NMR study of C-A-S-H structures

Hanamachi, Yuji*; Walker, C.*; Sasamoto, Hiroshi; Mihara, Morihiro

NIMS Bisai Kozo Kaiseki Purattofuomu Riyo Hokokusho (Internet), 2 Pages, 2023/12

A High-volume Fly ash Silica fume Cement (HFSC) has been considered as the use of concrete support of drift in deep disposal of radioactive wastes. JAEA has been carried out experiments and modeling studies to evaluate chemical stability of C-A-S-H gel synthesized which would be believed as the dominant component of the HFSC. For the modeling purpose, it is necessary to evaluate the chemical composition both of C-A-S-H gel synthesized and accompanied minerals in the experiment. In the year of 2020, Al and Si NMR measurement were performed to identify Al and Si distribution in the sample and chemical composition of C-A-S-H gel was derived. However, it was impossible to derive the C-A-S-H gel composition having the expected Al/Si molar ratio since there were several accompanied minerals produced in the experiment due to the short term of immersion. This time similar approach to derive C-A-S-H gel composition is adopted using NMR measurement for the sample of longer time (6 months).

New approach to understanding the experimental Cs NMR chemical shift of clay minerals via machine learning and DFT-GIPAW calculations

Okubo, Takahiro*; Takei, Akihiro*; Tachi, Yukio; Fukatsu, Yuta; Deguchi, Kenzo*; Oki, Shinobu*; Shimizu, Tadashi*

Journal of Physical Chemistry A, 127(4), p.973 - 986, 2023/02

https://doi.org/10.1021/acs.jpca.2c08880

The identification of adsorption sites of Cs on clay minerals has been studied in the fields of environmental chemistry. The nuclear magnetic resonance (NMR) experiments allow direct observations of the local structures of adsorbed Cs. The NMR parameters of Cs, derived from solid-state NMR experiments, are sensitive to the local neighboring structures of adsorbed Cs. However, determining the Cs positions from NMR data alone is difficult. This paper describes an approach for identifying the expected atomic positions of Cs adsorbed on clay minerals by combining machine learning (ML) with experimentally observed chemical shifts. A linear ridge regression model for ML is constructed from the smooth overlap of atomic positions descriptor and gauge-including projector augmented wave (GIPAW) ab initio data. The Cs chemical shifts can be instantaneously calculated from the Cs positions on any clay layers using ML. The inverse analysis from the ML model can derive the atomic positions from experimentally observed chemical shifts.

NMR study of C-A-S-H structures

Walker, C.*

NIMS Bisai Kozo Kaiseki Purattofuomu Riyo Hokokusho (Internet), 2 Pages, 2021/09

High content fly ash silica fume cement (HFSC) has been considering a candidate low alkali cements for the geological disposal of radioactive waste in Japan. JAEA has been currently performing many experiments and modeling studies relevant to validation for the long-term stability of the C-A-S-H gel which is a dominant component of the HFSC. For developing the C-A-S-H model of hydration and degradation, it is necessary to determine the composition of C-A-S-H gel and accompanied minerals when it reacts with water. In the present subject, the synthesized sample of C-A-S-H gels were analyzed by using the NMR spectra of Al and Si to determine the coordination of these element in the C-A-S-H gel.

Nonmagnetic-magnetic transition and magnetically ordered structure in SmS

Yoshida, Shogo*; Koyama, Takehide*; Yamada, Haruhiko*; Nakai, Yusuke*; Ueda, Koichi*; Mito, Takeshi*; Kitagawa, Kentaro*; Haga, Yoshinori

Physical Review B, 103(15), p.155153_1 - 155153_5, 2021/04

https://doi.org/10.1103/PhysRevB.103.155153

Pore distribution of compacted Ca-montmorillonite using NMR relaxometry and cryoporometry; Comparison with Na-montmorillonite

Okubo, Takahiro*; Yamazaki, Akio*; Fukatsu, Yuta; Tachi, Yukio

Microporous and Mesoporous Materials, 313, p.110841_1 - 110841_11, 2021/01

https://doi.org/10.1016/j.micromeso.2020.110841

Pore distributions in water-saturated Ca-montmorillonite were investigated using H NMR measurements under various dry densities (0.8 - 1.6 g/cm) and porewater salinity conditions (deionized water, 0.1 and 1 M CaCl), at the temperature range of 233 - 303 K. The volume fractions of the interlayer pore including two and three hydrated layers and the non-interlayer pore in compacted Ca-montmorillonite were quantified by NMR relaxometry including and distribution analysis, and were compared with NMR cryoporometry and X-ray diffractometry. These analysis provided consistent pictures on the pore distributions in compacted Ca-montmorillonite, in contrast to Na-montmorillonite. The main factor affecting the pore distribution in compacted Ca- and Na-montmorillonite is the density, whereas the effect of porewater salinity is relatively smaller. The effect of interlayer cations is also relatively smaller at higher density, although the differences in the pore structures are significant at low density.

