Search

Fast‐cooling after sintering or annealing of BiFeO3‐BaTiO3 mixed oxide ceramics yields core‐shell structures that give excellent functional properties, but their precise phase assemblage and nanostructure remains an open question. By comparing conventional electron energy loss spectroscopy (EELS) with scanning precession electron diffraction (SPED) mapping using a direct electron detector, we correlate chemical composition with the presence or absence of octahedral tilting and with changes in lattice parameters. This reveals that some grains have a 3‐phase assemblage of a BaTiO3‐rich pseudocubic shell; a BiFeO3‐rich outer core with octahedral tilting consistent with an R3c structure; and an inner core richer in Ba and even poorer in Ti, which seems to show a pseudocubic structure of slightly smaller lattice parameter than the shell region. This last structure has not been previously identified in these materials, but the composition and structure fit with previous studies. These inner cores are likely to be non‐polar and play no part in the ferroelectric properties. Nevertheless, the combination of EELS and SPED clearly provides a novel way to examine heterogeneous microstructures with high spatial resolution, thus revealing the presence of phases that may be too subtle to detect with more conventional techniques.

The use of fast pixelated detectors and direct electron detection technology is revolutionising many aspects of scanning transmission electron microscopy (STEM). The widespread adoption of these new technologies is impeded by the technical challenges associated with them. These include issues related to hardware control, and the acquisition, real-time processing and visualisation, and storage of data from such detectors. We discuss these problems and present software solutions for them, with a view to making the benefits of new detectors in the context of STEM more accessible. Throughout, we provide examples of the application of the technologies presented, using data from a Medipix3 direct electron detector. Most of our software is available under an open source licence, permitting transparency of the implemented algorithms, and allowing the community to freely use and further improve upon them., 16 pages, 7 figures, post revision

A carbon‐rich melt fragment from the Gardnos impact structure has been studied for a better understanding of the preservation and structural form(s) of carbon that have been processed by impact melting. The carbon was analyzed in situ in its original petrographic context within the melt fragment, using high‐resolution techniques including focused ion beam‐transmission electron microscopy and electron energy loss spectroscopy. Results show that the carbon is largely uniform and has a nanocrystalline grain size. The Gardnos carbon has a graphitic structure but with a large c/a ratio indicating disorder. The disorder could be a result of rapid heating to high temperatures during impact, followed by rapid cooling, with not enough time to crystallize into highly ordered graphite. However, temperature distribution during impact is extremely heterogenous, and the disordered Gardnos carbon could also represent material that avoided extreme temperatures, and thus, it was preserved. Understanding the structure of carbon during terrestrial impacts is important to help determine if the history of carbon within extraterrestrial samples is impact related. Furthermore, the degree of preservation of carbon during impact is key for locating and detecting organic compounds in extraterrestrial samples. This example from Gardnos, together with previous studies, shows that not all carbon is lost to oxidation during impact but that impact melting can encapsulate and preserve carbon where it is available.

The argon content of titanium dioxide doped tantalum pentoxide thin films was quantified in a spatially resolved way using HAADF images and DualEELS. Films annealed at 300$^{\circ}$C, 400$^{\circ}$C and 600$^{\circ}$C were investigated to see if there was a relationship between annealing temperature and bubble formation. It was shown using HAADF imaging that argon is present in most of these films and that bubbles of argon start to form after annealing at 400$^{\circ}$C and coarsen after annealing at 600$^{\circ}$C. A semi-empirical standard was created for the quantification using argon data from the EELS atlas and experimental data scaled using a Hartree Slater cross section. The density and pressure of argon within the bubbles was calculated for 35 bubbles in the 600$^{\circ}$C sample. The bubbles had a mean diameter, density and pressure of 22\r{A}, 870kg/m$^3$ and 400MPa, respectively. The pressure was calculated using the Van der Waals equation. The bubbles may affect the properties of the films, which are used as optical coatings for mirrors in gravitational wave detectors. This spatially resolved quantification technique can be readily applied to other small noble gas bubbles in a range of materials., Comment: 14 pages, 5 figures, data avilable at Enlighten: Research Data at 10.5525/gla.researchdata.1074

Fast pixelated detectors incorporating direct electron detection (DED) technology are increasingly being regarded as universal detectors for scanning transmission electron microscopy (STEM), capable of imaging under multiple modes of operation. However, several issues remain around the post acquisition processing and visualisation of the often very large multidimensional STEM datasets produced by them. We discuss these issues and present open source software libraries to enable efficient processing and visualisation of such datasets. Throughout, we provide examples of the analysis methodologies presented, utilising data from a 256$\times$256 pixel Medipix3 hybrid DED detector, with a particular focus on the STEM characterisation of the structural properties of materials. These include the techniques of virtual detector imaging; higher order Laue zone analysis; nanobeam electron diffraction; and scanning precession electron diffraction. In the latter, we demonstrate nanoscale lattice parameter mapping with a fractional precision $\le 6\times10^{-4}$ (0.06%)., 23 pages, 12 figures, add open data zenodo doi and revise precision discussion

