Jason Walker Powder Metallurgy 05/03/2012
Zirconium monoboride (ZrB) is a part of a family of materials that are called ultra-high temperatureceramics (UHTCs). At high temperatures, these compounds are physically and chemically stabile. WhileZrB is a historically under-investigated material, zirconium diboride (ZrB
) has been well studied. ZrB
exhibits properties such as high melting temperature (in excess of 3000 K), sufficient hardness, highthermal and electrical conductivity and high oxidation resistance. Because of this, it has gainedimportance in fields that require ultra-high thermal protection, such as aerospace. It is hypothesizedthat ZrB also possesses interesting and useful properties that will be applicable in numerous scientificfields. However, there is a current need to place more emphasis on the study of zirconium monoborideto determine its feasibility.Early investigation of multiple boron systems including titanium, zirconium, and hafnium, wasperformed in 1974 by Novikov and Borovinskaya
. They concluded that the only metal that could createa stable monoboride was titanium. ZrB was able to be produced in a combustion wave, but was notpresent in the end result. In fact, the Zr-B systems were believed to be complex compounds containingsmall amounts of oxygen, nitrogen, and carbon. Portnoi and Romashov confirmed this information,extending the fact that ZrB is only stable at high temperatures such as 1500°C
.However, it has been shown that ZrB can exist in the temperature range 1073-1523 K. The existence of ZrB in this range was confirmed by Haggerty et al.
and Champion et al. in separate experiments
. Still,the ZrB phase has an extremely narrow range of stability. The feasibility of synthesized ZrB is examinedherein.
As the only known chemically and thermally stable boride of zirconium, ZrB
research is welldocumented. It is a grey refractory solid and is considered to have the best oxidation resistance of allrefractory hard metals
. It is also known to possess excellent thermal shock resistance. Within the familyof UHTCs, ZrB
has the lowest theoretical density (6.09 g/cm
. Notable uses of ZrB
include as adiffusion barrier in semiconductors, as a container for molten metals, as a burnable absorber in nuclearreactor cores and, perhaps most popularly, as a thermal protective layer in aerospace systems includinghypersonic flight and atmospheric re-entry.Technical-grade ZrB
can be produced multiple ways. One such process involves reacting zirconiumsilicate (ZrSiO
) and boron oxide (B
) and carbon in a submerged-electrode arc furnace. The purecompound is produced by a co-reduction of zirconium tetrachloride (ZrCl
) and boron trichloride (BCl
)with hydrogen and aluminum in a chlorine bath. Another process involves a carbothermic reduction of zirconium dioxide (ZrO
) and boron carbide (B
C), among others.
There are seven phases in the Zr-B system: liquid, hcp-Zr, bcc-Zr, β-B, ZrB, ZrB
. Table 1includes information on the crystal structures of each phase. The zirconium-boron phase diagram is