Preparation of unagglomerated metal oxide particles with uniform particle size

• US 4,778,671 A
• Filed: 07/14/1986
• Issued: 10/18/1988
• Est. Priority Date: 07/14/1986
• Status: Expired due to Fees

• Current Assignee: Corning Glass Works Inc. (Corning Incorporated)
• Original Assignee: Corning Glass Works Inc. (Corning Incorporated)
• Inventors: Wusirika, Raja R.
• Primary Examiner(s): Pal, Asok
• Application Number:
  US06/884,973
• Time in Patent Office: 827 Days
• Field of Search: 423/592, 423/593, 423/598, 423/608, 423/263, 423/637, 423/639, 423/610, 423/604, 423/605, 423/606, 423/607
• US Class Current: 423/592.1
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01B 13/18 by thermal decomposition of compounds, e.g. of salts or hydroxides
• CPC Class Codes: C01F 11/02 Oxides or hydroxides production of lime C04B2/00
• CPC Class Codes: C01G 25/02 Oxides
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/50 Agglomerated particles
• CPC Class Codes: C01P 2004/52 highly monodisperse size distribution
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer

Abstract

Disclosed is a method for producing substantially unagglomerated submicron metal oxide particles having uniform size distribution. The process is readily adaptable to the production of multicomponent metal oxide particles. The method comprises the steps of (1) providing a solution of a complex of an oxygen-containing metal salt and a chelating agent selected from the group consisting of ethylenediaminetetraacetic acid, hydroxy ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentacetic acid, glycolic acid, lactic acid, citric acid, tartaric acid, succinic acid, alkali salts of the foregoing acids, and mixtures of these; (2) drying the solution by heating the solution under alkaline conditions for a time and at a temperature sufficient to remove substantially all the solvent from the solution and to leave a solid residue; (3) heating the solid residue for time and at a temperature sufficient to convert at least a substantial portion of the residue to substantially unagglomerated particles of the metal oxide having a mean diameter up to about one micron and a uniform particle size.

Claims

1. A process for the production of substantially unagglomerated metal oxide particles having a mean diameter of up to about 1 micron and a substantially uniform particle size comprising:

(a) providing a solution of an oxygen-containing nitrate of a first metal selected from the group consisting of alkaline earth metals, lanthanide metals, transition metals exclusive of vanadium, tungsten, molybdenum, niobium and tantalum, and mixtures of these;

(b) adding to the solution a chelating agent selected from the group consisting of tartaric acid, citric acid, and mixtures of these;

(c) adding to the solution a base selected from the group consisting of ammonium hydroxide, urea, and mixtures of these;

(d) drying the solution by heating for a time and at a temperature sufficient to remove substantially all the solvent from the solution to leave a solid residue; and

(e) calcining the solid residue for a time and at a temperature sufficient to form particles of said metal oxide.

2. The process of claim 1 wherein said first metal is selected from the group consisting of alkaline earth metals, lanthanide metals, metals from Group IVb of the periodic table, and mixtures of these.

3. The process of claim 1 wherein the solution has a solvent selected from the group consisting of C₁ -C₃ alcohols.

4. The process of claim 3 wherein said chelating agent is citric acid.

5. The process of claim 4 wherein said first metal is zirconium.

6. The process of claim 5 wherein said nitrate is zirconyl nitrate.

7. The process of claim 6 wherein the citric acid is added in an amount sufficient to produce a molar ratio of citric acid to zirconyl nitrate of at least about 0.5 to 1.

8. The process of claim 5 wherein said base is ammonium hydroxide.

9. The process of claim 5 further comprising the step of adding to the solution of step (a), (b) and/or (c) an oxygen containing salt of a second metal.

10. The process of claim 9 wherein said second metal salt is added in an amount sufficient to produce a second metal oxide in an amount up to about 10 mole percent of the oxide of the first metal.

11. The process of claim 10 wherein said second metal is selected from the group consisting of yttrium, magnesium and calcium.

