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HEAT TREATMENT
OF METALS
1996.2 p.40-42

Deep Cryogenic Treatm ent of Tool Steels: a Review

D. N. COLLINS

National Heat Treatment Centre, Ireland

As opposed to conventional sub-zero treatment to transform

retained austenite, deep cryogenic treatment at liquid-nitrogen
temperatures has been claimed to enhance the wear resistance
o f tool steels by additional hitherto ill-defined phenomena. In
summarising the current state o f knowledge, this review
clarifies the underlying mechanisms.

INTRODUCTION
From time to time over the last few decades, interest has been
shown in the effect of low temperatures during the heat treat
ment cycle on the performance of steels, particularly tool steels.
Published articles range from the merely promotional,
publicising various proprietary processes, to more detailed
metallurgical investigations.
To the casual reader, there may appear to be some confusion
between the conflicting claims of some of the literature. The
purpose of this review is to present a bibliography, to sum
marise the current state of knowledge in this area, and point to
the underlying mechanisms involved. In a future article, results
of work done on several grades of tool steel will be reported.
In order to avoid confusion, a distinction will be drawn between
"cold treatment", at temperatures down to about -80C
or thereabouts, and "deep cryogenic treatment", at about
liquid-nitrogen temperatures (-196C) since, as will be
discussed later, these two temperature ranges result in
different effects.
BASIC MICROSTRUCTURAL CONSIDERATIONS
The usual purpose of heat treating a tool steel is to achieve a
microstructure consisting of a suitable distribution of carbides
of desired type in a matrix of tempered martensite. In most
high-carbon and alloy tool steels, significant amounts of
austenite are retained after initial hardening, because the M f
may be substantially below room temperature. After comple
tion of the heat treatment cycle, the performance of the com
ponent will depend on the combined effect of each of the
microstructural constituents. In order to make any sense of the
effects of deep cryogenic treatment on properties, it is
necessary to view the process in the context of phenomena
relating to each of these main constituents.
Retained Austenite
Although the factors affecting retained austenite are numerous
and interrelated, the phenomena are reasonably well under
stood:
+ Alloying elements, especially carbon, in solution, strengthen
the austenite. More energy is thus required to effect the
shearing mechanism to produce martensite. A greater
degree of undercooling is thus required, lowering the Ms.
Strong carbide-formers may tie up carbon as undissolved
carbides, having little effect on Ms.
Increasing
austenitising
temperature
increases
austenite grain size, and also alloy and carbon dissolution,
further reducing Ms.
The transformation of austenite to martensite during cool
ing is not time-dependent, but related to the degree of cool
ing below the Ms.
Slow or interrupted cooling may allow stress relief and
possibly diffusion to occur, reducing the driving force for
40

martensite formation, again reducing Ms.

Some alloying elements promote austenite stabilisation,
whilst others inhibit it.
In plain-carbon and low-alloy steels, retained austenite
transforms to bainite, or is stabilised, at relatively low
tempering temperatures.
In high-alloy steels, austenite remains untransformed at
tempering temperatures up to about 450C or higher, at
which temperature it becomes "conditioned" by carbide
precipitation, transforming to martensite (of lower carbon
and alloy content) on cooling back to room temperature.

Martensite
A full treatment of the metallurgy of martensite is outside the
scope of this article. In relation to deep cryogenic treatment,
only a few points need to be noted:
Martensite is supersaturated with carbon which, during
tempering, precipitates out as carbides, the nature of which
depend on alloy content and tempering temperature.
The instability of martensite is associated with the strain
energy relating to its dislocation/twin structure, and with
interfacial energy associated with lath boundaries and
martensite/retained austenite boundaries (when the
austenite is present as thin inter-lath films).
Carbon atoms segregate to dislocation sites and interfaces,
and tend to cluster at such sites.
At very low temperatures, the activation energy for carbon
diffusion (and alloy diffusion) is too high to permit
formation of carbide precipitates as in the final stages of
tempering.
Tempered-martensite embrittlement may result from
cementite films precipitating from inter-lath austenite
during tempering.
Carbides
As with martensite, only a few points need to be noted here,
with specific reference to deep cryogenic treatment:
The type of carbide formed during tempering depends
mainly on alloy content and tempering temperature.
Some carbides in the final microstructure will be those that
remained undissolved during the austenitising treatment.
The size and distribution of carbides precipitated out from
the martensite (or retained austenite) during tempering will
be dependent on nucleation and growth phenomena,
influenced in turn by a number of factors, including prior
thermal history.
Nucleation and growth are time-dependent.
Secondary Hardening
The phenomenon of secondary hardening in some high-alloy
tool steels is caused by a combination of two main mecha
nisms:
Transformation of "conditioned" retained austenite to
martensite on cooling.
Precipitation of a fine distribution of alloy carbides
(especially the very hard, abrasion-resistant M2C and MC).
Other strengthening/hardening mechanisms include solution
hardening by the alloying elements, and strengthening due to
the prevention of grain coarsening by some of the alloy
carbides.
Heat Treatment o f Metals 1996.2

