Sealing glass compositions and pastes and use thereof

Claim 2

In a particulate glass composition comprising: a. at least about 70 weight percent of a PbO-containing glass frit component having a sealing temperature of between about 350° to about 415° C., and b. at least about 10-25 weight percent of at least one coarse particulate refractory filler component having a coefficient of thermal expansion of less than about 65 × 10.sup. -7 in./in./° C. (0°-300° C.) and a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 40-60 75 ≦ 30-45 50 ≦ 15-35 25 ≦ 7-20 10 ≦ 2-10 5 ≦ 0.5-3 ______________________________________ the improvement comprising: c. at least about 0.25-10 weight percent of at least one fine particulate refractory filler component having a coefficient of thermal expansion of less than about 65 × 10.sup. -7 in./in./° C. (0°-300° C.) and a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 5-10 75 ≦ 3-8 50 ≦ 2-4 25 ≦ 0.8-2.5 10 ≦ 0.5-2.0 5 ≦ 0.2-1.5 ______________________________________

Claim 3

In a particulate glass composition according to claim 1, in which component (B) has a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 7-9 75 ≦ 4-6 50 ≦ 2-4 25 ≦ 1.2-2.2 10 ≦ 0.8-1.6 5 ≦ 0.7-1.3 ______________________________________ and in which component (C) has a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 7-9 75 ≦ 4-6 50 ≦ 2-4 25 ≦ 1.2-2.2 10 ≦ 0.8-1.6 5 ≦ 0.7-1.3 ______________________________________ and in which each of said refractory filler components has a coefficient of thermal expansion of less than about 40 × 10.sup. -7 in./in./° C. (0°-300° C.).

Claim 4

In a particulate glass composition according to claim 2, in which said PbO-containing glass frit component is a lead-zinc-borate glass.

Claim 5

A particulate glass composition comprising: A. at least about 75 weight percent of a PbO-containing glass frit component having 1. a glassy edge of about 315° to about 390° C. as determined in a gradient boat test, 2. a devitrification edge of about 380° to about 425° C. as determined in a gradient boat test, 3. a button flow of about 1.050 to about 1.250 inches diameter, and 4. the inherent property when sealed to a glass reference rod of inducing a rod stress of about 1500 to about 3500 p.s.i. tension in a glass reference rod having essentially the following composition: ______________________________________ Composition % By Weight ______________________________________ SiO.sub.2 64.0 A1.sub.2 O.sub.3 3.9 Na.sub.2 O 7.7 K.sub.2 O 9.9 CaO 3.6 MgO 1.3 BaO 7.8 CeO.sub.2 0.3 Sb.sub. 2 O.sub.3 0.45 F.sub.2 1.0 Fe.sub.2 O.sub.3 0.05 ______________________________________ (b) about 14 to about 22 weight percent of a zirconium silicate component having a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 45-60 75 ≦ 35-40 50 ≦ 20-35 25 ≦ 10-20 10 ≦ 3-10 5 ≦ 1-3 ______________________________________ and C. about 0.5 to about 4 weight percent of a zirconium silicate component having a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 7-9 75 ≦ 4-6 50 ≦ 2-4 25 ≦ 1.2-2.2 10 ≦ 0.8-1.6 5 ≦ 0.7-1.3 ______________________________________

Claim 6

A particulate glass composition comprising: A. at least about 75 weight percent of a PbO-containing glass frit component having 1. a glassy edge of about 315° to about 390° C. as determined in a gradient boat test, 2. a devitrification edge of about 380° to about 425° C. as determined in a gradient boat test, 3. a button flow of about 1.050 to about 1.250 inches diameter, and 4. the inherent property when sealed to a glass reference rod of inducing a rod stress of about 1500 to about 3500 p.s.i. tension in a glass reference rod having essentially the following composition: ______________________________________ Composition % By Weight ______________________________________ SiO.sub.2 64.0 A1.sub.2 O.sub.3 3.9 Na.sub.2 O 7.7 K.sub.2 O 9.9 CaO 3.6 MgO 1.3 BaO 7.8 CeO.sub.2 0.3 Sb.sub. 2 O.sub.3 0.45 F.sub.2 1.0 Fe.sub.2 O.sub.3 0.05 ______________________________________ (b) about 14 to about 22 weight percent of a zirconium silicate component having a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 45-60 75 ≦ 35-40 50 ≦ 20-35 25 ≦ 10-20 10 ≦ 3-10 5 ≦ 1-3 ______________________________________ and C. about 0.5 to about 4 weight percent of a zirconium silicate component having a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 7-9 75 ≦ 4-6 50 ≦ 2-4 25 ≦ 1.2-2.2 10 ≦ 0.8-1.6 5 ≦ 0.7-1.3 ______________________________________

