Biocompatible copper-based single-crystal shape memory alloys

• US 9,539,372 B2
• Filed: 10/15/2013
• Issued: 01/10/2017
• Est. Priority Date: 11/30/2007
• Status: Active Grant

• Current Assignee: Ormco Corporation (Envista Holdings Corporation)
• Original Assignee: Ormco Corporation (Envista Holdings Corporation)
• Inventors: Johnson, Alfred David
• Primary Examiner(s): Kastler, Scott
• Assistant Examiner(s): LUK, VANESSA TIBAY
• Application Number:
  US14/053,744
• Publication Number:
  US 20140216607A1
• Time in Patent Office: 1,183 Days
• US Class Current: 1/1
• 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 27/50 Materials characterised by their function or physical properties , e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
• CPC Class Codes: A61L 31/022 Metals or alloys
• CPC Class Codes: A61L 31/14 Materials characterised by their function or physical properties , e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
• CPC Class Codes: C22C 9/01 with aluminium as the next major constituent
• CPC Class Codes: C30B 15/00 Single-crystal growth by pulling from a melt, e.g. Czochralski method under a protective fluid C30B27/00
• CPC Class Codes: C30B 15/36 characterised by the seed, e.g. its crystallographic orientation
• CPC Class Codes: C30B 29/52 Alloys
• CPC Class Codes: C30B 31/00 Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
• CPC Class Codes: C30B 33/005 Oxydation

Abstract

We describe herein biocompatible single crystal Cu-based shape memory alloys (SMAs). In particular, we show biocompatibility based on MEM elution cell cytotoxicity, ISO intramuscular implant, and hemo-compatibility tests producing negative cytotoxic results. This biocompatibility may be attributed to the formation of a durable oxide surface layer analogous to the titanium oxide layer that inhibits body fluid reaction to titanium nickel alloys, and/or the non-existence of crystal domain boundaries may inhibit corrosive chemical attack. Methods for controlling the formation of the protective aluminum oxide layer are also described, as are devices including such biocompatible single crystal copper-based SMAs.

Claims

1. A method of forming a biocompatible anisotropic, single crystal copper-aluminum shape memory alloy having hyperelastic properties, the anisotropic single crystal shape memory alloy material formed being deformable at a constant force at recoverable strain of at least 9% with a very narrow loading-unloading hysteresis, a recovery which is completely repeatable and complete and a very low yield strength when martensitic, the method comprising the steps of:

forming a single crystal copper-aluminum-based shape memory alloy from a seed of copper aluminum based alloy aligned on the <

100>

crystallographic direction;

in a surface region of depth greater than 1 nm below an exposed outer surface of the single crystal copper-aluminum-based shape memory alloy, diffusing aluminum atoms into the surface region to enrich the surface region in aluminum relative to copper; and

forming a controlled layer of aluminum oxide on the single crystal copper-based shape memory alloy by oxidizing the aluminum atoms in the surface region.

2. The method of claim 1, wherein the step of forming the single crystal copper-aluminum-based shape memory alloy comprises:

lowering the seed of a copper aluminum based alloy into a molten melt of a copper aluminum based alloy,

pulling a column of the alloy of arbitrary length from the melt by pulling at a pulling rate so that the rising column is cooled relative to the melt, to form a crystallization front above the surface of the melt, wherein the melt is kept at a constant temperature and has a composition so that the pulled single crystal column has a transition temperature from martensite to austenite that is below 37°

C.,

applying a predetermined hydrostatic pressure on the column and heating the column to a temperature less than 1100°

C., the pulling rate, hydrostatic pressure and temperature being sufficient to crystallize the alloy in the column into a single crystal, and

rapidly quenching the single crystal.

3. The method of claim 1, further comprising applying a sealant to the outer surface of the single crystal copper-based shape memory alloy.

4. The method of claim 1, further comprising preparing the surface of the single crystal copper-based shape memory alloy for the aluminum oxide.

5. The method of claim 3, further comprising polishing at least a portion of the outer surface of the single crystal copper-based shape memory alloy.

6. The method of claim 1, wherein the step of forming the single crystal copper-based shape memory alloy comprises forming a single crystal CuAlNi alloy.

7. The method of claim 1, wherein the depth of the surface region is greater than 10 nm below the exposed outer surface.

8. A method of forming a biocompatible single crystal copper-based shape memory alloy, the method comprising:

forming a single crystal copper-based shape memory alloy by

lowering a seed of a copper aluminum based alloy into a molten melt of a copper aluminum based alloy, wherein the seed is aligned on the <

100>

crystallographic direction in a direction of pulling,

pulling a column of the alloy from the melt so that the rising column is cooled relative to the melt, to form a crystallization front above the surface of the melt, wherein the melt is kept at a constant temperature and has a composition so that the pulled single crystal column has a transition temperature from martensite to austenite that is below 37°

C.,

applying a predetermined hydrostatic pressure on the column and heating the column to a temperature less than 1100°

C., the pulling rate, hydrostatic pressure and temperature being sufficient to crystallize the alloy in the column into a single crystal, and

rapidly quenching the single crystal;

preparing the exposed outer surface of the single crystal copper-based shape memory alloy;

in a surface region of depth greater than 1 nm below the exposed outer surface of the single crystal copper-aluminum-based shape memory alloy, diffusing aluminum atoms into the surface region to enrich the surface region in aluminum relative to copper; and

forming a controlled layer of aluminum oxide on the single crystal copper-based shape memory alloy by oxidizing the aluminum atoms in the surface region.

9. The method of claim 8, wherein the step of forming the single crystal copper-based shape memory alloy comprises forming a single crystal CuAlNi alloy.

10. The method of claim 8, wherein the step of preparing the surface of the single-crystal copper-based shape memory alloy comprises polishing or grinding the surface.

11. The method of claim 8, wherein the depth of the surface region is greater than 10 nm below the exposed outer surface.