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Title: Crystallographic and compositional contributions to the breakdown of the GdNi 1−x Co x solid solution

Authors:
ORCiD logo; ; ;
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1413044
Grant/Contract Number:
AC02-07CH11358
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Alloys and Compounds
Additional Journal Information:
Journal Volume: 696; Journal Issue: C; Related Information: CHORUS Timestamp: 2017-12-12 16:11:57; Journal ID: ISSN 0925-8388
Publisher:
Elsevier
Country of Publication:
Netherlands
Language:
English

Citation Formats

Prost, T. E., Chumbley, L. S., Mudryk, Y., and Pecharsky, V. K. Crystallographic and compositional contributions to the breakdown of the GdNi 1−x Co x solid solution. Netherlands: N. p., 2017. Web. doi:10.1016/j.jallcom.2016.11.312.
Prost, T. E., Chumbley, L. S., Mudryk, Y., & Pecharsky, V. K. Crystallographic and compositional contributions to the breakdown of the GdNi 1−x Co x solid solution. Netherlands. doi:10.1016/j.jallcom.2016.11.312.
Prost, T. E., Chumbley, L. S., Mudryk, Y., and Pecharsky, V. K. Wed . "Crystallographic and compositional contributions to the breakdown of the GdNi 1−x Co x solid solution". Netherlands. doi:10.1016/j.jallcom.2016.11.312.
@article{osti_1413044,
title = {Crystallographic and compositional contributions to the breakdown of the GdNi 1−x Co x solid solution},
author = {Prost, T. E. and Chumbley, L. S. and Mudryk, Y. and Pecharsky, V. K.},
abstractNote = {},
doi = {10.1016/j.jallcom.2016.11.312},
journal = {Journal of Alloys and Compounds},
number = C,
volume = 696,
place = {Netherlands},
year = {Wed Mar 01 00:00:00 EST 2017},
month = {Wed Mar 01 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.jallcom.2016.11.312

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  • The spinel system Zn{sub 0.4}Co{sub 0.6}Al{sub x}Fe{sub 2-x}O{sub 4} (x=0.0, 0.25, 0.50, 0.75, and 1.0) has been prepared in air at 1300 deg. C by standard solid state sintering method. X-ray and neutron powder diffraction measurements have been performed to characterize the materials. The crystal structure of the system has been found out by refining neutron diffraction data and cubic symmetry corresponding to the space group Fd3m has been confirmed for all the samples of the series. Zn and Al ions exclusively enter into the tetrahedral (A) and octahedral (B) sites, respectively, while Co and Fe ions are distributed overmore » both the A and B sites for the whole compositional range investigated. With increasing x, the occupation of Co gradually increases in A site and that in B site decreases, and the Fe ions gradually decrease in both the sites. The lattice constant decreases and the oxygen position parameter increases with increasing Al content in the system. The moment distributions in the two sublattices for different compositions have also been determined. The magnetization measurements show that the saturation magnetization and the Neel temperature decreases with increasing Al contents and the coercivity decreases initially and then increases when x>0.75.« less
  • The reaction between hexahydrated lanthanum(III) nitrate and 1,10-phenanthroline (phen) in acetonitrile solution was investigated by [sup 1]H, [sup 13]C, [sup 17]O, and [sup 139]La NMR spectroscopy. The crystal structure of trinitratobis(1,10-phenanthroline)lanthanum(III) (La-(NO[sub 3])[sub 3](C[sub 12]H[sub 8]N[sub 2])[sub 2]) was determined by X-ray diffraction as having a monoclinic lattice. In solution, [sup 139]La NMR spectra have shown up to three sites in slow exchange with variable intensities. They were attributed to solvated La(III) ions and to two complex species with one or two phen ligands in the La(III) coordination shell. A more complete structural analysis by [sup 17]O NMR spectroscopy indicatedmore » that during the course of the complexation by phen, coordinated water was totally expelled from the La(III) coordination sphere, whereas all three nitrate groups remained coordinated. Proton NMR data have confirmed the total displacement of water. In addition, the proton chemical shifts of phen, in comparison with the [sup 13]C NMR data, clearly showed an anisotropic shielding contribution when two phen ligands were coordinated to La(III). This indicates that the two phen molecules are in a close vicinity in the coordination sphere. From the NMR results, one can conclude that the structure in solution of the 2:1 complex, La(NO[sub 3])[sub 3](phen)[sub 2], is very similar to the solid-state one. From [sup 139]La NMR spectroscopy, the populations of the various La(III) species were obtained and the apparent formation constants were calculated.« less
  • The Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} [0{<=}x{<=}1] solid solution exhibits a complex magnetic behaviour due to the bond-frustration in its magnetic structure. Heat capacity measurements of the (x=0.1-0.5) phases show a three-dimensional magnetic ordering ({lambda} anomaly) that shifts to lower temperatures and becomes broader as the AsO{sub 4}{sup 3-} content increases. For x=0.75, no significant feature was observed whereas for higher arsenate ion content, x=0.9 and 1, a small maximum was detected. The magnetic structures of solid solution are consistent with the existence of predominant antiferromagnetic superexchange interactions through the |OH| and |XO{sub 4}| (X=P and As) groups betweenmore » the Co{sup +2} ions. The substitution of PO{sub 4}{sup 3-} by AsO{sub 4}{sup 3-} anions by more than 90% substantially modifies the magnetic exchange pathways in the solid solution, leading to an incommensurate antiferromagnetic structure in Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} [x=0.9 and 1] phases. - Graphical abstract: Magnetic structures of Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} [0{<=}x{<=}1]. The ordering of the magnetic moments of Co{sup 2+} is in c direction for the two crystallographic positions (dimers and chains) in all compounds. The unit cell is surrounded by a red line. Highlights: Black-Right-Pointing-Pointer Synthesis of a new adamite-type compounds, Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} (0.1, 0.25, 0.5, 0.75, 0.9) phases. Black-Right-Pointing-Pointer Co{sub 2}(OH)(PO{sub 4}){sub 1-x}(AsO{sub 4}){sub x} (0-1) solid solution; magnetic frustrated system. Black-Right-Pointing-Pointer High resolution neutron powder diffraction to determine the crystal structures. Black-Right-Pointing-Pointer Incommensurate magnetic structures at low temperature. Black-Right-Pointing-Pointer Magnetostructural correlations in cobalt-based Co{sub 2}(OH)XO{sub 4} (X=P and As) insulation compounds.« less