Investigation of the thermophysical properties of oxide ceramic materials at liquid-helium temperatures

The main regularities in the transport of thermal phonons in oxide ceramic materials are investigated at liquid-helium temperatures. The dependences of the thermophysical characteristics of ceramic materials on their structural parameters (such as the grain size R, the grain boundary thickness d, and the structure of grain boundaries) are analyzed. It is demonstrated that, in dense coarse-grained ceramic materials with qR?1 (where q is the phonon wave vector), the grain boundaries and the grain size are the main factors responsible for the thermophysical characteristics of the material at liquid-helium temperatures. A comparative analysis of the thermophysical characteristics of optically transparent ceramic materials based on the Y₃Al₅O₁₂ (YAG) and Y₂O₃ cubic oxides synthesized under different technological conditions is performed using the proposed criterion.     

Structure, properties, and formation models of optical ceramics

The structure, properties, and formation mechanisms of Y₃Al₅O₁₂, Y₂O₃, and Lu₂O₃ laser ceramics are investigated. Their microhardness and fracture toughness are determined. It is shown that the change in mechanical properties is related both to the grain size and grain boundary structure. Processes of plastic deformation of crystals by mechanical twinning are considered. Mechanisms of formation and motion of twins in crystals with FCC structure are determined. It is shown that the realization of similar mechanisms in crystals with HCP structure results in the phase transformations. Models of the formation and motion of twin boundaries are proposed which result in pore healing when preparing monolithic samples of highly transparent ceramics.     

Observation of stimulated Raman scattering in Y3Al5O12 single crystals and nanocrystalline ceramics and in these materials activated with laser ions Nd3+ and Yb3+

High-order Raman parametric generation was excited in the visible and near-IR regions on the Stokes and anti-Stokes lines of Y₃Al₅O₁₂ single crystals and nanocrystalline ceramics. All generation components, as well as the χ⁽³⁾-active vibrational modes of these materials, were identified. In connection with the extensive use of the Nd³⁺-and Yb³⁺-doped Y₃Al₅O₁₂ crystals and, in recent years, nanocrystalline Y₃Al₅O₁₂: Nd³⁺ ceramics in laser physics and quantum electronics, the applied aspect of the observed nonlinear properties of these materials is outlined.     

Nonequilibrium acoustic phonons in Y3Al5O12-based nanocrystalline ceramics

The phonon transport processes in high-transparency nanocrystalline laser ceramics based on cubic Y₃Al₅O₁₂ garnet oxide were investigated by the heat-pulse technique. The propagation kinetics of nonequilibrium acoustic phonons was studied in the range of helium temperatures (1.7–3.8 K). The structural model is suggested for the intergrain layers, and their thickness is estimated.     

XPS and ionic conductivity studies on Li1.3Al0.15Y0.15Ti1.7(PO4)3 ceramics

Li_1.3Al_0.15Y_0.15Ti_1.7(PO₄)₃ compound was synthesized by solid-state reaction, and ceramics were sintered. The surfaces of the ceramics were investigated by scanning electron microscopy and X-ray photoelectron spectroscopy. Li_1.3Al_0.15Y_0.15Ti_1.7(PO₄)₃ samples were tested in solid galvanic cells Ag|O₂+CO₂|Li₂CO₃|Li_1.3Al_0.15Y_0.15Ti_1.7(PO₄)₃|LiMnO₂+Mn₂O₃|O₂|Ag. The electromotive force measurements of this cell indicated that investigated samples are practically pure Li-ion conductors. Impedance spectroscopy studies have been performed in the frequency range 10^?2–3·10⁹ Hz and temperatures from ?57 °C to 334 °C. Three dispersion regions related to Li⁺ ionic transport in bulk, grain boundaries of the ceramics and to polarization of electrodes have been found. Total conductivity changes according to Arrhenius law in the studied temperature range, but an anomalous behavior was observed for the bulk conductivity of the ceramics.     

