Method for making photosensitive colored glasses

Claim 1

A method for making a glass article wherein at least a portion thereof is integrally colored by silver which comprises the steps: a. melting a batch for a glass containing the constituents of alkali fluoride, the constituents of at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide, and about 0.0 to 0.2% CeO 2 ; b. forming said melt into a glass article; c. exposing at least a portion of said article to high energy or actinic radiation selected from the group consisting of high velocity electrons, X-radiations, and ultra-violet radiations; d. heating at least said exposed portion of the article to a temperature between about the transformation range and the softening point of the glass for a period of time sufficient to cause nucleation and growth of microcrystals of sodium fluoride containing at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide to occur within said exposed portion; e. re-exposing at least said previously-exposed portion of said article to said high energy or actinic radiation; f. heating at least said re-exposed portion of said article to a temperature between the transformation range and the softening point of the glass for a period of time sufficient to cause metallic silver to be deposited as discrete colloidal particles less than about 200A in the smallest dimension, and/or deposited within said microcrystals, the sivler-containing part of the microcrystals being less than about 200A in the smallest dimension, and/or deposited on the surface of said microcrystals, the portion of the microcrystal coated with silver being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005% by volume; and then g. cooling said article to room temperature.

Claim 2

A method for making a glass article wherein at least a portion thereof is integrally colored by silver which comprises the steps: a. melting a batch for a glass containing the constituents of alkali fluoride, the constituents of at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide, and about 0.0 to 0.2% CeO 2 ; b. forming said melt into a glass article; c. exposing at least a portion of said article to high energy or actinic radiation selected from the group consisting of high velocity electrons, X-radiations, and ultra-violet radiations; d. heating at least said exposed portion of the article to a temperature between about the transformation range and the softening point of the glass for a period of time sufficient to cause nucleation and growth of microcrystals of sodium fluoride containing at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide to occur within said exposed portion; e. re-exposing at least said previously-exposed portion of said article to said high energy or actinic radiation; f. heating at least said re-exposed portion of said article to a temperature between the transformation range and the softening point of the glass for a period of time sufficient to cause metallic silver to be deposited as discrete colloidal particles less than about 200A in the smallest dimension, and/or deposited within said microcrystals, the sivler-containing part of the microcrystals being less than about 200A in the smallest dimension, and/or deposited on the surface of said microcrystals, the portion of the microcrystal coated with silver being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005% by volume; and then g. cooling said article to room temperature.

Claim 13

A method for making a glass article wherein at least a portion thereof is integrally colored by silver which comprises the steps: a. contacting the surface of a glass article containing Na 2 O, F, at least one halide selected from the group consisting of Cl, Br, and I, "and about 0 to 0.2% CeO 2 ." with a silver-containing material; b. heating said glass article and said silver-containing material in contact therewith for a sufficient length of time to effect an exchange of silver ions for sodium ions in at least the surface of the glass; c. exposing at least a portion of said article to high energy or actinic radiation selected from the group consisting of high velocity electrons, X-radiations, and ultra-violet radiations; d. heating at least said exposed portion of the article to a temperature between about the transformation range and the softening point of the glass for a period of time sufficient to cause nucleation and growth of microcrystals of sodium fluoride containing at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide to occur within said exposed portion; e. re-exposing at least said previously-exposed portion of said article to high energy or actinic radiation selected from the group consisting of high velocity electrons, X-radiations, and ultra-violet radiations; f. heating at least said re-exposed portion of said article to a temperature between the transformation range and the softening point of the glass for a period of time sufficient to cause metallic silver to be deposited as discrete colloidal particles less than 200A in the smallest dimension, and/or deposited within said microcrystals, the silver-containing part of the microcrystal being less than about 200A in the smallest dimension, and/or deposited on the surface of said microcrystals, the portion of the microcrystal coated with silver being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005% by volume; g. cooling said article to room temperature.

