Effect of Al2O3 on the structure and microwave dielectric properties of Ca0.7Ti0.7La0.3Al0.3O3

The effect of excess Al₂O₃ on the densification, structure and microwave dielectric properties of Ca_0.7Ti_0.7La_0.3Al_0.3O₃ (CTLA) was investigated. CTLA ceramics were prepared using the conventional mixed oxide route. Excess Al₂O₃ in the range of 0.1–0.5 wt% was added. It was found that Al₂O₃ improved the densification. A phase rich in Ca and Al was found in the microstructure of Al₂O₃ doped samples. Additions of Al₂O₃ coupled with the slow cooling after sintering improved the microwave dielectric properties. CTLA ceramics with 0.25 wt% Al₂O₃ cooled at 5 °C/h showed high density and a uniform grain structure with ɛ_r = 46, Q × f = 38,289 and τ_f = +12 ppm/°C at 4 GHz. XRD and TEM examinations showed the presence of (1 1 2) and (1 1 0) type twins arising from a⁻a⁻c⁺ tilt system with the presence of anti-phase domain boundaries from the displacement of A-site cations of the orthorhombic perovskite structure.     

Ca0.7Ti0.7La0.3Al0.3O3微波介质陶瓷微观组织结构与介电性能

采用固相反应法制备斜方晶系钙钛矿结构Ca07Ti07La0.3Al0.3O3微波介质陶瓷,研究了Al3+、Ca2、Ba2+和La3+离子掺杂对CTLA陶瓷微观组织结构和介电性能的影响.研究结果表明不同掺杂离子对于CTLA陶瓷的微观结构和介电性能有很大的影响,不同离子掺杂CTLA陶瓷的晶粒尺寸、气孔率、晶界析出相有很大的不同.Al3+、Ca2+、Ba2+和La3+离子掺杂可以有效降低CTLA陶瓷的谐振频率温度系数,但Ca2+、Ba2+离子掺杂同时也降低了CTLA陶瓷的致密度和Q×f值,Al3+、La3+离子掺杂不仅有效提高了CTLA陶瓷的致密度和Q×f值,并且有效降低了谐振频率温度系数.适量掺杂La3离子可以有效促进CTLA陶瓷的致密化,提高了CTLA陶瓷的微波介电性能.掺杂0.15mol％ La3+的CTLA陶瓷在4.7 GHz下测试介电性能为:εr=48.39,Q×f=32560 GHz,τf=23.68 ppm/C.     

Ca_(2.7)Sr_(0.3)Co_4O_9 和 Ca_(0.95)Sm_(0.05)MnO_3 热电材料的性能及器件(英文)

为了构造具有一定实用性能的氧化物热电器件,对 p 型 Ca3Co4O9和 n 型 CaMnO3过渡金属氧化物半导体进行研究,结果表明:Ca2.7Sr0.3Co4O9和 Ca0.95Sm0.05MnO3的热电性能良好。Ca2.7Sr0.3Co4O9陶瓷的微观形貌呈片层状及尖锐的(00?)相,说明具有高度织构,Ca0.95Sm0.05MnO3陶瓷为单一相正交晶系。分析了样品形成的化学反应过程。热电参数测试结果表明:Ca2.7Sr0.3Co4O9为 p 型半导体,空穴导电机制,Ca0.95Sm0.05MnO3为 n 型半导体,电子导电机制。两种材料的电阻均较低,在 870 K,Seebeck 系数分别为 170 μV/K 和–167 μV/K。在测量温度范围内,热导率变化很小,并计算出热电优值。利用此两种材料构造热电器件,并对其性能进行测试。     

Improvement of electrical and magnetic properties in La0.67Ca0.33Mn0.97Co0.03O3 ceramic by Ag doping

