Nero metnll. Vol. 32. No. 9. pp. 1457-1467, 1984 0001-6140’84 S3.00 + 0.

00
Printed in Great Bntain. All rights reserved Copyright ‘, 1984 Pcrgamon Press Ltd

HIGH RESOLUTION MICROANALYTICAL STUDY OF

PRECIPITATION IN A POWDER METALLURGICAL
HIGH SPEED STEEL
K. STILLER, L-E. SVENSSONf, P. R. HOWELL& WANG RONG, H-O. ANDRBN and
G, L. DUNLOP
Department of Physics, Chalmers University of Technofogy, 412 96 Gbteborg, Sweden

(Receiued 8 June 1983; in revisedfarm 23 January 1984)

Abrbact-The microstructure of a powder metallurgical high speed steel (ASP 60) has been investigated
by combined analytical electron microscopy and atom-probe field-ion microscopy. The compositions of
MC and M,C primary precipitates were determined. The tempering reaction at 560°C was studied in detail
and it was shown that extremely fine M,C precipitates dominated at optimum hardness (3 h). Some fine
MC precipitates were also present. The compositions of the secondary carbide precipitates were
determined by atom-probe analysis. Overageing at 700°C resulted in the transfo~ation of the fine
secondary carbide dispersion to coarse M,C and M& and a change in the matrix morphology from
martensitic plates to equiaxed recovered ferrite subgrains.

R&mn&Nous avons ttudii la microstructure dune poudre mitallurgique d’un acier rapide (ASP 60) en
combinant la microscopic electronique analytique et la microscopic a emission d’ions. Nous avons
determine les compositions MC et M,C des precipitis primaires. Nous avons hudii en ditaii k revenu
i 560X et nous avons month que des precipitis extr~mement fins de M,C dominent ion de Ia durete
optimale (3 h). Quelques precipitb fins de MC ttaient tgalement presents. Nous avons determine par
analyse avec la sonde atomique les compositions des precipitb de carbures secondaires. Un sur-
vieillissement $ 700°C conduisait P la transformation de la dispersion de fins carbures secondaires en M,C
et Mz3C6 grossiers et a un changement de la morphologie de la matrice de plaquettes martensitiques en
des sous-grains equiaxes de ferrite restauree.

Zusamm&asamg-Die Mikrostruktur ernes pulve~e~llur~~h~ H~hg~hwindi~eitss~hl~ (ASP 60)

wurde mit einer Kombination von anaiytischer Elektronenmikroskopie und der Atomprobe im Feld-
ionermikroskop untersucht. Die Zusammensetxung der prim&en Ausscheidungen MC und hi& wurde
bestimmt. Die Temperreaktion bei 56O’C wurde ausffihrlich untersucht; es zeigte sich. dag extrem feine
M,C-Ausscheidungen bei optimaler Hiirte (3 h) vorlagen. AuBerdem fanden sich einige MC-
Ausrheidungen. Die Zusammensetzung der sekundiiren Karbidausxheidungen wurden mit der Atom-
probe bestimmt. Uberaltem bei 7OO’C fiihrte dam, dag die feine Verteilung sekundiirer Karbide sich N
groben M6C und M&, umwandelte und die Mat~~o~holo~e sich von Ma~ensitplatten in gleichge-
richtete Subkiimer von erhohem Ferrit iinderte.

