International Journal of Refractory Metals and Hard Materials 119 (2024) 106493

Contents lists available at ScienceDirect

International Journal of Refractory

Metals and Hard Materials
journal homepage: www.elsevier.com/locate/IJRMHM

Sinter-based additive manufacturing of hardmetals: Review

Animesh Bose a, *, John P. Reidy b, Johannes Pötschke c
a
Optimus Alloys, LLC, Leesburg, VA 20176, USA
b
Desktop Metal, Inc., Burlington, MA 01803, USA
c
Fraunhofer IKTS, Fraunhofer Institute for Ceramic Technologies and Systems, Dresden 01277, Germany

A R T I C L E I N F O A B S T R A C T

Keywords: Hardmetals, commonly referred to as cemented tungsten carbide (WC) or simply tungsten carbide, is one of the
Additive manufacturing oldest liquid phase sintered, two phase composite, powder metallurgical (PM) product. In fact, this year marks
Hardmetals the 100th year since the first hardmetal patent was issued. The classic two-phase composite hardmetal structure
Cemented carbides
typically consists of hard ceramic-like WC particles that are embedded in a softer matrix binder phase primarily
3D printing
Sinter-based AM
consisting of cobalt (Co), sometimes in conjunction with other metals such as nickel and iron, that takes into
Review solution some tungsten and carbon.
Various shaping methods have been used to fabricate hardmetals into useful products. Traditional machining
to shape hardmetal components was extremely difficult due to the high hardness of these materials (significantly
harder than any steels used for cutting). Press and sinter was the process of choice for making relatively simple
shapes from hardmetals and is still extensively used. To accommodate some shape complexity, die pressed or
cold isostatically pressed “green” parts were machined followed by subsequent sintering to shape hardmetal
components. Extrusion using organic polymers was another technique that was adapted to make hardmetal rods
and bars. Using the powder injection molding (PIM) process to form more complex shapes from hardmetals was a
natural evolution. However, the tooling cost and the typically low volume of parts required for many hardmetal
applications was a major barrier. At the turn of the century, there was a rapid growth of the additive
manufacturing (AM) sector that is capable of fabricating extremely complex shaped components without the use
of any tooling. However, the early AM processes that gained commercial viability were founded on the melt-
based techniques, which was generally not conducive to processing of hardmetals. Since 2015, a number of
sinter-based AM technologies started to emerge and these technologies were found to be better suited for the
processing of hardmetals into complex shapes in an economic manner. This paper will review the developments
in the processing of hardmetals using some of the different sinter-based AM techniques.

1. Introduction 1.1. Brief history of hardmetals

2023 commemorates the 100-year anniversary of the invention of
hardmetals, based on the patent (DRP 420.689) that was granted to Karl
Schröter, in 1923 [1]. Even though the pure ceramic-like hard phase of
hardmetals, tungsten carbide, was first synthesized in 1897 by Henri
Moissan in an electric arc furnace (likely a mix of WC and W2C), the
application of the refractory carbides as useful components had to wait
for another quarter century. The following section provides a brief his­
torical perspective in the development of hardmetals.
Hardmetals were born out of the necessity for fabricating dies for
drawing tungsten wires for the electrical lighting industry. The dies
required hard and wear resistant materials and tungsten carbide was an
excellent candidate. Interestingly, though Schröter’s 1923 patent is
currently accepted as the origin of WC-Co-based hardmetals, Dr. Hein­
rich Baumhauer in March 1922 had applied for a patent based on
infiltrating porous tungsten carbide body with liquid iron to remove the
porosity and fabricate drawing dies [2]. In a strange twist of fate,
Baumhauer’s patent, though filed earlier than Schröter’s 1923 patent,
was granted later [3]. Thus, the 1923 patent by Schröter is recognized as
the origin of hardmetals, the first page of which is shown in Fig. 1.

* Corresponding author.
E-mail address: abose@optimusalloys.com (A. Bose).

https://doi.org/10.1016/j.ijrmhm.2023.106493
Received 7 September 2023; Received in revised form 7 November 2023; Accepted 8 November 2023
Available online 14 December 2023
0263-4368/© 2023 Elsevier Ltd. All rights reserved.
A. Bose et al.
Fig. 1. The first page of the 1923 patent by Schröter. Reproduced from [1].
Schröter during his development determined that the best properties
of the new hardmetal were attained only when a stoichiometric mono­
carbide of tungsten was used. Thus, the importance of maintaining strict
compositional control became evident from the earliest days of hard­
metal processing. The importance of the sintering atmosphere in
consolidation of the hardmetals was also established as it was shown
that reliable properties were only achieved when using hydrogen (coal
gas yielded poor results). Krupp Essen was granted the license to the
Schröter patent along with the rights to sublicense. Production of this
relatively new material was started in complete secrecy in April 1926.
The new material was given the trade name of WIDIA, which translated
from German meant “like diamond”. Large investments from Krupp
management allowed the investigation to progress quickly and soon
WIDIA hardmetal tips were soldered and used as inserts for the turning
and milling of cast iron and hardened steels. Interestingly, in the early
1930s, this new cutting material was extremely precious (1 g cost
around US $1.00) and was more expensive than 1 g of gold [3].
The history of hardmetals along with its processing and resulting
properties have been covered by several authors [3–13], including some
of the early chronicles that were published in the German language. The
first book on hardmetals was written in 1960 by Dr. Paul Schwarzkopf,
founder of the Metallwerke Plansee GmbH (Tyrol in Austria) and Dr.
Richard Kieffer who was the head of research and development [4]. This
was followed by a book written in German in 1965 by Kieffer and
Benesovsky [5] and another comprehensive book also in German writ­
ten by Schedler in 1988 [6]. A few books and book chapters on hard­
metals have been authored by Upadhyaya [7], Schubert, Lassner, and
2
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
Boehlke [8] and an excellent handbook in hardmetals has been pub­
lished by Brookes [9]. The latest addition is an overview authored by
Konyashin et al. [13].
1.2. Microstructure, properties, and applications of hardmetals
The earliest application of hardmetals was in tooling (dies) used for
drawing tungsten wires for the light bulbs. The suitability of hardmetals
for this application was primarily due to the combination of high
hardness and wear resistance along with its ability to resist fracture to
some extent. However, with time, it was determined that properly
processed hardmetal possess a unique combination of high hardness,
high compressive strength and modulus, excellent wear resistance, good
toughness, and corrosion resistance. Various combinations of strength,
hardness and toughness can be achieved through changes in the
composition (mainly through variation in the Co content) as well as the
grain size of the carbide particles. Thus, depending on the application,
the properties of hardmetals can be tailored.
This class of material finds applications in various industries
including but not limited to automotive, aerospace, oil and gas, mining,
medical, steel making (hot rolls, dies), defense, consumer, and sporting
goods. The applications can be divided into a couple of broad categories
that include cutting tools (cutting, drilling, boring, reaming, etc.) and
wear parts (waterjet nozzles, sand nozzles, wear resistant tools and dies
for various industries such as canned tooling, ceramic die pressing, glass
processing, etc.). Bose has [12] outlined some of the properties that
make this class of material extremely attractive for various industrial
sectors:
• Wear resistance that can be an order of magnitude higher than that of
steel
• Highest compressive strength among commercial materials
• Rigidity that is typically more than double than that of steel
• High hot hardness and elevated-temperature strength
• Impact toughness in some hardmetal compositions equal to that of
high-hardness tool steels
• Good strength and toughness from cryogenic temperatures to ~260
◦
C
• Good thermal and electrical conductivity often better than that of
steel
• Resistance to surface scratching and ability to be polished to a mirror
finish, providing a low surface friction
• Exceptional resistance to galling and welding
• Good resistance to thermal shock and oxidation up to ~650 ◦ C
• Compatibility with wear- and abrasion-resistant
• Applications in corrosive environments.
As discussed earlier, hardmetals are two phase composites that
include a very hard tungsten carbide phase that is cemented by a
metallic alloy binder usually consisting of cobalt (generally added as
pure metallic binder to mono WC). During the process of liquid phase
sintering of the WC-Co composition, upon reaching the liquidus tem­
perature, the cobalt melts and forms a cobalt-rich liquid by taking into
solution some of the tungsten and carbon. The resulting cobalt-rich
liquid forms between the tungsten carbide grains and at higher tem­
peratures rapidly spreads along the WC grains causing rapid rear­
rangement of the WC grains causing densification and bonding. As the
cobalt has solubility for both W and C, there is rapid dissolution of the
solid WC in the liquid cobalt that forms. Small WC grains are dissolved
earlier and is followed by reprecipitation on larger and still solid WC
grains. This causes grain growth. During cooling, the cobalt-rich liquid
that has spread along the solid WC grain boundaries solidifies, resulting
in a two-phase composite microstructure of WC grains that are
embedded in a tough and ductile cobalt-rich matrix. The high hardness
of the composite is generally due to the high hardness of the tungsten
carbide particles (which occupies the major volume fraction) while the
A. Bose et al. International Journal of Refractory Metals and Hard Materials 119 (2024) 106493

strength and toughness is imparted by the metallic alloy binder.
With similar tungsten carbide grain size, increasing the tungsten
carbide content (decreasing Co), generally results in an increase in the
hardness with a decrease in the fracture toughness. However, keeping
the same cobalt content but with decreasing tungsten carbide grain size,
the hardness of the composite can be increased. The fracture toughness
can be affected by both cobalt content of the composite as well as the
tungsten carbide grain size. It should be pointed out at this point that the
achievement of the optimal properties for a particular carbide grain size
and for a fixed cobalt content is dependent on the proper processing of
the hardmetal and the final attainment of a defect free two phase
microstructure consisting of just tungsten carbide and the metallic
binder phase. There is a narrow processing window that can result in the
desirable two-phase microstructure for WC-Co-based hardmetal.
Considering the phase diagram of W-C-Co system, the inability to
maintain the proper compositional balance can lead to the formation of
undesirable phases in the final microstructure that can include pure
carbon (graphite), β-W2C, eta (η) phases such as M6C (Co3.2W2.8C –
Co2W4C) or M12C (Co6W6C), etc. Fig. 2 shows a pseudo-binary phase
diagram showing the various phases along with the defect free two-
phase zone that is highlighted in yellow [14]. Optical
photomicrographs taken from two areas just outside the two-phase re­
gion are also shown in Fig. 2 (shows η-phase and graphite in addition to
WC and Co). Typically, the presence of the undesirable phases leads to
lowered mechanical properties of hardmetals.
The role of tungsten carbide grain size on the properties of hard­
metals has been a major research topic globally. With the findings that
the use of fine carbide grain size results in an increase in the bulk
hardness of the hardmetals, a flurry of development in processing of
finer and finer grain sizes, especially in lower cobalt containing hard­
metal compositions, were initiated among most hardmetal research
groups. The research efforts resulted in the finding that both hardness
and strength can be simultaneously increased using ultrafine or nano-
sized tungsten carbide grains in the final microstructure in properly
processed hardmetals. It was determined that it was necessary to use
dopants (minor additives) in the hardmetal compositions such as va­
nadium carbide and/or chromium carbide, to prevent the problem of
grain growth. The combinations of WC grain size and cobalt content in
hardmetals can result in a wide range of applications. Fig. 3 shows the
variation in the cobalt content versus the hardness of hardmetals as a
function of WC grain sizes. Research in ultrafine and nanocrystalline WC
grain sizes and grain growth inhibitors in hardmetals have grown since

Fig. 2. The central picture shows the different phases and the phase fields with varying carbon content and temperature for a W-10%Co (by weight) composition.
The two-phase microstructural region is shaded in yellow. Light optical photomicrograph shows the microstructure from a composition that is on the low carbon side
(left) of the phase diagram while the microstructure on the higher carbon side (right) shows the presence of graphite (right). Reproduced from Garcia et al, [14].

Fig. 3. Cobalt content versus hardness of hardmetals as a function of WC grain size for different carbide grain sizes. Data collection from Fraunhofer IKTS of
commercial and development grades.

3
A. Bose et al.
Fig. 4. Shows four different microstructures depending on the hardmetal
binder content and tungsten carbide grain size. Different applications that have
different property requirements can use this figure as a guide to gauge the type
of microstructure and composition necessary for a particular application.
Reproduced from [14].
the 1990’s and a large volume of literature is currently available
[15–40]. Advances in this area are important for future AM process
developments, as fine and ultrafine WC grain sizes is a direction that the
hardmetal industry will be headed.
The role of microstructure, composition, and proper processing are
keys to the development of the desired properties of hardmetals suitable
for different applications. It becomes obvious that no one process,
microstructure and property combination is suitable for diverse hard­
metal applications. For example, rock drilling tools for mining would
typically require coarse tungsten carbide grain size and higher cobalt
content to combat the high impact stresses that the parts are often
subjected to. On the other hand, for cutting tools, higher hardness, wear
resistance, and some edge toughness is required. This would tend to
dictate the use of ultrafine grain size with medium cobalt content. Other
applications that need resistance against high abrasion and wear with
little impact, can gain significantly when using fine grain size and low
binder. Garcia et al. [14] in their review has provided an excellent
pictorial guide to microstructures that can be produced with different
binder content and grain sizes and their corresponding properties. This
figure is reproduced in Fig. 4.
1.3. Non-AM shaping of hardmetals
Hardmetals are generally processed using the powder metallurgy
route. Due to the two-phase nature of hardmetals where the melting
points of the two components (WC and Co) are so different and WC
decomposes at high temperatures, conventional metal forming tech­
nology of melting and casting this class of material is not possible.
Traditional machining to shape hardmetal components out of fully
densified raw blocks is also extremely difficult due to the high hardness
and abrasive behavior of these materials (significantly harder than any
steels used for cutting). Here, only diamond-based grinding is used for
production of parts needed in low quantity.
The conventional powder metallurgical process of press and sinter
has been the main processing technique that has been used since the
early days to form hardmetal parts. However, the shape complexity
offered by the earlier press and sinter route is somewhat limited and
required parts with some axial symmetry. Earlier cutting tools were
simple in shape and could be easily formed by pressing into the green (as
pressed) shape followed by subsequent consolidation. However, as
cutting tools became more complex in shape (mainly due to the
4
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
introduction of chip breakers), simple die pressing became difficult. It
should be mentioned that the modern presses with advanced tool motion
controls and slides have led to the ability to fabricate more complex
shaped hardmetal parts. Another requirement for hardmetal compo­
nents that started to emerge is the component size combined with some
shape complexity. To address that challenge the hardmetal industry
adapted a process known as “pre-forming” which is achieved by green
machining of hardmetal powders compacted either by die pressing or
cold isostatic pressing (CIP). The process of CIP is capable of fabricating
large green billets. The green compacts (which are easier to machine
compared to sintered hardmetals) are subsequently machined using
conventional tooling to create relatively complex shaped hardmetal
components that must be subsequently consolidated. However, the
green machining of as-pressed hardmetals do suffer from poor yields due
to micro-cracks that can develop during machining and the process is
also quite slow. This process is however used in the industry to fabricate
larger sized more complex shaped hardmetal parts.
The continued demand for higher volume production of complex
shaped hardmetals led to the development of the process of powder
injection molding (PIM) of hardmetals [41–50]. The PIM process,
however, had its own set of challenges as it required expensive tooling
that also had very long lead times. As most wear parts made from
hardmetals are relatively large size (pushes the envelope of conventional
PIM size) and the number of parts required is quite low (between 100
and 1000 parts a year), it was difficult to amortize the high tooling cost
over a small number of parts. Thus, the conventional PIM process did not
gain commercial success. Low pressure powder injection molding (LP-
PIM) was an alternate process that was developed to address the issue of
the low number of hardmetal parts as well as the larger sizes required for
most hardmetal wear products compared to what conventional PIM
process was capable of handling. A handful of companies have used the
low-pressure PIM process to fabricate low volume (around 200 parts in a
year) relatively larger sized hardmetal parts [12]. This technology also
has not gained any significant commercial acceptance.
2. Additive manufacturing of metals and alloys
The start of the twenty-first century witnessed a rapid growth of the
additive manufacturing (AM) sector. The AM processes are capable of
fabricating extremely complex shaped components without the use of
any tooling. Early AM processes that gained commercial viability were
founded on the melt-based techniques, which did pose significant
challenges to the processing of hardmetals primarily due to the large
difference between the melting points of cobalt and WC and the
decomposition temperature of WC. Though a significant volume of
research has been devoted to the processing of hardmetals using various
melt-based AM processes, none of them have turned into commercial
reality.
The more recent proliferation of sinter-based AM techniques to shape
metal components has resulted in the separation of the geometric
shaping from the consolidation step. This process is more amenable to
the proper processing of hardmetals and has created new opportunities
for the processing of complex shaped hardmetals without any tooling.
Almost all the sinter-based AM technologies do utilize in some form
organic binders during the shape forming step and subsequently remove
the binders during the consolidation step. Thus, most of the sinter-based
AM technologies have a few steps that are like the PIM process. German
and Bose have provided a detailed discussion of several powder forming
processes using the assistance of polymeric materials [51]. This paper
will review the developments in the processing of hardmetals using
some of the different sinter-based AM techniques. At this point it will be
worthwhile briefly introducing some of the basics of AM (often referred
to as 3D printing) and then discuss in detail some of the sinter-based AM
technologies.
A. Bose et al.
2.1. Basics of 3D printing or additive manufacturing
Additive manufacturing (AM) has recently been drawing unprece­
dented attention and large funding from both private and government
sectors. The attraction for AM stems from the unique ability of the
process to create 3D objects without the use of any tooling. Extremely
complex shapes can be achieved by this process, thus allowing the de­
signers tremendous freedom. The AM process can add functionality
along with increasing geometrical complexity that is almost impossible
for other metal shaping technologies to match. The AM processes can
create complex organic shapes, infill structures, internal channels, in­
ternal porosity, customization of individual parts, and consolidation of
multiple components by integrating them into fewer integrated parts.
The above advantages are achieved in a cost-effective manner and in a
much shorter time compared to traditional processes. An early example
of such part consolidation was demonstrated by GE for a jet engine fuel
nozzle, in which a 20-component welded assembly was replaced by a
single printed part [52]. Metallic parts made by AM can also be used for
rapid tooling as well as rapid prototyping of parts as one does not have to
compromise using a lower performance polymeric part for form, fit and
function. These advantages have caused a phenomenal growth of AM
especially in the area of metals and alloys.
Though 3D printing has been around since the 1980s, it has shot into
the limelight around the turn of the century and more so after 2015. This
has resulted in the development of many variations in the 3D technology
platforms, some of which were aimed at getting around existing intel­
lectual property of other companies and some through natural evolution
and refinement of existing technologies. It was recognized early on that
there was the urgent need to try and bring some degree of general
consolidation among the plethora of 3D printing processes that were
spontaneously sprouting as without some degree of compartmentaliza­
tion there would be hundreds and hundreds of AM processes that
eventually would create problems for any attempts to create standards.
A class of technology platform that did not have any accepted standards
would be akin to a ship without a rudder that would result in confused
and eventually disgusted end users which would in the long run stunt or
delay the growth of the overall field. This situation has close similarity to
the powder injection molding or metal injection molding industry in the
1980s when there were no standards which initially resulted in some of
the larger customers from the medical arena to step back and wait till the
overall industry was able to come together and developed some stan­
dards. The difference in the case of AM is that compared to PIM or MIM,
the variations in the way the various AM platforms work are so different,
that even when trying to establish standards, there will likely be the
need for different standards for technologies that are totally different. As
a case in point if one considers the exact same material (some grade of
stainless steel or say same grade of nickel-based superalloy) and 3D
prints using a melt-based process like electron beam melting versus a
sinter-based process like material extrusion or binder jet, the properties
will likely be significantly different due to the inherent differences be­
tween the processes. The resulting microstructures for the end product
are also expected to be widely different with the sinter-based process
exhibiting a more uniform microstructure in the x, y, and z directions.
Thus, it would be important to recognize these major differences in the
different AM platforms and if they are indeed widely different, there will
be the need to have different standards to address the widely divergent
technologies. However, it would also be necessary to try and lump
together some of the similar AM technology platforms.
It should be recognized that in spite of the major differences in the
way different 3D printing processes work, all the 3D printing processes
fabricate the net or near-net shaped 3D parts by importing computer-
aided design (CAD) data files digitally followed by slicing the CAD
model into thin slices using well evolved slicing software and then
forming the part layer-by-layer (either to form a green part that then
5
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
needs to be consolidated to achieve the density and final properties or
forming the consolidated part directly using some of the melt-based
printing processes).
2.2. Classification of different AM processes
The predecessors to the current AM or 3D Printing processes were
known as rapid prototyping (RP) and rapid tooling (RT). It was believed
that the 3D printing process would be, at best good for quickly proto­
typing parts that could be tested for form, fit and function, and not for
actual manufacturing of net or near net-shaped parts. However, around
the turn of the century, the possibility of using the novel tool free process
to manufacture parts, started to emerge. The rapid growth of the tech­
nology led to the formation of the ASTM F42 committee to try and
standardize the terminology of this emerging AM technology that they
have defined as “The process of joining materials to make objects from
3D model data, usually layer upon layer, as opposed to subtractive
manufacturing technologies.” [53]. This definition was modified to
define AM technology as “a process of joining materials, generally in the
form of layer by layer addition, to make physical parts from 3D model
data, without the use of any physical tooling.” The tool free net or near-
net shape processing capability separated the AM processes from con­
ventional material shaping technologies such as subtractive (machining)
and formative manufacturing technologies (casting, powder injection
molding). Within the next five years (2015) an International Committee
was formed between ISO and ASTM to create a common ISO/ASTM
Standard on AM [54] that replaced the earlier ASTM Standard F2792. As
the number of different AM platforms started to grow, ASTM F42
Committee on Additive Manufacturing embarked on the arduous task of
trying to categorize the different AM processes. ISO/ASTM 52900:2015
(E) in Section 3.2 have listed various AM processes and described the
different names and explanation of the processes. ISO/ASTM 52900
have divided the process into two broad categories: Single-Step Process
and Multi-Step Process.
Single-Step Process: In this type of process, the desired geometric
shape, and the development of mechanical properties of the final
product are simultaneously achieved in a single step. Most of the melt-
based processes like Laser Beam Melting (LBM), Direct Metal Laser
Sintering (DMLS), Electron Beam Melting (EBM), Selective Laser
Melting (SLM), etc. fall in this category. The final part is generally
welded onto a solid metal plate and must be machined to separate the
part from the metal plate and the support structures.
Multi-Step Process: In this process classification, the geometric
fabrication of the part is separated from the consolidation step. The final
parts are fabricated in two or more different operations. The first
operation produces the basic geometry of the part (generally an over­
sized version of the final part) and the subsequent step(s) results in the
consolidation of the part that imparts the final properties of the part.
Almost all the sinter-based AM processes like binder jet, material
extrusion (and its variations), vat photopolymerization, metal jetting,
would fall under this category. Several of the processes in this category
also use some form of binder assist and have similarities with the PIM
process.
ISO/ASTM 52900 has further classified the AM processes into seven
different categories. Over the years, several different types of AM pro­
cesses have been developed that do not fall in the seven categories
outlined by ISO/ASTM. Some of these processes include hybrid additive
and subtractive processes, screen printing, cold spraying, gel and slurry
casting, 3D printing with paste, etc. The 7 AM processes according to
ISO/ASTM 52900 are outlined (primarily based on metal and alloy AM
processing and not pure polymers) in Table 1. As discussed earlier,
several new AM processes (some sinter-based) have emerged that are not
categorized in the ISO/ASTM 52900, and neither are they slight modi­
fications of the processes described in Table 1.
A. Bose et al. International Journal of Refractory Metals and Hard Materials 119 (2024) 106493

