12 Refractory Metals PDF

Ref. p.
12-23]
12 Refractory metals
12-1
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-beammelting, 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 1900s industrial use of refractory metals was confined mainly to pure metals. An
extensive development program was carried out beginning in the late 50s 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 g/g potassium
combined with a high amount of deformation ( > 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.
Lando lt -B rnst ein

New Ser ies VIII/2A2
12-2
[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 baseplates 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
Shaping and
compaction
Sintering
Full density
processing
die pressing
Mo,W,Ta
cold isostatic pressing

Mo,W,Ta
powder injection
molding
Mo,W
indirect heating
(resistance heating elements or
induction radiant heating)
Mo,W,Ta
deformation
Mo,W,Ta
extrusion of plasticized
powder
Mo,W
spray forming
W,Ta
direct heating
(self - resistance heating)
Mo,W,Ta
hot isostatic pressing or

uniaxial hot pressing
Mo,W,Ta
infiltration
Mo,W
Fig. 12.1: Large scale production routes for Mo, W and Ta.
Lando lt -Brnst ein
New Ser ies VIII/2 A2
99.97
99.9995
99.3
98.6
99.2-99.6
Mo50Re
Mo30W
52.4
69.7
Tungsten alloys
Pure W
UHP-W
AKS-W
Mo
Ta
Nb
Re
99.42
99.8-99.9
0.025
0.08
0.02
0.035
0.0480.1
0.100.12
0.010.07
Si
La
Ce
Th
97.9-98.9
0.370.43
W5Re
W26Re
AKS-W3Re
94.9
73.9
96.9
98.0
98.0
98.0-99.0
5.0
26
3.0
0.08
0.0130.07
00.06
0.0050.03
0.0040.01
0.150.3
0.28
0.24
0.120.24
0.5
Hf
1.2
47.5
W-La2O3
(WL)
W-Ce2O3 (WC)
W-ThO2 (WT)
AKS-W-ThO2
Zr
0.270.6
30
99.99
99.9995
99.98
Ti
Alloy
designation
Molybdenum
alloys
Pure Mo
UHP-Mo
TZM
MHC
Mo-La2O3
(ML)
M-Y2O3
(MY)
K-Si-Mo
Ref. p. 12-23]

New-Ser ies VIII/2A2
Table 1. Typical compositions of commercial refractory metal alloys (in wt.%, analyses of base-metal correspond to metallic purity)
0.851.7
1.62
0.0010.005
1.71
0.861.71
0.004
12-3
Alloy
designation
Tantalum
alloys
Pure Ta
Ta2.5W
Ta10W
Ta
2.5
10.0
99.95
97.4
89.9
10
9
28
Nb
99.9
98.9
88.8
60.8
60.8
53.1
Re
Si
La
Ce
Th
Ti
Zr
Hf
1.0
1
10
1
0.1
30
46.5
Niobium alloys
Pure Nb
Nb1Zr
C-103
FS-85
WC-3009
Nb-46.5Ti
Mo
12-4
Table 1. Typical compositions of commercial refractory metal alloys (in wt.%, analyses of base-metal correspond to metallic purity) (continued)
[Ref. p. 12-23
Lando lt -Brnst ein

New-Ser ies VIII/2 A2
Ref. p. 12-23]
12-5
Table 2. Commercial applications of refractory metals and alloys by industry.

Industry
Aerospace
and defence
industry
Products made of
molybdenum or
molybdenum alloys
jet vanes, shaped
charge liners, pipe
burners, stirring
nozzles
Automobile
spraying wires
industry
Chemical and support structures,
linings
pharmaceutical
industry
Lighting
industry
Materials
processing
industry

