Isostructural phase transition (IPT) in CaMoO4 with Scheelite structure

The ceramic compound CaMoO₄ is synthesized via a solid-state reaction technique. Rietveld refinement studies were done on the powder X-ray diffraction data of CaMoO₄ and revealed that the compound is crystallized in the tetragonal Scheelite structure with I4₁/a space group. The differential scanning calorimetry (DSC) studies on CaMoO₄ divulged an anomaly around 440 °C. This anomaly is further probed using the temperature-dependent Raman and dielectric spectroscopic measurements and are corroborating with the results obtained from DSC. A detailed investigation on the temperature-dependent Raman spectroscopic data revealed that the A_1g mode of CaMoO₄ showed a soft phonon behavior up to the phase transition temperature. It is observed that the A_1g mode displayed phonon hardening behavior with further increasing the temperature. The anomaly is attributed to an isostructural phase transition (IPT), a rarely observed phenomenon in the compounds with Scheelite structure. The IPT in CaMoO₄ is elucidated with a phonon softening mechanism.     

Defect control and ionic conductivity of oxynitride perovskite Sr0.83Li0.17Ta0.83O1.88N0.74

Perovskite lattice was tailored by introducing site vacancies and mixed anion composition, to produce Sr_0.83Li_0.17Ta_0.83O_1.88N_0.74 (Li02N). Further, Li02N was converted to a defect oxide Sr_0.83Li_0.17Ta_0.83O₃ (Li02O) by applying an optimized treatment: heating in air at 1173 K for 2 h. According to the neutron Rietveld refinement, Li02N and Li02O are tetragonal and orthorhombic, respectively, where the lattice volume of Li02O is significantly smaller than that of Li02N. The ionic conductivity (σ_ion) of Li02N and Li02O was evaluated by the ac impedance spectroscopy and the equivalent circuit analysis. Both Li02N (σ_ion = 10^?5.5 S/cm at 671 K) and Li02O (σ_ion = 10^?6.2 S/cm at 667 K) exhibited an Arrhenius behavior of ionic conductivity with activation energies of 0.87 eV and 0.75 eV, respectively. It is interpreted that the nitride component enhances the ionic conduction of Li02N, while the vacancy of the anion lattice makes an opposite effect.     

Methods and mechanisms for uniformly refining deformed mixed and coarse grains inside a solution-treated Ni-based superalloy by two-stage heat treatment

The uniform refinement mechanisms and methods of deformed mixed and coarse grains inside a solution-treatment Ni-based superalloy during two-stage annealing treatment have been investigated.The two-stage heat treatment experiments include an aging annealing treatment(AT)and a subsequent recrystallization annealing treatment(RT).The object of AT is to precipitate some δ phases and consume part of storage energy to inhibit the grain growth during RT,while the RT is to refine mixed and coarse grains by recrystallization.It can be found that the recrystallization grains will quickly grow up to a large size when the AT time is too low or the RT temperature is too high,while the deformed coarse grains cannot be eliminated when the AT time is too long or the RT temperature is too low.In addition,the mixed microstructure composed of some abnormal coarse recrystallization grains(ACRGs)and a large number of fine grains can be observed in the annealed specimen when the AT time is 3 h and RT tem-perature is 980℃.The phenomenon attributes to the uneven distribution of δ phase resulted from the heterogeneous deformation energy when the AT time is too short.In the regions with a large number of δ phases,the recrystallization nucleation rate is promoted and the growth of grains is limited,which results in fine grains.However,in the regions with few δ phases,the recrystallization grains around grain boundaries can easily grow up,and the new recrystallization nucleus is difficult to form inside grain,which leads to ACRGs.Thus,in order to obtain uniform and fine annealed microstructure,it is a prereq-uisite to precipitate even-distributed δ phase by choosing a suitable AT time,such as 12 h.Moreover,a relative high RT temperature is also needed to promote the recrystallization nucleation around δ phase.The optimal annealing parameters range for uniformly refining mixed crystal can be summarized as:900℃×12 h+990℃×(40-60 min)and 900℃×12 h+1000℃×(10-15 min).     

