CA1274857A - Lead-free glass frit compositions - Google Patents
Lead-free glass frit compositionsInfo
- Publication number
- CA1274857A CA1274857A CA000550627A CA550627A CA1274857A CA 1274857 A CA1274857 A CA 1274857A CA 000550627 A CA000550627 A CA 000550627A CA 550627 A CA550627 A CA 550627A CA 1274857 A CA1274857 A CA 1274857A
- Authority
- CA
- Canada
- Prior art keywords
- sio2
- zno
- na2o
- composition
- tio2
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 239000011521 glass Substances 0.000 title claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910011255 B2O3 Inorganic materials 0.000 claims abstract description 19
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 16
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 16
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 7
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 10
- 229910007472 ZnO—B2O3—SiO2 Inorganic materials 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 210000003298 dental enamel Anatomy 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical class [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004534 enameling Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000759 toxicological effect Toxicity 0.000 description 1
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
- 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
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
Abstract
LEAD-FREE GLASS FRIT COMPOSITIONS
Abstract of the Disclosure Lead-free glass frit compositions for use in vitreous coatings consisting essentially of Na2O-ZnO-B2O3-SiO2 in appropriate concentrations including molar amounts of at most 17.5 mole percent of B2O3 and at least 40 mole percent of SiO2.
Abstract of the Disclosure Lead-free glass frit compositions for use in vitreous coatings consisting essentially of Na2O-ZnO-B2O3-SiO2 in appropriate concentrations including molar amounts of at most 17.5 mole percent of B2O3 and at least 40 mole percent of SiO2.
Description
7~
Decorating compositions generally fall into two categories; glazes and enamels. The glazes are usually thought of as clear glasses, while enamels are glazes which contain a coloring material such as a pigment. In actual usage, ~he glazes and enamels are used in a finely divided form called a "frit", which is selectively applied to the surfaces of the glassware, glass-ceramic ware, chinaware and ceramic ware in accordance with the intended decorative or ornamental pattern. Any of several decorating techniques known in the industry can be used to achieve this result. Typically, the frit is in the form of a paste which consists of the finely divided glaze or enamel composition plus a vehicle. After application to the ware by silk screen or other technique, the ware is heated or fired to fuse the frit, to volatilize the vehicle or medium and to firmly bond the decoration to the surface of the ware.
There are a variety of decorating compositions avail-able which are used in the decorating of glassware, china-ware and the like, to produce selected patterns and ornamentation. These available compositions frequently contain lead and/or cadmium oxides. Lead oxide was previously used in these compositions to lower the melting point of the frit so that the frit could be fused onto the surface of the ware at as low a temperature as possible to avoid thermal deformation of the ware. Cadmium oxide had been used in the past as a colorant in certain frits.
However, adverse toxicological effects from these systems have resulted in various prohibitions on the use of lead and cadmium in decorative glazes. It has, therefore, been necessary to formulate glass frit products with e~uivalent or improved performance characteristics but with no lead or cadmium components.
-` ~.2~
A number of such lead-free products have been disclosed. By way of illustration, U.S. 4,376,169 discloses frits which require the presence of alkali oxide, B2O3, A12O3, SiO~, F, P2O5, ZnO and TiO2 and which have critical compositional limits; U.S. 4,446,241 discloses frits which require the presence of Li2O, B2O3 and SiO2 among other oxides; U.S. 4,537,862 discloses frits which require the presence of B2O3, SiO2, ZrO2 and rare earth oxides with the weight ratio of ZrO2 to rare earth oxides being critical U.S 4,554,258 discloses frits which require the presence of ~i2O3, B2O3, SiO2 and alkali metal oxides where the alkali metal oxides are necessarily present in specified concentrations and U.S. 4,590,171 discloses frits which require the presence of Li2o, Na2O, BaO, Ba2O3, A1203, Si2~ ZrO2 and F- It is thus seen that the formulations have varied the nature and concentration of the oxide components in an attempt to provide acceptable frit formulations. While such frits are alleged to exhibit a variety of desirable properties, they still exhibit deficiencies in one or more performance areas.
Accordingly~ it is the primary object of this invention to provide lead-free glass frit compositions which exhibit a broad range of improved performance characteristics.
It is a further object to provide such frits which are low melting and are particularly resistant to acid attac~.
Various other objects and advantages of this invention will become apparent from the following descriptive material.
~2'7~
It has now been surprisingly determined that the aforementioned objectives are met by preparing lead-free glass frits which consist of Na2O, ZnO, B2O3 and SiO2 in appropriate concentration ranges. Such systems meet the primary requirement of being operative in vitreous coatings without the presence of lead and cadmium components. In addition, these formulations exhibit a broad range of desirable properties including low melting points, suffi-ciently low thermal expansion to avoid crazing when applied over soda-lime-silica glass and low water solubility to facilitate their use in water based spray mediums. Of particular significance is the excellent resistance to acid attack, such as ~hat encountered from various acid-containing liquids such as juice. As a result, these glass frit compositions are available for a broad range of glazing, enameling and decorating applications on a wide variety of g7assware and chinaware. They can also be applied in a variety of printing methods.
More specifically, the glass frit compositions of this invention consist of Broad Range(mole ~) P erred Range(mole %~
Na2o3.9 - 18.5 5.0 - 14.0 ZnO4.0 - 30.0 8.0 ~ 25~0 B2O33.9 - 17.5 6.0 - 13.0 SiO240.0 - 74.0 45.0 - 60.0 It is particularly to be noted that coatings which significantly exceed the 17.5 mole percent B2O3 concentration do not exhibit the minimum level of acid resistance required for such products~ In addition, coatings which contain less than the minimum 40.0 mole percent Si2 content are likewise deficient in acid resistance.
