Large scale synthesis of nanostructured zirconia-based compounds from freeze-dried precursors

Nanocrystalline zirconia powders have been obtained at the multigram scale by thermal decomposition of precursors resulting from the freeze-drying of aqueous acetic solutions. This technique has equally made possible to synthesize a variety of nanostructured yttria or scandia doped zirconia compositions. SEM images, as well as the analysis of the XRD patterns, show the nanoparticulated character of those solids obtained at low temperature, with typical particle size in the 10–15 nm range when prepared at 673 K. The presence of the monoclinic, the tetragonal or both phases depends on the temperature of the thermal treatment, the doping concentration and the nature of the dopant. In addition,…

Itinerant Electron Metamagnetism in η-Carbide-Type Compound Co3Mo3C

We report the magnetic properties of the cobalt molybdenum η-carbide-type compounds Co 3 Mo 3 C and Co 3 Mo 3 N. The magnetic susceptibility χ of Co 3 Mo 3 C shows a Curie–Weiss temperature dependence at high temperatures and a broad maximum at around 100 K, whereas that of Co 3 Mo 3 N shows a nearly temperature-independent enhanced Pauli paramagnetic behavior. The absence of a magnetic long-range order was confirmed by the nuclear magnetic resonance technique in both the compounds. As expected from the broad maximum of χ, we observed an itinerant electron metamagnetic transition at around 37 T in Co 3 Mo 3 C.

High-pressure x-ray diffraction andab initiostudy ofNi2Mo3N,Pd2Mo3N,Pt2Mo3N,Co3Mo3N, andFe3Mo3N: Two families of ultra-incompressible bimetallic interstitial nitrides

We have studied by means of high-pressure x-ray diffraction the structural stability of ${\text{Ni}}_{2}{\text{Mo}}_{3}\text{N}$, ${\text{Co}}_{3}{\text{Mo}}_{3}\text{N}$, and ${\text{Fe}}_{3}{\text{Mo}}_{3}\text{N}$. We also report ab initio computing modeling of the high-pressure properties of these compounds, ${\text{Pd}}_{2}{\text{Mo}}_{3}\text{N}$ and ${\text{Pt}}_{2}{\text{Mo}}_{3}\text{N}$. We have found that the nitrides remain stable in the ambient-pressure cubic structure at least up to 50 GPa and determined their equation of state. All of them have a bulk modulus larger than 300 GPa. Single-crystal elastic constants have been calculated in order to quantify the stiffness of the i…

Synthesis of new vanadium–chromium and chromium–molybdenum oxynitrides by direct ammonolysis of freeze-dried precursors

Interstitial vanadium–chromium and chromium–molybdenum oxynitrides in the solid solution series V1 − zCrz(OxNy) and Cr1 − zMoz(OxNy) (z = 0.0, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0) have been obtained by direct ammonolysis of precursors resulting from the freeze-drying of aqueous solutions of the appropriate metal salts. A study of the influence of the preparative variables on the outcomes of this procedure is presented. Compounds in the V1 − zCrz(OxNy) series are prepared as single phases by nitridation at 1073 K, followed by fast cooling of the samples. Compounds in the Cr1 − zMoz(OxNy) series are prepared as nearly single phases by nitridation at different temperatures, optimized for each composi…

Electronic Properties of Mixed-Valence Manganates:  The Role of Mn Substitutional Defects

Single-phase perovskites in the solid solution series La0.7+yA0.3-yMn1-xMxO3 (with 0.00 ≤ x ≤ 0.10; A = Sr2+, M = Cu2+, Zn2+, Sc3+, Cr3+, Co3+, and Ga3+; A = Ba2+, M = Cu2+, Zn2+, and Sc3+) have been prepared via the acetic acid solutions freeze-drying method. This soft procedure makes possible strict stoichiometric control, and the synthetic variables allow one to maintain a constant proportion of Mn4+ (ca. 32%) in the 47 compounds prepared. In this way, the concentration of cationic vacancies at A and B sites is practically negligible in all cases. X-ray powder diffraction patterns corresponding to the 47 compounds have been completely indexed with rhombohedral perovskite cells. The cryst…

Synthesis of new molybdenum–tungsten, vanadium–tungsten and vanadium–molybdenum–tungsten oxynitrides from freeze-dried precursors

Abstract Interstitial molybdenum–tungsten, vanadium–tungsten and vanadium–molybdenum–tungsten oxynitrides in the solid solution series Mo1−zWz(OxNy) and V1−zWz(OxNy) (z=0, 0.2, 0.4, 0.5, 0.6, 0.8, 1), and V1−u−zMouWz(OxNy) (u, z=0.2, 0.33, 0.4, 0.6; u+z

ChemInform Abstract: Crystal Structure and Magnetic Properties of α-Mn(H2PO2)2× H2O.