Claim 7

A particulate glass composition according to claim 4 in which component (B) has a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 46-50 75 ≦ 36-40 50 ≦ 24-28 25 ≦ 10-14 10 ≦ 3-5 5 ≦ 1-3 ______________________________________

Claim 8

A particulate glass composition according to claim 5 in which said frit component consists essentially of about: ______________________________________ Weight Percent ______________________________________ PbO 80-86 B.sub.2 O.sub.3 10-15 ZnO 0-5 SiO.sub.2 0-3 BaO 0-3 ______________________________________

Claim 9

A particulate glass composition according to claim 5 in which said composition comprises: A. about 80 weight percent of a glass frit component consisting essentially of about: ______________________________________ Weight Percent ______________________________________ PbO 83.7 B.sub.2 O.sub.3 12.5 Zno 2.8 SiO.sub.2 0.4 BaO 0.6 ______________________________________ having a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 62-78 75 ≦ 36-46 50 ≦ 17-23 25 ≦ 8-10 10 ≦ 3-5 5 ≦ 2.5-3.5 ______________________________________ B. about 18 to about 19 weight percent of a zirconium silicate component having a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 48 75 ≦ 39 50 ≦ 26 25 ≦ 12 10 ≦ 4 5 ≦ 2 ______________________________________ and C. about 2 to about 1 weight percent of a zirconium silicate component having a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 8 75 ≦ 5 50 ≦ 3 25 ≦ 2 10 ≦ 1 5 ≦ 1 ______________________________________

Claim 10

In a sealing glass paste comprising at least about 70 weight percent of a PbO-containing glass frit component having a sealing temperature of about 350° C. to about 415° C., at least about 10-25 weight percent of at least one coarse particulate refractory filler component having a coefficient of thermal expansion of less than about 65 × 10 - 7 in./in./° C. (0°-300° C.) and a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 40-60 75 ≦ 30-45 50 ≦ 15-35 25 ≦ 7-20 10 ≦ 2-10 5 ≦ 0.5-3 ______________________________________ a binder selected from the group consisting essentially of nitrocellulose, hydroxypropyl cellulose and mixtures thereof, and a solvent for said binder, the improvement comprising the inclusion in said sealing glass paste of at least about 0.25-10 weight percent of at least one fine particulate refractory filler component having a coefficient of thermal expansion of less than about 65 × 10 - 7 in./in./° C. (0°-300° C.) and a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 5-10 75 ≦ 3-8 50 ≦ 2-4 25 ≦ 0.8-2.5 10 ≦ 0.5-2.0 5 ≦ 0.2-1.5 ______________________________________

Claim 11

In a sealing glass paste comprising at least about 70 weight percent of a PbO-containing glass frit component having a sealing temperature of about 350° C. to about 415° C., at least about 10-25 weight percent of at least one coarse particulate refractory filler component having a coefficient of thermal expansion of less than about 65 × 10 - 7 in./in./° C. (0°-300° C.) and a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 40-60 75 ≦ 30-45 50 ≦ 15-35 25 ≦ 7-20 10 ≦ 2-10 5 ≦ 0.5-3 ______________________________________ a binder selected from the group consisting essentially of nitrocellulose, hydroxypropyl cellulose and mixtures thereof, and a solvent for said binder, the improvement comprising the inclusion in said sealing glass paste of at least about 0.25-10 weight percent of at least one fine particulate refractory filler component having a coefficient of thermal expansion of less than about 65 × 10 - 7 in./in./° C. (0°-300° C.) and a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 5-10 75 ≦ 3-8 50 ≦ 2-4 25 ≦ 0.8-2.5 10 ≦ 0.5-2.0 5 ≦ 0.2-1.5 ______________________________________

Claim 12

In a sealing glass composition for sealing a faceplate to a funnel portion of a television tube comprising: a. at least about 70 weight percent of a PbO containing glass frit component having a sealing temperature of about 350° to about 415° C., b. at least about 10-25 weight percent of at least one course particulate refractory filler component having a coefficient of thermal expansion of less than about 65 × 10 - 7 in./in./° C. (0°-300° C.) and a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 40-60 75 ≦ 30-45 50 ≦ 15-35 25 ≦ 7-20 10 ≦ 2-10 5 ≦ 0.5-3 ______________________________________ and c. at least one additive in an amount sufficient to prevent the PbO in said glass frit from being chemically reduced upon exposure of said glass frit to reducing conditions at the sealing temperature thereof, the improvement comprising the inclusion in said sealing glass composition of: d. at least about 0.25-10 weight percent of at least one fine particulate refractory filler component having a coefficient of thermal expansion of less than about 65 × 10 - 7 in./in./° C. (0°-300° C.) and a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 5-10 75 ≦ 3-8 50 ≦ 2-4 25 ≦ 0.8-2.5 10 ≦ 0.5-2.0 5 ≦ 0.2-1.5 ______________________________________

