Dilatometric studies of phase transition in NaNH4SeO4·2H2O single crystal

Thermal expansion of NaNH₄SeO₄SeO₄2H₂O crystal was measured by means of dilatometric method along three crystallographic axes in the temperature range of 300-140 K. Anomalies of relative expansion and thermal expansion coefficients related to ferroelectric phase transition were observed and confirmed its continuous character.     

Phase transition of Eu2Ti2O7 under high pressure and a new ferroelectric phase with perovskite‐like layered structure

Ferroelectrics with perovskite‐like layered (PL) structure are well‐known for their high T_c and the application prospect of high‐temperature‐piezoelectric sensing. In this study, the PL‐structure Eu₂Ti₂O₇ was prepared by 1‐step high‐pressure sintering, which show the pyrochlore structure of Eu₂Ti₂O₇ would change into PL structure at 11 GPa, 1300°C. The PL‐structure Eu₂Ti₂O₇ is metastable, which will change back to pyrochlore structure at about 900°C in the air. The PL‐structure Eu₂Ti₂O₇ was confirmed as a high‐temperature ferroelectric material for the first time. The ferroelectric domain switching was directly observed using piezoelectric force microscope. The piezoelectric constant of the PL Eu₂Ti₂O₇ ceramic was measured as 0.7‐0.9 pC/N and its thermal depoling temperature (T_d) was determined as 800°C, which is associated with the PL‐pyrochlore transition.     

High‐pressure synthesis of a 12CaO·7Al2O3–12SrO·7Al2O3 solid solution

Solid solutions of 12CaO·7Al₂O₃ (C12A7) and 12SrO·7Al₂O₃ (S12A7) crystals were synthesized under high pressure. X‐ray diffraction patterns revealed that the lattice constants of the synthesized samples depend linearly on the compositional ratio of C12A7 and S12A7. Electron‐probe X‐ray microanalyses show that the chemical compositions of the crystals are represented by xC12A7·(1?x)S12A7 (0<x<1). These results indicate that the variation in the lattice constants is originated from a difference in the ionic radii of Ca²⁺ and Sr²⁺ ions. From impedance measurements, it was found that S12A7 has the highest conductivity (~1 × 10^?3 Scm^?1 at 550°C) among the solid solutions in the C12A7–S12A7 system.     

High‐pressure behavior of (Cs,K)Al4Be5B11O28 (londonite): A single‐crystal synchrotron diffraction study up to 26 GPa

The compressional behavior and the P‐induced deformation mechanisms at the atomic scale of (Cs,K)Al₄Be₅B₁₁O₂₈ (londonite, a ~7.31 Å and space group P3m) were investigated by in situ single‐crystal synchrotron X‐ray diffraction with a diamond anvil cell up to 26 GPa. No phase transition was observed within the P‐range investigated: this material exhibits isotropic compression (i.e., with cubic symmetry) in response to the applied pressure. Fitting the P–V data with a Birch‐Murnaghan isothermal equation of state, we obtained: V₀=390.8(3) ų, K_P0=212(7) GPa (β₀=1/K_P0=0.0047(1) GPa^?1) and K′=4.6(6). A series of structural refinements, based on the high‐pressure intensity data, were performed. The stiffness of londonite (similar to that of carbides) is governed by its close‐packing structure, and in particular by the very low compressibility of B‐ and Be‐tetrahedra and the modest compressibility of the Al‐octahedra. The Cs‐polyhedra are the most compressible units of the structure. The effects of pressure can be accommodated by intrapolyhedral compression or deformation, leading to a modest bulk compression. The high amount of boron in londonite (B₂O₃ ~50 wt%) makes its synthetic counterpart a potential neutron absorber. In addition, the high content of Cs makes londonite‐type materials as potential hosts for nuclear waste.     

