Sintered Al.sub.2 O.sub.3 material, process for its production and use of the material

• US 6,066,584 A
• Filed: 01/31/1997
• Issued: 05/23/2000
• Est. Priority Date: 04/19/1994
• Status: Expired due to Term

• Current Assignee: Ceramedic LLC (Acacia Research Corporation)
• Original Assignee: Fraunhofer Gesellschaft Zur Foerderung Der Angewandten Forsching E.V.
• Inventors: Krell, Andreas, Blank, Paul
• Primary Examiner(s): MARCHESCHI, MICHAEL A
• Application Number:
  US08/727,409
• Time in Patent Office: 1,208 Days
• Field of Search: 501/127, 501/153, 501/128, 501/132, 51/307, 51/309, 264/621, 264/653, 264/603, 264/645
• US Class Current: 501/127
• CPC Class Codes: A61F 2310/00203 containing alumina or aluminium oxide
• CPC Class Codes: A61L 27/105 containing Al2O3
• CPC Class Codes: C04B 35/111 Fine ceramics

Abstract

The invention relates to the field of ceramics and concerns sintered Al.s2 O₃ compositions produced from corundum powder and also methods for the use of the invented compositions as medical implants or tool material. To produce such materials, an initially unsintered precursor having a relative density of ρ≧55% is produced from α-Al₂ O₃ powder having defined properties using at least two different dispersing methods, this precursor is subsequently subjected to heat treatment and sintering.

Claims

1. A method, comprising the steps of:

a) dispersing α

-Al₂ O₃ powder having a mean particle size d₅₀ of ≦

0.30 μ

m and a chemical purity of ≧

99.9% α

-Al₂ O₃ in an aqueous solution to create a mixture, said mixture effected through the application of at least two different dispersing methods;

b) treating said mixture so as to create a shaped unsintered body having a relative density of p≧

55%;

c) heating said unsintered body; and

d) sintering said unsintered body so as to create a sintered material.

3. The method of claim 1, wherein said dispersing methods are selected from the group consisting of stirring, milling, and ultrasound.

4. The method of claim 1, wherein said α

-Al₂ O₃ powder of step (a) has a specific surface area of 10-17 m² /g.

5. The method of claim 1, wherein said sintering comprises pressureless sintering in air.

6. The sintered material produced according to claim 1, wherein said sintered material comprises a mean grain size of 1.5 μ

m or less, a density of no less than 98.5% of a theoretical density, and a Vickers hardness greater than or equal to 2,000 at a test load from 10 to 100 N, said sintered material having a frequency of inhomogeneities of less than 50×

10⁹ m^-2.

30. The method of claim 1, wherein said two different dispersing methods are applied in series.

31. The method of claim 1, wherein said two different dispersing methods are applied simultaneously.

32. The method of claim 1, wherein said particle size has a distribution of d₁₆ >

0.065 μ

m, d₅₀ ≦

0.30 μ

m, d₈₄ <

0.45 μ

m.

33. The method of claim 1, wherein said aqueous solution comprises dispersants selected from the group consisting of mineral acids, carboxylic acids and polycarboxylic acids.

34. The method of claim 1, wherein said mixture is supplemented with compounds containing one or more elements selected from the group consisting of Li, Mg, Ba, Sr, Zn, Fe, Co, Ni, Cr, Zr, Ti, Si, Y, Ce, La, and Y.

35. The method of claim 1, wherein said treating step comprises pressure filtration in a pressure range of 0.3 to 20.0 MPa.

36. The method of claim 1, wherein, after said treating step and prior to said heating, said unsintered body is subjected to cold isostatic pressing.

2. A method, comprising the steps of:

a) dispersing α

-Al₂ O₃ powder having a mean particle size d₅₀ of ≦

0.30 μ

m and a chemical purity of ≧

99.9% Al₂ O₃ in an aqueous solution comprising water, polyvinyl alcohol and glycerol to create a mixture;

b) treating said mixture so as to create a shaped unsintered body having a relative density of p≧

55%;

c) heating said unsintered body; and

d) sintering said unsintered body so as to create a sintered material.

