materials

Article
Interfaces between Model Co-W-C Alloys with
Various Carbon Contents and Tungsten Carbide
Igor Konyashin 1,2, *, Alexander Zaitsev 1 , Alexander Meledin 3,4 ID
, Joachim Mayer 3,4 ,
Pavel Loginov 1 , Evgeny Levashov 1 and Bernd Ries 2
1 Department of Powder Metallurgy and Functional Coatings, National University of Science and Technology
“MISiS”, Leninsky pr. 4, 119049 Moscow, Russia; [email protected] (A.Z.); [email protected] (P.L.);
[email protected] (E.L.)
2 Element Six GmbH, Städeweg 12-24, 36151 Burghaun, Germany; [email protected]
3 Central Facility for Electron Microscopy (GFE), RWTH Aachen University, Ahornstrasse 55, D-52074 Aachen,
Germany; [email protected] (A.M.); [email protected] (J.M.)
4 Ernst Ruska-Centre for Microscopy and Spectroscopy with Electrons Research Centre Juelich,
D-52425 Juelich, Germany
* Correspondence: [email protected]; Tel.: +49-5542-82412; Fax: +49-6652-82390

Received: 30 January 2018; Accepted: 7 March 2018; Published: 9 March 2018

Abstract: Interfaces between alloys simulating binders in WC-Co cemented carbides and tungsten
carbide were examined on the micro-, nano-, and atomic-scale. The precipitation of fine WC grains
and η-phase occurs at the interface of the alloy with the low carbon content. The precipitation of such
grains almost does not occur in the alloy with the medium-low carbon content and does not take place
in the alloy with the high carbon content. The formation of Co nanoparticles in the binder alloy with
the medium-low carbon content was established. Interfaces in the alloy with the medium-low carbon
content characterized by complete wetting with respect to WC and with the high carbon content
characterized by incomplete wetting were examined at an atomic scale. The absence of any additional
phases or carbon segregations at both of the interfaces was established. Thus, the phenomenon of
incomplete wetting of WC by liquid binders with high carbon contents is presumably related to
special features of the Co-based binder alloys oversaturated with carbon at sintering temperatures.

Keywords: cemented carbides; nanoparticles; model binder alloys; tungsten carbide; carbon content

1. Introduction
Interfaces and grain boundaries in metal-ceramic composites, particularly WC-Co cemented
carbides, play an important role with respect to obtaining high mechanical and performance properties
of such materials. The state of WC-Co grain boundaries in cemented carbides is thought to determine
a unique combination of different properties of such materials. Nevertheless, there is almost no
information in the literature on WC-Co interfaces in WC-Co materials that are not containing grain
growth inhibitors at an atomic level by use of high-resolution transmission electron microscopy
(HRTEM) studies. Such studies are complicated due to difficulties with respect to finding in
transmission electron microscopy (TEM) WC-Co interfaces with both WC and Co grains simultaneously
in a zone axis orientation.
Also, the interaction between Co-based binders and WC grains in WC-Co cemented carbides on
the initial stages of liquid-phase sintering plays an important role with respect to obtaining cemented
carbides with proper microstructures and properties. In the literature, there is no information on
interfaces between tungsten carbide grains and Co-based binders having various carbon contents
when liquid-phase sintering is interrupted in several seconds after the liquid phase formation.

Materials 2018, 11, 404; doi:10.3390/ma11030404 www.mdpi.com/journal/materials

Materials 2018, 11, 404 2 of 11

The interaction between Co-based binders and WC grains on early stages of liquid-phase sintering
can be strongly affected by the carbon content in the binders, which was established in refs. [1,2].
In ref. [1], it was found that the wettability of tungsten carbide by liquid Co-based binders is complete
at low carbon contents and incomplete at high carbon contents. However, a reason for the incomplete
wettability at high carbon contents is not understood so far. It can be supposed that the reason is
related either to the segregation of carbon atoms at the WC/binder interface or to special features the
Co-based binders oversaturated with carbon at sintering temperatures. In ref. [3], a dependence of the
wetting efficiency on the carbon chemical potential in the binder phase is predicted, which can explain
the better wetting of WC that was observed experimentally at low carbon contents.
The interaction between Co-based binders with different carbon contents and WC grains on early
stages of liquid-phase sintering is thought to affect the well-known phenomenon of segregation of
different grain growth inhibitors (vanadium carbide, chromium carbide, etc.) at WC/Co interfaces
in cemented carbides [4–6]. Also, the interaction between Co-based binders and WC can lead to the
formation of complexions in straight WC-Co cemented carbides that are not containing grain growth
inhibitors [7].
There is no information in the literature on the atomic structure of WC-Co interfaces obtained by
use of Co-based binder alloys with various carbon content. Meanwhile, understanding the nature of
WC-Co interfaces can clarify the well-known phenomenon of the liquid binder migration from the
WC-Co regions with high carbon contents into the regions with low carbon contents. This phenomenon
is widely employed for the fabrication of functionally graded cemented carbides having a surface
layer with a significantly reduced Co content and a core region with a high Co content [8–11]. It was
suggested in refs. [1,2] that this phenomenon occurs as a result of different wettability rates of WC
by binders with various carbon contents. However, a mechanism explaining the different wettability
rates with respect to the WC/Co interfaces on the micro-, nano-, and atomic-level is not understood.
The major objective of this work was to examine interfaces between model Co-W-C binder alloys
with various carbon contents and polycrystalline tungsten carbide samples after short sintering at
temperatures of slightly above the corresponding melting points.

