Microfluidic-Generated Seeds for Gold Nanotriangle Synthesis in Three or Two Steps.

Nanoparticle synthesis has drawn great attention in the last decades. The study of crystal growth mechanisms and optimization of the existing methods lead to the increasing accessibility of nanomaterials, such as gold nanotriangles which have great potential in the fields of plasmonics and catalysis. To form such structures, a careful balance of reaction parameters has to be maintained. Herein, a novel synthesis of gold nanotriangles from seeds derived with a micromixer, which provides a highly efficient mixing and simple parameter control is reported. The impact of the implemented reactor on the primary seed characteristics is investigated. The following growth steps are studied to reveal the phenomena affecting the shape yield. The use of microfluidic seeds led to the formation of well-defined triangles with a narrower size distribution compared to the entirely conventional batch synthesis. A shortened two-step procedure for the formation of triangles directly from primary seeds, granting an express but robust synthesis is further described. Moreover, the need for a thorough study of seed crystallinity depending on the synthesis conditions, which - together with additional parameter optimization - will bring a new perspective to the use of micromixers which are promising for scaling up nanomaterial production is highlighted.

Bifacial Dye Membranes: Ultrathin and Free-Standing although not Being Covalently Bound.

Layers of aligned dyes are key to photo-driven charge separation in dye sensitized solar cells, but cannot be exploited as rectifying membranes in photocatalysis to separate half-cells because they are not sufficiently stable. While impressive work on the fabrication of stable noncovalent membranes has been recently demonstrated, these membranes are inherently suffering from non-uniform orientation of the constituting dyes. To stabilize layers made from uniformly assembled and aligned dyes, they can be covalently cross-linked via functional groups or via chromophores at the expense of their optical properties. Here stable membranes from established dyes are reported that do not need to be elaborately functionalized nor do their chromophores need to be destroyed. These membranes are free-standing, although being only non-covalently linked. To enable uniform dye-alignment, Langmuir layers made from linear, water-insoluble dyes are used. That water-soluble charge transfer dyes adsorb onto and intercalate into the Langmuir layer from the aqueous subphase, thus yielding free-standing, molecularly thin membranes are demonstrated. The developed bifacial layers consist almost entirely of π-conjugated units and thus can conduct charges and can be further engineered for optoelectronic and photocatalytic applications.

Simulation of the Peritectic Phase Transition in Fe-C Alloys.

In this work, a multi-phase cellular automaton (CA) model is extended for the quantitative simulation of peritectic phase transition. First, the effects of cooling rate/supersaturation and temperature on the peritectic transformation kinetics in Fe-C alloys are investigated by utilizing the present CA model. The CA simulations show that supersaturations in the parent phases (liquid and δ-ferrite) increase the L/γ interface growth velocity remarkably, but tinily for the δ/γ interface migration velocity. There exists a transition supersaturation for isothermal transformations, at which the growth rates of the two interfaces are equal. The transition supersaturation is found to increase with decreasing temperature. Microstructural evolution at different cooling rates during peritectic transformation is simulated using the experimental conditions. At low cooling rates, the δ/γ interface propagates at a higher velocity than the L/γ interface. At high cooling rates, however, the γ-phase grows more into the L-phase with a cellular morphology. Then, the proposed CA model is applied to simulate the microstructural evolution during peritectic reaction. It is observed that the γ-phase propagates along the L/δ interface and finally encircles the δ-phase. Meanwhile, the intervenient γ-phase grows in thickness through peritectic transformation. The CA simulations are compared reasonably well with the experimental data and analytical calculations.

Modelling of liquid film migration in Al-Cu alloys.

Microstructural evolution in the presence of liquid film migration (LFM) is simulated for Al-Cu alloys using a cellular automaton (CA) model. Simulations are performed for the microstructural evolution and concentration distribution in an Al-4 wt.%Cu alloy with initially equiaxed grain structures holding in a temperature gradient. A slight deviation from local equilibrium, estimated from experimental data, is considered to be the driving force for LFM. The direction of LFM is triggered by concentration fluctuations setting a concentration gradient as a further driving force. The simulation successfully reproduces the experimentally observed microstructures generated by LFM accompanied by a particle free zone behind the liquid film. The solid concentration in the particle free zone is found to be the equilibrium solid concentration. The simulated concentration profile across the migrating liquid film agrees well with experimental measurements. The simulated grain structure becomes coarser and highly elongated after holding in the temperature gradient. The results reveal that the increase in transversal grain width is mainly controlled by LFM, while the grain elongation in longitudinal direction is attributed to both LFM and temperature gradient zone melting. The solid concentration decreases from the initial (supersaturated) composition to the local equilibrium solid concentration corresponding to the local temperature. This article is part of the theme issue 'Transport phenomena in complex systems (part 2)'.