Accelerated de novo formation of bone is a highly desirable aim of implants targeting musculoskeletal injuries. To date, this has primarily been addressed by biologic factors. However, there is an unmet need for robust, highly reproducible yet economic alternative strategies that strongly induce an osteogenic cell response. Here, we present a surface engineering method of translating bioactive nanopatterns from polymeric in vitro studies to clinically relevant material for orthopedics: three-dimensional, large area metal. We use a titanium-based sol-gel whereby metal implants can be engineered to induce osteoinduction both in vitro and in vivo. We show that controlled disordered nanotopographies presented as pillars with 15-25 nm height and 100 nm diameter on titanium dioxide effectively induce osteogenesis when seeded with STRO-1-enriched human skeletal stem cells in vivo subcutaneous implantation in mice. After 28 days, samples were retrieved, which showed a 20-fold increase in osteogenic gene induction of nanopatterned substrates, indicating that the sol-gel nanopatterning method offers a promising route for translation to future clinical orthopedic implants.

As the only stable binary compound formed between an alkali metal and nitrogen, lithium nitride possesses remarkable properties and is a model material for energy applications involving the transport of lithium ions. Following a materials design principle drawn from broad structural analogies to hexagonal graphene and boron nitride, we demonstrate that such low dimensional structures can also be formed from an s-block element and nitrogen. Both one- and two-dimensional nanostructures of lithium nitride, Li3N, can be grown despite the absence of an equivalent van der Waals gap. Lithium-ion diffusion is enhanced compared to the bulk compound, yielding materials with exceptional ionic mobility. Li3N demonstrates the conceptual assembly of ionic inorganic nanostructures from monolayers without the requirement of a van der Waals gap. Computational studies reveal an electronic structure mediated by the number of Li-N layers, with a transition from a bulk narrow-bandgap semiconductor to a metal at the nanoscale., Lithium nitride is the only stable binary alkali metal-nitrogen compound and shows promise for energy applications involving the transport of lithium ions. Here, the authors demonstrate that lithium nitride nanostructures can be grown as fibres and sheets despite the absence of a van der Waals gap.

Binding of nanoparticles (NPs) to mineral surfaces influences their transport through the environment. The potential, however, for growing minerals to immobilize NPs via occlusion (the process of trapping particles inside the growing mineral) has yet to be explored in environmentally relevant systems. In this study, the ureolytic bacteria Sporosarcina pasteurii was used to induce calcium carbonate precipitation in the presence of organo-metallic manufactured nanoparticles. As calcite crystals grew the nanoparticles in the solution became trapped inside these crystals. Capture of NPs within the calcite via occlusion was verified by transmission electron microscopy of thin foils. Nanoparticles with a negative surface charge were captured with greater efficiency than those with a positive surface charge, resulting from stronger attachment of negative nanoparticles to the positively charged calcite surfaces, which in turn facilitated occlusion. Thermodynamic and kinetic analysis, however, did not reveal a significant difference in kp (calcite precipitation rate constant) or the critical saturation at which precipitation initiates (Scrit), indicating the presence of different charged nanoparticles did not influence calcite precipitation at the concentrations used here. Overall, these findings demonstrate that microbially driven mineral precipitation has potential to immobilize nanoparticles in the environment via occlusion Binding of nanoparticles (NPs) to mineral surfaces influences their transport through the environment. The potential, however, for growing minerals to immobilize NPs via occlusion (the process of trapping particles inside the growing mineral) has yet to be explored in environmentally relevant systems. In this study, the ureolytic bacteria Sporosarcina pasteurii was used to induce calcium carbonate precipitation in the presence of organo-metallic manufactured nanoparticles. As calcite crystals grew the nanoparticles in the solution became trapped inside these crystals. Capture of NPs within the calcite via occlusion was verified by transmission electron microscopy of thin foils. Nanoparticles with a negative surface charge were captured with greater efficiency than those with a positive surface charge, resulting from stronger attachment of negative nanoparticles to the positively charged calcite surfaces, which in turn facilitated occlusion. Thermodynamic and kinetic analysis, however, did not reveal a significant difference in kp (calcite precipitation rate constant) or the critical saturation at which precipitation initiates (Scrit), indicating the presence of different charged nanoparticles did not influence calcite precipitation at the concentrations used here. Overall, these findings demonstrate that microbially driven mineral precipitation has potential to immobilize nanoparticles in the environment via occlusion.

The atomic structure of mixtures of titania (TiO_2) and tantala (Ta_2O_5) ion-beam sputtered amorphous thin film coatings at various post-deposition annealing temperatures have been studied using Ta LIII and Ti K edge Extended X-ray Absorption Fine Structure (EXAFS). The results indicate that post-deposition annealing produces subtle changes in the short range order (< 1 nm) for samples which remain amorphous. We also show that titania–tantala mixtures maintain a structure similar to that of pure tantala, with the titanium atoms preferring to sit at the second shell distance, which is similar to the Ta–Ta distance seen in the pure tantala structure. A discussion is also included on interpretation of the general trends identified in the EXAFS data and how this relates to previous and ongoing studies of the structure and mechanical loss measurements of titania–tantala coatings.

