R RE EF FR RA AC CT TO OR RY YM ME ET TA AL LS S A ME ET TA AL LA AL LL LO OY YS S AN ND DR RE EF FR RA AC CT TO OR RY YM

What makes these elements refractory metals? Why not include V, Cr, Zr, Hf or Ti? Refractory metals can be loosely described as metals exhibiting melting points greater than 2000C. This group includes Nb (previously known as Cb), Ta, Mo, W, and Re. The only other metals that could fit into this category are the platinum-group metals Os and Ir. However, they are not considered refractory metals. 1

Properties of Refractory Metals

NOTE: All have BCC crystal structures except Re. All have high densities. Only Nb is light enough to be used in aircraft. 2

Properties of Refractory Metals contd.

MarM-246

Whats so special about refractory metals? They are weaker than Nibase superalloys.

Superalloys loose strength or melt above ~1200C

Many refractory metal alloys are used in chemical processing, rockets, or microelectronics, where their corrosion resistance is important. Our focus, however, is on the high temperature properties. The physical properties for a variety of refractory metal alloys are provided in Table 2 (page 363) of Heat-Resistant Materials. 3

Properties of Refractory Metals contd.

NOTE: All are fairly strong at elevated temperatures. Now, lets consider the different classes.

Molybdenum and Its Alloys Z = 42; Tmp = 2610C; = 10.22 g/cm3; E = 324 GPa; BCC. The good! Mo has a high specific elastic modulus (i.e. E/) and good strength at high temperatures. It is attractive for applications requiring both high stiffness and low weight. In fact, more Mo is used annually than any other refractory metal. Most of it, however, is used as an alloying element in irons, steels and superalloys. Mo-base mill products occupy roughly 5% of the market. It also has a high thermal conductivity, a low specific heat, and a low coefficient of thermal expansion. This makes Mo resistant to thermal shock and fatigue (very important for microelectronics). The bad! Mo is a group VIA metal. This is a problem. Why? It has a BCC crystal structure. Thus it displays a ductile-tobrittle transition (DBTT). A common problem with the group VIA metals is that the DBTT lies above room temperature, which means that the metal is typically brittle at room temperature unless special efforts are taken during processing.

Classes of Mo Alloys Carbide-strengthened o Rely on formation of fine reactive metal carbides to dispersion strengthen and increase the recrystallization temperature. Solid-solution strengthened o Rely on addition of solid solution elements to inhibit diffusion. Combination alloy o Combined carbide strengthening and solid solution strengthening. Dispersion-strengthened PM alloys o Rely on second phase particles introduced during powder processing to increase resistance to recrystallization and stabilize the recrystallized grain structure.

Compositions and Properties of Some Mo-Based Alloys

Fig. 5 Elevated-temperature properties of Mo and Mo alloys. (a) Tensile strength. (b) Larson-Miller parameter (LMP) with temperature given in degrees Kelvin and the time to rupture, tr, give in hours.

Alloys are very resistant to recrystallization! 7

Carbide Strengthened Mo-Based Alloys Examples

Alloy TZM Ti 0.5 Zr 0.08 C 0.03 Hf --Comments Most popular. Brittle

TZC MHC ZHM

1.2 -----

0.03 --0.50

0.01 0.05 0.20

--1.5 1.5

These alloys are used as isothermal hot forging dies for Ni-base alloys. They are also used as equipment for glass making and as heating elements in vacuum furnaces.

Solid Solution Strengthened Mo-Base Alloys Mo-25W Mo-30W W-xRe (where x = 5 47.5%) These alloys were developed for their chemical resistance. They are primarily used in the processing of molten Zn. They are low cost, lightweight alternatives to W-based alloys. Mo-5Re and Mo-41Re are used for thermocouple wire and for structural applications in the aerospace market. Re imparts high temperature strength and low temperature ductility on Mo. The rhenium effect has also been observed in Cr and W. How does it work?

Dispersion Strengthened Mo-Based Alloys Z-6: Mo 0.5 ZrO2 MH (HD): Mo 100 ppm K 300 ppm Si KW: Mo 200 ppm K 300 ppm Si 100 ppm Al Dispersion strengthened alloys rely on P/M manufacturing. This method of processing makes it possible to produce alloys containing fine dispersions of second phases. These fine dispersions of particles can stabilize the wrought structure thus preventing recrystallization. Alternatively, they can also stabilize a recrystallized elongated grain structure. Useful for good low temperature properties. See Heat-Resistant Materials for more details. These alloys generally possess high resistances to creep.

