Method of forming transparent and opaque portions in a reducing atmosphere glass

Claim 1

A method for making a glass article wherein a portion thereof exhibits opacity and a portion thereof is transparent which comprises the steps: (a) melting a batch under reducing conditions for a glass consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 10-20% Na 2 O, 1.5-3% F, 0.001-0.03% total of at least one metal selected from the group consisting of Ag, Au, Cu, Pd, and Pt, 0.1-1% Sb 2 O 3 and/or 0.01-1% SnO, the total Sb 2 O 3 + SnO not exceeding about 1%, and the remainder SiO 2 ; (b) forming said melt into a transparent glass article containing submicroscopic particles of at least one metal selected from the group of Ag, Au, Cu, Pd, and Pt dispersed therein; (c) exposing a portion of said article to high energy or actinic radiation at ambient temperature to develop a transparent latent image therein containing a large number of metal nuclei; (d) heating said glass article to a temperature between about the transformation range of the glass and the softening point thereof for a sufficient length of time to cause nucleation and growth of microcrystals of NaF in said exposed portion of said article of insufficient size to scatter visible light, and the growth of NaF crystals on said submicroscopic particles of at least one metal selected from the group consisting of Ag, Au, Cu, Pd, and Pt in that portion of said article not exposed to high energy or actinic radiation of such size as to scatter visible light and impart opacity thereto, whereby said exposed portion of said article is transparent and said portion of said article not exposed to high energy or actinic radiation is opaque; and then (e) cooling said article to ambient temperature.

Claim 2

A method for making a glass article wherein a portion thereof exhibits opacity and a portion thereof is transparent which comprises the steps: (a) melting a batch under reducing conditions for a glass consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 10-20% Na 2 O, 1.5-3% F, 0.001-0.03% total of at least one metal selected from the group consisting of Ag, Au, Cu, Pd, and Pt, 0.1-1% Sb 2 O 3 and/or 0.01-1% SnO, the total Sb 2 O 3 + SnO not exceeding about 1%, and the remainder SiO 2 ; (b) forming said melt into a transparent glass article containing submicroscopic particles of at least one metal selected from the group of Ag, Au, Cu, Pd, and Pt dispersed therein; (c) exposing a portion of said article to high energy or actinic radiation at ambient temperature to develop a transparent latent image therein containing a large number of metal nuclei; (d) heating said glass article to a temperature between about the transformation range of the glass and the softening point thereof for a sufficient length of time to cause nucleation and growth of microcrystals of NaF in said exposed portion of said article of insufficient size to scatter visible light, and the growth of NaF crystals on said submicroscopic particles of at least one metal selected from the group consisting of Ag, Au, Cu, Pd, and Pt in that portion of said article not exposed to high energy or actinic radiation of such size as to scatter visible light and impart opacity thereto, whereby said exposed portion of said article is transparent and said portion of said article not exposed to high energy or actinic radiation is opaque; and then (e) cooling said article to ambient temperature.

