CRYOGENIC REATMENT OF TOOL STEELS Possible mechanisms are suggested for the wear resistance or hardness improvement obtained by conventional cold treatment and deep cryogenic treatment at liquid-nitrogen temperature. The austenitizing temperature plays a major role. by David N. Collins* National Heat Treatment Centre University College Dublin Ireland * Member of ASM International ADVANCED MATERIA ver the past few decades, interest hhas been shown in the effect of low-temperature treatment on the performance of steels, partic- ularly tool steels, Published arti- cles have ranged from the merely promotional, publicizing various proprietary processes, to more detailed metallurgical investigations. ‘The casual reader may be confused by the conflicting claims made in some of the literature. The purpose of this article is to summarize the current state of knowledge in this area, and to point to the underlying mechanisms involved. To avoid confusion, a dis- tinction will be made between “cold treatment,” at temperatures down to about -80°C, and "deep cryogenic treatment,” at about liquid-nitrogen temperature (-196°C), since, as will be discussed, these two temperature ranges produce different effects. Reported property gains In the various articles published over the years, a wide range of prop- cexty improvements have been claimed. for steels that were low-temperature treated. These include: * Hardness: In many cases, hard- ness increases of 1 to 3 points HRC have been aimed, although some au- thors report very little increase in steel hardness. * Toughness: Claims for increases in toughness (usually unnotched Charpy) have been made, but are not widespread. ‘* Wear resistance: One of the most | prevalent claims isan increase in wear resistance (with or without a hardness increase), Some claims also have been made for a more uniform wear pat- tem and an improved surface finish after grinding. SES 12/98 * Dimensional stability: This was the original purpose of cryogenic treat- ment — to stabilize part dimensions by climinating the possibility of spon- taneous transformation of retained austenite subsequent to the final heat treatment. * Intergranular corrosion resis- tance. One author has claimed an im- provement in intergranular corrosion resistance due to reduced grain- boundary diffusion. Why the apparent confusion? At first sight, there appears to be much confusion and conflict between the reported property improvements and the mechanisms postulated as being responsible for these effects. An added complication is that many au- thors do not provide the exact details of the low-temperature treatments that were used. Some of the apparent anomalies: * Why do some authors imply that the chief improvement is in hardness, due to the transformation of retained austenite, while others claim little change in hardness? * Why, if the main mechanism is transformation of retained austenite (not time-dependent), have slow cooling rates and long treatment times, (24hours or more) been specified? * Many treatments are performed ata temperature around -80°C, while others are performed at =196°C. Microstructure and properties The properties of an alloy, be ita tool steel or any other, are dependent on its microstructure. If we are to un- derstand how any factor affects prop erties, we must look at how this factor affects the microstructure of the alloy. ContinuedZero) hole ardness, HRC ott ee ceyogenie temperature, °C Fig. 1 — The effect of a prolonged holding time on the transformation of retain austenite in AISI D2 austenitized at 1075°C. Ifcryo- -genically treated immediately, almost all the Telained austenite will transform at about 80°C, caheres if held for along time at room temperature, a much lower eryogenic trent- ‘ment temperature is needed, ana even then not al of he austenite transforms, as evidenced by the lower hardness achieved. 200] € “ 7 0-00 180 Coyogenie temperature, C in| Fig. 2 — Effect of cryogenic treatment tem perature on the hardress of a D2 tool steel. There sa sharp increase in hariiness down to the My as reiained austenite transforms. Cooling below this temperature, however, ac- tally results in a slight decrease in hardness The data are for cryogenic treatment times of 38,120, 379, and 1200 minutes Effects explained by two quite different mechanisms. Ho4 ‘Throughout history, practice has nor- mally led understanding, but to effec- tively control and develop technology, a basic understanding is needed. For example, for centuries the effects of quenching and tempering on steel were known, but it