Crystallization and properties of some CaO-Al2O3-SiO2 system glass-ceramics with Y2O3 addition

The crystallization behavior and mechanical properties of CaO-Al2O3-SiO2 （CAS） system glass-ceramics with addition of Y2O3 were investigated. The optimal sintering temperatures of all heat-treated glasses were altered and the crystallization was accelerated with Y2O3 addition, and only wollastonite as a main crystalline phase was precipitated. The volume fraction of crystalline phase and density were increased with Y2O3 addition. The results suggest that the CAS glass-ceramics would get the lowest sintering temperature and optimal microstructure with the addition of Y2O3 by 3.25 %. The bending strength has a maximum due to the oriented and interlocked wollastonite crystal, which causes crack divert or blunts to limit the further development of the flaw size and increases the surface energy of fracture.     

Gd2 O3 -Yb2 O3 -Y2 O3 -ZrO2 热障涂层材料的热物理性能

目的通过多元稀土氧化物掺杂改性YSZ,提高传统热障涂层的性能。方法使用化学共沉淀法制备不同掺杂量的Gd2O3-Yb2O3-Y2O3-Zr O2(GYYZO)材料,并分别使用冷等静压-烧结和等离子喷涂工艺制备块材和涂层。通过测试块材的热导率和热膨胀系数,分析评价材料的热物理性能。对高温退火处理后的涂层进行X射线衍射分析,评价不同成分涂层的高温相稳定性。结果氧化锆基材料的热导率和热膨胀系数随总掺杂量升高而降低。氧化锆中稀土氧化物总掺杂量为5.5%~9.84%(摩尔分数)时,在1000℃下的热导率为1.25~1.56 W/(m·K),相对8YSZ材料下降了22%~37.5%;在200~1300℃的热膨胀系数为(10~11.1)×10-6/K,与传统8YSZ材料相当。在1400℃长时间退火处理后,低掺杂量GYYZO涂层中的单斜相含量明显低于8YSZ涂层。结论多元稀土氧化物掺杂改性氧化锆材料具有良好的高温相稳定性、低热导率和适当的热膨胀系数,可以作为高性能热障涂层的备选材料。     

Investigating mechanochemical behavior of Cr2O3–B2O3–Mg–C quaternary system

Fundamental aspects of reaction behavior and formation path in the Cr₂O₃–B₂O₃–Mg–C quaternary system have been studied to synthesize chromium boride–chromium carbide nanocomposite. In order to find the influence of simultaneous presence of magnesium and carbon on final products, various powder mixtures were chosen according to following reaction: B₂O₃ + Cr₂O₃ + (9 − x) Mg + x C. The value of x varied from 0 to 4. In the absence of carbon (x = 0), CrB₂ was synthesize through mechanically induced self-propagating reaction (MSR). In the presence of 8 mol Mg and 1 mol C (x = 1), the dominant boride phase was CrB while no chromium carbide was detected. By increasing C content (x = 2), the magnesiothermic reduction occurred in MSR mode; whereas, the synthesis of Cr₃C₂ initiated after combustion reaction and completed gradually during milling for 6 h. Further increase in C amount (x = 3) resulted in formation of Mg₃(BO₃)₂ as unwanted phases as well as CrB and Cr₃C₂. In the presence of 6 mol Mg and 4 mol (x = 4), no mechanical reaction was observed even after 8 h of milling. Optimum value of x for the formation of CrB–Cr₃C₂ nanocomposite was 2. Based on the morphological evolutions, it is evident that the mechanosynthesized powder is made up of nanometric particles.     

La2O3-Gd2O3-Mo secondary emission material

A new kind of materials La2O3-Gd2O3-Mo has been produced by powder metallurgy method.The composition and microstructure of the material were studied by XRD and SEM.It shows that no chemical reaction takes place among La2O3,Gd2O3,Mo and the rare earth oxides exist along molybdenum grain boundaries and in the pores.The emission property measurement results of this material show that adding rare earth oxide into molybdenum can improve the secondary emission coefficient of the emitter,and the emission property depends on the activation temperature.After La2O3-Gd2O3-Mo was activated at 1360℃,the maximum secondary emission coefficient can be high to 2.62,which has exceeded that for practical uses(2.0).     

