iJ~"~~~~~C~~~ •...........................................




Edited by ROfS'a. Shingledecker.

Ladifh Co.

Review Committee: Fred Bartkowski. Nelson ~{JI/ & Associates. ~bert Blumenthal. Marquette University; Allons De Ridder. Ladish Co.; David P. Dixon. Ampco Metal. R05ert W. Foreman. Park Chemical Co.; R. E. Haimbaugh. Induction Heal Treating Corp.; J. A. Hildebrandt. Clark €quipmenl Corp. (relired); W. James Laird. Jr.. Up/on Industries. Inc.; James T. Slaley. Aluminum Company of America; Dennis M. Wagen. W B Combustion. Inc.. Daniel S. Zamborsky. Bendix Corp.

Physical Metallurgy and the Heat Treatment of Steel .••....••..•....••••••..••....••••••..•. 28·1 Heat Treating of Steel 28·11 Stress-Relief Heat Treating of Steel _.. 28'11 Normalizing of Steel 28'11 Annealing of Steel 28·12 Austenitizing Temperatures for Hardening Carbon and Low-Alloy Steels __ 28·13 Quenching of Steel 28,13 Tempering of Steel 28'16 Martempering of Steel 28·17 Austempering of Steel __ 28·16 Cold Treating of Steel _ _ 28'19 Heat Treating of Ultrahigh-Strength Steels ....•..... 26·20 Heat Treating of Maraging Steels 28·20 Case Hardening of Steel 28·21 Gas Carburizing 28'21 Carbonitriding 28·23 Gas Nitriding 28'25 Pack Carburizing 28'26 Liquid Carburizing and Cyaniding _ 28·28 Liquid Nilriding 28·30 Gaseous Ferritic Nitrocarburlzing 28'31 Vacuum Carburizing 28·32 Methods 01 Measuring Case Depth 28·32 Heat Processing Equipment 28·33 Types of Heat Treating Furnaces 28'33 Salt Bath Equipment _•........ 28'33 Fluidized-Bed Equipment _....•.......... 28'34 Heal Treating in Vacuum Furnaces and AuxJliary Equipment _ _. 26·35 Heat·Resistant Alloys for Furnace Parts, Trays and Fixtures , 28·36 Furnace Control Instrumentation .••••.....••...•... 28·38 Temperature Control 28·38 Atmosphere Control 28'39

Furnace Safety 26·39 Furnace Atmospheres and Carbon Control ...•..•.. 28·40 FUrnace Atmospheres 28040 Control 01 Surface Carbon Content in Heat Treating of Steel 28'42 Evaluation of Carbon Control In Processed Parts 26'43 Localized Heat Treating 28-45 Induction Hardening and Temperlng 26·45 Flame Hardening 28-47 Laser Surface Transformation Hardening 28'50 Electron-Beam Heat Treating 28·50 Heat Treating of Cast Irons 28·52 Introduction to Heat Treating of Cast Irons 26-52 Heat Treating of Gray Irons 28·52 Heat Trealing of Ductile Irons 28·53 Heat Treating 01 Malleable Irons _ 28·54 Heat Treating of Austenitic lrons 28'54 Heat Treating Of Tool Steels •.•••..•.•••••. _..••••. 28·55 Heat Treating of Stainless Steels and Heat-Resisting Alloys 28060 Heat Treating 01 Stainless Steels 28·60 Heat Treating 01 Heat-Resisling Alloys 28·61 Principles of Heat Treatment of Nonferrous Alloys .• 28-64 Heat Treating of Nonferrous Alloys and Powder Metallurgy Parts •••.•....••..•......•.. 28·78 Heat Treating of Aluminum Alloys 28076 Heat Treating 01 Copper Alloys 28·83 Heal Treating of Lead and Lead Alloys 28'86 Heat Trealing of Magnesium Alloys _ _. 28'87 Heat Treating of Nickel and Nickel Alloys 26'87 Annealing of Precious Metals 28·89 Heat Trealing of Titanium and Titanium Alloys 28·89 Heat Treating of Tin-Rich Alloys 28·90 Heat Treating of Special-Purpose Alloys 28·91 Sinterlng _ 2M~2 Heat Trealing of Ferrous Powder Metallurgy Parts 28092

Thissecnon wascondensed fromMetals Handbook. Edition. olume Heat reating. ormoredetailed Ninth V 4. T F information, thereaders rslerred the largerwork. i to


Physical Metallurgy and the Heat - Treatment OT Steel
By George Krauss. Colorado School of Mines

THE HEAT TREATMENT of steel is based onthe physical metallurgical principles which reo lateprocess ing, properties and structure. In heat treatment.the processing is most often entirely thermal and modifies only structure. Thermomechanical treatments, which modify component shape and structure. and thermochemical treatments,which modify surface chemistry and structure, are also important processing approaches which fall into the domain of hell! treat-

men!. Scientific principles link the processing parameters to structure and properties. and arc increasingly necessary for proper application of the equipment and instrumentation now available for control of heat treatment processes. Examples of scientific efforts which directly support ~hetechnology of heal treatment include characterization of mechanisms of phase transformations which produce desired structures and properties of heat treated parts; determination of

phasetmnsformauonlind annealingkinetics which establish processing times. temperatures and cooling niles for heat treatments; and evaluation of mechanismsof deformation and fracture of the structures produced by heat treatment. In view of the importance of structure and its formation to heat treatment. [he purpose of this article is to describe the various microstructures which form in steels. the various factors which determine the formation of microstructures duro

