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1.
Phase equilibria in the silicon-rich part of the system Si-Yb (>60 at.% Si) have been established from DTA, LOM, EMPA, and X-ray diffraction experiments on arc-melted and annealed bulk alloys as well as on single crystals grown from pure gallium or indium metal used as a flux solvent. Phase relations are characterized by the existence of a defect disilicide showing polymorphism. Yb3Si5, the low-temperature modification with Th3Pd5 type, is a line compound at 62.5 at.% Si, stable below 947±7°C. Above this temperature Yb3Si5 transforms into the YbSi2−x (defect AlB2-derivative type) corresponding to a peritectoid equilibrium at 947±7°C: YbSi2−x+YbSi⇔Yb3Si5. YbSi2−x exhibits a small homogeneity region from ∼62.5 at.% to ∼63.5 at.% Si and melts incongruently at 1408±9°C at ∼63 at.% Si. On cooling it decomposes according to a eutectoid reaction at 763±7°C: YbSi2−x⇔Yb3Si5+(Si). The silicon-rich part of the diagram is characterized by a eutectic equilibrium at 1135+7°C and ∼81 at.% Si: L⇔YbSi2−x+(Si). From magnetic susceptibility and electrical resistivity measurements, performed on single-crystalline specimens, Yb3Si5 was found to be an intermediate valent system.  相似文献   

2.
Subsolidus phase relations in the CuOx-TiO2-Nb2O5 system were determined at 935 °C. The phase diagram contains one new phase, Cu3.21Ti1.16Nb2.63O12 (CTNO) and one rutile-structured solid solution series, Ti1−3xCuxNb2xO2: 0<x<0.2335 (35). The crystal structure of CTNO is similar to that of CaCu3Ti4O12 (CCTO) with square planar Cu2+ but with A site vacancies and a disordered mixture of Cu+, Ti4+ and Nb5+ on the octahedral sites. It is a modest semiconductor with relative permittivity ∼63 and displays non-Arrhenius conductivity behavior that is essentially temperature-independent at the lowest temperatures.  相似文献   

3.
采用基于密度泛函理论(DFT)的第一性原理方法,通过比较形成能(Eform)、价电子浓度(VEC)、弹性常数(Cij)、剪切模量(G)与体模量(B)的比值(G/B)以及派-纳力(τP-N)等参量的变化,研究了Ti、Cr、Al和B合金化对D81结构的α-Nb5Si3结构稳定性和力学性能的影响. 研究表明:合金化元素Ti、Cr、Al和B分别优先占据α-Nb5Si3中Nb4c、Nb4c、Si4a和Si8h位置;添加不同含量合金化元素的α-Nb5Si3仍保持稳定的D81结构;Ti、Al和B合金化使α-Nb5Si3的脆性增加,而随着Cr含量的增加,α-Nb5Si3的韧性逐渐增强. 此外,态密度(DOS)和Mulliken布居等电子结构的计算结果表明:Ti、Al和B合金化导致α-Nb5Si3脆性增加的主要原因是提高了共价键的强度;而Cr合金化的增韧作用主要来源于共价键数量的减少和强度的削弱,以及更多的反键态被占据.  相似文献   

4.
Fe3+-Nb5+ co-doped SnO2 was prepared at 1200 °C by a simple chemical co-precipitation method. The Sn1−2xFexNbxO2 solid solutions kept cassiterite structure in the range of 0<x?0.33, and their cell parameters decrease with increasing x. While x=0.40, a second phase with orthorhombic FeNbO4 structure co-exists with the cassiterite phase, and the second phase becomes dominant while x?0.45. The magnetic measurements indicated that low doping ratio sample (x=0.03) exhibits paramagnetic behavior. A paramagnetic-to-antiferromagnetic phase transition was observed for the samples with higher doping ratio (x?0.15).  相似文献   

