In situ energy dispersive X-ray diffraction analysis of the high-pressure–high-temperature stability of amorphous Co–Fe–Zr–B alloys

The pressure–temperature stability of Co₅₆Fe₁₆Zr₈B₂₀ amorphous alloys was investigated by energy dispersive X-ray diffraction. The in situ experiments were performed at the MAX80/F2.1 high-pressure beamline at the HASYLAB synchrotron radiation facility (Hamburg, Germany). Crystallization experiments were performed under different applied pressures up to 2 GPa. The effect of static pressure on the crystallization temperature stems from the pressure effect on the nucleation barriers and modified kinetics of solid-state diffusion under high-pressure–high-temperature conditions.     

Crystallization Control of Molten Ba(B0.9Al0.1)2O4 from Supercooled Pendant Drop

Crystallization process of molten Ba(B_0.9Al_0.1)₂O₄ from supercooled pendant drop was investigated on a viewpoint of a supercooling and a solid phase formation. Molten pendant drop was crystallized by a rod touching at an crystallization temperature under an adequate degree of supercooling. Three kinds of rods were used. Each rod was made of Pt, hBN and graphite which had different wettability to the molten drop. There were three kinds of phases on a solid Ba(B_0.9Al_0.1)₂O₄, such as a high temperature crystal phase, a low temperature crystal phase and a glass phase. All phases could be formed by the present method.     

Effect of foreign phases on the growth of NaBi(WO4)2 crystals

Single crystals of NaBi(WO₄)₂ (NBW) have been grown by Czochralski technique, employing differently synthesized starting charge and different axial temperature gradients. The causes behind inherent problems related to compositional changes and associated lowering in crystallization temperature have been probed by analyzing XRD and DTA patterns of post growth residual charge. Presence of low melting phases viz. Na₂WO₄ and hitherto unreported compound Na₅Bi(WO₄)₄ is thought to be responsible for the observed decrease in crystallization temperature. This problem was tackled by segregating pure phase material through re‐crystallization, under high axial temperature gradient. The use of re‐crystallized charge enabled transformation of almost the entire charge into a single crystal of high transparency. The effect of starting charge synthesis and temperature gradient on the optical transmission characteristics of NBW crystal has also been investigated. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Amorphization from the quenched high-pressure phase of silicon and germanium

The phase transitions from the quenched high-pressure phase, including amorphous state, have been investigated for crystalline silicon and germanium at various pressures. X-ray diffraction patterns have been measured at pressures up to 15 GPa and temperatures down to 90 K by an energy-dispersive method using synchrotron radiation and a diamond anvil cell. The quenched β-Sn phase undergoes an amorphous phase transition when heated at 1.5 GPa for c-Si and 2.0 GPa for c-Ge. On the other hand, the quenched β-Sn phase transforms into a metastable crystalline phase when heated at higher pressures. The phase behavior is discussed in relation to the pressure dependence of the height of potential barrier between the β-Sb and amorphous phases and that between the β-Sn and metastable phases. The coordination number for the pressure-induced amorphous germanium, obtained through amorphization from the quenched high-pressure phase, is estimated to be about 4.     

Crystallization temperature of amorphous Fe80B20 under pressure

The resistance of rapidly quenched Fe₈₀B₂₀ was recorded versus T at a rate of 7 K/min and various pressures up to 2.5 GPa. The onset of crystallization, T_x, was defined by extrapolation at the sharp change in resistance associated with crystal growth. The resulting slope of T_x is 15 K/GPa. Separate measurements at atmospheric pressure yielded T_x versus rate of temperature increase, R = dT/dt. crystallization times from the literature were recalculated to yield T_x, and the results are compared with our data. Nominally amorphous materials of the same composition show markedly different properties. It is also shown that the variation of T_x with R is mostly due to the change in viscosity.     

