Understanding the Effect of Oxygen on the Glass-Forming Ability of Zr55Cu55Al9Be9 Bulk Metallic Glass by ab initio Molecular Dynamics Simulations

Oxygen (O) is an inevitable impurity in bulk metallic glasses (BMGs) and its influence over the glass-forming ability (GFA) of BMGs is a longstanding controversy. The present ab initio molecular dynamics (AIMD) simulations indicate that the GFA decreases upon introducing 0.78 at. pct O in the amorphous Zr₅₅Cu₅₅Al₉Be₉ (at. pct), while examining the evolution of atomic configurations and kinetic properties in BMGs. This study includes a comprehensive analysis using pair correlation function (PCF), bond pair analysis (BPA), and Voronoi polyhedra construction. It is concluded that the incorporation of O leads to a decline in the closely packed icosahedral polyhedrons, where the atom O is coordinated with Be and Zr in the first nearest shell to form the O-centered clusters with enhanced ordering. Mean square displacement (MSD) analysis also shows that the trace O could induce remarkable acceleration of atomic mobility, therefore increasing crystallization tendency of the Zr₅₅Cu₅₅Al₉Be₉ alloy. The present results illuminate the role of O in the metallic glass-forming process and reveal the underlying role of O in the GFA of the Zr-Cu amorphous alloys.

     

Effect of Au Content on Thermal Stability and Mechanical Properties of Au-Cu-Ag-Si Bulk Metallic Glasses

The thermal stability, glass-forming ability (GFA), and mechanical and electrical properties of Au-based Au _x Si₁₇Cu_75.5–x Ag_7.5 (x = 40 to 75.5 at. pct) metallic glasses were investigated. The glass transition temperature (T _g ) and crystallization temperature (T _x ) decreased with increasing Au content. The ultralow T _g values below 373 K (100 °C) were obtained for alloys with x = 55 to 75.5. The alloys with x = 45 to 70 exhibited a high stabilization of supercooled liquid and a high GFA, and the supercooled liquid region and critical sample diameter for glass formation were in the range of 31 K to 50 K and 2 to 5 mm, respectively. The compressive fracture strength (σ _c,f ), Young’s modulus (E), and Vicker’s hardness (H _v ) of the bulk metallic glasses (BMGs) decreased with increasing Au content. A linear correlation between Au concentration and the characteristic temperature, i.e., T _g and T _x , and mechanical properties, i.e., σ _c,f , E, and H _v , as well as electrical resistivity can be found in the BMGs, which will be helpful for the composition design of the desirable Au-based BMGs with tunable physical properties.     

Ti-Cu-Zr-Fe-Sn-Si-Ag-Pd Bulk Metallic Glasses with Potential for Biomedical Applications

Ti₄₇Cu_38−xZr_7.5Fe_2.5Sn₂Si₁Ag₂Pd_x (x = 1, 2, 3, and 4 atomic percent, at. pct) bulk metallic glasses (BMGs) with potential for biomedical applications were fabricated by copper-mold casting. The Ti-based BMGs exhibited high glass-forming ability (GFA) with critical diameters of 4 to 5 mm and a supercooled liquid region over 50 K, though the high contents of Pd slightly decreased the GFA. The additions of 2 and 3 at. pct Pd benefited the improvement of plasticity, and the resultant BMGs showed the relatively low Young’s modulus of about 100 GPa, high compressive strengths of 2174 to 2340 MPa, and compressive plastic strain of around 4 pct. The addition of Pd also decreased the passive current density and increased the pitting potential of the Ti-based BMGs in the Hank’s solution, leading to the enhanced bio-corrosion resistance of the BMGs. Furthermore, the cell adhesion, viability, and proliferation behaviors revealed that the present Ti-based BMGs possess as good biocompatibility as that of the Ti-6Al-4V alloy. These results demonstrated the potential of the Ti-Cu-Zr-Fe-Sn-Si-Ag-Pd BMGs as biomedical materials.