Thermodynamic description of metastable fcc/liquid phase equilibria and solidification kinetics in Al-Cu alloys.

The thermodynamic description of the fcc phase in the Al-Cu system has been revised, allowing for the prediction of metastable fcc/liquid phase equilibria to undercoolings of ΔT = 421 K below the eutectic temperature. Hypoeutectic Al-Cu alloys that are prone to pronounced microsegregation were solidified containerlessly in electromagnetic levitation. Solidus and liquidus concentrations were experimentally determined from highly undercooled samples employing energy-dispersive X-ray analysis. Solid concentrations at a rapidly propagating solid/liquid interface were additionally calculated using a sharp interface model that considers all undercoolings and is based on solvability theory. Modelling results (front velocity versus undercooling) were also corroborated by in situ observation with a high-speed camera. A newly established thermodynamic description of the fcc phase in Al-Cu is compatible with existing CALPHAD-type databases. Inconsistencies of previous descriptions such as a miscibility gap between Al-fcc and Cu-fcc on the Al-rich side, an unrealistic curvature of the solidus line in the same composition range or an azeotropic point near the melting point of Cu, are amended in the new description. The procedure to establish the description of phase equilibria at high undercoolings can be transferred to other alloy systems and is of a general nature. This article is part of the theme issue 'Transport phenomena in complex systems (part 2)'.

Simultaneous Dimensional and Analytical Characterization of Ordered Nanostructures.

The spatial and compositional complexity of 3D structures employed in today's nanotechnologies has developed to a level at which the requirements for process development and control can no longer fully be met by existing metrology techniques. For instance, buried parts in stratified nanostructures, which are often crucial for device functionality, can only be probed in a destructive manner in few locations as many existing nondestructive techniques only probe the objects surfaces. Here, it is demonstrated that grazing exit X-ray fluorescence can simultaneously characterize an ensemble of regularly ordered nanostructures simultaneously with respect to their dimensional properties and their elemental composition. This technique is nondestructive and compatible to typically sized test fields, allowing the same array of structures to be studied by other techniques. For crucial parameters, the technique provides sub-nm discrimination capabilities and it does not require access-limited large-scale research facilities as it is compatible to laboratory-scale instrumentation.

The shape of dendritic tips: a test of theory with computations and experiments.

This article is devoted to the study of the tip shape of dendritic crystals grown from a supercooled liquid. The recently developed theory (Alexandrov & Galenko 2020 Phil. Trans. R. Soc. A 378, 20190243. (doi:10.1098/rsta.2019.0243)), which defines the shape function of dendrites, was tested against computational simulations and experimental data. For a detailed comparison, we performed calculations using two computational methods (phase-field and enthalpy-based methods), and also made a comparison with experimental data from various research groups. As a result, it is shown that the recently found shape function describes the tip region of dendritic crystals (at the crystal vertex and some distance from it) well. This article is part of the theme issue 'Transport phenomena in complex systems (part 1)'.

Nucleation Behavior of a Single Al-20Si Particle Rapidly Solidified in a Fast Scanning Calorimeter.

Understanding the rapid solidification behavior characteristics, nucleation undercooling, and nucleation mechanism is important for modifying the microstructures and properties of metal alloys. In order to investigate the rapid solidification behavior in-situ, accurate measurements of nucleation undercooling and cooling rate are required in most rapid solidification processes, e.g., in additive manufacturing (AM). In this study, differential fast scanning calorimetry (DFSC) was applied to investigate the nucleation kinetics in a single micro-sized Al-20Si (mass%) particle under a controlled cooling rate of 5000 K/s. The nucleation rates of primary Si and secondary α-Al phases were calculated by a statistical analysis of 300 identical melting/solidification experiments. Applying a model based on the classical nucleation theory (CNT) together with available thermodynamic data, two different heterogeneous nucleation mechanisms of primary Si and secondary α-Al were proposed, i.e., surface heterogeneous nucleation for primary Si and interface heterogenous nucleation for secondary α-Al. The present study introduces a practical method for a detailed investigation of rapid solidification behavior of metal particles to distinguish surface and interface nucleation.

Ultrafast Electron Transfer from CdSe Quantum Dots to an [FeFe]-Hydrogenase Mimic.

