Claims
- 1. A high energy beam-sensitive glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said body portion composed of a glass composition comprising in mole percent,
- about 12-18% Li.sub.2 O, Na.sub.2 O, K.sub.2 O and combinations thereof,
- about 3-10% TiO.sub.2,
- 0 - about 10% transition metal oxides,
- about 4-15% ZnO,
- about 0.5-5% Al.sub.2 O.sub.3,
- about 0.4-3% Cl, and
- about 65-75% SiO.sub.2,
- said IIES layer composed of an ion-exchanged glass of said glass composition that has been ion exchanged with ionic silver to substitute silver ions for the alkali metal ions in said IIES layer and alkali metal ions diffuse out of said IIES layer, said ion-exchanged glass composition containing,
- silver ions and/or silver salts, and
- silanol and/or water in an amount of between about 0.01 and 12% by weight H.sub.2 O,
- the concentration of the alkali metal oxides in the ion-exchanged glass of the IIES layer being less than in said glass composition of the body portion.
- 2. The glass article of claim 1 wherein the glass composition has been ion exchanged with an acidic aqueous solution containing soluble ionic silver.
- 3. The glass article of claim 2 wherein the silver salts in the IIES layer are in microcrystals and/or microphases in said IIES layer.
- 4. The glass article of claim 2 wherein the glass composition includes in mole percent one or more of the following,
- 0-about 15% MgO,
- 0-about 15% CaO,
- 0-about 15% SrO,
- 0-about 15% BaO,
- 0-about 15% PbO,
- 0-about 15% B.sub.2 O.sub.3, and
- 0-3% halide selected from the group consisting of F, Br, I and combinations thereof.
- 5. The glass article of claim 4 wherein the transition metal oxides are selected from the group consisting of Ta.sub.2 O.sub.5, ZrO.sub.2, Nb.sub.2 O.sub.5, La.sub.2 O.sub.3, Y.sub.2 O.sub.3, WO.sub.3 and mixtures thereof.
- 6. The glass article of claim 5 wherein in addition to ZnO and Al.sub.2 O.sub.3 the glass composition includes at least one additional acid-durability-and-glass network strengtheners selected from the group consisting of MgO, CaO and PbO.
- 7. The glass article of claim 2 wherein the glass composition contains at least two of the alkali metal oxides of Li.sub.2 O, Na.sub.2 O and K.sub.2 O.
- 8. The glass article of claim 2 wherein the glass composition contains Li.sub.2 O, Na.sub.2 O and K.sub.2 O and the molar concentration ratio of Li.sub.2 O and Na.sub.2 O to K.sub.2 O is more than 0.6.
- 9. The glass article according to claim 2 wherein the glass composition comprises at least 1 mole percent Li.sub.2 O.
- 10. The glass article of claim 5 wherein a portion of the silver ion in the IIES layer is present as glass-network-modifiers and a portion is associated with halides.
- 11. The glass article of claim 10 wherein the portion of silver ions present as glass-network-modifiers in said IIES layer are present in amounts up to 18% Ag.sub.2 O on the mole percent oxide basis, and the portion of silver ions directly associated with halides in said IIES layer are present in amounts up to 6% Ag.sub.2 O on the mole percent oxide basis.
- 12. The glass article of claim 2 wherein said content of the silanol groups and/or water in said integral surface layer ranges between about 0.1-6% by weight H.sub.2 O.
- 13. A high energy beam-sensitive glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said body portion composed of a glass composition comprising in mole percent,
- about 13-15.5% Li.sub.2 O, Na.sub.2 O, K.sub.2 O and mixtures thereof,
- about 4-5% TiO.sub.2,
- about 6.5-7.5% ZnO,
- about 1-2% Al.sub.2 O.sub.3,
- about 0.7-3% Cl, and
- about 69-70% SiO.sub.2,
- said IIES layer composed of an ion-exchanged glass of said glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to substitute silver ions for the alkali metal ions in said IIES layer and alkali metal ions diffuse out of said IIES layer, said ion-exchanged glass composition containing,
- silver ions and/or silver salts, and
- silanol and/or water in an amount of between about
- 0.01 and 12% by weight H.sub.2 O,
- the concentration of the alkali metal oxides in the ion-exchanged glass of the IIES layer being less than in said glass composition of the body portion.
- 14. A high energy beam-sensitive article bearing a recorded image readable in actinic radiation comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of. in mole percent on the oxide basis.
- about 5-25% of one or more alkali metal oxides,
- at least 1.5% TiO.sub.2, but not exceeding 35% TiO.sub.2, the composition containing at least an effective amount of TiO.sub.2 to render the IIES layer insensitive to at least a spectral portion of actinic radiation,
- 0-about 20% MgO.
- 0-about 20% CaO,
- 0-about 20% ZnO.
- 0-about 15% Al.sub.2 O.sub.3,
- 0-about 20% PbO,
- 0-about 20% BaO,
- 0-about 25% B.sub.2 O.sub.3,
- 0-about 25% P.sub.2 O.sub.5,
- 0-about 2-35% of at least one acid-durability-and-glass network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO, and CaO,
- 0-about 4% F,
- - about 2% Br.
- 0-about 2% I.
- 0-about 6% Cl, and
- about 50-89% SiO.sub.2.
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image said IIES layer comprising,
- silver ions,
- elemental silver, and
- water in a concentration between about 0.01% and 12% by weight H.sub.2 O.
- 15. The high energy beam-sensitive article of claim 14 wherein the glass composition contains in mole percent about 0.2-6% Cl.
- 16. The high energy beam-sensitive article of claim 14 wherein the glass composition contains in mole percent about 0.4-3% Cl.
- 17. The high energy beam-sensitive article of claim 14 wherein the glass composition contains in mole percent about 3-10% TiO.sub.2.
- 18. The high energy beam-sensitive article of claim 14 wherein the glass composition contains in mole percent 0-about 15% B.sub.2 O.sub.3.
- 19. The high energy beam-sensitive article of claim 14 wherein the glass composition contains in mole percent 0-7.2% B.sub.2 O.sub.3.
- 20. The high energy beam-sensitive article of claim 14 wherein the concentration of water in said IIES layer is between about 0.1-6% by weight H.sub.2 O.
- 21. The high energy beam sensitive article of claim 14 wherein the glass composition contains in mole percent 0.6-2.4% Al.sub.2 O.sub.3.
- 22. The high energy beam-sensitive article of claim 14 wherein the glass composition contains in mole percent about 4-10% ZnO.
- 23. The high energy beam-sensitive article of claim 14 wherein the thickness of said IIES layer is less than about 10 micrometers.
- 24. A high energy beam-sensitive article bearing a recorded image readable in actinic radiation comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams. said glass composition consisting essentially of, in mole percent on the oxide basis,
- 12-16% Li.sub.2 O, Na.sub.2 O, K.sub.2 O and combinations thereof,
- 3% to 10% TiO.sub.2, the glass composition containing a sufficient amount of TiO.sub.2 to render the IIES layer insensitive to at least a spectral portion of the actinic radiation,
- 4-10% ZnO,
- 0.5-5% Al.sub.2 O.sub.3,
- 0.8-6% Cl, and
- 68-75% SiO.sub.2,
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image.said IIES layer comprising,
- silver ions,
- elemental silver, and
- water in a concentration between about 0.01% and 12% by weight H.sub.2 O.
- 25. A high energy beam-sensitive article bearing a recorded image readable in actinic radiation comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 12-18% Li.sub.2 O, Na.sub.2 O, K.sub.2 O and combinations thereof,
- about 3-10% oxides of transition metals having 1 to 4 d-electrons in the atomic state, including about 3% to 10% TiO.sub.2, the glass composition containing a sufficient amount of the oxides of transition metals having 1 to 4 d-electrons in the atomic state to render the IIES layer insensitive to at least a spectral portion of the actinic radiation,
- about 4-15% ZnO.
- about 0.5-5% Al.sub.2 O.sub.3,
- about 0.4-3% Cl. and
- about 65-75% SiO.sub.2,
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image, said IIES layer comprising.
