Short-range and medium-range order in rapidly quenched Al50Mg50 alloy

The rapid quenching processes of a larger-scale Al₅₀Mg₅₀ alloy system consisting of 100,000 atoms have been simulated by using molecular dynamics method. The formation and structure of short-range order (SRO) and medium-range order (MRO) in the rapidly quenched Al₅₀Mg₅₀ alloy are investigated by means of several structural analysis methods. It is found that the massive icosahedra in the Al₅₀Mg₅₀ supercooled liquid prevent it from crystallizing and play a critical role in the formation of metallic glass. The SRO in Al₅₀Mg₅₀ metallic glass cannot be modeled by a uniquely prescribed stereo-chemical structure or five Bernal polyhedra, but various types of basic clusters in which the icosahedron is dominant. The MRO is characterized by some certain types of extended icosahedral clusters combined by intercross-sharing atoms in the form of chains or rings, which is different from the FCC and icosahedral building schemes for the MROs in metallic glasses with significant chemical SRO. The size distributions of these MRO clusters exhibit a magic number sequence of 19, 23, 25, 27, 29, 31, 33, 35, 37, 41….     

Structure changes in Al80Ni15Y5 amorphous alloy

The structure of Al₈₀Ni₁₅Y₅ amorphous alloy at various temperatures have been studied with X-ray diffraction methods. The obtained scattered intensities, structure factors, pair correlation functions and main structure parameters have been analyzed. Temperature dependences of the parameters suggest formation of Al, Al₃Ni and Al₂₃Ni₆Y₄ phases upon crystallization of an amorphous alloy.     

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.     

Crystallization behaviour of Al-based metallic glasses below and above the glass-transition temperature

The present paper aims to report an effect of a supercooled liquid region on crystallization behaviour of the Al₈₅Y_8−xNd_xNi₅Co₂ metallic glasses produced by rapid solidification of the melt. The paper describes the crystallization process at different regimes of heat treatment. It is found that crystallization behaviour of the above-mentioned Al-based metallic glasses above the glass-transition temperature and below it follows different transformation mechanisms. Formation of the primary nanoscale α-Al particles was observed during continuous heating or after isothermal annealing above the glass-transition temperature. During isothermal annealing below the glass-transition temperature an unknown metastable phase is formed conjointly with α-Al. The metastable phase formed in the Nd-free alloy varies from that in the Nd-bearing alloys. Al₈₅Nd₈Ni₅Co₂ amorphous alloy exhibiting no glass transition crystallizes equally during isothermal calorimetry at different temperatures and during continuous heating.     

The structure of Al–Cu and Al–Si eutectic melts

The structure of Al₈₃Cu₁₇ and Al₈₈Si₁₂ liquid eutectic alloys has been studied using the X-ray diffraction (XRD) and reverse Monte-Carlo (RMC) methods. The total and partial structure factors and pair correlation functions as well as structure parameters obtained therefrom have been analyzed. Chemically ordered Al–Cu groups significantly effect the structure in Al₈₃Cu₁₇, while a tendency to chemical ordering between atoms of an unlike kind is negligible in Al₈₈Si₁₂.     

Structural study of amorphous Al0.20As0.50Te0.30, Al0.10As0.40Te0.50 and Al0.10As0.20Te0.70 by X-ray diffraction (II)

A spherical-shaped model of Al_0.20As_0.50Te_0.30, Al_0.10As_0.40Te_0.50 and Al_0.10As_0.20Te_0.70 amorphous alloys has been performed by the random Monte Carlo method. These models describe quite well the experimental radial distribution functions and abide by the expected coordination numbers apart from the threefold coordinated Te, of which an excess has appeared. The structures are formed, basically, of distorted tetrahedra around the Al atoms whose corners are occupied by As or Te atoms. Also, a separated phase model for Al_0.10As_0.20Te_0.70 alloy has been built taking into account the results of thermodynamical study on this amorphous alloy system. The fitting of this model was better than that of the model generated under the hypothesis of a continuous phase.     

