Kenji Iwase

Phase transformation and crystal structure of La(2)Ni(7)H(x) studied by in situ X-ray diffraction.

The phase transformation of La(2)Ni(7) during hydrogenation was investigated by in situ X-ray diffraction. We found two hydride phases, La(2)Ni(7)H(7.1) (phase I) and La(2)Ni(7)H(10.8) (phase II), during the first absorption cycle. The metal sublattice of phase I was orthorhombic (space group Pbcn) with lattice parameters a = 0.50128(6) nm, b = 0.8702(1) nm, and c = 3.0377(1) nm. The sublattice for phase II was monoclinic (space group C2/c) with lattice parameters a = 0.51641(9) nm, b = 0.8960(1) nm, c = 3.1289(1) nm, and β = 90.17(1)°. The lattice parameter c increased with the hydrogen content, while a and b decreased in the formation of phase I from the alloy. Phase transformation from phase I to phase II was accompanied by isotropic expansion. The La(2)Ni(4) and LaNi(5) subunit expanded by 48.9% and 6.0% in volume, respectively, during hydrogenation to phase I. They expanded an additional 14% and 5.8%, respectively, in the formation of phase II. The obtained volume expansion suggested different hydrogen distribution in the La(2)Ni(4) and LaNi(5) subunit during hydrogenation.

Imaging of a spatial distribution of preferred orientation of crystallites by pulsed neutron Bragg edge transmission

A pulsed neutron transmission coupled with a two-dimensional position sensitive neutron detector gives a time-of-flight spectrum at each pixel of the detector, which depends on the total cross-sections of materials. In order to extract quantitative information of the preferred orientation included in the Bragg scattering total cross-section data, a spectral analysis software for the 2D imaging has been developed, and the transmission data of an unbent iron plate were analyzed. The 2D images with respect to the preferred orientation were successfully obtained, and the effectiveness of spectroscopic neutron transmission imaging was indicated.

In situ lattice strain mapping during tensile loading using the neutron transmission and diffraction methods

In this study, the change in internal lattice strain in an iron plate during tensile deformation was investigated by performing in situ measurements under applied force. The lattice strain was evaluated by neutron diffraction and Bragg-edge transmission. The neutron diffraction results showed that the averaged 110 lattice strain along the direction perpendicular to the applied force was between −422 and −109 × 10−6. The position dependence of the lattice strain and the change in the distribution of elastic strain in an iron plate with notches during tensile deformation was obtained by Bragg-edge transmission. It was also observed that, when the load increased over 30 kN, the area of plastic deformation increased around the positions of the notches.

Synthesis and crystal structure of a Pr5Ni19 superlattice alloy and its hydrogen absorption-desorption property.

The intermetallic compound Pr(5)Ni(19), which is not shown in the Pr-Ni binary phase diagram, was synthesized, and the crystal structure was investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Two superlattice reflections with the Sm(5)Co(19)-type structure (002 and 004) and the Pr(5)Co(19)-type structure (003 and 006) were observed in the 2θ region between 2° and 15° in the XRD pattern using Cu Kα radiation. Rietveld refinement provided the goodness-of-fit parameter S = 6.7 for the Pr(5)Co(19)-type (3R) structure model and S = 1.7 for the Sm(5)Co(19)-type (2H) structure model, indicating that the synthesized compound has a Sm(5)Co(19) structure. The refined lattice parameters were a = 0.50010(9) nm and c = 3.2420(4) nm. The high-resolution TEM image also clearly revealed that the crystal structure of Pr(5)Ni(19) is of the Sm(5)Co(19) type, which agrees with the results from Rietveld refinement of the XRD data. The P-C isotherm of Pr(5)Ni(19) in the first absorption was clearly different from that in the first desorption. A single plateau in absorption and three plateaus in desorption were observed. The maximum hydrogen storage capacity of the first cycle reached 1.1 H/M, and that of the second cycle was 0.8 H/M. The 0.3 H/M of hydrogen remained in the metal lattice after the first desorption process.

Synthesis of new compound Gd5Ni19 with a superlattice structure and hydrogen absorption properties.

We successfully synthesized the new intermetallic compound Gd(5)Ni(19) and determined its crystal structure by X-ray diffraction (XRD) and scanning transmission electron microscopy (STEM). The structure is a Sm(5)Co(19)-type superlattice structure (2H, space group P6(3)/mmc), and the lattice parameters were determined as a = 0.4950(1) nm and c = 3.2161(5) nm by X-ray Rietveld refinement. The XRD results agreed with the STEM analysis results. The P-C isotherm of Gd(5)Ni(19) was measured at 233 K. In the first absorption cycle, the maximum hydrogen capacity reached 1.07 H/M at 2.0 MPa. The sloping plateau was observed in the first absorption-desorption cycle. The maximum hydrogen capacity decreased by 0.87 H/M in the second absorption cycle, implying that hydrogen in the amount of H/M = 0.20 remained in the alloy before the second absorption-desorption cycle.

In situ XRD study of La2Ni7H(x) during hydrogen absorption-desorption.