Products made of
tungsten or tungsten
alloys
jet vanes, kinetic
energy penetrators,
balancing weights,
rocket engine
components
balance weights
Products made of
tantalum or tantalum
alloys
rocket engine
components,
explosively formed
penetrators
Products made of
niobium or
niobium alloys
thrust chambers,
exhaust nozzles
linings, heat
exchangers,
membranes, bursting
discs, autoclaves,
vessels, stirrers,
thermocouple
sheaths, evaporation
coils, condensers,
coolers, bayonet
heaters
welding aids, getters current supply
incandescent and
support wires for
and electrode
halogen lamp
incandescent and
mountings for
filaments, electrodes
halogen lamps, wire
Na-high pressure
leads, mandrel wires, for HID-lamps,
lamps
sealing foils and cups, furnace ware, sealing
rods
extension parts,
dimming cups,
furnace ware, joining
sleeves
crucibles for
TIG-welding
glass melting
electrodes, extrusion synthesis of artificial
electrodes, glassdiamonds and cubic
dies, resistance
stirrers / gobbers,
BN, heating
welding electrodes,
linings for glass
elements, radiation
hot zones and
melting furnaces,
shields, furnace
components for quartz radiation shields,
parts, boats for
furnace ware,
glass production,
thermal vapor
components for hot
isothermal forging
deposition,
isostatic presses,
tools, extrusion dies,
spinnerets for
components for
casting dies /
production of
thermocouple sheaths quartz glass
production, crucibles synthetic fibers
/ pumps / valves /
for production of
stirrers / nozzles /
sapphire single
linings for zinc
production, resistance crystals, nozzles for
production of
welding electrodes,
ceramic wool /
heating elements,
fibres, filaments for
radiation shields,
electron beam
components for hot
welding / melting
isostatic presses,
equipment,
furnace ware,
mountings for
crucibles for
production of sapphire machining tools,
electrodes for EDM,
single crystals,
12-6
Industry
Materials
processing
industry
(cont.)
Producers of
electrical /
electronic
devices
Producers of
medical
equipment
Producers of
sporting
goods /
premium
goods / others
Products made of
molybdenum or
molybdenum alloys
crucibles for synthesis
of artificial diamonds
and cubic BN,
electrodes for melting
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
semiconductor baseplates, components for
microwave devices,
heat sinks, heat
spreaders, mesh
filaments, sputtering
targets, anode grids
for electronic tubes,
pins for miniature
diodes, covering
masks for photoetching, components
for ion implantation
and MBE equipment
fixed / rotating anodes
for X-ray tubes, X-ray
detectors,
[Ref. p. 12-24
Products made of
Products made of
Products made of
tungsten or tungsten tantalum or tantalum niobium or
alloys
alloys
niobium alloys
electrodes for plasma
spraying, boats /
coils for thermal
vapor deposition
electrical contacts,
switches, heat sinks,
heat spreaders,
sputtering targets,
components for ion
implantation and
MBE equipment,
semiconductor base
plates, mesh-grid
cathodes,
components for
experimental fusion
reactors, filaments
for CRTs
fixed / rotating
anodes for X-ray
tubes, X-ray
detectors,
collimators, shields
for nuclear medicine
golf club weight
inserts, weights for
darts, weights for
fishing lines, balance
weights for tennisrackets, grit as
accelerator material
for trace analysis of
carbon and sulphur
sputtering targets,
wires / foils / bats
for capacitors,
components for
CRTs, components
for MBE equipment
superconducting
cables
implants,
components for
pacemakers, stents
for expanding of
arteries, scanner
plates
jewellery
Lando lt -Brnst ein

Ref. p. 12-23]
12-7
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;
2nd step: MoO2+2H2 Mo+2H2O;
heat of reaction = 46 kJ/mol [79U]

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 m to 5 m.
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 -W -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 -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 m to 4.5 m.

12-8
[Ref. p. 12-23
Metallic tantalum powder is produced by reducing potassium fluotantalate (K2TaF7) with sodium
according to the reaction equation:
K2TaF7+5NaTa+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 m. 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 m. 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
H 2 , > -40C
H 2 , > -40C
Mo4 O11
MoO 3
PSM
H 2 , > 40C
CVT
MoO 2
CVT
CVT
H 2 , < 20C
Mo
1.00
Fig. 12.2. Preferred reaction mechanism

