各组分对SOFC硼酸盐封接玻璃系统的影响

以BaO-Al2O3-B2O3-SiO2封接玻璃体系为主要研究对象,研究氧化钡、二价金属氧化物和硼硅比等对封接玻璃系统的影响.BaO能使封接玻璃结构较疏松并降低其粘度,同时热膨胀系数随着BaO含量的增加呈上升的趋势,而封接玻璃转变温度Tg和软化温度Ts则随BaO含量的增加呈下降的趋势;B2O3/SiO2摩尔比分别为0.35、0.4、0.5和0.6时,封接玻璃的TEC随着B2O3/SiO2的增大而逐渐减小,Tg和Ts随着B2O3的增多而显著降低;但是当B2O3/SiO2比大于0.5时,比例对Tg和Ts的影响较小,Tg和Ts温度下降的趋势逐渐平缓下来;在体系中引入RO(R=Ca,Zn)会使封接玻璃的Tg朝高温方向偏移,同时也能使封接玻璃的析晶温度退后,但不利于封接玻璃的长期稳定性.     

Al_2O_3含量对ITSOFC用SrO-La_2O_3-Al_2O_3-B_2O_3-SiO_2玻璃性能的影响(英文)

采用高温熔融法制备了中温固体氧化物燃料电池用系列硼硅酸盐玻璃,玻璃摩尔组成为40SrO-5La2O3-xAl2O3-(25-x)B2O3-30SiO2(x=0,2.5,5.0,10.0)。结果表明:随着Al2O3含量的逐渐增多,玻璃转变温度和析晶峰温度逐渐升高,而热膨胀系数(CTE)均在9.8×10-6/K左右,这与电极材料8%(摩尔分数)Y2O3稳定ZrO2(8YSZ)在相同温度范围内的CTE相接近。Al2O3摩尔含量为5%的硼硅酸盐玻璃在700℃热处理100h后未能检测到明显的析晶和CTE变化,同时与8YSZ电极材料在700℃保温100h没有观测到明显的界面反应,表明该玻璃具有良好的化学相容性。     

Er3+和Yb3+共掺锗硅酸盐玻璃的上转换发光性能

采用熔融-淬火法制备了基体为30SiO2-20GeO2-15Al2O3-5B2O3-30CaF2的Er3+和Yb3+共掺锗硅酸盐玻璃.采用X射线衍射仪、荧光光谱仪和热分析仪对样品进行了表征.结果表明:Er2O3含量从0.5％(摩尔分数,下同)增加到2.0％时,玻璃转变温度Tg和Tx-Tg(Tx为第一析晶温度)数值均有明显下降.Yb2O3含量从1.5％增加到4.5％时,玻璃上转换红光发光强度数量级由103提高到105,对其中1个样品在740℃热处理12h后发现,微晶化处理并未对Er的上转换发光产生有益影响.     

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。     

封接金属氧化物对微晶玻璃的晶化及封接界面的影响

应用差热分析、电子显微镜、X射线衍射、X射线能谱等实验技术研究了Li_2OAl_2O_3-SiO_2系统微晶玻璃中分别加入2%的Fe_2O_3,Co_2O_3,NiO时对微晶玻璃晶化及封接界面的影响。通过讨论,这些金属氧化物的加入,在不同程度上影响了玻璃和界面层的析晶速率及界面层的化学反应,从而明显地看出玻璃析晶速率高和玻璃转变为微晶玻璃时α变化大常是导致微晶玻璃封接件开裂的主要原因之一。而Co_2O_3的加入因抑制了玻璃的析晶,从而增强了封接件的封接界面的结合强度,对获得良好的微晶玻璃与可伐的封接提供了一可取的途径。     

CaO-Al2O3-SiO2系玻璃陶瓷的析晶动力学研究

采用差热分析方法(DTA)对CaO-Al2O3一SiO2体系玻璃陶瓷的析晶动力学参数进行了测定,研究了该系统微晶玻璃的析晶动力学.结果表明:随着CaO/SiO2比的增大,该系统玻璃的析晶活化能E变小,析晶动力学反应速率k(T)增大,玻璃稳定性变小.所有玻璃样品的析晶指数(n)约为1,为表面析晶机制.     

Na2O对固体氧化物燃料电池用透辉石封接微晶玻璃性能的影响

本文设计和制备了以透辉石为主晶相的R₂O-RO-Al₂O₃-B₂O₃-SiO₂系封接微晶玻璃,用于固体氧化物燃料电池(SOFC)的封接,研究了Na₂O含量(0%～10%,摩尔分数)对封接玻璃热膨胀系数(CTE)、析晶与烧结润湿特性的影响,表征了封接件在高温长时间热处理后玻璃与SUS403不锈钢的封接界面。结果表明,Na₂O可以显著改善玻璃的热性能,所制备的玻璃样品在封接温度范围内经热处理后可获得主晶相为透辉石(CaMgSi₂O₆)的微晶玻璃。随着Na₂O含量增加,主晶相透辉石的晶相含量不同,微晶玻璃的热膨胀系数由未晶化前的8.22×10^-6 K^-1提升至11.79×10^-6 K^-1,能够满足SOFC封装的热膨胀匹配。当Na₂O含量大于等于8...     