PROPERTY IMPROVEMENTS CLAIMED FOR

CRYOGENIC TREATMENT
In the various articles published over the years, a wide range of
property improvements have been said to be achieved. These
include:
Hardness. In many cases hardness increases of 1-3
Rockwell points have been claimed, although some authors
report very little increase in hardness.
Toughness. Claims for increases in toughness (usually
unnotched Charpy) are not widespread.
Wear resistance/more uniform wear pattern/better
ground surface finish. One of the most prevalent claims
is an increase in wear resistance (with or without a hard
ness increase). Some claims have also been made of
improved uniformity of wear pattern, and also improved
surface finish after grinding.
Dimensional stability. This was the original purpose of
cryogenic treatment, to stabilise dimensions by eliminating
the possibility of spontaneous transformation of retained
austenite subsequent to the final heat treatment.
Intergranular corrosion resistance. One author claimed
an improvement due to reduced grain-boundary diffusion.
Apparent Confusion
At first sight, there appears to be much confusion and conflict
between both the property improvements claimed, and also
the mechanisms postulated to cause the effects. An added
complication is that many of the authors do not specify the
exact details of the treatments undertaken. Some of the
apparent anomalies are:
Why do some authors imply that the chief improvement
is in hardness, due to the transformation of retained
austenite, whilst others claim little change in hardness?
Why, if the main mechanism is transformation of retained
austenite, have slow cooling rates and long treatment times
(24 hours or more) been specified?
Many treatments are performed in the region of -80C,
whilst some are at-196C.
AN EXPLANATION OF THE PHENOMENA INVOLVED IN
DEEP CRYOGENIC TREATMENT
In order to resolve the apparent anomalies, a research project
was undertaken at University College Dublin. Preliminary find
ings have been reported elsewhere, and a fuller report will
appear in a subsequent article. The results, based on both coldwork (D2) and high-speed (ASP 23) tool steels indicate that
there are two quite different phenomena or mechanisms
involved. These two phenomena have distinctly different
effects, and it is the confusion between them that has caused
the apparently conflicting results in some of the literature.
Mechanism 1: Transformation of Retained Austenite
This mechanism is well known, and is the result of cooling near
or below the effective Mf. The vast majority of the austenite in
the structure transforms to martensite with a resulting increase
in hardness. The elimination of the retained austenite also
stabilises the dimensions of the piece. This effect is largely
complete for most steels at temperatures of between -80C and
-110C, provided that the austenite has not been stabilised, by
long holding times at ambient temperatures or above, prior to
cryogenic treatment. The effect of this cryogenic treatment is:
an increase in hardness (the larger the amount of austenite
in the structure, the greater the hardness increase);
a reduction in toughness;
only a very modest, if any, improvement in wear resistance;
dimensional stability.
Mechanism 2: Low-temperature Conditioning of
Martensite.
Continued cooling of martensite, well below its formation
Heat Treatment o f Metals 1996.2