and intermediate phases for H2-reduction
of MoO3 in dependence on the dew point
() of the hydrogen,
PSM: solid state oxygen transport
mechanism (pseudomorphology),
CVT: chemical vapor transport mechanism,
MoO3: d50 (laser diffraction) = 4.4 m,
BET specific surface area = 3.35 m2/g,
filling weight = 100 mg,
temperature range / dew point range
investigated:
MoO3 Mo4O11 MoO2:
400 - 800 C
40 C < < + 25 C
MoO2 Mo: 500 - 1100 C
40 C < < + 25 C [98S1].
MoO 3
MoO 3
0.95
Weight loss m/m0
0.90
MoO 2
0.85
0.80
T = 400C
500C
600C
700C
800C
0.75
0.70
Mo
0.65
0.60
0
10
10 2
Time t [min]
10 3
10 4
Fig. 12.3. Weight loss vs. reduction time for isothermal

reduction of MoO3 at various temperatures,
MoO3: d50 (laser diffraction) = 0.41 m,
BET specific surface area = 3.10 m2/g,
filling weight (Pt-crucible) = 2 g,
reduction conditions: hydrogen with a flow rate of
8 l/h and a dew point of 0 C [98S1].
Lando lt -Brnst ein

Ref. p. 12-23]
12-9
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 m, 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
300s
900s
1800s
2700s
1h
1.5h
2h
20h
MoO3 [wt.%]
80
17
-
Mo4O11 [wt.%]
20
72
59
30
7
-
MoO2 [wt.%]
11
41
70
90
79
51
-
Mo [wt.%]
3
21
49
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 m, 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
1080s
1980s
3120s
4440s
20h
MoO3 [wt.%]
15
-
Mo4O11 [wt.%]
79
69
43
16
-
MoO2 [wt.%]
6
31
57
84
82
Mo [wt.%]
18
WO 3
1
WO 2.9
WO 2.72
6
WO 2
-W
10

-W
Fig. 12.4. Formation of oxide intermediates during the

hydrogen reduction of WO3. Under industrial conditions
(above 750 C and high oxygen partial pressure) a
stepwise reduction occurs following the sequence
1 4 6 9. The main reduction mechanism is a
chemical vapor transport reaction with WO2(OH)2 as the
gaseous transport phase. Under low oxygen partial
pressure reduction is determined by oxygen transport by
solid state diffusion (reduction paths 2, 5, 7 and 8)
[91S1].
12-10
[Ref. p. 12-23
1.00
WO 3
1 T = 800 C
870 C
2
3
900 C
950 C
4
5 1000 C
0.96
Weight loss m/m0
0.92
0.88
0.84
5 4
0.80
0.76
0
200
400
600
Time t [min]
800
1000
Fig. 12.5. Weight loss of WO3 vs. isothermal reduction

time for various temperatures,
WO3: Fisher subsieve size = 20 m, filling weight
(alumina crucible) = 90 mg, powder layer height =
3 mm, reduction conditions: hydrogen with a flow rate
of 15 l/h and a dew point of 40 C [96L].
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 AKStungsten, 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.
Lando lt -Brnst ein

Ref. p. 12-23]
12-11
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.
Fisher subsieve size [m]

Fractional apparent density
Yield strength at ambient temperature
(recrystallized condition) [MPa]
Grain shape
Typical compacting pressure [MPa]
Typical fractional green density
Mo
2-5
0.11 - 0.17
350 - 480
W
1.5 - 4.5
0.13 - 0.22
550 - 650
Ta
6 - 10
0.20 - 0.28
150 - 300
Nb
4-8
0.18 - 0.25
120 - 250
aggregate
200 - 500
0.60 - 0.68
aggregate
200 - 500
0.60 - 0.68
rounded
200 - 500
0.70 - 0.77
angular
200 - 500
0.73 - 0.83
0.8
1.00
3N Mo - powder
Fractional green density Dg /D0
0.7
0.6
0.5
0.4
0.75
0.50
Mo
Al
Fe
Ni
0.25
0.3
0.2
0
100
300
400
200
500
Compacting pressure p [MPa]
600
Fig. 12.6. Fractional green density vs. compacting

pressure for molybdenum,
(Dg = green density, D0 = theoretical density)
powder: 3N Mo, Fisher subsieve size = 4.5 m,
d50 (laser diffraction) = 8.9 m,
apparent density = 1.15 g/cm3,
compacting: die pressing, dia. of the die = 12 mm,
filling weight = 6 g.

