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At least 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Synthesis, crystal structure and magnetic properties of Li{sub 2}InMo{sub 3}O{sub 8}: A novel reduced molybdenum oxide containing magnetic Mo{sub 3} clusters

Powder samples and single crystals of Li{sub 2}InMo{sub 3}O{sub 8} were obtained by solid state reaction. The structure was determined by single-crystal X-ray diffraction (771 independent reflections for 33 refinable, R1=0.0158 and wR2=0.0354). Li{sub 2}InMo{sub 3}O{sub 8} is isomorphous with Li{sub 2}SnMo{sub 3}O{sub 8} and crystallizes in the hexagonal space group P6{sub 3}mc with unit-cell parameters a=5.7931(2) Å, c=10.4681(4) Å and Z=2. The crystal structure consists of distorted hexagonal-close-packed oxygen layers with stacking sequence abac along [0 0 1] and that are held together by alternating lithium–indium and molybdenum layers. The Li{sup +} and In{sup 3+} ions occupy, respectively, tetrahedral and octahedral sites in the ratio 2:1. The Mo atoms occupy octahedral sites and form strongly bonded triangular clusters involving three MoO{sub 6} octahedra that are each shared along two edges, constituting a Mo{sub 3}O{sub 13} unit. The variations of the Mo–Mo and Mo–O bond lengths according to the number of electrons per Mo{sub 3} cluster are discussed. The trivalent oxidation state of the indium leads to one unpaired electron per Mo{sub 3} and thus gives rise to a paramagnetic spin behavior with an effective magnetic moment of 1.5 μ{sub B} per Mo{sub 3} cluster. The magnetic susceptibility vs. temperature curve also shows a maximum at 25 K arising probably from an antiferromagnetic ordering between the Mo{sub 3} clusters. - Graphical abstract: We present here the synthesis, the crystal structure, and the magnetic properties of the new quaternary compound Li{sub 2}InMo{sub 3}O{sub 8} containing magnetic Mo{sub 3}O{sub 13} units with one unpaired electron. - Highlights: • The new quaternary reduced molybdenum oxide containing Mo{sub 3} clusters, Li{sub 2}InMo{sub 3}O{sub 8}, was synthesized by solid state reaction. • Single-crystal X-ray study. • One unpaired electron per Mo{sub 3} cluster leading to a paramagnetic spin behavior with an effective magnetic moment of 1.5 μ{sub B} per Mo{sub 3} cluster. • Magnetic susceptibility measurements show a maximum at 25 K arising probably from an antiferromagnetic ordering between the Mo{sub 3} clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Rare-earth transition-metal gallium chalcogenides RE{sub 3}MGaCh{sub 7} (M=Fe, Co, Ni; Ch=S, Se)

Six series of quaternary rare-earth transition-metal chalcogenides RE{sub 3}MGaCh{sub 7} (M=Fe, Co, Ni; Ch=S, Se), comprising 33 compounds in total, have been prepared by reactions of the elements at 1050 °C (for the sulphides) or 900 °C (for the selenides). They adopt noncentrosymmetric hexagonal structures (ordered Ce{sub 3}Al{sub 1.67}S{sub 7}-type, space group P6{sub 3}, Z=2) with cell parameters in the ranges of a=9.5–10.2 Å and c=6.0–6.1 Å for the sulphides and a=10.0–10.5 Å and c=6.3–6.4 Å for the selenides as refined from powder X-ray diffraction data. Single-crystal structures were determined for five members of the sulphide series RE{sub 3}FeGaS{sub 7} (RE=La, Pr, Tb) and RE{sub 3}CoGaS{sub 7} (RE=La, Tb). The highly anisotropic crystal structures consist of one-dimensional chains of M-centred face-sharing octahedra and stacks of Ga-centred tetrahedra all pointing in the same direction. Magnetic measurements on the sulphides reveal paramagnetic behaviour in some cases and long-range antiferromagnetic behaviour with low Néel temperatures (15 K or lower) in others. Ga L-edge XANES spectra support the presence of highly cationic Ga tetrahedral centres with a tendency towards more covalent Ga–Ch character on proceeding from the sulphides to the selenides. Band structure calculations on La{sub 3}FeGaS{sub 7} indicate that the electronic structure is dominated by Fe 3d-based states near the Fermi level. - Graphical abstract: The series of chalcogenides RE{sub 3}MGaS{sub 7}, which form for a wide range of rare-earth and transition metals (M=Fe, Co, Ni), adopt highly anisotropic structures containing chains of M-centred octahedra and stacks of Ga-centred tetrahedra. Display Omitted - Highlights: • Six series (comprising 33 compounds) of chalcogenides RE{sub 3}MGaCh{sub 7} were prepared. • They adopt noncentrosymmetric hexagonal structures with high anisotropy. • Most compounds are paramagnetic; some show antiferromagnetic ordering. • Ga L-edge XANES confirms presence of cationic Ga species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

