Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “OLIVINE”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS1974

Reinvestigation of the olivine-spinel transformation in Ni2SiO4 and the incongruent melting of Ni2SiO4 olivine

The olivine-spinel transformation and the melting behavior of Ni2SiO4 were investigated over the PT ranges of 20-40 kbar, 650-1200 C, and 5-13 kbar, 1600-1700 C, respectively. It was confirmed that Ni2SiO4 olivine melts incongruently at high pressures and that it is a stable phase until melting occurs. The PT slope of the incongruent melting curve is approximately 105 bars/deg. The olivine-spinel transformation curve was shown to be a reversible univariant curve, and could be expressed by the linear equation P(bars) equals 23,300 + 11.8 x T(deg C). The transformation curve determined by Akimoto et al. (1965) is nearly parallel to that of the present work, but lies at pressures about 12% lower.

Ma, C.-B.↗
DOE OSTI2015

Elastic plastic self-consistent (EPSC) modeling of plastic deformation in fayalite olivine

Elastic plastic self-consistent (EPSC) simulations are used to model synchrotron X-ray diffraction observations from deformation experiments on fayalite olivine using the deformation DIA apparatus. Consistent with results from other in situ diffraction studies of monomineralic polycrystals, the results show substantial variations in stress levels among grain populations. Rather than averaging the lattice reflection stresses or choosing a single reflection to determine the macroscopic stress supported by the specimen, an EPSC simulation is used to forward model diffraction data and determine a macroscopic stress that is consistent with lattice strains of all measured diffraction lines. The EPSC simulation presented here includes kink band formation among the plastic deformation mechanisms in the simulation. The inclusion of kink band formation is critical to the success of the models. This study demonstrates the importance of kink band formation as an accommodation mechanism during plastic deformation of olivine as well as the utility of using EPSC models to interpret diffraction from in situ deformation experiments.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFe x Co 1– x PO 4

The delithiation mechanisms occurring within the olivine-type class of cathode materials for Li-ion batteries have received considerable attention owing to the good capacity retention at high rates for LiFePO4. A comprehensive mechanistic study of the (de)lithiation reactions that occur when the substituted olivine-type cathode materials LiFexCo1-xPO4 (x = 0, 0.05, 0.125, 0.25, 0.5, 0.75, 0.875, 0.95 and 1) are electrochemically cycled is reported here, using in situ X-ray diffraction (XRD) data. On the first charge, two intermediate phases are observed and identified: Li1-x(Fe3+)x(Co2+)1- xPO4 for 0 < x < 1 (i.e. after oxidation of Fe2+ => Fe3+) and Li2/3FexCo1-xPO4 for 0 ≤ x ≤ 0.5 (i.e. the Co-majority materials). For the Fe-rich materials, we study how nonequilibrium, single-phase mechanisms that occur discretely in single particles, as observed for LiFePO4 at high rates, is affected by Co substitution. In the Co-majority materials, a two-phase mechanism with a coherent interface is observed, as was seen in LiCoPO4, and we discuss how it is manifested in the XRD patterns. We then compare the nonequilibrium, single-phase mechanism with the bulk single-phase and the coherent interface two-phase mechanisms. Despite the apparent differences between these mechanisms, we discuss how they are related and interconverted as a function of Fe/Co substitution and the potential implications for the electrochemistry of this system.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Dislocation interactions in olivine control postseismic creep of the upper mantle

Changes in stress applied to mantle rocks, such as those imposed by earthquakes, commonly induce a period of transient creep, which is often modelled based on stress transfer among slip systems due to grain interactions. However, recent experiments have demonstrated that the accumulation of stresses among dislocations is the dominant cause of strain hardening in olivine at temperatures ≤600 °C, raising the question of whether the same process contributes to transient creep at higher temperatures. Here, we demonstrate that olivine samples deformed at 25 °C or 1150–1250 °C both preserve stress heterogeneities of ~1 GPa that are imparted by dislocations and have correlation lengths of ~1 μm. The similar stress distributions formed at these different temperatures indicate that accumulation of stresses among dislocations also provides a contribution to transient creep at high temperatures. The results motivate a new generation of models that capture these intragranular processes and may refine predictions of evolving mantle viscosity over the earthquake cycle.

