Temperature‐dependent Raman scattering studies of Na2MoO4

The mode assignment of the cubic phase of anhydrous Na₂MoO₄ was carried out on the basis of lattice dynamic calculation using the classical rigid‐ion model. Temperature‐dependent studies indicate that this crystal remains in the cubic structure in the 15–773 K range and undergoes a phase transition at around 783 K. The behavior of the Raman modes indicates that this transition is strongly first‐order in nature and the phase above 773 K may have an orthorhombic symmetry. This transition is connected with tilting and/or rotations of the MoO₄ tetrahedra, which lead to a disorder at the MoO₄ sites. Our results give also evidence that the Mo O bond lengths decrease in the high‐temperature phase. Copyright © 2008 John Wiley & Sons, Ltd.     

Temperature‐dependent Raman scattering studies on Na2Mo2O7 disodium dimolybdate

Temperature–dependent Raman studies of disodium dimolybdate (Na₂Mo₂O₇) crystal are reported. Lattice dynamical calculation was used to predict both wavenumbers and atomic displacements (eigenvectors) for the vibrational modes. These calculations were based on the classical rigid‐ion model. The high‐temperature Raman scattering study of the crystal showed that it remains in the orthorhombic structure in the 8–848 K range and undergoes a structural phase transition between 848 and 854 K. This phase transition is most likely connected with weak tiltings and/or rotations of both MoO₄ (tetrahedra) and MoO₆ (octahedra) units, which lead to a disorder in the oxygen sublattice. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectroscopy study of Na2MoO4·2H2O and Na2MoO4 under hydrostatic pressure

Raman spectroscopy measurements of polycrystalline Na₂MoO₄·2H₂O (NMHO) and Na₂MoO₄ (NM) under hydrostatic pressure (from 0 to 10 GPa) were performed. This study allowed us to monitor the stretching and bending vibrations of MoO₄ ions as well as the translational modes as a function of pressure. The pressure dependence of the wavenumbers of the modes indicates that the Na₂MoO₄·2H₂O undergoes two phase transitions at about ∼3 and ∼4 GPa. When releasing pressure, we have observed that the original spectrum is recovered, thereby pointing to a reversible process. The Na₂MoO₄ (NM) starting phase was found to be stable up to 10 GPa. The pressure‐dependent Raman data for NM did not reveal any structural modification. The influence of the pressure‐transmitting medium on the phase transitions is also discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

High‐pressure polarized Raman spectra of Gd2(MoO4)3: phase transitions and amorphization

Polarized Raman spectra of a single crystal of gadolinium molybdate [Gd₂(MoO₄)₃] were obtained between 1 atm and 7 GPa. Using a mixture of alcohols as the pressure‐transmitting medium, YY, ZZ, XY components of scattering matrices were measured. The ZZ spectra were also obtained in argon. Five phase transitions and amorphization were identified. The first and second transitions are reversible, while amorphization is not. In alcohol, amorphization is observed above 6.5 GPa. With argon as the pressure‐transmitting medium, amorphization is progressive and begins above 3 GPa. The spectral changes with pressure affect the high wavenumber bands attributed to symmetric and antisymmetric MoO₄ stretching modes as well as the very low wavenumber modes such as librations of the tetrahedra. This means that both short‐range and long‐range organizations of the tetrahedra are involved in these phase transitions. The amorphization mechanism and its dependence on the pressure‐transmitting medium are discussed, and the steric hindrance between polyhedra is believed to be the most relevant mechanism. The TO and LO low wavenumber modes of A₁ symmetry, observed in the Y(ZZ)Y and Z(YY)Z geometries, respectively, below 50 cm⁻¹, soften continuously through the first three phases when increasing pressure. The strong A₂ mode observed in the Z(XY)Z spectra exhibits the same anomalous behavior by decreasing from 53 to 46 cm⁻¹ at 2 GPa. The softening of these modes is related to the orientation change of tetrahedra observed by ab initio calculations when the volume of the cell is decreased. These orientation changes can explain the wavenumber decrease of the Mo O stretching modes above 2 GPa, which indicates an increase of Mo coordination. Copyright © 2010 John Wiley & Sons, Ltd.     

