Formation and properties of the Zr75−xAlxNi10Cu10Ti5 bulk metallic glasses

Zr-based bulk metallic glasses (BMGs) exhibit interesting mechanical properties since they combine high fracture stress, elastic strain (up to 2%), significant fracture toughness and good corrosion resistance. Quaternary systems with general composition Zr–Ni–Cu–Ti show wide composition ranges in which BMG can be obtained. The addition of the another element to the quaternary alloys often increases the glass forming ability (GFA). The aim of this work was to study the influence of aluminium content on the GFA and on the mechanical properties of the Zr–Ni–Cu–Ti alloys. Multicomponent Zr_75−xAl_xNi₁₀Cu₁₀Ti₅ (x = 15, 20 at%) alloys were produced by melt spinning method obtaining ribbons, and by casting technique into a copper mould, manufacturing rod shape samples with maximum diameter of 2 mm. Supercooled liquid region depends on chemical composition and exceeds 45 °C. Vickers microhardness of studied alloys is comparable to the highest ones for other Zr-based BMG.     

Structural bulk metallic glasses with different length-scale of constituent phases

Bulk metallic glass composites containing constituent phases with different length-scales are prepared via an in situ method by copper mold casting homogeneous Zr–Ti–Nb–Cu–Ni–Al melts. The phase formation and the microstructure of the composite materials are investigated by X-ray diffraction, optical, scanning and transmission electron microscopy, and microprobe analysis. The composition of the melt as well as the cooling conditions realized during casting determine the type and the morphology of the phases present in the composite. The mechanical properties of composite materials with quasicrystalline or ductile bcc phase reinforcements are tested in uniaxial compression at room temperature, showing that the deformation is controlled by the type of the constituent phases and their morphology. Ductile phase-containing metallic glass composites demonstrate improved work hardening and ductility compared to monolithic metallic glasses. Similar results are obtained for composites with ductile bcc phase dendrites embedded in a nanocrystalline matrix. The improved ductility of the composites is due to the presence of the ductile second phase, which counteracts catastrophic failure by shear localization.     

Characterization of an amorphous–crystalline Mg-based composite

An amorphous–crystalline Mg-based composite with the nominal composition of Mg₆₅Cu₂₀Zn₅Y₁₀ has been formed by casting. X-ray diffractometry, differential scanning calorimetry, backscatter electron imaging, and energy dispersive X-ray analysis were used to characterize the structure of the composite, which is linked to the hardness, modulus, and fracture toughness obtained by Vickers and nanoindentation. Comparisons of the structure–property relationships are also made to composite materials of a similar composition. The effects of the crystalline microstructure on localized deformation through shear banding are discussed and related to the hardness and toughness results.     

Effect of similar elements on improving glass-forming ability of La–Ce-based alloys

To date the effect of unlike component elements on glass-forming ability (GFA) of alloys have been studied extensively, and it is generally recognized that the main consisting elements of the alloys with high GFA usually have large difference in atomic size and atomic interaction (large negative heat of mixing) among them. In our recent work, a series of rare earth metal-based alloy compositions with superior GFA were found through the approach of coexistence of similar constituent elements. The quinary (La_0.5Ce_0.5)₆₅Al₁₀(Co_0.6Cu_0.4)₂₅ bulk metallic glass (BMG) in a rod form with a diameter up to 32 mm was synthesized by tilt-pour casting, for which the glass-forming ability is significantly higher than that for ternary Ln–Al–TM alloys (Ln = La or Ce; TM = Co or Cu) with critical diameters for glass-formation of several millimeters. We suggest that the strong frustration of crystallization by utilizing the coexistence of La–Ce and Co–Cu to complicate competing crystalline phases is helpful to construct BMG component with superior GFA. The results of our present work indicate that similar elements (elements with similar atomic size and chemical properties) have significant effect on GFA of alloys.     

Synthesis and characterization of particulate reinforced Zr57Nb5Al10Cu15.4Ni12.6 bulk metallic glass composites

The Zr₅₇Nb₅Al₁₀Cu_15.4Ni_12.6 bulk metallic glass forming liquid is reinforced with WC, SiC, W, or Ta particles. Structure, microstructure and thermal stability of the composites are studied by X-ray diffraction, optical microscopy and differential scanning calorimetry. The metallic glass matrix remains amorphous after adding up to 20 vol.% of particles. The reactions at the interfaces between the matrix and the different reinforcing materials are investigated with scanning electron microscopy, transmission electron microscopy and electron microprobe. The mechanical properties of the composites are studied in compression and tension. The influence of the introduced particles on the thermal stability of the matrix as well as on the mechanical properties is discussed.     

