WO1990015782A1 - Lead-free glass - Google Patents
Lead-free glass Download PDFInfo
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- WO1990015782A1 WO1990015782A1 PCT/US1989/002847 US8902847W WO9015782A1 WO 1990015782 A1 WO1990015782 A1 WO 1990015782A1 US 8902847 W US8902847 W US 8902847W WO 9015782 A1 WO9015782 A1 WO 9015782A1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/06—Frit compositions, i.e. in a powdered or comminuted form containing halogen
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
Definitions
- This invention relates to a lead-free glass and more particularly, to lead-free glass frits that exhibit excellent alkali and acid resistance, possess low coefficients of linear or thermal expansion, and moderate maturation temperatures.
- This invention relates to a method of decorating architectural glass structures, such as glass spandrels, appliance glassware and other glass objects.
- a glaze is typically thought of as a clear glass
- an enamel is a glaze which contains a pigment or other particles in suspension.
- Such glazes and enamels are applied to glass surfaces in the form of a paste, the paste containing finely ground particles of the glaze or enamel, commonly called “frit” and a vehicle. After application of the glaze or enamel to the glass surface by silk screening or other techniques, the glass is fired to fuse the frit, bond the glaze or enamel to the glass surface and volatilize the vehicle.
- the use of lead oxide in these compositions served to lower the melting point of the frit so as to prevent any possible thermal deformation of the underlying glass. Recent efforts have been made at retaining the low melt temperature of these glazes and enamels but with the removal of the lead oxide for health reasons.
- a lead, cadmium and zinc-free glass frit for use in glazes or enamels having a low softening point (about 535°C to about 609°C) is taught by Francel et al in U.S. Patent 4,446,241. These frits contain a large amount of rare earths in addition to a large amount of lithium.
- a lead-free glass composition comprising:
- silicon dioxide from about 30% to about 51% by weight silicon dioxide, from about 19% to about 50% by weight boron oxide, from about 2% to about 20% by weight zirconium oxide, up to 14% by weight sodium oxide, up to about 6% by weight potassium oxide, up to about 19% by weight zinc oxide, and up to about 5% by weight lithium oxide; and from about 2 to about 8 parts by weight fluorine per 100 parts of the other components in said composition.
- up to about 8% by weight barium oxide and up to about 4% by weight titanium dioxide can be added to the foregoing glass composition.
- This invention relates to a lead- and cadmiumfree glass frit possessing not only a moderately low coefficient of thermal expansion but also possessing an excellent resistance to both alkali and acid environments. Furthermore, the maturation temperature for the glass systems herein described is moderate. Such glasses find utility as glazes or enamels for systems requiring excellent chemical and thermal stability. Examples of such applications include glazes or enameels for glass panels used in appliances and spandrels for architectural windows. Other outdoor applications where the glaze or enamel is exposed to acidic or alkaline environments are contemplated. This invention also provides for a method of decorating glass substrates by the application of a glass frit made according to this invention to a glass substrate and subsequent firing resulting in a lead-free glass coating.
- the moderate maturation temperature of the glazes and enamels of this invention minimizes thermal damage or distortion to the underlying glass during firing. Also, the low coefficient of thermal expansion of these systems (from about 69 ⁇ 10 cm/cm°C to about 84 ⁇ 10 -7 cm/cm°C) is desirable so as to yield a good compression in the glaze or enamel layer when fired onto commercial soda-lime glass.
- the glaze or enamel of the present invention preferably matures and is compatible with a relatively fast fire approximately 630°C to 690°C (glass temperature) for a relatively brief period, that is preferably about 1 to about 5 minutes. If, however, the glass is sagged or pressed into a curved shape, a slower fire is necessitated, with a longer hold, that is typically about 4 to about 20 minutes. In both such cases, a coefficient of linear thermal expansion of preferably about 85 ⁇ 10 cm/cm°C or less is desirable so as to yield some compression in the glaze or enamel layer.
- temperatures referred to herein are glass temperatures, that is to say the temperature of the glass itself, which may be somewhat lower than oven temperature, particularly in commercial applications.
- the glasses of the foregoing type can be melted in sintered fused silica crucibles at 1200-1250°C with little attack on the crucible, though melting time must be controlled somewhat closely because of fluorine loss and will vary according to the size of the batch.
- a preferred time for a 500 gm batch may be about 25 to about 30 minutes, while a preferred time for 1 kg batch of the same composition may be about 55 to about 65 minutes.
- the melt may be handled by any suitable means though typically it is quenched by steel rolls into flake or frit, using techniques well-known to those skilled in the art.
