Acta mater.

49 (2001) 2933–2939
www.elsevier.com/locate/actamat

ON THE REACTION SEQUENCE OF WC–Co FORMATION

USING AN INTEGRATED MECHANICAL AND THERMAL
ACTIVATION PROCESS
Z. G. BAN and L. L. SHAW†
Department of Metallurgy and Materials Engineering, Institute of Materials Science, University of
Connecticut, Storrs, CT 06269, USA

( Received 19 January 2001; received in revised form 17 May 2001; accepted 21 May 2001 )

Abstract—A systematic study on the reaction sequence of WC–Co composite formation by annealing high
energy ball milled WO3, CoO and graphite powder mixtures in a hydrogen atmosphere has been conducted.
X-ray diffraction has been used as the main tool to analyze the phase transformation of the powder mixture
during processing. It was observed that WO3 is reduced to W phase by passing through the intermediate
W20O58 and WO2 phases and the subsequent carburization sequence appears as
W→Co6W6C→Co3W3C→W2C→WC. The intermediate Co3W has been found in the reduction stage, which
can be subsequently carburized at higher temperatures.  2001 Acta Materialia Inc. Published by Elsevier
Science Ltd. All rights reserved.

Keywords: Reaction sequence

1. INTRODUCTION as h phases (Co6W6C and Co3W3C), ditungsten car-

bide (W2C), and the intermediate m phase (Co7W6).
The reaction sequence is often emphasized in syn-
It is evident that different starting materials for syn-
thesis of the WC–Co composite powder because a
thesis of WC–Co composites can lead to different
clear understanding of this would help to better con-
reaction sequences either in the reduction stage or in
trol a variety of the phases present in the final pro-
the carburization stage. WO3 and carbon are the typi-
duct, which are in close relationships with various
cal starting material of conventional methods for
properties such as hardness, toughness, wear resist-
ance and thermal conductivity [1]. The reaction making WC–Co cements with micrometer- or sub-
sequence for the formation of WC–Co composites can micrometer-sized particles [4]. WO3 is first reduced
be typically classified into two groups, one corre- in a hydrogen atmosphere, followed by the high tem-
sponding to the reduction stage, and the other corre- perature carburization of W powder with solid carbur-
sponding to the carburization stage. However, it has izers or carbon-containing gases to form WC. The
been reported that the reduction and the subsequent WC formed is then blended with Co powder with
carburization could be combined in one single oper- extensive milling to form a uniform WC–Co mixture.
ation [2]. The reaction sequence in the reduction stage In this method, Co is not involved in the reduction
is relatively simple and only involves the continuous and carburization stages, thereby avoiding the forma-
decomposition or reduction of the starting material. tion of the η phases and showing a relatively simple
The reaction sequence in the carburization stage, reaction sequence.
however, is very complicated, as it can be seen from The chemical processing, which is extensively pur-
the typical W–C–Co ternary phase diagram at 1300°C sued to generate nanostructured WC–Co powder, uses
that nine phases are present in the system [3]. The either homogeneous aqueous solutions of ammonium
complexity of the phase diagram is mainly due to the metaltungstate and cobalt nitrate or a polymer precur-
presence of several simple and complex carbides such sor, such as polyacrylonitrile as the starting material
[5, 6]. In the former case, the spray-dried powder of
the solution is decomposed and subsequently carbur-
ized by a CO/CO2 gas mixture. In the latter case, the
† To whom all correspondence should be addressed. Tel.:
+1-860-486-2592; fax: +1-860-486-4745.
starting material, which has the in situ carbon source,
E-mail address: [email protected] (L. L. is fired in the gas mixture of argon and hydrogen. As
Shaw) a result, complex carbide phases such as Co6W6C and

1359-6454/01/$20.00  2001 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 9 - 6 4 5 4 ( 0 1 ) 0 0 2 0 9 - 9
2934 BAN and SHAW: REACTION SEQUENCE OF WC–Co FORMATION

