Acta metall, mater. Vol. 40, No. 7, pp. 1727-1738, 1992 0956-7151/92 $5.00 + 0.

00
Printed in Great Britain. All rights reserved Copyright © 1992 Pergamon Press Ltd

THE ROLE OF A L L O Y C O M P O S I T I O N IN
THE P R E C I P I T A T I O N B E H A V I O U R OF H I G H
SPEED STEELS

WANG RONGI't, H.-O. ANDRI~N 1, H. WISELL 2 and G. L. DUNLOpI':~

~Department of Physics, Chalmers University of Technology, S-412 96 G6teborg, and
2Kloster Speedsteel AB, S-810 60 S6derfors, Sweden

(Received 28 August 1991)

A ~ t r a c t - - T h e role of alloy composition in determining the microstructure and microchemistry of a series

of related high speed steels has been investigated by a combination of analytical electron microscopy and
atom-probe field ion microscopy. The four steels which were investigated (M2, ASP 23, ASP 30 and ASP
60) cover a large range of C, V and Co contents. Excepting the Co content, the composition of primary
MC and M6C carbides and as-hardened martensite was similar in all four alloys and the major effect of
increasing the content of C and V was to increase the volume fraction of MC primary carbides.
Precipitation of proeutectoid carbides (mainly MC and M2C) occurred during hardening of all four steels
and the extent of this was greatest in the highly alloyed ASP 60. Tempering at 560°C resulted in the
precipitation of extremely fine dispersions of MC and M2C secondary carbides with very mixed
compositions in all four steels. It was found that, as well as hindering the formation of autotempered M3C
in the as-hardened martensite, additions of Co refined the secondary carbide dispersion and delayed
overaging reactions. Overaging at 600°C resulted in the precipitation of MaC, M6C and M23C6 at the
expense of the fine MC and M2C secondary carbide dispersion.

R r s u m r ~ O n 6tudie le r61e de la composition de l'alliage dans la drtermination de la microstructure

et de la microchimie d'une srrie d'aciers rapides en combinant la microscopie 61ectronique analytique
et la microscopie ionique fi sonde atomique. Les quatre aciers qui sont 6tudirs (M2, ASP 23, ASP 30
et ASP 60) couvrent une large gamme de teneurs en carbone, en vanadium et en cobalt. A l'exception
de la teneur en cobalt, les compositions des carbures primaires MC et MrC et de la martensite durcie
brute &aient identiques dans les quatre alliages et le principal effet de l'augmentation de la teneur
en carbone et en vanadium 6tait d'augmenter la fraction volumique des carbures primaires MC. La
prrcipitation des carbures pro-eutectoi'des (principalement MC et M 2C) se produit pendant le durcissment
des quatre aciers et celle-ci se drveloppe particulirrement dans l'alliage fortement alli6 ASP 60. Un revenu
fi 560°C produit la prrcipitation de carbures secondaires MC et M2C trrs finement dispersrs avec des
compositions trrs diffrrentes dans les quatre aciers. On trouve que, tout en emp6chant la formation de
MaC autorevenu dans la martensite brute de durcissement, des additions de cobalt affinent la dispersion
des carbures secondaires et retardent les tractions de survieillissement. Un survieillissement fi 600°C
entraine la prrcipitation de M aC, M 6C et M:3 C aux drpens des carbures secondaires MC et M 2C finement
dispersrs.

Zusammenfassung--Bei einer Reihe von Hochleistungsst/ihlen wird die Rolle der Legierungszusammenset-
zung bei der Festlegung von Mikrostruktur und Mikrochemie mit analytischer Elektronenmikroskopie
und Feldionenmikroskopie untersucht. Die untersuchten St/ihle (M2, ASP 23, ASP 30, ASP 60) decken
einen weiten Bereich an C-, V-und Co-Konzentrationen ab. Abgesehen vom Co-Gehalt war die
Zusammensetzung der prim/iren MC- und MrC-Karbide in allen vier Legierungen nach Martensith/irtung
/ihnlich; der wesentliche Effekt zunehmenden C- und V-Gehaltes besteht darin, dab der Volumanteil
der prim/iren MC-Karbide ansteigt. Proeutektoide Karbide (fiberwiegend MC und MEC ) scheiden sich
w/ihrend der H~irtung in allen vier St/ihlen aus, am St~rksten im hochlegierten ASP 60. Tempern bei 560°C
fiihrt in allen vier St/ihlen zur Ausscheidung extrem feiner Dispersionen von sekund/iren MC- und
M2C-Karbiden mit sehr gemischten Zusammensetzungen. Es ergibt sich, dab Co-Zugaben die Dispersion
sekund/irer Karbide verfeinert und Oberalterungsreaktionen verz6gert, neben einer Behinderung der
Bildung von selbstgetemperten MaC-Karbiden im geh/irteten Martensit. l~beralterung bei 600°C ffihrt
zur Ausscheidung von MaC, MrC und M23C6 auf Kosten der feinen Dispersion sekund~irer MC- und
M 2C-Karbide.

1. INTRODUCTION
tPresent address: Department of Metal Physics, Beijing
University of Iron and Steel Technology, Beijing, P. R. High speed steels are high c a r b o n steels c o n t a i n i n g
China.
significant quantities of strong carbide forming
:~Present address: Department of Mining and Metallurgical
Engineering, University of Queensland, Queensland elements, such as Cr, Mo, W a n d V, which provide
4072, Australia. a high volume fraction of carbide phases [l~J,].
AM 40/7--S
1727
1728 WANG RONG et al.: PRECIPITATION BEHAVIOUR OF HIGH SPEED STEELS
Table 1. Composition of the experimental materials
Steel C Si Mn Cr Mo W Co V Fe
M2 wt% 0.90 0.31 0.25 4.2 5.2 6.2 0.31 1.85 80.8
at.% 4.3 0.63 0.26 4.6 3.1 1.9 0.30 2.1 82.8
ASP 23 wt% 1.30 0,62 0.28 4.0 4.8 6.3 0.41 3.1 79.0
at.% 6.1 1.24 0.29 4.3 2.8 1.9 0.39 3.4 79.6
ASP 30 wt% 1.26 0.60 0.30 4.0 4.9 6.1 8.0 3.0 71.6
at.% 5.9 1.21 0.31 4.3 2.9 1.9 7.7 3.3 72.4
ASP 60 wt% 2.26 0.41 0.30 4.2 7.0 6.7 10.3 6.4 62.4
at.% 10.4 0.81 0.30 4.5 4.0 2.0 9.7 6.9 61.6