Table 1 Table 2
AM Process Classification according to ISO/ASTM 52900 and brief process Different sinter-based AM processes used for processing hardmetals.
description [54]. Sinter-based AM Variations on the different Companies /
ISO/ASTM Brief Description of the individual AM Processes processes used to Sinter-based AM Processes Organizations Involved
AM Process process hardmetals used for processing
Classification hardmetals

Liquid based bonding material is selectively deposited on a Thermoplastic 3D printing

Binder Material Fraunhofer IKTS,
thin layer of powder that is spread on a powder bed to join (T3DP);
Jetting Jetting AMAREA, XJet
the powder particles in the selected areas Nano-particle jetting (NPJ)
Focused thermal energy used to fuse materials by melting Fused Filament
Directed Energy
as they are being deposited. The thermal energy source can Fabrication (FFF);
Deposition
be laser, electron beam, or plasma arc. Bound Metal Deposition
Droplets of build materials (e.g. fine inorganic powders (BMD);
Material
suspended in organic solvents with photopolymer or Composite Extrusion Desktop Metal, Fraunhofer
Jetting Material
waxes) are selectively deposited to build the desired part. Modeling (CEM); IKTS, TU Vienna, KU
Extrusion
Material is selectively dispensed through a heated nozzle FFF using Ready to Press Leuven, DURIT
using a PIM feedstock (metal powder mixed with organic (RTP) powder;
binders) formed into coils, rods, or granules that are 3D gel-printing (3DGP)
Material extruded through a heated nozzle. The thin extrudate is Robo-Casting (Direct-Ink-
Extrusion deposited on a platform with precise x,y,z motion control Writing)
to build the final geometric shape which is subsequently Desktop Metal/ExOne,
subjected to debinding and consolidation to result in the Single pass jetting (SPJ); Teknalia, Fraunhofer IKTS,
final part. Triple ACT (Advanced University of Applied
Binder
Thermal energy is applied to selectively fuse regions of a Compaction Technology); Sciences and Arts Western
Jetting
powder bed to form the final desired part geometry. The Solvent on granule 3D- Switzerland, GTP,
Powder Bed Fusion thermal energy source may be a laser or electron beam and Printing (SG-3DP) Kennametal, Sandvik
depending on the intensity of the applied energy and the Additive, Hilti
material, the powders may be sintered or melted. Vat Photo- Lithography-based Metal Hochschule Aalen, Central
Thin sheets or foils of material cut into shape by a lase or polymerization Manufacturing (LMM) South University
Sheet Lamination knife and are bonded to form a 3D part. No sintering is
needed in this process.
A liquid photopolymer loaded with metal or ceramic 3.1. Material jetting
powder in a vat is selectively cured by light-activated
Vat Photo-
polymerization. With metals and/or ceramics, the polymer
polymerization Based on conventional inkjet printing, material jetting jets a viscous
is degraded and the geometric shape is consolidated by
sintering printing medium on a build platform. In contrast to processes belonging
to material extrusion, material is however not deposited in lines but
directly in droplets. For polymers, material jetting is one of the most
The rapid growth in the development of various AM processes has used AM technologies and known from companies such as Objet, now
resulted in an explosion in the patent and literature coverage of various Stratasys. Here, photopolymers are directly inkjet printed and solidified
AM processes. Numerous scholarly review articles have been published by UV curing allowing to print parts with a high definition and by using
covering the various metal AM technologies. Despite the rapid growth of different inks also to print colored 3D objects. Since hardmetals are not
the field (technical developments that may be considered state-of-the art photosensitive, other forms of achieving the solidification of droplets
at the time of writing a paper can become backdated by the time of have been studied.
publication), reviews in the area do provide some historical perspective
and do carry value especially when the fundamentals that do not change
quickly are adequately covered by the authors. Several review papers
that have attempted to cover most of the metal AM processes have had to
do so without getting in too deep and some review papers have tried to
cover a few of the processes in significant detail [55–72].
The AM processing of hardmetals, as touched on briefly, is quite
challenging due to the difference in the melting point of cobalt (1495 ◦ C)
and the dissociation temperature of WC which is around 2800 ◦ C [73]
and the relatively low vapor pressure of cobalt. This makes it difficult for
melt or beam-based AM processes to fabricate hardmetals. Nevertheless,
a lot of work was done regarding laser and electron beam-based AM,
which all yielded in material properties inferior to conventional pro­
duced hardmetal parts [74–99].

3. Sinter-based additive manufacturing of hardmetals

Some of the sinter-based AM processes and their variants that have

been used to fabricate hardmetals are shown in Table 2. Even though the
variations are classified under the broad categories (based on the pro­
cesses outlined by ISO/ASTM), it will be seen that the processes at times
are significantly different. Several review papers on AM of hardmetals
have been published that have covered in general both single step and
multi-step process (melt-based processes and sinter-based processes)
[100–103]. This paper will review only the sinter-based AM processes as
outlined in Table 2. Fig. 5. Schematic illustration of MJT technology NPJ, according to [104],
licensed according to Creative Commons license CC BY-NC-ND 4.0, https://cre
ativecommons.org/licenses/by-nc-nd/4.0/

6
A. Bose et al. International Journal of Refractory Metals and Hard Materials 119 (2024) 106493

3.1.1. Nano particle jetting
Nano particle jetting (NPJ) is material jetting variant developed and
patented by Israeli AM printer company XJet. NPJ uses a small particle
loaded suspension, that is held together with a back-bone solvent jetted
through ink-jet print heads as shown in Fig. 5.
Within the printer, part of the solvent evaporates by use of heat
lamps and a densely packed green part can be printed by iterations of
printing and drying. By using a secondary material as a support material,
extremely complex parts can be produced. NPJ is advertised to work
with ceramics and metals [105], however also hardmetal was investi­
gated and a corresponding ink patent granted in 2020 [106]. Work done
in collaboration with Fraunhofer IKTS between 2017 and 2020 showed
the feasibility of producing dense and complex hardmetal parts made
from submicron grained WC with 9 wt% Co [107], as shown in Fig. 6.
In contrast to most other AM technologies the high green density of
up to 51% theoretical density achieved in the NPJ process allows for the
production of parts with shrinkage ratios similar to conventional uni­
axially pressed or extruded hardmetal parts. After sintering using a
Sinter-HIP furnace, properties comparable to conventionally produced
parts with microstructures free of unwanted η-phase or free carbon
could be obtained as shown in Fig. 7.
Based on published literature NPJ seems to be a suitable AM tech­
nology especially for nano to submicron grained hardmetals which is
mainly due to the high green density and their higher sinter activity of
the fine powders. This also opens up the possibility for working with
lower Co containing hardmetals.
3.1.2. Thermoplastic 3D printing
Thermoplastic 3D printing (T3DP) was developed at Fraunhofer IKTS
in 2014 for printing of metal-ceramic composite green parts [108,109].
It is now also known as Multi-Material-Jetting (MMJ) and marked by
Fraunhofer IKTS´spin-off AMARA as printing solution for various sinter-
based materials. It is similar to direct inkjet printing (DIP) or drop on
demand (DOD) printing but, as in NPJ the ink is based on a homogenous
and stable suspension of ceramic or metal particles. Different from NPJ,
however, is that the backbone is not any solvent but a paraffin-based
thermoplastic polymer. Thus, both “ink” preparation as well as print­
ing must be done above the liquidus temperature of the thermoplastic
(wax) and solidification after printing happens by natural cooling as
shown in Fig. 8 for a DOD processes.
By controlling temperature, adjustments in terms of viscosity can be
made, which allows a large variety of possible volume loadings and a
wide material choice. Printing is done using piezo activated nozzles
which allow the jetting of droplets as small as 200 μm. Like in NPJ
different print heads allow for the parallel printing of either a later
removable support material or a second material.
For hardmetal 3D printing so far, different mono material composi­
tions of WC-12Co down to WC-6Co have been studied [110,111]. Since
as in NPJ, smaller WC grains seem more suitable for a stable suspension,
mainly nano to fine grained WC grades have been investigated as shown
in Table 3.

Fig. 6. Left: size comparison of printed and sintered hardmetal drill of WC-9
wt.-%Co produced by NPJ and subsequent Sinter-HIP sintering, right: details
of sintered drill with inner cooling channel of a diameter of ca. 140 μm
[reproduced from [107].

Fig. 8. Schematic illustration of DOD printing as analogy for T3DP where

particles are suspended with the wax, according to [104], licensed according to
Creative Commons license CC BY-NC-ND 4.0, https://creativecommons.
org/licenses/by-nc-nd/4.0/

Table 3
Physical properties of T3DP printed and sintered test parts, © Fraunhofer IKTS.
Composition wt.-% WC-10 Co WC-12 Co WC-6 Co

Density % theo. Density 100.0 99.8 99.7

Hardnesss HV10 2030 1470 1820
Fracture toughness MPa⋅m1/2 8.3 11.7 9.0
Magnetic saturation % theo. mS 80.7 87.9 84
Fig. 7. Microstructure of a NPJ printed and subsequently sintered, submicron Coercific force kA/m 47 17 23
grained WC-9 wt.-% Co drill. Reproduced from [107]. Mean WC grain size (class) Nano Sub-μ Sub-μ

7
A. Bose et al. International Journal of Refractory Metals and Hard Materials 119 (2024) 106493

Fig. 9. Left: hardmetal inserts produced by T3DP of WC-12 Co, middle: cross section showing the surface roughness, right: microstructure showing homogenous WC
grains. Reproduced from [107].

Even though the droplet size in T3DP is larger than in NPJ the res­ require the use of a precision tool while the material extrusion-based AM
olution in comparison to binder jetting or extrusion technologies is still processes are tool free. The remaining steps such as the feedstock
higher and lower surface roughness can be achieved. Fig. 9 shows some preparation, the debinding, and the consolidation by sintering are all
examples of printed and sintered test inserts produced from sub-μ mostly common. In fact, most of the sinter-based processes have some
grained WC-12 Co. commonality with the PIM/MIM process. Some of the differences be­
Both NPJ and T3DP are promising sinter-based AM technologies that tween the different sinter-based AM processes are the volume and
directly print droplets and allow a large variety of geometries and chemical compositions of organic material(s) that are left in the as-
possess the possibilities of multi-material printing of either different printed part (often known as the green part) that can vary signifi­
grades of hardmetal or hardmetal with other material combinations. cantly. The organic binder phase of the green part must be completely
removed before the densification of the inorganic particulates. The
3.2. Material extrusion debinding is often done in two separate steps; the first removing part of
the binder (filler phase) by different means (solvent, supercritical, cat­
As with many process platforms in the 3D printing area, polymeric alytic, or thermal) and the remaining binder (backbone) that holds the
materials generally come before metals and alloys. 3D printing using the shape is removed typically in the final sintering furnace. The debinding
material extrusion process had a similar origin through the pioneering and sintering step is significantly affected by the binder type and the
work of Crump in the late 1980s that resulted in a patent in 1992 [112]. binder volume in the as-printed part.
The process involved a movable dispensing head fed with a material that
freezes at a certain fixed temperature along with a movable base or build
platform. The base and the dispensing head can be moved relative to
each other along the three axes in a pattern that is already pre­
determined through a software while the semi-molten material is being
discharged continually through the dispensing head in a controlled
manner. The extruded semi-molten material solidifies upon contacting
the movable base or a previous layer of the extruded material. Thus, 3D
objects can be produced by repeated layering of solidifying material
until the desired shape is formed. Numerous organic materials were
shaped using this novel material extrusion process that became known
as Fused Deposition Modeling (FDM) and Fused Filament Fabrication
(FFF). More than one material can also be printed through the incor­
poration of multiple independent dispensing heads and different mate­
rial filament spools. Generally, machines would have at-least two
dispensing heads where one would extrude the actual build material and
the other would extrude a second material that often serves as a support
material (required for large overhangs or supporting round hole struc­
tures, etc.) that would be removed later in the process. In the case of
polymeric materials, the as build geometry or the geometry from which
the support structure is removed, becomes the final part.
The material evolution based on the material extrusion process soon
followed and included various thermoplastic polymeric materials that
were loaded with particulates (glass, ceramics) and chopped fibers.
Gradually, different variants evolved but in nearly all cases the as-
printed geometry was the final part geometry. None of these processes
were used to fabricate parts from monolithic metals and metallic alloys.
Most metal and alloy material extrusion processes have multiple Fig. 10. Schematic of the printing of a conventional FFF process used for
steps that are common to the PIM/MIM process described. The major polymer or metal AM based on particle filled polymers filaments, according to
difference between the material extrusion processes and the PIM/MIM [104], licensed according to Creative Commons license CC BY-NC-ND 4.0,
process is the geometrical shape forming step where PIM/MIM processes https://creativecommons.org/licenses/by-nc-nd/4.0/

