Method for producing refractory filaments

• US 5,827,797 A
• Filed: 08/30/1996
• Issued: 10/27/1998
• Est. Priority Date: 08/28/1989
• Status: Expired due to Fees

• Current Assignee: Advanced Cerametrics, Inc.
• Original Assignee: Advanced Cerametrics, Inc.
• Inventors: Loh, Roland R., Allen, Thomas C., Cass, Richard B.
• Primary Examiner(s): Fiorilla, Christopher A.
• Application Number:
  US08/707,170
• Time in Patent Office: 788 Days
• Field of Search: 264/28, 264/638, 264/639, 264/104, 264/183, 264/188, 264/189, 264/190, 264/191, 264/192, 264/193, 264/194, 264/195, 264/196, 264/197, 264/198, 505/430
• US Class Current: 505/430
• CPC Class Codes: C04B 35/62227 obtaining fibres
• CPC Class Codes: H01M 4/66 Selection of materials
• CPC Class Codes: H01M 4/664 Ceramic materials
• CPC Class Codes: H01M 4/8605 Porous electrodes
• CPC Class Codes: H01M 4/8621 containing only metallic or ceramic material, e.g. made by sintering or sputtering
• CPC Class Codes: H01M 4/8803 Supports for the deposition of the catalytic active composition H01M4/90 takes precedence
• CPC Class Codes: H01M 4/90 Selection of catalytic material
• CPC Class Codes: H01M 8/0295 Matrices for immobilising electrolyte melts
• CPC Class Codes: H10N 60/0801 Manufacture or treatment of filaments or composite wires
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y10T 428/2913 Rod, strand, filament or fiber

Abstract

A process for producing fibers of refractory material. In one embodiment, a dispersion of particles of refractory material is prepared first. The dispersion then is mixed with a carrier solution of a salt of cellulose xanthate to form a spin mix. Using general wet spinning techniques, a filament of regenerated cellulose is formed from the spin mix. The filament has the particles dispersed therein. At this point, the filament can be utilized as a mixture of cellulose and refractory material, or it can be heat treated. If heated, the filament is raised to sufficient temperatures and over sufficient durations to remove substantially all of the regenerated cellulose and to sinter the particles of refractory material to form a filament.

Claims

1. A process of producing at least one filament of refractory material, comprising:

preparing a dispersion of particles of refractory material;

preparing a spin mix by mixing said dispersion with a carrier solution comprising a salt of cellulose xanthate, wherein the weight ratio of said particles to cellulose of said cellulose xanthate in said spin mix is greater than about 2;

8;

wet spinning said spin mix to form at least one filament of cellulose having at least a portion of said particles dispersed therein;

heating said at least one filament to sufficient temperatures and over sufficient durations to remove substantially all of said regenerated cellulose and to sinter said refractory particles to thereby form said at least one filament of refractory material.

2. The process of claim 1, wherein a portion of said particles are low-reactivity particles selected from the group consisting of particles at least in part coated with an organic barrier, particles combined with an inorganic compound, and combinations thereof.

3. The process of claim 2, wherein said organic barrier is a material selected from the group consisting of ethylene, propylene, olefin and diene homopolymers and copolymers, olefin and diene homopolymers and copolymers having functional groups, hydrocarbon waxes, fluorocarbon polymers including polytetrafluoroethylene, polyvinylidene fluoride, perfluorinated acrylates and methacrylates, urethanes, polyamides, polyurethanes, polyesters, polyethers, polyvinyl chloride, and acrylate and methacrylate ester homo and copolymers.

4. The process of claim 3, wherein said dispersion contains a low-reactivity dispersion medium selected from the group consisting of an aqueous salt, a chelant solution, a non-aqueous medium, and combinations thereof.

5. The process of claim 1, wherein said refractory material is a ceramic material.

6. The process of claim 5, wherein said ceramic material is a precursor for a superconductive ceramic.

7. The process of claim 6, which further includes the step of magnetically classifying said particles under cryogenic conditions prior to preparing said spin mix.

8. The process of claim 5, wherein a portion of said refractory material is selected from the group consisting of silicon carbide, aluminum nitride, silicon nitride, aluminum oxide, tin oxide, titanium carbide, hafnium oxide, zirconium oxide, titanium dioxide, molybdenum disilicide, lithium aluminate, ferrite, PZT (lead zirconium titanate), and antimony oxide.

9. The process of claim 5, wherein said refractory material is a powdered, electrically conductive substoichiometric titanium dioxide having uniformly distributed within its molecular structure chemically combined metal selected from the group consisting of chromium, copper, nickel, platinum, tantalum, zinc, magnesium, ruthenium, iridium, niobium, vanadium, tin, and combinations thereof.

10. The process of claim 5, wherein said refractory material particles are powdered, electrically conductive substoichiometric titanium dioxide having the basic formula TiO_x wherein x is a number in the region of about 1.10 to about 1.95.

11. The process of claim 10, wherein said substoichiometric titanium dioxide has an electrocatalytically active surface on at least part of the surface of the titanium oxide.

12. The process of claim 11, wherein said electrocatalytically active surface includes a material selected from the group consisting of platinum group metals or alloys, platinum group metal oxides, lead and lead dioxide.

