Nova Book

Complimentary Copy
Complimentary Copy
Chemistry Research and Applications
No part of this digital document may be reproduced, stored in a retrieval system or transmitted in any form or
by any means. The publisher has taken reasonable care in the preparation of this digital document, but makes no
expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions. No
liability is assumed for incidental or consequential damages in connection with or arising out of information
contained herein. This digital document is sold with the clear understanding that the publisher is not engaged in
rendering legal, medical or any other professional services.
Complimentary Copy
Chemistry Research and Applications
The Chemistry of Gallic Acid and Its Role in Health and Disease
Jeff C. Murdoch (Editor)
2023. ISBN: 979-8-88697-672-4 (Softcover)
2023. ISBN: 979-8-88697-729-5 (eBook)
A Review of Hydrazine and Its Applications

Thomas W. Gerdes (Editor)
2023. ISBN: 979-8-88697-671-7 (Hardcover)
2023. ISBN: 979-8-88697-678-6 (eBook)
Pyrene: Chemistry, Properties and Uses

Charles R. Howe (Editor)
2023. ISBN: 979-8-88697-670-0 (Softcover)
2023. ISBN: 979-8-88697-677-9 (eBook)
Pyrimidines and their Importance

Roger G. Ward (Editor)
2023. ISBN: 979-8-88697-656-4 (Softcover)
2023. ISBN: 979-8-88697-663-2 (eBook)
What to Know about Lanthanum

Catherine C. Bradley (Editor)
2023. ISBN: 979-8-88697-615-1 (Softcover)
2023. ISBN: 979-8-88697-623-6 (eBook)
The Future of Biorefineries

Waldemar Nyström (Editor)
2023. ISBN: 979-8-88697-524-6 (Hardcover)
2023. ISBN: 979-8-88697-528-4 (eBook)
More information about this series can be found at

https://novapublishers.com/product-category/series/chemistry-research-and-
applications/
Complimentary Copy
William D. McMartin
Editor
Tungsten Carbides
Advances in Research and Applications
Complimentary Copy
Copyright © 2023 by Nova Science Publishers, Inc.
All rights reserved. No part of this book may be reproduced, stored in a retrieval system or transmitted
in any form or by any means: electronic, electrostatic, magnetic, tape, mechanical photocopying,
recording or otherwise without the written permission of the Publisher.
We have partnered with Copyright Clearance Center to make it easy for you to obtain permissions to
reuse content from this publication. Please visit copyright.com and search by Title, ISBN, or ISSN.
For further questions about using the service on copyright.com, please contact:
Copyright Clearance Center

Phone: +1-(978) 750-8400 Fax: +1-(978) 750-4470 E-mail: info@copyright.com
NOTICE TO THE READER
The Publisher has taken reasonable care in the preparation of this book but makes no expressed or
implied warranty of any kind and assumes no responsibility for any errors or omissions. No liability is
assumed for incidental or consequential damages in connection with or arising out of information
contained in this book. The Publisher shall not be liable for any special, consequential, or exemplary
damages resulting, in whole or in part, from the readers’ use of, or reliance upon, this material. Any
parts of this book based on government reports are so indicated and copyright is claimed for those parts
to the extent applicable to compilations of such works.
Independent verification should be sought for any data, advice or recommendations contained in this
book. In addition, no responsibility is assumed by the Publisher for any injury and/or damage to persons
or property arising from any methods, products, instructions, ideas or otherwise contained in this
publication.
This publication is designed to provide accurate and authoritative information with regards to the
subject matter covered herein. It is sold with the clear understanding that the Publisher is not engaged
in rendering legal or any other professional services. If legal or any other expert assistance is required,
the services of a competent person should be sought. FROM A DECLARATION OF PARTICIPANTS
JOINTLY ADOPTED BY A COMMITTEE OF THE AMERICAN BAR ASSOCIATION AND A
COMMITTEE OF PUBLISHERS.
Library of Congress Cataloging-in-Publication Data
ISBN: H%RRN
Published by Nova Science Publishers, Inc. † New York
Complimentary Copy
Contents
Preface .......................................................................................... vii

Chapter 1 Tungsten Carbide in Heterogeneous Catalysis:
An Application of Theory to Gain Insights into
Catalytic Processes ............................................................1
Carlos Jimenez-Orozco, Andrey Koverga,
Elizabeth Flórez and José A. Rodriguez
Chapter 2 Advances in Cemented Carbides for
Metal Machining ..............................................................85
Jialin Sun and Jun Zhao
Chapter 3 Recent Advances in the Synthesis of
Tungsten Carbide Nanoparticles..................................117
D.T. Usmanov
Chapter 4 Advances in Research and Applications of
Tungsten Carbides in Micro-EDM for
Titanium Alloy ...............................................................151
Phan Nguyen Huu, Dung Hoang Tien,
Shailesh Shirguppikar, Long Banh Tien,
Toan Nguyen Duc and Vaibhav Ganachari
Chapter 5 A Numerical Study of the Cracking Behaviour
of Coated Tungsten Carbide Cutting Tools
during the Machining Process ......................................179
K. Bounif, M. Abbadi and M. Nouari
Index .........................................................................................195
Complimentary Copy
Complimentary Copy
Preface
This book contains five chapters that detail Tungsten carbides. Chapter One
covers applications of Tungsten carbide (WC) and transition metal/Tungsten
carbide (M/WC) (M=Pt, Pd, Ag, Au, Ni, Cu, Rh) as heterogeneous catalysts
in several processes. Chapter Two attempts to comprehensively summarize
the current advances of nanostructured cemented carbide, functionally graded
cemented carbide and cemented carbide with an alternative binder to the metal
binder phase. Chapter Three analyzes published papers devoted to the research
and synthesis of tungsten carbide nanoparticles. Chapter Four presents recent
advances in the research and applications of tungsten carbides in micro-
electrical discharge machining for titanium alloy machining. Lastly, Chapter
Five investigates a finite element approach that has been developed to explore
the wear by cracking in cutting tools during machining processes.
Complimentary Copy
Complimentary Copy
Chapter 1
Tungsten Carbide in Heterogeneous Catalysis:

An Application of Theory to Gain Insights into
Catalytic Processes
Carlos Jimenez-Orozco1,, PhD

Andrey Koverga1,2, PhD
Elizabeth Flórez1, PhD
and José A. Rodriguez3, PhD
1Grupo de Materiales con Impacto (Mat&mpac), Facultad de Ciencias Básicas,
Universidad de Medellín, Medellín, Colombia
2Instituto de Quimica de São Carlos, Universidade de São Paulo, São Carlos, Brazil
3Chemistry Division, Brookhaven National Laboratory, New York, USA
Abstract
Heterogeneous catalysis is important for producing fuels and

commodities, with several processes using platinoids (i.e., Pt, Pd, Os, Rh,
Ru, and Ir) as core materials. However, the scarcity of these metals
implies a strong limitation for their use at large scale in the long term.
Tungsten carbide (WC) has been proposed as an alternative non-
expensive catalytic material, and using it as a support for Pt, or as an
active phase in several reactions, requires a better understanding of the
fundamental origins of its catalytic properties. Thus, the WC and M/WC
(M: transition metal) systems have been extensively studied as well-
defined catalysts in the last years, using calculations from first principles
to unveil their chemistry at the atomic level, where the knowledge gained
is useful as a key and preliminary step in the design of technical catalysts.

Corresponding Author’s Email: cjimenez@udemedellin.edu.co.
In: Tungsten Carbides

Editor: William D. McMartin
ISBN: 979-8-89113-221-4
© 2023 Nova Science Publishers, Inc.
Complimentary Copy
2 Carlos Jimenez-Orozco, Andrey Koverga, Elizabeth Flórez et al.
The theoretical studies offer a complete panorama as a bridge

between theory and experiment, since they account for relevant variables
such as surface coverage, temperature, and pressure conditions within the
thermodynamics landscape, together with the establishment of reaction
rates within a kinetic framework. The fundamental studies provide an
understanding at the atomic level, identifying surface active sites, plus
geometric and electronic properties which can be modulated to account
for a desired catalytic activity, according to the applications.
In many cases, the computations for WC and Pt/WC systems are
performed using periodic Density Functional Theory (DFT), within the
framework of solid-state physics. The conceptual topics and details of the
methodology are fundamental, since they provide the basis for building
technical catalysts and acquire relevant information. Therefore, it is quite
relevant to explore the behavior of WC and Pt/WC under different
chemical environments, together with their applications in several
processes as heterogeneous catalysts.
The current chapter covers applications of WC and M/WC (M=Pt,
Pd, Ag, Au, Ni, Cu, Rh) as heterogeneous catalysts in several processes,
including binding and transformation of key molecules (CO2, O2, CO,
H2O, ethylene, acetylene, ethane, ethylidyne, hydrogen, methanol,
ammonia, NOx, formic acid) in industrial operations linked to
hydrogenation and hydrodeoxygenation reactions. The applications to
electrocatalysis imply a particular connection experiment-theory in the
fundamental understanding of several phenomena. Therefore, the
Hydrogen Evolution Reaction (HER) involves experimental details
regarding synthesis methods and how the experimental conditions affect
the electrocatalytic performance of WC-based systems.
The chapter ends with conclusions, including an outlook regarding
the potential and future use of tungsten carbides in heterogeneous
catalysis, together with the challenges and knowledge gained from the
current fundamental understanding of several processes at the atomic
level by computing models.
Keywords: tungsten carbide, heterogeneous catalysis, DFT
Introduction
Heterogeneous catalysis is used to produce several commodities, fuels, and

fine chemicals, within the heart of the chemical industry. Many of these
systems use platinoids (i.e., Pt, Pd, Rh, Ir, Os, and Ru), due to the remarkable
catalytic activity of these Pt-group metals. Despite the high importance of
platinoids, there are some drawbacks concerning their use in the long term:
Complimentary Copy
Tungsten Carbide in Heterogeneous Catalysis 3
i) Pt-group metals are scarce elements in the Earth crust, implying a high cost
of extraction, purification, and commercialization, resulting in high prices of
the operation for the catalyzed processes even at small scales, and ii) A
common drawback of Pt-based catalyst is the poisoning due to sulfur, a typical
element found in the petrochemical industry, imposing restrictions for its use,
implying additional processes for recovery and re-use of huge amounts of
materials. Indeed, the use of Pt-group metals in the petrochemical industry is
key to producing fuels and even in the energy transition from fossil fuels to
the production of green hydrogen. These issues hinder the large-scale
deployment of target processes in medium to long term, and call for efforts to
explore alternative materials with several key characteristics: a) made with
highly available materials, i.e., non-expensive, b) easy to synthesize, c) sulfur
resistant, and d) with a catalytic activity comparable to that of Pt-group metals.
Tungsten carbide was put under the spotlight in the early 1970s (Levy &
Boudart, 1973) due to its Pt-like behavior as a heterogeneous catalyst for the
isomerization of 2,2-dimethylpropane to 2-methylbutane and water
production from oxygen and hydrogen at room temperature. Around the same
time (Vértes, Horányi, & Szakács, 1973), it was discovered that tungsten
carbide has catalytic activity for the reduction of aromatic nitro compounds
and quinones. Next, it was found that the carbide also catalyzed ethylene
hydrogenation (Isao Kojima, Miyakasi, Yasunobu, & Yasumori, 1979),
cyclohexane dehydrogenation (Vidick, Lemaître, & Leclercq, 1986), and the
benzene hydrogenation reaction (Marquez-Alvarez, Claridge, York, Sloan, &
Green, 1997), sometimes with a penalty of catalyst poisoning.
The use of tungsten carbide implies an advantage regarding sulfur
resistance. Indeed, it was found (Da Costa et al., 2001) that WC/Al2O3 has a
similar catalytic activity to Pt/Al2O3 for tetralin hydrogenation, with the
advantage that tungsten carbide is not as easily poisoned as Pt, conserving the
same activity even for 20 hours under a constant presence of H2S, while the
corresponding activity of Pt drops four orders of magnitude.
There are two strategies to overcome the issues related to platinoids-based
catalysts: a) substitute the platinoids with less expensive materials, b)
minimize the amount used of platinoids, locating them on surfaces of other
materials, attacking the drawbacks above, while keeping their catalytic
activity and being sulfur resistant. Tungsten carbides have been proposed on
both strategies, i.e., as an alternative catalyst to platinum (pristine tungsten
carbide) and also as a good support for platinum (Esposito & Chen, 2011).
The use of tungsten carbide as a support brings the advantage of minimizing
the amount of platinum in the system (see Figure 1), supporting thin films or
Complimentary Copy
monolayers (ML) of Pt, and even small clusters, with the concomitant and
reasonable decrease of costs associated with a limited use of the platinoids.
Figure 1. Schematics for the cost of platinoids at different loadings in the catalyst.
Several works have shown that tungsten carbide fulfills the requirements
to replace or minimize the use of Pt-group metals (Hwu & Chen, 2005).
Tungsten is among the most abundant metals in the Earth crust, tungsten
oxides are used as a starting material to produce the carbide, relying on simple
hydrocarbons like C2H4, both easy to get and cheap materials. Moreover,
tungsten carbide has a Pt-like behavior in several reactions, and it is sulfur-
resistant. The use of tungsten carbides also has new potential applications, like
in biomass valorization (Chan-Thaw & Villa, 2018), reversed water gas-shift
reaction (Morse, Juneau, Baldwin, Porosoff, & Willauer, 2020), dry reforming
of hydrocarbons (Czaplicka, Rogala, & Wysocka, 2021), valorization of large
organic oxygenated compounds (Führer, van Haasterecht, & Bitter, 2022; Guo
et al., 2017), and water splitting reaction (Sohail et al., 2022). Similarly,
tungsten carbide is a viable candidate material for electrochemical processes
significant for the field of energy storage/conversion, such as water splitting.
While materials based on noble metals remain unrivalled as catalysts for this
process in both acidic and alkaline media (Esposito, Hunt, Kimmel, & Chen,
2012; Greeley, Jaramillo, Bonde, Chorkendorff, & Nørskov, 2006; Michalsky,
Zhang, & Peterson, 2014), tungsten carbide-based compounds remain stable
Complimentary Copy
in working conditions and are characterized by a promising activity toward

the hydrogen evolution reaction.
Understanding of how a catalyst works is the basis to address
modifications of the material to modulate the properties of the catalyst and get
the desired behavior. For these purposes, fundamental studies at the atomic
level have been conducted through computational modelling. The increasing
development of computational capabilities during the last two decades had a
direct and positive impact on the fundamental studies of tungsten carbide as a
catalyst, providing an in-depth understanding of the catalytic processes,
covering the physics and chemistry of the solid, the study of adsorbates, the
interaction between them, and their transformation to achieve a particular
product and/or behavior. Indeed, the tools and models created to represent a
catalyst have provided useful insights which cover mainly four areas: i) the
chemical structure and crystal lattice of common types of tungsten carbide, ii)
the physical properties of the material, iii) the chemical reactivity towards a
desired product using different electronic descriptors, and iv) application to
several reactions studying the transformation of adsorbates over tungsten
carbide as substrate, together with the properties at the end of the process,
which usually involves both thermodynamic and kinetic analysis.
In this chapter, we cover mainly the use of computational modelling (and
some experimental techniques) to understand tungsten carbide and its
application in several key technical processes. This chapter includes the
following sections: i) Models and methodologies for studying tungsten
carbide-based systems, ii) Pristine tungsten carbides in heterogeneous
catalysis, iii) Tungsten carbides as a support of metals in composite catalysts,
iv) Applications in electrocatalysis, and v) Conclusions.
Models and Methodologies for Tungsten

Carbide-Based Systems
For the theoretical study of tungsten carbides, many surface models have been
developed within the framework of solid-state physics and using density
functional theory. In this section, we cover the models and computational
methodologies used to study tungsten carbide-based catalysts, starting with
the bulk WC, followed by the computational methodologies used to
investigate the pristine surfaces of WC, and finally the models for WC as
support for metal adlayers will be discussed.
Complimentary Copy
Bulk Tungsten Carbides
The combination between W and C to form a carbide, yields two atomic W/C
ratios for stable tungsten carbides, i.e., 1 (WC) and 2 (W2C), according to the
phase diagram of the W-C systems reported by (Alexey S Kurlov & Gusev,
2013). The W2C is not a trivial system, suffering structural changes in a wide
range of temperatures, due to the different location and distribution of C atoms
in the metallic lattice, including the presence of β’’-W2C, β’-W2C, and β-W2C
phases with disordered orthorhombic and hexagonal structures, usually
obtained at temperatures above 1523 K, but a complete and detailed
experimental information for these systems is limited. On the other hand, the
WC system is more stable, undergoing low to negligible structural changes
upon rising the temperature in a wide concentration of carbon, yielding only
one crystal system, i.e., hexagonal, obtained below 1523 K. Therefore, in
catalysis WC is used more often than W2C. For the ratio W/C=1, a cubic phase
also can be formed, with a rock salt-like structure, however, it is a metastable
system obtained at temperatures above 2700 K. After a while this cubic phase
converts back into a hexagonal one, in other words, the cubic system can be
considered as a structural modification of the hexagonal one at high
temperature conditions. The theoretical studies on this topic indicated that the
low stability of the cubic WC system is due to the occupation of antibonding
states (A. Y. Liu & Cohen, 1988).
The notation for the crystal systems of WC is confusing in the literature
since there is no general agreement on their nomenclature. However, the
tendency of several authors is to use the notation provided by Kurlov and
Gusev (Alexey S Kurlov & Gusev, 2013), where the hexagonal and cubic
systems are named α-WC and γ-WC, respectively. Therefore, the frequent use
of these notations in the last years, serves as a guide to establish a standard
notation system for tungsten carbides, and in this book Chapter, we will follow
this proposed nomenclature.
The bulk α-WC and γ-WC systems have a unique primitive cell each. The
unit cell of hexagonal α-WC has only two atoms, one tungsten (W) at a corner
and a carbon (C) atom inside of the cell as shown in Figure 2. Repeating the
unit cell along all three lattice vectors the bulk system can be obtained, as seen
in Figure 2, whose crystal structure model corresponds to the geometry
obtained from the minimization procedure using DFT and, therefore, describes
the most stable structure.
Complimentary Copy
Figure 2. Structural model of the hexagonal α-WC system. Left: primitive cell,
middle: unit cell, right: repeated unit cell. The cells are represented using black lines.
Surfaces of Pristine Tungsten Carbide
The heterogeneous catalysis operates on surfaces of solid catalysts. Therefore,

the question arises on the appropriate theoretical description of α-tungsten
carbide surfaces and their intrinsic catalytic activity toward various processes.
The photoemission experiments in the 1980s’ showed the existence of the α-
WC(0001) surface (Mattheiss & Hamann, 1984; Stefan et al., 1984), while the
studies of activity on α-WC(0001) and the structural models of the (0001)
surface started in the 1990s’ (Brillo, Hammoudeh, et al., 1998; Brillo,
Kuhlenbeck, & Freund, 1998; Brillo, Sur, Kuhlenbeck, & Freund, 1998a,
1998b). Since the beginning of 2000s’ the increase in computational resources
led to an increase of theoretical studies regarding the α-WC(0001) surface,
from fundamental understanding to applications in heterogeneous catalysis.
Indeed, computational studies focused on understanding the role of C
atoms in carbides, demonstrated that the presence of C atoms in WC carbides
moderates the chemical activity by limiting the exposure of metal atoms, a
phenomenon known as the ensemble effect. Moreover, the formation of C-W
interactions in the carbide’s crystalline structure induces a modification of the
bare W electronic structure, reducing the number of states at the Fermi level
minimizing the chemical reactivity of WC relative to metallic tungsten, a
phenomenon known as ligand effect. Both ensemble and ligand effects result
in the chemical reactivity of WC being more moderate than that of its parent
metal, yielding a catalyst able to adsorb and transform various chemical
compounds better than bare W. (Posada-Pérez, Viñes, Rodriguez, & Illas,
2015).
Complimentary Copy
The model of the α-WC(0001) surface can be seen in Figure 3 and is

characterized by the presence of C- and W-terminations. The process of
creation of the computational model for a surface involves several steps. Using
the optimized bulk structure, a desired surface plane is exposed and new lattice
vectors and symmetry operations are defined. The surface slab is then
propagated along its a and b lattice vectors to assure the availability of a
certain number of surface atoms, depending on the target coverage of the
adsorbates. A typical surface slab model has from three to eight atomic layers,
from which the upper ones are allowed to freely move together with adsorbates
during the energy minimization, while the bottom ones are frozen in bulk-like
geometry. To prevent interaction of the slabs repeating in a direction,
perpendicular to the surface plane, several layers of vacuum are added.
The computational modelling helped in characterizing the geometrical
and electronic properties of the α-WC(0001) surface (N. Jin et al., 2015). The
thermodynamic stability of both terminations was studied initially by (Siegel,
Hector, & Adams, 2002) and later by (Rao, Lou, Zhou, Zhang, & Zhong,
2021), where they found that the W-termination is more stable than the C-
termination. These findings addressed some theoretical studies to focus only
on W-termination, however, in a practical catalyst, both C- and W-
terminations are present in roughly 50:50 ratio, hence, both terminations
deserve detailed theoretical analyses (Jimenez‐Orozco, Flórez, & Rodriguez,
2023). Furthermore, since these terminations have different physcical and
chemical properties, they can be seen as extreme study cases for theoretical
models of tungsten carbide. Hence, the properties of practical WC-based
catalysts would lie somewhere in between those obtained for the polar W and
C-terminations. For the sake of clarity, the C- and W-terminations of the α-
WC(0001) surface are named as C-WC and W-WC, respectively (Koverga,
Flórez, Jimenez-Orozco, & Rodriguez, 2021a, 2021b). The binding of
adsorbates on both C- and W-terminations of the α-WC(0001) surface can be
performed on several sites, see Figure 3.
Though the hexagonal α-WC system is more stable than the cubic γ-WC,
some researchers have studied the cubic system on a fundamental level and its
applications in catalysis. The surface of the cubic system is γ-WC(001),
similar to the (001) surface of a rock salt structure (Jimenez-Orozco, Flórez,
Montoya, & Rodriguez, 2019), see Figure 4, favoring a direct comparison with
other similar TMC(001) surfaces (Viñes, Sousa, Liu, Rodriguez, & Illas,
2005).
Complimentary Copy
Figure 3. Model of the α-WC(0001) surface with W- (left) and C-termination (right).
Top and side (bottom) views of the slab. Sites for W-termination: top-W, bridge,
hollow-e, hollow-W. Sites for C-termination: 1 top-C, 2 bridge, 3 hollow-e, 4 hollow
W.
Figure 4. Model of the bulk γ-WC (top) and the γ-WC(001) surface (bottom) with
top (left).
Complimentary Copy
Tungsten Carbide as a Support of Metals
The use of WC as a support for Pt resembles a core-shell system, where the

supported Pt has the known properties of a bare platinum surface, with the
advantages of lower cost and avoiding the agglomeration of metallic particles
due to the strong adhesion of Pt over WC, in some cases yielding improved
catalytic performance, relative to bare Pt and WC. Indeed, some studies
indicated that the location of Pt over WC involves only slight changes in ligand
and strain effects (Pašti, Skorodumova, & Mentus, 2015), suggesting that a Pt
monolayer (ML) behaves as a massive Pt surface. This statement should be
taken with a grain of salt since important fundamental properties, often
correlated with catalytic activity, such as partial charges, Pt-Pt distances and
work function of Pt/WC surfaces do not coincide with those of the Pt(111)
with similar hexagonal arrangement of surface Pt atoms. Nonetheless, these
systems were explored by (Vasić, Pašti, & Mentus, 2013) using DFT and
models of the α-WC(0001) surface with C- and W-termination, i.e., Pt/C-WC
and Pt/W-WC, according to the recent nomenclature used for these systems
(Koverga, Flórez, Jimenez-Orozco, et al., 2021b, 2021a). It was found that α-
WC(0001) can be covered by a monolayer (Θ=1 ML) of Pt or Pd, starting from
Θ=0.25 ML and going even up to Θ=2 ML, see Figure 5. The location of
several Pt atoms form layers by occupying the preferential surface sites, viz.
Chcp and Ehcp sites (unique sites on the carbides terminations, roughly
corresponding to hcp and fcc three-fold hollow sites in fcc (111) surfaces) on
W-WC and C-WC, respectively, with respective adsorption energies of −6.50
eV and −6.02 eV (Koverga, Flórez, Jimenez-Orozco, et al., 2021a). The
location of a Pt layer over W-WC follows a hexagonal ABABA stacking of
the WC substrate, see Figure 6, i.e., Pt layers can spread epitaxially, which
also applies for a second Pt layer, i.e., a bilayer. The sites for location of
several adsorbates are included in Figure 5.
The raise in the number of Pt atoms from Θ=0.25 ML to upper values,
induces an increase of the Pt-WC distance on the W-WC system, yielding a
final geometry that stabilizes the Pt/W-WC system as compared to the bare
W-WC surface. On the contrary, on the C-WC, the location of Pt destabilizes
the C-WC system. On both W-WC and C-WC, the Pt-Pt distances are larger
in the Pt ML than in the bulk platinum, which yields a positive degree of strain
around +4%. The stabilization of the Pt/W-WC is due to the charge transfer
between W and Pt, which compensates the surface expansion upon Pt
adsorption, according to the downshifts of more than 1 eV the d-band center
of the Pt/α-WC(0001) relative to the Pt(111) surface, which correlates to the
Complimentary Copy
experimental XPS result for the shifting of the 4f peak of Pt of a platinum ML

over WC. The DFT results complement the landscape by indicating a charge
migration W → Pt for the Pt/W-WC system, leading to an average Pt atomic
charge of -0.43e, while for the Pt/C-WC system the charge transfer Pt → C
produces an average decrease of atomic charge of Pt of 0.19e. These electronic
views are complemented by using the cohesion energy (Ecoh,Pt) and adsorption
energy (Eads,Pt) descriptors. The cohesion energy refers to the energy of Pt
atoms to form the Pt bulk system, while the adsorption energy is related to the
measure of the Pt binding over the α-WC(0001) surface. If Ecoh,Pt > Eads,Pt, the
Pt atoms prefer to bind among them to form bulk Pt; however, if Ecoh,Pt < Eads,Pt,
the Pt prefers to cover the α-WC(0001) instead of forming bulk Pt. The results
showed that Eads,Pt is larger more than 5 eV relative to Ecoh,Pt indicating that
the formation of a stable Pt monolayer over α-WC(0001) is preferential,
referred as PtML/α-WC(0001).
Figure 5. Pt monolayer supported on the α-WC(0001) surface with W- (left) and C-

termination (right). Top and side (bottom) views of the slab. Labels of atoms as in
Figure 2., Pt is represented as white balls in the topmost layer. Surface sites in left: 1
top, 2 bridge, 3 Ehcp, 4 Whcp; in right: 1 top, 2 bridge, 3 Ehcp, 4 Chcp.
Complimentary Copy
Figure 6. Staking ABABA-type of the Pt/W-WC surface. Side view of the slab.
Once the PtML/α-WC(0001) is formed, the Density of States (DOS) for

this system is similar to that of the pristine Pt(111) surface, while Pt(111) and
α-WC(0001) alone are different among them as expected (Esposito et al.,
2010). An important fundamental property, often associated with the stability
of adsorbates on surfaces of transition metals is the d-band center, mentioned
above. It can be calculated as the first moment of the projected d-band density
of states, ρd, with respect to the Fermi level:

 Ed  E  EF  dE
d  

(1)
  d  E  EF  dE

Here ε represents the Kohn-Sham eigenvalues, n(ε) is the calculated d-

PDOS, and EF denotes the Fermi energy.
Being one of the factors defining the interaction of metallic surfaces with
reacting species and reaction intermediate during heterogeneous processes, the
d-band center of a material has a significant impact on its catalytic properties.
In its turn, the stability of an adsorbate on the catalyst’s surface is defined
as the difference between the total energy of the system comprising the surface
and adsorbate (Esurf+ads) and the sum of total energies of the surface (Esurf) and
the adsorbate moiety in gas phase (Eads):
E  Esurf  ads   Esurf  Eads  (2)
Complimentary Copy
Therefore, the properties of PtML/α-WC(0001) are close to those of a

pristine platinum surface, with the advantage of avoiding agglomeration of Pt
atoms supported on cheap WC. Then, the PtML/α-WC(0001) system have been
used to explore its catalytic capabilities in several systems.
While PtML/α-WC(0001) is the most know system, monolayers of other
metals have been explored in heterogeneous catalysis, viz., AuML/α-
WC(0001), PdML/α-WC(0001), NiML/α-WC(0001), AgML/α-WC(0001),
CuML/α-WC(0001) and RhML/α-WC(0001) (Kelly, Stottlemyer, Ren, & Chen,
2011; Jinhua Zhang & She, 2020b; X. Zhang, Lu, & Yang, 2016a; X. Zhang,
Yang, & Wu, 2018; W. Zhao et al., 2022; Y. Zhao, Zhang, & Yang, 2019).
Transition metal monolayers over tungsten carbide are a promising class of
materials to apply as catalysts for several applications, minimizing the amount
of the used platinoids and with the concomitant decrease of costs. Indeed,
cluster of metals have also been explored recently over tungsten carbide
surfaces (Koverga, Flórez, & Rodriguez, 2021; Prats & Stamatakis, 2022; Y.
Zhao, Zhang, & Yang, 2020), opening a new topic to explore in the research
field of the cluster/WC system and their applications in heterogeneous
catalysis.
Computational Methodologies
The computational details described below, apply not only to bulk WC but
also to WC surfaces and their applications in catalysis. The WC systems
models above have been studied theoretically by using methodologies within
the framework of solid-state physics and using density functional theory
(DFT). The total electronic energy of the structure and the geometric
parameters can be used to characterize the properties of the crystal system.
For the computation of the total electronic energy of the WC bulk system
and its respective surfaces using DFT, the use of exchange-correlation
functionals is mandatory. The Perdew–Burke–Ernzerhof (PBE) functional
(Perdew, Burke, & Ernzerhof, 1996) is the most widely used functional for
theoretical studies regarding transition metal carbides in the last years,
including tungsten carbides. Other functionals have been used as well, viz.,
Perdew–Wang (PW91) (Perdew et al., 1993), and the revised version of PBE
known as RPBE (Hammer, Hansen, & Nørskov, 1999), however the PBE
functional yields WC lattice parameters that are the closest to experimentally
measured values and fairly well describes the interaction of the carbide with
small molecule adsorbates. The optimization of the structures is usually
Complimentary Copy
carried out by using a gradient conjugate algorithm (within Generalized

Gradient Approximation to the exchange-correlation energy, GGA), which is
considered converged when the forces acting on W and C atoms are below a
threshold, for instance 0.01 eVÅ-1 or similar values. By using the GGA-PBE
approach, the electronic energy is explored on the potential energy surface
under a minimization procedure, following an iterative method (Self-
consistent field, SCF method). For the SCF method, it is common to establish
a threshold to achieve a minimized structure, where the criterium is energy
below 10-5 eV (or similar values) between successive iterations, hence
achieving a converged energy, which corresponds to the most stable geometry
for the given system.
The calculations above can be carried out by using several computational
codes, both commercial and open source. Though there are several codes
available, one of them is significantly more popular than the others and is
widely used in the field of theoretical chemistry. Specifically, the Vienna ab
initio simulation package (VASP), a commercial Fortran-based code
developed in Vienna (Kresse & Furthmüller, 1996). The performance of the
VASP code entails a remarkable development of pseudopotentials to describe
the internal electrons (core) of the atoms, while the valence electron density is
expanded in a set of plane-waves below a threshold of kinetic energy, usually
around 400 eV. The effect of the core electrons in the valence electron density
is described by the projected augmented wave (PAW) method (Blöchl, 1994),
implemented by Kresse and Joubert (Kresse & Joubert, 1999). Other packages
found for calculations of tungsten carbides in a few works are Dmol3 (Delley,
1990, 1995, 2000), CASTEP (Segall et al., 2002), Quantum ESPRESSO
(Giannozzi et al., 2009), SIESTA (Soler et al., 2002), ABINIT (Gonze et al.,
2009), and WIEN2k (Schwarz & Blaha, 2003).
The Brillouin zone is sampled by using the Monkhorst-Pack scheme, a
mesh of k-points. The choice of the k-points mesh depends upon many factors,
including the geometry of the cell, the presence or absence of a vacuum layer
in the system, and functional and cutoff energy among them. Usually, a
symmetric 5×5×5 k-mesh or higher is used for the bulk WC, while for the
surfaces of WC and their applications in catalysis, a 3×3×1 is a popular choice.
Significantly denser meshes of 11×11×1 or above are used in certain specific
cases, such as density of states and band structure calculations, while for
possible isolated adsorbate molecules, a single point 1×1×1 k-mesh is typically
employed. For large systems comprising 140 atoms or more, which is typical
size for ab initio molecular dynamics calculations, a single point k-mesh is
Complimentary Copy
used. These meshes could be different, according to the right balance

methodologies/time to achieve reasonable results in a certain code.
By using the computational setup above, the experimental information
available for bulk WC has been reproduced theoretically with low error
margins, including the lattice constants and cohesive energies (Viñes et al.,
2005). Indeed, the lattice parameters have been calculated with errors < 2%
relative to the experimental values (Jimenez-Orozco et al., 2019). The
theoretical results on band structure and the Density of States (DOS) agree
with the experiments, while the valence electron charge density shows a
metallic-type bonding for WC, similar to that seen in solid W (A. Y. Liu,
Wentzcovitch, & Cohen, 1988). Other studies, however, report a combined
metallic, covalent, and ionic nature of W-C bonding in the carbide
highlighting the complexity of this material (Li et al., 2010).
Pristine Tungsten Carbides in Heterogeneous Catalysis
Since Levy and Boudart discovered that WC exhibits Pt-like activity (Levy &
Boudart, 1973), numerous studies have found that WC is a promising material
in heterogeneous catalysis due to their distinctive catalytic behavior in
important reactions associated with the conversion of organic and inorganic
molecules (such as hydrogenolysis, hydrogenation, reforming, isomerization,
and deoxygenation) and the hydrogen evolution reaction (HER), among others
(Claridge et al., 1998; Frauwallner et al., 2011; Furimsky, 2003; Gong et al.,
2016; Hwu & Chen, 2005; Jimenez-Orozco, Flórez, Viñes, Rodriguez, & Illas,
2020; Koverga, Flórez, Jimenez-Orozco, et al., 2021b; Rodriguez et al., 2009;
Sullivan, Chen, & Bhan, 2016).
So far, structure-activity relationships for pristine WC have not been
elucidated. Understanding the origin of catalytic activity is important yet
challenging. In recent years, quantum chemical calculations have become a
fundamental tool to get insights, understand, and explain the WC role in
several catalytic reactions, showing the impact of surface defects, surface
carbon, and surface termination on the catalyst reactivity.
Since hydrogen is present in several catalytic processes on tungsten
carbides, its behavior on the carbide surfaces deserves a separate and detailed
analysis. As mentioned in the Introduction to this book chapter, tungsten
carbides can catalyze the hydrogenations of ethylene (I Kojima, Miyazaki,
Inoue, & Yasumori, 1979; Márquez-Alvarez, Calridge, York, Sloan, & Green,
1997). The material is also an active system for the hydrogen evolution
Complimentary Copy
reaction (HER) (Esposito et al., 2012; Greeley et al., 2006; Michalsky et al.,
2014). In general, there are many hydrogenation processes for which carbide
catalysts are useful (Esposito & Chen, 2011). Thus, on the basis of academic
and practical reasons, it is important to understand well the dissociation of H2
and H storage on tungsten carbide.
Hydrogen Adsorption and Dissociation
Calculations based on DFT have been used to study the adsorption and
dissociation of H2 on different terminations of tungsten carbides (Jimenez-
Orozco et al., 2023; Koverga et al., 2019; Koverga, Flórez, & Rodriguez,
2021). In its most stable phase, tungsten carbide usually adopts a hexagonal
crystal structure (Figure 2, α-WC), but a less stable cubic structure also can
exist (Figure 4, γ-WC). As described in the models section, the α-WC(0001)
surface can be either W or C terminated, and a γ-WC(001) surface exposes
50% of W and 50% of C atoms.
Figure 7. Calculated stable geometries for the interaction of H2 with C- and W-

terminated α-WC(0001) surfaces (top and center, respectively) and with a cubic γ-
WC(001) surface (bottom). Carbon and W atoms are represented by large black and
white spheres, respectively. The small grey spheres denote H atoms. Taken with
permission from (Koverga et al., 2019) Copyright (2019) American Chemical
Society.
Complimentary Copy
Figure 7 summarizes the calculated stable geometries for the interaction

of H2 with different sites in tungsten carbide surfaces (Koverga et al., 2019).
Molecular adsorption was observed only in a few cases. In general, the H―H
bond in the molecule did not survive and the produced H-adatoms ended
adsorbed on C or W atoms. At small coverages, H preferred to bind to C atoms
of the carbide, transforming them into active centers for hydrogenation
processes.
Figure 8. Calculated minimal energy paths for the H2 → 2H reaction on three types
of WC surfaces. Each diagram indicates the energy of the final configuration relative
to the initial system and, where possible, the energy barriers associated with the
dissociation, marked with triangles on the plot. Carbon and W atoms are represented
by large black and white spheres, respectively. The small gray spheres denote H
atoms. Taken with permission from (Koverga et al., 2019) Copyright (2019)
American Chemical Society.
Complimentary Copy
Figure 8 shows DFT calculated reaction paths for the dissociation of H2

on surfaces of tungsten carbide (Koverga et al., 2019). These results indicate
that H2 dissociation could occur readily on both terminations of the hexagonal
α-WC(0001) surface and on γ-WC(001). This is in good agreement with a
second theoretical study for the interaction of H2 with the extended α-
WC(0001) surface and small (WC)n (n= 1-10) clusters, where almost no
barrier was found for the cleavage of H―H bonds (Xi, Huang, Forrey, &
Cheng, 2014).
Since the dissociation of H2 on WC is relatively easy, how much atomic
hydrogen can one pack on surfaces of this carbide? The coverage of hydrogen
can have a big impact in hydrogenation reactions and in the HER process. DFT
and ab initio atomistic thermodynamics were used to explore the capability of
α-WC(0001) with C- and W-terminated surfaces to dissociate several H2
molecules and to form H-adatoms, achieving ΘH values in the range of 0.1 to
2.00 ML (Jimenez-Orozco et al., 2023).
Figure 9. DFT results for medium (top) and high (bottom) coverages of H on C- and
W-terminated surfaces of α-WC(0001) Size code: Large gray, W; Medium black, C;
Small gray, H. Taken from (Jimenez‐Orozco et al., 2023).
Complimentary Copy
It was found that both WC−C and WC−W surfaces have a remarkable
capability for easily dissociate several H2 molecules. Figure 9 summarizes
results for medium and high coverages of hydrogen (Jimenez-Orozco et al.,
2023). At both adsorbate coverages, The H-adatoms form a strong C−H
covalent bond, which could limit further applications in hydrogenation
reactions. In contrast, the H-adatoms on WC−W are more labile, serving as a
hydrogen reservoir for several catalytic applications (Jimenez-Orozco et al.,
2023).
A compact overlayer of H, bottom of Figure 9, could block the adsorption
of other adsorbates. Indeed, the binding energy of CO2, CO, H2O, C2H4, and
C2H2 decreased remarkably when the surface had a monolayer of H-adatoms,
ΘH=1.00 ML, as compared to the pristine surfaces (Jimenez-Orozco et al.,
2023) Thus, the modulation of ΘH should be a mandatory variable when
dealing with reactions with H2 streams at several conditions of pressure and
temperature.
Application of Pristine Tungsten Carbides in

Heterogeneous Catalysis
In this section we provide a concise overview of the potential applications of

pristine WC in heterogeneous catalysis from a computational point of view for
some representative systems, viz., activation of ethylene, methane activation
and coupling, NH3 decomposition, CO2 adsorption and dissociation, and
finally CO and H2O adsorption and reaction. Before addressing the
contributions from theoretical studies, a short context of the systems above is
included below.
The hydrogenation of unsaturated hydrocarbon is a process used to
produce clean fuels and raw materials, where the most used catalysts are Pt-
group metal-based materials, while the catalytic conversion of CO2 into value-
added products is an effective way for reducing its negative impact on the
environment. Junea et al. (Juneau, Yaffe, Liu, Agwara, & Porosoff, 2022)
investigated isolating the effects of tungsten carbide phase and particle size on
CO2 hydrogenation reaction efficiency, using tungsten carbide encapsulated
in silica. The authors reported that a micelle-based silica encapsulation
technique produces ∼10 nm tungsten carbide nanoparticles which are
potential catalysts for reverse water–gas shift (RWGS) reaction.
Complimentary Copy
The hydrogenation of ,β-unsaturated aldehydes like cinnamaldehyde is

an important step toward valuable chemicals for the pharmaceutical,
perfumery and flavour industries. The cinnamaldehyde hydrogenation on
tungsten carbide catalyst was reported recently (Führer et al., 2022), where the
carbide catalysts are 4–6 times less active than the Pt catalysts. However, since
transition metals are more abundant and therefore less expensive than noble
metals, the Mo-carbide is a viable non-noble alternative to Pt. Interestingly,
the authors found that the carbides and Pt are selective towards C═C
hydrogenation and unlike Pt, the carbides additionally form b-methylstyrene.
Another interesting process to explore is the efficient cleavage of C–O bonds
as an important step to produce value-added aromatic compounds, where
reported on the selective hydrogenolysis of inert aryl ether carbon-oxygen (C–
O) bonds to produce aromatic compounds by tungsten carbides with different
phase compositions. The authors found a new oncoming for the synthesis of
active carbide catalysts to demonstrate the effect of the active phases and the
way of carbon insertion by carburization for hydrogenolysis catalysis (H. Fang
et al., 2017).
Methane is a greenhouse gas and one of the main components of natural
gas. The reforming to produce syngas is one process to convert methane to
more valuable chemicals more promising (Cai & Hu, 2019). For this reaction
Claridge and co-workers (Claridge et al., 1998) found that high-surface-area
tungsten carbides could be active and stable to present activities comparable
to the supported noble metals catalysts.
Ammonia decomposition is a promising strategy for the potential use of
NH3 as a hydrogen storage medium (K. E. Lamb, Dolan, & Kennedy, 2019;
Lan, Irvine, & Tao, 2012). Various effective catalysts have been employed for
hydrogen production by NH3 decomposition (Karaboğa, 2021; K. E. Lamb et
al., 2019; Maier, Stass, Cerda, & Salmeron, 2012; Pinzón, Romero, de Lucas-
Consuegra, de la Osa, & Sánchez, 2022). Pensare, et al., (Pansare, Torres, &
Goodwin, 2007) reported a detailed study of NH3 decomposition on tungsten
carbide (WC). They found that the catalytic behavior of WC was strongly
dependent on pretreatment conditions and the complete decomposition of NH3
at 550°C. Also, it proposes that WC could be an excellent catalyst for use in
ammonia decomposition.
Activation of Ethylene
Jimenez-Orozco and co-workers (Jimenez-Orozco et al., 2019) studied the
binding and activation of C2H4 on α-WC(0001) and WC(001) surfaces as the
Complimentary Copy
first step in the hydrogenation reaction. They found that i) The most stable
structure on γ-WC(001) and α-WC-C surfaces has a di-σ-CC mode, while the
binding on α-WC-W implies hybrid surface site; ii) There is a preference for
ethylene to bind on α-WC-C (-2.91 eV), which could induce surface
poisoning. On the contrary, the binding on α-WC-C is weaker (-1.68),
indicating that this surface could be the most relevant in catalysis. iii) The
C2H4 molecule is activated on all the evaluated surfaces since there is an
elongation of the ethylene C–C bond length. The binding energy extend
compared with Pt (111) surface follows the trend: α-WC-C (-3.35 eV) > α-
WC-W (-2.24 eV) > Pt(111) (-1.78 eV) > γ-WC(001) (-1.19 eV).
Methane Activation and Coupling

Zhang, T., and co-workers (T. Zhang, Holiharimanana, Yang, & Ge, 2020)
reported a systematic computational study of methane activation and coupling
on two different surfaces of -WC, (0001) and (1120). They found i) WC is
active by C − H dissociation and C − C coupling and the reactivity depends
on the surface structure also, the distribution of products is sensitive to the
local structure of the system (see Figure 3 and Figure 6 origin article); ii) In
the W-terminated of α-WC(0001) surface, methane dissociates to (CH)ads by
successive C−H bond breaking steps and dimerization through C−C coupling
to (C2H2)ads, where the C2 is the dominant species on the surface and this
deportment is similar in the α-MoC(0001) surface. iii) In the WC (112̅0)
surfaces, C−H activation was increased, and the surface carbon may react with
(CH)ads from methane dissociation to form (C2H2)ads and it will not desorb as
acetylene.
Ammonia Decomposition
Rao, X. et al., (Rao et al., 2021) studied ammonia decomposition on WC
(0001) surface terminated by W and C using density functional theory (DFT)
with periodic slab models. For this study, it considered four adsorption sites
(top, hcp, bridge, and fcc) on the WC (0001) surface to probe the adsorption
configurations of all possible reactants and intermediates and for NH3, two
configurations; the first was that two hydrogen atoms point up and one
hydrogen atom points down; the second was the opposite configuration of the
prior. They found that the adsorption energies of NHx (x = 0 - 3) species on
the W-WC surface were in all cases higher than those on the C-WC surface to
promote the N-H bonds activation (see Figure 10). However, C-WC(0001)
Complimentary Copy
surface was more favorable for the decomposition of ammonia to produce

hydrogen.
Figure 10. The potential energy diagram for the dehydrogenation of NH 3 on tungsten
carbide.
Adsorption and Dissociation of CO2

The conversion of CO2 to CO is a desired pathway because the CO product
can be used as a component of syngas (CO + H2) for generation of chemicals
and fuels. This conversion involves first activation by bonding and then
cleavage of one or two C-O bonds. The elongation of these bonds is essential
in the activation process (Porosoff, Kattel, Li, Liu, & Chen, 2015).
Koverga and co-workers (Koverga et al., 2019) researched the adsorption
and dissociation on WC(0001) and W(001) surfaces. They found that i) CO2
adsorption on three-fold hollow sites of the (0001) C-terminated WC is
energetically the most favorable bonding configurations on hexagonal
surfaces. ii) a significant deformation of the internal geometry of the CO2
molecule, which is commonly explained because of a net charge transfer from
the carbide surface to the adsorbed molecule (Posada-Pérez et al., 2014). For
the (0001) of the hexagonal WC, the calculated charge transfer from the
surface to the adsorbate was ~1.08 e and ~1.13 e, for the C- and W-
terminations of WC(0001), respectively. For the cubic (001) surface, the total
charge transfer from the surface to the adsorbed moiety was the smallest
among the studied cases. iii) the W-terminated hexagonal WC(0001) surface
is able to dissociate spontaneously CO2 on most of the adsorption sites, this is
Complimentary Copy
similar to the behavior on Mo2C found by Posada-Perez et al. (Posada-Pérez

et al., 2014), where they reported an easy C-O bond cleavage for CO2 adsorbed
on top of a Mo atom; iv) CO2 adsorption on a top-C site of cubic WC(001)
surfaces results in carbon dioxide activation; v) For CO2 dissociation of energy
barriers on each surface is given in Figure 11. For C-terminated found an
energy barrier of 0.71 eV, for W-terminated a small barrier was found for CO2
dissociation. This CO2 dissociation could occur easier on the metallic
termination of tungsten hexagonal carbide than on the metallic termination of
orthorhombic Mo2C, where an energy barrier reported is of ~0.7 eV. For the
cubic (001) surface, carbon dioxide dissociation has the highest energy barrier.
This energy barrier is appreciably lower than the one found for CO2
dissociation on cubic δ-MoC (1.41 eV), indicating that this process would
occur easier on cubic tungsten carbide (Posada-Pérez et al., 2016).
Figure 11. Minimal energy path for a CO2 → CO + O dissociation on the studied
WC surfaces. Each diagram indicates the energy of the final configuration relative to
the initial system and the barrier associated with the dissociation. Figure 11. Adapted
with permission from (Koverga et al., 2019) Copyright (2019) American Chemical
Society.
Complimentary Copy
Adsorption and Reaction of CO and H2O

The adsorption and reaction of CO and H2O on WC tungsten carbide are
important to design and optimize the electrocatalyst of direct methanol fuel
cells (Sharma & Pollet, 2012). Tang, et al. (Tong, Wu, & Chen, 2018) studied
detailed the reaction mechanism of CO and H2O on hexagonal a-WC with the
W-terminated (0001) surface. Also, they studied the formation of derivates
such as HCO, COH, COOH, and CO2. They found that: i) for H2O, OH, O, H,
CO and CO2 preferable binding sites are top, hcp, hcp, fcc, top, and bridge
sites, respectively; ii) WC (0001) surface exhibits significantly reaction
activity toward the dehydrogenation of H2O and OH, being favorable both
kinetically and thermodynamically, which present barriers of 0.61 and 0.63
eV, respectively iii) WC (0001) surface presents less activity to the formation
of their derivates HCO, COH, COOH, and CO2 compared to the Cu (111) and
Pt (111) surfaces (see Table 2 in (Tong et al., 2018).
Tungsten Carbides as a Support of Metals in

