Preparation of high uniformity polycrystalline ceramics by presintering, hot isostatic pressing and sintering and the resulting ceramic

• US 5,013,696 A
• Filed: 09/25/1989
• Issued: 05/07/1991
• Est. Priority Date: 09/25/1989
• Status: Expired due to Term

• Current Assignee: General Electric Company
• Original Assignee: General Electric Company
• Inventors: Minnear, William P., Greskovich, Charles D., Riedner, Robert J., Brun, Milivoj K.
• Primary Examiner(s): Dixon, Jr., William R.
• Assistant Examiner(s): WRIGHT, ALAN
• Application Number:
  US07/412,237
• Time in Patent Office: 589 Days
• Field of Search: 501/153, 264/66
• US Class Current: 501/153
• CPC Class Codes: C04B 35/115 Translucent or transparent products
• CPC Class Codes: C04B 35/50 based on rare-earth compounds non-oxide rare earth compounds C04B35/5156
• CPC Class Codes: C04B 35/505 based on yttrium oxide
• CPC Class Codes: C04B 35/6455 Hot isostatic pressing

Abstract

Polycrystalline ceramic bodies having uniform transparent optical characteristics are produced by providing a green compact, presintering that compact at a temperature in the range from about 1,350° C. to about 1,650° C. until the closed porosity stage is reached, hot isostatic pressing the presintered compact to collapse substantially all pores disposed at grain boundaries and resintering the hot isostatically pressed compact at a temperature in the range from 1,700° C.-1,950° C. to cause grain growth under conditions in which pores, within those grains which are consumed by the growth of other grains, collapse as the grain boundary of the growing grain passes through the location of the pore in the smaller grain being consumed.

Claims

1. A method of producing a ceramic body comprising:

providing a green compact of appropriate configuration and composition;

presintering said compact at a temperature sufficient to promote grain growth to a substantially closed pore stage;

hot isostatic pressing said presintered compact at a temperature and pressure sufficient to eliminate most pores which are located at grain boundaries; and

resintering said body to induce further grain growth and further densification by reducing the number density of pores by a factor of at least 125.

2. The method recited in claim 1 wherein:

said resintering step is carried out at a higher temperature than said hot isostatic pressing step.

3. The method recited in claim 1 wherein:

after said presintering step said body has an average grain size of less than 10 microns.

4. The method recited in claim 3 wherein:

after said presintering step said body has an average grain size of between 10 microns and 200 microns.

5. The method recited in claim 3 wherein:

after said resintering step, said body has an average grain size of between 10 microns and 50 microns.

34. The method recited in claim 1 wherein:

said composition is single phased throughout the presintering, hot isostatic pressing and resintering steps.

35. The method recited in claim 1 wherein:

the presintering, hot isostatic pressing and resintering steps are all carried out at temperatures at which no liquid eutectic forms.

6. A method of making a high density ceramic with low residual porosity comprising:

providing a green ceramic body;

pre-sintering said green ceramic body until the body reaches the closed pore stage, under conditions in which a fine grain structure is produced;

hot isostatic pressing said pre-sintered body for a period of time and at a temperature sufficient to eliminate substantially all pores disposed at grain boundaries; and

sintering said hot isostatically pressed body at a temperature at which further densification and grain growth take place under conditions in which grain boundary migration is slow enough to permit pore disappearance for substantially all pores past which a grain boundary migrates.

7. The method recited in claim 6 wherein said ceramic has a cubic crystal structure.

8. The method recited in claim 7 wherein said ceramic comprises yttrium oxide.

9. The method recited in claim 8 wherein said ceramic comprises gadolinium oxide.

10. The method recited in claim 8 wherein:

said pre-sintering step is carried out in the temperature range between about 1,350°

C. and about 1,600°

C.;

said hot isostatic pressing step is carried out at substantially the same temperature as said pre-sintering step; and

said resintering step is carried out at a temperature in excess of 1,650°

C.

11. The method recited in claim 6 wherein:

said pre-sintering step is performed at a temperature in the range from 1,600°

C. to 1,650°

C.

12. The method recited in claim 11 wherein:

said hot isostatic pressing step is performed at a temperature in the range between 1,500°

C. and 1,550°

C. at a pressure in excess of 5,000 psi.

13. The method recited in claim 12 wherein said resintering step is performed at a temperature between about 1,700°

C. and 1,950°

C.