2. Materials and Methods

Powders of the model alloys containing 65 wt % Co, corresponding to the eutectic composition
in the pseudo-binary phase diagram W-Co-C, with various amounts of tungsten metal and carbon
black added were mixed in a Turbular mixer. A WC powder with a mean grain size of 0.8 µm and
carbon content of 6.13 wt % and a Co powder with mean grain size of nearly 1 µm were employed.
Three binder alloys with a low carbon content (1.53 wt % C), medium carbon content (2.61 wt % C)
and high carbon content (4.02 wt % C) were made. All the alloys were melted in alumina crucibles in a
vacuum at a temperature of 1500 ◦ C for 1 h. As a result, the Co-based model binder alloys contain some
dissolved carbon and tungsten, thus simulating the real binders in WC-Co that was cemented carbides.
Small samples having a cylindrical shape were cut off from the melted samples and employed for
experiments on examining the interaction between the model alloys and polycrystalline WC samples.
The polycrystalline WC samples were made from a near-nano WC powder with the WC mean
grain size of 0.2 µm. They were first subjected to hot pressing at temperature of 2000 ◦ C and pressure
of 60 MPa for 20 min, followed by hot isostatic pressing in Ar at a temperature of 2100 ◦ C and pressure
of 100 bar for 1 h. The samples have a residual porosity of roughly 2%.
Experiments on examining the interaction between the model binder alloys and the polycrystalline
WC samples were performed in a vacuum furnace. The cylindrical samples of the alloys were located
on the surface of the polycrystalline WC samples and slowly heated up to temperatures slightly
above their melting points and were subjected to liquid-phase sintering for 35 s. The melting points
were established by the DTA studies by use of the STA 449 F1 and STA 429 instruments (Netzsch,
Selb, Germany).
Materials 2018, 11, x FOR PEER REVIEW 3 of 11

Cross-sections of the WC/binder samples after liquid-phase sintering were examined on a light
Materials 2018, 11, 404 3 of 11
microscope and a scanning electron microscope (SEM, S-3400N, Hitachi, Tokyo, Japan), equipped
with a device for energy-dispersive X-ray microanalysis (EDX). X-ray diffraction (XRD) was
performedCross-sections
by the use ofofathe WC/binder
DRON-3 X-raysamples after liquid-phase
diffractometer sintering were examined
(Techoborudovanie, Moscow,on a light using
Russia)
microscope and a scanning electron microscope (SEM, S-3400N, Hitachi, Tokyo, Japan), equipped with
the Cu-Kα radiation. For transmission electron microscopy (TEM) studies, cross-sectional lamellae of
a device for energy-dispersive X-ray microanalysis (EDX). X-ray diffraction (XRD) was performed
the model alloy/WC interfaces were prepared by the focused ion beam (FIB) technique on a FEI
by the use of a DRON-3 X-ray diffractometer (Techoborudovanie, Moscow, Russia) using the Cu-Kα
Quanta 200 3DFor
radiation. FIBtransmission
instrumentelectron
(FEI, Hillsboro,
microscopy OR, USA).
(TEM) Highcross-sectional
studies, resolution TEM (HRTEM),
lamellae high angle
of the model
annular dark field
alloy/WC scanning
interfaces were TEM (HAADF-STEM)
prepared by the focused ionimaging, and technique
beam (FIB) selected on
area electron
a FEI Quantadiffraction
200
(SAED)
3Dwere performed
FIB instrument on Hillsboro,
(FEI, a JEOL-JEM-2100
OR, USA).transmission (JEOL,
High resolution TEMTokyo, Japan)
(HRTEM), highelectron microscope
angle annular
as well as field
dark on the both probe
scanning and image aberration
TEM (HAADF-STEM) corrected
imaging, and selectedFEI
areaTitan 80–300
electron transmission
diffraction (SAED) were electron
performed on a JEOL-JEM-2100 transmission
microscopes operated at 200 kV and 300 kV. (JEOL, Tokyo, Japan) electron microscope as well as on
the both probe and image aberration corrected FEI Titan 80–300 transmission electron microscopes
operated
3. Results andatDiscussion
200 kV and 300 kV.