Structural phase transition and high temperature phase structure of Friedels salt, 3CaO · Al2O3 · CaCl2 · 10H2O

Friedels salt, the chlorinated compound 3CaO · Al₂O₃ · CaCl₂ · 10H₂O (AFm phase), presents a structural phase transition at about 30°C from a monoclinic to a rhombohedral phase. It has been studied by X-ray powder diffraction and optical microscopy in transmitted light with crossed polarisers on single crystals prepared by hydrothermal synthesis. The high temperature phase was determined at 37°C from X-ray single crystal diffraction data. The compound crystallises in the space group R c with lattice parameters of a = 5.7358(6)Å and c = 46.849(9)Å (Z = 3 and D_x = 2.111 g/cm³). The refinement of 498 independent reflections with I > 2σ(I) led to a residual factor of 7.1%. The Friedels salt can be described as a layered structure with positively charged main layers of composition [Ca₂Al(OH)₆]⁺ and negatively charged layers of composition [Cl⁻,2H₂O]. The chloride anions are surrounded by 10 hydrogen atoms, of which six belong to hydroxyl groups and four to water molecules. The structural phase transition may be related to the size of the chloride anions, which are not adapted to the octahedral cavity formed by bonded water molecules.     

The influence of phase transition on electrocaloric effect in lead‐free (Ba0.9Ca0.1)(Ti1−xZrx)O3 ceramics

In this paper, the influence of phase evolution on polarization change and electrocaloric response in lead‐free (Ba_0.9Ca_0.1)(Ti_1?xZr_x)O₃ ceramics (BCTZ) was systematically investigated. With increasing Zr/Ti ratio, the phase structure and phase transition behavior were greatly changed, resulting in various temperature and electric field dependence of electrocaloric responses. For x=0.05, a peak electrocaloric temperature change 1.64 K (at 130°C) and corresponding entropy change 1.78 J·kg^?1·K^?1 were obtained for 0‐7 kV·mm^?1 electric field. Negative electrocaloric temperature change in ?0.1 K was obtained below Curie temperature (T_c), which may be induced by the orthorhombic‐tetragonal ferroelectric phase transition. With the increase in x, the peak value of the electrocaloric response decreased but much better temperature stability was observed. Simultaneously the negative electrocaloric response gradually disappeared with the disappearance of the low temperature ferroelectric‐ferroelectric phase transition. For x=0.2, electrocaloric response showed good temperature stability ranging from room temperature to 130°C, attributing to the relaxor ferroelectric feature.     

Dielectric and dilatometric studies of (CH3)2NH2Ga(SO4)2 · 6H2O (DMAGaS)

The results of dielectric, pyroelectric, spontaneous polarization and dilatometric investigations in the temparature interval 110 K-295 K are presented for DMAGaS crystal. At both phase transition temperature, 136 K and 116 K, discontinuous changes of dielectric permittivity, spontaneous polarization and length of bars are observed. Temperature dependences of alongation along the ferroelectric direction and of spontaneous polarization are quite similar.     

A green process for recovery of H2SO4 and Fe2O3 from FeSO4·7H2O by modeling phase equilibrium of the Fe(П)– –H+–Cl– system

Ferrous sulfate heptahydrate FeSO₄·7H₂O is a major waste produced in titanium dioxide industry by the sulfate process and has caused heavy environmental problem. A new green process for the treatment of FeSO₄·7H₂O was proposed to make use of iron source and recycle sulfate source as H₂SO₄. It was found that by adding concentrated HCl to the FeSO₄ solution, FeCl₂·4H₂O was crystallized out, which was subsequently calcined to produce Fe₂O₃ and HCl. Concentrated H₂SO₄ solution (about 65 wt %) was obtained by evaporating the FeCl₂·4H₂O‐saturated filtrate. To facilitate the process development and design, the solubilities of FeCl₂·4H₂O in HCl, H₂SO₄, and HCl + H₂SO₄ solutions were measured and the experimental data were regressed with both the mixed‐solvent electrolyte model and the electrolyte NRTL model. On the basis of the prediction of the optimum conditions for the crystallization of FeCl₂·4H₂O, material balance of the new process was calculated. FeCl₂·4H₂O and Fe₂O₃ were obtained from a laboratory‐scale test with about 70% recovery of ferrous source for a single cycle, indicating the feasibility of the process. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4549–4563, 2017     

Enhanced thermal stability of piezoelectricity in lead-free (Ba,Ca)(Ti,Zr)O3 systems through tailoring phase transition behavior