Ti-based bulk glassy composites obtained by replacement of Ni with Ga

This article evaluates the possibility to replace nickel by gallium, which is considered non-toxic for biomedical use, in a Ti-based bulk metallic glass. A new alloy with the atomic composition Ti_41.5Zr_2.5Hf₅Cu_37.5Ga_7.5Si₁Sn₅ free of Ni and other toxic elements was designed and manufactured by means of suction casting the molten alloy into copper molds. Cylindrical rods with diameters up to 3 mm and a length of 50 mm were successfully produced. Further investigations by differential scanning calorimetry and X-ray diffraction in Bragg-Brentano configuration, as well as in transmission using synchrotron radiation, evidenced the main crystalline phases in the new alloy, together with a small content of amorphous matrix. Further in-depth analyses using scanning electron microscopy coupled with elemental mapping, high-resolution transmission electron microscopy and high-angle annular dark-field imaging, revealed a fine microcrystalline structure consisting of γ-CuTi and complex GaTi/CuGaTi intermetallics, together with a remnant amorphous matrix. Such kind of composite samples may open the door for new biomedical devices.     

Nanostructure controlling in Zr-based metallic glasses using icosahedral local structure

Glass-nano(quasi)crystal composite materials based on Zr–Al–Ni–Cu metallic glasses have been synthesized by controlling the nucleation and growth rates of the precipitated phase correlated with a unique icosahedral local structure. It is well known that the Zr₆₅Al_7.5Ni₁₀Cu_17.5 metallic glass has a high glass-forming ability (GFA), which enables us to produce the glassy sample with a bulky shape. Controlling a substitution of QC-forming elements such as noble metals with Cu and annealing condition, the nanoscale icosahedral quasicrystalline phase (I-phase) with various grain sizes and nucleus densities can be formed. Moreover, we have succeeded to control the nano-QC phase nucleation by changing the atmosphere pressure during casting, which results in the formation of new bulk metallic glasses (BMGs). These nanoscale structure and nucleation controlling techniques in BMGs bring a significant improvement of mechanical properties such as high strength and good ductility.     

Kinetics and formation mechanism of amorphous Fe52Nb48 alloy powder fabricated by mechanical alloying

A single phase amorphous Fe₅₂Nb₄₈ alloy has been synthesized through a solid state interdiffusion of pure polycrystalline Fe and Nb powders at room temperature, using a high-energy ball-milling technique. The mechanisms of metallic glass formation and competing crystallization processes in the mechanically deformed composite powders have been investigated by means of X-ray diffraction, Mössbauer spectroscopy, differential thermal analysis, scanning electron microscopy and transmission electron microscopy. The numerous intimate layered composite particles of the diffusion couples that formed during the first and intermediate stages of milling time (0–56 ks), are intermixed to form amorphous phase(s) upon heating to about 625 K by so-called thermally assisted solid state amorphization, TASSA. The amorphization heat of formation for binary system via the TASSA, ΔH_a, was measured directly as a function of the milling time. Comparable with the TASSA, homogeneous amorphous alloys were fabricated directly without heating the composite multilayered particles upon milling these particles for longer milling time (86 ks–144 ks). The amorphization reaction here is attributed to the mechanical driven solid state amorphization. This single amorphous phase transforms into an order phase (μ phase) upon heating at 1088 K (crystallization temperature, T_x) with enthalpy change of crystallization, ΔH_x, of −8.3 kJ mol⁻¹.     

Effects of minor Cu and Si additions on glass forming ability and mechanical properties of Co-Fe-Ta-B Bulk metallic glass

Effect of Cu and Si substitutions for Co and B on the glass forming ability (GFA) of Co_(43-x)Cu_xFe₂₀Ta_5.5B_(31.5-x)Si_y (x=0-1.5 and y=5-10) were systematically investigated by X-ray diffraction, optical microscopy, scanning electron microscopy, and differential scanning calorimetry. In order to evaluate the contribution of copper and silicon, appropriate amounts of copper and silicon were individually introduced to the base alloy composition. By using the effects of copper and silicon together, significant enhancement was obtained and the critical casting thickness (CCT) of the base alloy was increased three times from 2 mm to 6 mm. Moreover, mechanical properties of the alloys were examined by compression tests and Vickers hardness measurements. The compression test results revealed that the glassy alloys having enhanced GFA shows high strength of about 3500-4000 MPa. In addition, existence of (Co,Fe)₂B and (Co,Fe)_20.82Ta_2.18B₆ crystalline phases in glassy matrix influences the hardnesses of the alloys compared to monolitic glassy structure having hardness of about 1200 Hv.     