Heterogeneous Catalysts
A common practice in heterogeneous catalysis to improve the performance of

a material implies the modification of the catalytic system by changing their
chemical and physical properties. These changes are usually carried out by
supporting metals or creating vacancies, together with changes in the synthesis
conditions to modulate the textural properties. Though transition metal
carbides, including tungsten carbides, show catalytic activity for several
chemical reactions, the location of metals over them pointed to an improved
catalytic performance.
Though Pt monolayers serve as a reference system to study MML/WC, not
only Pt ML can be located on the α-WC(0001) surface but monolayers of Pd,
Ag, Au, Ni, Cu and Rh (Kelly et al., 2011; W. Yu, Mellinger, Barteau, & Chen,
2012; Jinhua Zhang & She, 2020b; X. Zhang et al., 2016a, 2018; W. Zhao et
al., 2022; Y. Zhao et al., 2019) with reasonable stability and promising
catalytic performance in several reactions, see Figure 12. In this section, some
representative systems are discussed which cover a wide range of applications.
Complimentary Copy
Figure 12. Studied systems on MML/α-WC(0001) using DFT. M=Pt, Pd, Au, Ag, Cu,
Ni, and Rh.
Binding and Conversion of Methanol, Water, O2, CO, CO2

over MML/α-WC(0001)
The decomposition of methanol (CH3OH) has attracted the interest in the last
decades due to its potential applications in direct methanol fuel cells (DMFC)
and its applications in the chemical industry as a benchmark C1 chemical to
produce commodities (Jinhua Zhang & She, 2020b). Hence, the understanding
of methanol binding and decomposition details could provide key insights to
link to a several outcomes. Indeed, the methanol decomposition pathways
connect with other research fields of interest like oxygen reduction reaction
(ORR) and H2 production via steam reforming (Katsounaros et al., 2013). The
ORR also links various disciplines like energy conversion, materials science,
and biology, while methanol steam reforming focuses in the production of a
clean fuel (H2) in line with the migration from fossil fuels as energy sources
into cleaner ones. The authors (X. Zhang et al., 2016a) compared PtML/α-
WC(0001), PdML/α-WC(0001), and AuML/α-WC(0001) towards the OOR.
They found that the direct O2 dissociation is highly unlikely on all these
systems due to the high energy barriers (> 1 eV), but the formation and
dissociation of OHH is more feasible on AuML/α-WC(0001) than on the other
systems (lower barriers), where the hydrogenation of OH has a barrier of 0.83
eV being the rate-limiting step, pointing to AuML/α-WC(0001) as a promising
Pt-free system for ORR.
Complimentary Copy
For the DMFC, the Pt and Pd-based catalyst have the highest potential.
However, the use of Pt on a large scale is limited due to its higher costs and
easily poisoning upon CO presence, which is a primary decomposition product
of methanol. The utilization of Pd overcomes these issues of Pt, because Pd
exhibits a high CO tolerance, a lower cost (around five times) and a similar
catalytic performance than platinum. Indeed, the desorption temperature of
intermediates of methanol decomposition is lower than that on pristine
Pd(111) surface, indicating a strong capability of PdML/α-WC(0001) to reduce
surface poisoning. The authors (Jinhua Zhang & She, 2020b) identified the
surface sites for the binding of the intermediates of methanol decomposition,
i.e., CH3O, CH2O, CH2OH, CHOH (cis and trans), CHO, CO, H2O, OH and
H, where the stronger binding energy was found for CHO (-3.59 eV) and the
weaker for H2O (-0.60 eV). The authors studied several reaction mechanisms,
establishing the most feasible one according to the criterium of lower barriers:
CH3OH → CH2OH+H → trans-CHOH+H → CHO+H → CO+H2O,
concluding that the synergistic effect between the active phase (Pd) and the
support α-WC(0001) addresses a feasible CH3OH decomposition with low
barriers and also reducing the utilization of the Pd noble metal. Notice that the
methanol decomposition pathways vary with the supported metal monolayer
over WC, but the generality is that the decomposition of methanol leads to the
formation of carbon monoxide (CO) and water. See a typical CH3OH
decomposition pathway on PdML/α-WC(0001) in scheme of Figure 13.
Figure 13. General scheme for methanol (CH3OH) decomposition on PdML/α-

WC(0001). Surface represented as a rectangle with lines inside. The adsorbates
bonded on the surface are represented as a vertical line to connect adsorbate-surface.
Complimentary Copy
The methanol decomposition involves CO and H2O binding on the M/α-

WC(0001) surface (see Figure 13). Therefore, some independent studies focus
on the understanding the binding of H2O, CO and even CO2, since carbon
dioxide (CO2) is the product of complete oxidation of CO, due to the toxicity
and negative impact on human life of carbon monoxide (CO), an undesired
gas to release at the end of methanol decomposition process.
The binding energy of H2O was similar on both the PtML/α-WC(0001)
composite (-0.61 eV) and on the pristine Pt(111) surface (-0.56 eV) (Liang,
Chen, & Ma, 2017). Although both adsorption energies are similar, the authors
indicated that there is a preference of H2O for the PtML/α-WC(0001) system.
However, it is worth mentioning that -0.61 vs -0.56 eV is not a huge difference,
results from a model without inclusion of van der Waals effects and zero-point
energy contributions. The results for a system containing both CO and H2O
adsorption, followed by H2O dissociation (H2O* → OH* + H* → O* + 2H*)
and later CO2 formation (CO* + O* → CO2*), yields a non-conclusive
behavior on PtML/α-WC(0001) relative to Pt(111). For the H2O* → OH* + H*
step, the barrier on PtML/α-WC(0001) and Pt(111) was 1.21 eV and 0.91 eV,
respectively, while the respective barriers for the step OH* + H* → O* + 2H*
follows a similar trend, i.e., 1.90 vs 1.21 eV. Therefore, H2O dissociation was
not advantageous on PtML/α-WC(0001). However, the CO* + O* → CO2* step
has a barrier of only 0.47 on PtML/α-WC(0001), lower than on Pt(111) surface
(0.70 eV). An interesting behavior was studied by Liang Y. et al. (Liang, Chen,
& Ma, 2017) where they studied the effect of the CO coverage on the
adsorption energy. The authors found that the adsorption energy on PtML/α-
WC(0001) and Pt(111) at a coverage ΘCO = 0.17 ML was 1.58 and 1.88 eV,
respectively, however, the respective values at ΘCO = 1 ML was 0.64 and 0.69
eV. Interestingly, the CO binding energy tends to convert to a value close to
0.6 - 0.7 eV at a coverage of 1 monolayer of CO. Later, Zhang et al. (L. Zhang,
Yan, Lu, Zhang, & Yin, 2022) studied the binding of CO over PtML/α-
WC(0001) and Pt(111) considering a deeper analysis of surface sites. The
authors found that the most stable site in every case on PtML/α-WC(0001) and
Pt(111) had an adsorption energy of -1.44 and -1.83 eV, respectively, a
difference of ~0.4 eV. On the contrary, the difference between both systems
found by (Liang et al., 2017) was only 0.05 eV, i.e., energy degenerated
systems. Moreover, Zhang et al. (X. Zhang, Lu, & Yang, 2016b) found that
the CO binding energy for PtML/α-WC(0001) and Pt(111) was 1.59 and 1.85
eV, respectively, a difference ~0.3 eV. Therefore, besides the theoretical
results found, the role of PtML/α-WC(0001) is not completely understood yet
for carbon monoxide binding and oxidation to CO2 as compared to Pt(111).
Complimentary Copy
The pristine Pt(111) surface suffers poisoning due to the strong binding
of CO, blocking sites to operate in other reactions. Hence, the production of
CO as product in some reactions, e.g., methanol decomposition, is limited on
Pt surfaces. However, supporting a monolayer of Pt over WC, i.e., PtML/α-
WC(0001), yields to a non-poisoned surface (X. Zhang et al., 2018). In other
words, the role of WC as support is to increase the tolerance of the system
towards poisoning due to CO deposition, weakening the interaction
CO―surface. Indeed, the adsorption energy of CO on PtML/α-WC(0001) is
weaker than on Pt(111) (-1.44 vs -1.83 eV). Though the Pt ML limits CO
binding, this behavior is undesired from the point of view of CO oxidation to
CO2, together with the extend of the oxygen reduction activity. Therefore,
monolayers of Au, Ag, and Cu have been explored to account for a system
with an intermediate CO binding strength and with a high catalytic activity
towards CO2 formation, accounting for high oxygen reduction activity,
yielding promising results.
The binding of CO have been studied beyond Pt, particularly on pristine
surfaces of Au, Ag, and Cu, where the catalytic activity for CO oxidation (CO
+ O2 → CO2 + O) follows the trend: Ag(111) > Au(111) > Cu(111). Though
the pristine Ag(111) surface was the better, the key issue was the weak CO (-
0.29 eV) and O2 (-0.16 eV) binding capability on the silver surface. However,
the issue was overcame by supporting a silver monolayer, AgML/α-WC(0001),
yielding stronger binding energies for CO (-0.78 eV) and O2 (-0.59 eV).
Indeed, the barrier for the rate-limiting step of the CO oxidation process drop
on AgML/α-WC(0001) to 0.48 eV, from the value on the pristine Ag(111)
surface of 1.03 eV, i.e., the CO oxidation was improved by supporting a silver
ML over a tungsten carbide surface. It is worth mentioning that only the W-
terminated surface of α-WC(0001) was selected in these studies, due to its
higher thermodynamic stability as compared to the C-terminated surface (Y.
Zhao et al., 2019).
Binding and Conversion of C2+ Oxygenates and N-Based Compounds

on MML/α-WC(0001)
The use of formic acid (HCOOH) is useful for the understanding and
development of direct formic acid fuel cells (DFAFC), where HCOOH is
considered a promising hydrogen source system. Then, the studies in this field
focus on the HCOOH decomposition, particularly on Pt and Pd, which have
been widely used DFAFC. Though Pt has a good performance in HCOOH
decomposition into CO2 or CO, the use of Pd has the advantage of avoiding
the poisoning of the catalyst. Indeed, the use of Pd has a better performance
Complimentary Copy
than Pt, pointing to a rational choice of Pd instead of Pt in DFAFC. Hence,

HCOOH decomposition have been conducted recently over both PtML/α-
WC(0001) and PdML/α-WC(0001) (Jinhua Zhang & She, 2020a) (Jinhua
Zhang & She, 2020c), using WC as a support to minimize the amount of Pt
and Pd, preserving a good catalytic performance for HCOOH decomposition.
The DFT studies with PtML/α-WC(0001) (Jinhua Zhang & She, 2020a)
indicated that the most feasible route for the formic acid decomposition is
shown in Figure 14, where the rate-determining step is the formation of CO2.
Nonetheless, the authors explored several routes and found that the HCOO is
the main intermediate in the decomposition process of HCOOH towards CO2,
while the formation of cis-COOH, trans-COOH, and HCO yields to the
formation of CO. The study of HCOOH decomposition implies the analysis
of adsorption of several adsorbates including identification of surface sites for
everyone, viz. HCOOH, HCOO, cis-COOH, trans-COOH, HCO, CO, H2O,
OH, CO2 and H. An important conclusion is that the catalytic performance of
PtML/α-WC(0001) is almost the same to that of platinum, pointing to a
comparable activity of both materials but with a remarkable lower costs by
using PtML/α-WC(0001). It is worth mentioning that only the W-termination
was used for studying PtML/α-WC(0001), based on the higher stability of
Pt/W-termination over Pt/C-termination. The study of HCOOH
decomposition on PdML/α-WC(0001) has similar results than those seen on
PtML/α-WC(0001), in terms of decomposition pathways, intermediates, rate-
determining steps, and routes for the formation of CO and CO2. Nonetheless,
the advantage of PdML/α-WC(0001) over PtML/α-WC(0001) accounting for a
minimization of surface poisoning has not been studied theoretically yet.
The use of biodiesel is a promising alternative to fossil fuels, utilizing
biomass as a source material. The presence of oxygen in biodiesel limits the
performance as fuel, hence, the removal of oxygen is a desired behavior, and
the search for materials for this purpose is of growing interest, where tungsten
carbides have shown potential in cleavage C―O bonds, i.e.,
hydrodeoxygenation (HDO) reactions. The biomass is a complex system;
hence, model compounds are necessary to analyze on the tungsten carbide
surfaces, viz. guaiacol, diphenyl ether, phenetole, veratrole, dimethoxyphenol,
phenol and anisole. Among them, guaiacol is the most typical compound in
lignin-derived systems, moreover, it is known as the ideal probe molecule in
HDO (H. Fang, Wu, Chen, & Yuan, 2021). Though the importance of HDO
process and the experimental evidence for the performance of tungsten
carbide-based catalysts, there is a scarce theoretical and fundamental
understanding of the process, where the theoretical studies focus on the
Complimentary Copy
adsorption behavior, lacking of details regarding the use of models and robust
methodologies, since the studies have been used as a complement of
experimental studies, limiting the extent of the theoretical scopes for MML/WC
and even for pristine WC (Kelly, Ren, & Chen, 2015) (H. Fang et al., 2019)
(Humbert, Menning, & Chen, 2010) (Ren et al., 2014).
The nitrogen-based compounds have also been studied on MML/α-
WC(0001), since NOx (~90% NO) produced from diesel engines are harmful
for the human health, where the catalytic transformation of NOx into
innocuous N2 is desired, 4NO + 4NH3 + O2 → 4N2 + 6H2O, a reaction known
as selective catalytic reduction (SCR). However, if both NO and NO2 are
present in a mixture, they can be converted using ammonia, NO + NO2 + 2NH3
→ 2N2 + 3H2O, a reaction known as fast SCR. Therefore, the catalysts should
have performance for transformation NO → NO2 and strong adsorption of
NO2 on the surfaces to be later transformed into N2 and H2O. This issues were
explored on supported gold monolayer, AuML/α-WC(0001), to study the
catalytic capability to transform NO into NO2 (X. Zhang, Chen, & Yang,
2019), since the Au(111) surface has catalytic activity NO → NO2 but NO2
desorbs from the surface due to the low adsorption energy, a drawback that
could be attacked by supporting an Au monolayer on WC. The authors studied
theoretically the AuML/α-WC(0001) system, contrasting with the pristine
system. Only the W-terminated layer of the α-WC(0001) system was taken as
a model. On the pristine WC, the NO adsorption energy is -3.28 eV, a strong
chemisorption that favors an elongation of the N―O bond from 1.16 Å to 1.43
Å which follows a dissociation NO → N + O, with a low energy barrier of
0.19 eV, where there is a large electron density transfer from WC to NO. On
the contrary, NO over AuML/α-WC(0001) has a weaker adsorption energy of -
0.57 eV and the electron density transfer Au → NO is negligible, limiting the
elongation of the N―O bond, hence, NO is no dissociated on AuML/α-
WC(0001), indeed, the dissociation of the N―O bond has a high barrier of
2.68 eV. The adsorption energy of NO2 (0.99 eV) is stronger than NO on
AuML/α-WC(0001), while the desorption rate of NO and NO2 from the surface
at 300 K is 0.2×104 and 0.2×10-5, respectively, which indicates that once NO2
is formed on AuML/α-WC(0001), it remains on the surface instead of leaving
it, favoring further reactions to convert NO2 into N2 via SCR reaction. A
scheme of the reaction pathway for the formation of NO2 from NO is shown
in Figure 15.
The ammonia is a promising material itself as a COx-free hydrogen
source, hence, the understanding of NH3 binding and decomposition is
important for a rational design of catalysts. The catalytic activity of Ru is high,
Complimentary Copy
but the use of cheap materials like Nickel lead to alternative materials, but the
energies to break the first N―H bond on is 0.26 eV higher than the NH3
adsorption energy, an indication that NH3 would desorb instead to decompose
on the Ni(111) surface, an issue which is overcome by using Ni/Pt(111) (Shen
& Cao, 2016). However, the use of Pt as support is expensive, hence, the use
of WC as support of Ni (Ni/WC) provides a good alternative, since WC has a
Pt-like behavior. For these systems, the W-termination of the α-WC(0001)
surface was used. Indeed, the first N―H bond scission on NiML/α-WC(0001)
has an energy barrier of only 0.49 eV, a lower value of 1.11 eV seen on
Ni(111) and even on Ni/Pt(111) (0.67 eV). However, the N recombination to
produce N2 is limited on NiML/α-WC(0001) due to the high energy barrier of
2.64 eV, as compared to the barriers of 1.86 eV and 1.73 eV on Ni(111) and
Ni/Pt(111), respectively; see a scheme of the reaction pathway in Figure 14.
In all these systems, the high energy barriers indicates that the N2 production
is carried out at high temperatures, limiting the use of these materials as
practical catalysts.
Figure 14. Scheme of the most feasible reaction pathways for a) HCOOH
decomposition on PtML/α-WC(0001), b) NO → NO2 oxidation on AuML/α-WC(0001),
c) NH3 decomposition on NiML/α-WC(0001). The metal ML is represented as a
vertical line to connect adsorbate-surface.
Complimentary Copy
Hydrogen Adsorption and Dissociation over Pt/WC

Hydrogen is present in several systems in heterogeneous catalysis. Indeed,
many of the industrial processes involve in some part of the process the
interaction with hydrogen to produce fuels and commodities. Therefore, the
study of H2 dissociation (H2 → 2H) and atomic H behavior on surfaces is
mandatory to improve the catalyst design by understanding the details at the
atomic level. Though the interaction of hydrogen with WC and M/WC, the
fundamental understanding at the atomic level is scarce, with a few and recent
reports for the PtML/α-WC(0001) system and comparted to Pt(111) as the
reference catalyst for H2 dissociation in platinum-based systems.
Koverga et al. studied theoretically the location of Pt monolayer on both
C- and W-terminations (Koverga, Flórez, Jimenez-Orozco, et al., 2021a), an
interesting fundamental study which goes beyond the use of only W-
termination in most of the traditional reports in the field, including also
modelling of several hydrogen surface coverage regimes (ΘH from 1/8 ML to
1 ML), and H2 dissociation kinetics at different temperatures (Koverga,
Flórez, Jimenez-Orozco, et al., 2021b). The authors found the the PtML/α-
WC(0001) with C-termination of the carbide system has a Pt-like behavior at
medium and high hydrogen surface coverage values. Indeed, the energy
barrier for H2 dissociation on PtML/α-WC(0001)-C at medium and high
coverage of H-adatoms was 0.13 eV and 0.09 eV, respectively, a competitive
barriers to that seen on Pt(111) (0.06 eV and 0.12 eV, respectively). The
reaction rate for H2 dissociation at high ΘH and at 298 K on PtML/α-WC(0001)-
C was 1.52x1011s-1, while on Pt(111) was 2.59x1010 s-1, which indicates that
the performance of Pt/WC is better than the classical Pt(111) surface. The
temperature rising from 298 K up to 1200 K at high ΘH implies a linear-like
increase of seven times the reaction rate for H2 dissociation on PtML/α-
WC(0001)-C, while the increase of rate on Pt(111) was negligible. These
results put PtML/α-WC(0001)-C under the spotlight as an potential and cheap
alternative material to the expensive bulk platinum for hydrogen-related
reactions. On the other hand, a gold monolayer over tungsten carbide, AuML/α-
WC(0001) with W-termination, was analyzed for H2 dissociation and
compared the results with pristine Au(111) and Ni(111), with respective
energy barrier of 0.53 eV, 0.98 eV, and 0.08 eV (Y. Zhang & Yang, 2019).
The purpose of using nickel is to focus on materials sulfur-tolerant in fuel-
related research, particularly on Solid Oxide Fuel Cells (SOFCs) systems,
where the reference system is the Nickel/Yttria-stabilized zirconia (Ni/YSZ).
Though the barrier on AuML/α-WC(0001) is lower than on Au(111), it does
not compete with Ni(111). Hence, a strategy is doping the Au monolayer with
Complimentary Copy
a single Pt atom (Pt-d); indeed, the barrier of this AuMLPt-d/α-WC(0001) was

0.10 eV, similar to that seen on Ni(111). The introduction of sulfur (H2S) to
the system implies a high adsorption energy (5.24 eV) on Ni(111), which
decreased to 3.69 eV and 3.98 eV on Au(111), and AuML/α-WC(0001),
respectively. The impact of H2S and H2 partial pressures and the temperature
on the chemical processes was explored by the phase diagram of Ni(111) and
compared to that AuMLPt-d/α-WC(0001) and even contrasting with another
noble metals, i.e., Pt(111) and Rh(211). The results indicate that at typical
operation conditions of SOFCs (923 to 1073 K), an amount of 100 ppm of H2S
poisons the Pt(111) surface, while Rh(211) is poisoned with only 0.01 ppm.
The Ni(111) surface poisons with concentrations between 1 to 100 ppm.
However, the AuMLPt-d/α-WC(0001) surface is not poisoned at any
concentration of H2S, i.e., it is sulfur-free, indicating the remarkable potential
of AuMLPt-d/α-WC(0001) as an alternative material to those of bulk platinoids
and even to Ni/YSZ, with the advantage to be sulfur-tolerant in a wide range
of pressures and temperatures.
Hydroconversion of Small Hydrocarbons

Small hydrocarbons like acetylene (C2H2), ethylene (C2H4), and ethane (C2H6)
are useful probe molecules to analyze alkynes, olefins, and alkanes,
respectively. The hydroconversion from C2H2 to C2H6 also involves reactions
with a particular focus and interests. The hydrogenation from acetylene to
ethylene (C2H2 + H2 → C2H4) and avoiding C2H6 formation is known as
acetylene selective hydrogenation. On the other hand, the hydrogenation from
ethylene to ethane (C2H4 + H2 → C2H6) is useful to understand the
hydrogenation of olefins.
A recent study focused on the capability of PtML/α-WC(0001) with both
W- and C-terminations for acetylene selective hydrogenation (Jimenez-
Orozco et al., 2023). The authors found that the W-termination of the carbide
surface with supported Pt, PtML/α-WC(0001)-W, has the capability to
hydrogenate acetylene to ethylene with a reaction energy of -0.44 eV, an
improved energy compared to Pt(111) (-0.15 eV), see Figure 15. The
advantage of of PtML/α-WC(0001)-W is that any further reactions are not
feasible based on positive reaction energy values, while on Pt(111) the C2H4
is hydroconverted into C2H5 (-0.49 eV) and C2H6 (-0.55 eV), i.e., does not
apply for selective hydrogenation reaction. A scheme of the reactions studied
in hydrogenation of small hydrocarbons is shown in Figure 15. The authors
contrasted PtML/α-WC(0001)-W with pristine Pt(111) due to the Pt monolayer
deposition on tungsten carbide, but the Pd(111) reference system is not
Complimentary Copy
explored yet theoretically on PdML/α-WC(0001). The presence of ethylidyne

(CCH3) is related to surface poisoning due to the strong adsorption energies
on Pt-based systems (usually above 5 eV). The formation of CCH3 is feasible
on Pt(111) from C2H2 (-0.41 eV) and from C2H4 (-0.40 eV), but they are not
feasible on PtML/α-WC(0001)-W with respective energies of 0.28 eV and 0.71
eV. Once CCH3 is on the Pt(111) surface, it cannot be hydroconverted into
other species like C2H2, C2H4, C2H5 or C2H6. Hence, Pt(111) is poisoned by
the presence of ethylidyne, but the PtML/α-WC(0001)-W is not poisoned,
opening a window to explore a cheap new material for acetylene selective
hydrogenation. Once C2H4 is formed on the PtML/α-WC(0001)-W surface, the
authors predicted the desorption rate of ethylene at several temperature
conditions, from 340 K to 640 K, providing a theoretical bridge to further
experimental studies. Regarding the potential in hydrogenation of olefins,
neither PtML/α-WC(0001) nor bare α-WC(0001) surface are good candidates,
based in the non-feasibility energetics for ethylene hydrogenation into ethyl
intermediate (C2H4 + H2 → C2H5 + H) and from ethyl into ethane (C2H5 + H
→ C2H6), see Figure 15, an opposite behavior than that seen on Pt(111),
Pd(111) and other surfaces of platinoids (Heard, Hu, Skoglundh, Creaser, &
Grönbeck, 2016).
Figure 15. Reaction schemes for acetylene (C2H2) hydrogenation into ethane (C2H6)
on PtML/α-WC(0001)-W. a) scheme of initial adsorbates on the surface, b)
hydrogenation reactions, c) ethylidyne (CCH3) from acetylene, d) ethylidyne from
ethylene, e) conversion of ethylidyne into other hydrocarbons. Reaction energies in
eV unit. Values for Pt(111) in italics and non-bolded.
Complimentary Copy
Tungsten Carbides as Support of Metal Clusters

The formation, characterization, and application of transition metal-made
clusters is common in several catalytic systems during the last two decades.
Nonetheless, the use of WC as support of metal clusters is relatively new and
some theoretical works have explored the first steps for the building of models,
properties and applications of cluster/α-WC(0001) systems.
The α-WC(0001) surface was used as support of the Ag3Pd cluster, putting
Ag3Pd/α-WC(0001) as an alternative of PtML/α-WC(0001) in proton exchange
membrane fuel cell (PEMFC), since on PtML/α-WC(0001) some species can
be formed like CO and carboxyl intermediates affecting the performance of
the catalyst being poisoned by these kind of species (Y. Zhao et al., 2020). The
motivation is to use the cluster Ag3Pd to also avoid particle agglomeration on
the surface, together with an improved catalytic performance, where silver-
palladium bimetallics has a catalytic activity for CO oxidation to CO2 to avoid
catalysts’ poisoning. The use of Ag3Pd was inspired in part by the
experimental work of (Ham et al., 2012) with Pd3Au/WC for a similar system.
Nonetheless, the choice of Ag3Pd is not completely understood. It is worth to
highlight that some authors have explored a detailed theoretical search of
geometries of bimetallic clusters and metal carbides, even using stochastic
techniques (Alvarez-Garcia, Flórez, Moreno, & Jimenez-Orozco, 2020;
Jimenez-Orozco et al., 2022); nonetheless, the implementation of these
methodologies to metal clusters and their further support is recent, which
deserves further developments (Gorey et al., 2020; Ha, Baxter, Cass,
Anderson, & Alexandrova, 2017). With these considerations in mind, the
results of the authors for Ag3Pd/α-WC(0001) are interesting, which were
compared to a system with a supported silver monolayer, AgML/α-WC(0001).
The adsorption energy of CO on Ag3Pd/α-WC(0001) was -1.50 eV, while on
AgML/α-WC(0001) was -0.78 eV. For the case of CO2, the respective
adsorption energies are similar on both systems, -0.28 eV and -0.24 eV.
Beyond adsorption energy, the reaction pathways for O2 dissociation and CO
oxidation to CO2 were explored. For the O2 dissociation, the energy barrier
was 1.18 eV and 1.09 eV on Ag3Pd/α-WC(0001) and AgML/α-
WC(0001),respectively. The oxidation of CO to CO2 has three steps: i) CO +
O2 → OOCO, ii) OOCO → O + CO2, iii) O + CO → CO2. For the first step,
CO + O2 → OOCO, the respective barriers are 0.52 eV and 0.27 eV, being
lower on the system with a silver monolayer. The second step also shows a
lower barrier on AgML (0.19 eV) than on Ag3Pd (0.28 eV), however, the third
step shows a similar barrier (0.43 eV and 0.48 eV). The results indicate that
the use of a Ag3Pd cluster has a similar catalytic activity that a catalyst of a
Complimentary Copy
silver monolayer, proposing an alternative material with lower atomic

economy.
The location of a cluster of copper, Cu4, over both C- and W-terminations
of α-WC(0001) was reported and compared to a CuML/α-WC(0001) for the
hydrogen evolution reaction (Koverga, Flórez, & Rodriguez, 2021). The use
of monolayers and clusters provides a limiting case of metals supported over
tungsten carbides. However, intermediate bimetallic systems have been
developed. The supported Cu-Au alloy monolayer, MM’ML/α-WC(0001), was
explored for electrocatalytic applications (Chang, Zhang, & Yang, 2021). The
reader is referred to the section below Applications in electrocatalysis for
more details. On the other hand, (S.-Y. Wu & Ho, 2012) reported the use of
WC-Co alloy for the CO2 adsorption and hydrogenation. The authors used the
W-termination of α-WC(0001) to change W by Co atoms in different layers
of the slab, i.e., the WC was not considered strictly as support as well, but they
named the amount of Co atoms in the system in terms of coverage, since in
the topmost layer of the slab the extent of the Co atoms varies with metal
substitutions. The Electron Localization Function (ELF) was used to
investigate the effect of substituting W by Co atoms. An increase of Co
coverage to 0.50 ML yields to an energy barrier of 0.57 eV, a lower value than
1.15 eV and 0.78 eV obtained at other coverage of Co atoms.
The reports of α-WC(0001) as support of clusters is scarce, even for
supporting metal atoms instead of clusters; in these cases, the W-termination
is used instead of C-termination (Tu et al., 2019). Though interfaces like
Cu(111)/α-WC(0001) are studied recently (Y. Fang et al., 2022), their
application in catalysis is not performed yet. However, there is a new topic of
interest in catalysis for the use of transition metal carbides as support of metal
clusters, beyond tungsten carbides. Recently, Prats et al. performed a
comprehensive theoretical study to explore the capabilities of several
monocarbides (TiC, ZrC, HfC, VC, NbC, TaC, MoC and WC) to support
monometallic clusters (Rh, Pd, Pt, Au, Co, Ni and Cu) towards CO2 and CH4
conversion (Prats & Stamatakis, 2023); in these systems, the authors used the
cubic γ-WC, particularly the (001) surface to compare with the other
monocarbides, which share a similar rock salt-like structure. These systems
were inspired in part on the report of (López et al., 2018) who studied the use
of TiC(001) as support of metals like Cr, Hf, Mo, Nb, Ta, V, W, and Zr, for
CO2 capture and activation, complemented by studying TiC(001) as support
of atoms like Mg, Ca, Sr., Al, Ga, In, Si, Sn, Pd, Pt, Rh, Ir, La, and Ce, for the
same CO2 system (López, Viñes, Nolan, & Illas, 2020). The study of metals
over metal carbides has a focus on the fundamental understanding, however,
Complimentary Copy
going into clusters provides a closer approach to the experiment since the
cluster size systems can be achieved experimentally (Cong Liu et al., 2015)
(Yang et al., 2017). The models for clusters/MC (M = Ti, Zr, Hf, V, Nb, Ta,
Mo, and W) were built and carefully characterized recently (Prats &
Stamatakis, 2022), providing a theoretical basis to address several catalytic
applications of these kind of systems. The clusters/MC systems are interesting
due to the modulation of the properties according to the desired application,
since the electronic properties of the system changes, which yields to a
plethora of potential applications in several chemical systems. In other words,
the clusters/MC systems have a huge potential in heterogeneous catalysis as
low-cost materials, the first steps are being performed, hence a road in this
field is yet to be explored from experiment and theory.
Applications in Electrocatalysis
The use of tungsten carbides in the field of electrocatalysis deserves a

standalone section due to a particular connection experiment-theory in the
fundamental understanding of several phenomena. Therefore, this section
includes details regarding synthesis of tungsten and how the modulation of
experimental conditions affects the electrocatalytic performance of WC-based
systems. This section includes starts by a compact outlook regarding the
fundamentals of the hydrogen evolution reaction (HER), covering
experimental criteria, followed by synthesis methods of tungsten carbides to
connect with the catalytic activity of pristine WC as active phase and support
towards HER. Finally, WC supported on several materials is included.
Fundamental Aspects of Hydrogen Evolution Reaction
With constantly increasing energy demand the negative effect of traditional

fuels on environment has been growing over the years and came into focus of
world attention (W. F. Lamb et al., 2021; Magazzino, Toma, Fusco, Valente,
& Petrosillo, 2022; Rehman et al., 2022; Strielkowski, Civín, Tarkhanova,
Tvaronavičienė, & Petrenko, 2021; van Asselt, 2021; Yuan, Su, Umar, Shao,
& LOBONŢ, 2022). Coal, oil, and gas are foundation stones of modern
civilization and also the largest contributors to greenhouse gas emissions,
responsible for more than three-fourths of them (SEI, IISD, ODI, E3G, &
Complimentary Copy
UNEP, 2020). Therefore, a significant effort has been made to develop

renewable energy conversion systems, such as hydroelectric, wind- and solar-
powered. Despite great potential offered by their large-scale implementation,
intermittent nature of these solutions results in low average energy delivery
efficiency. Specifically, periods of high energy output are followed by
stretches of time when no energy is produced. A promising strategy to tackle
this problem is to employ an energy carrier to store a surplus of generated
energy and send it back to the grid when no energy is produced.
In this regard, several types of energy storage systems can be employed:
mechanical, thermal, electrochemical and chemical. Each approach has its
advantages and disadvantages related to its potential for scalability, energy
density, capacity and economic viability. Compared to other methods
chemical energy storage has the largest potential for large-scale energy
storage, and hydrogen is a very perspective energy carrier candidate because
of its abundancy in the nature and highest energy density among chemical
fuels (Møller, Jensen, Akiba, & Li, 2017). The majority of hydrogen nowadays
is obtained from a water-gas shift reaction with CO2 as a by-product, thus,
urging a search for more “green” production strategies.
Electrochemical water splitting into hydrogen and oxygen can be
considered as the most ecologically friendly way to produce hydrogen. This
approach to hydrogen production does not involve CO2 on any of its stages
and requires only water and electricity. Also, hydrogen obtained from water
splitting is characterized by high degree of chemical purity and can be directly
used for energy storage without undergoing complex purification procedures.
A significant advantage of this method of hydrogen synthesis is its zero
contribution to emission of carbonaceous species, which could allow to
significantly reduce the anthropological environmental impact.
In a water electrolysis setup, an external current is applied to overcome
the energy barrier of the reaction (237 kJ/mol) and at the cathode hydrogen
evolution reaction (HER) takes place while at the anode oxygen is produced
via oxygen evolution reaction. Despite this process being straightforward, the
large-scale application of water splitting for H2 production is presently not
available.
The high energy consumption on the electrode surface is main reason
hindering wide implementation of electrochemical water splitting for
hydrogen production, which can be resolved by employing an efficient
catalyst to improve the energy conversion efficiency. Presently, materials
based on noble metals remain unrivalled as water splitting catalysts in both
acidic and alkaline media (Esposito et al., 2012; Greeley et al., 2006;
Complimentary Copy
Michalsky et al., 2014). However, due to their scarcity and high pricing, an
ongoing search for alternative, highly active and cost-effective catalysts
became one of the top priorities for chemical and material science research.
An additional requirement for the prospective alternative catalytic materials is
that they must be characterized by a high stability in typical working
conditions of HER, which further increases the cost of these technologies.
Another possible approach to solving this problem is to employ a cheaper
carrier material to disperse noble metal and reduce its loading without
sacrificing significantly its catalytic activity. In this latter case the stability of
the support in the working conditions is required as well as closeness of its
electronic structure to that of precious metal catalyst.
At the first glance, transition metal carbides and, specifically, tungsten
carbide fulfil most of the requirements, listed above, both as an economic
alternative to precious metal catalysts and their support. Numerous studies
have been dedicated to investigating HER activity of tungsten carbide and
materials, based on it. The absolute majority, however, used experimental
approach, while purely theoretical studies are rather scarce, especially in the
last five years. Therefore, this review primarily focuses on experimental works
to give as complete idea of the state of art as possible. Thus, before discussing
catalytic properties of materials, based on tungsten carbide, toward HER, its
mechanism is briefly reviewed. Also, the most common experimental
approaches to evaluating catalytic performance of materials is discussed, i.e.,
what measurable parameters allow to decide whether a potential catalyst is
“good” or “bad” for hydrogen production from water splitting.
Overview of Hydrogen Evolution Mechanism

Hydrogen evolution reaction (HER) is considered one of the simplest and most
studied reactions in electrochemistry. Generally, HER is a multiple step
electrochemical process taking place at the electrode-electrolyte interface
either in acidic or alkaline media. In the former case hydrogen is produced
through reduction of protons, present in the solution, and in latter – through
water reduction.
Figure 16 demonstrates possible steps HER can take in acidic and alkaline
media. In acidic media hydrogen evolution reaction starts with the Volmer
step, during which proton adsorbs on the surface of the catalyst. After this one
possibility is that another H+ adsorbs on the catalyst’s surface via the Volmer
step and two H atoms combine on the surface, forming H2 molecule, which,
consequently, desorbs (Tafel step). Alternatively, during the Heyrovsky step
Complimentary Copy
adsorbed H atom interacts with a proton and an electron to form hydrogen

molecule.
Figure 16. Schematic representation of HER fundamental steps in acidic (upper

panel) and alkaline (bottom panel) media.
Similarly to the mechanism in acidic media, HER at high pH values also

starts with the Volmer step, but here H2O molecules are the reacting species.
After water adsorption and dissociation molecular hydrogen is formed through
interaction of atomic hydrogen present on the catalyst’s surface with another
adsorbed hydrogen atom via Tafel step, or with another water molecule
following the Heyrovsky route.
Depending on which elementary step is rate-determining (RDS), the HER
can have four different mechanisms: Volmer (RDS) – Tafel, Volmer – Tafel
(RDS), Volmer (RDS) – Heyrovsky and Volmer – Heyrovsky (RDS).
Generally, to determine the predominant mechanism by which HER is carried
out, the Tafel slope value from the HER polarization curve is evaluated, which
has a specific value in each above-listed case (Tian, Zhao, & Sheng, 2019).
Experimental Criteria for Catalytic Activity toward HER

Water splitting into hydrogen and oxygen is an uphill reaction with ΔG > 0
that also requires to overcome a kinetic barrier. Catalysts are crucial for
Complimentary Copy
lowering this barrier (Figure 17), and, therefore, their performance must be
quantified to make an informed decision whether a given material is better or
worse than a selected reference.
Figure 17. Role of a catalyst in reducing activation energy for water splitting. Solid
black line represents energy profile of the reaction without catalyst, while dashed line
corresponds to the catalyst-assisted process.
In general, a catalyst is characterized by its activity and stability. In the

context of electrocatalysts for HER, the most popular choices for measuring
activity are overpotential and exchange current density; for stability – changes
evolution of the overpotential or current with time.
Catalytic Activity Criteria: Overpotential and Exchange

Current Density
By definition, the overpotential, η, is the excess voltage needed to reach a fixed
current density. The thermodynamic potential for electrochemical water
splitting reaction at normal conditions is 1.23 V. Since a kinetic barrier (Figure
17) needs to be overcome, a higher potential is required for water electrolysis.
Thus, overpotential mainly comes from the necessity to overcome activation
barriers and is a very important descriptor to evaluate the activity of the
electrocatalysts. Typically, the overpotential value required to reach the
current density of 10 mA cm−2, η10, is used to compare the activities among
different catalysts. In the context of activity toward HER materials with lower
overpotential have higher electrocatalytic activity (Park et al., 2022).
Complimentary Copy
In some studies an onset overpotential, η0, is used, which is the

overpotential at which the reaction starts. However, often, it is difficult to
define experimentally the exact moment of the electrochemical process
beginning, therefore, it is a common practice to refer to the onset overpotential
as to overpotential at which current density of 1 mA/cm2 is achieved. Similarly
to η10, the lower is its value the more active an electrocatalyst is considered.
An opposite approach is to measure current density at a selected overpotential
and the higher is the measured current density the better is catalyst’s activity.
Plotting overpotential versus logarithm of current density, log j, a Tafel
plot can be obtained. Linear region of this plot is known as Tafel slope and it
can be expressed by the equation:
  a  b log j (3)
Here η is overpotential, b is the Tafel slope and j is the current density.

Exchange current density of the reaction, j0, is obtained at zero
overpotential and describes the intrinsic charge transfer under equilibrium
conditions. A larger j0 value implies higher electron transfer rate and better
kinetic performance (lower reaction barrier) of the catalyst.
To summarize, the optimal HER catalysts must be characterized by a low
onset overpotential, or overpotential required to reach certain reference current
density and high exchange current density values.
Experimental Evaluation of Catalyst’s Stability in Working Conditions

While a potential catalyst may demonstrate a great activity toward HER, its
low stability in working media will prevent its application in practical systems.
Therefore, catalyst’s ability to retain its activity in working conditions over
extensive stretches of time is an important characteristic which must be
evaluated in a reliable and reproducible manner.
Typically, a catalyst’s durability can be evaluated by constantly
monitoring the changes in overpotential at a certain current density with time
(chronopotentiometry), or, conversely, in the current density at the applied
constant overpotential (chronoamperometry). In these cases minimal changes
in the monitored values correspond to a better stability of the catalyst.
Another method is cyclic voltammetry that compares the current density
before and after the stability test during which the potential is cycled in the
selected range. Typically, at least 1000 cycles are required to draw the
conclusion about the catalyst’s stability.
Complimentary Copy
A variation of this method is an in situ characterization of the catalyst

before potential cycling and after and comparing the results, often allowing to
estimate a stability of a specific component of a catalyst in composite
materials. An example is shown in Figure 18 where X-ray adsorption
spectroscopy in the near-edge region (XANES) have been performed for
molybdenum carbide doped with iron and cobalt in a mildly alkaline solution
(pH=9). The measurements were taken before and immediately after 8 h of
continuous cycling within the working range of potentials (Koverga, Gómez-
Marín, Dorkis, Flórez, & Ticianelli, 2020). The conclusion can be made here
that since Fe XANES spectra for Mo2C modified with iron did not change
after the stability test, this material is stable in working conditions of HER. On
contrary, changes in XANES spectra for cobalt in the Co-modified material
demonstrated its lesser durability.
Figure 18. XANES spectra for Fe-Mo2C (a) and Co-Mo2C (b) at pH=9 before
(dashed line) and after (grey lines) cycling procedure (Based on data from (Koverga
et al., 2020)).
Synthesis of Tungsten Carbide
For a systematic and efficient experimental study of any given material, a

reliable and reproducible protocol to obtain stable structure is required. In case
of electrocatalysts additional prerequisites are large specific area and
sufficient active site exposure. Therefore, an overview of synthesis strategies
for tungsten carbide is presented below to draw a comprehensive picture of
the field.
Tungsten carbides mainly exist in two phases: WC with hexagonal
structure and W2C, which has several structural modifications (A. S. Kurlov
Complimentary Copy
& Gusev, 2006). Here, the main focus is given to WC because of its higher
chemical and thermodynamical stability.
The direct solid-state reaction of tungsten and carbon requires extended
time and very high temperature of more than 1400oC (Hatano et al., 2002;
Luković et al., 2015; Jianfeng Zhang, Hassan Saeed, & Li, 2018). Its
additional disadvantage is that the final product has uncontrollable particle
size and non-homogeneous carburization. Thus, this method is not very
popular and more viable alternatives have been sought, such as carbothermal
reduction, mechanical alloying and carbothermal reduction. It must be noted
here that these methods, in general, refer to preparation of the synthesis
precursor, containing source compounds of tungsten and carbon. Annealing at
high temperatures is an essential stage for all methods of WC obtention.
Typically, after synthesis the purity of obtained carbide phase is verified by
comparing its XRD patterns with the reference one (Figure 19). Below each
of these methods is reviewed in detail.
Figure 19. XRD pattern for WC (PDF 65-4539).
Carbothermal Reduction
Carbothermal reduction is the solid-solid reaction that typically uses tungsten-
containing compounds as precursors that react with a carbon source, such as
carbon black, coke, and graphite. Carbonaceous gases (Z.-Y. Chen et al.,
Complimentary Copy
2017) can be used as reducing agent as well in solid-gas carbothermal

reduction. In both cases the process takes place at high temperatures that are
still lower than temperatures required for the direct W and C reaction.
For the solid-solid carbothermal reduction, one of the most popular routes
is to employ tungsten oxides as a source material. In this regard, Wu et al.
successfully prepared WC nanopowders using microparticles of WO2.9 and
WO3 in the form of nanoparticles, nanorods and microparticles as tungsten
source and carbon black powder – as reducing agent and carbon source (H.
Wu et al., 2020). In each case tungsten oxide and carbon black were
mechanically mixed and carbothermal reduction has was carried out in
vacuum hot-pressing sintering furnace. Specifically, each prepared sample
was heated gradually to the temperature of carburization in the range between
850oC and 1080oC, depending on the tungsten precursor and, consequently,
treated isothermally for 3 hours. Phase composition was controlled by X-ray
diffraction analysis and synthetized products were further characterized using
scanning electron microscopy (SEM) and energy-dispersive X-ray
spectroscopy (EDS). The authors demonstrated that the WO3 micro-particles
are better precursor than other considered materials, since obtained WC
particles were smaller, had less aggregates and were more uniform than those,
obtained with other W-containing materials.
Similar method was employed by (K.-F. Wang, Sun, Wu, & Zhang, 2019)
to obtain ultrafine high purity WC phase. The precursor was prepared by
thoroughly mixing tungsten trioxide, WO3 with carbon black at molar ratios
of 2.7, 2.9, 3.1, 3.5 and 3.7. In the proposed two-stage method precursor
powder were first placed in the horizontal tube furnace and the sample was
heated to the target temperature of 1100oC at the rate of 5oC/min and held for
1h under constant flow of argon. At this temperature all the oxygen in the
oxide is removed and a mixture of W, W2C and WC is obtained. After bringing
the mixture to room temperature, the carbon content of the as-prepared sample
was evaluated, and carbon black was mixed with the obtained sample in the
quantity according to the difference between the carbon content of the as-
prepared powder and WC. This mixture was put into the constant temperature
zone of the furnace and brought to 1200oC at the rate of 5oC/min and held for
6 h to conduct the carburization process under the constant flow of hydrogen.
The obtained products were confirmed by X-ray diffraction analysis and their
morphology – by field-emission SEM and transmission electron microscopy
(TEM). A significant advantage of this two-step approach to WC synthesis is
that it allowed to reduce the size of WC particles by employing high C/WO3
molar ratio at the first step. Thus, although the carburization temperature was
Complimentary Copy
slightly higher than in the study of (H. Wu et al., 2020), the obtained single-
phase WC had a smaller particle size of about 200 nm.
Overall, the solid-solid carbothermal reduction is a perspective method of
WC synthesis, because it can be scaled to industrial applications, and it offers
a way to obtain product with controlled phase distribution and size of the
particles. The homogenization of the precursor mixture at the preparation
phase allows a more uniform carburization of tungsten precursor, compared to
direct solid-state reaction of tungsten and carbon and at lower temperatures.
The sintering of the final product, however, still presents a problem for a wider
implementation of this method, since the resulting phase often suffers a
reduced surface area, leading to a lower number of active sites on the catalyst.
The solid-gas synthesis route allows to somewhat mitigate the
disadvantages of the solid-solid approach by employing carbon-containing
gases as reducing agent and source of carbon. This allows to conduct the
synthesis at lower reaction temperatures, and, consequently, reduce the
sintering of the WC product. As the result the obtained WC is characterized
by better dispersion than that obtained from solid-solid reaction and smaller
size of the particles.
For instance, tungsten (IV) oxide, WO2, was successfully used by Dang,
Wu and Lv to obtain WC with CO as the reduction and carbonization agent
(Dang, Wu, Lv, & Lv, 2018). A WO2 sample was heated at a rate of 10oC/min
to a target temperature of either 813oC, 1102oC or 1179oC where it was held
for 30 min, 175 min and 222 min, resp. and a constant CO flow. As evidenced
from XRD characterization, at the lowest studied temperature of 813oC only
trace amounts of WC were observed, while at the highest 1179oC the oxide
was reduced to metallic tungsten. The synthesis conducted at 1102oC,
however, resulted in almost complete reduction of WO2 to WC with trace
amounts of W2C. This study clearly demonstrated the complexity of the
synthesis process of tungsten carbide and the impact of the reaction conditions
on the composition of the resulting phase.
Tungsten trioxide remains a popular choice for solid-gas WC synthesis
routes as well. Bulk tungsten carbide catalysis was successfully obtained using
WO3 as tungsten source and C2H6/H2 and C2H4/H2 carburizing mixtures by
(Decker, Löfberg, Bastin, & Frennet, 1997). Specifically, samples of WO3
powder were placed in a quartz flow reactor and carburizing mixtures in argon
were applied. For C2H6/H2 1/9, 1/4 and 1/1 mixtures (partial pressure ratio)
were considered while for C2H4/H2 mixture only 1/4 and 1/1 proportions were
used. The temperature was increasing at the rate of 360oC/h from room
temperature to 900oC, 850oC, and 800oC for C2H6/H2 1/9, 1/4 and 1/1 mixtures
Complimentary Copy
resp., and to 900oC and 950oC for C2H4/H2 1/4 and 1/1 mixtures resp. The
obtained results pointed to the fact that in C2H6/H2 mixtures a formation of
C2H4 is seen with increasing temperature due to dehydrogenation of ethylene
and ethane is the real carburizing agent. The formed WC phase in all cases has
a large excess of carbon deposited on it, which can be removed by means of
further postprocessing of the product. Another strategy to avoid the formation
of the excessive carbon is to employ a different carburizing agent.
In this regard, methane is one of the most popular carburizing agents due
to the lower amount of excess carbon deposited on the surface of the carbide
during the carburization compared to other hydrocarbons. Thus, a carburizing
CH4/H2 mixture was employed by Löfberg et al. to produce powder tungsten
carbide from tungsten trioxide (Löfberg, Frennet, Leclercq, Leclercq, &
Giraudon, 2000). According to their protocol WO3 powder was placed into a
flow microreactor and treated with mixtures of hydrogen and methane. At the
same time temperature programmed reaction (TPR) analysis has been
performed by increasing the temperature at the rate of 1oC/min. The gas phase
composition at the outlet of the reactor was controlled with a quadrupole mass
spectrometer. Using this method, the carburization of the precursor and
formation of WC was achieved in the temperature range between 627 and 950
K, which is noticeably lower than the carburization temperature for solid-solid
synthesis.
Synthesis via a temperature-programmed carburization with
phosphotungstic acid, H3PW12O40, as precursor in the carburizing atmosphere
of CH4 has been conducted by Wu et al. using mesoporous silica materials as
hard templates (Z. Wu et al., 2009). The precursor was prepared by dissolving
phosphotungstic acid (PTA) in ethanol and infiltrated into the pore channels
of silica hard templates. The obtained PTA@silica composites were
decomposed and carburized in situ under CH4 flow, forming WC
nanocrystallites, which were stabilized into the ordered mesostructured by
introducing graphitic carbon. Analysis of the TPR profiles showed that the
silica-confined precursor held for 3h at 900oC converted to WC nanocrystals.
The product obtained this way was characterized by high content of deposited
carbon. This can be mitigated by employing a CH4/H2 mixture as carburizing
agent, which allows to conduct the synthesis at even lower temperature and
results in a smaller amount of carbon deposited on the final WC
nanocristallites product.
Despite the obvious advantages offered by the sold-gas route, a significant
drawback of this method is that the flammable gases used as
carburizing/reducing agents present safety hazard during synthesis. Also, the
Complimentary Copy
incomplete conversion is difficult to avoid as the uniform propagation of the