Effect of liquid state on the crystallization of Zr65Al7.5Ni10Cu17.5 metallic glass

The correlation between the quenching temperature and the crystallization of the Zr₆₅Al_7.5Ni₁₀Cu_17.5 metallic glass was examined. The electrical resistivity and the thermal property were measured to monitor the structural change of the samples quenched at the temperature of 1473 K, 1573 K, 1673 K and 1773 K, respectively. The consistent results of DSC and d(ρ_(T)/ρ₀)/dT‐T curves indicated different crystallization behaviors of the samples. For the samples quenched from 1773 K, the increase in ΔT_x, T_rg and γ imply higher glass forming ability. Moreover, according to the XRD patterns of samples annealed at different temperatures, the melt temperature influences the formation of crystallized phases of amorphous Zr₆₅Al_7.5Ni₁₀Cu_17.5 alloy.     

Crystallization of amorphous Ni35Zr65 and Fe40Ni40P14B6 under proton irradiation

Two amorphous alloys, Ni₃₅Zr₆₅ and Fe₄₀Ni₄₀P₁₄B₆, were irradiated using 400 keV protons at several temperatures below the crystallization temperature, T_x, to peak doses in the neighborhood of 3.5 to 4.5 dpa. Irradiation at 250°C resulted in the crystallization of both alloys, which were examined by transmission electron microscopy of samples electrolytically polished to various distances from the irradiated surface to study the effect of dose. Samples masked from the proton beam remained amorphous during irradiation. In the Ni₃₅Zr₆₅ alloy crystallization of the equilibrium phases propagated throughout the entire sample, while the in the Fe₄₀Ni₄₀P₁₄B₆ alloy crystallization was observed only in those parts of the samples lying within the proton range. Neither alloy crystallized during irradiation at 100°C. In both these alloys the amorphous phase is therefore evidently stable at irradiation temperatures below approximately 0.6 T_x. An examination of the literature on irradiation damage of binary alloys and intermetallic compounds suggests that there is a tendency for initially amorphous alloys to remain amorphous at irradiation temperatures, T_irr < 0.3 T_L, where T_L (≈T_x) is the “melting” temperature (either a eutectic, peritectic or congruent melting temperature). Also, these same alloys, even when they are initially crystalline, transform to the amorphous state during irradiation at T < 0.3 T_L. Some other crystalline alloys have also been shown to transform to the amorphous state at T_irr < 0.3 T_L even though they have never been prepared in this condition by rapid quenching techniques. The temperature 0.3 T_L appears to be a lower limit, however, since the crystalline to amorphous transformation occurs in many of these alloys at temperatures greater than 0.3 T_L. It is suggested, by analogy with results on void formation in irradiated metals, that this low temperature limit is related to the low mobility of vacancies in these materials, although the mechanism of crystallization, or conversely amorphization, is not fully understood.     

Structure and properties of Ni60(Nb100−xTax)34Sn6 bulk metallic glass alloys

Refractory bulk metallic glasses and bulk metallic glass composites are formed in quaternary Ni-Nb-Ta-Sn alloy system. Alloys of composition Ni₆₀(Nb_100−xTa_x)₃₄Sn₆ (x = 20, 40, 60, 80) alloys were prepared by injection-casting the molten alloys into copper molds. Glassy alloys are formed in the thickness of half mm strips. With thicker strips (e.g., 1 mm), Nb₂O₅ and Ni₃Sn phases and the amorphous phase form an in situ composite. Glass transition temperatures, crystallization temperatures, and ΔT_x, defined as T_x1 − T_g (T_x1: first crystallization temperature, T_g: glass transition temperature) of the alloys increase dramatically with increasing Ta contents. These refractory bulk amorphous alloys exhibit high Young’s modulus (155-170 GPa), shear modulus (56-63 GPa), and estimated yield strength (3-3.6 GPa).     

