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1.
Strontium phosphate apatites containing different amounts of copper were prepared by a solid state reaction at 1100 °C or by arc melting above 1600 °C in air. The samples were characterized by X‐ray diffraction, ICP analysis, scanning electron microscopy, IR spectroscopy, MAS—1H—NMR, diffuse reflectance spectroscopy, and SQUID magnetometry. X‐ray crystal structure determination was carried out for a single crystal obtained from the melt. The compound is formulated as Sr5(PO4)3(CuO2)1/3 and has an apatite structure (space group P63/m, a = 9.7815(4)Å, c = 7.3018(4)Å, Z = 2) with linear CuO23— ions occupying hexagonal channels. For solid state synthesized samples, Rietveld refinement of powder XRD patterns was performed. The samples obtained at 1100 °C acquire the composition Sr5(PO4)3CuxOHy, with x changing from 0.01 to 0.62 and y < 1—x. The copper content can be increased to x = 0.85 by annealing in argon at 950 °C. The compounds represent a hydroxyapatite in which part of the protons is substituted by Cu+ and Cu2+ ions. The ions form linear O—Cu—O units which are progressively condensed creating the Cu—O—Cu bridges on increasing copper content. IR and NMR data testify existence of OH groups, non‐disturbed and disturbed by neighboring Cu atoms. In the electron spectra, the samples exhibit absorption bands at 7800‐7900, 14200‐14500 and 17500‐17550 cm—1, which were assigned to Cu2+ d‐electron transitions. By annealing the sample with x = 0.1 in oxygen at 800 °C copper is fully oxidized while retaining in channels in unusual for Cu2+ linear coordination.  相似文献   

2.
Copper-containing calcium phosphates Ca5 ? z Y z (PO4)3Cu x OH1 ? x ? z, where x = 0, 0.1, 0.3 and z = 0, 0.5, with an apatite structure and a partial substitution of yttrium for calcium have been synthesized by a solid-phase method at a temperature of 1100–1150°C. The compounds have been characterized by X-ray powder diffraction and diffuse reflectance spectroscopy. It has been established that yttrium substitutes for calcium only in the Ca(2) position, and the occupancy of this position corresponds to the yttrium content z = 0.4–0.43. The substitution by yttrium slightly decreases the unit cell parameter of the compound (by ~0.3%) and much more considerably (by 3%) reduces the diameter of a hexagonal channel formed by Ca(2) atoms. The predominant fraction of doping copper intrudes into hexagonal channels in both unsubstituted and yttrium-substituted calcium phosphates. Unsubstituted copper-containing phosphates are pink-crimson colored, whereas their yttrium-substituted analogues have much more pale colors from nearly white to greeny beidge. The absorption bands typical for a copper-containing calcium hydroxyapatite observed in diffuse reflectance spectra are strongly suppressed in yttrium-substituted samples probably due to a decreased average oxidation number of copper.  相似文献   

3.
A new chromophore has been identified in copper‐doped apatite pigments having the general composition [Sr10(PO4)6(CuxOH1?x?y)2], in which x=0.1, 0.3 and y=0.01–0.42. By using X‐ray absorption spectroscopy, low‐temperature magnetization measurements, and synchrotron X‐ray powder structure refinement, it has been shown that the oxygenated compounds contain simultaneously diamagnetic Cu1+ and paramagnetic Cu3+ with S=1. Cu3+ is located at the same crystallographic position as Cu1+, being linearly coordinated by two oxygen atoms and forming the OCuO? anion. The Raman spectroscopy study of [A10(PO4)6(CuxOH1?x?y)2,], in which A=Ca, Sr, Ba, reveals resonance bands at 651–656 cm?1 assigned to the symmetric stretching vibration (ν1) of OCuO?. The strontium apatite pigment exhibits a strong paramagnetic anisotropy with an unprecedentedly large negative zero‐field splitting parameter (D) of ≈?400 cm?1. The extreme magnetic anisotropy causes slow magnetization relaxation with relaxation times (τ) up to 0.3 s at T=2 K, which relates the compounds to single‐ion magnets. At low temperature, τ is limited by a spin quantum‐tunneling, whereas at high temperature a thermally activated relaxation prevails with Ueff≈48 cm?1. Strong dependence of τ on the paramagnetic center concentration at low temperature suggests that the spin‐spin relaxation dominates in the spin quantum‐tunneling process. The compound is the first example of a d‐metal‐based single‐ion magnet with S=1, the smallest spin at which an energy barrier arises for the spin flipping.  相似文献   

