Carbon-containing monolithic glasses and ceramics prepared by a sol-gel process

Claim 1

A method of preparing a carbon-containing, monolithic glassy ceramic which comprises drying and pyrolyzing at a temperature of 500° C. to 1500° C. in an inert atmosphere, or a vacuum, until a carbon-containing, monolithic glassy ceramic is obtained, a product comprising a stable gel selected from a group consisting essentially of (A) a gel obtained from a sol of an organosilsesquioxane having the unit formula RSiO.sub.3/2 wherein R is selected from a group consisting essentially of (a) CH 2 ═CH--; (b) CH 2 ═CHCH 2 --; (c) C 6 H 5 --; (d) alkyl radicals of 1 to 4 carbon atoms; (e) substituted monovalent organic radicals selected from the group consisting of CH 2 ═CHC(CH 3 )COO(CH 2 ) 3 --, ##STR2## HS(CH 2 ) 3 --, Cl(CH 2 ) 3 --, and NH 2 (CH 2 ) 2 NH(CH 2 ) 3 --; and (f) mixtures of (a), (b), (c), (d), and (e); (B) a gel obtained from a mixture of a sol of an organosilsesquioxane from (A), and a colloidal metal oxide or a mixture of colloidal metal oxides selected from a group consisting essentially of (i) SiO 2 (ii) Al 2 O 3 (iii) ZrO 2 (iv) TiO 2 (v) SnO 2 (vi) ZrSiO 4 (vii) B 2 O 3 (viii) La 2 O 3 and (ix) Sb 2 O 5 wherein said gel contains at least 10 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal oxide; (C) a gel obtained from a mixture of a sol of an organosilsesquioxanes from (A), and a metal alkoxide, or a mixture of metal alkoxides having the general formula M(OR').sub.x wherein M is any metal from a metal alkoxide which hydrolyzes and polymerizes in the presence of water, R' is an alkyl radical of 1 to 4 carbon atoms and x has a value equivalent to the metal ion valence wherein said gel contains at least about 50 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal M in said gel.

Claim 2

A method of preparing a carbon-containing, monolithic glassy ceramic which comprises drying and pyrolyzing at a temperature of 500° C. to 1500° C. in an inert atmosphere, or a vacuum, until a carbon-containing, monolithic glassy ceramic is obtained, a product comprising a stable gel selected from a group consisting essentially of (A) a gel obtained from a sol of an organosilsesquioxane having the unit formula RSiO.sub.3/2 wherein R is selected from a group consisting essentially of (a) CH 2 ═CH--; (b) CH 2 ═CHCH 2 --; (c) C 6 H 5 --; (d) alkyl radicals of 1 to 4 carbon atoms; (e) substituted monovalent organic radicals selected from the group consisting of CH 2 ═CHC(CH 3 )COO(CH 2 ) 3 --, ##STR2## HS(CH 2 ) 3 --, Cl(CH 2 ) 3 --, and NH 2 (CH 2 ) 2 NH(CH 2 ) 3 --; and (f) mixtures of (a), (b), (c), (d), and (e); (B) a gel obtained from a mixture of a sol of an organosilsesquioxane from (A), and a colloidal metal oxide or a mixture of colloidal metal oxides selected from a group consisting essentially of (i) SiO 2 (ii) Al 2 O 3 (iii) ZrO 2 (iv) TiO 2 (v) SnO 2 (vi) ZrSiO 4 (vii) B 2 O 3 (viii) La 2 O 3 and (ix) Sb 2 O 5 wherein said gel contains at least 10 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal oxide; (C) a gel obtained from a mixture of a sol of an organosilsesquioxanes from (A), and a metal alkoxide, or a mixture of metal alkoxides having the general formula M(OR').sub.x wherein M is any metal from a metal alkoxide which hydrolyzes and polymerizes in the presence of water, R' is an alkyl radical of 1 to 4 carbon atoms and x has a value equivalent to the metal ion valence wherein said gel contains at least about 50 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal M in said gel.

