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1.
The negative thermal expansion material Y2W3O12 belongs to Ln2W3O12 family of compositions. The thermal expansion behavior of Ln2W3O12 (Ln = La, Nd, Dy, Y, Er and Yb) members synthesized by the solid-state reaction have been studied and correlated to their crystal structure. The lighter rare earth tungstates (Ln = La, Nd and Dy) crystallize in monoclinic structure (C2/c) whereas the heavy rare earth tungstates (Ln = Y, Er and Yb) form the trihydrate orthorhombic Ln2W3O123H2O at room temperature and above 400 K transforms to unhydrated orthorhombic structure (Pnca). The hot pressed (1273 K and 25 MPa) ceramic pellets have been studied for thermal expansion property by dilatometry and high temperature X-ray diffraction. The heavy rare earth tungstates show a large initial expansion up to 400 K, followed by a thermal contraction. The light rare earth tungstates, on the other hand, show thermal expansion. The difference in the thermal expansion behavior in Ln2W3O12 series is attributed to the difference in the structural features. The heavy rare earth tungstates have corner sharing of LnO6 octahedra with WO4 tetrahedra, where the now well established mechanism of transverse vibrations operate. The light rare earth tungstates have edge sharing of LnO8 polyhedra where in such a mechanism is absent.  相似文献   

2.
By using crystal field theory, the optical spectra, zero field splitting and g factors have been calculated. The defect structure for V(3+) in ZnO crystal has been studied by using crystal field theory and first-principle calculations. The results show that, the V(3+) ions do not occupy the exact Zn(2+) site, but displaced along C(3) axis.  相似文献   

3.
用X射线粉末衍射法研究了Li2O-CaO-Gd2O3-SiO2:Eu,Bi发光体系的物相组成随Gd2O3含量的变化,探讨了不同硅酸盐物种和结构对Eu3+和Bi3+发光特性的影响。结果表明,无Gd2O3组分时发光体是β-CaSiO4多晶体,当Gd2O3/SiO2比超过2.5%时,Ca2Gd8(SiO4)6O2和LiGd9(SiO4)6O2物相逐渐增加,当其成为主要物相时,EU3+发光呈数倍增强,这2种含钆物相的结构既利于EU3+的红光发射又利于敏化剂向激活剂传输能量,所形成的固熔体是优良的发光基质材料。  相似文献   

4.
A series of ternary compounds RECu9Mg2 (RE=Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Yb) have been synthesized via induction melting of elemental metal ingots followed by annealing at 400 °C for 4 weeks. Scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDXS) was used for examining microstructure and phase composition. These phases crystallize with an ordered version of the binary hexagonal structure type first reported for CeNi3. The crystal structure was solved for TbCu9Mg2 from single crystal X-ray counter data (TbCu9Mg2-structure type, P63/mmc-space group, hP24-Pearson symbol, a=0.49886 (7) nm, c=1.61646 (3) nm, RF=0.0474 for 190 unique reflections). The Rietveld refinement of the X-ray powder diffraction patterns of RECu9Mg2 confirmed the same crystal structure for the reported rare earth metals. The unit cell volumes for RECu9Mg2 smoothly follow the lanthanide contraction. The existence of a RECu9Mg2 phase was excluded for RE=Er and Tm under the investigated experimental conditions.  相似文献   

5.
The title compounds were prepared by reaction of the elemental components at high temperatures. They crystallize with a new structure type which was determined from single‐crystal X‐ray data of Tm13Ni25As19: P 6, a = 1621.9(4) pm, c = 387.78(8) pm, Z = 1, R = 0.025 for 3164 structure factors and 119 variable parameters. The refinement of the occupancy parameters suggested a mixed Tm/Ni occupancy for one metal position and defects for one nickel site resulting in the composition Tm12.57(1)Ni25.22(2)As19. These arsenides belong to a large structural family with a metal to metalloid ratio of 2 : 1.  相似文献   