     

Thermal Stability and Crystallization Kinetics in Y-Based Metallic Glasses

The glass-forming ability (GFA) and thermal stability of Y_56–x Sc _x Al₂₄Co₂₀ (0 ≤ x ≤ 18) alloys produced by melt spinning and suction casting have been investigated. The results show that the addition of a Sc element improves the GFA of Y-based metallic glasses, and the Y₄₁Sc₁₅Al₂₄Co₂₀ alloy has a reduced glass transition temperature T _rg (=T _g /T _l ) as large as 0.641. A new bulk metallic glass (BMG), Y₄₁Sc₁₅Al₂₄Co₂₀, with a diameter of 5 mm was successfully fabricated. The superior GFA after the Sc addition can be attributed to the ability of Sc to effectively alleviate the detrimental effect of oxygen as well as appropriate atomic-size mismatch and large negative heat of mixing among constituent elements. Crystallization kinetic studies show that the activation energies for the Y₄₁Sc₁₅Al₂₄Co₂₀ BMG are E _g  = 4.92 eV and E _x  = 3.18 eV, for the glass transition and crystallization, respectively, which are the highest in all known rare-earth (RE)–based BMGs. The values of the fragility parameter m for the Y₅₆Al₂₄Co₂₀ and Y₄₁Sc₁₅Al₂₄Co₂₀ BMGs are 72 and 42, respectively. The significant decrease in m implies that the GFA and the thermal stability increase with the addition of Sc in the Y₅₆Al₂₄Co₂₀ alloy. This article is based on a presentation given in the symposium entitled “Bulk Metallic Glasses IV,” which occurred February 25–March 1, 2007 during the TMS Annual Meeting in Orlando, FL, under the auspices of the TMS/ASM Mechanical Behavior of Materials Committee.     

[(Fe<Subscript>0.5</Subscript>Co<Subscript>0.5</Subscript>)<Subscript>0.75</Subscript>B<Subscript>0.20</Subscript>Si<Subscript>0.05</Subscript>]<Subscript>96</Subscript>Nb<Subscript>4</Subscript> Metallic Glasses with Small Cu Additions

Recently, (Fe-Co)-B-Si-Nb bulk metallic glasses (BMGs) were produced. Such BMGs exhibit high glass-forming ability (GFA) as well as good mechanical and magnetic properties. These alloys combine the advantages of functional and structural materials. The soft magnetic properties can be enhanced by nanocrystallization. To force the nanocrystallization, small content of Cu was added to the starting composition. In this article, {[(Fe_0.5Co_0.5)_0.75Si_0.05B_0.20]_0.96Nb_0.04}_100–x Cu _x glassy alloys (x = 1, 2, and 3) were chosen for investigation. The GFA and the thermal stability of these alloys were evaluated. The effects of crystallization during heat-treatment processes on the phase evolution and the magnetic properties, including M _s , H _c , and T _c , in these alloys were investigated. The phase analyses were done with the help of the X-ray diffraction patterns recorded in situ by using the synchrotron radiation in transmission configuration.     

Ductile Ti-Based Bulk Metallic Glasses with High Specific Strength

Ti-based bulk metallic glasses (BMGs) with large compressive plasticity were developed in the Ti-rich part of Vitreloy series BMGs (Ti_65–x Zr _x Cu₉Ni₈Be₁₈ alloys with x = 0, 5, 10, 15, and 20). The current materials exhibit high fracture strength reaching ~2.3 GPa and plastic strains up to ~8.3 pct after partial substitution of Zr by Ti. The plasticity of the investigated alloys strongly depends on the Zr content, which affects the elastic constants, such as Poisson’s ratio and shear modulus. This, in turn, has an impact on the shear transformation zone (STZ) volume and, hence, on the shear banding of the glasses.     

Thermal Stability, Glass-Formation Ability, and Mechanical Properties of (Zr41.2Ti13.8Cu12.5Ni10Be22.5)100?xNbx Amorphous Alloys

Bulk amorphous alloys of (Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5)_100−x Nb _x with x = 0, 5, 11, and 13 were prepared by water quenching. Differential scanning calorimeter (DSC) analysis revealed that the addition of Nb enhances the thermal stability but appreciably decreases the glass-forming ability (GFA) of the alloys. Scanning electron microscope (SEM) and compression tests indicated that the Nb addition effectively improves the strength and plasticity of a Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 amorphous alloy, which benefits from multiple shear bands induced by ductile crystalline phase dispersing in the amorphous matrix. The bulk amorphous alloy with x = 5 exhibits a fracture stress of 2070 MPa and total strain to fracture of 25.8 pct, respectively. This article is based on a presentation given in the symposium entitled “Bulk Metallic Glasses IV,” which occurred February 25–March 1, 2007, during the TMS Annual Meeting in Orlando, FL, under the auspices of the TMS/ASM Mechanical Behavior of Materials Committee.