Additions of Co are made to some alloys in order to
improve the hot hardness [5-6]. Because of the large
volume fraction of carbide phases and the way in
which these are distributed in the microstructure, the
steels have high hardness, good wear resistance and
reasonable toughness when heat treated correctly.
This combination of properties makes them highly
suitable for use in such applications as metal cutting
tools and metal forming dies. The particular proper-
ties which may be attained through heat treatment of
steels of this type are of course dependent upon
composition and the exact heat treatment conditions.
The present paper makes a step towards understand-
ing the complex set of relationships which operates by
discussing the effects of compositional variables upon
the detailed microstructure in a series of four related
high speed steels.
Despite the large number of high speed steels which
are available, the sequence of phase transformations
and precipitation reactions which occur in the differ-
ent alloys is remarkably similar. Depending upon
the detailed alloy composition, the coarse eutectic
carbides which form during solidification are M2C
(rich in Mo, W, Cr, Fe), MC (rich in V), MrC (rich
in Fe, Mo, W), or sometimes M 2 3 C 6 (rich in Cr, Fe,
Mo, W) [7-10]. During soft annealing, hotworking
and subsequent austenitization the metastable eutec-
tic carbide M 2 3 C 6 goes into solution [10] while the
eutectic M2C carbide generally transforms to MC and
M6C which, for the alloys in question, are usually
more stable [11, 12]. These coarse (micron size) pri-
mary carbides are primarily responsible for the wear
resistance of the material.
Because of their high content of alloying elements,
high speed steels generally have good hardenability.
They are normally hardened by step-quenching into
molten salt at 500°C and air cooling to room tem-
perature. The microstructure at this stage consists of
coarse primary carbides embedded in heavily twinned
plate martensite which is interspersed with retained
austenite (up to 30 vol.%). A small volume fraction
of "proeutectoid" carbides is also likely to be present
because of precipitation at temperatures in the range
1000-900°C during the hardening operation [13].
Proeutectoid carbide precipitation reduces the super-
saturation of the as-hardened martensite and has the
r A S P = A s e a S t o r a Process. T h e s e h i g h s p e e d steels a r e
m a n u f a c t u r e d b y K l o s t e r Speedsteel A B , S b d e r f o r s ,
Sweden.
effect of reducing the secondary hardness, which can
be achieved during tempering.
The retained austenite is eliminated by repeated
tempering (2-3 times) at 550-560°C and fine sec-
ondary carbides also precipitate during this oper-
ation. These secondary carbides strengthen the ferrite
matrix and thus make an important contribution to
the overall hardness, strength and wear resistance of
the alloys. The detailed nature of the secondary
carbide dispersions under conditions of peak hard-
ness has earlier been subject to much conjecture
(see for example Refs [3, 14-18]). However, work
during the last ten years using transmission electron
microscopy and atom-probe field ion microscopy has
unambiguously shown that in two high speed steels
(ASP 23 and 60) the relevant secondary carbide
dispersions consist of extremely fine MC and M2C
precipitates with very mixed compositions [19-22].
The results of more recent atom-probe studies of
secondary precipitates in other high speed steels
(AISI designation TI, M2, M7) are in good agree-
ment with these findings [23-25]. It has also been
found, that depending upon the detailed alloy com-
position, cementite (M3C) may precipitate in the
martensite during hardening or during the early
stages of tempering. However, this carbide rapidly
coarsens or dissolves during tempering [22].
In the present work, a systematic investigation has
been made of the precipitation behaviour which
occurs during heat treatment of four powder metal-
lurgical high speed steels. Three of these alloys (the
ASPt series of high speed steels) are normally pro-
duced by powder metallurgical means while the
fourth, M2, is the most widely used cast and wrought
high speed steel. As can be seen from Table 1, the
ASP high speed steels are considerably more highly
alloyed than M2. ASP 23 (which corresponds to AISI
type M3:2) has an increased content of V + C and
ASP 30 has a similar composition to ASP 23 with the
exception that it contains 8 wt% Co. Thus a detailed
comparison of the behaviour of ASP 23 and ASP 30
should provide an improved understanding of the
role of Co in high speed steels. ASP 60 is very highly
alloyed and contains further large additions of V and
C, a higher Mo content and a substantially higher Co
content.
For the present investigation, M2 was prepared by
the same powder metallurgical process as the ASP
alloys in order to allow a valid comparison between
the different materials. It should be added here that
 WANG RONG et al.: PRECIPITATION BEHAVIOUR OF HIGH SPEED STEELS
70
68
A
¢,.)
n.
66
.~- ...... 577-~-===
/-" . ". . . . .
......
~--.. \\
,.r
64
I,Ig
#'*t 6 2
ee Harden'ng Temperature
,-e.
60
_ _ _,,8o; c,.s.23,
........ 12 o c,,,.2,
500 520 540 560
TEMPERING TEMPERATURE
Fig. 1. Hardness of M2, ASP 23, ASP 30 and ASP 60 after
hardening and then tempering 3 x 1 h at different tempera-
tures.
production by powder metallurgy results in a more
uniform microstructure which, as well as having
advantages for mechanical properties [26], enables a
more accurate characterization by modern techniques
of microscopy [19-22]. A combination of analytical
transmission electron microscopy (TEM/STEM/
EDX) and atom-probe field ion microscopy was
used to obtain detailed microstructural and micro-
compositional information. The results are discussed
in terms of the role of composition in determining the
precipitation behaviour.
2. EXPERIMENTAL
The compositions of the high speed steels which
were investigated are given in Table 1. All four alloys
were prepared by the ASP powder metallurgical
process [26] and were made available as forged and
hot rolled 20ram diameter bar. Hardnesses of the
different alloys after hardening and then tempering at
different temperatures are shown in Fig. 1.
All specimens were austenitized rapidly (3 min) in
a salt bath at either 1220°C (M2) or 1180°C (ASP
alloys). These are the recommended austenitizing
temperatures for the respective alloys. Hardening
involved step quenching into molten salt at 550°C
for 10 min followed by air cooling through the Ms
temperature (~200°C) to room temperature. The
standard tempering treatment for obtaining optimum
service properties involves repeated (3 × 1 h) temper-
ing at 560°C with intermediate air cools. Specimens
from all four alloys were examined in the standard
hardened condition and also in the standard tem-
pered condition. Overaging at 600°C for times of 1 h
and 24 h was also investigated for M2, ASP 23 and
ASP 30.
Thin foils for transmission electron microscopy
were prepared by jet electropolishing 3 mm diameter
discs at room temperature in a solution of 10%
1729
perchloric acid, 15% glycerol and 75% ethanol with
a current of approximately 0.4 A. Extraction replicas
were obtained by etching in a solution of 2% nital for
15-60 s and then coating with a thin layer of carbon.
The replicas were stripped from the specimens by
., etching in 3% nital for 1-2 hours.
Examination as carried out in a JEOL 200 CX
Temscan instrument (TEM/STEM) fitted with a Link
....% , " ' , \ 1 860 system for energy dispersive X-ray spectroscopy
(EDX). Quantitative microanalyses were undertaken
'".'%.\
using the Link Systems RTS-2/FLS computer pro-
gram which compares recorded peak shapes with
"1 those from standard spectra of pure elemental stan-
. I dards and applies the thin foil approximation [27]
580 600 620
with corrections or absorption [28]. The energy scale
of the spectra was calibrated against a generated zero
(°c)
strobe peak and the CuK~ peak of a spectrum which
was taken up at regular intervals from a Cu standard
specimen. The kxs~ sensitivity factors valid for the
instrumental set-up used in the investigation were
checked experimentally [29]. Determination of the
mass absorption correction for the EDX results, was
carried out using the K : L Intensity Ratio Method
[30]. An examination of the reliability and accuracy
of this method has been published elsewhere [31].
Analyses were made at more than 15 different par-
ticles or positions within each phase, so that a
satisfactory low standard deviation was obtained for
each quoted measurement.
Tip-shaped specimens for atom-probe field ion
microscopy were prepared from small pins by first
producing a necked specimen profile by electro-
polishing in a 6 mm layer of 10% perchloric acid,
20% glycerol and 70% ethanol floating on a bath
of trichloroethylene at room temperature. Final
polishing was carried out in a bath of 2% perchloric
acid in 2-butoxy ethanol. Specimens were examined
in an atom-probe field ion microscope, the function
of which has been fully described elsewhere [32].
Neon gas was used for imaging, and analyses were
carried out in ultra-high vacuum (less than 10-Tpa)
at 92 K.
3. RESULTS
3. I. General microstructure of hardened material
After quenching into molten salt at 550°C and air
cooling, the microstructure of all four high speed steel
consists mainly of coarse (1 y m in size) MC and M6C
primary carbides embedded in heavily twinned plate
martensite (see Fig. 2). As shown previously [21],
the martensite plates are interspersed with films of
retained austenite which is crystallographically
related to the martensite by the Kurdjumov-Sachs
[33] orientation relationship.
3.2. Composition of primary carbides
Average substitutional element compositions of
MC and M6C primary carbides, as determined by
STEM/EDX microanalysis, are shown in Table 2. In
1730 WANG RONG et aL: PRECIPITATION BEHAVIOUR OF HIGH SPEED STEELS

