A comparative study of the influence of the deposition technique (electrodeposition versus sputtering) on the properties of nanostructured Fe70Pd30 films.

Sputtering and electrodeposition are among the most widespread techniques for metallic thin film deposition. Since these techniques operate under different principles, the resulting films typically show different microstructures even when the chemical composition is kept fixed. In this work, films of Fe70Pd30 were produced in a thickness range between 30 and 600 nm, using both electrodeposition and sputtering. The electrodeposited films were deposited under potentiostatic regime from an ammonia sulfosalicylic acid-based aqueous solution. Meanwhile, the sputtered films were deposited from a composite target in radio frequency regime. Both approaches were proven to yield high quality and homogenous films. However, their crystallographic structure was different. Although all films were polycrystalline and Fe and Pd formed a solid solution with a body-centered cubic structure, a palladium hydride phase was additionally detected in the electrodeposited films. The occurrence of this phase induced internal stress in the films, thereby influencing their magnetic properties. In particular, the thickest electrodeposited Fe70Pd30 films showed out-of-plane magnetic anisotropy, whereas the magnetization easy axis lied in the film plane for all the sputtered films. The domain pattern of the electrodeposited films was investigated by magnetic force microscopy. Finally, nanoindentation studies highlighted the high quality of both the sputtered and electrodeposited films, the former exhibiting higher reduced Young's modulus and Berkovich hardness values.

Electrodeposition of Sr-substituted hydroxyapatite on low modulus beta-type Ti-45Nb and effect on in vitro Sr release and cell response.

Beta-type Ti-based alloys are promising new materials for bone implants owing to their excellent mechanical biofunctionality and biocompatibility. For treatment of fractures in case of systemic diseases like osteoporosis the generation of implant surfaces which actively support the problematic bone healing is a most important aspect. This work aimed at developing suitable approaches for electrodeposition of Sr-substituted hydroxyapatite (Srx-HAp) coatings onto Ti-45Nb. Potentiodynamic polarization measurements in electrolytes with 1.67 mmol/L Ca(NO3)2, which was substituted by 0, 10, 50 and 100% Sr(NO3)2, and 1 mmol/L NH4H2PO4 at 333 K revealed the basic reaction steps for OH- and PO43- formation needed for the chemical precipitation of Srx-HAp. Studies under potentiostatic control confirmed that partial or complete substitution of Ca2+- by Sr2+-ions in solution has a significant effect on the complex reaction process. High Sr2+-ion contents yield intermediate phases and a subsequent growth of more refined Srx-HAp coatings. Upon galvanostatic pulse-deposition higher reaction rates are controlled and in all electrolytes very fine needle-like crystalline coatings are obtained. With XRD the incorporation of Sr-species in the hexagonal HAp lattice is evidenced. Coatings formed in electrolytes with 10 and 50% Sr-nitrate were chemically analyzed with EDX mapping and GD-OES depth profiling. Only a fraction of the Sr-ions in solution is incorporated into the Srx-HAp coatings. Therein, the Sr-distribution is laterally homogeneous but non-homogeneous along the cross-section. Increasing Sr-content retards the coating thickness growth. Most promising coatings formed in the electrolyte with 10% Sr-nitrate were employed for Ca, P and Sr release analysis in Tris-Buffered Saline (150 mM NaCl, pH 7.6) at 310 K. At a sample surface: solution volume ratio of 1:200, after 24 h the amount of released Sr-ions was about 30-35% of that determined in the deposited Srx-HAp coating. In vitro studies with human bone marrow stromal cells (hBMSC) revealed that the released Sr-ions led to a significantly enhanced cell proliferation and osteogenic differentiation and that the Sr-HAp surface supported cell adhesion indicating its excellent cytocompatibility.

Electroless-Deposited Platinum Antennas for Wireless Surface Acoustic Wave Sensors.

In an effort to develop a cost-efficient technology for wireless high-temperature surface acoustic wave sensors, this study presents an evaluation of a combined method that integrates physical vapor deposition with electroless deposition for the fabrication of platinum-based planar antennas. The proposed manufacturing process becomes attractive for narrow, thick, and sparse metallizations for antennas in the MHz to GHz frequency range. In detail, narrow platinum-based lines of a width down to 40 µm were electroless-deposited on γ-Al 2O 3 substrates using different seed layers. At first, the electrolyte chemistry was optimized to obtain the highest deposition rate. Films with various thickness were prepared and the electrical resistivity, microstructure, and chemical composition in the as-prepared state and after annealing at temperatures up to 1100 ∘C were evaluated. Using these material parameters, the antenna was simulated with an electromagnetic full-wave simulation tool and then fabricated. The electrical parameters, including the S-parameters of the antenna, were measured. The agreement between the simulated and the realized antenna is then discussed.

Combining magnetic forces for contactless manipulation of fluids in microelectrode-microfluidic systems.

A novel method to drive and manipulate fluid in a contactless way in a microelectrode-microfluidic system is demonstrated by combining the Lorentz and magnetic field gradient forces. The method is based on the redox-reaction [Fe(CN)6]3-/[Fe(CN)6]4- performed in a magnetic field oriented perpendicular to the ionic current that crosses the gap between two arrays of oppositely polarized microelectrodes, generating a magnetohydrodynamic flow. Additionally, a movable magnetized CoFe micro-strip is placed at different positions beneath the gap. In this region, the magnetic flux density is changed locally and a strong magnetic field gradient is formed. The redox-reaction changes the magnetic susceptibility of the electrolyte near the electrodes, and the resulting magnetic field gradient exerts a force on the fluid, which leads to a deflection of the Lorentz force-driven main flow. Particle Image Velocity measurements and numerical simulations demonstrate that by combining the two magnetic forces, the flow is not only redirected, but also a local change of concentration of paramagnetic species is realized.

