Applied Surface Science 257 (2011) 8894–8900

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Experimental investigations and DICTRA simulations on formation of

diffusion-controlled fcc-rich surface layers on cemented carbides
José Garcia a,∗ , Orlando Prat b
a
Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, D-14109 Berlin, Germany
b
Max Planck Institute für Eisenforschung GmbH, Max Planck Str. 1, D-40237 Düsseldorf, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Wear resistant fcc-rich surface layers were produced on cemented carbides by nitridation of
Received 1 March 2011 W–Ti–Ta–Nb–Co–C compositions at 1400 ◦ C in nitrogen atmosphere. A 15 ± 3 ␮m thick (Ti,Ta,Nb,W)(C,N)
Received in revised form 5 May 2011 top-layer formed on the surface of the cemented carbides. The driving force for formation of the fcc-rich
Accepted 5 May 2011
layers was the difference in nitrogen activity between the sintering atmosphere and the cemented carbide
Available online 12 May 2011
bulk, which promoted in-diffusion of nitrogen and out-diffusion of Ti, Ta and Nb. The diffusion-controlled
process was modeled by DICTRA considering that all diffusion occurred in the liquid binder phase of a
Keywords:
dispersed system model with a labyrinth factor of (f) = f. Good agreement between experimental and
Cemented carbides
Nitridation
simulations regarding layer thickness, phase fraction distribution and element profiles was obtained for
Diffusion the presented model.
Fcc-rich surface layers © 2011 Elsevier B.V. All rights reserved.
DICTRA modeling

1. Introduction
Cemented carbides are composite materials consisting of hard
refractory carbide phases (WC, TiC, TaC, NbC, Mo2 C) embedded in
a ductile metal matrix binder phase (Co, Fe, Ni). Cemented carbides
are produced by powder metallurgy methods. Some applications
of cemented carbides are as cutting tools, wear parts, components
of drill bits or road headers and sharp cutting teeth [1].
In several industrial applications the production of graded
cemented carbides is necessary. The modification of the near-
surface microstructure (∼20 ␮m) on cemented carbides in order
to produce tough graded layers is a state-of-the-art process [2,3].
WC–Co-rich graded layers depleted of cubic mixed carbides (TiC,
TaC, NbC), known as fcc-free or ␥-phase free layers, improve the
surface toughness of coated cemented carbides. The graded lay-
ers prevent the propagation of thermal cracks – originated in the
coating layer during the cooling step of chemical vapor deposition
processes – into the bulk of the cemented carbide. Numerous inves-
tigations have been carried out on formation of fcc-free layers on
cemented carbides; see i.e. [4–7].
The production of hard wear resistant layers enriched in cubic
carbides and depleted of binder phase on cemented carbides (also
known as fcc-rich or ␥-phase rich layers) has been also investigated
[8–12]. Due to the higher hardness of mixed carbides (∼28 MPa)
∗ Corresponding author.Tel.: +49 30 8062 42764; fax: +49 30 8062 42047.
E-mail address: jose.garcia@helmholtz-berlin.de (J. Garcia).
compared to WC (∼22 GPa) and the absence of the ductile binder
phase, the fcc-rich graded layers present higher wear resistance as
compared to the bulk. Although the enrichment of mixed carbides
in the near-surface of cemented carbides improves the wear resis-
tance of cemented carbides, the mechanical properties of cemented
carbides containing fcc-rich layers are inferior to the mechanical
properties of coated cemented carbides. Nevertheless fcc-rich lay-
ers has gained industrial acceptance as surface conditioning for
further deposition of diamond layers (due to the suppression of
binder phase) [13] or deposition of Ti(C,N) layers (due to a bet-
ter chemical adhesion between the fcc-rich outer-surface and the
deposited layer) [14].
Both the formation of fcc-free and fcc-rich layers at liquid
phase sintering temperatures are diffusion-controlled processes.
The transport media for diffusion is the liquid binder phase, since
the diffusivity of the elements is higher in the liquid metal than in
the solid carbides.
The formation of graded layers on cemented carbides is con-
trolled by the thermodynamic coupling between Ti, Ta, Nb and
nitrogen [5–7]. Contrary, at the sintering conditions used for the
production of graded layers, W does not react with N to form stable
W-nitrides due to unfavorable thermodynamic conditions [10]. For
the nitride forming elements, the solubility of the nitride (i.e. TiN)
in the liquid binder depends on the nitrogen equilibrium partial
pressure (PN2 EQUIL ) of the system. If the nitrogen partial pressure
(PN2 ) is below PN2 EQUIL , such as in the case of vacuum sintering, the
metal (i.e. Ti) will dissolve in the binder phase releasing nitrogen,
which diffuses out from the material.