probe but not by STEM/EDX, it was found as

Fig. 2. General microstructure of the high speed steels.
Primary carbides are embedded in heavily twinned plate
martensite. ASP 23, as quenched condition. Thin foil elec-
tron micrograph.
essence the compositions of these carbides were simi-
lar in all four alloys but some differences may be
noted. Both MC and MrC in the highly alloyed ASP
60 steel have a significantly higher Mo content than
in the other alloys while the W content of MrC in
ASP 60 is lower. It can also be noted that the V
content of MC in ASP 60 is lower than in the other
three steels.
The Fe content of MC in M2 is higher than in the
other more highly alloyed steels and this higher Fe
content is accompanied by somewhat lower Cr, Mo
and W contents. Comparison of ASP 23 with ASP 30,
where the only significant difference in alloy compo-
sition is the Co content, shows that the amount of
strong carbide forming elements in MC is somewhat
greater (and the Fe content is less) for ASP 30 which
contains 8 wt% Co in its total composition. This
effect does not occur for MrC. Instead, as can be seen
for ASP 30 and ASP 60, Co enters into solution in
this carbide and comparison of the compositions of
MrC in ASP 23 and ASP 30 shows that Co enters the
carbide at the expense of Fe. The Co contd.nt of MrC
in the Co-containing alloys is however significantly
less than that of the bulk alloy compositions.
3.3. Composition of martensite prior to tempering
The composition of the martensite matrix for all
alloys was determined by both atom-probe field ion
microscopy and STEM/EDX. Taking into account
the possibility of measuring C contents by atom-
previously [19] that both methods of analysis gave
very consistent results. Because of the possibility
of sampling significantly larger volumes by STEM/
EDX, the results for substitutional elements shown in
Table 3 are those which were obtained by this method
of analysis. These results have been adjusted to allow
for the amounts of C detected by atom-probe. It can
be seen from Table 3 that except for the Co and Fe
contents, the compositions of the respective marten-
sitic matrices were essentially the same. Thus, for
comparison of the tempering reaction which takes
place in the four alloys, they all had virtually the same
matrix compositions with the exception of their Co
contents.
3.4. Volume fraction of primary carbides
Knowledge of the substitutional element compo-
sitions of MC, M r C and the martensitic matrix in
relation to the corresponding bulk alloy compositions
enabled the weight fractions of these phases to be
determined by applying a mass balance. Volume
fractions were then calculated from the weight frac-
tions and the densities of carbides and matrix. The
results for all four alloys are shown in Table 4. The
accuracy of this method was assessed by comparing
the results obtained for ASP 60 with volume fraction
estimates obtained for this alloy by quantitative
metallography on scanning electron micrographs of
electropolished thin foil surfaces. In this latter case
the type of carbide for each individual particle was
determined by using its EDX spectrum as a finger-
print. As can be seen from Table 5, volume fractions
of primary carbides obtained by the mass balance
method were less than those obtained by quantitative
metallography by about 15% relative.
Examination of Table 4 shows that, consistent with
its lower alloying element and C content, there was
a much lower volume fraction of MC in M2 than in
the other steels, but the volume fraction of M6C was
somewhat higher in this alloy, than for the other
steels. The obvious reason for this is the significantly
lower V and C content in the bulk composition of
M2. As shown in Table 2, V is the major substitu-
tional element responsible for the formation of MC.
It can also be noted that MC requires much more
carbon per unit volume of carbide than does M6C.
Comparison of the volume fractions of primary
carbides for ASP 23 and ASP 30 shows that the

Table 2. Average STEM/EDX analyses of substitutional elements (at.%) in primary carbides. Indicated error limits are standard deviations
of the spread between individual measurements. Results in parenthesis are not statistically significant
Carbide Steel V Cr Co Mo W Si Fe
MC M2 67.7__.4.5 6.4+__ 1.1 -- 11.9-t- 1.3 6.6-+- 1.0 -- 7.4+ 1.6
MC ASP 23 66.7--I-3.3 7.0_+0.8 -- 12.8_+0.9 7.9_+0.7 -- 5.1 _ 1.1
MC ASP30 67.2+1.6 7.5_+0.4 (0.2_+0.1) 13.6_+0.4 8.1_+0.4 -- 3.5_.+0.4
MC ASP60 61.6_+2.1 7.7-+0.8 (0.2_+0.1) 19.0_+1.0 8.7_+0.7 -- 2.8-+0.4
MrC M2 5.4 ± 0.5 5.1 -+ 0.6 -- 20.8 -+ 1.3 16.0 _+ 1.0 (5.0 -+ 5.0) 47.7 -+ 1.0
M6C ASP 23 5.1 _+0.3 5.7_+0.3 -- 20.2_+ 1.1 16.5_+0.6 (1.2-+ 1.2) 51.3-+2.4
MrC ASP 30 4.8 _+0.2 5.5 _+ 0.3 5.7 -+ 0.3 20.0 __.0.3 16.3 _+ 0.4 (3.0 _+ 1.2) 44.6 -4- 0.9
MaC ASP 60 4.7__.0.3 5.7_+0.5 7.5_+0.4 23.1 _ + 0 . 5 14.0_+0.4 (4.4_+3.2) 40.7_+0.9
 W A N G R O N G et al.: PRECIPITATION BEHAVIOUR OF HIGH SPEED STEELS 1731

Table 3. Average STEM/EDX analyses (at.%) of martens±tic matrix prior to tempering.

