Advanced Materials and Technologies 2A2 - Advanced Materials and Technologies) - P

1 Introduction 1-1
1 Introduction
P. BEISS, R. RUTHARDT, H. WARLIMONT
In conventional metallurgy the processing steps generally incorporate at least melting and casting, often
hot and cold working plus a large variety of secondary operations. In its broadest sense PM deals with
metallic powders which can be produced by numerous production techniques, e. g. reduction from oxides,
precipitation from liquids with or without assistance of electric current, mechanical impact or attrition,
atomization with gases or liquids and many other processes. Often several of these methods are applied
before the powder can be further processed, for instance reduction of ore plus mechanical crushing.
Sometimes metallic powders are used as such in particle form, i. e. without shaping and consolidation.
Examples are iron powders used in magnetic seed cleaning, magnetic particles dispersed in fluids,
powders incorporated in welding electrode coatings, reduced iron powders which set free gentle heat on
oxidizing with air as body warmers, solid state propulsion fuels or powders in fire works, powders for
coatings or claddings, e. g. wear resistant molybdenum, stellite or hard metal coatings, braze pastes,
metallic pigments for printing or in paints, and many others. The usage and processing of these
applications with the exception of powder manufacturing and some characteristics are not treated in this
volume.
Powder Metallurgy Data focuses on formed and consolidated products from powder and deals with
the properties of these products. Although there is no clear borderline between functional and structural
materials, it is generally understood that the chemical or physical properties of functional materials are of
higher importance for the application than geometry or mechanical strength, even if the application
affords shape and mechanical coherence. In this sense only few functional materials could be covered
here, the majority of the materials are structural in nature. Also ceramics and graphite products were
excluded, even though the manufacturing steps may be very similar to PM products.
Of the newer developments using metallic powders as raw material or feed stock many had to be
excluded for lack of data available to provide a systematic overview of the effect of processing variables.
Raw materials and many processing details usually affect decisively the property profile of a PM product,
and this information is often not yet generated in a sufficiently systematic way because the processes are
still too young. For this reason the rapid prototyping methods based on metallic powders, functionally
graded materials and nanomaterials were excluded, and so were metallic foams and materials
consolidated by self propagating high temperature synthesis.
Since metallic powder as a starting material is often far more expensive than its conventional
counterpart of equal chemical composition, there must be specific advantages for PM processing to
outweigh the material cost penalty. There is a variety of reasons to justify a PM approach, and for
different applications different reasons will usually apply, since there is no universal, common incentive
in favor of PM. Many PM materials cannot be manufactured any other way except PM, e. g. high melting
temperature metals, hard metals, immiscible alloys as used for electrical contacts and brake linings, or
several hard magnetic materials, high temperature superconductors and nano-grained materials. In other
areas the possibility to maintain a well defined interconnected porosity throughout the cross-section of a
structural part can be decisive, examples would be metallic filters or self-lubricating bearings. For high
alloy semi finished products the absence of macroscopic segregations and the potential to maintain fine
grained structures opened the route to industrial scale production, for instance with highly alloyed tool
steels or with unusually alloyed aluminum or copper base materials. PM structural parts found their niche
between cast and machined parts, because in general they offer better mechanical properties and
geometrical reproducibility than castings and have more favorable productivity than machined
components. This combination made structural PM parts produced from iron and steel one of the most
Lando lt -Bö rnst ein

New Ser ies VIII/2A2
1-2 1 Introduction
successful growth areas in metal processing technologies during the last fifty years and economically the
most important branch of powder metallurgy. As an example the following figure shows the development
of iron powder shipments in North America which are much better documented there than anywhere else
[75R, 81R, 85R, 88W, 89W, 90W, 91W, 93W, 95W, 98W, 99J, 00W, 01W]. Between 1950 and 2000
5
Iro n p ow d e r sh ip m en ts [1 0 5 m e tric to ns]
0
1943 53 63 73 83 93 20 0 3
Ye a r
Development of iron powder shipments in North America
the consumption increased by a factor of about 40 which corresponds to an average growth rate of 7.5 %
per year. Today 90 % of the iron powder production in North America is absorbed by the parts producing
industry, and 70 % of all part shipments serve the automotive industry. In Japan and Europe the volume is
smaller, but the growth and automotive dependence are similar to the development in North America.
There are estimates that during this decade the worldwide production of parts could exceed the one
million metric tons limit for the first time.
Defining the specific profile of material properties and advantages of PM processing compared with
competing technologies is part of each single chapter of this work.
Traditionally standards for PM materials allow much larger variations in chemical composition,
properties and processing details than is common for conventional materials. Therefore, even within the
limits of existing standards it was often not possible to trace the different dependencies from available
date, particularly when it comes to the effects of consolidation method or secondary operations on
properties. Many materials are not standardized and the manufacturers do not apply for standardization;
they stay rather with their more or less established trademarks and brand names. A systematic approach to
data sorting and evaluation becomes very difficult under these circumstances.
The editors see the limits of their endeavor and welcome helpful criticism by the users of this book in
order to achieve a better coverage of the subject in future editions. Comments and suggestions for
improvement are highly appreciated.
Finally, the editors would like to express their sincere thanks to all those who have contributed to this
new volume by volunteering as authors, by supplying data and giving permission to incorporate
unpublished data. We are grateful to the Editor in Chief, Prof. Werner Martienssen, for his support and
encouragement, and to the publisher, in particular to Dr. Rainer Poerschke and his staff, for their advice
and also for their patience.
Lando lt -Börnst ein

New Ser ies VIII/2 A2
1 Introduction 1-3
References for 1
75R K. H. Roll: State of the Industry - 1974; Progr. Powder Metall., Vol. 30, p. 207-213;
MPIF/APMI, Princeton, NJ, 1975.
81R K. H. Roll: Powder Metallurgy - The Technology for the New Decade; Modern Developm.
Powder Metall., Vol. 12, p. 1-15; MPIF/APMI, Princeton, NJ, 1981.
85R K. H. Roll: P/M Global Perspective - North America; Modern Developm. Powder Metall.,
Vol. 15, p. 1-11; MPIF/APMI, Princeton, NJ, 1985.
88W D. G. White: The Growing Internationalization of Powder Metallurgy; Modern Developm.
Powder Metall., Vol. 18, p. 1-8; MPIF/APMI, Princeton, NJ, 1988.
89W D. G. White: State of the P/M Industry in North America; Adv. in Powder Metall. 1989,
Vol. 1, p.1-8; MPIF/APMI, Princeton, NJ, 1989.
90W D. G. White: Powder Metallurgy - A Dynamic Industry; Adv. Powder Metall. - 1990, Vol. 1,
p. 1-13; MPIF/APMI, Princeton, NJ, 1990.
91W D. G. White: What’s Ahead for P/M ? Adv. Powder Metall. - 1991, Vol. 1, p. 1-14;
MPIF/APMI, Princeton, NJ, 1991.
93W D. G. White: State of the North American P/M Industry - P/M on the Rebound; Adv. Powder
Metall. & Particulate Mat. - 1993, Vol. 1, p.1-12; MPIF/APMI, Princeton, NJ, 1993.
95W D. G. White: State of the North American P/M Industry - P/M´s Promise Realized; Adv.
Powder Metal. & Particulate Mat. - 1995, Vol. 1. part 1, p. 1-13; MPIF/APMI, Princeton, NJ,
1995.
98W D. G. White: The Challenges of Growth: State-of-the-P/M Industry: North America Int. J.
Powder Metall. 34 (1998), 5, p. 27-35.
99J P. K. Johnson: APMI International - 40 Years Serving P/M Int. J. Powder Metall 35 (1999),
4, p. 43-45.
00W D. G. White: State-of-the-North American P/M Industry-2000; Int. J. Powder Metall.
36 (2000), 5, p. 41-47.
01W D. G. White: State-of-the-North American P/M Industry-2001; Int. J. Powder Metall.
37 (2001), 4, p. 33-41.

Ref. p. 12-23] 12 Refractory metals 12-1
12 Refractory metals
G. LEICHTFRIED
12.1 Introduction
Following the most common definition, refractory metals comprise elements of the group Va and VIa
possessing a melting point higher than 2000 °C; these are niobium, tantalum, molybdenum and tungsten.
In some publications the VIIa metal rhenium is also included, as it does not fit in any other classification.
Less common definitions describe a refractory metal as one having a melting point equal to or greater
than that of chromium, thus additionally including V, Tc, the reactive metal Hf and the noble metals Ru,
Os, Rh and Ir. This contribution will present data on molybdenum, tungsten, tantalum and niobium.
Powder metallurgy (P/M) is the only production route for commercial tungsten and tungsten alloys.
The P/M-processed percentage is also high in the case of molybdenum (97 %, remainder electron-beam-
melting, vacuum-arc-casting). The reason is the availability of pure, sinter-active and inexpensive
molybdenum powder produced by hydrogen-reduction of molybdenum oxide. Additionally, the finer
grain structure of P/M-material is advantageous both for the further processing and the mechanical
properties of the finished product. For some alloys such as those doped with potassium silicate, La2O3 and
Y2O3, P/M is the only possible production technique.
The requirements with regard to mechanical properties and microstructural homogeneity are again the
reasons for applying mainly P/M methods in producing Ta-wire as employed extensively in the
manufacture of capacitors. The larger percentage of the Ta sheet production is based on the use of
electron-beam molten material, as this production route is more economical. Also for reasons of higher
costs, there is no large scale P/M production of niobium and niobium alloys.
The industrial P/M production routes of Mo, W, Ta and their alloys are given in Fig. 12.1. The use of
net shape techniques such as powder injection molding and spraying on a dead mould is still limited to
some very specific applications in the field of electronic devices and aerospace products. Less than 10 %
of the production quantity is delivered in the as-sintered state. The most common processing techniques
for full density are deformation by rolling, forging, swaging and drawing.
In the early 1900’s industrial use of refractory metals was confined mainly to pure metals. An
extensive development program was carried out beginning in the late 50’s mainly driven by US aerospace
programs. Nowadays, a wide variety of alloys are commercially available. The compositions of solid
solution, precipitation and dispersion strengthened alloys are given in Table 1. Tungsten heavy metals
(W-Ni-Fe, W-Ni-Cu) are not considered in this contribution.
Carbide precipitation hardening (TZM, MHC) and the addition of deformable oxides (Mo-La2O3,
K-Si-Mo) resulting in oxide refining by deformation are the main strengthening mechanisms for
molybdenum. The former is effective up to a temperature of 1400 °C; the latter improves the creep
properties at temperatures higher than 1400 °C.
The commercially most important tungsten alloy is AKS-W. Its high creep resistance - making it the
material of choice for lighting applications - is a result of microdoping with 40 - 100 µg/g potassium
combined with a high amount of deformation (ϕ > 99 %) leading to an elongated interlocking
recrystallized grain structure. Alloying with rhenium lowers the ductile-to-brittle transition temperature
both in the case of tungsten and molybdenum. The insufficient availability and the high price of rhenium
limit the application of these alloys.

12-2 12 Refractory metals [Ref. p. 12-23
The addition of ThO2, BaO, SrO, Y2O3, Sc2O3 and rare-earth oxides lowers the electron work function of
tungsten. The production quantity of W-La2O3 and W-Ce2O3 as an electron emitting material is increasing
at the expense of the slightly radioactive material W-ThO2.
The production of capacitors - the dominating application for tantalum - requires material in its purest
state. Solid solution strengthened Ta2.5W finds its application as components in chemical apparatus.
Superconducting Nb46.5Ti accounts for more than half of all niobium alloys produced. Hafnium is the
main addition for Nb-based alloys used by the aerospace industry.
Refractory metals and their alloys are used in a wide variety of products and branches comprising
electrical and electronic devices, light sources, medical equipment, automobiles, aerospace and defence,
chemical and pharmaceutical industry or premium and sporting goods.
The producers of electrical and electronic devices including the lighting industry are the largest
consumers of refractory metal products. 1850 t of tungsten products were used in 1998 only for filaments
and electrodes in lamps. Significant quantities of molybdenum are consumed for semiconductor base-
plates for power rectifiers and various products for lamps, such as dipped beam shields or support wires.
Rapid growth in multimedia and wireless communication network systems has boosted the need for
W-Cu and Mo-Cu heat sink materials. These materials possess a high thermal conductivity combined
with a low thermal expansion, close to those of Si- and GaAs-semiconductors or certain packaging
materials. Also the amount of molybdenum and specifically Mo50W sputtering targets applied in the
production of wiring for large format thin-film transistor LCDs and PDPs has risen significantly because
of the unique combination of low resistivity and high resistance against Hillock formation. With around
70 % the electronic industry is the largest market for tantalum products, employing the metal mainly in
the manufacture of capacitors.
Refractory metals are also widely used by the materials processing industry. Molybdenum glass
melting electrodes, TZM and MHC isothermal forging tools weighing up to 4.7 t per part, MHC extrusion
dies, TZM piercing plugs for the production of stainless steel tubes, molybdenum and tantalum crucibles
for synthesizing artificial diamond or TIG-welding electrodes are examples for products in this field. In
order to improve the tribological properties of transmission and engine components for automobiles they
are coated with molybdenum. Recently developed products in the field of aerospace and defence industry
are shaped charge liners made of molybdenum or tungsten and explosively formed penetrators made of
tantalum. X-ray targets made of refractory metals are used in different areas of x-ray technology, from the
general diagnostics, angio-, cardiography to computer tomography. Besides metal targets graphite backed
W-Re / TZM composite targets are applied. The focal path consisting of W5Re or W10Re is bonded with
the TZM body by means of P/M techniques or produced by means of coating techniques. A complete list
of the various applications is given in Table 2.
powder
Mo,W,Ta
powder injection extrusion of plasticized

Shaping and die pressing cold isostatic pressing spray forming
molding powder
compaction Mo,W,Ta Mo,W,Ta W,Ta
Mo,W Mo,W
indirect heating
direct heating
Sintering (resistance heating elements or
(self - resistance heating)
induction radiant heating)
Mo,W,Ta
Mo,W,Ta
Full density hot isostatic pressing or

deformation infiltration
processing uniaxial hot pressing
Mo,W,Ta Mo,W
Mo,W,Ta
Fig. 12.1: Large scale production routes for Mo, W and Ta.

New-Ser ies VIII/2A2
Ref. p. 12-23]
Table 1. Typical compositions of commercial refractory metal alloys (in wt.%, analyses of base-metal correspond to metallic purity)
Alloy Mo W Ta Nb Re C O Si K Y La Ce Th Ti Zr Hf
designation
Molybdenum
alloys
Pure Mo 99.97
UHP-Mo 99.9995
TZM 99.3 0.025 0.02 0.5 0.08
MHC 98.6 0.08 0.035 1.2
Mo-La2O3 99.2-99.6 0.048- 0.27-
(ML) 0.1 0.6
M-Y2O3 99.42 0.10- 0.37- 0-
(MY) 0.12 0.43 0.06
K-Si-Mo 99.8-99.9 0.01- 0.013- 0.005-
0.07 0.07 0.03
Mo50Re 52.4 47.5
Mo30W 69.7 30
Tungsten alloys
Pure W 99.99
UHP-W 99.9995
AKS-W 99.98 0.004-
0.01
W-La2O3 97.9-98.9 0.15- 0.85-
(WL) 0.3 1.7
W-Ce2O3 (WC) 98.0 0.28 1.62
W-ThO2 (WT) 98.0 0.24 1.71
AKS-W-ThO2 98.0-99.0 0.12- 0.001- 0.86-
0.24 0.005 1.71
W5Re 94.9 5.0
W26Re 73.9 26
AKS-W3Re 96.9 3.0 0.004
12-3
12-4
Table 1. Typical compositions of commercial refractory metal alloys (in wt.%, analyses of base-metal correspond to metallic purity) (continued)
Alloy Mo W Ta Nb Re C O Si K Y La Ce Th Ti Zr Hf
designation
Tantalum
alloys
Pure Ta 99.95
Ta2.5W 2.5 97.4
Ta10W 10.0 89.9
Niobium alloys
Pure Nb 99.9
Nb1Zr 98.9 1.0
C-103 88.8 1 10
FS-85 10 28 60.8 1
WC-3009 9 60.8 0.1 30
Nb-46.5Ti 53.1 46.5
New-Ser ies VIII/2 A2
[Ref. p. 12-23
Table 2. Commercial applications of refractory metals and alloys by industry.
Industry Products made of Products made of Products made of Products made of

molybdenum or tungsten or tungsten tantalum or tantalum niobium or
molybdenum alloys alloys alloys niobium alloys
Aerospace jet vanes, shaped jet vanes, kinetic rocket engine thrust chambers,
and defence charge liners, pipe energy penetrators, components, exhaust nozzles
industry burners, stirring balancing weights, explosively formed
nozzles rocket engine penetrators
components
Automobile spraying wires balance weights
industry
Chemical and support structures, linings, heat
pharma- linings exchangers,
ceutical membranes, bursting
industry discs, autoclaves,
vessels, stirrers,
thermocouple
sheaths, evaporation
coils, condensers,
coolers, bayonet
heaters
Lighting support wires for incandescent and welding aids, getters current supply
industry incandescent and halogen lamp and electrode
halogen lamps, wire filaments, electrodes mountings for
leads, mandrel wires, for HID-lamps, Na-high pressure
sealing foils and cups, furnace ware, sealing lamps
extension parts, rods
dimming cups,
furnace ware, joining
sleeves
Materials glass melting TIG-welding crucibles for
processing electrodes, glass- electrodes, extrusion synthesis of artificial
industry stirrers / gobbers, dies, resistance diamonds and cubic
linings for glass welding electrodes, BN, heating
melting furnaces, hot zones and elements, radiation
components for quartz radiation shields, shields, furnace
glass production, furnace ware, parts, boats for
isothermal forging components for hot thermal vapor
tools, extrusion dies, isostatic presses, deposition,
casting dies / components for spinnerets for
thermocouple sheaths quartz glass production of
/ pumps / valves / production, crucibles synthetic fibers
stirrers / nozzles / for production of
linings for zinc sapphire single
production, resistance crystals, nozzles for
welding electrodes, production of
heating elements, ceramic wool /
radiation shields, fibres, filaments for
components for hot electron beam
isostatic presses, welding / melting
furnace ware, equipment,
crucibles for mountings for
production of sapphire machining tools,
single crystals, electrodes for EDM,

Industry Products made of Products made of Products made of Products made of

molybdenum or tungsten or tungsten tantalum or tantalum niobium or
molybdenum alloys alloys alloys niobium alloys
Materials crucibles for synthesis electrodes for plasma
processing of artificial diamonds spraying, boats /
industry and cubic BN, coils for thermal
(cont.) electrodes for melting vapor deposition
ceramics / enamels,
dip forming tools,
tools for isothermal
rolling, boats for
thermal vapor
deposition, substrate
carriers for CVD
equipment, hot runner
nozzles for plastic
injection molding,
piercing plugs for
steel
Producers of semiconductor base- electrical contacts, sputtering targets, superconducting
electrical / plates, components for switches, heat sinks, wires / foils / bats cables
electronic microwave devices, heat spreaders, for capacitors,
devices heat sinks, heat sputtering targets, components for
spreaders, mesh components for ion CRT´s, components
filaments, sputtering implantation and for MBE equipment
targets, anode grids MBE equipment,
for electronic tubes, semiconductor base
pins for miniature plates, mesh-grid
diodes, covering cathodes,
masks for photo- components for
etching, components experimental fusion
for ion implantation reactors, filaments
and MBE equipment for CRT´s
Producers of fixed / rotating anodes fixed / rotating implants,
medical for X-ray tubes, X-ray anodes for X-ray components for
equipment detectors, tubes, X-ray pacemakers, stents
detectors, for expanding of
collimators, shields arteries, scanner
for nuclear medicine plates
Producers of golf club weight jewellery
sporting inserts, weights for
goods / darts, weights for
premium fishing lines, balance
goods / others weights for tennis-
rackets, grit as
accelerator material
for trace analysis of
carbon and sulphur

12.2 Powder production
The refractory metals are extracted from ore concentrates, processed into intermediate chemicals, and
then reduced to the metal. The widely applied reducing agent for the production of Mo and W is
hydrogen, for Ta sodium and for Nb aluminum.
For the hydrogen reduction of Mo and W oxides the water vapor pressure in the powder bed plays a
crucial role determining the metal transport mechanism and as a consequence the powder properties.
Two transport mechanisms can be distinguished:
1) A gaseous transport phase occurs resulting in chemical vapor transport (CVT). During the
reduction process the morphology of the particles changes.
2) Oxygen transport via solid-state diffusion. The formed metal particles remain macroscopically
pseudomorphic to the oxide (PSM).
The most widely used raw materials for hydrogen reduced Mo powder is MoO3, to a smaller extent also
(NH4)2O.2MoO3 and (NH4)2O.6MoO3. Fig. 12.2 reveals the reduction path with the sequence MO3 →
Mo4O11 → MoO2 → Mo and the dominating mechanisms in dependence on the water vapor content of the
applied hydrogen.
The reaction product of the reduction process is H2O. The removal of H2O determines the water vapor
pressure in the powder bed. The rate of removal mainly depends on the apparent density of the powder
and the height of the powder bed. Also the reduction technology - push-type furnace or rotary furnace -
exerts an influence upon the H2O/H2 ratio, as the dynamic powder bed of the latter favors the exchange of
the gases. The effect of the dew point on the reaction kinetics and the phases formed can be seen in
Table 3 and Table 4. The kinetics of the hydrogen reduction of MoO2 powder is described in [79O, 92S].
Considering Fig. 12.3 it can be concluded that for a sufficiently high reaction rate, necessary for an
industrial production, a temperature higher than 800 °C has to be applied. However this would result in a
high loss of MoO3, owing to its high vapor pressure (T = 650 °C; p = 7 Pa [98S1]). Therefore the
industrial process is a two step process.
1st step: MoO3+H2 → MoO2+H2O; heat of reaction = – 46 kJ/mol [79U]

2nd step: MoO2+2H2 → Mo+2H2O; heat of reaction = + 67 kJ/mol [79U]
The first reduction step is carried out between 500 °C and 650 °C, the second between 900 °C and
1100 °C. The resulting particle size (Fisher subsieve size) amounts to 2 µm to 5 µm.
The raw materials for hydrogen reduced tungsten powders are ammonium paratungstate, WO3,
H2WO4 and tungsten blue oxide (TBO). The latter - most widely used - is a mixture of ammonium
tungsten bronze, hydrogen tungsten bronze, WO3, WO2.9 and WO2.72 formed during the calcination of
ammonium paratungstate under exclusion of air [91Z]. The TBO particles exhibit a high internal porosity
[91S3, 95L]. The large internal surface area enables ready uptake of liquid dopants, which is important
for the production of K-, Al-, Si-doped tungsten [95S]. Again under dry reduction conditions the oxygen
transport via solid-state diffusion dominates with the reduction sequence WO3 → WO2.9 → β-W → α-W
[91S1]. Under industrial conditions (750 °C < T < 1100 °C) and a high oxygen partial pressure the
gaseous tungsten oxide-hydroxide WO2(OH)2 is formed acting as the transport phase in the CVT
mechanism [76D, 81S1, 83H1, 91S1, 91S2] and the stepwise reduction WO3 → WO2.9 → WO2 → α-W is
observed, as illustrated in Fig. 12.4 [89Z, 91S2]. The influence of time and temperature on the weight loss
is shown in Fig. 12.5, additional kinetic data are given in [93F, 93S]. Compared to the hardmetal industry
where for the production of tungsten carbide a variety of tungsten powders is applied, with a big interest
in very fine-grained powders with a BET specific surface area up to 7 m2/g, the typical W-powders as
used for the P/M production of W-based alloys possess a particle size in the range 1.5 µm to 4.5 µm.

Metallic tantalum powder is produced by reducing potassium fluotantalate (K2TaF7) with sodium
according to the reaction equation:
K2TaF7+5Na→Ta+5NaF+2KF
The reduction takes place in a stirred retort containing a molten bath of K2TaF7 (melting point 765 °C)
and mixed diluent salts (KCl, NaCl, KF, NaF). After cooling the spongy product is crushed and the salts
are leached out with diluted acids. The remaining metallic tantalum powders are used for the production
of tantalum capacitors and are available with a Fisher subsieve size of 2 to 4 µm. The particles generally
have a very irregular shape with a high surface area which is desirable in capacitor applications. For P/M
products coarser powders with less surface area and higher tap density are favored. Processes to make
these powders often start with an ingot which may be made by melting sodium reduced powder as
described above or by melting tantalum scrap. The ingot is embrittled by hydriding, then crushed and
milled to a powder with a typical Fisher-sub sieve size of 9 µm. The powder finally is dehydrided and
deoxidized in a magnesium vapor atmosphere.
For the niobium production aluminothermically reduced, EB molten Nb is applied. In order to enable
pulverization niobium is embrittled by hydriding. After crushing and milling the powder is dehydrided.
Mo Fig. 12.2. Preferred reaction mechanism

and intermediate phases for H2-reduction
of MoO3 in dependence on the dew point
(τ) of the hydrogen,
H 2 , τ < 20°C PSM
PSM: solid state oxygen transport
H 2 , τ > -40°C H 2 , τ > -40°C mechanism (pseudomorphology),
MoO 3 Mo4 O11 MoO 2 CVT: chemical vapor transport mechanism,
MoO3: d50 (laser diffraction) = 4.4 µm,
CVT CVT BET specific surface area = 3.35 m2/g,
H 2 , τ > 40°C CVT filling weight = 100 mg,
temperature range / dew point range
investigated:
Mo MoO3 → Mo4O11 → MoO2:
400 - 800 °C
− 40 °C < τ < + 25 °C
MoO2 → Mo: 500 - 1100 °C
− 40 °C < τ < + 25 °C [98S1].
1.00 MoO 3
MoO 3
0.95
0.90 MoO 2
Weight loss m/m0
0.85
0.80 T = 400°C
500°C
0.75 600°C Fig. 12.3. Weight loss vs. reduction time for isothermal
700°C reduction of MoO3 at various temperatures,
0.70 800°C MoO3: d50 (laser diffraction) = 0.41 µm,
Mo BET specific surface area = 3.10 m2/g,
0.65 filling weight (Pt-crucible) = 2 g,
reduction conditions: hydrogen with a flow rate of
0.60 8 l/h and a dew point of 0 °C [98S1].
0 1 10 10 2 10 3 10 4
Time t [min]

Table 3. Weight percentage of Mo-oxide phases and Mo formed during reduction of MoO3 at 550 °C in
hydrogen, measuring method: XRD,
MoO3: d50 (laser diffraction) = 4.4 µm, BET specific surface area = 3.35 m2/g, particle shape:
deagglomerated, filling weight of MoO3 in Pt-crucible = 0.1 g, reduction conditions: hydrogen with a flow
rate of 8 l/h and a dew point of − 40 °C [98S1].
Reduction time MoO3 [wt.%] Mo4O11 [wt.%] MoO2 [wt.%] Mo [wt.%]

300s 80 20 - -
900s 17 72 11 -
1800s - 59 41 -
2700s - 30 70 -
1h - 7 90 3
1.5h - - 79 21
2h - - 51 49
20h - - - 100
Table 4. Weight percentage of Mo-oxide phases and Mo formed during reduction of MoO3 at 550 °C in
hydrogen, measuring method: XRD,
MoO3: d50 (laser diffraction) = 4.4 µm, BET specific surface area = 3.35 m2/g, particle shape:
deagglomerated, filling weight of MoO3 in Pt-crucible = 0.1 g, reduction conditions: hydrogen with a flow
rate of 8 l/h and a dew point of 2 °C [98S1].
Reduction time MoO3 [wt.%] Mo4O11 [wt.%] MoO2 [wt.%] Mo [wt.%]

1080s 15 79 6
1980s - 69 31
3120s - 43 57
4440s - 16 84
20h - - 82 18
WO 3
1
2 WO 2.9
4
3 5
WO 2.72
Fig. 12.4. Formation of oxide intermediates during the
6 hydrogen reduction of WO3. Under industrial conditions
7 8 (above 750 °C and high oxygen partial pressure) a
WO 2 stepwise reduction occurs following the sequence
1 → 4 → 6 → 9. The main reduction mechanism is a
β -W 9 chemical vapor transport reaction with WO2(OH)2 as the
gaseous transport phase. Under low oxygen partial
α -W pressure reduction is determined by oxygen transport by
10 solid state diffusion (reduction paths 2, 5, 7 and 8)
[91S1].

1.00
WO 3
1 T = 800 °C
0.96 2 870 °C
3 900 °C
4 950 °C
0.92 5 1000 °C
Weight loss m/m0
0.88
1
2
3
0.84 5 4 Fig. 12.5. Weight loss of WO3 vs. isothermal reduction
time for various temperatures,
0.80 WO3: Fisher subsieve size = 20 µm, filling weight
(alumina crucible) = 90 mg, powder layer height =
3 mm, reduction conditions: hydrogen with a flow rate
0.76 of 15 l/h and a dew point of − 40 °C [96L].
0 200 400 600 800 1000
Time t [min]
12.3 Powder compaction
Compaction of refractory metal powder is accomplished by die pressing and cold isostatic pressing. Large
tungsten billets, both for the rod and plate production, are cold isostatically pressed employing a wet bag
technique, whereas wire bars and small sheet bars are die pressed or cold isostatically pressed employing
a dry bag technique.
When discussing the compactibility of refractory metal powders it has to be distinguished between
molybdenum and tungsten on the one hand, and tantalum and niobium on the other hand, owing to
differences with regard to typical grain size, specific surface area, morphology and yield strength.
Essential data for the compacting process are given in Table 5.
The fractional green densities for molybdenum compacts in dependence on the compacting pressure
are shown in Fig. 12.6. The filling density is low, because of the large specific surface area and the
aggregated particle shape. The packing density can be increased by applying deagglomerated, e.g.
tumbled powder or vibration assisted filling techniques.
When analyzing the data of Fig. 12.6 according to Heckel [61H] it can be concluded, that up to a
pressure of around 60 MPa the main densification mechanism is the rearrangement of the particles.
Interparticle friction predominates more than any factor in this initial stage of compaction.
At higher pressures the formation of new contacts, the breaking of agglomerates and oxide skins and
cold welding become the dominant mechanisms. Within the pressure range investigated plastic
deformation was not observed. In Fig. 12.7 the compactibility of molybdenum is compared with that of
powders possessing a lower yield strength, such as Fe, Ni and Al. The corresponding graphs for AKS-
tungsten, tantalum and pure tungsten are given in Fig. 12.8, Fig. 12.9 and Fig. 12.10, respectively.
For tungsten neither gross plastic deformation nor fracturing of the individual powder particles was
observed within the investigated pressure range of 14 - 211 MPa [92B1]. The same author reports a
temperature increase in the green part of 10 °C for a pressurization rate of 10.8 MPa/s. In the case of
molybdenum and tungsten significant elastic strains are generated in the powder particles during
compaction, which can result in cracks during the decompression phase of the compaction cycle. At an
isostatic pressure of 211 MPa an elastic relaxation of 0.55 % was measured [92B1]. The typical
compacting pressures and the resulting densities for Mo, W, Ta and Nb are given in Table 5.

Table 5. Data of commercially applied refractory metal powders relevant for the compacting process
together with the compacting pressure as applied in large-scale production and the resulting fractional
densities.
Mo W Ta Nb
Fisher subsieve size [µm] 2-5 1.5 - 4.5 6 - 10 4-8
Fractional apparent density 0.11 - 0.17 0.13 - 0.22 0.20 - 0.28 0.18 - 0.25
Yield strength at ambient temperature 350 - 480 550 - 650 150 - 300 120 - 250
(recrystallized condition) [MPa]
Grain shape aggregate aggregate rounded angular
Typical compacting pressure [MPa] 200 - 500 200 - 500 200 - 500 200 - 500
Typical fractional green density 0.60 - 0.68 0.60 - 0.68 0.70 - 0.77 0.73 - 0.83
0.8
1.00
3N Mo - powder
0.7
Fractional green density Dg /D0
0.75
0.6
0.5 0.50
0.4 Mo
Al
0.25 Fe
0.3 Ni
0.2
0 100 200 300 400 500 600 0 500 1000 1500
Compacting pressure p [MPa] Compacting pressure p [MPa]
Fig. 12.6. Fractional green density vs. compacting Fig. 12.7. Fractional green density vs. compacting
pressure for molybdenum, pressure for molybdenum in comparison with nickel,
(Dg = green density, D0 = theoretical density) iron and aluminum,
powder: 3N Mo, Fisher subsieve size = 4.5 µm, powder:
d50 (laser diffraction) = 8.9 µm, Mo: Fisher subsieve size = 3.0 µm,
apparent density = 1.15 g/cm3, fractional apparent density = 0.33,
compacting: die pressing, dia. of the die = 12 mm, Ni: Fisher subsieve size = 50 µm,
filling weight = 6 g. fractional apparent density = 0.51,
Fe: Fisher subsieve size = 32 µm,
fractional apparent density = 0.39,
Al: Fisher subsieve size = 27 µm,
compacting method: isostatic pressing - wet bag tooling,
proposed empirical pressure-density relationship:
(1−Da/1−Dg) = 1 + qpr
with Da = apparent density, Dg = green density,
p = compacting pressure, q, r = constants [74S].

0.60 0.9
AKS - W powder 3N Ta - powder

Fractional green density Dg /D 0
0.55
0.8
0.50
0.7
0.45
0.40 0.6
0 50 100 150 200 250 100 200 300 400 500
Compacting pressure p [MPa] Compacting pressure p [MPa]
Fig. 12.8. Fractional green density vs. compacting Fig. 12.9. Fractional green density vs. compacting
pressure for AKS-tungsten, pressure for tantalum,
AKS-tungsten powder: Fisher subsieve size = 1.6 µm, powder: 3N tantalum, Fisher subsieve size = 10.5 µm,
compacting method: isostatic pressing - dry-bag tooling, apparent density = 3.7 g/cm3,
filling weight = 290 g, filling density = 4.0 ± 0.01 g/cm3 compacting: die pressing, dia. of the die = 12 mm,
[92B1]. filling weight = 10 g.
1.00
W - powder
0.75
Fig. 12.10. Fractional green density vs. compacting

pressure for tungsten,
powder:
0.50 W (0,004 mm): Fisher subsieve size = 4.0 µm,
W (0.015mm): Fisher subsieve size = 15 µm,
0.25 compacting: isostatic pressing - wet bag tooling,
W(0.004mm) proposed empirical pressure-density relationship:
W(0.015mm) (1−Da/1−Dg) = 1 + qpr
with Da = apparent density, Dg = green density,
p = compacting pressure, q, r = constants [74S].
0 500 1000 1500
Compacting pressure p [MPa]

12.4 Sintering
The major percentage of refractory metal products is made of deformed material. Therefore, the entire
processing route has to be optimized in such a way, that favorable forming properties are achieved. The
deformability is strongly related to the microstructure and grain boundary strength of the sintered
compact, the latter mainly influenced by grain boundary segregations. With regard to the microstructure,
the achievement of a low porosity combined with a fine grain is the primary goal. During the sintering
process the pores should be located at the grain boundaries as long as possible, in order to allow the
transport of vacancies by grain boundary diffusion. In the very final phase of the sintering process a
breaking-away of the pores from the grain boundaries is a favorable effect, as long as the resulting grain
coarsening is uniform and controllable. This positive effect can be explained by the weakening effect
being exerted by pores at grain boundaries. The impurity level in general and specifically contaminations
segregated at the grain boundaries should be as low as possible. This is determined by the purity of the
powder and the outgassing during sintering, mainly during that stage of the sintering process, where there
is still open porosity. Data on the evolution of the open porosity will be given for molybdenum and
tungsten. The minimum fractional sintered density, which is necessary for ensuring a smooth forming
operation amounts to around 0.93. The difference between the fractional green density, lying between 0.6
and 0.83, and the required sintered density is high, in other words considerable shrinkage occurs.
The selection of the sintering atmosphere is determined by the reaction of the refractory metals with
gases and carbon. The solubility for hydrogen, nitrogen, oxygen and carbon is low in the case of
molybdenum and tungsten, and high for niobium and tantalum. All of them form carbides and oxides, the
latter are volatile in the case of molybdenum and tungsten at temperatures above 600 °C. Niobium and
tantalum also form hydrides and nitrides. The usual sintering atmosphere for molybdenum and tungsten is
hydrogen with a dew point lower than 0 °C. Niobium and tantalum are sintered under vacuum typically
better than 5·10-3 Pa. Furnaces with resistance heating elements or induction radiant heating are
frequently used. Self-resistance heating is still applied for sintering tungsten, molybdenum and tantalum
rods, which are mainly used for the wire production. The typical sintering temperatures range from
1800 °C to 2200 °C for molybdenum, from 2100 °C to 2700 °C for tungsten, from 2100 °C to 2300 °C
for niobium and from 2400 °C to 2700 °C for tantalum. These sintering temperatures are based on
powders which are commercially applied (compare Table 5) and sintering times of 1 hour - 24 hours. For
this set of parameters with regard to temperature / time and powder particle size, grain boundary diffusion
is the dominating mechanism, which results in densification as described in [64K, 64V, 81S2, 92B2,
96B1, 96D].
From the variety of factors influencing the sintering process as generally described in [69T], the
impact of temperature, time, powder particle size, distribution of the powder particle size and atmosphere
will be considered in this section. Fig. 12.11 illustrates the effect of the green density on the sintering
behavior of molybdenum powder with a Fisher subsieve size of 4.6 µm. A higher green density, realized
by a higher compacting pressure, implies both a larger interparticle contact area and a higher defect
density. The result is a higher sintered density. The interparticle contact area can be increased also by
applying a powder with a smaller grain size. A comparison of the sintered density for molybdenum
compacts made of 3.0 µm and 4.55 µm powders, respectively, can be seen in Fig. 12.12. Additionally to
the larger interparticle contact area of powder with a smaller particle size, the grain boundary area of the
compact, developed during the evolution of the sintering process, is also larger up to that temperature,
where the grain boundaries extensively break away from the pores. The larger grain boundary area
enhances densification by grain boundary diffusion. For the molybdenum powders mentioned above and
sintered under the conditions as described in Fig. 12.12, the grain size number becomes equal (around
20.000 grains/mm2) at a temperature of 1900 °C.
The influence of the powder particle size on the sintering behavior of tungsten is illustrated in
Fig. 12.13 and Fig. 12.14. The use of a powder with a particle size of 2.15 µm instead of 4.05 µm makes
it possible to reduce the sintering temperature by around 400 °C, which is of great practical relevance,
especially for tungsten.

The particle size of the powder also determines the pore size in the sintered compact, which is illustrated
for molybdenum in Fig. 12.15. When comparing the pore sizes of sintered molybdenum compacts with
similar densities, the mean pore size is three times smaller for a sintered compact made of 2.6 µm powder
compared to a sintered compact made of 10 µm powder. Similar results were obtained both for
molybdenum [93B] and tungsten [96B2] by measuring the pore size by means of neutron small angle
scattering.
The advantages of fine powders are obvious. Although for tungsten sub-micron powders are
commercially available, as they are applied for the manufacturing of cemented carbides, only powders
with particle sizes larger than 1.5 µm are applied for P/M processing. The main disadvantages of fine
grained powders are the higher content of adsorbed gases and an impeded outgassing during the sintering
process.
While sintering molybdenum or tungsten, water vapor is formed inside the compact, because of the
reaction between hydrogen and the residual oxygen in the powder. This water vapor cannot be removed
sufficiently especially from the centre of the compact in the case of a low gas permeability. Decreasing
the particle size leads to a reduction of the gas permeability through the compact. This can be explained
by the higher specific surface of a fine powder, which intrinsically results in a lower gas permeability in
the green compact [01S2]. Additionally, the onset temperature from an open to a closed pore structure is
shifted towards lower temperatures, when applying a fine powder. As an example the evolution of the
pore structure of tungsten is shown in Fig. 12.16. Both effects - intrinsic lower gas permeability and early
reduction of the open porosity - impede the outgassing of impurities, especially of the water vapor formed
within the compact [01S1]. From dilatometer experiments with molybdenum samples (Fig. 12.17) it can
be concluded, that in the case of a high dew point the densification process is adversely affected. This
effect can also be observed in measuring the porosity (Fig. 12.18). It could be found, that the higher dew
point results in a reduction of surface area by a chemical vapor transport mechanism [01S2]. The lower
surface area implies a lower driving force for sintering.
By blending coarse and fine powders the green density can be increased [94G]. For a mixture of
molybdenum powders with particle sizes of 4.6 µm and 0.85 µm the maximum in green density occurs at
40 wt.% fine powder. However, the maximum in green density does not consequently result in the highest
sintered density, as it is demonstrated in Fig. 12.19. Bimodal powder blends tend to densify in a non-
uniform way and tend to form a bimodal pore structure, which is sensitive to coarsening by Ostwald
ripening [98S2].
The high solubility for gases and the strong impact of interstitials on the mechanical properties have to
be considered when sintering niobium and tantalum. One key requirement is the use of a powder with a
low oxygen content. Tantalum powders with an oxygen content lower than 150 µg/g are already available
[01K]. Typically, the sintering of niobium and tantalum is performed under vacuum control, in order to
ensure a low oxygen and nitrogen partial pressure during the entire sintering process. An effective
reduction especially of the oxygen content can be achieved only at a temperature higher than 2200 °C in
the case of niobium, and 2500 °C in the case of tantalum. Therefore, the typical homologous temperatures
for sintering niobium and tantalum are around one tenth higher compared to those for molybdenum and
tungsten. The results of a sintering study [96B1] are presented in Fig. 12.20.
The mechanical properties of the sintered compact are strongly influenced by the percentage of
porosity which is of practical relevance especially for the intrinsic brittle materials molybdenum and
tungsten. As an example the fracture toughness of tungsten in dependence on the percentage of porosity
and testing temperature is shown in Fig. 12.21.

0.96 1.00
Molybdenum Molybdenum
0.95 0.95
0.90
Fractional sintered density Ds /D0

0.94
0.85
0.93 0.80
0.92 0.75
0.70
0.91
0.65 3.00 µm
0.90 4.55 µm
0.60
0.89 0.55
0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 700 1100 1500 1900 2300
Fractional green density Dg /D0 Sintering temperature T [°C]
Fig. 12.11. Fractional sintered density vs. fractional Fig. 12.12. Fractional sintered density vs. sintering
green density for molybdenum specimens, temperature for molybdenum specimens,
(Ds = sintered density, D0 = theoretical density) powder:
powder: 3N molybdenum with Fisher subsieve size of 3N molybdenum with Fisher subsieve size of 3.0 µm
4.6 µm, apparent density = 1.36 g/cm3, (apparent density = 0.88 g/cm3, tap density = 1.97 g/cm3),
d50 (laser diffraction) = 11.0 µm, 3N molybdenum with Fisher subsieve size of 4.55 µm
compacting: die pressing (100 MPa < p < 500 MPa), (apparent density = 0.97 g/cm3, tap density = 2.22 g/cm3),
sintering: compacting: isostatic pressing with a compacting
indirect heating, sintering temperature = 2050 °C, pressure of 220 MPa, fractional density (Mo-powder
isothermal sintering time = 5 h, Fisher subsieve size of 3.0 µm) = 0.597,
sintering atmosphere: hydrogen [98S1]. fractional density (Mo-powder Fisher subsieve size of
4.55 µm) = 0.630,
sintering: indirect heating, heating rate: 300 °C/s,
isothermal sintering time = 1 min., sintering atmosphere:
hydrogen (dew point = – 30 °C).
20
Tungsten
18
Sintered density Ds [g/cm 3 ]
Fig. 12.13. Sintered density vs. sintering temperature for

16 tungsten specimens,
powder: 3N tungsten with Fisher subsieve size of 2.15 µm
and 4.05 µm,
14 compacting: die pressing with a compacting pressure of
300 MPa, diameter of the die = 12 mm, weight-in quantity =
12 g, green density = 11.7 g/cm³ (tungsten powders with
12
Fisher subsieve size of 2.15 µm) and 11.9 g/cm³
W 2.15 µm (tungsten powders with Fisher subsieve size of 4.05 µm),
W 4.05 µm
10 sintering: indirect heating, heating rate = 0.2 °C/s,
isothermal sintering time = 1 hour, sintering atmosphere:
hydrogen [96B2].
8
1000 1400 1800 2200 2600
Temperature T [°C]

1.0 40
Molybdenum
Tungsten
Densification param.(D s - Dg /D t - Dg )
0.9
30
Frequency [%]
0.8
20
2.5 µm
0.7 4.3 µm
10.0 µm
10
0.6
W 2.15 µm
W 4.05 µm
0.5
100 1000 10000 100000 0 5 10 15 20 25
Sintering time t [s] Pore size d [µm]
Fig. 12.14. Sintering densification parameter vs. Fig. 12.15. Pore size distribution of sintered 3N8
sintering time for tungsten compacts sintered at 2100 °C molybdenum specimens,
(Ds = sintered density, Dg = green density, powder / sintered density:
Dt = theoretical density), Fisher subsieve size = 2.6 µm: sintered density = 9.84 g/cm³,
powder: 3N tungsten with Fisher subsieve size of Fisher subsieve size = 4.6 µm: sintered density = 9.90 g/cm³,
2.15 µm and 4.05 µm, Fisher subsieve size = 10.0 µm: sintered density = 9.70 g/cm³,
compacting: die pressing with a compacting pressure of compacting: isostatic pressing with a pressure of
300 MPa, diameter of the die = 12 mm, filling weight = 12 g, 220 MPa.
green density = 11.7 g/cm³ (tungsten powders with
Fisher subsieve size of 2.15 µm) and 11.9 g/cm³
(tungsten powders with Fisher subsieve size of 4.05 µm),
sintering: indirect heating, heating rate = 0.2 °C/s,
sintering atmosphere: hydrogen.
0.5
Tungsten
total porosity
0.4 closed porosity
open porosity
Fractional porosity
0.3
Fig. 12.16. Total, closed and open porosity vs. sintering

0.2 temperature for tungsten specimens,
powder: tungsten with a mean particle size of 0.5 - 1 µm,
BET specific surface area = 0.6 m²/g,
0.1 compacting: die pressing with a green density of the
compacts of 11.6 g/cm³,
sintering: isothermal sintering time = 2 hours,
atmosphere: hydrogen [90R].
0 20 1000 1500 2000
Sintering temperature T [°C]

10 35
Molybdenum
0 Mo 3.05 µm/H 2 -
30
dew point = − 40 °C
-10 Molybdenum Mo 3.05 µm/N 2 - H 2 -
25
Length change ∆ L/L0
dew point = 0 °C
-20
Open porosity [%]

20
-30
15
-40
-50 10
Mo 3.05 µm/H 2 - dew point = − 40 °C
-60 Mo 3.05 µm/N 2 - H 2 - dew point = 0 °C 5
-70 0
0 200 400 600 800 1000 1200 1400 1600 1200 1400 1600 1800 2000 2200
Sintering temperature T [°C] Sintering temperature T [°C]
Fig. 12.17. Dilatometer curves; change in length ∆L/L0 Fig. 12.18. Open porosity vs. sintering temperature
vs. sintering temperature, measured by means of mercury porosimetry,
powder: 3N molybdenum with a Fisher subsieve size of powder: 3N molybdenum powder with a Fisher subsieve
3.05 µm, size of 3.05 µm,
compacting: isostatic pressing with a compacting compacting: isostatic pressing with a compacting
pressure of 220 MPa, pressure of 220 MPa,
dilatometric test: indirect heating, heating rate = 0.14 °C/s, sintering: indirect heating, heating rate = 0.14 °C/s,
atmosphere: hydrogen with a dew point of – 40 °C and atmosphere: hydrogen with a dew point of – 40 °C and
forming gas with a N2:H2 ratio of 95:5 and a dew point forming gas with a N2:H2 ratio of 95:5 and a dew point
of 0 °C, equivalent to a hydrogen atmosphere with a of 0 °C, equivalent to a hydrogen atmosphere with a dew
dew point of 50 °C [01S2]. point of 50 °C [01S2].
10.0
Molybdenum
9.5
9.0
green density
Densit y D [g/cm 3 ]
8.5 1000°C/1min. Fig. 12.19. Green and sintered density vs. composition
1400°C/1min. of 3N molybdenum powder mixtures made of coarse
1900°C/1min. grained (Fisher subsieve size = 4.6 µm) and fine grained
8.0
(Fisher subsieve size = 0.85 µm) powders for various
sintering temperatures,
7.5 compacting: die pressing with a compacting pressure of
350 MPa, dimension of the green parts: dia. = 10 mm,
7.0 h = 5 mm,
sintering: indirect heating, heating rate = 0.2 °C/s,
6.5 isothermal sintering time = 1 min., sintering atmosphere:
0 20 40 60 80 100 hydrogen with a dew point of – 20 °C.
Weight fraction fine powder [%]

1.0 24
6
Tantalum Tungsten
20
0.9 5
Fracture toughness KIC [MPa m 1/2]

1 porosity = 40%
16 2 porosity = 32%
3 porosity = 24%
0.8
4 porosity = 14.5% 4
12 5 porosity = 8%
6 porosity = 6%
0.7
8
3
0.6 4 2
1
0.5 0
−200 0 200 400
2400°C/1h
2600°C/3h
2400°C/5h
2200°C/3h
AS CIP
2400°C/3h
Testing temperature T [°C]
Fig. 12.20. Fractional sintered density in dependence on Fig. 12.21. Fracture toughness KIC of sintered tungsten
sintering conditions for tantalum, specimens with various porosities vs. testing temperature,
powder: tantalum, Fisher subsieve size = 9.9 µm, powder: tungsten with mean particle size of 0.5-1.0 µm,
apparent density = 3.82 g/cm³, tap density = 5.81 g/cm³, BET specific surface area = 0.6 m²/g,
oxygen content = 234 µg/g, hydrogen content = 651 µg/g, compacting: die pressing with a green density of the
compacting: isostatic pressing with a compacting compacts of 1.6 g/cm3,
pressure of 345 MPa (dia. = 25.4 mm), green density = sintering:
13.28 g/cm³, sintering temperature for porosity 6 %: 2000 °C
sintering: indirect heating, heating rate 1.6 °C/s, sintering temperature for porosity 8 %: 1900 °C
atmosphere: vacuum 1.3·10-2 Pa or better [96B1]. sintering temperature for porosity 14.5 %: 1800 °C
sintering temperature for porosity 24 %: 1600 °C
isothermal sintering for 2 hours, atmosphere hydrogen
[90R].

12.5 Properties
The atomic, structural and electrical properties are listed in Table 6, the thermophysical properties in
Table 7. The crystal structure of the Va and VIa metals is bcc, without phase change in the solid state.
Apart from their high melting point and the low vapor pressure the special features of refractory metals
are their low thermal expansion coefficient and in the case of molybdenum and tungsten a high thermal
and electrical conductivity. This combination of physical properties has opened up a wide range of new
applications during the last decade, especially in the field of electronics.
Refractory metals have an excellent resistance to many chemical agents. In particular tantalum is
outstanding in its performance. It is inert below 150 °C to all concentrations of hydrochloric and nitric
acid, to 98 % sulphuric acid, to 85 % phosphoric acid and aqua regia, whereas it is attacked by
hydrofluoric acid and strong alkalis. Molybdenum and tungsten are highly resistant to many glasses and
metal melts in the absence of free oxygen.
Refractory metals have to be protected from oxidizing environment, as they do not form protective
oxide layers. Oxidation of molybdenum and tungsten leads to a loss of material by formation of volatile
oxides at a temperature exceeding 600 °C, but without any significant impact on the mechanical
properties. Only an increased recrystallization temperature in the surface zone of molybdenum and
tungsten products, deformed at temperatures higher than 800 °C under air is reported with the explanation
of a higher oxygen concentration in this area [01G]. In the case of tantalum and niobium the solubility for
N, O, H and C is high. The uptake of these elements is linked with a significant increase of hardness and
loss of ductility. A comprehensive survey about the reaction of refractory metals with gases is given in
[76F]. The oxidation resistance can be improved by applying coatings. The best results can be achieved
with silicide coatings modified with boron and carbon [97D]. Recently developed Mo-Si-B alloys [94B]
and Nb-silicide composites [01B] exhibit an oxidation resistance sufficiently high for ensuring emergency
running properties.
The mechanical properties are sensitively dependent on the thermomechanical treatment. Both
strength and fracture toughness increase with increasing plastic deformation [97P2]. Additionally, the
mechanical properties are dependent on the type of deformation process, purity and heat treatment.
Special attention should be given to the gas content of niobium and tantalum.
One of the most challenging tasks is the increasing of the low-temperature plasticity of molybdenum
and tungsten. The low temperature brittleness is substantially determined by the existence of a rigid
covalent component of the interatomic bond in the edge of the bcc lattice cell. This specific feature
explaines the low solubility for interstitial elements. These elements occupy the octahedral sites of the
crystal lattice and cause its tetragonal distortion and a strong interaction of dislocations with the elastic
field surrounding the interstitial solutes and suppressing the dislocation movement [01M].
A rough ranking of the high temperature strength of molybdenum and tungsten alloys can be obtained
from the comparison presented in Table 8. Carbide precipitation strengthened Mo-based alloys (MHC,
TZM) and alloys high in rhenium (Mo-50Re, W-26Re) possess the highest strength. Alloys containing
potassium (AKS-W, AKS-W-ThO2) exhibit high strength only after high plastic deformation.
Also the recrystallization temperature is listed in Table 8. Those alloys (ML, K-Si-Mo, WL10, WL15,
WT20, AKS-W-ThO2) containing particles, which deform together with the matrix metal, reveal in the
highly deformed state a significantly increased recrystallization temperature. This can be explained by a
particle refining effect. During the deformation process the particles elongate into stringers. By annealing
these stringers break up and a pearl row of very small particles is formed. With the increasing number of
particles, the subgrain boundaries are pinned more and more effectively resulting in an increase of the
recrystallization temperature [92L]. Potassium doped tungsten shows a similar effect, with the difference,
that potassium containing bubbles are responsible for this effect.
A comparison of the warm strength of rods made of molybdenum, tungsten, niobium and tantalum in
their usual as-delivered condition is given in Fig. 12.22. The typical microstructure of stress relieved
molybdenum is a highly polygonized structure with up to five percent recrystallized grains. Depending on
the product shape, tungsten is delivered in the as-worked state, especially sheet material and wires, or
stress relieved with a polygonized microstructure. Niobium and tantalum are usually delivered in the
recrystallized state employing a heat treatment, which results in fine grained primarily recrystallized
microstructure. For a better comparison, the warm strength of stress relieved 1 mm sheets made of Mo-,
W- and Ta-based materials is shown in Fig. 12.23. For short term application under high stresses the

precipitation strengthened Mo alloys TZM and MHC offer the best performance up to a service
temperature of 1500 °C, for higher temperatures tungsten based materials should be applied. Tantalum
alloys are used only if additionally high ductility is required after cooling to room temperature.
The creep properties of refractory metals are very sensitive to composition, microstructural features
and test environment. The data base was mainly established in the sixties and seventies of the last century,
in the framework of basic development programs for space vehicles. A comprehensive survey is given in
[71C], but with partly not specified microstructural features. As especially the grain size exhibits a
decisive impact on the creep strength these data allow only a rough assessment of the high temperature,
long term performance. The 100 hour creep rupture data are summarized in Fig. 12.24.
Table 6. Atomic, structural and electrical properties of pure refractory metals [86P].
Mo W Ta Nb
Atomic number 42 74 73 41
Relative atomic mass 95.94 183.85 180.95 92.91
Atomic volume [m3] 1.53·10-29 1.59·10-29 1.80·10-29 1.80·10-29
Density at 20 °C [g/cm3] 10.2 19.3 16.6 8.6
Crystal structure bcc bcc bcc bcc
Lattice constant [nm] 0.3147 0.3165 0.3303 0.3294
Burgers vector [m] 2.73·10-10 2.74·10-10 2.86·10-10 2.86·10-10
Electrical resistivity at 20 °C [µΩ m] 0.052 0.055 0.125 0.140
Table 7. Thermopysical properties of pure refractory metals.
Source Mo W Ta Nb
Melting point [ °C] [64L] 2610 3410 2996 2468
Boiling point [ °C] [64L] 5560 5900 6100 ~4900
Vapor pressure at 2500 K [Pa] [97P1] 7·10-2 1·10-5 1·10-4 5.5·10-3
Coefficient of linear thermal Mo: [00P]
expansion [µm/(m K)] W: [86P]
Ta: [89P]
Nb: [64L]
20 °C 5.15 4.42 6.35 7.10
(100 °C)
300 °C 5.35 4.55 6.53 7.32
600 °C 5.56 4.70 6.73 7.64
900 °C 5.77 4.86 6,93 7.95
1200 °C 5.98 5.02 7.12
1500 °C 6.19 5.18 7.32
Thermal conductivity [W/(m K)] Mo: [00P]
W: [97P1]
Ta, Nb: [64L]
20 °C 141 159 54.4 52.3
(0 °C)
300 °C 133 143 58.6
600 °C 124 125 65.3
900 °C 116 118
1200 °C 107 112
1500 °C 101 72.8
(1430 °C)

Source Mo W Ta Nb
Specific heat [J/(g K)] Mo, W: [00P]
Ta, Nb: [89P]
20 °C 0.254 0.132 0.142 0.264
300 °C 0.268 0.138 0.147 0.282
600 °C 0.283 0.144 0.152 0.300
900 °C 0.298 0.150 0.158 0.318
1200 °C 0.313 0.156
1500 °C 0.324 0.162
Table 8. Typical recrystallization temperature and ultimate tensile strength at T = 1000 °C of commercial
molybdenum and tungsten based rod material with defined amount of deformation ϕ .
Alloy Composition Temperature for 100 % Typical ultimate tensile

designation recrystallized structure strength at 1000 °C
(t = 1 h)
wt.% °C MPa
Pure Mo 1100 (ϕ = 90 %) 250 (ϕ = 90 %)
TZM Mo, 0.5 % Ti, 0.08 % Zr, 0.025 %C 1400 (ϕ = 90 %) 600 (ϕ = 90 %)
MHC Mo, 1.2 % Hf, 0.08 % C 1550 (ϕ = 90 %) 800 (ϕ = 90 %)
ML Mo, 0.3 % La2O3 1300 (ϕ = 90 %) 300 (ϕ = 90 %)
2000 (ϕ = 99.99 %)
MY Mo, 0.48 % La2O3, 0.07 % Ce2O3 1100 (ϕ = 90 %) 300 (ϕ = 90 %)
1350 (ϕ = 99.99 %)
K-Si-Mo Mo, 0.05 % Si, 0.025 % K 1200 (ϕ = 90 %) 300 (ϕ = 90 %)
1800 (ϕ = 99.99 %)
Mo50Re Mo, 47.5 % Re 1300 (ϕ = 90 %) 600 (ϕ = 90 %)
Mo30W Mo, 30 % W 1200 (ϕ = 90 %) 350 (ϕ = 90 %)
Pure W 1350 (ϕ = 90 %) 350 (ϕ = 90 %)
AKS-W W, 0.005 % K 2000 (ϕ = 99.9 %) 800 (ϕ = 99.9 %)
WL10 W, 1.0 % La2O3 1500 (ϕ = 90 %) 400 (ϕ = 90 %)
2500 (ϕ = 99.99 %)
WL15 W, 1.5 % La2O3 1550 (ϕ = 90 %) 420 (ϕ = 90 %)
2600 (ϕ = 99.99 %)
WC20 W, 1.9 % Ce2O3 1550 (ϕ = 90 %) 420 (ϕ = 90 %)
2600 (ϕ = 99.99 %)
WT20 W, 2 % ThO2 1450 (ϕ = 90 %) 400 (ϕ = 90 %)
2400 (ϕ = 99.99 %)
AKS-W- W, 1 % ThO2, 0.004 % K 2400 (ϕ = 99.9 %) 1000 (ϕ = 99.9 %)
ThO2
W5Re W, 5 % Re 1700 (ϕ = 90 %) 500 (ϕ = 90 %)
W26Re W, 26 % Re 1750 (ϕ = 90 %) 900 (ϕ = 90 %)

700 1200
Mo Mo
600
W 1000 W
Ultimate tensile strength R m[MPa]
Ultimate tensile strength R m[MPa]

Ta Ta
500 Nb TZM
800 Ta 10W
400
600
300
400
200
100 200
0 400 800 1200 1600 2000 0 400 800 1200 1600 2000
Testing temperature T [°C] Testing temperature T [°C]
Fig. 12.22. Ultimate tensile strength vs. testing Fig. 12.23. Ultimate tensile strength vs. testing
temperature for Mo, W, Ta and Nb rods in their usual temperature for Mo, TZM, W, Ta and Ta10W sheets
as-delivered condition, with a thickness of 1 mm, material condition: stress
Mo, W: diameter = 25 mm, Ta, Nb: diameter = 12 mm, relieved.
Mo, W: material condition: stress relieved,
Ta, Nb: material condition: recrystallized.
1000
W
TZM
W - 25Re
Nb
Ta
100 Mo
Stress σ [MPa]
10
Fig. 12.24. Comparison of 100 h creep rupture data for

1 selected refractory metals [71C].
1000 1100 1200 1300 1400 1500 1600 1700 1800 1900
Testing temperature T [°C]

12 Refractory metals 12-23
References for 12
61H Heckel, R.W.: Trans. Metall. Soc. AIME, 221 (1961) 1001.
64K Kothari, N.C.: Powder Metall. 7 (1964) 251.
64L Landolt-Börnstein, 6. Auflage, IV. Band, Technik, 2.Teil, Bandteil b, Berlin: Springer Verlag
(1964).
64V Vasilos, T., Smith, J.T.: J. Appl. Phys. 35 (1964) 215.
69T Thümmler, F., Thomma, W.: Metall. Rev. 12 (1969) 69.
71C Conway, J.B., Flagella, B.N.: Creep Rupture Data for the Refractory Metals to High
Temperatures, New York: Gordon and Breach Science Publishers, 1971.
74S Schob, O., Geijtenbeek, J.J.F.: High Temp. High Pressures 6 (1974) 261.
76D Davis, G.: Philips Techn. Rev. 36 (1976) 36
76F Fromm, E., Gebhardt, E.: "Gase in Metallen", Berlin: Springer-Verlag (1976).
79O Orehotsky, J., Kaczenski, M.: Mater. Sci. Eng. 40 (1979) 245.
79U Ullmanns Enzyklopädie der Technischen Chemie, 4.Auflage, Band 17; Weinheim, New York:
Verlag Chemie, 1979, p. 23.
81S1 Sahle, W., Berglund, S.: J. Less Common Met. 2 (1981) 271.
81S2 Swinkels, F.B., Ashby, M.F.: Acta Metall. 29 (1981) 259.
83H1 Haubner, R., et al.: Int. J. Refract. Met. Hard Mater. 2 (1983) 108.
83H2 Haubner, R., et al.: Int. J. Refract. Met. Hard Mater. 2 (1983) 156.
86P Plansee Aktiengesellschaft, Material Data Base, Reutte (1986).
89Z Zhengji, T.: Int. J. Refract. Met. Hard Mater. 8 (1989) 179.
90R Rodchenko, P.Y., Podrezov, Y.N., Panichkina, V.V., Skorokhod, V.V.: Poroshkovaya
Metallurgiya (Minsk) 8 (1990) 36.
91S1 Schubert, W.D.: Int. J. Refract. Met. Hard Mater. 9 (1991) 178.
91S2 Schubert, W.D., Lassner, E.: Int. J. Refract. Met. Hard Mater. 10 (1991) 133.
91S3 Schubert, W.D., Lassner, E.: Int. J. Refract. Met. Hard Mater. 10 (1991) 171.
91V Van Put, J.W., Zegers, T.W., Liu, H.: Int. J. Refract. Met. Hard Mater. 10 (1991) 123.
91Z Zeiler, B., Schubert, W.D., Lux, B.: Int. J. Refract. Met. Hard Mater. 10 (1991) 83.
92B1 Bewlay, B.P.: Int. J. Refract. Met. Hard Mater. 11 (1992) 165.
92B2 Bewlay, B.P.: Proc. 5th Intern. Tungsten Symp., MPR Publishing Services Ltd (1992) 227.
92L Leichtfried, G.: Advances in Powder Metallurgy and Particulate Materials - 1992, Vol. 9;
Princeton NJ: MPIF/APMI, 1992, p.123.
92S Sichen, D., Seetharaman, S.: Metall. Trans. B 23 (1993) 317.
93B Blaschko, O., Glas, R., Krexner, G., Weinzierl, P., Leichtfried, G.: Proc. 13th Plansee Seminar,
Reutte 1 (1993) 531.
93F Fouad, N., Attyia, K.M.E., Zaki, M.I.: Powder Tech. 74 (1993) 31.
93S Savin, A.V.: Izv. Rossiiskoi Akad. Nauk. Metally 4 (1993) 16.
94B Berczik, D.: PCT/WO 96/22402.
94G German, R.M.: Powder Metallurgy Science, 2nd Ed., Princeton: MPIF, 1994, p. 168.
95L Lassner, E., Schubert, W.D.: Int. J. Refract. Met. Hard Mater. 13 (1995) 111.
95S Schubert, W.D., Lux, B., Zeiler, B.: Int. J. Refract. Met. Hard Mater. 13 (1995) 119.
96B1 Bingert, S.R., Vargas, V.D., Sheinberg, H.: Tantalum, The Minerals, Metals & Materials Soc.
(1996) 95.
96B2 Blaschko, O., Prem, M., Leichtfried, G.: Scr. Mater. 34 (1996) 1045.
96D Dubois, S.G., Ganesan, R., German, R. M.: Tantalum, The Minerals, Metals & Materials Soc.
(1996) 319.
96L Lackner, A., Molinari, T., Paschen, P.: Scand. J. Met. 25 (1996) 115.
97D Disam, J., Gohlke, D., Lübbers, K., Martinz, H.P., Roedhammer, P.: Proc. 14th Plansee
Seminar, Reutte 1 (1997) 269.
97P1 Plansee Aktiengesellschaft, Tungsten Brochure, Reutte, 1997.

12-24 12 Refractory metals
97P2 Parteder, E., Knabl, W., Stickler, R., Leichtfried, G.: Proc. 14th Plansee Seminar, Reutte 1
(1997) 985.
98S1 Schulmeyer, W.V.: Mechanismus der Wasserstoffreduktion, Thesis, Darmstadt, 1998.
98S2 Skorokhod, V.V., Panichkina, V.V.: Effect of Particle Size Distribution on Initial Powder
Sintering Stage, Special Interest Seminar Fundamentals of Sintering, PM World Congress,
Granada, 1998.
00B Buckman, R.W.: Int. J. Refract. Met. Hard Mater. 18 (2000) 253.
00D DiStefano, J.R.: Int. J. Refract. Met. Hard Mater. 18 (2000) 237.
01B Bewlay, B.P., Briant, C.L., Jackson, M.R., Subramanian, P.R.: Proc. 15th Plansee Seminar,
Reutte 1 (2001) 405.
01G Gnesin, B.A., Kireiko, V.V., Zuev, A.P.: Proc. 15th Plansee Seminar, Reutte 3 (2001) 161.
01K Kumar, P., Uhlenhut, H.: Proc. 15th Plansee Seminar, Reutte 1 (2001) 449.
01M Makarov, P., Povarova.: Proc. 15th Plansee Seminar, Reutte 1 (2001) 464.
01S1 Stallybrass, Ch.: Diploma Thesis, Montanuniversität Leoben, 2001.
01S2 Stallybrass, Ch., Leichtfried, G.: Proc. 15th Plansee Seminar, Reutte 1 (2001) 267.

Ref. p. 13-185] 13 Hard materials 13-1
13 Hard Materials
G.E. SPRIGGS
13.1 Introduction
13.1.1 Diamond and cubic boron nitride

Of all the hard materials, the premier position is still held by diamond, the oldest of the known materials.
The age of natural diamonds has been determined, using radioactive techniques on mineral inclusions
within the diamonds, as being from 990 to 3300 million years, although they were only brought into the
upper mantle of the earth ca. 100 to 1200 million years ago. The synthesis of diamond has always held a
fascination for scientists, ever since it was discovered that diamond was a form of carbon.
Table 1. high-lights some of the progress made in this quest and also the discovery of a new
synthesised material - cubic boron nitride.
Table 1. Chronological order of the evolution of diamond and cubic boron nitride.
Date Event Reference

990 - 3300 Formation of diamond at a depth of > 150 km below the earth's mantle 91K, 92H
million years (genesis age)
100 - 1200 Diamonds brought into the earth's upper mantle in Kimberlite and 91K, 92H
million years Lamproite rock types (eruption age)
1880 Hannay claimed to have produced diamonds in the laboratory. 1880H
1890 The first diamond drill hole (394 m) on the Mesabi iron range (Minnesota, 90L1
USA) was drilled with a hand-set diamond (carbonados) crown.
1894 Moissan claimed to have produced diamonds using his newly developed 1894M
electric arc furnace.
(Both the above Hannay and Moisson claims not substantiated) 63S
1907 Diamonds used in industry as wire-drawing dies for the production of fine 92Kl
tungsten wire required for electric light bulbs
1932 Metal bonded diamond grinding wheels introduced 70I
1933 Resin bonded diamond grinding wheels introduced 33W
1947 Bridgman reached temperatures and pressures which retarded the diamond 47B
to graphite reaction but could not produce diamond.
1953 Liander and Lundblad produced diamonds at the ASEA Laboratory 60L, 90L2
(Sweden) using the HPHT process.
1955 Berman and Simon produced a pressure-temperature equilibrium diagram 55B1
for diamond/graphite.

13-2 13 Hard materials [Ref. p. 13-185

1955 Scientists, notably Marshall, Nerad, Bundy, Strong, Hall, Wentorf, 55B2,
Bovenkerk and Cheney, at the General Electric Company, 94B2,
USA Laboratory, disclosed that they had produced diamonds using the 96G1
HPHT process and gave a description of a defined, reproducible
scientifically established process which led to the granting of patents.
1957 - 59 The first Man-Made1 diamonds were being produced by a controlled 90G, 94S,
HPHT process on a commercial basis. Transformation of hexagonal 57W
boron nitride to the hard cubic form achieved by R. H. Wentorf, Jr.,
at the General Electric Company, USA.
1960 - 65 New “types” of diamond were being commercially produced to match 90G, 94S,
application requirements. Control of crystal friability (toughness) could be 99B2
achieved.
1966 - 70 Metal coated diamond crystals were produced to assist in crystal retention 90G, 94S,
within resin bonds of grinding wheels, cubic boron nitride (CBN) crystals 96G1,
produced on a commercial scale for use in grinding wheels. 99B2, 68D
Polyimide resin introduced as a bond in diamond grinding wheels.
1971 - 75 Polycrystalline diamond products were introduced for the machining of 90G, 96G1,
non-ferrous and non-metallic materials. Similar products, based on CBN, 99B2,
were also introduced for the machining of hardened ferrous materials. 72S1, 73D,
Large single diamond crystals could be produced by the HPHT process 81S
using polycrystalline diamond as a carbon source and seed diamonds.
Russian scientists, notably Derjaguin and co-workers reported, in 1973, on
the deposition of diamond from the gas phase using a chemical vapour
deposition (CVD) technique.
1976 - 80 Improved diamond crystals with very defined structures and properties 90G, 96G1,
were produced to correspond to the specific requirements of individual 99B2
applications, e.g. grinding hardmetal-steel combinations, metal bond
sawing and drilling, electroplated tools etc.
Polycrystalline drill blanks mounted on a hardmetal support were
introduced for use in oil-well drilling and mining applications.
1981 - 85 Thermally stable drill blanks (polycrystalline) were introduced for coring 90G, 96G1,
bits. Improvements in the consistency of the properties of diamond crystals 90B, 82M
continued. Japanese scientists, notably Matsumoto and co-workers,
reported in 1982 that they had confirmed the earlier work of the Russians in
relation to the CVD process.
1986 - New grades of polycrystalline CBN containing a proportion of a ceramic, 96G1, 90B
to widen the application range, were introduced. Grading and definition of
diamond shape, particularly in the application area of sawing and grinding,
produced a range of crystals with superior crystal morphology. Special
coatings of diamond crystals were developed to enhance chemical bonding
and retention in metal matrix (bonds) tools.
In 1992 - 1993 CVD diamond products for cutting tools, wire drawing dies 92J, 92S2,
and free-standing pieces for optical and electronic applications became 93G1,
commercially available. 93S2,
94G1,
94G2,
98C1, 99B2
A more detailed account of diamonds, particularly their properties can be found in the following
references [92F, 79F].
1
Trademark of the General Electric Company, USA.

