Etude expérimentale et théorique du mûrissement d'Ostwald dans les systèmes magmatiques (Implications pétrologiques)

CLERMONT FD-BCIU Sci.et Tech. (630142101) / SudocFONTAINEBLEAU-MINES ParisTech (771862302) / SudocRENNES-Géosciences (352382209) / SudocSudocFranceF

Numerical Analysis of Thermal Stress in Semi-Transparent Oxide Crystals Grown by Czochralski and EFG Methods

International audienceCrystal growth of oxides is generally difficult since large curvatures of the growth interface in these systems generate high thermal stress, dislocations and crystal cracking. Three‐dimensional numerical modeling is applied to investigate thermal stress distribution in sapphire and langatate La3Ta0.5Ga5.5O14 (LGT) semi‐transparent crystals grown by Czochralski (Cz) and Edge‐defined Film‐fed Growth (EFG) techniques. The analysis of thermal stress distribution in a sapphire ingot grown in a Czochralski furnace shows high von Mises stresses distributed almost symmetrically on large areas in the crystal. Thermal stress computations for piezoelectric langatate crystals grown in a Czochralski configuration show non‐symmetrical von Mises distribution with higher stress on one side of the ingot. These numerical results are in agreement with experimental results showing non‐symmetrical cracking at the outer surface of the crystal. 3D modeling of multi‐die EFG growth of white sapphire ribbons shows that the von Mises stress is almost constant when the number of ribbons is increased from two to ten. Two models are applied to simulate the internal radiative heat transfer in the sapphire crystals: P1 approximation and the Rosseland radiation model. Numerical results show that applying Rosseland formula introduces significant errors in temperature field calculations especially in the case of the EFG configuration

Color Origins in Langatate Crystals

Langatate La3Ga5.5Ta0.5O14 is piezoelectric crystal from langasite family, commonly grown by Czochralski method from Ir crucible. Langatate crystals of different colors (colorless, orange, green) have been studied by optical spectroscopy in UV-Visible (200 – 800 nm) and IR (7000 – 1000 cm-1) ranges. Furthermore, the effects of irradiation by ultraviolet laser source (λ=266 nm) and post-growth annealing in N2+O2 atmosphere have been investigated. The yellow-orange is mainly due to an absorption centered in the ultraviolet that extends into the blue of the visible spectrum (250-500 nm). The IR optical absorption spectra of Langatate crystals exhibit an absorption band at 5370 cm-1. It seems linked to a point defect responsible for color. The intensity of the absorption band at 3430 cm-1 increases after annealing in oxygen containing atmosphere. We have discussed phenomenon that can occur simultaneously in langatate crystals and produce very similar colors which are related to structural defects. First, metal ions impurities (as Iron, Titanium…), whose presence is previously confirmed by femtosecond laser ablation coupled with ICP-MS spectroscopy, can contribute to langatate color. Second, ultraviolet absorption leads us to think about charge transfer phenomenon such as O2- → Fe3+ and/or Fe3+-Fe3+ pair transitions. Third, the irradiation by ultraviolet (λ=266 nm) laser source locally color the langatate sample by the creation of color centers. Origins of color centers, particularly those related to oxygen vacancies, ( , 2e′)x, are discussed. And, finally, point defects changes the band gap of langatate, leading to extend the absorption to visible light regions

High-Frequency Linear Array (20 MHz) based on Lead-Free BCTZ Crystal

International audienceCentimeter-sized BaTiO 3 -based crystals grown by top-seeded solution growth from the BaTiO 3 –CaTiO 3 –BaZrO 3 system were used to process a high-frequency (HF) lead-free linear array. Piezoelectric plates with (110)pc cut within 1° accuracy were used to manufacture two 1-3 piezo-composites with thicknesses of 270 and 78 μm for resonant frequencies in air of 10 and 30 MHz, respectively. The electromechanical characterization of the BCTZ crystal plates and the 10 MHz piezocomposite yielded thickness coupling factors of 40% and 50%, respectively. We quantified the electromechanical performance of the second piezocomposite (30 MHz) according to the reduction in the pillar sizes during the fabrication process. The dimensions of the piezocomposite at 30 MHz were sufficient for a 128-element array with a 70 μm element pitch and a 1.5 mm elevation aperture. The transducer stack (backing, matching layers, lens and electrical components) was tuned with the characteristics of the lead-free materials to deliver optimal bandwidth and sensitivity. The probe was connected to a real-time HF 128-channel echographic system for acoustic characterization (electroacoustic response, radiation pattern) and to acquire high-resolution in vivo images of human skin. The center frequency of the experimental probe was 20 MHz, and the fractional bandwidth at -6 dB was 41%. Skin images were compared against those obtained with a lead-based 20-MHz commercial imaging probe. Despite significant differences in sensitivity between elements, in vivo images obtained with a BCTZ-based probe convincingly demonstrated the potential of integrating this piezoelectric material in an imaging probe

Numerical modeling of Czochralski growth of Li2MoO4 crystals for heat-scintillation cryogenic bolometers

Lithium molybdate Li2MoO4 (LMO) crystals of mass ranging between 350 and 500 g are excellent candidates to build heat-scintillation cryogenic bolometers likely to be used for the detection of rare events in astroparticle physics. In this work, numerical modeling is applied in order to investigate the Czochralski growth of Li2MoO4 crystals in an inductive furnace. The numerical model was validated by comparing the numerical predictions of the crystal-melt interface shape to experimental visualization of the growth interface. Modeling was performed for two different Czochralski furnaces that use inductive heating. The simulation of the first furnace, which was used to grow Li2MoO4 crystals of 3–4 cm in diameter, reveals non-optimal heat transfer conditions for obtaining good quality crystals. The second furnace, which will be used to grow crystals of 5 cm in diameter, was numerically optimized in order to reduce the temperature gradients in the crystal and to avoid fast crystallization of the bath at the later stages of the growth process

Lead-free piezoelectric crystals grown by the micro-pulling down technique in the BaTiO3–CaTiO3–BaZrO3 system

BaTiO3-based crystal fibres with mm-sized grains were grown by the micro-pulling down technique from the BaTiO3–CaTiO3–BaZrO3 solid solution with pulling velocities of about 6, 9 and 15 mm h−1. The natural growth direction was identified as (001)pc. For the pulling velocities of about 15 mm h−1 and 9 mm h−1, effective partition coefficients have been calculated from Castaing micro-probe measurements, and gave, respectively, 1.3 and 2 for Zr, and 0.95 and 0.9 for Ca. Laser-induced breakdown spectroscopy measurements reveal a strong inhomogeneity and variations of Zr contents while Ca contents show an opposite variation trend with a more steady distribution. Coexistence of two crystallized perovskite solid solutions is suggested. Most efficient polycrystals with mm-sized grains and 0.5 mol% Zr and 11 mol% Ca as average contents exhibit Curie temperatures higher than 113 °C, electromechanical coupling factors kt up to 41% and piezoelectric charge coefficients d33 up to 242 pC N−1 at room temperature. These values are similar to piezoelectric coefficients reported in the literature for oriented flux-grown single crystals with close compositions. Both chemical and physical results obtained in the BCTZ system make the μ-PD technique a promising way to improve the piezoelectric response of lead-free solid solution-based single crystals