ccts 1

International Journal of Refractory Metals & Hard Materials 80 (2019) 40–68
Contents lists available at ScienceDirect
International Journal of Refractory Metals

& Hard Materials
journal homepage: www.elsevier.com/locate/IJRMHM
Cemented carbide microstructures: a review T

José García , Verónica Collado Ciprés, Andreas Blomqvist, Bartek Kaplan
⁎
AB Sandvik Coromant R&D, Lerkrogsvägen 19, SE-126 80 Stockholm, Sweden
ARTICLE INFO ABSTRACT
Keywords: Cemented carbides cover a wide range of applications in many relevant industries, i.e. as cutting tools (turning,
Cemented carbide milling, drilling) for machining of metal components in the automotive and/or aerospace industry, as compo-
Cermet nents of drill bits or road headers in the rock tools and mining area or as wear parts in wire drawing dies or
Microstructure punch tools. In this review selected cemented carbide and cermet microstructures are presented. The focus is on
Gradient
microstructures, both those that are already established in the cemented carbide industry and those which have
Binder
Properties
drawn scientific attention due to new potential applications. Cemented carbides are here divided in four groups
based on microstructure and chemistry: WC morphology and chemistry, cubic carbide containing cemented
carbide and cermets, functionally graded cemented carbides, and binder design of cemented carbides.
Furthermore, this review covers some historical background that motivated the microstructure design as well as
the status of each class of materials nowadays. The paper aims at categorising cemented carbides in a structured
way and to serve as an introduction to cemented carbide microstructures for engineers, researchers and scien-
tists.
1. Introduction materials by pressing and sintering. Tungsten monocarbide (WC) and

metals like Fe, Ni and Co where sintered in the presence of a liquid
Cemented carbides1 and cermets are one of the most widespread phase to produce a solid dense body [1]. In 1927 the German company
powder metallurgy products worldwide. The reason for this is their Friedrich Krupp marketed worldwide the first cemented carbide com-
outstanding combination of hardness and toughness compared to other posed of tungsten carbide and cobalt (WC-Co) under the name WIDIA
cutting materials, such as diamond or high speed steels. By selecting the (an acronym for the German words WIe DIAmant = like diamond).
appropriate combination of hard phases, metallic binder phase and They were primarily used as materials for wire drawing dies and wear
processing parameters, a wide combination of microstructures with a resistant parts. Already in the first years it was recognized that adding
variety of mechanical properties can be achieved. The broad variability other carbides (such as TiC) can improve the properties of the basic WC-
of cemented carbides concerning composition and properties has led to Co composition in certain machining operations. Later, the addition of
various international classification systems, being the most relevant nitrogen in the form of TiN or Ti(C,N) to carbides of the type TiC-Mo2C-
ones: the ISO-committee TC (29 April 1958), the US-Industrial code and Ni led to the first generation of cermets with increased performance for
the DIN 4990 (1948) [1]. In this work, we aim at categorising relevant high cutting speed in finishing operations [2–4].
microstructures of cemented carbides and cermets in four main groups, During the 80's, the introduction of hard refractory metal carbide
each containing five categories, as seen in Fig. 1. In the following and aluminum oxide coatings provided a dramatic increase in cutting
chapters this categorisation of microstructures will be referred to tool performance. By means of coating processes like chemical vapour
throughout the entire manuscript. deposition (CVD) or physical vapour deposition (PVD), hard coatings
In 2016, the 90th anniversary of cemented carbides was celebrated such as TiC, TiN, Ti(C,N) were deposited on the surface of cemented
in a special symposium during the Euro PM 2016 conference in carbides. Today standard coating materials differ in properties, cov-
Hamburg, Germany, pointing out that cemented carbides are quite new ering different application areas. Multilayer CVD coatings containing,
materials. The first patents about cemented carbides were issued in e.g., Al2O3, Ti(C,N), Zr(C,N) and (Ti,Al)N have proven to be advanta-
1923 to the German company “Osram Studiengesellschaft” for a geous for applications where high oxidation and wear resistance, as
method by K. Schröter (German patent DRP 420689) to produce hard well as low coefficient of friction are needed. For an overview of
⁎
Corresponding author at: Lerkrogsvägen 19, SE-126 80 Stockholm, Sweden.
E-mail address: [email protected] (J. García).
1
Cemented carbides can also be referred as to “hardmetals” or “hard metals”. In German only the term Hartmetall exists [1].
https://doi.org/10.1016/j.ijrmhm.2018.12.004
Received 13 August 2018; Received in revised form 5 December 2018; Accepted 9 December 2018
Available online 10 December 2018
0263-4368/ © 2018 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
J. García et al. International Journal of Refractory Metals & Hard Materials 80 (2019) 40–68
Fig. 1. Categorisation of cemented carbide microstructures selected in this work.
coating technology in cemented carbide industry the reader is referred about 4%, and polycrystalline diamond (PCD) and cubic boron nitride
to e.g. [5–7]. (CBN) 1% [9].
The global production of cemented carbides has grown rapidly in The properties of cemented carbides are given by the combination
the past 30 years. The total cemented carbide production in 1993 was of vastly different constituents, e.g., soft and ductile Co-based binder
around 20,000 tons and increased from 30,000 tons (2000) to almost with hard and wear resistant WC or cubic carbides [10,11]. By selecting
60,000 tons in 2008, particularly due to the entry of China on to the appropriate raw materials, compositions and suitable processing para-
market. From year 2000 and to date the cemented carbide production meters, a wide combination of mechanical properties can be achieved
in China raised from 7000 tons (2001) to 20,000 tons (2011) and (Fig. 2). In particular their unique combination of hardness and
28,000 (2017). In 2017 the tungsten metal consumption in China toughness make them attractive for many industrial applications (see
reached 55,000 tons which is almost 60% of the total world con- Fig. 3). In this review, we will occasionally mention the connection
sumption. It is estimated that today some 35% in the world's tungsten between the microstructure and the performance. However, it should
supply is recycled. Tungsten processing industry can treat almost every be noted that when performance testing is done on very different ma-
kind of tungsten-containing scrap to recover tungsten and, if present, terials, it is not possible to objectively conclude that the selected
other valuable constituents. Tungsten scrap, due to its high tungsten comparison displays a general trend. Therefore, any machining or wear
content in comparison to ore, is a valuable raw material [8]. Almost test result referred to in this study is to be considered as an example of
65% of the total cemented carbide production is related to metal cutting the specific test conditions applied by the respective authors.
tools. Mining, oil drilling, and rock industries hold about 15% of the
market share, whereas wood and construction industries account for
2. Constituents
10%. Compared to other hard materials, cemented carbides make up
50% of the total world market; high speed steels are 45%, ceramics
Cemented carbide consists of hard refractory carbides, nitrides or
41
3000 150
2750 140
130
2500
120
Hardne ss (V ic ke rs units)
2250 110
Toughness (MPam½)
2000 100
1750 90
80
1500
70
1250 60
1000 50
750 40
30
500
20
250 10
0 0
700 9000
650
8000
600
Compressive strength (MPa)

M odulus of e lastic ity (GPa)
550 7000
500
450 6000
400 5000
350
300 4000
250 3000
200
150 2000
100
1000
50
0 0
Fig. 2. Typical property ranges of different materials in relation to cemented carbide. Data from AB Sandvik.
carbonitrides of the transition metals (groups 4, 5 and 6 of the transi- subsequent process and the quality of the final product. Consequently,
tion metals in the periodic table) embedded in a ductile metal binder in the design of cemented carbide microstructures all production steps
matrix. The main phases present in cemented carbides are the hex- must be taken into consideration.
agonal WC phase, the mixed cubic carbide/carbonitride phase (also In terms of adjusting the microstructure and mechanical properties
called γ-phase or fcc-phase) and the Co binder phase, which can also be of cemented carbides the sintering step is one of the most important
Ni-based or a combination of Fe-Co-Ni metals. The γ-phase is composed process in the production of cemented carbides (Fig. 4). Densification
of carbonitrides of the groups 4 and 5 of the periodic table. The hard takes places during sintering, to get a pore-free microstructure and the
phases have exceptional hardness, high melting point, metallic lustre, final dimensions of the component. Cemented carbides are produced by
characteristic colours, and simple crystal structures. Furthermore, the liquid phase sintering. As reported in [16,17] there are four main steps
WC has high electrical and thermal conductivity, as well as good wet- during the sintering process. In the initial step shrinkage takes place
ting with metallic liquids. The γ-phase also forms solid solutions with mainly due to reduction of oxides and degassing of binder and im-
wide ranges of homogeneity with both substitutional and interstitial purities. In the second step, as the temperature increases, solid state
elements [12]. Properties of common carbides and nitrides used in the sintering begins. The binder phase begins to wet the WC grains and
production of cemented carbides are shown in Table 1. dissolution and transport of material takes place by solid state diffusion
and bulk transport. Porosity decreases as the temperature rises and
3. Processing material dissolved in the binder metal start to re-precipitate on un-
dissolved grains. Densification enhances due to re-arrangement of
The production of cemented carbide products is a complex powder particles. This is accompanied by further shrinkage. In the third step the
metallurgical process involving many processing steps, such as: raw melting temperature is reached (for a typical WC-Co alloy saturated in
powder production, mixing and milling of powders, spray drying to carbon is ~ 1300 °C) and liquid phase sintering begins. Grains dissolve
produce granulated ready to press powders, pressing, extruding or in the binder phase until its saturation, which is controlled by the so-
moulding to final shape, dewaxing and pre-sintering, sintering (i.e. li- lubility product. Smaller grains dissolve preferentially, and the larger
quid phase sintering, sinter-HIP, gradient sintering), post-sintering grains (which are not dissolved) grow on the expense of the smaller
treatment (i.e. grinding) and finishing operations (i.e. blasting) [15]. grains. This Ostwald Ripening process leads to coarsening of WC grains
All manufacturing processes are linked, meaning that any change in any but also to complete densification [18,19], see Fig. 5. In the fourth step
manufacturing step in the production chain will influence the (cooling down) the binder phase solidifies. Some re-precipitation is
42
10 Resource
extraction and
construction
5
Rolls
2
WC grain size (µm)
Can
tooling
Wear Metal 800
1 parts cutting
Wood
working
1000
0.5
1200
Composite
Wire machining
0.2 drawing
1400
1600
1800
2000
0 5 10 15 20 25 30
Cobalt content (wt%)
Fig. 3. Combinations of WC grain size and cobalt content in cemented carbides, showing a wide range of applications. The lines indicate values of isohardness
(Vickers a.u.). Data from AB Sandvik.
Table 1
Typical values of selected properties of carbides and nitrides to produce cemented carbides [13,14].
Compound Pearson symbol Lattice parameter(s) (nm) Density Micro-hardness Melting point Young‘s modulus Heat conductivity
(g cm−3) (GPa) (°C) (GPa) (Wm−1 K−1)
WC hP2 a = 0.29058 c = 0.28365 15.72 23 2776 707 120