<. Fe .0 Weight Percentage Carbon Fig. Ii I 1. ~ If equilibrium conditions are applicable.28·2 Heat Treat. Traditionally..f- i Ferrite Ferrite + cementite r)G " . especially in steels which contain clements which diffuse only sluggishly.-- --.. deforms and recrystallizes readily so that substantial reductions in section size by hot rolling or forging may be accomplished.06 2._-_ -~. I assumes equilibrium-i.77 E ~ . r-.r--- f--- _. care must be taken in the direct use of the Fe·C diagram to predict phase relationships in commercial alloys which contain elements in addition to Fe and C.---'_' ---. it is poss ible to produce a single-phase austenite microstructure. Steels and cast irons contain. I). the iron-carbon diagram is the most important reference for understanding the relationships between structure and heat treatment of steels. Alloys containing up to 2 wt % carbon are classified as steels. There is hysteresis in the transformation temperatures because continuous heating and cooling leave insufficient time to accomplish the diffusion-controlled phase transformations <Itthe true equilibrium temperatures.. (Ref 1) this article to illustrate the basis for microstructural formation in steels as well as Fe-C alloys. ..- .)900 f1)- RAJ 770" C.---- -- i ! . I SolUbility I I 01 .- --. The dashed lines represent the conditions where carbon is present as graphite rather thun as cementite. that the carbon and iron have had sufficient time to distribute themselves in the various phases as shown....- I --. the temperatures which arc the boundaries of the various phase fields arc frequently referred to as critical temperatures. and some of the cbaracrcristic properties of each (If the microstrucrures. carbon and other elements in steel are associated.. - '-.-. A.. and that the single-phase austenite field dominates the Fe-C diagram al high temperatures.5 2. service performance. The phase diagram shown in Fig. and therefore produce finer .:" 0. which precipitate as fine alloy carbonitrides at low temperatures.5 4.5 6.0 •I • .0 3.. 0..--- 738" 727" f- . the upper temperature range of the austenite field.26 - -..0 5. :i 800 700 600 500 400 300 200 100 0 h. in fact..._.. _-. In all low-alloy steels.e. Solid lines indicate Fe-FeJC diagram. and A. .-- -1--- I / f--- It I -- (&-F a) t-. '154' 1148" r-. in addition to iron and carbon..--. The Fe-C equilibrium diagram up to 6. If heating conditions (which raise the critical temperatures relative to equilibrium) apply. certain heat treatments such as hardening are designed to prevent formation of equilibrium structures.. The solid lines represent conditions where carbon. + 4.Dti'. The descriptions of the microstructures and principles presented here should be considered only introductory._-.. Thus the fact that equilibrium may not be achieved. Figure 1 shows that carbon in Fe-C alloys is soluble in austenite up to just over 2 wt %. cooling from the single-phase austenite field makes possible a wide variety of heat treatments based on transformation of the austenite.30 1 . alloys containing more than 2 wt % carbon are classified as cast irons. the subscript "c" being derived from the French word chauffan«..-- . 1. Elements such as Cr and' Mo are ferrite stabilizers and restrict the ranges of austenite stability..__ . Austenite.67 wt %. are new approaches to processing of steels (Ref 2 and 3). Structure-sensitive properties such as strength.m. In steels.::" ACl anti AC. and the addition of small amounts of alloying elements (rnicroalloying) such as niobium and vanadium... The details of the various heat treatments for many grades of steel are presented in the subsequent articles of this section.. I._ I-'394' s--. equilibrium is difficult to achieve. together with the shift of the phase-field boundaries by alloying elements.. This is invariably the case in steels. / Acm ~ r-.11 <.. a situution much more common in cast irons than in steel s. This characteristic is perhaps the most important feature of steels in that it enables steels to be hot worked or wrought.67 r- (.. Nevertheless. _." are used.0 2. I A.0 4_5 5. Figure I shows a portion of the iron-carbon phase diagram from pure iron through the carbon concentration of cementite. If cooling conditions (which lower the critical temperature relative to equilibrium) apply._._.. --=II. and. they are given the designation "A.5 3. and the references listed at the end of this article should be consulted for more information. ~ r+ . and Ae. and Ar. ductility and toughness establish the ease of manufacturing."I' are used as shown in Fig.5 7._'Cementite (Fe)C] ~2r I : 6. Since the critical temperatures are often identified by changes in slope or thermal arrests in heating and cooling curves.c 1S311" 14115' Liquid I .- .. when it exceeds its solubility in ferrite and austenite. place limitations on the direct use of the Fe-C phase diagram.. '/ ~- I I I - _. A.. also referred to as "I-iron.. without the obstacles which second phases present to dislocation motion and without the sites for fracture initiation which second-phase particles offer. will be used in 1100 1000 912" Austenite h-Fa) -.-.---J _ . .. THE IRON-CARBON PHASE DIAGRAM The microstructures which result from heat treatment of steel are composed of one or more phases in which the atoms of iron. Also. Hot deformation of austenite at lower temperatures or even in the twophase ferrite-austenite . or simply A. the designations Ar •• Ar.. and.. is present in the form of cementite (Fig. dashed lines indicate Fe-graphite diagram._-. (a-Fa) I J li- Austenite cementite I - ._ ." . Some alloying elements such as Mn and' Ni are austenite stabilizers and extend the temperature range over which austenite is stable. the designations Ac" Ae.field (controlled rolling)..- -. F• .f- -- 1J .m are used. Therefore. therefore.5 1. Sometimes.0 6... hot deformation is performed in. is the facecentered cubic crystal fonn or phase of iron which is stable at high temperatures. the subscript "r" being derived from the French word refroidissant. many other elements which shift the boundaries of the phase fields in the Fe-C diagram. The low-temperature deformation and/or precipitation retard or prevent austen ite recrystallization and grain growth. 1700 1600 1500 1400 1300 1200 f---.l~Z .67% C. and limitations to service conditions of heat treated steels. 6.n. The temperature and composition ranges in which the various phases exist are shown on the diagram. The single-phase austenite.ng ing heat treatment processing of steel. subject to the above limitations. 2. I. _- - -.