1000
500
1500

pressure for molybdenum in comparison with nickel,
iron and aluminum,
powder:
Mo: Fisher subsieve size = 3.0 m,
fractional apparent density = 0.33,
Ni: Fisher subsieve size = 50 m,
Fe: Fisher subsieve size = 32 m,
Al: Fisher subsieve size = 27 m,
compacting method: isostatic pressing - wet bag tooling,
proposed empirical pressure-density relationship:
(1Da/1Dg) = 1 + qpr
with Da = apparent density, Dg = green density,
p = compacting pressure, q, r = constants [74S].
12-12
0.9
0.60
3N Ta - powder
AKS - W powder
Fractional green density Dg /D 0
[Ref. p. 12-23
0.55
0.50
0.45
0.40
0
50
100
150
200
250

pressure for AKS-tungsten,
AKS-tungsten powder: Fisher subsieve size = 1.6 m,
compacting method: isostatic pressing - dry-bag tooling,
filling weight = 290 g, filling density = 4.0 0.01 g/cm3
[92B1].
0.8
0.7
0.6
100
300
400
200
500

pressure for tantalum,
powder: 3N tantalum, Fisher subsieve size = 10.5 m,
apparent density = 3.7 g/cm3,
compacting: die pressing, dia. of the die = 12 mm,
filling weight = 10 g.
1.00
W - powder
0.75
0.50
0.25
W(0.004mm)
W(0.015mm)
0
500
1000
1500

pressure for tungsten,
powder:
W (0,004 mm): Fisher subsieve size = 4.0 m,
W (0.015mm): Fisher subsieve size = 15 m,
compacting: isostatic pressing - wet bag tooling,
proposed empirical pressure-density relationship:
(1Da/1Dg) = 1 + qpr
with Da = apparent density, Dg = green density,
p = compacting pressure, q, r = constants [74S].
Lando lt -Brnst ein

Ref. p. 12-23]
12-13
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 510-3 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 m. 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 m and 4.55 m 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 m instead of 4.05 m makes
it possible to reduce the sintering temperature by around 400 C, which is of great practical relevance,
especially for tungsten.

12-14
[Ref. p. 12-23
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 m powder
compared to a sintered compact made of 10 m 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 m 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 m and 0.85 m 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 nonuniform 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 g/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.
Lando lt -Brnst ein

Ref. p. 12-23]
1.00
0.96
Molybdenum
0.95
Fractional sintered density Ds /D0
0.95
12-15
0.94
0.93
0.92
0.91
0.90
Molybdenum
0.90
0.85
0.80
0.75
0.70
3.00 m
4.55 m
0.65
0.60
0.89
0.45
0.50
0.55 0.60 0.65 0.70 0.75

0.80
Fig. 12.11. Fractional sintered density vs. fractional

green density for molybdenum specimens,
(Ds = sintered density, D0 = theoretical density)
powder: 3N molybdenum with Fisher subsieve size of
4.6 m, apparent density = 1.36 g/cm3,
d50 (laser diffraction) = 11.0 m,
compacting: die pressing (100 MPa < p < 500 MPa),
sintering:
indirect heating, sintering temperature = 2050 C,
isothermal sintering time = 5 h,
sintering atmosphere: hydrogen [98S1].
0.55
700
1100
1500
1900
Sintering temperature T [C]
2300
Fig. 12.12. Fractional sintered density vs. sintering

temperature for molybdenum specimens,
powder:
3N molybdenum with Fisher subsieve size of 3.0 m
(apparent density = 0.88 g/cm3, tap density = 1.97 g/cm3),
3N molybdenum with Fisher subsieve size of 4.55 m
(apparent density = 0.97 g/cm3, tap density = 2.22 g/cm3),
compacting: isostatic pressing with a compacting
pressure of 220 MPa, fractional density (Mo-powder
Fisher subsieve size of 3.0 m) = 0.597,
fractional density (Mo-powder Fisher subsieve size of
4.55 m) = 0.630,
sintering: indirect heating, heating rate: 300 C/s,
isothermal sintering time = 1 min., sintering atmosphere:
hydrogen (dew point = 30 C).
20
Sintered density Ds [g/cm 3 ]
Tungsten
18
16
14
12
W 2.15 m
W 4.05 m
10
8
1000
1400

