Int.

Journal of Refractory Metals and Hard Materials 30 (2012) 42–47

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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

Effect of cobalt replacement by nickel on functionally graded cemented carbonitrides

M. Mohammadpour ⁎, P. Abachi, K. Pourazarang
Sharif University of Technology, Department of Materials Science and Engineering, Azadi Street, Tehran, P.O. Box: 11365-9466, Iran

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

Article history: Functionally graded cemented carbonitrides (FGCCs) are applied in cutting tools industry. Indexable inserts
Received 22 May 2011 made from mentioned alloys have superior cutting performance and tool life thanks the formation of a surface
Accepted 1 July 2011 modified layer with enhanced properties as well as crater wear resistance. Cemented carbonitrides are made
of hard carbide/nitride/carbonitride particles that have been embedded in a metallic binder. Excellent wetting
Keywords:
ability of tungsten carbide with cobalt has made this metal the first choice as binder. However, cobalt has high
Powder metallurgy
Cemented carbonitride
cost and environmental pollution impacts. Substitution of cobalt with other metals has always been figured
Surface modification out. Some other metals that have been used as binder are iron, nickel and manganese. In addition to lower
Cutting tool cost, nickel has higher corrosion resistance than cobalt. In the present work, gradual substitution of cobalt
Nickel with nickel in WC/2.5TiC0.7N0.3/2.5TiC/0.2VC/8Co (numbers indicate wt.%) cemented carbonitride has been
Computational thermodynamics studied. This is supposed to make some alterations in mechanical and magnetic properties as well as
formation of Cubic Free Layer. As sintered samples with different binder characteristics were prepared by
powder metallurgy techniques and use of Hot Isostatic Pressure (HIP) and vacuum furnaces. Magnetic
saturation, coercive force, Vickers hardness, and transverse rupture strength tests were carried out together
with optical and scanning electron microscopy. Computational thermodynamics was applied to explain
changes in magnetic properties of investigated alloys as well as plotting phase diagrams. Complete
displacement of cobalt by nickel made an increase in transverse rupture strength (TRS) of final alloy by 37%
with less than 6% decrease in Vickers hardness and doubled the thickness of Cubic Free Layer.
© 2011 Elsevier Ltd. All rights reserved.

1. Introduction called “cemented carbonitrides” were developed. TiCN increases

Because of high hardness, tungsten carbide is being studied as a
part of hard materials. WC is also one of industrially important none-
oxide Ceramics. Since 1920, a wide group of materials under the name
of “cemented carbides” that are originally metal-carbide composites,
developed for being applied to wear resistance industry [1]. Because
of excellent combination of toughness and hardness, the metal is
cobalt most of the times [2].
Besides WC, other transition metal carbides are being added to
cemented carbide phase to increase resistance against different wear
mechanisms [3]. Addition of tantalum/niobium carbide solid solution
has a dramatic effect on diffusion wear resistance of cutting tools
during machining of steels. Addition of vanadium carbide and/or
titanium carbide decreases the Ostwald ripening mechanism and
consequently controls the grain growth of WC [1,4]. Since TiC has
lower toughness than WC, the concentration in the starting
formulation is not more than 18 wt.% [1].Cermets are a group of
cemented carbides that are based on titanium carbide or carbonitride
as hard phase and nickel as metallic binder [5]. After addition of
titanium nitride and carbonitride to cemented carbides, new alloys
⁎ Corresponding author. Tel.: + 98 9126191272.
E-mail addresses: mohammadpour@alum.sharif.edu,
meysammuhammadpour@gmail.com (M. Mohammadpour).
thermal and chemical stability at elevated temperatures of high
cutting speed demands. Microstructure of a typical as sintered
cemented carbonitride contains three different phases; a binder
matrix phase with metallic nature, a facetted WC phase with h.c.p.
crystallographic structure and a round carbonitride solid solution
phase with f.c.c. structure [5]. A surface modification process in
cemented carbonitrides was developed in 1995 [5]. During final
sintering steps of cemented carbonitrides that liquid phase is present,
inward or outward diffusion of nitrogen can occur at the surface layer
of about 10–60 μm based on sintering regime. This is the direct result
of interaction of substrate with sintering atmosphere. Nature of
diffusion implies that the concentration profile of nitrogen from
surface to bulk must be gradual. At the same time, other elements that
have different affinities to nitrogen diffuse in different directions but
perpendicular to the surface. The most important element that
migrates to areas with more nitrogen concentration is titanium
whereas tungsten and cobalt are less reactive with nitrogen. So they
diffuse to locations with less quantities of nitrogen. The final result of
described parallel diffusions is formation of a gradient in chemical
composition from surface to bulk [5,6]. There are two types of
functionally graded cemented carbonitrides (FGCCs) depending on
applied sintering atmosphere.
In type A of FGCCs the partial pressure of nitrogen in sintering or
post treatment atmosphere is lower than equilibrium partial pressure