8
A. Bose et al.
3.2.1. Fused filament fabrication (FFF) of hardmetals
A schematic of the FFF process as described earlier is shown in
Fig. 10. In this process the desired powders of the hardmetal composi­
tion are mixed with proprietary organic binder composition to create a
feedstock that is then formed into a filament that is wound into a coil in a
spool for storage. Filament from the spool is fed to the nozzle using the
two feed wheels at a precise feed rate. The filament travels through the
dispensing head into the heated nozzle where the solid filament is
melted into a viscous mass and pushed through the nozzle as an extru­
date of both the organic binder and the inorganic powders. The 3D part
is then built-up layer-by-layer by the deposition of the extruded mate­
rial. The 3D printed part, as in the case of the PIM/MIM parts, is an
oversized version of the final component. Some of the advantages of the
FFF process are outlined below:
a) PIM/MIM (already a mature technology) powders can be used in
FFF, giving FFF one of the widest material selections and lower
powder cost.
b) Less safety issues as the process does not deal with loose powders and
does not use lasers or electron beam.
c) Can use powders with a wide particle size distribution and a wide
range of powder morphology.
d) Can incorporate closed pores (intentionally printed) to achieve light-
weighting in the final structures that is not possible with powder bed
type processes (e.g., LPBF and BJT).
e) Can build off the PIM/MIM standards that are already published.
f) The equipment price is generally much lower compared to powder
bed processes.
g) Can create unsupported overhanging structures up to certain angles.
h) The major advantage over PIM/MIM is that no tooling is required.
Fraunhofer IKTS presented first results on printing of dense hard­
metal parts in 2018, that showed hardmetals having as low as 8 wt.-% Co
Fig. 11. Layers of FFF printed hardmetal part (left: lower magnification and right: higher magnification). Reproduced from [114].
Fig. 12. As-printed and sintered hardmetal part fabricated by FFF. a) FFF printed hardmetal part; b) FFF printed hardmetal part after sintering. Reproduced
from [114].
9
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
and a fine grain size (below 0.8 μm) and a resulting hardness of up to
1700 HV10 [113]. The used filaments were produced in-house using
either commercially available RTP (ready-to-press, pre-mixed and spray
granulated) powder or directly mixed and milled WC-Co powders.
This process has also been used by Lengauer et al. [114] in 2019 to
process hardmetals having a WC-10Co (wt.-%) composition. In their
detailed investigation, powders of the desired composition were ball
milled followed by vacuum drying. The powder was compounded with a
multi-component binder system in a kneading type of machine at 200 ◦ C
followed by granulation and sieving to attain the feedstock with a solids
loading of 50 vol%. The binder consisted of primarily two major com­
ponents, a filler phase and a backbone binder where the filler phase is
removed first during debinding using a solvent. Filament from the
feedstock was formed by extruding the feedstock through a nozzle with a
diameter of 1.75 mm. A relatively simple indexable cutting insert was
initially fabricated. The diameter of the nozzle through which the ma­
terial is extruded (for printing) was 600 μm. As the diameter of the
nozzle was relatively large, the surface roughness of the print was also
quite high (Fig. 11). Observation of the printing showed that the bottom
layer in contact with the print bed exhibited a relatively smooth and
continuous surface. Fig. 11 shows that the layers were well bonded
without any interlayer separation. There were some printing defects in
the form of small voids between the layers.
Debinding was carried out using the conventional two-step process
of solvent debinding followed by thermal debinding. The solvent
debinding was carried out using cyclohexane at 60 ◦ C for 48–72 h
(depending on the wall thickness). The solvent debound parts were dried
at 70 ◦ C in a vacuum oven followed by thermal debinding in a tube
furnace in a hydrogen or inert atmosphere. As solvent debinding opens
pore channels, moderate heating rates of 2–10 ◦ C/min to maximum
temperatures of 600–800 ◦ C were used. This step according to the au­
thors is critical for carbon control. Sintering was carried out in a vacuum
sintering furnace using a simple time-temperature profile with a hold at
A. Bose et al.
Fig. 13. Test components made of WC-8Ni (left), cross-section (middle) and SEM micrograph (right) produced using FFF. Reproduced from [107].
1150 ◦ C and 1430 ◦ C. The shrinkage between the printed part and the
sintered part was measured in the x-y and z direction and found to be
21% and 22%, respectively. Fig. 12a shows the picture of an as-printed
part (left) and Fig. 12b shows the picture of a sintered part (right). The
shrinkage of the sintered part from the as-printed (green) part can be
easily observed. The process can be used to create parts with reasonable
complexity; however, the surface roughness of the part is high. Also,
printing defects such as porosity is still a challenge with the as-printed
parts.
The conventional FFF process using the filaments and the process
described above have been used by various research groups to produce
hardmetal parts [115–118]. Further investigations carried out at
Fraunhofer IKTS on FFF of hardmetals showed that the process of FFF
was capable of fabricating both cavity and pore free parts with a wide
variety of hardmetal compositions. Dense parts with different cobalt
between 8 wt.-% to 12 wt.-% have been fabricated with hardness be­
tween 1200 and 1700 HV10. FFF printed, sintered and partially ground
as well as AlTiN coated indexable inserts made from submicron WC 8
wt.-% Co powders were also tested in machining S235JR steel. Results
showed a good performance and the basic suitability of FFF produced
prototype inserts for cutting operations [119]. Furthermore, hardmetals
with Ni [107] and other compositions such as TiCN based cermets [114]
were investigated. Some results of these investigations are captured in
Fig. 13.
Another investigation on the development of filaments from a WC-
10Co (wt.-%) hardmetal composition focused on the evaluation of the
critical powder loading or critical powder volume concentration (CPVC)
was carried out by Cerejo et al. [118]. The milled powder had an average
particle size of 8 μm. Parts using a filament with 48.5 (vol%) of the WC-
10Co material were extruded to produce simple geometries (cylinders)
and more complex parts such as spur gears. A suitable selection of
thermal parameters for debinding and sintering was developed to ach­
ieve the desired geometry and mechanical properties. The hardness and
the Youngs modulus of the consolidated material were 19.8 ± 2.5 GPa
and 678 ± 72 GPa, respectively and the linear shrinkage was found to be
22%.
It is often quite difficult for small AM companies to get the desired
hardmetal powders to convert into the filaments that can be used for FFF
fabrication. On the other hand, RTP and sinter powders for hardmetals
are quite easily available and are offered in a wide variety of
Table 4
Hardness (HV) and fracture toughness (KIC, Shetty) of hardmetal [120].
Material Thermal debinding Hardness
HV30
600 ◦ C, H2 1740
3D Hardmetal
800 ◦ C, H2 1750
10
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
compositions (some with only cobalt as the binder and some even
without cobalt). Thus, if there was a way to utilize RTP powders to make
FFF filaments that could be 3D printed, it would be one way to expand
the hardmetal compositions that can be printed. This issue was
addressed by Lengauer et al. [120]. In this development RTP powder
with a composition of 10% Co, 0.70% doping carbides, balance WC (wt.-
%) was used. The RTP powder was mixed with a multi-component
organic binder in a co-rotating twin extruder. The solids loading was
63 vol%, which was high as the powders were relatively more spher­
oidized compared to the pure WC and Co powders or when the two
powders are milled together. Filaments were prepared using a single
screw extruder through an extruder die having a diameter of 1.75 mm
and spooled. For extrusion, disc shaped samples 6 mm thick were
fabricated. The FFF machine used was set at an extrusion temperature of
250 ◦ C with the bed temperature set at 80 ◦ C. The extruded parts were
fully submerged in cyclohexane at 60 ◦ C while stirring the solvent. Based
on the experiments, a solvent immersion time of 72 h was used for all the
samples. After solvent debinding and drying, the samples were subjected
to thermal debinding using two different peak temperatures of 600 ◦ C
and 800 ◦ C and two atmospheres, nitrogen and hydrogen. Hardmetal
parts were vacuum sintered using a hold time of 30 min at a temperature
of 1150 ◦ C followed by a ramp up to a temperature of 1400 ◦ C using Ar at
elevated temperature to suppress cobalt evaporation. It was observed
that the thermal debinding condition played a significant role in the
attainment of the final hardmetal properties after sintering. The results
of the as-sintered properties are outlined in Table 4.
The investigations with the ready to press (RTP) powder are an
important step in making a wider range of compositions available for the
extrusion-based 3D printing industry (FFF). This allows printing com­
panies the freedom to use a special hardmetal composition of their
choice if they have the ability to form the filaments or subcontract out
the filament making to external entities, which more and more also offer
the on demand fabrication of hardmetal filled filaments.
Careful attention is necessary for the thermal debinding part of the
FFF processing cycle for the attainment of the desired hardmetal prop­
erties (especially proper carbon balance). The issues that the printing
companies must be aware are the type and amount of organic binder
already present in the RTP powder as these organics are expected to
interact with the actual FFF binder to be used for making the FFF fila­
ments. If the binder used in the RTP powder has high viscosity, then the
KIC Hardness reference KIC reference
MPa.m1/2 MPa.m1/2
9.8 1750 9.7
9.1 – –
A. Bose et al. International Journal of Refractory Metals and Hard Materials 119 (2024) 106493

rheology needed to make the material extrudable can be a challenge.

The amount of organic in the RTP powder is also important as that will
determine the final solids loading that subsequently influences the final
shrinkage of the part.

3.2.2. Bound metal deposition (BMD) of hardmetals

Bound Metal Deposition (BMD) builds on a modification of the FFF
process that was developed by Desktop Metal in 2016 and addresses the
challenge of lower solids loading and flexibility of the filaments in
conventional FFF process [121–123]. Other than that, the process fol­
lows the same processing scheme of FFF. The issue with the filament and
the feeding of the filament is addressed by converting the pelletized or
granulated feedstock into a precision rod with a larger cross section of 6
mm and a length of 150 mm, while the pushing of the rod through the
extrusion nozzle is achieved through the use of a finger at the top that
can apply a desired force (that is typically higher than that is possible in
FFF using the feed wheels). Other BMD developments include the
incorporation of a shrinking raft and a ceramic separation layer. The
shrinking raft was developed to reduce the frictional drag between the
parts and the sintering furniture by reducing the frictional drag. A thin
sacrificial structure (consisting of a few print layers) is first built with the
same material that the part is built from. Since the raft is built from the Fig. 14. Scanning Electron Micrograph (SEM) image of the WC-10%Co pow­
same feedstock material, and the part is built-up on it, the part and the der. Reproduced from [124].
raft can shrink together. The bottom of the raft is in contact with the
sintering furniture, but the top is free to shrink along with the part that is
built on top. The second development is the incorporation of a second
feedstock made from ceramic powder that is also fabricated in the form
of rods. The purpose of this ceramic material is to create a separation
layer between the part and the sacrificial raft as well as the part as the
support structure. The separation is achieved by printing a thin layer of
the ceramic feedstock where the raft or the support structure transitions
to the actual part. The ceramic powder is chosen so that it does not react
with the actual part material during sintering and converts into powder
after sintering. This allows for the easy separation of the part from the
raft as well as the support structures. This has been successfully used to
form parts from different materials that do not react with the ceramics
used as a separation layer [121-123]. Another advantage of this ceramic
separation layer is the ease of creating articulating structures. The
impact of the process on the overall AM industry is the promise of being
an office-friendly process capable of fabricating complex shaped 3D
printed metal parts economically without any tooling directly from a
digital CAD file. Fig. 15. Several hardmetal parts printed on the BMD Printer, in the as-printed
After printing, the parts are subjected to the usual debinding and state. Note the white ceramic seperation layers between the hardmetal raft and
sintering process. Earlier version of the BMD process relied on the two- the actual hardmetal part as well as the hardmetal support structure and the
step process of solvent debinding followed by sintering. This required actual hardmetal part. Reproduced from [124].
the use of three pieces of equipment, a printer, solvent debinding
equipment, and a sintering furnace. Current developments in the binder Nozzle Temperature: 160 ◦ C; Layer Height: 150 μm; Print Speed: 15
system have allowed the development of a more compact process that mm/s. Several complex shaped hardmetal parts were printed and are
eliminates the need for solvent debinding, thus, removing the need for shown in Fig. 15. The white ceramic separation layer between the
one piece of equipment and dealing with organic solvents and its printed raft as well as the support layers and the actual hardmetal part is
disposal. also shown in Fig. 15.
The development in the fabrication of hardmetals using the BMD Debinding was carried out by immersing the parts in a non-
process has been examined with encouraging results [124]. The inves­ flammable solvent that was held at a fixed temperature and removed
tigation was carried out using a WC-10%Co (wt.-%) with some grain at various times, dried, and weighed. From the data of weight loss with
growth inhibitors. The powder morphology is shown in Fig. 14. The D10, immersion time the required time to debind a part is determined. After
D50, and D90 of the powder was measured to be 1.24, 2.14, and 3.34 μm, the primary binder was removed, the solvent is drained from the
respectively. The surface area of the powder measured by BET surface chamber and the parts dried. Vacuum sintering was carried out in a
area measurement was 2.042 m2/g. metal hot-zone furnace using a peak sintering temperature of 1440 ◦ C.
Compounding of the feedstock was done in a double planetary mixer The sintering process uses several low temperature holds in hydrogen to
using a proprietary multi-component organic binder. The final solids ensure removal of all the secondary binder, following which the sin­
loading was 45 vol% and the melt flow rate of the feedstock was 27.7 tering atmosphere was switched to argon (atmosphere reduced to the
cm3/10 min, which was in the range suitable for the BMD process. The best possible vacuum while ramping up to the peak sintering tempera­
feedstock was granulated and was used to form the precision rods. The ture). As soon as the peak sintering temperature is reached, the furnace
nozzle used during printing had an orifice diameter of 400 μm. Some of pressure was increased to 600 Torr (argon) to reduce cobalt loss.
the print parameters that were established after print parameter opti­ The furnace profile for the vacuum sintering is shown in Fig. 16. Two
mization and used for printing the current hardmetal parts were: other consolidation techniques were also used to sinter these BMD

11
A. Bose et al.
Fig. 16. Vacuum sintering cycle used for sintering of the BMD hardmetal parts
that had been solvent debound (showing the time-temperature profile as well as
the atmosphere and the variation in gas pressure with time). Reproduced
from [124].
printed samples. A sinter-HIP (overpressure sintering) process and a
second vacuum sintering process at a peak temperature of 1465 ◦ C.
Some of the properties obtained from the three different sintering cycles
are shown in Table 5. The properties achieved by the BMD process are
comparable to the properties achieved by this material using conven­
tional PM processes.
It can be concluded that the BMD process is capable of printing and
processing complex shaped hardmetals to near full density with prop­
erties that are in the range of those obtained from conventional pro­
cessing of hardmetals of similar composition. The process can create
parts with large overhangs with support structures printed from the
same material. The use of sintering rafts printed from the same material
results in reduced distortion of the parts. The capability to easily sepa­
rate the actual part from the raft as well as the support structure provides
immense value in the creation of complex shaped parts using the BMD
process.
3.2.3. Composite-extrusion modeling (CEM) of hardmetals
In FFF and BMD, the granules or pellets are formed into filaments or
precision rods. The filaments or the rods are the feed material that is
used for printing and their fabrication is expensive. Thus, the concept of
directly using the feedstock granules or pellets as the feed for 3D
printing was quite attractive. Generally, granules or pellets are used by
almost all PIM/MIM companies as well as there are companies that
supply feedstock to the PIM/MIM companies. Thus, a 3D printing pro­
cess based on extrusion that could directly use the granules or pellets,
the cost would be less, and the availability of different materials will be
far broader. These advantages have led to the development of direct
pellet or granule-based printing using the material extrusion 3D printing
platform [125,126]. This processing concept has been adapted for
printing of hardmetals by Lengauer et al. [114]. They have named the
process Composite-Extrusion Modeling (CEM). Fig. 17 shows a sche­
matic of the CEM process that is analogous to the polymer based
Table 5
Properties of the consolidated parts [124].
Properties Sinter-HIP
at 1435 ◦ C and 1.8 MPa
Density (g/cm3) 14.38
Total Carbon (%) 5.34
TRS (MPa*) 1572
Hardness (HRA/VHN) 92 / 1575 (0.5-kgf)
Fracture Tughness (MPa.m1/2) 11.6
*
calculated from ksi to MPa.
12
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
Fig. 17. Schematic of the Composite-Extrusion Modeling (CEM) process, where
the polymer granules instead of being made from polymers only consists of
inorganic powder(s) and organic binder(s) according to [104], licensed ac­
cording to Creative Commons license CC BY-NC-ND 4.0, https://creativeco
mmons.org/licenses/by-nc-nd/4.0/
granulates where the polymer granules are replaced with a PIM/MIM
feedstock type of pellets.
In this case the feed mechanism for the granules (or pellets) is with
an auger that compresses and degasses the granules/pellets while ma­
terial is being moved from the hopper to the heated nozzle area. The
extrudate from the nozzle is the same for all the three processes and the
part build up method is also similar (layer-by-layer). The feed material
used by Lengauer et al. consisted of granules of a proprietary hardmetal-
polymer compounded material from PolyMIM (a feedstock supplier to
the PIM/MIM industry). The primary or filler phase of the binder was
water soluble. The hardmetal powder used was a submicron grade of WC
powder. The printing was carried out in an ExAM 255 printer from
AIM3D GmBH. The printer used a 0.3-mm diameter nozzle and a print
layer height of 0.1-mm (which was significantly finer than the one used
for the FFF type of process described earlier). The extruder was heated to
190 ◦ C while the print bed temperature used was 100 ◦ C. Printing time
varied from 15 and 20 min, depending on the size of the hardmetal part
being fabricated. The debinding was carried out by immersing the parts
in a mix of 98% water with 2% inhibitor at a temperature of 60 ◦ C for
hold times between 48 and 72 h. The water debound samples were dried
and thermally debound followed by vacuum sintering using a simple
time-temperature cycle like the hardmetal fabrication using the FFF
printing process (using a peak temperature of 1430 ◦ C). The shrinkage
Vacuum sintered Vacuum sintered
at 1465 ◦ C at 1440 ◦ C
14.43 14.43
4.45
92.8 91.3 / 1680 (1-kgf)
A. Bose et al.
Fig. 18. Prototype of a CEM-printed indexable hardmetal insert with a looped
cooling channel as shown in the CAD in (a) (top). The actual as-printed part is
shown in (b) (middle) and the sintered part is shown in (c). Reproduced
from [114].
along the x-y plane was 22.6% and 23.4% in the z-direction. Typically,
the shrinkage along the z-direction is slightly higher.
A complicated hardmetal part with an internal channel was fabri­
cated using the CEM process and is shown in Fig. 18 [114]. The part
shows a cutting tool with an internal cooling channel that loops parallel
to the circumference of the tool body. High speed cutting is usually
associated with high heat generation that could be mitigated to some
extent using active cooling where a cooling liquid is pumped through a
surface connected orifice and can escape through other surface con­
nected orifices. Fig. 18a show the CAD file of the conceptual tooling with
the cooling channel and three surface connected entry-exit ports at the
three corners of the tool that connect to the main cooling channel. This
concept is expected to keep a uniform thermal load in the tooling and
reduce the cooling fluid consumption.
The process has an inherent cost advantage in the raw feed material
for printing as well as more easily adaptable by PIM/MIM companies
interested in adding rapid prototyping and small volume serial pro­
duction to their available technology base. However, the process is still
quite slow for any moderate volume production and has some inherent
limitations in terms of production of pore free parts. The surface
roughness of the parts produced is also inferior to the parts produced by
PIM/MIM.
3.2.4. 3D gel printing (3DGP) of hardmetals
Another extrusion-based 3D printing process is known as 3D Gel
Printing. This process provides an interesting fusion of gel casting and
13
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
FDM [115,116,127,128]. In this process, powder is first formed into a
slurry in an organic solvent. Printing is carried out by adding the slurry
to a screw extruder in conjunction with an initiator and catalyst and then
extruding the mix through a nozzle. The radical polymerization of
organic monomers is the principle of gelation. This gelation creates a
macro-polymeric network that holds the powder particles together
allowing the extrudate to retain their shape.
The process begins with the formation of an organic monomer
solution-based slurry that is used as an ink that is conveyed to the screw
extruder of the 3DGP equipment under the specific pressure of com­
pressed air. Concomitantly, an initiator and catalyst in a certain pro­
portion is conveyed to the screw extruder. The materials are well mixed
in the screw extruder and extruded through a nozzle. The extrudate is
deposited onto a printing platform by selective motion between the
printing platform and the extruding nozzle to form the desired shape. A
schematic of the process is shown in Fig. 19 [127]. The organic binder
(monomers) in a short time cross-links and hardens to form and fix the
desired shape. In an investigation a hydroxyethyl methacrylate (HEMA)
monomer-based slurry was formed using a ball milled WC-20%Co (wt.-
%) composition. To form the slurry, the HEMA and N,N′-methylene-
bisacrylamide (crosslinker) are mixed and dissolved in toluene at a
concentration of 50% by volume of HEMA. The dispersant Solsperse-
6000 is added in a certain proportion and the WC-20Co suspensions
were ball milled for 2 h. The solid loadings were varied from 47 to 56 vol
% with 3 vol% increments. The quality of the slurry was dependent on
the solids loading and the viscosity. Using a shear rate of 20 s− 1, the
viscosity of the slurry was seen to increase with solid loading. It is
important to have a degree of fluidity to be able to extrude the material
through the nozzle and slurries with too high of a solid loading could not
be extruded. As the shear rate increases, the viscosity of the WC-20Co
slurry decreases significantly, indicating shear thinning behavior.
After extrusion, the shear force is no longer present, and the extruded
filaments stay relatively rigid instead of losing its shape. The key to the
success of the process is that idle time after extrusion and before the
crosslinking polymerization needs to be relatively short, as before
printing the next layer, the previous layer needs to have sufficient
strength to retain its own weight and the overall shape. The results
showed that the gelation behavior of the WC-20Co slurry was control­
lable, and the idle time decreased with increasing initiator concentra­
tion. Thus, with proper idle time control, the extruded paste can be
rapidly cured, and the layer is sufficiently strong to allow for the layup of
the next layer. The green parts are subsequently dried where the solvent
is removed typically below 100 ◦ C.
The green parts are debound and sintered to obtain the final part.
Due to the low content of organic binders, 3DGP printed green samples
only require thermal debinding. At temperatures around 600 ◦ C, the
binder burnout is complete. Sintering was carried out in vacuum at a
sintering temperature of 1360 ◦ C using the 56 vol% solid loading (along
with the three other loadings). The sintered density was 13.55 g/cm3
(99.93% theoretical density). Sintering of the highest loaded sample (56
vol%) showed the best hardness (HRA 87.7) and transverse rupture
strength (2612.8 MPa). The microstructure showed that the sintered
parts were near fully dense and did not exhibit any cracks or voids.
Fig. 20 shows the microstructure of the hardmetal parts sintered at 1360
◦
C at four different volume loadings [127]. Fig. 21 shows a 52 mm
diameter bevel milling cutter fabricated by vacuum sintering at 1360 ◦ C
of a 3DGP part made from WC-20Co composition. Tracks of the printed
layers can be observed on the surface of the bevel milling cutter even
though the part is near full density. Thus, additional surface finishing
treatments will be necessary to have these parts used in real life
applications.
Some of the advantages of the 3DGP process includes the wide range
of materials that the process can fabricate (metals, ceramics, cermets,
composites), lower cost of equipment compared to most other AM pro­
cesses (does not require powder spreading), low temperature process
requiring no special process gas cover. However, the process is slow
A. Bose et al. International Journal of Refractory Metals and Hard Materials 119 (2024) 106493