The results have been adjusted in order to account for C and Si detected by atom-probe.
The indicated error limits are standard deviations of spread between individual measure-
ments. Results in parenthesis are not statistically significant
Steel M2 ASP 23 ASP 30 ASP 60
Sia 0.7±0.1 1.6±0.2 1.5±0.1 1.2±0.1
V 1.3±0.2 1.1±0.1 1.0±0.1 1.1±0.2
Cr 4.6±0.3 4.5±0.1 4.5±0.1 4.6±0.2
Mn (0.2±0.2) (0.2±0.2) (0.3±0.1) 0.4±0.2
Fe 86.0±0.7 86.4±0.8 78.6±0.8 75.1±0.8
Co (0.2±0.2) (0.2±0.2) 7.9±0.3 11.7±0.2
Mo 2.1±0.3 1.8±0.2 1.8±0.2 1.7±0.4
W 1.1±0.1 0.8±0.1 0.9±0.1 0.8±0.1
Ca 3.8±0.3 3.4±0.2 3.5±0.2 3.4±0.2
aFrom atom-probe analysis. The data for Si include a small contribution from N.

presence of Co in ASP 30 makes no significant
difference to the amount of primary carbide which
forms. In direct relation to the significantly higher C,
V and Mo content of ASP 60, it can be seen that the
primary carbide content of this steel is considerably
greater than for the other steels (approximately twice
that of ASP 23 and ASP 30). This increase is due to
the much greater amount of MC since, in fact, the
volume fraction of M6C in ASP 60 is the lowest of all
the alloys.
3.5. Precipitation of proeutectoid carbides
Examination of extraction replicas taken from
specimens in the as-hardened condition showed that
precipitation of proeutectoid carbides had taken
place during hardening of all four steels (Fig. 3). As
discussed in a separate paper [13], these precipitates
were predominantly MC and M2C and existed in a
variety of morphologies viz:
(i) lamellar or rod-like (MC and M2C);
(ii) fan shaped or plate-like (M2C);
(iii) fine cube shaped (MC);
(iv) small intergranular carbides (MC, M6C,
M23C6).
The amount of proeutectoid precipitation was
approximately the same for M2, ASP 23 and ASP 30
while considerably more had occurred in ASP 60. It
was noted that, while there was a considerable vari-
ation in the size (5-50 nm) and spacings of the fine
cube shaped proeutectoid MC precipitates in each
alloy, these dispersions were finest in the Co contain-
ing alloys, ASP 30 and ASP 60. As shown elsewhere
[13] the proeutectoid MC and M2C precipitates were
rich in V, Mo and Cr.
3. 6. Precipitation of cement±re in as-hardened material
Cementite was occasionally observed to be
precipitated at prior-austenite grain boundaries in as-
hardened material. This occurred most often in M2
and ASP 23. Previous work has shown that this type
of precipitation occurs during cooling from the step-
quenching temperature of 550°C [13].
Fine precipitation of M3C also occurred at the
internal twin boundaries of the plate martensite in
M2 and ASP 23 [22] but not in the Co containing
alloys ASP 30 and ASP 60 (Fig. 4). The M3C was
crystallographically related to the martensite lattice
on one side of the twin boundaries by the Bagary-
atskii orientation relationship [34]. This indicated
that precipitation had occurred after the austenite to
martensite transformation, i.e. some autotempering
had taken place in the alloys which did not contain
Co.
3. 7. Tempering reaction at 560°C
In all four alloys the standard three stage (3 × 1 h)
tempering treatment at 560°C results in the complete
transformation of all of the retained austenite to
martensite and the fine-scale precipitation of MC
and M2C. The nature of this precipitation reaction
in alloy ASP 60 has previously been described
in detail [21], as well as the crystallography of
the reaction in ASP 23 [22]. The present results
show that the precipitation reaction was essentially
the same in all four alloys. The fine secondary
carbides could be detected in thin foils after just
1 h at 560°C but they were coarser and more
readily observable after longer tempering times.
During tempering the fine autotempered M3C in
the martensite of M2 and ASP 23, coarsened
rapidly and possibly partially dissolved. Some
cementite may also have formed during the early
stages of tempering, only to coarsen or redissolve
as the tempering reaction proceeded. As shown
in Fig. 5, MC and M2C precipitated both on the
internal twin boundaries of the plate martensite
and in the matrix between the twin boundaries. As

Table 4. Volume fractions (%) of primary carbides in the four high Table 5. Comparison of the two methods which were used to
speed steels in the hardened condition. The volume fractions were evaluate volume fractions (%) of primary carbides in ASP 60 in the
determined by applying a mass balance hardened condition
Carbide M2 ASP 23 ASP 30 ASP 60 Carbide Mass balance Quantitative metallography
MC 1.4 4.8 4.9 14.1 MC 14.1 16.0
MrC 6.1 5.5 5.9 4.9 MrC 4.9 6.6
Total 7.5 10.3 10.8 19.0 Total 19.0 22.6
1732 WANG RONG et al.: PRECIPITATION BEHAVIOUR OF HIGH SPEED STEELS
Fig. 3. Precipitation of proeutectoid carbides during harden-
ing. Extraction replica.
discussed previously [22], the plate shaped MC pre-
cipitates obeyed the Baker-Nutting orientation re-
lationship [35] with the matrix while the rod-shaped
M2C precipitates were found to obey both the
Pitsch-Schrader relationship [36] and also the re-
lationship recently discovered by Wang and Dunlop
[22]. At the short tempering time of 1 h a slight
deviation from the Pitsch-Schrader relationship was
detected and this can be explained by remanent
tetragonality of the martensite at this early stage of
tempering [22].
Electron microscopy of thin foils suggested that
the secondary precipitation was finer in the Co-
containing alloys, ASP 30 and ASP 60, than in M2
and ASP 23. This was confirmed by comparative field
ion microscopy of ASP 23 and ASP 30 in the 3 × 1 h
at 560°C tempered condition (Fig. 6). Because of
variable magnification across the field ion images it
was difficult to accurately determine the precipitate
sizes but the combined evidence from dark field
electron microscopy and field ion microscopy would
suggest the approximate precipitate sizes given in
Table 6. MC platelets and M2C rods in both alloys
had thicknesses of 1-2 nm.
Secondary carbide precipitates were not satisfac-
torily extracted onto replicas from tempered speci-
mens and this prohibited their analysis by STEM/
EDX. However, individual precipitates from ASP 23
and ASP 30 were analysed in the atom-probe field ion
Fig. 4. Autotempered cementite precipitated at martensite
twin boundaries. ASP 23, as-hardened. Thin foil, dark field
electron micrograph.
Fig. 5. Secondary precipitation of MC and M2C in plate
martensite during tempering 3 x 1 h at 560°C. (a) Dark field
electron micrograph of MC carbide in alloy M2. (b) Dark
field electron micrograph of M2C carbide in ASP 23. Thin
foils.
microscope. Because of the extremely small size and
thickness of the precipitates it was not usually poss-
ible to avoid collecting atoms from the surrounding
matrix in the volumes which were analysed for each
precipitate. Unless the precipitates were clearly large
enough, all of the Fe and Co in these analyses were
therefore designated as having come from the matrix.
Results from the present atom-probe analyses of
ASP 23 and ASP 30 are given in Table 7 together with
previous data from ASP 60 [21]. The analyses of MC
in ASP 23 and ASP 60 were derived from one single
relatively large plate shaped precipitate in each steel,
and no atoms from the matrix interfered with these
analyses. All of the other precipitate compositions
given in Table 7 are averages from analyses of several
very small precipitates. The differences between the
MC composition quoted for ASP 23 and ASP 30, and
also ASP 60 [21], are quite large, but should not be
overly emphasised because only one MC precipitate
was analysed in each of ASP 23 and ASP 60 and the
results for ASP 30 are only considered to be very
approximate.
It is interesting to note the very mixed composition
of MC, and the low V and high Cr content of these
very small precipitates. The compositions for M2C in
both ASP 23 and ASP 30 are in reasonable agreement
and, taking into account the omission of Fe from the
present analyses, are also in good agreement with
previous analyses of M2C in ASP 60 [21]. Again, the
composition was found to be very mixed, with high
levels of Cr and Mo.
 WANG R O N G et al.: PRECIPITATION BEHAVIOUR OF HIGH SPEED STEELS 1733