Electron energy-loss spectroscopy (EELS) is used to investigate the association of hydrogen with helium bubbles in zirconium. Conventional EELS data yield a signal at 13.5 eV (similar to the hydrogen K-edge, 13 eV), which is spatially distributed around the peripheries of bubbles and may correlate with the concentration of hydrogen/deuterium in the material. Ultra-high energy resolution EELS yields a signal at 148.6 meV (comparable to a range of ZrH bonds, 130–156 meV) from a region containing bubbles and no visible hydrides. These signals are interpreted in the context of either bubble surface chemisorption or bubble stress field trapping mechanisms.

A Ge-SiGe multiple quantum well structure created by low energy plasma enhanced chemical vapour deposition, with nominal well thickness of 5.4 nm separated by 3.6 nm SiGe spacers, is analysed quantitatively using scanning transmission electron microscopy. Both high angle annular dark field imaging and electron energy loss spectroscopy show that the interfaces are not completely sharp, suggesting that there is some intermixing of Si and Ge at each interface. Two methods are compared for the quantification of the spectroscopy datasets: a self-consistent approach that calculates binary substitutional trends without requiring experimental or computational k-factors from elsewhere and a standards-based cross sectional calculation. Whilst the cross section approach is shown to be ultimately more reliable, the self-consistent approach provides surprisingly good results. It is found that the Ge quantum wells are actually about 95% Ge and that the spacers, whilst apparently peaking at about 35% Si, contain significant interdiffused Ge at each side. This result is shown to be not just an artefact of electron beam spreading in the sample, but mostly arising from a real chemical interdiffusion resulting from the growth. Similar results are found by use of X-ray diffraction from a similar area of the sample. Putting the results together suggests a real interdiffusion with a standard deviation of about 0.87 nm, or put another way—a true width defined from 10%–90% of the compositional gradient of about 2.9 nm. This suggests an intrinsic limit on how sharp such interfaces can be grown by this method and, whilst 95% Ge quantum wells (QWs) still behave well enough to have good properties, any attempt to grow thinner QWs would require modifications to the growth procedure to reduce this interdiffusion, in order to maintain a composition of ≥95% Ge.

The nakhlite meteorites are clinopyroxenites that are derived from a ~1300 million year old sill or lava flow on Mars. Most members of the group contain veins of iddingsite whose main component is a fine-grained and hydrous Fe- and Mg-rich silicate. Siderite is present in the majority of veins, where it straddles or cross-cuts the Fe-Mg silicate. This carbonate also contains patches of ferric (oxy)hydroxide. Despite 40 years of investigation, the mineralogy and origins of the Fe-Mg silicate is poorly understood, as is the paragenesis of the iddingsite veins. Nanometer-scale analysis of Fe-Mg silicate in the Nakhla meteorite by electron and X-ray imaging and spectroscopy reveals that its principal constituents are nanoparticles of opal-A. This hydrous and amorphous phase precipitated from acidic solutions that had become supersaturated with respect to silica by dissolution of olivine. Each opal-A nanoparticle is enclosed within a ferrihydrite shell that formed by oxidation of iron that had also been liberated from the olivine. Siderite crystallized subsequently and from solutions that were alkaline and reducing, and replaced both the nanoparticles and olivine. The fluids that formed both the opal-A/ferrihydrite and the siderite were sourced from one or more reservoirs in contact with the Martian atmosphere. The last event recorded by the veins was alteration of the carbonate to a ferric (oxy)hydroxide that probably took place on Mars, although a terrestrial origin remains possible. These results support findings from orbiter- and rover-based spectroscopy that opaline silica was a common product of aqueous alteration of the Martian crust.

Magnesium hydroxide nanoplates ca. 50 nm in thickness can be prepared over minute timescales via hydrothermal synthesis in a multimode cavity (MMC) microwave reactor. This approach allows ca. 1 g of single-phase Mg(OH)2 to be synthesised in less than 3 minutes without the requirement of surfactants or non-aqueous solvents. The hydroxide nanomaterial dehydrates at temperatures >200 K below that of the equivalent bulk material and can be utilised as a precursor for the pseudomorphic synthesis of nanoplates of MgO as investigated by TG-DTA-MS, PXD and SEM measurements. Equally, the pseudomorphic synthesis can be performed by irradiating the Mg(OH)2 nanomaterial with microwaves for 6 minutes to produce single-phase MgO.

