HEATTREATMENT

OFMETALS
p.71-7
1997.3
4

forging/rollingdirection,and all surfaceswere fine-ground

to maximiseconsistencyof results.

DeepGryogenicTreatment
of a D2 Cold-vuorkTool Steel
D.N. COLLINS and J. DORMER
National Heat Treatment Centre, lreland
Deep cryogenic treatment at liquid-nitrogen temperatures
can enhance the wear resistanceof tool steels.This article
records some of the experimental investigations which
helped clarify the underlying mechanisms.

Heat Treatment
All hardening was carried out in a vacuum furnace,
temperaturesbeing measuredby a thermocoupleinserted
into a dummy pieceof similarsizeto the test pieces,as well
as by the furnacethermocouple.Controlwas basedon the
workpiecetem perature.
Ouenchingwas in all casesby 3bar nitrogen gas quench.
Cryogenictreatment down to -140"C was conductedin a
BOC Ellenifetype unit, at a controlled cooling rate (unless
specified otherwise, 2.5"Clmin). Cooling from -140 to
-196" C w as by i mmersi on i n l i qui d ni trogen. Unless
specifiedotherwise,warming up to ambient temperature
was in still air. All tempering was done in a forcedconvectionair-recirculating fu rnace.

Testing
All testingwas undertakenat ambienttemperature,afterthe
completionof the whole treatmentcycle.
INTRODUCTION
"C"
A previous articlel in HEAT TREATMENT OF METALS O Hardnesstestswere all standardRockwell ,10 readings
being
taken
for
each
test,
ensuring
that
thesewere
reviewedpublishedliteratureon deep cryogenictreatment
all
consistent
within
to
0.5
HRC.
The
average
of these 10
of tool steels,and pointed to two different processestaking
readings
was
used.
place:
O Toughness was measured by the standard Charpy
(1 ) the elim inat iono f re ta i n e da u s te n i te ,re s u l ti n gi n an
method,usingan Avery Universallmpacttesterand the
increasein hardness;
samples
describedearlier.Threereadingswere taken(in
(2) the process of "low-temperature conditioning" of
inconsistencyadditionalsampleswere tested),
cases
of
martensite,normally at liquid-nitrogentemperatures,
and
average
valuesused.
which initiates nucleation sites for subsequent
O
Abrasive
wear
resistance was measured, using a
precipitationof large numbers of very fine carbide
calibrated
Struers
Abrapol-2Micro Wear Tester,on the
pafticles,resultingin increasesin wear resistance.
7
x
10mm
face
of
the samples, with standard test
This article reports on a project undertakenat University
procedures. The abrasive was alumina, in a size
CollegeDublinon the effectof deep cryogenictreatmentof
distribution of 60/80 grit (40%1, 1201220(40%1,and
a D2 tool steelon its hardness,toughness,wear resistance
280/500
Q0%1.This was made into a slurry by mixing
and microstructure,
and presentsthe resultsof the study.
with butanediol, in the ratio of 75% aluminal2lo/o
butanedi ol .
EXPERIMENTAL METHOD AND PROPERTIES
O
Microstructures
were examinedby conventionaloptical
TESTED
metal l ography,usi ng a B uehl erOmni met l l au t om at ic
Samples
image analyserfor measuringthe distributionand sizes
All test pieceswere unnotchedCharpysamples,of dimenof carbideparticles,etc.Carbidesdefinedas "fine" were
sions 7 x 10 x 55 mm. All were preparedtransverseto the
those of lessthan 5pm.

bd

,F -7

64

62
I
o
o)
c
T

60

//
,

Gryosenicalli
/
treated (-1961'Cl//

58

56

54

\
o
\

Not /
cryogenically
treated

\
I

52
1000
1050
1100
oC
Austenitising
temperature,

Fig.l. Effect of austenitisingtemperatureon hardnessof D2 tool steel.

