Thermal instability of decahedral structures in platinum nanoparticles

We conduct molecular dynamics simulations of 887 and 1389-atom decahedral platinum nanoparticles using an embedded atom potential. By constructing microcanonical caloric curves, we identify structural transitions from decahedral to fcc in the particles prior to melting. The transitions take place during phase coexistence and appear to occur via melting of the decahedral structure and subsequent recrystallisation into the fcc structure.     

Dynamics of simple liquids at heterogeneous surfaces: Molecular-dynamics simulations and hydrodynamic description

In this paper we consider the effect of surface heterogeneity on the slippage of fluid, using two complementary approaches. First, MD simulations of a corrugated hydrophobic surface have been performed. A dewetting transition, leading to a super-hydrophobic state, is observed for pressure below a "capillary" pressure. Conversely, a very large slippage of the fluid on this composite interface is found in this super-hydrophobic state. Second, we propose a macroscopic estimate of the effective slip length on the basis of continuum hydrodynamics, in order to rationalize the previous MD results. This calculation allows to estimate the effect of a heterogeneous slip length pattern at the composite interface. Comparison between the two approaches shows that they are in good agreement at low pressure, but highlights the role of the exact shape of the liquid-vapor interface at higher pressure. These results confirm that small variations in the roughness of a surface can lead to huge differences in the slip effect. On the basis of these results, we propose some guidelines to design highly slippery surfaces, motivated by potential applications in microfluidics.     

Engineering embedded metal nanoparticles with ion beam technology

In this paper, we summarize our recent results of study on how to engineer the embedded metal nanoparticles in silica by ion implantation and ion irradiation technologies, including controlling the size, distribution and morphology of nanoparticles. The optical properties of the tailored nanoparticle composites are studied. Thermal annealing, electron beam irradiation, and chemical erosion are used to study the stability of these embedded nanoparticles by ex situ or in situ transmission electron microscopy observation.     

In situ SAXS study on size changes of platinum nanoparticles with temperature

Poly(vinylpyrrolidone) (PVP)-coated platinum (Pt) nanoparticles were prepared in methanol-water reduction method. In situ small-angle X-ray scattering (SAXS) and X-ray diffraction (XRD) techniques were used to probe the size change of particles and crystallites with temperature. Tangent-by-tangent (TBT) method of SAXS data analysis was improved and used to get the particle size distribution (PSD) from SAXS intensity. Scherrer’s equation was used to derive the crystallite size from XRD pattern. Combining SAXS and XRD results, a step-like characteristic of the Pt nanoparticle growth has been found. Three stages (diffusion, aggregation, and agglomeration) can be used to describe the growth of the Pt nanoparticles and nanocrystallites. Aggregation was found to be the main growth mode of the Pt nanoparticles during heating. The maximum growth rates of Pt nanoparticles and Pt nanocrystallites, as well as the maximum aggregation degree of Pt nanocrystallites were found, respectively, at 250 °C, 350 °C and 300 °C. These results are helpful to understanding the growth mode of nanoparticles, as well as controlling the nanoparticle size.     

Interface interaction and wetting of Sc<Subscript>2</Subscript>O<Subscript>3</Subscript> exposed to Cu–Al and Cu–Ti melts

Scandia is a thermodynamically stable oxide and could be used as a structural material for a crucible in order to avoid a melt contamination. In the present study wetting experiments of Cu–Al and Cu–Ti melts on Scandia substrate were preformed at 1423 K by a sessile drop method. It was established that Al and Ti additions lead to the improved wetting and that the final contact angle decreases with increasing the additives concentration. For Al containing melts, the contact angle changes gradually with time, and a relatively thick interaction layer, which consists of Al₂O₃, Sc₂O₃, and metallic channels, was formed at the Sc₂O₃/Cu–Al interface. For Ti containing melts, the final contact angle is achieved already during heating, and an extremely thin layer based on a Ti–Sc–O compound was detected by AES at the Sc₂O₃/Cu–Ti interface. The results of a thermodynamic analysis, which takes into account the formation free energy of the oxides, involved in the systems, and the thermodynamic properties of the liquid solutions are in a good agreement with the experimental observations.     

