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Title: Preparation and thermal expansion of (M{sub 0.5}{sup III}M{sup '}{sub 0.5}{sup V})P{sub 2}O{sub 7} with the cubic ZrP{sub 2}O{sub 7} structure

Abstract

A series of compounds (M{sub 0.5}{sup III}M{sup '}{sub 0.5}{sup V})P{sub 2}O{sub 7}, M{sup III}M{sup 'V}=AlTa, FeTa, GaTa, InNb, YNb, NdTa, and BiTa that are close structural relatives of cubic ZrP{sub 2}O{sub 7} were prepared. Annealing samples with M{sup III}M{sup 'V}=InNb or YNb at temperatures above 600 deg. C did not lead to any long-range cation ordering. The thermal expansion characteristics of samples quenched from 1000 deg. C with M{sup III}M{sup 'V}=AlTa, InNb and YNb were investigated by high-temperature powder diffraction over the temperature range 25-600 deg. C. There are no lattice constant discontinuities in this range, unlike ZrP{sub 2}O{sub 7}. (Al{sub 0.5}Ta{sub 0.5})P{sub 2}O{sub 7} and (In{sub 0.5}Nb{sub 0.5})P{sub 2}O{sub 7} show linear coefficients of thermal expansion (CTEs) of 11.5(2)x10{sup -6} and 11.8(2)x10{sup -6}K{sup -1}, respectively. These values are similar to that for the low-temperature ZrP{sub 2}O{sub 7} structure. However, the linear CTE for (Y{sub 0.5}Nb{sub 0.5})P{sub 2}O{sub 7} (4.8(2)x10{sup -6}K{sup -1}) is similar to that of the high-temperature form of ZrP{sub 2}O{sub 7}.

Authors:
 [1];  [2];  [3];  [4]
  1. School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA, 30332-0400 (United States)
  2. School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA, 30332-0400 (United States). E-mail: angus.wilkinson@chemistry.gatech.edu
  3. School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0245 (United States)
  4. Metals and Ceramics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6064 (United States)
Publication Date:
OSTI Identifier:
20784795
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 178; Journal Issue: 11; Other Information: DOI: 10.1016/j.jssc.2005.09.006; PII: S0022-4596(05)00409-3; Copyright (c) 2005 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALUMINIUM COMPOUNDS; ANNEALING; BISMUTH COMPOUNDS; DIFFRACTION; INDIUM COMPOUNDS; IRON COMPOUNDS; LATTICE PARAMETERS; NIOBIUM COMPOUNDS; PHASE TRANSFORMATIONS; PHOSPHATES; TANTALUM COMPOUNDS; TEMPERATURE RANGE 0273-0400 K; TEMPERATURE RANGE 0400-1000 K; THERMAL EXPANSION; YTTRIUM COMPOUNDS