Mo2C hP3 a = 0.30233 c = 0.47344 9.18 17 2520 530 15
Cr3C2 oP20 a = 0.28290 b = 0.55329 6.68 27 1810 380 14
c = 1.14719
TiC cF8 0.4328 4.93 28 3067 450 28.9
ZrC cF8 0.4700 6.46 25 3420 350 24.6
HfC cF8 0.4638 12.3 20 3930 420 25.1
VC0.88 cF8 0.4164 5.36 26 2650 430 26.8
NbC cF8 0.4470 7.78 18 3610 340 27.0
TaC cF8 0.4455 14.48 16 3985 290 22.1
TiN cF8 0.4242 5.39 17 3050 420 29
present in the last step leading to further coarsening. Typically sintering transport or surface decarburization during the liquid sintering step
is carried out in sintering furnaces with controlled conditions of tem- (controlled gas mixture). If needed, porosity can be eliminated by sin-
perature, pressure, atmosphere, heating/cooling rates and sintering tering with high gas pressure (sinter-HIP) in the last step of the sintering
times. Other processes to consolidate cemented carbides have been process [20].
explored, such as microwave sintering or spark plasma sintering, but A crucial aspect to consider when producing cemented carbide is the
are not established at industry. During the entire sintering cycle the control of carbon content. When being at low carbon contents, a sub-
control of the sintering atmosphere is of most relevance in order to stoichiometric carbide phase called η-phase can form. This phase tends
reduce the pressing binder (debinding), to reduce the oxide scales of the to decrease the toughness of cemented carbides, especially if it pre-
metal binder and carbides particles (vacuum step) and to avoid binder cipitates as large dendrites. If, on the contrary, a cemented carbide with
43
T (°C)
1600
1400
1200
1000
800
600
Debinding Vacuum Ar/CO/N2 HIP
400
200 Outgassing
Humidity organics
0
0 1 2 3 4 5 6 7 8
Time (h)
Fig. 4. Schematic description of a sintering process to produce cemented carbides. Regions for debinding, vacuum, reactive and protective gases and hot isostatic
pressing (HIP) are shown. The area for outgassing evolution during sintering is also indicated [20].
increasing carbon activity. If the C content of the cemented carbide is

less than the ideal ratio [C]/[W] = 1, the amount of tungsten dissolved
in Co increases. In modern manufacturing lines, carbon can be con-
trolled in ranges of 0.05 wt% [20].
4. WC morphology and chemistry
The hexagonal WC has the most prominent place of all hard phases
in cemented carbides. > 80% of all cemented carbide grades contain
WC, and many of them are pure WC-Co alloys. The WC phase (hex-
agonal close packed: hcp) has an extremely narrow homogeneity range.
The carbon content corresponds to the theoretical value of the stoi-
chiometric composition, 50 at.%C (~6.13 wt%C). WC melts under de-
composition at 2776 °C.
In sintered cemented carbides, the WC phase can be recognized as
prismatic grains in the microstructure. WC provides high hardness but
at the same time it also exhibits a significant ability for plastic de-
formation [21]. This combination of properties and the excellent wet-
ting of Co on WC, which is important for the sinterability of the final
product, are some of the most important factors for the properties of the
WC-Co system [Fig. 7]. Some attempts were carried out to replace WC
by Mo2C in conventional cemented carbides. However, the excellent
properties of WC-based cemented carbides could not be reached yet
[22].
Fig. 5. Temperature ranges for densification stages, together with an schematic

description of microstructure evolution and corresponding fracture images 4.1. WC-Co
(Scanning Electron Microscopy (SEM) during sintering of WC-Co cemented
carbide. Adapted from [19]. Cemented carbides are in many ways a unique class of materials.
Most notably, the matrix phase, i.e., the binder, is the minority phase.
The interplay between the binder and the carbide phases determine the
final microstructure. Many authors report on several different quan-
high carbon is produced, free carbon may precipitate as graphite and tities related to cemented carbide microstructures, e.g., WC grain size,
lower the mechanical properties of the material (Fig. 6). carbide contiguity, volume fraction of binder and binder mean free
Therefore, the carbon content of the sintered alloy must be kept path. However, these variables are clearly inter-related and most often
within narrow limits in which neither η-phase or graphite precipitate, it is sufficient to give only two of them, e.g., WC grain size and Co
which indeed depends on the overall composition of the material. It is content, for a full description of the microstructure (Fig. 8).
worth mentioning that the solubility of W in liquid Co decreases with By adjusting the binder content and WC grain size, desired
44
Fig. 6. Light optical microscopy pictures showing η-phase (left) and graphite (right) formation on a WC-10%Co cemented carbide. The phase diagram in the centre
shows the possible phases. The defect free two-phase region (WC: tungsten carbide, β: Co binder) is highlighted in yellow. Adapted from Ref. [20]. (For interpretation
of the references to colour in this figure legend, the reader is referred to the web version of this article.)
mechanical properties can be optimized; i.e. edgeline/bulk toughness, of mixture predictions invalid for cemented carbides. Exner and
hardness and thermal conductivity (see Fig. 9). These properties may Fischmeister [23], Roebuck and Bennett [24] and Golovchan and Li-
vary for depending on application, i.e. machining of alloyed, stainless toshenko [25] have all performed studies of WC contiguity and its re-
and austenitic steels; cast iron or composites. lationship to the volume fraction of binder and in some cases, also to
Contiguity is a measure of the proportion of WC/WC contacts in the WC grain size, see Table 2.
microstructure, which effectively form a skeleton of WC. Many of the Similarly, the mean free path of binder can be described as a
unique properties of cemented carbides are due to the formation of the function of average WC grain size and volume fraction of binder, as
WC skeleton, the occurrence of which in many cases makes simple rule shown by Gurland [26] Underwood [27] and Roebuck and Bennett
5µm
Ultrafine Submicron Fine Medium Coarse Extra coarse

0.2-0.5 µm 0.5-0.9 µm 1.0-1.3 µm 1.4-3.4 µm 2.5-5.0 µm >5.0 µm
Fig. 7. WC-Co microstructures for different WC grain sizes. Classification according to the Fachverband Pulvermetallurgie [1]. Images courtesy of AB Sandvik
Coromant R&D.
45
2400 Table 2
Evaluated empirical expressions relating contiguity to other microstructural
parameters. VCo is the volume fraction of Co binder, dWC is the measured
2200 average WC grain size and σWC is its standard deviation.
Reference Contiguity formula
2000 Ultrafine
Exner and Fischmeister [23] C = 0.074VCo−1
Roebuck and Bennett [24] C = 0.85 − 1.80VCo
Golovchan and Litoshenko [25]
( )
Hardnes s (Vickers units)
0.644 0.391 WC
1800 C=1 VCo exp
dWC
1600
Submicron Table 3
Mean free path expressions.
1400 Reference Mean free path formula
Gurland [26] λ = dWC(1 − C)−1VCo(1 − VCo)−1

1200 Underwood [27] λ = dWCVCo(1 − VCo)−1
Roebuck and Bennett [24] λ = dWC(0.1 + 2VCo)
Medium
1000
It should be noted that the relations presented here are of an em-
pirical nature and most often do not consider scatter due to WC grain
800 shape, width of the particle size distribution (this was indeed con-
0 5 10 15 20 25 30 sidered by Golovchan and Litoshenko [25]), bi- or multi-modal dis-
Cobalt content (wt%)
tributions, as well as any other carbide phases that may appear in the
Fig. 8. Hardness of cemented carbides as a function of WC grain size and cobalt microstructure.
content. Data from AB Sandvik Coromant.
4.1.1. Quality control of sintered WC-Co-based cemented carbide

