48 research outputs found
The Phonon Entropy of Transition Metals and Alloys: Effects of Impurities and of a Martensitic Phase Transition
For a fixed configuration of ions on a given crystalline lattice, low energy excitations around the static average configuration can be thermally activated and will contribute to the entropy of the system. As such, phonons, spin-waves or electronic excitations have their own entropic contribution. This thesis investigates the entropic effects of lattice vibrations in transition metal alloys, both from experimental and computational points of view.
Using inelastic neutron scattering, it is shown that a few percent of substitutional impurities from the transition metal series strongly affect the phonon density of states (DOS) of pure vanadium. Alloying with 6% Pt solutes produces a strong stiffening of the phonon DOS, inducing a large and negative vibrational entropy of mixing, which overcomes the increase in configurational entropy. A systematic study of chemical trends for different transition metal impurities was conducted. A previously unknown correlation is established between the vibrational entropy of alloying and the difference in electronegativity of the solute and the host. Density-functional theory calculations were conducted and confirmed the occurrence of systematic charge-transfers correlating with the electronegativity, which affect the interatomic force-constants and the phonons.
The effect of impurities on the anomalous temperature-dependence of phonons in vanadium is investigated. It is found that the solutes which affect the phonon density of states most strongly at room temperature also suppress the anomalous temperature behavior. Electron-phonon and phonon-phonon couplings are examined as potential sources of this effect, through a careful accounting of their contributions to the heat capacity, based on inelastic neutron scattering experiments, calorimetry measurements and electronic structure calculations.
Finally, the changes in the phonon DOS and the vibrational entropy across the low-temperature martensitic phase transformation in Fe71Ni29 are investigated. The respective contributions of the phonons and magnetism to the entropy of the direct and reverse transformation are evaluated from neutron scattering and differential scanning calorimetry measurements. A significant magnetic entropy is found in the reverse transformation, which is not present in the direct transformation. This result stresses the necessity to account for the respective contributions of all microscopic degrees of freedom in evaluating entropy changes in solid-solid phase transitions.</p
Thermoelectric properties of Co, Ir, and Os-Doped FeSi Alloys: Evidence for Strong Electron-Phonon Coupling
The effects of various transition metal dopants on the electrical and thermal
transport properties of Fe1-xMxSi alloys (M= Co, Ir, Os) are reported. The
maximum thermoelectric figure of merit ZTmax is improved from 0.007 at 60 K for
pure FeSi to ZT = 0.08 at 100 K for 4% Ir doping. A comparison of the thermal
conductivity data among Os, Ir and Co doped alloys indicates strong
electron-phonon coupling in this compound. Because of this interaction, the
common approximation of dividing the total thermal conductivity into
independent electronic and lattice components ({\kappa}Total =
{\kappa}electronic + {\kappa}lattice) fails for these alloys. The effects of
grain size on thermoelectric properties of Fe0.96Ir0.04Si alloys are also
reported. The thermal conductivity can be lowered by about 50% with little or
no effect on the electrical resistivity or Seebeck coefficient. This results in
ZTmax = 0.125 at 100 K, still about a factor of five too low for solid-state
refrigeration applications
Phonon anharmonicity and negative thermal expansion in SnSe
The anharmonic phonon properties of SnSe in the Pnma phase were investigated
with a combination of experiments and first-principles simulations. Using
inelastic neutron scattering (INS) and nuclear resonant inelastic X-ray
scattering (NRIXS), we have measured the phonon dispersions and density of
states (DOS) and their temperature dependence, which revealed a strong,
inhomogeneous shift and broadening of the spectrum on warming. First-principles
simulations were performed to rationalize these measurements, and to explain
the previously reported anisotropic thermal expansion, in particular the
negative thermal expansion within the Sn-Se bilayers. Including the anisotropic
strain dependence of the phonon free energy, in addition to the electronic
ground state energy, is essential to reproduce the negative thermal expansion.
From the phonon DOS obtained with INS and additional calorimetry measurements,
we quantify the harmonic, dilational, and anharmonic components of the phonon
entropy, heat capacity, and free energy. The origin of the anharmonic phonon
thermodynamics is linked to the electronic structure.Comment: 14 pages, 12 figure