This paper reviews the crystal chemistry, synthesis, densification, microstructure, mechanical properties, and oxidation behavior of zirconium diboride (ZrB2) and hafnium diboride (HfB2) ceramics. The refractory diborides exhibit partial or complete solid solution with other transition metal diborides, which allows compositional tailoring of properties such as thermal expansion coefficient and hardness. Carbothermal reduction is the typical synthesis route, but reactive processes, solution methods, and pre-ceramic polymers can also be used. Typically, diborides are densified by hot pressing, but recently solid state and liquid phase sintering routes have been developed. Fine-grained ZrB2 and HfB2 have strengths of a few hundred MPa, which can increase to over 1 GPa with the addition of SiC. Pure diborides exhibit parabolic oxidation kinetics at temperatures below 1100°C, but B2O3 volatility leads to rapid, linear oxidation kinetics above that temperature. The addition of silica scale formers such as SiC or MoSi2 improves the oxidation behavior above 1100°C. Based on their unique combination of properties, ZrB2 and HfB2 ceramics are candidates for use in the extreme environments associated with hypersonic flight, atmospheric re-entry, and rocket propulsion.

Refractory Diborides of Zirconium and Hafnium

This review paper illustrates the main normal and superconducting state properties of magnesium diboride, a material known since the early 1950s but only recently discovered to be superconductive at a remarkably high critical temperature Tc = 40 K for a binary compound. What makes MgB2 so special? Its high Tc, simple crystal structure, large coherence lengths, high critical current densities and fields, and transparency of grain boundaries to current promise that MgB2 will be a good material for both large-scale applications and electronic devices. During the last seven months, MgB2 has been fabricated in various forms: bulk, single crystals, thin films, tapes and wires. The largest critical current densities, greater than 10 MA cm−2, and critical fields, 40 T, are achieved for thin films. The anisotropy ratio inferred from upper critical field measurements is yet to be resolved as a wide range of values have been reported, γ = 1.2–9. Also, there is no consensus on the existence of a single anisotropic or double energy gap. One central issue is whether or not MgB2 represents a new class of superconductors, which is the tip of an iceberg awaiting to be discovered. To date MgB2 holds the record for the highest Tc among simple binary compounds. However, the discovery of superconductivity in MgB2 revived the interest in non-oxides and initiated a search for superconductivity in related materialss; several compounds have since been announced to be superconductive: TaB2, BeB2.75, C–S composites, and the elemental B under pressure.

https://iopscience.iop.org/article/10.1088/0953-2048/14/11/201/pdf

Review of the superconducting properties of MgB2

This review paper illustrates the main normal and superconducting state properties of magnesium diboride, a material known since early 1950's, but recently discovered to be superconductive at a remarkably high critical temperature Tc=40K for a binary compound. What makes MgB2 so special? Its high Tc, simple crystal structure, large coherence lengths, high critical current densities and fields, transparency of grain boundaries to current promises that MgB2 will be a good material for both large scale applications and electronic devices. During the last seven month, MgB2 has been fabricated in various forms, bulk, single crystals, thin films, tapes and wires. The largest critical current densities >10MA/cm2 and critical fields 40T are achieved for thin films. The anisotropy ratio inferred from upper critical field measurements is still to be resolved, a wide range of values being reported, between 1.2 and 9. Also there is no consensus about the existence of a single anisotropic or double energy gap. One central issue is whether or not MgB2 represents a new class of superconductors, being the tip of an iceberg who awaits to be discovered. Up to date MgB2 holds the record of the highest Tc in its class. However, the discovery of superconductivity in MgB2 revived the interest in non-oxides and initiated a search for superconductivity in related materials, several compounds being already announced to become superconductive: TaB2, BeB2.75, C-S composites, and the elemental B under pressure.

Review of superconducting properties of MgB2

and Perspectives Sophie Carenco,†,‡,§,∥,⊥ David Portehault,*,†,‡,§ Ced́ric Boissier̀e,†,‡,§ Nicolas Meźailles, and Cleḿent Sanchez*,†,‡,§ †Chimie de la Matier̀e Condenseé de Paris, UPMC Univ Paris 06, UMR 7574, Colleg̀e de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France ‡Chimie de la Matier̀e Condenseé de Paris, CNRS, UMR 77574, Colleg̀e de France, 11 Place Marcellin Berthelot, 75231 Paris Cedex 05, France Chimie de la Matier̀e Condenseé de Paris, Colleg̀e de France, 11 Place Marcellin Berthelot, 75231 Paris Cedex 05, France Laboratory Heteroelements and Coordination, Chemistry Department, Ecole Polytechnique, CNRS-UMR 7653, Palaiseau, France