Abstract The crystal structure of α-Mn(H2PO2)2·H2O has been refined from X-ray powder diffraction data. The cell is monoclinic (space group P21/c, Z − 4) with α = 7.8601(3) A , b = 7.4411(3) A , c = 10.7717(4) A and β = 102.859(2)°. The structure was refined with the Rietveld refinement principles, using as starting model the parameters of the presumably isostructural compound Zn(H2PO2)2·H2O. The structure can be described as being formed by dimeric entities Mn2O2 of edge-sharing manganese octahedra. Each group is linked through Mn-O-P-O-Mn bridges to four other groups, resulting in a three-dimensional network. The thermal variation in the susceptibility shows a sharp peak at T = 6.5 K and …

Compressibility and Structural Stability of Nanocrystalline TiO2 Anatase Synthesized from Freeze-Dried Precursors

The high-pressure structural behavior of 30 nm nanoparticles of anatase TiO2 was studied under hydrostatic and quasi-hydrostatic conditions up to 25 GPa. We found that the structural sequence is not sensitive to the use of different pressure transmitting media. Anatase-type nanoparticles exhibit a phase transition beyond 12 GPa toward a baddeleyite-type structure. Under decompression this phase transition is irreversible, and a metastable columbite-type structure is recovered at ambient conditions. The bulk modulus of anatase-type nanoparticles was determined confirming that nanoparticles of TiO2 are more compressible than bulk TiO2. Similar conclusions were obtained after the determination…

Crystal chemistry and redox behaviour of antimony strontium calcium perovskites

The compound Sr2Sb1.4Ca0.6O6 and their reduced forms Sr2Sb1.4Ca0.6O5.17 and Sr2Sb1.4Ca0.6O4.84 have been prepared and characterized by powder X-ray diffraction, electron diffraction, iodometric analyses and thermogravimetric analysis. The three phases with different oxygen stoichiometries are structurally related to the perovskite and show symmetry distortions from the ideal cubic structure (with cell parameter ap). The crystal structure of Sr2Sb1.4Ca0.6O6 may be refined by the Rietveld method from powder X-ray diffraction data using the space group P21/n, and the cell parameters a=5.776(2), b=5.7837(2), c=8.1718(3) A, β=90.039(3)° with the same structural model than for previously studied …

A field induced ferromagnetic-like transition below 2.8 K in Li2CuO2: An experimental and theoretical study

The low temperature magnetic properties of the Li2CuO2 compound have been investigated by means of superconducting quantum interference device magnetometry. We find in addition to an antiferromagnetic phase below 9.5 K a ferromagnetic-like steep rise of the magnetization around 2.8 K. The observed low temperature behavior is discussed by considering second and fourth order magnetocrystalline effective anisotropy coefficients, in addition to the exchange couplings reported in the literature. Work at the Institut de Ciencia dels Materials was supported by the Spanish Comisión Interministerial de Ciencia y Technología Grant No. CICYT MAT 96-1037.

Polymer solution processing of (Bi, Pb)SrCaCuO

Abstract A simple polymer processing route to the 110 K phase (Bi, Pb) 2 Sr 2 Ca 2 Cu 3 O 10+δ superconductor has been developed. The influence of the polymer to metal starting ratio, as well as the sintering temperature and time on the quality of the resulting superconducting powders has been studied by XRD, a.c. susceptibility and resistivity measurements. Microstructure of ceramic compacts has been studied by SEM, and qualitatively analysed by EDS for compositional homogeneity. The results indicate that the polymer synthesis route described here may offer a good alternative to the conventional solid state preparation methods towards attaining homogeneous 110 K superconductor powder withi…

Effect of disorder produced by cationic vacancies at theBsites on the electronic properties of mixed valence manganites