5.
Phase relations were established in the Sr-poor part of the ternary systems Sr-Ni-Si (900 °C) and Sr-Cu-Si (800 °C) by light optical microscopy, electron probe microanalysis and X-ray diffraction on as cast and annealed alloys. Two new ternary compounds SrNiSi3 (BaNiSn3-type) and SrNi9−xSi4+x (own-type) were found in the Sr-Ni-Si system along with previously reported Sr(NixSi1−x)2 (AlB2-type). The crystal structure of SrNi9−xSi4+x (own-type, x=2.7, a=0.78998(3), c=1.1337(2) nm; space group P4/nbm) was determined from X-ray single crystal counter to be a low symmetry derivative of the cubic, parent NaZn13-type. At higher Si-content X-ray Rietveld refinements reveal the formation of a vacant site (□) corresponding to a formula SrNi5.5Si6.51.0. Phase equilibria in the Sr-Cu-Si system are characterized by the compounds SrCu2−xSi2+x (ThCr2Si2-type), Sr(CuxSi1−x)2 (AlB2-type), SrCu9−xSi4+x (0≤x≤1.0; CeNi8.5Si4.5-type) and SrCu13−xSix (4≤x≤1.8; NaZn13-type). The latter two structure types appear within a continuous solid solution. Neither a type-I nor a type-IX clathrate compound was encountered in the Sr-{Cu,Ni}-Si systems.Structural details are furthermore given for about 14 new ternary compounds from related alloy systems with Ba.  相似文献   

6.
Phase relations have been established in the ternary system Ce-Rh-Si for the isothermal section at 800 °C based on X-ray powder diffraction and EPMA on about 80 alloys, which were prepared by arc melting under argon or by powder reaction sintering. From the 25 ternary compounds observed at 800 °C 13 phases have been reported earlier. Based on XPD Rietveld refinements the crystal structures for 9 new ternary phases were assigned to known structure types. Structural chemistry of these compounds follows the characteristics already outlined for their prototype structures: τ7—Ce3RhSi3, (Ba3Al2Ge2-type), τ8—Ce2Rh3−xSi3+x (Ce2Rh1.35Ge4.65-type), τ10—Ce3Rh4−xSi4+x (U3Ni4Si4-type), τ11—CeRh6Si4 (LiCo6P4-type), τ13—Ce6Rh30Si19.3 (U6Co30Si19-type), τ18—Ce4Rh4Si3 (Sm4Pd4Si3-type), τ21—CeRh2Si (CeIr2Si-type), τ22—Ce2Rh3+xSi1−x (Y2Rh3Ge-type) and τ24—Ce8(Rh1−xSix)24Si (Ce8Pd24Sb-type). For τ25—Ce4(Rh1−xSix)12Si a novel bcc structure was proposed from Rietveld analysis. Detailed crystal structure data were derived for τ3—CeRhSi2 (CeNiSi2-type) and τ6—Ce2Rh3Si5 (U2Co3Si5-type) by X-ray single crystal experiments, confirming the structure types. The crystal structures of τ4—Ce22Rh22Si56, τ5—Ce20Rh27Si53 and τ23—Ce33.3Rh58.2−55.2Si8.5−11.5 are unknown. High temperature compounds with compositions Ce10Rh51Si33 (U10Co51Si33-type) and CeRhSi (LaIrSi-type) have been observed in as-cast alloys but these phases do not participate in the phase equilibria at 800 °C.  相似文献   