[24], see Table 3. The volume fraction of binder is in turn proportional The quality of the sintered product can be estimated by non-de-
to the Co content. structive testing. The measurement of the magnetic properties is a well-
In summary, most properties of cemented carbides can be described established method to determine if the final product fits in the allow-
in a good way by relating them to the Co content and/or average WC able C-window, which ensures the best properties of the cemented
grain size. The hardness, and consequently the toughness, may be de- carbide. The non-destructive quality control is possible due to the fer-
scribed as a function of average WC grain size and content of Co. romagnetism of cobalt. Magnetic saturation is used as an indirect, quick
Contiguity and mean free path are complementary variables and may and reliable method of measuring the carbon content of sintered ce-
be used to describe such quantities as well. mented carbide. The advantage of this method is the linear relationship
Fig. 9. Correlation between binder content and WC grain size with main properties of cemented carbides.
46
+
MS
Graphite
- +
Hc
Coarse grained Fine grained
η-phase
-
Fig. 10. Interpretation and relationship between the values of magnetic saturation (MS), coercivity (Hc) and the microstructure of cemented carbides.
between the carbon content and the values of the magnetic saturation distribution in the batch was not uniform. Magnetic properties are
in the region of interest (i.e. WC-Co). The carbon content can be esti- measured upon norm DIN-ISO 3326. For cemented carbides with CreCo
mated to an accuracy of 0.01% by magnetic saturation measurements binders, the magnetic saturation need to be corrected to account the
for samples which are prepared within closely comparable conditions. change in the magnetization of the binder phase due to Cr alloying in
The magnetic saturation of the sintered cemented carbide increases as the binder. Furthermore, in Ni- and Fe-based cemented carbides, the
the amount of tungsten in solid solution in cobalt decreases and vice determination of the quality of cemented carbides by measuring the
versa. Magnetic saturation in the two-phase region is, therefore, an magnetic properties needs to consider the non-linear relationship be-
indication of the amount of tungsten dissolved in the binder phase. tween magnetic values and the carbon content in the WC-binder phase
There are exceptions for this rule, i.e. when high carbon alloys are region.
quickly cooled from the sintering temperature as observed by Freytag For cemented carbides processed at the same conditions, the only
and Exner [28]. difference being carbon content, low values of magnetic saturation are
The other magnetic property of practical importance for controlling coupled to a higher coercivity, indicating a fine-grained microstructure.
the quality of sintered cemented carbide is the coercive force (Hc). Conversely, when the Hc value decreases, the magnetic saturation value
Coercivity is a non-destructive evaluation of the microstructure of ce- increases, meaning that the microstructure tends to be coarse and the
mented carbides, such as degree of sintering, cobalt distribution, and binder is low alloyed due to the presence of a high carbon activity
grain size of the cemented carbide. The coercive force is inversely (Fig. 10).
proportional to the grain size of the alloy, meaning that high coercive Each cemented carbide type has a lower and upper limit of coercive
force values indicate a fine-grained microstructure and vice versa. It force and magnetic saturation. Within these limits, a microstructure
was demonstrated that Hc increases linearly with decreasing grain size. free of undesirable phases is found. It should be mentioned that state-of-
The coercive force decreases as the cobalt percentage increases [29]. art procedure is not just to be within the limits of the two-phase region,
Fang and Easan observed an increase in Hc with decreasing carbon but to aim for a certain position in that window (i.e. on the low carbon
content of WC. Coercive force values can also be used to optimize side). Finally, for reliable control of the microstructure of the sintered
milling conditions [30]. When milling is carried out improperly, the alloys, not only magnetic saturation measurements, but also micro-
values of coercive force show a large scatter, meaning that the cobalt structure investigations and chemical analysis are carried out to
47
Fig. 11. SEM -Back Scattered Electron micrographs of fine-grained (ultrafine) WC-10% Co cemented carbides with increasing addition of Ti (400, 1000, 1500 and
2500 at. ppm.). Note the presence of cubic (Ti,W)C precipitates, indicated by arrows. Courtesy of AB Sandvik Coromant R&D.
Fig. 12. SEM -Back Scattered Electron micrographs of submicron WC-Co (left) and fine-grained WC-Co-Cr cemented carbides. Courtesy of AB Sandvik Coromant R&
D.
determine the quality of the final sintered products. high precision and dimensional control is necessary. However, a pri-
mary issue lies already in performing an unambiguous and standardized
4.2. Fine and nano-grained WC determination or measurement of the WC grain size. Two measurement
methods dominate reported grain sizes, i.e., linear intercept and
The mechanical properties of WC–Co strongly depend on the size of equivalent circle diameter, where the latter is in general 1.15 times the
the WC grains. Reduction of the average WC grain size increases former [31]. In the following, the WC grain size will be discussed in
hardness, wear resistance, compressive strength and transverse rupture terms of the diameter of a circle, with an area corresponding to the
strength. This is of special interest for inserts with sharp edges (milling), average WC grain, as obtained from a 2D cross-section.
drills (aerospace industry) or microdrills (electronic industry), where It is difficult to know the WC grain size in the original (historical)
48
cemented carbides with precision [32]. However, the WC grain size was nanometer scale in size, it is possible that the driving force for grain
explored very shortly after the introduction of the first grade on the growth may exceed a threshold and thus the reduction of driving force,
market. While containing a significant portion of WC grains below and the kinetic barrier brought about by inhibitors, will be insufficient
1 μm, historical grades frequently exhibited grains up to 3 μm in size to retard grain growth.
[32]. Today, a narrower WC grain size distribution in the as-sintered In a recent study by Pötschke et al. [42] the various stages of con-
cemented carbide is possible. The key seems to lie in the WC raw ma- solidation and densification during sintering of WC-Co-Cr/V cemented
terial, where the initial grain size distribution of the W powder (or carbides are explored in detail. In this study, it is concluded that the
oxide precursor) is of vital importance. Furthermore, it is possible to gettering of oxygen by the inhibitors prevents decarburization of WC
add grain growth inhibitors. The most potent inhibitor is V, followed by and the formation of pure W, since the inhibitors are added as carbides,
Ti, Cr, Ta, Mo and Nb. However, issues with embrittlement have been and may thus act as a carbon source.
observed due to (V,W)C precipitates at the corner junctions of WC grain The process of grain growth inhibition is thus not fully understood.
boundaries [33]. An example of the effect of very small additions of Ti However, it is clear that the use of grain growth inhibitors and con-
on the microstructure of a WC-10% Co cemented carbide is given in ventional processing seems to have a limit. The powder metallurgy
Fig. 11, and for the addition of Cr in Fig. 12. In Fig.11 it is clearly seen route also presents limitations to produce composites with nanometric
that the increasing addition of Ti not only reduces the as-sintered (particle size after consolidation < 0.2 μm). Also, as shown by Schubert
average WC grain size (about 0.5 μm at 400 at. ppm. Ti down to 0.4 μm et al. [43] the conventional powder production methods, i.e., reduction
at 2500) but also dramatically decreases the occurrence of abnormally of tungstic acid to W powder and subsequent carburization or direct
large WC grains. Addition of grain growth inhibitors also affects the carburization of tungsten oxides, can produce WC powders with a grain
shape of the WC grains [34,35]. The addition of Cr can also increase the size down to about 50–150 nm. Therefore, other industrially viable
corrosion resistance of the cemented carbide. methods are needed if the grain size of WC powder has to be reduced
Conventional methods of cemented carbide production result in further. Recently a method to produce crystalline fine-grained compo-
considerable difficulties in reducing the average grain size of WC below sites starting from amorphous sol-gel masses containing W, Fe alkoxides
0.2 μm [36] and thus the advent of the nano-grain era has yet to occur and extra added carbon was described [44]. WC and Fe (of few nm)
on an industrial scale. Despite this, it is clear that nano-grained pre- precipitate in-situ during a two steps heating. However, substantial
cursors to WC-based cemented carbides can be produced [37]. The grain growth (relative to the initial grain size in the powder) is again
main issue is to retain the very fine grain size in a sintered component observed after consolidation.
[38]. Some authors report nano-scaled WC grain sizes in sintered
components by using alternative sintering strategies, such as pulsed 4.3. Bi-modal WC grain size distribution
currents, reduced sintering temperature and pressurized sintering [39].
However, different methods to account for WC particle size are used, Bi-modal WC grain size distribution may be formed intentionally or
such as X-ray diffraction [39] or image analysis of transmission electron unintentionally in a cemented carbide. This concept has been exploited
(TEM) micrographs [37]. Other authors make no distinction between in the cemented carbide industry to combine hardness and toughness by
initial WC powder and sintered WC grain size. tailoring the WC grain size.
WC grain growth during sintering mainly occurs through Ostwald In general, bimodality is characterized by two clearly separate peaks
ripening. Coalescence has been reported to account only for a minor in the WC grain size distribution. The occurrence of bimodality, when it
part of the WC grain growth due to the observed decrease in growth is intentional, often stems from using two different WC raw materials,
rate with increasing contiguity [16,17]. For extremely fine grains (na- each with different but preferably uniform WC grain size. Milling is in
nosize) coalescence might be more important during initial stages of this case often undesired as it tends to broaden the grain size dis-
sintering. The current understanding of the effect of grain growth in- tribution and increase the propensity for abnormal grain growth.
hibitor additions is the formation of thin cubic (M,W)C (M = Cr, V, Ti During sintering, the grain growth process will dissolve the smallest
etc.) films on the surfaces of WC grains, thereby not only lowering the grains, in favour of precipitating on the larger ones. It is therefore ne-
interfacial energy but also by acting as a kinetic barrier [40,41]. Due to cessary to adjust the proportions of the two raw materials accordingly,
the extreme ratio of surface/volume for WC grains approaching the so that the desired final distribution is achieved. Fig. 13 shows an ex-
ample of the microstructure of a bimodal WC-Co cemented carbide.
Several methods have been reported by which the milling step may
be omitted, or its effect reduced, the main issue to be addressed being
the even distribution of binder phase powder particles, which is nor-
mally done by extensive milling of WC and Co raw material powders. If
milling cannot be applied, other techniques must be used, and several
patented solutions exist. For example, in Ref. [45] a method of coating
WC particles by Fe, Co or Ni using a Sol-Gel technique is proposed,
thereby obtaining a uniform binder metal distribution already before
sintering, thus avoiding the necessity of an extensive milling process.
Waldenström [46] described a method based on pre-coating of the WC
powder with grain growth inhibitors, in combination with wet-mixing,
where it is essential that the mixing process does not change the initial
particle size distribution of the WC powders used.
Unintentional bimodality may be obtained when abnormal grain
growth is not controlled for, e.g., if extensive milling is conducted, or if
prolonged sintering is applied, without proper additions of WC grain
growth inhibitors.
Claimed advantages of bimodal WC grain size distribution in sin-
tered WC-Co compacts include increased resistance to plastic de-
Fig. 13. Light optical microscopy (LOM) image showing the microstructure of a formation due to the possibility to achieve dense packing of WC grains
bimodal WC-10%Co cemented carbide (Murakami etching). Image courtesy of and increased strength to toughness ratio due to optimized mean free
AB Sandvik Coromant R&D. path of the metallic binder phase [47].
49
a large amount of Ta doping in the WC grains had lower hardness than