Fig. 19. a) Picture of printer, b) schematic diagram of 3D gel-printing (3DGP). c) and d) schematic of printing bulk parts. Reproduced from [127].

Fig. 20. Microstructure of WC-20Co samples prepared by 3DGP with varying slurry solids loading: a) 56 vol%, b) 53 vol%, c) 50 vol%, and d) 47 vol%. It can be
observed that near full density parts were obtained with 56 vol.% solids loading while 47 vol.% solids loading showed significant amount of porosity. Reproduced
from [127].

14
A. Bose et al.
Fig. 21. A 52-mm diameter bevel milling cutter fabricated by vacuum sintering at 1360 ◦ C of a 3DGP part made from WC-20Co composition. Reproduced
from [127].
compared to binder jet and the surface finish is poor and needs special
surface finishing treatments.
3.2.5. Robocasting and direct ink writing of hardmetals
Another extrusion-based 3D printing process known as Robocasting
relies on the formation of a colloidal ink or slurry of a powder with
moderate solids loading and low quantities of organic additives. Pro­
cessing of a WC-8Co (wt.-%) by Robocasting has been developed by
Medeiros et al. [129]. In this process, WC with average particle size of
0.8 μm was planetary ball milled with deionized water, poly­
ethyleneimine (PEI), and Metamax 115. The milled powder was formed
into a suspension and high speed milled with Zusoplast C92 and poly­
vinylpyrrolidone (PVP). The solids loading was 45 vol% while the
deionized water volume was 28 vol%. For robocasting the nozzle
diameter is 0.6-mm, print speed 35 mm/s, and the layer thickness 200
μm. Other process variants tried included different deposition angles,
initial layer heights, and printing speed. Both round and rectangular
samples were printed. Some of the defects included warping and
cracking that were mostly attributable to rapid drying of the as-printed
parts. Drying was carried out as quickly as possible (after printing so that
there is no oxidation of the parts). Debinding involved the use of several
ramps and holds to a maximum temperature of 650 ◦ C. The optimally
dried samples were subsequently sintered at 1400 ◦ C. A maximum
Fig. 22. The microstructure of a sintered sample that is etched with Caro’s acid
to remove cobalt and then etched with Murakami’s reagent to reveal the grain
size. Reproduced from [129].
15
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
density of 99.7% of theoretical density (14.75 g/cm3) for the WC-8Co
composition was achieved, with the lowest density condition reaching
92%. The mean microhardness of the high-density samples was reported
to be 1652.1 HV2 and the coercive force measured was 236.8 Oe. The
microstructure of a well sintered sample that was etched to reveal the
grain size is shown in Fig. 22.
In another investigation by Huang et al. [130] on Direct Ink Writing
(DIW) was carried out using NbC-Ni and another powder mixture of
NbC-20Ni-8WC (wt.-%). The desired powders were mixed, dried, and
sieved to obtain uniform sized powder particles. A hydrogel was formed
using a PEO-PPO poloxamer triblock copolymer, pluronic-F127 initially
dissolved in distilled water with 25 wt.-% pluronic-F127 and stored at 4
◦
C for 24 h to form a homogeneous hydrogel. A dual asymmetric plan­
etary centrifugal mixer was used to disperse 40 vol% of the powder
mixture with 60 vol% of a 25 wt.-% hydrogel aqueous solution. The
cooling and mixing process was repeated 5 times to achieve ink homo­
geneity. A constant air pressure plunger is used to extrude the ink in the
form of a filament through an 840 μm diameter using a feed rate of 15
mm/s. To create dense structures, the center-to-center extrudate spacing
was adjusted to 780 μm and the layer thickness was fixed at 720 μm. The
air pressure used was controlled to 0.35 MPa and 20 ◦ C during printing.
Thermal debinding was carried out at a heating rate of 1 ◦ C/min, and
debinding was done at 650 ◦ C for 2 h in H2 atmosphere to remove all the
binder. The parts were densified by vacuum sintering at 1420 ◦ C. Near
fully dense structures were achieved with properties comparable to the
press and sintered parts that were also carried out. The linear shrinkage
of the NbC-20Ni-8WC DIW parts were around 21%. Though this process
has not been used to directly fabricate WC-Co based hardmetal parts, the
process has the potential to fabricate different hardmetal compositions.
3.3. Binder jetting
Binder jet additive manufacturing (BJT) was first pioneered in the
1990s at MIT by Ely Sachs and was originally referred to as 3-Dimen­
sional Printing [131]. The initial BJT work focused on prototyping
and production of some tooling using ceramics [132]. In the following
decades, BJT has been applied to a variety of metals, alloys, ceramics,
and cermets, including hardmetals. The process is now considered one of
the highest throughput AM technologies and has drawn much interest
for high volume production applications, such as in the automotive and
consumer electronics industries [133]. As with other powder bed AM
technologies, the first step of the BJT process is to spread powder in a
thin layer. The powder for the new layer is usually provided in a “bed-to-
bed” fashion or by powder dispensing. Bed-to-bed processes use a “feed
bed,” adjacent to the build area, that is filled with powder at the
A. Bose et al.
beginning of the print. The feed bed platen is raised at the beginning of
each new layer and a leveling mechanism (such as a doctor blade or
roller) then pushes the exposed powder from the feed bed onto the build
area. Powder dispensing methods hold powder in a hopper above the
build area and then evenly dispense powder across the build area. After
the powder has been dispensed, a leveling mechanism is used to spread
the powder into a uniform layer. The powder experiences very little
compaction throughout this process, in contrast to PIM. Once the new
powder layer has been spread, binder is applied by the printhead in the
desired areas according to the sliced CAD file, as displayed in Fig. 23.
Binder is typically composed of polymer suspended in a solvent, often
with additives used to control physical properties of the fluid, such as
surface tension and viscosity. Some researchers have examined the use
of polymer-alternatives, including nanoparticle suspensions [134–138]
and metal precursors [139–143]. The binder is ejected from the print­
head as droplets, which impact the powder bed. Upon impact, the binder
must wet the powder and penetrate the layer thickness to allow stitching
to the previously printed layer. Following binder deposition, some BJT
processes apply heat to the printed layer to promote evaporation of the
solvent and prevent migration of the binder from the desired printed
Fig. 23. Schematic illustration of BJT technology, according to [104], licensed
according to Creative Commons license CC BY-NC-ND 4.0, https://creativeco
mmons.org/licenses/by-nc-nd/4.0/
Fig. 24. Polymer (shown in orange) precipitation at the necks of adjacent powder particles forming pendular bonds, left. SEM image of WC-12Co pre-sintered and
spheroidized powder, with rough highly faceted surface, right. Reproduced from [148].
16
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
regions. The layering process is repeated as necessary to generate the
desired green geometry within the powder bed. Once the printing step is
complete, the build box, along with the printed parts embedded in the
loose powder, is subjected to a curing cycle, which applies heat to
remove the residual solvent and build strength in the green parts,
sometimes through the promotion of cross-linking between polymer
chains. Green parts are removed from the build box and unbound
powder is removed from surfaces and/or internal features via a
depowder step. Consolidation of the green parts uses thermal processing
to remove the binder and sinter the powder compact to reduce porosity.
Shrinkage during sintering must be accounted for by oversizing the
green parts.
Printing hardmetals presents several dissimilar challenges compared
with other alloys. The typical metal alloy powder utilized in BJT is
produced by gas atomization, a process that creates spherical particles
with relatively smooth surfaces. These powders can be free-flowing and
often have tap densities >60% of the theoretical density. Powder flow­
ability is critical to the printing process, as it can affect the prevalence of
spreading related defects and determine the density of the resulting
green body [69]. Printing commercially available RTP WC-Co powders
early on resulted in very low green densities. Initial work at MIT printing
alumina agglomerates led to an innovation in which the ceramic parti­
cles were suspended in a slurry to accommodate the spreading step
[132,144,145]. This change increased the green density from <40% to
55–62%. The technique was later applied to WC and Co3O4 (loaded in a
ratio to achieve a WC-10Co composition after the reduction of the cobalt
oxide), yielding a green density of ~47% [146].
Porosity within spray dried granules can also inhibit densification
during the sintering step. Fraunhofer IPT conducted research from 2007
to 2009 using pre-sintered powder composed of granulated WC-25Co,
demonstrating near full density printed components using a post-sinter
HIP process [147]. The pre-sinter step removes the organic compo­
nents used during the spray dry step and eliminates some of the porosity
in the granules. Additionally, the presence of these organics may change
the wetting characteristics of the BJT binder, leading to print defects or
poor interlayer adhesion.
Even with pre-sintered powder, hardmetal green parts suffer from
poor green strength. Enneti et al. reported transverse rupture strength in
the green state of <3 MPa for most print conditions using a WC-12Co
powder with an apparent density of 40% [148]. The low green
strength may be attributed to the lower green density achieved in
hardmetal parts (typically <50%), as well as lack of coordination to the
WC by the polymer binder. Powder morphology may also contribute to
lower green strength. The rough, faceted surfaces of the powder
A. Bose et al.
particles offer locations for the polymer to precipitate on drying away
from the necks of adjacent powder particles, Fig. 24.
Several groups have demonstrated the capability of BJT components
with 10–17% Co content to meet the properties of conventionally
manufactured hardmetals of equivalent grade. Fraunhofer IKTS has
investigated 12% Co and 17% Co compositions, with WC grain sizes of
fine and medium as early as 2016 [149–152]. This work utilized powder
produced by a granulation step followed by pre-sintering at 1100 ◦ C.
The resultant components produced on a Z510 printer from the former Z
Corporation (now 3Dsystems) as well as on a ExOne Innovent+ printer
and consequent sintering using a Sinter-HIP at 1400 ◦ C and 100 bar
Argon are nearly pore-free, and the microstructures are both isotropic
and similar to conventionally manufactured hardmetal, as shown in
Fig. 25 and Fig. 26.
Global Tungsten and Powders (GTP) have produced a line of pre-
sintered and plasma spheroidized WC-12Co powders intended for BJT.
Enneti et al. have shown that these powders can be printed to a green
density of 42% and sintering at 1485 ◦ C at a pressure of 1.83 MPa
produces near full density [153]. Debinding must occur in hydrogen to
sufficiently remove the polymer added by the BJT binder. Insufficient
Fig. 25. BJT demo parts produced by Fraunhofer IKTS from WC-12 Co powders, © Fraunhofer IKTS
Fig. 26. Microstructure of WC-12Co component produced by conventional press and sinter (left) and by binder jetting (right), © Fraunhofer IKTS. Reproduced
from [107].
17
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
debinding can lead to high carbon and the precipitation of graphite in
the microstructure. Conversely, exposure of hardmetals to hydrogen at
elevated temperature may lead to decarburization and the formation of
η-phase. Therefore, the debinding step must be tightly controlled to
yield the proper carbon content. Investigations of lower sintering tem­
peratures and vacuum sintering led to a drop in density, as low as 92%
when just vacuum sintering is applied at 1435 ◦ C.
The microstructure observed was made up of mostly 1.4–2.0 μm
carbide grains, with a population comprising 10% of the grains at a size
of ~20 μm. It was found that this duplex microstructure afforded su­
perior wear resistance, with a 44% reduction in material loss compared
to other 12% Co compositions containing 1.4–2.0 μm carbide grain size
[154]. It is postulated that the duplex structure arises from extreme
heating of the powder particles during the plasma spheroidization pro­
cess. Non-equilibrium phases may be formed during the heating step and
then the rapid cooling causes precipitation onto some carbide grains
leading to significant growth. Separate investigations using powder
from GTP confirmed the presence of these large grains in the powder
prior to the sintering process, seen in Fig. 27 [155]. This investigation
also revealed the presence of porosity in the large grains found in the
A. Bose et al.
Fig. 27. Particle with coarse WC grains in Co matrix, including porosity within
the carbide grain. Reproduced from [155].
Fig. 28. Sintered microstructure of coarse WC-12Co, showing uniform carbide
size without the presence of very large carbide grains. Reproduced from [157].
powder. Following sintering at 1400 ◦ C and at a pressure of 3.5 MPa, the
remaining porosity appeared to exist only within the large carbide
grains. A recent study by Cabezas et al. tests the mechanical properties of
BJT components with this duplex microstructure [156]. They observe
that the hardness and scratch resistance are isotropic. However, it was
found that at testing length scales approaching the length scale of the
microstructural inhomogeneity (such as with a low load hardness test),
the measurement variability increases dramatically. The presence of
large carbide grains in this study may also be attributed to the high
sintering temperature (1500 ◦ C) used to achieve full density.
GTP recently made changes to the powder production method,
enabling sintering to full density with a uniform carbide grain size of ~6
μm [157]. In this study, powders of WC-12Co and WC-10Co were pro­
duced with a coarse carbide size. After printing, the parts had a green
density of 40–45% of the theoretical density. Subsequent sintering of
printed test parts at 1460 ◦ C and 5 MPa of pressure produced nearly pore
free samples with uniform carbide grain size, Fig. 28. The hardness and
wear resistance are in the typical range for similar carbide grades pro­
duced by conventional powder metallurgy. However, the TRS is at the
low end of the equivalent range. A wide variety of complex components
were successfully produced using these powders, Fig. 29.
Researchers from Kennametal have focused on the challenges of
densifying hardmetals with low binder content. For low Co-content
compositions, low green density and the presence of print defects from
the BJT process lead to interlayer porosity. At higher binder content,
18
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
Fig. 29. BJT parts produced using coarse grained WC-10Co and WC-12Co
powder from GTP. Clockwise from top left: combination spur and helical
gear, impeller, pinion, helical gear with integral dog clutch, pump impeller.
Reproduced from [157].
there is enough liquid available during LPS to fill in even large pores.
Prichard investigated the importance of tailoring powder properties
(specifically particle size distribution) to achieve high density using a
WC-10 wt-% Co composition [158]. This work demonstrated that while
coarse particle size distributions are desirable from a spreading
perspective, they are not ideal for every step of the BJT process. Finer
powders are known to improve sintering performance, but they do not
spread as well and often suffer from low green density. Coarse powders
also are susceptible to particle ejection upon binder droplet impact
during the printing process, which can introduce interlayer porosity and
decrease green density. An optimized particle size distribution (15 μm <
D50 < 30 μm) was shown to produce the best tradeoffs between per­
formance in the printing process and subsequent sinterability. Kenna­
metal has demonstrated BJT of WC-17Co, WC-13(Co + Ni + Cr + Mo),
and WC-10Co compositions sintered to full density [159]. The me­
chanical properties and microstructures observed with compositions are
isotropic. In some samples, pooling of Co binder was observed in the
microstructure (cobalt lakes), thought to be a result of large interlayer
pores that are filled by liquid during the sintering process. An example of
such Co pooling is shown in Fig. 30 [160]. The hardness of each is
considered comparable to equivalent grades produced by conventional
methods. The TRS for each composition is slightly lower than its
equivalent conventional grade. A solid carbide endmill was printed
using the WC-10Co composition and subjected to a cutting test (Fig. 31)
in which the tool wear was measured. The performance was found to be
equivalent to the same geometry produced by conventional processing.
A couple of hardmetal parts that have been produced by Kennametal
using BJT are shown in Fig. 32 and Fig. 33 [161].
Sandvik has also announced the introduction of 3D printed hard­
metal components [162,163]. Technical data on the properties of the
printed components is sparse, but Sandvik has indicated an intention to
print in three compositions: 12 wt.-% Co, 13 wt.-% Co with <1 wt.-%
“other,” and 10 wt.-% Co with <1 wt.-% “other.” Notably, Sandvik has
filed a patent on the preparation of WC-Co powder feedstock for sub­
sequent printing by BJT [164,165]. This patent describes spray drying
powder, followed by a pre-sinter step to remove the organic binder, and
finally a milling step to reduce the particle size to a range desirable for
BJT printing (listed as 30–70 vol% <10 μm). Some examples of hard­
metal parts made using the BJT by Sandvik are shown in Fig. 34 and
Fig. 35. Fig. 34(a) shows a picture of a wire drawing nib made by BJT
using a straight WC-12%Co grade with hardness of 1300 (HV30) and (b)
shows a cut out of the wire drawing nib showing some of the internal
features made possible by BJT. The internal cooling channel was not a
A. Bose et al. International Journal of Refractory Metals and Hard Materials 119 (2024) 106493

Fig. 30. SEM image of sintered WC-12Co microstructure produced by BJT, showing Co pools depleted of WC grains [160].