Samplescryogenicallytreated (-196'C)were single temperedat 200'C;
those not cryogenically treated were given two tempers at 200.C.
Source- reference2.
HeatTreatment
of Metals1997.3

Fig.2. Effect of austenitising temperature and cryogenic treatment on

hardness of D2 tool steel. Cryogenically-treatedsamples were singletemperedat 200'C;standardsamples were tempered twice at 200'C.
71

ToolSteel
Treatment
of a D2Cold-work
DeepCryogenic

<s 62

o
o

for

The effect of cryogenictemperature on hardnessis shown

in Fig.3.After cryogenictreatment,the maximum hardness
achieved for any given treatment occurs when all the
retainedaustenitehas beentransformedto martensite.This
normally happens within the temperature range -80 to
-110"C.Loweringthe temperaturefurtherdoes not resultin
further increasein hardness;in fact, there is normally a
slight reductionin hardness,due to the onset of the lowtemperatureconditioningof the martensite.
The effectof time at cryogenictemperatureis illustratedin
Fig 4. After an initial reductionin hardness,believedto be
changesin the martensite,there
due to the crystallographic
is a very slightincreasein hardnessafterincreasingholding
times. This is probably due to the hardeningeffect of the
increasingnumber of very fine carbideparticlesas time at
cryogenictem perature i ncreases.
The effect of tempering on hardness of cryogenicallytreatedsamplesis shown in Fig.5. One interesting,but not
surprising,effect is the absenceof secondaryhardening
after cryogenictreatment.

Toughness
The effect of cryogenic temperature on toughness is
illustrated in Fig. 6. With the transformation of retained
austeniteto martensite,largelycompleteat about -100'C,
there is a significantieductionin toughness,of the order of
40%of the Charpyvalue,comparedwith a similar sample
D2
tool
steel
after
on
hardness
of
temperature
hardened
and doubletemperedat 200'C.lt may be interestEffect
cryogenic
Fig.3.
of
austenitising at various temperatures. All cryogenically-treated ing to notethat there is alsoa reductionin toughness,but of
samples held for 30 minutes at the cryogenic temperature,then single
about 25yo,i f a si mi l arsampl ew ere hardenedand double
temperedat 200'C;the +20"Cdata pointsare after double-temperingat
at about 525oc,tothe same hardnesslevel3.
tempered
200"c.
After treatment at lower temperatures,the toughness
begins to improve. This is believed to be due to the
RESULTS
The results presented here are mainly from this microstructuralchangestaking placewithin the martensite
investigation,but a few are taken from previouswork itself,which are indicated later. lt will be noted that the
improvement in toughness is greatest for samples
usingthesameprocedures.
elsewhere2,
described
austenitisedat low temperatures, in which there was
Hardness
initially more martensite present (i.e. less retained
temperaturebn hardnessis austenite).
The effectof austenitising

austenitisshownin Figs.1 and 2. As expected,increasing

butat
increases,
ingtemperatures
at firstresultin hardness
amountsof retained
the increasing
highertemperatures
austenitein the structureresultin an overallhardness
After cryogenictreatment,the peakhardnessis
decrease.
temperature.
higherandoccursat a higheraustenitising

Abrasive Wear Resistance

For the various austenitisingtemperatures,the effect of
cryogenictemperature on wear rate is illustratedin Fig. 7,
and the effectof time at cryogenictemperatureis shown in
Fig.8.lt will be seenthat lower cryogenictemperaturesand

,Cryogenically
treated (-196'C)

o-(J

Soo

-l'

6
o
o)

Not
-Gryog(
treatel

400
200
300
oC
temperature,
Tempering

Fig. . Effect of holding time at cryogenic temperature (-196"C)on

hardnessof D2 tool steel.All samplestemperedonce at 200'C.
72

Fig.S. Effect of tempering temperature and cryogenic treatment on

hardness of D2 tool steel. Cryogenically-treatedsamples single
tempered, non-cryogenicaIly-treated samp Ies doubIe-tempered. Note
the absence of a secondary hardening peak for the cryogenicallytreatedsamples.Source- reference2.
Heat Treatmentof Metals 1997.3

D ,N .C o l l i n a
s n dJ . D o r m e r

26

5.2

zo

5.1
a

E s.o

24

6)

-)
6
o

F +.g

zz

20

4.8

18

4.7

E
16
1 t
t +

12
10

Fig.8.Effect of time at cryogenic temperature (-196"C)on wear rate of

D2 tool steelafter austenitisingat various temperatures.Treatmentand
testing details as in brt.

