, ‘The time-to-rupture (¢) from either isother- smal stress-rupture or ereep-auptre testing is re sented as a function of stess as: Kyexp(00) ea and 0" cr ‘where Kj, Kanda are constants, and isthe stress ‘exponent for rupure. An example of time to-rup- ‘ure results andthe use of thes equations io describe the data at several temperatures are shown in Fig. 124) and (b). Genenlly, there isle difference between the exponential (Eq 1, Fig. 12a), or power law (Eq 2, Fig. 12b) descriptions of the times-to- -uptue. La both cases, the data ie on straight ines, and cosfisients of determination (R°) forte linear regression fits ofthe daa have high values. ‘When temperature effects as well as stress ef feets on timeto-rupture are to be considered, one ‘common presentation is wren(2) a ‘whore K's i a constant; Q, isthe aetivation enerpy {oe rupture; is the universal gas constant (8.314 Jd/mol: K); and 7 is the absolute temperaure in ddogroes Kelvin. Figure 12(¢) describes time-to-p- ture da for several temperatures as a singe line “The Larson Miller parameter (LMP) (Ref 12) rep- resents another approach using a single curve {0 represent data gathered under a variety of condi ‘ions, where: LMP =2€ + 681) ea and LMP =Kyloga + Ky (645) where C; Kana KS re constants Originally, was setequal 1020: however, Cis curently permitted to assume avaluc that best describes te dat Figure 126) ilustraes the use of the Larso-Miller pe rameter to combine time-to-rupaure data from sev- cal temperanures and stresses ito one curve. For ‘more infoemation on time-temperature parameters, sce the article “Assessment and Use of Creep-Rup ture Popesties” in this Volume. Creep curves generated by ether creep-rup- ture or interrupted ereep testing are usually pre- sented as strain versus time or log strain log time. Examples of both forms are given in Fig. 13. The linear presentation (Fig. 13a) gives an accurate representation ofthe three stages of, creep. However, the str andlor second-stage creep is de-emphasized if feonsiderable strain occurs in Also, the ime spent in primary and/or tertiary creep is de-emphasized if steady-state ereep ¢x- ists over a large fraction of the time-to-rupture. "The logarithm forma, on the other hand, em- phasizes the time and Strain during first-stage ‘reep and, wo some extent, the strain during sec- fond-stage creep at the expense of ime during second-stage creep and the strain and time of thind-stage creep. De-emphasis of tertiary creep incurned in frs- aebcomn rece, - | eee ~< : NES 2 + 4 ad i SS i. == 2 ose ROLE mee a 729% 10° 0.0872 0st 2, tal g pepo eee Ee < 7 cc \ ee : ie i + fit cto tec mr nana ah creased Intersonot eval emettares na Exponcal fom 1} Power frm 42 el Temperate compensated per lew im fq Lasoo pn UMP om Eq Sources Rein the logarithm presentation allows the low strain behavior to be highlighted, which is per- haps of mast interest for design purposes. ‘Steady-State Creep Rate. The most important creep parameter i terms of theoretical analysis is the steady-state creep rate és. lls dependence on sess is generally expressed 3 eK" (Eq6) scones acter) ats where Kana Ky are constants, is he stress expo rent for creep, and Qe isthe activation enerey for ‘aeep. Because of theoretical development, certain values of the stress exponent for creep have been comelated with deformation mechanisms, and the activation energy for creep has been corelated to the activation energy for diffusion Examples of steady-state creep rates as func= tions of stress and temperature are shown in Fig. 14,along withthe results of linear regression fits to power law creep (Eq 6) and temperature-com- pensated power law ereep (Eq 7). Note the gen feral agreersent of the compressive test results ‘withthe tensile data in Fig, 14 and the reproduci- bility of versus o behavior from two castings ofthe same material (Fig. 1), Deformation during Steady-State Creep. ‘The values of and Qe given in Eq 7 are sensitive to the processes controlling ereep (Ref 11). The region in which an individual process dominates can be obiained from a deformation mechanism ‘map (Ref 12). A deformation mechanism map is 2 plot of normalized stress, o/E, where E is Young's modulus (or shear siress divided by shear modulus) against normalized temperature, Tix. Figure 15 shows an example of such a plot Mechanical Properties at Elevated Temperatures / 21 for pure nickel. It includes contours of constant strain rate and can he used to establish the process controlling creep at a given stress and tempera- Deformation mechanism maps show two main ‘reep fields. In one, creep rate is governed by the ‘lide and climb of dislocations and has a power law stress dependence. In the othe, creep is con- twolled by the siess-directed diffusional flow of ‘atoms. Several specific models have been pro- ‘posed for these processes and the fields can be further subdivided, as indicated by the dasted lines in Fig. 15. When diffusional low domi- nates, the models give n= | and the appropriate Value of activation energy depends on whether grain boundary diffusion o latice diffusion con- trols. When power law ereep: domi typically predicted to bein the rang though much larger values are often measured in Practice), with dislocation motion being limited tthe lower temperatures by coe diffusion and at the higher temperatures by lice diffusion For a given mechanism, actual crop rates are dependent on material composition, microstrc ture, and grain size, The largest grain size de- pendence is observed in the diffusional flow re fon, with an increase in grain size resulting in a decrease in creep rate, Solid-solution and precipi ‘There sa general endeney foralloying additions 1 move mechanism boundaries to higher o/E and T/Ty4 ratios (Ref 12). An illustration of ths effect ean be seen in Fig. 16 for the nickel-base super- alloy MAR-M200 when comparison is made with pure nickel in Fig. 15. Stress to Produce 1.0% Strain. In many cases, the objective of testing isto determine the {otal amount of ereep strain that ean be expected uring stress/temperatre exposures. OF particu lar inlerest are the stresses required to produce 05, 1.0, and 2.0% stain in a cenain period of time a 9 funtion of temperature Atypical ex: tmp of sich presentation i shown in Fig. 17 Toreveral refractory alloys, Also lst sw casein which ametalugialvaable grin size) sexs factored into the analysis to aecou fo the Gifferenc in behavior etwoen he two It fhe tanal-base alloy Aste B11C ‘Monkiman-Grant Relationship. For levated- temperate tensile crep-uptre experiments the product of the me o-mptre and steady” até ereep rte cise othe power Mis apron rately a eonstant for many materials (Ret 1) f= By 648) ‘where Mand Ke are constants with values roughly ‘qual to 1. An example ofthis relationship is shown in Fig 18 using earranged form of Eq ogie= op Ky Mowe) eo ‘Once Mf and Kare known, reasonable predictions of either quantity can be made from knowledge of the vier. Other Testing Considerations Constant Load versus Constant Stress Test- ing. Most uniaxial creep and stress-rupture tests fre conducted under constant-load. conditions ‘Although the method is simple, the stress in the ‘age section varies with stain (ime). This can be seen by considering a bar of ength La and cross- sectional area Ao subjected toa tensile load P. At the initial engineering stress on the bat eq) ‘With the assumption of uniform deformation during creep the bar lengthens wo Land the cross-sectional a ‘ 1 om p 97h g | = [ 1 6906 Faw “ L Faw : | pete ; Eon ~1 = t008n i aes i | BL "ae = an Bie dl a 2 A CT a aa ; F 7? 1 Fig. 13. Crepcarvesio 100 orened NASA 100) (ojtog san loge. Sure: Ret 12 wo SSAKISC1.7MoTo1 10 (tl ingle crystals tse ia tensontorptre at 100°C 1830°F ina Sain vite22/ Introduction Table 3 crack initiation and crack propagation f-assessment techniques and their limitations for creep-damage evaluation for ‘Sock Suess, bi a eee » © Costing? 2 Gaeting? = Compression = aan Ince Tiptioaatpatexprene coe Noe ‘sues | [cmc (Gaventoml NDE gee esoaon anayes | | stom ig sscttor NE Netty Gevloed a is ‘Acmaemision ‘ie ecm ation Battaneenno nals aaa Srdiacaianmesnimnen —— Uncenany eaing ins aa Linker fatcerei 7 Diya dowsing esd i ice ; agin italy inanplernoa Remacing Daealy snes mocking, Me ‘conse vay oe natn te oe ofan peimen {aaa comets fem Minwinacvt ‘Coven mum Cababscaneniagmesiecmens {Lancome racers als Hadise nto Oise meer for tte, ‘umn sascanps wth remoting eae cing ost on ite Une inert Eres [Laka pth aie an ‘celine asked fr chrcering rack rom ssp ne eps guns ackofncon owen ecerom under ep ‘seo Dieses nen fi serie ‘pene some Re area decreases 10 A, because volume must be com served LA= ley eqn, “Therefore, e) } (8413) ‘Methods have been devised to account for the change in cross-sectional area during. creep. ‘These are hased on a rearranged form of Eq 13, where " itis (eq ‘Hy maintaining PL ata xed value, aconstant stress testcan be conducted. In genera, the form of in timebehavior under constant stress conditions isthe same as those shown in Fig. 3 and 4. However, he period of time spent in primary and sevondary creep Under constant stress can be much longer than under fn identical engincering stess (constant load, Hence, rupture fe is longer under constant stress conditions Fig. 19) ‘Typical constant-sress croep curves obiained for type 316 austenitic stainless steel at 705 °C (1300°F) are shown in Fig. 20. Ineach specimen, the test was ended soon afer tetiry creep began, ‘The maximum strain reached in these tests was slightly less than 604%, although the apparatus Wats designed to accommodate uniform stains of atleast 100% Failure under constant stress conditions even tally occurs due to some microstructural and/or ‘mechanical instability inthe sare manner a ina ‘constant load experiment. Once a local variation in cross-sectional aea is formed, the seta stress is higher than the imposed constant stress. and further deformation concentrates at this location. Tn reality, the basic assumptions of conserva- tion of volume andr uniform deformation have beet violated: therefore, Eq 4 is no longer valid. ‘When nonuniform deformation starts in either @ constant load ot constant stress test, the local siruin and strain rate vary along the gage section in an unknown manne. Engineering Strain versus True Strain. In creep experiments, there is litle difference be- toween strains calculated by the engineering stain ‘or tne strain definitions when the length change is approximately 10% or less. For greater length ‘changes, the calculated values of strain deviate [really Although this is of no consequence fo fension, the limit of a maxirmm engineering strain of 1.00 in compression places an ariticial ‘barrier on the description of compressive ereep. Hence, true stain is a much better indicator of, sess, T © 000% (190 “1 [8 $25°c i700) i i : Fig. 14 Ses cnp nn) 33 ton a ig 4 lia siess (} ond temperature (7) fortwo heats of ny ead EGA fo Sige ca eel sings enpantrs neo Et ference Lormenatd powcr Ln oom te 7 Stace ‘compressive ductility and creep characteristics, In particular, creep beliavior measured in tension 1nd compression can be compared only shen both are expressed as tre strain due to the lim ing engineering strain in compression. Effects of Creep on Microstructure and Fracture Morphology Microsteucture. During creep. significant i- crostuctural changes occur on all evels. On the ‘omic scale, dislocations are created and forced to move through the mesial. This leads to workMechanical Properties at Elevated Temperatures / 23 Tema, °C soo 0 200 _s00 ow 00010001200 1 wey ia san ovo Gotta seni 1 ve | Paster Pasty rmonfatsion-| sos woe wo - a4 Poworiaw oop SS 3 go \ NS £ as wi Wie é Fw ere g i Ro 5 ag | * 3 1a ot | \ 4 wE bot - ae w E Pog } : af swe aera le a * 0s (ean teardy son tiuser) he “ a P | | 105 Yiot ‘ mo Oz oa 8 oe 10 my 2 04 08 08 Morne terre 7 toreegous tpn 15, ekamation mechani map for pe ich wth again si of 100 wT Ccematon chan map he a ic ve peal MAR Y200 Fe 1S etmpeaure, i hgiriyseae, Sree Rel TS " 1 ea gan set 100 wm Souree Rel 12 sewn 2o0 ot ee | ecbexmo's ap = Sei fasor ag ot gel ieee |, to cha 7 . wleeckyeme] og :2 4 BO ina wa 5 4m . 