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Oxidation of Mo-Based Alloys These alloys cannot be used in air. Volatile oxides form. 3 Mo+ O 2 MoO3 ; F -180 kcal 2 m.p. of MoO3 795C b.p. of MoO3 1155C The liquid oxide is detrimental to these alloys because it permits easy transport of Mo and O ions through the oxide. High-temperature coatings are often used to protect these alloys.

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Coatings for Mo Metallic coatings for Mo

Process Type Electrodeposition Flame sprayed Clad or bonded Molten bath Material Cr, Ni, Au, Ir, Pd, Pt, Rh Ni-Cr-B, Ni-Si-B, Ni-Cr, NiMo Pt, Ni, Ni-Cr, Pt-Rh Cr Thickness Range (m) 12.7 76.2 127 254 50.8 508 12.7 25.4

Aluminide coatings for Mo

Type Al-Cr Al-Si Sn-Al Compositions 20%Al+80%(55Cr-40Si-3Fe-1Al) 88%Al-12%Si 90%(Sn-25Al)-10%MoAl3 Deposition Process Thermal spray Thermal spray, hot dip Slurry dip or spray Thickness Range (m) 178 254 12.7 178 50.8 203

Silicide Coatings for Mo Alloys

Type MoSi2 MoSi2 and Cr MoSi2 and Cr, B MoSi2 and Cr, Al, B MoSi2 and Sn-Al Deposition Process Fluidized bed, pack cementation, slip pack, plasma spray, electrophoresis Pack cementation Pack cementation Slip pack Cementation and impregnation

Above 1650C, only refractory oxides are suitable as coatings. Oxide Coatings for Mo
Type Zirconium oxide/glass Chromium-glass Chromium/aluminum oxide Aluminum oxide Zirconium oxide Zirconium oxide Deposition Process Frit, enamel Frit, enamel Thermal spray over chromium plate Thermal spray Thermal spray Troweling Thickness Range (m) 130 760 130 250 200 380 25 2500 25 2500 2500 7600

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Tungsten Based Alloys Z = 74; Tmp = 3410C; = 19.26 g/cm3; E = 414 GPa; BCC. Used in a variety of applications including light bulb filaments, in carbide cutting tools, as an alloying element in steels and superalloys, in aerospace applications, etc

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Groups of Tungsten-Based Alloys: Unalloyed W Doped W Solid solution alloys o Contain 2 20%Mo or 1 25%Re Dispersion-strengthened alloys o Contain 1 2%ThO2 or HfC W heavy alloys o W-Ni-Cu or W-Ni-Fe

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Unalloyed W Properties depend strongly on deformation history, purity, and testing orientation. Increased deformation (below the recrystallization temperature) raises strength and ductility and lowers the DBTT. This is due to the creation of mobile dislocations. Recrystallized structures exhibit poor ductility and fail by intergranular fracture. Grain refinement also improves ductility and strength (Hall-Petch relationship). Solid Solution W Alloys Additions of Mo or Re are typical. Mo reduces density and refines grain sizes in cast alloys. Mo also reduces the melting point, which makes processing easier. Re ductilizes W. W-Re alloys are often used in high temperature thermocouples, propulsion system components, and anodes for X-ray tubes (Re provides increases resistance to thermal fatigue and thermal shock). Dispersion Strengthened Alloys Thoriated W is the most common. It has been used in light bulb filaments. It is also a common electrode for arc welding. ThO2 reduces the work function of W (this means less evaporative loss of W at operating temperature). ThO2 also inhibits recrystallization and grain growth at high temperatures.

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W Heavy Alloys Essentially liquid phase sintered materials where W particles are encased within a transition metal matrix. See Fig. 8 on page 367 in Heat-Resistant Materials. They have been used in radiation shielding, electrical contacts, and anti-armor kinetic-energy penetrators (i.e. shells).

Oxidation of W Oxidation resistance is poor. WO3 becomes volatile between 800 and 1000C. Its behavior is similar to Mo. Alloys must be coated.

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Rhenium Alloys Z = 75; Tmp = 3180C; =21.04 g/cm3; E = 469 GPa; HCP. This metal and its alloys are very ductile. It is often added to W or Mo to improve ductility of those alloys. We noted this before. Why does it work as a ductilizing element? Re does not form carbides. Though it has a high melting point, it should not be used around molten Al, Fe or Ni because they will dissolve it. Re oxidizes catastrophically above 600C due to the formation of Re2O7, which melts at 297C and boils at 353C. See Heat-Resistant Materials for some common applications.