was only after a basic metallurgical understanding was gained that these processes could be developed and refined. This is probably still the case with cryogenic treatment: practice has been leading the way, with understanding lagging behind. Fortunately, informa- tion is now available to help fill in this knowledge gap. Microstructural considerations The usual purpose of heat treating tool steel is to achieve a microstruc ‘ture consisting of a suitable distribu- tion of carbides of desired type ina matrix of tempered martensite. In ‘most high-carbon and alloy tool steels, significant amounts of austenite are retained after initial hardening, be- cause the Mr — the temperature at which transformation of austenite to martensite is completed during cooling — may be substantially below room temperature. After completion of the heat treatment cycle, the p. formance of the component will de- pend on the combined effect of each of the microstructural constituents. To make any sense of the effects of deep cryogenic treatment on the properties of the steel, itis necessary to view the process in the context of phenomena relating to each of these main mi- crostructural constituents. Retained austenite: Although the factors affecting retained austenite are numerous and interrelated, the phe- nomena involved are reasonably well understood: * Alloying elements, especially carbon, in solution, strengthen the austenite. More energy is thus re- quired to effect the shearing mecha- nism to produce martensite. A greater degree of undercooling is thus re- quired, lowering the M, — the tem- perature at which transformation of austenite to martensite starts during cooling, * Strong carbide-formers may tie up carbon as undissolved carbides, having litle effect on M,, « Increasing austenitizing temper- ature increases austenite grain size, and also alloying element and carbon dissolution, further reducing M, ‘The transformation of austenite | to martensite during cooling is not ADVANCE! time-dependent, but related to the de- gree of cooling below the M, ‘Slow or interrupted cooling may allow stress relief and possibly diffu- sion to occur, reducing the driving force for martensite formation, again reducing M,. This hold-time effect is illustrated in Fig. L * Some alloying elements promote austenite stabilization, while others in- hibit. * In plain-carbon and low-alloy steels, retained austenite transforms to bainite, or is stabilized, at relatively low tempering temperatures. + Inhigh-alloy steels, austenite re- mains untransformed at tempering temperatures up to about 450°C or higher, at which temperature it be- comes “conditioned” by carbide pre- Gpitation, subsequently transforming to martensite (of lower carbon and alloying element content) on cooling back to room temperature. Martensite: A full treatment of the metallurgy of martensite is outside the scope of this article. However, in rela- tion to deep cryogenic treatment, only a few points need to be noted: ‘+ Martensite is supersaturated with carbon, which, during tempering, pre cipitates out as carbides, the nature of which depend on alloying element content and tempering temperature. * The instability of martensite is sociated with the strain energy rela to its dislocation/twin structure, and ‘with interfacial energy associated with lath boundaries and martensite/re- tained austenite boundaries (when the austenite is present as thin inter-lath films). * Carbon atoms segregate to dislo- cation sites and interfaces, and tend to luster at such sites. + At very low temperatures, the ac- tivation energy for carbon diffusion (and alloying element diffusion) is too high to permit formation of carbide precipitates as in the final stages of tempering. + Tempered-martensite embrittle- ment may result from cementite films precipitating from inter-lath austenite during tempering. Carbides: As with martensite, only a few points need to be noted with re spect to deep cryogenic treatment: The type of carbide formed during tempering depends mainly on alloying element content and tem- pering temperature. * Some carbides in the final microstructure will be those that remained undissolved during the MATERIALS & PROCESSES 12/98austenitizing treatment of the steel. * The size and distribution of car- bides precipitated out from the martensite (or retained austenite) during tempering will be dependent on nucleation and growth phe- nomena, influenced in turn by a number of factors, including prior thermal history. * Nucleation and growth are time- dependent. Secondary hardening: The