High-temperature stability of Mg(Al,Cr)2O4 spinel co-existing with calcium aluminates in air

Cr₂O₃ is a well-known corrosion resistant oxide used in refractory applications. However, it can oxidize into toxic and water-soluble Cr(VI) compounds upon reaction with calcium aluminate cement phases in the presence of oxygen, which subsequently causes disposal problems after use. This study describes the extent to which chromium in the spinel Mg(Al,Cr)₂O₄ phase can be oxidized to Cr(VI) when it reacts with the calcium aluminate cement phases C₁₂A₇, CA, CA₂ and free CaO at 1300 °C in air, using XRD, XPS and leaching tests (TRGS 613 standard) as analytical tools. On reaction with CaO, the Mg(Al,Cr^III)₂O₄ spinel mainly transformed into hauyne (Ca₄Al₆Cr^VIO₁₆) and Ca₅Cr₃O₁₂ which contains both Cr(IV) and Cr(VI). The reaction of C₁₂A₇ and CA with the spinel phase also resulted in the formation of Ca₄Al₆CrO₁₆. Conversely, the reaction of Mg(Al,Cr^III)₂O₄ spinel with CA₂ resulted in the formation of only a trace amount of Cr(VI). Water-soluble Cr(VI) leached in large quantities (>100 mg/L) from samples where the Mg(Al,Cr^III)₂O₄ reacted with either C₁₂A₇ or CA. Almost no Cr(VI) leached from the sample when Mg(Al,Cr^III)₂O₄ reacted with CaO, using the standard TRGS 613 leach test, but a significant amount of Cr(VI) was released into solution when leached with a HCl solution for 12 h. Both Cr(IV) and Cr(VI) present in the Ca₅Cr₃O₁₂ dissolved into acidic solution. Only a small amount of Cr(VI) leached from the sample that resulted when spinel was reacted with CA₂, even after a prolonged HCl leach. Cr(III) in spinel Mg(Al,Cr)₂O₄ is very stable and does not leach in either distilled water or acidic solution.     

发光体MAl2O4:Eu2+,RE3+的长余辉形成机理

提出了Eu^2 激活的MAl2O4:Eu^2 ,RE^3 （M＝Ca,Sr,Ba;RE=Dy,Nd,Ho,Er,Pr,Tb等稀土元素）系列铝酸盐发光体的长余辉发光机理。认为O^2-空位Vo是一种电子俘获陷际，是形成余辉的根本原因，RE^3 的引入使陷阱深度适宜而使余辉时间延长。缺陷在晶格中成簇分布，Vo和碱土金属离子空位VM在高温下可相互缔合。利用电子陷阱模型解释了实验中的一些普遍现象并提出了固相反应法合成此类发光体的工艺改进措施。     

Photocatalytic performance of Fe-substituted ZnAl2O4 powders under sunlight irradiation on degradation of industrial dyes

Using the sol–gel auto combustion method with diethanolamine (DEA) as fuel, a sequence of iron-substituted zinc aluminates, ZnFe_xAl_2-xO₄ powders, including variable Fe³⁺ ion concentrations (0 ≤ x ≤ 2) were effectively prepared. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), the Brunauer–Emmett–Teller (BET) method, UV–visible diffuse reflectance spectroscopy (UV-DRS), and vibrating sample magnetometer (VSM) were employed to examine the structures, chemical bonds, morphologies, composition, surface area, and optical properties as well as the magnetic behavior of the obtained samples. A single-phase spinel structure was obtained for the calcined aluminate powders with different interplanar spacing and crystallite sizes, as revealed by the classification results. The bandgap energy (E_g) of adapted aluminates was in the range of 2.04-3.14 eV, identified as being much lower compared to the pure sample (5.60 eV). Thus, Fe³⁺-substituted ZnAl₂O₄ samples could be successfully photoexcited using both ultraviolet and visible light, as suggested by the results. Examination of how the four main pollutant types decay when irradiated by sunlight was carried out to assess the samples and establish photocatalytic activity. These contaminants included rhodamine B (RhB), methylene blue (MB), methyl orange (MO), and methyl red (MR). The performance of photocatalytic degradation reached 98% after 150 min for all optimal samples of organic dyes. Besides, each of the altered photocatalysts could be recycled and displayed high stability. The S-shaped curve of ferrimagnetism can result in those samples as found by the magnetic measurements, though pure ZnAl₂O₄ displays diamagnetic characteristics. The adapted samples show intense improvement in the remanent magnetization (M_r) when compared to pure ZnAl₂O₄, signifying that magnetic photocatalyst recovery by applying an external magnetic field is easy. Thus, these results offer a convincing sign that ZnAl₂O₄ powders replaced by Fe³⁺ could provide the ability to aid in the ecologically friendly collection of solar energy.     

