Formation of MgAl2O4 in Al2O3-(Al-4wt.%Mg) composites

The Al₂O₃ particles are introduced into the Al-4wt.%Mg melt by the “vortex” method. After being cast, Al₂O₃-(Al-4wt.%Mg) composites are remelted at 700, 750, 800 and 850°C for different residence times to investigate the formation of MgAl₂O₄ (spinel).

The results show that MgAl₂O₄ is the unique interface of the Al₂O₃-(Al---Mg) composites held at 700–850°C. Fine MgAl₂O₄ crystals grow on the surface of the Al₂O₃ particle but, as the holding temperature and the residence time increase, some spinels will form themselves into pyramidal shape. The MgAl₂O₄ grows not only at the matrix-particle interface but also on the surface of the composite specimens. The formation reactions of interfacial MgAl₂O₄ are as follows: Mg(1) + 2Al(1) + 2O₂(g) = MgAl₂O₄(s)3Mg(1) + 4Al₂O₃(s) = 3MgAl₂O₄(s) + 2Al(1) Both of them are equally important.     

Strengthening mechanisms in Al2O3/SiC nanocomposites

A strengthening mechanism merely arising from internal (residual) microstresses due to thermal expansion mismatch is proposed for explaining the high experimental strength data measured in Al₂O₃/SiC nanocomposites. Upon cooling, transgranular SiC particles undergo lower shrinkage as compared to the surrounding matrix and provide a hydrostatic “expansion” effect in the core of each Al₂O₃ grain. Such a grain expansion tightens the internal Al₂O₃ grain boundaries, thus shielding both weakly bonded and unbonded (cracked) grain boundaries. It is shown that the shielding effect by intragranular SiC particles is more pronounced than the grain-boundary opening effect eventually associated with thermal expansion anisotropy of the Al₂O₃ grains, even in the “worst” Al₂O₃-grain cluster configuration. Therefore, an improvement of the material strength can be found. However, a large stress intensification at the grain boundary is found when intergranular SiC particles are present, which can produce a noticeable wedge-like opening effect and trigger grain-boundary fracture. The present model enables us to explain the experimental strength data reported for Al₂O₃/SiC nanocomposites and confirms that the high strength of these materials can be explained without invoking any toughening contribution by the SiC dispersion.     

On the structure of the NiO–Al2O3 systems, studied by diffuse-reflectance spectroscopy

Diffuse-reflectance spectra of the NiO–Al₂O₃ systems in the 350–800 nm spectral domain are analysed. Two types of Ni²⁺complexes in γ-Al₂O₃ have been found at low concentrations (<5%): [Ni²⁺6O²⁻] and [Ni²⁺4O²⁻] with octahedral (O_h) and tetrahedral (T_d) symmetries, respectively. Coexistence of these two complexes is discussed in connection with the sample preparation and their thermal treatment.     

Al2O3/BaZrO3双陶瓷界面微观组织演化及机理

以Al₂O₃为背层(硅溶胶为粘结剂), 电熔BaZrO₃作为面层材料(钇溶胶为粘结剂), 1550℃烧结后制成50 mm×25 mm×5 mm的Al₂O₃/BaZrO₃双陶瓷试样。通过光学显微镜(OM)、扫描电子显微镜(SEM)、X射线衍射仪(XRD)和EDS等手段观察了BaZrO₃层和Al₂O₃/BaZrO₃界面的显微结构, 研究了BaZrO₃与Al₂O₃的界面反应。结果表明, 面层由BaZrO₃基体和分布其上的大小10 μm左右的Y稳定的ZrO₂晶粒组成; Al₂O₃/BaZrO₃界面发生反应形成厚约300 μm的过渡层, 界面反应生成物有BaOAl₂O₃、ZrO₂和BaO·Al₂O₃·2SiO₂。界面从单纯的BaZrO₃/Al₂O₃双陶瓷结构演变为BaZrO₃、ZrO₂、BaO·Al₂O₃、BaO·Al₂O₃·2SiO₂和Al₂O₃等多种物相组成的复杂结构。反应过程中Al元素基本不迁移扩散, BaZrO₃中Ba元素向Al₂O₃所在的位置扩散形成BaO·Al₂O₃, 残留物形成一层条状ZrO₂, 而BaO·Al₂O₃·2SiO₂围绕着EC95(Al₂O₃+5%SiO₂)粉体颗粒周围生成。     