7.
Phase equilibria and crystal structures of ternary compounds were determined in the systems Ce-Pd-B and Yb-Pd-B at 850 °C in the concentration ranges up to 45 and 33 at% of Ce and Yb, respectively, employing X-ray single crystal and powder diffraction. Phase relations in the Ce-Pd-B system at 850 °C are governed by formation of extended homogeneity fields, τ2-CePd8B2−x (0.10<x<0.48); τ3-Ce3Pd25−xB8−y (1.06<x<1.87; 2.20<y<0.05), and CePd3Bx (0<x<0.65) the latter arising from binary CePd3. Crystallographic parameters for the new structure type τ2-CePd8B2−x (space group C2/c, a=1.78104(4) nm, b=1.03723(3) nm, c=1.16314(3), β=118.515(1)° for x=0.46) were established from X-ray single crystal diffraction. The crystal structures of τ2-CePd8B2−x and τ3-Ce3Pd25−xB3−y are connected in a crystallographic group-subgroup relationship. Due to the lack of suitable single crystals, the novel structure of τ1-Ce6Pd47−xB6 (x=0.2, C2/m space group, a=1.03594(2) nm, b=1.80782(3) nm, c=1.01997(2) nm, β=108.321(1)°) was determined from Rietveld refinement of X-ray powder diffraction data applying the structural model obtained from single crystals of homologous La6Pd47−xB6 (x=0.19) (X-ray single crystal diffraction, new structure type, space group C2/m, a=1.03988(2) nm, b=1.81941(5) nm, c=1.02418(2) nm, β=108.168(1)°).The Yb-Pd-B system is characterized by one ternary compound, τ1-Yb2Pd14B5, forming equilibria with extended solution YbPd3Bx, YbB6, Pd5B2 and Pd3B. The crystal structures of both Yb2Pd14B5 and isotypic Lu2Pd14B5 were determined from X-ray Rietveld refinements and found to be closely related to the Y2Pd14B5-type (I41/amd). The crystal structure of binary Yb5Pd2−x (Mn5C2-type) was confirmed from X-ray single crystal data and a slight defect on the Pd site (x=0.06) was established.The three structures τ1-Ce6Pd47−xB6, τ2-CePd8B2−x and τ3-Ce3Pd25−xB8−y are related and can be considered as the packings of fragments observed in Nd2Fe14B structure with different stacking of common structural blocks.Physical properties for Yb2Pd13.6B5 (temperature dependent specific heat, electrical resistivity and magnetization) yielded a predominantly Yb-4f13 electronic configuration, presumably related with a magnetic instability below 2 K. Kondo interaction and crystalline electric field effects control the paramagnetic temperature domain.  相似文献   

8.
Phase equilibria in the ternary systems Mn, Fe, Co, and Ni---Si---N are investigated and isothermal sections at 900°C (Fe---Si---N, Ni---Si---N), at 1000°C (Mn---Si---N, Co---Si---N) and at 1150°C (Fe---Si---N) are presented. In the system Mn---Si---N, Si3N4 coexists with MnSiN2, Mn3Si, Mn5Si3, MnSi, and MnSi2−x. In the systems Fe, Co, Ni---Si---N, Si3N4 coexists with all binary silicides but reacts rapidly with iron above 1120 ± 10°C, and cobalt and nickel above 1170 ± 10°C to form binary silicides and nitrogen gas.  相似文献   

9.
Transparent glasses of various compositions in the system (100−x)Li2B4O7x(SrO-Bi2O3-Nb2O5) (where x=10, 20, 30, 40, 50 and 60, in molar ratio) were fabricated via splat quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses. X-ray powder diffraction (XRD) and transmission electron microscopic studies confirmed the amorphous nature of the as-quenched and crystallinity in the heat-treated samples. Fluorite phase formation prior to the perovskite SrBi2Nb2O9 phase was analyzed by both the XRD and high-resolution transmission electron microscopy. Dielectric and the optical properties (transmission, optical band gap and Urbach energy) of these samples have been found to be compositional dependent. Refractive index was measured and compared with the values predicted by Wemple-Didomemenico and Gladstone-Dale relations. The glass nanocomposites comprising nanometer-sized crystallites of fluorite phase were found to be nonlinear optic active.  相似文献   

10.
Zusammenfassung Die Phasen Nb3Ga2, Ta5Ga3 und Ta5Al3Bx werden aus den Komponenten hergestellt. Nb3Ga2 kristallisiert im U3Si2-Typ, Ta5Ga3 hat Cr5Br3-Struktur (T 2) und Ta5Al3Bx ist mit Mn5Si3 (teilweise aufgefüllt) isotyp.  相似文献   