interlamellar spacings decrease. Figure 6 shows an isothermal transformation diagrurn for a cutcctoid steel. When the solubility of carbon in either austenite or ferrite is exceeded. is dissolved in the octahedral interstitial sites between iron atoms in ferrite and austenite (Ref 7). Also. for some reason. Scanning electron micro. Figure 2 shows an example of the brittle fracture which develops in ferrite stressed at low temperatures aml/nr high strain niles._- <. dis 10cation motion in the body-centered cubic structure is sevcrclv restricted (Ref 5 and 6). cemcnrue forms on ferrite grain boundaries.r-. 727°C in the Fe-C system. Ferrite. 4. and are responsible for the discontinuous yielding of low-carbon steels with largely fcrritic microstructures. Figure 4 shows an example of fine dendritic cementite particles which have formed by Quench lIging on dislocations in the ferrite of a low-carbon steel. 28-3 PEARLITE AND BAINITE Figure I shows that the austenite in an ironcarbon alloy containing 0. The other process i~ associated with precipitation of fine carbide panicles either on dislocations or in the ferrite Fig.. iron atoms must rearrange themselves by short-range diffusion from the face-centered cubic structure of austenite to their arrangements in the crystal structures of ferrite and cementite at the interface of the growing pearlite colonies.015 0. on slow cooling. forms. the thermodynamic driving force increases. Pearlite in a eutectoid steel is nucleated at austenite grain boundaries. The interstitial sites for carbon in ferrite arc much smaller than those in austenite. With increased undercooling . creases exponentially with increasing temperature. The compound cementite has higher strength and lower ductilitv than either ferrite or austenite and.0206 " 738' ~ 550 // 1/ 500 900F 1/ . and the ferrite gray. However.. the carbon is trapped in the interstitial -ircs and contributes to various aging phenomena unique to ferrite steels (Ref 5 and 8).trbtlum 40. also referred to as a-iran. Fe-tich side of Fe-C diagram. 770' (CURIE' TE'MPE'AirUREI 750 r-.Fe:\C -- I .C or a-carbide. graph showing pearlite In a eutectold rail steel. Fig. The rate of transport of carbon anti iron atoms is temperature dependent and in- I Fig. In Fe-C alloys and steels. Figure 5 shows pearlite which has formed in a eutcctoid steel. The diugrurn shows the beginning and end of the eutcctoid rrunsformution of austenite to pearlite for specimens cooled from the single-phase austenite field and held isothennally at temperatures between A.'nding on its morphology and distribution. Thus. graph showing cleavage of a bodycentered cubic microstructure. because of its small atomic size. Figure J shows an expanded portion of the iron-rich side of the F. I (-y-Fe) Austenite .77 wt % carbon must transform 10 ferrite and cementite at 727 "C. Carbon must diffuse 10 the growing cementite lamellae of the pearlite. 5. is the bodycentered cubic form or phase of iron which is stable at low temperatures.~nmenlal) 400 Fe Fig. Courtesy of F..010 0. Courtesy of J_ E. ZiaEbrahiml. The one process is associated with segregation of carbon atoms to dislocations and grain boundaries. If.(a-Fe) I IJ50F Ferrite 700 1250F 650 IISOF I I 600 10S0F l000F // / / / k::: <:: 0. Courtesy of F. also referred to as Fe.025 Weight Percentage Carbon 3.05 0. 0. cooling is too rapid for cementite formation. Thus cleavage is a direct reflection of the crystal structure of ferrile and presents a major Iimitation to the use of steels under certain service conditions. The fracture is termed cleavage because it occurs by cleaving or separation across {I DO} planes of the body-centered cubic structure. and 800 r-. the transformation of austenite to pearlite accelerates with decreasing temperature.t----_ Fe. and causes a low rate of growth for those colonies which manage to nucleate. Both strain aging and quench aging effectively pin dislocations.1-' eQu. Scanning electron micro.005 0. austenite grains and subsequently fine austenite transformation products during cooling after hot deformation. 850 !5OOF 1450F -. As a result of the: latter changes.. the phase cementite..020 0. Zla-Ebrahlml.ent of ferrite phase field and decrease of carbon solubility with decreasing temperature (Ref 1) .63Mn steel aged 115 h at 97 °c. Indacochea (Ref 9)_ 950 1700F 'C Atomic Percentage Carbon 0. del.. Microstructures in lowcarbon steels which consist largely of polycrystalline ferrite are highly formable at room temperature: dislocations move readily on the many slip systems of the body-centered cubic structure (Ref 4).OBC-O.02 wt % and with decreasing temperature becomes almost negligible. and grows as sphericalshaped colonies or nodules into the austenite. The coarse interlamellar spacing increases the diffusion distance for carbon. here.austenite interfaces and the ferrite-cementite interfaces within the pearlite colonies is low. Transmission electron micrograph showing cementite preCipitated on dislocations In an O. and theretore the solubility of carbon in ferrite is significantly lower than in austenite. At temperatures just below the eutectoid temperature.C diagram.Jl.. pearlite transfonnation at temperatures close to Ihe eurectoid temperatures is sluggish and the pearlite microstructure which forms is relatively coarse. the cementite appears white. the nucleation rate of pearlite colonies increases.. As a result of the decreasing solid solubility with decreasing temperature. the thermodynamic driving force for the eutectoid reaction (the decrease in free energy per unit volume when austenite is replaced by pearlite) available to offset the increase in energy associated with pearlite colony . ferrite grains fracture in a brittle manner with little plastic deformation at low temperatures. and the growth rate of colonies increases. a unique parallel array of ferrite and cementite lamellae termed pearlite develops as a result of the eutectoid reaction.10 900 isoos I. Carbon. 2.Fe·C eQulhbf1um le. showing ext. at low temperatures. contributes in a variety of ways to the strengthening.. As a result. The maximum solubility of carbon in ferrite is only about 0. As a result. deformation and fracture of steels.Physical Metallurgy and the Heat Treatment of Steel matrix and is referred to as Quench aging.. A solid-state reaction in which one phase transforms to two other phases is referred to as a eutectoid reaction. the nucleation rate of colonies is low and the spacing of cementite lamellae within the colonies is large.perlmenlal) 450 600F i t---- . and is referred to as strain aging.

