Epitaxial hard magnetic SmCo5 MFM tips - a new approach to advanced magnetic force microscopy imaging.

Cantilever based scanning force sensors, which probe a specific tip-sample interaction through a functional tip coating, are limited by the material performance achievable in the coating process. In case of the wide spread magnetic force microscopy (MFM) technique, the magnetic performance of MFM tips, especially the response to magnetic fields and the coercivity, fall far behind the quality known from permanent magnet films prepared with optimized process conditions on appropriate substrates. We resolve this limitation by starting from an optimized thin film architecture - a highly anisotropic SmCo5 film grown epitaxially on MgO(110) substrates - from which a tip is separated by focused ion beam and is attached to a cantilever. Not compromising on resolution and sensitivity, we demonstrate an unrivaled rigidity in magnetic fields, which will largely advance quantitative microscopic investigation of magnetic materials with strong stray fields and allows MFM measurements in external magnetic fields of currently up to 0.7 T. The material optimization for a specific sample - cantilever interaction without restrictions in substrate, film architecture, film preparation conditions and tip shape, is not limited to MFM but offers new opportunities also for other scanning force microscopy modes.

Reversible tuning of magnetocaloric Ni-Mn-Ga-Co films on ferroelectric PMN-PT substrates.

Tuning functional properties of thin caloric films by mechanical stress is currently of high interest. In particular, a controllable magnetisation or transition temperature is desired for improved usability in magnetocaloric devices. Here, we present results of epitaxial magnetocaloric Ni-Mn-Ga-Co thin films on ferroelectric Pb(Mg1/3Nb2/3)0.72Ti0.28O3 (PMN-PT) substrates. Utilizing X-ray diffraction measurements, we demonstrate that the strain induced in the substrate by application of an electric field can be transferred to the thin film, resulting in a change of the lattice parameters. We examined the consequences of this strain on the magnetic properties of the thin film by temperature- and electric field-dependent measurements. We did not observe a change of martensitic transformation temperature but a reversible change of magnetisation within the austenitic state, which we attribute to the intrinsic magnetic instability of this metamagnetic Heusler alloy. We demonstrate an electric field-controlled entropy change of about 31 % of the magnetocaloric effect - without any hysteresis.

Multislice simulations for in-situ HRTEM studies of nanostructured magnesium hydride at ambient hydrogen pressure.

The use of transmission electron microscopy (TEM) for the structural characterization of many nanostructured hydrides, which are relevant for solid state hydrogen storage, is hindered due to a rapid decomposition of the specimen upon irradiation with the electron beam. Environmental TEM allows to stabilize the hydrides by applying a hydrogen back pressure of up to 4.5 bar in a windowed environmental cell. The feasibility of high-resolution TEM (HRTEM) investigations of light weight metals and metal hydrides in such a "nanoreactor" is studied theoretically by means of multislice HRTEM contrast simulations using Mg and its hydride phase, MgH2, as model system. Such a setup provides the general opportunity to study dehydrogenation and hydrogenation reactions at the nanoscale under technological application conditions. We analyze the dependence of both the spatial resolution and the HRTEM image contrast on parameters such as the defocus, the metal/hydride thickness, and the hydrogen pressure in order to explore the possibilities and limitations of in-situ experiments with windowed environmental cells. Such simulations may be highly valuable to pre-evaluate future experimental studies.

Magnetic properties of single nanomagnets: Electron energy-loss magnetic chiral dichroism on FePt nanoparticles.

Electron energy-loss magnetic chiral dichroism (EMCD) allows for the quantification of magnetic properties of materials at the nanometer scale. It is shown that with the support of simulations that help to identify the optimal conditions for a successful experiment and upon implementing measurement routines that effectively reduce the noise floor, EMCD measurements can be pushed towards quantitative magnetic measurements even on individual nanoparticles. With this approach, the ratio of orbital to spin magnetic moments for the Fe atoms in a single L10 ordered FePt nanoparticle is determined to be ml/ms=0.08±0.02. This finding is in good quantitative agreement with the results of XMCD ensemble measurements.

Large pinning forces and matching effects in YBa2Cu3O(7-δ) thin films with Ba2Y(Nb/Ta)O6 nano-precipitates.

