Int.

Journal of Refractory Metals and Hard Materials 29 (2011) 38–43

Contents lists available at ScienceDirect

Int. Journal of Refractory Metals and Hard Materials

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / I J R M H M

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
For metal cutting operations, there is a need for a material that has
high hot hardness, high toughness and good wear resistance. In WC–
Co based cemented carbides the hardness from a WC skeleton is
combined with the toughness from the Co based binder. The material
is manufactured by powder metallurgy. Additions of carbides such as
TiC, ZrC, NbC or TaC to the powder mixtures are often done in order to
increase the wear resistance for high-speed machining operations of
steel [1].
The strength of WC/WC grain boundaries is very important as they
break up by Co infiltration during cutting and thereby make grain
boundary sliding possible [2]. Ab initio calculations predict submo-
nolayer segregation of Ti, V, Cr, Mn, Co and Ta to WC/WC grain
boundaries where the work of separation will be increased and a
strengthening of the grain boundary will take place [3–5]. Segregation
of V [6,7], Cr [7,8], Mn [7] and Co [7,8] has previously been
experimentally verified. One study [5] showed no sign of Ta
segregation to the boundaries. There exists no knowledge if the
prediction of Ti segregation is correct or any knowledge at all on the
possible segregation of Zr or Nb.
During sintering the WC grains grow. It is generally accepted that this
is mainly due to Ostwald ripening, a solution–reprecipitation process.
Due to their higher solubility, smaller WC grains are dissolved in the
liquid binder and larger WC grains can grow due to the resulting W and C
gradient. WC grain growth is also believed to take place due to grain
boundary migration [9]. For a cemented carbide with a constant volume
fraction of binder phase, a fine grained cemented carbide is harder than a
coarser grained [10]. Fine grained cemented carbide is also needed for
more precise cutting operations. For these reasons, there is a need for
controlling the WC grain growth during sintering. Addition of carbides
such as TiC, VC, Cr3C2, ZrC, NbC or TaC to the powder mixture is known to
inhibit WC grain growth [11]. For V, the grain growth inhibitor with the
highest effect [11], the presence of a one to four atomic layer thick V-rich
cubic carbide has been found at some WC/binder phase interfaces
[6,7,12–17]. It is believed that a continuous absorption and desorption
process of V-atoms at the interface during liquid phase sintering slows
down the Ostwald ripening process [17]. Also, a thin Cr-rich layer was
found at some WC/binder phase interfaces in a WC–Co based cemented
carbide with Cr additions [7,18,19]. Furthermore, it was recently
discovered that smaller amounts of Mn segregate to WC/binder phase
interfaces [7]. Mn has been found to have a very small inhibiting effect on
WC grain growth [20]. In one study [5], no signs of Ta segregation were
seen at WC/binder phase interfaces. In another study [21], it was found
that very small, non-quantified, amounts of Nb can segregate to WC/
binder phase boundaries. This study also found that Zr cannot segregate
to the WC/binder phase boundaries. As far as we know, no experimental
data exists on the microstructure of WC/binder phase boundaries in
WC–Co based cemented carbides with TiC additions.
In this paper, we have systematically analysed the chemistry of
WC/WC grain boundaries, WC/(M,W)C phase boundaries as well as
WC/binder phase boundaries in WC–Co based cemented carbides
with TiC, ZrC, NbC or TaC additions. Some preliminary results were
presented at the 17th Plansee Seminar 2009 [22].
2. Experimental details

Four different materials were produced from the same 1.7 μm WC

⁎ Corresponding author. Tel.: + 46 31 772 3137; fax: + 46 31 772 3224. powder with additions of TiC, ZrC, NbC or TaC. The materials were
E-mail address: jonathan.weidow@chalmers.se (J. Weidow). designed in the as-sintered condition to contain 20 vol.% cubic carbide

