Ni3(Tix,V1-x)合金系中的长周期结构

本文利用电子衍射及高分辨点阵象实验方法证实了Ni₃(Ti_x,V_1-x)合金系在铸态下存在有9R,10H,16H,20H,21H,44H等长周期结构以及2H结构。它们与体心四方基体相(结构与Ni₃V相同)及六角基体相(结构与Ni₃Ti相同)有固定取向关系:{001}_长周期∥{001}_(Ni3Ti)∥{112}_{Ni3V);〈100〉长周期∥〈100〉(Ni3Ti)∥〈110〉(Ni3V)。样品经长期高温退火处理后其它长周期结构均向9R结构转变。 关键词：}     

Lattice imaging of close-packed structures by high resolution electron microscopy: ABO3 perovskite polytypes

Lattice imaging technique of high resolution electron microscopy has been employed to examine 4H, 6H and 9R ABO₃ perovskite polytypes. The lattice images can be correlated with the lattice periodicity and the stacking sequence of AO₃ layers and BO₆ octahedra. The study shows the utility and validity of the lattice imaging technique for the study of relatively close-packed systems. Commonwealth Visiting Professor, University of Oxford (1974–75).     

Absence of a space-charge-derived enhancement of ionic conductivity in β|γ- heterostructured 7H- and 9R-AgI

Extreme room temperature conductivity enhancements have been reported for nanocrystalline AgI of up to ×?10(4) relative to bulk β-AgI (Guo et?al 2005 Adv.?Mater. 17 2815-9). These samples were identified as possessing 7H and 9R polytype structures, which can be considered as heterostructures composed of thin, commensurate layers in the β (wurtzite) and γ (zincblende) phases. It has been proposed that space-charge layer formation at β|γ-interfaces causes near complete disordering of the Ag(+)?sublattice in these polytypes, resulting in a massive intrinsic enhancement of ionic conductivity. We have performed molecular dynamics simulations of β- and γ-AgI and mixed β|γ?superlattices, to study the effect of heterostructuring on intrinsic defect populations and Ag(+) transport. The ionic conductivities and Ag(+)?diffusion coefficients vary as β?>?7H?≈?9R?≈?10L?>?γ. The β|γ-heterostructured polytypes show no enhancement in defect populations or Ag(+)?mobilities relative to the β-AgI phase, and instead behave as simple composites of β- and γ-AgI. This contradicts the proposal that the extreme conductivity enhancement observed for 7H and 9R polytypes is explained by extensive space-charge formation.     

Investigation on the 773 K isothermal section of Dy–Ni–Si ternary phase diagram by X-ray powder diffraction

The 773 K isothermal section of the Dy–Ni–Si ternary system was investigated and constructed by X-ray powder diffraction in this paper. Eighteen ternary phases (DyNiSi, DyNi₂Si₂, DyNiSi₂, Dy₂Ni₃Si₅, DyNiSi₃, Dy₂NiSi₃, Dy₃Ni₆Si₂, DyNi₁₀Si₂, Dy₄NiSi₇, DyNi₂Si, DyNi₅Si₃, DyNi₄Si, Dy₃NiSi₂, DyNi₆Si₆, Dy₈Ni₃₁Si₁₁, Dy₃Ni₂Si₄, Dy₄Ni₅Si and Dy₉Ni₂Si₁₄) were confirmed to exist in this work. In those ternary phases, Dy₉Ni₂Si₁₄ is a new phase, Dy₂NiSi₃ and Dy₄NiSi₇ have solid solution phenomena and the solid solution ranges are Dy_33.3Ni_14.7–18.7Si_52–48 and Dy₄Ni_0.3–1.2Si_7.7–6.8, respectively. We constructed 14 two phase regions and 52 three phase regions in the Dy–Ni–Si ternary phase diagram at 773 K. Because the phase relation is not very clear between 66.7 and 50 Si at.% in the Dy–Si binary system, we use dot lines to estimate tentative phase regions in this region.     

