Method of making carbide, nitride and boride powders

• US 4,851,262 A
• Filed: 05/27/1987
• Issued: 07/25/1989
• Est. Priority Date: 05/27/1987
• Status: Expired due to Fees

• Current Assignee: Carnegie Mellon University
• Original Assignee: Carnegie Mellon University
• Inventors: McFeaters, John S.
• Primary Examiner(s): Dixon, Jr., William R.
• Assistant Examiner(s): GROUP, KARL E
• Application Number:
  US07/054,874
• Time in Patent Office: 790 Days
• Field of Search: 501/87, 501/88, 501/96, 427/217, 427/226, 427/227, 427/250, 427/251, 427/255, 427/383.3, 423/289, 423/297, 423/411, 423/412, 423/439, 423/440, 75/0.5 B, 118/716
• US Class Current: 427/217
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01B 21/06 Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boronazides C01B21/08
• CPC Class Codes: C01B 32/90 Carbides
• CPC Class Codes: C01B 32/914 Carbides of single elements
• CPC Class Codes: C01B 32/921 Titanium carbide
• CPC Class Codes: C01B 32/949 Tungsten or molybdenum carbides
• CPC Class Codes: C01B 32/956 Silicon carbide
• CPC Class Codes: C01B 32/97 Preparation from SiO or SiO2
• CPC Class Codes: C01B 35/04 Metal borides
• 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: C30B 25/005 Growth of whiskers or needles
• CPC Class Codes: C30B 29/36 Carbides
• CPC Class Codes: C30B 29/38 Nitrides

Abstract

A method of making metal carbide, nitride, or boride powders and mixtures thereof by direct reduction of metal compounds comprises (a) forming a reactant mixture, (b) heating the reactant mixture to temperatures that cause solid reactants to vaporize and above which the metal precursor compounds are reduced, (c) passing the heated reactant mixture through a converging-diverging nozzle designed to reduce the temperature of the mixture to a temperature and for a time sufficient for further product species to form and for nuclei to form and grow by condensation to form the product powders, and (d) exhausting the mixture and product powders from the nozzle into an expansion chamber.

Claims

1. A method of making metal carbide, nitride, or boride product powders and mixtures thereof by direct reduction of metal compounds comprising the steps of

(a) forming a reactant mixture comprising one or more metal compounds, a source of carbon sufficient to reduce the metal compound to form metal, a source of carbon, nitrogen, or boron or mixtures thereof sufficient to react with substantially all of the metal formed by reduction, a small amount of gas or source of a gas selected from hydrogen or helium and mixtures thereof, and a heat exchange gas being substantially inert with respect to the product powders which gas may be selected from helium, argon, nitrogen and hydrogen, a source of a coating metal being added to said reactant mixture, said coating metal being vaporizable at the temperature to which the mixture is heated and having a vapor pressure higher than the product powders,

(b) heating the reactant mixture to temperatures that cause the solid reactants to vaporize and above which the metal compounds are reduced,

(c) passing the heated reactant mixture through a converging-diverging nozzle designed to reduce the temperature of the mixture to a temperature and for a time sufficient for further product species to form and for nuclei to form and grow by condensation to form the product powders, and such that after substantially all of the product powders have condensed from the reactant mixture in the nozzle the coating metals condense on the surface of the product powders,

(d) exhausting the reactant mixture and product powders from the nozzle into an expansion chamber in a manner to reduce the total enthalpy of the mixture and powders to quickly lower the temperature of the powders sufficiently that the rate of undesired reactions is insignificant, and

(e) recovering product powders with a metal coating.

2. A method according to claim 1 wherein the coating metal is selected from the group consisting of copper, gold, silver, tin, zinc, aluminum, cadmium, indium and mixtures thereof.

3. A method according to claim 1 wherein the coating metal is selected from metals in the lanthanide and actinide series having suitably high vapor pressures and mixtures thereof.

4. A method according to claim 1 wherein insufficient carbon, nitrogen or boron are provided in the reactant mixture to react with all of the metal formed by reduction thus providing a source of coating metal comprising the at least one metal that is also present in the product powders in reacted form.

5. The method according to claim 1 wherein ammonia is added to the mixture as a source of nitrogen and hydrogen.

6. The method according to claim 1 wherein a hydride of boride is added to the mixture as a source of boron and hydrogen.

7. A method according to claim 1 wherein the metal compounds for forming the reactant mixture are metal oxide compounds.

18. A method according to claims 1, 8, or 9 wherein the mixture is heated in excess of 2,000 degrees Kelvin prior to passing through the nozzle.

19. A method according to claims 1, 8, or 9 wherein the mixture is heated in the range 3000 to 4500 degrees Kelvin prior to passing through the nozzle.

20. The methods according to claims 1, 8, or 9 wherein the recovered powders have a particle size between 0.01 and 1 micron.

21. The methods according to claims 1, 8, or 9 wherein the gas selected from hydrogen and helium is present in sufficient amount such that as the mixture is passed through the nozzle energy stored in vibrational modes is sufficiently rapidly transferred to other energy storage modes such that condensation proceeds and undesirable reactions do not take place.

22. The methods according to claims 1, 8, or 9 wherein the gas selected from hydrogen and helium in the reactant mixture is between 5 and 75 mole percent.

