Search results for "stoichiometry"
showing 10 items of 270 documents
A Self-Sorting Scheme Based on Tetra-Urea Calix[4]arenes
2009
Size and shape do matter: When dimerized in nonpolar solvents, an equimolar mixture of eleven tetra-urea calix[4]arenes with different wide-rim substituents self-sorts into only six out of 35 different homo- and heterodimers (see picture). Since the calixarene scaffold and the four urea units are the same in all cases, the self-sorting process is driven only by the cooperative action of steric requirements and stoichiometry.
Synthesis and crystal structure of novel Ruddlesden–Popper strontium niobium oxynitrides
2002
Abstract The family (SrO)(SrNbO 2-x N) n is the first example of Ruddlesden-Popper strontium niobium oxynitrides and provides layered structures to obtain mixed valence niobium compounds with a variety of oxidation states and transport properties. We have prepared members with n =1 (Sr 2 NbO 3 N) and n =2 (Sr 3 Nb 2 O 5 N 2 ) by solid state reaction of Nb 2 O 5 and SrCO 3 at 900–1050 °C under ammonia flow. These compounds crystallize in the I4/mmm space group and show a range of anionic stoichiometry that together with the N/O ratio determines the formal oxidation state for niobium and therefore the resultant physical properties. Samples of the n =1 member show mixed valence Nb 5+ /Nb 4+ an…
Polymer-matrix route to (Bi, Pb)2Sr2Ca2Cu3O10+δ: The role of Ca2CuO3☆
1993
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, …
Extreme sensitivity of superconductivity to stoichiometry in Fe1+?Se
2009
The recently discovered iron arsenide superconductors appear to display a universal set of characteristic features, including proximity to a magnetically ordered state and robustness of the superconductivity in the presence of disorder. Here we show that superconductivity in Fe1+?Se, which can be considered the parent compound of the superconducting arsenide family, is destroyed by very small changes in stoichiometry. Further, we show that nonsuperconducting Fe1+?Se is not magnetically ordered down to 5 K. These results suggest that robust superconductivity and immediate instability against an ordered magnetic state should not be considered as intrinsic characteristics of iron-based superco…
The role of correlations in the high-pressure phase of FeSe
2011
This study addresses the structural and electronic properties of the NiAs- and MnP-type phases dominating in FeSe at high pressures. The analysis is performed using first-principle band structure calculations within the framework of the B3LYP hybrid exchange-correlation functional. Based on the volume-pressure relation deduced from the available experimental data, we optimize the form and internal coordinates of the unit cell, which agree reasonably well with experiment. In particular, the present calculations resolve the structural NiAs-MnP phase transition which occurs at about 10 GPa. Both structures are found to be semiconducting at low pressures and metallizing at about 80-90 GPa. Usin…
Magnetic phase diagrams in heavy-fermion compounds
1990
Magnetic phase diagrams have been explored in heavy-fermion (HF) compounds by controlled changes of the stoichiometry (UCu4+xAl8−x), dopant concentration (Ce(Cu1−xNix)2Ge2) and magnetic field (CeCu2Si2). The results demonstr competition (i) between Kondo and RKKY interactions in the former two compounds and (ii) between HF superconductivity and some cooperative state, presumably HF band magnetism, in the latter.
Surface Ordering and Surface Segregation in Binary Alloys
1996
Many technologically relevant properties of metallic alloys are determined by the structure of their surfaces, especially in the field of catalysis and corrosion. One important aspect of a surface or grain boundaries is, that the stoichiometry of the alloy close to the surface normally differs from the bulk stoichiometry. Due to different interaction energies and different atom sizes of the components, one of them will get enriched at the surface, a phenomenon called surface segregation[1].
Epitaxial growth of molybdenum on TiO2(110)
2003
Abstract Molybdenum was deposited on blue (i.e. non-stoichiometric) TiO2(1 1 0) surface using a very low deposition rate (less than 0.05 eqML min−1). The resulting deposit was investigated by means of X-ray photoelectron diffraction (XPD), LEED and XPS. Just after deposition, the film is mainly constituted of metallic molybdenum, contains oxygen homogeneously dispersed through the whole deposit and the broad features detected in XPD scans are interpreted as a coarse epitaxy between TiO2(1 1 0) surface and the (0 0 1) face of bcc molybdenum. The orientation relationship is: Mo(1 0 0)[0 0 1]//TiO2(1 1 0)[0 0 1]. After annealing the deposit at 673 K, XPD scans become sharper and epitaxy is ach…
Growth of thin films of single-chain magnets on functionalized silicon surfaces
2018
A one-pot strategy for the direct growth of continuous and regular thin films of a neutral oxamato-bridged heterobimetallic chain, synthesized from Co2+ nitrate and the tetramethylammonium salt of the anionic copper(II) complex (Me4N)2[Cu(2,6-Et2pa)2]·6H2O (1) (2,6-Etpa = N-2,6-diethylphenyloxamate) over Si(111) surfaces functionalized with carboxylic acid terminating groups has been developed. Variation of the growth conditions can provide important differences in the morphology of the obtained films when working in H2O at 20 °C. An anisotropic growth of 1-D fibers is observed under stoichiometric conditions (Co2+/1 = 1:1), while an isotropic growth of 3-D particles occurs for an excess of…
Preparation and characterization of gels with garnet structure: A3B2C3O12, using ‘non-classical’ solvents
1992
Abstract Synthesis and characterization of some crystalline garnets by sol-gel techniques is described. The effects of emthanol, dimethyl sulfoxide (DMSO), CH2Cl2 and toluene solvents on gelation of TEOS are considered. Multicomponent gel formation in systems with stoichiometries 3CaO·Cr2O3·3SiO2 and 3CaO·Al2O2 was studied using DMSO, a polar solvent, and toluene, an apolar solvent. The dried gel was thermally treated and the powder was characterized by X-ray diffraction, differential thermal analysis/thermogravimetric analysis and scanning electron microscopy.