Small-angle X-ray scattering from phase-separating amorphous metallic alloys undergoing nanocrystallization

We performed a combined small- and wide-angle X-ray scattering (SAXS/WAXS) study of nanocrystallization during annealing of binary Al₉₂Sm₈ and Al₉₁Gd₉ melt-spun glassy alloys. In course of the transformation an interference maximum develops in the SAXS region while WAXS spectra show formation of fcc-Al nanocrystals in the glassy phase. In order to determine the origin of the SAXS maximum the theoretical SAXS intensity and distance distribution function were calculated considering two structural models. The first model represented a single nanocrystal with a solute layer on its surface and the second one a phase-separated alloy with spatially correlated compositional fluctuations. The results of the calculations are compared with the experimental data. It is demonstrated that only the model representing correlated fluctuations reasonably reproduces the experimental results. We conclude that nano-scale glassy phase separation occurs in the investigated alloys and the nanocrystals form inside the Al-rich amorphous regions.     

Synthesis and characterization of amorphous Zr-based alloys with Ta and W additions

A reference Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅ bulk metallic glass as well as a number of alloys obtained by addition of refractory elements Ta or W (combined with Sn) to the main Zr–Cu–Al–Ni system were elaborated by mould casting, twin roll casting and planar flow casting. The chemical compositions were chosen according to empirical rules, and as combinations of the binary eutectics for strongly interacting elements, taking into account the corresponding enthalpies of mixing. Optical microscopy, X-ray diffractometry, differential thermal analysis, differential scanning calorimetry, scanning electron microscopy and tensile mechanical testing were used to characterize the fully and partially obtained amorphous materials. Correlation of glass forming ability, thermodynamic parameters, crystallization behaviour and mechanical properties with chemical composition and production technology is discussed.     

Formation, properties and microstructure of amorphous/crystalline composite Ag20Cu30Ti50 alloy using miscibility gap

The aim of the work was to produce the amorphous/crystalline composite with uniform distribution of fine crystalline soft phase. Silver–copper–titanium Ag₂₀Cu₃₀Ti₅₀ alloy was prepared using 99.95 wt% Ag, 99.95 wt% Cu, 99.95 wt% Ti that were arc-melted in argon atmosphere. Then the alloy was melt spun on a copper wheel with linear velocity of 33 m/s. Investigation of the microstructure for both arc-melt massive sample and melt-spun ribbons was performed with use of scanning electron microscope (SEM) with EDS, light microscope (LM) and X-ray diffraction. The thermal stability was evaluated by differential scanning calorimetry (DSC). The properties such as Young modulus and Vickers hardness number before and after crystallization of the amorphous matrix were measured with use of nanoindenter. The microstructure was investigated by transmission electron microscope (TEM). It was found, that the alloy has a tendency for separation within the liquid state due to the miscibility gap which resulted in segregation into Ti–Cu–Ag matrix and Ag-base spherical particles after arc-melting. During rapid cooling through the melt spinning the Ag₂₀Cu₃₀Ti₅₀ alloy formed an amorphous/crystalline composite of fcc silver-rich spherical particles within the amorphous Ti–Cu–Ag matrix.     

Tribological behaviors of Zr-based bulk metallic glass versus Zr-based bulk metallic glass under relative heavy loads

As a novel engineering material, bulk metallic glass (BMG) has received much attention. However, the knowledge concerning the tribological behavior of BMG versus BMG under relatively heavy loads is still insufficient. In this study, Zr₄₁Ti₁₄Cu_12.5Ni₁₀Be_22.5 metallic glass pins and discs were prepared by copper-mold suction casting. The dry sliding friction and the wear characteristics of the as-cast Zr-based BMG versus Zr-based BMG were tested under loads of 100, 125 and 150 N, respectively, using a pin-on-disc tribological apparatus at room temperature. The worn surfaces were studied by scanning electron microscopy in order to identify the wear mechanisms. The results showed that both the coefficient of friction and the wear rate increased with both the normal load and the rotational sliding velocity. X-ray diffraction patterns recorded after the tribological experiments indicated that no sliding-induced crystallization occurred. Transmission electron microscopy was also used to confirm the amorphous of the BMGs after sliding tests. In addition, the wear mechanisms changed with the experimental conditions. For a normal load of 100 N, the main mechanisms were abrasive wear, slight grooves and micro-cracks. For higher loads, adhesive wear was predominant, accompanied by abrasive wear and deeper grooves and more micro-cracks. When the rotational sliding velocity was increased, the dominant wear changed from slight grooves to viscous flow and adhesive wear.     