From Ag{sub 2}Sb{sub 2}O{sub 6} to Cd{sub 2}Sb{sub 2}O{sub 7}: Investigations on an anion-deficient to ideal pyrochlore solid solution

A complete solid solution between the anion-deficient pyrochlore Ag{sub 2}Sb{sub 2}O{sub 6} and the ideal pyrochlore Cd{sub 2}Sb{sub 2}O{sub 7} has been synthesized through the standard solid state ceramic method. Each composition has been characterized by various different techniques, including powder X-ray diffraction, optical spectroscopy, electron paramagnetic resonance and {sup 121}Sb Mössbauer spectroscopy. Computational methods based on density functional theory complement this investigation. Photocatalytic activity has been studied, and transport properties have been measured on pellets densified by spark plasma sintering. The analysis of the data collected from these various techniques enables a comprehensive characterization of the complete solid solution and revealed an anomalous behavior in the Cd-rich end of the solid solution, which has been proposed to arise from a possible radical O{sup −} species in small concentrations. - Graphical abstract: A complete solid solution between the anion-deficient pyrochlore Ag{sub 2}Sb{sub 2}O{sub 6} and the ideal pyrochlore Cd{sub 2}Sb{sub 2}O{sub 7} has been synthesized and investigated through various techniques including X-ray diffraction, electron paramagnetic spectroscopy, and {sup 121}Sb-Mössbauer spectroscopy. Optical and electrical measurements have been performed, and computational methods have been applied to determine the density of states. Photocatalytic activity was monitored by the degradation of Methylene Blue, and upon cadmium substitution, the degradation amount decreased, which is attributed primarily to the changing optical and electrical properties of the solid solution. Display Omitted - Highlights: • A complete solid solution between Ag{sub 2}Sb{sub 2}O{sub 6} and Cd{sub 2}Sb{sub 2}O{sub 7} has been synthesized. • XRD reveals a relatively constant lattice parameter as the series progresses. • Optical and electrical properties have been measured for the solid solution. • Computational methods have been used to determine the density of states. • Photocatalytic degradation of Methylene Blue decreased upon cadmium substitution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Magnetization, magnetic susceptibility, effective magnetic moment of Fe{sup 3+} ions in Bi{sub 25}FeO{sub 39} ferrite

Magnetic susceptibility for ferrite Bi{sub 25}FeO{sub 39} is measured at 5–950 K in the magnetic field of 0.86 T. It is shown that Bi{sub 25}FeO{sub 39} is paramagnetic in the temperature range 5−950 K. The saturation magnetization is equal to 5.04μ{sub B} per formula unit at 5 K in a magnetic field of 10 T. It is found that at 5−300 K the effective magnetic moment of Fe{sup 3+} ions in Bi{sub 25}FeO{sub 39} is equal to 5.82μ{sub B}. - Graphical abstract: The dependence of the magnetization (n, μ{sub B}) on the magnetic field for one formula unit of Bi{sub 25}FeO{sub 39} at 5 K. - Highlights: • Magnetic susceptibility for Bi{sub 25}FeO{sub 39} is measured at 5–950 K in the magnetic field of 0.86 T. • It is shown that Bi{sub 25}FeO{sub 39} is paramagnetic in the temperature range 5−950 K. • The saturation magnetization is equal to 5.04μ{sub B} per formula unit at 5 K in a magnetic field of 10 T.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Rare-earth transition-metal chalcogenides Ln{sub 3}MGaS{sub 7} (Ln=Nd, Sm, Dy, Er; M=Co, Ni) and Ln{sub 3}MGaSe{sub 7} (Ln=Nd, Sm, Gd, Dy, M=Co; Ln=Nd, Gd, Dy, M=Ni)

