Transmission X-ray microscopy : a new tool in clay mineral floccules characterization

Effective flocculation and dewatering of mineral processing streams containing clays are microstructure dependent in clay-water systems. Initial clay flocculation is crucial in the design and for the development of a new methodology of gas exploitation. Microstructural engineering of clay aggregates using covalent cations and Keggin macromolecules have been monitored using the new state of the art Transmission X-ray Microscope (TXM) with 60 nm tomography resolution installed in a Taiwanese synchrotron. The 3-D reconstructions from TXM images show complex aggregation structures in montmorillonite aqueous suspensions after treatment with Na+, Ca2+ and Al13 Keggin macromolecules. Na-montmorillonite displays elongated, parallel, well-orientated and closed-void cellular networks, 0.5–3 μm in diameter. After treatment by covalent cations, the coagulated structure displays much smaller, randomly orientated and openly connected cells, 300–600 nm in diameter. The average distances measured between montmorillonite sheets was around 450 nm, which is less than half of the cell dimension measured in Na-montmorillonite. The most dramatic structural changes were observed after treatment by Al13 Keggin; aggregates then became arranged in compacted domains of a 300 nm average diameter composed of thick face-to-face oriented sheets, which forms porous aggregates with larger intra-aggregate open and connected voids.

Smectite flocculation structure modified by AI13 macromolecules; as revealed by the Transmission X-ray Microscopy (TXM)

The aggregate structure which occurs in aqueous smectitic suspensions is responsible for poor water clarification, difficulties in sludge dewatering and the unusual rheological behaviour of smectite rich soils. These macroscopic properties are dictated by the 3-D structural arrangement of smectite finest fraction within flocculated aggregates. Here, we report results from a relatively new technique, Transmission X-ray Microscopy (TXM), which makes it possible to investigate the internal structure and 3-D tomographic reconstruction of the smectite clay aggregates modified by Al13 keggin macro-molecule [Al13(O)4(OH)24(H2O)12 ]7+. Three different treatment methods were shown resulted in three different micro-structural environments of the resulting flocculation.

Observing the in situ chiral modification of Ni nanoparticles using scanning transmission X-ray microspectroscopy

Enantioselective heterogeneous hydrogenation of Cdouble bond; length as m-dashO bonds is of great potential importance in the synthesis of chirally pure products for the pharmaceutical and fine chemical industries. One of the most widely studied examples of such a reaction is the hydrogenation of β-ketoesters and β-diketoesters over Ni-based catalysts in the presence of a chiral modifier. Here we use scanning transmission X-ray microscopy combined with near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) to investigate the adsorption of the chiral modifier, namely (R,R)-tartaric acid, onto individual nickel nanoparticles. The C K-edge spectra strongly suggest that tartaric acid deposited onto the nanoparticle surfaces from aqueous solutions undergoes a keto-enol tautomerisation. Furthermore, we are able to interrogate the Ni L2,3-edge resonances of individual metal nanoparticles which, combined with X-ray diffraction (XRD) patterns showed them to consist of a pure nickel phase rather than the more thermodynamically stable bulk nickel oxide. Importantly, there appears to be no “particle size effect” on the adsorption mode of the tartaric acid in the particle size range ~ 90–~ 300 nm.

X-Ray Imaging of SAPO-34 Molecular Sieves at the Nanoscale: Influence of Steaming on the Methanol-to-Hydrocarbons Reaction

The effect of a severe steaming treatment on the physicochemical properties and catalytic performance of H-SAPO-34 molecular sieves during the methanol-to-hydrocarbons (MTH) reaction has been investigated with a combination of scanning transmission X-ray microscopy (STXM), catalytic testing, and bulk characterization techniques, including ammonia temperature programmed desorption and 27Al and 29Si magic angle spinning nuclear magnetic resonance. For this purpose, two samples, namely a calcined and a steamed H-SAPO-34 catalyst powder, have been compared. It has been found that calcined H-SAPO-34 displays a high selectivity towards light olefins, yet shows a poor stability as compared to a zeolite H-ZSM-5 catalyst. Moreover, in situ STXM at the carbon K-edge during the MTH reaction allows construction of nanoscale chemical maps of the hydrocarbon species formed within the H-SAPO-34 aggregates as a function of reaction time and steam post-treatment. It was found that there is an initial preferential formation of coke precursor species within the core of the H-SAPO-34 aggregates. For longer times on stream the formation of the coke precursor species is extended to the outer regions, progressively filling the entire H-SAPO-34 catalyst particle. In contrast, the hydrothermally treated H-SAPO-34 showed similar reaction selectivity, but decreased activity and catalyst stability with respect to its calcined counterpart. These variations in MTH performance are related to a faster and more homogeneous formation of coke precursor species filling up the entire steamed H-SAPO-34 catalyst particle. Finally, the chemical imaging capabilities of the STXM method at the Al and Si K-edge are illustrated by visualizing the silicon islands at the nanoscale before and after steaming H-SAPO-34.