6.
Ruby‐red, bead‐shaped single crystals of C‐type La2Se3 (a = 905.21(6) pm), Pr2Se3 (a = 891.17(6) pm), and Gd2Se3 (a = 872.56(5) pm) are obtained by oxidation of the respective rare‐earth metal (M = La, Pr and Gd) with selenium (molar ratio 2 : 3) in evacuated silica tubes at 750 °C in the presence of fluxing CsCl within seven days. Their crystal structure belongs to a cation‐deficient Th3P4‐type variant (cubic, I 4 3d) according to M2.6670.333Se4 (Z = 4) or M2Se3 (Z = 5.333) offering coordination numbers of eight (Se2– arranged as trigonal dodecahedra) to the M3+ cations. In spite of the high Cs+ activity in molten CsCl, no cesium incorporation into the M5.3330.667Se8‐frame structure (e. g. as CsM5Se8 with Z = 2) could be achieved, judged from both results of electron beam X‐ray microanalyses and refined occupation factors of the metal position very close to x = 8/9 for M3xSe4.  相似文献   

7.
The rare earth-rich cadmium compounds RE 4 TCd (RE = Y, La–Nd, Sm, and Gd–Tm, Lu; T = Co, Ru, and Rh) were prepared from the elements in sealed tantalum ampoules in an induction furnace. All samples were characterized by X-ray powder diffraction. The structures of Y4RuCd (a = 1362.5(1) pm), La4RuCd (a = 1415.9(1) pm), Gd4RuCd (a = 1368.8(2) pm), La4CoCd (a = 1417.9(4) pm), Gd4CoCd (a = 1356.1(1) pm), and Gd4RhCd (a = 1368.7(1) pm) were refined from single crystal X-ray diffractometer data. The RE 4 TCd compounds crystallize with the cubic Gd4RhIn type structure, space group F ${\bar 4}The rare earth-rich cadmium compounds RE 4 TCd (RE = Y, La–Nd, Sm, and Gd–Tm, Lu; T = Co, Ru, and Rh) were prepared from the elements in sealed tantalum ampoules in an induction furnace. All samples were characterized by X-ray powder diffraction. The structures of Y4RuCd (a = 1362.5(1) pm), La4RuCd (a = 1415.9(1) pm), Gd4RuCd (a = 1368.8(2) pm), La4CoCd (a = 1417.9(4) pm), Gd4CoCd (a = 1356.1(1) pm), and Gd4RhCd (a = 1368.7(1) pm) were refined from single crystal X-ray diffractometer data. The RE 4 TCd compounds crystallize with the cubic Gd4RhIn type structure, space group F 3m. The transition metal atoms have tricapped trigonal prismatic rare earth coordination. The trigonal prisms are condensed via common edges, forming a rigid three-dimensional network with adamantane symmetry. Voids in these networks are filled by Cd4 tetrahedra (304 pm Cd–Cd in Gd4CoCd) and polyhedra of the RE1 atoms. The crystal chemical peculiarities are briefly discussed. Correspondence: Rainer P?ttgen, Institut für Anorganische und Analytische Chemie, Westf?lische Wilhelms-Universit?t Münster, Correnstrasse 30, 48149 Münster, Germany.  相似文献   

8.
The quaternary indides LaTIn3Mg (T = Rh and Ir) and CeIrIn3Mg were prepared from the elements in sealed tantalum ampoules in an induction furnace. The samples were characterized by X-ray powder and single crystal data: LaCoAl4 type, Pmma, Z = 2, a = 830.5(1), b = 436.1(1), c = 745.1(1) pm, wR2 = 0.038, 467 F 2 values for LaRhIn3.075Mg0.925, a = 832.9(1), b = 436.5(1), c = 746.9(1) pm, wR2 = 0.077, 471 F 2 values for LaIrIn3.091Mg0.909, and a = 832.2(1), b = 434.1(1), c = 743.9(1) pm, wR2 = 0.066, 465 F 2 values for CeIrIn3.07Mg0.93 with 25 variables for each refinement. The transition metal, indium, and magnesium atoms build up three-dimensional [TIn3Mg] networks which leave pentagonal prismatic voids for the lanthanum and cerium atoms. The transition metal atoms have tricapped trigonal prismatic coordination and the magnesium atoms fill distorted square prisms. All three crystals revealed a small degree of Mg/In mixing on the latter site.  相似文献   