58 GEOSCIENCES↗
DOE OSTI2017

Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases: Operando Investigation of Olivine NaFePO 4 [Accommodation of High Transformation Strain in Battery Electrodes via Formation of Nanoscale Intermediate Phases: Operando Structure Investigation of Olivine Sodium Iron Phosphate]

Virtually all intercalation compounds used as battery electrodes exhibit significant changes in unit cell volume during use. Na x FePO 4 (0 < x < 1, NFP) olivine, of interest as a cathode for sodium-ion batteries, is a model for topotactic, high strain systems as it exhibits one of the largest discontinuous volume changes (~17% by volume) during its first-order transition between two otherwise isostructural phases. Using synchrotron radiation powder X-ray diffraction (PXD) and pair distribution function (PDF) analysis, we discover a new strain-accommodation mechanism wherein a third, <10 nm scale nanocrystalline phase forms to buffer the large lattice mismatch between primary phases. The new phase has a and b lattice parameters matching one crystalline endmember phase and c lattice parameter matching the other, and is not detectable by powder diffraction alone. Finally, we suggest that this strain-accommodation mechanism may apply to systems with large transformation strains but in which true “amorphization” does not occur.

25 ENERGY STORAGE↗
DOE OSTI2015

Spinel-olivine-pryoxene equilibrium iron isotopic fractionation and applications to natural peridotites

Eight spinel-group minerals were synthesized by a flux-growth method producing spinels with varying composition and Fe3+/Fe-tot ratios. The mean force constants of iron bonds in these minerals were determined by synchrotron nuclear resonant inelastic X-ray scattering (NRIXS) in order to determine the reduced isotopic partition function ratios (beta-factors) of these spinels. The mean force constants are strongly dependent on the Fe3+/Fe-tot of the spinel but are independent, or weakly dependent on other structural and compositional parameters. From our spectroscopic data, it is found that a single redox-dependent calibration line accounts for the effects of Fe3+/Fe-tot on the beta-factors of spinels. This calibration successfully describes the equilibrium Fe isotopes fractionation factors between spinels and silicates (olivine and pyroxenes). Our predictions are in excellent agreement with independent determinations for the equilibrium Fe isotopic fractionations for the magnetite- fayalite and the magnetite-hedenbergite couples. Our calibration applies to the entire range of Fe3+/Fe-tot ratios found in natural spinels and provides a basis for interpreting iron isotopic variations documented in mantle peridotites. Except for a few exceptions, most of the samples measured so far are in isotopic disequilibrium, reflecting metasomatism and partial melting processes.

Geothermometer↗
DOE OSTI2017

Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate

Olivine lithium iron phosphate is a technologically important electrode material for lithium-ion batteries and a model system for studying electrochemically driven phase transformations. Despite extensive studies, many aspects of the phase transformation and lithium transport in this material are still not well understood. Here we combine operando hard X-ray spectroscopic imaging and phase-field modeling to elucidate the delithiation dynamics of single-crystal lithium iron phosphate microrods with long-axis along the [010] direction. Lithium diffusivity is found to be two-dimensional in microsized particles containing ~3%lithium-iron anti-site defects. Our study provides direct evidence for the previously predicted surface reaction-limited phase-boundary migration mechanism and the potential operation of a hybrid mode of phase growth, in which phase-boundary movement is controlled by surface reaction or lithium diffusion in different crystallographic directions. These findings uncover the rich phase-transformation behaviors in lithium iron phosphate and intercalation com-pounds in general and can help guide the design of better electrodes.

25 ENERGY STORAGE↗