双读出量能器用闪烁晶体研究进展

双读出量能器是一种全新设计的高能粒子探测装置, 它能同时测量到Cherenkov光和闪烁光, 因而能更全面地获得高能粒子的信息。目前, 双读出量能器主要有三种设计方式: (1)采用石英纤维产生Cherenkov光, 塑料闪烁纤维生成闪烁光; (2)分别以未掺杂的晶体纤维作为Cherenkov辐射体、Ce掺杂的同种晶体纤维作为闪烁体; (3)采用同种闪烁晶体有效分离Cherenkov光和闪烁光。第三种设计可以消除取样涨落、提高量能器的分辨率, 因而备受关注。本文基于第三种设计方式探讨了钨酸铅(PbWO₄)、锗酸铋(Bi₄Ge₃O₁₂)、硅酸铋(Bi₄Si₃O₁₂)和镥铝石榴石(Lu₃Al₅O₁₂)四种。闪烁晶体在双读出量能器方面的研究进展和可能的应用。Pr掺杂PWO晶体以及硅酸铋晶体都有可能用于双读出量能器, 而后者由于吸收边比锗酸铋更短, 更易于分离Cherenkov光和闪烁光, 在双读出量能器应用方面显示出明显的优势。稀土离子掺杂有望进一步提高硅酸铋晶体的性能, 开发出更适合双读出应用的闪烁材料。     

热等静压烧结制备细晶粒Ce,Y:SrHfO3闪烁陶瓷

Ce:SrHfO₃陶瓷因具有高密度和高有效原子序数, 对高能射线具有很强的阻止能力。同时, Ce:SrHfO₃陶瓷还具有快衰减和高能量分辨率等优异的闪烁性能, 引起了研究人员的广泛关注。由于传统的烧结方法难以实现非立方结构Ce:SrHfO₃陶瓷的透明化, 本研究采用真空长时烧结和短时真空预烧结合热等静压烧结(Hot Isostatic Pressing, HIP)方法制备Ce,Y:SrHfO₃陶瓷。以金属氧化物和碳酸盐为原料, 1200 ℃下煅烧8 h可以获得平均粒径为152 nm的纯相Ce,Y:SrHfO₃粉体。1800 ℃真空烧结20 h获得平均晶粒尺寸为28.6 μm的不透明的Ce,Y:SrHfO₃陶瓷, 而两步烧结法可以制备光学透过率良好的Ce,Y:SrHfO₃陶瓷。本研究详细分析了陶瓷致密化过程中微结构的演变, 探究了预烧结温度对Ce,Y:SrHfO₃陶瓷密度、显微结构和光学透过率的影响。真空预烧(1500 ℃×2 h)结合HIP后处理(1800 ℃×3 h, 200 MPa Ar)所获得的Ce,Y:SrHfO₃陶瓷在800 nm处的最高直线透过率为21.6%, 平均晶粒尺寸仅为3.4 μm。在X射线激发下, Ce,Y:SrHfO₃陶瓷在400 nm处产生Ce³⁺ 5d-4f发射峰, 其XEL积分强度比商用锗酸铋(BGO)晶体高3.3倍, Ce,Y:SrHfO₃陶瓷在1 μs门宽下的光产额约为3700 ph/MeV。良好的光学和闪烁性能可以拓宽Ce,Y:SrHfO₃陶瓷在闪烁探测领域的应用。     