Thermal stability and magnetic properties of Gd–Fe–Al bulk amorphous alloys

Gd₆₅Fe₂₀Al₁₅, Gd₆₅Fe₁₅Al₂₀ and Gd₇₀Fe₁₅Al₁₅ bulk amorphous alloys were produced by copper mold casting method with the maximum diameters of 2, 1 and 1 mm, respectively. The crystallization temperature (T_x) and melting temperature (T_m) of the Gd₆₅Fe₂₀Al₁₅ bulk amorphous alloy are 808 and 943 K, respectively. Accordingly, the temperature interval of T_m and T_x, ΔT_m (=T_m − T_x), is as small as 135 K and the reduced crystallization temperature (T_x/T_m) is as high as 0.86. The small ΔT_m and high T_x/T_m values are presumed to be the origin for the achievement of the high amorphous-forming ability of the Gd–Fe–Al bulk amorphous alloy. The Gd₆₅Fe₂₀Al₁₅, Gd₆₅Fe₁₅Al₂₀ and Gd₇₀Fe₁₅Al₁₅ bulk amorphous cylinders with a diameter of 1 mm exhibit superparamagnetism at room temperature, while the amorphous ribbon shows the paramagnetism at room temperature. Finally, the mechanical properties of Gd₆₅Fe₂₀Al₁₅ bulk amorphous alloys are investigated.     

Glass-formation and hardness of Cu–Y alloys

Metallic glasses exhibit particularly attractive mechanical properties, like high stresses to fracture and large elastic strain (up to 2%), but they show generally low plasticity. Aim of this work is to investigate the glass forming range in the Cu–Y system, in order to form the ductile CuY phase (CsCl structure) upon crystallization. Cu₅₈Y₄₂, Cu₅₀Y₅₀ and Cu₃₃Y₆₇ alloys have been prepared by rapid solidification and copper mould casting, obtaining ribbons and cylindrical shaped ingots, with diameter of 2 mm. Fully amorphous, partially amorphous and fully crystalline samples have been obtained for different compositions and quenching conditions. In some cases, the X-ray diffraction results, analysed using the Rietveld method, showed CuY nanocrystals embedded in an amorphous matrix. The microstructure was studied by transmission electron microscopy (TEM) and the presence of nanocrystals of the ductile phase CuY has been confirmed. Microhardness results showed a softening of the amorphous phase due to the presence of CuY nanocrystals and a hardening due to the Cu₂Y phase.     

He ion irradiation induced nanocrystallization in Cu50Zr45Ti5 glassy alloy

Partial nanocrystallization induced by ion irradiation can be used to improve the surface properties in metallic glasses. We investigated the crystallization behavior and the structure of the formed nanocrystalline phases in a melt-spun Cu₅₀Zr₄₅Ti₅ glassy alloy irradiated with 140 keV He ions to a fluence of 1.7 × 10¹⁷/cm². Crystalline nanoparticles were precipitated by He ion irradiation. The nanocrystalline phases were identified as a mixture of the orthorhombic Cu₁₀Zr₇ phase, tetragonal CuZr₂ phase and monoclinic CuZr phase. Hardness enhancement was observed at a depth close to the projected range of the He ions, which was related to the formation of the crystalline nanoparticles.     

Influence of fluxing in the preparation of bulk Fe-based glassy alloys

Fe-based master ingots, with composition [(Fe₅₀Co₅₀)₇₅B₂₀Si₅]₉₆Nb₄, have been prepared by arc-melting and subsequently purified using the fluxing technique. Rods, with diameters from 1 to 2.5 mm, ribbons and wires with a maximal diameter of 200 μm have been produced from these purified master ingots. The amorphous structure, thermal stability, hardness and magnetic properties of the specimens were studied. In particular, we show by high-energy synchrotron X-ray diffraction that the rods are fully amorphous up to a maximal diameter of 2 mm. Moreover, the [(Fe₅₀Co₅₀)₇₅B₂₀Si₅]₉₆Nb₄ glassy alloy exhibits high hardness (HV = 1050) combined with good soft-magnetic properties (H_c = 63 A/m).     

