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ZrB Intro Final

ZrB Intro Final

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Published by: fantasy373 on Jul 06, 2012
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Jason Walker Powder Metallurgy 05/03/2012
Introduction
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
2
) has been well studied. ZrB
2
 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
i
. 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
ii
.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.
iii
and Champion et al. in separate experiments
iv
. Still,the ZrB phase has an extremely narrow range of stability. The feasibility of synthesized ZrB is examinedherein.
 Zirconium Diboride
 
As the only known chemically and thermally stable boride of zirconium, ZrB
2
research is welldocumented. It is a grey refractory solid and is considered to have the best oxidation resistance of allrefractory hard metals
v
. It is also known to possess excellent thermal shock resistance. Within the familyof UHTCs, ZrB
2
has the lowest theoretical density (6.09 g/cm
3
)
vi
. Notable uses of ZrB
2
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
2
can be produced multiple ways. One such process involves reacting zirconiumsilicate (ZrSiO
4
) and boron oxide (B
2
O
3
) and carbon in a submerged-electrode arc furnace. The purecompound is produced by a co-reduction of zirconium tetrachloride (ZrCl
4
) and boron trichloride (BCl
3
)with hydrogen and aluminum in a chlorine bath. Another process involves a carbothermic reduction of zirconium dioxide (ZrO
2
) and boron carbide (B
4
C), among others.
Zr-B System
There are seven phases in the Zr-B system: liquid, hcp-Zr, bcc-Zr, β-B, ZrB, ZrB
2
and ZrB
12vii
. Table 1includes information on the crystal structures of each phase. The zirconium-boron phase diagram is
 
Jason Walker Powder Metallurgy 05/03/2012shown in Figure 1
viii
. Here it is shown that the melting point of ZrB
2
is approximately 3250°C and ZrB
12
 melts peritectically around 2030°C.
Table 1: Phases, structures and models of Zr-B system (Chen)Figure 1: Zr-B Phase Diagram. α = HCP, β = BCC (Okamoto)
Champion et al. also showed that ZrB could exist in a stable state at room temperature if it were cooledat a slow enough rate. It was shown that the compound forms by a peritectoid reaction between βZrand ZrB
2
at 1250°C and is most likely stabilized by the presence of light elements such as carbon,nitrogen and/or oxygen. In samples that were annealed at 1300°C and then cooled relatively quickly, itwas found that the ZrB did not exist. This indicates that only the equilibrium between βZr and ZrB
2
 
 
Jason Walker Powder Metallurgy 05/03/2012phases is likely to coexist above this temperature and that the phase transformation for the formationof ZrB is inhibited by slow atomic diffusion.The solubility of B in βZr appears to be small (<0.5 at.% B) at low temperature. However, it seems toincrease with temperature
ix
. Callmer et al. showed that the maximum solubility of B in βZr to be about 2at.% and corresponding to the composition ZrB
~51
at 2025 K
x
. In the previously discussed experiments byChampion et al., the at.% of B was 1.9.Li et al. investigated the theoretical crystal structure of ZrB based on the first-principles of moleculardynamics theory
xi
. Their optimization results showed that the crystal structure of ZrB is NaCl-type, face-centered cubic (FCC). This confirmed the early findings of Glaser and Post
xii
. This simulation was run at atemperature of 1000 K and a pressure of 400 GPa. The resulting theoretical density was 9.2 g/cm
3
.
 
Theboron atoms take the center and corners of the unit cube. The zirconium atoms locate in the middle of each edge of the unit cube. The lattice constrant α is known to be 4.900Å. This is much different thanZrB
2
which crystallizes in the hexagonal AlB
2
-type structure with a theoretical density of 6.7 g/cm
3
at1000 K and 400 Gpa. The crystal structures are shown in Figure 2.
Figure 2: Crystal Structures of ZrB (a) and ZrB2 (b) (Li)
Table 2 gives the predicted crystal space group, lattice parameters, atomic positions, unit cell volumeand heats of formation for ZrB and ZrB
2
at 0K. Where applicable, these numbers are compared topreviously published experimental and theoretical values.

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