Polar nanodomains and relaxor behaviour in (1 − x)Pb(Mg1/3Nb2/3)O3–xPbTiO3 crystals with x = 0.3–0.5

Phase transitions and dielectric properties of the (1 − x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ crystals with x = 0.3–0.5 are studied. The solid solutions in this composition range are shown to be relaxor ferroelectrics. The crystals with low x demonstrate a diffused maximum in the temperature dependences of the dielectric permittivity at T_m. T_m varies with frequency according to the Vogel–Fulcher law. The polarizing microscopy investigations reveal a first-order phase transition from the relaxor phase to the low-temperature ferroelectric phase at T_C, which is several degrees below T_m. The permittivity peak in the crystals with x = 0.5 is sharp, and T_m is equal to T_C and does not depend on frequency, as is typical of the transition from a ferroelectric to an ordinary paraelectric phase. Nevertheless, the relaxor, but not the paraelectric, phase is observed at T > T_m. This conclusion is confirmed by the observation of the temperature behaviour of complex dielectric permittivity at T > T_m, which is typical of relaxors and related to the existence of polar nanodomains.     

Bi2O3助熔剂对CaO-B2O3-SiO2/Al2O3玻璃陶瓷复合材料性能的影响

以CaO-B₂O₃-SiO₂(CBS)玻璃粉体和Al₂O₃陶瓷粉体为原料,通过在CBS与Al₂O₃的质量比固定为50:50的玻璃-陶瓷复合材料中添加适量的Bi₂O₃作为烧结助熔剂,探讨了Bi₂O₃助熔剂对CBS/Al₂O₃复合材料的烧结性能、介电性能、抗弯强度和热膨胀系数的影响规律.研究表明:Bi₂O₃助熔剂能通过降低CBS玻璃的转变温度和黏度促进CBS/Al₂O₃复合材料的致密化进程,于880 ℃下烧结即能获得结构较致密、气孔较少的CBS/Al₂O₃复合材料.然而,过量添加Bi₂O₃将使玻璃的黏度过低,从而恶化CBS/Al₂O₃复合材料的烧结性能、介电性能及抗弯强度.当Bi₂O₃的添加量为CBS/Al₂O₃复合材料的1.5wt%时,于880 ℃下烧结即能获得最为致密的CBS/Al₂O₃复合材料,密度为2.82 g·cm^-3,这一材料具有良好的介电性能(介电常数为7.21,介电损耗为1.06×10^-3),抗弯强度为190.34 MPa,0~300 ℃的热膨胀系数为3.52×10^-6 K^-1.     

Domain patterns on ferroelectric Rh:BaTiO3 single crystals

Single crystal growth and domain structure of Rh:Barium titanate (BaTiO₃) have been investigated. Rh doping in BaTiO₃ is effective for the growth of bulk crystals without twin formation. Atomic force microscope (AFM) and optical microscope studies reveal the formation 180° and 90° domains on the grown crystals. It has been observed that the complex 180° domain structure with typical size of around 20 μm exists in the c-domain of {0 0 1} face of Rh doped BaTiO₃ crystals.     

Domain structure studies on Pb(Zn1/3Nb2/3)O3–PbTiO3 mixed crystal system

In this investigation, ferroelectric Pb(Zn_1/3Nb_2/3)O₃–PbTiO₃ single crystals have been grown by modified flux technique with PbO self flux. Well-defined domain patterns were observed through polarized light on the as-grown crystals. Fingerprint like pattern and tweed pattern have also been observed. In PZN–PT system the fingerprint domain area is found to be elongated along one direction for increasing PT content.     

一步水热合成Sm3+-SrTiO3/TiO2复合纳米纤维及可见光催化性能

以电纺TiO₂纳米纤维为基体和反应物,通过一步水热法,将SrTiO₃原位构筑在TiO₂纳米纤维表面的同时将稀土Sm³⁺掺入SrTiO₃中,合成了Sm³⁺-SrTiO₃/TiO₂复合纳米纤维光催化材料.利用XRD、XPS、FESEM和HRTEM等测试手段对样品进行了表征.以罗丹明B和对氯苯酚模拟有机污染物进行光催化降解.结果表明：稀土Sm³⁺掺杂进入SrTiO₃晶格取代Sr²⁺,在SrTiO₃禁带内形成杂质能级,拓宽了光谱响应范围;同时在SrTiO₃晶格内引入了缺陷位,成为电子的捕获中心,降低了载流子的复合几率;而SrTiO₃与TiO₂复合形成异质结,进一步提高了光生电子-空穴的分离程度,Sm³⁺-SrTiO₃/TiO₂复合纳米纤维表现出良好的可见光催化活性。     

