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 biocompatible device for use within a body comprising a single crystal copper-based shape memory alloy having an exposed outer surface at and below which resides a surface region of depth greater than 1 nm below the exposed outer surface that is enriched in aluminum relative to copper, wherein the aluminum enriched in the surface region of the single crystal copper-based shape memory alloy is in the form of aluminum oxide thereby forming a protective outer layer comprising aluminum oxide greater than 1 nm thick that is formed at least in part by oxidizing the aluminum enriched in the surface region of the single crystal.
2. The device of claim 1 , wherein the single-crystal copper-based shape memory material comprises CuAlNi.
3. The device of claim 1 , wherein the protective outer layer comprising aluminum oxide is an amorphous layer of aluminum oxide.
4. The device of claim 1 , wherein the protective outer layer comprising aluminum oxide is substantially crystalline aluminum oxide.
5. The device of claim 1 , wherein the protective outer layer comprising aluminum oxide is greater than 100 nm thick.
6. The device of claim 1 , wherein the single crystal copper-based shape memory alloy is configured as at least one of: a joint replacement, a hip bone replacement, a guidewire, a clot retriever, a blood filter, a stent, and a dental arch.
7. The device 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 the biocompatible device of claim 1 , the method comprising the steps of:
forming the single crystal copper-based shape memory alloy from a seed of copper aluminum based alloy aligned on the <100>crystallographic direction; and
forming the protective outer layer comprising aluminum oxide in the surface region of the single crystal copper-based shape memory alloy by a controlled process of doping the surface region with Al after forming the single crystal copper-based shape memory alloy, anodizing the surface region of the single crystal copper-based shape memory alloy, and/or applying a high voltage to the single crystal copper-based shape memory alloy.
9. A biocompatible dental arch comprising a copper-aluminum single crystal shape memory alloy having an exposed outer surface from which extends a surface region of depth greater than 1 nm below the outer surface of the single crystal shape memory alloy that is enriched in aluminum relative to copper, wherein the surface region provides a protective outer layer comprising aluminum oxide formed at least in part by oxidizing the aluminum enriched in the surface region of the single crystal.
10. The device of claim 9 , wherein the protective outer layer comprising aluminum oxide is greater than 10 nm thick.
11. The device of claim 9 , wherein the single-crystal copper-based shape memory material comprises CuAlNi, and the protective outer layer comprising aluminum oxide is an amorphous layer of aluminum oxide of thickness greater than 100 nm.
12. The device of claim 9 , wherein the single-crystal copper-based shape memory material comprises CuAlNi, and the protective outer layer comprising aluminum oxide is substantially crystalline aluminum oxide of thickness greater than 100 nm.