Hafnium borides

Hafnium Boride. Hafnium diboride [12007-23-7] HfB2, is a gray crystalline soHd. It is usually prepared by the reaction of hafnium oxide with carbon and either boron oxide or boron carbide, but it can also be prepared from mixtures of hafnium tetrachloride, boron trichloride, and hydrogen above 2000°C, or by direct synthesis from the elements. Hafnium diboride is attacked by hydrofluoric acid but is resistant to nearly all other reagents at room temperature. Hafnium dodecaboride [32342-52-2] has been prepared by direct synthesis from the elements (56). 

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 ... 

Fig. 18. The Hf-B-C isothermal ternary cross sections at three different temperatures. Points A and B represent two possible stoichiometries for processing hafnium boride/hafnium carbide composites. After Rudy [57],...

Chromium boride Hafnium boride Molybdenum boride... 

Hafnium dioxide is formed by ignition of hafnium metal, carbide, tetrachloride, sulfide, boride, nitride, or hydrous oxide. Commercial hafnium oxide, the product of the separation process for zirconium and hafnium, contains 97—99% hafnium oxide. Purer forms, up to 99.99%, are available. 

Boron forms B—N compounds that are isoelectronic with graphite (see Boron compounds, refractoryboron compounds). The small size also has a significant role in the interstitial alloy-type metal borides boron forms. Boron forms borides with metals that are less electronegative than itself including titanium, zirconium, and hafnium. 

Apart from the reactions described above for the formation of thin films of metals and compounds by the use of a solid source of the material, a very important industrial application of vapour phase transport involves the preparation of gas mixtures at room temperature which are then submitted to thermal decomposition in a high temperature furnace to produce a thin film at this temperature. Many of the molecular species and reactions which were considered earlier are used in this procedure, and so the conclusions which were drawn regarding choice and optimal performance apply again. For example, instead of using a solid source to prepare refractory compounds, as in the case of silicon carbide discussed above, a similar reaction has been used to prepare titanium boride coatings on silicon carbide and hafnium diboride coatings on carbon by means of a gaseous input to the deposition furnace (Choy and Derby, 1993) (Shinavski and Diefendorf, 1993). 

In finely divided form, hafnium is pyrophoric, igniting in air spontaneously. However, bulk metal reacts slowly in oxygen or air above 400°C. The rate of oxidation increases with temperature. The product is hafnium dioxide, Hf02. It combines with nitrogen, carbon, boron, sulfur and silicon at very high temperatures to form hafnium nitride HfN, hafnium boride HfB, hafnium sulfide HfSi2, respectively. Nitride formation occurs at 900°C. 

New mixed borides of Hf and Mo (HfgMo B) and Zr and Mo (Zr9Mo4B) have been prepared and characterized as fc-borides by 2f-ray methods. The hafnium species will dissolve up to 14 atom% A1 at 1400 °C. 

With allowances for the actual metal content of zirconium (a small correction is also necessary for the hafnium content of about 2 /2%) and postulation of barium zirconate formation (see Table 27), reasonable accord between calculated and measured caloric output is established. However, the situation is more complex with boron mixtures where one encounters increase of heat output with increase of the percentage of boron in the mixtures much beyond the amounts of Equation (la). Thus, even with the reasonable assumption of secondary barium borate formation, the stoichiometry and heat output of the mixtures with more than about 10% of technical boron theoretical 8%) is obscure. Chromium boride formation may be a fector. 

In February, 1980, Sumitomo from Japan filed the patent Sintered compact for a machining tool and a method of producing the compact [161]. This patent basically covers any compact with 10-80 vol% cBN and a balance of binder material that can comprise any carbides, nitrides, borides, or silicides of metals of groups IVa, Va, or Via. Specifically mentioned are titanium, zirconium, hafnium, vanadium, niobium. 

Ceramic borides, carbides and nitrides are characterized by high melting points, chemical inertness and relatively good oxidation resistance in extreme environments, such as conditions experienced during reentry. This family of ceramic materials has come to be known as Ultra High Temperature Ceramics (UHTCs). Some of the earliest work on UHTCs was conducted by the Air Force in the 1960 s and 1970 s. Since then, work has continued sporadically and has primarily been funded by NASA, the Navy and the Air Force. This article summarizes some of the early works, with a focus on hafnium diboride and zirconium diboride-based compositions. These works focused on identifying additives, such as SiC, to improve mechanical or thermal properties, and/or to improve oxidation resistance in extreme environments at temperatures greater than 2000°C. 

Figure 6.13. The calculated stability diagram at 1125°C of a mixture of hafnium chloride, boron chloride, and methyl trichlorosilane. The solids expected to be in equilibrium with a gas of the stated composition are noted in the different concentration ranges. The composition of the gas mixture at which both silicon carbide and hafnium boride are stable is shaded. From W. J. Lackey, A. W. Smith, D. M. Dillard and D. J. Twait. Proc. 10th Intern. Conf. CVD, Honolulu (1987), p. 1008. Reproduced by permission of The Electrochemical Society, Inc.

Potentially useful single crystal HP-LCVD fibers include hafnium boride and tantalum carbide and have projected service temperatures ranging from 2170 to 2715 C. Presently envisioned applications include the potential use of these fibers as consumable sensors to monitor rocket exhaust temperatures. Other HP-LCVD sensor fibers, including Si, Ge and ZnSe, (Figure 15), promise to offer high value in premium automotive and medical sensor systems. Single crystal HP-LCVD germanium [20] and silicon carbide [21] fibers can now also become available for exploration. In summary, the HP-LCVD process is an ideally suited tool for the rapid fabrication and evaluation, without extensive process research, of test samples of potentially new fiber candidates for structural and sensor uses. 

Borides Chromium Diboride (CrB2) Hafnium Diboride (HfB2) Tantalum Diboride (TaB2) ZlxlO 10-12 X 10 oaxio room temp. 

J.J. Melendez-Martfnez, A. Dominguez-Rodn guez, F. Monteverde, C. Melandri and G. De Portu Characterisation and high temperature mechanical properties of zirconium boride-based materials. Journal of the European Ceramic Society 22, 2543-2549 (2002). W.G. Fahrenholtz, G.E. Hilmas, I.G. Talmy and J.A. Zaykoski Refractory diborides of zirconium and hafnium. Journal of the American Ceramic Society 90, 1347-1364 (2007). 

---