4 faci 6 bel ° 4 Em i : \ e : dee nad | 7 to qb'e 0) 2e| i FES a) ea eae wl Loan cin) « fel ened wie de ces ed oe wee TFB T8 escent con Sel ‘Tan en rm) TOT 180 1A7 Sees neces 1.7% sain in 10,000h 259 Fig-17 irae trperatre or several atau loys tested vac: Maia incase To, F222 (raanissiwoni0, and. pour 61iC. Cate $39.0 020 alles nw: Souce Rt 13 hardening ax the dislocation density increases and the dislocations encounter baries to their motion, AClow temperatures, an ever-diminish- {ng crop rate results; however, ifthe temperature is sufficiently high, dislocations rearange and anniilate through recovery events. ‘The combined action of hardening and recov- exy processes during primary creep can lead to ‘he formation of a stable distribution of subgrains ‘or loose three-dimensional dislocation networks in some materials, or an approximately uniform. islocation istibution without subgrains in ‘other materials. These stable dislocation configu rations are maintained and are characteristic of second-stage exp 18 Teo i) faction of steady ate Fig. 1B pvt 0] ced NAGAI 100 seeped on lepton Creep deformation also produces change in the light optical macto- and microstructures. Such changes include slip bands, grain-boundary sid- ing, cavity formation and growth, and cracking (grain-boundary, interphase boundary, and trans- granular), The mierostructual changes that lad to cracking are described below in the section “Creep Fracture "The microsiructure of an elevated-temperature creep of stress-rupture test specimen rarely re- sembles the initial microstructure. Most materials fare not thermodynamically stable; hence, pro- longed exposure under ereep conditions can re- sult in the precipitation of new phases, dissolu- tion or growth of desived phases, grain growth, and so on. Although many of the structural ‘changes can be duplicated through simple heat treatment, some changes will only occur under thecombined influence of stress and temperature. Figure 21 is an example of a stress/tempers- rure-dependent microstructure. Under, normal Isothermal annealing, the eube-shaped'y’(NisAD strengthening phase (Fig. 21a) inthe nickel-base superalloy NASAIR 100 undergoes Ostwald rip- ning (Fig. 21b), where ripening is characterized by an increase in panicle size without any shape change. However, during creep testing, the indi- Vidual precipitates grow together rapidly and form thin” plates where the ong dimensions of ‘each plat are perpendicularto the stress in tensile Creep (Fig. 21c) and parallel tothe applied stress in compressive reep (Fig. 216). ‘The changes in microstrcture that occur dure ing testing affect creep properties. Aihough such ‘changes may be unavoidable, in many eases ther ‘momechanieal processing schedules ean be es-24 // Introduction ¢ a2 ike toss 155 71008) mi rr | ig, 20, Tyicalcontancaves cep crves caine 2 70 Fig. 20 Jp Lablished to influence the changes so that they tend to strengthen the material or minimize the overall effect. For example. if a heterogeneous precipitate is formed during creep, a simple heat lweatment or cokd work followed by annealing prior to testing should give a homogeneous distr bution of precipitates Microstructural changes due to the combined influence of temperature and stress are the most difficult wo control. These changes enhance creep and therefore contributs to the observed strain, Even ifthe changes are essentially complete after primary creep and the resultant microstructure is ‘more creep resistant than the original structure, the creep strain from such changes may be so reat tha the material cannot be wsed. To circum. vent these changes, simulation of ereep exposure prior to actual use may be necessary. ‘Complete microstructural examination of tesiod and untested materials should be an essen tial par of any croep experiment. Asa minimum, Table 4 Neubauer classification of creep damage 7 ‘Uimaged Nocrep dame dessed 3 ‘Oremod Observe fix inspection itv a Mirorelod Uanaed sere on ope 5 Mogens inne pas some: Re27 Table 5 Correlation of damage level and life fraction consumed 2 ones =f aumD 4 sos ol 2B sou: R26 the as-received microstructure should be com- peared to thse at and aay from the fracture site for the shores-lived and longest-lived test speci ‘mens at cach temperature. This comparison aids Jdeattication of the relevant deformation mechs ‘ism, indicates whether environment i affecting creep, and reveals any significant microstructural ‘changes. Such information is vita for interpret ing and understanding creep behavior ‘Creep Fracture (Ref 18, As shown schemati cally in Fig. 22, intergranular ereep ruptures oc cur by either of two fracture processes: wiple- point cracking or grain-boundary cavitation. The Strain rate and temperature determine which fac ture process dominates. Relatively high stain rates and intermediate temperatures promote the formation of wedge eracks, or tripl-point cracks ig. 228), Grain-boundary sliding 95 reslt of an applied tensile stress can produce sufficient sHress concentration at grain-boundary tiple ‘points to initiate and propagate wedge cracks ‘Cracks can also nucleate i the grain boundary at locations other than the triple point by the inter- ‘ction of primary and secondary slip steps with 2 siding grain boundary. Any environment that lowers grain-boundary cohesion also promotes cracking. As siding procceds, ‘cracks propagate and join to form ecohesive fracture (Fig. 23) ‘At high temperatures and low sain rates grain-boundary sliding favors cavity formation (Fig, 2b). The grain-boundary cavities resultign fiom creep should not be confused with micto- voids formed in dimple rupture, The (wo are fundamentally diferent; the cavities are princi pally the result of a diffusion-coniolled process, While microvoids are the result of complex slip. Even at low strain rats, a sliding grain boundary can nucleate cavities at imegularites, such as second-phase inclusion particles. The nucleation cr “oh ree fg.21. Conpsionlniarucuralchagesnaytergtened ick ate peri) saped seg Fig. 21 ire ahace run fon bethernalsmeding Rl Ona pel wemphonmgstos or thenalaneaing et 1 al Mcesiuenal hangs Guo erste ceepandcanpresve cee, epee ed 1 Seetet ir detais belived co be a stain-contolled process (Ref 19,20), while the growth of the cavities ean be described by a diffusion growth mode! (Ref 2 23).and by @ power-law growth relationship (Ref 24, 25). lrespective of the growth model, as ‘deformation continues, the cavities join 10 form fan intergranular fracture. Figure 24 shows the Imicrostrcture and intergranvlar fractare: mor- phology of a type 316 stainless stecl that failed tue o grain-boundary cavitto Instead of propagating by a cracking ora cav- ity-Torming process, a creep rupture can oceur by Mechanical Properties at Elevated Temperatures / 25 combination of both. There may be no clear distinction between wedge cracks and cavities. ‘The wedge cracks can be the result ofthe linkage of cavities at tiple points. ‘There is a general rend toward transgranular failures at short rupture lifetimes (high strain rates) and relatively low temperatures. Fracture mechanism maps, similar 10 the steady-state ‘creep deformation maps described above, have also been developed 10 differentiate between Ueansgranular and intergranular fracture. An ex- amples shown in Fig. 25 for an 80Ni-20Cr alloy. ® Fig. 22 ele pom crcting ae aviation nearer cep pie Slats ri-bounay wing ho 10m Fig. 28 mpl nensrua ce acs (3) Wadgcrckingin coe 625.) Wo akin nek WO “This figure confirms the tendeney for transgranu lar fractures tobe favored by high strainsistresses and for intergranular fractures to be favored by low strains/stresses (ong rupture lifetime). Stress Relaxation ‘Traditional creep testing t0 develop descrip tions of strain rae, stress, and temperature behav jor ean be time-intensive and expensive, involv ing many ercep tet stands, many specimens, and thousands of hours of testing. Suess relaxation ‘offers the potential to eliminate this difficulty by producing. stain ratestress data over a wide ange of rates fom a single specimen. This infor mation is developed when the clastic stain of a specimen extended (oF compressed) a certain, ‘constant length is converted to plastic strain. AS @ 1am Fig 24 ocengosea want howe eis sir a 00°C 1470) at oe of 103 MPaCNS 4s Tra ‘pure 08h light mrogrphs ad) late ‘heroa rainteandary caves ht ike wp to cause Iegranular eve fctre Both a 90%. The SEM fo (graph cts the nerganolrtactare epg Taune26 / Introduction Tempore, "6 sor ge 600900 100012001400 Dynamic rece so Dees taete rk to? ——téyname reertaaton) “ernie “enslesesletie mosis wet ‘Shear avees 120°C. MPa 108 o 02 0a oy or 19 Homologous operate, Fy Fig. 25 foquemehansmmuoiorn N20 Cr shisldonshog he deen tac icant ‘hology on ses an epee, US, lmatetesie erg; = meta ale Source Re 19 the specimen slowly deforms, the load equitedto ‘maintain the constant length s reduced, hence the ferm'"stress relaxation” ts, In addition, this type fof experiment simulates the real engineering problem of the long-term loosening of tightened bolts and other fasteners, Tn its simplest form, 2 stess relaxation test involves loading (straining) a specimen to some predetermined load (strain), fixing the position of the specimen (halting the crosshead motion in a universal test machine, for example), and meas- tring the load asa function of time. With knowl- ‘edge of the elastic modulus ofthe specimen and the stiffness ofthe testing machine, the lead-time data can be converted to sresssirain-rate data ‘This information can then be used 10 determine the stress exponents and activation energies for ‘deformation, 1 Altes ating Damage rating consid ie aeton Fig, 26. Relion between Neubiu damsge ating (Table an consumes acto, Sure: Ret 27,28 (One major drawback wo stress relaxation testing isthe demands placed on the experimental eq ‘ment. The load-measuring system must be eap ble of making accurate measurements of very small changes a a function of time. The effect of the loading rate on the relaxation rat should be evident, In addition, room temperature, as well as specimen temperature must be precisely contr Jed throughout the experiment. This is critical, because even small ictuations in temperature will produce thermal expansion effects that can mask changes duc t relaxation. Also, the calev- lated stress exponents and activation enetpics ‘muy not be the same as those determined from creep testing. The processes that produce plastic flow could be different for these two situations. (Only comparison of the results form both types of testing can detect equivalent behavior. Remaining-Life-Assessment Methodologies (Ref 20) Failure due to ereep can be classified as result- {ng either from widespread bulk damage o fom localized damage, The structural components that are vulnerable to bulk damage (eg. boiler Aubes) are subjected to uniform foaing and wn form temperature distribution daring servie. Ifa sample of material from such & component is ‘examined, it will truly represent the stat of dam age inthe material surounding it The life of such component is elated tothe creep-rupture prop- trties. On the other hand, components that are Subjected to sess (stain) and temperature gradi- fens (ypicl of thick-section components) may tot fail by bulk creep ruptre. Ii likely that at the end ofthe preted reep-ruptre life, aerack ‘wll develop the ceitial location and propagate to cause failure. A similar situation exists where failure originates ata stress concentration or at pre-existing defects in the