Phase equilibrium studies in V2O5-Fe2O3 and V2O5-TiO2 systems

V₂O₅-Fe₂O₃ and V₂O₅-TiO₂ systems represent two important chemical systems with various applications, including energy, catalysts, and high-performance materials. In the present study, high-temperature phase equilibrium experiments were conducted at the temperature range of 670–1000°C in air. Electron probe X-ray micro-analyzer (EPMA) was used to analyze the microstructure and composition of the phases presented in quenched samples. Systematic experiments demonstrated that V₂O₅-containing systems should not be quenched by water-based quenching media. Phase diagrams in both systems were constructed, and the eutectic and peritectic points of the systems were confirmed and compared with previous studies. The present study improved the previous results and could be used as the base for thermodynamic modelings and further applications of the two systems.     

PbO-Fe2O3-V2O5-P2O5玻璃结构与性能研究

钒、铁磷酸盐玻璃作为一种半导体材料受到许多研究者的关注.选择了PbO-V2O5-P2O5、PbO-Fe2O3-P2O5和PbO-Fe2O3-V2O5-P2O5三组玻璃系统,研究了V2O5和Fe2O3对磷酸盐玻璃结构和性能的影响.通过红外光谱(IR)和差热分析(DTA)发现,V2O5和Fe2O3对磷酸盐玻璃结构的影响不同,Fe2O3不但会降低[PO4]基团的桥氧数,还会打断P=O双键,以[FeO4]形式参加网络结构,使玻璃结构趋于稳定.     

V2O5-TeO2-P2O5-Fe2O3系无铅低熔点封接玻璃性能研究

研究确定了V2 O5-TeO2-P2O5玻璃的形成范围,系统地探讨了P2O5/TeO2比及V2 O5对玻璃热膨胀系数、特征温度和耐水稳定性的影响规律,结果表明所涉及玻璃组成的耐水性低.对P2O5/TeO2/V2O5比为17.1/20.9/62,外掺Fe2O3玻璃的研究表明,Fe2O3掺入(0mol％～16mo1％),水侵蚀后质量损失由20.05％降低到1.73％,显著提高玻璃耐水稳定性,热膨胀系数由11.5×10-6/℃降低到8.9×10-6/℃,特征温度提高,其中转变温度Tg从267℃升高到310℃,膨胀软化温度Td从284℃升高到330℃.SEM分析发现,掺入Fe2O3玻璃的表面形成明显的未被侵蚀的网状结构,玻璃表面的Hench侵蚀机理由V类转变为Ⅱ类侵蚀机理.     

Some aspects of glass formation in R′2O−P2O5 and R″O−P2O5 systems

The limits of the glass-formation regions are established for the binary R′₂−P₂O₅ and R″O₅−P₂O₅ systems (R′=Li, Na, K: R″=Mg, Ca, Sr, Ba). It is shown that these boundaries closely correlate with those reported by other investigators despite the difference in the conditions in which these binary phosphate glasses were synthesized. The fact that all of the systems under study have about the same upper limits of glass-formation regions is attributed to the ratio R′₂O(R′O): P₂O₅, which for the systems in question is 1.0–1.5 rather than the individual crystal-chemical characteristics of the R⁺ and R²⁺ cations. Translated from Steklo i Keramika, No. 2, pp. 13–15 February, 1997.     

高浓度Sb2O5/水胶体直接制备Sb2O5/环己酮胶体

研究了以体积质量浓度为60％的高浓度水相Sb2O5胶体为原料制备阻燃剂环己酮／Sb2O5胶体的方法。直接向该水相Sb2O5胶体中加入数种表面活性剂和环己酮，经过胶团在水中聚沉、胶团表面改性、胶团重新分散于环己酮等几个步骤生成环己酮Sb2O5胶体，原水相Sb2O5胶体中的水随之一起成胶。试验表明，该胶体可以与聚氨酯以任意比例互相融合。     

P2O5-BaO-Nb2O5三元系统玻璃的形成及性能的研究

研究P2O5－BaO-Nb2O5三元系统的玻璃形成区,给出了该三元系统玻璃形成范围。结果发现该系统在网络形成体P2O5的摩尔分数仅为20％,Nb2O5的摩尔分数为30％,BaO的摩尔分数为50％的成分点仍成玻璃。讨论了Nb2O5在系数中的作用以及部分玻璃的着色问题。熔制了BaO的摩尔分数恒定为50％的（50－x)P2O5-xNb2O5-50BaO(x=0,1,10,25,30)和Nb2O5的摩尔分数恒定为10％的yP2O5-10Nb2O5-(90-y)BaO(y=40,50,60,70)玻璃。测定了其折射率、Abbe数、非线性折射率、转变温度、析晶温度、熔化温度、氧原子摩尔体积及密度和组成之间的关系,并从红外吸收光谱的结果初步探讨该玻璃结构。认为在该系统中Nb2O5的作用介于网络形成体和中间体之间。玻璃着色的原因是Nb^5 被还原。     