9.
The new compound Yb2+3—xPd12—3+xP7 x = 0.40(4)) was synthesized by sintering of a mixture of elemental components at 1100 °C with subsequent annealing at 800 °C. The crystal structure of Yb2+3—xPd12—3+xP7 was solved and refined from X‐ray single‐crystal diffraction data: space group P6¯, a = 10.0094(4)Å, c = 3.9543(2)Å, Z = 1; R(F) = 0.022 for 814 observed unique reflections and 38 refined parameters. The atomic arrangement reproduces a structure motif of the hexagonal Zr2Fe12P7 type in which one of the transition metal positions is substituted predominantly by ytterbium (Yb : Pd = 0.86(1) : 0.14). The ytterbium atoms are embedded in the 3D polyanion formed by palladium and phosphorus atoms. Two different environments for ytterbium atoms are present in the structure. Magnetic susceptibility measurements and XAS spectroscopy at the Yb LIII edge show the presence of ytterbium in two electronic configurations, 4?13 and 4?14. The following model was derived. Ytterbium atoms in the 3k site are in the 4?13 state, the two remaining positions contain ytterbium in intermediate‐valence states, giving totally 79 % ytterbium in the 4?13 electronic configuration.  相似文献   

10.
The four new compounds CsTmCoS3, CsYbCoS3, CsHoCoSe3, and CsYbCoSe3 have been synthesized at 1123 K. These black‐colored isostructural compounds crystallize in the KZrCuS3 structure type with four formula units in space group Cmcm of the orthorhombic system. The structure of these compounds is composed of layers separated by Cs atoms. Because there are no Q–Q bonds, the formal oxidation states of Cs/Ln/Co/Q are 1+/3+/2+/2?, respectively. CsHoCoSe3 shows paramagnetic behavior with μeff = 11.9(1) μB, whereas CsYbCoS3 displays an antiferromagnetic‐like transition at ~2.7 K with μeff = 5.85(1) μB. Both CsYbCoS3 and CsYbCoSe3 exhibit optical band gaps in the near infrared region and broad absorption bands at lower energies.  相似文献   

11.
New Thiophosphates: The Compounds Li6Ln3(PS4)5 (Ln: Y, Gd, Dy, Yb, Lu) and Ag3Y(PS4)2 The new thiophosphates Li6Ln3(PS4)5 (Ln: Y, Gd, Dy, Yb, Lu) were synthesized by heating mixtures of Ln, P, S, and Li2S4 at 900 °C (100 h) and they were investigated by single crystal X‐ray methods. The compounds with Ln = Y (a = 28.390(2), b = 10.068(1), c = 33.715(2) Å, β = 113.85(1)°), Gd (a = 28.327(2), b = 10.074(1), c = 33.822(2) Å, β = 114.297(7)°), Dy (a = 28.124(6), b = 10.003(2), c = 33.486(7) Å, β = 113.89(3)°), Yb (a = 28.178(3), b = 9.977(1), c = 33.392(4) Å, β = 113.65(1)°), and Lu (a = 28.169(6), b = 10.002(2), c = 33.432(7) Å, β = 113.54(3)°) are isotypic and crystallize in a new structure type (C2/c; Z = 12). Main feature are PS4 tetrahedra isolated from each other surrounding the Ln and Li atoms via their S atoms. The coordination number of the five crystallographically independent Ln atoms is eight, but the polyhedra are quite different and they are interlinked to larger units extending in [010]. The environment of the Li atoms is irregular and formed by five to six S atoms. The crystal structure is compared with that of Li9Ln2(PS4)5 (Ln: Nd, Gd). For the synthesis of Ag3Y(PS4)2 (a = 16.874(3), b = 9.190(2), c = 9.312(2) Å, β = 123.17(3)°) a mixture of Y, P, S, and Ag2S was heated to 700 °C (50 h). The thiophosphate crystallizes in a new structure type (C2/c; Z = 4) composed of isolated PS4 tetrahedra. The two crystallographically independent Ag atoms are surrounded by four S atoms in the shape of distorted tetrahedra. The Ag(1)S4 polyhedra are cornershared to strands running along [001], which are linked together via Ag(2)S4 tetrahedra. The environment of the Y atoms is composed of eight S atoms each building distorted square antiprisms. These polyhedra are connected with each other via common edges to a strand running along [001].  相似文献   