the expected for their grain size, agreeing with the hypothesis that
doping of Ta in the WC crystals has a softening effect on the material
and may improve the ductility of the WC phase.
Theoretical calculations by Suetin et al. [58] predicted that amongst
the 3d transition metals, Cr, V, Ti and Mn should be closest in energy to
form a solid solution with W in hexagonal WC. Weidow et al.'s study in
2011 measured by Atom Probe Tomography (APT) solubilities in the
10−3 to 10−4 range for Nb and V, in the 10−5 range for Cr and Ti and
even lower for Co, Hf and Zr. Theoretical calculations were performed
by ab initio giving the solubility of Nb, Cr and V in WC in the 10−3
atom fraction range, Ti and Mn 10−5 and for Co and Zr concentrations
were not detectable. Thus, good agreement was found between pre-
dicted and measured values [51].
Several authors have reported on the solubility of Cr in the WC
lattice [59–61]. Gladyshevskiy et al. already described a cubic carbide
(W,Cr)C formed in the ternary system W–Cr–C with carbon contents of
40–50 at.% [60]. However, Tükör et al. [61] found that it is possible to
dissolve Cr in hexagonal WC during carburization of the powder. The
Fig. 14. SEM micrograph of sintered (W,Ta)C-Co material. Bright areas corre-
authors found a hexagonal (W,Cr)C phase with a higher Cr content then
spond to WC and also to (Ta,W)C. Dark areas correspond to the Co based binder previously reported (W0.85,Cr0.15)C corresponding to 5 wt% CrC.
phase. APT reconstruction (largest diameter 51 nm, length 175 nm), in the Weidow et al. [51] confirmed the results from theoretical calculations
shape of a needle, of a part of a (W,Ta)C grain in the same material (left upper by atom probe measurements, giving the solubility of Cr in WC of 1.85 ∗
corner). Each dot represents one Ta atom [57]. 10−3 after sintering at 1410 °C.
The main challenge when doping hexagonal WC, from a processing
Recently, it was reported that a bimodal distribution of binder phase point of view, is to control the precipitation of cubic carbides or car-
regions (also called lakes or pools) may be achieved in fine grain WC-Co bonitrides from the doped-hex-WC, since these precipitates will affect
materials sintered at low temperatures [48]. This is perhaps not to be the toughness of the obtained sintered product. Methods to produce a
considered a true bimodal grain size distribution, since the binder phase cemented carbide using doped hexagonal WC [62] and to tailor the
usually consists of very large grains, thousands of times larger than thickness of the gradient by combining doped hexagonal WC and ni-
individual binder pools [49], due to its presence as a continuous matrix trogen [63] have been proposed.
phase. Nonetheless, the binder pool distribution exhibits two char-
acteristic sizes and could thus to be considered as a bimodal micro- 4.5. Platelet WC
structure. The benefit of such a microstructure is reported to increase
both hardness and fracture toughness. The shape of carbide crystals varies with the crystallographic
structure of the carbide and the nature of the binder influences the
properties of sintered cemented carbides. It is claimed that WC crys-
4.4. Doped Hexagonal-WC tallites presenting a platelet structure may improve the toughness of
cemented carbides.
Recently an alternative technique consisting of doping the WC The carbide crystal shape develops during the first minutes of the
grains while maintaining their hexagonal structure (hex) has been in- liquid phase sintering and it is influenced by two processes: shape re-
vestigated. Aim is to modify the intrinsic properties of hex-WC and also laxation and carbide crystal growth [64]. The first one considers the
to control the WC grain size by introducing the doping already in the interfacial energies of the facets, causing the shape to move towards the
WC phase. However, it has been difficult to alter the properties of the equilibrium shape, and the second one accounts for the dissolution and
hexagonal WC phase itself. Molybdenum forms a continuous solid so- growth kinetics of the facets leading to growth-determined shape. Both
lution of MoC in WC at temperatures below 1170 °C [50]. The solubility processes occur by dissolution followed by diffusion in the liquid binder
of other transition metal atoms in WC is so small that it is commonly phase and then their reprecipitation on the same crystal (for relaxation)
neglected [51–53]. or on another crystal (for growth).
In 2012, W.D. Schubert patented a method for producing doped Hexagonal carbide crystals in cemented carbides develop a trun-
hexagonal (W,Me)C raw powders [54] with Me being at least one cated trigonal prism shape and are formed by basal (0001) and pris-
transition metal of the groups 4, 5 and 7. The production process was matic (101̄0) planes [65]. However, growth rate anisotropy of WC
carried out by a two-step carburization method, including the forma- particles can result in a platelet shape (Fig. 15).
tion of a subcarbide (hex-(W,Me)2C) in the first step and a doped car- Platelets can be achieved by preventing nucleation of new basal
bide (hex-(W,Me)C) in the second step. By this method the solid solu- plane layers by doping the material with titanium [66]. Shatov et al.
bility of other transition metals could be enhanced. Weidow et al. [64] defined a shape parameter, PWC, referred to as the shape
produced Ta-doped WC through the two-step carburization process equiaxiality of WC crystals. It was observed that with increasing tita-
[54–56]. The solubility of Ta measured by atom probe tomography -and nium content the WC crystals became flatter regardless of the binder
expressed as Ta/(Ta + W)- was 0.086, four times higher than what phase content.
previously observed in [51]. Kawakami et al. [67] found that ultrathin Ti layers were formed on
WC powder pre-alloyed with Ta has successfully been used to pro- basal WC planes. Further on, a cubic ultrathin layer, possibly (Ti,W)CX,
duce both coarse grained and fine-grained WC-Co based cemented was observed in a WC grain in Ti doped WC-Co [66]. It was calculated
carbides with a confirmed high concentration of Ta remaining in the that ultrathin TiC cubic layers are formed on the basal WC/Co interface,
WC structure (Fig. 14). The Young's moduli of the doped crystals were while on the prismatic WC/Co interfaces no films were predicted to
significantly lower than for undoped WC. These were measured by segregate [68]. Recently, Scanning Transmission Electron Microscopy
nano-indentation in agreement with the lowering of the elastic con- (STEM) imaging and Energy-dispersive X-ray spectroscopy (EDX) con-
stants from ab initio calculations [57]. In addition, some materials with firmed the existence of two ultrathin monolayers, i.e. one Ti-rich
50
Fig. 15. SEM image of a platelet WC-Co cemented carbide [77].
adjacent to the WC and one W-rich adjacent to the Co binder, only on et al. claimed that the fracture toughness of a platelet (W,Ti)C-10Co
the basal planes of WC grains adjacent to the Co binder [69]. system was improved over that for WC-3TiC-10Co and WC-10Co due to
Basal crystal planes in WC grains have higher hardness than the an increased resistance to crack propagation [71]. The results are
others [65]. Flatter crystals have flatter dislocation planes and thus however inconclusive, since the difference in porosity between the
reduce the Frank-Read dislocation loop pile-up, explaining higher materials could also explain the observed trend. Furthermore, WC
hardness despite lower contiguity [70]. Platelets contain fewer basal platelets have been synthesized through high-energy ball milling and
plane layers, resulting in a lower possibility for stacking faults and have carbothermal reduction from pure WC without Co [75], via a molten
a high aspect ratio that interferes with the crack propagation, im- salt synthesis in NaCl [76] and produced as protruded crystallites by
proving the fracture toughness in the material [71]. controlled sintering [77].
Highly oriented plate-like WC grains can also be obtained by a) hot
extrusion of ultra-fine WC + Co mixed powder [72] or b) hot pressing
5. Cubic carbides and additional carbides
of sintered compact having plate-like WC grains [73]. However, these
have not been commercialized yet since an appropriate grain size and
5.1. WC-Co-γ-phase
alloy composition for practical usage is difficult and costly to obtain
through these methods.
The addition of TiC, TaC, NbC, and in some cases VC, ZrC or HfC, to
In 1999, Kinoshita et al. created a platelet cemented carbide by a
WC-Co cemented carbides will give rise to a secondary mixed (M,W)C
mixture of W and graphite powder. The fracture toughness and trans-
cubic carbide phase (here denoted γ-phase), where M = Ti, Ta, Nb, Zr,
verse-rupture strength were superior to those of a conventional WC-Co
Hf, V depending on the added carbides [2,4,9,10,65]. γ-phase is no-
alloy at an identical Co content and hardness. The plate-like grains were
ticeable in the microstructure of cemented carbides by distinct rounded
suggested to act as a strong barrier for crack propagation [74].
morphology and brownish colour in cross section images (Fig. 16). The
In 2010, Nam et al. produced a (W,Ti)C solid solution through a
solubility of these carbides in the liquid phase, at typical liquid phase
carbothermal reduction process, using WO3, TiO2 and C [71]. Nam
sintering temperatures, is also limited [78] and thus incomplete
Fig. 16. Light optical microscopy image of WC-(Ta,Nb)C-Co