carburizing agent through the solid sample cannot be assured, reducing
structural control over carbide surface.
Hydrothermal Method
Another perspective approach to WC synthesis is hydrothermal method which
is based on crystallizing substances from high-temperature aqueous solutions
at high vapor pressures. Roughly speaking, during hydrothermal synthesis the
crystal growth takes place in an autoclave in which a precursor is supplied
along with water under a constant temperature gradient between the inlet and
outlet of the reactor chamber. At the hotter end the dissolution of precursor
takes place, which is then delivered to reaction zone, and, consequently, the
reaction product is crystallized at the cooler end. In the specific case of WC
synthesis, hydrothermal method implies preparation and homogenization of
the precursor components through dissolution of W- and C-containing
compounds in water. This stage is followed by drying/crystallization of the
obtained precursor, which later is brought to carburization temperature in a
controlled environment, such as furnace, or quartz flow reactor, if specific
gases are required to facilitate the reaction or passivate the product.
Using this approach Sagadevan, Das, Singh and Podder synthetized WC
nanoparticles (NPs) from ammonium metatungstate [(NH4)6
(H2W12O40)∙nH2O] as source of tungsten and corn starch (C27H48O20) as source
of carbon (Sagadevan, Das, Singh, & Podder, 2017). In the proposed synthesis
the precursor was obtained by dissolving ammonium metatungstate (AMT) in
hot deionized water and adding corn starch to the solution. The obtained
mixture was transferred to a Teflon-lined autoclave, which then was kept
sealed in a stainless-steel tank at temperature 200oC for 8 h. After the
autoclave was cooled to room temperature, the precursor solution was taken
out and diluted. Dry precursor was finally obtained by spray-drying the
solution with hot air being blown at 250oC. After that the dry precursor was
heated in a vacuum furnace at 980oC for 1h to obtain the target product, which
was characterized with powder XRD, SEM and TEM. The obtained phase was
confirmed to have hexagonal structure with the average grain size of the WC
NPs about 24 nm, which is almost 10 times smaller than particle size of WC
obtained by carbothermal methods, described above.
AMT was also used in the synthesis reported by d'Arbigny et al. who used
varying amounts of glucose as source of carbon (Bernard d’Arbigny,
Taillades, Rozière, Jones, & Marrony, 2011). According to the employed
protocol AMT was mixed with glucose and water and sealed in an autoclave
Complimentary Copy
for 12 h at 170oC. After that the precursor mixture was dried overnight and
70oC and transferred to a furnace where it was held at 900oC in Ar flow for
2h. The remaining free carbon was later removed by heat treatment of the
sample in hydrogen from 20oC to 900oC. Nonetheless, obtained WC
microspheres had a fraction of residual carbon. Thus, to optimize the synthesis
and the content of residual carbon in the final product, the initial AMT/glucose
molar ratio was modified from 0.01 to 0.1 while maintaining the glucose
concentration constant at 2M. The obtained product was confirmed to have
good electric conductivity that increased with temperature until reaching
150oC, surpassing the electric conductivity of carbon powder at 120oC.
In general, syntheses, based on employing the ATM mixed with carbon-
containing compounds in varying ratios and mixing/reaction conditions are
prevailing throughout the hydrothermal-based methods, which proved to be a
reliable and reproducible method of WC NP synthesis (Boopathy,
Govindasamy, Nazari, Wang, & Umapathy, 2019) (Tang, Wang, Wu, & Duan,
2015) (Y. Wang, Song, Maragou, Shen, & Tsiakaras, 2009) (Y. Wang, Song,
Shen, Guo, & Li, 2009) (Xiong et al., 2015).
However, other tungsten compounds found their use as well in WC
hydrothermal-based synthesis for electrocatalytic applications. In the report
by (Y. Yan et al., 2012). Tungsten trioxide, prepared from sodium tungstate
dihydrate and ammonium sulfate, was mixed with glucose at molar W/C ratio
of 0.078 in deionized water and stirred for 20 minutes. The mixture was
transferred to autoclave and heated for 8h at 180oC and carbon-coated WO3
nanorods were formed. This precursor was then placed in a furnace at 900oC
for 3 hours under a constant flow of Ar/H2 mixture. An XRD analysis of the
product demonstrated that WC phase was the main product with traces of
W2C.
A similar approach was used in another study where carbon-coated WC
was obtained from WO3 and hexane (Singla, Singh, & Pandey, 2015). For the
synthesis several samples consisting of tungsten trioxide, Mg, used as
reducing agent and hexane were added into stainless steel autoclave and kept
for 2h, 10 h and 15h at temperature of 600oC and for 10 h at 700oC and 800oC.
This approach was used to detect intermediate phases at each step of the
synthesis. After cooling to room temperature, the samples were collected and
washed in HCl to remove MgO, and consequently washed with distilled water
to remove the acid. After that the final products were dried in vacuum at
100oC. Characterization of the obtained phases using powder XRD revealed a
pathway from the reduction and carburization of WO3: WO3 → WO2.76 →
WO2.625 → WO2 → W → W2C → WC.
Complimentary Copy
A higher W3O8 oxide precursor combined with glucose was used in

another study to prepare WC (Vijayakumar et al., 2015). W3O8 was first
obtained by mixing 1:2 molar ratio of sodium tungstate dihydrate and
ammonium sulfate in deionized water. HCl was added to the mixture to adjust
its pH value to 2 and the solution was transferred to autoclave where the
reaction was maintained at 180oC for 8 h. The obtained tungsten oxide
precipitate was isolated by filtration, washed with water and ethanol and dried
at 60oC. The synthetized oxide was mixed with glucose at molar W/C ratio of
1:12.8, placed in deionized water and stirred for 20 m. The obtained mixture
was hydrothermally treated in an autoclave for 8h at 180oC to from carbon
coated W3O8 nanorods. The obtained C-W3O8 nanorods then were thermally
treated for 3h at 900oC under H2/Ar flow and WC nanorods were obtained. X-
ray powder diffraction confirmed formation of WC, however, a significant
amount of W2C phase was obtained as byproduct.
Overall, this method allows preparation of very small WC particles with
high surface area. It also allows to control particle geometry and morphology.
Because of dissolution stage during precursor preparation, the sources of
tungsten and carbon are well mixed and the carburization process, therefore,
is uniform. The carburization typically takes place at 900oC, which implies
that lower energy is required in the process.
Pure WC Activity Toward HER
Tungsten carbide initially drew the attention of the scientific community

because of its “platinum-like” behavior in surface catalysis (Levy & Boudart,
1973) which motivated its further studies as a potential catalyst for HER.
The majority of studies dedicated to HER activity of unmodified tungsten
carbide have been reported more than five years ago and the most common
conclusion made about WC performance as HER electrocatalyst in acidic
media is that it has rather average activity. For instance, nanoporous WC was
obtained by thermal annealing of the anodized W foil at 800 °C for 4 h using
CO as carburizing agent. The obtained phase was confirmed by XRD analysis
and further characterized with Scanning electron microscopy (SEM) and
Tunneling electron microscopy (TEM) methods (Kang et al., 2017). Its
electrochemical characterization in 0.5 M H2SO4 yielded an overpotential at
10 mA/cm2 (η10) of 187.1 mV while under the same conditions Pt was
characterized by η10=11.5 mV, which indicates a significantly better catalytic
activity of the platinum catalyst (~10 times). A similar overpotential (η10=-193
Complimentary Copy
mV) value for WC catalyst in 0.5 M H2SO4 was reported by (Han et al., 2018),
for WC nanoarrays obtained by carburization of tungsten trioxide at 850oC by
Camphora.
These observations agree with an earlier study where it was demonstrated
that in acidic media tungsten carbide, synthetized from WO3 via a
carburization process, although showing a good activity, was able to reach
only 31% of the activity of platinum (Harnisch, Sievers, & Schröder, 2009).
The maximum current densities measured for WC at overpotentials of 760 mV
and 300 mV were -118 mA/cm2 and 26 mA/cm2, while for Pt the
corresponding values were -226 mA/cm2 and -84 mA/cm2. Changing the pH
to neutral values reduced the performance of all materials and for an
overpotential of 300 mV, effective hydrogen evolution current densities for Pt
and WC were of −15.2 mA/cm2 and −8.8 mA/cm2, respectively. Thus, under
these conditions tungsten carbide is able to reach about 57% of the activity of
platinum. This increase can be associated with the fact that the kinetics of the
HER at neutral pH is less hindered on tungsten carbide surfaces than it is on
platinum, thus highlighting an importance of pH of the solution when
analyzing activities of potential catalysts, especially novel and non-metallic
materials.
Atomic hydrogen is the only HER intermediate directly interacting with
catalyst’s surface (Figure 16) and is often considered as activity descriptor
(Michalsky et al., 2014) (Nørskov et al., 2005) (Trasatti, 1972). This makes
sense from the point of view of Sabatier’s principle that states that optimally
a catalyst must bind reacting species strongly enough for reaction to take place
and weakly enough to release products of the reaction (Sabatier, 1920). Thus,
HER activity of WC being an intermediate between parent metal and Pt can
be seen as the result of atomic hydrogen decreasing in order W > WC > Pt.
Another factor affecting HER activity of WC could be its mixed-atom nature.
This implies existence of C- and W-domains on the catalyst’s surface with
active sites with very different properties, while active sites on a pure metal
catalyst are very similar and uniform (although, sometimes, geometry of the
surface can have an effect on the properties of the catalyst and needs to be
taken into account).
In general, using theoretical approach it is possible to analyze well-
defined C- and W-terminated surfaces, which have different chemical and
catalytic properties (Koverga et al., 2019) (Koverga, Flórez, & Rodriguez,
2021) (Koverga, Flórez, Jimenez-Orozco, et al., 2021a). In a practical system,
however, the total catalytic activity of the carbide will be defined by the
statistical distribution of C- and W-active sites on the catalyst’s surface.
Complimentary Copy
Returning to stability of atomic hydrogen as HER activity descriptor, on C-

terminated (0001) WC surface it is -3.92 eV, while on W-terminated one it
was calculated to be 0.4 eV weaker (Koverga et al., 2019), thus, suggesting
that metal-terminated carbide surface would be more active toward HER than
carbon-terminated.
In favor of this argument is the study (Hunt, Nimmanwudipong, &
Román-Leshkov, 2014), where a reliable and reproducible protocol was
reported for W-terminated WC nanoparticles (NPs) synthesis in the 1-4 nm
range. Briefly, tungsten oxide NPs encapsulated in silica nanospheres were
obtained, which then were subjected to carburization process in CH4/H2 gas
mixture. Then carbide NPs were obtained by dissolving the SiO2 shells and
were supported on highly dispersed carbon. Assessing catalytic properties of
the obtained material in 0.5M H2SO4 demonstrated that it showed good
stability in the working conditions. HER activity of WC supported on carbon
black was significantly better than that of commercial WC material since the
former required an overpotential that was lower by more than 100 mV than
the latter to drive 1 mA/cm2 of cathodic current (165 mV vs. 290 mV, resp.).
This improved activity can be attributed to elimination of the hindering effect
of the active sites belonging to C-termination and increasing the number of the
metal ones.
In contrast to the above mentioned studies, Huang et al. reported that WC
NPs, prepared by carbonization of tungsten foil, showed a remarkable
performance as HER catalyst (Huang, Hong, Li, Wang, & Liu, 2020). The
authors prepared tungsten carbide catalyst by a bottom-up method, where a
WO2 film grown on W foil was oxidized in vacuum, exposing large surface
area. This stage was later followed by carbonization of the sample in a flow of
CH4. The resulting tungsten carbide supported on tungsten (WC/W) was
confirmed by XRD analysis and showed a good catalytic activity toward HER
in both acidic and alkaline media, outperforming most of the WC-based
catalysts reported to the date. To reach a current density of 10 mA an
overpotential of 87 mV was required in 0.5 M H2SO4 and 68 mV – in 1 M
KOH. The authors attributed this to the fact that in the WC/W system WC
forms an efficient electrical contact with the electron collecting tungsten
substrate, thus, allowing barrierless electron transport and minimizing the
impact of contact resistance on the HER performance.
The value of η10=68 mV measured in alkaline media can be considered as
high, since the typical overpotentials at 10 mA/cm2 for tungsten carbide in
these conditions are about 150-250 mV (Y. Chen, Zheng, Yue, & Huang,
2020). It must be mentioned here that this poor WC activity at high pH can be
Complimentary Copy
a result of two factors. First, in an alkaline solution an additional energy barrier

has to be overcome because hydrogen evolution reaction requires H–O–H
bond scission prior to active hydrogen atoms adsorption on active sites of the
catalyst (see Figure 16). Second, WC surface poisoning by highly stable OH*
intermediates disables active sites, reducing overall activity. Additionally, in
alkaline media a gradual oxidation of metal sites into inactive but stable
tungsten oxides renders the catalyst inert with time.
Additionally, to these factors, atomic hydrogen stability is still an
important factor affecting HER activity in alkaline media, despite water being
the reacting species (see Figure 16). In an earlier study by (Michalsky et al.,
2014) tungsten carbide was synthetized via carburization of metal sheets by
carbonaceous gases in a tube furnace and composition of the phase was
confirmed using XRD, EDX and SEM. HER activity was evaluated in a one-
chamber voltammetry cell with Pt as counter electrode at pH 11.3. The
measured exchange current density (at equilibrium) for WC, log jo was -4.8
A/cm2 allowed to conclude that WC was more active toward HER than pure
tungsten, but less active than Pt-group materials. The authors explained this
trend of activities was from the point of view of atomic H stability on catalyst’s
surface as well, in agreement with the W > WC > Pt stability trend discussed
above.
Thus, from the overview of experimental studies of WC activity toward
HER it becomes evident that incorporating carbon into tungsten lattice is
favorable for the electrocatalytic activity of the resulting carbide. Compared
to metallic tungsten adsorption of atomic hydrogen is less stable on the latter,
facilitating removal of the product from the surface, even from more strongly-
binding C-sites. An additional factor promoting HER activity on a
fundamental level is a higher d-band electronic density of states at the Fermi
level, typically associated with introduction of carbon into the lattices of non-
noble metals (W.-F. Chen, Muckerman, & Fujita, 2013). Nonetheless, HER
activity of pure WC remains far from desirable and needs further
improvements for it to be considered as a viable alternative to noble-metal
catalysts. Therefore, an overview of possible strategies used to enhance
electrocatalytic properties of tungsten carbide for hydrogen production from
water is presented below.
Complimentary Copy
HER Activity of WC-Based Materials
Metal Adlayers Supported on Tungsten Carbide

Taking into account similarities of electronic properties of WC and Pt, the
most obvious way to improve catalytic activity of tungsten carbide toward
HER is to combine its low cost with high activity of platinum. Specifically,
during the reaction most of the active sites in a pure platinum electrode are
hidden in its bulk and, therefore, not participating in the hydrogen production.
Thus, it would be reasonable to replace the inactive bulk part of the electrode
with a cheaper material with similar properties, such as tungsten carbide.
Practically, this approach has been studied by Esposito et al. who in their
work analyzed electrocatalytic properties toward HER of a system comprising
platinum monolayer, supported on tungsten carbide, or Pt/WC (Esposito et al.,
2010). In their study the authors deposited sub-monolayer to monolayer (ML)
coverages of Pt on single-phase polycrystalline WC thin films by thermal
evaporation (Humbert et al., 2010). HER activities were evaluated for a
polycrystalline platinum foil, for a sample consisting of 30 equivalent Pt MLs
supported on WC and for unmodified WC film were evaluated as well for
comparison. The electrocatalytic activity evaluation has been conducted in
acidic media (0.5 M H2SO4) at room temperature. In Figure 20 a plot of log
(jo) vs. platinum coverage on WC shows that the activity of pure phase WC
was significantly lower than the bulk platinum foil, in agreement with the
studies discussed above. The addition of Pt sub-ML, however, significantly
improved the activity of WC and after reaching one ML coverage the HER
activity came close to that of platinum foil and did not change significantly
with Pt coverage growing to 30 ML. To complement their experimental
findings the authors conducted a density functional theory study of hydrogen
interaction with platinum, tungsten carbide and Pt/WC surfaces. According to
their results, atomic hydrogen adsorption energy on the unmodified WC was
-0.99 eV, while on Pt and on Pt/WC surfaces it is significantly less stable (-
0.46 eV and -0.43 eV, resp.), which was attributed to electronic properties of
Pt in the Pt/WC system being very similar to those of pure platinum. Based on
these data the authors emphasized the importance of the optimal binding
strength of HER intermediate on catalyst’s surface and argued that a single
ML Pt supported on WC is sufficient to recreate catalytic properties of bulk
Pt, thus, significantly reducing the cost of the active catalyst, without
sacrificing its activity.
Complimentary Copy
Using a similar approach Liu and Mustain demonstrated that in 0.1 M

HClO4 identical HER activities were observed on Pt ML supported on WC
and commercial Vulcan XC-72R supported Pt (Pt/C) (Y. Liu & Mustain,
2012). The reaction kinetics was also found to be very similar on these two
materials, taking the Volmer-Heyrovsky path with an estimated activation
energy of ~ 35 kJ/mol. Importantly, after more than 300 potentiometric cycles
the Pt/WC lost only 4% of its activity while the activity of Pt/C decreased by
more than 20%. It is worth mentioning, that the bulk Pt electrode did not
undergo any decrease in its activity after the identical stability test. The authors
associated the better stability of Pt/WC material to the significantly stronger
Pt–WC binding energy compared to that of Pt–C. The 4% Pt/WC activity loss
was attributed to the conversion of small amounts of WO2, present in the
material sample after synthesis, to WO3. The authors emphasized that in the
considered potential window the oxidation of WC to WO2 did not take place,
thus, evidencing a good long-term stability of the Pt/WC in working
conditions of HER.
Figure 20. Dependence of the HER exchange current density (jo) on the platinum
coverage on WC. (Based on data from (Esposito et al., 2010)).
As an alternative approach to spare Pt loading the study by Wei and Li

proposed a synthesis of tungsten carbide composites coated with little
platinum nanoparticles instead of controlled monolayer coating (Wei & Li,
2019). The synthesized 3%Pt/WC/C10 material showed an excellent stability
Complimentary Copy
and electrocatalytic performance in acidic media (0.5 M H2SO4) with small

overpotential of 85 mV required to achieve 10 mA/cm2 current density, almost
reaching the activity of 10%Pt/C catalyst. These results were attributed to the
synergistic interaction of tungsten carbide and platinum and improved
conductivity in the composite material.
Tungsten carbide can be also an efficient support for other metals active
toward HER, besides Pt. In a study by Kelly et al. a successful synthesis of
WC was reported by temperature programmed carburization of W in a mixed
CH4/H2 atmosphere, which later underwent physical vapor deposition process
to deposit layers of palladium of varying thickness to evaluate the HER
activity of the resulting Pd/WC material (Kelly, Hunt, Esposito, & Chen,
2013). While the synthetized materials demonstrated a good stability under
extended stability test, the activities of even multilayer (up to 6 ML) Pd/WC
materials never reached that of unsupported palladium, unlike Pt/WC,
discussed above. This difference in activities of supported and pure palladium
may stem from its intrinsic ability to absorb hydrogen into its bulk which
results in currents several orders of magnitude greater than those from surface
processes. This, in principle, can be mitigated by supporting Pd multilayers
thick enough to enable the absorption process, however, additional studies are
required to estimate this minimal sufficient thickness.
In certain cases, fundamental properties of a metal adlayer supported on
WC being different from the bulk metal can present an opportunity to create a
catalyst with a better activity (at least theoretically estimated one) than that of
the pristine metal. A theoretical work by (Vasić Anićijević, Nikolić, Marčeta-
Kaninski, & Pašti, 2013) showed that not only Cu/WC systems will be active
toward HER, they would also demonstrate a good stability in its potential
range. This study was expanded by (Koverga, Flórez, & Rodriguez, 2021) who
also confirmed that copper monolayers and submonolayers supported on W-
terminated WC(0001) surface can be active for HER and explored the origins
of this activity enhancement. The authors explained it by the support-induced
stabilization of hydrogen on the Cu adlayer in respect to that on unmodified
copper, that is practically inactive for HER. Interestingly, C-terminated WC
support has a destabilizing effect on hydrogen adsorption on Cu adlayer, and
therefore, was concluded to further decrease HER activity of copper.
Expanding the idea of supporting adlayer of a single metal, Chang Q. et
al. investigated stability and HER activity of Cu-Au alloy monolayer on WC
(Chang, Zhang, & Yang, 2021). They showed that the Cu-Au/WC systems are
more stable than either Cu/WC or Au/WC, which is due to the Cu-induced
ligand and stress effect in the alloy system. It causes a charge redistribution,
Complimentary Copy
as compared to supported monometallic monolayer systems, leading to the

observed increased stability of the alloy adlayer. The HER activity of the alloy
being better than that of either Cu/WC or Au/WC was explained by the Cu
dopants acting as the electron donors upon alloying with Au, indirectly
enhancing the charge transfer between Au and H, stabilizing the latter on the
surface and leading to improved predicted HER activity.
Thus, in all cases the overall HER activity of composite Pt/WC and
Pd/WC systems is always superior to that of pure WC. At the same time only
a handful of systems comprising non-noble metals supported on WC has been
investigated as potential HER catalysts. Therefore, a deeper study of these
materials on fundamental and experimental levels is required, being a
promising research direction to provide a scientific basis for a design and
large-scale production of active and efficient HER electrocatalysts.
Doped Tungsten Carbide

After it was concluded that pure WC has an intermediate HER activity,
numerous studies have been dedicated to understanding the effect of dopants
on fundamental and catalytic properties of tungsten carbide. Indeed, doping
WC with foreign element atoms, both metals and non-metals, is another very
perspective strategy to tune its physicochemical properties and to improve its
catalytic properties. However, to employ this method in a systematic and
informed way, a deep understanding is required of how fundamental
properties of tungsten carbide and their changes affect the overall HER
activity of the resulting material. That is why a lot of studies in this area
employ a combination of theoretical and experimental approaches.
A good example is the above-mentioned work by (Han et al., 2018) where
the authors associated the measured HER activity with the fact that adsorbed
hydrogen atoms bind strongly to WC, thus facilitating H+ reduction but
hindering hydrogen desorption. Bearing in mind the importance of optimal
binding of atomic H by a surface, the authors estimated theoretically that on
N-doped WC atomic hydrogen would be less stable than on the unmodified
WC, thus, suggesting that N-modified tungsten carbide would demonstrate a
better HER activity than WC. This hypothesis was confirmed by the authors
experimentally, as a significantly smaller overpotential at 10 mA/cm2 of -113
mV was measured for N-doped WC material in acidic media. This was further
improved by nanostructuring this material into nanoarrays with a resulting
overpotential η10 of -89 mA, which is one of the best activities among non-
precious metal-based HER electrocatalyst in acid.
Complimentary Copy
In another work by Su et al. nitrogen-doped WC supported on carbon

sheets was synthetized using ammonium metatungstate (AMT) and glucose as
sources of tungsten and carbon, respectively (Su, Yan, Wei, Zhu, & Zhou,
2020). Using the hydrothermal methods, the precursor was prepared and
subjected to a temperature of 900oC for 1 h and the product was characterized
with XRD, EDS, SEM and TEM. Electrocatalytic HER activities of the
synthetized materials and the commercial 20% Pt/C were assessed in 0.5 M
H2SO4. The measurements showed that N-doped WC needed the
overpotential, η10 of 156 mV to achieve 10 mA/cm2 current density,
outperforming unmodified carbide with η10=241 mV. This material, however,
showed the catalytic performance inferior to that of the commercial Pt/C
catalyst. The stability test over 1000 voltammetry cycles evidenced a good
stability of N-doped WC, judging from a small increase of 5mV in η10. The
enhanced activity of the prepared samples was attributed to nitrogen-induced
effects on the properties of the WC, such as increase of the electroactive
surface area and facilitated electron transfer between WC and electrolyte.
Modifying WC with other transition metals, such as Co, Ni and Mo also
proved to be an efficient method to improve its electrocatalytic activity toward
HER. Thus, a similar hydrothermal-based synthesis method was used to obtain
Co-doped WC with noticeably improved the HER activity in alkaline media
(H. Jin, Chen, Mao, & Wang, 2018). Specifically, the Co-doped WC was
obtained using AMT and Co(NO3)2 ∙ 6H2O at different Co/W molar ratios as
sources of tungsten and cobalt, respectively. After annealing the precursor at
800oC in nitrogen atmosphere, the sample was characterized using XRD, X-
ray photoelectron spectroscopy (XPS) and X-ray absorption (XAS). A
simultaneous presence of hexagonal WC and metallic Co in the synthetized
phase was concluded as well as presence of a mixed Co3W3C phase.
Importantly, the introduction of Co into WC caused the contraction of WC
lattice, as evidenced from X-ray absorption fine structure (XAFS)
measurements. The HER activity of the sample was analyzed in 1 M KOH and
evidenced that the Co-doped WC with the Co/W molar ratio of 3 is highly
efficient toward HER with an onset potential of 31 mV. Exchange current
density for this material was estimated to be 0.4 mA/cm2 and overpotential of
only 98 mV was required to reach the current of 10 mA/cm2. Under the same
experimental conditions, the current densities of Co and WC were measured
to be 209 mV and 345 eV, resp. indicating that the synergistic effect of Co and
WC improves the activity of the resulting phase. Additionally, the effect of
WC doping with Ni and Fe was analyzed in a similar fashion and a conclusion
was made that Ni and Fe can also improve HER activity of the carbide,
Complimentary Copy
although not as much as Co. For Ni- and Fe-doped WC the overpotentials of
183 mV and 271 mV at 10 mA/cm2, respectively were measured, almost 2 and
3 times higher than the value of 98 mV measured for Co-modified carbide.
The experimental findings were complemented by a theoretical DFT-based
analysis that demonstrated that the incorporation of Co into lattice of the
carbide caused the electron transfer from the dopant to the carbide, increasing
its density of states near the Fermi level. This, in its turn, resulted in the
moderate stability of water and hydrogen, optimizing HER kinetics.
Another study of electrocatalytic HER activity of Ni-doped WC
confirmed that this is a perspective material for applications in electrochemical
hydrogen production (Y. Chen et al., 2020). To achieve current densities of 10
mA/cm2 in acidic (1 MHClO4), alkaline (1 M KOH) and neutral (0.5 M
Na2SO4) overpotentials, η10 of -110 mV, -190 mV and -300 mV, resp. were
required for Ni-doped WC, being 100-300 mV lower than that of other non-
precious metal electrocatalysts, not reaching, however the activity of platinum.
This conclusion was also confirmed by comparing the onset overpotentials for
Ni-modified WC and Pt/C in the full range of pH. For the W1-xNixC material
in acidic, neutral and alkaline solutions the values of η0 were 50 mV, 0 mV
and 30 mV, while Pt/C catalyst is characterized by zero onset overpotential in
the whole range of pH. The stability tests evidenced almost no decline in HER
activity of Ni-doped carbide in the wide range of pH.
These results disagree somewhat with a later work by Mabuea, Erasmus
and Swart where tungsten and molybdenum carbides were modified by doping
with nickel, cobalt and by their combination (Mabuea, Erasmus, & Swart,
2023). The authors concluded that in alkaline solution (1.0 M NaOH)
commercial Pt/C catalysts demonstrated better activity than any carbide-based
materials. However, in this study Ni-modified WC and MoC displayed better
performance than corresponding Co-modified and unmodified carbides. Thus,
while not being the most active catalyst, Ni-modified tungsten carbide
definitely be considered as a material active for HER in a wide range of pH
with an excellent stability.
Because molybdenum carbide is a material well-studied both
experimentally and theoretically, a logical step was to investigate properties
of bimetallic W-Mo carbide and its applicability as catalyst for HER. It was
demonstrated that doping WC with molybdenum has an impact on the
electronic structure of metallic centers in WC, which in its turn affect atomic
H stability on them (L. Wang et al., 2020). Specifically, the near-Fermi level
DOS population of WC increased after doping, thus, providing more available
electrons for the electrochemical process. Moreover, incorporation of
Complimentary Copy
molybdenum into tungsten carbide caused an overall d-band center downshift,

further away from the Fermi level. This shift of the d-band center is typically
associated with weakening of the H-surface interaction, and is expected to
improve electrocatalytic activity toward HER of tungsten carbide where
atomic hydrogen binds rather strongly (Michalsky et al., 2014). Theoretical
predictions were found to be in a good agreement with results of an
experimental study, which showed that Mo-doped WC is active an efficient
HER catalyst in a wide range of pH. In alkaline media it was characterized
with η10 overpotential of 179 mV, which was lower than of unmodified
tungsten carbide (281 mV), while in acidic and neutral media the gain in
performance of WC due to Mo presence in terms of η10 overpotential was 105
mV and 126 mV, resp.
Thus, it is evident that inclusion of other transition metals into WC
structure modifies it on the fundamental level, and, therefore, a link must be
established between the nature of the dopant and the shift in electrocatalytic
pretties of tungsten carbide. For this further experimental and theoretical
studies of materials based on tungsten carbide doped with other transition
metals, are required to elucidate an activity trend and expand the knowledge
of the origins of their activity to design catalysts based on the foundation of
this very promising strategy.
HER Activity of Bimetallic Tungsten-Based Carbides

Modifying tungsten carbide with other transition metals may result in
bimetallic carbides, as was seen in case of Co-modified WC, where traces of
Co3W3C byproduct were found (H. Jin et al., 2018). This class of WC-based
compounds also presents interest for designing electrocatalysts for HER, as it
offers a wide range of possibilities for fine-tuning of the fundamental
properties of the resulting materials to tailor them better for the target process.
Synthesis methods for the bimetallic carbides are quite similar to the
approaches used to obtain pure WC with the only difference that on the
precursor preparation stage, source compounds of carbon, tungsten and other
metal are required. Most of the studies in this area are focused on bimetallic
Mo-C carbides. The main reason behind it is that molybdenum carbide is more
active toward HER than tungsten carbide (Michalsky et al., 2014). Thus, while
resulting in a discussion of Mo-W bimetallic carbide properties, the majority
of the studies aim to improve HER activity of molybdenum carbide by
inclusion of tungsten. Nonetheless, these materials pertain to the scope of this
contribution and are discussed below.
Complimentary Copy
For instance, to synthetize a Mo-W carbide hollow spheres with a general

chemical formula MoxW2-xC, phosphomolybdic (H3PMo12O40 ∙ nH2O) and
phosphotungstic (H3PW12O40 ∙ nH2O) acids were used to prepare the precursor
with different Mo/W molar ratios (Lin, Chen, & Wu, 2018). Nanospheres of
SiO2 were synthetized and used as templates to shape the final product. After
adding pyrrole solution into the dispersion of SiO2 templates, mixed with
phosphotungstic and phosphomolybdic acids, the obtained precursor was
annealed at temperature 700oC in reducing atmosphere. The final product was
obtained by the removal of templates in hot basic solution. The product was
characterized using various techniques, TEM, XPS and EDX among them.
HER activity of MoxW2-xC hollow spheres was measured in the wide range of
pH, specifically solutions of 0.5 M H2SO4, 1 M phosphate buffer saline (PBS)
and 1 M KOH. For the sake of comparison, the activity of 20 wt% commercial
Pt/C was measured as well. In alkaline media the synthetized MoxW2-xC
catalyst with Mo/W molar ratio of 1.26/0.74 required η10 of 106 mV, which,
the authors concluded, was superior to most of the previously reported alkaline
HER electrocatalysts. In contrast η10 for Pt/C under the same conditions was
only 23 mV, significantly outperforming the activity of the bimetallic carbide.
However, in high current density region the carbide performs much better than
Pt: to achieve j of 300 mA/cm2 it requires overpotential (η300) of 237 mV while
Pt/C needed 250 mV. In acidic media the same, Mo1.26W0.74C, material
showed a good performance with η10=127 mV and only requiring 250 mV to
reach current density of 300 mA/cm2, substantially exceeding most of the
previously reported electrocatalysts, but being outperformed by the
commercial Pt/C with η10 of 21 mV and η300 of 67 mV. Finally, at neutral pH
Pt/C is significantly more active toward HER in low current density region
(but is outperformed by the Mo1.26W0.74C catalyst in high-j region thus,
resembling the trends in alkaline media. In all cases the bimetallic carbide was
outperforming molybdenum carbide, and, consequently, tungsten carbide,
which was attributed to a weakening of Mo-H bond, caused by introduction of
a proper amount of W leading to an increased electron density around
molybdenum atoms in the catalyst’s structure. Importantly, the stability test
conducted for the Mo1.26W0.74C material evidenced its excellent durability in
the whole range of pH.
Similarly, an improved HER activity of a catalyst with a hollow
architecture based on MoC1-x and WC1-x carbide compared to that of pure MoC
and WC was predicted from theoretically estimated optimized hydrogen
adsorption free energy (M. Yan et al., 2022). Further analysis of the electronic
structure of the bimetallic carbide revealed a shift of the d-band center on
Complimentary Copy
metallic active sites toward lower energies, similarly to the work, discussed
above. An experimental verification of HER activity of the bimetallic carbide
in acidic (0.5 M H2SO4) and alkaline media (1 M KOH) confirmed that as-
prepared catalyst displayed outstanding and durable electrocatalytic
performance with a low η10 overpotential of 103 mV and 163 mV, resp.
As it was demonstrated above Co-doped tungsten carbide presents a
viable candidate as a non-precious metal HER catalyst. Expanding this idea,
Chen et al. investigated HER activity of cobalt tungsten carbide, Co6W6C,
nanosheet embedded in N-doped carbon matrix in 1 M KOH (J. Chen, Ren,
Cui, & Wang, 2020). The synthesis of the carbide was based on employing
leaf-like zeolitic imidazolate frameworks nanosheet arrays to form a template
for the final product and, simultaneously, as carbon source. The
nanostructured carbide was obtained by immersing the templates into a mixed
solution and annealing them in a mixed atmosphere of hydrogen and argon.
The formation of the bimetallic phase was confirmed with XRD and
additionally characterized by means of SEM and TEM. Electrochemical
characterization of the synthetized catalyst demonstrated its good stability and
an increase in HER activity of the Co6W6C comparing to activities of cobalt
and tungsten carbide. To reach current density of 10 mA/cm2 only 59 mV
overpotential was required for cobalt-tungsten carbide, while η10 for the
unmodified tungsten carbide and cobalt were 147 mV and 300 mV, resp. The
exchange current density, j0 for Co6W6C is larger than that of tungsten carbide
(0.59 mA/cm2 vs. 0.02 m A/cm2), indicating a higher intrinsic activity of the
bimetallic compound. The authors argued that enhanced activity of the
Co6W6C could be attributed to the synergistic effect of Co and W atoms that
effectively tailors the electronic structure of the Co-W carbide, optimizing
adsorption energy of atomic hydrogen on it. Additionally, specific properties
of the porous nanosheet support had an enhancing effect as well: better
exposure of active sites due to specific structure its enhanced conductivity.
Thus, although not as many reports are available in literature on HER
activity of tungsten-based bimetallic carbides as there are on doped WC, it is
evident that this class of materials presents a promising alternative to
conventional electrocatalysts for hydrogen production. The reported data
suggest that the increase in HER activity of bimetallic carbides compared to
that of the corresponding monometallic carbides also stems from changes in
their fundamental properties (and in atomic H stability on the catalyst) due to
a complex interplay of their electronic structures.
Complimentary Copy
Tungsten Carbide Supported on Other Materials

Importantly, the work by Chen et al., discussed above, also showed that
support plays an important role in modulating HER activity of the complex
electrocatalytic systems. In another study, reviewed earlier, the authors
explored HER activity of WC supported on metallic tungsten (Huang et al.,
2020). The improved electrocatalytic properties of the composite WC/W
material was attributed to efficient electrical contact between WC and the
support that enabled barrierless electron transport and minimizing the impact
of contact resistance on the HER performance. Thus, a careful selection of the
support for WC can affect its electrocatalytic activity toward HER without
introducing any changes into its structural and chemical properties and can be
employed for designing WC-based materials with improved HER activity.
Carbon-based materials are the most popular choice for supporting
tungsten carbide. Among the vast choice of nanostructured carbon materials
carbon nanotubes (CNT) are often employed because of their high dispersion
and good conductivity. Preparation of WC-based materials supported on the
CNT is relatively straightforward and, therefore, has a good scalability.
For instance, WC nanocrystals anchored on CNTs were obtained by
mixing and ultrasonically dispersing WO3, multiwalled carbon nanotube and
Mg and annealing this precursor at 950oC (Cheng Liu et al., 2018). After
cooling down to room temperature the samples were washed with distilled
water and 1 M HCl solution and dried. Analysis of the final product with TEM
and XPS techniques showed that WC/CNT catalyst was comprised of W- and
C-containing nanoparticles (NPs) with sizes in most cases smaller than 5 nm
supported on CNT with trace presence of impurities such as metallic W. The
XRD analysis evidenced a simultaneous presence of WC and W2C phases in
the NPs. These samples were tested as electrocatalysts for HER in acidic
media (0.5 M H2SO4) together with commercial WC NPs and monodispersed
WC anchored on carbon black, taken for the reference (WC/C). The
commercial tungsten carbide showed poor activity for HER with almost no
current density at 400 mV (see Figure 21), while WC supported on carbon
black (WC/C) showed a noticeable improvement with 31.3 mA/cm2 current
density at 300 mV and 170 mV onset overpotential. Finally, among the tested
WC-based catalysts WC/CNT material demonstrated the best performance
with onset overpotential of 90 mV and current density of 93.2 mA/cm2 at 300
mV.
Complimentary Copy
Figure 21. Polarization curves for WC NPs, carbon-supported WC, CNT-supported

WC and Pt. (Based on data from (Cheng Liu et al., 2018).
The authors stated that even though the HER performance of the WC/CNT
material is still not close enough to those of commercial Pt electrode with onset
potential of 23 mV, the overall HER activity was one of the best among
tungsten carbide-based catalysts. The improved activities of WC/C and
WC/CNT were attributed to greater surface areas of these materials and better
connection of the WC NPS on the CNT substrate, improving overall
conductivity of the material. Additionally, on pure WC the H2 bonding was
much stronger than on Pt, thus, inhibiting its desorption. On the carbon-
supported WC materials H2-surface interaction strength was substantially
reduced since the anchored WC induced a charge transfer from W to C,
downshifting the d-band center of W. The consequent stability test of the
WC/CNT nanocatalyst was conducted by continuously running the HER
process for 3000 cycles in 0.5 M H2SO4 solution, and gave highly stable
polarization curves evidencing a long-term stability of this material.
In an earlier study similar conclusions about the role of support were made
about WC/CNT HER activity in acidic media, where these materials were
reported to have exchange current density of 117.6 mA/cm2 at 300 mV (Fan,
Zhou, & Guo, 2015). Also measuring WC/CNT activity in alkaline media
yielded the current density of 33.1 mA/cm2 at 300 mV, evidencing good
performance of this class of electrocatalysts in wide range of pH.
Complimentary Copy
As it is seen in Figure 21 HER activity of WC supported on carbon black

is higher than of unsupported phases, however, it still must be significantly
improved for this material to be considered as a viable candidate for
electrochemical hydrogen production. A possible approach to this problem is
additional functionalization of the support with heteroatoms, which is
expected to further weaken the binding strength of W-H bond, allowing the
earlier desorption of H2 from the catalyst.
An example of this approach is the work by Su et al. described above. The
authors investigated HER activity of tungsten carbide supported on nitrogen-
doped carbon sheets (WC/NC) (Su et al., 2020). Electrocatalytic HER activity
of the synthetized sample was tested in acidic media (0.5 M H2SO4) together
with the WC/C and commercial 20% Pt/C used for comparison. The WC/NC
material displayed an activity comparable to other WC-based materials
described above. It required the overpotential of 156 mV to reach current
density of 10 mA/cm2 and was not close to reach HER activity of commercial
Pt-based catalysts. An important observation, however, was that the WC/NC
material significantly outperformed WC/C catalyst, thus showing an
enhancing effect of including nitrogen into the structure of the support on
catalytic properties of the resulting material. This enhanced HER activity was
tied to high surface area of the carbon sheets and the support acting as current
collector facilitating the electron transfer between WC and electrolyte. Also,
it was argued that synergistic effect of WC nanoparticles and N-doped carbon
support could affect atomic H stability of WC nanoparticles, bringing it closer
to the value optimal for HER. Importantly, the stability of WC/NC catalyst in
working conditions is slightly lower than that of WC/C catalyst: as evidenced
for somewhat reduced activity of the WC/NC catalyst 1000 cycles. The XPS
analysis revealed that WC conversion into WO3 takes place and as result active
sites on the catalyst get blocked by inert tungsten carbide.
A somewhat complex method of producing cost-efficient WC-based HER
electrocatalysts was proposed by (X. Chen et al., 2019). It was based on the
ability of zeolitic imidazolate frameworks (ZIF) to produce nanoporous
carbons and their composites with metals, such as cobalt. These materials have
several characteristics that can be valuable for HER: homogeneous
distribution of heteroatoms, such as nitrogen, and graphitized carbon
facilitating charge transfer among them. To increase their low surface area and
porosity it was proposed to include a second metal into the structure of ZIF,
thus producing bimetallic ZIFs, or BMZ. In their work the authors synthetized
Pt-WC hybrids supported on BMZ, expecting the final material to take
advantage of the synergistic Pt-W coupling and of nanotubes present in BMZ
Complimentary Copy
structure together with their high surface area to yield an active and cost-
efficient HER catalyst. Briefly, the bimetallic Zn-Co ZIF with different molar
ratios of Zn and Co were synthetized by ultrasonically homogenizing mixture
of zinc nitrate hexahydrate and cobalt nitrate hexahydrate in deionized water.
To the obtained mixture a solution of 2-methyimidazole in deionized water
was added. The BMZ product was collected by centrifugation and dried in
vacuum at 80oC. To prepare the final Pt-WC/BMZ product the synthetized Zn-
Co BMZ was mixed with AMT and dissolved in chloroplatinic acid
hexahydrate, followed by the ultrasonic dispersion. After collecting the
precipitate by centrifugation, it was annealed at 900oC for 1.5 h. Several
samples with varying Pt/W weight ratio were prepared: 1:10, 0.7:10 and
2.5:10. Additionally Pt/BMZ and WC/BMZ materials were prepared to
compare HER activities of WC and Pt supported on BMZ to that of the hybrid
Pt-WC/BMZ materials. The electrochemical characterization of the
synthetized materials was conducted in acidic media, specifically, in 0.5 M
H2SO4. It revealed that the material with Pt/WC weight ratio of 1:10 and
Zn/Co molar ration of 1:2 presented the highest HER activity among the
studied catalysts. Specifically, its η10 value was 23 mV, which was 10 mV
lower than 20% Pt/C which required 33 mV to achieve current density of 10
mA/cm2. Interestingly, pure WC/BMZ without added Pt needed a significantly
higher overpotential of 180 mV to reach the same current density, indicating
its average performance for HER. The authors attributed this excellent HER
activity of the Pt-WC/BMZ catalyst to the synergistic effect between Pt and
WC. Specifically, they argued that the average d-band center shift on metallic
centers of the hybrid catalyst enabled an optimal binding strength of hydrogen
to the catalyst’s surface. The activity-enhancing role of the support was
explained in terms of its high specific surface area and improved electric
conductivity. Good stability of the synthetized Pt-WC/BMZ material in HER
conditions was evidenced by no visible drop in its activity after 1000 cycles
and only a minor catalyst’s degeneration after 3000 cycles. While being quite
promising HER catalyst, this material requires a multi-stage synthesis with
many chemical compounds mixed in very specific ratios. Therefore, aside
from presenting an interesting example of alternative WC-based HER
catalysts, its mass implementation can be problematic and at very least
requires further studies to develop a reliable and simpler synthesis protocol.
Complimentary Copy
Conclusion
As mentioned above, tungsten carbides can be useful materials for the

chemical processes associated with C1 chemistry and the conversion of
hydrocarbons. Theoretical studies with well-defined surfaces of the hexagonal
and cubic phases of WC have shed light in many fundamental aspects
associated with the binding and activation of small key molecules (H2, CH4,
C2H2, C2H2, CO2, CO, NO, NH3). These studies have shown important
differences in C- and W-terminated surfaces, and the activity of the C-centers
must not be neglected. In reactions of hydrogenation, H coverage is a big issue
and can affect the formed products and the rates of reaction. In the future,
computational studies need to be done for a larger set of adsorbates. At the
same time, it is necessary to explore in detail the behavior of surfaces that a
C/W ratio different from 1. This is an important variable in experimental
studies and theory can help to predict optimal C/W ratio for different catalytic
applications.
The rich chemistry seen for the extended surfaces of WC can be modified
when nanoparticles of this material are deposited on oxide surfaces or
dispersed inside zeolites or carbon nanotubes. This is an area in which some
experimental work has been published (Esposito & Chen, 2011), but more
theoretical work needs to be done. Interaction of the carbide with the O centers
of an oxide or zeolite could modify its chemical properties (Esposito & Chen,
2011), leading to catalytic properties that are very different from those seen
for extended surfaces of orthogonal and cubic phases of WC. Related to this
point, oxycarbides of W can exhibit interesting properties (Esposito & Chen,
2011), (Hwu & Chen, 2005) and need to be examined at a theoretical level.
The majority of studies dedicated to HER activity of WC and WC-based
materials are either purely experimental or use a combined experimental-
theoretical approach. Theory-based reports are scarce in this field mainly
because of the experimentally demonstrated intermediate HER activity of
tungsten carbide. As it was mentioned above this conclusion about possible
application of WC in hydrogen production from water also agrees well with
the data available from theoretical studies (Esposito et al., 2010) (Koverga et
al., 2019) (Koverga, Flórez, & Rodriguez, 2021) (Michalsky et al., 2014)
(Vasić Anićijević et al., 2013). One common thing about all approaches to
improve HER activity of tungsten carbide, discussed above, is that all methods
intended to change stability of atomic hydrogen on WC, although through
different means. Indeed, coating tungsten carbide with other metals,
incorporating them into its crystalline lattice, or completely substituting
Complimentary Copy
tungsten atom in the carbides structure invariably create new active centers on
the catalysts surface with fundamental properties different from those in the
original material.
The most used explanation for the changes in hydrogen stability on WC-
based materials is the d-band shift resulting from introduction of foreign atoms
into the WC phase. As the result of these changes, hydrogen stability on the
catalyst’s surface weakens leading to improvement of catalytic properties of
the modified WC-based material. While this is a promising strategy,
oftentimes the method of selection of modifying materials is based on “trial
and error” approach and still is lacking a more systematized scientific basis on
which a more informed choice could be made.
From the point of view of theory-based investigation methods activity
descriptors based on hydrogen stability on the surface must be expanded to
account for more factors, impacting electrocatalytic activity of a material.
Additionally, to having an optimal hydrogen binding energy, possible desired
characteristics for a material active for HER can include its d-band spanning
the Fermi level which can enable stable and long-range interaction with
hydrogen’s 1s orbital (Quaino, Juarez, Santos, & Schmickler, 2014).
Therefore, theory-based search for modifying elements bringing the electronic
structure of WC closer to these characteristics is a promising strategy for
improving its HER activity.
Furthermore, existing models consider only the electronic properties of
the surface, however, fundamental properties of the adsorbates and their
response to shift in electronic structure of the WC surface may impact the
electrocatalytic performance of the material as well (G.-Q. Yu et al., 2021).
Also, the argument of the d-band shift induced by foreign atoms does not fully
account for changes in hydrogen stability on carbon atoms of the carbide, that,
statistically, represent half of the total number of active sites available on the
WC surface. Therefore, a deeper exploration of changes in the fundamental
properties of both W and C active centers of the carbide, resulting from its
modification by other elements, must be conducted. This could offer a better
understanding of the correlation between the nature of the modifying element,
its location in the WC host and HER activity of the composite system.
Therefore, a plethora of factors exist that define electrocatalytic activity
of WC toward HER, and which ones play more important role than others
remains an open question. Employing computational methods, such as
machine learning and high-throughput calculations, and including a wider
range of possible modifying elements, both metals and non-metals, can
facilitate defining and development of new descriptors and provide more
Complimentary Copy
accurate structure-activity correlations. Also, the suitability and predictive