12.
The orthothioborates Ce[BS3], Pr[BS3] and Nd[BS3] were prepared from mixtures of the rare earth (RE) metals together with amorphous boron and sulfur summing up to the compositions CeB3S6, PrB5S9 and NdB3S6. The following preparation routes were used: solid state reactions with maximum temperatures of 1323 K and high-pressure high-temperature syntheses at 1173 K and 3 GPa. Pr[BS3] and Nd[BS3] were also obtained from rare earth chlorides RECl3 and sodium thioborate Na2B2S5 by metathesis type reactions at maximum temperatures of 1073 K. The crystal structure of the title compounds was determined from X-ray powder diffraction data. The thioborates are isotypic and crystallize in the orthorhombic spacegroup Pna21 (No. 33; Z=4; Ce: , , ; Pr: , , ; Nd: , , ) . The crystal structures contain isolated [BS3]3‐ groups with boron in trigonal-planar coordination. The sulfur atoms form the vertices of undulated kagome nets, which are stacked along [100] according to the sequence ABAB. Within these nets every second triangle is occupied by boron and the large hexagons are centered by rare earth ions, which are surrounded by overall nine sulfur species.  相似文献   

13.
Sol-gel synthesis of nano-sized BaTiO3, BaZrO3 and BaTi0.5Zr0.5O3 ceramics using alkoxide and semi-alkoxide routes has been investigated and the pervoskites obtained have been compared with respect to crystallisation temperature, crystallite size and compositional purity. Heterometal alkoxides containing two (for BaTiO3 and BaZrO3) and three (for BaTi0.5Zr0.5O3) different metals were used as single-source precursors in the alkoxide route while semi-alkoxide synthesis was performed by reacting barium hydroxide or acetate with Ti and/or Zr alkoxides. Semi-alkoxide synthesis also produces stoichiometric and phase-pure oxides, however, at temperatures higher than 1000°C. At temperatures below 1000°C, BaCO3 and small amounts of other undesired phases (e.g., BaTi2O4) were present in the oxides derived from semi-alkoxide synthesis. Thermal behaviour, studied by TGA/DTA measurements, shows that thermal decomposition occurs in three major steps and depends on the educt composition and the synthesis route. Among alkoxide derived powders, crystalline BaTi0.5Zr0.5O3 phase is formed at 400°C while complete crystallisation of BaMO3 ceramics occurs around 600°C. The cubic to tetragonal phase transition for BaTiO3 is clearly observed at relatively low-temperature of 800°C. The stoichiometry and phase homogeneity of the obtained powders were demonstrated by energy dispersive X-ray analysis and powder diffractometry. The averaged crystallite size of the obtained nano-ceramics was evaluated using the FormFit programme. SEM and TEM observations revealed a high microstructural uniformity.  相似文献   