11.
The luminescence of the following systems are reported: ScTa1−xNbxO4, Li3Ta1−xNbxO4, CaTa2−2xNb2xO6 and Mg4Ta2−2xNb2xO9. The dependence of the luminescence properties on x becomes more pronounced if the distance between the pentavalent ions becomes shorter. In these systems the NbO6 group gives an efficient blue emission at 300°K. The compound Mg4Ta2O9 gives an efficient ultraviolet emission at 300°K. At 77°K both Mg4Nb2O9 and Mg4Ta2O9 show in addition a weaker emission peaking at wavelengths longer than the wavelength of the room temperature emission. This low-temperature emission can be excited by radiation with wavelengths longer than that of the absorption edge. The Mn2+ ion in Mg4Ta2O9Mn acts as an efficient activator with a deep-red emission.  相似文献   

12.
A series of binary rare-earth metal silicides RE5Si3 and ternary boron-interstitial phases RE5Si3Bx (RE=Gd, Dy, Ho, Lu, and Y) adopting the Mn5Si3-type structure, have been prepared from the elemental components by arc melting. Boron “stuffed” phases were subsequently heated at 1750 K within a high-frequency furnace. Crystal structures were determined for both binary and ternary series of compounds from single-crystal X-ray data: hexagonal symmetry, space group P63/mcm, Z=2. Boron insertion in the host binary silicides results in a very small decrease of the unit cell parameters with respect to those of the binaries. According to X-ray data, partial or nearly full boron occupancy of the interstitial octahedral sites in the range 0.6-1 is found. The magnetic properties of these compounds were characterized by the onset of magnetic ordering below 100 K. Boron insertion induces a modification of the transition temperature and θp values in most of the antiferromagnetic binary silicides, with the exception of the ternary phase Er5Si3Bx which was found to undergo a ferromagnetic transition at 14 K. The electrical resistivities for all binary silicides and ternary boron-interstitial phases resemble the temperature dependence of metals, with characteristic changes of slope in the resistivity curves due to the reduced electron scattering in the magnetically ordered states. Zintl-Klemm concept would predict a limiting composition RE5Si3B0.6 for a valence compound and should then preclude the stoichiometric formula RE5Si3B. Density functional theory calculations carried out on some RE5Si3Zx systems for different interstitial heteroatoms Z and different x contents from 0 to 1 give some support to this statement.  相似文献   

13.
The synthesis, crystal structure, thermal stability and absorbance spectra of perovskite-type oxynitrides with the general formula SrTi1−xNbx(O,N)3 (x=0.05, 0.10, 0.20, 0.50, 0.80, 0.90, 0.95) have been investigated. Oxide samples were prepared by a polymerized complex synthesis route and post-treated under ammonia at 850 °C for 24 h to substitute nitrogen for oxygen. Synchrotron X-ray powder diffraction (XRD) evidenced that the mixed oxide phases were all transformed into oxynitrides with perovskite-type structure during a thermal ammonolysis. SrTi1−xNbx(O,N)3 with compositions x≤0.80 crystallized in a cubic and samples with x≥0.90 in a tetragonal structure. The Rietveld refinement indicated a continuous enlargement of the lattice parameters towards higher niobium content of the samples. Thermogravimetric analysis (TGA) and hotgas extraction revealed the dependence of the nitrogen incorporation upon the degree of niobium substitution. It showed that more nitrogen was detected in the samples with higher niobium content. Furthermore, TGA disclosed stability for all oxynitrides at T≤400 °C. Diffuse reflectance spectroscopy indicated a continuous decrease of the band gap’s width from 3.24 eV (SrTi0.95Nb0.05 (O,N)3) to 1.82 eV (SrTi0.05Nb0.95(O,N)3) caused by the increasing amount of nitrogen towards the latter composition.  相似文献   