component, In this ‘ase, most ofthe life ofthe component is spent in ‘rack propagation, and creep tupture-basedcrite- tia are of lite value. ‘Assessment of Bulk Creep Damage. The eurrent approaches to creep damage assessment Of components can be classified into two broad ‘categories: (a) histry-based| methods, in which ‘lant operating history in conjunction with stand rd material property data are crployed 0 cal late the fractional ereep life that has been ex- pended, using. the lile-raction rule or other tlmage rules and (b) methods based on post service evaluation ofthe actual component. Tnhistory-based methods, plant records and the time-temperature history of the component are reviewed. The ereeplife faction consumed for tac ime-emperature segment of the history can then he calculated and summed up using the Jower-bound ISO data and the life fraction rue, cathe damage rules. ‘The most common approach to calculation of curative creep. damage is 10 compute the mount of life expended by using time or strain fractions as measures of damage, When the frac- tional damages add up tunity, then failure is postulated to oceur, The most prominent rules are 4 fallow:Life fraction rule (LFR) (Ret 21): (eats) e416) e417) E18) ‘wheres a constant, and eae the time spent and sain aerted at condition i nd 4g and eae the rte life and rupture strain, respetively, under the sarne conditions. Goldho(f and Woodford (Ref 25) studied the Robinson liferation rule and determined that foruCr-Mo-V rotor ice it worked well for small changes in stress and temperature. GoldhotT Ref 26) assessed strain-hardening, liferation, and Stain-fiction rules under unsteady conditions for his steel. While all gave similar results, the stain-faction rule was found t bo the most sccurat om careful and critical examination of the aalable results, the following overall observa tions canbe stated (Ref 20) © Although several damage rues have been pro- posed, none has been demonstrated to have a ‘earet superiority over any ofthe others 1 The LPR is clearly not valid for stress-change experiments. Under service conditions where stress may be steadily increasing due wo comme- sion elated wastage (eg, in boiler tubes), ap- plications ofthe LFR will yield nonconserva live life estimates; that is, dhe actal life will be les than the predicted life. On the oer hand, residual-ife predictions using postexposure tests at high Siesses will yield unduly pessi- inistc and conservative results, ‘The LFR is generally vali for variable-tem- perature conditions as long. as changing creep Icchanisms and environmental inkeractions do aot interfere with test esuls, Hence, serv- joe life under Nuctuating temperatures and re- nal file based on accclerated-temperature tess canbe predicted reasonably accurately by use ofthe LFR. “Tho possible effects of material ductility Gr any) onthe applicability of the LFR nced wo be investigated A major limitation in applying the LER is thatthe properties of the vir matal must be known or assumed, Postex posure tests using mulkiple specimens often Mechanical Properties at Elevated Temperatures / 27 ‘cam obviate the need for assuming any damage rule Direct posiservice evaluations represent an im- provement over history-based methods, Because ‘no assumptions regarding material properties and past history are made. Unfortunately, direct ex- amination are expensive and time-consuming. The best strategy is 10 combine the wo ap- proaches, A history-based mothod is used to de- termine whether more detailed evaluations axe justified and to identify the critical locations, and this is followed by judicious postservice evalu- ation, Tuble 3 summarizes the techniques that are imuse for life assessment and some of the issues Pertaining to each technique. ‘Current postservice evaluation procedures ‘ehude conventional nondestructive evaluation (NDE) methods (e.g, ullrasonies, dye-penetrant inspection, et), dimensional (stain) measure ments, and ereep-life evaluations by means of accelerated creep damage and microstructural ‘damage, which ean be precursors of rapid unan- ticipated failures. Due to unknown variations in the original dimensions, changes in dimensions Dimen- cannot be determined with confide Sonal measurements fail to provide ind of local creep damage caused by localized strains, such as those in heat-affected zones of welds and regions of stress concentrations inthe base mel Cracking can frequently occur without manifest ‘overall strain, Furthermore the erica strain ac- cumulation preceding fracture can vary widely witha variety of operational material parameters and with stress state, ‘Surface replication is a well-known sample preparation fechnigue that can be used to assess the condition of high-temperature power plant and petrochemical components from creep dan ‘age. The usual method of metallographic invest _gtion involves cutting arg pieces from compo- ‘nents, which thus renders the component unfit for service. In contrast surface replication allows examination °f microstructural damage without ‘cutting sections from the component (sce the ar- ile "Replication Microscopy Techniques for NDE" in Nondestructive Evaluation and Quetity Control, Volume 17 of ASM Handbook). Replication teefniques ae suilicently soph. ticated to allow classifieations of microstructural damage Such asin Fable 4, for example) thatean be directly comelatd to life fractions (Fig. 26). A distinct correlation exists for these data, such that minimum and maximum remaining life faction «an be specified (such as in Table, for example) (Ref 27, 28). For assessed consumed life fraction, X, aller exposure time, Texp the remaining Ii Tre Tom Tay V1) 419) ‘The qualitative-quaniative retation is advantae ous because data fom surface replication can be predictive in terms of generating a conservative ‘minimum and maninu-life estimate. The maxi ‘mum ie is useful in predictive maintenance envi Croep zone ‘Smal scale cep (SCC) condition oy wen Crete zone Transition creep (TO) conaition \ (re0p 200 ‘Steady state csep (85) conation ig. 27, Schematic topreenation ofthe levels of cee Fig, 27 ction us which coeeperack glow can occur, Sours Ret 2 ronment, as it would dictate the planning of future repairs or replacement. ‘A common method of estimating the remaining ‘reep life i 10 conduct accelerated rupture tests Temperatures well above the service temperature, ‘The stress is kept as close as possible to the service suess value, because only isostres-var- {ed temperature tests are believed to hein compli ance ith the life-Faction rule, The time-t0-rup- ture results are then ploted versus test temperature. By extrapolating the test results 10 the service temperature, the remaining life under service conditions is estimated, Implementation of the above procedure r= ‘quires a reasonably accurate knowledge of the stresses involved. For cyclic stressing conditions, and in situations involving large stress gradients, Selection of the appropriate stress forthe isostress test is uncertain, Furthermore, the procedure in-28 / Introduction AINE! ial Deo | Fate eo specie of 8155 ly wb Fig. 28 [CaS i vasa tempest or est beng volves destructive tess requiring removal of large samples from operating components. There are limitations on the number of avaiable sam- ples and the locations from which they ean be taken, Periodic assessment of the remaining Tite js not possible. The costs of cutting out materia, ‘machining specimens, and conducting creep tests fan add up to a sigificant expenditure. These ‘costs ae further compounded by the plant outage ‘uring this extended period of evaluation and ‘decision making, Development of nondestructive techniques, particulary those based on metal- lographic and miniaure-specimen approaches, has therefore been a major focus ofthe programs aimed at predicting crack initiation. “Assessment of Creep Crack Growth. As de- seribed in the anicle “Elevated-Temperature Crack Growth of Structural Alloys” in this Vol ume, a number of facture mechanics parameters have been developed to describe the creep crack= growth behavior of materials. These include the Inogral C* and the crack-tip driving force pa rameters C. and Ci), The idea of a crack-tip parameter is that identical values of the appropri= fe parameter indifferently shaped specimens or Structures genorate identical conditions of stress andlor deformation near the crack tip, so thatthe ‘rack growth rate mast he the same provided that the material, the environment, and the tempera ture atthe erack tip are also the sare. Ths, such ‘parameter may be thought of as aransferfunc= tion from specimen to structural behavior. Ihen will be sufficient to measure the erack-growth tale as a funetion of the load parameter in the Taboratory, alto calculate the value ofthe rack: tip parameter forthe crack in the structure. The ‘expected crack-growit rate in the structure then can be estimated Tn the subcreep-temperature regime involving crack growth under elastic or elastic-plastic con- ston, the fracture-mechanies approach (involv ing the use ofthe siressintensity factor K and the ‘Hintegral) for predicting crack-growih behavior is well established. Inthe ereep-temperature = ime, the erack-tip parameter must take into ac= ‘count time-dependent creep. deformation. De- pending onthe material and onthe extent of creep ‘formation, various parameters mentioned above have been successfully correlated with rates of croep-ack growth, Three regimes of crack growth—namely, small-scale, transient, and steady-state—can be istinguished for materials exhibiting. elastic power-law ereep behavior, depending onthe size Of the crack-tip ereep zone relative tothe speci ‘men dimensions, as shown in Fig,27. Inthe early stages of erack growth, the creep zone may be ‘ery small and localized near the crack tp, This regime is defined asthe small-scale ereep regime. ‘At the other extreme, cracking may occur under ‘widespread creep conditions where th entire un- ‘racked ligament is subjected to creep deforms tion, as shown in Fig. 2%c). This regime is termed the large-scale or steady-state creep con tion. Even inthe latter case, ereep-erack growth ‘usually begins under small-scale conditions and, fas the creep proceeds, the steady-state ereep con- ditions develop. In between, the specimen passes ‘through the transition ereep conditions shown. Fig. 27) The transition time, 1. from smal scale ereep to steady-state creep conditions de- pends on several factors, including specimen ge- fometry and size, load level, loading rate temperatuce, and the kinetics of the creep. During the small-scale and transition creep conditions, the size of the creep zone and the stress at the crack tip change continuously with time. Under large-scale creep conditions, the erack-tip stress no longer changes with time. Hence, this regime is known as the steady-state regime. The nature (plasticity or creep) and size of the erack-tip de formation zone relative 1 the size ofthe spect ‘men determine which ofthe parameters K, J, C*, (Cid, and C; might be applicable 10 a given situ- jon. For ereeping materials, description of the pheniomenology surrounding C*, Cy, and Ct) is ‘adequate, The parameters K and J, which do not ‘account for time-dependent strain that occurs in the ereep regime, are not applicable her. Fatigue at Elevated Temperatures Creep-Fatigue Interaction. Failure by fatigue ‘ean usually occur at any temperature below the Imelting point of a metal and sill maintain the characteristic features of fatigue fractures, usu- ‘with Title deformation, over the whole tem strangtny Seat rupture song a 0 te Ga 8000 Fc empetin onthe aee oS Fig. 29 eyes umiersctntngatllud ate cueney of Heber peor perature range, At high temperatures, however, both the fatigue strength and the static sirength of ‘metal generally decrease as the operational tem- perature