Calcite incorporated in silica/collagen xerogels mediates calcium release and enhances osteoblast proliferation and differentiation.

Multiphasic silica/collagen xerogels are biomaterials designed for bone regeneration. Biphasic silica/collagen xerogels (B30) and triphasic xerogels (B30H20 or B30CK20) additionally containing hydroxyapatite or calcite were demonstrated to exhibit several structural levels. On the first level, low fibrillar collagen serves as template for silica nanoparticle agglomerates. On second level, this silica-enriched matrix phase is fiber-reinforced by collagen fibrils. In case of hydroxyapatite incorporation in B30H20, resulting xerogels exhibit a hydroxyapatite-enriched phase consisting of hydroxyapatite particle agglomerates next to silica and low fibrillar collagen. Calcite in B30CK20 is incorporated as single non-agglomerated crystal into the silica/collagen matrix phase with embedded collagen fibrils. Both the structure of multiphasic xerogels and the manner of hydroxyapatite or calcite incorporation have an influence on the release of calcium from the xerogels. B30CK20 released a significantly higher amount of calcium into a calcium-free solution over a three-week period than B30H20. In calcium containing incubation media, all xerogels caused a decrease in calcium concentration as a result of their bioactivity, which was superimposed by the calcium release for B30CK20 and B30H20. Proliferation of human bone marrow stromal cells in direct contact to the materials was enhanced on B30CK20 compared to cells on both plain B30 and B30H20.

Electron-beam induced synthesis of nanostructures: a review.

As the success of nanostructures grows in modern society so does the importance of our ability to control their synthesis in precise manners, often with atomic precision as this can directly affect the final properties of the nanostructures. Hence it is crucial to have both deep insight, ideally with real-time temporal resolution, and precise control during the fabrication of nanomaterials. Transmission electron microscopy offers these attributes potentially providing atomic resolution with near real time temporal resolution. In addition, one can fabricate nanostructures in situ in a TEM. This can be achieved with the use of environmental electron microscopes and/or specialized specimen holders. A rather simpler and rapidly growing approach is to take advantage of the imaging electron beam as a tool for in situ reactions. This is possible because there is a wealth of electron specimen interactions, which, when implemented under controlled conditions, enable different approaches to fabricate nanostructures. Moreover, when using the electron beam to drive reactions no specialized specimen holders or peripheral equipment is required. This review is dedicated to explore the body of work available on electron-beam induced synthesis techniques with in situ capabilities. Particular emphasis is placed on the electron beam-induced synthesis of nanostructures conducted inside a TEM, viz. the e-beam is the sole (or primary) agent triggering and driving the synthesis process.

Flash Joule heating for ductilization of metallic glasses.

Metallic glasses (MGs) inherit their amorphous structure from the liquid state, which predetermines their ability to withstand high loads approaching the theoretical limit. However, the absence of slip systems makes them very sensitive to the type of loading and extremely brittle in tension. The latter can be improved by precipitation of ductile crystals, which suppress a catastrophic propagation of shear bands in a glassy matrix. Here we report a novel approach to obtain MG-matrix composites with tensile ductility by flash Joule heating applied to Cu47.5Zr47.5Al5 (at.%) metallic glass. This homogeneous, volumetric and controllable rapid heat treatment allows achieving uniformly distributed metastable B2 CuZr crystals in the glassy matrix. It results in a significant tensile strain of 6.8±0.5%. Moreover, optimized adjustment of the heat-treatment conditions enables tuning of microstructure to achieve desired mechanical properties.

Synthesis of carbon-encapsulated iron nanoparticles by pyrolysis of iron citrate and poly(vinyl alcohol): a critical evaluation of yield and selectivity.

Carbon-encapsulated iron nanoparticles were synthesized by pyrolysis at 1000 °C of two solid precursors: poly(vinyl alcohol) and iron citrate. The weight ratio between the precursors controlled the reaction yield, crystallinity, morphological features and magnetic properties of the products. The encapsulation yield of iron nanoparticles in carbon shells was strongly influenced by the iron-to-carbon ratio and depended on the iron citrate content in the initial reactant mixtures. Despite the inherent simplicity of the process and the use of low cost starting materials the demonstrated route possesses limited selectivity, especially at high iron-to-carbon ratios. At these experimental conditions the as-obtained products contained non-encapsulated Fe particles and graphite in addition to magnetic carbon encapsulates. These by-products were effectively removed by a one-pot purification procedure that included acid treatment.