Claim 8

A method for making a glass article wherein a portion thereof exhibits opacity and a portion thereof is transparent and integrally colored which comprises the steps: (a) melting a batch under reducing conditions for a glass consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 10-20% Na 2 O, 1.5-3% F, 0.001-0.03% total of Ag and, optionally, at least one metal selected from the group consisting of Au, Cu, Pd, and Pt, an amount of at least one halide selected from the group consisting of Cl, Br, and I at least sufficient to react stoichiometrically with said Ag, but not more than about 2% total, 0.1-1% Sb 2 O 3 and/or 0.01-1% SnO, the total Sb 2 O 3 + SnO not exceeding about 1%, and the remainder SiO 2 ; (b) forming said melt into a transparent glass article having submicroscopic particles of Ag and, optionally, of at least one metal selected from the group of Au, Cu, Pd, and Pt dispersed therein; (c) exposing a portion of said article to high energy or actinic radiation at ambient temperature to develop a transparent latent image therein containing a large number of metal nuclei; (d) heating said glass article to a temperature between about the transformation range of the glass and the softening point thereof for a sufficient length of time to cause nucleation and growth of microcrystals of NaF containing silver halide, said halide being selected from the group consisting of Cl, Br, and I, in said exposed portion of said article of insufficient size to scatter visible light, and the growth of NaF crystals on said submicroscopic particles of Ag and, optionally, at least one metal selected from the group consisting of Au, Cu, Pd, and Pt in that portion of said article not exposed to high energy of actinic radiation of such size as to scatter visible light and impart opacity thereto, whereby said exposed portion of said article is transparent and said portion of said article not exposed to high energy or actinic radiation is opaque; (e) exposing said previously-exposed portion of said article to high energy or actinic radiation while at least that portion is at a temperature between about 200°-410° C. for a sufficient length of time to cause, in said exposed portion, Ag to be deposited as discrete colloidal particles less than 200A in the smallest dimension, and/or deposited within said microcrystals, the Ag-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 Ag being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005%, but less than about 0.1%, by volume and the size thereof not exceeding about 0.1 micron in diameter, whereby color is produced in said exposed portion of said article; and then (f) cooling said article to ambient temperature.

Claim 9

A method for making a glass article wherein a portion thereof exhibits opacity and a portion thereof is transparent and integrally colored which comprises the steps: (a) melting a batch under reducing conditions for a glass consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 10-20% Na 2 O, 1.5-3% F, 0.001-0.03% total of Ag and, optionally, at least one metal selected from the group consisting of Au, Cu, Pd, and Pt, an amount of at least one halide selected from the group consisting of Cl, Br, and I at least sufficient to react stoichiometrically with said Ag, but not more than about 2% total, 0.1-1% Sb 2 O 3 and/or 0.01-1% SnO, the total Sb 2 O 3 + SnO not exceeding about 1%, and the remainder SiO 2 ; (b) forming said melt into a transparent glass article having submicroscopic particles of Ag and, optionally, of at least one metal selected from the group of Au, Cu, Pd, and Pt dispersed therein; (c) exposing a portion of said article to high energy or actinic radiation at ambient temperature to develop a transparent latent image therein containing a large number of metal nuclei; (d) heating said glass article to a temperature between about the transformation range of the glass and the softening point thereof for a sufficient length of time to cause nucleation and growth of microcrystals of NaF containing silver halide, said halide being selected from the group consisting of Cl, Br, and I, in said exposed portion of said article of insufficient size to scatter visible light, and the growth of NaF crystals on said submicroscopic particles of Ag and, optionally, at least one metal selected from the group consisting of Au, Cu, Pd, and Pt in that portion of said article not exposed to high energy of actinic radiation of such size as to scatter visible light and impart opacity thereto, whereby said exposed portion of said article is transparent and said portion of said article not exposed to high energy or actinic radiation is opaque; (e) exposing said previously-exposed portion of said article to high energy or actinic radiation while at least that portion is at a temperature between about 200°-410° C. for a sufficient length of time to cause, in said exposed portion, Ag to be deposited as discrete colloidal particles less than 200A in the smallest dimension, and/or deposited within said microcrystals, the Ag-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 Ag being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005%, but less than about 0.1%, by volume and the size thereof not exceeding about 0.1 micron in diameter, whereby color is produced in said exposed portion of said article; and then (f) cooling said article to ambient temperature.