An alloy series of single-phased polycrystalline ${\mathrm{La}}_{1\ensuremath{-}x}{\mathrm{Na}}_{x}{\mathrm{MnO}}_{3+\mathrm{\ensuremath{\delta}}} (0l~xl~0.15)$ has been synthesized in order to study the effect of disorder on the electronic properties of mixed valence manganites. The synthetic variables allow one to maintain a constant proportion of ${\mathrm{Mn}}^{4+}$ in the samples $({\mathrm{Mn}}^{3+}{/\mathrm{M}\mathrm{n}}^{4+}=2.1\ifmmode\pm\else\textpm\fi{}0.2),$ while the similar size of ${\mathrm{La}}^{3+}$ and ${\mathrm{Na}}^{+}$ ions results in no appreciable change in the tolerance factor of the perovskite structure throughout the series. In this way, the sodium content x contro…

Structural effects of Co and Cr substitution in LaMnO3 + δ

Series of perovskite oxides with the composition LaMn1 − xMxO3 + δ (M = Cr, Co; 0 ≤ x ≤ 1) have been synthesized by thermal treatment of precursors obtained by freeze-drying of acetic acid solutions. The oxides have been characterized by X-ray diffraction, and the Mn4+ content and, thus, the oxygen excess, δ, has been determined by redox back-titration. LaMnO3.14 and LaCrO3 phases have the rhombohedral-LaAlO3 and the orthorhombic-GdFeO3 structures, respectively. The LaMn1 − xCrxO3 + δ phases have the rhombohedral structure for x ≤ 0.3, and the orthorhombic structure for x ≥ 0.5. LaCoO3 has, as LaMnO3.14, the rhombohedral structure. However, the LaMn1 − xCoxO3 + δ phases have orthorhombic st…

Influence of Mn site doping on electrical resistivity of polycrystalline La1-yAyMn1-xBxO3 (A=Ba, Sr; B=Cu, Cr, Co) Manganites

We have the measured electrical resistivity of La1-yBayMn1-xCuxO3 (0.17?y?0.30; 0.04?x?0.10), La1-ySryMn1-xCrxO3 and La1-ySryMn1-xCoxO3 (0.270?y?0.294; 0.02?x?0.10) polycrystalline samples in the 25-325 K temperature range. The increase of Mn site doping concentration leads to an increase of the electrical resistivity of the samples and the appearance of a ?double-peak? structure in the electrical resistivity versus temperature graphs. The first peak represents the insulator-metal transition in vicinity of the paramagnetic-ferromagnetic transition (TC). We have found that the intensity of the second peak increases with an increase of concentration of Mn substituents, due to the hole scatter…

Fast synthesis of single-phased 110 K bismuth superconductor by freeze-drying of acetic precursors. Kinetic role of calcium and copper oxides

Abstract Although the usefulness of solution procedures to improve the synthesis of bismuth HTSC has been argued, an adequate control of the procedural variables has allowed us to isolate the 110 K phase as the only superconducting phase after such a short sintering time as 22 h. The precursors used have been freeze-dried powders resulting from acetic solutions containing excess Ca and Cu. TGA-DTA and XRD experiments have been performed to follow the subsequent solid-state reaction processes. The initial formation of a mixed bismuth-lead oxoacetate, as intermediate to (Bi 1− y Pb y ) 2 CuO 4 , and the presence of an excess of Ca 2 CuO 3 in the last reaction step are two of the main factors …

Fast Solution Precursor Synthesis of the 2223 Phase: the Role of Lead in the Reaction Pathway

ABSTRACTValuable mechanistic information, about the reaction pathway in the formation of the 2223 phase, has been obtained by the use of a solution synthesis route. The presence of lead in the starting mixture has remarkable effects on the nature and stability of the different intermediates: i) the grain size and morphology of Bi2CuO4 is severely changed, ii) calcium carbonate is partially decomposed to yield the calcium plumbate, iii) the 2201 phase results stabilized against the formation of the collapsed phase Bi17Sr16Cu7O49-δ, iv) the melting point of the intermediate 2212 is lowered by about 10 °C. All these effects, due to lead substitution, contribute to promote the formation of the …

Exchange interactions through hydrogen-bond bridges. Crystal structure, spectroscopic characterisation and magnetic properties of the complex [{Cu(en)}2(μ-egta)]·4H2O (H4egta = 3,12-bis(carboxymethyl)-6,9-dioxa-3,12-diazatetradecanedionic acid)