- silver ions,
- elemental silver, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 26. A high energy beam-sensitive article bearing a recorded image readable in actinic radiation comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis.
- 13.4-20.9% Li.sub.2 O, Na.sub.2 O, K.sub.2 O, Rb.sub.2 O, Cs.sub.2 O and combinations thereof,
- 0.5-8.4% total of photosensitivity inhibitors (PI agents) and RS suppression agents (RSS agents) the composition containing at least an effective amount of PI agents to render said IIES layer insensitive to at least a spectral portion of the actinic radiation, including 0.5 to 7.4% TiO.sub.2.
- 3.6-7.6% ZnO,
- 0.6-2.4% Al.sub.2O.sub.3,
- up to 10.8% MgO,
- up to 4% CaO,
- up to 4% BaO,
- up to 3.5% PbO.
- up to 4% SrO,
- up to 7.2% B.sub.2 O.sub.3,
- up to 7.2% P.sub.2 O.sub.5,
- up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof,
- 0-3.8% Cl, and
- 58.5-73.2% SiO.sub.2,
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image, said IIES layer comprising,
- silver ions,
- elemental silver, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 27. A high energy beam-sensitive article bearing a recorded image readable in actinic radiation comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis.
- about 3-25% of one or more alkali metal oxides,
- at least 1.5%, but not more than 35%, of photosensitivity inhibitors (PI agents) selected from the group consisting of TiO.sub.2, Nb.sub.2 O.sub.5, Y.sub.2 O.sub.3, Ta.sub.2 O.sub.5 and combinations thereof, the composition containing at least an effective amount of the PI agents to render the IIES layer insensitive to at least a spectral portion of actinic radiation.
- 0-about 35% of acid-durability-and-glass-network strentheners (ADAGNS).
- 0-about 25% P.sub.2 O.sub.5,
- 0-about 25% B.sub.2 O.sub.3,
- 0-about 4% F,
- 0-about 6% Cl,
- 0-about 2% Br,
- 0-about 2% I, and
- about 20-93% SiO.sub.2,
- the sum amount of the above components constituting at least 75 mole percent of the glass composition said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image, said IIES layer comprising,
- silver ions.
- elemental silver, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 28. The high energy beam-sensitive article of claim 27 wherein the glass composition contains in mole percent about 0.2-6% Cl.
- 29. The high energy beam-sensitive article of claim 27 wherein the glass composition contains in mole percent about 0.4-3% Cl.
- 30. The high energy beam-sensitive article of claim 27 wherein the glass composition contains in mole percent about 3-10% TiO.sub.2.
- 31. The high energy beam-sensitive article of claim 27 wherein the glass composition contains in mole percent 0-about 15% B.sub.2 O.sub.3.
- 32. The high energy beam-sensitive article of claim 27 wherein the glass composition contains in mole percent 0-7.2% B.sub.2 O.sub.3.
- 33. The high energy beam-sensitive article of claim 27 wherein the concentration of water in said IIES layer is between about 0.01% and 12% by weight H.sub.2 O.
- 34. The high energy beam-sensitive article of claim 27 wherein the concentration of water in said IIES layer is betweeen about 0.1-6% by weight H.sub.2 O.
- 35. The high energy beam sensitive article of claim 27 wherein the glass composition contains in mole percent 0.6-2.4% Al.sub.2 O.sub.3.
- 36. The high energy beam-sensitive article of claim 27 wherein the glass composition contains in mole percent about 4-10% ZnO.
- 37. The high energy beam-sensitive article of claim 27 wherein the thickness of said IIES layer is less than about 10 micrometers.
- 38. A high energy beam-sensitive article bearing a recorded image readable in actinic radiation comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 3-25% of one or more alkali metal oxides,
- at least 1.5% TiO.sub.2, but not exceeding 25% TiO.sub.2, the composition containing at least an effective amount of TiO.sub.2 to render the IIES layer insensitive to at least a spectral portion of actinic radiation,
- 0-about 35% of acid-durability-and-glass-network strengtheners (ADAGNS),
- 0-about 25% P.sub.2 O.sub.5,
- 0-about 25% B.sub.2 O.sub.3,
- 0-about 4% F,
- 0-about 6% Cl,
- 0-about 2% Br,
- - about 2% I, and
- about 20-93% SiO.sub.2,
- the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image, said IIES layer comprising,
- silver ions,
- elemental silver, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 39. The high energy beam-sensitive article of claim 38 wherein the glass composition contains in mole percent about 0.2-6% Cl.
- 40. The high energy beam-sensitive article of claim 38 wherein the glass composition contains in mole percent about 0.4-3% Cl.
- 41. The high energy beam-sensitive article of claim 38 wherein the glass composition contains in mole percent about 3-10% TiO.sub.2.
- 42. The high energy beam-sensitive article of claim 38 wherein the glass composition contains in mole percent 0-about 15% B.sub.2 O.sub.3.
- 43. The high energy beam-sensitive article of claim 38 wherein the glass composition contains in mole percent 0-7.2% B.sub.2 O.sub.3.
- 44. The high energy beam-sensitive article of claim 38 wherein the concentration of water in said IIES layer is between about 0.01% and 12% by weight H.sub.2 O.
- 45. The high energy beam-sensitive article of claim 38 wherein the concentration of water in said IIES layer is between about 0.1-6% by weight H.sub.2 O.
- 46. The high energy beam sensitive article of claim 38 wherein the glass composition contains in mole percent 0.6-2.4% Al.sub.2 O.sub.3.
- 47. The high energy beam-sensitive article of claim 38 wherein the glass composition contains in mole percent about 4-10% ZnO.
- 48. The high energy beam-sensitive article of claim 38 wherein the thickness of said IIES layer is less than about 10 micrometers.
- 49. A high energy beam-sensitive article bearing a recorded image readable in actinic radiation comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 3-25% Li.sub.2 O, Na.sub.2 O, K.sub.2 O, Rb.sub.2 O, Cs.sub.2 O and combination thereof,
- 0.5-8.4% total of photosensitivity inhibitors (PI agents) and Rs-suppression agents (RSS agents), the composition containing at least an effective amount of PI agents to render said IIES layer insensitive to at least a spectral portion of the actinic radiation, including 0.5 to 7.4% TiO.sub.2,
- 3.6-7.6% ZnO,
- 0.6-2.4% Al.sub.2 O.sub.3,
- up to 10.8% MgO,
- up to 4% CaO,
- up to 4% BaO,
- up to 3.5% PbO,
- up to 4% SrO,
- up to 7.2% B.sub.2 O.sub.3,
- up to 7.2% P.sub.2 O.sub.5,
- up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof,
- 0.2-6% Cl, and
- 58. 5-73.2% SiO.sub.2,
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image, said IIES layer comprising,
- silver ions,
- elemental silver, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 50. A high energy beam-sensitive article bearing a recorded image readable in actinic radiation comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 5-25% of one or more alkali metal oxides,
- at least 1.5%, but less than 35%, of photosensitivity inhibitors (PI agents) selected from the group consisting of TiO.sub.2, Nb.sub.2 O.sub.5, Y.sub.2 O.sub.3, Ta.sub.2 O.sub.5, and combinations thereof, the composition containing at least an effective amount of the photosensitivity inhibitors to render the IIES layer insensitive to at least a spectral portion of the actinic radiation,
- - about 15% MgO,
- 0-about 15% CaO,
- 0-about 15% SrO,
- 0-about 20% ZnO,
- 0-about 15% Al.sub.2 O.sub.3,
- 0-about 15% PbO,
- 0-about 15% BaO,
- 0-about 15% B.sub.2 O.sub.3,
- about 2-35% of at least one acid-durability-and glass network-strengtheners (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO and CaO,
- 0-about 3% F, Br and I,
- 0-about6% Cl, and
- about 50-89% SiO.sub.2,
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image, said IIES layer comprising,
- silver ions,
- elemental silver, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 51. A high energy beam-sensitive article bearing a recorded image readable in actinic radiation comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 5-25% of one or more alkali metal oxides,
- about 0.5-35% total of at least one photosensitivity inhibitor (PI agent) and RS-suppression agent (RSS agent) selected from oxides of transition metals having 1 to 4 d-electrons in the atomic state,
- 0-about15% MgO,
- 0-about 15% CaO,
- 0-about 15% SrO,
- about 2-20% ZnO,
- 0-about 15% Al.sub.2 O.sub.3,
- 0-about 15% PbO, provided that the amount of acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO and CaO is from about 2% to 35%,
- 0-about 15% B.sub.2 O.sub.3,
- 0-about 3% F, Br and I,
- 0-about 6% Cl, and
- about 50-89% SiO.sub.2,
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image, said IIES layer comprising,
- silver ions,
- elemental silver, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 52. The high energy beam-sensitive article of claim 51 wherein the glass composition contains in mole percent about 0.2-6% Cl.