Claim 42

A method of forming a carbon-containing, monolithic glassy ceramic coating on a solid substrate which comprises (I) coating a solid substrate with a sol selected from a group consisting essentially of (A) a sol of organosilsesquioxane having the unit formula RSiO.sub.3/2 wherein R is selected from a group consisting essentially of (a) CH 2 ═CH--; (b) CH 2 ═CHCH 2 --; (c) C 6 H 5 --; (d) alkyl radicals of 1 to 4 carbon atoms; (e) substituted monovalent organic radicals selected from the group consisting of CH 2 ═CHC(CH 3 )COO(CH 2 ) 3 --, ##STR3## HS(CH 2 ) 3 --, Cl(CH 2 ) 3 --, and NH 2 (CH 2 ) 2 NH(CH 2 ) 3 --; and (f) mixtures of (a), (b), (c), (d), and (e); (B) a mixture of a sol of an organosilsesquioxane from (A), and a colloidal metal oxide or a mixture of colloidal metal oxides selected from a group consisting essentially of (i) SiO 2 (ii) Al 2 O 3 (iii) ZrO 2 (iv) TiO 2 (v) SnO 2 (vi) ZrSiO 4 (vii) B 2 O 3 (viii) La 2 O 3 and (ix) Sb 2 O 5 wherein said gel contains at least 10 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal oxide; (C) a mixture of a sol of an organosilsesquioxane from (A), and a metal alkoxide, or a mixture of metal alkoxides having the general formula M(OR').sub.x wherein M is any metal from a metal alkoxide which hydrolyzes and polymerizes in the presence of water, R' is an alkyl radical of 1 to 4 carbon atoms and x has a value equivalent to the metal ion valence wherein said gel contains at least about 50 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal M in said gel; (II) gelling the sol while the sol is on the solid substrate; (III) drying the gel to remove volatile materials; (IV) heat treating the gel to remove higher boiling volatiles; and (V) pyrolyzing the dried and heat treated gel at a temperature of 500° C. to 1500° C. in an inert atmosphere or a vacuum until a carbon-containing, monolithic glassy ceramic coated substrate is obtained.

Claim 43

A method of forming a carbon-containing, monolithic glassy ceramic coating on a solid substrate which comprises (I) coating a solid substrate with a sol selected from a group consisting essentially of (A) a sol of organosilsesquioxane having the unit formula RSiO.sub.3/2 wherein R is selected from a group consisting essentially of (a) CH 2 ═CH--; (b) CH 2 ═CHCH 2 --; (c) C 6 H 5 --; (d) alkyl radicals of 1 to 4 carbon atoms; (e) substituted monovalent organic radicals selected from the group consisting of CH 2 ═CHC(CH 3 )COO(CH 2 ) 3 --, ##STR3## HS(CH 2 ) 3 --, Cl(CH 2 ) 3 --, and NH 2 (CH 2 ) 2 NH(CH 2 ) 3 --; and (f) mixtures of (a), (b), (c), (d), and (e); (B) a mixture of a sol of an organosilsesquioxane from (A), and a colloidal metal oxide or a mixture of colloidal metal oxides selected from a group consisting essentially of (i) SiO 2 (ii) Al 2 O 3 (iii) ZrO 2 (iv) TiO 2 (v) SnO 2 (vi) ZrSiO 4 (vii) B 2 O 3 (viii) La 2 O 3 and (ix) Sb 2 O 5 wherein said gel contains at least 10 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal oxide; (C) a mixture of a sol of an organosilsesquioxane from (A), and a metal alkoxide, or a mixture of metal alkoxides having the general formula M(OR').sub.x wherein M is any metal from a metal alkoxide which hydrolyzes and polymerizes in the presence of water, R' is an alkyl radical of 1 to 4 carbon atoms and x has a value equivalent to the metal ion valence wherein said gel contains at least about 50 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal M in said gel; (II) gelling the sol while the sol is on the solid substrate; (III) drying the gel to remove volatile materials; (IV) heat treating the gel to remove higher boiling volatiles; and (V) pyrolyzing the dried and heat treated gel at a temperature of 500° C. to 1500° C. in an inert atmosphere or a vacuum until a carbon-containing, monolithic glassy ceramic coated substrate is obtained.

