Ultrafine metal oxide powders by flame spray pyrolysis

• US 5,958,361 A
• Filed: 11/22/1995
• Issued: 09/28/1999
• Est. Priority Date: 03/19/1993
• Status: Expired due to Term

• Current Assignee: Board of Regents of the University of Michigan (University of Michigan)
• Original Assignee: Board of Regents of the University of Michigan (University of Michigan)
• Inventors: Treadwell, David R., Waldner, Kurt F., Bickmore, Clint R., Laine, Richard M.
• Primary Examiner(s): BOS, STEVEN J
• Application Number:
  US08/562,296
• Time in Patent Office: 1,406 Days
• Field of Search: 423/592, 423/593, 423/278, 423/335, 423/624, 423/625, 423/618, 423/619, 423/608, 423/609, 423/610, 423/635, 423/641
• US Class Current: 423/610
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01B 13/34 by oxidation or hydrolysis of sprayed or atomised solutions
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/88 by thermal analysis data, e.g. TGA, DTA, DSC
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/04 obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• 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
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C08G 79/00 Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule

Abstract

Ultrafine metal oxide and mixed metal oxide ceramic particles are prepared by flame spray pyrolysis of a ceramic precursor solution containing one or more gycolato polymetallooxanes dissolved in a volatile organic solvent. Recycle of the nanosized particles disposed in additional ceramic precursor solution leads to larger particles. The metal oxide and mixed metal oxide particles may be converted to the respective nitrides by high temperature ammonolysis. The process produces high quality ceramic particles from inexpensive and relatively non-toxic reagents in high space-time yield.

Claims

1. A process for the preparation of ultrafine metal oxide or mixed metal oxide ceramic particles having mean particle sizes in the range of 2-500 nm, said process comprising:

a) aerosolizing a ceramic precursor solution comprising one or more glycolato polymetallooxanes in a volatile organic solvent or volatile flammable organic solvent mixture, said glycolato polymetallooxane(s) present in said volatile solvent(s) in an amount of from 1 weight percent to 30 weight percent of said ceramic precursor solution, said glycolato polymetallooxane(s) having bound therein in excess of 90% of the metal content of said metal oxide or mixed metal oxide, to form a ceramic precursor solution aerosol containing droplets of said ceramic precursor solution;

b) supplying oxygen to said ceramic precursor solution aerosol in an amount at least stoichiometrically equivalent to combustible material contained in said ceramic precursor solution aerosol to form an aerosol and oxygen mixture;

c) igniting said aerosol an oxygen mixture and forming metal oxide or mixed metal oxide ceramic particles thereby and a gaseous effluent containing products of combustion; and

d) separating said metal oxide or said mixed metal oxide ceramic particles from said gaseous effluent to recover an ultrafine ceramic particle product.

2. The process of claim 1 wherein at least one of said gycolato polymetallooxanes is prepared by the digestion of one or more metal oxides with a glycolato-providing moiety.

3. The process of claim 2 wherein said gycolato-providing moiety is selected from the group consisting of aliphatic hydroxyl-functional compounds having from two to four hydroxyl groups attached to one or more C_1-12 aliphatic hydrocarbon residues.

4. The process of claim 3 wherein at least one of said gycolato-providing moieties is selected from the group consisting of dialkanolamines, trialkanolamines and 1,1,1-tris(hydroxymethyl)aminomethane.

5. The process of claim 1 wherein said volatile, flammable organic solvent is selected from organic solvents having a boiling point lower than 300°

C.

6. The process of claim 5 wherein said volatile, flammable organic solvent is an oxygen-containing organic solvent.

7. The process of claim 6 wherein said oxygen-containing solvent is a solvent boiling below 100°

C. selected from the group consisting of the lower C_1-6 aliphatic and cycloaliphatic alcohols, ethers, ketones and esters.

8. The process of claim 6 wherein said oxygen-containing solvent comprises a C_1-6 aliphatic alcohol.

9. The process of claim 1 wherein said aerosolization is effected by directing a stream of ceramic precursor solution into a fast moving stream of gas comprising oxygen.

10. The process of claim 1 wherein said step of igniting is performed by igniting means selected from the group consisting of an oxyhydrogen torch, a hydrocarbon gas and oxygen torch, a glow wire, an electrical discharge, and laser energy.

11. The process of claim 1 wherein said aerosolization, said supplying of oxygen and said igniting take place in a flame pyrolysis chamber wherein the temperature in the proximity of a flame front provided by said igniting is at least 500°

C.

12. The process of claim 11 wherein connected downstream from said flame pyrolysis chamber is/are one or more electrostatic precipitators.