13.1.2 Hardmetal
As with many advances in science, the initial discovery was not the result of a specific experiment with
that advance in mind. So it was with the origin of hardmetal - an alloy of tungsten carbide and cobalt.
Experiments leading up to the breakthrough can be traced back to the initial work of Moissan, Paris,
[1897M] with his newly invented electric arc furnace. In the first instance he produced di-tungsten
carbide - W2C - and then later with Williams [1898W], working in the same laboratory, produced
tungsten mono-carbide - WC. Having reported that this carbide was extremely hard but brittle, various
workers, mainly in Germany, proceeded to attempt to produce practical tools. However, it was not until
scientists, at the Osram Studiengesellschaft für elektrische Beleuchtung, Berlin, working with tungsten
carbide powder, made the breakthrough, by adding a small account of cobalt to act as a binder. Thus,
"hardmetal" was born. A patent [23S] was applied for by Schröter (Osram) in 1923 and was awarded in
1925. Other workers at the laboratory, notably Skaupy, Fehse & Mathieu [92K1] were also involved. The
driving force was to produce a substitute for diamond wire-drawing dies for the production of fine
tungsten wire needed for electric light bulbs. This was achieved when hardmetal dies were satisfactorily
tested in the Osram works. The patent along with others, were purchased in 1925 by Fried. Krupp GmbH,
who then embarked upon the full commercial exploitation of the material named Widia2. Table 2
continues with some of the major advances in the development of the alloys with the generic term - hardmetal.
Table 2. Chronological order of the evolution of hardmetal.
Date Event Ref.

1923 - 25 K. Schröter granted the first patent for the production of hardmetal - a WC-Co alloy 23S, 25S,
by a powder metallurgy process 32S
1927 - 31 Krupp Widia N hardmetal was exhibited at the 1927 Leipzig Spring Fair cutting a 92KI
hard cast iron at speeds of up to 2 to 3 times those normally used.
A WC-TiC-Co Widia1, alloy was produced in 1931 especially for cutting steel.
Schwarzkopf-Metallwerk Plansee, Austria, was granted a series of patents for the 29S
production of homogeneous "mixed crystals" – alloys of carbon atoms and two or
more metal atoms.
Fansteel, USA, introduced the first tungsten free hardmetal based on TaC-Ni. 71L1
1932 - 39 WC-Co alloys with cobalt contents of up to 15 wt% were introduced by Krupp for a 51A
wider range of application.
A range of new WC-TiC-Co steel cutting alloys was introduced by Krupp 55D, 51A
The first fine grain WC-Co alloy to contain a grain growth inhibitor - VC and TaC - 95S
was produced by Krupp in 1939
McKenna, USA, (later to be Kennametal) was granted patents for the production of 38M
"mixed crystals" by the menstruum process.
He was also granted a patent for the pressing of complicated forms using the cold- 40M
isostatic pressing method and resilient moulds.
1940 - 50 Armour piercing shot manufactured from hardmetal alloys was extensively 85S1
produced during the period 1941 - 45.
In the latter part of this period Sandvik in conjunction with Atlas-Diesel developed a 87T
revolutionary rock drilling system based on WC-Co hardmetal tipped chisel bits
attached to light-weight, high frequency pneumatic hammers.
McKenna and co-workers were granted a patent for clamped indexable insert cutting 48M
tools in 1948.
This period saw the rapid advance in grades of hardmetal for the mining and coal
industries.
2
Trade name of Widia GmbH, Germany.

Date Event Ref.

1951 - 60 In 1951 Trent published the first paper dealing with the metallurgy of metal cutting. 51T
Brazed tools were superseded by the rapid extension of the use of indexable inserts
in metal cutting in the USA.
Large dies and anvils were produced for the high-pressure systems used to
synthesise diamonds.
1961 - 70 Many new “high-quality” premium grades of WC-TiC-TaC (NbC)-Co alloys were
produced for the rapidly expanding indexable-insert market.
Suzuki and Kubota published in 1966 clear evidence of the importance of carbon 66S
content on the strength of hardmetal.
Kennametal (1967 - 68) introduced Hot-Isostatic-Pressing (HIP) for the processing 83G1
of fully sintered components in order to reduce porosity to virtually zero, under the
trade name Keziz3.
In the period 1968 - 69 Krupp and Sandvik introduced TiC coated indexable cutting
inserts.
The process Chemical Vapour Deposition (CVD) was based on a patent granted to 60R
Rupert and Schwedler and work carried out at LSRH, Switzerland, under the
direction of Hintermann, respectively. This was a major milestone in the
development of hardmetal.
1971 - 80 Lux et al. were granted a patent, 1971, for the deposition of Al2O3 by the CVD 71L2
process. Commercial coated grades were launched by Carboloy (1971), Sandvik
(1974), Krupp (1978).
Schintlmeister was granted a patent (1973) for the CVD coating of a multiple layer 73S
composed of an initial layer of TiC, followed by a Ti(CN) intermediate layer and
finally a TiN outer layer.
The first papers on Physical Vapour Deposition (PVD) appeared in the early 70's. 72B
In 1972, Wimet introduced new sub-micron WC-Co alloys. 95S
Sumitomo introduced an ion-plating (PVD) process for coating hardmetal inserts 78H
with TiC and TiN in 1978.
Suzuki et al. published, in 1972, a detailed investigation into the influence of grain 72S2
growth inhibitors.
1981 - 90 In 1983 - 84 the first commercial Sinter-HIP furnaces became available, although 83L
the process had been declared much earlier. 83G2
Grab and Nemeth were granted a patent (1982) disclosing the enrichment of the 68S
outzone of a hardmetal insert, with binder phase by the addition of Group IVB or 82G
VB transition nitrides, hydrides or carbonitrides to the initial powder mix. 88A1
About 1985, improvements in the quality of coated indexable cutting inserts became
evident. Grades with multiple layers appeared.
Chip control surfaces on coated cutting inserts became very complex.
Japanese hardmetal manufacturers began to offer ultra-fine (> 0.5 µm) grain size 89E1
WC-Co alloys, especially for the production of micro-drills.
1991 - Many variations in coating techniques were developed to reduce stresses in the 97D2
coatings.
Nanostructured WC-Co hardmetals were produced by novel techniques. These 96M1
produced alloys with exceptional mechanical properties. 97J1
The now ubiquitous hardmetal alloys were being produced in an extremely wide
range of composition and grain size to suit the ever increasing service demands.
3
Trade name of Kennametal Inc., USA.

Date Event Ref.

Components were also being produced over an ever widening size range – from
balls (< 1 g) for ball-point pens, micro-drills (0.3 mm dia.) to very large anvils and
dies (> 250 kg) - for the synthesis of diamond. Every industry had a demanding
niche for a hardmetal part.
For an expanded view of the development of hardmetal alloys the following
references should be consulted: [97D2, 86B, 83G2, 82L, 79E]. A comprehensive
review of all matters pertaining to hard materials, including a complete list of
manufacturers and grades is included in the following reference [96B2]. A practical
review of hard materials is given in reference [88S1].
13.1.3 Cermets
The name "cermets" was developed from the desire to express a generic term for a group of alloys which
were composed of part cer (-amic) and part met (-al). Although the alloys based on tungsten carbide and
cobalt should be included in this term, its use has generally been confined to those based on titanium
carbide / titanium carbonitride bonded with cobalt / nickel with possible additions of other carbides. The
main area of application has been in high-speed metal cutting.
The initial alloys were developed by Schwarzkopf and Hirschl of Plansee [31S] in 1930/31 and were
to some degree formulated to avoid existing Krupp patents. Problems with inherent brittleness and
difficulties in brazing severely hampered their adoption as cutting tool materials.
The following Table 3 details some of the important steps in the evolution of these alloys.
Table 3. Chronological order of the development of cermets.

1930 - 31 Schwarzkopf and Hirschl of Metallwerk Plansee obtained a patent for 31S
the first cermet alloy - Titanit S - 42.5 % Mo2C - 42.5 % TiC - 14 % Ni
- 1 % Cr.
1938 - 45 Based on work by Kieffer and Hotop, Krupp produced an alloy based 55D, 51A
on titanium carbide and vanadium carbide with a complex binder of
iron and nickel with a small addition of chromium carbide by hot-
pressing in graphite dies.
1949 - 59 In 1950, Trent, Carter and Bateman published results on the high 50T
temperature properties of titanium carbide - cobalt / nickel - small
additions of chromium carbide alloys. It was proposed that they could
possibly be used in the then new jet engines. However, the inherent
brittleness of the material resulted in failure.
Kennametal released data in 1949 regarding alloys based on titanium
carbide, tantalum carbide, niobium carbide with a cobalt / nickel binder.
1960 - 69 In this period renewed interest in cermets was aroused by work 61H, 66M
published by Moskowitz and Humenic of the Ford Motor Co. The
development, was based on the choice of raw materials to improve the
wetting and bonding of the titanium carbide grains. Although the
strength of these alloys was improved, chipping and notching during
cutting was still a major problem.


1970 - 90 Kieffer, Ettmayer and co-workers (1968 - 70) showed that titanium 71K
nitride and titanium carbonitride could be used as the hard phase in
alloys, which had molybdenum or molybdenum carbide added to the
nickel binder phase, to improve wetting characteristics.
A so-called “spinoidal” cermet was developed by Rudy about 1973. 73R
This was based on research into the quaternary systems of Ti-Mo-C-N
and Ti-W-C-N. Despite improved physical properties, only restricted
use was made of these alloys in Europe and the USA.
However, in Japan, a considerable amount of research was concentrated
on these new cermets.
In 1977 Toshiba Tungalloy was granted a patent for a cermet based on 77Y
TiC-TaC-WC-ZrC-(Ni-Mo-Co) alloys.
The Ford Motor Co. Ltd, through Moskovitz and Humenic was still 80F
active in the field of cermets and was granted a patent for TiC-TiN-VC-
Mo2C-(Ni-Mo-Al) alloys.
The complexity of the alloys increased and additions of tantalum nitride 82H
were made to the now basic (TiCN) hard phase.
Mitsubishi, through Nishigaki and Urawa, in 1978, were granted a 78N
patent concerning an alloy composition which resulted in the formation
of a complex precipitation in the binder phase.
Research work by Kolaska and Ettmayer in 1988 showed that extremely 88K1
tough cermets could be produced by the addition of non-conventional
aluminum containing complex carbides / nitrides. The alloys had a
composition based on (Ti, Ta, Nb, V, Mo, W) (CN)-Ni-Co-Ti2AlC.
Based on this work Krupp Widia introduced two new cermets TTI4 and 88E
TTI-151.
The research work continued unabated in Japan and in 1988 - 89 89S2
Sumitomo introduced cermets with double the amount of nitrogen
(5 - 6 %) compared with previous grades (2 - 3 %).
The use of cermet alloys in Japan in 1988 increased to 25 - 27 % of the
domestic metal cutting market. They were especially suitable for high-
speed, light finishing metal cutting operations.
1990 - PVD and PCVD coating techniques were applied to selected cermets to 93K
improve cutting efficiency.
Sub-micron grained cermets were produced by scientists at Mitsubishi 97N
with improved wear resistance and toughness as determined by a
variety of cutting tests.
Further information on the development of cermets can be obtained by consulting the following
references [88E, 89E2, 94K, 97D1].
13.2 Raw materials used in the production of hard materials

Of the many forms of carbon, required as the raw material for the conversion to diamond, graphite is the
most commonly used. Properties of a typical material are shown in Table 4.
4
Trademark Widia GmbH, Germany.


1970 - 90 Kieffer, Ettmayer and co-workers (1968 - 70) showed that titanium 71K
nitride and titanium carbonitride could be used as the hard phase in
alloys, which had molybdenum or molybdenum carbide added to the
nickel binder phase, to improve wetting characteristics.
A so-called “spinoidal” cermet was developed by Rudy about 1973. 73R
This was based on research into the quaternary systems of Ti-Mo-C-N
and Ti-W-C-N. Despite improved physical properties, only restricted
use was made of these alloys in Europe and the USA.
However, in Japan, a considerable amount of research was concentrated
on these new cermets.
In 1977 Toshiba Tungalloy was granted a patent for a cermet based on 77Y
TiC-TaC-WC-ZrC-(Ni-Mo-Co) alloys.
The Ford Motor Co. Ltd, through Moskovitz and Humenic was still 80F
active in the field of cermets and was granted a patent for TiC-TiN-VC-
Mo2C-(Ni-Mo-Al) alloys.
The complexity of the alloys increased and additions of tantalum nitride 82H
were made to the now basic (TiCN) hard phase.
Mitsubishi, through Nishigaki and Urawa, in 1978, were granted a 78N
patent concerning an alloy composition which resulted in the formation
of a complex precipitation in the binder phase.
Research work by Kolaska and Ettmayer in 1988 showed that extremely 88K1
tough cermets could be produced by the addition of non-conventional
aluminum containing complex carbides / nitrides. The alloys had a
composition based on (Ti, Ta, Nb, V, Mo, W) (CN)-Ni-Co-Ti2AlC.
Based on this work Krupp Widia introduced two new cermets TTI4 and 88E
TTI-151.
The research work continued unabated in Japan and in 1988 - 89 89S2
Sumitomo introduced cermets with double the amount of nitrogen
(5 - 6 %) compared with previous grades (2 - 3 %).
The use of cermet alloys in Japan in 1988 increased to 25 - 27 % of the
domestic metal cutting market. They were especially suitable for high-
speed, light finishing metal cutting operations.
1990 - PVD and PCVD coating techniques were applied to selected cermets to 93K
improve cutting efficiency.
Sub-micron grained cermets were produced by scientists at Mitsubishi 97N
with improved wear resistance and toughness as determined by a
variety of cutting tests.
Further information on the development of cermets can be obtained by consulting the following
references [88E, 89E2, 94K, 97D1].
13.2 Raw materials used in the production of hard materials

Of the many forms of carbon, required as the raw material for the conversion to diamond, graphite is the
most commonly used. Properties of a typical material are shown in Table 4.
4
Trademark Widia GmbH, Germany.

Table 4. Chemical and physical properties of graphite used for conversion to diamond, Timrex SD 755
special graphite.
Guaranteed values
0.05 % max Ash
0.2 % max Moisture
100 nm min Crystallite height
0.3354 - 0.3358 nm Interlayer distance
85 % min (Laser) Particle size < 64 µm
16 - 23 µm d50
Typical values
Purity Crystallinity
0.016 % Ash > 100 nm LC
5 ppm Al 0.3355 c/2
30 ppm Ca Density
10 ppm Fe 2.25 g/cm3 Xylene
35 ppm Si 0.23 g/cm3 Scott
2 ppm Ti
1 ppm V
10 ppm S
Particle size distribution (laser diffraction) [µm]
1% <2
5% <4
18 % <8
44 % < 16
73 % < 32
88 % < 48
91 % < 64
100 % < 128
d50 19 µm
In the case of the HTHP conversion process for the formation of cubic boron nitride the raw material
commonly used is a high quality hexagonal boron nitride, such as that described in Table 5.
Table 5. Chemical and physical properties of hexagonal boron nitride used for conversion to cubic boron
nitride.
SHP-6106 combat boron nitride powder.

BN Ca O2 C Si Other Tracer B2O3
inorganic metals (not part of the chemical
analysis)
wt% wt% wt% wt% wt% ppm ppm wt%
99.5 0.02 0.3 0.04 0.005 0 - 10 0 - 10 0.03 max
Mean particle size Surface area Apparent density Tap density

µm m2/g g/cm3 g/cm3
5 - 10 5.76 0.21 0.38
5
Trademark and data from Timcal Ltd. CH-5643 Sins, Switzerland.
6
Trademark and name of Carborundum Corp., Boron Nitride Division, Amherst, N. York, USA.

13.2.2 Hardmetals
13.2.2.1 Production of ammonium paratungstate (APT)
There are two main ores of tungsten - woframite, (FeMn)WO4 and scheelite, CaWO4. Within the
wolframite term there are two minerals representing the iron - rich end - ferberite and the manganese -
rich end - hübnerite. The analysis of a range of high grade concentrates from both mineral types is given
in Table 6 [79Y].
Tungsten scrap is also a valuable source of tungsten for processing. Soft scrap is initially oxidised
while hard scrap is processed via an alkaline fusion step.
All these raw materials are processed to yield a very pure form of monoclinic white crystalline
ammonium paratungstate - (NH4)10 H2W12O42⋅4H2O in short APT as shown in Fig. 13.1 [95V]. Impurities
in high purity APT are at the level of 10 ppm or less for the following elements: Al, As, Ba, Ca, Cr, Cu,
Fe, K, Mg, Mn, Mo, Na, Ni, P, Si and Sn [95L1].
13.2.2.2 Production of tungsten metal
It is usual to calcine the APT by heating in a closed rotary furnace in the temperature range 400 - 800 °C.
Depending upon the temperature, time and atmosphere conditions within the furnace, the end product
may be tungsten oxide WO3 or the so-called blue oxide.
Table 6. Composition of high grade ore concentrates [79Y].
Scheelite [%] Wolframite [%]

WO3 66 - 72 60.5 - 65.8
(theor. 80.52) (theor. 76.34 Fe, 76.57 Mn)
CaO 10 - 20.3 2.14 - 2.30
(theor. 19.48)
Mg 0.03 - 0.84 0.04
B < 0.001 - < 0.01 0.005
Al 0.22 - 2.0 0.40 - 1.17
Si 0.77 - 2.94 1.36 - 2.73
Sn < 0.01 - 3.00 1.00
Pb 0.025 - 0.25 0.066
P 0.008 - 0.17 0.014 - 0.22
As 0.0066 - 0.17 0.058 - 1.00
Bi 0.006 - 0.10 0.045 - 0.20
S 0.056 - 0.41 0.50 - 1.10
Ti < 0.001 - 0.075 0.23
V < 0.004 - 0.01 0.015
Cr < 0.001 - 0.008 < 0.005 - 0.008
Mo < 0.01 - 2.00 < 0.003
MnO 0.052 - 0.654 2.53 - 10.8
(theor. 23.43)
FeO 0.28 - 3.74 13.2 - 17.0
(theor. 23.66)
Co < 0.005 0.05
Cu < 0.025 - 0.10 0.39 - 0.75
Ni 0.003 - 0.01 0.01
This latter material is chemically complex and may contain a number of oxides - WO3, W20O58, W18O47 -
together with ammonium and hydrogen tungsten oxide bronzes [95L2]. However, this is usually the
starting material of choice for the production of tungsten metal powder.

Reduction at an industrial level is carried out either in a pusher type furnace (boats containing blue oxide
being pushed through a hot zone with a counter current flow of hydrogen), or in a rotary furnace (the blue
oxide tumbles in spiral flow within the hot furnace tube with a counter current flow of hydrogen) [97L1].
Depending upon the reduction conditions, e.g. temperature (600 - 1100 °C), dwell at temperature,
hydrogen flow rate, moisture content of the hydrogen, depth of blue oxide bed etc., tungsten powder with
an average grain size between 0.2 µm to 60 µm may be obtained [83H, 90S1]. A schematic scheme of the
influencing factors is shown in Fig 13.2 [83H].
A typical range of commercially available tungsten metal powders is shown in Table 7.
Table 7. Typical range of tungsten metal powders.
Grade7 Grain8 size FSSS range of Impurities

FSSS target value Al Ca Co Fe Mo Ni O S Si
µm µm ppm
W05-10 0.50 - 0.99 ± 0.05 < 20 < 20 < 10 < 40 < 100 < 10 < 3500 < 20 < 30
W10-25 1.00 - 2.49 ± 0.08 < 20 < 20 < 10 < 50 < 100 < 10 < 2500 < 20 < 30
W25-50 2.50 - 4.99 ± 0.15 < 20 < 20 < 10 < 50 < 100 < 10 < 1500 < 20 < 30
W50-120 5.00 - 12.0 ± 0.5 < 20 < 20 < 10 < 100 < 100 < 20 < 500 < 20 < 30
As well as FSSS average grain size, the grain size distribution is extremely important in controlling the
future processing parameters and the final grain size of the hardmetal end product. Typical distribution
curves for a powder in the W05-10 range and for one in the W50-120 range are shown in Figs. 13.3 and
13.4, respectively.
13.2.2.3 Production of tungsten carbide
The production of tungsten carbide powder commences with the selection of a high purity form of carbon
or graphite as shown in Table 8 and Table 9.
Table 8. Physical and chemical properties of Cancarb9 Thermax N-990 UP and N-991 UP carbon
[flowform (pelletized) and powder respectively].
Thermax ultra pure flowform Thermax ultra pure powder

Min. carbon content [%] 99.6 99.6
Sulphur content [ppm] < 10 < 10
Max. ash content [%] < 0.02 < 0.02
Mean particle diameter [nm] 270 270
Particle diameter range [nm] 80 - 580 80 - 580
Nitrogen surface area [m2/g] 8.5 8.5
Iodine absorption no. [mg/g] 8 - 11 8 - 11
Pellet size distribution
+ 10 mesh [%] 0.0 -
10 x 12 mesh [%] 0.0 -
12 x 14 mesh [%] 0.0 -
14 x 18 mesh [%] 1.5 -
18 x 35 mesh [%] 34.5 -
35 x 60 mesh [%] 53.7 -
60 x 120 mesh [%] 7.4 -
−120 mesh 2.9 -
7
Trademark and data from Wolfram Bergbau- und Hüttengesellschaft mbH, Austria
8
Fisher Sub-Sieve Sizer, ASTM B330-82
9
Trade name and data from Cancarb Ltd., Medicine Hat, Alberta, Canada.

Thermax ultra pure flowform Thermax ultra pure powder

Pellet hardness (14 x 18mesh)
High [g] 50 -
Low [g] 5 -
Average [g] 20 -
Max. toluene extractables [%] 0.35 0.35
Apparent density [lbs/ft3] 40 22
[g/cm3] 0.64 0.35
Max. moisture [%] 0.1 0.1
Max. sieve residue [%]
35 mesh 0.001 0.001
325 mesh 0.02 0.02
Trace elements [ppm] [ppm]

Al <5 <5
As <2 <2
B <1 <1
Ca 4 4
Cr <1 <1
Cu <1 <1
Fe 10 10
Ga <3 <3
Mg 2 2
Pb <5 <5
Si 10 10
Na 8 8
Ti <5 <5
V <5 <5
Ni <1 <1
Zn 2 2
Table 9. Physical and chemical properties of Timcal, Timrex KS75 Graphite Powder10.
Guaranteed values
0.1 % max Ash
0.5 % max Moisture
100 nm min Crystallite height
0.3354 - 0.3358 nm Interlayer distance
95 % min (Laser) Particle size < 96 µm
95 % min (Airjet) Particle size < 75 µm
10
Trade name and data from Timcal Ltd., CH-5643 Sins Switzerland.

Typical values
Purity [ppm] Crystallinity
0.07 % Ash > 100 nm LC
0.1 % Moisture 0.3355 nm c/2
13 Al Density
< 0.5 As 2.235 g/cm3 Xylene
155 Ca 0.23 g/cm3 Scott
<1 Co Specific surface area
<1 Cr 6.5 m2/g BET
<1 Cu Particle size distribution
36 Fe (laser diffraction)[%] [µm]
<1 Mo 0.9 <2
1 Ni 4.6 <4
<1 Pb 16 <8
< 0.1 Sb 37 < 16
110 Si 65 < 32
7 Ti 84 < 48
4 V 89 < 64
40 S 100 < 128
d50 22.3 µm
The selected material is then ball milled with the appropriate tungsten metal powder to ensure intimate
mixing of the two constituents. It is usual to add slightly more carbon than the theoretical carbon value of
6.13 wt% - of the order of 6.15 - 6.18 wt%.
Heating of the mixture is carried out, in the temperature range 1350 °C (fine WC) to 1750 °C (coarse
WC), in either a carbon tube resistance furnace under hydrogen or a vacuum induction furnace. The
former is more usual. Carburisation occurs through the gas phase as follows:
2W + 2CO → W2C + CO2 (1)

W2C + 2CO → 2WC + CO2 (2)
and
2W + CH4 → W2C + 2H2 (3)
W2C + CH4 → 2WC + 2H2 (4)
The process proceeds, in the solid phases, as shown in Fig. 13.5 [87Z]. The tungsten-carbon equilibrium
diagram is shown in Fig. 13.6 [69R].
A typical range of available tungsten carbide powders is shown in Table 10.
The grain size distribution of the various tungsten carbide powders is extremely important and modern
commercial production processes are aimed at manufacturing grades with as narrow a distribution as
possible. This is particularly important for the sub-micron and ultra-fine types. Distribution curves for a
type WC05-06 and a WC50-120 are shown in Fig. 13.7 and 13.8, respectively.

Table 10. Typical range of tungsten carbide powders.
Grade11 Grain size FSSS Total Free carbon Impurities

FSSS range of carbon max at
target range of 6.13 % total
value target value carbon Al Ca Co Fe Mo Ni O S Si
µm µm % % ppm
WC05-06 0.5 - 0.6 - ±0.03 0.04 < 20 < 20 < 100 < 200 < 100 < 30 < 3500 < 20 < 30
WC06-10 0.61 - 0.99 ±0.03 ±0.03 0.04 < 20 < 20 < 100 < 200 < 100 < 30 < 3000 < 20 < 30
WC10-15 1.00 - 1.49 ±0.05 ±0.03 0.04 < 20 < 20 < 300 < 300 < 100 < 20 < 2000 < 20 < 30
WC15-50 1.50 - 4.99 ±0.15 ±0.03 0.04 < 20 < 20 < 300 < 200 < 100 < 20 < 1500 < 20 < 30
WC50-120 5.0 - 12.0 ±0.5 ±0.03 0.04 < 20 < 20 < 200 < 200 < 100 < 20 < 1000 < 30 < 30
V46, HT-WC - - 6.17±0.03 0.07 max < 20 < 20 < 100 < 100 < 100 < 10 < 600 < 20 < 30
8µm
V3M, HT-WC - - 6.17±0.03 0.10 max < 20 < 20 < 20 < 1100 < 100 < 10 < 400 < 20 < 30
12µm
V49, HT-WC - - 6.16±0.05 0.10 max < 20 < 20 < 20 < 150 < 100 < 10 < 200 < 20 < 30
25µm
V163, HT-WC- - 6.15±0.05 0.10 max < 20 < 20 < 30 < 300 < 100 < 10 < 200 < 20 < 30
50µm
Note (1) WC05-06 doped with Cr3C2 , VC or TaC as per customer

(2) WC06-10 doped with Cr3C2 , VC or TaC as per customer
(3) WC10-15 standard undoped but may be doped as per customer
(4) HT-series produced at a high temperature from tungsten metal powder with a grain size of
8 µm, 12 µm, 25 µm and 50 µm, respectively.
13.2.2.4 Production of cobalt
There is a number of cobalt ores which are used for the extraction and recovery of cobalt:
- sedimentary hydro-thermal cobalt bearing copper ore
- liquid magma-based nickel-copper seams
- oxide and silicate nickel laterite deposits
The former ore type is mined in Zambia and Dem. Rep. Congo and the process for refining this material
is shown in Fig. 13.9 [95K1].
Cobalt metal powder, suitable for hardmetal (and cermet) production, is obtained by one of the following
routes:
(1) Reduction of cobalt oxide, Co3O4 under hydrogen at temperatures in the region of 350 - 500 °C.
(2) Decomposition of cobalt oxalate di-hydrate, CoC2O4 - 2H2O, under a reducing atmosphere at temper-
atures of ca. 500 - 600 °C [75T].
(3) A process based on the reduction of cobaltous hydroxide by a mixture of ethylene glycol and di-
ethylene glycol at 210 °C [92P].
(4) The reduction at 175 - 205 °C, at a pressure of 3.1 MPa under hydrogen, of a complex cobaltous
solution [80C].
A range of cobalt metal powders used in the hardmetal and cermet industry is shown in Tables 11 and 12.
11
Trademark and data from Wolfram Bergbau- und Hüttengesellschaft mbH, Austria.

Table 11. Physical and chemical properties of cobalt metal powder.
Grade12 FSSS App. Impurities (typical values)

density Ni Fe Mn Cu Pb Zn Si Ca Mg Na S C O2
µm g/cm3 ppm
Extra fine 1.2 - 1.5 0.9 - 1.3 500 50 < 10 30 < 10 30 < 20 30 < 10 20 < 10 < 50 3500
Submicron 0.8 0.8 500 70 < 10 20 < 10 20 < 20 70 30 60 < 10 1000 8000
Table 12. Physical and chemical properties of cobalt metal powder.
Grade13 Particle size Coating Wax Impurities (typical values)

measured by agent content
SEM content Ca Cu Fe Mg Mn Na Ni S Si Zn
µm % % ppm
Submicron 0.4 2 2 < 5 10 < 5 < 5 < 5 < 50 600 20 20 < 10
type Co 9115
13.2.2.5 Production of titanium carbide
Titanium carbide is manufactured by the high temperature, ca. 2000 - 2200 °C, reduction and
carburisation of a mixture of high purity titanium di-oxide, TiO2, and carbon black or graphite powder
(see Table 8 and Table 9) in a vacuum induction furnace. The reduction and carburising processes
proceed in a stepwise manner with the formation of a series of oxides, e.g. Ti3O5, Ti2O3. Traces of oxygen
and nitrogen are bound to the titanium carbide in the form of a mixed crystal Ti (C, O, N) [96B1].
The titanium-carbon equilibrium diagram is shown in Fig. 13.10 [67S1]. A typical range of titanium
carbide powders commercially available is shown in Table 13.
Table 13. Physical and chemical properties of titanium carbide powder14.
FSSS Total carbon Free carbon Impurities (max)

µm % % ppm
min. max max Al Ca Fe N Si O2
1.2 - 1.4 19.0 19.9 0.50 50 50 300 2000 100 8000
1.4 - 2.0 19.0 19.9 0.50 50 50 300 2000 100 6000
2.0 - 3.0 19.0 19.9 0.50 50 50 300 2000 100 4000
13.2.2.6 Production of tantalum (niobium) carbide
The production of tantalum carbide follows the route of many other carbides, i.e. the simultaneous
reduction and carburising of the metal oxides with carbon. In the case of the tantalum pentoxide, Ta2O5,
there is invariably some niobium pentoxide, Nb2O5, present, due to their physical association in the ore.
The respective quantities of the pentoxide and pure carbon black or graphite powder (see Table 8 and
Table 9) are intimately mixed and then the mixture is heated to a temperature of 1400 - 1800 °C either
under hydrogen or a vacuum. By the selective choice of raw materials and carburising conditions sub-
micron powders with a narrow particle size range may be produced [91S].
The tantalum-carbon equilibrium diagram is shown in Fig. 13.11 [67S1] while Table 14 gives details
of the range of commercially available powders.
12
Trademark and data supplied by Union Miniere, Cobalt and Energy Products, Olen, Belgium.
13
Trademark and data supplied by Eurotungstene Metal Powders, Grenoble, France (Spherical Co particles coated
with a special agent and bonded together with wax).
14
Data supplied by Treibacher Industrie AG, Treibach, Austria.

Table 14. Physical and chemical properties of tantalum (niobium) carbide powder
Grade15
TaC TaNbC TaNbC TaNbC TaNbC NbC
100 90/10 80/20 60/40 50/50 100
Total carbon [%] 6.15 - 6.30 6.60 - 6.80 7.15 - 7.35 8.00 - 8.50 8.60 - 8.80 11.0 - 11.3
Free carbon [%] 0.15 max 0.15 max 0.15 max 0 - 15 max 0.15 max 0.15 max
Nb [%] 0.25 max 8.9 - 9.6 17.5 - 18.2 33.0 - 36.0 43.8 - 45.0 -
Ta [%] - 83.5 - 84.5 74.3 - 75.0 55.5 - 59.0 46.2 - 47.6 0.25 max
All grades with FSSS particle size: 0.8 - 1.3 µm 0.35 % O2 (max)
1.3 - 3.0 µm 0.20 % O2 (max)
Impurities all grades (max) [ppm]
Al Ca Fe N Si Ti
50 50 300 500 50 500
13.2.2.7 Production of vanadium carbide
The production of vanadium carbide follows the same route as for tantalum carbide, namely intimate
mixing of the pentoxide, V2O5, with pure carbon black or graphite powder (see Table 8 and Table 9) in
the appropriate quantities. Carburising follows at a temperature of ca. 1700 °C under a vacuum. It is
difficult to remove traces of oxygen and nitrogen as they form a stable mixed crystal, V (C, O, N).
The vanadium-carbon equilibrium diagram is shown in Fig. 13.12 [67S1]. The physical and chemical
properties of a commercially available powder is shown in Table 15.
Table 15. Physical and chemical properties of vanadium carbide powder.
Fine grade16 Standard grade16

Total carbon [%] 17.2 - 18.2 16.5 - 17.2
Free carbon (max) [%] 1.5 0.15
O2 (max) [%] 0.80 0.50
FSSS [µm] 0.9 - 1.4 1.5 - 2.5
Impurities (max) [ppm]

Al Ca Fe N Si
50 50 1000 1000 100
13.2.2.8 Production of chromium carbide
The chromium oxide, Cr2O3, is mixed with the appropriate quantity of pure carbon black or graphite
powder (see Table 8 and Table 9) to form an intimate mixture. This is heated to ca. 1600 °C under a
reducing atmosphere of hydrogen in a carbon tube resistance furnace. The chromium-carbon equilibrium
diagram shows three carbides - Cr23C6, Cr7C3 and Cr3C2 each with a very narrow carbon range. The Cr3C2
carbide is the one used in the hardmetal industry. A typical commercially available powder is shown in
Table 16.
Table 16. Physical and chemical properties of chromium carbide powder
Grade16 FSSS [µm] Total carbon [%]

Cr3C2160 ≤ 1.6 ≤ 13.3
15
Trademark and data supplied by Treibacher Industrie AG, Treibach, Austria.
16
Trademark and data supplied by H.C. Starck GmbH & CoKG, Goslar, Germany.

13.2.2.9 Production of carbide mixed crystals (mixed carbides)
Certain hardmetal alloys require additions of titanium carbide, tantalum (niobium) carbide or
combinations of both to the basic tungsten carbide-cobalt alloy. This can be made using the individual
carbides but it is more usual to use a so-called mixed crystal of the appropriate carbides. This is
manufactured using similar techniques to those used for the individual carbides. Thus, for tungsten
carbide-titanium carbide mixed crystal a mixture of tungsten metal powder, titanium dioxide, and carbon
black or graphite powder is prepared and heated to ca. 1900 °C under hydrogen. This material is broken-
down and re-carburised under vacuum at 2100 - 2200 °C to yield a typical 70 wt% WC-30 wt% TiC or a
50 wt% WC-50 wt% TiC mixed crystal. This method can be used to produce ternary mixed crystals of
WC-TiC-Ta(Nb)C. A typical range of mixed crystals is shown in Table 17 and 18.
Table 17. Physical and chemical properties of WC - TiC mixed crystal powder
Grade17
WC/TiC 70/30 WC/TiC 50/50
Total carbon [%] 9.7 - 10.2 12.5 - 13.0
Free carbon [%] 0.30 max 0.30 max
W [%] 64.5 - 66.0 46.0 - 47.5
Ti [%] 24.0 - 25.5 39.5 - 41.0
Within the two compositional grades, a choice of three grain size powders is available:
Particle size FSSS [µm] Oxygen [%]

1.2 - 1.5 0.50 max
1.5 - 2.0 0.35 max
2.0 - 2.5 0.25 max
Impurities of all grades (max) [ppm]

Al Ca Fe N Si
50 50 300 1000 50
Table 18. Physical and chemical properties of WC-TiC-TaC and WC-TiC-TaC-NbC mixed crystal powder
Grade17
WC/TiC/TaC : 50/30/20 WC/TiC/TaC/NbC : 33/33/26/8
Total carbon [%] 9.7 - 10.2 10.8 - 11.1
Free carbon [%] 0.15 max 0.15 max
W [%] 45.9 - 47.9 31.0 - 32.0
Ti [%] 23.0 - 25.0 26.4 - 27.4
Ta [%] 17.8 - 19.8 23.0 - 24.0
Nb [%]  6.8 - 7.4
O [ppm] 4000 max 3000 max
FSSS [µm] 1.1 - 1.6 1.3 - 2.1
Impurities of all grades (max) [ppm]

Al Ca Fe N Si
50 50 1000 1000 100
17
Trademark and data supplied by Treibacher Industrie AG, Treibach, Austria.

13.2.3 Cermets
13.2.3.1 Production of molybdenum carbide.
The production method usually adopted for the production of molybdenum carbide, β-Mo2C, is the direct
carburisation of molybdenum metal powder and pure carbon black or graphite powder (see Table 8 and
Table 9). The appropriate intimate mixture is heated to ca. 500 °C under hydrogen in a carbon tube
resistance furnace.
The molybdenum-carbon equilibrium diagram is shown in Fig. 13.13 [91M2]. The properties of a
commercially available molybdenum carbide powder is shown in Table 19.
Table 19. Physical and chemical properties of molybdenum carbide powder.
Molybdenum carbide18 Total carbon [%] Free carbon [%] FSSS [µm]
β-Mo2C160 5.7 - 6.0 ≤ 0.30 1.5 - 2.0
13.2.3.2 Production of titanium nitride
There is a number of methods which can be used to produce titanium nitride powder. Some techniques
produce purer material, especially in relation to traces of oxygen and carbon.
- Nitriding of titanium dioxide, in the presence of carbon, with nitrogen or ammonia at 1200 - 1400 °C
as follows:
TiO 2 + 2C + 0.5 N 2 → TiN + 2CO (5)
The reaction proceeds over a number of intermediate steps and the final product may contain
significant traces of oxygen and carbon.
- Nitriding of titanium metal or titanium hydride powders using nitrogen or ammonia at temperatures of
ca. 1200 - 1400 °C. In order to complete the reaction it is usually necessary to carry out the process
under a pressure of ca. 100 MPa. The product is of a very high level of purity.
- Reaction of titanium chloride or oxychloride with ammonia. This process is based on the thermal
decomposition of intermediate ammonia-halogen complexes.
The equilibrum diagram for titanium-nitrogen is shown in Fig. 13.14 [91L]. The properties of a
commercially available titanium nitride powder are given in Table 20.
Table 20. Physical and chemical properties of titanium nitride powder.
Grade18
Titanium nitride Nitrogen [%] Carbon [%] FSSS [µm]
TiN grade C ≤ 20 < 0.1 0.8 - 1.2
13.2.3.3 Production of titanium carbonitride
Although the exact method of producing titanium carbonitride powders is a commercial secret it is usual
to combine a carbothermic reduction and carburisation of titanium dioxide with a nitriding process.
The formation of specific ratios of carbon and nitrogen in titanium carbonitride, Ti (C1−x Nx), is a
function of the partial pressure of nitrogen, p(N2), at the reaction temperature. The reaction temperature is
ca. 1700 °C and holding times can be in the range 80 - 360 min. The grain size of the end product is very
18
Trade name and data supplied by H.C. Starck, Goslar, Germany.

important and is controlled by many factors, including the type and grain size of the initial titanium
dioxide. The exact step by step production process is therefore not disclosed [93G2, 97N].
A range of titanium carbonitride powders manufactured by one company is shown in Table 21.
Table 21. Physical and chemical properties of titanium carbonitride powder.
Grade19 Description FSSS [µm]

A Coarse grained, low oxygen 2-5
B Medium grain size, medium oxygen content 1.3 - 2.0
C Fine grained, higher oxygen content 1.0 - 1.3
D Fine grained, low oxygen content 1.0 - 1.5
E Very fine equiaxed grains, low oxygen content 0.7 - 0.95
O Coarse grained, very low oxygen content 7-9
The grades A, B, C and E can be produced as Ti(CN) 70 : 30, 50 : 50 and 30 : 70. Grade D as 50 : 50 and
70 : 30 and grade O as 50 : 50.
13.2.3.4 Production of nickel
One of the best known processes for the production of high purity nickel powder is based on the carbonyl
process. This produces nickel carbonyl gas which is decomposed by injecting the gas into a special chamber,
the walls of which are heated to ca. 500 °C. The gas decomposes instantly to form nickel powder in the form
of loosely bound filaments. By varying these conditions various powder forms may be obtained.
Two grades, used for producing special hardmetals and cermets, are shown in Table 22.
Table 22. Physical and chemical properties of nickel powder (Inco Products).
Grade20 FSSS App. density Impurities (typical values)

C Co Fe N O S other
µm g cm−3 ppm elem.
Type 255 2.2 - 2.8 0.5 - 0.65 2000 3 50 3 700 2 < 10
Type 210 0.5 - 1.0 < 0.5 < 1wt% - < 100 - < 1wt% < 10 trace
Extra fine
Fine nickel powder can also be produced by a hydrometallurgical process based on the reduction of a
nickel sulphate solution at 175 - 205 °C under a 3.1 MPa pressure of hydrogen. The process is described
in [80C]. Details of a typical commercially available nickel powder are shown in Table 23.
Table 23. Physical and chemical properties of nickel powder (Union Miniere, Olen, Belgium).
Grade21 FSSS App. density Impurities (typical values)

Co Fe Cu S C22 O22
µm g cm−3 ppm
2M Nickel powder 2.0 - 2.8 1.7 - 2.2 1000 900 20 140 1900 4000
19
Trade name and data supplied by H.C. Starck, Goslar, Germany.
20
Trademark and data supplied by Inco SPP, Swansea, U.K.
21
Trademark and data supplied by Union Miniere, Olen, Belgium.
22
Note: The majority of the carbon and oxygen is in the form of residual organic matter and most can be removed by
heating to 400 °C under hydrogen.

13.2.4 Properties of raw materials

13.2.4.1 Cobalt
Table 24. Physical and chemical properties of cobalt [98C2]
Cobalt (Co) - A silvery metal having a close packed hexagonal crystal structure.
(a) Atomic structure
Cobalt is a transition metal, appearing between iron and nickel in the first long period of the periodic
table. It is a group VIII metal with a configuration 3d74s2 total electrons.
1s22s22p63s23p63d74s2: 27 atomic number

Atomic mass = 58.99 (59) g/mol, 27 protons, 32 neutrons
The structure accounts for the variable valency of cobalt with Co+2 being the obvious one with the two
4s electrons removed. Cobalt ions Co+3 occur by electron addition and Co+1 occurs in a few complex salts.
(b) Physical constants
Density: 8.85 g/cm3

Melting point: 1493 °C (2719 °F)
Boiling point: 3100 °C (5612 °F)
Coefficient of linear expansion: 12.5 x 10−6/K (20 - 100 °C)
13.6 x 10−6/K (100 - 200 °C)
Coefficient of volume expansion: 35.6 x 10−6/K (100 °C)
Transition temp. hex to fcc: ~ 421 °C
Electrical resistivity: 6.24 µΩ cm
Curie point: 1121 °C
Allotropic transformation data (Transition at 421 °C)
Hexagonal Face centred cubic

Atoms/cell 4 6
Lattice parameter a = 0.25071 nm RT a = 0.35441 nm
Density 8.85 g/cm3 RT 8.80 g/cm3
Lin. coeff. expansion 12.5 · 10−6/K RT 14.2 · 10−6/K
Transformation temp. 421 °C
Lattice at transformation temp. a = 0.2541 nm 421 °C a = 0.3587 nm
Heat of transformation 1 cal/g = 4.2 J/g
Volume expansion 0.36 % approx.
Free energy change 500 J/mol (hex→fcc) (fcc→hex) 360 J /mol
Latent heat of fusion 61.75 cal/g = 258.5 J/g
Electrical resistivity at 20 °C 6.24 µΩ/cm
Temperature coefficient for 0 - 100 °C 0.00604/K
Standard electrode potential at 25 °C E0 (Co/Co++) = –0.277 V
Curie temperature 1121 °C
Saturation induction 17900 Gauss (1.79T)
Residual magnetisation 4900 Gauss (0.49T)
Coercive force 8.9 Oersted (707 A/m)
Initial permeability µ 68
Maximum permeability µ max 245

Physical and chemical properties of cobalt (cont.)
Modulus of elasticity (RT) 2.058 · 105 MPa

Shear modulus 0.76 · 105 MPa
Latent heat of vaporisation 1550 cal/g = 6510 J/g
Electrochemical equivalent (2) 0.305 mg/C
Hardness of electrodeposited cobalt 27 - 31 HV
Vapour pressure 1 · 10−6 atm = 10−1 Pa (at 1477 °C)
13.2.4.2 Carbides
Table 25. Physical and chemical properties of carbides [95K1].
WC TiC TaC
Relative molecular mass 195.97 59.91 192.96
Lattice structure hexagonal bcc bcc
Structure type Bh B1 B1
Lattice constant [nm] a = 0.29065 0.43305 0.4454
c = 0.28366
Density [g/cm3] 15.7 4.93 14.48
Microhardness HV0.05 2000 (basal plane) 3000 1800
1300 (prism face)
Elastic modulus [N/mm2 = MPa] 696000 451000 285000
Bending Strength [N/mm2 = MPa] 550 240 - 390 not determined
Melting point [°C] 2775 3070 3985
Coefficient of thermal expansion [K−1] a = 5.2 · 10−6 7.74 · 10−6 6.29 · 10−6
c = 7.3 · 10−6
Thermal conductivity [W/(cm K)] 1.21 0.21 0.22
Electrical resistivity [µΩ cm] 19 68 25
Heat of formation H296 [kJ/mol] −40.2 −183.4 −146.5
Specific heat 20 °C; [J/(mol K)] 39.8 47.7 36.4
Colour metallic grey metallic grey dark brown
NbC β-Mo2C VC Cr3C2

Relative molecular mass 104.92 203.91 62.96 180.05
Lattice structure bcc hexagonal bcc orthorhombic
Structure type B1 L'3 B1 D510

Lattice constant [nm] 0.4470 a = 0.300 0.4165 a = 1.147;
c = 0.4734 b = 0.554;
c = 0.283
Density [g/cm3] 7.78 9.18 5.36 6.68
Microhardness HV0.05 2000 1500 2900 1350
Elastic modulus [N/mm2 = MPa] 338.000 533.000 422.000 373.000
Bending Strength [N/mm2 = MPa] not determined not determined not determined not determined
Melting point [°C] 3615 2485 2650 1810
Coefficient of thermal expansion [K−1] 6.55 · 10−6 7.8 · 10−6 7.2 · 10−6 10.3 · 10−6
Thermal conductivity [W/(cm K)] 0.14 not determined not determined not determined
Electrical resistivity [µΩ cm] 35 71 60 75
Heat of formation H296 [kJ/mol] −140.7 −49 −124.8 −94.2
Specific heat 20 °C; [J/(mol K)] 36.8 30.3 32.3 32.7
Colour brownish metallic grey metallic grey metallic grey

13.2.4.3 Nitrides
Table 26. Physical and chemical properties of nitrides [91E2].

Part a
Nitride Homogeneity Structure Lattice Density Colour Microhardness
range a (1−x) at (Bravais parameter (RT)
1700 K lattice) (RT) [nm] [g cm−3] [HV]
TiN1−x 0.50 bcc 0.4215 - metallic grey 2300
1.00 0.4242 5.39 c golden yellow 1700
ZrN1−x 0.54 bcc 0.4585 - light yellow -
1.00 −0.4570 7.32 c light yellow 1500
HfN1−x 0.70 bcc 0.4523 - light yellow 1390 (940)
1.06 0.4514 13.83 c dark yellow 1590 (1000)
VN1−x 0.70 bcc 0.4060 6.05 brown yellow 1300
1.00 0.4138 6.04 brown yellow 570
NbN1−x 0.84 bcc 0.4380 8.24 (0.92) pale yellow 1300
1.00 0.4392 8.18 (0.95) pale yellow 1100
TaN1−x 0.72 (2200 K) bcc 0.4345 - - -
1.00 0.4328 15.9 c grey yellow 3200
TaN > 0.99 hex a 0.5190 14.3 dark grey 1100
1.00 c 0.2911 - -
CrN > 0.97 e bcc 0.4148 6.14 grey brown 1100
1.00 - - -
Cr2N 0.31 e hcp a 0.4750 g 6.51 grey 1200 g
c 0.4430 g
0.50 a 0.4796 - 1400 b
c 0.4470
MoN1−x 0.40 bcc 0.4139 - -
(Mo2N) 0.54 (1200 K) 0.4162 9.48 c grey 1700 b
MoN - hex a 0.5745 8.1 grey -
c 0.6122 9.1 c
For footnotes see next page

Table 26. Physical and chemical properties of nitrides (cont.).

Part b
Nitride Homogeneity Melting Heat conductivity Thermal exp. Electrical Superconductivity
b
range a (1−x) at point (RT) b coefficient at resistance transition temp.
1700 K [K] [W/(m K)] 1000 K (RT)b Tc [K]
[106/K] [µΩ cm] comp. (1−x)
comp. (1−x)
TiN1−x 0.50 - - - - <1
1.00 3320 29 9.4 (0.95) 25 5.8
ZrN1−x 0.54 - - - - -
1.00 3250 11 8.2 - 9.1 (0.92) 21 10.47
HfN1−x 0.70 - - - - 8.7 (0.85)
1.06 3600 11 8.6 33 6.92
VN1−x 0.70 - - 11.0 - 2.7 (0.76)
1.00 2620 11 10.8 65 8.9
NbN1−x 0.84 - - 9.5 (0.92) - 13.8 (0.84)
1.00 -d 3.8 10.2 (0.95) 60 17.2
TaN1−x 0.72 (2200 K) - - - -
1.00 -d 8.0 8.9 (0.94)
TaN > 0.99 - - - -
1.00 -d 9.54 - 128
CrN > 0.97 e 11.7 2.3 - -f
d
1.00 1300 - - 640 -
Cr2N 0.31 e - - - - -f
0.50 1800 - - 81
MoN1−x 0.40 - - -
(Mo2N) 0.54 (1200 K) - 9.3 −5.08
MoN - - - 15.1
a b
Nitrogen-rich phase boundary depends on nitrogen pressure. Exact composition unknown, probably
c d
close to 2:1 (CrN1−x, MoN1−x) or 1 : 1 (all others) stoichiometry. X-ray density. Decomposes.
e f g
Calculated. Not superconducting. Exact composition unknown.
13.2.5 Special processes

13.2.5.1 Menstruum process
A method of producing coarse carbide crystals and especially mixed crystals, WC-TiC, was patented by
McKenna in 1938 [38M]. A charge of tungsten metal, graphite chips, titanium dioxide and nickel is
heated to a temperature above 1600 °C. The tungsten and titanium atoms combine with carbon atoms to
form a mixed crystal within a molten bath of nickel. The mixed crystal particles are released by acid
dissolution of the cooled mass.
13.2.5.2 Direct reduction of ore
The direct reduction of tungsten ore scheelite - CaWO4 - can be achieved by an exothermic reaction to
produce a very coarse tungsten carbide [68M]. The process uses a mixture of iron oxide, aluminium,
carbon, calcium carbide and scheelite. On ignition, the exothermic reaction commences at a temperature
of ca. 2500 °C and tungsten carbide is formed. The WC-crystals are set-free by acid attack of the cooled
mass.

13.2.5.3 Zinc process
Based on an early patent of Trent [46T], a novel extraction method of utilising hardmetal scrap as the
starting material was developed [71B1]. The hard (sintered) scrap is treated with molten zinc and
subsequently the zinc is removed by distillation. Initially the zinc forms an alloy with the cobalt binder,
which disrupts the solid material. After removing the zinc, the residue can be re-milled to form alloy
powders.
13.2.5.4 Combined reduction and carburising
A combined reduction and carburising process using a mixture of tungsten trioxide, WO3, and carbon
black which is processed through two consecutively connected rotating furnaces yields a fine grain
tungsten carbide powder [88A2].
13.2.5.5 Production of nano grain size WC-Co alloy powder
This process [90M1] combines three distinct manufacturing stages. The first is the preparation of a mixed
starting solution, i.e. specific salts in a solution which expresses the required ratio of the final
constituents. The second is the spray drying of this solution to form homogeneous, spherical particles.
The final step is the conversion of these particles to the carbide / metal alloy by reduction / carburisation
in a fluid bed reactor. The resultant WC-grains are in the nano-size range.
13.3 Production methods
13.3.1 Hardmetals - cermets

The flow sheet shown in Fig. 13.15 is applicable to both hardmetals and cermets.
13.3.1.1 Powder milling
To obtain the maximum efficiency in ball milling hardmetal and cermet powders, the following operating
criteria are applicable [58I]:
- Speed of rotation of the mill is based on 60% of the critical speed of milling and is obtained from the
formula:
Critical speed (rpm ) = 42.4 / D (6)
where D is the diameter of the ball mill in metres.
- Fill volume of the mill chamber
0.4 - 0.5 of total mill volume
- Ball-weight to powder-weight
in the range 3 : 1 to 5 : 1
the higher ratio results in a more intensive milling action and leads to shorter milling times.
- Diameter of hardmetal (WC-7 wt% Co) balls
in the range 5 - 10 mm ∅
balls under 5 mm ∅ should be removed from the mill charge and the correct weight made up with
new clean 10 mm ∅ balls.
- Ratio of milling liquid to powder weight in the range 0.25 - 0.35 l/kg powder.
Depending upon the characteristics of the constituent raw materials, milling times are in the range
25 - 60 h. Milling liquids are based on inert, organic liquids, e.g. ethyl alcohol, acetone, hexane etc.

13.2.5.3 Zinc process
Based on an early patent of Trent [46T], a novel extraction method of utilising hardmetal scrap as the
starting material was developed [71B1]. The hard (sintered) scrap is treated with molten zinc and
subsequently the zinc is removed by distillation. Initially the zinc forms an alloy with the cobalt binder,
which disrupts the solid material. After removing the zinc, the residue can be re-milled to form alloy
powders.
13.2.5.4 Combined reduction and carburising
A combined reduction and carburising process using a mixture of tungsten trioxide, WO3, and carbon
black which is processed through two consecutively connected rotating furnaces yields a fine grain
tungsten carbide powder [88A2].
13.2.5.5 Production of nano grain size WC-Co alloy powder
This process [90M1] combines three distinct manufacturing stages. The first is the preparation of a mixed
starting solution, i.e. specific salts in a solution which expresses the required ratio of the final
constituents. The second is the spray drying of this solution to form homogeneous, spherical particles.
The final step is the conversion of these particles to the carbide / metal alloy by reduction / carburisation
in a fluid bed reactor. The resultant WC-grains are in the nano-size range.
13.3.1 Hardmetals - cermets

The flow sheet shown in Fig. 13.15 is applicable to both hardmetals and cermets.
13.3.1.1 Powder milling
To obtain the maximum efficiency in ball milling hardmetal and cermet powders, the following operating
criteria are applicable [58I]:
- Speed of rotation of the mill is based on 60% of the critical speed of milling and is obtained from the
formula:
Critical speed (rpm ) = 42.4 / D (6)
where D is the diameter of the ball mill in metres.
- Fill volume of the mill chamber
0.4 - 0.5 of total mill volume
- Ball-weight to powder-weight
in the range 3 : 1 to 5 : 1
the higher ratio results in a more intensive milling action and leads to shorter milling times.
- Diameter of hardmetal (WC-7 wt% Co) balls
in the range 5 - 10 mm ∅
balls under 5 mm ∅ should be removed from the mill charge and the correct weight made up with
new clean 10 mm ∅ balls.
- Ratio of milling liquid to powder weight in the range 0.25 - 0.35 l/kg powder.
Depending upon the characteristics of the constituent raw materials, milling times are in the range
25 - 60 h. Milling liquids are based on inert, organic liquids, e.g. ethyl alcohol, acetone, hexane etc.

Attritor23 milling is widely used in the hard materials industry: In this instance the mill chamber remains
stationary while the balls and charge are moved by a rotating series of arms as shown in Fig. 13.16. In
some units the milling slurry is pumped from the bottom to the top. The ball velocity of movement varies
across the diameter of the mill chamber as shown in Fig. 13.17.
The following operating conditions apply to attritor milling:
- Ball weight to powder weight 5 : 1
- Diameter of hardmetal (WC-7 wt % Co) balls in the range 4 - 7 mm ∅
- Mill volume of balls
the mill chamber is loaded with balls until the charge just covers the top rotating arm.
- Ratio of milling liquid to powder weight in the range 0.25 - 0.4 l per kg powder.
As with ball milling, the choice of milling liquid falls within the same range of organic liquids. Milling
times with attritor processing are radically reduced, when compared with ball milling: in the range 4 - 16 h.
13.3.1.2 Forming lubricants
Forming lubricants are required to fulfil two functions: The first is to assist the forming operation by
reducing friction between the powder and the forming tools and also between the powder particles. The
second, and of equal importance, is to provide green strength for the formed component.
A common type of lubricant is paraffin wax added in the range of 1 - 1½ wt% for dried powder and
1½ - 2 wt% for the granulated form. These materials have a complex chemical structure and are made up
of a number of compounds. The wax has to have the correct consistency at room temperature to fulfil the
forming requirements. This is usually defined by the melting point range. A typical paraffin wax has the
properties shown in Table 27.
Table 27. Physical and chemical properties of a fully refined paraffin wax.
Melting Penetration24 Solidifying Flash point Normal Iso- Cyclo- Alkyl-

range value range paraffins paraffins paraffins benzene
°C mm °C °C % % % %
53.5 - 55 14 - 18 52.8 - 53.4 216. 86.1 - 92.3 3.5 - 6.3 3.0 - 7.1 0.2 - 0.5
In order to improve the quality of spray dried granules (increased flow and handling properties),
polyethylene glycol (PEG), in some instances, has been substituted for paraffin waxes. Polyethylene
glycol has the general formula HC(CH2·CH2·O)n H where the value n denotes the polymer. The average
molecular mass of the polymers varies from 200 g/mol upwards, although polymers used as lubricants in
the hardmetal-cermet industries are in the range 1000 - 4000 g/mol. These latter materials are described as
soft waxy solids. A 1500 g/mol polymer has a solidifying temperature range of 44 - 48 °C, whilst a
4000 g/mol polymer has a range of 53 - 58 °C. In order to arrive at the desired lubrication and hardness
values, a mixture of two compounds may be used. The polymers are fully soluble in water but only
sparingly in ethyl alcohol. The normal addition, used for granulated products, is 3 wt% although 2 wt% is
sufficient in certain cases.
For special forming methods, e.g. extrusion [93F] a much higher lubrication content is required. It is
usual to add sufficient lubricant - 6 - 8 wt% - to produce a completely dense component after extrusion.
The type of lubricant used also varies according to the method of extrusion. Thus, manufacturers have, in
many instances, devised specific lubricants to suite their equipment.
The same reasoning applies to lubricants used for injection moulding. There is a whole range of
lubricants used from waxes to water soluble gelling polymers [97Y, 98N]. In many instances the
complete technique of injection moulding, from lubricant to de-binding / sintering has been patented
[78R].
23
Trademark of the Union Process Inc., Ohio, USA.
24
Penetration method: 0.14 mm ∅ needle, 25 °C, 100 g, 5s.

13.3.1.3 Drying and granulating
Normal vacuum drying of wet milled powders containing an addition of lubricant is carried out using a
heated closed container equipped with a rotating stirrer. The stirred, heated slurry is placed under a
vacuum which removes the milling liquid, leaving a dried powder with a uniform distribution of
lubricant. The precise operating parameters are dependant on the volume of slurry, type of milling liquid
and vacuum system. This powder is used as the basis for a number of forming processes - see Fig. 13.15.
Granulated powder with good flow characteristics is vitally important for the success of high speed,
high pressure, automatic die pressing. Two basic methods are used. The first is based on the rotation of
damp powder in an inclined drum. The action, when the conditions are satisfactory, produces semi-
rounded granules with a wide granule size range and variable hardness.
The second method - spray drying [82J] has been widely adopted in the hardmetal-cermet industries
for the production of high quality granules. A schematic representation of the essential features of the
process is shown in Fig. 13.18. The basic principals of operation are the spraying of liquid / solid droplets
into a counter-current flow of a hot inert gas. This evaporates the liquid which is carried away, leaving
solid, spherical dried granules. The following lists the important operating parameters:
- Viscosity of the slurry (based on alcohol and 2 wt% paraffin wax) ca. 4.0 Pa s at 25 °C. The values
shown in Table 28 give the solids content of various hardmetal alloys to achieve this viscosity.
Table 28. Solids content of slurry (alcohol and 2 wt% paraffin wax) for various hardmetal alloys to
achieve a viscosity of ca. 4.0 Pas at 25 °C.
Material Solids content

wt%
Fine grain – submicron 74 - 75
Medium grain size - 1 - 3 µm WC 80 - 82
Coarse grain size - 3 - 6 µm WC 83 - 85
Very coarse grain size - > 6 µm WC 85 - 86
High cobalt content - > 14 % 85 - 86
High mixed crystal content - > 6 % 77 - 78
- Nitrogen atmosphere: 0.3 % max O2 content

- Inlet temperature of nitrogen: 180 - 200 °C
- Nitrogen pressure in spray tower: ca. 2 kPa
- Outlet temperature of nitrogen: 90 - 100 °C
- Pressure drop across cyclone: ca. 1 kPa
- Spray pressure: 500 - 800 kPa
- Spray nozzle diameter: 1.1 to 1.2 mm ∅ for WC-Co alloys
1.4 to 1.8 mm ∅ for WC-TiC-TaC-Co alloys
The above values are typical for a ca. 120 kg h−1 spray drying unit.
The granules have a typical size range of 315 µm to 63 µm with a peak in the distribution curve
between 125 - 200 µm. By removing the coarse > 315 µm and the fine < 63 µm fractions the flow
characteristics can be improved to typically 18 - 24 s Hall flow (ASTM B 213-83).
13.3.1.4 Cold isostatic pressing
Cold isostatic pressing of hardmetals has been adapted from the process previously used for ceramics.
The process can be divided between wet bag and dry bag methods. In the former, large pressings are
produced by subjecting powder (usually with 0.5 wt% wax) contained in a rubber mould to an isostatic
pressure of up to 300 MPa using a water / oil mix. Comparison between the variation in contraction
within large pressed components produced by single action punch-metal die pressing and wet bag cold

isostatic pressing has shown a reduction from 2.2 % to 0.6 % [72L]. In the latter method, dry bag
pressing, the press tooling system is an integral part of the pressure vessel, whereby filling and compact
removal, whether automatic or manual, takes place without mould removal. Moulds, in this instance, have
to withstand repeated pressing cycles and are usually manufactured from polyurethane. Complicated
components with internal forms can readily be produced at pressures in the range 50 - 210 MPa and at
5 cycles per minute.
13.3.1.5 Extrusion
In order to achieve a fully plasticised mass suitable for extrusion, the powder and lubricant / plasticiser
has to be kneaded in a special machine as shown in Fig. 13.19. By this action a uniform mass of material
is produced which can be extruded in either a piston - or screw type machine. The latter tends to be used
for rod diameters of > 25 mm, especially where complicated internal channels are required. In relation to
lubricant / plasticisers, paraffin wax is still economically justified for rod diameters below 16 mm but
above this a new formulated plasticiser - plastic / organic solvent - has been developed [97F].
13.3.1.6 Injection moulding
Injection moulding has been used for the mass production of complicated components, the processing
stages being shown in schematic form in Fig. 13.20 [88P]. This section deals with the moulding process.
As mentioned in section 13.3.1.2 there is a very wide range of plasticisers / binders used in this
process. This means that data for one particular process is specific to the plasticisers type. In order to
achieve the necessary rheological properties the ratio powder to plasticiser is approximately 60 : 40. The
relative merits of a number of possible plasticicers is shown in Fig. 13.21 [88M]. References [88M, 98N]
review the subject of injection moulding.
13.3.1.7 Indirect shaping
This method of forming starts with pre-formed, simple shaped blocks, which have been manufactured by
either metal die or cold isostatic pressing. The strength required for various machining operations is
usually obtained by subjecting the pressed form to a pre-sintering operation at a temperature of
700 - 850 °C. Before maching commences, it is important to calculate the contraction which will occur on
sintering. Contraction depends not only on the pressing pressure but also on the grain size of the carbide
constituents and to some degree on the cobalt content [72L]. Typical values are shown in Table 29.
Table 29. Linear contraction dependency on pressing pressure for hardmetal alloys.
Hardmetal25 alloys Pressing pressure

Co Mixed Grain
crystal size 50 MPa 100 MPa 150 MPa 200 MPa
wt% wt% µm
Linear contraction = 100 [(pressed dimension / sintered dimension) – 1]
6 - 0.8 28 26.5 25.5 24.5
6 - 1.2 24.5 22.75 22 21
9 - 4.0 23 21 20.2 19.6
9 20 3.0 22.5 21 20.4 19.8
Machining can be carried out using all of the usual methods except that the cutting tools must be highly
resistant to abrasive wear.
25
Original powder contained 2 wt% paraffin wax.

13.3.1.8 High speed automatic die pressing
This pressing technique uses granulated powder which is automatically fed into an open die. Pressing
occurs by movement of both upper and lower punches. Complicated forms on the top and bottom faces of
the component can be produced at speeds up to 25 strokes per minute. Hydraulic, mechanical and hybrid
hydraulic / mechanical presses with pressing forces of 50 to 5000 kN are used together with automatic
pick and place systems for removing the pressed components [92M1, 96K].
The complete breakdown of the granulated powder during pressing is essential in order to achieve
minimum porosity after sintering. The strength (hardness) of the granules will thus require a minimum
force to achieve this. It is important to determine this value before designing press tools as this also
determines contraction which will occur on sintering. A schematic illustration of the influence of pressing
pressure on porosity is shown in Fig. 13.22. The critical press zone (CPZ) will be different for each type
of granulated powder, i.e. method of granulating, lubricant, granule size range.
13.3.1.9 Sintering
The sintering operation is the process which confers the mechanical, physical and chemical properties on
the material. During the process the pressed or formed components are heated under controlled conditions
either in a hydrogen atmosphere (may also be a mixed H2/N2 atmosphere) or under a vacuum (low
pressure). At the end of the process the components are fully dense and have acquired a specific
microstructure with the desired properties.
The process can be divided into stage 1, dewaxing / presintering and stage 2, sintering, although from
a technological viewpoint the stages may be merged into one operational sequence.
13.3.1.9.1 Dewaxing / presintering
Press lubricants have to be removed from the shaped components without causing any changes in the
component's physical form or chemical composition. This is usually accomplished by a low temperature
controlled heating cycle under non-oxidising conditions. In certain circumstances, with a special lubricant
used in extrusion or injection moulding, a leaching treatment with a solvent vapour is initially carried out.
The loss of paraffin wax with a melting range of 43 - 46 °C on heating in a stream of hydrogen is
shown in Fig. 13.23 [70S]. With higher amounts of wax - montan ester type - in extruded products a
prolonged dewaxing operation is required as shown in Fig. 13.24 [88M]. The various volatile
decomposition products obtained by heating a WC-6 wt% Co alloy, in one case containing 2 wt% paraffin
wax and in the other 2 wt% polyethylene glycol (PEG), under a flow of 5 l/h of argon, are shown in
Fig. 13.25 and in Fig. 13.26, respectively [92L1]. The atmosphere used in the dewaxing / depeging
operation has a significant influence on the way the various lubricants decompose. This is illustrated in
Fig. 13.27 [92L1] which details the various decomposition gases produced on heating the same alloys as
used previously under an argon or hydrogen atmosphere. The most notable feature is the production of
methane when paraffin wax is volatilised under hydrogen. When compacts are heated in hydrogen any
oxides of cobalt and tungsten are reduced as shown in Fig. 13.28 [70S]. Reduction commences at ca. 200
°C and a temperature of 700°C is required to achieve total reduction. Reaction between hydrogen and the
tungsten carbide in the WC-Co alloys occurs in the presintering temperature range 600 - 900 °C
according to the following:
WCCo + 2H2 → CH4 + WCo (7)
where the term WCCo denotes the influence of cobalt on the reaction.
The equilibrium for this reaction at 800 °C is 2 vol% CH4 in the dry hydrogen.
When oxidising agents are present, such as moisture or oxygen, in the hydrogen then the reaction proceeds as
follows:
WCCo + H2O → CO + H2 + WCo (8)

The presence of mixed crystal (W-Ti) C in the alloy also results in a carbon loss:
> 600 °C
(W-Ti) C + 2H2 ← → (W-Ti) + CH4 (9)
In an oxidising atmosphere the reaction can be divided as follows:
= 600 ° C
(W-Ti) C + H2O ← → (W-Ti) + CO + H2 (10)
and
> 700 °C
(W-Ti) C + 2H2O ← → (W-Ti) O + CO + 2H2 (11)
Further details concerning these reactions can be found in reference [79S].
The presence of the oxygen associated with titanium has serious consequences for carbon control
during the sintering operation as it can only be reduced by carbon.
Dewaxing / presintering in vacuum (ca. 13 Pa) results in the removal of paraffin wax according to the
vapour pressure of the various compositional fractions and requires a temperature of ca. 150 °C to
complete the process. However, it is usual in commercial units to use a flow of either an inert gas or
hydrogen, the latter being essential for satisfactory PEG removal. Any cobalt oxides are reduced by
carbon in the range 300 - 500 °C whilst tungsten oxides require a temperature in the range 650 - 900 °C
[79S, 97L2].
Presintered compacts are required to have sufficient strength to enable a variety of machining opera-
tions to be carried out. Transverse rupture tests on a series of hardmetal alloys, as detailed in Table 30,
were carried out on presintered test-pieces - 800 °C for 0.5 h under a vacuum - after pressing at various
pressures. The results are shown in Fig. 13.29 [80N].
Table 30. Hardmetal alloys used in the pressing pressure - presintering - strength experiments [80N].
Materials Particle size of WC powder Co (TiC + TaC)

µm wt% vol% wt %
A-2 2.0 5 8.5 0
C-4 4.0 8 13.3 0
D-2 2.0 9 14.8 0
D-3 3.0 9 14.8 0
D-5 4.7 9 14.8 0
P 20 3.5 8.5 12.1 15
P 40 2.0 13 19.2 10
13.3.1.9.2 Sintering
Sintering is associated with the onset of shrinkage of the hardmetal alloys and is often judged as
beginning to occur at a temperature of 750 - 850 °C. The progress of shrinkage together with mass loss,
mass loss rate, thermal effects and gas formation for the following two hardmetal alloys:
- WC26 - 6 wt% Co with 2 wt% paraffin wax

original grain size WC : dWC = 2.3 µm
- DS 60 WC26 - 10 wt% Co - 0.45 wt% VC - 0.6 wt% Cr3C2

original grain size WC : dWC = 0.6 µm
is shown in Fig. 13.30 and Fig. 13.31, respectively [97L2].
26
Manufactured from H.C. Starck GmbH, Goslar, Germany.