Fig. 31. BJT WC-10Co Kennametal Harvi1 TETM endmill 5-axis cutting 4140 steel (30 HRC). (a) Initial full slot 2D endmill, (b) standard tool Harvi1 TETM tool
(courtesy Kennametal).

Fig. 32. A hardmetal flow control device showing internal coolant channels
that was produced by BJT (courtesy Kennametal).

Fig. 33. Picture of a hardmetal impeller made by binder jet (cour­

realistic product geometry without AM. Keeping the internal surfaces
cool, enables a higher speed of the steel wire being drawn which
maintained quality and life of the nib, and thereby increase productivity.
The demonstrator design includes the cooling channel going in from one
hole, then makes 2.5 revolutions before going out through the other hole
(Courtesy of Sandvik Additive Manufacturing) [163].
tesy Kennametal).
Fig. 35 shows the picture of a nozzle which is a common product in
oil and gas deep hole drilling. The geometry of the nozzle, especially
with the threads, makes it challenging and costly to manufacture with
conventional manufacturing. The nozzles come in a range of sizes and

19
A. Bose et al.
Fig. 34. Wire drawing nib made by BJT using a WC-12%Co grade with a
hardness of 1300 (HV30). The figure on the left shows the full picture of the
wire drawing nib and the picture on the right shows a cut out of the nib
showing some internal features that are possible by BJT (courtesy of Sandvik
Additive Manufacturing) [163].
Fig. 35. Hardmetal nozzle made by BJT which is a common part used in oil and
gas deep hole drilling (courtesy of Sandvik Additive Manufacturing).
shapes which again makes it suitable for AM since to make the different
sizes, all that is needed are several CAD files instead of the same number
of molds or CNC programs. Having the AM capability also reduces the
inventory that the customer had to stock in the past due to the long lead
times to make the parts by conventional hardmetal processes (Courtesy
of Sandvik Additive Manufacturing).
While BJT of pre-alloyed hardmetal powder is the most common
method described in literature, it is also possible to utilize an infiltration
approach [166]. Pure WC powder is subjected to BJT to create the
geometric preforms, which are then pre-sintered and subsequently
infiltrated with liquid Co. This method requires careful control of both
green density and infiltrant dosing to ensure the pore space is filled
without significant distortion owing to excess dissolution of the WC
skeletal structure. A lean amount of Co relative to pore space was found
Fig. 36. Schematic of the SG-3DP process, with steps proceeding chronologically from left to right [170]. (Figure Courtesy of E. Carreño-Morelli.)
20
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
to be preferable for minimizing distortion during the infiltration process.
The optimal conditions produced WC-Co components with ~20% Co, at
a density of 98.5%. Minimal grain growth was observed, with an average
carbide grain size of 5.1 μm achieved. Importantly, this method only
produces 15% shrinkage from the green geometry, compared to 22–27%
for BJT of pre-alloyed powder. Additionally, the technique may be
modified to use a eutectic WC-Co composition rather than pure Co for
the infiltrant, enabling infiltration at lower temperature (1400 ◦ C
instead of 1520 ◦ C) [103]. Reduced processing temperature should
further limit the potential for carbide grain growth. Several micro­
structural defects have been observed in infiltration studies of tall
components [167]. Above a certain height, capillary forces are insuffi­
cient to draw the infiltrant into all the pore space, leading to low density.
Furthermore, a ternary phase (Co3W3C) is observed to form as the
critical infiltration height is approached.
A modified version of BJT, called the “solvent on granules” (SG-
3DP), has been applied to hardmetals by Carreño-Morelli [168-170],
Fig. 36. This method comprises two notable differences from conven­
tional BJT. First, the feedstock being spread is a powder-polymer
granule, rather than raw powder. Second, only a solvent is jetted dur­
ing the printing process instead of a solvent that has binder dissolved in
it. The solvent softens the polymer in the granules, bonding them in the
jetted regions. Green bodies produced by SG-3DP are then subjected to
the same processing as those produced by traditional BJT. This method
has been applied to both WC-17.7Co and WC-12Co compositions,
achieving close to full density after HIP in both cases. A percussion drill
plate was printed with the WC-12Co composition and preliminary drill
tests were found to be successful, with no broken plates.
While Co is the most popular metal binder for WC hardmetals, its
status as a conflict mineral and its adverse health effects have driven
research for potential Co replacements. Fraunhofer IKTS performed
some initial trials on WC-13 wt.-% Ni by BJT in 2017 [171]. Printed
samples were consolidated by sintering at 1600 ◦ C under 10 MPa of
argon. Two compositions were trialed, one without grain refiners and
one with 0.2 wt.-% Mo2C and 0.2 wt.-% Cr3C2. Components of both were
sintered to ~98% density, and the hardness of the composition with
grain refiners was higher (950 HV10 compared to 870 HV10). Further
work on Co free hardmetal compositions is also carried out by Desktop
Metal, even though no results are published yet [172].
Beyond WC hardmetals, researchers at Fraunhofer IKTS have
recently begun investigating BJT for other carbide based composites,
specifically TiCN based cermets [173,174]. This work examined the
impact of both metallic binder content (Ni with Mo2C added to lower the
solidus temperature) and particle size distribution on the resulting sin­
tering behavior. It was found that a composition with 29% Ni and 9%
Mo2C yielded the highest sintered density and most uniform micro­
structure among the trialed compositions. In the BJT trials with various
particle size distributions, a green density of just 24% was achieved.
Despite this low green density, samples sintered to >98% density using a
peak temperature of 1600 ◦ C. Improvements to the powder morphology
and tuning of the particle size distribution, combined with optimization
A. Bose et al. International Journal of Refractory Metals and Hard Materials 119 (2024) 106493

Table 6
Summary of current state-of-the-art for WC-Co by BJT.
Co Content (wt.-%) Process Notes WC Grain Size Hardness TRS /MPa Source

21 Infiltration 3–5 μm 918 HV0.5 – [166]

19 Infiltration 6–10 μm 850 HV10 – [103]
17 1.2–1.5 μm 1020 HV10 3022 [151]
17 1–11 μm 982 HV* 3150 [159]
13.5 (Co + Ni + Cr + Mo) 1–6 μm 1173 HV* 2814 [159]
13-Ni – – 870 HV10 – [171]
13-Ni 0.2-Mo2C 0.2-Cr3C2 – – 950 HV10 – [171]
12 SG-3DP – 1308 HV30 – [169]
12 6 μm 1050 HV30 2684 [157]
12 Duplex: 1.4–2.0 μm, 20 μm (10%) 1256 HV30 – [153,154]
12 Duplex: 1–3 μm, 20–40 μm (20%) 1205 HV10 2257 [155]
12 Duplex: 0.5–2.0 μm, 3–10 μm (20%) 1224 HV10 – [156]
12 1.2–1.5 μm 1170 HV10 3102 [151]
12 0.8–1.2 μm 1330 HV10 – [151]
10 1119 HV30 2231 [157]
10 <1 μm 1523 HV* 3420 [159]
*
Converted from HRA scale.

of print parameters, are likely necessary to increase green density and reported in literature likely acts as a barrier to commercialization of BJT
resultant sintering performance of BJT cermets. The relevant properties hardmetals as well. At low green strengths, it is much more likely for
for WC-Co components produced by BJT by various researchers have components to break during the depowder process, reducing the overall
been summarized in Table 6. yield of the process and making it difficult to resolve fine features. It is
BJT is among the most promising methods for applying additive quite exciting to note that GTP through private communication have
manufacturing to hardmetals. When compared with other sinter-based mentioned that they have been able to produce hardmetal parts by BJT
AM strategies, BJT has very high productivity while also requiring less that have a mass >20 kg, though at this time they did not have the
polymer for the formation of green bodies. The relatively low polymer permission to show the part. This is a breakthrough for BJT processing of
content in BJT green parts allows faster debinding [175] and reduces the hardmetals.
likelihood of introducing excess carbon into the microstructure. How­
ever, it should also be recognized that the binders that are typically used
in BJT are thermoset binder that achieve strength through crosslinking 3.4. Vat photo-polymerization
and not the simple thermoplastic binders that are used in a number of
sinter-based AM processes. Generally, the crosslinked polymeric mate­ Stereolithography (SLA), Direct Light Processing (DLP) or overall Vat
rials are more difficult to remove cleanly than the thermoplastic binders Photo-polymerization (VPP) based additive manufacturing is in case of
in spite of the lower volume of the binder in the BJT process. Thus, polymers and ceramics unbeaten in regards to precision, surface
proper care must be taken during the debinding and sintering stage to roughness and resolution [176]. It was first developed for polymers and
account for this. The surface finish of BJT parts is superior to those made later successfully demonstrated to also work for photoreactive resin with
by material extrusion methods, but inferior to parts produced by ma­ suspended ceramic particles [177]. Like in material jetting, the used ink
terial jetting. The surface finish achieved by BJT is still too high for
many hardmetal applications, though, and some final machining will be
necessary in those cases. Several groups have demonstrated BJT of fully
dense WC-Co components with Co contents of 10 and 12%. These groups
have found that the hardness and TRS of BJT hardmetal components are
comparable to hardmetals of equivalent grade produced by conven­
tional press and sinter methods (with the TRS falling at the very low end
of the range). Microstructural homogeneity has been identified as one
challenge for BJT of hardmetals. The plasma spheroidization process
used for some hardmetal powders has been shown to introduce spurious
large carbide grains, some with entrained porosity, into the powders.
Even with powder that has only undergone pre-sintering, growth of
large grains may occur due to the high sintering temperatures utilized to
reach full densification. This duplex microstructure has been shown to
present advantages with respect to wear properties, though. Some re­
searchers have also noted the presence of patches of Co, likely formed
from the binder filling in large voids formed during the print process.
The effects of these Co pools on the mechanical properties have not been
thoroughly studied. Efforts to produce WC-Co components by BJT with
<10% Co have so far been hindered by high porosity after sintering. The
maximum hardness achieved is in the range of 1300–1500 HV10 and
mean grain sizes are often above 1 μm. Increasing the green density of
BJT hardmetals may be necessary to enable sintering of lower Co-
content and lower WC grain size based hardmetals to full density. The
maximum green density reported in literature is <50%, and shrinkage is
often ~22–27%, which can make dimensional control difficult (when Fig. 37. Schematic illustration of SLA technology DLP, according to [104],
compared with BJT of other metal alloys). The low green strength licensed according to Creative Commons license CC BY-NC-ND 4.0, https://cre
ativecommons.org/licenses/by-nc-nd/4.0/