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Formation, Crystallization Behavior, and Soft Magnetic Properties of FeCSiBP Bulk Metallic Glass Fabricated Using Industrial Raw Materials

Formation of pseudo-binary Fe-C-Si-B-P bulk metallic glasses (BMGs) with good glass-forming ability (GFA) and soft magnetic properties prepared using industrial pig-iron and P-Fe alloys as raw materials was investigated. It was found that the GFA could be enhanced by tuning the content of carbon, and fully glassy rods with a maximum diameter of 2?mm were obtained in the Fe_77.3C_5.9Si_3.3B_4.8P_8.7 alloy. The crystallization behavior and its effects on the soft magnetic properties of the Fe_77.3C_5.9Si_3.3B_4.8P_8.7 alloy were analyzed. The superior magnetic properties, coupled with large GFA and low cost of raw materials, make the current Fe-based BMGs promising for potential applications in electric industries.     

Effect of B on the microstructure and mechanical properties of mechanically milled TiAl alloys

The present study is concerned with γ-(Ti₅₂Al₄₈)_100−x B _x (x=0, 0.5, 2, 5) alloys produced by mechanical milling/vacuum hot pressing (VHPing) using melt-extracted powders. Microstructure of the as-vacuum hot pressed (VHPed) alloys exhibits a duplex equiaxed microstructure of α₂ and γ with a mean grain size of 200 nm. Besides α₂ and γ phases, binary and 0.5 pct B alloys contain Ti₂AlN and Al₂O₃ phases located along the grain boundaries and show appreciable coarsening in grain and dispersoid sizes during annealing treatment at 1300 °C for 5 hours. On the other hand, 2 pct B and 5 pct B alloys contain fine boride particles within the γ grains and show minimal coarsening during annealing. Room-temperature compressing tests of the as-VHPed alloys show low ductility, but very high yield strength >2100 MPa. After annealing treatment, mechanically milled alloys show much higher yield strength than conventional powder metallurgy and ingot metallurgy processed alloys, with equivalent ductility to ingot metallurgy processed alloys. The 5 pct B alloy with the smallest grain size shows higher yield strength than binary alloy up to the test temperature of 700 °C. At 850 °C, 5 pct B alloy shows much lower strength than the binary alloy, indicating that the deformation of fine 5 pct B alloy is dominated by the grain boundary sliding mechanism. This article is based on a presentation made in the symposium “Mechanical Behavior of Bulk Nanocrystalline Solids,” presented at the 1997 Fall TMS Meeting and Materials Week, September 14–18, 1997, in Indianapolis, Indiana, under the auspices of the Mechanical Metallurgy (SMD), Powder Materials (MDMD), and Chemistry and Physics of Materials (EMPMD/SMD) Committees.     

Glass-Forming Ability and Competitive Crystalline Phases for Lightweight Ti-Be–Based Alloys

The glass-forming ability (GFA) for the Ti-Be–based alloys in the Ti-Be-Zr ternary system is systematically studied. It was found that the best GFA obtained at a composition of Ti₄₁Be₃₄Zr₂₅ (at. pct) in the Ti-Be-Zr ternary system, and the bulk-metallic-glass (BMG) rod samples with a diameter of 5 mm were fabricated by Cu-mold casting. The competitive crystalline phases around the composition of the best GFA materials were determined by scanning electron microscopy (SEM) and X-ray diffractometry (XRD). The GFA of the ternary alloys was further improved by an addition of 4 at. pct vanadium (V). The largest supercooled liquid region, ΔT _x (ΔT _x  = T _x − T _g , T _g is the glass-transition temperature, and T _x the crystallization temperature), in the ternary alloy system reaches about 110 K (110 °C) for the Ti₃₅Be₃₂Zr₃₃ alloy.     

