Methods of forming metallic glass multilayers

Patent metadata

Field	Value
Publication number	US-10166740-B2
Application number	US-201514808885-A
Country	US
Kind code	B2
Filing date	Jul 24, 2015
Priority date	Jul 24, 2014
Publication date	Jan 1, 2019
Grant date	Jan 1, 2019

Abstract

The disclosure is directed to methods of forming metallic glass multilayers by depositing a liquid layer of a metallic glass forming alloy over a metallic glass layer, and to multilayered metallic glass articles produced using such methods.

First claim

What is claimed is:

1. A method of forming a multilayer of metallic glass, the method comprising
providing a base layer of the metallic glass formed of an alloy having thickness d o , and initial temperature T o , wherein the alloy has a critical cooling rate R c and a time to crystallize at different temperatures upon heating the metallic glass formed of the alloy t h (T);
selecting a thickness d i and initial temperature T i for a molten layer of the alloy such that:
(i) an interface temperature T s determined by the Half-Enthalpy criterion is at least as high as the glass transition temperature T g of the metallic glass formed of the alloy,
(ii) a characteristic cooling rate of the molten layer given by α l π 2 (T i −T s )/4d i 2 , where (α l =3×10 −6 m 2 /s, is greater than Rc, and
(iii) a characteristic time scale of the base layer given by 4d o 2 /α o π 2 , where α o =3×10 −6 m 2 /s, is shorter than t h (T) at the interface temperature T s ,
depositing the molten layer with the thickness d i and initial temperature T i over the base layer forming a multilayer.

2. The method of claim 1 , where the interface temperature T s is at least 25° C. higher than T g .

3. The method of claim 1 , where a characteristic time scale of the molten layer is given by [(T L −T n )/(T i −T s )][4d i 2 /α l π 2 ], where T n is the crystallization nose temperature of the alloy, and where the characteristic time scale is shorter than the crystallization nose time of the alloy.

4. The method of claim 1 , where d i is less than the thickness given by (π/2)√[α l t cn (T i −T s )/0.2T L ], where T L is the liquidus temperature and t cn the crystallization nose time of the alloy.

5. The method of claim 1 , where d i is less than the critical casting thickness of the alloy.

6. The method of claim 1 , where d o is less than the thickness given by (π/2)√[α o t h (T s )], where t h (T s ) is the time to crystallize upon heating the metallic glass formed from the alloy at the interface temperature T s .

7. The method of claim 1 , where the metallic glass formed from the alloy has ΔT x of at least 50 K.

8. The method of claim 1 , where the metallic glass formed from the alloy has ΔT x /ΔT L of at least 0.1.

9. A multilayer produced according to the method of claim 1 .

10. The multilayer of claim 9 , where the multilayer is substantially amorphous.

11. The multilayer of claim 10 , where the bending stress of the multilayer substantially matches that of a monolithic metallic glass sample having substantially the same geometry.

12. The multilayer of claim 10 , where the bending strain of the multilayer substantially matches that of a monolithic metallic glass sample having substantially the same geometry.

13. A method of forming a composite metallic glass multilayer comprising depositing a molten layer of a metallic-glass forming alloy of a first alloy composition over a metallic glass layer of a second alloy composition,
where the first alloy composition and the second alloy composition are different,
where the thickness d i and initial temperature T i of the molten layer and the thickness d o and initial temperature T o of the metallic glass layer produce an instantaneous interface temperature T s that is at least as high as the effective glass transition temperature T g* ,
where the characteristic cooling rate in the molten layer given by α l π 2 (T i −T s )4d i 2 , where α l =3×10 −6 m 2 /s, is greater than the critical cooling rate of the metallic glass forming alloy,
where the characteristic time scale in the metallic glass layer following the deposition process given by 4d o 2 /α o π 2 , where α o =3×10 −6 m 2 /s, is shorter than the time for the metallic glass to crystallize at the interface temperature T s , and
where the effective glass transition temperature is given by T g* =0.5(T g1 +T g2 ), where T g1 and T g2 are the glass transition temperatures of the first alloy composition and the second alloy composition, respectively.

14. The method of claim 13 , where the difference between T g1 and T g2 is less than 50° C.

15. The method of claim 13 , where the difference between T L1 and T L2 is less than 150° C., where T L1 and T L2 are the liquidus temperatures of the first alloy composition and the second alloy composition, respectively.

16. The method of claim 13 , the difference between T x1 and T x2 is less than 50° C., where T x1 and T x2 are the crystallization temperatures of the first alloy composition and the second alloy composition, respectively.

17. A metallic glass multilayer composite comprising at least two bonded metallic glass layers,
where at least two layers comprise different metallic glass alloy compositions,
where the relative difference between the shear moduli of the metallic glass alloy compositions is at least 2%, and
where the thickness of each layer does not exceed the plastic zone radius of the metallic glass alloy composition of the layer.

18. The metallic glass multilayer composite of claim 17 , where the yield strength of the metallic glass multilayer composite is within 20% of the volumetric average between the yield strengths of the different metallic glass compositions.

19. The metallic glass multilayer composite of claim 18 , where the fracture toughness of the metallic glass multilayer composite is higher than the fracture toughness of the metallic glass alloy composition having the lowest fracture toughness.

20. The metallic glass multilayer composite of claim 18 , where the tensile ductility of the metallic glass multilayer composite is higher than the tensile ductility values of the metallic glass compositions.

21. The method of claim 1 , wherein no crystallization occurs in the molten and base layers of the multilayer.

22. The method of claim 1 , wherein the multilayer has a bending strength within 40% of the bending strength of a monolithic metallic glass formed of the alloy having substantially the same geometry.

Assignees

• Glassimetal Tech Inc
• Apple Inc

Inventors

• Johnson William L
• Demetriou Marios D
• Schramm Joseph P

Classifications

• C22C1/11

  Making amorphous alloys · CPC title

• C22C45/003

  with one or more of the noble metals as major constituent · CPC title

• B32B15/015

  the said other metal being copper or nickel or an alloy thereof · CPC title

• C22C45/10

  with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium {or Hf} as the major constituent · CPC title

• B33Y80/00

  Products made by additive manufacturing · CPC title