- 53. The high energy beam-sensitive article of claim 51 wherein the glass composition contains in mole percent about 0.4-3% Cl.
- 54. The high energy beam-sensitive article of claim 51 wherein the glass composition contains in mole percent about 3-10% TiO.sub.2, and 0-about 10% transition metal oxides selected from the group consisting of Ta.sub.2 O.sub.5 ZrO.sub.2, Nb.sub.2 O.sub.5, La.sub.2 O.sub.3, Y.sub.2 O.sub.3, WO.sub.3 and mixtures thereof.
- 55. The high energy beam-sensitive article of claim 51 wherein the glass composition contains in mole percent 0.5-7.4% TiO.sub.2.
- 56. The high energy beam-sensitive article of claim 51 wherein the glass composition contains in mole percent 0-7.2% B.sub.2 O.sub.3.
- 57. The high energy beam-sensitive article of claim 51 wherein the concentration of the water in said IIES layer is between about 0.01% and 12% by weight H.sub.2 O.
- 58. The high energy beam-sensitive article of claim 51 wherein the concentration of water in said IIES layer is between about 0.1-6% by weight H.sub.2 O.
- 59. The high energy beam sensitive article of claim 51 wherein the glass composition contains in mole percent 0.6-2.4% Al.sub.2 O.sub.3.
- 60. The high energy beam-sensitive article of claim 51 wherein the glass composition contains in mole percent about 4-10% ZnO.
- 61. The high energy beam-sensitive article of claim 51 wherein the thickness of said IIES layer is less than about 10 micrometers.
- 62. A high energy beam-sensitive article bearing a recorded image readable in actinic radiation comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- 3-25% of one or more alkali metal oxides,
- 0.5-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents, provided an effective amount of PI agents is included to render the IIES layer insensitive to at least a spectral portion of actinic radiation, including at least 0.5% TiO.sub.2,
- up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS),
- up to 20% BaO,
- up to 25% P.sub.2 O.sub.5,
- up to 25% B.sub.2 O.sub.3,
- up to 4% F,
- up to 6% Cl,
- up to 2% Br,
- up to 2% I, and
- 20-93% SiO.sub.2,
- the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image, said IIES layer comprising,
- silver ions,
- elemental silver, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 63. A high energy beam-sensitive article bearing a recorded image readable in actinic radiation comprising a glass said glass article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- 5-25% total of Li.sub.2 O, Na.sub.2 O and K.sub.2 O,
- 1.2-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents selected from the group consisting of TiO.sub.2, Ta.sub.2 O.sub.5, ZrO.sub.2, Nb.sub.2 O.sub.5, La.sub.2 O.sub.3, Y.sub.2 O.sub.3 and WO.sub.3, provided an effective amount of PI agents is included to render the IIES layer insensitive to at least a spectral portion of actinic radiation, including 1.2% to 25% TiO.sub.2,
- 2-20% ZnO,
- up to 10% Al.sub.2 O.sub.3,
- up to 20% MgO,
- up to 20% CaO,
- up to 20% PbO, provided that the amount of acid-durability-and-glass-network strengtheners (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO and CaO, is from 2 to 35%
- up to 15% B.sub.2 O.sub.3,
- up to 3% total of F, Br, and I,
- up to 6% Cl, and
- 50-89% SiO.sub.2,
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image, said IIES layer comprising,
- silver ions,
- elemental silver, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 64. The high energy beam-sensitive article of claim 63 wherein the glass composition contains in mole percent about 0.2-6% Cl.
- 65. The high energy beam-sensitive article of claim 63 wherein the glass composition contains in mole percent about 0.4-3% Cl.
- 66. The high energy beam-sensitive article of claim 63 wherein the glass composition contains in mole percent about 3-10% TiO.sub.2, and 0 about 10% transition metal oxides selected from the group consisting of Ta.sub.2 O.sub.5, ZrO.sub.2, Nb.sub.2 O.sub.5, La.sub.2 O.sub.3, Y.sub.2 O.sub.3, WO.sub.3 and mixtures thereof.
- 67. The high energy beam-sensitive article of claim 63 wherein the glass composition contains in mole percent 0-7.2% B.sub.2 O.sub.3.
- 68. The high energy beam-sensitive article of claim 63 wherein the concentration of water in said IIES layer is between about 0.01% and 12% by weight H.sub.2 O.
- 69. The high energy beam-sensitive article of claim 63 wherein the concentration of water in said IIES layer is between about 0.1-6% by weight H.sub.2 O.
- 70. The high energy beam sensitive article of claim 63 wherein the glass composition contains in mole percent 0.6-2.4% Al.sub.2 O.sub.3.
- 71. The high energy beam-sensitive article of claim 63 wherein lhe glass composition contains in mole percent about 4-10% ZnO.
- 72. The high energy beam-sensitive article of claim 63 wherein the thickness of said IIES layer is less than about 10 micrometers.
- 73. A method of forming an image readable with actinic radiation in a high energy beam-sensitive article, said high energy-beam-sensitive article comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) being sensitive to high energy beams, said method comprising radiating the IIES layer of the glass article with a high energy beam selected from the group consisting of electron beam, ion beam, molecular beam, X-ray and uv radiation having a wavelength of less than 300 nm in a predetermined geometric manner to record the desired image in the IIES layer by reducing at least a portion of silver ions in the IIES layer to elemental silver, said high energy beam having sufficient energy to penetrate at least 0.1 micrometers into said IIES layer of the glass article, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis.
- 5-25% of one or more alkali metal oxides,
- at least 1.5% TiO.sub.2, but not exceeding 35% TiO.sub.2, the composition containing at least an effective amount of TiO.sub.2 to render the IIES layer insensitive to at least a spectral portion of actinic radiation,
- 0-about 20% MgO,
- 0-about 20% CaO,
- 0-about 20% ZnO,
- 0-about 15% Al.sub.2 O.sub.3,
- - about 20% PbO,
- 0-about 20% BaO,
- 0-about 25% B.sub.2 O.sub.3,
- 0-about 25% P.sub.2 O.sub.5,
- about 2-35% of at least one acid-durability-and-glass network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO, and CaO.
- 0-about 4% F,
- 0-about 2% Br,
- 0-about 2% I,
- 0-about 6% Cl, and
- about 50-89% SiO.sub.2.
- said IIES layer comprising,
- silver ions, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 74. The method according to claim 73 wherein said high energy beam is an electron beam having an accelerating voltage of more than 1 kv.