Sm-Ni二元系合金相图

本文用X射线衍射、差热分析及金相分析方法测定了Sm-Ni二元系合金相图。在此二元系中观察到8个金属间化合物:Sm₃Ni(664℃分解),SmNi(熔点为1079℃),SmNi₂(1034℃分解),SmNi₃(1135℃分解),Sm₂Ni₇(1220℃分解),SmNi₄(1282℃分解),SmNi₅(熔点为1430℃)和Sm₂Ni₁₇(1288℃分解)。发生三个共晶反应:Sm₃Ni-SmNi(570℃,～32at%Ni),SmNi-SmNi₂(809℃,53.5at%Ni)和Sm₂Ni₁₇-Ni(1280℃,94at%Ni)。无论是Sm在Ni中或是Ni在Sm中,均未观察到明显的固溶度。 关键词：     

Magnetic and structural characteristics of the R3Ni7B2 compounds (R = rare earth)

Magnetic and structural behaviour and phase relationships of materials of composition R₃Ni₇B₂ (R = Nd-Lu) were investigated. Detailed X-ray analysis yields that two hexagonal structures are encountered. For the heavy rare earth (Gd-Lu) the compounds crystallize in the CeNi₃ structure. The space group is P6₃/mmc and each unit cell contains two formula units. The R₃Ni₇B₂ where R = Nd-Sm (including Yb₃Ni₇B₂) crystallize in the CeCo₄B structure. The space group is P6/mmm and each unit cell contains one formula unit. The detailed crystal structures are discussed. The magnetic measurements show that Yb₃Ni₇B₂ and Lu₃Ni₇B₂ are Pauli paramagnetic. Sm₃Ni₇B₂ is ferromagnetically ordered with a huge intrinsic magnetic hardness. The magnetization at the coercive field at low temperatures is extremely time dependent. The R₃Ni₇B₂ which crystallize in CeNi₃ structure are antiferromagnetic at low temperatures. All Mossbauer and magnetization experimental results can be explained assuming an antiferromagnetic exchange interaction in both 2(c) and 4(f) crystallographic sites and a ferromagnetic interaction between these sites.     

Photoluminescence properties of samarium-doped TiO2 semiconductor nanocrystalline powders

In this work, the luminescence properties of samarium ions-doped titanium dioxide prepared by the sol-gel process were studied. A strong orange red emission (⁴G_5/2−⁶H_7/2 (orange) and ⁴G_5/2-⁶H_9/2 (red)) ascribed to the electron transitions in 4f⁵ configuration of Sm³⁺ ions was observed upon excitation into TiO₂ host. The energy transfer from TiO₂ to Sm³⁺ was verified and the relevant mechanism was discussed. In addition, the impacts of metal ion codopants upon the TiO₂:Sm³⁺ luminescence properties were studied. The results indicated that the central excitation band shifted to blue in the bismuth-codoped materials (0.5-4% in molar ratio), while it shifted to red in the zirconium-codoped materials. Such materials may find applications in white light-emission diode (LED) and tunable solid lasers.     

Synthesis and photoluminescence properties of Sm-doped CaWO4 nanoparticles

The Sm³⁺-doped CaWO₄ nanoparticles were synthesized by hydrothermal method. The room temperature photoluminescence (PL) spectra of Sm³⁺-doped CaWO₄ nanoparticles doped with different Sm³⁺ concentrations under 405 nm excitation have been investigated. The PL spectra showed four strong emission peaks at 460, 571, 609, and 653 nm. The first emission peak at 460 nm could be due to a structural defect of the lattice, an oxygen-deficient WO₃ complex. The other three emissions at 571, 609, and 653 nm were due to the f-f forbidden transitions of the 4f electrons of Sm³⁺, corresponding to ⁴G_5/2→⁶H_5/2 (571 nm), ⁶H_7/2 (609 nm), and ⁶H_9/2 (653 nm), respectively. In addition, the optimum Sm³⁺ concentration in CaWO₄ nanoparticles for optical emission was determined to be 1.0%. The Sm³⁺⁴G_5/2→⁶H_7/2 (609 nm) emission intensity of Sm³⁺-doped CaWO₄ nanoparticles significantly increased with the increase of Sm³⁺ concentration, and showed a maximum when Sm³⁺ doping content was 1.0%. If Sm³⁺ concentration continued to increase, namely more than 1.0%, the Sm³⁺⁴G_5/2→⁶H_7/2 emission intensity would decrease. The present materials might be a promising phosphor for white-light LED applications.     