Fifteen new rare-earth transition-metal chalcogenides, Ln{sub 3}MGaS{sub 7} (Ln=Nd, Sm, Dy, Er; M=Co, Ni) and Ln{sub 3}MGaSe{sub 7} (Ln=Nd, Sm, Gd, Dy, M=Co; Ln=Nd, Gd, Dy, M=Ni), have been synthesized by solid state reactions. They are isostructural, adopt Ce{sub 3}Al{sub 1.67}S{sub 7}—related structure type, and crystallize in the non-centrosymmetric hexagonal space group P6{sub 3}. They adopt a three-dimensional framework composed of LnQ{sub 7} monocapped trigonal prisms with the interesting [MQ{sub 3}]{sup 4−} chains and isolated GaQ{sub 4} tetrahedra lying in two sets of channels in the framework. The magnetic susceptibility measurements on Ln{sub 3}CoGaQ{sub 7} (Ln=Dy, Er, Q=S; Ln=Dy, Q=Se) indicate that they are paramagnetic and obey the Curie–Weiss law over the entire experimental temperature, while the magnetic susceptibility of Sm{sub 3}CoGaSe{sub 7} deviates from the Curie–Weiss law as a result of the crystal field splitting. - Graphical abstract: Ln{sub 3}MGaS{sub 7} (Ln=Nd, Sm, Dy, Er; M=Co, Ni) and Ln{sub 3}MGaSe{sub 7} (Ln=Nd, Sm, Gd, Dy, M=Co; Ln=Nd, Gd, Dy, M=Ni) adopt a three-dimensional framework composed of LnQ{sub 7} monocapped trigonal prisms with interesting [MQ{sub 3}]{sup 4−} chains and isolated GaQ{sub 4} tetrahedra lying in two sets of channels in the framework. - Highlights: • New compounds, Ln{sub 3}MGaQ{sub 7} (Ln=rare-earth; M=Co, Ni; Q=S, Se), were synthesized. • They are isostructural and crystallize in the noncentrosymmetric space group P6{sub 3}. • They adopt a three-dimensional framework built by LnQ{sub 7} monocapped trigonal prisms. • Ln{sub 3}CoGaQ{sub 7} (Ln=Dy, Er; Q=S, Se) are paramagnetic and obey the Curie–Weiss law. • The magnetic susceptibility of Sm{sub 3}CoGaSe{sub 7} deviates from the Curie–Weiss law.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Behavior of the magnetocaloric effect and critical exponents in La{sub 0.67}Sr{sub 0.33}Mn{sub 1−x}V{sub x}O{sub 3} manganite oxide

We have investigated the magnetocaloric effect along with magnetic phase transition and critical exponent analysis in mixed manganite La{sub 0.67}Sr{sub 0.33}Mn{sub 1−x}V{sub x}O{sub 3} (0≤x≤0.15). To determine the nature of the paramagnetic to ferromagnetic phase transition, found to be of second-order, we performed a critical exponents study by dc-magnetization M(H,T) measurements around the Curie temperature T{sub C}. Modified Arrott plot method has been adopted to study the critical behavior of the compounds at their transition region, the values of critical exponents β, γ and δ are close to those expected for three-dimensional Heisenberg class with short-range interaction. A large magnetic entropy change |ΔS{sub M}| deduced from isothermal magnetization curves, has been observed in our samples with a peak centered on their respective T{sub C}. With increase in vanadium content, the temperature corresponding to the maximum entropy change as well as the magnetic transition temperature gradually shifts to low temperatures. The field dependence of the magnetic entropy change is also analyzed, which shows the power law dependence namely, ΔS{sub M}∝H{sup n}. Relative cooling power increases from 205 J/kg for x=0.00 to 258 J/Kg for x=0.15 making these materials a promising candidates for magnetic refrigeration near room temperature. - Graphical abstract: Scaling plot below and above T{sub C} using the β and γ exponents determined from the Arrot plot method of La{sub 0.67}Sr{sub 0.33}Mn{sub 1−x}V{sub x}O{sub 3} for x=0.15. - Highlights: • The paramagnetic to ferromagnetic phase transition of La{sub 0.67}Sr{sub 0.33}Mn{sub 1−x}V{sub x}O{sub 3} (0≤x≤0.15) is found to be of second-order. • The field dependence of the magnetic entropy shows the power law dependence namely, ΔS{sub M}∝H{sup n}. • Moderate values of −ΔS{sub M}{sup max} and RCP make the La{sub 0.67}Sr{sub 0.33}Mn{sub 1−x}V{sub x}O{sub 3} compounds potential candidates for magnetic refrigeration applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Toward a better understanding of the magnetocaloric effect: An experimental and theoretical study of MnFe{sub 4}Si{sub 3}

