Fig. 1. (a) X-ray diffraction patterns of as-spun Zr50M50, Zr50(M,Ag)50 and Zr50(M,Pd)50 (M = Fe, Co, Ni, Cu) alloy ribbons with thicknesses of 51, 34 and 34 μm, respectively. Bright-field TEM images and selected-area electron diffraction patterns of the (b,c) Zr50M50 with thicknesses of 51 μm, (d,e) Zr50(M,Ag)50 with thicknesses of 34 μm, and (f,g) Zr50(M,Pd)50 with thicknesses of 34 μm alloy ribbons. These ribbons are fully amorphous.

Fig. 2. (a) DSC curves of as-spun Zr50M50, Zr50(M,Ag)50 and Zr50(M,Pd)50 alloy ribbons (Fig. S1). (b) and (c) X-ray diffraction patterns (CuKα) of these ribbons: (b) annealed for 1.8 ks at 770?820 K, a temperature just above the first exothermic DSC peak; and (c) at 850 K, a temperature just above the second exothermic peak.

Fig. 3. Bright-field TEM images, selected-area electron diffraction patterns, high-resolution TEM images and nanobeam electron diffraction patterns of: (a?d) Zr50M50, (e?h) Zr50(M,Ag)50, and (i?l) Zr50(M,Pd)50 amorphous ribbons annealed for 1.8 ks at 770?820 K (above Tp1); and (m?q) Zr50M50 amorphous ribbon annealed for 1.8 ks at 850 K (above Tp2).

Fig. 4. X-ray diffraction patterns (CuKα) and bending plasticity of as-spun (a) Zr50M50, (b) Zr50(M,Ag)50 and (c) Zr50(M,Pd)50 alloy ribbons with different thicknesses. (d) SEM image showing the shear steps on the bent outer surface of the 58 μm-thick Zr50M50 amorphous ribbon. (e) Photograph of the three alloy ribbons bent through 180° and then recovered to the original straight state.

Fig. 5. Bright-field TEM images and selected-area electron diffraction patterns of: (a,b) Zr50M50; (c,d) Zr50(M,Ag)50; and (e,f) Zr50(M,Pd)50 alloy ribbons with thicknesses of 58, 58 and 52 μm, respectively, corresponding to the critical thickness at which the ductile-to-brittle transition occurs.

Fig. 6. Changes in the structure, Vickers hardness and bending plasticity with ribbon thickness for Zr50M50, Zr50(M,Ag)50 and Zr50(M,Pd)50 amorphous ribbons.

Fig. 7. (a) Tensile stress-elongation curves of: as-spun Zr50M50 amorphous ribbons with thicknesses of 51 and 58 μm; a 53 μm-thick Zr50(M,Ag)50 amorphous ribbon; and a 34 μm-thick Zr50(M,Pd)50 amorphous ribbon. For the Zr50M50 amorphous ribbon: (b?c) SEM images of the fracture surface; and (d) the air-side surface near the final fracture edge.

Fig. 8. (a) Schematic diagram showing the tensile fracture surface and TEM observation sites (A, B, C) for a Zr50M50 amorphous ribbon (51 μm thick) loaded in tension until fracture. Bright-field TEM images, selected-area electron diffraction pattern, high-resolution TEM images, and Fourier-transform images of: (b,c) region A; (d,e,i-k) region B; and (f?h) region C.

Fig. 9. A melt-spun Zr50M50 alloy ribbon cold-rolled to thickness reductions of up to 30% at room temperature: (a) changes in Vickers hardness, structure, and bending plasticity with reductions in thickness, and the corresponding (b) X-ray diffraction patterns, and (c) DSC curves. For the sample cold-rolled to 30% thickness reduction: (d,f) bright-field TEM images; (e,g) selected-area electron diffraction patterns; (h) high-resolution TEM image; (i) Fourier-transform images; and (j) SEM image of the bent outer surface.

Fig. 10. Schematic continuous cooling and heating transformation (CCT and CHT) curves for (a) Zr50M50, (b) Zr50(M,Ag)50 and (c) Zr50(M,Pd)50 amorphous alloys. A cold-rolling-induced transformation (CRT) curve for Zr50M50 amorphous ribbon is shown in (d).