A detailed characterization of nanostructured thin zirconium oxide films formed during aqueous corrosion of a nuclear-grade zirconium alloy (Zircaloy-4) has been carried out by means of two novel, ultra-high-spatial-resolution grain mapping techniques, namely automated crystal orientation mapping in the transmission electron microscope (TEM) and transmission electron backscatter diffraction (t-EBSD). While the former provided excellent spatial resolution with the ability to identify tetragonal ZrO2 grains as small as ∼5 nm, the superior angular resolution and unambiguous indexing with t-EBSD enabled verification of the TEM observations. Both techniques revealed that in a stress-free condition (TEM foil prepared by focused ion beam milling), the oxide consists mainly of well-oriented columnar monoclinic grains with a high fraction of transformation twin boundaries, which indicates that the transformation from tetragonal to monoclinic ZrO2 is a continuous process, and that a significant fraction of the columnar grains transformed from stress-stabilized tetragonal grains with (0 0 1) planes parallel to the metal-oxide interface. The TEM analysis also revealed a small fraction of size-stabilized, equiaxed tetragonal grains throughout the oxide. Those grains were found to show significant misalignment from the expected (0 0 1) growth direction, which explains the limited growth of those grains. The observations are discussed in the context of providing new insights into corrosion mechanisms of zirconium alloys, which is of particular importance for improving service life of fuel assemblies used in water-cooled reactors. © 2014 Acta Materialia Inc. Published by Elsevier Ltd.

Scanning transmission electron microscopy (STEM) data with atomic resolution can contain a large amount of information about the structure of a crystalline material. Often, this information is hard to extract, due to the large number of atomic columns and large differences in intensity from sublattices consisting of different elements. In this work, we present a free and open source software tool for analysing both the position and shapes of atomic columns in STEM-images, using 2-D elliptical Gaussian distributions. The software is tested on variants of the perovskite oxide structure. By first fitting the most intense atomic columns and then subtracting them, information on all the projected sublattices can be obtained. From this, we can extract changes in the lattice parameters and shape of A-cation columns from annular dark field images of perovskite oxide heterostructures. Using annular bright field images, shifts in oxygen column positions are also quantified in the same heterostructure. The precision of determining the position of atomic columns is compared between STEM data acquired using standard acquisition, and STEM-images obtained as an image stack averaged after using non-rigid registration. © The Author(s) 2017. This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.

Mid-infrared intersubband absorption from p-Ge quantum wells with Si 0.5 Ge 0.5 barriers grown on a Si substrate is demonstrated from 6 to 9 μm wavelength at room temperature and can be tuned by adjusting the quantum well thickness. Fourier transform infra-red spectroscopy measurements demonstrate clear absorption peaks corresponding to intersubband transitions among confined hole states. The work indicates an approach that will allow quantum well intersubband photodetectors to be realized on Si substrates in the important atmospheric transmission window of 8–13 μm.

Methods are described for measuring accurate absolute experimental inelastic mean free paths and differential cross-sections using DualEELS. The methods remove the effects of surface layers and give the results for the bulk materials. The materials used are VC0.83, TiC0.98, VN0.97 and TiN0.88 but the method should be applicable to a wide range of materials. The data was taken at 200keV using a probe half angle of 29mrad and a collection angle of 36mrad. The background can be subtracted from under the ionisation edges, which can then be separated from each other. This is achieved by scaling Hartree-Slater calculated cross-sections to the edges in the atomic regions well above the threshold. The average scaling factors required are 1.00 for the non-metal K-edges and 1.01 for the metal L-edges (with uncertainties of a few percent). If preliminary measurements of the chromatic effects in the post-specimen lenses are correct, both drop to 0.99. The inelastic mean free path for TiC0.98 was measured as 103.6±0.5nm compared to the prediction of 126.9nm based on the widely used Iakoubovskii parameterisation.

JAM would like to acknowledge the School of Chemistry, University of St Andrews for the allocation of a PhD studentship through the EPSRC doctoral training grant (EP/ K503162/1). The work carried out at the University of St Andrews and Queens University Belfast was carried out as part of an EPSRC-funded collaboration (EP/P02453X/1 and EP/P024637/1). The work carried out at the University of Glasgow was carried out as part of the EPSRC-funded CDT in Photonic Integration and Advanced Data Storage (EP/L015323/1). TTT and PSH thank the Welch Foundation (Grant E-1457) and NSF (DMR-1503573) for support. Since the observation that the properties of ferroic domain walls (DWs) can differ significantly from the bulk materials in which they are formed, it has been realized that domain wall engineering offers exciting new opportunities for nanoelectronics and nanodevice architectures. Here, a novel improper ferroelectric, CsNbW2O9, with the hexagonal tungsten bronze structure, is reported. Powder neutron diffraction and symmetry mode analysis indicate that the improper transition (TC = 1100 K) involves unit cell tripling, reminiscent of the hexagonal rare earth manganites. However, in contrast to the manganites the symmetry breaking in CsNbW2O9 is electronically driven (i.e., purely displacive) via the second-order Jahn-Teller effect in contrast to the geometrically-driven tilt mechanism of the manganites. Nevertheless CsNbW2O9 displays the same kinds of domain microstructure as those found in the manganites, such as the characteristic six-domain "cloverleaf" vertices and DW sections with polar discontinuities. The discovery of a completely new material system, with domain patterns already known to generate interesting functionality in the manganites, is important for the emerging field of DW nanoelectronics. Postprint

Graphical abstract, Highlights • Direct nanopatterning of titanium using nanopatterned diamond based stamps. • Quantify nanopillar matrix imprint depth with regards to feature size and density. • An account of a novel method of reducing the imprint load required to emboss titanium. • TEM and EELS analysis following our load reduction treatment. • The first demonstration of nanopatterning curved, bulk titanium., In this work the direct transfer of nanopatterns into titanium is demonstrated. The nanofeatures are imprinted at room temperature using diamond stamps in a single step. We also show that the imprint properties of the titanium surface can be altered by anodisation yielding a significant reduction in the required imprint force for pattern transfer. The anodisation process is also utilised for curved titanium surfaces where a reduced imprint force is preferable to avoid sample deformation and damage. We finally demonstrate that our process can be applied directly to titanium rods.