Nanoscaled metal borides and phosphides: recent developments and perspectives

Microstructural design of hard coatings

The electronic structure and ground state properties of ${\mathrm{AlB}}_{2}$ type transition metal diborides ${\mathrm{TMB}}_{2}$ (TM=Sc, Ti, V, Cr, Mn, Fe, Y, Zr, Nb, Mo, Hf, Ta) have been calculated using the self consistent tight-binding linear muffin-tin orbital method. The equilibrium volume, bulk moduli ${(B}_{0}),$ pressure derivative of bulk moduli ${(B}_{0}^{\ensuremath{'}}),$ cohesive energy ${(E}_{\mathrm{coh}}),$ heat of formation $(\ensuremath{\Delta}H),$ and electronic specific heat coefficient $(\ensuremath{\gamma})$ are calculated for these systems and compared with the available experimental and other theoretical results. The bonding nature of these diborides is analyzed via the density of states (DOS) histogram as well as the charge density plots, and the chemical stability is analyzed using the band filling principle. The variation in the calculated cohesive properties of these materials is correlated with the band filling effect. The existence of a pseudogap in the total density of states is found to be a common feature for all these compounds. The reason for the creation of the pseudogap is found to be due to the strong covalent interaction between boron p states. We have made spin polarized calculations for ${\mathrm{CrB}}_{2},$ ${\mathrm{MnB}}_{2},$ and ${\mathrm{FeB}}_{2}$ and found that finite magnetic moments exist for ${\mathrm{MnB}}_{2}$ and ${\mathrm{CrB}}_{2}$ whereas ${\mathrm{FeB}}_{2}$ is nonmagnetic.

Electronic structure, bonding, and ground-state properties of AlB 2 -type transition-metal diborides

First-principles study of crystal structure and stability of Al-Mg-Si-(Cu) precipitates

Metastable precipitate phase boundaries are difficult to ascertain experimentally and yet are important for controlling the microstructure of precipitation-hardenable alloys. We demonstrate how first-principles calculations of configurational and vibrational free energies can be used to predict precipitate phase boundaries of stable and metastable phases in Al–Cu alloys. Surprisingly, the formation entropy of a Cu impurity is found to be hugely positive (+2.7 kB/atom), leading to a dramatic enhancement in the solubility. The large entropy is dominated by the very low-frequency vibration of the small impurity atom (Cu) inside the large cage of the host (Al). The agreement between the GGA and experimental data is within 100 K for all phases, showing that accurate first-principles determination of metastable phase boundaries is now possible.

http://iopscience.iop.org/article/10.1209/epl/i2005-10462-x/pdf

Predicting metastable phase boundaries in Al–Cu alloys from first-principles calculations of free energies: The role of atomic vibrations

In this paper, we report the calculated phase diagrams of V-Nb, V-Ta, and Nb-Ta alloys computed by combining the total energies of 40–50 configurations for each system (obtained using density functional theory) with the cluster expansion and Monte Carlo techniques. For V-Nb alloys, the phase diagram computed with conventional cluster expansion shows a miscibility gap with consolute temperature T_c=1250 K. Including the constituent strain to the cluster expansion Hamiltonian does not alter the consolute temperature significantly, although it appears to influence the solubility of V- and Nb-rich alloys. The phonon contribution to the free energy lowers T_c to 950 K (about 25%). Our calculations thus predicts an appreciable miscibility gap for V-Nb alloys. For bcc V-Ta alloy, this calculation predicts a miscibility gap with T_c=1100 K. For this alloy, both the constituent strain and phonon contributions are found to be significant. The constituent strain increases the miscibility gap while the phonon entropy counteracts the effect of the constituent strain. In V-Ta alloys, an ordering transition occurs at 1583 K from bcc solid solution phase to the V_(2)Ta Laves phase due to the dominant chemical interaction associated with the relatively large electronegativity difference. Since the current cluster expansion ignores the V_(2)Ta phase, the associated chemical interaction appears to manifest in making the solid solution phase remain stable down to 1100 K. For the size-matched Nb-Ta alloys, our calculation predicts complete miscibility in agreement with experiment.

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First-principles calculation of phase equilibrium of V-Nb, V-Ta, and Nb-Ta alloys

The results of the electronic band structure calculations performed on ternary chalcogenides ABX 2 (A = Cu Ag: B = Ga, In; X = S,Se,Te) using the semi-relativistic Tight Binding Linear Muffin Tin Orbital method are reported. The equilibrium lattice constants and the bulk moduli obtained from the P-V curves agree very well with the experimental values. More generalized equations connecting the cell volumes and bulk moduli as well as bulk moduli and melting points are established. It is to be noted that since these equations hold good for all I-III-VI 2 compounds they could be used further for extracting the above parameters for other compounds that crystallize in the body centered tetragonal structure. The energy gap at ambient pressure is found to be direct in all the cases and the nature of the gap crucially depends on the manner in which the d-electrons of the A atoms are treated. The pressure derivatives of the energy gaps as well as the metallisation pressures are calculated and compared with the available experimental values.

C. Ravi

Papers

Electronic structure, bonding, and ground-state properties of AlB 2 -type transition-metal diborides

First-principles study of crystal structure and stability of Al-Mg-Si-(Cu) precipitates

Predicting metastable phase boundaries in Al–Cu alloys from first-principles calculations of free energies: The role of atomic vibrations

First-principles calculation of phase equilibrium of V-Nb, V-Ta, and Nb-Ta alloys

Electronic Structure Calculations and Physical Properties of ABX2(A = Cu, Ag; B = Ga, In; X = S, Se, Te) Ternary Chalcopyrite Systems