Metastable phases in Gallium-Indium eutectic alloy particles and their size dependence

In this paper, submicrometer-sized Ga-In eutectic alloy particles were dispersed into polymethylmethacrylate (PMMA) matrix by ultrasonic vibration and sedimentation method. The solidification and melting processes of Ga-In eutectic alloy particles were studied by differential scanning calorimeter (DSC). Four endothermal peaks with the onset temperature located at 16, −11, −22, and −27 °C were observed in DSC heating curves, which corresponded to the melting process of the stable Ga-In phase α-Ga(In) and three metastable phases of β-Ga(In), δ-Ga(In) and γ-Ga(In), respectively. The stable phase α-Ga(In) can only be formed when the size of alloy particle was larger than 0.58 μm. Conversely, metastable phases β-Ga(In), δ-Ga(In) and γ-Ga(In) are mainly formed. The result shows that phase structures in Ga-In eutectic alloy are size dependent.     

Studies of electron irradiation and annealing effects on TiO2 surfaces in ultrahigh vacuum using high-resolution electron microscopy

Electron-beam-induced surface damage and subsequent annealing processes in rutile crystals have been investigated with a 300 keV high-resolution electron microscope which has been modified for ultrahigh vacuum and equipped with a specimen heating holder. Room temperature irradiation produced a reduction sequence identical to that observed previously in conventional microscope vacuum, except for some evidence of enhanced sputtering. Irradiation at higher temperatures (200–400°C) increased the damage rate resulting in approximately the same amount of the surface TiO phase but producing larger areas of the intermediate TiO₂-II phase. Sputter pits in both rutile and TiO₂-II phases became markedly more facetted as the temperature was increased. Irradiation at temperatures greater than 500°C resulted in the formation of well-facetted holes in the rutile, but no accumulation of crystalline reduced phases was observed. Annealing of the damaged areas in the absence of the electron beam, as shown by the reformation of crystalline rutile, revealed a temperature dependence for the restoration of the stoichiometry of the reduced areas, while complete removal of the sometimes extensive sputter pits was observed at temperatures in excess of 200 ° C.     

Study of the polymorphism of binary solutions of molecular substances in microsamples

Previous studies have shown that certain molecular substances taken in microsamples (droplets of about 1 μm³ in volume dispersed within an emulsion) crystallize into metastable crystalline phases. These compounds are studied in solution with benzene which does not show metastable polymorphism. The binaries benzene-1-2 dichlorobenzene, benzene-chloroform and benzene-nitrobenzene in emulsion are investigated by D.S.C. techniques. Metastable phases appear, too, and it is possible to draw metastable liquidus and locate metastable eutectics in the phase diagrams. In benzene-chloroform solution at least one new metastable phase is detected. In the benzene-nitrobenzene binary a metastable phase is detected, although neither benzene nor nitrobenzene show a metastable crystalline phase when they are pure.     

Structures of BiInSn nanoparticles formed through laser ablation

The eutectic alloy of BiInSn was ablated in water by UV pulsed radiation. Electron microscopy of the ablated material shows spherical particles that fall into three size regimes: those with diameters of ～0.5 μm, crystalline and amorphous particles with dimensions of ～30 nm, and amorphous particles that are approximately 1 nm across. The 30-nm amorphous particles are homogeneous, while there are two types of 30-nm crystalline particles, those that separate into three phases and those that are homogeneous. The existence of different characteristic sizes is explained by two mechanisms: phase explosion and Rayleigh instability of the ejected melt.     

The effect of substrate heating on the tunability of rf-sputtered Bi2O3-ZnO-Nb2O5 thin films

Reactively rf-sputtered Bi₂O₃-ZnO-Nb₂O₅ (BZN) thin films were prepared on Pt(111)/TiO₂/SiO₂/Si with substrate heating. The effects of substrate heating on the structures, morphologies, dielectric properties, and voltage-tunable dielectric properties of the films were investigated. With heating, the BZN thin films could be deposited in crystalline form as the cubic pyrochlore phase. The amounts of secondary phases, such as zinc niobate and bismuth niobate, depended on the substrate temperature. The more compounding of the BZN crystalline phase proceeded at deposition, the less formation of secondary phases and stoichiometric change occurred after post-annealing. Therefore, improvement of the dielectric constant and tunability of thin films by grain-size enlargement might be possible with proper substrate heating and post-annealing. The BZN thin films sputtered with a substrate temperature of 550 °C and annealed at 800 °C showed a maximum tunability of 26.5% at a dc bias field of 1000 kV/cm and measurement frequency of 1 MHz. PACS 81.15.Cd; 77.55.+f; 77.84.Dy; 81.40.Tv     

Phases,phase transitions and excitons of the superionic conductor AgI in the temperature range between 4.2 K and 761 K detected by diffuse reflectance spectrometry