- 75. A method of forming an image readable with actinic radiation in a high energy beam-sensitive article, said high energy-beam-sensitive article comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) being sensitive to high energy beams, said method comprising radiating the IIES layer of the glass article with a high energy beam selected from the group oonsisting of electron beam, ion beam, molecular beam, X-ray and uv radiation having a wavelength of less than 300 nm in a predetermined geometric manner to record the desired image in the IIES layer by reducing at least a portion of silver ions in the IIES layer to elemental silver, said high energy beam having sufficient energy to penetrate at least 0.1 micrometers into said IIES layer of the glass article, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 12-18% Li.sub.2 O, Na.sub.2 O, K.sub.2 O and combinations thereof,
- about 3-10% oxides of transition metals having 1 to 4 d-electrons in the atomic state, including about 3% to 10% TiO.sub.2, the glass composition containing a sufficient amount of the oxides of transition metals having 1 to 4 d-electrons in the atomic state to render the IIES layer insensitive to at least a spectral portion of the actinic radiation,
- about 4-15% ZnO,
- about 0.5-5% Al.sub.2 O.sub.3,
- about 0.4-3% Cl, and
- about 65-75% SiO.sub.2,
- said IIES layer comprising,
- silver ions, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 76. The method according to claim 75 wherein said high energy beam is an electron beam having an accelerating voltage of more than 1 kv.
- 77. A method of forming an image readable with actinic radiation in a high energy beam-sensitive article, said high energy-beam-sensitive article comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) being sensitive to high energy beams, said method comprising radiating the IIES layer of the glass article with a high energy beam selected from the group consisting of electron beam, ion beam, molecular beam, X-ray and uv radiation having a wavelength of less than 300 nm in a predetermined geometric manner to record the desired image in the IIES layer by reducing at least a portion of silver ions in the IIES layer to elemental silver, said high energy beam having sufficient energy to penetrate at least 0.1 micrometers into said IIES layer of the glass article, said IIES layer composed of a glass layer of a glass oomposition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis.
- 13.4-20.9% Li.sub.2 O, Na.sub.2 O, K.sub.2 O, Rb.sub.2 O, Cs.sub.2 O and combinations thereof,
- 0.5-8.4% total of photosensitivity inhibitors (PI agents) and RS-suppression agents (RSS agents), the composition containing at least an effective amount of PI agents to render said IIES layer insensitive to at least a spectral portion of the actinic radiation, including 0.5 to 7.4% TiO.sub.2,
- 3.6-7.6% ZnO,
- 0.6-2.4% Al.sub.2 O.sub.3,
- up to 10.8% MgO,
- up to 4% CaO,
- up to 4% BaO,
- up to 3.5% PbO,
- up to 7.2% B.sub.2 O.sub.3,
- up to 7.2% P.sub.2 O.sub.5,
- up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof,
- 0-3.8% Cl, and
- 58.5-73.2% SiO.sub.2,
- said IIES layer comprising,
- silver ions, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 78. The method according to claim 77 wherein said high energy beam is an electron beam having an accelerating voltage of more than 1 kv.
- 79. A method of forming an image readable with actinic radiation in a high energy beam-sensitive article, said high energy-beam-sensitive article comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) being sensitive to high energy beams, said method comprising radiating the IIES layer of the glass article with a high energy beam selected from the group consisting of electron beam, ion beam, molecular beam, X-ray and uv radiation having a wavelength of less than 300 nm in a predetermined geometric manner to record the desired image in the IIES layer by reducing at least a portion of silver ions in the IIES layer to elemental silver, said high energy beam having sufficient energy to penetrate at least 0.1 micrometers into said IIES layer of the glass article, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES or sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 3-25% of one or more alkali metal oxides,
- at least 1.5%, but not more than 35%, of photosensitivity inhibitors (PI agents) selected from the group consisting of TiO.sub.2, Nb.sub.2 O.sub.5, Y.sub.2 O.sub.3, Ta.sub.2 O.sub.5 and combinations thereof, the composition containing at least an effective amount of the PI agents to render the IIES layer insensitive to at least a spectral portion of actinic radiation,
- 0-about 35% of acid-durability-and-glass-network strentheners (ADAGNS),
- - about 25% P.sub.2 O.sub.5,
- 0-about 25% B.sub.2 O.sub.3,
- 0-about 4% F,
- 0-about 6% Cl,
- 0-about 2% Br,
- 0-about 2% I, and
- about 20-93% SiO.sub.2,
- the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer comprising,
- silver ions, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 80. The method according to claim 79 wherein said high energy beam is an electron beam having an accelerating voltage of more than 1 kv.
- 81. A method of forming an image readable with actinic radiation in a high energy beam-sensitive article, said high energy-beam-sensitive article comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) being sensitive to high energy beams, said method comprising radiating the IIES layer of the glass article with a high energy beam selected from the group consisting of electron beam, ion beam, molecular beam, X-ray and uv radiation having a wavelength of less than 300 nm in a predetermined geometric manner to record the desired image in the IIES layer by reducing at least a portion of silver ions in the IIES layer to elemental silver, said high energy beam having sufficient energy to penetrate at least 0.1 micrometers into said IIES layer of the glass article, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis.
- about 3-25% of one or more alkali metal oxides,
- at least 1.5% TiO.sub.2, but not exceeding 25% TiO.sub.2, the composition containing at least an effective amount of TiO.sub.2 to render the IIES layer insensitive to at least a spectral portion of actinic radiation.
- 0-about 35% of acid-durability-and-glass-network strengtheners (ADAGNS).
- 0-about 25% P.sub.2 O.sub.5,
- 0-about 25% B.sub.2 O.sub.3,
- 0-about 4% F,
- 0-about 6% Cl,
- 0-about 2% Br,
- 0-about 2% I, and
- about 20-93% SiO.sub.2,
- the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer comprising,
- silver ions, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 82. The method according to claim 81 wherein said high energy beam is an electron beam having an accelerating voltage of more than 1 kv.
- 83. A method of forming an image readable with actinic radiation in a high energy beam-sensitive article, said high energy-beam-sensitive article comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) being sensitive to high energy beams, said method comprising radiating the IIES layer of the glass article with a high energy beam selected from the group consisting of electron beam, ion beam, molecular beam, X-ray and uv radiation having a wavelength of less than 300 nm in a predetermined geometric manner to record the desired image in the IIES layer by reducing at least a portion of silver ions in the IIES layer to elemental silver, said high energy beam having sufficient energy to penetrate at least 0.1 micrometers into said IIES layer of the glass article, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 3-25% Li.sub.2 O, Na.sub.2 O, K.sub.2 O, Rb.sub.2 O, Cs.sub.2 O and combinations thereof,
- 0.5-8.4% total of photosensitivity inhibitors (PI agents) and Rs-suppression agents (RSS agents), the composition containing at least an effective amount of PI agents to render said IIES layer insensitive to at least a spectral portion of the actinic radiation, including 0.5 to 7.4% TiO.sub.2,
- 3.6-7.6% ZnO,
- 0.6-2.4% Al.sub.2 O.sub.3,
- up to 10.8% MgO,
- up to 4% CaO,
- up to 4% BaO,
- up to 3.5% PbO,
- up to 4% SrO,
- up to 7.2% B.sub.2 O.sub.3,
- up to 7.2% P.sub.2 O.sub.5,
- up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof.
- 0.2-6% Cl, and
- 58.5-73.2% SiO.sub.2,
- said IIES layer comprising,
- silver ions, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 84. The method according to claim 83 wherein said high energy beam is an electron beam having an accelerating voltage of more than 1 kv.
- 85. A method of forming an image readable with actinic radiation in a high energy beam-sensitive article, said high energy-beam-sensitive article comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) being sensitive to high energy beams. said method comprising radiating the IIES layer of the glass article with a high energy beam selected from the group consisting of electron beam, ion beam molecular beam, X-ray and uv radiation having a wavelength of less than 300 nm in a predetermined geometric manner to record the desired image in the IIES layer by reducing at least a portion of silver ions in the IIES layer to elemental silver, said high energy beam having sufficient energy to penetrate at least 0.1 micrometers into said IIES layer of the glass article, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 5-25% of one or more alkali metal oxides,
- at least 1.5%, but less than 35% of photosensitivity inhibitors (PI agents) selected from the group consisting of TiO.sub.2, Nb.sub.2 O.sub.5, Y.sub.2 O.sub.3, Ta.sub.2 O.sub.5, and combinations thereof, the composition containing at least an effective amount of the photosensitivity inhibitors to render the IIES layer insensitive to at least a spectral portion of the actinic radiation,
- 0-about 15% MgO,
- - about 15% CaO,
- 0-about 15% SrO,
- 0-about 20% ZnO,
- 0-about 15% Al.sub.2 O.sub.3,
- 0-about 15% PbO,
- 0-about 15% BaO,
- 0-about 15% B.sub.2 O.sub.3,
- about 2-35% of at least one acid-durability-and glass-network-strengtheners (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO and CaO,
- 0-about 3% F, Br and I,
- 0 about 6% Cl, and
- about 50-89% SiO.sub.2,
- said IIES layer comprising,
- silver ions, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 86. The method according to claim 85 wherein said high energy beam is an electron beam having an accelerating voltage of more than 1 kv.