Abstract The structure and spectroscopic and magnetic properties of [{Cu(en)}2(μ-egta)]·4H2O (H4egta = 3,12-bis(carboxymethyl)-6–9-dio 3,12-diazatetradecanedioic acid) are described. The compound is built of centrosymmetric neutral dimeric {[Cu(en)}2(μ-egta)] entities linked through hydrogen bonds involving water molecules. -NH2 groups and -CO2 groups, affording a three-dimensional framework. The egta anion displays an opened-up structure acting as a bridging ligand between two copper atoms. The coordination geometry about the metal atoms can be viewed as 4 + 1 + 1 (CuN3OO′O″ chromophores). The EPR spectra are indicative of an essentially dv−v ground state for the copper(II) ions. Magnetic …

The effect of Cu substitution on the A1g mode of La(0.7)Sr(0.3)MnO3 manganites

We report on the first Raman data of Cu substituted La(1-y)Sr(y)Mn(1-x)Cu(x)O3 (0 < x < 0.10 and 0.17 < y < 0.3, accordingly in order to have the same Mn(4+)/[Mn(4+)+Mn(3+)] ratio), collected in the frequency range 100-900 cm-1 and at room temperature, with parallel and crossed polarizations of the incident and scattered light. Spectra were fitted with a Drude-Lorentz model, and peaks at 190-220 and 430 cm-1, together with two broad structures centered at near 500 and 670 cm-1, have been found. We also have observed that the A1g mode is substantially shifted with increasing Cu substitution. The A1g phonon shift is a linear function of the tolerance factor t and the rhombohedral …

Transport and Diamagnetic Properties of 2:2:1:2 and 2:2:2:3 (Bi-Pb)-Sr-Ca-Cu-O Superconducting Materials

AbstractBismuth superconducting oriented fibers of the compositions 2:2:1:2: and 2:2:2:3 have been grown by the Laser Floating Zone (LFZ) method. Growth conditions have been optimized in order to improve the superconducting properties. The 108 K onset in susceptibility measurements (associated to the 2:2:2:3 phase) only appears well defined when starting from Sr-defective precursors.

Freeze-dried precursor-based synthesis of new polymetallic oxynitrides, V1−u−zCruMoz(OxNy),V1−u−zCruWz(OxNy), Cr1−u−zMouWz(OxNy) (u, z=0.2, 0.33, 0.4, 0.6, u+z<1), and VzCrzMozWz(OxNy) (z=0.25)

Abstract Interstitial polymetallic oxynitrides in the solid solution series V 1− u − z Cr u Mo z (O x N y ), V 1− u − z Cr u W z (O x N y ) and Cr 1− u − z Mo u W z (O x N y ) ( u , z  = 0.2, 0.33, 0.4, 0.6, u  +  z z Cr z Mo z W z (O x N y ) ( z  = 0.25) composition, can be obtained by ammonolysis of precursors resulting from the freeze-drying of aqueous solutions of the simple metal salts NH 4 VO 3 , (NH 4 ) 2 CrO 4 , (NH 4 ) 6 Mo 7 O 24 ·4H 2 O and (NH 4 ) 6 W 12 O 39 ·18H 2 O. A study of the influence of the preparative variables on the outcomes of this procedure is presented. Compounds in the V 1− u − z Cr u Mo z (O x N y ) series have been prepared as single phases by direct ammonolys…

Theoretical and Experimental Study of the Crystal Structures, Lattice Vibrations, and Band Structures of Monazite-Type PbCrO4, PbSeO4, SrCrO4, and SrSeO4

The crystal structures, lattice vibrations, and electronic band structures of PbCrO4, PbSeO4, SrCrO4, and SrSeO4 were studied by ab initio calculations, Raman spectroscopy, X-ray diffraction, and optical-absorption measurements. Calculations properly describe the crystal structures of the four compounds, which are isomorphic to the monazite structure and were confirmed by X-ray diffraction. Information is also obtained on the Raman- and IR-active phonons, with all of the vibrational modes assigned. In addition, the band structures and electronic densities of states of the four compounds were determined. All are indirect-gap semiconductors. In particular, chromates are found to have band gap…

Catalytic combustion of ethane over high surface area Ln1−xKxMnO3 (Ln = La, Nd) perovskites: The effect of potassium substitution

Publisher Summary As a general trend, the substitution of the rare earth cation by potassium decreased the intrinsic activity, reduced the reaction order in oxygen, and, for the more substituted samples (x>0.10), it increased the selectivity to ethene. Supported platinum or palladium catalysts have so far been used almost exclusively, because of their excellent activity. However, their high price, tendency to be poisoned, and volatility in some applications have estimulated the search for suitable substitutes. LaCoO3, as a potential auto exhaust catalyst, starting a wide interest in the catalytic properties of perovskites. Their specific application as catalysts in flameless combustion has …