The crystalline phase transformations, at atmospheric pressure, of the hexagonal, wurtzite type, β-silver iodide powder were studied by spectrometry of the visible, diffusely remitted light. By increasing the temperature of β-AgI from room temperature, the superionic phase may be reached in two modes. One through the β-AgI phase followed by a pretransition β′-AgI phase, the other through a β″-AgI phase only. β-AgI was transformed, by a stochastic process, into β″-AgI which, by stepwise cooling, passed into the intermediate δ-AgI phase. Maintaining the stepwise cooling, below room temperature, δ-AgI transformed itself into a temperature sensitive ϵ(T)-AgI phase which eventually resulted in the ϵ-AgI phase. Slow continuous heating retransformed ϵ-AgI into ϵ(T)-AgI which by cooling gave a ζ-AgI phase, stable down to liquid helium temperature. The original β-AgI, cooled stepwise, transformed itself, at 279 K, by a first order transition, into the sphalerite type γ-AgI. The known α, β and γ phases as well as the new β′, β″, β‴, ϵ and ζ phases were characterized by their thermal activation energies of photon absorption as well as, at sufficiently low temperatures, by their exciton emission and absorption spectra. Stochastic processes played an important role in the formation particularly of the new phases.     

Microstructural evolution during containerless rapid solidification of Co-Si alloys

The Co-12%Si hypoeutectic, Co-12.52%Si eutectic and Co-13%Si hypereutectic alloys are rapidly solidified in a containerless environment in a drop tube. Undercoolings up to 207K (0.14T_E) are obtained, which play a dominant role in dendritic and eutectic growth. The coupled zone around Co-12.52%Si eutectic alloy has been calculated, which covers a composition range from 11.6 to 12.7%Si. A microstructural transition from lamellar eutectic to divorced eutectic occurs to Co-12.52%Si eutectic droplets with increasing undercooling. The lamellar eutectic structure of the Co-12.52%Si alloy consists of εCo and Co_3Si phases at small undercooling. The Co_3Si phase cannot decompose completely into εCo and αCo_2Si phases. As undercooling becomes larger, the Co_3Si phase grows very rapidly from the highly undercooled alloy melt to form a divorced eutectic. The structural morphology of the Co-12%Si alloy droplets transforms from εCo primary phase plus lamellar eutectic to anomalous eutectic, whereas the microstructure of Co-13%Si alloy droplets experiences a `dendritic to equiaxed' structural transition. No matter how large the undercooling is, the εCo solid solution is the primary nucleation phase. In the highly undercooled alloy melts, the growth of εCo and Co_3Si phases is controlled by solutal diffusion.     

Diffusionless crystal growth in rapidly solidifying eutectic systems

Using a local nonequilibrium model of solidification, experiments on rapid eutectic growth are analyzed. An analytical solution of a problem of rapid lamellar eutectic growth under local nonequilibrium conditions in the solute diffusion field is found. It is shown that solute diffusion-limited growth of a eutectic pattern is completely finished, and diffusionless growth of the chemically homogeneous crystalline phase begins to proceed at a critical point V = V(D), where V is the solid-liquid interface velocity and V(D) is the solute diffusion speed in bulk liquid. A suppression of eutectic decomposition occurs in the range V > or = V(D) that results in a growth of homogeneous crystal phase with the initial (nominal) chemical composition of the binary system.     

Formation of the crystal structure of intermetallic compounds in mechanically activated Ni-Al and Ti-Al systems during self-propagating high-temperature synthesis

The dynamics of structural and phase transitions during heterogeneous reaction in mechanically activated mixtures has been investigated by X-ray diffraction, scanning electron microscopy, and dynamic synchrotron radiation diffraction. It is shown that the mechanisms of formation of the structure of reaction products are significantly different, depending on the temperature mode of the synthesis. Upon slow heating, the process is multistage and includes several intermediate crystalline phases. Upon fast heating, the transformation in the combustion wave occurs much faster, with only one intermediate phase observed.     

Nucleation behaviour and anomalous eutectic formation in highly undercooled Fe2O3-La2O3 eutectic melts

Employing an aero-acoustic levitator, the Fe₂O₃-16.5 mol% La₂O₃ eutectic alloy was levitated, melted, undercooled and then solidified under a containerless condition when a continuous laser beam heating system was incorporated. By revealing the surface and cross-sectional microstructures, copious nucleation is confirmed to take place in the undercooled melts solidified by either an external seeding or spontaneous crystallization. The nucleation behaviour of eutectic alloys is summarized, indicating that copious nucleation may be an intrinsic attribute of a eutectic system with the exact eutectic composition in unconstrained solidification. Considering the complexity level of crystal structures of eutectic oxide phases in the Fe₂O₃-La₂O₃ alloy, the linear kinetic constants are approximately estimated and the growth kinetics are discussed. The sluggish growth kinetics of the perovskite-type phase, that is LaFeO₃ with a higher complexity level in a unit cell leads to a decoupled growth within a single eutectic colony when the melt is undercooled to exceed the critical undercooling ΔT = 125 K. It is the decoupled growth that results in the formation of anomalous eutectics. The present concept based on the kinetic constant of different phases can also be applicable to account for the growth behaviour of other oxide eutectics when considering the stable and metastable eutectic reactions in different solidification conditions. The nucleation behaviour and growth modes in some oxide eutectic systems have been predicted in the free solidification from an undercooled state.     