The measurements were made using Netzsch equipment27 402 E dilatometer, DSC 404 calorimeter, STA
429 thermobalance and a mass spectrometer QMG 42128 Balzers. The experiments were carried out using
5 l/h helium (Fig. 13.30) and 5 l/h argon (Fig. 13.31) and a heating and cooling rate of 10 K/min.
The results indicate the important stages in the sintering process and demonstrate the differences that
occur between the two alloys, particularly in relation to the temperature of the onset of shrinkage and the
shape of the shrinkage rate curve. The presence of grain growth inhibitors also markedly influences the
melting temperature of the alloys, as shown in Fig. 13.32 [96G3].
In this instance the 10 wt% Co hardmetal was produced using H.C. Starck DS 40 (0.4 µm) WC.
Before liquid phase sintering commences, a considerable amount of shrinkage has taken place in the
solid state. The remaining densification occurs very rapidly once the eutectic temperature is reached (Fig.
13.30 and Fig. 13.31). Final elimination of the remaining porosity occurs by solution and precipitation of
carbides according to Ostwald ripening. A comprehensive review of liquid phase sintering is contained in
reference [85G].
The relationship between composition, temperature and the various phases applicable to the Co-W-C
system [89G2] also plays an important role in the sintering process. The ternary equilibrium diagram at
1584 K - Fig. 13.33, the Co-WC vertical section of the Co-W-C phase diagram - Fig. 13.34, the vertical
section of the Co-W-C phase diagram at 6 wt% Co and at 10 wt% Co - Fig. 13.35 and Fig. 13.36,
respectively, all illustrate the importance of the carbon content of hardmetal alloys in achieving a two-
phase fcc β + WC structure [89G2]. At room temperature these values are somewhat narrower as shown
in Table 31. The carbon content also influences the volume fraction of the fcc β phase as shown by
Fig. 13.37 [94U]. Calculations and experimental measurements [98H] and [96L] respectively demonstrate
that the diffusion of tungsten and carbon from the tungsten carbide grains into the cobalt is extremely fast
even at temperatures below the liquidus - equilibrium is reached for tungsten by a temperature of 900 °C
at a heating rate of 0.33 °C/s.
The carbon content of the alloys also has a marked effect, even within the two-phase fcc β + WC field,
on tungsten carbide grain growth, as shown in Fig. 13.38 [72S2].
Table 31. Carbon limits for the two-phase fcc β + WC field at room temperature, theoretical density and
stoichiometric total carbon value (T.C.) for WC-Co alloys [79S].
Cobalt Density Stoichiometric T.C. Etaphase T.C. Free carbon T.C.
wt% g/cm3 wt% wt% wt%
1 15.56 6.07 6.05 6.07
2 15.44 6.01 5.97 6.01
3 15.33 5.94 5.89 5.96
4 15.22 5.88 5.81 5.90
5 15.10 5.82 5.74 5.84
6 14.99 5.76 5.66 5.78
7 14.89 5.70 5.58 5.72
8 14.78 5.64 5.50 5.67
9 14.67 5.58 5.42 5.61
10 14.57 5.52 5.34 5.55
11 14.47 5.46 5.26 5.49
12 14.37 5.39 5.18 5.43
13 14.27 5.33 5.10 5.37
14 14.17 5.27 5.02 5.32
15 14.07 5.20 4.95 5.26
16 13.98 5.15 4.86 5.20
17 13.88 5.09 4.79 5.14
18 13.79 5.03 4.71 5.08
19 13.70 4.96 4.63 5.02
20 13.60 4.90 4.56 4.97
25 13.17 4.60 4.16 4.68
30 12.76 4.29 3.77 4.39
27
Trademark Netzsch, Germany.
28
Trademark Balzers, Liechtenstein.

Stoichiometric values based on 6.1295 wt% for WC.

Carbon limit values calculated from:
Lower carbon deficient boundary: 6.13 - 0.079 wt% Co
Upper carbon rich boundary: 6.13 - 0.058 wt% Co
Density based on WC: 15.68 g/cm3
Co: 8.90 g/cm3
Nickel has been used as a binder for tungsten carbide in some special circumstances, for example where
cobalt is an unacceptable element. The processing parameters are similar to those used for the WC-Co
alloys. However, because of differences in the pseudo-eutectic temperature, 1342 °C as opposed to
1275 °C for cobalt and the carbon limits for the two-phase fcc β + WC field, changes to the sintering
temperature (higher) and the carbon content of the alloys (lower) are necessary. A partial isothermal
section at 1500 °C of the C-Ni-W system is shown in Fig. 13.39 [85P].
Binders consisting of alloys of cobalt, nickel and iron also lead to marked variations of the carbon
limits for the two-phase fcc β + WC field. Vertical sections of the Fe-Ni-W-C phase diagram calculated at
20 wt% Fe + Ni binder with the Fe : Ni ratio varying from 3 : 1 to 1 : 1 to 1 : 3 are shown in Fig. 13.40,
Fig. 13.41 and Fig. 13.42 respectively, illustrating this point [87G].
The importance of carbon control, in order to achieve the desired micro-structure, applies equally to
hardmetal alloys containing TiC, TaC, NbC or mixed carbides. The width of the three phase WC + β + (γ)
field for WC-TiC-Co alloys sharply extends with increasing TiC content. The same trend is found with
WC-TiC-TaC-Co alloys. However, in this instance, as shown in Fig. 13.43, the TaC content has very little
influence on the width of the field. The results indicate a three phase field width of some 0.35 wt% and
0.56 wt% carbon for a WC-TaC - 5 wt% TiC - 10 wt% Co and a WC-TaC - 15 wt% TiC - 10 wt% Co
alloy respectively [67S2].
Because of the complex composition of cermets, it is extremely difficult to follow the sintering cycle
and give details of a standard process. One of the important determining factors for this process is the
choice of raw materials, i.e. single carbides or nitrides, or complex binary, ternary or even quaternary
carbides / nitrides. The range of alloys is very wide but can be summarised as being based on 60 - 80 wt%
TiC, TiN, TiC1−XNX with additions of WC, Ta. NbC, Mo2C and in some instances carbides or nitrides of
V, Zr and Al. The initial binder consists of mixtures of Co and Ni.
The gas evolution occurring during the sintering cycle of a cermet, with the composition shown in
Table 32, is shown in Fig. 13.44 [91E1]. Fig. 13.45 shows the evolution of nitrogen [91E1].
Table 32. Composition of cermet II alloy [91E1]
TiC TiN WC Mo2C TaNbC Ni Co Ti2AlC

wt% 34.9 15.0 16.1 7.0 9.9 4.8 8.5 0.8
The sintering cycle is shown in Table 33.
Table 33. Sintering cycle for cermet II [91E1].
- Dewaxing up to 400 °C, - vacuum pump open - no analysis

- Presintering 400 - 1300 °C, - vacuum pump open, pressure 1 - 2 Pa
- Sintering 1300 - 1525 °C, - vacuum pump closed, pressure rise to 515 Pa
Fig 13.46 demonstrates that the nitrogen content of the TiC1−xNx phase has a marked influence on
shrinkage during sintering. The higher the amount, the higher the temperature at which shrinkage
becomes significant [93G2].
The relationship between the nitrogen and carbon of the carbonitrides also influences the sintering
process. This factor is controlled by the equilibrium partial pressure of the nitrogen and the composition
of the carbonitride. When Mo2C and / or WC are present the equilibrium pressure is reduced. These
relationships are illustrated in Fig. 13.47 [91E1].

Sintering is carried out in a number of commercial furnaces such as resistance wire-wound tube hydrogen
atmosphere, resistance carbon tube hydrogen atmosphere, resistance vacuum and most frequently in
multi-atmosphere / vacuum resistance sinter-HIP units [96E1]. This latter unit is capable of carrying out
all of the individual steps of the sintering cycle in one operation, and has the ability to apply an isostatic
inert-gas pressure, usually argon, to the components immediately after sintering and whilst they are still
held at the sintering temperature. This operation virtually eliminates any porosity within the components
and thus increases strength. This is demonstrated in Fig. 13.48 [89K].
The following table gives details of the sintering cycles associated with the various hardmetal and
cermet alloys.
Table 34. Sintering conditions for hardmetal and cermet alloys.
Hardmetal
Alloy Temperature Vacuum Hold time at max. Notes
temperature
°C Pa h
WC - ≤ 5 wt% Co 1420 - 1450 2 - 20 ½-1 H2 or Ar flow in range
RT - 400 °C to remove lubricants.
WC - ≤ 15 wt% Co 1380 - 1420 2 - 20 ½-1 H2 or Ar flow in range
WC - > 15 wt% Co 1360 - 1380 2 - 20 ½-1 H2 or Ar flow in range
Above 1250 °C back - fill with
4000 Pa Ar to restrict Co-loss.
WC - (TiTaNb)C - Co 1440 - 1480 2 - 20 ½-1 H2 or Ar flow in range
If a sinter-HIP furnace is used the following cycle can be used immediately after the sintering-hold step is
completed: increase pressure to 5 MPa Ar and hold for 30 min. This overpressure step is normally only
used for fine grain low cobalt alloys or components which will be used in highly stressed conditions, e.g.
mining tools, constructional parts etc.
Table 34 cont.
Cermets
Alloy Temperature Vacuum Hold time at max. temperature
°C Pa h
TiC - TiN - TiC1−xNx - 1400 - 1550 2 - 20 ½-1
Mo2C - WC - Ni - Co
The exact sintering conditions are very dependent upon a number of factors, not least being the TiC : TiN
and C : N ratio of the titanium carbonitride component. Part of the sintering cycle may be carried out
under a partial pressure of nitrogen. It may also be necessary, especially with high nitrogen alloys, to
complete the cycle by an overpressure step, immediately after completing the sintering step, of 5 - 6 MPa
Ar for 30min.

13.3.1.10 Post-sintering treatments
13.3.1.10.1 Hot isostatic pressing (HIP)
Due to the demand for improved strength, and of more importance, greater consistency of strength, efforts
are made to produce components with a minimum amount of porosity. Porosity in hardmetal and cermet
alloys, along with other structural defects, results in a marked reduction in strength properties [88N].
The process of hot isostatic pressing (HIP) has been successful in eliminating pores and increasing
strength. Fully sintered components are subjected to an isostatic inert gas (usually Ar) pressure of ca.
100 MPa at a temperature of ca. 1350 °C for 1 h. Fig. 13.48 [89K] illustrates the increase in transverse
rupture strength of three WC - 6 wt% Co alloys with different WC-grain sizes, while Fig 13.49 [85T]
shows the increase in strength for WC-Co alloys with a medium (1.3 µm) WC-grain size. The
improvement after hot isostatic pressing is evident.
13.3.1.10.2 Coating
The coating of hardmetals and cermets with a thin hard layer has enabled, when cutting ferrous base
materials, the cutting time or cutting speed to be extended or increased, respectively. In either case this
dramatically reduces the overall cost of machining. The technique has been applied to other tools used in
‘chipless’ forming, where marked advantages both in the life of the tool and in the quality of the product
have been achieved.
The technique can be divided into a number of practical processes, based on pressure and temperature,
as shown in Fig. 13.50 [97B1].
13.3.1.10.2.1 Chemical vapour deposition (CVD)
A typical schematic diagram of equipment for coating with TiC or TiN is shown in Fig. 13.51 [88K2]. In
the case of coating with TiC, a mixture of titanium tetra-chloride (TiCl4), methane (CH4) and hydrogen
(H2) is produced in a gas mixing unit, which is then led into a reaction chamber over the components to
be coated. The chamber is heated to a temperature of ca. 1000 °C. The reactions occurring within the
chamber are very complex and are determined by the enthalpy of reaction ∆G, which is dependant on
temperature. Some of the possible reactions for the formation of TiC and TiN are illustrated in Fig. 13.52
[88K2]. When ∆G is negative the reaction in the equations is displaced to the right. Thus, for eq. 1 in the
diagram, a minimum temperature of 990 °C is required for the formation of TiC. Equation 2 shows that
methane will break down to carbon within the complete temperature zone but this pyrolysis can be
avoided by the presence of excess hydrogen - eq. 6. It is also necessary to consider that TiC has a wide
carbon stoichiometric range - TiCx(0.55 < x < 0.98) and calculations can be made to relate eqs. 1, 2 and 6
(Fig. 13.52) to the partial pressures of TiCl4 and CH4. This is illustrated in Fig 13.53 [88K2] for a
temperature of 1300 K and a total pressure of 101.325 kPa and shows the domains for the deposition of
TiC, TiC + Ti, TiC + C. In order to deposit practically pure stoichiometric TiC an approximate gas
mixture of 3 vol% TiCl4 - 3 vol% CH4 - 94 vol% H2 is required at the above temperature and pressure.
However, it must be recognised that these conditions are only valid for a ‘neutral’ substrate that does not
influence the reactions. When the substrate contains carbon, as with hardmetal, this can be removed to
form TiC. Thus, the reactions within the chamber are extremely complex and the precise conditions for
the production of a satisfactory uniform coating over a large number of components has to be evolved
from practical experiments. This involves solving many engineering problems associated with gas
mixing, gas inlet design, temperature distribution, gas flow within the chamber and reaction product
removal.
The kinetics of the chemical reactions at the surface of the substrate are extremely important in
relation to the rate of growth of the respective layers. The factors controlling growth are many and are
complex in their inter-reaction. However, it can be shown that, in all cases, the deposition rate can be
divided into two distinct regions. The first region is controlled by surface reaction whilst the second is
controlled by mass transport of the reactants. Fig. 13.54 [83K] illustrates the change over for the
deposition of TiN on a TiC substrate using the Arrhenius plot of deposition rate versus deposition

temperature. At temperatures below 1000 °C the activation energy is 309 kJ/mol, indicating that surface
reaction is rate controlling, while above 1000 °C the activation energy is 39.4 kJ/mol, indicating that mass
transport is the rate controlling factor.
As shown in Fig. 13.50 it is also possible to deposit titanium carbonitride - Ti(CN) - as a coherent
layer on hardmetal substrates. However, because of problems of adhesion and unavoidable, detrimental
stress levels in different coating materials, titanium carbonitride is often used as an intermediary layer,
e.g. titanium carbide adjacent to the substrate followed by titanium carbonitride and finally titanium
nitride. The total layer thickness is typically 10 µm.
In order to enable the speed of machining to be increased - consequently an increase in temperature at
the cutting edge of the tool - a further layer, namely aluminium oxide (Al2O3) can be deposited on to
existing layers. The deposition follows the equation:
1000°C
2AlCl3 + 3CO2 + 3H2 ← → Al2O3 + 3CO + 6HCl (12)
As the enthalpy for this reaction, ∆G = −1758 kJ/mol is much higher than that for TiC or TiN, the
chemical reaction proceeds at a very high rate and is difficult to control. In practice the rate is controlled
by using a low pressure - 10 kPa - and diluting the reactant gases with excess hydrogen. At a deposition
temperature of greater than 850 °C, the aluminium oxide consists predominantly of the alpha form.
Through the development of the coating process it has become possible to deposit a layer of
aluminum oxinitride (Al-O-N). This material is often used as a multi-layer coating, e.g. Widia TN 20029,
with alternate layers of Al-O-N and TiN, each ca. 0.2 µm thick, built on initial layers of TiC, Ti(CN),
TiN. Such a combined layer exhibits a low level of stress.
It is possible to deposit Ti(CN) coating at lower temperatures than usual, 800 - 900 °C as opposed to
1000 - 1050 °C by using an organic C ≡ N component as the source of nitrogen. The process is referred to
as ‘medium’ temperature chemical vapour deposition, MT-CVD. In one such process the organic
compound is acetonitrile [90B] and the reaction can be approximated to the following:
3TiCl4 + CH3CN + 4½ H2 → 2TiC + TiN + 12HCl (13)
At 850 °C the coating consists of Ti(C0.63 N0.37) whilst at 780 °C it has the formula Ti(C0.54 N0.46). In order
to satisfactorily control the coating process it is usual to use a low pressure system: < 10 kPa. The
deposition rate compared with the standard CVD process is shown in Fig. 13.55 [97B1], along with a
comparison of some properties.
Referring again to Fig. 13.50, a further coating process, namely plasma chemical vapour deposition -
PCVD, can be used to deposit the usual range of hard compounds. In this process the reactant gas
molecules are ionised using an ionising glow discharge plasma within the reaction chamber. This is
achieved by establishing a negative voltage on the substrate components at a pressure of 100 - 300 Pa.
The remaining steps are as for the standard CVD process, except the temperature is in the range of
400 - 600 °C. This results in low levels of distortion especially with sensitive components.
13.3.1.10.2.2 Physical vapour deposition (PVD)
The equipment used for PVD coating techniques is continually being upgraded and modified to improve
the “quality” and “type” of deposited layers. The basic techniques are ion plating [78K], magnetron
sputtering [97B2] and cathodic arc deposition [97L3]. Hybrid techniques have been evolved, usually by
modifying the way in which the coating material is transferred from the target to the substrate and / or
increasing the ionisation gain of the reactant gases.
In all methods of coating, the substrate is heated to a temperature of 200 - 400 °C to ensure satis-
factory adhesion of the depositing atoms. The pressure within the reaction chamber is precisely controlled
in the range 0.1 - 1Pa and is composed of a mixture of reactant gas, e.g. nitrogen, methane or ethane and a
dilutant, e.g. argon. The systems all impart a high ionisation charge to the gas atoms through various
secondary electrode configurations and in some instances a superimposed bias voltage is applied to the
substrate. In the case of all gas / metal reactions at the substrate surface, the partial pressure of the
29
Trade name Widia GmbH, Germany.

selected reactant gas determines the ratio of the respective atoms. The rate of coating is usually in the
range 3 - 10 µm h−1.
As shown in Fig. 13.50 it is possible to deposit layers of TiN, Ti (CN) and (TiAl)N. This latter
material requires a special target material composed of the requisite titanium and aluminum ratio [97L3].
It is usual to coat hardmetals with a 5 µm thick layer.
13.3.1.10.2.3 Ion implantation
The ion implantation of hardmetals with various species of ions has been investigated and the most
effective of these in increasing surface hardness, has been nitrogen [86M]. The equipment required is
specialised and rather expensive [99T1].
Investigations [85D] have shown that with optimum flux of nitrogen ions and implanting temperature
it is possible to increase the microhardness of both WC - 6 wt% Co and WC - 25 wt% Co alloys.
However below an implant temperature of 200 °C both alloys demonstrate a reduction in hardness,
whilst in the temperature range of 300 - 500 °C, an increase in hardness is registered. In the case of the
higher cobalt hardmetal, the increase is more pronounced compared with the low cobalt alloy. These
results are shown in Fig. 13.56 and Fig. 13.57 [85D].
13.3.1.11 Functionally graded hard material
The use of components which possess different properties from the surface to the inner zones has been
exploited in hardmetals and cermets by coating the surface with layers of different materials - CVD and
PVD process. However, the idea of exploiting the differences in composition versus variations in
properties has progressed whereby the outer zones of the “solid” component can have marked variations
in composition compared with the inner zones. The depth of the outer zones, depending upon the
manufacturing method and the end use, can be from 20 - 30 µm to 3 - 5 µm. This material has the generic
term of “functionally graded hardmetal”.
The various techniques and resultant graded structures have been reviewed [97S2] and three types of
alloy, which are exploited, can be divided into three main groups: - WC-Co, WC - TiC - TaC - Co and
TiC - Ti(CN) - WC - Co - Ni.
In the first case the surface zone of a WC-Co alloy is enriched with tungsten carbide while cobalt
diffuses inwards towards the centre, forming a cobalt enriched intermediate zone [99S1]. The material -
DP-Carbide30 -exhibits the various zones as shown in Fig. 13.58 - cobalt variation, Fig. 13.59 - hardness
variation and Fig. 13.60 - residual stress levels. Such components posses a unique combination of surface
wear resistance with inner toughness and are applied in a number of highly stressed tools, e.g. drawing
mandrels, cold heading dies and drawing dies. The product can also be applied in mining tools [88A1].
The technique of producing a tough surface zone has also been exploited in the case of metal cutting
inserts, which are required to have good edge strength [81N]. The process is accomplished by developing
a 20 - 30 µm surface zone which is free from cubic carbides - (WTi)C - and thus is composed of only
tungsten carbide and cobalt. The cobalt content of this zone is also enriched as shown in Fig. 13.61. This
is usually carried out during vacuum sintering by removal of nitrogen from the Ti(CN) or TiN phases
contained within the bulk alloy. Thus, the nitrogen diffuses outward while titanium diffuses inward as
shown in Fig. 13.62 [88S2]. Both of these reactions are dependent on the diffusivities and solubilities of
titanium and nitrogen in the liquid binder phase. An example of time dependence of the thickness of the
cubic carbide-free zone is shown in Fig. 13.63 [88S2].
It is also possible to achieve a cubic carbide-free zone by vacuum sintering alloys without the
presence of nitrogen with a long holding time at the maximum sintering temperature [93Y]. It was found
that alloys produced using titanium carbide, as opposed to mixed crystal (50WC - 50TiC), develop a
cubic carbide-free zone more readily as shown in Fig. 13.64. The depth of the titanium free zone and the
cobalt enriched zone is illustrated in Fig. 13.65. It can be seen that cobalt variations form a series of
stratified layers. The controlling factor for this process is the inward diffusion of titanium which in turn is
30
Trade name of AB Sandvik Hard Materials, Sweden.

governed by the solubility in the liquid binder phase. Both carbon and / or oxygen gradients play an
important role in this respect.
A third method [89S1] of producing a cubic carbide-free zone in WC-TiC-TaC-Co metal cutting
inserts is to first nitride components which are still porous during the sintering cycle, i.e. before the
liquidus temperature. After holding for 1 - 4 h at a temperature in the range 1250 - 1290 °C and a nitrogen
partial pressure of ca. 40 kPa, a surface zone containing a significant amount of nitrogen is formed. After
pumping out the nitrogen, heating is continued to a sintering temperature of 1500 - 1550 °C under an
argon partial pressure of 100 - 200 Pa for a holding time of 1 - 4 h. This latter treatment removes nitrogen
and sets up a reverse flow of titanium as in the case of the previous technique.
In order to utilise the unique surface zone properties, it is usual to coat components (usually indexable
metal cutting inserts) with layers of Ti(CN), TiN, TiC and / or Al2O3. Thus, a combination of maximum
wear resistance, on metal cutting, with a very high impact edge strength is achieved. Such a material is
Kennametal K 935 grade31.
The method of producing functionally graded hard material has also been applied to cermets [96T2].
In this instance a cermet with a composition of 45 wt% TiN - 40 wt% WC - 10 wt% Co - 5 wt% Ni was
sintered using a controlled special (commercially undisclosed) sintering regime - temperature, atmosphere
and cooling rate - to produce a graded structure. The outermost zone, ca. 5 µm, is composed of pure
tungsten carbide and binder phase, while the next adjacent layer, ca. 20 µm, contains only titanium
carbonitride grains with no binder phase. The graded structure continues, inwards to the core, with
increasing amounts of titanium carbonitride and binder phase until the core zone with a proportion of
tungsten carbide is reached. For practical use the outermost tungsten carbide binder phase layer is
removed. The change in microhardness with depth from the pure Ti(CN) zone is shown in Fig. 13.66. The
variation in cobalt content and residual compressive stress is shown in Fig. 13.67 and Fig. 13.68,
respectively.
13.3.1.12 Joining and retaining hard materials
There are numerous methods used for joining hardmetal components to carriers or supporting units, such
as clamping, screwing, shrinking or force fitting, wire or strip winding. The former is used extensively in
metal machining, where an indexable hardmetal or cermet insert is clamped to a steel tool holder. In some
instances the insert has a central hole which helps with location. Shrinking or force fitting and wire or
strip winding are applied to a variety of components including dies of various sorts and in the former two
methods to button bits in mining tools.
A comparison between two methods of holding a hardmetal die in a steel casing - strip winding versus
shrinking at various imparted compressive stress levels - is shown in Fig. 13.69 [95K1]. The graph shows
the inner allowable pressure in relation to the diameter ratio D/d, where D is the outer diameter of the
steel casing and d is diameter of the hardmetal die.
Various types of adhesives have been used for joining hardmetal components but they suffer from
relatively low joint shear strength - ca. a tenth of that produced by brazing. A further restriction is the fall-
off in joint strength on heating above 50 °C and also in the presence of hot water.
Brazing is a fairly common method used to join hardmetal , though less so for cermets, to steel for the
production of a tool. Before indexable inserts became available, all metal cutting tools were manufactured
by brazing a hardmetal shaped blank onto a steel shank.
The problem associated with brazing stems from the large difference in the coefficient of thermal
expansion of the two materials. Thus, the value for hardmetal alloys is approximately one third to one half
of that of steel. The design of the brazed joint must take this into account in order to minimise the induced
thermal stresses in the component. Distortion of the component and / or cracking of the hardmetal blank
may result in total failure of the process. However, if this limiting factor is taken into account by using
low melting point braze alloys, copper sandwich braze material, slow cooling after brazing, steel to
hardmetal thickness of 3 : 1 and thick braze joints 0.05 - 0.5 mm, the negative effects of the thermal
expansion difference can be restricted.
31
Trademark of Kennametal Inc, Latrobe, USA.

Wetting of the hardmetal surface is usually not a problem if the surface is ground to remove any
contaminants and the correct flux is used to match the brazing alloy. Alternatively, brazing can be carried
out under a hydrogen atmosphere or in a vacuum. In the former case no flux is required, while in the
latter, only a small amount is necessary. The use of a vacuum is restricted to braze alloys which contain
no metals which are easily volatilised. It is possible to electrolytically coat hardmetal with a 3 - 5 µm
nickel layer to improve wetting during brazing.
There are two distinct brazing alloy groups for use with hardmetal. The first group is made up of a
series of alloys based on silver, which have a low working temperature combined with a good strength
and excellent wetting characteristics. A group of such alloys is shown in Table 35 [99J].
The second group consists of a series of copper base alloys with high working temperatures. These alloys
possess excellent strength and are able to penetrate joint gaps from thin interference fits up to 0.5 mm.
The high brazing temperatures can be an advantage, in some instances, where it is required to harden
the steel shank concurrently with the brazing operation, e.g. for rock drilling tools. Table 36 [99J] shows a
series of such alloys.
Table 35. Brazing alloys based on silver with low melting range [99J].
Alloy32 Nominal composition [wt%] Melting range [°C]

Easy-flo 50 % Ag-Cu-Cd-Zn 620 - 630
Easy-flo No 2 42 % Ag-Cu-Cd-Zn 608 - 617
Silver-flo 55 55 % Ag-Cu-Zn-Sn 630 - 660
Easy-flo No 3 50 % Ag-Cu-Cd-Zn-Ni 634 - 656
Argobraze 49H 49 % Ag-Cu-Zn-Ni-Mn 680 - 705
Easy-flo Trifoil C* 50 % Ag-Cu-Cd-Zn 620 - 630
Argobraze 49LM Trifoil* 49 % Ag-Cu-Zn-Ni-Mn 670 - 710
Argobraze 50 50 % Ag-Cu-Cd-Zn-Ni-Mn 639 - 668
Argobraze 40 40 % Ag-Cu-Zn-Ni 670 - 780
Argobraze 502 50 % Ag-Cu-Zn-Ni 660 - 750
*Trifoils have a central copper core.
Fluxes: Easy-flo flux powder and paste for hardmetal easy to wet.
Tenacity 6 flux powder and mattiflux 3A flux paste for hardmetals difficult to wet.
Table 36. Brazing alloys based on copper with high melting range [99J].
Alloy33 Nominal composition [wt%] Melting range [°C]

B-Bronze 97Cu-3Ni-0.02B 1081 - 1101
C-Bronze 85Cu-11Mn-2.5Ni 965 - 995
D-Bronze 86Cu-10Mn-4Co 980 - 1030
F-Bronze 58Cu-2Mn-2Co-38Zn 890 - 930
Fluxes: B-Bronze, Tenacity 12 or 125
C-Bronze, Tenacity 125
D-Bronze, Tenacity 5 or 125
F-Bronze, Tenacity 5 or 125
Further details on brazing hardmetals can be obtained in reference [69K].
32
All trade names and data from Johnson Matthey Metal Joining, U.K.
33
All trade names and data from Johnson Matthey Metal Joining, U.K.


13.3.2.1 Natural diamonds
The recovery of diamonds from mined rock is different from the normal process used for other minerals.
Firstly, it is desirable to recover as many diamonds as possible intact and secondly, the concentration of
diamond is so low - typically one part in 10 million by weight. Although the basic recovery method from
Kimberlite and alluvial deposits is similar for all mines, there are significant differences in the details,
depending upon a variety of factors. A typical flow sheet for diamond recovery is given in Fig. 13.70
[91C].
The recovered diamonds, having removed all gemstone material, are processed by a variety of
techniques to develop a number of strength and surface characteristics which are matched to the end use.
The diamonds can vary from needle to blocky shapes with sharp edges and from rough irregular to
polished smooth surfaces. These are available in a variety of closely graded grit sizes. A selection of such
commercially available diamonds is shown in Table 37 [99D].
13.3.2.2 Synthetic diamonds
Since the early days of the manufacture of diamonds via the HPHT process in the laboratory, enormous
strides have been made in the design and construction of large presses, with the necessary ancillary
equipment, for the mass-production of diamond of various forms.
The basic problem has been to construct equipment which would enable pressures of the order of
6.0 GPa and temperatures greater than 1600 K to be consistently reached and maintained. Various designs
of the pressure units and the inner cell-like capsules have been investigated and one such - a belt-type
apparatus - is shown in Fig. 13.71 [79W]. The exact design of the anvils, die and cell-like capsules is a
closely guarded commercial secret. Suffice to say that controlling the pressure and temperature to the
degree necessary to produce consistent diamond types, is extremely difficult [79W].
To achieve satisfactory diamond synthesis, it is absolutely essential to have a suitable solvent /
catalyst present with the carbon source within the capsule. The range of solvent / catalysts which promote
diamond growth is relatively extensive and they fall into two groups, namely, carbide formers and non-
carbide formers. The commercial producers tend to use alloys of two or more of these elements, e.g. iron-
nickel, cobalt-iron and manganese-nickel [92B].
The pressure and temperature required to initiate and maintain diamond growth is illustrated in
Fig. 13.72 [79W]. This graph has been constructed from a series of reconstitutional experiments in which
mixtures of diamond seed crystals and an iron solvent / catalyst were subjected to a variety of pressure-
temperature regimes. The resultant capsule material was examined to determine the end products of each
experiment. The graph also shows the eutectic line for the Fe-C, Co-C and Ni-C systems as well as the
three-phase equilibrium line - 3-Φ line - which is the locus of the pressure temperature composition space
of the three-phase equilibrium point. The mixture of carbon source (usually graphite) and the chosen
solvent / catalyst is maintained at pressures close to 6 GPa and temperatures above 1500 K, for times
varying from a few minutes to many hours depending upon the type and size of the diamond required.
For a fixed set of capsule design and solvent / catalyst carbon source mixture, the morphology of the
diamond crystals changes from octahedral at low pressure and high temperature, to cubic at high pressure
and low temperature within the diamond stable region, as shown in Fig. 13.73 [92B].
The resultant diamond crystals, the product of the HPHT process, are subjected to a wet chemical
treatment to remove all traces of metal / cell material. For a more fundamental review of the synthesis of
diamond, references [79F, 91C, 92F] should be consulted.
Depending up the end use, diamonds can be synthesised with various morphological, structural and
strength characteristics, e.g. blocky, near perfect crystals with maximum strength to the other end of the
spectrum mosaic, multi crystalline and very friable.
In order to improve retention of diamond grits within resin type bonds - usually phenolic or polyimide
base materials - a metal coating or cladding is applied to the diamond surfaces. The coating surface is

generally nodular although in some instances it may be spiky. This coating also helps reduce temperatures
at the interface with the bond during grinding and so improves retention and prolongs wheel life.
Nickel is applied by electroless as well as by electrolytic means, at levels of 30 wt%, 55 wt% for the
former and 60 wt% for the latter. Copper is applied using an electroless technique at a level of 50 wt%
[93D1]. Nickel and copper coated diamonds are recommended for phenolic resins and polyimide bonds
respectively, while titanium coated grit is supplied for use with metal bonds, e.g. cobalt with iron, steel
and / or bronze. Chromium coated diamonds are especially suited for bonds containing cobalt, tungsten
carbide and low levels of iron and / or bronze [98G].
The following tables illustrate the variety of diamond grits available for incorporating into a range of
tools for a variety of end uses. It should be noted that diamonds are available in different grit sizes to
match the type of tool. Table 38 [99D] shows a variety of synthetic and natural grits of the Prema Dia34
range of De Beers Industrial Diamond Division. The products are graded in relation to the strength at
room temperature and high temperature as well as the crystal structure. Some are recommended for metal
bonded and others for resin bonded grinding wheels. Coated grits are available when required.
34
Trade name of De Beers Industrial Diamond Division, S. Africa.

Table 37. Selection of commercially available natural diamond grit types35 of De Beers Industrial
Diamond Division, S. Africa [99D].
DEBDUST I & II EMB & EMBS SNDMB NRBT & NRBT55N RDPI&II & RDPS
DEBDUST I & II EMB Blocky natural SNDMB Strong, NRBT Flat, needle- RDPI Processed
are high quality diamond particles blocky, well-shaped shaped, friable natural diamond for
processed natural with irregular natural diamond natural diamond use in rotary
diamond for saws. surfaces for high particles with particles treated to dressers. RDPI has a
DEBDUST I has wear resistance and smooth regular improve the smooth highly
more highly good bond retention. faces, sharp cutting mechanical polished surface and
processed particles Strength and thermal edges. Good properties of the grit. is designed for
than DEBDUST II. stability ensure bonding and For resin or ceramic applications where
Both products have excellent outstanding thermal bond applications in very close tolerances
high strength and performance in stability. For metal wet and dry are required.
metal bond
total thermal stability bond applications in grinding. RDPII has a rougher
ensuring excellent applications for grinding and drilling NRBT55N NRBT surface ensuring
life and performance sawing and drilling glass, ceramics, coated to 55 % of firmer retention in
in metal bonds for stone, concrete, plastics, tungsten final product weight the bond.
sawing and drilling masonry and the carbide, and with nickel cladding Recommended
plain and reinforced planing and hardmetals or alloys. for bond retention, where heavy loads or
concrete and stone. grooving of Ideal diamond for anchors diamond in vibrations may be
concrete. EMBS electroplated tools. matrix even when experienced.
with special surface fractured. For resin RDPS is processed
treatment is bond applications in from premium
recommended for wet grinding quality diamond for
refractory materials carbides, where rotary dressers where
and concrete with superior finish is the very finest
tough aggregate and essential finishes are required.
steel reinforcement.
Processed natural Very blocky with Strong, blocky Needly and friable Extra strength - close
diamond particles for irregular surfaces tolerances (RDPII
saws rougher surface)
Sawing and drilling Sawing, drilling Grinding (usually Grinding Rotary profile
electroplated tools wet) electro plated dressing
tools
Plain and reinforced Stone, concrete Glass, ceramics, Carbides Conventional
concrete also masonry and carbide and stone grinding wheels
masonry and refractories
refractories
35

Table 38. Prema Dia Diamond Grits of De Beers Industrial Diamond Division, S. Africa.
PDA 999 PDA 989

Prema Dia PDA 999 is a specially Designed for use in the broad
synthesised, highly crystalline spectrum of high-productivity
diamond with excellent thermal metal bond grinding
and impact strengths, enabling it applications, the synthetic
to withstand the high dynamic material, Prema Dia PDA 989,
loads encountered in demanding performs particularly well in
metal bond applications, such as applications requiring a high-
the high stock removal of tough strength abrasive. It is a blocky,
materials. crystalline material with high
impact strength and thermal
stability.
Friable Strong Friable Strong
Particle strength room temperature
Particle strength high temperature
Mosaic Sharp Crystalline Mosaic Sharp Crystalline
Particle structure
PDA 878 PDA 768

With properties between PDA 989 Prema Dia PDA 768 contains
and PDA 768, PDA 878 is a high specially selected, sharp crystals,
performance, general purpose, with some blocky crystalline
metal bond abrasive. This product particles also present. This
is a crystalline material with a particular combination of shapes
high impact strength at both room makes it ideally suited for a
and high temperatures and is variety of applications which do
designed to give good not require a higher strength
performance over a wide variety material, such as Prema Dia 878.
of metal bond applications.
Particle structure

Table 38 (cont.). Prema Dia Diamond Grits of De Beers Industrial Diamond Division, S. Africa.
PDA 657 PDA 656

PDA 657 make it suitable for use An engineered synthetic diamond
in less demanding metal bond material, consisting mainly of
applications. Because it is an sharp, free cutting, well shaped
engineered material, it has a more particles with a very high thermal
irregular, but consistent, crystal strength. Prema Dia PDA 656
shape, whilst still possessing good possesses excellent bond retention
thermal strength. The nickel clad properties, which make it partic-
form, Prema Dia PDA 657N55, is ularly suitable for use in
ideal for grinding combinations of electroplated tools
tungsten carbide and steel.
Cladding option N55
Particle structure
PDA 446 PDA 665

The sharp particle shape of Prema Because natural diamond has a
Dia PDA 446 enhances its free very high thermal strength,
cutting characteristics, making it exposure to elevated temperatures
suitable for applications where barely affects the strength of the
high particle strength is not of crystal. As a premium natural
paramount importance. diamond material consisting of
Cladding option N55 engineered, blocky, well shaped
particles, Prema Dia PDA 665 is,
therefore, suited to many grinding
applications. In addition, its
characteristics make it highly
suitable for use in electroplated
tools.
Enhanced sizing of PDA 665
PDA 665 contains five specially
size micron abrasives.
Particle structure

Table 38 (cont.). Prema Dia Diamond Grits of De Beers Industrial Diamond Division, S. Africa.
PDA 555 PDA 545

Designed for applications where a A carefully controlled blend of
more friable particle is required, engineered natural and synthetic
Prema Dia PDA 555 is a natural diamond, Prema Dia PDA 545
diamond abrasive consisting of exhibits the excellent thermal
blocky, engineered particles with resistance of natural diamond,
irregular shapes. It has the high while its sharp, irregulary shaped
thermal strength and free cutting particles make it a free cutting
characteristics of natural diamond. product suitable for use in a wide
Cladding option variety of general-purpose
N55 applications. In addition, such
natural/synthetic diamond mixes
have shown good potential in
areas such as the polishing of
stone.
Particle structure
PDA 433 PDA 321

Prema Dia PDA 433 is a product Normally used in metal clad form,
which is highly suitable for use in Prema Dia PDA 321 is the
resin bonds. Normally used in recommended product for a very
nickel clad form, it provides an wide range of applications. Its
economical solution for a range of micro-chipping structure ensures
general purpose applications. the degree of friability required
Cladding options for resin bond applications. Its
N30, N55, P60, C50 structure and thermal resistance
are designed to ensure that the
blocky particles fracture in use to
give sharp cutting edges. In its
unclad form, Prema Dia PDA 321
is suitable for use in vitrified
bonds.
Cladding options
N30, N55, P60, C50
Particle structure

A specially graded series of diamonds for use, predominantly in metal bonded grinding wheels of General
Electric company is shown in Table 39 [96G2]. The table indicates the application regimes as well as the
material being processed. The relative crystal shape is shown in Fig. 13.74, while Fig. 13.75 illustrates the
relative crystal strength [96G2]. These grits may also be coated with nickel, copper, titanium or chro-
mium when required.
Table 39. Selection of MBG1 diamond grits of General Electric Company, USA [96G2].
Product MBG 660 MBG 640 MBG 620 MBG 610 MBG 600 MBG 300
(T)&(Ti)
Applica- Very high impact, High impact, Medium impact, Application
Electro Low impact/
tion high MRR application power high contact areas, requiring
plated, high contact
rigid machine restricted long arc lengths low forces
application areas
machine requiring
per crystal
sharpness
Glass Glass Glass Glass Glass
Automatic pencil edg- Automatic General pencil edging, Automatic Mirror edg-
ing, pencil edg- beveling flat glass & seaming, ing,
fluting crystal stems ing, mirrors, mirror edg- bevel pol-
automatic triple waterfall edging ing, ishing
seaming, bevel pol-
engraving ishing
crystal,
cut off
wheels
Granite Granite Granite Granite Granite Granite

Beveling/edging, Mid stage Trimming Polishing Polishing Finish polish-
trimming, polishing, ing
rough polishing calibrating
Marble/limestone Marble/limestone Marble Marble Marble

Trimming Trimming/polishing Polishing Polishing Polishing
Ceramic tiles Tungsten carbide Ceramic Ceramic Ceramic tiles

comp.
Trimming, Burr grinding Dental Dental Finish
rough polishing burrs, burrs polishing
cut off
wheels
Ferrite Ferrite Cast iron

Grinding motor cores Grinding Honing cylinder liners
motor cores
__________
1
Trade name and data of General Electric Company, USA.

A special chemical cleaning process, of the diamond surfaces, is available to assist in electroplating
[96G2, 99D].
A further type of synthetic diamond has been produced, which is aimed at the sawing and drilling of
concrete and various stone and rock formations. As with other groups, the diamonds have a variety of
shapes and strength characteristics to match the specific end uses. A range of MBS type1 diamonds is
shown in Table 40 [97G], which illustrates the strength and applications. A similar range of diamond grits
are manufactured by De Beers Industrial Diamond Division, S. Africa - DSN2-Series, SDA Plus2-Series,
SDB 1000 2-series - [96D]. A selection of these grits, for use in a range of metal bonds, can be supplied
with a specialised metal coating to assist in grit retention and reduce oxidation, during tool manufacture.
Table 40. Selection of MBS 1 type diamond grits of General Electric Corporation, USA [97G].
MBS 970 MBS 960 MBS 950 MBS 940 MBS 930 MBS 920 MBS 910
MBS 955 MBS 945 MBS 935 MBS 925 MBS 915
Very high impact, High impact, Medium impact Low impact Very low impact
high power machine, power restricted
high cutting rates machine
Concrete/asphalt Concrete/asphalt Concrete/asphalt Concrete/asphalt Concrete/asphalt
Reinforced, Reinforced, Non reinforced, Hand held equipment Hand held equipment,
tough aggregates all aggregates medium aggregates, DIY cutters
light aggregates
Granite Granit Granite Granite Marble/limestone/

loftstone
Wire sawing, Wire sawing, Trimming, Polishing Wire sawing,
multiblade slabbing, multiblade slabbing, calibrating frame sawing,
large blade slabbing, large blade slabbing, polishing
trimming trimming
Marble/limestone Hard marble/ lime- Soft marble/ lime- Natural diamond

stone stone
Belt sawing, Wire sawing, frame Wire sawing, frame Replacement
exploration/mining, sawing, trimming, sawing, trimming
core drilling calibrating
Micron size diamond grits from a mean size of 0.1 to 80 µm are available for all loose lapping and pol-
ishing operations.
Large high quality synthetic diamonds can be manufactured using the reconstitutional technique
whereby a carbon source diamond is maintained at a temperature 20 ~ 50 °C higher than spaced out dia-
mond seed crystals. A metal catalyst/solvent is placed between the two subjects and the cell is placed in a
HPHT apparatus as shown in Fig. 13.76 [98S1). Carbon is transferred through the molten solvent to the
seed crystal surfaces and as the whole cell is maintained in the pressure temperature region of diamond
stability, new diamonds are formed. The holding time, at the prescribed conditions, is extremely long and
dependant upon the size of the crystal required. As an example a cycle time of 5 days is required to grow
crystals of approximately 1 - 2 carats, i.e. a growth rate of 1.7 - 3.4 mg/h. The growth rate of diamonds
__________
1
Trade name of General Electric Corporation, USA.
2
All trade names of De Beers Industrial Diamond Division, S. Africa.

can be controlled by adjusting the temperature gradient between source and seeds. Such single crystal
diamonds can be grown with predominantly cubic or octahedral forms [91C]. Commercial diamonds are
available with dimensions of 4 - 5 mm in length and have applications as wire drawing dies, special cut-
ting tools, surgical scalpels, high pressure anvils, radiation detectors and heat sinks.
13.3.2.3 Cubic boron nitride (CBN) grits
The production of CBN crystals or grits is carried out using a similar technology to that for the production
of synthetic diamond.
The accepted phase diagram with the equilibrium line between hexBN and CBN is shown in
Fig. 13.77 [91C]. The pressure temperature relationship is similar to that for graphite diamond. Again, to
promote satisfactory conversion from one species to the other a suitable catalyst/solvent is necessary.
Experimental work has shown that alkali metals, alkali earth metals or their nitrides/borides act as satis-
factory conversion agents, for example Li3BN2, AlN and AlB2. A mixture of aluminium and magnesium
has also been found to yield satisfactory CBN crystals and also modifies the pressure temperature space
diagram as shown in Fig. 13.78 [94P]. Thus, instead of the usual 5.5 - 8.0 GPa pressure and temperatures
> 1600 °C, a pressure of 4.5 GPa and a temperature of 1460 °C with a 40% Al - 60% Mg alloy cata-
lyst/solvent yielded well developed crystals [94P].
As with the synthesis of diamond types, the relationship between cell design, catalyst/solvent, pres-
sure, temperature and time influences the size and morphology of the CBN crystals.
A selection of CBN grits manufactured by De Beers Industrial Diamond Division, S. Africa and used
for the manufacture of bonded tools is shown in Table 41. [93D2]
Table 41. Selection of CBN grits ABN1 types of De Beers Industrial Diamond Division, S. Africa [93D2].
ABN200 ABN260 ABN300 ABN360

Descriptions ABN200 is a black ABN260 is ABN200 ABN300 is a clear ABN360 is the
irregular shaped clad to 60% weight amber coloured form coated version of the
crystal, with sharp with an electroless of cubic boron ni- product ABN300,
cutting edges. Its nickel coating. This tride, with an ir- and is clad to 60%
basic crystal mor- results in a rough regular shape and a by weight with
phology is different surface texture similar strength to nickel, using an
from ABN300 and which enhances ABN200. However, electroless process.
ABN600, and is mechanical keying it has a slightly The cladding follows
characterised by a and leads to im- higher thermal sta- the particle contours
virtual absence of proved bond reten- bility than ABN200 enhancing the grit’s
cubic faces, and the tion. The combina- and a different mode surface roughness
presence of triangu- tion of the ABN200 of crystal fracture, and resulting in im-
lar growth features substrate grit and which has advan- proved anchorage in
on the octahedral nickel coating results tages in certain ap- resin bonds.
faces. This results in in a very free cutting plications. In par- ABN360 is recom-
a mode of fracture abrasive, giving a ticular, the combi- mended for use in
whereby small frag- good life and mak- nation of shape and wet and dry grinding
ments break off each ing it suitable for use mode of fracture of HSS, as well as
particle leaving the in a wide range of make it ideal for a stainless steels and
main bulk of the both wet and dry wide range of elec- nickel, chrome and
particle behind in a resin bond applica- troplated tools, as titanium alloys.
sharpened condition. tions. well as finding use
ABN200 is used in in sintered metal and
vitrified and electro- vitrified bond tools
plated tools where where a free cutting
its free cutting prop- action is required.
erties may be used to
advantage.
__________
1
Trademark of De Beers Industrial Diamond Division, S. Africa.

ABN200 ABN260 ABN300 ABN360

Particle Black, irregular, free Irregular, free cut- Amber, irregular, Irregular, sharp,
features cutting, uncoated ting, coated (60% by sharp, uncoated coated (60% by
weight electroless Ni weight electroless Ni
cladding) cladding)
Applica- Vitrified and elec- Resin bond tools Electroplated, as Resin bond tools
tions troplated bond tools well as metal and
vitrified bond tools
Workpiece Ferrous metals and Ferrous metals and Ferrous metals and Ferrous metals and
materials superalloys superalloys superalloys superalloys
Table 41 (cont.)
ABN600 ABN615 ABN660
Descriptions ABN600 is a black, ABN615 is a special ABN660 is the
blocky cubic boron Ti clad version of coated version of the
nitride grit, with a ABN600, particu- product ABN600,
much higher strength larly suited to vitre- and is clad to 60%
and thermal stability ous bond tool appli- by weight with Ni,
than ABN200 or cations. The addition using an electroless
ABN300, as well as of this cladding to process. The rough-
being available in a the ABN600 parti- ened texture that the
coarser range. cles results in a cladding provides
ABN600 is primarily product with high for the ABN600, as
designed for use in strength and thermal well as the inherent
sintered metal and stability, as well as a strength of the sub-
vitrified bond appli- compatibility with strate grit, gives
cations with high the high temperature increased perform-
impact loads and bond systems used ance in high stock
where a strong, for this type of tool removal resin bond
thermally stable applications. This
particle is required. makes it ideal for
creep feed and high
stock removal
grinding.
Particle Black, high strength, High strength, High strength,
features blocky, uncoated blocky, coated (Ti) blocky, coated (60%
by weight electroless
nickel)
Applica- Metal and vitrified Vitrified bond tools Resin bond tools
tions bond, as well as
electroplated tools
Workpiece Ferrous metals and Ferrous metals and Ferrous metals and
materials superalloys superalloys superalloys
13.3.2.4 Chemical vapour deposition (CVD)
The application of chemical vapour deposition techniques to the formation of layers of diamond and CBN
has been under intense investigation since the early 1980s.
The basic considerations are to evolve a system whereby the activation energy of a gas phase, that is
at least composed of carbon and hydrogen (sometimes oxygen is present), is raised sufficiently to produce
radicals which are transported from the region of the excitation towards a substrate. It is found that atomic
hydrogen (H·) plays a key role in the CVD process as it creates methyl (·CH3) and other radicals via
hydrogen extraction from CH4 and so allows crystals of diamond to form.

The control of gas composition, temperature (power input), temperature of the substrate, system pressure,
gas flow and distance from the substrate to the gas excitation source is critical for the deposition of a
consistent and satisfactory diamond layer.
Various practical systems have been developed to meet the above criteria, such as DC glow discharge,
microwave, hot filament, DC plasma jet and high current DC arc (HCDCA). All of these systems have
advantages and disadvantages, based on diamond growth rate, area of substrate which can be satisfacto-
rily coated etc. Table 42 [97H1] compares various systems in relation to these factors. Other problems
concern nucleation density, crystal orientation, freedom from spurious carbon forms, and of major im-
portance for certain cutting tools, adhesion between substrate and diamond film. These are discussed in
greater detail in references [90E, 91B, 92S1].
Table 42. Comparison of diamond deposition systems in relation to relative carbon conversion and other
factors [97H1].
Properties/conditions DC - glow Microwave 1.5 kW Microwave 5 kW Hot Filament

2 2 2
Reactor cross section 244 cm 176 cm about 90 - 180 cm 113 cm2
Substrate area 3 cm2 9 cm2 20 cm2 10 cm2
Power input 6 kW 1.4 kW 4.2 kW 1.3 kW
Gas flow 500 s cm3 800 s cm3 200 s cm3 500 s cm3
Methane concentration 4% 0.8 % 3% 1%
Carbon flux 53 mmol/h 16 mmol/h 16 mmol/h 13 mmol/h
Growth rate 27 µm/h 0.5 µm/h 2.6 - 13 µm/h 1 µm/h
Power density
(per substrate area) 2000 W/cm2 155 W/cm2 210 W/cm2 130 W/cm2
(per activation volume) 270 W/cm3 21 W/cm3 25 - 60 W/cm3 260 W/cm3
Absolute CCR* 4.6 % 1.2 % 9.5 % - 48 % 2.3 %

Relative CCR (substrate) 370 % 16 % 43 % - 420 % 25 %
Pressure 233 mbar 60 mbar 220 mbar 20 mbar

Substrate temperature 950 °C 850 °C 830 °C 850 °C
Reference [97H1] [92L2] [96M2] [93H]

* Absolute CCR = total C - flux: deposited diamond.
relative CCR = C - flux over the substrate: deposited diamond.
13.3.2.4.1 Diamond
Two basic diamond coatings have been produced to meet the requirements of the end uses.
The first concerns cutting tools which are made up of a strong substrate with a good toughness and
high compressive strength. Of prime importance is the adhesion between the substrate and the diamond
layer (6 - 40 µm). Hardmetals are the first choice but difficult problems have arisen with adhesion, so in
some cases Si3N4 and SiC have been substituted. Such a material is CVDITE1, which is composed of a
special SiC base with a polished 20 - 30 µm diamond film (1 µm grain size) on the rake face of an index-
able insert. The coating extends approximately half way down the flank sides of the insert. The polished
rake face improves edge sharpness and reduces the effect of the edge radius [92S2].
Attempts have been made to modify the surfaces of hardmetals, i.e. to control the negative influence
of the cobalt binder phase, and make them more receptive to diamond. Plasma etching [97K1] and other
techniques such as etching with alkalines and acids, as well as depositing intermediate layers (usually TiC
__________
1

or WC), forming stable cobalt compounds (silicides, borides etc.), modifying the carbon content and
using alloys, with a low cobalt and/or titanium carbide content, have improved diamond film adhesion.
Processes with high diamond depositing rates also help with this problem [97H2].
The second diamond coating method is arranged to produce thick - free standing - films [93S2, 94G2].
These films are > 100 µm and up to 1 mm thick with diameters up to 135 mm. In these instances the
deposition system has to accommodate the required large substrates, often tantalum or similar materials,
which are necessary for the nucleation and support of the depositing diamond. After completing the proc-
ess, the substrate is dissolved and the diamond film released as a free standing unit. These large pieces of
diamond, such as DIAFILM1 and CVDD2, have many applications in the electronics industry and as spe-
cial optical devices. They may be shaped by laser cutting [94G3, 98S2]. Metallisation processes have
been applied to free standing diamond sheets in order to improve and facilitate electrical connections to
other components in electronic circuitry. Both sputtering and CVD processes are equally satisfactory in
applying coatings. Results from tensile pull tests for a series of experiments are shown in Table 43
[94G3].
Table 43. Results of tensile pull tests on metal coated diamond film and single crystals [94G3].
Metallisation adhesion to diamond
# Coating Substrate Adhesion [MPa] Remarks
1 CVD Ti SXD 34 SXD separated
2 CVD Nb SXD 26 SXD separated
3 CVD Cr SXD 30 SXD separated
4 CVD Nb CVDD 69 Limit of test
5 CVD Cr CVDD 69 Limit of test
6 CVD Cr CVDD 69 T/C 400 °C - liqN2
7 CVD Ti CVDD 69 T/C 400 °C - liqN2
8 CVD Cr, CVD W CVDD 69 Limit of test
9 CVD Cr, El Ni CVDD 50 CVDD shattered
10 CVD Ti, El Ni CVDD 69 Limit of test
11 Sput Ti, Pt, Au CVDD 48 CVDD shattered
12 Sput TiW, Au CVDD 28 CVDD shattered
13 Sput Nb, Pt, Au CVDD 69 Limit of test
14 Sput Ti, Al CVDD 28 Test stopped
* SXD = single crystal diamond.
The metallisation technique has also been applied to free standing diamond pieces 250 - 500 µm thick,
which were subsequently brazed to strong, tough substrates, e.g. hardmetal, and used as cutting tools.
Brazing and grinding of the tools requires considerable care and recognition of the brittleness of diamond
[94G2].
Using physical and chemical vapour deposition processes similar to those used for depositing dia-
mond, and hydrocarbon source gases or solid carbon, it has been found that an amorphous hard carbon
can be deposited on a variety of substrates. Only very thin layers - less than 3 µm - can be deposited due
to problems associated with internal stresses which leads to disruption and disintegration of thicker films.
However, methods have been developed such that large areas up to ca. 9 m2, at low temperature
- ca. 60 °C - can be coated. In some instances surface treatment of the substrate may be necessary to
improve adhesion. In situ or post coating doping of the layer can be carried out to enhance certain proper-
ties [98C3].
__________
1
2
Trade name General Electric Corporation, USA.

13.3.2.4.2 Cubic boron nitride
Attempts have been made to deposit CBN from the gas phase on to suitable substrates but it has been very
difficult to achieve single phase CBN layers. It is generally agreed that the formation of CBN at low pres-
sures is only achievable when highly ionised gas phases are used. In this context a vast range of methods
has been evolved, all however producing high energy plasmas, such as PACVD, microwave plasma
CVD, r.f. plasma CVD, HCED excited plasma CVD, DC plasma CVD, etc. Only very thin CBN layers
-100 nm thick - have been so far achieved. No commercial products are available [97K3, 97K4].
13.3.2.5 Polycrystalline products
In order to manufacture tools, which can be used for a range of commercial applications, methods have
had to be evolved which can convert diamond and CBN grits into fairly large units. One of these has been
to apply the HPHT technique to grits - sometimes with the presence of a binder phase - and an “in situ”
strong substrate, e.g. hardmetal. This has resulted in a range of “polycrystalline” products being available
to industry.
13.3.2.5.1 Diamond
There is a vast number of patents covering the manufacture of polycrystalline diamond tools, most of
them eminating from General Electric Company, USA, De Beers Industrial Diamond Division, S. Africa,
and Sumitomo Electric Industry Ltd., Japan [92T].
The technique is, in most instances, to treat a quantity of diamond grit in a HPHT cell, together with a
metal catalyst/solvent which is usually in the form of a thin disc placed above or below the diamond grit.
Also included in the cell is a substrate, invariably a hardmetal alloy, WC - 6 - 13 wt% Co to which the
polycrystalline (PC) mass bonds during the process. An intermediate very thin metal layer is often inter-
posed between the hardmetal substrate and the diamond grit. The metal catalyst/solvent is usually cobalt
although in certain instances silicon or silicon carbide is infiltrated or mixed with grit. The pressure tem-
perature time process conditions are ca. 5 - 6 GPa; 1200 - 1500 °C; 3 - 15 min. In some cases the poly-
crystalline mass is produced as a free standing unit because of the particular end use.
The following Table 44 lists a selection of such polycrystalline products from various sources, to-
gether with their composition (when known) and available shape.
Table 44. Polycrystalline diamond products from various sources.
Company Product name Binderphase Diamond Comments

(all trade names) grain size
vol% µm
De Beers Syndite CTC 002 Cobalt 2 Available as ca. 0.5 mm thick layers
Industrial Syndite CTB 002 Cobalt 2 on a hardmetal substrate. Rounds,
Diamond Syndite CTB 010 2-8 10 squares and triangles.
Division, Syndite CTB 025 25
S. Africa Cobalt Layer thickness 0.8 mm with shapes
Syndrill SRC ca. 10 20 - 40 of various sizes - discs ca. 50 mm on a
Syndrill SSP 20 - 40 hardmetal substrate.
Syndax 3 SiC/Si 15 - 50 Free standing forms - rectangular,
triangular and pins.
Syndie CSB 008 8 CBS grades in the form of an inner
Syndie CSB 025 Cobalt 25 PC10 diamond core supported by a
Syndie SSB 004 ca. 10 4 hardmetal annulus SSB grades, self-
Syndie SSB 010 10 standing hexagonals.
Syndie NTB 020 20 NTB grade is a thermally stable natu-
ral diamond material in the form of
hexagonals.

Company Product name Binderphase Diamond Comments

(all trade names) grain size
vol% µm
Sumitomo Sumidia DA 90 50 Available as 0.5 mm thick layers on a
Electric Sumidia DA 150 5 hardmetal substrate in the form of
Industry Ltd, Sumidia DA 200 0.5 rounds, rectangles, segments and
Japan triangles.
Sumidia WD ca. 5 - 15 WD 100 in the form of free standing
100, 200, hexagon.
300, 400 Series WD 200 400 hardmetal annular.
with F ultrafine, WD 600 disc supported by a cermet.
N-micron,
EC- <50 µm
diamond size
General Compax 1600 Cobalt ca. 4 Available as ca. 0.5 mm thick layers
Electric Compax 1300 2-8 ca. 5 on a hardmetal substrate. Rounds,
Company, Compax 1500 ca. 25 rectangles, triangles and partial
USA rounds.
Stratapax 2500 Cobalt 25 - 125 Available as polycrystalline layer on a
2-8 hardmetal substrate. Round blanks,
Stratapax 2800 cylinders and stud cutters.
The 2800 series is designed for maxi-
mum abrasion resistance but is less
resistant to impact.
Geoset Thermally Free standing forms rectangular,
stable binder triangular, cylinders and rounds.
Available with a 100 µm nickel coat-
ing to assist bonding.
13.3.2.5.2 Cubic boron nitride
The technique for the production of polycrystalline CBN tools is fundamentally the same as that used for
the manufacture of polycrystalline diamond tools, i.e. the HPHT process. The formation of the various
component parts in the HPHT cell is the same as that for the diamond tools, except that CBN particles are
substituted for diamond. Patent claims indicate that an extensive range of materials can be used as the
catalyst/solvent, although aluminium, cobalt and nickel appear to be the materials most often used. In
many instances the polycrystalline CBN component only makes up 50 - 80 vol% of the cutting tool, the
remainder being made up of various abrasive particles, e.g. TiN, TiC, WC. A selection of commercially
available products is shown in Table 45.
Table 45. Polycrystalline cubic boron nitride (CBN) products from various sources.
Company Product name Secondary CBN grain Comments

(all trade names) phase size
µm
De Beers Amborite AMB 90 AlB2/AlN 8 - 10 Available as solid no

Industrial - 90% CBN backing material discs, up
Diamond to 101.6 mm dia, triangles,
Division, rectangles and rhombus
S. Africa forms. Discs can be laser
“stitched” to specified
blank dimensions.

Company Product name (all trade Secondary CBN grain Comments

names) phase size
µm
Amborite DBN 45 TiN < 1.0 Available as discs, triangles

- 45% CBN and rectangles as a 0.8 mm
layer on a hardmetal sub-
Amborite DBC 50 TiC, WC, 2 strate.
- 50% CBN AlB2, AlN
Amborite DBA 80 TiC, WC, 6

- 80% CBN AlB2, AlN
Sumitomo Sumiboron BN 200 TiN 3 Available as tipped nega-

Electric Sumiboron BN 250 TiN 2 tive and positive indexable
Industry Ltd, Sumiboron BN 300 TiN 0.5 inserts. BN 600 has a high
Japan Sumiboron BN 500 TiN CBN content while the
Sumiboron BN 600 TiN others in the BN series have
Sumiboron BNX 10 TiC a reducing CBN content
Sumiboron BNX 20 TiC from BN 200. BNX series
Sumiboron BNX 500 TiC have a relatively low CBN
content.
General BZN 6000 Ni/Co 3 Available in a variety of

Electric - high CBN content blanks consisting of a layer
Company, of PCBN bonded to a
USA BZN 8100 TiC 1-2 hardmetal substrate.
- relatively low
CBN content
13.3.2.6 Diamond and cubic boron nitride multi phase products
To fulfil the needs of industry with regard to tools which can cut extremely hard materials, e.g. hardmetal,
hardened steel, stone, concrete etc., a variety of specific components have evolved which contain some
form of diamond or CBN. In all cases the composition of the components is a balance between a satis-
factory bond, a filler and the appropriate abrasive grit. These are chosen so that during use wear of the
bond and filler is just sufficient to expose a distinct proportion of the abrasive grit to accomplish the cut-
ting action. The abrasive grit itself is chosen so that it breaks down in an appropriate manner to continu-
ally present new cutting edges. The following sections relate to these components and their production.
13.3.2.6.1 Grinding wheels
Grinding of hard materials has been in existence for many years and the abrasive grit was invariably
either silicon carbide or alumina. However, with the advent of diamond grit and CBN grit being commer-
cially available, new grinding wheels have been manufactured with extended applications.
The grit content of either type in a multi phase product is expressed in the form of “concentration”,
whereby 100 concentration equals 4.4 carats/cm3 and 50 concentration equals 2.2 carats/cm3 etc. Grinding
wheels are therefore made up of the selected concentration, grit type and size (see previous sections on
diamond and CBN grit types, 13.3.2.1, 13.3.2.2 and 13.3.2.3), a bonding agent and a so-called filler. Each
constituent plays an important role in forming a high quality grinding wheel for a specific use. The rela-
tionship between these constituents, including porosity, is shown in Fig. 13.79 [85C].
The type of bonding agent - resin, vitreous or metal - is often used to describe the three most commonly
manufactured wheels. The following tables give some typical data for the production of these wheel
types.

Table 46. Typical data for the production of diamond/CBN resin grinding wheel elements [68D, 72N1].
Bonding agent Wetting Grit types Concen Filler types Production conditions
agent tration-
range
Synthetic resins Furfural- Appropriate 50 - 200 For fine finish- For phenolic resins: hot press
based on pheno- aldehyde metal coated ing: hex. BN, 150 - 170 °C, 20 - 30 MPa,
lic thermosetting friable grits. talc, wood fibre, 15 - 20 min. Cure 175 °C/24 h.
resins magnesia. For For polyimides: hot press ca.
coarser finish- 270 °C, 350 MPa, 5 min. Cure
polyimides- ing: SiC, Al2O3, 300 °C, 16 h in vacuum, then
thermoplastics graphite, fine 450 °C, 30 min in inert atmos-
metal powders. phere.
The specific selected element may be bonded to the appropriate grinding wheel body after moulding or
“in situ” during moulding. The body may be plastic, metal filled plastic or metal (usually aluminum).
Table 47. Typical data for the production of diamond/CBN vitrous grinding wheel elements [72N2, 85C].
Bonding agent Grit types Concentration Filler types Production conditions

range
Glass frits depending Appropriate 125 - 200 SiC, ZrO2, Diamond vitreous: hot press
upon grit type. Hot metal coated or MoS2, Al2O3, ca. 730 °C, 15 - 30 min, may
pressed diamond: uncoated blocky graphite, require post pressing firing
SiO2, Na2O, CaO, or friable de- hex. BN cycle. CBN vitreous: cold
SiC, K2O. pending upon press and sinter ca. 900 °C
Cold pressed and application. time dependant upon frit com-
sintered CBN: SiO2, position.
Na2O, CaO, Al2O3,
B2O3, ZnO, LiO.
In some cases, the 3 - 5 mm thick abrasive containing element is produced, “in situ”, with a 15 - 20 mm
backing unit. This is then bonded to the appropriate grinding wheel body.
Table 48. Typical Data for the Production of Diamond/CBN Metal Grinding Wheel Elements [72N3, 99F].
Bonding agent Grit types Concentration Filler types Production conditions

range
Two basic types: Appropriate 50 - 200 Modifiers based Usually hot press method. For
iron/cobalt based specially coated on additions of iron/cobalt base: cold press ca.
blocky grits. other metals, e.g. 150 MPa release pressure, heat
copper/tin based tungsten, nickel to 800 - 950 °C/ca. 35 MPa/
etc. 3 min, release pressure and
cool. For copper/tin base: as
above except temperature
500 - 780 °C/ca. 40 MPa.
The abrasive containing element is brazed onto a metal grinding wheel body.

13.3.2.6.2 Saws and diamond wires
Saws may be of a circular or long blade construction while diamond wire consists of a series of diamond
impregnated beads threaded and equally spaced, onto a continuous multi stranded steel wire loop. In the
case of the former two types of saw the diamond abrasive is contained within segments, which are then
either brazed or laser welded to the steel body. In the latter instance, the diamond grit is contained within
the whole body of the beads, which have restricted movement on the wire.
The segments and beads are composed of the diamond abrasive grit, a bonding agent (metals and al-
loys) and a filler or modifier.
There are three basic methods of manufactoring these abrasive elements:
- infiltration - liquid phase penetrates around the diamond grit and filler/modifiers (rarely used
for saw segments/beads)
- cold press sinter - liquid phase may or may not be present during the sintering operation;
750 - 1050 °C/5 - 10 min
- hot press - liquid phase may or may not be present during hot pressing.
600 - 1000 °C/15 - 50 MPa/3 - 5 min
The actual production conditions will be determined by the composition of the “mix”, i.e. the diamond
grit, bond/matrices, filler/modifier/matrix and the tool/end use. The bonding agent (matrices) is either a
single metal or more usually an alloy with a relatively low melting point - required for the formation of a
liquid phase - and good wetting/bonding characteristics. The matrix/filler/modifier consists of a whole
range of materials, from metal powders to hard carbide powders. The diamond grit is invariably blocky
(see previous sections 13.3.2.1, 13.3.2.2) with a special coating, chromium or titanium to improve the
wetting and bonding characteristics. The relative additions of each of the basic constituents depend on the
type of tool and the area of application. Table 49 [90K] gives an overview of some of these factors.
Table 49. Matrices/matrix materials and applications [90K]
Infiltration/fusion matrices:
(decreasing matrix hardness/wear resistance)
Applications:
• oil and mining tools for rock drilling
• wear parts/dressing tools for industrial jobs
• cutting tools for concrete and asphalt
Matrix species:
• WC, WC/W2C, W modified with iron, nickel, cobalt; plus infiltrants or fusable powders (cop-
per based alloys)
Sintering matrices:
Applications:
• cutting, grinding, polishing and drilling of sandstone, concrete, asphalt, and granite
Matrix species:
• cobalt, iron, nickel powders modified with WC, WC/W2C, W
Fusion matrices:
Applications:
• cutting, grinding, polishing and drilling of asphalt, granite, marble and glass
Matrix species:
• copper, bronze, nickel, silver alloys modified with cobalt, iron or other materials
The hardness of various cobalt powders, supplied by Eurotungstene Metal Powders, Grenoble, France as
bonding/matrices agents for diamond tools, versus different hot pressing temperatures is shown in
Fig. 13.80 [99 E].

Two special pre-alloyed Co-Fe-Cu powders, NEXT-NXT 1001 and NEXT-NXT 2001 [98E] as well as the
same powders but incorporating 20 wt% WC (3 µm) powder, NEXT-NXT 11801 and NEXT-NXT 21801
[98E] are available as matrices and combined matrices/matrix for diamond tool production, respectively.
The hardness of these materials when hot pressed is shown in Table 50 [98E].
Table 50. Hardness of hot pressed NXT 1001, NXT 2001, NXT 11801 and NXT 21801 powders [98E].
Powder type Hot press conditions Hardness

1
NXT 100 750 °C/35 MPa 319 ± 7 HB
NXT 2001 750 °C/35 MPa 246 ± 7 HB
NXT 11801 775 °C - as sintered 350 HV10

NXT 21801 775 °C - as sintered 265 HV10
13.3.2.6.3 Drill bits
There are two distinct types of drill bits: coring bits and full hole bits. In the former case the bit head is in
the form of a ring containing the abrasive/cutting elements, while in the latter the full surface is impreg-
nated or covered with spaced cutting elements.
The various forms of coring bits and their manufacture are shown in Table 51.
Table 51. Construction of different forms of coring bits.
Type of bit and construction Method of manufacture Manufacturing conditions

[Similar to those for saw seg-
ment production]
1) Hand set 1) Hand set using low melting point 1) 600 - 750 °C/3 - 10 min
single diamonds. matrices with modifiers.
2) Impregnated diamonds. 2) Hot pressed using low melting point 2) 600 - 800 °C/15 - 35 MPa/
matrices with modifiers. 3 - 5 min
3) Impregnated diamonds 3) Infiltration with low melting point 3) 750 - 1000 °C/3 - 10 min
plus surface spaced Syn- matrices of diamond/matrix, with sur-
dax 3*/Geoset** poly- face spaced polycrystalline forms.
crystalline forms.
4) Surface set Syndax 3*/ 4) Infiltration with low melting point 4) 750 - 1000 °C/3 - 10 min
Geoset** polycrystalline matrices of modifiers/matrix of sur-
forms. face spaced polycrystalline forms.
* Syndax 3 is a trade name of De Beers Industrial Diamond Division, S. Africa.

** Geoset is a trade name of General Electric Company, USA.
The various forms of full hole bits and their manufacture is shown in Table 52.
__________
1
Trademarks of Eurotungstene Metal Powders, Grenoble, France.

Table 52. Construction of different full hole bits
Type of bit and construction Method of manufacture Manufacturing conditions [Similar

to those for saw segment produc-
tion]
1) Hand set single diamonds as for 1) Table 51

2) Impregnated diamonds as for 2) Table 51
3) Impregnated diamonds plus as for 3) Table 51
surface spaced Syndax 3**/
Geoset* polycrystalline forms
4) Surface Set Syndax 3**/ as for 4) Table 51
Geoset* polycrystalline forms
5) Surface set Stratapax*/ Brazed onto steel crown. Discs or Braze: low melting point alloys
Syndrill** hard metal backed studs can be used in a variety of with copper sandwich, 750 °C/
polycrystalline forms patterns 3 - 5 min. With Syndrill** SSP
temperatures of up to 800 °C and
times up to 15 min can be used
* Stratapax and Geoset are trade names of General Electric Company, USA.
** Syndrill and Syndax 3 are trade names of De Beers Industrial Diamond Division, S. Africa.
Further information can be obtained from references [91N, 93P, 98D, 98W].
13.3.2.6.4 Woodworking tools
The use of polycrystalline diamond blanks, such as Syndite CTC 0021 and Compax 16002, for the cutting
of wood and wood type products, e.g. chipboard, fibreboard, laminated board and fibre reinforced plas-
tics, has grown at an enormous rate since their introduction in the 1980s. They are used in saws, cutters,
hoggers, routers and drills. The usual method of construction is based on either mechanical clamping the
hardmetal backed abrasive element or brazing the complete unit onto a steel body. Brazing is carried out
either manually, or with fully automated equipment [90M2, 93C].
13.3.2.6.5 Degradation of diamond and CBN
In all cases, in the production of multi phase cutting tools with diamond abrasives, due recognition has to
be given to the fact that degradation of the diamond can occur during the heating cycle. This takes place
by apparent graphitisation of the diamond particles when oxygen is present at temperatures above 700 °C
and results in the formation of oxidation products CO2 and CO. In a vacuum no graphitisation is detect-
able below 1500 °C.
In polycrystalline and multi phase products the presence of metallic binders/modifiers has a marked
influence on graphitisation at the diamond/metal boundaries. This is particularly true when metals such as
cobalt, nickel and iron are present. This type of degradation results in a progressive reduction in strength
and abrasion resistance of the diamond grit and thus the tool as a whole.
To illustrate these points, Fig. 13.81 [75B1] shows the loss in strength of 40/50 US mesh SDA 1003
diamond grit when heated for 20 min at various temperatures in the presence of three different matrices
materials namely pure cobalt, WC - 25 wt% Co hardmetal and 80 wt% iron - 20 wt% bronze (80 wt% Cu
- 20 wt% Sn). The results show that pure cobalt has the greatest effect while iron/bronze has the least.
__________
1
Syndite CTC 002 is a trademark of De Beers Industrial Diamond Division, S. Africa.
2
Compax 1600 is a trademark of General Electric Company, USA.
3
SDA 100, Syndite and Syndrill are trademarks of De Beers Industrial Diamond Division, S. Africa.

