Andrew C. Jupe

The Oxford-Diamond In Situ Cell for studying chemical reactions using time-resolved X-ray diffraction

A versatile, infrared-heated, chemical reaction cell has been assembled and commissioned for the in situ study of a range of chemical syntheses using time-resolved energy-dispersive X-ray diffraction (EDXRD) on Beamline I12 at the Diamond Light Source. Specialized reactor configurations have been constructed to enable in situ EDXRD investigation of samples under non-ambient conditions. Chemical reactions can be studied using a range of sample vessels such as alumina crucibles, steel hydrothermal autoclaves, and glassy carbon tubes, at temperatures up to 1200 °C.

In-situ hydration studies using multi-angle energy-dispersive diffraction.

A new diffractometer has been built with which energy-dispersive diffraction patterns can be collected simultaneously at different angles. The first use of this system for dynamic (time-resolved) studies--the hydration of cements under various conditions--is reported. It is found that the optimization available with a three-element detector system enables collection of high-quality patterns over a much wider and more effective range of reciprocal space, and this yields improved and new information on the hydration processes.

Reducing the background from pressure vessels using a BRIM

A collimator and beam-stop assembly that can be inserted inside a temperature-controlled pressure vessel, to reduce dramatically the parasitic Bragg scattering from the vessel, has been designed and evaluated. High-energy X-ray powder diffraction data, suitable for the Rietveld refinement of simple crystal structures, were collected using this background-reducing internal mask (BRIM). ZrW2O8 was examined at up to 540 K and 124 MPa, using quite large pressure and temperature steps. No pressure dependence of the order–disorder transition temperature of this material was apparent. An orthorhombic to monoclinic phase transition (onset ∼83 MPa) was observed for Al2W3O12. Upon going through the transition, the bulk modulus of the material decreased from 41.8 to 20.8 GPa. Bulk moduli estimated for CaF2 and α-Al2O3, from data collected at up to 280 MPa, were in good agreement with prior literature.

Phase composition depth profiles using spatially resolved energy dispersive x-ray diffraction.

Spatially resolved energy dispersive X-ray diffraction, using high-energy synchrotron radiation (∼35-80 keV), was used nondestructively to obtain phase composition profiles along the radii of cylindrical cement paste samples to characterize the progress of the chemical changes associated with sulfate attack on the cement. Phase distributions were acquired to depths of ∼4 mm below the specimen surface with sufficient spatial resolution to discern features less than 200 μm thick. The experimental and data analysis methods employed to obtain quantitative composition profiles are described. The spatial resolution that could be achieved is illustrated using data obtained from copper cylinders with a thin zinc coating. The measurements demonstrate that this approach is useful for nondestructively visualizing the sometimes complex transformations that take place during sulfate attack on cement-based materials. These transformations can be spatially related to microstructure as seen by computed microtomography.

Sulfate deterioration of cement-based materials examined by x-ray microtomography

Sulfate ions present in soil, groundwater, seawater, decaying organic matter, acid rain, and industrial effluent adversely affect the long-term durability of portland cement concrete, but lack of complete understanding of the nature and consequences of sulfate attack hamper our ability to accurately predict performance of concrete in sulfate-rich environments. One impediment to improved understanding of sulfate deterioration of cement-based materials has been the lack of appropriate non-destructive characterization techniques. Laboratory x-ray microtomography affords an opportunity to study in situ the evolution of physical manifestations of damage due to sulfate exposure. The influence of materials selection and mixture parameters -- including water-to-cement ratio, cement type, and presence or absence of aggregate, as well as the influence of sulfate exposure conditions, including sulfate and cation type (i.e., Na2SO4 and MgSO4) and concentration -- have been examined by microtomography to determine their influence on the rate and character of the sulfate-induced deterioration.

Sample cell for powder x-ray diffraction at up to 500bars and 200°C

A low cost sample cell for powder diffraction at high pressure and temperature that employs either sapphire or steel pressure tubes is described. The cell can be assembled rapidly, facilitating the study of chemically reacting systems, and it provides good control of both pressure and temperature in a regimen where diamond anvil cells and multianvil apparatus cannot be used. The design provides a relatively large sample volume making it suitable for the study of quite large grain size materials, such as hydrating cement slurries. However, relatively high energy x rays are needed to penetrate the pressure tube.

Spatially Resolved Energy Dispersive X-Ray Diffraction (EDXRD) as a Tool for Nondestructively Providing Phase Composition Depth Profiles on Cement and Other Materials

The presence of sulfates in water or soils surrounding portland cement concrete structures leads to progressive degradation. Spatially resolved energy dispersive diffraction (EDXRD) in combination with computed microtomography (μCT) and mechanical measurements can provide the information needed to understand, in detail, the degradation mechanisms that are associated with sulfate attack and to validate accelerated test methods used to evaluate the sulfate resistance of cements. Highly penetrating, high-energy X-rays from synchrotron sources allow the use of EDXRD to nondestructively determine depth profiles for the crystalline phases in the cement paste specimens several millimeters below the sample surface. These depth profiles, and how they vary with sulfate exposure conditions and duration, can be correlated with mechanical changes and the crack patterns seen in the microtomographs. Spatially resolved EDXRD is in principle useful for phase composition mapping and depth profiling in a wide range of materials where the attenuation of high energy x-rays is not extreme. Suitable materials include many ceramic compositions.Copyright