Neutron diffraction study of the crystal and magnetic structures of antiferromagnetic manganese deuteride at high temperatures and high pressures

Machida, Akihiko*; Saito, Hiroyuki*; Aoki, Katsutoshi*; Komatsu, Kazuki*; Hattori, Takanori; Sano, Asami; Funakoshi, Kenichi*; Machida, Shinichi*; Sato, Toyoto*; Orimo, Shinichi*

Physical Review B, 111(22), p.224413_1 - 224413_6, 2025/06

https://doi.org/10.1103/yf8k-cy61

The crystal and magnetic structures of antiferromagnetic Mn deuterides formed by hydrogenating Mn metal at high temperature and high pressure, fcc -MnDx and hcp -MnDx, were investigated by in-situ neutron powder diffraction. Deuterium atoms partially occupied the octahedral interstitial positions of the fcc and hcp metal lattices. The site occupancies increased rapidly with decreasing temperature from 700 to 450 K and remained down to 300 K. Nel temperature of 543(10) K was determined for -MnD. For -MnD, saturation magnetic moment and Nel temperature were determined to be 0.82(1) and 347(3) K, respectively. The Nel temperatures determined for -MnD and -MnD are consistent with those predicted by the respective Slater-Pauling curves proposed in previous studies. The updated Nel temperatures provide insights into the development of more accurate Slater-Pauling curves based on electronic band structure calculations.

Hydrogenation of silicon-bearing hexagonal close-packed iron and its implications for density deficits in the inner core

Mori, Yuichiro*; Kagi, Hiroyuki*; Aoki, Katsutoshi*; Takano, Masahiro*; Kakizawa, Sho*; Sano, Asami; Funakoshi, Kenichi*

Earth and Planetary Science Letters, 634, p.118673_1 - 118673_8, 2024/05

https://doi.org/10.1016/j.epsl.2024.118673

To investigate silicon effects on the hydrogen-induced volume expansion of iron, neutron diffraction and X-ray diffraction experiments were conducted to examine hcp-FeSi under high pressures and high temperatures. Neutron diffraction experiments were performed on the deuterated hcp-FeSi at 13.5 GPa and 900 K, and at 12.1 GPa and 300 K. By combining the P-V-T equation of state of hcp-FeSi, present results indicate that the hydrogen-induced volume expansion of hcp-FeSi is 10% greater than that of pure hcp iron. Using the obtained values, we estimated the hydrogen content that would reproduce the density deficit in the inner core, which was 50% less than that without the effect of silicon. Possible hydrogen content, , in the inner core and the outer core was calculated to be 0.07 and 0.12-0.15, respectively, when reproducing the density deficit of the inner core with hcp-FeSiHx.

Hydrogen occupation and hydrogen-induced volume expansion in FeNiD at high conditions

Shito, Chikara*; Kagi, Hiroyuki*; Kakizawa, Sho*; Aoki, Katsutoshi*; Komatsu, Kazuki*; Iizuka, Riko*; Abe, Jun*; Saito, Hiroyuki*; Sano, Asami; Hattori, Takanori

American Mineralogist, 108(4), p.659 - 666, 2023/04

https://doi.org/10.2138/am-2022-8348

The phase relation and crystal structure of FeNiH (D) at high pressures and temperatures up to 12 GPa and 1000 K were clarified by in-situ X-ray and neutron diffraction measurements. Under conditions of the present study, no deuterium atoms occupied tetragonal () sites of face-centered cubic (fcc) FeNiD unlike fcc FeH(D). The deuterium-induced volume expansion per deuterium was determined as 2.45(4) and 3.31(6) for fcc and hcp phases, respectively, which were significantly larger than the corresponding values for FeD. The value slightly increased with increasing temperature. This study suggests that only 10% of nickel in iron drastically changes the behaviors of hydrogen in metal. Assuming that is constant regardless of pressure, the maximum hydrogen content in the Earth's inner core is estimated to be one to two times the amount of hydrogen in the oceans.

Neutron diffraction study on the deuterium composition of nickel deuteride at high temperatures and high pressures

Saito, Hiroyuki*; Machida, Akihiko*; Hattori, Takanori; Sano, Asami; Funakoshi, Kenichi*; Sato, Toyoto*; Orimo, Shinichi*; Aoki, Katsutoshi*

Physica B; Condensed Matter, 587, p.412153_1 - 412153_6, 2020/06

https://doi.org/10.1016/j.physb.2020.412153

The site occupancy of deuterium (D) atoms in face-centered-cubic nickel (fcc Ni) was measured along a cooling path from 1073 to 300 K at an initial pressure of 3.36 GPa via in situ neutron powder diffraction. Deuterium atoms predominantly occupy the octahedral (O) sites and slightly occupy the tetrahedral (T) sites of the fcc metal lattice. The O-site occupancy increases from 0.4 to 0.85 as the temperature is lowered from 1073 to 300 K. Meanwhile, the T-site occupancy remains c.a. 0.02. The temperature-independent behavior of the T-site occupancy is unusual, and its process is not yet understood. From the linear relation between the expanded lattice volume and D content, a D-induced volume expansion of 2.09(13) atom was obtained. This value is in agreement with the values of 2.14-2.2 atom previously reported for Ni and Ni Fe alloy.