ability of the existing descriptors must be reevaluated considering
fundamental properties of the materials in systems with solvent present.
Additional to computational screening of possible catalysts theoretical
approach can aid significantly in evaluating the mechanism of HER. Indeed,
works on electrochemical CO2 reduction to methane on WC and transition
metal-decorated phase (Wannakao, Artrith, Limtrakul, & Kolpak, 2015) and
on methanol electrooxidation on Pt/WC surfaces (Sheng et al., 2015) allowed
a better understanding of the impact of the supported adlayer properties on the
mechanism of the reaction and overall catalytic properties of the composite
WC-based systems. The DFT-based study also helped to identify Ag/WC
material as an active electrocatalyst for CO oxidation, an important process in
fuel cells, through a careful analysis of the reaction mechanism (Y. Zhao et
al., 2019). The resulting activity of the Ag/WC material for CO oxidation was
higher than that of Pt(111) and was attributed to WC-induced strengthening of
CO stability on the catalyst’s surface.
And while HER mechanism is significantly simpler than of the mentioned
reactions, knowing its specific details on a potential catalyst can provide an
important information facilitating the theory-based conclusion about
efficiency of a given material for hydrogen production.
As the final remark it must be said that while purely theoretical studies
can be useful for understanding the correlation between fundamental
properties of materials and their HER activity, an experimental study must be
always conducted to verify the obtained results. In general, any theoretical
investigation of HER activity of novel catalysts, ideally, must be conducted
together with a corresponding experiment, and vice versa, a theoretical model
can give a deeper insight into phenomena observed experimentally. This
combined approach could lead to a better understanding of other factors that
define the catalytic performance of the carbide and, therefore, a better
understanding of the atomic-level origins of its activity.
The methodologies in several studies lack of considering van der Waals
interactions and zero point energy contributions, a fundamental aspect when
modelling tungsten carbides, which could change remarkably the energy
values dealing with binding and transformation of adsorbates (Jimenez‐
Orozco et al., 2023). Even though the evidence shows that the reactivity relates
with the presence of vacancies and imperfections of the pristine WC, there is
a lack of studies regarding a systematic and comprehensive theoretical
analysis of their effect in the chemical reactivity. The modelling of reactions
at practical conditions of pressure and temperature was reported in a few
Complimentary Copy
works from a theoretical perspective, predicting the appropriate practical

conditions to perform future experiments (Jimenez-Orozco et al., 2023;
Jimenez‐Orozco et al., 2023; Koverga, Flórez, Jimenez-Orozco, et al., 2021b,
2021a). However, there is a lack of modelling WC-based systems at practical
T,p conditions is most of the reported systems, implying a need to implement
methodologies when dealing with computational approaches of WC-based
catalysts. The use of machine learning is still unknown for the modelling of
tungsten carbides as catalysts, implying a shift paradigm of the classical
models to explore WC catalysts from different angles.
Acknowledgments
The authors thank to Universidad de Medellín for the support (C. Jimenez-
Orozco, A. Koverga, and E. Florez). J. A. Rodriguez is supported by the Office
of Basic Energy Sciences of the U.S. DOE under the contract grant
SC0012704.
References
Alvarez-Garcia, A., Flórez, E., Moreno, A., & Jimenez-Orozco, C. (2020). CO2 activation
on small Cu-Ni and Cu-Pd bimetallic clusters. Molecular Catalysis, 484(September
2019), 110733. https://doi.org/10.1016/j.mcat.2019.110733.
Bernard d’Arbigny, J., Taillades, G., Rozière, J., Jones, D., & Marrony, M. (2011). High
Surface Area Tungsten Carbide with Novel Architecture and High Electrochemical
Stability. ECS Transactions, 41(1), 1207–1213. https://doi.org/10.1149/1.3635653.
Blöchl, P. E. (1994). Projector augmented-wave method. Physical Review B, 50(24),
17953–17979. https://doi.org/10.1103/PhysRevB.50.17953.
Boopathy, G., Govindasamy, M., Nazari, M., Wang, S.-F., & Umapathy, M. J. (2019).
Facile Synthesis of Tungsten Carbide Nanosheets for Trace Level Detection of Toxic
Mercury Ions in Biological and Contaminated Sewage Water Samples: An
Electrocatalytic Approach. Journal of The Electrochemical Society, 166(10), B761–
B770. https://doi.org/10.1149/2.0181910jes.
Brillo, J., Hammoudeh, A., Kuhlenbeck, H., Panagiotides, N., Schwegmann, S., Over, H.,
& Freund, H.-J. (1998). Structural studies of WC(0001) and the adsorption of benzene.
Journal of Electron Spectroscopy and Related Phenomena, 96(1–3), 53–60.
https://doi.org/10.1016/S0368-2048(98)00222-9.
Brillo, J., Kuhlenbeck, H., & Freund, H.-J. (1998). Interaction of O2 with WC(0001).
Surface Science, 409(2), 199–206. https://doi.org/10.1016/S0039-6028(98)00193-9.
Brillo, J., Sur, R., Kuhlenbeck, H., & Freund, H.-J. (1998a). Electron spectroscopic study
Complimentary Copy
of the interaction of WC(0001) with different adsorbates (C6H6, CO and NO). Journal
of Electron Spectroscopy and Related Phenomena, 88–91, 809–815.
https://doi.org/10.1016/S0368-2048(97)00214-4.
Brillo, J., Sur, R., Kuhlenbeck, H., & Freund, H.-J. (1998b). Interaction of CO and NO with
WC(0001). Surface Science, 397(1–3), 137–144. https://doi.org/10.1016/
S0039-6028(97)00725-5.
Cai, X., & Hu, Y. H. (2019). Advances in catalytic conversion of methane and carbon
dioxide to highly valuable products. Energy Science & Engineering, 7(1), 4–29.
https://doi.org/10.1002/ese3.278.
Chan-Thaw, C., & Villa, A. (2018). Metal Carbides for Biomass Valorization. Applied
Sciences, 8(2), 259. https://doi.org/10.3390/app8020259.
Chang, Q., Zhang, X., & Yang, Z. (2021). First-principles study on the Cu-Au alloy
monolayer supported on WC for hydrogen evolution. Applied Surface Science, 565,
150568. https://doi.org/10.1016/j.apsusc.2021.150568.
Chen, J., Ren, B., Cui, H., & Wang, C. (2020). Constructing Pure Phase Tungsten‐Based
Bimetallic Carbide Nanosheet as an Efficient Bifunctional Electrocatalyst for Overall
Water Splitting. Small, 16(23), 1907556. https://doi.org/10.1002/
smll.201907556.
Chen, W.-F., Muckerman, J. T., & Fujita, E. (2013). Recent developments in transition
metal carbides and nitrides as hydrogen evolution electrocatalysts. Chemical
Communications, 49(79), 8896. https://doi.org/10.1039/c3cc44076a.
Chen, X., Li, S., Sun, X., Liu, F., Li, C., Yu, J., & Mu, S. (2019). Coupling low platinum
and tungsten carbide supported on ZIFs-Derived porous carbon for efficient hydrogen
evolution. Electrochimica Acta, 328, 135077. https://doi.org/10.1016/
j.electacta.2019.135077.
Chen, Y., Zheng, Y., Yue, X., & Huang, S. (2020). Hydrogen evolution reaction in full pH
range on nickel doped tungsten carbide nanocubes as efficient and durable non-
precious metal electrocatalysts. International Journal of Hydrogen Energy, 45(15),
8695–8702. https://doi.org/10.1016/j.ijhydene.2020.01.132.
Chen, Z.-Y., Duan, L.-F., Sheng, T., Lin, X., Chen, Y.-F., Chu, Y.-Q., … Lin, W.-F. (2017).
Dodecahedral W@WC Composite as Efficient Catalyst for Hydrogen Evolution and
Nitrobenzene Reduction Reactions. ACS Applied Materials & Interfaces, 9(24),
20594–20602. https://doi.org/10.1021/acsami.7b04419.
Claridge, J. B., York, A. P. E., Brungs, A. J., Marquez-Alvarez, C., Sloan, J., Tsang, S. C.,
& Green, M. L. H. (1998). New Catalysts for the Conversion of Methane to Synthesis
Gas: Molybdenum and Tungsten Carbide. Journal of Catalysis, 180(1), 85–100.
https://doi.org/10.1006/jcat.1998.2260.
Czaplicka, N., Rogala, A., & Wysocka, I. (2021). Metal (Mo, W, Ti) Carbide Catalysts:
Synthesis and Application as Alternative Catalysts for Dry Reforming of
Hydrocarbons—A Review. International Journal of Molecular Sciences, 22(22),
12337. https://doi.org/10.3390/ijms222212337.
Da Costa, P., Lemberton, J.-L., Potvin, C., Manoli, J.-M., Perot, G., Breysse, M., & Djega-
Mariadassou, G. (2001). Tetralin hydrogenation catalyzed by Mo2C/Al2O3 and
WC/Al2O3 in the presence of H2S. Catalysis Today, 65(2–4), 195–200.
https://doi.org/10.1016/S0920-5861(00)00593-9.
Complimentary Copy
Dang, J., Wu, Y., Lv, Z., & Lv, X. (2018). Preparation of tungsten carbides by reducing
and carbonizing WO2 with CO. Journal of Alloys and Compounds, 745, 421–429.
https://doi.org/10.1016/j.jallcom.2018.02.224.
Decker, S., Löfberg, A., Bastin, J.-M., & Frennet, A. (1997). Study of the preparation of
bulk tungsten carbide catalysts with C2H6/H2 and C2H4/H2 carburizing mixtures.
Catalysis Letters, 44, 229–239.
Delley, B. (1990). An all-electron numerical method for solving the local density functional
for polyatomic molecules. The Journal of Chemical Physics, 92(1), 508–517.
https://doi.org/10.1063/1.458452.
Delley, B. (1995). DMol, a standard tool for density functional calculations: Review and
advances. https://doi.org/10.1016/S1380-7323(05)80037-8.
Delley, B. (2000). From molecules to solids with the DMol3 approach. The Journal of
Chemical Physics, 113(18), 7756–7764. https://doi.org/10.1063/1.1316015.
Esposito, D. V., & Chen, J. G. (2011). Monolayer platinum supported on tungsten carbides
as low-cost electrocatalysts: opportunities and limitations. Energy & Environmental
Science, 4(10), 3900. https://doi.org/10.1039/c1ee01851e.
Esposito, D. V., Hunt, S. T., Stottlemyer, A. L., Dobson, K. D., McCandless, B. E.,
Birkmire, R. W., & Chen, J. G. (2010). Low-Cost Hydrogen-Evolution Catalysts
Based on Monolayer Platinum on Tungsten Monocarbide Substrates. Angewandte
Chemie International Edition, 49(51), 9859–9862. https://doi.org/10.1002/anie.
201004718.
Esposito, D. V, Hunt, S. T., Kimmel, Y. C., & Chen, J. G. (2012). A new class of
electrocatalysts for hydrogen production from water electrolysis: metal monolayers
supported on low-cost transition metal carbides. Journal of the American Chemical
Society, 134(6), 3025–3033. https://doi.org/10.1021/ja208656v.
Fan, X., Zhou, H., & Guo, X. (2015). WC Nanocrystals Grown on Vertically Aligned
Carbon Nanotubes: An Efficient and Stable Electrocatalyst for Hydrogen Evolution
Reaction. ACS Nano, 9(5), 5125–5134. https://doi.org/10.1021/acsnano.5b00425.
Fang, H., Du, J., Tian, C., Zheng, J., Duan, X., Ye, L., & Yuan, Y. (2017). Regioselective
hydrogenolysis of aryl ether C–O bonds by tungsten carbides with controlled phase
compositions. Chemical Communications, 53(74), 10295–10298. https://doi.org/
10.1039/C7CC05487D.
Fang, H., Roldan, A., Tian, C., Zheng, Y., Duan, X., Chen, K., … Yuan, Y. (2019).
Structural tuning and catalysis of tungsten carbides for the regioselective cleavage of
C O bonds. Journal of Catalysis, 369, 283–295. https://doi.org/10.1016/j.jcat.
2018.11.020.
Fang, H., Wu, L., Chen, W., & Yuan, Y. (2021). Synergy of carbon defect and transition
metal on tungsten carbides for boosting the selective cleavage of aryl ether C O bond.
Applied Catalysis A: General, 613, 118023. https://doi.org/10.1016/
j.apcata.2021.118023.
Fang, Y., Wu, M., Ci, S., Liu, Q., Zhao, X., Qian, P., & Qu, X. (2022). First-principles
simulations of the interface adhesion and wettability: Cu(111)/TiC(111) versus
Cu(111)/WC(0001). Physica B: Condensed Matter, 646, 414336. https://doi.org/
10.1016/j.physb.2022.414336.
Frauwallner, M. L., López-Linares, F., Lara-Romero, J., Scott, C. E., Ali, V., Hernández,
Complimentary Copy
E., & Pereira-Almao, P. (2011). Toluene hydrogenation at low temperature using a

molybdenum carbide catalyst. Applied Catalysis A: General, 394(1–2), 62–70.
https://doi.org/10.1016/j.apcata.2010.12.024.
Führer, M., van Haasterecht, T., & Bitter, J. H. (2022). Cinnamaldehyde hydrogenation
over carbon supported molybdenum and tungsten carbide catalysts. Chemical
Communications, 58(98), 13608–13611. https://doi.org/10.1039/D2CC05322E.
Furimsky, E. (2003). Metal carbides and nitrides as potential catalysts for hydroprocessing.
Applied Catalysis A: General, 240(1–2), 1–28. https://doi.org/10.1016/S0926-
860X(02)00428-3.
Giannozzi, P., Baroni, S., Bonini, N., Calandra, M., Car, R., Cavazzoni, C., … others.
(2009). QUANTUM ESPRESSO: a modular and open-source software project for
quantum simulations of materials. Journal of Physics: Condensed Matter, 21(39),
395502.
Gong, Q., Wang, Y., Hu, Q., Zhou, J., Feng, R., Duchesne, P. N., … Lee, S.-T. (2016).
Ultrasmall and phase-pure W2C nanoparticles for efficient electrocatalytic and
photoelectrochemical hydrogen evolution. Nature Communications, 7(1), 13216.
https://doi.org/10.1038/ncomms13216.
Gonze, X., Amadon, B., Anglade, P.-M., Beuken, J.-M., Bottin, F., Boulanger, P., …
Zwanziger, J. W. (2009). ABINIT: First-principles approach to material and
nanosystem properties. Computer Physics Communications, 180(12), 2582–2615.
https://doi.org/10.1016/j.cpc.2009.07.007.
Gorey, T. J., Zandkarimi, B., Li, G., Baxter, E. T., Alexandrova, A. N., & Anderson, S. L.
(2020). Coking-Resistant Sub-Nano Dehydrogenation Catalysts: Pt n Sn x /SiO2 (n =
4, 7). ACS Catalysis, 10(8), 4543–4558. https://doi.org/10.1021/acscatal.0c00668.
Greeley, J., Jaramillo, T. F., Bonde, J., Chorkendorff, I., & Nørskov, J. K. (2006).
Computational high-throughput screening of electrocatalytic materials for hydrogen
evolution. Nature Materials, 5(11), 909–913. https://doi.org/10.1038/nmat1752.
Guo, H., Zhang, B., Qi, Z., Li, C., Ji, J., Dai, T., … Zhang, T. (2017). Valorization of Lignin
to Simple Phenolic Compounds over Tungsten Carbide: Impact of Lignin Structure.
ChemSusChem, 10(3), 523–532. https://doi.org/10.1002/cssc.201601326.
Ha, M.-A., Baxter, E. T., Cass, A. C., Anderson, S. L., & Alexandrova, A. N. (2017). Boron
Switch for Selectivity of Catalytic Dehydrogenation on Size-Selected Pt Clusters on
Al2O3. Journal of the American Chemical Society, 139(33), 11568–11575.
https://doi.org/10.1021/jacs.7b05894.
Ham, D. J., Han, S., Pak, C., Ji, S. M., Jin, S.-A., Chang, H., & Lee, J. S. (2012). High
Electrochemical Performance and Stability of Co-Deposited Pd–Au on Phase-Pure
Tungsten Carbide for Hydrogen Oxidation. Topics in Catalysis, 55(14–15), 922–930.
https://doi.org/10.1007/s11244-012-9875-2.
Hammer, B., Hansen, L. B., & Nørskov, J. K. (1999). Improved adsorption energetics
within density-functional theory using revised Perdew-Burke-Ernzerhof functionals.
Physical Review B, 59(11), 7413–7421. https://doi.org/10.1103/PhysRevB.59.7413.
Han, N., Yang, K. R., Lu, Z., Li, Y., Xu, W., Gao, T., … Sun, X. (2018). Nitrogen-doped
tungsten carbide nanoarray as an efficient bifunctional electrocatalyst for water
splitting in acid. Nature Communications, 9(1), 924. https://doi.org/10.1038/s41467-
018-03429-z.
Complimentary Copy
Harnisch, F., Sievers, G., & Schröder, U. (2009). Tungsten carbide as electrocatalyst for
the hydrogen evolution reaction in pH neutral electrolyte solutions. Applied Catalysis
B: Environmental, 89(3–4), 455–458. https://doi.org/10.1016/j.apcatb.
2009.01.003.
Hatano, Y., Takamori, M., Matsuda, K., Ikeno, S., Fujii, K., & Watanabe, K. (2002). Solid
state reaction between tungsten and amorphous carbon. Journal of Nuclear Materials,
307–311, 1339–1343. https://doi.org/10.1016/S0022-3115(02)00986-8.
Heard, C. J., Hu, C., Skoglundh, M., Creaser, D., & Grönbeck, H. (2016). Kinetic Regimes
in Ethylene Hydrogenation over Transition-Metal Surfaces. ACS Catalysis, 6(5),
3277–3286. https://doi.org/10.1021/acscatal.5b02708.
Huang, J., Hong, W., Li, J., Wang, B., & Liu, W. (2020). High-performance tungsten
carbide electrocatalysts for the hydrogen evolution reaction. Sustainable Energy &
Fuels, 4(3), 1078–1083. https://doi.org/10.1039/C9SE00853E.
Humbert, M. P., Menning, C. A., & Chen, J. G. (2010). Replacing bulk Pt in Pt–Ni–Pt
bimetallic structures with tungsten monocarbide (WC): Hydrogen adsorption and
cyclohexene hydrogenation on Pt–Ni–WC. Journal of Catalysis, 271(1), 132–139.
https://doi.org/10.1016/j.jcat.2010.02.016.
Hunt, S. T., Nimmanwudipong, T., & Román-Leshkov, Y. (2014). Engineering Non-
sintered, Metal-Terminated Tungsten Carbide Nanoparticles for Catalysis.
Angewandte Chemie, 126(20), 5231–5236. https://doi.org/10.1002/ange.201400294.
Hwu, H. H., & Chen, J. G. (2005). Surface chemistry of transition metal carbides. Chemical
Reviews, 105(1), 185–212. https://doi.org/Doi 10.1021/Cr0204606.
Jimenez-Orozco, C., Figueras, M., Flórez, E., Viñes, F., Rodriguez, J. A., & Illas, F. (2022).
Effect of nanostructuring on the interaction of CO 2 with molybdenum carbide
nanoparticles. Physical Chemistry Chemical Physics, 24(27), 16556–16565.
https://doi.org/10.1039/D2CP01143C.
Jimenez-Orozco, C., Flórez, E., Montoya, A., & Rodriguez, J. A. (2019). Binding and
activation of ethylene on tungsten carbide and platinum surfaces. Physical Chemistry
Chemical Physics, 21(31), 17332–17342. https://doi.org/10.1039/C9CP03214B.
Jimenez-Orozco, C., Flórez, E., Viñes, F., Rodriguez, J. A., & Illas, F. (2020). Critical
Hydrogen Coverage Effect on the Hydrogenation of Ethylene Catalyzed by δ-
MoC(001): An Ab Initio Thermodynamic and Kinetic Study. ACS Catalysis, 10(11),
6213–6222. https://doi.org/10.1021/acscatal.0c00144.
Jimenez-Orozco, C., Koverga, A. A., Flórez, E., & Rodriguez, J. A. (2023). Selective
hydrogenation of acetylene to ethylene: Performance of a Pt monolayer over an α-
WC(0001) surface for binding and hydroconversion of acetylene. Surface Science,
728, 122197. https://doi.org/10.1016/j.susc.2022.122197.
Jimenez‐Orozco, C., Flórez, E., & Rodriguez, J. A. (2023). The α‐WC(0001) Surface as a
Hydrogen Sponge: A First Principle Study of H 2 Dissociation and Formation of Low
and High Coverages. ChemCatChem. https://doi.org/10.1002/cctc.202300165.
Jin, H., Chen, J., Mao, S., & Wang, Y. (2018). Transition Metal Induced the Contraction of
Tungsten Carbide Lattice as Superior Hydrogen Evolution Reaction Catalyst. ACS
Applied Materials & Interfaces, 10(26), 22094–22101. https://doi.org/10.1021/
acsami.8b04553.
Jin, N., Yang, Y., Luo, X., Liu, S., Xiao, Z., Guo, P., & Huang, B. (2015). First-principles
Complimentary Copy
calculation of W/WC interface: Atomic structure, stability and electronic properties.

Applied Surface Science, 324, 205–211. https://doi.org/10.1016/j.apsusc.
2014.10.119.
Juneau, M., Yaffe, D., Liu, R., Agwara, J. N., & Porosoff, M. D. (2022). Establishing
tungsten carbides as active catalysts for CO 2 hydrogenation. Nanoscale, 14(44),
16458–16466. https://doi.org/10.1039/D2NR03281C.
Kang, J. S., Kim, J., Lee, M. J., Son, Y. J., Jeong, J., Chung, D. Y., … Sung, Y.-E. (2017).
Electrochemical synthesis of nanoporous tungsten carbide and its application as
electrocatalysts for photoelectrochemical cells. Nanoscale, 9(17), 5413–5424.
https://doi.org/10.1039/C7NR00216E.
Karaboğa, S. (2021). Tungsten(VI) oxide supported rhodium(0) nanoparticles; highly
efficient catalyst for H2 production from dimethylamine borane. International Journal
of Hydrogen Energy, 46(34), 17763–17775. https://doi.org/10.1016/
j.ijhydene.2021.02.188.
Katsounaros, I., Schneider, W. B., Meier, J. C., Benedikt, U., Biedermann, P. U., Cuesta,
A., … Mayrhofer, K. J. J. (2013). The impact of spectator species on the interaction
of H2O2 with platinum – implications for the oxygen reduction reaction pathways.
Physical Chemistry Chemical Physics, 15(21), 8058. https://doi.org/10.1039/
c3cp50649e.
Kelly, T. G., Hunt, S. T., Esposito, D. V., & Chen, J. G. (2013). Monolayer palladium
supported on molybdenum and tungsten carbide substrates as low-cost hydrogen
evolution reaction (HER) electrocatalysts. International Journal of Hydrogen Energy,
38(14), 5638–5644. https://doi.org/10.1016/j.ijhydene.2013.02.116.
Kelly, T. G., Ren, H., & Chen, J. G. (2015). Decomposition pathways of C2 oxygenates on
Rh-modified tungsten carbide surfaces. Surface Science, 640, 89–95.
https://doi.org/10.1016/j.susc.2015.03.008.
Kelly, T. G., Stottlemyer, A. L., Ren, H., & Chen, J. G. (2011). Comparison of O−H, C−H,
and C−O Bond Scission Sequence of Methanol on Tungsten Carbide Surfaces
Modified by Ni, Rh, and Au. The Journal of Physical Chemistry C, 115(14), 6644–
6650. https://doi.org/10.1021/jp112006v.
Kojima, I, Miyazaki, E., Inoue, Y., & Yasumori, I. (1979). Catalytic activities of TiC, WC,
and TaC for hydrogenation of ethylene. Journal of Catalysis, 59(3), 472–474.
https://doi.org/10.1016/S0021-9517(79)80019-6.
Kojima, Isao, Miyakasi, E., Yasunobu, I., & Yasumori, I. (1979). Catalytic Activities of
TiC, WC, and TaC for Hydrogenation of Ethylene. Journal of Catalysis, 59(3), 472–
474.
Koverga, A. A., Flórez, E., Dorkis, L., & Rodriguez, J. A. (2019). CO, CO 2, and H2
Interactions with (0001) and (001) Tungsten Carbide Surfaces: Importance of Carbon
and Metal Sites. The Journal of Physical Chemistry C, 123(14), 8871–8883.
https://doi.org/10.1021/acs.jpcc.8b11840.
Koverga, A. A., Flórez, E., Jimenez-Orozco, C., & Rodriguez, J. A. (2021a). Not all
platinum surfaces are the same: Effect of the support on fundamental properties of
platinum adlayer and its implications for the activity toward hydrogen evolution
reaction. Electrochimica Acta, 368, 137598. https://doi.org/10.1016/j.electacta.
2020.137598.
Complimentary Copy
Koverga, A. A., Flórez, E., Jimenez-Orozco, C., & Rodriguez, J. A. (2021b). Spot the
difference: hydrogen adsorption and dissociation on unsupported platinum and
platinum-coated transition metal carbides. Physical Chemistry Chemical Physics,
23(36), 20255–20267. https://doi.org/10.1039/D1CP02974F.
Koverga, A. A., Flórez, E., & Rodriguez, J. A. (2021). Pushing Cu uphill of the volcano
curve: Impact of a WC support on the catalytic activity of copper toward the hydrogen
evolution reaction. International Journal of Hydrogen Energy, 46(49), 25092–25102.
https://doi.org/10.1016/j.ijhydene.2021.05.055.
Koverga, A. A., Gómez-Marín, A. M., Dorkis, L., Flórez, E., & Ticianelli, E. A. (2020).
Role of Transition Metals on TM/Mo 2 C Composites: Hydrogen Evolution Activity
in Mildly Acidic and Alkaline Media. ACS Applied Materials & Interfaces, 12(24),
27150–27165. https://doi.org/10.1021/acsami.0c04806.
Kresse, G., & Furthmüller, J. (1996). Efficient iterative schemes for ab initio total-energy
calculations using a plane-wave basis set. Physical Review B, 54(16), 11169–11186.
https://doi.org/10.1103/PhysRevB.54.11169.
Kresse, G., & Joubert, D. (1999). From ultrasoft pseudopotentials to the projector
augmented-wave method. Physical Review B, 59(3), 1758–1775.
https://doi.org/10.1103/PhysRevB.59.1758.
Kurlov, A. S., & Gusev, A. I. (2006). Tungsten carbides and W-C phase diagram. Inorganic
Materials, 42(2), 121–127. https://doi.org/10.1134/S0020168506020051.
Kurlov, Alexey S, & Gusev, A. I. (2013). Phases and Equilibria in the W–C and W–Co–C
Systems. In Tungsten Carbides. Structure, Properties and Application in Hardmetals
(1st ed., pp. 5–56). https://doi.org/10.1007/978-3-319-00524-9_2.
Lamb, K. E., Dolan, M. D., & Kennedy, D. F. (2019). Ammonia for hydrogen storage; A
review of catalytic ammonia decomposition and hydrogen separation and purification.
International Journal of Hydrogen Energy, 44(7), 3580–3593.
Lamb, W. F., Wiedmann, T., Pongratz, J., Andrew, R., Crippa, M., Olivier, J. G. J., …
Minx, J. (2021). A review of trends and drivers of greenhouse gas emissions by sector
from 1990 to 2018. Environmental Research Letters, 16(7), 073005.
https://doi.org/10.1088/1748-9326/abee4e.
Lan, R., Irvine, J. T. S., & Tao, S. (2012). Ammonia and related chemicals as potential
indirect hydrogen storage materials. International Journal of Hydrogen Energy, 37(2),
Levy, R., & Boudart, M. (1973). Platinum-Like Behavior of Tungsten Carbide in Surface
Catalysis. Science (New York, N.Y.), 181(4099), 547–549.
Li, Y., Gao, Y., Xiao, B., Min, T., Fan, Z., Ma, S., & Xu, L. (2010). Theoretical study on
the stability, elasticity, hardness and electronic structures of W–C binary compounds.
Journal of Alloys and Compounds, 502(1), 28–37.
https://doi.org/10.1016/j.jallcom.2010.04.184.
Liang, Y., Chen, L., & Ma, C. (2017). Kinetics and thermodynamics of H2O dissociation
and CO oxidation on the Pt/WC (0001) surface: A density functional theory study.
Surface Science, 656, 7–16. https://doi.org/10.1016/j.susc.2016.08.009.
Lin, L., Chen, M., & Wu, L. (2018). Synthesis of Molybdenum–Tungsten Bimetallic
Carbide Hollow Spheres as pH‐Universal Electrocatalysts for Efficient Hydrogen
Complimentary Copy
Evolution Reaction. Advanced Materials Interfaces, 5(23), 1801302.

https://doi.org/10.1002/admi.201801302.
Liu, A. Y., & Cohen, M. L. (1988). Theoretical study of the stability of cubic WC. Solid
State Communications, 67(10), 907–910. https://doi.org/10.1016/0038-
1098(88)90454-1.
Liu, A. Y., Wentzcovitch, R. M., & Cohen, M. L. (1988). Structural and electronic
properties of WC. Physical Review B, 38(14), 9483–9489. https://doi.org/10.1103/
PhysRevB.38.9483.
Liu, Cheng, Wen, Y., Lin, L., Zhang, H., Li, X., & Zhang, S. (2018). Facile in-situ
formation of high efficiency nanocarbon supported tungsten carbide nanocatalysts for
hydrogen evolution reaction. International Journal of Hydrogen Energy, 43(33),
Liu, Cong, Yang, B., Tyo, E., Seifert, S., DeBartolo, J., von Issendorff, B., … Curtiss, L.
A. (2015). Carbon Dioxide Conversion to Methanol over Size-Selected Cu4 Clusters
at Low Pressures. Journal of the American Chemical Society, 137(27), 8676–8679.
Liu, Y., & Mustain, W. E. (2012). Evaluation of tungsten carbide as the electrocatalyst
support for platinum hydrogen evolution/oxidation catalysts. International Journal of
Hydrogen Energy, 37(11), 8929–8938. https://doi.org/10.1016/j.ijhydene.
2012.03.044.
Löfberg, A., Frennet, A., Leclercq, G., Leclercq, L., & Giraudon, J. M. (2000). Mechanism
of WO3 Reduction and Carburization in CH4/H2 Mixtures Leading to Bulk Tungsten
Carbide Powder Catalysts. Journal of Catalysis, 189(1), 170–183.
https://doi.org/10.1006/jcat.1999.2692.
López, M., Broderick, L., Carey, J. J., Viñes, F., Nolan, M., & Illas, F. (2018). Tuning
transition metal carbide activity by surface metal alloying: a case study on CO 2
capture and activation. Physical Chemistry Chemical Physics, 20(34), 22179–22186.
https://doi.org/10.1039/C8CP03648A.
López, M., Viñes, F., Nolan, M., & Illas, F. (2020). Predicting the Effect of Dopants on CO
2 Adsorption in Transition Metal Carbides: Case Study on TiC (001). The Journal of
Physical Chemistry C, 124(29), 15969–15976. https://doi.org/10.1021/
acs.jpcc.0c03893.
Luković, J., Babić, B., Bučevac, D., Prekajski, M., Pantić, J., Baščarević, Z., & Matović,
B. (2015). Synthesis and characterization of tungsten carbide fine powders. Ceramics
International, 41(1), 1271–1277. https://doi.org/10.1016/j.ceramint.
2014.09.057.
Mabuea, B. P., Erasmus, E., & Swart, H. C. (2023). Molybdenum-Tungsten carbides based
electrocatalysts for hydrogen evolution reaction. International Journal of Sustainable
Energy, 42(1), 91–102. https://doi.org/10.1080/14786451.2023.
2176700.
Magazzino, C., Toma, P., Fusco, G., Valente, D., & Petrosillo, I. (2022). Renewable energy
consumption, environmental degradation and economic growth: the greener the
richer? Ecological Indicators, 139, 108912. https://doi.org/10.1016/
j.ecolind.2022.108912.
Maier, S., Stass, I., Cerda, J. I., & Salmeron, M. (2012). Bonding of Ammonia and Its
Complimentary Copy
Dehydrogenated Fragments on Ru(0001). The Journal of Physical Chemistry C,

116(48), 25395–25400. https://doi.org/10.1021/jp308835x.
Márquez-Alvarez, C., Calridge, J. B., York, A. P. E., Sloan, J., & Green, M. L. H. (1997).
Benzene hydrogenation over transition metal carbides. https://doi.org/
10.1016/S0167-2991(97)80047-X.
Marquez-Alvarez, C., Claridge, J., York, A., Sloan, J., & Green, M. (1997). Benzene
hydrogenation over transition metal carbides. In G. F. Froment, B. Delmon, & P.
Grange (Eds.), Studies in Surface Science and Catalysis (Vol. 106, pp. 485–490).
Elsevier Science.
Mattheiss, L. F., & Hamann, D. R. (1984). Bulk and surface electronic structure of
hexagonal WC. Physical Review B, 30(4), 1731–1738. https://doi.org/10.1103/
PhysRevB.30.1731.
Michalsky, R., Zhang, Y.-J., & Peterson, A. A. (2014). Trends in the Hydrogen Evolution
Activity of Metal Carbide Catalysts. ACS Catalysis, 4(5), 1274–1278.
https://doi.org/10.1021/cs500056u.
Møller, K. T., Jensen, T. R., Akiba, E., & Li, H. (2017). Hydrogen - A sustainable energy
carrier. Progress in Natural Science: Materials International, 27(1), 34–40.
https://doi.org/10.1016/j.pnsc.2016.12.014.
Morse, J. R., Juneau, M., Baldwin, J. W., Porosoff, M. D., & Willauer, H. D. (2020). Alkali
promoted tungsten carbide as a selective catalyst for the reverse water gas shift
reaction. Journal of CO2 Utilization, 35, 38–46. https://doi.org/10.1016/
j.jcou.2019.08.024.
Nørskov, J. K., Bligaard, T., Logadottir, A., Kitchin, J. R., Chen, J. G., Pandelov, S., &
Stimming, U. (2005). Trends in the Exchange Current for Hydrogen Evolution.
Journal of The Electrochemical Society, 152(3), J23. https://doi.org/10.1149/
1.1856988.
Pansare, S. S., Torres, W., & Goodwin, J. G. (2007). Ammonia decomposition on tungsten
carbide. Catalysis Communications, 8(4), 649–654. https://doi.org/10.1016/
j.catcom.2006.08.016.
Park, S., Lee, Y.-L., Yoon, Y., Park, S. Y., Yim, S., Song, W., … An, K.-S. (2022).
Reducing the high hydrogen binding strength of vanadium carbide MXene with
atomic Pt confinement for high activity toward HER. Applied Catalysis B:
Environmental, 304, 120989. https://doi.org/10.1016/j.apcatb.2021.120989.
Pašti, I. A., Skorodumova, N. V., & Mentus, S. V. (2015). Theoretical studies in catalysis
and electrocatalysis: from fundamental knowledge to catalyst design. Reaction
Kinetics, Mechanisms and Catalysis, 115(1), 5–32. https://doi.org/10.1007/s11144-
014-0808-x.
Perdew, J. P., Burke, K., & Ernzerhof, M. (1996). Generalized Gradient Approximation
Made Simple. Physical Review Letters, 77(18), 3865–3868. https://doi.org/10.1103/
PhysRevLett.77.3865.
Perdew, J. P., Chevary, J. A., Vosko, S. H., Jackson, K. A., Pederson, M. R., Singh, D. J.,
& Fiolhais, C. (1993). Erratum: Atoms, molecules, solids, and surfaces: Applications
of the generalized gradient approximation for exchange and correlation. Physical
Review B, 48(7), 4978–4978. https://doi.org/10.1103/PhysRevB.48.4978.2.
Pinzón, M., Romero, A., de Lucas-Consuegra, A., de la Osa, A. R., & Sánchez, P. (2022).
Complimentary Copy
COx-free hydrogen production from ammonia at low temperature using Co/SiC

catalyst: Effect of promoter. Catalysis Today, 390–391, 34–47.
https://doi.org/10.1016/j.cattod.2021.12.005.
Porosoff, M. D., Kattel, S., Li, W., Liu, P., & Chen, J. G. (2015). Identifying trends and
descriptors for selective CO2 conversion to CO over transition metal carbides.
Chemical Communications, 51(32), 6988–6991. https://doi.org/10.1039/
C5CC01545F.
Posada-Pérez, S., Ramírez, P. J., Evans, J., Viñes, F., Liu, P., Illas, F., & Rodriguez, J. A.
(2016). Highly Active Au/δ-MoC and Cu/δ-MoC Catalysts for the Conversion of
CO2: The Metal/C Ratio as a Key Factor Defining Activity, Selectivity, and Stability.
Journal of the American Chemical Society, 138(26), 8269–8278.
Posada-Pérez, S., Viñes, F., Ramirez, P. J., Vidal, A. B., Rodriguez, J. A., & Illas, F. (2014).
The bending machine: CO 2 activation and hydrogenation on δ-MoC(001) and β-Mo
2 C(001) surfaces. Phys. Chem. Chem. Phys., 16(28), 14912–14921.
https://doi.org/10.1039/C4CP01943A.
Posada-Pérez, S., Viñes, F., Rodriguez, J. A., & Illas, F. (2015). Fundamentals of Methanol
Synthesis on Metal Carbide Based Catalysts: Activation of CO2 and H2. Topics in
Catalysis, 58(2–3), 159–173. https://doi.org/10.1007/s11244-014-0355-8.
Prats, H., & Stamatakis, M. (2022). Atomistic and electronic structure of metal clusters
supported on transition metal carbides: implications for catalysis. Journal of Materials
Chemistry A, 10(3), 1522–1534. https://doi.org/10.1039/D1TA08468B.
Prats, H., & Stamatakis, M. (2023). Stability and reactivity of metal nanoclusters supported
on transition metal carbides. Nanoscale Advances, 5(12), 3214–3224.
https://doi.org/10.1039/D3NA00231D.
Quaino, P., Juarez, F., Santos, E., & Schmickler, W. (2014). Volcano plots in hydrogen
electrocatalysis – uses and abuses. Beilstein Journal of Nanotechnology, 5, 846–854.
https://doi.org/10.3762/bjnano.5.96.
Rao, X., Lou, Y., Zhou, Y., Zhang, J., & Zhong, S. (2021). First-principles insights into
ammonia decomposition on WC (0001) surface terminated by W and C. Applied
Surface Science, 566, 150635. https://doi.org/10.1016/j.apsusc.2021.150635.
Rehman, A., Alam, M. M., Ozturk, I., Alvarado, R., Murshed, M., Işık, C., & Ma, H.
(2022). Globalization and renewable energy use: how are they contributing to upsurge
the CO2 emissions? A global perspective. Environmental Science and Pollution
Research, 30(4), 9699–9712. https://doi.org/10.1007/s11356-022-22775-6.
Ren, H., Chen, Y., Huang, Y., Deng, W., Vlachos, D. G., & Chen, J. G. (2014). Tungsten
carbides as selective deoxygenation catalysts: experimental and computational studies
of converting C3 oxygenates to propene. Green Chem., 16(2), 761–769.
https://doi.org/10.1039/C3GC41256C.
Rodriguez, J. A., Liu, P., Takahashi, Y., Nakamura, K., Viñes, F., & Illas, F. (2009).
Desulfurization of Thiophene on Au/TiC(001): Au−C Interactions and Charge
Polarization. Journal of the American Chemical Society, 131(24), 8595–8602.
https://doi.org/10.1021/ja901522a.
Sabatier, P. (1920). La catalyse en chimie organique. Encyclopédie Des Sciences Chimique
Appliquées.
Complimentary Copy
Sagadevan, S., Das, I., Singh, P., & Podder, J. (2017). Synthesis of tungsten carbide
nanoparticles by hydrothermal method and its Characterization. Journal of Materials
Science: Materials in Electronics, 28(1), 1136–1141. https://doi.org/10.1007/
s10854-016-5638-3.
Schwarz, K., & Blaha, P. (2003). Solid state calculations using WIEN2k. Computational
Materials Science, 28(2), 259–273. https://doi.org/10.1016/S0927-0256(03)00112-5.
Segall, M. D., Lindan, P. J. D., Probert, M. J., Pickard, C. J., Hasnip, P. J., Clark, S. J., &
Payne, M. C. (2002). First-principles simulation: ideas, illustrations and the CASTEP
code. Journal of Physics: Condensed Matter, 14(11), 2717–2744.
https://doi.org/10.1088/0953-8984/14/11/301.
SEI, IISD, ODI, E3G, & UNEP. (2020). The production gap report: 2020 Special report.
Retrieved from https://productiongap.org/2020report/.
Sharma, S., & Pollet, B. G. (2012). Support materials for PEMFC and DMFC
electrocatalysts—A review. Journal of Power Sources, 208, 96–119.
https://doi.org/10.1016/j.jpowsour.2012.02.011.
Shen, A., & Cao, Y. (2016). Adsorption and Decomposition of NH3 on Ni/Pt(111) and
Ni/WC(001) Surfaces: A First-Principles Study. Chinese Journal of Chemical
Physics, 29(6), 710–716. https://doi.org/10.1063/1674-0068/29/cjcp1604082.
Sheng, T., Lin, X., Chen, Z.-Y., Hu, P., Sun, S.-G., Chu, Y.-Q., … Lin, W.-F. (2015).
Methanol electro-oxidation on platinum modified tungsten carbides in direct methanol
fuel cells: a DFT study. Physical Chemistry Chemical Physics, 17(38), 25235–25243.
https://doi.org/10.1039/C5CP02072G.
Siegel, D. J., Hector, L. G., & Adams, J. B. (2002). Adhesion, stability, and bonding at
metal/metal-carbide interfaces: Al/WC. Surface Science, 498(3), 321–336.
https://doi.org/10.1016/S0039-6028(01)01811-8.
Singla, G., Singh, K., & Pandey, O. P. (2015). Synthesis of carbon coated tungsten carbide
nano powder using hexane as carbon source and its structural, thermal and
electrocatalytic properties. International Journal of Hydrogen Energy, 40(16), 5628–
5637. https://doi.org/10.1016/j.ijhydene.2015.02.127.
Sohail, U., Pervaiz, E., Ali, M., Khosa, R., Shakoor, A., & Abdullah, U. (2022). Role of
tungsten carbide (WC) and its hybrids in electrochemical water splitting application-
A comprehensive review. FlatChem, 35, 100404. https://doi.org/10.1016/
j.flatc.2022.100404.
Soler, J. M., Artacho, E., Gale, J. D., García, A., Junquera, J., Ordejón, P., & Sánchez-
Portal, D. (2002). The SIESTA method for ab initio order- N materials simulation.
Journal of Physics: Condensed Matter, 14(11), 2745–2779. https://doi.org/10.1088/
0953-8984/14/11/302.
Stefan, P. M., Shek, M. L., Lindau, I., Spicer, W. E., Johansson, L. I., Herman, F., …
Brogen, G. (1984). Photoemission study of WC(0001). Physical Review B, 29(10),
5423–5444. https://doi.org/10.1103/PhysRevB.29.5423.
Strielkowski, W., Civín, L., Tarkhanova, E., Tvaronavičienė, M., & Petrenko, Y. (2021).
Renewable Energy in the Sustainable Development of Electrical Power Sector: A
Review. Energies, 14(24), 8240. https://doi.org/10.3390/en14248240.
Su, W., Yan, P., Wei, X., Zhu, X., & Zhou, Q. (2020). Facile one-step synthesis of nitrogen-
doped carbon sheets supported tungsten carbide nanoparticles electrocatalyst for
Complimentary Copy
hydrogen evolution reaction. International Journal of Hydrogen Energy, 45(58),

Sullivan, M. M., Chen, C.-J., & Bhan, A. (2016). Catalytic deoxygenation on transition
metal carbide catalysts. Catalysis Science & Technology, 6(3), 602–616.
https://doi.org/10.1039/C5CY01665G.
Tang, C., Wang, D., Wu, Z., & Duan, B. (2015). Tungsten carbide hollow microspheres as
electrocatalyst and platinum support for hydrogen evolution reaction. International
Journal of Hydrogen Energy, 40(8), 3229–3237.
Tian, X., Zhao, P., & Sheng, W. (2019). Hydrogen Evolution and Oxidation: Mechanistic
Studies and Material Advances. Advanced Materials, 31(31), 1808066.
https://doi.org/10.1002/adma.201808066.
Tong, Y.-J., Wu, S.-Y., & Chen, H.-T. (2018). Adsorption and reaction of CO and H2O on
WC(0001) surface: A first-principles investigation. Applied Surface Science, 428,
579–585. https://doi.org/10.1016/j.apsusc.2017.09.191.
Trasatti, S. (1972). Work function, electronegativity, and electrochemical behaviour of
metals. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry,
39(1), 163–184. https://doi.org/10.1016/S0022-0728(72)80485-6.
Tu, X., Shan, Q., Li, Z., Zhang, F., Wang, Z., & Yan, Z. (2019). The adsorption properties
of Fe, Co, and Ni atoms on α -WC(0001) surface: a first principles study. Materials
Research Express, 6(7), 075609. https://doi.org/10.1088/2053-1591/
ab11b0.
van Asselt, H. (2021). Governing fossil fuel production in the age of climate disruption:
Towards an international law of ‘leaving it in the ground.’ Earth System Governance,
9, 100118. https://doi.org/10.1016/j.esg.2021.100118.
Vasić Anićijević, D. D., Nikolić, V. M., Marčeta-Kaninski, M. P., & Pašti, I. A. (2013). Is
platinum necessary for efficient hydrogen evolution? – DFT study of metal
monolayers on tungsten carbide. International Journal of Hydrogen Energy, 38(36),
Vasić, D. D., Pašti, I. A., & Mentus, S. V. (2013). DFT study of platinum and palladium
overlayers on tungsten carbide: Structure and electrocatalytic activity toward
hydrogen oxidation/evolution reaction. International Journal of Hydrogen Energy,
38(12), 5009–5018. https://doi.org/10.1016/j.ijhydene.2013.02.020.
Vértes, G., Horányi, G., & Szakács, S. (1973). Selective catalytic behaviour of tungsten
carbide in the liquid-phase hydrogenation of organic compounds. J. Chem. Soc.,
Perkin Trans. 2, (10), 1400–1402. https://doi.org/10.1039/P29730001400.
Vidick, B., Lemaître, J., & Leclercq, L. (1986). Control of the catalytic activity of tungsten
carbides III. Activity for ethylene hydrogenation and cyclohexane dehydrogenation.
Journal of Catalysis, 99(2), 439–448. https://doi.org/10.1016/
0021-9517(86)90368-4.
Vijayakumar, P., Senthil Pandian, M., Lim, S. P., Pandikumar, A., Huang, N. M.,
Mukhopadhyay, S., & Ramasamy, P. (2015). Facile synthesis of tungsten carbide
nanorods and its application as counter electrode in dye sensitized solar cells.
Materials Science in Semiconductor Processing, 39, 292–299. https://doi.org/
10.1016/j.mssp.2015.05.023.
Complimentary Copy
Viñes, F., Sousa, C., Liu, P., Rodriguez, J. A., & Illas, F. (2005). A systematic density
functional theory study of the electronic structure of bulk and (001) surface of
transition-metals carbides. The Journal of Chemical Physics, 122(17), 174709.
https://doi.org/10.1063/1.1888370.
Wang, K.-F., Sun, G.-D., Wu, Y.-D., & Zhang, G.-H. (2019). Fabrication of ultrafine and
high-purity tungsten carbide powders via a carbothermic reduction–carburization
process. Journal of Alloys and Compounds, 784, 362–369. https://doi.org/10.1016/
j.jallcom.2019.01.055.
Wang, L., Li, Z., Wang, K., Dai, Q., Lei, C., Yang, B., … Hou, Y. (2020). Tuning d-band
center of tungsten carbide via Mo doping for efficient hydrogen evolution and Zn–
H2O cell over a wide pH range. Nano Energy, 74, 104850. https://doi.org/10.1016/
j.nanoen.2020.104850.
Wang, Y., Song, S., Maragou, V., Shen, P. K., & Tsiakaras, P. (2009). High surface area
tungsten carbide microspheres as effective Pt catalyst support for oxygen reduction
reaction. Applied Catalysis B: Environmental, 89(1–2), 223–228.
https://doi.org/10.1016/j.apcatb.2008.11.032.
Wang, Y., Song, S., Shen, P. K., Guo, C., & Li, C. M. (2009). Nanochain-structured
mesoporous tungsten carbide and its superior electrocatalysis. Journal of Materials
Chemistry, 19(34), 6149. https://doi.org/10.1039/b902744k.
Wannakao, S., Artrith, N., Limtrakul, J., & Kolpak, A. M. (2015). Engineering Transition-
Metal-Coated Tungsten Carbides for Efficient and Selective Electrochemical
Reduction of CO 2 to Methane. ChemSusChem, 8(16), 2745–2751.
https://doi.org/10.1002/cssc.201500245.
Wei, X., & Li, N. (2019). Tungsten carbide/carbon composites coated with little platinum
nano particles derived from the redox reaction between in-situ synthesized WC1−x
and chloroplatinic acid as the electrocatalyst for hydrogen evolution reaction. Applied
Surface Science, 463, 1154–1160. https://doi.org/10.1016/j.apsusc.
2018.09.043.
Wu, H., Wang, Q., Qin, M., Yin, R., Zhang, Z., Jia, B., & Qu, X. (2020). Synthesis of
tungsten carbide nanopowders by direct carbonization of tungsten oxide and carbon:
Effects of tungsten oxide source on phase structure and morphology evolution.
Ceramics International, 46(7), 8787–8795. https://doi.org/10.1016/j.ceramint.
2019.12.118.
Wu, S.-Y., & Ho, J.-J. (2012). Adsorption, Dissociation, and Hydrogenation of CO 2 on
WC(0001) and WC-Co Alloy Surfaces Investigated with Theoretical Calculations.
The Journal of Physical Chemistry C, 116(24), 13202–13209. https://doi.org/
10.1021/jp302901r.
Wu, Z., Yang, Y., Gu, D., Li, Q., Feng, D., Chen, Z., … Zhao, D. (2009). Silica-Templated
Synthesis of Ordered Mesoporous Tungsten Carbide/Graphitic Carbon Composites
with Nanocrystalline Walls and High Surface Areas via a Temperature-Programmed
Carburization Route. Small, 5(23), 2738–2749.
https://doi.org/10.1002/smll.200900523.
Xi, Y., Huang, L., Forrey, R. C., & Cheng, H. (2014). Interactions between hydrogen and
tungsten carbide: a first principles study. RSC Adv., 4(75), 39912.
https://doi.org/10.1039/C4RA06225F.
Complimentary Copy
Xiong, L., Zheng, L., Liu, C., Jin, L., Liu, Q., & Xu, J. (2015). Tungsten Carbide
Microspheres with High Surface Area as Platinum Catalyst Supports for Enhanced
Electrocatalytic Activity. Journal of The Electrochemical Society, 162(4), F468–
F473. https://doi.org/10.1149/2.0961504jes.
Yan, M., Zhao, Z., Wang, T., Chen, R., Zhou, C., Qin, Y., … Yang, Y. (2022). Synergistic
Effects in Ultrafine Molybdenum–Tungsten Bimetallic Carbide Hollow Carbon
Architecture Boost Hydrogen Evolution Catalysis and Lithium‐Ion Storage. Small,
18(37), 2203630. https://doi.org/10.1002/smll.202203630.
Yan, Y., Zhang, L., Qi, X., Song, H., Wang, J.-Y., Zhang, H., & Wang, X. (2012).
Template-Free Pseudomorphic Synthesis of Tungsten Carbide Nanorods. Small,
8(21), 3350–3356. https://doi.org/10.1002/smll.201200877.
Yang, B., Liu, C., Halder, A., Tyo, E. C., Martinson, A. B. F., Seifert, S., … Vajda, S.
(2017). Copper Cluster Size Effect in Methanol Synthesis from CO2. The Journal of
Physical Chemistry C, 121(19), 10406–10412. https://doi.org/10.1021/acs.jpcc.
7b01835.
Yu, G.-Q., Huang, B.-Y., Chen, S.-M., Liao, J.-W., Yin, W.-J., Teobaldi, G., & Li, X.-B.
(2021). The Combined Role of Faceting and Heteroatom Doping for Hydrogen
Evolution on a WC Electrocatalyst in Aqueous Solution: A Density Functional Theory
Study. The Journal of Physical Chemistry C, 125(8), 4602–4613.
https://doi.org/10.1021/acs.jpcc.0c11104.
Yu, W., Mellinger, Z. J., Barteau, M. A., & Chen, J. G. (2012). Comparison of Reaction
Pathways of Ethylene Glycol, Acetaldehyde, and Acetic Acid on Tungsten Carbide
and Ni-Modified Tungsten Carbide Surfaces. The Journal of Physical Chemistry C,
116(9), 5720–5729. https://doi.org/10.1021/jp210756f.
Yuan, X., Su, C.-W., Umar, M., Shao, X., & LOBONŢ, O.-R. (2022). The race to zero
emissions: Can renewable energy be the path to carbon neutrality? Journal of
Environmental Management, 308, 114648. https://doi.org/10.1016/j.jenvman.
2022.114648.
Zhang, Jianfeng, Hassan Saeed, M., & Li, S. (2018). Recent progress in development of
high-performance tungsten carbide-based composites. In Advances in Ceramic Matrix
Composites (pp. 307–329). https://doi.org/10.1016/B978-0-08-102166-8.00013-X.
Zhang, Jinhua, & She, Y. (2020a). Decomposition mechanism of HCOOH on Pt/WC(0001)
surfaces: a density functional theory study. Molecular Simulation, 46(13), 947–956.
https://doi.org/10.1080/08927022.2019.1663845.
Zhang, Jinhua, & She, Y. (2020b). Mechanism of methanol decomposition on the
Pd/WC(0001) surface unveiled by first-principles calculations. Frontiers of Chemical
Science and Engineering, 14(6), 1052–1064. https://doi.org/10.1007/
s11705-019-1908-y.
Zhang, Jinhua, & She, Y. (2020c). Unveiling the decomposition mechanism of formic acid
on Pd/WC(0001) surface by using density function theory. Chinese Journal of
Catalysis, 41(3), 415–425. https://doi.org/10.1016/S1872-2067(19)63463-7.
Zhang, L., Yan, L., Lu, J., Zhang, Y., & Yin, Y. (2022). First-principles calculations of CO
and CH3OH adsorption on Pt monolayer modified WC (0 0 0 1) surface.
Computational and Theoretical Chemistry, 1207, 113510. https://doi.org/10.1016/
j.comptc.2021.113510.
Complimentary Copy
Zhang, T., Holiharimanana, D., Yang, X., & Ge, Q. (2020). DFT Study of Methane
Activation and Coupling on the (0001) and (112̅0) Surfaces of α- WC. The Journal of
Physical Chemistry C, 124(49), 26722–26729. https://doi.org/10.1021/
acs.jpcc.0c06928.
Zhang, X., Chen, Y., & Yang, Z. (2019). Au monolayer on WC(0001) with enhanced
activity towards NO oxidation: A theoretical study. Applied Surface Science, 481,
369–373. https://doi.org/10.1016/j.apsusc.2019.03.117.
Zhang, X., Lu, Z., & Yang, Z. (2016a). A comparison study of oxygen reduction on the
supported Pt, Pd, Au monolayer on WC(0001). Journal of Power Sources, 321, 163–
173. https://doi.org/10.1016/j.jpowsour.2016.04.135.
Zhang, X., Lu, Z., & Yang, Z. (2016b). A theoretical understanding on the CO-tolerance
mechanism of the WC(0001) supported Pt monolayer: Some improvement strategies.
Applied Surface Science, 389, 455–461. https://doi.org/10.1016/j.apsusc.2016.
07.133.
Zhang, X., Yang, Z., & Wu, R. (2018). A Au monolayer on WC(0001) with unexpected
high activity towards CO oxidation. Nanoscale, 10(10), 4753–4760.
https://doi.org/10.1039/C7NR09498A.
Zhang, Y., & Yang, Z. (2019). High activity of Au monolayer doped by Pt atom on WC
(0001) surface towards H2 dissociation and high tolerance of sulfur poisoning. Journal
of Alloys and Compounds, 775, 330–334. https://doi.org/10.1016/j.jallcom.
2018.10.141.
Zhao, W., Guan, Z., Li, D., Wang, B., Fan, M., & Zhang, R. (2022). Syngas Conversion to
C 2 Species over WC and M/WC (M = Cu or Rh) Catalysts: Identifying the Function
of Surface Termination and Supported Metal Type. ACS Applied Materials &
Interfaces, 14(17), 19491–19504. https://doi.org/10.1021/acsami.2c02217.
Zhao, Y., Zhang, X., & Yang, Z. (2019). Activation mechanisms of silver toward CO
oxidation by tungsten carbide substrate: A density functional theory study. Physics
Letters A, 383(20), 2436–2442. https://doi.org/10.1016/j.physleta.2019.04.062.
Zhao, Y., Zhang, X., & Yang, Z. (2020). Efficient capturing and oxidation of CO through
bimetallic surface alloying on WC (0001). Journal of Alloys and Compounds, 844,
156125. https://doi.org/10.1016/j.jallcom.2020.156125.
Complimentary Copy
Chapter 2
Advances in Cemented Carbides for

