Detached solidification of InSb on earth

Detached solidification of lightly gallium-doped indium antimonide was achieved in the laboratory only when the ampoule was coated with hexagonal boron nitride and when the material appeared to be oxide-free. A furnace was constructed with the temperature increasing with height in order to minimize bouyancy-driven convection, so as to maximize transport of segregated dissolved gases into the gap between the growing solid and the ampoule wall. There appeared to be no difference in results with freezing rates of 5 and 10 mm/h. Best results were obtained when the ampoule was backfilled with 20 kPa of Ar-10% H₂ prior to sealing. The detached portions were depressed by several μm from adjacent attached regions, were dull, and sometimes had microfacets and steps.     

Sea water desalination by dynamic layer melt crystallization: Parametric study of the freezing and sweating steps

This work aims at developing a dynamic layer crystallizer operated batchwise, for freezing desalination of sea water. The experiments were performed with water/NaCl solutions and with samples of sea water from Nice, Rabat and Marseille. The pilot crystallizer consists of a cooled tube immersed in a cylindrical double jacketed tank. The solution is poured into the tank and the crystallization takes place on the external surface of the tube, by applying a cooling ramp in the tube. The solution is agitated by air bubbling. The whole process involves the freezing step, leading to the crystallization of the ice layer and the sweating step, which consists of purifying in depth the ice layer by melting the impure zones. A parametric study on the effect of the operating parameters has allowed quantifying the role of the different key parameters of the freezing and sweating steps. Three experiments allowed reaching salinities lower than 0.5 g/kg, satisfying the standards of drinking water. The duration of the whole process dropped to only 8 h (5 h for freezing and 3 h for sweating), with a yield of sweating equal to about 50%, provided severe conditions were applied for sweating. Higher yields required longer times. Overall, the results show the feasibility of the technique.     

The liquid state of large clusters with pairwise atomic interactions

Formation of the liquid state for clusters with a pair interaction between atoms is examined within the framework of the void model, in which configurational excitation of atoms results from formation of voids. Void parameters are found from computer simulation by molecular dynamics methods for Lennard-Jones clusters and from real thermodynamic parameters of the liquid states of condensed inert gases. Phase transitions are analyzed in terms of two aggregate states. This information allows us to divide the entropy jump during the solid-liquid phase transitions in two parts, so that one corresponds to configuration excitation at zero temperature, and the other is a contribution from thermal vibrations of atoms. The latter part contributes from approximately 40% for Lennard-Jones clusters consisting of 13 and 55 atoms up to 56% for bulk inert gases. These magnitudes explain the validity of melting criteria based on thermal motion of atoms, even though this phase transition results from configurational excitation of ensembles of bound atoms. It is shown that the void concept allows us to analyze various aspects of the liquid state of clusters including the existence of the freezing temperature below which no metastable liquid state exists, and the properties of glassy states which may exist below the freezing point.     

Distinct property effects on rapid solidification of a thin liquid layer on a substrate subject to self-consistent melting

Heat transfer of a molten splat in a thin layer rapidly solidified on a cold substrate subject to self-consistent melting and distinct thermal and physical properties has been numerically investigated. Micro-electro-mechanical systems, semi-conductor technology, splat cooling, plasma or powder spray deposition, single and twin-roller melt spinning, strip and slab casting, melt extraction, etc. are usually characterized by rapid solidification of a thin liquid layer on a cold substrate. This work has proposed that the one-dimensional rapid freezing in the splat is governed by nonequilibrium kinetics at the solidification front while the melting in the substrate is determined from the traditional phase change condition. The results show that to delay the freezing of the splat and accelerate the melting of the substrate, an increase in the splat-to-substrate specific heat ratio and decreases in Stefan number, dimensionless solid conductivity of the substrate and substrate-to-splat density ratio are suggested. The freezing of the splat and melting of the substrate are delayed by increasing dimensionless initial temperature and decreasing dimensionless nucleation temperature of the splat. An early melting of the substrate while maintaining the same onset time for the freezing of the splat can be achieved by increasing the dimensionless kinetic coefficient and equilibrium melting temperature of the splat and decreasing the dimensionless equilibrium melting temperature of the substrate. The effects of the parameters on enthalpies and interface velocities in the splat and substrate are also presented.     