The intermetallic compound MnFe{sub 4}Si{sub 3} has been studied by high-resolution Time of Flight (TOF) neutron powder diffraction. MnFe{sub 4}Si{sub 3} crystallizes in the hexagonal space group P6{sub 3}/mcm with lattice constants of a=b=6.8043(4) Å and c=4.7254(2) Å at 310 K. Magnetic susceptibility measurements show clearly the magnetic transition from paramagnetism to ferromagnetism at about 302(2) K. Magnetic structure refinements based on neutron powder diffraction data with and without external magnetic field reveal strong evidence on the origin of the large magnetocaloric effect (MCE) in this material as a partial reordering of the spins between ∼270 K and 300 K. In addition, electronic structure calculations using the self-consistent, spin-polarized Tight Binding-Linear MuffinTin Orbital (TB-LMTO) method were also accomplished to address the “coloring problem” (Mn/Fe site preference) as well as the unique ferromagnetic behavior of this intermetallic compound. - Graphical abstract: Theoretical and experimental reinvestigation of the magnetic structure of MnFe{sub 4}Si{sub 3} for a better understanding of its large magnetocaloric effect (MCE). - Highlights: • Strong magnetic transition from paramagnetism to ferromagnetism at about 302(2) K. • MCE associated to a partial reordering of the spins between ∼270 K and 300 K. • DFT calculations show strong relation between MCE and spintronic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Two interpenetrating Cu{sup II}/Ni{sup II}-coordinated polymers based on an unsymmetrical bifunctional N/O-tectonic: Syntheses, structures and magnetic properties

Two new interpenetrating Cu{sup II}/Ni{sup II} coordination polymers, based on a unsymmetrical bifunctional N/O-tectonic 3-(pyrid-4′-yl)-5-(4″-carbonylphenyl)-1,2,4-triazolyl (H{sub 2}pycz), ([Cu-(Hpycz){sub 2}]·2H{sub 2}O){sub n} (1) and ([Ni(Hpycz){sub 2}]·H{sub 2}O){sub n} (2), have been solvothermally synthesized and structure characterization. Single crystal X-ray analysis indicates that compound 1 shows 2-fold parallel interpenetrated 4{sup 4}-sql layers with the same handedness. The overall structure of 1 is achiral—in each layer of doubly interpenetrating nets, the two individual nets have the opposite handedness to the corresponding nets in the adjoining layers—while 2 features a rare 8-fold interpenetrating 6{sup 6}-dia network that belongs to class IIIa interpenetration. In addition, compounds 1 and 2 both show similar paramagnetic characteristic properties. - Graphical abstract: Two new Cu(II)/Ni(II) coordination polymers present 2D parallel 2-fold interpenetrated 4{sup 4}-sql layers and a rare 3D 8-fold interpenetrating 6{sup 6}-dia network. In addition, magnetic susceptibility measurements show similar paramagnetic characteristic for two complexes. - Highlights: • A new unsymmetrical bifunctional N/O-tectonic as 4-connected spacer. • A 2-fold parallel interpenetrated sql layer with the same handedness. • A rare 8-fold interpenetrating dia network (class IIIa)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Synthesis, structural and electronic properties of monodispersed self-organized single crystalline nanobricks of isocubanite CuFe{sub 2}S{sub 3}

