CRYOGENIC

TREATMENT OF
TOOL STEELS

N a tio n a l H ea t Treatm ent C entre

U niversity C o lle g e D ublin
Ireland

ver the past few decades, interest

has 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 -80C, and "deep cryogenic
treatment," at about liquid-nitrogen
temperature (~196C), since, as will be
discussed, these two temperature
ranges produce different effects.

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Reported property gains

In the various articles published
over the years, a wide range of prop
erty improvements have been daimed
for steels that were low-temperature
treated. These include:
Hardness: In many cases, hard
ness increases of 1 to 3 points HRC
have been daimed, 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 daims is an increase in wear
resistance (with or without a hardness
increase). Some daims also have been
made for a more uniform wear pat
tern and an improved surface finish
after grinding.

Possible mechanisms a re
suggested fo r the w e a r
resistance o r hardness
im provem ent o b tain ed b y
conventional cold
treatm ent a n d deep
cryogenic treatm ent a t
liquid-nitrogen tem perature.
The austenitizing
tem perature plays
a m a jo r role.
by David N. Collins*

ADVANCED MATERIALS & PROCESSES 1 2 / 9 8

Dimensional stability: This was

the original purpose of cryogenic treat
ment to stabilize part dimensions
by eliminating the possibility 6f spon
taneous transformation of retained
austenite subsequent to the final heat
treatment.
Intergranular corrosion resis
tance. One author has daimed an im
provement in intergranular corrosion
resistance due to reduced grainboundary 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 tim e-dependent), have slow
cooling rates and long treatment times 1
(24 hours or more) been specified?
Many treatments are performed
at a temperature around -80C, while
others axe performed at -196C.
Microstructure and properties
The properties of an alloy, be it a
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

H 23

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.
Fig. 1 The effect o f a prolonged holding
time on the transformation of retained austenite
in AISID2 austenitized at 1075C. Ifcryogenically treated immediately, almost all the
retained austenite will transform at about
-80C, ivhereas if heldfor a long time at room
temperature, a much lower cryogenic treat
ment temperature is needed, and even then not
all of the austenite transforms, as evidenced by
the lower hardness achieved.

perature on the hardness o f a.D2 tool steel.

There is a sharp increase in hardness doivn to
the Mp as retained austenite transforms.
Cooling below this temperature, however, ac
tually 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 q u ite d iffe re n t

mechanisms.

H24

Microstractural 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 in a
matrix of tempered martensite. In
most high-carbon and alloy tool steels,
significant amounts of austenite are
retained after initial hardening, be
cause the Mf 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 per
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, it is 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 Ms the tem
perature at which transformation of
austenite to martensite starts during
cooling.
Strong carbide-formers may tie
up carbon as undissolved carbides,
having little effect on Ms.
Increasing austenitizing temper
ature increases austenite grain size,
and also alloying element and carbon
dissolution, further reducing Ms.
The transformation of austenite
to martensite during cooling is not

time-dependent, but related to the de

gree of cooling below the Ms.
Slow or interrupted cooling may
allow stress relief and possibly diffu
sion to occur, reducing the driving
force for martensite formation, again
reducing Ms. This hold-time effect is
illustrated in Fig. 1.
Some alloying elements promote
austenite stabilization, while others in
hibit it.
In plain-carbon and low-alloy
steels, retained austenite transforms
to bainite, or is stabilized, at relatively
low tempering temperatures.
In high-alloy steels, austenite re
mains untransformed at tempering
temperatures up to about 450C or
higher, at which temperature it be
comes "conditioned" by carbide pre
cipitation, 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 as
sociated with the strain energy relating
to its dislocation/twin structure, and
with interfadal 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
cluster 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 form ed
during tempering depends mainly on
alloying element content and tem
pering temperature.
Som e carbides in the final
m icrostructure will be those that
remained undissolved during the

ADVANCED MATERIALS & PROCESSES 1 2 /9 8

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 timedependent.
Secondary hardening: The phe
nomenon of secondary hardening in
some high-alloy tool steels is caused
by a combination of two main microstructural mechanisms:
Transformation of "conditioned"
retained austenite to martensite on
cooling.
Precipitation of a fine distribution
of alloy carbides (especially the very
hard and abrasion-resistant M2C and
MC carbides, where "M " is a metallic
element).
Other strengthening/hardening
mechanisms that can occur in highalloy 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.

fective Mf. The vast majority of the

austenite in the structure transforms
to martensite 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 -130C
(Fig. 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
larger the amount of austenite in the
microstructure, the greater the hard
ness increase.)
A reduction 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).

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 AISID2
(UNS T30402). The high-speed steel
was ASP 23, a powder metallurgy
steel made by Erasteel Kloster AB of
Sweden using the ASEA-Stora process
(ASP). It is equivalent to AISI M3,
Class 2 (UNS T11323).

Conditioning of martensite
The second mechanism is the lowtemperature conditioning of marten
site. Continued cooling of martensite
to well below its formation tempera
ture such as, to Kquid-nitrogen tem-

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

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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-

ondary hardening. The tempering curves for

cryogenically treated (~196C) and untreated
(20C) D2 steel illustrate the disappearance of
the secondary hardening peak in the cryogeni
cally treated samples, and the convergence o f
the hardnesses o f treated and untreated sam
ples at high tempering temperatures.