Comparative spectroscopic investigation of Yb3x Y3(1 ? x )Al5O12 (x = 3, 5, 10 and 15%) transparent ceramics

Transparent Yb_3x Y_{3(1 ? x} )Al₅O₁₂ (x = 3, 5, 10 and 15%) ceramics were fabricated by solid-state reaction and vacuum sintering method with a mixture of commercial Al₂O₃, Y₂O₃ and Yb₂O₃ powders. Ethanol and 0.5 wt % tetraethoxysilane were doped. Transparent fully dense samples with grain sizes of several micrometers were obtained by sintered at 1750 K. The absorption spectra, emission spectra and fluorescence life time of these transparent Yb_3x Y_{3(1 ? x} )Al₅O₁₂ ceramics at room temperature have been measured and calculated. The air annealed effects of Yb_3x Y_{3(1 ? x} )Al₅O₁₂ ceramics have been compared with un-annealed Yb:YAG transparent ceramics which shows the difference of the Yb³⁺ ions between annealed and unannealed Yb:YAG ceramics is less than 1%.     

Magneto-transport and ferromagnetic resonance studies of polycrystalline La0.6Pb0.4MnO3 thin films

To understand the nature of grain boundaries in polycrystalline materials, magneto-transport and ferromagnetic resonance measurement have been performed in polycrystalline La_0.6Pb_0.4MnO₃ (LPMO) thin films prepared by pulsed laser deposition. Films are found to undergo a semiconductor to metal transition at 230 K and re-enter into the semiconducting state below 130 K. Microwave absorption measurements carried out as function of applied field show two components of resonant absorption signal. First component is in accordance with ferromagnetic transition of grains at Curie temperature and the second component shows antiferromagnetic transition of grain boundaries at 160 K. An additional non-resonant absorption signal centered at zero field has also been observed that supports transition from conducting to insulating grain boundaries at ∼160 K. Further, temperature dependence of resistance in semiconducting state at low temperatures is in accordance with coulomb blockade model indicating insulating nature of AFM grain boundaries.     

Resonant scattering of nonequilibrium phonons (<Emphasis Type="Italic">λ</Emphasis><Subscript>ph</Subscript> = 10–50 nm) in nanostructured ceramics based on YSZ + Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composites

Specific features of the transport of weakly nonequilibrium thermal phonons (λ _ph = 10–50 nm) in nanoscale ceramics at a transition from micro-to nanosizes have been investigated. On the basis of the model of spherical shells randomly distributed in space and modeling grain boundaries, whose elastic properties differ from the elastic properties of grains, features of the phonon spectrum in the wavelength range λ _ph ～ R _g have been studied. The conditions leading to the occurrence of a gap in the phonon spectrum of nanoscale materials are analyzed. It is shown that the position of the top gap edge in the phonon spectrum is determined to a large extent by the structure of phase boundaries, while the presence of inclusions (pores, other phases) with characteristic sizes smaller than that of grains of the main ceramic material shifts the gap to high frequencies in the phonon spectrum. Temperature dependences of the diffusion coefficient of nonequilibrium phonons near the top gap edge in the phonon spectrum have been measured for multiphase ceramics based on YSZ + 14.3% Al₂O₃ composites.     

Cr3+:Al2O3透明多晶陶瓷光谱特性分析

对透光性良好的Cr³⁺:Al₂O₃透明多晶陶瓷的光谱性能 进行了研究，其吸收光谱中吸收峰与单晶红宝石相一致，按吸收光谱和Tanabe-Sugano能级 图，算出其晶场强度参数D_q及Racah参数B分别为1792cm^-1， 689cm ^-1，D_q/B=2.6，陶瓷中Cr³⁺离子所处格位的晶体场强 比单晶弱一些，但Cr³⁺:Al₂O₃透明陶瓷仍属于强场晶 体材料；当Cr³⁺掺杂浓度到达0.8wt%时，陶瓷的发射谱仍保持较好的R线发射 ；随Cr³⁺掺杂浓度的增大，激发峰位发生“红移”.在Cr³⁺:Al₂O₃透明多晶陶瓷的荧光谱上，发现一个波长为670nm的发射峰，经激发 谱确认为Cr³⁺的发射峰. 关键词： 氧化铝 透明陶瓷 离子格位 光谱性质     

Phonon kinetics in solid solutions of ceramics in the ZrO2-Y2O3-MgO-Al2O3 system

The propagation of weakly nonequilibrium phonons is studied in ceramics based on ZrO₂-Y₂O₃-MgO-Al₂O₃. Under the assumption of a large dispersion in the ceramic grain sizes, the characteristics of phonon scattering are studied as a function of the temperature and duration of isothermal annealing of the samples and the contribution of the intergrain boundaries to the phonon kinetics is isolated. Fiz. Tverd. Tela (St. Petersburg) 39, 1091–1093 (June 1997)     

