Method for making silver-containing glasses exhibiting thermoplastic properties and photosensitivity

Claim 1

A method for making a transparent, essentially colorless glass body exhibiting thermoplastic properties wherein at least a surface portion thereof contains Ag + ions which comprises melting a batch for an anhydrous glass body consisting essentially, in mole percent on the oxide bases, of about 3-25% Na 2 O and/or K 2 O, 50-95% SiO 2 , up to 25% of at least one oxide selected from the group of BaO, B 2 O 3 , CaO, PbO, and ZnO, up to 35% MgO, up to 20% Al 2 O 3 , and up to 10% Li 2 O, and then contacting said anhydrous glass body in thickness dimensions no greater than about 5 mm. with an aqueous solution environment containing Ag + ions having a pH less than about 4, the oxidation state of the glass being controlled in both the batch composition and in said aqueous solution environment, said oxidation state of said aqueous solution environment being controlled by including an oxidizing agent therein, this contact being made at a temperature in excess of 100° C. and at a pressure in excess of 20 psig for a period of time sufficient to hydrate at least a surface portion on said glass body having an amount of H 2 O absorbed therein effective to impart thermoplastic properties thereto and to cause the replacement of Na + and/or K + ions with Ag + ions in said hydrated glass, the proportion of Na + and/or K + ions in said hydrated glass being less with a corresponding increase in Ag + ions.

Claim 2

A method for making a transparent, essentially colorless glass body exhibiting thermoplastic properties wherein at least a surface portion thereof contains Ag + ions which comprises melting a batch for an anhydrous glass body consisting essentially, in mole percent on the oxide bases, of about 3-25% Na 2 O and/or K 2 O, 50-95% SiO 2 , up to 25% of at least one oxide selected from the group of BaO, B 2 O 3 , CaO, PbO, and ZnO, up to 35% MgO, up to 20% Al 2 O 3 , and up to 10% Li 2 O, and then contacting said anhydrous glass body in thickness dimensions no greater than about 5 mm. with an aqueous solution environment containing Ag + ions having a pH less than about 4, the oxidation state of the glass being controlled in both the batch composition and in said aqueous solution environment, said oxidation state of said aqueous solution environment being controlled by including an oxidizing agent therein, this contact being made at a temperature in excess of 100° C. and at a pressure in excess of 20 psig for a period of time sufficient to hydrate at least a surface portion on said glass body having an amount of H 2 O absorbed therein effective to impart thermoplastic properties thereto and to cause the replacement of Na + and/or K + ions with Ag + ions in said hydrated glass, the proportion of Na + and/or K + ions in said hydrated glass being less with a corresponding increase in Ag + ions.

Claim 8

A method for making a transparent, essentially colorless glass body wherein at least a surface portion thereof exhibits thermoplastic properties and wherein at least said surface portion thereof contains Ag + ions which comprises the steps of: (a) melting a batch for an anhydrous glass body consisting essentially, in mole percent on the oxide basis, of about 3-25% Na 2 O and/or K 2 O, 50-95% SiO 2 , up to 25% of at least one oxide selected from the group of BaO, B 2 O 3 , CaO, PbO, and ZnO, up to 35% MgO, up to 20% Al 2 O 3 , and up to 10% Li 2 O; (b) hydrating said anhydrous glass body by exposing said body to a H 2 O-containing gaseous atmosphere having a relative humidity of at least about 75% at a temperature of at least about 100° C. for a period of time sufficient to develop at least a surface portion which is essentially saturated with H 2 O; (c) dehydrating said body through contact thereof with a gaseous environment wherein the relative humidity is less than about 90% of that employed in said hydration step for a period of time sufficient to reduce the water content at least within said surface portion but leaving an amount therein effective to impart thermoplastic properties thereto; and then (d) contacting said hydrated glass body with an aqueous solution environment containing Ag + ions having a pH less than about 5, this contact being made at a temperature in excess of 100° C. for a period of time sufficient to cause the replacement of Na + and/or K + ions in said hydrated glass with Ag + ions, the proportion of Na + and/or K + ions in said hydrated glass being less with a corresponding increase in Ag + ions, the oxidation state of the glass being controlled in both the batch composition and in said aqueous solution environment, said oxidation state of said aqueous solution being controlled by including an oxidizing agent thereof.