- This invention relates to a lead-free glass comprising the following components exclusive of fluorine:
- F 2 is present in these compositions at a concentration of about 2 to about 8 parts, preferably about 3 to about 7 parts by weight based on a total of 100 parts of the other components in these compositions.
- the glass enamels are made according to the following technique. Glass frits, in flake or granular form, are ball-milled to an average particular size of about 3 to about 4 microns as measured on a Microtrac at the 50% level, with either a water or a water and an alcohol solution (e.g., 50% water and 50% isopropyl alcohol), dried, and blended with a screen printing vehicle (e.g., a glycol ether acetate-based system). The resulting ink composition is screen-printed on glass substrates by methods known in the art and then fired.
- a screen printing vehicle e.g., a glycol ether acetate-based system
- a glass enamel composition indicated in Table I as Formulation A is prepared by ball milling the indicated materials in an alcohol solution until a particle size of about 3 microns to about 4 microns, as determined by a Microtrac at a 50% level, is achieved. The particles are dried. The dried particles are blended into a screen printing vehicle, and applied to glass substrates, and then fired. Some samples are held for 45 minutes at the following temperatures: 1050°F, 1100°F, 1150°F, 1200°F, and 1250°F. Other samples are fast-fired at 1250°F for 3, 4, 5 and 6 minutes. All samples are then cooled to room temperature.
- a second glass enamel composition, screenable ink and decorative coating is prepared by using Formula B in Table I and following the steps set forth in Example 1.
- Example 3 A second glass enamel composition, screenable ink and decorative coating is prepared by using Formula B in Table I and following the steps set forth in Example 1.
- a third glass enamel composition, screenable ink and decorative coating was prepared by using Formula I in Table I and following the steps set forth in Example 1.
- Table I discloses physical data on ten formulations, all of which exhibit coefficients of linear thermal expansion (CLTE) ranging from about 73 ⁇ 10 -7 cm/cm°C to about 84 ⁇ 10 -7 cm/cm°C.
- Table I includes the glass transition temperatures (Tg), the dilatometric softening points (DSP) where the viscosity is approximately 10 11.4 poise, and the fiber softening points (FSP) where the viscosity is 10 7.6 poise, within the limits of measurement.
- the firing temperature is approximately 100°C higher than the fiber softening point.
- Subtotal 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
- the gloss measurements are relative reflection measurements known to the art.
- the reflectance measurements are made as a function of firing temperatures, all reflectance measurements taken at room temperature. For the following temperatures: 1050°F, 1100°F, 1150°F, 1200°F and 1250°F, the enamel coatings are fired for 45 minutes, other firing times are as indicated.
- the fit is determined by optical technique known to the art whereby a one-inch section is submerged in a butye phthalate solution and the stress between the substrate glass and the enamel coating is measured. A determination as to whether the enamel coating is in tension or compression can be made.
- the citric acid test involves exposing the fired glass enamel for 15 minutes to a drop of a 10% solution by weight of citric acid at room temperature and visually accessing the damage to the glass enamel.
- the citric acid solution is freshly made for each test.
- the hydrochloric acid test is done by exposing the glass enamel to a drop of a 3.5% by volume solution of hydrochloric acid for 15 minutes at room temperature and rating the appearance of the enamel using the same rating scheme as used for the citric acid test.
- alkali tests are performed by exposing the fired glass enamel to 10% by weight sodium hydroxide solution in water for 2 hours at 200°F and subsequently measuring the weight loss in grams per square centimeter (25 cm sample area).
- Another alkali test is performed by exposing the fired enamel to a 160°F solution of 9.5% by weight sodium hydroxide and .5% by weight trisodium phosphate for 8 hours and subsequently measuring the weight loss in grams per square centimeter (49 cm sample area).
- Table II compares and contrasts the glosses as a function of temperature, the frits, the citric acid tests and the gloss for samples using Formulations A, B and J indicated in Table I that were fast-fired at 1250°F for 3, 4, 5 and 6 minutes for two samples, No. 1 and No. 2.
- Table III depicts, by weight, modified recipes of glasses A through J whose formulations are disclosed in Table I. These new formulations, indicated by primes, and in the case of J' and J", comprise the glass recipes disclosed in Table I with the addition of an amount, by weight, of a black pigment and in the case of J", a small amount of a conventional additive.
- Table III reports gloss data, including the gloss measured on samples fired for 6 minutes at 1250°F, the fit data on a one-inch section, the citric acid spot test data, the hydrochloric acid test data (3.5% by volume), the sodium hydroxide test data (10% by weight. 200°F, 2-hour exposure) and the sodium hydroxide (9.5% by weight) trisodium phosphate (0.5% by weight) data (160°F, 8 hours).