Co3W3C are often present in the final system although denoted as Specimen A thereinafter, was high energy
better control of the composition and processing para- milled using a modified Szegvari attritor that has been
meters can avoid these undesirable phases. shown to be effective in producing uniform milling
Elemental W, Co and C powders are often used as products within the powder charge [16]. Tungsten
the starting material in mechanical alloying, which is carbide (WC) balls (4.76 mm in diameter) were used
an alternative route to synthesize nanostructured WC– as the milling media and mixed with powder at a ball-
Co composites. It typically consists of milling the to-powder weight ratio of 60:1. The charged canister
mixture of W, C and Co powders at room tempera- was evacuated up to 10⫺2 torr, flushed with argon,
ture, followed by the hot isostatic processing of the followed by evacuation and finally back filled with
milled powder [7]. For this method, only carburiz- argon of purity 99.95% at a pressure of about 1.5 atm
ation reactions are present. before the onset of milling. The milling canister was
Recently, we have reported a different process, cooled using circulation water with a flow rate of
termed as integrated mechanical and thermal acti- about 770 ml/min throughout the process and the tem-
vation (IMTA) process or sometime mechanically perature of the canister was monitored with an E-type
activated synthesis (MAS), that allows for large-scale thermocouple attached to the bottom of the canister.
production of nanostructured carbides (e.g. SiC, TiC A milling speed of 600 rpm was employed.
and WC) [8–11], nitrides (e.g. Si3N4, CrN and TiN) The milled powder was subsequently subjected to
[12–14] and their composites (e.g. WC/Co) [11, 15]. reduction and carburization reactions. For the
The basic form of the IMTA process is to mechan- reduction reaction the as-milled powder was loosely
ically activate reactants at room temperature through loaded in a tube furnace and reduced at a desirable
high energy milling (the mechanical activation step), temperature range in a flowing gas mixture of H2
followed by completing the synthetic reaction at high (PH2 = 0.5 atm) and Ar (PAr = 0.5 atm). After the
temperatures (the thermal activation step). In com- reduction, the furnace was cooled to room tempera-
parison with the mechanical alloying approach, the ture. The subsequent carburization of the reduced
distinct advantage of the IMTA process is that it can powder was conducted in the same furnace at 1000°C
be applied to material systems that have a large posi- in an argon atmosphere. In both reactions, a heating
tive free energy of formation for forming compounds rate of 480°C/h was employed. Most experimental
at ambient temperature. Therefore, WC–Co can be results presented in this study were carried out using
synthesized via the IMTA process using WO3, CoO the aforementioned conditions. However, in some
and C as the starting material, instead of W, Co and cases the milled powder was directly heated to
C. Because of the mechanical activation at ambient 1000°C in an argon atmosphere for 2 h, thereby for-
temperature, the synthetic reaction of the IMTA pro- ming nanostructured WC–Co materials by simul-
cess can be carried out at much lower temperatures taneous reduction and carburization at 1000°C.
and/or shorter time than those used in the conven- Phase identification of the as-milled and reacted
tional carbothermic reduction [11, 15]. Due to the low powder mixtures was conducted using X-ray diffrac-
synthetic temperature, the nanocrystalline structure tion (XRD) method with Cu Ka radiation (Bruker Axs
can be easily obtained. Furthermore, because of the D5005D X-ray Diffractometer). The average size of
low reaction temperature and short reaction time, the crystallites was determined using the “Win-Crysize”
IMTA process appears to be a cost–effective process software [17] that is based on the Warren–Averbach
for making large quantities of nanostructured WC–Co theory [18] and includes the consideration of the
materials [11, 15]. instrumental broadening. The morphology of powder
To fully utilize the potential of the IMTA process particles was characterized with scanning electron
and to optimize the IMTA process for making nanos- microscopy (SEM).
tructured WC–Co, it is necessary to investigate the
reaction sequence of the IMTA process, which could
be quite different from those in other synthesis 3. RESULTS AND DISCUSSION
methods. In the following sections, the reaction 3.1. Formation of nanostructured WC–Co
sequence for the mechanically activated WO3, CoO
and C powder mixture exposed to the gas mixture of Figure 1 shows the XRD patterns of Specimen A
hydrogen and argon at elevated temperatures is before milling and milled for different times at ambi-
described. The mechanisms controlling each reaction ent temperature. It can be seen that the starting
step are also discussed. material of WO3, CoO and graphite are crystalline.
With the increase of milling time, some distinct fea-
tures can be identified. First, the integral intensity of
2. EXPERIMENTAL
graphite peaks was substantially reduced in 6 h of
Tungsten trioxide (WO3) powder (Alfa, 99.8%, 10– milling, which is believed to be caused by the amor-
20 µm), graphite powder (Alfa, 99.9%, ⫺100 mesh) phization of graphite [16]. Second, the intensity of
and cobalt oxide (CoO) powder (Alfa, 99%, ⫺325 WO3 peaks decreases with the increase of milling
mesh) were used as the starting material. The sample time and also the preserved reflections of the remain-
with a molar ratio of WO3–C–CoO fixed at 1:2.4:0.7, ing crystalline WO3 exhibit broadening, suggesting
 BAN and SHAW: REACTION SEQUENCE OF WC–Co FORMATION 2935