Non-equilibrium phase synthesis in Al2O3–Y2O3 by spray pyrolysis of nitrate precursors

The phase evolution in the Al₂O₃–Y₂O₃ system has been studied for 4, 10, 15 and 37.5% Y₂O₃ amorphous powders prepared by spray pyrolysis of nitrate precursor solutions. Two distinct metastable transformation sequences were identified for the amorphous powders upon heat treatment. Crystallisation accompanied by partitioning leads to a mixture of hexagonal YAlO₃ and γ-Al₂O₃ (spinel structure). Partitionless crystallisation, on the other hand, leads directly to a γ-Al₂O₃ solid solution in dilute alloys, and garnet at temperatures as low as 800°C in the stoichiometric composition provided segregation is avoided during decomposition. Further heat treatment of a yttria-supersaturated γ-Al₂O₃ leads to the precipitation of the orthorhombic YAlO₃ that is stable up to temperatures as high as 1600°C, while hexagonal YAlO₃ converts to garnet, Y₃Al₅O₁₂. A rationalisation of the phase evolution sequence has been attempted on the basis of kinetic considerations, cation coordination and semi-quantitative free energy–composition curves for the various competing phases.     

Combustion synthesis of FeAl−Al2O3 composites with TiB2 and TiC additions via metallothermic reduction of Fe2O3 and TiO2

Combustion synthesis involving metallothermic reduction of Fe₂O₃ and TiO₂ was conducted in the mode of self-propagating high-temperature synthesis (SHS) to fabricate FeAl-based composites with dual ceramic phases, TiB₂/Al₂O₃ and TiC/Al₂O₃. The reactant mixture included thermite reagents of 0.6Fe₂O₃+0.6TiO₂+2Al, and elemental Fe, Al, boron, and carbon powders. The formation of xFeAl−0.6TiB₂−Al₂O₃ composites with x=2.0−3.6 and yFeAl−0.6TiC−Al₂O₃ composites with y=1.8−2.75 was studied. The increase of FeAl causes a decrease in the reaction exothermicity, thus resulting in the existence of flammability limits of x=3.6 and y=2.75 for the SHS reactions. Based on combustion wave kinetics, the activation energies of E_a=97.1 and 101.1 kJ/mol are deduced for the metallothermic SHS reactions. XRD analyses confirm in situ formation of FeAl/TiB₂/Al₂O₃ and FeAl/TiC/Al₂O₃ composites. SEM micrographs exhibit that FeAl is formed with a dense polycrystalline structure, and the ceramic phases, TiB₂, TiC, and Al₂O₃, are micro-sized discrete particles. The synthesized FeAl−TiB₂−Al₂O₃ and FeAl−TiC−Al₂O₃ composites exhibit the hardness ranging from 12.8 to 16.6 GPa and fracture toughness from 7.93 to 9.84 MPa·m^1/2.     

Sol-gel formation of γ-Fe2O3/SiO2 nanocomposites

Fe₂O₃–SiO₂ nanocomposites with Fe/Si molar concentrations ranging between 0.25 and 0.57 were prepared by the sol-gel route. Tetraethoxysilane and iron(III) nitrate solution in ethanol were mixed and the hydrolysis reaction was promoted by the hydration water of the salt. The sols were gelated in air and then treated at 400°C for 4 h. The effect of the gelation process on the formation of the final nanocomposites has been investigated by studing different factors, such as temperature and surface of evaporation/volume ratio of the sol. Nanoparticles of γ and/or α iron oxide phase of different size were obtained in the silica matrix depending on the gelation conditions and on the later heat treatments. γ-Fe₂O₃–SiO₂ nanocomposites were obtained only when organic material was present into the pores of the gel silica matrix supporting their formation through a magnetite phase. At temperatures >400°C, the γ-phase begins to transform to the α-phase.     

Influence of AlF3 and hydrothermal conditions on morphologies of α-Al2O3

Homogeneous α-Al2O3 platelets were synthesized by introducing AlF3 to alumina precursor.The effects of AlF3 additive on the phase transformation and morphology of the prepared α-Al2O3 platelets were investigated.The results show that a single phase of α-Al2O3 with an average particle size of 8μm can be obtained at 900℃ with 2% AlF3 additive.The transformation temperature decreasing IS attributed to introduction of Al3 vacancy and to the formation of intermediate compound of AlOF,which is considered to accelerate the mass transportation from transitional Al2O3 to α-Al2O3.AlF3 concentration and hydrothermal temperature can also affect the morphology of α-Al2O3.When hydrothermal temperature is 120℃,the morphology of α-Al2O3 transforms from irregular to flat hexangular platelet with increasing AlF3 concentration.As hydrothermal temperature increases,the morphology of α-Al2O3 with 2% AlF3 additive changes from polyhedron to hexangular platelet and then to vermicular.     

