高硼区B_2O_3-Al_2O_3-SiO_2系微晶玻璃

在B_2O_3-Al_2O_3-SiO_2系统中不易得到玻璃体,加入10wt％BaO,能得到均匀、透明的玻璃,此玻璃组成可作为B_2O_3-Al_2O_3-SiO_2 系统微晶玻璃的基础组成。组成为46.5％B_2O_3、23.0％Al_2O_3、20.5％SiO_2、10.0％ BaO的玻璃,退火后存在相分离。热处理时,硼酸铝晶体(9Al_2O_3·2B_2O_3)和莫来石(3Al_2O_3·2SiO_2)晶体析出,形成固溶体,得到能耐高温的微晶玻璃。由于B_2O_3的挥发,玻璃加热时存在热失重。在一定温度下,失重量与时间平方根成线性关系。得到了实用的PWB高硼微晶玻璃扩散源。     

Tm~(3+)掺杂65GeS_2-25Ga_2S_3-10CsI微晶玻璃光谱特性

采用适当的热处理工艺制备了系列掺Tm~(3+)的透明GeS_2-Ga_2S_3-Csl硫卤微晶玻璃。测试了基质玻璃和微晶玻璃样品的密度、显微硬度、红外光谱以及在800nm激光泵浦下的近红外及中红外荧光光谱。结果表明:热处理后样品析出的晶相颗粒为Ga_2S_3和GeS_2的混合体,晶粒尺寸限制在100nm以内;而原本掺杂在玻璃基质中的Tm~(3+)富集在析出的Ga_2S_3和GeS_2晶体的周围,引起了Tm~(3+)周围环境的改变。因此,热处理后的微晶玻璃样品的近红外和中红外荧光强度增强。     

基于ZnO对Yb~(3+)能量传递的宽带光谱转换微晶玻璃

通过熔融冷却方法制备出无掺杂和Yb~(3+)掺杂的40SiO_2·10Al_2O_3·40ZnO·10K_2CO_3·xYb_2O_3(x=0,0.3)玻璃,之后分别在680、730、780℃下对其进行热处理得到含ZnO纳米晶的微晶玻璃。通过X射线衍射、透射电子显微镜验证了不同温度热处理后ZnO纳米晶在玻璃基质中的析出以及Yb~(3+)掺杂对析晶尺寸和析晶度的影响;通过稳态和时间分辨光谱研究了Yb~(3+)掺杂玻璃及微晶玻璃的发光性能。结果表明:微晶玻璃中.ZnO纳米晶尺寸和析晶度均随热处理温度的升高以及Yb~(3+)掺杂浓度的增加而增大。紫外光激发下Yb~(3+)掺杂玻璃的红外发射是基于Yb~(3+)电荷迁移态(CTS)吸收;395 nm激发下Yb~(3+)掺杂微晶玻璃的红外发射是源于ZnO纳米晶对Yb~(3+)离子的能量传递。ZnO纳米晶的可见发光强度随着热处理温度的提高而随之减弱:而源于Yb~(3+)的~2F_(5/2)→~2F_(7/2)跃迁的红外发射的强度在730℃热处理的微晶玻璃中最强。     

Y_2O_3对BaO-Al_2O_3-SiO_2系封接玻璃结构与性能的影响

研究了应用于固体氧化物燃料电池的BaO-Al_2O_3-SiO_3系封接玻璃性能。通过DSC、XRD、SEM及热膨胀仪等方法,研究了Y_2O_3含量、热处理温度、时间热处理条件下封接玻璃结构与性能。研究结果表明:随着Y_2O_3含量的增加,BaO-Al_2O_3-SiO_2封接玻璃,析出的晶体主要是板柱的六方钡长石H-BaAl_2Si_2O_8。玻璃析晶后其微观结构致密,微晶玻璃的热膨胀系数由10.51×10~(-6)·℃~(-1)降低到10.27×10~(-6)·℃~(-1)。Y-1封接玻璃料浆与8YSZ电解质在900℃下热处理2h完成封接,并于820℃下烧结与微晶化10 h,封接玻璃与8YSZ电解质封接界面之间无裂纹、孔洞、反应层的形成,界面结合性能良好。Y-1微晶玻璃在450℃、500℃电阻率为2.27×10~8W·cm、3.71×10~7W·cm。Y-2玻璃在450℃、500℃电阻率为2.21×10~8 W·cm、2.31×10~7 W·cm。     