高功率激光照明用Al2O3-YAG:Ce复相陶瓷荧光体的组分设计与性能优化

结合蓝色激光二极管和黄色荧光转换器制备的固态激光照明引起了人们极大的关注, 但荧光转换材料的热猝灭效应显著影响了高功率激光照明的实现。通过组分设计和性能优化可以提高荧光转换器的热导率和发光均匀性。本工作采用固相反应烧结技术制备了一系列不同Al₂O₃含量的Al₂O₃-YAG:Ce复相陶瓷荧光体, 研究了Al₂O₃含量对Al₂O₃-YAG:Ce陶瓷荧光体微观结构、相组成、光学性能和热学性能的影响。Al₂O₃-YAG:Ce陶瓷荧光体在800 nm处的总透过率随着Al₂O₃含量的增加(0→90%)而下降(82.6%→23.6%)。Al₂O₃-YAG:Ce陶瓷荧光体的激发和发射强度随Al₂O₃含量的增加先增大后减小。当Al₂O₃/Al₂O₃-YAG:Ce的质量比为70%时, 陶瓷荧光体在室温下的热导率高达25.7 W·m^-1·K^-1, 且表现出最高的发射强度。当采用功率密度为20 W·mm^-2的蓝光二极管泵浦 70% Al₂O₃-YAG:Ce复相陶瓷荧光体时, 可获得3724 lm的高光通量和239.4 lm·W^-1的高流明效率。此外, 当功率密度从1 W·mm^-2增大到20 W·mm^-2时, 流明效率仅下降10.5%, 光通量持续增加且未出现发光饱和。上述结果显示, Al₂O₃-YAG:Ce复相陶瓷荧光体具有良好的发光效率和热稳定性, 将在高功率激光照明中具有广阔的应用前景。     

Spectra and laser properties of Er, Yb:phosphate glasses

The effects of Al₂O₃, Yb₂O₃, Er₂O₃ and OH on spectral properties of P₂O₅·Na₂O·SrO·Al₂O₃·Yb₂O₃·Er₂O₃ erbium phosphate glass were studied. 5, 8, 13 mol% Al₂O₃, 4, 5, 6, 7 and 8 mol% Yb₂O₃ and 0.05, 0.2, 0.4 mol% Er₂O₃ were used. It was found Al₂O₃ improves fluorescent lifetime of Er³⁺ ions, but the integrated absorption cross-section of Er³⁺ ions decreases with the increase of Al₂O₃ concentration. Evaluating from energy transfer efficiency of Yb³⁺ to Er³⁺ and spectral parameters of Yb³⁺ and Er³⁺, lower Al₂O₃ content, 6 mol% Yb₂O₃ and 0.2–0.4 mol% Er₂O₃ are preferred for LD pumped microchip laser application. OH groups in glass greatly affect fluorescent intensity and lifetime of Er³⁺, Yb³⁺:phosphate glass. The OH absorption coefficient at 3000 cm⁻¹ should be <1 cm⁻¹ for laser applications. Pumped with a 2 W, 974 nm InGaAs laser diode, CW laser centered at 1530 nm with slope efficiency of 10.6% and maximum output of 43 mW was achieved in our 2 mm thick Er³⁺, Yb³⁺:phosphate glass at room temperature.     

Joining particulate and whisker ceramic composites by plastic flow

Joining of bulk ceramics by plastic flow has been demonstrated for several fine-grained ceramics. We have joined, for example, submicrometer 3 mol% Y₂O₃ partially stabilized ZrO₂ (YSZ) and YSZ-toughened Al₂O₃. The interlayers in these cases consisted of dense, submicrometer-grain-sized pieces of ceramics that have been shown to exhibit superplastic flow. We have extended the joining work to include incorporation of 15 vol.% SiC or 20 vol.% TiC whiskers within the bond layer. Unlike YSZ/Al₂O₃, because of the presence of the whiskers, YSZ/Al₂O₃/SiC and YSZ/Al₂O₃/TiC do not deform superplastically. However, virtually perfect YSZ/Al₂O₃ joints with and without whiskers could be made by compressing at 1300–1350 °C and stresses of <20 MPa.     

