High-strength Cu-based bulk glassy alloys in Cu–Zr–Ti and Cu–Hf–Ti ternary systems

New Cu-based bulk glassy alloys were formed in Cu–Zr–Ti and Cu–Hf–Ti systems by the copper mold casting method. The critical diameter is 4 mm for the Cu₆₀Zr₃₀Ti₁₀ and Cu₆₀Hf₂₅Ti₁₅ alloys which are larger than 1 mm for the Cu₆₀Zr₄₀ and Cu₆₀Hf₄₀ glassy alloys. The substitution of Zr or Hf for Ti causes an increase in the glass-forming ability (GFA). As the Ti content increases, the glass transition temperature (T_g), crystallization temperature (T_x), and the supercooled liquid region ΔT_x(=T_x−T_g) decrease for both Cu₆₀Zr_40−xTi_x and Cu₆₀Hf_40−xTi_x alloys. In contrast, the liquid temperature (T_l) has a minimum value of 1127 K for the Cu₆₀Zr₂₀Ti₂₀ alloy and 1175 K for the Cu₆₀Hf₂₀Ti₂₀ alloy, resulting in a maximum T_g/T_l of 0.63 and 0.62, respectively. The alloys with the highest T_g/T_l value showed the highest GFA for these Cu-based alloys. The bulk glassy alloys exhibit high tensile fracture strength of 2000–2160 MPa, compressive fracture strength of 2060–2150 MPa and compressive plastic elongations of 0.8–1.7%. The finding of the new Cu-based bulk glassy alloys with high GFA, high fracture strength above 2000 MPa and distinct plastic elongation is encouraging for the future development of a new type of bulk glassy alloy which can be used for structural materials.     

Consolidation and mechanical properties of ball milled Zr50Cu50 glassy ribbons

Bulk Zr₅₀Cu₅₀ partially crystallized glassy specimens have been produced by powder metallurgy methods. Zr₅₀Cu₅₀ powder has been prepared by controlled milling of melt spun glassy ribbons and subsequently consolidated by hot pressing into bulk cylindrical samples of 10 mm diameter and 10 mm length. The consolidated material exhibits interesting mechanical properties, namely, a perfect elastic regime of 1.5%, high strength of about 1350 MPa and hardness of 4.80 GPa. However, no macroscopic ductility is visible, most likely due to the residual porosity of the consolidated specimens. These results indicate that powder metallurgy methods may become a valid alternative to casting techniques for the production of glassy and partially crystallized Zr-based alloys.     

Bulk metallic glass formation in binary Cu-rich alloy series – Cu100−xZrx (x=34, 36, 38.2, 40 at.%) and mechanical properties of bulk Cu64Zr36 glass

The compositional dependence of a glass-forming ability (GFA) was systematically studied in a binary alloy series Cu_100−xZr_x (x=34, 36, 38.2, 40 at.%) by the copper mold casting method. Our results show the critical casting thickness jumps from below 0.5 mm to above 2 mm when x changes from 34 to 36 while further increase in x reduces the critical casting thickness. The best glass former Cu₆₄Zr₃₆ does not correspond to either the largest undercooled liquid region (ΔT=T_x1−T_g, where T_g is the glass transition temperature, and T_x1 is the onset temperature of the first crystallization event upon heating) or the highest reduced glass transition temperature (T_rg=T_g/T_l, where T_l is the liquidus temperature). Properties of bulk amorphous Cu₆₄Zr₃₆ were measured, yielding a T_g∼787 K, T_rg∼0.64, ΔT∼46 K, H_v (Vicker's Hardness) ∼742 kg/mm², Young's Modulus ∼92.3 GPa, compressive fracture strength ∼2 GPa and compressive strain before failure ∼2.2%.     

Structure and crystallization kinetics of a Cu50Zr45Ti5 glassy alloy

The crystallization kinetics and structure changes in a melt-spun Cu₅₀Zr₄₅Ti₅ glassy alloy on heating were investigated by X-ray diffractometry, transmission electron microscopy, differential scanning calorimetry and differential isothermal calorimetry. The glassy phase in the Cu₅₀Zr₄₅Ti₅ alloy was crystallized forming Cu₁₀Zr₇ and CuZr₂ phases upon thermal annealing. The activation energy for crystallization obtained by the Arrhenius equation was 435 kJ/mol. The crystallization process took place by nucleation and growth mechanism, and an Avrami exponent of about 3.3 may indicate a three-dimensional interface-controlled growth of nuclei with a decreasing nucleation rate.     