The addition of mixed double perovskite Ba2Y(Nb/Ta)O6 (BYNTO) to YBa2Cu3O(7-δ) (YBCO) thin films leads to a large improvement of the in-field current carrying capability. For low deposition rates, BYNTO grows as well-oriented, densely distributed nanocolumns. We achieved a pinning force density of 25 GN/m(3) at 77 K at a matching field of 2.3 T, which is among the highest values reported for YBCO. The anisotropy of the critical current density shows a complex behavior whereby additional maxima are developed at field dependent angles. This is caused by a matching effect of the magnetic fields c-axis component. The exponent N of the current-voltage characteristics (inversely proportional to the creep rate S) allows the depinning mechanism to be determined. It changes from a double-kink excitation below the matching field to pinning-potential-determined creep above it.

Designing new biocompatible glass-forming Ti75-x Zr10 Nbx Si15 (x = 0, 15) alloys: corrosion, passivity, and apatite formation.

Glass-forming Ti-based alloys are considered as potential new materials for implant applications. Ti75 Zr10 Si15 and Ti60 Zr10 Nb15 Si15 alloys (free of cytotoxic elements) can be produced as melt-spun ribbons with glassy matrix and embedded single ß-type nanocrystals. The corrosion and passivation behavior of these alloys in their homogenized melt-spun states have been investigated in Ringer solution at 37°C in comparison to their cast multiphase crystalline counterparts and to cp-Ti and ß-type Ti-40Nb. All tested materials showed very low corrosion rates as expressed in corrosion current densities icorr < 50 nA/cm(2). Electrochemical and surface analytical studies revealed a high stability of the new alloys passive states in a wide potential range. This corresponds to low passive current densities ipass = 2 ± 1 µA/cm(2) based on the growth of oxide films with thickness d <10 nm. A homogeneous constituent distribution in the melt-spun alloys is beneficial for stable surface passivity. The addition of Nb does not only improve the glass-forming ability and the mechanical properties but also supports a high pitting resistance even at extreme anodic polarization up to 4V versus SCE were oxide thickness values of d ∼35 nm are reached. With regard to the corrosion properties, the Nb-containing nearly single-phase glassy alloy can compete with the ß-type Ti-40Nb alloy. SBF tests confirmed the ability for formation of hydroxyapatite on the melt-spun alloy surfaces. All these properties recommend the new glass-forming alloys for application as wear- and corrosion-resistant coating materials for implants.

High field superconducting properties of Ba(Fe1-xCox)2As2 thin films.

In general, the critical current density, Jc, of type II superconductors and its anisotropy with respect to magnetic field orientation is determined by intrinsic and extrinsic properties. The Fe-based superconductors of the '122' family with their moderate electronic anisotropies and high yet accessible critical fields (Hc2 and Hirr) are a good model system to study this interplay. In this paper, we explore the vortex matter of optimally Co-doped BaFe2As2 thin films with extended planar and c-axis correlated defects. The temperature and angular dependence of the upper critical field is well explained by a two-band model in the clean limit. The dirty band scenario, however, cannot be ruled out completely. Above the irreversibility field, the flux motion is thermally activated, where the activation energy U0 is going to zero at the extrapolated zero-kelvin Hirr value. The anisotropy of the critical current density Jc is both influenced by the Hc2 anisotropy (and therefore by multi-band effects) as well as the extended planar and columnar defects present in the sample.

Silicon carbide embedded in carbon nanofibres: structure and band gap determination.

Materials drastically alter their electronic properties when being reduced to the nanoscale due to quantum effects. Concerning semiconductors, the band gap is expected to broaden as a result of the quantum confinement. In this study we report on the successful synthesis of wide bandgap SiC nanowires (with great potential for applications) and the local determination of their band gap. Their value was found to be higher with respect to bulk SiC. The nanowires are grown as a heterostructure, i.e. encapsulated in carbon nanofibres via dc hot-filament Plasma-Enhanced Chemical Vapour Deposition on the Si/SiO2 substrate. The structure of the as-produced carbon nanofibres was characterized by means of aberration-corrected high-resolution transmission electron microscopy. Two different pure SiC polytypes, namely the 3C (cubic) and the 6H (hexagonal) as well as distorted structures are observed. The SiC nanowires have diameters in the range of 10-15 nm and lengths of several hundred nanometers. The formation of the SiC is a result of the substrate etching during the growth of the CNFs and a subsequent simultaneous diffusion of not only carbon, but also silicon through the catalyst particle.

Near-surface strain in icosahedra of binary metallic alloys: segregational versus intrinsic effects.

