Refractory materials

Abstract

Refractory materials are provided which contain P 2 O 5 /R 2 O 3 constituents, where R is Y, Sc, Er, Lu, Yb, Tm, Ho, Dy, Tb, Gd, or a combination thereof, and/or V 2 O 5 /R′ 2 O 3 constituents where R′ is Y, Sc, one or more rare earth elements, or a combination thereof. In certain embodiments, the refractory materials are xenotime-type materials and/or xenotime-stabilized zircon-type materials. The refractory materials can be used in the manufacture of glass and glass-ceramics. For example, the refractory materials, especially those that contain P 2 O 5 /R 2 O 3 constituents, can be used as forming structures (“isopipes”) in the fusion process for making flat sheets of glass such as the glass sheets used as substrates in the manufacture of flat panel displays.

What is claimed is: 
     
       1. Apparatus for producing a glass or a glass-ceramic, said apparatus comprising a refractory body having a surface adapted to contact the glass or the glass-ceramic when the glass or the glass-ceramic is in a molten state, the refractory body comprising a phase which, on an oxide basis, consists of:
 (i) 2.5-13.0 mole percent P 2 O 5  (the first constituent); 
 (ii) 2.5-13.0 mole percent Y 2 O 3 , Sc 2 O 3 , Er 2 O 3 , Lu 2 O 3 , Yb 2 O 3 , Tm 2 O 3 , Ho 2 O 3 , Dy 2 O 3 , Tb 2 O 3 , Gd 2 O 3 , or a combination thereof (the second constituent); and 
 (iii) the remainder of the phase being ZrSiO 4  HfSiO 4  ThSiO 4 , or a combination thereof; 
 wherein:
 (a) (i) and (ii) are in a dissolved state in (iii), 
 (b) the refractory body has a volume of at least 200 cubic centimeters, and 
 (c) the phase comprises at least 90 volume percent of the refractory body. 
 
 
     
     
       2. The apparatus of  claim 1  wherein the refractory body is at least 50 volume percent of the apparatus. 
     
     
       3. The apparatus of  claim 1  wherein the refractory body is the entire apparatus. 
     
     
       4. The apparatus of  claim 1  wherein:
 (i) the apparatus comprises a core and a coating on the core, said core and coating having different compositions; 
 (ii) the surface adapted to contact the molten glass or the molten glass-ceramic is a surface, or a portion of a surface, of the coating; and 
 (iii) the refractory body comprises at least a portion of the coating. 
 
     
     
       5. The apparatus of  claim 1  wherein the surface adapted to contact the molten glass or the molten glass-ceramic directs a flow of the molten glass or the molten glass-ceramic. 
     
     
       6. The apparatus of  claim 5  wherein the apparatus is a forming trough of a fusion process. 
     
     
       7. The apparatus of  claim 6  wherein the refractory body is the entire trough. 
     
     
       8. The apparatus of  claim 6  wherein the forming trough has a length sufficient to produce sheets of the glass or the glass-ceramic having a width of at least 2.5 meters. 
     
     
       9. The apparatus of  claim 1  wherein the second constituent is Y 2 O 3 . 
     
     
       10. The apparatus of  claim 9  wherein the first and second constituents substantially satisfy the compositional formula YPO 4 . 
     
     
       11. The apparatus of  claim 1  wherein the remainder of the phase substantially satisfies the compositional formula ZrSiO 4 . 
     
     
       12. The apparatus of  claim 1  wherein on an oxide basis, the phase has at least 5 mole percent of the first constituent and at least 5 mole percent of the second constituent. 
     
     
       13. The apparatus of  claim 1  wherein on an oxide basis, the phase has 13 mole percent of the first constituent and 13 mole percent of the second constituent. 
     
     
       14. The apparatus of  claim 1  wherein the first and second constituents substantially satisfy the compositional formula YPO 4  and the remainder of the phase substantially satisfies the compositional formula ZrSiO 4 . 
     
     
       15. A method for producing a glass or a glass-ceramic comprising:
 (I) providing apparatus for producing the glass or the glass-ceramic, wherein: 
 (A) the apparatus comprises a refractory body having a surface adapted to contact the glass or the glass-ceramic when the glass or the glass-ceramic is in a molten state; and 
 (B) the refractory body comprises a phase which, on an oxide basis, consists of: 
 (i) 2.5-13.0 mole percent P 2 O 5  (the first constituent); 
 (ii) 2.5-13.0 mole percent Y 2 O 3 , Sc 2 O 3 , Er 2 O 3 , Lu 2 O 3 , Yb 2 O 3 , Tm 2 O 3 , Ho 2 O 3 , Dy 2 O 3 , Tb 2 O 3 , Gd 2 O 3 , or a combination thereof (the second constituent); and 
 (iii) the remainder of the phase being ZrSiO 4  HfSiO 4  ThSiO 4 , or a combination thereof; 
 wherein:
 (a) (i) and (ii) are in a dissolved state in (iii), 
 (b) the refractory body has a volume of at least 200 cubic centimeters, and 
 (c) the phase comprises at least 90 volume percent of the refractory body; and 
 
 (II) contacting at least a portion of the surface with the glass or the glass-ceramic in a molten state. 
 