Claim 14

A method for making a glass article wherein at least a portion thereof is integrally colored by silver which comprises the steps: a. contacting the surface of a glass article containing Na 2 O, F, at least one halide selected from the group consisting of Cl, Br, and I, "and about 0 to 0.2% CeO 2 ." with a silver-containing material; b. heating said glass article and said silver-containing material in contact therewith for a sufficient length of time to effect an exchange of silver ions for sodium ions in at least the surface of the glass; c. exposing at least a portion of said article to high energy or actinic radiation selected from the group consisting of high velocity electrons, X-radiations, and ultra-violet radiations; d. heating at least said exposed portion of the article to a temperature between about the transformation range and the softening point of the glass for a period of time sufficient to cause nucleation and growth of microcrystals of sodium fluoride containing at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide to occur within said exposed portion; e. re-exposing at least said previously-exposed portion of said article to high energy or actinic radiation selected from the group consisting of high velocity electrons, X-radiations, and ultra-violet radiations; f. heating at least said re-exposed portion of said article to a temperature between the transformation range and the softening point of the glass for a period of time sufficient to cause metallic silver to be deposited as discrete colloidal particles less than 200A in the smallest dimension, and/or deposited within said microcrystals, the silver-containing part of the microcrystal being less than about 200A in the smallest dimension, and/or deposited on the surface of said microcrystals, the portion of the microcrystal coated with silver being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005% by volume; g. cooling said article to room temperature.

Claim 17

A method for coating a glass, glass-ceramic, ceramic, or metal substrate with a colored glaze comprising the steps of: a. melting a batch for a glass containing the constituents of sodium fluoride and the constituents of at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide; and about 0-0.2% CeO 2 ; b. forming said melt into a glass and comminuting said glass into a frit; c. applying said frit to the substrate to be coated; d. firing the coated substrate at a temperature sufficient to sinter the frit into a tightly-adherent glaze; e. exposing at least a portion of said glazed substrate to high energy or actinic radiation, selected from the group consisting of high velocity electrons, X-radiations, and ultra-violet radiations; f. heating at least said exposed portion of the glazed substrate to a temperature between about the transformation range and the softening point of the glaze for a period of time sufficient to cause nucleation and growth of microcrystals of sodium fluoride containing at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide to occur within said exposed portion; g. re-exposing at least said previously-exposed portion of said glazed substrate to high energy or actinic radiation, selected from the group consisting of high velocity electrons, X-radiations, and ultra-violet radiations; h. heating at least said re-exposed portion of the glazed substrate to a temperature between the transformation range and the softening point of the glaze for a period of time sufficient to cause metallic silver to be deposited as discrete colloidal particles less than 200A in the smallest dimension, and/or deposited within said microcrystals, the silver-containing part of the microcrystal being less than about 200A in the smallest dimension, and/or deposited on the surface of said microcrystals, the portion of the microcrystal coated with silver being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005% by volume; and then i. cooling said glazed substrate to room temperature.

Claim 18

A method for coating a glass, glass-ceramic, ceramic, or metal substrate with a colored glaze comprising the steps of: a. melting a batch for a glass containing the constituents of sodium fluoride and the constituents of at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide; and about 0-0.2% CeO 2 ; b. forming said melt into a glass and comminuting said glass into a frit; c. applying said frit to the substrate to be coated; d. firing the coated substrate at a temperature sufficient to sinter the frit into a tightly-adherent glaze; e. exposing at least a portion of said glazed substrate to high energy or actinic radiation, selected from the group consisting of high velocity electrons, X-radiations, and ultra-violet radiations; f. heating at least said exposed portion of the glazed substrate to a temperature between about the transformation range and the softening point of the glaze for a period of time sufficient to cause nucleation and growth of microcrystals of sodium fluoride containing at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide to occur within said exposed portion; g. re-exposing at least said previously-exposed portion of said glazed substrate to high energy or actinic radiation, selected from the group consisting of high velocity electrons, X-radiations, and ultra-violet radiations; h. heating at least said re-exposed portion of the glazed substrate to a temperature between the transformation range and the softening point of the glaze for a period of time sufficient to cause metallic silver to be deposited as discrete colloidal particles less than 200A in the smallest dimension, and/or deposited within said microcrystals, the silver-containing part of the microcrystal being less than about 200A in the smallest dimension, and/or deposited on the surface of said microcrystals, the portion of the microcrystal coated with silver being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005% by volume; and then i. cooling said glazed substrate to room temperature.