Wear and thermal properties of Zr-based amorphous surface alloyed materials fabricated by high-energy electron beam irradiation

Zr-based amorphous surface alloyed materials were fabricated by high-energy electron beam irradiation in this study. A mixture of Zr-based amorphous powders and LiF + MgF₂ flux was deposited on a pure copper substrate, and then an electron beam was directed on this powder mixture to fabricate a one-layered surface alloyed material. A two-layered surface alloyed material was also fabricated by irradiating electron beam again onto the powder mixture deposited on the one-layered surface alloyed material. The microstructural analysis results indicated that a number of coarse crystalline phase particles were formed in the one-layered surface alloyed layer, whereas a small amount of fine and hard crystalline particles were homogeneously distributed in the amorphous matrix of the two-layered surface alloyed layer. Owing to these fine and hard crystalline particles, the hardness and wear resistance of the two-layered surface alloyed layer improved over the one-layered surface alloyed layer or other kinds of surface alloyed layers. The thermal conductivity of the two-layered surface alloyed layer was much lower than that of titanium-alloy-based or stainless-steel-based surface alloyed layers. These findings suggested the possibility of applying Zr-based amorphous surface alloyed materials to high wear-resistant thermal barrier coatings or parts.     

Reinforcement of Al–Fe–Ni alloys with the in situ formation of composite materials

One of the most effective methods for the improvement of the mechanical properties of metals is their reinforcement with non-metallic materials. In the present work powder of K₂TiF₆ and KBF₄ was added in an Al–Fe–Ni alloy while the alloy was in liquid form at 1060 °C with a 5 wt.% mixture of powders and with simultaneous stirring for 30 min. The liquid was squeeze-casted at 150 bar. The as-cast specimens were examined with electron microscopy and X-ray diffraction. SEM analysis revealed that the as-formed material is composed by needle-like crystallites along with a dentritic form and an interdendritic phase. The composition of the needle-like crystallites may presumably be expressed by the formula (Fe-Ni)Al₃. The rest of the matrix consists of almost pure Al grown dentritically, while the interdendritic phase contains Fe and Ni dissolved in Al. EDS analysis also proved the existence of spots with high Ti concentration, which probably refer to the Ti–B compounds. Finally TEM verified the presence of nanocrystals in the matrix.     

Influence of thermally induced structural transformations on hardness in Fe89.8Ni1.5Si5.2B3C0.5 amorphous alloy

Effect of heat treatment on mechanical behavior of Fe_89.8Ni_1.5Si_5.2B₃C_0.5 amorphous alloy was investigated by measuring microhardness. It was shown that the as-prepared amorphous alloy has an unexpectedly high microhardness. This can be attributed not only to boron dispersed in the alloy, but also to the structure which exhibits aspects of a nanocomposite of nanoparticles dispersed in an amorphous matrix. As the alloy crystallizes at temperatures above 540 °C, microhardness decreases continuously as a function of heating temperature. This is attributed to separation of boron out of the amorphous matrix into nanocrystals of Fe₂B phase. Further decrease in microhardness is attributed to crystallite growth with the accompanying change in the dominant nature of the interfaces from amorphous/crystal to crystal/crystal, and creation of a porous structure. When the crystallization is complete, the alloy exhibits microhardness close to that of a hypothetical mixture of α-Fe and Fe₂B phases of the same composition.     

Formation and thermal stability of new Zr–Cu-based bulk glassy alloys with unusual glass-forming ability

The simultaneous addition of Al and Ag to Zr–Cu binary alloys increased in the stabilization of supercooled liquid, the reduced glass transition temperature and γ value, leading to greatly enhance the glass-forming ability (GFA). The Zr–Cu–Ag–Al glassy alloy samples with diameters above 15 mm were obtained in the wide composition range of 42–50 at% Zr, 32–42 at% Cu, 5–10 at% Ag, and 5–12 at% Al. The best GFA was obtained for Zr₄₈Cu₃₆Ag₈Al₈ alloy, and the glassy samples with diameters up to 25 mm were fabricated by an injection copper mold casting. The Zr₄₈Cu₃₆Ag₈Al₈ glassy alloy exhibited high tensile and compressive fracture strength of over 1800 MPa.     

Formation of centimeter Fe-based bulk metallic glasses in low vacuum environment

The formation of a Fe_43.7Co_7.3Cr_14.7Mo_12.6C_15.5B_4.3Y_1.9 bulk metallic glass (BMG) was attempted in low vacuum environment and in air using commercial raw materials. The glass forming ability of the Fe-based alloys was studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and differential thermal analyzer (DTA). It was found that cylindric rods with diameters ranging from 10 mm to 5 mm could be successfully fabricated by copper-mold casting in the pressures from 1.5 Pa to 10⁵ Pa (10⁵ Pa = 1 atm). All BMGs exhibit a distinct glass transition and wide supercooled liquid region. The preparation condition seems not significantly affected by the thermodynamic parameters of BMG, such as supercooled liquid region, glass transition temperature and melting process. The oxygen content of the alloys prepared in different vacuum conditions was measured by a LECO oxygen analyzer, which revealed that the oxygen content was less than 100 ppm for all BMGs prepared, even in air. The good glass forming ability and excellent oxidation resistance for the present Fe-based alloy are discussed.     