     
     
       16. The method of  claim 15  wherein in step (II), the glass or glass-ceramic in a molten state has a temperature above 1280° C. 
     
     
       17. The method of  claim 15  wherein the refractory body is the entire apparatus. 
     
     
       18. The method of  claim 15  wherein the surface adapted to contact the molten glass or the molten glass-ceramic directs a flow of the molten glass or the molten glass-ceramic. 
     
     
       19. The method of  claim 18  wherein the apparatus is a forming trough of a fusion process. 
     
     
       20. The method of  claim 19  wherein the refractory body is the entire trough. 
     
     
       21. The method of  claim 19  wherein the forming trough has a length sufficient to produce sheets of the glass or the glass-ceramic having a width of at least 2.5 meters. 
     
     
       22. The method of  claim 15  wherein the second constituent is Y 2 O 3 . 
     
     
       23. The method of  claim 22  wherein the first and second constituents substantially satisfy the compositional formula YPO 4 . 
     
     
       24. The method of  claim 15  wherein the remainder of the phase substantially satisfies the compositional formula ZrSiO 4 . 
     
     
       25. The method of  claim 15  wherein on an oxide basis, the phase has at least 5 mole percent of the first constituent and at least 5 mole percent of the second constituent. 
     
     
       26. The method of  claim 15  wherein the first and second constituents substantially satisfy the compositional formula YPO 4  and the remainder of the phase substantially satisfies the compositional formula ZrSiO 4 . 
     
     
       27. The method of claim 15 wherein the apparatus is formed by a process which comprises firing a green body and said firing is performed on platinum or zirconia. 
     
     
       28. Apparatus for producing a glass or a glass-ceramic, said apparatus comprising a refractory body having a surface adapted to contact the glass or the glass-ceramic when the glass or the glass-ceramic is in a molten state, the refractory body being characterized by at least one of the following:
 (1) the refractory body comprises a phase which, on an oxide basis, consists of:
 (i) 2.5-13.0 mole percent P 2 O 5 ; 
 (ii) 2.5-13.0 mole percent Y 2 O 3 , Sc 2 O 3 , Er 2 O 3 , Lu 2 O 3 , Yb 2 O 3 , Tm 2 O 3 , Ho 2 O 3 , Dy 2 O 3 , Tb 2 O 3 , Gd 2 O 3 , or a combination thereof; and 
 (iii) the remainder of the phase being ZrSiO 4 , HfSiO 4 , ThSiO 4 , or a combination thereof; 
 wherein:
 (a) (i) and (ii) are in a dissolved state in (iii), 
 (b) the refractory body has a volume of at least 200 cubic centimeters, and 
 (c) the phase comprises at least 90 volume percent of the refractory body; 
 
   (2) the refractory body comprises a phase which, on an oxide basis, comprises:
 (i) at least 30 mole percent P 2 O 5 ; and 
 (ii) at least 30 mole percent Y 2 O 3 , Sc 2 O 3 , Er 2 O 3 , Lu 2 O 3 , Yb 2 O 3 , Tm 2 O 3 , Ho 2 O 3 , Dy 2 O 3 , Tb 2 O 3 , Gd 2 O 3 , or a combination thereof; 
 wherein:
 (a) the refractory body has a volume of at least 200 cubic centimeters, and 
 (b) the phase comprises at least 90 volume percent of the refractory body; and/or 
 
   (3) the refractory body comprises a Phase I and a Phase II wherein:
 (a) Phase I, on an oxide basis, consists of:
 (i) 2.5-13.0 mole percent P 2 O 5 ; 
 (ii) 2.5-13.0 mole percent Y 2 O 3 , Sc 2 O 3 , Er 2 O 3 , Lu 2 O 3 , Yb 2 O 3 , Tm 2 O 3 , Ho 2 O 3 , Dy 2 O 3 , Tb 2 O 3 , Gd 2 O 3 , or a combination thereof; and 
 (iii) the remainder of the phase being ZrSiO 4 , HfSiO 4 , ThSiO 4 , or a combination thereof; 
 wherein (i) and (ii) are in a dissolved state in (iii); 
 
 (b) Phase II, on an oxide basis, comprises:
 (i) at least 30 mole percent P 2 O 5 ; and 
 (ii) at least 30 mole percent Y 2 O 3 , Sc 2 O 3 , Er 2 O 3 , Lu 2 O 3 , Yb 2 O 3 , Tm 2 O 3 , Ho 2 O 3 , Dy 2 O 3 , Tb 2 O 3 , Gd 2 O 3 , or a combination thereof; 
 
 (c) the refractory body has a volume of at least 200 cubic centimeters, and 
 (d) Phase I and Phase II together comprise at least 90 volume percent of the refractory body. 
   
     
     
       29. The apparatus of claim 28 wherein the apparatus has an operating temperature above 1280° C. 
     
     
       30. The apparatus of claim 28 wherein the surface adapted to contact the molten glass or the molten glass-ceramic directs a flow of the molten glass or the molten glass-ceramic. 
     
