Hafnium carbide

Hafnium has been successfully alloyed with iron, titanium, niobium, tantalum, and other metals. Hafnium carbide is the most refractory binary composition known, and the nitride is the most refractory of all known metal nitrides (m.p. 3310C). At 700 degrees C hafnium rapidly absorbs hydrogen to form the composition HfHl.86. 

Hafnium carbide [12069-85-1] can be used as surface coating on cemented-carbide cutting tools, shows promise as a stable field emission cathode... 

Most hafnium compounds have been of slight commercial interest aside from intermediates in the production of hafnium metal. However, hafnium oxide, hafnium carbide, and hafnium nitride are quite refractory and have received considerable study as the most refractory compounds of the Group 4 (IVB) elements. Physical properties of some of the hafnium compounds are shown in Table 4. 

Hafnium Carbide. Hafnium carbide, HfC, is a dark gray brittle soHd. This carbide can be prepared by heating an intimate mixture of the elements or by the reaction of hafnium tetrachloride with methane at 2100°C, but is commonly produced by the reaction of hafnium oxide with lampblack... 

Hafnium carbide is inert to most reagents at room temperature, but is dissolved by hydrofluoric acid solutions which also contain an oxidising agent. Above 250°C, hafnium carbide reacts exothermically with halogens to form hafnium tetrahaUde, and above 500°C, with oxygen to form hafnium dioxide. At higher temperatures in a flow of hydrogen, hafnium carbide slowly loses some of its carbon. 

At room temperature, hafnium dioxide is slowly dissolved by hydrofluoric acid. At elevated temperatures, hafnium dioxide reacts with concentrated sulfuric acid or alkaU bisulfates to form various sulfates, with carbon tetrachloride or with chlorine in the presence of carbon to form hafnium tetrachloride, with alkaline fluorosiUcates to form alkaU fluorohafnates, with alkaUes to form alkaline hafnates, and with carbon above 1500°C to form hafnium carbide. 

Niobium carbide is used as a component of hard metals, eg, mixtures of metal carbides that are cemented with cobalt, iron, and nickel. Along with tantalum carbide, niobium carbide is added to impart toughness and shock and erosion resistance. The spiraling rise in the price of tantalum has spurred the development of a hafnium carbide—niobium carbide substitute for tantalum carbide (68). These cemented carbides are used for tool bits, drill bits, shovel teeth, and other wear-resistant components turbine blades and as dies in high pressure apparatus (see Carbides). 

The first carbonitride alloys based on Ti(C,N)—Ni—Mo were iatroduced ia 1970 foUowed by (Ti, Mo)(C,N)-based compositions having fine microstmctures that provided a balance of wear resistance and toughness (4). Continued research on the titanium carbonitride alloys, often called TiC—TiN cermets, ia the 1980s led to the developmeat of complex cermets having a variety of additives such as molybdeaum carbide(2 l) [12069-89-5] M02C, TaC, NbC, zirconium carbide [12020-14-3], ZrC, hafnium carbide [12069-85-1], HfC, WC, vanadium carbide [12070-10-9], VC, chromium carbide (3 2)... 

Hafnium Carbide. The need of pure zirconium [7440-67-7] for nuclear reactors prompted the large-scale separation of hafnium [7440-58-6] from zirconium. This in turn made sufficient quantities of hafnium dioxide [12055-23-17, Hf02, or Hf metal sponge available for production of HfC for use in cemented carbides (see Hafniumand hafnium compounds). 

Hafnium carbide can be prepared industrially from hydrided hafnium sponge at 1500—1700°C or from Hf02 at 2000—2200°C by carburization in vacuum in the presence of hydrogen. The resulting carbide contains almost the theoretical quantity of carbon, 6.30 wt % C, of which a maximum of 0.1 wt % is unbound. 

Other compounds have been deposited by fluidized-bed CVD including zirconium carbide (from ZrCl4 and a hydrocarbon), hafnium carbide (from HfC and methane or propylene), and titanium carbide (from TiCl3 and propylene). 

Hafnium carbide (HfC) is an interstitial carbide which, with tantalum carbide, is the most refractory compound known. Its characteristics and properties are summarized in Table 9.4. 

Chemical Resistance. Hafnium carbide oxidizes in air at 500°C. It is not as chemically resistant as TiC and is similar to ZrC in that respect. 

In spite of its excellent properties, hafnium carbide has only limited industrial importance, possibly because of its high cost. Some experimental applications are as follows ... 

Futamoto, M., Yuito, I, andKawabe, U., Hafnium Carbide and Nitride Whisker Growth by Chemical Vapor Deposition, /. Cryst. Growth, 61(l) 69-74 (Jan./Feb. 1983)... 

Hafnium carbide and hafnium nitride whiskers from HfCl4, CH4 or N2, and H2 in the presence of a nickel catalyst at 1000-1450°C.P l... 

The silvery, shiny, ductile metal is passivated with an oxide layer. Chemically very similar to and always found with zirconium (like chemical twins, with almost identical ionic radii) the two are difficult to separate. Used in control rods in nuclear reactors (e.g. in nuclear submarines), as it absorbs electrons more effectively than any other element. Also used in special lamps and flash devices. Alloys with niobium and tantalum are used in the construction of chemical plants. Hafnium dioxide is a better insulator than Si02. Hafnium carbide (HfC) has the highest melting point of all solid substances (3890 °C record ). 

Of a series of powdered refractory compounds examined, only lanthanum hexa-boride, hafnium carbide, titanium carbide, zirconium carbide, magnesium nitride, zirconium nitride and tin(II) sulfide were dust explosion hazardous, the 2 latter being comparable with metal dusts. Individual entries are ... 

Hafnium carbide, 0521 Lanthanum hexaboride, 0193 Magnesium nitride, 4698 Tin(II) sulfide, 4900 Titanium carbide, 0561 Zirconium carbide, 0565 Zirconium nitride, 4733... 

Hafnium carbide (HfC) This alloy has one of the highest melting points of any binary compound (3.890°C). It is extremely hard and resists corrosion while absorbing slow neutrons. Therefore, it is an ideal metal in the manufacture of control rods for nuclear reactors. 

Reaction with carbon at 1,500°C produces hafnium carbide, HfC. 

Reaction with methane at 2,100°C produces hafnium carbide, a dark-gray, brittle solid, which is not a true stoichiometric compound. It probably is a homogeneous mixture in which carbon impregnates interstitial sites in the face-centered cubic lattice of hafnium. 

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