Claim 79

A method of forming a carbon-containing, monolithic glassy ceramic coating on a solid substrate which comprises (I) coating a solid substrate with a stable gel selected from a group consisting essentially of (A) a gel obtained from a sol of an organosilsesquioxane having the unit formula RSiO.sub.3/2 wherein R is selected from a group consisting essentially of (a) CH 2 ═CH--; (b) CH 2 ═CHCH 2 --; (c) C 6 H 5 --; (d) alkyl radicals of 1 to 4 carbon atoms; (e) substituted monovalent organic radicals selected from the group consisting of CH 2 ═CHC(CH 3 )COO(CH 2 ) 3 --, ##STR4## HS(CH 2 ) 3 --, Cl(CH 2 ) 3 --, and NH 2 (CH 2 ) 2 NH(CH 2 ) 3 --; and (f) mixtures of (a), (b), (c), (d), and (e); (B) a gel obtained from a mixture of a sol of an organosilsesquioxane from (A), and a colloidal metal oxide or a mixture of colloidal metal oxides selected from a group consisting essentially of (i) SiO 2 (ii) Al 2 O 3 (iii) ZrO 2 (vi) ZrSiO 4 (vii) B 2 O 3 (viii) La 2 O 3 and (iv) TiO 2 (v) SnO 2 (ix) Sb 2 O 5 wherein said gel contains at least 10 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal oxide; (C) a gel obtained from a mixture of a sol of an organosilsesquioxane from (A), and a metal alkoxide, or a mixture of metal alkoxides having the general formula M(OR').sub.x wherein M is any metal from a metal alkoxide which hydrolyzes and polymerizes in the presence of water, R' is an alkyl radical of 1 to 4 carbon atoms and x has a value equivalent to the metal ion valence wherein said gel contains at least about 50 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal M in said gel; (II) drying the gel to remove volatile materials; (III) heat treating the gel to remove higher boiling volatiles; and (IV) pyrolyzing the dried and heat treated gel at a temperature of 500° C. to 1500° C. in an inert atmosphere or a vacuum until a carbon-containing, monolithic glassy ceramic coated substrate is obtained.

Claim 80

A method of forming a carbon-containing, monolithic glassy ceramic coating on a solid substrate which comprises (I) coating a solid substrate with a stable gel selected from a group consisting essentially of (A) a gel obtained from a sol of an organosilsesquioxane having the unit formula RSiO.sub.3/2 wherein R is selected from a group consisting essentially of (a) CH 2 ═CH--; (b) CH 2 ═CHCH 2 --; (c) C 6 H 5 --; (d) alkyl radicals of 1 to 4 carbon atoms; (e) substituted monovalent organic radicals selected from the group consisting of CH 2 ═CHC(CH 3 )COO(CH 2 ) 3 --, ##STR4## HS(CH 2 ) 3 --, Cl(CH 2 ) 3 --, and NH 2 (CH 2 ) 2 NH(CH 2 ) 3 --; and (f) mixtures of (a), (b), (c), (d), and (e); (B) a gel obtained from a mixture of a sol of an organosilsesquioxane from (A), and a colloidal metal oxide or a mixture of colloidal metal oxides selected from a group consisting essentially of (i) SiO 2 (ii) Al 2 O 3 (iii) ZrO 2 (vi) ZrSiO 4 (vii) B 2 O 3 (viii) La 2 O 3 and (iv) TiO 2 (v) SnO 2 (ix) Sb 2 O 5 wherein said gel contains at least 10 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal oxide; (C) a gel obtained from a mixture of a sol of an organosilsesquioxane from (A), and a metal alkoxide, or a mixture of metal alkoxides having the general formula M(OR').sub.x wherein M is any metal from a metal alkoxide which hydrolyzes and polymerizes in the presence of water, R' is an alkyl radical of 1 to 4 carbon atoms and x has a value equivalent to the metal ion valence wherein said gel contains at least about 50 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal M in said gel; (II) drying the gel to remove volatile materials; (III) heat treating the gel to remove higher boiling volatiles; and (IV) pyrolyzing the dried and heat treated gel at a temperature of 500° C. to 1500° C. in an inert atmosphere or a vacuum until a carbon-containing, monolithic glassy ceramic coated substrate is obtained.