14.
The aim of this study is to improve the dielectric and mechanical properties of HDPE/BaTiO3 composites by binary BaTiO3 particles, when the volume fraction of BaTiO3 is constant. In this study, it was found that the pack density of binary BaTiO3 particles in HDPE/BaTiO3 composite relies on particle ratio and volume fraction of small particles. It is found that the addition of 50 vol % 1600 nm BaTiO3 particles can boost the dielectric constant of HDPE control from 2 to 30 (14 times higher) at 40 Hz and 19 (8.5 times higher) at 40 MHz, respectively. When the particle ratio was 4, the substitution of 10 vol % 1600 nm BaTiO3 particles by 10 vol % 400 nm BaTiO3 particles can further enhance the dielectric constant of HDPE/L‐BT (10/10) from 30 to 50 (67% increase) at 40 Hz and from 19 to 42 (121% increase) at 40 MHz, respectively, without greatly influencing the volume resistivity of HDPE composites. In addition, the thermal conductivity of HDPE with binary BaTiO3 particles were all above 2.0 W/(m•K). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1101–1108  相似文献   

15.
A series of nano-sized particle materials containing ZrO2 was prepared and their compositions were determined by elemental analysis and thermogravimetric analysis (TGA). The effect of particle size and crystal structure type (lattice and space group) on the ER performance of these materials was investigated by X-ray diffraction (XRD) analysis, Raman spectra, the particle size analysis and rheological measurement. Their electrorheological (ER) effects show that the ER activities of the ZrO2 materials doped with rare earth (RE=Y, La, Ce, Gd, Tb), whose grain sizes were less than that of pure ZrO2, were lower than that of pure ZrO2, which belongs to the tetragonal crystal system. The ER activity of Y2O3-ZrO2 is the strongest among all the RE-doped ZrO2 materials. The ER activity of the tetragonal phase ZrO2 is higher than that of the monoclinic phase ZrO2.  相似文献   

16.
The ternary rare earth boride carbides R2B4C (R=Tb, Dy, Ho, Er) have been synthesized by reacting the elements at temperatures between 1800 and 2000K. The crystal structure of Dy2B4C has been determined from single-crystal X-ray diffraction data. It crystallizes in a new structure type in the orthorhombic space group Immm (a=3.2772(6) Å, b=6.567(2) Å, c=7.542(1) Å, Z=2, R1=0.035 (wR2=0.10) for 224 reflections with Io>2σ(Io)). Boron atoms form infinite chains of fused B6 rings in [100] joined with carbon atoms into planar, two-dimensional networks which alternate with planar sheets of rare earth metal atoms. The electronic structure of Dy2B4C was also analyzed using the tight-binding extended Hückel method.  相似文献   

17.
采用熔融硼酸法合成了一种具有层状结构的新型水合稀土多硼酸盐, La[B5O8(OH)(H2O)]NO3•2H2O, 并利用单晶X射线衍射技术确定了它的结构. 它属于单斜晶系, P21/n空间群. 其基本构建单元 (fundamental building block, 简称FBB)是由三个BO4和两个BO3基团所构成的一个双三元环[B5O12]基团. 结构中每一个FBB通过共顶点氧原子与周围四个同样的单元连接成具有九元环窗口的二维[B5O10]层, La3+位于九元环中心附近. [B5O10]层沿着b方向进行堆积, 硝酸根离子和结构中部分结晶水分子位于相邻的[B5O10]层之间.  相似文献   

18.
Summary. The equiatomic rare earth metal–iridium–silicides REIrSi (RE=Ce, Pr, Er, Tm, Lu) were prepared by arc-melting of the elements and subsequent annealing. All silicides were characterized through their X-ray powder patterns. The structures of CeIrSi, ErIrSi, and LuIrSi were refined from X-ray single crystal diffractometer data: LaIrSi type, P213, a=629.15(2)pm, wR2=0.1232, 280F2 values, and 11 variable parameters for CeIrSi; TiNiSi type, Pnma, a=673.4(1), b=416.07(5), c=744.88(9)pm, wR2=0.0705, 339F2 values, and 20 variable parameters for ErIrSi, and a=664.0(3), b=412.9(1), c=742.6(1)pm, wR2=0.0398, 496F2 values, and 20 variable parameters for LuIrSi. The iridium and silicon atoms in CeIrSi, ErIrSi, and LuIrSi build three-dimensional [IrSi] networks where the iridium atoms have three (CeIrSi, Ir–Si 229pm) and four (ErIrSi, Ir–Si 247–258pm; LuIrSi, Ir–Si 245–256pm) silicon neighbors. The [IrSi] networks leave larger channels in which the cerium, erbium, and lutetium atoms are located. Temperature dependent susceptibility data for LuIrSi indicate Pauli paramagnetism. CeIrSi shows Curie-Weiss paramagnetism above 100K with an experimental magnetic moment of 2.56(2)B/Ce atom. With samarium as rare earth metal component the silicide SmIr0.266(8)Si1.734(8) with -ThSi2 type structure was obtained: I41/amd, a=409.3(1), c=1397.2(5)pm, wR2=0.0575, 161F2 values, and 9 variable parameters. Within the three-dimensional [Ir0.266Si1.734] network the Ir/Si–Ir/Si distances range from 230 to 237pm.  相似文献   