可磁分离Fe3O4/g-C3N4复合材料的制备及其性能

为了利用Fe₃O₄的磁响应性及石墨相C₃N₄（g-C₃N₄）优良的光催化活性,首先采用高温热聚合法,以尿素为前驱体制备g-C₃N₄,然后采用水热法合成了可磁分离Fe₃O₄/g-C₃N₄复合材料。利用TEM、XRD、TGA、BET和振动样品磁强计（VSM）等多种测试手段表征分析Fe₃O₄/g-C₃N₄复合材料的形貌、晶型结构、比表面积、成分、饱和磁化强度等。通过模拟太阳光下Fe₃O₄/g-C₃N₄复合材料光催化吸附降解亚甲基蓝（MB）的实验,评价了Fe₃O₄/g-C₃N₄复合材料的吸附性能及光催化性能。结果表明,可磁分离Fe₃O₄/g-C₃N₄复合材料具有较大的比表面积,约为71.89 m²/g;且具有较好的磁性,饱和磁化强度为18.79 emu/g,可实现复合材料的分离回收;光照240 min时,Fe₃O₄/g-C₃N₄复合材料对MB的去除率为56.54%。所制备的Fe₃O₄/g-C₃N₄复合材料具有优良的吸附性能、光催化活性和磁性,并可通过外加磁场进行分离与回收。     

Effects of growth conditions on the domain structure and dielectric properties of (1 − x)Pb(Sc1/2Nb1/2)O3–xPbTiO3 single crystals

The studies of the (1 − x)Pb(Sc_1/2Nb_1/2)O₃–xPbTiO₃ (PSN–PT) single crystals reveal that the chemical and physical properties of the materials are affected by the growth conditions. By the measurements of the dielectric constant as a function of temperature upon cooling, it is found that crystals grown from the same charged stoichiometric composition (x = 0.425), but under different flux environments (i.e. the composition of flux and the flux to PSN–PT ratios are varied), show anomalies (i.e. phase transitions) at different temperatures. This phenomenon is attributed to the complex local chemical structure of the PSN–PT solid solution single crystals with B-site random occupancy of three different cations (Sc³⁺, Nb⁵⁺ and Ti⁴⁺). The dielectric and domain structure of the PSN–PT crystals with composition near the morphotropic phase boundary (MPB) are investigated, showing much more complex situations compared with Pb(Sc_1/2Nb_1/2)O₃.     

Al2O3掺杂BaTi0.85Sn0.15O3陶瓷的制备及性能表征

通过传统固相二次烧结法来制备x wt% Al₂O₃（x=0、1.0、1.5）/BaTi_0.85Sn_0.15O₃（BTS）陶瓷。研究了掺杂不同含量Al₂O₃对BTS陶瓷的微观结构、介电性能及挠曲电性能的影响。结果表明,掺杂Al₂O₃的BTS陶瓷不改变陶瓷的晶体结构,仍为标准钙钛矿结构晶型;Al₂O₃的掺入能够有效降低晶粒尺寸,具有明显的细晶作用。随着Al₂O₃含量的增大,Al₂O₃/BTS陶瓷的介电常数减小,介电损耗得到明显改善,居里峰逐渐宽化且向温度高的方向偏移。Al₂O₃/BTS陶瓷的挠曲电系数随着Al₂O₃含量的增加和测试环境温度的升高均减小。此外,Al₂O₃/BTS陶瓷的挠曲电系数和介电常数之间存在一种近线性关系,但当温度非常接近于居里温度时,这种线性关系减弱。     