Good thermal stability in lead-free BaTiO₃ ceramics is important for their applications above room temperature. In this study, thermal stable piezoelectricity in lead-free (Ba,Ca)(Ti,Zr)O₃ ceramics was enhanced by tailoring their phase transition behaviors. Comparison between (1-x)Ba(Ti_0.8Zr_0.2)O₃-x(Ba_0.65Ca_0.35)TiO₃ and (1-y)Ba(Ti_0.8Zr_0.2)O₃-y(Ba_0.95Ca_0.05)TiO₃ revealed that latter system at y?=?0.80 had much better thermal stable piezoelectric coefficient than the former at x?=?0.45. Both systems crystalized in tetragonal to orthorhombic phase boundary at room temperature. The phase transition temperature and degree of diffusion were adjusted by Ca and Zr ions contents and demonstrated great influence on temperature dependent dielectric permittivity, hysteresis loops, and in-situ domain structures. The improved thermal stability of (1-y)Ba(Ti_0.8Zr_0.2)O₃-y(Ba_0.95Ca_0.05)TiO₃ prepared at y?=?0.80 was linked to its higher paraelectric to ferroelectric phase transition temperature (T_m?=?115.7?°C) and less degree of diffusion (degree of diffusion constant γ?=?1.35). By comparison, (1-x)Ba(Ti_0.8Zr_0.2)O₃-x(Ba_0.65Ca_0.35)TiO₃ prepared at x?=?0.45 revealed T_m?=?81.3?°C and γ?=?1.65. Overall, these findings look promising for future stimulation of phase transition behaviors and design of piezoelectric materials with good thermal stabilities.     

Global phase behavior of imidazolium ionic liquids and compressed 1,1,1,2‐tetrafluoroethane (R‐134a)

Novel processes involving ionic liquids with refrigerant gases have recently been developed. Here, the complete global phase behavior has been measured for the refrigerant gas, 1,1,1,2‐tetrafluoroethane (R‐134a) and 1‐n‐alkyl‐3‐methyl‐imidazolium ionic liquids with the anions hexafluorophosphate [PF₆], tetrafluoroborate [BF₄] and bis(trifluoromethylsulfonyl)imide [Tf₂N] from ～0°C to 105°C and to 33 MPa. All of the systems studied were Type V from the classification scheme of Scott‐van Konynenburg with regions of vapor‐liquid equilibrium, miscible/critical regions, vapor‐liquid‐liquid equilibrium, and upper and lower critical endpoints (UCEP and LCEP). The effect of the alkyl chain length has been investigated, for ethyl‐([EMIm]), n‐butyl‐([BMIm]), and n‐hexyl‐([HMIm]). With increasing chain length, the temperature of the lower critical end points increases and pressure at the mixture critical points decrease. With a common cation, the temperature of the LCEP increased and the mixture critical point pressures decreased in the order of [BF₄], [PF₆], and [Tf₂N]. © 2008 American Institute of Chemical Engineers AIChE J, 2009     

Continuous and scale‐up synthesis of high purity H2O2 by safe gas‐phase H2/O2 plasma reaction

A new generation of double dielectric barrier discharge (DDBD) reactor featured by a metal powder (MP) high voltage electrode is presented. The MP high voltage electrode not only has excellent homogeneous discharge performance but also has the advantage of without regular maintenance. Therefore, the MP‐DDBD reactor was proved to be suitable for the uninterrupted and safe synthesis of high purity H₂O₂ aqueous solution with up to 65 wt % concentration from the H₂/O₂ mixture. The scale‐up synthesis of H₂O₂ was successfully attempted in an integrated device based on the MP‐DDBD reactor. The future practical H₂O₂ synthesizer based on the MP‐DDBD reactor will be small and movable, and therefore, be convenient to supply high purity H₂O₂ on site for small scale users like semiconductor industry. © 2013 American Institute of Chemical Engineers AIChE J 60: 415–419, 2014     

Synthesis and Properties of Bi2Fe4O9 with FeCl2·6H2O Addition

Single‐phase Bi₂Fe₄O₉ is synthesized successfully by the solid‐state reaction technique with FeCl₂·6H₂O additives. The two optical band gaps, and the iron ion's chemical valence state both decrease with the addition of FeCl₂·6H₂O, which may be attributed to the decrease in the split energy of iron 3d orbital.     