Fig.6. Effect of cryogenic temperature on toughness of D2 tool steel.

All samples held for 30 minutes at temperature;tempering details as
previous figures.

1070'c

- t t '

5.6

I
I

5.7

5.5
@
L

5.5
tr -,

L
1040.c
or -----_\

3.4

5.2

(D

?rr

970"c

I
I

II

3. 1

F s.s
=

G-- Joron
\
\ \
\\

v.v

c)

Notcryogenicallytreated
treatedat -100"C
I Cryogenically
treatedat -196"C
I Cryogenically
)

5.0

5.2

,,| o
5. 1

ot

5.0

oz

Hardness,
HRC

Fig.7.Effectof cryogenictemperatureon wear rate of D2 tool steelafter

austenitisingat various temperatures.Treatmentand testing details as
in brt.

Fig.9. Hardnessand wear rates of D2 tool steel after austenitising at

various temperatures,and cryogenicallytreating (the individual points
on each line). The lowest cryogenic temperaturein each casegave the
lowest wear rate.

increased time at cryogenic temperature improve wear

carbides. lt should be noted that all metallography was

resistance.lt is apparentthat the best wear resistancewas

undertaken
on samplesat ambienttemperature,
afterthe
obtainedfor lower austenitisingtemperatures,which is in
completionof the totalheattreatmentcycle,includingthe
sharp contrastto the effectof austenitisingtemperatureon
finaltemper,
normally
at 200"C.
hardness (Fig.2). lt is clear from this that, contrary to the
normal expectation,there is no direct relationshipbetween
hardness and wear resistance(Fig. 9). The reason is that
wear resistanceis greatly influenced by microstructure,
ratherthan solelyby hardness.
Cautionmust always be exercisedwhen interpretingdata
on wear since,unlike hardness,tensilestrengthetc.,wear
resistanceis not an absolutepropertythat can be given an
E
exact,unambiguous,numericalvalue.The per-formance
of
o
a paft in servicewill be greatlyinfluencedby the particular
e n vi ro nm entand wea r m e c h a n i s mp re v a i l i n gi n th e gi ven
circumstance.
Theseresultscan thereforeonly be taken as
31
i n d i ca t iv eand denot in gg e n e ra l tre n d sS. m a l ld i ffe re nces
in
O
the results of these tests could translate into Iarge
differencesin performancein practice.
C J J

0)

Microstructure
All cryogenic treatments at temperatures below about
-80"C resultedin negligibleamountsof retainedaustenitein
the microstructure,and no measurable amounts were
observed in any of the samples thus treated. The only
significantmicrostructuralvariablethat could be observed
by optical microscopy was the size and distribution of
Heat Treatmentof Metals 1997.3

+20

-30

-80
-130
Cryogenic
temperature,
"C

-180

Fig.l0 Effect of cryogenic temperature on carbide counts in D2 tool

steel, after austenitising at various temperatures. Tempering as
previously described.
73

DeepCryogenicTreatmentof a D2Cold-workToolSteel

20
30
Timeat cryogenic
temperature,
h

Fig.l1. Effect of holding time at -196'C on carbide counts in D2 tool

steel,after austenitisingat various temperatures.

5.2

I s,r
E

'u,o
6

* +.s
4.8
4.7

Fig.12.Carbide counts and wear rates for D2 tool steel,after various

austenitising temperatures and cryogenic treatments at -196'C (the
individual points on each line, correspondingto those in Fig. 11).

The effect of cryogenic temperature on carbide count

(carbidesfiner than 5pm) is shown in Fig. 10,and the effect
of time at cryogenictemperaturein Fig. 11.Thesignificant
effect of carbide count on wear resistanceis illustratedin
Fig. 12.This is in agreementwith other publishedworka-6.
ln
order to derive maximum benefit from deep cryogenic
treatment, holding times at cryogenic temperatureof at
least24 hoursare recommended.
DISCUSSION
From these results,it is clearly evident that there are two
distinctly different phenomena taking place during
cryogenictreatment.
(1) At temperatures down to about -100"C, retained
austenitein the as-quenchedmicrostructuretransforms
to martensite,resulting in an increasein hardness,a
reduction in toughness, but little effect on wear
resistance.
The greaterthe amount of retainedaustenite
in the as-quenched structure (i.e. the higher the
austenitisingtemperature),the greateris this effect.
(2) At much lower temperatures,down to liquid-nitrogen
temperatures(and below?),crystallographic
and microstructuralchangestake place in the martensiteformed
during the initialquench.Changesin martensitelattice
parameter and a high density of lattice defects have
74