4.
Ca5(PO4)3CuyO y + δ(OH)0.5 ? y ? δX0.5 compounds (for X = OH, y = 0.01–0.3; for X = F, y = 0.01–0.1; for X = Cl, y = 0.1) have been synthesized by heat treatment of oxide-carbonate mixtures at 1150°C in air and have been characterized by X-ray diffraction, electronic spectroscopy, and magnetic measurements. The compounds have an apatite structure in which copper atoms substitute for part of the hydroxyl hydrogen atoms in hexagonal channels. The electronic spectrum shows two main absorption bands due to d-d transitions in copper(II) linearly coordinated to two oxygen atoms, as well as extra, weaker bands, whose contribution to the overall spectrum decreases with decreasing y. The latter are assignable to copper atoms occupying other sites in the crystal lattice. The temperature dependence of the magnetic susceptibility of the compounds obeys the Curie-Weiss law with a Curie constant close to zero. The Weiss constant characterizes the copper(II) content of the compounds and correlates qualitatively with the intensity of the main absorption bands in the visible spectrum. The fraction of copper(II) in the total amount of copper in the apatites increases in the substituent order X: Cl, OH, F, as well as upon the low-temperature annealing of the compounds in air. At the same time, copper(II) fraction depends only slightly on the total copper content. As the copper(II) content increases, the color of apatite changes from pink to dark claret.  相似文献   

5.
荧光材料基质的结构调制对于调控发光材料的发光性能,探索固体结构-性能关系具有重要的研究意义。本文以Y2SiO5基质为模型,分别利用Si/Al和Si/P取代,以[AlO4]和[PO4]四面体替换[SiO4]四面体,设计合成了一系列组成为Y1.95Si1-xAlxO5-xFx∶0.05Ce3+(x=0.05,x=0.1,x=0.2,x=0.4,x=1)和Y1.95-yCaySi1-yPyO5∶0.05Ce3+(y=0,y=0.02,y=0.04,y=0.06,y=0.08,y=0.2)的荧光材料。结合X射线衍射、荧光光谱、荧光寿命等测试手段对其进行了表征分析。结果表明,在x≤0.2,y≤0.04时得到的产物能够保持Y2SiO5的结构特征,在一定的基质组成替换范围内,设计合成的样品Y1.95Si1-xAlxO5-xFx∶0.05Ce3+、Y1.95-yCaySi1-yPyO5∶0.05Ce3+能提高发光强度,发射光谱呈现蓝移现象。荧光寿命测试表明这两个系列的化合物中Ce3+所处的基质环境变化较小,Ce3+发光也未产生较大的变化。  相似文献   

6.
On Hexagonal Perovskites with Cationic Vacancies. XXXII. Photoluminescence of Trivalent Rare Earth in the Systems Ba2?ySryLa2?xRExMgW2□O12 In the series Ba2?ySryLa2?xRExMgW2□O12 the Ba2+ can be completely substituted by Sr2+. All compounds crystallize in the rhombohedral 12 L-type (space group R3 m; sequence (hhcc)3). By doping the stacking polytypes with some of the trivalent rare earths efficient visible photoluminescence is obtained. The simultaneous incorporation of two different rare earth ions leads to two-color-phosphors, which, according to the excitation energy used, emit either mainly the typical spectrum from one or the other activator; the corresponding luminescence mechanism are discussed.  相似文献   

7.
Superconducting oxides of the type Hg1-xTlxSr4-yBayCu2CO3O7-δ show complex modulated structures with a modulation vector along [010] and a wavelength varying between 6 and 8 times the basic perovskite unit. High resolution electron microscopy indicates that the modulation is introduced by an ordering of CO3 groups on the (Hg-Tl) sublattice. Such modulated structures are discussed in general; they are the result of a minimization of the internal stresses due to the differences in ionic sizes of the constituents.  相似文献   

8.
Crystals of the chemical composition Ba7F12Cl2 were modified by adding a small amount of Ca2+ to allow the synthesis of the corresponding bromine compound Ba[Ca]7F12Br2. These samples were prepared in a NaBr flux and characterized by single crystal x‐ray diffraction. The new structure crystallizes in a disordered arrangement in the hexagonal space group P63/m (176). The calcium ion has a coordination number of 6. Solid solutions on the heavy halide position can be synthesised in a NaCl/NaBr flux to obtain the compounds Ba7?xCaxF12(ClyBr1?y)2 with x = ~0.5 and 0 < y < 1. Regardless the amount of calcium used in the preparation process, the Ca stoichiometry in the compound is always between 0.3 and 0.5. The lattice parameters differ depending on the Ca‐ and Br‐content between 1053.81(5) ? a = b ? 1058.93(3) pm and 421.21 ? c ? 426.78(3) pm.  相似文献   