The nanoparticles with a pure cubic phase of isocubanite CuFe{sub 2}S{sub 3} are successfully synthesized for the first time. The particles are self-organized into the single crystalline nanocomposites with a shape of “bricks” which are well ordered in a certain anisotropic orientation. All bricks have nearly the same shape and dimensions and may be considered as monodispersed nanobricks. Magnetic measurements show paramagnetic behavior of the compound down to 4.2 K with the antiferromagnetic correlation between iron ions. An average magnetic moment is about 2.8–3.0 μ{sub B} per formula unit CuFe{sub 2}S{sub 3}. Mössbauer spectroscopy data reveal that the ferric ions in isocubanite are in the high-spin state (spin S=5/2) whereas the ferrous ions are in the intermediate-spin state (S=1). The Fe{sup 3+} and Fe{sup 2+} ions are distributed randomly over tetrahedral sites and the electron exchange between these ions is absent. This can explain nonmagnetic behavior of isocubanite. In the suggested method, the combined nanocomposites containing the magnetic chalcopyrite CuFeS{sub 2} and the nonmagnetic isocubanite CuFe{sub 2}S{sub 3} can be synthesized in a certain sequence. Such composites could be useful for the applied nanotechnology. - Graphical abstract: Self-organized single crystalline “nanobricks” of isocubanite CuFe{sub 2}S{sub 3} synthesized by a thermal pyrolysis method. - Highlights: • Self-organized single crystalline “nanobricks” of CuFe{sub 2}S{sub 3} were synthesized. • All bricks are nearly monodispersed and well-ordered in a certain anisotropic orientation. • XRD, HRTEM, magnetic measurements and Mössbauer spectroscopy were used for characterization. • Nanobricks are paramagnetic down to 4.2 K with effective magnetic moment about 3.0 μ{sub B} per f.u. • Mössbauer spectroscopy data indicate different spin states of Fe{sup 2+} and Fe{sup 3+} ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

New complex bismuth oxides in the Bi{sub 2}O{sub 3}–NiO–Sb{sub 2}O{sub 5} system and their properties

Phase equilibria in the Bi{sub 2}O{sub 3}–NiO–Sb{sub 2}O{sub 5} system have been investigated. The isothermal section of the system (650°) has been constructed. For the first time the existence of the pyrochlore structure solid solution, (Bi{sub 2−x}Ni{sub x})Ni{sub 2/3−y}Sb{sub 4/3+y}O{sub 7±δ}, x=0.1−0.35, y=0−0.1, and a new compound Bi{sub 3}Ni{sub 2/3}Sb{sub 7/3}O{sub 11} of KSbO{sub 3} structure type have been discovered. The structures and properties of these compounds were studied by XRD, XAFS, diffuse reflection spectroscopy and magnetic methods. Rietveld refinement of synchrotron radiation-based powder XRD data for pyrochlore sample of 38.43Bi{sub 2}O{sub 3}–33.0NiO–28.57Sb{sub 2}O{sub 5} composition and Bi{sub 3}Ni{sub 2/3}Sb{sub 7/3}O{sub 11} compound was performed. The best possible refinement of the positional parameters for both pyrochlore and Bi{sub 3}Ni{sub 2/3}Sb{sub 7/3}O{sub 11} structures was achieved for disordered models. Magnetic, diffuse reflection and an X-ray absorption spectroscopy study confirmed that in both compounds nickel ions are mainly in a 2+ oxidation state. According to magnetic data, Bi{sub 1.84}Ni{sub 0.16}(Ni{sub 0.63}Sb{sub 1.37})O{sub 7} pyrochlore and Bi{sub 3}Ni{sub 2/3}Sb{sub 7/3}O{sub 11} are overall paramagnetic in nature. - Graphical abstract: Isothermal section of the Bi{sub 2}O{sub 3}–NiO–Sb{sub 2}O{sub 5} system at 650 °C in air and variation of magnetic susceptibility and inverse susceptibility with temperature for Bi{sub 1.84}Ni{sub 0.79}Sb{sub 1.37}O{sub 7} pyrochlore. - Highlights: • We have constructed the isothermal section of the system Bi{sub 2}O{sub 3}–NiO–Sb{sub 2}O{sub 5}. • The boundaries of pyrochlore structure solid solution have been determined. • New Bi{sub 3}Ni{sub 2/3}Sb{sub 7/3}O{sub 11} compound of KSbO{sub 3} structure type have been discovered. • The structures were studied by means of synchrotron X-ray diffraction and XAFS. • Magnetic measurements revealed that both compounds are paramagnetic at 2–350 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Influence of gadolinium content on the tetragonal to cubic phase transition in zirconia-silica binary oxides