Surface properties and catalytic performance for ethane combustion of La1−xKxMnO3+δ perovskites

Abstract The influence of K substitution in LaMnO3 perovskite on the surface properties and catalytic oxidation of ethane has been studied. La1−xKxMnO3+δ perovskites (x=0.05, 0.10, 0.15, 0.20 and 0.25) with BET surface area of 20–26 m2 g−1 have been prepared by the freeze-drying method and characterized by X-ray diffraction patterns (XRD), TPR, TPD and XPS. The XRD analyses showed the presence of a single crystalline phase (x≤0.15) with the linear increase of the lattice parameter corroborating the incorporation of potassium in the perovskite structure. The XPS studies revealed an enrichment of the perovskite surface with potassium accompanied by an increase in the surface Mn4+/Mn3+ ratio. …

Ordered Mesoporous Silicon Oxynitrides

From nitrides to carbides: topotactic synthesis of the η-carbides Fe3Mo3C and Co3Mo3C

The molybdenum bimetallic interstitial carbides Fe(3)Mo(3)C and Co(3)Mo(3)C have been synthesized by temperature-programmed reaction (TPR) between the molybdenum bimetallic interstitial nitrides Fe(3)Mo(3)N and Co(3)Mo(3)N and a flowing mixture of CH(4) and H(2) diluted in Ar. These compounds have been characterized by X-ray diffraction, laser Raman spectroscopy, elemental analysis, energy dispersive analysis of X rays, thermal analysis (in air) and scanning electron microscopy (field emission). Their structures have been refined from X-ray powder diffraction data. These carbides crystallize in the cubic system, space group Fd3m[a= 11.11376(6) and 11.0697(3)[Angstrom] for Fe and Co compound…

Short range charge/orbital ordering in La1−xSrxMn1−zBzO3 (B = Cu,Zn) manganites

We have measured the reflectivity spectra of La1−x SrxMn1−zBzO3 (B = Cu, Zn; 0.17 x 0.30; 0 z 0.10) manganites over wide frequency (100–4000 cm −1 )a nd temperature (80–300 K) ranges. Besides the previously observed infrared active modes or mode pairs at about 160 cm −1 (external mode), 350 cm −1 (bond bending mode) and 590 cm −1 (bond stretching mode), we have clearly observed two additional phonon modes at about 645 and 720 cm −1 below the temperature T1 (T1 < TC), which coincides with the phase transition temperature when the system transforms from ferromagnetic metallic into a ferromagnetic insulator state. This transition is related to the formation of short range charge/orbitally orde…

Crystal structure, magnetic and spectroscopic properties of the bis(dimethyl sulfoxide) adduct of tetra-μ-formato-dicopper(II), a new tetracarboxylato-bridged copper(II) dimer

The crystal and molecular structure of a new tetracarboxylato-bridged copper(II) dimer, the bis(dimethyl sulfoxide)tetrakis(μ-formato)dicopper(II) has been determined by X-ray diffraction methods. It crystatlizes in the tetragonal space group I41/a, with Z=8 in a cell of dimensions a=17.688(2), c=10.408(1) Å. The structure is built up of centrosymmetric neutral dimers [Cu2(HCOO)4(dmso)2], where four bidentate carboxylate anions form syn-syn bridges between the metal atoms which are in a 4 + 1 environment. Magnetic susceptibility data show that the copper atoms are strongly antiferromagnetically coupled with J=-434 cm-1. The obtained triplet-singlet energy gap is compared with those reported…

Nanostructured Alumina from Freeze-Dried Precursors

Nanocrystalline alumina has been obtained on the 100 g scale by thermal decomposition of precursors resulting from the freeze-drying of aqueous solutions of different aluminum-containing products, namely aluminum acetate and aluminum L-lactate. Samples prepared at different temperatures (from 873 to 1573 K in steps of 100 K) were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and surface area measurements. In the acetate case, the transformation sequence involves the formation of θ-Al 2 O 3 as an intermediate phase between γ-Al 2 O 3 and α-Al 2 O 3 , whereas this θ phase is not observed in the lactate case. TEM…

