Bulk nickel-based chromium and phosphorous bearing metallic glasses

• US 9,085,814 B2
• Filed: 08/22/2012
• Issued: 07/21/2015
• Est. Priority Date: 08/22/2011
• Status: Active Grant

• Current Assignee: California Institute of Technology
• Original Assignee: California Institute of Technology
• Inventors: Na, Jong Hyun, Demetriou, Marios D., Johnson, William L., Garrett, Glenn
• Primary Examiner(s): Wyszomierski, George
• Application Number:
  US13/592,095
• Publication Number:
  US 20130048152A1
• Time in Patent Office: 1,063 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C22C 1/023 Alloys based on nickel
• CPC Class Codes: C22C 1/11 Making amorphous alloys
• CPC Class Codes: C22C 19/058 without Mo and W
• CPC Class Codes: C22C 45/04 with nickel or cobalt as the major constituent
• CPC Class Codes: C22F 1/002 by rapid cooling or quenching; cooling agents used therefor
• CPC Class Codes: C22F 1/10 of nickel or cobalt or alloys based thereon

Abstract

Ni-based Cr- and P-bearing alloys that can from centimeter-thick amorphous articles are provided. Within the family of alloys, millimeter-thick bulk-glassy articles can undergo macroscopic plastic bending under load without fracturing catastrophically.

Claims

1. A metallic glass alloy comprising:

Ni<sub>(68.6−

w−

x−

y−

z)</sub>Cr_8.7+wNb_3+xP_16.5+yB_3.2+z,

where w, x, y, and z are positive or negative atomic percentages that represent a deviation from the base composition having absolute values that satisfy;

0.21|w|+0.84|x|+0.96|y|+1.18|z|<

1.89, and

wherein the alloy has a critical rod diameter of at least 3 mm.

2. The metallic glass alloy of claim 1, where w, x, y, and z have absolute values that satisfy the condition:

0.21|w|+0.84|x|+0.96|y|+1.18|z|<

1.05, and

wherein the alloy has a critical rod diameter of at least 5 mm.

3. The metallic glass alloy of claim 1, where w, x, y, and z have absolute values that satisfy the condition:

0.21|w|+0.84|x|+0.96|y|+1.18|z|<

0.43, and

wherein the alloy has a critical rod diameter of at least 8 mm.

4. A metallic glass alloy comprising:

Ni<sub>(100−

a−

b−

c−

d)</sub>Cr_aNb_bP_cB_d

where a, b, c, and d represent atomic percentages, and where;

a is greater than 2.5 and less than 15,

b is greater than 1.5 and less than 4.5,

c is greater than 14.5 and less than 18.5, and

d is greater than 1.5 and less than 4.5; and

wherein the alloy has a critical rod diameter of at least 4 mm.

5. The metallic alloy of claim 4, wherein a is greater than 6 and less than 10.5, b is greater than 2.6 and less than 3.2, c is greater than 16 and less than 17, d is greater than 2.7 and less than 3.7, and the alloy has a critical rod diameter of at least 8 mm.

6. The metallic alloy of claim 4, wherein a is between 3 and 7, and the stress intensity at crack initiation K_Q, when measured on a 3 mm diameter rod containing a notch with length between 1 and 2 mm and root radius between 0.1 and 0.15 mm, is at least 60 MPa m^1/2.

7. The metallic alloy of claim 4, wherein b is between 1.5 and 3, and the stress intensity at crack initiation K_Q, when measured on a 3 mm diameter rod containing a notch with length between 1 and 2 mm and root radius between 0.1 and 0.15 mm, is at least 60 MPa m^1/2.

8. The metallic alloy of claim 4, wherein a is between 3 and 7, and the plastic zone radius r_p, defined as (1/π

)(K_Q/σ

_y)², where K_Q is the stress intensity at crack initiation measured on a 3 mm diameter rod containing a notch with length between 1 and 2 mm and root radius between 0.1 and 0.15 mm, and where σ

_y is the compressive yield strength obtained using the 0.2% proof stress criterion, is greater than 0.2 mm.

9. The metallic alloy of claim 4, wherein b is between 1.5 and 3, and the plastic zone radius r_p, defined as (1/π

)(K_Q/σ

_y)², where K_Q is the stress intensity at crack initiation measured on a 3 mm diameter rod containing a notch with length between 1 and 2 mm and root radius between 0.1 and 0.15 mm, and where σ

_y is the compressive yield strength obtained using the 0.2% proof stress criterion, is greater than 0.2 mm.