V2O5负载量对V2O5／TiO2催化剂SCR法脱硝的影响

以TiO2载体,采用浸渍法制备了不同V2O5负载量的用于选择性催化还原NOx的V2O5／TiO2催化剂。利用BET,SEM和Ⅺ①,对不同V2O5负载量的催化剂组成、结构、形貌和性能进行了表征,考察不同V2O5负载量对催化剂制备的影响。结果表明制备的催化剂具有较多的中孔和微孔,催化剂中V2O5含量的增加,会降低催化剂的表面积;V2O5含量为2％的V2O5／TiO2催化剂样品比表面积最大,但是其活性非常低;V2O5含量为4％催化剂比表面积较大,NOx脱转化率高;V2O5的负载量小时,V2O5主要以等轴聚合的钒基型式（V3O7和V6O13）存在,这些钒基是催化剂的活性中心;当负载量超过6％,V2O5主要以结晶相存在,占据大量活性位,降低催化效果。     

Ta_2O_5掺杂Bi_2O_3–ZnO–Nb_2O_5陶瓷的晶体结构、结晶化学及介电性能

采用固相反应法制备Bi1.5ZnNb1.5–xTaxO7陶瓷,研究了不同掺杂量Ta2O5对Bi2O3–ZnO–Nb2O5陶瓷相结构、晶体化学特性和介电性能的影响。结果表明:当x≤0.1时,样品均保持单一的立方焦绿石结构(α–BZN)。通过对样品结晶化学计算发现,随着Ta2O5掺杂量的增加,晶格常数a逐渐减小,结晶化学参数键价和AV(O')[A4]增大,AV(O)[A2B2]减小,48f(O)坐标ξ增加。在组成样品晶体结构的多面体中,由6个48f(O)组成的八面体结构(BO6)逐渐变得扭曲,而6个48f(O)和2个8b(O')组成的六面体结构逐渐变得规则,向正立方体结构变化。室温下样品的介电常数和损耗随Ta2O5掺杂量的增加而减小,弛豫度逐渐减小。     

P2O5含量对Al2O3-SiO2-P2O5系统玻璃结构和析晶性能的影响

采用高温熔融冷淬法制备Al2O3-SiO2-P2O(5ASP)系统玻璃,用原位晶化法获得了磷酸盐微晶玻璃;用IR、DSC、XRD、SEM等测试方法表征了玻璃结构及析晶性能,讨论了P2O5含量对ASP玻璃结构和析晶性能的影响。结果表明:P2O5含量在35～50%能形成稳定的ASP玻璃。在磷含量较低时,玻璃结构中的P5 主要以不含P=O双键的[PO4]四面体形式存在,P2O5含量较高时,结构中的P-O-键削弱,P=O双键加强,P5 部分以含P=O双键的[PO4]四面体形式存在。随着P2O5含量的增加,玻璃稳定性变差,析晶趋势增强;晶化后的玻璃以AlPO4为主晶相,同时含有少量的Al(PO)3晶相,当晶化温度由650℃升高到800℃时,晶相含量增加并出现YPO4晶相。     

PbO—Fe2O3-V2O5-P2O5玻璃结构与性能研究

钒、铁磷酸盐玻璃作为一种半导体材料受到许多研究者的关注。选择了PbO-V2O5-P2O5、PbO-Fe2O3-P2O5和PbO-Fe2O3-V2O5-P2O5三组玻璃系统,研究了V2O5和Fe2O3对磷酸盐玻璃结构和性能的影响。通过红外光谱(IR)和差热分析(DTA)发现,V2O5和Fe2O3对磷酸盐玻璃结构的影响不同,Fe2O3不但会降低[PO4]基团的桥氧数,还会打断P=O双键,以[FeO4]形式参加网络结构,使玻璃结构趋于稳定。     