- Architectural glass coatings and glass coatings for coating appliances can be made by firing the inventive compositions at temperatures in the range of about 530°C to about 590°C.
- Glass spandrels or architectural glass can be decorated by coating the spandrel or glass with the coating composition comprising the inventive glass compositions using conventional techniques, and firing the composition at a temperature in the range of about 630°C to about 690°C. Glass used on appliances and other glass objects can be similarly coated using the inventive compositions and the foregoing firing temperature range.
- Ink compositions used in these techniques typically comprise about 15% to about 25% by weight vehicle, about 8% to about 16% by weight pigment, and about 50% to about 90% by weight of the inventive glass compositions.
- the vehicle typically comprises from about 77% to about 84% by weight pine oil, from about 15% to about 20% by weight acrylic resin, and from about 1% to about 3% by weight surfactant.
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Abstract
A lead-free glass composition comprising: from about 30 % to about 51 % by weight silicon dioxide, from about 19 % to about 50 % by weight boron oxide, from about 2 % to about 20 % by weight zirconium oxide, up to 14 % by weight sodium oxide, up to about 6 % by weight potassium oxide, up to about 19 % by weight zinc oxide, and up to about 5 % by weight lithium oxide; and from about 2 to about 8 parts by weight fluorine per 100 parts of the other components in said composition. Additionally, up to about 8 % by weight barium oxide and up to about 4 % by weight titanium dioxide can be added to the foregoing glass composition.
Description
Title: LEAD-FREE GLASS
This application is a Continuation-in-Part of U.S. Application Serial No. 134,518, filed December 17, 1987, said prior application being incorporated herein by reference in its entirety.
Field of the Invention
This invention relates to a lead-free glass and more particularly, to lead-free glass frits that exhibit excellent alkali and acid resistance, possess low coefficients of linear or thermal expansion, and moderate maturation temperatures. This invention relates to a method of decorating architectural glass structures, such as glass spandrels, appliance glassware and other glass objects.
Background of the Invention
Lead containing glazes and enamels for glass substrates are well known in the ceramic art. A glaze is typically thought of as a clear glass, whereas an enamel is a glaze which contains a pigment or other particles in suspension. Such glazes and enamels are applied to glass surfaces in the form of a paste, the paste containing finely ground particles of the glaze or enamel, commonly called "frit" and a vehicle. After application of the glaze or enamel to the glass surface by silk screening or other techniques, the glass is fired to fuse the frit, bond the glaze or enamel to the glass surface and volatilize the vehicle.
In the past, the use of lead oxide in these compositions served to lower the melting point of the frit so as to prevent any possible thermal deformation of the underlying glass. Recent efforts have been made at retaining the low melt temperature of these glazes and enamels but with the removal of the lead oxide for health reasons.
As elucidated by Eppler in U.S. Patent 4,312,951, one of the difficulties encountered in these systems is the development of a low-melting glass system which retains a favorable durability; that is, frits which are minimally soluble in water at moderate temperatures. Typically, a decrease in the melt temperature also diminishes the durability of the glass frit. Eppler teaches a low-melting lead-free durable glass with a low-water solubility, the glasses formed from selected compositions in the alkali-ZnO-Al2O3-B2O3- P2O5-SiO2-TiO2-F system. These particular glass systems exhibit large coefficients of thermal expansion (from 9.8 to 15.1 × 10-6 cm/cm°C) and thus are unsuitable for glass decoration purposes.
As disclosed by Francel et al in U.S. Patent 4,537,862, it is beneficial in some applications to use a lead-free, cadmium-free and zinc-free glass having an improved alkali and acid reistance. These glaze and enamel frits find use in decorating food service ware for applications such as glass tumblers and china ware. These glazes contain large amounts of rare earths in addition to strontium oxide, calcium oxide and tungsten oxide. Of further interest, as indicated by Barlier et al in U.S. Patent 4,532,221, are enamel systems having a low coefficient of thermal expansion suitable for the decoration of glass-ceramics. The systems disclosed by
Barlier et al, however, contain lead oxide. A lead, cadmium and zinc-free glass frit for use in glazes or enamels having a low softening point (about 535°C to about 609°C) is taught by Francel et al in U.S. Patent 4,446,241. These frits contain a large amount of rare earths in addition to a large amount of lithium.