10. The metallic alloy of claim 4, wherein a is between 3 and 7, and a wire made of such glass having a diameter of 1 mm undergoes macroscopic plastic bending under load without fracturing catastrophically.

11. The metallic alloy of claim 4, wherein b is between 1.5 and 3, and a wire made of such glass having a diameter of 1 mm undergoes macroscopic plastic bending under load without fracturing catastrophically.

12. The metallic alloy of claim 4, wherein b is between 2.5 and 3.5, and the alloy has a critical rod diameter of at least 5 mm.

13. The metallic alloy of claim 4, wherein d is greater than 2 and less than 4, and the alloy has a critical rod diameter of at least 5 mm.

14. The metallic alloy of claim 4, wherein c+d is between 18.5 and 20.5, and the alloy has a critical rod diameter of at least 5 mm.

15. The metallic glass alloy of claim 4, wherein up to 1.5 atomic % of Nb is substituted by a materials selected from the group consisting of Ta, V, or combinations thereof.

16. The metallic glass alloy of claim 4, wherein up to 2 atomic % of Cr is substituted by Fe, Co, Mn, W, Mo, Ru, Re, Cu, Pd, Pt, Ti, Zr, Hf, or combinations thereof.

17. The metallic glass alloy of claim 4, wherein up to 2 atomic % of Ni is substituted by Fe, Co, Mn, W, Mo, Ru, Re, Cu, Pd, Pt, Ti, Zr, Hf, or combinations thereof.

18. The metallic glass alloy of claim 4, wherein a rod formed of the materials having a diameter of at least 0.5 mm undergoes macroscopic plastic bending under load without fracturing catastrophically.

19. The metallic glass alloy of claim 4, wherein the compressive yield strength, σ

_y, obtained using the 0.2% proof stress criterion is greater than 2000 MPa.

20. The metallic glass alloy of claim 4, wherein the temperature of the alloy is raised to 1100°

C. or higher prior to quenching below the glass transition to form a glass.

21. The metallic glass alloy of claim 4, wherein the Poisson'"'"'s ratio is at least 0.35.

22. The metallic glass alloy of claim 4, wherein the corrosion rate in 6M HCl is not more than 0.01 mm/year.

23. A metallic glass alloy comprising:

Ni<sub>(100−

a−

b−

c−

d−

e)</sub>Cr_aNb_bP_cB_dSi_e

where a, b, c, d, and e are atomic percentages, and wherein;

a is between 4 and 14,

b is between 1.8 and 4.3,

c is between 13.5 and 17.5,

d is between 2.3 and 3.9, and

e is up to 2; and

wherein the alloy has a critical rod diameter of at least 3 mm.

24. The metallic glass alloy of claim 23, wherein a is greater than 7 and less than 10, and the stress intensity at crack initiation when measured on a 3 mm diameter rod containing a notch with length between 1 and 2 mm and root radius between 0.1 and 0.15 mm is at least 60 MPa m^1/2.

25. The metallic glass alloy of claim 23, wherein b is greater than 1.5 and less than 3, and the stress intensity at crack initiation when measured on a 3 mm diameter rod containing a notch with length between 1 and 2 mm and root radius between 0.1 and 0.15 mm is at least 60 MPa m^1/2.

26. The metallic glass alloy of claim 23, wherein a is greater than 7 and less than 10, and the plastic zone radius r_p, defined as (1/π

)(K_Q/σ

_y)², where K_Q is the stress intensity at crack initiation measured on a 3 mm diameter rod containing a notch with length between 1 and 2 mm and root radius between 0.1 and 0.15 mm, and where σ

_y is the compressive yield strength obtained using the 0.2% proof stress criterion, is greater than 0.2 mm.

27. The metallic glass alloy of claim 23, wherein b is greater than 1.5 and less than 3, and the plastic zone radius r_p, defined as (1/π

)(K_Q/σ

_y)², where K_Q is the stress intensity at crack initiation measured on a 3 mm diameter rod containing a notch with length between 1 and 2 mm and root radius between 0.1 and 0.15 mm, and where σ

_y is the compressive yield strength obtained using the 0.2% proof stress criterion, is greater than 0.2 mm.

28. The metallic glass alloy of claim 23, wherein a is greater than 7 and less than 10, and a wire made of such glass having a diameter of 1 mm undergoes macroscopic plastic bending under load without fracturing catastrophically.

29. The metallic glass alloy of claim 23, wherein b is greater than 1.5 and less than 3, and a wire made of such glass having a diameter of 1 undergoes macroscopic plastic bending under load without fracturing catastrophically.