Robust determination of Young's modulus of individual carbon nanotubes by quasi-static interaction with Lorentz forces.

Young's modulus of an individual multi-wall carbon nanotube has been determined by the method of quasi-static transverse bending due to a Lorentz force observed in situ in a transmission electron microscope. The deflection of the nanotube allows the determination of Young's modulus using Euler-Bernoulli's beam equation. Because we determine the specific dependence of the deflection on the position along the nanotube axis, it is possible to gain insight into the type of mountings and furthermore allows for an estimation of the homogeneity of the nanotube. Both properties have been found to be of importance to determine Young's modulus. It was found to be higher by up to a factor of 1.6 compared to the value obtained by assuming rigid mountings.

Dispersion and diameter separation of multi-wall carbon nanotubes in aqueous solutions.

Comparative studies on dispersing of multi-wall carbon nanotubes (CNTs) using two anionic surfactants (sodium dodecyl sulphate, SDS, and sodium dodecyl benzenosulfonate, SDBS) are presented. The studies were conducted on the surfactant concentrations that were close to the critical micelle concentration (CMC). The stability of CNTs suspensions obtained for surfactant solutions at concentrations lower than the CMC was investigated. It was also found that the surfactant structure has an influence on the diameter distribution of dispersed CNTs.

Preparation of CNT-copper matrix composite films.

Copper matrix composite thin films reinforced with multiwall carbon nanotubes (CNT-Cu-MC) have been processed by electroplating on conducting or insulating underlayers on oxidized (100)Si substrates using iron catalyst particles. The nanotubes were grown by thermal or plasma enhanced catalytic CVD process. Enhanced interfacial strength to copper was achieved after covering the CNTs by plasma enhanced atomic layer deposition (PEALD) of a thin Ta-N or Ta-N/Zr-O interlayer. For copper plating a conventional copper electrolyte with additives (Ethone) was applied. The density of CNTs and their growth determine primarily the quality of the composite films. A sufficient dispersion of CNTs in the copper matrix and homogeneous copper plating were obtained for low density of CNTs. The CNT reinforcement changes the microstructure and electrical properties of electroplated copper films. The resistivity of the Cu films increases by multiwall CNT reinforcement as a result of changed microstructure.

ELNES study of chemical solution deposited SrO(SrTiO(3))(n) Ruddlesden-Popper films: experiment and simulation.

This article analyzes electron energy-loss near-edge fine structures of the SrO(SrTiO(3))(n=1) Ruddlesden-Popper system and of the parent compounds SrTiO(3) and SrO by comparison with first principles calculations. For that, the fine structures of chemical solution deposited Ruddlesden-Popper films have been experimentally recorded by means of transmission electron microscopy. Moreover, density of states computations using an all-electron density-functional code have been performed. It is shown that the appearance and shape of the experimental O-K and Ti-L(2,3) fine structure features result from the crystallography-dependent electronic structure of the investigated oxides, which display technologically interesting dielectric as well as lattice-structural properties.

Epitaxial Fe3Si films on GaAs(100) substrates by means of electron beam evaporation.