Prediction of Glass-Forming Compositions in Metallic Systems: Copper-Based Bulk Metallic Glasses in the Cu-Mg-Ca System

A novel methodology for predicting specific compositions for glass-forming alloys based on efficiently packed atomic cluster selection, liquidus lines, and ab initio calculations is presented. This model has shown applicable adaptation to many known metallic and ceramic oxide glass-forming systems and has led to the discovery of soon to be reported Ag- and Zn-based bulk metallic glasses (BMGs). As a model system, glass formation in the Cu-Mg-Ca ternary system has been assessed using this alloy design methodology, which has led to the discovery of a number of Cu-based BMGs with compositions ranging from Cu-33 to 55 at. pct, Mg-18 to 45 at. pct, and Ca-18 to 36 at. pct. Included in this work are the calculated values of associated cluster binding energies and correlations between physical and thermal properties of these glassy compositions, which show significant physical evidence to support the likely existence of such clusters.     

Microstructure, mechanical properties, and fracture mechanism of As-cast (Ti0.5Cu0.25Ni0.15Sn0.05Zr0.05)100−x Mo x composites

Copper mold cast cylinders of (Ti_0.5Cu_0.25Ni_0.15Sn_0.05Zr_0.05)_100−x Mo _x composites are prepared. Addition of Mo in the bulk glass-forming alloy induces the formation of a dendrite/matrix composite. For 3-mm-diameter cylinders, the matrix exhibits a homogenous ultrafine microstructure for Mo content of 2.5 at. pct, and a fine eutectic microstructure for 5 at. pct Mo. For 5-mm-diameter cylinders, the matrix exhibits a dendritic microstructure for 2.5 at. pct Mo, and exhibits a coarser eutectic microstructure for 5 at. pct Mo. Despite the formation of a dendrite/nanostructured matrix composite in the cylinders, the quenched surface layer with a nanoscale grain size dominates the deformation and fracture of the 3-mm-diameter cylinders. More than 56 vol pct quenched layer leads to a distensile fracture mode and the samples exhibit high fracture strength and high Young’s modulus but low ductility. For 5-mm-diameter cylinders, the composite microstructure becomes dominant due to its more than 64 vol pct volume fraction leading to a cone-shaped fracture surface. The samples exhibit lower yield strength and lower Young’s modulus but better ductility compared to the 3-mm-diameter cylinders. The mechanical behavior of the Mo-bearing composites strongly depends on the microstructural homogeneity and casting defects formed upon solidification.     

Glass-Forming Ability of Mg–Cu–Ni–Gd Bulk Metallic Glasses with High Strength

The glass-forming ability (GFA) of Mg–Cu–Ni–Gd alloy system was evaluated using copper mold casting. A three-dimensional composition map of Mg–Cu–Ni–Gd system with GFA over 6 mm was revealed, confirming that the Ni addition decreased the GFA of Mg–Cu–Gd system. The maximum Ni tolerance was about 6 at.% for the Mg–Cu–Ni–Gd BMGs with GFA over 6 mm. The compressive tests displayed that the Ni addition as small as 3.45 at.% could result in higher strength for the Mg–Cu–Gd BMGs. The Mg–Cu–Ni–Gd system with small Ni content can be balanced candidates for the Mg-based BMGs with both acceptable GFA and high strength.     

The effect of processing and microstructure development on the slip and fracture behavior of the 2.1 wt pct Li AF/C-489 and 1.8 wt pct Li AF/C-458 Al-Li-Cu-X alloys

Although Al-Li-Cu alloys showed initial promise as lightweight structural materials, implementation into primary aerospace applications has been hindered due in part to their characteristic anisotropic mechanical and fracture behaviors. The Air Force recently developed two isotropic Al-Li-Cu-X alloys with 2.1 wt pct Li and 1.8 wt pct Li designated AF/C-489 and AF/C-458, respectively. The elongation at peak strength was less than the required 5 pct for the 2.1 wt pct Li variant but greater than 10 pct for the 1.8 wt pct Li alloy. The objectives of our investigations were to first identify the mechanisms for the large difference in ductility between the AF/C-489 and AF/C-458 alloys and then to develop an aging schedule to optimize the microstructure for high ductility and strength levels. Duplex and triple aging practices were designed to minimize grain boundary precipitation while encouraging matrix precipitation of the T₁ (Al₂CuLi) strengthening phase. Certain duplex aged conditions for the AF/C-489 alloy showed significant increases in ductility by as much as 85 pct with a small decrease of only 6.5 and 2.5 pct in yield and ultimate tensile strength, respectively. However, no significant variations were found through either duplex or triple aging practices for the AF/C-458 alloys, thus, indicating a very large processing window. Grain size and δ′ (Al₃Li) volume fraction were determined to be the major cause for the differences in the mechanical properties of the two alloys.     

