One- and two-photon absorption properties of a series of derived pyrazolines

The one-photon absorption and two-photon absorption (TPA) properties of a series of pyrazoline derivatives have been theoretically investigated by means of density functional theory and ZINDO-SOS method. On the basis of optimized geometry and UV–vis spectrum, the position and strength of the TPA for molecules are reported. The theoretical findings are consistent with the experimental observations. It is found that a most crucial role in increasing TPA cross-section is played by the conjugated length and the introduction of donors. The calculated maximum TPA cross-section values are in the range of 360–1760 × 10⁻⁵⁰ cm⁴ s/photon. The TPA response will be as another possible application for derived pyrazoline.     

溶胶pH值对氢化锆表面阻氢膜层性能的影响

目的采用溶胶-凝胶法在氢化锆表面制备氧化锆阻氢膜层,探究溶胶p H值对阻氢膜层性能的影响。方法以正丙醇锆为前驱体,通过滴加盐酸分别得到p H值为1、3、5、7、9的溶胶。利用扫描电子显微镜(SEM)、激光共聚焦显微镜(CLSM)和X射线衍射仪(XRD),分析了氧化锆膜层的截面形貌、表面形貌和物相组成,并利用真空脱氢实验测试了膜层的阻氢性能。结果溶胶p H值影响溶胶的涂覆性能,致使氢化锆基体表面所得膜层的连续性、均匀性及厚度存在差异。溶胶pH值的变化对形成膜层的物相组成没有显著影响,所得膜层由单斜相氧化锆(m-ZrO2)和四方相氧化锆(t-ZrO_2)组成。当p H值在1～9范围内时,随着溶胶pH的增加,膜层中t-ZrO_2的体积分数和PRF值均呈现出先升高后降低的变化趋势,t-ZrO_2的体积分数介于13.16%～46.84%之间,膜层的PRF值介于10.13～19.46之间。结论溶胶pH值影响溶胶的涂覆性能,进而影响膜层质量、膜层中各物相的含量以及膜层的阻氢效果。当溶胶p H值为3时,溶胶涂覆性能良好,所得氧化锆膜层均匀、连续,膜层较厚且致密,膜层中t-ZrO_2的体积分数最大,为46.84%,同时膜层的氢渗透降低因子(PRF值,Permeation Reduction Factor)达到最大值19.46。     

Crack healing mechanisms in atmospheric plasma sprayed Yb-silicate coatings during post-process heat treatment

The microstructural evolution of partially amorphous, atmospheric plasma-sprayed Yb-silicate coatings was investigated after heat treatment (HT, 1300 °C). Open porosity as well as crack area and widths in the coatings were characterized. A correlation was found between the increasing amorphous content of the as-sprayed coatings and the reduction in crack area due to crack healing after HT. Characterization results also suggested larger crack widths in the coatings after HT. The first crack-healing mechanism proposed was the capillarity-driven viscous flow of the amorphous phase in the coatings. It was experimentally shown that viscous flow-driven crack spheroidization (crack width enlargement), and crack healing started in the coatings at 1050 °C. Secondly, metastable to stable phase transformation (> 1100 °C) induced expansion in the constrained coatings was discussed as a crack healing mechanism. Finally, a two-step heat treatment was designed to prevent crack width enlargement during HT resulting in reduced porosity.     

Enhancing CMAS corrosion resistance of PS-PVD Si/Yb2Si2O7 EBCs via Al-modification

Enhancing the resistance to molten silicate corrosion is crucial for the long service life of environmental barrier coatings (EBCs). In this study, we used the Al-modification technique to enhance the CMAS corrosion resistance of Si/Yb₂Si₂O₇ coatings prepared by plasma spray-physical vapor deposition. The results show that the Al-modified Yb₂Si₂O₇ coating had higher resistance to CMAS corrosion than the Yb₂Si₂O₇ coating annealed at 1300 ℃ for 100 h, which is related to the refractory mullite and Yb₂Mg(AlO₂)₂O₃ generated during the CMAS exposure of Al-modified Yb₂Si₂O₇ coating. The Al-modified Yb₂Si₂O₇ coating also exhibited excellent resistance to oxygen penetration. The Al-modification technology provides the direction for the corrosion resistance of Yb₂Si₂O₇ system to CMAS.     