cemented carbide showing the WC grains (grey phase), Co
binder phase (white) and (Ta,Nb)C γ-phase (brown phase).
Surface SEM -Back Scattered Electron image of WC-(Ta,Nb)C-
Co showing the different morphology of WC (facetted grains)
and cubic carbide phase (rounded grains) (left upper corner)
[80] (Light Optical Microscopy image courtesy of AB Sandvik
Coromant R&D). (For interpretation of the references to
colour in this figure legend, the reader is referred to the web
version of this article.)
51
Fig. 17. SEM image of a sintered cermet where the darkest areas correspond to
the core, the dark grey area to the rim and the brightest area to the binder.
Image courtesy of AB Sandvik Coromant R&D. Fig. 18. New generation cermet Ti(C,N)-WC-NbC-Co. The core is composed of
undissolved Ti(C,N). The inner rim is composed of W-rich (Ti,Nb,W)(C,N), the
outer rim is composed of (Ti,Nb,W)(C,N) and the binder is mainly Co. Image
dissolution of the added carbide particles may be observed. This often
courtesy of AB Sandvik Coromant R&D.
leads to the formation of a γ-phase presenting a core rim structure,
although much less pronounced than for, e.g., cermet materials. The
formation of such a core-rim structure is dependent on the composition with the same lattice structure as the core [82]. The rim can be further
and processing. sub-divided into two parts, the inner rim and the outer rim [83]. In
Only very low additions of these carbide formers can be permitted if cermets no WC phase is present in the microstructure, but W can form
secondary carbide precipitates are undesired, owing to the very low part of the core-rim structure.
solubility of cubic carbide formers in the solid Co-based binder at the The first Ti-based cemented carbide was patented in 1931, it was
high carbon activities in typical cemented carbide materials. composed of a (Ti,Mo)Cx alloy with a Ni binder phase [84]. In the
From the technological point of view, already in the origins of the middle of the 50's Ford Motor Comp. added Mo2C to TiC and Ni
cemented carbide industry the influence of adding cubic carbide for- [85,86]. Part of the Mo carbide dissolved in the Ni, hardening the
mers in cemented carbides was noticed [2,3]. TiC is a very hard and binder, and part reacted with the TiC particles forming (Ti,Mo)C, im-
stable carbide, which provides wear resistance to WC-Co. Owing to the proving the wettability with the binder.
higher hardness of TiC as compared to WC, additions of TiC will in- In the 70's Kieffer and co-workers introduced the use of TiN, which
crease the hardness of cemented carbides. TiC additions were initially greatly reduced the grain growth [87], significantly improving the
made to increase the resistance to crater wear of uncoated tools in steel mechanical properties [88] and enhancing the resistance to erosion and
cutting [79], which forms by abrasion and is often accompanied by oxidation. Moskowitz et al. demonstrated that a TiN/TiC ratio of
chemical interaction and diffusive wear due to the elevated tempera- 0.4–0.5 provides the maximum tool life [89]. Nitrogen thus provides
ture close to the cutting edge. On the other hand, TaC, NbC and ZrC strong chemical inertness and acts as a growth inhibitor, while carbon
enhance the resistance to plastic deformation, especially TaC because of provides wear resistance [90]. Ti(C,N) based cermets rose in popularity
its higher wear resistance and hardness at high temperatures. in the 1980's [91]. Other constituents were added such as Co, VC, NbC,
Barbatti et al. [80] investigated the effect of partial replacement of TaC and WC – introducing the first modern cermets. NbC and TaC in-
WC by cubic refractory carbides (TiC and (Ta,Nb)C) on the oxidation crease the resistance to thermal shock [92], whereas dissolution of WC
resistance of WC–Co cemented carbides at 600 and 800 °C. The oxida- hardens the binder and improves the wettability between Ti-carbides
tion kinetics obeys a linear function and the increasing content of and Co [93].VC and Cr3C2 have a high solubility in the binder, but also
(Ta,Nb)C causes a reduction of the oxidation rate; at higher tempera- act as growth inhibitors of the hard phase [94].
ture oxidation resistance at 800 °C is only attained by TiC addition; thus In the 1990's, Rolander et al. [95] developed a new generation of
the main factor affecting the oxidation resistance is the content of WC cermets, based on Ti(C,N)-WC-Co. This cermet fully replaced Ni with
after the replacement by the mixed carbides and the passivation effect Co, solving previous issues with coatability [96]. Despite adequate
of the Ti, Ta and Nb oxides. toughness, this material lacked in terms of plastic deformation re-
Nowadays, due to the superior performance of CVD and PVD coated sistance. Adding TaC was shown to maximize the plastic deformation
cemented carbide grades, the use of cemented carbides containing a resistance without compromising the wear resistance [97,98]. Due to
significant proportion of this mixed cubic carbide phase is limited. the beginning mass production of mobile phones in 2000 the significant
Applications are found in milling applications (interrupted cut ma- increase in Ta price lead to a replacement of TaC by NbC [99]. Fig. 18
chining) where cubic carbides are present with a total content of less shows the microstructure of NbC-based cermet.
than a few volume percent. The use of nitrogen-containing γ-phase to Recently, researchers have put special emphasis on the preparation
produce functionally graded cemented carbides is state-of-art in coated of ultrafine Ti(C,N)-based cermets. These materials have enhanced
inserts for turning of steel. hardness, mechanical strength, toughness and wear resistance. They
can be prepared by using nano-sized powders and fast sintering tech-
niques [100,101].
5.2. Cermets
Cermets are mainly used as cutting tools in surface finishing op-
erations due to their high chemical stability and good high-temperature
The main hard phase of cermets is a Ti-based cubic carbide, nitride
hardness, as compared to WC-based cemented carbides. Although PVD-
or carbonitride. This hard phase normally exhibits a core-rim structure,
coated cemented carbides can also be used for these operations, Ti
see Fig. 17. The rim, formed by means of the dissolution-precipitation
(C,N)-based cermets provide better dimensional accuracy in work
mechanism [81], is a (Ti,Me)(C,N) solid solution (Me = Mo/W/Ta/Nb),
52
Fig. 19. Microstructure of WC-8%Co cemented carbides with increasing content of carbon. Finely dispersed η-phase is present for strong understoichiometric carbon
contents (left). Close to the η-phase limit, massive dendritic η-phase is formed. The η-phase free carbide can be produced by adjusting the carbon content (right).
Images courtesy of AB Sandvik Coromant R&D.
pieces and good resistance to chipping [102,103]. Also, materials that 5.3. WC-Co-η-phase
form built-up edge wear are machined with cermets due to their low
chemical reactivity [104]. The main drawback of cermets is their Decarburized cemented carbides containing η- phase in the micro-
comparatively poor toughness, especially at low temperatures. They structure are used e.g. for the production of dual-properties gradient
possess a low heat conductivity and a high thermal expansion coeffi- cemented carbides.
cient compared to cemented carbides. These properties make cermets Eta-phase (η- phase) is a ternary carbide formed by W, Co and C that
extremely sensitive to thermo-mechanical cracks, which can form forms when there is a deficiency of carbon in the WC-Co system. η-
during milling operations. However, Ti(C,N)-based cermets can be used phase has two different carbide forms, namely M6C and M12C. M6C
for milling and rough machining of steel grades when reducing the composition ranges from Co3.2W2.8C to Co2W4C [109] and is stable at
amount of TaC or NbC to approximately 10%, losing resistance to low temperatures, whereas M12C has a fixed composition of Co6W6C
plastic deformation but increasing toughness [104–106]. Ultrafine/ and is stable above 1000 °C [110].
nano Ti(C,N)-based cermets exhibit better wear and oxidation re- M6C and M12C crystallize both in cubic structure but are distin-
sistance than coarse grained cermets [107]. However, due to the pro- guishable with X-ray diffraction (XRD). M6C may remain as a me-
cessing challenges and adverse effects on hardness, these have not yet tastable phase at low temperatures, and can undergo an in-situ de-
been commercialized [108]. composition (M6C➔binder+M12C + WC) by a slow reaction [111]. In
Fig. 20. SEM images of a TiC whisker reinforced TiC-based cermet [119] (left) and ultrafine WC–Ni–VC–TaC reinforced with cBN particles cemented carbide [118]
(right).
53
commercial tungsten carbide alloys with a relatively fast cooling rate, decreased from 1950 to 1250 MPa.
the presence of M6C is more probable than that of M12C [112]. The TiC whisker reinforced TiC-based cermets were also prepared by
level of carbon deficiency in the system and the cooling rate will greatly Xiong et al. [119] and compared to both microsize and ultrafine cer-
influence the amount and shape of the eta-phase in the alloy. mets. TiC whiskers were prepared by carbothermal reduction, with a
Firstly, at extremely minor carbon deficiency levels η- phase can TiC whisker yield around 80–90 wt%. Compared to SiC whiskers, TiC
completely disappear during cooling (Fig. 19). Secondly, at minor whiskers showed a better interface morphology and bonding strength.
carbon deficiency levels, η- phase is produced upon cooling from the The whisker reinforced cermets owned a much higher toughness of
sintering temperature (i.e., WC + liq ➔ WC + η- + liq.) and nucleates 12.43 MPa m1/2 than the conventional microsized and ultrafine grade
in specific areas. Further cooling into the solidus range can produce cermets, with a hardness between them. However, a lower transverse
peritectic decomposition of η- phase (liq. + η + WC ➔ WC + binder) rupture strength of 1580 MPa is achieved, most likely due to the high
[113]. Even though the decomposition of the η-phase is thermo- porosity level.
dynamically possible, at these carbon contents, the process is slow and
thus η-phase may remain in the microstructure even after cooling. 5.5. NbC-based cermets
Furthermore, due to the appearance of massive dendritic η-phase re-
gions across the material (Fig. 19, coarse η-phase) this type of η-phase is Extensive research has been devoted to the replacement of WC by
particularly detrimental. Therefore, these carbon contents are avoided other carbides, such as NbC in cemented carbides. This is mainly driven
in cemented carbide production, since the existence of large areas of by market reasons, since Niobium reserves largely exceed those of
brittle η-phase greatly diminishes the mechanical properties of the ce- tungsten and new deposits have recently been found [9]. NbC can be
mented carbide. produced via carbothermal conversion of Nb2O5 or metallurgical
With higher carbon deficiency levels η- phase is present at the sin- growth followed by leaching-out [120]. Nb can form a cubic carbide
tering temperature and tends to be retained after cooling. The finely over a wide range of carbon stoichiometry, as well as hexagonal Nb2C
dispersed particles of η-phase increases both in particle size and in [121].
volume fraction with an increase in carbon deficiency (Fig. 20, fine- NbC-based cermets can be embedded in the same binder metals, and
dispersed η-phase) [114]. be processed and sintered in the same way, as WC-based cemented
The amount of carbon in cemented carbides can be described by the carbides. NbC and Nb2O5 are not known to pose any risk to human
total carbon balance, which is equal to zero at the stoichiometric health and are not of very high concern in the REACH classification
composition. Negative carbon balance indicates sub stoichiometric [122]. It is important to clarify that WO3 has also no known danger
carbide compositions. The factors that affect the carbon balance are: a) towards human health and is not listed in REACH, contrary to what is
the added carbon in the alloy, b) the oxygen content in the WC powder occasionally stated in publications [120]. Tribo-oxidatively formed
and the milling time, both contributing to increased oxygen content, Nb2O5 melts at 1512 °C, whereas WO3 tends to sublimate above
which reduces the carbon content during sintering, and c) the de- 750–800 °C causing a loss in tribo-oxidative wear protection for WC
binding process during the sintering, which can be decarburising de- [123].
pending on temperature, atmosphere and holding times. Initially, NbC-Co and NbC-Co-B cermets have been studied. It was
The sub-stoichiometric carbon content in WC-Co systems has two shown that increasing the boron content caused the shape of the NbC
effects: the first one is the formation of the η-phase as described above. grains to change from faceted with rounded edges to spherical, also
The second effect is the increased solubility of W in the Co binder phase increasing their growth rate [124].
during sintering. H. Jonsson described the reaction paths taking place Huang et al. examined the microstructure and mechanical proper-
during the isothermal decomposition of the supersaturated solution of ties of NbC-Co cermets as a function of sintering temperature, Co
W (and C) in Co [115]. content and WC addition [125]. NbC-Co has a very poor wettability
Kim Jiwoong et al. calculated the Young modulus and hardness of which results in a much lower fracture toughness than that of NbC-Ni
several eta-phases by ab initio [116]. The η-phases show substantially [126]. It was demonstrated that additional carbides improved the
lower elastic moduli than WC and are much softer (10–13 GPa) than wetting and minimized the grain growth [127]. NbC grain growth in-
both WC and W2C. hibition can be achieved by adding Al to a NbC-Fe alloy and a NbC-Ni
alloy as well as by adding Mo2C and VC to a NbC-Ni cermet [120].
5.4. Particle reinforced cemented carbide The grain growth of NbC occurs by a solution/precipitation process
controlled by the diffusion of NbC through the liquid phase [128]. In
Reinforcement of the cemented carbide matrix by adding other NbC-Ni, the shape of the large NbC grains is well-faceted, with a slight
dispersed hard phases (such as oxides, silicides or borides in form of rounding of the edges, while the small grains can be almost spherical
whiskers, or dispersed particles) is another possible route to tailor the [129]. Both hardness and fracture toughness increase with a decreasing
properties of cemented carbides. These particles do not participate in overall carbon content. Fig. 21 shows the microstructure of NbC cer-
the formation of a carbide skeleton, in contrast to the γ-phase. Although mets, presenting both rounded and facetted NbC grains. The potential
the method has not been exploited extensively in industry, interesting application of NbC-based materials for wear resistant components was
features and properties have been described. first reported by Woydt and Mohrbacher in 2013 [130,131]. NbC has a
WC-Ni cemented carbides reinforced by SiC nano-whiskers [117] very high melting point, which limits thermal softening and the ten-
additions have been investigated. The consolidation of particle re- dency to adhesive wear. The higher coefficient of thermal expansion
inforced cemented carbides usually depends on the volume fraction of and lower Youngs modulus of NbC indicate smaller thermal stresses
added particles. Samples containing small amounts of SiC nano-whis- between NbC and the metallic binder than those for WC (see Table 1).