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 M. Mohammadpour et al. / Int. Journal of Refractory Metals and Hard Materials 30 (2012) 42–47 43

of nitrogen (e.g. in vacuum sintering). So nitrogen in cemented

carbonitride substrate is thermodynamically unstable and transfers to
gas phase from the surface. Nitrogen depletion at the surface causes a
concentration gradient that launches a diffusion process. As a result,
titanium tends to leave the surface and diffuse to the bulk where more
amounts of nitrogen are still present. Metallic binder that has less
affinity to nitrogen diffuses to surface at the same time. Finally, a
surface layer that is free of carbonitrides and rich in tough binder will
form. Since the carbonitride phase has cubic structure this layer is
called Cubic Free Layer (CFL) [6].
In type B of FGCCs partial pressure of nitrogen in atmosphere is
higher than equilibrium partial pressure of nitrogen. Therefore, the
reverse conditions affect the diffusion process. Enhanced concentra-
tion of nitrogen at the surface and diffusion of titanium make a
carbonitride rich layer at the surface. In both types of FGCCs, it has
been observed that other carbonitride former transition metal
carbides follow the same route that titanium does [7,8]. There are
several works that describe formation mechanisms of gradient layer
in FGCCs [9]. However, kinetic aspects are more interesting from an
industrial point of view. Because of diffusion nature, thickness of
graded zone corresponds to parabolic law [8]. Here comes some
manufacturing design parameters that influence formation rate of
mentioned gradient layer; initial cubic phase composition of
cemented carbonitride can affect the formation rate and microstruc-
ture of graded zone [10]. Addition of NbC can increase the graded zone
formation rate [10]. Diffusion coefficient in liquid phase as diffusion
medium is hundreds of times larger than solid phase. As a result,
increasing the volume fraction of binder phase as the only stable
liquid phase can increase the kinetics of graded zone formation as well
as increasing the nitrogen partial pressure [8].
Formation of microcracks in CVD coatings is inevitable. These
cracks may propagate into substrate during working conditions and
cause failure. In type A-FGCCs, ductile CFL acts as a barrier for
propagation of CVD coating crack residue [11].
Cutting tools industry is the main application area of FGCCs. Crater
and flank wear phenomena reduce the tool life and its performance.
Measuring depth of formed crater (KT) and width of worn flank
(VBmax) are good means to evaluate wear resistance of tool in cutting
conditions (e.g. cutting speed and work piece material) [5,12].
Continuous measurement of KT and VBmax during machining using
a traditional cemented carbide and a type B-FGCCs, revealed that tool
life of an indexable insert having a TiN layer that was built by high
pressure nitrogen sintering, was five times longer than traditional one Fig. 1. SEM micrograph of: a) WC, b) Co and c) Ni powder.
[5].
Other than tool life and cutting performance studies of cemented
carbides, there are some trends to find alternative materials for was coated on all powder samples to increase sharpness of images.
tungsten carbide and cobalt. Some reasons are scarcity and high prices WC, Co and nickel had mean particle size of 2.5, 1 and 3 μm
of extraction from main ore deposits and environmental pollution respectively. Particle size distribution of all additive carbides and
viewpoints. Iron and nickel were precisely studied to become carbonitrides was in the range of 1–3 μm. The chemical composition
nominates for cobalt replacement [13]. However, iron showed poor of investigated specimens is given in Table 1. The composition was
corrosion and wear resistance and tendency to form unwanted phases designed so that Ni/(Ni + Co) ratio was gradually increased and hard
when combined with WC and as a result of unsatisfactory properties. phase composition was kept at the same. After ball milling and
Because of crystallographic similarity to cobalt, nickel has more compaction of powder mixtures into green parts, specimens were
potential to become an alternative. However, there is not enough placed on a graphite tray and sintered spontaneously in an industrial
experimental dealing with complete and partial displacement of scale HIP furnace with 1420 °C maximum sintering temperature for
cobalt by nickel and outcome of that on mechanical and microstruc-
tural properties as well as magnetic behavior of FGCCs. It has been
Table 1
proved that addition of grain growth inhibitor carbides is necessary to
Powder mixture of studied specimens.
control grain size of carbide phase in WC–Ni alloys [4,14].
Specimen no. Composition (wt.%)
2. Experimental WC Co Ni TiC0.7N0.3 VC WC/TiC (50/50)

