Berylllium bearing amorphous metallic alloys formed by low cooling rates

• US 5,288,344 A
• Filed: 04/07/1993
• Issued: 02/22/1994
• Est. Priority Date: 04/07/1993
• Status: Expired due to Term

• Current Assignee: California Institute of Technology
• Original Assignee: California Institute of Technology
• Inventors: Johnson, William L., Peker, Atakan
• Primary Examiner(s): Roy, Upendra
• Application Number:
  US08/044,814
• Time in Patent Office: 321 Days
• Field of Search: 148/403, 420/422, 420/417
• US Class Current: 148/403
• CPC Class Codes: C22C 45/10 with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent

Abstract

Alloys which form metallic glass upon cooling below the glass transition temperature at a rate appreciably less than 10⁶ K/s comprise beryllium in the range of from 5 to 52 atomic percent and at least one early transition metal in the range of from 30 to 75% and at least one late transition metal in the range of from 2 to 52%. A preferred group of metallic glass alloys has the formula (Zr_1-X Ti_X)_a (Cu_1-y Ni_y)_b Be_c. Generally, a is in the range from 30 to 75% and the lower limit increases with increasing x. When x is in the range of from 0 to 0.15, b is in the range of from 5 to 52%, and c is in the range of from 6 to 47%. When x is in the range of from 0.15 to 0.4, b is in the range of from 5 to 52%, and c is in the range of from 5 to 47%. When x is in the range of from 0.4 to 0.6, b is in the range of from 5 to 52%, and c is in the range of from 5 to 47%. When x is in the range of from 0.6 to 0.8, b is in the range of from 5 to 52%, and c is in the range of from 5 to 42%. When x is in the range of from 0.8 to 1, b is in the range of from 5 to 52%, and c is in the range of from 5 to 30%. Other elements may also be present in the alloys in varying proportions.

Claims

1. A metallic glass formed of an alloy having the formula

View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9)

2. A metallic glass as recited in claim 1 wherein ETM is only Cr and a2 is in the range of from 0 to 0.2al.

3. A metallic glass as recited in claim 1 wherein ETM is selected from the group consisting of V, Nb and Hf.

4. A metallic glass as recited in claim 1 wherein b2 is 0 and y is in the range of from 0.35 to 0.65.

5. A metallic glass as recited in claim 1 wherein LTM is only Fe.

6. A metallic glass as recited in claim 1 wherein

(a1+a2) is in the range of from 43 to 67%,

(b1+b2) is in the range of from 10 to 38%,

b2 is in the range of from 0 to 25%, and

c is in the range of from 10 to 35%.

7. A metallic glass as recited in claim 6 wherein b2 is 0 and y is in the range of from 0.35 to 0.65.

8. A metallic glass as recited in claim 7 wherein the alloy further comprises up to 15% Al and c is not less than 6.

9. A metallic glass as recited in claim 7 wherein the alloy further comprises additional elements selected from the group consisting of Si, Ge, and B, up to a maximum of 5%, and up to a total of 2% of other elements.

10. A metallic glass formed of an alloy having the formula

View Dependent Claims (11, 12, 13, 14, 15, 16, 17, 18, 19, 20)

11. A metallic glass as recited in claim 10 wherein ETM is only Cr and a2 is in the range of from 0 to 0.2al.

12. A metallic glass as recited in claim 10 wherein ETM is selected from the group consisting of V, Nb and Hf, and a2 is in the range of from 0 to 0.4al.

13. A metallic glass as recited in claim 10 wherein b2 is 0 and y is in the range of from 0.35 to 0.65.

14. A metallic glass as recited in claim 10 wherein LTM is only Fe.

15. A metallic glass as recited in claim 10 wherein the alloy further comprises additional elements selected from the group consisting of Si, Ge, and B, up to a maximum of 5%, and up to a total of 2% of other elements.

16. A metallic glass as recited in claim 10 wherein

(A) when x is in the range of from 0.4 to 0.6:

(a1+a2) is in the range of from 43 to 67%,

(b1+b2) is in the range of from 10 to 38%,

b2 is in the range of from 0 to 25%, and

c is in the range of from 10 to 35%;

(B) when x is in the range of from 0.6 to 0.8;

(a1+a2) is in the range of from 45 to 67%,

(b2+b2) is in the range of from 10 to 38%,

b2 is in the range of from 0 to 25%, and

c is in the range of from 10 to 30%; and

(C) when x is in the range of from 0.8 to 1, either;

(1) (a1+a2) is in the range of from 45 to 55%,

(b1+b2) is in the range of from 37 to 47%,

b2 is in the range of from 0 to 25%, and

c is in the range of from 5 to 13%, or

(2) (a1+a2) is in the range of from 65 to 75%,

(b1+b2) is in the range of from 5 to 15%,

b2 is in the range of from 0 to 25%, and

c is in the range of from 17 to 27%.