Tm~(3+)和Dy~(3+)共掺氟氧铝硼硅酸盐玻璃微晶化及白光发射性能

采用高温熔融-淬火/热处理方法在空气气氛中制备了Tm_2O_3和Dy_2O_3共掺氟氧铝硼硅酸盐玻璃及透明微晶玻璃。用转靶多晶X射线衍射仪、荧光分光光度计和热分析仪对玻璃样品进行了表征。结果表明:样品在640～660℃热处理4h和在640℃热处理4～16h可制得透明的含Ba_2LaF_7纳米晶玻璃。增大Tm-Dy共掺浓度并降低La_2O_3浓度时,Ba_2LaF_7析晶倾向降低。此外,热处理析出Ba_2LaF_7微晶相后,样品的Tm_2O_3和Dy_2O_3共掺浓度淬灭点由1%(摩尔分数,下同)提高到了2%。掺杂不同浓度Tm_2O_3和Dy_2O_3时,白光发光色度保持不变。     

ZnO-Al_2O_3-SiO_2系微晶玻璃的热膨胀性能及其影响因素

应用热谱、X射线衍射和透射电镜分析研究了ZnO—Al_O_3—SiO_2系微晶玻璃成分、晶核剂种类和热处理条件对其热膨胀特性的影响和机理。试验表明,在研究的成分范围内,玻璃主要折晶相为α—Zn_2SiO_4、ZnOAl_2O_3以及BaMgAl_3(Si_9Al_3O_(30))和少量β—石英固溶体。其折晶程序和主要晶相组成受玻璃成分、晶核剂和热处理制度控制并本质地影响微晶玻璃的热膨胀特性,从而可能在较宽范围内调节微晶化后玻璃的热膨胀系数,以满足不同的使用要求。     

Yb~(3+)/Er~(3+)共掺锗酸盐氧氟微晶玻璃的白光输出

对组成为50GeO_2-20Al_2O_3-15CaF_2-15LiF稀土离子锗酸盐氧氟玻璃在550℃微晶化热处理24h,得到了透明的微晶玻璃。X射线衍射表明:玻璃中析出了CaF_2纳米晶粒,晶粒尺寸在17 nm左右。在980 nm泵浦光的激发下,Yb~(3+)/Er~(3+)双掺微晶玻璃产生了蓝绿红上转换荧光。随着玻璃中Yb~(3+)的掺杂浓度的增加蓝光和红光荧光强度增大,其中5%Yb~(3+)/1%Er~(3+)(摩尔分数,下同)的微晶玻璃样品的上转换发光已经出现白光效果。通过研究一系列高Yb~(3+)/Er~(3+)浓度比的共掺微晶玻璃样品,实现了对上转换红光绿光与蓝光的荧光强度比例的调整,当Yb~(3+)掺杂浓度为12%、Er~(3+)掺杂浓度为0.01%时,微晶玻璃的上转化发光接近白光。     

ZnO-Al_2O_3-SiO_2系统微晶玻璃的研究

作者利用二液分相的原理,在研究了ZnO-Al_2O_3-SiO_2系统玻璃析晶条件的基础上,用添加B_2O_3的方法成功地制得了微晶玻璃,获得了一个具有实用价值的№6307微晶玻璃组成。研究了形成玻璃和微晶化的工艺制度,并讨论了B_2O_3对玻璃分相和微晶化的作用。     