High‐Performance Small‐Amount Fe2O3‐Doped (K,Na)NbO3‐Based Lead‐Free Piezoceramics with Irregular Phase Evolution

[(K_0.43Na_0.57)_0.94Li_0.06][(Nb_0.94Sb_0.06)_0.95Ta_0.05]O₃ + x mol% Fe₂O₃ (KNLNST + x Fe, x = 0~0.60) lead‐free piezoelectric ceramics were prepared by conventional solid‐state reaction processing. The effects of small‐amount Fe₂O₃ doping on the microstructure and electrical properties of the KNLNST ceramics were systematically investigated. With increasing Fe³⁺ content, the orthorhombic‐tetragonal polymorphic phase transition temperature (T_O‐T) of KNLNST + x Fe ceramics presented an obvious “V” type variation trend, and T_O‐T was successfully shifted to near room temperature without changing T_C (T_C = 315°C) via doping Fe₂O₃ around 0.25 mol%. Electrical properties were significantly enhanced due to the coexistence of both orthorhombic and tetragonal ferroelectric phases at room temperature. The ceramics doped with 0.20 mol% Fe₂O₃ possessed optimal piezoelectric and dielectric properties of d₃₃ = 306 pC/N, k_p = 47.0%, = 1483 and tan δ = 0.023. It was revealed that the strong internal stress in the KNLNST + x Fe ceramics with higher Fe³⁺ contents (x = 0.40, 0.60) stabilized the orthorhombic phase, leading to the irregular “V” type rather than the usually observed monotonic phase transition with composition change in the ceramics.     

298 K 时(NH4)2S2O3-(NH4)2SO4-H2O三元体系相平衡研究

通过改良合成复体法对(NH4)2S2O3-(NH4)2SO4-H2O三元体系在298 K下的溶液相平衡进行研究。利用X-射线粉末衍射法(XRD)表征平衡固相组成。结果证实:该方法能很好地用于(NH4)2S2O3-(NH4)2SO4-H2O三元体系平衡固相组成的分析。依据水、硫酸铵及硫代硫酸铵组成的饱和溶液各组分的质量分数绘制了(NH4)2S2O3-(NH4)2SO4-H2O在298 K下的三元体系相图。依据三元体系相图,结果显示:硫代硫酸铵的结晶区远远大于硫酸铵的结晶区,同时在该温度下,硫代硫酸铵、硫酸铵及水形成简单三元体系,体系中没有水合物形成。     

A practical approach to produce Mg‐Al spinel based on the modeling of phase equilibria for NH4Cl‐MgCl2‐AlCl3‐H2O system

Based on chemical modeling of phase equilibria for the NH₄Cl‐MgCl₂‐AlCl₃‐H₂O system, a practical approach to produce Mg‐Al spinel (MgAl₂O₄) (widely used as refractory brick, supports in catalysts, and inert material for oxygen carriers) is proposed and proven feasible. This novel process includes coprecipitation of Mg₄Al₂(OH)₁₄·3H₂O from the NH₃‐MgCl₂‐AlCl₃‐H₂O system; calcination of Mg₄Al₂(OH)₁₄·3H₂O to obtain Mg‐Al spinel and recovery of NH₄Cl from NH₄Cl‐rich solutions by feeding MgCl₂‐AlCl₃. A MSMPR reactor was applied to investigate the effect of temperature, feed concentration, and NH₄Cl addition on coprecipitation of precursor Mg₄Al₂(OH)₁₄·3H₂O from MgCl₂‐AlCl₃ solutions with Mg/Al ratio = 2 through gradual addition of NH₄OH. The phase equilibria of the NH₄Cl‐MgCl₂‐AlCl₃‐H₂O system were determined over the temperature range 283.2 to 363.2 K using dynamic method. The experimental solubilities were regressed to obtain new Bromley‐Zemaitis model parameters. These newly obtained parameters were verified by predicting the quaternary system. A chemical model for the NH₄Cl‐MgCl₂‐AlCl₃‐H₂O system has been established with the OLI platform. All the results generated from this study will provide the theoretical basis for Mg‐Al spinel production. The high quality Mg‐Al spinel was prepared by calcination of precursor from 773.2 to 1273.2 K, and the NH₄Cl was successfully recovered through the common ion effect of MgCl₂‐AlCl₃ addition. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1855–1867, 2013     

Synthesis,structural characterization,and photoluminescence properties of Eu3+‐doped Mg3‐xEux(BO3)2 phosphor