1 Balance 8 – 2.5 0.2 2.5

Initial powders including WC, cobalt, nickel, TiC0.7N0.3, VC and WC/ 2 Balance 6 2 2.5 0.2 2.5
TiC (50/50 solid solution) were weighted to form initial powder 3 Balance 4 4 2.5 0.2 2.5
mixture of investigated specimens. SEM micrographs of WC, Co and Ni 4 Balance 2 6 2.5 0.2 2.5
5 Balance – 8 2.5 0.2 2.5
powders are shown in Fig. 1a–c. A thin (less than 20 nm) film of gold
44 M. Mohammadpour et al. / Int. Journal of Refractory Metals and Hard Materials 30 (2012) 42–47
hold time of 20 min and under argon pressure of 20 atm to eliminate
almost all porosities in sintered specimens. For production of type A-
FGCC specimens, another set of compacts prepared from the same
powder mixtures, were sintered in 0.5 mbar vacuum furnace with
1450 °C maximum temperature, and equivalent hold time of 4 h.
Transverse rupture strength tests were carried out on HIPed
samples using Zwick-1465 series machine. After performing magnetic
tests, samples were cut, mounted in resin and polished. Vickers
hardness tests were performed using a Wolpert-MC110 instrument.
Microstructure studies were conducted on etched specimens using a
Hitachi-S4160 scanning electron microscope equipped with second-
ary electron detector. Murakami solution was used as etchant.
Thicknesses of CFL on each specimen were measured using built-in
scale of an Olympus-BX51M series optical microscope.
Thermodynamic computations that are carried out by “Thermo-
Calc® version P” software prepare useful phase diagrams and
thermodynamic data necessary for advanced materials design [15].
Some thermodynamic computations were made by the mentioned
software. “SSOL” database is used to retrieve necessary thermody-
namic data of stable phases [15]. Thermodynamic computations are
based on atmospheric pressure and graphite as reference state for
carbon element.
3. Results and discussion
3.1. Phase diagrams
Equilibrium phase diagrams of W–C–8wt.%Co and W–C–8wt.%Ni
that have been plotted using Thermo-Calc® version P software are
shown in Figs. 2 and 3 respectively. Additive carbides effects are
ignored in plotted phase diagrams due to simplification of computa-
tions and making generally applicable results. For this reason, W, C, Ni
and Co are the only species present in computations. However,
stability lines may be shifted in the presence of carbides/carbonitrides.
The stable phases in plotted diagrams are metallic binder with f.c.c.
crystallographic structure (fcc), free carbon (graphite), tungsten
carbide(WC), liquid binder (liquid) and eta phase (M6C at high
temperatures and M12C at low temperatures). Eta phase has chemical
composition of M12C at temperatures up to 1152 °C and M6C at higher
Fig. 2. Vertical section of W–C–Co for a system containing 8 wt.% Co under atmospheric
pressure representing stability regions of available phases.
Fig. 3. Vertical section of W–C–Ni system calculated in 8 wt.% of nickel under
atmospheric pressure.
temperatures in W–C–Co system (M represents cobalt and tungsten).
Complete substitution of cobalt by nickel increases the eutectic and
peritectic reaction temperatures up to 1343 °C and 1429 °C respec-
tively. Minimum temperature at which liquid phase is present has an
important role in sintering cycle design [7]. According to computa-
tions, the mentioned temperature in W–C–8wt.%Ni alloy is 70 °C more
than that of containing 8 wt.%Co. There are also some changes in
minimum and maximum carbon contents of the system at which two
phases (fcc and WC) just after equilibrium solidification are stable.
The mentioned quantities are 5.48 and 5.63 wt.% for cobalt binder and
5.39 and 5.57 wt.% for nickel binder respectively. As a result, no
unfavorable phases will appear theoretically in the final sintering
stage, which is in agreement with previous works [1,16]. WC is
considered as a stoichiometric phase with 6.1232 wt.% of carbon
content. This fact implies that in equilibrium sintering of W–C–8wt.%
Ni alloy, it is necessary to add metallic tungsten and/or non-
stoichiometric carbides such as titanium carbide to prevent formation
of eta phase and free carbon (graphite).
3.2. Magnetic behavior
Because of metallic and ferrous nature, binder is the only phase in
