US4567104A — High energy beam colored glasses exhibiting insen…

Claim 1

Independent Claim 281 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of TiO 2 in chloride containing glass composition of the glass article increases; said body portion composed of a 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 2 , but not exceeding 35% TiO 2 , the composition containing at least an effective amount of TiO 2 to render the IIES layer insensitive to at least a spectral portion of actinic radiation, up to 20% MgO, up to 20% CaO, up to 20% ZnO, up to 15% Al 2 O 3 , up to 20% PbO, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , - 35% of at least one acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO, and CaO, up to 4% F, up to 2% Br, up to 2% I, up to 6% Cl, and 50-89% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 2

Dependent Claim 281 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of TiO 2 in chloride containing glass composition of the glass article increases; said body portion composed of a 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 2 , but not exceeding 35% TiO 2 , the composition containing at least an effective amount of TiO 2 to render the IIES layer insensitive to at least a spectral portion of actinic radiation, up to 20% MgO, up to 20% CaO, up to 20% ZnO, up to 15% Al 2 O 3 , up to 20% PbO, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , - 35% of at least one acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO, and CaO, up to 4% F, up to 2% Br, up to 2% I, up to 6% Cl, and 50-89% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 3

Dependent Claim 32 words

The glass article of claim 1 wherein at least a portion of the silver ions in the IIES layer are in microcrystals in halides and/or halide containing microphases in said IIES layer.

Claim 4

Dependent Claim 26 words

The glass article according to claim 2 wherein the average grain size of the microcrystals and microphases in the IIES layer are less than 0.1 micrometer.

Claim 5

Dependent Claim 28 words

The glass article according to claim 3 wherein the average grain size of the microcrystals and microphases in the IIES layer are less than 0.03 micrometer in diameter.

Claim 6

Dependent Claim 29 words

The glass article according to claim 4 wherein at least a portion of said microcrystals and microphases in the IIES layer have grain size of less than 80 angstroms.

Claim 7

Dependent Claim 39 words

The glass article of claim 2 wherein said microcrystals and/or microphases also containing at least trace amounts of at least one of the following: alkali metal ions, PI agents, RSS agents, and other ingredients contained in said IIES layer.

Claim 8

Dependent Claim 31 words

The glass article of claim 1 wherein the silver ion concentration in the IIES layer is between about 0.1% and 25% Ag 2 O on the mole percent anhydrous glass basis.

Claim 9

Dependent Claim 26 words

The glass article of claim 1 wherein the glass composition contains in mole percent, 2-20% ZnO, 0.5-5% Al 2 O 3 and 1.5-25% TiO 2 .

Claim 10

Dependent Claim 24 words

The glass article of claim 1 wherein said ADAGNS are selected from the group consisting of ZnO, Al 2 O 3 and mixtures thereof.

Claim 11

Dependent Claim 26 words

The glass article of claim 9 wherein the glass composition contains in mole percent, 2-20% ZnO, 0-10% Al 2 O 3 and 1.5-25% TiO 2 .

Claim 12

Dependent Claim 30 words

The glass article of claim 10 wherein the alkali metal oxides are selected from the group consisting of Li 2 O, Na 2 O, K 2 O and mixtures thereof.

Claim 13

Dependent Claim 21 words

The glass article of claim 11 wherein the glass composition contains, in mole percent, 10-20% alkali metal oxide, and 0.8-6% Cl.

Claim 14

Dependent Claim 23 words

The glass article of claim 12 wherein the glass composition contains, in mole percent, 3-10% TiO 2 , and 60-82% SiO 2 .

Claim 15

Dependent Claim 27 words

The glass article of claim 12 wherein the concentration of the water in said IIES layer is between about 0.1% and 12% by weight H 2 O.

Claim 16

Dependent Claim 88 words

The glass article of claim 12 wherein the portion of silver ions directly associated with chloride in the IIEs layer are present in amounts up to 3% Ag 2 O on the mole percent anhydrous glass basis, the portion of silver ions present as dissolved ions in the IIES layer are present in amounts up to 20% Ag 2 O on the mole percent anhydrous glass basis, and the concentration of alkali metal ions in the IIES layer decreases as the concentration of the dissolved silver ions increases.

Claim 17

Dependent Claim 35 words

The glass article of claim 11 wherein the glass composition contains at least two of the alkali metal oxides selected from the group consisting of Li 2 O, Na 2 O and K 2 O.

Claim 18

Dependent Claim 42 words

The glass article to claim 11 wherein the glass composition contains Li 2 O, Na 2 O and K 2 O and the molar concentration ratio of Li 2 O and Na 2 O to K 2 O is more than 0.6.

Claim 19

Dependent Claim 44 words

The glass article of claim 1 wherein said IIES layer also comprises at least a trace amount of copper ions, that are diffused into said IIES layer during the ion exchange with the acidic aqueous solution wherein said solution also contains soluble ionic copper.

Claim 20

Dependent Claim 19 words

The glass article of claim 1 wherein the thickness of said IIES layer is more than about 0.1 micrometers.

Claim 21

Dependent Claim 19 words

The glass article of claim 1 wherein the thickness of said IIES layer is less than about 10 micrometer.

Claim 22

Dependent Claim 19 words

The glass article of claim 1 wherein the thickness of said IIES layer is less than about 3 micrometers.

Claim 23

Dependent Claim 61 words

The glass article according to claim 1 wherein the glass composition contains at least sufficient amounts of PI agents, RSS agents and ADAGNS selected from the group consisting of ZnO, Al 2 O 3 , MgO, CaO and PbO to prevent even the slightest etching of the surface of the IIES layer by the aqueous ion exchange solution during ion exchange.