实验优化设计中频反应溅射Al2O3:Ce薄膜发光性质研究

为了得到最优发光的薄膜材料成分参数,采用均匀设计和二次通用旋转组合设计相结合的方法建立发光强度与薄膜中氧含量和Ce³⁺ 离子掺杂浓度的回归方程,并用遗传算法求其取最大值时的解。用中频反应磁控溅射技术制备了相应成分的Al₂O₃:Ce非晶薄膜。在320nm光激发下,获得了较理想的发射光谱,对薄膜发光机理分析表明:薄膜的光致发光来自于Ce³⁺ 离子的5d1激发态向基态4f1的两个劈裂能级的跃迁。发光强度强烈的依赖于薄膜的掺杂浓度和氧元素含量。XPS检测表明,Al₂O₃:Ce薄膜中存在Ce³⁺ 。Ce³⁺ 含量和薄膜的化学成分是通过X射线散射能谱(EDS)测量的。薄膜试样的晶体结构应用X射线衍射分析。     

Femtosecond Z-scan measurements of nonlinear refraction in nonlinear optical crystals

We report an investigation of third-order optical nonlinearities in several nonlinear optical crystals using the Z-scan technique with femtosecond laser pulses at 780 nm wavelength. The crystals studied include LiNbO₃:MgO, KTiOAsO₄, KTiOPO₄, β-BaB₂O₄ and LiB₃O₅, which are extensively used for ultrashort-pulse second-harmonic generation and optical parametric oscillation. The nonlinear refractive index n₂ in these crystals has been determined to be in the range from 10⁻¹⁶ to 10⁻¹⁵ cm²/W. No two-photon absorption has been observed. The experimental results are compared with the two-band model for the bound electronic Kerr nonlinearity. It is shown that the measured n₂ values in β-BaB₂O₄ and LiB₃O₅ are one order of magnitude smaller than those of LiNbO₃:MgO, KTiOAsO₄, KTiOPO₄, which is in agreement with the theoretical prediction.     

Mg共掺杂Gd3(Al,Ga)5O12:Ce晶体快发光的作用机理

Gd₃(Al,Ga)₅O₁₂:Ce (GAGG:Ce)闪烁体综合性能优异, 应用前景广阔。为加快GAGG的发光衰减速度, 本研究通过提拉法生长了Mg共掺的Gd₃(Al,Ga)₅O₁₂:Ce单晶。测试结果显示, 随着Mg²⁺掺杂浓度增加, 晶体的闪烁衰减速度加快, 光输出降低。传统解释认为, Mg²⁺通过电荷补偿作用将部分Ce³⁺转换成Ce⁴⁺, 后者的发光速度更快。本研究尝试从缺陷的形成与抑制的角度来讨论Mg改善GAGG:Ce晶体闪烁性能的作用机理。由于Ce的离子半径比Gd大, Ce离子掺入将导致发光中心Ce_Gd附近的晶格发生畸变。畸变结果为近邻的八面体格位空间变大, 反位缺陷将更容易在这些变大的八面体格位形成。最终每个发光中心Ce_Gd被四个反位缺陷Gd_Al包裹, 后者捕获载流子, 延缓从基体到发光中心的能量传递, 导致发光速度变慢。由于Mg的离子半径介于Gd和Al之间, Mg_Al将更容易在上述畸变的八面体格位形成, 这会抑制反位缺陷Gd_Al在发光中心Ce_Gd附近形成(或富集), 最终降低(甚至消除)反位缺陷对发光中心的不良影响。XEL测试结果显示, 随着Mg掺杂量增大, 与反位缺陷相关的发射峰强度变弱, 这可以证明Mg对反位缺陷有抑制作用。     