cemented carbonitrides that has ferromagnetic characteristics [17].
Since the formation of eta phase (M6C or M12C) consumes metallic
binder, magnetic quantities such as coercive force and magnetic
saturation may be reduced by formation of this unfavorable phase. No
eta (η) phase and free carbon (graphite) were observed in SEM
micrographs. Magnetic saturation and coercive force measurements
were carried out according to ASTM B886 and ASTM B887 standards
respectively.
3.2.1. Magnetic saturation
Cobalt, nickel and their alloys show ferromagnetic properties.
Alloying with WC reduces magnetic saturation of binder phase to
some extent [13]. Fig. 4 represents evaluated magnetic saturation
(Ms) of investigated specimens. It can be seen that there is a linear
relationship between increasing Ni/(Ni + Co) ratio in composition and
measured Ms. Since magnetic saturation quantities of pure cobalt and
nickel are 202 and 68 μTm 3/kg respectively and no eta phase was
 M. Mohammadpour et al. / Int. Journal of Refractory Metals and Hard Materials 30 (2012) 42–47
Fig. 4. Effect of gradual cobalt substitution by nickel on magnetic saturation of
investigated specimens.
observed in studied specimens, gradual substitution of cobalt by
nickel is responsible for decreasing total Ms of specimens. The linear
relationship has also been supported by previous works [13].
3.2.2. Coercive force
A decrease in natural Ms of metals leads to a decrease in measured
values of Hc (shrinkage of hysteresis loop). Coercive force is supposed
to decrease by increasing nickel proportion in starting composition of
alloys. However, there is a maximum in measured Hc that corre-
sponds to 25%Ni/(Ni + Co) ratio (Fig. 5). Since solution of tungsten in
binder increases coercive force, thermodynamic computations were
carried out to find the amount of solved tungsten in binder phase
during sintering process. Solution of tungsten in metallic binder alters
its ferromagnetic nature from soft to hard. For more amounts of
solved tungsten in binder, more Hc is measured since harder
ferromagnetism needs more force to eliminate magnetization.
Calculated equilibrium solubility of tungsten in binder (Fig. 6)
revealed that there is a maximum at around 25% of Ni/(Ni + Co) in
W mole fraction solved in binder phase. Consequently, abnormal
changes in Hc can be related to the different solubility values of
tungsten in binder. Equilibrium W solubility in binder phase along
with Ms test results explain changes in coercive force.
3.3. Mechanical properties
Two mechanical tests are common for experimental study and
massive production quality control; Vickers hardness test and
Fig. 5. The coercive force values versus Ni/(Ni + Co) ratio.
45
Fig. 6. Equilibrium solubility of tungsten in WC/2.5TiC/2.5TiC0.7N0.3/0.2VC/8(Co + Ni)
alloys; Thermodynamic computations were carried out at 1100 °C and atmospheric
pressure which all studied binder phases are thermodynamically solidified.
transverse rupture strength. The quantity of Vickers test that 30 kg
indentation load is common (Hv30), is proportional to wear resistance.
Transverse rupture strength (TRS) represents ductility of final
material. Vickers hardness and transverse rupture strength tests
were carried out according to ASTM B294 and ASTM B406-96
standards respectively.
3.3.1. Hardness tests
Indentations were made by 30 kg indenter load. So-called
Palmqvist cracks emanated from corners of indentations during the
tests [18]. WC grain size is the major factor affecting final hardness of
cemented carbides in constant volume fraction of binder phase [1].
Because of less WC/Co interface energy than WC/Ni, Ostwald ripening
mechanism is supposed to promote in nickel containing cemented
carbides, resulting in enhanced carbide grain growth (Fig. 7) [14]. For
constant sintering conditions, lower hardness amounts were mea-
sured in Ni containing alloys (Fig. 8). However, TiC, TiC0.7N0.3 and VC
Fig. 7. SEM micrograph of specimen No.5 with complete substitution of cobalt with
nickel; mean grain size of facetted WC is slightly larger than those in specimen No. 1.
46 M. Mohammadpour et al. / Int. Journal of Refractory Metals and Hard Materials 30 (2012) 42–47