The present study reports the effect of gadolinium (Gd{sup 3+}) in zirconia-silica (ZrO{sub 2}-SiO{sub 2}) binary oxides. The pure ZrO{sub 2}-SiO{sub 2} synthesized at 1100 °C was tetragonal. The addition of Gd{sup 3+} in the concentration range of 5%–10% resulted in the formation of t-ZrO{sub 2}, whereas higher contents of Gd{sup 3+} led to the formation of cubic ZrO{sub 2} (c-ZrO{sub 2}). The presence of Gd{sup 3+} also affected the lattice parameters of both t-ZrO{sub 2} and c-ZrO{sub 2}. Magnetic studies confirmed a steady increase in the paramagnetic behaviour with increasing content of Gd{sup 3+}. - Graphical abstract: t-ZrO{sub 2} to c-ZrO{sub 2} phase transition influenced by Gd{sup 3+} content. - Highlights: • Sol-gel synthesis of Gd{sup 3+} added SiO{sub 2}-ZrO{sub 2} binary oxides. • Significant role of Gd{sup 3+} content in the tetragonal and cubic stabilization of ZrO{sub 2}. • Phase stability of either tetragonal or cubic stabilization till 1100 °C. • Gd{sup 3+} additions ensured additional paramagnetic behaviour in SiO{sub 2}-ZrO{sub 2} binary oxide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Structures and magnetic properties of new fluorite-related quaternary rare earth oxides LnY{sub 2}TaO{sub 7} and LaLn{sub 2}RuO{sub 7} (Ln=rare earths)

New fluorite-related quaternary rare earth oxides LnY{sub 2}TaO{sub 7} (Ln=La–Dy) and LaLn{sub 2}RuO{sub 7} (Ln=Eu–Tb) have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space groups C222{sub 1} and Cmcm, respectively. The results of the Rietveld analysis for LnY{sub 2}TaO{sub 7} (Ln=La–Dy) indicate that there exists no structural ordering of the Ln and Y ions at the eight-coordinate 4b site and the seven-coordinate 8c site, but the larger Ln ions occupy the eight-coordinate 4b site rather than the seven-coordinate 8c site, with increasing the Ln ionic radius. On the other hand, the results of the Rietveld analysis for the X-ray diffraction profiles of LaTb{sub 2}RuO{sub 7} showed that La and Tb atoms are almost situated at the eight-coordinated site (4a site) and seven-coordinated site (8g site), respectively, i.e., cation ordering occurs on the 4a and 8g sites. All compounds LnY{sub 2}TaO{sub 7} (Ln=La–Dy) are paramagnetic down to 1.8 K. On the other hand, LaTb{sub 2}RuO{sub 7} shows an antiferromagnetic transition at 17 K. In addition, another magnetic anomaly has been found at 10 K. Analysis of the magnetic specific heat for LaTb{sub 2}RuO{sub 7} indicates that the magnetic transitions at 10 and 17 K are due to the magnetic ordering of Tb{sup 3+} and Ru{sup 5+} ions, respectively. - Graphical abstract: Two magnetic anomalies have been observed in the temperature dependence of ∂(χT)/∂T for LaTb{sub 2}RuO{sub 7}. It is discussed that the anomalies at 10 and 17 K are due to the magnetic ordering of Tb{sup 3+} and Ru{sup 5+} ions, respectively. - Highlights: • New fluorite-related quaternary rare earth oxides Ln′Ln″{sub 2}MO{sub 7} have been prepared. • All compounds LnY{sub 2}TaO{sub 7} (Ln=La–Dy) are paramagnetic down to 1.8 K. • LaTb{sub 2}RuO{sub 7} shows two magnetic anomalies at 10 and 17 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

The exchange interactions and the state of manganese atoms in the solid solutions in Bi{sub 3}NbO{sub 7} of cubic and tetragonal modifications

The comparative analysis of magnetic behavior of manganese-containing solid solutions Bi{sub 3}Nb{sub 1−x}Mn{sub x}O{sub 7−δ} (x=0.01−0.10) of cubic and tetragonal modifications was performed. Based on the results of magnetic susceptibility studies paramagnetic manganese atoms in solid solutions of cubic and tetragonal modifications were found to be in the form of Mn(III), Mn(IV) monomers and exchange-coupled dimers of Mn(III)–O–Mn(III), Mn(IV)–O–Mn(IV), Mn(III)–O–Mn(IV). The exchange parameters and the distribution of monomers and dimers in solid solutions as a function of the content of paramagnetic atoms were calculated. - Graphical abstract: Structural transition of cubic to tetragonal Bi{sub 3}NbO{sub 7−δ}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Synthesis and characterization of amorphous mesoporous silica using TEMPO-functionalized amphiphilic templates

