metals

Article
Effects of Cr3C2 Addition on Wear Behaviour of
WC-Co Based Cemented Carbides
Luca Boccarusso , Fabio Scherillo and Umberto Prisco *
Department of Chemical, Materials and Production Engineering, University of Napoli Federico II,
Piazzale Tecchio, 80-80125 Naples, Italy; luca.boccarusso@unina.it (L.B.); fabio.scherillo@unina.it (F.S.)
* Correspondence: umberto.prisco@unina.it; Tel.: +39-081-768-2336




Received: 8 October 2018; Accepted: 25 October 2018; Published: 1 November 2018


Abstract: Microstructure, hardness, transverse rupture strength, and abrasion resistance of WC-10
wt% Co cemented carbides modified with the addition of different mass fraction of Cr3 C2 , in the
range of 0–3 wt%, are studied. The influence of the microstructure, composition and hardness on
the mechanical properties and wear resistance is analysed. Considering that the material under
investigation can be used as die for the extrusion process of hard ceramic materials, the tribological
behaviour was evaluated by performing sliding wear tests in wet conditions using a block-on-ring
tribometer. Wear mechanism principally based on binder removal and subsequent fragmentation
and microabrasion of the WC grains is proposed. Carbide grain size and bulk hardness can be tuned
as function of specific applications by adding different amounts of Cr3 C2 . In particular, increasing
hardness and reducing grain size by the addition of Cr3 C2 are demonstrated to considerably enhance
the wear performance of these carbides.

Keywords: cemented carbides; binder modification; hardness; transverse rupture strength;

wear resistance

1. Introduction
WC-Co cemented carbides are known for their excellent properties and extraordinary resistance
to heat even after long-term exposure to high temperatures [1–4]. Their outstanding mix of strength,
wear resistance, hardness and toughness is the result of the combination of the hard carbides and the
ductile metallic binder [5–7]. For these reasons, WC-Co carbides are extensively employed in applications
requiring exceptional mechanical properties and wear resistance [8], e.g., cutting tools [9,10], bearings,
drilling and mining equipment [5], dies and punches [11].
The material characteristics of the WC-Co hardmetals are strictly related to their chemical
composition and microstructure, which in turn is influenced by the process parameters. In particular,
it is known that it is possible to adjust the final properties of WC-Co alloys to fit each specific application
by varying the binder content [12], the grain size, or by using additives as: chromium carbide
(Cr3 C2 ) [13,14], nickel or vanadium carbide (VC) [9,14,15]. For example, it was demonstrated that the
wear resistance of WC-Co cemented carbides generally increases as the volume fraction of cobalt and
the WC grain size are reduced [9,16]. Almond and Roebuck [17] found that the wear performance of
the WC-Co hardmetal increases dramatically as the grain size is reduced to nanometre scale.
Cr3 C2 has been used in small amounts in WC-Co cemented carbides as an inhibitor of grain
growth [16]. However, other properties, such as hardness, magnetic coercivity and transverse rupture
strength (TRS), have been found to be affected by the addition of Cr3 C2 [15,18]. Mostly the above
cited works studied the tribological and wear behaviour in dried conditions, however considering that
WC-10 wt% Co can be used as material of the die for the extrusion processes of hard ceramic materials,
it could be interesting to test this material in wet conditions.

Metals 2018, 8, 895; doi:10.3390/met8110895 www.mdpi.com/journal/metals

Metals 2018, 8, 895 2 of 9

Therefore, in the present work, the tribological behaviour of WC-10Co grades containing different
mass fraction of Cr3 C2 , ranging from 0 to 3 wt% was studied in wet conditions by using a block-on-ring
tribometer. The structure, density, hardness, and TRS of the different grades were studied as
function of Cr3 C2 content. The volume losses of the different grades were measured and compared.
The wear surfaces were analyzed to identify the wear mechanisms. Correlations between volume loss,
microstructure, hardness, and TRS were determined.

2. Materials and Methods

The WC-10Co specimens were fabricated using conventional production routes. The average
particle size of the WC powder, before the sintering process, was 5 µm. The binder and the WC were
mixed firstly by dry ball milling and then by wet milling with acetone. The Cr3 C2 was previously
mixed into the binder and, subsequently, the carbide was added. A 1–2 wt% of powder wax was added
to the charge three hours before the end of the milling. The whole mixing stage went on for 20 hours.
Green compacts were obtained pressing the powder premix in a die under 180 MPa. A green density
of 55% of the theoretical value was obtained for all specimens. The green compacts were first dewaxed
in a furnace at 350 ◦ C for 2 h in hydrogen and then sintered in the same furnace for 1 h at 1400 ◦ C
under vacuum. Afterwards, the samples were finished by grinding to obtain the final dimensions
and tolerances according to ASTM B611-13, which was applied in the following tribological tests [19].
The average roughness, Ra, of the samples’ surfaces was measured to be 0.7 µm. The test-pieces were
25 mm × 76 mm × 12 mm in size. Seven alloys based on WC-10 wt% Co with additions of 0–3 wt%
Cr3 C2 partly replacing the WC were studied. Alloy compositions are given in Table 1.