0169-4332/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2011.05.024
 J. Garcia, O. Prat / Applied Surface Science 257 (2011) 8894–8900
The interaction of the sintering body with the sintering atmo-
sphere is crucial on the formation of graded outer-surface layers.
During liquid phase sintering dissolution and re-precipitation of
hard phases in the metal binder take place but also chemical
reactions with the sintering atmosphere, which changes the local
composition of the sintering body [15]. These changes on local com-
positions are the driving force for the formation of surface graded
layers [5,6].
Simplified schemes for both fcc-free and fcc-rich surface layer
formation on WC–Ti(C,N)–Co cemented carbides are shown in
Fig. 1. The fluxes of Ti and N, which are a consequence of activity
differences, are schematized.
In TiN-containing cemented carbides, the formation of fcc-free
layers (Fig. 1a) is due to dissolution of TiN in the binder. Nitro-
gen is released out of the material due to the nitrogen activity
difference between the bulk (aN BULK > 0) and the vacuum sinter-
ing atmosphere (aN ATM = 0). Due to the thermodynamic coupling
between Ti and N, inward diffusion of Ti to regions of high nitrogen
content is established, which promotes the formation of a WC–Co
layer free of TiN.
For the formation of fcc-rich layers it is necessary to sinter
cemented carbides in a nitrogen-containing atmosphere. A higher
nitrogen activity on the surface compared to the bulk promotes
the out-diffusion of Ti towards the surface and the formation of
a Ti(C,N)-rich layer (Fig. 1b). A way to produce such fcc-rich lay-
ers is by sintering TiC-containing cemented carbides without any
nitrides in the starting formulation (aN BULK = 0) in a nitrogen rich
atmosphere (aN ATM > 0).
The production of fcc-free and fcc-rich layers with other type
of cubic carbides (TaC or NbC) is also possible. Here the different
thermodynamic coupling between Ta, Nb and N must be considered
[16] in order to drive the out-diffusion of Ta and Nb towards the
surface in the presence of a nitrogen-rich atmosphere.
The formation of fcc-free layers on cemented carbides has been
previously modeled by DICTRA [17–19]. The thermodynamic cal-
culations have been carried out with ThermoCalc using a special
thermodynamic database for cemented carbides [20]. The exper-
imental and simulated data showed good agreement indicating
that DICTRA simulations are an important tool for the prediction
of graded layer formation on cemented carbides.
To the date no thermodynamic modeling on the kinetics of for-
mation of fcc-rich graded layers on cemented carbides has been
reported in the literature.
In this work fcc-rich layers were produced on
WC–Ti(C,N)–(Ta,Nb)C–Co cemented carbides by nitridation at
liquid phase temperatures. The microstructure was characterized
by scanning electron microscopy (SEM) and X-ray diffraction
(XRD). The formation of fcc-rich graded layers was simulated by
DICTRA. The simulation results were compared to the experimental
results to validate the DICTRA predictions.
2. Material and methods
2.1. Experimental
Cemented carbides samples were prepared from a mixture of
WC, Co, TiC and (Ta,Nb)C with additions of 2 wt.% wax. Raw pow-
ders provided by the companies H.C. Starck (WC with a Ctotal of
6.13 ± 0.05, TiC a with a Ctotal of 19.12 ± 0.05 wt.% and (Ta,Nb)C
50/50 with a Ctotal of 8.75 ± 0.15 wt.%) and Umicore (Co extra fine
quality (1.2–1.5 ␮m) containing 0.2% impurities) were used for the
production of the samples. The powders were mixed in a planetary
milling unit for 8 h, dried and pressed in an uniaxial compact-
ing unit. The powder mixture of the cemented carbide is given in
Table 1. Samples were dewaxed and sintered in vacuum at 1450 ◦ C
8895
Table 1
Powder mixture composition (in wt.%).
WC Co TiC (Ta0.5 Nb0.5 )C
57.5 9.5 18.0 15.0
for 1 h. In a second step the as-sintered samples were nitrided at
1400 ◦ C for 5 h in a nitrogen atmosphere of 200 mbar and cooled
down in the nitrogen-rich atmosphere. Nitrided samples were cut,
embedded in resin and polished. The formation of the fcc-rich layer
was investigated by light microscopy and SEM. Element distri-
bution in the near-surface was determined by SEM–EDX (energy
dispersive X-ray spectroscopy) of cross sectioned samples. Mea-
surements of phase fraction distributions on the near-surface area
were performed on SEM images using the software analysis 5.0
[21]. The contrast between phases of the SEM image was used for
the determination of the phase fraction distribution as a function
of depth. XRD of the surface of as-sintered and nitrided samples
was carried out using Cu K␣-radiation. The surface roughness was
measured with a diamond sensor after DIN 4768/1.
2.2. DICTRA model for simulation
As previously mentioned the formation of the fcc-rich layers is
due to the interaction between Ti, Ta and Nb and nitrogen. The
Ti, Ta and Nb fluxes towards the surface are driven by the higher
nitrogen activity on the surface compared to the bulk, but also by
the presence of other elements in the liquid cobalt phase, so that the
fluxes of all diffusing elements are coupled by their thermodynamic
interaction.
The multi-component diffusion theory was applied for the
description of the fluxes of species driven by a concentration gradi-
ent [22]. The law relating flux and concentration gradient is given
by the multi-component extension of Fick’s first law:

n−1
∂cj
Jk = − n
Dkj (1)
∂z
j=1
where Jk is the flux of species k in the direction of the z-axis and
∂cj /∂z is the concentration gradient of species. The diffusion coef-
n , is a product of two matrices; one consisting only
ficient matrix Dkj
of pure thermodynamic information and one consisting of the so-
called mobilities, and can be expressed as follows:
  
n ∂i ∂i
Dkj = (ıik − xk )xi Mi − (2)
∂xj ∂xn
i
indicating that the diffusion of one element depends on the con-
centration gradient of other elements. Here xk is the mole fraction
of element k and i is the chemical potential of the element i, and n
is an arbitrary chosen reference element. ıik is the Kronecker delta;
i.e. ıik = 1 when j = k and ıik = 0 otherwise.
By absolute-reaction theory argumentation [22] the mobility
parameter Mk , for an element k in a given phase, can be divided
into a frequency factor Mk0 and an activation energy factor Qk :
Mk0  −Q 
k
Mk = exp (3)
RT RT
where R is the gas constant and T is the absolute temperature. Mk0
and Qk are not constant; hence their values depend on temperature,
pressure and composition.
A diffusion model considering a continuous matrix with dis-
persed phases available in the DICTRA software was used for the
kinetic simulations. Since the diffusion occurs only in the liquid
binder, the hard phases are considered obstacles, which presence
reduces the diffusion paths. To simulate this effect, a so-called
8896 J. Garcia, O. Prat / Applied Surface Science 257 (2011) 8894–8900

Fig. 1. Simplified schemes for graded layer formation on cemented carbides indicating the titanium and nitrogen fluxes which lead to the graded layer formation. (a) Fcc-free
layer formation and (b) fcc-rich layer formation.

labyrinth factor, (f), can be defined which reduces the diffusion

coefficient matrix:

n n
Dkj eff
= (f )Dkj (4)

where Dkj n is the effective diffusion coefficient matrix.

