The role of Si impurities in the transient dopant segregation and precipitation in yttrium-doped alumina

Y-doped alumina was sintered at 1500 degrees C for 10 h under ultra-clean experimental conditions without experiencing any abnormal grain growth. The yttrium was fairly homogeneously distributed at the grain boundaries, with a mean value of (Gamma) over bar (Y) = 5.5 at nm(-2). The Y-Al-O precipitates in the clean, Y2O3-doped alumina specimen were the YAP (YAlO3) phase, whereas only the YAG (Y3Al5O12) phase was present in the Y2O3-doped alumina samples contaminated with SiO2. The excess concentrations of Y and Si atoms at the grain boundaries that, at the same time, provoke the formation of structurally complex YAG precipitates and abnormal grain growth were both estimated to be at 4-5 at nm(-2). The compositions of the triple point pocket phases found in the region of the exaggeratedly grown alumina grains indicate the presence of alumino-silicate bulk liquids at the sintering temperature

TEM and STEM investigations of Sr(Ti,Nb)O3-δ thermoelectric with the addition of CaO and SrO

It is known that thermoelectric properties, i.e. figure of merit ZT of oxide-based polycrystalline thermoelectric materials can be improved by introducing planar faults into the microstructure of these materials. It is assumed that in-grown planar faults will reduce thermal conductivity without reducing electrical properties which would consequently increase the ZT value. In order to successfully tailor thermoelectric properties of chosen thermoelectric materials, it is prerequisite to know the structure and chemical composition of introduced planar faults. This is why we used HR TEM and HAADF STEM imaging with EDXS in order to study structure and chemical composition of the Ruddlesden-Popper-type (RP) planar faults1,2 in Sr(Ti,Nb)O3-d (STNO) thermoelectric material with the addition of SrO and/or CaO. All results were obtained in a Jeol ARM-200F with a CFEG and Cs probe corrector. HAADF imaging was performed at angles from 70 to 175 mrad (ADF from 42 to 168 mrad). EDX spectra were acquired using JEOL Centurio Dry SD100GV SDD Detector. TEM bright-field images of pure STNO showed that the STNO solid solution grains contained no planar faults of any kind. Furthermore, the interfaces between the grains were clean with no observable interface phase. However, when SrO and/or CaO were added to the STNO, various nanostructured features were observed. In SrO-doped STNO, one can observe three distinctly different regions, i.e. the STNO solid solution, the regions with ordered SrO faults and the region with a network of random SrO planar faults (Figure 1). In the ordered regions one SrO layer is always followed by two perovskite STNO blocks, which corresponds to the Sr3(Ti1-xNbx)2O7 RP-type phase in which Nb and Ti occupy the same crystallographic site. While the measured HAADF intensities across Sr atomic columns at the RP fault do not scatter significantly, the mixed (Ti1-xNbx)O6 atom columns on the other hand exhibit significant differences in measured intensities thus indicating variation in Nb and Ti content within a single mixed atom column (Figure 2). Semi-quantitative HAADF STEM of the perovskite matrix, i.e. the comparison of measured integrated intensities of the atom columns with the calculated intensities showed that that the Nb content on the Ti sites within the perovskite structure varied from app. X=0.05 to X=0.35 (from Sr(Ti0.95Nb0.05)O3-d to Sr(Ti0.65Nb0.35)O3-d). When RP-type planar faults are isolated they run parallel to the {001} low-index zone axes of the perovskite structure. A similar structural phenomenon was observed in STNO with excess of CaO. Again, ordered and/or random 3D networks of RP-type planar faults were observed in the STNO grains (Figure 3). In very thin regions of CaO-doped STNO specimen many orthogonal loops of RP faults were observed that were not detected in SrO doped STNO (Figure 4). The EDX analysis from a single fault and from the matrix showed higher concentration of Ca at the fault. This is in agreement with previously reported investigations3 since smaller Ca ions are easier incorporated at the RP fault than in the perovskite matrix. The TEM and STEM investigations thus confirmed that the addition of SrO and/or CaO to the STNO perovskite solid solution is structurally compensated via the formation of RP-type planar faults within the STNO grains. Finally, thermoelectric measurements confirmed that the existence of RP-type faults in the perovskite STNO matrix reduced the thermal conductivity of this oxide thermoelectric material