Thickness dependence of the phase transition temperature in Ag2Te thin films

Electrical resistance measurements of Ag₂Te thin films of different thicknesses, vacuum deposited on clean glass substrates held at room temperature in a vacuum of 5 × 10^?5 Torr, have been carried out from about 300 to 450 K. A semiconducting-to-metallic-phase transition, which takes place during heating, is indicated by a sharp change in the slope of the resistance-vs-temperature curve. For films of different thicknesses the phase transition is found to occur at different temperatures. The size-dependent phase transition is explained by taking into account the varying surface and intergrain surface (interface) energy contributions to the total energy of the stable phase as a function of thickness and the difference in specific surface and integrain surface energies of the two phases. An order of magnitude of the difference in the function of specific surface and interfacial energies of the two phases is also made.     

Quasicrystals in a monodisperse system

We investigate the formation of a two-dimensional quasicrystal in a monodisperse system, using molecular dynamics simulations of hard-sphere particles interacting via a two-dimensional square-well potential. We find that more than one stable crystalline phase can form for certain values of the square-well parameters. Quenching the liquid phase at a very low temperature, we obtain an amorphous phase. By heating this amorphous phase, we obtain a quasicrystalline structure with fivefold symmetry. From estimations of the Helmholtz potentials of the stable crystalline phases and of the quasicrystal, we conclude that the observed quasicrystal phase can be the stable phase in a specific range of temperatures.     

Phases and phase transitions of the superionic conductor Ag2HgI4 in the temperature range between 4.2 K and 370 K detected by diffuse reflectance spectrometry

Diffuse reflectance spectra of the superionic conductor Ag₂HgI₄ powder were recorded between 4.2 K and 370 K and transformed into the Kubelka-Munk function. Six parameters of the spectral band of this function, related to the absorption band of the particular phase, were considered. The graph representing the logarithm of the integrated Kubelka-Munk spectral band versus inverse temperature was most informative. The Arrhenius behaviour of this function, in a temperature interval, was related to the existence of a phase with constant lattice structure. The non-Arrhenius behaviour was tentatively attributed to a temperature sensitive phase. Thus fifteen different crystalline phases were found, only four of them having been, up to now, unquestionably admitted. In particular, evidence was given for the existence of two superionically conducting phases and two room temperature phases. All the graphs representing the chosen parameters versus inverse temperature pointed to the existence of two separate sequences of phases: one generated by cooling gradually the β-phase, stable at room temperature, to low temperatures (β sequence), the other by heating the β-phase above the σ → β (T)₊ transition point and cooling gradually the formed α'′-phase (α′ sequence). The concept of photon absorption thermal activation energy was introduced. Its largest value was of the order of magnitude of the electrical conductivity thermal activation energy of Ag₂HgI₄. Estimates of energy band gaps and their evolution with temperature were made. It is suggested that the polymorphism of the substance is the main reason for the hysteresis loop in the superionic conductivity transition region. The low temperature phases manifested luminescence caused by exciton decay.     

On the nature of striped phases: striped phases as a stage of “melting” of 2D crystals

We discuss striped phases as a state of matter intermediate between two extreme states: a crystalline state and a segregated state. We argue that this state is very sensitive to weak interactions, compared to those stabilizing a crystalline state, and to anisotropies. Moreover, under suitable conditions a 2D system in a striped phase decouples into (quasi) 1D chains. These observations are based on results of our studies of an extension of a microscopic quantum model of crystallization, proposed originally by Kennedy and Lieb.     

The influence of crystalline grain size on the thermal stability of the Er<Subscript>0.45</Subscript>Ho<Subscript>0.55</Subscript>Fe<Subscript>2</Subscript> compound

The phase composition and the temperature dependence of the magnetization of the Er_0.45Ho_0.55Fe₂ compound in coarse-grained, microcrystalline, and submicrocrystalline states are investigated experimentally. It is found that, upon heating under vacuum, the Er_0.45Ho_0.55Fe₂ microcrystalline powder with a crystalline grain size of ∼1 μm undergoes decomposition into pure iron and rare-earth (erbium and holmium) oxides and nitrides at a temperature of 500 K. The changes observed in the phase composition of the microcrystalline powder due to annealing are confirmed by x-ray diffraction analysis. Heating of the Er_0.45Ho_0.55Fe₂ submicrocrystalline sample leads to a partial change in the phase composition. The phase composition of a large crystal (∼1 mm in size) remains unchanged upon heating to 1080 K. It is shown that the thermal stability of the Er_0.45Ho_0.55Fe₂ compound depends on the crystalline grain size. __________ Translated from Fizika Tverdogo Tela, Vol. 44, No. 6, 2002, pp. 1060–1063. Original Russian Text Copyright ? 2002 by Mulyukov, Sharipov, Korznikova.     