BaO含量与热处理制度对BaO-Al2O3-B2O3-SiO2体系封接玻璃性能的影响

燃料电池的长寿命安全使用对相关联的封接玻璃提出了更高的要求,为明确封接玻璃的组成和晶相析出对封接玻璃转变温度、热膨胀系数等的影响规律.以BaO-Al2O3-B2O3-SiO2作为基础玻璃体系,通过测试玻璃的DSC、XRD、CTE等性能参数,研究组成中BaO含量和热处理制度对玻璃封接性能的影响.结果 表明,BaO能够增大玻璃的热膨胀系数,降低玻璃的特征温度.随着BaO含量的增加,基础玻璃的CTE从9.24×10-6 K-1增加到11.26×10-6 K-1.其中B3组玻璃满足SOFC的使用要求,可用作封接玻璃.B3组基础玻璃在模拟电池的工作温度下热处理后,主晶相为正交晶系的BaSiO3,微晶玻璃的膨胀系数提高至10.53×10-6 K-1,同样能够满足与电解质YSZ(CTE:10.5×10-6K-1)、以及Corfer22APU连接板(CTE:12×10-6 K-1)的匹配要求;析晶后玻璃的软化温度提高至830℃,提高了封接玻璃的使用温度,在SOFC工作温度(700 ～ 800℃)下,所制备的封接微晶玻璃在软化温度以下不会过度流动,能够保证良好的密封,满足封接的功能需求.     

氧化物添加对Bi_2O_3–B_2O_3–ZnO低熔点玻璃结构与性能的影响

采用常规的熔体冷却法制备了以Bi2O3–B2O3–ZnO为基体,外加氧化物（SiO2、GeO2、TeO2和Sb2O5）的玻璃试样,对比研究了氧化物对玻璃结构、转变温度、软化温度、析晶温度、热膨胀系数、抗弯强度和化学稳定性的影响规律。结果表明：在基体中加入SiO2,对降低玻璃的热膨胀系数最有效;加入TeO2,对降低玻璃的转变温度和软化温度最有效;加入Sb2O5,不仅能降低玻璃的转变温度和软化温度,使ΔT最大,而且能改善铋酸盐玻璃在封接过程中易析晶的问题,热膨胀系数较低,抗弯强度最大,化学稳定性最好。通过利用Fourier红外光谱、X射线衍射和热分析研究了玻璃结构的变化。     

核化温度对CaO-Al2O3SiO2系微晶玻璃晶化行为的影响

利用DTA技术测定了某一配方的CaO-Al2O3SiO2系玻璃的玻璃转变温度 (Tg)与玻璃晶化温度(Tp),在Tg温度稍上,进行了不同温度的预核化处理.经预核化处理后的试样的DTA和SEM分析结果表明,随预核化温度的增加,晶化峰向低温方向移动,表明析晶能力在增强.在晶化温度稍上热处理,玻璃表面析晶,玻璃从表面到内部长成粗大的柱状晶,并以树枝状方式生长.在玻璃内部,尺寸细小的等轴晶镶嵌在玻璃相中.     

金属氧化物吸收微波辐射的能力与其结构的关系

考察了８种金属氧化物及６种复合金属氧化物在微波场中的升温行为，并对升温行为与其结构的关系进行了初步探讨。     

中国专用氧化镁开发现状及其发展建议

介绍了氧化镁系列产品应用领域及生产现状,中国专用氧化镁如活性氧化镁、电工级氧化镁、硅钢级氧化镁、高纯氧化镁等开发是成功的,其中高纯氧化镁已达到世界领先水平;硅钢级氧化镁不仅已工业化,并成功应用于武钢硅钢片的生产上,取得显著经济效益,但总体上看研发技术虽然成功,工业化生产量还不足。提出了中国专用氧化镁发展必须充分利用中国十分丰富镁资源,扬长避短,发挥原料及生产方法优势,采用先进设备,提升装置及自控水平,建立万吨级骨干企业,提高专用化率等建议,提高精细氧化镁品种及产量以满足国内外市场需求。     

纯正黑色釉的研制

研究了用金属氧化物和硅酸盐材料直接制取纯正黑色釉的可行性，探讨了氧化铁、氧化铝、氧化钢、氧化信和氧化锰对黑釉性质的影响。     

Formation of self-ordered nano-tubular structure of anodic oxide layer on titanium

Room temperature anodization of titanium foil specimens was carried out in 0.5 M phosphoric acid solution with addition of various halide ions. Addition of 0.138 M HF or NaF resulted in self-ordered nano-tubular oxide structure. Addition of bromide and chloride ions initiated only pitting and nano-pores were not observed during anodization. Acidified fluoride solution is found to be necessary to obtain ordered nano-structure as neutral fluoride solution did not form nano-pores. Instability of the oxide layer during anodization and formation of the self-ordered structure can be explained by the perturbation theory. Separation of individual nano-tubes of titanium oxide layer from the inter-connected nano-pores could be attributed to the possible repulsion forces of the cation vacancies.     