For the perovskite manganite La_1-xCa_xMnO₃, achieving high temperature coefficient of resistance (TCR) and magnetoresistance (MR) is the key to realize its potential applications. In this study, high-quality La_0.67Ca_0.33Mn_0.97Co_0.03O₃:Ag_x polycrystalline ceramics were prepared by the sol-gel method. The results show that Ag doping has important impact on metal-insulator and ferromagnetic-paramagnetic transitions. A Ag doping amount increases, the grain size of the samples increases at x = 0.05 and then decreases. The doping of Ag can improve the crystalline quality of the samples and enhance the connectivity between grains, thereby improving the metallicity of the system. Additionally, with Ag doping amount increases, the resistivity of the samples gradually decreased, while the Curie temperature and the metal-insulator transition temperature gradually increased. Especially after Ag doping, both the TCR peak (TCR_peak) and the MR peak (MR_peak) values are significantly improved. The TCR_peak reaches 65.2%·K^?1 at x = 0.1, while the MR_peak is as high as 82.6% at x = 0.05 under 1 T magnetic field. Doping perovskite manganite ceramics with Co and Ag can greatly optimize their TCR and MR, favoring the potential applications of these materials.     

Co~(3+)掺杂对La_(0.7)Sr_(0.3)Mn_(1-x)Co_xO_3的结构及光催化性能的影响

本文采用溶胶-凝胶法制备了钙钛矿型复合氧化物La0.7Sr0.3Mn1-xCoxO3。利用XRD,SEM对纳米颗粒的结构、形貌进行了表征。结果表明,合成的样品为钙钛矿型,呈立方颗粒状,粒径均匀,边长约为1μm。根据甲基橙的降解情况对其光催化活性进行了研究。结果表明,经过B位Co3+离子掺杂的La0.7Sr0.3Mn1-xCoxO3样品,光催化活性明显提高。     

Electrical transport properties of Sm-doped La0.7Ca0.3MnO3 polycrystalline ceramics

Improving the magnetoresistance effect of perovskite ceramic materials under a low applied magnetic field to expand its application range is one of the main research directions of this type of material. In this study, La_0.7Ca_0.3MnO₃ was doped with different levels of Sm by the sol-gel method to yield a series of La_0.7-xSm_xCa_0.3MnO₃ (LSCMO) polycrystalline ceramics. X-ray diffraction (XRD) results revealed that LSCMO ceramics possessed standard perovskite structures. Scanning electron microscopy (SEM) showed grains closely connected without obvious holes. In addition, the grain size gradually decreased with the increase in Sm doping content. The resistivity temperature curves displayed a clear metal-insulator transition behavior of LSCMO accompanied by a steep change from ferromagnetic to paramagnetic behavior (FM-PM). The metal-insulator transition temperature (T_p) values of the as-obtained LSCMO gradually shifted toward lower temperatures with increase in Sm content. Moreover, resistivity temperature coefficient (TCR) and magnetoresistance (MR) values also gradually increased with Sm doping content. The transport properties in polycrystalline ceramics could be adequately explained by the double exchange model, which would be useful for interpreting the CMR effects when used in magnetic devices.     

La0.3Ca0.7Mn1-xVxO3体系的电荷序和自旋序

通过对样品La0.3Ca0.7Mn1-xVxO3(x=0.05,0.10,0.134,0.20)的磁化强度-温度(magnetization-temperature, M-T)曲线、电阻率-温度(resistivity-temperature, p-T)曲线、电子自旋共振谱的测量,研究了Mn位V掺杂La0.3Ca0.7MnO3体系电荷序和自旋序的影响.结果表明:当0.05≤x≤0.134时,体系存在电荷有序(CO)相,体系自旋序随温度降低发生顺磁(paramagnetism, PM)-荷有序(charge ordering, CO)-反铁磁(antiferromagnetism, AFM)变化.当x=0.20时,电荷有序融化,体系出现再入型自旋玻璃行为.     

Influence of the processing way for La3+-doping on crystal structure,microstructure, and microwave dielectric properties of Ca0.7Ti0.7La0.3Al0.3O3 ceramics

Perovskite ceramics with a formula of Ca_0.7Ti_0.7La_0.3Al_0.3O₃ (CTLA) were produced through a conventional solid-state reaction procedure following three different La³⁺-doping methods using powders of La₂O₃, or La₂O₃/Al₂O₃ powder mixture, or LaAlO₃. La³⁺ doping favored grain growth and densification, affected the grain size distribution, and improved the dielectric properties of the produced sintered CTLA ceramics. The doping methods had a strong influence on these properties. More specifically, doping with La₂O₃ and La₂O₃/Al₂O₃ resulted in formation of solid solution, while a secondary phase formed in the CTLA ceramics doped with LaAlO₃, which caused a coarsening of the microstructure and lowered the La³⁺ doping effects on the dielectric properties. The experimental results suggest that La³⁺ doping improves the dielectric properties of the sintered CTLA perovskite ceramics, which are further enhanced by doping with Al³⁺ ions in small amounts. However, further increase of Al³⁺ ions content jeopardizes them.     