Table 1. Compositions in wt% of the seven alloys.

Alloy WC Cr3 C2 Co
0 wt% Cr3 C2 90 0 10
0.5 wt% Cr3 C2 89.5 0.5 10
1 wt% Cr3 C2 89 1 10
1.5 wt% Cr3 C2 88.5 1.5 10
2 wt% Cr3 C2 88 2 10
2.5 wt% Cr3 C2 87.5 2.5 10
3 wt% Cr3 C2 87 3 10

The density of the samples was determined by hydrostatic weighing using Archimedes’
principle. The porosity was obtained knowing the measured density and the theoretical density
of each composition calculated from the rule of mixtures (WC = 15.77 g/cm3 , Cr3 C2 = 6.74 g/cm3 ,
and Co = 8.85 g/cm3 ).
Selected compacts representative of the seven experimental alloys were polished firstly using
7 µm diamond pastes and then colloidal silica (0.05 µm) suspension. The polished specimens were
eventually etched using the Murakami reagent for 80 s. The microstructure of the prepared samples
was investigated with optical microscopy (Zeiss Axioplain 2 imaging, Zeiss, Germany) and a scanning
electron microscopy (SEM, Hitachi TM 3000, Hitachi, Tokyo, Japan) equipped with an energy dispersive
X-ray analyser (EDX, Hitachi TM 3000, Hitachi, Tokyo, Japan). The grain size distribution was
measured using the linear intercept method. At least 1000 grains from four photomicrographs taken
arbitrarily from different specimen locations were measured for each grade.
The hardness of the sintered compacts was measured on the polished surfaces of the samples
according to ISO 6507-1:2018 using an indentation load of 30 kg [20].
The transverse rupture strength of the sintered specimens was measured according to ASTM
B406-76 under three-point loading [21].
Abrasion tests were performed according to ASTM B611–13 in a specially built block-on-ring
tribometer [5,19]. The blocks were pressed against the steel disk (Ø 169 mm) with a normal load
(Fn = 200 N) and at a constant sliding speed (50 rpm). Wear tests were conducted under wet conditions
 Metals 2018, 8, x FOR PEER REVIEW 3 of 9
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Abrasion tests were performed according to ASTM B611–13 in a specially built block-on-ring
Abrasion
tribometer tests
[5,19]. Thewere performed
blocks were pressedaccording
againstto the
ASTMsteelB611–13
disk (Øin 169a mm)
specially
withbuilt block-on-ring
a normal load (Fn
at room temperature in accordance to the adopted standard. Wear loss of the hardmetal samples was
tribometer [5,19]. The blocks were pressed against the steel disk (Ø 169 mm)
= 200 N) and at a constant sliding speed (50 rpm). Wear tests were conducted under wet conditions with a normal load (Fn
measured
= 200
by
N)
weighing
and at a
the
constant
block before
sliding speed
and
(50
after
rpm).
the sliding
Wear tests
using
were
a digital
conducted
at room temperature in accordance to the adopted standard. Wear loss of the hardmetal samples was
balance.
under wet
The volume loss
conditions
was calculated
measured from
at room temperature
by the mass
weighing in the loss and
accordance
block tothe
before the density
adopted
and after theof each sample.
standard.
sliding Wear loss
using of the
a digital hardmetal
balance. Thesamples was
volume loss
For
was each
measured of the
by weighing
calculated above
from thethe tests,
block
mass five repetitions
lossbefore
and theand were
after the
density performed
sliding
of each using afor
sample. each
digital alloy grade.
balance. The volume The loss
average
values with the
was calculated ± 2 sigma
For each offrom error
the mass
the above bars (~95%
lossfive
tests, confidence
andrepetitions
the densitywere intervals)
of each are reported in the following
sample.for each alloy grade. The average
performed figures.
values For each
with theof±2the above
sigma tests,
error five
bars repetitions
(~95% confidencewereintervals)
performed arefor each alloy
reported in thegrade. The average
following figures.
3. Results
valuesandwithDiscussion
the ±2 sigma error bars (~95% confidence intervals) are reported in the following figures.
3. Results and Discussion
For the sake of comparison, Figure 1 reports the microstructures of the sinterized hardmetal
3. Results and Discussion
without Cr ForCthe sake of comparison, Figure 1 reports the microstructures of the sinterized hardmetal
3 2 addition and of the one with 1.5 wt% of Cr3 C2 . The main effect of the Cr3 C2 addition is
withoutForCr
the
3Csake of comparison,
addition and of theTheFigure
one 1 1.5
with reports
wt% the
of Cr microstructures
3C2. The main effectof the
of sinterized
the Cr3C hardmetal
2 addition
the refinement of 2the WC grain size. arrows in Figure 1a points to some very large WC grainsiswhich
without
the Cr3C2 addition
refinement of the WC andgrain
of the oneThe
size. witharrows
1.5 wt% in of Cr3C21a
Figure . The main
points toeffect
someofvery
the large
Cr3C2 WCaddition is
grains
are not observed in the materials sintered with the addition of Cr3 C2 . It was already demonstrated
the refinement
which are not of the WC in
observed grain
thesize. The arrows
materials in Figure
sintered with 1a thepoints to some
addition of Crvery
3C2. large
It was WCalready
grains
that small addition of
which are notthat
Cr3 C2 restricts
observed
the grain
in the materials
growthwith
sinteredthe
of the WC
thegrowth
due toofthe
addition
slower
Cr3Cdue
2. It to
grainalready
was
boundary
demonstrated small addition of Cr3C2 restricts grain of the WC the slower
migration and
demonstrated
grain hence
boundarythat limited coalescence
small addition
migration and hence of
of limitedWC grains
Cr3C2 restricts caused
the grain
coalescence by
of WCgrowththe
grains ofCr segregation
the WC
caused to the WC grain
dueCrtosegregation
by the the slower
boundaries
grain
to [22,23].
the boundary
WC grain migration
boundariesand hence limited coalescence of WC grains caused by the Cr segregation
[22,23].
to the WC grain boundaries [22,23].