3. Results
Figure and Discussion
1 shows microstructures of the three alloys with various carbon contents after their initial
sintering at a temperature
Figure of 1500 °C.ofAccording
1 shows microstructures the three alloysto XRD resultscarbon
with various and microstructural
contents after theirexamination
initial
results, the microstructure
sintering at a temperature of the
of 1500 ◦
alloyC.with the lowtocarbon
According content
XRD results and(Figure 1a,b) comprises
microstructural examinationη-phase,
results, the microstructure of the alloy with the low carbon content (Figure
WC in the form of needle-like grains, and a Co-based binder. It was established that melting of this 1a,b) comprises η-phase,
alloy WC
startsin the form °C
at 1370 of needle-like
and ends grains,
at 1399 and°C. a Co-based binder. It wasofestablished
The microstructure the alloy that
withmelting of this
the medium-low
alloy starts at 1370 ◦ C and ends at 1399 ◦ C. The microstructure of the alloy with the medium-low
carbon content (Figure 1c,d) comprises only WC grains surrounded by a Co-based binder matrix.
carbon content (Figure 1c,d) comprises only WC grains surrounded by a Co-based binder matrix.
It was established that melting of this alloy starts at 1332◦ °C and ends at 1366 °C. According to the
It was established that melting of this alloy starts at 1332 C and ends at 1366 ◦ C. According to the
XRD XRD
results the Co-based
results the Co-based binder
binderphase
phaseconsists
consists of of fcc
fccCo.
Co.TheThemicrostructure
microstructure of alloy
of the the alloy
with thewith the
high carbon content
high carbon (Figure
content 1e,f)
(Figure 1e,f)comprises
comprisesWC, WC, Co, andgraphite
Co, and graphite inin form
form of needle-like
of needle-like precipitates.
precipitates.
It wasItestablished
was established thatthat
melting
melting ofofthis
thisalloy
alloystarts at1299
starts at 1299 C ◦ °Cand
and ends
ends ◦
at 1330
at 1330 C. °C.
The The Co-based
Co-based binderbinder
phasephase
of this
of alloy comprises
this alloy comprises a mixture
a mixtureof of fcc
fcc Co andhcp
Co and hcpCo. Co.
The precipitation
The precipitation behavior
behavior andthe
and thephase
phase constitution
constitution ofofthe thethree model
three modelbinder alloysalloys
binder can becan be
related to the results of thermodynamic calculations of the W-Co-C phase diagram at 65%wt
related to the results of thermodynamic calculations of the W-Co-C phase diagram at 65 wt Co,% Co,
which were obtained in ref. [1]. Particularly, special features of the microstructure of the model alloy
which were obtained in ref. [1]. Particularly, special features of the microstructure of the model alloy
with the low carbon content can be understood when taking into account that it crystallizes from the
with the low carbon content can be understood when taking into account that it crystallizes from the
region of the phase diagram, where only the liquid phase and no solid WC phase are present at the
regionsintering
of the phase diagram,
temperature (1500where
◦ C). The only the liquid phase
microstructures and no
of the alloys withsolid WC phase
medium-low andare present
high carbon at the
sintering temperature
contents are obtained (1500
as a°C).
resultTheof microstructures
cooling down from ofthe
theregion
alloysofwith medium-low
the phase diagram, andwherehigh
bothcarbon
contents are obtained
the Co-based liquidasphase
a result
and ofthecooling
solid WCdown phasefrom
coexist the
at region of thetemperature
the sintering phase diagram, ◦
of 1500 where
C. both
the Co-based liquid
Figure phase
2 shows SEM and the solid
images and EDXWCelemental
phase coexist
maps of atthe
theWC/Co
sintering temperature of 1500 °C.
interfaces.