残余应力对涂覆Al2O3涂层的ZrO2陶瓷的强度和裂纹扩展阻力的影响

本研究在ZrO₂基体表面涂覆一薄层Al₂O₃涂层, 利用基体与涂层之间热膨胀系数不匹配, 在Al₂O₃-ZrO₂预应力陶瓷(简称A_CZ_S预应力陶瓷)表层引入压应力。采用维氏压痕法评价残余应力对A_CZ_S预应力陶瓷的表层和基体中裂纹扩展阻力的影响。理论分析结合实验结果表明: 表层的压应力使得A_CZ_S预应力陶瓷的裂纹扩展阻力增大, 最终导致强度和损伤容限提高; 且A_CZ_S预应力陶瓷表层的压应力和裂纹扩展阻力随着基体截面积与涂层截面积比值的增加而增大。当ZrO₂基体表层的Al₂O₃涂层厚度为40 μm时, 表层压应力使A_CZ_S预应力陶瓷的弯曲强度达到(1207±20) MPa, 相比于同种工艺下制备的ZrO₂陶瓷强度提高了32%, 同时也是Al₂O₃强度的3倍。此外, A_CZ_S预应力陶瓷也表现出很好的抗热震性能。     

大尺寸硅酸铋晶体的原料合成、晶体生长及闪烁性能研究

以Si(OC₂H₅)₄和Bi(NO₃)₃·5H₂O作为前驱体、柠檬酸作为溶剂, 按化学计量比配料, 采用溶胶-凝胶法合成并经高温烧结制备了纯相Bi₄Si₃O₁₂多晶粉末, 每批次可合成250 g。以此为原料、<001 >取向BSO为籽晶, 在坩埚下降炉内生长了BSO晶体, 讨论了晶体的析晶行为, 获得了30 mm × 30 mm × 210 mm的高质量BSO晶体。闪烁性能测试表明, 该晶体能量分辨率为18.9%, 光输出为同等条件下CSI(T1)晶体的7.2%。     

MnTe and ZnTe grown on sapphire by molecular beam epitaxy

We report on growth of MnTe layers by molecular beam epitaxy on Al₂O₃ substrates and of ZnTe layers on hybrid MnTe/Al₂O₃ substrates. The aim of our work was to prepare hexagonal phases of epitaxial thin films of these two materials. In the case of MnTe, the hexagonal NiAs-type phase was prepared by depositing the film directly on Al₂O₃ substrates. On the other hand, the crystal structure of ZnTe layers grown on hybrid MnTe/Al₂O₃ substrates was found to depend on the layer thickness: layers thinner than 0.05 μm grew in a metastable hexagonal wurtzite structure, but with further increases of the thickness, the cubic zinc blende phase of ZnTe tended to appear. The structural properties of MnTe and ZnTe layers were characterized by high energy electron and X-ray diffraction methods. Electrical properties of MnTe films were assessed by the Hall effect measurements. The topography and microstructure were analyzed by atomic force microscope. The Néel temperature and magnetic domains structure of antiferromagnetic hexagonal MnTe layers were obtained from neutron experiments.     

Gd3(Al,Ga)5O12:Ce闪烁晶体扭曲生长、组分偏析与性能研究

新型闪烁晶体Gd₃(Al,Ga)₅O₁₂:Ce(简写为GAGG:Ce)在制备过程中易出现多晶扭曲生长、组分偏析等问题, 严重影响晶体的性能。为了得到大尺寸高质量的GAGG:Ce晶体, 采用X射线衍射(XRD)、电感耦合等离子体发射光谱(ICP-OES)和X射线激发发射谱(XEL)等手段, 结合熔体特性分析了GAGG:Ce晶体多晶扭曲生长、组分偏析的形成机制。通过调整温场、抑制组分挥发等方法生长出φ50 mm×120 mm的GAGG:Ce晶体, 并重点研究了GAGG:Ce晶体的光谱特性与闪烁性能。结果表明: GAGG:Ce晶体的光输出达58000 ph./MeV, 能量分辨率为6.4%@662 keV, 在550~800 nm波长区间的透过率约为82%。晶体闪烁衰减快分量为126 ns (83%), 慢分量为469 ns (17%)。晶体的发射峰中心波长在550 nm左右, 与硅光电倍增管的接收波长匹配, 且发光峰值处的透过率EWLT(Emission Weighted Longitudinal Transmittance)值高达79.8%。GAGG:Ce晶体兼具高光输出与高能量分辨率, 在中子和伽马射线探测领域具有广阔的应用前景。     