Claim 13

In a sealing glass composition for sealing a faceplate to a funnel portion of a television tube comprising: a. at least about 70 weight percent of a PbO containing glass frit component having a sealing temperature of about 350° to about 415° C., b. at least about 10-25 weight percent of at least one course particulate refractory filler component having a coefficient of thermal expansion of less than about 65 × 10 - 7 in./in./° C. (0°-300° C.) and a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 40-60 75 ≦ 30-45 50 ≦ 15-35 25 ≦ 7-20 10 ≦ 2-10 5 ≦ 0.5-3 ______________________________________ and c. at least one additive in an amount sufficient to prevent the PbO in said glass frit from being chemically reduced upon exposure of said glass frit to reducing conditions at the sealing temperature thereof, the improvement comprising the inclusion in said sealing glass composition of: d. at least about 0.25-10 weight percent of at least one fine particulate refractory filler component having a coefficient of thermal expansion of less than about 65 × 10 - 7 in./in./° C. (0°-300° C.) and a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 5-10 75 ≦ 3-8 50 ≦ 2-4 25 ≦ 0.8-2.5 10 ≦ 0.5-2.0 5 ≦ 0.2-1.5 ______________________________________

Claim 14

In a sealing glass composition according to claim 9, in which component (B) has a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 = 45-60 75 = 35-45 50 = 20-35 25 = 10-20 10 = 3-10 5 = 1-3 ______________________________________ and component (D) has a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 = 7-9 75 = 4-6 50 = 2-4 25 = 1.2-2.2 10 = 0.8-1.6 5 = 0.7-1.3 ______________________________________ and each of said refractory filler components has a coefficient of thermal expansion of less than about 40 × 10 - 7 in./in./° C. (0°-300° C.).

Claim 15

In a sealing glass composition according to claim 10, in which said PbO-containing glass frit component has: a. a glassy edge of about 315° C. to about 390° C. as determined in a gradient boat test, b. a devitrification edge of about 380° C. to about 425° C. as determined in a gradient boat test, c. a button flow of about 1.050 to about 1.250 inches diameter, and d. the inherent property when sealed to a glass reference rod of inducing a rod stress of about 1500 to about 3500 p.s.i. tension in a glass reference rod having essentially the following composition: ______________________________________ Composition % By Weight ______________________________________ SiO.sub.2 64.0 A1.sub.2 O.sub.3 3.9 Na.sub.2 O 7.7 K.sub.2 O 9.9 CaO 3.6 MgO 1.3 BaO 7.8 CeO.sub.2 0.3 Sb.sub. 2 O.sub.3 0.45 F.sub.2 1.0 Fe.sub.2 O.sub.3 0.05 ______________________________________

Claim 16

In a sealing glass composition according to claim 11 in which said frit component is a lead-zinc-borate glass frit.

Claim 17

In a sealing glass composition for sealing a face plate to a funnel portion of a television tube comprising: A. at least about 75 weight percent of a PbO-containing glass frit component having 1. a glassy edge of about 315° to about 390° C. in a gradient boat test, 2. a devitrification edge of about 380° C. to about 425° C. in a gradient boat test, and 3. a button flow of about 1.050 to about 1.250 inches diameter; B. about 14 to about 22 weight percent of zirconium silicate component having a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 45-60 75 ≦ 35-40 50 ≦ 20-35 25 ≦ 10-20 10 ≦ 3-10 5 ≦ 1-3 ______________________________________ C. bi(NO 3 ) 3 .5H 2 O in an amount sufficient to prevent PbO in said frit from being chemically reduced when said solder glass is being fired in the presence of reducing conditions at a temperature sufficient to seal said face plate to said funnel portion; the improvement comprising the inclusion in said sealing glass composition of: D. about 0.5 to about 4 weight percent of zirconium silicate component having a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 7-9 75 ≦ 4-6 50 ≦ 2-4 25 ≦ 1.2-2.2 10 ≦ 0.8-1.6 5 ≦ 0.7-1.3 ______________________________________