Summary of the Invention
A lead-free glass composition comprising:
from about 30% to about 51% by weight silicon dioxide, from about 19% to about 50% by weight boron oxide, from about 2% to about 20% by weight zirconium oxide, up to 14% by weight sodium oxide, up to about 6% by weight potassium oxide, up to about 19% by weight zinc oxide, and up to about 5% by weight lithium oxide; and from about 2 to about 8 parts by weight fluorine per 100 parts of the other components in said composition. Additionally, up to about 8% by weight barium oxide and up to about 4% by weight titanium dioxide can be added to the foregoing glass composition.
Detailed Description of the Invention This invention relates to a lead- and cadmiumfree glass frit possessing not only a moderately low coefficient of thermal expansion but also possessing an excellent resistance to both alkali and acid environments. Furthermore, the maturation temperature for the glass systems herein described is moderate. Such glasses find utility as glazes or enamels for systems requiring excellent chemical and thermal stability. Examples of such applications include glazes or enameels for glass panels used in appliances and spandrels for architectural windows. Other outdoor applications where the glaze or enamel is exposed to acidic or alkaline environments are contemplated.
This invention also provides for a method of decorating glass substrates by the application of a glass frit made according to this invention to a glass substrate and subsequent firing resulting in a lead-free glass coating.
The moderate maturation temperature of the glazes and enamels of this invention minimizes thermal damage or distortion to the underlying glass during firing. Also, the low coefficient of thermal expansion of these systems (from about 69 × 10 cm/cm°C to about 84 × 10-7 cm/cm°C) is desirable so as to yield a good compression in the glaze or enamel layer when fired onto commercial soda-lime glass.
For use in conjunction with substantially flat glass substrates, the glaze or enamel of the present invention preferably matures and is compatible with a relatively fast fire approximately 630°C to 690°C (glass temperature) for a relatively brief period, that is preferably about 1 to about 5 minutes. If, however, the glass is sagged or pressed into a curved shape, a slower fire is necessitated, with a longer hold, that is typically about 4 to about 20 minutes. In both such cases, a coefficient of linear thermal expansion of preferably about 85 × 10 cm/cm°C or less is desirable so as to yield some compression in the glaze or enamel layer. Unless otherwise indicated, temperatures referred to herein are glass temperatures, that is to say the temperature of the glass itself, which may be somewhat lower than oven temperature, particularly in commercial applications.
The glasses of the foregoing type can be melted in sintered fused silica crucibles at 1200-1250°C with little attack on the crucible, though melting time must
be controlled somewhat closely because of fluorine loss and will vary according to the size of the batch. A preferred time for a 500 gm batch may be about 25 to about 30 minutes, while a preferred time for 1 kg batch of the same composition may be about 55 to about 65 minutes. The melt may be handled by any suitable means though typically it is quenched by steel rolls into flake or frit, using techniques well-known to those skilled in the art.
This invention relates to a lead-free glass comprising the following components exclusive of fluorine:
More Preferred
Preferred Range Range
Component (Wt.%) (Wt.%)
SiO2 30-51 35-45
B2O3 19-50 20-30
ZrO2 2-20 5-14
Na2O 0-14 6-10
K2O 0-6 2-6
Li2O 0-5 0-2
ZnO 0-19 10-18
BaO 0-8 0-3
TiO2 0-4 0-3
Al2O3 0-22 0-20
La2O3 0-8 0-5
Bi2O3 0-7 0-5
Sb2O5 0-7 0-5
P2O5 0-7 0-5
CeO2 0-7 0-5
SrO 0-5 0-3
CaO 0-4 0-2
SuO 0-4 0-3
SuO2 0-4 0-2
SuF2 0-4 0-2
Nb2O5 0-4 0-2
V2O5 0-4 0-2
Nb2O5 0-4 0-2
Y2O3 0-4 0-2
F2 is present in these compositions at a concentration of about 2 to about 8 parts, preferably about 3 to about 7 parts by weight based on a total of 100 parts of the other components in these compositions.
The glass enamels are made according to the following technique. Glass frits, in flake or granular form, are ball-milled to an average particular size of about 3 to about 4 microns as measured on a Microtrac at the 50% level, with either a water or a water and an alcohol solution (e.g., 50% water and 50% isopropyl alcohol), dried, and blended with a screen printing vehicle (e.g., a glycol ether acetate-based system). The resulting ink composition is screen-printed on glass substrates by methods known in the art and then fired.
By way of illustration and not by any limitation, the following examples will describe specific glass compositions within the scope of the present invention. Unless otherwise indicated, all parts and percentages are by weight, and all temperatures are in degrees Centigrade.