14.
Phase equilibria in the LaVO4-Nb2O5-Ta2O5 system were analyzed. New solid solutions LaTa2−2xNb2xVO9−δ (x=0-0.1) and LaNb2−2xTa2xVO9−δ (x=0-0.4) were detected in this system. The structures of the vanadate-niobate LaNb2VO9 and vanadate-tantalate LaTa2VO9 are not known. The structures of the vanadate-tantalate LaTa2VO9 and LaTa2VO9-based solid solutions are similar to the structure of LaTa7O19, which refers to the hexagonal crystal system. The influence of the oxygen nonstoichiometry δ(x) on crystallochemical characteristics and spectral properties of these solid solutions were examined by the X-ray phase analysis, IR and radio spectroscopic methods. A correlation between the nonstoichiometry δ(x) and the volume of a unit cell V(x) of solid solutions LaTa2−2xNb2xVO9−δ was found. The IR spectrum of LaTa2VO9−δ transformed in going from δ=0 to δ≠0. Two types of VO4 tetrahedra were formed in solid solutions LaNb2−2xTa2xVO9−δ depending on δ(x).  相似文献   

15.
The crystalline transition behaviors under different crystalline conditions of newly synthesized long alkane nylon 12 20 and nylon 10 20 are studied by wide-angle X-ray diffraction (WAXD) and real time Fourier transform infrared spectroscopy (FT-IR). The results show that their crystalline transition behaviors under WAXD were, to a large extend, related to the condition under which the crystals were prepared. The dilute solution-grown lamellar crystals of nylons 12 20 and 10 20 did not show distinct Brill transition behaviors before melting. Unlike the lamellar crystals of many other even-even nylons which display two crystal signals until melting temperature (TM), they presented a broad amorphous-like signal when the temperature increased to around 10 °C below TM. However, the post-annealing samples of nylons 12 20 and 10 20 displayed Brill transition at 155 and 157 °C, respectively, and the solution casting samples of nylons 12 20 and 10 20 at 110 and 135 °C, respectively. Furthermore, the IR spectra of nylons 12 20 and 10 20 displayed an interesting phenomenon: the intensity of the peak at 942 cm−1 declined on heating and finally disappeared around Brill temperature (TB), instead of TM as is in usual nylons. This suggests that the long alkane segments, introduced by 18-octadecanedicarboxylic acid, may undergo a local melting at TB.  相似文献   

16.
Phase equilibria, crystal structure, and transport properties in the (100−x) La0.95Ni0.6Fe0.4O3-xCeO2 (LNFCx) system (x=2-75 mol%) were studied in air. Evolution of phase compositions and crystal structure of components was observed. The LNFCx (2≤x≤10) are three-phase and comprise the perovskite phase with rhombohedral symmetry (R3?c), the modified ceria with fluorite structure (Fm3?m), and NiO as a secondary phase. These multiphase compositions exhibit metallic-like conductivity above 300 °C. Their conductivity gradually decreases from 395.6 to 260.6 S/cm, whereas the activation energy remains the same (Ea=0.04-0.05 eV), implying the decrease in the concentration of charge carriers. Phase compositions in the LNFCx (25≤x≤75) are more complicated. A change from semiconducting to metallic-like conductivity behavior was observed in LNFC25 at about 550 °C. The conductivity of LNFCx (25≤x≤75) could be explained in terms of a modified simple mixture model.  相似文献   