(a) (b)

Figure 1. Cont.
Materials 2018, 11, 404 4 of 11
Materials 2018, 11, x FOR PEER REVIEW 4 of 11

(c) (d)

(e) (f)
Figure 1. Microstructures of model binder alloys with various carbon contents after their original
Figure 1. Microstructures of model binder alloys with various carbon contents after their original
sintering at a temperature of 1500 ◦°C: (a,b) With a low carbon content (a) needle-like WC grains and
sintering at a temperature of 1500 C: (a,b) With a low carbon content (a) needle-like WC grains and
(b) Dendritic
(b) Dendritic η-phase
η-phase crystals);
crystals); (c,d)
(c,d) With
With aa medium-low
medium-low carbon
carbon content
content at
at different
different magnifications;
magnifications;
(e,f) With a high carbon content at different magnifications. All of the micrographs except
(e,f) With a high carbon content at different magnifications. All of the micrographs except for for (e)
(e) are
are
obtained after
obtained after etching
etching in
in the
the Murakami
Murakami reagent.
reagent.

Figure 2 shows SEM images and EDX elemental maps of the WC/Co interfaces.
As one can see in Figure 2a small grains precipitate from the alloy with the low carbon content on
As one can see in Figure 2a small grains precipitate from the alloy with the low carbon content
the surface of the polycrystalline tungsten carbide sample. These precipitates consist of WC and η-type
on the surface of the polycrystalline tungsten carbide sample. These precipitates consist of WC and
phase, as some of them do not contain any Co and some of them contain some Co. The precipitation of
η-type phase, as some of them do not contain any Co and some of them contain some Co. The
the fine grains in the initial stage of liquid-phase sintering, which was not described in the literature
precipitation of the fine grains in the initial stage of liquid-phase sintering, which was not described
before, is presumably related to the well-known fact that the model alloy with the low carbon content
in the literature before, is presumably related to the well-known fact that the model alloy with the
is oversaturated with tungsten metal [12]. As a result of the interaction of such a binder alloy that was
low carbon content is oversaturated with tungsten metal [12]. As a result of the interaction of such a
oversaturated with tungsten with the polycrystalline tungsten carbide sample, the excess of tungsten
binder alloy that was oversaturated with tungsten with the polycrystalline tungsten carbide sample,
presumably reacts with the carbon containing in the surface layer of the polycrystalline sample leading
the excess of tungsten presumably reacts with the carbon containing in the surface layer of the
to its partial decarburization and formation of the fine grains of WC and η-type phase.
polycrystalline sample leading to its partial decarburization and formation of the fine grains of WC
Figure 2b shows a SEM image of the interface region after melting the alloy with the medium-low
and η-type phase.
carbon content on the surface of the polycrystalline tungsten carbide sample. As it can be seen in
Figure 2b shows a SEM image of the interface region after melting the alloy with the medium-
Figure 2b, the interface region comprises very few precipitates of small WC grains deposited directly
low carbon content on the surface of the polycrystalline tungsten carbide sample. As it can be seen in
on the surface of the polycrystalline tungsten carbide sample. This is presumably related to the fact
Figure 2b, the interface region comprises very few precipitates of small WC grains deposited directly
that this model alloy comprises significantly less dissolved tungsten metal than the alloy with the low
on the surface of the polycrystalline tungsten carbide sample. This is presumably related to the fact
carbon content.
that this model alloy comprises significantly less dissolved tungsten metal than the alloy with the
Figure 2c
low carbon shows a SEM image of the interface region after melting the alloy with the high carbon
content.
content on the surfacea of
Figure 2c shows theimage
SEM polycrystalline tungsten
of the interface carbide
region after sample. Onealloy
melting the can with
see that
the there are no
high carbon
precipitates
content on thethatsurface
are similar to those
of the forming intungsten
polycrystalline the case of the model
carbide alloyOne
sample. withcan
thesee
lowthat
carbon
therecontent,
are no
and there are also no inclusions of free carbon at the Co/WC interface.
precipitates that are similar to those forming in the case of the model alloy with the low carbon
Figure
content, and3athere
showsarethe appearance
also of the
no inclusions of polycrystalline WCCo/WC
free carbon at the sampleinterface.
with a film of the binder alloy
with the medium-low carbon content after its melting and spreading over the WC sample. The wetting
Materials 2018, 11, 404 5 of 11

angle is close to 0 in this case indicating complete wetting. A FIB lamella was cut off from the region
of the sample indicated by an arrow in Figure 3a. Figure 3b shows the nano-structure of the WC/Co
interface for the model binder alloy with the medium-low carbon content with insets indicating SAED
patterns. It was not possible to index the binder phase as fcc or hcp Co by the use of electron diffraction,
Materials 2018, 11, x FOR PEER REVIEW 5 of 11
however, XRD results indicate that Co is present in this sample as the cubic modification.