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
phase and 10 vol.% binder phase. Thermodynamic calculations were
performed in order to get correct as-sintered compositions with the same
carbon potential for the different materials. This was done using Thermo-
Calc [23] with a for the materials suitable database [24]. The materials
were produced by a standard powder metallurgy route. The milling time
was 45.5 h and sintering was performed at 1430 °C with a 1 h holding
time in a 40 mbar Ar atmosphere. In order to facilitate atom probe
specimen production, the materials were produced in the square
SNUN120408 insert shape (12.7×12.7×4.76 mm3). The materials have
previously been investigated with scanning electron microscopy (SEM)
including electron backscatter diffraction (EBSD) [25]. The WC grain size
was measured with EBSD as equivalent circle diameter. Compared with a
reference material without any cubic carbide additions, the mean WC
grain size was 40% smaller for the WC–TiC–Co material, 15% smaller for
the WC–TaC–Co material, 9% smaller for the WC–ZrC–Co material and 8%
smaller for the WC–NbC–Co material.
Production of sharp needle specimens for atom probe was started
by cutting the inserts in 12 mm long rods with 200 μm square cross
section. The tip of the rods was dipped in Lacomite, a highly viscous
lacquer, repeated times until they were covered with a three to four
mm diameter lacquer sphere. The rods were electropolished to tip-
shape. This was done in an electrolyte consisting of 5% H2SO4 in
ethanol cooled to − 30 °C with a gold ring as counter electrode and
using a DC voltage of 29 V. The high current at the end caused an
oxide layer at the tip. This was removed by a couple of 10 ms 40 V
pulses in 5% H2SO4 in methanol cooled to − 20 °C with a platinum foil
as counter electrode. A couple of additional shorter pulses could
sharpen the specimen further. However, preferential etching of
different phases in the different materials made the controlled back
polishing method [26] unusable. The final sharpening was instead
performed in a FEI Strata DB 235 DualBeam. This instrument
combines a scanning electron microscope with a focused ion beam
milling workstation. The high (52°) angle between the electron
column and the ion column enables sputtering with up to 30 kV Ga+
ions incident parallel to the tip axis with control of the process from
the side using SEM imaging.
In atom probe tomography, traditionally a standing voltage is
applied to the specimen which together with voltage pulsing causes
field evaporation of surface atoms. The high electric field at the tip will
cause a mechanical stress on the specimen, thus creating a substantial
risk for specimen fracture. Using laser pulsing instead of voltage pulsing
and thereby having thermally activated field evaporation, the risk is
reduced. However, the high electric field that is needed for field
evaporation of WC, 58–64 V/nm [27], still implies that the volume of
interest should be within the outer 100 nm of the specimen. For
production of specimens with a phase boundary in the tip region of the
specimen, sputtering in the DualBeam workstation was continued until
this was the case. The voltage and current were low (10 kV and 300 pA)
in order to decrease the radiation damage due to the sputtering. For
production of specimens with a WC/WC grain boundary in the tip region
of the specimen, the contrast was not sufficient in the DualBeam to
detect the position of the grain boundary. Instead, the specimens were
investigated in a FEI Tecnai G2 transmission electron microscope (TEM)
between periods of sputtering.
The atom probe specimens were analysed in an Imago LEAP 3000X
HR atom probe tomography (APT) instrument. The instrument was
run with a specimen temperature of 66 K in laser mode with the pulse
energy 0.35 nJ and pulse frequency 200 kHz. These parameters
correspond to a 12C+/12C2+ charge state distribution of 0.34–0.42 in
a WC analysis. Data was analysed with the Imago software IVAS 3.4.1.
TEM specimens were created in the DualBeam workstation using
the in situ lift-out technique. The specimens were analysed with the
FEI Tecnai G2 TEM equipped with an EDAX rTEM energy dispersive X-
ray spectrometer (EDX) or with a FEI Titan 80-300 TEM equipped with
a condenser spherical aberration corrector and an Oxford Instruments
Inca X-sight EDX detector.
39
3. Results
3.1. WC/WC grain boundaries
The Tecnai TEM was used to analyse several WC/WC grain
boundaries with EDX. For the WC–TiC–Co material, six grain
boundaries were analysed, for the WC–ZrC–Co material two, for the
WC–NbC–Co material six and for the WC–TaC–Co two. Co segregation
was observed in all grain boundaries. Segregation of any other
elements could not be observed with this instrument.
The Titan TEM was used to analyse one WC/WC grain boundary in
the WC–ZrC–Co material with EDX. Apart from Co segregation to the
boundary, a very small Zr segregation was also observed, as well as a
small Ti segregation.
With APT, one WC/WC grain boundary in the WC–TiC–Co material
(Fig. 1), one in the WC–ZrC–Co material, one in the WC–NbC–Co material
and two grain boundaries in the WC–TaC–Co material were analysed. It
was seen that the total amount of segregated atoms to the grain
boundaries corresponded to approximately one monolayer of close
packed Co (Table 1). In the WC–TiC–Co material 28% of the grain
boundary atoms were Ti atoms, in the WC–ZrC–Co material 2% were Zr
atoms and in the WC–NbC–Co material 11% were Nb atoms. Ta has a