Doping mechanism and properties of Zn-doped GaN-epitaxial layers

The role of oxygen in the process of doping GaN by Zn is established. It is shown theoretically and experimentally that Zn is dissolved in GaN in the form of complexes Zn O when oxygen or water vapour is present in the ambient of the growth reactor. Most of the complexes are neutral. Only the small part of Zn introduced is situated in electrically active positions. This fact can explain the enormously high Zn concentration which is necessary to obtain the compensation of GaN native donors. The electrical and luminescence properties of GaN epitaxial layers doped by Zn are given and the relation of these properties to the growth and doping conditions are considered.     

Separation of glucose and fructose by freezing crystallization

This work comprises the implementation of a methodology for the study of an industrial crystallization process by freezing and cooling to be applied in the separation of sugars with industrial relevance (glucose and fructose). The main interest is the production of fructose. This sugar is obtained by sucrose hydrolysis in acidic solutions, which yields an equimolar mixture of glucose and fructose. The developed separation process is based on the solubility difference between the sugars. Experiments were carried out in a jacketed glass crystallizer where the solution coming from the sucrose acid inversion was submitted to a slow cooling. Since glucose has lower solubility than fructose, it crystallizes in the bulk as the temperature is lowered, thus it can be removed from the solution by fliltration or centrifugation. Best fructose‐glucose separation was achieved for a total sugar concentration of 50 wt%. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Rayleigh scattering in silica glass with heat treatment

We investigated Rayleigh scattering in silica glass with heat treatment under various conditions, including quenching and slow cooling, and its relation to fictive temperature. The Rayleigh scattering intensity varied according to the conditions of the heat treatment. The scattering intensity in slowly cooled samples is less than that in quenched samples after heating at the same temperature. We evaluated fictive temperatures based on measurements of infrared absorption and Raman scattering. The Rayleigh scattering intensity was related to the fictive temperature regardless of the heat treatment conditions, and a linear relation between them was obtained. In addition, we suggest that the decrease in scattering intensity in slowly cooled samples results from structural relaxation due to viscous flow during the cooling process.     

Development of scale formed on cooling surface towards equilibrium state

Changes in the morphology of scale deposited on the surface of a submerged cooling element during its prolonged contact with a saturated solution of oxalic acid were studied. Needle-like crystals formed during the initial stage of oxalic acid scale depositing bring about a markedly rough surface. During a longer contact with the solution, however, the needle-like crystals are gradually dissolved and the scale surface is becoming smooth. After a steady state has been established, i.e. when mass transfer between the solution and scale does not take place any longer, the scale recrystallises completely forming a smooth crystalline coating on the cooling wall and neither its morphology nor weight are changing any further.     

Precipitation of In2O3 nano-crystallites from glasses in the system Na2O/B2O3/Al2O3/In2O3

Glasses in the system Na₂O/B₂O₃/Al₂O₃/In₂O₃ were melted and subsequently tempered in the range from 500 to 700 °C. Depending on the chemical composition, various crystalline phases were observed. From samples without Al₂O₃, In₂O₃ could not be crystallized from homogeneous glasses, because either spontaneous In₂O₃ crystallization occurred during cooling, or other phases such as NaInO₂ were formed during tempering. The addition of alumina, however, controlled the crystallization of In₂O₃. Depending on the crystallization temperature applied, the crystallite sizes were in the range from 13 to 53 nm. The glass matrix can be dissolved by soaking the powdered glass in water. This procedure can be used to prepare nano-crystalline In₂O₃-powders.     

Growths of bubble/pore sizes in solid during solidification—an in situ measurement and analysis

The sizes of a bubble trapped in solid after nucleation on the solidification front during an upward freezing of water containing a dissolved oxygen or carbon dioxide gas are experimentally measured and quantitatively predicted in this work. The sizes of the bubble include the height, radius and contact angle of the cap on the solidification front and the length of the bubble in the solid. From in situ measurements of bubble shapes in solid at cold temperatures of −25° and −15°C, it quantitatively shows that pore formation can be divided into five regimes: (1) nucleation on the solidification front, (2) spherical growth, (3) solidification rate-controlled elongation, (4) disappearance of the bubbles, and (5) formation of the pores in solid. To interpret experimental results, equations incorporated with the growth rate of a spherical bubble and solidification rate to predict bubble shapes in the solid during the spherical growth and solidification rate-controlled elongation are successfully proposed. It is found that the time to reach the regime of solidification rate-controlled elongation corresponding to the maximum radius of the bubble is increased by decreasing solidification rate and increasing spherical growth rate of the bubble. Experimental data show the effects of initial gas concentration and solidification rate on geometries of the bubble in solid. Valuable database for more systematical studies of pore formation in solids are provided.     