Citation Formats

Varga, Tamas, Wilkinson, Angus P., Haluska, Michael S., and Andrew Payzant, E. Preparation and thermal expansion of (M{sub 0.5}{sup III}M{sup '}{sub 0.5}{sup V})P{sub 2}O{sub 7} with the cubic ZrP{sub 2}O{sub 7} structure. United States: N. p., 2005. Web. doi:10.1016/j.jssc.2005.09.006.
Varga, Tamas, Wilkinson, Angus P., Haluska, Michael S., & Andrew Payzant, E. Preparation and thermal expansion of (M{sub 0.5}{sup III}M{sup '}{sub 0.5}{sup V})P{sub 2}O{sub 7} with the cubic ZrP{sub 2}O{sub 7} structure. United States. doi:10.1016/j.jssc.2005.09.006.
Varga, Tamas, Wilkinson, Angus P., Haluska, Michael S., and Andrew Payzant, E. Tue . "Preparation and thermal expansion of (M{sub 0.5}{sup III}M{sup '}{sub 0.5}{sup V})P{sub 2}O{sub 7} with the cubic ZrP{sub 2}O{sub 7} structure". United States. doi:10.1016/j.jssc.2005.09.006.
@article{osti_20784795,
title = {Preparation and thermal expansion of (M{sub 0.5}{sup III}M{sup '}{sub 0.5}{sup V})P{sub 2}O{sub 7} with the cubic ZrP{sub 2}O{sub 7} structure},
author = {Varga, Tamas and Wilkinson, Angus P. and Haluska, Michael S. and Andrew Payzant, E.},
abstractNote = {A series of compounds (M{sub 0.5}{sup III}M{sup '}{sub 0.5}{sup V})P{sub 2}O{sub 7}, M{sup III}M{sup 'V}=AlTa, FeTa, GaTa, InNb, YNb, NdTa, and BiTa that are close structural relatives of cubic ZrP{sub 2}O{sub 7} were prepared. Annealing samples with M{sup III}M{sup 'V}=InNb or YNb at temperatures above 600 deg. C did not lead to any long-range cation ordering. The thermal expansion characteristics of samples quenched from 1000 deg. C with M{sup III}M{sup 'V}=AlTa, InNb and YNb were investigated by high-temperature powder diffraction over the temperature range 25-600 deg. C. There are no lattice constant discontinuities in this range, unlike ZrP{sub 2}O{sub 7}. (Al{sub 0.5}Ta{sub 0.5})P{sub 2}O{sub 7} and (In{sub 0.5}Nb{sub 0.5})P{sub 2}O{sub 7} show linear coefficients of thermal expansion (CTEs) of 11.5(2)x10{sup -6} and 11.8(2)x10{sup -6}K{sup -1}, respectively. These values are similar to that for the low-temperature ZrP{sub 2}O{sub 7} structure. However, the linear CTE for (Y{sub 0.5}Nb{sub 0.5})P{sub 2}O{sub 7} (4.8(2)x10{sup -6}K{sup -1}) is similar to that of the high-temperature form of ZrP{sub 2}O{sub 7}.},
doi = {10.1016/j.jssc.2005.09.006},
journal = {Journal of Solid State Chemistry},
number = 11,
volume = 178,
place = {United States},
year = {Tue Nov 15 00:00:00 EST 2005},
month = {Tue Nov 15 00:00:00 EST 2005}
}
  • A series of compounds (M{sup III}{sub 0.5}M'{sup V}{sub 0.5})P{sub 2}O{sub 7}, M{sup II}M{sup V}=AlTa, FeTa, GaTa, InNb, YNb, NdTa, and BiTa that are close structural relatives of cubic ZrP{sub 2}O{sub 7} were prepared. Annealing samples with M{sup II}M{sup V}=InNb or YNb at temperatures above 600 {sup o}C did not lead to any long-range cation ordering. The thermal expansion characteristics of samples quenched from 1000 {sup o}C with M{sup II}M{sup V}=AlTa, InNb and YNb were investigated by high-temperature powder diffraction over the temperature range 25--600 {sup o}C. There are not lattice constant discontinuities in this range, unlike ZrP{sub 2}O{sub 7}. (Al{submore » 0.5}Ta{sub 0.5})P{sub 2}O{sub 7} and (In{sub 0.5}Nb{sub 0.5})P{sub 2}O{sub 7} show linear coefficients of thermal expansion (CTEs) of 11.5(2)x10{sup -6} and 11.82(2)x10{sup -6}, respectively. These values are similar to that for the low-temperature ZrP{sub 2}O{sub 7} structure. However, the linear CTE for (Y{sub 0.5}Nb{sub 0.5})P{sub 2}O{sub 7} (4.8(2)x10{sup -6} K{sup -1}) is similar to that of the high-temperature form of ZrP{sub 2}O{sub 7}.« less
  • The [M{sub x}{sup II}M{sub 2.5-x}{sup III}(H{sub 2}O){sub 2}(HP{sup III}O{sub 3}){sub y}(P{sup V}O{sub 4}){sub 2-y}F; M=Fe (1), x=2.08, y=1.58; M=Co (2), x=2.5, y=2; Ni (3), x=2.5, y=2] compounds have been synthesized using mild hydrothermal conditions at 170 deg. C during five days. Single-crystals of (1) and (2), and polycrystalline sample of (3) were obtained. These isostructural compounds crystallize in the orthorhombic system, space group Aba2, with a=9.9598(2), b=18.8149(4) and c=8.5751(2) A for (1), a=9.9142(7), b=18.570(1) and c=8.4920(5) A for (2) and a=9.8038(2), b=18.2453(2) and c=8.4106(1) A for (3), with Z=8 in the three phases. An X-ray diffraction study reveals that themore » crystal structure is composed of a three-dimensional skeleton formed by [MO{sub 5}F] and [MO{sub 4}F{sub 2}] (M=Fe, Co and Ni) octahedra and [HPO{sub 3}] tetrahedra, partially substituted by [PO{sub 4}] tetrahedra in phase (1). The IR spectra show the vibrational modes of the water molecules and those of the (HPO{sub 