Tomographic Study of Mesopore Formation in Ceria Nanorods.

Porosity in functional oxide nanorods is a recently discovered new type of microstructure, which is not yet fully understood and still under evaluation for its impact on applications in catalysis and gas/ion storage. Here we explore the shape and distribution of pores in ceria in three dimensions using a modified algorithm of geometric tomography as a reliable tool for reconstructing defective and strained nanoobjects. The pores are confirmed as "negative-particle" or "inverse-particle" cuboctahedral shapes located exclusively beneath the flat surface of the rods separated via a sub-5 nm thin ceria wall from the outside. New findings also comprise elongated "negative-rod" defects, seen as embryonic nanotubes, and pores in cube-shaped ceria. Furthermore, we report near-sintering secondary heat treatment of nanorods and cubes, confirming persistence of pores beyond external surface rounding. We support our experiments with molecular modeling and predict that the growth history of voids is via diffusion and aggregation of atomic point defects. In addition, we use density functional theory to show that the relative stability of pore (shape) increases in the order "cuboidal" < "hexagonal-prismatic" < "octahedral". The results indicate that by engineering voids into nanorods, via a high-temperature postsynthetic heat treatment, a potential future alternative route of tuning catalytic activities might become possible.

The relationship between particle morphology and rheological properties in injectable nano-hydroxyapatite bone graft substitutes.

Biomaterials composed of hydroxyapatite (HA) are currently used for the treatment of bone defects resulting from trauma or surgery. However, hydroxyapatite supplied in the form of a paste is considered a very convenient medical device compared to the materials where HA powder and liquid need to be mixed immediately prior to the bone treatment during surgery. In this study we have tested a series of hydroxyapatite (HA) pastes with varying microstructure and different rheological behaviour to evaluate their injectability and biocompatibility. The particle morphology and chemical composition were evaluated using HRTEM, XRD and FTIR. Two paste-types were compared, with the HA particles of both types being rod shaped with a range of sizes between 20 and 80nm while differing in the particle aspect ratio and the degree of roundness or sharpness. The pastes were composed of pure HA phase with low crystallinity. The rheological properties were evaluated and it was determined that the pastes behaved as shear-thinning, non-Newtonian liquids. The difference in viscosity and yield stress between the two pastes was investigated. Surprisingly, mixing of these pastes at different ratios did not alter viscosity in a linear manner, providing an opportunity to produce a specific viscosity by mixing the two materials with different characteristics. Biocompatibility studies suggested that there was no difference in vitro cell response to either paste for primary osteoblasts, bone marrow mesenchymal stromal cells, osteoblast-like cells, and fibroblast-like cells. This class of nanostructured biomaterial has significant potential for use as an injectable bone graft substitute where the properties may be tailored for different clinical indications.

Preparation and Antibacterial Properties of Silver-Doped Nanoscale Hydroxyapatite Pastes for Bone Repair and Augmentation.

The treatment of deep bone infections remains a significant challenge in orthopaedic and dental surgery. The relatively recent commercial manufacture of nanoscale hydroxyapatite has provided surgeons with an injectable biomaterial that promotes bone tissue regeneration, and with further modification it may be possible to incorporate antimicrobial properties into these devices. Silver-doped nanoscale hydroxyapatite pastes (0, 2, 5 and 10 mol.% silver) were prepared using a rapid mixing method. When the process was modified to prepare a 10 mol.% silver-doped material, silver phosphate was detected in addition to nanoscale hydroxyapatite. Thermal decomposition occurred more readily with greater silver content following calcination at 1000 °C for 2 h. Silver-doped nanoscale hydroxyapatite pastes showed antibacterial activity against Staphylococcus aureus and Pseudomonas aeruginosa in a dose dependent manner using both agar diffusion assays and suspension cultures. It was concluded that the enhanced antibacterial activity of the silver-doped pastes was due to the action of diffusible silver ions. Based on these results, silver-doped nanoscale hydroxyapatite pastes represent a highly promising new biomaterial system for the prevention and treatment of deep infections in bone tissue.

Reactive multilayers examined by HRTEM and plasmon EELS chemical mapping.

We examine chemical mapping of reaction phases in a Cu-Al multilayer system using low-loss electron energy loss spectroscopy spectrum imaging and image spectroscopy techniques. The sensitivity of the plasmon peak position and shape to various crystal structures and phases is exploited using postprocessing of spectra into second derivative plasmon maps and line scans. Analytical transmission electron microscopy is complemented by studies of the orientation relationship of the multilayer system using high-resolution electron microscopy of interfaces and selected area diffraction. The techniques have been applied to the Cu-Al multilayer sample and sharply bound epitaxial phases are found, before and after heat treatment.

Electron tomography of regularly shaped nanostructures under non-linear image acquisition.

Electron tomography allows the 3D quantitative characterization of nanostructures, provided a monotonic relationship is fulfilled between the projected signal and the atomic number and thickness of the specimen. This requirement is not satisfied if the micrographs are affected by (i) diffraction contrast, (ii) detector saturation or (iii) contrast inversion due to absorption (high-angle scattering) at high thickness. Artefacts related to the non-monotonic tomography acquisition are examined using computer simulations and experimental tilt series of tungsten tips and CeO(2) nanoparticles. Conditions are derived under which in spite of the non-linear artefacts the information is sufficient for reconstructing the 3D morphology of convex objects by geometric tomography.