Claim 24

Dependent Claim 21 words

The glass article according to claim 1 wherein said spectral portion of the actinic radiation has wavelengths longer than 300 nm.

Claim 25

Dependent Claim 21 words

The glass article according to claim 1 wherein said spectral portion of the actinic radiation has wavelengths longer than 400 nm.

Claim 26

Dependent Claim 31 words

The glass article according to claim 1 wherein the glass composition contains a saturated concentration of Cl at its glass melting temperature provided the concentration of Cl does not exceed 6%.

Claim 27

Dependent Claim 15 words

The glass article according to claim 1 wherein the glass article is transparent and colorless.

Claim 28

Dependent Claim 127 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of TiO 2 in chloride-containing glass composition of the glass article increases; said body portion composed of a glass composition consisting essentially, in mole percent on the oxide basis, of, 12-16% Li 2 O, Na 2 O, K 2 O and combinations thereof, 3% to 10% TiO 2 , the glass composition containing a sufficient amount of TiO 2 to render the IIES layer insensitive to at least a spectral portion of the actinic radiation, 4-10% ZnO,

Claim 29

Dependent Claim 127 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of TiO 2 in chloride-containing glass composition of the glass article increases; said body portion composed of a glass composition consisting essentially, in mole percent on the oxide basis, of, 12-16% Li 2 O, Na 2 O, K 2 O and combinations thereof, 3% to 10% TiO 2 , the glass composition containing a sufficient amount of TiO 2 to render the IIES layer insensitive to at least a spectral portion of the actinic radiation, 4-10% ZnO,

Claim 30

Dependent Claim 78 words

5-5% Al 2 O 3 , 0.8-6% Cl, and 68-75% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer containing, silver ions, and water in an amount of between about 0.01% and 12% by weight H 2 O.

Claim 31

Dependent Claim 78 words

5-5% Al 2 O 3 , 0.8-6% Cl, and 68-75% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer containing, silver ions, and water in an amount of between about 0.01% and 12% by weight H 2 O.

Claim 32

Dependent Claim 32 words

The glass article of claim 27 wherein at least a portion of the silver ions in the IIES layer are in microcrystals of halides and/or halide containing microphases in said IIES layer.

Claim 33

Dependent Claim 44 words

The glass article of claim 28 wherein said microcrystals and/or microphases also contain at least trace amounts of at least one of the following: alakli metal ions, TiO 2 , and ZnO, Al 2 O 3 and other ingredients contained in said IIES layer.

Claim 34

Dependent Claim 32 words

The glass article of claim 27 wherein a first portion of the silver ions in the IIES layer is dissolved in the IIES layer and a second portion is associated with halides.

Claim 35

Dependent Claim 55 words

The glass article of claim 30 wherein the first portion of the silver ions is present in amounts up to 16% Ag 2 O on the mole percent anhydrous glass basis, and the concentration of alkali metal ions in the IIES layer decreases as the concentration of the first portion of the silver ions increases.

Claim 36

Dependent Claim 30 words

The glass article of claim 27 wherein the glass composition contains at least two of the alkali metal oxides of Li 2 O, Na 2 O and K 2 O.

Claim 37

Dependent Claim 42 words

The glass article of claim 27 wherein the glass composition contains Li 2 O, Na 2 O and K 2 O and the molar concentration ratio of Li 2 O and Na 2 O to K 2 O is more than 0.6.

Claim 38

Dependent Claim 19 words

The glass article of claim 27 wherein the glass composition comprises at least 1 mole percent Li 2 O.

Claim 39

Dependent Claim 25 words

The glass article of claim 27 wherein the amount of said water in said IIES layer is between about 0.1-6% by weight H 2 O.

Claim 40

Dependent Claim 41 words

The glass article according to claim 27 wherein the glass composition contains at least sufficient amounts of TiO 2 , ZnO and Al 2 O 3 to prevent even the slightest etching by the aqueous ion exchange solution during ion exchange.

Claim 41

Dependent Claim 21 words

The glass article according to claim 27 wherein said spectral portion of the actinic radiation has wavelengths longer than 300 nm.

Claim 42

Dependent Claim 21 words

The glass article according to claim 27 wherein said spectral portion of the actinic radiation has wavelengths longer than 400 nm.

Claim 43

Dependent Claim 31 words

The glass article according to claim 27 wherein the glass composition contains a saturated concentration of Cl at its glass melting temperature provided the concentration of Cl does not exceed 3%.

Claim 44

Dependent Claim 15 words

The glass article according to claim 27 wherein the glass article is transparent and colorless.

Claim 45

Dependent Claim 43 words

The glass article of claim 27 wherein said IIES layer also comprises at least a trace amount of copper ions that are diffused into said IIES layer during the ion exchange with the acidic aqueous solution wherein said solution contains soluble ionic copper.

Claim 46

Dependent Claim 81 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of photosensitivity inhibitors in chloride containing glass composition of the glass article increases; said body portion composed of a glass composition consisting essentially, in mole percent on the oxide basis, of

Claim 47

Dependent Claim 81 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of photosensitivity inhibitors in chloride containing glass composition of the glass article increases; said body portion composed of a glass composition consisting essentially, in mole percent on the oxide basis, of

Claim 48

Dependent Claim 196 words

4-20.9% Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 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 2 , 3.6-7.6% ZnO, 0.6-2.4% Al 2 O 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 2 O 3 , up to 7.2% P 2 O 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 2 , said IIES layer composed of a surface layer of said 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 IIES layer containing, silver ions, and water in an amount of between about 0.01% and 12% by weight H 2 O.