9.
In the context, SrxY10−x(SiO4)y(PO4)6−yO2 doped with 1 mol%Eu3+ (x = 2, y = 6; x = 4, y = 4; x = 5, y = 3; x = 8, y = 0) were synthesized by using 3-aminopropyl-triethoxysilane (APES) as the sources of the silicate network. X-ray diagrams confirm that SrxY10−x(SiO4) y(PO4)6−yO2: Eu3+ solid solutions are formed as a pure apatitic phase. The SEM picture shows that there exist some novel unexpected coral like morphological structures. The luminescent intensity is the strongest for the host composition of Sr4Y6(SiO4)4(PO4)2O2 although the effect of the composition on the luminescent intensity is little.  相似文献   

10.
The scientific principles were formulated that underlie an integrated approach to development and synthesis of bulk and membrane catalysts for methanol transformation to dimethyl ether and hydrogen which are environmentally friendly fuels. The results were summarized for studies into relationships in formation of phosphates MZr2(PO4)3 (M = Na, K, Rb, Cs, Mg0.5, Ca0.5, Sr0.5, Ba0.5, Zr0.25), Cu0.5(1+y)Fe y Zr2−y (Po4)3, molybdate phosphates Na1−y Zr2(Moo4) y (Po4)3−y , and molybdate Ni0.3Cr0.4Fe1.4(Moo4)3 with the desired structure and properties controllable by variation of their chemical composition and synthesis parameters. The surface characteristics and catalytic properties of the resulting systems and the yields of the target product formed from methanol transformations in inert and oxidizing atmospheres were analyzed in relation to the catalyst synthesis condition.  相似文献   

11.
X‐ray diffraction analysis of single crystals of three new arsenates adopting apatite‐type structures yielded formula Sr5(AsO4)3F for strontium arsenate fluoride, (I), (Sr1.66Ba0.34)(Ba2.61Sr0.39)(AsO4)3Cl for strontium barium arsenate chloride, (II), and Cd5(AsO4)3Cl0.58(OH)0.42 for cadmium arsenate hydroxide chloride, (III). All three structures are built up of isolated slightly distorted AsO4 tetrahedra that are bridged by Sr2+ in (I), by Sr2+/Ba2+ in (II) and by Cd2+ in (III). Compounds (I) and (II) represent typical fluorapatites and chlorapatites, respectively, with F at the 2a (0, 0, ) site and Cl at the 2b (0, 0, 0) site of P63/m. In contrast, in (III), due to the requirement that the smaller Cd2+ cation is positioned closer to the channel Cl anion (partially substituted by OH), the anion occupies the unusual 2a (0, 0, ) site. Therefore, Cl is similar to F in (I), coordinated by three A2 cations, unlike the octahedrally coordinated Cl in (II) and other ordinary chlorapatites. Furthermore, in (III), using FT–IR studies, we have inferred the existence of H+ outside the channel in oxyhydroxyapatites and provided possible atomic coordinates for a H atom in HAsO42−, leading to a proposed formulation of the compound as Cd5(AsO4)3−x(HAsO4)xCl0.58(OH)0.42−x−(y/2)Ox+(y/2)y/2.  相似文献   

12.
On Hexagonal Perovskites with Cationic Vacancies. XXXIII. Compounds of Type Ba6?xSrxB2?y3+SEy3+W3□O18 In the series Ba6?xSrxLu2?ySEy3+W3□O18 a substitution of Sr2+ for Ba2+ is possible. According to intensity calculations on powder data of BaSr5Lu1,6Ho0,4W3□O18 the compounds crystallize in a rhombohedral 18 L type with the sequence (hhcccc)3; space group R3 m. The refined, intensity related R' value is 11.5%. The differences in properties (diffuse reflectance spectra, photoluminescence) between the hexagonal modifications Ba6B2?y3+SEy3+W3□O18 (B3+ ? Gd, Y, Lu; SE3+ ? Sm, Eu, Tb, Dy, Ho, Er, Tm) and the corresponding cubic HT modifications are discussed.  相似文献   