relatively large solubility in WC compared with the solubility of Ti, Zr or
Nb [28]. Therefore, for the analyses of grain boundaries in the WC–TaC–Co
material, an isosurface was created at the interface and a proxigram
showed the concentration of different elements as a function of the
distance to the interface. No higher Ta concentration was observed (Fig. 2)
in any of the two boundaries, so Ta cannot be said to segregate to the
boundaries. In the boundaries in the different materials, smaller amounts
(below 2% of the segregant atoms) were seen of Cr, Fe and P and, for the
WC–ZrC–Co material, also of B. For the analysed grain boundary in the
WC–TiC–Co material, a striped pattern of the segregant atoms could be
seen where the Co and Ti atoms seemed to occupy alternating stripes
(Fig. 3). For all analysed grain boundaries, the Co atoms seemed to replace
the C atoms with the W concentration being constant.
3.2. WC/(M,W)C phase boundaries
With EDX in the Tecnai TEM, one WC/(M,W)C phase boundary was
analysed for each of the materials and Co segregation was observed in
all of these interfaces.
With APT, two WC/(Ti,W)C, one WC/(Zr,W)C, two WC/(Nb,W)C
and three WC/(Ta,W)C phase boundaries were analysed (Table 2). As
seen, all boundaries showed Co segregation corresponding to
between 0.35 and 1.02 monolayers of close packed Co. Smaller
amounts of Cr, Fe and P were also seen at the interfaces.
3.3. (M,W)C/(M,W)C grain boundary
With APT, one (Ta,W)C/(Ta,W)C grain boundary was analysed and
Co segregation was observed in the interface. The amount of Co (9818
atoms) corresponded to 1.10 monolayers of close packed Co. Smaller
amounts of Cr, Fe and P were also found at the interface.
3.4. WC/binder phase boundaries
With EDX in the Tecnai TEM, two out of two analysed boundaries
in the WC–TiC–Co material showed Ti segregation. One boundary was
analysed in the WC–ZrC–Co material without any sign of Zr
segregation and five boundaries were analysed in the WC–NbC–Co
material without any sign of Nb segregation.
Several WC/binder phase boundaries were also analysed with APT.
For the WC–TiC–Co material, two out of five analysed boundaries
showed a larger amount of Ti segregation to the phase boundary and
the other three a smaller amount of Ti segregation. For the WC–ZrC–Co
material, one out of four analysed phase boundaries showed a small Zr
40 J. Weidow, H.-O. Andrén / Int. Journal of Refractory Metals and Hard Materials 29 (2011) 38–43
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
very small Zr segregation. For the WC–NbC–Co material, three phase
boundaries were analysed. One showed a small Nb segregation to the
boundary, one indicated a possible small Nb segregation to the
boundary and one showed no segregation to the boundary at all. For
the WC–TaC–Co material three phase boundaries were analysed. One
phase boundary showed larger amount of Ta segregation to the
boundary (Figs. 4–5), one showed smaller amounts of Ta segregation
and one no Ta segregation at all. A small amount of Cr segregation was
observed in some WC/binder phase boundaries in the different
materials as well as B segregation to boundaries in the WC–ZrC–Co
material. For the interfaces with the highest amount of segregation for
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
without any W mixing and suitable corresponding lattice parameters
[29] at the interface was assumed. Thereby a thickness of such a layer
in terms of close packed atom layers could be estimated (Table 3). As
seen in Fig. 4, the difference in field evaporation field for the two
phases will incorrectly be interpreted by the software as a change in
specimen radius. This was kept in mind and corrected for when the
number of atomic planes at the interfaces was calculated.
4. Discussion
In general, the results are different depending on what method of
microanalysis was used. Regarding the results from the Tecnai TEM it
Table 1
WC/WC grain boundaries analysed with APT.
Co (atoms) Ti (atoms)
WC–TiC–Co 27,911 10,983
WC–ZrC–Co 9456
WC–NbC–Co 2059
WC–TaC–Co 2409
WC–TaC–Co 390
must be considered that this instrument used a thermionic W
filament when our experiments were performed. The relatively low
intensity as well as the larger beam makes it difficult to detect signals
from layers much thinner than one atomic layer. It is therefore not
surprising that submonolayer segregation detection needs either a
state of the art TEM or an APT instrument.
When analysing the binder phase with APT, we find dissolved Cr,
Fe and Ni. These elements are not added by purpose to the materials.
Instead, they are believed to have worn off from the inside of the
stainless steel lined mill during the milling process. We also find B and
P atoms in the material and they are believed to exist as impurities in
the powder mixtures.
4.1. WC/WC grain boundaries
The results that Co and Ti segregate to the boundaries are in
agreement with ab initio calculations [3–5]. The thickness of the Co
layer that we measure is a little bit higher than the 0.5 monolayer that
the calculations predict as most energetically favorable. On the other
hand these calculations are performed for a specific grain boundary
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
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
ab initio calculations [4]. That Zr and Nb can segregate to the grain
boundary was previously not known. Even if the segregation is
Zr (atoms) Nb (atoms) Ta (atoms) Monolayers
0.80
212 1.22
272 0.97
– 0.94
0.82
 J. Weidow, H.-O. Andrén / Int. Journal of Refractory Metals and Hard Materials 29 (2011) 38–43 41

