IP Library Granted Patent US 9,688,566
Granted Patent B2
US 9,688,566 · App. 15/227,136 · Granted Jun 27, 2017

Nickel-free and chromium-free forehearth colors for glass tanks

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Quick Facts
Patent No.
US 9,688,566
App. No.
15/227,136
Granted
Jun 27, 2017
Kind
B2
Abstract

The invention relates to the field of forehearth frits, pearls, and/or concentrates for use in glass compositions. In particular, the present invention provides a system of forehearth frits, pearls, and/or concentrates that is capable of imparting a brown color to a glass composition for forming colored glass in the forehearth of a glass furnace, and a method of using the colored system of forehearth frits, pearls, and/or concentrates. The invention further provides a glass composition for use in forming the color system or for use directly in a forehearth.

Claims (114)

1. A color glass frit free of nickel and chromium, the frit comprising in weight %:

from about 30 to about 50% SiO 2 ,

from about 15 to about 30% Na 2 O,

from about 1 to about 10% B 2 O 3 ,

from about 10 to about 30% Fe 2 O 3 ,

from about 0.1 to about 5% ZnO,

from about 0.1 to about 5% Al 2 O 3 ,

from about 0.1 to about 5% CuO,

from about 0.01 to about 1% CoO,

from about 0.1 to about 5% Se;

from about 1 to about 8% SnO/SnO 2 ,

no nickel and

no chromium.

2. The color glass frit of claim 1 wherein the color glass frit is further devoid of at least one heavy metal other than nickel and chromium.

3. The color glass frit of claim 1 wherein the color glass frit is further devoid of all heavy metals.

4. A method for coloring a molten base glass in the forehearth of a glass furnace comprising the steps of:

a. forming a frit that is free of nickel and chromium, the frit comprising in weight %:

i. from about 30 to about 50% SiO 2 ,

ii. from about 15 to about 30% Na 2 O,

iii. from about 1 to about 10% B 2 O 3 ,

iv. from about 10 to about 30% Fe 2 O 3 ,

v. from about 0.1 to about 5% ZnO,

vi. from about 0.1 to about 5% Al2O3,

vii. from about 0.1 to about 5% CuO,

viii. from about 0.01 to about 1% CoO,

ix. from about 0.1 to about 5% Se; and

x. from about 1 to about 8% SnO/SnO 2 .

b. combining the frit with the molten glass contained in a forehearth so as to impart color to the molten glass; and

c. cooling the molten glass to form a color glass composition.

5. A system of at least two color glass frits free of nickel and chromium, the first frit comprising in weight %:

from about 30 to about 50% SiO 2 ,

from about 15 to about 30% Na 2 O,

from about 1 to about 10% B 2 O 3 , and

from about 10 to about 30% Fe 2 O 3 ,

from about 0.1 to about 5% ZnO,

from about 0.1 to about 10% Al 2 O 3 .

from about 0.1 to about 5% CuO,

from about 0.01 to about 1% CoO,

from about 0.1 to about 5% Se, and

the second frit comprising in weight %:

from about 30 to about 65% SiO 2 ,

from about 5 to about 15% Na 2 O,

from about 1 to about 5% B 2 O 3 ,

from about 1 to about 5% ZnO,

from about 5 to about 17% SnO or SnO 2 ,

from about 0.1 to about 3% Al 2 O 3 ,

from about 3 to about 10% K 2 O,

from about 3 to about 10% BaO,

from about 2 to about 6% CaO.

6. The color system of claim 5 wherein the first frit is devoid of at least one of SnO/SnO 2 K 2 O, BaO, CaO and MgO.

7. The color glass frit of claim 5 wherein the color glass frit is further devoid of at least one heavy metal other than nickel and chromium.

8. The color glass frit of claim 5 wherein the color glass frit is further devoid of all heavy metals.

9. A method for coloring a molten base glass in the forehearth of a glass furnace comprising the steps of:

a. forming a first frit that is free of nickel and chromium, the first frit comprising in weight %:

i. from about 30 to about 50% SiO 2 ,

ii. from about 15 to about 30% Na 2 O,

iii. from about 1 to about 10% B 2 O 3 ,

iv. from about 10 to about 30% Fe 2 O 3 ,

v. from about 0.1 to about 5% ZnO,

vi. from about 0.1 to about 10% Al 2 O 3 .