Figure 1. Optical
Figure micrographs
1. Optical of of
micrographs thethe
microstructure:
microstructure: (a)
(a) 00 wt%
wt%ofofCr
Cr
3C32Cand
2 and
(b) (b) 1.5 wt%
1.5 wt% of Crof
3CCr
2. 3 C2 .

Figure 1. Optical micrographs of the microstructure: (a) 0 wt% of Cr3C2 and (b) 1.5 wt% of Cr3C2.
The The
inverse
inverse relation
relationbetween
betweenWC WCgrain
grain size
size and
and CrCr33CC content
2 2content is is further
further evidenced
evidenced by theby the
quantitativeThe metallographic
quantitativeinverse relation
metallographic study
studyininFigure
between WCFigure 2.
grain2. The
size
The WCWCgrain
and grainsize
Cr 3 C 2 size decreases
content is
decreases further
withwith
the the
evidenced increase
increase of theof the
by the
2quantitative
Cr3 CCr 3C2 content.
content. metallographic
Actually,ititseems
Actually, studythat
seems in Figure
that aaminimum2. Thegrain
minimum WC grain
grain issize
sizesize isdecreases
reached for Cr
reached with the
3C2 Cr
for values
3Cincrease
2 around
values of the
1.5
around
Cr3Csince
wt%,
1.5 wt%, content.
2since withActually,
with higher it seems
highervalues
values ofofthat
the Cra3Cr
the minimum
C grainthe
2 substitution
C substitutionsize is reached
average
the grainfor
average Crslightly
size
grain3C2 values
size around
increases.
slightly 1.5
The
increases.
3 2
wt%, sinceofwith
existence this higher
minimum values of the
cannot be Cr 3C2 substitution
statistically provedtheconsidering
average grain the size slightly
overlap of increases.
the The
confidence
The existence of this minimum cannot be statistically proved considering the overlap of the confidence
existenceatof1.5this
interval wt%minimum
with those cannot be statistically
measured for largerproved considering
Cr3C2 content. thebeoverlap
It can concluded of the confidence
then that the
interval at 1.5 wt% with those measured for larger Cr3 C2 content. It can be concluded then that the
interval
grain sizeatdecreases
1.5 wt% withfrom those measured
a starting value of for2.1
larger Cr3C2 content.
μm, observed without It can
the be concluded
addition of thethen that the
additive, to
graingrain
size decreases from a starting value of of 2.1μm, observed
µm,observed without addition
the addition of the additive,
1.6–1.8size
μmdecreases
when thefrom Cr3Ca2 starting
content value
reaches 2.11–1.5 wt%; without theto
this corresponds of the additive,
a 20% decrease. Further to
to 1.6–1.8 µm
1.6–1.8
addition μm when
of when
Cr thetheCr
3C2 above Cr C
31.5 content
3C22 wt%
content reaches
doesreaches
not seem 1–1.5
1–1.5 wt%;
wt%;
to have this
this
any corresponds
corresponds
effect to ato20%
on decreasing athe
20% decrease.
decrease.
grain Further
Further
size.
addition of Crof3 CCr
addition 2 3above
C2 above1.51.5wt%wt%does
doesnot notseem
seem to haveany
to have anyeffect
effectonon decreasing
decreasing the the
grain grain
size.size.