Microstructure and electric properties of Pr-doped Pb(Zr0.52Ti0.48)O3 ceramics

Improving the piezoelectric activity of lead zirconate titanate (PZT) ceramics is of great importance for practical applications. In this study, the influence of Pr³⁺ doping on the ferroelectric phase composition, microstructure, and electric properties on the A-site of (Pb_1-1.5xPr_x)(Zr_0.52Ti_0.48)O₃ is extensively investigated. A dense and fine microstructural sample is obtained with the introduction of Pr³⁺. The results show that the morphotropic phase boundary (MPB) moves to the rhombohedral phase region. The rhombohedral and tetragonal phases exhibit an ideal coexistence in the 4 mol.% Pr³⁺ doped (PPZT4) samples. Lead vacancy and the reduction of the potential energy barrier are considered to be the key mechanisms for donor doping, which is upheld by the Pr³⁺ doping. Combining the I-E hysteresis loops with the P-E hysteresis loops, it becomes apparent that both contribution maximums of the domain switching and residual polarisation are in PPZT4. Moreover, the thermal aging resistance of PZT is improved by doping, and the temperature stability is optimised from 83% in PZT to 96% in PPZT4. Hence, an appropriate amount of Pr³⁺ doping can effectively improve the piezoelectric activity of PZT ceramics in the MPB area and optimise the performance stability of the material under application temperatures.     

Electrical polarization and ionic conduction properties of β-tricalcium phosphate bioceramics with controlled vacancies by sodium ion substitution

With the aim to understand electric polarization mechanisms of β-tricalcium phosphate as an advanced biomaterial, Na ion-substituted β-Ca₃(PO₄)₂ (Na-β-TCPs) ceramics with controlled lattice vacancies were synthesized and structural refinement was performed by the Rietveld method. The Rietveld analysis revealed that Ca and vacancies at Ca(4) sites in the β-TCP structure decreased with an increase in Na substitution. Electrical measurements by the complex impedance method revealed that the conductivity and the activation energy calculated from Cole-Cole plots rapidly decreased to a constant value with an increase in Na substitution and decrease in vacancies. The thermally stimulated depolarization current (TSDC) curve of the electrically polarized Na-β-TCP showed one large peak at 530–610 °C. However, the accumulated charge decreased with an increase in Na ions and decrease in vacancies up to 2.37 mol%, after which it became constant. These results are consistent with the presumed formation of a dipole moment between aligned Ca²⁺ ions and their vacancies along the direction of the external polarization field applied at high temperature. We conclude that the large amount of stored charge in β-TCP caused by electrical polarization is due to the low site occupancy of calcium ions and vacancies at Ca(4) sites in the β-TCP structure, which is not the case for hydroxyapatite (HAp), as previously reported.     

云南镇源难处理金精矿工艺矿物学研究

利用X射线衍射、X射线荧光光谱（XRF）、X射线能谱分析（EDX）和矿物解离分析（MLA）等检测手段对云南镇源难处理金精矿的化学组成、矿物组成、硫化物特征以及金的分布情况进行了详细的工艺矿物学研究。结果显示：该金矿以硫化矿、碳酸盐和硅酸盐类矿物为主，含有3.18%的有机碳和2.37%的无机碳。通过金的诊断浸出发现96.16%的金被硫化物包裹，少量金以单体形式存在。通过对主要载金矿物黄铁矿、辉锑矿和毒砂的粒度、包裹及裸露情况进行分析，得出大部分硫化矿以解离单体的形式存在，少部分与其他矿物共生。根据MLA测试及金的诊断浸出，认为大部分金被硫化矿完全包裹，处理该矿石时应先进行硫化物包裹层的氧化处理，再进行金矿的浸出。     

Hydrogen embrittlement and associated surface crack growth in fine-grained equiatomic CoCrFeMnNi high-entropy alloys with different annealing temperatures evaluated by tensile testing under in situ hydrogen charging

The effect of the annealing temperature after cold rolling on hydrogen embrittlement resistance was investigated with a face-centered cubic (FCC) equiatomic CoCrFeMnNi high-entropy alloy using tensile testing under electrochemical hydrogen charging. Decreasing annealing temperature from 800 °C to 750 °C decreased grain sizes from 3.2 to 2.1 μm, and resulted in the σ phase formation. Interestingly, the specimen annealed at 800 °C, which had coarser grains, showed a lower hydrogen embrittlement susceptibility than the specimen annealed at 750 °C, although hydrogen-assisted intergranular fracture was observed in both annealing conditions. Because the interface between the FCC matrix and σ was more susceptible to hydrogen than the grain boundary, the presence of the matrix/σ interface significantly assisted hydrogen-induced mechanical degradation. In terms of intergranular cracking, crack growth occurred via small crack initiation near a larger crack tip and subsequent crack coalescence, which has been observed in various steels and FCC alloys that contained hydrogen.     