Effect of Ni on glass-forming ability of Cu-Ti-based amorphous alloys

1 Introduction Recently, a number of bulk metallic glassy alloys have been reported, such as La-Al-Ni[1], Cu-Ti-Zr-Ni [2, 3], Cu-Ti-Zr-Ni-Be[4, 5], Cu-Ti-Zr-Ni-Si[6?8] and Cu-Ti-Zr-Ni-Sn[9]. Because of the exceptional good glass-forming ability, these mu…     

Structural and magnetic nanoclusters in Cu50Zr50−xGdx (x = 5 at.%) metallic glasses

It is shown that phase-separated metallic glasses on the nanoscale can be prepared by rapid quenching of Cu₅₀Zr_50−xGd_x melts with a low concentration of gadolinium (x = 5 at.%). Gd-enriched clusters of 2 nm size are formed as early stages of decomposition in the deeply undercooled melt. The key physical parameter to obtaining such a nanoclustered microstructure upon quenching is the critical temperature of liquid-liquid phase separation which has to be close to the glass transition temperature. Thus, the thermodynamic properties of the liquid phase even in the metastable deeply undercooled melt essentially determine the structure formation. Analysis of the spatial atomic arrangement by atom probe tomography after annealing in the supercooled liquid state provides direct evidence of the spinodal character of the decomposition by uphill diffusion. The Gd-enriched nanoclusters exhibit ferromagnetic ordering below 50 K and the cluster size regime derived from magnetization measurements is in good agreement with that obtained from atom probe tomography investigations. The first stage of crystallization of Cu₅₀Zr₄₅Gd₅ glass is observed to be Ostwald-type ripening on a nanoscale. The phase-separated glass acts as a precursor for the formation of a metastable nanocrystalline structure.     

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.     

Properties of the Ti<Subscript>40</Subscript>Zr<Subscript>10</Subscript>Cu<Subscript>36</Subscript>Pd<Subscript>14</Subscript> BMG Modified by Sn and Nb Additions

The results of investigation of the influence of additions of 2 and 3 at.% of Sn and simultaneously of Sn and 3 at.% Nb on microstructure and properties of the bulk metallic glasses of composition (Ti₄₀Cu_36?x Zr₁₀Pd₁₄Sn _x )_100?y Nb _y are reported. It was found that the additions of Sn increased the temperatures of glass transition (T _g), primary crystallization (T _x ), melting, and liquidus as well as supercooled liquid range (ΔT) and glass forming ability (GFA). The nanohardness and elastic modulus decreased in alloys with 2 and 3 at.% Sn additions, revealing similar values. The 3 at.% Nb addition to the Sn-containing amorphous phase decreased as well all the T _g, T _x , T _L, and T _m temperatures as ΔT and GFA; however, relatively larger values of this parameters in alloys containing larger Sn content were preserved. In difference to the previously published results, in the case of the amorphous alloys containing small Nb and Sn additions, a noticeable amount of the quenched-in crystalline phases was not confirmed, at least of the micrometric sizes. In the case of the alloys containing Sn or both Sn and Nb, two slightly different amorphous phase compositions were detected, suggesting separation in the liquid phase. Phase composition of the alloys determined after amorphous phase crystallization was similar for all compositions. The phases Cu₈Zr_3, CuTiZr, and Pd₃Zr were mainly identified in the proportions dependent on the alloy compositions.     