Ge on Si micro-disk, ring and racetrack cavities are fabricated and strained using silicon nitride stressor layers. Photoluminescence measurements demonstrate emission at wavelengths ≥ 2.3 μm, and the highest strained samples demonstrate in-plane, tensile strains of > 2%, as measured by Raman spectroscopy. Strain analysis of the micro-disk structures demonstrate that shear strains are present in circular cavities, which can detrimentally effect the carrier concentration for direct band transitions. The advantages and disadvantages of each type of proposed cavity structure are discussed.

Mid-infrared intersubband absorption from p-Ge quantum wells with Sio.sGeo.s barriers grown on a Si substrate is demonstrated from 6 to 9 μm wavelength at room temperature and can be tuned by adjusting the quantum well thickness.

The discovery of unusual nanorod precipitates in bismuth ferrite doped with Nd and Ti is reported. The atomic structure and chemistry of the nanorods are determined using a combination of high angle annular dark field imaging, electron energy loss spectroscopy, and density functional calculations. It is found that the structure of the BiFeO3 matrix is strongly modified adjacent to the precipitates; the readiness of BiFeO3 to adopt different structural allotropes in turn explains why such a large axial ratio, uncommon in precipitates, is stabilized. In addition, a correlation is found between the alignment of the rods and the orientation of ferroelastic domains in the matrix, which is consistent with the system's attempt to minimize its internal strain. Density functional calculations indicate a finite density of electronic states at the Fermi energy within the rods, suggesting enhanced electrical conductivity along the rod axes, and motivating future investigations of nanorod functionalities.

Lanthanum doping of zirconium rich lead zirconate titanate gives rise to incommensurate, long-period antiferroelectric structures. The structure of two stacking sequences in this incommensurate phase is determined using quantitative analysis of high-resolution scanning transmission electron microscopy images, with the lead atom positions located with an exceptional precision of about 6 pm. This allows the estimation of local polarisation variations across the stacking units, and the polarisation varies in an approximately sinusoidal fashion along the stacking direction. The measured peak Pb atom displacements of about 28 pm and peak polarisation values of about 60 mu C cm-2 match extremely well to reported values for the commensurate antiferroelectric PbZrO3 phase.

Parallel stacking faults on (010) planes are frequently observed in hot-pressed Y2Si2O7. A combination of conventional dark-field imaging and high-resolution transmission electron microscopy was used to investigate the structure of these faults and it was found that they consist of the repeat of one layer of the two layer γ-Y2Si2O7 structure with an associated in-plane rigid body displacement. The resulting structure was confirmed by image simulation of high-resolution images from two perpendicular projections. A model for the formation of the stacking faults is proposed as a consequence of a transformation from β-Y2Si2O7 to γ-Y2Si2O7 in the hot pressing.

Hot-pressed yttrium disilicate ceramics have been characterized using analytical transmission electron microscopy (TEM). The microstructure consists of large grains of the γ phase of stoichiometric γ-Y2Si2O7 containing rounded glassy Y-doped SiO2 inclusions; excess glassy SiO2-rich material is also found at the grain boundaries. Two main reasons are found for the inhomogeneity: a slight SiO2 excess is inferred from the composition measurements, and the LiF flux used in hot pressing would also promote glass formation. Improved high-temperature mechanical properties would only be possible if residual glass formation was minimized, strategies for doing so are discussed, and the importance of analytical TEM for studying such submicron scale inhomogeneity is underlined.

Ultramicroscopy 154, 57-63 (2015). doi:10.1016/j.ultramic.2015.03.016, Published by Elsevier Science, Amsterdam

The atomic structure and chemistry of thin films of Bi(Fe,Mn)O-3 (BFMO) films with a target composition of Bi2FeMnO6 on SrTiO3 are studied using scanning transmission electron microscopy imaging and electron energy loss spectroscopy. It is shown that Mn4+-rich antiphase boundaries are locally nucleated right at the film substrate and then form stepped structures that are approximately pyramidal in three dimensions. These have the effect of confining the material below the pyramids in a highly strained state with an out-of-plane lattice parameter close to 4.1 angstrom. Outside the area enclosed by the antiphase boundaries, the out-of-plane lattice parameter is much closer to bulk values for BFMO. This suggests that to improve the crystallographic perfection of the films whilst retaining the strain state through as much of the film as possible, ways need to be found to prevent nucleation of the antiphase boundaries. Since the antiphase boundaries seem to form from the interaction of Mn with the Ti in the substrate, one route to perform this would be to grow a thin buffer layer of pure BiFeO3 on the SrTiO3 substrate to minimise any Mn-Ti interactions.

