Effect of Gun Current on Electrical Properties of Atmospheric Plasma-Sprayed Lanthanum Silicate Coatings

Apatite-type lanthanum silicate (ATLS) electrolyte coatings for use in intermediate-temperature solid oxide fuel cells were deposited by atmospheric plasma spraying (APS). Plasma-sprayed coatings with typical composition La₁₀(SiO₄)₆O₃ exhibiting good densification and high oxide ionic conductivity were obtained by properly adjusting the spraying parameters, particularly the gun current. The highest obtained ionic conductivity value of 3.3 mS/cm at 1,173 K in air is comparable to other ATLS conductors. This work demonstrated empirically that utilization of the APS technique is feasible to synthesize dense La₁₀(SiO₄)₆O₃ electrolyte coatings using gun currents within an unusually broad range.     

Thermal conductivity and thermal cycle life of La2O3 and HfO2 doped ZrO2-Y2O3 coatings produced by EB-PVD

The effects of La₂O₃ and HfO₂ addition on thermal conductivity and thermal cycle life of EB-PVD YSZ coatings were investigated. La₂O₃ and HfO₂ were selected as additives, because they significantly suppress the sintering of YSZ. The developed coating showed low thermal conductivity as well as high resistance to sintering. Burner rig tests confirmed that the developed coating have a superior thermal insulating effect and have a longer life than that of a coating with conventional composition.     

Effect of (NaPO3)6 concentrations on corrosion resistance of plasma electrolytic oxidation coatings formed on AZ91D magnesium alloy

Different plasma electrolytic oxidation (PEO) coatings were prepared on AZ91D magnesium alloy in electrolytes containing various concentrations of (NaPO₃)₆. The morphologies, chemical compositions and corrosion resistance of the PEO coatings were characterized by environmental scanning electron microscopy (ESEM), X-ray diffractometer (XRD), energy dispersive analysis of X-rays (EDAX), potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) test. The results showed that the PEO coatings were mainly composed of MgO, Mg₂SiO₄, MgAl₂O₄ and amorphous compounds. As the (NaPO₃)₆ concentrations increased from 0 to 10 g/l, the thickness and surface roughness of the coatings approximately linearly increased; the MgO and Mg₂SiO₄ phase increased within the concentration range of 0–3 and 0–5 g/l, and then decreased within the range of 3–10 and 5–10 g/l, respectively, while the MgAl₂O₄ phase gradually decreased. Moreover, the corrosion resistance of the coatings increased within the range of 0–5 g/l and then decreased within the range of 5–10 g/l. The best corrosion resistance coating was obtained in electrolyte containing 5 g/l (NaPO₃)₆, it had the most compact microstructure. Besides, a reasonable equivalent circuit was established, and the fitting results were consistent with the results of the EIS test.     

Synthesis of silicate coating by layer-by-layer self-assembly of Yb2O3 and SiO2 particles

Multilayer particle assemblies that contained both Yb₂O₃ and SiO₂ particles were prepared on Si substrates by layer-by-layer self-assembly (LBLSA) as a new non-line-of-sight avenue of producing dense and uniform Yb₂O₃-SiO₂ coating microstructures. Morphological characteristics of the multilayer particle assemblies upon viscous sintering in the temperature range of 1300 to 1350 °C were evaluated in reference to those of multilayer assemblies that only contained SiO₂ or Yb₂SiO₅ particles. A 4-layer 0.5-μm SiO₂ particle assembly could be easily transformed to a dense and continuous coating structure after sintering. In contrast, a 4-layer 1.7-μm Yb₂SiO₅ particle assembly could not be consolidated and densified, as anticipated from the absence of the viscous sintering mechanism provided by the SiO₂ phase. Most of the coatings produced from sintering of Yb₂O₃-SiO₂ (0.5 μm) particles assemblies were dense and continuous with Yb₂Si₂O₇ and Yb₂SiO₅ as two predominant phases. The results suggest the feasibility of producing dense and uniform silicate coating structures by integrating the LBLSA concept with the viscous flow sintering mechanism provided by the SiO₂ particles.     