Even so, strength as determined by the De Beers Friatest method, is significantly reduced in all cases, at
temperatures above 800 °C.
With polycrystalline products, e.g. Syndite1, Syndrill1, Compax3 and Stratapax3, where cobalt and/or
nickel is present in the structure of the compact and the abrasive element is bonded to a hardmetal support
element, problems of expansion differences between the metals/hardmetal and diamond also become
evident. Fig. 13.82 [84B] shows the difference in volume expansion between cobalt and diamond that
occurs on heating and is applicable to the abrasive element, while Fig. 13.83 [84B] is applicable to the
abrasive element/hardmetal support element. Tests on Syndite1 have elucidated the acceptable
time/temperature working parameters for brazing such products onto steel tool shanks or supports as
shown in Fig. 13.84 [84B].
In all cases of processing these products, it is recommended that low melting point infiltrants/matrices
binders and braze alloys be used together with short time interval at the working temperature [84B].
Thermally stable polycrystalline products containing non-metallic binders, such as Syndax 31 and
Geoset2, do not possess the same thermal problems associated with the above products. This is demon-
strated in Fig. 13.85 [88C] where test results from heat treating Syndax 31 elements and using them in
granite turning tests have shown only a relatively slight wear degradation even with heat treatment tem-
peratures as high as 1200 °C [88C].
Natural and synthetic diamond grit for use with metal infiltrants/metallic matrices are available with
special metal coatings - chromium and titanium [96G2, 99D]. These coatings enhance retention of the
diamond particles in the matrices and at the same time suppress degradation of the diamond.
Because of the insensitivity of CBN to temperature and oxygen - up to 1400 °C - no special precau-
tions are required when incorporating this abrasive into multi phase cutting tools.
13.3.2.6.6 Electroplated tools
The production of electroplated tools is based on the electrodeposition of a metal, invariably nickel, onto
a steel mandrel or form wheel, while at the same time bonding and entrapping diamond or CBN particles
onto the same surface. Although it is possible to produce multilayers, it is usual to bond a single diamond
or CBN layer onto the form tool. A number of abrasive grit types are recommended for electroplating and
it is also advised, in the case of diamond, that the grit be chemically pretreated to enhance plating char-
acteristics. The following Table 53 illustrates some of the typical data associated with this process.
Table 53. Electrodeposition parameters
Bath type Current pH T Deposition Diamond grit type CBN grit type
density rate
A/dm2 °C µm/h
Nickel sul- 2 - 15 3.5 - 4.0 25 - 50 25 - 50 *EGB, MBG T, *CBN Type 1,
phamate 640T, 660T, 600T, 500, 570;
**EMB, SNDMB, **ABN 200, 300,
EDC, SDA, MDA 600
(chemical treatment
T or E)
* EGB, MBG T, 640T, 660T, 600T, T, CBN Type 1, 500, 570 trade names and marks of General Electric
Corporation, USA.
** EMB, SNDMB, EDC, SDA, MDA with E, ABN 200, 300, 600 trade names and marks of De Beers
Industrial Diamond Division, S. Africa.
__________
1
Syndite, Syndrill and Syndax 3 are trade names of De Beers Industrial Diamond Division, S. Africa.
2
Geoset is a trade name of General Electric Company, USA.
3
Compax and Stratapax are trade names of General Electric Company, USA.

The process may be carried out on the basis of a one or two stage system. In the latter case the abrasive
grit is tacked onto the surface in the first stage and then the coating is built up to the desired thickness in
the second stage. In the former case, both stages are carried out in one bath. A sufficient thickness is re-
quired to firmly retain the abrasive grit but the level of the free abrasive protrusion is varied according to
the application. Thus, the coating thickness should be 30 - 40 % of the abrasive grit diameter for high
speed grinding. When cutting glass fibre reinforced plastics it should be 30 - 50 %, while for machining
ceramics or hardmetal 60 - 70 % and for machining stone 100 %. The type and size of the abrasive grit is
dependent upon the application and material to be machined [66G, 74G, 93G3, 93P, 99D].
13.3.3 Shaping of solid components

Although in many instances the near final shape of a component is attained during the production stage, it
is often necessary to carry out a final shaping/finishing operation to achieve the requisite standards de-
manded by the application. For example, the cutting edge of a tool may have to be finished to a precise
sharpness with exact cutting angles or the surface of a roll or press tool has to have a defined flatness
and/or surface finish. Dimensional accuracy also necessitates some form of final finishing operation, e.g.
for press form tools. All of these requisites can only be achieved by this final manufacturing stage.
13.3.3.1 Hardmetal and cermets
The usual technique for shaping fully sintered hardmetals and cermets is by grinding with diamond abra-
sive wheels. There are various means of grinding such as reciprocating surface, plunge, form, cylindrical
etc. and each may be carried out wet or dry, i.e. with or without coolants, respectively.
There are numerous factors controlling the efficiency of the grinding operation including the follow-
ing:
- grinding wheel: type, size and concentration of the abrasive grit
type of bond, resin, metal, vitreous or electrolytic
- machine: overall rigidity, stability of bearings
- machine operating conditions: surface speed of wheel, down feed (in feed), cross feed, table speed,
with wet grinding, coolant type and flow conditions
- grade of hardmetal or cermet: composition, grain size of hard constituent.
All of these play an important role in the total concept of grinding efficiency.
The latter factor, grade of hardmetal or cermet, is demonstrated by the values of the grinding ratio (G)
in Table 54 [92G2]. The grinding ratio (G) is the quotient of the volume of material removed and the
volume of wheel consumed. The higher the value of G the longer the wheel life. Although all wheel types
may be used for grinding these hard materials, it is usually considered that resin bonded wheels are the
most satisfactory [92G2].
Table 54. Effect of hardmetal grade on grinding ratio - wet reciprocating surface grinding with resin type
IAI wheel [92G2].
Hardmetal composition [wt%] Hardmetal Grinding ratio G

WC Co TiC TaC grain size [µm]
(1) 94 6 - - 1-2 340

(2) 91 9 - - 3-4 225
(3) 94 6 - - 1-4 270
(4) 87 13 - - 1-4 205
(5) 72 8.5 8 11.5 3-5 145
(6) 64 6 25.5 4.5 3-5 260

With dry form grinding the difference in the grinding ratio is also evident with the same set of hardmetal
grades as shown in Table 55 [63K].
Table 55. Effect of hardmetal grade on grinding ratio - dry form grinding with resin type DIIV9 wheel [63K].
Hardmetal grade Grinding ratio as expressed as a relative

value to that for grade (1) [%]
(1) 100
(2) 60
(3) 100
(4) -
(5)* 65
(6)* 110
* The grinding conditions were modified because of heat checking and so the table speed and feed were
reduced. This results in a much lower stock removal rate than for the other WC - Co grades.
In general, the highest G values are achieved, both under wet or dry conditions, with fine grain tungsten
carbide - low cobalt alloys.
The economic material removal rate is in the range 16.4 32.8 cm3/h for dry form grinding and
32.8 - 164 cm3/h for wet reciprocal surface grinding [92G2].
Grinding can also involve combinations of steel and hardmetal, e.g. a hardmetal die held in a cylindri-
cal steel body. Table 56 [92G2] illustrates the fact that different diamond grit types are required for opti-
mum results and different grinding conditions.
Table 56. Optimum diamond abrasive grit types in resin bonded grinding wheels for various grinding
conditions [92G2].
Type of abrasive* Dry grinding Wet grinding

Hardmetal Hardmetal/steel Hardmetal Hardmetal/steel
RVG Fair Good Good Good
RVG W56 Good Better 0 - 15% steel Better Better
RVG W30 Good Best overall No No
RVG 880 Better No Best No
RVG D Best No No No
CSG 11 No Best over 33% steel No Best
* All trademarks of General Electric Company, USA.
For more information references [63K, 69H, 92G2] should be consulted.

Grinding of cermets is considered to be more difficult than hardmetals because of the generation of
high normal loads and the production of relatively fine grinding debris which loads the surface of the
grinding wheel. This adds to the already high normal loads. Resin bonded wheels are recommended for
this application and Fig. 13.86 [99B1] indicates the improvement in wheel life that can be achieved by the
correct selection of the diamond abrasive grit. It is evident that a low impact strength friable grit with a
55 wt% Ni coating - 1PDA 211 N55 - more than doubles the G ratio when compared with a blocky type -
1
PDA 657 N55.
Honing and lapping are specific forming operations used where restrictions of shape and dimensions of
the work material are to the fore.
__________
1
Trademarks of de Beers Industrial Diamond Division, S. Africa.

Honing is usually confined to the bore of a component and the abrasive elements are in the form of
strips bonded to a carrier. The technique is applied where accuracy of dimensions, particularly, out of
roundness, and a good surface finish over a relatively long distance are essential. For an abrasive element
containing a 15 µm diamond grit, an Rt value of 0.5 µm can be achieved.
Lapping is carried out using loose abrasive grit - silicon carbide, boron carbide or diamond - sus-
pended in a paste or liquid which is placed on top of a carrier plate. A variety of surfaces may be treated
depending upon the technique employed. A number of operating factors influence surface finish, such as
abrasive grit size, distribution and concentration, lapping pressure, tracking speed and type of carrier
plate. Removal rates of 0.2 mm/min can be achieved using optimum conditions while surface finishes of
Ra = 0.008 µm and Rt = 0.065 µm may be attained using a 3 µm diamond grit and a soft carrier cloth
[95K1].
Electro Discharge Machining (EDM) is carried out using a variety of electrode shapes, e.g. discs
(wheels), mandrels or wire. These may be constructed from copper, copper tungsten alloys, graphite and
in the case of wire, copper or zinc coated copper. The operating conditions of the various machines avail-
able are relatively complex and reference to machine manufacturers are recommended [91A, 99C1, 99L,
99T2].
The composition and grain size of the hardmetal play important roles in determining the rate of re-
moval and the surface finish of the eroded material. These are demonstrated in Fig. 13.87 and Fig. 13.88
respectively. The results show that with increasing binder content, the removal rate is reduced, while the
surface finish deteriorates [91M1]. Increase in WC grain size results in an increase in the rate of removal
whilst also increasing surface roughness [89G1].
Although laser machining has been suggested for the shaping of hardmetals, very little practical use
has been made of the technique. In some cases the technique has been adopted to permanently mark
hardmetal components.
13.3.3.2 Diamond and CBN
The mechanical grinding of polycrystalline diamond (PCD) and CBN (PCBN) tools has been used since
their introduction in the mid 1970s. However, the grinding costs have been exceptionally high due to the
very low G ratios typically 0.005 - 0.02, the wheel costs and high cutting forces. It is common to use resin
bonded wheels with a high diamond grit content - > 150 concentration - and a friable type of grit. How-
ever, under certain circumstances vitreous bonded wheels, again with an exceptionally high diamond
content - ≥ 200 concentration - can be used.
By far the most common method of shaping PCD, and certain low concentration PCBN tools has been
by electro discharge machining (EDM), either with a wire for slicing and shaping, or a disc/wheel for
sharpening. Because of the complexities of the machines and their operating conditions reference should
be made to the manufacturers [91A, 94V, 99C1, 99L, 99T2].
In operating the machines, the type of polycrystalline product markedly influences the efficiency of
the process. The major factor concerns the specific electrical conductivity - it should be ≥ 10−2 S/cm.
However, the type and distribution of the abrasive grit and the volume fraction of the conductive ma-
trix/binder also influences the efficiency of the EDM process.
Fig. 13.89 [96A] shows the G-ratio achieved with various polycrystalline products with different peak
currents. A graphite wheel was used and the on-off cycle was 100 µs on-time and 10 µs off-time. All
other operating conditions were identical for all tests. The results show that of the PCD products, the fine
grain material gives the highest G-ratio value. However, the low concentration mixed PCBN product
gives substantially better results over the full peak current settings.
The results shown in Fig. 13.90 and Fig. 13.91 [97S3] demonstrate the cutting rate and surface finish
obtained on three PCD products, as well as a hardmetal (WC-10 wt% Co), when wire EDM processed.
The wire in-feed was 30 µm, the on-off time ratio was 0.23 while all other conditions were held constant,
except the pulse frequency, which was varied over the range ca. 80 to ca. 210 kHz.
The results, under these cutting conditions, show that the cutting rate is highest for the fine grain ma-
terial, although the difference between the grades is not pronounced. The cutting rate for the hardmetal is
three to four times higher than for the PCD materials. An increase in pulse frequency results in an in-
crease in cutting rate for all materials. The surface finish of all materials decreases in a linear manner with

increasing pulse frequency. The highest quality finish is achieved with the fine grain PCD and worst with
the hardmetal.
Laser machining has been used on PCD and PCBN products though it tends to be confined to high
concentration > 95 % CBN tools.
13.4 Properties of hardmetals and cermets

The first section details the standard test methods applicable to hardmetals and cermets. Although no
specific standards have been alloted to cermets, it is usual practice in the industry, to use the same
methods as those used for hardmetal. However, care should be taken in applying these techniques with
certain types of cermet.
The properties of hardmetals and cermets are dealt with, in the first instance, under the property list-
ings of a number of manufacturers using the appropriate grade designations. The scope is expanded to
look at a number of properties and their relationship to the composition and grain size (structure) of a
number of selected materials.
13.4.1 Standards
The majority of standards associated with hardmetal and cermets eminate from the International Organi-
sation for Standardisation (ISO) which operates in conjunction with various organisations associated with
Specific Countries, e.g. DIN-Germany, BSI-U.K. etc. In the USA, the American National Standards In-
stitute (ANSI) operates as a unifying organisation for a number of groups including the American Society
for Testing Materials (ASTM). The Japanese Industrial Standards (JIS) organisation is responsible for
standards in Japan.
The following sections give information relating to the various topics under the heading of Chemical,
Physical/Mechanical and Machining. Within the former section, standards dealing with powders are con-
solidated.
13.4.1.1 Chemical
The relevant standards dealing with the chemical investigation of both powder and sintered hardmetals
are given in Table 57. Table 58 deals with standards associated with the physical testing of powders.
13.4.1.2 Physical/mechanical
The standards applicable to the physical/mechanical investigation of sintered hardmetals are shown in
Table 59. For an appraisal of the problems associated with the physical and mechanical testing of sintered
hardmedals, the following references should be consulted [92R, 95R, 96R2].
13.4.1.3 Machining
The internationally accepted standard for designating codes for hardmetals, cermets, ceramics, diamond
and cubic boron nitride (CBN) used in metal cutting operations is ISO 513 : 1991 E. Because of the im-
portance of this standard it is shown in its complete form in Table 60. The overwhelming majority of
cutting operations are carried out with indexable cutting inserts which are held by some form of clamping
in a tool holder. The following standards govern this application area.
ISO 1832 Designations for indexable inserts

ISO 5608 Designations for turning and copying tool holders and cartridges
ISO 6261 Designations for boring bars.

increasing pulse frequency. The highest quality finish is achieved with the fine grain PCD and worst with
the hardmetal.
Laser machining has been used on PCD and PCBN products though it tends to be confined to high
concentration > 95 % CBN tools.
13.4 Properties of hardmetals and cermets

The first section details the standard test methods applicable to hardmetals and cermets. Although no
specific standards have been alloted to cermets, it is usual practice in the industry, to use the same
methods as those used for hardmetal. However, care should be taken in applying these techniques with
certain types of cermet.
The properties of hardmetals and cermets are dealt with, in the first instance, under the property list-
ings of a number of manufacturers using the appropriate grade designations. The scope is expanded to
look at a number of properties and their relationship to the composition and grain size (structure) of a
number of selected materials.
13.4.1 Standards
The majority of standards associated with hardmetal and cermets eminate from the International Organi-
sation for Standardisation (ISO) which operates in conjunction with various organisations associated with
Specific Countries, e.g. DIN-Germany, BSI-U.K. etc. In the USA, the American National Standards In-
stitute (ANSI) operates as a unifying organisation for a number of groups including the American Society
for Testing Materials (ASTM). The Japanese Industrial Standards (JIS) organisation is responsible for
standards in Japan.
The following sections give information relating to the various topics under the heading of Chemical,
Physical/Mechanical and Machining. Within the former section, standards dealing with powders are con-
solidated.
13.4.1.1 Chemical
The relevant standards dealing with the chemical investigation of both powder and sintered hardmetals
are given in Table 57. Table 58 deals with standards associated with the physical testing of powders.
13.4.1.2 Physical/mechanical
The standards applicable to the physical/mechanical investigation of sintered hardmetals are shown in
Table 59. For an appraisal of the problems associated with the physical and mechanical testing of sintered
hardmedals, the following references should be consulted [92R, 95R, 96R2].
13.4.1.3 Machining
The internationally accepted standard for designating codes for hardmetals, cermets, ceramics, diamond
and cubic boron nitride (CBN) used in metal cutting operations is ISO 513 : 1991 E. Because of the im-
portance of this standard it is shown in its complete form in Table 60. The overwhelming majority of
cutting operations are carried out with indexable cutting inserts which are held by some form of clamping
in a tool holder. The following standards govern this application area.
ISO 1832 Designations for indexable inserts

ISO 5608 Designations for turning and copying tool holders and cartridges
ISO 6261 Designations for boring bars.

Table 57. Standards for the chemical investigation of hardmetals.
Standard Description
reference
number
ISO 3907 Determination of total carbon content - gravimetric method
ISO 3908 Determination of insoluble (free) carbon content - gravimetric method
ISO 3909 Determination of cobalt - potentiometric method
ISO 4491/1 Determination of the loss of mass on hydrogen reduction - general directive
ISO 4491/2 Determination of the loss of mass on hydrogen reduction
ISO 4501 Determination of titanium - photometric peroxide method
ISO 4503 Determination of contents of metallic elements by X-ray fluorescence - fusion method
ISO 4883 Determination of contents of metallic elements by X-ray fluorescence - solution method
ISO 7627/1 Chemical analysis by flame atomic absorption spectrometry -
Part 1: General requirements
Part 2: Determination of calcium, magnesium and sodium in contents from 0.001 - 0.02 %
Part 3: Determination of cobalt, iron, manganese and nickel in contents from 0.01 - 0.5 %
Part 4: Determination of molybdenum, titanium and vanadium in contents
from 0.01 % - 0.5 %
Part 5: Determination of cobalt, iron, manganese and nickel in contents from 0.5 - 2.0 %
Part 6: Determination of chromium in contents from 0.01 - 2.0 %
ISO 10854 Determination of silicon content in carbonaceous material by photometric method
ISO 11873 Determination of sulphur and carbon contents in cobalt metal by IR-method
ISO 11874 Determination of phosphorus content in cobalt metal - photometric method
ISO 11875 Determination of aluminium content in cobalt metal - FAAS method
ISO 11876 Determination of calcium, copper, iron, potassium, magnesium, sodium, nickel and zinc
in cobalt metal - FAAS method
ISO 11877 Determination of silicon content in cobalt metal - photometric method
ISO 10850 Determination of the ash content of carbonaceous material
ISO 10851 Determination of moisture content in carbonaceous materials - gravimetric method
ISO 10852 Determination of sulphur content in carbonaceous material - cambo method
ISO 10853 Determination of calcium, iron, magnesium and sodium in carbonaceous material -
FAAS method
Table 58. Standards for the physical investigation of powders.
reference number
ISO 3923/1 Determination of apparent density - Part 1 - funnel method
ISO 3923/2 Determination of apparent density - Part 2 - Scott volumeter method
ISO 4884 Sampling and testing of powders using sintered test pieces
ASTM B213 Flow rate of metal powders (applicable to granules)
ASTM B330 Average particle size of powders of refractory metals and their compounds
by the Fisher sub-sieve sizer.

Table 59. Standards for the physical/mechanical investigation of sintered hardmetals.
Reference Number
ISO 4489 Sintered hardmetals - sampling and testing
ISO 4499 Metallographic determination of microstructure
ISO 4505 Metallographic determination of porosity and uncombined carbon
ISO 3312 Determination of Young’s modulus
ISO 3326 Determination (of the magnetization) of coercivity
ISO 3327 Determination of transverse rupture strength
ISO 3369 Determination of density
ISO 3878 Vickers hardness test
ASTM B294 Hardness testing - Rockwell
ISO 4506 Compression test
ASTM B611 Abrasion wear resistance of cemented carbides
ISO 12692 Abrasive wear test for hardmetals
ASTM B421 Electrical resistivity of cemented tungsten carbides
Table 60. International standard ISO 513:1991 E.

Application of hard cutting materials for machining by chip removal - Designation of the main groups of
chip removal and groups of application.
1 Scope
This international standard specifies the designation for hard cutting materials which includes hard
metals, ceramics, diamond, and boron nitride, for machining by chip removal, and establishing their
application.
It is not applicable for other uses (such as, for example, mining and other percussion tools, wire
drawing dies, tools operating by deformation of the metal, comparator contact tips, etc.).
2 Normative reference
The following standard contains provisions which, through reference in this text, constitute provisions of
this International Standard. At the time of publication, the edition indicated was valid. All standards are
subject to revision, and parties to agreements based on this International Standard are encouraged to in-
vestigate the possibility of applying the most recent edition of the standard indicated below. Members of
IEC and ISO maintain registers of currently valid International Standards.
ISO 504 : 1975, Turning tools with carbide tips - Designation and marking.
3 Designation
The designation of groups of application for hard cutting materials includes the letter symbols in accor-
dance with Tables A to D, followed by a dash and the designation of the main group of chip removal and
of the group of application, as specified in Table D.

Table A Hardmetals
Letter symbol Group of hardmetal

HW (optional) Uncoated hardmetal containing primarily tungsten carbide (WC)
HT* Uncoated hardmetal containing primarily titanium carbides (TiC) or titanium
nitrides (TiN) or both
HC Hardmetals as above, but coated
*These hardmetals are also named “cermets”.
Table B Ceramics
Letter symbol Group of ceramics

CA Oxide ceramics containing primarily aluminum oxide (Al2O3)
CM Mixed ceramics based on aluminum oxide (Al2O3) but containing components other
than oxides
CN Nitride ceramics containing primarily silicon nitride (Si3N4)
CC Ceramics as above, but coated
Table C Diamond
Letter symbol Group of diamond

DP Polycrystalline diamond*
* Polycrystalline diamond and polycrystalline boron nitride are also named “superhard cutting materials”.
Table D Boron nitride
Letter symbol Group of boron nitride

BN Polycrystalline boron nitride*
* Polycrystalline boron nitride and polycrystalline diamond are also named “superhard cutting materials”.
Examples
HW - P 10 or P 10 (optionally)
HC - K 20
CA - K 10

4 Classification
4.1 General
Hard cutting materials are classified in Table E, according to their application, in main groups of chip
removal and these groups are subdivided into groups of application.
The groups of application are designated by a letter (P, M or K) indicating the relevant main group
followed by a distinguishing number and these groupings define the fields of application within which
manufacturers of hard cutting materials may classify their own particular grades of hard cutting materials.
The letters P, M and K are thus intended exclusively for the general classification of hard cutting ma-
terials and should never be used, either separately or in conjunction with another letter, as a commercial
designation for a particular grade.
4.2 Main groups of chip removal
This International Standard provides for three main groups of chip removal, based on three broad classes
of material to be machined, as indicated in Table E, which are designated by the letters P, M and K
respectively.
These letters are purely conventional and have no other significance in themselves; they are not the
initials of particular words.
Each of these groups has a corresponding distinctive colour marking, blue, yellow or red.
4.3 Groups of application
Each main group is subdivided into groups of application based on the working conditions in which it is
used.
These working conditions are expressed in Table E in very general terms and manufacturers of hard
cutting materials may possibly describe them, for their own purposes, in terms more directly related to the
fields of use for the hard cutting materials which they manufacture.
The groups of application are designated by the letter for the main group to which they belong,
followed by a distinguishing number.
The higher the number within each main group, the lower is the wear resistance and the greater the
toughness of the hard cutting material.
Where there is a real need for an intermediate group of application, it should be designated by an
intermediate number, for example K 15 between K 10 and K 20, but there should never be more than one
group interpolated between two of the tabulated groups of application; there is no point in introducing
such a group unless the hard cutting material so classified differs appreciably from the neighbouring
groups and this would not be the case if too many further interpolations were adopted.
In the particular case of the P 01 group of application, however, this group may be subdivided by
using the decimal designations P 01.1, P 01.2, P 01.3, etc., if necessary, to distinguish the different
degrees of wear resistance and toughness in the finishing operations on materials with long chips which
constitute this group of application.

13-64
Table E. Classification of hard cutting materials according to use.
Main groups of chip removal Groups of application Direction of increase in

characteristic
Symbol Broad Distin- Desig- Material to be machined Use and working conditions
of cut of hard
categories guishing nation
cutting
of material to colours
materials
be machined
Toughness
Increasing feed
P 01 Steel, steel castings Finish turning and boring; high cutting
speeds, small chip section, accuracy of
dimensions and fine finish, vibration-free
operation.
P 10 Steel, steel castings Turning, copying, threading and milling,

high cutting speeds, small or medium chip
13 Hard materials
sections.
P 20 Steel, steel castings Turning, copying, milling, medium cutting

malleable cast iron with speeds and chip sections, planing with small
long chips chip sections.
Ferrous P 30 Steel, steel castings Turning, milling, planing, medium or low
blue
P metals with Malleable cast iron with cutting speeds, medium or large chip
long chips long chips sections, and machining in unfavourable
conditions.1
P 40 Steel Turning, planing, slotting, low cutting
Steel castings with sand speeds, large chip sections with the
inclusion and cavities possibility or large cutting angles for
machining in unfavourable conditions1 and
work on automatic machines.
Increasing speed
P 50 Steel For operations demanding very tough hard
Wear resistance
Steel castings of medium or cutting materials: turning, planing, slotting,
[Ref. p. 13-185
low tensile strength, with low cutting speeds, large chip sections, with
sand inclusion and cavities the possibility of large cutting angles for
machining in unfavourable conditions1 and
work on automatic machines.
Ref. p. 13-185]
Table E. Classification of hard cutting materials according to use (continued).

characteristic
Symbol Broad Distin- Desig- Material to be machined Use and working conditions of cut of hard cutting
categories guishing nation materials
of material to colours
be machined
Toughness
Increasing feed
M 10 Steel, steel castings, Turning, medium or high cutting speeds.
manganese steel Small or medium chip sections.
Grey cast iron, alloy cast iron
M 20 Steel, steel castings, Turning, milling, medium cutting speeds

austenitic or manganese steel, and chip sections.
Ferrous me-
grey cast iron
tals with long
13 Hard materials
yellow
or short chips
M M 30 Steel, steel castings, Turning, milling, planing. Medium
and non-
austenitic steel, grey cast cutting speeds, medium or large chip
ferrous
iron, high temperature sections.
metals
Increasing speed
resistant alloys
Wear resistance
M 40 Mild free cutting steel, Turning, parting off, particularly on
low tensile strength steel automatic machines.
Non-ferrous metals and light
alloys
13-65
13-66
Table E. Classification of hard cutting materials according to use (continued).

characteristic
Symbol Broad Distin- Desig- Material to be machined Use and working conditions of cut of hard
categories guishing nation cutting
of material to colours materials
be machined
Toughness
Increasing feed
K 01 Very hard grey cast iron, Turning, finish turning, boring, milling,
chilled castings of over 85 scraping.
Shore, high silicon
aluminium alloys, hardened
steel, highly abrasive plastics,
hard cardboard, ceramics
K 10 Grey cast iron over 220 HB, Turning, milling, drilling, boring,
13 Hard materials
malleable cast iron with short broaching, scraping.
Ferrous chips, hardened steel, silicon
metals with aluminium alloys, copper
short chips, alloys, plastics, glass, hard
red
K non-ferrous rubber, hard cardboard,

metals and porcelain, stone.
non-metallic
K 20 Grey cast iron up to 220 HB, Turning, milling, planing, boring,
materials
non-ferrous metals: copper, broaching, demanding very tough hard
brass, aluminium cutting materials.
K 30 Low hardness grey cast iron, Turning, milling, planing, slotting, for
Increasing speed
Wear resistance
low tensile strength steel, machining in unfavourable conditions1 and
compressed wood with the possibility of large cutting angles.
K 40 Soft wood or hard wood Turning, milling, planing, slotting, for
Non-ferrous metals machining in unfavourable conditions1 and
with the possibility of large cutting angles.
[Ref. p. 13-185
1
Raw material or components in shapes which are awkward to machine: casing or forging skins, variable hardness, etc., variable depth of cut, interrupted
cut, work subject to vibrations.
5 Important remarks
5.1 Particular attention is drawn to the fact that a group of application is not a grade of hard cutting mate-
rial and should not be confused with the latter. It only defines the extent of the field of use and the work-
ing conditions and the manufacturers are responsible for classifying their hard cutting materials within the
group. Grades classified in the same group of application by different manufacturers may differ from one
another as far as their properties for machining by chip removal are concerned; for this reason, no combi-
nation of groups of application and grades of hard cutting materials can be regarded as representing
"a comparative table of hard cutting material grades".
This is why the letters P, M and K, intended exclusively for the general classification of the main
groups of chip removal, should never be used, either separately or in conjunction with another letter, as a
commercial designation for a particular grade; the groups of application which are essentially designated
by these letters cannot, in fact, be identified with grades of hard cutting materials and the latter therefore
cannot have the same designations.
5.2 The practice of distinguishing grades of hard cutting materials by colours as well as by symbols has,
until now, given rise to more inconvenience than simplification, but only because the multiplicity of
grades led to the simultaneous use of a number of colours.
This practice should be abandoned, and the use of colours in accordance with this International Stan-
dard reserved solely for the indication of the main groups of chip removal.
The symbols and distinguishing colours shall be used for the marking of tools in accordance with the
requirements of ISO 504.
5.3 On lathe tools, the symbols and colour markings shall be applied as specified in ISO 504.
13.4.2 Hardmetals and cermets
13.4.2.1 General and structures
The following Tables list the grades of hardmetal and cermets, based on composition and average grain
size, commercially available, together with their major property values. The lists are made up of available
data obtained from a number of major world manufacturers but similar grades and data are available from
other sources.
Table 61 [99S2] shows the extensive range of grades of hardmetal based on tungsten carbide (WC)
and cobalt (Co) which are available. The variation in properties is achieved by varying the grain size of
the WC phase and the volume of the Co binder phase. This is demonstrated in Fig. 13.92 [99S2] which
illustrates the structure of three grades with increasing WC grain size and constant cobalt content -
9.5/10.0 wt%, with their respective major properties listed adjacent to the photomicrographs. Fig. 13.93
[99S2] demonstrates the alternative technique of keeping the medium WC grain size constant and varying
the cobalt content 6 - 10 - 12 wt%.
Hardmetal grades containing proportions of tungsten carbide (WC), titanium carbide (TiC), tanta-
lum/niobium carbide (TaNb)C and cobalt (Co) are shown in Table 62 [99P]. These grades are almost
exclusively used for machining metals and as such carry the ISO codes for the various applications. The
variation in properties is mainly achieved by varying the composition, particularly the TiC and (TaNb)C
contents. A representative structure for such alloys is demonstrated in Fig. 13.94, Tizit S40T1 [99P]. This
is made up of angular WC-grains, rounded mixed crystal (W Ti Ta Nb)C grains and the cobalt rich binder
phase.
Table 63 [99W] shows a range of grades, based on tungsten carbide (WC) and cobalt (Co) with small
additions of other carbides, developed, but not exclusively, for metal cutting operations in the ISO K
__________
1
Trademark of Plansee Tizit GmbH, Reutte, Austria.

series. Again, properties are adjusted by changing the WC grain size, the cobalt volume and the amount
and type of additional carbides.
Special hardmetal grades are required for various applications - usually in the so-called “wear-parts”
area - where corrosion and other properties, such as being non-magnetic, are of prime importance. Such a
range of alloys is shown in Table 64 [99S2]. The composition covers a range of different carbides with
different grain sizes and binder metals, such as WC, TiC, Mo2C, Cr3C2 and Co, Ni, Al respectively.
The majority of hardmetal grades used in the area of metal cutting are now composed of a base hard-
metal alloy with a CVD or PVD coating of one or more refractory compounds. There is now an extensive
range of grades, as shown in Table 65 [99K], which covers the complete spectrum of the ISO K, M, P
application codes. Table 66 [99K] gives a more detailed appraisal of these grades together with more
specific application data. To illustrate the complexities of coated hardmetal grades, the structure shown in
Fig. 13.95 [99K] of Kennametal KC9351 shows a three layer coating - TiCN (adjacent to a cobalt en-
riched and mixed crystal depleted zone), TiC and an Al2O3 outer coating. This complex structure pro-
duces a combination of properties, from excellent toughness through to enhanced resistance to flank and
crater wear, which is impossible to obtain with a more conventional material.
Modern cermet grades, which first appeared in Japan, are also used in metal cutting applications.
Table 67 [99W] gives details of composition and properties of three modern alloys. The compositions are
based on mixed carbonitrides in a complex alloy binder which yield complicated structures. Fig. 13.96
[99W] demonstrates two structures, examined using backscattered scanning electron micrography. The
Widia TT1152 grade shows a mixture of different hard phase structures in a complex binder, while Widia
TT1252 grade shows a predominance of one type - dark grains in the photomicrograph. A descriptive
explanation for the composition of these structures in shown in Fig. 13.97 [99W]. As a comparison, and
to illustrate the complexity of the structures, the diagram also shows the structure of a standard hardmetal
grade containing the mixed crystal phase. To confirm the composition of the different phases, Fig. 13.98
[92G1] shows a profile line scan using Energy Dispersive Spectrometry (EDS) of a core-shell type grain.
Further details of these structures are discussed in references [89R, 92G1].
Table 61. Composition and properties of WC-Co hardmetal grades - data and grade designations are the
property of Sandvik Hard Materials, Stockholm, Sweden.
Part a
Composition Properties
Grade WC Co TiC, Other WC grain size Density Hardness Transverse
TaC, rupture
NbC strength
TRS**
ρ 20 °C 20 °C 20 °C
wt% wt% wt% wt% g/cm3 HV30 HRA* MPa
3UF 96.4 3.0 - 0.6 Ultrafine 15.15 > 2250 > 94.9 2500
6UF 93.1 6.0 - 0.9 Ultrafine 14.75 2050 94.4 2850
8UF 91.0 8.0 - 1.0 Ultrafine 14.50 1900 93.8 3150
H3F 97.0 3.0 - - Extrafine 15.30 1925 93.9 3300
H6FF 93.5 6.0 - 0.5 Extrafine 14.85 1850 93.5 3400
H6F 93.7 6.0 - 0.3 Extrafine 14.90 1775 93.1 3500
H10F 89.5 10.0 - 0.5 Extrafine 14.50 1600 92.1 3750
H15F 84.3 15.0 - 0.7 Extrafine 13.95 1400 90.4 3900
H3M 96.5 3.5 - - Fine 15.20 1750 93.0 1900
H4M 95.0 5.0 - - Fine 15.00 1750 93.0 2000
H5M 94.5 5.5 - - Fine 14.95 1700 92.8 2100
H6M 93.5 6.0 0.5 - Fine 14.95 1625 92.2 2150
H7M 93.5 6.5 - - Fine 14.85 1650 92.4 2200
H8M 92.5 7.0 0.5 - Fine 14.75 1575 91.9 2250
__________
1
Trademark of Kennametal Inc., Latrobe, USA. 2 Trademark of Widia GmbH, Essen, Germany

Grade WC Co TiC, Other WC grain size Density Hardness Transverse
TaC, rupture
NbC strength
TRS**
ρ 20 °C 20 °C 20 °C
wt% wt% wt% wt% g/cm3 HV30 HRA* MPa
H6N 94.0 6.0 - - Medium 15.00 1600 92.1 2200
H7N 94.0 6.0 - - Medium 14.90 1500 91.4 2200
H8N 91.5 8.5 - - Medium 14.65 1450 90.9 2400
H9N 91.5 8.5 - - Medium 14.70 1425 90.6 2450
H10N 90.5 9.5 - - Medium 14.50 1400 90.4 2600
H11N 89.0 11.0 - - Medium 14.40 1250 88.7 2700
H12N 88.0 12.0 - - Medium 14.30 1300 89.3 2800
H13N 87.0 13.0 - - Medium 14.25 1240 88.6 2900
H15N 85.0 15.0 - - Medium 13.90 1150 87.5 3050
H20N 80.0 20.0 - - Medium 13.50 1100 86.9 3150
H25N 75.0 25.0 - - Medium 13.20 950 84.9 3000
H27N 72.5 27.5 - - Medium 12.90 800 83.0 2900
H6P 94.0 6.0 - - Medium-coarse 14.90 1430 90.7 2300
H9P 91.0 9.0 - - Medium-coarse 14.65 1260 88.9 2600
H10P 90.5 9.5 - - Medium-coarse 14.50 1210 88.3 2600
H15P 85.0 15.0 - - Medium-coarse 13.90 1030 86.0 3050
H20P 80.0 20.0 - - Medium-coarse 13.60 910 84.3 2900
H25P 75.0 25.0 - - Medium-coarse 13.10 810 83.5 2750
H30P 70.0 30.0 - - Medium-coarse 12.70 700 82.5 2700
H6C 93.5 6.5 - - Coarse 14.85 1400 90.4 2650
H9C 91.0 9.0 - - Coarse 14.60 1250 88.7 2900
H10C 90.5 9.5 - - Coarse 14.50 1210 88.3 3000
H11C 89.0 11.0 - - Coarse 14.40 1150 87.5 3200
H13C 87.0 13.0 - - Coarse 14.20 1070 86.5 2700
H15C 85.0 15.0 - - Coarse 13.90 950 85.5 2900
H20C 80.0 20.0 - - Coarse 13.50 900 85.0 2700
H6T 94.0 6.0 - - Extra-coarse 14.80 1300 89.0 2300
H10T 90.0 10.0 - - Extra-coarse 14.55 1000 85.6 3100
* Approximate values converted from HV30.
** In accordance with ISO 3327, Type B, ground, average values.

Table 61 (continued) Part b

Grade Thermal Electrical Linear expansion Fracture Compres- Young’s Poisson’s
conductivity1 resistivity coefficient toughness sive modulus ratio
strength E ν
λ ρ 20 - 400 °C 20 - 800 °C KIC 20 °C

W/(m K) µΩ cm 10−6/K 10−6/K MPa m1/2 MPa GPa
3UF 90 20 4.8 5.2 5 11500 670 0.22

6UF 85 20 5.3 5.5 8 9000 630 0.22
8UF 85 19 5.6 5.8 10 7700 600 0.22
H3F 95 20 4.6 5.0 7 7800 670 0.22
H6FF 90 20 5.2 5.5 9 7400 630 0.22
H6F 90 20 5.1 5.4 10 6900 630 0.22
H10F 85 19 5.7 5.8 13 6300 580 0.22
H15F 85 17 6.2 6.4 16 5300 540 0.23
H3M 100 20 4.5 5.0 9 6900 670 0.22
H4M 95 20 4.8 5.2 10 6900 645 0.22
H5M 95 20 4.9 5.3 10 6700 635 0.22
H6M 95 20 5.0 5.4 11 6400 630 0.22
H7M 95 19 5.1 5.4 11 6500 625 0.22
H8M 95 19 5.2 5.5 11 6200 615 0.22
H6N 100 20 4.9 5.3 12 6200 630 0.22
H7N 100 19 4.9 5.3 12 5500 630 0.22
H8N 95 19 5.3 5.5 13 5200 600 0.22
H9N 95 19 5.3 5.5 13 5200 600 0.22
H10N 95 19 5.4 5.6 14 5200 585 0.22
H11N 95 18 5.6 5.7 15 4600 575 0.22
H12N 95 18 5.8 5.9 16 4600 560 0.22
H13N 95 17 5.8 5.9 16 4600 545 0.22
H15N 90 17 6.0 6.2 18 4000 540 0.23
H20N 90 17 6.5 6.9 22 3900 495 0.23
H25N 90 16 7.0 7.4 25 3000 460 0.24
H27N 90 16 7.1 7.8 26 2600 450 0.24
H6P 105 19 4.9 5.3 14 5500 630 0.22
H9P 105 19 5.2 5.5 17 4700 590 0.22
H10P 105 19 5.3 5.6 17 4200 590 0.22
H15P 100 17 5.8 6.2 22 3500 530 0.23
H20P 95 17 6.5 6.9 22 3600 495 0.24
H25P 90 17 7.2 7.6 25 3300 450 0.24
H30P 85 17 7.5 8.0 27 3000 415 0.25
H6C 105 19 4.8 5.3 16 5200 630 0.22
H9C 105 19 5.1 5.5 17 4500 600 0.22
H10C 105 19 5.2 5.6 17 4400 590 0.22
H11C 100 18 5.3 5.7 19 3900 575 0.22
H13C 100 18 5.5 5.9 21 3800 550 0.22
H15C 100 17 5.8 6.2 24 3600 530 0.23
H20C 95 17 6.5 6.9 25 3500 495 0.24
H6T 105 19 4.9 5.3 16 4300 630 0.22
H10T 105 18 5.2 5.8 21 3500 580 0.22
1
At ambient temperature (20 °C).

Table 62. Composition and properties of WC-TiC-Ta (Nb)C-Co hardmetal grades - data and grade desig-
nations the property of Plansee Tizit GmbH, Reutte, Austria.
Part a
Symbol Chemical composition [wt%] Average Transverse Density Hardness ISO
grain size rupture code(s)
strength
WC TiC Ta(Nb)C Co µm MPa g/cm3 HV
S22T 71.5 9 11 8.5 1-2 1700 12.1 1570 P20-P25

S26T 69.9 8.6 12 9.5 1 - 1.5 1700 12.2 1550 P20-P30
S36T 76.5 4 7.5 12 1-2 2100 13.0 1390 P30-P40
S40T 77 4 8 11 1-2 2400 13.3 1420 P40
U10T 83.5 5 5.5 6 1 1700 13.4 1680 M10

U17T 86 2.5 5.5 6 1-2 1900 14.0 1570 M15
U20T 77 4 10 9 1-2 1800 13.2 1460 M20
Part b
Symbol Compres- Young’s Modulus of Poisson’s Electrical Thermal Mean ther-
sive modulus rigidity ratio resistivity conductivity mal expan-
strength sion coeffi-
cient 20 °C
GPa GPa GPa µΩ cm W/(m K) 10−6/K
S22T 5.2 540 221 0.22 37 40 6

S26T 5.1 550 225 0.22 30 50 6
S36T 5 560 230 0.22 25 60 5.5
S40T 4.9 540 220 0.22 24 60 6
U10T 5.7 620 255 0.22 24 60 5.5

U17T 5.3 580 230 0.22 25 60 5.5
U20T 5.1 550 225 0.22 28 60 5.5

Table 63. Composition and properties of WC - Co hardmetal grades with small additions of other car-
bides - data and grade designations the property of Widia GmbH, Essen, Germany.
Part a
WIDIA THM-U THM-F THR-U THR-S THR-F THA-F THA-S
hardmetal grade
Application range ISO 513 K05 K10 K10 K25 K25 K35 -
Composition
WC [%] 93.0 91.8 90.0 89.5 87.9 84.2 83.2
Dopant carbides [%] 0.9 1.7 0.9 0.5 1.6 2.3 0.8
Co [wt%] 6.1 6.5 9.1 10.0 10.5 13.5 16.0
Density (ISO 3369) 14.7 14.8 14.4 14.5 14.4 14.0 13.8
[g/cm3]
Vickers hardness HV30 (ISO 2020 1780 1840 1570 1530 1460 1350
3878)
Compressive strength 7500 6000 7000 5500 5300 5700 -

(ISO 4506) [MPa]
Transverse rupture strength 39001 3000 40001 38001 3200 3400 3800
(ISO 3327) [MPa]
Modulus of elasticity 635 640 560 600 590 530 -

(ISO 3312) [GPa]
Fracture toughness 7.2 10.8 7.4 9.7 13.8 11.2 -

[MPa m1/2]
Poisson’s ratio 0.21 0.21 0.21 0.22 0.21 0.21 -
Thermal conductivity 34 46 51 43 42 46 -
[W/(m K)]
Coefficient of thermal 5.4 6.2 5.9 6.2 6.7 6.9 -

expansion [10−6/K]
(293 - 1073 K)
Electrical resistance 31 23 28 40 26 26 -
[µΩ cm]
1
rods ∅ 3 mm

Table 63 (continued) Part b

WIDIA THF THM THR THA GT30
hardmetal grade
Application range ISO 513 K05 K15 K30 K40 -
Composition
WC [%] 94.1 93.8 90.8 85.3 83.4
Dopant carbides [%] 1.9 0.2 0.2 2.7 1.6
Co [wt%] 4.0 6.0 9.0 12.0 15.0
Density (ISO 3369) 15.0 14.9 14.6 14.2 14.0

[g/cm3]
Vickers hardness HV30 (ISO 1730 1580 1420 1290 1150

3878)
Compressive strength 5700 5400 5000 4500 4100

(ISO 4506) [MPa]
Transverse rupture strength (ISO 1600 2000 2350 2450 2700

3327) [MPa]
Modulus of elasticity 650 630 590 580 540

(ISO 3312) [GPa]
Fracture toughness 9.0 9.6 12.3 12.7 13.8

[MPa m1/2 ]
Poisson’s ratio 0.21 0.22 0.22 0.22 0.23
Thermal conductivity 80 94 70 65 60
[W/(m K)]
Coefficient of thermal 5.0 5.5 5.6 5.9 6.5

expansion [10−6/K]
(293 - 1073 K)
Electrical resistance 20 19 18 18 17
[µΩ cm]

Table 64. Composition and properties of complex corrosion resistant hardmetal grades - data and grade
designations the property of Sandvik Hard Materials, Stockholm, Sweden.
Grade Hard Binder WC Density ρ Hardness at 20 °C Transverse rupture
phase phase grain size strength TRS** at 20 °C
wt% wt% g/cm3 HV30 HRA* MPa
DC03 97.0 3.0 Extrafine 15.25 1900 93.8 2100
DC05 94.9 5.1 Extrafine 15.00 1800 93.3 2350
DZ05 95.0 5.0 Extrafine 15.00 1900 93.8 2300
C0F > 99.7 ≈0 Fine 14.60 1900 93.8 1000 Non magnetic
DC08 89.8 10.2 Fine 14.45 1425 90.6 2650
C9M 91.0 9.0 Fine 14.60 1375 90.1 2600 Non magnetic
DC30 69.2 30.8 Fine 12.50 1000 85.6 3850
C7N 92.8 7.2 Medium 12.70 1750 93.0 1600 Non magnetic
C7P 93.1 6.9 Medium-coarse 14.90 1390 90.3 2700 Non magnetic
C25P 75.0 25.0 Medium-coarse 13.00 750 83.0 2700
C30P 70.0 30.0 Medium-coarse 12.70 650 82.0 2700
C10C 90.0 10.0 Coarse 14.40 1100 86.7 2700
C15C 85.0 15.0 Coarse 14.00 900 85.0 2900
C20C 80.0 20.0 Coarse 13.50 800 83.5 2700
C30T 70.0 30.0 Extra-coarse 12.70 600 81.5 2700
* Approximate values converted from HV30.
** In accordance with ISO 3327, type B, ground, average values.
Table 65. Composition and data of coated indexable insert metal cutting grades - data and grade designa-
tions the property of Kennametal Inc., Latrobe, USA.
Substrate Designation Type Coating layers Coating ISO Code(s)

thickness
µm P M K
Special KC210 CVD TiC + TiCN + TiN 11 05-30

Special KC250 CVD TiC + TiCN + TiN 11 30-45 25-35
Special KC710 PVD TiN 3 15-25 15-25
Special KC720 PVD TiN 3 25-45 30-40 25-35
Special KC725M PVD TiCN + TiN 5 15-35 25-45
Special KC732 CVD + PVD TiN(CVD) + TiCN(CVD) + 8 05-15
TiN(PVD)
Special KC740 PVD TiN 3 05-15
Special KC792M CVD + PVD TiN(CVD) + TiCN(CVD) + 8 10-20
TiN(PVD)
Special KC840 CVD TiC + TiCN + TiN 11 25-35
Special KC910 CVD TiC + Al2O3 8 01-20 05-20 01-15

Substrate Designation Type Coating layers Coating ISO Code(s)

thickness
µm P M K
Special KC935 CVD TiCN + TiC + Al2O3 8 20-40 25-40 20-30
Special KC950 CVD TiC + Al2O3 + TiN 11 10-25 10-25 10-20
Special KC990 CVD TiCN + Al2O3 + TiN + Al2O3 12 10-25 10-25 05-25
+ TiN + Al2O3 + TiN
Special KC992M CVD TiCN + Al2O3 4 10-25
Special KC994M CVD TiCN + Al2O3 4 20-30
Special KC9010 CVD TiCN + Al2O3 + TiN 14 01-20 05-20 01-15
Special KC9025 CVD TiCN + Al2O3 + TiN 14 15-35 20-35 15-25
Special KV9040 CVD TiN + TiCN + TiC + TiCN + 9 30-45 30-40 25-35
Al2O3 + TiN
Special KV9045 CVD TiN + TiCN + TiC + TiCN + 9 35-50 35-45 30-40
Al2O3 + TiN
Special KCD25 Plasma CVD Diamond 30 02-08
Table 66. Construction and application data for coated indexable insert metal cutting grades - data and
grade designations the property of Kennametal Inc, Latrobe, USA.
PVD coated grades
Grade Coating Insert styles Composition and application C class ISO class
KC6725 TiN A3 deep Composition: A PVD TiN coated grade C2 K15 - K25
grooving with a tough ultra-fine grain, unalloyed C6 M25 - M35
substrate. P25 - P40
Application: Available only in the A3
tooling system. For general purpose ma-
chining of most steels, stainless steels, high
temperature alloys, titanium, irons, and
non-ferrous materials. Speeds may vary
from low to medium, and will handle inter-
ruptions and high feed rates. Cutting edges
are lightly honed.
KC710 TiN Threading, Composition: A PVD TiN coating over a C6 - C7 M15 - M30
grooving general purpose alloyed substrate. P20 - P35
Application: Use to cut steel at medium to
high speeds. Grade KC710 will greatly im-
prove productivity, and allow higher speed
capabilities in comparison to uncoated car-
bide. Available in threading and grooving
geometries where upgrades from uncoated
carbides are common. Most cutting edges
are lightly honed. Positive rake Top Notch
inserts are sharp.

PVD coated grades

KC720 TiN Turning, Composition: A tough, durable PVD TiN C1 K25 - K35
boring, coating over an unalloyed substrate. C5 M30 - M40
profiling, Application: Developed for cutting high P25 - P45
threading, temperature alloys, most stainless steels,
grooving, and titanium alloys at low to moderate
cutoff speeds. Its unique mechanical and thermal
shock resistant properties and resistance to
edge build-up enable grade KC720 to de-
liver superior performance and reliability
on difficult operations like cutoff and inter-
rupted turning. Consider it to be your
problem solving grade. Most ground pe-
riphery inserts have a sharp edge, others
are lightly honed.
KC722 TiN Threading, Composition: A PVD TiN coating over a C2 K15 - K25
cutoff, medium tough WC/Co unalloyed substrate. C6 M25 - M35
face grooving Application: This grade was specifically P25 - P40
developed for threading, cutoff, and for the
Ranger face grooving system. Use in all
types of steel, austenitic, ferritic, and
martensitic stainless steel, tool steels, high
temperature alloys, and titanium. The fine
grain substrate provides just the right
amount of wear resistance and toughness
for the intended applications. The coating
contributes crater wear resistance and re-
sistance to built-up edge, as well as higher
speed capability when desired. Mot inserts
are lightly honed. Positive rake Top Notch
inserts are sharp.
KC730 TiN Turning, Composition: A PVD TiN coating over a C2 - C4 K05 - K20
boring, very wear-resistant unalloyed substrate. M10 - M25
profiling, Application: For general purpose ma- P10 - P20
threading, chining of high temperature alloys, aero-
grooving space materials, refractory metals and 200
or 300 series stainless steels. The thin, uni-
formly dense, smooth coating increases
wear resistance and reduces problems with
built-up edge. It also provides an unusually
good combination of properties for ma-
chining difficult to machine materials and
aluminum. The substrate offers superior
thermal deformation resistance, depth of
cut notch resistance and edge strength. Run
at higher speeds than uncoated grades.
Most ground periphery inserts have a sharp
edge.

PVD coated grades

KC732 TiN Turning, Composition: A CVD/PVD coating over a C3 - C4 K05 - K15

TiCN boring, very wear resistant unalloyed substrate. M10 - M20
TiN profiling, Application: This grade was designed for
grooving semifinishing to finishing of high tem-
perature alloys and titanium. Grade KC732
benefits from the combined strengths of
two coating processes. The CVD layer
provides exceptional adherence to the sub-
strate, and the PVD coating is crack free
and very smooth. This patented grade al-
lows higher cutting speeds than other PVD
grades, which leads to greater productivity,
reduced cycle times, and lower costs. Most
ground periphery inserts have a sharp edge.
KC6840 TiN A3 deep Composition: This grade has a wear re- C5 M30 - M40
TiCN grooving, sistant TiCN coating over a coarse grained P40 - P50
light profiling and very tough substrate.
Application: Available exclusively in the
A3 multipurpose tooling system. Designed
for heavy duty grooving applications sub-
ject to severe mechanical edge loading.
Use at low to medium speeds on most car-
bon, alloy, and stainless steels. Consider
KC6840 to be your workhorse grade for
steel applications. For medium cutting
conditions, use grade KC6920.
KC6920 TiN A3 deep Composition: A moderately thick alumina C6 - C7 K15 - K25

Al2O3 grooving, coating over a hard substrate. M10 - M20
TiC light profiling Application: Available exclusively in the P10 - P30
TiCN A3 deep grooving system. Engineered for
general purpose use on carbon steel, alloy
steel, ductile iron and cast iron. The Al2O3
coating is highly abrasion resistant, allows
higher speeds and offers better surface
finishes. The coating layers allow eco-
nomic use at a wide range of speeds and
feeds. Use as your first grade choice for the
above materials. Withstands moderate in-
terruptions. For heavy interrupted cuts, use
grade KC6840.

PVD coated grades

KC810 TiN Turning, Composition: A multilayered coating over C6 - C7 P10 - P30

TiCN boring, an alloyed carbide substrate.
TiC profiling, Application: An economical choice for
threading, general steel machining at low to moderate
grooving speeds. For better tool life at moderate to
higher speeds, consider upgrading to grade
KC935.
KC820 TiN Cuttoff Composition: A multilayered CVD coat- C5 M10 - M30

TiCN ing over a tough steel cutting substrate. P20 - P35
TiC Application: Available exclusively in the
Separator and Separator PL cutoff tools.
For use on carbon and alloy steel, ductile
iron, and ferritic and martensitic stainless
steels. The CVD coating provides wear
resistance, while the substrate provides the
toughness required for cutoff applications.
For most operations running at medium to
higher cutting speeds, consider upgrading
to grade KC935.
KC850 TiN Turning, Composition: A tri-phase coating on an C5 - C6 M30 - M45

TiCN boring, extra strong cobalt enriched substrate. P25 - P45
TiC profiling, Application: Grade KC850 has long been
grooving considered the industry’s leading choice
for general purpose machining of many
workpiece materials. With the advent of
higher machine tool spindle speeds, today
it finds its best application in heavy cutting
of low, medium, and high carbon steels, as
well as medium hardness alloy and tool
steels. Excellent thermal and mechanical
shock resistance makes grade KC850 ide-
ally suited for difficult applications with
interruptions. Consider using grade KC935
for lighter cuts.

PVD coated grades

KC9010 TiN Turning, Composition: A thick alumina coated C3 K10 - K20

Al2O3 boring, grade with a moderately hard, deformation C7 M10 - M20
TiCN profiling resistant substrate. P01 - P20
Application: This is a great finishing
grade for use in a large variety of work-
piece materials including most steels, fer-
ritic and martensitic stainless steel, and
irons. The thick coating is the preferred
choice for cast iron machining because it
has outstanding abrasion resistance and
maintains hardness at high cutting speeds.
Best economy and productivity can be at-
tained when used at high speeds. Can with-
stand some interruptions. For rougher cut-
ting, use grade KC9025.
KC9025 TiN Turning, Composition: A thick alumina coated C2 - C3 K15 - K25

Al2O3 boring, grade with a cobalt enriched substrate. C6 - C7 M15 - M25
TiCN profiling Application: Grade KC9025 can be con- P15 - P35
sidered the industry’s best high speed, gen-
eral purpose turning grade. Workpiece ap-
plications include most steels, ferritic and
martensitic stainless steels and irons. The
smooth coating results in less microchip-
ping, reduced frictional heat, and produces
better surface finishes. The substrate
maintains both toughness and edge
strength. Performs well in moderately
heavy roughing to semifinishing. Use
grade KC9010 for the finish cut.
KC9040 TiN Turning, Composition: An alumina coated grade C5 - C6 M30 - M40

Al2O3 boring, with a tough cobalt enriched substrate. P30 - P45
TiC profiling Application: For heavy roughing applica-
TiCN tions on all types of steels, stainless steels,
and most other materials when tool edge
strength is critical. A specially designed
coating preparation assures prolonged tool
life. Apply with confidence on tough jobs.
KC9045 TiN Turning, Composition: An alumina coating over a C5 M35 - M45

Al2O3 boring, coarse grained substrate that has a minimal P35 - P50
TiC profiling amount of solid solution carbide.
TiCN Application: Designed for heavy to violent
roughing of all types of materials where
bulk toughness is essential. Reserve this
grade for your most difficult interrupted
cutting applications.

PVD coated grades

KC9120 TiN Turning, Composition: A TiCN/Al2O3/TiN coating C3 K10 - K30

Al2O3 boring, over a carefully chosen substrate.
TiCN profiling, Application: Grade KC9120 was specifi-
grooving cally engineered for short chipping ductile
irons and grey irons. The newly developed
tool coating cycle used for this grade pre-
serves the substrate strength and reduces
thermal cracks. The substrate and coating
combination perform well in heavy inter-
ruptions as well as smooth cutting. Apply
at speeds up to 370 m/min in both high and
low tensile strength materials.
KC910 Al2O3 Turning, Composition: A thin alumina coating over C3 K01 - K20
TiC boring, a hard, deformation resistant substrate. C7 M05 - M20
profiling, Application: This grade excels in two P01 - P20
grooving main application areas; high speed finish-
ing of grey cast irons, and medium speed
finishing of alloy steels that are in a hard-
ness range of 35 to 50 HRC. The hard sub-
strate prolongs tool life in these applica-
tions. The alumina coating allows higher
cutting speeds. The TiC layer contributes
abrasion resistance, which is important for
intended uses. Can withstand light inter-
ruptions. For heavy interrupted cuts, use
grade KC9025.
KC935 Al2O3 Turning, Composition: A multilayered coating with C2 K20 - K30

TiC boring, optimized layer thickness over a cobalt C6 M20 - M35
TiCN profiling, enriched substrate. P20 - P40
cutoff Application: Grade KC935 is fast becom-
ing the favorite grade for soft and gummy
workpiece materials. Successfully apply on
most steels, ferritic, martensitic, and aus-
tenitic stainless steels, and heavier cutting
in nickel base alloys. The TiCN/TiC coat-
ing layers are effective at low to medium
speeds, and the outer alumina coating
maintains hot hardness at medium to high
speeds. The well balanced substrate main-
tains toughness and edge strength. The
specially engineered coating surface pro-
vides a smooth, stable cutting edge that
resists build-up and microchipping. If you
like grade KC850, try grade KC935, and
bring real flexibility to your metalcutting
operations.

PVD coated grades

KC950 TiN Turning, Composition: A multilayered coating over C4 - C4 K10 - K20

Al2O3 boring, a hard, cobalt enriched substrate. C7 - C8 M10 - M25
TiC profiling, Application: Best applied in tough, fairly P05 - P20
grooving hard, 35 to 45 HRC alloy and bearing
steels. This unique grade offers a substrate
that combines hardness and toughness, and
a coating design that resists crater and
abrasive wear. Can withstand interruptions.
Use for moderate roughing to semifinish-
ing at medium to high cutting speeds and
feeds. Consider using grade KC9025 for
general purpose use.
KC990 TiN Turning, Composition: A multilayered alumina C3 K05 - K20

Al2O3 boring, coated grade with a high strength substrate. C7 P10 - P20
TiN profiling Coated with TiCN and then alternating
Al2O3 layers of Al2O3 and TiN.
TiN Application: Engineered for finishing of
Al2O3 carbon and alloy steels, and ductile, nodu-
TiCN lar, or malleable irons. The thin alumina
coating layers are very hard. Best speed
range is above 200m/min in smooth cuts.
In most applications, grade KC990 may be
replaced by grade KC9010, with better
machining results.
Table 67. Composition and properties of cermets - data and grade designations the property of Widia
GmbH, Essen, Germany.
WIDIA TTI05 TTI15 TTI25

hardmetal grade
Application range ISO 513 P05 P10 P20

Composition:
Carbonitride [%] 94.0 85.7 82.3
Dopant carbides [%] 0.3 0.8 1.0
Co/Ni [%] 5.7 13.5 16.7
Density (ISO 3369) [g/cm3] 6.1 7.0 7.0
Vickers hardness [HV30] (ISO 3878) 1750 1600 1450
Compressive strength (ISO 4506) [MPa] 6100 4700 4600
Transverse rupture strength (ISO 3327) [MPa] 1500 2300 2500
Modulus of elasticity (ISO 3312) [GPa] 470 450 440
Fracture toughness [MPa m1/2] 5.7 7.9 10.0
Poisson’s ratio 0.20 0.22 0.21
Thermal conductivity [W/(m K)] 9.6 11.0 15.7
Coefficient of thermal expansion [10−6/K] 8.2 9.4 9.1
(293 - 1073 K)
Electrical resistance [µΩ cm] 97 91 48

13.4.2.2 Physical and mechanical properties - ambient temperature
13.4.2.2.1 Density
For the basic WC-Co hardmetals, the density follows the law of mixtures and values from 15.56 g/cm3 for
a WC-1 wt% Co alloy to 12.76 g/cm3 for a WC-30 wt% Co alloy are obtained (see Table 31). The more
complex hardmetals and cermets yield densities which are strongly influenced by composition and the
presence of complex phases - see Tables 62, 63, 64 and 67.
13.4.2.2.2 Hardness
Hardness values vary over a wide range and depend upon the grain size of the constituent hard phases and
the binder phase volume. Tables 61, 62, 63, 64 and 67 give individual values for different alloys. For the
WC-Co hardmetals, hardness values from > 2250 HV30 for a 0.4 µm WC-3 wt% Co alloy to 800 HV30
for a 1.5 µm WC-27.5 wt% Co alloy are obtained. Fig. 13.99 [96G4] illustrates that the inverse hardness
value of sintered alloys with varying Co content and different grain size WC starting powders (0.6 µm to
30 µm) has a straight line relationship with the volume fraction cobalt content.
Examination of a considerable amount of hardness data, covering an arithmetic mean linear intercept
WC grain size of 0.29 µm to 3.25 µm, showed that the Hall-Petch model gives a reasonably good fit be-
tween hardness (HV30) and the inverse square root of this grain size - Fig. 13.100 [95R]. However, it was
pointed out that extrapolation to grain size values of less than 0.3 µm should be treated with care.
The influence on hardness by the substitution of cobalt with nickel is shown in Fig. 13.101 [84E] for
two series of alloys with 10 wt% binder and 15 wt% binder, respectively.
13.4.2.2.3 Magnetic coercivity
Consideration of all measured values of magnetic coercivity has resulted in an expression which relates
coercivity to WC grain size [95R]:
Hc = a + b d −WC
1
(14)
where Hc = coercivity in kA m−1, a and b are constants and dWC is the WC arithmetic mean linear inter-
cept in µm.
A plot of many values of basic WC-6 wt% Co alloys is shown in Fig. 13.102 [95R]. The fit at WC
grain sizes greater than about 2 µm was not particularly good so a bilinear fit was carried out for data
Hc > 12.5 kA m−1 and Hc < 12.5 kA m−1.
This resulted in two sets of expressions:
Hc < 12.5 kA m−1

Hc = 1.79 + 10.9 d −WC
1
(15)
and
Hc > 12.5 kAm−1
Hc = 6.71 + 7.39 d −WC
1
(16)
A further consideration, shown in Fig. 13.103 [96G4], for two sets of alloys - one based on
WC-6 wt% Co and the other on WC-10 wt% Co illustrates a deviation from the predicted single straight
line.

13.4.2.2.4 Magnetic saturation
Measurement of magnetic saturation of hardmetal alloys can be used to predict the tungsten, and also
other solute elements such as Fe, Ni, Cr etc. content of the binder phase [96R1]. A prerequisite for meas-
uring these values is that a sufficient field strength be available to fully magnetise the alloys (> 0.75 T). In
the control of the carbon content of hardmetals it is common to measure the magnetic saturation polariza-
tion and relate it to the density for comparisons. This yield the unit mT m3 kg−1. As the carbon content of
hardmetal alloys decreases, so the tungsten content of the binder phase increases. This has a direct influ-
ence on the magnetic saturation and moment values such that:
4πσB = 4π (σCo − 0.275 mw) (17)
where 4πσCo is 202 µT m3 kg−1 and mw is the wt% W in the cobalt binder phase. The measured magnetic
saturation, for comparison purposes, is commonly divided by the density of the alloy yielding the dimen-
sion µT m3 kg−1. When a value of 160 µT m3 kg−1 is reached, eta phase begins to form in the alloy and so
the range 202 - 160 µT m3 kg−1 for the magnetic saturation of the cobalt phase defines the two phase field
in WC-Co hardmetals. Typical ranges of magnetic saturation values for some typical alloys are shown in
Table 68 [96R1]. It has been pointed out that for accurate correlations, it is preferable to have an inde-
pendent analysis of the cobalt content (not the assumed figure, based on the make-up of the alloy) and
also some information on other solutes that might be present.
Table 68. Typical ranges of magnetic saturation values in µT m3 kg−1 [96R1].
5 wt% Co 10 wt% Co 15 wt% Co

Hardmetal
Magnetic saturation, 4 πσB 8.0 - 10.1 16.1 - 20.2 24.1 - 30.3
Percentage saturation 80 - 100 80 - 100 80 - 100
Binder-phase
Magnetic saturation, 4 πσB 160 - 202 160 - 202 160 - 202
Percentage saturation 80 - 100 80 - 100 80 - 100
13.4.2.2.5 Toughness
A value of toughness for hardmetal alloys is difficult to define because of the interpretation of the word,
particularly in relating this to scientific terms. The most frequent methods of measurement are based on
plain strain fracture [88R] and Palmqvist fracture toughness [99R]. Both methods have inherent problems
of measurement but there is a general trend, for hardmetal alloys, indicating that toughness decreases
with increase in hardness - Fig. 13.104 [95R]. In the range of fine grained WC-Co alloys (with and with-
out grain growth inhibitors), it has been shown that the Palmqvist test can be used to indicate a number of
features relating hardness to fracture toughness - Fig. 13.105 [97S1]. Results comparing fracture tough-
ness versus binder content at a fixed hardness, show that a high binder content does not necessarily mean
a high toughness. Especially at the lower hardness range, this relationship does not exist. At the higher
hardness range, a higher binder content can to some degree result in an improvement in the hardness to
toughness relationship. However, other factors such as sintering conditions, type of grain growth inhibi-
tor, precursor source etc. also play an important role in determining this relationship.
13.4.2.2.6 Transverse rupture strength
The measurement of this property is quite difficult, in the sense of producing accurate and comparable
data, due to the variety of test procedures and the preparation of the specimens [96R2]. Different values
are also ascribed to hardmetal alloys, for what is termed coarse, medium and fine etc. WC grain size. As
there are no standard procedures for measuring grain size, this throws doubt on the ability to compare

results from one investigation with another. Fig. 13.106 [99S2] demonstrates the general influence of WC
grain size within two groups - fine and medium - and cobalt content on transverse rupture strength. A
further two factors markedly influence transverse rupture strength values - carbon content and porosity
level of the alloys. To illustrate this, Fig. 13.107 [95K1] shows the influence of carbon content on these
values. This is quite evident, even within the two phase WC-Co field, and is due to the amount of tung-
sten in solid solution within the cobalt binder. Porosity, particularly in the size range > 25 µm, has an
enormous effect on these strength values, as shown in Fig. 13.108 [95K1]. The positive influence of HIP
treatment is also demonstrated by these results.
As an example of the correct presentation of transverse rupture data, Fig. 13.109 [95K1] illustrates not
only the complete history of the test results, expressed in a Weibull distribution diagram, but also the full
test procedural parameters. Once again the positive influence of HIP treatment, on reducing the scatter of
individual results, by increasing the Weibull parameter - m - from 8.35 to 13.7 is evident.
13.4.2.2.7 Compressive strength
Compressive strength of hardmetals is of particular interest in applications, such as construction parts in

high pressure equipment, e.g. production of synthetic diamond and CBN.
The compressive strength increases with decreasing binder content and decreasing WC grain size as
shown in Fig. 13.110 [99S2]. With a cobalt content of 3 wt% and a WC grain size of < 0.5 µm a compres-
sive strength of 11500 MPa can be reached. A range of values for different alloys is shown in Table 61.
13.4.2.2.8 Modulus of elasticity (Young’s modulus)
In measuring compressive strength, a linear relationship between strain and load applies as per Hooke’s
Law. The modulus of elasticity - E - can be determined from the slope of the straight line. However, be-
cause it is difficult to obtain accurate values by this means, the ISO 3312 standard specifies a resonance
technique. The modulus of elasticity of hardmetal is extremely high and decreases in a linear mode with
increasing cobalt content, as shown in Fig. 13.111 [99S2].
13.4.2.2.9 Poisson’s ratio
Poisson’s ratio ν can be determined from the elastic/plastic deformation characteristics observed during
compressive strength measurements or by using values of E and G (shear modulus) determined by the
resonance method and calculated from the formula:
E
ν= −1 (18)
2G
Poisson’s ratio has values of between 0.22 and 0.24 for hardmetals and increases with increase in cobalt
content, as shown in Fig. 13.111 [99S2].
13.4.2.2.10 Tensile strength
The uniaxial technique of measuring tensile strength of hardmetals is extremely difficult due to their low
ductility. However it has been possible to use a modified bend testpiece to yield satisfactory values [79R].
The results indicate that alloys with a cobalt content of from 6 - 11 wt% and WC grain sizes from 1.2 µm
to 4 µm, all have tensile strengths that fall in a narrow band from 2200 MPa to 2600 MPa. These values
are higher than those often quoted, based on various evaluations (50 - 56%) of the transverse rupture
strength [95K1, 99S2].