kers can be consolidated with high density; but as the added fraction of Although the hardness of NbC is lower than that of WC, the elastic
SiC nano-whiskers increases, agglomeration and inhomogeneous dis- modulus and hardness are quite stable with increasing temperature.
persion of the SiC whiskers decrease the properties of the cemented The micro-hardness and especially the hot hardness can be adjusted by
carbides. An optimum addition of SiC nano-whiskers could improve the C/Nb ratio, even exceeding the hardness of WC [120]. NbC can also
flexural strength and Vickers hardness (Fig. 20). Rong et al. [118] be embedded in Fe-based alloys, due to the particularly low solubility of
showed that the addition of cBN particles modifies the properties of the NbC in iron [132]. However, in sintered components, these studies
Ni-based cemented carbide. For a fraction increment of cBN particles indicate that the advantageous mechanical properties of WC can still
from 0 up to 50 vol% in 8wt%Ni-0.7/0.3wt%VC/TaC cemented carbide, not be reached with NbC. Some studies claim that NbC-based materials
the hardness increased from 2100 to 3200 HV, but the flexural strength can be used as cutting tools [133]. In addition, NbC reinforced castings
54
Fig. 21. SEM -Back Scattered Electron images of a NbC-12 vol% Co + 0.9 vol% Cr3C2 cermet (left) and of a NbC-12 vol% Ni cermet (right). Courtesy of Dr. Shuigen
Huang (KU Leuven).
demonstrate a longer lifetime of components used in the mining in- 6.1. γ-phase free gradient
dustry and NbC-based guide rolls provide the hardness and micro-
structure of the equivalent WC-Co commercial rolls [134]. The most industrially used gradient cemented carbide is the γ-phase
free gradient. The main benefit of γ-phase free gradients (thickness: 10-
30 μm) is the increased toughness in the surface layer. In cemented
6. Gradients carbides coated with CVD it is necessary to prevent the propagation of
thermal cracks formed in the coating during the cooling step of the CVD
Cemented carbide properties can be tailored in such a way that a process, while keeping the necessary mechanical properties in the bulk.
single cemented carbide component with different regions can be pro- Such a microstructure is the established cemented carbide used in
duced. Functionally graded cemented carbides combine stiffness and cutting inserts for turning of steels, for heavy and interrupted-cutting
toughness in a single sintered body. The most common gradient car- operations.
bides are the so-called γ-phase-free gradients (of few micrometers) used The formation of γ-phase free gradients is a diffusion-controlled de-
in metal cutting industry [135,136] and Co-depleted surface macro- nitridation process; usually by denitridation of a N-containing phase,
gradients (hundreds of micrometers) used in rock tools applications that leads to inwards diffusion of Ti and increased cobalt content in the
[137,138]. Other gradients aim at enriching the surface of cemented surface [141,142]. Additionally, the diffusion process leads to the for-
carbide with γ-phase, which can be used to improve adhesion of further mation of a cone enriched in γ-phase at the cutting edge of the insert to
coatings for machining of metallic and non-metallic materials improve wear resistance, see Fig. 22. Understanding the gas evolution
[139,140]. phenomena has been a clue to tailor the γ-phase free gradient micro-
structure formation. For nitrogen containing cemented carbides of the
type WC-Ti(C,N)-Co, a nitrogen gas evolution during vacuum sintering
Fig. 22. Light Optical Microscopy image of a functionally graded WC-Ti-Ta-Nb-C-Co cemented carbide showing a γ-phase depleted surface and the characteristic
cone enriched in γ-phase at the corner of the insert (right) and corresponding magnification of the gradient region by SEM (WC: white phase, Co: black phase, γ-
phase: grey phase).
55
Fig. 23. Light Optical Microscopy image of a functionally graded WC-Ti-Ta-Nb-C-Co cemented carbide showing a nitrogen containing γ-phase enriched surface
(right) and SEM image of the interface region between the gradient and the bulk (left). Adapted from Ref. [146].
has been observed between 1100 and 1380 °C due to the decomposition modelling of gradient formation kinetics in Ni- and Fe-based cemented
of nitrides and carbonitrides(with a maximum at 1300 °C). Moreover, carbides has been carried out [153]. Recently, ab-initio molecular dy-
the intensity depends on the amount of nitrogen containing hard phases namics were used to calculate the diffusivities of relevant elements in
in the starting formulation [143]. The main N2 evolution is abruptly liquid Co, providing more fundamental quantities than what has been
interrupted at temperatures between 1350 °C and 1355 °C and it is as- used before to model the elemental mobilities [154].
sociated with the formation of the liquid phase, where a burst of re-
arrangement and densification, followed by solution/re-precipitation
6.2. γ-phase-enriched gradient
and grain shape accommodation occurs. Hence a very important topic is
the control of the sintering atmosphere during manufacturing of gra-
The production of surface gradients in cemented carbides and cer-
dient structures on cemented carbides. All technologically relevant
mets by nitridation has also been a matter of extensive research. γ-
gradients are a consequence of adjusting the composition of the ce-
phase-rich surface layers produced by nitridation of cubic carbide
mented carbide and the sintering conditions (time, temperature, at-
containing cemented carbides has been reported [155–158]. This type
mosphere) to achieve the desired microstructures [144].
of gradient is opposite to γ-phase free gradients, because a hard surface
Recently, research has mainly focussed on the production, char-
layer enriched in cubic carbonitrides and nitrogen is produced to im-
acterization and modelling of either γ-phase-free gradients, produced
prove wear resistance (see Fig. 23). Additionally, this surface gradient
by a) de-nitridation of TiN-containing cemented carbides in vacuum
has been claimed to improve the adhesion of carbonitride coatings
atmospheres, or b) by nitridation during the open porosity stage of the
[139].
sintering process, with subsequent de-nitridation. γ-phase free gradients
The effect of cubic carbide composition (TiC, TaC, NbC) and sin-
can be produced by nitridation sintering [140] which requires good
tering parameters (liquid phase sintering, solid state sintering) on the
technological knowledge of nitridation and sintering to produce the
formation of γ-phase rich wear resistant surfaces on cemented carbides
desired microstructures [143].
has been reported [155]. The formation of the wear resistant surface
Special interest has been devoted to the effect of alternative binders
layers depends on the TiC/(Ta,Nb)C ratio, the sintering time, tem-
(Fe-Ni-Co compositions) on the formation of gradients and their prop-
perature and atmosphere. The thickness and morphology of the graded
erties [145–148]. Independent of the binder composition, the growth of
layers depends on the treatment temperature. Samples which were ni-
γ-phase free surface layers has shown to obey a parabolic law, in-
trided at liquid phase temperatures show higher roughness than sam-
dicating a diffusion-controlled process. Thermodynamic calculations
ples nitrided at solid state conditions. The thickness of the nitrided γ-
have been used to understand driving forces responsible for the for-
rich outer-surfaces increases with the addition of Fe to the Co and Ni
mation of gradients. Correlations between nitrogen diffusion coeffi-
binders [146].
cients and nitrogen solubility levels in Fe–Ni–Co systems were pre-
Future work will elucidate if the Ti or N solubility or diffusivity in
sented to understand the mechanisms governing the formation of
the binder phase is driving the formation of such gradients. The diffu-
graded layers with Fe–Ni–Co alternative binders [145,148].
sion-controlled process leading to the formation of γ-phase rich layers
Computational thermodynamics has also been applied to model the
on cemented carbides was modelled by DICTRA considering that all
kinetics of gradient formation of gradients on Co-based and NieFe
diffusion occurred in the liquid binder phase of a dispersed system
based cemented carbides [145,149–153]. In DICTRA (Diffusion Con-
model [152]. Here, a good agreement between experiment and simu-
trolled TRAnsformations) simulations, the influence of the mobilities
lation regarding layer thickness, phase fraction distribution and ele-
for all diffusing elements in the liquid binder phase at the sintering
ment profiles was obtained.
temperature was investigated [145,150,153]. Best agreement between
The role of cemented carbide functionally graded outer-layers on
experiments and simulations was obtained by assuming the mobility of
the wear performance of coated cutting tools is summarized. The
all metallic elements is two times slower than the mobility of the non-
functionally graded substrate/coating combinations were designed for
metallic elements [145]. A detailed work on effect of mobilities on
interrupted and finishing turning conditions [139]. Nitrided cemented
DICTRA kinetic simulation is presented by Frisk et al. [150]. DICTRA
carbides showed increased wear performance compared to standard
56
Fig. 24. Macro-gradient cemented carbide with dual properties presenting three different zones in the microstructure: binder-depleted surface (blue zone), binder
enriched rim (yellow zone) and η-phase containing core (red core) [137]. (For interpretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.)
grades. The cubic carbide enriched outer-surface behaves like a coating hardness, b) an intermediate region with WC and high cobalt content
layer. Best cutting results in longitudinal turning were obtained for the and toughness and c) a bulk containing WC, η-phase and average cobalt
combination of nitrided substrate coated with CVD multilayers. In op- levels (see Fig. 24). These cobalt gradients in the three microstructural
erations dominated by interrupted cutting conditions with high loads/ zones, together with their differences in thermal expansion, redistribute
impacts coated cemented carbides with γ-phase free surface gradients internal stresses. It is for example possible to create a very hard and
gave superior wear properties mainly due more secure cutting edge wear-resistant surface layer which is simultaneously pre-loaded with
performance [139]. compressive stresses to prevent the initiation and propagation of cracks.
Carbide having such a distribution of properties are typically char-
acterized by high wear resistance at the surface combined with a tough
6.3. Dual properties carbide
core.
Guo et al. presented a comprehensive work on macro-gradient ki-
Cemented carbides may present gradients not only in the micro-
netics in WC-Co, focusing on the relationship between carbon activity
scopic but also in the macroscale (that extend over several millimetres).
and cobalt transport in WC-Co systems, indicating that cobalt transport
The “Dual Property” (DP) cemented carbides for mining applications
takes place from high carbon to lower carbon activities [159]. A review
are one of the most well-known and industrially established cemented
of liquid phase migration was done by Fan et al. [160] and experi-
carbides with macro-gradients, where the distribution of the binder
mental descriptions of macro-gradients were presented by Konyashin
phase has been modified in such a way as to create a material with
et al. [161]. Recently, a review on mechanical properties and wear
different properties in the surface zone compared to the bulk. Such
resistance of functionally graded WC-Co was done by Wang et al. [162].
“Functionally Graded” cemented carbides are beneficial in rock drilling
applications, where high wear and impact resistance are required in the
same component. The process (carburizing of an η-phase containing 6.4. Bi-layer WC-Co
cemented carbide) was first developed by Fischer et al. [137] and en-
ables to produce components which contain three distinct micro- Bi-layer cemented carbides can be produced by sintering two dif-
structural zones: a) a surface zone with WC and reduced cobalt and high ferent carbides parts with distinct WC particle size, binder content and
57
Fig. 25. SEM image of bi-layer WC-Co/WC-FeNi cemented carbide (top) and corresponding EBSD image showing two distinct WC grain sizes and a sharp interface
(bottom) [163].
composition (see Fig. 25). Different hardness/toughness ratios over binder may be inhibited by maintaining the same liquid phase migra-
large volumes can be achieved with this method [163]. This technology tion pressure in all parts of the bi- or multi-layer material. Binder mi-
can be used in the production of solid end mills with two distinct migration was also observed from coarse WC to finer WC and from higher
crostructures, one in the vast and one in the cutting edge. binder to lower binder contents. For this reason, the production of bi-
Fan et al. thoroughly reviewed the phenomenon of liquid phase layered cemented carbides with large difference in WC particle size
migration in bi-layer cemented carbides, which is observed under cer- and/or in binder content requires precise control of sintering process.
tain conditions when two dissimilar WC-Co cemented carbides are Shape distortions that may arise due to differences in shrinkage during
joined [160]. In general, the WC grain size and carbon content both liquid phase sintering of bi-layered WC-Co composites can be adjusted
affect the distribution of the liquid phase during sintering. Additionally, by binder content and sintering process. If other binders rather than
the initial Co content, and thus the fraction of liquid binder, in the two cobalt are used, inter-diffusion gradients at the by-layered interface
halves is also a factor affecting the redistribution of the binder. It is (with gradual change of mechanical properties) are also observed
important to consider these variables if a gradient is to be kept or [163].
avoided, depending on the desired functionality. The phenomenon of
liquid phase migration, and the gradients that occur, may not only 6.5. Macro gradients Co-migration
change the properties of both of the two halves of the bi-layer material,
but may also have a detrimental effect on the interface or joint, in- Konyashin et al. reported on binder redistribution due to carbur-
cluding swelling, unless the liquid phase migration is controlled prop- ization of pre-sintered compacts, the final step being gas-pressurized
erly. Fan et al. [160] established an empirical model based on the liquid sintering to full density [161] (Fig. 26). In this case, the initial Co
phase migration pressure, parameterized with WC grain size, liquid content was constant in all parts of the compact and the WC grain size
phase volume fraction and carbon content. It can be used to design was uniform. The redistribution of the binder is therefore solely due to
multi-layer cemented carbides. They showed that the redistribution of the carburization step, where a gradient in carbon content will form
58
Fig. 26. Macro-gradient cemented carbide with same WC grain size and two different cobalt concentrations in the microstructure: Cobalt-depleted surface and binder
enriched core produced by cobalt migration due to carbon potential. Adapted from [161], SEM images courtesy of Dr. Konyashin (Element Six, Germany).
throughout the compact, affecting the redistribution of the binder 7. Binders

