Xiaojun Hu

Partitioning experiments and the chemistry of iron meteorites indicate that the light element nitrogen could be sequestered into the metallic core of rocky planets during core–mantle differentiation. The thermal conductivity and the mineralogy of the Fe–N system under core conditions could therefore influence the planetary cooling, core crystallization, and evolution of the intrinsic magnetic field of rocky planets. Limited experiments have been conducted to study the thermal properties and phase relations of Fe–N components under planetary core conditions, such as those found in the Moon, Mercury, and Ganymede. In this study, we report results from high-pressure experiments involving electrical resistivity measurements of Fe–N phases at a pressure of 5 GPa and temperatures up to 1400 K. Four Fe–N compositions, including Fe–10%N, Fe–6.4%N, Fe–2%N, and Fe–1%N (by weight percent), were prepared and subjected to recovery experiments at 5 GPa and 1273 K. These experiments show that Fe–10%N and Fe–6.4%N form a single hexagonal close-packed phase (ɛ-nitrides), while Fe–2%N and Fe–1%N exhibit a face-centered cubic structure (γ-Fe). In separate experiments, the resistivity data were collected during the cooling after compressing the starting materials to 5 GPa and heating to ~1400 K. The resistivity of all compositions, similar to the pure γ-Fe, exhibits weak temperature dependence. We found that N has a strong effect on the resistivity of metallic Fe under rocky planetary core conditions compared to other potential light elements such as Si. The temperature-dependence of the resistivity also revealed high-pressure phase transition points in the Fe–N system. A congruent reaction, ε ⇌ γ’, occurs at ~673 K in Fe–6.4%N, which is ~280 K lower than that at ambient pressure. Furthermore, the resistivity data provided constraints on the high-pressure phase boundary of the polymorphic transition, γ ⇌ α, and an eutectoid equilibrium of γ’ ⇌ α + ε. The data, along with the recently reported phase equilibrium experiments at high pressures, enable construction of a phase diagram of the Fe–N binary system at 5 GPa.

On the basis of the van der Pauw method, we developed a new technique for measuring the electrical resistivity of metals in a cubic multi-anvil high-pressure apparatus. Four electrode wires were introduced into the sample chamber and in contact with the pre-pressed metal disk on the periphery. The sample temperature was measured with a NiCr–NiSi (K-type) thermocouple, which was separated from the sample by a thin hexagonal boron nitride layer. The electrodes and thermocouple were electrically insulated from each other and from the heater by an alumina tube as well. Their leads were in connection with cables through the gap between the tungsten carbide anvils. We performed experiments to determine the temperature dependence of electrical resistivity of pure iron at 3 and 5 GPa. The experiments produce reproducible measurements and the results provide an independent check on electrical resistivity data produced by other methods. The new technique provides reliable electrical resistivity measurements of metallic alloys and compounds at high pressure and temperature.

Understanding the effect of carbon on the density of hcp (hexagonal-close-packed) Fe-C alloys is essential for modeling the carbon content in the Earth’s inner core. Previous studies have focused on the equations of state of iron carbides that may not be applicable to the solid inner core that may incorporate carbon as dissolved carbon in metallic iron. Carbon substitution in hcp-Fe and its effect on the density have never been experimentally studied. We investigated the compression behavior of Fe-C alloys with 0.31 and 1.37 wt % carbon, along with pure iron as a reference, by in-situ X-ray diffraction measurements up to 135 GPa for pure Fe, and 87 GPa for Fe-0.31C and 109 GPa for Fe-1.37C. The results show that the incorporation of carbon in hcp-Fe leads to the expansion of the lattice, contrary to the known effect in body-centered cubic (bcc)-Fe, suggesting a change in the substitution mechanism or local environment. The data on axial compressibility suggest that increasing carbon content could enhance seismic anisotropy in the Earth’s inner core. The new thermoelastic parameters allow us to develop a thermoelastic model to estimate the carbon content in the inner core when carbon is incorporated as dissolved carbon hcp-Fe. The required carbon contents to explain the density deficit of Earth’s inner core are 1.30 and 0.43 wt % at inner core boundary temperatures of 5000 K and 7000 K, respectively.