17.
New niobium oxynitrides containing either magnesium or silicon were prepared at 1000 °C by ammonia nitridation of oxide precursors obtained via the citrate route. The products had rock-salt type crystal structures. Crystallinity was improved by annealing in 0.5 MPa N2 and the final compositions were (Nb0.95Mg0.05)(N0.92O0.08) at 1500 °C and (Nb0.87Si0.090.04)(N0.87O0.13) at 1200 °C. The magnesium and oxide ions partially co-substitute the niobium and nitride ions in the octahedral sites of the δ-NbN lattice, respectively. Silicon ions were also successfully doped together with oxide ions into the rock-salt type NbN lattice. The Si doped product exhibited relatively large displacement at the octahedral sites and was accompanied by a small amount of cation vacancies. Superconductivity was improved by annealing to obtain critical temperatures/volume fractions of Tc=17.6 K/100% for Mg- and Tc=16.2 K/95% for the Si-doped niobium oxynitrides.  相似文献   

18.
Single crystals of Sr3B2SiO8 were obtained by solid-state reaction of stoichiometric mixture at 1200 °C. The crystal structure of the compound has been solved by direct methods and refined to R1=0.064 (wR=0.133). It is orthorhombic, Pnma, a=12.361(4), b=3.927(1), c=5.419(1) Å, V=263.05(11) Å3. The structure contains zigzag pseudo-chains running along the b axis and built up from corner sharing (Si,B)−O polyhedra. Boron and silicon are statistically distributed over one site with their coordination strongly disordered. Sr atoms are located between the chains providing three-dimensional linkage of the structure.The formation of Sr3B2SiO8 has been studied using annealing series in air at 900-1200 °C. According powder XRD, the probe contains pure Sr3B2SiO8 over 1100 °C. The compound is not stable below 900 °C. In the pseudobinary Sr2B2O5-Sr3B2SiO8 system a new series of solid solutions Sr3−xB2Si1−xO8−3x (x=0-0.9) have been crystallized from melt. The thermal behavior of Sr3B2SiO8 was investigated using powder high-temperature X-ray diffraction (HTXRD) in the temperature range 20-900 °C. The anisotropic character of thermal expansion has been observed: αa= −1.3, αb=23.5, αc=13.9, and αV=36.1×10−6 °C−1 (25 °C); αa= −1.3, αb=23.2, αc=5.2, and αV=27.1×10−6 °C−1 (650 °C). Maximal thermal expansion of the structure along of the chain direction [0 1 0] is caused by the partial straightening of chain zigzag. Hinge mechanism of thermal expansion is discussed.  相似文献   

19.
Lithium ferrite, a mixed-inverse spinel of type AxBy[A1−xB1−y]O4 was produced through solid state synthesis by calcining a Li2CO3/Fe2O3 mixture at 900 °C. The presence of both the ordered α-phase and disordered β-phase of LiFe5O8 was confirmed by XRD analysis, while formation of the latter was achieved by air quenching from high temperature. Laser Raman analysis was performed on both the α-LiFe5O8 and β-LiFe5O8 powders in order to achieve a reference set of Raman shifts for the spinel. The strongest, characteristic Raman peaks were determined to be 493, 382, 358, 300, and 263 cm−1 for both phases while smaller peaks at 202 and 236 cm−1 present in the α-phase were diminishing in intensity when the β-phase was present, thus providing unique identifiers for the presence of the disordered ferrite structure. SEM images taken of the synthesized LiFe5O8 powders showed particle sizes of less than 300 nm and an even particle size distribution.  相似文献   

20.
The binary and ternary systems M'O(M'CO3)-Nb2O5 and M'O(M'CO3)-MO-Nb2O5, where M'=Ca,Sr and Ba and M=Cu, Ni, Cd, Zn and Pb, were investigated by means of thermal analysis in the temperature range 20–1500°C. The boundaries of stability of the solid solutions Sr2−xMexNb2O7,Sr2−xMxNb2O7, Sr4−xMxNb2O9 and Sr6−xMxNb2O11 were determined by means of X-ray diffraction, and IR and Raman spectroscopy. The possibility of prognostication of the phase fields of stable solid solutions by calculation from the diagrams of the ‘comparative electronegativity of atoms vs. tolerance factor’ was demonstrated. The kinetic parameters of the interactions in theSrCO3+MO+Nb2O5 powder mixtures were established. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

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