13.4.2.2.11 Fatigue strength
The fatigue strength, under pulsating compression loading, of a number of WC-Co hardmetal alloys, is
shown in Fig. 13.112 [99S2]. The results demonstrate that no defined fatigue strength limit is reached
with an infinite life, as is the case with the majority of steels. A reduction in WC grain size and a decrease
in cobalt content leads to an increase in fatigue strength. Further results [85S2] have shown that the sur-
face condition of the material, such as sintered, ground, polished etc. along with external and internal
defects, have a marked effect on fatigue strength. Alloys with a high cobalt content - 25 wt% - show fa-
tigue striations, through the binder phase, on the fractured faces.
13.4.2.2.12 Electrical resistivity
A typical value of electrical resistivity of the WC-Co hardmetals is 20 µΩ cm - Table 61 -, while for al-
loys containing high amounts of (Ti Ta Nb)C it rises to 24 - 40 µΩ cm - Table 62. Cermets, however,
have a very much higher value of 48 - 97 µΩ cm - Table 67.
13.4.2.2.13 Abrasion wear resistance
There are many wear resistance tests which have been applied to hardmetals, such as “pin on disc” (dry)
and "alumina slurry between a steel wheel and the specimen" (wet). However, only this latter test -
ASTM B611 - is fully internationally recognised [96R2]. Even this test has limitations and the results
cannot be universally applied to all wear situations. The value of wear resistance (abrasive wear) - WN
(wear number) - obtained from the ASTM B611 test is calculated from the inverse of the abrasion resis-
tance, that is density of the specimen divided by mass loss of the specimen giving a term - cm−3. The
results from testing many alloys, shown in Fig. 13.113 [99S2], indicate values increase with decrease in
WC grain size and cobalt content in the range of 5 to 125.
Using this test and a number of WC-6 wt% Co alloys, the following empirical relationship between
wear resistance and hardness was found [92R]:
VL = a exp (bH) , (19)
where VL is the volume loss (cm3), H is the hardness (HV30) and “a” and “b” are constants having values
of 50.4 and −0.0046, respectively. However, it was pointed out that values derived from this relationship
should be applied with caution.
Alloys with a high (Ti Ta Nb)C content show a lower wear resistance, when compared with WC-Co
alloys with the same volume of binder.
Although there is no standard erosion test for hard materials, it is of some importance, because of
certain applications, to have some understanding of this property. A number of investigations have shown
the importance of cobalt content of WC-Co alloys on the resistance to impact erosion by 100 grit SiC
particles travelling at 40 m s−1. Fig. 13.114 [87P] also shows the influence of the incidence angle of par-
ticle impingement. The results show a maximum weight loss at ca. 10 wt% Co which can be explained by
the structural characteristics of the alloys. Care should be exercised in applying these results to other
situations of wear since wear resistance is not an independent materials property, it rather depends on
various parameters of the system in which wear occurs.
13.4.2.3 Thermal properties
13.4.2.3.1 Linear coefficient of thermal expansion
The linear coefficient of thermal expansion of hardmetal alloys is very low being only approximately half
that of martensitic/ferritic steels and only a quarter that of austenitic steels. The WC-Co alloys demon-
strate a range of 5.0 to 7.8 · 10−6/K in the temperature range 20 - 800 °C , increasing with increasing
cobalt content. The alloys containing (Ti, Ta, Nb)C, in the cobalt range 8 - 11 wt% Co, show slightly
higher values - 6.3 to 7.2 · 10−6/K (Table 67).

13.4.2.3.2 Thermal conductivity
Hardmetal alloys possess relatively good thermal conductivity properties, being approximately a third that
of copper. At room temperature, the values range from 85 - 100 W/(m K) for WC-Co alloys to 20 W/(m K)
for alloys with high amounts of titanium carbide. Cermets have quite low values - 9 - 15 W/(m K).
Because of the interest in this property in relation to various applications, the values at higher tem-
peratures are of significance. These are shown in Table 69 [85K] for a number of alloys.
Table 69. Thermal conductivity of WC-Co hardmetals in relation to temperature [85K].
Temperature Thermal conductivity [W/(m K)]

°C
WC-6Co WC-6Co WC-9Co WC-15Co WC-20Co
(fine grain) (coarse grain) (fine grain) (fine grain) (fine grain)
500 68.9 68.3 70.4 not determined not determined
550 67.6 69.0 68.6 65.1 63.8
600 66.7 68.8 68.4 68.8 62.5
650 66.0 68.6 66.8 63.1 61.6
700 64.8 68.0 64.7 62.6 61.4
Temperature Thermal conductivity [W/(m K)]

°C
WC-6Co WC-9Co WC-15Co
(very coarse grain) (coarse grain) (coarse grain)
500 76.3 83.4 72.5
550 75.3 80.4 71.8
600 72.5 77.4 68.6
650 71.2 74.5 67.0
13.4.2.3.3 Specific heat
Specific heat values for WC-Co alloys lie in the range 150 - 350 J(kg/K). Table 70 [85K] shows the val-
ues for a number of WC-Co alloys measured in the temperature range of 87 - 687 °C.
Table 70. Specific heat of WC-Co hardmetals in relation to temperature [85K].
Temperature Specific heat cp [kJ/(kg/K)]

°C

(fine grain) (coarse grain) (fine grain) (fine grain) (fine grain)
87 0.213 0.218 0.222 0.232 0.247
177 0.234 0.238 0.243 0.259 0.272
277 0.247 0.251 0.259 0.272 0.289
377 0.259 0.264 0.268 0.285 0.301
477 0.264 0.268 0.276 0.293 0.314
577 0.268 0.276 0.280 0.301 0.318
687 0.276 0.285 0.289 0.314 0.331

13.4.2.3.4 Themal diffusivity
Thermal diffusivity values are of significance in determining the temperature distribution within tools
operating under conditions of high temperature. Thermal conductivity and thermal diffusivity are related
to each other by the following expression:
λ = a ρ cp (20)
where λ = thermal conductivity

a = thermal diffusivity
ρ = density
cp = specific heat
Table 71 illustrates the dependency of thermal diffusivity on temperature for fine and coarse grain WC-
Co alloys within the range 500 - 1200 °C.
Table 71. Thermal diffusivity of WC-Co hardmetals in relation to temperature [85K].
Temperature Thermal diffusivity [cm2 s−1]

°C

(coarse grain) (coarse grain) (fine grain) (fine grain) (coarse grain)
500 0.177 0.173 0.175 not determined not determined
600 0.166 0.165 0.165 0.154 0.146
700 0.159 0.158 0.154 0.143 0.138
800 0.156 0.153 0.148 0.139 0.130
900 0.144 0.145 0.137 0.127 0.118
1000 0.141 0.146 0.139 0.125 0.117
1100 0.137 0.139 0.135 0.123 0.116
1200 0.131 0.133 0.128 0.116 0.110
Temperature Thermal diffusivity [cm2 s−1]

°C
WC-6Co WC-9Co WC-12Co WC-15Co

(very coarse grain) (coarse grain) (coarse grain) (coarse grain)
500 0.185 0.195 0.171 0.170
600 0.173 0.181 0.163 0.161
700 0.164 0.169 0.155 0.153
800 0.159 0.160 0.148 0.145
900 0.148 0.155 0.139 0.135
1000 0.148 0.144 0.138 0.135
1100 0.142 0.141 0.135 0.132
1200 0.137 0.135 0.126 0.125

13.4.2.4 Low temperature properties
13.4.2.4.1 Hardness
The measurement of hardness of four hardmetal alloys - 6 wt% and 11 wt% Co, each with WC grain sizes
of 1.4 µm and 5.0 µm - at temperatures down to –196 °C, showed a marked increase for all alloys. As an
example, as shown in Fig. 13.115 [83A], the ambient temperature value for the 6 wt% Co - 1.4 µm WC
grain size alloy of 1535 - 1560 HV30 increased to 1860 - 2000 HV30 at −196 °C. Similar results were
obtained for other WC-Co and WC-Ni alloys [78S].
The transverse rupture strengths for WC- 10 - 20 wt% Co and WC- 10 - 20 wt% Ni alloys were measured
at temperatures down to –196 °C. The WC-Co alloys showed an increase of 7.5 - 11% while the WC-Ni
alloys showed an increase slightly lower of 2 - 3% [78S].
13.4.2.5 High temperature properties
13.4.2.5.1 Hardness
The decrease in hardness for WC-Co alloys is shown in Fig. 13.116 [95K1], while Fig. 13.117 [95K1]
illustrates the fall for WC-(Ti Ta Nb)C-Co alloys. An addition of (Ti, Ta, Nb)C significantly increases
the hot hardness of hardmetals; for example a typical ISO-P10 alloy - WC-30 wt% (Ti Ta Nb)C - 10 wt%
Co - still retains ca. half of the ambient temperature hardness at 800 °C, while the hardness of a WC-
10 wt% Co alloy, at the same temperature is reduced to approximately 35%.
The change in micro-hardness (HV0.2) with an increase in temperature for a cermet alloy - 15.8 %
WC, 21.16 % TiC, 21.20 % TiN, 10 % (Ta Nb)C, 1.34 % C, 12.00 % Co, 3.5 % Ni, 15 % (Ti2 Al)C
(all wt%) - is shown in Table 72 [95G2].
Table 72. Decrease in hardness of a cermet alloy with an increase in temperature [95G2].
Temperature [°C] 20 200 400 600 700 800 900 1000
Hardness HV0.2 1759 1403 1162 880 739 562 463 346
Transverse rupture strength decreases with an increase in temperature, as shown in Fig. 13.118 [95K1] for
a WC-9 wt% Co alloy. It is noticeable that the reduction in strength becomes quite marked above ca.
750 °C. The influence of cobalt content, WC-grain size and carbon content on transverse rupture strength
at 1273 K is shown in Fig. 13.119 [82S]. Here it can be seen that maximum values of strength are ob-
tained at the WC grain sizes of 4.0 and 5.0 µm in high and low carbon alloys respectively, independently
of the cobalt content - 10 wt% or 20 wt%.
13.4.2.5.3 Compressive strength
As with all of the different strength values, compressive strength falls with an increase in temperature.
Fig. 13.120 [95K1] illustrates the reduction for three alloys - WC-6 wt% Co, WC-20 wt% (Ti Ta Nb)C -
9 wt% Co and WC-11.5 wt% (Ti Ta Nb)C - 6.5 wt% Co. It can be seen that, for all three alloys, compres-
sive strength falls to below 3000 MPa when a temperature of 800 °C is exceeded.
Fig. 13.121 [67T] shows the 5 % compressive proof stress values for three tungsten carbide alloys -
WC grain size 1.4 µm with 6 wt%, 11 wt% and 20 wt% Co, respectively. At 770 MPa the 20 wt% Co
alloy shows 5 % strain at 860 °C, the 11 wt% Co alloy at 960 °C, and the 6 wt% Co alloy at

1025 °C. With all three alloys the proof stress drops rapidly with further rise in temperature, but more
rapidly the lower the cobalt content, so that the curves converge at a temperature of approximately
1150 °C at a stress near to 77 MPa.
13.4.2.5.4 Creep
Compression creep was measured for three hardmetals - WC with 10 vol% Co, 10 vol% Ni and 10 vol%
Ni-Ni3Al, grain size 1.1 µm - in the temperature range 480 - 760 °C. The secondary creep rate (strain rate)
values for various loads at the three temperatures are shown in Table 73 [85R].
The creep curves for all the hardmetals were typical in showing an elastic displacement as the load
was applied, followed by a primary and then a secondary stage.
Table 73. Secondary compression creep rates for three hardmetals in the temperature range 480 - 760 °C
[85R].
WC-10 vol% Co WC-10 vol% Ni WC-10 vol% Ni-Ni3Al

⋅ ⋅ ⋅
Stress Strain rate ε Stress Strain rate ε Stress Strain rate ε
MPa 10−6/min MPa 10−6/min MPa 10−6/min
480 °C 605 °C 760 °C 480 °C 605 °C 760 °C 480 °C 605 °C 760 °C
1084 0.15 1000 1.8 1035 0.2

1026 2.05 1410 7.4 1780 2.7
1897 2.90 1084 a 2.05 2370 25
2222 14.4 1545 a 52.5 2755 110
2601 105 1897 697
890 < 0.5 550 < 0.5 570 < 0.5
1075 5.7 920 10 975 4.3
1550 41 1320 290 1410 29
1955 230 1800 290
435 5.8 380 10 420 13
710 16 560 29 630 29
975 110 760 140 435 b 13
1000 1300 590 b 25
870 b 180
a
New sample.
b
Sample tested previously at 480 °C.
Fig. 13.122 [87L] shows an Arrhenius plot of the steady state creep rate for various values of applied
compressive stress for a WC - 2.2 µm grain size - 37 vol% Co alloy. This indicates that the apparent creep
activation energy is independent of the applied stress. The apparent activation energy of the creep process
has a constant value of QA = 5 to 5.4 eV.
13.4.2.5.5 Oxidation
The oxidation resistance of hardmetals and cermets in air at high temperatures is not only dependent on
the oxidation resistance of the hard phase but also on that of the binder phase. Fig. 13.123 [92K2] shows
that the resistance of the cermet alloy, 85.7 wt% Ti(CN) - 0.8 wt% dopant carbides - 13.5 wt% Co/Ni is
superior to that ofthe WC-31 wt% (Ti Ta Nb)C - 9 wt% Co alloy and very superior to that of the
WC-6 wt% Co alloy.

13.4.2.5.6 Fracture toughness/hot hardness
In many applications the choice of an alloy to meet the required objectives is dependent on a number of
properties. Very often toughness, hardness and wear resistance are of equal importance and, in some
instances, high temperature properties are an essential feature. The interaction between properties of dif-
ferent alloys and alloy types is therefore of interest to the user. Fig. 13.124 [93G2] shows the relationship
between ambient temperature fracture toughness and hot hardness at 800 °C for a selection of hardmetals
and cermets. Each alloy group shows a distinct pattern, with the WC-Co alloys demonstrating the best
combination. However, the highly developed cermet alloys with a high nitrogen content and a homogene-
ous structure (optimised) reveal a combination which is very close to the WC-Co alloys.
13.4.2.6 Chemical properties
13.4.2.6.1 Corrosion resistance
It is possible to determine the corrosion resistance of different types of hard materials by comparing re-
sults obtained from current density/potential curves. Thus, the current density at the same potential is a
measure of corrosion resistance: The higher the current density, the poorer is the corrosion resistance.
This is demonstrated in Fig. 13.125 [95K1], where for the specific test conditions, it can be seen that the
WC-9.5 % Ni/Cr alloy shows a higher resistance to corrosion than the normal WC-9 % Co alloy.
Table 74 [95K1] shows the rate of corrosion for a number of hardmetal alloys in different liquids at
ambient temperature. In general, it can be stated that with WC-Co alloys, the resistance to corrosion in
acids decreases with an increase in cobalt content. The resistance is markedly increased if the cobalt is
replaced by nickel or better still nickel/chromium. In ammonia solutions, hardmetals with a cobalt binder
demonstrate a poor resistance due to the formation of cobalt hexamine complexes.
Table 74. Rate of corrosion of different hardmetal alloys in different liquids at ambient temperature
[95K1].
Test solution Hardmetal composition [wt%]

91 WC 82 WC 90,5 WC 85 WC
9 Co 3 (Ta, Nb)C 9,5 Ni/Cr 15 Ni/Cr
15 Co
Rate of corrosion [g/(m−2d)]
10 % HCI 1.0 2.3 0.8 1.4
10 % H2SO4 6.8 11 0.2 0.2
10 % HNO3 220 560 0.2 0.05
25 % NH4OH 1.0 1.1 0.05 < 0.01
20 % NaOH 0.06 0.06 < 0.01 0.02
25 % CH3COOH n. d.* n. d.* < 0.01 0.04
Sea water < 0.01 0.2 < 0.01 0.02
Essen tap water n. d.* n. d.* < 0.01 0.02
(Germany)
* n. d. = not determined.

13.5 Properties of diamond and cubic boron nitride
13.5.1 Standards
Three organisations, associated with standards which apply to diamond and CBN products, are, in
Europe: Fédération Européene des Fabricants des Produits Abrasifs (FEPA), 20 Avenue Reille, 75014
Paris; in America: American National Standards Institute (ANSI) and in Japan: Japanese Industrial Stan-
dards (JSI).
The following FEPA standards cover such products:
1) Standard for diamond and CBN grinding wheels

2) Standard for diamond grain sizes
3) Standard for diamond micron sizes
4) Standard for measuring metal coated weight on diamond and CBN
5) Standard for measuring the relative strengths of saw diamond grits
6) Standard for diamond saws
In the USA the following standards are applicable:
1) ANSI B74.3 shapes and sizes of diamond or CBN abrasive products, specifications for
2) ANSI B74.13 markings for identifying grinding wheels and other bonded abrasives
3) ANSI B74.16 checking the size of diamond abrasive grain
4) ANSI B74.17 bulk density of diamond abrasive grains, test for
5) ANSI B74.20 grading of diamond powder in sub-sieve sizes.
The identification of diamond and cubic boron nitride grit (particle) dimensions is extremely important in
any type of tool. As two methods are used - one in Europe and one in the USA - the following Table
enables a comparison to be made between the two methods.
Table 75. Comparison between FEPA and ANSI methods of grading diamond and CBN grit (particle).
ANSI FEPA Theoretical

Method Method median particle
(mesh size) (opening in mesh) diameter [mm]
20/30 D 852 0.760

30/40 D 602 0.539
40/50 D 427 0.378
50/60 D 301 0.288
60/80 D 252 0.226
80/100 D 181 0.174
100/120 D 151 0.148
120/140 D 126 0.123
140/170 D 107 0.103
170/200 D 91 0.086
200/230 D 76 0.075
230/270 D 64 0.066
270/325 D 54 0.057
325/400 D 46 0.048

13.5.2 Diamond - natural and synthetic
13.5.2.1 General
The general properties of diamond are shown in Table 76 [99D]. It can be noted that under composition
there is a marked difference between natural and synthetic diamond, in as much that synthetic diamond
can contain a significant proportion of the elements nickel, cobalt and iron. The particular elements and
amounts depend upon the type of solvent/catalyst used, and the conditions of manufacture. In the subdivi-
sion of diamonds into various classifications, it is stated that most natural diamonds fall into the group
Type I a, whilst almost all synthetic are of Type I b.
13.5.2.2 Mechanical properties
The mechanical properties of diamond are shown in Table 77 [99D]. Although the measurement of hard-
ness of diamond is quite difficult, and the values obtained are markedly influenced by the crystallographic
surface and direction, it has been shown in one investigation that hardness is also influenced by the nitro-
gen content as shown in Fig. 13.126 [98S1]. Here it can be seen that the hardness of synthetic diamond
lies in a fairly narrow band within a nitrogen content of 10 - 100 ppm, whilst natural diamond shows a
decrease with contents up to 1000 ppm, followed by a rapid rise above this level.
Strength values are very dependent on crystal orientation and also impurity levels within the crystals.
Therefore, wide variations in value are reported.
Table 76. General properties of diamond - data supplied and property of De Beers Industrial Diamond
Division, S. Africa.
I Chemical composition
Diamond is composed of the element carbon. Only nitrogen and boron are known with certainty to be
incorporated in the diamond lattice.
Major impurities: Nitrogen, up to 0.2 % in natural Type I a diamond (see section II below).
Nickel, iron etc. up to 10 % as inclusions in synthetic diamond (ppm or less in natural
diamond).
Aluminum, up to 10 ppm in natural diamond. Boron, up to ~ 0.25 ppm in natural Type
II b and 270 ppm in specifically doped Type II b synthetic diamond - now thought to
be responsible for semiconducting properties of Type II b diamond. Many other impu-
rities are also believed to be present in the form of inclusions.
Inclusions: Twentyfive mineral species have been positively identified.
References: [67L1, 68H, 71C1, 71C2, 75S1]
II Classification
Type I a diamond: Contains nitrogen as an impurity in fairly substantial amounts (of the order of
0.1 %), and which appears to have segregated into small aggregates. Also contains
platelets, associated with the nitrogen impurity, the exact structure of which is not
known. Most natural diamonds are of this type.
Type I b diamond: Also contains nitrogen as an impurity but in dispersed substitutional form. Almost
all synthetic diamonds are of this type.

Type II a diamond: Effectively free of nitrogen impurity. Very rare in nature, these diamonds have en-
hanced optical and thermal properties.
Type II b diamond: A very pure type of diamond which has semiconducting properties: generally blue in
colour. Extremely rare in nature. Semiconduction properties can be imparted to
synthetic crystals by the incorporation of boron.
References: [34R, 52C, 59K, 65D1, 73E]
Note: Classification is based principally on optical properties. Further subdivisions can be made almost
ad infinitum (indeed, almost every diamond is different in some way) but the above classification
is universally accepted. Some diamonds have been shown to consist of more than one type, e.g. a
complex interweaving of Type I and Type II material.
III Crystal structure
7
Space Group: Cubic Fd3m-O h
Unit cell: Lattice constant between 0.356683 ± 0.000001 and 0.356725 ± 0.000003 nm at 298 K.
Atoms located at: (000), ( 1 1 0), (0 1 1 ), ( 1 0 1 ), ( 1 1 1 ), ( 3 3 1 ), ( 1 3 3 ), ( 3 1 3 ).
22 22 2 2 444 444 444 444
Nearest neighbour distance: 0.154450 ± 0.000005 nm at 298 K.
Atomic mass: 12.01 g/md
Atomic radius: 0.077 nm
Number of atoms in a unit cell: 8
Number of atoms m−3: 1.77 · 1029
References: [47L, 57S, 59K]
IV Density
Average of 35 diamonds (3.51524 ± 0.00005) · 103 kg m−3 at 298 K. Spread 0.77 kg m−3.
Average of 19 Type I (3.51537 ± 0.00005) · 103 kg m−3.
Average of 14 Type II (3.51506 ± 0.00005) · 103 kg m−3.
Note: Calculation from the lattice constant gives 3.51525 · 103 kg m−3; the spread is due to lattice faults
and impurities and not to experimental error.
Reference: [64M]
Note: Additional values (including diamond coat and polycrystalline diamond) see [70B1, 71D]
V Graphitization
When diamonds are heated to a high temperature, the changes that take place depend markedly on the
environment around the diamond. If oxygen (or other active agent) is present, a black coating can form on
the surface of diamond above about ~ 900 K. This is not true graphitization (which involves the transition
of diamond to graphite without the aid of external agents). If diamonds are heated in an inert atmosphere,
the onset of graphitization can just be detected at ~ 1800 K and the rate of graphitization increases rapidly
until at ~ 2400 K a 0.1 carat octahedron is converted totally into graphite in less than 3 minutes. The oc-
tahedral diamond surface graphitizes with an activation energy of 1060 ± 80 kJ mol−1 and the dodecahe-
dral surface graphitizes more rapidly with an activation energy of 730 ± 50 kJ mol−1. The activation vol-
ume for the graphitization process is about 10 cm3 mol−1. It appears that the graphitization process in-
volves the removal of one atom at a time from the diamond surface. For an octahedral surface three car-

bon-carbon bonds are broken when the atom is detached and for the dodecahedral face, two carbon-
carbon bonds are broken.
References: [63S, 64E, 72D2]
VI Resistance to chemical attack
Diamond is extremely inert chemically and is not affected at all by any acids or any other chemicals,
except those which at high temperatures act as oxidising agents - these provide the only effective way to
attack diamond at temperatures below ~ 1300 K and at normal pressures. Substances such as sodium
nitrate are known to attack diamond in the molten state at temperatures as low as ~ 700 K. In oxygen
itself, diamond starts to be oxidised at perhaps ~ 900 K.
The only other possible form of chemical attack is by two groups of metals. The members of the first
group are avid carbide formers, and include tungsten, tantalum, titanium and zirconium. At high tem-
peratures these will react chemically with diamond to form their respective carbides. The second group
includes iron, cobalt, manganese, nickel and chromium, and also the platinum group of metals. In the
molten state these metals are true solvents for carbon.
Table 77. Mechanical properties of diamond - data supplied and property of De Beers Industrial Diamond
I Hardness
(a) Scratch hardness (Mohs scale)
The Mohs hardness is a scratch hardness test and is related to the indentation hardness of the solid (see
below). If the Mohs number is M and the indentation hardness in kg/mm2 is H, the relation between these
quantities is approximately
log H = 0.2 M + 1.5
There is reasonable "equality of intervals" between the first 9 integers on the Mohs scale, but the interval
between 9 (corundum) and 10 (diamond) represents a much larger difference in indentation hardness than
a single unit on the Mohs scale would suggest.
Typical values of very hard materials are:
SiC (carborundum), Al2O3 9
WC, W2C, VC 9 - 9.5
Diamond 10
Reference: [54T]
(b) Indentation hardness (Knoop scale)
Value ((001) diamond surface): 5700 - 10400 HK, depending on crystallographic direction and with nor-
mal loads 4.91 N, 9.81 N and 19.62 N.
There are many other scales, some appropriate to all materials, some only to metals. A Knoop indenter
produces a wedge-shaped indentation in the form of a parallelogram with one diagonal at least seven
times longer than the other diagonal, and this method is generally considered to be the most accurate for
crystalline solids. On any scale diamond is the hardest known material.

It has recently been shown that the measured hardness value is significantly influenced by the normal
load, the indenter shape and its crystallographic relationship with that of the indented surface. It has also
been shown that the indentation hardness of diamond decreases with increasing temperature.
Diamond ((111) surface, <110> direction, 4.61 N load): 9000 HK

Cubic boron nitride ((111) surface, <110> direction, 4.61 N load): 4500 HK
Boron carbide (surface, direction and load not known): 2250 HK
Silicon carbide (surface, direction and load not known): 1875 - 3980 HK
Tungsten carbide (surface, direction and load not known): 2190 HK
Titanium carbide (surface, direction and load not known): 2190 HK
Aluminum oxide (surface, direction and load not known): 2000 HK
All above measurements were made at 298 K.
References: [39K, 67L2, 70B2, 71B2, 74B]
(c) Abrasion resistance
The resistance of diamond to abrasion depends greatly on the method of abrasion. For a description of the
very great dependence of the rates of polishing diamond by the normal polishing methods see [72W]. For
a comparison of the abrasion resistance of diamond with other gemstones see [73W]. For the wear of
diamond when rubbing at low speeds, under loads, on a range of metals, see [72C1].
(d) Friction
The coefficient of friction in air, µ, is about 0.1, but the value depends on load, geometry, polishing di-
rection and especially orientation. On the (111) plane µ ~ 0.05 and is approximately constant in all direc-
tions. On the (100) cube plane values vary between µ ~ 0.05 along <011> to 0.1 - 0.15 along <010> for
polishing along <100>. After polishing in other directions the fourfold symmetry can change to twofold.
µ in air is little affected by lubricants or sliding speed in the range of few microns per second up to a few
millimetres per second.
µ in vacuum approaches 1 [66B].
References: [58S, 66B, 72C2, 72W, 78T]
II Elastic properties
(a) Elastic moduli [ 100 GPa]
C1 1 = 9.5 C1 2 = 3.9 C4 4 = 4.3 [46B]

C1 1 = 11.0 C1 2 = 3.3 C4 4 = 4.4 [53P]
C1 1 = 10.76 C1 2 = 1.25 C4 4 = 5.76 [57M]
C1 1 = 10.76 C1 2 = 2.75 C4 4 = 5.19 [65M]
C1 1 = 10.79 C1 2 = 1.24 C4 4 = 5.78 [72M]
C1 1 = 10.764 C1 2 = 1.252 C4 4 = 5.774 [75G]
Pressure and temperature coefficients [72M]
dC/dP 1/C(dC/dT) [K−1]
C1 1 6.0 ± 0.7 −(1.4 ± 0.2) · 10−5

C1 2 3.1 ± 0.7 −(5.7 ± 1.5) · 10−5
C4 4 3.0 ± 0.3 −(1.25 ± 0.1) · 10−5

(b) Bulk modulus
1
K= 3 (C1 1 + 2C1 2)
K = 580 GPa [46B]

K = 590 GPa [53P]
K = 442 GPa [57M]
K = 542 GPa [65M]
K = 560 GPa [66D]
K = 442 GPa [72M]
K = 442 GPa [75G]
Diamond has the highest values of elastic moduli of any material next to tungsten with K = 299 GPa
calculated from C1 1 = 501, C1 2 = 198, C4 4 = 151.4 GPa.
(c) Poisson’s ratio
C1 2
ν 21 = = 0.103 - 0.291.
C1 1 + C1 2
Excluding the oldest measurement, the average from the five sets of data remaining is
ν = 0.144 ± 0.055
(d) Young’s modulus
( C 1 1 − C 1 2 ) (C 1 1 + 2 C 1 2 ) 1
E1 1 = =
C 1 1 + C1 2 S1 1
[72M, 75G] report Young's modulus values of E = 1050 GPa,

the average from the five newer sets of data is E = (1013 ± 52.6) GPa
(e) Anistropy
2 C4 4
The condition for isotropy is =1
C 1 1 − C1 2
For diamond this ratio is close to unity (1.215), so that Young’s modulus does not vary greatly with ori-
entation.
III Strength
(a) Cleavage plane
Diamond normally cleaves on the (111) plane, but cleavage has been observed on the (110) plane, and, to
a lesser extent, some other planes [28S]. Curved cracks can be produced by gradual loading with a spheri-
cal indenter [66L]. Ring cracks are found frequently on diamond surfaces and can be made by both slow
and impact loading with indenters, not necessarily diamond.

(b) Cleavage energy
Theoretical cleavage energies for diamond.

Plane Angle between plane Cleavage energy
and (111) plane [Jm−2]
111 0° and 70°32΄ 10.6
332 10°0΄ 11.7
221 15°48΄ 12.2
331 22° 0΄ 12.6
110 35° 16΄ and 90° 13.0
322 11°24΄ 13.4
321 22°12΄ 14.3
211 19°28΄ 15.0
320 36°48΄ 15.3
210 39°14΄ 16.4
311 29°30΄ 16.6
100 54°44΄ 18.4
Note: to obtain a fracture surface energy, γ, divide by 2.
Cleavage energy can be computed by calculating the number of bonds which cross the unit area of a cho-
sen plane and multiplying this by the C-C bond strength. The values are obtained by using a value of
389 kJ mol−1 or 5.8 · 10−19 J for the C-C bond [60P].
A value of 5.3 J m−2 is predicted for the fracture surface energy of the (111) plane. An experimental
measurement [79F] giving 6 J m−2 suggests that there is a negligible contribution from plastic deforma-
tion fracture at room temperature.
(c) Velocity of cleavage
Cleavage velocities of a few thousand metres per second are common. Velocities up to 7,200 m s−1 have
been recorded [79F].
(d) Theoretical strength
Theoretical strengths of ideal solids [79F].

Material Strength in tension Strength in shear
Direction σth σth/E System σth σth/G
GPa GPa
C (diamond) <111> 190 0.17 <1 1 0>{111} 121 0.24
Si <111> 32 0.17 <1 1 0>{111} 13.7 0.24
MgO <100> 37 0.15 <1 1 0>{110} 16 0.12
NaCl <100> 4.3 0.10 <1 1 0>{110} 2.8 0.12
Cu <111> 39 0.20 <1 1 2 >{111} 1.2 0.039
Ag <111> 24 0.20 <1 1 2 >{111} 0.77 0.039
The ratio of tensile to shear strengths is predicted to close to unity, but as the table is descended the ratio
becomes large, i.e. the materials in the table range from highly brittle (top) to highly ductile (bottom).
Note: Accurate calculations on diamond are difficult.

(e) Tensile strength
Experimental values for strength show wide variations. This is partly a reflection of the difficulty en-
countered in making tests with diamonds, but also indicates that the strength of individual diamonds is
significantly affected by the defects, inclusions and impurities which they contain. Values quoted in the
literature are also dependent on the values chosen by the authors for the elastic moduli and Poisson’s ratio.
pc and pc' are the average stresses obtained by dividing the load by the crack area and the observed, or
calculated, area respectively, when determining tensile strength using the ring crack indentation method.
Strength data for diamond. Data recalculated with E = 1050 GPa and γ = 0.2 [79F].
Ref. Face Identer pc p c'

radius
mm GPa GPa
65H Octahedral 0.5 tungsten 10.3
Cube carbide 13.2
Dodecahedral 11.8
65H Octahedral 10.8 13.8
Cube 0.39 diamond 10.8 32.4
Dodecahedral 17.6
65B1 Cube 0.28 diamond 13.7 32.4
75B2 Cube 0.245 diamond 29.4
75C Cube 0.25 diamond 16.4 - 32.4
75C Synthetic 0.25 diamond 21.6 - 32.4
octahedral
and cube
( f ) Shear strength
Theoretical value: 120 GPa [66T]

Experimental values: 8.7 GPa (from a friction experiment) [64B]
0.3 GPa (from a torsion test). [66H]
Note: Doubt must exist as to whether these strength values are genuine ‘shear’ strengths; it is very likely
that the diamonds still failed by cleavage. The variation is because of the very different method of
test. In the friction experiment only a very small area of material would be stressed, while in the
torsion test failure would probably start at a comparatively large defect at the specimen edge.
(g) Compressive strength
(i) Average value for natural octahedral containing no visible flaws or inclusions [66H]:
= 8.68 GPa
Maximum value = 16.53 GPa
(Area of faces over which load applied approximately 10−6 m2).
(ii) Synthetic micro-diamonds

A variety of methods are available for strength testing micro-diamonds. The single grit compression
test allows a systematic study of particle strength and factors affecting it. Crushing experiments on
synthetic grit with well defined contact faces give strength values of ~ 10 GPa for good quality ma-
terial of 35/40 US mesh. In general, small diamonds (or small loaded areas) usually exhibit greater
strength than large diamonds (or large loaded areas), i.e., there is a size effect [79F].

(h) Plastic flow
The temperatures for significant dislocation mobility are ≥ 2100 K (Ia diamond) and ≥ 1900 K
(IIa diamond) [65E].
Thermal properties are given in Table 78 [99D]. Once again the influence of impurities on properties can
be seen, particularly with regard to thermal conductivity.
Table 78. Thermal properties of diamond - data supplied and property of De Beers Industrial Diamond
I Thermal conductivity [65B2]
Typical values (at 293 K): Type Ia 600 - 1000 W/(m K)

Type II 2000 - 2100 W/(m K)
Maximum at ~ 80 K Type Ia 2000 - 4000 W/(m K)
Type IIa up to 1.5 · 104 W/(m K)
II Thermal expansion (linear) [56T, 57S, 75S2]
At 293 K (0.8 ± 0.1) · 10−6/K

193 K (0.4 ± 0.1) · 10−6/K
400 - 1200 K (1.5 - 4.8) · 10−6/K
Grüneisen’s law obeyed between 420 K and 1200 K.
III Specific heat [79F]
At 300 K both cp and cV = 6.195 J g−1

For values at other temperatures see References.
Effective Debye temperature 273 - 1100, θD = 1860 ± 10 K.
Effective Debye temperature 0 K, θD = 2220 ± 20 K.

13.5.2.4 Optical and electrical properties
Optical and electrical properties are provided in Table 79 [99D].
Table 79. Optical and electrical properties of diamond - data supplied and property of De Beers Industrial
Diamond Division, S. Africa.
I Refractive index [23P, 77F]
At Hg green 546.1 nm µ = 2.4237

C-line 656.28 nm µC = 2.40990
D-line 589.29 nm µD = 2.41726
F-line 486.13 nm µF = 2.43554
(µ D - 1)/( µ F - µ C) = 55.3
Near cut-off in ultraviolet at λ = 226.5 nm, µ = 2.7151, Brewster angle (at D-line) = 67.53 °.
Coefficient of reflection (normal incidence) 0.17
ε1λ 2 ε2λ 2
Note: µ2 - 1 = +
λ 2
− λ 12 λ 2 − λ 22
where ε1 = 0.3306
ε2 = 4.3356
λ1 = 175.0 nm
λ2 = 106.0 nm
Reference [23P]
1  dµ 
  = 4.04 × 10− 6 K −1
µ  dT  P
1  dµ 
  = 0.36 × 10−1 2 Pa −1
µ  dP  T
Reference [77F]
II Dielectric constant [77F]
ε = 5.70 ± 0.05 at 300 K

ε = 5.70111 - 5.35167 · 10−5 T + 1.6603 · 10−7 T2
1  dε  − 6 −1
  = 8 ⋅ 09 × 10 K
ε 300  dT  P
1  dε  −1 2 −1
  = −0 ⋅ 72 × 10 Pa
ε  dP  T

III Optical transparency [34R, 56C]
Type IIa diamond 225 nm - 2.5 µm, > 6 µm.

Type I diamond ~ 340 nm - 2.5 µm, > 10 µm.
Note: Visible region 400 - 700 nm.
Any colouration is due to absorption bands in this region, or in the case of Type IIb diamonds to the tail
of the infrared absorption spectrum associated with the acceptor centre. The yellow colouration of
Type Ib diamonds results from the tail of the ultraviolet absorption associated with the substitutional
nitrogen impurity.
IV Optical spectra
For a guide to optical spectra in the visible region see [74C]. For a comprehensive review see [77D].
V Resistivity [65K, 67D]
Type I and most Type IIa, > 1018 Ω m

Type II b, 103 - 105 Ω m
Note: Figures for diamond only apply in the dark since there is considerable photoconductivity in ultra-
violet light.
Note: Diamonds exist which would normally be classified as Type IIa, but which have resistivities in-
termediate between Type IIb and Types I and IIa. These fall within a range from 105 - 1016 Ω m at
293 K. However, most diamonds are insulators with a resistivity of > 1016 Ω m.
Comment: Insulating diamond can have a very high resistivity, comparable with or better than many
insulators in commercial use. The best insulator is probably fused silica (> 5 · 1020 Ω m).
VI Hole effective mass
m0 = free electron mass
(a) cyclotron resonance measurements [62R]

heavy hole band m* = 2.1 m0
light hole band m* = 0.7 m0
split-off band m* = 1.06 m0
(b) average from Hall effect measurements

Wedepohl m* = 0.25 m0 [63M]
Kemmey m* = 0.4 m0 [63M]
Williams m* = 0.75 m0 [70W]
Lightowlers m* = 1.1 m0 [65D2]
(c) average from Faraday rotation measurements

m* = 0.88 m0 [64P]
VII Hall mobility and coefficient
µH = 0.16 m2 V−1 s−1 (typical value at 290 K)

The exact value is sample dependent and strongly temperature dependent. Values for synthetic semi-
conducting diamond are generally lower, and are much lower in heavily doped material.
R = 0.1 m3/K (typical value at 290 K)
Again, the precise value depends on the sample and very strongly on temperature. (Both these must be so
because R is related to the number of free holes). Synthetic semi-conducting diamond values of Hall
coefficient in the range 10−3 < R < 0.3 m3/K at 290 K may be obtained.
13.5.3 Cubic boron nitride (CBN)

13.5.3.1 General
Boron nitride is a man-made material and does not exist in nature. The usual form, which has been known
to industry for sometime, consists of a white material used as a solid lubricant and as a refractory mate-
rial. The lattice structure is hexagonal similar to that of graphite.
The cubic form was only realised after the discovery, in 1957, by R. H. Wentorf Jr. of the General
Electric Company, USA, that the hexagonal form could be transformed to the cubic by the use of high
temperatures and pressures.
The general properties of cubic boron nitride are shown in Table 80 [72D1].
13.5.3.2 Mechanical properties
The mechanical properties are shown in Table 81 [72 D1].

The accepted hardness value of 4500 HK is about half that of diamond.
The quoted elastic constants have been calculated by extrapolating data derived from empirical rela-
tionships among III-V compounds.
The thermal properties are shown in Table 82 [72D1]. The specific heat values are approximately twice
that for diamond, whilst the thermal conductivity value is much lower than that of diamond. The values
for thermal expansion between 430 °C and 1160 °C are slightly higher than those for diamond.
Cubic boron nitride is extremely stable in air, nitrogen or vacuum - temperatures ca. 1400 - 1550 °C
have to be exceeded before any change in stability occurs. This is in marked contrast to diamond which
starts to form a graphite surface film at temperatures ca. 650 °C in the presence of oxygen.
13.5.3.4 Optical and electrical properties
The optical and electrical properties are shown in Table 83 [72D1].
13.5.3.5 Thermodynamic properties
The thermodynamic properties are shown in Table 84 [72D1].
13.5.3.6 Miscellaneous
A number of other properties, including some comments on magnetic traits, are shown in Table 85
[72D1].
(A number of values in the various tables have been converted to the appropriate SI-units.)
For a more detailed review of the properties reference [72D1] should be consulted especially in rela-
tion to various sources of data and information.

Table 80. General properties of cubic boron nitride - data supplied and property of General Electric
Company, USA [72D1].
Property and units Value and remarks

Formula BN Essentially stoichiometric but small amounts
(generally < 1%) of impurities C, O, Li, Be, S, P,
and others may be present depending on chem-
istry of growth system
Molecular Weight 24.8177 43.6 wt% B; 56.4 wt% N
Name Cubic boron nitride
Cubic BN; CBN
BORAZONT General Electric Co. trademark for abrasive
grain
β-BN Russian scientific literature
Elbor Russian abrasive
Cubonite Russian abrasive
Crystallographic Properties
Crystal system Cubic
Structure type Zincblende
Space group F 4 3m
Atoms/unit cell 4B, 4N
Lattice constant (25 °C) [nm] 0.3615 ± 0.0001
Ionic distance (B-N) [nm] 0.157
3
Density [g/cm ] 3.48 calculated from X-ray data
3.45 measured
Crystal habit truncated tetrahedra or octahedra {111}
hexagonal plates {111}
{111} and {100}
{111} and {110}
crystals twinned on {111}
irregular blocky forms
Twinning growth twinning on {111}
Cleavage perfect on {011}
Surface triangular and hexagonal steps
microstructure triangular etch pits
(as grown) twin planes
Etched microstructure on {111} and {111}: positive and negative truncated trigonal and ditrigonal
pyramids; negative forms only on {111}; dendritic formations. Etched with
NaNO3, 520 - 530 °C, 3h
{ 1 1 1 } maintained polished surface during etching; etch pits on {111}.
KOH, 380 °C, 0.5 - > 4 hours
{111} Boron surface shows crystallographic shaped etch pits.
{ 1 1 1 } Nitrogen surface shows rough irregular etched surface. LiOH,
600 °C, < 1 min.

Property and units Value and remarks
Internal microstructure Alternating color zones probably due to differential impurity adsorption
during growth.
Zones revealed by contrast in secondary electron scattering in scanning
electron microscope; also by polishing.
Chemical reactivity With metals

Mo - in 10−2 Pa vacuum - reaction with CBN - 1360 °C
Ni - in 10−2 Pa vacuum - wets CBN at 1360 °C
Fe, Ni, Co - argon, reaction with CBN begins - 1350 - 1400 °C
Fe, Ni, Co - in 10−3 Pa vacuum - wetting of hex BN
Fe and/or Ni-based alloys containing Al - reaction with CBN 1250 - 1300 °C
Al in 10−3 Pa vaccum, 1050 °C - marked wetting and reaction with CBN
and hex BN
Si in 10−3 Pa vacuum, 1500 °C - wetting of CBN
Fe, Co, Ni, Si in 10−3 Pa vacuum, 1550 °C - wet hex BN work of wetting -
1000 - 3500 erg/cm2
Cu, Ag, Au, Ga, In, Ge, Sn - 10−3 Pa vacuum, 1100 °C - no wetting of CBN
or hex BN
work of wetting = 60 - 350 erg/cm2

B - does not wet hex BN even at 2200 °C; addition of 0.1 - 1% Ti or Cr
increases wetting
With oxides
Al2O3 + B2O3 - vac. 10−2 Pa, no reaction at 1360 °C
ZnO-PbO-B2O3-SiO2 - glasses used as binder for Cubonite tool - wetting
indicated
Na2O-CaO-B2O3-SiO2 - argon 800 °C, cubic BN wetted by liquids in this
system.
ZrO2 and K2O additions decrease wetting
V2O5 and TiO2 additions increase wetting
Li-Al silicate plus fireclay fired at 905° - 1000 °C to bind CBN grains in
grinding wheel - suggests wetting by molten silicate
Li2O - B2O3 liquid wets CBN at 5 GPa and 1400 - 1700 °C
With acids and bases

insoluble in usual acids
soluble in alkaline molten salts, LiOH, KOH, NaOH-Na2CO3, NaNO3.
These are used for etchants.
Soluble in molten nitrides such as Li3N, Mg3N2, Sr3N2, Ba3N2, Li3BN2.
With biological systems

BN (along with Si3N4, NbN, and BNC) are reported to show weak fibri-
genic activity and cause pneumoconiosis. Maximum concentration recom-
mended for nitrides of nonmetals is 10 mg/m3; for AlN, 4; for ZrN, 4.

Table 81. Mechanical properties of cubic boron nitride - data supplied and property of General Electric
Hardness 4366, 4695 (undoped); 4572 (Be-doped)

[HK] 4500 on {111} in <110>
~ 4500
Elastic constants C11 = 7.12 · 1011 calculated from C11/Co

[Pa] C12 = 0.8 · 1011 estimated
C44 = 3.34 · 1011 calculated from C44/Co
C11 + 2C12
bulk modulus K = ≈ 2.9 × 1011
3
Compressibility 0.24 - 0.37 · 10−12 calculated range from various relationships

[cm2 10 µN−1] 0.34 · 10−12 calculated from elastic constants (1/K)
Temperature for dislocation mo- > 1300
bility [°C]
Fracture mode Cleaves easily on the 6 {011} planes

Some crystals crack on heating to about 900 °C
Table 82. Thermal properties of cubic boron nitride - data supplied and property of General Electric
Specific heat 12.55 at 300 K

[J/(mol K)] 25.1 at 600 K
Debye temperature 1700 from IR spectra

[K] 1900 from extrapolated elastic constants
Thermal conductivity 200 measured on dense polycrystalline compacts

[W/(m K)] (25 °C) 1300 calculated
87.5 by extrapolation of data from porous compacts
Linear thermal expansion 4.80 at 430 °C

[10−6/K] 4.30 at 700 °C
5.60 at 900 °C
5.80 at 1160 °C
Thermal stability Air, oxygen: B2O3 protective layer prevents further oxidation to
at < 1 atm ~ 1300 °C; no conversion to hexagonal form at 1400 °C.
Nitrogen: some conversion to hex at 1525 °C in 12 h, vac.
Vacuum (10−5 Pa): threshold temperature for conversion to hex,

1550 - 1600 °C.
at high pressure 3125 - 3225 °C, threshold conversion temperature for flash heating at
5 - 9 GPa.

Table 83. Optical and electrical properties of cubic boron nitride - data supplied and property of General
Electric Company, USA.
Band gap direct indirect method

[eV] 14.3 10.5 pseudopotential calculation
8.9 7.2 Augmented Plane Wave (APW, calcu.)
7.6 3.0; 3.4 Orthogonal Plane Wave (OPW, calcu.)
10.6 - 10.7 surface energy relationship (calcu.)
8.0 from reflectivity data
≥ 6.6 from UV transmission data
Valence band width

2 sub-bands: 12.2 and 5.2 OPW
13.5 and 5.2 soft X-ray emission spectra
18.0
Refractive index 2.117 taken from dispersion curve determined by Becke immersion
(at 589.3 nm) method using S-Se melts
Phonon spectra LO 1304 (161.6) Raman spectrum, polycrystalline BN
[cm−1 ] (meV) LO 1340 (166) IR reflection, polycrystalline compacts
LO 1365 (169) IR transmission, powder in acetone
TO 1056 (130.9) Raman
TO 1065 (132) IR reflection
TO 1075 (133) IR transmission, powder
LA 685 ( 85) IR transmission, single crystals
TA 348 ( 43) IR transmission, single crystals
center frequency 1175 (145.7) IR reflection
Dispersion --- 687.0 nm - 397.0 nm

n λ1 − n λ 2 0.044 687.0 nm - 430.8 nm
0.028 656.3 nm - 486.1 nm
Colour Colourless (rare); generally yellow (amber, honey, cinnamon), orange,

black (B-doped), brown, deep blue (Be-doped). Yellow and orange crys-
tals are thermochromic and become opaque about 450 °C.
IR and UV Spectra peak at ≈ 9.1 µm

Electrical
Resistivity p-type (Be-doped)

[Ω cm] 102 - 104 0.19 - 0.23 eV (activation energy for conduction)
n-type (B, S, Si, CN-doped)

103 - 107 0.05 - 0.41 eV (activation energy for conduction)
1010 undoped; resistance of undoped yellow crystals decreases

from ~ 1010 to ~ 107 from 25 °C to 500 °C (colour change ac-
companies resistance decrease)
Dielectric constant εo = 7.1

ε ∞ = 4.5 (n = 2.117; n2 = 4.48)

Table 84. Thermodynamic properties of cubic boron nitride - data supplied and property of General
Electric Company, USA [72D1].
Melting point at triple point ~ 3500 at 10.5 GPa

[K]
Heat of formation −251 value for the graphitic layer lattice form at 298 K
[kJ mole−1] −266 calculated value for CBN
Entropy
S [J mol−1 K−1] 0.58 calculated at 298 K
∆Sf [J mol−1 K−1] −48.45 calculated at 298 K
Cubic - hex transformation p = (0.0037 T [K] −1.8 ) [GPa], applicable from ~ 4.5 to 7.5 GPa with
solvent catalyst such as Li3BN2
∆V [cm3/mol] −1.89 calculated (at 298 K)
∆S [J mol−1 K−1] −1.3 calculated (at 298 K)
dP/dT [MPa K−1] + 2.84 calculated
+ 3.69 experiment (from 4.5 to 7.5 GPa with solvents)
Hexagonal → wurtzite > 12.5 GPa at RT

11 - 12 GPa at 2000 K
Lattice energy, U 22608

[kJ mol−1] 14319
Cohesive energy, ∆Gs 1214 spectroscopic analysis

[kJ mol−1] 1315 calculated
Surface energy ε111 4820 · 10−7 (calculation)

[J cm−2] σ111 (free specific surface energy) 4720 · 10−7 (calculation)
Table 85. Miscellaneous properties of cubic boron nitride - data supplied and property of General Electric
Piezoelectric shear constant 0.843 estimated from an empirical relationship between charge and
e14 [C/m2] interionic spacing
Electromechanical 0.14 estimated

coupling coefficient
k14
Electroacoustical 1.66 · 106 estimated

attenuation factor
2
α = k14 /V44 [s/m]
Piezoelectricity no response using Giebe-Scheibe apparatus with powders

Electron paramagnetic in hex BN, centers of paragmagnetic absorption are positively charged
resonance vacancies of N
Magnetic susceptibility χhex ≈ χcubic
Nature of bonding 27 spectroscopic analysis
[% ionicity] 22 IR spectrum
22 calc. from Pauling’s relationship for % ionicity:
100 {1 − exp [−¼(xB − xN)2]}, where x = electronegativity

13.5.4 CVD diamond and diamond like carbon (DLC)
Because of the various techniques available for the production of CVD diamond and DLC, properties can
be varied to suite specific applications. Thus, it has been possible to produce very high quality free-
standing polycrystalline diamond components of large dimensions in a range of grades. Optical grades
exhibit the highest optical transparency, while mechanical grades are optically opaque but possess high
mechanical strength. A range of thermal grades is also available for specific thermal applications. Finally,
the CVD process can be applied to deposit a diamond layer onto a strong substrate, which can then be
used as a cutting tool.
In the case of DLC coatings, the process allows thin wear resistant layers to be deposited onto a vari-
ety of metals and nonmetals.
13.5.4.1 Optical quality CVD diamond
The optical properties of diafilm1 are shown in Table 86 [99D], along with those for sapphire and ZnSe
for comparative purposes.
Table 86. Properties of De Beers Diafilm1, optical quality CVD diamond, compared with other optical
materials - data supplied and property of De Beers Industrial Diamond Division, S. Africa [99D].
Property Optical diafilm Sapphire ZnSe

[1] [1]
Hardness [GPa] 81 ± 18 16 1.05 [1]
Fracture toughness [MPa m1/2] 5.8 - 7.0 [1] 2 [1] 0.5 [1]
Young’s modulus [GPa] 1000 - 1100 [1] 344 [1] 70.3 ± 2.8 [1]
Poisson’s ratio 0.1 a [1] 0.27 [1] 0.28 [1]
Tensile strength [MPa]
Nucleation surface [Weibull modulus] 800 [11] [4] 400 [7] 50 [1]
Growth surface [Weibull modulus] 400 [23] [4]
Rain impact DTV [m/s] 2 mm drop size 525 [2] 457 - 533 [2] 137 [2]
Sand erosion [mg/kg] at 80 m/s C25/52 sand 0.18 [2] 85 [2] > 20000 [2]
Thermal conductivity at 300 K [W/(m K)] 1900 - 2200 [4] 34 [1] 16 [1] - 18 [3]
Thermal conductivity at 500 K [W/(m K)] 1100 [4] 6 [3] -
Thermal expansion coefficient [16−6/K] 1.0 at 300 K [4] 5.3 [1] 7.1 at 300 K [1]
4.4 at 1000 K [4] 10.9 at 800 K
Thermal shock FOM [· 103 W/m] * ~ 1000 [4] 5.4 [1] 1.1 [1]
Refractive index 2.375 [at 10 µm] [1] 1.77 [at 633 nm] [1] 2.4 [at 10 µm] [1]
dn/dT [1/K] 9.6 · 10−6 [1] 12 · 10−6 [1] 57 · 10−6 [1]
Dielectric constant D [35 GHz] 5.68 ± 0.15 [5] 9.4 - 11.6 [1] 8.98 [1]
% increase in D at 773 K 4.3 % [5] 6.5 % [5] -
Loss tangent 145 GHz [10−6] 8 - 50 [4] 200 [4] -
8 - 12 µm absorption coefficient [1/cm] < 0.07 [4] > 1000 [1] 0.0005 [1]
3 - 5 µm absorption coefficient [1/cm] min 0.8 0.01 - 0.04 [1] 0.015 [3]
at 3.7 µm [5]
Emissivity at 10 µm 0.02 at 573 K a, 0.03 N/A -
at 773 K a [5]
__________
1

Property Optical diafilm Sapphire ZnSe

Integrated forward scatter 8 - 12 µm [%] 0.1 - 0.7 [5] N/A -
Integrated forward scatter visible [%] < 4 [5] 0.1 [1] -
Density [103 kg/m3] 3.515 [7] 3.980 [7] 5.27 [7]
Specific heat capacity [J/(g K)] 300 K 0.52 [1] 0.75 [1] 0.34 [1]
Transmission 8 - 200 µm [1 mm thick] 71.4 % b [4] N/A -
Transmission 633 nm [1 mm thick] > 64 % b [4] 84.5 % [6] 60.8 % [6]
a
Measured on CVD diamond not made by De Beers
b
Reflection and scattering loss limited
N/A Not applicable

* FOM = S (1 - ν) k/(α E)
with
α Expansion coefficient
E Young’s modulus
ν Poisson’s ratio
S Strength
k Thermal conductivity
[1]
Harris, D.C.: Infrared Window and Dome Materials: SPIE Tutorial Text Series,
Volume TT10, (1992).
[2]
Cavendish Laboratory measurement.
[3]
Handbook of Infrared Optical Materials, Klocek, P.,(ed.) : Optical Engineering: Vol. 30,
Marcel Dekker Inc., ISBN 9-8247-8468-5, (1991).
[4]
De Beers measurement.
[5]
Harris, D.C., :Development of Chemical-Vapour-Deposited Diamond for Infrared Optical Applica-
tions: Status Report and Summary of Properties, Report No. NAWCWPNS TP 8210, (1994).
[6]
Calcualted.
[7]
Savage, J.A.: Infrared Optical Materials and their Antireflection Coatings, Adam Hilger Ltd, ISBN
0-85274-790-X (1985).
13.5.4.2 Mechanical quality CVD diamond
The fracture stress of free-standing diamond film can be measured using a 3-point bend geometry. The
results from such measurements, using both optical and mechanical quality grades, against layer thickness
for the growth (coarse grain) and nucleation (fine grain) surfaces in tension, are shown in Fig. 13.127 and
Fig. 13.128 [98S2] respectively. The results indicate a strong dependency on thickness and grain size of
the diamond film.
The Weibull moduli values, calculated from the above results for samples in the thickness range of
0.4 - 1.4 mm, are shown in Table 87 [98S2].
Table 87. Weibull module calculated from the data in Fig. 13.127 and Fig. 13.128 [98S2].
CVD diamond type Growth surface Growth surface Nucleation surface
(corrected for thickness variation)
Mechanical grade 9.8 11.6 6.5

Optical grade 11.6 23.1 11.0
These results indicate that there is a high degree of reproducibility of strength for both grades and that
strength is controlled by flaws which are related to the size of the crystal grains.

13.5.4.3 Thermal quality CVD diamond
One important property of the thermal grade films is thermal conductivity. Typical values versus tem-
perature for the optical, three thermal grades and natural Type II a diamond are shown in Fig. 13.129
[98S2]. Two of the thermal grades show values which are virtually independent of temperature, over the
measured range, while the optical grade more or less follows the trend of the natural Type II a diamond.
13.5.4.4 Diamond like carbon (DLC) and CVD diamond coated cutting tools
Diamond like carbon (DLC) is in fact an amorphous hard carbon and, apart from a high hardness and
scratch resistance, has few properties similar to natural or synthetic diamond. Table 88 [98C3] illustrates
the thermal and electrical properties of DLC films and CVD diamond while Table 89 [98C3] shows the
mechanical properties. These properties are very dependent upon the deposition technique and therefore,
significant variations can be reported.
The structure of CVDITE1, a CVD diamond coating (ca. 50 µm thick) on a silicon carbide substrate is
shown in Fig. 13.130 [99D]. This cutting tool is used for turning operations on a number of nonferrous
and plastic type materials. The cross-section clearly illustrates the conformal nature of the coating, with a
rounded contour at the cutting edge, and the columnar nature of the deposit.
Table 88. Thermal and electrical properties of DLC films and CVD diamond [98C3].
Property DLC films *) CVD diamond **)
Thickness limit Less than 3 µm Many mm

Composition Up to 40 at% H2 Much less than 1 at% H2
Density [g/cm3] 2.4 - 2.6 (dependent on at% H2) 3.52
Microstructure Amorphous Polycrystalline, cubic
Atom bonding state sp2 graphite and sp3 sp3 tetrahedral
Optical transparency Dark brown at less than 1 µm From opaque to colourless
Opaque at 3 µm (depending on grade)
Infrared transparency Transparent between 4 - 6 µm Transparent between 1 - 3 µm
and 8 - 14 µm
Refractive index (at 0.589 µm) 1.8 - 2.4 (dependent on at% H2) 2.42
Main features of Raman spectrum Broad humps at 1330 and Sharp peak at around 1332 cm−1
1550 cm−1
Thermal conductivity at 25 °C Approximately 2 Typically from 4 - 20
[W cm−1 K−1] (depending on grade)
Thermal expansivity [10−6/K] Not applicable 0.6 - 3 over 0 - 400 °C tem-
perature range
Specific heat capacity at 20 °C Not applicable 0.515
[J/(g K)]
Electrical resistivity [Ω cm] 102 - 1016 (dependent on at% H2) 109 - 1016 (depending on grade)
Dielectric strength [MV/cm] 0.01 10
Bandgap [eV] 1 - 3 (dependent on atomic % H2) 5.4
*) Bull, S.J., Chalker, P.R.: “High performance diamond and DLCs”, Journal of Materials,
April 1995, pp 16 - 19.
**) De Beers own measurements.
__________
1

Table 89. Mechanical properties of DLC films and CVD diamond [98C3].
Property DLC films *) CVD diamond **)

Thermal stability in air [°C] Approximately 400 (transforms Approximately 600 (transforms
to soot, loses H2) to soot rapidly)
Thermal stability in vacuum Approximately 400 (transforms Approximately 1400 (trans-
at 10 Pa [°C] to soot, loses H2) forms to soot slowly)
Young’s modulus at 23 °C [GPa] 700 - 850 910 - 1250
Flexural strength at 23 °C [MPa] Not applicable 2940
Tensile strength at 23 °C [MPa] Not applicable 3440
Compression strength at 23 °C Not applicable 96500
[MPa]
Hardness [HV] 3000 - 6000 (dependent on at% H2) 8400 - 12200 (orientation dependent)
Poisson’s ratio Not applicable 0.10 - 0.16
Coefficient of friction (at 20 °C, 0.7 for DLC on metal (0.02 - 0.04 0.1 for diamond on metal
lubricated, smooth faces in contact DLC on DLC or diamond) (0.02 - 0.1 diamond on diamond)
in air) (dependent on at% H2) (approaches 1 in vacuum)
*) Bull, S.J., Chalker, P.R.: “High performance diamond and DLCs”, Journal of Materials,
April 1995, pp 16 - 19.
**) De Beers own measurements.
13.5.5 Polycrystalline products

13.5.5.1 Diamond
As shown in section 13.3.2.5.1 - Table 44, there is a considerable number of commercial polycrystalline
diamond (PCD) products available. Not all manufacturers have disclosed the properties of such materials.
Table 90 [99D] illustrates a selection of properties of grades and compares them with those of mono-
crystalline diamond and a hardmetal - WC-6 wt% Co.
Table 90. Physical properties of some polycrystalline diamond (PCD) products [99D].
Property Syndite a) Syndrill a) Syndax a) Mono-cristalline Hardmetal

CTB 010 SRC 3 diamond WC-6 Co
Density [g/cm3] 4.12 3.99 3.42 3.52 14.7
Compressive strength [GPa] 7.60 7.61 4.192 8.68 4.438
Fracture toughness [MPa m1/2] 8.81 9.80 6.89 3.46 10.48
Knoop hardness [HK] 50 50 50 57 - 104 17
Young’s modulus [GPa] 776 810 925 1141 593
Thermal expansion [10−6 K−1] 4.2 4.6 3.8 1.5 - 4.8 5.4
Thermal conductivity [W/(m K)] 540 760 120 500 - 2000 100
Wear coefficient 3.89 3.97 2.99 2.14 - 5.49 1.15
a
) Trade names and trademarks of De Beers Industrial Diamond Division, S. Africa.
Fig. 13.131 [99D] illustrates the structure of three Synditea PCD grades with different diamond particle
sizes. The surfaces were etched to remove residual solvent/catalyst material and reveal the high degree of
inter particle sintering which occurs during manufacture and imparts the high strength and wear charac-
teristics of these products.

13.5.5.2 Cubic boron nitride
There is a considerable number of polycrystalline CBN products available for a variety of machining
operations, as shown in section 13.3.2.5.2 - Table 45. The properties of many of these products have not
been disclosed. However, Table 91 [99D] illustrates some of the important properties of Amborite1
AMB901 DBC 501 and DBA801 and compares them with those of an aluminum oxide ceramic cutting
tool material.
Table 91. Physical properties of some polycrystalline CBN products [99D].

Property Amborite a) Amborite a) Amborite a) Al2O3+ TiC
AMB90 DBC50 DBA80
Density [g/cm3] 3.42 4.28 3.52 4.28
Compressive strength [GPa] 2.73 3.552 - 4.50
Fracture toughness [MPa m1/2] 6.4 3.7 5.9 2.94
Knoop hardness [HK] 31.5 27.5 30 17
Young’s modulus [GPa] 680 587 649 390
Thermal expansion [10−6/K] 4.9 4.7 4.6 7.8
Thermal conductivity [W/(m K)] 100 44 85 9.0
Wear Coefficient 1.90 1.34 1.76 0.92
a
13.5.6 Diamond and CBN multi-phase products

Because of the very varied nature of the multi-phase products and the proprietary nature of these tools,
virtually no specific properties have been published. The combination of all of the factors governing the
composition of the different tools allows an extremely wide range of individual components to be used -
see sections 13.3.2.6.1 through to 13.3.2.6.6 . This results, in many instances, in the selection of compo-
nents to be based on the results obtained from field trials. Therefore, the measurement of properties, e.g.
density and matrices/matrix hardness, is confined to quality control aspects of manufacture.
13.6 Applications
The range of the application of hardmetals, cermets, diamond and cubic boron nitride is extremely wide
and, it is true to say, covers every aspect associated with wear, and the requirement of specific properties,
e.g. high compression strength.
The size of hardmetal components ranges over such small tools as 0.2 mm diameter microdrills,
weighing a fraction of a gramme, to 500 kg high pressure dies and anvils for the synthesis of diamond and
cubic boron nitride. Diamond and cubic boron nitride, in turn, by their very nature are relatively small in
themselves - fractions of a gramme but are incorporated into tools varying from very small hones and
grinding wheels to extremely large mining and boring tools.
13.6.1 Machining
The term machining covers an extremely wide spectrum such as turning, drilling, milling, skiving etc.
with the added variants of rough, normal and fine being applied to the type of operation. The machining
__________
1
Trade names and trademarks of De Beers Industrial Diamond Division, S. Africa.

There is a considerable number of polycrystalline CBN products available for a variety of machining
operations, as shown in section 13.3.2.5.2 - Table 45. The properties of many of these products have not
been disclosed. However, Table 91 [99D] illustrates some of the important properties of Amborite1
AMB901 DBC 501 and DBA801 and compares them with those of an aluminum oxide ceramic cutting
tool material.
Table 91. Physical properties of some polycrystalline CBN products [99D].

Property Amborite a) Amborite a) Amborite a) Al2O3+ TiC
AMB90 DBC50 DBA80
Density [g/cm3] 3.42 4.28 3.52 4.28
Compressive strength [GPa] 2.73 3.552 - 4.50
Fracture toughness [MPa m1/2] 6.4 3.7 5.9 2.94
Knoop hardness [HK] 31.5 27.5 30 17
Young’s modulus [GPa] 680 587 649 390
Thermal expansion [10−6/K] 4.9 4.7 4.6 7.8
Thermal conductivity [W/(m K)] 100 44 85 9.0
Wear Coefficient 1.90 1.34 1.76 0.92
a
13.5.6 Diamond and CBN multi-phase products

Because of the very varied nature of the multi-phase products and the proprietary nature of these tools,
virtually no specific properties have been published. The combination of all of the factors governing the
composition of the different tools allows an extremely wide range of individual components to be used -
see sections 13.3.2.6.1 through to 13.3.2.6.6 . This results, in many instances, in the selection of compo-
nents to be based on the results obtained from field trials. Therefore, the measurement of properties, e.g.
density and matrices/matrix hardness, is confined to quality control aspects of manufacture.
13.6 Applications
The range of the application of hardmetals, cermets, diamond and cubic boron nitride is extremely wide
and, it is true to say, covers every aspect associated with wear, and the requirement of specific properties,
e.g. high compression strength.
The size of hardmetal components ranges over such small tools as 0.2 mm diameter microdrills,
weighing a fraction of a gramme, to 500 kg high pressure dies and anvils for the synthesis of diamond and
cubic boron nitride. Diamond and cubic boron nitride, in turn, by their very nature are relatively small in
themselves - fractions of a gramme but are incorporated into tools varying from very small hones and
grinding wheels to extremely large mining and boring tools.
13.6.1 Machining
The term machining covers an extremely wide spectrum such as turning, drilling, milling, skiving etc.
with the added variants of rough, normal and fine being applied to the type of operation. The machining
__________
1

conditions, i.e. speed, feed, depth of cut, interrupted cut and whether the operation is carried out with a
liquid coolant or dry, also add to the variables to be considered when assessing the optimum cutting tool
material. A final variant is of course the material being machined - steels, cast-irons, non-ferrous alloys,
high temperature and stainless alloys, composites and plastics etc. This indicates the complexity of the
simple term-machining.
The following examples have been selected, from a vast number in the literature, just to indicate the
range of such operations and the influence the conditions have on the cutting tool materials. The judge-
ment as to suitability of the cutting tool material is usually presented in terms of life, based on wear char-
acteristics, i.e. chipping, crater or flank wear or number of components produced to the level of required
quality, e.g. surface finish, dimensions etc.
For a more comprehensive view of machining and tool cutting materials, references [91T, 93E] should
be consulted.
13.6.1.1 Hardmetals and cermets
It is usual to consider the assessment of the cutting tool design/cutting tool material for a specific applica-
tion, on the basis of a number of sequential steps:
- Material to be machined - see ISO classification 513 (Table 60)

- Type of machining operation - see ISO classifications 513, 1832, 5608 and 6261
- Machining conditions - select cutting insert geometry, including type of chip breaker from manufac-
turer’s catalogue
- Cutting tool material - consult manufacturer’s catalogue, e.g. section 13.4.2.2, Tables 62, 63, 65, 66 and 67.
The following examples indicate the advantages of certain cutting tool materials when used for specific
materials and machining conditions.
As a general rule certain cutting tool materials are recommended for machining specific materials
under certain cutting conditions. This is usually portrayed in graphs indicating these characteristics as
shown in Fig. 13.132 [97K1]. This indicates the general conditions for turning operations of stainless
steels when using a PCVD coated ultrafine grained WC-Co alloy. Similar graphs are shown in manufac-
turer’s literature for other combinations.
An example, shown in Fig. 13.133 [97K1], of the results obtained from different cutting tool materials
when skive shaping case-hardened tooth flanks, indicates that the difference in flank wear is quite
marked, particularly between coated and uncoated inserts.
Figure 13.134 [95E] shows the increase in tool life between uncoated hardmetal, coated hardmetal and
a cermet insert when finish turning (dry) a globular cast iron (GGG40). The cermet shows a distinct ad-
vantage. However with a harder cast iron (GGG70) the coated hardmetal proved superior to the cermet.
This indicates that care is required in applying results from one set of conditions to another. The influence
of a change in the cutting tool material, i.e. from uncoated to coated is shown in Fig. 13.135 [95E], where
the latter insert proved superior.
Drilling of high strength, fully hardened steel, high silicon containing aluminum and glass fibre rein-
forced plastics is often carried out using TiN coated fine WC grain size-Co alloys. The influence of WC
grain size of a TiN-PVD coated WC-6 wt% Co series is shown in Fig. 13.136 [97D1], where the ultra-
fine material exhibited a marked increase in the number of satisfactorily drilled holes.
The use of multi-phase coated, cobalt enriched substrate metal cutting inserts for arduous cutting con-
ditions, e.g. Kennametal KC 8501 and KC 9351 (see Fig. 13.95) has made a substantial impact on the
metal cutting economy of such operations. The results shown in Fig. 13.137 [81N] indicate how the co-
balt enriched substrate increases the ability to withstand interrupted cutting conditions (increase in edge
strength).
All of the above examples indicate the necessity to fully analyse the individual cutting operation before
selecting a cutting tool material.
__________
1
Trademark of Kennametal Inc., USA.