Determination of structure and chemistry of long-persistence strontium aluminate phosphor compounds in aberration-corrected tem/stem

Representing a source of short-term stored energy, strontium aluminate phosphor compounds of nominal stoichiometry (SrO)•(Al2O3)2 co-doped with 1 mol% Eu2+ and 1 mol% Dy3+ (SA2ED) exhibit long persistence that is even further extended by the incorporation of boron1. To elucidate the effect of boron on afterglow persistence, we synthesized the phosphor powders using a sol-gel (i.e., modified Pechini) method2 and investigated the chemistry and structure by applying high-resolution STEM imaging, energy dispersive X-ray (EDX) spectroscopy, and electron energy-loss spectroscopy (EELS). Large single-crystal grains were analyzed from as-reduced powders suspended on carbon-coated lacey formvar on copper support grids. Individual crystalline particles were tilted onto a low-index [0001] zone axis and imaged in both high resolution TEM and STEM, using a JEOL JEM-ARM 200CF, equipped with a cold field-emission tip and a probe-side Cs aberration corrector. High-angle annular dark-field (HAADF) images were formed using an annular detector with an inner diameter of 70 mrad and an outer diameter of 175 mrad, while annular bright-field (ABF) images were obtained from an annular detector of 11-mrad inner diameter and 23-mrad outer diameter. EDX spectra were collected using a JEOL Centurio Dry SD100GV SDD detector. EELS analysis was enabled by a Gatan GIF Quantum ER spectrometer. Rietveld refinement of XRD spectra obtained from the powders revealed a mixture of (SrO)4•(Al2O3)7, (SrO)•(Al2O3)2 , and (SrO)•(Al2O3)6 phases. Single crystal particles of the (SrO)•(Al2O3)6 phase were the most stable and allowed for tilting onto the [0001] zone axis for qualitative identification of the atomic columns in HAADF and ABF micrographs. Quantitative image simulations of the measured intensities are in progress. Local variations were observed in the energy loss near-edge fine structure of the B-K, O-K, Al-L2,3 edges

Coercivity increase of the recycled HDDR Nd-Fe-B powders doped with DyF3 and processed via Spark Plasma Sintering & the effect of thermal treatments

The magnetic properties of the recycled hydrogenation disproportionation desorption recombination (HDDR) Nd-Fe-B powder, doped with a low weight fraction of DyF3 nanoparticles, were investigated. Spark plasma sintering (SPS) was used to consolidate the recycled Nd-Fe-B powder blends containing 1, 2, and 5 wt.% of DyF3 grounded powder. Different post-SPS sintering thermal treatment conditions (600, 750, and 900 °C), for a varying amount of time, were studied in view of optimizing the magnetic properties and developing characteristic core-shell microstructure in the HDDR powder. As received, recycled HDDR powder has coercivity (HCi) of 830 kA/m, and as optimally as SPS magnets reach 1160 kA/m, after the thermal treatment. With only 1−2 wt.% blended DyF3, the HCi peaked to 1407 kA/m with the thermal treatment at 750 °C for 1 h. The obtained HCi values of the blend magnet is ~69.5% higher than the starting recycled HDDR powder and 17.5% higher than the SPS processed magnet annealed at 750 °C for 1 h. Prolonging the thermal treatment time to 6 h and temperature conditions above 900 °C was detrimental to the magnetic properties. About ~2 wt.% DyF3 dopant was suitable to develop a uniform core-shell microstructure in the HDDR Nd-Fe-B powder. The Nd-rich phase in the HDDR powder has a slightly different and fluorine rich composition i.e., Nd-O-F2 than in the one reported in sintered magnets (Nd-O-F). The composition of reaction zone-phases after the thermal treatment and Dy diffusion was DyF4, which is more abundant in 5 wt.% doped samples. Further doping above 2 wt.% DyF3 is ineffective in augmenting the coercivity of the recycled HDDR powder, due to the decomposition of the shell structure and formation of non-ferromagnetic rare earth-based complex intermetallic compounds. The DyF3 doping is a very effective single step route in a controlled coercivity improvement of the recycled HDDR Nd-Fe-B powder from the end of life magnetic products