Concept of chemical short range order domain and the glass forming ability in multicomponent liquid

The concept of multicomponent chemical short-range order (MCSRO) domain is systematically developed by the experimental investigation of Zr–Ti–Cu–Ni–Al bulk metallic glass (BMG) and thermodynamic modeling and calculation. The existence of MCSRO domains in Zr-based BMG is verified by the observations of high-resolution transmission electron microscopy (HRTEM) images and the analysis of nano-beam electron diffraction patterns. The size of the nano-beam used in this work is 0.5 nm in diameter. Thermodynamic evaluation of the melt composed of multiple-MCSRO domains and glass-forming ability (GFA) based on the concept of MCSRO domains has also been conducted. It is indicated that the thermodynamic calculation of the GFA based on MCSRO model is consistent with the experimental data of crystallization activation energy and glass transition temperature for Ni-Zr and Zr-Cu binary alloys, and with supercooled liquid region (ΔT_x) for Zr–Ni–Al ternary alloy. The existence of MCSRO domain lowers the free energy of the melt (ΔG_MCSRO), resulting in a large undercooling and a larger energy barrier to the nucleation of a critical crystalline nucleus. Large ΔG_MCSRO, low melting point as well as co-existence of multiple MCSRO domains are valid criterion for the valuation of GFA.     

Ti_(45)Cu_(35)Zr_8Ni_7Pd_5块体非晶合金的形成能力及力学性能(英文)

利用铜模铸造方法制备了Ti45Cu35Zr8Ni7Pd5合金圆棒。通过XRD、SEM和DSC等手段研究了合金的组织,讨论了合金的玻璃形成能力,测定了合金的力学性能。结果表明,直径为2mm的圆棒为单一金属玻璃相,3mm和4mm直径的圆棒由金属玻璃相和TiCu结晶相组成。直径为2mm的圆棒具有最高的压缩断裂强度(2160MPa)和最高的硬度(维氏硬度,5600MPa)。压缩强度和硬度随着圆棒直径的增加而降低,但变形能力增加。     

Low temperature sintering and properties of CaO–B2O3–SiO2 system glass ceramics for LTCC applications

The P₂O₅ + ZnO, ZrO₂ + TiO₂, B₂O₃ and a low-melting-point CaO–B₂O₃–SiO₂ glass (LG) are selected as the sintering additives, and the effect of their additions on the microwave dielectric properties, mechanical properties and microstructures of CaO–B₂O₃–SiO₂ system glass ceramics is investigated. It is found that the sintering temperature of pure CBS glass is higher than 950 °C and the sintering range is about 10 °C. With the above additions, the glass ceramics can be sintered between 820 °C and 900 °C. The dielectric properties of the samples are dependent on the additions, densification and microstructures of sintered bodies. The major phases of this material are CaSiO₃, CaB₂O₄ and SiO₂. With 10 wt% B₂O₃ and LG glass additions, the CBS glass ceramics have better mechanical properties, but worse dielectric properties. The _r values of 6.51 and 7.07, the tan δ values of 0.0029 and 0.0019 at 10 GHz, are obtained for the CBS glass ceramics sintered at 860 °C with 2 wt% P₂O₅ + 2 wt% ZnO and 2 wt% ZrO₂ + 2 wt% TiO₂ additions, respectively. This material is suitable to be used as the LTCC material for the application in wireless communications.     

Ni对Mg-Cu-Tb非晶合金形成及力学性能的影响

利用熔体铜模喷铸法制备出直径为3 mm的Mg65Cu25-xNixTb10(x=0,5,10)非晶合金。利用X射线衍射、差热分析、压缩实验分析和扫描电镜分析了添加Ni元素对Mg-Cu-Tb非晶合金形成能力及力学性能的影响。研究表明:随着Ni含量的增加,合金的玻璃转变温度Tg增大;开始结晶温度Tx降低;过冷液相区宽度ΔTx减小,约化玻璃转变温度Trg从0.562降至0.530,非晶形成能力逐渐降低。压缩实验结果表明:当Ni含量增加到5%时可以明显提高Mg-Cu-Tb-Ni非晶合金的断裂强度。     

Calorimetric and structural analysis of the new phase Al33Ni16Zr51 produced by direct synthesis and mechanical alloying

A new phase has been synthesized in the ternary phase diagram Al–Ni–Zr: its nominal composition is Al₃₃Ni₁₆Zr₅₁. For the Al₃₃Ni₁₆Zr₅₁ compound obtained by mixing the three components in suitable proportions, a study has been carried out by direct synthesis (calorimetry) and mechanical alloying in our laboratory. With the first method we know directly the enthalpy of formation of this alloy. For the amorphous alloys prepared by mechanical alloying we can determine the crystallisation enthalpy with the differential scanning calorimetry (DSC) method. So it is possible to determine a fundamental piece of information: the amorphous alloy formation enthalpy.     