A systematic structural analysis of FePt, CuAu, and Au icosahedral nanoparticles is presented. The uncovered particles are prepared by inert gas condensation and thermally equilibrated through in-flight optical annealing. Aberration-corrected high-resolution transmission electron microscopy reveals that the crystal lattice is significantly expanded near the particle surface. These experimental findings are corroborated by molecular statics simulations that show that this near-surface strain originates from both intrinsic strain due to the icosahedral structure and a partial segregation of the larger of the two alloy constituents to the particle surface.

Oxypnictide SmFeAs(O,F) superconductor: a candidate for high-field magnet applications.

The recently discovered oxypnictide superconductor SmFeAs(O,F) is the most attractive material among the Fe-based superconductors due to its highest transition temperature of 56 K and potential for high-field performance. In order to exploit this new material for superconducting applications, the knowledge and understanding of its electro-magnetic properties are needed. Recent success in fabricating epitaxial SmFeAs(O,F) thin films opens a great opportunity to explore their transport properties. Here we report on a high critical current density of over 10(5) A/cm(2) at 45 T and 4.2 K for both main field orientations, feature favourable for high-field magnet applications. Additionally, by investigating the pinning properties, we observed a dimensional crossover between the superconducting coherence length and the FeAs interlayer distance at 30-40 K, indicative of a possible intrinsic Josephson junction in SmFeAs(O,F) at low temperatures that can be employed in electronics applications such as a terahertz radiation source and a superconducting Qubit.

Magnetic domain pattern in hierarchically twinned epitaxial Ni-Mn-Ga films.

Magnetic shape memory alloys exhibit a hierarchically twinned microstructure, which has been examined thoroughly in epitaxial Ni-Mn-Ga films. Here we analyze the consequences of this 'twin within twins' microstructure on the magnetic domain pattern. Atomic and magnetic force microscopy are used to probe the correlation between the martensitic microstructure and magnetic domains. We examine the consequences of different twin boundary orientations with respect to the substrate normal as well as variant boundaries between differently aligned twinned laminates. A detailed micromagnetic analysis is given which describes the influence of the finite film thickness on the formation of magnetic band domains in these multiferroic materials.

Production of Porous ß-Type Ti-40Nb Alloy for Biomedical Applications: Comparison of Selective Laser Melting and Hot Pressing.

We used selective laser melting (SLM) and hot pressing of mechanically-alloyed ß-type Ti-40Nb powder to fabricate macroporous bulk specimens (solid cylinders). The total porosity, compressive strength, and compressive elastic modulus of the SLM-fabricated material were determined as 17% ± 1%, 968 ± 8 MPa, and 33 ± 2 GPa, respectively. The alloy's elastic modulus is comparable to that of healthy cancellous bone. The comparable results for the hot-pressed material were 3% ± 2%, 1400 ± 19 MPa, and 77 ± 3 GPa. This difference in mechanical properties results from different porosity and phase composition of the two alloys. Both SLM-fabricated and hot-pressed cylinders demonstrated good in vitro biocompatibility. The presented results suggest that the SLM-fabricated alloy may be preferable to the hot-pressed alloy for biomedical applications, such as the manufacture of load-bearing metallic components for total joint replacements.

Clarifying the mechanism of reverse structuring during electrodeposition in magnetic gradient fields.

Deviating from the common expectation, magnetoelectrochemical structuring during deposition of diamagnetic ions was demonstrated, very recently. To achieve this, electrochemically inert paramagnetic ions have to be added to the electrolyte and the deposition has to be performed in a magnetic gradient field. A reverse structuring occurs, yielding thinner deposits near high gradient regions. In this paper we aim to clarify the mechanism of this reverse structuring. Potentiodynamic and potentiostatic investigations were performed, including measurements of the deposited mass with an electrochemical quartz crystal microbalance (EQCM). The convection of the electrolyte was studied in situ by astigmatism particle tracking velocimetry (APTV). It was revealed that during the reverse structuring a convection is induced in the electrolyte, which is directed away from the working electrode in regions of high magnetic gradients. Due to this additional convection, the overall deposition rate is increased, whereby it is locally reduced in regions of high magnetic gradients. The mechanism for reverse structuring is discussed in detail. Also, the influence of all relevant magnetic forces is addressed.

Magnetic nanostructures by adaptive twinning in strained epitaxial films.

We exploit the intrinsic structural instability of the Fe(70)Pd(30) magnetic shape memory alloy to obtain functional epitaxial films exhibiting a self-organized nanostructure. We demonstrate that coherent epitaxial straining by 54% is possible. The combination of thin film experiments and large-scale first-principles calculations enables us to establish a lattice relaxation mechanism, which is not expected for stable materials. We identify a low twin boundary energy compared to a high elastic energy as key prerequisite for the adaptive nanotwinning. Our approach is versatile as it allows to control both, nanostructure and intrinsic properties for ferromagnetic, ferroelastic, and ferroelectric materials.