Figure 2. Effect of the Cr3C2 addition on the WC grain size of the WC-10Co cemented carbide.
Figure 2. Effect
Figure of the
2. Effect Cr3Cr
of the C23Caddition
2 additionon
on the WC grain
the WC grainsize
sizeofofthe
the WC-10Co
WC-10Co cemented
cemented carbide.
carbide.

The EDX analyses showed that no trace of Cr3 C2 is present in the alloys and hence the additive
was completely dissolved during the sintering. The added Cr is entirely present into the Co binder,
while the carbide grains do not contain any Cr. The chromium content of the binder was measured to
 Metals 2018, 8, x FOR PEER REVIEW 4 of 9
Metals 2018, 8, 895 4 of 9

The EDX analyses showed that no trace of Cr3C2 is present in the alloys and hence the additive
was completely dissolved during the sintering. The added Cr is entirely present into the Co binder,
vary between 4 and 7 at% at higher level of Cr3 C2 addition, whereas the W content of the binder was
while the carbide grains do not contain any Cr. The chromium content of the binder was measured
roughly equal to 1 at% despite the added amount of Cr3 C2 , see Figure 3a.
to vary between 4 and 7 at% at higher level of Cr3C2 addition, whereas the W content of the binder
At Cr3 C2 contents
was roughly
higher than 2 wt% a Cr-rich phase was observed. Figure 3b shows an area
equal to 1 at% despite the added amount of Cr3C2, see Figure 3a.
of this chromium-rich phase
At Cr3C2 contents higherobserved withathe
than 2 wt% SEM.
Cr-rich The was
phase composition of this3b
observed. Figure chromium-rich
shows an area of phase
is compatible to the presence of a M
this chromium-rich phase observed7 with C 3 the SEM. The composition of this chromium-rich phase isbeen
carbide, whose chromium and cobalt contents have
demonstrated
compatibletotodepend on theofamount
the presence of Cr3 Cwhose
a M7C3 carbide, 2 added to the starting
chromium powder,
and cobalt contentsseehave
[12,22,24,25].
been
demonstrated
The phase diagramtocalculated
depend on bythe Zackrisson
amount of Cret 3Cal.
2 added to the starting
[22] shows powder,
that some M7 Csee
3 [12,22,24,25].
can precipitateThefrom
phase diagram calculated by Zackrisson et al. [22] shows that some M
the liquid for Cr3 C2 contents higher than 1 wt%, although there is a primary precipitationthe
7 C3 can precipitate from of the
solid liquid
binderfor forCrCr
3C2 contents higher than 1 wt%, although there is a primary precipitation of the solid
3 C2 contents lower than 3.5 wt%. M7 C3 is not stable at room temperature and
there binder for Cr3C2 contents lower than 3.5 wt%. M7C3 is not stable at room temperature and there is a
is a driving force which promotes its transformation into M3 C2 . However, the kinetics of
driving force which promotes its transformation into M3C2. However, the kinetics of this
this transformation is expected to be very slow due the slow rate of diffusion of the involved
transformation is expected to be very slow due the slow rate of diffusion of the involved species [26].
species
The[26]. The volume
volume fraction
fraction of of this chromium-rich
this chromium-rich phase istoexpected
phase is expected to increase
increase with with of
the addition theCraddition
3C2.
of Cr3This
C2 . This was indeed observed since the volume fraction of M C rises to 2%
was indeed observed since the volume fraction of M7C3 rises 7to 32% with the 3 wt% of Cr with the 3 3wt%
C2 of
Cr3 C2substitution.
substitution.

3. SEM
FigureFigure microstructure and EDX analysis: (a) the binder phase and (b) the M C3 carbide
3. SEM microstructure and EDX analysis: (a) the binder phase and (b) the M7C37carbide
observed at 3 wt% addition
observed at 3 wt% of Cr
addition C32C(concentrations
of 3Cr are in at%).
2 (concentrations are in at%).

The addition of Cr
The addition of3 C does
Cr23C not
2 does nothave
haveany
anyeffect
effect on the densification
on the densification ofof
thethe WC-10Co
WC-10Co cemented
cemented
carbides.
carbides. The decrease in the measured densities of the studied alloys is perfectly compatible withwith
The decrease in the measured densities of the studied alloys is perfectly compatible
the added amount
the added of chromium
amount of chromium carbide
carbideatatthe
thesame
same level ofporosity,
level of porosity,see
seeFigure
Figure 4. All
4. All the the samples
samples
were measured to have an equal porosity of ~2% in average without regard to the amount of Cr3 C2 .
This is expected considering the consistency of the applied manufacturing process. The measured
porosity is in agreement with the values of the porosity showed by sintered WC-10Co carbides in
similar conditions [15].
 Metals 2018, 8, x FOR PEER REVIEW 5 of 9
Metals 2018, 8, x FOR PEER REVIEW 5 of 9
were measured to have an equal porosity of ~2% in average without regard to the amount of Cr3C2.
were
This ismeasured
expectedtoconsidering
have an equal
the porosity of ~2%
consistency in average
of the applied without regard to
manufacturing the amount
process. of Cr3C2.
The measured
MetalsThis is
8, expected considering the consistency of the applied manufacturing process. The measured
porosity is in agreement with the values of the porosity showed by sintered WC-10Co carbides in 5 of 9
2018, 895
porosity is in agreement
similar conditions [15]. with the values of the porosity showed by sintered WC-10Co carbides in
similar conditions [15].