Bi_2O_3-B_2O_3-WO_3系统微晶玻璃的制备

采用熔融法制备了0.97[x Bi2O3(1-x)B2O3]·0.03WO3(0.25≤x≤O.75)基础玻璃,通过差热分析确定玻璃的特征温度,经热处理制备微晶玻璃.结果表明所制备的玻璃中只有x =0.67和x=0.60两个组成经热处理生成了微晶玻璃,颜色为乳黄色,晶相分别为BiO2和Bi2WO6,在扫描电镜下观察两种晶体的形貌均为颗粒状,晶粒尺寸在0.8～1.0μm.该体系玻璃的密度较大而硬度较小,但热处理后的微晶玻璃的密度和硬度均大于处理前的基础玻璃.     

Na_2O对MgO-Al_2O_3-B_2O_3-SiO_2体系微晶玻璃结构和性能的影响

利用烧结法制备Na_2O-MgO-Al_2O_3-B_2O_3-SiO_2微晶玻璃。采用FT-IR、DSC、XRD和SEM等分析方法,研究玻璃组成中Na_2O对MgO-Al_2O_3-B_2O_3-SiO_2系统微晶玻璃的结构、析晶性能、热膨胀系数以及化学稳定性的影响。结果表明:随着Na_2O含量的增加,玻璃结构中出现了[SiO_4]被破坏和[BO_3]转变为[BO_4]的现象。Na_2O的添加明显降低了样品的玻璃化转变温度与析晶峰值温度,增强了MgO-Al_2O_3-B_2O_3-SiO_2体系微晶玻璃的析晶能力。未加Na_2O的微晶玻璃主晶相为球状顽辉石,添加后的微晶玻璃析出镁橄榄石颗粒和柱状硼镁钛石,最终A_3、A_4只析出硼镁钛石,并且颗粒逐渐细化。随着Na_2O量的增加,微晶玻璃的热膨胀系数呈逐渐增大的趋势。微晶玻璃的耐酸碱侵蚀能力随Na_2O含量的增加先增强后减弱,其中耐碱腐蚀能力相对较强。     

钕-铝系稀土色料的研制

通过钕-铝系列色料合成实验,分析不同配比及不同矿化剂等对色料呈色效果的影响,确定最佳工艺方法。对实验结果进行XRD及色度分析,确定其主晶相为钕酸铝,试样的明度均在70以上,色彩鲜艳亮丽。     

Polycrystalline In2O3 and In2O3/Y2O3 photoanodes

Single crystal In₂O₃ shows promise as a photoanode for the decomposition of water. Because of various difficulties in the preparation of the single crystal material, two simple techniques were developed for the preparation of polycrystalline In₂O₃ anodes. One method involves the thermal decomposition of the nitrate while the other utilizes the chemical vapour deposition technique. Voltammograms and photoresponse spectra of these anodes are compared to the single crystal material. Among other observations, it is noted that the quantum efficiencies of the thermally decomposed films are comparable to the single crystal material. It is also shown that the on-set potential can be shifted to more negative values by forming the mixed oxide In₂O₃/Y₂O₃.     