Claim 17

A method for making a glass article wherein a portion thereof exhibits opacity and a portion thereof is transparent which comprises the steps: (a) melting a batch under reducing conditions for a glass consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 10-20% Na 2 O, 1.5-3% F, 0.001-0.03% total of at least one metal selected from the group consisting of Ag, Au, Cu, Pd, and Pt, 0.1-1% Sb 2 O 3 and/or 0.01-1% SnO, the total Sb 2 O 3 + SnO not exceeding about 1%, and the remainder SiO 2 ; (b) forming said melt into a transparent glass article containing submicroscopic particles of at least one metal selected from the group of Ag, Au, Cu, Pd, and Pt dispersed therein; (c) exposing a portion of said article to high energy or actinic radiation while the entire article is heated to a temperature between about 200°-410° C. for a sufficient length of time to cause nucleation and growth of microcrystals of NaF in said exposed portion of the article of insufficient size to scatter visible light, and the growth of NaF on said submicroscopic particles of at least one metal selected from the group of Ag, Au, Cu, Pd, and Pt in said unexposed portion of said article to a sufficient size to scatter visible light, whereby said exposed portion of said article is transparent and said unexposed portion of said article is opaque; and then (d) cooling said article to ambient temperature.

Claim 18

A method for making a glass article wherein a portion thereof exhibits opacity and a portion thereof is transparent which comprises the steps: (a) melting a batch under reducing conditions for a glass consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 10-20% Na 2 O, 1.5-3% F, 0.001-0.03% total of at least one metal selected from the group consisting of Ag, Au, Cu, Pd, and Pt, 0.1-1% Sb 2 O 3 and/or 0.01-1% SnO, the total Sb 2 O 3 + SnO not exceeding about 1%, and the remainder SiO 2 ; (b) forming said melt into a transparent glass article containing submicroscopic particles of at least one metal selected from the group of Ag, Au, Cu, Pd, and Pt dispersed therein; (c) exposing a portion of said article to high energy or actinic radiation while the entire article is heated to a temperature between about 200°-410° C. for a sufficient length of time to cause nucleation and growth of microcrystals of NaF in said exposed portion of the article of insufficient size to scatter visible light, and the growth of NaF on said submicroscopic particles of at least one metal selected from the group of Ag, Au, Cu, Pd, and Pt in said unexposed portion of said article to a sufficient size to scatter visible light, whereby said exposed portion of said article is transparent and said unexposed portion of said article is opaque; and then (d) cooling said article to ambient temperature.

Claim 25

A method for making a glass article wherein a portion thereof exhibits opacity and a portion thereof is transparent and integrally colored which comprises the steps: (a) melting a batch under reducing conditions for a glass consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 10-20% Na 2 O, 1.5-3% F, 0.001-0.03% total of Ag and, optionally, at least one metal selected from the group consisting of Au, Cu, Pd, and Pt, an amount of at least one halide selected from the group consisting of Cl, Br, and I at least sufficient to react stoichiometrically with said Ag, but not more than about 2% total, 0.1-1% Sb 2 O 3 and/or 0.01-1% SnO, the total Sb 2 O 3 + SnO not exceeding about 1%, and the remainder SiO 2 ; (b) forming said melt into a transparent glass article having submicroscopic particles of Ag and, optionally, of at least one metal selected from the group of Au, Cu, Pd, and Pt dispersed therein; (c) exposing a portion of said article to high energy or actinic radiation at ambient temperature to develop a transparent latent image therein containing a large number of metal nuclei; (d) heating said glass article to a temperature between about the transformation range of the glass and the softening point thereof to cause nucleation and growth of microcrystals of NaF containing silver halide, said halide being selected from the group consisting of Cl, Br, and I, in said exposed portion of said article of insufficient size to scatter visible light, and the growth of NaF crystals on said submicroscopic particles of Ag and, optionally, at least one metal selected from the group consisting of Au, Cu, Pd, and Pt in that portion of said article not exposed to high energy or actinic radiation of such size as to scatter visible light and impart opacity thereto, whereby said exposed portion of said article is transparent and said portion of said article not exposed to high energy or actinic radiation is opaque; (e) exposing said previously-exposed portion of said article to high energy or actinic radiation at ambient temperature; (f) heating at least said exposed portion of of said article to a temperature between about the transformation range of the glass and the softening point thereof for a sufficient length of time to cause, in said exposed portion, Ag to be deposited as discrete colloidal particles less than 200A in the smallest dimension, and/or deposited within said microcrystals, the Ag-containing part of the microcrystal being less than about 200A in the smallest dimensions, and/or deposited on the surface of said microcrystals, the portion of the microcrystal coated with Ag being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005%, but less than about 0.1%, by volume and the size thereof not exceeding about 0.1 micron in diameter, whereby color is produced in said exposed portion of said article; and then (g) cooling said article to ambient temperature.