不同添加剂对SrAl2O4:(Eu,Dy)磷光体发光性能的影响

在较低的温度下用燃烧合成法快速合成了 Eu2 ,Dy3 掺杂的SrAl2O4长余辉磷光体发光材料.研究了P2O5,CaF2,H3BO3,NaF 几种添加剂对SrAl2O4:(Eu,Dy)粉体发光性能的影响.结果发现:H3BO3和P2O5的添加有利于改善磷光体的发光性能,而在配料中加入CaF2和NaF,磷光体发光效率降低.随着这几种添加剂的加入,SrAl2O4:(Eu,Dy)磷光体材料发射光谱的主发射峰不同程度的出现蓝移.根据实验结果分析了添加剂的作用机理.     

水化放热曲线在研究铝酸钙水泥和浇注料中的应用

为了预测水泥或浇注料的凝结性和强度发展趋势,取1500g按一定程序搅拌好的水泥胶砂或浇注料,迅速倒入模具中,振动10s后置入j-型热电偶,由计算机绘制出其水化放热曲线。浇注料的水化放热曲线形貌不仅能反映水泥的矿物组成和反应活性,而且能反映浇注料中其他原材料(如骨料、氧化铝或二氧化硅微粉和外加剂等)和作业环境对水泥及浇注料的影响,为此可用于水泥与浇注料流变特性的研究和控制,同时也为浇注料用原材料的甄选提供了一种有用的工具。     

Activity–Composition Relations in NiAl2O4─MnAl2O4 Solid Solutions and Stabilities of NiAl2O4 and MnAl2O4 at 1300° and 1400°C

Activities of NiO were measured in the oxide and spinel solutions of the system MnO–NiO–Al₂O₃ at 1300° and 1400° C with the aim of deriving information on the thermodynamic properties of the spinel phases. Synthetic samples in selected phase assemblages of the system were equilibrated with metallic nickel and a gas phase of known oxygen partial pressures at a total pressure of 1 atm. The data on NiO activities and directions of conjugation lines between coexisting oxide and spinel phases were used to establish the activity–composition relations in spinel solid solutions at 1300° and 1400°C. The MnAl₂O₄–NiAl₂O₄ solid solutions exhibit considerable negative deviations from ideality at these temperatures. The free energy of formation of MnAl₂O₄ from its oxide components (MnO + Al₂O₃) at 1300° and 1400°C is calculated to be −24.97 and −26.56 kJ. mol⁻¹, respectively. The activities determined in the stoichiometric spinel solid solutions are more negative as compared with those predicted from cation distribution models.     

铝酸盐长余辉材料的制备方法进展

对碱土金属铝酸盐体系的长余辉荧光材料的光谱特性以及近几年研究较为关注的几种制备方法进行了详细的介绍说明,比较了各材料体系的荧光性能以及各种制备方法的优劣,并对新的合成方法进行了展望。     

掺杂的SrAl2O4:Eux2+,Dyy3+长余辉粉的合成、表征及发光性质

采用自蔓延高温合成法制备了组成为SrAl2O4:Eu2+x,Dy3+y的2组(x:y=1:1,x:y=1:2)12种铝酸锶长余辉发光粉,测试结果表明,组成为SrAl2O4:Eu2+0.0125,Dy3+0.0125的发光亮度最好。以上述配比为依据,又分别引入了可以用于制备荧光材料的阳离子Li+、Be2+,以及既可以用于制备荧光材料也可以用于制备自激活荧光材料的阳离子Zn2+、Cd2+、Pb2+,共制得5个系列22种铝酸锶(SrAl2O4)长余辉发光粉。Zn2+0.0125的掺杂使得SrAl2O4:Eu2+0.0125,Dy3+0.0125的余辉亮度得到大幅度提高,而且SrAl2O4:Eu2+0.0125,Dy3+0.0125,Zn2+0.0125的衰减速度也明显慢于SrAl2O4:Eu2+0.0125,Dy3+0.0125。X射线衍射结果表明,掺杂少量稀土离子(Eu2+和Dy3+)不会改变SrAl2O4基质的晶体结构。另外,透射电镜分析和粒度分布结果表明,产物为疏松多孔的蘑菇云状固体,粒度在10μm左右。     

HfO2 Gate Dielectrics for Future Generation of CMOS Device Application

Introduction High- k gate dielectrics have been extensivelystudied as alternates to conventional gate oxide( Si O2 ) due to the aggressive downscaling of Si O2thickness in CMOS devices,and hence the exces-sive gate leakage.Hf O2 has emerged as one...     

Removal of NOx: Part II. Species formed during the sorption/desorption processes on barium aluminates

The formation of various species formed during the adsorption of NO_x issued from a synthetic lean-burn exhaust gas upon barium aluminates was studied using FTIR and TGA. The results have been systematically compared to those obtained with bulk BaO. Two factors are responsible for the difference observed during adsorption/desorption tests on the two solids. On one hand, stable carbonates are formed on BaO whereas no carbonate is formed on barium aluminate. On the other hand, the structure of the nitrates formed on these two compounds is very different, an N-bounded nitrate is formed on barium aluminate and not on bulk BaO.