D.N.Collins
andJ. Dormer
been reportedT.lt is here suggested that these defect
sites may act a nucleationsites for the precipitationof
the fine array of carbidesafterwarming up to or above
ambient temperature.The time-dependence,
and long
times over which these changes take place, can be
explainedby the very slow rate of diffusion at these very
low temperatures.
This second phenomenonwe have called "low-temperature conditioning" of martensite.lt is suggestedthat the
temperature must be lowered by a significant amount
below the original martensiteformation temperaturefor
these microstructuralchanges to be initiated.Martensite
formed at or above room temperature becomes "conditioned" at liquid nitrogen temperatures, but this
temperature is not low enough to condition martensite
formed from retainedausteniteat say 0"C during cold
treatment. Thus samples treated at high austenitising
temperatures,with more retainedaustenite(lessmartensite
after the initial quench) are less affected by the deep
cryogenictreatment, have less fine carbides,less recovery
of toughness, etc. Those samples treated at the lower
austenitisingtemperatures,with more martensite in the
initial as-quenchedmicrostructure,undergo more "conditioning" at the deep cryogenictemperature,and displaythe
resultsseen in this work.
CONCLUSION
In additionto the well-known effectof transforming retained
austeniteto maftensite,with the consequentincreasein
hardness, deep cryogenic treatment has an effect on
martensite.lt causescrystallographicand microstructural
changeswhich, on reheating,resultin the precipitationof a
finer distribution of carbides in the tempered microstructure,with consequentincreasesin both toughnessand
wear resistance.
Furtherwork is neededto identifythe exact mechanismof
the crystallographicchanges that take place in the
martensiteat the low temperature,and to isolatethesefrom
changestaki ng pl aceduri ng the subsequentw ar m ing- up
afterthe treatment.
ACKNOWLEDGEMENT
The authorswish to thank BOC Gasesfor their support of
this project.
REFERENCES
1. GollinsD. N. Deepcryogenic
treatment
of toolsteels:
a review.
HEATTREATMENT
OFMETALS.1996.2,Vol.23,40-42.
2. MooreK. E.and GollinsD. N. Cryogenictreatment
of threeheat
treatedtool steels.Key EngineeringMaterials.1993,Vol.86-87,
47-54.
3. GrennanE. D. Secondary
hardening
of high-alloy
tool steels.
Final-yearProject, Department of MechanicalEngineering,
UniversityCollegeDublin,1995(unpublished).
4. Alexandru 1.,Coman G. and BulanceaV. Thechangeof the
substructure
elementsand the redistribution
of the alloying
elementsby meansof cryotreatments
in alloy tool steels.
Proceedings
of the 5th lnternational
Congresson HeatTreatment
of Materials(Budapest,
Oct.20-241986),
Vo\.,2,901-908.
5. Alexandru1.,Baciu G. and Ailincai G. Contributions
on the
studyof theincrease
of durability
of thehigh-alloyed
toolsteelsby
thermaftreatments
atcryogenic
temperatures.
Memoires
etEtudes
Vol.87,No.6,383-389.
Sci.Rev.Metall.1990,
6. Barron R. F. Cryogenic
treatments
of metalsto improvewear
resistance.
Aug.1982,Vol.22,No.S,
Cryogenics.
409-413.
7. Popandopulo
A. N. and ZhukovaL.T.Transformations
in highspeedsteelsduring cold treatment.Metal Scienceand Heat
Treatment.
1980,VoL22,708-710.
AUTHORS'ADDRESS
The authors are with the NationalHeat TreatmentCentre,
University College Dublin, Department of Mechanical
E ngi neeri ng,
D ubl i n4,l rel and.
N
Heat Treatmentof Metals 1997.3