Methods of synthesizing hydroxyapatite powders and bulk materials

• US 5,858,318 A
• Filed: 11/27/1996
• Issued: 01/12/1999
• Est. Priority Date: 11/27/1996
• Status: Expired due to Term

• Current Assignee: Berkeley Advanced Biomaterials, Inc. (GNI Group Ltd.)
• Original Assignee: Berkeley Advanced Biomaterials, Inc. (GNI Group Ltd.)
• Inventors: Luo, Ping
• Primary Examiner(s): LANGEL, WAYNE A
• Application Number:
  US08/757,849
• Time in Patent Office: 776 Days
• Field of Search: 423/308, 423/309, 423/311
• US Class Current: 423/308
• CPC Class Codes: C01B 25/325 Preparation by double decomposition
• CPC Class Codes: C04B 35/447 based on phosphates , e.g. hydroxyapatite
• CPC Class Codes: C04B 35/622 Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products

Abstract

Methods are provided for producing non-porous controlled morphology hydroxyapatite granules of less than 8 μm by a spray-drying process. Solid or hollow spheres or doughnuts can be formed by controlling the volume fraction and viscosity of the slurry as well as the spray-drying conditions. Methods of providing for homogenous cellular structure hydroxyapatite granules are also provided. Pores or channels or varying size and number can be formed by varying the temperature at which a hydroxyapatite slurry formed in basic, saturated ammonium hydroxide is spray-dried. Methods of providing non-porous controlled morphology hydroxyapatite granules in ammonium hydroxide are also provided. The hydroxyapatite granules and bulk materials formed by these methods are also provided.

Claims

1. A method for synthesizing non-porous hydroxyapatite materials of controlled morphology comprising:

(a) preparing a hydroxyapatite slurry;

(b) adjusting the concentration, viscosity and pH values of the hydroxyapatite slurry to a concentration ranging from about 0 volume fraction to about 0.25 volume fraction and a viscosity ranging from about 0.5 cst to about 50 cst;

(c) spray drying the hydroxyapatite slurry to form granules using atomization pressure ranging from about 1 kg/cm² to about 5 kg/cm², and optionally, employing a heated coaxial air;

(d) heating the spray-dried granules to a temperature ranging from about 400°

C. to about 500°

C. to remove residual water;

(e) collecting the hydroxyapatite granules of step (d) wherein the concentration, viscosity and pH values of the hydroxyapatite slurry and the atomization pressure are varied to produce non-porous granules of 8 μ

m or less and a controlled morphology selected from the group consisting of hollow spheres and doughnuts; and

(f) sintering the collected granules from step (e) to form ceramic hydroxyapatite hollow spheres and doughnuts.

2. The method according to claim 1, further wherein the hydroxyapatite slurry is centrifuged and then washed to remove any residual ammonium prior to step (b).

3. The method according to claim 1, wherein the calcium and phosphate are present in the hydroxyapatite in a ratio ranging from about 1.5 to about 1.8.

4. The method according to claim 1, wherein the coaxial flow is approximately from 0.5 to 1.0 m³ /min.

5. The method according to claim 1, wherein the hydroxyapatite granules are sintered from about 10 minutes to about 1.5 hours.

6. A method for producing controlled morphology hydroxyapatite granules having cellular structures comprising the steps of:

(a) preparing a hydroxyapatite slurry containing saturated ammonium hydroxide;

(b) adjusting the concentration of the hydroxyapatite slurry up to 0.5 volume fraction and the viscosity to a range from about 0.5 cst to about 50 cst;

(c) spray drying the hydroxyapatite slurry containing saturated ammonium hydroxide at a temperature ranging from about 25°

C. to about 150°

C. to form hydroxyapatite granules;

(d) collecting the hydroxyapatite granules of step (c) wherein the spray temperature, the concentration, the viscosity of the hydroxyapatite slurry, and the spray atomization pressure are varied to produce hydroxyapatite granules containing residual ammonium hydroxide;

(e) heating the collected granules from step (d) from 400°

-500°

C. to form cellular hydroxyapadite granules;

wherein the temperature of the spray-drying in step (c) correlates to the amount of residual ammonium hydroxide which vaporizes or decomposes during the post heating process resulting in the size and number of interconnected pores; and

(f) sintering the granules of step (e) at about 900°

C. to about 1100°

C. to allow for formation of struts to form cellular ceramic hydroxyapatite granules.

7. The method according to claim 6, wherein the calcium and phosphate are present in the hydroxyapatite in a ratio ranging from about 1.5 to about 1.8.

8. The method according to claim 6, wherein the hydroxyapatite granules are sintered for from about 10 minutes to about 1.5 hours.

9. The method according to claim 6, wherein the atomization pressure ranges from about 1 kg/cm² to about 5 kg/cm².

10. The method according to claim 6, wherein the cellular granules have interconnected channels and struts.

11. The method according to claim 6, wherein the cellular ceramic hydroxyapatite granules are spheres and doughnuts.