Example 1
A glass enamel composition indicated in Table I as Formulation A is prepared by ball milling the indicated materials in an alcohol solution until a particle size of about 3 microns to about 4 microns, as determined by a Microtrac at a 50% level, is achieved. The particles are dried. The dried particles are blended into a screen printing vehicle, and applied to glass substrates, and then fired. Some samples are held for 45 minutes at the following temperatures: 1050°F, 1100°F, 1150°F, 1200°F, and 1250°F. Other samples are fast-fired at 1250°F for 3, 4, 5 and 6 minutes. All samples are then cooled to room temperature.
Example 2
A second glass enamel composition, screenable ink and decorative coating is prepared by using Formula B in Table I and following the steps set forth in Example 1.
Example 3
A third glass enamel composition, screenable ink and decorative coating was prepared by using Formula I in Table I and following the steps set forth in Example 1.
Table I discloses physical data on ten formulations, all of which exhibit coefficients of linear thermal expansion (CLTE) ranging from about 73 × 10-7 cm/cm°C to about 84 × 10-7 cm/cm°C. Table I includes the glass transition temperatures (Tg), the dilatometric softening points (DSP) where the viscosity is approximately 1011.4 poise, and the fiber softening points (FSP) where the viscosity is 107.6 poise, within the limits of measurement. The firing temperature is approximately 100°C higher than the fiber softening point.
TABLE I
A B C D E F G H I J
SiO2 40 39 41 41 40 40 42 42 40 40 .91
B2O3 24 22 24 24 23 24 24 24 23 27 .27 ZrO2 10 8 8 8 8 9 7 7 7 6. 82
Na2O 8.06 θ 8.06 8. 06 8 8.06 8.06 8.06 8 7. 63
K2O 4.44 4 4.44 4. 44 4 4.44 4.44 4.44 4 3. 74Li2O 0.50 1 0.50 0. 50 1 0.50 0.50 0.50 1 -- ZnO 13 17 14 13 15 13 13 14 15 11 .36 BaO -- -- -- -- -- -- -- -- -- 2. 27 TiO2 -- 1 -- 1 1 1 1 -- 2 --
Subtotal 100 100 100 100 100 100 100 100 100 100
F2 6 6 6 6 6 6 6 6 6 4.55
Total 106 106 106 106 106 106 106 106 106 104.55
CLTE×10-7 (cm/
cm°C) 83.5 80.7 80.7 80.7 83.6 73.5 77.8 75.6 81.5 69.1 Tg(ºC) 418 403 403 406 400 408 403 409 416 437 DSP(ºC) 480 459 455 460 450 461 460 458 469 490 FSP(°C) -- 552 552 546 538 564 575 566 552 588
Other tests of glass enamels are known to the art as well as the literature. For example, the gloss of glass enamels, in part for aesthetic reasons, is an important parameter to measure, the frit of the glass enamel is indicative as to whether the glass enamel will be in tension or compression╌compression desirable, citric acid spot test and alkali tests are grouped together, termed, and are important as durability tests. Another test (reported in Table III) is the hydrochloric acid test. Although this test is not a standarized test, it is an appropriate one in that some of the masonary materials contain hydrochloric acid as a component and this test anticipates spattering of these materials onto the glass enamel and attempts to evaluate the resulting damage to the glass enamel.
The gloss measurements are relative reflection measurements known to the art. The reflectance measurements are made as a function of firing temperatures, all reflectance measurements taken at room temperature. For the following temperatures: 1050°F, 1100°F, 1150°F, 1200°F and 1250°F, the enamel coatings are fired for 45 minutes, other firing times are as indicated. The fit is determined by optical technique known to the art whereby a one-inch section is submerged in a butye phthalate solution and the stress between the substrate glass and the enamel coating is measured. A determination as to whether the enamel coating is in tension or compression can be made. The citric acid test involves exposing the fired glass enamel for 15 minutes to a drop of a 10% solution by weight of citric acid at room temperature and visually accessing the damage to the glass enamel. The citric acid solution is freshly made for each test. The hydrochloric acid test is done by
exposing the glass enamel to a drop of a 3.5% by volume solution of hydrochloric acid for 15 minutes at room temperature and rating the appearance of the enamel using the same rating scheme as used for the citric acid test. The ratings used to conform to the following criteria:
(1) No attach apparent.
(2) Appearance of irridescence or visible stain on the exposed surface when viewed at a 45° angle, but not apparent at angles less than 30°.
(3) A definite stain which does not blur reflected images and is visible at angles less than 30°.
(4) Definite stain with a gross color change or strongly irridescent surface visible at angles less than 30° and which may blur reflected images.
(5) Surface dull or matte, with chalking possible.