Orbitally defined field-induced electronic state in a Kondo lattice

Lessux, G. G.*; Sakai, Hironori; Hattori, Taisuke*; Tokunaga, Yo; Kambe, Shinsaku; Kuhns, P. L.*; Reyes, A. P.*; Thompson, J. D.*; Pagliuso, P. G.*; Urbano, R. R.*

Physical Review B, 101(16), p.165111_1 - 165111_6, 2020/04

https://doi.org/10.1103/PhysRevB.101.165111

CeRhIn is a Kondo-lattice prototype in which a magnetic field 31T induces an abrupt Fermi-surface (FS) reconstruction and pronounced in-plane electrical transport anisotropy all within its antiferromagnetic state. Here we report low-temperature nuclear magnetic resonance (NMR) measurements revealing a pronounced decrease in the In formal Knight shift, without changes in crystal or magnetic structures, of CeRhIn at fields () spanning . We discuss the emergent state above in terms of a change in Ce's 4 orbitals that arises from field-induced evolution of crystal-electric field (CEF) energy levels. This change in orbital character enhances hybridization between the 4 and the conduction electrons that leads ultimately to an itinerant quantum-critical point at 50T.

NMR studies on antiferromagnetic fluctuation in UPt

Aoyama, Taisuke*; Kotegawa, Hisashi*; To, Hideki*; Kimura, Noriaki*; Haga, Yoshinori; Yamamoto, Etsuji; Onuki, Yoshichika*

Physica B; Condensed Matter, 570, p.349 - 351, 2019/10

https://doi.org/10.1016/j.physb.2018.02.031

Pu nuclear magnetic resonance in the candidate topological insulator PuB

Dioguardi, A. P.*; Yasuoka, Hiroshi*; Thomas, S. M.*; Sakai, Hironori; Cary, S. K.*; Kozimor, S. A.*; Albrecht-Schmitt, T. E.*; Choi, H. C.*; Zhu, J.-X.*; Thompson, J. D.*; et al.

Physical Review B, 99(3), p.035104_1 - 035104_6, 2019/01

https://doi.org/10.1103/PhysRevB.99.035104

We present a detailed nuclear magnetic resonance (NMR) study of Pu in bulk and powdered single-crystal plutonium tetraboride (PuB), which has recently been investigated as a potential correlated topological insulator. The Pu NMR spectra are consistent with axial symmetry of the shift tensor showing for the first time that Pu NMR can be observed in an anisotropic environment and up to room temperature. The temperature dependence of the Pu shift, combined with a relatively long spin-lattice relaxation time (), indicate that PuB adopts a nonmagnetic state with gaplike behavior consistent with our density functional theory calculations. The temperature dependencies of the NMR Knight shift and imply bulk gaplike behavior confirming that PuB is a good candidate topological insulator.

Pore distribution of water-saturated compacted clay using NMR relaxometry and freezing temperature depression; Effects of density and salt concentration

Okubo, Takahiro*; Ibaraki, Moe*; Tachi, Yukio; Iwadate, Yasuhiko*

Applied Clay Science, 123, p.148 - 155, 2016/04

https://doi.org/10.1016/j.clay.2016.01.014

The pore distribution of water-saturated compacted clay (Na-montmorillonite at 0.8 and 1.4 g/cm saturated by three salt concentrations) was evaluated using H NMR relaxometry and freezing point depression. The populations of interlayer water with four hydrated state and non-interlayer water were calculated from the assumed thresholds. The sample with lower density exhibits higher population of non-interlayer water up to 55%. Low-temperature H NMR experiments in view of freezing point depression indicated that mesopore water in approximately 4 nm space observed in the calorimetric study was considered as non-interlayer water and the threshold temperature. The result showed that population of non-interlayer water by expected from freezing point depression agreed with H NMR relaxometry within 10%. Correlation experiments between longitudinal () and transverse relation times () at -10C suggested that high-mobility bulk-like water molecules existed at a clay density of 1.4 g/cm.

Distributed twofold ordering in URuSi

Kambe, Shinsaku; Tokunaga, Yo; Sakai, Hironori; Walstedt, R. E.*

Physical Review B, 91(3), p.035111_1 - 035111_8, 2015/01

https://doi.org/10.1103/PhysRevB.91.035111

In previous Si NMR basal-plane field rotation measurements, a modest breaking of the fourfold symmetry was suggested in the hidden-order state of URuSi. Here, the angular dependence of the Si NMR linewidth is analyzed in detail, indicating the occurrence of a distribution of twofold local fields at the Si sites even in a high-quality single crystal. The relation between sample quality and the occurrence of effects having twofold symmetry is discussed.