Modeling and measurement of residual stresses in a bulk metallic glass plate

The recent advent of multi-component alloys with exceptional glass forming ability has allowed the processing of large metallic specimens with amorphous structure. The possibility of formation of thermal tempering stresses during the processing of these bulk metallic glass (BMG) specimens was investigated using two models: (i) instant freezing model, and (ii) viscoelastic model. The first one assumed a sudden transition between liquid and elastic solid at the glass transition temperature. The second model considered the equilibrium viscosity of BMG. Both models yielded similar results although from vastly different approaches. It was shown that convective cooling of Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 plates with high heat transfer coefficients could potentially generate significant compressive stresses on the surfaces balanced with mid-plane tension. The crack compliance (slitting) method was then employed to measure the stress profiles in a BMG plate that was cast in a copper mold. These profiles were roughly parabolic suggesting that thermal tempering was indeed the dominant residual stress generation mechanism. However, the magnitude of the measured stresses (with peak values of only about 1.5% of the yield strength) was significantly lower than the modeling predictions. Possible reasons for this discrepancy are described in relation to the actual casting process and material properties. The extremely low residual stresses measured in these BMG specimens, combined with their high strength and toughness, serve to further increase the advantages of BMGs over their crystalline metal counterparts.     

Ice-Nucleation Activity of AgI Particles on the Surface of Water and into the Volume

The ice-nucleation activity of AgI particles is investigated. The critical supercoolings are determined for water drops with particles situated on the drop surface and suspended into the drop volume. The ice-nucleation activity of the AgI particles decreases with the gradually penetration of the particles into the volume. A large alteration (about 10 °C) for the mean freezing temperature is established. An attempt is made to explain this phenomenon with the lowering of the nucleation work on the three-phase particle/water/water vapour contact.     

Observation of the boundary layer on the top of ice growing from melt

The boundary layer appearing near the ice front during directional freezing of water was investigated by the Mach-Zehnder interferometer. Temperature profiles in the cell during experiments were displayed. Properties of this layer were measured in dependence on growth rate and properties of water. The gas bubbles capturing and building of air channels in the ice were also observed. Nature of the observed transition layer is briefly discussed.     

Generation of slanted gas-filled icicles

A procedure for the generation of slanted gas-filled icicles by freezing, using a domestic refrigerator, is described. The freezing vessel was a plastic ice-cube tray, which was filled both with tap and deionized water and was frozen successively from the outer to the inner compartments of the tray. Icicles having slanted elevations grew out of the surface of the deionized water of the innermost compartments. The erection angle of the icicles to the horizontal lay between 30° and 60°, for the three longest and thinnest specimens it was almost exactly 30°. All icicles have gas inclusions. Their shape varies between an irregular distribution of circular bubbles and a nearly uninterrupted axial gas channel together with dendrite-like, radially distorted bubbles. If a cold (-18°C) specimen comes into contact with warm and humid room-air, then hoarfrost is observed at the bottom and the top of the icicle, while the area in between remains transparent.     

TiO2 thin films as sensing gas materials

TiO₂ thin films were prepared by DC reactive magnetron sputtering on heated Si, quartz and glass substrates using O₂ and water vapor as reactive gases. The percentage of anatase and rutile as well as the grain size strongly depend on the deposition conditions, as revealed by X-ray diffraction patterns. The films deposited on Si substrates are pure rutile, while a mixed anatase/rutile structure occurs in the films deposited on glass and quartz substrates. Smaller grain rutile and anatase films were prepared in a water vapor atmosphere, in contrast to the films grown in oxygen. The former choice considerably increases the sensing properties of titanium dioxide films. The gas sensitivity was investigated for some reducing gases (methane, acetone, ethanol and liquefied petroleum gas) and the optimum operating temperatures were found.     