Conductivity of a new pyrophosphate Sn0.9Sc0.1(P2O7)1−δ prepared by an aqueous solution method

New pyrophosphate Sn_0.9Sc_0.1(P₂O₇)_1−δ was prepared by an aqueous solution method. The structure and conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ have been investigated. XRD analysis indicates that Sn_0.9Sc_0.1(P₂O₇)_1−δ exhibits a 3 × 3 × 3 super structure. It was found that Sn_0.9Sc_0.1(P₂O₇)_1−δ prepared by an aqueous method is not conductive. The total conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ in open air is 2.35 × 10⁻⁶ and 2.82 × 10⁻⁹ S/cm at 900 and 400 °C respectively. In wet air, the total conductivity is about two orders of magnitude higher (8.1 × 10⁻⁷ S/cm at 400 °C) than in open air indicating some proton conduction. SnP₂O₇ and Sn_0.92In_0.08(P₂O₇)_1−δ prepared by an acidic method were reported fairly conductive but prepared by similar solution methods are not conductive. Therefore, the conductivity of SnP₂O₇-based materials might be related to the synthetic history. The possible conduction mechanism of SnP₂O₇-based materials has been discussed in detail.     

New dielectric material system of La(Mg1/2Ti1/2)O3–Ca0.6La0.8/3TiO3 for microwave applications

The microstructure and microwave dielectric properties of xLa(Mg_1/2Ti_1/2)O₃–(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics system with ZnO additions (0.5 wt.%) investigated by the conventional solid-state route have been studied. Doping with ZnO (0.5 wt.%) can effectively promote the densification and the dielectric properties of xLa(Mg_1/2Ti_1/2)O₃–(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics. 0.6La(Mg_1/2Ti_1/2)O₃–0.4Ca_0.6La_0.8/3TiO₃ ceramics with 0.5 wt.% ZnO addition possess a dielectric constant (_r) of 43.6, a Q × f value of 48,000 (at 8 GHz) and a temperature coefficient of resonant frequency (τ_f) of −1 ppm/°C sintering at 1475 °C. As the content of La(Mg_1/2Ti_1/2)O₃ increases, the highest Q × f value of 62,900 (GHz) for x = 0.8 is achieved at the sintering temperature 1475 °C. A parallel-coupled line band-pass filter is designed and simulated using the proposed dielectric to study its performance.     

SiO_2含量对激光熔覆含La_2O_3生物陶瓷涂层性能的影响

采用激光熔覆技术,利用CaHPO_4·2H_2O,CaCO_3,La_2O_3,SiO_2粉末和Ti粉在医用钛合金Ti-6Al-4V表面制备掺杂的质量分数分别为0%,5%,10%,15%SiO2的含La2O3梯度生物陶瓷涂层,并研究了SiO_2含量对涂层性能的影响。利用金相显微镜、扫描电镜、能谱仪、X射线分析仪分别对涂层进行显微结构、表面元素、物相组成分析,利用MTT细胞活性检测法对涂层上种植的小鼠破骨前体细胞(RAW264.7)进行细胞活性分析。结果显示:掺杂10%~15%的SiO_2后,涂层的裂纹明显减少,且厚度变均匀。涂层在模拟体液(SBF)中浸泡2周后,羟基磷灰石(HA)在掺杂10%SiO_2涂层表面的沉积量最多,涂层表面的金属元素含量稀少,这表明含10%SiO_2涂层在SBF中具备更加优良的沉积HA的能力,同时有效的阻碍了基体中重金属离子的析出。MTT结果表明,掺杂SiO_2的涂层对破骨前体细胞的活性有更加明显的抑制作用。     

Investigation of the microwave dielectric properties of Ca1−xMgxLa4Ti5O17 ceramics for application in coplanar patch antenna

In this paper, the dielectric properties of Ca_1−xMg_xLa₄Ti₅O₁₇ ceramics at microwave frequency have been studied. The diffraction peaks of Ca_(1−x)Mg_xLa₄Ti₅O₁₇ ceramics nearly unchanged with x increasing from 0 to 0.03. Similar X-ray diffraction peaks of Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic were observed at different sintering temperatures. A maximum density of 5.3 g/cm³ can be obtained for Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h. A maximum dielectric constant (_r) and quality factor (Q × f) of Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h are 56.3 and 12,300 GHz (at 6.4 GHz), respectively. A near-zero temperature coefficient of resonant frequency (τ_f) of −9.6 ppm/°C can be obtained for Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h. The measurement results for the aperture-coupled coplanar patch antenna at 2.5 GHz are presented. With this technique, a 3.33% bandwidth (return loss <−10 dB) with a center frequency at approximately 2.5 GHz has been successfully achieved.     