MRT letter: full-tilt electron tomography with a piezo-actuated rotary drive.

Piezoelectric nanoactuation, which is rapidly becoming established as state-of-the-art positioning control in transmission electron microscopy (TEM), is extended here to include a rotational degree of freedom. A piezoelectric goniometer with both translational and rotary drive action has been designed with high level of miniaturization to fit into a standard TEM specimen holder shaft without compromising any of the performance of the default TEM goniometer and without any modifications to the TEM. Enhanced functionality of such a goniometer-in-goniometer is outlined and experimental results for electron tomography of nanostructures over a full tilt range of views, without any missing angles, are demonstrated.

Cerium and boron chemistry in doped borosilicate glasses examined by EELS.

Spatially resolved measurements of boron coordination and cerium valency in a doped borosilicate glass with crystalline nano-precipitates are described. The fine structure of the boron K-edge and the white-line ratio of the cerium M-edge doublet were evaluated from EELS line scans. Due to high beam sensitivity it was found that reliable boron-coordination measurements in some of the glasses studied required extrapolation of results acquired after different periods of irradiation back to a zero-irradiation. However, borosilicates that contained heavy alkali atoms were found to suffer very little structural change. The Ce valency of a 4% (molar) doped alkali-borosilicate glass was found to be mixed +III/+IV in the glass matrix and purely +IV (indicative of CeO2) in the precipitates. A significant dependency of the valence results on the data processing method was found and explained.

Subsurface nanoindentation deformation of Cu-Al multilayers mapped in 3D by focused ion beam microscopy.

A new technique for the three-dimensional analysis of subsurface damage of nanocomposites is presented. Cu-Al multilayers, grown epitaxially on (0001)Al2O3 single crystals by ultra high vacuum molecular beam epitaxy, have been deformed by nanoindentation. Systematic slicing and imaging of the deformed region by focused ion beam microscopy enables a 3D data set of the damaged region to be collected. From this 3D data set, profiles of the deformed sub-surface interfaces can be extracted. This enables the deformation of the individual layers, substrate and overall film thickness to be determined around the damage site. These 3D deformation maps have exciting implications for the analysis of mechanical deformation of nanocomposites on a sub-micrometre scale.

Probability calculus for quantitative HREM. Part I: Monte-Carlo and point cloud techniques.

A new approach to a central question of modern high-resolution electron microscopy (1-IREM) is presented: How precisely can we locate atom positions in crystal defects using computer-controlled structure retrieval algorithms? The purpose is not just to give error bars for the determined atomic column positions, but to derive estimations for the continuous probability functions. In the first part of this two-part paper, we present techniques which analyse point clouds of fluctuating fit-results for atom coordinates. The point clouds are obtained in a first approach from multiple input images differing in noise, commonly known as Monte-Carlo error estimation. Furthermore, we exploit the response obtained during a global optimisation-based refinement process for which all the trial structures are evaluated resulting in a second type of point cloud. In comparison, the Monte-Carlo-type technique turns out to be the most robust one. Using examples from current research on SrTiO3-bicrystals and Cu-Al2O3 interfaces, we study two largely different crystallographic and statistical situations.

Probability calculus for quantitative HREM. Part II: entropy and likelihood concepts.

The technique of extracting atomic coordinates from HREM images by R-factor refinement via iterative simulation and global optimisation is described in the context of probability density estimations for unknown parameters. In the second part of this two-part paper we discuss in comparison maximum likelihood and maximum entropy techniques with respect to their suitability of application within HREM. We outline practical difficulties of likelihood estimation and present a synthesis of two point-cloud techniques as a recommendable solution. This R-factor refinement with independent Monte-Carlo error calibration is a highly versatile method which allows adaptation to the special needs of HREM. Unlike simple text-book estimation methods, there is no requirement here on the noise being additive, uncorrelated, or Gaussian. It also becomes possible to account for a subset of systematic errors.

Direct versus iterative structure retrieval for a Cu/Ti misfit dislocation: a comparison of various 1Å HREM technologies.

Using an interface between Cu/Ti as an example, two HREM-based image analysis techniques, strain mapping and iterative digital image matching, are compared. The validity limit of these techniques is discussed as a function of specimen thickness and microscope technology. Two criteria are used to assess the limits: (i) the difference between two geometric phase maps, one calculated in image plane and one in object plane, and (ii) a difference image from two HREM simulations of two structure models differing in one atomic column. The latter displays the overall delocalisation of information by the microscope due to diffraction and imaging. It is outlined how far images and strain maps, obtained for high-voltage microscopy at 1250 kV and CS correction at 200 kV, are identical. Both techniques exhibit a significantly increased regime of applicability of strain mapping near defect cores. Simulations for a 400 kV HREM and a 300 kV FEGTEM with and without focal series reconstruction complement the study.