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Grain and phase boundary segregation in WC–Co with TiC, ZrC, NbC or TaC additions
Jonathan Weidow ⁎, Hans-Olof Andrén
Department of Applied Physics, Chalmers University of Technology, SE-412 96 Göteborg, Sweden
a r t i c l e i n f o a b s t r a c t
Article history: The microstructure of interfaces in WC–Co based cemented carbides with TiC, ZrC, NbC or TaC additions was
Received 31 March 2010 analysed using energy dispersive X-ray analysis in a transmission electron microscope and using atom probe
Accepted 18 June 2010 tomography. Segregation to WC/WC grain boundaries and WC/(M,W)C phase boundaries corresponding to
between 0.4 and 1.2 atomic layers of close packed monolayers of Co was observed in all the materials. In
Keywords:
addition to Co, Ti, Zr and Nb, but not Ta, segregate to the WC/WC grain boundaries. Segregation was also
APT
TEM
observed for B, P, Fe and Cr, but not Ni, to the boundaries. These are impurities that originate from the
EDX material production. Segregation of Ti, Zr, Nb and Ta to WC/binder phase boundaries was observed. If
formation of a MC phase at the interface is assumed, the segregation corresponded to a thickness less than a
monolayer.
© 2010 Elsevier Ltd. All rights reserved.
1. Introduction coarser grained [10]. Fine grained cemented carbide is also needed for
more precise cutting operations. For these reasons, there is a need for
For metal cutting operations, there is a need for a material that has controlling the WC grain growth during sintering. Addition of carbides
high hot hardness, high toughness and good wear resistance. In WC– such as TiC, VC, Cr3C2, ZrC, NbC or TaC to the powder mixture is known to
Co based cemented carbides the hardness from a WC skeleton is inhibit WC grain growth [11]. For V, the grain growth inhibitor with the
combined with the toughness from the Co based binder. The material highest effect [11], the presence of a one to four atomic layer thick V-rich
is manufactured by powder metallurgy. Additions of carbides such as cubic carbide has been found at some WC/binder phase interfaces
TiC, ZrC, NbC or TaC to the powder mixtures are often done in order to [6,7,12–17]. It is believed that a continuous absorption and desorption
increase the wear resistance for high-speed machining operations of process of V-atoms at the interface during liquid phase sintering slows
steel [1]. down the Ostwald ripening process [17]. Also, a thin Cr-rich layer was
The strength of WC/WC grain boundaries is very important as they found at some WC/binder phase interfaces in a WC–Co based cemented
break up by Co infiltration during cutting and thereby make grain carbide with Cr additions [7,18,19]. Furthermore, it was recently
boundary sliding possible [2]. Ab initio calculations predict submo- discovered that smaller amounts of Mn segregate to WC/binder phase
nolayer segregation of Ti, V, Cr, Mn, Co and Ta to WC/WC grain interfaces [7]. Mn has been found to have a very small inhibiting effect on
boundaries where the work of separation will be increased and a WC grain growth [20]. In one study [5], no signs of Ta segregation were
strengthening of the grain boundary will take place [3–5]. Segregation seen at WC/binder phase interfaces. In another study [21], it was found
of V [6,7], Cr [7,8], Mn [7] and Co [7,8] has previously been that very small, non-quantified, amounts of Nb can segregate to WC/
experimentally verified. One study [5] showed no sign of Ta binder phase boundaries. This study also found that Zr cannot segregate
segregation to the boundaries. There exists no knowledge if the to the WC/binder phase boundaries. As far as we know, no experimental
prediction of Ti segregation is correct or any knowledge at all on the data exists on the microstructure of WC/binder phase boundaries in
possible segregation of Zr or Nb. WC–Co based cemented carbides with TiC additions.
During sintering the WC grains grow. It is generally accepted that this In this paper, we have systematically analysed the chemistry of
is mainly due to Ostwald ripening, a solution–reprecipitation process. WC/WC grain boundaries, WC/(M,W)C phase boundaries as well as
Due to their higher solubility, smaller WC grains are dissolved in the WC/binder phase boundaries in WC–Co based cemented carbides
liquid binder and larger WC grains can grow due to the resulting W and C with TiC, ZrC, NbC or TaC additions. Some preliminary results were
gradient. WC grain growth is also believed to take place due to grain presented at the 17th Plansee Seminar 2009 [22].
boundary migration [9]. For a cemented carbide with a constant volume
fraction of binder phase, a fine grained cemented carbide is harder than a 2. Experimental details
0263-4368/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijrmhm.2010.06.010
J. Weidow, H.-O. Andrén / Int. Journal of Refractory Metals and Hard Materials 29 (2011) 38–43 39
Fig. 1. APT reconstruction (largest diameter 75 nm, length 152 nm) of a WC/WC grain boundary in a WC–TiC–Co material. Left image: green dots = W atoms, red = C, blue = Co,
pink = Ti. Right image: pink dots = Ti atoms.
