High strength vacuum deposited nitinol alloy films and method of making same

• US 8,083,908 B2
• Filed: 10/19/2007
• Issued: 12/27/2011
• Est. Priority Date: 11/19/1999
• Status: Expired due to Term

• Current Assignee: Vactronix Scientific, LLC
• Original Assignee: Advanced Bio Prosthetic Surfaces, Ltd.
• Inventors: Marton, Denes, Boyle, Christopher T., Wiseman, Roger W., Banas, Christopher E.
• Primary Examiner(s): MCDONALD, RODNEY GLENN
• Application Number:
  US11/875,629
• Publication Number:
  US 20080171214A1
• Time in Patent Office: 1,530 Days
• Field of Search: 204/192.12, 204/192.15
• US Class Current: 204/192.15
• CPC Class Codes: A61F 2/91 made from perforated sheet material or tubes, e.g. perforated by laser cuts or etched holes
• CPC Class Codes: A61F 2/915 with bands having a meander structure, adjacent bands being connected to each other
• CPC Class Codes: A61F 2002/91541 Adjacent bands are arranged out of phase
• CPC Class Codes: A61L 2400/16 Materials with shape-memory or superelastic properties
• CPC Class Codes: A61L 27/047 Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
• CPC Class Codes: A61L 27/06 Titanium or titanium alloys
• CPC Class Codes: A61L 27/40 Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
• CPC Class Codes: A61L 29/106 Inorganic materials other than carbon
• CPC Class Codes: A61L 31/088 Other specific inorganic materials not covered by A61L31/084 or A61L31/086
• CPC Class Codes: A61L 31/12 Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
• CPC Class Codes: A61L 31/16 Biologically active materials, e.g. therapeutic substances A61L31/047 takes precedence
• CPC Class Codes: C23C 14/0005 Separation of the coating from the substrate
• CPC Class Codes: C23C 14/165 by cathodic sputtering
• CPC Class Codes: C23C 14/35 by application of a magnetic field, e.g. magnetron sputtering C23C14/3457 takes precedence
• CPC Class Codes: Y10S 428/913 Material designed to be responsive to temperature, light, moisture
• CPC Class Codes: Y10T 29/301 Method
• CPC Class Codes: Y10T 428/12 All metal or with adjacent metals
• CPC Class Codes: Y10T 428/12431 Foil or filament smaller than 6 mils
• CPC Class Codes: Y10T 428/125 Deflectable by temperature change [e.g., thermostat element]

Abstract

A vacuum deposition method for fabricating high-strength nitinol films by sputter depositing nickel and titanium from a heated sputtering target, and controlling the sputter deposition process parameters in order to create high-strength nitinol films that exhibit shape memory and/or superelastic properties without the need for precipitation annealing to attenuate the transition conditions of the deposited material. A vacuum deposited nitinol film having high-strength properties equal to or better than wrought nitinol films and which are characterized by having non-columnar crystal grain structures.

Claims

1. A method for fabricating nitinol film using a vacuum sputter deposition apparatus having a magnetron, a cathode, a cooling device thermally coupled to the cathode and a deposition chamber capable of being selectively isolated from the atmosphere, the method comprising the steps of:

a. disposing at least one cylindrical target selected from the group consisting of nickel, titanium and nickel-titanium alloy in the deposition chamber;

b. disposing a cylindrical substrate that is spatially separated from and concentric with the cylindrical target in the deposition chamber;

c. supplying a working gas to the deposition chamber;

d. sputter depositing material from the at least one cylindrical target to form a substantially non-columnar crystalline film under conditions where the mean free path of the sputtered particles is greater than about half the distance between the cylindrical target and the cylindrical substrate;

e. removing the deposited material from the cylindrical substrate.

2. The method of claim 1, wherein step a. further comprises providing at least one nickel target and at least one titanium target.

3. The method of claim 1, wherein the cathode and the target are at least partially thermally isolated.

4. The method of claim 3, wherein the sputter deposition apparatus further comprises a thermally insulating ceramic material in insulating contact between the target and the cathode.

5. The method of claim 1, wherein at least a portion the substrate has a surface roughness with an R_a value less than about 50 nm.

6. The method of claim 1, wherein the working gas in step c. is selected from the group consisting of He, Ne, Ar, Kr, and Xe.

7. The method of claim 1, wherein the substrate is heated to a temperature between about 400°

C. to 550°

C. prior to step d.

8. The method of claim 1, wherein step b. further comprises applying a bias voltage to the substrate.

9. The method of claim 8, wherein the bias voltage is a negative voltage.

10. The method of claim 9, wherein the bias voltage is less than or equal to about −

120 V.

11. The method of claim 1, wherein step c. further comprises the step of admitting Ar gas into the vacuum deposition system to a pressure between about 0.1 to about 30 mTorr.

12. The method of claim 1, wherein step d. further comprises the step of positioning the deposition substrate and the target such that a throw distance between the deposition substrate and the target is less than about 25 mm.

13. The method of claim 1, wherein the cylindrical substrate is disposed along the central axis of the deposition chamber.

14. The method of claim 13, wherein step d. further comprises the step of rotating the substrate such that the deposited film is tubular in shape.

15. The method of claim 1, wherein step d. further comprises the step of quenching the deposited nitinol film within the sputtering apparatus.

16. The method of claim 1, further comprising the step of visually inspecting the deposited nitinol film and qualitatively determining surface roughness of the deposited nitinol film based upon the luster of the deposited nitinol film.

17. A method for fabricating nitinol film, comprising the steps of:

a. providing a vacuum deposition apparatus;

b. providing at least one cylindrical target selected from the group consisting of nickel, titanium, nickel-titanium alloy, nickel-titanium-X alloy wherein X is selected from the group consisting of copper, chromium, tantalum and zirconium;

c. providing and heating a cylindrical substrate disposed concentrically with the cylindrical target before and during a deposition run;

d. vacuum depositing nitinol metal from the at least one cylindrical target onto the cylindrical substrate to form a substantially non-columnar crystalline film;

e. controlling at least one vacuum deposition processing parameter selected from the group of isothermally heating the cylindrical target, controlling the base vacuum pressure, deoxygenating the working gas, controlling the deposition pressure, controlling surface roughness of the cylindrical substrate, controlling the composition of the cylindrical substrate, applying a negative bias voltage to the cylindrical substrate and controlling the throw distance between the cylindrical substrate and the cylindrical target;

f. removing the deposited nitinol film from the cylindrical substrate.

18. The nitinol film of claim 17, wherein the nitinol film has an ultimate strength of at least about 1000 MPa.

19. The nitinol film of claim 18, wherein the nitinol film has a maximum strain of at least about 10%.

20. A method for fabricating nitinol film comprising the steps of:

a. sputter depositing nitinol in a vacuum system having a magnetron, a cylindrical target, a cylindrical substrate disposed concentrically with the cylindrical target, a cooling device thermally coupled to a cathode and a deposition chamber capable of being selectively isolated from the atmosphere; and

b. controlling the energy of particles emitted from the cylindrical target such that the mean free path of the emitted particles is greater than about one-half the throw distance between the cylindrical target and the cylindrical substrate.