Table 6. Approximate sizes of secondary precipitates in tempered

high speed steel showing the effect of Co in reducing the precipitate
size for ASP 30. Platelets and rods in both alloys were 1-2 nm thick
MC plate length M2C rod length
Steel (nm) (nm)
ASP 23 5 l0
ASP 30 3 5

but further precipitation of M 3 C , M 6 C a n d M23C 6

took place at twin boundaries, martensite plate
boundaries, prior-austenite grain boundaries and on
the surface of primary carbides (see Fig. 7). After 24 h
at 600°C it was apparent that the original MC and
M2C secondary carbides in all three alloys had coars-
ened but this had occurred to a lesser degree in the
Co-containing alloy ASP 30. The size of MC precipi-
tates was typically 10-30 nm × 4-5 nm (length x
thickness) in alloys M2 and ASP 23, whereas in ASP
30, typical dimensions were 8-15 n m × 3 nm.
The precipitation of other carbides at interfaces in
the microstructure became more prevalent after 24 h
at 600°C. M 3 C predominated within the martensite
plates at positions corresponding to the twin bound-
aries while M 6 C and M 2 3 C 6 occurred more frequently
at the other interfaces. The M 3 C precipitates tended
to be larger in M2 and ASP 23 than in the Co-
containing ASP 30 (Fig. 8) and it was apparent, from
the depletion of MC and M2C in the vicinity of M 3 C
precipitates (see Fig. 9), that the coarse M3C grew at
the expense of the fine MC and M2C secondary
carbides.

Fig. 6. Field ion m i c r o g r a p h s of s e c o n d a r y M2C c a r b i d e in
the 3 × I h at 560°C t e m p e r e d c o n d i t i o n . (a) A S P 23;
micrograph is approximately 160 nm across. (b) ASP 30;
micrograph is approximately 70 nm across.
3.8. Overaging at 600~C
Specimens of M2, ASP 23 and ASP 30 which had
been previously given the standard tempering treat-
ment of 3 × 1 h at 560°C, were further aged for times
of 1 h or 24 h at 600°C. Such treatments correspond
to overheating, which can occur during service and
which results in deteriorated properties.
After 1 h at 600°C the secondary MC and MzC
carbides did not show any significant increase in size
4. DISCUSSION
4. I. The role of alloy composition in determining the
composition and amount of globular primary carbides
The MC and M 6 C globular primary carbides in
thermomechanically treated high speed steels form
through decomposition of M2C eutectic carbides
[1 l, 12] and also through spheriodisation of MC and
M 6 C carbides which are already present in the as-
solidified microstructure.
Although there are large differences in the total
amounts of alloying elements and carbon in the high
speed steels which were investigated here, there are
also many compositional similarities between them.
All four alloys are strongly dependent upon the
propensity of Cr, Mo, W and V to form carbide
precipitates and their Si, Mn, Cr and W contents are
approximately the same. Reference to Table 1 shows