Glass forming ability and stability: Ternary Cu bearing Ti,Zr, Hf alloys

Four Cu bearing alloys of nominal composition Zr₂₅Ti₂₅Cu₅₀, Zr₃₄Ti₁₆Cu₅₀, Zr₂₅Hf₂₅Cu₅₀ and Ti₂₅Hf₂₅Cu₅₀ have been rapidly solidified in order to produce ribbons. All the alloys become amorphous after melt-spinning. In the Zr₃₄Ti₁₆Cu₅₀ alloy localized precipitation of cF24 Cu₅Zr phase can be observed in the amorphous matrix. The alloys show a tendency of phase separation at the initial stages of crystallization. The difference in crystallization behavior of these alloys with Ni bearing ternary alloys can be explained by atomic size, binary heat of mixing and Mendeleev number. It has been observed that both Laves and Anti-Laves phase forming compositions are suitable for glass formation. The structures of the phases, precipitated during rapid solidification and crystallization can be viewed in terms of Bernal deltahedra and Frank–Kasper polyhedra.     

Phase formation and thermal stability in Cu–Zr–Ti(Al) metallic glasses

In the present study we investigate the phase formation and the thermal stability of Cu₅₀Zr_50 ? xTi_x (0 ≤ x ≤ 10) and (Cu_0.5Zr_0.5)_100 ? xAl_x glass-forming alloys. Parameters indicating the glass-forming ability (GFA) are calculated from isochronal and isothermal calorimetric experiments. A high Ti content in the Cu–Zr–Ti alloys causes the precipitation of a metastable ternary Laves phase (C15), which does not form in Cu–Zr–Al. Accompanied with it is a significant drop in the activation energy of crystallization. Also the supercooled liquid region (ΔT_x = T_x ? T_g), the reduced glass transition temperature (T_rg = T_g/T_liq), and the γ parameter (γ = T_x/(T_g + T_liq)) (T_x: crystallization temperature, T_g: glass transition temperature and T_liq: liquidus temperature) are sensitive to the change in the crystallization sequence. The fragility values calculated are believed to overestimate the GFA of the investigated alloys. Careful selection of the alloy composition enables the targeted precipitation of different crystalline phases.     

Zr-Co(Cu)-Al bulk metallic glasses with optimal glass-forming ability and their compressive properties

The formation of bulk metallic glasses (BMGs) in the ternary Zr₅₆Co₂₈Al₁₆ and quaternary Zr₅₆Co_28–xCu_xAl₁₆ (x=2, 4, 5, 6, 7, mole fraction, %) glassy alloys was investigated via the copper mold suction casting method. The main purpose of this work was to locate the optimal BMG-forming composition for the quaternary ZrCo(Cu)Al alloys and to improve the plasticity of the parent alloy. The X-ray diffractometry (XRD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC) were used to investigate the glassy alloys structure and their glass forming ability (GFA). In addition, the compression test, microhardness, nano-indentation and scanning electron microscopy (SEM) were utilized to discuss the possible mechanisms involved in the enhanced plasticity achievement. The highest GFA among Cu-containing alloys was found for the Zr₅₆Co₂₂Cu₆Al₁₆ alloy, which was similar to that of the base alloy. Furthermore, the plasticity of the base alloy increased significantly from 3.3% to 6% for the Zr₅₆Co₂₂Cu₆Al₁₆ BMG. The variations in the plasticity and GFA of the alloys were discussed by considering the positive heat of mixing within Cu and Co elements.     

Glass-forming ability of RE–Al–TM alloys (RE=Sm,Y; TM=Fe,Co, Cu)

The glass-forming ability (GFA) of RE–Al–TM (RE=Sm, Y; TM=Fe, Co, Cu) upon melt-spinning and die-casting into a copper mold has been studied. Melt-spun ribbons for both Sm- and Y-based alloys show a fully amorphous structure. However, die-casting revealed that Sm-based alloys exhibit a higher GFA than Y-based alloys. The as-cast Sm₇₀Fe₂₀Al₁₀, Sm₆₀Fe₂₀Al₁₀Co₁₀ and Sm₆₀Fe₂₀Al₁₀Co₅Cu₅ cylinders (3 mm×50 mm) contain a mixture of amorphous and crystalline phases after copper-mold casting. A new bulk metallic glass was obtained for the Sm₆₀Fe₁₀Al₁₀Co₁₅Cu₅ alloy, which shows ferromagnetic behavior. In contrast, as-cast Y-based alloys are completely crystalline. Based on the data of the activation energy for crystallization of the amorphous phase, E_x, and the crystallization temperature, T_x, together with magnetic measurements, it is concluded that the as-cast Sm₆₀Fe₁₀Al₁₀Co₁₅Cu₅ cylinder displays a tendency for clustering. The improved glass-forming ability of Sm-based alloys is interpreted in terms of classical nucleation theory.     