A new approach to the synthesis of intermetallic compounds: mild synthesis of submicrometric CoxMy (M = Mo, W; x∶y = 3∶1 and 7∶6) particles by direct reduction of freeze-dried precursors

A simple processing route to cobalt–molybdenum and cobalt–tungsten intermetallics (CoxMy, where M = Mo and W, and x∶y = 3∶1 and 7∶6) has been developed, on the basis of the use of precursors resulting from freeze-drying of aqueous solutions of the appropriate common metal salts. The influence of the preparative variables on the outcomes of this procedure is examined. These compounds are prepared as single phases by thermal reduction of amorphous freeze-dried powders under a hydrogen–argon atmosphere (8% H2), followed by slow cooling of the samples. The materials have been characterised by X-ray powder diffraction, metal analysis, scanning electron microscopy and thermogravimetry under an ox…

Pd2Mo3N: a new molybdenum bimetallic interstitial nitride

The molybdenum bimetallic nitride Pd2Mo3N has been synthesized by ammonolysis of the stoichiometric mixture of low sized pure oxide crystallites (2PdO/3MoO3) as resulting from low temperature thermal decomposition of precursor powders obtained by freeze-drying of aqueous solutions of the appropriate metal salts. This compound has been characterized by elemental analysis, energy dispersive analysis of X-rays, X-ray diffraction, scanning electron microscopy (field emision) and thermogravimetry under oxygen atmosphere. Pd2Mo3N crystallizes in the cubic space group P4132 (no. 213) (Pd2Mo3N, a = 6.81770(3) A, Z = 4), and presents the unusual filled β-manganese structure. It is stable under oxyge…

(Bi,Pb)2Sr2Ca2Cu3O10+δ superconductor composites: Ceramics vs. fibers

Abstract Well characterized (Bi, Pb) 2 Sr 2 Ca 2 Cu 3 O 10+δ superconductor powder has been used to prepare superconductor-glass, -metal and -alloy composites through solid state reaction method. A recently developed Laser Floating Zone (LFZ) apparatus has been used to transform the ceramic precursors into oriented fibers. The diamagnetic properties have been studied by a.c. susceptibility. The microstructure of fibers has been studied by SEM and compared with that of the original ceramic precursors. XRD has been used to study phase composition on representative composite samples and fibers. The results indicate some potential for the 2223-Ag composite, which displays improved diamagnetic p…

Raman and infrared studies ofLa1−ySryMn1−xMxO3(M=Cr, Co, Cu, Zn, Sc or Ga): Oxygen disorder and local vibrational modes

We present results of our study of polarized Raman scattering and infrared reflectivity of rhombohedral ceramic La1-ySryMn1-xMxO3 manganites in the temperature range between 77 and 320 K. In our samples, a part of the Mn atoms is substituted by M = Cr, Co, Cu, Zn, Sc, or Ga with x in the range 0-0.1. The hole concentration was kept at the optimal value of about 32% by tuning the Sr content y. We have monitored distortions of the oxygen sublattice by the presence of broad bands in the Raman spectra, the increase of dc resistivity extracted from the infrared reflectivity, and the change of the critical temperature of the ferromagnetic transition. Our results support the idea that these proper…

Compressibility and structural stability of ultra-incompressible bimetallic interstitial carbides and nitrides

We have investigated by means of high-pressure x-ray diffraction the structural stability of Pd 2Mo 3N, Ni 2Mo 3C 0.52N 0.48, Co 3Mo 3C 0.62N 0.38, and Fe 3Mo 3C. We have found that they remain stable in their ambient-pressure cubic phase at least up to 48 GPa. All of them have a bulk modulus larger than 330 GPa, the least compressible material being Fe 3Mo 3C, B 0 = 374(3) GPa. In addition, apparently a reduction of compressibility is detected as the carbon content is increased. The equation of state for each material is determined. A comparison with other refractory materials indicates that interstitial nitrides and carbides behave as ultra-incompressible materials. © 2012 American Physic…

Synthesis and characterization of NdNiO3 prepared by low temperature methods

Abstract NdNiO3 has been prepared with an orthorhombic perovskite structure by a low temperature and low oxygen pressure method starting from a nickel(III) oxide precursor, β-NiO(OH). The compound LaNiO3 has also been obtained by this method. This chemical-precursor-based synthesis overcomes problems related to the use of high oxygen pressures in the synthesis.