Figure
Figure 4. Effect
4. Effect of the
of the CrCr
3 C32Caddition
2 addition on
on the
the density
densityofofthe WC-10Co
the cemented
WC-10Co carbide.
cemented carbide.
Figure 4. Effect of the Cr3C2 addition on the density of the WC-10Co cemented carbide.
The hardness
The hardness of the
of the WC-10Co
WC-10Co cementedcarbides
cemented carbides increases
increaseswith
withthe addition
the additionof Cr C2.3The
of3Cr C2 . total
The total
The hardness
registered increaseof
is the
equalWC-10Co
to 200 cemented
HV, Figure carbides
5. increases
Considering thewith the addition
constancy of the of Cr3C2. The
porosity withtotal
the the
registered increase is equal to 200 HV, Figure 5. Considering the constancy of the porosity with
registered
Cr increase is equal to 200 HV, Figure 5. Considering the constancy of the porosity with the
3C2 content, the following conclusions can be drawn about the causes of hardness increment. Up
Cr3 C2Crcontent, the the
C2 content,
following
following
conclusions can bebedrawn about the causes ofhardness
hardnessincrement.
increment. Up to
to 31.5 wt% addition of Cr3C2conclusions canincrease
, the hardness drawn about the
is mainly causes
related to of
the refinement of the WC Up
1.5 wt% addition
to 1.5 wt% This of Cr3 C
addition of2 ,Cr
the hardness increase is mainly related to the refinement of the WC grain
3C2, the hardness increase is mainly related to the refinement of the WC
grain size. is responsible of an increase of 140 HV, which corresponds to 70% of the total
size. grain
This is responsible
size.increase of an
This isofresponsible increase of 140 HV, which corresponds to 70% of the total observed
observed 200 HV. of an increase of 140 HV, which corresponds to 70% of the total
increase of 200increase
observed HV. of 200 HV.

Figure 5. Effect of the Cr3C2 addition on the hardness of the WC-10Co cemented carbide.
Figure 5. Effect
Figure of the
5. Effect CrCr
of the 3 C32Caddition
2 addition on
on the hardnessofofthe
the hardness the WC-10Co
WC-10Co cemented
cemented carbide.
carbide.
On the other hand, the remaining 30% portion of the total hardness increment of 200 HVis due
On
to theOn
the the other
other
gradual hand,hand,
increase the
theof remaining
remaining
the weight30%30% portion
portion
fraction ofofthe
of the thetotal
hard total hardness
andhardness increment
incrementofof200
brittle chromium-rich M200 HVis
7C3 HVis
due
carbidedue to
to
the gradualthe gradual
into the increase increase
binder [27]. of The of the
the weight weight fraction
effect of fraction of
of the
solid solution the hard
hard anddue
hardening and
brittlebrittle chromium-rich
to thechromium-rich
increased presence M
M7 of C
C3Cr
7 3 carbide
carbide
in the into
into
the binder
binderthe binder
[27].
when The [27].
the Cr3The
effect
C2of effect
solidofsolution
addition solid solution
increases hardening
hardening
can be due
thetoincreased
duediscarded
easily to the increased
according topresence
presence of Cr
of Cr in in
the Hume–Rothery thethe
binder
binder[28].
rules when the Cr3C2 addition increases can be easily discarded according to the Hume–Rothery
when the Cr3 C2 addition increases can be easily discarded according to the Hume–Rothery rules [28].
rulesAs[28].
shown in Figure 6, the additionofofupupto
to 1.5
1.5 wt%
As shown in Figure 6, the addition wt%of ofCrCr3C3 2Cincreases the TRS of the hardmetal.
2 increases the TRS of the hardmetal.
As shown
However, larger inamounts
Figure 6,of the addition
such of uphave
additions to 1.5the
wt% of Cr3effect
reverse C2 increases
due to the
the TRS of the presence
increased hardmetal.
However, larger amounts
However,
of such additions have the reverse effect due to the increased presenceofof the
the brittle larger amountsinto
M7C3 carbide of such additions
the binder. have the
Indeed, the first
reverse effect
strong due to the
decrease increased
of the TRS is presence
visible atof2
brittletheM7 C3 carbide into the binder. Indeed, the first strong decrease of the TRS is visible at 2 wt% of
wt%brittle
of Cr3M C27.CThis
3 carbide into the binder. Indeed, the first strong decrease of the TRS is visible at 2
is the lowest value of Cr3C2 content at which the M7C3 was firstly observed.
Cr3 Cwt%
2 . This is 3the
of Cr lowest
C2. This value
is the of Cr
lowest 3 C2of
value content at which
Cr3C2 content the Mthe
at which 7 C3Mwas firstly
7C3 was observed.
firstly observed.
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Figure 6. 6.
Figure Effect
Effectof the CrCr
of the 3C32C 2 addition
addition ontransverse
on the the transverse ruptureofstrength
rupture strength of the
the WC-10Co WC-10Co
cemented
Figure 6. Effect of the Cr3C2 addition on the transverse rupture strength of the WC-10Co cemented
carbide.
cemented carbide.
carbide.
FigureFigure 7 reports
7 reports the the volume
volume lossloss during
during thetribological
the tribologicaltests
tests by
by each
each tested
testedsample
sampleasasfunction
function of
of Figure
the Cr 3C7 reports the volume
2 substitution level. loss addition
The during theof tribological
the hard tests has
phase by each
a tested
quite sampleeffect
positive as function
onresulting
the
the Cr3 C2 substitution level. The addition of the hard phase has a quite positive effect on the
of the Cr3wear
C2 substitution level. The addition of theThehard phase has decreases
a quite positive effect on the
wear resistance of the cemented carbide. The wear volume decreases with the increase of the of
resulting resistance of the cemented carbide. wear volume with the increase Cr3 C2
resulting
the Cr3C2 wear resistance
substitution of the
level, butcemented carbide.
with different lawsThe wearand
at low volume decreases
high Cr withThe
3C2 content. the addition
increase of
of
substitution
the Cr
level,
3C2 to
but with
substitution
different
level,about
laws
but with
at low laws
different
and high Crand
3 C2high
content. The addition of Cr3 Cof
2 up to
Cr3C 2 up 1.5 wt% brings a strong decrease ofatthe low
wear volumeCrwith
3C2 content.
the Cr3CThe addition
2 content.
1.5 wt% brings about a strong decrease of the wear volume with
Cr3C2 up to 1.5 wt% brings about a strong decrease of the wear volume with the Cr C content.
3 2 the Cr3C2 content.