13. The process of claim 12 wherein at least two electrostatic precipitators are employed in parallel, said electrostatic precipitators having shut-off means associated with said precipitators located between said precipitators and said flame pyrolysis chamber, said shut-off means effective when closed to substantially prevent passage of effluent gas and ceramic particles into said electrostatic precipitators, the process further comprising closing at least one of said shut-off means and removing ceramic particles from said electrostatic precipitator while one shut-off means associated with at least one electrostatic precipitator remains open providing an exit for effluent gas and ceramic particles from said flame pyrolysis chamber.

14. The process of claim 1 wherein said ceramic metal oxide or mixed metal oxide particles are converted into metal nitride or mixed metal nitride particles respectively by treating said particles with anhydrous ammonia at a temperature of from 500°

C. to 2000°

C. until substantially all metal oxides are converted to metal nitrides.

15. The process of claim 1 further comprising dispensing said ultrafine ceramic particle product in a further ceramic precursor solution, repeating steps (a) through (d) to recover a ceramic particle product having larger mean particle size than said ultrafine ceramic particle product.

16. The process of claim 15 wherein the mean particle size of said ceramic particle product is from greater than 500 nm to 20 μ

m.

17. The process of claim 1 wherein said glycolato polymetallooxane comprises a polymetallooxane comprising the moiety:

##STR6## wherein M¹ is selected from the group consisting of trivalent or tetravalent B, Al, Ga or In, or tetravalent, pentavalent, or hexavalent Si, Ge, Sn, Pb, Ti, Zr, and Hf;

n is 2, 3 or 4 when M¹ is B, Al, Ga or In; and

n is 3, 4, 5, or 6 when M¹ is Si, Ge, Sn, Pb, Ti, Zr, or Hf;

R¹ and R² are independently selected from the group consisting of H, OH, C_1-8 alkyl, C_1-6 alkoxy, C_2-8 alkenyl, C_6-12 aryl, C_1-8 hydroxyalkyl, C_1-8 thioalkyl, C_2-12 alkoxyalkyl, C_4-20 heteroaromatic, C_1-10 alkylsilane, C_1-10 alkylsiloxane and combinations thereof;

O'"'"' is bonded to M¹, M² or H wherein

M² is selected from the group consisting of Si, Ge, Sn, Pb, B, Al, Ga, In, Ti, Zr, and Hf, an ammonium or phosphonium species, or a Group Ia or IIa metal of the Periodic Table;

wherein when one O'"'"' is bonded to M¹, n is 2 or 3 when M¹ is B, Al, Ga, or In and at least one O'"'"' is bonded to M² ;

wherein when two O'"'"' are bonded to M¹, n is 2 when M¹ is B, Al, Ga or In;

wherein when one O'"'"' is bonded to M¹, n is 3, 4, or 5 when M¹ is Si, Ge, Sn, Pb, Ti, Zr, or Hf and at least one O'"'"' is bonded to M² ; and

wherein when two O'"'"' are bonded to M¹ and M¹ is Si, Ge, Sn, Pb, Ti, Zr, or Hf, n is 3 or 4 and at least one O'"'"' is bonded to M² ; and

R³ is independently selected from the group consisting of (CR₂)_y, (CR₂ CR₂)_y N(CR₂)_y, (CR₂ CR₂)_y NR(CR₂)_y, (CR₂ CR₂)_y O!_y --(CR₂)_y, and combinations thereof wherein R is selected from the group consisting of H, OH, C_1-8 alkyl, C_1-6 alkoxy, C_2-8 alkenyl, C_6-12 aryl, C_1-8 hydroxyalkyl, C_1-8 thioalkyl, C_2-12 alkoxyalkyl, C_4-20 heteroaromatic, C_1-10 alkylsilane, C_1-10 alkylsiloxane and combinations thereof, and where y is a number from 1 to 10 and wherein said polymetallooxane contains at least one M².

18. The process of claim 1 wherein said glycolato polymetallooxane comprises the heterocyclic moiety:

##STR7## wherein M is B, Al, Ga, In, Si, Ge, Sn, Pb, Ti, Zr, of Hf;

wherein when M is B, Al, Ga, or In, p is 0 or 1; and

when M is Si, Ge, Sn, Pb, Ti, Zr, or Hf, p is 1, 2, or 3;

when M is B, Al, Ga, or In and p is 1, Q⁺ is a group Ia, group IIa or ammonium or phosphonium moiety, and when M is Si, Ge, Sn, Pb, Ti, Zr, or Hf and p is 2 or 3, Q⁺ is a group Ia, group IIa or ammonium or phosphonium compound;

wherein when Q⁺ is R₄ N⁺ or R₄ P⁺, R is independently selected from the group consisting of H, OH, C_1-8 alkyl, C_1-6 alkoxy, C_2-8 alkenyl, C_6-12 aryl, C_1-8 hydroxyalkyl, C_1-8 thioalkyl, C_2-12 alkoxyalkyl, C_4-20 heteroaromatic, C_1-10 alkylsilane, C_1-10 alkylsiloxane and combinations thereof and wherein n is from 1 to about 150.