segregation to the boundary. The other three showed indications of a must be considered that this instrument used a thermionic W
very small Zr segregation. For the WC–NbC–Co material, three phase filament when our experiments were performed. The relatively low
boundaries were analysed. One showed a small Nb segregation to the intensity as well as the larger beam makes it difficult to detect signals
boundary, one indicated a possible small Nb segregation to the from layers much thinner than one atomic layer. It is therefore not
boundary and one showed no segregation to the boundary at all. For surprising that submonolayer segregation detection needs either a
the WC–TaC–Co material three phase boundaries were analysed. One state of the art TEM or an APT instrument.
phase boundary showed larger amount of Ta segregation to the When analysing the binder phase with APT, we find dissolved Cr,
boundary (Figs. 4–5), one showed smaller amounts of Ta segregation Fe and Ni. These elements are not added by purpose to the materials.
and one no Ta segregation at all. A small amount of Cr segregation was Instead, they are believed to have worn off from the inside of the
observed in some WC/binder phase boundaries in the different stainless steel lined mill during the milling process. We also find B and
materials as well as B segregation to boundaries in the WC–ZrC–Co P atoms in the material and they are believed to exist as impurities in
material. For the interfaces with the highest amount of segregation for the powder mixtures.
the different materials, the number of segregant atoms (Ti, Zr, Nb or
Ta) was counted from the APT reconstructions. These reconstructions
were also used to measure the interface area. A thin cubic MC layer 4.1. WC/WC grain boundaries
without any W mixing and suitable corresponding lattice parameters
[29] at the interface was assumed. Thereby a thickness of such a layer The results that Co and Ti segregate to the boundaries are in
in terms of close packed atom layers could be estimated (Table 3). As agreement with ab initio calculations [3–5]. The thickness of the Co
seen in Fig. 4, the difference in field evaporation field for the two layer that we measure is a little bit higher than the 0.5 monolayer that
phases will incorrectly be interpreted by the software as a change in the calculations predict as most energetically favorable. On the other
specimen radius. This was kept in mind and corrected for when the hand these calculations are performed for a specific grain boundary
number of atomic planes at the interfaces was calculated. geometry and we have no reason to believe that the boundaries that
we have analysed exactly fulfill these geometric conditions. The
fraction of Ti atoms in the boundary (28%) is a little bit lower than
4. Discussion what was found for materials with V or Cr additions but higher than
for Mn [7]. This is in agreement with the interfacial energy trend from
In general, the results are different depending on what method of ab initio calculations [4]. That Zr and Nb can segregate to the grain
microanalysis was used. Regarding the results from the Tecnai TEM it boundary was previously not known. Even if the segregation is
Table 1
WC/WC grain boundaries analysed with APT.
Table 2
WC/(M,W)C phase boundaries analysed with APT.
Co (atoms) Monolayers
the geometry of the interface rather than the addition of Ti. Probably it
originates from structural dislocations in the grain boundary. A similar
effect has been observed earlier with atom probe [31], in this case Ni
segregation to grain boundary dislocations in W.
The reason why Ti segregation to a WC/WC grain boundary could
be observed in a WC–ZrC–Co material is not completely understood.
Fig. 2. APT reconstruction proxigram across an analysis of a WC/WC grain boundary in a This observation was done with TEM-EDX. Both the K-peak and the L-
WC–TaC–Co material showing Co but no Ta segregation. peak in the EDX spectrum were very distinct. Thus, it is not believed
that the element identification is incorrect. Ti is believed to be present
relatively small, it might have beneficial effects on the strength of the in the material as an impurity.
material. The lack of Ta segregation to the boundaries is in
contradiction to calculations [5] but in agreement with experimental
data from an earlier study [5]. However, this study only used TEM- 4.2. WC/(M,W)C phase boundaries
EDX and therefore we now have a higher certainty in our conclusion
that Ta does not segregate to the boundaries. Some of the worn off Segregation of Co to a WC/(Ti,W)C interface has earlier been
material from the milling process was found at the grain boundaries. reported [8] but now seems to be generalised to all WC/(M,W)C
That Cr segregates to grain boundaries was seen in earlier studies interfaces. It is interesting to see that the amount of segregated Co is
[7,8]. That Fe segregates to the boundaries and Ni does not was almost equal in all the analysed boundaries and that it is almost the
previously not known. The impact of Fe segregation on the material same as for WC/WC grain boundaries. The segregation of Cr to the
properties is at present not known. The amount of segregated Cr and boundaries has not been reported earlier and the probable reason is
Fe is very low as an effect on the low total amount in the material. that the methods used in previous work on a WC/(Ti,W)C interface [8]
From a recent study we have seen that Cr can replace up to one third were not accurate enough or the lining of the mill was different.