Table 7. Atom-probe analysis of small secondary precipitates after tempering 3 x 1 h at 560°C. Data from
ASP 60 are from Stiller et al. [19]. The iron content could only be determined for the MC precipitate in ASP
23 and for M2C in ASP 60. The error limit given is that due to counting statistics only
Precipitate type Steel Precipitate formula
MC ASP 23 (V0.19± o.o~Moo.15+ 0.07W0.12± 0.06Cr0.35+ o.loFeo.15± 0.07Si0.04+ o.o,)Co9 ± o2
MC ASP 30 (Vo.3± o.iMoo.2 ± o lWo.2± o.iCro.3± o.j)Co.8± o.3
MC ASP 60 (Vo.32± 0.07M00.39± 0o~Wo.07± 0.03Cr0.21± 0.06)C0.s6± o.17
MEC ASP 23 (Vo.i3± o.o2M00.26± o.03WoA1± o.o2Cro.46± 0.04Si0.04± 0.01)2Ci.o± o.I
M2C ASP 30 (Vo.09± 0.02M00.33± 0.03W0.12± o.02Cro.41± 0.03Si0.05± o.ol)2CLl± o.1
M2C ASP 60 (Vo.o4± o.olM00.25± 0.o2Wo.o7± o.olCro.40± 0.o3Feo.24± o.o2)2C0.86± 0.06
1734 WANG RONG et al.: PRECIPITATION BEHAVIOUR OF HIGH SPEED STEELS
Fig. 7. Precipitation of M3C , MrC, M23C6 at twin bound-
aries, martensite plate boundaries and prior-autstenite grain
boundaries, during overaging at 600°C. (a) Corresponds to
the condition after overaging for 1 h and (b) after 24 h. Note
that after longer overaging the size of the coarse precipitates
does not change very much but the amount increases
significantly. ASP 23, thin foils.
Fig. 8. Precipitation of cementite at twin boundaries after
overaging 24 h at 600°C in (a) the cobolt-free alloy, ASP 23
and (b) the cobalt containing alloy, ASP 30. Note that the
size distribution of cementite precipitates is much broader in
the cobalt-free alloy than that in the cobalt containing alloy.
Thin foil electron micrographs.
Fig. 9. Depletion of the fine secondary carbide dispersion of
MC around the coarse cementite precipitates formed during
overaging. (a) Bright field and (b) dark field of cementite
precipitates, and (c) dark field of secondary carbide MC.
ASP 23, overaged for 24h at 600°C. Thin foil electron
micrograph.
that there is a substantial increase (6 at.%) in the C
content of the alloys going down the table from M2
to ASP 60. There is also a substantial increase
(5 at.%) in V content. This, together with an approxi-
mately 1 at.% increase in Mo between M2 and ASP
60, provides an approximate 1:1 balance with the
increased C content.
The other important difference between the alloys
is that Co is added in substantial quantities to ASP
30 and ASP 60 in order to improve hot hardness. As
mentioned earlier, this addition of Co to the alloy
composition is the only significant difference between
ASP 23 and ASP 30.
It can be seen from Tables 2 and 3 that, with the
exception of their Co contents, the major phases in
the hardened condition (viz. MC, MrC and the
martensitic matrix) have essentially similar compo-
sitions in all of the alloys. Some detailed differences
in the compositions of primary carbides were noted
 WANG RONG et al.: PRECIPITATION BEHAVIOUR OF HIGH SPEED STEELS
in Section 3.2; in particular the higher Mo content of
MC and M6C in the highly alloyed ASP 60, the lower
W content of M6C and the lower V content of MC
in the same steel. It has been suggested [2] that
(W + Mo) in MC and M6Ctends to increase with the
proportion of Mo in the steel. As can be seen in
Table 3, there is a clear tendency for this to occur in
MC but (W + Mo) is approximately the same for
M6C in all of the ASP alloys which were austenitized
at the same temperature. Instead the important effect
in the case of M6C would appear to be that the
M o : W ratio in M6C increases with the M o : W ratio
for the steel as a whole.
The major effect of varying the proportions of C,
V and Mo between these alloys is to alter the volume
fractions of primary carbides. As shown in Table 4,
ASP 23 and ASP 30 contain more than 3 times the
amount of primary MC carbides than does M2, while
ASP 60 contains approximately 10 times this amount.
Because of the increased proportion of Mo and W
with respect to V in M2, this alloy has a somewhat
greater amount of M6C primary carbides than the
other alloys.
The net result of the 2.5 times increase in C content
and the doubling of the Mo + V content when going
from M2 to ASP 60 is to increase the total volume
fraction of primary carbides by a factor of approxi-
mately 2.5. This effect may have been enhanced
slightly by the fact that M2 was, as is usually the case,
austenitized at a temperature of 1220°C which is 40°C
higher than the austenitizing temperature employed
for the ASP steels.
4.2. Proeutectoid precipitation
Proeutectoid precipitation occurred during harden-
ing of all four steels and to a somewhat greater extent
in the highly alloyed ASP 60. It has been shown
elsewhere [13] that these precipitates, which are pre-
dominantly MC and M2C and which are rich in the
valuable carbide forming elements Mo, Cr and V,
form predominantly during cooling through the tem-
perature range 1000-900°C. Proeutectoid precipi-
tation has the deleterious effect of reducing the
attainable supersaturation of martensite with respect
to Mo, Cr, V and C. The secondary hardness, which
can be reached via the tempering reaction, is thus
reduced. In order to avoid the negative effects of
proeutectoid precipitation, cooling should be as rapid
as possible through the upper temperature range.
4.3. Autotempering during hardening
As discussed in Section 3.6, cementite, which is
crystallographically related to adjacent martensite,
may precipitate at prior-austenite grain boundaries
and twin boundaries during cooling below the M~
temperature. It has been pointed out by Honeycombe
and Davenport [37] that such cementite can provide
in situ nucleation sites for secondary carbides during
tempering and the secondary carbides which nucleate
on these sites tend to be coarser than those nucleated
1735
at crystal defects such as dislocations. It was also
found in the present investigation that these auto-
tempered M3C precipitates do not completely dis-
solve and transform to MC and M2C during the
standard 3 x 1 h, 560°C tempering treatment. Thus,
the negative effect of autotempering is twofold: it can
lead to non-uniform dispersions of MC and M2C
with a reduced strengthening effect and an increased
propensity to coarsen through Ostwald ripening and
it also acts to reduce the total volume fraction of
secondary MC and M2C precipitates by decreasing
the availability of carbon.
It is important to note that no M3C at all was
found in ASP 60, which contained nearly 12 at.% Co
in its martensitic matrix and no twin boundary M3C
was found in ASP 30, which contained 8 at.% Co in
its martensite. By way of comparison, significant
quantities of M3C were found in both M2 and ASP
23. It can thus be seen that Co plays an important
role in restricting the amount of autotempered
cementite which forms in the martensite during hard-
ening.
4.4. Secondary precipitation during tempering
Microanalysis by STEM/EDX and atom-probe
field ion microscopy showed that in all four alloys
the martensitic matrix prior to tempering had essen-
tially the same composition with the exception of the
7.9at.% Co present in ASP 30 and 11.7at.% Co
in ASP 60 (see Table 3). Slightly higher C, V,
Mo and W levels were recorded for the martensite
in M2 and, although these measurements are with-
in one standard deviation of the corresponding
contents for the other alloys, it is likely that the effect
may be a real one due to the higher austenitizing
temperature which was used for the M2 steel.
With the exception of the Co additions to ASP 30
and ASP 60, all four alloys have approximately
similar matrix compositions after hardening and
can therefore be expected to display the same type
of precipitation behaviour during tempering. Thus,
the relevant composition for the tempering reaction
is that of an alloy containing (at.%): 3.5C;
1 V; 4.5 Cr; 2 Mo; and 1 W; with or without additions
of Co.
The secondary hardening, which occurs during
tempering of high speed steels of the type investigated
here, is due to the very fine-scale precipitation of MC