Inorganic–organic hybrid materials based on amorphous mesoporous silica containing organized nitroxide radicals within its mesopores have been prepared using the micellar self-assembly of TEOS solutions containing the nitroxide functionalized amphiphile (4-(N,N-dimethyl-N-hexadecylammonium)-2,2,6, 6-tetramethyl-piperidin-N-oxyl-iodide) (CAT-16). This template has been used both in its pure form and in various mixtures with cetyl trimethylammonium bromide (CTAB). The samples have been characterized by chemical analysis, N{sub 2} sorption studies, magnetic susceptibility measurements, and various spectroscopic methods. While electron paramagnetic resonance (EPR) spectra indicate that the strength of the intermolecular spin–spin interactions can be controlled via the CAT-16/CTAB ratio, nuclear magnetic resonance (NMR) data suggest that these interactions are too weak to facilitate cooperative magnetism. - Graphical abstract: The amphiphilic radical CAT-16 is used as a template for the synthesis of amorphous mesoporous silica. The resulting paramagnetic hybrid materials are characterized by BET, FTIR, NMR, EPR and magnetic susceptibility studies. - Highlights: • Amphiphilic CAT-16 as a template for mesoporous silica. • Comprehensive structural characterization by BET, FTIR; EPR and NMR. • Strength of radical-radical interactions tuable within CAT-16/CTAB mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Flexible porous coordination polymer of Ni(II) for developing nanoparticles through acid formation and redox activity of the framework

Immobilization of the nanoparticles (NPs) in a two dimensional porous coordination polymer (PCP) is currently an emerging field for a number of applications. But still it is a great challenge to fabricate any specified metal NPs in a single network. Herein the synthesis of Au, Pd, Mn, Fe, Cu, Zn, Mg, Li, Fe/Cu, Zn/Mg etc, NPs in a highly flexible PCP of Ni(II); {[Ni_3(TBIB)_2(BTC)_2(H_2O)_6]·5C_2H_5OH·9H_2O}{sub n} [TBIB = 1,3,5-tri(1H-benzo[d]imidazol-1-yl)benzene, H{sub 3}BTC = 1,3,5-benzenetricarboxylic acid] have been reported. This universal host is able to grow mixed metal NPs from mixed metal precursors. Monodentate carboxylate groups of BTC linker act as anchoring sites for the metal ions of the metal precursors. This is the main driving force to grow NPs within the cavities along with the high flexibility of this polymer at room temperature. Mechanism involves acid formation followed by redox reaction to synthesize metal NPs explained by EPR and FTIR. Paramagnetic properties have been shown by as-synthesized Fe NPs integrated framework at room temperature under applied magnetic field up to 17,500 Oe. - Graphical abstract: A number of nanoparticles including Au, Pd, Mn, Fe, Cu, Zn, Mg, Li as well as mixed NPs Fe/Cu, Zn/Mg have been synthesized at room temperature without use of any surfactant and reducing agent. Display Omitted - Highlights: • Different types of NPs have been synthesized in a 2D polymer at room temperature. • Surfactant and reducing agents have not been used for NPs synthesis. • Monodentate carboxylate groups of BTC linker act as anchoring sites for metal ions. • NPs were synthesized by acid formation and redox activity of the framework. • Fe NPs integrated framework shows paramagnetic properties at room temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Synthesis, structural and magnetic studies of the CuCr{sub 1-x}Rh{sub x}O{sub 2} delafossite solid solution with 0 {<=} x {<=} 0.2

