不锈钢表面SiO2-ZrO2-Al2O3-Cr2O3陶瓷涂层性能的研究

将氧氯化锆、正硅酸乙脂、无水乙醇3种物质按物质的量比135放进烧杯搅拌均匀后,再放进微波炉加热10s取出,得到SiO2-ZrO2溶胶。然后,将100mL氨水、50mL硝酸铝溶液和50mL硝酸铬溶液混合均匀后,放进微波炉加热1min后取出,即制得Al2O3-Cr2O3溶胶。取SiO2-ZrO2溶胶和Al2O3-Cr2O3溶胶按n(SiO2)n(ZrO2)n(Al2O3)n(Cr2O3)=6211混合,搅拌2h,得到SiO2-ZrO2-Al2O3-Cr2O3复合溶胶。将打磨、除锈、除油处理后的不锈钢基体浸入SiO2-ZrO2-Al2O3-Cr2O3溶胶一定时间后,以浸渍提拉法得到均匀的溶胶涂层,真空干燥48h,经700℃热处理1h后便可得到SiO2-ZrO2-Al2O3-Cr2O3复合陶瓷涂层。采用XRD、IR和SEM对不同条件热处理的复合陶瓷涂层的物相组成、表面形貌进行分析,并对复合陶瓷涂层的性能进行了研究。结果表明(1)SiO2-ZrO2-Al2O3-Cr2O3复合溶胶热处理后为非晶态材料,且在凝胶中形成了三维的硅氧四面体网络骨架;(2)涂层试样不出现龟裂或脱落的循环次数(900℃,空冷)在15~30次范围内,涂层的抗热震性较好;(3)在700℃热处理1h条件下,涂层单位面积的质量损失最小,具有较好的抗腐蚀性;(4)有涂层试样较无涂层试样的氧化速率低,且以3次涂膜的氧化速率最低;涂层由粒径为2~3μm左右的微粒组成,涂层较致密,抗氧化性较好;(5)有涂层试样的耐磨性均优于无涂层试样,有涂层试样的以3次涂膜的耐磨性最好。     

煤灰渣在Cr2O3-Al2O3-ZrO2砖表面润湿与渗入行为的研究

将灰分(w)为6.81%,挥发分(w)为32.68%的煤制成煤灰后,压成圆柱形的煤灰柱放在Cr2O3(w)含量约为90%的Cr2O3-Al2O3-ZrO2砖上,再推入管式加热炉中,在Ar气氛下,通过升温试验(升温至1200℃)和保温试验(升温至1165℃保温20min),考察了煤灰渣在Cr2O3-Al2O3-ZrO2砖表面的润湿与渗入行为。结果表明无论是升温试验还是保温试验,煤灰柱的变化过程完全一致,都经历了变形、熔融和润湿等一系列的变化。对升温试验过程中煤灰柱变化的观察和照片的处理结果均表明煤灰柱在1100℃时局部凹进去形成不规则形状;在1165℃时煤灰完全熔化,煤灰柱变成半球形;在1180℃时接触角<90°,煤灰渣开始在Cr2O3-Al2O3-ZrO2砖表面发生润湿。对升温试验后的Cr2O3-Al2O3-ZrO2砖表面和渣表面的化学组成分析表明有大量Fe堆积在煤灰渣与Cr2O3-Al2O3-ZrO2砖表面接触处,而邻近处几乎没有发现Fe,可能是由于Fe与Cr2O3-Al2O3-ZrO2砖中的一些组分形成了某种晶相,使得Fe很难进入Cr2O3-Al2O3-ZrO2砖;接近煤灰渣的Cr2O3-Al2O3-ZrO2砖表面组成中出现了Ca,说明熔融灰渣中的Ca渗入Cr2O3-Al2O3-ZrO2砖;同时,煤灰渣中出现了Cr,表明在熔融灰渣渗入Cr2O3-Al2O3-ZrO2砖的同时,砖中的Cr也熔入了熔渣中。     