属特殊结构系列的若干碳化硅多型体的晶体结构

碳化硅(SiC)是典型的层状结构化合物。到目前为止,已发现了150种以上的多型体。作者曾发展了一种特殊的劳厄法可有效地鉴定碳化硅多型体。这种方法,我们发现了85种碳化硅新多型体。为了测定其中一些多型体的结构,拍摄了回摆和魏森堡照相作结构分析,但没有成功。因为这些照相中只有一些基本类型6H,15R和8H的衍射斑点而没有高层多型体的斑点,这是由于新多型体在晶体中含量很少且这些薄晶体多型体处于基本类型6H,8H,15R中间的缘故。本文提出了一种测定碳化硅多型体晶体结构的劳厄法。提出了计算劳厄斑点衍射强度的方法。对结构系列[(33)_m32]₃,[(33)_m34]₃,[(22)_m23]₃和[(44)_m43]₃多型体的结构因子F_hkl的计算方法作了简化。利用这种方法对9种碳化硅新多型体的晶体结构作了测定,其结构用z字形堆垛(Жданов符号)表示时为231R:[(33)₁₂32]₃,249R:[(33)₁₃32]₃,321R:[(33)₁₇32]₃, 339R:[(33)₁₈32]₃,237R:[(33)₁₂34]₃,417R:[(33)₂₂34]₃, 453R:[(33)₂₄34]₃,93R:[(44)₃43]₃,261R:[(44)₁₀43]₃。 关键词：     

Magnetic and magnetocaloric properties of Gd1−xScxNi2 solid solutions

Magnetic and heat capacity measurements have been carried out on the polycrystalline Gd_1−xSc_xNi₂ solid solutions (0≤x≤1), which crystallize in the cubic C15 Laves phases superstructure (space group F4?3m). These solid solutions are ferromagnetic with a Curie temperature below 76 K. Their Curie temperature decreases from 75.4 K for GdNi₂ to 13.6 K for Gd_0.2Sc_0.8Ni₂. At high temperatures, all solid solutions, except ScNi₂, are Curie-Weiss paramagnets. The Debye temperature as well as phonon, conduction electron and magnetic contributions to the heat capacity have been determined from heat capacity measurements. The magnetocaloric effect has been estimated both in terms of isothermal magnetic entropy change and adiabatic temperature change for selected solid solutions in magnetic fields up to 3 T.     

Structure and properties of CaNb2O6:Sm3+ thin films by pulsed laser deposition

CaNb₂O₆:Sm³⁺ films were prepared on quartz glass and α-Al₂O₃(001) substrates by pulsed laser deposition. The structural, morphological, and optical properties of the CaNb₂O₆:Sm³⁺ films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), emission-scan electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and photoluminescence spectroscopy (PL) measurements. The results show that the structure and properties of CaNb₂O₆:Sm³⁺ films were dependent on substrates. The CaNb₂O₆:Sm³⁺ films on Al₂O₃(0001) substrate have better crystallinity. The full-width at half-maximum (FWHM) of (131) peak are 0.45 and 0.32 for the CaNb₂O₆:Sm³⁺ film on glass and Al₂O₃(001), respectively. The crystallite size of CaNb₂O₆:Sm³⁺ films grown on glass and Al₂O₃(001) was about 8.22 and 9.98 nm, respectively. The oxidation state of the Sm element on the films was Sm³⁺ state. The photoluminescence (PL) spectra were measured at room temperature, the CaNb₂O₆:Sm³⁺ films on Al₂O₃(001) substrate have a better PL intensity, the identified emission bands were by the intra 4f transitions of Sm³⁺ from the excited level to the lower levels at 567 nm for ⁴G_5/2→⁶H_5/2 transition, at 609 nm for ⁴G_5/2→⁶H_7/2 transition, and at 657 nm for ⁴G_5/2→⁶H_9/2 transition.     