Table 2
WC/(M,W)C phase boundaries analysed with APT.

Co (atoms) Monolayers

WC–TiC–Co 7170 0.46

WC–TiC–Co 17,407 0.56
WC–ZrC–Co 11,907 0.41
WC–NbC–Co 37,991 1.02
WC–NbC–Co 2861 0.37
WC–TaC–Co 952 0.35
WC–TaC–Co 6759 0.75
WC–TaC–Co 1063 0.74

Fig. 2. APT reconstruction proxigram across an analysis of a WC/WC grain boundary in a
WC–TaC–Co material showing Co but no Ta segregation.
relatively small, it might have beneficial effects on the strength of the
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-
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
material from the milling process was found at the grain boundaries.
That Cr segregates to grain boundaries was seen in earlier studies
[7,8]. That Fe segregates to the boundaries and Ni does not was
previously not known. The impact of Fe segregation on the material
properties is at present not known. The amount of segregated Cr and
Fe is very low as an effect on the low total amount in the material.
From a recent study we have seen that Cr can replace up to one third
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
and P for cemented carbides is not known. If embrittling, efforts
should be made to reduce the amount of such impurities in the
powder mixtures.
Regarding the striped pattern in the APT reconstruction of a grain
boundary in the WC–TiC–Co material, this is believed to be caused by
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.
This observation was done with TEM-EDX. Both the K-peak and the L-
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
in the material as an impurity.
4.2. WC/(M,W)C phase boundaries
Segregation of Co to a WC/(Ti,W)C interface has earlier been
reported [8] but now seems to be generalised to all WC/(M,W)C
interfaces. It is interesting to see that the amount of segregated Co is
almost equal in all the analysed boundaries and that it is almost the
same as for WC/WC grain boundaries. The segregation of Cr to the
boundaries has not been reported earlier and the probable reason is
that the methods used in previous work on a WC/(Ti,W)C interface [8]
were not accurate enough or the lining of the mill was different.
4.3. (M,W)C/(M,W)C grain boundary
The presence of a thin Co layer in the analysed (Ta,W)C/(Ta,W)C
grain boundary is in agreement with earlier results for (M,W)C/(M,
W)C grain boundaries [8]. However, this is the first time Cr
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
Due to the way WC grains grow during sintering, it is interesting to
know what the microstructure of the WC/binder phase boundaries
looks like. For V, the most effective grain growth inhibitor [11], a thin
V-rich carbide has been seen [6,7,12–17]. Kawakami et al. has
reported that the thickness is larger for a slowly cooled specimen
than for a rapidly cooled specimen [17]. The conclusion made from
this is that the carbide actually nucleates during cooling after the
liquid state sintering. The grain growth inhibiting effect during liquid
phase sintering is therefore believed to originate from a continuous
adsorption and desorption process of V-atoms at the interface. This
makes it more difficult for W and C atoms to reach the WC/binder
phase boundary thus inhibiting the grain growth. What we see is that
there is an excess of M atoms at some WC/binder phase boundaries,
especially this is the case for Ti atoms in the WC–TiC–Co material. The
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
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.
Still, whether there is a segregation or a thin carbide film at the
Fig. 5. APT reconstruction proxigram across an analysis of a binder/WC phase boundary
in a WC–TaC–Co material.