纳米BiVO4/BaTiO3复合材料光催化降解性能

通过混合烧结法将BiVO₄与BaTiO₃复合获得BiVO₄/BaTiO₃复合光催化剂。采用XRD和FTIR分析了产物的物相,可知,BiVO₄/BaTiO₃复合材料中仅含有BiVO₄和BaTiO₃,无杂相生成。TEM观察发现,粒径约为55 nm的纳米BaTiO₃颗粒较好地附着在平均颗粒尺寸为~400 nm的BiVO₄颗粒表面,形成异质结构。选用酸性橙7（AO7）作为反应物模型,以模拟太阳光作为光源,研究了BiVO₄/BaTiO₃复合材料的光催化降解性能。结果表明:与BaTiO₃相比,BiVO₄/BaTiO₃复合材料的光催化降解活性显著提高;当BiVO₄的含量为8wt%时,BiVO₄/BaTiO₃复合材料的光催化效果最佳,光照6 h染料的降解率可达~68%,为BaTiO₃的1.9倍。BiVO₄/BaTiO₃复合材料的光催化性能较为稳定,循环使用3次后AO7的降解率仍有~62%。催化机制分析说明,BaTiO₃与BiVO₄复合后,光生电子和空穴能够向对方迁移,促进了光生电荷的分离,有利于光催化效率的提高。      

Z-scheme mechanism for methylene blue degradation over Fe2O3/g-C3N4 nanocomposite prepared via one-pot exfoliation and magnetization of g-C3N4

The low surface area, high recombination rate of photogenerated charge carriers, narrow visible range activity, and difficulty in the separation from cleaned solutions limit the wide application of g-C₃N₄ as a photocatalyst. Herein, we have succeeded in developing a one-pot strategy to overcome the above-mentioned difficulties of g-C₃N₄. The broadening of the visible-light response range and inducing magnetic nature to g-C₃N₄ was succeeded by preparing a nanocomposite with Fe₂O₃ via a facile solvothermal method. The preparation method additionally imparted layer exfoliation of g-C₃N₄ as evident from the XRD patterns and TEM images. The strong interaction between the components is revealed from the XPS analysis. The broadened visible-light absorbance of Fe₂O₃/g-C₃N₄ with a Z-scheme photocatalytic degradation mechanism is well evident from the UV‒Vis DRS analysis and PL measurement of the composite with terephthalic acid. The active species of photocatalysis were further investigated using scavenging studies in methylene blue degradation that revealed hydroxyl radicals and holes as the major contributors to the activity of Fe₂O₃/g-C₃N₄.     

Spectroscopic investigation of Nd ion in LiNbO3, MgO:LiNbO3 and LiTaO3 single crystals relevant for laser applications

The polarized absorption and luminescence properties of Nd³⁺ doped isostructural LiNbO₃, MgO:LiNbO₃ and LiTaO₃ nonlinear bulk single crystals are reported. Pump-probe experiments associated with the Judd-Ofelt approach are used to estimate two types of room temperature cross sections: polarized emission cross sections of the dominant ⁴F_3/2 → ⁴I_1//2 transition near 1085 and 1093 nm and polarized excited-state absorption cross sections in the same spectral domain and in the green spectral range corresponding to self frequency doubling. Self frequency-doubling results are also given in Nd:LiNbO₃ and Nd:MgO:LiNbO₃ versus sample temperature.     

Influence of semiconductor surface preparation on photoelectric properties of Al–Zn3P2 contacts

The Schottky barriers formed by Al on Zn₃P₂ p-type crystals have been studied. Three types of crystals (monocrystal, large-grain crystal and polycrystal) were used for device fabrication. The samples were separated in two groups according to the type of structure and the methods of surface preparation. The samples from the first group were different in structure (monocrystal, large-grain crystal and polycrystals) but prepared in the same way. Three polycrystals with differently prepared surfaces were collected in the second group. Two samples from this group were also annealed in open air at 523 K for 24 h. Measurements of photovoltaic effect at room temperature were carried out to test the impact of surface preparation on photoelectric properties of Al–Zn₃P₂ contacts. Substantial differences in shape and intensity of PV signal were observed depending on whether the surface of semiconductor was mechanically polished, chemically etched or/and heat treated. The height of potential barrier, Φ_B, and optical transitions in semiconductor were determined. The value of Φ_B changed from 0.747 to 0.767 eV for unheated samples and from 0.724 to 0.755 eV for the heated ones. The quality of semiconductor surface seems to have an essential influence on spectral characteristics of Al–Zn₃P₂ junctions, especially in the case of polycrystals. It appeared that thorough preliminary mechanical polishing of crystals surface provides quite good photoelectric properties of Al–Zn₃P₂ junctions.     