Ga_2O_3和P_2O_5掺入对碲钡锶铌系玻璃Raman性能的影响

研究了在TeO_2-BaCO_3-SrCO_3-Nb_2O_5(TBSN)玻璃体系中单独引入P_2O_5(TBSN-P)或同时引入P_2O_5和Ga_2O_3对TBSN玻璃的Raman散射和热稳定性的影响。结果表明:TBSN-P体系中,相对Raman散射截面随P_2O_5含量的增加逐渐减小,Raman增益带宽则显著增加;在TBSN-10Ga-P[(7-x)TeO_2-5BaO-5SrO-5Nb_2O_5-10Ga_2O_3-xP_2O_5(x=0,4,8,12,16,20,摩尔比,下同)]与TBSN-16P-Ga-[(69-y)TeO_2-5BaO-5SrO-5Nb_2O_5-16P_2O_5-yGa_2O_3(y=0,2,4,6,8,10)]系列中,Ga_2O_3的存在使得350～1250 cm~(-1)的整体谱形更加平坦,但Raman增益带宽和相对Raman散射截面均有所下降。计算了各玻璃样品的Raman增益系数和增益带宽,发现TBSN-4P玻璃具有最大的Raman增益系数(8.70×10~(-12)m/W),TBSN-24P玻璃具有最大Raman增益带宽(621 cm~(-1)),分别为熔石英玻璃的45倍和2.95倍。对玻璃的热稳定性研究表明,在TBSN-P体系中,P_2O_5的引入可以使玻璃的热稳定性能显著提高,而在Ga_2O_3与P_2O_5同时被引入时,Ga_2O_3含量的增加会导致玻璃的热稳定性变差。     

低熔点P2O5-ZnO-MgO-Na2O玻璃性能研究

通过正交实验方法,对低熔点P2O5-ZnO-MgO-Na2O玻璃的组分与玻璃软化温度、膨胀系数、耐酸性和折射率之间的关系进行了详细的研究。实验结果显示,合理地选择各组分的比例,能够得到软化温度低于400℃,膨胀系数在(80~90)×10-7℃-1,稳定性良好的釉用低熔点无铅无镉玻璃。     

Oxidative dehydrogenation of ethane to ethylene over V2O5/Nb2O5 catalysts

V₂O₅/Nb₂O₅ catalysts with various V₂O₅ contents were prepared by impregnation and characterized by various techniques in detail. Oxidative dehydrogenation of ethane was carried out in a fixed bed quartz reactor at 500–600 °C. XPS analysis indicated a clear enrichment of vanadium on the near-surface-region and UV–vis diffuse reflectance spectroscopy revealed the nature of VO_x structures formed. 10 wt.% V₂O₅/Nb₂O₅ catalyst has displayed the best performance (X = 28%, S = 38% at 600 °C) due to enrichment of vanadium in the near-surface-region and formation of optimum amount of monomeric/oligomeric VO_x species.     

Hot corrosion behavior of NdYbZr2O7 exposed to V2O5 and Na2SO4 + V2O5 molten salts

In order to evaluate the application prospects of NdYbZr₂O₇ as a novel TBC material, NdYbZr₂O₇ ceramic was synthesized via a solid-state reaction sintering method, and its hot corrosion behavior exposed to V₂O₅ and Na₂SO₄ + V₂O₅ molten salts at 900 °C, 1000 °C, and 1100 °C was comparatively investigated. For the V₂O₅ salt, the primary corrosion products were granular (Nd,Yb)VO₄ as well as cube-like m-ZrO₂. The corrosion layer consisted of two distinct layers, one of which was Zr-rich layer and another was V-rich layer. In the case of Na₂SO₄ + V₂O₅, NaVO₃, as an intermediate product, played an important role in dissolving the NdYbZr₂O₇ ceramic. Herein, the (Nd,Yb)VO₄ exhibited a rod/plate-like morphology, which could be attributed to the synergistic effect of low driving force and low nucleation rate. Since the molten salt infiltration rate was superior to the pore filling rate throughout the hot corrosion, the thickness of corrosion layer increased with the rise of temperature. The hot corrosion mechanisms of NdYbZr₂O₇ ceramic in various molten salts were discussed based on the phase diagram, Lewis acid-base rule and chemical thermodynamics. On this basis, the NdYbZr₂O₇ coating was prepared by atmospheric plasma spray (APS) and it exhibits a higher corrosion resistance compared to YSZ coating.     