vii. from about 0.1 to about 5% CuO,

viii. from about 0.01 to about 1% CoO, and

ix. from about 0.1 to about 5% Se and

b. forming a second frit that is free of nickel and chromium, the second frit comprising in weight %

i. from about 30 to about 65% SiO 2 ,

ii. from about 5 to about 15% Na 2 O,

iii. from about 1 to about 5% B 2 O 3 ,

iv. from about 1 to about 5% ZnO,

v. from about 5 to about 17% SnO or SnO2,

vi. from about 0.1 to about 3% Al 2 O 3 ,

vii. from about 3 to about 10% K 20 ,

viii. from about 3 to about 10% BaO, and

ix. from about 2 to about 6%) CaO,

c. combining the first and second frits with the molten glass contained in a forehearth so as to impart color to the molten glass; and

d. cooling the molten glass to form a color glass composition.

10. A color system including at least one frit that is free of nickel and chromium and at least one pearl that is free of nickel and chromium, the color glass frit comprising in weight %:

from about 30 to about 50% SiO 2 ,

from about 15 to about 30% Na 2 O,

from about 1 to about 10% B 2 O 3 , and

from about 10 to about 30% Fe 2 O 3 ,

from about 0.1 to about 5% ZnO,

from about 0.1 to about 10% Al 1 O 3,

from about 0.1 to about 5% CuO,

from about 0.01 to about 1% CoO, and

from about 0.1 to about 5% Se, and

the pearl comprising a glass frit comprising in weight:

from about 15 to about 45% SiO 2 ,

from about 20 to about 50% Na 2 O,

from about 0.5 to about 5% B 2 O 3 ,

from about 15 to about 35% SnO or SnO 2 , and

from about 0.1 to about 3% CaO.

11. The color glass system of claim 10 wherein the color glass frit is further devoid of at least one heavy metal other than nickel and chromium.

12. The color glass system of claim 10 wherein the color glass frit is further devoid of all heavy metals.

13. The color glass system of claim 10 wherein the color glass frit is devoid of at least one of SnO/SnO 2 , K 2 O, BaO, CaO and MgO.

14. The color glass system of claim 10 wherein the pearl is devoid of at least one of Fe 2 O 3 , ZnO, Al 2 O 3 , CoO, CuO, Se, K 2 O, BaO and MgO.

15. A method for coloring a molten base glass in the forehearth of a glass furnace comprises the steps of:

a. forming a first frit that is free of nickel and chromium, the first frit comprising in weight %:

i. from about 30 to about 50% SiO 2 ,

ii. from about 15 to about 30% Na 2 O,

iii. from about 1 to about 10% B 2 O 3 ,

iv. from about 10 to about 30% Fe 2 O 3 ,

v. from about 0.1 to about 5% ZnO,

vi. from about 0.1 to about 10% Al 2 O 3 .

vii. from about 0.1 to about 5% CuO,

viii. from about 0.01 to about 1% CoO, and

ix. from about 0.1 to about 5% Se and

b. forming a pearl that is free of nickel and chromium and comprises in weight %:

i. from about 15 to about 45% SiO 2 ,

ii. from about 20 to about 50% Na 2 O,

iii. from about 0.5 to about 5% B 2 O 3 ,

iv. from about 15 to about 35% SnO or SnO 2 , and

v. from about 0.1 to about 3% CaO.

c. combining the first frit and pearl with the molten glass contained in a forehearth so as to impart color to the molten glass; and

d. cooling the molten glass to form a color glass composition.

Assignments (4)
SECURITY INTEREST Recorded May 2, 2022
From: CHROMAFLO TECHNOLOGIES CORPORATION; FERRO CORPORATION; FERRO ELECTRONIC MATERIALS INC.; PRINCE ENERGY LLC; PRINCE MINERALS LLC; PRINCE SPECIALTY PRODUCTS LLC
To: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS ADMINISTRATIVE AGENT
Reel/Frame 059845/0082 →
RELEASE OF SECURITY INTEREST IN PATENTS RECORDED AT R/F 041736/0178 Recorded Apr 21, 2022
From: PNC BANK NATIONAL ASSOCIATION, AS COLLATERAL AGENT
To: FERRO CORPORATION
Reel/Frame 059747/0129 →
SECURITY INTEREST Recorded Feb 16, 2017
From: FERRO CORPORATION
To: PNC BANK, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 041736/0178 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 29, 2016
From: DARBOURET, BENOIT; GRAPTON, JEAN-LUC; SAKOSKE, GEORGE E.
To: FERRO CORPORATION
Reel/Frame 039561/0701 →