Size-dependent effects in solutions of small metal nanoparticles

A new theoretical approach for the calculation of optical properties of complex solutions is proposed. It is based on a dielectric matrix ε_m with included small metallic inclusions (less than 3 nm) of spherical shape. We take into account the mutual interactions between the inclusions and the quantum finite-size effects. On the basis of the effective medium model, TDLDA and Kohn-Sham theories, some analytical expressions for the effective dielectric permittivity of the solution are obtained.     

Synthesis and characterization of silica nanosprings by a low temperature chemical vapor deposition

Silica nanosprings were synthesized using a simple, low temperature, chemical vapor deposition method via a vapor–liquid–solid mechanism. Nanosprings with excellent uniformity and helicity in high and repeatable yields have been observed. The morphology and crystal structure of the nanosprings were characterized by scanning electron microscopy and transmission electron microscopy. The chemical composition of the nanosprings was determined using the energy-filtered transmission electron microscopic method. The as-grown nanomaterials were confirmed to be amorphous silica with irregularly shaped Au catalytic particles located at the tips. In addition, we propose a spontaneous spinning growth model to explain the formation of such helical nanostructures.     

Effects of polydispersity on the order-disorder transition of diblock copolymer melts

The effect of polydispersity on an AB diblock copolymer melt is investigated using lattice-based Monte Carlo simulations. We consider melts of symmetric composition, where the B blocks are monodisperse and the A blocks are polydisperse with a Schultz-Zimm distribution. In agreement with experiment and self-consistent field theory (SCFT), we find that polydispersity causes a significant increase in domain size. It also induces a transition from flat to curved interfaces, with the polydisperse blocks residing on the inside of the interfacial curvature. Most importantly, the simulations show a relatively small shift in the order-disorder transition (ODT) in agreement with experiment, whereas SCFT incorrectly predicts a sizable shift towards higher temperatures.     

2D aggregate sizing by combining laser-induced incandescence (LII) and elastic light scattering (ELS)

The combination of laser-induced incandescence and elastic light scattering has been further developed to allow for a quantitative two-dimensional determination of characteristic properties of soot aggregates, namely radius of gyration R _g and number N _p of primary particles per aggregate. In demonstrating the principle of the method, we have in a first approach approximated the particle ensemble as monodisperse and used a structure factor with an exponential cut-off function. Nonetheless, experiments performed on a laminar premixed ethene flame demonstrate basically good agreement with observations from literature and data from electron microscopy on thermophoretically obtained samples.     

Enhanced magnetization of nanoparticles of Mg x Fe(3? x )O4 (0.5≤ x ≤1.5) synthesized by combustion reaction

For the first time nanocrystalline magnetic particles of Mg _x Fe_(3−x)O₄ with x ranging from 0.5 to 1.5 have been synthesized by a combustion reaction method using iron nitrate Fe(NO₃)₃.9H₂O, magnesium nitrate Mg(NO₃)₂.6H₂O, and urea CO(NH₂)₂ as fuel without intermediate decomposition and/or calcining steps. X-ray diffraction patterns of all systems showed broad peaks consistent with cubic inverse spinel structure of MgFe₂O₄. The absence of extra reflections in the diffraction patterns of as-prepared materials ensures the phase purity. The mean crystallite sizes determined from the prominent (311) peak of the diffraction using Scherrer’s equation and transmission electron microscopy micrographs were c.a. 40 nm with spherical morphology. Fourier transform infrared spectra of the as-prepared material showed traces of organic and metallic salt by-products; however, these could be removed by washing with deionized water. Typical hysteresis curves were obtained for all specimens in magnetic field up to 14 T between 4 and 340 K. The saturation magnetization was 48.3 emu/g and 31.3 emu/g, 44.8 emu/g, and 28.4 emu/g for x=1.0 and 0.8 at 4 K and 340 K, respectively. The saturation magnetization, M _s , of nanoparticles of the MgFe₂O₄ specimen is about 50% higher when compared to the bulk. The enhanced magnetization measured in our nanoparticles MgFe₂O₄ specimens may be attributed to the uncompensated magnetic moment of iron ions between the A- and B-sites, i.e., changes in the inversion factor. Our magnetization results of MgFe₂O₄ specimens are comparable to the existing data for the same compound but with different particle size and prepared by different synthesis methods.     