Dynamics of Single Hydrogen Bubbles at a Platinum Microelectrode.

Bubble dynamics, including the formation, growth, and detachment, of single H2 bubbles was studied at a platinum microelectrode during the electrolysis of 1 M H2SO4 electrolyte. The bubbles were visualized through a microscope by a high-speed camera. Electrochemical measurements were conducted in parallel to measure the transient current. The periodic current oscillations, resulting from the periodic formation and detachment of single bubbles, allow the bubble lifetime and size to be predicted from the transient current. A comparison of the bubble volume calculated from the current and from the recorded bubble image shows a gas evolution efficiency increasing continuously with the growth of the bubble until it reaches 100%. Two different substrates, glass and epoxy, were used to embed the Pt wire. While nearly no difference was found with respect to the growth law for the bubble radius, the contact angle differs strongly for the two types of cell. Data provided for the contact point evolution further complete the image of single hydrogen bubble growth. Finally, the velocity field driven by the detached bubble was measured by means of PIV, and the effects of the convection on the subsequent bubble were evaluated.

The anodic stripping voltammetry of nanoparticles: electrochemical evidence for the surface agglomeration of silver nanoparticles.

Analytical expressions for the anodic stripping voltammetry of metallic nanoparticles from an electrode are provided. First, for reversible electron transfer, two limits are studied: that of diffusionally independent nanoparticles and the regime where the diffusion layers originating from each particle overlap strongly. Second, an analytical expression for the voltammetric response under conditions of irreversible electron transfer kinetics is also derived. These equations demonstrate how the peak potential for the stripping process is expected to occur at values negative of the formal potential for the redox process in which the surface immobilised nanoparticles are oxidised to the corresponding metal cation in the solution phase. This work is further developed by considering the surface energies of the nanoparticles and its effect on the formal potential for the oxidation. The change in the formal potential is modelled in accordance with the equations provided by Plieth [J. Phys. Chem., 1982, 86, 3166-3170]. The new analytical expressions are used to investigate the stripping of silver nanoparticles from a glassy carbon electrode. The relative invariance of the stripping peak potential at low surface coverages of silver is shown to be directly related to the surface agglomeration of the nanoparticles.

Analysis of the electrolyte convection inside the concentration boundary layer during structured electrodeposition of copper in high magnetic gradient fields.

To experimentally reveal the correlation between electrodeposited structure and electrolyte convection induced inside the concentration boundary layer, a highly inhomogeneous magnetic field, generated by a magnetized Fe-wire, has been applied to an electrochemical system. The influence of Lorentz and magnetic field gradient force to the local transport phenomena of copper ions has been studied using a novel two-component laser Doppler velocity profile sensor. With this sensor, the electrolyte convection within 500 µm of a horizontally aligned cathode is presented. The electrode-normal two-component velocity profiles below the electrodeposited structure show that electrolyte convection is induced and directed toward the rim of the Fe-wire. The measured deposited structure directly correlates to the observed boundary layer flow. As the local concentration of Cu(2+) ions is enhanced due to the induced convection, maximum deposit thicknesses can be found at the rim of the Fe-wire. Furthermore, a complex boundary layer flow structure was determined, indicating that electrolyte convection of second order is induced. Moreover, the Lorentz force-driven convection rapidly vanishes, while the electrolyte convection induced by the magnetic field gradient force is preserved much longer. The progress for research is the first direct experimental proof of the electrolyte convection inside the concentration boundary layer that correlates to the deposited structure and reveals that the magnetic field gradient force is responsible for the observed structuring effect.

Get more out of your data: a new approach to agglomeration and aggregation studies using nanoparticle impact experiments.

Anodic particle coloumetry is used to size silver nanoparticles impacting a carbon microelectrode in a potassium chloride/citrate solution. Besides their size, their agglomeration state in solution is also investigated solely by electrochemical means and subsequent data analysis. Validation of this new approach to nanoparticle agglomeration studies is performed by comparison with the results of a commercially available nanoparticle tracking analysis system, which shows excellent agreement. Moreover, it is demonstrated that the electrochemical technique has the advantage of directly yielding the number of atoms per impacting nanoparticle irrespective of its shape. This is not true for the optical nanoparticle tracking system, which requires a correction for the nonspherical shape of agglomerated nanoparticles to derive reasonable information on the agglomeration state.

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.

Enrichment of Paramagnetic Ions from Homogeneous Solutions in Inhomogeneous Magnetic Fields.

Applying interferometry to an aqueous solution of paramagnetic manganese ions, subjected to an inhomogeneous magnetic field, we observe an unexpected but highly reproducible change in the refractive index. This change occurs in the top layer of the solution, closest to the magnet. The shape of the layer is in accord with the spatial distribution of the largest component of the magnetic field gradient force. It turns out that this layer is heavier than the underlying solution because it undergoes a Rayleigh-Taylor instability upon removal of the magnet. The very good agreement between the magnitudes of buoyancy, associated with this layer, and the field gradient force at steady state provides conclusive evidence that the layer formation results from an enrichment of paramagnetic manganese ions in regions of high magnetic field gradient.

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.