Claim 9

A method for making a transparent, essentially colorless glass body wherein at least a surface portion thereof exhibits thermoplastic properties and wherein at least said surface portion thereof contains Ag + ions which comprises the steps of: (a) melting a batch for an anhydrous glass body consisting essentially, in mole percent on the oxide basis, of about 3-25% Na 2 O and/or K 2 O, 50-95% SiO 2 , up to 25% of at least one oxide selected from the group of BaO, B 2 O 3 , CaO, PbO, and ZnO, up to 35% MgO, up to 20% Al 2 O 3 , and up to 10% Li 2 O; (b) hydrating said anhydrous glass body by exposing said body to a H 2 O-containing gaseous atmosphere having a relative humidity of at least about 75% at a temperature of at least about 100° C. for a period of time sufficient to develop at least a surface portion which is essentially saturated with H 2 O; (c) dehydrating said body through contact thereof with a gaseous environment wherein the relative humidity is less than about 90% of that employed in said hydration step for a period of time sufficient to reduce the water content at least within said surface portion but leaving an amount therein effective to impart thermoplastic properties thereto; and then (d) contacting said hydrated glass body with an aqueous solution environment containing Ag + ions having a pH less than about 5, this contact being made at a temperature in excess of 100° C. for a period of time sufficient to cause the replacement of Na + and/or K + ions in said hydrated glass with Ag + ions, the proportion of Na + and/or K + ions in said hydrated glass being less with a corresponding increase in Ag + ions, the oxidation state of the glass being controlled in both the batch composition and in said aqueous solution environment, said oxidation state of said aqueous solution being controlled by including an oxidizing agent thereof.

Claim 15

A method for making a transparent, essentially colorless glass body exhibiting thermoplastic properties and photosensitivity to ultraviolet radiation, and wherein at least a surface portion thereof contains Ag + ions, which comprises melting a batch for an anhydrous glass body consisting essentially, in mole percent on the oxide basis, of about 3-25% Na 2 O and/or K 2 O, 50-95% SiO 2 , up to 25% of at least one oxide selected from the group of BaO, B 2 O 3 , CaO, PbO, and ZnO, up to 35% MgO, up to 20% Al 2 O 3 , up to 10% Li 2 O, and about 0.1-3% of a halide selected from the group F - , Cl - , Br - , and I - , and then contacting said anhydrous glass body in thickness dimensions no greater than about 5 mm. with an aqueous solution environment containing Ag + ions having a pH less than about 4, the oxidation state of the glass being controlled in both the batch composition and in said aqueous solution environment, said oxidation state of said aqueous solution environment being controlled by including an oxidizing agent therein, this contact being made at a temperature in excess of 100° C. and at a pressure in excess of 20 psig for a period of time sufficient to hydrate at least a surface portion on said glass body having an amount of H 2 O absorbed therein effective to impart thermoplastic properties thereto and to cause the replacement of Na + and/or K + ions with Ag + ions in said hydrated glass, the proportion of Na + and/or K + ions in said hydrated glass being less with a corresponding increase in Ag + ions.