and M2C secondary carbides. In an earlier investi-
gation it was found difficult to distinguish between
these two secondary carbides using transmission
electron microscopy because of the extensive streak-
ing and overlapping of precipitate reflections in
electron diffraction patterns [21]. Subsequently, more
detailed diffraction and crystallographic analysis has
however shown that many reflections from the two
precipitate types can in fact be separated [22]. This
has made possible the use of selective dark field
electron microscopy to separately image both MC
and MzC and show that both types of secondary
1736 WANG RONG et al.: PRECIPITATION BEHAVIOUR OF HIGH SPEED STEELS
carbide are present in roughly equal quantities in this
series of high speed steels.
It is clear from the atom-probe compositional
results in Table 7 that both MC and M2C have very
mixed compositions with respect to their substi-
tutional element contents and that all of the strong
carbide forming elements participate in their for-
mation. The carbide forming elements, which are
primarily responsible for the precipitation of M2C,
appear to be Mo and Cr. While V does not participate
very strongly in the formation of M2C, it is, as may
be expected, present to a much larger degree in MC.
However, Mo, W and Cr also all participate strongly
in this latter carbide. Similar results have also been
obtained from atom-probe studies of secondary pre-
cipitates in high speed steels of type T1, M2 and M7
[23, 24]. It seems likely that the mixed compositional
nature of these carbide precipitates is a strong con-
tributing factor in determining their fineness and
resistance to coarsening during tempering. Earlier
work by Seal and Honeycombe [38] has shown that
small additions of a second strong carbide forming
element substantially increases the secondary harden-
ing effect due to M2C precipitation in F e - M o - C
alloys. Similarly it was shown by Dunlop and Honey-
combe [39] that mixed MC type carbides precipitate
in finer dispersions in low alloy steels and coarsen less
rapidly than their equivalent unmixed carbides.
A reason for the surprisingly high content of Cr in
the secondary precipitates is no doubt its effect to
reduce the lattice parameter of both MC and M2C
[40]. Fe, which probably also is included in the
precipitates although its concentration could only be
determined in a few cases, also diminishes the lattice
parameter as does the measured sub-stoichiometry
with respect to carbon. The precipitates are expected
to be coherent with the matrix [22], so a lower lattice
parameter means a reduced mismatch and therefore
a reduced strain energy contribution to the activation
energy for precipitation. This decrease may well
be larger than the decrease in volume free energy
(driving force) which occurs when strong carbide
formers are replaced by Cr and Fe in the precipitates.
It can be noted that a similar effect occurs in stabil-
ised austenitic stainless steels, where initially sub-
stoichiometric, Cr-rich MC are precipitated. During
high temperature ageing, the Cr content goes down
and full stoichiometry is approached [41].
Another important factor in determining the fine-
ness of the secondary carbide precipitate dispersion is
the inclusion of Co and many high speed steel
compositions. A direct comparison between ASP 23
and ASP 30 (see Table 6), whose compositions only
differ with respect to Co content, makes it clear that
the inclusion of Co results in finer dispersions of MC
and M:C.
4.5. Overaging of the secondary carbide dispersion
Because it was found that M3C, M6C and M23C6all
precipitated after further aging for 1 h at 600°C and
that the fine MC and M2C dispersion was not
markedly changed by this treatment, it is apparent
that the alloys are still supersaturated with respect to
a number of carbide phases after the standard 3 x 1 h
560°C tempering treatment. This is consistent with
observations of continued precipitation when temper-
ing for 24 h at 560°C and also with atom-probe
measurements of high carbon contents in the marten-
site between the fine precipitates after Short temper-
ing times [20]. Precipitation of M3C , M6C and M23C6
continued when overaging for 24 h at 600°C and it
was found that the M3C, which formed within the
martensitic plates, developed at the expense of the
fine MC and M2C precipitate dispersion.
Cementite in these alloys is not simply Fe3C , but is
significantly alloyed with strong carbide forming
elements and, as such, its range of stability may well
be considerably extended. A typical substitutional
element analysis obtained for M3C in ASP 30 was
(wt%): 6 Mo; 15 Cr; 6 W; 2 V; 3.5 Co and 67 Fe [13].
It is worth noting that Co additions play a strong role
in reducing the effects of overaging, since they restrict
the growth of secondary carbides, and thus improve
hot hardness.
Karag6z and co-workers have recently studied
overaging at 600°C of high speed steels T1 and
M2 [42, 43]. They also found that the size of MC
precipitates was relatively constant during the first
few hours of aging, and that actually the density
of MC initially increased somewhat. By contrast
the density of M2C exhibited a constant decrease
during overaging. The composition of MC and
M2C, as determined by atom-probe, did not change
very much except that the W content, which initially
was rather low, increased during aging. After 2-5 h
of overaging the density of MC also started to
decrease, and the hardness of the alloys, which
initially was nearly constant, gradually decreased.
These findings are thus in general agreement with the
present results.
4.6. The role of cobalt in high speed steels
It is well known that Co additions improve the
secondary hardening response and, most impor-
tantly, they improve the hot hardness of high
speed steels [6]. The latter effect is generally con-
sidered to be related to an improved resistance to
overaging of the secondary carbide dispersion but it
has also been suggested that it may be due to the
effect of Co in increasing the elastic modulus of ferrite
[441.
In the preceding sections it was shown that the
inclusion of Co in high speed steel compositions:
(i) limits the formation of autotempered
cementite while cooling below the Ms tempera-
ture during hardening;
(ii) refines the dispersion of MC and M2C
secondary carbide precipitates which forms
during tempering; and
 WANG RONG et al.: PRECIPITATION BEHAVIOUR OF HIGH SPEED STEELS
(iii) reduces the rate of coarsening of the sec-
ondary carbide dispersion during overaging as
well as
(iv) limits the formation of other carbides (eg
M3C), which may consume the fine MC and
MzC secondary precipitates, during overaging.
It has been suggested that Co acts to increase the
activity of C and may also decrease the diffusivity of
C in ferrite [45]. Although this may be the case, it is
difficult to rationalize the current metallographic
observations in these terms since a simple increase in
carbon activity should not substantially change the
stability of M3C with respect to MC and M2C.
The higher density and smaller size of MC and
M2C precipitates found in the cobalt containing
alloys can be caused by both a higher rate of nucle-
ation and a lower rate of growth of these precipitates.
From the MC primary carbide compositions given
in Table 2 and results previously published for
secondary MC and M2C in ASP 60 [21] it would
appear that Co is virtually insoluble in both MC and
M2C, while it displays some solubility in other less
strongly bound carbides (see for example, the analysis
of M,C in Section 4.5 and M6C in Table 2). The lack
of solution of Co in both MC and M2C strongly
suggests that the presence of Co in ferrite should
increase the driving force for nucleation of these
compounds while its partial solution in the less
strongly bound carbides suggests that it may, rela-
tively speaking, discourage the formation of M3C.
A fundamental reason for the effects of cobalt on
the relative stability of the carbide phases may be its