13.6.1.2 Diamond and CBN
The following table indicates the machining application range for polycrystalline diamond (PCD) and
polycrystalline cubic boron nitride (PCBN) tools. Because the thermochemical stability of diamond is
very sensitive to quite modest temperatures, the cutting temperature has to be restricted to ca. 700 °C and
the workpiece material has to exhibit no affinity with carbon. This rules out cutting any form of ferrous
material. On the other hand CBN can be used with the majority of ferrous based materials - exceptions are
austenitic steels and ferritic cast irons - especially in a fully hardened condition where machining can
compete with grinding operations.
Table 92. Applications of PCD/PCBN according to workpiece material [99D].
PCD PCBN
• Nonferrous and precious metals and their • Hard ferrous metals (45-65 HRC)
alloys, such as aluminum, copper, silver,
magnesium, gold, etc. • Martensitic cast iron, eg: Ni-HARD, high chrome
white cast iron, chilled cast iron, hardened cold
• Plastics and wood composites work steel, hardened bearing steel, case hardened
GRP’s, CFK’s steel, hardened high speed steel, martensitic stain-
chipboard, hardwood, less steel
MDF, etc.,
polymer concrete • Various cobalt, nickel and iron based hard facing
alloys
• Mineral based materials
stone, ceramics, • Soft ferrous metals with short chipping characteris-
cement board tics, e.g.: pearlitic grey cast iron, sintered iron
Figure 13.138 [88S3] demonstrates the wear-land width of Syndite1 PCD025, PCD010, Syndax 3 1, PCD
and PCBN cutting inserts on machining a 90% glass fibre reinforced epoxy resin. The results show no
significant difference between the two Syndite grades. However, the thermally stable Syndax 3 material
exhibits a higher wear-land width at the start of cutting, which then does not change with increase in
cutting time. The PCBN material shows an inferior tool life behaviour compared with the PCD products.
However, under other highly abrasive machining conditions there is a marked difference in flank wear
between the different Syndite1 grades. The lowest flank wear occurs with the grade with the coarsest -
25 µm - diamond particles, whilst the fine particle - 2 µm - grade with a higher bond content exhibits the
highest wear.
These results once again demonstrate the importance of not relating machining results from one set of
conditions to another.
There has been a considerable increase in the use of metal matrix composites (MMC) - combinations
of high strength ceramics reinforcing light metal alloys, e.g. silicon carbide/aluminum alloys, in recent
years. Because of the extremely abrasive nature of these products, it has been recognised that machining
can only satisfactorily be carried out using diamond cutting tools. The following table lists the recom-
mended cutting parameters.
__________
1

Table 93. Recommended conditions for machining MMC’s using Syndite1 PCD 025 [98C4].
Operation Cutting speed Feed rate Depth of cut Coolant

m/min mm/rev mm
Turning 300 - 800 0.2 - 0.6 < 5.0 Yes/No
Milling 200 - 1000 0.1 - 0.4 < 3.0 Yes/No
Drilling 50 - 200 0.05 - 0.2 - Yes
The results of turning tests on an 18% Si-Al alloy using a CVD diamond coated silicon carbide substrate -
CVDITE1 has shown this cutting material to be markedly superior to a hardmetal (K10) WC-6 wt% Co
alloy, as shown in Fig. 13.139 [99D]. However, when compared with Syndite1 PCD 010 tools, at higher
cutting speeds the PCD product proved to be superior - see Fig. 13.140 [99D].
In further turning tests on an MMC alloy (20% SiC-Al), with polycrystalline diamond tools (PCD)
and a brazed-on thick diamond layer tool (CVDD), the latter product proved to be superior as shown in
Fig. 13.141 [94G2].
Table 94 [99D] shows the recommended machining applications for different CBN products.
Table 94. Characteristics and recommended applications for high and low CBN tools [99D].
High CBN content Low CBN content
Characteristics, properties CBN content 80 - 95% CBN content < 60%

fracture toughness compressive strength
high thermal conductivity low thermal conductivity
Preferred applications Roughing
• hardened steel
• chilled cast iron
• hard facing
(cobalt, nickel, iron based)
• pearlitic grey cast iron
Preferred applications Finishing Finishing
• chilled cast iron • hardened steel
• pearlitic grey cast iron • hard facing
(cobalt, nickel, iron based)
• cast iron
Figure 13.142 [98U] demonstrates that the correct CBN tool material (see Table 45) has to be chosen in
order to achieve optimum machining results. The roughing operation, turning high speed tool steel, is
very severe and a tooling material with poor strength eventually fails by fracture of the cutting edge.
However, it can be seen that the Sumiboron BN 6002 grade (high CBN content with excellent toughness)
yields satisfactory results.
__________
1
2
Trade name and trademark of Sumitomo Electric Industries Ltd., Japan

13.6.1.3 Machining of wood and wood type materials
Although in the past, the machining of wood and wood type materials, e.g. medium density fibreboard
(MDF) was carried out using high speed steel tools, a rapid turn over to hardmetal alloys occurred with
the introduction of mass production techniques for the manufacture of house construction units and fur-
niture. The fine grain WC-6-10 wt% Co alloys, were quickly found to yield optimum results and they are
still extensively used both professionally and as DIY tools for the amateur. However, since the late 1980s
PCD diamond tools are replacing the former in the majority of factory operations.
Table 95 [94C] shows a comparison between PCD and hardmetal tools used for a variety of
wood/wood type machining operations. It can readily be seen that the PCD tools, of all types, are more
efficient than the equivalent hardmetal types.
Table 95. Comparison between average lives of PCD tipped and hardmetal tipped tools (figures refer to
linear metres of cut wood based material [94C].
Tool Hardmetal PCD Ratio of PCD to
[m] [m] tungsten carbide tool life
Saw blade 2 500 400 000 160 : 1

Straight router 3 000 50 000 17 : 1
Profiled router 2 500 40 000 16 : 1
Hogging blade 25 000 400 000 16 : 1
Joint cutter 6 000 350 000 58 : 1
Groover 20 000 1 300 000 65 : 1
As a further example a 5 mm diameter PCD drill was developed specifically for drilling holes in mela-
mine covered chip board. This is a particularly difficult operation as any wear of the drill cutting edge
leads to chipping at the hole edge. After 5000 holes, hardmetal tipped drills had to be re-sharpened, whilst
after 100,000 holes the PCD tipped drill was still producing satisfactory holes [92D].
Fig. 13.143 [85H] shows the wear on the cutting edge of turn-over-knives used for machining the edge
of plastic coated chipboard. The difference in wear is very pronounced, with the hardmetal tool edge
showing significant wear after only cutting 100 m.
13.6.2 Grinding
Certain hard and brittle type materials can only be shaped by grinding. This operation has been developed
over many years - starting with alumina and silicon carbide bonded wheels. The modern equivalent
wheels contain either diamond or cubic boron nitride grit, bonded with either metal, vitreous or resin
materials. The grits are carefully graded for size, shape and strength characteristics as these parameters
play an important role in the grinding operation - see sections 13.3.2.1, 13.3.2.2, 13.3.2.3 and 13.3.2.6.1,
also Tables 37, 38 and 41.
Grinding wheels containing diamond grit, both natural and synthetic, are used for grinding a very
wide range of workpiece materials, such as all types of glass, hardmetals, engineering ceramics, rein-
forced plastics, natural stone, metal matrix composites (MMC), semi-conductor materials, polycrystalline
diamond (PCD) and polycrystalline cubic boron nitride (PCBN).
The equivalent grinding wheels, containing cubic boron nitride grit, are extensively used for grinding,
honing and fine lapping a range of hardened ferrous alloys and difficult to machine alloys, such as hard-
ened carbon steels, alloy tool and die steels, bearing steels, cast irons, superalloys, hardened stainless
steel.

13.6.2.1 Diamond
To emphasise the importance of grit “type”, the following three illustrations [94B1] clearly demonstrate
the influence of grit characteristics on grinding criteria.
Fig. 13.144 illustrates the effect of nickel cladding on the life of a resin bonded grinding wheel and the
power requirements during the wet surface grinding of hardmetal. For the same diamond grit type, the
addition of 55 wt% nickel cladding improves the G-ratio by approximately 70 % while the power re-
quirement only increases by 40 %.
As an alternative requirement for the grinding of glass with metal bonded wheels, Fig. 13.145 demon-
strates the influence of grit strength on wheel life. The natural diamond grit - PDA 6651 - gives the lowest
life, while the strongest synthetic abrasive grit - PDA 9891 - yields the highest G-ratio. If, however the
surface finish of the glass is the prime requirement, then the results shown in Fig. 13.146 indicate that the
free cutting abrasive - PDA 6651 is the correct choice.
Test surface grinding of a number of engineering ceramics using a bronze bonded diamond wheel -
Fig. 13.147 [97J2] - showed that the G-ratio varied quite markedly depending upon the type of workpiece
material. The lowest value was obtained with boron carbide, whilst the Si/SiC and reaction bonded silicon
nitride (RBSN) yielded the two highest values. In an attempt to assess the ease of grinding, the ratio of the
normal force Fn to the tangential force Ft was measured during grinding. However, these figures did not
establish a direct relationship with wheel life.
Grinding of polycrystalline diamond products, e.g. Syndite 0101, is extremely difficult as the operat-
ing parameters involve diamond against diamond. However, the operation can be carried out albeit the
G-ratio is extremely low - 0.005 - 0.014. The life of the grinding wheel, however, is not necessarily the
major factor in this operation, as the quality of the cutting edge of the PCD tool is extremely important. In
this respect, Fig. 13.148 [92M2] shows that resin bonded wheels yield the optimum value for cutting edge
quality. On the other hand, this type of wheel yields the lowest G-ratio.
Lapping and polishing natural stone for architectural embellishment of monuments and buildings has
rapidly expanded in recent times. The quality aspect, in relation to gloss value and surface finish, has
become a key issue, in the overall context of the economy of the stone industry.
An investigation into these factors has shown that among other aspects, the rotational speed of the
resin bonded polishing discs using 1000 mesh and 2000 mesh diamond powder influences the surface
finish of white granite (shore hardness 88HS) [92N]. With the polishing equipment used in the test, the
optimum surface finish was obtained at a disc speed of 500 rpm, which, with a 150 mm diameter disc,
equates to a peripheral speed of 16 m/s. However, as expected the greatest influence on the surface finish
was the diamond mesh size and number of polishing passes, as shown in Fig. 13.149 [92N].
Using resin bonded CBN (nickel clad) abrasive grits, surface grinding tests on M2 high speed steel
showed that the grit with the highest strength - both at ambient and high temperature - ABN 8601 yielded
the highest G-ratio figures for the lowest power requirements - see Fig. 13.150 [98B].
Electroplated single layer CBN grinding wheels can readily be manufactured and have been used for
the rough grinding of cast-iron GGG70 automobile crankshafts on special machines. Grinding tests
showed that increasing the cutting speed significantly, reduced the normal grinding forces without in-
ducing any thermal damage in the zone beneath the surface of the workpiece. This demonstrates that
grinding conditions, as well as the choice of the abrasive grit type, influence the overall economy of a
grinding operation - see Fig. 13.151 [96T1].
__________
1
Trademarks of De Beers Industrial Diamond Division, S. Africa.

13.6.3 Mining
Mining, in relation to hardmetal and diamond, is concerned with drilling holes or shearing and planing
away large masses of soft rock or minerals. The choice of mining technique depends upon many factors,
not least being the hardness of the rock or minerals.
The following table - Table 96 [92C] - gives a summary of the application range for drilling holes in a
variety of rocks using different drilling crowns. Although the selection is not precise, it can be seen that
hardmetal tipped bits have a limited range, whilst the different forms of diamond crowns cover the com-
plete spectrum of rock types. It should be borne in mind that the type of drilling equipment available -
percussive - rotary/percussive - rotary, also dictates the type of drilling bit/crown which can be used.
Shearing and planing tools are invariably tipped with hardmetal inserts, although some attempts have
been made to use very tough polycrystalline diamond products.

Ref. p. 13-185]
Table 96. Application range for different drilling bits/crowns [92C].
Hard- Rock Approx. Hardmetal SYNDRILL1 Surface-set SYNDAX 31 SYNDAX 31 SYNDAX 31 Impregnated
ness description UCS insert bits PCD insert diamond bits TSP cube and TSP pin bits TSP hybrid diamond bit
group [MPa] bits triangle bits bits
1 Clay Soft
Soft shale rock
Soft limestone 1-25
Gypsum
2 Loose Soft
sandstone to
Shale medium
Medium hard 25-50
limestone
13 Hard materials
Salt
3 Soft sandstone Medium

Sandy shale hard non-
Claystone abrasive
Soft schist rock
50-100
4 Medium hard Medium

sandstone hard
Siltstone abrasive
Medium hard rock
linestone 50-100
Hard shale
5 Hard limestone Hard

Dolomitic slightly
limestone abrasive
Schist rock
Serpentine 100-200
13-119
13-120
Table 96. Application range for different drilling bits/crowns [92C]. (continued).
Hard- Rock Approx. Hardmetal SYNDRILL1 Surface-set SYNDAX 31 SYNDAX 31 SYNDAX 31 Impregnated
ness description UCS insert bits PCD insert diamond bits TSP cube and TSP pin bits TSP hybrid diamond bit
group [MPa] bits triangle bits bits
6 Hard limestone Hard non-

Dolomite abrasive
Marble rock
Andesite 100-200
7 Gneiss Very
Granite hard
Basalt rock
Gabbro > 200
8 Conglomerate Very
13 Hard materials
Abrasive abrasive
quartzite rock
Rock with > 200
pyrite
Banded
hematite
[Ref. p. 13-185
1
Tradename of DeBeers Industrial Diamond Division, S. Afrika.
13.6.3.1 Hardmetal
Percussive drilling is carried out, using either hardmetal tipped integral steel drill rods or crown bits, in
medium to hard rocks. In the former case the hardmetal chisel is brazed into a slot in the drill rod head
whilst in the latter instance, the hardmetal buttons are shrink fitted into a series of patterned holes in the
crown. The hardmetal quality used for these operations is usually in the 6 - 9 wt% Co and medium to
medium - coarse WC grain size range. Rotary drilling is usually carried out using winged rotary heads
tipped with hardmetal in the 6 - 9 wt% Co and medium fine to medium WC grain size. These alloys tend
to be harder than those for percussive tools. In the combined percussive/rotary drilling technique, the drill
head is rotated and at the same time hit by a blow at the rear of the drill rod. This double action results in
a very rapid penetration rate with an overall reduction in wear of the drilling head. According to the type
of rock, hardmetal covering the above two ranges of material is used for the drilling elements. Shear and
planing is used to extract coal from seams within rock and is the most economically method available for
this mining operation. Shearing is also used in the boring of large tunnels and is safer in many respects
than drilling and blasting. As the flat or point attack picks are subjected to severe impacts during cutting,
the choice of hardmetal is restricted to extremely tough grades in the range 9 - 15 wt% Co and a coarse
6 - 20 µm WC grain size. Experimental grades with a 20 - 40 µm WC grain size have in some instance
increased tool life by a factor of 3 to 5. In the majority of cases all hardmetal inserts are either sintered
using a Sinter/HIP unit or have a HIP treatment after normal sintering.
13.6.3.2 Diamond
Diamonds are used in mining tools in many forms, e.g. surface set single diamond crystals, impregnated
diamond crystals and two types of polycrystalline diamond elements, as shown in Table 96 [92C] and
covered in sections 13.3.2.5.1, 13.3.2.6.2 and 13.3.2.6.3. The choice of drilling crown is very dependent
upon the type of rock being drilled and the drilling equipment available.
The following examples illustrate the application range and the success achieved in applying the dif-
ferent drilling crowns.
A hybrid drilling bit, composed of Syndax 31 rectangular pins set into a diamond impregnated crown,
was compared with a standard impregnated element, when drilling broken crystal tuff. The results, dis-
played in Fig. 13.152 [93S1] show that the average penetration rate for the hybrid bit was 20 m/min for a
full hole depth of 143.6 m. By comparison, the standard impregnated bit had to be changed three times for
a very much reduced penetration rate.
In another drilling trial, in a coal exploration site, comparing a surface set diamond 210 mm diameter
coring bit with a similar crown set with 2.5 mm Syndax 31 cubes, the latter had a bit life twice that of the
former. The penetration rate was also double, as shown in Table 97 [99C2].
Table 97. Comparison of drill bit performance in a coal exploration site [99C2].
Bit type Surface-set diamond (15 spc) Syndax 3 1 TSP
Ground formation Sandstone - 35% Sandstone - 35%
Shale - 60% Shale - 60%
Coal - 5% Coal - 5%
Drill rig Failing 2500 SE Failing 2500 SE
Weight on bit [tons] 3.0 3.0
Speed [rpm] 300 300
Water flow [l/min] 80 80
ROP [ft/min] 0.10 - 0.17 0.27 - 0.33
Bit life [ft] 1000 - 1200 2300
__________
1

Comparison between a hardmetal roller tricone bit and a non-coring crown set with 2.5 mm Syndax 31
cubes in a spiral configuration, on drilling a limestone with bands of chert for 60 - 140 m long 60 mm
diameter grouting holes, demonstrated that the penetration rate of the latter was three to four times that of
the hardmetal tricone bit. The mean life of the crown was also longer - see Table 98 [92C].
Table 98. Comparison of drill bit performance on drilling grout holes [92C]
Bit type Hardmetal roller (tricone) SYNDAX 3 1 non-coring (L222)
Bit size 60 mm 62 mm
Rock formation Limestone with bands of chert up to Limestone with bands of chert up to
240 MPa 240 MPa
Drill rig type Diamec 260 Diamec 260
Weight on bit [tons] 1 - 2.5 1 - 2.5
Rotation speed [rpm] 500 - 1000 500 - 1000
Water flow rate [l/min] 120 - 140 120 - 140
Mean ROP [cm/min] 5 - 10 22 - 34
Mean bit life [m] 30 - 120 45 - 189
Drilling tests, using 45 mm diameter three wing bits employing three 13.3 mm diameter Syndrill1 blanks
set at 20° negative rake with an additional 9.5 mm diameter centre cutter blank, in a hard and abrasive
Pennant sandstone, showed that the load applied to the bits, through the drilling rig, is extremely impor-
tant in achieving optimum life - see Fig. 13.153 [88C]. The bit run at the highest load of 0.8 tons per-
formed satisfactorily while those at the lower loads had much reduced lives.
Turbo-drilling in the northern North Sea using Stratapax2 blanks mounted on 12 ¼ý diameter bits
showed an average penetration rate of 15.2 m/h over 915 m compared with 5.5 m/h over 91 m for a
hardmetal roller cone bit [92G3].
Geoset2 set drilling crowns also show improved penetration rates and bit life compared with surface
set natural diamond crowns, when drilling siltstone, claystone, shale and limestone. The fomer crown has
a penetration rate of 25.4 cm/min compared with 15.2 cm/min for the surface set crown and an average
life of 762 m compared with 366 m for the latter [92G3].
Diamond circular/band saws, as well as wire saws, are used in the construction, highway and airport
runway maintenance industries, as well as in quarrying for the extraction of large blocks of natural stone
for use in buildings.
Diamond wire sawing of marble and other high value natural stones has become almost the only eco-
nomic method of extracting large blocks from quarries. Diamond wire saws, see section 13.3.2.6.2, enable
massive 8 tonne blocks, with an excellent surface condition, to be extracted at cutting speeds of 3 to
7 m2/h. Table 99 [91D] indicates the cutting speed and life of 20 m long wires equipped with 10 mm
diameter 6 mm long spaced beads containing 40/50 mesh SDA 1001 high strength synthetic diamond.
Table 99. Wire life and performance related to cutting various natural stones [91D]
Material Country of origin Cutting speed [m2/h] Life of a 20 m length of wire [m2]
Carrara marble Italy 7 500
Tivoli travertine Italy 7 600
Pierre bleue Belgium 3 400
Boulonnais marble France 4 400
Pink and white marbles Portugal 4 400
White marbles Greece 6 400
Cambrain green shale U.K. 3 300
Data supplied by Diamant Boart SA, Brussels, Belgium.
__________
1
Trade name of De Beers Industrial Diamond Division, S Africa.
2
Trade name of General Electric Company, USA.

The production of 1 cm thick granite tiles using 32 × 1000 mm diameter ganged diamond saw blades in a
block cutter, with each blade containing segments composed of SDA 100+1 or SDA 85+1synthetic dia-
monds and a metal bond, has yielded a cutting rate of around 0.6 m2/h per·blade. There is no other tech-
nique available for the production of such objects [91D].
The reconditioning of the surface of highways and airport runways has many economic advantages
over total removal and renewal. In one case [93B] a road surface was ground to provide flatness and fine
grooves of 4 mm deep × 2.5 mm wide and spaced 3 mm apart. The equipment consisted of a 960 mm
wide multi-blade grinding head, with each blade being set with 2.5 mm wide segments containing SDA
100+1 high strength synthetic diamonds. The cutting (travel) rate was 2.5 - 4 m/min.
The above references illustrate the extremely wide range of application of diamonds in the mining and
construction industries.
13.6.4 Chipless forming applications

The use of hardmetal and diamond, the latter restricted to wire drawing dies, as tools for the production of
components without machining, has been practised virtually since the introduction of the two generic
materials.
Single crystal diamonds were used as wire drawing dies for the production of tungsten wire, required
for the electric lamp industry, since the start of the 20th century. In fact, the high cost of such dies led to
the initiation of the research work to find a cheap substitute. Thus, the first application of hardmetal was
as wire drawing dies. Since the introduction of modern PCD material, the wheel has turned full circle and
hardmetal dies, in some cases, have been displaced by the new polycrystalline diamond dies.
Hardmetal alloys have been specifically developed, over many years, to fulfil the role of high quality
dependable tools for the metal forming industries - these include cold rolls, hot rolls, cold forging tools,
extrusion dies and punches, deep drawing dies and punches, stamping tools, warm forging tools and pow-
der metallurgy dies and punches. Thus, it can readily be stated that without these alloys a number of
forming techniques would never have been economically developed [76S, 83E, 98K, 95K2].
13.6.4.1 Hardmetal
The following examples are taken from the vast number of applications, which impact on every industry
concerned with modern methods of production. They are by no means complete but it is hoped that they
will illustrate the importance of hardmetal as a modern tool material.
Since the introduction of hardmetal rolls for the hot rolling of steel rods in “no-twist” mills in the late
1970s, many thousands of tonnes of product have been manufactured. The success of this application has
required a considerable amount of research and field testing, and also a different approach to design and
use of the rolls. This has led to recommendations of different hardmetal alloys for different rolling posi-
tions within the mill train - the toughest at the start, with a gradual reduction to the final position -, as
shown in Table 100 [99S3]. A number of alloys has been developed by modifying the binder with addi-
tions of nickel and chromium to the cobalt, to resist corrosion by fluctuating cooling water quality. The
correct application of cooling water to the roll surface is extremely important so as to minimise thermal
fatigue cracks. After a predetermined rolling campaign, the rolls are removed for regrinding to remove
any cracks and to reshape the passform. Extreme care is required in carrying out this operation. However,
the success of this application can be measured by the fact that virtually every rod mill in the world is
equipped with hardmetal rolls.
__________
1
Trademark of De Beers Industrial Diamond Division, S. Africa.

Table 100. Hardmetal grades for ‘No-Twist’ rod mill rolls. [99S3] - data supplied and property of
Sandvik Hard Materials, Sweden.
Grade recommendations
Intermediate stands Finishing block
16 17 18 19 20 21 22 23 24 25
!! ! ! ! ! ! ! ! ! ! !
!! ! ! ! ! ! ! ! ! ! !
Grade
C30P, C30T, H30P ● ○ ○ ■
C25P, H25P ○ ○
C20C, H20C ● ● ● ●
C15C, H15C ○ ○ ● ● ● ● ● ●
H13C ● ●
H6T ● ●
● = 1st recommendation
○ = 2nd recommendation
■ = rolls for reinforcing bar
SANDVIK standard roll grades

Grade data
Grade Composition Carbide Den- Hardness Transverse Trans- Compres-
grain size sity 20 °C rupture verse sive
strength rupture strength
20 °C energy
wt% µm g/cm3 HV3 HRA MPa J MPa
WC Co Ni Cr
C15C 85 7 7 1 Coarse (4) 14.0 900 85.0 2900 3.8 3400
C20C 80 9 9 2 Coarse (4) 13.5 800 83.5 2700 5.0 3200
C25P 75 12 12 1 Medium-coarse 13.0 750 83.0 2700 5.5 3100
(3.5)
C30P 70 13 15 2 Medium-coarse 12.7 650 82.0 2700 7.0 3000
(3.5)
C30T 70 13 15 2 Extra-coarse (5) 12.7 600 81.5 2700 8.0 3000
H6T 94 6 - - Extra-coarse (5) 14.8 1300 89.0 2300 1.2 4300
H13C 87 13 - - Coarse (4) 14.2 1070 86.5 2700 3.0 3800
H15C 85 15 - - Coarse (4) 13.9 950 85.5 2900 4.0 3600
H20C 80 20 - - Coarse (4) 13.5 900 85.0 2700 5.1 3500
H25P 75 25 - - Medium-coarse 13.0 800 83.5 2700 5.5 3300
(3.0)
H30P 70 30 - - Medium-coarse 12.7 700 82.5 2700 7.0 3000
(3.0)

The backward extrusion and piercing of small fastener components - 4 mm long × 1 mm wall thickness -
from materials such as highly alloyed stainless steels and titanium alloys has been successfully carried out
using hardmetal dies and punches. In this instance, the punch had a diameter of 2.92 mm, was 42 mm
long and was manufactured from a 10 wt% Co - 0.8 µm WC grain size alloy. The ratio of length to di-
ameter of 14.4 demonstrates the high modulus of elasticity of this alloy [76S].
At the other end of the scale of backward extrusion, brake cylinders are produced using hardmetal dies
and punches. The punches are 85.5 mm diameter × 300 mm long and the cylinders have a wall thickness
of 13 mm and a height of 130 mm. Production is at the rate of 3 per minute and the punch life is of the
order of 60000 components. The hardmetal used for this operation lies in the range 11 - 15 wt% Co -
medium to medium coarse WC grain size [76S].
The production of thin steel components by hardmetal punches and dies in blanking and piercing con-
figurations has brought considerable economic savings to this operation. This is due to the exceptional
long life of the tools with the concomitant reduced down time of the presses. Armature laminations are
produced by such means at a rate of 450 strokes · min−1 and outputs of 1.6 to 1.7 million parts between re-
grinds. A total tool life of 80 million parts is not unusual for this operation. The construction of the die
and punch allows for replacement of any broken or unusually worn part. With the high quality modern
hardmetal alloys available, it is usual to construct the segments from 10 - 15 wt% Co - 0.8 µm WC grain
size alloys [76S, 72P].
Although, in some cases, hardmetal wire-drawing dies have been replaced by polycrystalline diamond
products, the former dies are still used in a wide range of applications. In particular, the use of a
3 wt% Co - 0.5 µm WC grain size alloy, with a hardness in excess of 2200 HV30, in the drawing of brass
coated high tensile strength steel tyre cord wire has been very successful. This alloy is particularly resis-
tant to galling and attrition wear, which is exacerbated by the attack of zinc on the binder [76S].
The production of various forms of beverage cans in steel or aluminum exceeds many billion per an-
num. The manufacturing process, to produce a two-piece can, is based on a deep draw and wall ironing
technique, which, to be economical, requires hardmetal tooling. The blanked strip is drawn to form a
shallow cup which is then processed through a series of redraw (for aluminum) and up to six ironing dies.
The initial cup wall is thinned during the ironing process as it is progressively squeezed between a punch
sleeve and the die wall. Before being filled with the appropriate beverage, the lengthened can body is
trimmed to the correct height and then necked and flanged. The production rate of a complete draw-iron-
neck-flange press unit is of the order of 125 - 150 strokes per minute and the life expectancy of such tools
is up to six million cans. It is obvious that the highest quality, particularly with respect to surface integrity
is required for both the dies and punch sleeves and it is a prerequisite that the hardmetal be either sinter-
HIP or sintered and then HIP treated to minimise porosity. A typical hardmetal alloy, developed to en-
hance resistance to galling and adhesion wear, would be in the range 9.5 - 12 wt% Co, 0.5 - 1 µm WC
grain size with additions of titanium and tantalum carbides. In some cases the tooling is PCVD or PVD
coated with titanium nitride [98K, 95K2].
Hardmetal alloys in the range 20 - 30 wt% Co, - 1.2 - 3 µm WC grain size have been used for many
decades as dies and punches in the cold heading of a range of products, such as wood screws, metal
thread screws, self-tapping screws, bolts and other such components with a formed head. Hardmetal dies
are used in machines operating at a rate of well in excess of 250 strokes per minute using coiled wire
stock. The punches, used to form the head shape, are also made from high quality hardmetal alloys in the
range 20 - 25 wt% Co, - 4-5 µm WC grain size. This provides the highest impact strength required for
such an operation [98K].
As has been stated previously, hardmetal was discovered by research work carried out to develope a
cheap substitute for diamond wire drawing dies. After many years of use in a vast range of applications,
hardmetal has now become the essential element in the manufacture of synthetic diamond and the newly
discovered cubic boron nitride. The requirement of a system to simulate the temperature and pressure
inside the earth's mantel led to a search for material with an extremely high compressive strength. This
material is hardmetal!
The pressure system, which is commercially used, is described in sections 13.3.2.2 and 13.3.2.3 and is
essentially a die shrunk into a multi-belt ring unit with a top and bottom anvil [95K2, 92F]. Typical
dimensions and arrangements are shown in Fig. 13.154 [99S4]. The size of the units has markedly
increased as the demand for larger quantities of synthetic diamond, cubic boron nitride grits, and larger

pieces of polycrystalline diamond/cubic boron nitride has evolved. It has now reached the stage where
one anvil will weigh as much as 500 kg. This is manufactured from a hardmetal, typically in the range
9 - 11 wt% Co, - 1.4 - 2.0 µm WC grain size, to exceptional quality standards, particularly in relation to
freedom from pores and inclusions. Thus, one hard material product is totally dependent on another hard
material product.
13.6.4.2 Diamond
Diamonds are extensively used as wire drawing dies for the production of a whole range of metals and
alloys. The polycrystalline diamond (PCD) products, e.g. Syndie1, Sumidia WD2 and Compax3, as well as
single synthetic diamond crystals, e.g. Monodie1 and CVDD3, wire dies are used in a range of bore sizes
[90S2, 93D2, 93G1].
The metals and alloys drawn range from copper, aluminum, stainless steel, zinc and copper plated
steel, high carbon steel, brass coated high tensile steel, nickel alloys, gold, platinum to tungsten and mo-
lybdenum (the latter two hot drawn).
As one example, a string of seven Syndie CSB 0251 dies was used to draw down a 20 mm diameter
copper rod to 8 mm diameter. The first die had a bore of 17.85 mm while the finishing die had a bore of 8
mm. The output of copper wire was increased by a factor of 500 compared with that achieved with a
similar hardmetal die string [91R]. Other examples show increases in life, over hardmetal dies, from 100
times for aluminum to 6 - 20 for stainless steel [90S2]. The hot drawing (600 - 700 °C) with a 10 die
string (Syndie NTB 0201) of tungsten filament wire showed an increase in life of 50 times that achieved
with hardmetal. The surface finish of the wire was also vastly improved [93D2].
The use of synthetic single diamond crystals, e.g. Monodie1, has shown that they can substitute natural
diamonds as wire drawing dies, with, in some cases, an improvement in life. They can be used with the
indicated range of metals and alloys but naturally in the finer size ranges. Wire drawing parameters are
used, in terms of drawing speeds and elongation ratio, similar to those adopted for natural diamonds
[93D2]. The CVDD4 die blanks, manufactured by a chemical vapour deposition technique, are available
as small - 1 to 2.5 mm diameter × 0.6 to 1.2 mm thick - units. They are particularly recommended for
drawing fine wire used in the medical and electronic industries [93G1].
13.6.5 Wear parts

13.6.5.1 Hardmetal
The number of applications in the category known as wear parts is enormous. The range covers items as
diverse as balls for ball-point pens, wear pads, guides, paper trimming knives, slitters for audio- and
video-tapes, seal rings, bearings, nozzles, valve seats and stems, cylinders and pistons for high pressure
chem-ical processes etc. In fact, the list covers every known manufacturing and processing technique
where wear or corrosion is a problem.
A whole range of hardmetal alloys has been developed to match the various operating conditions.
These cover situations associated with specific wear characteristics, i.e. abrasive, attrition and adhesion
wear, together with the added problem of corrosion. Such alloys are shown in Table 64 which have, in
many cases, modified binders containing cobalt/nickel/chromium. For specific problems, coating the
basic hardmetal, by PCVD or PVD, with titanium nitride has conferred extra protection against certain
corrosive media. The combination of corrosion and wear can be difficult to diagnose and therefore, care is
necessary in selecting an alloy for these applications.
__________
1
2
Trade name of Sumitomo Electric Industries Ltd, Japan.
3
Trade name of General Electric Inc., USA.
4
Trademark of General Electric Inc. USA.

As just one example, from this wide range of use, sealing rings in pumps are an important area of ap-
plication. Because of the very varied nature of the medium being pumped - from pure liquid with pH
values above and below 7, to heavy slurries - the choice of hardmetal for the sealing rings, to obtain opti-
mum life, is crucial.
Sealing rings, by their very construction, run against another sealing face. Thus, combinations of ma-
terials are often used in this situation, e.g. hardmetal against carbon, hardmetal against silicon carbide,
hardmetal against filled plastics and hardmetal against hardmetal. A very detailed programme is therefore
necessary to investigate all of these possibilities. One of the major factors is the so called PV-factor,
which is the operating fluid pressure times the circumferential speed. This is used to judge the operating
conditions at which the seals fail usually by leakage. Leakage can occur due to the face of the seal be-
coming disrupted by wear/corrosion or by heat cracking. This latter factor is very important especially
when seals may have to run under dry conditions. It is therefore essential to have materials with a high
thermal conductivity and thermal shock resistance. High PV-pumps, and especially when run under high
temperature conditions, are recommended to be fitted with a carbon and hardmetal combination. For
slurries and high viscosity liquids, where sliding abrasive wear dominates, both rings should be made of
hardmetal. Thus, the advantages of hardmetal can be summarised as:
- Suitable for use under all PV-conditions but especially suited for high PV-values.
- Ability to handle abrasive slurries and high viscosity liquids.
- Special alloys available to combat corrosive conditions.
It can be seen that hardmetals are very suitable for this application and because of the ability to vary
the composition and grain size, alloys can be matched to every situation [89N, 98K, 99S5].
13.6.6 Optical and electronic applications

13.6.6.1 Diamond
Diamond possesses a unique multi-spectral transparency, from 220 nm wavelength in the ultraviolet to
the far infrared and over much of the microwave radar frequencies - except for the intrinsic phonon band
between 4000 cm−1 to 1500 cm−1, as shown in Fig. 155 [93S2]. It can be seen that the transparency range
is far wider than that of other optical substances.
The combined properties of diamond - high thermal conductivity, low absorption coefficient and a
low value of the temperature coefficient of refractive index - make this material a good candidate for high
power laser windows. Other possible applications are windows for domes for infrared thermal imaging
systems, windows for high vacuum interrogation ports, windows for use in monitoring of aggressive
chemical processes, infrared beam splitters etc. [93S2, 95G1, 98S2].
The thermal conductivity of diamond at room temperature is the highest of all known materials. A
comparison with copper shows diamond to be five times better, and for other commonly used conductive
electric insulators by a factor of ten. Thermal diffusivity, which is a measure of the speed at which heat
can be propagated through a material, is also important. Because of the low value of heat capacity, the
relative value of thermal diffusivity of diamond is greater than that of copper by a factor of 7 to 10.
One of the practical applications, to take these properties into account, is the use of a CVD diamond
plate as a submount for a high power laser diode, as shown in Fig. 13.156 [93S2]. This construction al-
lows the diamond to act as a heat spreader, reducing the overall thermal resistance of the laser diode. It
can be appreciated that this arrangement can be built upon to include an array of such laser diode chips
[98S2, 93S2].
An application related to the low dielectric loss of diamond is the use of CVD diamond as output win-
dows of high power microwave tubes, such as Gyrotron tubes operating in the 70 to 170 GHz frequency
region with output powers in excess of 1 MW [98S2].
An important aspect of using diamond in electronic applications, is the ability to make sound and con-
sistent electrical connections. The metallisation of the diamond surface is a prerequisite for these connec-
tions to be made. This has been solved using a multi-layer approach with a thin gold layer being the top-
coat [94G3].

13.7 Health, safety and ecology
The following organisations are concerned with health, safety and ecology regulations:
1) American Conference of Governmental Industrial Hygienists (ACGIH), USA.

2) Commission of the European Communities, Employment, Social Affairs and Education, Health and
Safety Directorate, Luxembourg.
3) National Institute for Occupational Safety and Health (NIOSH), USA.
4) Occupational Safety and Health Administration (OSHA), USA.
5) World Health Organisation, International Programme on Chemical Safety, Switzerland.
6) Japanese Ministry of Labour, Labour Health and Safety, Tokyo, Japan.
Note: Most countries have governmental departments dealing with health and safety and these should be
contacted for current regulations. Member countries of the EU fall under the appropriate directives and
regulations of this organisation.
The following trade organisations are also concerned with health, safety and environmental directives and
regulations:
1) Cobalt Development Institute,

167 High Street, Guildford, Surrey GUI 3AJ. UK.
2) International Tungsten Industry Association,
Unit 7 Hackford Walk, 119 - 123 Hackford Road, London SW9 OQT, UK.
3) Nickel Development Institute, 42 Weymouth Street, London WIN 3LQ, UK.
and
Nickel Development Institute, 214 King Street West-Suite 510, Toronto, Ontario M5U 3S6, Canada
The following table lists the occupational exposure limits (OEL) as established in the listed countries:
Table 101. Existing occupational exposure limits (OEL) as established in the listed countries. (OEL mg / m3)
Countries Metallic nickel Metallic cobalt

and insoluble nickel species1 and insoluble cobalt species2
Australia 1.0 0.05
Austria 0.05
Belgium 1.0 0.02
Bulgaria 0.5
Canada 1.0
China 1.0
Czech Rep. 0.05
Denmark 0.05 0.05
Egypt 0.1
Finland 1.0 (0.1 nickel oxide and carbonate) 0.05
France 1.0 0.05
Germany 0.05 0.1 - 0.5
Hungary 0.1
Ireland 0.1
Italy 1.0 0.05
Japan 0.05
Luxembourg 1.0
Netherlands 1.0 (0.1 nickel oxide and carbonate) 0.1

Countries Metallic nickel Metallic cobalt

and insoluble nickel species1 and insoluble cobalt species2
Norway 0.1 0.05
Phillipines 0.1
Poland 0.05
Portugal 1.0
Russia 0.05 0.5 (STEL)
Spain 1.0
Sweden 0.5 (0.1 nickel oxide and carbonate) 0.05
Switzerland 0.1
S. Africa 0.1
UK 0.5 (MEL) 0.1 (MEL)
USA 1.0 (PEL) 0.1 (OSHA-PEL)
1.5 Nickel (ACGIH-TLV)
0.2 Insoluble Ni (ACGIH-TLV)
European Union 1.0 Metallic nickel
0.5 Nickel oxide
The OSHA-PEL for an 8 hour exposure to cobalt metal, dust and fume is 0.05 mg / kg. The ACGIH have
adopted a TLV-TWA (8 hours) of 0.02 mg / m3 for cobalt and its inorganic compounds.
1
Source Nickel Development Institute (Jan. 1998).
2
Source Cobalt Development Institute (Oct. 1998).
Tungsten and its compounds show generally low toxicity compared with most other metals and their
compounds. The typical metal threshold limit value for tungsten metal is 5 mg · m−3.
Ecotoxicity tests for cobalt and its chemical compounds have shown that under certain circumstances
cobalt metal powder and sulphate would be classified as very toxic to aquatic organisms and the oxide
would be considered harmful. It is assumed that the nitrate, chloride and acetate would also be classified
as very toxic. Ongoing acceptable toxicity tests are necessary to arrive at a more precise definition of the
status of cobalt and its compounds. This also applies to both nickel and tungsten and their compounds.
Hazard identification EU regulations, within EU member countries, have to be observed. The follow-
ing codes apply:
Nickel metallic powder

Xn, Harmful. Category 3 carcinogen
R 40 - possible risk of irreversible effects
R 43 - may cause sensitisation by skin contact
S 22 - do not breath dust
S 36 - wear suitable protective clothing
Cobalt metallic powder

Xn, Harmful
R 42 - may cause sensitisation by inhalation
R 43 - may cause sensitisation by skin contact
S 22 - do not breath dust
S 24 - avoid contact with skin
S 37 - wear suitable gloves
In the USA cobalt and its compounds are rated 2B by IARC (possible human carcinogen).
The above information has been given as general information and should not be relied on in any legal
manner. It is strongly advised that correct, up-to-date data should be obtained from the relevant authori-
ties in each country. This applies especially to all health matters concerning workers in those industries
concerned with these materials.

13.8 Acknowledgements
Grateful thanks are due to the many companies and organisations who provided data, information and
some of the illustrations. In particular, the author would like to thank De Beers Industrial Diamond Divi-
sion, Ascot, UK; Sumitomo Electrical Industries (Hardmetal), Princess Risborough, UK; General Electric
Company, Worthington, USA; Sandvik Hard Materials AB, Stockholm, Sweden; Kennametal Inc.
Latrobe, USA; Widia GmbH, Essen, Germany; and Plansee Tizit, Tyrol, Austria, for their generous help
and patience in dealing with many enquiries. The author is also indebted to numerous colleagues and
friends, in the various industries, organisations and universities for their personal help in locating infor-
mation and, not least, to all the authors of the various papers and publications used in this work.

Figures for 13
Scheelite Wolframite Soft scraps Hard scraps

HCI Na2 CO 3 NaNO3/NO2
O2 NaOH
Pressure Pressure
Leaching Oxidation Fusion
leaching leaching
Waste
Solid/liquid liquid Solid/liquid
separation Leaching residues
separation HCI, CoCl 2
Fe(OH)3, Mn(OH)2, CaCO3
Na2WO4 Co(OH)2,TiO2,Ta(Nb)2O5
WO3⋅H2O solution
sludge
Activated
carbon H2SO4
Precipitation of
Dissolution As, P, Si Precipitate
purification NH4OH
Al2(SO4) 3 impurities Al(OH)3, Mg(OH)2
MgSO4 As2O5, P2O5
Filtration
Mother
liquor APT NH3
H2 SO4
crystallization Precipitation of H2S
Mo(As)
NaHS impurities Precipitate
MoS3(As2S5)
APT crystal Filtration
CaWO4 sludge Sodium

(for synthetic scheelite isopolytungstate
preparation) solution
CaCl 2 H2SO4
CaWO 4 Waste
NaCl H2 O Solvent Na2SO4 solution
H2 O precipitation extraction
washing solution NH4OH stripping
Ammonium tungstate
solution
NaHS
pH adjustment NH 3
HCI Mo complexing Mother APT
liquor crystallization
NH 3
NaOH Na2WO4 APT crystal
conversion
Fig. 13.1. The main hydrometallurgical steps in APT manufacturing processes [95V].

13-132 13 Hard materials [Ref. p 13-185
Time Temperature Cycle
Hydrogen Blue oxide

Flow H2O
rate content
Apparent Particle size Layer

Laminar or density agglomeration height
turbulent gas flow
[H2O]/[H2] H2O Production rate Individual
exchange rate porosity
H2O Removal rate
Global gas permeability
Non - isothermal industrial
of powder layer
Quality of W powder
Layer heigh (cm)
[H2O] difference - Grain size and shape

across powder layer - Grain size distribution
- Apparent density
- Degree and size of agglomeration
Local WO 2 (OH) 2 vapor pressure Oxide morphology
Interface kinetics
Reaction rate
Local
supersaturation
gradients
of WO2(OH)2,H2
H2O
Dimension of grain size (µm)
Material transport rate

Micro − convection
Isothermal local
diffusion Transport distance
W growth rate W nucleation rate
Particle size and shape Number of particles
Size, shape, number of individual W particles
Fig. 13.2. Influence of different reduction parameters on tungsten nucleation and growth (schematic) [83H].

Sample 1777/98/WBV Sample 1763/98/WBV

Density 19.30 g cm–3 Density 19.30 g cm–3
Suspension fluid water Suspension fluid water
Dispersing agent extran Dispersing agent extran
Ultrasonic mixer time 20 s Ultrasonic mixer time 20 s
Comments 2' vibracell + extran Comments 2' vibracell + extran
100 100
W - powder W05-10 W - powder W50-120
80 80
Undersize [wt %]
Undersize [wt %]
60 60
40 40
20 20
0 0
0.1
1 10 60 0.1
1 10 60
Grain diameter d [µm] Grain diameter d [µm]
Median size 0.72 µm Median size 13.25 µm
Diameter for 10 % 0.38 µm Diameter for 30 % 10.15 µm
Specific surface area 5054 cm2/g Specific surface area 406 cm2/g
d [µm] 0.1 0.2 0.3 0.4 0.5 0.6 0.7 d [µm] 0.1 0.2 0.3 0.4 0.5 0.6 0.7
% 0.2 1.5 4.8 11.1 22.5 35.9 48.3 % 0.0 0.1 0.2 0.3 0.5 0.8 1.0
d [µm] 0.8 0.9 1.0 1.1 1.2 1.3 1.4 d[µm] 0.8 0.9 1.0 1.1 1.2 1.3 1.4
% 59.0 67.9 75.2 81.0 85.5 89.1 91.8 % 1.2 1.4 1.6 1.8 1.9 2.1 2.2
d[µm] 1.6 1.8 2.0 2.2 2.5 2.8 3.1 d[µm] 1.6 1.8 2.0 2.2 2.5 2.8 3.1
% 95.3 97.1 98.2 98.8 99.3 99.7 99.9 % 2.4 2.6 2.7 2.9 3.2 3.5 3.9
d [µm] 3.5 − 60 d[µm] 3.5 4.0 4.5 5.0 5.5 6.0 6.5
% 100 % 4.4 5.3 6.4 7.7 9.1 10.7 12.5
d [µm] 7.0 8.0 9.0 10.0 11.0 12.0 13.0
Fig. 13.3. Grain size distribution curve of a tungsten % 14.4 18.6 23.5 29.0 35.1 41.6 48.3
metal powder type W05-10 supplied by Wolfram
d[µm] 14.0 16.0 18.0 20.0 22.0 24.0 26.0
Bergbau- und Hüttengesellschaft m.b.H., St. Peter i.S,
% 55.0 68.0 79.1 87.6 93.5 97.1 99.1
Austria
Determined using a Cilas*- HR850 granulometer high d [µm] 28.0 − 60
resolution laser diffraction apparatus. (* Trademark of % 100
Alcatel, Marcoussi, France).
Fig. 13.4. Grain size distribution curve of a tungsten
metal powder type W50-120 supplied by Wolfram
Bergbau- und Hüttengesellschaft m.b.H., St. Peter i.S,
Austria.
Determined using a Cilas*- HR850 granulometer high
resolution laser diffraction apparatus. (* Trademark of

WC WC
C
W W W2 C
CO
W2 C
Single crystal tungsten particle
WC
C
W2 C
CO
Polycrystalline tungsten particle
WC
C
CO W
W W2 C
Fig. 13.5. Schematic representation of the
Tungsten particle with grain boundary. progress of carburisation of a tungsten
(Carburisation proceeds simultaneously from the particle [87Z].
outer surface and along the grain boundary)
3800
W-C
3600
ca.3550
3423±26 liquid
3400 liquid
+C gas
(0.1 MPa)
3200
2720±12
Temperature T [°C]
2747±12 [41]
W [39] liquid
3000 + +
liquid 2735±12
C
[38.5]
2776±12
[42] 2776±10
2800 [ca.031]
2710±12
γ −W2 C
[<1] [22] [25.6] α −WC 1−x
2600 2490±30 2530±20
[32.6] [ca.38] WC+C
2400 2380±30
W + W2 C
β −W2 C [ca.33.4]
2200 W2 C+WC
WC
α−W2 C
2000 Fig. 13.6. Equilibrium diagram of

0 10 20 30 40 50 60 tungsten-carbon [69R].
W C content cC [at %]

Sample 1644/B/97/WCV/FG Sample 1779/A/98/WCV

Density 15.65 g cm–3 Density 15.65 g cm–3
Suspension fluid water Suspension fluid water
Dispersing agent extran Dispersing agent extran
Ultrasonic mixer time 20 s Ultrasonic mixer time 20 s
Comments 2' vibracell + extran Comments 2' vibracell + extran
100 100
WC - powder WC 05-06 WC - powder WC 50-120

80 80
Undersize [wt %]
Undersize [wt %]
60 60
40 40
20 20
0 0
0.1
1 10 60 0.1
1 10 60
Grain diameter d [µm] Grain diameter d [µm]
Median size 0.61 µm Median size 9.73 µm
Specific surface area 7702 cm2/g Specific surface area 671 cm2/g
d [µm] 0.1 0.2 0.3 0.4 0.5 0.6 0.7 d [µm] 0.1 0.2 0.3 0.4 0.5 0.6 0.7
% 0.6 3.6 10.4 21.1 35.0 48.9 60.7 % 0.0 0.1 0.2 0.3 0.5 0.9 1.2
d [µm] 0.8 0.9 1.0 1.1 1.2 1.3 1.4 d [µm] 0.8 0.9 1.0 1.1 1.2 1.3 1.4
% 70.2 77.8 83.7 88.2 91.6 94.2 96.0 % 1.6 1.9 2.2 2.4 2.7 2.9 3.2
d [µm] 1.6 1.8 2.0 2.2 2.5 − 60.0 d [µm] 1.6 1.8 2.0 2.2 2.5 2.8 3.1
% 98.3 99.3 99.7 99.9 100 % 3.6 4.1 4.6 5.2 6.2 7.2 8.4
d [µm] 3.5 4.0 4.5 5.0 5.5 6.0 6.5
Fig. 13.7. Grain size distribution curve of a tungsten % 9.9 11.8 13.6 15.6 17.8 20.4 23.4
carbide powder type WC 05-06 supplied by Wolfram d [µm] 7.0 8.0 9.0 10.0 11.0 12.0 13.0
Bergbau- und Hüttengesellschaft m.b.H., St.Peter i.S, % 26.8 34.7 43.4 52.3 60.8 68.6 75.5
Austria. d [µm] 14.0 16.0 18.0 20.0 22.0 24.0 − 60.0
Determined using a Cilas* HR850 granulometer high
% 81.4 90.3 95.7 98.5 99.7 100
Fig. 13.8. Grain size distribution curve of a tungsten
carbide powder type WC50-120 supplied by Wolfram
Bergbau- und Hüttengesellschaft mbH., St. Peter i.S,
Austria.
Determined using a Cilas* -HR850 granulometer high

Oxidic Cu - Co ores Cu - Co sulphide concentrates

Concentrates
Roasting to sulphate
Leaching
Extraction Residue
Cu - Co liquor
Electrolysis Cu
Co liquor
Purification
Fe, Al, Cu etc
Limewater
Co - precipitation
Dissolution
Co electrolysis
Filtration
Cathode - Co
CaSO4
Electric furnace Chemical processes

refining
Granulation Spheroidal Oxide

99.5% Co powder salts
Fig. 13.9. Processing of Katanga ores (schematic) [95K1].

3067 4000
3000 Ti - C
Ta- C
2776
liquid
liquid 3500
2500 3330±100
3400±50
3014 β −Ta2C TaC TaC + C

liquid 3000
2000 TiC
Temperature T [°C]
Temperature T [°C]
+ TiC + 2830±25
TiC C Ta
1668
1645
1500 2500
β −Ti
β −Ti + TiC 2180
ca.1930
1000 2000 α−Ta2 C
920
α −Ti
α−Ti + TiC
500 1500
0 10 20 30 40 50 0 10 20 30 40 50 60 70 80
C content cC [at %] C content cC [at %]
Fig. 13.10. Equilibrium diagram of titanium-carbon Fig. 13.11. Equilibrium diagram of tantalum-carbon
[67S1]. [67S1].

3000 3000
V-C liquid + C Mo - C η − Mo3C3
liquid
2500 liquid
2670 β δ − MoC1−x
liquid + VC
2500 2000
Mo(C)
Temperature T [°C]
2165 ± 25
1500
liquid VC
2000 +V2 C 1000
VC + C
Temperature T [°C]
V+ liquid
β’ − Mo2C MoC
V2 C 500
V 1630 ± 20
1500 0
0 10 20 30 40 50 60
C content cC [at %]
V + V2 C
Fig. 13.13. Equilibrium diagram of molybdenum-
1000 carbon [91M2].
←
Fig. 13.12. Equilibrium diagram of vanadium-carbon
500 [67S1].
0 10 20 30 40 50 60
C content cC [at %]
Content ratio [N] / [Ti]

0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
3500
Ti - N
3000 liquid δ − TiN1-x
[N] / [Ti]
0.40 0.50
1300
1570
2500 δ
1280 1550
Temperature T [°C]
Temperature T [°C]
Temperature T [K]
1380
ζ − Ti4N3−x
1100
η − Ti3N2−x
2000 1360
1080
1340
1060 ε
β −TiN
1500 24 28 32 36
at % N
α−TiN
1000
ε − Ti2N
Fig. 13.14. Equilibrium diagram
500 of titanium-nitrogen [91L].
0 5 10 15 20 25 30 35 40 45 50
N content cN [at %]

WC Co Ni Ta(Nb)C,WC - TiC,TiC,
WC - TiC - Ta(Nb)C, Mo2C,
VC, Cr3C2
Milling liquid
Wet milling
Ball,attritor Pressing lubricant
Plasticiser Special binders
Vacuum Vacuum Vacuum Spray Granulating

drying drying drying drying
Kneading
Powder Granulated
Extrusion Injection powder
moulding
Cold isostatic
pressing, High - pressure
low - pressure automatic die
die - pressing pressing
Fig. 13.15. Schematic flow diagram for the production of hardmetal and cermet alloy powders.
Fig. 13.16. Schematic representation of an attritor mill. Fig. 13.17. Schematic representation of the ball
velocity gradient across an attritor mill.
Scrubber-
condenser
Drying Indirect heater
chamber (liquid phase) Cooling
water
Feed
system
Cyclone
Nozzle
atomiser
Press
powder Solvent
collection recovery Fig. 13.18. Schematic flow diagram of
spray drying [82J].

Vacuum connection
Lid
< Paraffin waxes
Polyethylene waxes
Water inlet
Mass Low density polyethylene 250 MFI
Microcrystalline paraffin waxes

Carnauba grey wax
Kneading arm 1
Kneading arm 2 with n 1 Montan ester waxes
with n 2
Water outlet 50 55 60 65 70
Hardmetal in plastisol [vol %]
Kneading trough
Fig. 13.21. Relative merits of various polymers and
Fig. 13.19. Schematic illustration of kneading waxes in forming high volume fraction plastisols with
operation, n1= ½ n2 for the speed of rotation of the two satisfactory rheological characteristics in the shear
arms. range 102 - 103 s. [88M].
H2 Ar N2 /H2
Powders ∆l~0% Debinding
Blending Kneading Extrusion Debinding part

H2 Ar N2 /H2
Plastifying Feed stock
Sintering
Injection ∆l:10 - 20%

Green part
moulding Sintering part
Fig. 13.20. Flow schedule for injection moulding [88P]
Gaps between
Loose granules granules Porosity
T oo low a pressing pressure Sin tering
Porosity
Contraction [%]
B06
A06 −
04
>B Porosity
B04
6
A02 > B02
A 0
4−
A0
02 2
<B B0
A02 <
B02
A02 2<
A0
A02 <
B02
Critical Fig. 13.22. Influence of pressing

press zone pressure on granulated powder and
porosity after sintering.
Increasing pressing pressure [MN m−2 ]

100 800 100
300°C Wax - hardmetal

250°C
80
80 600
Wax - hardmetal
Loss of binder mass [%]

Temperature T [°C]
60
Loss of wax [%]
60
400
200°C 40
40
200
20
20
0 0
150°C 0 200 400 600 800 1000 1200 1400
Time t [min]
0 1 2 3
Time t [h] Fig. 13.24. Dewaxing schedule for a 31 wt% montan
ester wax - hardmetal extruded component. (area:
Fig. 13.23. Loss of paraffin wax (melting range volume 11.8) in a hydrogen / nitrogen atmosphere
43-46 °C) on heating in a flow of hydrogen (3 m/min) Open circles: left hand scale; open triangles: right hand
[70S]. scale [88M].
3
Co - WC hardmetal with paraffin m 55
m 28 2.1 m 69
m 44 2.1 m 111 1.8
m 127
0.8
2
m 55/A⋅10 −10
m 69/A⋅10 −10
m 28/A⋅10 −8
m 44/A⋅10 −9
m 111/A⋅10 −
1.7
Mass intensity
1.3 1.0
1 0.4
1.3
0.9 0 0.5 0 0.2

0 200 400 600 800 0 200 400 600 800
a Temperature T [°C] b Temperature T [°C]
Fig. 13.25a, b. Mass spectroscopy of gases produced during heating of a 6 wt% Co-WC hardmetal with paraffin
(2 wt%)
(a) Intensity distribution for CO (m28) and CO2 (m44)
(b) Intensity distribution for different hydrocarbons (m55, m69, m111, m127) [92LI].

5 8 8
Co - WC hardmetal with PEG
m 55
1.6
m 57
m 28 4
m 44 4 m 71 6 6
m 55/A⋅10 −10
m 57/A⋅10 −10
m 44/A⋅10 −8
m 28/A⋅10 −8
m 71/A⋅10 −
Mass intensity
3 4 4
0.8
2
2 2 2
1 0 0 0 0
0 200 400 600 800 0 200 400 600 800
Fig. 13.26a, b. Mass spectroscopy of gases produced during heating of a 6 wt% Co-WC hardmetal with PEG (2 wt%)
(a) Intensity distribution for CO (m28) and CO2 (m44)
(b) Intensity distribution for different hydrocarbons (m55, m57, m71) [92LI].
WC - 6 wt % Co with 2 wt % parafin WC - 6 wt % Co with 2 wt % PEG
IR spectroscopy st - strong IR spectroscopy IR spectroscopy st - strong IR spectroscopy

m - medium m - medium
in Ar w - weak in H2 in Ar in H2
w - weak
m Hydrocarbons w st Hydrocarbons st
with with
carbonyl groups carbonyl groups
m w m st
Ethylene Ethylene
Intensity
Intensity
m w st st
Dioxane Dioxane
st w m
no proof Methane Methane
w w
CO 2 no proof CO 2 no proof
m m m m
CO CO
200 400 600 800 200 400 600 800 200 400 600 800 200 400 600 800
Temperature T [°C] Temperature T [°C] Temperature T [°C] Temperature T [°C]
Fig. 13.27a, b. IR spectroscopy of gases produced during heating of a hardmetal in an argon or a hydrogen
atmosphere.
(a) For WC-6 wt% Co with paraffin (2 wt%)
(b) For WC-6 wt% Co with PEG (2 wt%) [92L1].

800 °C
100
700 °C 700 °C u.800 °C
600 °C
600 °C 20
500 °C 500 °C
400 °C Hardmetal alloys
75 D-2
300 °C
Reduction of oxides [%]
400 °C
200 °C 15 D-3
Transverse rupture strength [N mm−2 ]

50
300 °C
100 °C D-5
25 10
200 °C Water C-4
WC - Co content
P 40
100 °C
0 4 6 2 8
A-2
Time t [h] 5
Fig. 13.28. The progressive reduction of oxides within P 20
a WC-6 wt% Co compact heated in a stream of dry
hydrogen [70S].
Fig. 13.29. Relationship between pressing pressure and 0

transverse rupture strength of hardmetal alloys 50 70 90 110 130 150
presintered at 800 °C/0.5 h under a vacuum [80N].
Pressing pressure p [MN m−2 ]
Codes refer to alloys shown in Table 30. →
WC - Co Shrinkage
Shrinkage doped WC - Co rate
rate
Thermal Thermal
effects effects
Shrinkage Shrinkage
Mass loss Mass loss

rate rate
I
Mass loss
Mass loss
m44
Gas m44 (CO2)
m43 formation Gas
formation
m29
m28 m28 (CO)
0 250 500 750 1000 1250 1500 1750 0 250 500 750 1000 1250 1500 1750
Temperature T [°C] Temperature T [°C]
Fig. 13.30. Compilation of results from a combined use of Fig. 13.31. Compilation of results from a combined use of
thermal analysis and gas analysis during sintering of a thermal analysis and gas analysis during sintering of a
normal grained WC-6 wt% Co hardmetal (dWC = 2.3 µm). VC/Cr3C2 doped WC DS 60 - 10 wt% Co hardmetal
Conditions: inert atmosphere (helium 5 l/h). Heating rate (dWC = 0.6 µm). Conditions: inert atmosphere (argon 5 l/h),
10 K/min [97L2]. heating rate 10 K/min [97L2].

35 C
undoped 1374 °C 1.0
WC - Co T = 1548 K
0.9
30
TaC 1367 °C 0.8
Cr3C2 1355 °C 0.7
25
C
0.6
tion
DSC signal [µV]
WC
VC 1346 °C fcc + graph.
ac
0.5
l fr
20
Mo
0.4 M2C
VC/Cr3C2 1328 °C
0.3 liq.
15 M6 C
0.2
0.1 M12C
10 bcc
0
0 fcc 0.2 0.4 µ 0.6 0.8 1.0
5 Co Mol fraction W W
1200 1240 1280 1320 1360 1400 1440 1480
Temperature T [°C]
Fig. 13.33. The isothermal section of Co-W-C phase
diagram at 1584 K. Calculated [89G2].
Fig. 13.32. Influence of VC, Cr3C2 and TaC grain
growth inhibitor doping on the melting point of WC DS 40
(0.4 µm)-10 wt% Co hardmetals [96G3].
4000 1500
Co - WC 6 wt % Co -W - C liq.+ WC+ graph.
3500 liq.+ WC + M6C
1400
liquid
liq.+ graph. a
3000
Temperature T [°C]
Temperature T [K]
1300
2500 b
liq.+graph.+WC fcc + M6C + WC
1200 fcc + WC
2000 liq + WC
1100 fcc + WC + M12 C fcc + WC+ graph.

1500
fcc fcc + WC 6 wt % Co
1000 1000
0 0.2 0.4 0.6 0.8 1.0 5.4 5.7 6.0
Mol fraction WC C content wC [ wt %]
Fig. 13.34. The Co-WC vertical section of the Co-W-C Fig. 13.35. Vertical section of the Co-W-C phase
phase diagram. Calculated [89G2]. diagram. Calculated at 6 wt% Co. The points denoted
by „a“ and „b“, respectively, define minimum and
maximum carbon contents of alloys which are in a two-
phase state of fcc + WC just after the equilibrium
solidification [89G2].

1500 0.14
liq.+ graph.+WC
6 wt % Co-W -C
liq.+ WC + M6C
0.12
1400 liq.+ WC
Volume fraction of fcc Co - phase

a 0.10
Temperature T [°C]
1300
0.08
fcc + M6C + WC b +0.1 %C
0.06 5.76 %C
1200
fcc + WC fcc + WC+ graph. − 0.1 %C
0.04
1100
fcc + WC + M12 C 0.02
10 wt % Co - W - C
1000 0
5.4 5.7 6.0 1000 1100 1200 1300 1400
C content wC [ wt % ] Temperature T [°C]
Fig. 13.36. Vertical section of the Co-W-C phase Fig. 13.37. Calculated volume fractions of the fcc
diagram calculated at 10 wt% Co. The points denoted cobalt phase at three carbon levels for a Co-W-C alloy
by „a“ and „b“ define, respectively, minimum and containing 6 wt% Co [94 U].
maximum carbon content of alloys which are in a two-
phase state of fcc + WC just after equilibrium
solidification [89G2].
0.7
0.357
Lattice parameter of fcc phase [ nm]
0.6 aγ
Mean grain size WC [ µm ]
0.356
0.5
dWC 0.355 Fig. 13.38. Effects of carbon content on mean tungsten
carbide grain size and lattice parameter of the fcc (β)
0.4 WC + (W,V)C WC + (W,V)C phase in a WC-20 wt% Co-1 wt% VC alloy sintered at
1400 °C for 1 h. Mean grain size of starting tungsten
+β + η WC + (W,V)C + β +β + C 0.354
carbide powder 0.34 µm [72S2].
0.3 (C content: converted values to WC wt%).
5.8 5.9 6.0 6.1 6.2 6.3 6.4
C content wC [ wt % ]

C - Ni - W
0.60
1460 °C
1500 °C
0.50 1550 °C
1645 °C
liq.+ WC+graphite
nC
0.40
c tio
l fra
liq.+ graphite
0.30
Mo
liq.+ WC
0.20 liq.+ WC + M6C
Fig. 13.39. Partial isothermal section at
0.10 1500 °C for the C-Ni-W system
liq.+M6C + Wcc
liq.+ fcc determined by phase decantation
technique [85P].
Ni 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 W
Mol fraction W
1500 1500
Fe - Ni - W - C Fe - Ni - W - C
WC + liq. +M6C WC + liq. WC + liq.
WC + liq. +M6C WC + liq.
1400 1400 +graph.
4.84
WC + liq.
4.98 +graph. WC
Temperature T [°C]
Temperature T [°C]
1300 1300 + fcc

+liq.
WC
+ fcc 4.99
1200 +liq. 1200
WC + fcc +M6C WC + fcc +M6C
5.10
WC + fcc WC + fcc +graphite
1100 1100
WC + fcc WC + fcc +graphite
1000 1000
4.0 4.5 5.0 5.5 6.0 4.0 4.5 5.0 5.5 6.0
C content wC [ wt % ] C content wC [ wt % ]
Fig. 13.40. Vertical section of the Fe-Ni-W-C phase Fig. 13.41. Vertical section of the Fe-Ni-W-C phase
diagram calculated at Fe + Ni = 20 wt% and diagram calculated at Fe + Ni = 20 wt% and
%Fe:%Ni = 3:1. The full circle on the composition axis %Fe:%Ni = 1:1. The full circle on the composition axis
represents the stoichiometric composition [87G]. represents the stoichiometric composition [87G].

1500 0.6
Fe - Ni - W - C WC + liq.
WC + liq.
WC + liq. +M6C 4.66 +graph. 0.5
1400
Carbon content wC [wt % ]

0.4
Temperature T [°C]
1300 4.92
WC + fcc +liq. composition of γ - phase
0.3 in WC TiC TaC
WC
1200 100 0 0
+ fcc 70 30 0
WC + fcc +M6C 0.2
63 27 10
WC - 10wt % Co 49 21 30
1100 WC + fcc +graphite 42 18 40
0.1 35 15 50
21 9 70
1000
4.0 4.5 5.0 5.5 6.0 0 5 10 15 20
C content wC [ wt % ] TiC content wTiC [wt %]
Fig. 13.42. Vertical section of the Fe-Ni-W-C phase

Fig. 13.43. The effect of the TiC content and the
diagram calculated at Fe + Ni = 20 wt% and
composition of the γ-phase on the (WC+β+γ) three
%Fe: %Ni = 1:3. The full circle on the composition
phase field of WC-TiC-TaC-10 wt% Co alloys [67S2].
curve represents the stoichiometric composition [87G].
Width of the WC + β + γ field - wt% C to
carbides vs. TiC wt% content in the carbides.
100 20
Cermet II Cermet II
CO 10 10
80 16 Total pressure
1 500 samples 1
Total pressure p [m bar]
Gas content [%]
Total pressure p [m bar]

60 12
Gas content [%]
N2
Total
pressure 10 −1 50 samples 10 −1
40 H2 8
N2
10 −2 10 −2
20 4
H2O
H2
0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Time t [h] Time t [h]
100 400 700 1000 1300 1520 1520 1320 100 400 700 1000 1300 1520 1520 1320
Temperature T [ °C ] Temperature T [ °C ]
Fig. 13.44. Evolution of CO, H2 and H2O during a Fig. 13.45. Evolution of nitrogen during sintering
sintering cycle with ca. 500 samples of Cermet II cycles of 50 and 500 samples of Cermet II. (See Table
(See Table 32 and Table 33) [91E1]. 32 and Table 33) [91E1].

0.05 −10
(1) TiC c.a.s.
(4) TiC0.3N0.7 (2) TiC0.7N0.3
0 −20
(1) TiC c.a.s. (3) TiC0.5N0.5
Shrinkage rate [ µm⋅min−1 ]

− 0.05 (2) TiC0.7N0.3 (4) TiC0.3N0.7
− 50
Shrinkage [ ∆l/lo]
(3) TiC0.5N0.5
− 0.10
− 80
− 0.15
−.020 −110
−0.25 −140
600 800 1000 1200 1400 1600 600 800 1000 1200 1400 1600
Fig. 13.46a, b. Shrinkage (a) and rate of shrinkage (b) of cermets with different nitrogen content. Composition: 76 %
TiC1-xNx-9 % Mo2C-15 % Ni/Co: x = 0 (TiC c.a.s), (2) x = 0.30, (3) x = 0.50, (4) x = 0.70 [93G2].
Grain size:
ultra - fine
3000
2600
10 5 2200
1800
Transverse rupture strength [ N/mm 2 ]
N2 pressure pN2 [bar]
N2 - pressure in equilibrium with C fine

10 3000
2600
2200
1800
−5
10
coarse
N2 - pressure in equilibrium with Mo2C or WC 3000
2600
0 0.2 0.4 0.6 0.8 1.0 2200
Mol fraction TiN 1800
Fig. 13.47. Nitrogen equilibrium pressure of titanium Processes: Sintering Sintering Sintering/HIP
carbonitrides of different compositions for carbon plus HIP, combined,
(upper curve) and Mo2C or WC (lower curve) [91E1]. 120 MPa 5 MPa
Fig. 13.48. Influence of various sintering processes on

the transverse rupture strength of WC-6 wt% Co alloys
with ultra-fine, fine and coarse WC grain sizes [89K].

3430
Zr(C,N) TiC
Ti(C,N) TiN
Ti(C,N)
Transverse rupture strength [N mm−2 ]
2940 10 5 Al2O3
TiC
TiN 104
MT - CVD CVD
Ti(C,N) 103
Pressure p [Pa]
2450 Al2O3 10 2
PCVD
10
1
TiN 10 1
−
1960 Ti(C,N)
10 2 PVD
−
(Ti,Al)N 400 600 800 1000 1200
Temperature T [°C]
1470
Fig. 13.50. Pressure-temperature zones for methods of
hard material coating [97B1].
980 CVD: Chemical Vapour Deposition
0 2 4 6 8 10
MT-CVD: Medium Temperature Chemical
Co content wCo [wt %]
Vapour Deposition
PCVD: Plasma Chemical Vapour Deposition
Fig. 13.49. Transverse rupture strength (measured by PVD: Physical Vapour Deposition
JIS-method) vs. cobalt content. Comparison of
transverse rupture strength of WC-Co alloys of vacuum
sintered (1450 °C-1h) (lower curve) and vacuum
sintered-HIP treated alloys (1350 °C - 100 MPa - 1 h)
(upper curve). [85T].
Furnace
Reactor 0 - 1000 mbar

−200 - +200 mbar
Pump for
Regulating valve preliminary
evacuation
Liebig−
cooler Cyclone
Flowmeter
TiCl 4 0 - 1000 mbar
Ar Rotary liquid pump

H2 CH 4 N2 Washer
Fig. 13.51. Schematic diagram of equipment for coating with TiC or TiN [88K2].

250
3 TiCl 4 + 2H 2 = Ti + 4HCl
200
150
Free enthalpy ∆G [kJ/mol]
100 6 TiCl4 + C + 2H2 = TiC + 4HCl 5 4TiCl 3 = 3TiCl 4 + Ti
50 4 TiCl4 + 1/2H2 = TiCl3 + HCl

7 TiCl4 + 1/2N2 + 2H2 = TiN + 4HCl
0
− 50 2 CH4 = C + 2H 2
_100 1 TiCl4 + CH4 = TiC + 4HCl

Fig. 13.52. Free enthalpy of reaction ∆G
600 700 800 900 1000 1100 1200 1300 1400 for TiC and TiN formation [88K2].
Temperature T [°C]
Temperature T [°C]
1100 1000 900
8⋅1
T = 1300K, p tot = 1 atm
6
1
TiC 0.9 TiN
4
39.4 kJ/mol
10 −1
Deposition rate [µm h−1]
Ti Cl4 partial pressure pTiCl [atm]
TiC 0.8
10−2
4
2
TiC 0.7
10 −3 TiC 0.6 TiC0.98
+ 1
−4 Ti C 309 kJ/mol
10 8
+
TiC0.55 6
10 −5
4⋅10 −1
7.0 7.4 7.8 8.2 8.6
10 −6
−5 −3 −2 −1 Inv.temperature 1/T [10 − 4 K −1]
10 −6 10 10−4 10 10 10
CH 4 partial pressure pCH 4 [atm]
Fig. 13.54. Temperature dependence of TiN deposition
rate. Conditions:
Fig. 13.53. Domains for the deposition of TiC, TiC + –
H2 flow rate = 300 cm3 min 1;
Ti, and TiC + C [88K2]. N2 flow rate = 300 cm min–1;
3
total flow rate = 600cm3 min–1;

p(TiCl4) = 0.296·10–2 Pa;
p(H2 ) = 4.794·10–2 Pa;
total pressure system p = 9.87·10–2 Pa [83K].

8 2400
Ti(C,N) MT − CVD coating 80 mbar
7 WC - Co
6
Deposition rate [µm h−1]
2200
5 Non- impl.
0.245 N
4
2000
Non- impl.
Knoop hardness
3 0.491 N
Ti(C,N) standard CVD coating 700 mbar
2
1800
1
0
700 800 900 1000 1100 1600
Temperature T [°C]
Load 0.245 N
Standard CVD MT − CVD Load 0.491 N
1400
Microhardness 1900 − 2100 2200 − 2400 0 100 200 300 400 500 600
Ti(CN) Implant temperature T [°C]
Structure Granular Columnar
Fig. 13.56. Knoop hardness measured in a WC-
+
Wear Good Better 6 wt% Co hardmetal implanted with 7·1017 N ions cm–2, as
resistance a function of the implantation temperature [85D].
Fig. 13.55. Deposition rate for the MT-CVD process

compared with that of the standard CVD technique.
comparison of some properties [97B1].
1700 35
WC - Co DP - Carbide
1600 30
1500 25
Surface Core
20 layer
1400
Knoop hardness
Non- impl.
0.098 N
1300 15
Intermediate
Non- impl. 10 layer
1200 0.245 N
1100 5
Load 0.098 N
Load 0.245 N
1000
0 100 200 300 400 500 0 1 2 3 4 5 6 7
Implant temperature T [°C] Depth from surface [mm]
Fig. 13.57. The Knoop hardness measured in a WC- Fig. 13.58. Difference in cobalt content from the
25 wt% Co hardmetal implanted with 7·1017 N
+ surface layer to the core of DP-Carbide. (Trade name of
–2
ions·cm , as a function of the implantation temperature Sandvik Hard Materials, AB, Sweden) [99S1].
[85D].