On the fracture and fatigue properties of Mo-Mo<Subscript>3</Subscript>Si-Mo<Subscript>5</Subscript>SiB<Subscript>2</Subscript> refractory intermetallic alloys at ambient to elevated temperatures (25 °C to 1300 °C)

The need for structural materials with high-temperature strength and oxidation resistance coupled with adequate lower-temperature toughness for potential use at temperatures above ∼1000 °C has remained a persistent challenge in materials science. In this work, one promising class of intermetallic alloys is examined, namely, boron-containing molybdenum silicides, with compositions in the range Mo (bal), 12 to 17 at. pct Si, 8.5 at. pct B, processed using both ingot (I/M) and powder (P/M) metallurgy methods. Specifically, the oxidation (“pesting”), fracture toughness, and fatigue-crack propagation resistance of four such alloys, which consisted of ∼21 to 38 vol. pct α-Mo phase in an intermetallic matrix of Mo₃Si and Mo₅SiB₂ (T₂), were characterized at temperatures between 25 °C and 1300 °C. The boron additions were found to confer improved “pest” resistance (at 400 °C to 900 °C) as compared to unmodified molybdenum silicides, such as Mo₅Si₃. Moreover, although the fracture and fatigue properties of the finer-scale P/M alloys were only marginally better than those of MoSi₂, for the I/M processed microstructures with coarse distributions of the α-Mo phase, fracture toughness properties were far superior, rising from values above 7 MPa √m at ambient temperatures to almost 12 MPa √m at 1300 °C. Similarly, the fatigue-crack propagation resistance was significantly better than that of MoSi₂, with fatigue threshold values roughly 70 pct of the toughness, i.e., rising from over 5 MPa √m at 25 °C to ∼8 MPa √m at 1300 °C. These results, in particular, that the toughness and cyclic crack-growth resistance actually increased with increasing temperature, are discussed in terms of the salient mechanisms of toughening in Mo-Si-B alloys and the specific role of microstructure.     

Preparation and properties of fine grain β- CuAlNi strain- memory alloys

A method has been developed to produce grain sizes as small as 5 μm in alloys of β-CuAlNi. The alloys were of eutectoid composition and a procedure was developed for determining the composition of a eutectoid alloy having any required value for transition temperature (M _s ). The thermo-mechanical treatment involved two sequential stages of warm rolling followed by recrystallization. The alloys produced were single phase β-type with no second phase being present. Characteristic two-stage stress-strain curves were obtained for most of the specimens. It was generally found that the tensile strength and strain to failure increased with decreasing grain size according to a Hall-Petch type relationship down to a grain size of 5 μm. A fracture strength of 1200 MPa and a fracture strain of 10 pct were obtained in the best alloy. It was found that the major recovery mode, whether pseudoelastic or strain-memory, did not have any significant effect on the total recovery obtained. Recovery properties were not affected significantly by decreasing grain size, and 86 pct recovery could still be obtained at a grain size of around 10 μm. Grain refinement improved the fatigue life considerably, possibly due to the high ultimate fracture stress and ductile fracture mode. A fatigue life of 275,000 cycles could be obtained for an applied stress of 330 MPa and a steady state strain of 0.7 pct. At fine-grain sizes most of the fractures were due to transgranular-type brittle fracture and micro void-type ductile fracture, depending on the alloy composition. It was suggested that the difference between the alloys was due to differences in oxygen segregation at the grain boundaries.     