eff
Frykholm et al. [18] found out that the binder content deter-
mines the rate of gradient formation. They demonstrated that the
only effect of high binder contents is that larger binder volumes
allow for higher diffusion fluxes and thus faster gradient growth
is achieved. They found out that by using a labyrinth factor  = f
– where f is the volume fraction of the matrix – good agreement
between experiments and simulations were obtained, meaning
that the gradient zone width and the binder content show a linear
relationship. In this work a labyrinth factor  = f was then chosen.
For the kinetic model this means that the value of the frequency
factor Mk0 will depend on the thermodynamic description utilized
as well as the choice of labyrinth factor (f).
In the kinetic database used by DICTRA, parameters for the
atomic mobilities of the elements in a given phase are stored Fig. 2. Scheme of DICTRA model used for simulation.
rather than diffusivities. For liquid binder systems the availabil-
ity of such data is limited and assumptions are needed. In this
work the same mobility for all diffusing elements in the liquid Co
was assumed. Similar values for the activation energy and the fre-
quency factor as reported in [17] were considered; Q = 65,000 J/mol
and Mk0 = 9.24 × 10−7 m2 /s. The nitriding atmosphere was mod-
eled considering a nitrogen activity of 0.2 at the surface. For the
DICTRA simulation a planar geometry with 300␮m of cell size
was defined. Spherical geometry was assumed for the dispersed
phases. The model used for the simulations is exemplified in
Fig. 2.
The ThermoCalc database TCFe6 was used for the thermo-
dynamic calculations. This database includes thermodynamic
formulations for the systems of interest. The main limitation of this
database is the lack of description of the element Ta. The calcula-
tions were performed with the elements Co, W, Ti, Nb, C and N. The
Ta content was not considered for performing the calculations (see
Table 2). Fig. 3. SEM image of nitrided cemented carbide (1400 ◦ C/5 h/200 mbar N2 ). A fcc-
rich graded layer of ∼15 ␮m ± 3 is formed on the near-surface of the cemented
carbide. Light gray phase (WC), gray phase (fcc-phase), dark phase (cobalt).

3. Results and discussions

Table 2
Composition by element used for DICTRA modeling (in wt.%). 3.1. Experimental results
Co C Ti Nb W
In Fig. 3 a SEM image of the cross section of the cemented car-
9.5 8.46 14.39 6.64 Balance
bide after the nitridation process is shown. The light gray phase
 J. Garcia, O. Prat / Applied Surface Science 257 (2011) 8894–8900 8897

Fig. 4. SEM micrograph (top-view) of the cemented carbide surface for the condition as-sintered and nitrided. EDX measurements of elements at the surface showing the
formation of a (Ti,W,Ta,Nb)(C,N) phase on the surface of the nitrided sample.