结合剂对Al2O3-MgAl2O4-SiC-C质铁沟浇注料性能的影响

以电熔镁铝尖晶石(粒度为5～3mm、3～1mm)和电熔白刚玉颗粒(粒度<1mm)以及白刚玉细粉、碳化硅细粉、活性αAl2O3微粉、Si粉和球状沥青等为主要原料,在保持基料的配比不变的条件下分别采用铝酸钙水泥(w,3%) SiO2微粉(w,2%)及ρAl2O3(w,4%)为结合剂,振动成型为Al2O3-MgAl2O4-SiC-C试样,室温养护24h后脱模,分别于110℃24h、1100℃3h和1500℃3h(埋炭)条件下热处理,然后测定试样的体积密度、显气孔率、线变化率、抗折强度、耐压强度和抗渣性。试验结果表明:铝酸钙水泥 SiO2微粉结合的浇注料流动性较好,经110℃24h、1100℃3h和1500℃3h(埋炭)热处理后,试样的显气孔率较小,体积密度较大,常温耐压强度和常温抗折强度优于以ρAl2O3为结合剂的;但是,采用铝酸钙水泥 SiO2微粉作结合剂的试样经1500℃埋炭3h处理后的线变化率较大,试样的高温抗折强度和抗侵蚀性能也明显低于ρAl2O3结合试样的。     

添加高Al2O3粉煤灰对高炉用炮泥性能的影响

本论文以粘土,SiO2微粉,SiC微粉,棕刚玉,高温沥青粉为原料,以焦油为结合剂,分别外加质量分数为0%、10%、15%和20%的高Al2O3粉煤灰,制备无水炮泥,并对其抗折强度、体积密度和抗渣性能进行了研究.研究了炮泥试样的微观结构,探讨了粉煤灰添加量对其性能的影响.研究结果表明:添加高Al2O3粉煤灰使炮泥试样的抗折强度略有降低,但仍能满足生产的要求,其中添加15%高Al2O3粉煤灰的炮泥试样抗折性能最好.在还原气氛下,添加高Al2O3粉煤灰的炮泥具有良好的抗渣性.     

危废焚烧炉用Al2O3-Cr2O3-ZrO2砖抗渣侵蚀性及六价铬形成研究

Al2O3-Cr2O3-ZrO2砖具有较优良的抗渣侵蚀性能和力学性能,被作为内衬材料应用于危废垃圾焚烧炉.然而,危废垃圾来源广,成分复杂,其焚烧所产生的渣对砖的侵蚀程度及机理也必然不同.此外,砖中的Cr2O3在高温下可能氧化为含Cr(Ⅵ)的有害物质.为此,通过静态抗渣实验研究了四种不同组成危废灰渣对Al2O3-Cr2O3-ZrO2砖的侵蚀过程及机理,并通过浸出实验研究了熔渣对砖中Cr(Ⅵ)形成的影响.结果 表明:不同渣对Al2O3-Cr2O3-ZrO2砖的侵蚀程度及机理各不相同.高钙渣A侵蚀过程中,生成了高熔点的CA6、Ca2Al2SiO7和Ca2SiO4相,在一定程度上减缓了渣的侵蚀速度,砖体表现出最好的抗侵蚀性.高铁渣D侵蚀过程中生成熔点较低的CaFe2O4相,加之砖中Al2O3在Fe2O3-SiO2渣中的溶解度较高,因此高铁渣D对砖体的侵蚀程度最严重.高硅渣B和C侵蚀过程中主要生成钙铝黄长石新相,渣对砖体的侵蚀程度居中.不同的渣侵蚀后,渗透层中的Cr(Ⅵ)含量均增加,且渣的组成对Cr(Ⅵ)含量影响较大.由于CaO能显著促进Cr(Ⅲ)氧化为Cr(Ⅵ),高钙渣A侵蚀后,渗透层中的Cr(Ⅵ)含量最高,为84.7 mg/kg.SiO2可优先与CaO和Na2O等碱金属氧化物反应生成稳定化合物,高硅渣B和C侵蚀后,渗透层中的Cr(Ⅵ)含量较低,分别为9.9 mg/kg和13.6 mg/kg.对于高铁渣D,浸出过程会有含Cr(Ⅵ)的水化相(3CaO· Al2O3·CaCrO4·nH2O)形成,降低了Cr(Ⅵ)的浸出能力.     