Structural transformation in Mn-substituted Sr2Bi2Ta2TiO12 Aurivillius phase synthesized by hydrothermal method: A comparative study and dielectric properties

In this study, a hydrothermal method was applied to synthesize the three-layer Aurivillius phase Sr₂Bi₂Ta₂TiO₁₂ (SBTTO) and Mn-substituted Sr_1·5Bi_2·5Ta₂Ti_0·5Mn_0·5O₁₂ (SBTTMO), with the use of NaOH as a mineralizer. The crystal structure, morphology, dielectric properties, and the correlation between the structural transformation and dielectric properties were investigated. The XRD data reveal that the SBTTO sample adopts a tetragonal crystal structure with the I4/mmm space group and is then transformed into an orthorhombic structure with the B2cb space group for SBTTMO. The morphology of both samples was observed by SEM, which showed anisotropic plate-like grains. With the Mn substitution, the ferroelectric transition temperature (T_c) significantly increases as the influence of the 6s² lone pair of Bi³⁺ increases, and this in turn further induces the relaxor-ferroelectric behavior. Consequently, the increase in T_c confirms the structural transformation from the paraelectric-tetragonal to the ferroelectric-orthorhombic phase.     

Coexistence of antiferro- and ferrimagnetism in the spinel ZnFe2O4 with an inversion degree δ lower than 0.3

Samples with inversion parameter values (δ) ranging from 0.27 to 0.14 while maintaining the crystallite size value have been successfully fabricated from commercially available powders by mechanical grinding and thermal annealing treatments at temperatures ranging between 400 and 600 °C. Detailed characterization studies of these samples using X-ray, neutron diffraction and magnetic measurements have confirmed for the first time the simultaneous coexistence at 2 K of short range antiferromagnetic and ferrimagnetic ordering for a wide range of the inversion parameter. The magnetic phase diagram obtained is different from the one previously reported, which shows at 2 K the coexistence of long range antiferromagnetic order and short range order for values of inversion parameters less than 0.1 and the presence of a ferrimagnetic order only for values of δ > 0.2. At room temperature, the Rietveld analysis of NPD patterns and the magnetization curves showed a paramagnetic behavior in the samples with δ ≤ 0.1. For the samples with higher cationic inversion, typical hysteresis curves of ferrimagnetic materials were observed and the saturation magnetization values obtained agree quite well with the net magnetic moment obtained from the Rietveld refinement of the neutron diffraction patterns.     

Design and analysis adaptivity in multiresolution topology optimization

Multiresolution topology optimization (MTO) methods involve decoupling of the design and analysis discretizations, such that a high-resolution design can be obtained at relatively low analysis costs. Recent studies have shown that the MTO method can be approximately 3 and 30 times faster than the traditional topology optimization method for two-dimensional (2D) and three-dimensional (3D) problems, respectively. To further exploit the potential of decoupling analysis and design, we propose a dp-adaptive MTO method, which involves locally increasing/decreasing the polynomial degree of the shape functions (p) and the design resolution (d). The adaptive refinement/coarsening is performed using a composite refinement indicator that includes criteria based on analysis error, presence of intermediate densities, as well as the occurrence of design artifacts referred to as QR-patterns. While standard MTO must rely on filtering to suppress QR-patterns, the proposed adaptive method ensures efficiently that these artifacts are suppressed in the final design, without sacrificing the design resolution. The applicability of the dp-adaptive MTO method is demonstrated on several 2D mechanical design problems. For all the cases, significant speedups in computational time are obtained. In particular for design problems involving low material volume fractions, speedups of up to a factor of 10 can be obtained over the conventional MTO method.