(a)

(b)

Figure 2. Cont.
Materials 2018, 11, 404 6 of 11
Materials 2018, 11, x FOR PEER REVIEW 6 of 11

(c)
Figure 2. Scanning electron microscope (SEM) images and elemental maps of C, Co, and W in the
interface region between the model binder alloys and polycrystalline WC samples: (a) Alloy with the
low carbon content; (b) Alloy with the medium-low carbon content (precipitates of fine WC grains
are indicated by arrows); (c) Alloy with the high carbon content.

Figure 3a shows the appearance of the polycrystalline WC sample with a film of the binder alloy
with the medium-low carbon content after its melting and spreading over the WC sample.
The wetting angle is close to 0 in this case indicating (c) complete wetting. A FIB lamella was cut off from
the region of the sample indicated by an arrow in Figure 3a. Figure 3b shows the nano-structure of
Figure 2.
the WC/Co
Figure 2.interface
Scanning electron
Scanningfor microscope
the model
electron binder
microscope (SEM)
alloyimages
(SEM) with and
images the elemental
and elemental maps
medium-low of
of C,
C, Co,
mapscarbon and
and W
content
Co, in the
Wwith
in theinsets
interface region
region between
between the
interface
indicating SAED patterns. Itthe model binder
notbinder
model
was alloys and
alloys
possible and polycrystalline
to indexpolycrystalline WC
WC samples:
the binder phase samples: (a)
as fcc or(a) Alloy
Alloy with
hcp Cowith the
by the
the use
low carbon
low carbon content; (b)
content; (b) Alloy with
Alloy with the medium-low
theresults
medium-low carbon
carbon content (precipitates of fine WC grains
of electron diffraction, however, XRD indicate thatcontent
Co is (precipitates of fine
present in this WC grains
sample arecubic
as the
are indicated
indicated by arrows);
by arrows); (c) Alloy
(c) Alloy withwith the high
the high carbon
carbon content.
content.
modification.
Figure 3a shows the appearance of the polycrystalline WC sample with a film of the binder alloy
with the medium-low carbon content after its melting and spreading over the WC sample.
The wetting angle is close to 0 in this case indicating complete wetting. A FIB lamella was cut off from
the region of the sample indicated by an arrow in Figure 3a. Figure 3b shows the nano-structure of
the WC/Co interface for the model binder alloy with the medium-low carbon content with insets
indicating SAED patterns. It was not possible to index the binder phase as fcc or hcp Co by the use
of electron diffraction, however, XRD results indicate that Co is present in this sample as the cubic
modification.

(a) (b)
Figure 3.
Figure 3. WC-Co
WC-Cointerfaces
interfacesinin
thethe sample
sample obtained
obtained afterafter melting
melting the with
the alloy alloythe
with the medium-low
medium-low carbon
content on the WC surface: (a) The sample appearance with an arrow indicating where a where
carbon content on the WC surface: (a) The sample appearance with an arrow indicating focuseda
focused
ion beamion beam
(FIB) (FIB)
lamella waslamella
cut off was
fromcutthe off from region
interface the interface region
(note that (note that
the sample the sample by
is characterized is
characterized by complete wetting); (b) Interface nano-structure with insets indicating selected
complete wetting); (b) Interface nano-structure with insets indicating selected area electron diffraction area
electronpatterns.
(SAED) diffraction (SAED) patterns.

Figure 4a–e show the WC/Co interface for the binder alloy with the medium-low carbon content
at an atomic scale. In Figure 4a,b, it(a) can be seen that the Co-based alloy (b)comprises Co nanoparticles of
several nanometer
Figure 3. WC-Coin interfaces
size having different
in the samplecrystal lattice
obtained afterorientations, which
melting the alloy wasthe
with established
medium-low for the
first time in content
carbon the present work.
on the WC Itsurface:
should(a)beThe
mentioned that the mean
sample appearance withgrain size ofindicating
an arrow the Co-based
wherebinders
a
in industrial cemented
focused ion carbides
beam (FIB) after
lamella was conventional
cut off fromsintering is ofregion
the interface the order
(noteofthat
100 the or larger
µm sample is [12].
The presence of such
characterized Co nanoparticles
by complete wetting); after the short
(b) Interface liquid-phasewith
nano-structure sintering
insets indicates
indicatingthat the Co-based
selected area
electron diffraction (SAED) patterns.
 Figure 4a–e show the WC/Co interface for the binder alloy with the medium-low carbon content
at an atomic scale. In Figure 4a,b, it can be seen that the Co-based alloy comprises Co nanoparticles
of several nanometer in size having different crystal lattice orientations, which was established for
the first 2018,
Materials time11,in404
the present work. It should be mentioned that the mean grain size of the Co-based 7 of 11
binders in industrial cemented carbides after conventional sintering is of the order of 100 µm or larger
[12]. The presence of such Co nanoparticles after the short liquid-phase sintering indicates that the
binder canbinder
Co-based be nanostructured. This can beThis
can be nanostructured. a result
can beof athe presence
result of theofpresence
the liquidofphase for aphase
the liquid short time,
for a
followed by its fast cooling. The nanoparticles presumably form due to the formation
short time, followed by its fast cooling. The nanoparticles presumably form due to the formation of a great number of
of solid Co nuclei in the whole volume of the liquid model alloy, which
a great number of solid Co nuclei in the whole volume of the liquid model alloy, which are are maintained due to the
rapid binderdue
maintained solidification.
to the rapidAccording to ref. [12], binder
binder solidification. alloys to
According of ref.
cemented carbides
[12], binder withoflow
alloys carbon
cemented
contents comprise relatively much dissolved tungsten (up to 20 wt %), which
carbides with low carbon contents comprise relatively much dissolved tungsten (up to 20 wt %), can play an important
role with
which canrespect
play antoimportant
formationrole
of such
withCo nanoparticles.
respect to formation of such Co nanoparticles.