- 87. A method of forming an image readable with actinic radiation in a high energy beam-sensitive article, said high energy-beam-sensitive article comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) being sensitive to high energy beams said method comprising radiating the layer of the glass article with a high energy beam selected from the group consisting of electron beam, ion beam, molecular beam, X-ray and uv radiation having a wavelength of less than 300 nm in a predetermined geometric manner to record the desired image in the IIES layer by reducing at least a portion of silver ions in the IIES layer to elemental silver, said high energy beam having sufficient energy to penetrate at least 0.1 micrometers into said IIES layer of the glass article, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis.
- about 5-25% of one or more alkali metal oxides,
- about 0.5-35% total of at least one photosensitivity inhibitor (PI agent) and RS-suppression agent (RSS agent) selected from oxides of transition metals having 1 to 4 d-electrons in the atomic state,
- 0-about 15% MgO,
- 0-about 15% CaO,
- 0-about 15% SrO,
- about 2-20% ZnO,
- 0-about 15% Al.sub.2 O.sub.3,
- 0-about 15% PbO, provided that the amount of acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO and CaO is from about 2% to 35%,
- 0-about 15% B.sub.2 O.sub.3,
- 0-about 3% F, Br and I,
- 0-about 6% Cl, and
- about 50-89% SiO.sub.2,
- said IIES layer comprising,
- silver ions, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 88. The method according to claim 87 wherein said high energy beam is an electron beam having an accelerating voltage of more than 1 kv.
- 89. A method of forming an image readable with actinic radiation in a high energy beam-sensitive article, said high energy-beam-sensitive article comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) being sensitive to high energy beams, said method comprising radiating the IIES layer of the glass article with a high energy beam selected from the group consisting of electron beam, ion beam, molecular beam, X-ray and uv radiation having a wavelength of less than 300 nm in a predetermined geometric manner to record the desired image in the IIES layer by reducing at least a portion of silver ions in the IIES layer to elemental silver, said high energy beam having sufficient energy to penetrate at least 0.1 micrometers into said IIES layer of the glass article, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis.
- 3-25% of one or more alkali metal oxides,
- 0.5-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents, provided an effective amount of PI agents is included to render the IIES layer insensitive to at least a spectral portion of actinic radiation, including at least 0.5% TiO.sub.2,
- up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS),
- up to 20% BaO,
- up to 25% P.sub.2 O.sub.5,
- up to 25% B.sub.2 O.sub.3,
- up to 4% F,
- up to 6% Cl,
- up to 2% Br,
- up to 2% I. and
- 20-93% SiO.sub.2,
- the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer comprising,
- silver ions, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 90. The method according to claim 89 wherein said high energy beam is an electron beam having an accelerating voltage of more than 1 kv.
- 91. A method of forming an image readable with actinic radiation in a high energy beam-sensitive article, said high energy-beam-sensitive article comprising a glass article, said glass article comprising an integral ion-exchanged surface layer (IIES layer) being sensitive to high energy beams, said method comprising radiating the IIES layer of the glass article with a high energy beam selected from the group consisting of electron beam, ion beam, molecular beam, X-ray and uv radiation having a wavelength of less than 300 nm in a predetermined geometric manner to record the desired image in the IIES layer by reducing at least a portion of silver ions in the IIES layer to elemental silver, said high energy beam having sufficient energy to penetrate at least 0.1 micrometers into said IIES layer of the glass article, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis.
- 5-25% total of Li.sub.2 O, Na.sub.2 O and K.sub.2 O,
- 1.2-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents selected from the group consisting of TiO.sub.2, Ta.sub.2 O.sub.5, ZrO.sub.2, Nb.sub.2 O.sub.5, La.sub.2 O.sub.3, Y.sub.2 O.sub.3 and WO.sub.3, provided an effective amount of PI agents is included to render the IIES layer insensitive to at least a spectral portion of actinic radiation, including 1.2% to 25% TiO.sub.2,
- 2-20% ZnO,
- up to 10% Al.sub.2 O.sub.3,
- up to 20% MgO,
- up to 20% CaO,
- up to 20% PbO, provided that the amount of acid-durability-and-glass-network strengtheners (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO and CaO, is from 2 to 35%
- up to 15% B.sub.2 O.sub.3,
- up to 3% total of F, Br, and I,
- up to 6% Cl, and
- 50-89% SiO.sub.2,
- said IIES layer comprising,
- silver ions, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 92. The method according to claim 91 wherein said high energy beam is an electron beam having an accelerating voltage of more than 1 kv.
- 93. A method of erasing a recorded image readable with actinic radiation in a high energy beam-sensitive article, said article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said method comprising the step of heating the recorded image in the IIES layer to a temperature in excess of 100 degree C., but less than the softening point temperature of the IIES layer to erase the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 5-25% of one or more alkali metal oxides,
- at least 1.5% TiO.sub.2, but not exceeding 35% TiO.sub.2, the composition containing at least an effective amount of TiO.sub.2 to render the IIES layer insensitive to at least a spectral portion of actinic radiation,
- 0-about 20% MgO,
- 0-about 20% CaO,
- 0-about 20% ZnO,
- 0-about 15% Al.sub.2 O.sub.3,
- 0-about 20% PbO,
- 0-about 20% BaO,
- 0-about 25% B.sub.2 O.sub.3,
- 0-about 25% P.sub.2 O.sub.5,
- about 2-35% of at least one acid-durability-and glass network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO, and CaO,
- 0-about 4% F,
- 0-about 2% Br,
- 0-about 2% I,
- 0-about 6% Cl, and
- about 50-89% SiO.sub.2,
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded iamge, said IIES layer comprising
- silver ions,
- elemental silver and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 94. A method of erasing a recorded image readable with actinic radiation in a high energy beam-sensitive article, said article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said method comprising the step of heating the recorded image in the IIES layer to a temperature in excess of 100 degree C., but less than the softening point temperature of the IIES layer to erase the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 12-18% Li.sub.2 O, Na.sub.2 O, K.sub.2 O and combinations thereof,
- about 3-10% oxides of transition metals having 1 to 4 d-electrons in the atomic state, including about 3% to 10% TiO.sub.2, the glass composition containing a sufficient amount of the oxides of transition metals having 1 to 4 d-electrons in the atomic state to render the IIES layer insensitive to at least a spectral portion of the actinic radiation,
- about 4-15% ZnO,
- about 0.5-5% Al.sub.2 O.sub.3,
- about 0.4-3% Cl, and
- about 65-75% SiO.sub.2,
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded iamge, said IIES layer comprising
- silver ions,
- elemental silver and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 95. A method of erasing a recorded image readable with actinic radiation in a high energy beam-sensitive article, said article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said method comprising the step of heating the recorded image in the IIES layer to a temperature in excess of 100 degree C., but less than the softening point temperature of the IIES layer to erase the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- 13.4-20.9% Li.sub.2 O, Na.sub.2 O, K.sub.2 O, Rb.sub.2 O, Cs.sub.2 O and combinations thereof,
- 0.5-8.4% total of photosensitivity inhibitors (PI agents) and RS-suppression agents (RSS agents), the composition containing at least an effective amount of PI agents to render said IIES layer insensitive to at least a spectral portion of the actinic radiation, including 0.5 to 7.4% TiO.sub.2,
- 3.6-7.6% ZnO,
- 0.6-2.4% Al.sub.2 O.sub.3,
- up to 10.8% MgO,
- up to 4% CaO,
- up to 4% BaO,
- up to 3.5% PbO,
- up to 4% SrO,
- up to 7.2% B.sub.2 O.sub.3,
- up to 7.2% P.sub.2 O.sub.5,
- up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof,
- 0-3.8% Cl, and
- 58.5-73.2% SiO.sub.2,
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded iamge, said IIES layer comprising
- silver ions,
- elemental silver and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 96. A method of erasing a recorded image readable with actinic radiation in a high energy beam-sensitive article, said article comprising an integral ion exchanged surface layer (IIES layer) bearing the recorded image, said method comprising the step of heating the recorded image in the IIES layer to a temperature in excess of 100 degree C., but less than the softening point temperature of the IIES layer to erase the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 3-25% of one or more alkali metal oxides,