Structural changes of La2Ni7H(x) during the first and second absorption-desorption processes along the P-C isotherm were investigated by in situ X-ray diffraction (XRD). Orthorhombic (Pbcn) and monoclinic (C2/c) hydrides coexisted in the first absorption plateau, but only a monoclinic (C2/c) hydride was observed in the first desorption plateau. Phase transformation of La2Ni7H(x) was irreversible between the first as well as the second absorption-desorption process. The lattice parameters and expansion of the La2Ni4 and LaNi5 cells during the absorption-desorption process were refined using the Rietveld method. The lattice parameters a and b of the orthorhombic hydride (Pbcn) decreased, while the lattice parameter c increased with increasing hydrogen content in the first absorption. During the first absorption, the volume of the orthorhombic La2Ni4 cell expanded by more than 50%, while the expansion of the LaNi5 cell was below 10%. The monoclinic La2Ni4 cell expanded to approximately four times the size of the LaNi5 cell in the first absorption. The lattice parameters a, b, and c of the monoclinic hydride (C2/c) decreased with decreasing hydrogen content in the first desorption. These La2Ni4 and LaNi5 cells contracted isotropically in the first desorption.

Structural parameters of Pr3MgNi14 during hydrogen absorption-desorption process.

Structural parameters of Pr(3)MgNi(14) after a cyclic hydrogen absorption-desorption process were investigated by X-ray diffraction. Pr(3)MgNi(14) consisted of two phases: 80% Gd(2)Co(7)-type structure and 20% PuNi(3)-type structure. The pressure-composition (P-C) isotherm of Pr(3)MgNi(14) indicates a maximum hydrogen capacity of 1.12 H/M (1.61 mass %) at 298 K. The cyclic property of Pr(3)MgNi(14) up to 1000 cycles was measured at 313 K. The retention rate of the sample was 87.5% at 1000 cycles, which compares favorably with that of LaNi(5). After 1000 cycles, the expansions of lattice parameters a and c and the lengths along the c-axes of the PrNi(5) and PrMgNi(4) cells of the Gd(2)Co(7)-type structures were 0.20%, 1.26%, 0.47%, and 3.68%, respectively. The metal sublattice expanded anisotropically after the cyclic test. The isotropic and anisotropic lattice strains can be refined by Rietveld analysis. The anisotropic and isotropic lattice strains were almost saturated at the first activation process and reached values of 0.2% and 0.1%, respectively, after 1000 cycles. These values are smaller by 1 order of magnitude than those of LaNi(5).

Various regimes of quantum behavior in anS=12Heisenberg antiferromagnetic chain with fourfold periodicity

We have succeeded in synthesizing single crystals of the verdazyl radical beta-2,6-Cl2-V [= beta-3-(2,6-dichlorophenyl)-1,5-diphenylverdazyl]. The ab initio MO calculation indicated the formation of an S = 1/2 Heisenberg antiferromagnetic chain with four-fold magnetic periodicity consisting of three types of exchange interactions.We have successfully explained the magnetic and thermodynamic properties based on the expected spin model by using the quantum Monte Carlo method. Furthermore, we revealed that the alternating and unique Ising ferromagnetic chains become effective in the specific field regions and observed a cooperative phenomenon caused by the magnetic order and quantum fluctuations. These results demonstrate that verdazyl radical could form unconventional spin model with interesting quantum behavior and provide a new way to study a variety of quantum spin systems.

Fine-Tuning of Magnetic Interactions in Organic Spin Ladders

We have succeeded in synthesizing two types of new organic radical crystals 3-I-V [= 3-(3-iodophenyl)-1,5-diphenylverdazyl] and 3-Br-4-F-V [= 3-(3-bromo-4-fluorophenyl)-1,5-diphenylverdazyl]. Their crystal strucutures are found to be isomorphous to that of previously reported spin ladder 3-Cl-4-F-V. Through the quantitative analysis of their molecular arrangements and magnetic properties, we confirm that these materials form ferromagnetic chain-based spin ladders with slightly modulated magnetic interactions. These results present the first quantitative demonstration of the fine-tuning of magnetic interactions in the molecular-based materials.We have succeeded in synthesizing two types of new organic radical crystals 3-I-V [= 3-(3-iodophenyl)-1,5-diphenylverdazyl] and 3-Br-4-F-V [= 3-(3-bromo-4-fluorophenyl)-1,5-diphenylverdazyl]. Their crystal strucutures are found to be isomorphous to that of previously reported spin ladder 3-Cl-4-F-V. Through the quantitative analysis of their molecular arrangements and magnetic properties, we confirm that these materials form ferromagnetic chain-based spin ladders with slightly modulated magnetic interactions. These results present the first quantitative demonstration of the fine-tuning of magnetic interactions in the molecular-based materials.

Crystal structure and cyclic hydrogenation property of Pr4MgNi19.

The hydrogen absorption-desorption property and the crystal structure of Pr4MgNi19 was investigated by pressure-composition isotherm measurement and X-ray diffraction (XRD). Pr4MgNi19 consisted of two phases: 52.9% Ce5Co19-type structure (3R) and 47.0% Gd2Co7-type structure (3R). Sm5Co19-type structure (2H) and Ce2Ni7-type structure (2H) were not observed in the XRD profile. The Mg atoms substituted at the Pr sites in a MgZn2-type cell. The maximum hydrogen capacity reached 1.14 H/M (1.6 mass%) at 2 MPa. The hysteresis factor, Hf = ln(Pabs/Pdes), was 1.50. The cyclic hydrogenation property of Pr4MgNi19 was investigated up to 1000 absorption-desorption cycles. After 250, 500, 750, and 1000 cycles, the retention rates of hydrogen were reduced to 94%, 92%, 91%, and 90%, respectively. These properties were superior to those of Pr2MgNi9 and Pr3MgNi14.