increases. Figure 28 shows typical SN curves for reversed-bending fatigue tess con- ‘ducted on a structural motalalloy at various ten peratures, The fatigue limits clearly Tower atthe higher temperatures. Mechanical-propery data fon most alloys at high temperatures also show tha, just as at room temperature, the fatigue sirength is closely related to the tensile strength, unless the temperature is high enough for the fatigue strength to be affected by creep phenom- [At high temperatures, application ofa constant load to a metal component produces continuous deformation or creep, which will eventually led ined fora sufficient Fength of time, With increases in temperature stress-rupture strength decreases rapidly 10 val- tes that may be considerably lower than fatigue strength. Therefore, the primary requirement of « metal thar wil be subjected to high temperatores is that it have adequate stress-rupture strength Many alloys that possess good creep resistance re also resistant to fatigue; however, the condi tion ofan alloy that will provide maximum stress- rupture strength is not necessarily the condition that provides maximum fatigue siength. In prac tice, it is necessary to design against failure by fatigue and against excessive distortion or frac: ture by creep, just a is necessary to consider ‘combined tensile and fatigue loads at room tem- perature |At room temperature, and except at very igh frequencies, the Frequency at which cyelic loads are applied has litle effect onthe fatigue strength ‘Of most metals. The effect, however, becomes uch greater as the temperature increases and creep becomes more ofa factor. Athigh tempera- tures, the fatigue strength often depends on the total time the stress is applied rather than solely fon the number of cycles, This behavior occurs 240 Mo, rot 2 eerie, cat 2 icemov 8 incon X780 1 Type316 35 2 Nowe love a a a ‘emperatre,"C fg 30 Vail age crack prow esas fun Fig. 30 enor temperature at AK = 30 Mion 7 sin Source: Rel 20.because of continuous deformation under load at high temperatures. Under Muctuating stress, the ‘elie quency affects both the fatigue life and the amount of crep. This is shown in Fig. 29, ‘ypical constant-tife diagram that illustrates the temperature behavior of $816 alloy tested under fluctuating axial load. At room temperature, the curves converge at the tensile strength, plotted slong the mean-sress axis. At high temperature, ‘he curves terminate a the stress-rupture strength, hich, being a time-dependent property, results ‘in ermination ata series of end points along the ‘The principal method of studying exeep-fatigue ierations has been to conduct strain-controlled. faigue tests with variable frequencies with and without holding period (hold time) during some potion of the test. The lower frequencies (= 10° ‘yces) andthe bold times ean allow creep to take place. Tn pure fatigue tests, at higher frequencies tn short hold mes, the fatigue mode dominates tnd flues sturt near the surface and propagate transgranvlanly. As the hold time is increased, or the frequency decreases, the ere=p component begins to play arole with increasing creep fatigue intention. Inhis region, fractures are of amined ‘mode involving both fatigue eracking and creep Cavitation, With prolonged hold times with ecca- sional interspersed cycles, creep processes com- pletely dominate and can be treated almost as ure cases of creep. In instances where oxidation fffets contribute significantly to the ereep-fa- tig inleraction, the situation is mote complex than described above. A more detailed descrip- tionofereep-fatigu effects and methodologies to predict creep fatigue behavior ean be found inthe ale “Creep-Fatgue Interaction” in this Vol- ‘Thermal and Thermomechanical Fatigue. ‘Thermal-fatigue failure i the result of termpera- ture cycling (without external loading), a8 op- posed to fugue at high temperatures caused by Stain eycling. Two conditions necessary for ther Ind fatigue are some form of mechanical con- sai anda temperature change. Thermal expan ‘on or contraction caused by a temperature ‘hange acting agains a constraint causes thermal stress Constraint may be exiernal-—for example, ‘omsiraint imposed by rigid mountings for pipes—or it may be intemal, in which ease its sec up by a temperature gradient within the part Inthick sections, eemperature gradients are Hkely {0 occur both along and through the material, casing highly wiaxal stresses and reducing teil ductility, even though the uniaxial ductility olen inereases with increasing temperature. Re- action inthe ductility ofthe material gives rise 10 fractures that have a brittle appearance, often with many cleavagelike facets in evidence. ‘Thermomechanical fatigue involves simula. ‘cous changes in temperature and mechanical stn, It differs from creep-fatigue in that the Taner scared out at constant nominal tempera ‘ure (sothermal) conditions. As such, the defor- ‘mation and fatigue damage due to. ther- ‘momechanical fatigue cannot be predicted based ‘nisotbermal creep-fatigue daa ‘Mechanical Properties at Elevated Temperatures / 29 se 0 Hardness, HRC Tomperaue. °C ‘A summary of thermal and thermomechanical test methods, property data, and lie prediction ‘methods can be found inthe artiele Thermal and ‘Thermomechanical Fatigue of Stractual Alloys" in this Volume. This article also describes fail ures due other forms of thermal cyeling such as thermal shock and thermal ratcheting. Elevated-Temperature Fatigue Crack Growth. “The stess-intensity factor, K, is used for charac terizing fatigue crack propagation, Most fatigue crack growth data are plowed in terms of erack ‘owth pereycle, dav, versus the stess-inten- sity factor range, AK. Methods for determining K for various load/erack configurations have been derived and are listed in various publications, including Volume 8, Mechanical Testing, and ‘Volume 19, Fatigue and Fracture, of ASM Hand- book. Inde power-law (Pars equation) crack growth regime, the effects of temperature, stress ratio (R), and hold times have been investigated for ‘many high-temperature alloys. Typical behavior and crack growih results for spevific alloys are covered elsewhere in this Volume. However, a general comparison of temperature effets on fae ligue erack growth of several different high-em perature alloys is shown in Fig, 30. Because The reported data are obtained at various AK ranges nd temperature ranges, the general comparison is based on a constant AK (arbitrarily chosen as 30 MPa Ym. or27 ksiin.). clear trend of crack ‘growth rat increase with increasing temperature ‘ean be seen as shown in Fig. 30. At temperatures ‘up to about 50% ofthe melting point (550 to 600 °C, oF 1020 10 1110 °F), the growth rates are 31 Comput oft harness vals of vars cuting tol material relatively insensitive to temperature, but the sen sitivity increases eypidly at higher temperatures. The crack growth rates for all the materials at lemperatures up 10 600 °C, relative to the room lemperatute rates, can be estimated by a maxi- ‘num correlation factor ofS 2 for feritic sees), Besides temperature, cyelic frequency, or dura- tion ofa stress cycle @ with hold time) i a key variable in high-temperature crack growth, Athigh frequency—that is, fast loadin rate with short hold time. (or no hold time)—the crack growin rate is eycle dependent and can be ex- Dressed in terms of da/dN. At low frequency (oF ‘with long hold time), however, the crack growih rates time dependent; thats, da“ is in propor- tion tothe Loal time span of a given eycle. For tests of different cycle times, all erack grow ate data points are collapsed into a single curve of which daft isthe dependent variable. A mixed region exisis in between the two extremes. The transition from one type of behavior to another depends on material, temperature, frequency, and BR (Ref 29), Fora given material and temperature ‘combination, the iransition frequency is a fune- ‘ion of R, The frequency range at which the crack growth rats remain time dependent increases as Re increases (Ref 29) The limiting case is R ap proaching unity. It is equivalent to erack growth tndor sustained loa, for which the crack growth rates at any frequency will be totally time de- pendent "To further understand the complex interaction ‘mechanisms of stress, temperature time, and en vironmental exposure, a vast amount of experi ‘mental and analytical data was compiled (from a30 / Introduction bibliography of 42 references) and reviewed Crock growth behavior for 36 types of loading profiles, which were in excess af 60 combins tions in material, temperature, frequency, and time variations, were examined. A compilation of the results is presented in Ref 30 Hot Hardness “The ability 10 retain hardness at elevated tem- peratures (pot harness) is critical property for Inaterals used for cutting toolsinserts and metal- Working dies (e., hot forging dies). Tests for determining hot hardness valucs are carried out in Standard Rockwell or Vickers hardness testers with high-temperature capability (up to 1200 °C, ‘6r2100 °F) Figure 31 compares the ht hardness properties of a variety of cutting tool material For high-speed tool steels, cobalt additions in crease the hot hardness. For cemented carbides, Towering the eobalt hinder content increases hot hardness, For hot-work wool stels used for hot die forging applications, _high-tungsten-content sraes containing 9 to 19% W have hot hardness values that are superior to those of hot-work secls, OF the ceramic tool materials, slicon-ni- fride-hase materials exhibit higher hot hardness ‘Values than do alumina-base materials, Adah tional hot hardness property dat for these mate- Fils can be found in the ASM Specialty Hund- book: Tool Materials. ACKNOWLEDGMENTS ‘The information in this article i largely taken from: = J.D, Whiuenberger, Introduction to Creep. ‘ress-Rupture, and Stcess-Relaxation Test ing, Mechanical Testing, Vol 8, ASM Hand: book, (formerly Vol 8, 90s ed, Metals Hand: book), American Society for Metals, 1985, 301-307 ‘© FR. Morml, Testing of Superalloys, Proper- ties and Selection: Siainless Steels, Tool Mate~ rials and Special-Purpose Metals. Vol 3, th fed, Metals Handbook American Society for Metals, 1980, p 220-237 ‘© PF Timmons, Failure Contol in Process Opera- tions, Fatigue end Fracture, Vo 19, ASM Hand: brook, ASM Intemational, 1996, p 468-482 ‘* AF Liv, High-Temperature Life Assessment Fatigue and Fracture, Vol 19, ASM Hand- book, ASM International, 1996, p 520-526 ‘# SD. Antolovich and A. Saxena, Fatigue Fail- tures, Failure Analysis and Prevention, Vol 1, ASM Handbook, (formetly Vol 11, 9th ed, Metals Handbook), American Society for Met- als, 1986, 102-135, REFERENCES, WAR. Brown, Je, Ed, Aerospace Siruciural ‘Metals Handbook, Meals and Ceramic Infor ‘mation Center, Columbus, OH, 1982 ‘TD. Moore, El, Sirueural Alloys Handbook, Meals and Ceramic formation Center, Com Jumbus, OF, 1982 “High Temperature, High Strength Nickel Base Alloys.” International Nickel Co., New York, wn TE, Ticta and 1.W. Wilson, Behavior and Propenies of Refractory Metals, Stanford i- verity Press, Stanford, CA, 1965 SK. Mitra and D. McLean, Work Hardening and Recovery in Croep, Prac. Roy. Soc, Vol 295, 1966, p 288-299 GP Tily and GP. Harrison, Interpretation of ‘Tensile and Compressive Crecp Behavior of ‘TwoNickel Alloys,J. Strain Anal, Wol 8, 1973, pris} HH. Gray, “Transverse Tensile and Stress Rupture Properties of yy’ Directionally Soliified Eutectic.” NASA TMX-73451, 1979 R.A. Mackay, “Mogphological Changes of ‘Gana Prime Precipitates in Nickel-Base Su- peralloy Single Crystals.” NASA TM-3698, 1984 9, FR Larson and. Miller, A Time-Temperatre Relationship for Rupture and Creep Stresses, ‘Trans. ASME, Vo74, 1952, p 765-775 MLV, Natal, “nfluesce of Cobalt, Tantalum, ‘and Tungsten on the High Temperature Me chanical Propertis of Single Crystal Nickel: Base Superalloys,” NASA TM-83479, 1984 GA. Webster and R.A, Ainsworth, High Tem perature Component Life Assessment, Chap ‘man Val, 1988, p 40-49 HJ. Frost and MF, Ashby, Deformation “Mechanism Maps, Pergamon Pres, 1982 WD. Klopp, RIL Titan, and K.D. Shes, “Long-Time Creep Behavior of the Tantalum, ‘Alloy Astr 811C." NASA'TP-1681, 1980 | F.C. Monkman ad NJ. Grant, "An Empirical Relationship between Rupture Life and) Mii ‘mum Creep Rate,” Deformation and Fracture ft Elevated Temperatures, N4.Grant and A.W, Mallendore, Ea, MIT Press, Cambridge, MA, 1965, p 91-103 IN. Da C. Andrade, On the Viseuous Flow in Metals and Allied Phenomena, Prac. Royal Soc. London, Vol 84, Series A, 1910-1911, | 5. F. Garafalo, O, Richmond, and W.P, Domis, Design of Apparatus for Constant-Stess oF Is, 8. 