Claim 49

Dependent Claim 196 words

4-20.9% Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 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 2 , 3.6-7.6% ZnO, 0.6-2.4% Al 2 O 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 2 O 3 , up to 7.2% P 2 O 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 2 , said IIES layer composed of a surface layer of said 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 IIES layer containing, silver ions, and water in an amount of between about 0.01% and 12% by weight H 2 O.

Claim 50

Dependent Claim 32 words

The glass article of claim 42 wherein at least a portion of the silver ions in the IIES layer are in microcrystals of halides and/or halide containing microphases in said IIES layer.

Claim 51

Dependent Claim 40 words

The glass article according to claim 43 wherein said microcrystals and/or microphases also contain at least trace amounts of at least one of the following: alkali metal ions, PI agents, RSS agents, and other ingredients contained in said IIES layer.

Claim 52

Dependent Claim 52 words

The glass article of claim 42 wherein the PI agents and the RSS agents are selected from the group consisting of TiO 2 , Ta 2 O 5 , ZrO 2 , Nb 2 O 5 , La 2 O 3 , Y 2 O 3 , WO 3 and mixtures thereof.

Claim 53

Dependent Claim 33 words

The glass article according to claim 45 wherein a first portion of the silver ions in the IIES layer is dissolved in the IIES layer and a second portion is associated with halides.

Claim 54

Dependent Claim 55 words

The glass article of claim 46 wherein the first portion of the silver ions is present in amounts up to 20.9% Ag 2 O on the mole percent anhydrous glass basis, and the concentration of alkali metal ions in the IIES layer decreases as the concentration of the first portion of the silver ions increases.

Claim 55

Dependent Claim 38 words

The glass article of claim 45 wherein in addition to ZnO and Al 2 O 3 the glass composition includes at least one additional acid-durability-and-glass network strengthener selected from the group consisting of MgO, CaO, SrO and PbO.

Claim 56

Dependent Claim 31 words

The glass article according to claim 42 wherein the glass composition contains at least two of the alkali metal oxides of Li 2 O, Na 2 O and K 2 O.

Claim 57

Dependent Claim 43 words

The glass article according to claim 42 wherein the glass composition contains Li 2 O, Na 2 O and K 2 O and the molar concentration ratio of Li 2 O and Na 2 O to K 2 O is more than 0.6.

Claim 58

Dependent Claim 20 words

The glass article according to claim 42 wherein the glass composition contains at least 1 mole percent Li 2 O.

Claim 59

Dependent Claim 26 words

The glass article according to claim 42 wherein said amount of the water in said IIES layer is between about 0.1-6% by weight H 2 O.

Claim 60

Dependent Claim 38 words

The glass article according to claim 42 wherein the glass composition contains at least sufficient amounts of PI agents, RSS agents and ADAGNS to prevent even the slightest etching by the aqueous ion exchange solution during ion exchange.

Claim 61

Dependent Claim 26 words

The glass article of claim 42 wherein the glass composition contains 13.4% to 15.3% Li 2 O, Na 2 O, K 2 O and mixtures thereof.

Claim 62

Dependent Claim 17 words

The glass article of claim 54 wherein the glass composition contains 1.5% to 5.9% TiO 2 .

Claim 63

Dependent Claim 17 words

The glass article of claim 55 wherein the glass composition contains 3% to 4.5% TiO 2 .

Claim 64

Dependent Claim 30 words

The glass article of claim 42 wherein the glass composition contains a saturated concentration of Cl at its glass melting temperature provided the concentration of Cl does not exceed 3.8%.

Claim 65

Dependent Claim 15 words

The glass article according to claim 42 wherein the glass article is transparent and colorless.

Claim 66

Dependent Claim 43 words

The glass article of claim 42 wherein said IIES layer also comprises at least a trace amount of copper ions that are diffused into said IIES layer during the ion exchange with the acidic aqueous solution wherein said solution contains soluble ionic copper.

Claim 67

Dependent Claim 281 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of photosensitivity inhibitors in chloride containing glass composition of the glass article increases; said body portion composed of a glass composition consisting essentially of, in mole percent on the oxide basis, 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 2 , Nb 2 O 5 , Y 2 O 3 , Ta 2 O 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, up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS), up to 25% P 2 O 5 , up to 25% B 2 O 3 , up to 4% F, up to 6% Cl, up to 2% Br, up to 2% I, and 2- 93% SiO 2 , the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer composed of a surface layer of said 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 the IIES layer sensitive to high energy beams, said IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 68

Dependent Claim 281 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of photosensitivity inhibitors in chloride containing glass composition of the glass article increases; said body portion composed of a glass composition consisting essentially of, in mole percent on the oxide basis, 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 2 , Nb 2 O 5 , Y 2 O 3 , Ta 2 O 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, up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS), up to 25% P 2 O 5 , up to 25% B 2 O 3 , up to 4% F, up to 6% Cl, up to 2% Br, up to 2% I, and 2- 93% SiO 2 , the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer composed of a surface layer of said 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 the IIES layer sensitive to high energy beams, said IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 69

Dependent Claim 34 words

The glass article of claim 60 wherein the glass composition includes at least one acid-durability-and-glass-network strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, CaO, PbO, SrO and Al 2 O 3 .

Claim 70

Dependent Claim 33 words

The glass article of claim 61 wherein the total mole percent of the ZnO, Al 2 O 3 , CaO, MgO, SrO and PbO in the glass composition is from 2% to 35%.

Claim 71

Dependent Claim 24 words

The glass article of claim 61 wherein said ADAGNS are selected from the group consisting of ZnO, Al 2 O 3 and mixtures thereof.

