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

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


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

electron microscopy (TEMISTEMIEDX) and atom-
The microstructure of high speed steels consists of probe field-ion microscopy. The ~mbination of these
large primary carbide particles (diameter 1-2 pm) two techniques enables the microanalysis of a wide
dispersed in a tempered martensitic matrix containing range of microstructural features with a number of
a much finer dispersion of secondary carbides which points of cross reference for verification of the accu-
precipitate during tempering [l]. In general these racy of the results [2,3].
steels contain large amounts of a variety of alloying Previous studies of high speed steels ([l] and
elements and it is important for further alloy devel- references therein) have shown that MC and M&C
opments to understand the function of these in the primary carbides form during solidification or soft
microstructure. A first step towards this under- annealing because of the generally high contents of V,
standing can be gained by studying the distribution W and MO. In addition, depending on the exact
of phases with the best available resolution and composition of the steel, primary carbides of the
determining their ‘detailed compositions. In the M&, hi& or M+Z types may also fotm. However,
present work this has been done at various stages these latter carbides usually dissolve during the hard-
ening treatment.
Because of the extremely fine nature of the second-
tPm~w~t~&ess: ESAB AR, Box 8004. 402 77 Giiteborg,
ary carbides at peak hardness very few clear images
SPresent address: Department of Metallurgy. Pennsylvania of these precipitates have been obtained under opti-
State University, University Park, PA 16802, U.S.A. mum tempering conditions. Thus, it has not usually

been possible to determine the exact nature of the of the peak hardness condition to a short period of
phases which are responsible for peak secondary over-heating.
hardness. However, depending upon the alloy com- The technique used for the preparation of thin foils
position, they are usually considered to be either MC for transmission electron microscopy has been de-
or M2C [ 1,4-lo]. Sometimes MC (cementite) is also scribed previously [2]. Examination was carried out in
claimed to be present at peak hardness [I, 71. a JEOL 200 CX Temscan instrument (TEM;STEM)
The alloy chosen for the present investigation was fitted with a Link 860 system for energy dispersive
the highly alloyed powder metallurgical steel, ASP X-ray spectroscopy (EDX). Typical detector live-
60. The powder metallurgical technique used in its times of 100-250 set were used for each microanalysis
production enables high concentrations of alloying by EDX. The energy scale of the spectra was cali-
elements to be used while keeping the microstructure brated against a generated zero strobe peak and the
free from large scale heterogeneities (e.g. banding, CuKn peak of a spectrum which was taken up at
segregation, slag inclusions) which are common to regular intervals from a Cu standard specimen. The
cast and wrought high speed steels [ 1I]. As is the case microanalyses were made quantitative by using the
for most other high speed steels, the optimum combi- Link Systems RTS-Z/FLS computer programme
nation of hardness, yield strength and toughness is which compares peak shapes with those from stan-
obtained by repeated tempering at 56OC with inter- dard spectra of pure elemental standards and applies
mediate air-toolings. For ASP 60 a three stage tem- the thin foil approximation [14] with corrections for
pering treatment is necessary to attain complete absorption.
transformation and tempering of the substantial The kxsl sensitivity factors valid for the electron
amounts of austenite, which are retained in the microscope and EDX system used in the investigation
microstructure after hardening. The tempering tem- were checked experimentally [3, 151. For most ele-
perature of 56O’C is slightly over the minimum which ments of interest it was found that the k,,, factors
is necessary to ensure complete transformation of the predicted by theory (161 were satisfactory but it has
retained austenite (121. Tempering at higher tem- been found necessary to use experimentally deter-
peratures or for longer times results in a substantial mined kxs, factors at low X-ray photon energies. In
decrease in secondary hardness. Because of the prac- particular it should be mentioned that the kxs, factors
tical importance of the tempering treatment at 560°C for W, and MoL lines were checked experimentally.
the present investigation has concentrated upon the Although primary compositional information for W
detailed microstructural developments which occur at and MO was obtained from the W, and MO, line
this temperature. The effect of overageing at 7OO’Cof intensities, knowledge of the relative intensity values
an initially optimum microstructure is also consid- W&V, and MoL/Mo, proved extremely useful in
ered. Such a heat treatment simulates a severe over- subsequent quantification.
heating which could possibly occur during service of Correction of the EDX results for absorption of
alloys of this type. Some of the results which are X-rays in the specimen required determination of the
presented here have previously appeared in pre- specimen thickness at the position where analysis was
liminary reports [2, 131. carried out. Because of the high amount of strain
contrast within the martensitic matrix this was gener-
2. EXPERIMENTAL ally impossible to establish by normal experimental
procedures. Instead, the thickness of the matrix and
The composition of the alloy under investigation is primary M,C and MC carbides were determined by
shown in Table 1. Specimens for subsequent micro- finding which estimated thickness gave the same
structural examination were austenitized in a salt compositional results from the RTS-2IFLS computer
bath at 1180°C for 3 min and hardened by quenching programme when the MO line intensities were deter-
into a molten salt bath at 55OC and air cooling to mined using either the MO, or MO, lines. The general
room temperature. The step cooling treatment elimi- accuracy of this method has been confirmed pre-
nates quench cracking. The standard tempering treat- viously (171, and in the present case was checked by
ment of three times 1 h at 56OC, which eliminates studies of spade shaped field ion microscope speci-
retained austenite and provides optimum hardness, mens which could be tilted 90’ in the microscope for
was investigated together with shorter and longer visual determination of local thickness. In situations
times at the same temperature. Other heat treatments where the local W composition was relatively high
were carried out at 7OO’C in order to investigate the (e.g. -30 wt% in M6C) it was found that the peak
tempering reaction at a temperature higher than that stripping routine in the computer programme did not
for peak hardness and also to investigate the response always satisfactorily separate the Sik peak from the