2000 900
DP - Carbide DP - Carbide
600
1500 Tangential
Core 300
Vickers hardness HV3
Stress [MPa]
Radial
1000 Surface
layer −300
Intermediate Core
− 600 layer
500 Intermediate Axial
layer − 900 Surface
layer
−1200
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
Depth from surface [mm] Depth from surface [mm]
Fig. 13.59. Hardness variation from the surface layer to Fig. 13.60. Residual stresses from the surface layer to
the core of DP-Carbide (Trade name of Sandvik Hard the core of DP-Carbide (Trade name of Sandvik Hard
Materials, AB, Sweden). [99S1] Materials, AB, Sweden) [99S1].
300 Surface
WC - TiC - TaC - 6 wt % Co WC + Co
I
WC + (Ti,W)C +
Co content rel.to bulk value [%]
Rake (Ti,W)(C,N) + Co Ti
200 N
II
WC + (Ti,W)C +
Flank TiN +
(Ti,W)(C,N) + Co
100
0 25 50 75 100
Fig. 13.62. Schematic plot of the fronts where the cubic
Depth from surface [µm]
carbide crystals (I) and where the nitrides and the
carbonitrides present in the bulk alloy (II) become
Fig. 13.61. Variation of cobalt concentration (relative unstable. (The arrows indicate directions of nitrogen
to bulk value -6 wt%) with depth from the rake surface and titanium fluxes] [88S2].
of a WC-TiC-TaC-6 wt% Co alloy. (KC 850-
Kennametal Inc., USA, Trademark) [81N].

35
WC - TiN - Co - C
16⋅10 3 WC - Co - TiC
30
Square of the thickness x 2 [ µm2 ]
Cubic carbide free depth [ µm ]

12⋅103 25
1540 °C
1490 °C 20
3
8⋅10
15
4⋅103 10
5
1390 °C
0 2 4 6 8 10 12 14 16 18
Holding time t at Tann [h] 0 100 200 300 400 500 600
Holding time t at Tsint [min]
Fig. 13.63. Time dependence of the thickness of the

cubic-carbide free zone at three annealing temperatures Fig. 13.64. Cubic carbide-free depth versus holding
of a WC- 12.9 wt% (70 WC: 30TiC)- 1,5 wt% TiN- time at a sintering temperature of 1550 °C for four
9 wt% Co- 0.4 wt% C alloy [88S2]. alloys:
open circles: TC 7C- WC-6.8 wt% Co -5.5 wt% TiC
filled circles: TC 8C- WC-6.8 wt% Co -5.5 wt% TiC
[(WTi)C].
open triangles: TC 9C- WC-16.9 wt% Co -5.5 wt% TiC
filled triangles: TC 10C- WC-16.9 wt% Co -5.5% TiC
[(WTi)C] [93Y].
35 28 2200
TC 9 C Ti (CN )
30 24
2000
% Cobalt
25 20
Vickers micro hardness MHV
Co content [at %]
Ti content [at %]
20 16 1800
15 12
1600
10 8
% Titanium
4 1400
5
0 0
0 20 40 60 80 100 0 20 40 60 80 100 120
Depth of surf.zone [µm] Depth from surface [µm]
Fig 13.65. Cobalt and titanium profiles as a function of Fig 13.66. Profile of micro hardness distribution from
the depth for the TC9C alloy (see Fig 13.64) held at the pure Ti(CN) zone to the core [96T2].
1550 °C for 300 min [93Y].

40 0.8
Ti (CN ) Ti (CN )
30 0.6
Compressive res.stress [GPa]

EPMA Co intensity [cps]
20 0.4
10 0.2
0 20 40 60 80 100 120 0 20 40 60 80 100

Depth from surface [µm] Depth from surface [µm]
Fig. 13.67. Profile of cobalt distribution from the pure Fig. 13.68. Profile of the compressive residual stress
Ti(CN) zone to the core [96T2]. from the pure Ti(CN) zone to the core [96T2].
3500 Hard metal die in steel casing

Strip winding
compressive stress
3000
3000 N/mm 2
Allowable inner pressure [ N/mm 2 ]
2800 N/mm 22
2500 2200 N/mm
2000
1500 Shrinkage
compressive stress Fig. 13.69. Comparison between two methods of
1000 3400 N/mm 2 retaining a hardmetal die in a steel casing-strip winding
2800 N/mm 22 and shrinking [95K1].
2200 N/mm The allowable inner pressure in the die vs. the
500
ratio of the outer diameter of the steel casing and
the outer diameter of the hardmetal die: D/d.
0 2 4 6 8 10 12
Ratio of diameters D/d

Run - of - mine ore
Primary crushing
(size reduction)
Secondary crushing
(coarse diamond liberation)
Sreening
(sizing)
Dense medium separation Tails Screening DMS

(primary concentration) (sizing) tailings
Concentrate
Re - crush
(fine diamond liberation)
Screening
(sizing)
Tails
Concentrate Dense medium separation
(primary concentration)
Recovery
(secondary concentration) Recovery tailings
Sorthouse
(tertiary concentration)
Fig. 13.70. Flow sheet for the recovery of diamonds from diamond bearing rock [91C].

10 1 4
9
3
10 5 6 7 8
Fig. 13.71. Schematic section through a typical belt-type apparatus for the production of synthetic diamond.
1) Tungsten carbide anvil; 2) Tungsten carbide die; 3) Steel support rings; 4) Steel support rings for the anvil;
5) Ceramic tube; 6) Electrical contacts; 7) Reaction volume; 8) Heater sleeve; 9) Gaskets; 10) Press platten [79W].
65
line
3-∅
Fe - C Eutectic
60 Maximum Fig. 13.72. Reconstitution experiment

Ni - C Eutectic (strong)
error bars using an iron solvent catalyst. Double

rhombus: capsule unmolten; rhombus
Co - C Eutectic
with bar: only large graphite flakes

Pressure p [ kbar ]
line
i b r ium ) precipitated at cool end of reaction
i l on
55 Equ Sim
chamber; filled rhombus: only
γ - S an and diamonds precipitated at cool end of
rm
(B e reaction chamber; circled rhombus:
diamonds plus large graphite flakes at
Diamond Graphite
crystal Cold flakes cool end; filled circles: source diamond
powder completely converted to
50 graphite.
Molten Source
solvent diamond Each experiment was calibrated for
metal
pressure using the melting points of
Heater
gold and silver. Standard Pt:Pt 10% Rh
Hot
sleeve Insulation thermocouples were used for
45 temperature measurement [79W].
1400 1500 1600 1700 1800
Temperature T [K]

7.5 tough
Diamond MBG 660 Diamond
7.0 MBG 640
Crystal strength
MBG 620
Pressure p [GPa]
6.5
MBG 610
6.0 Cube Cubo - octahedron Octahedron
MBG 600
Berman - Simon line MBG 300
5.5 friable
blocky angular
Solvent/catalyst melting line Shape
5.0
1300 1400 1500 1600 Fig. 13.74. Relative diamond grit shape of the MBG*-
Temperature T [°C] diamond series of General Electric Corporation, USA.
(*Trademark of General Electric Corporation, USA)
Fig. 13.73. Morphological forms of synthetic diamond [96G2].
as a function of pressure and temperature. [92B]
tough
MBG 660
Diamond
MBG 640
MBG 620
Crystal strength
MBG 610
MBG 600
MBG 300
Fig. 13.75. Relative diamond grit toughness of the

MBG*-diamond series of General Electric Corporation,
friable USA. (*Trademark of General Electric Corporation,
60/80 100/200 140/170 200/230 USA) [96G2].
80/100 120/140 170/200 230/270
Mesh size

Pressure
Carbide piston
Carbide die Carbon source Solvent metal
High temperature
Temperature
difference
..............
.....
(20~50 °C)
Low temperature
Pressure medium
Seed crystal
Sumicrystal *)
Heater
Pressure
7
Diamond stable
Metal - Carbon
Pressure p [GPa]
6
eutectic line
Seed Carbon source
line
uilibrium
5 D - G Eq
Temperature difference 20~50 °C

Known as graphite stable
4
1300 1400 1500 1600
Temperature T [°C]
Fig. 13.76. Schematic details of the synthesis conditions for producing large single diamond crystals. *) Sumicrystal
is a trade name of Sumitomo Electric Industries Ltd., Japan [98SI]
6 4.7
5 4.6
Stable region for cubic BN Cubic BN
4.5
4
Pressure p [GPa]
Pressure p [GPa]
4.4
3
4.3
Stable region for
2 hexagonal BN
4.2
1 Hexagonal BN
4.1
0 4.0
500 1000 1500 2000 2500 1300 1400
1100 1200 1500 1600 1700
Temperature T [K] Temperature T [°C]
Fig. 13.77. Pressure temperature space equilibrium Fig. 13.78. Pressure temperature space equilibrium
diagram for hexagonal BN and cubic BN [91C]. diagram for hexagonal BN and cubic BN when using a
40% Al- 60% Mg solvent [94P].

Conventional
abrasive tools
trat
ion Cubic BN tools
50
cen
Hot pressed
Con
100 0 (and most resin

100 and metal bond tools)
150
200
es
asiv
abr
40
e%m
Vol
Volu
50
u
55
me
%p
68 40 ore
s
17
Fig. 13.79. Volumetric relationship
100 between constituents in different grinding
0 wheels [85C].
0 5 25 50 100
Volume % bond
350 111.1 100

Co - powders hot pressed Diamond
340 110.2
Iron/Bronze
COUF
330 109.2 80
COF
Strength / Strength at 25 °C [%]
320 COC 108.2

Tungsten carbide
Rockwell B (equivalent) hardness
310 107.3 60
COD 106.2
300
Brinell hardness
Matrix : Cobalt
290 105.2 40
280 104.1
270 COH 103.1 20
260 102.0
250 100.5 0
25 800 900 1000 1100 1200
240 99.0 Process temperature T [°C]
230 97.5
Fig. 13.81. Strength loss of 40/50 US mesh SDA 100*
220 96.0 diamond when heated for 20 min in three different
750 850 950 1050 matrices. (*Trade name of De Beers Industrial
Temperature T [°C] Diamond Division, S.Africa) [75B1].
Fig. 13.80. Hardness of various cobalt powders hot

pressed at different temperatures.
COUF*= 0.9 ± 0.15 µm; COF*. = 1.25 ± 0.2 µm;
COC*. = 1.60 ± 0.15 µm; COD*. = 1.80 ± 0.2 µm;
COH* . = 3.50 ± 0.5 µm [99E]. (*Trademark of
Eurotungstene Metal Powders Grenoble, France).

5 0.4
4 Tungsten carbide
0.3
α = 6.4⋅10 −6/ °C
Volume expansion [%]
Linear expansion [%]

3
Cobalt
α = 4.9⋅10 −5/ °C 0.2
2
Heating Diamond
α = 1.07⋅10 −5/ °C PCD layer
0.1
α = 3.8⋅10− 6/ °C
1
Cooling
0 200 400 600 800 1000 1200 0 200 400 600 800
Fig. 13.82. Thermal expansion of constituents in Fig. 13.83. Thermal expansion of polycrystalline
Syndite* abrasive element [84B]. (*Trade name of De diamond layer (PCD) and hardmetal backing of
Beers Industrial Diamond Division, S.Africa). Syndite* [84B]. (*Trade name of De Beers Industrial
Diamond Division, S. Africa).
Syndite *) Grade 025 Grade 010,002

900 900
Thermal Thermal
damage zone damage zone
800 800
Temperature T [°C]
Temperature T [°C]
700 700
600 600 Working zone

Working zone
500 500
400 400
0 2 4 6 8 10 0 2 4 6 8 10
Time t [min] Time t [min]
Fig. 13.84. Time temperature parameters in air for Syndite* Grade 025 (left) and Syndite* Grades 010 and 002 (right)
[84B]. (*Trade names of De Beers Industrial Diamond Divisions, S.Africa).

2000 200
150
G - ratio [%]
1500 100
Vrock / Vwear [cm3/mm3]
Syndax 3*) and granite 50
1000 0
PDA211N55 PDA321N55 PDA433N55 PDA657N55
Abrasive type
Wheel specifications: Parameters:
500 Wheel type: D6A2 Wheel speed: 16m/s
Wheel size: 100⋅5mm Feed: 0.1mm/min
Grit size: 230/270# Coolant: Emulsion
Conc: 100
0 Bond: Phenolic resin
500 700 900 1100 1300
Heat treatment temperature T [°C]
Fig. 13.86. Improvement in G-ratio when grinding a
cermet with resin bonded wheels and different grit
Fig. 13.85. Turning tests on granite with heat treated
types [99B1]. (Trademark of De Beers Industrial
Syndax 3* compacts (all 30 min in a closed graphite
Diamond Divisions, S.Africa).
boat and a reducing atmosphere) [88C]. (*Trade name
of De Beers Industrial Diamond Divisions, S.Africa).
22 0.6
21
Removal rate [ mm2/min ]
0.5
Roughness [ µm]
20
0.4
19
18 0.3
0 10 20 30 0 10 20 30
CO Cobalt content wCo[ wt % ] Cobalt content wCo [wt % ]
Fig. 13.87. Influence of cobalt content on the removal Fig. 13.88. Influence of cobalt content on the surface
rate by EDM processing [91M1]. finish by EDM processing [91M1].

2.5
2.0
1.5
G - ratio
Fig. 13.89. The effect of peak current on G-ratio
1.0 for EDM graphite wheel machining of various
3A PCD/PCBN composites [96A]. (*Syndite is a
Peak
trade name of De Beers Industrial Diamond

2A 0.5 Divisions, S. Africa. *Compax and BZN are trade
curr
1A names of General Electric Corporation, USA).

ent
0
Syndite Syndite Compax Syndite Compax BZN BZN
CTB002 CTB010 1600 CTB025 1500 6000 8000
150 10
Wire infeed:30 µm Wire infeed:30µm
τ = 0.23 τ = 0.23
120 8
Average peak - to - valley height [µm]
Cutting rate [ mm 2/min]
90 PCD 002 6
PCD 010
PCD 025
60 Tungsten carbide 4
PCD 002
30 2 PCD 010
PCD 025
Tungsten carbide
0 50 100 150 200 250 0 50 100 150 200 250

Pulse frequency f [kHz] Pulse frequency f [kHz]
Fig. 13.90. Cutting rate as a function of pulse frequency Fig. 13.91. Surface finish as a function of pulse
on wire EDM of various PCD grades and a hardmetal frequency on wire-EDM of various PCD grades and a
(WC- 10 wt% Co) [97S3]. (*PCD002, 010 and 025 are hardmetal (WC- 10 wt% Co) [97S3]. (*PCD 002, 010
trademarks of De Beers Industrial Diamond Divisions, and 025 are trademarks of De Beers Industrial
S.Africa). Diamond Divisions, S.Africa).

Structure H10F
Density: 14.50 g/cm3

Hardness: 1600 HV30
Transverse rupture strength: 3750 N/mm2
Compressive strength: 6300 N/mm2
Structure H10N

Hardness: 1400 HV30
Structure H10C

Hardness: 1210 HV30
Fig. 13.92. Structure of three hardmetal grades with

increasing WC grain size and constant binder content,
9.5-10 wt%. Magnification 1500:1 [99S2]. (H10F,
H10N and H10C are trademarks of Sandvik Hard
Materials AB, Stockholm, Sweden).

Structure H6N

Hardness: 1600 HV30
Structure H10N

Hardness: 1400 HV30
Structure H12N

Hardness: 1300 HV30
Fig. 13.93. Structure of three hardmetal grades with

constant medium WC grain size and increasing cobalt
content: 6, 10, 12 wt%. Magnification 1500:1 [99S2].
(H6N, H10N, H12N are trademarks of Sandvik Hard
Materials AB, Stockholm, Sweden).

Structure S40T
Density: 13.3 g/cm3

Hardness: 1420 HV30
Fig. 13.94. Structure of a 77 wt% WC- 4 wt% TiC-

8 wt% Ta (Nb) C - 11 wt% Co alloy, Tizit*S40T. ]
Magnification 1500:1 [99P]. (*Trademark of Plansee
Tizit, Reutte, Austria)
Al2O3
TiC
TiCN
Co -
enriched
zone
Fig. 13.95. Structure of a coated

indexable metal cutting insert
(Kennametal KC935*) Magnification
2500:1 [99K]. (*Trademark of
Kennametal Inc., Latrobe, USA.

TT115
TT125
Fig. 13.96. Structure of Widia TT115* and TT125*

cermets. Backscattered scanning electron microscopy
[99W]. (*Trademarks of Widia GmbH, Essen,
Germany).
Hardmetal HW P10 Cermet HT − P15

Hard phases Hard phases
WC TiN
(Ti,Ta,W) (C, N)
(Ti,Ta,W) C (Ti,Ta,W, Mo) (C,N)
(Ti,Ta,W, Mo) (C, N)
Binder phase Binder phase

Co,(Ti,Ta,W, C) Co,Ni, (Ti,Ta,W, Mo, C)
Fig. 13.97. Microstructure of conventional hardmetals and cermets. (Schematic description) [99W].

100 2200
Cermet WC - Co - hardmetals
2000
80
Vickershardness HV 30
1800
Ti
Mo 1600
Concentration c [ at %]
60 W
Ta
1400
Shell Core Shell
40 1200
1000
0.4 0.8 1.2 1.6 2.0
20 Mean linear WC intercept [ µm − 1/2 ]
Fig. 13.100. Hall-Petch fit to hardness and WC

arithmetic mean linear intercept data [95R].
0
−1 − 0.6 − 0.2 0 0.2 0.6 1 1.4 1.8 2.2
Rel.position [ µm]
Fig. 13.98. Composition line profile by EDS across a

core-shell grain in a cermet [92G1].
16
0.6 µm
R 2 = 0.9906
0.8 µm
R 2 = 0.9975 WC - Co -hardmetals
1.1 µm 1.3 µm
14 R2 = 0.994 R2 = 0.9975
2.0 µm 5.0 µm
Inv.Vickers hardness 104/HV 30
R 2 = 0.9976 R2 = 0.9965
12 12.0 µm 30.0 µm
R 2 = 0.9945 R2 = 0.9978
10
8
Fig. 13.99. Fit of experimental
6 hardness data of hardmetals with WC
- as received powder from 0.6 to 30
µm FSSS and volume fraction Co-
4 binder from 6 to 25 wt% [96G4].
6 11 16 21 26 31 36 41
Fraction of Co - binder [vol %]

40
WC - Co
89 35
30
Magnetic coercivity H c [ kA m−1 ]

WC - 10 (Co - Ni)
88
Hardness [HRA]
25
20
87 15
WC - 15 (Co - Ni)
10
86 5
0 0.2 0.4 0.6 0.8 1.0

0 1 2 3 4
Ni fraction in (Co - Ni) Inv.intercept 1/dWC [ µm −1]
Fig. 13.101. Variation of hardness of WC-(Co-Ni)

alloys with increasing amounts of nickel [84E]. Fig. 13.102. Magnetic coercivity and WC arithmetic
mean linear intercept (inverse) of commercial WC-Co
hardmetals (showing linear regression fit) [95R].
40 30
WC - Co NPL
Sandvik
25
30
Magnetic coercivity H c [ kA m−1 ]
Fracture toughness [ MN m −3/2 ]
20
20 15
10
10 WC - 10 wt % Co [96 G 4]
R2 = 0.9864 5
WC - 6 wt % Co [95 R]
R2 = 0.9594
0
0 1 2 3 4 5 500 1000 1500 2000 2500
Inv.intercept 1/dWC [ µm −1 ] Vickers hardness HV 30
Fig. 13.103. Magnetic coercivity Hc in dependence on Fig. 13.104. Comparison of NPL and Sandvik data on
inverse arithmetic mean linear intercept 1/dWC [96G4]. the fracture toughness of a range of WC-Co hardmetals
[95R].

14 4
0.5 - 0.9 µmWC
WC - Co WC - Co
13
Transverse rupture strength [ kNmm −2 ]

Fracture toughness [ MN m −3/2 ]
12
3
11 1.4 - 2.0 µmWC
10
2
9
7 1
1300 1500 1700 1900 2100 2300 2500 0 10 20 30
Vickers hardness HV 30 Co content w Co [wt %]
Fig. 13.105. Relationship between fracture toughness Fig. 13.106. The influence of WC-grain size and cobalt
and hardness of fine grained WC-Co alloys [97S1]. content on transverse rupture strength [99S2].
3500 3000
WC - Co Sintered condition
3000 Sintered and HIP - ped
Transverse rupture strength N/mm 2
Transverse rupture strength [N/mm 2 ]
2500
2500
2000 2000
1500
WC - Co - η WC - Co WC - Co - C 1500
1000
Tungsten content of the binder phase [wt %]
20.2 10.3 2.6 1.0
500 1000
4.0 4.25 4.4 4.52 4.89 A02 A04 Pore size: Pore size:
Carbon content of the hardmetal [wt %] Porosity as per ca.30/cm2 ca.50/cm 2
ISO 4505 25 − 150 µm 25 − 150 µm
Fig. 13.107. Transverse rupture strength of a WC- in sintered condition Pores are produced
25 wt% Co alloy as a function of the tungsten content artificially
of the binder phase and the carbon content of the
hardmetal [95K1]. Fig. 13.108. Transverse rupture strength of a WC-9
wt% Co alloy in the sintered and HIP-ed condition with
varying initial porosity [95K1].

Sample no:n i
1 2 3 4 5 6 7 8 9 10 11 12 10000
7000
6000 WC - 6 wt % Co WC - grain - Co
5000 0.7
HIP condition
4000
Transverse rupture strength [ N/mm 2 ]
8000
Compressive strength [ N/mm2 ]

3000
0.5
Sintered condition
2000 Extra fine
0.4 6000
1500
Slope s w
1000 Medium
800 0.2 4000
600 Extra coarse Medium coarse

0.2
400 0 2000
10 20 30 40 50 60 70 80 90 0 5 10 15 20 25
Probability of failure P in% Co content wCo [wt %]
Fig. 13.109. Statistical evaluation of transverse rupture Fig. 13.110. Compressive strength as a function of
strength values [95K1]. cobalt content for different WC-grain sizes [99S2].
700 0.26 8000

Ultra fine, 6 wt % Co WC - Co
WC - Co
Compressive fatigue strength [ N/mm 2 ]
650 0.25 Fine, 6 wt % Co

E
Modulus of elasticity E [ kN/mm2 ]
6000
600 0.24
Poissons ratio ν
ν
550 Coarse, 8 wt % Co
0.23
4000
500 0.22 Coarse, 15 wt % Co
450 0.21 2000

0 5 10 15 20 25 10 102 104 10 6 10
8
Co content wCo [wt %] Number of loading cycles
Fig. 13.111. Modulus of elasticity and Poisson's ratio as Fig. 13.112. Wöhler curves from compressive fatigue
a function of cobalt content [99S2]. testing of different hardmetals. Lower load limit is
250 MPa [99S2].

120 0.25
WC - Co WC - Co
100 ϕ = 90°
0.20
Wear resistance WN [ cm −3]
80 60°
Extra fine
60
Erosion rate [ mg⋅g −1 ]

45°
0.15
40
Medium
0.10
20 30°
Medium coarse
0 5 10 15 20 25
0.05
15°
Fig. 13.113. Wear resistance WN as a function of cobalt

content for alloys with different WC grain sizes. Test
method ASTM B611 [99S2]. 0 5 10 15 20 25 30 35
Fig. 13.114. Particle erosion damage (loss per g of

erodent) of WC-Co alloys as a function of binder
content for a number of incident angles ϕ. [87P].
2000 2000
WC - Co
6F
1600
11F WC - 6 wt % Co
1500
Vickers hardness HV 30
6C 1200
WC - 9 wt % Co
11C
800
1000
Hardness 400
500
−200 −100 0 0 200 400 600 800 1000
Fig. 13.115. Increase in hardness for WC-Co alloys Fig. 13.116. Decrease in hardness for WC-Co alloys in
with a reduction in temperature [83A]. relation to an increase in temperature [95K1].
6F = 6 wt% Co - 1.4 µm WC;
11F = 11 wt% Co - 1.4 µm WC;
6C = 6 wt% Co - 5.0 µm WC;
11C = 11 wt% Co - 5.0 µm WC.

2000 3000
WC ( Ti,Ta,Nb) C - Co WC - 9 wt % Co
1600 2500
Transverse rupture strength [ N/mm2 ]

A
B 2000
1200
C
1500
800
1000
400
500
0 200 400 600 800 1000 0 250 500 750 1000 1250
Fig. 13.117. Decrease in hardness for WC-(Ti Ta Nb) Fig. 13.118. Transverse rupture strength of a WC-9
C-Co alloys in relation to an increase in temperature wt% Co alloy in relation to an increase in temperature
[95K1]. [95K1].
A: WC- 30 wt% (Ti Ta Nb) C- 10 wt% Co;
B: WC- 20 wt% (Ti Ta Nb) C- 9 wt% Co;
C: WC- 10 wt% (Ti Ta Nb) C- 11.5 wt% Co.
1.0 6000
WC - Co WC ( Ti,Ta,Nb) C - Co
0.9
10 wt % Co 5000
Transverse rupture strength[ GPa ]
A
0.8 B
low C
Compressive strength [N/mm 2 ]
4000
0.7 C
high C
0.6 3000
low C
20 wt % Co
0.5
high C 2000
0.4
1.0 2.0 3.0 4.0 5.0 6.0
WC grain size [µm ] 1000
Fig. 13.119. Effect of WC grain size, cobalt and carbon

contents on transverse rupture strength at 1273 K [82S].
0 200 400 600 800 1000 1200
Temperature T [°C]
Fig. 13.120. Change in compressive strength of

different hardmetal alloys in relation to temperature
[95K1].
A: WC-6 wt% Co;
B: WC-20 wt% (Ti Ta Nb) C-9 wt% Co;
C: WC-11.5 wt% (Ti Ta Nb) C-6.5 wt% Co.

924 10
−3
C B A WC - Co WC - Co
770
5 % Compressor proof stress [ MNm−2 ]
10 − 4
616
Creep rate [s −1 ]
462 10 − 5
100 MPa
308 200 MPa
−6
10
154 70 MPa
Compressive stress = 50 MPa
10 − 7
800 850 900 950 1000 1050 1100 1150 1200 1250 6.2 6.4 6.6 6.8 7.0 7.2 7.4 7.6
Temperature T [°C]
Inv.temperature 1/T [10− 4 K −1]
Fig. 13.121. Effect of temperature on 5 % compressive
Fig. 13.122. Arrhenius plot of the steady state creep
proof stress on three WC-Co alloys [67T].
rate for various values of applied compressive stress for
A: 1.4 µm WC- 6 wt% Co;
a WC-37 vol% Co alloy with 2.2 µm grain size. [87L]
B: 1.4 µm WC-11 wt% Co;
C: 1.4 µm WC-20 wt% Co.
7 20
Hardmetal and T = 700 °C T = 1000 °C A
cermet alloys
6
A 15
5
Increase in weight [%]
B
Increase in weight [%]
4
10
3
2
5
1
B
C C
0 5 10 15 0 5 10 15
Time t [h] Time t [h]
Fig. 13.123. Oxidation of hardmetal and cermet alloys in air at 700 °C and 1000 °C.
A: WC- 6 wt% Co;
B: WC- 3 wt% (Ti Ta Nb) C- 9 wt% Co;
C: 85.7 wt% Ti(CN)- 0.8 wt% dopant carbides- 13.5 wt% Co/Ni [92K2].

18 400
T = 800°C WC - Co
WC - (W,Ti,Ta) C - Co
16 TiC - Mo2C - Ni
200
TiCN - Mo2C - Ni/Co
Fracture toughness [MPam1/2 ]
(Standard)
14 TiCN - Mo2C - Ni/Co
Potential EGKE [mV]

(Optimized structure)
0
WC - 9.5 Ni/Cr WC - 9 Co
12
− 200
10
− 400
8
6 − 600
4
400 500 600 700 10−1 1 10 10 2 10 3 10 105
Hot Vickers hardness HV 30 Current density I [µA ⋅cm−2 ]
Fig. 13.124. Hot hardness-fracture toughness Fig. 13.125. Current density/potential curves for WC-
combinations of TiCN-cermets with an optimized Co and WC-Ni/Cr hardmetals [95K1].
structure in relation to standard TiCN-cermets, TiC- Electrolyte: 300 mg Cl–/l ; 200 mg SO4– – /l
Mo2C-Ni cermets and conventional WC- and WC-(W pH-value: 4; test temperature: 60 °C;
Ti Ta) C-hardmetals [93G2]. potential feed: 10 mV/min; flooding with N2 .
25000 800
Natural diamonds CVD - Diamond
Sumicrystal (Ib) Mechanical grade
Optical grade
20000
600
Fracture stress [ MPa ]
Knoop hardness
15000
400
10000
5000 200
0 100 1000 10000 0 0.5 1.0 1.5 2.0 2.5 3.0
Nitrogen content c N [ppm] Layer thickness [mm ]
Fig. 13.126. Knoop hardness of synthetic and natural Fig. 13.127. Fracture stress as a function of layer
diamonds in relation to their nitrogen content [98S1]. thickness of CVD diamond (growth surface in tension).
Mechanical and optical grades [98S2].

1400 5
Diafilms*) Grade:
CVD - Diamond Optical
1200 Mechanical grade Thermal 1
Optical grade 4
Thermal 2
Thermal conductivity λ [ W/mK ]

Thermal 3
Fracture stress [ MPa ]
Natural Type II a
1000 3
800 2
600 1
400 0
0 0.5 1.0 1.5 2.0 2.5 3.0 150 200 250 300 350 400 450
Layer thickness [mm ] Temperature T [K]
Fig. 13.128. Fracture stress as a function of layer Fig. 13.129. Temperature dependence of thermal
thickness of CVD diamond (nucleation surface in conductivity of diafilm* specimens of different grades,
tension). Mechanical and optical grades [98S2]. [98S2]. (*Trade name of De Beers Industrial Diamond
Division, S. Africa).
Fig. 13.130. Cross-section

through a CVD diamond coated
(SiC) tool insert: CVDITE*.
Magnification 300:1. Diamond
coating ca. 50 µm. (*Trade name
of De Beers Industrial Diamond
Division, S. Africa).

Fig. 13.131a - c. Microstructures of

(a) Syndite CTB 002*,
(b) Syndite CTB 010* and
(c) Syndite CTB 025* [99D].
Etched to remove residual solvent/catalyst.
White marker equals 10 µm. (*Trade name
c of De Beers Industrial Diamond Division,
S. Africa).

180 0.50
WC - Co
Sta
inl 0.40
ess
120 ste
els 3 1 2
Cutting speed [ m⋅min −1 ]
: R
eco
Flank wear [mm ]

me 0.30
nen
ded
60 app
lica
Other workpiece materials: tion
are 0.20
Wrought Aluminium a
Nonferrous Heavy Metals
30 Low Carbon Steels
0.10 5
Ni and Co Base Exotics
4
0 150 225 240 270 300 375 450 0 50 100 150 200 250 300 350
Brinell hardness Machined gaps per tool tooth
Fig. 13.132. Areas of application for coated fine grain Fig. 13.133. Skive shaping of case hardened tool tooth
hardmetals in turning operations [97K1]. flanks with various hardmetal grades [97K1].
Material machined: 16MnCr5E, 63 HRC.
Fine grained hardmetal WC-10 wt% Co
1) uncoated, 2) TiN coated.
fW = 0.8 mm/DH, with coolant.
Ultrafine grained hardmetal WC-7.5 wt% Co
3) uncoated, 4) Ti(C,N) coated, 5) Ti(C,N) partly coated,
fW = 0.4 mm/DH, without coolant.
∆s = 0.1 mm/flank, vC = 20 m/min, sloping flank.
40 0.4
30 0.3
Flank wear [mm ]
Tool life [ min ]
20 0.2
10 0.1
0 0
Uncoated Coated Cermet Cermet Cermet
Hardmetal Hardmetal coated uncoated
Fig. 13.134. Finish turning of globular cast iron Fig. 13.135. Copy turning of a gear shaft with coated
GGG40 with cermet cutting tools compared with and uncoated cermet grades [95E]. Workpiece material:
uncoated and coated hardmetal grades [95E]. Cf53V, 650-750 N/mm2; insert: DNMG 150608-4.
Workpiece material: GGG40, 155 HB; insert: TNMG Cutting conditions: cutting speed vC = 300 m/min,
160408. depth of cut ap = 0.5 mm, feed rate f = 0.3 - 0.45 mm,
Cutting conditions: cutting speed vC = 300 m/min, cutting time t = 15 min.
depth of cut ap = 1 mm, feed rate f = 0.2 mm,
without coolant.

500 10
4
Drilling
Workpiece : 100 Cr6 (60 HRC)
400 Drill : 6 mm ∅
Number of impacts [edge strength]

Depth of hole : s = 12 mm 10 3
Number of holes drilled
Cutting speed : vc = 50 m/min

300 Feed : f = 0.02 mm
Coolant : Emulsion, 10% Cobalt enriched
2
10
200
100 10
Non - enriched
0
Standard Fine grain Ultra - fine grain 1.0 2.0 2.5
0 0.5 1.5
WC grain size of alloys Feed [ mm/revolution ]
Fig. 13.136. Drilling test results for TiN-PVD coated Fig. 13.137. Results of edge strength (slotted bar) test
WC- 6 wt% Co alloys. [97D1]. demonstrating the nearly two orders of magnitude
improvement in edge strength due to cobalt enrichment.
The vertical arrows indicate that at least one insert did
not fail at 1200 impacts [81N].
Cutting inserts: Kennametal KC850* SNG433.
(*Trademark of Kennametal Inc., USA).
Cutting conditions: speed 107 - 152 m/min, depth of
cut 2.54 mm, feed rate 0.51 - 2.03 mm/rev.
Material: AISI 41L50 steel, hardness 26 HRC.
10.00 1.2
Workpiece material:epoxy resin reinforced with Test parameters
90% glass roving fabric EPRU 5 Test material:18% Si-Al alloy
α 0 γ 0 λs εr rε ap f vc κr 1.0
3.00 Dimensions: 250∅⋅100mm length
5° 0° 0° 80° 0.8mm 2mm 0.1mm 200m/min 90° Feed rate:0.1 mm/rev
Tool: Depth of cut:0.25 mm
1.00 0.8
Wear - land width [ mm ]
Coolant:Syntilo‘R’
Tool flank wear [ mm ]
Syndite PCD 025

0.60 Syndite PCD 010
Syndax 3 PCD K 10 carbide tool
0.30 PCBN 0.6
Tool life criterion 800 m/min
land wear
= 0.2 mm
0.10 0.4
0.06 K 10 carbide tool
500 m/min
0.03 0.2 CVDITE tool CVDITE tool
800 m/min 500 m/min
0.01
1 3 6 10 30 60 100 300 1000 0 50 100 150 200
Cutting time [ min ] Cutting time [ min ]
Fig. 13.138. Wear-land width as a function of cutting Fig. 13.139. CVDITE* versus tungsten carbide grade
time for various polycrystalline tool materials [88S3]. K10 tool life tests [99D]. (* Trade name of De Beers
(*Trade names and marks of De Beers Industrial Industrial Diamond Division, S. Africa).
Diamond Division, S. Africa).

0.25 0.25
Test parameters
Test material:18% SiAl alloy Medium PDC blanks
Dimensions:250 ∅ ⋅100mm length
Cutting speed:1200m/min Coarse PDC blanks
0.20 0.20
Feed rate:0.1 mm/rev CVDD blanks
Depth of cut:0.25 mm
CVDITE tool Coolant:Syntilo‘R’

0.15 Syndite 010 0.15

CVDITE tool tool
CVDITE tool
0.10 0.10
Cutting speed 670 m min −1

0.05 0.05 Feed 0.13 mm rev −1
Depth of cut 0.5 mm
Syndite 010
tool
0 50 100 150 200 0 5 10 15 20 25 30 35 40 45
Cutting time [ min ] Cutting time [ min ]
Fig. 13.140. CVDITE* versus Syndite* PCD grade 010 Fig. 13.141. Turning MMC (20 % SiC-Al) alloy with
tool life tests [99D]. (* Trade names and marks of De PDC and CVDD tools. [94G2].
Beers Industrial Diamond Division, S. Africa).
0.20
BNX 20 *) BN 100 *)
Breakage Breakage Tool wear
0.15
100
BN 600 *) HM
0.10
80
60
Tool wear [ µm ]
0.05
40
0 2 4 6 8 10
Cutting time [ min ]
20
PCD
Fig. 13.142. Roughing of high speed tool steel [98U].
(* Trademark of Sumitomo Electric Industries, Japan).
Work: SKH 51 (62 HRC), insert: RNGN 0903 M0B. 200 400 600 800 1000
0
Conditions: v = 70 m/min, d = 1.0 mm, f = 0.4 mm/rev,
Length of chipboard edge [ m ]
wet.
Fig. 13.143. The wear of hardmetal and PCD tools
versus linear metres of chipboard edge machined
[85H].

200 150
G ratio PDA 989*)
Power
PDA 768*)
150
PDA 665*)
100
Relative G ratio [%]

Relative value [%]
100
50
50
0
0 PDA 321*) PDA 321N55*) Grit types
Grit types
Fig. 13.145. The effect of particle strength on G-ratio
Fig. 13.144. The effect of nickel cladding on the wet on grinding glass [94BI]. (* Trademark of De Beers
surface grinding of hardmetal [94B1]. (* Trademark of Industrial Diamond Division, S. Africa).
De Beers Industrial Diamond Division, S. Africa).
2.5 50 125
PDA 989*) Force ratio Fn /Ft
2.0 40 100
PDA 768*)
Surface finish R t [µm]
1.5
30 75
Force ratio Fn /Ft
PDA 665*)
1.0
20 50
0.5
10 25
0
Grit types
0 0
B4C SiSiC HPSN RBSN Al2O3
Fig. 13.146. The effect of particle structure on the Workpiece materials
surface finish on grinding glass [94B1]. (* Trademark
of De Beers Industrial Diamond Division, S. Africa).
Fig. 13.147. The influence of ceramic type on G-ratio
and force ratio on surface grinding with a bronze
bonded diamond grinding wheel [97J2].
Wheel diameter = 40 mm, D126, 120/140 US mesh,
100 conc., bronze bond.
3
vs = 20 m/s, Qw = 2 mm /(s mm)

25 1.00
Workpiece:PCD010 Wheel speed: vC = 20 m/s 1000 mesh - 1 pass
Grinding wheel: Contact force: FA = 250 N 1000 mesh - 2 passes
6A2 125×20×4 D46 M 75 Relative contact force:
20 F A’ = 37.5 N/mm 2 2000 mesh - 1 pass
Sharpening cycle: t d = 10 s 0.75 2000 mesh - 2 passes
Cutting edge roughness [µm]
Grinding cycle: ts = 15 s
Surface finish [µm]

15
0.50
10
0.25
5
0
Resin Vitrified Metal 0 300 400 500 600 700
Grinding wheel type Disc speed [rpm]
Fig. 13.148. The effect of wheel bond type on cutting Fig. 13.149. The influence of diamond powder size,
edge roughness of Syndite 010* [92M2]. (* Trade number of polishing passes and polishing disc speed on
name of De Beers Industrial Diamond Division, S. the surface finish of white granite (shore hardness
Africa). 88HS) [92N].
300 700
G - ratio
250 Grinding power [W] 600
500
200
Grinding power [W]
400
G - ratio
150
300
100 Fig. 13.150. Comparison between two cubic boron
200 nitride (nickel coated) grits on surface grinding on M2
high speed steel [98B]. (* Trademark of De Beers
50 100 Industrial Diamond Division, S. Africa).
Wheel: 125 x 6 mm, speed: 34 m/s,
0 0 depth of cut: 0.025 mm, table speed: 15 m/min,
ABN 660*) ABN 860*)
cross feed: 1.5 mm.
Abrasive type [nickel clad]

80
F’n F ’t Fig. 13.151. Effect of cutting speed on grinding forces
when grinding cast iron GGG 70 with an electro plated
single layer CBN wheel [96T1].
60 F ’p Grinding process:
F’n
Grinding forces [N/mm]
vc = 80 m/s - 180 m/s

vft = 4200 mm/min
ae = 2 mm
40 Grinding wheel:
B251 400/21, 6/5/3
single layer
F ’t cubic BN wheel
20 Workpiece:
GGG70
F ’p Coolant:
CMT Wiolan SH 10
0 pKSS = 4 bar
80 100 120 140 160 180
QKSS = 200 l/min
Cutting speed [ m/s]
200 250
Impregnated bits
Hybrid pin bit Speed = 600 rpm
bit load 0.8 tons
200 bit load 0.4 tons
150
Penetration rate [ cm min −1]
bit load 0.2 tons

Penetration [m]
150
Bit change due to wear
100 (108m)
100
Bit change when broken and
sheared zones hit (74m)
50
Bit change when fine grained tuff hit (38m) 50
0 10 20 30 40 0 5 10 15 20 25 30
Drilling time [h] Depth drilled [m]
Fig. 13.152. Comparison of penetration rates for a Fig. 13.153. Variation of rate of penetration with depth
Syndax 3* hybrid bit and a conventional impregnated drilled at three different bit loads in pennant sandstone
diamond bit [93S1]. (* Trademark of De Beers [88C].
Industrial Diamond Division, S. Africa).

6 - anvil type tools
Typical
dimensions, [mm]
D
70 20
90 25
120 35
175 50
∅D
Belt type tools, straight bore Belt type tools, V - shape bore
∅D1 ∅D1
∅ d1 30° ∅ d1
H1 H2 H1 H2
ϕ ϕ
60° ∅D2 ∅D2
90°
Typical dimensions, mm Typical dimensions, mm

d1 H1 D1 D2 H 2 d1 H1 D1 D2 H 2
40 82 127 83 76 40 100 155 95 80
50 110 155 100 95 60 150 250 150 120
60 120 185 120 110 75 185 290 160 125
80 160 255 160 145 80 250 325 165 145
100 180 280 210 200
125 250 335 250 225
Fig. 13.154. Typical dimensions of dies and anvils used in the production of synthetic diamond/ cubic boron nitride
grits and polycrystalline products. Data supplied and property of A.B. Sandvik Hard Materials, Sweden [99S4].

Diamond Diamond Laser diode

Diamond
Sapphire submount
Germanium
Copper heat - sink
ZnS Junction
Heat - sink Laser diode chip

ZnSe
main body Diamond submount
GaP
0.1 1 10 100
Wavelength [µm]
Fig. 13.155. Transmission spectral range of diamond Fig. 13.156. An example of a diamond plate used as a
compared with other optical materials [93S2]. heat spreader in a laser diode package [93S2].

13 Hard materials 13-185
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Field, J.E., (ed.); London, UK: Academic Press Ltd.
92C Clark, I.E., Mackenzie, K.A., Tomlinson, P.N.: Ind. Diamond Rev. 52 (1992) 186.
92D De-Beers Report: Ind. Diamond Rev. 52 (1992) 26.
92F Field, J.E. (ed): The Properties of Natural and Synthetic Diamond; London, UK: Academic
Press Ltd., 1992.
92G1 Gee, M.G., Reece, M.J., Roebuck, B.: J. Hard Mater. 3 (1992) 119.
92G2 General Electric Company, USA: Brochure SMD 93-204R (1992).
92G3 General Electric Company, USA: Brochure SMD 37-468R (1992).
92H Harris, J.W.: The Properties of Natural and Synthetic Diamond, Field, J.E. (ed.); London,
UK: Academic Press Ltd., 1992, p. 374.
92J Jones, B. L.: Ind. Diamond Rev. 52 (1992) 175.
92K1 Kolaska, H.: Powder Metall. Int. 24 (1992) 311.
92K2 Kolaska, H., Dreyer, K.: 20 Jahre Zerspanungsforschung-Uni Dortmund, Germany, 4 (1992) 1.
92L1 Leitner, G., Jaenicke-Rössler, K., Wagner, H.: Conf. Adv. in Hard Materials Prod. 13-1
(1992); UK: EPMA,.
92L2 Lindlbauer, A., Haubner, R., Lux, B.: Int. J. Refract. Met. Hard Mater. 11 (1992) 247.
92M1 Moser, G.: Conf. Adv. in Hard Materials Prod. 9-1 (1992); UK: EPMA.
92M2 Muhliskenter, I.: Ind. Diamond Rev. 52 (1992) 75.
92N Nakayama, M., Kudo, K., Sakakibara, T., Nomura, H.: Ind. Diamond Rev. 52 (1992) 250.
92P Pastor, H., Bonneau, M., Pillot, J.: Conf. Adv. in Hard Materials Prod. 6-1 (1992); UK:
EPMA.
92R Roebuck, B., Coles, B.: Conf. Adv. in Hard Materials Prod. 30-1 (1992); UK: EPMA.
92S1 Sato, Y., Kamo, M.: The Properties of Natural and Synthetic Diamond 2 (1992) 423; Field,
J.E. (ed.); London, UK: Academic Press Ltd.
92S2 Sen, P.K.: Ind. Diamond Rev. 52 (1992) 228.
92T Tomlinson, P.N.: The Properties of Natural and Synthetic Diamond 4 (1992) 637; London,
UK: Academic Press Ltd.
93B Buys, R.: Ind. Diamond Rev. 53 (1993) 25.
93C Clark, I.E.: Ind. Diamond Rev. 53 (1993) 73.
93D1 De Beers Industrial Diamond Division: Ind. Diamond Rev. 53 (1993) 82.
93D2 De Beers Industrial Diamond Division: Brochure NH 40001093 (1993).
93E Edwards, R.: Cutting Tools (1993); London, UK: The Inst. of Materials.
93F Friedrichs, K.: Met. Powder Rep., Dec. (1993) 26.
93G1 General Electric Company, USA: Brochure GES-93-1025 (1993).
93G2 Gille, G.: 6th Int. Tungsten Symp. - W93 - (1993); London, UK: Int. Tungsten Industry Ass.
93G3 General Electric Company, USA: Brochure GES-85-606, Revised 93 (1993).
93H Haubner, R., Lux, B.: Diamond Relat. Mater. 2 (1993) 1277.
93K Knotek, O., Löffler, F., Kramer, G.: Proc. 13th Plansee Seminar, Reutte 3 (1993) 236.
93P Przyklenk, K.: Ind. Diamond Rev. 53 (1993) 192.
93S1 Sheppard, N., Dolly, B.: Ind. Diamond Rev. 53 (1993) 309.
93S2 Sussman, R.S.: Ind. Diamond Rev. 53 (1993) 63.
93Y Yohe, W.C.: Proc. 13th Plansee Seminar, Reutte 2 (1993) 151.
94B1 Bailey, M.W., Juchem, H.O.: Ind. Diamond Rev. 54 (1994) 8.

94B2 Bundy, F.P.: Conf. Proc. Am. Inst. Phys. 309 (1994) 495.
94C Clark, E., Jennings, M.P.: Ind. Diamond Rev. 54 (1994) 63.
94K Kolaska, H.: Spanende Fertigung, 7, Dec. 1994; Essen, Germany: Vulkan-Verlag.
94P Park, J.K., Park, S.T., Eun, K.Y.: Int. J. Refract. Met. Hard Mater. 12 (1993–1994) 224.
94S Spanitz, J.F.: General Electric Company, USA: Brochure GES-94-1057 (1994).
94U Uhrenus, B.: Int. J. Refract. Met. Hard Mater. 12 (1993–1994) 121.
94V Vollmeyer Werke Maschinenfabrik GmbH, Biberach, Germany, Brochure (1994).
95B Brookes, K.J.A.: Met. Powder Rep., Dec. (1995) 22.
95E Ettmayer, P., Kolaska, H., Lengauer, W., Dreyer, K.: Int. J. Refract. Met. Hard Mater. 13
(1995) 343.
95G1 General Electric Company, USA: Brochure GES-95-1074 and GES-96-1095.
95G2 Grewe, H., Kolaska, H.: Metall (Berlin) 49 (1995) 326.
95K1 Kolaska, H. (ed.): Powder Metall. of Hardmetal, Lectures (1995); UK: EPMA.
95K2 Kolaska, H., Weith, W.: Metall (Berlin) 2 (1995) 104; 5 (1995) 355.
95L1 Lassner, E.: Int. J. Refract. Met. Hard Mater. 13 (1995) 35.
95L2 Lassner, E., Schubert, W.D.: Int. J. Refract. Met. Hard Mater. 13 (1995) 111.
95R Roebuck, B.: Int. J. Refract. Met. Hard Mater. 13 (1995) 265.
95S Spriggs, G.E.: Int. J. Refract. Met. Hard Mater. 13 (1995) 241.
95V Vadusdi, K.: Int. J. Refract. Met. Hard Mater. 13 (1995) 15.
96A Asprinwall, D.K., Thoe, A.T.B., Wu, R.S.L., Barr, V., Heckenjaan, P., Blocker, T.: Conf.
Adv. in Hard Materials Prod. (1996) 551; UK: EPMA.
96B1 Berger, L-M., Langholf, E.: Conf. Adv. in Hard Materials Prod. (1996) 53; UK: EPMA.
96B2 Brookes, K.J.A.: World Directory and Handbook of Hardmetals and Hard Materials, 6th Ed.,
(1996); International Carbide Data, 33 East Barnet, Herts, UK.
96D De Beers Industrial Diamond Division, S. Africa: Brochure (1996).
96E1 Ermel, E.: Conf. Adv. in Hard Materials Prod. (1996) 127; UK: EPMA.
96E2 Exner, H.E.: Conf. Adv. in Hard Materials Prod. (1996) 255; UK: EPMA.
96G1 General Electric Company, USA: Brochure GES 96-1098 (1996).
96G2 General Electric Company, USA: Brochure GES 96-1104 (1996).
96G3 Gille, G., Szesny, B.: 7th Int. Tungsten Symp. (1996) 150; London, UK: Int. Tungsten
Industry Ass.
96G4 Gille, G., Leitner, G., Roebuck, B.: Conf. Adv. in Hard Materials Prod. (1996) 195; UK:
EPMA.
96K Komage GmbH, Germany: Brochure 5/1996 (1996).
96L Lavergne, O., Hodaj, F., Allibert, C. H.: Conf. Adv. in Hard Materials Prod. (1996) 153; UK:
EPMA.
96M1 Mc Candlish, L.E., Seegopaul, D.: Met. Powder Rep., April (1996) 16.
96M2 Müller Sebert, W., Wörner, A., Fuchs, F., Wild, C., Koidl, P.: Appl. Phys. Lett. 68 (6) (1996)
759.
96P Pastor, H.: Conf. Adv. in Hard Materials Prod. (1996) 3; UK: EPMA.
96R1 Roebuck, B.: Int. J. Refract. Met. Hard Mater. 14 (1996) 419.
96R2 Roebuck, B., Gee, M.G., Morrell, R.: Powder Metall. 39 (1996) 213.
96T1 Tönshoff, H.K., Falkenburg, Y.: Ind. Diamond Rev. 56 (1996) 115.
96T2 Tsuda, K., Ikegaya, A., Isobe, K., Kitagawa, N., Nomura, T.: Conf. Adv. in Hard Materials
Prod. (1996) 45; UK: EPMA.
97B1 Berg, H. van den, König, U., Westphal, H., Sollke, V., Taberksy, R.: Workshop:
Verschleißschutz von Werkzeugen f. Zerspanung und Umformtechnik; Hannover, Germany:
EMO, Sept. 1997.
97B2 Brozek, V., Dufek, V., Vyskocil, J.: Proc. 14th Plansee Seminar, Reutte 3 (1997) 264.
97D1 Dreyer, K.: Hartbearbeitungs-Forum; Frankfurt, Germany: Precima, 1997.

97D2 Dreyer, K., Daub, W., Holzhauer, H., Orths, S., Kassel, D., Rödiger, K.: Symp. Hartstoffe,
Hartschichten, Werkzeuge, Verschleiß 13/14 (1997), DGM/FPM, Germany.
97F Friedrichs, K.: Proc. 14th Plansee Seminar, Reutte 2 (1997) 552.
97G General Electric Company, USA: Brochure GES 97-1111 (1997).
97H1 Hartmann, P., Haubner, R., Lux, B.: Proc. 14th Plansee Seminar, Reutte 3 (1997) 129.
97H2 Haubner, R., Schubert, W.D., Lux, B.: Proc. 14th Plansee Seminar, Reutte 3 (1997) 16.
97J1 Jia, K., Fischer, T.E.: Mater. Res. Soc. Symp. Proc. 457 (1997) 303.
97J2 Juchem, H.O.: Ind. Diamond Rev. 57 (1997) 114.
97K1 Kassel, D., Schaaf, G., Dreyer, K.: Met. Powder Rep., April (1997) 16.
97K2 Kesong, Z., Tongchun, K., Mingjiang, D., Dezheng, W.: Proc. 14th Plansee Seminar, Reutte 3
(1997) 31.
97K3 Klages, C-P., Fryda, M., Matthee, T., Schäfer, L., Dimigen, H.: Proc. 14th Plansee Seminar,
Reutte 3 (1997) 1.
97K4 Konyashin, I., Loeffler, J., Bill, J., Aldinger, F.: Proc. 14th Plansee Seminar, Reutte 3 (1997)
41.
97L1 Lassner, E., Schubert, W.D.: Section 26-Tungsten, Handbook of Extractive Metallurgy,
Habashi, F. (ed.); Weinheim, Germany: Wiley-VCH, 1997.
97L2 Leitner, G., Gestrich, T.: Proc. 14th Plansee Seminar, Reutte 2 (1997) 86.
97L3 Lugscheider, E., Knotek, O., Barimani, C., Guerreiro, S.S.: Proc. 14th Plansee Seminar,
Reutte 3 (1997) 223.
97N Nakawara, S., Fujisawa, T., Takaoka, H., Tanase, T.: Proc. 14th Plansee Seminar, Reutte 2
(1997) 54.
97S1 Schubert, W.D., Neumeister, H., Kinger, G., Lux, B.: Proc. 14th Plansee Seminar, Reutte 4
(1997) 241.
97S2 Spačil, J.: Proc. 14th Plansee Seminar, Reutte 2 (1997) 338.
97S3 Spur, G., Appel, S.: Ind. Diamond Rev. 57 (1997) 124.
97Y Youseffi, M., Menzies, I.A.: Powder Metall. 40 (1997) 62.
98B Bailey, M.W., Juchem, H.O.: Ind. Diamond Rev. 58 (1998) 83.
98C1 Clark, I.E., Sen, P.K.: Ind. Diamond Rev. 58 (1998) 40.
98C2 Cobalt Facts: London, UK: Cobalt Development Institute, 1998.
98C3 Collins, J.L.: Ind. Diamond Rev. 58 (1998) 90.
98C4 Cook, M.W.: Powder Metall. 41 (1998) 87.
98D Dwan, J. D.: Powder Metall. 41 (1998) 84.
98E Eurotungstene Metal Powders, France: Brochure - NEXT (1998).
98G General Electric Company, USA: Brochure GES-98-1164 (1998).
98H Hagland, S., Ågren, J.: Acta Mater. 48 (1998) 2801.
98K Kennametal Inc., USA: Brochure A93-350(10)A5 (1998).
98N Nyborg, L., Carlström, E., Warren, A., Bertilsson, H.: Powder Metall. 41 (1998) 41.
98S1 Sumitomo Electric Industries Ltd; Japan: Brochure EV-29R3 (1998-1).
98S2 Sussman, R.S., Brandon, J.R., Coe, S.E., Pickles, C.S.J. Sweeney, C.G., Wasenczuk, A.,
Wort, C.J.H., Dodge, C.N.: Ind. Diamond. Rev. 58 (1998) 69.
98U Uesaka, S., Fukaya; T., Shiraishi, J., Nakai, T.: Sumitomo Electr. Ind. Tech. Rev. A 5 (1998)
95.
98W Weber, G., Burckhardt, S.: Ind. Diamond Rev. 58 (1998) 111.
99B1 Bailey, M.W., Garrord, R., Juchem, H.O.: Ind. Diamond Rev. 59 (1999) 10.
99B2 Blossom, P.: Private Communication, (1999), De Beers Industrial Diamond Division, UK.
99C1 Charmilles Technologies SA, Geneva, Switzerland: Brochure (1999).
99C2 Clark, I.E., Bex, P.A.: Ind. Diamond Rev. 59 (1999) 43.
99D De Beers Industrial Diamond Division, S. Africa: Catalogue and Product Chart (1999).
99E Eurotungstene Metal Powders, France: Brochure, Metal Powders for the Diamond Tool
Industry (1999).
99F Dr. Fritsch KG, Germany: Brochure, Sintering Metal Powders for the Diamond Tool Industry
(1999).
99J Johnson Matthey Metal Joining UK: Brochure 1100: B (1999).

99K Kennametal Inc., Latrobe, USA (1999).

99L Jakob Lach GmbH & Co KG, Hanau, Germany: Brochure (1999).
99P Plansee Tizit GmbH, Reutte/Reutte, Tyrol, Austria (1999).
99R Roebuck, B., Bennett, E., Lay, L., Merrel, R.: Measurement and Good Practice Guide, No. 9
(1999), National Physical Laboratory, London, UK.
99S1 Sandvik, A.B.: Hard Materials, Sweden: Catalogue, H-9097 ENG (1999).
99S2 Sandvik, A.B.: Hard Materials, Sweden: Catalogue H 9100b-ENG (1999).
99S3 Sandvik, A.B.: Hard Materials, Sweden: Catalogue, H-9096 ENG and H-9076 ENG (1999).
99S4 Sandvik, A.B.: Hard Materials, Sweden: Catalogue H-3002 ENG (1999).
99S5 Sandvik, A.B.: Hard Materials, Sweden: Catalogue H-6043 ENG, H-6044 ENG, H-6045
ENG, H-6048 ENG (1999).
99T1 TecVac, Cambridge, UK: Catalogue (1999).
99T2 Toolmasters Ltd, Middlesex, UK: Brochure (1999).
99W Widia GmbH, Essen, Germany (1999).

Ref. p. 14-38] 14 Intermetallic materials 14-1
14 Intermetallic materials
G. SAUTHOFF
14.1 Introduction
Intermetallics is the short and summarising designation for the intermetallic phases and compounds which
result from the combination of two or more metals and the crystal structures of which are different from
those of the constituents [95S1]. Intermetallics have been applied since the beginning of metallurgy,
Table 1. Recently intermetallics have found an increasing interest in materials science and technology
with respect to use as magnets and for applications at high temperatures. It is expected that a new class of
high temperature structural materials is developed on the basis of intermetallics. It should be noted that
intermetallics with particular physical properties have given rise to developments of new functional
materials much earlier. The brittle nature of most intermetallics requires powder metallurgical processing.
This chapter gives basic information and data of recent developments of new intermetallic structural
materials which are applied currently or are expected to be applied in the near future.
Table 1. Some applications of intermetallics, past and present [89S1].
Since approx. Material or process Phase Application Ref.

2500 B.C. Cementation Cu3As Coating of bronze tools 77W
etc. (Egypt, Anatolia,
Britain)
100 B.C. Yellow brass CuZn Coins, ornamental parts 55G
(Rome)
0 High tin bronze Cu31Sn8 Mirror (China) 77W
600 Amalgam Ag2Hg3 + Sn6Hg Dental restorative (China) 77W, 90W
1500 Amalgam Cu4Hg3 Dental restorative 76P, 77W, 90W
(Germany)
1505 Amalgam Sn8Hg Mirror surface (Venice) 77W
1540 Type metal SbSn Printing 77W
1910 Acutal (Cu,Mn)3Al Fruit knife (Germany) 89H
1921 Permalloy Ni3Fe High permeability 51B
magnetic alloy
1926 Permendur FeCo(-2V) High permeability 51B, 61C
magnetic alloy
1931 Alnico NiAl-Fe-Co Permanent magnet 69D
material
1935 Sendust Fe3(Si,Al) Magnetic head material 80Y
1938 Cu-Zn-Al, Cu-Al-Ni CuZn-Al, Shape memory alloys 90H
(Cu,Ni)3Al
1950 Pack aluminide NiAl, CoAl Surface coating for 91N
coating protection from
environment
1956 Kanthal Super, MoSi2 Electric heating elements 58F, 58H
Mosilit

14-2 14 Intermetallic materials [Ref. p. 14-38
Since approx. Material or process Phase Application Ref.

1961 A15 compound Nb3Sn Superconductors 77W, 86G
1962 Nitinol NiTi Shape-memory alloy 74D, 90H
1967 Co-Sm magnets Co5Sm Permanent magnets 77W, 86B, 91S
14.2 Topical intermetallic materials

The attractive physical properties of various intermetallic phases initiated developments of important
functional materials already in the past.
The outstanding mechanical properties of intermetallic phases - in particular their high strength
besides oxidation resistance at high temperatures - resulted in promising intermetallic materials
developments only in the recent past because the low ductility and toughness of most intermetallic phases
at low temperatures makes processing and design of components difficult. Even the most advanced
successful developments of intermetallic structural materials are only on the brink of commercialisation
since after the technical feasibility being established the economic success will still have to be
demonstrated. Table 2 lists the major intermetallic materials of present interest which are being applied
or ready for applications.
The following sections concentrate on new intermetallic materials for structural applications which are
based on various aluminide phases, i.e. titanium aluminides, iron aluminides and nickel aluminides, or on
the silicide MoSi2. Various other intermetallic phases have been or are being considered for structural
alloy development [95S1], but have not yet left the laboratory stage and are not included in this chapter.
Table 2. Intermetallic materials which are applied or ready for application.
Alloy Majority phase Application Ref.

Functional materials
(physical)
A15 compounds Nb3Sn Superconductor 95S6
Cu-Al-Ni β-Cu-Al-Ni Shape-memory alloy 95S3
Cu-Zn-Al β-Cu-Zn-Al Shape-memory alloy 95S3
Fe-Al-Si Fe2Si Thermoelectric generator 98O
Rare earth magnet SmCo5 Permanent magnet 97Y, 98B2; see
materials Sm2Co17 section 9.3
Sm2Fe17(C,N)
Nd2Fe14B
GaAs GaAs Transistor, laser diode, 95E, 95M1
optoelectronic device, solar cell,
acoustoelectric device
Kanthal Super, Mosilit MoSi2 Electric heating elements 96D1
Ni-Ti NiTi Shape-memory alloy 95S3
Permalloy Ni3Fe High permeability magnetic alloy 95S5; see
section 9.2
Permendur FeCo High permeability magnetic alloy 95S5
Sendust Fe3(Si,Al) Magnetic head material 96T1
Silicide thin film Transition metal Microelectronics, silicon integrated 95M3, 95K1
alloys silicides, precious circuits
metal silicides
Terfenol-D (Tb,Dy)Fe2 Giant magnetostrictive actuator 95G
Thermoelectrics Bi2Te3 Thermoelectric generator 95V1

Alloy Majority phase Application Ref.

Functional materials
(chemical)
M-Cr-Al-Y NiAl Coating 95N
Pt aluminide Pt3Al Coating 98K4
Rare earth hydrides LaNi5 Hydrogen storage, rechargeable 95S4, 96K2,
battery 97Y
Silicides transition metal coating 95K1
silicides
Structural materials
(under development)
Advanced nickel Ni3Al High temperature wear resistant Section 14.4.4.2
aluminide alloys components
Alpha-2 titanium Ti3Al Jet engine components etc. Section 14.4.2.2
aluminide alloys
B2 nickel aluminide NiAl Gas turbine and automotive Section 14.4.4.3
alloys components
Gamma titanium TiAl Aircraft, jet engine, automotive Section 14.4.2.3
aluminide alloys components etc.
Iron aluminide alloys Fe3Al, FeAl Chemical engineering Section 14.4.3
Molybdenum MoSi2 Aircraft, automotive components Section 14.4.5
disilicide alloys etc.
A variety of powder metallurgical techniques are used successfully to produce intermetallic phases and
composites [94K4, 96W, 96S7, 98K2]. Table 3 lists the processes used with examples of application. It
should be noted that the success of densification depends on both the process and the material as is
exemplified by available data [96S7]. This applies in particular to reactive sintering techniques which
lead to Kirkendall diffusion induced porosity.
Table 3. Powder metallurgy processes and examples of materials processed.
Process Material processed Ref.

Powder production:
Cryo-milling NiAl 94K4
Electrode induction melting, gas TiAl 98G4
atomisation (EIGA)
Electron beam rotating atomisation SUperalloys 89B
(EBRP)
High pressure gas atomisation Fe-Al, LaNi5 97M5, 97P3, 98T3
(HPGA)
Hydrogenation, decomposition, Nd-Fe-B, Sm2Fe17 , Ti 95T1, 96M5, 96S2
desorption, recombination (HDDR)
Inert gas atomisation (IGA) Fe3Al, Ni3Al, NiAl, TiAl 89B, 96G1
Mechanical alloying (MA), milling FeAl, MoSi2, Ni3Al, NiAl, TiAl 89B, 96G1, 98K2
Melt spinning, melt extraction FeAl, Nd-Fe-B 89B
Plasma atomisation NiAl 96G1
Plasma inert gas atomisation TiAl 92G
(PIGA)

Process Material processed Ref.

Plasma rotating electrode process Fe3Al, Ni3Al, Ti3Al, TiAl 96G1
(PREP)
Rapid solidification rate atomisation Superalloys 89B
(RSR)
Reactive synthesis (RS) Fe3Al, Ni3Al, NiAl, TiAl 96G1
Rotating electrode process (REP) superalloys 89B
Vacuum atomisation (VA) Ni3Al, NiAl 89B, 96G1
Consolidation:
Cold isostatic pressing - hot Fe3Al 96G1
isostatic pressing (CIP-HIP)
Cold isostatic pressing - hot TiAl 97S3
extrusion reactive sintering (CIP
reactive sintering)
Cold isostatic pressing -vacuum Al 98H2
sintering process (CIP-sinter)
Combustion synthesis, self- Fe3Al, MoSi2, Ni3Al, NiAl, TiAl 94D, 96S7, 97N1,
propagating high temperature 98G2, 98D2
synthesis (SHS)
Explosive compaction Ti3Al 96G1
Gas atomisation reaction synthesis Al 94F
(GARS)
Hot extrusion Fe3Al, FeAl, Ni3Al 89B, 96G1
Hot isostatic pressing (HIP) Fe3Al, Ni3Al, NiAl, Ti3Al, TiAl 89B, 96G1
Inert gas hot pressing (IGHP) MoSi2 89B, 96G1
Metal foam process Al 98Y3
Nanocrystallisation Ni3Al, TiAl 94X, 97T, 98V3
Powder injection molding (PIM), MoSi2, NiAl, TiAl 89B, 96G1, 97K1,
metal injection molding (MIM) 97P2
Rapid omnidirectional compaction Ni3Al, TiAl 89B, 96G1
(ROC or pseudo-HIP)
Reactive HIPing (RHIP) Fe3Al, Ni3Al, NiAl, Ti3Al, TiAl 94D, 96G1, 96S7
Reactive hot pressing NiAl, TiAl 94D
Reactive shock synthesis (RSS) Ni3Al, NiAl 94D
Reactive sintering (RS) Fe3Al, Ni3Al, NiAl, Ti3Al, TiAl 94D, 96G1, 96S7
Reactive spray deposition (RSD) Ni3Al, NiAl 94D
Thermal spraying, spray forming MoSi2, Ni3Al, NiAl, Ti3Al, TiAl 89B, 94J, 96G1, 96S7,
97H3, 97L1, 98V4
Vacuum hot pressing (VHP) Fe3Al, MoSi2, Ni3Al, NiAl, TiAl 96G1
XD® process NiAl, CoAl, TiAl, MoSi2, Al22Ti8Fe3 94K4

14.4 Intermetallic materials for structural high temperature

applications
14.4.1 Basic properties of constituent phases

Various intermetallic phases offer a high potential for the developments of new structural materials for
high temperature applications and have been selected as bases for alloy developments [95S1]. Basic
properties of primary importance for any application are: low density - in view of developing lightweight
materials, high melting temperature - in view of high temperature stability, and alloy fabrication as well
as elastic modulus and diffusion coefficient - in view of their effects on the mechanical behaviour at low
and high temperatures, respectively. Representative data for the selected intermetallic phases are shown in
Table 4.
Table 4. Basic properties of major constituent phases: crystal structure with Strukturbericht symbols
[91V2], density ρ at room temperature, melting temperature Tm (with prior disordering temperature in
brackets if applicable), Young’s modulus E at room temperature, and self-diffusion coefficient D at 4Tm/5
(extrapolations in brackets).
Phase Crystal ρ Ref. Tm Ref. E Ref. D4Tm/5 Ref.

structure g/cm3 °C GPa m2/s
Fe3Al D03 6.72 90L2 1520- 90M 180 97H4 10-13 97M4
1430 (Fe, Al)
(560)
FeAl B2 6.10- 86H 1310 90M 244-267 86H 10-14 97M4
5.56 (Fe, Al)
MoSi2 C11b 6.24 93K, 2080 93K 440 93K ---
93P1
Ni3Al L12 7.50 90L2 1383 91V1 180 89S3 3⋅10-16 98K3
(Ni)
≈10-16
(Al)
NiAl B2 6.50- 95M2 1638 90M 225-235 87H 2⋅10-14 96M3
5.35 (Ni)
Ti3Al D019 4.15-4.7 85L 1480- 90M, 144-149 98Y2 (2⋅10-15) 96R4
1680 94K1 (Ti)
(1210)
TiAl L10 3.76 85L 1480 90M 176-185 98Y2 3⋅10-16 99H3
(Ti)
14.4.2 Titanium aluminide alloys

The low density of Ti-Al alloys makes them most attractive for the development of lightweight materials
and correspondingly the titanium aluminides Ti3Al and TiAl were selected early as candidate phases for
extended high temperature materials developments [85L]. Table 5 compares Ti3Al-base and TiAl-base
alloys with conventional Ti alloys and Ni-base superalloys. The data indicate highly attractive specific
properties (per unit density). Presently the titanium aluminide alloys are the most advanced intermetallic
materials, which are considered for various automotive and aerospace applications because of their low
density.