30. The metallic glass alloy of claim 23, wherein b is between 2.5 and 3.5, and the alloy has a critical rod diameter of at least 4 mm.

31. The metallic glass alloy of claim 23, wherein d is between 2.9 and 3.5, and the alloy has a critical rod diameter of at least 4 mm.

32. The metallic glass alloy of claim 23, wherein e is up to 1.5, and the alloy has a critical rod diameter of at least 4 mm.

33. The metallic glass alloy of claim 23, wherein c+d+e is between 18.5 and 20.5, and the alloy has a critical rod diameter of at least 4 mm.

34. The metallic glass alloy of claim 23, wherein up to 1.5 atomic % of Nb is substituted by a materials selected from the group consisting of Ta, V, or combinations thereof.

35. The metallic glass alloy of claim 23, wherein up to 2 atomic % of Cr is substituted by Fe, Co, Mn, W, Mo, Ru, Re, Cu, Pd, Pt, Ti, Zr, Hf, or combinations thereof.

36. The metallic glass alloy of claim 23, wherein up to 2 atomic % of Ni is substituted by Fe, Co, Mn, W, Mo, Ru, Re, Cu, Pd, Pt, Ti, Zr, Hf, or combinations thereof.

37. The metallic glass alloy of claim 23, wherein a rod formed of the materials having a diameter of at least 0.5 mm undergoes macroscopic plastic bending under load without fracturing catastrophically.

38. The metallic glass alloy of claim 23, wherein the compressive yield strength, σ

_y, obtained using the 0.2% proof stress criterion is greater than 2000 MPa.

39. The metallic glass alloy of claim 23, wherein the temperature of the alloy is raised to 1100°

C. or higher prior to quenching below the glass transition to form a glass.

40. The metallic glass alloy of claim 23, wherein the Poisson'"'"'s ratio is at least 0.35.

41. The metallic glass alloy of claim 23, wherein the corrosion rate in 6M HCl is not more than 0.01 mm/year.

42. A metallic glass alloy selected from the group consisting of:

Ni₆₉Cr_8.5Nb₃P₁₇B_2.5, Ni₆₉Cr_8.5Nb₃P_16.75B_2.75, Ni₆₉Cr_8.5Nb₃P_16.5B₃, Ni₆₉Cr_8.5Nb₃P₁₆B_3.5, Ni₆₉Cr_8.5Nb₃P_15.75B_3.75, Ni₆₉Cr₉Nb_2.5P_16.5B₃, Ni₆₉Cr_8.75Nb_2.75P_16.5B₃, Ni₆₉Cr_8.25Nb_3.25P_16.5B₃, Ni₆₉Cr₈Nb_3.5P_16.5B₃, Ni₆₉Cr_7.5Nb₄P_16.5B₃, Ni_72.5Cr₅Nb₃P_16.5B₃, Ni_71.5Cr₆Nb₃P_16.5B₃, Ni_70.5Cr₇Nb₃P_16.5B₃, Ni_69.5Cr₈Nb₃P_16.5B₃, Ni_68.5Cr₉Nb₃P_16.5B₃, Ni₆₈Cr_9.5Nb₃P_16.5B₃, Ni_67.5Cr₁₀Nb₃P_16.5B₃, Ni_66.5Cr₁₁Nb₃P_16.5B₃, Ni_65.5Cr₁₂Nb₃P_16.5B₃, Ni_68.5Cr₉Nb₃P₁₆B₃Si_0.5, Ni_68.5Cr₉Nb₃P_15.5B₃Si₁, Ni₆₉Cr_8.5Nb₃P₁₆B₃Si_0.5, Ni₆₉Cr_8.5Nb₃P_15.5B₃Si₁, Ni_69.03Cr_8.75Nb_3.02P_16.08B_3.12, Ni_68.17Cr_8.65Nb_2.98P_16.92B_3.28, Ni_67.75Cr_8.59Nb_2.96P_17.34B_3.36, Ni₆₉Cr_8.5Nb_2.5Ta_0.5P_15.5B₃Si₁, and Ni_69.5Cr_8.5Nb_2.5Ta_0.5P_15.5B₃Si₁;

wherein the alloy has a critical rod diameter of at least 3 mm.

43. A metallic glass alloy comprising:

Ni_68.6Cr_8.7Nb₃P_16.5B_3.2;

wherein the alloy has a critical rod diameter of at least 3 mm.

44. A metallic glass alloy comprising:

Ni_68.6Cr_8.7Nb₃P₁₆Si_0.5B_3.2;

wherein the alloy has a critical rod diameter of at least 3 mm.