Table 3 tering step. XRD patterns of the surface of the cemented carbide in
Surface metal element concentration in wt.% (SEM–EDX).
the as-sintered condition showed reflections of, as expected, three
Element As-sintered Nitrided phases: WC, fcc and Co (see Fig. 5a).
TiK 13.0 ± 0.2 30.5 ± 0.2 The surface morphology of the nitrided cemented carbide is
NbL 6.0 ± 0.2 7.8 ± 0.2 shown in Fig. 4b. Small irregular rounded particles are observed.
TaL 7.5 ± 0.2 29.3 ± 0.2 SEM–EDX analyses reveal high Ti and Ta contents on the surface
CoK 10.5 ± 0.2 2.0 ± 0.2 as compared to the as-sintered condition (Table 3). A reduced
WL 55.6 ± 0.2 24.8 ± 0.2
content of W (∼55 wt.% as-sintered/∼24 wt.% nitrided) was mea-
sured. A very low Co content was determined compared to the
as-sintered condition (∼2 wt.% nitrided/∼10 wt.% as-sintered). The
corresponds to WC, the gray phase is the mixed cubic carbide
nitrogen and carbon contents were not measured due to limita-
phase (fcc-phase) and the dark phase is the cobalt binder. It can
tions of the characterization method. XRD analysis of the nitrided
be observed that a fcc-rich graded layer of ∼15 ␮m ± 3 formed
sample revealed reflections of the fcc phase, but also a clear WC0 0 2
on the near-surface of the cemented carbide. A rough fcc-rich
reflection (Fig. 5b).
layer (roughness Ra = 2.0 ± 0.2 ␮m) formed after nitridation. Sim-
A lattice parameter of 4.346 Å was determined for the fcc-rich
ilar effects on surface roughness due to nitridation on presence of
phase which corroborate the formation of a complex mixed car-
a liquid phase have been reported previously in [16,23]. Few WC
bide of the type (Ti,W,Ta,Nb)(C,N). Since the lattice parameter of
inclusions and few pores were found in the graded layer. Beneath
the Ti(C,N) phase varies between 4.241 Å (TiN) and 4.328 Å (TiC) it
the graded layer, the cemented carbide was not affected by the
turns out that considerable contents of Ta, Nb are present in the
nitridation process showing the microstructure of the as-sintered
fcc-rich layer. The lattice parameters of TaC and NbC are 4.455 Å
condition.
and 4.470 Å respectively [24]. Hence both Ta and Nb increases the
A SEM micrograph of the cemented carbide surface (top-view)
lattice parameter of the Ti(C,N) phase.
for the conditions as-sintered and nitrided is shown in Fig. 4. On the
As previously mentioned the high nitrogen activity on the
top surface of the as-sintered cemented carbide rounded fcc-phase
surface promotes the out-diffusion of the elements showing a
crystals and sharp-edged WC crystallites are clearly seen (Fig. 4a).
high affinity to nitrogen, the so-called carbonitride former ele-
The measured concentration of the metallic elements at the sur-
ments (Ti, Ta and Nb). The out-diffusion occurs through the
face (Table 3) showed similar element concentrations as for the
liquid cobalt binder matrix. Ti, Ta and Nb reacts with nitrogen
as-sintered bulk sample (Table 4). A higher Co content on the sur-
to form a (Ti,Ta,Nb)N layer on the surface of the cemented car-
face compared to the bulk of the sample was measured, which can
bide. However, due to the presence of carbon and some tungsten
be explained by Co-transport to the surface during the vacuum sin-
dissolved in the liquid binder; these elements will also combine
with the Ti, Ta, Nb and N to form the complex mixed carbonitride
Table 4 (Ti,Ta,Nb,W)(C,N). Doi et al. [25] made thermodynamic calcula-
Analyzed chemical composition by element after sintering (in wt.%). tions of the equilibrium pressure of nitrogen of some (Ti,W)(C,N)
compounds, showing that by substituting carbon with nitrogen
Co W Ti Ta Nb C N
the solubility of W in the (Ti,W)(C,N) phase decreased. Due to the
9.5 ± 0.5 54.0 ± 0.5 14.0 ± 0.5 7.0 ± 0.5 6.3 ± 0.5 8.5 ± 0.5 0.0 high nitrogen content of the (Ti,Ta,Nb,W)(C,N) carbonitride phase
8898 J. Garcia, O. Prat / Applied Surface Science 257 (2011) 8894–8900

Fig. 5. XRD (E = 8.05 keV, Cu K(-radiation, ( = 0◦ ) difractogramms for cemented carbides (a) as-sintered and (b) nitrided.

formed upon this process, the W content in the fcc-rich layer is
low compared to the content of Ti, Ta and Nb. This observation
is in agreement with the measured metal element concentrations
(Table 3) and SEM–EDX mappings of Ti, W and Nb of the nitrided
surface of the cemented carbide. SEM–EDX mappings of the ele-
ments W, Co, Ti and Nb on the near-surface area (cross-section)
of the nitrided cemented carbide are shown in Fig. 6. The graded
layer is rich in Ti and Nb. The W content in the layer is lower
compared to the bulk. Few Co is present on top of the fcc-rich
layer.
3.2. DICTRA simulation results
The results of the DICTRA simulation after 5 h nitridation at
1400 ◦ C in 200 mbar N2 and the experimental results of the phase
fraction distribution are shown in Fig. 7. The phase fraction dis-
tribution was determined on SEM images of the nitrided sample.
The quantitative determination of phase fractions shows the for-
mation of a fcc-rich layer of ∼15 ␮m. The high fcc-content at the
surface decreases towards the bulk. Beneath the fcc-rich layer a
slight decrease of the fcc-phase was measured. This effect was
expected since the out-diffusion of the carbonitride former ele-
ments Ti, Ta and Nb towards the surface produces a depletion
of such elements and the total amount of fcc-phase beneath the
fcc-rich layer. The DICTRA simulation of the fcc-phase distribu-
tion shows a good agreement with the experimental values. Also
the simulated volume fraction of WC and cobalt shows a good
agreement with the experimental results. A very reduced amount
of cobalt (below 1 wt.%) was measured by EDX on top of the
fcc-rich layer. DICTRA simulations predict however a Co-free fcc-
rich layer. This discrepancy can be explained by the fact that the
initial condition at the outer-surface was modified due to the