interface might be uninteresting since what we measure is the
microstructure at temperatures when all diffusion has stopped.
Therefore, the finding of Ti, Zr, Nb and Ta at some interfaces is more
a hint that they were there at the sintering temperature, probably
having a grain growth inhibiting effect and then it will depend on
interfacial energies whether a thin carbide film will be created or not
upon cooling. That segregation only seems to occur to some WC/
binder interfaces and the difference in amount of segregation is
believed to be an effect of the orientation relationship of the two
phases. Segregation might be energetically beneficial to some
interfaces but not to other.
It has been reported that neither Ta [5] nor Zr [21] segregates to WC/
binder phase boundaries. In these studies, the less sensitive TEM-EDX
technique was used and if a small segregation existed, it would have been
very difficult to detect. It should be mentioned that the Ta and Zr contents
in the materials these authors studied were lower than those in this study.
5. Conclusions
Four different cemented carbides with 10 vol.% binder phase and
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.
Lattice parameter (nm) Monolayers
WC–TiC–Co 0.432 0.53
WC–TiC–Co 0.432 0.34
WC–ZrC–Co 0.469 0.01
WC–NbC–Co 0.447 0.06
WC–TaC–Co 0.446 0.20
 J. Weidow, H.-O. Andrén / Int. Journal of Refractory Metals and Hard Materials 29 (2011) 38–43
Segregation to WC/binder phase boundaries was observed for Ti,
Zr, Nb and Ta. Assuming a pure cubic MC phase in the interface, the
segregation corresponded to submonolayer thickness. The thickest
layer, 0.53 close packed monolayers, was found in the WC–TiC–Co
material. Segregation to the phase boundaries was also observed for B
and Cr.
Acknowledgements
Bo Jansson and Jenni Zackrisson from Seco Tools AB are thanked
for the material production and valuable discussions. Göran Wahn-
ström and Sven Johansson from Chalmers University of Technology
and Susanne Norgren from Sandvik Tooling AB are thanked for the
valuable discussions. Eva Olsson from Chalmers University of
Technology is thanked for her assistance with the FEI Titan TEM
instrument.
Financial support was received from Sandvik Tooling AB, Seco
Tools AB and the Swedish Research Council (Vetenskapsrådet).
References
[1] Exner HE. Physical and chemical nature of cemented carbides. Int Met Rev 1979;4:
149–73.
[2] Östberg G, Buss K, Christensen M, Norgren S, Andrén H-O, Mari D, et al.
Mechanisms of plastic deformation of WC–Co and Ti(C, N)–WC–Co. Int J Refract
Met Hard Mater 2006;24:135–44.
[3] Christensen M, Wahnström G. Effects of cobalt intergranular segregation on
interface energetics in WC–Co. Acta Mater 2004;52:2199–207.
[4] Christensen M, Wahnström G. Strength and reinforcement of interfaces in
cemented carbides. Int J Refract Met Hard Mater 2006;24:80–8.
[5] Östberg G, Buss K, Christensen M, Norgren S, Andrén H-O, Mari D, et al. Effect of
TaC on plastic deformation of WC–Co and Ti(C, N)–WC–Co. Int J Refract Met Hard
Mater 2006;24:145–54.
[6] Taniuchi T, Okada K, Tanase T. Sintering behavior of VC-doped micro-grained
cemented carbide. In: Kneringer G, Rödhammer P, Wilhartitz P, editors.
Proceedings of the 14th International Plansee Seminar 1997. Wattens, Austria:
Plansee AG; 1997. p. 644–57. vol. 2.
[7] Weidow J, Andrén H-O. Grain and phase boundary segregation in WC–Co with
small V, Cr or Mn additions. Acta Mater 2010;58:3888–94.
[8] Henjered A, Hellsing M, Andrén H-O, Nordén H. Quantitative microanalysis of
carbide/carbide interfaces in WC–Co-base cemented carbides. Mater Sci Technol
1986;2:847–55.
[9] Kishino J, Nomura H, Shin SG, Matsubara H, Tanase T. Computational study on