Claim 21

A method for making a glass article wherein at least a portion thereof is integrally colored by silver in a single color which comprises the steps: a. melting a batch for a glass containing the constituents of sodium fluoride, the constituents of at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide, about 0 to 0.2% CeO 2 " and a thermoreducing agent; b. forming said melt into a glass article; c. subjecting at least a portion of said glass article to an elevated temperature between about the transformation range and the softening point of the glass for a period of time sufficient to reduce part of the silver to metallic silver and initiate nucleation and growth of microcrystals of sodium fluoride containing at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide; d. exposing at least said portion of the glass article subjected to said elevated temperature to high energy or actinic radiation selected from the group consisting of high velocity electrons, X-radiations, and ultra-violet radiations; e. heating at least said exposed portion to a temperature between the transformation range and the softening point of the glass for a period of time sufficient to cause metallic silver to be deposited as discrete collodial particles less than 200A in the smallest dimension, and/or deposited within said microcrystals, the silver-containing part of the microcrystal being less than about 200A in the smallest dimension, and/or deposited on the surface of said microcrystals, the portion of the microcrystal coated with silver being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005% by volume; and then f. cooling said article to room temperature.

Claim 22

A method for making a glass article wherein at least a portion thereof is integrally colored by silver in a single color which comprises the steps: a. melting a batch for a glass containing the constituents of sodium fluoride, the constituents of at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide, about 0 to 0.2% CeO 2 " and a thermoreducing agent; b. forming said melt into a glass article; c. subjecting at least a portion of said glass article to an elevated temperature between about the transformation range and the softening point of the glass for a period of time sufficient to reduce part of the silver to metallic silver and initiate nucleation and growth of microcrystals of sodium fluoride containing at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide; d. exposing at least said portion of the glass article subjected to said elevated temperature to high energy or actinic radiation selected from the group consisting of high velocity electrons, X-radiations, and ultra-violet radiations; e. heating at least said exposed portion to a temperature between the transformation range and the softening point of the glass for a period of time sufficient to cause metallic silver to be deposited as discrete collodial particles less than 200A in the smallest dimension, and/or deposited within said microcrystals, the silver-containing part of the microcrystal being less than about 200A in the smallest dimension, and/or deposited on the surface of said microcrystals, the portion of the microcrystal coated with silver being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005% by volume; and then f. cooling said article to room temperature.

Claim 25

A method for making a glass article wherein at least a portion thereof is integrally colored and polarizing which comprises the steps: a. melting a batch for a glass containing the constituents of sodium fluoride, the constituents of at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide and about 0 to 0.2% CeO 2 "; b. forming said melt into a glass article; c. exposing at least a portion of said article to high energy or actinic radiation, selected from the group consisting of high velocity electrons, X-radiations, and ultraviolet radiations; d. heating at least said exposed portion of the article to a temperature between about the transformation range and the softening point of the glass in such a manner and for a period of time sufficient to cause nucleation and growth of microcrystals of sodium fluoride containing at least silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide to occur in linear orientation within said exposed portion; e. re-exposing at least said previously-exposed portion of said article to high energy or actinic radiation, selected from the group consisting of high velocity electrons, X-radiations, and ultraviolet radiations; f. heating at least said re-exposed portion of said article to a temperature between the transformation range and the softening point of the glass for a period of time sufficient to cause metallic silver to be deposited as discrete colloidal particles less than 200A in the smallest dimension, and/or deposited within said microcrystals, the silver-containing part of the microcrystal being less than about 200A in the smallest dimension, and/or deposited on the surface of said microcrystals, the portion of the microcrystal coated with silver being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005% by volume; and then g. cooling said article to room temperature.

Claim 26

A method for making a glass article wherein at least a portion thereof is integrally colored and polarizing which comprises the steps: a. melting a batch for a glass containing the constituents of sodium fluoride, the constituents of at least one silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide and about 0 to 0.2% CeO 2 "; b. forming said melt into a glass article; c. exposing at least a portion of said article to high energy or actinic radiation, selected from the group consisting of high velocity electrons, X-radiations, and ultraviolet radiations; d. heating at least said exposed portion of the article to a temperature between about the transformation range and the softening point of the glass in such a manner and for a period of time sufficient to cause nucleation and growth of microcrystals of sodium fluoride containing at least silver halide selected from the group consisting of silver chloride, silver bromide, and silver iodide to occur in linear orientation within said exposed portion; e. re-exposing at least said previously-exposed portion of said article to high energy or actinic radiation, selected from the group consisting of high velocity electrons, X-radiations, and ultraviolet radiations; f. heating at least said re-exposed portion of said article to a temperature between the transformation range and the softening point of the glass for a period of time sufficient to cause metallic silver to be deposited as discrete colloidal particles less than 200A in the smallest dimension, and/or deposited within said microcrystals, the silver-containing part of the microcrystal being less than about 200A in the smallest dimension, and/or deposited on the surface of said microcrystals, the portion of the microcrystal coated with silver being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005% by volume; and then g. cooling said article to room temperature.