Claim 26

A method for making a glass article wherein a portion thereof exhibits opacity and a portion thereof is transparent and integrally colored which comprises the steps: (a) melting a batch under reducing conditions for a glass consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 10-20% Na 2 O, 1.5-3% F, 0.001-0.03% total of Ag and, optionally, at least one metal selected from the group consisting of Au, Cu, Pd, and Pt, an amount of at least one halide selected from the group consisting of Cl, Br, and I at least sufficient to react stoichiometrically with said Ag, but not more than about 2% total, 0.1-1% Sb 2 O 3 and/or 0.01-1% SnO, the total Sb 2 O 3 + SnO not exceeding about 1%, and the remainder SiO 2 ; (b) forming said melt into a transparent glass article having submicroscopic particles of Ag and, optionally, of at least one metal selected from the group of Au, Cu, Pd, and Pt dispersed therein; (c) exposing a portion of said article to high energy or actinic radiation at ambient temperature to develop a transparent latent image therein containing a large number of metal nuclei; (d) heating said glass article to a temperature between about the transformation range of the glass and the softening point thereof to cause nucleation and growth of microcrystals of NaF containing silver halide, said halide being selected from the group consisting of Cl, Br, and I, in said exposed portion of said article of insufficient size to scatter visible light, and the growth of NaF crystals on said submicroscopic particles of Ag and, optionally, at least one metal selected from the group consisting of Au, Cu, Pd, and Pt in that portion of said article not exposed to high energy or actinic radiation of such size as to scatter visible light and impart opacity thereto, whereby said exposed portion of said article is transparent and said portion of said article not exposed to high energy or actinic radiation is opaque; (e) exposing said previously-exposed portion of said article to high energy or actinic radiation at ambient temperature; (f) heating at least said exposed portion of of said article to a temperature between about the transformation range of the glass and the softening point thereof for a sufficient length of time to cause, in said exposed portion, Ag to be deposited as discrete colloidal particles less than 200A in the smallest dimension, and/or deposited within said microcrystals, the Ag-containing part of the microcrystal being less than about 200A in the smallest dimensions, and/or deposited on the surface of said microcrystals, the portion of the microcrystal coated with Ag being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005%, but less than about 0.1%, by volume and the size thereof not exceeding about 0.1 micron in diameter, whereby color is produced in said exposed portion of said article; and then (g) cooling said article to ambient temperature.

