Structural Transitions in Nanosized Zn0.97Al0.03O Powders under High Pressure Analyzed by in Situ Angle-Dispersive X-ray Diffraction.
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ABSTRACT: Nanosized aluminum-doped zinc oxide Zn1-xAlxO (AZO) powders (AZO-NPs) with x = 0.01, 0.03, 0.06, 0.09 and 0.11 were synthesized by chemical precipitation method. The thermogravimetric analysis (TGA) indicated that the precursors were converted to oxides from hydroxides near 250 °C, which were then heated to 500 °C for subsequent thermal processes to obtain preliminary powders. The obtained preliminary powders were then calcined at 500 °C for three hours. The structure and morphology of the products were measured and characterized by angle-dispersive X-ray diffraction (ADXRD) and scanning electron microscopy (SEM). ADXRD results showed that AZO-NPs with Al content less than 11% exhibited würtzite zinc oxide structure and there was no other impurity phase in the AZO-NPs, suggesting substitutional doping of Al on Zn sites. The Zn0.97Al0.03O powders (A₃ZO-NPs) with grain size of about 21.4 nm were used for high-pressure measurements. The in situ ADXRD measurements revealed that, for loading run, the pressure-induced würtzite (B4)-to-rocksalt (B1) structural phase transition began at 9.0(1) GPa. Compared to the predicted phase-transition pressure of ~12.7 GPa for pristine ZnO nanocrystals of similar grain size (~21.4 nm), the transition pressure for the present A₃ZO-NPs exhibited a reduction of ~3.7 GPa. The significant reduction in phase-transition pressure is attributed to the effects of highly selective site occupation, namely Zn2+ and Al3+, were mainly found in tetrahedral and octahedral sites, respectively.
Project description:This article reports on energy-dispersive micro Laue (µLaue) diffraction of an individual gold nanowire that was mechanically deformed in three-point bending geometry using an atomic force microscope. The nanowire deformation was investigated by scanning the focused polychromatic X-ray beam along the nanowire and recording µLaue diffraction patterns using an energy-sensitive pnCCD detector that permits measurement of the angular positions of the Laue spots and the energies of the diffracted X-rays simultaneously. The plastic deformation of the nanowire was shown by a bending of up to 3.0 ± 0.1°, a torsion of up to 0.3 ± 0.1° and a maximum deformation depth of 80 ± 5 nm close to the position where the mechanical load was applied. In addition, extended Laue spots in the vicinity of one of the clamping points indicated the storage of geometrically necessary dislocations with a density of 7.5 × 1013 m-2. While µLaue diffraction with a non-energy-sensitive detector only gives access to the deviatoric strain, the energy sensitivity of the employed pnCCD offers absolute strain measurements with a resolution of 1%. Here, the residual strain after complete unloading of the nanowire amounted to maximum tensile and compressive strains of the order of +1.2 and -3%, which is comparable to the actual resolution limit. The combination of white-beam µLaue diffraction using an energy-sensitive pixel detector with nano-mechanical testing opens up new possibilities for the study of mechanical behavior at the nanoscale.
Project description:The mechanical properties and stability of metal nanoparticle colloids under high-pressure conditions are investigated by means of optical extinction spectroscopy and small-angle X-ray scattering (SAXS), for colloidal dispersions of gold nanorods and gold nanospheres. SAXS allows us to follow in situ the structural evolution of the nanoparticles induced by pressure, regarding both nanoparticle size and shape (form factor) and their aggregation through the interparticle correlation function S(q) (structure factor). The observed behavior changes under hydrostatic and nonhydrostatic conditions are discussed in terms of liquid solidification processes yielding nanoparticle aggregation. We show that pressure-induced diffusion and aggregation of gold nanorods take place after solidification of the solvent. The effect of nanoparticle shape on the aggregation process is additionally discussed.