Study on crystallization kinetics of Al65Cu20Ti15 amorphous alloy

The crystallization behavior and thermal stability of amorphous phases of Al₆₅Cu₂₀Ti₁₅ alloy obtained by mechanical alloying were investigated by using in-situ X-ray diffraction and differential scanning calorimetry (DSC) under non isothermal and isothermal conditions. The result of a Kissinger analysis shows that the activation energy for crystallization is 1131 kJ/mol. The higher stability against crystallization of Al₆₅Cu₂₀Ti₁₅ amorphous alloy is attributed to the stronger interaction of atoms in the Al-Cu-Ti system and formed of complicated compound like Al₅CuTi₂ and Al₄Cu₉ as primary phases. The isothermal crystallization was modeled by using the Johnson-Mehl-Avrami (JMA) equation. The Avarami exponents suggest that the isothermal crystallization is governed by a three-dimensional diffusion-controlled growth.     

Pressure dependence of the Boson peak in glassy As2S3 studied by Raman scattering

A detailed pressure dependence study of the low energy excitations of glassy As₂S₃ is reported over a wide pressure range, up to 10 GPa. The spectral features of Boson peak are analyzed as a function of pressure. Pressure effects on the Boson peak are manifested as an appreciable shift of its frequency to higher values, a suppression of its intensity, as well as a noticeable change of its asymmetry leading to a more symmetric shape at high pressures. The pressure-induced Boson peak frequency shift agrees very well with the predictions of the soft potential model over the whole pressure range studied. As regards the pressure dependence of the Boson peak intensity, the situation is more complicated. It is proposed that in order to reach proper conclusions the corresponding dependence of the Debye density of states must also be considered. Comparing the low energy modes of the crystalline counterpart of As₂S₃, as well as the experimental data concerning the pressure dependencies of the Boson peak frequency and intensity, a structural or glass-to-glass transition seems to occur at the pressure ∼4 GPa related to a change of local dimensionality of the glass structure. Finally, the pressure-induced shape changes of the Boson peak can be traced back to the very details of the excess (over the Debye contribution) vibrational density of states.     

Crystallization kinetics of (Ni0.75Fe0.25)78Si10B12 amorphous alloy

Amorphous ribbon specimen of (Ni_0.75Fe_0.25)₇₈Si₁₀B₁₂ has been prepared by a single roller melt-spinning technique in the air atmosphere. The crystallization kinetics of the alloy has been investigated using different thermal analysis by means of continuous heating and isothermal heating. The activation energy of the alloy has been calculated by using Kissinger plot method and Ozawa plot method based on differential thermal analysis data, respectively. The products of crystallization have been analyzed by X-ray diffraction. A single phase of γ-(Fe, Ni) solid solution with grain size of about 10.3 and 18.5 nm precipitates in the amorphous matrix after annealing at temperatures 715 and 745 K, respectively. The crystallized phases are γ-(Fe, Ni) solid solution, Fe₂Si, Ni₂Si, Fe₃B and unidentified phase after annealing at 765 K. The details of nucleation and growth during the isothermal crystallization are expatiated in terms of local Avrami exponent and local activation energy.     

Effects of the addition of SiC on the crystallization of Al84Ni8Co4Y3Zr1 (at.%) amorphous ribbons

Amorphous alloys present exceptional values of mechanical strength but lack any significant plasticity at room temperature. Deformation of amorphous alloys occurs in shear transformation zones that connect to form shear bands, which are easier to deform than the surrounding matrix, thus facilitating further deformation in the same location of the specimen. However, the presence of particles dispersed in the amorphous matrix can modify such strain softening behavior, resulting in real plastic deformation before fracture. Also, depending on the type of particles and how they are introduced, they can modify the crystallization behavior of the amorphous matrix by acting as heterogeneous nucleation sites. In this context, this paper reports on the effects of the addition of SiC particles on the crystallization of Al₈₄Ni₈Co₄Y₃Zr₁ amorphous ribbons. Pre-alloyed ingots with and without added SiC particles were melt-quenched into amorphous ribbons by the single-roller melt-spinning technique and then selectively and partially crystallized at the first and second crystallization temperatures, as determined by differential scanning calorimetry. Primary crystallization of nanometric-sized fcc-Al crystals was found to occur in both ribbons (with and without added SiC), confirming that crystallization reactions were not altered by the ceramic particles. Aluminum carbide (Al₄C₃) crystals resulting from high-temperature liquid metal/SiC reactions were observed as coatings on the SiC particles and as isolated particles dispersed in the amorphous solid matrix. In both cases, the Al₄C₃ particles also did not change the crystallization behavior of the amorphous Al₈₄Ni₈Co₄Y₃Zr₁ matrix, since no heterogeneous nucleation of fcc-Al crystals was observed.     

