Development of FeNiNbSiBP bulk metallic glassy alloys with excellent magnetic properties and high glass forming ability evaluated by different criterions

Fe₃₈Ni₃₈Nb_2.5B_21.5−x−yP_xSi_y (x, y = 1–8) bulk metallic glassy alloys with high glass forming ability and excellent magnetic properties were developed. Bulk samples with maximum diameters of 3 mm are fabricated by copper mold casting method. The glassy alloys have large ΔT_x of 40–70 K. The alloys exhibit excellent magnetic properties like extremely low H_c of 0.5–0.8 A/m, high μ_e of 1.6–2.85 × 10⁴ and comparatively high B_s of 0.6–0.8 T which changes regularly with the content variations of P, B and Si. By ascertaining applicability of the empirical GFA criterions, T_rg, α, β and γ can be used in evaluating the GFA of FeNiBSiPNb system alloys.     

Microstructure and mechanical properties of a spray-formed Ti-based metallic glass former alloy

A Ti_45.8Zr_6.2Cu_39.9Ni_5.1Sn₂Si₁ composite plate was spray deposited on a copper substrate. From the bottom substrate-contact surface to the upper free surface of the deposit, a layered microstructure evolution in the order of fully amorphous (for the region 1-2 mm perpendicularly away from the substrate), amorphous/nanocrystalline (3-4 mm from the substrate), ultrafine-grained crystalline (5-6 mm from the substrate) and micron-sized crystalline phases (7-8 mm from the substrate) was observed. The oversprayed powders bellow 50 μm exhibit fully amorphous structure, while the ones above 50 μm show certain crystallization behavior. The fracture strength of 1.58-1.85 GPa with obvious plastic strain can be achieved under compressive tests for the spray-formed deposit. Spray forming can therefore produce bulk-sized high strength Ti-based alloy which evolves gradually from certain non-equilibrium towards equilibrium during deposition, which were considered to be attributable to the chill effect at the bottom substrate-contact surface and the following heat entrapment from the successively deposited droplets or powders.     

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.     

Casting effect on softening of metallic glasses

Cooling rate-induced softening in Y-based metallic glasses were verified in this work. By varying the speed of the roller in the melt-spinning process, it is found the hardness of the ribbon decrease with the cooling rate. Nanoindentation test also indicated that the ribbon at a higher cooling rate shows higher deformation energy. Contrary to crystalline materials, whose hardness usually increases with the cooling rate, the softening of metallic glasses is attributed to high concentration of defects frozen by fast cooling, and thus more structural relaxation during deformation.     

FeSiBPNbCu alloys with high glass-forming ability and good soft magnetic properties

Effects of Cu addition on the glass-forming ability (GFA), thermal stability, magnetic properties and crystallization process of (Fe_0.76Si_0.09B_0.1P_0.05)_99−xNb₁Cu_x (x = 0, 0.25, 0.5, 0.75, 1) alloys were investigated. The introduction of Cu effectively stimulates the precipitation of the α-Fe(Si) without obvious deterioration of the GFA, and successfully modifies the simultaneous precipitation of α-Fe(Si), Fe₂B and Fe₃(B,P) phases in (Fe_0.76Si_0.09B_0.1P_0.05)₉₉Nb₁ alloy into separable precipitation of each phase at different temperatures during annealing, leading to the enhancement of soft magnetic properties. The saturation magnetic flux density of the representative (Fe_0.76Si_0.09B_0.1P_0.05)_98.25Nb₁Cu_0.75 alloy could be enhanced from 1.43 to 1.51 T after annealing at 530 °C for 10 min due to the precipitation of α-Fe(Si) nanoparticles with a diameter of about 22 nm dispersing randomly in the amorphous matrix. The integration of high GFA and excellent soft magnetic properties makes the FeSiBPNbCu alloys promising soft magnetic materials for industrial applications.     

