Jasper Rikkert Plaisier

In situ reaction furnace for real-time XRD studies.

The new furnace at the Materials Characterization by X-ray Diffraction beamline at Elettra has been designed for powder diffraction measurements at high temperature (up to 1373u2005K at the present state). Around the measurement region the geometry of the radiative heating element assures a negligible temperature gradient along the capillary and can accommodate either powder samples in capillary or small flat samples. A double capillary holder allows flow-through of gas in the inner sample capillary while the outer one serves as the reaction chamber. The furnace is coupled to a translating curved imaging-plate detector, allowing the collection of diffraction patterns up to 2θ ≃ 130°.

Phosphonium-based tetrakis dibenzoylmethane Eu(III) and Sm(III) complexes: synthesis, crystal structure and photoluminescence properties in a weakly coordinating phosphonium ionic liquid

Highly luminescent anionic Ln(III) β-diketonate complexes of the formula [P8,8,8,1][Ln(dbm)4], with Ln = Eu3+ and Sm3+, [P8,8,8,1] = trioctylmethylphosphonium and dbm = 1,3-diphenylpropane-1,3-dione were synthesized. The single crystal X-ray structure of the samarium and europium complexes showed that the metal ion was surrounded by four ligands and that no water or solvent molecules were coordinated. The solid complexes showed good thermal stability up to 250 °C. The complexes easily dissolved in the ionic liquid trioctylmethylphosphonium bis(trifluoromethylsulfonyl)imide [P8,8,8,1][Tf2N], due to the presence of a common phosphonium countercation in the ionic liquid and in the Eu(III) and Sm(III) complexes. The photoluminescence of the complexes was studied in the solid state and in an ionic liquid as well as in acetonitrile (MeCN) as a solvent.

High-temperature and high-pressure behavior of carbonates in the ternary diagram CaCO3-MgCO3-FeCO3

Abstract We report the thermal expansion and the compressibility of carbonates in the ternary compositional diagram CaCO3-MgCO3-FeCO3, determined by in situ X-ray powder and single-crystal diffraction. High-temperature experiments were performed by high-resolution X-ray synchrotron powder diffraction from ambient to decarbonation temperatures (25–850 °C). Single-crystal synchrotron X ray diffraction experiments were performed in a variable pressure range (0–100 GPa), depending on the stability field of the rhombohedral structure at ambient temperature, which is a function of the carbonate composition. The thermal expansion increases from calcite, CaCO3, α0 = 4.10(7) ×10–5 K–1, to magnesite, MgCO3, α0 = 7.04(2) ×10–5 K–1. In the magnesite-siderite (FeCO3) join, the thermal expansion decreases as iron content increases, with an experimental value of α0 = 6.44(4) ×10–5 K–1 for siderite. The compressibility in the ternary join is higher (i.e., lower bulk modulus) in calcite and Mg-calcite [K0 = 77(3) GPa for Ca0.91Mg0.06Fe0.03(CO3)] than in magnesite, K0 = 113(1) GPa, and siderite, K0 = 125(1) GPa. The analysis of thermal expansion and compressibility variation in calcite-magnesite and calcite-iron-magnesite joins clearly shows that the structural changes associated to the order-disorder transitions [i.e., R3c calcite-type structure vs. R3 CaMg(CO3)2 dolomite-type structure] do not affect significantly the thermal expansion and compressibility of carbonate. On the contrary, the chemical compositions of carbonates play a major role on their thermo-elastic properties. Finally, we use our P-V-T equation of state data to calculate the unit-cell volume of a natural ternary carbonate, and we compare the calculated volumes to experimental observations, measured in situ at elevated pressure and temperatures, using a multi-anvil device. The experimental and calculated data are in good agreement demonstrating that the equation of state here reported can describe the volume behavior with the accuracy needed, for example, for a direct chemical estimation of carbonates based on experimental unit-cell volume data of carbonates at high pressures and temperatures.

The crystal structure of mineral fibres: 1. Chrysotile

This work reports the result s of the structural study of three representative chrysotile samples of different provenance (Canadian UICC, and Italian Balangero and Valmalenco) . Chemical composition was determined using EMPA and TG data. An innovative wet cryo-milling procedure was used to powder the resistant-to-abrasion chrysotile fibres. X-ray powder diffraction patterns were collected using both conventional and non-conventional sources. Collected data were used for Rietveld structural refinements and results were compared with available literature data. The three samples display similar structure models, although small differences were detected in the position of the oxygen atoms. Both the structural refinements and spectroscopic investigations confirms that Fe 2+ and Fe 3+ atoms in chrysotile are located in the octahedral cavities only, substituting for Mg 2+ . Regarding the atom coordinates, UICC chrysotile is the more similar to the model reported by Falini et al. (2004). About the lattice parameters, the Valmalenco chrysotile is the more similar, if compared with the Balangero and UICC, to both the model proposed by Whittaker (1956a,b) and Falini et al. (2004) . This work is intended as a basis for subsequent studies aimed at understanding the potential toxicity of these mineral fibres.

Influence of Lattice Defects on the Grain Growth Kinetics of Nanocrystalline Fluorite

The growth process of nanocrystalline fluorite was studied by in situ synchrotron radiation X-ray diffraction. The two studied samples had comparable crystalline domain size, but quite different content of lattice defects as a result of the different preparation procedures: ball milling of coarse CaF2 powder or coprecipitation of CaCl2 and NH4F. It is shown that the high dislocation density in the ball-milled fluorite is responsible for a recrystallization process above 773xa0K (500xa0°C), which is not observed in the chemically synthesized fluorite. The linear thermal expansion coefficients of both nanocrystalline powders, as obtained and also from the in situ X-ray diffraction data, show a smaller increase with temperature than suggested by the literature on coarse-grained fluorite.