The combination of CdSe nanoparticles as photosensitizers with [FeFe]-hydrogenase mimics is known to result in efficient systems for light-driven hydrogen generation with reported turnover numbers in the order of 104-106. Nevertheless, little is known about the details of the light-induced charge-transfer processes. Here, we investigate the time scale of light-induced electron transfer kinetics for a simple model system consisting of CdSe quantum dots (QDs) of 2.0 nm diameter and a simple [FeFe]-hydrogenase mimic adsorbed to the QD surface under noncatalytic conditions. Our (time-resolved) spectroscopic investigation shows that both hot electron transfer on a sub-ps time scale and band-edge electron transfer on a sub-10 ps time scale from photoexcited QDs to adsorbed [FeFe]-hydrogenase mimics occur. Fast recombination via back electron transfer is observed in the absence of a sacrificial agent or protons which, under real catalytic conditions, would quench remaining holes or could stabilize the charge separation, respectively.

Single Femtosecond Laser-Pulse-Induced Superficial Amorphization and Re-Crystallization of Silicon.

Superficial amorphization and re-crystallization of silicon in <111> and <100> orientation after irradiation by femtosecond laser pulses (790 nm, 30 fs) are studied using optical imaging and transmission electron microscopy. Spectroscopic imaging ellipsometry (SIE) allows fast data acquisition at multiple wavelengths and provides experimental data for calculating nanometric amorphous layer thickness profiles with micrometric lateral resolution based on a thin-film layer model. For a radially Gaussian laser beam and at moderate peak fluences above the melting and below the ablation thresholds, laterally parabolic amorphous layer profiles with maximum thicknesses of several tens of nanometers were quantitatively attained. The accuracy of the calculations is verified experimentally by high-resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray spectroscopy (STEM-EDX). Along with topographic information obtained by atomic force microscopy (AFM), a comprehensive picture of the superficial re-solidification of silicon after local melting by femtosecond laser pulses is drawn.

Electrochemical growth mechanism of nanoporous platinum layers.

Porous platinum is a frequently used catalyst material in electrosynthesis and a robust broadband absorber in thermoelectrics. Pore size distribution and localization determine its properties by a large extent. However, the pore formation mechanism during the growth of the material remains unclear. In this work we elucidate the mechanism underlying electrochemical growth of nanoporous platinum layers and its control by ionic concentration and current density during electrolysis. The electrode kinetics and reduction steps of PtCl4 on platinum electrodes are investigated by cyclic voltammetry and impedance measurements. Cyclic voltammograms show three reduction steps: two steps relate to the platinum cation reduction, and one step relates to the hydrogen reduction. Hydrogen is not involved in the reduction of PtCl4, however it enables the formation of nanopores in the layers. These findings contribute to the understanding of electrochemical growth of nanoporous platinum layers in isopropanol with thickness of 100 nm to 500 nm.

Resolidification of a mushy-zone and directional solidification: a method for efficient alloy development demonstrated using the example of Cu-Ga-Sn.

An experimental method for alloy development that allows to systematically scan multicomponent alloy systems is presented using the Cu-Ga-Sn system as an example. Rods with homogeneous concentration distribution of different initial compositions are annealed in a steep temperature gradient with temperatures in the range from above liquidus to below solidus temperature. During resolidification of the initially formed mushy-zone, a continuously varying composition over the length of the rods develops. Further concentration gradients of the alloying elements are generated during subsequent directional solidification. The graded samples are evaluated for different properties. Vickers hardness as a function of composition was measured along the length of the samples to get first information on the mechanical behavior of bulk samples. The melting range of selected compositions (cylindrical disks of 1 mm thickness cut out of the rods) was determined by differential scanning calorimetry and compared to liquidus temperatures extrapolated from the binary systems with a fitting method and the Calphad method. With the procedure introduced here, it is possible to determine several alloy properties over an extended composition range of a multicomponent system with significantly reduced experimental effort.

Simultaneous melting and solidification of a columnar dendritic microstructure in a temperature gradient: Numerical modeling and experiments⋆.

The microstructural evolution of a SCN-ACE alloy in a temperature gradient is studied by cellular automaton (CA) modeling and in situ experiments. The initially columnar dendrites gradually evolve to a completely solid region with a planar solid/liquid interface. The CA simulations and in situ observations present the migration of secondary dendrite arms and liquid pockets due to temperature gradient zone melting (TGZM), and the movement of the interface between a mushy zone and a fully liquid zone. The CA simulations show that the interface movement toward the lower temperature region is caused by the increasing concentration of the fully liquid region. Through updating the concentration in the fully liquid zone to the initial concentration in the CA simulation for mimicking the efficient stirring in liquid, the movement of the interface between the mushy zone and the fully liquid zone is hindered. The simulated liquid fractions and mean concentrations throughout the mushy zone decrease with time, which agree well with the analytical predictions. The simulated concentrations in the resolidified mushy zone are not higher than the temperature-dependent solidus concentrations, implying that no supersaturation remains after the mushy zone fully solidifies.