Metal Machining
Jialin Sun1,2,*
and Jun Zhao3
1School of Mechanical, Electrical & Information Engineering, Shandong University
(Weihai), Weihai, Shandong, China
2Shenzhen Research Institute of Shandong University, Shenzhen, China
3Key Laboratory of High Efficiency and Clean Mechanical Manufacture of MOE,
School of Mechanical Engineering, Shandong University, Jinan, Shandong, China
Abstract
Traditionally, cemented carbide is essentially a composite of hard carbide

phase (WC) and the metal binder phase (Co). Cemented carbide performs
the dominant role in machining tool market, however, its mutually
exclusive mechanical properties (hardness and toughness, strength and
wear resistance, etc.) together with unsatisfactory high-temperature
performances determine its poor adaptability to the heterogeneous
thermal-mechanical-chemical multi-field coupling and interaction during
high-speed machining process. This chapter attempts to comprehensively
summarize the current advances of nanostructured cemented carbide,
functionally graded cemented carbide and cemented carbide with
alternative binder to Co, so as to provide reference for those who would
like to enhance the performance of cemented carbide to meet the
customized requirement for high-speed machining.
Keywords: machining tool materials, nanostructured cemented carbide,

functionally graded cemented carbide, alternative binder to Co
*
Corresponding Author’s Email: sunjialin@sdu.edu.cn.

ISBN: 979-8-89113-221-4
Complimentary Copy
86 Jialin Sun and Jun Zhao
Introduction
As suggested by Oakley (1964) in Man the tool-maker, human beings are

progressing gradually with the invention of new tool materials. In some sense,
the development history of metal machining could be defined as that of cutting
tool materials. Scanning the developing history of tool materials (Figure 1)
from carbon steel to high-speed steel, and to cemented carbide, ceramics,
polycrystalline diamond, etc. we can see that the occurrences of new tool
materials have contributed to the significant enhancement of cutting efficiency
and tool life. For example, just in the first year of high-speed steel tool
appearance, the American machinery manufacturing industry increased its
output value by US $8 billion through inputting US $20 million on developing
high-speed steel cutting tools. The emergence of high-speed steel cutting tool
was hailed as machines replacing horses and rotary motion replacing
reciprocating motion. Since then, the emergence of cemented carbide cutting
tool is another milestone in the history of cutting processing, and its impact is
as great as that of high-speed steel cutting tools. Cemented carbide cutting tool
further innovated machining work through achieving steel machining speeds
of 100 to 150 m/min, approximately four times of that of high-speed steel
cutting tool (20 to 40 m/min) (Tsuda, 2016). From the perspective of historical
chronology, the leading elements in production and life have always been used
to name the era of human development, such as the stone age, the bronze age,
the iron age, the steel age, etc. There is no doubt that tungsten is the leading
element of manufacturing production tools in current society. Therefore, at
some point, current society is in the era of tungsten or cemented tungsten
carbide as illustrated in Figure 2.
Cemented carbides or hardmetals have enjoyed the proud history since it
was invented in 1923 by Karl Schroeter at Osram Studiengesellschaft and
placed on the market as a cutting tool by Krupp AG in 1927 in Germany
(Tsuda, 2016). It has since been developed as a base material for cutting tools.
Traditionally, cemented carbide is essentially a composite of hard carbide
phase (WC) and the metal binder phase (Co) (Sun et al., 2019). The hard
carbide phase endows the composite excellent hardness, strength and wear
resistance, whereas the metallic binder phase imparts the fracture toughness
and impact resistance of the material. The most notable characteristic of WC-
Co family is that it has a combination of strength and toughness, making them
uniquely different from either ductile metal alloys or brittle ceramic materials
(Figure 3) (Ashby, 2009). Specifically, WC-Co is in general harder and more
brittle than metal alloys, but it is tougher and more impact-resistance than
Complimentary Copy
Advances in Cemented Carbides for Metal Machining 87
ceramic materials as shown in Figure 3, which makes it unique and

indispensable as a tool material. For example, almost all indexable inserts
were composed of cemented carbide as illustrated in Figure 4. To achieve the
outstanding combination of mechanical properties, the role of metallic binder
in cemented carbide is crucial. Metallic binder is not only important for
hardness and fracture toughness, but also critical to thermal properties,
corrosion resistance, and compatibility to environment, all of which in
combination affect the performance of cemented carbide as real industrial
tools.
Figure 1. Historical development of tool materials (Abele, 2007; Zhao 2014).
Figure 2. Human development named as leading elements in production.
Complimentary Copy
Figure 3. Ashby diagrams for materials. Left: Young’s modulus v.s. strength, right:
wear-rate constant v.s. hardness. (Ashby, 2009).
74%
8%
3%
Cermet 15%
Coated cemented carbide
Cemented carbides
Other materials
Figure 4. Percentages of indexable insert materials (Tsuda, 2016).
As implied above, Co is by far the most commonly employed binder phase

due to a combination of fundamentally synergistic reasons including the
favorable wettability of Co on WC, interfacial strength between WC and Co,
the plasticity of Co phase in the composite, temperature-dependent solubility
coupled with the self strength and wear resistance of Co. However, the
addition of Co lowers the hardness, elevated temperature strength, and the
oxidation resistance of cemented carbide matrix. The optimum Co content in
WC-Co depends on specific requirements of specific applications.
Furthermore, excessive addition of Co is detrimental to thermal fatigue
resistance of WC-Co, resulting from the mismatch of the coefficient thermal
expansion between Co and WC. Besides, sever adhesive wear occurs easily to
rake face of WC-Co tool during machining high-plasticity hard-to-cut
materials as pure iron, because of the existence of Co with low melting point
(Sun et al., 2016). Consequently, traditional WC-Co tool was generally
Complimentary Copy
employed in medium or low-speed machining with the assistance of cutting

fluid as shown in Figure 5.
Cemented carbide performs the dominant role in machining tool market,
however, its mutually exclusive mechanical properties (hardness and
toughness, strength and wear resistance, etc.) together with unsatisfactory
high-temperature performances determine its poor adaptability to the
heterogeneous thermal-mechanical-chemical multi-field coupling and
interaction during high-speed machining process. In the last decades, both the
research community and industry have continuously enhanced the
performance of cemented carbide to meet the requirement of high-speed
machining. Cemented carbide with alternative binder to Co, functionally
graded cemented carbide and nanostructured cemented carbide were
developed to further enhance the machining efficiency and service life of
cemented carbide cutting tool. This chapter attempts to comprehensively
summarize the current advances of functionally graded cemented carbides,
nanostructured cemented carbides and alternative binder for cemented
carbides, so as to provide reference for those who would like to enhance the
performance of cemented carbides with better reliability and prepare the
material in a way that is environment friendly, harmless to human health and
low in production cost. Sections 2, 3, 4 discuss the design and fabrication of
nanosized cemented carbide, functionally graded cemented carbide as well as
cemented carbide with alternative biner to Co, respectively.
Figure 5. Effect of tool material on machining speed (Stephenson and

Agapiou, 1997).
Complimentary Copy
Figure 6. The percent of densification of WC-Co as a function of the temperature

during continuous heating for various initial particle sizes (Maheshwari et al., 2007).
Development of Nanosized Cemented Carbides
The mechanical properties of cemented carbide matrix strongly depend on the

grain size of WC. Generally, reduction of grain size is rather effective in
enhancing the hardness, strength and wear resistance of hardmetal.
Nanocrystalline cemented carbide is expected to perform enhanced machining
efficiency and service life resulting from its dramatically improved
mechanical properties. However, while initially appealing, the development
of true nanosized cemented carbide (WC grain size < 100 nm) is still even
more challenging, due to the difficulties of retaining nano grain size in the
bulk product after sintering of nanosized powders. The advent of nanosized
cemented carbide era has yet to occur on an industrial scale. This section
focuses on the sintering and mechanical properties of nanosized cemented
carbides.
Sintering of Nanosized Cemented Carbides
Based on various sintering models, from the two-sphere model for the initial
sintering stage to the microstructural model for the intermediate sintering
stage, sintering temperature strongly depends on the grain size. This is
Complimentary Copy
especially true for nanosized cemented carbides. Fang et al. (2009) and
Maheshwari et al. (2007) performed a comprehensive study on the
densification of WC-10wt.% Co powders ranging in size from 10nm to 30μm.
As demonstrated in Figure 6, nanopowders (10nm) achieve over 90%
densification at 1200°C, while coarser powder is just beginning to densify. It
is proposed that nanosized WC-Co powders started to densify at 600°C, while
submicron-sized powders began at 1100°C and regular micro-sized powders
at 1320°C (WC-Co liquidus point), further conforming the effect of initial
powder size especially nanoscale on the onset sintering temperature of
cemented carbides. Based on this theory, the nanosized cemented carbide
could be consolidated in solid phase at a lower sintering temperature. While
initially appealing, it is found that grain growth of nanosized WC powders did
perform rapid stage before achieving the liquid phase sintering temperature,
indicating that the occurrence of rapid grain growth process of nano WC
powders was in solid phase sintering stage (Fang et al., 2005). Furthermore,
based on Gibbs-Thomson effect, nanosized cemented carbide performs
accelerated solution/re-precipitation and re-arrangement/ coalescence
processes during liquid phase sintering stage, consequently resulting in
significant grain growth (Ren et al., 2013). Therefore, the preparation of
nanosized cemented carbide is really a big challenge to achieve full
densification with initial nanosized powders employing conventional
fabrication process.
Generally speaking, there are two feasible strategies to achieve the full
density of nanosized cemented carbide free of grain growth: 1) employing
advanced sintering techniques; 2) incorporating grain growth inhibitor.
The advanced sintering techniques, such as spark plasma sintering (SPS),
reactive spark plasma sintering (RSPS), high-frequency induction-heated
sintering (HFIHS) as well as pulsed current active sintering (PCAS), have
been employed in laboratory scale to prepare nanosized cemented carbide.
Particularly, SPS, also named electric pulse assisted consolidation (EPAC) or
pulsed electric current sintering (PECS), is currently the most applied sintering
method to consolidate nanosized cemented carbide. In the early 1960s, Inoue
et al. (1966) proposed the concept of SPS based on the idea of employing
plasma on electric discharge machine for sintering ceramics and metals. The
concept received further development from the mid 1980s to the early 1990s.
It was in 1998 that SPS was first experimentally verified to enhance the
densification of advanced materials (Mishra et al., 1998). As demonstrated in
Figure 7, SPS, applying pulsed electrical fields together with resistance
heating and pressure, can densify materials rapidly, uniformly and thoroughly
Complimentary Copy
as a function of the large pulse direct current during heat treatment of powders
in the graphite die. The external field is prone to enhance the mass transport
during the sintering process, and the effect can be determined through the
electro migration theory (Munir et al., 2006):
𝐷𝑖 𝐶𝑖 𝑅𝑇 𝜕𝑙𝑛𝐶𝑖
𝐽𝑖 = − 𝑅𝑇
[ ð𝑥
+ 𝐹𝑧 ∗ 𝐸] (1)
where Ji is the flux of the diffusing ith species, Di is the diffusivity of ith
species, Ci is the concentration of ith species, F is Faraday’s constant, z∗ is the
effective charge on the diffusing species, E is the field, R is the universal gas,
and T is absolute temperature.
On the other hand, the grain growth of cemented carbide may well be
impeded through incorporating suitable grain growth inhibitors, such as VC,
Cr3C2, TaC, NbC, ZrC and their certain combinations. The most efficient
inhibitors are VC, Cr3C2 and their certain combinations, due to that they enjoy
excellent solubility and mobility in Co binder at low temperatures. The mostly
accepted mechanism of grain growth inhibition is that the inhibitors retard the
dissolution-reprecipitation process of WC grains through dissolving in the
binder and segregating at the WC-Co interfaces. Furthermore, combined
addition of VC and Cr3C2 with an appropriate ratio performed a more
pronounced effectiveness on inhibiting grain growth of WC than single
addition of VC or Cr3C2 did (Sun et al., 2011). Table 1 summarizes the
densification, grain sizes as well as mechanical properties of cemented
carbides obtained through various sintering techniques.
Mechanical Properties of Nanosized Cemented Carbides
Hardness and fracture toughness, the two basic mechanical properties of

cemented carbides, are the foundation of other mechanical responses including
transverse rupture strength, impact resistance as well as wear resistance.
Hardness represents the stress standing for the resistance against non-
recoverable or plastic deformation, whereas fracture toughness characterizes
the material’s resistance to crack propagation. Hardness and fracture
toughness are considered to be a conflict with respect to cemented carbides, in
other words, compromise is always in cemented carbides with either hardness
or fracture toughness set aside.
Complimentary Copy
Table 1. The densification, grain sizes as well as mechanical properties of cemented carbides obtained through various
sintering techniques
Heating Relative Fracture

Sintering Temperature Pressure Starting powder Grain Hardness
rate density toughness
process and holding time (MPa) and grain size size (nm) (GPa)
(℃/min) (%) (MPa·m1/2)
HP (Jia et al., 1300℃/90min N/A 25 WC-11Co, 80nm 99.9 700 92HRA N/A
2007)
HP (El- 1700℃/43ks N/A 1500 WC-14Co, 7nm 100 95 11 14
Eskandarany et
al., 2000)
RHP 1300℃/15min 120 35 WC-10Co-0.8VC- 99.9 250 93.6HRA N/A
(Sun et al., 2003) 0.2Cr3C2, 32nm
PS (Mahmoodan 1410℃/60min N/A N/A WC-10Co-0.7VC- 94 380 18.3 8.7
et al., 2011) 0.6TaC, 50nm
PS (Aleksandrov 1420℃/80min 5 N/A WC-6Co-0.41VC- 98.9 195 22.4 9.13
Fabijanić et al., 0.8Cr3C2, 95nm
2016)
PS (Bonache et 1400℃/60min 10 N/A WC-12Co, 40- 100.73 720 16.6 10.2
al., 2011) 80nm
PS (Bonache et 1400℃/30min 10 N/A WC-12Co, 40- 99.2 747 15.3 12.8
al., 2011) 80nm
SPS (Bonache et 1100℃/5min 100 80 WC-12Co, 40- 99.94 216 18.5 10.6
al., 2011) 80nm
SPS (Bonache et 1100℃/5min 100 80 WC-12Co-1VC, 98.95 154 20.4 10.1
Complimentary Copy
al., 2011) 40-80nm
SPS (Bonache et 1100℃/5min 100 80 WC-12Co-1Cr3C2, 99.79 207 19.1 10.4
al., 2011) 40-80nm
SPS (Al-Aqeeli, 1300℃/10min 100 50 WC-12Co-0.8VC- 99.3 50 17.2 12.5
2015) 0.2Cr3C2, 40-80nm
Table 1. (Continued)
Heating Relative Fracture

Sintering Temperature Pressure Starting powder Grain Hardness
rate density toughness
process and holding time (MPa) and grain size size (nm) (GPa)
(℃/min) (%) (MPa·m1/2)
SPS (Wei et al., 1160℃/10min 100 60 WC-10Co-0.2VC- N/A 350 17.4 12.1
2012) 0.8Cr3C2, 190nm
SPS (Sun et al., 1100℃/5min N/A 25 WC-11Co, 80nm 100 780 N/A N/A
2007)
SPS (Cha et al., 1000℃/10min 100 100 WC-10Co, 100nm 99 300 17.4 12
2003)
SPS (Shi et al., 1100℃/10min N/A 50 WC-6.29Co, 30nm 99.1 350 98HRA N/A
2005)
SPS (Huang et 1240℃/2min 100 60 WC-12Co, 50nm N/A 280 15.6 9.4
al., 2007)
TSSPS (Wang et 1300℃/3min- 100 30 WC-12Co-0.4VC, 99.49 271 18.06 12.25
al., 2019) 1200℃/5min 60nm
HFIHS (Kim et 1200℃/55s 100 60 WC-12Co, 100nm 99.9 240 19.2 13.5
al., 2007)
PPS (Michalski 1100℃/5min 600 60 WC-12Co, 40- 99 50 23 15.3
and Siemiaszko, 80nm
2007)
PPS (Kupczyk, 1247℃/8.3min N/A 60 WC-5Co, 40-80nm 99.9 150-300 21.4 N/A
2015)
Complimentary Copy
Figure 7. Fracture toughness versus hardness relationship of WC-Co materials using

nanosized WC-Co powders as listed in Table 1.
Figure 7 demonstrated fracture toughness versus hardness relationship of

WC-Co materials using nanosized WC-Co powders as listed in Table 1. As
shown in Figure 7 and Table 1, the decreased grain size contributed to the
enhancement of hardness of cemented carbides, which was well in agreement
with Hall-Petch relationship. Nevertheless, the effect of grain size on fracture
toughness was not clear according to Figure 7. Though employing nanosized
starting powders, most sintered bulk cemented carbide did exhibit microsized
grain size. For traditional cemented carbides, the fracture toughness improved
with the increase of grain size. However, as illustrated in Figure 7, the true
nanosized cemented carbide (50nm, indicated by the arrow) enjoyed the
optimal combination of fracture toughness and hardness. For example, in
terms of WC-12Co samples, the sintered microsized (747nm), submicrosized
(280nm, 240nm) and nanosized (50nm) ones possessed hardness of 15.3, 15.6,
19.2, 23 GPa and fracture toughness of 12.8, 9.4, 13.5, 15.3 MPa·m1/2,
respectively.
As well known that the primary tool for Ti6Al4V titanium alloy
machining is uncoated straight cemented carbide, which exhibited better
cutting performance than high-speed steel, coated carbide, cermet, and
ceramic cutting tool. As presented in Figure 8, the tool degradation
mechanisms included the impact of wear mechanisms on the tool material, the
involvement of workpiece in the interaction, as well as the complex interplay
between wear mechanisms and interactions. Based on this analysis, the
Complimentary Copy
mechanical properties of tool materials critically influenced the machining

performance of the cutting tool. As discussed above, nanosized cemented
carbides performed superior mechanical properties to traditional ones,
consequently, nanosized cemented carbides should be the most potential tool
for the high-speed machining of titanium alloy.
Development of Functionally Graded Cemented Carbide
Functionally graded cemented carbide (FGCC), developed by Sandvik in the

1980s, offers a solution to the trade-off of fracture toughness and hardness
through varying the content or/and grain size of the components from surface
to the core in the sintered samples. Therefore, compared with traditional
cemented carbide, FGCC cutting tool performs superior adaptability and
resistance to thermal-mechanical-chemical multi-field coupling and
interaction during high-speed machining process. This section focuses on the
fabrication and mechanical properties of FGCC.
Figure 8. Graphic of the degradation mechanisms in cemented carbide when

machining Ti6Al4V (Lindvall et al., 2021).
Complimentary Copy
Figure 9. Sketch diagram of the cross-section of typical WC-Co dual phase

cemented carbide button (Ren et al., 2013; Zhang et al., 2008).
Fabrication of Functionally Graded Cemented Carbide
According to the formation mechanism of gradient structure, the preparation

methods of FGCC could be divided into transmission and construction
methods. Transmission method is to generate gradient structure in cemented
carbide by means of fluid flow, atomic diffusion or heat transfer. At present,
two major prefabricated component systems have been developed: cemented
carbide with non-equilibrium carbon and nitrogen-containing cemented
carbide. The former can prepare so-called dual-phase carbide (Figure 9) for
rock drilling tools through carburization process, while the latter can realize
nitridation or denitrification according to the difference between nitrogen
balance partial pressure in the material and environmental nitrogen partial
pressure, forming a hardened layer with cubic phase rich at the surface or a
ductile layer with binder phase rich at the surface.
Construction method is to accurately stack certain component in powder
compact based on the desired gradient structure before sintering process.
Compared with transmission method, the construction method is simple and
flexible. The preparation methods mainly include hot pressing sintering, spark
plasma sintering, microwave sintering and electrophoretic deposition. As the
solid phase sintering usually leads to insufficient densification, FGCC is
generally manufactured through liquid phase sintering. However, during
liquid phase sintering, the liquid phase could easily migrate, resulting in the
elimination of any initial gradient of Co content built in the powder compact.
It is generally preferred that the migration pressure of liquid phase is
Complimentary Copy
dependent on three key factors including the volume fraction of liquid Co, WC
grain size and C content (Fan et al., 2013). As demonstrated in Figure 10, other
things being equal, Co will migrate from high-Co region to low-Co region,
from coarse-grain region to fine-grain region, from region with excessive C to
region with deficient C. Sun et al. (Sun and Zhao, 2018; Sun et al., 2018)
proposed that graphene with a predesigned gradient opposite the predesigned
cobalt gradient can maximally enhance the stability of predesigned Co
gradient during liquid phase sintering process. It is obvious that the graphene-
free specimen (F-FGCC) presented a complete loss of predesigned Co
gradient, whilst the graphene reinforced sample (M-FGCC) maintained the
predesigned Co gradient perfectly (Figure 11). The major Co gradient stability
enhancing mechanisms were graphene preferential orientation, graphene
induced generation of the liquid Co phase and graphene wrapping matrix
grains.
The migration direction

of Co
More liquid Co Less liquid Co
Coarser WC Finer WC
Higher C content Lower C content
Figure 10. Direction of Co migration dependent on the gradients of liquid-Co

volume, WC-grain size and C content in liquid Co phase (Fan et al., 2013).
Complimentary Copy
F-FGCC
15 M-FGCC
Co content (wt.%) 10
5 Co 10 Co 15 Co
0.0 0.5 1.0 1.5 2.0 2.5 3.0

Depth (mm)
Figure 11. Effect of graphene on the Co gradient after liquid phase sintering (Sun
and Zhao, 2018).
Mechanical and Machining Performance of Functionally Graded

Cemented Carbide
FGCC with Co-enriched surface layer is mainly used as the substrate of coated
tools. The Co-enriched surface has good strength and toughness, which can
absorb the energy otherwise inducing micro cracks in the coating, preventing
the cracks in the coating from expanding to the substrate of tool material to a
certain extent, then improving the bonding strength between the coating and
the substrate. Compared with homogeneous cemented carbide coated tools,
Co-enriched FGCC coated tools demonstrated better mechanical impact
resistance and intermittent cutting performance, but an unimproved
continuous cutting performance (Garcia and Pitonak, 2013; Chen et al., 2006).
FGCC with Co-enriched surface showed certain advantages as coating
substrate, but it did not fundamentally solve the problem of the mismatch of
chemical composition, thermal conductivity and thermal expansion
coefficient between coating and substrate.
FGCC with cubic-enriched surface layer is the latest research direction of
FGCC tools. They have high hardness and high wear resistance, especially
suitable for high-speed cutting of difficult-to-machine materials as titanium
alloys. Tang et al. (2016; 2019) developed FGCC tool with Ti(C, N)-enriched
surface layer through microwave heating nitriding sintering. They performed
Complimentary Copy
dry turning quenched and tempered 40Cr tests using this FGCC and
homogeneous tool. The results showed that FGCC exhibited reduced tool-chip
friction coefficient and flank wear in comparison with homogeneous tool. The
tool life of FGCC enhanced by more than 67% at low-speed cutting compared
to that of the homogeneous tool, while it increased by 130% in case of high-
speed cutting. Sun et al. (Sun and Zhao, 2018; Sun et al., 2018) produced
FGCC with an increased Co content from surface layer to core layer as shown
in Figure 11. They investigated its machining performance through dry turning
pure iron. Results showed that compared with commercially available YG6
tool, FGCC tool yielded reduced cutting forces, cutting temperature and
friction coefficient at the tool-chip interface together with enhanced shear
angle (Sun et al., 2021). The tool life of FGCC was about three times of
reference YG6 cutting tool at high-speed machining as shown in Figure 12.
Nomura et al. (1999) investigated the FGCC tool with hard surface layer as
Table 2. The FGCC demonstrated superior wear resistance and breakage
resistance to traditional cermet. Moreover, FGCC tool also exhibited better
machining performance in comparison with coated cemented carbide tool.
Peeling of coating occurred easily because of built-up edge, while peeling did
not readily occur in FGCC tool as a function of the continuous transition and
metallurgical bonding between the hard surface and the internal layer.
Cutting time (min)

0 2 4 6 8 10 12
0.4 YG6
MLG/WC-Co
Flank wear VB (mm)
0.3
0.2
0.1
0.0
0 460 920 1380 1840 2300 2760

Cutting distance (m)
Figure 12. Flank wear VB of the FGCC and homogeneous tool at different cutting
distance (ν = 230 m/min) (Sun et al., 2021).
Complimentary Copy
Table 2. Some practical applications of FGCC tool (Nomura et al., 1999)
Complimentary Copy
Figure 13. The potential and possible combinations of alternative binder in

cemented carbides.
Development of Cemented Carbide with Alternative Binder
As discussed in the introduction, recently there have been concerns about the
challenges associated with the use of Co, i.e., price instability (the major
incentive for the development of alternative binder), toxicity and properties
degeneration. In 1980s, due to the geopolitical situations in Congo, one of the
countries in a dominant position with 40% of world Co mineral deposit (Banza
et al., 2009), Co was classified as a strategic resource in most western
developed countries including the United States, which drove the cost of
cobalt up. In the following three decades, the cobalt market fluctuated, so did
the resolve and the efforts of the industry to replace Co with other materials.
An ideal alternative binder to Co should satisfy four conditions: ⅰ) possessing
the thermal-physicochemical-mechanical properties matching the high
strength, toughness and wear resistance of cemented carbide; ⅱ) featuring
excellent wettability for WC; ⅲ) having limited solubility for W and C to form
a liquid at the moderate temperature during the sintering process; ⅳ)
guaranteeing no brittle phase formation during the whole sintering process. In
1920s, transitional metals such as iron, nickel, and molybdenum were first
identified as the alternative binder to Co in cemented carbides. In the 1990s,
intermetallic compounds such as iron aluminides and nickel aluminides
emerged as the promising candidate for alternative binder for tungsten carbide.
In the 2000s, some ceramic binders (metal oxide/ carbide) were developed as
Complimentary Copy
a novel binder to replace Co in cemented carbide. In 2010s, certain high-

entropy alloys were investigated as alternative biner in cemented carbide.
Figure 13 illustrated the potential and possible combinations of alternative
binder in cemented carbides. This section focuses on metal, intermetallic,
ceramics and high-entropy alloy bonded cemented carbides.
Metal as Alternative Binder in Cemented Carbide
The main metal alternative binders to Co are Fe, Ni and their alloys including
Fe-Ni, Fe-Mn, Fe-Cu, Fe-Cr, Fe-Mo, Ni-Si, Ni-Mo and Ni-Al, etc. Besides,
stainless steel and metallic glass were also employed as alternative binder in
cemented carbide. The key research focuses on densification, carbon window,
phase transformation toughening and mechanical properties of alternative
metal bonded cemented carbide, of which Fe-Ni bonded cemented carbide is
the most representative one. Compared with single Fe or Ni, hybrid Fe-Ni
binder phase can effectively not only expand the carbon window of cemented
carbide, but also contribute the carbon window to the normal carbon content
values. It is proposed in Figure 14 that the two-phase range gets broader with
increasing Fe + Ni binder content. With respect to the given Fe + Ni binder
content, the width of the two-phase field is firstly diminished and then
increased with increasing Ni/(Fe + Ni) ratio. Appropriate Fe:Ni ratio and
carbon content are the key factors for the operation of martensitic
transformation toughening in Fe-Ni bonded cemented carbide. Liu (2014)
investigated the effect of Fe:Ni ratio on the mechanical properties of Fe-Ni
bonded cemented carbide. As illustrated in Figure 15, the purple line
representing the WC-FeNi(82Fe18Ni) specimens, emerged above all other
lines, which was indicative of the most exceptional combination of hardness
and toughness. Moskovitz et al. (1970) proposed that the ratio 30% of
Ni/(Fe + Ni) was a critical demarcation value, above which there would no
occurrence of martensitic transformation. Thus, no martensitic transformation
occurred to the 15Fe85Ni binder, resulting in the red line signifying the
15Fe85Ni bonded alloys situated below other lines. The WC-
FeCoNi(70Fe12Co18Ni) and WC-FeNi(72Fe28Ni) samples were both close
to the deep blue line representing the WC-Co specimens, suggesting the
similar performance of 70Fe12Co18Ni and 72Fe28Ni to Co being the binder
phase of tungsten carbide cemented carbides.
Complimentary Copy
Figure 14. (a) Temperature projection of a section of the Fe-Ni-W-C phase diagram
calculated at Fe + Ni=10 wt.%. (b) Temperature projection of a section of the Fe-Ni-
W-C phase diagram calculated at Fe + Ni=20 wt.%. The lines describe the
compositions of a mixture of WC and liquid in equilibrium with fcc + M6C (to the
left), and of a mixture of WC + fcc in equilibrium with liquid + graphite (to the right)
(Guillermet, 1978). The solid symbol on the composition axis on both pictures
indicates the stoichiometric composition.
30
Expon. (Co)
Fracture toughness MPa.m1/2
Expon. (15Fe85Ni)
25 Expon. (72Fe28Ni)
Expon. (82Fe18Ni)
Expon. (70Fe12Co18Ni)
20
15
10 50Fe25Co25Ni
5
1100 1200 1300 1400 1500 1600 1700 1800
Hardness HV30
Figure 15. Exponential regressions for cemented carbides with various binders
(Liu, 2014).
Complimentary Copy
Intermetallic as Alternative Binder in Cemented Carbide
The intermetallic alternative binders to Co are mainly aluminum based

compounds including iron aluminum compounds (FeAl), nickel aluminum
compounds (Ni3Al) and titanium aluminum compounds (TiAl3 or TiAl). The
key research focuses on densification, carbon window, oxygen content and
mechanical properties of intermetallic alternative bonded cemented carbide,
of which FeAl and Ni3Al compounds are the most representative. The oxygen
content of powder is the critical factor affecting the phase composition,
microstructure and properties of WC-FeAl cemented carbide. The oxygen
molecules existing in the WC-FeAl powders could fall into three types during
the sintering process: (a) desorbing at low temperatures with respect to oxygen
adsorbing on the powder surface; (b) generating CO2 through reacting with
carbon at high temperatures concerning those adsorbing on the powder surface
or incorporating in the powders; (c) forming oxides including Al2O3, FeAl2O4
and Fe2O3 at high temperatures regarding the ones incorporating in the
powders (Furushima et al., 2015). Therefore, both the molar ratios of Fe in the
FeAl phases and carbon content in WC-FeAl cemented carbide are sensitive
to the oxygen content in the composites. It was proposed that WC-FeAl
possessed the competitive mechanical properties as WC-Co (Figure 16). WC-
Ni3Al cemented carbides must be doped with alloying elements (B, Zr, Cr,
Mo, etc.) inducing solid solution strengthening, so as to improve the
mechanical properties (Katou et al., 2019). TiAl3 or TiAl as alternative binder
can effectively inhibit grain growth, induce crack deflection, and improve
fracture toughness without an appreciable influence on hardness of the
cemented carbides (Jung et al., 2016; Kwak et al., 2016).
Ceramic as Alternative Binder in Cemented Carbide
Ceramic alternative binder is a novel non-metallic binder phase, including

certain metal oxide (Al2O3, MgO, Y2O3, ZrO2, etc.) and metal carbide (TiC,
Cr3C2, ZrC, etc.). The densification mechanisms of ceramic bonded cemented
carbides are defect enhanced sintering and liquid-phase enhanced sintering.
Carbide binder tends to form solid solution with WC matrix, increasing the
defect (lattice substitution, dislocation, etc.) concentration, consequently
realizing lattice activation to promote the densification process. Oxide binder
may possess lower melting point than WC, thus a small amount of liquid phase
is generated during the sintering process, which could lower the grain
Complimentary Copy
boundary energy, consequently accelerating the grain boundary migration and

mass transfer rate.
Figure 16. KIC-HV plots for WC-Co and WC-FeAl (Furushima et al., 2014).
Figure 17. Summary of toughening for ceramic bonded cemented carbide

(Sun et al., 2022).
Complimentary Copy
Table 3. The hardness and fracture toughness of some reported pure WC and cemented carbides with various ceramic
binders (Sun et al., 2020)
Relative density Sintered grain size Hardnessa Fracture toughnessb

Material
(%) (nm) (Hv) (MPa·m1/2)
WC 99.2 200 2925 8.9
WC 100 130 3061 7.3
WC 98.5 380 2854 7.1
WC 99 87 3020 7.1
WC 99.8 220 2959 7.2
WC 97.6 360 2480 6.6
WC-20 at.%TiC 98.5 200 2032 6.3
WC-20 at.%TiC 99 200 2240 7.5
WC-3wt.%TiC-2wt.%TaC-0.2wt.%Cr3C2-0.2wt.%VC 600 2300 7.9
WC-6wt.%Mo2C 250 2400 8.4
WC 99.9 280 2795 4.38
WC-1wt.%VC 96.5 280 2795 4.2
WC-1wt.%VC 99.8 272 2585 6.9
WC-1wt.%Cr3C2 100 277 2605 7.2
WC-0.3wt.%VC-0.5wt.%Cr3C2 97.5 240 2875d 6.05
WC-0.33wt.%VC-0.54wt.%Cr3C2 97.9 730 2464 4.4
WC 100.6 171 2720 7.0
WC-1wt.%Mo2C 100.8 183 2630 6.6
Complimentary Copy
WC-1wt.%Mo2C 99 450 2461 4.8
WC-1wt%TaC 99.7 202 2570 6.9
WC-1wt%ZrC 98.8 236 2420 6.5
WC-1wt%NbC 99.6 214 2540 6.6
Table 3. (Continued)
Relative density Sintered grain size Hardnessa Fracture toughnessb

Material
(%) (nm) (Hv) (MPa·m1/2)
WC-6mol.%SiC-2mol.%ZrC 99 720 2193e 6.7
WC-20mol.%SiC-0.3mol.%Cr3C2 99 420 2193 6.4
(WC-0.8mol.%Cr3C2)-5vol.%SiCw 100.4 1500 2041 7
WC-14.3wt%Al2O3-0.5wt.%VC 98 2000 2103 11.54
WC-10wt%Al2O3w-0.5wt.%VC 98 2000 2103 13.8
WC-10vol.%Al2O3 99.8 101 2540 9.4
WC-4.3wt.%MgO 99 2590 1878f 12.95
WC-6wt.%ZrO2 100 660 1876 10.8
WC-3wt.%AlN 99.6 700 2400 7.5
WC-10wt.%Si3N4w 100 1260 1801 10.94
WC-1.0wt.%CNT 101 200 2328 8.95
WC-3wt.Al2O3-2wt.TiC-0.15wt.MLGc 98.9 400 2255 14.5
a For convenience of comparison, the original hardness values from papers were converted to Vickers hardness values.
b Fracture toughness value was calculated from indentation method.
C This is the surface layer of a functionally graded WC-Al O -TiC-MLG composites.
2 3
d
This is a value of HV0.5.
e
This is a value of HV1.0.
f
This is a value of HV30.
Complimentary Copy
The toughening methods of ceramic bonded cemented carbide include

particle-dispersion toughening, phase-transformation toughening, whisker or
fiber toughening, nanocomposite toughening, graphene/ carbon nanotube
toughening, in-situ self-toughening, gradient/ laminate structure toughening
and synergistic toughening (Figure 17). Particle-dispersion toughening refers
to impeding the crack propagation through the uniform dispersion of the
second-phase particles, which is the basis of the other toughening methods.
Transformation toughening enhances the toughness by means of the fine-
regulation of the ceramic binder composition to achieve stress-induced
tetragonal to monoclinic (t-m) martensitic transformation in metastable ZrO2
phase at room-temperature. Whisker or fiber toughening improves the
toughness of the matrix by the incorporation of high-modulus and high-
strength whiskers (SiC whisker (SiCw), Si3N4w, Al2O3w, etc.) or fibers (i.e.,
carbon fiber (Cf), SiCf, Al2O3f) into the ceramic bonded cemented carbide
matrix. Nanocomposite toughening is defined as the method to significantly
increase the strength and toughness of cemented carbide through incorporating
second phase with dimensions in the nanometer range. Graphene/ carbon
nanotube toughening enhances the strength and toughness of cemented
carbide matrix by doping graphene or carbon nanotube as the reinforcement.
In-situ self-toughening aims to improve the toughness by means of in-situ
synthesized self-toughening components, such as elongated grain, platelet
grain, or whisker. Gradient or laminate structure toughening is the method to
improve the toughness of the host matrix by introducing the compressive
stress in the surface layer and the interfaced distribution of compressive/
tensile stresses between the neighboring layers by taking advantage of the
thermal expansion coefficient mismatch between the materials composing the
compressive and tensile layers. Table 3 illustrates the hardness and fracture
toughness of some reported pure WC and cemented carbides with various
ceramic binders.
High-Entropy Alloy as Alternative Binder in Cemented Carbide
Based on the high-entropy effect in thermodynamics, hysteresis diffusion

effect in dynamics, lattice distortion effect on structure and cocktail effect in
properties, high-entropy alloy (HEA) exhibits superior microstructure stability
and thermal-mechanical-chemical properties to the traditional alloys, and is
considered as the most potential substitute for Co in cemented carbides.
Currently, the investigation on HEA bonded cemented carbide is still in its
Complimentary Copy
infancy. Chen et al. (2022) reported that HEA performed effectively on

inhibiting the grain growth of WC, contributing to the enhanced mechanical
properties of WC-HEA than traditional WC-Co cemented carbides. Luo et al.
(2021) suggested that Al content in HEA exerted critical influence on the
wetting behavior and interfacial microstructure between HEA and WC.
Solodkyi et al. (2022) proposed that HEA was helpful in inducing brittle W2C
to form plate WC, which can significantly improve the strength and toughness
of the WC-HEA alloy. Qian et al. (2022) further enhanced the fracture
toughness of WC-HEA cemented carbide through adjusting the carbon content
in starting powder. Holmström et al. (2018) compared the machining
performance of WC-HEA and WC-Co cutting tool by longitudinal turning of
a steel cylinder made from SS2541, Al-oxidized and tempered steel (Figure
18). The results showed that WC-HEA exhibited an exceptionally high
resistance against plastic deformation at all tested cutting speeds in the
machining test, outperforming the reference WC-Co insert, which illustrated
a linear increase in edge depression with increasing cutting speed.
State-of-the-art cutting
TURING TEST tool inserts that are
used as reference in the
SCHEMATIC VIEW OF THE MACHING TEST test.
The depth-of-cut is radial In the test, the

difference between the part of feed is 0.7mm/turn
cylinder that has been cut and the depth-of-
and the untouched surface. cut is 2mm.
Cutting
tool
The graph shows the resulting edge

deformations of the cutting tools after 30
s of turning at different turning speeds.
70
60 Reference
Feed HEA binder
Deformation (m)
direction 50
40
Workpiece 30
rotation
20
The feed is the speed of
Depth of cut movement of the tool in 10
the longitudinal direction
0
along the cylinder. It is 90 100 110 120 130 140 150 160
measured in mm/turn. Turning speed (m/min)
Figure 18. A schematic view of the machine test, the results of the HEA bonded
product compared to a state-of-the-art reference with Co as binder phase. The actual
shape of the tested inserts is the third from the top (Holmström et al., 2018).
Complimentary Copy
Conclusion
This chapter attempts to comprehensively summarize the progress of

nanostructured cemented carbide, functionally graded cemented carbide, and
cemented carbide with alternative binder, so as to provide reference for those
who would like to enhance the performance of cemented carbides and prepare
the material in a way that is environment friendly, harmless to human health
and low in production cost. The advent of nanosized cemented carbide era has
yet to occur on an industrial scale, and the development of true nanosized
cemented carbide (WC grain size < 100 nm) is still even more challenging,
due to the difficulties of retaining nano grain size in the bulk product after
sintering of nanosized powders. Functionally graded cemented carbide offers
a solution to the trade-off of fracture toughness and hardness through varying
the content or/and grain size of the components from surface to the core in the
sintered samples, showing superior adaptability and resistance to thermal-
mechanical-chemical multi-field coupling and interaction during high-speed
machining process. The alternative binder to Co has developed from metal,
intermetallic to ceramic and high-entropy alloy. Especially, ceramic and high-
entropy alloy bonded cemented carbides are the most potential cutting tools
for high-speed machining of hard-to-cut materials.
Finally, based on the above findings, we propose an outlook on the future
development trends of cemented carbide machining tool.
 High-entropy cemented carbide may be proposed in future, and will

certainly play a significant role in high-speed cutting tools.
 Investigation should be performed on the additive manufacturing
cemented carbide cutting tool with complex geometries.
 Advanced micromechanical testing is required and further performed
to establish processing-composition-microstructure-property
relationships governing cemented carbides.
 Multiscale modeling together with performance prediction towards
cemented carbide by means of density functional theory, etc. is still
rather challenging to assist the design and development of novel
matrix with tailor properties.
Complimentary Copy
Acknowledgments
This work is supported by the National Natural Science Foundation of China