Formation of long-period nanostructural phases in Ni<Subscript>2</Subscript>MnGa-based <Emphasis Type="Italic">L</Emphasis>2<Subscript>1</Subscript> alloys with thermoelastic martensitic transitions

The crystalline structures of martensite phases in Ni₂MnGa-based ternary alloys have been studied in a wide range of temperatures and compositions transmission and scanning electron microscopy, X-ray diffraction, and electron diffraction. It is found that long-period nanostructural phases with thin-plate morphology are formed as a result of martensitic transformation in Ni₂MnGa-based alloys.     

Enhanced photoluminescence of Sm/Bi co-doped Gd2O3 phosphors by combustion synthesis

Gd₂O₃:Sm³⁺ and Gd₂O₃:Sm³⁺,Bi³⁺ powders were prepared by a combustion method. Their structures were determined using X-ray diffraction. UV-visible absorption and photoluminescence spectra were investigated for Gd₂O₃:Sm³⁺ and Gd₂O₃:Sm³⁺,Bi³⁺ at different annealing temperatures and different doping concentrations. The emission spectra of all samples presented the characteristic emission narrow lines arising from the ⁴G_5/2→⁶H_J transitions (J=5/2, 7/2, and 9/2) of Sm³⁺ ions upon excitation with UV irradiation. The emission intensity of Sm³⁺ ions was largely enhanced with introducing Bi³⁺ ions into Gd₂O₃:Sm³⁺ and the maximum occurred at a Bi³⁺ concentration of 0.5 mol%. The relevant mechanisms were discussed with the sensitization theory by Dexter and the aggregation behavior of Bi³⁺ ions.     

Synthesis and photoluminescence properties of Dy3+, Sm3+ activated Sr5SiO4Cl6 phosphor

Dy³⁺ and Sm³⁺ doped Sr₅SiO₄Cl₆ phosphors were prepared by the modified solid state method and their luminescent properties were studied. From a powder X-ray diffraction (XRD) analysis the formation of Sr₅SiO₄Cl₆ was confirmed. In the photoluminescence emission spectra, the Sr₅SiO₄Cl₆:Dy³⁺ phosphors show efficient blue and yellow band emissions, which originates from the ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions of Dy³⁺ ion, respectively. Photoluminescence properties of Sm³⁺ doped Sr₅SiO₄Cl₆ phosphor exhibited characteristic orange-red emission coming from the intra-4f-shell ⁴G_5/2 →⁶H_J electron transitions.     

Synthesis of α -SiC nanocrystals by carbothermal reduction of spherical nanoparticles of amorphous silicon dioxide

The method for carbothermal reduction of spherical particles of amorphous silicon dioxide is developed, and hexagonal α-SiC polytype nanocrystals are synthesized. The prepared samples are characterized by X-ray diffraction, Raman spectroscopy, photoluminescence spectroscopy, and electron microscopy. The silicon carbide nanocrystals prepared have sizes in the range 5–50 nm depending on the diameter of initial silicon dioxide particles. A detailed analysis of the positions of the lines in the Raman spectra, their broadening, and shift makes it possible to reliably establish that the samples under investigation predominantly contain the 6H and 4H silicon carbide polytypes and insignificant amounts of the 2H and 3C phases. The 15R and 21R polytypes in the samples are absent. It is noted that the samples are characterized by a substantial size effect: the luminescence intensity of small silicon carbide nanocrystals is more than three times higher than that of large SiC nanocrystals.     

High pressure luminescence study of Sm3+: K–Ba–Al fluorophosphate glass

The luminescence spectra and decay curves for the ⁴G_5/2 level of Sm³⁺ ions in 55.95P₂O₅+14K₂O+6KF+14.95BaO+9Al₂O₃+0.1Sm₂O₃ glass, referred to as PKFBASm01, have been studied as a function of pressure up to 40.5 GPa at room temperature. With the increase in pressure, a continuous red shift of the ⁴G_5/2→⁶H_{9/2, 7/2, 5/2} transitions and a progressive increase in the magnitude of the crystal-field splittings for these transitions are observed. The decay curves for the ⁴G_5/2 level of the Sm³⁺ ions in PKFBASm01 glass are found to exhibit single exponential behavior at ambient pressure and become non-exponential at higher pressures, accompanied by shortening of lifetimes. A generalized Yokoto–Tanimoto model has been used to explain the pressure-induced non-exponential nature of the decay curves.     