Instrumentation at Synchrotron Radiation Beamlines

Today there are a number of third-generation synchrotron facilities around the world, which are dedicated to the production of extremely intense radiation, ranging from infrared to hard X-rays. The wavelength tunability and the very high brightness of these sources have opened a wide range of new characterization procedures for research purposes. This paragraph is intended to describe various facets of both technological and analytical methods using synchrotron radiation, in order to help researchers and students who are interested in the study of materials. First, a concise introduction to synchrotron facilities and an overview of the main characteristics of the existing third-generation sources are presented. Then a basic line-up of beamlines for different energy ranges as well as the problems associated to beamline constructions and choices are described. Finally, for each energy range, a brief description of some techniques available in third-generation synchrotron facilities is given.

Crystal-chemistry and vibrational spectroscopy of ferrinatrite, Na 3 [Fe(SO 4 ) 3 ]·3H 2 O, and its high-temperature decomposition

The crystal structure of ferrinatrite, Na3[Fe(SO4)3]·3H2O, was refined based on a new single-crystal X-ray diffraction experiment on a sample from the type locality Sierra Gorda, Chile. The data allowed H to be successfully located and the H-bonding system to be defined. Infrared and Raman spectra are presented and discussed for this compound on the basis of the crystal structure. The Oacceptor···H–Odonor bond distances determined from the structure refinement agree well with the geometric correlation obtained from spectroscopic data. The thermal stability and dehydration process of ferrinatrite was investigated by in situ high temperature (HT) synchrotron X-ray powder diffraction, Raman and Fourier transform infrared spectroscopies.

Impact of Average, Local, and Electronic Structure on Visible Light Photocatalysis in Novel BiREWO6 (RE = Eu and Tb) Nanomaterials

Crystal structures of hydrothermally synthesized BiEuWO6 and BiTbWO6 nanomaterials are deduced for the first time by combined Rietveld refinement of neutron and synchrotron data using the ordered and disordered models available in literature. The ordered model is validated for the average structure of these nanomaterials, and it is further supported by the local structure analysis using neutron pair distribution function. Nanomaterials are characterized by field-emission scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller surface area, diffused reflectance spectroscopy, and Raman Spectroscopy. Rare-earth-substituted nanomaterials are found to be efficient photocatalysts over the parent Bi2WO6 under visible light irradiation for Congo-red dye degradation. Particularly, BiTbWO6 shows an enhanced photocatalytic (PC) activity compared to BiEuWO6, as evidenced from the photoelectrochemical and time-resolved fluorescence studies. The difference in the observed PC activity of these nanomaterials is also explored through a detailed comparison of crystal structure and electronic structure calculated through the density functional theory method.

Chitosan-fatty acid interaction mediated growth of Langmuir monolayer and Langmuir-Blodgett films

The interaction of chitosan with bio-membranes, which plays important role in deciding its use in biological applications, is realized by investigating the interaction of chitosan with stearic acid (fatty acid) in Langmuir monolayers (at air-water interface) and Langmuir-Blodgett (LB) films (after transferring it onto solid substrate). It is found from the pressure-area isotherms that the chitosan insertion causes an expansion of chitosan-fatty acid hybrid monolayers, which reduces the elasticity and make the film heterogeneous. It is likely that at low surface pressure chitosan is situated at the interface, interacting with stearic acid molecules via electrostatic and hydrophobic interactions whereas at high pressure chitosan mainly located at subsurface beneath stearic acid molecules. In the latter case the interaction is predominantly electrostatic yielding very small contribution to the surface pressure. The reduction of temperature of the subphase water allows more number of chitosan molecules to reach surface to increase the pressure/interaction. On the other hand, although pure chitosan is found difficult to relocate on the substrate from air-water interface due to its hydrophilic-like nature, it alongside stearic acid (amphiphilic molecules) can be transferred onto substrate using LB technique as evident from infrared spectra. Their out-of-plane and in-plane structures, as extracted from two complementary surface sensitive techniques- X-ray reflectivity and atomic force microscopy, are found strongly dependent on the chitosan mole fraction and the deposition pressure. These analysis of the film-structure will essentially allow one to model the system better and provide better insight into the interaction.

Laser shock peening on a 6056-T4 aluminium alloy for airframe applications

Laser Shock Peening (LSP) is a material enhancement process used to introduce compressive residual stresses in metallic components. This investigation explored the effects of different combinations of LSP parameters, such as irradiance (GW/cm2) and laser pulse density (spots/mm2), on 3.2 mm thick AA6056-T4 samples, for integral airframe applications. The most significant effects that are introduced by LSP without a protective coating include residual stress and surface roughness, since each laser pulse vaporizes the surface layer of the target. Each of these effects was quantified, whereby residual stress analysis was performed using X-ray diffraction with synchrotron radiation. A series of fully reversed bending fatigue tests was conducted, in order to evaluate fatigue performance enhancements with the aim of identifying LSP parameter influence. Improvement in fatigue life was demonstrated, and failure of samples at the boundary of the LSP treatment was attributed to a balancing tensile residual stress.