(6) Significant removal of enamel with pinholing evident.
(7) Complete removal of enamel in exposed area.
One of the alkali tests is performed by exposing the fired glass enamel to 10% by weight sodium hydroxide solution in water for 2 hours at 200°F and subsequently measuring the weight loss in grams per square centimeter (25 cm sample area). Another alkali test is performed by exposing the fired enamel to a 160°F solution of 9.5% by weight sodium hydroxide and .5% by weight trisodium phosphate for 8 hours and subsequently measuring the weight loss in grams per square centimeter (49 cm sample area).
Table II compares and contrasts the glosses as a function of temperature, the frits, the citric acid
tests and the gloss for samples using Formulations A, B and J indicated in Table I that were fast-fired at 1250°F for 3, 4, 5 and 6 minutes for two samples, No. 1 and No. 2.
TABLE II
Sample No. 1 Sample No. 2
Formulation A:
Gloss - after
firing at:
1050°F 60 50
1100°F 60 60
1150°F 155 110
1200°F 185 170
1250°F 195 200
1300°F 180 205
Lehr 170 140
Fit 1" section -5 -5
Citric spot test 5 5
Gloss - fast fire
at 1250°F for:
3 minutes 170 140
4 minutes 170 180
5 minutes 175 175
6 minutes 185 190
Sample No. 1 Sample No. 2
Formulation B:
Gloss - after
firing at:
1050°F 60 65
1100°F 125 115
1150°F 175 165
1200°F 185 185
1250°F 205 185
1300°F 185 170
Lehr 195 190
Fit 1" section -20 -15
Citric spot test 5 5
Gloss - fast fire
at 1250°F for:
3 minutes 195 195
4 minutes 180 170
5 minutes 180 170
6 minutes 185 170
Sample No. 1 Sample No. 2
Formulation J:
Gloss - after
firing at:
1050ºF 50 50
1100°F 55 55
1150°F 125 95
1200°F 185 165
1250°F 200 185
1300°F 180 190
Lehr 150 100
Fit 1" section +5 +20
Citric spot test 5 5
Gloss - fast fire
at 1250°F for:
3 minutes 150 150
4 minutes 175 175
5 minutes 190 175
6 minutes 170 165
The upper part of Table III depicts, by weight, modified recipes of glasses A through J whose formulations are disclosed in Table I. These new formulations, indicated by primes, and in the case of J' and J", comprise the glass recipes disclosed in Table I with the addition of an amount, by weight, of a black pigment and in the case of J", a small amount of a conventional additive. Table III reports gloss data, including the gloss measured on samples fired for 6 minutes at 1250°F, the fit data on a one-inch section, the citric acid spot test data, the hydrochloric acid test data (3.5% by volume), the sodium hydroxide test data (10% by weight.
200°F, 2-hour exposure) and the sodium hydroxide (9.5% by weight) trisodium phosphate (0.5% by weight) data (160°F, 8 hours).
TABLE III
A' B' C' D' E' F'
A 92.5
B 92.5
C 92.5
D 92.5
E 694
F 694
G
H
I
J
Black Pigment 7.5 7.5 7.5 7.5 5 56
Conventional Additive
Gloss after firing at 1050ºF 10 5 5 5 20 10
" 1100ºF 10 20 5 10 60 5
" 1150ºF 110 130 105 105 110 30 " 1200ºF 110 140 125 130 130 100 " 1250ºF 110 135 120 110 135 120
Lehr 40 115 60 100 125 80
1250°F, 6-m1nute firing time 120-130 130 120 120 150 150
Fit, 1" section 0 -25 -10 -10 -65 -10
Citric spot test 4 4 4 4 4 4
Hydrochloric add test 4 4 4 4 4 4
Sodium hydroxide test-200ºF, (2 hrs) 0.0017 0.0016 0.0014 0.0014 0.0036 0.0042
Sodium hydroxide, tri-sodium phosphate test: 160ºF, (8 hrs) 0.0022 0.0024 0.0025 0.0024 0.0027 0.0024
TABLE III (Contd)
G' H' J' J"
A
B
C
D
E
F
G 694
H 694
I
J 85 85
Black Pigment 56 56 15 15
Conventional Additive 5
Gloss-after firing at 1050ºF 5 5
" 1100°F 5 5
" 1150ºF 50 35
" 1200ºF 115 110
" 1250ºF 125 125
Lehr 100 85
1250°F, 6-minute firing time 140 130 110
Fit, 1" section -15 -20 +20 +5
Citric spot test 4 4 2 4
Hydrochloric add test 4 4
Sodium hydroxide test-200ºF, (2 hrs) 0.0025 0.0028
Sodium hydroxide, tri-sodium phosphate test: 160ºF, (8 hrs) 0.0019 0.0022
Architectural glass coatings and glass coatings for coating appliances can be made by firing the inventive compositions at temperatures in the range of about 530°C to about 590°C.