21
A. Bose et al.
Fig. 38. a) Spray granulated and pre-sintered WC-12 Co granules, b) cross section of the VVP printed green part, according to [183] licensed according to Creative
Commons license CC BY 4.0, https://creativecommons.org/licenses/by/4.0/
or feedstock is a particle filled suspension. However, here the part is
built turned up out of a bath of ink, geometrically defined by either a
laser curing (SLA) or a precise digital light processing (DLP) projection
system that simultaneously cures a whole layer by activation of photo­
polymers within the ink, as shown in Fig. 37.
After the whole layer is solidified, the just printed layer is moved out
of the bath and the next layer is cured. One of the advantages of VPP is
its ability to produce highly detailed objects. Together with its ability to
produce complex geometries with smooth surfaces this AM technology
offers for some application the direct use of printed and subsequent
sintered part. The whole process works fine for light transmitting
polymers or translucent ceramics suspended in these polymers, but
materials with high absorption of the used wavelength (such as WC in
hardmetals) can under normal circumstances not be processed and a
fully solidified (layer upon the previous layer is not possible). Thus, it
was long believed that hardmetals could not be produced by VPP at all.
However, in recent years more and more “dark ceramics”, like AlN, SiC
or Si3N4, have been successfully produced by adjusted VPP technologies
[178–180]. Thus, also some basic research has been published about
VPP of hardmetals by researcher of Aalen university, in Germany
Fig. 39. a) Optical microscope overview image of sintered test cube, b) SEM image of microstructure of sintered test cube, according to [183], licensed according to
Creative Commons license CC BY 4.0, https://creativecommons.org/licenses/by/4.0/
22
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
[181–183]. Even though initial research focused on producing stable
suspensions based on ca. 1 μm diameter sized WC and Co grains, final
advancements were only made with larger pre-sintered WC-Co granules,
as used for binder jetting of hardmetals. The reason behind it is again
that the possible curing depth can be enhanced with larger particles
(here the pre-sintered WC-Co granules) due to a higher possibility of
larger gaps between them, through which the light source can cure
lower laying areas of the printing layer. Examples of using pre-sintered
WC-12 Co granules are shown in Fig. 38a. Printing was done using a
Lithoz CeraFab 7500, a layer thickness of 45 μm and a quite high
exposure of 97.76 mW/cm2 for 30 s. Green parts as shown in Fig. 38b,
with a green density of ca. 40% and a resulting linear shrinkage of 26.6%
(nearly the same in all direction) were produced and sintered in 1 bar
Argon at 1450 ◦ C for 1 h.
After sintering a density of around 91% of theoretical density was
achieved, with defects originating from the printing of up to 100–200
μm (Fig. 39a). Still, in many places a dense and homogenous WC-Co
microstructure was formed and no η-phase or free carbon was detec­
ted (Fig. 39b).
Due to the high porosity both hardness and fracture toughness values
A. Bose et al.
Fig. 40. a) Prototype WC-12Co insert with internal cooling channel, b) detailed view of inner structure, according to [183], licensed according to Creative Commons
license CC BY 4.0, https://creativecommons.org/licenses/by/4.0/
were low, with 1160 HV10 and 12 MPa*m1/2, respectively. Printed
prototypes of inserts showed that also complex inner structures and nice
surfaces were possible (Fig. 40).
Further work has also been done by Zigong Cemented Carbide Co.,
Ltd. working in conjunction with Central South University [164]. The
process developed by them combines the characteristics of hardmetals
with sol-gel, light curing and other methods, using salt solution as the
raw material, supplemented by light curing method as develop for re­
fractory metal Tungsten [184]. The process steps include ink configu­
ration, light curing, 3D print, followed by degrease and sintering. The
research efforts used low-cost printing equipment to make precision-
molded carbide blanks and they claim that the process is capable of
delivering finished products having surface quality that is close to that of
molded hardmetals. This process does seem to offer a promising tech­
nological platform; however, details of the complete process are lacking.
Even though the research work on VPP or DLP of WC-Co is believed
to be terminated, the results were nevertheless promising. Considering
for the VPP trials the unsuitable sintering conditions under standard
atmospheric pressure (no vacuum sintering, no sinter-HIP sintering, just
Ar) and the use of starting powders with a quite high inner porosity,
promising results can be expected if the work is picked up again and
adjusted VPP technologies are used. One promising lithography based
new printing technology is “lithography-based Metal Manufacturing”
(LMM) from Incus, which is already successfully used in the fabrication
of 316 L metal parts [185] and could be used to produce hardmetals with
microstructures like the ones achievable by BJT.
4. Perspectives on hardmetal sinter-based AM processes
Hardmetals and its processing is quite unique among the class of
industrial materials that are in use. Among hardmetals, compositions
based on WC and Co are the oldest (100 years) but remain the most
heavily used hardmetal class. In spite of major concerns with the toxicity
of hardmetals and Co being identified as a critical and strategic material,
Table 7
Qualitative comparison of the four major sinter-based AM methods used for hardmetals.
Process Development stage Tested in use cases
Material +++ no
Jetting
Material ++ yes
Extrusion
Binder ++++ Yes, many
Jetting
Vat Photo- + no
polymerization
23
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
WC-Co based compositions still dominate the field of hardmetals. The
fabrication of this material into complicated shapes is a true challenge as
the hardness of this material makes it almost impossible for it to be
shaped by conventional machining (it is a material that is used for
machining) techniques when fully dense. This led to the use of primarily
simple shaped hardmetals, ironically for shaping other metals (tungsten
wire drawing dies and cutting tools) during the early years of its
development primarily using the powder metallurgy technique of
pressing and sintering. As the demand for more complex shaped hard­
metals increased, innovations in the processing of this class of material
also increased. Some of the processing strategies adopted included green
machining of as-pressed parts, powder injection molding using hard­
metal powders, low pressure powder injection molding technology, as
well as significant improvements in the pressing technology that com­
bined with the improvements in spray drying of hardmetal powders into
agglomerates for improved flow and die fill. All these processing tech­
nologies have their pros and cons, but have one common challenge, and
that is to achieve a near fully dense part with proper carbon control
resulting in a clean two-phase microstructure in the final part. Thus,
shaping of this class of material not only has the challenge of limited
shaping options after full densification, but also the attainment of the
proper carbon level and microstructure in the final part. With the 3D
printing technologies gaining more traction, and due to the ability of this
technology to make shapes without tooling, it led to a major R&D effort
in this area. Since the melt-based AM technologies were the earliest 3D
printing platforms, it was natural that hardmetal processing was first
investigated using the melt-based printing platforms despite the known
challenges. Though major research efforts were devoted in this area, the
technology challenges proved to be too powerful and the processing did
not gain commercial viability.
All the sinter-based AM processes that have been covered in this
review have one thing in common, which is the separation of the
geometrical shape formation and the consolidation that is achieved by
sintering. The resultant sintered microstructure (if processed properly)
speed precision size Geometrical freedom
++ +++ ++ +++
+ + + ++
+++ ++ +++ ++
+ +++ + ++
A. Bose et al.
is homogeneous in nature unlike the melt-based processes. Thus, these
processes do lend themselves to the proper processing of hardmetals and
the development of normal two-phase microstructures. In these sinter-
based AM platforms, the desired properties that depends on the proper
processing and compositions of the hardmetals can be achieved.
This review has covered most of the prominent sinter-based metal
AM process that have been explored in processing of hardmetals into the
desired shapes and attainment of the desired properties. Table 7 pro­
vides a form the authors agreed upon to assess the four major AM pro­
cess classes and to provide some qualitative scoring on several aspects of
manufacturing readiness. The classification is based on a maximum
score of 4 stars (4 being excellent) and 1 being applied for processes that
are just being explored.
Among the sinter-based AM platforms, the vat photopolymerization
process that is also known as lithography technique, is still in its infancy.
However, exploration in this area has been initiated. The difficulty in
achieving success with this technology lies in the inherent characteris­
tics of hardmetals that have high absorption of the wavelengths that are
used in vat photopolymerization processes which did not allow the
transmission of light that is essential for this process. Thus, the typical
suspension of the desired materials in the photopolymers used in this
process platform has not yielded success. However, some successes have
been gained by researchers from Germany using coarser pre-sintered
granular powder, similar to binder jet powders, instead of the fine
micron sized powders that is typically used in this platform. Thus, this
process could create very fine details with some of the best surface
finishes that is achievable on nearly all the current metal AM platforms.
That the process is capable of fabricating various metallic parts with
high precision and low surface roughness has been demonstrated
already by Incus and research partners such as Fraunhofer IFAM and
others. There are also reports of work from China related to the use of
this technology platform to create hardmetal parts with surface finish
that is comparable to molded parts (process details are lacking).
Therefore, in the opinion of the authors, research in this area for hard­
metal processing will continue. It should be noted that the process will
be slow as the fine features and excellent surface finish are achieved
using small surface layer thickness.
The material jetting platform, which has a couple of different ver­
sions, is a relatively new technology that holds promise in hardmetal AM
processing. One of the variants known as nano-particle jetting (NPJ), as
the name suggests, uses ultrafine to nano sized hardmetal particles
suspended in a solvent that can be jetted through print heads. As the
name suggests, NPJ platform lends itself to ultrafine and even nano sized
hardmetal powder particles. As discussed earlier, one of the trends in
hardmetals is to go toward finer and finer WC grain size. The NPJ pro­
cess, to maintain hardmetal particles in suspension (without appreciable
segregation), naturally seeks to use the fine powders. Investigations
carried out reveal the fine features that are possible when using this
platform as well as it can produce parts with ultrafine grain sizes. Since
this platform does not require powder spreading like in case of binder
jet, it can use submicron and irregular shaped powders directly. The
powder loading in this process is slightly above 50 vol% which results in
shrinkages like press and sinter parts of similar compositions. The pro­
cess also holds the promise of being able to use low cobalt containing
high hardness hardmetal compositions. The second variant, Thermo­
plastic 3D printing (T3DP) developed by Fraunhofer IKTS and now
commercialized by AMAREA, also jets molten drops of a stable sus­
pension of hardmetal particles in paraffin wax (ink). This hot ink is
jetted to form the desired part. In this case also, submicron or nano
powders are better as it helps to form stable suspensions. This platform
has been used to process WC-12Co and WC-6Co. The process, due to
slightly larger droplet size than the NPJ process, results in slightly
coarser surface finish but yields surface finish better than material
extrusion or binder jet. This process can use lower cobalt compositions.
Both the material jetting platforms, NPJ and T3DP, do hold the promise
of becoming a viable commercial processing platforms with the
24
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
capability of printing different hardmetal compositions as well as use
submicron to nano particle sizes that is generally difficult with other
sinter-based AM platforms. These processes also have the capability of
multi-material printing thus allowing the creation of novel multi-
material structures and graded hardmetals.
The material extrusion process is one that has had some actual ap­
plications in hardmetals. This is a relatively more mature technology
among the sinter-based AM processes. This platform has the largest
variety of processing schemes with all variants resulting in an extrudate
that goes to build up the part layer-by-layer. The variations are based on
the different forms that the feed material is supplied to the dispensing
chamber.
The productivity of the material extrusion-based processes is quite
slow, resulting in the process not being amenable for high volume pro­
duction parts such as cutting tools. However, the process is capable of
printing prototype tooling for design verification and testing and in
some instances can also be used for low volume serial production of a
part with the same design. Among the processes, FFF (or FDM) type of
processes are extremely popular mainly due to their simplicity and lower
cost of the machines. However, the inherent advantages of the BMD
process (forming of rods and their use as feed material) is leading to this
process gaining traction. The fabrication of the raw material for the
printing in the form of filament that can be coiled in a spool while
maintaining a moderately high solids loading is a challenge and is quite
expensive. Lower solids loading leads to higher shrinkage and therefore
higher probability for part distortion. The problem is further amplified
in the case of hardmetals as the hardmetal powders are typically fine and
is quite irregular in shape, thus, resulting in lower critical solids loadings
(often below 50 vol%) compared to conventional spherical MIM pow­
ders that can be as high as 65 to 69 vol%. Another challenge for the FFF
process is the filament feed system that is dependent on the driving
wheel. The filament needs to have enough mechanical strength so that it
does not break when being pulled by the drive wheel and does not
buckle as it nears the area before the zone where the material is liquified.
There also must be enough friction created between the wheel and the
filament to force the filament toward the nozzle. The issues with the
conventional filament based FFF type of process has resulted in the
exploration of several variants of the material extrusion-based tech­
niques. The processing steps involved are usually like the PIM/MIM
process. Thus, the natural evolution that suggested itself was the direct
use of granulated or pelletized feedstock (instead of converting it into
rods or filaments). This process of direct use of feedstock granules has
gained some traction and is expected to be explored further. The slurry-
based extrusion techniques (3DGP or robocasting) also do hold some
promise, though there is the need for further research both in terms of
processing development as well as machine development. It is expected
that the material extrusion-based processes will continue to receive
attention for fabricating smaller hardmetal parts in low volumes or for
rapid prototyping and rapid tooling of mostly cutting tools.
The process of binder jet (BJT) has achieved the highest level of
technology readiness and has already been used to fabricate hardmetal
parts that are both large and small as well as with high degree of shape
complexity. The process has the highest speed (production volume) and
the BJT technology for metal shaping has been embraced by several
large companies and there are several companies that are currently
supplying sophisticated BJT production machines. Almost all the large
and medium sized companies involved in hardmetals, have in some form
worked with or taken BJT inhouse for developmental purposes and some
for R&D and production of actual hardmetal parts. There are several
variants of the BJT technology practiced by different companies. The
differences mainly stem from the way the powder is delivered to the
build bed (bed-to-bed transfer versus powder delivered in front of the
roller, use of ultrasonic vibration to augment the powder delivery for
cohesive powders), the way the powder layer is spread and/or com­
pacted, the manner in which the binder is jetted and its controls, the
binder chemistry, the wetting of the powder by the binder, the manner
A. Bose et al.
in which the individual layers are dried, the way the overall bed is cured
to crosslink the binder, the manner in which the depowdering is carried
out, and how the debinding and the sintering steps are executed. As one
can imagine, there are numerous variables that can influence the BJT
process and the attainment of the final shape and the properties. The
powder and its spreading have a major effect on the BJT process. The
powder flow which is dependent on the powder cohesion influences how
well the powder spreads. The wetting characteristic of the binder is
dependent on the powder-binder interaction and depending on that
interaction, the spread of the binder both in the x-y plane as well as
along the z-direction (which affects the stitching between the layers) is
affected. The binder imbibition rate is also another factor that influences
the BJT process. The BJT process is the fastest process capable of
moderate to high production volumes. Due to the low binder content in
BJT process, large size hardmetal parts can be fabricated by this process.
Some of the truly large parts (high mass) have been fabricated by GTP
showing the ability of the process to fabricate large parts. This tech­
nology platform is expected to grow at a rapid rate. This is a technology
that also has the potential to mass produce moderately high volume of
the same product (cutting tools, drill bits, etc.). Though BJT has pro­
gressed rapidly and can be considered a viable manufacturing process, it
still has some limitations including the high machine and accessory costs
(upfront cost), requires powders that can be spread fairly well in a thin
layer, which involves handling and dispensing of large mass of powders
that would require atmospheric cover during the printing process. A
significant part of the powder needs to be recycled to control the process
cost. The nature of the hardmetal powders (fine, irregular, high surface
area), especially the sub-micron and nano powders, do not lend itself to
easy and uniform spreading. Thus, special powders such as spray dried
powders that are either sintered or plasma sprayed, often need to be
used, limiting the powder availability. However, with substantial R&D
investments, several large companies have been able to use the BJT
platform to fabricate hardmetals with submicron grains (though pro­
cessing as well as powder details have been confidential).
As the developments in sinter-based AM platforms keep expanding, it
will be interesting to see which of the process platforms gain prominence
in the fabrication of hardmetal components. At the current time, two