Influence of AlF3 and hydrothermal conditions on morphologies of α-Al2O3

Homogeneous α-Al2O3 platelets were synthesized by introducing AlF3 to alumina precursor.The effects of AlF3 additive on the phase transformation and morphology of the prepared α-Al2O3 platelets were investigated.The results show that a single phase of α-Al2O3 with an average particle size of 8μm can be obtained at 900℃ with 2% AlF3 additive.The transformation temperature decreasing IS attributed to introduction of Al3 vacancy and to the formation of intermediate compound of AlOF,which is considered to accelerate the mass transportation from transitional Al2O3 to α-Al2O3.AlF3 concentration and hydrothermal temperature can also affect the morphology of α-Al2O3.When hydrothermal temperature is 120℃,the morphology of α-Al2O3 transforms from irregular to flat hexangular platelet with increasing AlF3 concentration.As hydrothermal temperature increases,the morphology of α-Al2O3 with 2% AlF3 additive changes from polyhedron to hexangular platelet and then to vermicular.     

Effect of NiO content on corrosion behaviour of Ni-xNiO-NiFe2O4 cermets in Na3AlF6-Al2O3 melts

5Ni-xNiO-NiFe2O4 cermets with different NiO contents were prepared and the corrosion behaviour in Na3AlF6-Al2O3 melts was investigated in laboratory electrolysis tests. The results indicate that adding NiO is unfavorable to the densifieation of NiFe2O4-xNiO ceramics, while small Ni doping can greatly improve the sintering property. The electrolysis tests show that excess NiO is beneficial to the reduction of Fe while has little effects on that of Ni in the bath; the steady-state concentrations of Ni, Fe are below the corresponding solubilities of NiFe2O4-xNiO, implying that corrosion mechanism changes while electrifying. Post-electrolysis examination of anodes shows that Ni metal leaches at the anode surface, yet the substrate ceramic prevents the penetration of bath and the further loss of metal phase.     

Synthesis of GdF3 from the Gd2O3-NH4HF2 system

GdF3 was synthesized with Gd2O3 and NH4HF2 under atmospheric pressure and vacuum. The effects of pressure,temperature,and reactant ratio on the reaction process were investigated. A new mechanism for the synthesis of GdF3 was proposed. Powdered Gd2O3 started to react with NH4HF2 at low temperature,and the products were GdNH4F4,NH4F,NH3,and H2O. GdNH4F4 decomposed to GdF3 and NH4F after further high-temperature treatment,accompanying the volatilization and decomposition of NH4F. The whole process could be divided into three steps： synthesis,decomposition,and deamination. The initial and final reaction temperatures decreased under vacuum condition. An optimized process for the preparation of GdF3 was obtained： synthesis under atmospheric pressure at low temperature and decomposition and deamination under vacuum at high temperature.     

Hydrothermal synthesis and characterization of Eu-doped GaOOH/α-Ga2O3/β-Ga2O3 nanoparticles

Eu-doped GaOOH nanoparticles with size of 5-8 nm were prepared by hydrothermal method using sodium dodecylbenzene sulfonate (SDBS) as surfactant. Eu-doped α-Ga₂O₃ and β-Ga₂O₃ were further fabricated by annealing GaOOH:Eu and then characterized by X-ray diffraction(XRD), transmission electron microscopy (TEM) and photoluminescence (PL). The TEM results show that monodisperse Eu³⁺-doped GaOOH nanoparticles form and then transform into Eu³⁺-doped α-Ga₂O₃ and β-Ga₂O₃ through annealing the GaOOH:Eu nanoparticles at 600 and 900 °C, respectively. PL studies indicate that GaOOH:Eu has the highest intensity at 618 nm. Luminescence quenching is observed at higher Eu³⁺ concentration in all samples.     

Fe2O3对SiO2-Al2O3-MgO-Fe2O3-F-系玻璃陶瓷析晶的影响

采用高温熔融法制备不同Fe2O3含量的SiO2-Al2O3-MgO-Fe2O3-F-系基础玻璃,应用扫描电子显微镜(SEM)和X射线衍射(XRD)等技术研究了Fe2O3含量对玻璃析晶的影响规律.结果表明在所研究的玻璃体系中,当玻璃中引入2.0%(质量分数,下同)Fe2O3后,促进了玻璃体的分相,在800℃较低温度下析出氟云母晶体,氟云母晶体的形状受到分相区尺寸的限制.提高析晶温度有利于氟云母晶体的析出.当玻璃中Fe2O3提高到6.0%后,仍能获得透明玻璃体,但是在重新加热时首先形成FeFe2O4相,而抑制了云母晶体的析出.     