Self-Assembled Graphene/MWCNT Bilayers as Platinum-Free Counter Electrode in Dye-Sensitized Solar Cells.

We describe the preparation and properties of bilayers of graphene- and multi-walled carbon nanotubes (MWCNTs) as an alternative to conventionally used platinum-based counter electrode for dye-sensitized solar cells (DSSC). The counter electrodes were prepared by a simple and easy-to-implement double self-assembly process. The preparation allows for controlling the surface roughness of electrode in a layer-by-layer deposition. Annealing under N2 atmosphere improves the electrode's conductivity and the catalytic activity of graphene and MWCNTs to reduce the I3- species within the electrolyte of the DSSC. The performance of different counter-electrodes is compared for ZnO photoanode-based DSSCs. Bilayer electrodes show higher power conversion efficiencies than monolayer graphene electrodes or monolayer MWCNTs electrodes. The bilayer graphene (bottom)/MWCNTs (top) counter electrode-based DSSC exhibits a maximum power conversion efficiency of 4.1 % exceeding the efficiency of a reference DSSC with a thin film platinum counter electrode (efficiency of 3.4 %). In addition, the double self-assembled counter electrodes are mechanically stable, which enables their recycling for DSSCs fabrication without significant loss of the solar cell performance.

Nanostructured Cu2O Synthesized via Bipolar Electrochemistry.

Cuprous oxide (Cu2O) was synthesized for the first time via an open bipolar electrochemistry (BPE) approach and characterized in parallel with the commercially available material. As compared to the reference, Cu2O formed through a BPE reaction demonstrated a decrease in particle size; an increase in photocurrent; more efficient light scavenging; and structure-correlated changes in the flat band potential and charge carrier concentration. More importantly, as-synthesized oxides were all phase-pure, defect-free, and had an average crystallite size of 20 nm. Ultimately, this study demonstrates the impact of reaction conditions (e.g., applied potential, reaction time) on structure, morphology, surface chemistry, and photo-electrochemical activity of semiconducting oxides, and at the same time, the ability to maintain a green synthetic protocol and potentially create a scalable product. In the proposed BPE synthesis, we introduced a common food supplement (potassium gluconate) as a reducing and complexing agent, and as an electrolyte, allowing us to replace the more harmful reactants that are conventionally used in Cu2O production. In addition, in the BPE process very corrosive reactants, such as hydroxides and metal precursors (required for synthesis of oxides), are generated in situ in stoichiometric quantity, providing an alternative methodology to generate various nanostructured materials in high yields under mild conditions.

Wettability Analysis of Water on Metal/Semiconductor Phases Selectively Structured with Femtosecond Laser-Induced Periodic Surface Structures.

Femtosecond (fs) laser-induced periodic surface structures (LIPSS) were selectively generated on the surface of an Ag-Si alloy consisting of a metallic and a semiconducting phase. For this purpose, the alloy was irradiated with linearly polarized fs-laser pulses (τ = 300 fs, λ = 1025 nm, frep = 100 kHz) using a laser peak fluence F = 0.30 J/cm2. Due to the different light absorption behaviors of the semiconductor (Si) and the metal (Ag) phases that result in different ablation thresholds of the respective phases, pronounced LIPSS with a period of Λ ≈ 950 nm and a modulation depth of h ≈ 220 nm were generated solely on the Si phase. The alloy surface was characterized by scanning electron microscopy, optical microscopy, white-light interference microscopy, and atomic force microscopy before and after laser irradiation. The chemical analysis was carried out by energy-dispersive X-ray spectroscopy, revealing surface oxidation of the Si phase and no laser-induced chemical modification of the Ag phase. The surface wettability of the alloy was evaluated with distilled water and compared to those of the single constituents of the composites. After fs-laser irradiation, the surface is characterized by a reduced hydrophilic water contact angle. Furthermore, the alloy selectively structured with LIPSS revealed a droplet shape change due to the distinctly different contact angles on the Si (θ = 5°) and Ag (θ = 74°) phases. This phenomenon was evaluated and discussed by local contact angle analyses using a confocal laser scanning microscope and Rhodamine B dye. In addition, it was shown that the shape change due to different contact angles of the components allowed a targeted droplet movement on a macroscopic material boundary (Ag/Si) of the alloy. Selectively structured metal/semiconductor surfaces might be of particular interest for microfluidic devices with a directional droplet movement and for the fundamental research of wettability.

