Method of forming berryllium bearing metallic glass

• US 5,368,659 A
• Filed: 02/18/1994
• Issued: 11/29/1994
• 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:
  US08/198,873
• Time in Patent Office: 284 Days
• Field of Search: 148/403, 148/672, 420/417, 420/422, 420/421
• 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 2 to 47 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 5 to 62%. 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 62%, 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 62%, and c is in the range of from 2 to 47%. When x is in the range of from 0.4 to 0.6, b is in the range of from 5 to 62%, and c is in the range of from 2 to 47%. When x is in the range of from 0.6 to 0.8, b is in the range of from 5 to 62%, and c is in the range of from 2 to 42%. When x is in the range of from 0.8 to 1, b is in the range of from 5 to 62%, and c is in the range of from 2 to 30%. Other elements may also be present in the alloys in varying proportions.

Claims

1. A method for making a metallic glass having at least 50% amorphous phase comprising the steps of:

forming an alloy having the formula

space="preserve" listing-type="equation">(Zr.sub.1-x Ti.sub.x).sub.a1 ETM.sub.a2 (Cu.sub.1-y Ni.sub.y).sub.b1 LTM.sub.b2 Be.sub.c

where x and y are atomic fractions, and a1, a2, b1, b2, and c are atomic percentages, wherein;

ETM is at least one early transition metal selected from the group consisting of V, Nb, Hf, and Cr, wherein the atomic percentage of Cr is no more than 0.2 a1;

LTM is a late transition metal selected from the group consisting of Fe, Co, Mn, Ru, Ag and Pd;

a2 is in the range of from 0 to 0.4a1;

x is in the range of from 0 to 0.4; and

y is in the range of from 0 to 1; and

(A) when x is in the range of from 0 to 0.15;

(a1+a2) is in the range of from 30 to 75%,

(b1+b2) is in the range of from 5 to 62%,

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

c is in the range of from 6 to 47%;

(B) when x is in the range of from 0.15 to 0.4;

(a1+a2) is in the range of from 30 to 75%,

(b1+b2) is in the range of from 5 to 62%,

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

c is in the range of from 2 to 47%; and

cooling the entire alloy from above its melting point to a temperature below its glass transition temperature at a sufficient rate to prevent formation of more than 50% crystalline phase.

2. A method as recited in claim 1 wherein ETM is only Cr and a2 is in the range of from 0 to 0.2 a1.

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

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

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

6. A method as recited in claim 1 wherein

(a1+a2) is in the range of from 40 to 67%,

(b1+b2) is in the range of from 10 to 48%,

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

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

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

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

9. A method 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 method for making a metallic glass having at least 50% amorphous phase comprising the steps of:

forming an alloy having the formula

space="preserve" listing-type="equation">(Zr.sub.1-x Ti.sub.x).sub.a1 ETM.sub.a2 (Cu.sub.1-y,Ni.sub.y).sub.b1 LTM.sub.b2 Be.sub.c

where x and y are atomic fractions, and a1, a2, b1, b2, b3 and c are atomic percentages, wherein;

ETM is an early transition metal selected from the group consisting of V, Nb, Hf, and Cr wherein the atomic percentage of Cr is no more than 0.2a1;

LTM is a late transition metal selected from the group consisting of Fe, Co, Mn, Ru, Ag and Pd;

a2 is in the range of from 0 to 0.4 a1;

x is in the range of from 0.4 to 1; and

y is in the range of from 0 to 1; and

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

(a1+a2) is in the range of from 35 to 75%,

(b1+b2) is in the range of from 5 to 62%,

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

c is in the range of from 2 to 47%;

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

(a1+a2) is in the range of from 35 to 75%,

(b1+b2) is in the range of from 5 to 62%,

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

c is in the range of from 2 to 42%; and

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

(a1+a2) is in the range of from 35 to 75%,

(b1+b2) is in the range of from 5 to 62%,

b2is in the range of from 0 to 25%, and

c is in the range of from 2 to 30%,

under the constraint that 3c is up to (100-b1-b2) when (b1+b2) is in the range of from 10 to 49%; and

cooling the entire alloy from above its melting point to a temperature below its glass transition temperature at a sufficient rate to prevent formation of more than 50% crystalline phase.

11. A method as recited in claim 10 wherein ETM is only Cr and a2 is in the range of from 0 to 0.2 a1.

12. A method 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 0.4a1.

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

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

15. A method 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 method 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 40 to 67%,

(b1+b2) is in the range of from 10 to 48%,

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 40 to 67%,

(b1+b2) is in the range of from 10 to 48%,

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 38 to 55%,

(b1+b2) is in the range of from 35 to 60%,

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

c is in the range of from 2 to 15%, 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 method 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 method as recited in claim 16 wherein b2 is 0 and y is in the range of from 0.35 to 0.65.

19. A method 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 method as recited in claim 18 wherein the alloy further comprises up to 15% aluminum and c is not less than 6.