Novel thermal barrier coatings based on La2Ce2O7/8YSZ double-ceramic-layer systems deposited by electron beam physical vapor deposition

Novel thermal barrier coatings based on La₂Ce₂O₇/8YSZ double-ceramic-layer (DCL) systems, which were deposited by electron beam physical vapor deposition (EB-PVD), were found to have a longer lifetime compared to the single layer La₂Ce₂O₇ (LC) system, and even much longer than that of the single layer 8YSZ system under burner rig test. The DCL coating structure design can effectively alleviate the thermal expansion mismatch between LC coating and bond coat, as well as avoid the chemical reaction between LC and Al₂O₃ in thermally grown oxide (TGO), which occurs above 1000 °C as determined by differential scanning calorimetry (DSC) analysis. The failure mechanism of LC/8YSZ DCL coating is mainly due to the sintering of LC coating surface after long-term thermal cycling.     

In situ formation of La containing dispersed phase on the sinter skin of La2O3 and Cr3C2 unitedly doped WC–Co cemented carbide

The as-sintered sinter skin of WC–11 wt% Co–0.71 wt% Cr₃C₂–0.06 wt% La₂O₃ cemented carbide was observed and analyzed by scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction. It was unexpectedly discovered that lanthanum which was added in the form of oxide could migrate directionally from the alloy to the sinter skin during the sintering process. As a result, La₂O₂S and LaCoO₃ phases were formed in situ on the sinter skin. It is significant that both phases are characterized with layered-structure related self-lubricating function and high melting point. Noteworthily, La₂O₂S grains preferentially grew up along a group of parallel faces with orientation index [0 0 1] in the WC + β matrix. It was revealed that the alloy had a diffusion-resulted dual structure (i.e., core and skin structure), i.e., WC + β + η three-phase structure in the inner part and WC + β + La₂O₂S + LaCoO₃ four-phase structure on the sinter skin. Cr₃C₂ with carbon-donation ability and the impurity elements from the sintering atmosphere with much bigger electronegative parameters than lanthanum are thought to be the driving force behind the directional migration.     

Phase relationships in the systems RE2O3-Al2O3-SiO2 (RE = rare earth element, Y, and Sc)

A literature survey and recent results on phase relationships in the quasi-ternary systems RE₂O₃-Al₂O₃-SiO₂ are given. The investigated systems exhibit extended ternary solid solutions, RE_9.33+2x(Si_{1_x}Al_xO₄)₆O₂ (withx up to ~0.33) and/or RE₄Al_{2(1_X)}Si_2xO_9+x (withx up to ~0.3), which are based on the quasi-binary phases RE_9.33(SiO₄)₆O₂ and RE₄A1₂O₉, respectively. The former is encountered only in systems with laige RE³⁺ ions (e.g., La³⁺), whereas the latter is found in systems with small RE³⁺ ions (e.g., Yb³⁺); in systems with medium-sized KE³⁺ ions (e.g., Gd³⁺) both types exist Quasi-ternary compounds are known only in the La, Ce, and Sc systems. Severe discrepancies in reported ternary eutectic temperatures led to a need for their accurate redeteimination.     

Structures, electrical and thermal expansion properties of Sr-doped La2Mo2O9 oxide-ion conductors

The oxide-ion conductors (La_1−xSr_x)₂Mo₂O_9−δ (x = 0.01–0.08) were prepared by means of a conventional solid-state reaction. The effects of Sr doping for La site on the structures, electrical and thermal expansion properties of the oxide-ion conductor La₂Mo₂O₉ were investigated using X-ray diffraction, direct current four-probe method, thermal dilatometer and scanning electron microscopy, respectively. The results show that the lattice constants were first decreased, then increased, and decreased again with the increase of Sr doping content. The solid solubility of Sr in (La_1−xSr_x)₂Mo₂O_9−δ is x = 0.07. The sinterability of samples is markedly improved with the increase of Sr doping content. The sintered density of sample x > 0.07 is higher than 96% of its theoretical density. When x > 0.02, doping Sr in La₂Mo₂O₉ can inhibit the excessive growth of grains, thus increases the sintered density of samples. The structural transition temperature shifts to the low side with the increase of Sr doping content, and the phase transition is completely suppressed when the doping content reaches 0.07. The conductivity of sample increases with the increase of Sr doping content. The conductivity of sample x = 0.07 reaches a maximum of 0.078 S/cm and 0.101 S/cm at 800 °C and 850 °C, respectively. In this study, it was demonstrated that doping 7 mol% Sr for La site not only can completely suppress the structural phase transition in La₂Mo₂O₉, but also can effectively enhance electrical conductivity of samples at higher temperature.     