Hexagonal close-packed iron hydride behind the conventional phase diagram

Machida, Akihiko*; Saito, Hiroyuki*; Hattori, Takanori; Sano, Asami; Funakoshi, Kenichi*; Sato, Toyoto*; Orimo, Shinichi*; Aoki, Katsutoshi*

Scientific Reports (Internet), 9(1), p.12290_1 - 12290_9, 2019/08

https://doi.org/10.1038/s41598-019-48817-7

Hexagonal close-packed iron hydride, hcp FeHx, is absent from the conventional phase diagram of the Fe-H system, although hcp metallic Fe exists stably over extensive temperature () and pressure () conditions, including those corresponding to the Earth's inner core. X-ray and neutron diffraction measurements at temperatures ranging from 298 to 1073 K and H pressures ranging from 4 to 7 GPa revealed that the hcp hydride was formed for FeH compositions when . Hydrogen atoms occupied the octahedral interstitial sites of the host metal lattice both partially and randomly. The hcp hydride exhibited a H-induced volume expansion of 2.48(5) /H-atom, which was larger than that of the face-centered cubic (fcc) hydride. The hcp hydride showed an increase in with , whereas the fcc hydride showed a corresponding decrease. The present study provides guidance for further investigations of the Fe-H system over an extensive -- region.

Phase diagram of the Eu-H system at high temperatures and high hydrogen pressures

Saito, Hiroyuki; Machida, Akihiko; Matsuoka, Takehiro*; Aoki, Katsutoshi*

Solid State Communications, 205, p.24 - 27, 2015/03

https://doi.org/10.1016/j.ssc.2014.12.019

Site occupation state of deuterium atoms in fcc Fe

Aoki, Katsutoshi*; Machida, Akihiko*; Saito, Hiroyuki*; Hattori, Takanori; Sano, Asami

Hamon, 25(1), p.26 - 31, 2015/02

https://doi.org/10.5611/hamon.25.1_26

The deuterization process of fcc Fe to form solid1solution fcc FeD was investigated by neutron diffraction measurements at high temperature and high pressure. In a completely deuterized specimen at 988 K and 6.3 GPa, deuterium atoms occupy the octahedral and tetrahedral interstitial sites with an occupancy of 0.532(9) and 0.056(5), respectively, giving a deuterium composition of 0.64(1). During deuterization, the metal-lattice expands approximately linearly with deuterium composition at a rate of 2.21 per deuterium atom. The minor occupation of tetrahedral site is likely driven by the intersite movement of deuterium atoms along the 111 direction in the fcc metal lattice. These results provide implications for the light elements in the Earth's core and the mechanism of hydrogen embrittlement of ferrous metals.

Site occupancy of interstitial deuterium atoms in face-centred cubic iron

Machida, Akihiko; Saito, Hiroyuki; Sugimoto, Hidehiko*; Hattori, Takanori; Sano, Asami; Endo, Naruki*; Katayama, Yoshinori; Iizuka, Riko*; Sato, Toyoto*; Matsuo, Motoaki*; et al.

Nature Communications (Internet), 5, p.5063_1 - 5063_6, 2014/09

https://doi.org/10.1038/ncomms6063

Iron hydride FeH, is thermodynamically stable only at high hydrogen pressure of several GPa. To investigate the hydrogenation process and hydrogen state in iron hydride, it is necessary to carry out the in-situ measurement under high pressure and high temperature. In this study, we performed the in-situ neutron diffraction measurement of Fe-D system using the high pressure neutron diffractometer PLANET in the MLF, J-PARC, and determined the deuterium occupying sites and occupancies in fcc-FeD. We found the minor occupation of tetrahedral sites under high pressure and high temperature. We considered the mechanism of the minor occupation based on the Quantum-mechanical calculation.

Disproportionation reaction of LaH at high pressure and low temperature

Machida, Akihiko; Watanuki, Tetsu; Kawana, Daichi*; Aoki, Katsutoshi

Journal of Physics; Conference Series, 500(2), p.022001_1 - 022001_5, 2014/05

https://doi.org/10.1088/1742-6596/500/2/022001

We found that LaH decomposed into two different molar-volume phases at 11 GPa at room temperature through synchrotron radiation X-ray diffraction (SR-XRD) measurements. Observed decomposition suggests that the H-poor and H-rich phases are spontaneously formed by pressurization, namely, a pressure-induced disproportionation reaction. Observed disproportionation reaction accompanies the transfer of the H atoms between the interstitial sites. Diffusivity of the H atoms suppresses as the temperature decreases. Hence we have investigated this disproportionation of LaH in the low H diffusivity case at low temperature.SR-XRD measurements at high pressure and low temperature were carried out at BL22XU, SPring-8. We found the disproportionation at 13.5 GPa even at 200 K. The volume fraction of the H-poor phase at 200 K is larger than that at room temperature. The disproportionation at low temperature will be discussed on the basis of the X-ray diffraction data.

Synthesis and formation process of AlCuH; A New class of interstitial aluminum-based alloy hydride

Saito, Hiroyuki; Takagi, Shigeyuki*; Endo, Naruki; Machida, Akihiko; Aoki, Katsutoshi; Orimo, Shinichi*; Katayama, Yoshinori

APL Materials (Internet), 1(3), p.032113_1 - 032113_7, 2013/09

https://doi.org/10.1063/1.4821632