23. The methods according to claims 1, 8, or 9 wherein the temperature of the reactant mixture and product powders in the expansion chamber are reduced to below 1300 degrees Kelvin.

24. The method according to claims 1, 8, or 9 wherein the amount of heat exchange gas in the mixture is sufficient to absorb sufficient heat of condensation during the expansion through the nozzle to enable the condensation to continue.

25. The method according to claims 1, 8, or 9 wherein the pressure on the inlet side of the nozzle is between 1 and 100 atmospheres.

26. The method accordng to claims 1, or or 9 wherein the nozzle has an orifice between 0.1 and 5.0 cm in radius and a length between 0.2 and 2 meters and the outlet cone has an L value between 5 and 35.

27. The method according to claims 1, 8, or 9 wherein the nozzle orifice area to outlet area ration (A/A*) is at least 2.

28. The method according to claims 1, 8, or 9 wherein the nozzle orifice area to inlet area ratio (A/A*) is between 5 and 100 such that inlet flow from the reactor is initially at a low speed.

29. The method according to claim 3 wherein the particle size of the metal oxide introduced into the mixture is minus 65 mesh.

30. The method according to claim 1, 8, or 9 wherein the mixture is heated in a dispersed discharge reactor in which a strong turbulence is maintain.

31. The methods according to claim 30 wherein the method is a continuous process.

32. The methods according to claim 31 wherein the residence time in the reactor is about 1 second.

8. A method of making metal carbide, nitride or boride powders and mixtures thereof by direct reduction of metal oxide compounds comprising the steps for

(a) forming a reactant mixture comprising one or more metal oxide compounds, a source of carbon comprising a gaseous hydrocarbon sufficient to reduce the metal compound to form metal, and a source of carbon, nitrogen or boron or mixtures thereof sufficient to react with substantially all of the metal formed by reduction, a small amount of gas or source of a gas selection from hydrogen or helium and mixtures thereof, and a heat exchange gas being substantially inert with respect to the product powders which gas may be selected from helium, argon, nitrogen and hydrogen,

(b) heating the reactant mixture to temperatures that cause the solid reactants to vaporize and above which the metal compounds are reduced,

(c) passing the heated reactant mixture through a converging-diverging nozzle designed to reduce the temperature of the mixture to a temperature and for a time sufficient for products to form and for nuclei to form and grow by condensation to form the product powders,

(d) exhausting the reactant mixture and product powders from the nozzle into an expansion chamber in a manner to reduce the total enthalpy of the mixture and product powders to quickly lower the temperature of the product powders sufficiently that the rate of undesired reactions is insignificant, and

(e) recovering product powders.

9. A method of making metal carbide product powders by direct reduction of metal oxides comprising the steps for

(a) forming a reactant mixture comprising one or more metal oxides, a source of carbon sufficient to reduce the metal oxide to form metal, a source of carbon comprising a gaseous hydrocarbon sufficient to react with substantially all of the metal formed by reduction, a small amount of gas or source of a gas selected from hydrogen or helium and mixtures thereof, and a heat exchange gas being substantially inert with respect to the product powders which gas may be selected from helium, argon, nitrogen and hydrogen,

(b) heating the reactant mixture to temperatures that cause the solid reactants to vaporize and above which the metal oxides are reduced and above which the formation of carbides are favored,

(c) passing the heated reactant mixture through a converging-diverging nozzle designated to reduce the temperature of the mixture to a temperature and for a time sufficient for additional carbides to form and for nuclei to form and grow by condensation to form the product metal carbide powders,

(d) exhausting the mixture and metal carbide product powders from the nozzle into an expension chamber maintained at a pressure below the exhaust pressure of the nozzle and mixing with co-flowing steams of heat exchange gas in a manner to reduce the total enthalpy of the mixture and metal carbide powders to quickly lower the temperature of the metal carbide powders sufficiently that the rate of oxide formation is insignificant, and

(e) electrostatically recovering metal carbide powders.

10. A method according to claim 9 for making carbides of the group IVb transition metal selected from the group consisting of titanium, zirconium and hafnium wherein the oxide comprises a reactant mixture selected from the group IVb transition metals in powdered form.

11. A method according to claim 9 for making carbides of the group Vb transition metal selected from the group consisting of vanadium, niobium, and tantalum wherein the oxide comprises a reactant mixture selected from the group Vb transition metals in powdered form.

12. A method according to claim 9 for making carbides of the group VIb transition metal selected from the group consisting of chronium, molybdenum, and tungsten wherein the oxide comprises a reactant mixture selected from the group VIb transition metals in powdered form.

13. A method according to claim 9 for making aluminum carbide wherein the reactant mixture comprises an oxide of aluminum in powdered form.

14. A method according to claim 9 for making silicon carbide wherein the reactant mixture comprises an oxide of silicon in powdered form.

15. The method according to claim 9 wherein the carbon source is methane.

16. The method according to claim 9 wherein the mole ratio of inert gas in the reactant mixture to metal oxide in the mixture is between 0.1:

1 and 10;

1.

17. The method according to claim 9 wherein the mole ratio of inert gas in the reactant mixture of metal oxide in the mixture is at least 1:

1.