1. INTRODUCTION during heat treatment by a combination of analytical

The microstructure of high speed steels consists of
large primary carbide particles (diameter 1-2 pm)
dispersed in a tempered martensitic matrix containing
a much finer dispersion of secondary carbides which
precipitate during tempering [l]. In general these
steels contain large amounts of a variety of alloying
elements and it is important for further alloy devel-
opments to understand the function of these in the
microstructure. A first step towards this under-
standing can be gained by studying the distribution
of phases with the best available resolution and
determining their ‘detailed compositions. In the
present work this has been done at various stages
tPm~w~t~&ess: ESAB AR, Box 8004. 402 77 Giiteborg,
SPresent address: Department of Metallurgy. Pennsylvania
State University, University Park, PA 16802, U.S.A.
I457
electron microscopy (TEMISTEMIEDX) and atom-
probe field-ion microscopy. The ~mbination of these
two techniques enables the microanalysis of a wide
range of microstructural features with a number of
points of cross reference for verification of the accu-
racy of the results [2,3].
Previous studies of high speed steels ([l] and
references therein) have shown that MC and M&C
primary carbides form during solidification or soft
annealing because of the generally high contents of V,
W and MO. In addition, depending on the exact
composition of the steel, primary carbides of the
M&, hi& or M+Z types may also fotm. However,
these latter carbides usually dissolve during the hard-
ening treatment.
Because of the extremely fine nature of the second-
ary carbides at peak hardness very few clear images
of these precipitates have been obtained under opti-
mum tempering conditions. Thus, it has not usually
1458 STILLER er a/.: PRECIPITATION
been possible to determine the exact nature of the
phases which are responsible for peak secondary
hardness. However, depending upon the alloy com-
position, they are usually considered to be either MC
or M2C [ 1,4-lo]. Sometimes MC (cementite) is also
claimed to be present at peak hardness [I, 71.
The alloy chosen for the present investigation was
the highly alloyed powder metallurgical steel, ASP
60. The powder metallurgical technique used in its
production enables high concentrations of alloying
elements to be used while keeping the microstructure
free from large scale heterogeneities (e.g. banding,
segregation, slag inclusions) which are common to
cast and wrought high speed steels [ 1I]. As is the case
for most other high speed steels, the optimum combi-
nation of hardness, yield strength and toughness is
obtained by repeated tempering at 56OC with inter-
mediate air-toolings. For ASP 60 a three stage tem-
pering treatment is necessary to attain complete
transformation and tempering of the substantial
amounts of austenite, which are retained in the
microstructure after hardening. The tempering tem-
perature of 56O’C is slightly over the minimum which
is necessary to ensure complete transformation of the
retained austenite (121. Tempering at higher tem-
peratures or for longer times results in a substantial
decrease in secondary hardness. Because of the prac-
tical importance of the tempering treatment at 560°C
the present investigation has concentrated upon the
detailed microstructural developments which occur at
this temperature. The effect of overageing at 7OO’Cof
an initially optimum microstructure is also consid-
ered. Such a heat treatment simulates a severe over-
heating which could possibly occur during service of
alloys of this type. Some of the results which are
presented here have previously appeared in pre-
liminary reports [2, 131.
2. EXPERIMENTAL
The composition of the alloy under investigation is
shown in Table 1. Specimens for subsequent micro-
structural examination were austenitized in a salt
bath at 1180°C for 3 min and hardened by quenching
into a molten salt bath at 55OC and air cooling to
room temperature. The step cooling treatment elimi-
nates quench cracking. The standard tempering treat-
ment of three times 1 h at 56OC, which eliminates
retained austenite and provides optimum hardness,
was investigated together with shorter and longer
times at the same temperature. Other heat treatments
were carried out at 7OO’C in order to investigate the
tempering reaction at a temperature higher than that
for peak hardness and also to investigate the response
Table I. Composition of the experimental material
C Sl Mn
wt,.
0 2.26 0.41 0.30
at.O, 10.41 0.8 I 0.30
IN POWDER METALLURGICAL STEEL
of the peak hardness condition to a short period of
over-heating.
The technique used for the preparation of thin foils
for transmission electron microscopy has been de-
scribed previously [2]. Examination was carried out in
a JEOL 200 CX Temscan instrument (TEM;STEM)
fitted with a Link 860 system for energy dispersive
X-ray spectroscopy (EDX). Typical detector live-
times of 100-250 set were used for each microanalysis
by EDX. The energy scale of the spectra was cali-
brated against a generated zero strobe peak and the
CuKn peak of a spectrum which was taken up at
regular intervals from a Cu standard specimen. The
microanalyses were made quantitative by using the
Link Systems RTS-Z/FLS computer programme
which compares peak shapes with those from stan-
dard spectra of pure elemental standards and applies
the thin foil approximation [14] with corrections for
absorption.
The kxsl sensitivity factors valid for the electron
microscope and EDX system used in the investigation
were checked experimentally [3, 151. For most ele-
ments of interest it was found that the k,,, factors
predicted by theory (161 were satisfactory but it has
been found necessary to use experimentally deter-
mined kxs, factors at low X-ray photon energies. In
particular it should be mentioned that the kxs, factors
for W, and MoL lines were checked experimentally.
Although primary compositional information for W
and MO was obtained from the W, and MO, line
intensities, knowledge of the relative intensity values
W&V, and MoL/Mo, proved extremely useful in
subsequent quantification.
Correction of the EDX results for absorption of
X-rays in the specimen required determination of the
specimen thickness at the position where analysis was
carried out. Because of the high amount of strain
contrast within the martensitic matrix this was gener-
ally impossible to establish by normal experimental
procedures. Instead, the thickness of the matrix and
primary M,C and MC carbides were determined by
finding which estimated thickness gave the same
compositional results from the RTS-2IFLS computer
programme when the MO line intensities were deter-
mined using either the MO, or MO, lines. The general
accuracy of this method has been confirmed pre-
viously (171, and in the present case was checked by
studies of spade shaped field ion microscope speci-
mens which could be tilted 90’ in the microscope for
visual determination of local thickness. In situations
where the local W composition was relatively high
(e.g. -30 wt% in M6C) it was found that the peak
stripping routine in the computer programme did not
always satisfactorily separate the Sik peak from the
Cr MO W Co V Fe
4.2 7.0 6.7 10.3 6.4 62.4
4.5 4.0 2.0 9.7 6.9 61.6
 STILLER ef al.: PRECIPITATfOh! IN POWDER METALLURGICAL STEEL 1459