Andreev reflection and experimental temperature dependences of the critical current in heterogeneous high-temperature superconductors (polycrystals and related composites)

The temperature dependences of the critical current of Y_3/4Lu_1/4Ba₂Cu₃O₇ polycrystalline high-temperature superconductors subjected to annealing for different times and those of Y_3/4Lu_1/4Ba₂Cu₃O₇ + BaPbO₃ composites were measured. The results obtained were analyzed in terms of the Gunsenheimer-Schüssler-Kümmler theory considering the Andreev reflection of carriers in a “superconductor-normal metal-superconductor” (S-N-S) junction. Good agreement between the experimental and theoretical temperature dependences of the critical current over a wide temperature range for polycrystals with both natural and artificially created boundaries (composites) made it possible to estimate the effective length of grain boundaries in the high-temperature superconductors. It was revealed that the critical current density measured at 4.2 K is an exponential function of the length of grain boundaries in samples of both types.     

Passive mode-locking of a diode-pumped Tm:GdLiF4 laser

We propose an optical near-field assisted sputtering method for repairing scratches on the surface of polycrystalline ceramics in a self-assembling manner. An Al₂O₃ source was sputtered on substrates with laser radiation of wavelength 473 nm. The average depth of the scratched grooves on polycrystalline Al₂O₃ ceramic substrate decreased from 3.2 nm to 0.79 nm. Using a Hough transform, we also confirmed the selective repair of scratches.     

Al2O3-Y2O3-ZrO2三相复合陶瓷的介电谱研究

采用传统的固相反应法,在1400–1500 ℃下烧结,制备得到Al₂O₃-Y₂O₃-ZrO₂三相复合陶瓷.样品的结构、形貌和电性能分别用X射线衍射(XRD)、扫描电子显微镜(SEM)及介电谱表征.XRD表明此三相复合体系无其他杂相,加入Y₂O₃及ZrO₂后使得Al₂O₃成瓷温度降低;SEM表明此体系晶粒直径为200–500 nm,并且样品随烧结温度的升高而变得更加致密,晶界更加清晰;介电损耗谱中出现峰值弛豫现象,根据Cole-Cole复阻抗谱得出其为非德拜弛豫. 关键词： 2O₃-Y₂O₃-ZrO₂三相陶瓷')" href="#">Al₂O₃-Y₂O₃-ZrO₂三相陶瓷 介电弛豫 阻抗谱 热导率     

Mechanism of grain-boundary magnetoresistance in Fe O films

The magnetotransport properties of magnetite films with different microstructures were investigated in order to identify prerequisites for the attainment of a large tunnelling magnetoresistance in polycrystalline samples. Epitaxial films on MgAl₂O₄, polycrystalline films on Al₂O₃ and rough MgAl₂O₄ substrates and a polycrystalline La_0.7Ca_0.3MnO₃ film on MgO were compared. Although grain boundaries induce a large high-field magnetoresistance in magnetite films, the low-field magnetoresistance characteristic for spin-polarized tunnelling was virtually absent in these samples. Two factors might be responsible for this behaviour: (1) grain boundaries in magnetite are conducting and do not form tunnelling barriers and (2) the spin-polarization near grain boundaries is suppressed due to non-stoichiometry. Received 15 April 2002 Published online 13 August 2002     

Laser ceramics: Mechanisms of solid-state reactions

The role of twinning in synthesizing Y₃Al₅O₁₂ from Al₂O₃ and Y₂O₃ powders during milling and compacting is shown by the example of obtaining laser ceramics based on yttrium-aluminum garnet. Simulation of twins in aluminum and yttrium oxides revealed the possibility of forming fragments of the garnet structure near the twin boundary. It is concluded that process of solid-state reactions is mainly associated with twinning, which leads to local variation in the symmetry and/or phase transitions.     