- at least 1.5%, but not more than 35%, of photosensitivity inhibitors (PI agents) selected from the group consisting of TiO.sub.2, Nb.sub.2 O.sub.5, Y.sub.2 O.sub.3, Ta.sub.2 O.sub.5 and combinations thereof, the composition containing at least an effective amount of the PI agents to render the IIES layer insensitive to at least a speciral portion of actinic radiation,
- 0-about 35% of acid-durability-and-glass-network strentheners (ADAGNS),
- 0-about 25% P.sub.2 O.sub.5,
- 0-about 25% B.sub.2 O.sub.3,
- 0-about 4% F,
- 0-about 6% Cl,
- 0-about 2% Br,
- 0-about 2% I, and
- about 20-93% SiO.sub.2,
- the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the receorded image, said IIES layer comprising
- silver ions,
- elemental silver and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 97. A method of erasing a recorded image readable with actinic radiation in a high energy beam-sensitive article, said article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said method comprising the step of heating the recorded image, in the IIES layer to a temperature in excess of 100 degree C., but less than the softening point temperature of the IIES layer to erase the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 3-25% of one or more alkali metal oxides,
- at least 1.5% TiO.sub.2, but not exceeding 25% TiO.sub.2, the composition containing at least an effective amount of TiO.sub.2 to render the IIES layer insensitive to at least a spectral portion of actinic radiation,
- 0-about 35% of acid-durability-and-glass-network strengtheners (ADAGNS),
- 0-about 25% P.sub.2 O.sub.5,
- 0-about 25% B.sub.2 O.sub.3,
- 0-about 4% F,
- 0-about 6% Cl,
- 0-about 2% Br,
- 0-about 2% I, and
- about 20-93% SiO.sub.2,
- the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded iamge, said IIES layer comprising
- silver ions,
- elemental silver and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 98. A method of erasing a recorded image readable with actinic radiation in a high energy beam-sensitive article, said article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said method comprising the step of heating the recorded image in the IIES layer to a temperature in excess of 100 degree C., but less than the softening point temperature of the IIES layer to erase the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 3-25% Li.sub.2 O, Na.sub.2 O, K.sub.2 O, Rb.sub.2 O, Cs.sub.2 O and combination thereof,
- 0.5-8.4% total of photosensitivity inhibitors (PI agents) and Rs-suppression agents (RSS agents), the composition containing at least an effective amount of PI agents to render said IIES layer insensitive to at least a spectral portion of the actinic radiation, including 0.5 to 7.4% TiO.sub.2,
- 3.6-7.6% ZnO,
- 0.6-2.4% Al.sub.2 O.sub.3,
- up to 10.8% MgO,
- up to 4% CaO,
- up to 4% BaO,
- up to 3.5% PbO,
- up to 4% SrO,
- up to 7.2% B.sub.2 O.sub.3,
- up to 7.2% P.sub.2 O.sub.5,
- up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof,
- 0. 2-6% Cl, and
- 58.5-73.2% SiO.sub.2,
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image, said IIES layer comprising,
- silver ions,
- elemental silver, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 99. A method of erasing a recorded image readable with actinic radiation in a high energy beam-sensitive article, said article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said method comprising the step of heating the recorded image in the IIES layer to a temperature in excess of 100 degree C., but less than the softening point temperature of the IIES layer to erase the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 5-25% of one or more alkali metal oxides,
- at least 1.5%, but less than 35%, of photosensitivity inhibitors (PI agents) selected from the group consisting of TiO.sub.2, Nb.sub.2 O.sub.5, Y.sub.2 O.sub.3, Ta.sub.2 O.sub.5, and combinations thereof, the composition containing at least an effective amount of the photosensitivity inhibitors to render the IIES layer insensitive to at least a spectral portion of the actinic radiation,
- 0-about 15% MgO,
- 0-about 15% CaO,
- 0-about 15% SrO,
- 0-about 20% ZnO,
- 0-about 15% Al.sub.2 O.sub.3,
- 0-about 15% PbO,
- 0-about 15% BaO,
- 0-about 15% B.sub.2 O.sub.3,
- about 2-35% of at least one acid-durability-and glass-network-strengtheners (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO and CaO,
- 0-about 3% F, Br and I,
- 0-about 6% Cl, and
- about 50-89% SiO.sub.2,
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image, said IIES layer comprising,
- silver ions,
- elemental silver, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 100. A method of erasing a recorded image readable with actinic radiation in a high energy beam-sensitive article, said article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said method comprising the step of heating the recorded image in the IIES layer to a temperature in excess of 100 degree C., but less than the softening point temperature of the IIES layer to erase the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 5-25% of one or more alkali metal oxides,
- about 0.5-35% total of at least one photosensitivity inhibitor (PI agent) and RS-suppression agent (RSS agent) selected from oxides of transition metals having 1 to 4 d-electrons in the atomic state,
- - about 15% MgO,
- 0-about 15% CaO,
- 0-about 15% SrO,
- about 2-20% ZnO.
- 0-about 15% Al.sub.2 O.sub.3,
- 0-about 15% PbO, provided that the amount of acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO and CaO is from about 2% to 35%,
- 0-about 15% B.sub.2 O.sub.3,
- 0-about 3% F, Br and I,
- 0-about 6% Cl, and
- about 50-89% SiO.sub.2,
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image, said IIES layer comprising,
- silver ions,
- elemental silver, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 101. A method of erasing a recorded image readable with actinic radiation in a high energy beam-sensitive article, said article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said method comprising the step of heating the recorded image in the IIES layer to a temperature in excess of 100 degree C., but less than the softening point temperature of the IIES layer to erase the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- 3-25% of one or more alkali metal oxides,
- 0.5-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents, provided an effective amount of PI agents is included to render the IIES layer insensitive to at least a spectral portion of actinic radiation, including at least 0.5% TiO.sub.2,
- up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS),
- up to 20% BaO,
- up to 25% P.sub.2 O.sub.5
- up to 25% B.sub.2 O.sub.3,
- up to 4% F,
- up to 6% Cl,
- up to 2% Br,
- up to 2% I, and
- 20-93% SiO.sub.2,
- the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image, said IIES layer comprising,
- silver ions,
- elemental silver, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 102. A method of erasing a recorded image readable with actinic radiation in a high energy beam-sensitive article, said article comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said method comprising the step of heating the recorded image in the IIES layer to a temperature in excess of 100 degree C., but less than the softening point temperature of the IIES layer to erase the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- 5-25% total of Li.sub.2 O, Na.sub.2 O and K.sub.2 O,
- 1.2-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents selected from the group consisting of TiO.sub.2, Ta.sub.2 O.sub.5, ZrO.sub.2, Nb.sub.2 O.sub.5, La.sub.2 O.sub.3, Y.sub.2 O.sub.3, and WO.sub.3, provided an effective amount of PI agents is included to render the IIES layer insensitive to at least a spectral portion of actinic radiation, including 1.2% to 25% TiO.sub.2,
- 2-20% ZnO,
- up to 10% Al.sub.2 O.sub.3,
- up to 20% MgO,
- up to 20% CaO,
- up to 20% PbO, provided that the amount of acid-durability-and-glass-network strengtheners (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO and CaO, is from 2 to 35%
- up to 15% B.sub.2 O.sub.3,
- up to 3% total of F, Br, and I,
- up to 6% Cl, and
- 50-89% SiO.sub.2,
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image, said IIES layer comprising,
- silver ions,
- elemental silver, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 103. A method of imparting the surface of a high energy beam-sensitive article, bearing a recorded image of a latent image, with a surface relief pattern corresponding to the recorded image, said article bearing the recorded image comprising an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said IIES layer to render said IIES layer sensitive to high energy beams, said glass composition consisting essentially of, in mole percent on the oxide basis,
- about 5-25% of one or more alkali metal oxides,
- about 0.5-35% total of at least one photosensitivity inhibitor (PI agent) and RS-suppression agent RSS agent) selected from oxides of transition metals having 1 to 4 d-electrons in the atomic state,
- 0-about 15% MgO,
- 0-about 15% CaO,
- 0-about 15% SrO,
- about 2-20% ZnO,
- 0-about 15% Al.sub.2 O.sub.3,
- 0-about 15% PbO, provided that the amount of acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO and CaO is from about 2% to 35%,
- 0-about 15% B.sub.2 O.sub.3,
- 0-about 3% F, Br and I,
- 0-about 6% Cl, and
- about 50-89% SiO.sub.2,
- said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image, said IIES layer comprising,
- silver ion,
- elemental silver, and
- water in a concentration of between about 0.01 and 12 weight percent H.sub.2 O,
- the method comprising etching the surface of the IIES layer bearing the recorded image of the glass article by wet chemical etching or plasma etching.
