Al_2O_3—SiO_2混合溶胶—凝胶涂层对工程陶瓷表面改性的研究

利用溶胶—凝胶法在SG4工程陶瓷基体上成功制备了Al2 O3—SiO2 混合涂层 ;通过X射线仪测定了Al2 O3—SiO2 凝胶粉末的晶相组成。对精磨、热处理、Al2 O3涂层和Al2 O3—SiO2 混合涂层四种试样抗弯强度的样本均值和样本标准离差进行了比较 ,并通过观察四种试样表面的SEM形貌和两种涂层试样断面的SEM形貌初步分析了表面改性的原因。分析结果表明 :溶胶涂层对基体表面微裂纹有一定的弥合作用 ,可以提高基体的抗弯强度而降低材料强度的分散性 ,其效果好于单纯的热处理 ,Al2 O3—SiO2 混合涂层试样的表面质量优于Al2 O3涂层试样 ;Al2 O3—SiO2 混合涂层渗入基体更深 ,可以更好地弥合基体表面微裂纹 ,有效提高基体的抗弯强度。     

用溶胶—凝胶法制备Al2O3涂层工程陶瓷的表面改性研究

分析了溶胶－凝胶法制备Al2O3溶胶的适宜工艺条件。在氧化铝基陶瓷基体上成功地制备了Al2O3涂层;利用X射线衍射分析和差热分析（DTA）方法对Al2O3凝胶粉末的相变过程进行了研究,通过分析精磨,热处理,Al2O3一次和二次溶胶涂层4种试样的抗弯强度测量值对材料总体性能进行了估计,结果表明：Al2O3涂层工程陶瓷可以提高基体的抗弯强度而降低其分散性,效果好于单纯的热处理,通过观察4种试样的表面SEM形貌和两种涂层试样的断面SEM形貌提出了溶胶涂层钝化或弥合表面微裂纹的理论模型。     

溶胶-凝胶法对Al2O3陶瓷表面改性的研究

研究了八种不同陶瓷试样的抗弯强度和韦布尔模数。结果表明 ,试样的抗弯强度按线切割、粗磨、精磨、抛光、热处理、氧化铝一次涂层、氧化铝二次涂层、Al2 O3-SiO2 混合涂层的次序依次提高。而韦布尔模数以Al2 O3-SiO2 混合涂层最高 ,其次是热处理试样。理论分析可知 ,热处理过程可使裂纹钝化甚至弥合 ,减少了裂纹半径C ,因此提高了抗弯强度。涂层方法可以提高试样的抗弯强度 ,但可能使晶界与晶粒产生裂纹而导致韦布尔模数下降。由Al2 O3-SiO2 混合涂层试样的横截面SEM形貌图可知 ,该方法可使溶胶颗粒渗入基体更深 ,可以很好地弥合试样表层裂纹。     

用溶胶-凝胶法制备Al_2O_3涂层工程陶瓷的表面改性研究

分析了溶胶 -凝胶法制备Al2 O3 溶胶的适宜工艺条件 ,在氧化铝基陶瓷基体上成功地制备了Al2 O3 涂层 ;利用X射线衍射分析和差热分析 (DTA)方法对Al2 O3 凝胶粉末的相变过程进行了研究 .通过分析精磨、热处理、Al2 O3 一次和二次溶胶涂层 4种试样的抗弯强度测量值对材料总体性能进行了估计 .结果表明 :Al2 O3 涂层工程陶瓷可以提高基体的抗弯强度而降低其分散性 ,效果好于单纯的热处理 .通过观察4种试样的表面SEM形貌和两种涂层试样的断面SEM形貌提出了溶胶涂层钝化或弥合表面微裂纹的理论模型     

溶胶-凝胶工艺制备ZrO2涂层对工程陶瓷表面改性的研究

采用无机盐先驱体 ,溶胶 -凝胶工艺在氧化铝基工程陶瓷上成功制备了ZrO2 涂层。用差热分析(DTA)、扫描电子显微镜 (SEM)、X射线衍射 (XRD)等分析手段对ZrO2 涂层的物相组成、表面和断面形貌进行了表征。对精磨、热处理、ZrO2 涂层试样的抗弯强度和Weibull模数进行了比较。结果表明 :ZrO2 涂层可以明显改善陶瓷的表面质量 ;涂层与基体结合紧密 ,无明显的界面层 ;涂层试样的抗弯强度和Weibull模数均比未涂层试样有明显的提高。     