sizes of WO3, CoO and C powders are all reduced to

the submicrometer range in just 3 hours of milling,
i.e. a reduction in particle size from about 40 µm to
0.3 µm. However, beyond the 3 h of milling little
change in the particle size occurs as shown in Fig. 2.
Thus, from the XRD and SEM examination, we can
conclude that the powder mixture with high energy
milling has finer particle sizes, larger specific surface
areas and a higher free energy due to the smaller crys-
tallite sizes and/or internal strain than the powder
mixture without milling. Therefore, we expect a
higher chemical reactivity of the milled powder than
the powder mixture without mechanical activation.
The milled powder mixture, therefore, is very suitable
Fig. 1. XRD patterns of Specimen A milled for various times
in argon. Key: 쐌, WO3; 䉬, CoO; 䊊, Graphite. for the subsequent low temperature reduction and car-
burization that in turn will generate nanostructured
WC–Co.
the reduced crystallite size and/or the introduction of Such an expectation is indeed confirmed by experi-
the internal strain due to high energy milling. Third, ments. Figure 3 compares XRD spectra of two WO3,
the peak broadening and intensity decrease also occur CoO and C powder mixtures after being heated at
to CoO, again suggesting the reduced crystallite size 1000°C in argon for 2 h. The two powder mixtures
and/or the introduction of the internal strain. Based shown have the same starting composition but one
on the peaks broadening, the average size of WO3 with milling for 12 h and the other without milling.
crystallites is estimated to be 21, 12 and 12 nm for It can be seen that the tungsten oxide in the powder
6, 9 and 12 h of milling, respectively. mixture with milling has been completely reduced
SEM images of the starting and milled powder and carburized to form WC, whereas the powder mix-
mixtures are shown in Fig. 2. It can be seen that the ture without milling still contains a substantial

Fig. 2. SEM images of WO3–CoO–graphite powder mixtures with (a) no milling, (b) milling for 3 h, (c) 6 h,
and (d) 12 h.
2936 BAN and SHAW: REACTION SEQUENCE OF WC–Co FORMATION

for 6 h, followed by heating at different temperatures

ranging from 450°C to 650°C for 2 h in a gas mixture
of hydrogen (PH2 = 0.5 atm) and argon
(PAr = 0.5 atm). It can be seen from Fig. 4 that the
temperature required to reduce CoO to Co is much
lower than that required to reduce WO3 to W. At
450°C, CoO has been completely reduced to Co. At
450°C, the WO3 has also been completely reduced to
W20O58 that in turn transforms to WO2 at or below
500°C. The transformation of WO2 to W starts at
570°C; however, the reduction of WO2 to W does not
complete until 650°C. Thus, the reduction of WO3 to
W takes place in at least three steps, following the
Fig. 3. XRD patterns of original and milled WO3–CoO–graph-
ite powder mixtures after heated at 1000°C in an argon atmos-
route: WO3→W20O58→WO2→W, which is consistent
phere for 2 h. with the result for WO3 without milling reported in
the literature [19, 20]. This result indicates that high
amount of the tungsten oxide. This result clearly dem- energy milling prior to the high temperature reaction,
onstrates that high energy milling before car- although enhancing the formation of WC (Fig. 3),
bothermic reduction and carburization can greatly does not alter the reduction sequence established for
enhance the formation of WC–Co materials. Based coarse–grained WO3. Based on these results, the reac-
on the XRD peak broadening, the size of WC crystal- tions for reduction of WO3 by H2 can be expressed as:
lites is estimated to be 32 nm, which is very close
to the result obtained from the study of transmission 20WO3 + 2H2 = W20O58 + 2H2O (1)
electron microscopy [15].
3.2. Reduction sequence W20O58 + 18H2 = 20WO2 + 18H2O (2)
The reaction of the powder mixture exposed to the
H2/Ar gas mixture can be divided into two stages:
stage I the reduction of CoO and WO3, and stage II WO2 + 2H2 = W + 2H2O (3)
the carburization of the reduced powder to form car-
bides. The reaction sequence corresponding to the The mechanism of formation of various intermedi-
stage I is discussed in this section, while the reaction ate oxides during the reduction of WO3 has been
sequence of the stage II will be discussed in the described by Haber et al. [20]. It is well known that
next section. the valence state of the cation is dependent on the
Figure 4 is the XRD patterns of Specimen A milled coordination number of the polyherdra and the way