In-situ synthesis and mechanical properties of Zr-based bulk metallic glass matrix composites manipulated by nitrogen additions

Our study investigates in-situ synthesis and mechanical properties of Zr-based bulk metallic glass (BMG) matrix composites via arc plasma-induced accelerated displacement reaction (APADR) process. The aluminum nitride precursor under arc plasma-induced ultra-high temperature results in higher contents of dissolved nitrogen as well as precipitation of zirconium nitride (ZrN) particles in a Zr-based amorphous matrix. The nitrogen in the matrix results in a decrease of crystallization resistance (lower T_x and reduced glass-forming ability), but an increase of mechanical stability (a decrease of strain burst sizes). In particular, in-situ formed ZrN, which exhibits a homogeneous distribution and strong interfacial bonding with the matrix, causes an increase in compressive fracture strength and significant plastic deformation in the composite compared with the monolithic BMG. The formation of multiple shear bands and the enhancement of shear band interactions by the dissolved nitrogen as well as the in-situ formed ZrN particles were carefully confirmed by a statistical analysis on serrated flows. These results give us a guideline on how to manipulate nitrogen contents and fabricate in-situ BMG matrix composites with improved mechanical properties via APADR process.     

On the applicability of a mesoscopic interface sliding controlled model for understanding superplastic flow in bulk metallic glasses

It is demonstrated that a mesoscopic interface sliding controlled flow model, which has already been shown to account for superplastic deformation in different types of crystalline materials, is also capable of describing superplastic flow in bulk metallic glasses. The only difference is that the random high-angle grain boundaries in crystalline materials along which deformation is concentrated, have to be replaced by the transient interfaces which are formed by interconnecting shear transformation zones in the region of homogeneous flow in bulk metallic glasses. Comparison with experimental results concerning superplastic flow in eight bulk metallic glasses shows that the numerical solutions obtained in the paper for the transcendental stress–strain rate equation of superplastic deformation lead to accurate predictions.     

Critical obstacle size to deflect shear banding in Zr-based bulk metallic glass composites

The Zr₅₃Cu₂₂Ni₉Al₈Ta₈ bulk metallic glass composite (BMGC) rods have been reported to present superior plastic strain up to 30% at room temperature. The remarkable plasticity is demonstrated to be contributed by the in-situ Ta-rich precipitates in micro-sized (10–20 micro-meter) plus nano-sized (5–15 nm) scales, homogeneously distributed in the amorphous matrix. These Ta-rich particles act as discrete obstacles, separating and restricting the highly localized shear-banding, avoiding catastrophic shear-through of the whole sample and dramatically enhancing plasticity, as compared with the ZrCuNiAl monolithic BMG. To explore the critical particle size that can effectively deflect the shear banding, the Zr-based BMGC rods were plastically deformed to different strain levels (3%–25%) before fracture for investigating the interaction between the Ta-rich particles (micro- and nano-sized) and shear banding. The results suggest that the critical size of single particle or particle cluster for deflecting the shear band is greater than 20 nm and less than 100 nm. The best estimation suggests about 80 ± 20 nm.     

Preparation and properties of quaternary CoMoPB bulk metallic glasses

A new series of Co_80−xMo_xP₁₄B₆ (x = 7, 9, and 11 at%) bulk glassy alloys were successfully prepared by a combination method of fluxing treatment and J-quenching technique. The glass-forming ability (GFA) of the obtained Co-based alloys is sensitive to the Mo content substituted for Co, and the maximum attainable diameter for a fully amorphous state can reach 4.5 mm at x = 9. The compressive tests show that the obtained Co-based BMGs exhibit a compressive strength of 3.3–3.9 GPa, but nearly zero compressive plasticity. The new Co-based BMGs possess good soft magnetic properties, and their saturated magnetization values decrease from 47 emu/g (0.45 T) to 14 emu/g (0.14 T) with increasing the content of the Co substitute from 7 at% to 11 at%, which may be attributed to the anti-ferromagnetic coupling between the Mo and Co atoms. Because of their good GFA, high Co content, few constituting elements, and relatively high strength, the obtained Co-based BMGs (especially Co₇₁Mo₉P₁₄B₆ BMG) can be considered promising as starting alloys to develop the new Co-based BMGs for the advanced structural and functional applications.     

Enhancement of plasticity in Zr-based bulk metallic glasses electroplated with copper coatings

Electrodeposition was used to coat copper films on the surface of the BMG pillars (bulk metallic glasses) of Zr_52.5Cu_17.9Ni_14.6Al₁₀Ti₅ (Vit. 105) with the film thicknesses of 71.5 and 161.1 μm. The experimental results of the compression tests of the bare Vit. 105 pillars and the coated Vit. 105 pillars revealed that the copper costing increased the density of shear bands in the Vit. 105 pillars formed during the tests, resulting in the improvement of plasticity. The plastic strain was 6.1% for the coated pillars with a coating thickness of 161.1 μm, which is 3.59 times of 1.7% of the bare Vit. 105 pillars. The deformation of the copper films dissipated the strain energy and limited the propagation of shear bands, which led to the initiation and formation of multiple shear bands. The technique developed in this work provides an effective way to enhance the plasticity of BMGs at room temperature.     