Glass spandrels or architectural glass can be decorated by coating the spandrel or glass with the coating composition comprising the inventive glass compositions using conventional techniques, and firing the composition at a temperature in the range of about 630°C to about 690°C. Glass used on appliances and other glass objects can be similarly coated using the inventive compositions and the foregoing firing temperature range. Ink compositions used in these techniques typically comprise about 15% to about 25% by weight vehicle, about 8% to about 16% by weight pigment, and about 50% to about 90% by weight of the inventive glass compositions. The vehicle typically comprises from about 77% to about 84% by weight pine oil, from about 15% to about 20% by weight acrylic resin, and from about 1% to about 3% by weight surfactant.
While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.
Claims
Claims
1. A lead-free glass composition comprising: from about 30% to about 51% by weight silicon dioxide, from about 19% to about 50% by weight boron oxide, from about 2% to about 20% by weight zirconium oxide, up to 14% by weight sodium oxide, up to about 6% by weight potassium oxide, up to about 19% by weight zinc oxide, and up to about 5% by weight lithium oxide; and from about 2 to about 8 parts by weight fluorine per 100 parts of the other components in said composition.
2. The composition of claim 1 further comprising up to about 8% by weight barium oxide and up to about 4% by weight titanium dioxide.
3. The composition of claim 1 comprising:
Parts/Wt.
SiO2 40
B2O3 24
ZrO2 10
Na2O 8.06
K2O 4.44
Li2O 0.50
ZnO 13
F2 6
The composition of claim 1 comprising
Parts/Wt.
SiO2 41
B2O3 24
ZrO2 8
Na2O 8.06
K2O 4.44
Li2O 0.50
ZnO 14
F2 6
The composition of claim 1 comprising
Parts/Wt.
SiO2 42
B2O3 24
ZrO2 7
Na2O 8.06
K2O 4.44
Li2O 0.50
ZnO 14
F2 6
6. The composition of claim 1 comprising
Parts/Wt.
SiO2 39
B2O3 22
ZrO2 8
Na2O 8
K2O 4
Li2O 1
ZnO 17
TiO2 1
F2 6
7. The composition of claim 1 comprising
Parts/Wt.
SiO2 41
B2O3 24
ZrO2 8
Na2O 8.06
K2O 4.44
Li2O 0.50
ZnO 13
TiO2 1
F2 6
8 . The composition of claim 1 comprising:
Parts/Wt.
SiO2 40
B2O3 23
ZrO2 8
Na2O 8
K2O 4
Li2O 1
ZnO 15
TiO2 1
F2 6
9. The composition of claim 1 comprising:
Parts/Wt.
SiO2 40
B2O3 24
ZrO2 9
Na2O 8.06
K2O 4.44
Li2O 0.50
ZnO 13
TiO2 1
F2 6
1 0 , The composition of claim 1 comprising:
Parts/Wt.
SiO2 42
B2O3 24
ZrO2 7
Na2O 8.06
K2O 4.44
Li2O 0.50
ZnO 13
TiO2 1
F2 6
11. The composition of claim 1 comprising:
Parts/Wt.
SiO2 40
B2O3 23
ZrO2 7
Na2O 8
K2O 4
Li2O 1
ZnO 15
TiO2 2
F2 6
12. The composition of claim 1 comprising:
Parts/Wt.
SiO2 40.91
B2O3 27.27
ZrO2 6.82
Na2O 7.63
K2O 3.74
ZnO 11.36
. BaO 2.27
F2 6
13. A lead-free architectural glass-coating made by firing the composition of claim 1 at a temperature of from about 530° C to about 590°C until said composition is fused and cured.
14. A lead -free appliance glass-coating made by firing the composition of claim 1 at a temperature of from about 530°C to about 590°C until said composition is fused and cured.
15. An ink composition comprising from about 15% to about 25% by weight vehicle, from about 8% to about 16% by weight pigment, and from about 50% to about 90% by weight of the composition of claim 1.
16. The composition of claim 15 wherein said vehicle comprises from about 77% to about 84% by weight pine oil, from about 15% to about 20% by weight acrylic resin, and from about 1% to about 3% by weight surfactant.
17. A method of decorating a glass spandrel or architectural glass comprising coating said spandrel or architectural glass with the composition of claim 1 and firing said composition at a temperature of from about 630°C to about 690°C until said composition is fused and cured.