1800
2200
Temperature T [C]
2600
Fig. 12.13. Sintered density vs. sintering temperature for

tungsten specimens,
powder: 3N tungsten with Fisher subsieve size of 2.15 m
and 4.05 m,
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/cm (tungsten powders with
Fisher subsieve size of 2.15 m) and 11.9 g/cm
(tungsten powders with Fisher subsieve size of 4.05 m),
sintering: indirect heating, heating rate = 0.2 C/s,
isothermal sintering time = 1 hour, sintering atmosphere:
hydrogen [96B2].
12-16
[Ref. p. 12-23
40
1.0
Molybdenum
0.9
30
Frequency [%]
Densification param.(D s - Dg /D t - Dg )
Tungsten
0.8
0.7
20
2.5 m
4.3 m
10.0 m
10
0.6
W 2.15 m
W 4.05 m
0.5
100
1000
10000
Sintering time t [s]
100000
Fig. 12.14. Sintering densification parameter vs.

sintering time for tungsten compacts sintered at 2100 C
(Ds = sintered density, Dg = green density,
Dt = theoretical density),
powder: 3N tungsten with Fisher subsieve size of
2.15 m and 4.05 m,
300 MPa, diameter of the die = 12 mm, filling weight = 12 g,
green density = 11.7 g/cm (tungsten powders with
Fisher subsieve size of 2.15 m) and 11.9 g/cm
(tungsten powders with Fisher subsieve size of 4.05 m),
sintering atmosphere: hydrogen.
10
15
Pore size d [m]
20
25
Fig. 12.15. Pore size distribution of sintered 3N8

molybdenum specimens,
powder / sintered density:
Fisher subsieve size = 2.6 m: sintered density = 9.84 g/cm,
compacting: isostatic pressing with a pressure of
220 MPa.
0.5
Tungsten
total porosity
closed porosity
open porosity
Fractional porosity
0.4
0.3
Fig. 12.16. Total, closed and open porosity vs. sintering

temperature for tungsten specimens,
powder: tungsten with a mean particle size of 0.5 - 1 m,
BET specific surface area = 0.6 m/g,
compacting: die pressing with a green density of the
compacts of 11.6 g/cm,
sintering: isothermal sintering time = 2 hours,
atmosphere: hydrogen [90R].
0.2
0.1
20 1000
1500
2000
Lando lt -Brnst ein

Ref. p. 12-23]
10
35
Molybdenum
Mo 3.05 m/H 2 dew point = 40 C

Mo 3.05 m/N 2 - H 2 dew point = 0 C
30
-10
Molybdenum
25
-20
Open porosity [%]
Length change L/L0
12-17
-30
-40
-50
Mo 3.05 m/H 2 - dew point = 40 C
Mo 3.05 m/N 2 - H 2 - dew point = 0 C
-60
-70
0
15
10
5
400 600 800 1000 1200 1400 1600

200
20
Fig. 12.17. Dilatometer curves; change in length L/L0

vs. sintering temperature,
powder: 3N molybdenum with a Fisher subsieve size of
3.05 m,
pressure of 220 MPa,
dilatometric test: indirect heating, heating rate = 0.14 C/s,
atmosphere: hydrogen with a dew point of 40 C and
forming gas with a N2:H2 ratio of 95:5 and a dew point
of 0 C, equivalent to a hydrogen atmosphere with a
dew point of 50 C [01S2].
0
1200
1400
1800
2000
1600
2200
Fig. 12.18. Open porosity vs. sintering temperature

measured by means of mercury porosimetry,
powder: 3N molybdenum powder with a Fisher subsieve
size of 3.05 m,
pressure of 220 MPa,
atmosphere: hydrogen with a dew point of 40 C and
forming gas with a N2:H2 ratio of 95:5 and a dew point
of 0 C, equivalent to a hydrogen atmosphere with a dew
point of 50 C [01S2].
10.0
Molybdenum
9.5
Densit y D [g/cm 3 ]
9.0
green density
1000C/1min.
1400C/1min.
1900C/1min.
8.5
8.0
7.5
7.0
6.5
0
20