20, 24 26 28 », 30 Constant Load, J. Basie Eng, Vol 84, 1982, p 287-293 MY. Nathal and LJ, Bbert, Gamma Prime Shape Changes daring Creep of Nickel-Base Superloy, Seripta Met, Vol 17, 1983,p 115 154 YV. Keatins and A. Philips, Modes of Fracture, Fractography, Vol 12, ASM Handbook, ASM {nemmational, 1987, p 12-71 ME. Ashby, C. Gandhi, and DMR. Taplin, Fracture-Mechanismn Maps and Their Com- struction for FOC Metals and Alloys, Acta Met. all, Vol 27, 1979, p 699-729 R. Viswanathan, Damage Mechanisms and Life Assessment of High-Temperature Component, ‘ASM International, 1989, p 59-110, 164-167 ELL. Robinson, Filect of Temperature Variation fon the Creep Strength of Stels, Trans. ASME, Vol 160, 1938, p 253-259 Y. Liberman, Relasation, Tensile Strength and Failure of EI 512 and KI F-L Secs, Metal. loved Term Obrabxke Metzl, Vol 4, 1982, p 13 FER, Voorhees and FW. Proeman, “Notch Sen- sitivity of Aircraft Suuctaral and Engine Al: Joys,” Wright Air Development Center “Technical Repor, Part 1, Jan 1959, p25, MM. Abo El Ata and I Fine, “A Soy of Creep Damage Rules,” ASME Paper 71 WAMMet-1, American Seciety of Mechanical Engincers, Dc 1971 RM Goldhotfand D.A. Woolford. Te Eval. ation of Creep Deanage ina CrMoV Steel, STP $515, American Society for Testing and Mate Als, 1982, p89. RM, Goidhotf, Stress Concentration and Size fects in a CeMoV Stel at Elevated Fempora- tures, Joint International Conference on Creep, Insite of Mechanical Engineers, London, 1963 B, Neubauer and U. Wed, NDT: Replication ‘Avoids Unnecessary Replacement of Power lant Components, Power Eng. May 1984, p 4 ILM, Brear, et al, “Possbilistic and Prob: dhilistc Assessment of Creep Cavitation,” ICM. 6, Pergamon, 1991 ‘T Nicholas and N-E. Ashlaugh, Fatigue Crick Grovth at High Load Ratios inthe Time-De ppendont Regime, Fracture Mechanics—19, STP969, ASTM, 1988, p 800-817 ‘AP, Liu, “Blement of Fracture Mechanics in Elevated Temperature Crack Growth.” AIA — Paper 90-0928, Colletion of Technical Papers, pat 2, AIAAIASME/ASCH/AHS/ASC 31st Structures, Stuctural Dynamies and Materials Conference.2-4 April 1990 (Long Beach, CA), p9st-on4Corrosion at Elevated Temperatures HIGH-TEMPERATURE CORROSION play's an important role inthe selection of materials for Consirction of industrial equipment ranging from yas tusbines to heat weating retorts, The principal modes of high-temperature corrosion Fementy responsible Tr eqpment problems ane (Ref I: + Oxidation 1 Carhurization «= Sullidaion * Nirdation 4 Halogen gas corrosion 1 Ash/salt deposit cotrosion ‘Molten alt corrosion © Liguid metal corrsion Etch ofthese modes of corrosionis described inthis atic with emphasis placed inthe thenodynamic ‘siderations the kinetics of earosion in gas, andthe principles associates with sale formation. In addition, laboratory and field tests designe for aracerizing material performance for specific ap- ‘lietionvenvironments arc also described. Data ‘ompilations related to clevatodemperate coro- son essance/suseepabilty can be found in the nicks in this Volume that dal with speci alloys rceramics General Background (Ref 1) ‘The imporant environments and principal ‘modes of high-temperature corrasion encoun- fered in various industrial processes are briefly described below. These are summarized sche- matialy in Fig. 1, whieh strates that in each carrion mode there will be interactions be- tween oxygen activity and a principal corrodent activity. Table 1 shows the various types of eor ‘usin tat can be anticipated in differen indus- Wal processes. Oxidation is the most important high-tem- erature corrosion reaction. Metals or alloys are bidized when heated to elevated temperatures in Air or highly oxidizing environments, such as a combustion atmosphere with excess air or oxy- en, Oxidation cam also take place in reducing favironments (Le. those characterized by low ‘oxygen activity). Most industrial environments have sufficient oxygen activities to allow oxida- tion to participate in the high-temperature comro- sion reaction regardless of the predominant mode ‘of corrosion. In fact, the alloy often relies on the ‘oxidation reaction to develop a proteetive oxide scale to resist corrosion attack, such as sulfida- tion, carburization, ash/salt deposit corrosion, and soon, ‘Onidation in air occurs in many industrial proc- esses, Heat ueating furnaces and chemical reac- tion vessels ure often heated by eletrical resis- tance in air, Under these conditions te alloy is ‘oxidized by oxygen, For many other industrial processes, heat is ‘generated by combustion, accomplished in many ‘eases by using ait and relatively “clean” fuels such as natural gas or No. 1 or No, 2 fuel ol ‘These fucls generally have low concentrations of ‘contaminants, such as sulfur, chlorine, als, and vanadium. Many hightemperature proc= ‘esses use excess air to ensure complete combus- tion of the fuel, The combustion products thus consist primarily of O2, Na, COp, and H20. Al. though alloys in these environments are oxidized hy oxygen, other combustion products, such as H20 and COp, may play an important role in affecting oxidation behavior ‘When combustion takes place under stoichiometric or substoichiometric conditions, the resultant cavironment becomes “reducing” ‘This type of environment is generally charac Sehamatc sowing the princi ineseonteucen oxen sey a tn nen ig Fig.1 Maken ‘ne spectre como it redtiab eminent aswel 5 the cower act. Source! Rel32/ Introduction ‘Table 1 Modes of corrosion encountered in various process industries — Tapio Topco ‘Chemicayparechemi Eyre searching fries 1 1001850) Cater onan Scinetimangatee ‘ote ‘Osan caution Visto es {380 1200) egos yucca ter fosso4iia0) Sed, Paranoia pear: isis) (Cee ton atoning ‘omni, Onde Haake S580-1090(1740-1985) Ost: hrm rig san, ‘sna Caton dite mets ss0,1se) Sain caren: ees eure pravoe ara ears 80.500.80.990)—_Nisng Other proces ‘Tonmproacioonarue ves 50 150) Ordon tation Nin cle S201) ido eng tdae Nockarrpmesgreaas 3S S00(1380-160) Ouse: aoe > Obese pees 50-500{1500 1650) Relsheamoson Gt tnearee 109s0(174) ‘Silene: oxen sh Wasenenenoptess 10085) ‘Cron alan ond ete aegis mnueurnerpio 103011085) ‘ron so: tn sas terized by low oxygen activity. Under these con- ditions, the oxygen activity is typically controlled by the CO/CO> or Ha/H20 ratios, and the oxida- tion kinetics are generally slow. The develop- ‘ment of a protective oxide scale can be sluggish for most alloys. As a resul, the effets of eomro- sive contaminant ean become more pronounced, resulking in ther modes of high-temperature cor: rosion. For example, ifthe sulfur level in the ‘environment is high, sulfidation then becomes the predominant made of corrosion, eventhough ‘oxidation also takes parti te corosion reaction, ‘Thus, majority of high-temperature corrosion problems in reducing environments are due to ‘modes of corosion attack other than oxidation “The rate of oxidation for metals or alloys is creases with increasing temperature. There is. large spectrum of engineering alloys available for applications in different temperature ranges. Many oxidation problems result from the use of an alloy in a temperature region exceeding the Capability of that alloy. Materials of construction for high-temperature corrosive environments ‘must withstand excessive metal loss by scale for ‘mation from oxidation and from penetration by {nternal oxidation products that could reduce the remaining cross-sectional area toa level that can ‘not sustain the load-bearing requirements, The ‘component will then yield and may swell or dis- tort Insome cases the internal lid pressures can be sulicieat to burst the component, releasing ‘hot, possibly toxic oF flammable Mids, Heating ‘and cooling rates can also be significant because ‘of possible thermal stress (fatigue effets. Sulfidation. When an environment has a high fur activity, the corrosion reaction will more ikely be dominated by sulfidation. The reaction will also be influenced by oxygen activity. Low- ‘ering the oxygen activity ends 10 make the envi- onment more sulfidizing, resulting in increased domination by sulfidation. Conversely, inereas- ing the oxygen activity generally esults in a less sulfidizing environment. The reaction is then ine creasingly dominated by oxidation. Thus, sufi~ {ation is controlled by both sulfur and oxygen Carburization and Nitridation, Carburiza- tion behaves in similar fashion. The reaction is ‘controlled by both carbon and oxygen activites, Lowering the oxygen activity tends to make the ‘environment more carburizing, and vice versa Nitridation isthe same in thatthe reaction be- comes more severe when the environment is te- ‘ducing. In halogen corrosion, oxygen activity influ- ences the reaction differently. For example, high- temperature corrosion in chlorine-bearing envi- ronments is generally attbuied tothe formation of volatile metallic chlorides. Oxidizing environ: ‘meni cause some alloys with high levels of mo- Iybdenum and tungsten to suffer significantly high corrosion rates, presumably by forming very volatile oxyeblorides. Reducing environments often are less corrosive. Nevertheless, the reac tion is controled by both halogen and oxygen activities. ‘Ash/Salt Deposits. Many industrial environ- ‘ments may contain several corrosive Contam fants that fond to form ashvsalt deposits on metal surfaces during high-temperature exposure. ‘These ash/salt deposis can play a significant role in the corrosion reaction. “Hot corrosion” of gas- lurhine components is a good example. Sulfur from the fuel and NaCl rom the ingested air may react during combustion to form sll vapors, such ‘as NapSO4, These salt vapors may then deposit at Tower temperatures on metal surfaces, resulting in accelerated corrosion attack. In fossil-fuel: fired power generation ashvsalt deposits are also very common because of sulfur and vanadium in the fuel oil, particularly low-grade fuels, and al kali metals, chlorine, and sulfur in the coal. The accelerated corrosion due to asisale deposits in this ease is frequently refered to as fuel ash ‘corrosion. Both hot corosion and fuel ash corro~ ‘ion are generally believed to be related to liquid salt deposits, which destroy the protective oxide Seale on the metal surface. Waste incineration generals very complex ash/salt deposits, which ‘often contain sulfur. sodium, potassium, chlorine, zinc, lead, phosphorus, und other elements ‘Ashisalt deposits ae common in waste-heat re ‘covery systems for industrial processes, such as Aluminum remelting operations and pulp and pa- per recovery boilers, and are also common in taleining operations for various chemical prod- ‘cts, This mode of corrosion is referred 10 as ‘shalt deposit corrosion. Effect of Low-Melting Compounds. There are other types of low-melting compounds that ‘can form on the metal surface during the high- temperature reaction. The mast common ones include V20s, Mos, and nickel-phosphorus ‘compounds, These liquid phases can easily de- ‘roy the protective oxide seale and result in ac- celerated corrosion attack. When V20s or MoOs is involved, the attack is referred