An official website of the United States government
Abstract Iron nitrides are possible constituents of the cores of Earth and other terrestrial planets. Pressure‐induced magnetic changes in iron nitrides and effects on compressibility remain poorly understood. Here we report synchrotron X‐ray emission spectroscopy (XES) and X‐ray diffraction (XRD) results for ε‐Fe7N3and γ′‐Fe4N up to 60 GPa at 300 K. The XES spectra reveal completion of high‐ to low‐spin transition in ε‐Fe7N3and γ′‐Fe4N at 43 and 34 GPa, respectively. The completion of the spin transition induces stiffening in bulk modulus of ε‐Fe7N3by 22% at ~40 GPa, but has no resolvable effect on the compression behavior of γ′‐Fe4N. Fitting pressure‐volume data to the Birch‐Murnaghan equation of state yieldsV0 = 83.29 ± 0.03 (Å3),K0 = 232 ± 9 GPa,K0′ = 4.1 ± 0.5 for nonmagnetic ε‐Fe7N3above the spin transition completion pressure, andV0 = 54.82 ± 0.02 (Å3),K0 = 152 ± 2 GPa,K0′ = 4.0 ± 0.1 for γ′‐Fe4N over the studied pressure range. By reexamining evidence for spin transition and effects on compressibility of other candidate components of terrestrial planet cores, Fe3S, Fe3P, Fe7C3, and Fe3C based on previous XES and XRD measurements, we located the completion of high‐ to low‐spin transition at ~67, 38, 50, and 30 GPa at 300 K, respectively. The completion of spin transitions of Fe3S, Fe3P, and Fe3C induces elastic stiffening, whereas that of Fe7C3induces elastic softening. Changes in compressibility at completion of spin transitions in iron‐light element alloys may influence the properties of Earth's and planetary cores.
more »
« less
A thermodynamic explanation of the Invar effect
The anomalously low thermal expansion of Fe-Ni Invar has long been associated with magnetism, but to date, the microscopic underpinnings of Invar behavior have eluded both theory and experiment. Here, we present nuclear resonant X-ray scattering measurements of the phonon and magnetic entropy under pressure. By applying a thermodynamic Maxwell relation to these data, we obtain the separate phonon and magnetic contributions to thermal expansion. We find that the Invar behavior stems from a competition between phonons and spins. In particular, the phonon contribution to thermal expansion cancels the magnetic contribution over the 0 - 3 GPa pressure range of Invar behavior. At pressures above 3 GPa the cancellation is lost, but our analysis reproduces the positive thermal expansion measured separately by synchrotron X-ray diffractometry. Ab initio calculations informed by experimental data show that spin-phonon interactions improve the accuracy of this cancellation over the range of Invar behavior. Spin-phonon interactions also explain how different phonon modes have different energy shifts with pressure.
more »
« less
- Award ID(s):
- 1904714
- PAR ID:
- 10469771
- Publisher / Repository:
- Nature Physics
- Date Published:
- Journal Name:
- Nature Physics
- ISSN:
- 1745-2473
- Subject(s) / Keyword(s):
- Invar spin-phonon interactions thermodynamics nuclear resonant X-ray scattering ab initio thermodynamics
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
null (Ed.)Thermoelastic behavior of transition metal boride Os2B3 was studied under quasi-hydrostatic and isothermal conditions in a Paris-Edinburgh cell to 5.4 GPa and 1273 K. In-situ Energy Dispersive X-ray diffraction was used to determine interplanar spacings of the hexagonal crystal structure and thus the volume and axial compression. P-V-T data were fitted to a 3rd Order Birch-Murnaghan equation of state with a temperature modification to determine thermal elastic constants. The bulk modulus was shown to be K0 = 402 ± 21 GPa when the first pressure derivative was held to K0’ = 4.0 from the room temperature P-V curve. Under a quadratic fit α=α_0+α_1 T-α_2 T^(-2), the thermal expansion coefficients were determined to be α_0=1.862×10^(-5) K-1, α_1=0.841×10^(-9) K-2, and α_2=-0.525 K. Density functional theory (DFT) with the quasi-harmonic approximation (QHA) were further employed to study Os2B3, including its P-V-T curves, phonon spectra, bulk modulus, specific heat, thermal expansion, and the Grüneisen parameter. A good agreement between the first-principle theory and experimental observations was achieved, highlighting the success of the Armiento-Mattsson 2005 generalized gradient approximation functional employed in this study and QHA for describing thermodynamic properties of Os2B3.more » « less
-
In this study, phase transitions (structural and magnetic) and associated magnetocaloric properties of stoichiometric MnCoGe have been investigated as a function of annealing pressure. Metastable phases were generated by annealing at 800 °C followed by rapid cooling under pressures up to 6.0 GPa. The x-ray diffraction results reveal that the crystal cell volume of the metastable phases continuously decreases with increasing thermal processing pressure, leading to a decrease in the structural transition temperature. The magnetic and structural transitions merge and form a first-order magnetostructural transition between the ferromagnetic orthorhombic and paramagnetic hexagonal phases over a broad temperature range (>80 K) spanning room temperature, yielding considerable magnetic entropy changes. These findings demonstrate the utility of thermal processing under high pressure, i.e., high-pressure annealing, to control the magnetostructural transitions and associated magnetocaloric properties of MnCoGe without altering its chemical composition.more » « less
-
Carbon materials display intriguing physical properties, including superconductivity and highly anisotropic thermal conductivity found in graphene. Compressive strain can induce structural and bonding transitions in carbon materials and create new carbon phases, but their interplay with thermal conductivity remains largely unexplored. We investigated the in situ high-pressure thermal conductivity of compressed graphitic phases using picosecond transient thermoreflectance and first-principles calculations. Our results show an anomalous thermal conductivity that peaks to 260 W/mK at 15–20 GPa but drops to 3.0 W/mK at ∼35 GPa. Together with complimentary in situ Raman and x-ray diffraction results, the abnormal thermal conductivity trend of compressed carbon is attributed to phonon-mediated conductivity influenced by interlayer buckling and 𝑠𝑝2 to 𝑠𝑝3 transition and, subsequently, the formation of 𝑀-carbon nanocrystals and amorphous carbon. Strain-induced structural and bonding variations provide a wide-range manipulation of thermal and mechanical properties in carbon materials.more » « less
-
null (Ed.)Abstract The high-pressure phases of oxyhydroxides (δ-AlOOH, ε-FeOOH, and their solid solution), candidate components of subducted slabs, have wide stability fields, thus potentially influencing volatile circulation and dynamics in the Earth’s lower mantle. Here, we report the elastic wave velocities of δ-(Al,Fe)OOH (Fe/(Al + Fe) = 0.13, δ-Fe13) to 79 GPa, determined by nuclear resonant inelastic X-ray scattering. At pressures below 20 GPa, a softening of the phonon spectra is observed. With increasing pressure up to the Fe 3+ spin crossover (~ 45 GPa), the Debye sound velocity ( v D ) increases. At higher pressures, the low spin δ-Fe13 is characterized by a pressure-invariant v D . Using the equation of state for the same sample, the shear-, compressional-, and bulk-velocities ( v S , v P , and v Φ ) are calculated and extrapolated to deep mantle conditions. The obtained velocity data show that δ-(Al,Fe)OOH may cause low- v Φ and low- v P anomalies in the shallow lower mantle. At deeper depths, we find that this hydrous phase reproduces the anti-correlation between v S and v Φ reported for the large low seismic velocity provinces, thus serving as a potential seismic signature of hydrous circulation in the lower mantle.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1038/s41567-023-02142-z