3}){sup 2-} tetrahedral oxoanions. The thermal study indicates that the limit of thermal stability of these phases is 195 deg. C for (1) and 315 deg. C for (2) and (3). The electronic absorption spectroscopy shows the characteristic bands of the Fe(II), Co(II) and Ni(II) high-spin cations in slightly distorted octahedral geometry. Magnetic measurements indicate the existence of global antiferromagnetic interactions between the metallic centers with a ferromagnetic transition in the three compounds at 28, 14 and 21 K for (1), (2) and (3), respectively. Compound (1) exhibits a hysteresis loop with remnant magnetization and coercive field values of 0.72 emu/mol and 880 Oe, respectively. - Abstract: Polyhedral view of the crystal structure of the [M{sub x}{sup II}M{sub 2.5-x}{sup III}(H{sub 2}O){sub 2}(HP{sup III}O{sub 3}){sub y}(P{sup IV}O{sub 4}){sub 2-y}F; M=Fe, x=2.08, y=1.58; M=Co, Ni, x=2.5, y=2] compounds showing the sheets along the [001] direction.« less
  • The two diphosphates, Cd{sub 5}M{sub 2}{sup III}(P{sub 2}O{sub 7}){sub 4} with M - V, Fe, isotypic with Fe{sub 5}{sup II}Fe{sub 2}{sup III}(P{sub 2}O{sub 7}){sub 4}, have been synthesized. They crystallize in the space group C222 with a {approximately}8.8 {angstrom}, b {approximately}9.9 {angstrom}, and c {approximately}24.1 {angstrom}. The single crystal structure determination of the V phase and the Moessbauer spectroscopy study of the Fe phase, show that the cationic distribution is different from that observed in Fe{sub 5}{sup II}Fe{sub 2}{sup III}(P{sub 2}O{sub 7}){sub 4}, i.e., V(III) or Fe(III) is located in two kinds of sites instead of one kind of site.more » A detailed analysis of this structure shows that its octahedral layers consist of rock salt type ribbons, themselves built up from infinite chains of edge-sharing octahedra, interconnected through trioctahedral units of edge-sharing octahedra. On the basis of this description, the different cationic distribution compared to the pure Fe phase is then explained by the mismatch between infinite octahedral chains and trioctahedral units, due to the larger size of Cd(II) compared to Fe(II).« less
  • A new mixed valence compound, NH{sub 4}V{sub 3}O{sub 7}, as single crystals, has been synthesized hydrothermally. It crystallizes in the monoclinic system, space group I2/m with lattice parameters a=12.198(1)A, b=3.7530(2)A, c=13.178(1)A, {beta}=100.532(6){sup o}, V=593.11(7)A{sup 3}, Z=4. The crystal structure determined with R=0.038 consists of (V{sub 3}O{sub 7}){sub n} layers linked by ammonium cations. The layer is built up by replication through symmetry elements of three independent distorted octahedra sharing edges and corners. The distortion of vanadium octahedra tends to vary and the coordination number CN is reasonably selected as equal to 5+1. KV{sub 3}O{sub 7}, synthesized by the mild hydrothermalmore » route as a largely pure phase, is isostructural and its semi-conductive character is indicative of the presence of V{sup 4+} and V{sup 5+} sites. These are mixed valence compounds MV{sup 5+}V{sub 2}{sup 4+}O{sub 7}, the vanadium localization on three independent crystallographic sites enabling their electric behavior by electron hopping.« less
  • Hydrothermal reactions of molybdenum-oxide precursors with polyalcohols in the presence of base yielded two series of mixed-valence oxomolybdenum clusters, the hexadecanuclear species [XH{sub 12}(Mo{sup VI}O{sub 3}){sub 4}Mo{sup V}{sub 12}O{sub 40}]{sup m{minus}}(X=Na{sup +}, m=7; X=2H{sup +}, m=6) and the superclusters [XH{sub n}Mo{sup VI}{sub 6}Mo{sup V}{sub 36}O{sub 109}(OCH{sub 2}){sub 3}CR{sub 7}]{sup m{minus}} (X=Na-(H{sub 2}O){sub 3}{sup +}, m=9, n=13; X=Na(H{sub 2}O){sub 3}{sup +}, m=7, n=15; X=MoO{sub 3}, m=9, n=14; X=MoO{sub 3}, m=10, n=13). In a representative synthesis for the hexadencanuclear class of materials, the hydrothermal reaction of a mixture of Na{sub 2}MoO{sub 4}{center_dot}2H{sub 2}O, MoO{sub 3}, Mo metal, and NH{sub 4}Cl produced (NH{submore » 4}){sub 7}[NaMo{sub 16}(OH){sub 12}O{sub 40}]{center_dot}4h{sub 2}O (1{center_dot}4H{sub 2}O) as red-orange crystals. The compound (Me{sub 3}NH){sub 4}K{sub 2}[H{sub 2}Mo{sub 16}(OH){sub 40}]{center_dot}8H{sub 2}O(2{center_dot}8H{sub 2}O(2{center_dot}8H{sub 2}O) was prepared in a similar fashion. The structure of the anion of 1 consists of an {epsilon}-Keggin core H{sub 12}Mo{sub 12}O{sub 40}, capped on four hexagonal faces by MoO{sub 3} units and encapsulating a Na{sup +} cation. The structure of the oxomolybdenum framework of 2 is essentially identical to that of 1; however, the central cavity is now occupied by 2H{sup +}.« less