The influence of physical state on shikimic acid ozonolysis: a case for in situ microspectroscopy

Atmospheric soluble organic aerosol material can become solid or semi-solid. Due to increasing viscosity and decreasing diffusivity, this can impact important processes such as gas uptake and reactivity within aerosols containing such substances. This work explores the dependence of shikimic acid ozonolysis on humidity and thereby viscosity. Shikimic acid, a proxy for oxygenated reactive organic material, reacts with O3 in a Criegee-type reaction. We used an environmental microreactor embedded in a scanning transmission X-ray microscope (STXM) to probe this oxidation process. This technique facilitates in situ measurements with single micron-sized particles and allows to obtain near-edge X-ray absorption fine structure (NEXAFS) spectra with high spatial resolution. Thus, the chemical evolution of the interior of the particles can be followed under reaction conditions. The experiments show that the overall degradation rate of shikimic acid is depending on the relative humidity in a way that is controlled by the decreasing diffusivity of ozone with decreasing humidity. This decreasing diffusivity is most likely linked to the increasing viscosity of the shikimic acid–water mixture. The degradation rate was also depending on particle size, most congruent with a reacto-diffusion limited kinetic case where the reaction progresses only in a shallow layer within the bulk. No gradient in the shikimic acid concentration was observed within the bulk material at any humidity indicating that the diffusivity of shikimic acid is still high enough to allow its equilibration throughout the particles on the timescale of hours at higher humidity and that the thickness of the oxidized layer under dry conditions, where the particles are solid, is beyond the resolution of STXM.

Investigating the structure of biomass-derived non-graphitizing mesoporous carbons by electron energy loss spectroscopy in the transmission electron microscope and X-ray photoelectron spectroscopy

We have investigated the microstructure and bonding of two biomass-based porous carbon chromatographic stationary phase materials (alginic acid-derived Starbon® and calcium alginate-derived mesoporous carbon spheres (AMCS) and a commercial porous graphitic carbon (PGC), using high resolution transmission electron microscopy, electron energy loss spectroscopy (EELS), N2 porosimetry and X-ray photoelectron spectroscopy (XPS). The planar carbon sp -content of all three material types is similar to that of traditional nongraphitizing carbon although, both biomass-based carbon types contain a greater percentage of fullerene character (i.e. curved graphene sheets) than a non-graphitizing carbon pyrolyzed at the same temperature. This is thought to arise during the pyrolytic breakdown of hexauronic acid residues into C5 intermediates. Energy dispersive X-ray and XPS analysis reveals a homogeneous distribution of calcium in the AMCS and a calcium catalysis mechanism is discussed. That both Starbon® and AMCS, with high-fullerene character, show chromatographic properties similar to those of a commercial PGC material with extended graphitic stacks, suggests that, for separations at the molecular level, curved fullerene- like and planar graphitic sheets are equivalent in PGC chromatography. In addition, variation in the number of graphitic layers suggests that stack depth has minimal effect on the retention mechanism in PGC chromatography. © 2013 Elsevier Ltd. All rights reserved.

X-ray diffraction of permalloy nanoparticles fabricated by laser ablation in water

Permalloy (NiFeMo) nanoparticles were fabricated by laser ablation of bulk material in water with a UV pulsed laser. Transmission electron microscope images showed that approximately spherical particles about 50 nm in diameter were formed in the ablation process. All diffraction peaks corresponding to the bulk material were present in the nanoparticles. In addition to these peaks several new peaks were observed in the nanoparticles, which were attributed to nickel oxide.