Carbon is rejected from the ferrite and concentrates to form relati vely coarse cementite particles between the ferrite laths.20Mn-O.11' bon (hypereutectoid steels) than the eul~Ltl'IJ composition must first form either ferrite "I .'" " I~ '~ III 10~ 66 III Fig... The growth of proeutectoid ferrite is u~r-:n· dent on the rejection of carbon atoms into the austenite and the transfer of iron atoms <lCW" the ferrite/austenite interface from the fac~.19Sl steel blocky or feathery appearance of upper bainite. Jacobs (Ref 12). - 400 I- ~~ \ . I a: I I !I. ~ t. Fig...r- 0. 9...40 41 II Lower bainite . Light micrograph (nltal etCh) showing lower balnHe (dark plales) formed In 41 SO steel. Fig. Therefore.. TIME .. giving an acicular or needle-like appearance to the microstructure rather than the Figure I shows that alloys which contain either less carbon (hypoeutectoid steels) or more c. ".. T '~II End or A - .. Carbon Two forms of bainite develop in steels. ~.. 6.'. Light micrograph (nltal etch) showing microstr4cture of proeutectold ferrite (white) and pearlite (dark) In a 0. I I .! II 11I1 I I 1IIII II 11II en rJ) Austenite L_l I I Beginning of transformation _. then etched in nital to reveal bainite patches.28·4 °C Heat Treating OF '_' II 11II 1400 1200 . Instead of an atom-byatom transfer across an interrace.( of the pearlite colonies appear uniformly I>IJ..\ 600 \~ . the diffusion of iron atoms is reduced to the extent that they can no longer be readily transferred even the very short distance across the pearlite/austenite interface. \... The white grains are proeutectoid ferrite which ha\c nucleated on and grown from the austenite ~1J!n boundaries." +1".. \J 1000 " -~"""~I . 8.. Bain... carbon was rejected into the austenite grain boundaries Eventually. Figure I! shows lower bainite which has formed in a 4150 steel.. -. \ . Jacobs (Ref 12)• \i. I--- 200 r~ r.·. Figure 7 shows patches of upper bainite formed by partial transformatlon of the austenite at 460 "C. r-' 800 "'A " .~ ....:-.....·1rc... who did much pioneering work in the characterization of austenite transformation and hardenability of steels (Ref I I).~-. the mechanism for the change in crystal structure from austenite to ferrite changes from diffusion to shear. I-- f-.." rnentite when slowly cooled from the singlc-plu« austenite field.. PROEUTECTOID FERRITE AND CEMENTITE Etched in saturated picric acid plus a wetting agent to reveal austenite grain boundaries.It t~ interface.SECONDS Specimens were austenitized at 900·C and had an austenite grain size or ASTM NO... .or plate-shaped crystals of ferrite.·. Isothermallransformatlon 0.~...l because the light is scattered by the lamclhr structures which are too closely spaced 111 It' be solvable in the light micrograph. The other type of bainite is termed lower bainite because it forms at lower temperatures than docs upper bainite.76% Mn (Ref 10) diagram for 1080 steel containing 0. +F+ I .tMooI \* -10. Light micrograph showing patches of upper bainite formed in 4150 steel partially transformed at 460 ·C. - - I-- '_' _ A I _ .tri I~ 5 10 Estimated II 'IIII 10' 1 HOUR I I" . ~ .. [he u laucr process is dependent on the degree Ilf .6...5 12 r' M90j * \' t- I-TDIAGRAM I I ~I I 10' ITii~. 7. Courtesy 01 F. The ferrite or cementite fl'rltll'J before the eutectoid reaction are termed pfl'<. The ferrite takes a plate morphology and the cementite is present as very fine particles within the ferrite plates.-t-rt..I I}e>/ - 38 40 Fig.._ V .. C'· .--_- FJ~ - w Z I o a: < 11 32 - .--'Upper bainite . Also under some conditions.'U· tectoid ferrjle or proeutectoid cementite. 7. . large numbers of iron atoms shear or move cooperatively to fonn lath. after Edgar C. The general morphology of upper bainite is shown in Fig.. Again the very fine carbide particles in the buinne plates are not resolvable in the light miLII" graph. The acceleration of the transformation with decreasing temperature is apparent.ul'fl' cient for pearlite formation. Rgure 9 shows the mie-rostructure of a 1\. and the balance "I the microstructure transformed to pearlite.f " u III... As the ferrite grains grew. diffusion and cementite formation must still occur because of the low solubility of carbon in the body-centered cubic Ferrite. .C- .17C-1.. but the cementite forms as separate particles rather than as conti nuous lamellae as in pearlite.--- \'. The austenite which did not transform at 460°C formed martensite (light background phase) on quenching to room temperature.- M.. The microstructure produced by both shear and diffusion is termed bainite.. Upper bainite forms in patches containing many parallel laths of ferrite. 50%':._ I-I 55 57 tilli."· carbon steel after air cooling from austenite. A. Courtesy of F.I" herency or disorder in atom arrangement .. A. the carbon concentration wus ..79% C and .transtormation _F . just below the range of pearlite formation. One is termed upper bainite because it forms at relatively high temperatures.-Coarse pearlite Fine pearlite ' I I ! .". The bainite plates arc at angles with respect to each other. 540 ·C.43 50 r-f ""'" .·nI'·IC\I cubic to the bod y-ccntered cubic SlrU. but the ferrite laths am! cementite particles arc 100 fine to be resolvable in the light micrograph. At temperatures below 540 DC.. ~. 'lIb'hr u- . \1.