(No. 52375451, 52005396), Shandong Provincial Natural Science Foundation
(ZR2023YQ052), Young Taishan Scholars Program of Shandong Province,
Guandong Basic and Applied Basic Research Foundation
(2023A1515010044), Shandong Provincial Technological SME Innovation
Capability Promotion Project (2023TSGC0848), Young Talent fund of
University Association for Science and Technology in Shaanxi (No.
20210414) and Qilu Youth Scholar Project Funding of Shandong University
(No. 1050522300003).
References
Abele, E. (2007). Werkzeugmaschinen und Industrieroboter, Auszugausdem
Vorlesungsskript. Institut fur Produktionsmanagement, Technologie und
Werkzeugmaschinen [Machine tools and industrial robots, excerpt from the lecture
notes. Institute for Production Management, Technology and Machine Tools], TU
Darmstadt, Germany, 45.
Aleksandrov Fabijanić, T., Jakovljević, S., Franz, M., et al. (2016). Influence of grain
growth inhibitors and powder size on the properties of ultrafine and nanostructured
cemented carbides sintered in hydrogen. Metals, 6(9), 198.
Al-Aqeeli, N. (2015). Characterization of nano-cemented carbides Co-doped with
vanadium and chromium carbides. Powder Technol, 273, 47-53.
Ashby, M. F. (2009). The CES EduPack Resource Booklet 2: Material and Process
Selection Charts. Granta Design Limited: Cambridge.
Bonache, V., Salvador, M. D., Fernández, A., et al. (2011). Fabrication of full density near-
nanostructured cemented carbides by combination of VC/Cr3C2 addition and
consolidation by SPS and HIP technologies. Int J Refract Met H, 29(2), 202-208.
Banza, C. L. N., Nawrot, T. S., Haufroid, V., et al. (2009). High human exposure to cobalt
and other metals in Katanga, a mining area of the Democratic Republic of Congo.
Environ. Res., 109(6), 745-752.
Bonache, V., Salvador, M. D., Busquets, D., et al. (2011). Synthesis and processing of
nanocrystalline tungsten carbide: Towards cemented carbides with optimal
mechanical properties. Int J Refract Met H, 29(1), 78-84.
Chen, L., Wu, E. X., Yin, F., et al. (2006). Effects of gradient structure on the
microstructures and properties of coated cemented carbides. Int J Refract Met H, 13,
363-367.
Cha, S. I., Hong, S. H., and Kim, B. K. (2003). Spark plasma sintering behavior of
nanocrystalline WC-10Co cemented carbide powders. Mater Sci Eng A, 351(1-2), 31-
38.
Complimentary Copy
Chen, R. Z., Zheng, S., Zhou, R., et al. (2022). Development of cemented carbides with
CoxFeNiCrCu high-entropy alloyed binder prepared by spark plasma sintering. Int J
Refract Met H, 103, 105751.
El-Eskandarany, M. S., Mahday, A. A., Ahmed, H. A., et al. (2000). Synthesis and
characterizations of ball-milled nanocrystalline WC and nanocomposite WC-Co
powders and subsequent consolidations. J Alloy Compd, 312(1-2), 315-325.
Fan, P., Fang, Z. Z., and Guo, J. (2013). A review of liquid phase migration and methods
for fabrication of functionally graded cemented tungsten carbide. Int J Refract Met H,
36, 2-9.
Fang, Z. Z., Wang, X., Ryu, T., et al. (2009). Synthesis, sintering, and mechanical
properties of nanocrystalline cemented tungsten carbide-a review. Int J Refract Met
H, 27(2), 288-299.
Fang, Z., Maheshwari, P., Wang, X., et al. (2005). An experimental study of the sintering
of nanocrystalline WC-Co powders. Int J Refract Met H, 23(4-6), 249-257.
Furushima, R., Katou, K., Shimojima, K., et al. (2015). Changes in constituents and FeAl
composition with oxygen content in WC-FeAl composites. Int J Refract Met H, 50,
298-303.
Furushima, R., Katou, K., Nakao, S., et al. (2014). Relationship between hardness and
fracture toughness in WC-FeAl composites fabricated by pulse current sintering
technique. Int J Refract Met H, 42, 42-46.
Garcia, J., and Pitonak, R. (2013). The role of cemented carbide functionally graded outer-
layers on the wear performance of coated cutting tools. Int J Refract Met H, 36, 52-
59.
Guillermet, A. F. (1978). An assessment of the Fe-Ni-W-C phase diagram. Z Metallkd,
78(3), 165-171.
Holmström, E., Lizarraga, R., Linder, D., et al. (2018). High entropy alloys: Substituting
for cobalt in cutting edge technology. Appl Mater Today, 12, 322-329.
Huang, S. G., Li, L., Vanmeensel, K., et al. (2007). VC, Cr3C2 and NbC doped WC–Co
cemented carbides prepared by pulsed electric current sintering. Int J Refract Met H,
25(5-6), 417-422.
Inoue, K. (1966). US Patent, No 3 241 956.
Jia, C., Sun, L., Tang, H., et al. (2007). Hot pressing of nanometer WC-Co powder. Int J
Refract Met H, 25(1), 53-56.
Jung, G. N., Kim, B. S., Yoon, J. K., et al. (2016). Properties and rapid sintering of
nanostructured WC and WC-TiAl hard materials by the pulsed current activated
heating. J Ceram Process Res, 17(4), 295-299.
Katou, K., Shimojima, K., and Hosokawa, H. (2019). Preparation for WC-Ni3Al hard metal
by vacuum sintering. Mater Trans, 60(3), 471-475.
Kim, H. C., Shon, I. J., Jeong, I. K., et al. (2007). Rapid sintering of ultrafine WC and WC-
Co hard materials by high-frequency induction heated sintering and their mechanical
properties. Metals Mater Int, 13(1), 39-45.
Kupczyk, M. J. (2015). Cutting edges with high hardness made of nanocrystalline cemented
carbides. Int J Refract Met H, 49, 249-255.
Complimentary Copy
Kwak, B. W., Song, J. H., Kim, B. S., et al. (2016). Mechanical properties and rapid
sintering of nanostructured WC and WC-TiAl3 hard materials by the pulsed current
activated heating. Int J Refract Met H, 54, 244-250.
Lindvall, R., Lenrick, F., M’Saoubi, R., et al. (2021). Performance and wear mechanisms
of uncoated cemented carbide cutting tools in Ti6Al4V machining. Wear, 477,
203824.
Liu, C. (2014). Alternative binder phases for WC cemented carbides [Master Thesis].
Stockholm: KTH Royal Institute of Technology.
Luo, W. Y., Liu, Y. Z., and Tu, C. (2021). Wetting behaviors and interfacial characteristics
of molten AlxCoCrCuFeNi high-entropy alloys on a WC substrate. J Mate Sci Tech,
78, 192-201.
Mahmoodan, M., Aliakbarzadeh, H., and Gholamipour, R. (2011). Sintering of WC-10%
Co nano powders containing TaC and VC grain growth inhibitors. T Nonferr Metal
Soc, 21(5), 1080-1084.
Michalski, A., and Siemiaszko, D. (2007). Nanocrystalline cemented carbides sintered by
the pulse plasma method. Int J Refract Met H, 25(2), 153-158.
Maheshwari, P., Fang, Z. Z., and Sohn, H. Y. (2007). Early-stage sintering densification
and grain growth of nanosized WC-Co powders. Int J Powder Metall, 43(2), 41-47.
Moskowitz, D., Ford, M. J., and Humenik, M. (1970). High-strength tungsten carbides. Int
J Powder Met, 6(4), 55-64.
(2016) 54, 244-250.
Mishra, R. S., Risbud, S. H., and Mukherjee, A. K. (1998). Influence of initial crystal
structure and electrical pulsing on densification of nanocrystalline alumina powder. J
Mater Res, 13(1), 86-89.
Munir, Z. A., Anselmi-Tamburini, U., and Ohyanagi, M. (2006). The effect of electric field
and pressure on the synthesis and consolidation of materials, A review of the spark
plasma sintering method. J Mater Sci, 41(3), 763-777.
Nomura, T., Moriguchi, H., Tsuda, K., et al. (1999). Material design method for the
functionally graded cemented carbide tool. Int J Refract Met H, 17(6), 397-404.
Oakley, K. P. (1964). Man the tool-maker. Chicago: University of Chicago Press.
Qian, C., Liu, Y., Cheng, H. C., et al. (2022). Effect of the carbon content on the
morphology evolution of the η phase in cemented carbides with the CoNiFeCr high
entropy alloy binder. Int J Refract Met H, 102, 105731.
Ren, X., Miao, H., and Peng, Z. (2013). A review of cemented carbides for rock drilling:
an old but still tough challenge in geo-engineering. Int J Refract Met H, 39, 61-77.
Shi, L., Shao, G., Duan, X., et al. (2005). Mechanical properties, phases and microstructure
of ultrafine hardmetals prepared by WC-6.29Co nanocrystalline composite powder.
Mater Sci Eng A, 392(1-2), 335-339.
Solodkyi, I., Teslia, S., Bezdorozhev, O., et al. (2022). Hardmetals prepared from WC-W2C
eutectic particles and AlCrFeCoNiV high entropy alloy as a binder. Vacuum, 195,
110630.
Stephenson, D. A., and Agapiou, J. S. (1997). Metal Cutting Theory and Practice e
Manufacturing Engineering and Materials Processing. Marcel Dekker.
Sun, J., Zhao, J., Chen, Y., et al. (2022). Macro-micro-nano multistage toughening in nano-
laminated graphene ceramic composites. Mater Today Phys, 22, 100595.
Complimentary Copy
Sun, J., Zhao, J., Huang, Z., et al. (2020). A review on binderless tungsten carbide:
development and application. Nano-Micro Lett, 12(1), 1-37.
Sun, J., Huang, Z., Zhao, J., et al. (2021). Nano-laminated graphene-carbide for green
machining. J Clean Prod, 293, 126158.
Sun, J., and Zhao, J. (2018) Multi-layer graphene reinforced nano-laminated WC-Co
composites. Mater Sci Eng A., 723, 1-7.
Sun, J., Zhao, J., Gong, F., et al. (2018). Design, fabrication and characterization of multi-
layer graphene reinforced nanostructured functionally graded cemented carbides. J
Alloy Compd, 750, 972-979.
Sun, J., Zhao, J., Gong, F., et al. (2019). Development and application of WC-based alloys
bonded with alternative binder phase. Crit Rev Solid State, 44(3), 211-238.
Sun, J., Zhou, Y., Deng, J., et al. (2016). Effect of hybrid texture combining micro-pits and
micro-grooves on cutting performance of WC/Co-based tools. Int J Adv Manuf Tech,
86(9), 3383-3394.
Sun, J., Zhang, F., and Shen, J. (2003). Characterizations of ball-milled nanocrystalline
WC-Co composite powders and subsequently rapid hot pressing sintered cermets.
Mater Lett, 57(21), 3140-3148.
Sun, L., Jia, C., and Xiong, J. (2011). VC, Cr3C2 doped ultrafine WC-Co cemented carbides
prepared by spark plasma sintering. Int J Refract Met H, 29(2), 147-152.
Sun, L., Jia, C. C., and Xian, M. (2007). A research on the grain growth of WC-Co
cemented carbide. Int J Refract Met H, 25(2), 121-124.
Tang, S., Li, P., Liu, D., et al. (2019). Cutting performance of a functionally graded
cemented carbide tool prepared by microwave heating and nitriding sintering. High
Temp Mat Processes, 38, 582-589.
Tang, S., Liu, D., Li, P., et al. (2016). Microstructure and mechanical properties of
functionally gradient cemented carbides fabricated by microwave heating nitriding
sintering. Int J Refract Met H, 58, 137-142.
Tsuda, K. (2016). History of development of cemented carbides and cermet. SEI Tech. Rev.,
82, 16-20.
Wang, Z., Jia, J., Wang, B., et al. (2019). Two-step spark plasma sintering process of
ultrafine grained WC-12Co-0.2 VC cemented carbide. Materials, 12(15), 2443.
Wei, C. B., Song, X. Y., Fu, J., et al. (2012). Microstructure and properties of ultrafine
cemented carbides-differences in spark plasma sintering and sinter-HIP. Mater Sci
Eng A, 552, 427-433.
Zhang, L., Wang, Y. J., Yu, X., et al. (2008). Crack propagation characteristic and
toughness of functionally graded WC-Co cemented carbide. Int J Refract Met H, 26,
295-300.
Zhao, J. (2014). The use of ceramic matrix composites for metal cutting applications. In:
Advances in ceramic matrix composites. Low IM, Woodhead Publishing, 623-654.
Complimentary Copy
Complimentary Copy
Chapter 3
Recent Advances in the Synthesis of Tungsten

Carbide Nanoparticles
D.T. Usmanov*
Arifov Institute of Ion-Plasma and Laser Technologies, Uzbekistan Academy of Sciences,
Tashkent, Uzbekistan
Abstract
In this review chapter we analyzed papers devoted to research and

synthesis of tungsten carbide nanoparticles published papers in the last
decades. Tungsten carbide is one of the hardest ceramics known today, it
is comparable in hardness to diamond. In addition to hardness, tungsten
carbide has a high melting point and wear resistance. At the present time
a tungsten carbide is being applied in many fields due to unique physic-
mechanical properties. However, to increase significantly physic-
mechanical properties of tungsten carbide is expected only when using
crystalline powders with grains smaller than 100 nm. Carbon forms two
different chemical compounds with tungsten such as tungsten
monocarbide WC and tungsten semi carbide W 2C. The first of them is
less stable and hard, however, having the ability to form crystals in a
tungsten melt, it is used as an integral part of various mineral-ceramic
compositions. In contrast to tungsten monocarbide, tungsten semi carbide
has a significantly higher temperature resistance, and can also easily be
embedded in WC solid solutions with other metals like iron, cobalt, etc.
In addition, tungsten semi carbide has an extremely high wear resistance.
Therefore, until now many physic-chemical methods have been
developed for the synthesis of tungsten carbide nanoparticles. The
advantages and disadvantages of these methods were thoroughly
discussed.
*
Corresponding Author’s Email: usmanov@iplt.uz.

ISBN: 979-8-89113-221-4
Complimentary Copy
118 D.T. Usmanov
Keywords: tungsten carbide, nanoparticles, physic-mechanical

properties, physic-chemical methods
Introduction
Tungsten carbide is the most used alloy in cutting instrumental production

because of its hardness. Its hardness is comparable in hardness to diamond. In
addition to hardness, tungsten carbide has a high melting point and wear
resistance. In addition, the rare combination of strong bonding and metallic
conductivity makes tungsten carbide an attractive material for high
temperature contacts or as conductive protective layers in sensor applications.
At the present time a tungsten carbide is being applied in many fields due to
unique physic-mechanical properties (Sickafoose et al. 2002; Rao 2009;
Karimi et al. 2020; Mostajeran et al. 2020; Hamp et al. 2011).
The development of engineering and technology has necessitated the use
of tools with such mechanical properties that they are able to work under
conditions of increased abrasive wear and high loads with high productivity.
Such tools are made on the basis of hard alloys, which, in terms of their
mechanical and thermal characteristics, are many times superior to the
material being processed. Hard alloys have high hardness and wear resistance,
which determines their use as a material for the manufacture of cutting and
drilling tools, as well as products with increased requirements for wear
resistance.
The most important component of hard alloys is tungsten carbide, WC.
Tungsten carbide is actively used in engineering for the manufacture of tools
that require high hardness and corrosion resistance. This material is used in
the manufacture of various cutters, abrasive discs, drills, milling cutters, drill
bits and other cutting and stamping tools. Fine-grained tungsten carbide hard
alloys, when used in the manufacture of cutting tools, have higher
performance properties compared to traditional hard alloys based on silicon
carbide (grain sizes 3-8 microns). However, in recent years, a whole class of
low-dimensional tungsten carbide powders has emerged. These powders are
classified as submicrometer (0.8 µm), ultrafine (0.4 µm) and very fine (0.2
µm) powders and are already produced by industry in leading countries and
are used in the composition of hard alloys. At the same time, a sharp increase
in the physical and mechanical properties of materials is expected only when
nanometer-sized powders (less than 100 nm) are used. However, to date, there
Complimentary Copy
Recent Advances in the Synthesis of Tungsten Carbide Nanoparticles 119
is no industrial high-performance process for obtaining tungsten carbide

nanopowders.
Carbon forms two different chemical compounds with tungsten - tungsten
monocarbide WC and tungsten semicarbide W2C. The first of them is less
stable and hard, however, having the ability to form crystals in a tungsten melt,
it is used as an integral part of various mineral-ceramic compositions. In
contrast to tungsten monocarbide, tungsten semicarbide has a significantly
higher temperature resistance, and can also easily be embedded in WC solid
solutions with other metals - iron, cobalt, etc. In addition, tungsten
semicarbide has an extremely high wear resistance.
The reduction of particles to nanometer sizes leads to the manifestation of
the so-called “quantum size effects” in them, when the sizes of the objects
under study are comparable to the de Broglie wavelength of electrons,
phonons and excitons. In spheroidal nanoparticles, there is a three-
dimensional quantization of levels, which allows us to speak, depending on
the composition of the nanoparticles, about the formation of “quantum dots”,
“quantum crystallites” and other objects with zero dimension. One of the main
reasons for the change in the physical and chemical properties of small
particles as their size decreases is the increase in the relative fraction of
“surface” atoms under different conditions (coordination number, symmetry
of the local environment, etc.) than the atoms inside the bulk phase. From the
energy point of view, a decrease in particle size leads to an increase in the role
of surface energy. At present, the unique physical properties of nanoparticles
arising from surface or quantum size effects are the subject of intense research
(Baraton 2002).
Advanced Synthesis Methods
All groups of methods for obtaining nanopowders can be conventionally

divided into two groups. The first group includes technologies based on
chemical processes, and the second - on physical processes. In accordance
with this, we will briefly consider the main methods currently used for
obtaining nanopowders.
Complimentary Copy
120 D.T. Usmanov
Gas-Phase Synthesis
A comparative analysis of technologies for the chemical synthesis of

nanopowder materials shows that at present the technology of aerosol
synthesis (the method of chemical vapor condensation) is one of the most
promising, since it allows one to obtain nanoparticles of almost any chemical
composition in a wide range of sizes and concentrations of alloying elements,
to make the process of their production is continuous with the possibility of
its application on an industrial scale, as well as environmentally friendly and
low-waste (Gusev 2007).
The initial product for obtaining nanoparticles is a certain volatile, usually
volatile organometallic chemical substance “precursor”, which in a liquid or
solid state is supplied to a thermostat, where it evaporates at some given
sufficiently low temperature. The precursor vapor is captured by the carrier
gas flow and enters the reactor heated to a temperature higher than the
thermostat. Pyrolysis of the precursor vapor occurs in the reactor with the
formation of a supersaturated vapor of the required component (for example,
metal), further condensation of the supersaturated vapor with the formation of
nanoparticles from this substance. Also, chemical reactions of vapors of a
component with a gas phase or vapors of several components among
themselves, coalescence of already formed particles, etc. can also occur in the
reactor. Particles in the form of an aerosol enter the working chamber with a
controlled pressure. Particles can be collected using electrostatic traps or from
the surface of a rotating disk cooled with liquid nitrogen, or simply from the
bottom and walls of the inner space of the working chamber.
The main parameters controlled in the process of obtaining nanoparticles
by this method and affecting the shape, average size, phase and chemical
composition of powder particles are the concentration of the initial metal-
containing substance in the gas phase, the residence time of the gas mixture in
the hot zone of the reactor, the decomposition temperature, and the type of
gases used (Gusev 2004).
Method of Thermal Decomposition and Recovery of Salts
During thermal decomposition, complex elemental and organometallic

compounds, hydroxides, carbonyls, nitrates, oxalates, and other compounds
are used, which decompose at a certain temperature with the formation of a
Complimentary Copy
synthesized substance and the release of a gas phase (this process is also called
pyrolysis).
This method can be used to obtain agglomerated metal powders with an
internal grain size of less than 100 nm (Lyakhov et al. 2014). In general, the
method consists of several stages: (1) preparation of a solution of water-
soluble salts containing the required metal components - usually nitrates,
carbonates, etc. (2) spray drying the aqueous solution with hot air, which
results in the formation of the original powder; (3) oxidative annealing to
decompose salts, remove volatile components and obtain the corresponding
oxides - oxide powder can be the final product, for example, in the production
of ferrites or high-temperature superconductor ceramics; (4) recovery or other
processing of the oxide powder in order to obtain a metal or composite powder
of the desired phase and chemical composition.
The advantages of the method include relative simplicity, the absence of
mechanical impact on the material, and as a result, the high purity of the alloy
metal, and the homogeneous distribution of alloying components.
The main disadvantage of thermal decomposition is the relatively low
selectivity of the process. The reaction product is usually a mixture of the
desired product and other compounds.
Thermal Evaporation
With this method, the evaporated substance is heated in a crucible. Currently,

different heating methods are used, as a rule, using high-intensity energy
sources: high-frequency induction, electron beam, electric arc, plasma, laser
(Chen et al. 2003). The powders obtained by this method have a spherical or
faceted shape and can be both metallic and represent intermetallic compounds
or other compounds.
The advantage of the method is the production of pure powders with a
narrow particle size distribution, and the disadvantage is the low productivity
of the process. This shortcoming is temporary and is caused not by the process
technology itself, but by the lack of large-scale installations for the production
of nanopowders on an industrial scale.
Explosive Evaporation
This method is currently being developed rapidly. It is based on the release of

a very large amount of energy in a short period of time. In this case, the
Complimentary Copy
122 D.T. Usmanov
material evaporates, and then, due to a rapid increase in volume, it is cooled

with the condensation of vapors into small particles. In some cases, a part of
the material may not have time to evaporate; it melts and explosively separates
into liquid drops (Lerner et al. 2009; Kotov 1999; Yavorovsky et al. 1995;
Kotov et al. 1997; Kotov et al. 2000; Sedoy et al. 1999). An additional factor
contributing to the atomization may be the release of gases dissolved in the
starting material. To supply the required amount of energy, a powerful electric
current pulse, an arc discharge, or a laser radiation pulse are used. The most
widespread variant of this technology is used in which an explosion of a wire
with a diameter of 0.1-1 mm is used under the action of a current pulse with a
duration of 10-5-10-6 s, a voltage of 10-15 kV and a current density of 104-
106 A/mm2. The scheme for obtaining powder from wire by explosive
evaporation is shown in Figure 1. In this case, the current discharge is created
by a capacitor. The particle size and structure are controlled mainly by
changing the density and velocity of the supplied energy. The method makes
it possible to produce high-purity spherical powders with particle sizes up to
5–10 nm, including those from metals with a high melting point and high
chemical activity. The disadvantages of the method are: a significant energy
consumption and, as a result, the relative high cost of the obtained
nanopowders and the difficulty of removing particles of the micron size range
that arise from melt drops.
Figure 1. Scheme for obtaining powder from wire by explosive evaporation: 1-

charging circuit, 2-discharge circuit, 3-exploding wire, 4-chamber with an inert gas.
Complimentary Copy
Evaporation in an Inert Gas Flow (Levitation-Jet Method)
With this method, metal evaporation is carried out in an inert gas flow, for
example, from a drop of melt at the end of a wire heated by a high-frequency
magnetic field (Zhigach et al. 2012). The size of the resulting particles depends
on the gas flow rate - with increasing speed, it can decrease from 500 to 10 nm
with a simultaneous decrease in the particle size spread. Using the method
under consideration, I obtain, in particular, Mn and Sb nanopowders. The
latter powder was amorphous due to the high quenching rate in the gas jet.
There is a variant of the method under consideration, called the cryogenic
melting method. It lies in the fact that the melting of the wire is carried out in
a liquid with a very low temperature, for example, in liquid nitrogen.
Electrical Explosion of the Conductor
A rapidly developing method for obtaining finely dispersed powders is the

electric explosion of a conductor, which is a sharp change in the physical state
of the metal as a result of intense energy release in it when a high-density
pulsed current is passed (Domashenko et al. 2004). For this purpose, a wire
with a diameter of 0.1-1.0 mm is used.
An electric explosion is accompanied by the generation of shock waves
and creates the possibility of rapid heating of metals at a rate of more than 1 ×
107 K/s to high temperatures (Lerner and Shamansky 2004). The ability of
electrically exploding conductors to dramatically change their properties and
effectively convert the primary electrical energy of storage devices into other
types of energy (thermal energy, radiation energy of the resulting plasma,
shock wave energy, etc.) has found, in particular, application for obtaining fine
powders. At the initial stage of the electric explosion, the heating of the
conductor is accompanied by its linear expansion at a relatively low speed of
1-3 m/s. At the stage of the actual explosion, as a result of the passage of a
current pulse, the metal overheats above the melting temperature, the
expansion of the substance of the exploded conductor occurs at a speed of up
to 5-103 m/s, and the overheated metal explosively disperses. The pressure and
temperature at the front of the emerging shock wave reach several hundred
MPa (thousands of atmospheres). As a result of condensation in a stream of
rapidly expanding vapor, very small particles are formed. By adjusting the
explosion conditions, it is possible to obtain powders with particle sizes from
100 µm to 50 nm.
Complimentary Copy
124 D.T. Usmanov
Plasma Chemical Synthesis
Plasma-chemical synthesis of nanopowders (NPs) is a chemical method for

obtaining highly dispersed powders of nitrides, carbides, borides and oxides,
which consists in the reaction proceeding in a low-temperature plasma far
from equilibrium at a high rate of formation of nuclei of a new phase and a
low rate of their growth. As is known, plasma is the “fourth state of matter” -
or partially ionized gas, which, in particular, allows to stabilize its state by
acting on the plasma jet with an electromagnetic field. Thermal or low-
temperature plasma has been used in chemical technology and metallurgy,
which, unlike space or thermonuclear plasma, is characterized by a
temperature range from 103 to 104 K, achievable in special electric discharge
devices called plasmatrons. As a rule, their electric arc version is used in
metallurgy, but electrodeless high-frequency installations can also be used to
obtain highly pure materials, since the plasma is formed as a result of an arc
discharge and then stabilizes, and secondly, it is formed due to a discharge
between the capacitor plates or when exposed to high-frequency fields to the
gas environment.
Plasma chemical synthesis is one of the widespread chemical methods for
obtaining finely dispersed powders of nitrides, carbides, borides, and oxides
(Wang et al. 2016). It is carried out using low-temperature plasma of arc or
glow discharges. Metals, halides or other compounds are used as feedstock.
The main conditions for obtaining highly dispersed powders by this method
are the reaction proceeding far from equilibrium and the high rate of formation
of nuclei of a new phase at a low rate of their growth. Under real conditions
of plasma-chemical synthesis, it is advisable to obtain nanoparticles by
increasing the cooling rate of the plasma flow in which condensation from the
gas phase occurs; this reduces the size of the resulting particles, and also
suppresses the growth of particles by merging them upon collision. In plasma-
chemical synthesis, low-temperature (4000-8000 K) nitrogen, ammonia,
hydrocarbon, argon plasma of arc, glow, high- or microwave-frequency
discharges is used. The characteristics of the resulting powders depend on the
raw materials used, the synthesis technology, and the type of plasma torch.
The particles of plasma-chemical powders are single crystals and have sizes
from 10 to 100-200 nm or more. Plasma-chemical synthesis provides high
rates of formation and condensation of the compound and is characterized by
a fairly high productivity.
Complimentary Copy
Research and Application of Tungsten Carbide Materials
Zhao et al. (2013) successfully synthesized ultrafine WC nanoparticles using

DC arc discharge plasma process with 23 A discharge current at atmospheric
pressure. The synthesis process was occurred in the plasma reactor which is
composed of DC arc generator, plasma reactor chamber and gas flow system.
In this system the thermal plasma was produced by an electric arc discharge
between tungsten electrodes with 6 mm in diameter connected to DC power
supply. Argon was used as plasma gas, and benzene as carbon source. Benzene
was carried into the reactor by argon flow. Plasma gas and benzene were
injected simultaneously at atmospheric pressure with flow rates of 80 l/h. The
synthesized products were deposited on the tungsten positive electrode ends.
The synthesis of WC ultrafine nanoparticles was done in different discharge
current and times. Figure 2 shows these results that synthesized nanoparticles
were analyzed using X-ray diffractometer (XRD). As we can see in the Figure
2 when discharge current was 16 A the WC nanoparticles were not formed
under the process. The formation of NPs is directly depended on discharge
current and discharge time. WC and W2C were formed when discharge current
and time were 23 A and 60 s respectively. Interestingly, when discharge
current was below 23 A, no tungsten carbide obtained. TEM images show the
particles sizes of tungsten carbide varied in the range from 3 to 7 nm.
Samokhin et al. (2013) synthesized WC nanopowders using DC thermal
plasma reactor in air–methane and nitrogen–hydrogen environment. Plasma
jet was generated by DC arc plasma torch with the input power up to 20 kW.
In case of tungsten carbide synthesis, the torch operated on the mixture of air
and methane (20–25 vol.% methane), and in some runs on the nitrogen–
hydrogen mixture. Authors claimed that they used low cost material tungsten
oxide for synthesizing nanopowders WC.
Due to the high temperature of the plasma stream, the injected metal oxide
particles vaporized, reacted, and condensed, forming nanopowder clusters.
Nanoparticles are deposited on the inner surfaces of the reactor and the
collector. Intensive cooling of these surfaces as well as regular cleaning
prevented the sintering of nanoparticles and the formation of a crust on the
water-cooled surfaces. Nanopowders were produced in the W-C system by
injecting WO3 powder using CH4 as carrier gas into a nitrogen-hydrogen or
air-methane plasma flame. TEM images shows the obtained NPs have average
size less than 45 nm (Figure 3). Figure 4 shows the XRD spectrum of obtaining
NPs. It can be seen the crystallographic phases as W, W2C, WC1-x, WC, C
were observed; however, the NP phase compositions were dominated by the
Complimentary Copy
126 D.T. Usmanov
presence of W, W2C, WC1-x. The reaction of WO3 tungsten oxide with

methane in the H2–N2 or CH4-air plasma stream results in the formation of
nanopowders with a maximum particle size of 120 nm. The crystal structure
of nanopowder is shown by WC1-x, W2C and W crystalline phases. The total
carbon content of can be controlled in the range of 4-8% by weight.
Figure 2. XRD patterns of the products obtained with different discharge times and
currents (Zhao et al. 2013).
Figure 3. TEM image of the synthesized nanopowders in W–C nanosystem

(Samokhin et al. 2013).
Complimentary Copy
Figure 4. X-ray diffraction patterns of the synthesized powders in W–C nanosystem

(Samokhin et al. 2013).
Sagadevan et al. (2017) synthesized tungsten carbide (WC) nanoparticles

using hydrothermal method. The synthesized nanoparticles (NPs) were
analyzed powder X-ray diffractogram (PXRD), SEM, TEM and dielectric
studies techniques. Authors also investigated the dielectric and electronic
properties of WC NPs as well as in addition to the electronic properties such
as valence electron plasma energy, average energy gap or Penn gap, Fermi
energy and electronic polarizability, dielectric properties. These
characteristics of the WC nanoparticles were reported for the first time in this
paper. Analysis of the PXRD pattern of clearly showed the hexagonal structure
of WC NPs, and their grain size was 24 nm. SEM images confirmed the
spherical shape of WC-NPs. The size of WC nanoparticles was distinguished
by using TEM, which also helped to determine the size of prepared WC
nanoparticles. The average particle size of determined by TEM analysis of
WC nanoparticles was 20-50 nm, which is consistent with the PXRD.
Dielectric data showed that both dielectric constant and dielectric loss vary
inversely, i.e., decreased frequency rapidly.
Isaeva et al. (2013) were studied the processes of obtaining nanoparticles
of tungsten carbides, as well as other transition metal carbides using plasma-
chemical reduction synthesis. The main patterns of obtaining powders of given
dispersion and composition are revealed. The characteristic sizes of carbide
particles were 40–80 nm. In order to obtain a homogeneous mixture of WC–
Co nanopowders with an exact mass content, a method has been developed for
cobalt deposition on tungsten carbide powder with the simultaneous
Complimentary Copy
128 D.T. Usmanov
introduction of additives of inhibitor carbides, such as chromium, vanadium,

and tantalum carbides. Synthesis of tungsten carbide nanopowders from
plasma-chemical powders of the W–C system was carried out on a flow plant,
consisting of resistance furnaces by Naberterm, systems gas supply with gas
flow control from 0.6 up to 90 l/h and a quartz reactor in which restoration and
actual synthesis. To obtain a nanosized WC–Co composition with additives of
inhibitor carbides, we used the method of cobalt salt precipitation from
solution followed by its reduction in hydrogen in the same setup.
According to XRD data, it was revealed that nanopowders W–C systems
(Figure 5a) consist of a mixture of W2C, β-WC (WC1–x), W, WC, C with phase
predominance W, W2C, β-WC at total carbon content 5–8 wt.%. Specific
surface area of obtained samples changed in the range Ssp = 15÷50 m2/g.
Nanopowders consist mainly of particles W smaller than 30 nm (Figure 5b),
moreover, the presence of a layer is noted on their surface carbon [Krasovsky
et al. 2008]. It has been established that the main parameter determining
carbon content obtained in plasma powders, is the ratio of the elements С/W
in initial reagents. Specific surface area determined mainly by enthalpy plasma
jet and again by the ratio C/W. An increase in enthalpy leads to a decrease Ssp
of nanopowder with increasing proportion carbide phases in the resulting
product.
Figure 5. X-ray pattern (a) and micrograph (b) of powders of the W–C system after
plasma-chemical reductive synthesis (Isaeva et al. 2013).
Complimentary Copy
Figure 6. Change in the phase composition of the material depending on the

composition of the gas phase (Isaeva et al. 2013).
Figure 7. Effect of synthesis time on the phase composition of the powder at t =

1030°С (Isaeva et al. 2013).
To find out which gaseous medium is preferably, the synthesis of

nanopowders was carried out W–C systems in N2, Ar, and H2 media at t =
950°С and 1100°С, τ = 1 h. Maximum output target phase of tungsten
monocarbide was obtained using hydrogen, but in argon and especially
nitrogen, the results are lower (Figure 6). Apparently, active carbon is
transferred to the surface of the particles in the form of hydrocarbons formed
in the interaction of H and C in the powder. Direct synthesis processes from
Complimentary Copy
130 D.T. Usmanov
tungsten and carbon, as is known from industrial practice, at much higher

temperatures. Figure 7 shows the change in the phase composition powder
depending on the synthesis time. Study of the synthesis of WC nanopowders
showed that their properties are influenced by several factors. Increasing
temperature and time process increases the yield of the target phase α-WC,
however, in this case, the growth of carbide particles occurs tungsten.
Tungsten carbide powders with the main phase content close to 100% and Ssp
= 6 ÷ 8 m2/g can be obtained in 3–5 hours at t = 970 ÷ 1050°С.
One of the developing approaches to the production of metallic and
nonmetallic carbides, in particular tungsten carbides, is electric arc synthesis
in a direct current arc discharge plasma (Karpov et al. 2014; Zhao et al. 2013;
Saito et al. 1997; Pak et al. 2020]. The process is usually carried out in a
vacuum or in an inert gas to prevent oxidation of the synthesis products by
atmospheric oxygen. Depending on the temperature field of gradients, the rate
of temperature change, and the ratio of initial precursors, as a result of the
electric arc process, products are obtained containing various crystalline
phases of tungsten carbide: WC (hexagonal), W2C (rhombic and hexagonal),
WC1–x (cubic) (Saito et al. 1997).
In work (Sivkov et al. 2021), cubic tungsten carbide WC1–x was obtained
in a supersonic jet of carbon-tungsten electric discharge plasma generated by
a coaxial magneto-plasma accelerator with graphite electrodes. Plasma-
dynamic synthesis of cubic tungsten carbide was carried out in a system that
basically consisted of a capacitive storage energy, coaxial magneto-plasma
accelerator and working chamber-reactor. Capacitive energy storage is
designed for pulsed power supply of coaxial magneto-plasma accelerator,
which is a device for generating and accelerating electric discharge plasma.
The influence of the parameters of a gaseous medium (pressure, type) on the
process of development of the shock-wave structure of a plasma jet flowing
into the free space of the reactor chamber and on the formation of particles of
the synthesis product is analyzed in this work. Figure 8 shows the attenuation
rates of the electric discharge plasma jet during the passage of the shock wave
structure through the free space of the reactor chamber and shows a significant
influence of the pressure in the chamber on the initial jet velocity υj, as well
as on the deceleration of the formed plasma jet as a whole. Figure 9 shows the
results of XRD analysis of the products synthesized under a fore vacuum
(pressure 1 × 104 Pa, Figure 9a) and at a pressure of 5 × 104 Pa (Figure 9b). It
can been seen that under low vacuum pressure dominated WO2 and W in the
XRD spectrum. Dominance in the product of oxide phases and metal tungsten
is only explained the fact that in this mode in a rarefied atmosphere the sphere
Complimentary Copy
leaves traces of the air atmosphere due to the imperfection of the vacuum
system. The main dominant phase of products, obtained at higher pressures (5
× × 104 Pa and above), was the crystalline phase cubic system WC1 – x. In this
work, the most optimal pressure ranges and the type of gaseous medium were
determined, which make it possible not only to synthesize cubic tungsten
carbide with a purity of up to ~90 wt. %, but also to control the average size
of the resulting particles.
Figure 8. Velocity decay curves υ (Sivkov et al. 2021).
Figure 9. Data from XRD analysis of products obtained at different pressures in the
reactor chamber: (a) – XRD-picture of the product synthesized at Р = 1 × 104 Pa;
(b) – typical XRD pattern typical for products irradiated at P = 0.5–3.0 atm. (Sivkov
et al. 2021).
Complimentary Copy
132 D.T. Usmanov
An experimental setup for the synthesis of tungsten carbide nanopowders

with a size of less than 100 nm directly from tungsten trioxide based on
plasma-chemical processes was developed (Kudaykulov et al. 2022; Ashurov
et al. 2021). In this system, the ignition of an electric arc having a discharge
current of 80–200 A and a discharge voltage of 20–30 V is carried out between
a graphite electrode (cathode) and a composite (anode) electrode. Tungsten
carbide nanopowders were synthesized directly from tungsten oxide at low-
temperature plasma by the vacuum arc discharge method. It was found that
during the synthesis of tungsten carbide nanopowders, various phases are
formed, such as WC, W2C and WC1-x, which are explained by the parameters
of the electric arc discharge and the distribution of precursors. The formation
of the W2C and WC1-x phases during synthesis is explained by the high
temperature gradient and uneven distribution of the initial precursors in the
volume of the reaction zone during the low-vacuum electric arc discharge. The
average size of tungsten carbide nanopowders was in the range of less than
100 nm. Glucose precursor showed the best result in comparison with carbon
black and oxalic acid. The yield of tungsten monocarbide WC in the course of
synthesis increases by approximately two times with glucose.
Figure 10. Electrode system for testing the process of obtaining nanopowders by the
vacuum-arc method: 1 - cooled screen, 2 - graphite electrode-anode, 3 - graphite
electrode-cathode, 4 - sample, 5 - technological hole for initiating a vacuum arc, 6 -
holder, 7 - flange, 8 – inlet (Kudaykulov et al. 2022; Ashurov et al. 2021).
Complimentary Copy
Figure 11. Scheme of the main elements of the carbide plasma synthesis setup: (1)
nozzle (anode), (2) branch for supplying a plasma forming gas and a charge
(cathode), (3) cooling system, (4) gas removal channel, (5) flow fairing, and (6)
synthesis chamber (plasma-chemical reactor). C stands for concentrate; G, graphite
(Balakhonov et al. 2020).
Balakhonov et al. (2020) studied the plasma-chemical synthesis of

tungsten carbides from multicomponent oxide-containing concentrates. In this
work authors developed a method for producing refractory metal carbides
from multicomponent tungsten-containing mineral raw materials by plasma-
chemical synthesis. For experiments, a scheelite concentrate and calcium
tungstate were selected as raw materials and graphite was used as a carbon
source. Figure 11 schematically shows the plasma-chemical synthesis setup
and the supplying of a charge into the reactor chamber.
It can be seen the phase analysis of samples revealed the presence of the
main phases of tungsten carbide, namely, W2C and WC (Figure 12). The
carbon content in WC was 6.2–7.1 wt % (57 at % W, 43 at % C), In the W2C
phase, carbon reached 3.4 wt% (72 at % W, 28 at % C). The content of reduced
tungsten in the nanocrystalline powder (WC–W2C) was found to be 7.5 wt%.
Excess tungsten (in at %) in WC and W2C indicates the presence of free
tungsten atoms. Authors also investigated the dependence of mass of
synthetized tungsten carbide as a function the plasma flow temperature and
the plasma flow action time (Figures 13 and 14). These results demonstrate
the prospects of plasma-chemical synthesis of tungsten carbides from
tungsten-containing mineral concentrates.
Complimentary Copy
134 D.T. Usmanov
Figure 12. X-ray diffraction pattern of the nanocrystalline W‒C powder formed
from scheelite concentrate by plasma-chemical synthesis (Balakhonov et al. 2020).
Figure 13. Mass of synthesized tungsten carbide vs. the plasma flow temperature
and the fraction of graphite introduced into a charge: (a) scheelite concentrate and (b)
calcium tungstate (Balakhonov et al. 2020).
Ilin et al. (2012) investigated the properties of nanopowders of tungsten

carbides, titanium, tantalum, aluminum produced by electric explosion of
conductors in gaseous and liquid hydrocarbons. The effect of synthesis
conditions on the disperse and phase composition of metal carbides is
established. The study of the phase composition of the products of electrical
tungsten conductor explosion in an acetylene-argon gas medium showed that
the obtained powders contain phases β-WC (WC1-x), W2C, α-W and β-W.
Relative content carbide phases, defined as the ratio of the intensities of 100%
phase reflections W2C and WC1-x on radiographs are presented in Table 1.
Complimentary Copy
Figure 14. Mass of synthesized tungsten carbide vs. plasma flow action time τ and
the fraction of graphite introduced into a charge: (a) scheelite concentrate and (b)
calcium tungstate (Balakhonov et al. 2020).
Table 1. The composition of the products of the electrical explosion of

tungsten conductors in acetylene argon gas environment (Ilin et al. 2012)
e/ec eД/ec Ar:C2H2 W2C:WC1-x

0,9 0,4 9:1 0,55
0,7 0,1 4:1 0,47
0,8 0,2 4:1 0,34
0,9 0,4 4:1 0,20
0,9 1,5 4:1 0,12
Under the method in an acetylene-argon mixture with a molar ratio of

Ar:C2H2 = 4:1 with an increase in the energy introduced into the conductor
from 0.7 es to 0.9 es and the energy of the arc stage from 0.1 es to 1.5 es, there
is a decrease in the relative content of tungsten carbide W2C less saturated
with carbon and an increase in the content of the WC1-x phase (Table 1). A
decrease in the relative yield of the W2C phase with respect to WC1-x was
observed with a decrease in the degree of dilution of acetylene with argon from
9:1 to 4:1 molar ratios. An increase in the relative yield of the W2C phase with
respect to WC1-x was caused by the replacement of acetylene by propane at a
molar ratio of Ar:C3H8 = 2:1.
Complimentary Copy
136 D.T. Usmanov
Figure 15. SEM image of products of electric explosion of tungsten conductors in

acetylene-argon gas medium, e/ec = 0.9, u/ec = 1.5 (Ilin et al. 2012).
Figure 16. AFM morphology after 60 s annealing in propane diluted in hydrogen at

(a) 1000oC and (b) 1350oC (Romanus et al. 2000).
Tungsten carbide powders obtained by the method in gaseous

hydrocarbons consist of spherical particles with a diameter of 0.01 to 2 μm,
hich have a smooth surface (Figure 15). The particle size tends to decrease as
the energy consumed by the conductor before the explosion increases. It has
been established that the factors affecting the disperse, phase and chemical
composition of the resulting powders are the energy introduced into the
conductor before the explosion, the energy of the arc stage, and the properties
of the medium surrounding the exploding conductor are taken into account.
Complimentary Copy
The investigation of thin layers for hard coatings or electrical applications

requires the preparation of a homogeneous material. Romanus et al. (2000)
prepared tungsten carbide layers using sputtering from a stoichiometric WC
target and subsequent annealing. Carbide formation was found at temperatures
above 800°C.
Annealing in pure hydrogen leads to depletion of the layers in carbon and
the formation dominant phase of W2C. In this work authors that the addition
of propane to the annealing medium stimulates the transformation of the
tungsten-carbon layers to the stoichiometric WC phase. Changing the propane
concentration allows to continuously change the layer structure between
single-phase WC and mixed layer with dominant W2C and adjustment of
various values of electrical resistance and optical resistance constants. It can
be seen that the morphology changes drastically at increased annealing
temperatures (Figure 16). At 1000°C crystallites appear at the surface which
become larger at higher temperatures (Figure 16 a). Above 1200°C a definite
grainy surface arises. The resulting surface roughness increases monotonically
at higher temperatures. Depending on the propane concentration, the ratio
between the WC and W2C phases can be varied and different electrical
resistances and optical constants can be controlled.
Figure 17. X-ray patterns of various tungsten carbide/carbon composites

(Lian et al. 2020).
Complimentary Copy
138 D.T. Usmanov
Figure 18. X-ray patterns of (a) nanopowder synthesized by alternating current arc
discharge and (b) nanopowder synthesized by direct current arc discharge (Burakov
et al. 2008).
In work (Lian et al. 2020), the authors obtained a series of solvent-free

tungsten carbide/carbon composites, where a solid mixture of dicyandiamide
(DCA) and ammonium metatungstate (AM) were used as precursors. Figure
17 shows X-ray diffraction patterns of tungsten carbide/carbon composites
from different DCA/AM weight ratios. It can be seen that all samples show
three identical and well-resolved peaks at 37.0°, 62.0° and 74.2°. It is known
that tungsten carbide has three crystal structures, namely, the hexagonal WC
phase, the close-packed hexagonal W2C phase, and the face-centered cubic
Complimentary Copy
WC1−x phase. Three peaks of these composites can be exactly matched to the
(111), (220), and (311) WC1 – x (Kim et al. 2009; Kim et al. 2018) planes,
respectively, indicating that tungsten carbide mainly exists as WC1 – x in these
composites. Using these measured templates, it can be calculated that the
average cell parameter (a) of a cubic WC1 – x nanoparticle here is about 0.4223
nm. As determined, the WC1 – x phase usually forms under conditions rich in
carbon (Kim et al. 2018). Although the minimum weight ratio of DCA to AM
is only 2.0, the actual C/W molar ratio is greater than 10.0 and thus the
formation of WC1−x nanoparticles in these composites will be more clearly
understood. A large excess of DCA not only promotes the formation of WC1−x
nanoparticles, but also produces individual carbon components, while these
individual carbon components cannot present any characteristic peaks due to
their amorphous nature.
Kurlov and Gusev (2006) studied the phase transformation of tungsten
carbide particles in detail and they suggested that a was a parabolic function
of the carbon content in WC1–x particles, and their relationship can be
described by formula 1.
a = 0.4015 + 0.0481(1 − x) − 0.0236(1 − x)2 (1)
Based on Equation 1, the resulting value of 1 - x is about 0.62, using

