Influence of composition on the structure and properties of Fe-Pd-P and Ni-Pd-P amorphous alloys

Ternary alloys of nickel-palladium-phosphorus and iron-palladium- phosphorus containing 20 atomic % phosphorus were rapidly quenched from the liquid state. The structure of the quenched alloys was investigated by X-ray diffraction. Broad maxima in the diffraction patterns, indicative of a glass-like structure, were obtained for 13 to 73 atomic % nickel and 13 to 44 atomic % iron, with palladium adding up to 80%.

Radial distribution functions were computed from the diffraction data and yielded average interatomic distances and coordination numbers. The structure of the amorphous alloys could be explained in terms of structural units analogous to those existing in the crystalline Pd₃P, Ni₃P and Fe₃P phases, with iron or nickel substituting for palladium. A linear relationship between interatomic distances and composition, similar to Vegard's law, was shown for these metallic glasses.

Electrical resistivity measurements showed that the quenched alloys were metallic. Measurements were performed from liquid helium temperatures (4.2°K) up to the vicinity of the melting points (900°K- 1000°K). The temperature coefficient in the glassy state was very low, of the order of 10^-4/°K. A resistivity minimum was found at low temperature, varying between 9°K and 14°K for Ni_x-Pd_80-x -P₂₀ and between 17°K and 96°K for Fe_x-Pd_80-x -P₂₀, indicating the presence of a Kondo effect. Resistivity measurements, with a constant heating rate of about 1.5°C/min,showed progressive crystallization above approximately 600°K.

The magnetic moments of the amorphous Fe-Pd-P alloys were measured as a function of magnetic field and temperature. True ferromagnetism was found for the alloys Fe₃₂-Pd₄₈-P₂₀ and Fe₄₄-Pd₃₆-P₂₀ with Curie points at 165° K and 380° K respectively. Extrapolated values of the saturation magnetic moments to 0° K were 1.70 µ_B and 2.10 µ_B respectively. The amorphous alloy Fe₂₃-Pd₅₇-P₂₀ was assumed to be superparamagnetic. The experimental data indicate that phosphorus contributes to the decrease of moments by electron transfer, whereas palladium atoms probably have a small magnetic moment. A preliminary investigation of the Ni-Pd-P amorphous alloys showed that these alloys are weakly paramagnetic.

Origin of Th/U variations in chondritic meteorites

Isotope dilution thorium and uranium analyses of the Harleton chondrite show a larger scatter than previously observed in equilibrated ordinary chondrites (EOC). The linear correlation of Th/U with 1/U in Harleton (and all EOC data) is produced by variation in the chlorapatite to merrillite mixing ratio. Apatite variations control the U concentrations. Phosphorus variations are compensated by inverse variations in U to preserve the Th/U vs. 1/U correlation. Because the Th/U variations reflect phosphate ampling, a weighted Th/U average should converge to an improved solar system Th/U. We obtain Th/U=3.53 (1_-mean=0.10), significantly lower and more precise than previous estimates.

To test whether apatite also produces Th/U variation in CI and CM chondrites, we performed P analyses on the solutions from leaching experiments of Orgueil and Murchison meteorites.

A linear Th/U vs. 1/U correlation in CI can be explained by redistribution of hexavalent U by aqueous fluids into carbonates and sulfates.

Unlike CI and EOC, whole rock Th/U variations in CMs are mostly due to Th variations. A Th/U vs. 1/U linear correlation suggested by previous data for CMs is not real. We distinguish 4 components responsible for the whole rock Th/U variations: (1) P and actinide-depleted matrix containing small amounts of U-rich carbonate/sulfate phases (similar to CIs); (2) CAIs and (3) chondrules are major reservoirs for actinides, (4) an easily leachable phase of high Th/U. likely carbonate produced by CAI alteration. Phosphates play a minor role as actinide and P carrier phases in CM chondrites.

Using our Th/U and minimum galactic ages from halo globular clusters, we calculate relative supernovae production rates for ²³²Th/²³⁸U and ²³⁵U/²³⁸U for different models of r-process nucleosynthesis. For uniform galactic production, the beginning of the r-process nucleosynthesis must be less than 13 Gyr. Exponentially decreasing production is also consistent with a 13 Gyr age, but very slow decay times are required (less than 35 Gyr), approaching the uniform production. The 15 Gyr Galaxy requires either a fast initial production growth (infall time constant less than 0.5 Gyr) followed by very low decrease (decay time constant greater than 100 Gyr), or the fastest possible decrease (≈8 Gyr) preceded by slow in fall (≈7.5 Gyr).

Advanced density functional theory methods for materials science

In this work we chiefly deal with two broad classes of problems in computational materials science, determining the doping mechanism in a semiconductor and developing an extreme condition equation of state. While solving certain aspects of these questions is well-trodden ground, both require extending the reach of existing methods to fully answer them. Here we choose to build upon the framework of density functional theory (DFT) which provides an efficient means to investigate a system from a quantum mechanics description.

Zinc Phosphide (Zn₃P₂) could be the basis for cheap and highly efficient solar cells. Its use in this regard is limited by the difficulty in n-type doping the material. In an effort to understand the mechanism behind this, the energetics and electronic structure of intrinsic point defects in zinc phosphide are studied using generalized Kohn-Sham theory and utilizing the Heyd, Scuseria, and Ernzerhof (HSE) hybrid functional for exchange and correlation. Novel 'perturbation extrapolation' is utilized to extend the use of the computationally expensive HSE functional to this large-scale defect system. According to calculations, the formation energy of charged phosphorus interstitial defects are very low in n-type Zn₃P₂ and act as 'electron sinks', nullifying the desired doping and lowering the fermi-level back towards the p-type regime. Going forward, this insight provides clues to fabricating useful zinc phosphide based devices. In addition, the methodology developed for this work can be applied to further doping studies in other systems.

Accurate determination of high pressure and temperature equations of state is fundamental in a variety of fields. However, it is often very difficult to cover a wide range of temperatures and pressures in an laboratory setting. Here we develop methods to determine a multi-phase equation of state for Ta through computation. The typical means of investigating thermodynamic properties is via ’classical’ molecular dynamics where the atomic motion is calculated from Newtonian mechanics with the electronic effects abstracted away into an interatomic potential function. For our purposes, a ’first principles’ approach such as DFT is useful as a classical potential is typically valid for only a portion of the phase diagram (i.e. whatever part it has been fit to). Furthermore, for extremes of temperature and pressure quantum effects become critical to accurately capture an equation of state and are very hard to capture in even complex model potentials. This requires extending the inherently zero temperature DFT to predict the finite temperature response of the system. Statistical modelling and thermodynamic integration is used to extend our results over all phases, as well as phase-coexistence regions which are at the limits of typical DFT validity. We deliver the most comprehensive and accurate equation of state that has been done for Ta. This work also lends insights that can be applied to further equation of state work in many other materials.