7. A method, comprising the steps of:

a) dispersing α

-Al₂ O₃ powder having a particle size of d₁₆ greater than 0.065 μ

m, d₅₀ not less than 0.2 μ

m and not greater than 0.4 μ

m, d₈₄ not less than 0.45 μ

m and not greater than 0.8 μ

m, and a chemical purity of ≧

99.9% α

--Al₂ O₃, in an aqueous solution to create a mixture, said mixture effected through the application of at least two different dispersing methods;

b) treating said mixture so as to create a shaped unsintered body having a relative density of p≧

55%;

c) heating said unsintered body; and

d) sintering said unsintered body so as to create a sintered material.

8. The method of claim 7, wherein said mixture in step (a) has a pH of between 3 and 7.

9. The method of claim 7, wherein said mixture in step (a) has a pH of between 4 and 6.

10. The method of claim 7, wherein said mixture in step (a) has a pH of approximately 5.

11. The method of claim 7, wherein said mixture further comprises chemical substances containing one or more elements selected from the group consisting of Li, Mg, Ba, Sr, Zn, Fe, Co, Ni, Cr, Zr, Ti, Si, Y, Ce, La and Y.

12. The method of claim 7, wherein said dispersing methods are selected from the group consisting of stirring, milling, and ultrasound.

13. The method of claim 7, wherein said sintering comprises pressureless sintering in air.

14. The sintered material produced according to claim 7, wherein said sintered material comprises a mean grain size of 2.0 μ

m or less, a density of no less than 98.5% of a theoretical density, a Vickers hardness greater than or equal to 1,750 at a test load from 10 to 100 N, and a flexural strength of 800 MPa or greater, said sintered material having a dimensionless defect density of less than 30×

10^-3.

37. The method of claim 7, wherein said two different dispersing methods are applied in series.

38. The method of claim 7, wherein said two different dispersing methods are applied simultaneously.

15. A method, comprising the steps of:

a) dispersing α

-Al₂ O₃ powder having a mean particle size d₅₀ of ≦

0.30 μ

m and a chemical purity of ≧

99.9% Al₂ O₃ in an aqueous solution to create a mixture, said dispersing comprising stirring said solution and subsequently milling;

b) treating said mixture so as to create a shaped unsintered body having a relative density of p≧

55%;

c) heating said unsintered body; and

d) sintering said unsintered body so as to create a sintered material.

16. The method of claim 15, wherein said α

-Al₂ O₃ powder of step (a) has a specific surface area of 10-17 m² /g.

17. The method of claim 15, wherein said sintering comprises pressureless sintering in air.

18. The sintered material produced according to claim 15, wherein said sintered material comprises a mean grain size of 1.5 μ

m or less, a density of no less than 98.5% of a theoretical density, and a Vickers hardness greater than or equal to 2,000 at a test load from 10 to 100 N, said sintered material having a frequency of inhomogeneities of less than 50×

10⁹ m^-2.

19. A method, comprising the steps of:

a) dispersing α

-Al₂ O₃ powder having a chemical purity of ≧

99.9% Al₂ O₃ in an aqueous solution to create a mixture, said dispersing comprising stirring said solution and simultaneously subjecting said solution to ultrasound;

b) treating said mixture so as to create a shaped unsintered body;

c) heating said unsintered body; and

d) sintering said unsintered body so as to create a sintered material.

20. The method of claim 19, wherein said aqueous solution comprises water and one or more dispersants selected from the group consisting of mineral acids, carboxylic acids and polycarboxylic acids.

21. The method of claim 19, wherein said treating of step (b) comprises pressure filtration.

22. The method of claim 19, wherein the treated mixture is dried such that a residual moisture content of between 2% and 3% is achieved.

23. The method of claim 19, wherein said sintering comprises pressureless sintering in air.

24. The sintered material produced according to claim 19, wherein said sintered material comprises a mean grain size of 1.5 μ

m or less, a density of no less than 98.5% of a theoretical density, and a Vickers hardness greater than or equal to 2,000 at a test load from 10 to 100 N, said sintered material having a frequency of inhomogeneities of less than 50×

10⁹ m^-2.

25. Sintered Al₂ O₃ material comprising a mean grain size of 1.5 μ

m or less, a density of no less than 98.8% of a theoretical density, and a Vickers hardness greater than or equal to 2,160 at a test load from 10 to 100 N, said sintered material having a frequency of inhomogeneities of less than 50×

10⁹ m^-2.