Structural relaxation and related viscous flow of Zr–Cu–Al-based bulk glasses produced from the melts with different glass-forming ability

The relaxation ability of Zr₄₆(Cu_4/5Ag_1/5)₄₆Al₈ and Zr₄₆Cu₄₆Al₈ bulk glasses displaying different glass-forming ability (GFA) in the liquid state has been studied by measurements of the shear modulus, creep and stress relaxation. It has been found that the four-component alloy with higher GFA always displays higher relaxation ability in the glassy state. This fact does not seem to correlate with the amount of the frozen-in free volume as dependent on the GFA. It has been argued that the relaxation centers responsible for structural relaxation and related viscous flow are similar to dumbbell interstitials in simple metals. Such an approach precisely describes the kinetics of shear modulus relaxation and reasonably agrees with a phenomenological interpretation of structural relaxation-induced viscoelastic phenomena in metallic glasses.     

Low temperature heat capacity and electrical resistivity of the Ti40Zr25Cu12Ni3Be20 glass forming alloy

Gaining knowledge of electronic structure provides useful information for understanding unique properties of metallic glasses. In this study, low temperature heat capacity and electrical resistivity of the glass forming Ti₄₀Zr₂₅Cu₁₂Ni₃Be₂₀ alloy with glassy, quasicrystalline, or crystalline states below 300 K were investigated. The precipitation of the I-phase was revealed in the initial crystallization process of the Ti₄₀Zr₂₅Cu₁₂Ni₃Be₂₀ BMG. The glassy state has higher state density at Fermi level than its quasicrystalline or crystalline counterparts, which could be interpreted by the electron localization in glassy state as well as a pseudo-Brillouin zone formed nearby Fermi surface in the quasicrystalline state. None of the three states showed superconductivity phenomenon down to 1.9 K. Temperature dependence of resistivity for both the glassy state and the quasicrystalline state exhibited negative temperature coefficient and was less sensitive to temperature than the crystalline state. The electrical resistivity showed a smaller value for the I-phase than that for the glass due to lower structural integrity of I-phase. Electrical resistivity as well as heat capacity measurements indicated that the electronic structure of the quasicrystalline state is quite similar to glassy state but far from crystalline state.     

Influence of oxygen on the crystallization behavior of Zr65Cu27.5Al7.5 and Zr66.7Cu33.3 metallic glasses

The influence of oxygen on the crystallization behavior of Zr_65−xCu_27.5Al_7.5O_x (x=0.14, 0.43 and 0.82) and Zr_66.7−xCu_33.3O_x (x=0.14 and 0.82) metallic glasses has been studied. The supercooled liquid regime (ΔT_x) decreases with increase in oxygen content for the Zr–Cu–Al alloy, while it increases for the Zr–Cu metallic glass. In the case of the Zr–Cu metallic glass, the crystallization product (Zr₂Cu) is not influenced by the oxygen content, while in Zr–Cu–Al alloys the oxygen level has a strong influence on the crystallization sequence. At low oxygen level (x=0.14), the ternary glass crystallizes polymorphously to Zr₂(Cu,Al). At higher oxygen content, the ternary amorphous alloy crystallizes in two stages by primary crystallization into an icosahedral phase and subsequently to the stable Zr₂(Cu,Al) phase. Three-dimensional atom probe results have shown that the composition of the icosahedral and amorphous phases is close to Zr₇₅Cu₁₅Al₅O₅ and Zr₆₂Cu₂₄Al₁₄, respectively.     

A new glass-forming ability criterion for bulk metallic glasses

A new indicator of glass-forming ability (GFA) for bulk metallic glasses (BMGs) is proposed based on crystallization processes during cooling and reheating of the supercooled liquid. The interrelationship between this new parameter and the critical cooling rate or critical section thickness is elaborated and discussed in comparison with two other representatives, i.e. reduced glass transition temperature T_rg (=T_g/T_l, where T_g and T_l are the glass transition temperature and liquidus temperature, respectively) and supercooled liquid range ΔT_xg (=T_x−T_g, where T_x is the onset crystallization temperature and T_g the glass transition temperature). Our results have shown that ΔT_xg alone cannot infer relative GFA for BMGs while the new parameter γ, defined as T_x/(T_g+T_l), has a much better interrelationship with GFA than T_rg. An approximation of the critical cooling rate and critical section thickness for glass formation in bulk metallic glasses is also formulated and evaluated.     