Phase composition,microstructure and thermophysical properties of the Srx(Zr0.9Y0.05Yb0.05)O1.95+x ceramics

Sr_x(Zr_0.9Y_0.05Yb_0.05)O_1.95+x (x=1.0, 0.9, 0.8, 0.7) ceramics were prepared by solid state reaction sintering. The sintered Sr_1.0(Zr_0.9Y_0.05Yb_0.05)O_2.95 is a single-phase solid solution while the sintered Sr_x(Zr_0.9Y_0.05Yb_0.05)O_1.95+x (x=0.9?0.7) are composites, and a significant grain growth inhibition is observed in the sintered Sr_x(Zr_0.9Y_0.05Yb_0.05)O_1.95+x (x=1.0, 0.9). Rare-earth elements distribution in the bulk materials indicates that Yb and Y preferentially substitute Zr-sites in SrZrO₃, and the highest solubility of RE₂O₃ in pure SrZrO₃ is ～0.8 mol%. The sintered Sr_x(Zr_0.9Y_0.05Yb_0.05)O_1.95+x have high thermal expansion coefficients up to ～11.0×10^?6 K^-1 (1200°C). Sr_0.8(Zr_0.9Y_0.05Yb_0.05)O_2.75 has the lowest thermal conductivity of 1.38 W·m^-1·K^-1 at 800°C. Sr_x(Zr_0.9Y_0.05Yb_0.05)O_1.95+x (x=1.0, 0.9, 0.8) show no phase transition from 600 to 1400°C, whereas Sr_x(Zr_0.9Y_0.05Yb_0.05)O_1.95+x (x=0.9, 0.8) have excellent high-temperature phase stability over the whole investigated temperature range. Therefore, Sr_x(Zr_0.9Y_0.05Yb_0.05)O_1.95+x (x=1.0, 0.9, 0.8) are considered as promising TBCs materials that might be operated at higher temperatures compared to YSZ.     

单相双稀土改性SrZrO3热障涂层的热物理性能

由于SrO和ZrO₂的蒸气压不同, 造成等离子喷涂SrZrO₃涂层组分偏离原始粉末化学计量比, 从而导致制备态涂层中出现第二相ZrO₂。为了获得高相稳定性的单相涂层, 实验采用固相合成法合成并经过喷雾造粒制备了双稀土改性Sr过量SrZrO₃(Sr_1.1(Zr_0.9Yb_0.05Gd_0.05)O_3.05)热喷涂粉末, 采用大气等离子喷涂方法制备了相应的涂层, 研究了单相双稀土改性SrZrO₃热障涂层的热物理性能及其热循环寿命。研究结果表明, 制备态Sr_1.1(Zr_0.9Yb_0.05Gd_0.05)O_3.05涂层中无第二相产生, 1600 ℃热处理360 h后Sr_1.1(Zr_0.9Yb_0.05Gd_0.05)O_3.05保持单相SrZrO₃结构, 高温相稳定性良好。Sr_1.1(Zr_0.9Yb_0.05Gd_0.05)O_3.05涂层的烧结系数为7.27×10 ^-6 s ^-1, 热处理360 h后该涂层的热膨胀系数为(9.0~11.0)×10 ^-6 K ^-1 (200~1400 ℃), 热导率为2.83 W/(m?K) (1000 ℃)。Sr_1.1(Zr_0.9Yb_0.05Gd_0.05)O_3.05/YSZ双层涂层的火焰循环次数为1000次, 失效区域主要发生在Sr_1.1(Zr_0.9Yb_0.05Gd_0.05)O_3.05陶瓷层内。在喷涂粉末中增加SrO的含量能够弥补在大气等离子喷涂过程中Sr元素过量挥发的问题, 成功制备了单相双稀土改性Sr_1.1(Zr_0.9Yb_0.05Gd_0.05)O_3.05热障涂层。双稀土掺杂能够明显提高涂层的热膨胀系数, 且单相双稀土改性Sr_1.1(Zr_0.9Yb_0.05Gd_0.05)O_3.05涂层的抗烧结性能明显优于SrZrO₃涂层, 但单相Sr_1.1(Zr_0.9Yb_0.05Gd_0.05)O_3.05涂层热导率比含有第二相的SrZrO₃涂层高。     

烧结钕铁硼磁体等离子喷涂-晶界扩散氧化镝研究

目的 采用悬浮液等离子喷涂技术,在烧结Nd-Fe-B磁体表面制备结构完整、厚度可控、结合力较强的Dy2O3涂层,并通过晶界扩散提高Nd-Fe-B磁体的矫顽力.方法 制备Dy2O3悬浮液,在烧结Nd-Fe-B表面,利用悬浮液等离子喷涂技术制备Dy2O3涂层.利用激光粒度仪测试粉体粒度.采用光学显微镜、扫描电子显微镜(SE...     