(a) (b)

(c) (d)

(e)
Figure 4. WC-Co interfaces in the sample obtained after melting the alloy with the medium-low
Figure 4. WC-Co interfaces in the sample obtained after melting the alloy with the medium-low
carbon content on the WC surface: (a) Binder nano-structure near the interface (JEOL JEM-2100);
carbon content on the WC surface: (a) Binder nano-structure near the interface (JEOL JEM-2100);
(b–d) Aberration corrected high-resolution transmission electron (HRTEM) images of the interface at
(b–d) Aberration corrected high-resolution transmission electron (HRTEM) images of the interface at
different magnifications (nanoparticles in the Co-based alloy are indicated by arrows), (e) High Angle
different magnifications (nanoparticles in the Co-based alloy are indicated by arrows), (e) High Angle
Annular Dark Field Scanning TEM (HAADF STEM) after gamma-correction and high-pass filtering
(FEI Titan 80–300).
Materials 2018, 11, x FOR PEER REVIEW 8 of 11

Annular
Materials Dark
2018, 11, 404 Field Scanning TEM (HAADF STEM) after gamma-correction and high-pass filtering8 of 11
(FEI Titan 80–300).

As it can be seen Figure 4c–e, the crystal lattices of Co and WC are obviously incoherent incoherent and and the
interface isisclean
interface cleanand
and free
free of any
of any inclusions,
inclusions, defects,
defects, or disorders,
or disorders, which which
explainsexplains the complete
the complete wetting
wetting
of WC byofthe WC by the Co-based
Co-based binders
binders with the with the medium-low
medium-low carbon contents
carbon contents [1,2]. [1,2].
Figure 5a
Figure 5ashows
showsthe thepolycrystalline
polycrystallineWC WCsample
sample with
with a droplet
a droplet of the
of the binder
binder model
model alloy
alloy withwith
the
the high
high carboncarbon content
content after
after its its melting
melting followed
followed by solidification.
by solidification. The wetting
The wetting angle is angle
equal is
to equal
roughly to
15 ◦
roughly 15°
in this in this
case case indicating
indicating thatiswetting
that wetting is incomplete.
incomplete. A FIBwas
A FIB lamella lamella was
cut off fromcutthe
off region
from theof
region
the of the
sample sample indicated
indicated by an arrowby an
in arrow
Figurein5a.
Figure
Figure5a.5b
Figure
shows 5bthe
shows the interface
interface nano-structure
nano-structure for the
for the model
binder binderalloy
model alloy
with thewith
highthe high content
carbon carbon content with
with insets insets indicating
indicating SAED patterns,
SAED patterns, which
which provide
provide evidence
evidence that Co isthat Co isin
present present
the fccin the fccmodification.
crystal crystal modification.

(a)

(b)
Figure 5.5.WC-Co
Figure WC-Cointerfaces
interfacesinin
thethe sample
sample thatthat
waswas obtained
obtained after after melting
melting the with
the alloy alloythe
with
highthe high
carbon
carbon content on the WC surface: (a) The sample appearance with an arrow indicating
content on the WC surface: (a) The sample appearance with an arrow indicating where a FIB lamella where a FIB
lamella was cut off from the interface region (note that the sample is characterized by
was cut off from the interface region (note that the sample is characterized by incomplete wetting); incomplete
wetting);
(b) (b)nano-structure
Interface Interface nano-structure
with insetswith insets indicating
indicating SAED patterns.
SAED patterns.