Claim 72

Dependent Claim 321 words

A glass article comprising a body portion and an integral ion-exchanged surfacer layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of photosensitivity inhibitors in chloride containing glass compositions of the glass article increases, said body portion composed of a glass composition consisting essentially of, in mole percent on the oxide basis, 5-25% total of Li 2 O, Na 2 O and K 2 O, 1.2-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents selected from the group consisting of TiO 2 , Ta 2 O 5 , ZrO 2 , Nb 2 O 5 , La 2 O 3 , Y 2 O 3 and WO 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 2 , 2-20% ZnO, up to 10% Al 2 O 3 , up to 20% MgO, up to 20CaO, 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 2 O 3 , PbO and CaO, is from 2 to 35%, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , up to 3% total of F, Br, and I, up to 6% Cl, and 50-89% SiO 2 said IIES layer composed of a surface layer of said 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 IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 73

Dependent Claim 321 words

A glass article comprising a body portion and an integral ion-exchanged surfacer layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of photosensitivity inhibitors in chloride containing glass compositions of the glass article increases, said body portion composed of a glass composition consisting essentially of, in mole percent on the oxide basis, 5-25% total of Li 2 O, Na 2 O and K 2 O, 1.2-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents selected from the group consisting of TiO 2 , Ta 2 O 5 , ZrO 2 , Nb 2 O 5 , La 2 O 3 , Y 2 O 3 and WO 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 2 , 2-20% ZnO, up to 10% Al 2 O 3 , up to 20% MgO, up to 20CaO, 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 2 O 3 , PbO and CaO, is from 2 to 35%, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , up to 3% total of F, Br, and I, up to 6% Cl, and 50-89% SiO 2 said IIES layer composed of a surface layer of said 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 IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 74

Dependent Claim 51 words

The glass article of claim 64 wherein at least a portion of the silver ions in the IIES layer are in microcrystals of halides and/or halide containing microphases in said IIES layer, and the average grain size of the microcrystals and microphases in the IIES layer is less than 0.1 micrometer.

Claim 75

Dependent Claim 28 words

The glass article according to claim 65 wherein the average grain size of the microcrystals and microphases in the IIES layer is less than 0.03 micrometer in diameter.

Claim 76

Dependent Claim 29 words

The glass article according to claim 66 wherein at least a portion of said microcrystals and microphases in the IIES layer has grain size of less than 80 angstroms.

Claim 77

Dependent Claim 31 words

The glass article of claim 65 wherein the silver ion concentration in the IIES layer is between about 0.1% and 25% Ag 2 O on the mole percent anhydrous glass basis.

Claim 78

Dependent Claim 20 words

The glass article of claim 65 wherein the glass composition contains in mole percent, 0.5-5% Al 2 O 3 .

Claim 79

Dependent Claim 30 words

The glass article of claim 69 wherein the alkali metal oxides are selected from the group consisting of Li 2 O, Na 2 O, K 2 O and mixtures thereof.

Claim 80

Dependent Claim 21 words

The glass article of claim 70 wherein the glass composition contains in mole percent, 10-20% alkali metal oxide, and 0.8-6% Cl.

Claim 81

Dependent Claim 23 words

The glass article of claim 71 wherein the glass composition contains in mole percent, 3-10% TiO 2 , and 60-82% SiO 2 .

Claim 82

Dependent Claim 27 words

The glass article of claim 71 wherein the concentration of the water in said IIES layer is between about 0.1% and 12% by weight H 2 O.

Claim 83

Dependent Claim 88 words

The glass article of claim 71 wherein the portion of silver ions directly associated with chloride in the IIES layer are present in amounts up to 3% Ag 2 O on the mole percent anhydrous glass basis, the portion of silver ions present as dissolved ions in the IIES layer are present in amounts up to 20% Ag 2 O on the mole percent anhydrous glass basis, and the concentration of alkali metal ions in the IIES layer decreases as the concentration of the dissolved silver ions increases.

Claim 84

Dependent Claim 35 words

The glass article of claim 70 wherein the glass composition contains at least two of the alkali metal oxides selected from the group consisting of Li 2 O, Na 2 O and K 2 O.

Claim 85

Dependent Claim 42 words

The glass article of claim 70 wherein the glass composition contains Li 2 O, Na 2 O and K 2 O and the molar concentration ratio of Li 2 O and Na 2 O to K 2 O is more than 0.6.

Claim 86

Dependent Claim 43 words

The glass article of claim 65 wherein said IIES layer also comprises at least a trace amount of copper ions that are diffused into said IIES layer during the ion exchange with the acidic aqueous solution wherein said solution contains soluble ionic copper.

Claim 87

Dependent Claim 19 words

The glass article of claim 65 wherein the thickness of said IIES layer is more than about 0.1 micrometers.

Claim 88

Dependent Claim 19 words

The glass article of claim 65 wherein the thickness of said IIES layer is less than about 10 micrometer.

Claim 89

Dependent Claim 19 words

The glass article of claim 65 wherein the thickness of said IIES layer is less than about 3 micrometers.

Claim 90

Dependent Claim 38 words

The glass article according to claim 65 wherein the glass composition contains at least sufficient amounts of PI agents, RSS agents and ADAGNS to prevent even the slightest etching by the aqueous ion exchange solution during ion exchange.

Claim 91

Dependent Claim 21 words

The glass article according to claim 65 wherein the spectral portion of the actinic radiation has wavelengths longer than 300 nm.

Claim 92

Dependent Claim 21 words

The glass article according to claim 65 wherein said spectral portion of the actinic radiation has wavelengths longer than 400 nm.

Claim 93

Dependent Claim 30 words

The glass article of claim 65 wherein the glass composition contains a saturated concentration of Cl at its glass melting temperature provided the concentration of Cl does not exceed 6%.