Fig. 6. SEM–EDX mapping of nitrided cemented carbide showing the metal element distributions. The graded layer is rich in Ti and Nb.
 J. Garcia, O. Prat / Applied Surface Science 257 (2011) 8894–8900
Fig. 7. Results of DICTRA simulation for the Co binder phase, WC phase and fcc-
phase and corresponding experimental data. The volume fraction of phases was
measured in the nitrided sample by imaging analysis.
Fig. 8. DICTRA simulations of element profile distribution on the near-surface of the cemented carbide after nitridation.
8899
Co-enrichment during the initial vacuum sintering step (see Section
3.1). This situation was not considered in the DICTRA simula-
tions.
DICTRA simulations of the element profiles for N, Ti, W and Co
on the near-surface of the cemented carbide after nitridation are
shown in Fig. 8. A clear nitrogen gradient from the surface towards
the bulk is simulated. The nitrogen content decreases in the first
∼20 ␮m of the near outer-surface, which corresponds with the
thickness of the fcc-rich layer. A maximal nitrogen in-diffusion of
∼100 ␮m into the bulk was simulated. The titanium profile shows
an increment of the content of Ti in the region of the fcc-rich layer
of ca. 2 times compared to the bulk conditions. Beneath the graded
layer region the Ti profile decreases until the bulk conditions are
reached. A similar profile as for Ti was modeled for the element
Nb (not shown in Fig. 8). The cobalt distribution is almost zero
in the region of the fcc-rich layer. Beneath the graded layer an
increment of Co is modeled, which decreases to reach the bulk con-
ditions value. The simulated W content decreases, as expected, in
the fcc-rich layer zone.
The element profile distributions were not measured in this
work due to lack of resolution of the characterization techniques
used. However, the simulated N, Ti, W and Co profiles fit with
the element profiles measured by electron microprobe analy-
sis (EPMA) and glow discharge optical spectroscopy (GDOS) in
8900 J. Garcia, O. Prat / Applied Surface Science 257 (2011) 8894–8900
cemented carbides presenting similar fcc-rich layers on previous
works [10,11].
4. Conclusions
Fcc-rich graded layers were produced by liquid phase sinter-
ing of cemented carbides in a nitrogen atmosphere of 200 mbar
at 1400 ◦ C for 5 h. The production process leads to the formation
of (Ti,Ta,Nb,W)(C,N) layers of ca. 15 ␮m with considerable high
roughness on the surface of the cemented carbide.
Simulations of the diffusion-controlled process were performed
with the software DICTRA. The kinetic simulations of formation
of the fcc-rich layers showed a good agreement with the experi-
mental results, which shows that the defined boundary conditions
and fitting parameters (mobilities, labyrinth factor, liquid transport
media) are adequate for this specific experimental situation. The
thickness of the graded layer, the phase distribution in the near-
outer surface area and the element profiles for all diffusion species
were successfully modeled.
Acknowledgements
José Garcia thanks financial support of the joint research group
“Microstructural analysis”,Helmholtz-Zentrum Berlin für Materi-
alien und Energie GmbH/Ruhr Universität Bochum. Dr. H. Pinto and
Dr. C. Barbatti (both former Max Planck Institut für Eisenforschung
GmbH) are acknowledged for XRD and SEM support.
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