Highlights: {yields} Rh non-magnetic replacement of the Cr in the magnetic frustrated delafossite CuCrO{sub 2}. {yields} Delafossite solid solution is maintained up to 0.2 in this system. {yields} Strain generated by Rh substitution is strongly anisotropic. {yields} M{sup 3+}-O bond strength is affected. {yields} High temperature paramagnetic behavior and weak ferromagnetism at low temperature. -- Abstract: The CuCr{sub 1-x}Rh{sub x}O{sub 2} series is investigated by X-ray diffraction, magnetization measurements and Raman spectroscopy on ceramic samples. It is found that a delafossite solid solution is maintained up to x = 0.2 in CuCr{sub 1-x}Rh{sub x}O{sub 2}. The small observed variation in cell parameters is consistent with the small difference between the ionic radii of Cr{sup 3+} and Rh{sup 3+}. A significant broadening of X-ray reflections is observed and when analyzed using the Williamson-Hall relationship showed that the strain generated by Rh substitution is strongly anisotropic, affecting mainly (Cr,Rh)-O bonds in the ab plane. Room temperature Raman spectra displayed three main Raman active modes. All modes shift to lower frequency and undergo significant changes in intensity with increasing Rh content, showing the effect of Rh atoms on the M{sup 3+}-O bond strength. The magnetic behavior of CuCr{sub 1-x}Rh{sub x}O{sub 2} samples was investigated as a function of temperature and applied field. At high temperature paramagnetic behavior, and at low temperature, evidence for weak ferromagnetism, reinforced by a hysteresis loop at 4 K is observed. The magnetic behavior of CuCr{sub 1-x}Rh{sub x}O{sub 2} is attributed to the disorder of Cr and Rh in octahedral sites resulting in short-range Cr-O-Cr and Cr-O-Rh interactions, which give rise to short-range weak ferromagnetism.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Rare earth niobium oxynitrides, LnNbON{sub 2-{delta}} (Ln = Y, La, Pr, Nd, Gd, Dy): Synthesis, structure and properties

Graphical abstract: Ammonolysis of LnNbO{sub 4} (Ln = rare earth or Y) leads to the formation of oxynitrides of different structures depending on the size of the rare earth. Highlights: {yields} We have carried out ammonolysis of LnNbO{sub 4} (Ln = rare earth and Y) to form oxynitrides of different structures depending on the size of the rare earth. {yields} Infrared spectroscopy shows the marked difference between oxides and the corresponding oxynitrides. {yields} The oxynitrides are stable in air upto {approx}400 {sup o}C above which an intermediate phase with nitrogen molecules attached to the oxide lattice forms. {yields} Gadolinium niobium oxynitride shows paramagnetism. -- Abstract: Ammonolysis of rare earth niobates of the type LnNbO{sub 4} (Ln = Y, La, Pr, Nd, Gd, Dy) yields oxynitrides of different structures. When Ln = La, Nd and Pr, the structure is that of an orthorhombic perovskite of the general formula LnNbON{sub 2}. As the size of the rare earth decreases, the oxynitride has a nitrogen-deficient defect fluorite (Ln = Pr, Nd, Gd), or pyrochlore (Ln = Y) structure. The IR spectra of the oxynitrides and the corresponding oxides are significantly different. Thermogravimetric analysis suggests the formation of an intermediate phase wherein the N{sub 2} molecule is attached to the oxide lattice above 400 {sup o}C and decomposes to give the oxide on heating in an oxygen atmosphere. Raman spectra of the intermediate phases show evidence for the N{identical_to}N stretching vibration. Gadolinium niobium oxynitride is found to be paramagnetic.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Magnetic phase composition of strontium titanate implanted with iron ions

Highlights: Black-Right-Pointing-Pointer The origin of RT-ferromagnetism in iron implanted strontium titanate. Black-Right-Pointing-Pointer Metallic iron nanoclusters form during implantation and define magnetic behaviour. Black-Right-Pointing-Pointer Paramagnetic at room temperature iron-substituted strontium titanate identified. -- Abstract: Thin magnetic films were synthesized by means of implantation of iron ions into single-crystalline (1 0 0) substrates of strontium titanate. Depth-selective conversion electron Moessbauer spectroscopy (DCEMS) indicates that origin of the samples magnetism is {alpha}-Fe nanoparticles. Iron-substituted strontium titanate was also identified but with paramagnetic behaviour at room temperature. Surface magneto-optical Kerr effect (SMOKE) confirms that the films reveal superparamagnetism (the low-fluence sample) or ferromagnetism (the high-fluence sample), and demonstrate absence of magnetic in-plane anisotropy. These findings highlight iron implanted strontium titanate as a promising candidate for composite multiferroic material and also for gas sensing applications.

36 MATERIALS SCIENCE↗