Figure 7. Volume loss of the WC-10Co cemented carbides vs. the Cr3C2 content. The two regression
Figure 7. Volume
Figure
lines 7. Volume
fitted lossdata
to the of the
loss of WC-10Co
the
at low (≤1 wt%)cemented
WC-10Co cemented
and carbides
carbides
high (≥1.5 wt%)vs.vs. theCr3C2
the
Cr3C2 Cr3C2
content content.
content.
are TheThe
two two
reported. regression
regression
lines lines
fittedfitted
to theto data
the dataat low
at low(≤(≤1
1 wt%)
wt%)and and high (≥1.5wt%)
high (≥1.5 wt%) Cr3C2
Cr3C2 content
content are reported.
are reported.
A regression analysis of the data in this interval indicates a good linear relationship between the
A A regression
regression
volume loss and analysis
analysis
the Crof3C2ofthe the data
data
content (rin2in=this
this interval
with pindicates
interval
0.973 < 0.001). aThe
indicates agood
good linear
slope relationship
linear relationship
coefficient of thebetween
between
fitted the the
line
volume
volumewasloss loss
andand
calculated the tothe
Cr Cr
C23Ccontent
be3−0.025 2 content
cm3/(wt%(r(r2 2=of
= 0.973
0.973
Cr3C2).with
with
Abovepp<<1.5
0.001).
0.001).
wt%, The
theslope
The slope
wear coefficient of the
coefficient
volume drops of fitted line line
thelightly
more fitted
was
withcalculated
the Crto3Cbe
was calculated 2 to −be0.025
content.−0.025In cm
cmthis
3/(wt% of Cr3C2). Above 1.5 wt%,
3 /(wt%
case theof Cr linear regression (r2wt%, thethe
= 0.915 wear
with volume drops
p <volume
0.001) moremore
predicts alightly
slope
3 C2 ). Above 1.5 wear drops lightly
with the Crof
coefficient 3C2thecontent.
fitted In
linethis casetothe
equal linearcm
−0.003 regression
3/(wt% of(r 2 = 0.915 with p < 0.001) predicts a slope
Cr2 3C2), which is one order of magnitude
with the Cr3 C2 content. In this case the linear regression (r = 0.915 with p < 0.001) predicts a slope
coefficient
lower than of the
thefitted
valuefitted line equal
previously to −0.003 cm33/(wt% of Cr3C2), which is one order of magnitude
observed.
coefficient of the line equal to −0.003 cm /(wt% of Cr3 C2 ), which is one order of magnitude
lowerThethan the value previously
microscopic analysis ofobserved.
the wear track shows that all samples underwent the same wear
lower than the value
The microscopic
previously
analysis
observed.
mechanism. The profile of theofwear the wear
trackstrack shows that all smooth
is macroscopically samplesand underwent
shallow.theThissame wear
indicates
The microscopic
mechanism. The analysis
profile of of wear
the the wear tracks track
is shows that all
macroscopically samples
smooth and underwent
shallow. Thisthe same wear
indicates
that plastic deformations of the asperities occurred during the test. Ploughing grooves running
mechanism.
that Thedeformations
plastic
longitudinally profile of the
to the sliding of wear
the tracks
asperities
direction are is macroscopically
occurred
also during
visible, Figure the8.smooth
test. andmaterial
Ploughing
Fractured shallow. andThis
grooves indicates
running
traces of
that plastic deformations
longitudinally to the of
sliding the asperities
direction are occurred
also during
visible, Figure the
8.
binder removed from the surface were found along these grooves. The pits visible on the surface test.
Fractured Ploughing
material grooves
and traces running
of
of
binder
Figure removed
longitudinally8 aretoleft
theby fromthethe
sliding surface
direction
carbide were
are found
particles also along
that visible,
were these
Figure
pulled grooves.
out 8.from Thematerials.
Fractured
the pitsmaterial
visible on
and thetraces
surface of of
binder
Figure 8 are left by the carbide particles that were pulled out from
removed from the surface were found along these grooves. The pits visible on the surface of Figure 8 the materials.
are left by the carbide particles that were pulled out from the materials.
Metals 2018, 8, x FOR PEER REVIEW 7 of 9