煅烧气氛对Al2O3-Si材料组成、结构和性能的影响

以电熔白刚玉、α-Al2O3微粉和Si粉为主要原料,以酚醛树脂为结合剂,制备Al2O3-Si复合材料试样.研究了煅烧气氛对1 500℃烧后试样性能、组成和显微结构的影响.结果表明:1)在氧化气氛和弱氧化气氛中煅烧后,试样表面生成含莫来石的玻璃膜,保护了试样内部的单质Si;由于单质Si的液相助烧结作用,试样的致密度和常温强度较高,但其高温抗折强度和抗热震性较低.2)在弱还原气氛和还原气氛中煅烧后,试样中的单质Si完全与Al2O3和通过气孔进入的CO、N2反应,生成晶须状SiC、粒状Si2N2O(或絮状O'-SiAlON),试样的致密度和常温强度减小,高温强度和抗热震性提高.3)在氮气气氛中煅烧后,Si完全反应生成短柱状β-SiAlON 和晶须状SiC,试样的高温强度和抗热震性明显提高.     

Al2O3/SiO2比和煅烧温度对煤系高岭土物理性能与显微结构的影响

以内蒙产的煤系高岭土为原料,通过添加α-Al2O3和SiO2细粉,以羧甲基纤维素为结合剂,在1450℃、1500℃、1550℃、1600℃的煅烧温度下制备了不同Al2O3/SiO2(Al/Si)比的试样.对试样的体积密度、显气孔率、耐压强度、线变化率等物理性能进行了检测.采用SEM与EDS分析,研究了试样的显微结构.研究表明:随着煤系高岭土中Al2O3/SiO2比从0.856增加到4.5,试样的体积密度从2.55下降到2.14 g/cm3,气孔率从5％增加到30％,耐压强度从20 MPa增加到50 MPa,体积变化从-17％增加到7％.当Al2O3/SiO2比为2.6时,试样经过1500℃×3h后,可以生成大量的柱状莫来石,具有良好的物理性能,可以作为一种有用的Al2O3-SiO2系低蠕变耐火材料.     

尖晶石对Al2O3-SiC-C质铁沟浇注料性能的影响

以新型亚白刚玉(8~5 mm、5~3 mm、3~1 mm、≤1 mm、≤0.044 mm)、SiC(≤1 mm、≤0.088 mm)、尖晶石粉(≤0.044 mm)、SiO2微粉、α-Al2O3微粉、铝酸钙水泥、Si粉和球状沥青等为主要原料,在Al2O3-SiC-C质铁沟浇注料的配料组成中分别加入质量分数为0、4%、7%、10%、13%的镁铝尖晶石粉,混练均匀后振动成型为40 mm×40 mm×160 mm的条状试样和50/20 mm×50/20mm的坩埚试样,经110℃24 h和1 450℃3 h热处理后测定试样的体积密度、显气孔率、常温抗折强度、常温耐压强度、烧后线变化率和抗渣性能,并且进行了XRD、SEM和EDS分析。结果表明:加入适量镁铝尖晶石粉后,由于改善了试样的成型密度,促进了试样的烧结,因而提高了试样的密度、强度、体积稳定性和抗渣性;但是,由于尖晶石和刚玉的热膨胀系数不同,加入过多的镁铝尖晶石粉会导致试样中产生过多的微裂纹,从而对试样的密度、强度、体积稳定性和抗渣性不利;本试验中,尖晶石粉的最佳加入量(质量分数)为10%;尖晶石加入量为10%的试样中有长度为30~80μm的SiC晶须生成,并且其颗粒与基质之间结合紧密。     

ZrO2基Al2O3-ZrO2-C质高温陶瓷材料抗渣性能研究

以板状刚玉、活性α—氧化铝、氧化锆(PSZ)、碳黑为主要原料,以金属硅和碳化硼作为添加剂,以热固性酚醛树脂作为结合剂,制备了ZrO2基Al2O3-ZrO2-C质材料。实验证明添加稳定氧化锆的Al2O3-ZrO2-C质高温陶瓷材料的抗渣性能优于添加单斜氧化锆、纳米氧化锆、金属铝的Al2O3-ZrO2-C质高温陶瓷材料。     

Al2O3-SiC系制品中添加物α-Cr2O3的行为

以电熔刚玉和SiC为基料的制品中添加适量亚微米级的绿铬(α-Cr2O3)时,烧成过程中α-Cr2O3生长到1～5 μm,并与刚玉表面接触区发生互扩散行为.SiC在氧化层中氧化并形成玻璃纤维,使氧化层的组分变为Al2O3-Cr2O3-SiO2系.所形成的高硅质液相能促进(Al2-x,Crx)O3固溶体析晶,晶体呈较大的六方柱状自形晶,长度达5～20 μm,长径比(a)为5～10.但此液相中不含Cr2O3.     

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.