during the final liquid phase sintering step. It is also possible to create a
Co-enriched surface by performing a decarburization process instead of The metal component of cemented carbides is necessary to form the
carburization. In any case, the mechanical properties change along the liquid phase during liquid-phase sintering, providing toughness to the
Co gradient. Depending on the depth and extension of the carburization whole component. The dominating metal used as binder is cobalt; fol-
process, the gradient that forms may reach several mm into the sample. lowed by nickel and iron. The reasons for the use of cobalt are its
Compressive residual stresses could be observed in the near-surface outstanding wettability to WC, as well as its advantageous mechanical
region. This was explained by the much higher Co content in the core of properties. Pure cobalt is stable in the hexagonal modification up to
the material, due to the redistribution of Co during sintering [161]. The 417 °C, while a cubic modification (fcc) exists at higher temperatures
binder exhibits significantly higher thermal expansion and will shrink [164]. After sintering, when the binder solidifies, the high temperature
more than the WC-skeleton during cooling from the liquid phase sin- fcc structure is retained. This is attributed to dissolution of W and the
tering step, leaving a state of tension in the Co-rich core region and a much higher thermal expansion of Co compared to the hard phase,
state of compression in the near-surface region. Compressive stresses in leaving the binder phase in tension after cooling. Consequently, re-
the surface are usually viewed as beneficial, since they add to the ne- sidual stresses result in planar faults (twins, stacking faults), where the
cessary total external stress that must be applied to break the material. binder locally managed to transform to the stable hcp structure [165].
Tensile stresses in the surface would facilitate crack generation and Nickel has been proposed to replace cobalt, but Ni behaves differently
propagation. in several aspects. Owing to its much higher stacking fault energy [Ni:
Fan et al. also reported on the formation of Co-content gradients by 125 mJ/m2 vs. Co: 20 mJ/m2], work hardening of nickel is only mod-
carburization [160]. In their study, the carburization is performed in a erate, since the lower density of stacking faults in Ni is less effective in
special heat-treatment cycle, which is done after liquid phase sintering causing dislocation pile-up, and hence less energy is dissipated during
to full density. Furthermore, the carburization is performed at tem- crack propagation [166]. Iron binder has not gained much industrial
peratures in-between the liquidus and solidus of the binder phase. Since acceptance because of its tendency to form martensite during the
both the liquidus and solidus drop to lower temperatures with in- cooling cycle. However, combinations between Co, Ni, and Fe in var-
creasing carbon content, the volume fraction of liquid binder will in- ious proportions have produced acceptable results, particularly for
crease continuously, starting at the surface, during the carburization wood cutting applications [167].
process.
The main application for this type of macroscopic gradient has, si-
milarly to the DP gradient, been found in inserts for rock drilling. In 7.1. Fe-Ni-Co binders
these applications, the hard and Co-depleted outer surface provides
abrasion resistance and minimizes the effect of erosion and corrosion of Cemented carbides with alternative binders (free of cobalt, or Co-
the binder phase, simply due to the reduced binder content. The Co- substituted) has gained again in attention due to both, a new classifi-
enriched core, together with the compressive residual stresses in the cation of toxic substances driven by the new European Community
surface, provides toughness and reduces the risk of early breakages. Regulation on chemicals and their safe use, known as the REACH
programme [122] and by the increased demand of cobalt from the
59
Fig. 27. SEM images of WC with 10% binder phase consisting of Ni, Co and Fe. The samples were made from the same WC raw powder [174].
electric vehicle industry. Reports on health risk associated to the use of toughness higher than those observed in similar WC-Co. Guo et al.
cobalt by Co-WC inhalation, its contact with human cells and the in- [181] reported on Ti(C,N)–15%Mo2C–20%Fe cermets. The formation
fluence of particle size can be found in [168–171]. of (Ti,Mo)(C,N) phases and reduced Ti(C,N) particle sizes improved
Cemented carbides with certain Fe–Ni–Co binder compositions can hardness and transverse rupture strength values. Alvaredo et al. pro-
be of interest for the cemented carbide industry in applications where duced Fe-based cermets by pressure-less sintering and spark plasma
improved fatigue strength and toughness are required. sintering; exhibiting remarkable changes in hardness, phase formation
A pioneer work by L. Prakash on Fe-based binders processing and and composition of the Ti(C,N) phase [182].
applications for cemented carbides [172] led to the production of
commercial Fe-Ni-Co binder alloys under the name AMPERSINT® 7.2. Precipitate reinforced binder
[173].
Addition of Fe reduces the allowable “carbon window” (WC-binder Several ternary complex carbide phases occur in the W-Co-C system
region free of η-phase and graphite) making it more difficult to adjust [165]. The most well-known are the two η-phases, M6C and M12C. In
the carbon balance of the alloy to avoid defects on the final micro- addition, the κ-phase, M4C, is also stable in the system, but usually at
structure. Changes of temperatures for the tie-lines and solid-liquid extremely low C-contents, which is why it is usually not observed in
transitions also affect the sintering behaviour of the Fe-Ni-Co-based cemented carbides. The Co-binder can form as layers with thicknesses
cemented carbides, which reflects in smaller WC grain size in sintered of up to a few μm. The performance of these materials is determined by
Fe-based cemented carbides (Fe-WC systems present lower eutectic the hardness and wear resistance of the binder.
temperature compared to Co and Ni). A tendency to coarser micro- H. Jonsson [115] reported on heat treatment of WC-Co carbides
structures in Ni-based cemented carbides is found, due to higher W with understoichiometric carbon contents. Heat treatments were car-
solubility compared to Co-based, see Fig. 27. Fe-based alloys also tend ried out for 100 h in a range of temperature between 500 and 800 °C to
to form martensite and Ni-based carbides are difficult to coat by con- precipitate fine coherent nanoparticles of the type Co3W in the binder
ventional Chemical Vapour Deposition [175]. phase to improve hardness/toughness behavior of cemented carbides
WC-Ni cemented carbides present better performance in oxidation for mining applications. Precipitation of dispersed nanoparticles in the
and corrosion conditions than that of WC-Co cemented carbides and has binder acts as barriers for dislocation movement increasing the strength
found applications in wear parts where corrosion resistance is needed. of the binder during deformation.
However, the mechanical properties (hardness and strength) of WC-Ni The same concept has been exploited to produce road picks for road
cemented carbides are relatively inferior to those of WC-Co. The major planing applications [183]. An improvement of the combination of
drawback of Ni-based cemented carbides is their reduced mechanical hardness, wear resistance, bending strength and resistance to the for-
strength compared to Co-based. The performance shortcomings of WC- mation and propagation of thermo-mechanical cracks can be achieved
Ni cemented carbides can be improved by producing submicron or by reinforcing the binder by precipitation of certain nanoparticles in the
close-to-nano WC-Ni cemented carbides and inhibiting the growth of W-Co-C system; which decompose isothermally from fcc-Co into hcp-Co
WC grains during sintering; or by adding other carbides to increase and Co3W. Konyashin et al. describe a process which mainly consists of
strength and/or hardness into the matrix of WC-Ni cemented carbides a heat treatment of an already sintered cemented carbides at tem-
[176]. Ultrafine WC-Ni cemented carbides with VC and TaC as WC peratures between 600 and 800 °C for periods of 0.5–10 h [183]. They
grain inhibitors produced by spark plasma sintering present good explain that the intermetallic precipitates are non-equilibrium nano-
combination of flexural strength and hardness. particles with a cubic Cu3Au crystal lattice different to the well-known
The role of the morphology and grain inhibition of WC with alter- hexagonal intermetallic Co3W phase. These intermetallic phases are
native binders has been investigated as well as the effect of flatter WC normally not stable in cemented carbides and are most likely transient
shape (platelet WC) on hardness of WC-Ni cemented carbidess with phases on the way towards formation η- phase precipitates. The particle
little addition of TiC has been modelled [177]. Carpenter [178] re- size of these nano-particles is in the range of 2–10 nm. The specific
ported on the production of cemented carbidess using of pre-alloyed nano-character and the Cu3Au lattice would produce binder strength-
625 stainless steel binder with improved properties for corrosive ap- ening by deformation of the Co-lattice. The verification of the nano-
plications. Aristizabal et al. [179] investigated the addition of Cr (and precipitates can only be done by TEM microscopy (Fig. 28). The for-
Co) to Ni-binders in cemented carbides, showing higher oxidation re- mation of the nano-precipitates results in increased values of coercivity
sistance and acceptable strength in wear part applications. On the same by almost constant magnetic saturation, indicating that the movement
line, CreFe binders have been used to produce wear pars for hard-fa- of the of Co-dipoles are hindered by the formation of lattice distortions
cing applications. Correa et al. investigated the effect of adding Si to Ni in the cobalt phase. This is the same effect observed by Jonsson [115].
binders in cemented carbides for wear parts [180]. They mentioned
that there is a solution strengthening of the nickel binder by silicon, 7.3. High entropy alloys
which improved significantly the mechanical properties of the NieSi
based cemented carbides, giving flexural strength and fracture Recently investigations on the use of high entropy alloys (HEA) in
60
Fig. 28. SEM image of the microstructure of a heat-