Fig. 4. XRD patterns of Specimen A milled for 6 h in Ar, followed by annealing in a temperature range of
450–650°C for 2 h in the H2 and Ar mixture (PH2 = 0.5 atm, PAr = 0.5 atm). Key: q, Co3W; h, Co6W6C.
 BAN and SHAW: REACTION SEQUENCE OF WC–Co FORMATION 2937

in which the coordination polyhedra is linked ture increases to 720°C, at which trace of the strong-
together. Thus, based on the mechanism proposed by est peak of W2C can be detected, and finally become
Haber et al. the reduction sequence of WO3 to W weaker at 750°C. Note that the weakening of Co3W3C
could be explained as follows. In the initial reduction intensities at 750°C is accompanied by the formation
stage, W5.8+ ions are at first formed at the surface of of W2C and WC, suggesting that the transformation
WO3 particles probably due to the chemisorption of of large amount of Co3W3C to W2C has occurred at
hydrogen. The isolated oxygen vacancies are then 750°C. Thus, based on the XRD analysis, it can be
generated around the cation W6+, resulting in the for- proposed that the carburization reaction occurs in the
mation of the intermediate W4+. With the further following route: W (and Co3W)→Co6W6C→Co3
exposure of the powder to the strong reduction atmos- W3C→W2C→WC. According to this route, the fol-
phere, the pure metal–metal bond is formed, resulting lowing reactions can be proposed for the carburiz-
in the formation of pure W. ation in the IMTA process:
The most interesting phenomenon occurring in the
reduction of the milled powder mixture is the forma- 6W + 6Co + CH4 = Co6W6C + H2 (4)
tion of the intermediate compound Co3W (q phase in
Fig. 4), which is not reported in any other synthesis
routes. It can be seen from Fig. 4 that Co3W phase 3W + Co3W + CH4 = Co6W6C + H2 (5)
becomes detectable at 570°C right after the occur-
rence of W, accompanied by the disappearance of Co
phase, which was formed, from CoO at a lower tem- Co6W6C + CH4 = 2Co3W3C + H2 (6)
perature. Thus, it can be claimed that once W is for-
med in the reduction, it will subsequently react with
Co, which is in contact with W, leading to the forma- 2Co3W3C + CH4 = 3W2C + 6Co + H2 (7)
tion of Co3W. The W–Co binary phase diagram indi-
cates that two intermediate compounds are present in
the W–Co system, namely, Co3W and Co7W6 [21]. W2C + CH4 = 2WC + H2 (8)
The phenomenon that only Co3W is detectable in
XRD spectra could be elucidated on the basis of the
reaction kinetics. Generally, the diffusivity of an Note that the form of the carbon source in the pro-
element is inversely proportional to its atomic weight. posed reactions above is assumed to be CH4, which
Consequently, Co, which is much lighter than W, dif- is formed by the reaction between solid carbon and
fuses faster in the W phase than W in the Co phase. hydrogen. Although solid carbon can react with W
Similarly, Co is expected to diffuse faster in Co3W and various intermediate carbides directly and there
and Co7W6 phases than W. Thus, once Co7W6 and is also C2H2 in the gas phase, it is reasonable to state
Co3W are formed at the W–Co interface, Co7W6 will that the carburization process is dominated by reac-
be converted to Co3W very soon because of the fast tions (4) to (8). Such a statement is consistent with
diffusion of Co in Co3W. As a result, little Co7W6 is commercial production of coarse-grained WC by car-
present in the specimen. burization using a CH4-dominated atmosphere that is
generated by heating a W-plus-C mixture under
3.3. Carburization sequence
hydrogen [22]. Our thermodynamic calculation also
The most complicated reactions take place at the confirms that CH4 is the dominant component of the
carburization step in the hydrogen atmosphere. Figure gaseous phase when graphite reacts with H2 at tem-
5 is the XRD patterns of Specimen A milled for 6 h, peratures below 850°C.
followed by heating at different temperatures ranging Co6W6C and Co3W3C, both of which have a cubic
from 650°C to 750°C for 2 h in a gas mixture of structure, are very common intermediate carbides
hydrogen (PH2 = 0.5 atm) and argon (PAr = 0.5 atm). present in the Co–W–C system. Co6W6C starts to
Figure 5 clearly shows that Co6W6C phase, denoted form in our experiments at 650°C through reaction
as η phase, starts to appear at 650°C, with only the (4), (5) and/or both, which is followed by the conver-
strongest peak (2q = 43.2°) detectable in the XRD sion to Co3W3C at 700°C in accordance with reaction
spectrum. As temperature increases, the other peaks (6). As pointed out before, Co6W6C continues to
corresponding to Co6W6C become evident, together increase up to 750°C, while as a comparison, Co3W3C
with the increase of the peak intensities of the existing increases first and then decreases at 750°C. The
peaks, indicating that more and more Co6W6C phases decrease in Co3W3C is accompanied by the formation
have been formed. This phenomenon persists up to of W2C and WC. This suggests that part of Co3W3C
750°C, which is the highest temperature we have used has been transformed to W2C through reaction (7)
to heat the powder mixture in the hydrogen and argon predominantly at 750°C. At 750°C, trace of WC can
gas mixture. Co3W3C, denoted as h2 in Fig. 5, exhib- be identified, indicting that the conversion from W2C
its a different behavior from Co6W6C. The peaks cor- to WC [i.e. reaction (8)] has also occurred at this tem-
responding to Co3W3C are detectable in the XRD perature.
spectrum at 700°C, then become stronger as tempera- Based on these analyses, we can summarize the
2938 BAN and SHAW: REACTION SEQUENCE OF WC–Co FORMATION