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。     

溶胶凝胶法制备Al_2O_3-SiO_2包覆金刚石的性能研究

利用溶胶-凝胶法制备了Al2O3-SiO2溶胶,并将溶胶包覆金刚石,利用扫描电镜、热分析、红外光谱、冲击韧性测试等手段对包覆Al2O3-SiO2溶胶的金刚石性能进行表征。结果表明:金刚石表面包覆了一层致密的Al2O3-SiO2涂层及溶胶后,抗氧化性能、热性能以及机械性能均有明显提高。     

溶胶—凝胶法对A12O3陶瓷表面改性的研究

研究了八种不同陶瓷试样的抗弯强度和韦布尔模数。结果表明，试样的抗弯强度按线切割、粗磨、精磨、抛光、热处理、氧化铝一次涂层、氧吕二次涂层、Ａ１２Ｏ３－ＳｉＯ２混合涂层的次序依次提高。而韦布尔模数以Ａ１２Ｏ３－ＳiＯ２混合涂层最高，其次是热处理试样。理论分析可知，热处理过程可使裂纹印化甚至弥合，减少了裂纹半径Ｃ，因此提高了抗弯强度。涂层方法可以提高试样的抗弯强度，但可能使晶界与晶料产生裂纹而导致韦布尔     

Al2O3-SiO2-TiO2复合陶瓷膜的研制

本文用Sol-Gel法制备了掺杂TiO2、SiO2改性的γ-Al2O3膜,Al2O3-SiO2-TiO2混合溶胶的比例为:Al:Si:Ti=1:4:1(mol比),加入硝酸调节其pH值位1.2-2.5,可得到稳定的Al2O3-SiO2-TiO2溶胶。通过XRD分析,膜的相组成为非晶态SiO2、γ-Al2O3和Al4Ti2SiO12及TiO2,SEM分析膜主要特征为层状表面结构,平铺在支撑体上。研究发现添加剂、pH值、膜与基体之间的应力作用、浸渍时间、热处理过程对膜的形成的影响甚大。     

溶胶-凝胶法制备不锈钢表面SiO2-ZrO2-Al2O3-Cr2O3涂层的研究

用溶胶-凝胶法在不锈钢表面制备了SiO2-ZrO2-Al2O3-Cr2O3，涂层，并用XRD、SEM等手段对其相结构、界面形貌进行了表征，且完成了900℃高温下的抗氧化性实验及FeCl3腐蚀实验。结果表明：预涂Al2O3-Cr2O3过渡层可使基体与涂层结合较好；涂有薄膜的不锈钢抗氧化性、耐腐蚀性均有显著提高。     

Photocatalytic activity of Cu2O/TiO2, Bi2O3/TiO2 and ZnMn2O4/TiO2 heterojunctions

Cu₂O/TiO₂, Bi₂O₃/TiO₂ and ZnMn₂O₄/TiO₂ heterojunctions were studied for potential applications in water decontamination technology and their capacity to induce an oxidation process under VIS light. UV–vis spectroscopy analysis showed that the junctions-based Cu₂O, Bi₂O₃ and ZnMn₂O₄ are able to absorb a large part of visible light (respectively, up to 650, 460 and 1000 nm). This fact was confirmed in the case of Cu₂O/TiO₂ and Bi₂O₃/TiO₂ by photocatalytic experiments performed under visible light. A part of the charge recombination that can take place when both semiconductors are excited was observed when a photocatalytic experiment was performed under UV–vis illumination. Orange II, 4-hydroxybenzoic and benzamide were used as pollutants in the experiment. Photoactivity of the junctions was found to be strongly dependent on the substrate. The different phenomena that were observed in each case are discussed.     

ZrB2质与TiB2质耐火材料

介绍了ZrB     

Properties of char particles obtained under O2/N2 and O2/CO2 combustion environments

Pulverized coal combustion in O₂/N₂ and O₂/CO₂ environments was investigated with a drop tube furnace. Results present that the reaction rate and burn-out degree of O₂/CO₂ chars (obtained in O₂/CO₂ environments) are lower than that of O₂/N₂ chars (obtained in O₂/N₂ environments) under the same experimental condition. It indicates that a higher O₂ concentration in O₂/CO₂ environment is needed to achieve the similar combustion characteristic to that in O₂/N₂ environment. The main differences between O₂/N₂ and O₂/CO₂ chars rely on the pore structure determined by N₂ adsorption and chemical structure measured by FT-IR. For O₂/CO₂ char, the surface is thick and the pores are compact which contribute to the fragmentation reduction of particles burning in O₂/CO₂ environment. The organic functional group elimination rate from the surface of O₂/CO₂ chars is slower or delayed. The present research results might have important implications for further understanding the intrinsic kinetics of pulverized coal combustion in O₂/CO₂ environment.     