Figure 6 shows HRTEM image of the WC/Co interface between the binder model alloy with the
Figure 6 shows HRTEM image of the WC/Co interface between the binder model alloy with
high carbon content and tungsten carbide. The interface between WC and the Co-based binder with
the high carbon content and tungsten carbide. The interface between WC and the Co-based binder
the high carbon content shown in Figure 6a,b is characterized by defects, disorders, and the presence
with the high carbon content shown in Figure 6a,b is characterized by defects, disorders, and the
of a dark contrast layer at the interface. The Co grain shown in Figure 6a appears to be highly
presence of a dark contrast layer at the interface. The Co grain shown in Figure 6a appears to be highly
twinned. In contrast to the sample with the medium-low carbon content, there are no nanoparticles
twinned. In contrast to the sample with the medium-low carbon content, there are no nanoparticles in
Materials 2018, 11, 404 9 of 11
Materials 2018, 11, x FOR PEER REVIEW 9 of 11

the Co-based
in the alloy
Co-based with
alloy thethe
with high carbon
high content,
carbon which
content, is presumably
which a result
is presumably of oversaturating
a result this
of oversaturating
alloy with carbon, resulting in low concentrations of tungsten being dissolved in this model alloy.
this alloy with carbon, resulting in low concentrations of tungsten being dissolved in this model alloy.

(a) (b)

(c) (d)

(e)
Figure 6. WC-Co interfaces in the sample obtained after melting the alloy with the high carbon content
Figure 6. WC-Co interfaces in the sample obtained after melting the alloy with the high carbon content
on the WC surface: (a) Binder nano-structure near the interface (JEOL JEM-2100); (b) HRTEM image
on the WC surface: (a) Binder nano-structure near the interface (JEOL JEM-2100); (b) HRTEM image of
of the interface (JEOL JEM-2100); (c) HAADF STEM (Z-contrast) image of the interface; (d) ADF STEM
the interface (JEOL JEM-2100); (c) HAADF STEM (Z-contrast) image of the interface; (d) ADF STEM
(both diffraction- and Z-contrasts) image of the interface; (e) Fourier-filtered high-resolution STEM
(both diffraction- and Z-contrasts) image of the interface; (e) Fourier-filtered high-resolution STEM
image of the interface (FEI Titan 80–300).
image of the interface (FEI Titan 80–300).

Additional high-resolution STEM studies of the WC-Co interface were carried out in order to
clarify the atomichigh-resolution
Additional structure of theSTEM studies
interface, of the
which WC-Co
cannot interface
be clearly were carried
established by useout in order
of the high-
to clarify the atomic structure of the interface, which cannot be clearly established
resolution TEM (Figure 6a,b). Figure 6c shows a HAADF STEM (Z-contrast) image of the interface by use of the
high-resolution
and Figure 6d TEMshows (Figure 6a,b).STEM
an ADF Figure(both
6c shows a HAADF
diffraction- STEM
and (Z-contrast)
Z-contrasts) image
image ofofthe
theinterface.
interface
and
The Figure 6d shows
WC surface an ADFmade
roughness STEM (both
the diffraction-
investigation ofand
the Z-contrasts) imagedifficult.
WC-Co interface of the interface.
However, The WC
it was
possible to find a region with a relatively sharp WC-Co interface. As one can see in the HAADF STEM
Materials 2018, 11, 404 10 of 11

surface roughness made the investigation of the WC-Co interface difficult. However, it was possible to
find a region with a relatively sharp WC-Co interface. As one can see in the HAADF STEM (Z-contrast)
image (Figure 6c), there is no dark contrast layer at the WC/Co interface providing evidence for the
absence of carbon inclusions, precipitations, or segregated carbon atoms at the interface. The Co-layer
adjacent to the WC-Co interface is formed by a twinned single crystal. The bright diffraction contrast
indicates the strained dislocation regions in the Co layer near the WC/Co interface shown in Figure 6d,e.
Therefore, incomplete wetting of WC by the model binder alloy with the high carbon content is
presumably related to the special features of the Co-based alloys oversaturated with carbon, which
corresponds well to the theoretical prediction that is obtained in ref. [3].