Pressure‐induced structural transformations in In2‐xYx(MoO4)3 systems

In this work, we report results of high‐pressure Raman experiments (P < 8 GPa) on In_2‐xY_xMo₃O₁₂ for x = 0.0 and 0.5. A crystalline to crystalline structural phase transition and pressure‐induced amorphization (PIA) have been identified. The structural phase transition takes place at 1.5 and 1.0 GPa for In₂(MoO₄)₃ and In_1.5Y_0.5(MoO₄)₃, respectively, resulting in the change of structure from monoclinic P2₁/a to a more denser structure. The PIA started at 5 and 3.4 GPa for In₂Mo₃O₁₂ and In_1.5Y_0.5Mo₃O₁₂, respectively. The amorphization process takes place in two stages in the case of In_1.5Y_0.5Mo₃O₁₂ phase, while for In₂Mo₃O₁₂, it is not complete until the pressure is as high as 7 GPa. Our results also suggest that with increase of ionic size of the A³⁺ ions, the octahedral distortion increases and consequently larger local structural disorder is introduced in the A₂(MoO₄)₃ system, where A is a trivalent ion (In, Y³⁺, Sc³⁺, Fe³⁺, etc.). Copyright © 2015 John Wiley & Sons, Ltd.     

Pressure-induced structural and electronic transition in KTb(MoO4)2 through Raman and optical studies

Raman and optical absorption studies under pressure have been conducted on KTb(MoO₄)₂ up to 35.5 GPa. A phase transformation occurs at 2.7 GPa when the crystal is pressurized at ambient temperature in a hydrostatic pressure medium. The sample changes to a deep yellow color at the transition and visibly contracts in theα-axis direction. The color shifts to red on further pressure increase. The Raman spectral features and the X-ray powder pattern change abruptly at the transition indicating a structural change. The pressure-induced transition appears to be a property of the layer-type alkali rare earth dimolybdates. However, the color change at the transition in KTb(MoO₄)₂ is rather unusual and is attributed to a valence change in Tb initiated by the structural transition and consequent intervalence charge transfer between Tb and Mo.In situ high pressure X-ray diffraction data suggest that phase II could be orthorhombic with a unit cell having 3 to 4% smaller volume than that of phase I.     

Temperature‐dependent Raman scattering study of multiferroic MnWO4

We have measured polarized Raman spectra of MnWO₄ single crystals at low temperatures, and studied the temperature dependence of the various phonon modes. From our Raman studies of the MnWO₄, a new transition temperature, ∼180 K, was found. We have completely assigned the symmetries of the 18 observed Raman modes of the MnWO₄, as expected from a group theoretical analysis. These Raman modes have been classified into three groups according to weak, intermediate and strong temperature dependence of the modes in each group. Six internal modes have been identified by their weak temperature dependence of the Raman wavenumbers. The temperature dependence of the wavenumbers of the B_g modes in Mg O bonds, modes of intermediate temperature dependence group, shows an anomalous behavior under 50 K. The phonon modes of strong temperature dependence show an anomalous change at ∼180 K in the linewidths. This is believed to be a new transition temperature which involves the changes in the inter‐WO₆ octahedra structure. Copyright © 2009 John Wiley & Sons, Ltd.     

Pressure‐induced phase transitions in palmitic acid: C form

In this article, we report a high‐pressure Raman spectroscopy study of palmitic acid (PA, C form) from ambient pressure up to 21 GPa. The effects of hydrostatic pressure on the vibrational spectrum of PA are reported, and the data show that PA experiences a rich sequence of phase transformations. These changes in the crystal structure occur gradually as the pressure increases and they are related to the highly flexible crystalline structure. Copyright © 2011 John Wiley & Sons, Ltd.     

Temperature‐dependent low wavenumber Raman scattering studies in LiCsSO4 crystal

The Raman lattice modes in the LiCsSO₄ crystal were measured in the temperature range of 17–303 K. Two right‐angle scattering geometries were used: z(xx)y and z(xz)y, to observe A_g and B_g (or B_2g) modes, respectively. Critical phenomena were observed in the spectra at temperatures of about 200, 180 and 100 K. They correspond to structural phase transitions in the crystal from D_2h to C_2h at 200 K and to C_s symmetry at 100 K. The nature of the transition at 180 K is supposed to be of a lock‐in type, but it needs further investigation. Copyright © 2010 John Wiley & Sons, Ltd.     