AgMgAl metallic glassy and intermetallic thin films for electric contact applications

The AgMgAl thin films, in an attempt in replacing the expensive pure Au contact films, are prepared by co-sputtering. The surface morphology, roughness, amorphous or crystalline atomic structure, grain size, and electric resistivity are systematically examined. Depending on the film compositions, the films can be fully amorphous or fully nanocrystalline, or a composite with the mixture of nanocrystalline phases dispersed in the amorphous matrix. Under the as-sputtered condition, the crystalline group has the lowest resistivity, ranging from 27 to 37 μΩ·cm, the composite group lies in the middle, 31–70 μΩ·cm, and the fully amorphous group possesses the highest resistivity, 87–122 μΩ·cm. Appropriate short thermal annealing for the amorphous films can drastically lower the resistivity down to as low as 9 μΩ·cm, already compatible to pure Au (3–7 μΩ·cm). This study demonstrates the feasibility of the AgMgAl films in replacing the pure Au.     

Quasi-static and dynamic compression behaviors of metallic glass matrix composites

Compressive tests were conducted on metallic glass matrix composites at a series loading rates. It was found that mechanical properties of the composite, e.g. yielding stress and plasticity, have a week dependence on strain rates of 4.0 × 10⁻⁴ s⁻¹–4.0 × 10⁻¹ s⁻¹. Four composites were tested at a constant strain rate of 2.3 × 10 s⁻¹ to uncover the dynamic deformation behaviors. Compared with the quasi-static case, the yielding strength increased under dynamic loading rate, but the plasticity decreased significantly. On the other hand, the dynamic compressive has closely relation with the dendrite size and volume fraction. The decreasing of the dendrite size and volume fraction leaded to the dynamic yielding strength increased but the plasticity decreased. For a same composite, e.g. T1 alloy, the yielding strengths increased slightly but fracture strain decreased with increasing of dynamic strain rates.     

Microstructure and mechanical properties of metallic glass/metallic glass composites

We report microstructure and mechanical properties of bulk metallic glass (BMG)/metallic glass composites fabricated by mechanical alloying with subsequent consolidation process. The microstructural investigations of a bulk composite reveal that a submicron-scale layered structure with irregular interfaces consists of three amorphous phases in tornado-like morphology. Based on these results, poor plasticity of the metallic glass composite can be understood possibly due to the irregular interfacial morphology of the submicron-scale heterogeneous amorphous phases throughout the materials.     

Effect of minor Cu content on microstructure and mechanical property of NiTiCu bulk alloys fabricated by crystallization of metallic glass powder

Ultrafine-grained Ni_50.2−xTi_49.8Cu_x (x = 0, 2.5, 5, and 7.5) bulk shape memory alloys were fabricated by sintering of metallic glass (MG) powder and crystallization of amorphous phase. Non-isothermal crystallization kinetic analysis reveals that the crystallization mechanism of the synthesized x = 5 MG powder is typical interface-controlled two dimensional growth of nuclei followed by volume diffusion-controlled three dimensional growth of nuclei. In contrast, the crystallization mechanism of the synthesized x = 7.5 MG powder is typical volume diffusion-controlled three dimensional growth of nuclei in whole crystallization process. Correspondingly to different crystallization mechanisms, the two sintered and crystallized (SCed) bulk alloys have the same crystallized phases of bcc B2, fcc NiTi₂ phases, and monoclinic B19′, but these phases display different morphologies and distributions. The SCed x = 5 bulk alloy has a microstructure of bcc B2 matrix surrounding fcc NiTi₂ phase region, while the SCed x = 7.5 bulk alloy possesses discontinuous bcc B2 phase region. Consequently, the different crystallization mechanisms and microstructures causes extreme high yield strength and large plasticity for the SCed x = 5 bulk alloy and low strength and no plasticity for the SCed x = 7.5 bulk alloy. Especially, the yield strength of the SCed x = 5 bulk alloy is at least two times of that of the counterpart alloy prepared by melt solidification. The results provide a method fabricating high performance bulk alloys by tailoring crystallization mechanism using powder metallurgy.     

