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Structure formation during solidification of a Pd-Ni-Cu-P melt is studied. It is demonstrated that changes in the heat transfer conditions lead to a nonlinear change in the characteristics of the structure. The article presents the regimes of cooling the samples and the results of their structure and composition studies. It is found that a decrease in the cooling rate of the alloy leads to an increase in the size, proportion and composition of nanoinclusions in an amorphous matrix. X-ray diffraction method, electron probe microanalysis, transmission microscopy and scanning calorimetry are used for samples characterization. This article is part of the theme issue 'Transport phenomena in complex systems (part 2)'.
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Thermodynamic driving forces and growth rates in rapid solidification are analysed. Taking into account the relaxation time of the solute diffusion flux in the model equations, the present theory uses, in a first case, the deviation from local chemical equilibrium, and ergodicity breaking. The second case of ergodicity breaking may exist in crystal growth kinetics of rapidly solidifying glass-forming metals and alloys. In this case, a theoretical analysis of dendritic solidification is given for congruently melting alloys in which chemical segregation does not occur. Within this theory, a deviation from thermodynamic equilibrium is introduced for high undercoolings via gradient flow relaxation of the phase field. A comparison of the present derivations with previously verified theoretical predictions and experimental data is given. This article is part of the theme issue 'Heterogeneous materials: metastable and non- ergodic internal structures'.
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Phase-field analysis for the kinetic transition in an ordered crystal structure growing from an undercooled liquid is carried out. The results are interpreted on the basis of analytical and numerical solutions of equations describing the dynamics of the phase field, the long-range order parameter as well as the atomic diffusion within the crystal/liquid interface and in the bulk crystal. As an example, the growth of a binary A50B50 crystal is described, and critical undercoolings at characteristic changes of growth velocity and the long-range order parameter are defined. For rapidly growing crystals, analogies and qualitative differences are found in comparison with known non-equilibrium effects, particularly solute trapping and disorder trapping. The results and model predictions are compared qualitatively with results of the theory of kinetic phase transitions (Chernov 1968 Sov. Phys. JETP26, 1182-1190) and with experimental data obtained for rapid dendritic solidification of congruently melting alloy with order-disorder transition (Hartmann et al. 2009 Europhys. Lett.87, 40007 (doi:10.1209/0295-5075/87/40007)).This article is part of the theme issue 'From atomistic interfaces to dendritic patterns'.
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Controlling the morphology, electronic properties, and growth direction of nanowires (NWs) is an important aspect regarding their integration into devices on technologically relevant scales. Using the vapor-solid-solid (VSS) approach, with Ni as a catalyst and octachlorotrisilane (Si(3)Cl(8), OCTS) as a precursor, we achieved epitaxial growth of rectangular-shaped Si-NWs, which may have important implications for electronic mobility and light scattering in NW devices. The process parameters were adjusted to form cubic α-NiSi(2) particles which further act as the shaping element leading to prismatic Si-NWs. Along with the uncommon shape, also different crystallographic growth directions, namely, [100] and [110], were observed on the very same sample. The growth orientations were determined by analysis of the NWs' azimuths on the Si (111) substrates as well as by detailed transmission electron microscopy (TEM) and selected area electron diffraction (SAED) investigations.
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Microstructure of Al-40 wt%Si samples solidified in electromagnetic levitation furnace is studied at high melt undercooling. Primary Si with feathery and dendritic structures is observed. As this takes place, single Si crystals either contain secondary dendrite arms or represent faceted structures. Our experiments show that at a certain undercooling, there exists the microstructural transition zone of faceted to non-faceted growth. Also, we analyze the shape of dendritic crystals solidifying from liquid Si as well as from hypereutectic Al-Si melts at high growth undercoolings. The shapes of dendrite tips grown at undercoolings >100 K along the surface of levitated Al-40 wt%Si droplets are compared with pure Si dendrite tips from the literature. The dendrite tips are digitized and superimposed with theoretical shape function recently derived by stitching the Ivantsov and Brener solutions. We show that experimental and theoretical dendrite tips are in good agreement for Si and Al-Si samples.