Ex Situ X-ray Diffraction, X-ray Absorption Near Edge Structure, Electron Spin Resonance, and Transmission Electron Microscopy Study of the Hydrothermal Crystallization of Vanadium Oxide Nanotubes: An Insight into the Mechanism of Formation

The nucleation and growth of vanadium oxide nanotubes (VOx-NT) have been followed by a combination of numerous ex situ techniques. long the hydrothermal process. Intermediate solid phases extracted at different reaction times have been characterized by powder X-ray diffraction, scanning and transmission electron microscopy, electron spin resonance, and V-K edge :X-ray absorption near-edge structure spectroscopy. The supernatant vanadate solutions extracted during the hydrothermal treatment have been studied by liquid V-51 NMR and flame. spectroscopy. For short durations of the hydrothermal synthesis, the initial V2O5-surfactant intercalate. is progressively transformed into VOx-NT whose crystallization starts to be detected after a hydrothermal treatment of 24 h. Upon heating from 24 h to 7 days, VOx-NT are obtained in larger amount and with an improved crystallinity. The detection of soluble amines and cyclic metavanadate V4O12](4-) in the supernatant solution along the hydrothermal process suggests that VOx-NT result from a dissolution precipitation mechanism. Metavanadate species V4O12](4-) could behave as molecular precursors in the polymerization reactions leading to VOx-NT.

A transmission electron microscopy and X-ray photoelectron spectroscopy study of annealing induced gamma-phase nucleation, clustering, and interfacial dynamics in reactively sputtered amorphous alumina thin films

Pure alpha-Al2O3 exhibits a very high degree of thermodynamical stability among all metal oxides and forms an inert oxide scale in a range of structural alloys at high temperatures. We report that amorphous Al2O3 thin films sputter deposited over crystalline Si instead show a surprisingly active interface. On annealing, crystallization begins with nuclei of a phase closely resembling gamma-Alumina forming almost randomly in an amorphous matrix, and with increasing frequency near the substrate/film interface. This nucleation is marked by the signature appearance of sharp (400) and (440) reflections and the formation of a diffuse diffraction halo with an outer maximal radius of approximate to 0.23 nm enveloping the direct beam. The microstructure then evolves by a cluster-coalescence growth mechanism suggestive of swift nucleation and sluggish diffusional kinetics, while locally the Al ions redistribute slowly from chemisorbed and tetrahedral sites to higher anion coordinated sites. Chemical state plots constructed from XPS data and simple calculations of the diffraction patterns from hypothetically distorted lattices suggest that the true origins of the diffuse diffraction halo are probably related to a complex change in the electronic structure spurred by the a-gamma transformation rather than pure structural disorder. Concurrent to crystallization within the film, a substantially thick interfacial reaction zone also builds up at the film/substrate interface with the excess Al acting as a cationic source. (C) 2015 AIP Publishing LLC.

An Electron-Microscope X-Ray-Diffraction And Amino-Acid-Analysis Study Of The Opercular Filament Cuticle Calcareous Opercular Plate And Habitation Tube Of Pomatoceros Lamarckii Quatrefages (Polychaeta Serpulidae)

The structure, X-ray diffraction and amino acid compositions of the opercular filament cuticle, calcareous opercular plate and habitation tube of the polychaete serpulid, Pomatoceros lamarckii quatrefages, are reported. The opercular filament cuticle is made up of protein and chitin. The chitin is probably in the crystallographic α form. The structure and amino acid composition of the organic components of the opercular filament cuticle and calcareous opercular plate have similarities but are distinctly different from those of the calcareous habitation tube. The opercular plate and habitation tube are composed of different polymorphs of calcium carbonate, aragonite and calcite respectively. Comparisons are made with other chitin-protein systems, structural and calcified proteins.

Measurements of the XUV transmission of aluminium with a soft x-ray laser

We have used XUV lasers to make absolute measurements of the photoabsorption coefficient of Al at energies just below that of the L3 absorption edge at 72.7 eV. Transmission measurements at photon energies of 53.7 and 63.3 eV have been made using Ne-like Ni and Ge XUV lasers. The XUV laser output was recorded in first and second orders using a flat-field spectrometer. Al foils with steps of various thicknesses were placed over the first order diffracted signal, while the second order diffraction was used to monitor the beam profile at each position. The transmission data agree extremely well with the original measurements at these wavelengths made by Henke and co-workers (Henke B L, Gullikson E M and Davis J C 1993 At. Data Nucl. Data Tables 54 18 1), but are in conflict with subsequent measurements which are currently in common use (Gullikson E M, Denham P, Mrowka S and Underwood J H 1994 Phys. Rev. B 49 16 283). The exact values of the absorption coefficients in this region of the spectrum have significant implications for the diagnosis of the energy and intensity output of XUV lasers.

IMAGING WITH THE VULCAN X-RAY LASER

An imaging microscope, comprising a Schwarzchild condenser and zone plate optical arrangement, has been established on the Vulcan Nd-glass laser system at the Rutherford Appleton Laboratory (RAL). Images of simple test structures have been taken in X-ray transmission using doublet X-ray laser radiation at 23.2 nm and 23.6 nm from collisionally pumped Ne-like germanium. Image resolution of about 0.15 mum has been measured.