13. The process of claim 10, wherein said x is about 1.65 to about 1.9.

14. The process of claim 13, wherein said x is about 1.7 to about 1.8.

15. The process of claim 1 wherein said at least one filament of refractory material has one or more defined properties selected from current carrying capacity, range of physical or mechanical properties, electrochemical properties, electrorestrictive properties or other properties which are substantially the same as the corresponding properties of said refractory material from which said at least one filament is prepared.

16. The process of claim 1, wherein said particles comprises particles each having a maximum dimension of from less than 1 to about 5 microns.

17. The process of claim 1, wherein said dispersion contains a low-reactivity dispersion medium selected from the group consisting of an aqueous salt, a chelant solution, a non-aqueous medium, and combinations thereof.

18. The process of claim 1, wherein said dispersion contains a dispersant.

19. The process of claim 1, wherein said dispersion contains a modifier.

20. The process of claim 1, wherein said weight ratio of said particles to said cellulose in said spin mix is greater than 1:

1.

21. The process of claim 20, wherein said weight ratio of said particles to said cellulose in said spin mix is greater than 7:

3.

22. The process of claim 21, wherein said weight ratio of said particles to said cellulose in said spin mix is greater than 8:

2.

23. The process of claim 1, wherein said spin mix is formed immediately before spinning such that contact time between said particles and said carrier solution is minimized.

24. The process of claim 1, wherein a portion of said carrier solution is a low-reactivity carrier solution selected from the group consisting of a carrier solution with substantially no excess hydroxide, a carrier solution with said salt of a cellulose xanthate dispersed in a non-aqueous medirboxmethylcellulose, hydroxyethyl cellulose, methyl cellulose, and combinations thereof.

25. The process of claim 1, wherein said spin mix contains a modifier.

26. The process of claim 25, wherein at least one modifier is selected from the group consisting of 1-amino-2-propanol and its isomers, polyethylene glycol, aminoalcohols including triethanolamine, diethanolamine, monoethanolamine, ethoxylated and/or propoxylated amines, aminomorpholine, aminophenol, aminopropanediol, aminomethyl propanol, aminomethylpropanediol, diethylethanolamine, amino pyridine, 2-(2-aminoethylanino)ethanol, (2-(2-aminoethoxy) ethanol, aminoethylpropanediamine, aminomethylbutanol, aminocarboxylic, sulfuric, sulfonic and phosphoric acids, di-, tri- and tetra-amines, polyamines, copolymers of ethylene oxide and propylene oxide, polypropylene glycol and propylene oxide and alkylene oxide adducts, and combinations thereof.

27. The process of claim 25, wherein said modifier is a combination of 1-amino-2-propanol and polyethylene glycol with a molecular weight of from about 1300 to about 1600 in ratios of about 90:

10 to about 10;

90.

28. The process of claim 27, wherein said modifier is a combination of 1-amino-2-propanol and polyethylene glycol with a molecular weight of approximately 1500 in ratios of about 75:

25 to about 25;

75.

29. The process of claim 25, wherein said modifier is an amine that also serves as a dispersing agent.

30. The process of claim 25, wherein said modifier is a polyethylene glycol having a molecular weight of about 1300 to about 1600.

31. The process of claim 25, wherein said spin mix is frozen for a certain duration before spinning.

32. The process of claim 25, wherein the content of said modifier is about 2% to about 10% by weight of cellulose in said carrier solution.

33. The process of claim 32, wherein the content of said modifier is about 4% to about 8% by weight of cellulose is said carrier solution.

34. The process of claim 25, wherein the content of said modifier is above about 2.5% by weight of cellulose in said carrier solution.

35. The process of claim 1, wherein said wet spinning step utilizes a spin bath containing zinc sulfate.

36. The process of claim 1, wherein said spin mix ages from about one hour to about 72 hours before spinning.

37. The process of claim 1, wherein said carrier solution comprises sodium cellulose xanthate.

38. The process of claim 37, wherein said carrier solution contains an excess of a strong base.

39. The process of claim 38, wherein said strong base is NaOH.

40. The process of claim 1, wherein said spinneret contains from 1 to about 20,000 holes each having a diameter of from about 18 to about 400 microns.

41. The process of claim 1, wherein said spin mix is spun into an acidic bath.

42. The process of claim 41, wherein said bath contains an inorganic acid.

43. The process of claim 42, wherein said inorganic acid is selected from the group consisting of sulfuric acid, hydrochloric acid, and phosphoric acid.

44. The process of claim 41, wherein said bath contains an inorganic salt derived from a strong base and a strong acid.

45. The process of claim 44, wherein said salt is selected from sodium sulfate, ammonium sulfate and potassium sulfate.

46. The process of claim 1, wherein said heating of said at least one filament to drive off said carrier is conducted in an oxygen-containing environment at a temperature of from about 200°

C. to about 600°

C.

47. The process of claim 46, wherein said sintering of said refractory particles is conducted in a furnace at a temperature of from about 750°

C. to about 2200°

C.

48. The process of claim 46, wherein said sintering of said refractory particles is conducted under a hydrogen atmosphere.