This paper presents results on the preparation, structural, electrical and magnetic properties of Fe(3)Si films as a representative for a Heusler alloy-like compound which are known as half-metallic materials with ferromagnetic behaviour. The films have been prepared by means of ultra-high vacuum (UHV) electron beam evaporation with the aim of achieving epitaxial growth on GaAs(100) substrates. The main focus of this work is the structural characterization of the Fe(3)Si films grown on GaAs by means of high resolution transmission electron microscopy (TEM) to confirm the epitaxial growth. For Fe(3)Si with a composition in the vicinity of stoichiometry an almost lattice-matched growth on GaAs(001) has been observed characterized by a high crystalline quality and a good interface perfection. Besides the studies on cross-sectional samples by TEM data from reflection high energy electron diffraction (RHEED) and x-ray diffraction (XRD) were also included into the discussion. The electrical and magnetic parameters of the films studied are found to be in good agreement with data reported for the best Fe(3)Si molecular beam epitaxy (MBE) layers. As evidenced by x-ray diffraction, transmission electron microscopy, resistivity and magnetic measurements, we find an optimum growth temperature of 280-350 degrees C to obtain ferromagnetic layers with high crystal and interface perfection as well as a high degree of atomic ordering.

Single-walled carbon nanotubes synthesis: a direct comparison of laser ablation and carbon arc routes.

Carbon arc and chemical vapor deposition are at present the most efficient methods for mass production of single-walled carbon nanotubes. However, laser ablation is renowned for high quality nanotubes with narrow diameter distributions and hence is also of great interest. The aim of this work was to compare both the carbon arc and laser ablation techniques with respect to the quality--and relative yield of the produced SWCNTs. For this comparative study we used Fe as the catalyst, which is known not to be very active in laser ablation. However, we show this is not the case when H2 is included in the reaction. The reactions for both synthesis routes were carried out in a N2-H2 (95-5% vol.) atmosphere. The same homogenous carbon rods with different iron contents, between 1 and 5 at.% were used as the carbon feedstock and catalyst supply in both synthesis routes. Additionally, two types of carbon rods containing 1 at.% Fe with different graphitization degrees were also investigated. In the arc-discharge case, the low-graphitized electrode produced a web-like product rich in SWCNTs, while the high-graphitized carbon rods yielded soot containing carbon-encapsulated iron nanocrystallites, amorphous carbon nanoparticles, and surprisingly a small fraction of SWCNTs. With laser ablation synthesis, the Fe content and the reactor temperature significantly influenced the SWCNTs yield. Carbon arc plasma diagnostics were also performed. By using optical emission and Absorption spectroscopy the plasma temperature, C2 and CN radical content in the arc zone were determined.

Determination of manganese valency in La1-xSrxMnO3 using ELNES in the (S)TEM.

In this article several experimentally identified Mn valence-sensitive ELNES quantities for the La1-xSrxMnO3 compound class are presented, namely the energy separations between Mn-L3 and O-Ka, between O-Kb and O-Ka edges, the Mn-L2,3 white line intensity ratio, and the Mn-L3 line width. Valence sensitivities of these quantities are evaluated, and possible additional influences on them are considered. At high signal-to-noise ratio the two energy separations display most sensitively changes of the Mn valency. An experiment-based estimation of the total uncertainties of the quantities indicates that at low signal-to-noise ratio, which is the case when studying interface effects at high spatial resolution, again both energy separations allow to resolve the smallest valency changes.

Structure and giant magnetoresistance behaviour of Co-Cu/Cu multilayers electrodeposited under various deposition conditions.

Electrodeposited Co-Cu/Cu multilayers were prepared under a variety of deposition conditions on either a polycrystalline Ti foil or on a silicon wafer covered by a Ta buffer and a Cu seed layer. X-ray diffraction (XRD) revealed a strong (111) texture for all multilayers with clear satellite peaks for the multilayers on Si/Ta/Cu substrates, in some cases for up to three reflections. Cross-sectional transmission electron microscopy investigations indicated a much more uniform multilayer structure on the Si/Ta/Cu substrates. The bilayer periods from XRD satellite reflections were in reasonable agreement with nominal values. An analysis of the overall chemical composition of the multilayers gave estimates of the sublayer thickness changes due to the Co-dissolution process during the Cu deposition pulse. The XRD lattice spacing data indicated a behaviour close to a simple "multilayer" Vegard's law which was, however, further refined by taking into account elastic strains as well. In agreement with the structural studies, magnetoresistance data also indicated the formation of more perfect multilayers on the smooth Si/Ta/Cu substrates. An analysis of the magnetoresistance behaviour revealed the presence of superparamagnetic (SPM) regions in the magnetic layers. The contribution of these SPM regions to the total observed giant magnetoresistance was found to be dominating under certain deposition conditions, e.g., for magnetic layer thicknesses less than 1 nm (about 5 monolayers).