19.
The crystal structure of the known compounds Ln5Re2O12 (Ln = Y, Gd, Dy–Lu) and the new isotypic terbium rhenate Tb5Re2O12 was determined from X‐ray data of a twinned crystal of Ho5Re2O12: B2/m, a = 1236.5(4) pm, b = 748.2(2) pm, c = 563.8(1) pm, γ = 107.73(3)°, Z = 2, R = 0.034 for 379 structure factors and 37 variable parameters. The rhenium atoms (oxidation number +4.5) have octahedral oxygen coordination. These ReO6 octahedra share edges, thus forming infinite strings with alternating short and long Re–Re distances: 243.6(2) and 320.1(2) pm. Of the three holmium positions two are surrounded by seven oxygen atoms and the third one has octahedral oxygen coordination. The crystal structure of Pr3ReO8 was refined from single‐crystal X‐ray data: P21/a, a = 1498.0(2) pm, b = 749.09(8) pm, c = 610.48(9) pm, γ = 110.39(1)°, R = 0.017 for 2082 F values and 110 variable parameters. It is isotypic with a structure first determined for Sm3ReO8. The new compounds Pr3Re2O10 and Pr4Re2O11 were prepared by reaction of elemental praseodymium with the metaperrhenate Pr(ReO4)3. They were characterized through their X‐ray powder diagrams. Pr3Re2O10 was found to be monoclinic: a = 778.47(9) pm, b = 773.62(9) pm, c = 706.10(8) pm, β = 114.77(1)°. It is isotypic with La3Os2O10 and La3Re2O10. Pr4Re2O11 crystallizes with Nd4Re2O11 type structure with the tetragonal lattice constants a = 1272.49(3) pm, c = 562.29(2) pm. The compounds Nd4Re2O11 and Sm4Re2O11 are confirmed. The magnetic properties of Ho5Re2O12, Tb5Re2O12, Pr3Re2O10, Pr4Re2O11, Nd4Re2O11, and Sm4Re2O11 were investigated with a Faraday balance. None of these compounds shows magnetic order above 200 K.  相似文献   

20.
The crystal structure of the RE2PbS4 (RE = Y, Dy, Ho, Er and Tm) compounds (space group Cmc21, Pearson symbol oC112, a = 0.79301(3) nm, b = 2.86966(9) nm, c = 1.20511(5) nm, RBragg = 0.0979 for Y2PbS4; a = 0.79484(8) nm, b = 2.8721(3) nm, c = 1.2039(1) nm, for Dy2PbS4; a = 0.79081(2) nm, b = 2.86222(7) nm, c = 1.20220(4) nm, RBragg = 0.0859 for Ho2PbS4; a = 0.7863(2) nm, b = 2.8525(5) nm, c = 1.1995(2) nm, R1 = 0.0482 for Er2PbS4 and a = 0.78419(3) nm, b = 2.84184(9) nm, c = 1.19655(4) nm, RBragg = 0.0893 for Tm2PbS4) was investigated by means of X‐ray single crystal and powder diffraction. Each RE atoms is octahedrally coordinated by six S atoms. Each Pb atoms is surrounded by seven S atoms to form a mono‐capped trigonal prism.  相似文献   

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