mary carbides (see next section) dispersed in heavily

Fig. 1, Twinned plate martensite after step quenching from
1180-C.
twinned plate martensite (see Fig. I), which may be
expected from the high carbon and alloying element
content of the alloy 1201. Dark field microscopy
showed that the martensite plates were generally
separated by films of retained austenite (Fig. 2), but
the observed volume fraction of retained austenite
was significantly less than the approximately 307;
known to be present in bulk material from X-ray
measurements. The lower observed volume fraction
in thin foil specimens was no doubt due to a reduc-
tion of mechanical constraints which are important
for the retention of austenite at low temperatures.
The martensite and the retained austenite obeyed the
Kurdjumow-Sachs [21] crystallographic orientation
relationship, i.e.
( Ill)., ii{ 1lotr
(110);//(111),

Whl peak. (These two lines are only separated by Prior austenite grain boundaries were often decorated
36eV in the EDX spectrum.) In these cases the two by MC carbides.
peaks were stripped manually, knowing from pre- The composition of the martensitic matrix (includ-
vious calibration work the true relative intensities of ing retained austenite). which provides the relevant
W, and W, lines. For all of the carbide precipitates starting composition for the tempering reaction, was
analyzed. the particles penetrated both top and bot- determined by both STEMI;EDX and atom-probe
tom surfaces of the thin foils and they were field-ion microscopy. Results from these analyses are
sufficiently large (- 1 pm) to avoid errors due to
beam spreading.
For all elements of interest, the experimental errors
in individual EDX analyses due to counting statistics
and the errors in she sensitivity factor k,,, were, as
has been shown previously 1181.in the order of 10:;
relative at the 990/, confidence level. Consideration of
other possible sources of error such as surface films
on the specimen and errors in estimation of specimen
thickness suggested that the most satisfactory expres-
sion of confidence in the results was to state the
standard deviation for a series of measurements made
at different positions in the same phase. In general a
total of 10 such measurements gave a satisfactory low
standard deviation. The validity of the results were
further cross checked with analyses made by atom-
probe field ion microscopy where the most important
source of error arises from counting statistics.
The method of specimen preparation for atom-
probe field ion microscopy has been described pre-
viously [2] as has the particular instrument which was
used in this investigation [ 191.All field ion specimens
were examined by transmission electron microscopy
prior to inserting in the atom-probe field ion micro-
scope in order to provide a cross check with the thin
foil electron microscopy work and also to determine
the suitability of the specimens for field ion micros-
COPY.