Phase equilibrium in binary La2O3-Dy2O3 and ternary CeO2-La2O3-Dy2O3 systems

Cerium oxide doped with oxides of rare earth elements is a multifunctional material, a wide range of uses which is associated with its unique physicochemical properties. Phase diagrams of multicomponent systems are the physicochemical basis for the creation of new materials with improved characteristics.In this work, phase equilibria in ternary CeO₂–La₂O₃–Dy₂O₃ and binary La₂O₃–Dy₂O₃ systems in the whole concentration range were studied. No new phases have been identified in these systems. An isothermal section of the phase diagram of the CeO₂–La₂O₃–Dy₂O₃ system at a temperature of 1500 °С is constructed. No new phases have been detected in the system. It was found that in the studied ternary system solid solutions are formed on the basis of (F) modification of CeO₂ with structure of fluorite type, monoclinic (B), cubic (C) and hexagonal (A) modifications of Ln₂O₃.In the La₂O₃–Dy₂O₃ binary system (1500–1100 °С) three types of solid solutions are formed: based on hexagonal modification A-La₂O₃, monoclinic modification B-Dy₂O₃ and cubic modification C-Dy₂O₃ separated by two-phase fields (A+B) and (B+C), respectively. The boundaries of the regions of homogeneity of solid solutions based on A-La₂O₃ are determined by compositions containing 35–40, 20–25, 15–20 mol% Dy₂O₃ at 1500, 1250, 1100 °C, respectively. From the obtained data it follows that the solubility of Dy₂O₃ in the hexagonal modification of lanthanum oxide is 39 mol% at 1500 °C, 23 mol. % at 1250 °C and 16 mol% at 1100 °C. The limits of existence of solid solutions based on monoclinic B-modification are determined by compositions containing 30–35, 65–60 (1250 °С), 35–40, 55–60 (1100 °С) 40–45, 70–75 (1500 °C) mol% Dy₂O₃.In the studied system, with a decrease in temperature from 1500° to 1100°C, there is a decrease in the solubility of La₂O₃ in the crystal lattice of cubic solid solutions of C-type from 16 to 10 mol%.     

Na2O-Al2O3-Fe2O3系烧结过程中铝、铁的反应行为

以Al2O3, Fe2O3和Na2CO3为原料,对Na2O-Al2O3-Fe2O3系烧结过程中的反应行为进行了详细研究. 基于溶出率与时间、温度的关系,证明Na2O×Al2O3和Na2O×Fe2O3的生成反应动力学都服从Zhuralev-Lesokin-Tempelman模型,表观活化能分别为186.59和80.92 kJ/mol,表明Na2O×Fe2O3比Na2O×Al2O3在动力学上更易形成;Al2O3易与Na2O×Fe2O3反应形成Na2O×Al2O3和Fe2O3,在1273 K烧结30 min,所得熟料Al2O3溶出率达98.51%;Fe2O3对Na2O×Al2O3的形成有双重作用,在1273 K下可加速Na2O×Al2O3的形成,超过1323 K,促使Na2O×Al2O3分解成Na2O和b-Al2O3,且随着温度升高或时间延长,分解程度增高,从而导致熟料中Al2O3溶出率显著降低.     

Fe2O3-MnO-Cr2O3-La2O3系统紫色颜料的制备及表征

采用溶胶均匀共沉淀法于低温下合成了含少量稀土氧化物La2O3的紫色颜料，并采用颜色测定、SEM、XRD等手段对颜料的颜色、检度及结晶构造等进行了表征。     

Separation of Phases by Spinodal Decomposition in the Systems Al2O3−Cr2O3 and Al2O3−Cr2O3−Fe2O3

Separation of phases was investigated in the hexagonal (rhombohedral) systems Al₂O₃−Cr₂O₃ and Al₂O₃−Cr₂O₃−Fe₂O₃. The binary system shows a miscibility gap with a T_c of 950°C; the miscibility gap for the ternary system was determined for a constant Cr₂O₃ content of 16.6 mol%. Dark field transmission electron microscopy of solid solutions annealed within the miscibility gap showed dark and light lamellas ∼50 to 200 Å thick. X-ray diffraction results for the solid solutions in the ternary system indicated that, in the early stages of annealing, broadening occurred only on (hkl) reflections where l≠0. There was no major change in the X-ray diffraction patterns of the annealed solid solutions in the binary system. Electron diffraction results indicated, however, that phase separation in both systems proceeded in the [001] direction. Solid solutions in the binary system separated very slowly; the separation could be enhanced hydrothermally. The mechanism of the separation of phases in both systems is spinodal and proceeds as follows: solid solution→intermediate modulated phase→equilibrium phases.     