Charge compensation, electrical and dielectric behavior of lanthanum doped CaCu3Ti4O12

Mechanism of charge compensation on lanthanum, (La³⁺) substitution on Ca site in calcium copper titanate (CaCu₃Ti₄O₁₂), and its effect on resulting electrical and dielectric properties has been studied in the present investigation. For this purpose samples were prepared according to two stoichiometries viz. La_xCa_(1−3x/2)Cu₃Ti₄O₁₂ (x ≤ 0.09) and La_xCa_(1−x)Cu₃Ti₄O₁₂ (x = 0.03) by solid state ceramic route. The former represents ionic compensation while the later is in accordance with electronic compensation. Nature of charge carriers is identified by measuring Seebeck coefficient which is found to be negative in the entire range of measurement. In order to understand the mechanism of conduction, ac conductivity is measured as a function of temperature and frequency. Space charge polarization is the dominant polarization mechanism phenomenon at low frequency and high temperature while orientation polarization dominates at low temperature and high frequency. Impedance analysis confirms the formation of internal barrier layers which is responsible for high dielectric constant in these samples.     

Low temperature sintering and properties of CaO–B2O3–SiO2 system glass ceramics for LTCC applications

The P₂O₅ + ZnO, ZrO₂ + TiO₂, B₂O₃ and a low-melting-point CaO–B₂O₃–SiO₂ glass (LG) are selected as the sintering additives, and the effect of their additions on the microwave dielectric properties, mechanical properties and microstructures of CaO–B₂O₃–SiO₂ system glass ceramics is investigated. It is found that the sintering temperature of pure CBS glass is higher than 950 °C and the sintering range is about 10 °C. With the above additions, the glass ceramics can be sintered between 820 °C and 900 °C. The dielectric properties of the samples are dependent on the additions, densification and microstructures of sintered bodies. The major phases of this material are CaSiO₃, CaB₂O₄ and SiO₂. With 10 wt% B₂O₃ and LG glass additions, the CBS glass ceramics have better mechanical properties, but worse dielectric properties. The _r values of 6.51 and 7.07, the tan δ values of 0.0029 and 0.0019 at 10 GHz, are obtained for the CBS glass ceramics sintered at 860 °C with 2 wt% P₂O₅ + 2 wt% ZnO and 2 wt% ZrO₂ + 2 wt% TiO₂ additions, respectively. This material is suitable to be used as the LTCC material for the application in wireless communications.     

Anti-corrosion microarc oxidation coatings on SiCP/AZ31 magnesium matrix composite

The corrosion-resistant ceramic coatings up to 80 μm thick were fabricated on SiC_P/AZ31 magnesium matrix composite by microarc oxidation (MAO) technique in Na₃PO₄ + KOH + NaF solution. The microstructure, composition and phase constituent of ceramic coatings were analyzed by SEM and XRD, and the electrochemical corrosion behaviour of coatings was evaluated by the electrochemical polarization method. The thicker coating is compact and displays a good adhesion to the composite substrate. The ceramic coatings consist of MgO, Mg₂SiO₄, MgF₂, Mg₃(PO₄)₂, furthermore, a few residual SiC phases were also found in the coatings by means of SEM observation and EDX analysis. Most of SiC reinforced particles in the oxidized composite substrate have transformed into the oxides under microarc discharge sintering, but a few residual SiC reinforcements in the MAO coatings have not disrupted the continuity of coatings. So the corrosion resistance of the SiC_P/AZ31 composite is greatly improved by MAO surface treatment, however, the corrosion resistance of coated composite also depends on the coating thickness.     

Novel thermal barrier coatings based on La2(Zr0.7Ce0.3)2O7/8YSZ double-ceramic-layer systems deposited by electron beam physical vapor deposition

Double-ceramic-layer (DCL) thermal barrier coatings (TBCs) of La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) and yttria stabilized zirconia (YSZ) were deposited by electron beam-physical vapor deposition (EB-PVD). The thermal cycling test at 1373 K in an air furnace indicates the DCL coating has a much longer lifetime than the single layer LZ7C3 coating, and even longer than that of the single layer YSZ coating. The superior sintering-resistance of LZ7C3 coating, the similar thermal expansion behaviors of YSZ interlayer with LZ7C3 coating and thermally grown oxide (TGO) layer, and the unique growth modes of columns within DCL coating are all very helpful to the prolongation of thermal cycling life of DCL coating. The failure of DCL coating is mainly a result of the reduction-oxidation of cerium oxide, the crack initiation, propagation and extension, the abnormal oxidation of bond coat, the degradation of t′-phase in YSZ coating and the outward diffusion of Cr alloying element into LZ7C3 coating.     