超细In2O3-SnO2复合催化剂的制备及其催化性能的研究

以InCl3·4H2O及SnCl4·5H2O为原料,用共沉淀法制备超细In2O3SnO2复合催化剂,用XRD、TEM、TPD等对所制备的样品催化剂进行表征.XRD、TEM测定结果表明,所制备的样品粒径20～30 nm,分布窄,用TPD测定了样品对O2及CH4的脱附情况.CH4的催化燃烧试验表明,所制备的In2O3-SnO2复合催化剂具有良好的催化反应活性.     

CuO／Ce1-xZrxO2催化分解NO的研究

NO对环境的影响日益严重,如果不有效将其消除掉,将会对环境及人的健康产生极大的危害。因此,目前各国都在研究廉价消除NO污染的方法。采用共沉淀法制备了催化剂CuO／Ce1-xZrxO2,利用XRD对其晶相进行表征,H2-TPR研究了其氧化还原能力,以NO的转化效率作为评价指标。结果表明：适当比例zr的加入以及适当比例的CuO能提高活性。     

Sintering of Zinc Oxide Doped with Antimony Oxide and Bismuth Oxide

The phase change, densification, and microstructure development of ZnO doped with both Bi₂O₃ and Sb₂O₃ are studied to better understand the sintering behavior of ZnO varistors. The densification behavior is related to the formation of pyrochlore and liquid phases; the densification is retarded by the former and promoted by the latter. The pyrochlore phase, whose composition is Bi_3/2ZnSb_3/2O₇, appears below 700°C. The formation temperature of the liquid phase depends on the Sb/Bi ratio: about 750°C for Sb/Bi < 1 by the eutectic melting in the system ZnO—Bi₂O₃, and about 1000°C for Sb/Bi > 1 by the reaction of the pyrochlore phase with ZnO. Hence, the densification rate is determined virtually by the Sb/Bi ratio and not by the total amount of additives. The microstructure depends on the sintering temperature. Sintering at 1000°C forms intragrain pyrochlore particles in ZnO grains as well as intergranular layers, but the intragrain particles disappear at 1200°C by the increased amount of liquid phase, which enhances the mobility of the solid second phase.     

Effect of Additives on the Hydration Resistance of Materials Synthesized from the Magnesia–Calcia System

The effect of a variety of doping additives on the hydration resistance of calcined materials in the MgO–CaO system was investigated. Samples were prepared from lightly calcined flotation magnesite that was mixed with dolomite, as well as from analytically pure CaO and MgO; then, the samples were doped with additives that contained cations with various valences (monvalent to tetravalent). Both the hydration rate and the powdering rate were measured. The important role of the higher-valence cations in improving the hydration resistance of the MgO–CaO materials was revealed. This behavior is believed to be due to the formation of vacancies in solid solutions of CaO or MgO with higher-valence cations. The Ti⁴⁺ cation forms a solid solution with CaO, which reduces the Ca²⁺ concentration and leads to the improved hydration resistance of calcined materials from the MgO–CaO system.     

非水解溶胶-凝胶过程制备锡/硅复合氧化物

以无水四氯化锡和正硅酸乙酯为前驱物、环己烷为溶剂,在无氧无水条件下采用非水解溶胶-凝胶过程制备了锡/硅复合氧化物,并对其进行了表征分析。结果表明,在原料Sn/Si摩尔比为1∶2、反应温度为30℃、焙烧温度为500℃时,所得复合氧化物的产率为31.3%,Sn/Si摩尔比为7.4∶1,粒径10nm左右,比表面积22.58cm2.g-1,平均孔径14.3nm,比孔容0.047cm3.g-1,主要为颗粒堆积孔;复合氧化物的主要组成为无定形氧化硅和氧化锡晶体,在焙烧温度达到500～600℃时仍有Sn-O-Si杂键存在。     

The characterization of the V species and the identification of the promoting effect of dopants in V/Ti/O catalysts for o-xylene oxidation

The present work deals with the study of the role of promoters in TiO₂-supported vanadium oxide, catalyst for the oxidation of o-xylene to phthalic anhydride. Two different series of catalysts were prepared, the first one consisting of undoped samples having different vanadium oxide content, and the second one of samples having 7 wt.% V₂O₅ and variable amounts of Sb and Cs as promoters. All the samples were characterized by means of Raman spectroscopy, X-ray diffraction and thermal-programmed reduction and oxidation, in order to define a method for the quantification of the different V species (i.e., isolated vanadium, dispersed polyvanadate and bulk vanadium oxide) that develop on TiO₂ support in the presence of promoters. It was found that polyvanadate and bulk vanadium oxide spontaneously release molecular oxygen at 600–650 °C, whereas the isolated V is not susceptible of self-reduction. The latter species is predominant in samples having low vanadium oxide loading (≤2 wt.% V₂O₅, with TiO₂ surface area 22.5 m²/g), and possesses the highest intrinsic activity in o-xylene conversion. The presence of Sb, a promoter of activity, increases the dispersion of the most active species and also hinders its segregation in the reaction environment. These promoting effects are more pronounced when both Cs and Sb are present.