Initial proeutectoid cementite growth appears to depend only on diffusion of carbon and therefore proceeds very rapidly. however. a transgranular fracture morphology (see Fig._ Shear or the displacive. Figure II shows an example of 52100 steel quenched from 1000 °C (Ref 15). if the austenite in hypereutectoid steels is rapidly cooled.. Courtesy of J. Figure 12 shows the microstructure of an intercritically austenitized and hardened bearing steel. Later stages of cementite growth require partitioning of substitutional alloying clements such as chromium and therefore are very sluggish (Ref 14). 9. develops in rapidly cooled low-carbon steels. IO(b). the ferrite structure if they are ferrite stabilizers or rejected from the ferrite if they are austenite stabilizers. 1 . tionalalloying elements must be incorporated into . Arrows point to fine spherical carbide par· tlcles. and is the base structure for hardened steels. Generally under conditions of slow cooling.esy of M. The spheroidized cementite particles (white) are dispersed in a matrix of martensite (dark). In view of the brittleness which continuous networks of proeutectoid cementite impart . 10. D. Figure IO(b) shows fracture that has followed proeutectoid cementite interfaces which are characterized by many flat facets with intervening ledges. The presence of small amounts of cementite is. Scanning electron micrograph showing Intergranular frac· ture In 52100 steel all quenched from 1000 'C (Ref 15) MARTENSITE Martensite is the phase fonned in steels by a diffusionless. . proeutectoid cementite networks as well as the lamellae of cementite in pearlite partially dissolve and spheroidize.12C-1.Physical Metallurgy and the Heat Treatment of St. 13. Martensite is not shown on the Fe-C diagram because it does not fonn under equilibrium conditions. however. Scanning electron micrograph ·of fracture surface of 52100 steel Intercrltlcally austenltlzed at 800 and 011 quenched. Courtesy of T. (Ref 15) ac liIIod swl_ In_ -RegIon aI pIaatIc - \ (~) Fig. shear transformation of austenite. 14. resistance are required). During the intercritical healing. Tfe balance of the microstructure is martensite which formed on quenching after the cementite network had developed. (a) Light micrograph (nltal etch) showing cementite network on prior austenite grain boundaries In an Fe-1. the transfer of iron atoms across ferrite/austenite interfaces is restricted. cooperative movement of many atoms has already been mentioned as a mechanism by which bainite and acicularproeutectoid ferrue fonn. When martensite forms. Recent experimental and theoretical work on the effects of alloy element partitioning and interface structure on the formation of proeutectoid ferrite is reviewed in Ref 13. an analytical technique capable of determining chemical compositions of very thin layers (Ref 16). 12 is fractured. Bruce Kelley. frequently referred to as acicular or Widmansttitten ferrite. even the carbon atoms cannot diffuse. and the diffusion-controlled growth of ferrite is replaced by a shear mechanism. Court.". proeutectoid cementite nucleates and grows on austenite grain boundaries during cooling from the austenite phase field. Fig. As expected from the Fe-C diagram.• hypereutectoid steels arereheated inl. The fonnation of the latter structures. in contrast to Fig. I i . Thus Fig. .ercrilically into the austenite/cementite two-phase field for annealing (if maximum ductility and machinability are desired) or for hardening (if wear and fatigue 28-5 ! . . martensite eventually decomposes to a mixture of ferrite and cementite if heated below A. established by Auger electron spectroscopy. The fracture is initiated at the fi ne spherical carbide particles and the toughness is related to spacing of the particles (Ref 17). The intergranular fracture facets are quite smooth. occurs under conditions such that carbon diffusion accompanies the formation of body-centered cubic ferrite . Figure 10(a) shows a continuous network of proeutectoid cementite which has formed on austenite grain boundaries of an Fe·Cr-C alloy. generally rapid cooling to temperatures well below A. the proeutectoid cementite and martensite is quite brittle. showing spheroldlzed eementltepartlcles In a matrix of martensite produced by Intercrltlcal austenltlzlng and quenching.. When a hardened steel with a microstructure similar to that shown in Fig. Schematic illustration of shear and surface tilt associated with formation of a martensite plate. Substitutional alloying elements such as manganese tend to retard the formation of equlaxed ferrite grains and promote acicular ferrite formation. (al Fig.. (b) Scanning electron micrograph showing cementite Interfacefracture morphology in same alloy. Light micrograph (nltal etch) of a high-carbon bearing steel. The interface between Fig. In hypereutectoid steels. is required to fonn martensite. 13) developsrather than intergranular fracture (Fig. 12. Gelb (adapted from Ref 19). 11. Ando. theproeutectoid ferrite grows unifonnly into austenite and an equiaxed ferrite grain structure develops as shown in Fig. As a result a plate-shaped morphology of ferrite. However.5Cr alloy. and no cementite is visible in this scanning electron micrograph. The very rapid initial growth of proeutectoid cementite may occur even during oil quenching for hardening and is associated with the intergranular fracture often observed in high-carbon steel quenched from temperatures above A.. 1 I . II).