Ductility improvement of Zr-Cu-Ni-Al glassy alloy

We studied the relationship between the phase diagrams and formation of crystalline inclusions in cast samples in order to improve the ductility of Zr-Cu-Ni-Al bulk amorphous alloy. A Zr₅₀Cu₄₀Al₁₀ bulk amorphous alloy with a composition close to the ternary eutectic point has no crystalline inclusions and possesses superior mechanical properties of tensile strength σ_B=2000 MPa, Young’s modulus E=107 GPa and Vickers hardness HV=580. Oxygen embrittlement of Zr-Cu-Ni-Al bulk amorphous alloys can be avoided in the Zr₅₀Cu₃₀Ni₁₀Al₁₀ bulk amorphous alloy, which exhibits superior ductility and resistance to oxidation. Furthermore, we tried to improve ductility by cold rolling by making use of the apparent work-softening phenomenon of Zr-Cu-Ni-Al bulk amorphous alloys. Preliminary studies indicated that cold rolling to produce a fine slip-band structure, which enabled uniform deformation and superior deformability, is an important procedure for improving the ductility of Zr-Cu-Ni-Al bulk amorphous alloys.     

The effect of Ag addition on the glass-forming ability of Mg–Cu–Y metallic glass alloys

The effect of Ag substitution for Cu on the glass forming ability was studied in Mg₆₅Cu_25−xAg_xY₁₀ (x=0,5,10,15,20,25) alloys by using thermal analysis and X-ray diffractometry (XRD). With increasing x from 0–25, the glass transition temperature, T_g, of melt spun Mg₆₅Cu_25−x Ag_xY₁₀ alloys increases slightly from 426 to 436 K, and the crystallization temperature, T_x, decreases from 494 to 459 K, resulting in a decrease in the supercooled liquid region. However, a partial substitution of Cu by Ag in Mg₆₅Cu₂₅Y₁₀ promotes the glass formation. The maximum diameter for amorphous phase formation by injection casting increases from 4 mm in Mg₆₅Cu₂₅Y₁₀ to 6 mm in Mg₆₅Cu₁₅Ag₁₀Y₁₀ alloy. Both amorphous Mg₆₅Cu₁₅Ag₁₀Y₁₀ alloys prepared by melt spinning and injection casting showed similar crystallization process during continuous heating in differential scanning calorimetry (DSC). The relationship between the critical diameter for the formation of an amorphous phase in injection casting and the parameters reflecting glass-forming ability was examined.     

The formation and crystallization of amorphous Al65Fe20Zr15

Amorphous Al₆₅Fe₂₀Zr₁₅ alloy has been prepared by mechanical alloying. The as-milled powders were analyzed by XRD and DTA. The fully amorphous alloy was identified by the hallo rings of XRD pattern. The effective activation energy of crystallization was estimated with modified Kissinger’s plot and it is 321.0 kJ/mol evaluated from the peak temperature of crystallization. The product phases of crystallization composed of Al₃Zr, Al₈₂Fe₁₈, AlFeZr and an unidentified phase. The crystallization kinetics was also discussed by using the isochronal DTA scans and the values of corresponding kinetic parameters were determined.     

Influence of Gd and Fe on crystallization of Al87Y5Ni8 amorphous alloy

Crystallization of amorphous Al-based alloys (Al-Y-Gd-Ni-Fe) was investigated by applying differential scanning calorimetry (DSC), X-ray diffraction (XRD) and high resolution electron microscopy (HREM). It was shown that the crystallization in the examined alloys proceeds in three stages (DSC maxima). The two first stages are attributed to formation of solid solution of fcc Al(RE) nanograins in amorphous matrix. In the third stage the precipitation of ternary compound Al₁₉Ni₅RE₃ of the orthorhombic Al₁₉Ni₅Gd₃-type structure was observed. A partial substitution of Ni by Fe causes a change of stoichiometry and crystal structure of the ternary compounds: Al₈TM₄RE (TM = Fe, Ni; RE = Y, Gd) of the tetragonal ThMn₁₂ (Al₈Mn₄Ce)-type structure. A partial replacing of Y atoms by Gd in the Al₈₇Y₅Ni₈ based alloy shifts the Al(RE) nanocrystallization to lower temperatures. In contrast to this a partial replacing of Ni by Fe shifts the nanocrystallization to higher temperatures.     

Effect of Al substitution on the magnetic properties of amorphous Fe73.5Cu1Mo3Si13.5−xAlxB9 alloy

We have synthesized FINEMET type amorphous Fe_73.5Cu₁Mo₃Si_13.5−xAl_xB₉ alloy by the single wheel melt spinning technique. The effect of Al substitution on the magnetic properties has been studied using a vibrating sample magnetometer, SQUID and Mössbauer spectroscopy. Magnetization and Curie temperature of the amorphous phase of the alloys were found to decrease with Al concentration. The results are attributed to the dilution effect of Al on the magnetic moment of Fe and to the increase in Fe–Fe interaction distance resulting in the weakening of exchange interaction.     