Oxidation behavior of amorphous and nanoquasicrystalline Zr–Pd and Zr–Pt alloys

Oxidation behavior of amorphous and nanoquasicrystalline Zr₇₀Pd₃₀ and Zr₈₀Pt₂₀ alloys melt-spun at different wheel speeds has been studied in air by non-isothermal and isothermal techniques. Oxidation resistance of amorphous alloys has been found to be the lowest in comparison to the partially and fully crystallized Zr alloys. It has also been observed that oxidation does not induce crystallization of the amorphous phase. It has been shown that the oxygen diffusion rate increases gradually in the order of crystalline, nanoquasicrystalline, partially nanocrystalline and amorphous states of these alloys. Possible micromechanism of oxidation and the role of different grain/interface boundaries on the oxygen diffusion has been discussed.     

A novel photocatalyst and improvement of photocatalytic properties by Cu doping

A new series of photocatalysts, Bi₂Zn_2/3−xCu_xTa_4/3O₇ (Cu-β-BZT) crystals with pyrochlore structure were synthesized by the method of solid-state reaction (SSR). With small amount of Cu doped (0.01 ≤ x ≤ 0.04), the phase structure was kept to be monoclinic pyrochlore as pure β-BZT. The diffuse reflectance spectrum of Cu-β-BZT samples showed a red shift. The method of Cu doping enhanced the photocatalytic activity, and when the value of x is 0.03, the sample showed the highest activity, which is about 10 times higher than that of pure β-BZT under UV light. Especially, the samples of Cu-β-BZT showed photocatalytic activities under visible light irradiation (λ > 400 nm). Effects of the Cu doped on the photocatalytic activities of the catalysts were also discussed.     

On the amorphous and nanocrystalline Zr–Cu and Zr–Ti co-sputtered thin films

In the current study, we examined and compared the mixing and vitrification behavior of the Zr–Cu and Zr–Ti binary systems in the form of co-sputtered thin films with or without post-annealing. The co-sputtered Zr–Cu films are all amorphous under various co-sputtering conditions, suggesting the high vitrification tendency. The amorphous Zr–Cu thin film will start to crystallize into nano-crystalline Zr₂Cu and Zr₇Cu₁₀ phases upon long exposure at temperatures above 350 °C. On the other hand, it is difficult to form amorphous film with the Zr–Ti system, except at a low sputtering power of 30–50 W. The low powers enable the co-sputtered Zr–Ti thin film to exhibit the diffuse hump in the X-ray diffraction. Examination by high resolution transmission electron microscopy reveals numerous fine nano-crystalline phases around 2 nm in the amorphous matrix. Upon exposure at 700 °C, the Zr–Ti films transform into crystalline hexagonal close-packed α and body-centered cubic β phases.     

Glycolthermal synthesis and characterization of hexagonal CdS round microparticles in flower-like clusters

Hexagonal CdS round microparticles in flower-like clusters were synthesized by glycolthermal reactions of CdCl₂ and thiourea as cadmium and sulphur sources in 1,2-propylene glycol (PG) at 100-200 °C for 10-30 h. Phase and morphology were detected using X-ray diffraction (XRD), and scanning and transmission electron microscopy (SEM, TEM). The products were pure phase of hexagonal wurtzite CdS. The quantitative elemental analysis of Cd:S ratio was detected using energy dispersive X-ray (EDX) analyzer. Raman spectrometer revealed the presence of fundamental and overtone modes at 296 and 595 cm⁻¹, corresponding to the strong 1LO and weak 2LO modes, respectively. Photonic properties were investigated using UV-visible and photoluminescence (PL) spectroscopy. They showed the same absorption at 493-498 nm, and emission at 431 nm due to the excitonic recombination process. A possible formation mechanism was also proposed, according to experimental results.     

Synthesis of copper-based bulk metallic glasses in the ternary Cu–Mg–Ca system

This paper reports the discovery of novel copper-based bulk metallic glasses free of group IV transition metals (Zr, Hf and Ti) in the Ca–Cu–Mg ternary system. Alloys of compositions ranging from Cu-33–55 at.%, Mg-18–36 at.% and Ca-18–36 at.%, located far from eutectic reactions, were found to exhibit high glass-forming ability (up to 8 mm using conventional copper mold casting), high hardness (up to 328H_V) and low densities (2.9–4.0 g/cm³).