treated low carbon cemented carbide and TEM
images of the cubic Cu3Au lattice type nanoparticle
reinforced binder. (a) dark field TEM with the ap-
propriate electron diffraction pattern (insert). The
satellite reflection corresponding to the image in (a)
arises from the nanoparticles and is marked by blue;
(b) and (c) High Resolution TEM images of nano-
particles embedded in the fcc Co matrix and the
corresponding Fast Fourier Transform pattern (insert
in (b)), where the reflections from the nanoparticles
are marked by blue and those from the fcc Co matrix
are marked by red. (c) two nanoparticles are marked
by red circles. Adapted from [183]. (For interpreta-
tion of the references to colour in this figure legend,
the reader is referred to the web version of this ar-
ticle.)
determine the equilibrium state of a chemical system at constant tem-

perature and pressure. An essential part of the Gibbs energy is the
configurational entropy, which in overall may increase the stability of a
solid solution if it is the dominant term. To increase the configurational
entropy, the number of components/elements, should be increased. It
has been discussed that the term HEA might be misleading, since in-
creasing the number of dissimilar components also affects other con-
tributions to the Gibbs energy [184] and, also, that mixing itself is not a
thermodynamic process [185]. However, HEA is nowadays accepted as
the standard designation for equiatomic or near-equiatomic alloys with
5 or more components.
The concept of HEA has been extended to cemented carbides [186]
and cermets [187,188]. For cemented carbides, the HEA concept has so
far been applied mainly to the metallic binder phase, where the prin-
cipal elements have been selected as Fe, Ni, Co and Cr as well as W,
which will dissolve in the binder during sintering, and occasionally V
and Mn. In addition, the cubic carbide or carbonitride γ-phase, if pre-
Fig. 29. SEM -Back Scattered Electron image of a WC-γ-HEA cemented carbide. sent, may also constitute a multicomponent solid solution, containing,
Light grey particles are WC, medium grey particles are cubic carbides (γ-phase) e.g., Ti, Ta, Nb, Cr and W, apart from C and N.
and the dark regions correspond to HEA binder. Images from AB Sandvik A micrograph of the microstructure of a WC-γ-HEA alloy is shown in
Coromant R&D [189]. Fig. 29, where the HEA binder is made up of Co, Fe, Ni, Cr and W. No
obvious difference to a regular WC-γ-Co material can be discerned. EDX
cemented carbides has gained in attention. The attractiveness of HEA analysis of the binder phase indicates correspondence to a 5Cr-26Fe-
stems from maximizing the solid solution hardening, as well as in- 34Co-32Ni-3 W alloy on average, while the γ-phase consists of 45Ti-
creasing the chemical stability of both the binder and the carbide 4Cr-5Nb-16Ta-30 W, excluding C (all values in at. %) [189]. Naturally,
phases. the W content in the binder will depend on the overall C content. This
HEA originate from the concept of configurational entropy in che- particular alloy is situated more towards higher C content, with respect
mical thermodynamics and statistical mechanics. Their main char- to graphite, meaning that less W will dissolve in the binder. There is no
acteristic is the presence of one single solid solution phase (usually bcc evident inhomogeneity in the γ-phase (very even Back Scattered Elec-
or fcc) due to the use of 5 or more different elements. In chemical tron contrast), indicating the HEA character of the cubic carbide phase.
thermodynamics, the Gibbs energy is the state function that will Considering HEA cermets, the so far reported mechanical properties
61
Fig. 30. Microstructure of a WC-38.6Co-11.4Ni3Al alloy sintered at 1350 °C for 1 h in vacuum. a) SEM image of binder phase; b) Bright Field-TEM image of the
microstructure. Adapted from Long et al. [193].
indicate considerable brittleness. Fracture toughness values in the range resistance at high temperatures than do most other binder systems such
of 4–7 MPam1/2 at a binder content of 20 wt%, and a hardness in the as cobalt, nickel aluminides, or 304 stainless steel [195]. In addition,
range of 700–1300 HV5, were reported in [188]. This corresponds to a WC has sufficient wettability with FeAl [196]. Mosbah et al. studied the
WC-20 wt% Co material of medium or medium coarse WC grain size, abrasive wear of WC-FeAl cemented carbides at ambient temperature
but only 1/5 of the fracture toughness. Further research into this type of [197]. They showed that WC-FeAl composites exhibited a higher wear
material is needed to determine conclusively whether or not any de- resistance than that of WC-Co composites. However, these composites
leterious phases have precipitated. had lower fracture toughness than WC-Co cemented carbides due to the
For cemented carbides, Chen et al. reported more promising me- low ductility of the FeAl binder. The ductility of aluminides may be
chanical properties of their HEA-WC alloys [190]. At 20 wt% of HEA enhanced by reducing the grain size or increasing the alloying elements
binder alloy, the fracture toughness obtained was 17.4 (presumably in [198]. It has been shown that minor additions of boron to hot pressed
MPam1/2). This indicates that deleterious phases could be avoided. WC–FeAl–B composites results in increased toughness and inhibition of
Most reported work on HEA materials was conducted using com- WC grain growth [199] as well as also improving the wear resistance at
plicated synthesis routes, including extensive pre-milling. For materials ambient temperature compared to conventional WC–Co composites
based on multi-element cubic carbides, this could be justified, since it [200].
might be difficult to homogenize individual carbide particles on the WC-FeAl-B alloys have also been claimed to be suitable alternative
atomic level during sintering. However, the binder will melt during binder alloys for corrosive wear applications [201]. A recent study
liquid phase sintering and can thus easily be homogenized, as was comparing the wear behaviour of hot pressed WC/ 40 vol%(FeAl-B) to
shown by Linder et al. [191]. In fact, they also showed that conven- hot pressed WC-40 vol%Co and to commercial WC-16 vol%Co (H10F)
tional cubic nitride and carbonitride raw materials may be used, in concluded that the first one had the maximum sliding wear resistance at
conjunction with conventional processing, to produce γ-phase free all the experimental temperatures (ranging from ambient to 600°). This
gradient sintered cemented carbide. is claimed to be due to the higher hardness and higher strength at high
temperatures of the FeAl-B matrix compared to the Co matrix, but the
study is inconclusive [202].
7.4. NieAl, FeeAl and Ru binders WC-Co-Ru cemented carbides are established in the cutting in-
dustry. Adding Ruthenium to a WC-Co cemented carbide [203,204]
Apart from exploring metallic binder systems based on Fe, Ni and increases the hardness of the cemented carbide without losing the
Co, some research has been performed on intermetallic compounds as corresponding amount of toughness. The hardening of the binder leads
binder phase, e.g., Ni3Al or Fe3Al as potential binders for cemented to improved abrasion resistance. The addition of Ru also improves the
carbides. corrosion resistance of the cemented carbide [205]. Lisovskii showed
The Ni3Al phase crystallizes in an ordered fcc structure, with de- that the improved properties are due to precipitation hardening of the
signated positions for Ni and Al respectively. Ni3Al is a common com- binder phase [206] due to the formation of a CoeRu binder solid so-
ponent in Ni-based superalloys for high temperature applications re- lution with stable hexagonal structure at higher temperatures compared
quiring retained strength and sufficient corrosion resistance, such as to Co binders.
turbine blades. Since cutting tool edges are subjected to high tem-
peratures during machining, it is of interest to explore the properties of
Ni3Al as a binder. A WC-Ni3Al cemented carbide was produced by Liang 7.5. Binder-free carbides
et al. by means of Spark Plasma Sintering and subsequent shaping, in-
cluding grinding [192]. Recently Long et al. reported on cemented The so-called binder-free, or binderless, cemented carbides consist
carbides of the type WC-Co-Ni-Al with Ni3Al strengthened binder phase essentially only of hard phase materials, with no metallic binder pre-
[193], see Fig. 30. It is claimed that the hot hardness of cemented sent, except for impurities, which originate from powder processing
carbides with Ni3Al strengthened binder phase is higher than conven- and/or raw materials. Their processing was already addressed in the
tional Co-based cemented carbides; and that the Ni3Al precipitates can first patents about sintered carbide [1,2].
restrain rapid wear by holding WC grains firmly and avoid detachment Due to the absence of binder, binderless carbide can thus potentially
during wear degradation. be polished to a very fine surface roughness and can therefore also be
Iron aluminides possess high hardness and high elastic modulus and used in micro-tools, i.e. as a micro-die for electrical micro-devices.
are, therefore, promising materials for tribological applications in ag- WC-Co cemented carbides can normally be sintered to full density in
gressive environments [194]. Iron aluminides exhibit a higher wear vacuum furnaces at moderate temperatures. One of the main
62
differences in processing of binderless materials is thus the necessity to the smallest WC grain size was in all cases obtained at substoichio-
apply much higher temperatures and pressures to achieve full density, metric compositions. Additionally, Pötschke et al. found that the use of
since there is no metallic binder which may melt and distribute effi- common grain growth inhibitors, such as Cr, had a strong effect on the
ciently during the sintering process. Alternatively, a very fine WC WC grain size. Other common additives, apart from grain growth in-
powder may be used to improve sinterability [207]. Strict control of the hibitors, are the cubic carbides TiC and TaC, which are added for their
grain growth is necessary in such a case. Another issue is related to the mechanical properties [210].
carbon content, since the absence of Co or any other binder metal, to- Nino et al. also reported on the hardness and Youngs modulus of
gether with the extremely narrow stoichiometry of WC means that any their sintered materials, as a function of carbon content. Thus, the
carbon deficiency will result in W2C, while a surplus will inevitably strong variation in grain size makes it difficult to judge how the pre-
result in graphite precipitates. sence of W2C affects the mechanical properties, since the grain size
Pötschke et al. conducted a thorough study on the sinterability and seems to be the dominating factor. However, Nino et al. [211] also
microstructure of binderless WC materials [208]. An overview of their reported on the hardness of WC and W2C materials and determined that
results is shown in Fig. 31. It is noticeable that overstoichiometric or polycrystalline W2C could have a hardness comparable to WC, de-
near-stoichiometric blends tend to demonstrate dramatic WC grain pending on the grain size. For example, WC with a linear intercept grain
growth, with elongated (in a 2D cross-section) grains, of > 100 μm in size of 0.43 μm showed hardness of approximately 25 GPa, while the
length. hardness dropped to 19 and 17.5 GPa at a linear intercept grain size of
Nino et al. [209] reported less extensive WC grain growth at over- 1.4 and 2.5 μm, respectively (the hardness values given here are taken
stoichiometric carbon by using a resistance heated hot press and a from the study of Nino et al. at maximum load). Comparatively, in the
lower temperature than that reported by Pötschke et al. Nevertheless, study of Nino et al., W2C exhibited a hardness of 17 GPa (unspecified
Fig. 31. Sintered microstructures of binderless materials. Left column pure WC with or without C addition. Right column WC + Cr3C2 with or without C addition.
Top to bottom: Overstoichiometric, nearly stoichiometric and understoichiometric composition. All sintered at 1900 °C and 100 bar Ar pressure. Note the very fine
grain size at substochiometric carbon content (bottom of left column) and the fine grain size for any carbon content if Cr3C2 is added (right column). Courtesy of Dr. J.
Pötschke at Fraunhofer IKTS.
63
grain size). selectively affect to a larger extent the binder phase than the carbide
Imasoto et al. investigated the mechanical properties of a WC-TiC- phase. Also, ion beam milling will produce a similar effect, where the
TaC binderless material with Cr3C2 and VC additions [210]. Increased binder is selectively etched [212] being not the case in binderless car-
additions of VC were found to have a negative effect on the transverse bides [213].
rupture strength and only a minor positive effect on hardness, above an
addition of 0.4 mass-% of Cr3C2 + VC. Presumably, this is the result of
8. Summary
precipitation of bulk VC, which, as already explained, has a detrimental
embrittling effect in WC-Co cemented carbides. The absence of a me-
In this work, we have presented and summarized selected -and from
tallic binder significantly lowers toughness and transverse rupture
the author's point of view- relevant microstructures that can be pro-
strength, wherefore binderless materials are used in applications where
duced in the cemented carbide industry. Some of them are established
resistance to abrasion or corrosion are of prime importance. This in-
in products (i.e. fine-grained or γ-phase containing carbides; γ-phase
cludes, first and foremost, mechanical seals and sliding parts, subjected
free gradient or DP-carbides) and other microstructures are research
to extensive wear and sometimes corrosion. Furthermore, the difference
trends focusing on solving present and future needs (i.e. alternative
in hardness and chemical properties between the WC, TiC or TaC grains
binders or NbC-cermets). The aim of the review is to present possibi-
compared to a metallic binder often means that it is difficult to obtain a
lities to design and produce cemented carbide microstructures on pur-
surface of low roughness. For example, mechanical polishing will often
pose to achieve specific properties, that can be used in current and
Fig. 32. Map of real microstructures covered in this work.
64
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International Journal of Refractory Metals & Hard Materials 80 (2019) 40–68

Contents lists available at ScienceDirect

International Journal of Refractory Metals

Cemented carbide microstructures: a review T

AB Sandvik Coromant R&D, Lerkrogsvägen 19, SE-126 80 Stockholm, Sweden

ARTICLE INFO ABSTRACT

1. Introduction materials by pressing and sintering. Tungsten monocarbide (WC) and

Fig. 1. Categorisation of cemented carbide microstructures selected in this work.

Compressive strength (MPa)

WC hP2 a = 0.29058 c = 0.28365 15.72 23 2776 707 120

increasing carbon activity. If the C content of the cemented carbide is

4. WC morphology and chemistry

Fig. 5. Temperature ranges for densification stages, together with an schematic

Ultrafine Submicron Fine Medium Coarse Extra coarse

Gurland [26] λ = dWC(1 − C)−1VCo(1 − VCo)−1

4.1.1. Quality control of sintered WC-Co-based cemented carbide

Coarse grained Fine grained

a large amount of Ta doping in the WC grains had lower hardness than

Fig. 15. SEM image of a platelet WC-Co cemented carbide [77].

Fig. 16. Light optical microscopy image of WC-(Ta,Nb)C-Co

throughout the compact, affecting the redistribution of the binder 7. Binders

Fig. 28. SEM image of the microstructure of a heat-

determine the equilibrium state of a chemical system at constant tem-

Fig. 32. Map of real microstructures covered in this work.

105/106 (1988) 225–231. Reutte, Vol. 2 2009 Austria. (HM 5).

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