Electromagnetic levitation containerless processing of metallic materials in microgravity: thermophysical properties.

Transitions from the liquid to the solid state of matter are omnipresent. They form a crucial step in the industrial solidification of metallic alloy melts and are greatly influenced by the thermophysical properties of the melt. Knowledge of the thermophysical properties of liquid metallic alloys is necessary in order to gain a tight control over the solidification pathway, and over the obtained material structure of the solid. Measurements of thermophysical properties on ground are often difficult, or even impossible, since liquids are strongly influenced by earth's gravity. Another problem is the reactivity of melts with container materials, especially at high temperature. Finally, deep undercooling, necessary to understand nucleus formation and equilibrium as well as non-equilibrium solidification, can only be achieved in a containerless environment. Containerless experiments in microgravity allow precise benchmark measurements of thermophysical properties. The electromagnetic levitator ISS-EML on the International Space Station (ISS) offers perfect conditions for such experiments. This way, data for process simulations is obtained, and a deeper understanding of nucleation, crystal growth, microstructural evolution, and other details of the transformation from liquid to solid can be gained. Here, we address the scientific questions in detail, show highlights of recent achievements, and give an outlook on future work.

Thermophysical properties of liquid Zr52.5Cu17.9Ni14.6Al10Ti5-prospects for bulk metallic glass manufacturing in space.

Bulk metallic glasses are of critical interest for a wide range of applications, including their use in spacecraft gearboxes and mechanisms due to their excellent low-temperature, unlubricated wear resistance. Also of interest, is the potential for in-space manufacturing of metal alloys and the use of microgravity to determine fundamental thermophysical properties to inform ground-based modeling and experimentation. In this work, a Zr-based bulk metallic glass was processed in the electromagnetic levitator ISS-EML to determine undercooling, electrical resistivity, specific heat capacity, surface tension, and viscosity. A 6.5 mm sphere was vitrified during the processing, resulting in the first bulk metallic glass manufactured on board the international space station (ISS).

Structure and dynamical properties of liquid Ni64Zr36 and Ni65Hf35 alloys: an ab initio molecular dynamics study.

Ab initio molecular dynamics simulations are performed to investigate the atomic structures and dynamics of Ni64Zr36 and Ni65Hf35 metallic liquids in a temperature range of 1400-2500 K. Calculated results are in good agreement with recently reported high temperature experimental data. Local atomic structures are analyzed and compared for Ni64Zr36 and Ni65Hf35 metallic liquids in terms of average bond length, coordination number, Honey-Andersen index, Bond-orientation order, spatial correlation and Voronoi tessellation methods. It is found that Zr-Zr bonds have larger average length of 3.32 Å than 3.22 Å for Hf-Hf bonds, causing sluggish diffusion in Ni65Hf35 liquids. Zr and Hf atom-centered clusters with higher coordination numbers are inclined to aggregate with high-coordinated clusters, while Ni atom-centered clusters with lower coordination numbers prefer to avoiding to be the nearest neighbor with each other. Temperature dependent diffusion coefficients reveal the decoupled diffusion in both liquids, which are related with different spatial correlations for Ni- and Zr- (or Hf-) centered clusters.

Plasmonic reflection color filters with metallic random nanostructures.

We develop reflective color filters with randomly distributed nanodisks and nanoholes fabricated with hydrogen silsesquioxane and Ag films on silicon substrate. They exhibit high resolution, angle-independence and easily up-scalable fabrication, which are the most important factors for color filters for industrial applications. We uncover the underlying mechanism after systematically analyzing the localized surface plasmon polariton coupling in the electric-field distribution. The agreement of the experimental results with those from the simulation indicates that tunable colors across the visible spectrum can be obtained by simply varying the diameter of the nanodisks, promoting their applications.

Hybrid 3D structures of ZnO nanoflowers and PdO nanoparticles as a highly selective methanol sensor.

The present study concerns the enhancement of methanol selectivity of three dimensional (3D) nanoflowers (NFs) of ZnO by dispersing nickel oxide (NiO) and palladium oxide (PdO) nanoparticles on the surface of the nanoflowers to form localized hybrid nano-junctions. The nanoflowers were fabricated through a liquid phase deposition technique and the modification was achieved by addition of NiCl and PdCl2 solutions. In addition to the detailed structural (like X-ray diffraction (XRD), electron dispersive spectroscopy (EDS), X-ray mapping, XPS) and morphological characterization (by field emission scanning electron microscopy (FESEM)), the existence of different defect states (viz. oxygen vacancy) was also confirmed by photoluminescence (PL) spectroscopy. The sensing properties of the pristine and metal oxide nanoparticle (NiO/PdO)-ZnO NF hybrid sensor structures, towards different alcohol vapors (methanol, ethanol, 2-propanol) were investigated in the concentration range of 0.5-700 ppm at 100-350 °C. Methanol selectivity study against other interfering species, viz. ethanol, 2-propanol, acetone, benzene, xylene and toluene was also investigated. It was found that the PdO-ZnO NF hybrid system offered enhanced selectivity towards methanol at low temperature (150 °C) compared to the NiO-ZnO NF and pristine ZnO NF counterparts. The underlying mechanism for such improvement has been discussed with respective energy band diagram and preferential dissociation of target species on such 3D hybrid structures. The corresponding improvement in transient characteristics has also been co-related with the proposed model.