17. A metallic glass as recited in claim 16 wherein ETM is selected from the group consisting of V, Nb and Hf, and a2 is in the range of from 0 to 0.4a1.

18. A metallic glass as recited in claim 16 wherein b2 is 0 and y is in the range of from 0.35 to 0.65.

19. A metallic glass as recited in claim 18 wherein the alloy further comprises additional elements selected from the group consisting of Ge, Si and B up to a maximum of 5%, and up to 2% of other elements.

20. A metallic glass as recited in claim 18 wherein the alloy also comprises up to 15% aluminum and c is not less than 6.

21. A metallic glass formed of an alloy having the formula

View Dependent Claims (22, 23, 24, 25, 26, 27, 28, 29, 30, 31)

22. A metallic glass as recited in claim 21 wherein the (Zr_1-x Ti_x) moiety also comprises additional metal selected from the group consisting of from 0 to 25% Hf, from 0 to 20% Nb, from 0 to 15% Y, from 0 to 10% Cr, from 0 to 20% V;

and

the (Cu_1-y Ni_y) moiety also comprises additional metal selected from the group consisting of from 0 to 25% Fe, from 0 to 25% Co and from 0 to 15% Mn.

23. A metallic glass as recited in claim 21 wherein the alloy also comprises up to 20% aluminum and c is not less than 6.

24. A metallic glass as recited in claim 21 wherein y is in the range of from 0.35 to 0.65.

25. A metallic glass as recited in claim 21 wherein the alloy also comprises up to 5% of other transition metals and a total of no more than 2% of other elements.

26. A metallic glass as recited in claim 21 wherein the alloy further comprises additional elements selected from the group consisting of Si, Ge and B up to a maximum of 5%.

27. A metallic glass alloy as recited in claim 21 wherein

the (Zr_1-x Ti_x) moiety also comprises additional metal selected from the group consisting of from 0 to 25% Hf, from 0 to 20% Nb, from 0 to 15% Y, from 0 to 10% Cr, from 0 to 20% V, from 0 to 5% Mo, from 0 to 5% Ta, from 0 to 5% W, and from 0 to 5% lanthanum, lanthanides, actinium and actinides;

the (Cu_1-y Ni_y) moiety also comprises additional metal selected from the group consisting of from 0 to 25% Fe, from 0 to 25% Co, from 0 to 15% Mn and from 0 to 5% of other Group 7 to 11 metals;

the Be moiety also comprises additional metal selected from the group consisting of from 0 to 15% Al with c not less than 6, from 0 to 5% Si and from 0 to 5% B; and

the alloy comprises no more than 2% of other elements.

28. A metallic glass as recited in claim 21 wherein a is in the range of from 43 to 67%, b is in the range of from 10 to 38%, and c is in the range of from 10 to 35%.

29. A metallic glass as recited in claim 28 wherein the alloy also comprises up to 15% aluminum and c is not less than 6.

30. A metallic glass as recited in claim 28 wherein y is in the range of from 0.35 to 0.65.

31. A metallic glass alloy as recited in claim 28 wherein

the (Zr_1-x Ti_x), moiety also comprises additional metal selected from the group consisting of from 0 to 25% Hf, from 0 to 20% Nb, from 0 to 15% Y, from 0 to 10% Cr, from to 20% V, from 0 to 5% Mo, from 0 to 5% Ta, from 0 to 5% W, and from 0 to 5% lanthanum, lanthanides, actinium and actinides;

the (Cu_1-y Ni_y), moiety also comprises additional metal selected from the group consisting of from 0 to 25% Fe, from 0 to 25% Co, from 0 to 15% Mn and from 0 to 5% of other Group 7 to 11 metals;

the Be moiety also comprises additional metal selected from the group consisting of from 0 to 15% Al with c not less than 6, from 0 to 5% Si and from 0 to 5% B; and

the alloy comprises no more than 2% of other elements.

32. A metallic glass formed of an alloy having the formula

View Dependent Claims (33, 34, 35, 36, 37, 38, 39, 40, 41, 42)

33. A metallic glass as recited in claim 32 wherein

the (Zr_1-x Ti_x), moiety also comprises additional metal selected from the group consisting of from 0 to 25% Hf, from 0 to 20% Nb, from 0 to 15% Y, from 0 to 10% Cr, from 0 to 20% V;

and

the (Cu_1-y Ni_y) moiety also comprises additional metal selected from the group consisting of from 0 to 25% Fe, from 0 to 25% Co and from 0 to 15% Mn.

34. A metallic glass alloy as recited in claim 32 wherein

the (Zr_1-x Ti_x) moiety also comprises additional metal selected from the group consisting of from 0 to 25% Hf, from 0 to 20% Nb, from 0 to 15% Y, from 0 to 10% Cr, from to 20% V, from 0 to 5% Mo, from 0 to 5% Ta, from 0 to 5% W, and from 0 to 5% lanthanum, lanthanides, actinium and actinides;

the (Cu_1-y Ni_y) moiety also comprises additional metal selected from the group consisting of from 0 to 25% Fe, from 0 to 25% Co, from 0 to 15% Mn and from 0 to 5% of other Group 7 to 11 metals;

the Be moiety also comprises additional metal selected from the group consisting of from 0 to 15% Al with c not less than 6, from 0 to 5% Si and from 0 to 5% B; and

the alloy comprises no more than 2% of other elements.