溶胶凝胶法合成La_(0.7)Sr_(0.3)Fe_(0.8)Co_(0.2)O_3影响因素的研究

以合成中温固体氧化物燃料电池阴极La0.7Sr0.3Fe0.8Co0.2O3(LSFC)粉体为研究对象,探讨了PVA改进的溶胶凝胶法合成粉体的影响因素,获得最优实验条件。当pH值=7,柠檬酸与金属离子摩尔比为1.6∶1;PVA与硝酸盐质量比为1∶4时,能够形成形态良好且透明澄清的溶胶,再经12 h的陈化形成凝胶,然后在155℃烘箱中使凝胶膨化制得LSFC前驱体。LSFC前躯体在900℃煅烧2 h后形成晶体结构稳定、粒径分布均匀、具有单一钙钛矿结构的粉体。     

Electrical transport and magnetic properties of Mn3O4-La0.7Ca0.3MnO3 ceramic composites prepared by a one-step spray-drying technique

La_0.7Ca_0.3MnO₃/Mn₃O₄ composites can be synthesized in one step by thermal treatment of a spray-dried precursor, instead of mixing pre-synthesized powders. Another advantage of this composite system is that a long sintering step can be used without leading to significant modification of the manganite composition. The percolation threshold is reached at ∼20 vol% of manganite phase. The 77 K low field magnetoresistance is enhanced to ∼11% at 0.15 T when the composition is close to the percolation threshold.     

Microwave sintered Bi0.90La0.10Fe0.95Mn0.05O3 nanocrystalline ceramics: Impedance and modulus spectroscopy

Multiferroic Bi_0.90La_0.10Fe_0.95Mn_0.05O₃ (BLFMO) nanoceramics were synthesized by PVA sol-gel method, followed by microwave sintering. The structural, microstructural and electrical properties of BLFMO were investigated. The crystal symmetry and unit cell dimensions were determined from the experimental data using Rietveld analysis. BLFMO revealed only one electroactive region as verified from impedance and modulus spectroscopy. Overlapping large polaron tunneling transport mechanism was observed from AC conductivity analysis. Conduction below 250 °C (−30 °C≤T≤250 °C) was attributed to translational hopping while above 250 °C (250 °C≤T≤350 °C) corresponds to electron hopping between charge defects. The relative permittivity varies from 66 to 203 at 1 kHz over the measured temperature range (−150 °C≤T≤350 °C). The electrical conductivity of the microwave sintered BLFMO has been discussed based on defect reaction with Mn doping. The measured DC conductivity in the range of 10⁻¹³ S/cm at −130 °C to 10⁻⁴ S/cm at 350 °C revealed the insulating behavior of the sample. At room temperature, the DC resistivity of the sample was over ~50 MΩ cm. The stretching constant (β) obtained from KWW (Kohlrausch-Williams-Watts) equation indicates that the sample inclined towards ideal Debye behavior as the temperature increases.     

Modified self-propagating high-temperature synthesis of nanosized La0.7Ca0.3MnO3

A modified solid-state combustion route was developed for the preparation of nanocrystalline manganite La_0.7Ca_0.3MnO₃ in a single-step process, using metal nitrates and glucose/KNO₃ redox mixture. The obtained sample was found to crystallize within O′ type of orthorhombic perovskite structure (space group Pnma), without the presence of other structural phases or impurities. Nanoparticles are found to have particle size in the range 12–35 nm, and to be highly crystalline without the presence of amorphous surface layer. Magnetic measurements show that nanoparticles display bulk-like magnetic properties, with ferromagnetic phase transition at 125 K and the absence of superparamagnetic or spin-glass behavior.     