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This review article summarizes current theories of the steady-state growth mode of dendrites in the form of elliptical paraboloids. The shape of dendrite tips is analyzed, temperature and solute concentration distributions are described in its vicinity, and a solution of the hydrodynamic problem of a viscous incompressible fluid flowing against a dendrite tip is developed. A significant difference in analytical solutions describing a dendrite tip as an elliptic paraboloid as compared to an axisymmetric morphology is shown. The system of nonlinear equations for determining the stationary velocity of dendrite growth and the radii of curvature of the dendrite tip along the major and minor axis of the ellipse, respectively, is derived. The developed theory is compared with experimental data on the growth of ice crystals consisting of D2O or H2O.
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Ohmic pulse heating is applied to investigate diffusion and interface controlled solid-state phase transformations. The developed device uses extensive solid-state electronics providing a high current, low voltage approach that overcomes the limitations of existing setups, most notably the use of sample geometries that allow for the reliable measurement of local temperatures and their assignment to microstructures. Power for heating is supplied by a capacitor array with adjustable voltage, and the process is controlled by microcontrollers and a solid-state relay, which allows for controlled pulses that are adjustable in microseconds. Electric currents of up to 22 kA at 90 V can be realized by the setup. Electric data are monitored and collected during the experiments, and temperature data are captured using a high-resolution infrared camera at high frame rates (1200 fps). The capabilities of the setup are demonstrated by rapid heating (106 K/s) and subsequent cooling of a brass sample. Two distinct areas of the sample are analyzed in detail, showing similar heating, but different cooling curves with rates of 104 and 102 K/s. Local microstructure analysis shows that different phase transformation mechanisms were dominant, and thus, the setup fulfills its purpose.
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Motivated by an important application of dendritic crystals in the form of an elliptical paraboloid, which widely spread in nature (ice crystals), we develop here the selection theory of their stable growth mode. This theory enables us to separately define the tip velocity of dendrites and their tip diameter as functions of the melt undercooling. This, in turn, makes it possible to judge the microstructure of the material obtained as a result of the crystallization process. So, in the first instance, the steady-state analytical solution that describes the growth of such dendrites in undercooled one-component liquids is found. Then a system of equations consisting of the selection criterion and the undercooling balance that describes a stable growth mode of elliptical dendrites is formulated and analyzed. Three parametric solutions of this system are deduced in an explicit form. Our calculations based on these solutions demonstrate that the theoretical predictions are in good agreement with experimental data for ice dendrites growing at small undercoolings in pure water.
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Recent experiments have evidenced sub-nanometer resolution in plasmonic-enhanced probe spectroscopy. Such a high resolution cannot be simply explained using the commonly considered radii of metallic nanoparticles on plasmonic probes. In this contribution the effects of defects as small as a single atom found on spherical plasmonic particles acting as probing tips are investigated in connection with the spatial resolution provided. The presence of abundant edge and corner sites with atomic scale dimensions in crystalline metallic nanoparticles is evident from transmission electron microscopy (TEM) images. Electrodynamic calculations based on the Finite Element Method (FEM) are implemented to reveal the impact of the presence of such atomic features in probing tips on the lateral spatial resolution and field localization. Our analysis is developed for three different configurations, and under resonant and non-resonant illumination conditions, respectively. Based on this analysis, the limits of field enhancement, lateral resolution and field confinement in plasmon-enhanced spectroscopy and microscopy are inferred, reaching values below 1 nanometer for reasonable atomic sizes.
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Medical grade Ni-Ti alloys with shape memory or pseudo-elastic behavior exhibit good biocompatibility because of an electrochemically passive oxide layer on the surface. In this work, the mechanical stability of surface oxide layers is investigated during reversible pseudo-elastic deformation of commonly applied medical grade Ni-Ti wires. Surface oxide layers with varying thickness were generated by varying annealing times under air atmosphere. The thicknesses of the surface oxide layers were determined by means of Rutherford backscattering spectrometry. In situ scanning electron microscopy investigations reveal a damage mechanism, which is assumed to have a significant influence on the biocompatibility of the material. The conditions that lead to the appearance of cracks in the surface oxide layer or to the flaking of surface oxide layer particles are identified. The influence of the thickness of the surface oxide layer on the damage mode is characterized. The possible impact of the damaged surface oxide layer on the material's biocompatibility and the potentials to reduce or avoid the damage are discussed.