Claim 94

Dependent Claim 15 words

The glass article according to claim 62 wherein the glass article is transparent and colorless.

Claim 95

Dependent Claim 254 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of TiO 2 in chloride containing glass composition of the glass article increases; said body portion composed of a glass composition consisting essentially of, in mole percent on the oxide basis, 3-25% of one or more alkali metal oxides, at least 1.5% TiO 2 , but not exceeding 25% TiO 2 , the composition containing at least an effective amount of TiO 2 to render the IIES layer insensitive to at least a spectral portion of actinic radiation, up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS), up to 25% P 2 O 5 , up to 25% B 2 O 3 , up to 4% F, up to 6% Cl, up to 2% Br, up to 2% I, and 2- 93% SiO 2 , the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer composed of a surface layer of said 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 the IIES layer sensitive to high energy beams, said IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 96

Dependent Claim 254 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of TiO 2 in chloride containing glass composition of the glass article increases; said body portion composed of a glass composition consisting essentially of, in mole percent on the oxide basis, 3-25% of one or more alkali metal oxides, at least 1.5% TiO 2 , but not exceeding 25% TiO 2 , the composition containing at least an effective amount of TiO 2 to render the IIES layer insensitive to at least a spectral portion of actinic radiation, up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS), up to 25% P 2 O 5 , up to 25% B 2 O 3 , up to 4% F, up to 6% Cl, up to 2% Br, up to 2% I, and 2- 93% SiO 2 , the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer composed of a surface layer of said 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 the IIES layer sensitive to high energy beams, said IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 97

Dependent Claim 13 words

The glass article according to claim 86 wherein the additional ADAGNS is ZnO.

Claim 98

Dependent Claim 15 words

The glass article according to claim 86 wherein the glass article is transparent and colorless.

Claim 99

Dependent Claim 43 words

The glass article of claim 86 wherein said IIES layer also comprises at least a trace amount of copper ions that are diffused into said IIES layer during the ion exchange with the acidic aqueous solution wherein said solution contains soluble ionic copper.

Claim 100

Dependent Claim 19 words

The glass article of claim 86 wherein the thickness of said IIES layer is less than about 10 micrometer.

Claim 101

Dependent Claim 255 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of TiO 2 in the glass article increases; said body portion composed of an alkali metal silicate glass composition consisting essentially, in mole percent on the oxide basis, of, 1- 16% Li 2 O, Na 2 O, K 2 O and combinations thereof, 3-10% TiO 2 , the composition containing at least an effective amount of TiO 2 to render the IIES layer insensitive to at least a spectral portion of the actinic radiation, 4.5-35% total concentration of acid-durability-and-glass-network-strengtheners, provided the amount of ZnO is 4-10% and the amount of Al 2 O 3 is 0.5-5%, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , up to 3% halide selected from the group consisting of F, Br, I and combinations thereof, 0.8-6% Cl, and the balance SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer containing, silver ions, and water in an amount of between about 0.01% and 12% by weight H 2 O.

Claim 102

Dependent Claim 255 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of TiO 2 in the glass article increases; said body portion composed of an alkali metal silicate glass composition consisting essentially, in mole percent on the oxide basis, of, 1- 16% Li 2 O, Na 2 O, K 2 O and combinations thereof, 3-10% TiO 2 , the composition containing at least an effective amount of TiO 2 to render the IIES layer insensitive to at least a spectral portion of the actinic radiation, 4.5-35% total concentration of acid-durability-and-glass-network-strengtheners, provided the amount of ZnO is 4-10% and the amount of Al 2 O 3 is 0.5-5%, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , up to 3% halide selected from the group consisting of F, Br, I and combinations thereof, 0.8-6% Cl, and the balance SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer containing, silver ions, and water in an amount of between about 0.01% and 12% by weight H 2 O.

Claim 103

Dependent Claim 41 words

The glass article according to claim 91 wherein the glass composition contains at least sufficient amounts of TiO 2 , ZnO and Al 2 O 3 to prevent even the slightest etching by the aqueous ion exchange solution during ion exchange.

Claim 104

Dependent Claim 37 words

The glass article of claim 91 wherein in addition to ZnO and Al 2 O 3 the glass composition includes at least one additional acid-durability-and-glass-network strengthener selected from the group consisting of MgO, CaO, SrO and PbO.

Claim 105

Dependent Claim 15 words

The glass article according to claim 91 wherein the glass article is transparent and colorless.

Claim 106

Dependent Claim 43 words

The glass article of claim 91 wherein said IIES layer also comprises at least a trace amount of copper ions that are diffused into said IIES layer during the ion exchange with the acidic aqueous solution wherein said solution contains soluble ionic copper.

Claim 107

Dependent Claim 206 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of photosensitivity inhibitors in chloride containing glass composition of the glass article increases; said body portion composed of a glass composition consisting essentially, in mole percent on the oxide basis, of 10-20% Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 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 2 , 3.6-7.6% ZnO, 0.6-2.4% Al 2 O 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 2 O 3 , up to 7.2% P 2 O 5 , up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof,

Claim 108

Dependent Claim 206 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of photosensitivity inhibitors in chloride containing glass composition of the glass article increases; said body portion composed of a glass composition consisting essentially, in mole percent on the oxide basis, of 10-20% Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 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 2 , 3.6-7.6% ZnO, 0.6-2.4% Al 2 O 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 2 O 3 , up to 7.2% P 2 O 5 , up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof,

Claim 109

Dependent Claim 72 words

8-6% Cl, and 58.5-73.2% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer containing, silver ions, and water in an amount of between about 0.01% and 12% by weight H 2 O.