26. Sintered Al₂ O₃ material comprising a mean grain size of 2.0 μ

m or less, and a density of no less than 98.8% of a theoretical density, a Vickers hardness greater than or equal to 1,750 at a test load from 10 to 100 N, and a flexural strength of 800 MPa or greater, said sintered material having a dimensionless defect density of less than 30×

10^-3.

27. The sintered material of claim 26, wherein the dimensionless defect density is 10×

10^-3.

28. The sintered material of claim 26, wherein the dimensionless defect density is 4×

10^-3.

29. The sintered material of claim 26, wherein the dimensionless defect density is 0.6×

10^-3.

39. A method, comprising the steps of:

a) dispersing α

-Al₂ O₃ powder having a mean particle size d₅₀ of ≦

0.30 μ

m and a chemical purity of ≧

99.9% α

-Al₂ O₃, a polymerizable monomer, and a polymerization initiator in an aqueous solution to create a mixture, wherein said mixture has a solids content of α

-Al₂ O₃ powder of greater than 60% by mass, said mixture effected through the application of at least two different dispersing methods;

b) treating said mixture by degassing said mixture under a reduced pressure of 100-300 mbar, and initiating polymerization of said polymerizable monomer through the addition of a catalyst or increasing the temperature to 55-80 degrees Celsius so as to create an unsintered body having a relative density of p≧

55%;

c) heating said unsintered body; and

d) sintering said unsintered body so as to create a sintered material.

40. The method of claim 39, wherein said monomer comprises acrylamide.

41. The method of claim 39, wherein said two different dispersing methods are applied in series.

42. The method of claim 39, wherein said two different dispersing methods are applied simultaneously.

43. The method of claim 39 wherein said particle size has a distribution of d₁₆ >

0.065 μ

m, d₅₀ ≦

0.30 μ

m, d₈₄ <

0.45 μ

m.

44. The method of claim 39, wherein said treating of said unsintered body comprises pressure filtration in a pressure range of 0.3 to 20.0 MPa.

45. A method, comprising the steps of:

a) dispersing α

-Al₂ O₃ powder having a mean particle size d₅₀ of ≦

0.30 μ

m and a chemical purity of ≧

99.9% α

-Al₂ O₃ in an aqueous solution to create a mixture, said dispersing of said α

-Al₂ O₃ powder effected through the application of at least two different dispersing methods;

b) treating said mixture so as to create a shaped unsintered green intermediate product having a relative density of p≧

55%;

c) heating said unsintered green intermediate product so as to create an unsintered precursor;

d) crushing said unsintered precursor; and

e) sintering said crushed unsintered precursor so as to create a sintered material.

46. The method of claim 45, wherein said dispersing methods are selected from the group consisting of stirring, milling, and ultrasound.

47. The method of claim 45, wherein said two different dispersing methods are applied in series.

48. The method of claim 45, wherein said two different dispersing methods are applied simultaneously.

49. The method of claim 45, wherein said particle size has a distribution of d₁₆ >

0.065 μ

m, d₅₀ ≦

0.30 μ

m, d₈₄ <

0.45 μ

m.

50. The method of claim 45, wherein said aqueous solution comprises dispersants selected from the group consisting of mineral acids, carboxylic acids and polycarboxylic acids.

51. The method of claim 45, wherein said mixture is supplemented with compounds containing one or more elements selected from the group consisting of Li, Mg, Ba, Sr, Zn, Fe, Co, Ni, Cr, Zr, Ti, Si, Y, Ce, La, and Y.

52. A method, comprising the steps of:

a) dispersing α

-Al₂ O₃ powder having a mean particle size d₅₀ of ≦

0.30 μ

m and a chemical purity of ≧

99.9% α

-Al₂ O₃ in an aqueous solution to create a mixture, said mixture effected through the application of at least two different dispersing methods;

b) treating said mixture with a pressure process so as to create an unsintered precursor having a relative density of p≧

55%;

c) heating said unsintered precursor; and

d) sintering said unsintered precursor so as to create a sintered material.

53. The method of claim 52, wherein the pressure process is selected from the group consisting of pressure filtration, cold isostatic pressing, extrusion, and injection molding.