Project description:Fission track thermochronology is routinely used to investigate the thermal history of sedimentary basins, as well as tectonic uplift and denudation rates. While the effect of temperature on fission track annealing has been studied extensively to calibrate the application of the technique, the effect of pressure during annealing is generally considered to be negligible. However, a previous study suggested elevated pressure results in a significantly different annealing behaviour that was previously unknown. Here, we present a method to study track annealing in situ under high pressure by using synchrotron-based small angle x-ray scattering (SAXS). To simulate fission tracks in a controlled environment, ion tracks were created in apatite from Durango, Mexico using 2 GeV Au or Bi ions provided by an ion accelerator facility. Samples were annealed at 250 °C at approximately 1 GPa pressure using diamond anvil cells (DACs) with heating capabilities. Additional in situ annealing experiments at ambient pressure and temperatures between 320 and 390 °C were performed for comparison. At elevated pressure a significantly accelerated annealing rate of the tracks was observed compared with annealing at ambient pressure. However, when extrapolated to geologically relevant temperatures and pressures, the effects become very small. The measurement methodology presented provides a new avenue to study materials behaviour in extreme environments.
Project description:AbstractThe effects of post-hydration heating over a broad range of temperatures are evident in many Mighei-like carbonaceous (CM) chondrites as a variety of mineral transitions. To better understand these processes and how a CM chondrite's starting composition may have affected them, we experimentally heated two meteorites with different degrees of aqueous alteration, Allan Hills 83100 and Murchison, at 25 °C temperature steps from 200 °C to 950 °C and 300 °C to 750 °C, respectively. During heating, synchrotron in situ X-ray diffraction patterns were collected. With the exception of calcite decomposition and its products, most mineral transitions were unaffected by starting composition. Key observations include: (1) partial decomposition of tochilinite at 200 °C, which indicates that tochilinite breakdown might be a two-stage process due to its intergrown layers of brucite/amakinite and mackinawite; (2) the breakdown of serpentine occurring at 300 °C with transitional phases appearing at 525 °C and 575-600 °C, while secondary olivine formed at 600 °C; (3) cronstedtite decomposing faster than lizardite, (4) the formation of secondary enstatite at 750 °C, and (5) calcite decomposition temperature differing significantly between meteorites, occurring at 725 °C and 575 °C in ALH 83100 and Murchison, respectively. The results for calcite are likely controlled by differences in its microstructure and chemical composition, related to the meteorite's impact history and degree of aqueous alteration. The difference in calcite decomposition temperature also explains the contrasts in the observed breakdown products, with clinopyroxene occurring in both meteorites, and oldhamite only in ALH 83100. Mineral transitions due to post-hydration heating have been characterized with a high resolution XRD method, enabling a better understanding of processes occurring on the parent asteroids of CM chondrites.Graphical abstractSupplementary informationThe online version contains supplementary material available at 10.1186/s40623-024-02116-2.
Project description:A novel experimental setup dedicated to the study of liquid and amorphous materials, on the white beam station of the PSICHÉ beamline at SOLEIL, is described. The Beer-Lambert absorption method has been developed using a broad-spectrum (white) incident beam for in situ density measurements at extreme conditions of pressure and temperature. This technique has been combined with other existing X-ray techniques (radiographic imaging, tomography and combined angle energy dispersive X-ray diffraction). Such a multi-technical approach offers new possibilities for the characterization of liquid and amorphous materials at high pressure and high temperature. The strength of this approach is illustrated by density measurements of liquid gallium at pressures up to 4 GPa, combining the three independent X-ray techniques (the Beer-Lambert absorption method, tomography and X-ray diffraction).
Project description:Since high-pressure devices have been used at synchrotron facilities, accurate determination of pressure and temperature in the sample has been a crucial objective, particularly for experiments that simulate the Earth's interior. However, in some cases using a thermocouple may have a high likelihood of failure or is incompatible with a high-pressure assembly. To address these challenges and similar issues, we aim to expand a previously proposed solution: to jointly estimate pressure and temperature (PT) through in situ X-ray diffraction, to cover a wider range of internal PT calibrants tested over larger PT ranges. A modifiable Python-based software is offered to quickly obtain results. To achieve these aims, in situ large volume press experiments are performed on pellets of intimately mixed powders of a halide (NaCl, KCl, KBr, CsCl) or MgO and a metal (Pt, Re, Mo, W, Ni) in the pressure range 3-11 GPa and temperature range 300-1800 K. Although the pressure range was chosen for practical reasons, it also covers an equally important depth range in the Earth (down to 350 km) for geoscience studies. A thermocouple was used to validate the PT conditions in the cell assemblies. The key results show that choosing the appropriate calibrant materials and using a joint PT estimation can yield surprisingly small uncertainties (i.e. <±0.1 GPa and <±50 K). This development is expected to benefit current and future research at extreme conditions, as other materials with high compressibility or high thermal pressure, stable over large PT ranges, may be discovered and used as PT calibrants.