3. RESULTS

3.1. The microstructure of hardened material

Fig. 2. Retained austenite in as-formed martensite. (a)
After quenching into molten salt at 550°C and air bright field. note the edge of a primary precipitate at P.
cooling. the microstructure consisted of coarse pri- (b) dark field taken using an austenite reflection.
I460 STILLER er al.: PRECIPITATION
Table 2 STEM EDX and atom-probe anal-
yses (at.“,) of martensitic matrix prior to
tempermg
STEM atom-probe
Si - 1.2_+0.?
v 1.1 IO.2 0.8 f 0.2
Cr 4.6 2 0.2 4.2 * 0.4
Fe 76.2 + 0.8 75.9 2 0.P
Mn 114~0.2
co II.8 = Il.2 I I .4 f0.5
Md 1.7 r0.4 ?.I r0.3
w 0.8 IO.1 1.010.2
C 3.4 * 0.3
-.
Total 96.6”,, 100.0””
‘Inciudes Mn (peak overlap).
The STEM EDX results have been adjusted
to sum to 96 6”,, in order to account for
C detected b) atom-probe but not by
STEM EDX. The indicated error hmtts
for STEM EDX are standard deviations
of the spread between individual mea-
surements. The atom-probe results are
from IO.OXi atoms analyzed from 2
spectmens. Here the indicated error
limits are based upon the standard devi-
atlon of the \tatlstlcal counting error.
presented in Table 2 where it can be seen that good
agreement was obtained between the two techniques.
It can be noted that. because of the existence of the
primary carbides MC and M&. the concentration of
the strong carbide-forming elements (V. MO and W)
was considerably less in the martensite than given by
the bulk composition of the steel (Table 1). The high
carbon content of the martensite (3.4 at.::), as deter-
mined by atom-probe. indicates a high super-
saturation with respect to carbide phases prior to the
tempering reaction. Approximately 1.2at.?; Si was
detected in the martensite by atom-probe but the Si
content was too low for statistically significant mea-
surements by STEM,‘EDX. There exists a possibility
that the atom-probe measurements give a slight over-
estimate of the Si content because of selective field
evaporation between the applied high voltage pulses
[22]. This possible overestimate of the Si content is
also present in the atom-probe analyses of the tem-
pered matrix in Table 6. Another atomic species,
which was dificult to anafyse accurately in the atom-
probe is Mn. This is due to peak overlaps with Fe.
3.2. Primary carbides
The large carbides which formed during the origi-
nal solidification of the powder particles occupied
approximately 20 vokO, of the material. An example
of the dispersion of primary carbides is shown in
Fig. 3. Electron diffraction showed that these car-
bides were of two types: MC and M,C; and EDX
analysis gave characteristic spectra (see Fig. 4) which
could be used for rapid identification of the carbides.
Average compositions of the two types of primary
carbides, as determined by STEMjEDX analyses of
a number of precipitates are given in Table 3. Two
M,C and two MC primary carbides were obtained at
the tips of four different field-ion microscope speci-
IN POWDER METALLURGICAL STEEL
mens. Analyses of these precipitates by both atom-
probe and STEM/EDX techniques confirmed the
general validity of the thin foil results shown in
Table 3 [2,3]. The carbon contents of the carbides
could aLo be determined by atom-probe analysis and
the results from these few measurements are included
in Table 3 in order to give an indication of the
stoichiometry of the primary carbides. It can be noted
that the MC carbides were rich in V but also con-
tained a significant quantity of MO while the M,C
carbides contained large amounts of. in order of
importance, Fe, MO and W. As expected, the MC
carbides were found to be understoichiometrjc. No
significant differences were noted in the compositions
of the primary carbides between the as-quenched and
different tempered conditions.
3.3. Tempering at 560 C
The standard three-stage tempering treatment of
three times 1 h at 560 C with intermediate air cool-
ings, which gives optimum hardness for this alloy.
resulted in the transformation of all of the retained
austenite to plate martensite. The original mor-
phology of the highly twinned plate martensite was
retained and as shown in Fig. 5 a very fine, but
dense, dispersion of secondary carbides precipitated
both on the martensite plate boundaries and within
the plates. In some regions of the microstructure.
precipitation had apparently occurred on the bound-
aries of the internal twins within the martensite plates
[Fig. 5(b)] while in other regions precipitation was
independent of such features [Fig. 5(a)]. The very fine
precipitate sizes combined with the highly strained
nature of the martensite and the ferromagnetism of
the material made imaging of the secondary precip-
itates in the electron microscope exceedingly difficuft
and, moreover, chemical analysis of these precipitates
by STEM/EDX was impossible because of the large
amount of matrix material which was present in any
volume sampled by this method. Satisfactory extrac-
tion replicas which would enable analysis of the fine
Fig. 3. Primary carbides identified by EDX analysis and
observed in a thin foil of tempered ASP-60.
 STILLER et al.: PRECIPITATION IN POWDER METALLURGiCAL STEEL 1451

Energy i keVf

5 10 15
Energy 1keV)

Fig. 4. Characteristic BDX spectra obtained from primary carbides (a) MC; (b) M,C.

