Refractory nitride, carbide, ternary oxide, nitride/oxide, oxide/carbide, oxycarbide, and oxynitride materials and articles

• US 5,934,900 A
• Filed: 03/24/1997
• Issued: 08/10/1999
• Est. Priority Date: 03/29/1996
• Status: Expired due to Fees

• Current Assignee: Garth W. Billings
• Original Assignee: Integrated Thermal Sciences, Inc.
• Inventors: Billings, Garth W.
• Primary Examiner(s): TURNER, ARCHENE A
• Application Number:
  US08/823,350
• Time in Patent Office: 869 Days
• Field of Search: 428/698, 428/701, 428/469, 428/472, 428/697, 428/699, 51/307, 51/309, 65/374.13, 432/156, 432/262, 432/264
• US Class Current: 432/264
• CPC Class Codes: B22C 1/00 Compositions of refractory mould or core materials; Grain structures thereof refractory materials in general C04B35/00; Chemical or physical features in the formation or manufacture of moulds
• CPC Class Codes: B22C 3/00 Selection of compositions for coating the surfaces of moulds, cores, or patterns
• CPC Class Codes: C04B 35/48 based on zirconium or hafnium oxides, zirconates, zircon or hafnates
• 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 35/5603 with a well-defined oxygen content, e.g. oxycarbides
• CPC Class Codes: C04B 35/58 based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides containing free binder metal C22C29/00
• CPC Class Codes: C04B 35/58028 based on zirconium or hafnium nitrides
• CPC Class Codes: C04B 35/6365 Cellulose or derivatives thereof
• CPC Class Codes: C04B 35/65 Reaction sintering of free metal- or free silicon-containing compositions C04B35/573, C04B35/591 take precedence
• CPC Class Codes: C23C 26/00 Coating not provided for in groups C23C2/00 - C23C24/00
• CPC Class Codes: C23C 30/00 Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process C23C26/00, C23C28/00 take precedence
• CPC Class Codes: Y10T 428/12792 Zn-base component

Abstract

Refractory ceramics and composite materials consisting of nitrides, carbides, mixed carbides and oxides, oxycarbides, mixed nitrides and oxides, and oxynitrides of Group IVB metals Hf, Zr, and Ti, Group IIA metals Be, Mg, Ca, Sr, and Ba, and Group IIIB metals Sc, Y, and lanthanides La through Lu are used to form refractory articles, or as coatings for refractory articles. These materials and articles have high resistance to molten metals, molten salts, erosion, and high temperature corrosive environments, and can be engineered to have desirable thermal and electrical properties. The refractory materials encompass nitrides, carbides, reacted ternary and quaternary oxides, mixed carbides and oxides, oxycarbides, mixed nitrides and oxides, and oxynitrides and have the general chemical formula M_x1 M'"'"'_x2 M"_x3 N_y C_w O_z where M is Hf, Zr, or Ti, M'"'"' is Be, Mg, Ca, Sr, or Ba, M" is Sc, Y, and lanthanides La through Lu, N is nitrogen, C is carbon, O is oxygen. In particular, nitrides having at least 54 atomic percent metal, ternary oxides having no more than 66.6 atomic percent oxygen, and oxynitrides having at least 33.4 atomic percent metal are preferred. Substoichiometric GroupIVB-GroupIIA and Group IVB-GroupIIIB ternary oxides are also preferred.

Claims

1. A refractory material comprising ternary or quaternary oxides having the formula M_x1 M'"'"'_x2 M"_x3 O_z, where M is Hf, Zr, or Ti, M'"'"' is Be, Mg, Ca, Sr, or Ba, M" is Sc, Y, or a lanthanide metal La through Lu, O is oxygen, and x1>

0, x2 and x3≧

0 but x2+x3≠

0, and z>

0, and having a sub-stoichiometric atomic ratio.

2. A refractory material of claim 1 wherein x3=0, comprising ternary oxides having the formula M_x M'"'"'_x2 O_z, where M is a Group IVB metal selected from Hf, Zr, and Ti, and M'"'"' is a Group IIA metal selected from Be, Mg, Ca, Sr, and Ba, and O is oxygen.