Molecular dynamics of shear transformation zones in metallic glasses

Molecular dynamics simulations have been employed to investigate the dynamics of atomic rearrangements in Ni₅₀Zr₅₀ amorphous alloys sheared at different pressures. Local atomic dynamics has been characterized in terms of number of displacing atoms as well as of apparent activation volume and energy. The dimensionality of rearranging atom clusters has been also evaluated. Numerical findings, although not conclusive, indicate that atomic rearrangements are probably triggered by a free volume redistribution. Highly localized and cooperative, such plastic rearrangements occur in regions tending to a two-dimensional occupancy of space.     

FeCo-based multiphase composites with high strength and large plastic deformation

A family of FeCo-based multiphase composites with a microstructure consisting of nano-lamellar phase strengthened α-(Fe,Co) dendritic cores surrounded by a network of reinforcement phases of ultrafine eutectics was produced by copper mold casting. The hypoeutectic composites exhibit a high yield stress, which is up to 7 times higher than the equiatomic FeCo alloy, and plastic deformation up to 18% during compressive test. Multiscale o-(Fe,Co)₃(B,C) reinforcement phases are responsible for the remarkable improvement of strength, and α-(Fe,Co) dendrites play a key role to inhibit the propagation of microcracks sourced from the eutectics. Furthermore, a fracture model for explaining the relationship between fracture strain and morphologic characteristics of the composites is presented.     

Designing a toxic-element-free Ti-based amorphous alloy with remarkable supercooled liquid region for biomedical application

A series of toxic-element-free Ti–Zr–Ta–Si amorphous alloy ribbons have been successfully prepared by melt-spinning. The differential scanning carlorimetry (DSC), X-ray diffraction analysis, bending test and microhardness test are conducted for studying the thermal and mechanical properties. The results show that the Ti₄₂Zr₄₀Ta₃Si₁₅ metallic glass ribbon present excellent ductile behavior by the bending testing, without any fracture cracking after bending over 180 degree. In addition, this amorphous alloy possesses a very high glass transition and crystallization temperature of 799 and 898 K, respectively, as well as a very wide supercooled liquid region of 99 K. This amorphous alloy exhibits promising thermal stability during isothermal annealing at the middle temperature of its supercooled region, with more than 3000 s incubation time for isothermal annealing at 823 K (550 °C). This amorphous alloy also shows much lower value of corrosion current density (2.27 × 10⁻⁹ A/m²) than the 304 stainless steel in the 0.3 mass% sodium cloride solutions. This Ti₄₂Zr₄₀Ta₃Si₁₅ alloy is believed to be a promising based alloy for fabricating the bulk metallic glass foam by the spacer technique in the application of biomedical implants.     

Fe-based soft magnetic amorphous alloys with high saturation magnetization above 1.5 T and high corrosion resistance

Fe-rich amorphous alloys with minor-addition of Cr and/or Nb were examined with the aim of developing Fe-based amorphous alloys exhibiting simultaneously high saturation magnetization above 1.5 T and good corrosion properties. Fe₈₂Cr₂B₈P₄Si₃C and Fe₈₂NbB₉P₄Si₃C amorphous alloys were found to exhibit high saturation magnetizations of 1.49 T and 1.57 T, respectively, and rather good corrosion resistance in 3.5 mass% NaCl solution at 298 K. The minor-addition of Cr or Nb enables the formation of amorphous alloy particles without harmful oxide layer by water atomization process which makes these alloys suitable for applications as soft magnetic core materials. The addition of 1 at% Nb improved the corrosion resistance through the increase in E_corr value, which makes easy to reach passive state, and the suppression of pitting corrosion. Besides, it has been proved that the simultaneous addition of Nb and Cr has an effect on forming protective passive film.     

A quinary Ti–Zr–Hf–Be–Cu high entropy bulk metallic glass with a critical size of 12 mm

A quinary Ti₂₀Zr₂₀Hf₂₀Be₂₀Cu₂₀ high entropy bulk metallic glass (HE-BMG), with a critical diameter (D_c) of 12 mm—the largest size in the reported quinary high entropy alloys (HEAs), has been successfully prepared by copper mold casing. This novel HE-BMG possesses a supercooled liquid region ΔT (=T_x − T_g) of 78 K, indicating a better thermal stability than those of other HE-BMGs. In addition, the HE-BMG exhibits a relatively good compressive plasticity (2.2 ± 0.1%) among the HE-BMGs. The newly developed HE-BMG may offer insights for the indepth understanding of the fundamental issues associated with the glass formation and the unique structure-property relationship when combining the features of HEAs and BMGs together.