In situ crystallization of lithium disilicate glass: Effect of pressure on crystal growth rate

Crystallization of a Li₂O · 2SiO₂ (LS₂) glass subjected to a uniform hydrostatic pressure of 4.5 and 6 GPa was investigated up to a temperature of 750 °C. The density of the compressed glass is ∼2% greater at 4.5 GPa than 1 atm and, depending on the processing temperature, up to 10% greater at 6 GPa. Crystal growth rates investigated as a function of temperature and pressure show that lithium disilicate crystal growth is an order of magnitude slower at 4.5 GPa than 1 atm resulting in a shift of +45 °C (±10 °C) in the growth rate curve at high pressure compared to 1 atm conditions. At 6 GPa lithium disilicate crystallization is suppressed entirely, while a new high pressure lithium metasilicate crystallizes at temperatures 95 °C (±10 °C) higher than those reported for lithium disilicate crystallization at 1 atm. The observed decrease in crystal growth rate with increasing pressure for the lithium disilicate glass up to 750 °C is attributed to an increase in viscosity with pressure associated with fundamental changes in glass structure accommodating densification.     

Plastic deformation behavior of amorphous Fe78Si9B13 alloy at elevated temperature

The plastic deformation behavior of amorphous Fe₇₈Si₉B₁₃ alloy was investigated under uniaxial tension and gas pressure bulging. The deformed specimens were studied by means of XRD and SEM. It is shown that amorphous Fe₇₈Si₉B₁₃ ribbon has good deformation ability in the temperature range from 450 °C to 500 °C. The elongation of 36.3% and the relative bulging height (RBH) of 0.45 were obtained at 500 °C. In the uniaxial tension test, the amount of the crystalline α-Fe phase increases with deformation temperature below the crystallization temperature, which also suggests that the tensile stress promotes the crystallization of amorphous Fe₇₈Si₉B₁₃ ribbon. The suitable gas pressure bulging conditions for the specimens are 500 °C, 3.4 MPa and 30 min.     

Characterization of nanocrystals in laser condensates deposited through vanadium evaporation in an oxygen atmosphere

The influence of the substrate temperature T _sub (20–360°C) and the oxygen pressure P(O₂) (5 × 10⁻³−0.13 Pa) in an evaporation chamber on the structure and phase composition of films prepared through laser sputtering of a vanadium target is investigated by electron diffraction and in situ transmission electron microscopy (with the use of the bend extinction contour technique for determining the bending of the crystal lattice). It is demonstrated that the oxygen content in the films increases with an increase in the oxygen pressure P(O₂) at a fixed substrate temperature T _sub and decreases with an increase in the substrate temperature T _sub at a fixed oxygen pressure P(O₂). The conditions responsible for the formation and composition of the crystalline (VO_0.9) and amorphous (V₂O₃) phases in the films are determined. It is established that the phase composition of the film depends on the angle of condensation of the vapor-plasma flow. The crystallization of the V₂O₃ amorphous phase is accompanied by an increase in the density by 9.2%. It is revealed that the V₂O₃ spherulites growing in the amorphous film have a bent crystal lattice. The bending of the crystal lattice can be as large as ∼42 deg/μm.

     

The effect of high pressure on crystallization of splat-cooled V2O5

Crystallization of splat-cooled V₂O₅ under high pressure was examined. By X-ray diffraction and thermal analysis, it is shown that the non-crystalline V₂O₅ crystallizes dramatically up to about 6 kb. Crystallization temperature increases with increasing pressure under this pressure range.At higher pressure (20–60 kbar), crystallization occurs gradually and the crystallization temperature has a slight tendency to decrease with increasing pressure.     