3. A refractory material of claim 1 wherein x2=0, comprising ternary oxides having the formula M_x1 M"_x3 O_z, where M is a Group IVB metal selected from Hf, Zr, and Ti, M" is a Group IIIB metal selected from Sc, Y, and lanthanide metals La through Lu, and O is oxygen.

4. A refractory material comprising oxycarbides having the formula M_x1 M'"'"'_x2 M"_x3 C_w O_z, where M is Hf, Zr, or Ti, M'"'"' is Be, Mg, Ca, Sr, or Ba, M" is Sc, Y, or a lanthanide metal La through Lu, C is carbon, O is oxygen, and x1, x2, x3≧

0 but x1+x2+x3≠

0, and both w,z>

0.

5. An article of manufacture comprising a shaped body having at least a surface thereof formed of a refractory material comprising carbides, reacted ternary and quaternary oxides, mixed carbides and oxides, and oxycarbides, of group IVB metals selected from Hf, Zr, and Ti, Group IIA metals selected from Be, Mg, Ca, Sr, and Ba, and Group IIIB metals selected from Sc, Y, and lanthanides La through Lu, and mixtures and composites thereof.

6. The article of claim 5 wherein the shaped body is formed substantially entirely of the refractory material.

7. The article of claim 5 wherein the shaped body is formed of a host material and a coating of the refractory material on the host material.

8. The article of claim 5 wherein the article is selected from crucibles, molds, containment vessels, tubes, probes, stirrers, tools, furnace liners, refractory bricks and mortar.

9. The article of claim 5 for use in containment of or protection from molten metals and molten salts.

10. The article of claim 5 for use in containment of or protection from molten reactive metals selected from Ti, Zr, Hf, V, Nb, Ta, and Be;

molten lanthanide metals;

molten actinide metals;

or molten salts selected from alkali halide salts, alkaline earth halide salts, actinide halide salts, or lanthanide halide salts.

11. The article of claim 5 wherein the refractory material comprises one or more materials having the formula M_x1 M'"'"'_x2 M"_x3 C_w O_x, where M is Hf, Zr, or Ti, M'"'"' is Be, Mg, Ca, Sr, or Ba, M" is Sc, Y, or a lanthanide metal La through Lu, C is carbon, O is oxygen, and each of x1, x2, x3, w, z≧

0 but x1+x2+x3≠

0 and w+z≠

0, and at most only one of x1, x2, x3=0 if w=0.

12. The article of claim 11 wherein the refractory material has the formula M_x1 C_w O_z where M is Hf, Zr, or Ti, and w>

0, and z≧

0.

13. The article of claim 11 having the formula M_x1 C_w :

MO₂.

14. The article of claim 11 wherein the refractory material has the formula M_x1 M'"'"'_x2 O_z where M is Hf, Zr, or Ti, and M'"'"' is Be, Mg, Ca, Sr, or Ba, and O is oxygen.

15. The article of claim 14 wherein the refractory material has a sub-stoichiometric composition.

16. The article of claim 6 wherein the refractory material has the formula M_x1 M'"'"'_x2 M"_x3 C_w O_z where M is Hf, Zr, or Ti, M'"'"' is Be, Mg, Ca, Sr, or Ba, M" is Sc, Y, and lanthanide metals La through Lu, C is carbon, O is oxygen, and x1>

0, x2 and x3≧

0, and w and z≧

0 but w+z≠

0, and x2+x3≠

0 if w=0.

17. The article of claim 16 wherein the refractory material has a sub-stoichiometric composition.

18. The article of claim 11 wherein the refractory material has the formula M_x1 M"_x3 O_z where M is Hf, Zr, or Ti, and M" is Sc, Y, and lanthanide metals La through Lu, and O is oxygen.

19. The article of claim 18 wherein the refractory material has a sub-stoichiometric composition.

20. The article of claim 18 for use in containment of or protection from molten metals and molten salts.

21. The article of claim 18 for use in containment of or protection from molten reactive metals selected from Ti, Zr, Hf, V, Nb, Ta, and Be;

molten lanthanide metals;

molten actinide metals;

or molten salts selected from alkali halide salts, alkaline earth halide salts, actinide halide salts, or lanthanide halide salts.