Observation of metastable phase separation and amorphous phase in Fe67Co33 alloy thin films synthesized by pulsed laser depositions

Pulsed laser deposition technique has been used to manipulate the structural order of Fe₆₇Co₃₃ films grown at various substrate temperatures. Films deposited at room temperature exhibited two phases including the stable crystalline phase embedded in the amorphous phase. The crystalline phase separated into two distinct bcc phases as evident from the splitting of (110) reflections, as compared to the bulk counterpart which crystalize into the single phase bcc structure. Both crystalline phases and the amorphous phase were metastable. Films prepared at higher substrate temperatures (∼500 °C), crystallized into the single stable equilibrium bcc structure. Orientation dependent magnetic properties are also presented for the films prepared at both room temperature and higher substrate temperatures. As expected, the easy axes lie parallel to the plane of the substrate due to shape anisotropy. Out of plane magnetization for the films which exhibited short range ordering is found to saturate at smaller field compared to films where single phase bcc structure is stabilized.     

New antiferroelectric liquid crystal for use in LCD

In this work, the physical properties of newly synthesized liquid crystalline compound exhibiting two liquid crystalline phases (ferroelectric and antiferroelectric) were studied. Based on the results of differential scanning calorimetry, polarizing microscopy, and photoelastic modulator methods, the temperature dependences of spontaneous polarization, tilt angle, switching time, and birefringence in the ferroelectric, as well as antiferroelectric phases were determined. Furthermore, the influence of the external electric field on the liquid crystalline textures was studied and the phase sequences at heating and cooling were revealed. The temperature dependence of spontaneous polarization was analysed by means of Landau mean-field theory, and the critical parameter β obtained for ferroelectric liquid crystalline and isotropic liquid transition was 0.21 which is close to 0.25, the value characteristic for tri-critical point.     

Crystallization of Fe-B amorphous alloy powders produced by chemical reduction

The crystallization behaviour of the Fe?B amorphous alloy powders prepared by the chemical reduction method has been investigated by Mössbauer spectroscopy. In comparison to amorphous ribbons prepared by melt-spinning, a different crystallization behaviour has been observed. After annealing the amorphous samples entirely crystallized into three crystalline phases: α-Fe, Fe₃B, and Fe₂B. In the case of Fe₈₀B₂₀ amorphous alloy ribbons produced by melt-spinning technique eutectic crystallization is commonly observed and results in the crystalline phases: α-Fe and Fe₃B. This kind of crystallization was not observed in the chemically prepared samples. The metastable tetragonal Fe₃B phase transformed completely into α-Fe and Fe₂B after annealing at 973 K for one hour.     

Structural Phase Transformations in Al/Pt Bilayer Thin Films during the Solid-State Reaction

A sequence of phases forming during the solid-phase reaction in Al/Pt bilayer thin films has been investigated by in situ electron diffraction. It is shown that the amorphous PtAl₂ phase forms first during the solid-phase reaction initiated by heating. Upon further heating, PtAl₂, Pt₂Al₃, PtAl, and Pt₃Al crystalline phases sequentially form, which is qualitatively consistent with an effective formation heat model. The content of phases forming during the reaction has been quantitatively analyzed and the structural phase transformations have been examined.

     

(Fe0.1Co0.55Ni0.35)78Si8B14金属玻璃的晶化过程及压力的影响(Ⅰ)——晶化时的相析出过程

用X射线衍射法研究了(Fe_0.1Co_0.55Ni_0.35)₇₈Si₈B₁₄金属玻璃在常压下及20kbar高压下晶化过程中的析出相及析出过程。结果表明在上述压力下晶化过程都分成两个阶段,分别对应于初级晶化和共晶晶化。在常压下,初级晶化时析出fcc-Co晶体,而共晶晶化对应着Ni₃₁Si₁₂和(FeCoNi)₃(SiB)相的析出。随着回火温度的增高或时间的延长,(FeCoNi)₃(SiB)相逐渐转变为(FeCoNi)₂₃B₆相。20kbar高压下的晶化析出过程与常压下不同的是:提高了晶化温度,在共晶晶化阶段出现了Co₂B相。此外,压力还阻止(FeCoNi)₂₃B₆相的形成。从热力学和动力学的角度讨论了压力对金属玻璃晶化过程的影响。 关键词：