secondary carbides by STEM/EDX could not he and were generally highly streaked. As shown in
obtained. Reflections from the precipitated phase in Fig. 6 selected area diffraction suggested that the
selected area diffraction patterns had a low intensity secondary precipitates were either MC obeying the
Baker-Witting [23] crystallographic orientation re-
Table 3. Average STEM/EDX analyses of s&riruticurul elements
(at.%) in primary carbides lationship with the matrix or M2C being close to the
MC Pits&-Schrader [24] o~entat~on relationship.
M.5C
The high num~r density and very fine particle
si - 4.4 It 2.9
V 59.3 f 2.1 4.7 + 0.3 sizes of the secondary precipitates was confirmed by
Cr 7.6 f 1.8 5.6 i 0.6 field-ion microscopy. The most frequently observed
Fc 4.2 * 0.8 40.7 + 0.9
co 0.7 * 0.5 7.5 * 0.4 precipitate morphology was fine elongated platelets
MO 19.4 * 1.6 23.1 iO.5 of approximately 2 nm thickness [see Fig. 7(a)] but in
W 8.8 * 0.8 14.0 + 0.4 one particular area larger platelets (up to 20nm in
Stoichiomctry MCo,s+oos M 1*+01C
(from atom-probe anatysw) diameter) of the type shown in Fig. 7(b) were ob-
Indicated error limits are based upon standard deviations of the
served. Results of atom-probe analyses of these two
spread bctwccn individual measurements. types of precipitate are given in Table 4. The fine
1462 STILLER er al.: PRECIPITATION IN POWDER METALLURGICAL STEEL

times 1 h but the secondary precipitate particle sizes

were considerably smaller and diffraction from the
precipitate was very weak and diffuse. However. as
shown in Fig. 8 the fine precipitate dispersion was
readily imaged by field-ion microscopy. Atom-probe
analysis of several precipitates showed that they
corresponded to the same type of carbon-deficient
M2C carbide as mentioned previously. An average
composition for these precipitates is given in Table 5.
In general 60-70 ions were collected from each
precipitate which was analysed during field evapo-
ration through the thickness direction of the precip-
itates. Consideration of the effective diameter of the
probe aperture suggests that the precipitates were
approximately 1 nm in thickness.
The composition of the matrix excluding all precip-
itates after tempering for I h at 560 C was deter-
mined by atom-probe analysis. Three FIM specimens
were found to contain no precipitates whatsoever in

Fig. 5. Secondary carbide precipitation after 3 x 1 h temper

at 560X (precipitate dark field micrographs). (a) general
precipitation. (b) precipitation at martensite boundaries and
internal twin boundaries.

precipitates corresponded to either M>C (cementite)

or to carbon-deficient M?C with the approximate
formula (Cr, 4o Fe024 MoOzs Voo WO& COR6. The
possibility that the precipitate could be cementite is
discounted since the evidence from electron dif-
fraction is consistent with it being hexagonal M&
but not the orthorhombic M,C. It can be noted that
cementite precipitated in alloy steels is generally
considerably more rich in Fe and precipitates as
much coarser particles at temperatures in this range.
It has been shown previously that M,C can be
substoichiometric in carbon content and the com-
position may extend to MJ while retaining the
M2C hexagonal crystal structure [25]. As shown in
Table 4 the larger precipitates of Fig. 7(b) corre-
sponded to carbon deficient MC with the approxi-
mate formula (V,,z MoO.jgWO,, Cr,?,) CoB6.This ratio
of metal to carbon atoms is well within the stoichio-
metric range for MC-type carbides [26]. Fig. 6. Selected area diffraction from tempered martensite
In order to obtain further information on the (3 x 1 h, 56O’C) containing secondary carbide precipitates.
tempering sequence at 560-C some specimens were (a) Expected positions in 100 ferrite zone of reflections from
MC and M,C obeying Baker-Nutting and Pitsch-Schrader
also tempered for 1 h, 24 h and 100 h. After the short
orientation relationships respectively. (b) Selected area
term ageing treatment of I h the electron microscope diffraction pattern of similar orientation to (a) but ulted
observations were approximately the same as for 3 about (OZO),.
 STILLER er al.: PRECIPITATION IN POWDER METALLURGICAL STEEL 1463

Table 4. Awranr atom-probe analyses tai.“,,l of small secondary

ear&de\ after temtxrmi? 3 x I h at 560 C
_~~“_“_~~~~._.~_-~.-~~~_~_
._--__L- ---
MC M,C
St 0.4 2 0.’
V IT=4 3.1 2 0.5
Cr IT-
*_- 7 28.0= 1.8
Fe -_ 16.4 - I.0
co _- 1.3: 0.4
MO 71 f4 1?.4= I?
W 417 ‘L? t 0.6
C 46 I 5 28.7 + 1.8
Total atoms caunted 104 1409
Indicated error iimlta are hased upon standard deviations of the
statistical countmg Crr*T*.

for 3 times 1 h (see Figs 5 and 6). In general the

precipitate reilections in selected area diffraction
patterns were still too streaked to determine whether
they were due to either MC or M,C or to the presence
of both types of carbide. However. in certain areas
such as that shown in Fig. IO it could be clearly
shown that MC and M,C coexisted. In some regions
of specimens tempered for 100 h. coarse M-C, precip-
itates were observed. Atom-probe field-ion micros-
copy of a number of specimens which had been
tempered for 24 h (see Fig. 1If only resulted in the
detection of M&Z and the average from these analyses
is given in Table 5.