ß-Al2O3 synthesis from m-Al2O3

-Al₂O₃ formation fromm-Al₂O₃ was found by a new convenient technique. By thermal decomposition of a complex compound, trioxalatoaluminate Na _x (NH₄)_3–x [Al(C₂O₄)₃]yH₂O(0.091 x 0.333;y= 3), a very fine powder ofm-Al₂O₃ was formed. The decomposition process was examined by thermal analysis and X-ray diffraction and the phase relation of the system Na₂O-Al₂O₃ in the midtemperature region between 600 and 1200° C is discussed briefly. The tablet ofm-Al₂O₃ was fired at 1600° C for 30 min to prepare dense-Al₂O₃ ceramics, the apparent density of which was greater than 95% of the theoretical value. The sintered tablet was examined from the structural point of view and the electrical conductivity was measured by an a.c. method to verify that the procedure of the complex decomposition is a suitable technique for-Al₂O₃ synthesis.     

Oxide/oxide composites in the system Cr2O3-Y2O3-Al2O3

Ceramic compacts in the systems Al₂O₃–Y₂O₃, Cr₂O₃–Y₂O₃ and Y₃(Cr_yAl_1-y)₅O₁₂ (Cr-doped YAG) were prepared by solid state reaction in calcined co-precipitated powder mixtures of appropriate compositions. Various solid-solution phases were formed, e.g. Y₃(Al_1-xCr_x)₅O₁₂, YAl_yCr_1-yO₃ and Al_2-xCr_xO₃. Composite materials in the pseudo-binary or ternary systems Al₂O₃–Y₃Al₅O₁₂, Cr₂O₃–Y₂O₃ and Y₃(Al_1–xCr_x)₅O₁₂–YAl_yCr_1–yO₃–(Al_zCr_1−z)₂O₃ were obtained by hot-pressing appropriate powder precursors at 1600–1650°C for 1 h. The microstructure of the prepared materials was studied in a scanning electron microscope with element analysis facilities. X-ray diffraction was used to reveal the phases present and their lattice parameters. The chemical compatibility of these phases was investigated. The results are discussed with a special emphasis on the solubility of Cr in the YAG structure, and on the compatibility relationship between Cr-doped YAG and its neighbouring phases. A gel-coating process for preparing Al₂O₃–YAG composites with tailored microstructures is also described.     

Bactericidal Effectiveness of O3, O3/H2O2 and O3/TiO2 on Clostridium perfringens

The purpose of this research is to evaluate the bactericidal capacity of different Advanced Oxidation Treatments (AOTs) based on ozone: ozone, ozone/hydrogen peroxide and ozone/titanium dioxide on a wild strain of Clostridium perfringens, a fecal bacterial indicator in drinking water. The dose of ozone consumed ranges from 0.6 mg L^?1 min^?1 to 5.13 mg L^?1 min^?1 depending on the process and on the sample. In the treatments combined with O₃, H₂O₂ dose utilized is 0.04 mM and TiO₂ dose, 1 g L^?1. In order to evaluate the influence of natural organic matter and suspension solids over the disinfection rate, treatments are performed with two types of water – natural water from Ebro River (Zaragoza, Spain) and NaCl solution 0.9%. To achieve 4 log units of inactivation, 3.6 mg O₃ L^?1 is necessary in O₃ treatment, 4.25 mg O₃ L^?1 in O₃/TiO₂ system and 2.7 mg O₃ L^?1 in O₃/H₂O₂ after processing the natural water. In NaCl solution, to get the same inactivation, 0.42 mg O₃ L^?1 is necessary in O₃ treatment, 1.15 mg O₃ L^?1 in O₃/TiO₂ system and 0.06 mg O₃ L^?1 in O₃/H₂O₂ process. Even though the three treatments studied have a high bactericidal activity due to the number of surviving bacteria decreases to non-detectable levels, O₃/H₂O₂ is the most effective system for eliminating C. perfringens cells in a lower contact time, followed by O₃ and finally O₃/TiO₂ system.