Dynamical scaling analysis using the Lillie Number for vitrification of deeply supercooled glycerol

Thermal response was measured for a deeply supercooled glycerol specimen by applying calorimetric temperature scanning rate spectroscopy, cooling the specimen from liquid at a slow constant cooling rate until glass transition was observed. The effective fraction of glass as a function of temperature was determined and a new definition of glass transition temperature, T_gC, as the temperature at which the effective glass fraction to be 0.5 was presented. The relation between this and the cooling rate showed the Arrhenius behavior. The effective glass fraction curves shifted linearly as a function of ln(cooling rate). When T was scaled to the Lillie Number, the glass fraction lay on a master curve, which was successfully fitted with a Kohlrausch–Williams–Watts function. The Kohlrausch exponent, the relaxation time as a function of temperature and the kinetic fragility index were determined. The results were compared with literature values.     

Evaluation of glass-forming ability criterion from phase-transformation kinetics

Applying kinetic analysis upon crystallization of metallic glass, a quantitative relation between the critical cooling rate and the onset temperature of crystallization was obtained for glass-forming alloys. Effects of the onset temperature of crystallization, the liquidus temperature and the glass transition temperature on the critical cooling rate were analytically described. Three rules guiding the development of more reliable glass-forming ability criteria are suggested.     

Rotational probe relaxation and scaling in fragile glass formers

The rotational dynamics of a stiff paramagnetic tracer dissolved in supercooled SALOL is investigated via electron spin resonance spectroscopy. The study shows that the molecular rotation follows different dynamical regimes as the temperature is lowered. In particular, on cooling through the critical temperature T_C of the SALOL, the coupling between rotational relaxation and viscosity weakens and enhanced rotational diffusion is observed. In this temperature interval, the relationship between rotational correlation times and viscosity is fairly well described by a power law τ∝η^ξ (Fractional Debye-Stokes-Einstein law). Activated reorientation is observed in the temperature region around the glass transition of the SALOL. The rotational dynamics of the tracer dissolved in SALOL are compared with its rotation in ortotherphenyl (OTP) investigated in previous studies, and a scaling procedure is proposed.     

Thermodynamische Betrachtungen zur Nitridbildung auf Eisen bei Gasnitrieren

The instructions about the calculation of the thermodynamic conditions for the formation of iron-nitrogen-phases (nitrided α-iron, γ′-nitrides, ϵ-nitrides) are compiled. The results calculated according to these instructions are in good correspondence with the experimental results stated in the technical publications. It is pointed out that there is a want of knowledge on the relation of equilibrium between the nitrogen content of ϵ-nitride and the conditions of nitriding (temperature, pressure, composition of the gas). Resulting from the experimental investigations a valid relation is set up for the nitrogen content of ϵ-nitride which adjusts at equilibrium with the gas phase in the range of temperatures from 550 to 570°C. By means of X-ray tests the dependence of the hexagonal ϵ-nitride lattice constant relation on the content of dissolved nitrogen is mathematically determined.     

Viscosity and glass transition temperature of hydrous float glass

Viscosity of water-bearing float glass (0.03-4.87 wt% H₂O) was measured in the temperature range of 573-1523 K and pressure range of 50-500 MPa using a parallel plate viscometer in the high viscosity range and the falling sphere method in the low viscosity range. Melt viscosity depends strongly on temperature and water content, but pressure up to 500 MPa has only minor influence. Consistent with previous studies on aluminosilicate compositions we found that the effect of dissolved water is most pronounced at low water content, but it is still noticeable at high water content. A new model for the calculation of the viscosities as a function of temperature and water content is proposed which describes the experimental data with a standard deviation of 0.22 log units. The depression of the glass transition temperature T_g by dissolved water agrees reasonably well with the prediction by the model of Deubener [J. Deubener, R. Müller, H. Behrens, G. Heide, J. Non-Cryst. Solids 330 (2003) 268]. Using water speciation measured by near-infrared spectroscopy we infer that although the effect of OH groups in reducing T_g is larger than that of H₂O molecules, the difference in the contribution of both species is smaller than predicted by Deubener et al. (2003). Compared to alkalis and alkaline earth elements the effect of protons on glass fragility is small, mainly because of the relatively low concentration of OH groups (max. 1.5 wt% water dissolved as OH) in the glasses.