Figure 14 shows schematically a martensite plate which has formed in austenite adjacent to a free surface. A practical benefit or the decomposition is increased toughness. Electron microscopy is required to show that the fine structure of lath martensite consists of a high density of tangled dislocations and that retained Fig. Consistent with the low M.i. The lath morphology forms in low.. is the reduced amount of martensite which forms on cooling to room temperature. below the resolution of the light microscope. Tq: f = I . with only the largest laths resolvable. of this alloy.BON 316 -i---~_ PLATE 1.) the carbon atoms are trapped in Ihe octahedral interstitial sites. formed by quenching to any temperature. anti the austenite plane along which the martensite forms is termed the habit plane. the amount of martensite formed on quenching to any temperature below M. of a given steel is known. can be established. 17._..Tq)] Thus.4 204 93 0 1.exp . large volume fractions of austenite may be retained in high-carbon steels. Examples of microcracks are shown in the large plate of Fig. A wide range of microstructures may be PIlI. As a result of these characteristics. Therefore. 0. and consists of regions or packets where many fine laths or board-Shaped crystals are arranged parallel to one another. and therefore the microstructure appears very uniform.[0. Investigations Indicated are Identified by their numbers in that reference. 0. or (259).0 CAR. The carbon range in which a mixed morphology of lath and plate martensite forms is scnsitive to alloy content and is not well known. not only must the face-centered cubic austenite lattice transfonn to the bodycentered tetragonal lattice of martensite.J9C alloy cooled to room temperature.2 Fig. Figure 17 shows a plate martensite microstructure in an FeI.6 WEIGHT -. Figure 15 shows M. creating a supersaturated ferrite with a body-centered tetragonal crystal structure. The higher the concentration of carbon atoms. but the martensite crystal once formed must accommodate itself to the constraints of the surrounding bulk austenite and the restrictions imposed by the plane-strain deformation parallel to the habit plane (Ref 19). . The width of most of the laths is less than 0.. M. TEMPERED MARTENSITE As-quenched martensite is supersaturated with carbon. The following equation has been developed (Ref 20) for estimating the volume fraction of martensite. and/or dislocation arrays typical of low-temperature plastic deformation. temperature is a function of the carbon and alloying-element content of a steel. and may coexist with retained au. by lowering the carbon concentration of the austenite by intercritical ausrenhizing (thereby developing a more parallel martensite morphology and less impingement). contains a high density of dislocations which store considerable strain energy. Light micrograph (nUal etCh) Showing lath martensite In 434Csteel 011 quenched from 940 ·C and tempered at 35D ·C (Ref 23) creasing amounts of carbon in solid solution in the austenite. :I w ~""""""'QI <.. Figure 15 indicates that two types of martensite form in carbon steels. if the M. Light micrograph (aqueous 10% sodium bisulfide etch) showIng plate martensite and retained austenite In an Fe-1. The martensitic transformation is characterized by athermal kinetics. The plate morphology of martensite forms in high-carbon steels and consists of martensite plates which form at angles with respect to each other on either (225). The habit plane of the laths is close to but nOI. and by tcmpering. Figure 16 demonstrates the above characteristics of lath martensite in a 4340 steel. 15. (Ref 2. The decrease in M.e . The two categories are based on morphology and microstructural characteristics of the martensite (Ref 7 and 21). a heat treatment process which is referred to as tempering. The M. temperature as a function of carbon content In steels.. The fine structure of plate martensite consists of thin twins. a large amount of retained austenite is present. 16.4 0.8 PERCENT 1. Even in the range of carbon contents where lath martensite forms.011 (M. <. .6 0 0 0.39C alloy (ReI 24) . and a number of relationships have been developed to relate M. martensitic microstructures are quite unstable. duced by tempering of martensite. temperature. An important consequence of low M. with increasing carbon content is related to the increased shear resistance produced by in- austenite is present as thin films between the martensite laths (Ref 22). ano decompose when heated. temperature. Carbon atom. as a function of carbon content. about 10 nm thick. In order to accomplish the shape deformation shown. Composition ranges of lath and plate martensite In Fe-C alloys are also shown. This accommodation is accomplished by slip or twinning of the martensite plate. habit planes. 17. and as a result martensite in steels contains a high residual density of dislocations and/or fine twins. and flIT this reason almost all hardened steels are hcned to some temperature below Ac I. according to the above equation.exactly {I I I}. to composition (Ref 7). i. rearrange themselves into various configurations Fig. LATH • :I 600 400 200 .2 1.· tenite. there is a gradual decrease in the definition of packets with increasing carbon content (Ref 26).5 )Lm-i.28-6 •F 1600 Heat Treating ·C 871 • GRENINGER (8) o TROIANO AND GRENINGER (10) • COHEN ET AL (24) • DIGGES (25) • GRENINGER AND TROIANO (26) 6 KAUFMAN AND COHEN (27} Q ESSER ET AL (28) DBIBBY AND PARR (29) 760 649 538 427 ~1000 ~ ~ :::l a: 800 w a.e. The martensite surface is lilted by the shear transformation. volume associated with the fine laths or plates of the murtensitic microstructure. the temperature at which martensite starts to form on cooling in a given steel. The density of microcracks in plate martensite is reduced by formation of martensite in fine-grained austenite.• the amount of martensite formed is independent of time and is a function only of the amount of undercooling below the M.. the greater the tetragonality (Ref 18). has a very high interfacial energy per uni.and medium-carbon steels. The impingement of nonparallel plates during development of a martensite rnicrostructure sometimes causes microcracks to form in the martensite (Ref 25).