Comparative study of the effect of cold rolling on the structure of Al–RE–Ni–Co (RE = rare-earth metals) amorphous and glassy alloys

The present paper aims to compare the deformation-induced crystallization behavior of the rapidly solidified ribbon samples of Al₈₅Y₈Ni₅Co₂, Al₈₅Nd₈Ni₅Co₂, Al₈₅Gd₈Ni₅Co₂ and Al₈₅Mm₈Ni₅Co₂ non-crystalline alloys subjected to cold rolling with 33% reduction. It is found that amorphous Al₈₅Y₈Ni₅Co₂ alloys exhibiting glass-transition and Al₈₅Nd₈Ni₅Co₂ alloys exhibiting no glass-transition have somewhat different stabilities against crystallization under deformation at room temperature though their crystallization temperatures under heating without load or deformation are almost equal. Al₈₅Gd₈Ni₅Co₂ and Al₈₅Mm₈Ni₅Co₂ alloys (Mm = Mischmetal) did not exhibit deformation-induced crystallization at the reduction ratio used. Although, the formation of the primary nanoscale α-Al particles was observed in both Al₈₅Y₈Ni₅Co₂ and Al₈₅Nd₈Ni₅Co₂ alloys after the cold rolling, the size and volume fraction of the particles are larger in the Nd-bearing amorphous alloy as compared to the Y-bearing alloy. It is found that contrary to crystallization on heating no intermetallic compounds but only α-Al nano particles were formed during the deformation-induced crystallization of Al₈₅RE₈Ni₅Co₂ amorphous alloys. The local heating on deformation is hypothesized to affect the crystallization.     

Hardness and Bonding of Silicate Garnets

Abstract  

The chemical bond properties of the andradite garnet Ca₃Fe₂Si₃O₁₂, grossular garnet Ca₃Al₂Si₃O₁₂, and pyrope garnet Mg₃Al₂Si₃O₁₂ have been investigated using a chemical bond theory of complex crystals. The calculated hardness, isomer shifts of these garnets are in good agreement with the available experimental data. Predictions are made for those cases where no experimental data have been reported.     

Comparison of amorphous and liquid palladium-silicon alloys

The Pd_82,5Si_17,5 alloy has been investigated by X-ray diffraction in an amorphous state obtained by rapid quenching from the liquid state and also in the liquid state at a temperature just above T_f. The differences seen in the interference functions obtained relative to both states are not only due to a temperature effect. From the two atomic radial distribution functions it was possible to evaluate the Pd–Pd distances and the Pd–Si distances as well as the number of nearest neighbours. These distances have the same values, but the displacements of the atoms are more important in the liquid. The contribution of Pd–Pd bonds, for the metal-metal distances equal to 1.65 times the particle diameter, decreases in the liquid.     

Ca–Mg mixing in aluminosilicate glasses: An investigation using 17O MAS and 3QMAS and 27Al MAS NMR

To better understand non-framework cation mixing in Ca–Mg aluminosilicate glasses, ¹⁷O MAS and 3QMAS NMR studies were done on glasses on the Mg₃Al₂Si₃O₁₂–Ca₃Al₂Si₃O₁₂ join as well as several compositions with lower Al/Si ratios. While not all of the oxygen sites are fully resolved, the non-bridging oxygen associated with two Ca and one Mg cations is under-represented relative to that predicted by a model assuming random Ca/Mg mixing. Therefore, local non-bridging oxygen environments are rich in Mg, and extra Ca must be associated with charged bridging oxygens such as Al–O–Si. The deviation from random mixing increases as the Al/Si ratio decreases and as X_Mg approaches 0.50, suggesting a reduction in configurational entropy that may be compensated for by other sources, including mixing of network forming cations. Al–O–Al is detected, and appears to increase with increasing X_Mg and increasing Al/Si. High field ²⁷Al MAS NMR also shows that these glasses all have substantial concentrations of ^[5]Al, but no detectable ^[6]Al (0.5% detection limit). The amount of ^[5]Al increases non-linearly as X_Mg increases and very slightly as Al/Si increases.     