21. A method for making a metallic glass having at least 50% amorphous phase comprising the steps of:

forming an alloy having the formula

space="preserve" listing-type="equation">(Zr.sub.1-x Ti.sub.x).sub.a (Cu.sub.1-y Ni.sub.y).sub.b Be.sub.c

where x and y are atomic fractions, a, b and c are atomic percentages, wherein y is in the range of from 0 to 1, x is in the range of from 0 to 0.4, and wherein;

when x is in the range of from 0 to 0.15, a is in the range of from 30 to 75%, b is in the range of from 5 to 62%, and c is in the range of from 6 to 47%; and

when x is in the range of from 0.15 to 0.4, a is in the range of from 30 to 75%, b is in the range of from 5 to 62%, and c is in the range of from 2 to 47%; and

cooling the entire alloy from above its melting point to a temperature below its glass transition temperature at a sufficient rate to prevent formation of more than 50% crystalline phase.

22. A method 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 method as recited in claim 21 wherein the alloy further comprises up to 20% aluminum and c is not less than 6.

24. A method as recited in claim 21 wherein b.y is in the range of from 5 to 15.

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

26. A method 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 method alloy as recited in claim 21 wherein

the (Zr_1-x Ti_x) moiety further 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 further 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 further 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 method as recited in claim 21 wherein a is in the range of from 40 to 67%, b is in the range of from 10 to 48%, and c is in the range of from 10 to 35%.

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

30. A method as recited in claim 28 wherein b.y is in the range of from 5 to 15.

31. A method alloy as recited in claim 28 wherein

the (Zr_1-x Ti_x) moiety further 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 further 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 further 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 method for making a metallic glass having at least 50% amorphous phase comprising the steps of:

forming an alloy having the formula

space="preserve" listing-type="equation">(Zr.sub.1-x Ti.sub.x).sub.a (Cu.sub.1-y Ni.sub.y).sub.b Be.sub.c

where x and y are atomic fractions, a, b and c are atomic percentages, wherein y is in the range of from 0 to 1, x is in the range of from 0.4 to 1, and wherein;

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

a is in the range of from 35 to 75%,

b is in the range of from 5 to 62%, and

c is in the range of from 2 to 47%;

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

a is in the range of from 35 to 75%,

b is in the range of from 5 to 62%, and

c is in the range of from 2 to 42%; and

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

a is in the range of from 35 to 75%,

b is in the range of from 5 to 62%, and

c is in the range of from 2 to 30%, under the constraint that 3c is up to (100-b) when b is in the range of from 10 to 49%; and

cooling the entire alloy from above its melting point to a temperature below its glass transition temperature at a sufficient rate to prevent formation of more than 50% crystalline phase.

33. A method as recited in claim 32 wherein

the (Zr_1-x Ti_x) moiety further 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 further 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 method alloy as recited in claim 32 wherein

(Zr_1-x Ti_x) moiety further 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 further 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 further 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 method as recited in claim 32 wherein the alloy further comprises up to 20% Al and c is not less than 6.

36. A method as recited in claim 32 wherein b.y is in the range of from 5 to 15.

37. A method 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 method 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 method 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 40 to 67%,

b is in the range of from 10 to 48%, 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 40 to 67%,

b is in the range of from 10 to 48%, 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 38 to 55%,

b is in the range of from 35 to 60%, and

c is in the range of from 2 to 15%, 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 method as recited in claim 39 wherein b.y is in the range of from 5 to 15.

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

42. A method 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 method for making a metallic glass having at least 50% amorphous phase comprising the steps of:

forming an alloy having the formula

space="preserve" listing-type="equation">((Zr,Hf,Ti).sub.x ETM.sub.1-x).sub.a (Cu.sub.1-y Ni.sub.y).sub.b1 LTM.sub.b2 Be.sub.c

where x and y are atomic fractions, and a, b1, b2, and c are atomic percentages;

the atomic fraction of Ti in the ((Hf,Zr,Ti) ETM) moiety is less than 0.7;

x is in the range of from 0.8 to 1;

LTM is a late transition metal selected from the group consisting of Ni, Cu, Fe, Co, Mn, Ru, Ag and Pd;

ETM is an early transition metal selected from the group consisting of V, Nb, Y, Nd, Gd and other rare earth elements, Cr, Mo, Ta, and W;

a is in the range of from 30 to 75%;

(b1+b2) is in the range of from 5 to 57%; and

c is in the range of from 6 to 45%; and

cooling the entire alloy from above its melting point to a temperature below its glass transition temperature at a sufficient rate to prevent formation of more than 50% crystalline phase.

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

46. A method 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 method as recited in claim 43 wherein LTM is only Fe.

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

49. A method as recited in claim 43 wherein

a is in the range of from 40 to 67%;

(b1+b2) is in the range of from 10 to 48%; and

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

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

52. A method 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 method 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.