Stability and crystallization of Fe-Co-Nb-B amorphous alloys

New soft magnetic amorphous alloys with a wide supercooled liquid region were obtained by increasing the boron content (up to 30 at.%) and by addition of cobalt (composition range between 5 and 42 at.%) in FeNbB based materials. Upon thermal treatments, the stability and the crystallization behavior of Fe₅₂Co₁₀Nb₈B₃₀ and Fe₂₂Co₄₀Nb₈B₃₀ have been studied by using X-ray diffraction (XRD) and transmission electron microscopy (TEM). On the other hand, the Curie temperature change, T_c, of the remaining amorphous phases has been determined by thermomagnetic analysis (TMG). Sub-micrometric fcc-(Co,Fe) and fcc-(Fe,Co)₂₁Nb₂B₆ grains were observed to crystallize at a relatively high temperature (950-970 K) providing an excellent stability of the amorphous states. Due to the partitioning behavior, occurring during crystallization, the Curie temperature of the remaining amorphous structure is observed to increase in the case of the Fe₅₂Co₁₀Nb₈B₃₀ composition while a decrease of T_c to the lower temperatures is observed with the Fe₂₂Co₄₀Nb₈B₃₀ composition.     

Polycrystalline silicon with large disk-shaped grains by Ni-mediated crystallization of doped amorphous silicon

Silicide mediated crystallization (SMC) of p-doped amorphous silicon (a-Si) has been studied. There are the different grain-shapes of crystallization of doped and non-doped a-Si. Non-doped a-Si is crystallized with needle-shaped grains, while it is observed the disk-shaped grains are formed in crystallized doped a-Si. The crystallization of slightly doped a-Si exhibits larger grain size compared with non-doped and heavily doped films. The p-dopant in a-Si suppresses the formation of the NiSi₂ precipitate which act as a crystallization nucleus, causing continuous grain growth and the formation of disk-shaped grains.     

Study of the structure of PyHReO4 under high pressure

The structure of deuterated pyridinium perrhenate (d₅PyH)ReO₄ (C₅D₅NHReO₄) is studied by X-ray diffraction at room temperature and pressures up to 3.5 GPa and by neutron diffraction in the temperature range 10–293 K and at pressures up to 2.0 GPa. Under normal conditions, this compound belongs to the orthorhombic space group Cmc2₁ (ferroelectric phase II). At room temperature and pressures above P > 0.7 GPa, a transition to an orthorhombic phase (paraelectric phase II) is observed. This paraelectric phase is described by the space group Cmcm. At a pressure as high as P = 2.0 GPa, phase I remains stable at temperatures down to 10 K. This fact indicates that the high pressure suppresses the ferroelectric state in deuterated pyridinium perrhenate (d₅PyH)ReO₄.     

Nanocrystallization and structure of Fe78.5Ni1.0Mo0.5Si6.0B14.0 amorphous alloy

The effect of Ni and Mo alloying additions on crystallization of an Fe–Si–B based amorphous alloy was studied by applying various experimental techniques – DSC, XRD and TEM. It was shown that both alloying additions Ni and Mo change the crystallization temperature as well as the activation energy of primary crystallization. The phases formed during primary crystallization for the Fe₈₀Si₆B₁₄ and Fe_78.5Ni₁Mo_0.5Si₆B₁₄ alloys were the same, however the morphologies were significantly different. The addition of 1.0 at.% of Ni and 0.5 at.% Mo changed the crystallization mechanism and the type of formed phases. Such additions also resulted in formation of nanocrystals. The kinetic and thermodynamic characteristics of annealed specimens of amorphous metallic Fe₈₀Si₆B₁₄ and Fe_78.5Ni₁Mo_0.5Si₆B₁₄ alloys were established. These characteristics were determined based on measurements of instantaneous changes of electrical strength. It was shown that the method of electromotive force measurements was more sensitive to structural changes and the phase composition of amorphous metallic electrodes in comparison with the X-ray method.