Catalyst poisoning by amorphous carbon during carbon nanotube growth: fact or fiction?

The influence of amorphous carbon on FePt catalyst particles under chemical vapor deposition conditions typically applied for CNT growth is examined through two routes. In the first, FePt catalyst particles supported on alumina are exposed to a well-established cyclohexane thermal CVD reaction at various temperatures. At higher temperatures where self-pyrolysis leads to copious amorphous carbon and carbon tar formation, carbon nanotubes are still able to form. In the second route, an amorphous carbon film is first deposited over the catalyst particles prior to the CVD reaction. Even for reactions where further amorphous carbon is deposited due to self-pyrolysis, graphitization is still demonstrated. Our findings reveal that the presence of amorphous carbon does not prevent catalytic hydrocarbon decomposition and graphitization processes. We also show an additional catalytic reaction to be present, catalytic hydrogenation, a process in which carbon in contact with the catalyst surface reacts with H(2) to form CH(4).

In situ analysis of three-dimensional electrolyte convection evolving during the electrodeposition of copper in magnetic gradient fields.

A novel three-dimensional particle tracking velocimetry technique was used to examine the flow during electrodeposition of Cu. For the first time electrode-normal, circumferential, and radial velocities were spatially resolved during deposition in superimposed low and high magnetic gradient fields. In this way the complex interaction of magnetic field gradient force and Lorentz force induced convective effects could be measured and analyzed. Magnetic field gradient force induced electrolyte flow was detected only in high gradient magnetic fields, and it was found to be directed toward regions of gradient maxima. Since this electrode-normal flow causes enhanced transport of Cu(2+) ions from the bulk electrolyte to those regions of the working electrode where maxima of magnetic gradients are present, a structured deposit is formed during diffusion-limited electrodeposition. Lorentz force driven convection was observed during deposition in the low and the high magnetic gradient experiments. The overall fluid motion and the convection near the working electrode were determined experimentally and discussed with regard to the acting magnetic forces and numerical simulations.

Novel sodium aluminium borohydride containing the complex anion [Al(BH4,Cl)4]-.

The synthesis of a novel alkali-metal aluminium borohydride NaAl(BH4)xCl4-x from NaBH4 and AlCl3 using a solid state metathesis reaction is described. Structure determination was carried out using synchrotron powder diffraction data and vibrational spectroscopy. An orthorhombic structure (space group Pmn2(1)) is formed which contains Na+ cations and complex [Al(BH4,Cl)4]- anions. Due to the high chlorine content (1 < or = x < or = 1.43) the hydrogen density of the borohydride is only between 2.3 and 3.5 wt.% H2 in contrast to the expected 14.6 wt.% for chlorine free NaAl(BH4)4. The decomposition of NaAl(BH4)xCl4-x is observed in the target range for desorption at about 90 degrees C by differential scanning calorimetry (DSC), in situ Raman spectroscopy and synchrotron powder X-ray diffraction. Thermogravimetric analysis (TG) shows extensive mass loss indicating the loss of H2 and B2H6 at about 90 degrees C followed by extensive weight loss in the form of chloride evaporation.

Al3Li4(BH4)13: a complex double-cation borohydride with a new structure.

The new double-cation Al-Li-borohydride is an attractive candidate material for hydrogen storage due to a very low hydrogen desorption temperature (approximately 70 degrees C) combined with a high hydrogen density (17.2 wt%). It was synthesised by high-energy ball milling of AlCl(3) and LiBH(4). The structure of the compound was determined from image-plate synchrotron powder diffraction supported by DFT calculations. The material shows a unique 3D framework structure within the borohydrides (space group=P-43n, a=11.3640(3) A). The unexpected composition Al(3)Li(4)(BH(4))(13) can be rationalized on the basis of a complex cation [(BH(4))Li(4)](3+) and a complex anion [Al(BH(4))(4)](-). The refinements from synchrotron powder diffraction of different samples revealed the presence of limited amounts of chloride ions replacing the borohydride on one site. In situ Raman spectroscopy, differential scanning calorimetry (DSC), thermogravimetry (TG) and thermal desorption measurements were used to study the decomposition pathway of the compound. Al-Li-borohydride decomposes at approximately 70 degrees C, forming LiBH(4). The high mass loss of about 20 % during the decomposition indicates the release of not only hydrogen but also diborane.