- 104. An article bearing a recorded image readable in actinic radiation comprising a high energy beam-sensitive glass, said glass composed of a glass composition consisting essentially of, in mole percent on the anhydrous glass basis,
- 3-25% of one or more alkali metal oxides,
- at least 1.5% TiO.sub.2, but not exceeding 35% TiO.sub.2, the composition containing at least an effective amount of TiO.sub.2 to render the glass insensitive to actinic radiation,
- up to 20% MgO,
- up to 20% CaO,
- up to 20% ZnO,
- up to 15% Al.sub.2 O.sub.3,
- up to 20% PbO,
- up to 20% BaO,
- up to 25% B.sub.2 O.sub.4,
- up to 25% P.sub.2 O.sub.5,
- 2-35% of at least one acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO and CaO,
- up to 4% F,
- up to 2% Br,
- up to 2% I,
- up to 6% Cl,
- 0.1-25% Ag.sub.2 O,
- 50-89% SiO.sub.2, and
- water in a concentration of between about 0.01 and 12 weight percent H.sub.2 O,
- said glass having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of silver ions in said glass to elemental silver to produce the recorded image.
- 105. An article bearing a recorded image readable in actinic radiation comprising a high energy beam-sensitive glass, said glass composed of a glass composition consisting essentially of, in mole percent on the anhydrous glass basis,
- 3-25% of one or more alkali metal oxides,
- 3% to 10% TiO.sub.2, the glass composition containing a sufficient amount of TiO.sub.2 to render said glass insensitive to at least a spectral portion of the actinic radiation,
- 4-10% ZnO,
- 0.5-5% Al.sub.2 O.sub.3,
- 0.8-6% Cl,
- 0.1-25% Ag.sub.2 O,
- 68-75% SiO.sub.2, and
- water in an amount of between about 0.01% and 12% by weight H.sub.2 O,
- said glass having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of silver ions in said glass to elemental silver to produce the recorded image.
- 106. An article bearing a recorded image readable in actinic radiation comprising a high energy beam-sensitive glass, said glass composed of a glass composition consisting essentially of, in mole percent on the anhydrous glass basis,
- 3-25% of one or more alkali metal oxides,
- 0.5-8.4% total of photosensitivity inhibitors (PI agents) and RS-suppression agents (RSS agents), the composition containing at least an effective amount of PI agents to render said glass insensitive to at least a spectral portion of the actinic radiation, including 0.5 to 7.4% TiO.sub.2,
- 3.6-7.6% ZnO,
- 0.6-2.4% Al.sub.2 O.sub.3,
- up to 10.8% MgO,
- up to 4% CaO,
- up to 4% BaO,
- up to 3.5% PbO,
- up to 4% SrO,
- up to 7.2% B.sub.2 O.sub.3,
- up to 7.2% P.sub.2 O.sub.5,
- up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof,
- 0-3.8% Cl,
- 0.1-25% Ag.sub.2 O,
- 58.5-73.2% SiO.sub.2, and
- water in an amount of between about 0.01% and 12% by weight H.sub.2 O,
- said glass having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of silver ions in said glass to elemental silver to produce the recorded image.
- 107. An article bearing a recorded image readable in actinic radiation comprising a high energy beam-sensitive glass, said glass composed of a glass composition consisting essentially of, in mole percent on the anhydrous glass basis,
- 5-25% of one or more alkali metal oxides,
- 0.5-35% total of at least one photosensitivity inhibitor (PI agent) and RS-suppression agent (RSS agent), selected from oxides of transition metals having 1 to 4 d-electrons in the atomic state,
- up to 20% MgO,
- up to 20% CaO,
- 2-20% ZnO,
- up to 15% Al.sub.2 O.sub.3,
- up to 20% PbO, provided that the amount of acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO and CaO is from 2% to 35%,
- up to 20% BaO,
- up to 25% B.sub.2 O.sub.3,
- up to 25% P.sub.2 O.sub.5,
- up to 4% F,
- up to 2% Br,
- up to 2% I,
- up to 6% Cl,
- 0. 1-25% Ag.sub.2 O,
- 50-89% SiO.sub.2, and
- water in a concentration of between about 0.01% and 12% by weight H.sub.2 O,
- said glass having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of silver ions in said glass to elemental silver to produce the recorded image.
- 108. An article bearihg a recorded image readable in actinic radiation comprising a high energy beam-sensitive glass, said glass composed of a glass composition consisting essentially of, in mole percent on the anhydrous glass basis,
- 3-25% of one or more alkali metal oxides,
- 0.5-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents, provided an effective amount of PI agents is included to render said glass insensitive to at least a spectral portion of actinic radiation, including at least 0.5% TiO.sub.2,
- up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS),
- up to 20% BaO,
- up to 25% P.sub.2 O.sub.5,
- up to 25% B.sub.2 O.sub.3,
- up to 4% F,
- up to 6% Cl,
- up to 2% Br,
- up to 2% I,
- 0. 1-25% Ag.sub.2 O
- 20-93% SiO.sub.2, and
- water in a concentration of betweeen about 0.01 and 12 weight percent H.sub.2 O,
- the sum amount of the above components consisting at least 75 mole percent of the glass composition, said glass having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of silver ions in said glass to elemental silver to produce the recorded image.
- 109. A high energy beam-sensitive article comprising a body portion and a film of high energy beam-sensitive glass, said glass affixed to and supported by said body portion, said glass composed of a glass composition comprising of, in mole percent,
- 3-25% of one or more alkali metal oxides,
- 3% to 10% TiO.sub.2, the glass composition containing a sufficient amount of TiO.sub.2 to render said glass insensitive to at least a spectral portion of the actinic radiation,
- 4-10% ZnO,
- 0.5-5% Al.sub.2 O.sub.3,
- 0.8-6% Cl,
- 0.1-25% Ag.sub.2 O,
- 68-75% SiO.sub.2, and
- water in an amount of between about 0.01 and 12 weight percent H.sub.2 O.