Fe3O4/SiO2/Bi2WO6磁性复合光催化剂的制备及其光催化性能

钨酸铋(Bi₂WO₆),结构最简单的Aurivillius相化合物,是近期受到研究者关注的新型光催化材料。然而,光催化剂粉末在反应介质中难被回收,工业化应用成本较高。本文用三步方法合成了可回收的Fe₃O₄/SiO₂/Bi₂WO₆磁性复合光催化剂,通过溶剂热法合成具有磁性的Fe₃O₄,用溶胶凝胶法在Fe₃O₄表面覆盖SiO₂层,后将磁性颗粒与Bi₂WO₆纳米片相结合。光催化剂的形貌结构及性能通过XRD、SEM、PL、UV-vis进行表征测试。结果表明,直径约500 nm的Fe₃O₄微球附着在边长约500 nm的Bi₂WO₆纳米片的表面,SiO₂在两者之间起到了粘连作用。光催化剂Fe₃O₄/SiO₂/Bi₂WO₆对于罗丹明B的光降解活性较好,且有一定磁性,可以通过外加磁场将其从溶液中分离,有较大的应用潜力。     

A novel proton conducting Ba0.95K0.05Ce0.6Zr0.2Gd0.16Zn0.04O3−δ for SOFC

A new proton conducting Ba_0.95K_0.05Ce_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ electrolyte membrane was prepared on NiO-based anode support by suspension spray followed by a co-sintering at 1400 °C for 4 h. Chemical stability test shows that this new proton conductor displays adequate chemical stability against CO₂ at intermediate temperatures. The conductivity of Ba_0.95K_0.05Ce_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ in humidified H₂ is about 50% higher than that of BaCe_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ from 500 to 800 °C. With La_0.8Sr_0.2MnO_3−δ cathode, fuel cell with Ba_0.95K_0.05Ce_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ electrolyte shows 1.02 V of OCV and 354 mW/cm² of maximum power density at 700 °C, respectively. And the cell performance did not degrade after running at least for 10 h.     

Effect of La2O3 on corrosion resistance of laser clad ferrite-based alloy coatings

The ferrite-based alloy powders with different contents of La₂O₃ were laser clad on a steel substrate. The microstructural features and phase structure of these coatings were studied by scanning electron microscope (SEM) and X-ray diffraction (XRD), respectively. The results showed that the microstructure of the coatings with La₂O₃ was refined and purified. The main phase of the coatings was γ (Fe, Ni). Moreover, the electrochemical properties of the coatings were investigated by anodic polarization curves and electrochemical impedance spectroscopy (EIS). Anodic polarization results indicated that both polarizing voltage and polarization current density were reduced with the addition of La₂O₃. EIS results showed that, with the increment of La₂O₃, the inductive arcs shrunk and capacitive arcs expanded. The inductive arc at low frequency was disappeared and changed to capacitive arc thoroughly when the content of La₂O₃ reached 1.2 wt.%. The corrosion weight loss experiment results showed that the corrosion rate was lower and the corrosion attack was lighter in the coatings with La₂O₃ than that without La₂O₃, resulting in a substantial improvement of the corrosion resistance.     

Effect of Sm2O3 content on microstructure and thermal conductivity of Spark Plasma Sintered AlN ceramics

Dense aluminum nitride ceramics were prepared by Spark Plasma Sintering at a lower sintering temperature of 1700 °C with Sm₂O₃ as sintering additives. The effect of Sm₂O₃ content on the density, phase composition, microstructure and thermal conductivity of AlN ceramics was investigated. The results showed that Spark Plasma Sintering could fabricate dense AlN ceramics with superior thermal properties in a very short time. Sm₂O₃ not only facilitated the densification via the liquid-phase sintering mechanism but also improved thermal conductivity by decreasing oxygen impurity. Thermal conductivity decreased with increasing amount of Sm₂O₃ and the highest thermal conductivity was obtained for the AlN ceramics with 2 wt.% Sm₂O₃ content. During Spark Plasma Sintering process, only 2–3 wt.% sintering additives was enough to fabricate dense AlN ceramics, and the microstructures played a key role in controlling the thermal conductivity of AlN ceramics.