Materials science and technology : MST 32(3, Special Issue: SI), 242-247 (2015). doi:10.1179/1743284715Y.0000000115, Published by Taylor and Francis, London

We report the synthesis of stearate functionalized nanobubbles of SiO2 with a few aniline\ud molecules inside, represented as C6H5NH2@SiO2@stearate, exhibiting fluorescence with red-shifted\ud emission. Stearic acid functionalization allows the materials to be handled just as free molecules, for dissolution,\ud precipitation, storage etc. The methodology adopted involves adsorption of aniline on the surface of\ud gold nanoparticles with subsequent growth of a silica shell through monolayers, followed by the selective\ud removal of the metal core either using sodium cyanide or by a new reaction involving halocarbons. The\ud material is stable and can be stored for extended periods without loss of fluorescence. Spectroscopic and\ud voltammetric properties of the system were studied in order to understand the interaction of aniline with\ud the shell as well as the monolayer, whilst transmission electron microscopy has been used to study the\ud silica shell.

The paper presents an overview of a number of unusual phase transformations which take place in pearlitic steels in conditions of the severe deformation, i.e. combination of high pressure and strong shear strain. Strain-induced cementite dissolution is a well-documented phenomenon, which occurs during cold plastic deformation of pearlitic steels. Recently new results which can shed additional light on the mechanisms of this process were obtained thanks to 3DAP and HRTEM investigations of pearlitic steel deformed by high pressure torsion (HPT). It was shown that the process of cementite decomposition starts by carbon depletion from the carbides, which indicates that the deviation of cementite’s chemical composition from the stoichiometric is the main reason for thermodynamic destabilisation of cementite during plastic deformation. Important results were obtained regarding the distribution of released carbon atoms in ferrite. It was experimentally confirmed that carbon segregates to the dislocations and grain boundaries of nanocrystalline ferrite. Another unusual phase transformation taking place in nanocrystalline pearlitic steel during room temperature HPT is a stress induced α→γ transformation, which never occurs during conventional deformation of coarse grained iron and carbon steels. It was concluded that this occurred due to a reverse martensitic transformation. The atomistic mechanism and the thermodynamics of the transformation, as well as issues related to the stability of the reverted austenite will be discussed.

Transmission electron microscopy has been used to investigate the junction between two lamellar bands in a tetragonal lead zirconate titanate (PZT) ceramic. It is found that significant bending occurs in the area due to the matching of different domains on planes. Analysis of CBED patterns shows that the orientation relationships between the long boundaries between lamellae is much as expected and allows quantification of local c/a ratios. The short boundaries at the band junction, however, are highly stressed and deviate significantly from ideal misorientation values. This reveals that the areas between the 4- domain junctions in the band junction are highly stressed with peak stresses in the GPa range, which are highly likely to function as the source of microcracks under the additional strains found in device application.

Carbon onions have been known since Iijima first observed them in 1980 [1]. In 1992 Ugarte et al. made carbon onions by irradiating carbon soot by an intense electron beam in a transmission electron microscope [2]. There are reports in the literature on the production of carbon structures in water medium by generating an electric arc to create high temperatures [3,4]. It was found that several metals including gold catalyze carbon onion growth from various precursor species. Multiwalled carbon nanotubes have also been coated with silica (SiO2) [5,6]. It has previously been demonstrated that gold and silver nanoparticles react with halocarbons leading to the complete leaching of the metals along with deposition of carbon in an amorphous form [7]. This method, if used with core–shell nanoparticles such as Au@SiO2 [8] makes possible the deposition of amorphous carbon species inside ceramic nanoshells. The nano dimension of the cavity may force a reaction between the carbon species in the solution phase itself, with or without catalysis by the metals or their ions. With this conjecture, we investigated the metal oxide nanoshells after leaching the metal core of core–shell nanoparticles. Carbon onion structures within silica shells were detected in these experiments. It may be noted that the main objective of this work is not to introduce a new method for the synthesis of carbon onions, but to introduce a new material where carbon onions have been made inside the silica shell. Chloroauric acid and trisodium citrate were purchased from CDH fine chemicals, India. (3-amino) propyl trimethoxysilane (APS) and tetra methoxysilane (TMS) were purchased from Aldrich and were used without additional purification. Ethanol and 2-propanol were purchased from E. Merck. CCl4 was purchased from Ranbaxy Chemicals, India. Triply distilled water was used for all the experiments. Gold nanoparticles of size 15 nm were prepared using the Turkevich reduction method [9]. In order to cover this gold particle with silica, a method adopted by Makarova et al. [10] was followed. Further growth of the silica shell was achieved by following the Stober method [11]. To 50 ml of the gold sol, 0.25 ml of millimolar solution of freshly prepared solution of 3-aminopropyl trimethoxysilane (APS) was added with vigorous stirring. This mixture was allowed to stand for around 15 min for complete complexation. A solution of active silica was prepared by adjusting the pH to 10–11 of a 0.54 wt.% of sodium silicate solution by progressive addition of a cation exchange resin, Dualite C 225–Na 14–52 mesh. Two milliliters of active silica thus prepared was added to 50 ml of the surface modified gold sol. The resulting mixture was allowed to stand for one day so that the active silica polymerizes on the surface of the gold particle to form Au@SiO2. The solution thus obtained was centrifuged for around 1 h and the particles were collected and re-dispersed in about 50 ml of 2propanol. To this solution, around 5 ml of CCl4 solution was added. The reaction between themetal core and CCl4 happens over a period of several days and was studied by UV/Vis spectroscopy in a time dependent manner. It was found that the reaction between the gold nanoparticle and CCl4 is quite slow and the reason for this slow rate may be the thickness of the silica shell. It is reported that silica covering of Au@SiO2 is porous in nature, and gold core is accessible for halocarbons. Earlier studies including ours onAu@SiO2 shows that after leaching the core with CN ion a well-defined shell exists showing that shell is permeable for ions [10] and possibly, molecules. Same way clear shells were seen in the case of mineralization of silver core of Ag@ZrO2 using CCl4 [12]. The plasmon absorption of the Au@SiO2 nanoparticles at 524 nm progressively reduces in intensity as the reaction occurs. Once the reaction is complete, a peak corresponding to Au3þ appears at around 320 nm in the UV/Vis spectrum of the solution. Chlorine is removed as Cl . At this point, the solution is pale yellow in