Eu³⁺‐doped Mg_3‐xEu_x(BO₃)₂ (x = 0.000, 0.005, 0.010, 0.020, 0.050, and 0.100) phosphors were synthesized for the first time by solution combustion synthesis method, which is a fast synthesis method for obtaining nano‐sized borate powders. The optimization of the synthesis conditions of phosphor materials was performed by TG/DTA method. These phosphors were characterized by XRD, FTIR, SEM‐EDX, and photoluminescence, PL analysis. The XRD analysis exhibited that all of the prepared ceramic compounds have been crystallized in orthorhombic structure with space group Pnnm. Also, the influence of europium dopant ions on unit cell parameters of host material was analyzed using Jana2006 program and the crystalline size was determined by Debye‐Scherrer's formula. The luminescence properties of all Eu³⁺‐doped samples were investigated by excitation and emission spectra. The excitation spectra of Mg_3‐xEu_x(BO₃)₂ phosphors show characteristic peak at 420 nm in addition to other characteristic peaks of Eu³⁺ under emission at 613 nm. The emission spectra of Eu³⁺‐doped samples indicated most intensive red emission band dominated at 630 nm belonging to ⁵D₀→⁷F₂ magnetic dipole transition. Furthermore, the optimum or quenching concentration of Eu³⁺ ion has been determined as x = 0.010 showed the maximum emission intensity when it was excited at 394 nm.     

Piezoelectric properties of (Na0.5K0.5)(Nb1‐xSbx)O3‐SrTiO3 ceramics with tetragonal‐pseudocubic PPB structure

CuO‐added 0.96(Na_0.5K_0.5)(Nb_1‐xSb_x)O₃‐0.04SrTiO₃ ceramics sintered at the low temperature of 960°C for 10 hours showed dense microstructures and high relative densities. The specimens with 0.0 ≤  x ≤ 0.04 had orthorhombic‐tetragonal polymorphic phase boundary (PPB) structure. Tetragonal‐pseudocubic PPB structure was observed in specimens with 0.05 ≤  x ≤ 0.07, while the specimen with x = 0.08 has a pseudocubic structure. The structural variation in the specimens is explained by the decreases in the orthorhombic‐tetragonal transition temperature and Curie temperature with the addition of Sb⁵⁺ ions. The specimens with 0.05 ≤  x ≤ 0.07, which have tetragonal‐pseudocubic PPB structure, had large electric field‐induced strains of 0.14%‐0.016%. Moreover, these specimens also showed increased d₃₃ values between 280 pC/N and 358 pC/N. In particular, the specimen with x = 0.055 showed particularly enhanced piezoelectric properties: d₃₃ of 358 pC/N, k_p of 0.45, and the electric field‐induced strain of 0.16% at 4.5 kV/mm.     

Structural characterization of a layered double salt Mn3(OH)2(SO4)2(H2O)2 · K2SO4

The title layered double salt Mn₃(OH)₂(SO₄)₂(H₂O)₂ · K₂SO₄ (1) was obtained from a simple hydrothermal reaction of CdSO₄ · 8/3H₂O, MnCl₂ · 4H₂O, α-aminopyridine (apy) and KI. X-ray analysis reveals that the two-dimensional (2-D) sheet of 1 is built up of the dimers of edge-sharing Mn(1) octahedral, extended by the apices of Mn(2) octahedral together with μ₃ and μ₄ SO₄ groups. With free K⁺ ion as guest species, the 2-D sheets are further self-assembled into a 3-D supramolecular network with 1-D channels through the Ow-H ⋯ O hydrogen-bonded interactions. The magnetic property of 1 was investigated, and a classical behavior is observed with an antiferromagnetic order below 12.5 K.     

Hydrothermal synthesis,crystal structure and photoluminescent property of a novel 3-D [La2(C2O4)2(NO3)(OH)(H2O)] · 3H2O

A novel 3D [La₂(C₂O₄)₂(NO₃) (OH)(H₂O)] · 3H₂O 1 has been synthesized under hydrothermal conditions and characterized by elemental analyses, IR, TGA, X-ray powder diffraction, X-ray single crystal diffraction and photoluminescence. The bridging modes of both nitrates and oxalates in compound 1 are uncommon. We have unexpectedly generated an unusual compound by using the simplest ligands, oxalates and nitrates in the presence of nicotinate (HIN).