(b)
Fig. 7. Field-ion microscopy of secondary carbide precip-
itates (3 x I h. 560 C). (a) Fine platelets of M,C. (b) Larger
plate shaped MC.

their imaged volumes* and the average of analyses

from these specimens is shown in Table 6 together
with the average analysis of the matrix between
precipitates in 2 other specimens. The matrix analyses
on specimens containing secondary precipitates were
obtained while imaging the precipitates with a low
background pressure of Ne imaging gas. The probe
hole for microanalysis was kept over the matrix
between the fine secondary r~::;pnates by manipu-
lating the specimen while sim ,, I.~neousiy imaging and
pulse field evaporation.
Tempering for longer times (2-l and 100h) resulted
in a general coarsing of the secondary carbide precip-
itate dispersion. A typical bright field micrograph is
shown in Fig. 9. Electron microscopy of most areas
gave results which were very similar to those obtained

+Electron microscopy of these specimens showed that they

were martensitic. It is possible that they represent re-
gions of retained austenite which either transformed as
a result of the 1h tempering treatment or as a result of
specimen preparation and therefore precipitation had Fig 8. Field-ion microscope images of k&C secon dary
not yet commenced carbide precipitates after 1h. 560 C temper.
1464 STILLER er al.: PRECIPITATION IN POWDER METALLURGICAL STEEL

Table 5. Average chemical formulae for M,C secondary carbides at diKerent

times during temoerine at 560 C
._
Agetog
time Formula
Ih (Crl,1~,,,,!Fe,,,,I,,,hlo,l,.,,,?V,,f,,:W,,,,,,,,),C,,,,I,,,,,
3x Ih Kr,,;I,,, c,lllFe,,?,,,,,,Mo,?~ Tu,,~V,~,luc,,Wo.,r,,~,)~C~,“~~~~
24 h (Cr,,,g-oo,Fe,,,,,:Moo,i,uo?V,,,,,b,W,,x~a.a?):C,,,,o,o
Indicated error limits are based upon standard deviations of the statistical
counting errors

Table 6. Atom-probe analyses of martensite matrix before and after

temoerine I h at 560 C
I h 560 c
I h 560 C No secondary
As-quenched specimens contained precipitates
martensite secondary precipitates present
Si 1.2 * 0.2 I.1 +0.2 l.liO.2
V 0.8 * 0.2 0.4 2 0.2 0.6 i 0.2
CI 4.2 k 0.4 2.5 t 0.4 3.6 ? 0.4
Fe’ 75.9 * 0.8 77.5 2 I.4 75.2 z 1.3
co I I.4 * 0.5 13.0 i: 0.9 13.4 2 0.8
MO ?.I io.3 1.6iO.5 2.2 i 0.5
W 1.0+0.2 0.4 50.2 0.7 & 0.2
c 3.4 f 0.3 3.5 i: 0,s 3.2 f 0.4
Total IO.085 3161 3933
atoms
counted
No. of 2 2 3
specimens
analysed
*Includes Mn (peak overlap).
indicated error limits are based upon the standard deviation of the
statistical counting errors

3.4, Overageing at 7WC

Specimens which had previously been given the
standard tempering treatment of 3 times 1 h at 560X
were aged for times from Smin up to I h at 7OO’C.
Such a treatment corresponds to a severe overheating
which may occur during service and results in deteri-
orated properties. As shown in Fig. 12 considerable
changes occurred in the microstructure after just
5 min at 700X. The original secondary carbide pre-
cipitate dispersion of M2C or MC coarsened rapidly
and coarse precipitates of M,C and M,,C, also
appeared. The martensite plate boundaries were
heavily decorated by carbide precipitates. After