0.4223, and thus the specific expression of the tungsten carbide nanoparticles
in these composites should be WC 0.62.
In work (Burakov et al. 2008), a tungsten carbide nanopowder was
obtained by a pulsed discharge of bulk tungsten and graphite rods immersed
in pure ethanol. The effect of the discharge parameters on the performance of
the final product has been investigated. The structural and morphological
characterization of the nanopowder was carried out using X-ray diffraction
analysis and transmission electron microscopy. In order to determine the
possibility of using the synthesized material as an electrocatalyst, tungsten
carbide nanopowder was tested for hydrogen evolution. A correlation was
found between the morphology of nanoparticles in their phase composition
and electrocatalytic activity. X-ray diffraction data were collected to
characterize the samples. The nanopowder also contained a small amount of
body-centered cubic W (diffraction peak at 40.3°, not shown in Figure 18)
when the synthesis was carried out by a direct current spark discharge with a
tungsten rod as a cathode. Here, stress should be a feature of the behavior of
this discharge, showing a sufficiently high ability to synthesize W2C.
Moreover, unlike the other discharge spark, the synthesized material contained
Complimentary Copy
140 D.T. Usmanov
a relatively small amount of graphite. On the other hand, the use of tungsten
as a cathode material appears to reduce the content of C in the nanopowder
obtained by the arc discharge method too. As a rule, the content of C was
higher and the content of WC1–x was lower in spark discharge synthesis.
Figure 19. TEM images of (a) nanopowder synthesized by alternating current arc
discharge and (b) nanopowder synthesized by direct current arc discharge. The size
distribution of nanoparticles is shown as an inset (Burakov et al. 2008).
Figure 19 shows representative TEM images of (a) a nanopowder

synthesized by an arc and (b) a spark discharge. Both images were taken at
100,000 times magnification. Nanoparticles obtained by arc discharge were
Complimentary Copy
observed in agglomerated form. Due to the agglomeration, it was difficult to

correctly measure their size. However, as can be seen from Figure 19a, these
agglomerations consisted of primary particles typically 5–10 nm in size. The
basic nanoparticles seemed to form three-dimensional (3D) structures. The
small dark spots in Figure 19a probably indicate this process. The
agglomerated nanoparticles were surrounded by gray areas with arrows, which
were probably layers of carbon, as shown in Figure 19a. This typical
appearance was seen throughout the TEM images of the arc-synthesized
product for both AC and DC discharges regardless of electrode polarity.
This fact means that the morphology of the synthesized nanopowders was
controlled by the current pulse duration and peak current value rather than by
the polarity of the electrodes. Figure 19b demonstrates that the spark-
synthesized nanoparticles were almost spherical with an average diameter of
7 nm. The particle size distribution with a standard deviation of 0.4 nm is
shown in the inset to Figure 19b. Comparison of the morphology of
nanoparticles from Figure 19 a and b it follows that agglomeration could have
occurred at the time of discharge. Otherwise, nanoparticle agglomeration will
be observed in all experiments. The agglomeration process requires a low peak
current (a few A) and a long continuous discharge (a few ms).
Hard alloys have a set of properties that are simultaneously inherent in all
their constituent components, which significantly expands the scope of
practical application of such composite materials in all areas of production.
Designations of grades of alloys are built according to the following principle:
alloys containing tungsten carbide and cobalt are designated by the letters TC
(tungsten-cobalt), after which the percentage of cobalt Co in the alloy is
indicated by numbers (Geller et al. 1989). The physical and mechanical
properties of TC alloys are determined by the dimensional parameters of
carbide grains, the content of Co (from 1.5 to 32%) in the total mass, and
technological differences in the production processes of sintering and casting.
Coarseness of tungsten carbide grains makes the alloy more ductile and at the
same time leads to an increase in hardness. With an increase in the
concentration of Co, the strength-cutting characteristics improve, but the
strength and wear resistance deteriorate. That is why alloys with a low
concentration of Co (TC2, TC3, TC4), which are characterized by relatively
low values of stiffness and wear resistance. Due to their low strength, it is
advisable to use them in the manufacture of tools intended for surface
finishing. According to the manufacturing method, hard alloys are divided into
two categories: sintered, produced by sintering carbide powders WC, TiC,
TaC with a metal binder in the form of Co; cast, obtained as a result of melting
Complimentary Copy
142 D.T. Usmanov
and subsequent molding pressing of bars (Arzamasov et al. 2001). Products

made from sintered alloys cannot be machined. Processing is possible using
physicochemical (acid etching), laser and ultrasonic methods. All varieties of
cast hard alloys are used for welding on the working edges of cutting and
mining equipment, as well as for applying protective and hardening coatings
on metal surfaces. They can be processed both mechanically and thermally
(hardening, annealing, aging, etc.). The category of sintered hard metal-
ceramic alloys, or cermets, includes a line of composite materials (solid
solutions) obtained by mold pressing followed by sintering in vacuum-
hydrogen environments at 1550-2100°C of carbide powder components
(tungsten or titanium carbides, as well as complex carbides W, Ti and that,
less often - other carbides, borides, etc.) with a damping matrix binder, which
is used as softer and more ductile metals/alloys. Usually Co, which does not
react with C and does not form its own carbides, acts as such a binder;
sometimes - Ni or Ni-Mo alloy. The ability of hard alloys to maintain initially
high hardness and resistance to deformation effects in high-temperature
conditions, combined with acceptable strength characteristics, is their
undeniable advantage over the lines of all other tool materials.
Conclusion
This brief literature review shows that until now the production of tungsten
carbide nanoparticles and their application have significantly advanced. The
application of tungsten carbide materials widens from instrumental
application to jewelry field as well as medicine. Nowadays, to produce
tungsten carbide nanopowders has been used many physical and chemical
synthesized methods. Every of these methods has advantageous and
disadvantageous. Among them, the most common are plasma-chemical, gas-
phase, thermal evaporation, electric explosion of a conductor, and
hydrothermal methods. The synthesized nanoparticles by these methods have
a small and spherical size. The WC, W2C, and WC1-x phases are formed during
the synthesis of tungsten carbide nanoparticles in various methods depending
on the experimental parameters. In spite of such progress, the development of
low-cost, efficient and fast technologies for the production of tungsten carbide
nanoparticles, as well as the acceleration of their application in various fields,
remains an urgent task in this area.
Complimentary Copy
References
Ashurov, Kh. B., Arustamov, V. N., Khudaikulov, I. Kh., et al. (2021). Studies of tungsten
carbide nanoparticles obtained by the plasma-chemical method. Uzbek Journal of
Physics, 23(3), 17-23.
Balakhonov, D. I., and Makarov, I. A. (2020). Plasma-Chemical Synthesis of Tungsten
Carbides from Multicomponent Oxide-Containing Concentrates. Russ Metall, 870–
876.
Baraton, M. I. (2002). Synthesis, Functionalization, and Surface Treatment of
Nanoparticles. Am. Sci., Los-Angeles.
Burakov, V. S., Butsen, A. V., Bruser, V., et al. (2008). Synthesis of tungsten carbide
nanopowder via submerged discharge method. J Nanopart Res, 10, 881–886.
Chen, S. J., Li, J., Chen, X. T., et al. (2003). Solvothermal synthesis and characterization
of crystalline CaWO4 nanoparticles. Journal of Crystal Growth, 253, 361 – 365.
Domashenko, V. V., Lerner, M. I., and Psakhie, S. G. (2004). Synthesis of composite metal
nanoparticles by the method of electrical explosion of conductors. Journal of
Structural Chemistry, 45, 23-129.
Geller, Yu. A. (1989). Materials Science: Textbook for High Schools. Geller YuA,
Rakhshtadt AG; ed. A.G. Rakhstadt. M.: Metallurgy.
Gusev, A. I., and Rempel, A. A. (2004). Nanocrystalline Materials. Cambridge: Cambridge
International Science Publishing.
Gusev, A. I. (2007). Nanomaterials, nanostructures, nanotechnologies. Moscow: Fizmatlit.
Hamp, R., Gorr, E., and Cameron, K. (2011). Four-Stroke Motocross and Off-Road
Performance Handbook. MotorBooks International.
Ilyin, A. P., Nazarenko, O. B., and Tikhonov, D. V. (2012). Synthesis of metal carbides by
electric explosion of conductors. Bulletin of Science of Siberia, 3 (4), 80-88.
Isaeva, N. V., Blagoveshchensky, Yu. V., Blagoveshchenskaya, N. V., et al. (2013).
Obtaining nanopowders of carbides and hard alloy mixtures using low-temperature
plasma. Izvestiya VUZov, PMiFP, 3, 7-15.
Karimi, H., and Morteza, H. (2020). Effect of sintering techniques on the structure and dry
sliding wear behavior of WC-FeAl composite. Ceramics International, 46 (11, Part
B),18487–18497.
Karpov, I. V., Ushakov, A. V., Fedorov, L. Y., et al. (2014). Method for producing
nanomaterials in the plasma of a low-pressure pulsed arc discharge. Tech Phys, 59,
559–563.
Khudaykulov, I. Kh., Ravshanov, Zh. R., Ashurov, Kh. B., et al. (2022). X-Ray Phase
Analysis of Tungsten-Carbide Nanoparticles Synthesized Using the Vacuum-Arc
Technique. Journal of Surface Investigation: X-ray, Synchrotron and Neutron
Techniques, 16(4), 599–604.
Kim, I., Park, S., and Kim, D. (2018). Carbon-encapsulated multi-phase nanocomposite of
W2C@WC1−x as a highly active and stable electrocatalyst for hydrogen generation.
Nanoscale, 10, 21123–21131.
Kim, J., Jang, J., Lee, Y., et al. (2009). Enhancement of electrocatalytic activity of platinum
for hydrogen oxidation reaction by sonochemically synthesized WC 1−x nanoparticles.
J. Power Sources, 193, 441–446.
Complimentary Copy
144 D.T. Usmanov
Kotov, Yu. A., Beketov, Yu. V., Somatov, O. M., et al. (1997). Patent RU 2093311 C1,
IPC 6 B22F9/14. Installation for obtaining ultrafine powders of metals, alloys and
chemical compounds by the method of electric wire explosion – 94042588/02;
Published 20.10.1997.
Kotov, Yu. A., Beketov, I. V., and Samatov, O. M. (2000). Patent RU 2149735 C1, IPC
B22F9/14. Installation for obtaining highly dispersed powders of metals, alloys and
their chemical compounds by the method of electric wire explosion - 98118257/02;
Published 27.05.2000.
Kotov, Yu. A. (1999). Obtaining nanopowders by the EEW method. IV All-Russian Conf.
“Physical chemistry of ultrafine systems”. Sat. scientific works. M; 60-66.
Krasovsky, P. V., Blagoveshchenskiy, Yu. V., and Grigorovich, K. V. (2008).
Determination of oxygen content in WC–Co nanopowders. Inorg. Mater., 44(8), 1–6.
Kurlov, A. S., and Gusev, A. I. (2006). Tungsten Carbides and W–C Phase Diagram.
Inorganic Materials, 42(2), 121–127.
Lerner, M. I., and Shamansky, V. V. (2004). Formation of nanoparticles when a metal
conductor is exposed to a high-power current pulse. Journal of Structural Chemistry,
45, 112-115.
Lerner, M. I., Svarovskaya, N. V., Psakhie, S. G., et al. (2009). Production technology,
characteristics and some areas of application of electro explosive metal nanopowders.
Russian Nanotechnologies, 4(9), 59-64.
Lian, Y., Han, B., Liu, D., et al. (2020). Solvent-Free Synthesis of Ultrafine Tungsten
Carbide Nanoparticles-Decorated Carbon Nanosheets for Microwave Absorption.
Nano-Micro Lett, 12, 153.
Lyakhov, N. Z., Yukhin, Yu. M., and Tukhtaev, R. K. (2014). Obtaining metallic
nanopowders by reduction in organic liquids. Chemistry for sustainable development,
22, 409-416.
Materials Science: Proc. for universities. Arzamasov BN, Makarova VI, Mukhin GG, et al;
Under total ed. Arzamasova BN, Mukhina GG. - 3rd ed., revised. and additional. M .:
Publishing house of MSTU; 2001.
Mostajeran, A., Shoja-Razavi, R., Hadi, M., Erfanmanesh, M., and Karimi, H. (2020). Wear
behavior of laser cladded WC-FeAl coating on 321 stainless steel substrate. Journal
of Laser Applications, 32 (4), 042015.
Pak, A. Ya., Shanenkov, I. I., Mamontov, G. Y., and Kokorina, A. I. (2020). Vacuumless
synthesis of tungsten carbide in a self-shielding atmospheric plasma of DC arc
discharge. Int J Refract Met Hard Mater, 93, 105343
Rao, P. (2009). Manufacturing Technology Vol. II 2E. Tata McGraw-Hill Education.
Romanus, H., Cimalla, V., Schaefer, J. A., et al. (2000). Preparation of single phase
tungsten carbide by annealing of sputtered tungsten-carbon layers. Thin Solid Films,
359(2), 146-149.
Sagadevan, S., Das, I., Singh, P., et al. (2017). Synthesis of tungsten carbide nanoparticles
by hydrothermal method and its Characterization. J Mater Sci: Mater Electron, 28,
1136–1141.
Saito, Y., Matsumoto, T., and Nishikubo, K. (1997). Encapsulation of carbides of
chromium, molybdenum and tungsten in carbon nanocapsules by arc discharge. J
Cryst Growth, 172(1–2), 163-170.
Complimentary Copy
Samokhin, A. V., Alekseev, N. V., Kornev, S. A., et al. (2013). Tungsten Carbide and
Vanadium Carbide Nanopowders Synthesis in DC Plasma Reactor. Plasma Chem
Plasma Process, 33, 605–616.
Sedoy, V. S., Kotov, Yu. A., and Samatov, O. M. (1999). Patent RU 2139777 C1, IPC
B22F9/14. Installation for the production of fine powders - 98115703/02; Published
20. 10.1999.
Sickafoose, S. M., Smith, A. W., and Morse, M. D. (2002). Optical spectroscopy of
tungsten carbide (WC). J. Chem. Phys, 116 (3), 993-1002.
Sivkov, A. A., Shanenkov, I. I., Shanenkova, Yu. L., et al. (2021). Plasma Dynamic
Synthesis of Cubic Tungsten Carbide and the Influence of the Gas Atmosphere
Parameters. Journal of Surface Investigation: X-ray, Synchrotron and Neutron
Techniques, 15, 361-370.
Wang, B. B., Zheng, K., Gao, D., et al. (2016). Plasma-chemical synthesis, structure and
photoluminescence properties of hybrid graphene nanoflake–BNCO nanowall
systems. J. Mater. Chem. C, 4, 9788-9797.
Yavorovsky, N. A., Davydovich, V. I., and Bill, B. A. (1995). Patent RU 2048278 C1, IPC
6V22F9/14. Installation for the production of highly dispersed powders of inorganic
materials by electric explosion and a reactor for the explosion of a metal billet -
5004107/02; Published 20.11.1995.
Zhao, S. Q., Jin, S. W., and Wang, Y. X. (2013). The Preparation of Ultrafine Tungsten
Carbide Nanoparticles by DC Arc Discharge Plasma Process. Modern Physics Letters
B, 27(19), 1341003.
Zhao, S. Q., Jin, S. W., and Wang, Y. X. (2013). The preparation of ultrafine tungsten
carbide nanoparticles by dc arc discharge plasma process. Mod Phys Lett B, 27(19),
1341003.
Zhigach, A. N., Kuskov, M. L., Leipunsky, I. O., Stoenko, N. I., and Storozhev, V. B.
(2012). Levitation-jet method for obtaining ultrafine powders of metals, alloys, metal
compounds by the gene-miller method: history, current state, prospects. Proceedings
of the Russian Academy of Sciences. Energy, 3, 80-96.
Biographical Sketch
Name: Usmanov Dilshadbek Tursunbaevich

Affiliation: Arifov Institute of Ion-Plasma and Laser Technologies,
Uzbekistan Academy of Sciences
Education: PhD (2009), DSc (2018), Professor (2022)
Business Address: Durmon Yoli street 33, 100125, Tashkent, Republic
of Uzbekistan
Research and Professional Experience: Mass spectrometry, physical
chemistry, analytical chemistry and emission electronics: Development of
vacuum and atmospheric pressure ionization methods for sensitive detection
Complimentary Copy
146 D.T. Usmanov
organic compounds including biological samples. Basics of ionization

process. Cluster formations and multiple charges.
Material sciences: Development of effective synthesis technologies.

Synthesis of nanoparticles and determination of their physicochemical
properties.
Developed the SI/MS method for an express detection of trace amounts
of drugs in various bio samples.
Developed several new ambient and atmospheric pressure ionization
sources for sensitive detection drugs and explosive compounds.
Under his guidance the surface ionization method was applied for post
ionization of neutral gallium arsenide atoms in secondary ion mass-
spectrometry.
Under his guidance the new plasma-based method was developed for
effective synthesis of tungsten carbide nanoparticles.
Supervised 3 PhD and 2 DSc (Doctor of Science)
Professional Appointments: Member of Editorial Board of Austin

Biochemistry journal, Principal scientist, Scientific secretary
Honors: MSSJ AWARD for Excellent Article 2021 (with co-authors),

The Mass Spectrometry Society of Japan (2021)
Article was selected for the front page of the journal “Front Featured
Cover image” (RCMS, with co-authors) (2020)
Article was selected for the front page of the journal (RCMS, with co-
authors) (2018)
Article was selected as one of the top 10% of papers published in the
journal (Analytical methods, with co-authors) (2017)
Article was selected as featured article and for the front page of the journal
(Journal of Mass Spectrometry, with co-authors) (2015)
Prize of State Committee on Science and Technology of the Republic of
Uzbekistan (2003)
Prize of Uzbekistan Academy of Sciences for young scientists (2002)
Publications from the Last 3 Years:

[1] Akhunov, S. D., Kakhramonova, G. P., and Usmanov, D. T. (2023). Ion-photon
emission under bombardment of Ta target with cluster and multiply charged Bi ions.
Vacuum, 213, 112160.
Complimentary Copy
[2] Hiraoka, K., Usmanov, D. T., Ninomiya, S., Rankin-Turner, S., and Akashi, S.
(2023). Site-specific sodiation of peptides studied by pulsed nanoelectrospray
ionization. International Journal of Mass Spectrometry, 490, 117073
[3] Abdullaeva, B., K., Amatov, Sh. Ya., Shermetova, A. S., Akhunov, Sh. J.,
Kakhramonova, P. G., and Usmanov, D. T. (2023). Research on the yield of
secondary particles during the bombardment of a GaAs single crystal with multiply
charged Biq+ ions, Bulletin of the Khorezm Academy of Mamun, 2/1, 166-17
[4] Radjabov, A. Sh., Khasanov, U., Iskhakova, S. S., Akhmedov, Sh. M.,
Kakhramanova, G. P., Akhunov, Sh. Dj., and Usmanov, D. T. (2023). Analytical
capabilities of a thermodesorption spectrometer with a surface-ionization detection
of organic molecules in air. Technical Physics, Vol. 68, No. 3, 389-396.
[5] Rakhmanov, G. T., Umirzakov, B. E., and Usmanov, D. T. (2023). Determination
of the kinetic characteristics of thermodesorption and the heterogeneous reaction of
the dissociation of morpine molecules on the surface of oxidated tungsten. Journal
of Surface Investigation: X-ray, Synchrotron and Neutron Techniques, 17(3), 542–
547.
[6] Rakhmanov, G. T., and Usmanov, D. T. (2023). Determination of kinetic
characteristics of molecule thermodesorption on the surface of oxidated
molybdenum. International Journal of Chemical Kinetics, 1-7. DOI:
10.1002/kin.21655
[7] Rakhmanov, G. T., and Usmanov, D. T. (2022). Mass-spectrometric studies of
kinetic characteristics of codeine molecule thermodesorption by non-stationary
surface ionization method, Eur J Mass Spectrom, 28(5-6), 127-131.
[8] Г. Т. Рахманов, Д. Т. Усманов, (2022). Исследование диссоциативной
поверхностной ионизации молекул тебаина нестационарными методами
поверхностной ионизации, Письма в ЖТФ, том 48, вып. 20, 27-30 [Rakhmanov,
G. T., and Usmanov, D. T. (2022). Investigation of dissociative surface ionization
of thebaine molecules by non-stationary methods of surface ionization, JTF Letters,
vol. 48, no. 20, 27-30].
[9] Ashurov, R. Kh., Ashurov, Kh. B., Arustamov, V. N., Khudaikulov, I. Kh., and
Usmanov, D. T. (2022). Synthesis of tungsten nanoparticles by electron beam
evaporation, Uzbek Journal of Physics, Vol. 24, No. 4, pp. 268-272.
[10] Akhunov, Sh. Dj., Kakhramonova, G. P., Axmedov, Sh. M., Kasimov, B. Sh., and
Usmanov, D. T. (2022). Sputtering of GaAs target under Bim+ cluster ions
bombardment, Nuclear Instruments and Methods in Physics Research Section B:
Beam Interactions with Materials and Atoms, V. 528, Pages 15-19.
[11] Khudaykulov, I. Kh., Ravshanov, Zh. R., Ashurov, Kh. B., Arustamov, V. N., and
Usmanov, D. T. (2022). X-Ray Phase Analysis of Tungsten-Carbide Nanoparticles
Synthesized Using the Vacuum-Arc Technique. Journal of Surface Investigation:
X-ray, Synchrotron and Neutron Techniques, Vol. 16, No. 4, pp. 599–604.
[12] Radjabov, A. S., Iskhakova, S. S., and Usmanov, D. T. (2022). Investigation of the
Operation Speed of Surface-Ionization Detectors. Tech. Phys., 67, pp. 104–111.
https://doi.org/10.1134/ S106378422201011X.
[13] Akhunov, Sh. D., Kasimov, B. Sh., Ashurov, Kh. B., and Usmanov, D. T. (2021).
Development of a Surface Ionization Mass Spectrometry Method for the Highly
Complimentary Copy
148 D.T. Usmanov
Sensitive and Highly Selective Analysis of Morphine in Biofluid. Journal of

Analytical Chemistry, volume 76, pages 1499–1504.
[14] Ashurov, Kh. B., Arustamov, V. N., Khudaikulov, I. Kh., Ravshanov, Zh. R., and
Usmanov, D. T. (2021). Studies of tungsten carbide nanoparticles obtained by the
plasma-chemical method. Uzbek Journal of Physics, Vol. 23, No. 3, pp. 17-23.
[15] Shovkatjon Akhunov, Khatam Ashurov, Sherzod Axmedov, Beknazar Kasimov,
Vladimir Rotshteyn, Azim Radjabov and Dilshadbek Usmanov. (2021).
Development of surface ionization mass spectrometry for detection of stimulants in
human urine. European Journal of Mass Spectrometry, Vol. 27(1), 29–38.
[16] Akhunov, Sh. Dj., Rasulev, U. Kh., and Usmanov, D. T. (2021). On the Sputtering
of Copper Phthalocyanine Molecules on a GaAs Substrate under Bombardment with
Multiply Charged Ions. Journal of Surface Investigation: X-ray, Synchrotron and
Neutron Techniques, Vol. 15, No. 2, pp. 396–400.
[17] Kasimov, B. Sh., Akhunov, Sh. J., Akhmedov, Sh. M., and Usmanov, D. T. (2021).
Surface ionization of narcotic stimulants in biological samples. Uzbek Journal of
Physics, Vol. 23, No. 1, pp. 75-81.
[18] Akhunov, Sh. J., and Usmanov, D. T. (2020). Sputtering of a CaCO3 target upon
bombardment with Bim+ cluster ions. Uzbek Journal of Physics, Vol. 22, No. 6, pp.
350-355.
[19] Iskhakova, S. S., Khasanov, U., Usmanov, D. T., Radzhabov, A. Sh., Toirov, M. T.
(2020). Thermionic mass and thermal desorption spectrometry of psychotropic
drugs. Uzbek Journal of Physics, Vol. 22, No. 6, pp. 374-382.
[20] Hiraoka, K., Ariyada, O., Usmanov, D. T., Chen, L. C., Ninomiya, S., Yoshimura,
K., Takeda, S., Yu, Z., Mandal, M. K., Wada, H., Rankin-Turner, S., and Nonami,
H. (2020). Probe electrospray ionization (PESI) and its modified versions: dipping
PESI (dPESI), sheath-flow PESI (sfPESI) and adjustable sfPESI (ad-sfPESI)
(review), Mass spectrometry (Japan), Article ID: A0092,
https://doi.org/10.5702/massspectrometry.A0092.
[21] Khasanov, U., Iskhakova, S. S., and Usmanov, D. T. (2020). Examination of the
effect of air atmosphere on heterogeneous reactions under surface ionization of
psychotropic drug molecules, European Journal of Mass Spectrometry, European
Journal of Mass Spectrometry, Vol. 26(6), 409–418.
[22] Iskhakova, S. S., Khasanov, U., Rasulev, U. Kh., and Usmanov, D. T. (2020).
Thermodesorption Spectrometer of Hard-Volatile Active Organic Compounds.
Technical Physics Letters, Vol. 46, No. 12, pp. 1231–1234.
[23] Satoshi Ninomiya, Shunpei Iwamoto, Dilshadbek Usmanov, Shinichi Yamabe, and
Kenzo Hiraoka. (2021). Negative-mode mass spectrometric study on dc corona, ac
corona and dielectric barrier discharge ionization in ambient air containing H 2O2,
2,4,6-trinitrotuluene (TNT), and 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), Int. J.
Mass Spectr., 459, 116440 https://doi.org/10.1016/j.ijms.2020.116440 .
[24] Dilshadbek T. Usmanov, Satoshi Ninomiya, Kenzo Hiraoka. (2020). Flash
desorption of low-volatility compounds deposited on the heated solid substrate
(90оC) by dripping liquid methanol, Rapid Comm. Mass Spectr., Volume 34, Issue
23.
Complimentary Copy
[25] Kenzo Hiraoka, Osamu Ariyada, Ryo Sekine, Satoshi Ninomiya, Dilshadbek T.
Usmanov, Hiroshi Wada, and Hiroshi Nonami. (2020). Robotic sheath-flow probe
electrospray ionization (sfPESI) equipped with a touch sensor for samples in a
multiwell plastic plates. Analytical Methods, Vol.12 (22), pp. 2812-2819.
[26] Dilshadbek T. Usmanov, Satoshi Ninomiya, Kenzo Hiraoka, Shinichi Yamabe,
(2020). A novel contrast of the reactions of 2,4,6-trinitrotoluene (TNT) in
atmospheric-pressure O2 and N2 plasma: Experimental and theoretical study,
International Journal of Mass Spectrometry, 450, 116308.
[27] Usmanov, D. T., and Saydumarov, M. M., (2020). Surface ionization mass
spectrometry of physiologically active organic compounds and its application,
Tashkent, “Tafakkur Bo’stoni”, p. 152.
[28] Usmanov, D. T., Akhunov, Sh. Dj., Khasanov, U., Rotshteyn, V. M., and Kasimov,
B. Sh. (2020). Direct detection of morphine in human urine by surface-ionization
mass spectrometry, European Journal of Mass Spectrometry, Vol. 26(2) 153–157.
Complimentary Copy
Complimentary Copy
Chapter 4
Advances in Research and Applications

of Tungsten Carbides in Micro-EDM
for Titanium Alloy
Phan Nguyen Huu1

Dung Hoang Tien1
Shailesh Shirguppikar2
Long Banh Tien3
Toan Nguyen Duc3
and Vaibhav Ganachari2
1Faculty of Mechanical Engineering, Hanoi University of Industry, BacTuLiem District,
Hanoi, Vietnam
2Department of Mechatronics Engineering, Rajarambapu Institute of Technology, Shivaji
University, Sakharale, India

3
Hanoi University of Science and Technology, Hanoi, Vietnam
Abstract
Titanium alloys are widely used in various industries due to their

excellent mechanical properties and corrosion resistance. However, their
high strength and low thermal conductivity pose challenges in machining
processes, especially in micro-electrical discharge machining (micro-
EDM). Tungsten carbide (WC) is a promising material with exceptional
hardness and wear resistance, making it suitable for micro-EDM
applications. This chapter presents recent advances in the research and
applications of tungsten carbides in micro-EDM for titanium alloy
machining. The first part discusses the synthesis and characterization
techniques of WC-based materials, including different WC grain sizes,

ISBN: 979-8-89113-221-4
Complimentary Copy
152 Nguyen Huu Phan, Dung Hoang Tien, Shailesh Shirguppikar et al.
binder phases, and composite structures. The influence of these

parameters on the mechanical and electrical properties of WC-based
electrodes is analyzed, highlighting their impact on the machining
performance. The second part focuses on the utilization of WC-based
electrodes in micro-EDM for titanium alloy machining. Various process
parameters, such as discharge current, pulse duration, and electrode
material composition, are investigated to optimize the machining
efficiency and surface integrity. The effects of these parameters on
material removal rate, tool wear, surface roughness, and recast layer
formation are thoroughly examined. The findings of this study
demonstrate the significant potential of tungsten carbides in micro-EDM
for titanium alloy machining. The use of WC-based electrodes can
improve the machining efficiency and surface quality while minimizing
electrode wear. Furthermore, this research contributes to a better
understanding of the fundamental mechanisms involved in micro-EDM
of titanium alloys and provides valuable insights for future research and
development in this field.
Keywords: literature review, micro-EDM, Titanium alloy
Introduction
Titanium alloys are metals that contain a mixture of titanium and other
chemical elements. These alloys have very high tensile strength and toughness
(even at extreme temperatures). They are lightweight, have extraordinary
corrosion resistance and the ability to withstand extreme temperatures.
However, the high cost of raw materials and processing limits their use to
military applications, aircraft, spacecraft, bicycles, medical devices, jewelry,
highly stressed components such as the rods of expensive sports cars and some
high-end sports equipment and consumer electronics. Although
“commercially pure” titanium has acceptable mechanical properties and has
been used for orthopedic and dental implants, for most applications, titanium
is alloyed with small amounts of aluminum and vanadium, typically 6% and
4% respectively, by weight. This mixture has a solid solubility which varies
considerably with temperature, allowing it to undergo an increase in
precipitation. This heat treatment process is carried out after the alloy has been
formed into its final form but before it is put into service, which facilitates the
manufacture of a high strength product. Applications of Titanium Alloys such
as Aerospace, Industrial, Medical Field, Architecture. Ti-6Al-4V is one of the
most widely used alloys due to its ability to retain exceptional physical
Complimentary Copy
Advances in Research and Applications of Tungsten Carbides … 153
properties even at high temperatures. The various properties of these alloys
embody the light weight associated with high strength, excellent resistance
to fatigue and creep, good protection in corrosive environments, and
biocompatibility. Ti-6Al-4V is used in various fields such as automotive
industry, biomedical industry, aerospace industry, marine industry and
chemical process industry [1]. Due to machining limitations, conventional
machining, non- conventional machining methods such as laser processing,
electrochemical methods, and this alloy with an EDM process (such as low
thermo-physical phenomena and work hardening) used to machine some
materials [2, 3, 4]. Electric discharge machining (EDM) is the thermal erosion
method during which material is removed by melting or vaporizing minuscule
areas at the surface of workpiece. The EDM method removes material by
controlled erosion of the workpiece by repetitive electrical sparks between
the work and tool electrode submerged in a dielectric medium [5]. The EDM
technique was developed during 1940’s by Russian scientists B. R Lazarenko
and N. I Lazarenko. The electro-discharge machining is extensively employed
in the assembly of dies, molds tools made from tungsten carbide, hard alloy
steels, hastalloy, nimonic, etc., [6]. EDM is widely used as non-traditional
machining method within the current manufacturing situation. Basically,
EDM is employed to machine those materials that are tough to machine by the
traditional machining method. Finishing components of aeronautical and
automobile industries are machined by the EDM method [7]. R. Garn, A.
Schubert and H. Zeidler studied Analysis of the effect of vibrations on the
micro-EDM process at the workpiece surface in 2011. In this study, the effect
of vibrations on the electrical discharges in the micro-EDM (electrical
discharge machining) process was investigated. The experiments were
performed on steel strip of 1 mm thickness and tungsten carbide rod served as
electrode rod. The effect of tool rotation, pulse on time and workpiece
vibration has been investigated on MRR and SR. It was evident that by
application of vibration onto the micro-EDM process, the machining time can
be reduced significantly. The reduction or elimination of the start-up process
delivers a significant part of the machining time savings. Process time
decreases with increased vibration frequency and constant amplitude. Causes
for the start-up process are arc discharges and the resulting retracting
movements of the tool electrode, which leads to an open circuit state. The total
duration of the arcing events is reduced by the application of vibration and
decreases with increasing frequency [8]. U. Maradia, M. Scuderi et. al. studied
Super-finished surfaces using meso-micro EDM in 2013. Surface defects such
as inhomogeneity, cracks, arc spots and black spots have been analyzed and
Complimentary Copy
reduced, while improving material removal rate with lower tool wear. Super-
finished surfaces thus generated have uniform white layer (re-solidified layer)
with an average thickness below 1μm. Copper was used as the tool electrode
and hot-work steel 1.2343 was used as the workpiece. Super-finished surfaces
having Ra < 0.06μm have been generated using die sinking EDM in meso-
micro scale using a novel stochastic orbiting strategy and a low stray
capacitance power circuit. The stochastic orbiting strategy reduces the pre-
polishing requirement of the tool electrode. Ra values as low as 0.05μm and
evenly distributed white layer (re-solidified layer) with thickness of less than
1μm can be achieved with milled, turned or wire-eroded copper electrodes
having Ra ≤ 0.2μm [9]. Optimization of micro-EDM drilling of inconel 718
super alloy studied by Mustafa Ay, Ulaş Çaydaş and Ahmet Hasçalık in 2013.
Inconel 718 nickel-based super alloy flat plates in 4.76 mm thickness were
used as the target material while copper as tool electrode. The process
parameters were current and pulse on time to investigate tool wear rate and
Surface roughness. They conclude that the pulse current has a greater effect
on multi-performance characteristics than pulse duration parameter. Electrode
wears were increased with the increase in both discharge current and pulse
duration almost linearly due to the higher energy density. The crack and
damage characteristics of machined surfaces were reduced by decreasing the
discharge current and shortening the pulse duration [10]. Micro Drilling EDM
with High rotation speed of tool electrode using the electrostatic induction
feeding method studied by Yuna Yahagi, Tomohiro Koyano et.al. This paper
has investigated the influence of high spindle speeds on machining
performance. The experiments were performed to investigate electrode wear
by varying spindle speed and pulse on time. In micro drilling EDM, the
influence of high spindle speed was investigated using the electrostatic
induction feeding method. As a result, it was found that high aspect ratio can
be machined with lower tool wear ratio with 50000rpm spindle speed. This is
because rotation is effective in flushing debris particles from the gap and
increasing cooling rate at the tool electrode surface [11]. Influence of the
Process Parameters to Manufacture Micro cavities by Electro Discharge
Machining (EDM) has been covered by D. Gurguí, E. Vázquez and I. Ferrer
in 2013. Increasing demand for micro-products has driven the development of
innovative manufacturing processes to these new requirements as well as the
adaptation of conventional metal cutting process to these micro-scale
applications. In the medical field a huge variety of products can be found in
prosthesis, surgery devices or tissue engineering. Cavities have been created
on steel using copper as electrode. Two process parameters were used such
Complimentary Copy
that voltage and pulse on time to investigate surface topography of cavities

[12]. C.A.A. Rashed, L. Romoli, et.al worked on Experimental optimization
of micro-electrical discharge drilling process from the perspective of inner
surface enhancement measured by shear-force microscopy in 2014. The
micro-electrical discharge drilling process was studied by means of
experiments with the twofold objective of increasing the surface quality while
minimizing the drilling time. To characterize the inner surface of micro-drilled
holes obtained by EDM a specifically conceived scanning probe microscopy
technique was used. Experimental work had been carried out on stainless steel
as workpiece and tungsten carbide as tool electrode. The response variables
MRR, surface topography and surface roughness were investigated by varying
spindle speed rotation, pulse on time and current. It was concluded that surface
morphology reveals that for the highest discharge energy in the tested range,
combining relatively long duration and high peak current. Deep and wide
craters generated by high currents and long pulse-on duration can be smoothed
by final refining phase at low spark energy resulting in an average peak-to-
valley distance of 230 nm with a periodicity of 8 - 9 mm. Surface roughness
is decreased of about 32% with respect to the conventional production process
condition, maintaining the same process time of 12 seconds [13]. Comparative
Assessment of the Laser Induced Plasma Micromachining and the Micro-
EDM Processes studied by K. Pallav, P. Han, et. al. in 2014. The experiments
were performed on stainless steel using copper electrode. The investigation of
MRR, TWR and SR has studied by varying respective process parameters.
The comparative assessment of the two processes revealed that, micro
channels with better geometrical characteristics such as near vertical walls,
uniform transverse and longitudinal depth profile, uniform longitudinal width
profile, high aspect ratio, minima built-up edge, and machined surfaces of
lower surface roughness at higher MRR were obtained by LIP-MM. Since
LIP-MM does not require a tool for plasma generation, it also circumvents the
various tool related limitations associated with micro-EDM, including low
productivity due to time involved in on-machine tool machining, dimensional
limitations imposed by tool size, and significant reduction in geometrical
accuracy and formation of unmachined zones due to tool wear. Moreover,
LIP-MM is capable of machining materials irrespective of their electrical
conductivity and hence overcomes the difficulties encountered in the
machining of nonconductive materials [14]. The requirement of different
performance characteristics lead to fine powder addition into the dielectric
liquid that resulted in improved machining performance [15] and assured
higher precision and good surface quality [16].
Complimentary Copy
Methodology in Research
Taguchi Method
The design of experiments is used to design the experiment in proper manner

according to their number of parameters and levels. DoE minimizes repetition
and improves accuracy of the experimentation. There are generally four
methods used for design of experiments - Taguchi method, Response surface
method, Mixture design method and Factorial method. During literature
review it is found that a number of researchers used Taguchi method for design
of experiments [17, 18]. The researchers stated that Taguchi method has
become a powerful tool in the design of experiments as it improves
performance characteristics by optimizing the process parameters and reduces
sensitivity of the system performance to noise [19, 20]. In our literature review
However, Taguchi method can optimize single performance characteristics at
a time. Hence Taguchi approach is coupled with fuzzy logic for optimization
of multiple quality characteristics [21, 22]. In this method experiments can be
designed on the basis of process parameters, response variables and their
levels. The analysis of experiments is done using Minitab 16 software.
Detailed explanation of design of experiments by Taguchi method has been
explained by Madhav Phadake [23].
Experimental Conditions
Workpiece Material: In present work, Titanium alloy of Ti6Al4V used as

workpiece material. Titanium alloy (Ti6Al4V) alloy was designed for a good
balance of characteristics, including strength, ductility, fracture toughness,
high temperature strength, creep characteristics, weldability, workability and
thermal process ability. Also, it has high strength to weight ratio, excellent
erosion resistance and compatibility with composite structure. Chemical
composition and physical properties of Ti-6Al-4V are given in Table 1 and
Table 2 respectively.
Electrode Material: Tungsten carbide electrodes were the toughest variety
of EDM drill. Toughness allows tungsten carbide electrodes to drill through
the most stubborn target materials. Toughness also allows tungsten carbide
electrodes to be manufactured at smaller sizes than copper or brass, allowing
for smaller holes to be drilled. Tungsten Carbide electrode was used when the
target material is extremely durable. If even copper electrodes were not tough
Complimentary Copy
enough for a particular application, tungsten carbide would get the job done.
Also, when the hole that needs to be drilled was extremely small, Tungsten
carbide electrodes can be manufactured at diameters down to .045 mm.
Properties of tungsten carbide electrode were given in Table 3. Tungsten
Carbide of mean Diameter of 490 μm used for experiments.
Table 1. Chemical composition of Ti-6Al-4V
Contents Ti Al V Fe O C N H
Percent
89.86 5.89 3.93 0.165 0.128 0.017 0.005 0.002
%
Table 2. Physical properties of Ti-6Al-4V
Hardness Yield Strength Ultimate Tensile Strength

(HRC) (MPa) (MPa)
34 952 1062
Table 3. Properties of tungsten carbide
Tensile Compress
Density Hardness Melting Point Toughness
Strength Strength
(gm/cm3) (HRA) (0C) (kg/mm2)
(kg/mm2) (kg/mm2)
15.1 87.0 1587 179 410 50
Selection of Dielectric Fluid: In micro EDM drilling, dielectric plays an

important role during machining operation. The machining characteristics
were greatly influenced by the nature of dielectric used during micro EDM
drilling. There were different types of dielectrics such as kerosene, deionized
water, EDM oil, hydrocarbon oil etc. These dielectrics influences on the
performance criteria such as material removal rate, tool wear rate, diameter
variance at entry and exit hole and surface integrity during machining of
titanium alloy (Ti-6Al-4V). In Experimental setup of micro EDM: In this
study all the experiments including preliminary and final, were conducted on
Hyper 10 Micro Electric Discharge Machining. This machine tool is available
at Veermata Jijabai Technological Institute (VJTI), is an engineering college
located in Matunga (Mumbai), Maharashtra, India, and one of the oldest
engineering colleges in Asia. Figure 1 shows Spindle of Hyper 10 EDM and
Figure 2 shows photographs of Hper-10 Machine. Hyper-10 is a table-top type
miniature Machine Tool performing multiple machining processes such as
Micro Milling, Micro EDM, Micro Drilling, and Micro Wire EDM with its
various optional accessories. Its versatile flexibility provides the best solution
Complimentary Copy
in developing as integrated hybrid process using both conventional

mechanical and non-conventional processes such as EDM and ECM.
Figure 1. Spindle of Hyper 10 EDM.
Figure 2. Hyper 10 Micro EDM.
Complimentary Copy
Process parameters and their levels for experiments: Extensive literature

review gave clear idea that as voltage increases Material Removal Rate (MRR)
also increases. But there were always conflicts between Voltage and MRR in
EDM. As voltage increases in between sparking surfaces, spark energy also
gets stimulation thereby tool and workpiece temperatures increases rapidly
and causes TWR. Therefore, voltage levels are taken as 120V, 140V and
160V.
Experimental L9 orthogonal array for experiments: Orthogonal array for
final experiments with three levels of voltage, capacitance and RPM are shown
in Table 4. There are four sets of L9 orthogonal array for four different
electrodes.
Table 4. Experimental L9 orthogonal array for final experiments
Expt. Voltage Capacitance Spindle Rotations

No. (V) (pF) (RPM)
1 120 100 200
2 120 1000 400
3 120 10000 600
4 140 100 400
5 140 1000 600
6 140 10000 200
7 160 100 600
8 160 1000 200
9 160 10000 400
Quality criteria are assessed

Tool Wear Rate (TWR): The TWR indicates amount of material removed
from tool. TWR is calculated as per equation
𝑔𝑚 𝑊𝑡𝑏 (𝑔𝑚𝑠)− 𝑊𝑡𝑎 (𝑔𝑚𝑠)

𝑇𝑊𝑅 (𝑚𝑖𝑛) = 𝑡 (𝑚𝑖𝑛)
(1)
where,
Wtb= weight of tool before machining

Wta = weight of tool after machining
t = time required for machining
Overcut (OVC): Overcut measured by
Complimentary Copy
𝐷 (𝐷𝑖𝑎𝑚𝑒𝑡𝑒𝑟 𝑜𝑓 𝑊𝑜𝑟𝑘𝑝𝑖𝑒𝑐𝑒 ℎ𝑜𝑙𝑒)−𝑑 (𝐷𝑖𝑎𝑚𝑡𝑒𝑟 𝑜𝑓 𝐸𝑙𝑒𝑐𝑡𝑟𝑜𝑑𝑒)

𝑂𝑉𝐶 = 2
(2)
For Project Work facilities were used from different Institutes, Table 4
shows Instruments used and Facility used.
Table 5. Instruments used for assessment of response variables
Response Variables Instruments Used

TWR Weighing Machine
Overcut Image Analyzer
Z Co-Ordinate (Z): The Z Co-Ordinate was reading shown by Machine

on screen related to depth of the electrode in the drilled hole cavity.
Results, Analysis and Discussion
Experimental Results
There are three input parameters such as Voltage, Capacitance and RPM.
Recorded readings for L9 orthogonal array were mentioned below Table 6. It
shows that TWR and Overcut are minimum for first and ninth experiment. Z
is minimum for second and maximum for sixth experiment as shown in Table
6. The standard time of 15 minutes kept constant for all experiments.
Table 6. Experimental results with tungsten carbide electrode [31]
Process parameters Response variables

Expt.
Voltage Capacitance RPM Z TWR Overcut
No.
(V) (pF) (rpm) (mm) (mg/min) (μm)
1 120 100 200 0.596 0.0134 102.575
2 120 1000 400 1.1625 0.04 23.945
3 120 10000 600 2.1503 0.085 92.665
4 140 100 400 0.7139 0.02 79.45
5 140 1000 600 1.3947 0.055 90.02
6 140 10000 200 2.8105 0.08 180.55
7 160 100 600 0.6259 0.0184 176.585
8 160 1000 200 1.1797 0.045 90.685
9 160 10000 400 2.2485 0.0884 63.59
Complimentary Copy
Analysis of Variance for Quality Criterias in Micro-EDM
Analysis of Variance for Tool Wear Rate
ANNOVA for Tungsten Carbide Electrode was carried out by Minitab 17

Analysis Software. Analysis of TWR, Overcut and Z Co-ordinate shown in
Table 7;
TWR was measured by weight reduction method. Table 7, shows that
Capacitance plays dominant role in wearing of electrode but remaining
parameter such as Voltage and RPM were non-significant for TWR of
Tungsten Carbide Electrode. The absolute values of tool wear show that there
are two phenomenon governing tool wear characteristics: erosion of electrode
material and deposition of material on the electrode. When high spark energy
conditions exist, large amount of debris are formed, and the amount of material
deposited on the tool increases. Under such conditions, the amount of actual
material removed from the tool also increases.
Table 7. Analysis of variance for TWR with tungsten carbide Electrode
Source DF SS MS F ratio P value Contribution (%)

Voltage
2 0.000052 0.000026 0.90 0.527 0.74
(V(amp)
Capacitance (µs) 2 0.006809 0.003405 117.99 0.008 97.48
RPM 2 0.000067 0.000033 1.16 0.464 0.95
Error 2 0.000058 0.000029 0.83
Total 8 0.006985
S = 0.0053715 R-Sq = 99.17% R-Sq(adj) = 96.70%
Similarly, for low saprk conditions the amount of debris deposited on tool
and amount of actual tool material removed is also low. Since TWR was
calculated by measuring the difference in tool weight before and after
machining, the combined effect of deposition and removal of material from
tool was included in the measured TWR. The constant value of TWR indicates
that the difference between material removed from tool and material deposited
on tool remains constant even when the process parameters are changed. Main
effects plot for TWR is shown in Figure 3.
Complimentary Copy
Figure 3. Main Effects Plot for TWR with Tungsten Carbide Electrode.
In this experiment three levels of voltage were used i.e., 120V, 140V and
160V. Table 7, it was observed that erosion of tool was maximum at 10nF and
deposition of workpiece material on tool at 140V and 160V. During
assessment of TWR it is found that for 140V and 160V, initially TWR was
higher but once protective layer of carbon deposition covers the surfaces then
TWR as well as Z Co-ordinate reduces with respect to time. From the main
effects plot it can be said that tool wear increases as increase in Voltage and
Capacitance. This was due to a higher product of Voltage and Capacitance
producing stronger spark thereby temperature increases so melting starts at
earlier, also spark energy is low at low lower levels. Hence, as the Capacitance
increases the tool wear rate increases due to increasing spark energy. From the
main effect plot it’s clear that, as RPM increases TWR also increases. This is
due to the fact that RPM stimulates good flushing action, therefore MRR and
TWR also slightly increase at higher RPM.
Optimal Design for TWR
The S/N ratio consolidates several repetitions into one value and is an
indication of the amount of variation present. The S/N ratios have been
Complimentary Copy
calculated to identify the major contributing factors and interactions that

cause variation in the TWR. TWR is ‘Lower is better’ type response. An
analysis of variance (ANOVA) was verified for the signal to noise ratio of
both the main and interaction terms. The F values of the parameters have
shown which parameters were the most influential on providing the optimal
values of the TWR. Table 8 shows the ANOVA for S/N ratio for TWR at 90%
confidence interval. It is observed that the capacitance is the most significant
factor which contributes TWR followed by voltage and RPM, Table 9. The image
given in Figure 4 shows the influence of the process parameters on the S/N
factor of the TWR. These results showed that voltage of 120 V, capacitance
of 100 pF and RPM of 200 rpm have a positive influence on the S/N factor of
the TWR. These parameters greatly impacted the optimal results of the TWR.
Estimated value of the TWR at optimal conditions: Reasonable process
parameters of the TWR consisted of the following: U1, C1, and RPM1. The
TWR's value was determined by the formula given in equation (4.3):
 B , E ,G , B G  TWRop  U1  C1  RPM 1  2  T  0, 0147mg / min

2 3 1 2 1
(3)
Confirmation Experiments: Confirmation Experiments were conducted

with the process parameters determined through calculations of the Ti-6Al-4V
workpiece material, the WC electrode, voltage of 120 V, capacitance of 100
pF, and RPM of 200 rpm. The results of the TWR = 0,0134 mg/min, and the
difference between the calculated results and the experimental results was
8.8%.
Table 8. ANOVA for S/N ratio of TWR
Source DF Seq SS MS F ratio P value

Voltage (V(amp) 2 5,801 2,901 6,62 0,131
Capacitance (µs) 2 296,089 148,045 337,80 0,003
RPM 2 4,353 2,176 4,97 0,168
Error 2 0,877 0,438 - -
Total 8 307,120
S = 0,6620 R-Sq = 99,7% R-Sq(adj) = 98,9%
Complimentary Copy
Table 9. Respone table for S/N ratio of TWR
Input parameters
Level
Voltage Capacitance RPM
1 28,94 35,38 28,78
2 27,04 26,70 27,67
3 27,57 21,47 27,10
Delta 1,91 13,91 1,67
Rank 2 1 3
Figure 4. Main effects plot for S/N of TWR.
Analysis of Variance for Overcut
The ANNOVA for Overcut of Non-coated Tungsten Carbide Electrode shown

in Table 10. It was found that all parameters are non-significant for Overcut.
For Tungsten Carbide Electrode, Overcut increases as voltage increase up to
140V. But at higher voltage level of 160V overcut decreases due to protective
layer of carbon is formed at surfaces. The layer lessens the spark. Thus, instead
of increase in overcut, it was observed reduction in overcut. At Second level
of Capacitance (1000pF) overcut is less for all sets. From the theories, at level
1 (100pF) there should be less overcut; however, there are some anomalies
points due to the arcing effect at low capacitance level (Level 0 and Level 1).
Complimentary Copy
Since the low capacitance causes short circuit, resulting in no material

removal. Hence, even with the increase in discharge energy, the machining
time increases at those points.
Table 10. Analysis of variance for overcut with tungsten carbide electrode

Voltage (V(amp) 2 3328 1664 1.01 0.497 16.53
Capacitance (µs) 2 4627 2314 1.41 0.416 22.98
RPM 2 8885 4442 2.70 0.270 44.13
Error 2 3293 1646 16.35
Total 8 20133
S = 40.5741 R-Sq = 83.65% R-Sq(adj) = 34.58%
In the case of RPM of tool tungsten carbide, RPM produces vibrations and
whirling motion as shown in Figure 5. Due to whirling motion of tip of tool
side wise erosion of the cavity occurs. Every machine has different
characteristics. For that machine 400 rpm shows better results. The range
above and below 400 rpm shows an increase in whirling motion. As whirling
motion increases, hard tungsten carbide erodes the sides of cavity. Also, the
shape of the electrode becomes hemispherical at these RPM levels. Hence, at
lower (200rpm) and higher (600rpm) levels overcut is maximum.
Figure 5. Main Effects Plot for Overcut using with Tungsten Carbide Electrode.
Complimentary Copy
Optimization of Overcut
From the results of ANOVA of the mean and S/N ratio for the overcut, the
most significant main were obtained. Table 11 shows the ANOVA results of
S/N for overcut with 90% confidence intervals. Comparing the F values of the
parameters calculated with Ftable indicates that the voltage (F = 51.41),
capacitance (F = 67.21), and RPM (F = 127.56) are the main factors that affect
the overcut. It is observed that the RPM is the most significant factor which
contributes overcut followed by capacitance and voltage, Table 12. The image
given in Figure 6 shows the influence of the process parameters on the S/N
factor of the overcut. These results showed that voltage of 120 V, capacitance
of 1000 pF and RPM of 400 rpm have a positive influence on the S/N ratio of
the overcut.
Estimated value of the overcut at optimal conditions: From the results of
ANOVA on the S/N ratio for the overcut, the main terms were obtained; the
results are given in Table 11. The estimated value of the overcut under optimal
conditions: U1, C2, and RPM2, was determined as follows:
 B , E ,G , B G  OVCop  U1  C2  RPM 2  2  T  25.127  m (4)

2 3 1 2 1
Confirmation Experiments: Confirmation experiments were carried out

using the optimal process parameters such as the material workpiece (Ti-6Al-
4V), material electrode (WC), voltage (120 V), capacitance (1000 pF), and
RPM (400 rpm). The OVC obtained after confirmation experiments was
23.945 mm3/min. This study aimed at optimizing the OVC by using Taguchi
method and identifying the main factors that influence the OVC. And the
difference between the calculated results and the experimental results was
4.4%.
Table 11. ANOVA for S/N ratio for overcut

Voltage (V(amp) 2 44,549 22,2747 51,41 0,019
Capacitance (µs) 2 58,236 29,1182 67,21 0,015
RPM 2 110,526 55,2629 127,56 0,008
Error 2 0,866 0,4332 - -
Total 8 214,178 -
S = 0,6582 R-Sq = 99,6% R-Sq(adj) = 98,4%
Complimentary Copy
Table 12. Respone table for S/N ratio of overcut
Input parameters
Level
1 -35,71 -41,05 -41,50
2 -40,74 -35,27 -33,88
3 40,05 -40,18 -41,12
Delta 5,03 5,78 7,62
Rank 3 2 1
Figure 6. Main effects plot for S/N of overcut.
Analysis of Variance for Z Co-Ordinate
The ANNOVA for Z Co-ordinate of Non-coated Tungsten Carbide Electrode

shown in Table 13. ANOVA for Z Co-ordinate shown in Table 9 and found
that Capacitance was the most significant parameter for Z Co-ordinate and no
other parameter seemed to be significant. A method to achieve a specific depth
in this case was non-compensated for wear of the electrode by constant
electrode feeding in the Z-axis. This method requires an accurate model for
estimating the volumetric wear ratio (the ratio of electrode wear and
workpiece wear).
Complimentary Copy
Table 13. Analysis of variance for Z Co-ordinate with tungsten carbide

electrode [33]