temperature (e.g. liquid-nitrogen temperatures for martensite

formed at or above room temperature), and holding at the low
temperature for sufficient time, promotes the formation of
large numbers of very fine carbide particles on tempering. The
result is an improvement in wear resistance and toughness, but
little or no increase in hardness. (There is in fact an initial reduc
tion in hardness, but this is largely recovered after a sufficiently
long holding time). The appearance of this fine carbide distribu
tion has been reported by a number of authors.
The exact mechanism of this "low-temperature conditioning"
of martensite is not yet fully understood. It is possible that the
continued cooling increases the strain energy and instability of
the martensite, and possibly also affects its dislocation
structure as the lattice contracts. Given sufficient time at the low
temperature, carbon atoms may migrate and cluster (albeit
slowly at these temperatures; hence the long holding times
necessary, e.g. 24 - 72 hours). On subsequent heating up to or
above room temperature, these sites act as nuclei for the
formation of the fine carbide particles observed in deepcryogenically-treated steels.
This mechanism has the most beneficial effect on work
pieces with least retained austenite (most martensite) in their
structure, indicating that the effect is on martensite, not on the
retained austenite. It also indicates that -196C 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 (holding time at the deep
cryogenic temperature) dependent; the lower the temperature
and the longer the holding time, the finer is the carbide distribu
tion and the greater the increase in wear resistance. The overall
effect of this deep cryogenic treatment mechanism is:
a much greater number of fine carbide particles in the
microstructure;
a different partition of alloying elements between matrix
and carbides, compared with conventionally-treated steels;
an improvement in wear resistance;
an increase in toughness: it is possible that temperedmartensite embrittlement 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
austenitising process is used, which is different from the
conventional optimum);
no secondary hardening occurs if tempered in the normal
secondary-hardening temperature range.
TOTAL HEAT TREATMENT CYCLE
Neither cold treatment nor deep cryogenic treatment should be
considered as an "add-on" to a conventional heat treatment
cycle, if optimum properties are to be expected. In particular,
careful selection of austenitising treatment is all-important:
If the objective is to maximise hardness, then a high
austenitising temperature should be selected, to maximise
carbon and alloy solution, accepting the increased per
centage of retained austenite, which is then transformed to
martensite by cold treatment. This can be followed by a
single low-temperature temper. Using this type of
treatment, it is quite feasible to achieve 65HRC from a D2
steel, for example (but at the loss of some toughness, it
should be noted).
If an increase in wear resistance is the desired objective,
then this can be achieved by using a lower-than-normal
austenitising temperature (to minimise the amount of
retained austenite) and then deep-cryogenically treating.
This results in a significant improvement in wear resistance,
(for example at a hardness of 58HRC in a D2 steel), and
toughness similar to or better than conventionally-treated
samples.
41

HEAT TREATMENT
OF METALS

There is thus a choice between hardness and wear

resistance:cryogenic/deep cryogenic treatment can give signifi
cant improvements in either of these properties, but not both at
the same time.

review

BIBLIOGRAPHY
Bayer H.E. Can I benefit from the use of low temperature treatment?
Steel Processing. Oct. 1953,502-508.
Nordquist W.N. Low-temperature treatment of metals. Tooling and
Production. July 1953, 72-100.
Morris V. Below zero chilling toughens metals, increases tool life.
Machine and Tool Blue Book. Jan. 1955, 124-134.
Andrews K.W. Empirical formulae for the calculation of some trans
formation temperatures. Journal o f the Iron & Steel Institute, 1965,
Vol.203, No. 7, 721-727.
Cryogenic quenching cuts warpage. Iron Age. May18, 1967,88-89.
Moore C. Development of the BOC Ellenite process (cold treatment of
metals with liquid nitrogen). Heat Treatment '73. The Metals Society,
1975, Book no. 163, 157-161.
Barron R.F. Effect of cryogenic treatment on lathe tool wear. Progress
in Refrigeration Science and Technology. 1973, Vol. 1,529-534.
Barron R.F. Yes, cryogenic treatment can save you money! Here's
why. Tappi Corrugated Containers Conference, Denver, Colorado,
1973,35-40.
Bowes R.G. The theory and practice of sub-zero treatment of metals.
HEAT TREATMENT OF METALS. 1974.1, Vol.1,29-32.
Barron R.F. Cryogenic treatment produces cost savings for slitter
knives. Tappi J. May 1974, Vol. 57, No. 5, 137-139.
Taylor J. Cold plunge gives tools an extra lease of life. Metalworking
Production. May 1978, 73-77.
Barron R.F. and M ulhem C. Cryogenic treatment of AISI-T8 and
C1045 steels. Advances in Cryogenic Engineering Materials. 1980,
Vol. 26, 171-179.
Miller P. Cryogenics: deep cold solves. Tooling and Production. 1980,
Vol 45, No. 11,82-86.
Popandopulo A.N. and Zhukova L.T. Transformations in high
speed steels during cold treatment. Metal Science and Heat Treatment.
1980, Vol.22, 708-710.
Barron R.F. Cryogenic treatment of metals to improve wear
resistance. Cryogenics. Aug. 1982, Vol.22, No.5,409-413.
Keen A.R. Cryogenic treatment to improve wear resistance of steel by
the "Cryotough" process. Metals Australasia. Aug. 1982, Vol. 14, No.7,
12-13,21.
Alexandru I., Picos C. and Ailincai G. Contributions on the study of
the increase of durability of the high-alloyed tool steels by thermal
treatments at cryogenic temperatures. Proceedings o f the 2nd
International Congress on Heat Treatment o f Materials (Florence,
Sept.20/24, 1982), 573-579.
Frey R. Cryogenic treatment improves properties of drills and P/M
parts. Industrial Heating. Sept 1983, Vol. 50, No.9,21-23.
Leonard L. Enhancing metals properties with supercold; fact or fancy.
Materials Engineering. 1985, Vol. 102, No. 2,29-32.
Sweeney T.P. Deep cryogenics: the great cold debate. Heat Treating.
Feb. 1986, Vol. 18, No.2,28-32.
Pillai R.M., Pai P.C. and Satyanarayana K. Deep cryogenic
treatment of metals. Tool and Alloy Steels. June 1986,205-208.
New dry refrigerent treatments improve characteristics and wear
resistance of metal parts. Industrial Heating. Mar. 1986, Vol. 53, No.3,
36-38.
Alexandru I., Coman G. and Bulancea V. The change of the
substructure elements and the redistribution of the alloying elements
by means of cryotreatments in alloy tool steels. Proceedings o f the 5th
International Congress on Heat Treatment o f Materials (Budapest, Oct.
20/24, 1986), Vol.2,901-908.
Gilmore V.E. Frozen tools. Popular Science. June 1987,64-67, 106-109.
Reasbeck R.B. Improved tool life by the Cryotough treatment.
Metallurgia. Apr. 1989, Vol. 56, No.4, 178-179.
Alexandru I., Ailincai G. and Baciu C. Influence of cryogenic
treatments on life of alloyed high-speed steels. Memoires et Etudes Sci.
Rev. Metall. 1990, Vol 87, No.6, 383-389.
Carlson E.A. Cold treating and cryogenic treatment of steel. ASM
Handbook. 1991, Vol. 4,203-206.
Paulin P. Mechanism and applicability of heat treating at cryogenic
temperatures. Industrial Heating. Aug. 1992, Vol. 59, No.8,24-27.
Albert M. Cutting tools in the deep freeze. Modern Machine Shop.
Jan. 1992,54-61.
Moore K. and Collins D.N. Cryogenic treatment of three heat-treated
tool steels. Key Engineering Materials. 1993, Vol. 86-87, 47-54.