t0 as cata sophie oxidation. When the environment con tains phosphonss,high-nickel alloys may react with it to form low-melting nickel-phosphorus eutectics, which then destoy the protective oxide scale. The subsequent oxidation or other mode of attack i thus aocelerated, ‘Molten salt and liquid metal corrosion are to other important high-temperature corrosion ‘modes. Oxygen activity may sill play an impor- tant roe in the corrosion reaction for both envi ronments. For example, in a molten salt pot the ‘worst attack frequently occurs athe air-saltinter- face, presumably because that is where oxygen activity is highest Fundamental Data. Essential to an under= standing of the gaseous corrosion of a metal are the erystal structure and the molar volume ofthe metal on which the oxide builds, both of which may affect growth suesses inthe oxide. Forhigh- temperature service itis necessary to know the melting point of the metal, which indicates the practical temperature limits, and the structural ‘changes that take place during heating and cool- ing which affect oxide adherence. These data are presented in Table 2 for pure metals. For the ‘oxides, their structures, melting and boiling points, molar volume, and oxide/metal volume ‘aio (Pilling-Bedworth ratio) are shown in Table 3. The structure data were taken from many Thermodynamics of High-Temperature Corrosion in Gases Free Energy of Reaction. The driving force for reaction of a metal with a gas isthe Gibbs ‘energy change, AG. For the usual conditions of constant temperature and pressure, AG is de- scribed by the Second Law of Thermodynamics ag=ait— Tas eq‘where A/T isthe enthalpy of reaction, 7's the abso- Inte temperature, an AS isthe entropy change. No reaction will proceed spontancously unless AG is egative FAC =O, the sytem is atequilibim, and ‘Gis postive, dhe reaction is thermody namically ‘unfivorable; that i, the reverse reaction will pro- zed spontaneously. ‘The driving force AG fora reaction such as aA +B = cC + dD ean be expressed in terms of the Standard Gibbs energy change, AG", by: arnt wee 2 ‘where the chemical setivity, a, of each reactant or products raised wo the powder ofits stoichiometric cxeffcient, and Ris the gas constant. For example, {nthe oxidation ofa metal by the reaction: mM Zoy=M,0, where Mis the reacting metal, M,Oyisitsoxide and Kandy are the moles of meal and oxygen, respec tively in | mol of the oxide. "The Gibbs energy change forthe reaction is: sa~a0%+ eri 8} nF 3 Inmmost eases, the activites ofthe solids (metal and oxide) are invariant that is, their activities = 1 for pure sods, and forthe relatively high temperatures and moderate pressures encountered in oxidation reactions, ap, can be approximated by is pressure. ‘Therefor, a oquilibrium where AG = 4) whee po isthe patal pressure of oxygen. In solid solutions, such a am alloy, the partial molar Gibbs energy of a substance is usually called is chemical potential y, If1 mol of pure A ‘sdissolved in an amount of solution so large that the solution concentration remains virtually un- ‘hanged, the Gibbs energy change for the mole of Ais ATpeva-vh=RTiag ws whore pis the chemical potential of fmol of pure ‘the chemical potential a #6 the value in the soln, and ai the activity of A in the slain, Metastable Oxides. Thermodynamieally un- stable oxides are often formed in coresion by tases. The Gibbs eneey of formation ofthe ox- ie, AG, less negative than fora sable Oxide, tut infact an unstable oxide can often exis in Aefinitly with no measorable wansformation ‘Acommon example is wusite (FeO), which s fore daring the het oling of eel. Thermody- taal, unstable blow 570 °C (1060 °F), bu emais the major componcat of mill scale fat room temperature because the decomposition Kinetics is extremely slow. ‘As another example rapid kinetics can favor the formation of less stable oxide on an alloy, An alloy AB could oxie to form oxides AO and BO. ‘but if BO is more stable than AO, then any AO Formed in contact with 8 soul 10 BO by the reaction: ByAO-=BOSA [Nevertheless if AO gross rapidly compared with BO ani the conversion reaction i low, AO can be the main oxide found on the alloy. “Thermodynamically unstable crystal structures of oxides are also sometimes found. A growing ‘oxide film tends to uy to align is crystal siructure in some way with tha of the substrate from which itis growing. This epitary can cause the forma- tion of an unstable strctue that fits the substrate best. For example, cubic aluminum oxide {(Al203) may form on aluminum alloys instead of the stable srombohedeal AlOs. Corrosion at Elevated Temperatures / 33, Free Energy-Temperature Diagrams. Metal oxides become less stable as temperature ‘creases, The relative stabilities are usually shown ‘on a Gibbs energy-cemperature diagram, some- times called an Ellingham diagram (Fig. 2), for ‘Similar diagrams are available for sulfides, vides, and other gas-metal reactions. In Fig 2, the reaction plotiod in every cas is: 2 440,-2M0, Fuso} “That i, 1 mol of O: gas is always the reactant, 90 that AG*=RTIm po, 40) For example, the Gibbs energy of formation of ‘AlO+ at 1000 °C (1830 °F), as ead from Fig, 2, is approximately -840 13 (-200 keal) for 23 mol of ‘ALO3, 3O> Arp may “Dhange of tte Clement One WWeioapoin ow OD aoingpom 8 (a) wo 0100, ra m0 rane Ce) 2 ee oe ew Fig. 2 sundi Gtbs ene offrmation of eected ides funciona temperature. Souice: Res34 / Introduction Table2 Structures and thermal properties of pure metals ‘The equilibrium pial pressure of Oss trae yam von (08 Sa ieee oo) 9) wat ei ee " io te Sat BMF 108 08 can ao be ea ly from Fi. 2 who = = sonitnnsis 237 gist aleaiton hy aso i po, sae along the btm =, = "3 SiS tegrated a a "as Som om nine pm tab Oa oper of oe 32 re) ath O55) Geigramanengh dn 000" 1890° point on st = Big “ns 213) 10 AVALOS lng, erst he po, sea cues & & 0) 078 Meximay 10am, whch ithe Go pati pre ee 7 5 « sie in ein wath ami and ALO a cm ein in doo“ 830 fT eas tat yO: psa at ae) pene an 10°? am emis onde me an om = er Mas ie fm, whe A503 would en to Scopes fo = oS oe we ser Ts AA On agi i te sme oak be lcs © es a = 2. & teow 10° un Obvnaly AnOssanextony oe © Za ma G2 ‘ae oxide. a a “Thc eatin of aml by water vapor canbe oe Pr corned inh same way Te eon ‘ti = som ie een 2 2 om aS “ate Iho=M0, 90 a 0 “ ? et le aetna oan xe any cm See : onus ek temper car Boda by consign = e was aso Frome inex point on theese oF Fi. Pr tit) pki a cramp for be ean oe aie fey = ma Galea Gt 2aKD +314048)= ALO) Ee se A sco: opin 0 mn 3s om Sn to FOS R10 Aratgreaer tants tendo dive he a Oh uv SL econo ee reducing ISO te mal A tate oe 2p 13 at estan 10 pees more oxide oe 8 a Ea 138 “Sim. the oxtation of tals by carbon aw OU 15 pile gone (COD) aa shown in Fag 2 For the Ug mein te SHS on eacton ml e ie”) toe Mone oe ‘oem an sty 00)=M,0, +900 hoes Ske fio io 135 Ons sa oa im & et 884 theeqilheamcrbonmonoxite(COJCO? rns os 80a keane pointer on eke Sey Se GRP GRO A G55 fttedagam, Oxon fara y COs at ee 28. 832 quia COCO: ra nyonimaly 1 ei isha te Tanne asso, mas = TS) ate 738) cam "ehermal Stability Diagrams. For site Sua & Ske Bash ine he are moe completed than ingle owen = im igo "E42 tsi eur in single oiling pasts common to nanen £ zB HS nei) Fhe tmp some paca ale a Prin apy tndiasis asin itty gates plot the oer variables of gas presaes or alloy a sia)” “nine” ibs hash Sease Composition against each ether Ths predes feat, : 2‘ “ton "Sh sotermal sabtiy agrams, or predominance Pamdmin we Suis tip ace dupa, ich show te specks tha il oe fis si Jo mod ate ay oof cee oe mS One Meu and Tve Gases, These diagrams, a ie often ced Kellogg agra, ae consaced = 6 a fram he sad Chl mesic of forion, Sew Re fey ‘S0" ofall elements a compounds key wo be ®t : rest inthe sytem or expe fr the .0- mb woti System the AG values of nie menor sem @ Ry tin ati ae (MO), ckel mononle (Ni) (mek a ee ee Sine ist tar nse 09 ha °c) Turton (SO (and $C) ar eee. in Fig 9, the unary beween the Ni (and (os fa ceme rt base he go ci pa team, NiO (8) eons represents the equim Ni) ‘Sant tx hep it tremely Vonecag peta seg rensen ©) + VAOp (a) ~ NiO (9) therefore, the diagram Sevtncs Cir Hr rtonatmenemn fe umetor nessa eC Se Shows that at 1250 K any Op prestre aboveTable2 (continued) Siw ‘e Sm he Sin fos Seamus fe ss 15 whe awn ee Tesi Tobi Hip aise @ te mama) io ie ® we Team we Biss @ he Tum ep Te mo iia Sse Teen) ip msm Os uns be : Vani (a) ocho ie Domine 1 ISI6 the Yootim GB) fe 7 as Yin ta} ep waa oo te ap Peck a) ep woe ® 1 28O 3.16 1450, fie did ae ee SHS 109. es wes Rhus 138. Wis oils psy tase ios st bm 1208 wis ail 130 is 2a 2 Lae 2 21944636 LIT 1a 0668 1230 0:68 10 30788 ewan sn Or (81H a6 20 “ws 97 0389 sin 04s ne (as faecences ai: tbo, hrbobel ext eee cab hep egal sek atta: ‘Sopa uu i cur 0) geo eng soe) Mayline 25°C (7 erates peat er soe eae 5 CF) See Bel about 10° am wil wend to form NiO frm etc nctl i slows Spry, Sa gos presage a shout 10? an wll em NS om nickel at low poy Aso mined pa of 1 am eah of Sy an soul for Sly ‘eeqtonu ao of NO (3) nd NSO) te rina gases of rest wore SOs tnd Cr the came AG" ds could be wed wo construct A dag of po, eras pap oro In 3. Fron arscante adn ire he ted ‘and 2 will form only NiO at 1250 K, with either the sulfide nor sulfate being ws sable. When nickel metal is heated to 1250 K in the open air with sulfu-containing gases, Pso,+Ps2+Po2~02 atm. The situation is ‘Shown by the dashed line in Fg, 3 labeled p = 0.2 atm. Corrosion at Elevated Temperatures / 35, AnAlloy System and a Ges. othermal stabi diagrams for oxidation of many important alloy systems have been worked out, such as that for the Fe-Cr-O system shown in Fig 4, In this dia- fram, the mole fraction of chromium in the alloy is plotted against log pop 50 that for any alloy ‘composition the most stable oxide or mixture of ‘oxides is shown at any gas pressure. Fran alloy system in gases containing more than one reactive component, the pressures ofall hut one of the gases must be fixed at reasonable Values t be able to draw an isothermal stability diagram in two dimensions. Figure 5 shows an ‘example of sucha situation: the Fe-Zn system in ‘equilibrium with sulfur and oxygen-containing ‘2488 with SO3 pressure set at | atm and temperi- ture set at 1168 K. Limitations of Predominance Area Dia- ‘grams. Isothermal stability diagrams, ke all re- ominance area diagrams, including Pourbaix potenialpH diagrams, must be read with an un- derstanding of their ules: ‘* Each area on the diagram is labeled with the predominant phase that is stable under the specified conditions of pressure or tempera- lure, Other phases may also be stable in that area, but in smaller amounts ‘© The boundary line separating wo pred nance arcas shows the conditions of equi ‘um between the two phases. Aso, the imitations ofthe diagrams must be under- ‘ood tobe able o use them intelligently: ‘© The diagrams ae forthe equilibrium situation. Equilibrium may be reaches! quickly in high: temperature oxidation, but ifthe metal is then cooled, equilibrium is often not reestablished, ‘© Microcnvionments, such as gases in voids or cracks, can create situations that differ from Hines). Thus, a mixed gas of 10° atm each of SOy nko, + rao, os BORO, Be, [nraresoe § é ‘ ‘2nd + 2nke 1 } i. i ce | | real ‘ f = a, > | i" nFeiFe,0,| BH ’ Seal e eo STE | | FE are PACT a Sane een | weer] oa Lewd Tere] a a a, Mostar tan iia Fig.3 The N05 sytem at 205K. Source: Rl ig. Sob awa forte FCO sysem 1500 Fig 4 Conon The feZnSO memo Ay Hamat 164K Fig.5 et? eee36 / Introduction Ot 2 0% 9 sesomon TLV TLE Oh ge Oni racleston = growth DOT oomewsion LIN fj, monsmenon Zi. S cnitoe Li VHENE, Fig. 6 Sematilnrain ofthe pincpa phecmens Inking place ding te eacton of res wih conypen. Sue: Rl the situations expected for the bulk reactant phases, ‘©The diagrams often show only the major com ponents, omitting impurities that are