Preparation of W–15 wt%Ti prealloyed powders

W–15 wt%Ti prealloyed powders were prepared by high-energy milling W and TiH₂ powders, and the prealloyed powders were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). The size of W and TiH₂ grains was estimated by Williamson–Hall formula from width of XRD peaks. The results show that the grain size decreases with increasing milling time, while the lattice parameter increases. After milling for 40 h, nanocrystalline β-W_xTi_1−x solid solution with the form of thin laminar exists in the W–TiH₂ prealloyed powders.     

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.     

Mechanical and microstructural behaviour of 2024–7075 aluminium alloy sheets joined by friction stir welding

The aim of the present work is to investigate on the mechanical and microstructural properties of dissimilar 2024 and 7075 aluminium sheets joined by friction stir welding (FSW). The two sheets, aligned with perpendicular rolling directions, have been successfully welded; successively, the welded sheets have been tested under tension at room temperature in order to analyse the mechanical response with respect to the parent materials. The fatigue endurance (S–N) curves of the welded joints have been achieved, since the fatigue behaviour of light welded sheets is the best performance indicator for a large part of industrial applications; a resonant electro-mechanical testing machine load and a constant load ratio R=σ_min/σ_max =0.1 have been used at a load frequency of about 75 Hz. The resulted microstructure due to the FSW process has been studied by employing optical and scanning electron microscopy either on ‘as welded’ specimens and on tested specimen after rupture occurred.     

Superplasticity in a bulk amorphous Pd-40Ni-20P alloy:a compression study

Compressive deformation behavior of a cast Pd₄₀Ni₄₀P₂₀ bulk metallic glass in the supercooled liquid region (589–670 K) was investigated at strain rates ranging from 10⁻⁴ to 10⁻² s⁻¹. The material exhibited excellent mechanical formability in the supercooled liquid region. However, in contrast to a Newtonian behavior generally observed in oxide glasses, the present alloy also showed a non-Newtonian behavior, depending upon the temperature and applied strain rate. Specifically, the alloy is like a Newtonian fluid at high temperatures, but becomes non-Newtonian at low temperatures and high strain rates. Structures of the amorphous material, both before and after deformation, were examined using X-ray diffraction and high-resolution transmission electron microscopy. The non-Newtonian behavior is proposed to be associated with the glass instability during deformation.     

Effect of deformation temperature on microstructures and properties of 7075/6009 alloy

The 7075/6009 aluminum composite ingot with the diameter of 65 mm was prepared by double-stream-pouring continuous casting. The deformation behavior and the mechanical properties of the composite ingot compressed at 543, 573, 623, 673 and 723 K were analyzed. The results show that the gradient distributions of composition and hardness in the transition layer of the composite plates still exist after plastic deformation of the ingots. Meanwhile, the thickness of the transition layer reduces from millimeter order to micrometer order. The mechanical properties of the composite plate increase with the increase in deformation temperature from 543 K to 673 K. The best mechanical properties of the 7075/6009 aluminum composite are: σ_b=381 MPa, σ_0.2=322 MPa and δ=16.6%. The appropriate deformation temperature range is (0.75–0.85)T_M, where T_M is the melting point of 7075 alloy.     

Low-temperature brazing of titanium by the application of a Zr–Ti–Ni–Cu–Bebulk metallic glass (BMG) alloy as a filler

Titanium (Ti) was successfully brazed at low temperatures below 800 °C by employing a Zr_41.2Ti_13.8Ni_10.0Cu_12.5Be_22.5 (at.%) bulk metallic glass (BMG) alloy as a filler. Through the use of this alloy filler, the detrimental segregation of Zr–Cu–Ni filler elements was completely eliminated by heating to well below 800 °C, so the resultant joint was quite homogeneous with a coarse acicular structure. The disappearance of the Zr–Cu–Ni segregated region was rate-controlled by the diffusion of the filler elements in the Ti base metal. Remarkably, the mechanical property and corrosion resistance of the homogeneous joint brazed at 800 °C for 10 min were mostly comparable to those of bulk Ti.