14. The method recited in claim 6 wherein said pre-sintering step is carried out at a temperature of substantially 1,625°

C. for about 4 hours in dry hydrogen followed by about 1 hour in wet hydrogen;

said hot isostatic pressing is carried out at a temperature of about 1,650°

C. at a pressure of about 25,000 psi or more; and

said resintering step is carried out at a temperature of at least 1,850°

C. for a period of about 2

15. The method recited in claim 14 wherein:

said resintering step is carried out at a temperature of about 1,925°

C.

16. The method recited in claim 6 wherein:

said ceramic has a hexagonal crystal structure.

17. The method recited in claim 16 wherein:

said ceramic comprises aluminum oxide.

36. The method recited in claim 6 wherein:

said composition is single phased throughout the pre-sintering, hot isostatic pressing and resintering steps.

37. The method recited in claim 6 wherein:

the presintering, hot isostatic pressing and resintering steps are all carried out at temperatures at which no liquid eutectic forms.

18. A polycrystalline ceramic body:

having a volume of at least 1 mm³ ;

having an optical attenuation coefficient of less than 10 cm^-1, at a measurement frequency in the visible region of the electromagnetic spectrum whereby said body is transparent; and

being free of pore clusters larger than 10 microns across.

19. The ceramic body recited in claim 18 wherein:

said body consists of material having a cubic crystal structure.

20. The ceramic body recited in claim 19 wherein:

said body comprises yttrium oxide.

21. The ceramic body recited in claim 20 wherein:

said body comprises gadolinium oxide.

22. The ceramic body recited in claim 18 wherein:

said body comprises gadolinium oxide.

23. The ceramic body recited in claim 18 exhibiting an optical attenuation coefficient which, at a fixed measurement frequency in the visible region of the electromagnetic spectrum, is uniform throughout said body to within 10%.

24. The ceramic body recited in claim 18 wherein:

said optical attenuation coefficient is less than 3 cm^-1.

25. The ceramic body recited in claim 18 wherein:

said ceramic is substantially 67 mole percent Y₂ O₃, 30 mole percent Gd₂ O₃, 3 mole percent Eu₂ O₃ and 150 ppm Pr₂ O₃.

26. The ceramic body recited in claim 25 wherein:

said body has less than one pore cluster per cm³.

27. The ceramic body recited in claim 18 exhibiting an optical attenuation coefficient which, at a fixed measurement frequency in the visible region of the electromagnetic spectrum, is uniform throughout said body to within 1%.

28. A polycrystalline ceramic body:

exhibiting an optical attenuation coefficient which, at a fixed measurement frequency in the visible region of the electromagnetic spectrum, is uniform throughout said body to within 3% and less than 10 cm^-1.

29. The ceramic body recited in claim 28 having:

an average grain size of less than 10 microns.

30. The ceramic body recited in claim 28 having:

an average grain size between 10 microns and 200 microns.

31. The ceramic body recited in claim 28 having:

an average grain size of between 10 microns and 50 microns.

32. A polycrystalline ceramic body:

having a non-cubic crystal structure;

having a volume of at least 1 mm³ ;

having an optical attenuation coefficient of less than 15 cm^-1, at a measurement frequency in the visible region of the electromagnetic spectrum; and

being free of pore clusters larger than 12 microns across.

33. The ceramic body recited in claim 32 wherein said body comprises alumina.

38. A method of producing a transparent ceramic body comprising:

providing a green compact of appropriate configuration and composition;

presintering said compact at a temperature sufficient to promote grain growth to a substantially closed pore stage;

hot isostatic pressing said presintered compact at a temperature and pressure sufficient to eliminate most pores which are located at grain boundaries; and

resintering said body to induce further grain growth and densification by reducing the number density of pores by a factor of at least 125 and to render said body transparent.

39. A method of making a transparent high density ceramic with low residual porosity comprising:

providing a green ceramic body;

pre-sintering said green ceramic body until the body reaches the closed pore stage, under conditions in which a fine grain structure is produced;

hot isostatic pressing said pre-sintered body for a period of time and at a temperature sufficient to eliminate substantially all pores disposed at grain boundaries; and

resintering said hot isostatically pressed body at a temperature at which further densification and grain growth take place under conditions in which grain boundary migration is slow enough to permit pore disappearance for substantially all pores past which a grain boundary migrates to thereby render said body transparent.