Microstructure and properties of cold consolidated amorphous ribbons from (NiCu)ZrTiAlSi alloys

Amorphous ribbons of compositions (Ni₅₆Cu₂)Zr₁₈Ti₁₃Al₆Si₅ and (Ni₃₆Cu₂₃)Zr₁₈Ti₁₄Al₅Si₄ were consolidated by high pressure torsion (HPT) at room temperature. In the HPT experiments a 6 GPa pressure and two turns were applied. Samples in the form of discs, 6–7 times thicker than the ribbons and about 10 mm in diameter were achieved. The minimal deformation for the homogenous consolidation was estimated to be in the range of 400%. XRD showed that the microstructure was dependent on the composition. The sample with high Cu content remained amorphous while the sample with low Cu content revealed some crystallization. DSC experiments allowed a comparison of the glass transition temperature T_g and crystallization process of the amorphous ribbon and HPT sample which were different. The glass transition temperature T_g of the amorphous HPT sample of (Ni₃₆Cu₂₃)Zr₁₈Ti₁₄Al₅Si₄ composition decreased. For both alloys the nanohardness and the elastic modules showed decrease for cold consolidated samples in comparison to the ribbons.     

Devitrification and phase transformation of (Ti0.5Cu0.25Ni0.15Sn0.05Zr0.05)100 − xMox metallic glasses

The thermal stability and the crystallization behavior of the melt-spun ribbons of (Ti_0.5Cu_0.25Ni_0.15Sn_0.05Zr_0.05)_100 − xMo_x metallic glasses were investigated in terms of the thermal analysis. The crystallization during the glass devitrification and the solidification of the liquid for the alloys exhibit a strong similarity.     

Glass formation and magnetic properties of Fe-based metallic glasses fabricated by low-purity industrial materials

Fe-based metallic glasses of (Fe₇₄Nb₆B₂₀)_100-xCr_x (x=1, 3, 5) with high glass forming ability (GFA) and good magnetic properties were prepared using low-purity raw materials. Increasing Cr content does not significantly change glass transition temperature and onset crystallization temperature, while it enhances liquidus temperature. The addition of Cr improves the GFA of the (Fe₇₄Nb₆B₂₀)_100-xCr_x glassy alloys compared to that in Cr-free Fe-Nb-B alloys, in which the supercooled liquid region (ΔT_x), T_rg and γ are found to be 50–54 K, 0.526–0.538, and 0.367–0.371, respectively. The (Fe₇₄Nb₆B₂₀)_100–xCr_x glassy alloys exhibit excellent soft magnetic properties with high saturation magnetization of 139–161 A·m²/kg and low coercivity of 30.24–58.9 A/m. Present Fe-Nb-B-Cr glassy alloys exhibiting high GFA as well as excellent magnetic properties and low manufacturing cost make them suitable for magnetic components for engineering application.     

Glass formation and mechanical properties of (Cu50Zr50)100−xAlx (x = 0, 4, 5, 7) bulk metallic glasses

The effect of Al content on the glass formation and mechanical properties was studied for (Cu₅₀Zr₅₀)_100−xAl_x (x = 0, 4, 5, 7) bulk metallic glasses. The crystallization temperatures of fully amorphous Cu₅₀Zr₅₀, Cu₄₈Zr₄₈Al₄, Cu_47.5Zr_47.5Al₅ and Cu_46.5Zr_46.5Al₇ as-cast rods are 724 K, 753 K, 758 K and 782 K, respectively. The mechanical properties were investigated under compression at room temperature. As-cast Cu_46.5Zr_46.5Al₇ shows the highest yield strength (1867 MPa), whereas Cu_47.5Zr_47.5Al₅ shows the largest fracture strain of 11.2%. The fracture surfaces of the compressed samples were investigated by scanning electron microscopy and their morphology has been correlated with the compressive plasticity.