Claim 110

Dependent Claim 72 words

8-6% Cl, and 58.5-73.2% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer containing, silver ions, and water in an amount of between about 0.01% and 12% by weight H 2 O.

Claim 111

Dependent Claim 267 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation; and (c) rigid at room temperature and free of thermoplasticity; said body portion composed of a 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 2 , but not exceeding 25% TiO 2 , the composition containing at least an effective amount of TiO 2 to render the IIES layer insensitive to at least a spectral portion of actinic radiation, up to 20% MgO, up to 20% CaO, up to 20% ZnO, up to 15% Al 2 O 3 up to 20% PbO, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , - 35% of at least one acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO, up to 4% F, up to 2% Br, up to 2% I, up to 6% Cl, and 50-89% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 112

Dependent Claim 267 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation; and (c) rigid at room temperature and free of thermoplasticity; said body portion composed of a 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 2 , but not exceeding 25% TiO 2 , the composition containing at least an effective amount of TiO 2 to render the IIES layer insensitive to at least a spectral portion of actinic radiation, up to 20% MgO, up to 20% CaO, up to 20% ZnO, up to 15% Al 2 O 3 up to 20% PbO, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , - 35% of at least one acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO, up to 4% F, up to 2% Br, up to 2% I, up to 6% Cl, and 50-89% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 113

Dependent Claim 19 words

The glass article of claim 97 wherein the thickness of said IIES layer is less than about 10 micrometer.

Claim 114

Dependent Claim 308 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of photosensitivity inhibitors in chloride containing glass composition of the glass article increases; said body portion composed of a 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%, but less than 35%, of photosensitivity inhibitors (PI agents) selected from the group consisting of TiO 2 , Nb 2 O 5 , Y 2 O 3 , Ta 2 O 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, up to 20% MgO, up to 20% CaO, up to 20% ZnO, up to 15% Al 2 O 3 , up to 20% PbO, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , 2-35% of at least one acid-durability-and-glass-network-strenghtener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO, up to 4% F, up to 2% Br, up to 2% I, up to 6% Cl, and 50-89% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 115

Dependent Claim 308 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of photosensitivity inhibitors in chloride containing glass composition of the glass article increases; said body portion composed of a 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%, but less than 35%, of photosensitivity inhibitors (PI agents) selected from the group consisting of TiO 2 , Nb 2 O 5 , Y 2 O 3 , Ta 2 O 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, up to 20% MgO, up to 20% CaO, up to 20% ZnO, up to 15% Al 2 O 3 , up to 20% PbO, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , 2-35% of at least one acid-durability-and-glass-network-strenghtener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO, up to 4% F, up to 2% Br, up to 2% I, up to 6% Cl, and 50-89% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 116

Dependent Claim 19 words

The glass article of claim 99 wherein the thickness of said IIEES layer is less than about 10 micrometer.

Claim 117

Dependent Claim 294 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation; and (c) rigid at room temperature and free of thermoplasticity; said body portion composed of a 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%, but less than 35%, of photosensitivity inhibitors (PI agents) selected from the group consisting of TiO 2 , Nb 2 O 5 , Y 2 O 3 , Ta 2 O 5 , and combinations thereof, the composition containing at least an effective amount of photosensitivity inhibitors to render the IIES layer insensitive to at least a spectral portion of the actinic radiation, up to 20% MgO, up to 20% CaO, up to 20% ZnO, up to 15% Al 2 O 3 , up to 20% PbO, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , 2-35% of at least one acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO, up to 4% F, up to 2% Br, up to 2% I, up to 6% Cl, and 50-89% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 118

Dependent Claim 294 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation; and (c) rigid at room temperature and free of thermoplasticity; said body portion composed of a 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%, but less than 35%, of photosensitivity inhibitors (PI agents) selected from the group consisting of TiO 2 , Nb 2 O 5 , Y 2 O 3 , Ta 2 O 5 , and combinations thereof, the composition containing at least an effective amount of photosensitivity inhibitors to render the IIES layer insensitive to at least a spectral portion of the actinic radiation, up to 20% MgO, up to 20% CaO, up to 20% ZnO, up to 15% Al 2 O 3 , up to 20% PbO, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , 2-35% of at least one acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO, up to 4% F, up to 2% Br, up to 2% I, up to 6% Cl, and 50-89% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 119

Dependent Claim 19 words

The glass article of claim 101 wherein the thickness of said IIES layer is less than about 10 micrometer.

Claim 120

Dependent Claim 90 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of photosensitivity inhibitors increases; and (c) rigid at room temperature and free of thermoplasticity; said body portion composed of a glass composition consisting essentially of, in mole percent on the oxide basis, 5-25% of one or more alkali metal oxides,

Claim 121

Dependent Claim 90 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of photosensitivity inhibitors increases; and (c) rigid at room temperature and free of thermoplasticity; said body portion composed of a glass composition consisting essentially of, in mole percent on the oxide basis, 5-25% of one or more alkali metal oxides,

Claim 122

Dependent Claim 194 words

5-35% total of at least one photosensitivity inhibitor (PI agent) and RS-suppression agent (RSS agent), provided an effective amount of PI agent is included to render the IIES layer insensitive to at least a spectral portion of actinic radiation; up to 20% MgO, up to 20% CaO, 2-20% ZnO, up to 15% Al 2 O 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 2 O 3 , PbO and CaO is from 2% to 35%, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , up to 4% F, up to 2% Br, up to 2% I, up to 6% Cl, and 50-89% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 123

Dependent Claim 194 words

5-35% total of at least one photosensitivity inhibitor (PI agent) and RS-suppression agent (RSS agent), provided an effective amount of PI agent is included to render the IIES layer insensitive to at least a spectral portion of actinic radiation; up to 20% MgO, up to 20% CaO, 2-20% ZnO, up to 15% Al 2 O 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 2 O 3 , PbO and CaO is from 2% to 35%, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , up to 4% F, up to 2% Br, up to 2% I, up to 6% Cl, and 50-89% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 124

Dependent Claim 19 words

The glass article of claim 103 wherein the thickness of said IIES layer is less than about 10 micrometer.