ZrO2/SiO2- and La2O3/Al2O3-supported platinum catalysts for CH4/CO2 reforming

Surface-phase ZrO₂ on SiO₂ (SZrOs) and surface-phase La₂O₃ on Al₂O₃ (SLaOs) were prepared with various loadings of ZrO₂ and La₂O₃, characterized and used as supports for preparing Pt/SZrOs and Pt/SLaOs catalysts. CH₄/CO₂ reforming over the Pt/SZrOs and Pt/SLaOs catalysts was examined and compared with Pt/Al₂O₃ and Pt/SiO₂ catalysts. CO₂ or CH₄ pulse reaction/adsorption analysis was employed to elucidate the effects of these surface-phase oxides.

The zirconia can be homogeneously dispersed on SiO₂ to form a stable surface-phase oxide. The lanthana cannot be spread well on Al₂O₃, but it forms a stable amorphous oxide with Al₂O₃. The Pt/SZrOs and Pt/SLaOs catalysts showed higher steady activity than did Pt/SiO₂ and Pt/Al₂O₃ by a factor of three to four. The Pt/SZrOs and Pt/SLaOs catalysts were also much more stable than the Pt/SiO₂ and Pt/Al₂O₃ catalysts for long stream time and for reforming temperatures above 700 °C. These findings were attributed to the activation of CO₂ adsorbed on the basic sites of SZrOs and SLaOs.     

Modeling char conversion under suspension fired conditions in O2/N2 and O2/CO2 atmospheres

The aim of this investigation has been to model combustion under suspension fired conditions in O₂/N₂ and O₂/CO₂ mixtures. Experiments used for model validation have been carried out in an electrically heated Entrained Flow Reactor (EFR) at temperatures between 1173 K and 1673 K with inlet O₂ concentrations between 5 and 28 vol.%. The COal COmbustion MOdel, COCOMO, includes the three char morphologies: cenospheric char, network char and dense char each divided between six discrete particle sizes. Both combustion and gasification with CO₂ are accounted for and reaction rates include thermal char deactivation, which was found to be important for combustion at high reactor temperatures and high O₂ concentrations. COCOMO show in general good agreement with experimental char conversion profiles at conditions covering zone I-III. From the experimental profiles no effect of CO₂ gasification on char conversion has been found. COCOMO does however suggest that CO₂ gasification in oxy-fuel combustion at low O₂ concentrations can account for as much as 70% of the overall char consumption rate during combustion in zone III.     

Partial oxidation of methane to CO and H2 over nickel and/or cobalt containing ZrO2, ThO2, UO2, TiO2 and SiO2 catalysts

The influence of different metal oxide supports (i.e. ZrO₂, ThO₂, UO₂, TiO₂ and SiO₂) on the performance of Ni- and/or Co-containing catalysts [Ni and/or Co/MO₂ mole ratio (where M=Zr, Th, U, Ti or Si)=1.0] in the oxidative methane-to-syngas conversion at very low contact time (GHSV=5.2×10⁵ cm³ g⁻¹ h⁻¹ at STP) was investigated. The nickel-containing ZrO₂, ThO₂ and UO₂ catalysts (with or without pre-reduction by hydrogen at 500°C) showed good performance in the process; the order of their performance is NiO–ThO₂>NiO–UO₂>NiO–ZrO₂. The NiO–TiO₂ showed appreciable catalytic activity only after its reduction at 800°C. However, this catalyst and the NiO–SiO₂ catalyst showed poor performance in the process. These two catalysts are also deactivated very fast, mostly because of sintering of Ni and/or formation of catalytically inactive binary metal oxide phases by solid–solid reaction at the high catalyst calcination and/or catalytic reaction temperature. Although the Ni-containing ThO₂, UO₂ and ZrO₂ catalysts showed good performance, carbon deposition on them during the process is fast. However, because of the addition of cobalt to these catalysts (with Co/Ni=1.0), the rate of carbon deposition on them in the process is drastically reduced. This Co addition however resulted in a significant decrease in both the conversion and selectivity; the decrease in the selectivity was small.     