Highly oriented electrospun polycaprolactone micro/nanofibers prepared by a field-controllable electrode and rotating collector

Novel ZnO tetrapod-shaped nanostructures with pearl-necklace-shaped arms were successfully synthesized using mixture of Zn, ZnO, and carbon powder as source. The definite supersaturation ratio provided by Zn, ZnO, and carbon powder was considered as the crucial factor of determining the formation of this kind of structure, and a negative feedback growth model combined with octahedral nucleation mechanism was proposed. Two other comparative experiments were also conducted to study the growth behavior of reagent species under different supersaturation ratios. Our experiments provided a beneficial experimental exploration in controlled growth of nanostructures through modulating supersaturation ratio by source, and these obtained novel nanostructures were also expected to have potential application as functional blocks in nanodevices. Furthermore, the study of photoluminescence indicated that the physical properties were strongly dependent on the crystal structure.     

Optical characterization and manipulation of alkali metal nanoparticles in porous silica

Rubidium and cesium metal nanoparticles were grown in nanoporous silica samples placed in alkali vapor cells. Their size and shape were investigated by measuring the sample optical transmittance. Spectral changes due to photodesorption processes activated by weak light were also analyzed. Alkali atoms photoejected from the silica walls diffuse through and out of the nanopores, modifying both the nanoparticle distribution in the silica matrix and the atomic vapor pressure in the cell volume. The number of rubidium and cesium atoms burst out of the samples was measured as a function of photon energy and fluence. The optical absorption measurements together with the analysis of the photodesorption yield give a complete picture of the processes triggered by light inside the nanopores. We show that atomic photodesorption, upon proper choice of light frequency and intensity, induces either growth or evaporation of nanosized alkali metal clusters. Cluster size and shape are determined by the host-guest interaction.     

Fabrication of fluorescent nanoparticles of dendronized perylenediimide by laser ablation in water

Highly fluorescent organic nanoparticles with size of about 300 nm were prepared by nanosecond laser ablation of micrometer-sized powder of dendronized perylenediimide dispersed in water. The nanoparticle colloidal solution provided a fluorescence quantum yield of 0.58. The absorption and emission spectral studies demonstrated that the bulky dendron groups at the side bays of perylenediimide chromophore efficiently suppress the interchromophoric interactions in the nanoparticles. Fluorescence measurement on several single nanoparticles underlines that the prepared nanoparticles are bright and photo-stable enough to be a useful probe for single particle fluorescence investigation.     

Morphology studies of the metal surfaces with enhanced absorption fabricated using interferometric femtosecond ablation

Recently, the enhancing of bulk metals optical absorption with focused femtosecond pulses was demonstrated. This absorption enhancement is caused by different nano- and micro-structures which are formed during laser ablation with ultrashort pulses. In this paper we study the evolution of the surface structures using interferometric ablation and compare it to normal fs-ablation. Previously we have shown that interferometric femtosecond ablation is an efficient method to fabricate absorbing metal surfaces. In this study we ablated large areas of hole-array structures with different pulse numbers in polished stainless steel and copper samples. The evolution of surface morphology and the depth of the holes for these structured surfaces are presented. In addition, the reflectance of laser generated surface structures are measured at the wavelength range of 200–2300 nm using a standard spectrophotometer.     

Description of electrons correlation in1,3S-states of negative ion of positronium

The energy of ground^1,3S-states of negative positronium ion in the hyperspherical coordinates method has been calculated in Born-Oppenheimer and adiabatic approximations accounting the contribution of angle and radial correlation. Quasi-crossing points for autodetaching adiabatic potentials were revealed, which forms a structure in nonadiabatic potential. The received energy values have been compared with results of calculations performed using other methods. It was shown that in order to receive energy values with accuracy of 10⁻⁴ a.u. it is necessary to include more than 70 elements into the basis for determination of adiabatic potentials or to use Padé approximation on the basis dimension. Presented at the 11th Colloquium “Quantum Groups and Integrable Systems”, Prague, 20–22 June 2002. The work is supported by the Slovak Agency for Science, Grant 2/7157/20.     