35. A metallic glass as recited in claim 32 wherein the alloy further comprises up to 20% Al and c is not less than 6.

36. A metallic glass as recited in claim 32 wherein y is in the range of from 0.35 to 0.65.

37. A metallic glass as recited in claim 32 wherein the alloy further comprises up to 5% other transition metals and a total amount of no more than 2% of other elements.

38. A metallic glass as recited in claim 32 wherein the alloy further comprises additional elements selected from the group consisting of Si, Ge, and B, up to a maximum of 5%.

39. A metallic glass as recited in claim 32 wherein

(A) when x is in the range of from 0.4 to 0.6:

a is in the range of from 43 to 67%,

b is in the range of from 10 to 38%, and

c is in the range of from 10 to 35%;

(B) when x is in the range of from 0.6 to 0.8;

a is in the range of from 45 to 67%,

b is in the range of from 10 to 38%, and

c is in the range of from 10 to 30%; and

(C) when x is in the range of from 0.8 to 1, either;

(1) a is in the range of from 45 to 55%,

b is in the range of from 37 to 47%, and

c is in the range of from 5 to 13%, or

(2) a is in the range of from 65 to 75%,

b is in the range of from 5 to 15%, and

c is in the range of from 17 to 27%.

40. A metallic glass as recited in claim 39 wherein y is in the range of from 0.35 to 0.65.

41. A metallic glass as recited in claim 39 wherein the alloy further comprises up to 15% Al and c is not less than 6.

42. A metallic glass as recited in claim 39 wherein the alloy further comprises up to 5% other transition metals and a total amount of no more than 2% of other elements.

43. A metallic glass formed of an alloy having the formula

View Dependent Claims (44, 45, 46, 47, 48, 49, 50, 51, 52, 53)

44. A metallic glass as recited in claim 43 wherein ETM is an early transition metal selected from the group consisting of Y, Nd, Gd and other rare earth elements.

45. A metallic glass as recited in claim 43 wherein ETM is an early transition metal selected from the group consisting of V and Nb.

46. A metallic glass as recited in claim 43 wherein ETM is an early transition metal selected from the group consisting of V, Nb, Cr, Ta, Mo, and W.

47. A metallic glass as recited in claim 43 wherein LTM is only Fe.

48. A metallic glass as recited in claim 43 wherein x is 1 and b2 is 0.

49. A metallic glass as recited in claim 43 wherein

a is in the range of from 43 to 57%;

(b1+b2) is in the range of from 10 to 38%; and

c is in the range of from 10 to 35%;

50. A metallic glass as recited in claim 43 wherein the alloy further comprises additional elements selected from the group consisting of Si, Ge and B up to a maximum of 5%.

51. A metallic glass as recited in claim 48 wherein the alloy further comprises up to 15% Al and c is not less than 6.

52. A metallic glass as recited in claim 49 wherein x is 1, b2 is 0 and y is in the range of from 0.35 to 0.65.

53. A metallic glass as recited in claim 49 wherein the alloy further comprises up to 15% Al and the atomic percentage of Be is not less than 6.

54. A metallic glass formed of an alloy having the formula

View Dependent Claims (55, 56, 57)

55. A metallic glass as recited in claim 54 wherein

(A) when ETM is selected from the group consisting of Y, Nd, Gd, and other rare earth elements:

a is in the range of from 43 to 67%;

(b1+b2+b3) is in the range of from 10 to 38%,

b3 is in the range of from 0 to 25%,

b1 is in the range of from 0 to 50%, and

c is in the range of from 10 to 35%;

(B) when ETM is selected from the group consisting of Cr, Ta, Mo and W;

a is in the range of from 35 to 50%;

(b1+b2+b3) is in the range of from 15 to 35%,

b3 is in the range of from 0 to 25%,

b1 is in the range of from 0 to x(b1+b2+b3)/2, and

c is in the range of from 15 to 35%; and

(C) when ETM is selected from the group consisting of V and Nb;

a is in the range of from 35 to 55%;

(b1+b2+b3) is in the range of from 15a to 35%,

b3 is in the range of from 0 to 25%,

b1 is in the range of from 0 to x(b1+b2+b3)/2, and

c is in the range of from 15 to 35%.

56. A metallic glass as recited in claim 55 wherein the alloy comprises at least two late transition metals.

57. A metallic glass as recited in claim 55 wherein the alloy further comprises additional elements selected from the group consisting of Si, Ge and B up to a maximum of 5% and a total of up to 2% of other elements.