Novel phase transitions in B-site doped manganites

We have examined the infrared reflectivity and the electrical resistivity of La 1-x [Sr(Ba)] x Mn 1-z [Cu(Zn)] z O 3 samples in ferromagnetic metallic and insulator regime. Several phase transitions are observed, the most obvious being the transition from a ferromagnetic metallic to a ferromagnetic insulator phase that is related to the formation of short-range orbitally ordered domains. The temperature T 1 of the phase transition is dependent on doping concentration and for optimally doped samples (∼32% of Mn 4+ ions) we have found T 1 0.93 T C .

Precursor-based synthetic pathways to nanometer NdNiO3−x particles

Abstract The oxygen deficient neodymium nickel perovskite, NdNiO3−x, has been obtained by different low temperature-low oxygen pressure synthetic procedures. Besides a solid-matrix based route, both ordered and disordered chemical-precursors have been used as starting products. X-ray powder diffraction shows that the structure of this defective perovskite is orthorhombic. The study of the grain morphology of the products as resulting from the different synthetic procedures indicates that the main parameter determining the average particle size, which is in the nanometer range, is the maximum temperature achieved in the synthesis. Resistivity and DSC measurements show the existence of a meta…

A new improved synthesis of the 110 K bismuth superconducting phase: freeze-drying of acetic solutions

Abstract Metastability has greatly hindered the separated synthesis of the high-temperature superconducting phases represented as (Bi1−x, Pbx)2Sr2Can−1CunO4 + 2n (n = 2, 2-2-1-2, Tc≈80 K, and n = 3, 2-2-2-3, Tc≈110 K). By careful control of the synthetic variables, it becomes possible to obtain the 110 K phase as the only superconducting one through processing of freeze-dried acetic solutions. This technique leads to homogeneously sized (5–10 μm) micaceous platelets of the superconducting material.

1D antiferromagnetism in spin‐alternating bimetallic chains

The magnetic and thermal properties of the ordered bimetallic chain CoNi(EDTA)⋅6H2O in the very low‐temperature range are reported. The magnetic behavior does not exhibit the characteristic features of 1D ferrimagnets, but a continuous decrease of χmT towards zero at absolute zero. This 1D antiferromagnetic behavior results from an accidental compensation between the moments located at the two sublattices. This behavior, as well as the specific‐heat results, are modeled on the basis of an Ising‐exchange model that considers both alternating spins and Landé factors, and a zero‐field splitting on the Ni site. Eugenio.Coronado@uv.es ; Fernando.Sapina@uv.es

Nanostructured Solids from Freeze-Dried Precursors: Multigram Scale Synthesis of TiO2 -Based Powders

Nanocrystalline TiO2 and Ti1−xVxO2 (x = 0.01) powders have been prepared by thermal decomposition, in air, of amorphous precursors resulting from the freeze-drying of appropriate solutions. In addition, TiO2−xNy (anatase and rutile) and TiOxNy (rock-salt) have been prepared by thermal treatment in ammonia of a crystalline precursor (TiO2 obtained at 673 K). TEM and SEM images, as well as the analysis of the X-ray diffraction (XRD) patterns, show the nanoparticulated character of those solids obtained at low temperatures, with typical particle sizes in the 10–20 nm range when prepared at 673 K. The UV–Vis results indicate both the insertion of V in the anatase lattice and the feasibility of …

Synthesis and processing of nanocrystalline tungsten carbide: Towards cemented carbides with optimal mechanical properties

Abstract Nanocrystalline tungsten carbide has been obtained by reduction/carburization at low temperature from precursors obtained by freeze-drying of aqueous solutions. Nanocrystalline WC powders with a adequate content of carbon were mixed with submicrometric Cobalt powder (12 wt.%), obtained by same synthesis method, and sintered in vacuum furnace. The cemented carbides fabricated from experimental powders were compared with both commercial ultrafine and nanocrystalline WC-12Co mixtures consolidated by the same route. The synthesised powders were characterized by X-ray powder diffraction, elemental analysis and scanning and high resolution transmission electron microscopy. On the other h…

Monitoring the carburization of molybdenum bimetallic nitrides and oxynitrides with CH4/H2/Ar mixtures: identification of a new carbonitride.