Adsorption of CO2 from dry gases on MCM-41 silica at ambient temperature and high pressure. 2: Adsorption of CO2/N2, CO2/CH4 and CO2/H2 binary mixtures

Adsorption equilibrium capacity of CO₂, CH₄, N₂, H₂ and O₂ on periodic mesoporous MCM-41 silica was measured gravimetrically at room temperature and pressure up to 25 bar. The ideal adsorption solution theory (IAST) was validated and used for the prediction of CO₂/N₂, CO₂/CH₄, CO₂/H₂ binary mixture adsorption equilibria on MCM-41 using single components adsorption data. In all cases, MCM-41 showed preferential CO₂ adsorption in comparison to the other gases, in agreement with CO₂/N₂, CO₂/CH₄, CO₂/H₂ selectivity determined using IAST. In comparison to well known benchmark CO₂ adsorbents like activated carbons, zeolites and metal-organic frameworks (MOFs), MCM-41 showed good CO₂ separation performances from CO₂/N₂, CO₂/CH₄ and CO₂/H₂ binary mixtures at high pressure, via pressure swing adsorption by utilizing a medium pressure desorption process (PSA-H/M). The working CO₂ capacity of MCM-41 in the aforementioned binary mixtures using PSA-H/M is generally higher than 13X zeolite and comparable to different activated carbons.     

Gas-solid oxidations with RuO2---TiO2 and RuO2---SiO2 membranes

The activity of the RuO₂---TiO₂ and RuO₂---SiO₂ membrane catalysts in oxidation with air of the isopropylic alcohol was determined at temperatures ranging from 40 to 120°C. The RuO₂---TiO₂ and RuO₂---SiO₂ membranes were prepared by the sol-gel process and supported on microporous glass membranes. The catalysts were characterized by scanning electron microscopy, IR spectroscopy and X-ray diffraction studies.     

Kinetics of CO and H2 oxidation over CuO-CeO2 catalyst in H2 mixtures with CO2 and H2O

The kinetics of CO and H₂ oxidation over a CuO-CeO₂ catalyst were simultaneously investigated under reaction conditions of preferential CO oxidation (PROX) in hydrogen-rich mixtures with CO₂ and H₂O. An integral packed-bed tubular reactor was used to produce kinetic data for power-law kinetics for both CO and H₂ oxidations. The experimental results showed that the CO oxidation rate was essentially independent of H₂ and O₂ concentrations, while the H₂ oxidation rate was practically independent of CO and O₂ concentrations. In the CO oxidation, the reaction orders were 0.91, −0.37 and −0.62 with respect to the partial pressure of CO, CO₂ and H₂O, respectively. In the H₂ oxidation, the orders were 1.0, −0.48 and −0.69 with respect to the partial pressure of H₂, CO₂ and H₂O, respectively. The activation energies of the CO oxidation and the H₂ oxidation were 94.4 and 142 kJ/mol, respectively. The rate expressions of both oxidations were able to predict the performance of the PROX reactor with accuracy. The independence between the CO and the H₂ oxidation suggested different sites for CO and H₂ adsorption on the CuO-CeO₂ catalyst. Based on the results, we proposed a new reaction model for the preferential CO oxidation. The model assumes that CO adsorbs selectively on the Cu⁺ sites; H₂ dissociates and adsorbs on the Cu⁰ sites; the adsorbed species migrates to the interface between the copper components and the ceria support, and reacts there with the oxygen supplied by the ceria support; and the oxygen deficiency on the support is replenished by the oxygen in the reaction mixture.     

New acrylic monolithic carbon molecular sieves for O2/N2 and CO2/CH4 separations

The modification of activated carbon fibres prepared from a commercial textile acrylic fibre into materials with monolithic shape using phenolic resin as binder was studied. The molecular sieving properties for the gas separations CO₂/CH₄ and O₂/N₂ were evaluated from the gas uptake volume and selectivity at 100 s contact time taken from the kinetic adsorption curves of the individual gases. The pseudo-first order rate constant was also determined by the application of the LDF model. The samples produced show high CO₂ and O₂ rates of adsorption, in the range 3-35 × 10⁻³ s⁻¹, and in most cases null or very low adsorption of CH₄ and N₂ which make them very promising samples to use in PSA systems, or similar. Although the selectivity was very high, the adsorption capacity was low in certain cases. However, the gas uptake in two samples reached 23 cm³ g⁻¹ for CO₂ and 5 cm³ g⁻¹ for O₂, which can be considered very good. The materials were heat-treated using a microwave furnace, which is a novel and more economic method, when compared with conventional furnaces, to improve the molecular sieves properties.