magnetic properties. Nishizawa et al. [46] have shown
that additions of cobalt to ferrite strongly increase the
chemical potential of alloying elements due to mag-
netic interaction. As an example, in the ternary
system F e - C c ~ M o the solubility of Mo in ferrite at
560°C is calculated to decrease to one half as the
cobalt content is increased from 0 to 12% [46]. By
contrast, the chemical potential of iron is not strongly
affected by the presence of cobalt. This could explain
the effect of cobalt to enhance precipitation of MC
and M2C, rich in alloying elements, relative to M3C,
rich in iron.
Once nucleated the carbide precipitates will grow
by diffusion. The diffusivity of substitutional atoms in
ferrite at temperatures below the Curie temperature
is much lower than can be expected from a simple
extrapolation from the paramagnetic temperature
range (see e.g. [47]). Good low temperature diffusion
data exist for Fe [48] and Co [49]. For these elements
the difference between measured and extrapolated
diffusivity is about two orders of magnitude at 560°C,
and the diffusion length x/(Dt) during 1 h of both Fe
and Co is only 2 nm at 600°C and 0.7 nm at 560°C
[50]. Since the effect of adding 10% Co to the alloy
is to increase the Curie temperature by about 100°C
and thus to further decrease the diffusivity of substi-
tutional atoms in ferrite, a lower growth rate of
I737
carbide precipitates during tempering and overaging
can be expected.
5. CONCLUSIONS
1. With the exception of Co content, the major
phases (MC and M6C primary carbides and the
martensitic matrix) had similar compositions in the
hardened condition in all four high speed steels which
were investigated.
2. The main effect of increasing the carbon and
carbide-forming element content in these high speed
steels is to increase the volume fraction of coarse
primary carbides.
3. Proeutectoid precipitation of carbides (mainly
MC and M2C) occurs during hardening of all four
steels. The extent of proeutectoid precipitation is
greatest for the highly alloyed steel, ASP 60.
4. Autotempered M3C precipitates at martensite
twin boundaries and grain boundaries during harden-
ing of high speed steels which do not contain Co. This
reaction is hindered by additions of Co.
5. Because of the similar compositions of the
as-hardened martensite in the steels investigated the
tempering reactions are also very similar. Repeated
tempering at 560°C results in the transformation
of retained austenite to martensite and the very
fine-scale precipitation of MC and M2C secondary
carbides.
6. The secondary carbides have specific crystallo-
graphic orientation relationships with the matrix.
Both MC and M2C have very mixed compositions:
they both contain Mo, Cr, V, W and probably also
some Fe, and are generally sub-stoichiometric with
respect to carbon.
7. The secondary carbide dispersions, which are
formed during tempering, are refined by additions of
Co which also restrains overaging of the precipitate
dispersions.
8. During overaging at 600°C, M3C precipitates
at twin boundaries and M3C, M6C and M23C6 all
precipitate at martensite plate boundaries and prior-
austenite grain boundaries. These reactions occur at
the expense of the fine MC and M2C secondary
carbide dispersions.
Acknowledgements--Financial support from the Swedish
Board for Technical Development and the Swedish Natural
Science Research Council is acknowledged. The experimen-
tal materials were supplied by Kloster Speedsteel AB and
discussions with H. Nord6n, G. Wirmark and Professor
K. H. Kuo are gratefully acknowledged.
REFERENCES
1. H. J. Goldschmidt, J. Iron Steel Inst. 170, 189 (1952).
2. I. K. Kupalova, Zav. Lab. 49, 27 (1983).
3. T. Mukherjee, in Materials for Metal Cutting, No. 126,
p. 80. ISI Publ. (1970).
4. R. Riedl, S. Karag6z, H. Fischmeister and J. Jeglitsch,
Berg- u. Hiittenm. Mh. 129, 71 (1984).
5. K. Kuo, J. Iron Steel Inst. 174, 223 (1953).
1738 WANG RONG et al.: PRECIPITATION BEHAVIOUR OF HIGH SPEED STEELS
6. J. P. Hirth, E. J. Dulis and V. K. Chandhok, in
Strength of Metals and Alloys (ICSMA 6) (edited
by R. C. Gifkins), p. 185. Pergamon Press, Oxford
(1982).
7. M. R. Ghomaschchi and C. M. Sellars, Metals Sci. 18,
44 (1984).
8. E. Haberling and H. H. Weigand, T. Z. Prakt. Metall-
bearb. 70, 139 (1976).
9. H. Fredriksson and M. Nica, Scand. J. Metall. 8, 243
(1979).
10. F. Kayser and M. Cohen, Metal Prog. 61, 79 (1952).
11. H. Fredriksson, M. Hillert and M. Nica, Scand.
J. Metall. 8, 115 (1979).
12. R. Riedl, M. R. Gregg, S. Karag6z and H. Fisehmeister,
Sonderbginde prak. Metall. 14, 369 (1983).
13. Wang Rong, H. Wisell and G. L. Dunlop, to be
published.
14. C. H. White and R. W. K. Honeycombe, J. Iron Steel
Inst. 197, 21 (1961).
15. R. L6v~que and A. Condylis, M~m. scient. Revue
M~tall. 68, 87 (1971).
16. E. Horn, D. E. W. Techn. Ber. 13, 171 (1973).
17. B. Pacal, T. Podrabsky and P. Fremunt, Pract. Metal-
logr. 18, 574 (1981).
18. C. S. Wright and R. S. Irani, J. Mater. Sci. 19, 3389
(1984).
19. H.-O. Andr6n, Scripta metalL 15, 749 (1981).
20. L.-E. Svensson, P. R. Howell, H.-O. Andr6n, H.
Nord6n and G. L. Dunlop, in Quantitative Micro-
analysis with High Spatial Resolution, p. 256. Metals
Society Book 277, London (1981).
21. K. Stiller, L-E. Svensson, P. R. Howell, Wang Rong,
H.-O. Andr6n and G. L. Dunlop, Acta metall. 32, 1457
(1984).
22. Wang Rong and G. L. Dunlop, Acta metall. 32, 1591
(1984).
23. K. Stiller, S. Karag6z, H.-O. Andr6n and H. Fischmeis-
ter, J. Physique 48, C6-405 (1987).
24. H. F. Fischmeister, S. Karag6z and H.-O. Andr6n, Acta
metall. 36, 817 (1988).
25. H.-O. Andr6n, Proc. 1st Int. High Speed Steel
Conf. (edited by G. Hackl and B. Hribernik), p. 392.
Montanuniversitfit Leoben, Austria (1990).
26. P. Hellman, Metal Powder Rep. 32, (1977).
27. G. Cliffand G. W. Lorimer, J.Microsc. 103, 203 (1975).
28. J. I. Goldstein, in Introduction to Analytical Electron
Microscopy and Analysis (edited by J. J. Hren et aL), p.
83. Plenum, New York (1979).
29. G. Wirmark, T. Thorvaldsson and H. Nord6n, Electron
Microscopy and Analysis (edited by P. Doig), p. 71. Inst.
Phys Conf. SeE No. 68, Bristol (1983).
30. P. L. Morris, M. D. Ball and P. L. Statham, Electron
Microscopy and Analysis (edited by T. Mulvey), p. 413.
Inst. Phys. Conf. Set. No. 52, Bristol (1980).
31. Wang Rong, G. Wirmark and G. L. Dunlop, Proc.
Anal. Electron Microsc. Workshop, Bethlehem, p. 51.
San Francisco Press (1984).
32. H.-O. Andr6n and H. Nord6n, Scand. J. Metall. 8, 147
(1979).
33. G. Kurdjumov and G. Sachs. Z. Phys. 64, 325 (1930).
34. U. A. Bagaryatskii, Dokl. Akad. Nauk. S.S.S.R. 73,
1161 0950).
35. R. G. Baker and J. Nutting, Iron Steel Inst. Spec. Rep.
No. 64, p. 1 (1959).
36. W. Pitsch and A. Schrader, Arch. Eisenhiittenwes. 29,
715 (1958).
37. A.T. Davenport and R. W. K. Honeycombe, Metals
Sci. 9, 201 (1975).
38. A. K. Seal and R. W. K. Honeycombe, J. Iron Steel
Inst. 188, 343 (1958).
39. G. L. Dunlop and R. W. K. Honeycombe, Metals Sci.
12, 367 (1978).
40. K.W. Andrews and H. Hughes, J. Iron Steellnst. (1959)
p. 304.
41. H.-O. Andr6n, A. Henjered and H.Nord6n, J. Mater.
Sci. 15, 2365 (1980).
42. H.-O. Andr6n, S. Karag6z, Cai Guangjun, L. Lundin
and H, Fischmeister, Surf. Sci. 246, 246 (1991).
43. S. Karag6z, H. F. Fischmeister, H.-O. Andr6n and Cai
Guangjun, Metall. Trans. in press.
44. B. Lehtinen, Swedish Inst. Met. Res. Report Nr. 1859
(1984).
45. V. K. Chandhok, J. P. Hirth and E. J. Dulis, Trans.
MetalL Soc. A.I.M.E. 224, 858 (1962).
46. T. Nishizawa, M. Hasebe and M. Ko, Acta metall. 27,
817 (1979).
47. Smithells Metals Reference Book (edited by E. A.
Brandes), 6th edn, Chap 13. Butterworths, London
(1983).
48. G. Hettich, H. Mehrer and K. Maier, Scripta metall. 11,
795 (1977).
49. H. Mehrer, D. H6pfel and G. Hettich, Proc. DIMETA-
82 (edited by F. J. Kedves and D. L. Beke), p. 360.
Trans Tech Publications, Switzerland (1983).
50. J. Kucera, L. Kozak and H. Mehrer, Physica status
solidi (a) 81, 497 (1984).