A new carbonitride Ni2Mo3(CxNy) has been synthesized by temperature-programmed carburization of the Ni2Mo3N precursor with a CH4/H2/Ar gas mixture at 923 K. This compound has been characterized by X-ray diffraction, elemental analysis, Auger electron spectroscopy, laser Raman spectroscopy, thermogravimetric analysis and field-emission scanning electron microscopy. Ni2Mo3(CxNy) crystallizes in the cubic space group P4(1)32, with a lattice parameter of a=6.64575(3) A, corresponding to the unusual filled beta-Mn structure. Its formation occurs by partial substitution of N by C via a topotactic and pseudomorphic reaction and its stability in air is higher that of Ni2Mo3N. A two-phase mixture wi…

Crystal structure and magnetism of Co(HPO3)⋅H2O : A novel layered compound of Co(II)

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The Influence of Morphological Aspects in the Reaction Pathway and Superconductive Properties of Bi2223-Ca2CuO3 Ceramic Composites

ABSTRACTA variation of the solid-state matrix technique has been developed as a procedure for the preparation of 2223 bismuth superconducting phases [(Bi,Pb)2Sr2Ca1-nCunO4+2n, n=3]. The adequate processing of samples of nominal compositions 2223+x 0021, obtained both by this procedure and by the polymer matrix method, has allowed the modification of the microstructure of the calcium copper excess, with no noticeable change in that of the 2223 grains. The study of the phase evolution in the processing of the samples has shown that the formation rate of the 2223 phase is faster when the particle size of the calcium cuprate is smaller. A dependence of the intergranular superconducting properti…

Polymer-matrix route to (Bi, Pb)2Sr2Ca2Cu3O10+δ: The role of Ca2CuO3☆

Abstract The use of polyethylenimine as active matrix agent has provided a fast synthesis method for (Bi, Pb)2Sr2Ca2Cu3O10+δ, starting from aqueous acetic solutions combined with careful control of the procedural variables. The 110 K phase is obtained as the only superconducting phase after sintering in air during 42 h at 860°C. This technique yields homogeneously sized, large (ca. 20 μm) platelets of the superconducting material. The presence of an excess of calcium and copper over the stoichiometric requirements accelerates the formation of the superconducting phase. This excess, which appears in the resulting material as Ca2CuO3, influences the superconducting properties, other than Tc, …

ChemInform Abstract: Synthesis and Characterization of NdNiO3 Prepared by Low Temperature Methods.

Abstract NdNiO3 has been prepared with an orthorhombic perovskite structure by a low temperature and low oxygen pressure method starting from a nickel(III) oxide precursor, β-NiO(OH). The compound LaNiO3 has also been obtained by this method. This chemical-precursor-based synthesis overcomes problems related to the use of high oxygen pressures in the synthesis.

Submicrometer CaCuO2 and Ca2CuO3 particles from bimetallic formate precursors

Abstract CaCuO2 and Ca2CuO3 are readily obtained by thermal decomposition of two new calcium and copper formates, CaCu(HCOO)4 and Ca2Cu(HCOO)6. These chemical-precursor based syntheses, while overcoming problems related to the stoichiometry of the final products, involve very short diffusion path lengths. This, in turn, results in soft treatments yielding pure phases constituted by submicrometer (≈0.4 μm) homogeneous particles.

Effect ofA-site andB-site substitution on the infrared reflectivity spectra ofLa1−yAyMn1−xBxO3(A=Ba,Sr;B=Cu,Zn,Sc;0&lt;y&lt;~0.3;0&lt;~x&lt;~0.1)manganites

We have measured the infrared reflectivity spectra of ${\mathrm{La}}_{1\ensuremath{-}y}[\mathrm{Sr}(\mathrm{Ba}){]}_{y}{\mathrm{Mn}}_{1\ensuremath{-}x}[\mathrm{Cu}(\mathrm{Zn},\mathrm{Sc}){]}_{x}{\mathrm{O}}_{3}$ $(0lyl~0.3,0l~xl~0.10)$ manganites, in a wide frequency $(100\char21{}4000{\mathrm{cm}}^{\ensuremath{-}1})$ and temperature (80 K\char21{}300 K) range. The reflectivity spectra were analyzed by a fitting procedure based on a model that includes Drude, midinfrared electronic, and phonon oscillator contributions to the dielectric constant. Six infrared active ${(3A}_{u}$ and ${3E}_{u})$ modes of rhombohedral symmetry are clearly observed. We assigned all observed modes according to e…

The ferrimagnetic compounds CoM[M’(EDTA)]2⋅4H2O(M,M’=Co,Ni): Magnetic characterization of CoCo[Ni(EDTA)2]⋅4H2O

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