40
60
80
Weight fraction fine powder [%]
100
Fig. 12.19. Green and sintered density vs. composition

of 3N molybdenum powder mixtures made of coarse
grained (Fisher subsieve size = 4.6 m) and fine grained
(Fisher subsieve size = 0.85 m) powders for various
sintering temperatures,
350 MPa, dimension of the green parts: dia. = 10 mm,
h = 5 mm,
isothermal sintering time = 1 min., sintering atmosphere:
hydrogen with a dew point of 20 C.
12-18
24
1.0
Tungsten
Tantalum
20
0.9
Fracture toughness KIC [MPa m 1/2]
[Ref. p. 12-23
0.8
0.7
0.6
2600C/3h
2400C/5h
2400C/3h
2400C/1h
2200C/3h
AS CIP
0.5
Fig. 12.20. Fractional sintered density in dependence on

sintering conditions for tantalum,
powder: tantalum, Fisher subsieve size = 9.9 m,
apparent density = 3.82 g/cm, tap density = 5.81 g/cm,
oxygen content = 234 g/g, hydrogen content = 651 g/g,
pressure of 345 MPa (dia. = 25.4 mm), green density =
13.28 g/cm,
sintering: indirect heating, heating rate 1.6 C/s,
atmosphere: vacuum 1.310-2 Pa or better [96B1].
16
12
1 porosity = 40%
2 porosity = 32%
3 porosity = 24%
4 porosity = 14.5%
5 porosity = 8%
6 porosity = 6%
8
3
2
4
0
200
1
0
200
Testing temperature T [C]
400
Fig. 12.21. Fracture toughness KIC of sintered tungsten

specimens with various porosities vs. testing temperature,
powder: tungsten with mean particle size of 0.5-1.0 m,
BET specific surface area = 0.6 m/g,
compacting: die pressing with a green density of the
compacts of 1.6 g/cm3,
sintering:
sintering temperature for porosity 6 %: 2000 C
sintering temperature for porosity 14.5 %: 1800 C
isothermal sintering for 2 hours, atmosphere hydrogen
[90R].
Lando lt -Brnst ein

Ref. p. 12-23]
12-19
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
12-20
[Ref. p. 12-23
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].
Atomic number
Relative atomic mass
Atomic volume [m3]
Density at 20 C [g/cm3]
Crystal structure
Lattice constant [nm]
Burgers vector [m]
Electrical resistivity at 20 C [ m]
Mo
42
95.94
1.5310-29
10.2
bcc
0.3147
2.7310-10
0.052
W
74
183.85
1.5910-29
19.3
bcc
0.3165
2.7410-10
0.055
Ta
73
180.95
1.8010-29
16.6
bcc
0.3303
2.8610-10
0.125
Nb
41
92.91
1.8010-29
8.6
bcc
0.3294
2.8610-10
0.140
Table 7. Thermopysical properties of pure refractory metals.

Mo
2610
5560
710-2
W
3410
5900
110-5
Ta
2996
6100
110-4
Nb
2468
~4900
5.510-3
5.15
4.42
6.35
5.35
5.56
5.77
5.98
6.19
4.55
4.70
4.86
5.02
5.18
6.53
6.73
6,93
7.12
7.32
7.10
(100 C)
7.32
7.64
7.95
20 C
141
159
54.4
300 C
600 C
900 C
1200 C
1500 C
133
124
116
107
101
143
125
118
112
Melting point [ C]
Boiling point [ C]
Vapor pressure at 2500 K [Pa]
Coefficient of linear thermal
expansion [m/(m K)]
Source
[64L]
[64L]
[97P1]
Mo: [00P]
W: [86P]
Ta: [89P]
Nb: [64L]
20 C
300 C
600 C
900 C
1200 C
1500 C
Thermal conductivity [W/(m K)]
Mo: [00P]
W: [97P1]
Ta, Nb: [64L]
52.3
(0 C)
58.6
65.3
72.8
(1430 C)
Lando lt -Brnst ein