Voltage
2 0.19889 0.09945 3.76 0.210 3.91
(V(amp)
Capacitance 0.011
2 4.79015 2.39507 90.66 94.20
(µs) 0.
RPM 2 0.04304 0.02152 0.81 0.551 0.84
Error 2 0.05284 0.02642 1.03
Total 8 5.08492
S = 0.162541 R-Sq = 98.96% R-Sq(adj) = 95.84%
Certain factors affecting the wear ratio are difficult to assess and control,
like flushing conditions in a deep hole for instance. This could easily result in
wrong estimation of the wear ratio and therefore errors in the produced depth.
The shape of the electrode also changes during machining towards a
hemisphere, which causes errors in the produced bottom surface. One solution
is to repeat the process a number of times with new or reground micro-
electrodes until the required depth or pre-determined time period is obtained.
This is called the multiple electrode strategy [24].
Figure 7 shows main effect plots for depth reached by tool. Depth
increases linearly with Capacitance. At lower Voltage gap i.e., 120V and
lower Capacitance level i.e., Level 1 (100pF) depth is less due to less energy
produced in electrode gap. Less depth was achieved at 160V. This is due to
the combined effect of non-compensated TWR from bottom of the electrode
as well as at higher voltage due to carbon layer formation reduction in spark
energy taking place. Hence depth increases linearly up to 140V voltage.
In the case of RPM, it provides better flushing action due to revolutions
of the tool. As revolutions of tools increase flushing actions stimulates
ionization and plasma channel formation. Hence RPM is directly related to
flushing action in spark gap. But researchers in MEDM always cope with
randomness of flushing action of dielectric fluid. This randomness in flushing
action of dielectric fluid produces anomalies at 200rpm, reduces depth.
Beyond 400rpm it shows satisfactorily increase in depth [25].
Complimentary Copy
Figure 7. Main Effects Plot for Z Co-ordinate with Tungsten Carbide Electrode [33].
Optimization of Z Co-Ordinate
From the results of ANOVA of the mean and S/N ratio for the Z, Table 14.
The results show that the ANOVA results of S/N for Z with 90% confidence
intervals. The voltage (F = 28.58), capacitance and (F = 972.43) are the main
factors that affect the Z, and RPM (F = 0.25) is insignificant to affect Z. It is
observed that the capacitance is the most significant factor which contributes
Z followed by voltage and RPM, Table 15. The image given in Figure 8 shows
the influence of the process parameters on the S/N factor of the Z. These
results showed that voltage of 120 V, capacitance of 1000 pF and RPM of 400
rpm have a positive influence on the S/N ratio of the overcut.
Estimated value of the overcut at optimal conditions: From the results of
ANOVA on the S/N ratio for the Z, the main terms were obtained. The
estimated value of the Z under optimal conditions: U2 and C2, was determined
as follows:
 B , E ,G , B G  Z op  U 2  C2  T  3.032mm
2 3 1 2 1
(5)
Complimentary Copy
Table 14. ANOVA for S/N ratio for Z

Voltage (V(amp) 2 5,714 2,8570 28,58 0,034
Capacitance (µs) 2 194,436 97,2181 972,43 0,001
RPM 2 0,050 0,025 0,25 0,800
Error 2 0,200 0,1000 - -
Total 8 200,400 -
S = 0,3162 R-Sq = 99,9% R-Sq(adj) = 99,6%
Table 15. Respone table for S/N ratio of Z
Input parameters
Level
1 1,154 -3,831 1,972
2 2,979 1,878 1,806
3 1,468 7,555 1,823
Delta 1,825 11,385 0,166
Rank 2 1 3
Figure 8. Main effects plot for S/N of Z.
Confirmation Experiments: Confirmation experiments were carried out

using the optimal process parameters such as the material workpiece (Ti-6Al-
4V), material electrode (WC), voltage (140 V), capacitance (10000 pF), and
RPM (200 rpm). The Z obtained after confirmation experiments was 2,8105
Complimentary Copy
mm, and the difference between the calculated results and the experimental
results was 7.3%.
Figure 9. Holes after micro-EDM [31].
Figure 10. SEM of machined surface of Holes after micro-EDM [31].
Surface Quality Analysis of Machined Hole [30]
The shape and size of the experimental hole at the optimal condition are shown
in Figure 9. The machined surface of the hole is adhered to by many particles
as shown in Figure 10. The reason may be that the materials of the workpiece
and electrode were melted and evaporated, they were cooled very quickly by
the dielectric solution, so it adhered to the machined surface [26]. The shape,
Complimentary Copy
size and distribution of adhesion particles and micro-cracks on the machined

surface are shown in Figure 11. Micro-cracking is caused by thermal residual
stress generated on the surface layer machined by micro-EDM [26]. The
results show that the size and shape of the adhesion particles are very different,
and the adhesion and micro cracking particles are distributed without any
rules. The topography of the machined surface is a collection of micro-craters
and micro-voids, Figure 12. Craters are formed by the impact of micro-energy
of electrical sparks, and micro-voids are formed by gas bubbles that appear
during machining [27]. This has resulted in a significant reduction in the gloss
of the machined surface, and micro-cracks and micro-voids will affect the
wear and fatigue strength of the machined surface [28]. EDX analysis of the
machined surface has shown that the integer composition of the micro-EDM
machined surface is different from that of the substrate layer, Figure 13. The
content of W appearing on the machined surface on the machined surface is
negligible, which indicates very little wear of the electrode [29]. The
percentage of C on the machined surface is very large, because the oil
dielectric fluid is cracked by electric sparks [30]. All of the above changes will
significantly affect the working condition of the hole.
Micro-
cracking
Figure 11. Adhesive particles and micro-cracks of machined surface [31].
Complimentary Copy
Figure 12. Structure of the machined surface [31].
Figure 13. EDX of machined surface in micro-EDM [31].
Complimentary Copy
Conclusion
The experiments were performed using Taguchi method of design of

experiments and analysis were carried out using Minitab16 software. Titanium
Grade 5 (Ti-6Al-4V) used as workpiece in both cases. The L9 orthogonal array
was performed with varying levels of Voltage, Capacitance and RPM to obtain
Response Variables such as Tool Wear Rate (TWR), Overcut and Z Co-
ordinate (Depth) in Micro EDM process. Experimental study of Tungsten
Carbide against same input parameter is recorded and comparatively analyzed.
The findings were derived from experimental investigations.
 The 140V of voltage could produce better machinability with the

capacitance of 10nF and electrode speed of 400rpm.
 The optimal parameters can produce better surface finish with better
machining accuracy.
 The only fewer agglomeration of tool electrodes was observed over
the machined titanium specimen.
 The tungsten carbide electrode can produce fewer micro cracks and
voids over machined titanium specimens.
References
[1] Jin J. T., C. Huang and L. Shi Y. Zhang, “Microstructure and properties of laser
melting deposited titanium matrix composite coating on titanium alloy,” Rare Metal
Materials and Engineering 2010. , vol. 39, no. 8, pp. 1403-1406,
[2] Liu Y., Y. Zhang, Z. Wang, R. Li, and C. Zheng F. Wang, “Compound machining
of titanium alloy by super high speed edm milling and arc machining,” Journal of
Materials Processing Technology, vol. 214, no. 3, pp. 531-538, 2014.
[3] Senthilkumar V., and V. Kumawat D. Arulkirubakaran, “Effect of micro- textured
tools on machining of ti–6al–4v alloy: An experimental and numerical approach,”
International Journal of Refractory Metals and Hard Materials, vol. 54, pp. 165-
177, 2016.
[4] Lee H., D. Aspinwall, R. Dewes and E. Aspinwall J. Simao, “Workpiece surface
modification using electrical discharge machining,” International Journal of
Machine Tools and Manufacture, vol. 43, no. 2, pp. 121-128, 2003.
[5] Norliana Mohd Abbas Noriah Yusoff Rohidatun Mahmod, “Electrical discharge
machining (edm): practices in malaysian industries and possible change towards
green manufacturing,” in Procedía Engineering, vol. 41, 2012, pp. 1684-1688.
Complimentary Copy
[6] Sushil Kumar Choudhary R. S Jadoun, “Current Advanced Research Development

of Electric Discharge Machining (EDM): A Review,” International Journal of
Research in Advent Technology, vol. 2, no. 3, 2014.
[7] Ho K. and S. Newman, “State of the art electrical discharge machining (EDM),”
International Journal of Machine Tools and Manufacture, vol. 43, no. 13, pp. 1287-
1300, 2003.
[8] Schubert A. and H. Zeidler R. Garn, “Analysis of the effect of vibrations on the
micro-EDM process at the workpiece surface,” Precision Engineering, vol. 35, pp.
364-368, 2011.
[9] Scuderi M., R. Knaak, M. Boccadoro, I. Beltramib, J. Stirnimann and K. Wegener
U. Maradia, “Super-finished surfaces using meso-micro EDM,” Procedia CIRP,
vol. 6, pp. 157-162, 2013.
[10] Ulaş Çaydaş and Ahmet Hasçalık Mustafa Ay, “Optimization of micro-EDM
drilling of inconel 718 Superalloy have studied,” International Journal Advance
Manufacturing Technology, vol. 66, pp. 1015-1023, 2013.
[11] Tomohiro Koyano, Masanori Kunieda, and Xiaodong Yang Yuna Yahagi, “Micro
Drilling EDM with High Rotation Speed of Tool Electrode Using the Electrostatic
Induction Feeding Method,” Procedia CIRP, vol. 1, pp. 162-165, 2012.
[12] Vázquez E. and I. Ferrer D. Gurguí, “Influence of the Process Parameters to
Manufacture Micro-cavities by Electro Discharge Machining (EDM),” Procedia
Engineering, pp. 499-505, 2013.
[13] Romoli L., F. Tantussi, F. Fuso, L. Bertoncini, M. Fiaschi, M. Allegrini and G. Dini
C.A.A. Rashed, “Experimental optimization of micro-electrical discharge drilling
process from the perspective of inner surface enhancement measured by shear-force
microscopy,” CIRP Journal of Manufacturing Science and Technology, vol. 7, pp.
11-19, 2014.
[14] P. Han, J. Ramkumar, Nagahanumaiah and K. F. Ehmann K. Pallav, “Comparative
Assessment of the Laser Induced Plasma Micromachining and the Micro-EDM
Processes,” Journal of Manufacturing Science and Engineering, vol. 136, pp. 1-16,
2014.
[15] H. Kumar, “Development of mirror like surface characteristics using nano powder
mixed electric discharge machining (NPMEDM),” The International Journal of
Advanced Manufacturing Technology, vol. 76, no. 1-4, pp. 105-113, 2015.
[16] M. Mahardika, M. Hamdi, Y. San Wong, N. Miki, and K. Mitsui G. S. Prihandana,
“Study of workpiece vibration in powder-suspended dielectric fluid in micro-edm
processes,” International Journal of Precision Engineering and Manufacturing, vol.
14, no. 10, pp. 1817–1822, 2013.
[17] Kumanan S., and Sivakumaran N. Ahilan C., “Application of Grey Based Taguchi
Method on Multi Response Optimization of Turning Process,” Advances in
Production Engineering and Management, pp. 171-180, 2010.
[18] Unses E. and C. Cogun, “Improvement of electric discharge machining (EDM)
performance of Ti-6Al-4V alloy with added graphite powder to dielectric,” Journal
of Mechanical Engineering, vol. 61, no. 6, pp. 409-418, 2015.
Complimentary Copy
[19] Vázquez E. and I. Ferrer D. Gurguí, “Influence of the Process Parameters to

Manufacture Micro-cavities by Electro Discharge Machining (EDM),” Procedia
Engineering, pp. 499-505, 2013.
[20] N. Ekmekci and B. Ekmekci, “Electrical discharge machining of ti6al4v in
hydroxyapatite powder mixed dielectric liquid,” Materials and Manufacturing
Processes, vol. 31, no. 13, pp. 1663-1670, 2016.
[21] Romoli L, F. Tantussi, F. Fuso, L. Bertoncini, M. Fiaschi, M. Allegrini and G. Dini
C.A.A. Rashed, “Experimental optimization of micro-electrical discharge drilling
process from the perspective of inner surface enhancement measured by shear-force
microscopy,” CIRP Journal of Manufacturing Science and Technology, vol. 7, pp.
11-19, 2014.
[22] Amirthagadeswaran K. S. Jothimurugan R. S., “Performance of Silver Coated
Copper Tool with Kerosene-servotherm Dielectric in EDM of Monel 400TM,”
Journal of Applied Sciences, vol. 12, no. 10, pp. 999-1005, 2012.
[23] Phadke M. S., Quality Engineering Using Robust Design.: AT and T Laboratories,
Prentice Hall, Englewood Cliffs, 1989.
[24] Dimo S. S. Pham D. T., “Micro-EDM—recent developments and research issues,”
Journal of Materials Processing Technology, vol. 149, pp. 50-57, 2004.
[25] Jahan M. P. Asma S. P., “An Experimental Study on the Effect of Operating
Parameters during the Micro-Electro-Discharge Machining of Ni Based Alloy,”
International Journal of Materials and Metallurgical Engineering, vol. 10, pp. 111-
152, 2016.
[26] Amirthagadeswaran K.S. Jothimurugan R. S., “Performance of Silver Coated
Copper Tool with Kerosene-servotherm Dielectric in EDM of Monel 400TM,”
Journal of Applied Sciences, vol. 12, no. 10, pp. 999-1005, 2012.
[27] Panchal D. G. Biradar S. V., “Optimization of EDM Process with Coated Electrode
using GRA,” International Journal of Innovative Science, Engineering &
Technology, vol. 3, no. 10, pp. 2348-7968, 2016.
[28] Choudhary S. K. and R. Jadoun, “Current advanced research development of electric
discharge machining (EDM): A Review,” International Journal of Research in
Advent Technology, vol. 2, no. 3, pp. 273-297, 2014.
[29] Sahoo A. K., P. C. Mishra, R. Kumar, and A. Panda R. K. Das, “Comparative
machinability performance of heat treated 4340 steel under dry and min imum
quantity lubrication surroundings,” Procedia Manufacturing, vol. 20, pp. 377-385,
2018.
[30] Liu Y., Y. Shen, R. Ji, Z. Li, and C. Zheng Y. Zhang, “Investigation on the influence
of the dielectrics on the material removal characteristics of EDM,” Journal of
Materials Processing Technology, vol. 5, pp. 1052-1061, 2014.
[31] Phan, N. H., Muthuramalingam T, Dong P. V., Shailesh S., Tung N. N., Tam N. C.,
Ly N. T., “Multi-objective optimization of micro EDM using TOPSIS method with
Tungsten carbide electrode”. Sādhanā 47, 133, 2022. https://doi.org/10.1007/
s12046-022-01900-8.
[32] Phan N, H., “Multi-objective decision making for Z Coordinator and overcut in μ -
EDM process using tungsten carbide electrode for machining of titanium alloy”.
Journal of Machine Engineering”, Vol. 22, No. 1, 2022, 138–149.
Complimentary Copy
[33] Phan N. H., Shirguppikar S., Long B.T., Bich M.T., Dung L.Q., “Experimental
Investigation of the Influence of Processes Parameters on Z Coordinate in Micro
EDM for Ti-6Al-4V”, Lecture Notes in Mechanical Engineering, 2022.
https://doi.org/10.1007/978-3-030-99666-6_73.
Biographical Sketch
Name: Nguyen Huu Phan
Affiliation: Faculty of Mechanical Engineering, Hanoi University of

Industry, 298 CauDienstr., BacTuLiem District, Hanoi, Vietnam, 100000
Education: Hanoi University of Industry, 298 CauDienstr., BacTuLiem
District, Hanoi, Vietnam, 100000 Business Address: No Research and
Professional Experience: EDM
Professional Appointments: No Honors: Prof.
Publications from the Last 3 Years
1) Experimental Investigation of White Layer Formation on Machining Silicon

Steel in PMEDM Process 2021 Silicon.
2) Surface quality measures analysis and optimization on machining titanium alloy
using CO2 based Laser beam drilling process 2021, Journal of manufacturing
processes.
3) Experimental Investigation Of Uncoated Electrode And PVD AlCrNi coating on
surface roughness in electrical discharge machining of TI6Al-4V 2021,
International Journal of Engineering: TRANSACTIONS A.
4) Influence Of Process Parameters On The Microstructural Characteristics And
Mechanical Properties Of Recast Layer Thickness Coating On Die Steel
Machined Surface After Electrical Discharge Machining 2021, International
Journal of Engineering TRANSACTIONS B: Applications.
5) Assessing the effects of uncoated and coated electrode on response variables in
electrical discharge machining for Ti6Al-4V titanium alloy 2021, Tribology in
Industry.
6) Multi- Object Optimization In EDM Using AlCrNi Coated Electrode 2021, The
International Journal of Advanced Manufacturing Technology.
7) Investigation of Surface Quality in Cost of Goods Manufactured (COGM)
method of µ-Al2O3 Powder-Mixed-EDM Process on Machining of Ti-6Al-4V
2021, The International Journal of Advanced Manufacturing Technology.
8) Study on Multi-Objects Optimization in EDM with Nickel Coated Electrode
using Taguchi - AHP – Topsis 2022, International Journal of Engineering
TRANSACTIONS B: Applications.
Complimentary Copy
9) Enhancing surface morphology of machined SKD61 die steel in EDM process

using DEAR approach based multi criteria decision making 2022, International
Journal on Interactive Design and Manufacturing.
10) Effect of ultrasonic low frequency vibration and its direction on machinability in
WEDM process 2021, Materials and Manufacturing Processes.
11) Multi-Objective Decision Making For Z Coordinator and Overcut in µ - EDM
process using Tungsten Carbide Electrode for machining of Titanium Alloy
2022, Journal of Machine Engineering.
12) Enhancing the machinability of SKD61 die steel in powder mixed EDM process
with TGRA based multi criteria decision making 2022 Journal of the Mechanical
Behavior of Materials.
13) Multi-objective optimization of micro EDM using Topsis method with tungsten
carbide electrode 2022, Sådhanå.
14) Multi-Criteria decision making in electrical discharge machining with Nickel
Coated Aluminium Electrode for Titanium Alloy using Preferential Selection
Index 2022, Manufacturing Review.
15) Multi-objects optimization in µ- EDM using AlCrN coated tungsten carbide
electrode by Deng’s method 2022, Manufacturing Review.
16) Performance Analysis of Copper Coated Aluminum Tool in Electrode Discharge
Machining of Ti-6Al-4V Alloy 2022 Proceedings of the International
Conference on Advanced Mechanical Engineering, Automation, and Sustainable
Development 2021.
17) Multi-objects Optimization in Μ-Edm Using Alcrni Coated Tungsten Carbide
Electrode for Ti-6al-4v 2022, The International Journal of Advanced
Manufacturing Technology.
18) Multi-objective optimization in microelectrical discharge machining using
titanium nitride coated WC electrode 2023, International Journal on Interactive
Design and Manufacturing.
19) Development of AHPembedded Deng’s hybrid MCDM model in microEDM
using carbon-coated electrode 2023, Journal of the Mechanical Behavior of
Materials.
20) Simultaneous improvement of Z-coordinate and overcut in EDM of titanium
grade 5 alloy using a carbon-coated micro-tool electrode 2023 Modern Physics
Letters B.
21) Minimum roughness value in PMEDM with lowfrequency vibration applied to
workpiece, 2023 Modern Physics Letters B.
22) Influence of graphene coating in edm with aluminum electrode 2023 Journal of
the Mechanical Behavior of Materials.
23) Influence of carbon coated wc electrode on drilling measures of ti-6al-4v alloy in
µ - edm process 2023 Sadhana.
Complimentary Copy
Chapter 5
A Numerical Study of the Cracking Behaviour

of Coated Tungsten Carbide Cutting Tools
during the Machining Process
K. Bounif1,2, PhD
M. Abbadi1, PhD
and M. Nouari2, PhD
1ENSA, Laboratoire des sciences de l’ingénieur, Équipe Lean Manufacturing et
Modélisation Mécanique, Université Mohamed 1er, Oujda, Morocco

2LEM3, Université de Lorraine, GIP-InSIC, Nancy, France
Abstract
In this investigation, a finite element approach has been developed to

explore the wear by cracking in cutting tools during machining processes.
This mechanism which inevitably leads to delamination of the coating,
proved to be among the main failure modes affecting cutting tools.
The calculation of the stress intensity factor is a major tool to study
the behaviour of cracks at the edge radius of a coated cutting tool. The
effect of the crack length on the stress intensity factor in mode I was
evaluated numerically and analytically to fully understand the crack
propagation. The same factor in mode II was also computed to study the
influence of the substrate behaviour model on the same crack. Finally,
the effect of the stiffness of the coating material on the crack behaviour
is also investigated.
Keywords: crack, machining, tool, coating, finite element, fracture mechanics

ISBN: 979-8-89113-221-4
Complimentary Copy
180 K. Bounif, M. Abbadi and M. Nouari
Introduction
The cutting tool is a major element in the machining process, and any problem
it faces directly affects this process which in turn affects the condition of the
part to be machined. This is why it must be chosen very carefully, both in
terms of the choice of substrate and coating. The substrate supports the
mechanical and thermal stresses of machining [1]. The coating, on the other
hand, must protect the substrate against wear [2], provide thermal and
chemical protection and ensure resistance to cracking [1, 3]. The latter is
considered among the essential elements that affect the performance and life
of cutting tools during machining operations as the delamination of the coating
always occurs [4, 5].
Many works have been devoted to the study of the wear mechanism of
diamond coated tools, which is widely used in shaping applications [6]. This
is due to its good mechanical properties such as good hardness, extreme
stiffness, very high thermal conductivity, low friction coefficient and good
chemical stability [7]. However, it is characterised by poor adhesion with the
substrate [8], which leads to the appearance of the phenomenon of
delamination of the coating interfaces [9] and coating breakage [10]. The latter
contribute mainly to the limitation of the service life of coated tools.
Bounif et al., [4, 5] have been working on the initiation and propagation
of cracks in cutting tools. They have worked on several parameters of
machining and cutting tools such as edge radius, thickness and stiffness of the
coating, substrate stiffness as well as the cutting angle with a diamond coated
tool. P. Lu et al., [11] worked on the interface delamination wear of diamond
coated carbide tools. They showed that the higher stiffness of the coating
increases the probability of initiating cracks and decreases the delamination of
coating. They [12] characterised the interface by tests and simulations of
scratches. F. Qin [13] works on the delamination wear of cutting tools coated
with nano-diamond in the machining of composite materials and finds that this
kind of tools has a higher resistance to the delamination wear of the coating
than the conventional tools coated with microcrystalline diamond. While he
shows in another work [14] that the increase of the coating thickness increases
the residual stresses at the coating-substrate interface. On the other hand,
increasing the coating thickness will generally increase the resistance to
cracking and delamination of the coating. Thicker coatings will result in larger
edge radii; however, the extent of the effect on cutting forces also depends on
the machining conditions. The life of diamond-coated tools increases with
coating thickness due to delayed delamination. Polini [15] explored the
Complimentary Copy
A Numerical Study of the Cracking Behaviour … 181
adhesion of the coating/substrate interface and showed that the presence of Co

in carbide tools leads to the formation of a non-diamond carbon layer on the
surface of the substrate, resulting in poor interface adhesion. On the other
hand, diamond is very brittle and cracking of the coating due to local fractures
can induce catastrophic tool failures. Thus, it is desired to quantitatively
characterise the interface adhesion of diamond-coated tools and how coating
fractures can affect interface delamination. Oles et al., [16] have investigated
the effect of abrasive wear on the tool flank face and found that this type of
wear is a common wear mechanism in CVD diamond coated tools. However,
delamination of the coating interface [17] or coating fractures [18] mainly
decrease the service life of CVD diamond coated tools in machining.
In this investiagtion, the stress intensity factor is used to study and analyse
the wear by cracking of a diamond coated cutting tool during machining
operation.
The objective of this work is to explore by finite element method using
the Abaqus computational code, the effects of the crack length, the substrate
behaviour model and the coating stiffness on the behaviour of a crack initiated
in the edge radius of a coated cutting tool during the machining process. The
obtained results are compared and validated by the approach of Barsoum [19,
20].
Theoretical Study
Linear fracture mechanics (LFM) is essentially concerned with the study of

macroscopic cracks. It applies when there are discontinuities in the material.
Current fracture mechanics is largely based on the work of Griffith [21]. In
particular, fracture mechanics is based on the study of crack propagation in
materials. It uses solid mechanics methods to calculate the stress intensity at
the crack tip and experimental solid mechanics methods to characterise the
resistance of the material to fracture. As a result, several modes of fracture can
occur depending on the loading mode. In fracture mechanics, a crack is usually
characterised by the irreversible separation of a continuous medium into two
distinct parts. This introduces a discontinuity in the displacement field of the
crack lips. The relative displacement modes of the crack lips define a specific
mode of failure. The latter depends on how the force that creates the crack was
applied. Thus, three possible cracking modes take place as below [22]:
Mode I: crack opening mode where displacements at the crack lips are
perpendicular to the direction of propagation;
Complimentary Copy
Mode II: in-plane shear mode, the displacements at the lips of the crack
are parallel to the direction of propagation;
Mode III: out-of-plane shear mode, in this case the displacements at the
crack lips are parallel to the crack front.
Actually, the opening mode of a crack is a combination of its different
modes, called mixed mode [23].
Westergaard-Irwin-williams [24, 25] proposed a solution for stresses and
displacements as a function of Stress Intensity Factors in the vicinity of the
crack tip and more precisely in the singular zone characterised by a stress field
1
with a singularity in r −2.
This Stress Intensity Factor depends on the loading and the geometry of
the specimen. It is used to describe the level of loading in the vicinity of the
crack and to design the structure. Depending on the mode of failure, the Stress
Intensity Factor is noted KI, KII or KIII.
Simulations and Results
Numerical Method
In order to study the wear by cracking in cutting tools during machining

processes, a 2D model based on the use of the classical finite element method
(FEM) has been developed from the Abaqus calculation code as illustrated in
Figure 1.
In this work, a diamond coated tungsten carbide cutting tool and a steel
workpiece (Figure 1) are considered, with the parameters displayed in
Table 1.
A displacement of 10 µm is applied to the workpiece along the x axis and
a reference point is applied to consider it as a rigid body. The mechanical
properties of tungsten carbide, diamond and steel are shown in Table 2.
Table 1. The parameters of the cutting tool
Cutting angle Clearance angle Edge radius Coating thickness

0° 7° 1 µm 6 µm
Complimentary Copy
Study area
Tool
Workpiece
Figure 1. Finite element model and boundary conditions.
Table 2. Material properties used
Young’s modulus [GPa] Poisson's ratio

Tungsten carbide 619.5 0.24
Diamond 1200 0.07
Steel 210 0.24
Mesh Study
To optimise the finite element mesh, a convergence study with a variable mesh
density was performed until results became independent of the mesh used.
Traditionally in finite element simulations, a refined mesh provides accurate
results. Moreover, the larger the mesh size, the longer the computation time.
For this purpose, several steps have been proposed to study the convergence
of the mesh:
 Creation of a study area around the edge radius where the crack will
initiate.
Complimentary Copy
 Create a mesh using a reasonable number of elements, then analyse

the model.
 Recreate the mesh by increasing the mesh density, recalculate KI,
and compare the results with the first calculation.
 Continue to increase the mesh density and then check that the results
converge satisfactorily (i.e., until an almost constant KI is obtained
for the ten measurements as shown in Figure 2.)
The numerical simulation, based on linear elements and a structured mesh,

showed a convergence for the mesh size elements of 4 µm
(Cf. Figure 2). This mesh, carried out in two dimensions under the condition
of plane stress, is characterised by the four-node bilinear quadrilateral
elements with reduced integration (CPS4R) provided by the element library
of Abaqus program as illustrated in Figure 3.
70
6 µm
8 µm
60
Stress intensity factor in mode I [Mpa.mm^1/2]
4 µm
2 µm
50
40
30
20
10
0
0 2 4 6 8 10 12
Number of contours
Figure 2. Variations of KI vs. Number of contours for element mesh size varying
from 2 to 8 µm.
Complimentary Copy
Figure 3. Mesh used.
Discussion
In this section, two numerical studies are presented, the first study concerns
the calculation of the stress intensity factor at the edge radius of a cutting tool
for the case of elastic and plastic substrate in order to compare with the
analytical results in the literature [19, 20]. The second study, however,
concerns the effect of coating’s rigidity.
Study of Stress Intensity Factors
The study consists of a crack initiating in the edge radius of a cutting tool in
both cases of elastic and plastic substrate. For this purpose, the stress intensity
factor KI was calculated for each crack length a, numerically by the finite
element method provided by ABAQUS code and compared with the values of
the analytical solution (Barsoum approach) given by:
Complimentary Copy
𝑎
𝐾𝐼 = 𝜎√𝑎𝜋𝑓(𝑤) (1)
𝑎 𝑎 𝑎 2 𝑎 3
𝑓 (𝑤) = 1.122 − 0.231 (𝑤) + 10.550 (𝑤) − 21.71 (𝑤) +
𝑎 4
30.382 (𝑤) (2)
where:
𝑎
𝑓 ( ) represents a geometric factor depending on the shape of the crack.
𝑤
σ is the applied stress.
𝑎 indicates the length of the crack.
Figure 4 shows the variation of KI in the case where the substrate is elastic
as a function of the length of the crack. KI is found to increase linearly with
increasing the length of the crack. This variation is justified by the stiffness of
the substrate (tungsten carbide) which resists the crack opening.
90
80
70
60
50
40 Analytic
30 Numerical
20
10
0
0 0,001 0,002 0,003 0,004 0,005 0,006
Crack length [mm]
Figure 4. The variation of the stress intensity factor KI [MPa.mm1/2] as a function of

the crack length for the case where the substrate is elastic.
Complimentary Copy
80
Stress intensity factor in mode I [Mpa.mm^1/2] 70
60
50
Analytic
40
Numerical
30
20
10
0
0 0,001 0,002 0,003 0,004 0,005 0,006
Crack length [mm]
Figure 5. The variation of the stress intensity factor KI [MPa .mm1/2] as a function of
the crack length (the case where the substrate is plastic).
Figure 5 shows the variation of KI as a function of the crack length in the

case where the substrate is plastic. It is found that KI increases with the
increase of the crack length, which still shows the influence of the substrate
stiffness that resists the crack opening. Thus, a very good agreement between
the numerical results and those provided by the Barsoum analytical solution is
observed [19, 20] for both cases.
Comparison between Elastic and Plastic Substrates
The variation of KI and KII, in the case where the substrate is elastic and
plastic, is explored to fully understand the effect of the substrate plasticity. For
this purpose, the crack length is varied and KI and KII are computed for both
cases.
Figure 6 shows the variation of KI as a function of the length of the crack
in the case where the substrate is elastic and plastic. It is noted that KI in the
case of elastic substrate is greater than that of plastic substrate which shows
Complimentary Copy
that the plasticity of the substrate significantly delays the cracking in the
coating of the cutting tool. Also, the difference between the values is found to
be very small for large crack lengths. This finding is explained by the fact that
the elastic effect is negligible at the approach of the coating/substrate interface.
Figure 7 shows the variation of KII as a function of the crack length for
both configurations of elastic and plastic substrates. A decrease of KII is
observed when the crack length is increased. This result implies that the shear
decreases with the increase in the crack length. In addition, KII in the elastic
case proved to be smaller as compared to that of the plastic case when the
crack propagates closer to the substrate. This is due to the shear decrease when
moving closer to the substrate and to the influence of the substrate in the
plastic case.
90
80
70
60
50
40 Plastic
30 Elastic
20
10
0
0 0,001 0,002 0,003 0,004 0,005 0,006
Crack length [mm]
Figure 6. Variations of KI as a function of crack length in the case where the

substrate is plastic and elastic.
Complimentary Copy
15
Elastic
Stress intensity factor in mode II [Mpa.mm^1/2]
10
Plastic
0
0 0,001 0,002 0,003 0,004 0,005 0,006
-5
-10
-15
Crack length [mm]
Figure 7. KII as a function of crack length for both elastic and plastic substrates.
The Influence of the Coating Stiffness
To understand the influence of the coating stiffness on the cracking wear of

the cutting tool during the machining process, two coating materials, namely
diamond and steel, are considered. Then, the stress intensity factor for each
crack length is calculated.
Figure 8 shows the variation of the stress intensity factor with the length
of the crack in the edge radius for diamond and steel. It is observed that KI
increases with the increase of the coating stiffness (Young’s modulus). This
implies that the increase in coating stiffness increases the probability of crack
initiation in the edge radius of the cutting tool.
Young’s modulus is the proportionality factor in the mathematical
description of Hooke’s law. So the stress intensity factor KI, is given by:
𝑎
K = Ɛ. E. √𝜋𝑎 𝑓 (𝑤) (3)
Complimentary Copy
This implies that when the Young’s modulus increases, the stress intensity
factor also increases, which explains the results obtained in the present study.
These results are comparable to those found by K. Bounif et al., [4, 5] who
calculated the displacement required to initiate and propagate a crack in the
edge radius of a cutting tool for several coating materials. The found results
indicated that increasing the stiffness of the coating increases the probability
of crack initiation and propagation. Similarly, Ping Lu et al., [11, 12] showed
that the critical load for coating cracking decreases and that for delamination
increases when the Young’s modulus increases. The same authors in a
previous study showed that the stiffness of the coating delays delamination.
90
Diamond
80
70 Steel
60
50
40
30
20
10
0
0 0,001 0,002 0,003 0,004 0,005 0,006
Crack length [mm]
Figure 8. The influence of Young’s modulus on the stress intensity factor KI.
Conclusion
In this paper a numerical simulation has been performed by ABAQUS

computational code to model and study the phenomenon of cracking in the
coating of a cutting tool by the standard finite element method (FEM).
Complimentary Copy
The first part of this article concerns the study of the length influence of a
crack initiated in the coating of the cutting tool on the stress intensity factor in
mode I and II.
The numerical computation of KI by ABAQUS software and its
comparison with the analytical approach showed a very good agreement
between the numerical results and the analytical Barsoum approach solution.
In the case where the substrate is elastic, KI is found to linearly increase with
the increase of the crack length. This variation is justified by the stiffness of
the substrate (tungsten carbide) which resists the crack opening.
When the substrate is plastic, KI increases with the increase of the crack
length, which still shows the influence of the substrate stiffness that resists the
crack opening. Thus, a very good agreement between the numerical results
and those of the analytical solution for both cases of substrate is observed.
The second work, concerns the comparison of the stress intensity factor
in the case where the substrate is elastic and plastic. KI in the case where the
substrate is elastic is found to be greater than that of plastic substrate which
shows that the plasticity of substrate delays considerably the cracking in the
coating of the cutting tool. Moreover, the difference between the values found
in the two cases is very small for the larger lengths of the crack. This is
explained by the fact that the elastic effect is negligible at the approach of the
coating/substrate interface.
It was found that KII decreases as the crack length increases, which implies
that the shear mechanism decreases with the increase in the crack length. It is
also noted that the difference between the values found in the two cases
became greater for larger crack lengths. This behaviour is due to the shear
decrease when approaching the substrate and to the influence of the substrate
in the plastic case.
In the last part, concerning the influence of the coating stiffness on the
cracking wear of the cutting tool during the machining process, two coating
materials, namely diamond and steel, are investigated. It was observed that KI
increases with the increase of the coating stiffness. This implies that the
increase in coating stiffness increases the probability of crack initiation in the
edge radius of the cutting tool.
Disclaimer
None.
Complimentary Copy
References
[1] C. Pagès, Comportement de revêtements céramiques sur outil en tournage à sec de

finition. Mécanique (Behavior of ceramic coatings on tools during dry finishing
turning. Mechanical). France, Ecole Centrale de Lyon (2003).
[2] F. Klocke, T. Krieg, Coated Tools for Metal Cutting - Features and Applications,
CIRP Annals – ManufacturingTechnology 48(2) (1999) 515–525.
[3] B. Vasques, Etude du comportement du rayon d’arrête et de son influence sur
l’intégrité de surface en tournage à sec, Université François- Rabelais de Tours 2008
(Study of the behavior of the edge radius and its influence on surface integrity in dry
turning, University François-Rabelais of Tours 2008).
[4] K. Bounif, M. Abbadi, M. Nouari, R. Selvam, A numerical approach for crack-
induced damage in tungsten carbide cutting tools during machining. Engineering
Failure Analysis, Volume 128, 2021, 105617, ISSN 1350-6307.
[5] K. Bounif, M. Abbadi, S. Atlati, M. Nouari, R. Selvam, Modeling and Numerical
Simulation of the Cracking of a Diamond-Coated Cutting Tool During Machining,
Key Engineering Materials 820, (2019) 29-39.
[6] J. Karner, M. Pedrazzini, I. Reineck, M. E. Sjostrand, E. Bergmann, Mater. Sci. Eng.,
A Struct. Mater.: Prop. Microstruct. Process. 209 (1996) 405.
[7] J. Hu, Y. K. Chou, R. G. Thompson, Cohesive zone effects on coating failure
evaluations of diamond-coated tools. Surface & Coatings Technology 203 (2008)
730–735.
[8] R. Polini, P. D’Antonio, S. Lo Casto, V. F. Ruisi, E. Traversa, Surf. Coat. Technol.
123 (2000) 78.
[9] J. M. Sanchez, S. ElMansy, B. Sun, T. Scherban, N. Fang, D. Pantuso, W. Ford, M.
R. Elizalde, J. M. Martinez-Esnaola, A. Martin Meizoso, J. Gil-Sevillano, M.
Fuentes, J. Maiz Acta Mater. 47 (1999), p. 4405.
[10] H. Chai Int. J. Fract., 119 (2003), p. 263.
[11] P. Lu, X. Xiao, Y. K. Chou, Interface delamination study of diamond-coated carbide
tools considering coating fractures, Surface and Coatings Technology, Volume 260,
2014, Pages 239-245, ISSN 0257-8972.
[12] P. Lu, X. Xiao, M. Lukitsch, A. Sachdev, Y. K. Chou, Interface characterizations of
diamond-coated tools by scratch testing and simulations, Surface and Coatings
Technology, Volume 206, Issue 7, 2011, Pages 1860-1866, ISSN 0257-8972.
[13] F. Qin, J. Hu, Y. K. Chou, R. G. Thompson, Delamination wear of nano-diamond
coated cutting tools in composite machining, Wear, Volume 267, Issues 5-8, 2009,
Pages 991-995, ISSN 0043-1648.
[14] F. Qin, Y. K. Chou, D. Nolen, R. G. Thompson, Coating thickness effects on
diamond coated cutting tools, Surface and Coatings Technology, Volume 204,
Issues 6–7, 2009, Pages 1056-1060, ISSN 0257-8972.
[15] R. Polini, P. D’Antonio, S. Lo Casto, V. F. Ruisi, E. Traversa Surfer. Manteau.
Technol., 123 (2000), p. 78.
[16] E. J. Oles, A. Inspektor, C. E. Bauer Diam. Relat. Mater., 5 (1996), p. 617.
Complimentary Copy
[17] J. M. Sanchez, S. ElMansy, B. Sun, T. Scherban, N. Fang, D. Pantuso, W. Ford, M.

R. Elizalde, J. M. artinez-Esnaola, A. Martin Meizoso, J. Gil-Sevillano, M. Fuentes,
J. MaizActa Mater., 47 (1999), p. 4405.
[18] H. Chai Int. J. Fract., 119 (2003), p. 263.
[19] Y. Murakami Intensité du stress Factors Handbook Press, Oxford, Royaume-Uni
(1987)
[20] H. Tada, P. C. Paris, G. R. Irwin Manuel d’analyse des contraintes des fissures
Société américaine des ingénieurs mécaniciens (Handbook of Crack Stress Analysis
American Society of Mechanical Engineers 2001).
[21] Griffith A. A. The phenomena of rupture and flow in solids. Phil. Trans. Roy. Soc.
of London, 1920, A221, pp. 163-197.
[22] K. Nasri Analyse du comportement des fissures dans les bi-matériaux en zinc/acier
TRIP 800, Thèse ENSA, d’Oujda, 2014 (Analysis of crack behavior in zinc/steel bi-
materials TRIP 800, ENSA thesis, Oujda, 2014).
[23] A. Y. Rahmani magister “contribution à la modélisation de la fissuration dans les
structures en béton par la méthode X-FEM” Université Abou Bakr Belkaid- Tlemen
(“contribution to the modeling of cracking in concrete structures by the X-FEM
method” University Abou Bakr Belkaid-Tlemen).
[24] G. R. Irwin. Analysis of Stresses and Strains near the End of a Crack Traversing a
Plate Journal of Applied Mechanics 1957; 24: 361-364.
[25] H. M. Westergaard (1939). “Bearing pressures and cracks.” Trans. ASME, J.
ApplMech., 6:49-53.
Complimentary Copy
Complimentary Copy
Index
A
E
adsorption and dissociation of H2, 16
alternative binder to Co, 85, 89, 102, 111 electric explosion, 123, 134, 136, 142, 143,
ammonia decomposition, 20, 21, 76, 79 145
electrical discharge machining (EDM),
B 151, 153, 156, 157, 158, 159, 172, 174,
175, 176, 177, 178
bulk tungsten carbides, 6 ethylene, 2, 3, 15, 19, 20, 21, 33, 34, 47,
74, 75, 81, 83
explosive evaporation, 121, 122
C
capacitance, 154, 159, 160, 161, 162, 163, F
164, 165, 166, 167, 168, 169, 170, 174
cemented carbide, v, vii, 85, 86, 88, 89, 90, finite element, vii, 179, 181, 182, 183, 185,
91, 92, 93, 95, 96, 97, 99, 100, 102, 103, 190
104, 105, 106, 107, 109, 111, 112, 113, finite element method (FEM), 181, 182,
114, 115 185, 190, 193
coating, 55, 67, 99, 100, 144, 174, 177, formic acid (HCOOH), 2, 28, 31, 83
178, 179, 180, 181, 182, 185, 188, 189, fracture mechanics, 179, 181
190, 191, 192 functionally graded cemented carbide
coating stiffness, 181, 189, 191 (FGCC), vii, 85, 89, 96, 97, 99, 100,
crack, 92, 105, 109, 115, 154, 179, 181, 101, 111, 114, 115
182, 183, 185, 186, 187, 188, 189, 190,
191, 192, 193 G
cutting tool, v, vii, 86, 89, 95, 96, 100, 110,
111, 113, 114, 118, 179, 180, 181, 182, gas phase, 12, 47, 120, 121, 124, 129
185, 188, 189, 190, 191, 192
H
D
H2 dissociation, 18, 32, 84
Density Functional Theory (DFT), 2, 6, 10, heterogeneous catalysis, v, 1, 2, 5, 7, 13,
11, 13, 16, 18, 21, 25, 29, 59, 69, 80, 81, 15, 19, 24, 32, 37
83, 84 hydrocarbons, 4, 33, 34, 47, 67, 71, 129,
direct formic acid fuel cells (DFAFC), 28 134, 136
direct methanol fuel cells (DMFC), 24, 25, hydrogen evolution reaction (HER), 2, 5,
26, 80 15, 16, 18, 36, 37, 38, 39, 40, 41, 42, 43,
50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60,
Complimentary Copy
196 Index
61, 62, 63, 64, 65, 67, 68, 69, 72, 74, 75, 120, 124, 125, 127, 139, 140, 141, 142,
76, 77, 78, 81, 82 143, 144, 145, 146, 147, 148
Hyper 10 Micro EDM, 158 nanosized cemented carbides, 90, 91, 92,
96
nanostructured cemented carbide, vii, 85,
I 89, 111, 112
inert gas flow, 123
O
L
overcut, 159, 160, 161, 164, 165, 166, 167,
L9 orthogonal array, 159, 160, 174 169, 174, 176, 178
Levitation-Jet Method, 123
linear fracture mechanics (LFM), 181 P
literature review, 142, 152, 156, 159
physic-chemical methods, 117, 118
physic-mechanical properties, 117, 118
M
plasma-chemical synthesis, 124, 133, 134,
machining, v, vii, 85, 86, 88, 89, 90, 95, 143
96, 99, 100, 110, 111, 114, 115, 151, plastic substrates, 187, 188, 189
153, 157, 159, 161, 165, 168, 172, 174, pristine tungsten carbide (pristine WC), 3,
175, 176, 177, 178, 179, 180, 181, 182, 7, 15, 19, 30, 37, 69
189, 191, 192
machining process, v, vii, 85, 89, 96, 111, R
151, 157, 179, 180, 181, 182, 189, 191
machining tool materials, 85 response variables, 155, 156, 160, 174, 177
mesh, 14, 183, 184, 185
metal binder phase (Co), vii, 36, 43, 58, 59,
60, 62, 66, 73, 76, 79, 81, 82, 85, 86, 88,
S
89, 90, 91, 92, 95, 97, 98, 99, 100, 102, stress intensity, 179, 181, 182, 185, 186,
103, 105, 106, 109, 110, 112, 113, 114, 187, 189, 190, 191
115, 127, 141, 144, 160, 161, 162, 167,
168, 169, 181
methane activation and coupling, 19, 21
T
methanol, 2, 25, 26, 27, 28, 69, 75, 77, 79, Taguchi method, 156, 166, 174, 175
80, 83, 148 Ti6Al4V, 95, 96, 114, 156
micro-cracks of machined surface, 172 titanium alloy, v, vii, 95, 99, 151, 152, 157,
micro-electrical discharge machining 174, 176, 177, 178
(micro-EDM), v, vii, 151, 152, 153, tool, 15, 72, 85, 86, 87, 88, 89, 95, 99, 100,
161, 171, 172, 173, 175, 176 101, 111, 114, 115, 142, 152, 153, 156,
157, 159, 161, 162, 165, 168, 174, 175,
N 176, 178, 179, 180, 191
tool wear rate (TWR), 154, 157, 159, 160,
nanoparticles, v, vii, 19, 45, 48, 52, 55, 63, 161, 162, 163, 164, 168, 174
65, 67, 73, 74, 75, 80, 117, 118, 119,
Complimentary Copy
Index 197
V Z
voltage, 41, 122, 132, 155, 159, 160, 161, Z Co-ordinate (Depth), 174
162, 163, 164, 165, 166, 167, 168, 169,
170, 174
Complimentary Copy
Complimentary Copy

Nova Book

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Nova Book

Uploaded by

Copyright:

Available Formats

Complimentary Copy

A Review of Hydrazine and Its Applications

Pyrene: Chemistry, Properties and Uses

Pyrimidines and their Importance

What to Know about Lanthanum

The Future of Biorefineries

More information about this series can be found at

Copyright Clearance Center

NOTICE TO THE READER

Library of Congress Cataloging-in-Publication Data

ISBN:  H%RRN

Published by Nova Science Publishers, Inc. † New York

Preface .......................................................................................... vii

Tungsten Carbide in Heterogeneous Catalysis:

Carlos Jimenez-Orozco1,, PhD

Heterogeneous catalysis is important for producing fuels and

In: Tungsten Carbides

The theoretical studies offer a complete panorama as a bridge

Keywords: tungsten carbide, heterogeneous catalysis, DFT

Heterogeneous catalysis is used to produce several commodities, fuels, and

in working conditions and are characterized by a promising activity toward

Models and Methodologies for Tungsten

Bulk Tungsten Carbides

Surfaces of Pristine Tungsten Carbide

The heterogeneous catalysis operates on surfaces of solid catalysts. Therefore,

The model of the α-WC(0001) surface can be seen in Figure 3 and is

Tungsten Carbide as a Support of Metals

The use of WC as a support for Pt resembles a core-shell system, where the

experimental XPS result for the shifting of the 4f peak of Pt of a platinum ML

Figure 5. Pt monolayer supported on the α-WC(0001) surface with W- (left) and C-

Once the PtML/α-WC(0001) is formed, the Density of States (DOS) for

Here ε represents the Kohn-Sham eigenvalues, n(ε) is the calculated d-

E  Esurf  ads   Esurf  Eads  (2)

Therefore, the properties of PtML/α-WC(0001) are close to those of a

carried out by using a gradient conjugate algorithm (within Generalized

used. These meshes could be different, according to the right balance

Pristine Tungsten Carbides in Heterogeneous Catalysis

Hydrogen Adsorption and Dissociation

Figure 7. Calculated stable geometries for the interaction of H2 with C- and W-

Figure 7 summarizes the calculated stable geometries for the interaction

Figure 8 shows DFT calculated reaction paths for the dissociation of H2

Application of Pristine Tungsten Carbides in

In this section we provide a concise overview of the potential applications of

The hydrogenation of ,β-unsaturated aldehydes like cinnamaldehyde is

Methane Activation and Coupling

surface was more favorable for the decomposition of ammonia to produce

Adsorption and Dissociation of CO2

similar to the behavior on Mo2C found by Posada-Perez et al. (Posada-Pérez

Adsorption and Reaction of CO and H2O

Tungsten Carbides as a Support of Metals in

A common practice in heterogeneous catalysis to improve the performance of

Binding and Conversion of Methanol, Water, O2, CO, CO2

Figure 13. General scheme for methanol (CH3OH) decomposition on PdML/α-

The methanol decomposition involves CO and H2O binding on the M/α-

Binding and Conversion of C2+ Oxygenates and N-Based Compounds

than Pt, pointing to a rational choice of Pd instead of Pt in DFAFC. Hence,

Hydrogen Adsorption and Dissociation over Pt/WC

a single Pt atom (Pt-d); indeed, the barrier of this AuMLPt-d/α-WC(0001) was

Hydroconversion of Small Hydrocarbons

explored yet theoretically on PdML/α-WC(0001). The presence of ethylidyne

Tungsten Carbides as Support of Metal Clusters

silver monolayer, proposing an alternative material with lower atomic

The use of tungsten carbides in the field of electrocatalysis deserves a

Fundamental Aspects of Hydrogen Evolution Reaction

ISBN: H%RRN