Polarization-independent plasmonic subtractive color filtering in ultrathin Ag nanodisks with high transmission.

We demonstrate a TE/TM polarization-independent plasmonic subtractive color filtering scheme employing ultrathin two-dimensional Ag nanodisks. These TE/TM polarization-independent subtractive color filters exhibit small feature sizes (below 200 nm) and high transmission up to 70% in the visible spectral region, superior to previously reported plasmonic color filters. Simulated optical transmission spectra and colors are in good agreement with experimental results. The color-filtering behaviors strongly depend on thickness and period of nanodisks. Underlying mechanisms are also discussed in detail.

Effect of relative nanohole position on colour purity of ultrathin plasmonic subtractive colour filters.

Plasmonic subtractive color filters through patterning periodic nanostructures on ultrathin Ag films deposited on a glass substrate, exhibiting good durability, simple fabrication, and flexible color tunability, have attracted considerable attention due to their tremendous potential applications. While previous studies have mainly focused on their extraordinary physical mechanisms, color purity, which is another key parameter for high quality imaging applications, has been much less investigated. In this work, we demonstrate that the relative position of nanoholes patterned on ultrathin Ag films can largely affect the color purity of plasmonic subtractive color filters. The calculated results agree reasonably well with the experimental data, revealing that the purity of subtractive colors can be improved by changing the nanohole arrays from square lattice to triangular lattice without reducing transmission at visible frequencies. In addition, underlying mechanisms are clarified by systematically analyzing the dominant valley in transmission spectra.

Consecutive magnetic and magnetocaloric transitions in herringbone nanostructured Heusler Mn50Ni41Sn9 alloy.

A herringbone nanostructured Mn-rich Heusler Mn50Ni50-Sndelta (8 - 9) alloy exhibits tailored magnetocaloric properties in the martensite and ferro <-> paramagnetic transitions concur in a narrow temperature window. In a Sn --> Ni substitution 8 - 9, the martensite (M) <-- austenite (A) transition up-lifts adequately well above the room temperature - 310.5 K in the DSC thermogram and magnetization scanned with temperature. A noninterrupted heating following a cooling in DSC at a given rate gives a smaller enthalpy change deltaH(M <-- A) - deltaH(M --> A approximately equal to 282 mJ/g (deltaC(P)(M <-- A) - deltaC(P)(M --> A) approximately equal to 0.025 mJ/g-K in the heat capacity), i.e., the M <-> A transition process lacks a complete reversibility. Warming a zero-field cooled sample retains lower magnetization (sigma) at low fields B, e.g., by 58% over the field cooled value at 5 mT, wherein merely low field magnetic susceptibility imparts the magnetization process. A reversible thermal hysteresis thus the transition traces in cooling and heating. The field diminishes difference in two sigma-values progressively, e.g., only - 12% lasts at 5 T. The two curves bifurcate below 160 K (B-5 mT) and the gap grows exponentially over lower temperatures before sigma(M <-- A) gets steady near 60 K in a superparamagnetic (SPM) behavior. The SPM feature (follows the Langevin model) below a paramagnetic regime begins (> or = 250 K) before a ferromagnetic A-state lines-up the successive transitions. Temperature and frequency dependence ac and dc susceptibilities describe the surface spins dynamics.

Color tuning by local sputtering metal nanolayer on microstructured porous alumina.

This article reports a novel color tuning method by local sputtering nanolayers on microstructured porous alumina (PA) templates with different pore depths. With the aid of scanning electron microscopy observation, physical models of the original and sputtered PA templates are set up, and the details of the color tuning method are further proposed. Two series of colors covering the whole visible range are first obtained by respectively sputtering Cr and Ag nanolayers on two groups of PA templates with pore-depths ranging from 230 to 490 nm. A vivid colorful pattern of "Butterfly wings" is then prepared by local sputtering such Cr and Ag nanolayers on the surface of a PA with 310 nm pore-depth. The scanning electron microscopy images of Cr and Ag sputtered PA surfaces show different microstructures, which is in agreement with different color exhibiting. This method is expected to have a potential of being widely applied in the fields of micro-optics, microstructures, advanced materials, and micro/nanotechnology.

Structure and nano-mechanical characteristics of surface oxide layers on a metallic glass.

Owing to their low elastic moduli, high specific strength and excellent processing characteristics in the undercooled liquid state, metallic glasses are promising materials for applications in micromechanical systems. With miniaturization of metallic mechanical components down to the micrometer scale, the importance of a native oxide layer on a glass surface is increasing. In this work we use TEM and XPS to characterize the structure and properties of the native oxide layer grown on Ni(62)Nb(38) metallic glass and their evolution after annealing in air. The thickness of the oxide layer almost doubled after annealing. In both cases the oxide layer is amorphous and consists predominantly of Nb oxide. We investigate the friction behavior at low loads and in ambient conditions (i.e. at T = 295 K and 60% air humidity) of both as-cast and annealed samples by friction force microscopy. After annealing the friction coefficient is found to have significantly increased. We attribute this effect to the increase of the mechanical stability of the oxide layer upon annealing.