Fig. 8. Vickers hardness test values of sintered specimens versus Ni/(Ni + Co) ratio.
Fig. 10. Changes in CFL thickness versus Ni/(Ni + Co) ratio.

additives have restricted grain growth in all investigated alloys so that

difference between maximum and minimum hardness is less than 5%.

3.3.2. Transverse rupture strength

Two standard test specimens were prepared by surface milling and
polishing for each alloy and average amounts of measured TRS were
reported. The surfaces of as HIP sintered specimens were removed
during preparation of standard TRS test samples as well as probably
formed CFL. As a result, the measured TRS values are dependent on
bulk mechanical properties. TRS of cemented carbides is in direct
relationship with mean carbide grain size for WC grain sizes of less
than 4 μm [1]. As it can be seen from hardness test results
(Section 3.3.2) increase in Ni/(Ni + Co) ratio enhanced hardness and
mean WC grain size as well. This fact supports changes in TRS of
studied alloys with different nickel and cobalt contents (Fig. 9).

3.4. Cubic Free Layer thickness

Studying the microstructure of vacuum sintered specimens

revealed formation of type A-FGCCs. As can be seen in Fig. 10,
increasing Ni/(Ni + Co) ratio increased CFL thickness. Nickel has less
affinity to carbon and nitrogen as well [13]. Therefore, enhanced
formation kinetics of CFL in nickel containing alloys can be attributed
to increase in atomic mobility of nickel.
Surface roughness of specimens changed proportionally with final
CFL thickness (Fig. 11). Increasing final thickness of CFLs through

Fig. 11. Optical surface microstructure of top) specimen No. 1 and bottom) specimen
No. 5; specimens were sintered in vacuum atmosphere (~ 0.5 mbar) at 1450 °C for
about 4 h; cubic carbonitride phase is in dark and black when WC phase is white and
gray; CFLs of about 30–60 μm were observed in all studied alloys.

altering any kinetically accelerating factors such as cubic carbide

composition and binder phase volume fraction is also reported that
increases final surface roughness (Ra) [19]. So it can be concluded that
change in Ra made by altering binder is roughly due to increase in CFL
thickness regardless of nature of binder phase.

4. Conclusions

Nickel containing FGCCs were prepared by the present laboratory

and industrial instrument with almost no production defects and
Fig. 9. Transverse rupture strength values of different specimens. some outstanding properties than cobalt containing replicas.
 M. Mohammadpour et al. / Int. Journal of Refractory Metals and Hard Materials 30 (2012) 42–47
Changes in properties of WC/2.5TiC0.7N0.3/2.5TiC/0.2VC/8Co
cemented carbonitride were observed trough gradual substitution of
cobalt by nickel as follows:
• Decrease in magnetic saturation and coercive force
• Increase in transverse rupture strength by 37% with less than 5%
scarifying Vickers hardness
• Doubling final thickness of CFL and enhanced surface roughness.
Acknowledgements
The authors are grateful for financial support and instrument
supply of Mr. Reza Rahimi (Almasesaz Company). Mrs. Ehteram
Dastafshan and Mr. Jalal-al-din Sadrabadi (Iran Powder Metallurgy
Complex) are thanked for powder preparation.
Professor Nader Parvin from Amirkabir University of Technology,
Department of Materials Science is thanked for excellent support and
encouragement.
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