Structural Investigations on the Compositional Anomalies in Lanthanum Zirconate System Synthesized by Coprecipitation Method

The study set out to investigate the compositional inconsistency in lanthanum zirconate system revealed the presence of nonstoichiometry in lanthanum zirconate powders when synthesized by coprecipitation route. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) investigations confirmed the depletion of La3+ ions in the system. Analysis using Vegard's law showed the La/Zr mole ratio in the sample to be around 0.45. An extra step of ultrasonication, introduced during the washing stage followed by the coprecipitation reaction, ensured the formation of stoichiometric La2Zr2O7. Noteworthy is also the difference between crystal sizes in the samples prepared by with and without ultrasonication step. This difference has been explained in light of the formation of individual nuclei and their scope of growth within the precipitate core. The differential scanning calorimetry (DSC) analyses revealed that optimum pH for the synthesis of La2Zr2O7 is about 11. The ultrasonication step was pivotal in assuring consistency in mixing and composition for the lanthanum zirconate powders.

Thickness of the near-interface regions and central bulk ohmic resistivity in lead lanthanum zirconate titanate ferroelectric thin films

Thickness of the near-interface regions (NIR) and central bulk ohmic resistivity in lead lanthanum zirconate titanate ferroelectric thin films were investigated. A method to separate the low-resistive near-interface regions (NIRs) from the high-resistive central bulk region (CBR) in ferroelectric thin films was presented. Results showed that the thickness of the NIRs depended on the electrode materials in use and the CBR resistivity depended on the impurity doping levels.

Lanthanum zirconate ceramic toughened by BaTiO3 secondary phase

La2Zr2O7 (LZ) is a promising thermal barrier coating material for the high-temperature applications, which could be significantly toughened by the BaTiO3 piezoelectric phase incorporated into the matrix. The composites of xBaTiO(3)/(l-x)LZ (x=5, 10, 15, 20 vol%, LZ-x-BaTiO3) were densified by means of high-pressure sintering (HPS) under a pressure of 4.5 GPa at 1450 degrees C for 10 min, by which a high relative density above 93% could be obtained.

Effects of deposition conditions on composition and thermal cycling life of lanthanum zirconate coatings

Lanthanum, zirconate (La2Zr2O7, LZ) coatings were prepared under four different deposition conditions by electron beam-physical vapor deposition (EB-PVD). The composition, crystal structure, surface and cross-sectional morphology, cyclic oxidation behavior of these coatings were studied. Elemental analysis indicates that the coating composition has partially deviated from the stoichiometry of pyrochlore, and the existence of excess La2O3 is also observed. The deviation could be reduced by properly controlling the electron beam current or by changing the ingot composition.

Effects of Y2O3 addition on the phase evolution and thermophysical properties of lanthanum zirconate

Lanthanum zirconate (La2Zr2O7, LZ) powders with the addition of various Y2O3 contents for potential thermal barrier coatings (TBCs) application were synthesized by solid-state reaction. The structure evolution, sintering-resistance and thermophysical properties of the synthesized powders and sintered ceramics were systematically studied. X-ray diffraction (XRD) results indicate that LZ containing 3-12 wt.% Y2O3 mainly keeps a pyrochlore-type structure, and two new phases of LaYO3 and Y0.18Zr0.82O1.91 are also detected. Raman spectra confirm that the higher the Y2O3 content, the easier is the formation of LaYO3.

Effect of the addition of YAG(Y3Al5O12) nanopowder on the mechanical properties of lanthanum zirconate

La2Zr2O7 (LZ) is a promising thermal barrier coating material for the high-temperature applications, which could be significantly toughened by the YAG nanopowder incorporated into the matrix. The composites of xYAG/(1-x)LZ (Y=10, 15, 20 vol. %, LZ-x-YAG) were densified by means of high-pressure sintering (HPS) under a pressure of 4.5 GPa at 1650 degrees C for 5 min, by which a high-relative density above 93% could be obtained. The morphologies of the fractured surfaces were investigated by the scanning electron microscope, and the fracture toughness and Vicker's-hardness of the composites were evaluated by the microindentation. The grain size of the LZ matrix drops significantly with the addition of YAG nanoparticles and the fracture type changes from the intergranular to a mixture type of the transgranular and intergranular in the nanocomposites. The LZ-20-YAG nanocomposite has a fracture toughness of 1.93 MPa m(1/2), which is obviously higher than that of the pure LZ (1.57 MPa m(1/2)), and the toughening mechanism is discussed in this paper.