Fig. 5. XRD patterns of Specimen A milled for 6 h in Ar, followed by annealing in a temperature range of
650–750°C for 2 h in the H2 and Ar mixture (PH2 = 0.5 atm, PAr = 0.5 atm). Key: q, Co3W; h, Co6W6C; h2,
Co3W3C.

carburization sequence in this study as shown in Fig. once Co3W3C has formed from Co6W6C, it will be
6. For comparison, a 1400°C isothermal section of further carburized to form W2C according to reaction
the W–Co–C ternary equilibrium phase diagram [23] (7). Although not consistent with the 1400°C equilib-
is also included in Fig. 6. The selection of this phase rium phase diagram, the absence of CoW3C in favor
diagram for comparison is because there are no equi- of the equilibrium between Co3W3C and W2C at
librium phase diagrams below 1000°C available in 1000°C has also been observed by other investigators
the literature. In the phase diagram shown, M12C, [23]. Further, it is interesting to note that both W2C
which exhibits a small homogeneous composition and Co3W3C are metastable phases below 1100°C [3].
range, is the common shorthand for Co6W6C and Thus, the observed equilibrium between Co3W3C and
M6C, sometimes formularized as Co2+XW4⫺XC, has a W2C and the absence of CoW3C in this study are
wide composition range spreading between Co3W3C believed to be related to the metastability of the W–
and Co2W4C. The ␬-carbide CoW3C (previously Co–C system.
known as Co3W9C4) is often chosen to be neglected
due to the limited availability of its thermodynamic
4. CONCLUDING REMARKS
data. Although the equilibrium phase diagram is
established at a higher temperature, the carburization A systematic study on the reaction sequence of
sequence established in our experiments matches it WC–Co composite formation through the IMTA pro-
quite well with the following three discrepancies. cess using the WO3, CoO and graphite powder mix-
First, the intermediate phase Co3W is present, while ture in the hydrogen-containing atmosphere has been
Co7W6 is not detected in our study. Second, ␬-carbide conducted. From this study, the following conclusions
CoW3C is not found in our experiment. Third, W2C can be made:
can be formed from Co3W3C in our study.
These discrepancies can be explained as follows. 1. High energy milling prior to carbothermic
Although there is no Co3W phase in the 1400°C equi- reduction and carburization has led to finer particle
librium phase diagram, the W–Co binary phase dia- sizes, larger specific surface areas, smaller crystal-
gram [21] shows that Co3W phase is thermodyn- lite sizes and internal strains in the WO3–CoO–C
amically stable below 1093°C. Further, Pollock and powder mixture. Such milled powder mixtures
Stadelmaier [23] have found that Co3W can be in have high chemical reactivity and result in the
equilibrium with Co6W6C phase at 1000°C. Thus, our enhanced formation of nanostructured WC–Co
findings are consistent with these studies [21, 23], i.e. materials.
Co3W is a stable phase at the temperature range we 2. The reduction sequence of the milled WO3 in the
investigated and could be carburized to form Co6W6C hydrogen-containing atmosphere has been ident-
as shown by reaction (6). ified as WO3→W20O58→WO2→W, a result con-
The second and third discrepancies can be sistent with the reduction sequence of WO3 with-
explained as follows. Our study has revealed that out milling reported in the literature.
 BAN and SHAW: REACTION SEQUENCE OF WC–Co FORMATION 2939

are related to the metastability of the W–Co–C

system.

Acknowledgements—The financial supports from the National

Science Foundation under grant No. DMR-9710265 as well as
the University of Connecticut Research Foundation are gre-
atly appreciated.

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