Diffusionless (chemically partitionless) crystallization and subsequent decomposition of supersaturated solid solutions in Sn-Bi eutectic alloy.

Results of a study on microstructural evolution of eutectic Sn-57 wt.% Bi processed with cooling rates of 10-2, 1 K s-1 and approximately 105 K s-1 are presented. In order to distinguish different mechanisms of microstructure formation, a comparison with microstructures of different hypoeutectic alloys with compositions down to below the maximum solubility of Bi in Sn-Bi is undertaken. It is found that at the cooling rates of 10-2 and 1 K s-1, coupled eutectic growth occurs, leading to lamellar structures with different length scales. At the rapid quenching rates of approximately 105 K s-1, structure formation in the eutectic alloy is qualitatively different. Partitionless solidification resulting in a supersaturated solid solution with the initial composition is observed in both eutectic and hypoeutectic alloys. It is shown that the observed microstructure of the rapidly solidified alloys forms by the decomposition of the supersaturated solid solution. This article is part of the theme issue 'Heterogeneous materials: metastable and non-ergodic internal structures'.

Structure of Ni(OH)2 intermediates determines the efficiency of NiO-based photocathodes - a case study using novel mesoporous NiO nanostars.

We report the wet chemical synthesis of mesoporous NiO nanostars (NS) as photocathode material for dye-sensitized solar cells (DSSCs). The growth mechanism of NiO NS as a new morphology of NiO is assessed by TEM and spectroscopic investigations. The NiO NS are obtained upon annealing of preformed ß-Ni(OH)2 into pristine NiO with low defect concentrations and favorable electronic configuration for dye sensitization. The NiO NS consist of fibers self-assembled from nanoparticles yielding a specific surface area of 44.9 m2 g-1. They possess a band gap of 3.83 eV and can be sensitized by molecular photosensitizers bearing a range of anchoring groups, e.g. carboxylic acid, phosphonic acid, and pyridine. The performance of NiO NS-based photocathodes in photoelectrochemical application is compared to that of other NiO morphologies, i.e. nanoparticles and nanoflakes, under identical conditions. Sensitization of NiO NS with the benchmark organic dye P1 leads to p-DSSCs with a high photocurrent up to 3.91 mA cm-2 whilst the photoelectrochemical activity of the NiO NS photocathode in aqueous medium in the presence of an irreversible electron acceptor is reflected by generation of a photocurrent up to 23 µA cm-2.

Interaction of local solidification and remelting during dendrite coarsening - modeling and comparison with experiments.

The microstructural evolution of dendrite coarsening during isothermal holding is simulated using a quantitative cellular automaton (CA) model involving the mechanisms of both solidification and melting. The present model encompasses the essential aspects of thermodynamics and kinetics, particularly the evolution/influence of composition, temperature, and curvature, leading to valid simulations of simultaneous solidification and melting. Model validation is performed through a comparison of the CA simulations with analytical predictions for a liquid pool migrating in the mushy zone of a SCN-0.3 wt.% ACE alloy due to temperature gradient zone melting. The model is applied to simulate the microstructural evolution of columnar dendrites of a SCN-2.0 wt.% ACE alloy during isothermal holding in a mushy zone. The simulation results are compared with those of a previous CA model that does not include the melting mechanism under otherwise identical conditions. The role of melting for dendrite coarsening is quantified, showing how the melting influences the coarsening process. The present model effectively reproduces the typical dendrite coarsening features as observed in experiments reported in the literature. The simulations reveal how local solidification and melting stimulate each other through the complicated interactions between phase transformation, interface shape variation, and solute diffusion.

Alternating-magnetic-field induced enhancement of diffusivity in Ni-Cr alloys.

For applying an alternating magnetic field (AMF) in materials processing it is of high significance to understand the physical mechanisms behind the change in diffusivity in the AMF. In this work, the effect of the AMF on interdiffusion in a Ni-Cr alloy was investigated with a diffusion couple. The interdiffusion coefficient was found to increase with increasing AMF intensity. The faster diffusivity is a consequence of the enhancement of the dislocation density in the diffusion couples that was confirmed by the broadening of X-ray diffraction peaks. The higher dislocation density is attributed to the magnetoplastic effect (MPE). Theoretical considerations on the relation of MPE, dislocation density and diffusivity are in agreement with the experimental results.