13.
Sr5(VO4)3(CuO) was prepared via solid state reactions from mixed powders of the metal oxides or carbonates in corundum crucibles in air (1173–1740 K). The compound is transparent and stable in air. The color changes with the preparation temperature from light gray (1173 K) to gray (1740 K). The crystal structure (space group P63/m, No. 176; Z = 2; a = 10.126 Å, c = 7.415 Å) is a derivative of the apatite Ca5(PO4)3OH, and is characterized by isolated [VO4]3– anions (d(V–O) = 1.710 Å) and infinite linear 1∞[CuO]1– chains (d(Cu–O) = 1.854 Å) inserted in the channels parallel to the hexagonal axis. The compound prepared at 1740 K contains vacancies at the copper and oxygen positions of the linear chains (about 10% and 5%, respectively).  相似文献   

14.
The homogeneous substitution of cations (K+) and anions (H2PO4) for CsHSO4 is performed. The dependences of protonic conductivity and structure of (1 − x)CsHSO4-xKH2PO4 (x = 0.05–0.9) compounds on the composition are studied. It is found that the introduction of KH2PO4 leads to the formation of a new highly conductive phase. At small amounts of introduced KH2PO4 (x = 0.05), a mixed salt forms; its low-temperature conductivity is by more than two orders of magnitude higher than that of the source salts. The thermal behavior of mixed salt (1 − x)CsHSO4-xKH2PO4 of various compositions and the peculiarities of crystal structure are studied. The structural parameters of the salt at x = 0.05–0.5 are close to those of Cs3(HSO4)2(H2PO4). At higher x, another phase forms, whose structure has yet to be determined. The thermal stability of the salt decreases with increasing fraction of KH2PO4 introduced. The conductivity of the composites based on the mixed salt and silicon dioxide (1 − y){xKH2PO4-(1 − x)CsHSO4}-ySiO2 (x = 0.05, 0.1; y = 0.1–0.7) is studied. It is shown that, in the low-temperature range, the conductivity of composite systems increases within an order of magnitude, passes through a maximum, and, then, decreases at y > 0.5 due to the percolation effect.  相似文献   

15.
Superconducting oxide ceramics of composition Y(Ba1–x Sr x )2Cu4O8 (x = 0.00, 0.10, and 0.20) have been prepared by a simple sol-gel method based on the complexation of metal ions in aqueous medium, by chelating acetate and tartarate ligands. Homogeneous sols were obtained by complexing copper ions with tartaric acid, which prevented the flocculation of copper acetate during the gelation process. Single-phase bulk samples were obtained after firing the mixed-metal polymeric acetate-tartarate precursor to 835°C for 70 h in flowing oxygen atmosphere. Thermal decomposition of the gels was studied by thermogravimetry. Effect of strontium substitution on the properties of the compounds was studied by X-ray powder diffraction, electron microscopy, X-ray photoemission spectroscopy and resistivity measurements. These data indicate that nearly monophasic Y(Ba1–x Sr x )2Cu4O8 superconducting samples were obtained for x < 0.30. The Sr-doping in the YBa2Cu4O8 (Y-124) phase shows a pronounced effect on the superconducting properties enhancing the critical temperature from 78 K (for the non-substituted sample) to 88 K (for Y(Ba1–x Sr x )2Cu4O8).  相似文献   

16.
We have used electron–positron annihilation to study superconducting cuprates Sm1+x Ba2–x Cu3O y . We have determined the average radii for oxygen ions in Sm1+x Ba2–x Cu3O y . Taking into account the ion coordinates and their radii, we have constructed a geometric model for the arrangement of copper and oxygen ions in CuO2 layers in the [b, c] plane, responsible for the superconductivity. From these data, we have determined the length of the ionic/covalent bonds and the width of the interionic gaps. We have established the effect of the features of the atomic structure of Sm1+x Ba2–x Cu3O y on the superconducting transition temperature T c and we have shown that T c increases as X inceases.  相似文献   

17.
On Hexagonal Perovskites with Cationic Vacancies. XXVII. Systems Ba4?xSrxBIIRe2□O12, Ba4B CaxRe2□O12, and Ba4?xLaxBIIRe2?xWx□O12 with BII = Co, Ni In the systems Ba4?xSrxBIIRe2□O12, Ba4BCaxRe2□O12 and Ba4?xLaxBIIRe2?xWx□O12 (BII = Co, Ni) hexagonal perovskites with a rhombohedral 12 L structure (general composition A4BM2□O12; sequence (hhcc)3; space group R&3macr;m) are observed. With the exception of Ba4NiRe2□O12 the octahedral net consists of BO6 single octahedra and M2□O12 face connected blocks (type 1). In type 2 (Ba4NiRe2□O12) the M ions are located in the single octahedra and in the center of the groups of three face connected octahedra. The two outer positions of the latter are occupied by B ions and vacancies in the ratio 1:1. The difference between type 1 and 2 are discussed by means of the vibrational and diffuse reflectance spectra.  相似文献   

18.