18. A method of decorating glass used in appliances or other glass objects comprising coating said glass with the composition of claim 1 and firing said composition at a temperature of from about 630°C to about 690°C until said composition is fused and cured.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1989/002847 WO1990015782A1 (en) | 1987-12-17 | 1989-06-21 | Lead-free glass |
| CA 2010098 CA2010098A1 (en) | 1989-06-21 | 1990-02-14 | Lead-free glass |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/134,518 US4859637A (en) | 1987-12-17 | 1987-12-17 | Lead-free U.V. absorbing glass |
| PCT/US1989/002847 WO1990015782A1 (en) | 1987-12-17 | 1989-06-21 | Lead-free glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1990015782A1 true WO1990015782A1 (en) | 1990-12-27 |
Family
ID=26779799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1989/002847 WO1990015782A1 (en) | 1987-12-17 | 1989-06-21 | Lead-free glass |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO1990015782A1 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4201286A1 (en) * | 1992-01-20 | 1993-07-22 | Schott Glaswerke | LEAD- AND CADMIUM-FREE GLASS COMPOSITION FOR GLAZING, ENAMELING AND DECORATING AND THEIR USE |
| US5252521A (en) * | 1992-10-19 | 1993-10-12 | Ferro Corporation | Bismuth-containing lead-free glass enamels and glazes of low silica content |
| US5306674A (en) * | 1992-09-04 | 1994-04-26 | Ferro Corporation | Lead-free glass coatings |
| WO1995025009A1 (en) * | 1994-03-16 | 1995-09-21 | Ferro Corporation | Lead-free glass enamels for decorating glass beverage containers and methods for using the same |
| US5633090A (en) * | 1993-01-21 | 1997-05-27 | Schott Glaswerke | Lead-and cadmium-free glass composition for glazing, enameling and decorating glass |
| US5976999A (en) * | 1992-07-01 | 1999-11-02 | Proceram | Unleaded transparent vitreous ceramic compositions |
| EP3437623A4 (en) * | 2016-03-28 | 2019-11-20 | GC Corporation | Glass powder for dental use |
| US10646410B2 (en) | 2016-03-28 | 2020-05-12 | Gc Corporation | Dental cement |
| US10806680B2 (en) | 2016-06-13 | 2020-10-20 | Gc Corporation | Dental polymerizable composition |
| US10918577B2 (en) | 2016-06-30 | 2021-02-16 | Gc Corporation | Dental treatment material and dental treatment material kit |
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|---|---|---|---|---|
| DE4201286A1 (en) * | 1992-01-20 | 1993-07-22 | Schott Glaswerke | LEAD- AND CADMIUM-FREE GLASS COMPOSITION FOR GLAZING, ENAMELING AND DECORATING AND THEIR USE |
| US5976999A (en) * | 1992-07-01 | 1999-11-02 | Proceram | Unleaded transparent vitreous ceramic compositions |
| US5306674A (en) * | 1992-09-04 | 1994-04-26 | Ferro Corporation | Lead-free glass coatings |
| US5252521A (en) * | 1992-10-19 | 1993-10-12 | Ferro Corporation | Bismuth-containing lead-free glass enamels and glazes of low silica content |
| US5326591A (en) * | 1992-10-19 | 1994-07-05 | Ferro Corporation | Bismuth-containing lead-free glass enamels and glazes of low silica content |
| US5633090A (en) * | 1993-01-21 | 1997-05-27 | Schott Glaswerke | Lead-and cadmium-free glass composition for glazing, enameling and decorating glass |
| US5725919A (en) * | 1994-03-16 | 1998-03-10 | Ferro Corporation | Lead-free glass enamels for decorating glass beverage containers and methods for using the same |
| WO1995025009A1 (en) * | 1994-03-16 | 1995-09-21 | Ferro Corporation | Lead-free glass enamels for decorating glass beverage containers and methods for using the same |
| EP3437623A4 (en) * | 2016-03-28 | 2019-11-20 | GC Corporation | Glass powder for dental use |
| US10646408B2 (en) | 2016-03-28 | 2020-05-12 | Gc Corporation | Dental glass powder |
| US10646410B2 (en) | 2016-03-28 | 2020-05-12 | Gc Corporation | Dental cement |
| US10806680B2 (en) | 2016-06-13 | 2020-10-20 | Gc Corporation | Dental polymerizable composition |
| US10918577B2 (en) | 2016-06-30 | 2021-02-16 | Gc Corporation | Dental treatment material and dental treatment material kit |
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