Biocompatible copper-based single-crystal shape memory alloys
View Patent ↗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.
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.