Ca$lt;sub$gt;0.64$lt;/sub$gt;WO$lt;sub$gt;4$lt;/sub$gt;:Eu$lt;sub$gt;0.24$lt;/sub$gt;陶瓷的高温相变机理及其对发光性能的影响

纯的CaWO₄具有优异的耐压、耐热稳定性,化学组成为Ca_0.64WO₄:Eu_0.24的陶瓷也具有CaWO₄结构,但Ca²⁺晶格位置含有12 mol%的肖特基缺陷. 这种缺陷浓度高的CaWO₄ 相是否具有良好的高温稳定性还有待研究. 本文探讨了过度烧结对Ca_0.64WO₄:Eu_0.24陶瓷相结构的影响,揭示了在高温下产生相变的可能原因,并研究了该相变对材料发光性能的影响. 研究表明,当烧结温度超过1100 ℃时,被肖特基缺陷束缚的部分氧离子会解离,造成Ca_0.64WO₄:Eu_0.24陶瓷体相中氧元素含量严重不足,诱发CaWO₄相发生相变,析出单斜晶系的Eu₂WO₆;研究还发现,CaWO₄相的晶面间距在高温相变后会增大;这可能是导致Ca_0.64WO₄:Eu_0.24陶瓷发光强度显著降低的一个重要原因. 关键词： 相变 钨酸钙 铕 发光     

新型红色荧光粉NaLa_(0.7)(MoO_4)_(2-x)(WO_4)_x∶0.3Eu~(3+)的制备及发光性质研究

采用高温固相法合成具有余辉性能的发光材料NaLa_(0.7)(MoO_4)_(2-x)(WO_4)_x∶0.3Eu~(3+)(x=0,0.5,1,1.5,2)。用X射线衍射(XRD)和荧光光谱对样品的晶体结构和发光特性进行表征。测试结果表明,在900℃下烧结8 h所合成的NaLa_(0.7)(MoO_4)_(2-x)(WO_4)_x∶0.3Eu~(3+)样品为纯相Na La(Mo O_4)_2,样品可被近紫外光393nm和蓝光462 nm有效激发,其发射主峰位于615 nm处,属于Eu3+的5D0-7F2跃迁。Na La_(0.7)(Mo O_4)_(2-x)-(WO_4)_x∶0.3Eu~(3+)的发光强度随着W6+浓度的增加而增大,当W6+掺杂量x=1时发光最强,而后随W6+掺杂浓度的增加出现浓度猝灭现象。通过计算得到样品在393 nm和462 nm激发下的色坐标,当W6+的掺杂量x=1时,样品的红光色纯度最好。     

Micro‐Raman study of Zr‐substituted Bi4Ti3O12 ceramics

We have studied the lattice vibrational modes of Zr‐substituted Bi₄Ti₃O₁₂ ceramics using micro‐Raman spectroscopy. Replacement of Zr at the Ti site in the perovskite block is found from the increase in the lattice parameters as a function of Zr contents. Combined X‐ray diffraction patterns and Raman analysis suggested less than 40 mole% Zr solubility in Bi₄Ti₃O₁₂. At 40 mole% of Zr substitution or above, the unreacted monoclinic‐phase ZrO₂ is observed in the X‐ray diffraction patterns and the Raman spectra. The incorporation of Zr in Bi₄Ti₃O₁₂ reduces the soft mode wavenumber and the transition temperature. Moreover, temperature dependent studies confirmed the ferroelectric to paraelectric transition in Bi₄Ti₃O₁₂ at about 675 °C. On increasing the Zr content up to 40% on the Ti sites of Bi₄Ti₃O₁₂, a systematic decrease in the phase transition temperature from 675 to 630 °C was observed. Copyright © 2007 John Wiley & Sons, Ltd.     

Temperature‐dependent Raman spectra of Ba2BiSbO6 ceramics

In this work, we have performed Raman scattering measurements in Ba₂BiSbO₆ ceramics in the temperature range from 10 to 573 K. The Raman spectra were examined using group theory to analyze the decomposition of the reducible representation of the vibrational modes and with a virtual octahedral model. At room temperature, five modes were observed. At low temperatures, the spectra subtly showed the rhombohedral–monoclinic phase transition, which was identified by changes in the Raman intensity of the bending and symmetrical stretching SbO₆ octahedral modes. The cubic–rhombohedral phase transition was not clearly evident in the high‐temperature Raman data. Copyright © 2009 John Wiley & Sons, Ltd.     

A2( MoO4)3(A=Al,Cr,Fe)结构与相变的Raman光谱研究

用XRD、Raman光谱和DSC研究了Al2 (MoO4)3、Cr2( MoO4)3和Fe2 (MoO4)3的结构与相变.Al2(MoO4)3、Cr2 (MoO4)3和Fe2 (MoO4)3在室温下为单斜相,分别在483 K、673 K和783 K附近转变为正交相.发现MO4四面体的对称和反对称伸缩振动模的频率和相对强...     