- 110. A high energy beam-sensitive article comprising a body portion and a film of high energy beam-sensitive glass, said glass affixed to and supported by said body portion, said glass composed of a glass composition comprising of, in mole percent,
- 3-25% of one or more alkali metal oxides
- 0.5-8.4% total of photosensitivity inhibitors (PI agents) and RS-suppression agents (RSS agents), the composition containing at least an effective amount of PI agents to render said glass insensitive to at least a spectral portion of the actinic radiation, including 0.5 to 7.4% TiO.sub.2,
- 3.6-7.6% ZnO,
- 0.6-2.4% Al.sub.2 O.sub.3,
- up to 10.8% MgO,
- up to 4% CaO,
- up to 4% BaO,
- up to 3.5% PbO,
- up to 4% SrO,
- up to 7.2% B.sub.2 O.sub.3,
- up to 7.2% P.sub.2 O.sub.5,
- up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof,
- 0-3.8% Cl,
- 0.1-25% Ag.sub.2 O,
- 58.5-73.2% SiO.sub.2, and
- water in an amount of between about 0.01 and 12 weight percent H.sub.2 O.
- 111. A high energy beam-sensitive article comprising a body portion and a film of high energy beam-sensitive glass, said glass affixed to and supported by said body portion, said glass composed of a glass composition comprising of, in mole percent,
- 3-25% of one or more alkali metal oxides,
- 0.5-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents, provided an effective amount of PI agents is included to render said glass insensitive to at least a spectral portion of actinic radiation, including at least 0.5% TiO.sub.2,
- up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS),
- up to 20% BaO,
- up to 25% P.sub.2 O.sub.5,
- up to 25% B.sub.2 O.sub.3,
- up to 4% F,
- up to 6% Cl,
- up to 2% Br,
- up to 2% I,
- 0.1-25% Ag.sub.2 O
- 20-93% SiO.sub.2, and
- water in an amount of between about 0.01 and 12 weight percent H.sub.2 O,
- the sum amount of the above components constituting at least 75 mole percent of the glass composition.
- 112. A high energy beam-sensitive article comprising a body portion and a film of high energy beam-sensitive glass, said glass affixed to and supported by said body portion, said glass composed of a glass composition comprising of, in mole percent,
- 5-25% of Li.sub.2 O, Na.sub.2 O and K.sub.2 O,
- 1.2-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents selected from the group consisting of TiO.sub.2, Ta.sub.2 O.sub.5, ZrO.sub.2, Nb.sub.2 O.sub.5, La.sub.2 O.sub.3, Y.sub.2 O.sub.3 and WO.sub.3, provided an effective amount of PI agents is included to render the glass insensitive to at least a spectral portion of actinic radiation, including 1.2% to 25% TiO.sub.2,
- 2-20% ZnO,
- up to 10% Al.sub.2 O.sub.3,
- up to 20% MgO,
- up to 20% CaO,
- up to 20% PbO, provided that the amount of acid-durability-and-glass-network strengtheners (ADAGNS) selected from the group consisting of MgO, ZnO, Al.sub.2 O.sub.3, PbO and CaO, is from 2 to 35%,
- up to 20% BaO
- up to 25% B.sub.2 O.sub.3,
- up to 25% P.sub.2 O.sub.5,
- up to 3% total of F, Br, and I,
- up to 6% Cl,
- 0.1-25% Ag.sub.2 O,
- 50-89% SiO.sub.2, and
- water in a concentration greater than about 0.01% by weight H.sub.2 O.
- 113. The high energy beam-sensitive article of claim 112 wherein the glass composition contains in mole percent about 0.2-6% Cl.
- 114. The high energy beam-sensitive article of claim 112 wherein the glass composition contains in mole percent about 0.4-3% Cl.
- 115. The high energy beam-sensitive article of claim 112 wherein the glass composition contains in mole percent about 3-10% TiO.sub.2, and 0-about 10% transition metal oxides selected from the group consisting of Ta.sub.2 O.sub.5, ZrO.sub.2, Nb.sub.2 O.sub.5, La.sub.2 O.sub.3, Y.sub.2 O.sub.3, WO.sub.3 and mixtures thereof.
- 116. The high energy beam-sensitive article of claim 112 wherein the glass composition contains in mole percent 0-15% B.sub.2 O.sub.3.
- 117. The high energy beam-sensitive article of claim 112 wherein the glass composition contains in mole percent 0-7.2% B.sub.2 O.sub.3.
- 118. The high energy beam-sensitive article of claim 112 wherein the concentration of water in said glass is between about 0.1-6% by weight H.sub.2 O.
- 119. The high energy beam sensitive article of claim 112 wherein the glass composition contains in mole percent 0.6-2.4% Al.sub.2 O.sub.3.
- 120. The high energy beam-sensitive article of claim 112 wherein the glass composition contains in mole percent about 4-10% ZnO.
- 121. The high energy beam-sensitive article of claim 112 wherein the thickness of said film is less than about 10 micrometers.
- 122. A high energy beam-sensitive article comprising a body portion and a film of high energy beam-sensitive glass, said glass affixed to and supported by said body portion, said glass composed of a glass composition comprising of, in mole percent,
- 0-about 25% of one or more alkali metal oxides,
- about 0.5-35% of photosensitivity inhibitors (PI agents) and RS-suppression agents (RSS agents) selected from oxides of transition metals having 1 to 4 d-electrons in the atomic state,
- 0-about 6% Cl,
- about 0.1-25% Ag.sub.2 O,
- about 50-89% SiO.sub.2, and
- silanol and/or water in a concentration of between about 0.01 and 12 weight percent H.sub.2 O.
- 123. The article of claim 122 wherein the glass composition includes in mole percent,
- 0-about 20% MgO,
- 0-about 20% CaO,
- 0-about 20% ZnO,
- 0-about 15% Al.sub.2 O.sub.3,
- 0-about 20% SrO,
- 0-about 20% PbO,
- 0-about 20% BaO,
- 0-about 25% P.sub.2 O.sub.5,
- 0-about 35% B.sub.2 O.sub.3, and
- 0-about 3% halide selected from the group consisting of F, Br, I and mixtures thereof, provided that the total mole percent of ZnO, Al.sub.2 O.sub.3, CaO, MgO and/or PbO is from 2 to about 35%.
- 124. The article of claim 123 wherein the alkali metal oxides are Li.sub.2 O, Na.sub.2 O and K.sub.2 O, and the PI agents and RSS agents are selected from the group consisting of TiO.sub.2, Ta.sub.2 O.sub.5, ZrO.sub.2, Nb.sub.2 O.sub.5, La.sub.2 O.sub.3, Y.sub.2 O.sub.3 WO.sub.3 or mixtures therof.
- 125. The article of claim 124 wherein the glass composition comprises in mole percent,
- 0-about 15% alkali metal oxides,
- about 1.2-25% TiO.sub.2,
- about 2-20% ZnO,
- 0-about 10% Al.sub.2 O.sub.3, and
- about 0.2-6% Cl.
- 126. The article of claim 125 wherein the glass composition comprises in mole percent,
- about 3-10% TiO.sub.2, and
- about 60-80 % SiO.sub.2.
Parent Case Info
This is a continuation-in-part application of pending U.S. patent application Ser. No. 507,681, filed June 24, 1983, now U.S. Pat. No. 4,567,104, on HIGH ENERGY BEAM COLORED GLASSES EXHIBITING INSENSITIVITY TO ACTINIC RADIATION by Che-Kuang Wu which is incorporated herein by this reference.
US Referenced Citations (50)
Foreign Referenced Citations (1)
Number |
Date |
Country |
0074157 |
Apr 1982 |
EPX |
Non-Patent Literature Citations (3)
Entry |
Reprint from Journal of Non-Crystalline Solids, vol. 41, No. 3, Dec. 1980, pp. 381-398, "Stable Silicate Glasses Containing up to 10 Weight Percent of Water", Che-Kuang Wu. |
Reprint from Journal of The American Ceramic Society, 63[7-8], 453-457 (1980), "Nature of Incorporated Water in Hydrated Silicate Glasses", Che-Kuang Wu. |
Reprint from Chemical Abstracts, vol. 94, No. 20, May 1981, p. 281, abstract 161254s, Columbus, Ohio, US; P. Balta et al.: "Crystallized photosensitive glass properties". |
Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
507681 |
Jun 1983 |
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