grain growth in cemented carbides. Int J Refract Met Hard Mater 2002;20:31–40.
[10] Roebuck B, Bennett EG, Byrne WP, Gee MG. Characterisation of baseline
hardmetals using property maps. NPL Report CMMT(A)172; April 1999.
43
[11] Hayashi K, Fuke Y, Suzuki H. Effects of addition carbides on the grain size of WC–
Co alloy. J Jpn Soc Powder Met 1972;19:67–71.
[12] Egami A, Ehira M, Machida M. Morphology of vanadium carbide in submicron
hardmetals. In: Bildstein H, Eck R, editors. Proceedings of the 13th International
Plansee Seminar 1993. Wattens, Austria: Plansee Metal AG; 1993. p. 639–48. vol. 3.
[13] Jaroenworaluck A, Yamamoto T, Ikuhara Y, Sakuma T, Taniuchi T, Okada K, et al.
Segregation of vanadium at the WC/Co interface in VC-doped WC–Co. J Mater Res
1998;13:2450–2.
[14] Yamamoto T, Ikuhara Y, Sakuma T. High resolution transmission electron
microscopy study in VC-doped WC–Co compound. Sci Technol Adv Mater
2000;1:97–104.
[15] Lay S, Hamar-Thibault S, Lackner A. Location of VC in VC, Cr3C2 codoped WC–Co
cermets by HREM and EELS. Int J Refract Met Hard Mater 2002;20:61–9.
[16] Lay S, Thibault J, Hamar-Thibault S. Structure and role of the interfacial layers in
VC-rich WC–Co cermets. Philos Mag 2003;10:1175–90.
[17] Kawakami M, Terada O, Hayashi K. Effect of sintering cooling rate on V segregation
amount at WC/Co interface in VC-doped WC–Co fine-grained hardmetal. J Jpn Soc
Powder Powder Metall 2004;8:576–85.
[18] Yamamoto T, Ikuhara Y, Watanabe T, Sakuma T, Taniuchi Y, Okada K, et al. High
resolution microscopy study in Cr3C2-doped WC–Co. J Mater Sci 2001;36:
3885–90.
[19] Delanoë A, Bacia M, Pauty E, Lay S, Allibert CH. Cr-rich layer at the WC/Co interface
in Cr-doped WC–Co cermets: segregation or metastable carbide? J Cryst Growth
2004;270:219–27.
[20] Weidow J, Norgren S, Andrén H-O. Effect of V, Cr and Mn additions on the
microstructure of WC–Co. Int J Refract Met Hard Mater 2009;27:817–22.
[21] Yamamoto T, Yamanaka Y, Taniuchi T, Shirase F, Tanase T, Ikuhara Y. HRTEM study
for cemented carbides doped with transition metal carbides of VC, NbC and ZrC.
In: Sigl LS, Rödhammer P, Wildner H, editors. Proceedings of the 17th
International Plansee Seminar 2009. Volders, Austria: Plansee Group; 2009.
vol. 3, AT5.
[22] Weidow J, Andrén H-O, Jansson B, Zackrisson J, Norgren S. Analysis of interfaces in
WC–Co with cubic carbide additions. In: Sigl LS, Rödhammer P, Wildner H, editors.
Proceedings of the 17th International Plansee Seminar 2009. Volders, Austria:
Plansee Group; 2009. vol. 2, HM3.
[23] Andersson J-O, Helander T, Höglund L, Shi PF, Sundman B. Thermo-Calc and
DICTRA, computational tools for materials science. Comp Tools Mater Sci 2002;26:
273–312.
[24] Thermo-Calc Software AB. http://www.thermocalc.com/res/pdfDBD/
dbd_ccc1.pdf. March 29 2010.
[25] Weidow J, Zackrisson J, Jansson B, Andrén H-O. Characterisation of WC–Co with
cubic carbide additions. Int J Refract Met Hard Mater 2009;27:244–8.
[26] Rolander U. A method for sharpening FIM-specimens. J Phys 1986;47:449–52 [C7].
[27] Andrén H-O, Henjered A, Kingham D. On the charge state of tungsten ions in the
pulsed-field atom probe. Surf Sci 1984;138:227–36.
[28] Weidow J, Johansson S, Andrén H-O, Wahnström G. Transition metal solubilities in
WC in cemented carbides. Submitted for publication.
[29] Gale WF, Totemeier TC. Smithells metals reference book 8th ed. Great Britain:
Elsevier Butterworth-Heinemann; 2004.
[30] Bhadeshia HKDH, Honeycombe RWK. Steels microstructure and properties 3rd ed.
Great Britain: Elsevier Butterworth-Heinemann; 2006.
[31] Lai Z, Nordén H. The enhanced concentration of Ni at structural dislocations in a
grain boundary in W. J Phys 1988;49:341–5 [C6].