The fine dark streaks mark positions of rows of very fine carbide particles. tempering is performed at relatively low temperatures. 28-7 Clustering is associated with diffuse spikes around fundamental electron diffraction spots of martensite Identified by satellite spots around electron diffraction spots of martensite Identi fied by superstructure spots in electron diffraction patterns Recent work identifies carbides as eta (orthorhombic. Fcz. The carbide is not the equilibrium Fe. segregation of carbon atoms to dislocations and boundaries Modulated clusters of carbon atoms on (102) martensite planes (A2) Long period Precipitation Transformation ordered phase with ordered carbon atoms (A3) of transition carbide as aligned 2-nm-diam particles of retained austenite to ferrite and cementite (T2) CommOllts .-----------------------Table1.------. subject to the development of various ernbrittlernent phenomena. Therefore..22C alloy tempered at 350 ·C (Ref 33) I i' .Rlc microstructure of an Fe-1. (Ref 28 and 29).. Significant increases in toughness are achieved by tempering at temperatures above 150 DC. The reactions which produce the carbides have long been recognized and are classified as stages of tempering: T Tl. The mix and composition of the carbides may change significantly with time (T4) Segregation and cosegregation of impurity and substitutional alloying elements v- and structures within the martensite crystals even at temperatures well below 100 DC (Ref 27).. Tempering between . ' Table I lists the various reactions and microstructural changes which may be developed by tempering steel (Ref 29). Many of the reactions or microstructural states require further characterization.. -----. .. and retained austenite transforms to . iron. 19. In general.. . but a transition carbide. In 'steels tempered between 200 and 350°C. toughness increases and hardness decreases. and therefore steel composition. time and temperature determine where a given tempering treatment stops in the sequence of structural changes indicated in Table I. The hardness. . The aging and tempering classifications serve primarily to mark microstructures which form on the way to equilibrium. remains high because of the extremely fine carbide dispersion and the retention of much of the dislocation substructure introduced by the martensitic transformation. The particles themselves are masked by the strain which accompanies the precipitation and which causes the dark contrast in [he transmission electron micrograph. and W-containing steels..Ji' I 4 § 3 "i c: II> c: ~ E fl 2 tl 0 I... ctlon IIId symbol (tr clnisuatod) Clustering of 2 to 4 carbon atoms on octahedral sites of martensite (AI). ultimately a microstructure which consists of spheroidized carbide particles dispersed in a matrix of equiaxed ferrite grains. I ..nge. and others may yet be discovered.~'" x. 20. A portion of a single plate of martensite in an Fe-L 22C alloy tempered at 150 DC is shown. Fe~). o~ . etc. 'I '" t! ~--------------200 300 400 100 Tempering temperature ("C) Fig.. and/or alloying elements.and medium-carbon steels This stage now appears to be initiated by chi-carbide formation in highcarbon Fe-C alloys The alloy carbides produce secondary hardening and pronounced retardation of softening during tempering or long-lime service exposure around 500 ·C Responsible for temper embrinlernent Physical Metallurgy and the Heat Treatment 01 Steel 20 to 100 60 to 80 [00 to 200 (Tt) 200 !O 350 250 to 700 500 to 700 350 to 550 Formation of ferrite and cementite. however. ·C -40 to 100 R.. The reactions are controlled by diffusion of carbon.. but more recently designated eta-carbide with an orthorhombic structure as identified by electron diffraction (Ref 32). which have precipitated from the supersaturated martensite (Ref 30).. in applications where high hardness must be retained. . and to distinguish those reactions from the carbide-forming reactions it has been suggested that they be classified as aging reactions: A" Al> etc.C) Associated with tempered-martensite embriulemeru in low.~ 5 o 4t30A + 41308 x 4130C -===== X~_~/>:·_'" J "/ I I tI .C. some occur concurrently. . each about 2 nm in diameter. first designated as epsilon-carbide with a hexagonal structure as identified by x-ray dif- Fig. Steels tempered to develop the fine transition carbides show a modest but significant increase temperature in toughness. 0'" . usually between 150 and 200"c' Figure 18 shows me fine structure which develops in martensite as a result of low-temperature tempering. Transmission electron micrograph showing chl-carblde In the marten.100 DC and ACt produces various types of carbide-particle dispersions as well as major changes in [he matrix martensite.. as tempering temperature increases.. eventual development of wellspheroidized carbides in a matrix of equiaxed ferrite grains (T3) Formation of alloy carbides in Cr-.22C alloy (Ref 30) 5 • ~. earlier studies identified the carbides as epsilon (hexagonal. Mo-. Tempering reactiDns In sleet Temperature .. Transmission electron micrograph showing fine structure In a plate of martenalte In an Fe-1. Retained austenIte and cementite as a function of tempering In several medlum-carbon steels (Ref 34) fraction (Ref 31). • 4340 FIg.• I . -. the transition carbide is replaced by cementite or x-carbide. . Both the epsilon-carbide and eta-carbide have carbon contents substantially higher than that of cementite. The reactions which depend on very" short-range rearrangement of carbon atoms in the as-quenched martensite prior [0 carbide formation have only recently been studied.:. 18.-:x . .

This decrease in impact toughness produced by tempering in the range of 250 to 400 ·C is referred to as tempered martensite embrittlement. However. vanadium and other carbide-forming elements may also develop depending on the composition of the steel.22C alloy tempered at 350 ·C (Ref 33).2% Mo. In order 10 characterize the conditions which produce the various microstructures. Figure 21 shows the structure of a 4130 steel quenched to form martensite and tempered at 650 ·C. the temperature range 350 to 550 DC.2S·'min) 1 600 / . In alloy steels. The coarse carbides produced by replacement of the transition carbides and transformation of the retained austenite. A number of other carbides of chromium. an increase in hardness may develop. 10 Fig. or slow cooling through. 21 have a specific habit plane and have been identified as MOle (Ref 35).28·8 Heat Treating Austenitizing temperature = 860·C I 800 . persists because of the pinning of the lath boundaries by carbides. hardness and strength drop rapidly and toughness improves significantly.ACl '(O. form during high-temperature tempering. if the alloy carbide dispersions are sufficiently fine and dense. (Ref 38) denum. \ \lO \ ~ 1\ 1'--_ 'I. This phenomenon develops during tempering in. Continuous transformation (solid lines) and Isothermal transformation (dashed lines) diagrams for steel containing nominally 0."'" after cooling to room temperature ~ 10 " i t j . ~I\ \ \ ~ 400 Ms \ ~ 300 200 _ 100 ~. and is accomplished by various recovery mechanisms. if impurities such as phosphorus. I -0 . Courtesy of F. The carbide particles are considerably coarser than the transition carbides in Fig. The intralath carbides in Fig. Tempering at temperatures above 400 ·C produces substantial coarsening of the microstructure. toughness increases significantly with increasing tempering ternperature. that the austenite is stable throughout the temperingtemperature runge in which the transition carbide forms. Several cooling rates are related to positions on a Jomlny end-quench specimen. 21. 22... and that the austenite begins to transform at temperatures above 200 ·C.C _\~~~ f\\~-~~--.2 Mo. Isother· mal transformation (IT) diagrams are based on the austenite decomposition at constant temperatures. \\\~ . and is referred to as temper embrittlement.. ferrite and cementite. Carbide particles are present within and between the remanent martensite laths. Transmission electron micrograph showing microstructure of 4130 steel water quenched from 900·C and tempered 500 min at 650 "C..4 C. 1. As tempering temperature increases above 400 ·C.0 Cr and 0. while continuous transfonnation (CT) . these elements may segregate to grain boundaries and/or carbide-matrix interfaces and cause large reductions in impact toughness (Ref 36). various alloy carbides. temperature of transformation. which contains nominally) % Cr and 0. I I ~ . reduce impact toughness.~I~IN" ~~~.j_ f\\ II 53 52X52) @ \~~l \ 00 ~ I(28121A21))<W® O·~H-ar-:'-dn-eS-S.:'RC=-. I I· 90 100 •l o '0 20 30 40 50 60 70 80 Distance trom quenched end Fig.. and cooling rate. The impurity atom segregation may be accompanied by the cosegregation of the substitutional alloying elements present in steels (Ref 37). but also the martensitic matrix is significantly altered. The reduction in dislocation density is driven by the reduction of the strain energy which accompanies the elimination of the dislocations.I'I I\A I \1\ B'\. 19. in addition to cementite. and are present at the interfaces of the martensite plates as well as within the plates. This increase in hardness due to alloy carbide precipitation high in the tempering-temperature range is referred to as secondary hardening. Not only do the cementite panicles coarsen and spheroidize. together with a limited recovery of the dislocation substructure of the martensite. In alloy steels such as 4130. As noted.-':-H:-. Figure 19 shows a dense distribution of carbide panicles. when it transforms on tempering. Figure 20 shows that small amounts of austenite are present even in medium-carbon steels. identified as x-carbide. The X-carbideis a complex carbide with a monoclinic structure which forms in tempered high-carbon martensites and is eventually replaced by cementite. in an Fe-1. the development of fine alloy carbide dispersions offsets the softening which accompanies the changing dislocation substructure and coarsening of the lath and cementite structure. The lath morphology. although coarsened. Woldow. two types of transformation diagrams have been developed. I I TRANSFORMATION DIAGRAMS The previous sections have shown that the transformation of austenite produces a wide variety of microstructures in response to such factors as steel composition. molyb- i \ (I\\~~ainitellormatir\~~'\"~~-I\*"~\" \~. ~ 500 !. i MartensSlailrte ~'l\ \\ ~\ 1tS[\ \I\\~I\"\~II / \\ 1\ \ 1\ 1\ \ \ CT diagram I gOI~I~gr. Austenite in medium-carbon steels is retained between martensite laths and."I / A· End-quench test It' r"I ::! 40 GI c: l~ / 'iB '0 :c 3 20 _l m <. The laths are almost dislocation-free and are now ferrite because all carbon has completely precipitated as carbides. In fact. • I I 60 u 50 II: :c _. antimony and tin are present in a steel. produces relatively coarse plates of interlath cementite (Ref 22).