Metals 2018, 8, 895 7 of 9

Metals 2018, 8, x FOR PEER REVIEW 7 of 9

Figure 8. Optical micrograph of the of the worn surfaces.

Based on the aboveFigure Figure

results, 8. 8.itOptical
is fair
Optical micrograph
to propose
micrograph of
of thea ofwear
the ofthe
theworn surfaces.
mechanism
worn surfaces.mainly based on binder
extrusion and microabrasion. During the initial phase of the process, the ductile Co matrix in
Based Based the on the above results,it itisisfair
fairtoto propose
propose aa wear mechanism mainly based on binder
between theonhard above
WC results,
particles is plastically deformed wear by the mechanism
compressive mainly couplingbased on binder
force. This
extrusion and microabrasion. During the initial phase of the process, the ductile Co matrix in
extrusion
causesbetween and
the extrusion microabrasion. During the initial phase of the process, the ductile Co matrix in
the hardofWC theparticles
binder and its subsequent
is plastically deformed removal, which occurs
by the compressive by a combination
coupling force. This of
between
plasticcauses the
deformationhard WC particles
andofmicroabrasion is plastically deformed by the compressive coupling force. This causes
the extrusion the binder and [29]. When sufficient
its subsequent removal, binder has been
which occurs by a removed,
combinationthe of WC
the extrusion
particles
plastic
of
aredeformationthe binder
no longer adequately and its
and microabrasion
subsequent
supported, [29]. so
removal,
Whenthatsufficient which
they become occurs
binderloose
by
has and
a combination
been can develop
removed,
of
theaWC
plastic
motion
deformation
relative to theare
particles and microabrasion
binder.
no longerThisadequately [29].
triggers the When sufficient
microcracking
supported, so that andbinder
they then has
become been
theloose removed,
fragmentation
and can developthe WC
of thea WCparticles
motion are
grains,
no longer
until relative
their adequately
to theor
partial supported,
binder.
complete This triggers so that
pull-out the
fromthey become
microcracking
the material. loose
and thenandthe can develop a motion
fragmentation of the WC relative
grains,to the
binder. This
until theirtriggers
partial the
or microcracking
complete pull-out andfromthenthe the fragmentation
material.
It is well known that the abrasive wear resistance of coarse-grained cemented carbides of the WC grains, until their partialis
or complete It is well
pull-out known
from that
the the abrasive
material. wear resistance of
usually lower than that of fine grain size [5,9]. Furthermore, it is fair to infer that the initial phase ofcoarse-grained cemented carbides is
usually
It welllower
is process, known thanthat
thatthe of fine grain size
abrasive wear[5,9]. Furthermore,
resistance it is fair to infer that the initial phase of
the wear namely the binder extrusion, is easierofthe coarse-grained
more ductilecementedthe binder carbides
is. Indeed,is usually
Pirso
lower the wear
than thatprocess,
of finenamely
grain the
size binder
[5,9]. extrusion,
Furthermore, is easier
it is the
fairmore
to ductile
infer that the
thebinder
initial is. Indeed,
phase ofPirso
the wear
et al. [5] correlated the bulk hardness of these composites with their abrasive wear resistance
et al. [5] correlated the bulk hardness of these composites with their abrasive wear resistance
process,
demonstratingnamely the
thatthat binder
the the
wear extrusion,
coefficient is easier the more ductile the binder is. Indeed, Pirso et al. [5]
demonstrating wear coefficientisisinversely
inversely proportional
proportional totothe the bulk
bulk hardness
hardness for WC–Co
for WC–Co
correlated the bulk hardness of these composites with their abrasive wear resistance demonstrating
alloys. alloys.
that The
the wearabove coefficient
The above experimental is inversely
experimental observations proportional
observationsconfirm
tothe
confirm the
theproposed
bulk hardness
proposed for
wearmechanism
wear
WC–Co
mechanism alloys.
andand furthermore
furthermore
are inThe
are above
fullin agreementexperimental
full agreement with withwhatobservations
what previously
previously confirm
reported
reported the proposed
in literature
literature wear mechanism
[5,9].
[5,9]. Figure
Figure 9 and
9 shows shows furthermore
the the average
average are
in full agreement
volume loss with
versus what
the previously
average reported
hardness. It in literature
clearly
volume loss versus the average hardness. It clearly demonstrates that the wear volume loss is [5,9].
demonstrates Figure
that 9
theshows
wear the
volumeaverageloss volume
is
loss versus
inversely
inversely therelated
related average
to the hardness.
to the hardness
hardness It clearly
of of
the demonstrates
thecemented
cemented carbides.
carbides. thatHowever,
the weara volume
However, bimodal
a bimodal loss is inversely
dependence,
dependence, related
as theas the
to the
one one previously
hardnessobserved
previously observed
of the cemented in Figure
in Figurecarbides. 7, is evident.
7, is evident.However, For
For low low Cr
a bimodal3 C 2 content, there
dependence,
Cr3C2 content, is a strong
there isasa the strong decrease
onedecrease of
previously of
the volume
observed in Figureloss7,with
is the hardness.
evident. For low ThisCr happens
C content,in the composition
there is a strong range for
decrease which
of thethe Cr
volume 3C2 loss
the volume loss with the hardness. This happens 3 2 in the composition range for which the Cr3C2
with addition
additionthe hardness. generates a happens
generates aThis
decrease of
decrease of the inthethe grain size. Above
composition
grain size. Above rangethe for
1.5 wt% of the
the 1.5which
Cr3C2, the
wt% of CrCr 3C32C
slight decrease
2 addition
, the
in
generates
slight decrease ina
wear loss is due to the increase of the bulk hardness caused by the presence of the new M7C3 hard
decrease
wear loss of is the
duegrain
to thesize. Above
increase ofthe the1.5bulk wt% of Cr3 Ccaused
hardness 2 , the slightby thedecrease
presence in ofwear thelossnewisM due
7C3 to the
hard
phase.
increase
phase. of the bulk hardness caused by the presence of the new M C
7 3 hard phase.