main platforms, binder jetting and material extrusion, have emerged as
the leading technologies for fabricating hardmetal parts. Development is
continuing on other promising platforms such as material jetting (NPJ
and T3DP) that holds the promise of being able to print with submicron
and nano size particles and low cobalt compositions in extremely com­
plex shapes. Only BJT platform has currently achieved technology
maturity to fabricate hardmetal parts in a mass scale. However, for BJT,
special powder preparation is necessary as the powder available for
press and sinter is typically fine and non-flowable in nature and would
not spread well and will be unsuitable for BJT. Thus, the fine powders
would need to be agglomerated and pre-sintered or sintered to achieve
flowable powder that can easily be spread. This does create an increase
in the powder price as well as limiting the hardmetal compositions to
>10 wt.-% Co and currently only to hardness values well below 1600
HV. The BJT process also has a surface finish that is worse than what can
be achieved by material jetting and vat photo-polymerization platforms
but is better than the material extrusion processes. In contrast, the ma­
terial extrusion platforms can use nearly all kinds of powder while the
material jetting platforms require the use of submicron or nano sized
powders and can have good surface finish.
The cost of producing hardmetal parts in different sinter-based AM
processes is quite complex as it depends not only on the cost of the
printers but also on the subsequent processing equipment that is
necessary to complete the process. The processing of hardmetals to
achieve optimal properties introduces another layer of complexity.
Thus, the cost to fabricate a hardmetal part should really be tailored to
the application itself. As an example, if a truly massive wear part needs
to be fabricated, BJT should become the choice platform. However, if
there is the requirement for only a few small size parts (around 1–5 cm3
25
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
or lower part volume), it will not be ideal to try and push the part to BJT
as it would be a major overkill. Depending on the surface finish
requirement for the small volume and low number of hardmetal parts,
one should consider the material extrusion-based technologies or the
material jetting technologies (if the surface finish requirements are
high). The powder cost is another factor that would need to be consid­
ered. The special powders required for BJT come at a premium and the
choice of the powders are so far also somewhat limited. This, coupled
with the cost of the BJT printer and the auxiliary support equipment
does have a high upfront capital expenditure along with the cost to run
the full process. Of course, one of the most important considerations
would be if the desired properties are achievable in the platform that is
being contemplated. For example, the demand for a part with excellent
surface finish and properties that are only achievable with submicron or
nano carbide grains, is difficult to fabricate by BJT. Thus, the choice of
the 3D printing platform should be dictated by the application and the
desired hardmetal properties. For now, there is no one process that
would fit the requirements for the myriad of hardmetal compositions,
property requirements as well as all kinds of part sizes and kind of ge­
ometries combined with the wish of a cheap powder source and printer
solution.
5. Summary and outlook
Within this review a general introduction to hardmetals, their unique
properties and microstructures as well as to the conventional
manufacturing routes were introduced and additive manufacturing in
general and suitable AM technologies for hardmetals in depth were
discussed. The focus was on the four sinter-based AM technologies
material jetting, material extrusion, binder jetting and stereo­
lithography. Where possible results regarding the achieved final
microstructure and resulting properties were presented and discussed.
Without question, advancements in the development of these and for
sure also other sinter-based AM technologies will in future allow the
production of all kinds of hardmetal compositions, currently produced
by conventional shaping technologies. Next to the complex shape, the
prototyping and the possibility of a comparable cheap decentralized
hardmetal fabrication, some of the AM technologies open the develop­
ment also to novel multi-material parts. Here, material jetting as well as
material extrusion maybe used for application designed multi-material
tools and wear parts consisting either of different hardmetal composi­
tions or qualities (virgin and recycled etc.) or composites of hardmetal
with steel, TiCN based cermets or even ceramics.
Some of the trends that are specific to hardmetals that must be taken
into consideration for 3D printing to succeed in penetrating the hard­
metal market in a major way include the push toward finer and finer WC
grain sizes in the final structure and the partial or complete replacement
of the critical and strategic metal cobalt as the binder phase. Though
WC-Co based hardmetals have withstood the test of time for 100 years,
the need for the replacement and/or reduction of cobalt as binder have
become more and more urgent (toxicity, strategic and critical nature,
and supply chain issues where a large part of the mines are located in
conflict countries). With the global push for Co replacement R&D, it may
be a matter of time that the classic WC-Co hardmetals witness the
gradual replacement of Co as the binder. However, the authors do not
envision that happening in the very near future. The sinter-based AM
processes should be prepared for and embrace the different hardmetal
compositions with partial or complete replacement of cobalt. The other
trend alluded to (moving to sub-micron and nano-sized powders) due to
the benefits in the overall properties of hardmetals, is a natural evolu­
tion and is something that the sinter-based AM community need to be
ready to cater to in terms of processing. The material jetting based
platforms that are suitable for using these ultrafine hardmetal powders
may gain more prominence. The other sinter-based AM platforms would
need to be innovative with the powders to adapt to this demand of using
ultrafine powders.
A. Bose et al.
Authors statement
Animesh Bose: Conceptualization, Writing and original draft (par­
tial preparation), Reviewing and editing, Project administration,
Supervision.
John Reidy: Writing and original draft (partial preparation) Writing
- Review & editing.
Johannes Pötschke: Validation, Writing - review & editing, Writing,
original draft (partial preperation).
Declaration of Competing Interest
None.
Data availability
This is a review paper on sinter-based AM. So we are reviewing data
from papers that are already published with our own comments at the
end. So there is no specific data that was generated and used.
Acknowledgements
The authors would like to thank several individuals for their help in
providing figures and input for the preparation of the manuscript.
Several individuals from Sandvik Additive Manufacturing include
Mikael Schuisky, Anders Ohlsson, and Emma Sjölund who have pro­
vided help with several figures for this manuscript. The authors are also
grateful for the help provided by Jay Verellen, GM, Additive
Manufacturing, at Kennametal, Inc. and Paul Prichard, from Kennametal
Inc. The authors would also like to thank Thomas A. Wolfe, R&D Man­
ager, Engineered Powders at Global Tungsten Powders for his discus­
sions regarding Binder Jet processing of hardmetals. Furthermore,
authors thank Christian Berger from Fraunhofer IKTS for supplying
Figures about Binder Jet printed parts and further details. The authors
would also like to thank Efrain Carreño-Morellia, from University of
Applied Sciences and Arts Western Switzerland, for help with a partic­
ular figure used in the manuscript. Lastly the authors would thank the
help from Heinrich Kestler, Corporate Research and Development, CR-
N, Plansee SA for permission to use several figures from Plansee
Seminar Proceedings.
References
[1] K. Schröter, Gesinterte harte Metallegierung und Verfahren zu ihrer Herstellung;
DE420689(DE420689), 1923.
[2] H. Baumhauer, Procedure for the Fabrication of Pieces and Tools, Especially
Drawing dies(DRP 443.911), 1922.
[3] V.K. Sarin, D. Marie, L. Llanes, Comprehensive Hard Materials, Elsevier, Oxford,
England, Waltham, Massachusetts, 2014.
[4] P. Schwarzkopf, R. Kieffer, Cemented Carbides, The Macmillan Co, New York,
NY, 1960.
[5] R. Kieffer, F. Benesovsky, Hartmetalle, Springer Vienna, Vienna, 1965.
[6] W. Schedler, P.T. GmbH, F.D. Hartmetall, Praktiker, VDI-Verlag, Düsseldorf,
1988.
[7] G.S. Upadhyaya, Cemented Tungsten, WAP, Carbides, 1998.
[8] W.D. Schubert, E. Lassner, W. Böhlke, Cemented carbides – a success story, in:
International Tungsten Industry Association Newsletter, 2010.
[9] K.J.A. Brookes, World Directory and Handbook of Hardmetals, 3rd ed.,
Engineers’ digest Ltd and International carbide data, 1982. London.
[10] H. Kolaska, The dawn of the hardmetal age, Powder Metall. Int. 24 (5) (1992)
311–314.
[11] J. Gurland, J.D. Knox, From sintered tungsten to cemented tungsten carbide: A
historical review of two related technologies, Tungsten Refract. Metals (1995)
219–227.
[12] A. Bose, A perspective on the earliest commercial PM metal-ceramic composite:
cemented tungsten carbide, Int. J. Powder Metall. 47 (2) (2011) 31–50.
[13] I. Konyashin, B. Ries, Cemented Carbides, Elsevier, Amsterdam, 2022.
[14] J. García, V.C. Ciprés, A. Blomqvist, B. Kaplan, Cemented carbide
microstructures: a review, Int. J. Refract. Met. Hard Mater. 80 (2019) 40–68.
[15] R. Porat, S. Burger, A. Rosen, New cemented carbide compositions based on
ultrafine and Nanocrystalline WC-co powders, Tungsten Refract. Metals 5 (2000)
131–139.
26
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
[16] R. Porat, S. Burger, A. Rosen, Cemented carbide from micron grain size to nano
size, Plansee Proceed. 2 (1997) 183–196.
[17] W.D. Schubert, H. Neumeister, G. Kinger, B. Lux, Hardness to toughness
relationship of fine-grained WC-Co hardmetals, Int. J. Refract. Met. Hard Mater.
16 (2) (1998) 133–142.
[18] Z. Fang, J.W. Eason, Study of nanostructured WC-Co composites, in: Proceedings
of the 13th International Plansee Seminar 3, 1993, pp. 625–638.
[19] E.A. Almond, B. Roebuck, Some characteristics of very fine grained hard metals,
Metal Powder Report 42 (7–8) (1987) 512–515.
[20] R.K. Sadangi, L.E. Mccandlish, B.H. Kear, P. Seegopaul, Grain growth inhibition
in sintered nanophase WC/Co alloys, Int. J. Powder Metall. 35 (1999) 27–33.
[21] P. Seegopaul, Multistep Process to Incorporate grain GROWTH Inhibitors into
WC-Co(US patent No. 5,885,372), 1999.
[22] Z. Huchun, F. Jinglian, Y. Wenhua, Z. Zhongjian, L. Tao, Influence of VC/Cr3C2
and mixed carbon content on microstructure and properties of ultrafine WC-
0.5Co cemented carbide, Health Environ. Res. Online 44 (4) (2015) 912–917.
[23] Q. Yang, J. Yang, Y. Wen, Q. Zhang, L. Chen, H. Chen, A novel route for the
synthesis of ultrafine WC-15 wt %Co cemented carbides, J. Alloys Compd. 748
(2018) 577–582.
[24] Z.Z. Fang, H. Wang, V. Kumar, Coarsening, densification, and grain growth
during sintering of nano-sized powders—a perspective, Int. J. Refract. Met. Hard
Mater. 62 (2017) 110–117.
[25] D. Xiao, Y. He, W. Luo, M. Song, Effect of VC and NbC additions on microstructure
and properties of ultrafine WC-10Co cemented carbides, Trans. Nonferrous
Metals Soc. China 19 (6) (2009) 1520–1525.
[26] S. Farag, I. Konyashin, B. Ries, The influence of grain growth inhibitors on the
microstructure and properties of submicron, ultrafine and nano-structured
hardmetals – a review, Int. J. Refract. Met. Hard Mater. 77 (2018) 12–30.
[27] K.-F. Wang, X.-H. Yang, X.-C. Deng, K.-C. Chou, G.-H. Zhang, Enhancement of the
mechanical properties of ultrafine-grained WC-Co cemented carbides via the in-
situ generation of VC, J. Alloys Compd. 903 (2022), 163961.
[28] E.A. Almond, B. Roebuck, Very fine-grained hard metals, Int. J. Refract. Met.
Hard Mater. 6 (3) (1987) 137–144.
[29] Z. Xue, S. Ma, Y. Liu, J. Ma, T. Wang, B. Li, et al., Study on the preparation
mechanism of novel WC-Cr2(C, N)-Co nanocomposites, J. Alloys Compd. 943
(2023), 169036.
[30] Z.Z. Fang, X. Wang, T. Ryu, K.S. Hwang, H.Y. Sohn, Synthesis, sintering, and
mechanical properties of nanocrystalline cemented tungsten carbide – a review,
Int. J. Refract. Met. Hard Mater. 27 (2) (2009) 288–299.
[31] J.J. Stiglich, C.C. Yu, T.S. Sudarshan, Synthesis of Nano WC/Co for tools and dies,
in: Tungsten, Refractory Metals and Alloys 3, 1995, pp. 229–236.
[32] D. Sivaprahasam, S.B. Chandrasekar, R. Sundaresan, Microstructure and
mechanical properties of nanocrystalline WC–12Co consolidated by spark plasma
sintering, Int. J. Refract. Met. Hard Mater. 25 (2) (2007) 144–152.
[33] V. Richter, M. Ruthendorf, H. Kubsch, On hardness and toughness of ultrafine and
nanocrystalline hard materials, in: Sixth International Conference on the Science
of Hard Material, 1998, pp. 73–74.
[34] V. Richter, M. Ruthendorf, On hardness and toughness of ultrafine and
nanocrystalline hard materials, Int. J. Refract. Met. Hard Mater. 17 (1–3) (1999)
141–152.
[35] V. Richter, J. Pötschke, R. Holke, Development of the Microstructure of
Nanostructured Materials during Sintering: Metallurgy, in: Proceedings of the
2012 Powder Metallurgy World Congress: PM, 2012.
[36] V. Richter, J. Pötschke, R. Holke, A. Michaelis, Nanoscaled hardmetals - Fiction or
reality?, in: Proceedings of the 18th International Plansee Seminar, 2013,
pp. 1257–1273.
[37] J. Pötschke, V. Richter, T. Gestrich, T. Säuberlich, J.A. Meese-Marktscheffel,
Grain growth inhibition in ultrafine hardmetals, Int. J. Refract. Met. Hard Mater.
66 (2017) 95–104.
[38] T.A. Fabijanić, J. Pötschke, V. Alar, Ž. Alar, Influence of C Content on
electrochemical corrosion resistance of nanostructured Hardmetals, in: EPMA -
European Powder Metallurgy Association, 2017.
[39] J. Pötschke, T. Gestrich, V. Richter, Grain growth inhibition of hardmetals during
initial heat-up, Int. J. Refract. Met. Hard Mater. 72 (2018) 117–125.
[40] J. Pötschke, T. Säuberlich, A. Vornberger, J.A. Meese-Marktscheffel, Solid state
sintered nanoscaled hardmetals and their properties, Int. J. Refract. Met. Hard
Mater. 72 (2018) 45–50.
[41] R.M. German, A. Bose, Injection Molding of Metals and Ceramics, Metal Powder
Industries Federation, Princeton, N.J, 1997.
[42] L. Nyborg, E. Carlström, A. Warren, H. Bertilsson, Guide to injection Moulding of
ceramics and Hardmetals: special consideration of fine powder, Powder Metall.
41 (1) (1998) 41–45.
[43] X. Yang, R.J. Petcavich, A. Bose, Powder Injection Molding of WC-co, Hard Metals
and Refractory Alloys V, Tungsten, 2000, pp. 89–95.
[44] A. Fayyaz, N. Muhamad, A.B. Sulong, J. Rajabi, Y.N. Wong, Fabrication of
cemented tungsten carbide components by micro-powder injection moulding,
J. Mater. Process. Technol. 214 (7) (2014) 1436–1444.
[45] S. Shahbudin, M.H. Othman, S.Y.M. Amin, M. Ibrahim, A review of Metal
injection molding- process, optimization, defects and microwave sintering on WC-
Co cemented carbide, IOP Conf. Ser.: Mater. Sci. Eng. 226 (2017) 12162.
[46] J.L. Johnson, D.F. Heaney, N.S. Myers, Metal injection molding (MIM) of heavy
alloys, refractory metals, and hardmetals, in: Handbook of Metal Injection
Molding, Elsevier, 2012, pp. 526–567.
[47] X.C. Xie, C.G. Lin, C.C. Jia, R.J. Cao, Effects of process parameters on quality of
ultrafine WC/12Co injection molded compacts, Int. J. Refract. Met. Hard Mater.
48 (2015) 305–311.
A. Bose et al.
[48] M.T. Martyn, P.J. James, The processing of hardmetal components by powder
injection moulding, Int. J. Refract. Met. Hard Mater. 12 (2) (1993) 61–69.
[49] S.N.F. Khairudin, H.F. Pahroraji, S.K. Alias, M.H.I. Ibrahim, A review of Metal
injection Moulding on WC-Co cemented carbide comprised of grain growth
inhibitors (GGI), Int. J. Integrat. Eng. 14 (1) (2022) 84–101.
[50] H.F. Pahroraji, M.H. Irwan Ibrahim, P. Muniandy, S.Y.M. Amin, S.K. Alias,
Parameter optimization of WC-TaC-6Co green part in injection Moulding using
Taguchi method, IOP Conf. Ser.: Mater. Sci. Eng. 834 (1) (2020) 12077.
[51] R.M. German, A. Bose, Binder and Polymer Assisted Powder Processing, ASM
International, Materials Park, Ohio, 2020.
[52] A. Kover, Transformation In 3D: How A Walnut-Sized Part Changed The Way GE
Aviation Builds Jet Engines. https://www.ge.com/news/reports/transformation
-3d-walnut-sized-part-changed-way-ge-aviation-builds-jet-engines, 2018.
[53] F42 Committee, Terminology for Additive Manufacturing Technologies, ASTM
International, West Conshohocken, PA, 2012, https://doi.org/10.1520/F2792-
12.
[54] ISO/ASTM, Additive Manufacturing – General Principles, ISO/ASTM
International, Terminology(ISO/ ASTM 52900:2021), 2021.
[55] N. Tuncer, A. Bose, Solid-state Metal Additive manufacturing: a review, JOM 72
(9) (2020) 3090–3111.
[56] A. Vafadar, F. Guzzomi, A. Rassau, K. Hayward, Advances in Metal Additive
manufacturing: a review of common processes, industrial applications, and
current challenges, Appl. Sci. 11 (3) (2021) 1213.
[57] K.V. Wong, A. Hernandez, A review of Additive manufacturing, ISRN Mechan.
Eng. 2012 (2012) 1–10.
[58] C. Buchanan, L. Gardner, Metal 3D printing in construction: a review of methods,
research, applications, opportunities and challenges, Eng. Struct. 180 (2019)
332–348.
[59] J.C. Najmon, S. Raeisi, A. Tovar, Review of additive manufacturing technologies
and applications in the aerospace industry, in: Additive Manufacturing for the
Aerospace Industry, Elsevier, 2019, pp. 7–31.
[60] M. Yakout, M.A. Elbestawi, S.C. Veldhuis, A review of Metal Additive
manufacturing technologies, SSP 278 (2018) 1–14.
[61] D.-G. Ahn, Direct metal additive manufacturing processes and their sustainable
applications for green technology: a review, Int. J. Precis. Eng. and Manuf.-Green
Tech. 3 (4) (2016) 381–395.
[62] B. Wu, Z. Pan, D. Ding, D. Cuiuri, H. Li, J. Xu, et al., A review of the wire arc
additive manufacturing of metals: properties, defects and quality improvement,
J. Manuf. Process. 35 (2018) 127–139.
[63] F. Calignano, D. Manfredi, E.P. Ambrosio, S. Biamino, M. Lombardi, E. Atzeni, et
al., Overview on Additive manufacturing technologies, Proc. IEEE 105 (4) (2017)
593–612.
[64] M. Burns, C. Wangenheim, Metal 3D Printing Applications in the Oil & Gas
Industry, in: Day 3 Wed, March 20, SPE, 2019, p. 2019.
[65] M.K. Thompson, G. Moroni, T. Vaneker, G. Fadel, R.I. Campbell, I. Gibson, et al.,
Design for Additive Manufacturing: trends, opportunities, considerations, and
constraints, CIRP Ann. 65 (2) (2016) 737–760.
[66] J.J. Lewandowski, M. Seifi, Metal Additive manufacturing: a review of
mechanical properties, Annu. Rev. Mater. Res. 46 (1) (2016) 151–186.
[67] W.E. Frazier, Metal Additive manufacturing: a review, J. Mater. Eng. Perform. 23
(6) (2014) 1917–1928.
[68] J. Johns, Current perspectives on metal AM: hype, volume manufacturing and the
geographies of production, Metal AM 6 (1) (2020) 123–133.
[69] M. Ziaee, N.B. Crane, Binder jetting: a review of process, materials, and methods,
Addit. Manuf. 28 (2019) 781–801.
[70] N.P.V. Sebbe, F. Fernandes, V.F.C. Sousa, F.J.G. Silva, Hybrid manufacturing
processes used in the production of complex parts: a comprehensive review,
Metals 12 (11) (2022) 1874.
[71] A. Bose, A perspective on Metal Additive manufacturing and emergence of
powder-binder based processes, Int. J. Powder Metall. 55 (2) (2019) 29–42.
[72] E.M. Sefene, Y.M. Hailu, A.A. Tsegaw, Metal hybrid additive manufacturing:
state-of-the-art, Prog. Addit. Manuf. 7 (4) (2022) 737–749.
[73] A.S. Kurlov, A.I. Gusev, Tungsten carbides and W-C phase diagram, Inorg. Mater.
42 (2) (2006) 121–127.
[74] G. Zong, Y. Wu, N.T. Tran, I. Lee, D.L. Bourell, J.J. Beaman, et al., Direct selective
laser sintering of high temperature materials, Cent. Mater. Sci. & Eng. (1992)
72–85.