High temperature properties of the monolithic CVD β-SiC materials joined with a pre-sintered MAX phase Ti3SiC2 interlayer via solid-state diffusion bonding

Monolithic high purity CVD β-SiC materials were successfully joined with a pre-sintered Ti₃SiC₂ foil via solid-state diffusion bonding. The initial bending strength of the joints (∼ 220 MPa) did not deteriorate at 1000 °C in vacuum, and the joints retained ∼ 68 % of their initial strength at 1200 °C. Damage accumulation in the interlayer and some plastic deformation of the large Ti₃SiC₂ grains were found after testing. The activation energy of the creep deformation in the temperature range of 1000 – 1200 °C in vacuum was ∼ 521 kJmol⁻¹. During the creep, the linkage of a significant number of microcracks to form a major crack was observed in the interlayer. The Ti₃SiC₂ interlayer did not decompose up to 1300 °C in vacuum. A mild and well-localized decomposition of Ti₃SiC₂ to TiC_x was found on the top surface of the interlayer after the bending test at 1400 °C in vacuum, while the inner part remained intact.     

Effects of Li doping and point defect on the magnetism of ZnO

The magnetism sources and magnetic mechanism of Li doping and point defect, which coexist in the presence of hexagonal wurtzite ZnO, are controversial. To solve these problems, the effects of Li doping and point defect on the magnetism of ZnO were studied using geometry optimization and energy calculation based on the first-principle generalized gradient approximation + U (GGA + U) method of density functional theory. Results showed that the coexistence of Li doping and Zn vacancy can achieve ferromagnetic long-range order, and the Curie temperature of the doping system can achieve room temperature. In addition, results showed that magnetic moments are significantly different when the structures of the systems are also different with the same doping amount and doping method, which are advantageous for the enhancement of the magnetic properties of dilute magnetic semiconductors. The magnetism source of Zn₁₄LiO₁₆ is the hybrid coupling electron exchange effect between O-2p and Zn-3d orbits. With the coexistence of Li replacing Zn and Zn vacancy, the closest relative distance between doping and vacancy leads to the lowest formation energy and highest stability. In the condition of the highest stability of the ground state, all the doping systems of Li replacing Zn and O vacancy, doping system of interstitial Li and Zn vacancy, and doping system with the coexistence of Li replacing Zn, interstitial Li, and Zn vacancy are non-magnetic, which are considered worthless in the design and preparation of diluted magnetic semiconductors (DMSs).     

Al2O3 triggered in-situ crystallization of Gd3Al2Ga3O12 in glass and enhancement in magnetic and Faraday rotating properties

Nanocrystals doped transparent glasses or glass ceramics have shown promising tunable magnetic and magneto-optical performance. In this study, the Al₂O₃-induced in-situ crystallization of Gd₃Al₂Ga₃O₁₂ in tellurite glass was reported. 10–20 nm-cubic Gd₃Al₂Ga₃O₁₂ (Ia3d space group) nanocrystals formed in tellurite glass with Al₂O₃ content ≤ 0.75 mol% by 400 °C-heat treatment. When Al₂O₃ content in glass was higher than 0.75 mol%, excessive Al₂O₃ triggered the crystallization of orthorhombic GdAlO₃ (Pnma) in which the Gd and Al ions existed as octahedral GdO₈ and AlO₆ units at a temperature higher than 398 °C. The in-situ crystallization influenced the glass network structure, broke the linkage of tetrahedral TeO₄, and BO₄, and formed trigonal pyramids TeO₃ and BO₃ instead. At the same time, nuclear magnetic resonance spectra revealed the conversion of AlO₄→ AlO₆, GaO₄→ GaO₆, and the changes from bridging oxygen to non-bridging oxygen as well. From energy-dispersive X-Ray analysis, Gd³⁺ clusters were observed, leading to the ferromagnetism of glass. Electron paramagnetic resonance spectra witnessed an enhancement of the Zeeman effect which is the reason for the improvement of Faraday rotation. Tellurite glass with 0.75 mol% Al₂O₃ after 400 °C-annealing (A75) showed a giant Verdet constant of 93 rad/T.m at 633 nm which is superior to most of the values from the literature.