Ref. p. 12-23]
12-21
Specific heat [J/(g K)]

20 C
300 C
600 C
900 C
1200 C
1500 C
Source
Mo, W: [00P]
Ta, Nb: [89P]
Mo
Ta
Nb
0.254
0.268
0.283
0.298
0.313
0.324
0.132
0.138
0.144
0.150
0.156
0.162
0.142
0.147
0.152
0.158
0.264
0.282
0.300
0.318
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 .
Alloy
Composition
designation
Typical ultimate tensile

strength at 1000 C
Pure Mo
TZM
MHC
ML
Temperature for 100 %

recrystallized structure
(t = 1 h)
C
wt.%
1100 ( = 90 %)
Mo, 0.5 % Ti, 0.08 % Zr, 0.025 %C 1400 ( = 90 %)
Mo, 1.2 % Hf, 0.08 % C
1550 ( = 90 %)
Mo, 0.3 % La2O3
1300 ( = 90 %)
2000 ( = 99.99 %)
Mo, 0.48 % La2O3, 0.07 % Ce2O3
1100 ( = 90 %)
1350 ( = 99.99 %)
Mo, 0.05 % Si, 0.025 % K
1200 ( = 90 %)
1800 ( = 99.99 %)
Mo, 47.5 % Re
1300 ( = 90 %)
Mo, 30 % W
1200 ( = 90 %)
1350 ( = 90 %)
W, 0.005 % K
2000 ( = 99.9 %)
W, 1.0 % La2O3
1500 ( = 90 %)
2500 ( = 99.99 %)
W, 1.5 % La2O3
1550 ( = 90 %)
2600 ( = 99.99 %)
W, 1.9 % Ce2O3
1550 ( = 90 %)
2600 ( = 99.99 %)
W, 2 % ThO2
1450 ( = 90 %)
2400 ( = 99.99 %)
W, 1 % ThO2, 0.004 % K
2400 ( = 99.9 %)
MPa
250 ( = 90 %)
600 ( = 90 %)
800 ( = 90 %)
300 ( = 90 %)
W, 5 % Re
W, 26 % Re
500 ( = 90 %)
900 ( = 90 %)
MY
K-Si-Mo
Mo50Re
Mo30W
Pure W
AKS-W
WL10
WL15
WC20
WT20
AKS-WThO2
W5Re
W26Re

1700 ( = 90 %)
1750 ( = 90 %)
300 ( = 90 %)
300 ( = 90 %)
600 ( = 90 %)
350 ( = 90 %)
350 ( = 90 %)
800 ( = 99.9 %)
400 ( = 90 %)
420 ( = 90 %)
420 ( = 90 %)
400 ( = 90 %)
1000 ( = 99.9 %)
12-22
700
1200
Mo
W
Ta
Nb
500
Mo
W
Ta
TZM
Ta 10W
1000
Ultimate tensile strength R m[MPa]
Ultimate tensile strength R m[MPa]
600
400
300
200
800
600
400
200
100
[Ref. p. 12-23
400
800
1200
1600
2000
Fig. 12.22. Ultimate tensile strength vs. testing

temperature for Mo, W, Ta and Nb rods in their usual
as-delivered condition,
Mo, W: diameter = 25 mm, Ta, Nb: diameter = 12 mm,
Mo, W: material condition: stress relieved,
Ta, Nb: material condition: recrystallized.
400
800
1200
1600
2000
Fig. 12.23. Ultimate tensile strength vs. testing

temperature for Mo, TZM, W, Ta and Ta10W sheets
with a thickness of 1 mm, material condition: stress
relieved.
1000
Stress [MPa]
100
W
TZM
W - 25Re
Nb
Ta
Mo
10
1
1000 1100 1200 1300 1400 1500 1600 1700 1800 1900
Fig. 12.24. Comparison of 100 h creep rupture data for