Magnetic properties and microstructure of Sm2Fe17−xTax compounds

The magnetic properties and microstructure of cast and annealed Sm₂Fe_17−xTa_x (0 ≤ x ≤ 2) alloys were investigated by means of microstructural, X-ray diffraction and thermomagnetic analysis. A process for obtaining the Sm₂Fe₁₇ phase nearly free of iron in the as-cast state is described. The method consists of adding 5 at% of Ta to the melt. By this addition of Ta to the basic alloy, a two phase structure of the as-cast ingots consisting of Sm₂Fe₁₇ phase and a Pauli paramagnetic hexagonal Laves phase - TaFe₂, can be obtained. X-ray diffraction showed an increase of the lattice spacing dependent upon the tantalum concentration in the alloy, which indicated some solid solubility of Ta in the Sm₂Fe₁₇ phase. Quantitative electron probe microanalysis confirmed the solid solubility of tantalum in the Sm₂Fe₁₇ phase of up to 2.3 (± 0.5) at%. This resulted in an increase of the Curie temperature of the Sm₂Fe_17−x phase, which was determined by means of thermomagnetic analysis.     

Preparation and photoluminescence properties of the Eu2+, Sm3+ co-doped Li2SrSiO4 phosphors

A series of Eu²⁺ and Sm³⁺ co-doped Li₂SrSiO₄ phosphors are prepared by the high temperature solid-state reaction. The morphology, structure and spectroscopic properties of the prepared samples are characterized by scanning electron microscopy, X-ray diffraction, diffuse reflection spectra, photoluminescence spectra and electron paramagnetic resonance spectra, respectively. The effect of Sm³⁺ doping concentration on the photoluminescence intensity of the prepared samples is also investigated. The results indicate that the crystal structure of Li₂SrSiO₄ is not changed with the Eu²⁺, Sm³⁺ co-doping. The spherical-like particle size of the obtained product is about 20–30 nm in diameter. When the Sm³⁺ concentration is 0.3 mol% and the Eu²⁺ concentration is 0.7 mol%, the phosphors show the maximum emission intensity, which is 50% higher than that of Eu²⁺ doped Li₂SrSiO₄. Excited at 420 nm, the phosphor presents a single broad emission band peaking at 558 nm, which is ascribed to the 4f⁶5d¹ → 4f⁷ transitions of Eu²⁺ and ⁴G_5/2 → ⁶H_5/2 and ⁴G_5/2 → ⁶H_7/2 transitions of Sm³⁺. The Commission International de I′Eclairage chromaticity coordinates of Li₂SrSiO₄:0.7 mol% Eu²⁺, 0.3 mol% Sm³⁺ are x = 0.28, y = 0.28.     

A promising novel orange–red emitting SrZnV2O7:Sm3+ nanophosphor for phosphor-converted white LEDs with near-ultraviolet excitation

A novel trivalent samarium doped SrZnV₂O₇ nanophosphors was developed via urea assisted solution combustion method using metal nitrates as initial raw materials. The qualitative and quantitative phase analysis was carried out using Rietveld refinement technique. It was found to crystallize in monoclinic lattice with the P12₁/n1 (14) space group. The photoluminescent spectral study of SrZnV₂O₇:Sm³⁺ revealed that the excitation of 405 nm yields the characteristic emission peaks at 569, 599, 640 and 702 nm due to ⁴G_5/2→⁶H_5/2, ⁴G_5/2→⁶H_7/2, ⁴G_5/2→⁶H_9/2 and ⁴G_5/2→⁶H_11/2 respectively. The optimum concentration of Sm³⁺ ion in SrZnV₂O₇ for best luminescence was found to be 2 mol%. The luminescence intensity was further enhanced by incorporating compensator charge R⁺ (R=Li, Na, and K) into the SrZnV₂O₇:0.02Sm³⁺ nanophosphor. The critical distance for non-radiative energy transfer was calculated to be 26.64 Å. Dipole–dipole (d–d) interactions were ascribed as the major factor responsible for concentration quenching arising from the over-doping of the activator ions. The results indicate that these nanophosphors are suitable candidate for PC-WLEDs using near UV excitation.