Ta2O5与Nb2O5对TiO2基压敏陶瓷电性能的影响

研究了Ta2O5与Nb2O5对TiO2基压敏陶瓷电性能的影响.按照配方TiO2+0.003(按摩尔计)(SrO+Bi2O3+SiO2)+x Ta2O5+yNb2O5配制3种组分的圆片试样,各组分摩尔量分别为x=0.000 75,y=0;x=0.000 375,y=0.000 375及x=0,y=0.000 75.采用电流-电压、电容测量、阻抗分析和势垒高度测量等实验手段,分析了Ta2O5和Nb2O5的作用机理.结果发现,x=0.000 75的样品显示出最低的压敏电压梯度(E10 mA=7.9 V/mm)和最大的表观介电常数(εra=5.88×104),y=0.000 75的样品显示出最高的压敏电压梯度(E10mA=48.9 V/mm)和最小的表观介电常数(εra=1.39×104).这表明,掺Ta2O5可有效地降低压敏电压,提高介电常数.     

Bi2O3-CaO-ZnO-Nb2O5系陶瓷介电性能研究

借助XRD,SEM,HP4140B微电流计和HP4274A阻抗分析仪等测试手段,研究实验制备的BCZN[(Bi1.5Ca0.5)(Zn0.5Nb1.5)O7]陶瓷试样介电性能,并第一次提出了介电常数临界温度和介质损耗临界温度的概念。结果表明:BCZN陶瓷是高频稳定形陶瓷,具有面心立方焦绿石结构,且在最佳烧结温度和保温时间下,为均一的α相单相结构;在很宽的频率范围内,介电常数较高(εr≈81)且很稳定,介质损耗很小(tanδ≈-1.0×10-4);它的介电常数在温度低于介电常数临界温度时,与温度呈线性关系,在温度高于介电常数临界温度时,发生高温突变;介质损耗在温度低于介质损耗临界温度时几乎不变,在温度高于介质损耗临界温度时,发生高温突变;介电常数临界温度和介质损耗临界温度都随频率的升高而升高。     

Crystallization Hierarchy of CaO-P2O5-SiO2-Al2O3-TiO2 Glass-Ceramics

Glasses in the tricalcium phosphate-anorthite (Ca₃(PO₄)₂-CaAl₂Si₂O₈ or TCP-CAS₂) system with additional TiO₂ were melted. Crystallization was investigated using thermal analysis, X-ray diffraction, and transmission optical and electron microscopies. During the heat treatment, as the growth temperature increases, successive crystalline phases separate from the glass matrix. The phases present in the fully heat-treated glass-ceramic are ß-TCP, anor-thite (CAS₂), and rutile (TiO₂). Apart from TiO₂, these phases evolve from other polymorphs during the heat treatment. The metastable phases, pseudo-orthorhombic CAS₂ and alpha-TCP, appear first around 880°C and transform into the stable phases, triclinic anorthite CAS₂ and ß-TCP, around 940° and 1000°C, respectively. The material crystallizes in stages. The first stage is the separation from the glass matrix of rutile and what is believed to be a calcium phosphate phase, with crystal sizes varying from 20 to 200 nm. This is followed by the appearance of larger crystals (1-2 µm) of the metastable pseudo-orthorhombic CAS₂, surrounding the previously crystallized phases. Finally, this pseudo-orthorhombic CAS₂ phase transforms to anorthite (15-20 µm) spherulites. TiO₂ does not act as a direct nucleating agent in the glass composition studied: no sign of heterogeneous nucleation and growth from TiO₂ crystals has been found, and moreover, TiO₂-free base glass crystallizes in a manner similar to that of the glass containing TiO₂.     

Electrical characterization of co-precipitated LaBaCo2O5+δ and YBaCo2O5+δ oxides

REBaCo₂O_5+δ layered perovskite oxides (RE = Rare Earth) are promising cathodes for IT-SOFCs. In this work, a simple co-precipitation synthesis in aqueous medium was applied to prepare LaBaCo₂O_5+δ (LBC) and YBaCo₂O_5+δ (YBC) cathodes. The chemical and electrochemical properties of both materials were characterized via XRD, SEM, TPO, TG–DTA, 4-probe conductivity measurement, and EIS tests on symmetric cells. The coprecipitation synthesis revealed a promising preparation route: the measured ASR values of both materials were well comparable with the literature ones. A kinetic investigation of the O₂ reduction process was performed on LBC (600–800 °C, 5–100% O₂, v/v), whose results were analyzed with equivalent circuits. The main steps were identified (oxygen diffusion and charge transfer at high frequency, O₂ chemisorption at medium frequency), and their activation energy and reaction order were quantified. Aging tests (500 h time on stream, 500–800 °C) revealed quick deactivation for YBC and good stability for LBC.