Bi2O3/B2O3质量比对Bi2O3-B2O3-ZnO系低熔点玻璃结构及性能的影响

采用熔融法制备了用于真空玻璃封接用的铋系低熔点非晶基础玻璃焊料,利用X射线衍射、红外吸收光谱和X射线光电子能谱对所得玻璃焊料进行了结构分析,采用浸泡腐蚀的方法对焊料的耐酸性进行了测试,使用热膨胀仪和综合热分析仪对其热学性能进行了测试,采用扫描电镜对焊料烧结后的表面形貌进行了观察,测试了焊料对母材的润湿性,研究了Bi2O...     

ZnO-Al2O3-B2O3-SiO2系微晶玻璃的研究

研究了能与可伐合金匹配封接的ZnO-Al2O3-B2O3-SiO2系微晶玻璃,其膨胀系数为5.2×10-6/℃,采用该微晶玻璃的封接器件绝缘电阻可达1×1013Q·cm.通过对该微晶玻璃的差热曲线分析,确定了其热处理制度;用X射线衍射仪和扫描电镜研究了该系统的主晶相,其主晶相为ZnAl2 O4、ZnB2O4和少量的NaSiAl2O4晶体.通过控制碱金属离子进入晶格,可明显提高微晶玻璃的绝缘电阻.     

Solubility of ammonium paratungstate in the system NH_3·H_2O·H_2O

The equilibrium solubilities of 5(NH4)O·12WO3·5H2O (APT·5H2O) were determined at the terminal ammonia concentration of 2 mol/L at 87-95℃. Experimental data were regressed. The linear functional relation between the solubility of APT- 5H2O and the temperature (t /℃) is given as y = - 588.08 + 7.28t. The solubility of the species as a function of the terminal ammonia concentration (x / mol · L-1) is also achieved: y = 36.76 + 18.86x. The solubility of APT · 5H2O produced by ion-exchange method in China is much lower, which is due to much lower silica, much higher NH4Cl, and a small amount of APT · 7H2O with low solubility in the APT crystals. APT · 7H2O forms because of a large amount of NH4Cl and the low activity of water in the crystallization.     

Y2O3含量对SiO2-Al2O3-B2O3-K2O-Li2O系统微晶玻璃的析晶及性能的影响

以SiO2-Al2O3-B2O3-K2O-Li2O为玻璃组成,P2O5和ZrO2为复合成核剂,Sb2O3为澄清剂,Y2O3为添加物,通过传统熔体冷却方法制得了该系统基础玻璃.利用DSC、XRD、SEM及性能测试等手段,研究了Y2O3含量的变化对玻璃析晶行为、析出晶相种类、晶粒尺寸、晶粒分布以及微晶玻璃的力学性能的影响.研究结果表明:随着Y2O3含量的增加,玻璃的析晶峰值温度升高,且析晶峰也逐渐变宽、变钝;Y2O3的加入并不影响微晶玻璃中主晶相的组成,但对其微观结构有明显影响;当Y2O3含量低于2.0%(摩尔分数)时,微晶玻璃的抗弯强度随Y2O3含量增加而增加;当Y2O3含量为2.0%时,获得微晶玻璃的抗弯强度值最高,达到217 MPa;当2.0%≤x(Y2O3)≤2.5%时,抗弯强度反而降低;当Y2O3含量为2.5%时,获得的微晶玻璃具有良好的半透明性,并具有较好的力学性能(抗弯强度为198 MPa);与一步法热处理相比,采用两步晶化热处理有利于提高微晶玻璃的力学性能.     

Phase reaction and sintering behavior of a Al2O3–20wt%AlN–5wt%Y2O3 system

Two major problems exist in the processing of AlN. The first is the difficulty in achieving full densification even at relatively high sintering temperatures. The second is the formation of the spinel phase, AlON. Pure AlN sintered at temperatures up to 2000°C have produced no more than 90–93% densification in the former case, while AlN rich ternary systems (AlN–Al₂O₃-sintering agent) have resulted in the detrimental formation of AlON well before full densification can occur. This paper reports on the phase reaction and sintering behavior of a ternary Al₂O₃–AlN–Y₂O₃ system near the critical temperature range of 1600–1700°C, in a carbo-thermal reduction furnace in a fully nitrogen environment. Full densification (>98%) for AlN without the formation of AlON was achieved by sintering an initial Al₂O₃ rich ternary system (Al₂O₃–20wt%AlN–5wt% Y₂O₃) at a relatively low temperature of 1680°C. Formation of the AlON was delayed until 1700°C, at which a stoichiometric γ-AlON (Al₃O₃N) with spinel type structure was obtained. Thermal conductivity values for a sintered substrate obtained with low oxygen content within the AlN matrix reached 125 W m⁻¹ K⁻¹.