Synthesis and properties of hydroxyapatite-containing porous titania coating on ultrafine-grained titanium by micro-arc oxidation.

Equal channel angular pressing results in ultrafine-grained (approximately 200-500 nm) Ti with superior mechanical properties without harmful alloying elements, which benefits medical implants. To further improve the bioactivity of Ti surfaces, Ca/P-containing porous titania coatings were prepared on ultrafine-grained and coarse-grained Ti by micro-arc oxidation (MAO). The phase identification, composition, morphology and microstructure of the coatings and the thermal stability of ultrafine-grained Ti during MAO were investigated subsequently. The amounts of Ca, P and the Ca/P ratio of the coatings formed on ultrafine-grained Ti were greater than those on coarse-grained Ti. Nanocrystalline hydroxyapatite and alpha-Ca(3)(PO(4))(2) phases appeared in the MAO coating formed on ultrafine-grained Ti for 20 min (E20). Incubated in a simulated body fluid, bone-like apatite was completely formed on the surface of E20 after 2 days, thus evidencing preferable bioactivity. Compared with initial ultrafine-grained Ti, the microhardness of the E20 substrate was reduced by 8% to 2.9 GPa, which is considerably more than that of coarse-grained Ti (approximately 1.5 GPa).

Optical properties in nanofluids of gold nanoparticles in poly(vinylpyrrolidone).

Nanofluids of selective visible colors are developed in gold nanoparticles embedded in polymer molecules of polyvinyl pyrrolidone (PVP) in water. A simple HAuCl4 reaction with PVP molecules (a weak reductant) in aqueous solution at 60-70 degrees C yields the nanofluid in a single process step with an AU3+ --> Au caloric reduction. Part of PVP molecules, which binds to a resulting Au-nanoparticle of nascent surfaces, insulates it from the Au3+ species and thus disrupts it to grow further, by immobilizing in the PVP molecules. Varying the 0-1.0 wt% Au-contents (in Au-PVP) tunes effectively the Au-surface plasmon bands (SPR) in Au-core-shell particles in conjunction with the surface PVP molecules. Characteristic SPR absorption band shifts regularly from at 535 nm in 0.05 wt% Au to a value as large as 571 nm upon increasing the Au-content to 1.0 wt%. The SPR band favors emission at approximately 440 nm in a core --> shell energy transfer in core-shell particles of an exchange coupled system, when irradiating at approximately 250 nm in the 5d(10)6s --> 5d(9)6sp (Au) interband transition. Electron microscopic images, with the electron diffraction, reveal small Au-crystallites in shapes of cuboids (or bars) of core-shells, with 5-10 nm width (5-15 length), and their clusters of mostly pentagons.

X-ray photoelectron spectrum in surface interfacing of gold nanoparticles with polymer molecules in a hybrid nanocomposite structure.

In situ Au3+--> reaction and dispersion of the resulting gold in the form of nanoparticles (NPs) in a reactive polymer medium, such as poly(vinyl alcohol) (PVA) molecules in hot water, are explored to devise a composite Au-PVA structure of self-standing films. The Au-NPs (0-2 wt%) tailor a violet to purple to a yellowish color of films from a colorless base polymer. A distinct surface interface (of thickness 2-5 nm) from the core (20-30 nm diameter) is resolved in transmission electron microscope images. The x-ray photoelectron spectrum (XPS) in the 81-91 eV range accounts for the effect which causes asymmetric shapes of the 4f(7/2) and 4f(5/2) Au bands. In a model structure, the asymmetry arises in the contribution of the surface Au atoms, which extend a chemical bridging with surface O atoms from the PVA molecules in a surface layer. A similar asymmetry also arises in C 1s and O 1s bands in the counterpart PVA molecules at 287.79 and 532.35 eV, respectively. At Au content as large as 2 wt%, no separate XPS band arises on a negligibly small fraction of surface Au atoms when Au-NPs have been grown in thin laminates (or cuboids and prisms).

Gold nanoparticles reinforced poly (vinyl alcohol) of self-standing optical films.

A simple one-step process is developed to synthesize self-standing optical films of Au-doped polymer of poly(vinyl alcohol) (PVA). The visible color could be tuned precisely over a wide range from the violet to a yellowish with selective Au-contents from 0.1 to 5.0 wt%. The synthetic procedure involves a caloric Au3+ --> Au reaction in aqueous PVA at 60-90 degrees C temperatures followed by casting the sample (Au-nanocrystals (NCs) embedding in the PVA polymer molecules) as films or other shapes. Stable color persists of nanocolloids as well as films. The NCs are thin platelets of triangular, square, rectangular, or hexagonal shapes. There are very few pentagonal platelets and nanorods. As analyzed with microstructure, the NCs formation results in a structural anisotropy by the preferential adsorption of PVA on selective facets. An Au-content dependent emission occurs in the 400-650 nm regions, useful for possible optical data storage, nonlinear optical devices, and color pigments.