In:Ga2O3氧化物半导体晶体的生长与性能研究

β-Ga₂O₃晶体是一种新型宽禁带氧化物半导体材料, 本征导电性差。为了在调控导电性能的同时兼顾高的透过率和结晶性能, 离子掺杂是一种有效的途径。采用光学浮区法生长出ϕ8 mm×50 mm蓝色透明In:Ga₂O₃晶体, 晶体具有较高的结晶完整性。In³⁺离子掺杂后, β-Ga₂O₃晶体在红外波段出现明显的自由载流子吸收, 热导率稍有减小。室温下, In:Ga₂O₃晶体的电导率和载流子浓度分别为4.94×10^-4 S/cm和1.005×10¹⁶ cm^-3, 其值高于β-Ga₂O₃晶体约1个数量级。In:Ga₂O₃晶体电学性能对热处理敏感, 1200℃空气气氛和氩气气氛退火后电导率降低。结果表明, In³⁺离子掺杂能够调控β-Ga₂O₃晶体的导电性能。     

Synthesis of MoSi2–Al2O3 nanocomposite by mechanical alloying

MoSi₂–Al₂O₃ nanocomposite was synthesized by mechanical alloying (MA) of MoO₃, SiO₂ and Al powder mixture. The structural evolution of the powders was studied by X-ray diffraction (XRD). Both β-MoSi₂ and -MoSi₂ were obtained after 3 h of milling. The spontaneous formation of β-MoSi₂ during milling proceeded by a mechanically induced self propagating reaction (MSR), analogous to that of the self propagating high temperature synthesis (SHS). After 70 h of milling the β-phase transformed to -phase. The crystallite size of -MoSi₂ and Al₂O₃ after milling for 100 h was 12 and 17 nm, respectively. Residual Mo and Si in the 3 and 70 h milled samples formed β-MoSi₂ and Mo₅Si₃ during heating at 1000 °C, respectively.     

Processing, microstructure and properties of C40 Mo(Si,Al)2/Al2O3 composites

The C40 Mo(Si_0.75Al_0.25)₂/Al₂O₃ composites were prepared by spark plasma sintering (SPS) of mechanically alloyed (MA) powders. The Mo(Si_0.75Al_0.25)₂/0–20 vol.% Al₂O₃ materials, showing micron and submicron composite structure, possess a hardness of 13.9–14.6 GPa but a poor toughness of 1.78–1.80 MPa m^1/2. The addition of 30 vol.% Al₂O₃ leads to the formation of the micron C40 Mo(Si_0.75Al_0.25)₂/Al₂O₃ composite with an intergranular distribution of Al₂O₃, that results in a drop of the hardness to 10.2 GPa and an improvement of the toughness to 3.67 MPa m^1/2. The transition of the cleavage facets to the intergranular fracture with the addition of Al₂O₃ is assumed as the main toughening mechanism.     

Fiber single crystal growth by LHPG technique and optical characterization of Ce-doped Lu2SiO5

The laser heated pedestal growth (LHPG) technique has been applied to grow undoped and doped Lu₂SiO₅:Ce³⁺ (LSO:Ce) single crystals fibers with stable diameter. The starting cerium concentration in the melt was [0.05–1] at.%. The thermal and growth conditions allowing pulling transparent single crystals fiber’s were optimised. The fibers have been grown under N₂ + 1% O₂ atmosphere (1 bar). The Ce³⁺ segregation coefficient is 0.28 greater than the crystal grown by Czochralski technique. The as grown fibers demonstrated scintillating properties.