Claim 33

A method for making a glass article wherein a portion therein exhibits opacity and a portion thereof is transparent and integrally colored which comprises the steps: (a) melting a batch under reducing conditions for a glass consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 10-20% Na 2 O, 1.5-3% F, 0.001-0.03% total Ag and, optionally, at least one metal selected from the group consisting of Au, Cu, Pd, and Pt, an amount of at least one halide selected from the group consisting of Cl, Br, and I at least sufficient to react stoichiometrically with said Ag, but not more than about 2% total, 0.1-1% Sb 2 O 3 and/or 0.01-1% SnO, the total Sb 2 O 3 + SnO not exceeding about 1%, and the remainder SiO 2 ; (b) forming said melt into a transparent glass article containing submicroscopic particles of Ag and, optionally, at least one metal selected from the group of Au, Cu, Pd, and Pt dispersed therein; (c) exposing a portion of said article to high energy or actinic radiation while the entire article is heated to a temperature between about 200°-410° C. to develop a transparent latent image therein containing a large number of metal nuclei; (d) removing said high energy or actinic radiation and heating said glass article to a temperature between about the transformation range of the glass and the softening point tereof for a sufficient length of time to cause nucleation and growth of microcrystals of NaF containing silver halide, said halide being selected from the group consisting of Cl, Br, and I, in said exposed portion of the article of sufficient size to scatter visible light, and the growth of NaF crystals on said submicroscopic particles of Ag and, optionally, at least one metal selected from the group consisting of Au, Cu, Pd, and Pt in that portion of said article not exposed to high energy or actinic radiation of such size as to scatter visible light and impart opacity thereto, whereby said exposed portion of said article is transparent and said portion of said article not exposed to high energy or actinic radiation is opaque; (e) exposing said previously-exposed portion of said article to high energy or actinic radiation while at least that portion of the article is heated to a temperature between about 200°-410° C. for a sufficient length of time to cause, in said exposed portion, Ag to be deposited as discrete colloidal particles less than 200A in the smallest dimension, and/or deposited within said microcrystals, the Ag-containing part of the microcrystal being less than about 200A in the smallest dimensions, and/or deposited on the surface of said microcrystals, the portion of the microcrystal coated with Ag being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005%, but less than about 0.1%, by volume and the size thereof not exceeding about 0.1 micron in diameter, whereby color is produced in said exposed portion of said article; and then (f) cooling said article to room temperature.

Claim 34

A method for making a glass article wherein a portion therein exhibits opacity and a portion thereof is transparent and integrally colored which comprises the steps: (a) melting a batch under reducing conditions for a glass consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 10-20% Na 2 O, 1.5-3% F, 0.001-0.03% total Ag and, optionally, at least one metal selected from the group consisting of Au, Cu, Pd, and Pt, an amount of at least one halide selected from the group consisting of Cl, Br, and I at least sufficient to react stoichiometrically with said Ag, but not more than about 2% total, 0.1-1% Sb 2 O 3 and/or 0.01-1% SnO, the total Sb 2 O 3 + SnO not exceeding about 1%, and the remainder SiO 2 ; (b) forming said melt into a transparent glass article containing submicroscopic particles of Ag and, optionally, at least one metal selected from the group of Au, Cu, Pd, and Pt dispersed therein; (c) exposing a portion of said article to high energy or actinic radiation while the entire article is heated to a temperature between about 200°-410° C. to develop a transparent latent image therein containing a large number of metal nuclei; (d) removing said high energy or actinic radiation and heating said glass article to a temperature between about the transformation range of the glass and the softening point tereof for a sufficient length of time to cause nucleation and growth of microcrystals of NaF containing silver halide, said halide being selected from the group consisting of Cl, Br, and I, in said exposed portion of the article of sufficient size to scatter visible light, and the growth of NaF crystals on said submicroscopic particles of Ag and, optionally, at least one metal selected from the group consisting of Au, Cu, Pd, and Pt in that portion of said article not exposed to high energy or actinic radiation of such size as to scatter visible light and impart opacity thereto, whereby said exposed portion of said article is transparent and said portion of said article not exposed to high energy or actinic radiation is opaque; (e) exposing said previously-exposed portion of said article to high energy or actinic radiation while at least that portion of the article is heated to a temperature between about 200°-410° C. for a sufficient length of time to cause, in said exposed portion, Ag to be deposited as discrete colloidal particles less than 200A in the smallest dimension, and/or deposited within said microcrystals, the Ag-containing part of the microcrystal being less than about 200A in the smallest dimensions, and/or deposited on the surface of said microcrystals, the portion of the microcrystal coated with Ag being less than about 200A in the smallest dimension, said microcrystals having a concentration of at least 0.005%, but less than about 0.1%, by volume and the size thereof not exceeding about 0.1 micron in diameter, whereby color is produced in said exposed portion of said article; and then (f) cooling said article to room temperature.