Table 5. Properties at room temperatur , RT, or higher temperature of alloys based on the titanium
aluminides Ti3Al and TiAl in comparison to conventional titanium alloys and nickel-base superalloys
[80M, 85L, 89K, 90K, 91F, 95H2].
Property Ti-base Ti3Al-base TiAl-base Superalloys

Structure A3/A2 D019/A2/B2 L10/D019 A1/L12
Density [g/cm3] 4.5-4.6 4.1-4.7 3.7-3.9 7.9-9.1
Thermal conductivity 21 7 22 11
[W/(m K)]
Young's modulus [GPa] 95-115 100-145 160-180 195-220
at RT
Yield strength [GPa] at 380-1150 700-990 400-650 250-1310
RT
Tensile strength [MPa] 480-1200 800-1140 450-800 620-1620
at RT
Temperature limit [°C] 600 760 1000 1090
due to creep
Temperature limit [°C] 600 650 900 1090
due to oxidation
Tensile strain to fracture 10-25 2-26 1-4 3-50
[%] at RT
Tensile strain to fracture 12-50 10-20 10-60 8-125
[%] at high temperature
Fracture toughness KIc high 13-42 10-20 25
[MPa m1/2]
at RT
14.4.2.1 Phase diagrams
Various versions of the binary Ti-Al phase diagram are available [90M], which are still under discussion
because of conflicting results on the various phase equilibria - see [94K1, 96P1, 97Z2, 99F]. The phase
diagram in Fig. 14.1 considers recent results. The alloy developments on the base of the titanium
aluminides have made use of alloying with further elements, in particular Nb, V, and Cr. The respective
ternary phase diagrams are shown in Figs. 14.2 - 14.4. Informations on other ternary systems are found in
[97P1, 98H3].
1600
Ti1-x Al1+x
β - Ti Ti5Al11
Ti2Al5
Temperature T [°C]
1400
α-Ti
1200
γ - TiAl
r/h - TiAl 2
α 2 - Ti 3Al
1000
α - Ti TiAl 3
Fig. 14.1. Ti-Al phase diagram
[94K1, 00O, 01S].
Ti 10 30 50 70 90 Al
Al content c [at.%]

T = 1000°C Ti
β - Ti α - Ti
20 80
Ti3Al
Ti c
%]
ont
.
Nb [at
40 60
ent
ct
c Ti
ten
TiAl
[at.
c on
%]
β
Nb
60 40 Al Ti
2
Ti2Al5
Al 3Ti
80 20
Fig. 14.2. Isothermal section of the Ti-Al-Nb
(Nb,Ti)Al 3 phase diagram at 1000 °C [98H4] - see also
[97P1, 98W, 98S1, 98T2].
Nb 20 Nb2 Al 40 60 80 Al
Al 3Nb
Al content cAl [at.%]
Nb3 Al
T = 900°C Ti
β - Ti α - Ti
Ti3Al
20 80
Ti c
.%]
o
[w t
TiAl
nte
40 60
nt
V
w
w Ti
ent
β2 Al 2Ti
[w t
ont
. %]
Vc
60 40
Al 3Ti
80 20
Fig. 14.3. Isothermal section of the Ti-Al-V

phase diagram at 900 °C [94A2].
V 20 40 δ 60 Al 3V 80 Al
Al content wAl [wt.%]

T = 1025°C Ti
β - Ti
α - Ti
20 80
Ti3Al
Ti c
%]
ont
[at.
40 60
ent
Cr
c
c Ti
ent
TiAl
[at.
ont
%]
Cr c
60 40
α - TiCr2 TiAl2
γ - TiCr2 Ti2Al5
(Ti,Cr)Al 3
80 20
(Nb,Ti)Al 3 Fig. 14.4. Isothermal section of the Ti-Al-Cr

phase diagram at 1025 °C [97P1] - see also
Cr 20 40 60 CrAl4 80 Al [97X1, 98H3].
Al content cAl [at.%] Cr9 Al17
14.4.2.2 Ti3Al-base alloys
14.4.2.2.1 Compositions and applications
Various Ti3Al-base alloys have been developed which contain niobium as major alloying element and
further elements for obtaining an optimised balance of strength, deformability, toughness and oxidation
resistance. The alloys are two-phase or three-phase and contain additional phases besides the phase Ti3Al,
which is known as the α2 phase. The usual additional phases are the β phase, which is Ti-rich and which
has the b.c.c. structure or is ordered with B2 structure, the orthorhombic O phase based on Ti2AlNb,
and/or the ω-type phase Ti4Al3Nb with B82 structure [92B1, 95B]. In addition, Ti3Al-base alloys have
been used as matrices for intermetallic matrix composites, which rely primarily on strengthening by the
SiC fibre SCS-6 [92L]. Current Ti3Al-base alloys with engineering significance are listed in Table 6.
Table 6. Important Ti3Al-base alloys [92B1, 95B].
Type Alloy [at.%] Designation Phases

α2 Ti-24Al-11Nb 24-11 α2 + β
α2 Ti-25Al-11Nb 25-11 α2 + β
α2 Ti-25Al-8Nb-2Mo-2Ta 8-2-2 α2 + β
Super-α2 Ti-25Al-16Nb 25-16 α2 + β + O
Super-α2 Ti-27Al-15Nb-1Mo 27-15-1 α2 + β + O
Super-α2 Ti-25Al-10Nb-3V-1Mo 10-3-1 α2 + β + O
O Ti-25Al-24Nb 25-24 O+β
O Ti-22Al-27Nb 22-27 O+β
O Ti-30Al-20Nb 30-20 (1986) O+ω
α2 composite SCS/6Ti-24Al-11Nb SCS-6/24-11 α2 + β + SiC

The α2 alloy 24-11 and the super-α2 alloy 10-3-1 have already been produced on a production mill scale
[95B]. Superplastic forming is possible. Various processing techniques involving hot pack rolling and
cold rolling have been developed to produce foils for applications in honeycomb or sandwich structures,
and sound joints can be obtained by arc welding, laser welding, friction and resistance welding and
diffusion bonding [95B]. Powder metallurgical processing has been applied [96G1]. A jet engine
compressor rotor was produced successfully by a powder metallurgy approach with HIP of PREP powder
(Table 3) [96F]. High pressure turbine stator inner support rings and high pressure compressor casing
sections were produced for a demonstrator jet engine and tested successfully under service conditions
[96F]. The O phase alloy 30-20 was proposed for high temperature compressor blade applications [95R]
as well as for foil-/fiber composites and honeycomb panels [95T2].
14.4.2.2.2 Physical properties
The physical properties have not yet been determined systematically for the complex advanced Ti3Al-
base alloys of Table 6 which are of primary practical interest. Density, elastic moduli and thermal
expansion data are available only for selected simple Ti3Al-base alloys, Tables 7 - 10. The property
variation with progress of powder compaction is exemplified by Table 9. The densities of composites are
determined by the densities of the constituent phases according to a simple rule of mixtures whereas the
elastic moduli of composites additionally depend on the orientation of the strengthening phases [92L].
Table 7. Density ρ of selected Ti3Al-base alloys [92L].
Alloy [at.%] ρ [Mg/m3]

Ti-24Al-11Nb 4.67
Ti-24Al-17Nb-1Mo 4.93
Table 8. Elastic moduli, i.e. Young's modulus E, shear modulus G, Poisson's ratio ν and bulk modulus K
at various temperatures T for selected simple Ti3Al-base alloys.
Alloy [at.%] T [°C] E [GPa] G [GPa] ν K [GPa] Ref.

Ti-25.5Al 27 144 56.2 0.283 96T3
Ti-25.5Al -270 151 59.0 0.280 96T3
Ti-25Al-10Nb- 23 72 97K3
3V-1Mo
(coarse globular)
Ti-25Al-10Nb- 23 120 97K3
3V-1Mo
(fine lamellar)
Ti-25Al-10Nb- 23 159 97K3
3V-1Mo
(coarse lamellar)
Ti-26.6Al-4.9Nb 26 - 883 134.47-0.0482 T 53.56-0.0180 T 0.257-0.00004 T 77S
Ti-27.4Al- 25 128.8 48.8 0.32 118.4 97C1
20.3Nb
Ti-22Al- 25 201 ± 8 94M
23Nb/Ultra-SCS
Ti-22Al- 649 173 94M
23Nb/Ultra-SCS
Ti-22Al- 760 135 ± 8 94M
23Nb/Ultra-SCS

Table 9. Variation of Young's modulus E and shear modulus G with progress of densification (relative
density ρrel) for an α2 alloy [97M1].
ρrel [%] E [GPa] G [GPa]

70 18 7
80 34 14
87 56 22
100 95 35
Table 10. Temperature (T)dependence of the thermal expansion coefficient α in the temperature range
80 - 950 °C for selected simple Ti3Al-base alloys [89S2].
Alloy [at.%] Treatment α(T) [1/K]

Ti-24.9Al-4.8Nb Hot rolled 9.54⋅10-6 + 8.97⋅10-9 T – 4.47⋅10-12 T 2
Ti-24.9Al-4.8Nb Hot rolled & annealed 9.76⋅10-6 + 7.19⋅10-9 T – 8.62⋅10-13 T 2
Ti-25.5Al-7.9Nb Hot rolled 8.80⋅10-6 + 1.24⋅10-8 T – 6.99⋅10-12 T 2
Ti-25.5Al-7.9Nb Hot rolled & annealed 8.18⋅10-6 + 1.34⋅10-8 T – 6.79⋅10-12 T 2
14.4.2.2.3 Mechanical properties
Strength, ductility and toughness of the Ti3Al-base alloys are sensitive functions of both composition and
microstructure which is controlled by prior processing [90K, 95B, 96F]. Characteristic data are shown in
Table 11 for various alloys. Different property data for the same alloy composition indicate the effect of
different prior thermomechanical treatments. The temperature dependence of yield stress is exemplified by
Table 12. The effect of microstructure on toughness is exemplified by Table 13. Particularly high strengths can
be obtained by intermetallic Ti3Al-base matrix composites as is visible in Table 14. It is noted that Ti3Al-base
alloys suffer from hydrogen embrittlement due to the dissolution of hydrogen [96S4].
Table 11. Selected tensile data for yield stress σy, fracture stress σf, total elongation εf, toughness KIc at
room temperature, and creep time to rupture tr at 650 °C and 380 MPa for various Ti3Al-base alloys [90K,
96F].
Alloy [at.%] σy [MPa] σf [MPa] εf [%] KIc [MPa m1/2] tr [h]

Ti-25Al 538 538 0.3
Ti-24Al-11Nb 787 824 0.7 44.7
Ti-24Al-11Nb 510 2.0 20.7
Ti-24Al-11Nb 761 967 4.8
Ti-24Al-14Nb 831 977 2.1 59.5
Ti-24Al-14Nb 790 3.3 15.8 60.4
Ti-15Al-22.5Nb 860 963 6.7 42.3 0.9
Ti-25Al-10Nb-3V-1Mo 825 1042 2.2 13.5 360
Ti-25Al-10Nb-3V-1Mo 823 950 0.8
Ti-25Al-10Nb-3V-1Mo 745 907 1.1
Ti-25Al-10Nb-3V-1Mo 759 963 2.6
Ti-25Al-10Nb-3V-1Mo 942 1097 2.7
Ti-24.5Al-17Nb 952 1010 5.8 28.3 62
Ti-24.5Al-17Nb 705 940 10.0
Ti-25Al-17Nb-1Mo 989 1133 3.4 20.9 476
Ti-22Al-23Nb 863 1077 5.6
Ti-22Al-27Nb 1000 5.0 30.0
Ti-22Al-20Nb-5V 900 1161 18.8
Ti-22Al-20Nb-5V 1092 1308 8.8

Table 12. Temperature T dependence of tensile yield stress σy of the Ti3Al-base alloy Ti-25Al-9Nb [89G,
94P1].
T [°C] σy [MPa]
27 520
227 444
427 394
627 370
Table 13. Effect of microstructure variation on toughness KIc at room temperature for a Ti-25Al-10Nb-
3V-1Mo alloy [97K3].
Microstructure KIc [MPa m1/2]

Coarse globular 11
Fine globular 10
Coarse bimodal 11
Fine bimodal 14
Fine lamellar 8
Coarse lamellar 50
Table 14. Tensile yield stress σy, fracture stress σf, and total elongation εf of the intermetallic matrix
composite Ti-22Al-23Nb/Ultra-SCS at various temperatures T [94M].
T [°C] σy [MPa] σf [MPa] εf [%]

23 1690 ± 63 2213 ± 35 1.48 ± 0.02
649 - 1820 1.35
760 - 1248 ± 133 1.22 ± 0.04
14.4.2.2.4 Chemical properties
The oxidation resistance of the Ti3Al-base alloys is higher than that of conventional Ti alloys with TiO2
formation, but lower than that of Al2O3 forming alloys [96R3]. The rate controlling mechanisms are
complex and change with atmosphere, temperature and time [92W, 96R3, 96R2, 98V2]. Oxidation is
moderate with porous scales up to 800 °C whereas spallation occurs at higher temperatures [96R3, 98V2].
The addition of Nb to the Ti3Al-base alloys is beneficial to the oxidation resistance as well as nitrogen in
the atmosphere [96R3, 96R2]. Table 15 presents characteristic data for oxidation at 800 °C.
Table 15. Characteristic oxidation data for various Ti3Al-base alloys at 800 °C, i.e. apparent parabolic
rate constant kp and apparent activation energy Q.
Alloy [at.%] Atmosphere Test duration [h] kp [10-12 g2cm-4s-1] Q [kJ/mol] Ref.
Ti-25Al O2 9 19 289 96R3
Ti-25Al-11Nb O2 4 2.0 330 96R3
Ti-24Al-15Nb O2 6 2.2 329 96R3
Ti-24Al-15Nb 20 % O2 + 5 0.25 274 96R2
80 % N2
Ti-24Al-10Nb-3V-1Mo 20 % O2 + 15 1150 217 98V2
80 % N2
Ti-25Al-10Nb-3V-1Mo air 24 2.4 248 92W
The corrosion behaviour of Ti3Al-base alloys in other environments has been studied only occasionally
[92M2, 94B, 94N, 95D2].

It is noted that hydrogen is dissolved in Ti3Al-base alloys readily leading to hydrogen embrittlement
[96S4] and stress corrosion cracking [92Z]. It is further noted that the thermal stability of intermetallic
Ti3Al-base matrix composites - in particular SCS-6 SiC/Ti-25Al-10Nb-3V-1Mo - is affected by chemical
reactions between matrix and strengthening phase [98Y1].
14.4.2.3 TiAl-base alloys
The interest in titanium aluminide alloys concentrates on alloys on the basis of the TiAl-phase. They are
known as γ-TiAl alloys or gamma titanium aluminides and excel by their high specific strength, i.e.
strength per unit density [99D]. These alloys contain the α2 phase Ti3Al as a second phase and are alloyed
with further elements for property optimisation. The composition range is given by Ti-(45-48)Al-
(0-2)(Cr,Mn,V)-(0-5)(Nb,Ta,W)-(0-2)(Si,B,Fe,N) [at.%] possibly with additional Hf, Sn, C and/or
0.8 – 7 vol.% TiB2 for dispersion strengthening [94K3]. These alloys can be produced by both powder
metallurgy and ingot metallurgy [96G1]. They are processed in various ways to produce different
microstructures with different property combinations which can be modified by thermomechanical
treatments. Table 16 shows the standard microstructures and Table 17 lists the alloys of primary interest.
Table 16. Standard microstructures of TiAl-base alloys [94K3].
Type Phase distribution

Near-gamma (NG) γ grains + α2 particles
Duplex (DP) γ grains + α2 plates or particles
Nearly lamellar (NL) Lamellar γ + γ grains
Fully lamellar (FL) Lamellar γ + residual γ grains on grain boundaries
Modified NL (MNL) Lamellar γ + fine γ grains
Modified FL (MFL) Lamellar γ
Table 17. Important TiAl-base alloys with microstructures of Table 16 [94K3].
Designation Composition [at.%] Microstructure type

48-1-(0.3C) Ti-48Al-1V-0.3C-0.2 O DP
48-1-(0.2C) Ti-48Al-1V-0.2C-0.14 O DP/NL
48-2-2 Ti-48Al-2Cr-2Nb DP, NL, DP/FL
G1 Ti-47Al-1Cr-1V-2.6Nb DP/FL
Sumitomo Ti-45Al-1.6Mn NL
IHI Alloy Ti-47.3Al-0.7V-1.5Fe-0.7B -
ABB Alloy Ti-47Al-2W-0.5Si DP
47XD Ti-47Al-2Mn-2Nb-0.8TiB2 NL + TiB2
45XD Ti-45Al-2Mn-2Nb-0.8TiB2 MFL + TiB2
GE Alloy 204b Ti-46.2Al-xCr-y(Ta,Nb) NL
Ti-47Al-2Nb-2Cr-1Ta Ti-47Al-2Nb-2Cr-1Ta DP
Alloy 7 Ti-46Al-4Nb-1W NL
Alloy K5 Ti-46.5Al-2Cr-3Nb-0.2W DP/MFL
Ti-48Al-2Cr [95W1, 97C2] Ti-48Al-2Cr NG, DP, FL
γ-TAB [95W1, 99S4] Ti-47Al-1.5Nb-1Cr-1Mn-0.7Si-0.5B MFL
γ-Met [99C1] Ti-46.5Al-4(Cr,Nb,Ta,B) MFL
TiAl-base alloys have been developed worldwide and are on the brink of commercialisation. A number of
components have been identified for application of TiAl-base alloys (Table 18) and various jet engine and

car engine components have been produced successfully using powder metallurgy approaches [95H2,
96F, 97I, 98E, 98N2, 99C1]. Particularly noteworthy is the production of large sheets, which allow
forming under superplastic conditions and joining by diffusion bonding [97C2, 99C1]. In addition,
components can be joined by welding and brazing [97X2, 98B1, 98N2, 99S3, 99L1].
Table 18. Possible applications of TiAl-base alloys [94K2].
Automotive Aerospace: gas turbine engine

Turbocharger rotor High pressure compressor: blades, stator, vanes, cases
Exhaust engine valve Combustor: diffuser case, swirler
Turbine: cases, side plates, low-pressure blades
Nozzle: flaps, outer skin, substructures
Tubing
Specific data for the TiAl-base alloys of actual interest are not available in the open literature. Unspecific
data for density, thermal conductivity and Young's modulus are given in Table 5. Selected elasticity data
for single-phase TiAl and a TiAl composite are presented in Table 19 whereas thermal data for single
crystalline and polycrystalline TiAl alloys are shown in Tables 20 and 21.
Table 19. Elastic Moduli, i.e. Young's modulus E, shear modulus G, Poisson's ratio ν and bulk modulus K , for
single phase TiAl and a TiAl composite.
Alloy [at.%] T [°C] E [GPa] G [GPa] ν K [GPa] Ref.

–7
Ti-49.4Al 25-935 173.59 – 0.0342 T 70.39 – 0.0141 T 0.234 + 67·10 T 77S
Ti-50Al 25 185 75.7 110 96T2
Ti-50Al -273 190 78.3 112 96T2
Ti-47Al-2V- 27 180 95K2
7 vol.% TiB2
Ti-47Al-2V- 647 162 95K2
7 vol.% TiB2
Table 20. Temperature T dependence of the thermal expansion coefficient α for monocrystalline TiAl
[97H1].
Alloy [at.%] T [°C] α[100] [1/K] α[001] [1/K]

Ti-56Al 25 - 500 9.77x10-6 + 4.46x10-9 (T + 273) 9.26x10-6 + 3.76x10-9 (T + 273)
Table 21. Thermal expansion coefficient α, thermal conductivity λ and specific heat cp at various
temperatures T for polycrystalline TiAl alloys.
Alloy [at.%] T [°C] α [1/K] λ [W/(m K)] cp [J/(g K)] Ref.

Ti-50Al 27 11·10-6 11 0.4 93Y
Ti-50Al 850 13·10-6 19 0.5 93Y
Ti-48Al-2Cr 100 9.1·10-6 - - 95W1
Ti-48Al-2Cr 700 11.8·10-6 - - 95W1

Strength, ductility and toughness of the Ti3Al-base alloys are sensitive functions of both composition and
microstructure which is controlled by prior processing [94K3]. Characteristic data are shown in Table 22
for various alloys. Different property data for the same alloy composition indicate the effect of different
prior thermomechanical treatments. It is noted that TiAl-base alloys are subject to hydrogen /
environmental embrittlement depending on the amount of α2-Ti3Al [96S4, 98T1]. Creep and fatigue data
are available [94K3, 95W1].
Table 22. Selected tensile data for yield stress σy, fracture stress σf, total elongation εf, toughness KIc at
room temperature RT or higher temperature T for the TiAl-base alloys of Table 17 with microstructures
of Table 16 [94K3].
Alloy Alloy condition T σy σf εf KIc

(processing,
microstructure) °C MPa MPa % MPa m1/2
48-1-(0.3C) Forging + HT RT 392 406 1.4 12.3
437 - - - 22.8
760 320 470 10.8 -
Casting-duplex RT 490 - - 24.3
48-1-(0.2C) Forging + HT RT 480 530 1.5 -
815 360 450 720 -
48-2-2 Casting + HIP + HT RT 331 413 2.3 20-30
760 310 430 - -
Extrusion + HT: RT 480/454 - 3.1/0.5 -
DP/FL
760 403/405 - 40/3 -
870 330/350 - 53/19 -
PM extrusion + HT RT 510 597 2.9 -
700 421 581 5.2 -
G1 Forging + HT: DP/FL RT 480/330 548/383 2.3/0.8 12/30-36
600 383/- 507/- 3.1/- 16/-
800 324/290 492/378 55/1.5 -/40-70
Sumitomo Reactive sintering RT 465 566 1.4 -
800 370 540 14 -
IHI Alloy Casting RT - 520 0.6 -
800 - 424 40 -
ABB Alloy Casting + HT RT 425 520 1.0 22
760 350 460 2.5 -
47XD Casting + HIP + HT RT 402 482 1.5 15-16
760 344 458 - -
45XD Casting + HIP + HT RT 550-590 670-720 1.5 15-19
600 440 650 - -
760 415 510 19 -
GE Alloy Casting + HIP + HT RT 442 575 1.5 34.5
204b
760 382 560 12.4 -
840 381 549 12.2 -
Ti-47Al-2Nb- Casting + HIP + HT RT 430 515 1.0 -
2Cr-1Ta 800 363 495 23.3 -
870 334 403 14.6 -
Alloy 7 Extrusion + HT RT 648 717 1.6 -
760 517 692 - -

Alloy Alloy condition T σy σf εf KIc

(processing,
microstructure) °C MPa MPa % MPa m1/2
Alloy K5 Forging + HT: RT 462/473 579/557 2.8/1.2 11/20-22
DP/MFL 800 345/375 468/502 40/3.2 -
870 -/362 -/485 -/12.0 -
Ti-48Al-2Cr Casting + HIP + HT RT 390 405 1.5
[95W1,
97C2]
700 340 395 2.7 -
γ-TAB Casting + HIP + HT RT 475 - 1.6
[95W1, 99S4] 700 385 - 6.0 -
The oxidation behaviour of TiAl alloys is complex with formation of Al2O3 and/or TiO2 and parabolic
rate constants kp between 3x10-13 and 3x10-9 g2cm-4s-1 at 950 °C depending not only on alloy composition,
atmosphere and temperature, but also on alloy surface quality [96M4]. The oxidation rate is higher in air
than in pure oxygen. Alloying additions of Nb, W, Ta, or Si generally improve the oxidation resistance.
Additions of V and Mo promote Al2O3 formation above 900 °C, which is beneficial, but accelerates scale
growth at lower temperatures, i.e. at possible service temperatures. Small additions of Cr reduce the
oxidation resistance whereas larger amounts improve it. Small additions of P or Cl have been found to
increase the oxidation resistance [96M4]. Some characteristic data are shown in Table 23.
Table 23. Characteristic oxidation data for some TiAl-base alloys of Table 17, i.e. apparent parabolic rate
constant kp at 800 °C in air [96B].
Alloy [at.%] Test duration [h] kp [10-12 g2 cm-4 s-1]

48-2-2 500 2
Alloy K5 1000 0.5
Alloy 7 (with 5 at.% Nb) 1000 0.1
TiAl-base alloys usually contain α2-Ti3Al as second phase and so are subject of hydrogen uptake and
hydrogen/environmental embrittlement depending on the amount of α2-Ti3Al [96S4, 98T1]. Corrosion
data are available only for few special cases, see e.g. [97N2, 97O, 99T].
14.4.3 Iron aluminides

Iron aluminide alloys, which are based on the intermetallic phases Fe3Al or FeAl or both, are most
attractive because of high corrosion resistance and low cost [96M2, 97B2, 97S5]. Pertinent alloy
developments are in progress.
The generally accepted binary Fe-Al phase diagram is shown in Fig. 14.5. The iron aluminide alloys
usually contain Cr as major alloying element. A representative isothermal section of the ternary Fe-Al-Cr
phase diagram is shown in Fig. 14.6. It is noted that the available phase diagram information on this and
other ternary Fe-Al systems is scarce and sometimes conflicting [94P2,95V2].

Al content c Al [wt.%]
0 20 40 60 80 100
1600
L
1400
(α Fe) 1310°C
1232°C
1200 1169°C ~1160°C
ε
Temperature T [°C]
(γ Fe)
1102°C
1000
Fe2 Al5
912°C FeAl FeAl 2
FeAl 3
800
770°C
655°C
660°C
600
Fe3Al (Al) Fig. 14.5. Fe-Al phase diagram
400 [90M].
0 20 40 60 80 100
Fe Al content c Al [at.%] Al
T = 750°C Cr
20 80
Cr c
%]
ont
[at.
40 60
ent
Fe
c
c Cr
nt
nte
[at.
Al8Cr5
o
%]
Fe c
60 40
Al9Cr4
α - Fe - Cr
Al4Cr
80 20
γ - Fe Al2 Fe
L Fig. 14.6. Isothermal section at 1000 °C of the
Fe-Al-Cr phase diagram [97P1].
Fe 20 40 60 Al Fe 80 Al
Al5Fe4 3
Al content c Al [at.%]

14.4.3.2 Fe3Al-base alloys
Fe3Al-base alloys of practical interest are given in Table 24. The alloys have been developed for
applications at high temperatures in oxidising, sulphidising or carburising atmospheres and are on the
brink of commercialisation [97S5]. Possible applications are listed in Table 25. The upper temperature
limit for structural applications is about 700 °C due to strength and 1200 °C due to corrosion [97D4].
Apart from conventional ingot metallurgy, Fe3Al-base alloys have been produced successfully by
powder metallurgy methods [96M2, 96G1, 97S5, 98S3]. The heat of formation is -67.0 kJ/mol for Fe3Al
[97S5]. Powders can be produced by gas atomisation and water atomisation. Powders can be sintered into
products of controlled porosity for application as filters for hot-gas clean up [96D2, 97S5]. Fully dense
bars with grain size of < 100 µm have been obtained by hot extrusion at 1000 °C with an area reduction
ratio of ≥ 9:1 [96M2]. Welding is possible with a general propensity for cold cracking and a specific
dependence of hot cracking on minor changes in alloying additions [96M2, 97S1, 98S3].
Table 24. Fe3Al-base alloys of practical interest [96M2, 96D2].
Designation Composition [at.%] Composition [wt.%]

FAS Fe-28Al-2Cr-0.05B Fe-15.9Al-2.2Cr-0.01B
FAL Fe-28Al-5Cr-0.1Zr-0.05B Fe-15.9Al-5.5Cr-0.15Zr-0.01B
FA-129 Fe-28Al-5Cr-0.5Nb-0.2C Fe-15.9Al-5.5Cr-1.0Nb-0.05C
FAH Fe-28Al-5Cr-0.5Nb-0.5Mo-0.1Zr-0.2B Fe-15.9Al-5.5Cr-1.04Nb-1.0Mo-0.15Zr-0.04B
Table 25. Possible applications of Fe3Al-base alloys [96M2].
Application Component system

Heating elements Toasters, stoves, ovens, cigarette lighters, dryers
Wrapping wire Insulation wrapping for investment casting molds
Regenerator discs Automotive gas turbine engines
Hot-gas filters Coal gasification system
Piping, tubing Coal gasification system, automotive systems
Tooling Dies for superplastic forming of titanium based alloys
Shields Superheater and reheater tubes in coal fired power plants
Automotive Exhaust manifolds, catalytic converters, exhaust support hangers
Other Components needing high temperature sulphidation and oxidation resistance
A data base for Fe3Al-base alloys is available [96M2, 96D2, 97S5], and characteristic data are shown in
Tables 26 - 28 with respect to melting, density, elasticity and thermal expansion. It is noted that Fe3Al-
base alloys show order transitions at critical temperatures - 543 °C and 924 °C for alloy FA-129 - leading
to thermal expansion peaks at those temperatures [93P2]. The electrical resistivity of alloy FA-129
(Table 24) is 150 µΩ cm and increases up to about 160 µΩ cm in the temperature range 500 - 1000 °C,
whereas it varies between 190 µΩ·cm at room temperature and 200 µΩ cm at 300 - 400 °C for FAH in the
temperature range 0 – 1000 °C [96D2]. Thermal conductivity data are given in Table 29.
Table 26. Melting temperature Tm and density ρ of alloys in Table 24 [97S5].
Alloy Tm [°C] ρ [g/cm3]

FAS 1430 – 1477 6.53
FAL 1430 – 1477 6.51
FA-129 1430 – 1477 6.54

Table 27. Young's modulus E of alloys in Table 24 (sheet material) at various temperatures T [97S5].
T [°C] E [GPa]
FAS FAL FA-129
23 183 201 207
150 178 193 198
300 167 179 -
500 160 161 166
700 135 148 144
900 117 135 130
1100 100 109 108
Table 28. Mean thermal expansion coefficient α (room temperature to specified temperature) of alloy FA-129
(electroslag remelted and extruded at 1000 °C) in Table 24 at various temperatures T [93P2, 97S5].
T [°C] α [10-6/K]
100 15.4
200 15.9
300 16.7
400 17.9
500 19.2
600 20.4
700 21.0
800 21.8
900 22.8
1000 23.4
1100 23.4
1200 23.5
Table 29. Temperature (T) dependence of the thermal conductivity λ for alloy FA-129 (Table 24) [94S1].
T [°C] λ [W/(m K)]

200 13.5
300 14.6
400 15.8
500 17.4
600 17.8
700 18.4
800 19.4
900 19.9
1000 21.8
1100 23.8
Characteristic strength and ductility data are shown in Table 30 for some Fe3Al-base alloys of practical
interest. It is noted that Fe3Al-base alloys show an anomalous temperature dependence of the yield stress.
It is further noted that Fe3Al-base alloys suffer from environmental embrittlement in the presence of water
vapour [96M2, 98S3]. Additional data are available with respect to creep [97S5, 98S3] and fatigue
[98S3]. Effects of mechanical alloying processing on the mechanical properties have been described
[94S2].

Table 30. Selected tensile data for yield stress σy, fracture stress σf and total elongation εf at room
temperature RT or higher temperature T for Fe3Al-base alloys of Table 24 [97S5].
Alloy T [°C] σy [MPa] σf [MPa] εf [%]

FAS RT 385 828 14
200 250 740 13
535 290 450 37
700 183 135 60
FAL RT 442 965 18

200 381 910 22
535 401 531 42
700 100 104 100
FA-129 RT 412 828 8

200 358 1021 8
425 392 792 10
700 217 240 -
The oxidation resistance of Fe3Al-base alloys is good as is known for other Al2O3 forming alloys. The
scale adherence is improved by the usual microalloying additions. Characteristic data are shown in
Table 31. The high hot gas corrosion resistance is exemplified by data in Tables 32 - 34 with respect to
carburisation and sulphidation. Additional data on high temperature corrosion in various environments are
available [98T4, 98N1]. It is noted that the high carburisation resistance is observed only at carbon
activities aC < 1 or at high temperatures. At high carbon activities aC > 1 and intermediate temperatures
400 °C - 900 °C so-called metal dusting is observed, i.e. corrosion with high rate leading to alloy
disintegration - see Table 35 [96S6]. It is further noted that Fe3Al-base alloys suffer from environmental
embrittlement in the presence of water vapour [96M2, 98S3].
Table 31. Characteristic oxidation data for some Fe3Al -base alloys (see Table 24), i.e. apparent parabolic rate
constant kp at 1200 °C for isothermal exposures in dry flowing oxygen [96P2].
Alloy kp [10-12 g2cm-4s-1]

FAS (extruded) 13 (in dry flowing air)
FAS + 0.2Y 2.3 - 3.5
FAS + 0.1Ce 6.9
FAS + 0.2Hf 11
FAS + 0.0.2Nd 5
FAS + 0.0.2Sc 13
FAS + 0.0.2Yb 5.1
FAS + 0.0.2Zr 5.3
FAL 6.0 - 7.4
Table 32. Mass change ∆m of Fe3Al-base alloys (MM = Mischmetall) by carbon pick-up at temperature T
after 1008 h of cyclic exposure in carburising CH4/H2 gas with a carbon activity aC = 0.8 [96K1].
Alloy [wt.%] T [°C] ∆m [g/m2]

Fe-10.6Al-1.9Cr-0.06Hf-0.013C 1000 2.4 ± 0.3
Fe-15.5Al-2.0Cr-0.10Hf-0.022C-0.18MM 1000 2.8 ± 0.3
Fe-16.2Al-2.2Cr-0.067C 850 1.7 ± 1.2
1100 10.0 ± 0.5

Table 33. Mass change ∆m of a Fe3Al-base alloy at temperature T after 2016 h of cyclic exposure in
sulphidising 1 % SO2/air [96K1].

Fe-10.6Al-1.9Cr-0.06Hf-0.013C 650 1
750 2
850 3
Table 34. Mass change ∆m of Fe3Al-base alloys at temperature T after 2016 h of cyclic exposure in
sulphidising 1 % H2S/ 10 % CO2/H2 [96K1].

Fe-9.9Al-2.0Cr-0.15Hf-0.01C 550 –352
Fe-15.5Al-2.0Cr-0.10Hf-0.022C-0.18MM 550 +1
Fe-16.2Al-2.2Cr-0.067C 550 +1
Table 35. Mass change ∆m of Fe3Al-base alloys at 650 °C after an exposure of 24 h in carburising
CO/H2/H2O (pCO = 0.25 bar) with a carbon activity aC = 41.5 [96S6].
Alloy [wt.%] ∆m [g/m2]

Fe-14Al 320
Fe-14Al-2.2Cr 2.2
Fe-16Al-4.8Cr-0.15Zr 0.16
14.4.3.3 FeAl-base alloys
FeAl-base alloys are of high interest because of the outstanding high temperature oxidation and corrosion
resistance in various aggressive environments, which has initiated serious alloy development efforts
[98L2]. Some FeAl-base alloys of current interest are listed in Table 36. FeAl -base alloys have been
produced successfully by powder metallurgy methods from elemental powders and ceramic additives
have been used for strengthening [96G1, 98L2]. The heat of formation is –50.2 kJ/mol for FeAl [97S5].
Alloy powders can be made in inert gas or water coolant and compacted by hot pressing or hot extrusion
in the temperature range 950 °C - 1100 °C. FeAl alloys are chemically compatible with various ceramics,
e.g. TiC, WC, TiB2, TiZr2, and respective composites with ceramic volume fractions up to 60 % can be
produced by liquid phase sintering at about 1450 °C in vacuum [98L2]. Sheet material has been produced
by powder metallurgical processing with roll compaction, tape casting or plasma spraying of powder
[98H1]. Welding is possible [92M1, 96M2, 97M3, 98I]. Possible applications of FeAl-base alloys are
listed in Table 37. The upper temperature limit for structural applications is about 800 °C due to strength
and 1200 °C due to corrosion [97D4].
Table 36. FeAl-base alloys of current interest [97M3].
Designation Composition [at.%]

FA-324 Fe-35.8Al
FA-350 Fe-35.8Al-0.05Zr-0.24B
FA-385 Fe-35.8Al-0.2Mo-0.05Zr-0.13C
FA-385M1 Fe-35.8Al-0.2Mo-0.05Zr-0.13C-0.01B
FA-386M1 Fe-36Al-0.2Mo-0.07Zr-0.28C-0.02B

Table 37. Possible applications of FeAl-base alloys [98L2, 98S2].
Application Application
-Gas metal filters, cladding for boilers, heat -Fabric cutting blade
exchangers and other components in coal energy -Die and tool components
conversion systems -Piston valves and rings, exhaust manifolds,
-Heating elements catalytic converter substrates and other automotive
-Structural components in carburising environments parts
-Food industry parts without hazardous materials -Rails for walking beam furnaces
such as Ni and Cr -Protective coatings
The density ρ [g/cm3] of binary FeAl alloys varies with Al content XAl [at.%] according to [86H]:
ρ = 8.615 – 0.06264 XAl , (1)
whereas the elastic Young's modulus E [GPa] depends on Al content XAl [at.%] and temperature T [°C]
according to
E = 287.75 – 0.219 (T + 273) – 0.0035 XAl2 + 0.00305 XAl (T + 273) . (2)
Both relations rely on data for FeAl alloys with Al contents between 40 at.% and 49 at.% and
temperatures between room temperature and 850 °C.
Characteristic thermal expansion data are listed in Table 38. It is noted that FeAl-base alloys show an
order-disorder transition at a critical temperature - 1190 °C for alloy FA-385 - leading to a thermal
expansion peak at that temperature [93P2]. A thermal conductivity of 13 W/(m K) was observed for
binary FeAl alloys with Al contents between 47 and 51 at.% [97S6].
Table 38. Mean thermal expansion coefficient α (room temperature to specified temperature T) of alloy
FA-385 (arc-melted and drop cast) in Table 36 [93P2].
T [°C] α [10-6/K]
100 18.3
200 19.0
300 19.6
400 20.3
500 20.6
600 21.1
700 21.6
800 22.2
900 22.9
1000 23.8
1100 24.8
1200 26.5
Characteristic strength and ductility data are shown in Table 39. FeAl-base alloys are subject to
environmental embrittlement and vacancy hardening. Environmental embrittlement results from the
presence of water vapour in the atmosphere. The data in Table 39, which refer to testing in air, indeed
include the effect of environmental embrittlement, whereas testing in e.g. dry oxygen yields higher
stresses and strains at fracture [98L2]. Vacancy hardening, which results from the presence of excess

vacancies, leads to increased strength and reduced ductility and can be avoided only by long anneals at
low temperatures - typically 400 °C - and slow cooling [97B1]. The data in Tables 40 and 41 reveal the
effect of cooling rate and annealing.
The yield strength of FeAl-base alloys depends on temperature in an anomalous way leading to a yield
strength peak at intermediate temperatures, e.g. 480 °C for well-annealed Fe-40 at.%Al [98G3]. Data on
yielding, hardening and creep in the temperature range between room temperature and 750 °C are
available for powder processed Fe - 40 at.% Al alloys [98D1] as well as creep rupture data for various
developmental alloys [97M3]. Likewise the fatigue behaviour has been studied in this temperature range
for engineering design considerations [98J].
Table 39. Selected tensile strength data for yield stress σy, fracture stress σf and total elongation εf at
room temperature in air for various FeAl-base alloys (see Table 36) [90L1, 97M2].
Alloy Fabrication σy [MPa] σf [MPa] εf [%]

FeAl-36.5 at.% Al Arc-melting, drop casting, hot forming, 360 412 2.2
annealing
FeAl-40.0 at.% Al Arc-melting, drop casting, hot forming, 390 405 1.2
annealing
FeAl-40.0 at.% Al- Arc-melting, drop casting, hot forming, 391 577 4.3
300 wt ppm B annealing
FA-385 Vacuum-induction melting, extrusion at 900 °C 410 760 8.4
Nitrogen atomisation, extrusion at 950 °C 670 1080 12.4
Nitrogen atomisation, extrusion at 950 °C, 590 895 6.2
1h annealing at 1100 °C
FA-385M1 Vacuum-induction melting, extrusion at 900 °C 435 850 10
Table 40. Tensile yield stress σy, fracture stress σf and total elongation εf at room temperature in air for
Fe-45 at.% Al as a function of heat treatment [97B1].
Treatment σy [MPa] σf [MPa] εf [%]

As-extruded - 790 0
Air cool - 622 0
Air cool + 400 °C anneal 312 - 1.1
Furnace cool 554 - 0.7
Furnace cool + 400 °C anneal 261 - 1.6
Table 41. Tensile yield stress σy, fracture stress σf and total elongation εf at various temperatures T in air
for FA-350 (Table 35) as a function of heat treatment [94A1].
T [°C] Treatment σy [MPa] σf [MPa] εf [%]

22 Oil quench 460 561 2
Furnace cool 390 647 4
200 Oil quench 405 711 6
Furnace cool 366 801 9
400 Oil quench 345 686 21
600 Oil quench 345 404 52

The oxidation of FeAl alloys is initiated by the rapid formation of metastable scales (stage I), and only
then - after about 10 h at 1000 °C - protective α-Al2O3 scales are formed (stage II) [96R1]. Table 42
shows some data for a binary FeAl alloy with 48 at.% Al, the oxidation behaviour of which does not
differ from that of Fe-40 at.%Al [96R1].
FeAl alloys show advantageous high temperature corrosion properties [94T2, 98T4]. In particular, they
are uniquely corrosion resistant in mixed gas environments containing sulphur and oxygen, and they have
an excellent high temperature carburisation performance. Some information on aqueous corrosion
resistance is available [97R]. The presence of water vapour in air leads to environmental embrittlement as
mentioned in the preceding section.
Table 42. Apparent parabolic rate constant kp for oxidation of Fe-48 at.% Al with exposures of 300 h
in 1 bar He-1 % O2 as a function of temperature T with initial stage I and final stage II [96R1].
T [°C] kp(I) [g2cm-4s-1] kp(II) [g2cm-4s-1]

800 2.6⋅10-14 -
850 7.9⋅10-14 -
900 2.3⋅10-13 -
950 3.2⋅10-13 2.4⋅10-15
1000 4.4⋅10-13 3.5⋅10-15
1050 - 5.5⋅10-15
1100 - 5.8⋅10-14

14.4.4 Nickel aluminides

The nickel aluminide alloys of practical interest are based on the intermetallic phases Ni3Al or NiAl.
Ni3Al-base alloy developments have reached maturity and commercialisation has been initiated.
NiAl-base alloy developments are still in progress.
The binary Ni-Al phase diagram in Fig. 14.7 considers new results on the Ni3Al phase equilibria. The
nickel aluminide alloys usually contain Cr as major alloying element. A representative isothermal section
of the ternary Ni-Al-Cr phase diagram is shown in Fig. 14.8. It is noted that the available phase diagram
information on this and other ternary Ni-Al systems is scarce and sometimes conflicting [94P2, 95V2].
Ni content wNi [wt.%]

0 20 40 60 80 100
1800
1638°C
1600
1455°C
AlNi
1400 1380°C 1383°C
Temperature T [°C]
1200 1133°C
(Ni)
1000
854°C
660°C
800
Al3Ni 2 ~700°C
640°C
600 Fig. 14.7. Ni-Al phase diagram
Al3Ni Al3 Ni5 AlNi 3
(Al) [95S1].
400
0 20 40 60 80 100
Al Ni content c Ni [at.%] Ni
T = 1025°C 0 100
Al
20 80
40 60
Al c
20 80
%]
ont
[at.
Al c
. %]
40
ent
60 Al3Cr2 Ni3Al2
Cr
ont
[wt
c
w Al
60
ent
40
ent
Cr
ont
[wt
w
c
ent
Al
Cr c
. %]
20
[at.
80
ont
60 NiAl 40
%]
Cr c
Ni3Al
80 20
100
0
Fig. 14.8. Isothermal section at 1025 °C of the
Cr 20 80 Ni Ni-Al-Cr phase diagram [94P2].
40 60
Ni content c Ni [at.%]
0 20 40 60 80 100
Ni content wNi[wt.%]

14.4.4.2 Ni3Al-base alloys
Ni3Al is the well-known strengthening phase in the familiar Ni-base superalloys. Ni3Al has been regarded
as an intermetallic model phase, and the respective alloy design efforts have resulted in the development
of several Ni3Al-base alloys - see Table 43 - with attractive properties for structural use, which are ready
for application [96D2, 96S3, 96S5, 97L2]. Powder metallurgical processing has been applied successfully
[96G1] including gas atomisation [97S4], reaction synthesis [97S4, 97D3], and plasma spray processing
[97H3]. Alloys IC-50, IC-221W and IC-396M are produced in powder form by nitrogen gas atomisation
[97S4]. The heat of formation is –153.2 ± 5.02 kJ/mol for Ni3Al [97S5]. Welding is possible [97S1,
97D4]. Alloy IC-221W has been designed as weld filler metal for the other alloys [97S4]. Ni3Al-base
alloys are already applied as is exemplified by Table 44. The upper temperature limit for structural
applications is about 1100 °C due to strength and 1150 °C due to corrosion [97D4]. The Ni3Al alloy
IC-50 of Table 43 has been used as binder phase in WC-Ni3Al composites for application as corrosion-
resistant tool bits for the pulp and paper industry [96D2].
Table 43. Ni3Al-base alloys selected for commercial applications [96D2, 96S3, 96S5, 97L2, 97S4].
Designation Composition [at.%] Composition [wt.%]

IC-50 Ni-21.7Al-0.34Zr-0.1B Ni-11.3Al-0.6Zr-0.02B
IC-218 Ni-16.6Al-7.9Cr-0.4Zr-0.1B Ni-8.5Al-7.8Cr-0.8Zr-0.02B
IC-218LZr Ni-17.0Al-8.2Cr-0.1Zr-0.1B Ni-8.7Al-8.1Cr-0.2Zr-0.02B
IC-221 Ni-16.6Al-7.9Cr-1.0Zr-0.1B Ni-8.5Al-7.8Cr-1.7Zr-0.02B
IC-221M Ni-15.9Al-8.0Cr-0.8Mo-1.0Zr-0.04B Ni-8.0Al-7.7Cr-1.7Zr-1.4Mo-0.008B
IC-221W Ni-15.9Al-8.0Cr-1.8Zr-0.8Mo-0.015B Ni-8.0Al-7.7Cr-3.0Zr-1.5Mo-0.003B
IC-396, Ni-15.9Al-8.0Cr-1.7Mo-0.5Zr-0.025B Ni-8.0Al-7.7Cr-3.0Mo-0.8Zr-0.005B
IC-396M
MX-246 Ni-16.6Al-7.9Cr-1.0Zr-1.0Ti-0.48Mn-0.5B- Ni-8.5Al-7.8Cr-1.7Zr-0.9Ti-0.5Mn-0.1B-
0.4C 0.1C
Table 44. Applications of the Ni3Al-base alloy IC-221M of Table 43 [96D2, 97S5].
Application Component
Furnace fixtures Trays, nuts and bolts for carburising furnaces
Grate bars, pallet tips, and roll guides in
phosphate ore calcination furnaces
Transfer rolls in steel heat treatment furnaces
Radiant burner tubes for gas-fired furnaces
Rails for walking beam furnaces
Other Dies for closed die hot forging
Paddles for mixing ceramic slurries
Melting temperature, density and elasticity data are given in Tables 45 - 46 for three Ni3Al alloys,
whereas thermal expansion and thermal conductivity data are shown in Table 47 only for the Ni3Al alloy
IC-221M, which is already applied. Additional data - electrical resistivity, Seebeck coeffient
characterising the thermopower besides thermal expansion and thermal conductivity - are presented in
Table 48 for the unalloyed phase Ni3Al. The comparison of the thermal expansion and thermal
conductivity data in Tables 47 and 48 demonstrates the effect of the alloying elements and the changed
Al content on the physical properties, in particular the thermal conductivity.

Table 45. Melting temperature Tm and density ρ of alloys in Table 43 [97S5].
Alloy Tm [°C] ρ [g/cm3]

IC-50 1395 7.6
IC-218LZr 1387 7.77
IC-221M 1171 - 1353 7.86
Table 46. Young's modulus [GPa] of alloys in Table 43 at various temperatures T [97S5].
T [°C] IC-50 IC- 218LZr IC-221M

20 204 225 200
150 198 223 195
300 - 218 184
500 178 207 163
700 163 194 157
900 136 - 139
1100 127 170 114
Table 47. Mean thermal expansion coefficient α (room temperature to specified temperature T) and
thermal conductivity λ of alloy IC-221M in Table 43 at various temperatures T [93P2, 97S5].
T [°C] α [10-6/K] λ [W/(m K)]

100 12.8 11.9
200 13.1 13.9
300 13.4 15.2
400 13.7 16.7
500 14.0 18.0
600 14.3 20.3
700 14.7 23.0
800 15.2 25.2
900 15.8 27.5
1000 16.6 30.2
Table 48. Mean thermal expansion coefficient α (room temperature to specified temperature T), thermal
conductivity λ, electrical resistivity ρ, and absolute Seebeck coefficient q of pure Ni3Al at various
temperatures T [96S5].
T [°C] α [10-6/K] λ [W/(m K)] ρ [µΩ cm] q [µV/K]

–269 - - 1.54 -
27 12.5 28.85 32.59 +5.4
127 13.0 33.72 39.00 +4.1
227 13.5 35.13 44.75 +1.8
327 14.0 36.18 50.13 -0.4
427 14.6 37.07 55.27 -2.4
527 15.2 37.27 60.54 -4.3
627 16.0 36.86 66.50 -5.5
727 16.8 36.12 73.02 -6.3

A wealth of data is available which primarily refer to cast alloys [96D2, 96S5, 97S5, 97L2].
Characteristic strength and ductility data referring to testing in air are shown in Table 49 for cast, wrought
and powder-metallurgically processed Ni3Al-base alloys. The data include the effects of environmental
embrittlement, which result from the presence of water vapour in the test atmosphere, i.e. higher fracture
stresses and fracture strains are obtained when the presence of water vapour is avoided, e.g. by testing in
dry oxygen [97L2]. It is noted that environmental embrittlement reduces ductility not only at room
temperature, but also at intermediate temperatures with a ductility minimum at about 800 °C which
affects hot working [95L].
The yield stress depends anomalously on temperature with a peak at intermediate temperatures of the
order of 700 °C as is visible in Table 49. Additional data on high temperature deformation and creep
[96S5, 97S5] as well as fatigue [96S5] are available.
Table 49. Selected data for 0.2 % yield stress σy, tensile fracture stress σf, and tensile total elongation εf
at room temperature RT or higher temperature T for cast, wrought and powder metallurgically (PM)
processed Ni3Al-base alloys tested in air (Table 43) [96D2, 97S4].
Alloy Fabrication T [°C] σy [MPa] σf [MPa] εf [%]

IC-50 Wrought RT 487 1200 40
600 637 663 2
1000 130 170 92
IC-218 Cast & worked (1060 °C 1h) RT 655 1390 37
700 672 778 12
1000 27 74 465
IC-218 PM & worked (1060 °C 1h) RT 544 1425 33
800 440 555 11
1000 112 148 30
IC-218LZr Wrought RT 562 1310 44
650 600 787 11
1000 131 205 45
IC-221M Cast RT 618 900 14
800 720 845 13
1000 413 470 10
IC-221W PM RT 1217 1348 7
650 1217 1326 6
870 225 288 13
IC-396 Cast RT 583 825 18
800 683 750 9
1000 368 438 10
Ni3Al-base alloys show an excellent corrosion resistance in air as well as in carburising and
chlorinating/oxidising atmospheres - see Table 50 - whereas the corrosion resistance is low in
sulphidising atmospheres. Cr and Zr additions improve the corrosion resistance in oxygen deficient
chlorinating atmospheres whereas they reduce the corrosion resistance in oxygen containing atmospheres
[99K1].

Table 50. Mass change ∆m of Ni3Al-base alloys - see Table 43 - at temperature T after exposure (time t)
in various atmospheres.
Alloy or composition [wt.%] Atmosphere T [°C] t [h] ∆m [g/m2] Ref.

IC-50 Air-5 % H2O 1100 960 < +10 97S5
H2-1 % CH4 1000 840 +3 97S5
IC-218 Air-5 % H2O 1100 960 < +10 97S5
H2-1 % CH4 1000 840 +10 97S5
IC-221 Air-5 % H2O 1100 960 < +10 97S5
H2-1 % CH4 1000 840 +20 97S5
Ni-11.7Al0.2Cr-0.02B-0.012C Air 1100 1008 +6 99K1
CH4/H2 1000 1008 +3 99K1
(aC = 0.8)
10 % HCl/H2 850 1008 –343 99K1
0.25 % Cl2/ 850 1008 +7 99K1
20 % O2/Ar
10 % SO2/ 750 1800 +433 99K1
90% N2
Ni-13.3Al H2-10 % H2S 900 25 +525 96S1
Ni-10.5Al-0.4Zr-0.021B-0.01C Air 1100 1008 +32 99K1
Ni-8.3Al-7.9Cr-0.97Zr-0.032B-0.021C Air 1000 1008 +18 99K1
CH4/H2 1000 1008 +56 99K1
(aC = 0.8)
10 % HCl/H2 850 1008 +32 99K1
SO2/90 % N2 750 1800 +630 99K1
Ni-10.8Al-6.0Cr-0.8Hf-0.1Mn-0.06C-0.05B Air 920 40 +3 90F
1010 45 +15 90F
Air-1.2 % SO2 920 40 +54 90F
960 40 + 64 90F
110 40 +115 90F
Air-3 % SO2 920 40 +110 90F
Ni-11.1Al-6.1Cr-0.8Zr-0.06Mn-0.04C-0.05B Air 920 40 +8 90F
960 45 +45 90F
1010 45 +130 90F
Air-3 % SO2 920 40 +120 90F
14.4.4.3 NiAl-base alloys
NiAl -base alloys excel by their high melting temperature, high thermal conductivity and high oxidation
and corrosion resistance. The upper temperature limit for structural applications is about 1200 °C due to
strength and 1400 °C due to corrosion [97D4]. Alloy developments, which are still in progress, have
resulted in various NiAl-base alloys of practical importance - see Table 51. Powder metallurgy methods
have been applied successfully for producing NiAl-base alloys [96G1, 97H3, 97S4, 97W3, 98K1, 98L1,
99Z]. NiAl-base alloys can be joined by friction welding, diffusion bonding, transient liquid phase
processing and brazing [94T1, 97D2, 98G1, 99G, 99S3].
NiAl-base alloys have been used since long for protective coatings on Ni-base and Co-base superalloys,
which are applied by a pack cementation process [93M2]. NiAl-base alloys are attractive for other new
applications as are listed in Table 52.

Table 51. NiAl-base alloys of practical importance.
Designation Fabrication Composition [at.%] Composition [wt.%] Ref.

NAL-109 PM combustion Ni-49.7Al-0.2Mo-0.2Fe- Ni-31.2Al-0.45Mo- 97D4
synthesis + hot 0.08Zr 0.26Fe-0.17Zr
extrusion
AFN-12 Single crystal Ni-48.45Al-1.0Ti-0.5Hf- Ni-29.8-1.1Ti- 97D1
0.05Ga 2.0Hf-0.08Ga
AFN-20 Single crystal Ni-44.45Al-5.0Ti-0.5Hf- Ni-26.8Al-5.4Ti- 97D1
0.05Ga 2.0Hf-0.08Ga
D176 Single crystal Ni-49.5Al-0.5Hf-0.05Ga Ni 30.6Al-2.0Hf- 97W2
(with unintentional 0.2Si) 0.08Ga
D218 Single crystal Ni-48.3Al-1.0Ti-0.5Hf- Ni-29.7Al-1.1Ti- 97W2
0.2Ga (with unintentional 2.0Hf-0.3Ga
0.2Si)
ODS-NiAl PM mechanical Ni-44.7Al-1.9Fe-0.75Y- Ni-28Al-2.5Fe- 98A
alloying 2.5 O-0.1C-0.1N 1.6Y-0.9O-0.04C-
0.03C
NiAl-AlN PM cryomilling + Ni-46.4-1.5N-0.9 O- Ni-29.2Al-0.5N- 97H2
2.7 HIP 0.08Fe-0.05Zr-0.07C 0.35O-0.1Fe-0.1Zr-
0.02C
NiAl-AlN PM cryomilling + Ni-48.5Al-16.7N-1.1 O- Ni-37Al-6.6N- 97H2
30.4 HIP 0.1Fe-0.03Zr-0.09C 0.52O-0.2Fe-0.08Zr-
0.03C
Ni20Al30Fe Casting Ni-30Fe-20Al Ni-32.5Fe-10.5Al 96G2
Alloy 10Al Casting + hot rolling Ni-27.6Fe-19.0Al-7.9Cr- Ni-30Fe-10Al-8Cr- 97K2, 99L2
0.03Hf 0.1Hf
NiAlCr27 Casting, directional Ni-36.5Al-27Cr Ni-21.7Al-30.1Cr 97P2, 97S2
solidification, PM
- Casting, directional Ni-33Al-34Cr Ni-19.4Al-38.5Cr 95J2
solidification
- Directional Ni-33Al-33Cr-1Mo Ni-19.2Al-37.0Cr- 95J2
solidification 2.1Mo
- Directional Ni-42.75Al-14.5Ta Ni-18.4Al-41.7Ta 95J1
solidification
IP75 Casting, investment Ni-45Al-7.5Cr-2.5Ta Ni-25.8Al-8.3Cr- 99Z
casting 9.6Ta
PM75 PM gas atomisation Ni-45Al-7.5Cr-2.5Ta Ni-25.8Al-8.3Cr- 99Z
+ HIP 9.6Ta
Table 52. Possible applications of NiAl-base alloys (see Table 51).
Application Ref.
Gas turbine: vane, combustor liner 97D2, 97W1, 97P2, 99Z
Automotive: diesel engine pre-chamber pin, brake disc 99Z
Coating 93M2
Semiconductor metallisation 93M2
High voltage electrode in vacuum circuit breakers 93M2
Surface catalysts 93M2
High temperature sensors and actuators 93M2

The density ρ [g/cm3] of binary NiAl alloys at room temperature varies with Ni content XNi [at.%]
according to [93N]:
ρ = 0.118 XNi for 45 ≤ XNi ≤ 50 (3)

and
ρ = 3.15 + 0.055 XNi for 50 ≤ XNi ≤ 60 (4)
The thermal expansion coefficient α [1/K] of NiAl is a strong function of temperature T [°C] but not of
composition [93N]:
α = 1.16026⋅10-5 + 4.08531⋅10-9 (T + 273) – 1.58368⋅10-12 (T + 273)2 + 4.18374⋅10-16 (T + 273)3 (5)

for 20 °C ≤ T ≤ 1000 °C
Respective data for some alloys of Table 51 are shown in Table 53. Thermal conductivity data for binary
NiAl are given in Table 54. Other thermodynamic, thermophysical, electrical, magnetic and optical
property data are available [93N, 93M2, 97S6].
The elastic properties are known as a function of temperature and composition for monocrystalline
and polycrystalline NiAl [93N, 93M2]. The data for Young's modulus E [GPa], shear modulus G [GPa],
and Poisson's ratio ν of powder metallurgically processed NiAl (hot pressing to full consolidation) are
described as a function of temperature T [°C] by the following relations.
E = 199.8 – 0.040 (T + 273) (5)

G = 76.6 – 0.017 (T + 273) (6)
ν = 0.307 + 2.15⋅10-5 (T + 273) (7)
It is noted that the elastic moduli are strongly anisotropic and are affected sensitively by texture.
Table 53. Mean thermal expansion coefficient α (room temperature to specified temperature T) of some
alloys of Table 51 .
Alloy T [°C] ρ [g/cm3] α [10-6/K] Ref.

D176 23 - 13 97D2
1200 - 16 97D2
NiAlCr27 23 6.28±0.03 - 97S2
500 - 11.8 97S2
IP75 23 6.35 - 95S2
1000 - 13.5 95S2
Table 54. Thermal conductivity λ of NiAl-base alloys (Table 51) at various temperatures T [97D2].
Alloy T [°C] λ [W/(m K)]

NiAl 20 77
600 79
1200 73
AFN-12 20 47
600 68
1000 68
AFN-20 20 25
600 42
1100 42

The mechanical behaviour of monocrystalline and polycrystalline NiAl-base alloys has been studied
extensively as a function of stress, temperature and alloying additions including fracture toughness and
fatigue [93N, 93M2, 96N, 97D1, 97D2, 97H2]. Much emphasis has been put on the high temperature
deformation behaviour and creep [93N, 93M2, 95W2, 96N, 97D1, 97D2, 97N3, 97W2, 97W4]. As to the
alloys of practical interest, complete data sets including tensile room temperature strength and ductility
are available only in few cases. Table 55 presents strength and ductility data for selected NiAl-base alloys
of Table 51 with additional data in the respective references.
Table 55. Selected data for tensile 0.2 % yield stress σy, tensile fracture stress σf, and tensile total
elongation εf at various temperatures T for cast and powder metallurgically processed (PM) NiAl-base
alloys (Table 51) tested in air.
Alloy Fabrication T [°C] σy [MPa] σf [MPa] εf [%] Ref.

NAL-109 PM 20 300 315 1 97S4
200 235 293 1 97S4
400 468 593 2 97S4
600 190 273 55 97S4
800 190 300 40 97S4
1050 70 70 50 97S4
NiAlCr27 Investment casting 600 300 304 0.2 97S2

800 184 284 56 97S2
1100 80 132 22 97S2
PM75 PM 23 - 441 0 99Z

800 255 295 11.2 99Z
900 172 187 5.7 99Z
1000 106 115 7.3 99Z
1200 58 94 13.1 99Z
PM + isothermal forging 800 237 298 7.9 99Z
1000 61 88 27.0 99Z
Ni20Al30Fe Extruded 23 850 - 7 97M6

Alloy 10Al Cast + hot rolled 23 593 1140 10.4 99L2
300 562 1140 13.9 99L2
450 618 1090 15.9 99L2
600 495 577 15.3 99L2
750 203 230 24.1 99L2
1000 25 50 >34 99L2

NiAl excels by its high oxidation resistance [95D1, 96M4]. Table 56 shows characteristic data which
indicate an initial stage I with fast growth of various Al2O3 modifications and a subsequent stage II with
formation of a protective α-Al2O3 scale. The oxidation rate constant of NiAl is increased by alloying NiAl
with Cr by less than an order of magnitude [92B3], whereas alloy IP75 with Cr and Ta shows a reduced
rate [98Z]. As to the oxidation and high temperature corrosion resistance of the alloys of Table 51, only
few data are available. Examples are given in Tables 57 - 58.
Table 56. Apparent parabolic rate constant kp for oxidation of pure NiAl in He/O2 (p(O2) = 133 mbar)
with initial stage I and final stage II as a function of temperature T [92B3].
T [°C] kp(I) [g2cm-4s-1] kp(II) [g2cm-4s-1]

700 5.7⋅10-16
800 8.3⋅10-15 -
850 3.1⋅10-14 -
900 1.7⋅10-13 -
950 5.9⋅10-13 2.7⋅10-15
1000 9.9⋅10-13 2.3⋅10-14
1050 3.4⋅10-12 7.4⋅10-14
1100 - 3.2⋅10-13
1200 - 2.0⋅10-12
1300 - 1.6⋅10-11
1400 - 5.9⋅10-11
Table 57. Mean apparent parabolic rate constant kp for oxidation of alloy 10Al as a function of
temperature T for exposures in air up to 16 h [97K2].
T [°C] kp(I) [g2cm-4s-1]

1000 8.3⋅10-13
1100 1.6⋅10-12
1200 1.2⋅10-11
1300 3.9⋅10-11
Table 58. Mass change ∆m of selected NiAl-base alloys - see Table 51 - at temperature T after exposure
(time t) in various atmospheres.
Alloy Atmosphere T [°C] t [h] ∆m [g/m2] Ref.

Alloy 10Al Air 1100 1008 (cyclic) +25 97K2
10 % SO2/air 650 1008 +1 97K2
1 % H2S/10 % CO2/H2 600 1008 +0.3 97K2
CH4/H2 (aC = 0.8) 1100 1008 ≈0 97K2
IP75 He/O2 (p(O2) = 133 mbar) 1100 70 +0.8 98Z
Air (cyclic) 1200 8330 +660 99H2
1 % SO2/air 850 2000 +3 98Z

14.4.5 Silicides
Various transition metal silicide phases are considered as promising candidate phases for the development
of new high temperature materials because of attractively high melting temperature, strength, oxidation
resistance and low density [95S1, 96M1, 99P2, 99S5]. Up to now only the molybdenum disilicide MoSi2,
which is used since long for heating element applications (see Table 1), has given rise to advanced
developments of new structural materials for high temperature applications which are covered in the
present section.
The phase diagrams for the alloy systems with Si and transition metals are usually not well established
and are subject of ongoing research. The available information is documented in the standard phase
diagram collections [90M, 95V2]. In view of the developments of new alloys and composites on the base
of MoSi2 Figs. 14.9 - 14.11 present the available information on the binary Mo-Si system and the ternary
Mo-Si-C and Mo-Si-N systems.
Si content w Si [wt.%]
0 10 20 30 50 70 100
2623°C
L
2400
2180°C
Temperature T [°C]
25.72
2030°C
2025°C 2020°C
2000 ~4
26.4 37 1900°C
40 54
1414°C
(Mo) Mo3Si Mo5Si3 αMoSi 2
1600
1400°C
Fig. 14.9. Updated Mo-Si phase
98.3
diagram [90M, 98F].
(Si)
1200
0 20 40 60 80 100
Mo Si content c Si [at.%] Si

T = 1200°C Mo
20 80
Mo 3Si
Mo 2C
Mo
%]
Mo5Si3
con
[at.
40 60
ten
C
c
Mo5Si3C
t c Mo
ent
ont
[at.
Cc
60 40
%]
MoSi2
80 20
Fig. 14.10. Updated isothermal section at 1200 °C of

L the Mo-Si-C phase diagram [94C, 95V2].
C 20 40 SiC 60 80 Si
Si content c Si [at.%]
T = 1400°C N
20 80
. %]
Nc
40 60
o [at
ont
Si3N4
cM
ent
t
ten
cN
con
[at.
60 40
%]
Mo
80 20
(Mo) Fig. 14.11. Isothermal section at 1400 °C of the

Mo-Si-N phase diagram [95V2].
Mo 20 40 60 80 Si
Mo 3Si Mo5Si3 MoSi2
Si content c Si [at.%]

14.4.5.2 MoSi2-base alloys
The intermetallic phase MoSi2 is most attractive for structural high temperature applications because of
low cost, high melting temperature, low density and ease of machining apart from excellent oxidation
resistance and electrical and thermal conductivity, on which its past and present application as heating
elements has relied [99H1, 99Y2]. Problems are poor toughness at low temperature, poor creep resistance
at high temperatures and catastrophic "pest" oxidation at intermediate temperatures at about 400 to 600 °C,
which have been overcome by using MoSi2 as matrix or strengthening phase in ceramic composite
materials. The MoSi2 materials - as well as other silicide materials - are usually fabricated by the familiar
powder metallurgy methods [99S5, 99Y2]. Joining of MoSi2 materials is possible by brazing [97C3,
98V1]. Advanced structural MoSi2 materials are shown in Table 59 with possible applications.
Table 59. New structural MoSi2-base materials of practical importance and prospective applications.
Material 2nd phases [vol.%] Application Ref.

MoSi2 - Glass fabrication 93P1, 95K1,
99P2, 99Y2
Industrial gas burners 99Y2
MoSi2-Al2O3 82 Molten metal lances 95K3, 99Y2
microlaminate tubes
MoSi2-SiC 10 - 30 Wear resistant components at 97J, 98P,
high temperatures in 99P2, 99S2
oxidative/corrosive
environments
MoSi2-Si3N4 30 - 50 Blade outer air seal 99H1, 99Y2
components for aircraft engines
Si3N4-MoSi2 20 - 30 Ceramic glow plug for Diesel 99Y1
engine
SiC(f)/MoSi2-Si3N4(p) 20 - 35 Si3N4 particulate, Blade outer air seal 99H1, 99Y2
30 SCS-6 SiC fibers components for aircraft engines
Physical properties of MoSi2 and other silicides have been determined only in few cases - see e.g. [94G].
The available data scatter because of differences in material quality as a result of different processing.
Table 60 shows characteristic data. Data for the composite materials in Table 59 may be estimated by
using a rule of mixtures with the data of Table 61 for the constituent composite phases, which vary
appreciably as a function of the materials origin.
Table 60. Physical property data for MoSi2.
Property T [°C] Ref.

Density [g/cm3] 6.23 23 70Z
Melting temperature [°C] 2030 - 98F
Average linear thermal expansion coefficient [10-6/K] 7.4 200 92B2
8.1 659 92B2
9.15 1200 92B2
Young's modulus [GPa] 420 23 91L
385 600 91L
350 1100 91L

Property T [°C] Ref.

Shear modulus [GPa] 180 23 91L
165 600 91L
150 1100 91L
Poisson's ratio 0.15 23 90N
Heat capacity [J/(g K)] 0.435 23 92B2
0.49 300 92B2
0.53 700 92B2
Thermal conductivity [W/(m K)] 0.64 23 92B2
0.33 700 92B2
0.28 1400 92B2
Table 61. Average physical property data for the constituent phases of MoSi2 composites [93S, 99C2].
Phase Density [g/cm3] Melting Young's modulus Thermal expansion

temperature [°C] [GPa] coefficient [10-6/K]
MoSi2 6.2 2030 400/425 7.1/8.1
Al2O3 4.0 2050 524 9.1
Si3N4 3.2 1900 300/380 3.4/3.7
SiC 3.2 3600 407/690 4.0/5.5
HiNicalon SiC fibre 2.7 - 270 3.1
SCS-6 SiC fibre 3.00 - 400 4.8
MoSi2-base materials are brittle at room temperature with ductilities < 0.2 % and the brittle-to-ductile
transition temperature for MoSi2 is of the order of 1000 °C [99Y2]. The data for materials of different
origin may differ within broad limits due to different fabrication methods and may change as a result of
progressing developments. Representative data are shown in Table 62. Creep and fatigue data are
available [99S1].
Table 62. Representative data - i.e. fracture strength in tension (σft) or 4-point-bending (σfb) and fracture
toughness KIc in 4-point-bending at temperature T -for MoSi2-base materials of practical importance.
Material 2nd phases T [°C] σft [MPa] σfb [MPa] KIc [MPa m1/2] Ref.
[vol.%]
MoSi2 - 23 - 320 - 91L
- 23 - 2.5 – 4.5 93H
1000 - 285 - 91L
1380 - 60 - 91L
MoSi2-SiC 30 23 - 420 7.9 93H
900 - 610 11.0 93H
1050 - 490 8.0 93H
1250 - 120 - 93H
MoSi2-Si3N4 30 23 - - 5.2 99H1
1000 - - 10.0 99H1
SiC(f)/ 20 - 35 Si3N4 23 960 - - 99H1
MoSi2- Particulate, 640 760 - - 99H1
Si3N4(p) 30 SCS-6 SiC 1200 220 - - 99H1
fibers

MoSi2 is most attractive because of its outstandingly high oxidation resistance at very high temperatures
up to 1600 °C which relies on the formation of a protective SiO2 scale [93M1, 99Y2]. At intermediate
temperatures in the range 300 °C - 600 °C accelerated oxidation occurs, which may lead to disintegration
and powderisation known as pesting phenomenon. Available data are rare and depend sensitively on the
material quality. Examples are given in Table 63. As to corrosion in other media, only data for corrosion
in liquid glass are available [99P1].
Table 63. Mass change ∆m of selected MoSi2-base materials - see Table 59 - at temperature T after
exposure (time t) in various atmospheres.
Material Atmosphere T [°C] t [h] ∆m [g/m2] Ref.

MoSi2 (HIP) Air, oxygen 500 165 < +60 93M1
MoSi2 (sintered: dense) Air 500 111 +20 99K2
MoSi2 (sintered: porous) Air 500 100 +220 99K2
MoSi2 Air, oxygen 600 - 170 ≤ 0, 93M1
1400 > -10
MoSi2 (HIP) Air 1250 1330 +21 99H1
(cyclic)
MoSi2-50Si3N4 (HIP) Air 1250 1440 +10 99H1
(cyclic)
SCS-6/MoSi2-50Si3N4 (HIP) Air 1250 25 -20 99H1
(cyclic)
1300 +36 99H1
(cyclic)
MoSi2-SiC Air 1200 170 +40 93M1

14-38 14 Intermetallic materials
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1 Introduction 1-1

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Development of iron powder shipments in North America

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Lando lt -Bö rnst ein

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powder injection extrusion of plasticized

Full density hot isostatic pressing or

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Table 2. Commercial applications of refractory metals and alloys by industry.

Industry Products made of Products made of Products made of Products made of

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Industry Products made of Products made of Products made of Products made of

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12.2 Powder production

1st step: MoO3+H2 → MoO2+H2O; heat of reaction = – 46 kJ/mol [79U]

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Mo Fig. 12.2. Preferred reaction mechanism

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Reduction time MoO3 [wt.%] Mo4O11 [wt.%] MoO2 [wt.%] Mo [wt.%]

Reduction time MoO3 [wt.%] Mo4O11 [wt.%] MoO2 [wt.%] Mo [wt.%]

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12.3 Powder compaction

Lando lt -Börnst ein

Lando lt -Bö rnst ein

Fractional green density Dg /D0

Fig. 12.10. Fractional green density vs. compacting

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Lando lt -Bö rnst ein

Lando lt -Börnst ein

Fractional sintered density Ds /D0

Fig. 12.13. Sintered density vs. sintering temperature for

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Fig. 12.16. Total, closed and open porosity vs. sintering

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Open porosity [%]

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Fracture toughness KIC [MPa m 1/2]

Testing temperature T [°C]

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Table 7. Thermopysical properties of pure refractory metals.

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Alloy Composition Temperature for 100 % Typical ultimate tensile

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Ultimate tensile strength R m[MPa]

Fig. 12.24. Comparison of 100 h creep rupture data for

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13.1.1 Diamond and cubic boron nitride

Date Event Reference

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Date Event Reference

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Table 2. Chronological order of the evolution of hardmetal.

Date Event Ref.

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