Shape transformation transitions in a model of fixed-connectivity surfaces supported by skeletons

A compartmentalized surface model of Nambu and Goto is studied on triangulated spherical surfaces by using the canonical Monte Carlo simulation technique. One-dimensional bending energy is defined on the skeletons and at the junctions, and the mechanical strength of the surface is supplied by the one-dimensional bending energy defined on the skeletons and junctions. The compartment size is characterized by the total number L^′ of bonds between the two-neighboring junctions and is assumed to have values in the range from L^′ = 2 to L^′ = 8 in the simulations, while that of the previously reported model is characterized by L^′ = 1, where all vertices of the triangulated surface are the junctions. Therefore, the model in this paper is considered to be an extension of the previous model in the sense that the previous model is obtained from the model in this paper in the limit of L^′↦1. The model in this paper is identical to the Nambu-Goto surface model without curvature energies in the limit of L^′↦∞ and hence is expected to be ill-defined at sufficiently large L^′. One remarkable result obtained in this paper is that the model has a well-defined smooth phase even at relatively large L^′ just as the previous model of L^′↦ 1. It is also remarkable that the fluctuations of surface in the smooth phase are crucially dependent on L^′; we can see no surface fluctuation when L^′≤ 2, while relatively large fluctuations are seen when L^′≥ 3.     

Sound absorption by a solution of nanoparticles

Absorption of an acoustic wave in a colloidal solution via two mechanisms: due to viscous friction in the liquid and due to energy dissipation on nanoparticles is studied. The dependence of the imaginary part of the wave vector on the frequency is estimated in both cases. It is shown that in typical colloidal solutions, the first absorption mechanism dominates at low frequencies, and the second one, at higher, ultrasonic frequencies.     

Self-cleaning characteristics on a thin-film surface with nanotube arrays of anodic titanium oxide

Self-cleaning of a surface of nanotube arrays of anodic titanium oxide (ATO) is demonstrated. The ATO was prepared in fluoride ion containing sulfate electrolytes with a structure of 0.4 μm length, 100 nm pores diameter, 120 nm interpore distance, 25 nm pore wall thickness, a 8×10⁹ pores cm⁻² pore density, and 68.2% porosity. Prepared as thin films either directly from a Ti foil or on a glass substrate, these arrays have the property that water drops spread quickly over the surface of the films without irradiation. In contrast, a flat anatase TiO₂ film requires irradiation with UV light for several minutes before the contact angle decreases to zero. The observed self-cleaning behavior of the ATO thin films is due to the capillary effect of the nanochannel structure and the superhydrophilic property of the anatase TiO₂ surface inside the tube.     

The effect of Ti on the wetting of CaF<Subscript>2</Subscript> substrate by In–Ti and Ga–Ti alloys. Ab-initio consideration

CaF₂ is a thermodynamically stable, non-reactive compound, displaying a relatively high contact angle with pure liquid metal melts. A remarkable decrease of this contact angle takes place when small amounts of Ti are added to liquid In (a decrease from 125 to 20°) or to liquid Ga (from 118 to 60°). Thermodynamic analysis indicates that this feature cannot be attributed to chemical reactions between the substrate and the melt. It was suggested that the reason for this behavior may be a preferential titanium adsorption from the liquid In–Ti or Ga–Ti solution at the substrate surface. In order to understand the nature of the In–Ti or Ga–Ti bonding in the vicinity of the CaF₂ surface, the adsorption energy of 0.5 monolayer of In and Ga was computed for three different surface conditions: (i) clean CaF₂(111), (ii) CaF₂(111) with In or Ga adatoms, and (iii) CaF₂(111) with Ti adatoms. The differences in adsorption energies for these configurations are related to the electron charge redistribution in the vicinity of the interface, and to the density of states of the electronic subsystems. It was found that the adsorption energy of In or Ga increases due to the lateral interactions with the adatoms. According to the analysis, a strong lateral interaction exists between Ti adatoms and Me, while relatively weak interaction exists between Me and Me adatoms. The difference of the lateral interactions was considered in order to explain the improvement of the wetting of CaF₂ substrate by Ti alloying of In and Ga.