We report a new nanomaterial in which ciprofloxacin molecules are incorporated inside silica nanobubbles, denoted as ciprofloxacin@SiO2. The material has been characterised using UV/Vis absorption spectroscopy, transmission electron microscopy, cyclic voltammetry, and emission spectroscopy. The material is stable and the freestanding particles can be precipitated and redispersed in several solvents. Confinement of the molecule is complete as leaching through the shell is minimal. The material behaves like free ciprofloxacin in solution; however, effects of confinement are manifested. Energy transfer reaction between ciprofloxacin@SiO2 and Tb3+ was monitored by emission spectroscopy. The emission intensity decreased with metal ion exposure indicating selective electronic interaction.

The grain growth and densification have been investigated in very high-purity α-alumina doped with varying amounts of yttrium (0 to 3000 wt ppm of yttria) and sintered in air at 1450, 1550 and 1650 °C. Yttrium doping inhibited densification and coarsening at 1450 °C, but had very little effect at 1550 °C and no effect at 1650 °C. The change in densification behaviour is suggested to be related to the transition with increasing temperature from grain boundary diffusion to lattice diffusion controlled densification. The coarsening rate increases faster with temperature than the densification rate. This was correlated with a higher measured activation energy for grain growth than for the diffusion processes, which control the densification.

The segregation behaviour of a cation (yttrium) with a low solubility in the polycrystalline oxide host (α-Al2O3) has been investigated at temperatures between 1450 and 1650°C using analytical scanning transmission electron microscopy. Three distinct segregation regimes were identified. In the first, the yttrium adsorbs to all grain boundaries with a high partitioning coefficient, and this can be modelled using a simple McLean-Langmuir type absorption isotherm. In the second, a noticeable deviation from this isotherm is observed and the grain boundary excess reaches a maximum of 9 Y-cat/nm2 and precipitates of a second phase (yttrium aluminate garnet, YAG) start to form. In the third regime, the grain boundary excess of the cation settles down to a value of 6–7 Y-cat/nm2 that is in equilibrium with the YAG precipitates. In a material (accidentally) co-doped with Zr, the Zr seems to behave in a similar way to the Y and the Y + Zr grain boundary excess behaves in the same way as the Y grain boundary excess in the pure Y-doped system. In this latter system, Y-stabilised cubic zirconia is precipitated in addition to YAG at higher Y + Zr concentrations.

A self doping contact consisting of a silver/antimony alloy that produces an Ohmic contact to moderately doped n-type germanium (doped to a factor of four above the metal-insulator transition) has been investigated. An evaporation of a mixed alloy of Ag/Sb (99%/1%) onto n-Ge ( ND=1×1018 cm−3) annealed at 400 °C produces an Ohmic contact with a measured specific contact resistivity of (1.1±0.2)×10−5 Ω-cm2. It is proposed that the Ohmic behaviour arises from an increased doping concentration at the Ge surface due to the preferential evaporation of Sb confirmed by transmission electron microscope analysis. It is suggested that the doping concentration has increased to a level where field emission will be the dominate conduction mechanism. This was deduced from the low temperature electrical characterisation of the contact, which exhibits Ohmic behaviour down to a temperature of 6.5 K.

To achieve optimal mechanical properties in high manganese steels, the precipitation of nanoprecipitates of vanadium and niobium carbides is under investigation. It is shown that under controlled heat treatments between 850°C and 950°C following hot deformation, few-nanometre precipitates of either carbide can be produced in test steels with suitable contents of vanadium or niobium. The structure and chemistry of these precipitates are examined in detail with a spatial resolution down to better than 1 nm using a newly commissioned scanning transmission electron microscope. In particular, it is shown that the nucleation of vanadium carbide precipitates often occurs at pre-existing titanium carbide precipitates which formed from titanium impurities in the bulk steel. This work will also highlight the links between the nanocharacterisation and changes in the bulk properties on annealing.