[75] T. Laoui, J. Bonse, J.P. Kruth, L. Froyen, Influence of Powder Parameters on
Selective Laser Sintering of Tungsten-Carbide Cobalt, in: Proceedings of the 8th
European, 1998, pp. 271–280.
[76] X.C. Wang, T. Laoui, J. Bonse, J.P. Kruth, B. Lauwers, L. Froyen, Direct selective
laser sintering of hard Metal powders: experimental study and simulation, Int. J.
Adv. Manuf. Technol. 19 (5) (2002) 351–357.
[77] K. Maeda, T. Childs, Laser sintering (SLS) of hard metal powders for abrasion
resistant coatings, J. Mater. Process. Technol. 149 (1–3) (2004) 609–615.
[78] T. Gläser, T. Bergs, F. Klocke, Liquid phase sintering of tungsten carbide with both
cobalt and nickel binder phases by laser radiation, in: Proceedings of the 2006
International Conference of Tungsten, Refractory, and Hardmetals VI, 2006,
pp. 132–140.
[79] Y. Xiong, J.E. Smugeresky, L. Ajdelsztajn, J.M. Schoenung, Fabrication of WC–Co
cermets by laser engineered net shaping, Mater. Sci. Eng. A 493 (1–2) (2008)
261–266.
[80] J.A. Picas, Y. Xiong, M. Punset, L. Ajdelsztajn, A. Forn, J.M. Schoenung,
Microstructure and wear resistance of WC–Co by three consolidation processing
techniques, Int. J. Refract. Met. Hard Mater. 27 (2) (2009) 344–349.
27
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
[81] S. Kumar, Manufacturing of WC–Co moulds using SLS machine, J. Mater. Process.
Technol. 209 (8) (2009) 3840–3848.
[82] E. Uhlmann, A. Bergmann, W. Gridin, Investigation on Additive manufacturing of
tungsten carbide-cobalt by selective laser melting, Procedia CIRP 35 (2015) 8–15.
[83] S.K. Ghosh, A.K. Das, P. Saha, Selective laser sintering: A case study of tungsten
carbide and cobalt powder sintering by pulsed Nd:YAG laser, in: S.N. Joshi, U.
S. Dixit (Eds.), Lasers Based Manufacturing, Springer India, New Delhi, 2015,
pp. 441–459.
[84] T. Schwanekamp, M. Reuber, Additive Manufacturing of application optimized
tungsten carbide precision tools, in: iCAT: Proceedings of 6th International
Conference on Additive Technologies, 2016, pp. 100–114.
[85] T. Schubert, W. Baumann, D. Sellmer, M. Schneider, J. Kress, T. Bernthaler,
Einsatz von pulvermetallurgischen Werkstoffen bei einem Werk-zeughersteller –
Additive Fertigung von Wolframcarbid-Cobalt-Hartmetallen, in: Hagener
Symposium Pulvermetallurgie: Zerspanung von und mit pulvermetallurgischen
Werkstoffenorträge und Ausstellerbeiträge des Hagener Symposiums, 2016,
pp. 163–176.
[86] R.S. Khmyrov, V.A. Safronov, A.V. Gusarov, Obtaining crack-free WC-Co alloys by
selective laser melting, Phys. Procedia 83 (2016) 874–881.
[87] S. Kumar, A. Czekanski, Optimization of parameters for SLS of WC-co, RPJ 23 (6)
(2017) 1202–1211.
[88] A. Domashenkov, A. Borbély, I. Smurov, Structural modifications of WC/Co
nanophased and conventional powders processed by selective laser melting,
Mater. Manuf. Process. 32 (1) (2017) 93–100.
[89] E. Uhlmann, A. Bergmann, R. Bolz, Manufacturing of carbide tools by selective
laser melting, Procedia Manufact. 21 (2018) 765–773.
[90] T. Schwanekamp, M. Reuber, Parameter study on laser beam melting of WC-Co at
800◦ C pre-heating temperature, in: Proceedings of 7th International Conference
on Additive Technologies, 2018, pp. 78–84.
[91] I. Konyashin, H. Hinners, B. Ries, A. Kirchner, B. Klöden, B. Kieback, et al.,
Additive manufacturing of WC-13%Co by selective electron beam melting:
achievements and challenges, Int. J. Refract. Met. Hard Mater. 84 (2019),
105028.
[92] A. Fortunato, G. Valli, E. Liverani, A. Ascari, Additive manufacturing of WC-Co
cutting tools for gear production, Lasers Manuf. Mater. Process. 6 (3) (2019)
247–262.
[93] D. Bricin, A. Kriz, Processability of WC-Co powder mixtures using SLM additive
technology, MM SJ 2019 (2) (2019) 2939–2945.
[94] M. Padmakumar, Additive manufacturing of tungsten carbide Hardmetal parts by
selective laser melting (SLM), selective laser sintering (SLS) and binder jet 3D
printing (BJ3DP) techniques, Lasers Manuf. Mater. Process. 7 (3) (2020)
338–371.
[95] S. Fries, S. Genilke, M.B. Wilms, M. Seimann, A. Weisheit, A. Kaletsch, et al.,
Laser-based Additive manufacturing of WC–Co with high-temperature powder
bed preheating †, Steel Research Int. 91 (3) (2020) 1900511.
[96] S. Son, J.M. Park, S.H. Park, J.-H. Yu, H. Kwon, H.S. Kim, Correlation between
microstructural heterogeneity and mechanical properties of WC-Co composite
additively manufactured by selective laser melting, Mater. Lett. 293 (2021),
129683.
[97] H. Ibe, Y. Kato, J. Yamada, M. Kato, A. Suzuki, N. Takata, et al., Controlling WC/
Co two-phase microstructure of cemented carbides additive-manufactured by
laser powder bed fusion: effect of powder composition and post heat-treatment,
Mater. Des. 210 (2021), 110034.
[98] L. Zhang, C. Hu, Y. Yang, R. Misra, K. Kondoh, Y. Lu, Laser powder bed fusion of
cemented carbides by developing a new type of Co coated WC composite powder,
Addit. Manuf. 55 (2022), 102820.
[99] T. Schwanekamp, G. Marginean, M. Reuber, A. Ostendorf, Impact of cobalt
content and grain growth inhibitors in laser-based powder bed fusion of WC-Co,
Int. J. Refract. Met. Hard Mater. 105 (2022), 105814.
[100] Z. Zhao, R. Liu, J. Chen, X. Xiong, Additive manufacturing of cemented carbide
using analogous powder injection molding feedstock, Int. J. Refract. Met. Hard
Mater. 111 (2023), 106095.
[101] Y. Yang, C. Zhang, D. Wang, L. Nie, D. Wellmann, Y. Tian, Additive
manufacturing of WC-Co hardmetals: a review, Int. J. Adv. Manuf. Technol. 108
(5–6) (2020) 1653–1673.
[102] J. Pötschke, Additive manufacturing of hardmetals: an evaluation of potential
processes for tool production, Metal AM 6 (3) (2020).
[103] C.L. Cramer, T.G. Aguirre, N.R. Wieber, R.A. Lowden, A.A. Trofimov, H. Wang, et
al., Binder jet printed WC infiltrated with pre-made melt of WC and Co, Int. J.
Refract. Met. Hard Mater. 87 (2020), 105137.
[104] S. Ritter, S.F. Wenzler, Formnext AM FIELD GUIDE: Entdecke die Welt der
additiven Fertigung eine praktische Orientierungshilfe für die spannende Welt der
generativen Fertigung, 2019th ed., Mesago Messe Frankfurt GmbH, Stuttgart,
2019.
[105] Material, Homepage XJet. https://xjet3d.com/additive-manufacturing-solutuins
/materials/, 2023.
[106] A. Benichou, L. Laufer, Tungsten-Carbide/Cobalt Ink Composition for 3d Inkjet
Printing(EP3058037B1), 2020.
[107] Pötschke J. Additive, Fertigung von Hartmetallen, Vergleich einstufiger und
zweistufiger 3D-Druckverfahren, in: C. Broeckmann (Ed.), Pulvermetallurgie -
nachhaltige Lösungen und neue Märkte: Vorträge und Ausstellerbeiträge des
Hagener Symposiums am 25. November und 26. November 2021 in Hagen,
Heimdall Verlag, Dortmund, 2021, pp. 263–291.
[108] U. Scheithauer, A. Bergner, E. Schwarzer, Studies on thermoplastic 3D printing of
steel–zirconia composites, J. Mater. Res. 29 (2014) 1931–1940.
A. Bose et al.
[109] U. Scheithauer, T. Slawik, E. Schwarzer, Additive manufacturing of Metal-
ceramic-composites by thermoplastic 3D-printing (3DTP), J. Ceram. Sci. Technol.
6 (2) (2014) 125–132.
[110] U. Scheithauer, J. Pötschke, S. Weingarten, Droplet-based Additive
manufacturing of hard Metal components by thermoplastic 3D printing (T3DP),
J. Ceram. Sci. Technol. 8 (2017) 155–160.
[111] J. Pötschke, S. Weingarten, U. Scheithauer, Thermoplastic 3D Printing of
Hardmetals, in: Euro PM2019 Congress & Exhibition, 2019, pp. 1–6.
[112] S. Crump, Apparatus and Method for Creating Three-Dimensional Objects(US
Patent No. 5,121,329), 1992.
[113] PIM International, Fraunhofer IKTS introduces Fused Filament Fabrication for
hardmetals. https://www.pim-international.com/fraunhofer-ikts-introduces-fus
ed-filament-fabrication-for-hardmetals/, 2018.
[114] W. Lengauer, I. Duretek, M. Fürst, V. Schwarz, J. Gonzalez-Gutierrez,
S. Schuschnigg, et al., Fabrication and properties of extrusion-based 3D-printed
hardmetal and cermet components, Int. J. Refract. Met. Hard Mater. 82 (2019)
141–149.
[115] J. Pötschke, C. Berger, J. Abel, T. Moritz, Properties of Additive Manufactured
Hardmetal Components produced by Fused Filament Fabrication (FFF), in: Euro
PM 2018 Congress and Exhibition, 2018.
[116] J. Gonzalez-Gutierrez, S. Cano, S. Schuschnigg, C. Kukla, J. Sapkota, C. Holzer,
Additive manufacturing of metallic and ceramic components by the material
extrusion of highly-filled polymers: a review and future perspectives, Materials
(Basel, Switzerland) vol. 11 (5) (2018).
[117] A. Aramian, N. Razavi, Z. Sadeghian, F. Berto, A review of additive manufacturing
of cermets, Addit. Manuf. 33 (2020), 101130.
[118] F. Cerejo, A. Silva, M.-T. Vieira, F.M. Barreiros, Fused Deposition of WC+Co
powder, in: Euro PM2019 Congress & Exhibition, 2019.
[119] B. Denkena, B. Bergmann, A. Relard, M. Hein, J. Abel, J. Pötschke, Energie
einsparen mit additiv gefertigten Zerspanwerkzeugen, VDI-Z 164 (09) (2022)
48–50.
[120] W. Lengauer, I. Duretek, M. Fürst, J.G. Gutierrez, S. Schuschnigg, C. Kukla, Fused-
Filament Printing of Hardmetals and Cermets with Feedstock from RTP Powders,
in: Euro PM2019 Congress & Exhibition, 2019.
[121] A. Bose, C.A. Schuh, J.C. Tobia, N. Tuncer, N.M. Mykulowycz, A. Preston, et al.,
Traditional and additive manufacturing of a new tungsten heavy alloy alternative,
Int. J. Refract. Met. Hard Mater. 73 (2018) 22–28.
[122] A. Bose, J.P. Reidy, N. Tuncer, L. Jorgensen, Processing of tungsten heavy alloy by
extrusion-based additive manufacturing, Int. J. Refract. Met. Hard Mater. 110
(2023), 106021.
[123] A. Bose, J.P. Reidy, L. Jorgensen, N. Tuncer, Processing of copper by extrusion-
based Additive manufacturing, in: Advances in Additive Manufacturing with
Powder Metallurgy 2022, 2022, pp. 169–188.
[124] A. Bose, J.P. Reidy, L. Jorgensen, N. Tuncer, R. Enneti, T. Jewett, et al., Bound
Metal Deposition of Tungsten Carbide, in: 20th Plasnee Seminar Proceeding, 2022.
[125] A. Siddiqui, Metal and Ceramic 3D Printing Made Cheap and Fast with AIM3D’s
Pellet Extruder. https://3dprint.com/284328/metal-and-ceramic-3d-printing-
made-cheap-and-fast-with-aim3ds-pellet-extruder/, 2021.
[126] BASF, Metal Filaments. https://forward-am.com/material-portfolio/ultrafuse-fila
ments-for-fused-filaments-fabrication-fff/metal-filaments/, 2023.
[127] X. Zhang, Z. Guo, C. Chen, W. Yang, Additive manufacturing of WC-20Co
components by 3D gel-printing, Int. J. Refract. Met. Hard Mater. 70 (2018)
215–223.
[128] X. Ren, H. Shao, T. Lin, H. Zheng, 3D gel-printing—an additive manufacturing
method for producing complex shape parts, Mater. Des. 101 (2016) 80–87.
[129] M. Medeiros, M. Faria, S. Olhero, F. Rodrigues, J. Sacramento, F.S. Rui, et al., 3D
carbide - Additive manufacturing of hard Metal components, in: yCAM, 2020.
[130] S.G. Huang, E. Wong, B. Göksel, J. Qian, J. Vleugels, Direct Ink Writing Of Open
And Dense NbC-Ni Matrix Cermet Structures, in: World PM2022 Published by
European Powder Metallurgy Association (EPMA), 2022.
[131] E. Sachs, M. Cima, J. Cornie, Three-dimensional printing: rapid tooling and
prototypes directly from a CAD model, CIRP Ann. 39 (1) (1990) 201–204.
[132] J. Yoo, M. Cima, S. Khanuja, E. Sachs, Structural ceramic components by 3D
printing, Department. Mater. Sci. Eng. Mechan. Engineering (1993) 40–50.
[133] B. Berman, 3-D printing: the new industrial revolution, Bus. Horiz. 55 (2) (2012)
155–162.
[134] J. Bai, K.D. Creehan, H.A. Kuhn, Inkjet printable nanosilver suspensions for
enhanced sintering quality in rapid manufacturing, Nanotechnology 18 (18)
(2007), 185701.
[135] A. Bailey, A. Merriman, A. Elliott, M. Basti, Preliminary Testing of Nanoparticle
Effectiveness in Binder Jetting Applications, 2023, pp. 1069–1077.
[136] J.A. Bai, K. Creehan, H.A. Kuhn, Powder Particle Layerwise Three-Dimensional
Printing Process(US Patent Application 2015/0069649 A1), 2015.
[137] Y. Bai, C.B. Williams, The effect of inkjetted nanoparticles on metal part
properties in binder jetting additive manufacturing, Nanotechnology 29 (39)
(2018), 395706.
[138] P. Kunchala, K. Kappagantula, 3D printing high density ceramics using binder
jetting with nanoparticle densifiers, Mater. Des. 155 (2018) 443–450.
[139] J. Liu, In Situ Created Metal Nanoparticle Strengthening of Metal Powder Articles
(WO2006049619A1), 2006.
[140] H.J. Yoo, Reactive Binders for Metal Parts Produced by Three Dimensional
Printing, MIT Department of Mechanical Engineering, 1995.
[141] C. Hadjiloucas, Low Shrinkage Metal Skeletons by Three Dimensional Printing,
MIT Department of Mechanical Engineering, 1997.
[142] Y. Bai, C.B. Williams, Binder jetting additive manufacturing with a particle-free
metal ink as a binder precursor, Mater. Des. 147 (2018) 146–156.
28
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
[143] S. Huang, C. Ye, H. Zhao, Z. Fan, Q. Wei, Binder jetting yttria stabilised zirconia
ceramic with inorganic colloid as a binder, Adv. Appl. Ceram. 118 (8) (2019)
458–465.
[144] M.A. Caradonna, The Fabrication of High Packing Density Ceramic Powder Beds
for the Three Dimensional Printing Process, MIT Department of Mechanical
Engineering, 1997.
[145] A. Kelley, E. Sachs, Tungsten Carbide-Cobalt by Three- Dimensional Printing, MIT
Department of Mechanical Engineering, 1998.
[146] B.D. Kernan, E.M. Sachs, M.A. Oliveira, M.J. Cima, Three-dimensional printing of
tungsten carbide–10wt% cobalt using a cobalt oxide precursor, Int. J. Refract.
Met. Hard Mater. 25 (1) (2007) 82–94.
[147] T. Gläser, K. Arntz, M. Schlüter, T. John, F. Bechmann, R. Döhler, et al., GENIAL-
Generative Fertigung von Extrusionswerkzeugen aus HartmetallBericht
Lasersintern HM, 2009, pp. 41–45.
[148] R.K. Enneti, K.C. Prough, Effect of binder saturation and powder layer thickness
on the green strength of the binder jet 3D printing (BJ3DP) WC-12%Co powders,
Int. J. Refract. Met. Hard Mater. 84 (2019), 104991.
[149] Fraunhofer 3D prints hardmetal tools, Metal Powder Report 72 (1) (2017) 69.
[150] J. Pötschke, Additive Fertigung von Hartmetallen: Druck von komplexen
Hartmetallwerkzeugen, 2017. IW14-IW16.
[151] J. Pötschke, C. Berger, H.-J. Richter, U. Scheithauer, S. Weingarten, Additive
manufacturing of hardmetals, in: Euro PM 2017 Congress and Exhibition, 2023.
[152] A.M. Metal, Fraunhofer IKTS Develops Complex Additively Manufactured
Hardmetal Tools, 2016.
[153] R.K. Enneti, K.C. Prough, T.A. Wolfe, A. Klein, N. Studley, J.L. Trasorras, Sintering
of WC-12%Co processed by binder jet 3D printing (BJ3DP) technology, Int. J.
Refract. Met. Hard Mater. 71 (2018) 28–35.
[154] R.K. Enneti, K.C. Prough, Wear properties of sintered WC-12%Co processed via
binder jet 3D printing (BJ3DP), Int. J. Refract. Met. Hard Mater. 78 (2019)
228–232.
[155] M. Mariani, I. Goncharov, D. Mariani, Gpd Gaudenzi, A. Popovich, N. Lecis, et al.,
Mechanical and microstructural characterization of WC-Co consolidated by
binder jetting additive manufacturing, Int. J. Refract. Met. Hard Mater. 100
(2021), 105639.
[156] L. Cabezas, C. Berger, E. Jiménez-Piqué, J. Pötschke, L. Llanes, Testing length-
scale considerations in mechanical characterization of WC-Co hardmetal
produced via binder jetting 3D printing, Int. J. Refract. Met. Hard Mater. 111
(2023), 106099.
[157] T. Wolfe, R. Shah, K. Prough, J.L. Trasorras, Coarse cemented carbide produced
via binder jetting 3D printing, Int. J. Refract. Met. Hard Mater. 110 (2023),
106016.
[158] P.D. Prichard, Z. Wang, H. Miyanaji, Microstructural Development in Binder Jet
Additive Manufacturing of WC-Co, in: Proceedings of the 20th Plansee Seminar,
2022.
[159] Z. Wang, P.D. Prichard, M. Perez, H. Miyanaji, Q. Wu, Tungsten Carbide with Low
Metallic Binder Contents Via Binder Jetting, in: Proceedings of Additive
Manufacturing with Powder Metallurgy, 2022.
[160] J.P. Reidy, Cobalt Pools in WC-12Co Components Produced by BJT, E-mail
message, 2023.
[161] B. North, Kennametal: the story of the successful commercialization of AM
hardmetal and steel solutions, Metal AM Magaz. 9 (2) (2023) 111–121.
[162] Sandvik, Sandvik Introduces 3D-Printed Cemented Carbide. https://www.home.
sandvik/en/news-and-media/news/2022/04/sandvik-introduces-3d-printed-ce
mented-carbide/, 2022.
[163] A.M. Metal, Sandvik Now Offers Additively Manufactured Cemented Carbide
Components. https://www.metal-am.com/sandvik-now-offers-additively-manufa
ctured-cemented-carbide-components/, 2023.
[164] Fleo, How Will 3D Printed Carbide Be in the Future?. https://www.ukocarbide.
com/blog/how-will-3d-printed-carbide-be-in-the-future/, 2020.
[165] J.D. Flon, Cermet or Cemented Carbide Powder and Three Dimensional Printing
Thereof(EP3442728B1), 2021.
[166] C.L. Cramer, R.A. Lowden, A.M. Elliott, Infiltration studies of additive
manufacture of WC with Co using binder jetting and pressureless melt method,
Addit. Manuf. 28 (2019) 333–343.
[167] C.L. Cramer, N.R. Wieber, T.G. Aguirre, R.A. Lowden, A.M. Elliott, Shape
retention and infiltration height in complex WC-Co parts made via binder jet of
WC with subsequent Co melt infiltration, Addit. Manuf. 29 (2019), 100828.
[168] E. Carreño-Morelli, P. Alveen, S. Moseley, M. Rodriguez-Arbaizar, K. Cardoso,
Three-dimensional printing of hard materials, Int. J. Refract. Met. Hard Mater. 87
(2020), 105110.
[169] E. Carreño-Morelli, P. Alveen, S. Moseley, M. Rodriguez-Arbaizar, K. Cardoso,
A comparative study of cemented carbide parts produced by solvent on granules
3D-printing (SG-3DP) versus press and sinter, Int. J. Refract. Met. Hard Mater. 97
(2021), 105515.
[170] E. Carreño-Morelli, Images for SG-3DP Method, E-mail message, 2023.
[171] J. Pötschke, BJT of WC-Ni, E-mail message, 2023.
[172] 3D Print Magazine, Desktop Metal Develops High-Volume Manufacturing Process
for Cobalt-Free Hardmetal Parts, 2020.
[173] C. Berger, J. Pötschke, M. Fries, T. Moritz, A. Michaelis, Binder-Jetting of TiCN-
Based Cermets, in: Proceedings of Euro PM, 2021.
[174] C. Berger, J. Pötschke, M. Fries, T. Moritz, A. Michaelis, Binder-jetting of TiCN-
based cermets, Powder Metall. 65 (5) (2022) 382–389.
[175] T. Gestrich, J. Pötschke, M. Mayer, C. Berger, J. Abel, D. Gruner, et al., Analysis of
debinding and sintering of additive manufactured green bodies of cemented
carbides, in: Proceedings of the 20th Plansee Seminar, 2022.
A. Bose et al.
[176] E. Schwarzer, M. Götz, D. Markova, D. Stafford, U. Scheithauer, T. Moritz,
Lithography-based ceramic manufacturing (LCM) – viscosity and cleaning as two
quality influencing steps in the process chain of printing green parts, J. Eur.
Ceram. Soc. 37 (16) (2017) 5329–5338.
[177] M. Schwentenwein, J. Homa, Additive manufacturing of dense alumina ceramics,
Int. J. Appl. Ceram. Technol. 12 (1) (2015) 1–7.
[178] A.A. Altun, T. Prochaska, T. Konegger, M. Schwentenwein, Dense, strong, and
precise silicon nitride-based ceramic parts by lithography-based ceramic
manufacturing, Appl. Sci. 10 (3) (2020) 996.
[179] G. Ding, R. He, K. Zhang, C. Xie, M. Wang, Y. Yang, et al., Stereolithography-
based additive manufacturing of gray-colored SiC ceramic green body, J. Am.
Ceram. Soc. 102 (12) (2019) 7198–7209.
[180] E. Schwarzer-Fischer, U. Scheithauer, A. Michaelis, CerAMfacturing of aluminum
nitride with high thermal conductivity via lithography-based ceramic vat
Photopolymerization (CerAM VPP), Ceramics 6 (1) (2023) 416–431.
29
International Journal of Refractory Metals and Hard Materials 119 (2024) 106493
[181] T. Rieger, T. Schubert, J. Schurr, M. Butschle, M. Schwenkel, T. Bernthaler, et al.,
Slurry development for lithography-based additive manufacturing of cemented
carbide components, Powder Technol. 383 (2021) 498–508.
[182] T. Rieger, T. Schubert, J. Schurr, D. Kolb, H. Riegel, T. Bernthaler, et al.,
Cemented Carbide Development for Additive Manufacturing (AM), in: Euro
PM2019 Congress & Exhibition, 2019, pp. 1–6.
[183] T. Rieger, T. Schubert, J. Schurr, A. Kopp, M. Schwenkel, D. Sellmer, et al., Vat
Photopolymerization of Cemented Carbide Specimen, Materials (Basel,
Switzerland) vol. 14 (24) (2021).
[184] X. Zan, X. Wang, K. Shi, Y. Feng, J. Shu, J. Liao, et al., Three-dimensional porous
tungsten via DLP 3D printing from transparent ink, J. Phys. D. Appl. Phys. 55 (44)
(2022), 444004.
[185] G. Mitteramskogler, M. Schwentenwein, C. Burkhardt, Lithography-based Metal
Manufacturing (LMM) Of 316L Powder, in: Euro PM 2018 Congress and
Exhibition, 2018.