4. Conclusions
A phenomenon of precipitating fine grains of WC and η-phase was for the first time observed in
the interface region of the binder model alloy with the low carbon content. This phenomenon almost
does not occur in the model alloy with the medium-low carbon content and does not occur in the
model alloy with the high carbon content. The formation of Co nanoparticles in the binder model
alloy with the medium-low carbon content near the WC/Co interface was established for the first
time. The WC/Co interface is free of any inclusions, defects, or disorders at an atomic scale in the case
of the binder alloy with the medium-low carbon content. The interface between WC and the binder
model alloy with the high carbon content is free of any carbon segregation or precipitation at an atomic
scale. Therefore, it is thought that the incomplete wetting of WC by liquid Co-based binders with
high carbon contents in cemented carbides is related to special features of the binder alloys that were
oversaturated with carbon at sintering temperatures.

Acknowledgments: This work was supported by the Ministry of Education and Science of the Russian
Federation in the frame of the Federal Target Program «Investigations and Developments over Priority
Directions of the Scientific and Technology Complex of Russia for 2014–2020», agreement No. 14.575.21.0156,
project RFMEFI57517X0156.
Author Contributions: A. Zaitsev and E. Levashov conceived and designed the experiments; A. Meledin,
and P. Loginov performed the experiments and measurements; J. Mayer and I. Konyashin analyzed the data;
I. Konyashin and B. Ries wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Konyashin, I.; Zaitsev, A.A.; Sidorenko, D.; Levashov, E.A.; Ries, B.; Konishev, S.N.; Sorokin, M.;
Mazilkin, A.A.; Herrmann, M.; Kaiser, A. Wettability of tungsten carbide by liquid binders in WC-Co
cemented carbides: Is it complete for all carbon contents? Int. J. Refract. Met. Hard Mater. 2017, 62, 134–148.
[CrossRef]
2. Konyashin, I.; Zaitsev, A.A.; Sidorenko, D.; Levashov, E.A.; Konischev, S.N.; Sorokin, M.; Hlawatschek, S.;
Ries, B.; Mazilkin, A.A.; Lauterbach, S.; et al. On the mechanism of obtaining functionally graded hardmetals.
Mater. Lett. 2017, 186, 142–145. [CrossRef]
3. Petisme, M.V.G.; Johansson, S.A.E.; Wahnström, G. A computational study of interfaces in WC-Co cemented
carbides. Model. Simul. Mater. Sci. Eng. 2015, 23, 045001. [CrossRef]
4. Lay, S.; Hamar-Thibault, S.; Lackner, A. Location of VC in VC, Cr3 C2 codoped WC-Co cermets by HRTEM
and EELS. Int. J. Refract. Met. Hard Mater. 2002, 20, 61–69. [CrossRef]
5. Warbichel, P.; Hoferm, F.; Grogger, W.; Lackner, A. EFTEM-EELS Characterization of VC and Cr3 C2
Doped Cemented Carbides. In Proceedings of the 15th International Plansee Seminar, Reutte, Austria,
25–29 May 2001; Kneringer, G., Rödhammer, P., Wildner, H., Eds.; Plansee: Reutte, Austria, 2001; Volume 2,
pp. 65–74.
6. Johansson, S.A.E.; Wahnström, G. First-principles study of an interfacial phase diagram in the V-doped
WC-Co system. Phys. Rev. 2012, 86, 035403. [CrossRef]
7. Konyashin, I.; Sologubenko, A.; Weirich, T.; Ries, B. Complexion at WC-Co grain boundaries of cemented
carbides. Mater. Lett. 2017, 187, 7–10. [CrossRef]
Materials 2018, 11, 404 11 of 11

8. Guo, J.; Fan, P.; Fang, Z. A new method for making graded WC-Co by carburizing heat treatment of fully
densified WC-Co. In Proceedings of the 17th International Plansee Seminar, Reutte, Austria, 25–29 May 2009;
Sigl, L., Rödhammer, P., Wildner, H., Eds.; Plansee: Reutte, Austria, 2009; Volume 2, pp. 1–6.
9. Zhang, L.; Wang, Y.; Yu, X.; Chen, S.; Xiong, X. Crack propagation characteristics and toughness of
functionally graded WC-Co cemented carbides. Int. J. Refract. Met. Hard Mater. 2008, 26, 295–300. [CrossRef]
10. Konyashin, I.; Ries, B.; Lachmann, F.; Fry, A.T. Gradient Hardmetals: Theory and Practice. Int. J. Refract. Met.
Hard Mater. 2013, 36, 10–21. [CrossRef]
11. Konyashin, I.; Ries, B.; Lachmann, F.; Fry, A.T. A novel sintering technique for fabrication of functionally
gradient WC-Co cemented carbides. J. Mater. Sci. 2012, 47, 7072–7084. [CrossRef]
12. Tretyakov, V.I. Bases of Materials Science and Technology of Fabrication of Sintered Cemented Carbides; Metallurgiya:
Moscow, Russia, 1975.

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