usually present in industrial situations and may beim portant. ‘© The diagrams are based on thermodynamic data and do not show rates of reaction. Kinetics of Oxidation In this section, the commonly observed kine {sof oxidation will be described and related to the corrosion mechanisms. These mechanisms fare shown schematically in Fig. 6. The gas first absorbs on the metal surface as atomic oxygen, (Oxide nucleates at favorable sites and most com- monly grows laterally to form a complete thin film, As the layer thickens, it provides a protec~ tive scale barrier wo shield the metal from the pas For scale growth, electrons must move through the oxide o reach the oxygen atoms absorbed on the surface, and oxygen ions, metal ions, o¢ both ‘must move through the oxide barrier. Oxygen ‘may also diffuse ito the metal “Growth stresses in the seale may create cavities and mieroeracks inthe scale, modifying the ox- dation mechanism or even causing the oxide to Dect noni rsa Schathy dec. Fig. 7 Pel doer. Yoconees are indicted by pe squats tral on shown nha ci fail go protect the metal from the gas, Improved ‘oxidation resistance can be achiewed by devetop- ing better allays and by applying protective coat- ings, These subjects ae addressed inthe urticles "Design for Oxidation Resistance” and “Protec: tive Coatings for Superalloys.” respectively, in this Volume. Mechanisms of Oxidation Pilling-Bedworth Theory. in 1923, N.B. Pil ing and R-E, Bedworth classified oxidizable met- als into two groups: those that formed protective ‘oxide scales and those that did not (Ref 9). They Suggested that unprotective scales formed if the volume of the oxide layer was less than the vol lume of metal reacted. For example, the oxiation of aluminum 2AL+%403-+ ALO the Pilling-Bedworth ratio is: Volare of 1 mat of ALOy Volume of? malof AT where the volumes can be calculated from moeeu- la and atomic weights and the denies of the phases, the ratios less than 1, 2 isthe case for alkalt and alkaline earth metals, the oxide scales are usually unprotective, with the scales being po- ous of eacked duet tensile stresses and provide ing no efficient barrier to penetration of gas to the metal surface, If the ratio is more than 1, the protective sale shields the metal from the gas 80 that oxidation ean proceed only by solid-state diffusion, which is slow even at high tempers- tures. Ifthe ratio is much over 2 and the scale is rowing at the metalioxide interface, the large compressive stresses that develop in the oxide as It grows thicker may eventually cause the scale to spill of, leaving the metal unprotected. Exceptions (othe Pilling-Bedworth theory are ‘numerous, and it has been foundly criticized and ‘ejected by many. Its main flaw isthe assumption that metal oxides grow by diffusion of oxygen inward through the oxide layer to the metal. In fact itis much more common for metal ions to diffuse outward through the oxide to the gas. Also, the possiblity of plastic low by the oxide for metal was not considered, Nevertheless, his- toricully, Pilling and Bedworth made the first step in achieving understanding of the processes by ‘which metals react with gases. And although there may be exceptions, the volume ratio, 38 a rough rue-of thumb, is usually comect. The Pill- ing: Bedworth volume ratios for many common ‘oxides are listed in Table 3, Oxide Structure and Texture Defect Structure of lonic Oxides. tonic ‘compounds ean have appreciable ionic conduc- tivity due to Schottky defects andr Frenkel de- fects, Schottky defects are combinations of cation ‘vacancies and anion vacancies inthe proper ratio ‘necessary to maintain electrical neutrality. Figure 7) illustrates a Schottky defect in a stoichiomet- ric toni enystal. With Schottky defects, the ions tus diffuse into the appropriate adjacent vacan- ios 10 allow mass transfer and ionic electrieal ‘conductivity, Fg. 8 lesan ofthe onic arangementin pre NO Fig. 8 ie caion vacancies ae hated ope snares The canon ae aed ig, 9 Mustain te onic nangamenin mye Fig. 9 [frescos oO intra cabo ae tad Aeoekctors nena aCorrosion at Elevated Temperatures / 37 Frenkel defeets are also present in joie crys- Table 3. Structures and thermal properties of selected oxides ‘alsin such a way that electrical neutrality and stoichiometry are maintained (Fig. 7b). This type ig ie comp ofdefeetisacombinationof seation vacancy and oxide sree * 7 oe an interstitial cation. Metal eations are generally fmch anal than te oxygen anions Limied GANDY ORGroahed mh DOS ini lai! conductivity possible in ich Bas” nach ba la say Gifstn of caons mersitaly and oy eemcacy SiG ate : ee ot ma So Sa Dyan extons ino te eaion acini. BO BD he Meullic oxides are seldom, if ever, 2 BLN a stichiometic and cannot grow by mece dif. Gs es & de Shnby Schorky and Frenkel deters Foroxida. S60, BSE) tion to continue when a metal is protected by a C02 aw Inj of oxide, eleewons mist be abe w migrate $0, MISA divs aie fiom the metal, though the oxide, w adsorbed Clo; nga) onygen teenies inrface Neveeles, C1} Pay BA isin ia ‘Schottky and Frenkel defects may provide the C0 ‘Hexagonal (CIC) wa ae mechanism fr ionic diffusion necessary for ox- 3s Gabe 2 mm um Eprom, exo Bs iim atin a es Defect Structure af Semiconductor Or- 0, Gey a moi iS ides Oude growing oproideprtetecaes yor Saw} 5 re fe cecrnic semiconductors that ao allow 2, HS Pd mh Bee ame ‘mass transport of ions through the scale layer. * i a eae aay be conveniclly categorized at ype ei0, Baa visas iis sg Imei cera vipe turnegaive caren, mr) Mepm site aio 23k omer (cepouivecanic) wiype ortepave caren, rs ihe ndamphotric semiconductor Examples oT G9, gan jae at the ype ae inte in Table 4 ir Oke Soe ws ta The prope menidefet oxides are nom Melee) oe ‘e sabiimche Si con vacuees prea, gos 2 ht 3 ‘They wi aso have sme Schonky and Frees 5 A : ee a defeat add tothe fonicconauctviy. Apr, Sas iis ton i tio Galeanples NiO, scatondefriem oxide iso" cry burn dee os provides additonal clerons needed forianic MEO BUN mo ia on os tending and elecrical neutrality by donating MAO INCH, ie in ecctsiromtie Msbstctvotaracconatthe Meth, ety tte ao ticket ions inthis way forever ton vicanty Guin, vena Fie i aM pce nie nice wo msl iom NP) wil eo” Simm TS 33 rent Fig #) Each Ni hava owenersy 2, GCE eed = poaively charged eecron pole tht eiscom Nic! Meo seo se in ‘from other nickelous ions (Ni'*) can easily move NiO “BLiNaC) 1990 3014 170, io, The positive orpaype semiconductorscarry 02 CATO) jw o 3 ocofticaret yes othe rsive 9, aa SS Gy in ie) ‘Cains an dfxetrogh he scale fromthe AD, Alito dios is NiNiO interface by cation vacancies, to the RbOs Th) io oe visa a MOtpsimcracewretcyreatwithobea ‘SOQ Mowe, is i ‘oxygen. Electrons migrate from the metal sur- so Cte 1700 son 6 a faery cecron holes 10 te atborhed oxygen So» Sutmminecy BS ae 8 aos, whchifenbocome oxygen anions inthis Sur ie 1 fry, wile Ni cations andcecrons move ute S02 40D a “in a Spee cone te eee Soran eas — Tas “Triclnie ‘900 a a Yornces and eecon hols move ward to. WO." ENO ke is ain i ardthemell.Comequenly, asthe scale hick: Tr GIG van Ske his ‘ens, the cation vacancies tend to accumulate to 710. rel = £2 = : fSraeia a he INO incre Gime, The mine iemconductor ones have vegas 0, jn it Gis Star tvely-caged re electons asthe major charge U0,” Cita awe carers, They may be either eaion excess or 30 Hews ew 2m tion dicen. Bey oxide (BeO) types YH, SAO te Be 2 te calgrercest oxides because the benim vo! atomic aoc aie 3 ‘ion (Be) is small enough to move interstitially — WO» C4190) 1580 RD 1266 wy Sieh eB wk, ssc stowmin, NOs SER yy iw BLO Fis. on m0 “om ve th ‘oxygen inthe gas adsorbs on he BeO wurace J! BUS, i Se sas Tae soi'plts wp fee gcerns fom ihe Beto #0 COmumine BBB a ‘become adsorbed O* ions, which then react with Nee ae act inteeucany MS eSane 25 C07 erin np fancies sei 8°C 07S38 / Introduction 10) theststionol bionic arangement in ypean lomdtcien 2307 Anon vacances are cated son gure 72a ate shed Fig. 11. new oxdion kines from the beryllium metal. The free electrons ‘coming from the metal surface asthe beryllium fonizes travel rapidly through vacant high-energy levels. As with p-type oxides, the cation-oxcess type oxides grow atthe oxide/gas imerface 3s cations diffuse outward through the sale "Another group of m-4ype semiconducting ox ides is anion deficient, as exemplified by zrco rium dioxide (202). In this cas, although most ‘ofthe cations are contributing four electrons to the ionic bonding, a smal fraction ofthe zirco- ium cations only contributes two electrons to become the zirconium ion ZF", Therefore, 10 ‘maintain electrical neuwality an equal number of anion vacancies must be present in the oxie. ‘This arrangement is shown in Fig 10. The oxide arovis atthe metaVoxide interface by inward df= fusion of OF through the anion vacancies inthe oxide, “Amphoteric Oxides. A number of compounds ‘ean be nonstoichiometric with ether «deficiency ‘of cations ora deficiency of anions. An example is lead sulide (PbS), which has « minimum in clectrcal conductivity a the stoichiometric com- ‘position, Thus, ifthe composition is PhaiS. itis ype and iit is PUSca, iis ype Similarly, nisic semiconductors, such acu pric oxide (CuO), have a few electron holes in thee valence band and an equal nomber of tree ‘electrons in their neatly vacant conduction band, ‘Coment is carried both by migration of electron holes in the low-energy bonding levels and by free electrons in the high-energy conduction ev- eh, ‘Oxide Texture: Amorphous Oxides. In the very early stages of oxidation and especially at Tow temperatures, some oxides appear to grow Table 4 Classification of oxide and sulfide electrical conductors ‘Matarecersenicondaaoe 5p) a MgO, CAD $0.1, HS 5. C0 THO UO, Uso Oa iy sh TNL Vay VS). NGetesdu isn Mio, Oe WS, Mads FD Mahbg Zaledy 20 (Cues, Za CBD. CS, HISimiNALO, MeAAO, 7440, 110, Gn. Sos; Metadtictsemicondactrs (6) W059 (68, C204 (250°, 290°. MEO, Fe gOy C2004 290104, 0WO, Ma Mad. M54 Ninzd es 0 es, NO NSC, (CO. O, Gyb.ba8,Ag0.CaAL0, NALD, 30) TS, (GO) S860 Sb) Amphoterconductors ‘TO, TOs), VO 0421290, 2280, MeO TSO EO) RIG, FOS (a) Meticonter Sure: R10 with an amogphous structure. In genera, these ‘oxide glasses Contain more oxygen than metal in ‘ther formulas so that oxygen wiangles or tetrac- dra form around each of the metal ions. The random network fing structures that result allow large anions or molocular oxygen 10, move through them more readily than the smaller ca fons do, Amorphous oxides tend to crystallize as they age, Examples are silicon dioxide (SiO), ‘A13Os, tantalum pentoxide (Taz0s), and niobium ‘pentoxide (Nb:0s) Tncontrast, oxides with MO and MO formulas have structures in which the small cations can ‘move readily, They are apparently always crys talline. Examples ure NiO, cuprous oxide (C420), and zine oxide (Zn0). ‘Oxide Texture: Epitaxy. As a cysalline ox- ide grows on a metal surface, it often aligns its crystal structure to be compatible withthe suc- ture ofthe metal substrate. This epitaxy Finds the best fit, not a perfet Fit, between the two crystal siructures, For example, either (111) oF (001) planes of Cu20 grow parallel w the Cu (001) plane with the (110) dgeetions of Cu20 parallel to the( 110) of copper Ref 11), Stress develops in an epitaxial oxide layer as it grows because of the slight misfit between the ‘oxide and metal crystals. The stress is likely t0 produce dislocation arrays. in the oxide that ‘would be paths of easy diffusion for mass trans port through the film. & mosaic structure may evelop in the oxide because of the growth stressas. The mostic structure consists of small crystallites with orientations very slightly tilted ‘or twisted with respect teach other. The bounda- ries between the crystallites are dislocation arrays that serve as easy diffusion paths. ‘Stresses in epitaxial layers inetease asthe films grow