Table I. Composition of the experimental material

C Sl Mn Cr MO W Co V Fe
0 2.26 0.41 0.30 4.2 7.0 6.7 10.3 6.4 62.4
at.O, 10.41 0.8 I 0.30 4.5 4.0 2.0 9.7 6.9 61.6

mary carbides (see next section) dispersed in heavily

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
Fig. 1, Twinned plate martensite after step quenching from relationship, i.e.
1180-C. ( Ill)., ii{ 1lotr

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 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-


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.

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

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.
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

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),.

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

ear&de\ after temtxrmi? 3 x I h at 560 C
._--__L- ---
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.

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.

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

times during temoerine at 560 C
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
No. of 2 2 3
*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

24 h at 560°C. (a) Bright field micrograph, (b) precipitate
I 0.2pm dark field micrograph taken using the streaked reflection
marked X in (c), (c) selected area diffraction pattern. 100
Fig, 9. Microstructure after tempering 100 h at 560°C. matrix zone. Separation of M?C and MC reflections is
Primary carbides at P. Note the precipitation at the mar- indicated. The reflection marked T is due to martensite
tensite plate boundaries (arrowed). (Low magnification internal twins. As shown by the solution in Fig. 6(a), X can
bright field micrograph.) be due to both M2C and MC.

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.
Fig. 11. Field-ion .nicroscope image of M,C precipitates A similar microstructural development also oc-
after tempering for 24 h a~ 560 C. curred when as-quenched specimens were directly
tempered at 700°C without prior-tempering at 560-C.
1Smin at 700-C the amount of fine M,C or MC The major exception here was that no fine precip-
precipitate inherited from the 560 C tempering treat- itation of M,C or MC occurred during the early
ment had diminished substantially (Fig. 13) and stages of tempering and coarse particles of M,C and
many of the martensite plate boundaries were bowed M,,C6 precipitated rapidly on martensite plate
indicating that some boundary migration had oc- boundaries, twin-boundaries and irregularly within
curred. the matrix. Tempering for 1 h at 700 C resulted in
After 1 h at 700 C the plate martensite structure microstructures similar to that shown in Fig. 13.
had fully recovered to form an equiaxed fine grained
ferrite microstructure containing subgrains which 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. 12. Secondary precipitation after 3 x I h at 56O’C

followed by 5 min overageing at 700 C. (a) Low magnifi- Fig. 13. Dissolution of fine secondary precipitates after
cation, (b) detail at a martensite plate boundary. 15 min overageing at 700-C (dark field).

with mixed MC type carbides 127-291 in low alloy

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
Fig. 14. Microstructure after 1h overageing at 700-C. The from the matrix, thus making the precipitates appear
secondary precipitates are M,C and M2&,. (a) Scanning
electron micrograph of an electropolished surface showing more carbon deficient than they really were. Consid-
secondary precipitation at primary carbide matrix interface. erably more confidence is placed in the data obtained
(b) equiaxed ferrite subgrain structure with M,C precipitates after longer tempering times (3 and 24 h) where larger
at subgrain boundaries. precipitates were analysed. Here the size of the pre-
cipitates made it possible to ensure that the probe
change their compositions during tempering. Thus, hole was completely over the precipitates during the
the relevant composition for the tempering reaction whole analysis. Also, detailed examination of the
is that of the as-formed martensite. sequence of arrival of ions at the detector helped
Both electron microscopy and field-ion microscopy eliminate any signals which may have been collected
have shown the very fine and dense nature of the after the precipitates had been completely field evap
secondary precipitate dispersion responsible for the orated. The presence of Fe in the precipitates was
secondary hardening peak at 560 C. Electron confirmed by the fact that signals from this element
diffraction information is consistent with secondary arrived uniformly during the sequence of analysis of
precipitate phases corresponding to either MC or each precipitate. This is consistent with previous
M2C (see Fig. 6) but the compositional information work on atom-probe analysis of small MC precip-
from atom-probe analysis suggests that the vast itates [ZS]. The atom-probe analyses indicate that
majority of these precipitates are carbon-deficient both the Fe and V contents of M?C secondary
M$. The main ~rbide-forming elements responsible precipitates decreased with increasing tempering time
for the formation of these secondary precipitates were (see Table 5).
Cr and MO but V and W were also present to a It is interesting to note that no M,C (cementite)
greater proportion than in the as-formed martensite was observed in any of the heat treatments which
(compare Tables 2 and 4). It is possible that the were investigated. Cementite has been observed in a
“mixed” nature of these carbides is a contributing number of other investigations of tempered high
factor to their fineness and resistance to coarsening speed steels [l, 4,S, 7,9] but in these cases the alloys
during tempering. Seal and Honeycombe [27] showed in question did not contain Co. Other work indicates
that small additions of a second strong carbide that less cementite is present if the alloy contains Co
forming element substantially increases the secon- [30,31] and this is consistent with the present results.
dary hardening peak due to M&I precipitation in It has also been suggested that Co increases the rate
Fe-Mo-C alloys. Similar effects have also been noted of nucleation of alloy carbides (e.g. M$) but de-

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