Claim 89

A method of preparing a carbon-containing, monolithic glassy ceramic which comprises drying and pyrolyzing at a temperature of 500° C. to 1500° C. in an inert atmosphere, or a vacuum, until a carbon-containing, monolithic glassy ceramic is obtained, a product comprising a mixture of (A) a stable gel obtained from a sol of an organosilsesquioxane having the unit formula RSiO.sub.3/2 wherein R is selected from a group consisting essentially of (a) CH 2 ═CH--; (b) CH 2 ═CHCH 2 --; (c) C 6 H 5 --; (d) alkyl radicals of 1 to 4 carbon atoms; (e) substituted monovalent organic radicals selected from the group consisting of CH 2 ═CHC(CH 3 )COO(CH 2 ) 3 --, ##STR5## HS(CH 2 ) 3 --, Cl(CH 2 ) 3 --, and NH 2 (CH 2 ) 2 NH(CH 2 ) 3 --; and (f) mixtures of (a), (b), (c), (d), and (e); (B) a colloidal metal oxide or a mixture of colloidal metal oxides selected from a group consisting essentially of (i) SiO 2 (ii) Al 2 O 3 (iii) ZrO 2 (iv) TiO 2 (v) SnO 2 (vi) ZrSiO 4 (vii) B 2 O 3 (viii) La 2 O 3 and (ix) Sb 2 O 5 wherein said gel contains at least 10 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal oxide; (C) a metal alkoxide, or a mixture of metal alkoxides having the general formula M(OR').sub.x wherein M is any metal from a metal alkoxide which hydrolyzes and polymerizes in the presence of water, R' is an alkyl radical of 1 to 4 carbon atoms and x has a value equivalent to the metal ion valence, wherein said gel contains at least about 50 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal M in said gel.

Claim 90

A method of preparing a carbon-containing, monolithic glassy ceramic which comprises drying and pyrolyzing at a temperature of 500° C. to 1500° C. in an inert atmosphere, or a vacuum, until a carbon-containing, monolithic glassy ceramic is obtained, a product comprising a mixture of (A) a stable gel obtained from a sol of an organosilsesquioxane having the unit formula RSiO.sub.3/2 wherein R is selected from a group consisting essentially of (a) CH 2 ═CH--; (b) CH 2 ═CHCH 2 --; (c) C 6 H 5 --; (d) alkyl radicals of 1 to 4 carbon atoms; (e) substituted monovalent organic radicals selected from the group consisting of CH 2 ═CHC(CH 3 )COO(CH 2 ) 3 --, ##STR5## HS(CH 2 ) 3 --, Cl(CH 2 ) 3 --, and NH 2 (CH 2 ) 2 NH(CH 2 ) 3 --; and (f) mixtures of (a), (b), (c), (d), and (e); (B) a colloidal metal oxide or a mixture of colloidal metal oxides selected from a group consisting essentially of (i) SiO 2 (ii) Al 2 O 3 (iii) ZrO 2 (iv) TiO 2 (v) SnO 2 (vi) ZrSiO 4 (vii) B 2 O 3 (viii) La 2 O 3 and (ix) Sb 2 O 5 wherein said gel contains at least 10 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal oxide; (C) a metal alkoxide, or a mixture of metal alkoxides having the general formula M(OR').sub.x wherein M is any metal from a metal alkoxide which hydrolyzes and polymerizes in the presence of water, R' is an alkyl radical of 1 to 4 carbon atoms and x has a value equivalent to the metal ion valence, wherein said gel contains at least about 50 weight percent of said organosilsesquioxane from (A) based on the total weight of said organosilsesquioxane and said metal M in said gel.