Claim 16

A method for making a transparent, essentially colorless glass body exhibiting thermoplastic properties and photosensitivity to ultraviolet radiation, and wherein at least a surface portion thereof contains Ag + ions, which comprises melting a batch for an anhydrous glass body consisting essentially, in mole percent on the oxide basis, of about 3-25% Na 2 O and/or K 2 O, 50-95% SiO 2 , up to 25% of at least one oxide selected from the group of BaO, B 2 O 3 , CaO, PbO, and ZnO, up to 35% MgO, up to 20% Al 2 O 3 , up to 10% Li 2 O, and about 0.1-3% of a halide selected from the group F - , Cl - , Br - , and I - , and then contacting said anhydrous glass body in thickness dimensions no greater than about 5 mm. with an aqueous solution environment containing Ag + ions having a pH less than about 4, the oxidation state of the glass being controlled in both the batch composition and in said aqueous solution environment, said oxidation state of said aqueous solution environment being controlled by including an oxidizing agent therein, this contact being made at a temperature in excess of 100° C. and at a pressure in excess of 20 psig for a period of time sufficient to hydrate at least a surface portion on said glass body having an amount of H 2 O absorbed therein effective to impart thermoplastic properties thereto and to cause the replacement of Na + and/or K + ions with Ag + ions in said hydrated glass, the proportion of Na + and/or K + ions in said hydrated glass being less with a corresponding increase in Ag + ions.

Claim 21

A method for making a transparent, essentially colorless glass body exhibiting thermoplastic properties and photosensitivity to ultraviolet radiation, and wherein at least a surface portion thereof contains Ag + ions, which comprises the steps of: (a) hydrating a glass body consisting essentially, in mole percent on the oxide basis, of about 3-25% Na 2 O and/or K 2 O, 50-95% SiO 2 , up to 25% of at least one oxide selected from the group of BaO, B 2 O 3 , CaO, PbO, and ZnO, up to 35% MgO, up to 20% Al 2 O 3 , up to 10% Li 2 O, and about 0.1-3% of a halide selected from the group F - , Cl - , Br - , and I - , by exposing said body to a H 2 O-containing gaseous atmosphere having a relative humidity of at least about 75% at a temperature of at least about 100° C. for a period of time sufficient to develop at least a surface portion which is essentially saturated with water; (b) dehydrating said body through contact thereof with a gaseous environment wherein the relative humidity is less than about 90% of that employed in said hydration step for a period of time sufficient to reduce the water content at least within said surface portion but leaving an amount therein effective to impart thermoplastic properties thereto; and (c) contacting said hydrated glass body with an aqueous solution containing Ag + ions having a pH less than about 5, this contact being made at a temperature in excess of about 100° C. for a period of time sufficient to cause the replacement of Na + and/or K + ions in said hydrated glass with Ag + ions, the proportion of Na + and/or K + ions in said hydrated glass being less with a corresponding increase in Ag + ions, the oxidation state of the glass being controlled in both the batch composition and in said aqueous solution, the oxidation state of said aqueous solution being controlled by including an oxidizing agent therein.

Claim 22

A method for making a transparent, essentially colorless glass body exhibiting thermoplastic properties and photosensitivity to ultraviolet radiation, and wherein at least a surface portion thereof contains Ag + ions, which comprises the steps of: (a) hydrating a glass body consisting essentially, in mole percent on the oxide basis, of about 3-25% Na 2 O and/or K 2 O, 50-95% SiO 2 , up to 25% of at least one oxide selected from the group of BaO, B 2 O 3 , CaO, PbO, and ZnO, up to 35% MgO, up to 20% Al 2 O 3 , up to 10% Li 2 O, and about 0.1-3% of a halide selected from the group F - , Cl - , Br - , and I - , by exposing said body to a H 2 O-containing gaseous atmosphere having a relative humidity of at least about 75% at a temperature of at least about 100° C. for a period of time sufficient to develop at least a surface portion which is essentially saturated with water; (b) dehydrating said body through contact thereof with a gaseous environment wherein the relative humidity is less than about 90% of that employed in said hydration step for a period of time sufficient to reduce the water content at least within said surface portion but leaving an amount therein effective to impart thermoplastic properties thereto; and (c) contacting said hydrated glass body with an aqueous solution containing Ag + ions having a pH less than about 5, this contact being made at a temperature in excess of about 100° C. for a period of time sufficient to cause the replacement of Na + and/or K + ions in said hydrated glass with Ag + ions, the proportion of Na + and/or K + ions in said hydrated glass being less with a corresponding increase in Ag + ions, the oxidation state of the glass being controlled in both the batch composition and in said aqueous solution, the oxidation state of said aqueous solution being controlled by including an oxidizing agent therein.