Fig. 10. Secondary carbide precipitation after tempering

I 0.2pm
Fig, 9. Microstructure after tempering 100 h at 560°C.
Primary carbides at P. Note the precipitation at the mar-
tensite plate boundaries (arrowed). (Low magnification
bright field micrograph.)
24 h at 560°C. (a) Bright field micrograph, (b) precipitate
dark field micrograph taken using the streaked reflection
marked X in (c), (c) selected area diffraction pattern. 100
matrix zone. Separation of M?C and MC reflections is
indicated. The reflection marked T is due to martensite
internal twins. As shown by the solution in Fig. 6(a), X can
be due to both M2C and MC.
 STILLER et al.: PRECIPITATION IN POWDER METALLURGICAL STEEL
Fig. 11. Field-ion .nicroscope image of M,C precipitates
after tempering for 24 h a~ 560 C.
1Smin at 700-C the amount of fine M,C or MC
precipitate inherited from the 560 C tempering treat-
ment had diminished substantially (Fig. 13) and
many of the martensite plate boundaries were bowed
indicating that some boundary migration had oc-
curred.
After 1 h at 700 C the plate martensite structure
had fully recovered to form an equiaxed fine grained
ferrite microstructure containing subgrains which
Fig. 12. Secondary precipitation after 3 x I h at 56O’C
followed by 5 min overageing at 700 C. (a) Low magnifi-
cation, (b) detail at a martensite plate boundary.
1465
were 0.2-0.5pm in size. The secondary carbides
present after this treatment were M&Z and M,,C,.
These precipitates often nucleated at the interfaces of
primary carbides with the ferrite matrix or else they
acted as pinning points for the subgrain boundary
network (see Fig. 14). Analysis of these carbides
showed that the M,C secondary carbides had a
similar composition to the M,C primary carbides and
that the M,,C, carbides contained substantial
amounts of Cr and Fe [2]. Compared with the
original matrix composition in the as-quenched con-
dition, or even to some extent the matrix composition
after tempering at 56O’C. the content of strong
carbide forming elements (V, Cr. MO. W) in the
matrix had diminished substantially 121.
A similar microstructural development also oc-
curred when as-quenched specimens were directly
tempered at 700°C without prior-tempering at 560-C.
The major exception here was that no fine precip-
itation of M,C or MC occurred during the early
stages of tempering and coarse particles of M,C and
M,,C6 precipitated rapidly on martensite plate
boundaries, twin-boundaries and irregularly within
the matrix. Tempering for 1 h at 700 C resulted in
microstructures similar to that shown in Fig. 13.
4. DISCUSSION
As shown in Table 3 the primary carbides had
complex mixed compositions. As may be expected V
was strongly concentrated in the MC primary car-
bides while MO and W were the alloying elements
primarily responsible for the formation of M,C. Cr
was present in both types of primary carbide to a
slightly greater extent than in the bulk composition
and the only major alloying element which was
rejected by the primary carbides was Co. The strong
concentration of V and C in the primary carbides
meant that the martensitic matrix prior to tempering
had a composition which was considerably less rich
in these elements than the bulk composition (com-
pare Tables 1 and 2). The primary carbides did not
Fig. 13. Dissolution of fine secondary precipitates after
15 min overageing at 700-C (dark field).
1466 STILLER et al.: PRECIPITATION IN POWDER METALLURGICAL STEEL
Fig. 14. Microstructure after 1h overageing at 700-C. The
secondary precipitates are M,C and M2&,. (a) Scanning
electron micrograph of an electropolished surface showing
secondary precipitation at primary carbide matrix interface.
(b) equiaxed ferrite subgrain structure with M,C precipitates
at subgrain boundaries.
change their compositions during tempering. Thus,
the relevant composition for the tempering reaction
is that of the as-formed martensite.
Both electron microscopy and field-ion microscopy
have shown the very fine and dense nature of the
secondary precipitate dispersion responsible for the
secondary hardening peak at 560 C. Electron
diffraction information is consistent with secondary
precipitate phases corresponding to either MC or
M2C (see Fig. 6) but the compositional information
from atom-probe analysis suggests that the vast
majority of these precipitates are carbon-deficient
M$. The main ~rbide-forming elements responsible
for the formation of these secondary precipitates were
Cr and MO but V and W were also present to a
greater proportion than in the as-formed martensite
(compare Tables 2 and 4). It is possible that the
“mixed” nature of these carbides is a contributing
factor to their fineness and resistance to coarsening
during tempering. Seal and Honeycombe [27] showed
that small additions of a second strong carbide
forming element substantially increases the secon-
dary hardening peak due to M&I precipitation in
Fe-Mo-C alloys. Similar effects have also been noted
with mixed MC type carbides 127-291 in low alloy
steels.
The drop in concentration of carbide-forming
elements in the martensitic matrix during the first
hour of tempering is readily apparent from Table 6
but the still significant carbon content points to a
strong supersaturation at this stage of the tempering
process. This is consistent with microscopic evidence