thicker until at some point the bulk scale ands to become polycrystalline and epitaxy is rdually lost, Epitaxy may last up to about 50, ‘am in many cases, bu is seldom strong much ‘over 100 nm. ‘Oxide Texture: Preferred Orientation. As ciation produces thicker layers, the oxide grin sine inereases. Crystals that are favorably ofi~ ented for growth wil grow at the expense oftheir neighboring grains until the oxide surface con- sist of few large grains with similar orientation, ‘The variation in growth rate of different oxide ‘rains produces the roughening ofthe sealed sut- face that is commonly observed (Oxidation Reaction Rates Linear Oxidation Reaction Rates. Ifthe met- al surface is not protected by a barrier of oxide, the oxidation ate usually remains constant with time, and one ofthe steps inthe oxidation eac- tion is rate controlling rather than a transport ‘process being rate controlling. This situation isto be expected if the Pilling-Bedworth ratio is less than I. if the oxide is volatile oF molten if the sce spall off or cracks due to internal sreses, oF if « porous, unprotective oxide forms on the metals “The linear oxidation rates Ps b ak 8) where 1s the mass or thickness of oxide formed, {s the time of oxidation, and ky isthe finear rate constant The rate constants a function ofthe meta the gas composition and pessure, and the tempera: Ttegrated, the linear oxidation equation is ache 9 “The oxidation never lows down aftr long mes at high temperatures, the metal will be completely destroyed. Figure I shows the relationship be- ‘eon oxide mass and time for linear oxidation Logarithmic and Inverse Logarithmic Reac- tion Rates, Atlow temperatures when only thin film of oxide has formed (eg, under 100 nm), the ‘oxidation is usually observed t0 follow either logs fo inverse logarithmic kinetics. “Transport processes across the film ae rae con- trolling, with the driving force being electric fields across the film. The logarithmic equation sokgbonter +) 10 where e anda are constants. “The inverse logarithmic equation is Pab- kilos eqn, where b and ky are constants, Under the difficult ‘experimental conditions involved in making mea ‘urements in te thin film ange, tis nearly impossi- bie to distinguish berween logarithmic and inverse logarithmic oxidation, Both equations have two constants that ean be adjusted to fit the data quite ‘well. Metals oxidizing with logarithmic or inverse Tog kinetics reach a limiting film thickness at which ‘oxidation apparently stops. Figure 12 shows the ‘eunes for both logarithmic and inverse logarithmie inovs.Parabolic Kinetics. When the rate-contolling step inthe oxidation process is the diffusion of fons though a compact barrier layer of oxide ‘With the chemical potential gradient as the driv- ing force, the parabolic rate law is usually ob served. As the oxide grows thicker, the diffusion disance increases, and the oxidation rate slows wn. Tho rato is inversely proportional to the oxide thickness, oF: cay $.8 412) Upon integration, the parabolic equation is ob- tne: s oe, ot ea) where kp isthe parabolic rate constant. Figure 13, shows the parabolic oxidation curve (Other Reaction Rate Equations. number ofotherkinetes equations have been fied tothe txporimental data, but it is beloved that they deseribe a combination of the new mechanisms deseribed above, rather than any new basic proc: cs. A cubic relationship: aks e414) hs often been reported. Itean be shown mathemti> tally to be an intermediate stage between logarith ‘ic and parabolic kinties Fig. 14) Initial Oxidation Process ‘Adsorption and Nucleation ‘To begin oxidation, oxygen gas is chemisorbed ‘nthe metal surface until a complete two-dimen= sional invisible oxide layer forms. Some atomic nygen also dissolves into the metal at the same line. After the monolayer forms, discrete nuclei ‘of three-dimensional oxide appear on the surface tnd begin expanding laterally at an ever-increas- ing rate (Fig. 6). The nuclei may originate at structural defects, such as grain boundaries, im- purity particles, and dislocations. The eoncentra- tion of nuclei depends primarily on the crystal tvienaton of the meta, with more nucle form- ing at high pressures and low temperatures These oxide islands grow outward rapidly by surface diffusion of adsorbed oxygen until a com plete film three or four monolayers thick covers the met, The oxidation rate then drops abruptly. ; mart tg : 3 in Time. t Fig. 12 lott rime atc ondon ties If chemisorption were still the rat-controling (low) step in oxidation after the thin film is ‘completed, a logarithmic vate law should be ob- served. A logarithmic rate law is found, but itis mare likely the result of the strong electric Field ‘across the film that affects the oxidation. Thin-Film Mechanisms A large number of theories have been proposed to explain the oxidation mechanism at low tem- ‘erates of inthe early stages of high-tempera- ture oxidation where logarithmic kinetics is com- monly observed. None of the theories is ‘completed secepted yet, and perhaps none is completely correct, but they have common threads of agreement that indicate reasonably Well what is happening. Some of dhe most impor- ‘ant dhoories wail be briefly described. ‘The Cabrera-Mott theory, probably the best «established theory of thin film oxidation, applies to films up to about 10 nm thick (Ref 12), It ‘proposes that clectrons from the metal easly pass {through the thin film by tunneling to reach ad- sorbed oxygen at the oxide/gas surface and form ‘oxygen anions. A potential of approximately 1 V is set up between the extoral oxide surface and ‘the metal, Fora film I nm thick, the field strength ‘would be 10” Véem, powerful enough t pull cations from the metal and through the film, The rate-conteolling step isthe ransfer of cations (or anions) into the oxide or the movement of the {ons tough the oxide, The electric field reduces thisbarver. The structure ofthe oxide determines ‘whether cations of anions migrate through the oxide. A8 the film grows thicker. the field Strength decreases uni it has so litle effect on the ions that the rate-contolling- mechanism changes. 'N. Cabrera and NF, Mott developed an inverse logarithmic kinetic equation to describe the ‘mechanism. A logarithmic equation is more ‘monly observed, but it can be derived from the Carera-Mott mechanism ifthe activation energy for ionic migration is 2 function of film thickness. Such a situation would exist if the oxide film ‘were intially amorphous and become more crys- talline with aging piving «constant field strength ‘through the film inscad ofa constant voltage. ‘The Hauffe-lschner theory, « modification ‘of Mot's original concept of a Space charge de- ‘veloped across the oxide film, proposes that Quanum-mechanical tunneling of electrons isthe rate-contolling step (Ref 13). After the film m_ Oxide Wiekness x 5.13. Prbolc oxidation itis Corrosion at Elevated Temperatures / 39 thickness reaches about 10-nm, tunneling be- comes increasingly difficult, and the observed reaction rate decreases grealy. For film thick- nesses up to perhaps 20:nm, a Fogarithmic equ- tion results. For films from 20 to 200 nm thick, the inverse logarithmic relationship holds. Poten- fials across thin films have been measured: change in sign ofthe potential is intepreted as a change from electronic transport contro to ionic contol The Grimley-Trapnell Theory (Ref 14).T.B. Grimley and B.MLW. Trapnell used the Cabrera- ‘Mott model, but assumed a constant electri field instead of a constant potential, They assumed that the adsorbed oxygen layer would always be com- plow, oven at high temperatures. and low pres- sure. The adsorbed oxygen would take electrons from cations in the oxide, not from the metal, 80 that a space charge would. develop at the MO/Osi, interface and be independent of the ‘oxide thickness, If the rate-controing step is diffusion of cations through vacancies, logariti- ‘mic Kinotics should be observed. If some other proces i ate controling, inear kinetics is mast likely. ‘The Uhlig theory, developed by HL. Uhlig ‘and amplified by Fromhold, also predicts loga- fithmic kinetics at temperatures upto 600 K (Ref 15), The rate-controlling step i the thermal emis: sion of electrons from the meal into the oxide (or electron holes from the adsorbed O” tothe oxide) tunder the combined effects of induced potential ‘and applied fild. The field is created by the diffusing ions. Because growth of the film de pends on the electronic work Function ofthe met- al, the theory explains oxidation rate changes at tryst and magnetic transformations; most other theories do not Solid-State Diffusion Diffusion processes in solids play a key roe in the oxidation of metals, Mass transfer may be the result of diffusion of mal ions from the metal face through the oxide layer to the adsorbed ‘oxygen anions atthe oxide/gas interface, or the result of the diffusion of anions inward through waeage ‘compat ofthe om of knee cues that ‘pee vorous hema Segradton posses Fig. 1440 / Introduction the oxide tothe metal. The diffusion of atomic ‘o4ygen into the metal fom the oxide othe gs ‘an also be involved. Within an alloy, the dia Son of oxidizable metal atoms toward te surface andthe back diffusion of unreactive atoms fom the meal surface inward 10 the unaltered alloy Diffusion Mechanisms, Atoms orions difuse through solids by any of several mechaniss “The most common is vacancy diffusion. A metal ceysial always contains large numbers of vacan- ‘es, while ionic oxides contain Schotky- and Frenkel defects that also involve vacancies. An om or ion siting on a regular latie site can diuse by jumping to a vacant identical site nearby Fig. 188) For metal atoms, his is rela- tively easy Beease he jump distances are short. For ionic crystals, the jump distances are much Dili mechani.) Vacancy itso. Iria afstn. 4) rowionSitaon Fig. 15 longer because cation sites are surrounded by anion sites, and vice versa ‘Small interstitial atoms diffuse readily from ‘one interstitial position t another. In ionic ox ‘de, the cations may diffuse interstitally, but the anions are usually not small enough to do so. Interstitial diffusion is shown in Fig. 150), In ionic erystals, an interstitial ion may crowd ino a regular lati site, displacing anion, which is forced to move into aninerstit the next latice site, This “crowdion” effect may extend for several atomic spacings along. line or ‘equivalent direction. Figure 15(c) shows “crow- dion” diffusion, Fick’s Law. In 1855, A. Fick formulated his two laws of diffusion for the simplest sor of diffusion system: a binary system at constant temperature and pressure, with net movement of atoms in only one direction, This is the usual situation for diffusion through an oxide growing fon a pure metal Fick's first law states thatthe rate of mass ‘wansfer is proportional t the concentration gra sical, Mathematically ri 15) ‘where Ji the lox oF mass diffusing per second ‘through a unit cross socton in the concentration _padient Ac) and Dis the diffusion coeficient, oF ‘fusivig in square centimeters per second, which is a function ofthe diffusing atoms, the stuctare through which they are difusing, and the tempers- ture, For diffusion of cations through a protective ‘oxide, the entry of cations into the oxide atthe ‘metaloxide terface will very nal equal the fx ‘of ations delivered tothe oxygen atthe oxide/eas imertace. For diffusion of oxygen into the metal, the concentration of oxygen changes with ime inside the mou, Fick's second law describes this change as: z-2(03) Equation 16 must be solved forthe particular ge- fomercy and boundary conditions involved (lator (e416) Table 5 Selected diffusion data in metal oxides round specimens, and so on). For oxygen atoms sifusing inward from a fat surface, with w constant

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