12. A process for the production of substantially unagglomerated metal oxide particles having a mean diameter of up to about 1 micron and a substantially uniform particle size comprising:

(a) providing an alkaline solution of a salt of a first metal having an ammonium cation and a carbonate anion, said first metal being selected from the group consisting of alkaline earth metals, lanthanide metals, transition metals exclusive of vanadium, tungsten, molybdenum, niobium and tantalum, and mixtures of these;

(b) adding a chelating agent to the solution to form a chelated solution, said chelating agent being a sodium salt of an acid selected from the group consisting of EDTA, H-EDTA, NTA, DTPA, lactic acid, glycolic acid, succinic acid, and mixtures of these;

(c) drying the chelated solution by heating for a time and at a temperature sufficient to remove substantially all the solvent from the solution to leave a solid residue; and

(d) heating the solid residue for a time and at a temperature sufficient to convert at least a substantial portion of the residue to said metal oxide.

13. The process of claim 12 wherein said first metal is selected from the group consisting of alkaline earth metals, lanthanide metals, metals from Group IVb of the periodic table, and mixtures of these.

14. The process of claim 13 wherein said chelating agent is a sodium salt of EDTA.

15. The process of claim 14 wherein said metal is zirconium.

16. The process of claim 14 wherein said salt is ammonium zirconium carbonate.

17. The process of claim 16 wherein the sodium salt of EDTA is added in an amount sufficient to produce a molar ratio of sodium salt to ammonium zirconium carbonate of at least about 0.5 to 1.

18. The process of claim 15 further comprising the step of adding to the solution of step (a), (b) and/or (c) an oxygen containing salt of a second metal.

19. The process of claim 18 wherein said second metal salt is added in an amount sufficient to produce a second metal oxide in an amount up to about 10 mole percent of the oxide of the first metal.

20. The process of claim 19 wherein said second metal is selected from the group consisting of yttrium, magnesium and calcium.

21. A process for the production of substantially unagglomerated metal oxide particles having a mean diameter of up to about 1 micron and a substantially uniform particle size distribution comprising:

(a) providing a solution of a chelated complex of a salt of a first metal having an ammonium cation and a carbonate anion and a chelating agent, said chelating agent being a rubidium cesium, or sodium salt of an acid selected from the group consisting of EDTA, H-EDTA, NTA, DTPA, glycolic acid, succinic acid, lactic acid, and mixtures of these, said first metal being selected from the group consisting of alkaline earth metals, lanthanide metals, transition metals exclusive of vanadium, tungsten, molybdenum, niobium and tantalum, and mixtures of these;

(b) heating the solution under alkaline conditions for a time and at a temperature sufficient to remove

substantially all of the solvent from the solution to leave a solid residue; and

(c) heating the solid residue for a time and at a temperature sufficient to form particles of said metal oxide.

22. The process of claim 21 wherein said first metal is selected from the group consisting of alkaline earth metals, lanthanide metals, metals from Group IVb of the periodic table, and mixtures of these.

23. The process of claim 22 wherein said chelating agent is a sodium salt.

24. The process of claim 23 wherein said chelating agent is a disodium salt.

25. The process of claim 24 wherein said provided solution is an alkaline solution.

26. The process of claim 25 wherein said first metal is a metal from Group IVb of the periodic table.

27. The process of claim 26 wherein said first metal is zirconium.

28. The process of claim 21 wherein the step of heating the solution under alkaline conditions further comprises the step of adding a base to the solution to produce alkaline conditions.

29. The process of claim 28 wherein said heating is carried out for between about 4 hours and 2 days at a temperature of between about 50°

C. and 100°

C.

30. The process of claim 28 wherein the solvent of said solution is water.

31. The process of claim 21 wherein said first metal is zirconium.

32. The process of claim 31 wherein said provided solution contains an oxygen containing salt of a second metal.

33. The process of claim 32 wherein said second metal salt is present in an amount sufficient to produce a second metal oxide in an amount up to about 10 mole percent of the oxide of the first metal.

34. The process of claim 33 wherein said second metal is selected from the group consisting of yttrium, magnesium, and calcium.