Crystallization processes in amorphous Zr54Cu46 alloy

The crystallization of amorphous Zr₅₄Cu₄₆ alloy was investigated by using X-ray diffraction (XRD), differential scanning calorimetry (DSC) and transmission electron microscopy (TEM) techniques. The experimental results show that an endothermic peak in DSC traces for amorphous Zr₅₄Cu₄₆ alloy exists at about 1006 K, indicating following eutectoid reaction occurs, namely, Cu₁₀Zr₇+CuZr₂↔CuZr in amorphous Zr₅₄Cu₄₆ alloy during heating. With increasing the heating rate, the glass transition temperature T_g and onset crystallization temperature T_x of amorphous Zr₅₄Cu₄₆ alloy increase in parallel, and the supercooled liquid region ΔT_x (=T_x−T_g) holds almost constant with an average value of 44 K. Both XRD and TEM results prove that Cu₁₀Zr₇ and CuZr₂ are main crystallization products for amorphous Zr₅₄Cu₄₆ alloy under continuous heating conditions. No CuZr phase is identified because of its small precipitation amount. Finally, the crystallization processes of amorphous Zr₅₄Cu₄₆ alloy were summarized.     

Thermal stability of amorphous Mg50Ni50 alloy produced by mechanical alloying

Amorphous Mg₅₀Ni₅₀ alloy was produced by mechanical alloying (MA) of the elemental powders Mg and Ni using a SPEX 8000D mill. The alloyed powders were microstructurally characterized by X-ray diffraction (XRD). The thermal transformation of amorphous Mg₅₀Ni₅₀ into stable intermetallics (Mg₅₀Ni₅₀ → remaining amorphous + Mg₂Ni → Mg₂Ni + MgNi₂) was analyzed using the Kissinger and isoconversional methods based on the non-isothermal differential scanning calorimetry (DSC) experiments. The apparent activation energies (E_a) and the transformation diagrams, temperature-time-transformation (T-T-T) and temperature-heating rate-transformation (T-HR-T), were obtained for both processes. A good agreement was observed between the calculated transformation curves and the experimental data, which verifies the reliability of the method utilized.     

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.     

Structural investigation of amorphous and liquid Ge0.175Te0.825 by neutron scattering

The angular distribution of intensities of 1.003 Å neutrons scattered by an alloy of Ge_0.175Te_0.825 both in the amorphous and in the liquid state have been measured. The bulk amorphous sample, prepared by water quenching of the melt, has been examined at room temperature and just above the crystallization temperature T_x. The liquid sample has been examined at 400, 600 and 800°C. The analysis of the structure factors obtained from the corrected and scaled intensities indicates that the structural features of the amorphous sample are similar to those which would be expected if it were possible to cool the alloy to room temperature, while maintaining it in the liquid state. The analysis of the radical distribution functions, from Fourier inversion of the structure factors, indicates that a change of the coordination number n₁ from 2.43 to 3.25 occurs in passing from the amorphous to the liquid state at 400°C. This result has been interpreted in terms of coordination models. In the liquid state, it has been found that a model with fourfold coordinated Ge and threefold coordinated Te is consistent with n₁=3.25. The internal consistency of this model for the liquid state allows us to make a reasonable choice between the possibility of a 3 or 4 fold coordination for Ge in the glass. We conclude that a model based on four-fold coordinated Ge and twofold coordinated Te seems an appropriate representation for the coordination of the amorphous material.     

Water-soluble amorphous alumina-based ceramic precursors and alumosols: Structural and chemical characterization

We examined the solid-state water-soluble amorphous precursors that are formed by partial thermal decomposition of Al(NO₃)₃·9H₂O (aluminum nitrate nonahydrate: ANN) using Raman and FTIR and solid-state magic-angle spinning NMR spectroscopy. We also studied the species formed in the aqueous alumosols formed by dissolution of the pre-ceramic precursors using ²⁷Al NMR spectroscopy. Species identified in the alumosols included the Al³⁺(H₂O)₆ monomer, the [AlO₄Al₁₂(OH)₂₄(H₂O)₁₂]⁷⁺(Al₁₃) Keggin ion, and the Al₃₀ polycation, [Al₃₀O₈(OH)₅₆(H₂O)₂₄]¹⁸⁺, as well as various other oligomers or nanoparticles containing IV-, V- and VI-coordinated Al³⁺ ions.