Lanthanum zirconate nanofibers with high sintering-resistance

The PVP/lanthanum nitrate/zirconium oxychloride (PVP-precursor) nanofiber was prepared by electrospinning technique. Lanthanum zirconate (La2Zr2O7, LZ) in the nanofiber is formed after calcination at 800 degrees C and the nanofiber with pyrochlore structure and a diameter of 100-500 nm can be obtained by calcination of the above precursor fiber at 1000 degrees C for 12 h. The surface of the fiber is rough but the continuous microstructure is still maintained after calcination. LZ fibers stack randomly, resulting in a structure with a low contact area between the fibers. This special structure makes the fiber to have a high resistance to sintering at elevated temperatures. The BET (Brunauer-Emmett-Teller) specific surface areas of the LZ fiber and powder calcined at different temperatures are shown in this paper, and the fiber was characterized by TG-DTA (thermal gravimetry-differential thermal analysis), XRD (X-ray diffraction), N-2 absorption-desorption porosimetry and SEM (scanning electron microscopy).

Preparation and structural characterization of rare-earth doped lead lanthanum zirconate titanate ceramics

A new preparation route towards rare-earth (RE) doped polycrystalline lead lanthanum zirconate titanate (PLZT) ceramics (RE = Y(3+), Nd(3+), Yb(3+)), based on the use of doped lanthanum oxide or zirconia, is reported. Structural characterization by X-ray powder diffraction reveals that secondary phase formation can be substantially diminished in comparison to conventional preparation methods. The distribution of the rare-earth dopants was investigated as a function of concentration by static (207)Pb spin echo NMR spectra, using Fourier Transformation of Carr-Purcell-Meiboom-Gill spin echo trains. For the Nd- and Yb-doped materials, the interaction of the (207)Pb nuclei with the unpaired electron spin density results in significant broadening and shifting of the NMR signal, whereas these effects are absent in the diamagnetic Y(3+) doped materials. Based on different concentration dependences of the NMR lineshape parameters, we conclude that the structural role of the Nd(3+) dopants differs significantly from that of Yb(3+). While the Nd(3+) ions appear to be statistically distributed in the PLZT lattice, incorporation of Yb(3+) into PLZT appears to be limited by the appearance of doped cubic zirconia as a secondary phase. (C) 2009 Elsevier Masson SAS. All rights reserved.

Solid state NMR as a new approach for the structural characterization of rare-earth doped lead lanthanum zirconate titanate laser ceramics

To facilitate the design of laser host materials with optimized emission properties, detailed structural information at the atomic level is essential, regarding the local bonding environment of the active ions (distribution over distinct lattice sites) and their extent of local clustering as well as their population distribution over separate micro- or nanophases. The present study explores the potential of solid state NMR spectroscopy to provide such understanding for rare-earth doped lead lanthanum zirconate titanate (PLZT) ceramics. As the NMR signals of the paramagnetic dopant species cannot be observed directly, two complementary approaches are utilized: (1) direct observation of diamagnetic mimics using Sc-45 NMR and (2) study of the paramagnetic interaction of the constituent host lattice nuclei with the rare-earth dopant, using Pb-207 NMR lineshape analysis. Sc-45 MAS NMR spectra of scandium-doped PLZT samples unambiguously reveal scandium to be six-coordinated, suggesting that this rare-earth ion substitutes in the B site. Static Pb-207 spin echo NMR spectra of a series of Tm-doped PLZT samples reveal a clear influence of paramagnetic rare-earth dopant concentration on the NMR lineshape. In the latter case high-fidelity spectra can be obtained by spin echo mapping under systematic incrementation of the excitation frequency, benefiting from the signal-to-noise enhancement afforded by spin echo train Fourier transforms. Consistent with XRD data, the Pb-207 NMR lineshape analysis suggests that statistical incorporation into the PLZT lattice occurs at dopant levels of up to 1 wt.% Tm3+, while at higher levels the solubility limit is reached. (C) 2008 Elsevier Masson SAS. All rights reserved.

Processing and structural properties of random oriented lead lanthanum zirconate titanate thin films

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Methods for melting temperature calculation

Melting temperature calculation has important applications in the theoretical study of phase diagrams and computational materials screenings. In this thesis, we present two new methods, i.e., the improved Widom's particle insertion method and the small-cell coexistence method, which we developed in order to capture melting temperatures both accurately and quickly.

We propose a scheme that drastically improves the efficiency of Widom's particle insertion method by efficiently sampling cavities while calculating the integrals providing the chemical potentials of a physical system. This idea enables us to calculate chemical potentials of liquids directly from first-principles without the help of any reference system, which is necessary in the commonly used thermodynamic integration method. As an example, we apply our scheme, combined with the density functional formalism, to the calculation of the chemical potential of liquid copper. The calculated chemical potential is further used to locate the melting temperature. The calculated results closely agree with experiments.