新型异质结LaCO3OH/In(OH)3/In2S3的制备及其可见光下催化降解罗丹明B的性能

采用原位湿化学方法合成了LaCO3OH/In(OH)3/In2S3异质结光催化剂。采用XRD、 SEM、 XPS、 BET、 TG等表征技术对所制备LaCO3OH/In(OH)3/In2S3异质结光催化剂的组成、结构和形貌等进行分析。以可见光下(λ≥420 nm)降解罗丹明B(RhB)为探针反应,研究了LaCO3OH含量不同时LaCO3OH/In(OH)3/In2S3异质结光催化剂的光催化活性。结果表明,当La/In的摩尔比为15mol%时, LaCO3OH/In(OH)3/In2S3异质结光催化剂具有最高的降解活性,与In(OH)3/In2S3相比,活性提高约一倍。这可能是由于LaCO3OH/In(OH)3/In2S3异质结光催化剂具有较高的比表面积、合适的能带结构和较好的吸附性能。以对苯二甲酸为探针分子,光催化实验证明羟基自由基(·OH)是重要的活性物种。并提出了可能的降解机制。     

Deposition chemistry in the Cat-CVD processes of the SiH4/NH3 system

Laser spectroscopic as well as mass-spectrometric techniques were employed to examine the deposition chemistry in the catalytic chemical vapor deposition processes of the SiH₄/NH₃ system. The absolute densities of NH, NH₂ and SiH₃ radicals were measured under various conditions. The densities of the stable products, H₂ and N₂, as well as those of the reactants, NH₃ and SiH₄, were also measured. The NH₂ density is always higher than that of NH and both densities decrease by the addition of SiH₄. The SiH₃ density increases nonlinearly with the increase in the SiH₄ pressure. The SiH₃ density was found to be much higher than that of NH₂ under near practical deposition conditions to fabricate Si₃N₄ films (an NH₃ to SiH₄ flow-rate ratio of 50:1, a total pressure of 20 Pa and a catalyzer temperature of 2300 K). No aminosilane molecules were identified, suggesting that the contribution of aminosilyl radicals to the film deposition is minor. Thus, NH₂ and SiH₃ must be the major deposition species to form Si₃N₄.     

Al2O3颗粒形貌对注凝成型ZrO2/Al2O3陶瓷性能的影响

采用3种不同形貌的Al₂O₃原料对注凝成型制备ZrO₂/Al₂O₃（ZTA）陶瓷工艺中悬浮体的流变性能进行了研究。以低毒的单体N,N-二甲基丙烯酰胺（DMAA）制备了ZrO₂/Al₂O₃坯体和陶瓷。讨论了3种不同形貌的Al₂O₃原浆料的分散剂用量、球磨时间和固含量对浆料流变性的影响。Al₂O₃粉体呈扁平状有利于降低浆料的黏度,Al₂O₃粉体呈棒状对生坯强度的提高有利。制得的3种ZrO₂/Al₂O₃坯体颗粒间结合紧密,抗弯强度分别达到21.45,19.87,25.90 MPa。Al₂O₃粉体呈颗粒状有利于最终陶瓷力学性能的提高,陶瓷的抗弯强度及断裂韧性分别为680 MPa和7.49 MPa·m^1/2,453.1 MPa和6.8 MPa·m^1/2,549.4 MPa和6.34 MPa·m^1/2。     

SrTiO3/TiO2 heterostructure nanowires with enhanced electron--hole separation for efficient photocatalytic activity

Heterostructure is an effective strategy to facilitate the charge carrier separation and promote the photocatalytic performance. In this paper, uniform SrTiO₃ nanocubes were in-situ grown on TiO₂ nanowires to construct heterojunctions. The composites were prepared by a facile alkaline hydrothermal method and an in-situ deposition method. The obtained SrTiO₃/TiO₂ exhibits much better photocatalytic activity than those of pure TiO₂ nanowires and commercial TiO₂ (P25) evaluated by photocatalytic water splitting and decomposition of Rhodamine B (RB). The hydrogen generation rate of SrTiO₃/TiO₂ nanowires could reach 111.26 mmol·g⁻¹·h⁻¹ at room temperature, much better than those of pure TiO₂ nanowires (44.18 mmol·g⁻¹·h⁻¹) and P25 (35.77 mmol·g⁻¹·h⁻¹). The RB decomposition rate of SrTiO₃/TiO₂ is 7.2 times of P25 and 2.4 times of pure TiO₂ nanowires. The photocatalytic activity increases initially and then decreases with the rising content of SrTiO₃, suggesting an optimum SrTiO₃/TiO₂ ratio that can further enhance the catalytic activity. The improved photocatalytic activity of SrTiO₃/TiO₂ is principally attributed to the enhanced charge separation deriving from the SrTiO₃/TiO₂ heterojunction.     