Claim 125

Dependent Claim 269 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation; and (c) rigid at room temperature, and free of thermoplasticity; said body portion composed of a glass composition consisting essentially of, in mole percent on the oxide basis, - 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 2 , Nb 2 O 5 , Y 2 O 3 , Ta 2 O 5 and combinations thereof, the composition containing at least an effective amount of photosensitivity inhibitors to render the IIES layer insensitive to at least a spectral portion of actinic radiation, up to 35% of acid-durability-and-glass-netwlrk-strengtheners (ADAGNS), up to 20% BaO, up to 25% P 2 O 5 , up to 25% B 2 O 3 , up to 4% F, up to 6% Cl, up to 2% Br, up to 2% I, and 20-93% SiO 2 , the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer composed of a surface layer of said 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 the IIES layer sensitive to high energy beams, said IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 126

Dependent Claim 269 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation; and (c) rigid at room temperature, and free of thermoplasticity; said body portion composed of a glass composition consisting essentially of, in mole percent on the oxide basis, - 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 2 , Nb 2 O 5 , Y 2 O 3 , Ta 2 O 5 and combinations thereof, the composition containing at least an effective amount of photosensitivity inhibitors to render the IIES layer insensitive to at least a spectral portion of actinic radiation, up to 35% of acid-durability-and-glass-netwlrk-strengtheners (ADAGNS), up to 20% BaO, up to 25% P 2 O 5 , up to 25% B 2 O 3 , up to 4% F, up to 6% Cl, up to 2% Br, up to 2% I, and 20-93% SiO 2 , the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer composed of a surface layer of said 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 the IIES layer sensitive to high energy beams, said IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 127

Dependent Claim 19 words

The glass article of claim 105 wherein the thickness of said IIES layer is less than about 10 micrometer.

Claim 128

Dependent Claim 245 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation; and (c) rigid at room temperature, and free of thermoplasticity; said body portion composed of a glass composition consisting essentially of, in mole percent on the oxide basis, 3-25% of one or more alkali metal oxides, at least 1.5% TiO 2 , but not exceeding 35% TiO 2 , the composition containing at least an effective amount of TiO 2 to render the IIES layer insensitive to at least a spectral portion of actinic radiation, up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS), up to 20% BaO, up to 25% P 2 O 5 , up to 25% B 2 O 3 , up to 4% F, up to 6% Cl, up to 2% Br, up to 2% I, and 2- 93% SiO 2 , the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer composed of a surface layer of said 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 the IIES layer sensitive to high energy beams, said IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 129

Dependent Claim 245 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation; and (c) rigid at room temperature, and free of thermoplasticity; said body portion composed of a glass composition consisting essentially of, in mole percent on the oxide basis, 3-25% of one or more alkali metal oxides, at least 1.5% TiO 2 , but not exceeding 35% TiO 2 , the composition containing at least an effective amount of TiO 2 to render the IIES layer insensitive to at least a spectral portion of actinic radiation, up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS), up to 20% BaO, up to 25% P 2 O 5 , up to 25% B 2 O 3 , up to 4% F, up to 6% Cl, up to 2% Br, up to 2% I, and 2- 93% SiO 2 , the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer composed of a surface layer of said 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 the IIES layer sensitive to high energy beams, said IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 130

Dependent Claim 19 words

The glass article of claim 107 wherein the thickness of said IIES layer is less than about 10 micrometer.

Claim 131

Dependent Claim 267 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of photosensitivity inhibitors in chloride-containing glass composition of the glass article increases; (c) rigid at room temperature, and free of thermoplasticity; said body portion composed of a 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 2 , up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS), up to 20% BaO, up to 25% P 2 O 5 , up to 25% B 2 O 3 , up to 4% F, up to 6% Cl, up to 2% Br, up to 2% I, and 20-93% SiO 2 , the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer composed of a surface layer of said 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 the IIES layer sensitive to high energy beams, said IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 132

Dependent Claim 267 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of photosensitivity inhibitors in chloride-containing glass composition of the glass article increases; (c) rigid at room temperature, and free of thermoplasticity; said body portion composed of a 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 2 , up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS), up to 20% BaO, up to 25% P 2 O 5 , up to 25% B 2 O 3 , up to 4% F, up to 6% Cl, up to 2% Br, up to 2% I, and 20-93% SiO 2 , the sum amount of the above components constituting at least 75 mole percent of the glass composition, said IIES layer composed of a surface layer of said 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 the IIES layer sensitive to high energy beams, said IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 133

Dependent Claim 19 words

The glass article of claim 109 wherein the thickness of said IIES layer is less than about 10 micrometer.