24. 6) in that proeutectoid ferrite forms.th carbon or create very fine carbide dispersions.. Hardness as a function of carbon content for various microstructures In steels.A1J. For example. Hardnessas a function of carbon cq~t~t. 22 shows that all of the phase transformations are shifted to lower temperatures and longer times by continuous cooling. Comparison of the IT and CT diagrams in Fig. Figures 23 and 24 demonstrate the great versatility of steels and the major effect of carbon content on establishing mechanical properties.ns. . (After Ref 39) diagrams follow microstructural development as a function of cooling rate. An example of an IT diagram for a eutectoid steel has already been shown in Fig. it IOUY be impossible to produce fully manensitic structures in all but the very thinnest sections. The microstructures in the medium-carbon steel (Fig.. L. Also the alloying elements in the 4140 steel significantl y retard formation of ferrite and pearlite and thereby increase the range of cooling rates which form martensite and bainite. medium. (Sir cooled) k!:: r--1' I .'. More detail regarding the effect of tempering is shown in Fig.. ' SUMMARY: CARBON CONTENT MICROSTRUCTURE AND PROPERTIES Figure 23 shows hardness as a function of carbon content for the various types of microstruc- tures which may be formed by heat treatment of steel. For a given quench.el 1100 1000 800 700 600 500 400 300 200 100 .c . The shear transformations produce fine crystals (laths or plates).~ii~8 :~~~o~~~~~:~~es Carbon. containing nominally 0.he If- / structures Ternper&d mlne-nsilk and _ microstrtJclut!!l5 I I ba~l'Itc 50 I-- F.of . 28·9 -: IIT I __.r. Superimposed on the diagram arc various cooling rates. ~:. 1% Cr and 0. ~ V§b'. nickel and/ or molybdenum may have such high hardenability for martensite or.In:.~-----------------------Physical Metallurgy and the l. The lower-strength microstructures are produced "by diffusion-controlled transfer. 22) are more varied than in the eutectoid steel (Fig."".. Figure 22 shows CT (solid lines} and IT (dashed lines} diagrams for a medium-carbon alloy steel. reduced distortion and/or prevention of quench cracking...4% C.0 7'. Figure 22 shows that an important effect of alloying is to retard the formation of microstructures of low hardness. ~ ... in low-carbon steels which have very low hardcnability.Fe-C alloys (Ref 40)' . supersaturate the structure wi. > r <Ii iii r "0 en <I> c: o Carbon. and introduce a high dislocation density into the product phases. Cross-hatched area shows effect of retained austenIte.microstructural changes which pro- or . Most heat treatments are performed by continuous cooling. percent tempered at various temperatures Fig. 6. At the other extreme.fOatl~n~l~e . The CT diagrams provide the basis of hardenabiliry. bainite formation that it is very difficult 10 form ferrite-pearlite microstructures except under conditions of very slow cooling in very heavy 'sections. alloying increases depth of martensite formation in a part.o. Low-carbon steels are therefore invariably used with ferritepearlite microstructures where the high ductility of ferrite is beneficial for cold working and formability. The microstructures with the highest hardness are formed by transformations which involve shcari.• the rnartcnsjtc or bainite transformations or the tempering of the shear-produced martensite microstructures... 4140.".. Figures 23 and 24 show that the higher (he carbon content the higher the hardness of a given microstructure.e. 23. rnations or .Ieat Treatment of St. M.2% Mo... some of which are related to positions on a Jominy end-quench specimen. the technology which is concerned with estimating the depth and distribution of martensite in hardened components as a function of cooling rate and composition. '4 -- ~ - 40 :lO 20 10 Fig. and therefore CT diagrams more accurately than IT diagrams represent the conditions encountered in commercial practice."".and highcarbon steels alloyed with chromium._. Not all of the microstructures may be readily funned in all steels. . Therefore. The more-rapid cooling rates produce microstructures of higher hardness as indicated. Hardness is a readily measured property which in general is directly proportional to strength and inversely proportional to ductility . martensite formation may be accomplished by less-severe quenching with the advantages of lower residual surface tensile stresses. • ••. 24.

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