Calcium phosphate granules and methods of making them

1. Porous ceramic granules, the porous ceramic granules made by the process of heating pore-forming agent particles to a temperature above a glass transition temperature for the pore-forming agent particles having a size range of about 40 μm to about 700 μm; contacting the heated pore-forming agent particles with a ceramic material to form a mixture of pore-forming agent particles and ceramic material; heating the mixture to remove the pore-forming agent particles from the mixture to form porous ceramic material; and micronizing the porous ceramic material to obtain the porous ceramic granules, wherein the porous ceramic granules have an average diameter from about 50 μm to 800 μm, and each of the porous ceramic granules comprises micropores having a diameter from about 0.1 to about 10 microns and an interconnected porous structure and an outer surface comprising a plurality of concave shapes each having a diameter of about 400 to about 600 microns.

2. The porous ceramic granules of claim 1 , wherein each of the porous ceramic granules have a Brunauer-Emmett-Teller (BET) surface area from about 0.2 to about 10 m 2 /g.

3. A porous ceramic granule, the porous ceramic granule comprising hydroxyapatite in an amount of about 8 to about 22 wt. % and beta-tricalcium phosphate in an amount of about 78 to about 92 wt. %, the porous ceramic granule having a microporosity and each of the micropores have a diameter of less than about 10 μm, and a BET surface area from about 0.2 to about 10 m 2 /g, and an average diameter from about 50 μm to 800 μm, the porous ceramic granules made by mixing the porous ceramic granules with pore-forming agent particles having a size range of about 40 μm to about 700 μm to form a mixture and heating the mixture to remove the pore-forming agent particles from the mixture to form the porous ceramic granules, wherein each of the porous ceramic granules comprises micropores having a diameter from about 0.1 to about 10 microns and an interconnected porous structure and an outer surface comprising a plurality of concave shapes, wherein each of the porous ceramic granules have a Brunauer-Emmett-Teller (BET) surface area from about 0.2 to about 10 m 2 /g.

4. The porous ceramic granule of claim 3 , wherein the porous ceramic granule is crystalline, amorphous or a combination thereof.

5. The porous ceramic granule of claim 3 , wherein the porous ceramic granules comprise a calcium to phosphate ratio of between 1.0 to about 2.0.

6. A method of making the porous ceramic granules of claim 1 , the method comprising heating pore-forming agent particles to a temperature above a glass transition temperature for the pore-forming agent particles, the pore-forming agent particles having a size range of about 40 μm to about 700 μm; contacting the heated pore-forming agent particles with a ceramic material to form a mixture of pore-forming agent particles and ceramic material; heating the mixture to remove the pore-forming agent particles from the mixture to form a porous ceramic material; and micronizing the porous ceramic material to obtain the porous ceramic granules of claim 1 , wherein the porous ceramic granules have an average diameter from about 50 μm to 800 μm, and each of the porous ceramic granules comprises micropores having a diameter from about 0.1 to about 10 microns and an interconnected porous structure and an outer surface comprising a plurality of concave shapes each having a diameter of about 400 to about 600 microns.

7. The method of claim 6 , wherein the porous ceramic granules have the average diameter from about 90 μm to about 600 μm.

8. The method of claim 6 , wherein the porous ceramic granules have the average diameter from about 200 μm to about 500 μm.

9. The method of claim 6 , wherein the pore-forming agent particles comprise polymethyl methacrylate (PMMA), polymethacrylate (PMA), polystyrene, polyethylene or a combination thereof.

10. The method of claim 6 , wherein the pore-forming agent particles comprise polymethyl methacrylate (PMMA).

11. The method of claim 6 , wherein heating the pore-forming agent particles to a temperature above a glass transition temperature for the pore-forming agent particles occurs in a thermoforming process.

12. The method of claim 11 , wherein the thermoforming process occurs at a temperature from about 150° C. to about 180° C. for a period of time from about 14 to about 18 hours.

13. The method of claim 12 , wherein the heated pore-forming agent particles during the thermoforming process creates the interconnected porous structure.

14. The method of claim 6 , wherein heating the mixture to remove the pore-forming agent particles from the mixture to form the porous ceramic material is performed at a temperature from about 200° C. to about 300° C. for a period of time.

15. The method of claim 6 , wherein the porous ceramic granules are micronized by passing the porous ceramic granules through a sieve using a crushing force.

16. The method of claim 6 , wherein the ceramic material comprises hydroxyapatite and beta-tricalcium phosphate powder in a suspension or a slurry.

17. The method of claim 16 , wherein the ceramic material comprises a calcium to phosphate ratio of between 1.0 to about 2.0.

18. The method of claim 6 , wherein the ceramic material is a biphasic calcium phosphate comprising hydroxyapatite in an amount of about 8 to about 22 wt. % and beta-tricalcium phosphate in an amount of about 78 to about 92 wt. %.