Incongruent pulsed laser deposition strategy for thin film growth of Ca3Co4O9 thermoelectric compound

Pulsed laser deposition (PLD) is commonly used to grow thin film materials with complex stoichiometry and crystal structures, since it achieves a congruent transfer of the target cation elements to the substrate. Although the incongruent PLDs were previously observed via regulating the plasma/background interaction regimes, the incongruent PLDs were seldom investigated and applied practically for the thin film depositions. Herein, we demonstrate the incongruent pulsed laser deposition of Ca₃Co₄O₉ thermoelectric thin films, via regulating the target compositions and the oxygen background pressures to preferential scattering the plasma cation compositions. To compare the deposition properties via incongruent and congruent thin film growth, we systematically investigate the crystal structures, surface morphologies, elemental distributions and thermoelectric transportation behaviors for Ca₃Co₄O₉ thin films grown at various target compositions and background pressure ranges. A stoichiometric Ca₃Co₄O₉ thin film composition is achievable via designing an incongruent PLD strategy, in which case the Ca/Co ratios in the targets are enlarged actively while the PLDs are performed at a pressure range of 10⁰ Pa to further preferential scatter of the lighter Ca compared to Co. Nevertheless, the incongruently grown thin films exhibit lower thermoelectric performances, compared to the one at a similar composition grown via the congruent PLD strategy. This result may associate to the localized composition inhomogeneity in the Ca₃Co4O₉ grown incongruently, and their electronical resistivities are largely elevated by the resultant impurities that are hardly detectable by X-ray diffractions. The present work reveals the complexity in deposition mechanism and kinetics when performing incongruent PLDs, in particular, for growing multiple elemental thin film materials.     

Enhanced Room Temperature Multiferroic Properties of (Bi0.95La0.05)(Fe0.97Mn0.03)O3/CoFe2O4 and CoFe2O4/(Bi0.95La0.05)(Fe0.97Mn0.03)O3 Double‐Layered Thin Films

Multiferroic (Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃/CoFe₂O₄ and CoFe₂O₄/(Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃ double‐layered thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates via a chemical solution deposition method. In both the thin films, superior multiferroic properties were observed at room temperature. However, substantial enhancements in magnetic properties, such as saturated ferromagnetic hysteresis loop with large 2M_r (68.8 emu/cm³) and 2H_c (11.7 kOe), as well as moderate ferroelectric properties, such as 2P_r (58 μC/cm²) with low leakage current density (4 × 10^?9 A/cm² at 100 kV/cm), were observed in the (Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃/CoFe₂O₄ at room temperature. Structural distortion, deformation of [(Fe, Mn)O₆] oxygen octahedra, and superexchange interaction in the (Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃ are attributed to the enhanced properties.     

Dielectric properties of (Ba0.95Ca0.05)(Ti1-yCay)O3-y ceramics

Calcium doped barium titanate ceramics with composition (Ba_0.95Ca_{0. 05}) (Ti_1-yCa_y)O_3-y prepared by a liquid mixing technique were used to measure the dielectric properties. The pure barium titanate and lightly-Ca-doped materials obey a Curie Weiss law when the temperature is above the Curie temperature. It has been found that the average cubic-tetragonal phase transition temperature moves downward when the octahedrally-coordinated Ca concentration increases, and heavily-Ca-doped barium titanate ceramics show relaxor behavior with a diffuse phase transition characteristic (DPT). Above the average transition temperature T_av the dielectric properties for heavily doped materials do not obey the Curie Weiss law, but can be described by a quadratic relation over a wide range of temperature. Experiments have shown that there exists an extra K(T) peak attributable to the existence of separate microregions of Ba_0.95Ca_0.05TiO₃ in a matrix of (Ba_0.95Ca_0.05) (Ti_1-yCa_y)O_3-y (where y ≤ 2%).     

