Simon D. M. Jacques

Implementation of a combined SAXS/WAXS/QEXAFS set-up for time-resolved in situ experiments

It has previously been shown that there are many benefits to be obtained in combining several techniques in one in situ set-up to study chemical processes in action. Many of these combined set-ups make use of two techniques, but in some cases it is possible and useful to combine even more. A set-up has recently been developed that combines three X-ray-based techniques, small- and wide-angle X-ray scattering (SAXS/WAXS) and quick-scanning EXAFS (QEXAFS), for the study of dynamical chemical processes. The set-up is able to probe the same part of the sample during the synthesis process and is thus able to follow changes at the nanometre to micrometre scale during, for example, materials self-assembly, with a time resolution of the order of a few minutes. The practicality of this kind of experiment has been illustrated by studying zeotype crystallization processes and revealed important new insights into the interplay of the various stages of ZnAPO-34 formation. The flexibility of this set-up for studying other processes and for incorporating other additional non-X-ray-based experimental techniques has also been explored and demonstrated for studying the stability/activity of iron molybdate catalysts for the anaerobic decomposition of methanol.

Pixellated Cd(Zn)Te high-energy X-ray instrument

We have developed a pixellated high energy X-ray detector instrument to be used in a variety of imaging applications. The instrument consists of either a Cadmium Zinc Telluride or Cadmium Telluride (Cd(Zn)Te) detector bump-bonded to a large area ASIC and packaged with a high performance data acquisition system. The 80 by 80 pixels each of 250 μm by 250 μm give better than 1 keV FWHM energy resolution at 59.5 keV and 1.5 keV FWHM at 141 keV, at the same time providing a high speed imaging performance. This system uses a relatively simple wire-bonded interconnection scheme but this is being upgraded to allow multiple modules to be used with very small dead space. The readout system and the novel interconnect technology is described and how the system is performing in several target applications.

Tomographic Energy Dispersive Diffraction Imaging To Study the Genesis of Ni Nanoparticles in 3D within γ-Al2O3 Catalyst Bodies

Tomographic energy dispersive diffraction imaging (TEDDI) is a recently developed synchrotron-based characterization technique used to obtain spatially resolved X-ray diffraction and fluorescence information in a noninvasive manner. With the use of a synchrotron beam, three-dimensional (3D) information can be conveniently obtained on the elemental composition and related crystalline phases of the interior of a material. In this work, we show for the first time its application to characterize the structure of a heterogeneous catalyst body in situ during thermal treatment. Ni/gamma-Al(2)O(3) hydrogenation catalyst bodies have been chosen as the system of study. As a first example, the heat treatment in N(2) of a [Ni(en)(3)](NO(3))(2)/gamma-Al(2)O(3) catalyst body has been studied. In this case, the crystalline [Ni(en)(3)](NO(3))(2) precursor was detected in an egg-shell distribution, and its decomposition to form metallic Ni crystallites of around 5 nm was imaged. In the second example, the heat treatment in N(2) of a [Ni(en)(H(2)O)(4)]Cl(2)/gamma-Al(2)O(3) catalyst body was followed. The initial [Ni(en)(H(2)O)(4)]Cl(2) precursor was uniformly distributed within the catalyst body as an amorphous material and was decomposed to form metallic Ni crystallites of around 30 nm with a uniform distribution. TEDDI also revealed that the decomposition of [Ni(en)(H(2)O)(4)]Cl(2) takes place via two intermediate crystalline structures. The first one, which appears at around 180 degrees C, is related to the restructuring of the Ni precursor on the alumina surface; the second one, assigned to the formation of a limited amount of Ni(3)C, is observed at 290 degrees C.

Pair distribution function computed tomography

An emerging theme of modern composites and devices is the coupling of nanostructural properties of materials with their targeted arrangement at the microscale. Of the imaging techniques developed that provide insight into such designer materials and devices, those based on diffraction are particularly useful. However, to date, these have been heavily restrictive, providing information only on materials that exhibit high crystallographic ordering. Here we describe a method that uses a combination of X-ray atomic pair distribution function analysis and computed tomography to overcome this limitation. It allows the structure of nanocrystalline and amorphous materials to be identified, quantified and mapped. We demonstrate the method with a phantom object and subsequently apply it to resolving, in situ, the physicochemical states of a heterogeneous catalyst system. The method may have potential impact across a range of disciplines from materials science, biomaterials, geology, environmental science, palaeontology and cultural heritage to health.

Non-invasive imaging of the crystalline structure within a human tooth

The internal crystalline structure of a human molar tooth has been non-destructively imaged in cross-section using X-ray diffraction computed tomography. Diffraction signals from high-energy X-rays which have large attenuation lengths for hard biomaterials have been collected in a transmission geometry. Coupling this with a computed tomography data acquisition and mathematically reconstructing their spatial origins, diffraction patterns from every voxel within the tooth can be obtained. Using this method we have observed the spatial variations of some key material parameters including nanocrystallite size, organic content, lattice parameters, crystallographic preferred orientation and degree of orientation. We have also made a link between the spatial variations of the unit cell lattice parameters and the chemical make-up of the tooth. In addition, we have determined how the onset of tooth decay occurs through clear amorphization of the hydroxyapatite crystal, and we have been able to map the extent of decay within the tooth. The described method has strong prospects for non-destructive probing of mineralized biomaterials.