Pressure induced magnetic and semiconductor–metal phase transitions in Cr_2MoO_6

We investigate magnetic ordering and electronic structures of Cr_2MoO_6under hydrostatic pressure. To overcome the band gap problem, the modified Becke and Johnson exchange potential is used to investigate the electronic structures of Cr_2MoO_6. The insulating nature at the experimental crystal structure is produced, with a band gap of 1.04 eV, and the magnetic moment of the Cr atom is 2.50 μB, compared to an experimental value of about 2.47 μB. The calculated results show that an antiferromagnetic inter-bilayer coupling–ferromagnetic intra-bilayer coupling to a ferromagnetic inter-bilayer coupling–antiferromagnetic intra-bilayer coupling phase transition is produced with the pressure increasing. The magnetic phase transition is simultaneously accompanied by a semiconductor–metal phase transition. The magnetic phase transition can be explained by the Mo–O hybridization strength, and ferromagnetic coupling between two Cr atoms can be understood by empty Mo-d bands perturbing the nearest O-p orbital.     

Temperature‐dependent Raman spectroscopy study in MoO3 nanoribbons

This paper reports a study of vibrational, structural and morphological properties of molybdenum oxide nanoribbons. Temperature‐dependent Raman spectroscopy measurements in MoO₃ nanoribbons revealed morphological changes in the 150–350 °C temperature range. No structural phase transitions were observed, thus showing that the orthorhombic phase is stable from room temperature (nanoribbons) up to 650 °C (bulk‐like phase) where large plates have been formed by the coalescence of the nanoribbons. The interpretation of temperature‐dependent Raman data (wavenumber and linewidths) is supported by scanning electron microscopy that is used to directly probe the morphological changes in MoO₃ samples. The observed phenomena in the Raman data for MoO₃ nanoribbons can be applied to other nanomaterials. Copyright © 2012 John Wiley & Sons, Ltd.     

Raman study of phase transition in ferroelectric Ba0.95Ca0.05TiO3

Raman scattering investigation of phase transition in the ferroelectric Ba_0.95Ca_0.05TiO₃ is reported. The results suggest onset of significant dynamic disorder at 105°C. This corroborates findings of recent structural study regarding large positional disorder associated with Ti and O1 atoms well below the tetragonal to cubic transition temperature (∼150°C).     

Ferroelectric Q and antiferroelectric P phases' coexistence and local phase transitions in oxygen‐deficient NaNbO3 single crystal: micro‐Raman,dielectric and dilatometric studies

Micro‐Raman studies of oxygen‐deficient gray‐colored NaNbO₃ single crystals have shown that at room temperature both antiferroelectric P and ferroelectric Q phases are present simultaneously as separate regions tens of micrometers in size. Phase transitions in P and Q regions have been elucidated by dielectric, dilatometric and micro‐Raman studies. For the first time, the sequence of phase transitions between antiferroelectric phase P and ferroelectric Q and N phases has been revealed. Copyright © 2012 John Wiley & Sons, Ltd.     

ESR evidence of a low-temperature phase transition in Na2SeO4

Abstract

ESR investigations of gamma-irradiated sodium selenate in powder form indicates a number of paramagnetic species as SeO^? ₂, SeO^? ₃, and SeO^? ₄, identified on the basis of their g-tensors. The appearance of a new ESR line at g = 2.0260 attributed to the SeO^? ₄ radical indicates a possible structural phase transition at 165 K in Na₂SeO₄.     

六氯铅铵晶体相变的拉曼散射研究

在５Ｋ～３００Ｋ温度范围内对六氯铅铵晶体进行了拉曼散射测量，该晶体在Ｔｃ＝７８Ｋ发生从立方结构（Ｏ＾５４）至三方结构（Ｃ＾２３ｉ）的二级相变，ＰｂＣｌ＾２－６八面体Ａ１ｇ模和ＮＨ＾＋４四面体Ａ１模的拉曼频移在Ｔｃ时出现极大值，八面体Ｔ２ｇ模，四面体Ｔ２模和外振动Ｔ２ｇ模在Ｔｃ以下发生连续分裂，另外在Ｔｃ以下观测到对应于高温相ＰｂＣｌ＾２－６八面体Ｔ１ｇ模的软模。