selected refractory metals [71C].
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12-23
References for 12
61H
64K
64L
64V
69T
71C
74S
76D
76F
79O
79U
81S1
81S2
83H1
83H2
86P
89P
89Z
90R
91S1
91S2
91S3
91V
91Z
92B1
92B2
92L
92S
93B
93F
93S
94B
94G
95L
95S
96B1
96B2
96D
96L
97D
97P1
Heckel, R.W.: Trans. Metall. Soc. AIME, 221 (1961) 1001.

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

12-24
97P2
98S1
98S2
00B
00D
00P
01B
01G
01K
01M
01S1
01S2
Parteder, E., Knabl, W., Stickler, R., Leichtfried, G.: Proc. 14th Plansee Seminar, Reutte 1
(1997) 985.
Schulmeyer, W.V.: Mechanismus der Wasserstoffreduktion, Thesis, Darmstadt, 1998.
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.
Buckman, R.W.: Int. J. Refract. Met. Hard Mater. 18 (2000) 253.
DiStefano, J.R.: Int. J. Refract. Met. Hard Mater. 18 (2000) 237.
Bewlay, B.P., Briant, C.L., Jackson, M.R., Subramanian, P.R.: Proc. 15th Plansee Seminar,
Reutte 1 (2001) 405.
Gnesin, B.A., Kireiko, V.V., Zuev, A.P.: Proc. 15th Plansee Seminar, Reutte 3 (2001) 161.
Kumar, P., Uhlenhut, H.: Proc. 15th Plansee Seminar, Reutte 1 (2001) 449.
Makarov, P., Povarova.: Proc. 15th Plansee Seminar, Reutte 1 (2001) 464.
Stallybrass, Ch.: Diploma Thesis, Montanuniversitt Leoben, 2001.
Stallybrass, Ch., Leichtfried, G.: Proc. 15th Plansee Seminar, Reutte 1 (2001) 267.
Lando lt -Brnst ein


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Ref. p.

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cold isostatic pressing

hot isostatic pressing or

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

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12.2 Powder production

heat of reaction = 46 kJ/mol [79U]

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Fig. 12.2. Preferred reaction mechanism

Weight loss m/m0

Fig. 12.3. Weight loss vs. reduction time for isothermal

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Fig. 12.4. Formation of oxide intermediates during the

Weight loss m/m0

Fig. 12.5. Weight loss of WO3 vs. isothermal reduction

12.3 Powder compaction

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Fisher subsieve size [m]

Fractional green density Dg /D0

Fig. 12.6. Fractional green density vs. compacting

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Fig. 12.7. Fractional green density vs. compacting

Fig. 12.8. Fractional green density vs. compacting

Fig. 12.9. Fractional green density vs. compacting

Fractional green density Dg /D0

Fig. 12.10. Fractional green density vs. compacting

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Fractional sintered density Ds /D0

0.55 0.60 0.65 0.70 0.75

Fig. 12.11. Fractional sintered density vs. fractional

Fig. 12.12. Fractional sintered density vs. sintering

Sintered density Ds [g/cm 3 ]

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Fig. 12.13. Sintered density vs. sintering temperature for

Fig. 12.14. Sintering densification parameter vs.

Fig. 12.15. Pore size distribution of sintered 3N8

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

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Mo 3.05 m/H 2 dew point = 40 C

Length change L/L0

400 600 800 1000 1200 1400 1600

Fig. 12.17. Dilatometer curves; change in length L/L0

Fig. 12.18. Open porosity vs. sintering temperature

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Fig. 12.19. Green and sintered density vs. composition

Fracture toughness KIC [MPa m 1/2]

Fractional sintered density Ds /D0

Fig. 12.20. Fractional sintered density in dependence on

Fig. 12.21. Fracture toughness KIC of sintered tungsten

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Table 7. Thermopysical properties of pure refractory metals.

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Specific heat [J/(g K)]

Typical ultimate tensile

Temperature for 100 %

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