3D chemical imaging in the laboratory by hyperspectral X-ray computed tomography

We report the development of laboratory based hyperspectral X-ray computed tomography which allows the internal elemental chemistry of an object to be reconstructed and visualised in three dimensions. The method employs a spectroscopic X-ray imaging detector with sufficient energy resolution to distinguish individual elemental absorption edges. Elemental distributions can then be made by K-edge subtraction, or alternatively by voxel-wise spectral fitting to give relative atomic concentrations. We demonstrate its application to two material systems: studying the distribution of catalyst material on porous substrates for industrial scale chemical processing; and mapping of minerals and inclusion phases inside a mineralised ore sample. The method makes use of a standard laboratory X-ray source with measurement times similar to that required for conventional computed tomography.

Rapid whole-rock mineral analysis and composition mapping by synchrotron X-ray diffraction

We show that 25–140 keV X-rays from high-brilliance synchrotron sources can penetrate through 25 mm of intact rock. Powder diffraction patterns are obtained rapidly by energy-dispersive detection. Data acquisition time is reduced by a large factor (say 102–103) compared with standard laboratory powder diffraction methods. Data are presented on sedimentary rock cores and mineral standards. Full-pattern fitting is used for quantitative modal analysis of the composition. Using acquisition times of only 20 s for each pattern, we show the feasibility of line traverse (conveyor-belt) X-ray diffraction analysis and compositional tomography with sub-millimeter resolution.

Dark-field hyperspectral X-ray imaging

In recent times, there has been a drive to develop non-destructive X-ray imaging techniques that provide chemical or physical insight. To date, these methods have generally been limited; either requiring raster scanning of pencil beams, using narrow bandwidth radiation and/or limited to small samples. We have developed a novel full-field radiographic imaging technique that enables the entire physio-chemical state of an object to be imaged in a single snapshot. The method is sensitive to emitted and scattered radiation, using a spectral imaging detector and polychromatic hard X-radiation, making it particularly useful for studying large dense samples for materials science and engineering applications. The method and its extension to three-dimensional imaging is validated with a series of test objects and demonstrated to directly image the crystallographic preferred orientation and formed precipitates across an aluminium alloy friction stir weld section.

A CdTe detector for hyperspectral SPECT imaging

A Cadmium Telluride (CdTe) detector has been developed for multiple-radioisotope SPECT imaging. The 2 × 2 cm detector has 80 × 80 pixels on a 250 μm pitch and a three-side buttable design so that it can be tiled into larger arrays. The detector is termed hyperspectral as it measures the energy of every photon that interacts in the CdTe to give fully spectroscopic information from 5–200 keV in each pixel. The detector has been tested for applications in multiple-radioisotope SPECT imaging using a 1 mm diameter pinhole configuration and standard phantom test objects containing Tc-99m, I-123 and Ga-67. The detector has an average pixel energy resolution (FWHM) of 0.75% at the I-123 photopeak of 159 keV. We demonstrate the systems capability of resolving spatial features of 2 mm, although the spatial resolution of the detector is limited only by the pixel size and pinhole magnification factor. These characteristics are superior to alternative detectors currently in use in clinical SPECT systems. When imaging multiple radioisotopes simultaneously, we show that there is very little cross-talk between adjacent photopeaks, leading to superior image contrast. The detector is also capable of resolving fluorescence x-rays from the radioactive source, which could be used to improve image count statistics or derive information about the attenuation properties of the source. The performance presented here, and the ability to tile the detector modules to create a clinically useful field of view, makes this technology a strong candidate to be used in future solid-state SPECT cameras.

A synchrotron tomographic energy-dispersive diffraction imaging study of the aerospace alloy Ti 6246

A titanium alloy sample (#6246) containing a linear friction weld has been imaged nondestructively using tomographic energy-dispersive diffraction imaging (TEDDI). The diffraction patterns measured at each point of the TEDDI image permitted identification of the material and phases present (±5%). The image also showed the preferred orientation and size–strain distribution present within the sample without the need for any further sample preparation. The preferred orientation was observed in clusters with average dimensions very similar to the experimental spatial resolution (400 µm). The length scales and preferred orientation distributions were consistent with orientation imaging microscopy measurements made by Szczepanski, Jha, Larsen & Jones [Metall. Mater. Trans. A (2008), 39, 2841–2851] where the microstructure development was linked to the grain growth of the parent material. The use of a high-energy X-ray distribution (30–80 keV) in the incident beam reduced systematic errors due to the source profile, sample and air absorption. The TEDDI data from each voxel were reduced to an angle-dispersive form and Rietveld refined to a mean χ2 of 1.4. The mean lattice parameter error (δd/d) ranged from ∼10−4 for the highly crystalline regions to ∼10−3 for regions of very strong preferred orientation and internal strain. The March–Dollase preferred orientation errors refined to an average value of ±2%. A 100% correlation between observed fluorescence and diffraction peak broadening was observed, providing further evidence for vicinal strain broadening.