AUTHOR'S ADDRESS
David Collins is with the National Heat Treatment Centre,
University College Dublin, Department of Mechanical
Engineering, Dublin 4, Ireland.
0
42

SURFACE MODIFICATION TECHNOLOGIES VIII

T.S. Sudarshan and M. Jeandin (Eds.), Book 617, The Institute o f
Materials, 1 Carlton House Terrace, London SW1Y 5DB. 1995. pp976.
ISBN 0-901716-69-3. 100 ($200 to non-EU purchasers).
This volume contains 103 papers presented at the Eighth International
Conference on Surface Modification Technologies held in Nice during
September 1994. Previous confcrcnccs have similarly had proceedings
published by the Institute of Materials. In this instance, the contents are
divided into the following main subject areas:
Wear,
Advanced Coatings,
Advanced Investigation
Advanced Processes,
Techniques,
Modelling,
Lasers,
Thermal Spraying,
Ion Beam and Electron
Biomedical Applications,
Beam Techniques,

Corrosion and Miscellaneous.

The range of subject matter covered by these ten headings is extremely
wide, with much of the research work reported directed at assessing in
detail the improvement in properties that can be obtained from the
application of individual surface modification techniques to specific
materials, both metallic and non-metallic. Other papers concentrate on
the problems faced by particular components that suffer wear and/or
corrosion, for example orthopaedic implants, and aim to establish
surface treatments for improving life and reducing costs.
Conventional heat treatments, as well-established and researched
processes, barely rate a mention in this volume. This is quite under
standable, however, since many of the materials being studied are not
suited to or do not respond to surface heat treatment techniques, or can
only be treated by niche processes, such as laser treatments, to
improve their surface characteristics. There are occasional papers of
direct heat treatment interest, (covering such diverse topics as the
surface hardening of copper alloy by laser boronising, electron beam
surface melting to increase hardness and wear resistance of aluminium
bronze, and the kinetics of gas nitriding of steel) but these are a distinct
minority.
The strength of surface engineering, as represented by this volume, lies
in the diversity of processes available and under development, the
ultimate aim being to obtain the best match between substrate, surface
condition and the working environment.

S3

C.G. Williams.

HEAT TREATMENT
OF METALS

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Heat Treatment o f Metals 1996.2