Comparison of Segregation Behaviors for Special and General Boundaries in Polycrystalline Al2O3 with SiO2-TiO2 Impurities

A systematic study of grain boundaries with an elongated grain morphology in TiO₂-doped polycrystalline Al₂O₃ materials with SiO₂ impurities is reported in this paper. Over 20 grain boundaries, all having common (0001) basal plane surface on one side, were investigated by using HRTEM and analytical TEM. A few of them were basal plane twin boundaries or other non-wetting boundaries, and the majority of grain boundaries were covered by amorphous phases, either as continuous films or with small pockets bounded by surface facets. Si and Ti were segregated to all boundaries, however, two categories of segregation were observed. Excesses of both segregants were between 1.0–4.0 atom/nm² at special and non-wetting boundaries, while they were in the range of 7.0–30 atom/nm² at boundaries with amorphous phases. A variation of amorphous film thickness was also observed, which has a clear relation with Si excess level while Ti excess remained at the same level. This observation suggests that the amorphous phases were primarily made of SiO₂ but Ti segregants were attached to grain surfaces. The variation in thickness of SiO₂-based film is strongly related to the surface structure of anisotropic Al₂O₃ grains.     

Specific heat and velocity of sound in a moderate heavy-fermion compound YbZnCu4

The specific heat at a constant pressure (C _p) and the velocity of sound (v) are measured for a moderate heavy-fermion compound YbZnCu₄ in the temperature range 3.5–250 K and at 77 K, respectively. The experimental values of C _p and v obtained in this study and the phonon thermal conductivity previously measured in the temperature range 5–300 K are used to calculate the phonon mean free path l for this compound. The temperature dependence of the phonon mean free path l thus determined is characteristic of classical amorphous materials.     

Fabrication of low-loss channel waveguides in Al2O3 and Y2O3 layers by inductively coupled plasma reactive ion etching

Etching of amorphous Al₂O₃ and polycrystalline Y₂O₃ films has been investigated using an inductively coupled reactive ion etch system. The etch behaviour has been studied by applying various common process gases and combinations of these gases, including CF₄/O₂, BCl₃, BCl₃/HBr, Cl₂, Cl₂/Ar and Ar. The observed etch rates of Al₂O₃ films were much higher than Y₂O₃ for all process gases except for Ar, indicating a much stronger chemical etching component for the Al₂O₃ layers. Based on analysis of the film etch rates and an investigation of the selectivity and patterning feasibility of possible mask materials, optimized optical channel-waveguide structures were fabricated in both materials. In Al₂O₃, channel waveguides were fabricated with BCl₃/HBr plasma and using a standard resist mask, while in Y₂O₃, channel waveguides were fabricated with Ar and using either a resist or a sputter deposited Al₂O₃ mask layer. The etched structures in both materials exhibit straight sidewalls with minimal roughness and sufficient etch depths (up to 530 nm for Al₂O₃ and 250 nm for Y₂O₃) for defining waveguides with strong optical confinement. Using the developed etch processes, low additional optical propagation losses (on the order of 0.1 dB/cm) were demonstrated in single-mode ridge waveguides in both Al₂O₃ and Y₂O₃ layers at 1550 nm. PACS 42.70.-a; 42.82.-m; 42.82.Cr     

Influence of the size effect on the electrical conductivity of partially stabilized zirconia

The volume component of the electrical conductivity of bulk ceramics of the partially stabilized zirconia (ZrO₂)_0.94(Y₂O₃)_0.05(Al₂O₃)_0.01 is found to increase by a factor of 1.7 with the grain size decreasing from 600–800 to 200–300 nm. The observed effect is explained by the action of the pressure produced by surface tension forces, which shifts equilibrium toward the point of the polymorphic transition to the cubic phase.     

Preparation and characterization of transparent Nd:YAG ceramics

Transparent Nd:YAG ceramics were produced by solid.state reaction of high.purity (4N) nanometric oxides powders, i.e., Al₂O₃, Y₂O₃ and Nd₂O₃. After sintering, mean grain sizes of 2% Nd:YAG samples were about 20 μm and their transparency were a bit worse than that of 0.9% Nd:YAG single crystal. Two types of active elements: rods and slabs were fabricated and characterized in several diode pumping schemes. In end pumping configuration as a pump source 20.W fiber coupled laser diode operating in low duty cycle regime (1 ms pump duration/20 Hz) was deployed. In the best case, 3.7 W of output power for 18 W of absorbed pump power, M² < 1.4 were demonstrated for uncoated ceramics Nd:YAG rod of ϕ 4×3mm size in preliminary experiments. For the ceramics of two times lower Nd dopant level above 30% slope efficiency was achieved. In case of Nd:YAG ceramic slab side pumped by 600.W laser diode stack above 12 W was demonstrated with slope efficiency of 3.5%.