Project description:A microfluidic platform was used to address the problems of obtaining diffraction-quality crystals and crystal handling during transfer to the X-ray diffractometer. Crystallization conditions of a protein of pharmaceutical interest were optimized and X-ray data were collected both in situ and ex situ.
Project description:Defect aggregates in doped ceria play a crucial role in blocking the movement of oxygen vacancies and hence in reducing ionic conductivity. Nevertheless, evaluation of their amount and the correlation between domain size and transport properties is still an open issue. Data derived from a high-pressure X-ray diffraction investigation performed on the Ce1-x(Nd0.74Tm0.26)xO2-x/2 system are employed to develop a novel approach aimed at evaluating the defect aggregate content; the results are critically discussed in comparison to the ones previously obtained from Sm- and Lu-doped ceria. Defect clusters are present even at the lowest considered x value, and their content increases with increasing x and decreasing rare earth ion (RE3+) size; their amount, distribution, and spatial correlation can be interpreted as a complex interplay between the defects' binding energy, nucleation rate, and growth rate. The synoptic analysis of data derived from all of the considered systems also suggests that the detection limit of the defects by X-ray diffraction is correlated to the defect size rather than to their amount, and that the vacancies' flow through the lattice is hindered by defects irrespective of their size and association degree.
Project description:Films made of colloidal CsPbBr3 nanocrystals packed in isolated or densely-packed superlattices display a remarkably high degree of structural coherence. The structural coherence is revealed by the presence of satellite peaks accompanying Bragg reflections in wide-angle X-ray diffraction experiments in parallel-beam reflection geometry. The satellite peaks, also called “superlattice reflections“, arise from the interference of X-rays diffracted by the atomic planes of the orthorhombic perovskite lattice. The interference is due to the precise spatial periodicity of the nanocrystals separated by organic ligands in the superlattice. The presence of satellite peaks is a fingerprint of the high crystallinity and long-range order of nanocrystals, comparable to those of multilayer superlattices prepared by physical methods. The angular separation between satellite peaks is highly sensitive to changes in the superlattice periodicity. These characteristics of the satellite peaks are exploited to track the superlattice compression under vacuum, as well as to observe the superlattice growth in situ from colloidal solutions by slow solvent evaporation.
Project description:Iron nitride (Fe3N) and iron carbide (Fe3C) nanoparticles can be prepared via sol-gel synthesis. While sol-gel methods are simple, it can be difficult to control the crystalline composition, i.e., to achieve a Rietveld-pure product. In a previous in situ synchrotron study of the sol-gel synthesis of Fe3N/Fe3C, we showed that the reaction proceeds as follows: Fe3O4 → FeOx → Fe3N → Fe3C. There was considerable overlap between the different phases, but we were unable to ascertain whether this was due to the experimental setup (side-on heating of a quartz capillary which could lead to thermal gradients) or whether individual particle reactions proceed at different rates. In this paper, we use in situ wide- and small-angle X-ray scattering (wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS)) to demonstrate that the overlapping phases are indeed due to variable reaction rates. While the initial oxide nanoparticles have a small range of diameters, the size range expands considerably and very rapidly during the oxide-nitride transition. This has implications for the isolation of Rietveld-pure Fe3N, and in an extensive laboratory study, we were indeed unable to isolate phase-pure Fe3N. However, we made the surprising discovery that Rietveld-pure Fe3C nanoparticles can be produced at 500 °C with a sufficient furnace dwell time. This is considerably lower than the previous reports of the sol-gel synthesis of Fe3C nanoparticles.