Preparation of dense La0.7Ca0.3MnO3 ceramics from freeze-dried precursors

Sinterability of La_0.7Ca_0.3MnO₃ precursors, obtained by the freeze-drying method, is studied in order to develop a technique for preparation of dense (>95%) ceramics for CMR measurements and sputtering applications. Single phase powders, obtained by thermal decomposition at 650°C, were subjected to deagglomeration by ultrasonic or mechanical treatment. Sintering of deagglomerated powders for several hours at T=1200–1300°C allowed to achieve densities up to 97–98%. The best sinterability is demonstrated by mechanically processed powder, but further sintering of ceramics, obtained from this precursor, results in significant dedensification (up to 85% at 1300°C). Analysis of precursors and dedensified samples shows at high temperature decomposition of carbonates in closed pores to be the most probable reason for the observed process.     

Structural,morphological, and magnetic properties of sol-gel derived La0.7Ca0.3MnO3 manganite nanoparticles

La_0.7Ca_0.3MnO₃ (LCMO) manganite nanoparticles are synthesized via a sol-gel route at different annealed temperatures. Their structural, morphological, and magnetic properties are investigated. The X-ray diffraction patterns coupled with electron diffraction confirm that all the LCMO samples are single phase and crystallize in the orthorhombic perovskite structure (Pnma space group). The morphology of the samples observed by TEM, reveals a spherical shape with an average grain size lower than 50 nm. The resolved lattice fringes in high-resolution TEM images also reveal the single crystalline nature of the LCMO nanoparticles. Magnetization measurements versus temperature under low magnetic field (0.01 T) show a paramagnetic - ferromagnetic transition for all the samples. The Curie temperature (T_c) is found to be decreased with increasing the annealed temperature. A bifurcation is observed in the zero field-cooled and field-cooled magnetizations, indicating a competition between ferromagnetic and antiferromagnetic interactions in the nanoparticles at low temperatures. Field-cooled hysteresis measurements suggest a cluster glasslike behavior of the nanoparticles. Room temperature and low temperature M - H loops demonstrate that all the samples exhibit ferromagnetic behavior at 5 K, whereas a paramagnetic behavior at room temperature. Resistivity behavior of the LCMO samples shows that they exhibit a metal - insulator transition. Magnetoresistance of ~ 50% at the field up to 8 T was observed at 2 K in the LSCO samples annealed at 600 °C.     

Magnetic properties of Er(Co,Mn)O3 perovskites

The erbium-based manganite ErMnO₃ has been partially substituted at the manganese site by Co in the general formula ErCo_xMn_1−xO₃. The perovskite orthorhombic structure is found from x(Co) = 0.3 up to x(Co) = 0.7, provided that the synthesis is performed under oxygenation conditions to favour the presence of Co³⁺. Magnetic properties show unusual phenomena, correlated with the presence of different magnetic entities (i.e., Er³⁺, Co²⁺, Co³⁺, Mn³⁺, Mn⁴⁺): the overall magnetic moment reverses its sign when the sample is cooled under an external magnetic field, while the magnetization loops performed at T < 4 K show intersecting branches at low fields and a sudden jump at high fields. A phenomenological model of two interacting sublattices, coupled by an antiferromagnetic exchange interaction, explains the inversion of the overall spin, while the high-field discontinuity is explained in terms of dynamical models.     

Influence of cobalt and sintering temperature on structure and electrical properties of BaZr0.05Ti0.95O3 ceramics

Pure and Co-modified BaZr_0.05Ti_0.95O₃ ceramics were fabricated by the traditional solid state reaction technique. The influence of cobalt and sintering temperature on structure, dielectric, ferroelectric properties and diffuse phase transition of BZT ceramics were investigated systematically. 1300 °C was the optimal sintering temperature for BZT ceramics. The solid solubility limit of Co ions in BZT matrix was determined to be 0.4 mol%. The introduction of a moderate amount of Co ions was believed to benefit the microstructure development and make the grain size more uniform. Compared with undoped counterparts, 0.4 mol% Co-modified ceramics showed equivalent ferroelectric properties with a high remnant polarization (P_r=9.6 μC/cm²) and a low coercive field (E_c=0.21 kV/mm). Besides these, a relative high dielectric coefficient (ε_r=2030) and a low dielectric loss (tan δ=1.85%) were also obtained on this composition. The degree of diffuse phase transition was enhanced by the addition of Co ions. The related mechanism of the diffused phase transition behavior was discussed.