35. A process for the production of substantially unagglomerated metal oxide particles having a substantially uniform particle size distribution and a mean diamerter of less than about 1 micron comprising;

(a) providing a chelated solution selected from the group consisting of;

(1) a solution of a chelated complex of an oxygen containing nitrate of a first metal selected from the group consisting of alkaline earth metals, lanthanide metals, transition metals exclusive of vanadium, tungsten, molybdenum, niobium and tantalum, and chelating agent selected from the group consisting of tartaric acid, citric acid, and mixtures of these; and

(2) a solution of a chelated complex of an oxygen-containing salt of a first metal selected from the group consisting of alkaline earth metals, lanthanide metals, transition metals exclusive of vanadium, tungsten, molybdenum, niobium and tantalum, and a chelating agent selected from the group consisting of;

EDTA;

H-EDTA;

NTA;

DTPA;

lactic acid;

succinic acid;

sodium, rubidium, or cesium salts of the foreging acids; and

a mixture of these;

(b) heating the chelated solution under alkaline conditions, said heating step carried out for a time and at a temperature sufficient to remove substantially all the solvent from the solution to leave a solid residue; and

(c) heating the solid residue for a time and at a temperature sufficient to form particles of said metal oxide.

36. The process of claim 35 wherein said chelated solution is a solution of a chelated complex of an oxygen-containing nitrate of a metal and a chelating agent selected from the group consisting of tartaric acid, citric acid, and mixtures of these.

37. The process of claim 36 wherein said metal is selected from the group consisting of alkaline earth metals, lanthanide metals, and metals in Group IVb of the periodic table.

38. The process of claim 37 wherein said metal is zirconium.

39. The process of claim 38 wherein the solution has a solvent selected from the group consisting of C₁ to C₃ alcohols.

40. The process of claim 35 wherein said chelated solution is a solution of a chelated complex of a salt of a metal having an ammonium cation and a carbonate anion and a chelating agent selected from the group consisting of EDTA;

H-EDTA;

NTA;

DTPA;

glycolic acid;

lactic acid;

succinic acid; and

sodium, rubidium or cesium salts of the foregoing acids.

41. The process of claim 40 wherein said chelated solution is a solution of a chelated complex of a salt of a metal having an ammonium cation and a carbonate anion, and a chelating agent consisting of succinic acid.

42. The process of claim 41 wherein said metal is selected from the group consisting of alkaline earth metals, a lanthanide metals, and metals in group IVb.

43. The process of claim 42 wherein said metal is zirconium.

44. The process of claim 35 wherein said chelated solution is a solution of a chelated complex of an oxygen containing chloride of a metal and a chelating agent consisting of a sodium salt of glycolic acid.

45. The process of claim 44 wherein said first metal is selected from the group consisting of alkaline earth metals, lanthanide metals, and metals in Group IVb of the periodic table.

46. The process of claim 44 wherein said metal is zirconium.

47. The process of claim 35 further comprising the step of adding to the solution of step (a), (b) and/or (c) an oxygen containing salt of a second metal.

48. The process of claim 47 wherein said second metal is added in an amount sufficient to produce a second metal oxide in an amount up to about 10 mole percent of the oxide of the first metal.

49. The process of claim 48 wherein said second metal is selected from the group consisting of yttrium, magnesium and calcium.

50. A process of the production of substantially unagglomerated metal oxide particles having a substantial uniform particle size distribution and a mean diameter of less than about 1 micron comprising:

(a) providing a solution of chelated complex of an oxygen containing salt of a metal selected from the group consisting of alkaline earth metals, lanthanide metals, transition metals exclusive of vanadium, tungsten, molybdenum, niobium and tantalum, and a chelating agent selected from the group consisting of;

EDTA;

H-EDTA;

NTA;

DTPA;

glycolic acid;

lactic acid;

succinic acid;

tartaric acid;

citric acid;

phthalic acid;

alkali salts of the foregoing acids; and

mixtures of these;

(b) heating the chelated solution under alkaline conditions, said heating step carried out for a time and at a temperature sufficient to remove substantially all the solvent from the solution to leave a solid residue; and

(c) heating the solid residue for a time and at a temperature sufficient to convert at least a substantial portion of the residue to said metal oxide.

51. The process of claim 50 wherein metal is selected from the group consisting of alkaline earth metals, lanthanide metals, and metals in group IVb of the periodic table.

52. The process of claim 51 wherein said metal is zirconium.

53. The process of claim 50 further comprising the step of adding to the solution an oxygen containing salt of a second metal.

54. The process of claim 53 wherein said second metal salt is added in an amount sufficient to produce a second metal oxide in an amount up to about 10 mole percent of the oxide of the first metal.

55. The process of claim 54 wherein said second metal is selected from the group consisting of yttrium, magnesium and calcium.