Modification of UV-VIS optical absorption properties caused by MgO incorporation in MgO-doped LiNbO3 crystals

MgO-doped LiNbO₃ single crystals were investigated in the UV-VIS range to study the effect of MgO in the LiNbO₃ host. Congruent LiNbO₃ has an optical absorption edge of 3.75 eV. Analysis of the absorption edge gave an estimate of the indirect band gap for MgO-LiNbO₃ solid solutions. The band gap shows an MgO threshold effect in the absorption coefficient. An additional indirect transition at 2.2–2.5 eV was revealed when MgO was incorporated into the lithium niobate structure. This indirect transition also has a MgO threshold effect around 5 mol% MgO.     

Dislocation, annealing and quenching effects on the microindentation hardness of Bi2Te3 and Bi2Te2.9Se.1 single crystals

Stoichiometric crystals of Bi₂Te₃ and Bi₂Te_2.9Se_.1 have been grown from the melt by the horizontal zone melting (HZM) technique. X-ray powder diffraction and energy dispersive X-ray analysis could prove that the grown crystals are stoichiometric with lattice constants a=0.4374 nm, c=3.044 nm for Bi₂Te₃ and a=0.4374 nm, c=3.038 nm for Bi₂Te_2.9Se_.1. Dislocation density measurements are carried out by etch pit technique and are observed by scanning electron and optical micrograph. The mechanical strength of the as-grown, quenched and annealed crystals is assessed by the Vickers hardness measurements.     

Al2O3纤维对SiO2基陶瓷型芯的烧缩阻滞

向SiO₂基体粉料中添加Al₂O₃纤维,采用热压注法制备Al₂O₃/SiO₂陶瓷型芯。分析Al₂O₃纤维含量对陶瓷型芯性能的影响。研究结果表明：Al₂O₃纤维含量对Al₂O₃/SiO₂陶瓷型芯的线收缩率、体积密度和抗弯强度均有较大的影响。当Al₂O₃纤维含量大于1wt%时,Al₂O₃/SiO₂陶瓷型芯的线收缩率大幅度降低,稳定在0.335%左右,体积密度随之降低,稳定在1.790 g · cm^-3左右;当Al₂O₃纤维含量为1wt%时,陶瓷型芯抗弯强度达最大值20.48 MPa。分析了Al₂O₃纤维对Al₂O₃/SiO₂陶瓷型芯烧结收缩的阻滞作用机制。     

碳纤维表面改性增强Fe3Al-Al2O3复合材料的制备及组织性能

采用溶胶-凝胶分散和热压烧结制备了短切碳纤维（CF_s）/Fe₃Al-Al₂O₃复合材料。分别通过电化学镀Cu和化学气相沉积SiC对CF_s表面修饰和改性,研究了Cu镀层和SiC涂层对CF_s/Fe₃Al-Al₂O₃复合材料显微组织、相组成、力学性能及断裂行为的影响。结果表明,未修饰的CF_s在Fe₃Al-Al₂O₃基体中受到严重侵蚀,CF_s/Fe₃Al-Al₂O₃复合材料致密度低,抗弯强度仅为239.0 MPa,与Fe₃Al-Al₂O₃强度相当;表面镀Cu可有效保护CF_s不被侵蚀,同时提高了CF_s/Fe₃Al-Al₂O₃复合材料的烧结致密性和界面结合强度,从而明显提高了复合材料的断裂强度,但断裂过程中纤维拔出较短;CF_s表面沉积SiC的CF_s/Fe₃Al-Al₂O₃复合材料组织均匀致密,表面涂层完整,且与纤维及基体之间结合力相当,断裂过程中,涂层既可随纤维一起拔出基体,也可与CF_s分离而留在基体之中,SiC涂层与纤维及基体之间的弱相互作用很大程度上促进了纤维脱黏和拔出,从而促进CF_s/Fe₃Al-Al₂O₃复合材料韧化所需的渐进破坏机制。