La1-xAxCoO3-δ (A = Sr, Ba) nanoparticles used as an inert anode in molten salts were characterized using phonon vibrations, and their compositions and morphologies were investigated. These nanoparticles were used for nanostructure fabrication of an inert anode to reduce oxide ion transportation. The singularity structure changes with increasing Sr ion content in La1-xSrxCoO3-δ nanoparticles showed a transient of spin state change from a low-spin state to intermediate- and/or high-spin states. The valencies of Co ion in La1-xSrxCoO3-δ were 3.2 and 3.3 for La0.8Sr0.2CoO3-δ and La0.6Sr0.4CoO3-δ, respectively, suggesting that oxygen defects were introduced by Sr ion doping in La1-xSrxCoO3-δ nanoparticles. In contrast, the valencies of Co ion in La1-xBaxCoO3-δ were 3.1 and 3.0 for La0.5Ba0.5CoO3-δ and La0.4Ba0.6CoO3-δ, respectively, suggesting that oxygen defects were introduced slightly by Ba ion doping in La1-xBaxCoO3-δ nanoparticles. The isotropic phonon vibrations of La1-xAxCoO3-δ nanoparticles were estimated using high-temperature synchrotron radiation X-ray diffraction measurements. Crystal anisotropy measurements of phonon vibrations indicated that the oxide ions diffused preferentially along the (a, b) plane in the La1-xSrxCoO3-δ crystal lattice and toward the c-axis direction in the La1-xBaxCoO3-δ crystal lattice. These results suggest that the oxide ion transportation was curtailed using layered nanoparticles to fabricate an inert anode.

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19.
原位制备钛酸锶钡/铌酸锶钡复相陶瓷的研究   总被引:2,自引:0,他引:2  
0引言驰豫型铁电陶瓷是近年来广泛研究和迅速发展的一种新型功能陶瓷[1]。通过把具有不同相变温度的驰豫型铁电体层层叠加,可以获得具有稳定的介电常数鄄温度关系的复合材料[2]。钛酸锶钡Ba1-xSrxTiO3和铌酸锶钡SrxBa1-xNb2O6都是重要的驰豫型铁电体,并且其居里温度均随Ba/Sr比  相似文献   

20.
Phase composition, electroconductivity, oxygen ion transport number, and microhardness of samples of Ln1 − x SrxGa0.5 − y/2Al0.5 − y/2MgyO3 − δ (Ln = La, Pr, Nd; x, y = 0.10, 0.15) synthesized by a ceramic methods are studied. Methods of x-ray diffraction analysis and scanning electron microscopy reveal the La-containing samples to be homogeneous and have a perovskite structure. Magnesium does not dissolve in Pr-and Nd-containing systems but forms an individual phase based on magnesium oxide. Apart from magnesium oxide, in these systems there form extrinsic phases, specifically, LnSrGa3O7 and an unknown phase. The electroconductivity of La1 − x SrxGa1 − y MgyO3 − δ decreases after substituting Al for Ga. Ceramic La1 − x SrxGa0.5 − y/2Al0.5 − y/2MgyO3−δ is a purely ionic conductor in the temperature interval 500 to 1000°C; NdxSrxGa0.5 − y/2Al0.5 − y/2MgyO3 − δ has predominantly ionic conduction; and the predominant type of conduction in Pr1 − x SrxGa0.5 − y/2Al0.5 − y/2MgyO3 − δ is electronic below 700–800°C, with the contribution of ionic conduction increasing at higher temperatures. Substituting Al for Ga raises the hardness of ceramics under study. Among the compositions studied, La0.85Sr0.15Ga0.45Al0.45Mg0.10O3 − δ and La0.85Sr0.15Ga0.425Al0.425Mg0.15O3 − δ exhibit a combination of electroconductivity and hardness that is optimal for application as electrolyte at reduced temperatures (600–800°C). The Pr1 − x SrxGa0.5 − y/2Al0.5 − y/2MgyO3 − δ system possesses mixed ionic-electronic conduction and high hardness, which makes it appealing for application as oxygen-penetrable membranes. Original Russian Text ? Yu.V. Danilov, A.D. Neuimin, L.A. Dunyushkina, L.A. Kuz’mina, N.S. Zybko, Z.S. Martem’yanova, A.A. Pankratov, 2007, published in Elektrokhimiya, 2007, Vol. 43, No. 1, pp. 57–65.  相似文献   

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