phe- nomenon of secondary hardening in some high-alloy tool steels is caused by a combination of two main micro- structural mechanisms: + Transformation of “conditioned” retained austenite to martensite on cooling. * Precipitation of afine distribution of alloy carbides (especially the very hard and abrasion-resistant MsC and MC carbides, where “M” is a metallic element) Other strengthening /hardening mechanisms that can occur in high” alloy tool steels include solution hard- ening by the alloying elements, and strengthening due to the prevention of grain coarsening by some of the alloy carbides. Explanation of the phenomena ‘To resolve the apparent anomalies, a research project was undertaken at University College Dublin. Some find- ings have been reported elsewhere (see selected references). Results based on studies of both cold-work and high-speed tool steels indicate that there are two quite different phe- nomena or mechanisms involved: transformation of retained austenite and low-temperature conditioning of martensite. These phenomena have distinctly different effects, and it is probably the confusion between them that has caused the apparently con- flicting results in some of the technical literature. ‘The cold-work steel was AISI D2 (UNS T30402). The high-speed steel was ASP 23, a powder metallurgy steel made by Erastecl Kloster AB of Sweden using the ASEA Stora process (ASP). It is equivalent to AISI M3, Class 2 (UNS T11323). ‘Transformation of austenite ‘The first mechanism is the transfor- mation of retained austenite. This mechanism is well known, and is the result of cooling near or below the ef- fective My. The vast majority of the austenite in the structure transforms tomartensite with a resulting increase in hardness. The elimination of the re- tained austenite also stabilizes the di- mensions of the workpiece. This effect is largely complete for most steels at temperatures between -80 and —130°C ig. 2), provided that the austenite has not been stabilized prior to cryogenic treatment by long holding times at ambient temperatures or above. ‘The effects of this treatment are: * An increase in hardness. (The Jarger the amount of austenite in the microstructure, the greater the hard- ness increase.) * Areduction in toughness. * Only a very modest, if any, im- provement in wear resistance. * Dimensional stability. + The absence of a secondary hard- ening peak on the tempering curve following cryogenic treatment (Fig. 3) Conditioning of martensite The second mechanism is the low- temperature conditioning of marten- site. Continued cooling of martensite to well below its formation tempera- ‘ture — such as, to liquid-nitrogen tem- Introducing the ASM Practical Learning Series™ Our first series: Heat Treating © Furnaces and Associated Equipment « Instrumentation and Controls, © Equipment Operation and Maintenance Sy ea Furnaces and Associated Equipment Contents: + Tnodcion to traces $ tastes af eat Weting including heat treating processes ad econ «Selig te ight umae for diterent peso parts {Bases ofunaes, nding eat soure, peo in, lmaspore temperature range, and mode of hea ransmission « Furnace ensvucton, ncting components, shel, and nulaton [o-Aiep instrumentation and Controls en Convenes: * pas of con instruments available o heat troaters and how they operate © Haw coil systems send commands to valves, switches, and on-off or Variable-conirol devices to establish and maintain tumace conditions «+ How temperature and umace atmospheres are controlled Primary it Order #270891 ‘Pack Replasoment Kit Orer #270982 Price: $124 ASH Member: $ 99 25-Pack Replacement Kit Order #270389 Price: $409_ ASH Member: $399 Equipment Operation : and Maintenance : Contents: ® Basie start-up and operating procedures for various furnace types ' Maintenance ofeach furvace type = Two basic methods of heating and their maintenance G Primary Kit Order WTO ice: $311 ASM Member: 249 ‘Pack Replacement Ki Order #270802 Price: $124 ASM Member:§ 99 | , * Types of furnaces, including batch vs. continuous Primary Kit Order #270291 Price: $311_ASW Member $249 ‘Pack Replacement Ki Order #270282 Price: $124_ ASH Member: § 99 25-Pack Replacement Kit Order #270299 Price: $499 ASM Member: $309 | 2 Pack placement Ki Order TOSS Price: $49, ASM Member: $300] For ull course descriptions, Materials t Pale Engineering institute ‘itip/iwvew.asmi-fatl.ory zee, arene Circle 29 on reader service card96 : i we i ‘oo. 200 300 on S00 0 ‘Tempering temperature, °C Fig. 3 — Cryogenic treatment and see ondary hardening. The tempering curves for cryogenicaly