of the segregated Co atoms [7]. How much Fe that would segregate if
there was more Fe available is not known. It is known that segregation
of P to interfaces has an embrittling effect for steel [30]. The effect of B 4.3. (M,W)C/(M,W)C grain boundary
and P for cemented carbides is not known. If embrittling, efforts
should be made to reduce the amount of such impurities in the The presence of a thin Co layer in the analysed (Ta,W)C/(Ta,W)C
powder mixtures. grain boundary is in agreement with earlier results for (M,W)C/(M,
Regarding the striped pattern in the APT reconstruction of a grain W)C grain boundaries [8]. However, this is the first time Cr
boundary in the WC–TiC–Co material, this is believed to be caused by segregation was detected at a (M,W)C/(M,W)C grain boundary.
Fig. 3. APT reconstruction of the volume surrounding the WC/WC grain boundary from Fig. 1 showing Co atoms (left) and Ti atoms (right).
42 J. Weidow, H.-O. Andrén / Int. Journal of Refractory Metals and Hard Materials 29 (2011) 38–43
Fig. 4. APT reconstruction (largest diameter 122 nm, length 178 nm) of a binder/WC phase boundary in a WC–TaC–Co material. Left image: green dots = W atoms, red = C, blue = Co,
pink = Ta. Right image: pink = Ta atoms.
4.4. WC/binder phase boundaries interface might be uninteresting since what we measure is the
microstructure at temperatures when all diffusion has stopped.
Due to the way WC grains grow during sintering, it is interesting to Therefore, the finding of Ti, Zr, Nb and Ta at some interfaces is more
know what the microstructure of the WC/binder phase boundaries a hint that they were there at the sintering temperature, probably
looks like. For V, the most effective grain growth inhibitor [11], a thin having a grain growth inhibiting effect and then it will depend on
V-rich carbide has been seen [6,7,12–17]. Kawakami et al. has interfacial energies whether a thin carbide film will be created or not
reported that the thickness is larger for a slowly cooled specimen upon cooling. That segregation only seems to occur to some WC/
than for a rapidly cooled specimen [17]. The conclusion made from binder interfaces and the difference in amount of segregation is
this is that the carbide actually nucleates during cooling after the believed to be an effect of the orientation relationship of the two
liquid state sintering. The grain growth inhibiting effect during liquid phases. Segregation might be energetically beneficial to some
phase sintering is therefore believed to originate from a continuous interfaces but not to other.
adsorption and desorption process of V-atoms at the interface. This It has been reported that neither Ta [5] nor Zr [21] segregates to WC/
makes it more difficult for W and C atoms to reach the WC/binder binder phase boundaries. In these studies, the less sensitive TEM-EDX
phase boundary thus inhibiting the grain growth. What we see is that technique was used and if a small segregation existed, it would have been
there is an excess of M atoms at some WC/binder phase boundaries, very difficult to detect. It should be mentioned that the Ta and Zr contents
especially this is the case for Ti atoms in the WC–TiC–Co material. The in the materials these authors studied were lower than those in this study.
amount of atoms is not enough to sum up to one monolayer. On the
other hand, if the M-rich layer is a (M,W)C carbide, it would be 5. Conclusions
enough that approximately half of the metal atoms would be W-
atoms in order to produce a monolayer of close packed (Ti,W)C phase. Four different cemented carbides with 10 vol.% binder phase and
Still, whether there is a segregation or a thin carbide film at the 20 vol.% cubic carbide phase were studied. The cubic carbides were
TiC, ZrC, NbC or TaC. The interfaces were studied with TEM-EDX and
atom probe tomography.
Co segregation to WC/WC grain boundaries as well as to WC/(M,W)C
phase boundaries and (Ta,W)C/(Ta,W)C grain boundaries was observed.
The total amount of segregating atoms corresponded to between a half
and one monolayer of close packed Co. For the WC/WC grain boundaries,
also Ti, Nb and Zr were seen to segregate. In the analysed grain
boundaries, Ti accounted for 28% of the segregated atoms, Zr for 7% and Nb
for 10%. Ta was found not to segregate to WC/WC grain boundaries.
Segregation to the boundaries was also observed for impurity B, P, Cr and
Fe, but not for impurity Ni. Cr, Fe and Ni are believed to originate from the
powder milling process.
Table 3
Thickness of MC layer at WC/binder phase boundaries from APT analysis.
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