that the volume fraction of secondary precipitates
increased considerably after longer tempering times.
The somewhat higher carbide-forming element con-
tent of those FIM specimens which did not contain
secondary precipitates is consistent with them corre-
sponding to regions of retained austenite. Although
some C may have diffused away from these regions
during tempering and thus allowing transformation
to martensite during cooling to room temperature.
the substitutional alloying element content of these
regions would not have changed very much during
tempering because of the much slower rates of
diffusion of these elements.
Some changes in the average compositions of M&Z
with increasing tempering times were measured (see
Table 5). It should be mentioned here that there is
some uncertainty about the exact stoichiometry of
the precipitates after the shortest tempering time of
1 h at 56O’C. The extremely fine nature of the precip-
itates at this stage meant that some overlap with the
matrix could have occurred in some of the analyses.
Some of the Fe which was detected could have come
from the matrix, thus making the precipitates appear
more carbon deficient than they really were. Consid-
erably more confidence is placed in the data obtained
after longer tempering times (3 and 24 h) where larger
precipitates were analysed. Here the size of the pre-
cipitates made it possible to ensure that the probe
hole was completely over the precipitates during the
whole analysis. Also, detailed examination of the
sequence of arrival of ions at the detector helped
eliminate any signals which may have been collected
after the precipitates had been completely field evap
orated. The presence of Fe in the precipitates was
confirmed by the fact that signals from this element
arrived uniformly during the sequence of analysis of
each precipitate. This is consistent with previous
work on atom-probe analysis of small MC precip-
itates [ZS]. The atom-probe analyses indicate that
both the Fe and V contents of M?C secondary
precipitates decreased with increasing tempering time
(see Table 5).
It is interesting to note that no M,C (cementite)
was observed in any of the heat treatments which
were investigated. Cementite has been observed in a
number of other investigations of tempered high
speed steels [l, 4,S, 7,9] but in these cases the alloys
in question did not contain Co. Other work indicates
that less cementite is present if the alloy contains Co
[30,31] and this is consistent with the present results.
It has also been suggested that Co increases the rate
of nucleation of alloy carbides (e.g. M$) but de-
 STILLER ei al.: PRECIPITATION IN POWDER METALLURGICAL STEEL
creases the rate of growth of these precipitates [30].
It would seem that this effect is related to cobalt
causing an increased carbon activity and also de-
creasing the diffusivity of carbon in ferrite [32]. This
can be an additional explanation for the low growth
rate of secondary precipitates observed in the present
investigation. Other work has shown that Co en-
hances the transfo~ation of austenite to martensite
(33,341 suggesting that because the addition of Co
reduces the amount of retained austenite after hard-
ening, it leads to a microstructurally more evenly
tempered final product. These effects lead to im-
proved secondary hardness and, most importantly.
improved hot hardness and resistance to overagelog
1301.
The present investigation was conducted by com-
bining the attributes of analytical electron micros-
copy and atom-probe field-ion microscopy. At their
present stages of development neither of these tech-
niques alone is capable of providing all of the infor-
mation which is required for a fufl microstructural
description (viz. ~stallo~aphy, morphology and
local composition) of complex alloys of the type
studied here. The present work provides a good
illustration of the wide range of complementary
microstructural information which can be obtained
by the comprehensive use of both techniques.
5. CONCLUSIONS
1. The compositions of large primary precipitates
of MC and M,C were determined by STEM IEDX
and confirmed by atom-probe field-ion microscope
measurements.
2. The combined evidence from electron micros-
copy and atom-probe field-ion microscopy is that
MzC is the predominant finely dispersed secondary
precipitate which is responsible for peak hardness
during tempering at 56O’C.
3. Some MC secondary precipitates are also
present after tempering at 560% and these become
more apparent after longer tempering times.
4. The compositions of the fine secondary precip-
itates were determined by atom-probe field-ion mi-
croscopy.
5. Matrix compositions were determined both be-
fore and after tempering.
6. Overageing at 700°C results in a change in the
ferrite morphology to a recovered subgrain micro-
structure. The fine secondary precipitate dispersion
transforms to coarse M6C and M2&.
Acknowl&ements-Financial support from the Swedish
Board for Technical Development and the Swedish Natural
Science Research Council is acknowledged. The experi-
mental material was supplied by Klostcr Speedsteel AB and
discussions with H. Wise11are gratefully acknowledged as
are discussions with H. Norden and G. Wirmark
1467
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