Claim 18

In a sealing glass composition for sealing a face plate to a funnel portion of a television tube comprising: A. at least about 75 weight percent of a PbO-containing glass frit component having 1. a glassy edge of about 315° to about 390° C. in a gradient boat test, 2. a devitrification edge of about 380° C. to about 425° C. in a gradient boat test, and 3. a button flow of about 1.050 to about 1.250 inches diameter; B. about 14 to about 22 weight percent of zirconium silicate component having a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 45-60 75 ≦ 35-40 50 ≦ 20-35 25 ≦ 10-20 10 ≦ 3-10 5 ≦ 1-3 ______________________________________ C. bi(NO 3 ) 3 .5H 2 O in an amount sufficient to prevent PbO in said frit from being chemically reduced when said solder glass is being fired in the presence of reducing conditions at a temperature sufficient to seal said face plate to said funnel portion; the improvement comprising the inclusion in said sealing glass composition of: D. about 0.5 to about 4 weight percent of zirconium silicate component having a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 7-9 75 ≦ 4-6 50 ≦ 2-4 25 ≦ 1.2-2.2 10 ≦ 0.8-1.6 5 ≦ 0.7-1.3 ______________________________________

Claim 19

In a sealing glass composition according to claim 13 in which component (B) has a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 46-50 75 ≦ 36-40 50 ≦ 24-28 25 ≦ 10-14 10 ≦ 3-5 5 ≦ 1-3 ______________________________________

Claim 20

In a sealing glass composition according to claim 13 in which said frit component consists essentially of about: ______________________________________ Weight Percent ______________________________________ PbO 80-86 B.sub.2 O.sub.3 10-15 ZnO 0-5 SiO.sub.2 0-3 BaO 0-3 ______________________________________

Claim 21

In a sealing glass composition according to claim 13 in which said composition comprises: A. about 79.92 to about 79.7 weight percent of a frit component consisting essentially of about: ______________________________________ Weight Percent ______________________________________ PbO 83.7 B.sub.2 O.sub.3 12.5 Zno 2.8 SiO.sub.2 0.4 BaO 0.6 ______________________________________ and having a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 62-78 75 ≦ 36-46 50 ≦ 17-23 25 ≦ 8-10 10 ≦ 3-5 5 ≦ 2.5-3.5 ______________________________________ B. about 18 to about 19 weight percent of a coarse zirconium silicate component having a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 48 75 ≦ 39 50 ≦ 26 25 ≦ 12 10 ≦ 4 5 ≦ 2 ______________________________________ C. about 2 to about 1 weight percent of a fine zirconium silicate component having a particle size distribution of about: ______________________________________ % of Particles Microns ______________________________________ 90 ≦ 8 75 ≦ 5 50 ≦ 3 25 ≦ 2 10 ≦ 1 5 ≦ 1 ______________________________________ and D. about 0.08 to about 0.3 weight percent of Bi(NO 3 ) 3 .5H 2 O.

Claim 22

A sealing glass paste comprising: A. a sealing glass composition according to claim 9. B. a binder selected from the group consisting of nitrocellulose, hydroxypropyl cellulose and mixtures thereof; and C. a solvent for said binder.

Claim 23

A sealing glass paste according to claim 17 wherein said binder comprises a mixture of hydroxypropyl cellulose and nitrocellulose, said hydroxypropyl cellulose being present in an amount sufficient to impart stability to said paste.

Claim 24

A sealing glass paste according to claim 18 in which said solvent is selected from the group consisting of amyl acetate, ethylene glycol methyl ether, ethylene gycol ethyl ether, methyl amyl acetate, ethyl hexyl acetate, n-butyl acetate, isobutyl acetate, sec. butyl acetate and diethylene glycol monobutyl ether acetates.

Claim 25

A sealing glass paste according to claim 18 wherein said hydroxypropyl cellulose has an average molecular weight of from between about 40,000 and about 300,000.

Claim 26

A sealing glass paste according to claim 20 wherein said solvent is amyl acetate.

Claim 27

A sealing glass paste according to claim 20 in which said solvent is ethylene glycol methyl ether.

Claim 28

A sealing glass paste according to claim 18 in which said binder consists essentially of nitrocellulose and a hydroxypropyl cellulose having a molecular weight of about 40,000 to about 300,000, and said solvent comprises amyl acetate in admixture with ethylene glycol methyl ether.

Claim 29

A sealing glass paste according to claim 23 in which said hydroxypropyl cellulose has an average molecular weight of about 60,000.

Claim 30

A sealing glass paste according to claim 23 which comprises about 5 to 30% by weight of a 4-weight percent solution of hydroxypropyl cellulose in equal parts by weight of amyl acetate and ethylene glycol methyl ether, and about 95 to 70% by weight of a 1 to 6.2 weight percent solution of nitrocellulose in amyl acetate.

Claim 31

A sealing glass paste comprising: A. a sealing glass composition according to claim 13, B. a binder selected from the group consisting of nitrocellulose, hydroxypropyl cellulose and mixtures thereof, and C. a solvent for said binder.

Claim 32

A sealing glass paste comprising: A. a sealing glass composition according to claim 16, B. a binder selected from the group consisting of nitrocellulose, hydroxypropyl cellulose and mixtures thereof, and C. a solvent for said binder.