Extraction of EELS white-line intensities of manganese compounds: methods, accuracy, and valence sensitivity.

This article evaluates the valence sensitivity and accuracy of selected EELS white-line extraction methods based on the white-line intensity ratio in case of manganese oxides, predominantly in the valency range [Mn3+ ; Mn4+]. For this purpose Mn-L2,3 ionization edges of several Mn oxides were measured and four different methods were applied to extract the intensities. The obtained ratios have been analyzed in terms of their errors, their scatter, and their sensitivity on manganese valency. We found that the maximum-intensity as well as the Pearson and Walsh-Dray methods show larger relative changes of the ratio between Mn3+ and Mn4+ than curve-fitting. Taking the scatter into account, Walsh-Dray distinguishes more clearly between those two valencies than curve-fitting. Thus the Walsh-Dray method promises the most accurate determination of small valency shifts.

Microstructure and composition of annealed Al/Ti-metallization layers.

Al/Ti multilayers with columnar grains were deposited by electron-beam evaporation on piezoelectric LiNbO(3) substrates. After annealing in air and under vacuum conditions dissolution of the Ti interlayer was observed for all samples. The original Ti interlayer dissolved completely and globular Al(3)Ti grains were formed within an Al matrix. All samples had an oxidized adhesive Ti bottom layer and a 10 nm thin Al layer below this adhesive Ti bottom layer, which remains intact after the applied heat treatment. This resistance against dissolution by interdiffusion could be caused by the oxidation. These changes in the microstructure and in the chemical composition were investigated by conventional and analytical TEM.

Validity of the dipole-selection rule for the Al-L2,3 edge of alpha-Al2O3 under channeling conditions.

The validity of the dipole-selection rule for the Al-L2,3 electron energy-loss edge of alpha-Al2O3 is investigated. Dipole forbidden transitions can be observed in a transmission electron microscope operated with large collection apertures. In addition, it is shown that channeling along a highly symmetrical zone axis in alpha-Al2O3 can lead to the detection of dipole forbidden transitions even with small collection apertures. For an incident electron direction parallel to the <0001> orientation it is observed experimentally that the fine structure of the Al-L2,3 edge shows additional features compared to measurements with the electron beam parallel to <1100>. This effect is due to the occurrence of channeling conditions, indicated by the dependence of the additional dipole forbidden features on the sample thickness. These additional features disappear when tilting the crystal by 1.8 degrees (0.84 A(-1)) or even into the less-symmetrical <1100> zone axis. It is suggested that these observations are explained by differences in local symmetry at the excited center with respect to the incident beam directions.

Quantitative atomic-scale analysis of interface structures: transmission electron microscopy and local density functional theory.

Transmission electron microscopy (TEM) and local density functional theory (LDFT) are combined to analyze the microscopic structure of the rhombohedral twin interface in alpha-Al2O3. LDFT provides interfacial energetics and atomic and electronic structures for three competing models. With high-resolution TEM the atomic structure at the interface is imaged quantitatively along two orthogonal zone axes. Electron energy loss spectroscopy in TEM with nanoscale spatial resolution yields the interfacial electronic structure. Both experiments confirm the theoretically preferred model quantitatively.

Core-hole effect in the ELNES of alpha-Al2O3: experiment and theory.

The occurrence of the core-hole effect at the Al-K and Al-L1 edge in alpha-Al2O3 was studied by comparing experimental electron energy-loss near-edge structures (ELNES) and results of band-structure calculations with and without accounting for core-hole effects by the Z + 1 approximation. It was found that the theoretically calculated unoccupied p-like projected densities of states (PDOS) without Z + 1 approximation matches better to the experimental Al-L1 ELNES, whereas the PDOS with Z + 1 approximation matches better to the experimental Al-K ELNES. We conclude that the localisation of the initial state is an important prerequisite for the observability of the core-hole effect in the ELNES.