Fig. 4 Development o f fine carbides after

cryogenic treatment. This graph illustrates both
the time-dependence (hours at -196C) of the
cryogenic treatment, and also the effect of tem
pering temperature. The data indirectly imply
that the carbides actually form during tem
pering, but are nucleated at the cryogenic treat
ment temperature.

Fig. 5 Effect of fine carbide count on wear

rate. Deep cryogenic treatment increases the
number o f fine carbides, which play a major
role in improving wear resistance.

H 26

resistance (Fig. 5) and toughness, but

little or no increase in hardness. (There
is in fact an initial reduction in hard
ness, but this is largely recovered after
a 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 "lowtemperature 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 nuclei 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
eficial 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 -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 timedependent (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

Fig. 6 Effect o f austenitizing tempera

ture and cryogenic treatment on hardness. Peak
hardness ofnoncryogenically treated D2 (20C)
is reached when the austenitizing temperature
is'about 1030C. Above this temperature, in
creasing amounts of retained austenite reduce
hardness. When cryogenic treatment at -196C
is used to transform this retained austenite,
higher hardnesses can be obtained at higher
austenitizing 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, with a
fairly stable distribution of alloy car
bides in place.
Continued

ADVANCED AAATERIALS & PROCESSES 1 2 / 9 8

Belfield, Dublin 4, Republic of Ireland; tel:

+353-1-7061745 or 7061760; fax: +353-17061736; e-mail: david.collins@ucd.ie or
heat.treatment@ucd.ie.

Fig. 7 Effect o f austenitizing tempera

ture and cryogenic treatment on wear rate. In
contrast to the effect on hardness (Fig. 6), im
proved wear resistance (lower wear rate) is ob
tained when cryogenically treating samples of
D2 that were austenitized at lower tempera
tures. (More martensite in the as-quenched mi
crostructure leads to more fine carbides in the
final microstructure after cryogenically treating
and tempering:)

Careful selection of the austenitizing

treatment is all-important:
If the objective is to maximize hard
ness, select a high austenitizing tem
perature to maximize carbon and al
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-temperature temper. Using this type of
treatment, it is quite feasible to achieve
65 HRC from a D2 steel (Fig. 6), for ex
ample (but at the loss of some tough
ness, it should be noted).
If the 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
hardness level (for example, at a hard
ness of 58 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. HTP

Selected references
These papers deal with the metallur
gical effects of deep cryogenic treatment
of tool steels.
"The Theory and Practice of Sub-Zero
Treatment of Metals," by R.G. Bowes: Heat
Treatment Of Metals, Vol. 1, No. 1,1974, p.
29-32.
"Transformations in High-Speed Steels
During Cold Treatment," by A.N. Popandopulo 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 R.F. Barron:
Cryogenics, Vol. 22, No. 5, August 1982, p.
409-113.
"Contributions on the Study of the In
crease of Durability of the High-Alloyed
Tool Steels by Thermal Treatments at
Cryogenic Temperatures," by I.
Alexandra, C. Picos, and G. Ailincai: Pro
ceedings o f the 2nd International Congress on
Heat Treatment of Materials (Florence, Italy,
20-^24 Sept. 1982), Associazione Italiana di
Metallurgia (AIM), Milan, Italy, 1983, p.
573-579.
"The Change of the Substructure Ele
ments and the Redistribution of the Al-

For more information: Mr. Collins is di

rector, National Heat Treatment Centre,
Dept, of Mechanical Engineering, Univer
sity College Dublin, Engineering Building,

ADVANCED MATERIALS & PROCESSES 1 2 / 9 8

loying Elements by Means of Cryotreatments in Alloy Tool Steels," by I.

Alexandru, G. Coman, and V. Bulancea:
Proceedings o f the 5th International Congress
on Heat Treatment o f Materials (Budapest,
Hungary, 20-24 Oct. 1986), Vol. 2, Scien
tific Society of Mechanical Engineers
(GTE), Budapest, Hungary, 1987, p.
901-908.
"Influence of Cryogenic Treatments on
Life of Alloyed High-Speed Steels," by I.
Alexandru, G. Ailincai, and C. Badu: M
moires et Etudes Scientifiques de la Revue de
Mtallurgie, Vol. 87, No. 6,1990, p. 383-389.
"Cryogenic Treatment of Three HeatTreated Tool Steels," by K.E. Moore and
D.N. Collins: Key Engineering Materials, Vol.
86-87,1993, p. 47-54.
"Deep Cryogenic Treatment of a D2
Cold-Work Tool Steel," by D.N. Collins
and I. Dormer: Heat Treatment o f Metals,
Vol. 24, No. 3,1997, p. 71-74.
"Deep Cryogenic Treatment of HighSpeed Steel and its Mechanism," by Dong
Yun, Lin Xiaoping, and Xiao Hongshen:
Heat Treatment o f Metals, Vol. 25, No. 3,
1998, p 55-59.
How useful did you find the in formal ion
presented in this article?
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