treated (196°C) and wostreated (20°C) D2 ste ilustrate the disappearance of the secondary hardening peak i the cryageni- cally treated samples, andthe convergence of the hardnesses of treated and untreated sani= ples at high tempering temperatures Sac moet na & a i Tr temper dara : Bo: g = 0 20 | ‘Time at 136°C, 4 Fig. 4 — Development of fine carbides after cryogenic treatment. Ths graph illustrates bot the time dependence (hours at -196°C) of the cryogenic treatment, an also the efecto tem peringteraprature. Te data indiretiy imply that the carbides actually form during tem pring, but ave ruceated atthe cryogenic treat ‘ment temperature. iB fe 200°C temper = ga 2 a 560°C temper m2 a2 | a AD Carbides, 10 particlesimam: Fig. 5 — Effect of fine carbide count on wear vate. Deep cryogenic treatment increases the number of fine carbides, which play a major role in improving wear resistance. H26 perature for martensite formed at or above room temperature — and holding at the low temperature for sufficient time promotes the forma- tion of large numbers of very fine car- bide particles on tempering (Fig. 4). The result is an improvement in wear resistance (Fig. 5) and toughness, but litle or no increase in harciness. (There is in fact an initial reduction in hard- ness, but thisis largely recovered after sufficiently long holding time.) The appearance of this fine carbide distri- bution has been reported by a number of authors. The exact mechanism of this “low- temperature conditioning” of marten- site is not yet fully understood. It is possible that the continued cooling in- creases the strain energy and insta- bility of the martensite, and possibly also affects its dislocation structure as the lattice contracts. Given sufficient time at the low temperature, carbon. and alloying element atoms may mi- grate and cluster (albeit slowly at these temperatures, which may explain the requirement for long, 24 to 72 hour holding. times). On subsequent heating, these sites act as nucle for the formation of the fine carbide particles, observed in deep cryogenically treated steels. It has also been reported that the composition (alloying element con- tent) of the carbides subsequently formed on tempering may also be in- fluenced by this treatment. This mechanism has the most ben- ficial effect on workpieces having the least retained austenite (most marten- site) in their microstructure, indicating that the effect is on the martensite, not on the retained austenite. It also indi- cates that -196°C is not a low enough ‘temperature to condition martensite formed at very low temperatures, as in the first stage of cold treatment. The effect is both temperature- and time- dependent (holding time at the deep cryogenic temperature) — the lower the temperature and the longer the holding time, the finer is the carbide distribution and the greater the in- crease in wear resistance. The effects of this deep cryogenic treatment mechanism are: * A much greater number of fine carbide particles in the microstructure. © A different partition of alloying elements between matrix and car- bides, compared with conventionally treated steels. * An improvement in wear resis- tance of the steel. © An increase in toughness. It is ey pec] Hardaess HRC a 1 350 i000 405000, 0 Asstenitzing temperature, °C Fig. 6 — Eifect of austeitizing tempera ture and eryogenic treatment on hardness. Peak hardness of noncryogenialy tented D2 20°C) i reached oe the austenilzing temperature is about 1030°C. Above this temperature, in- creasing amounts of retained austenite reduce fuariness, When cryogenic treatrent at 196°C is used to transform this retained austenite, higher harnesses can be obtained a higher austeitizing temperatures. possible that tempered martensite em- brittlement is eradicated by one or both of these mechanisms, by either eliminating the inter-lath retained austenite, or causing nucleation of fine carbides rather than cementite films. * Little or no increase in hardness (if the most beneficial austenitizing process is used, which is different from the conventional optimum process). * No secondary hardening occurs if the workpiece is tempered in the normal secondary-hardening tem- perature range. Key role of austenitizing Neither cold treatment nor deep cryogenic treatment should be con- sidered as an “add-on” to a conven- tional heat treatment cyde, if optimum properties are to be expected. In most of the metallurgical investigations to date, the greatest benefit has been de- rived when cryogenic treatment has been inserted between hardening (quenching) and tempering. Cryo- genic processing of fully heat treated workpieces, already multiple tem- pered at high temperature, is not as effective as treating immediately after hardening. This is hardly surprising, since at this stage there is little or no retained austenite, and the martensite will already be fully tempered, witha fairly stable distribution of alloy car- bides in place. Continued ADVANCED MATERIALS & PROCESSES 12/98,30) 40-0, | a8) Cryogenic temperature,“ Fig. 7 — Effect of austenitzing tempera- ture and cryogenic treatment on wear rate, In contrast to the effect on hardness (Fig. 6), im proved wear resistance (ower wear rate) is ob- tained cohen cryogenically treating samples of D2 that were austenitized at lower tempera tures. (More martesit in the as-querched i- ‘orostructure lends to more fine carbides in the final microstructure after cryogenic treating ‘and tempering.) Careful selection of the austenitizing treatment is all-important: «If the objective isto maximize hard- ness, elect a high austenitizing te perature to maximize carbon and loying elements in solution, accepting the increased percentage of retained austenite, which is then transformed to martensite by cold treatment. This can be followed by a single low-tem- perature temper. Using this type of {treatment itis quite feasible to achieve 65HRC from aD? steel (Fig. 6), for ex- ample (but atthe loss of some tough- ness, it should be noted). «Ifthe objective is to increase wear re- sistance, select a lower-than-normal austenitizing temperature to minimize the amount of retained austenite, and then deep cryogenically treat (Fig. 7). This results in a significant improve ment in wear resistance at the same hardiness level (for example, ata hard- ness of 88 HRC in a D2 steel), and toughness similar to or better than conventionally treated samples. There is thus a choice between hard- ness and wear resistance. Cold treat- ment deep cryogenic treatment can provide significant improvements in either of these properties, but not necessarily both at the same time. HIP For more information: Mr. Collins is di- rector, National Heat Treatment Centre, ‘Dept. of Mechanical Engineering, Univer- sity College Dublin, Engineering Building, ADVANCED MATERIALS & PROC MAI Bellield, Dublin 4, Republic of Ireland; tel 4353-1-7061745 or 7061760; fax: +353-1- 7061736; e-mail: david.collins@ucd.ie or heat treatment@ued ie. Selected references These papers deal with the metallur- gical effects of deep cryogenic treatment 6f tool stels, # "The Theory and Practice of Sub-Zero ‘Treatment of Metals,” by RG. Bowes: Heat Trentment Of Metals, Vol. 1, No. 1, 1974, p. 29-92. ‘ “Transformations in High-Speed Steels During Cold Treatment,” by AN, Popan- dopulo and L.T. Zhukova: Metal Science and Heat Treatment, Vol. 22, 1980, p. 708-710. * “Cryogenic Treatment of Metals to Im- prove Wear Resistance,” by RF. Barron: Cryogenics, Vol. 22, No. 5, August 1982, p. 409-413. + “Contributions on the Study of the In- crease of Durability of the Hligh-Alloyed Tool Steels by Thermal Treatments at Cryogenic Temperatures,” by _ I Alexandr, C, Picos, and G. Ailincai: Pro- ceectings ofthe 2nd International Congress on Heat Treatment of Materials (Florence, Naly, 20-24 Sept, 1982), Associazione Italiana di Metallurgia (AIM), Milan, Italy, 1983, p. 373-579. + “The Change of the Substructure Ele- ments and the Redistribution of the Al- loying Elements by Means of Cryotreat- ments in Alloy Tool Steels,” by 1 Alexandru, G. Coman, and V. Bulancea: Proceedings ofthe Sth International Congress ‘on Heat Treatment of Materials (Budapest, Hungary, 20-24 Oct. 1986), Vol. 2, Scien tific Society of Mechanical Engineers (GTE), Budapest, Hungary, 1987, p. 501-808. * “Influence of Cryogenic Treatments on Life of Alloyed High-Speed Steels,” by 1 Alexandru, G. Ailincai, and C. Baciu: Mé- moines et Etudes Scientfiques de la Reoue de Métallurge, Vol. 87, No. 6, 1990, p. 383-389. + “Cryogenic Treatment of Three Heat- Treated Tool Steels,” by KE, Moore and DN. Collins: Key Engineering Materials, Vol. 86-87, 1993, p. 47-54 + “Deep Cryogenic Treatment of a D2 Cold-Work Tool Steel,” by DN. Collins and J. Dormer: Heat Treatment of Metal, Vol. 24, No. 3, 1997, p. 71-74 = “Deep Cryogenic Treatment of High- Speed Steel and its Mechanism,” by Dong Yun, Lin Xiaoping, and Xiao Hongshen: Heat Treatment of Metals, Vol. 25, No. 3, 1998, p 55-59. ene” Very sofa Circle 313 arr SES 12/98 TOOL ROOM CHAMP The First Choice of Tool Rooms Everywhere. 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