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Tantalum Alloys Z = 73; Tmp = 2996C; = 16.6 g/cm3; E = 185 GPa; BCC. Ta has excellent resistance to corrosion. It is often used to make crucibles for high temperature chemical reactions or for heating elements. Above 400C, oxidation is catastrophic. The most widely used Ta alloys are: Ta-10W Ta-2.5W Ta-2.5W is often used in heat exchangers because these alloys can be formed easily. Ta also resists attack by the human body, which makes it useful in biological implants or for surgical staples. It also has an elastic modulus that is very similar to that of human bone. This has caused a veritable explosion of research into new Ta-based or Ta containing alloys for biological applications. Coatings have been developed to enhance the oxidation resistance.

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Niobium Alloys Z = 41; Tmp = 2468C; = 8.57 g/cm3; E = 103 GPa; BCC.
Alloy
B-66 Nb-1Zr C-103 FS-85 Cb-1

Nb Mo V Zr W Hf Ti Ta Other Properties
Bal Bal Bal Bal Bal 5 5 1 1 1 1 10 30 10 1 27 0.05 C Moderate strength & ductility Low strength & ductility Low strength & ductility Moderate strength & ductility High strength

A more complete listing is provided on page 372 of Heat-Resistant Materials.

Niobium has the lowest melting temperature, density, and room temperature elastic modulus of the refractory metals. Niobium also has the highest thermal expansion coefficient (14.9 psi 106). Niobium has a thermal-neutron cross section of 1 barn/atom (i.e., 1.1 10-28 m2/atom). It is stable in a wide variety of normal and corrosive environments.

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Uses of Some Common Alloys B-66 has been used in re-entry vehicle parts. Nb-1Zr is used for the SP100 space nuclear power plant. C-103 has been used in rocket components. FS-85 has been used in re-entry vehicle parts.

Strengthening of Nb Alloys Substitutional solutes: Mo, W, V, Ta Reactive elements: Zr, Hf, Ti Interstitials: C, N Ti also enhances oxidation resistance. W and Ta are generally added for high temperature strength. See Figs. 16 20 in Heat-Resistant Materials (pp. 372-373). All of these elements form carbides, so we try to dissolve them and precipitate them out at use temperatures. Niobium alloys have good properties at elevated temperatures but they are not used. WHY?

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Nb-alloys are prone to oxidation Oxide Nb NbO NbO2 Nb2O5 Wt.% O2 14.7 25.6 30.1 Tmp (C) 2468 1945 1915 1480 F ~-100 kcal ~-190 kcal ~-450 kcal

In other words, the oxide will flow, and coat the alloy. Nb dissolves O2, which then makes them brittle.

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Can you coat Nb alloys? The general problem is that the coating mustnt melt. Thus we must use refractories. However, refractories are brittle and have different CTEs than Nb alloys. They could spall off. We can use silicides coatings. Some have been used successfully. CVD silicides. 4M + 3SiCl4 4 MCl3 + 3Si
O2 Si Nb-Si Nb

Sometimes we add some interlayers to improve performance

O2 Si Ti-50Cr Nb

Ti

Additions of V to Si also improve performance. However this improvement is only good up to 1650C. Above that, nothing will work. High Al coatings (e.g., ~30-40 at.% Al, 20-25 at.% Ti, 3 at.%. Cr) can work 22

R RE EF FR RA AC CT TO OR RY YM ME ET TA AL LS S A ME ET TA AL LA AL LL LO OY YS S AN ND DR RE EF FR RA AC CT TO OR RY YM

The bottom line is that these refractory metals just dont work for long periods at high temperatures in air due to oxidation. They can be used in vacuum, space, or in some other oxygen-free environments.

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Whats New and Exciting w/ Refractory Metals?

Refractory metal in-situ composites Nb-Cr-Si Refractory metal silicides Mo-Si-B Refractory high entropy alloys W-Nb-Mo-Ta-V W-Nb-Mo-Ta V-Nb-Mo-Ta-W Ta-Nb-Hf-Zr-Ti

Some Sources for General Overviews MRS Bulletin, v. 28, n. 9 JOM, v. 63, n. 12 There are other review papers available in the literature.

Assignment
Please select one of the topics above. Write a one page (maximum) summary of the properties and performance of these alloys.

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