Microstructure and high-temperature tensile deformation of tiai(si) alloys made from elemental powders

Two ternary TiAl-based alloys with chemical compositions of Ti-46.4 at. pct Al-1.4 at. pct Si (Si poor) and Ti-45 at. pct Al-2.7 at. pct Si (Si rich), which were prepared by reaction powder processing, have been investigated. Both alloys consist of the intermetallic compounds y-TiAl, α₂-Ti₃Al, and ξ-Ti₅(Si, Al)₃. The microstructure can be described as a duplex structure(i.e., lamellar γ/α₂ regions distributed in γ matrix) containing ξ precipitates. The higher Si content leads to a larger amount of ξ precipitates and a finer y grain size in the Si-rich alloy. The tensile properties of both alloys depend on test temperature. At room temperature and 700 °C, the tensile properties of the Si-poor alloy are better than those of the Si-rich alloy. At 900 °C, the opposite is true. Examinations of tensile deformed specimens reveal ξ-Ti₅(Si, Al)₃ particle debonding and particle cracking at lower test temperatures. At 900 °C, nucleation of voids and microcracks along lamellar grain boundaries and evidence for recovery and dynamic recrystallization were observed. Due to these processes, the alloys can tolerate ξ-Ti₅(Si, Al)₃ particles at high temperature, where the positive effect of grain refinement on both strength and ductility can be utilized.     

Effects of R-ratio on the fatigue crack growth of Nb-Si(ss) and Nb-10Si In Situ composites

The effects of changes in R ratio on the fatigue crack growth behavior of a Nb-10 at. pct Si composite as well as bulk Nb-1.24 at. pct Si were determined. Fatigue crack growth experiments were performed over a range of ΔK levels at R ratios of 0.1 and 0.4. Qualitative and quantitative scanning electron microscopy studies were performed to characterize the fatigue fracture features of the composites and alloys, in order to determine the factors controlling these fracture features. The results of this work indicate that increases in R ratio reduce the observed threshold stress intensities in both materials. Somewhat higher fatigue thresholds were observed in the Nb-Si _(ss) compared to pure Nb in the literature. In contrast to the bulk Nb-Si _(ss) alloy, which exhibited no evidence of cleavage fracture in fatigue at any R ratio or ΔK level, the Nb-Si _(ss) constituent in the Nb-10 at. pct Si composite exhibited a distinct fracture mode transition from ductile tearing near threshold and low ΔK to cleavage fracture with an increase in ΔK and K _max. Possible reasons for such observations are provided. This article is based on a presentation made in the symposium “Fatigue and Creep of Composite Materials” presented at the TMS Fall Meeting in Indianapolis, Indiana, September 14–18, 1997, under the auspices of the TMS/ASM Composite Materials Committee.     

Preparation,mechanical strengths,and thermal

Ni-based amorphous wires with good bending ductility have been prepared for Ni₇₅Si₈B₁₇ and Ni₇₈P₁₂B₁₀ alloys containing 1 to 2 at. pct Al or Zr by melt spinning in rotating water. The enhancement of the wire-formation tendency by the addition of Al has been clarified to be due to the increase in the stability of the melt jet through the formation of a thin A1₂O₃ film on the outer surface. The maximum wire diameter is about 190 to 200 μm for the Ni-Si (or P)-B-Al alloys and increases to about 250 μm for the Ni-Si-B-Al-Cr alloys containing 4 to 6 at. pct Cr. The tensile fracture strength and fracture elongation are 2730 MPa and 2.9 pct for (Ni_0.75Si_0.08B_{0.17 99}Al₁) wire and 2170 MPa and 2.4 pct for (Ni_0.78P_0.12B_0.1)₉₉Al₁ wire. These wires exhibit a fatigue limit under dynamic bending strain in air with a relative humidity of 65 pct; this limit is 0.50 pct for a Ni-Si-B-Al wire, which is higher by 0.15 pct than that of a Fe₇₅Si₁₀B₁₅ amorphous wire. Furthermore, the Ni-base wires do not fracture during a 180-deg bending even for a sample annealed at temperatures just below the crystallization temperature, in sharp contrast to high embrittlement tendency for Fe-base amorphous alloys. Thus, the Ni-based amorphous wires have been shown to be an attractive material similar to Fe- and Co-based amorphous wires because of its high static and dynamic strength, high ductility, high stability to thermal embrittlement, and good corrosion resistance.