We propose the small-cell coexistence method based on the statistical analysis of small-size coexistence MD simulations. It eliminates the risk of a metastable superheated solid in the fast-heating method, while also significantly reducing the computer cost relative to the traditional large-scale coexistence method. Using empirical potentials, we validate the method and systematically study the finite-size effect on the calculated melting points. The method converges to the exact result in the limit of a large system size. An accuracy within 100 K in melting temperature is usually achieved when the simulation contains more than 100 atoms. DFT examples of Tantalum, high-pressure Sodium, and ionic material NaCl are shown to demonstrate the accuracy and flexibility of the method in its practical applications. The method serves as a promising approach for large-scale automated material screening in which the melting temperature is a design criterion.

We present in detail two examples of refractory materials. First, we demonstrate how key material properties that provide guidance in the design of refractory materials can be accurately determined via ab initio thermodynamic calculations in conjunction with experimental techniques based on synchrotron X-ray diffraction and thermal analysis under laser-heated aerodynamic levitation. The properties considered include melting point, heat of fusion, heat capacity, thermal expansion coefficients, thermal stability, and sublattice disordering, as illustrated in a motivating example of lanthanum zirconate (La₂Zr₂O₇). The close agreement with experiment in the known but structurally complex compound La₂Zr₂O₇ provides good indication that the computation methods described can be used within a computational screening framework to identify novel refractory materials. Second, we report an extensive investigation into the melting temperatures of the Hf-C and Hf-Ta-C systems using ab initio calculations. With melting points above 4000 K, hafnium carbide (HfC) and tantalum carbide (TaC) are among the most refractory binary compounds known to date. Their mixture, with a general formula Ta_xHf_1-xC_y, is known to have a melting point of 4215 K at the composition Ta₄HfC₅, which has long been considered as the highest melting temperature for any solid. Very few measurements of melting point in tantalum and hafnium carbides have been documented, because of the obvious experimental difficulties at extreme temperatures. The investigation lets us identify three major chemical factors that contribute to the high melting temperatures. Based on these three factors, we propose and explore a new class of materials, which, according to our ab initio calculations, may possess even higher melting temperatures than Ta-Hf-C. This example also demonstrates the feasibility of materials screening and discovery via ab initio calculations for the optimization of "higher-level" properties whose determination requires extensive sampling of atomic configuration space.

基于PLZT的电光偏转器的特性研究

采用具有高二次电光效应的掺镧锆钛酸铅陶瓷材料（PLZT），设计和制备了一种基于折射率随外加电压发生变化的电光偏转器。构建了测试系统，测得PLZT的电光系数是R33=2.1

基于掺镧锆钛酸铅电光材料的光学相控阵光束扫描器

基于掺镧锆钛酸铅(PLZT)电光陶瓷材料的光学特性,提出了一种具有上下电极结构的光学相控阵高速光束扫描器。在理论上,分析了具有这种结构的光学相控阵的光束电光偏转特性和机制;在实验上,分析了掺镧锆钛酸铅材料的相位调制特性和损耗特性,制作了相关的光学相控阵器件,并构建了相应的测试系统,获得了光束在空间的角度偏转,与理论分析结果相符。

基于电光材料的光学相控阵技术研究进展

综述了基于电光材料的光学相控阵(OPA)的研究进展。介绍了光学相控阵技术的基本原理以及不同电光材料(铌酸锂电光晶体,AlGaAs光波导,液晶和掺镧锆钛酸铅(PLZT)电光陶瓷)光学相控阵技术的基本构想和涉及的关键技术;着重介绍近年来基于PLZT电光陶瓷材料光学相控阵技术的发展情况以及在这方面的最新研究成果,包括单级相控阵、级联相控阵、不同电极结构(表面电极和上下电极结构)相控阵技术等;最后简要介绍了光学相控阵技术在激光雷达等军事领域中的应用。

Influence of the deposition energy on the composition and thermal cycling behavior of La-2(Zr0.7Ce0.3)(2)O-7 coatings

Lanthanum-zirconium-cerium composite oxide (La-2(Zr0.7Ce0.3)(2)O-7, LZ7C3) coatings were prepared under different conditions by electron beam-physical vapor deposition (EB-PVD). The composition, crystal structure, surface and cross-sectional morphologies, cyclic oxidation behavior of these coatings were studied. Elemental analysis indicates that the coating composition has partially deviated from the stoichiometry of the ingot, and the existence of excess La2O3 is also observed.