Claim 134

Dependent Claim 311 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation; and (c) rigid at room temperature and free of thermoplasticity; said body portion composed of a glass composition consisting essentially of, in mole percent on the oxide basis, - 25% total of Li 2 O, Na 2 O and K 2 O, 1.2-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents selected from the group consisting of TiO 2 , Ta 2 O 5 , ZrO 2 , Nb 2 O 5 , La 2 O 3 , Y 2 O 3 and WO 3 , provided an effective amount of PI agents is included to render the IIES layer insensitivity to at least a spectral portion of actinic radiation, including 1.2% to 25% TiO 2 , 2-20% ZnO, up to 10% Al 2 O 3 , up to 20% MgO, up to 20% CaO, 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 2 O 3 , PbO and CaO is from 2% to 35%, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , up to 3% total of F, Br, and I, up to 6% Cl, and 50-89% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 135

Dependent Claim 311 words

A glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation; and (c) rigid at room temperature and free of thermoplasticity; said body portion composed of a glass composition consisting essentially of, in mole percent on the oxide basis, - 25% total of Li 2 O, Na 2 O and K 2 O, 1.2-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents selected from the group consisting of TiO 2 , Ta 2 O 5 , ZrO 2 , Nb 2 O 5 , La 2 O 3 , Y 2 O 3 and WO 3 , provided an effective amount of PI agents is included to render the IIES layer insensitivity to at least a spectral portion of actinic radiation, including 1.2% to 25% TiO 2 , 2-20% ZnO, up to 10% Al 2 O 3 , up to 20% MgO, up to 20% CaO, 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 2 O 3 , PbO and CaO is from 2% to 35%, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , up to 3% total of F, Br, and I, up to 6% Cl, and 50-89% SiO 2 , said IIES layer composed of a surface layer of said 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 IIES layer comprising, silver ions, and water in a concentration greater than about 0.01% by weight H 2 O.

Claim 136

Dependent Claim 19 words

The glass article of claim 111 wherein the thickness of said IIES layer is less than about 10 micrometer.

Claim 137

Dependent Claim 323 words

A monolithic glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of TiO 2 in chloride containing glass composition of the glass article increases; said body portion composed of a first 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 2 , but not exceeding 25% TiO 2 , the composition containing at least an effective amount of TiO 2 to render the IIES layer insensitive to actinic radiation, up to 20% MgO, up to 20% CaO, up to 20% ZnO, up to 15% Al 2 O 3 , up to 20% PbO, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , 2-35% of at least one acid-durability-and-glass-network strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO, up to 4% F, up to 2% Br, up to 2% I, up to 6% Cl, and 50-89% SiO 2 , said IIES layer composed of a second glass composition comprising water in a concentration of between about 0.01 and 12 weight percent H 2 O, one or more alkali metal oxides, at least 1.5% TiO 2 , at least one acid-durabilityand-glass-network strengthener selected from the group consisting of MgO, CaO, ZnO, Al 2 O 3 , and PbO, at least one halide selected from the group consisting of F, Cl, Br and I, and SiO 2 , and, in mole percent on the anhydrous glass basis, 0.1-25% Ag 2 O, the concentration of the alkali metal oxides in the second glass composition being less than in the first glass composition.

Claim 138

Dependent Claim 323 words

A monolithic glass article comprising a body portion and an integral ion-exchanged surface layer (IIES layer), said glass article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of TiO 2 in chloride containing glass composition of the glass article increases; said body portion composed of a first 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 2 , but not exceeding 25% TiO 2 , the composition containing at least an effective amount of TiO 2 to render the IIES layer insensitive to actinic radiation, up to 20% MgO, up to 20% CaO, up to 20% ZnO, up to 15% Al 2 O 3 , up to 20% PbO, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , 2-35% of at least one acid-durability-and-glass-network strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO, up to 4% F, up to 2% Br, up to 2% I, up to 6% Cl, and 50-89% SiO 2 , said IIES layer composed of a second glass composition comprising water in a concentration of between about 0.01 and 12 weight percent H 2 O, one or more alkali metal oxides, at least 1.5% TiO 2 , at least one acid-durabilityand-glass-network strengthener selected from the group consisting of MgO, CaO, ZnO, Al 2 O 3 , and PbO, at least one halide selected from the group consisting of F, Cl, Br and I, and SiO 2 , and, in mole percent on the anhydrous glass basis, 0.1-25% Ag 2 O, the concentration of the alkali metal oxides in the second glass composition being less than in the first glass composition.

Claim 139

Dependent Claim 221 words

An article comprising a high energy beam-sensitive glass, said article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of TiO 2 in chloride containing glass composition of the glass article increases; 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 2 , but not exceeding 35% TiO 2 , the composition containing at least an effective amount of TiO 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 2 O 3 , up to 20% PbO, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , - 35% of at least one acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO, up to 4% F, up to 2% Br, up to 2% I, up to 6% Cl, 0.1-25% Ag 2 O, 50-89% SiO 2 , and water in a concentration of between about 0.01 and 12 weight percent H 2 O.

Claim 140

Dependent Claim 221 words

An article comprising a high energy beam-sensitive glass, said article exhibiting the following properties: (a) sensitivity to high energy beams; and (b) insensitivity to at least a spectral portion of actinic radiation, and being insensitive to radiation of shorter wavelengths as concentration of TiO 2 in chloride containing glass composition of the glass article increases; 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 2 , but not exceeding 35% TiO 2 , the composition containing at least an effective amount of TiO 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 2 O 3 , up to 20% PbO, up to 20% BaO, up to 25% B 2 O 3 , up to 25% P 2 O 5 , - 35% of at least one acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO, up to 4% F, up to 2% Br, up to 2% I, up to 6% Cl, 0.1-25% Ag 2 O, 50-89% SiO 2 , and water in a concentration of between about 0.01 and 12 weight percent H 2 O.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1989-01-27	1989-07-29	1990-01-28	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1993-01-27	1993-07-29	1994-01-28	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1997-01-27	1997-07-29	1998-01-28	$7700.00	Window Closed / Lapsed

High energy beam colored glasses exhibiting insensitivity to actinic radiation

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