Figure 9. Wear volume vs. the hardness of the WC-10Co cemented carbides.

Figure9.
Figure Wear volume
9.Wear volume vs.
vs. the
thehardness
hardness of
of the
the WC-10Co
WC-10Co cemented
cemented carbides.
carbides.
Metals 2018, 8, 895 8 of 9

4. Conclusions
The addiction of Cr3 C2 to WC-10Co cemented carbides has a double effect on their properties.
Up to 1.5 wt%, it determines a decrease of the grain size. For addition of Cr3 C2 larger than 1.5 wt%,
a hard and brittle phase, the chromium-rich M7 C3 carbide, is formed into the microstructure.
Its chromium content and volume fraction increase as the amount of Cr3 C2 added to the stating
power increases. The M7 C3 carbide produces a modification of the binder which becomes harder and
then more brittle. These two effects control the resulting properties of the cemented carbide.

• Addition of up to 1.5 wt% of Cr3 C2 greatly increases the hardness of the WC-10Co hardmetal due
to the effect of grain size refinement. The slight increase in hardness observed beyond 1.5 wt%
addition is caused only by the increased presence of M7 C3 .
• The addition of Cr3 C2 , up to 1.5 wt%, greatly improves the TRS of the WC-10Co hardmetal.
However, larger amounts of such additions have the reverse effect due to the embrittlement of
the binder.
• Wear performance is significantly enhanced by the addition of Cr3 C2 due to the hardness increase
and reduction of the grain size. However, addition of Cr3 C2 above 1.5 wt% brings about a
moderate increase of the wear performance which is produced just by the progressively increasing
presence of the M7 C3 carbide and not by a further decrease of grain size. Aiming at the combined
optimization of the wear resistance and the mechanical properties of the WC-10Co cemented
carbides, to add amounts of Cr3 C2 higher than 1.5 wt% is then detrimental.

Author Contributions: The contribution of each author was equally distributed, specifically: L.B. performed
the experiments and wrote the paper, F.S. performed the experiments and designed the investigation and the
methodology, U.P. wrote the paper and analyzed the data.
Conflicts of Interest: The authors declare no conflict of interest.

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