Using the white line intensities, electron energy-loss spectroscopy in a transmission electron microscope has been applied to characterizing the valence state of manganese in the system (La1−xYx)0.5(Ca1−ySry)0.5MnO3 at room temperature and lower temperature (93 K), respectively. The results show that the valence state of manganese keeps consistent (close to 3.5) in this system at room temperature and lower temperature.

Electron energy-loss spectroscopy (EELS) has been used to determine the valence state of manganese for all the samples at low temperature (93 K). EELS results indicate that the valence state of manganese keeps constant (∼3.5) for all the samples. The effects of the A-site cation size mismatch on the charge ordering (CO) behaviors in the manganites (La1−xYx)0.5(Ca1−ySry)0.5MnO3 are studied by transmission electron microscopy (TEM). TEM images show that the size mismatch and disorder of A-site cations have a suppression effect on the CO transition. The schematic models are proposed for the incommensurate CO modulation in the samples with size mismatch σ2⩽0.003. The disappearance of the CO transition in the sample with the largest mismatch (σ2=0.005) is explained by the random arrangements of Mn3+ and Mn4+ ions.

Transmission electron microscopy (TEM) has been conducted on the ferroelectric domain structure in Pb(Zr, Ti)O3 (PZT), SrBi2Ta2O9 (SBT) and Bi4Ti3O12 (BTO). Using space group analysis it may be shown that only 90° and 180° domain walls can exist in PZT, whereas in SBT and BTO, which both have layered perovskite structure, anti-phase boundaries (APBs) may also exist. APBs in SBT have been identified using TEM observations, but have not been found in BTO. Based on the in-situ TEM study on the mobility of polarization domains in SBT, a new switching mechanism is proposed, which may explain the difference in fatigue properties between PZT, SBT and BTO.

The formation mechanisms of barium titanate particles from an amorphous TiO2 gel during synthesis in aqueous solution at temperatures between 20 and 80°C have been investigated. It was found that barium ions diffuse into the gel almost immediately, with nanocrystalline BaTiO3 particles being formed after heating to just 40°C. These particles grew to dimensions of about 100 nm as the temperature was increased to 80°C, consuming the remaining TiO2 gel. Some remnants of gel were found on particle surfaces in a sample taken at this temperature but after holding the sol at 80°C for 2 or 4 h, the particle surfaces became “cleaner” and more rounded. It is proposed on the basis of these observations that the BaTiO3 particles were formed by an in-situ transformation of the amorphous TiO2 gel. The mechanism by which (i) the particles were then rounded off and (ii) the final gel fragments were incorporated into the main BaTiO3 particles was, however, less clear.

Powders of the microwave dielectric material barium magnesium tantalate Ba(Mg1/3Ta2/3)O3 have been produced by hydrothermal synthesis at moderately low temperatures (160 to 350°C). It was found that while it is relatively straightforward to produce the material in the desired perovskite phase at or below 200°C, the powder particles tend to be highly irregular in morphology with extremely small dimensions (of the order of 10 nm) and deficient in magnesium (with some precipitation of the excess magnesium as the hydroxide). The effects of both higher synthesis temperatures and different feedstock preparation were thus investigated with the aim of improving the precipitation of magnesium under hydrothermal conditions in order to produce a more homogeneous, stoichiometric powder and significant progress was made. It was found that when near-stoichiometric particles are formed, they adopt rounded morphologies and exhibit larger particle sizes (around 30–50 nm). These results show that the hydrothermal feedstock and the synthesis temperature used have a profound effect on particle stoichiometry, which in turn affects the growth morphology of the particles.

A transmission electron microscopy study and geometric analysis has been performed on a vicinal 78.7° high-angle grain boundary in pure Ti which has mixed tilt-twist character and exhibits a characteristic dislocation arrangement. There is no feasible constrained coincident site lattice which could be adopted as the reference structure by this boundary and an alternative structure is proposed which corresponds to a two-dimensional atomic arrangement inclined at about 18° to the boundary plane. The dislocation configuration required to accommodate the deviation from the reference structure orientation was predicted using an O-lattice algorithm for class 1 interfacial dislocations and this matched well the arrangement observed experimentally.

The structure of a near-tilt grain boundary with o=12.29degree in deformed and annealed Ti has been studied using transmission electron microscopy. The observed structure has been compared with modelled structures and shown to be a good match to that expected for a stepped low-angle grain boundary.

A high angle grain boundary in titanium containing a regular dislocation network has been studied using transmission electron microscopy. It was shown that the reference structure for this grain boundary was unlikely to be a CCSL and that a more feasible reference structure corresponded to the existence of near-2d periodicity in a plane which made a small angle with the grain boundary plane. The dislocation arrangement that would be required to accommodate the angular deviation from the relative orientation for this reference structure was calculated using an 'O' lattice method. This showed a good semi-quantitative agreement with that which was observed experimentally indicating that the proposed reference structure was the one adopted by this grain boundary.