Whitlockite ceramic

• US 4,195,366 A
• Filed: 12/23/1977
• Issued: 04/01/1980
• Est. Priority Date: 12/23/1977
• Status: Expired due to Term

• Current Assignee: Sanofi S.A. (Sanofi )
• Original Assignee: Sterling Drug, Inc. (GSK plc)
• Inventors: Jarcho, Michael, Salsbury, Ronald L.
• Primary Examiner(s): Mack, John H.
• Assistant Examiner(s): Bell, Mark
• Application Number:
  US05/863,721
• Time in Patent Office: 830 Days
• Field of Search: 106/39.5, 106/63, 106/40 R, 106/35, 3/1.9, 32/10 A, 128/92 C, 423/311
• US Class Current: 623/23.56
• CPC Class Codes: A61F 2310/00293 containing a phosphorus-containing compound, e.g. apatite
• CPC Class Codes: A61L 2430/02 for reconstruction of bones; weight-bearing implants
• CPC Class Codes: A61L 27/12 Phosphorus-containing materials, e.g. apatite
• CPC Class Codes: C01B 25/325 Preparation by double decomposition
• CPC Class Codes: C04B 35/447 based on phosphates , e.g. hydroxyapatite

Abstract

A novel, polycrystalline whitlockite ceramic in either pore-free or porous form, processes for the preparation thereof and methods of using the same as biological implant materials are disclosed.

Claims

1. A translucent, isotropic, substantially pore-free polycrystalline ceramic consisting essentially of whitlockite containing within the crystal lattice thereof about 0.1 to 2.2 percent by weight sulfate ion and characterized by an average crystallite size in the approximate range 0.3 to 3 microns and a density greater than about 98 percent of the theoretical density of β

-whitlockite.

2. A ceramic according to claim 1 wherein the whitlockite is β

-whitlockite.

3. A ceramic according to claim 1 shaped or formed substantially into a flat sheet.

4. A ceramic according to claim 1 shaped or formed substantially into a cylindrical rod.

5. A strong, dense, resorbable artificial bone prosthesis in the form of a polycrystalline ceramic according to claim 1.

11. A process for producing a ceramic according to claim 1 which comprises reacting calcium ion with phosphate ion in a molar ratio in the approximate range 1.2-1.5 to 1 in aqueous medium at a pH of about 10 to 12 to produce a gelatinous precipitate of calcium phosphate having a molar ratio of calcium to phosphorus in the approximate range 1.50-1.53 to 1, separating said gelatinous precipitate from the solution, washing said precipitate free of soluble salts with water, homogeneously suspending the washed precipitate in 1 to 3 percent (w/w) aqueous ammonium sulfate in the amount of about 10 to 20 ml. per gram of theoretically expected whitlockite ceramic, separating the precipitate from the ammonium sulfate solution, drying said precipitate and heating the dried precipitate in the approximate range 1000°

C. to 1350°

C. for about 0.5 to 4 hours.

12. A process according to claim 11 wherein the dried precipitate is heated at about 1150°

C. to 1200°

C. for approximately 1 hour.

13. A process according to claim 12 wherein the product is subsequently heated at about 900°

C. for approximately 4 hours whereby the resulting whitlockite ceramic consists essentially of β

-whitlockite.

18. In a method for filling a void in a living bone which includes the step of filling said void with a biocompatible ceramic, the improvement which comprises employing a biocompatible ceramic according to claim 1.

20. In a method for prosthetically reconstructing a defective living bone which includes the step of implanting an artificial bone prosthesis, the improvement which comprises implanting an artificial bone prosthesis according to claim 5.

6. A polycrystalline foamed ceramic body consisting essentially of whitlockite containing within the crystal lattice thereof about 0.1 to 2.2 percent by weight sulfate ion and characterized by an average crystallite size in the approximate range 0.3 to 3 microns, a total pore volume in the approximate range 20 to 80 percent, said pore volume comprising a substantially uniform distribution of open pores having a pore size diameter in the approximate range 50 to 300 microns.

7. A foamed ceramic body according to claim 6 wherein the whitlockite is β

-whitlockite.

8. A foamed ceramic body according to claim 6 shaped or formed substantially into a flat sheet.

9. A foamed ceramic body according to claim 6 shaped or formed substantially into a cylindrical rod.

10. A resorbable artificial bone prosthesis in the form of a polycrystalline ceramic according to claim 6.

14. A process for producing a polycrystalline foamed ceramic body according to claim 6 which comprises reacting calcium ion with phosphate ion in a molar ratio of about 1.2-1.5 to 1 in aqueous medium at a pH of about 10-12 to produce a gelatinous precipitate of calcium phosphate having a calcium to phosphorus molar ratio of about 1.50-1.53 to 1, separating said gelatinous precipitate from the solution, washing said precipitate free of soluble salts with water, homogeneously suspending the washed precipitate in 1 to 3 percent (w/w) aqueous ammonium sulfate in the amount of about 10 to 20 ml. per gram of theoretically expected whitlockite ceramic, separating the precipitate from the ammonium sulfate solution, mixing the precipitate with about 0.5 to 10 percent by weight of a blowing agent and about 0.5 to 10 percent by weight of a foam stabilizer, heating the resulting mixture at about 70°

C. to 90°

C. until decomposition of the blowing agent and drying of the resultant foam are substantially complete, and then heating the dried foam at about 1000°

C. to 1350°

C. until volatilization of the foam stabilizer and sintering of the resulting product are substantially complete.

15. A process according to claim 14 wherein the blowing agent is azodicarbonamide and the foam stabilizer is egg albumen.

16. A process according to claim 15 wherein the mixture of the calcium phosphate precipitate, azodicarbonamide and egg albumen is dried at about 70°

C. to 90°

C. for approximately 8 to 20 hours and the resulting dried foam is heated at about 1050°

C. to 1150°

C. for approximately 1 hour.

19. In a method for filling a void in a living bone which includes the step of filling said void with a biocompatible ceramic, the improvement which comprises employing a biocompatible ceramic according to claim 6.

21. In a method for prosthetically reconstructing a defective living bone which includes the step of implanting an artificial bone prosthesis, the improvement which comprises implanting an artificial bone prosthesis according to claim 10.

17. A process for producing non-ceramic, crystalline whitlockite containing within the crystal lattice thereof about 0.1 to 2.2 percent by weight sulfate ion which comprises reacting calcium ion with phosphate ion in a molar ratio in the approximate range 1.2-1.5 to 1 in aqueous medium at a pH of about 10 to 12 to produce a gelatinous precipitate of calcium phosphate having a molar ratio of calcium to phosphorus in the approximate range 1.50-1.53 to 1, separating said gelatinous precipitate from the solution, washing said precipitate free of soluble salts with water, homogeneously suspending the washed precipitate in 1 to 3 percent (w/w) aqueous ammonium sulfate in the amount of about 10 to 20 ml. per gram of theoretically expected whitlockite ceramic, separating the precipitate from the ammonium sulfate solution, drying said precipitate and heating the dried precipitate in the approximate range 725°

C. to 900°

C. for about 0.5 to 4 hours.