     
       31. The apparatus of claim 30 wherein the apparatus is a forming trough of a fusion process. 
     
     
       32. The apparatus of claim 31 wherein the forming trough has an operating temperature above 1280° C. 
     
     
       33. The apparatus of claim 31 wherein the forming trough has a length sufficient to produce sheets of the glass or the glass-ceramic having a width of at least 2.5 meters. 
     
     
       34. The apparatus of claim 33 wherein the forming trough has an operating temperature above 1280° C. 
     
     
       35. A method for producing a glass or a glass-ceramic comprising: 
       (I) providing apparatus for producing the glass or the glass-ceramic, wherein:
 (A) the apparatus comprises a refractory body having a surface adapted to contact the glass or the glass-ceramic when the glass or the glass-ceramic is in a molten state; and 
 (B) the refractory body is characterized by at least one of the following: 
 (1) the refractory body comprises a phase which, on an oxide basis, consists of:
 (i) 2.5-13.0 mole percent P 2 O 5 ; 
 (ii) 2.5-13.0 mole percent Y 2 O 3 , Sc 2 O 3 , Er 2 O 3 , Lu 2 O 3 , Yb 2 O 3 , Tm 2 O 3 , Ho 2 O 3 , Dy 2 O 3 , Tb 2 O 3 , Gd 2 O 3 , or a combination thereof; and 
 (iii) the remainder of the phase being ZrSiO 4 , HfSiO 4 , ThSiO 4 , or a combination thereof; 
 wherein:
 (a) (i) and (ii) are in a dissolved state in (iii), 
 (b) the refractory body has a volume of at least 200 cubic centimeters, and 
 (c) the phase comprises at least 90 volume percent of the refractory body; 
 
 
 (2) the refractory body comprises a phase which, on an oxide basis, comprises:
 (i) at least 30 mole percent P 2 O 5 ; and 
 (ii) at least 30 mole percent Y 2 O 3 , Sc 2 O 3 , Er 2 O 3 , Lu 2 O 3 , Yb 2 O 3 , Tm 2 O 3 , Ho 2 O 3 , Dy 2 O 3 , Tb 2 O 3 , Gd 2 O 3 , or a combination thereof; 
 wherein:
 (a) the refractory body has a volume of at least 200 cubic centimeters, and 
 (b) the phase comprises at least 90 volume percent of the refractory body; and/or 
 
 
 (3) the refractory body comprises a Phase I and a Phase II wherein:
 (a) Phase I, on an oxide basis, consists of:
 (i) 2.5-13.0 mole percent P 2 O 5 ; 
 (ii) 2.5-13.0 mole percent Y 2 O 3 , Sc 2 O 3 , Er 2 O 3 , Lu 2 O 3 , Yb 2 O 3 , Tm 2 O 3 , Ho 2 O 3 , Dy 2 O 3 , Tb 2 O 3 , Gd 2 O 3 , or a combination thereof; and 
 (iii) the remainder of the phase being ZrSiO 4 , HfSiO 4 , ThSiO 4 , or a combination thereof; 
 wherein (i) and (ii) are in a dissolved state in (iii); 
 
 (b) Phase II, on an oxide basis, comprises:
 (i) at least 30 mole percent P 2 O 5 ; and 
 (ii) at least 30 mole percent Y 2 O 3 , Sc 2 O 3 , Er 2 O 3 , Lu 2 O 3 , Yb 2 O 3 , Tm 2 O 3 , Ho 2 O 3 , Dy 2 O 3 , Tb 2 O 3 , Gd 2 O 3 , or a combination thereof; 
 
 (c) the refractory body has a volume of at least 200 cubic centimeters, and 
 (d) Phase I and Phase II together comprise at least 90 volume percent of the refractory body; and 
 
 
       (II) contacting the surface adapted to contact the molten glass or the molten glass-ceramic with the glass or the glass-ceramic in a molten state. 
     
     
       36. The method of claim 35 wherein in step (II), the glass or glass-ceramic in a molten state has a temperature above 1280° C. 
     
     
       37. The method of claim 35 wherein the surface adapted to contact the molten glass or the molten glass-ceramic directs a flow of the molten glass or the molten glass-ceramic. 
     
     
       38. The method of claim 37 wherein the apparatus is a forming trough of a fusion process. 
     
     
       39. The method of claim 38 wherein in step (II), the glass or glass-ceramic in a molten state has a temperature above 1280° C. 
     
     
       40. The method of claim 38 wherein the forming trough has a length sufficient to produce sheets of the glass or the glass-ceramic having a width of at least 2.5 meters. 
     
     
       41. The method of claim 40 wherein in step (II), the glass or glass-ceramic in a molten state has a temperature above 1280° C. 
     
     
       42. The method of claim 38 wherein sheets of the glass or the glass-ceramic produced using the forming trough have a defect level that is less than or equal to 0.1 defects per pound. 
     
     
       43. The method of claim 35 wherein the apparatus is formed by a process which comprises firing a green body and said firing is performed on platinum or zirconia.