~2~7~8~
In addi~ion to the oxides listed above, the coatings may contain one or more of the following witho~t adversely ! effecting the performance characteristics:
mole percent K20 0- 8.0 Li2O 0- 5.0 CaO 0- 8.0 SrO 0- 8 0 BaO ~ 9 0 Bi23 0-10.0 A1203 0- 4.0 Zr2 0- 6.0 I Ti~2 0- 7.0 WO3 O- l.O
The K2O and Li2O will generally replace a portion of the Na2O content. The K2O will tend to increase the firing temperature and thermal expansion, while the Li2O will lower the firing temperature but may create some thermal stresses. The CaO, SrO and BaO can be added as partial replacement for the ZnO, such components increasing firing temperature and thermal expansion. Addi~ions of ZrO2 will improve alkali resistance, while the TiO2 will improve acid resistance.
The glass frits can be prepared by mixing together the oxide producing materials, such materials being well known to those skilled in the art, charging the raw material mix into a glass melting furnace at temperatures of 1000-1200C to produce the fused glass and then fritting the glass as by pouring into water or passing through water-cooled rolls. If required, the frit can be ground into powder by conventional grinding techniquesO The 12~L8~a'7 resulting products generally haYe melting points in the range of 450 to 600C and coefficients of thermal expansion in the range of 70 to 90 X 10-7 per C.
1, The frits of the present inventlon are particularly useful for vitrifiable glass decorating colors, but they may also be used in related applications such as coatings on ceramic substrates. For example, to use these materials as a glass decorating color, a slip made up of the frit of the present invention, titanium dioxide and an alcohol-water mixture is prepared. This slip is then applied to the exterior of a glass jar or a light bulb (e.g. by spraying) and the coated surface is then fired at 680C for three minutes. The result is a smooth vitreous coating which will resist attack from a variety of acidic and alkaline materials. It is also to be noted that colorants and pigments can be dissolved and/or suspended in the frits to yield colored glazes and enamels.
The following examples further illustrate the embodiments of this invention. In these examples, known techniques are utilized to mix the appropriate raw batch glass compositions, to melt them at generally about 1200C
for about 45 minutes and then to frit the compositions.
Testing is conducted by adding 4.0 grams of the glass frit to 1.0 gram of a pine oil-based medium and screen printing the resulting dispersion onto glass slides at a wet thickness of 2 mils~ The slides are fired at several temperatures to determine "Gloss Temperature", i.e. the lowest temperature which enables the glass powder to flow sufficiently to form a smooth transparent coating.
.
Acid resistance is evaluated first by utilizing ASTM
C724-81 and then by immersing the coated glass slides in 4%
~ acetic acid for a period of 24 hours. Coatin~s rated "A"
I in the first test and coatings which are not etched or only marginally etched in the second test are deemed to be acid resistant.
Typical frit formula~ions of this invention and one control ~ormulation and their attendant performance characteristics are noted in the following table.
Ingredient _ Formulation(mole %) Na2O 12.1 11.4 12.1 11.4 11.4 5.7 13.2 ZnO 18.2 17.2 13.7 17.1 8.6 17.2 13.2 B2O3 12.2 11~4 12.1 17.1 17.1 17.1 21.0 SiO2 54.5 51.4 54.6 51.5 51.4 51.4 47.4 TiO2 3.0 2.9 3.0 2.9 2.9 2.9 3.9 Li2o ~ ~ 4.5 K2O - - - - - 5.7 Bi23 _ 5.7 BaO - - - - 8.6 F2 - - - - - - 1.3 Gloss Temp(C) 650 607 621 650 677 650 621 Acid Rating A A A A A A C
not not not sl. sl. sl. coating 4~ Acetic Acid etched etched etched etch etch etch removed These results thus indicate the excellent performance benefits of the instant systems, particularly in ~he area of acid resi~stance. In addition, the results of control Formulation A illustrate the adverse effects obtained by I utilizing B203 in excess of the prescribed amounts.
¦ A similar composition can be prepared using, on a mole percent basis, 13.1% Na20, 19.7% ZnO, 8.2% B203 and 59.0~ SiO2, with the expectation of comparable performance characteristics.
Summarizing, this invention is seen to provide lead-free glass frit compositions exhibiting excellent performance characteristics particularly in the area of acid resistance. Variations may be made in procedures, proportions and materials without departing from the scope of the invention as defined by the following claims.
Decorating compositions generally fall into two categories; glazes and enamels. The glazes are usually thought of as clear glasses, while enamels are glazes which contain a coloring material such as a pigment. In actual usage, ~he glazes and enamels are used in a finely divided form called a "frit", which is selectively applied to the surfaces of the glassware, glass-ceramic ware, chinaware and ceramic ware in accordance with the intended decorative or ornamental pattern. Any of several decorating techniques known in the industry can be used to achieve this result. Typically, the frit is in the form of a paste which consists of the finely divided glaze or enamel composition plus a vehicle. After application to the ware by silk screen or other technique, the ware is heated or fired to fuse the frit, to volatilize the vehicle or medium and to firmly bond the decoration to the surface of the ware.
There are a variety of decorating compositions avail-able which are used in the decorating of glassware, china-ware and the like, to produce selected patterns and ornamentation. These available compositions frequently contain lead and/or cadmium oxides. Lead oxide was previously used in these compositions to lower the melting point of the frit so that the frit could be fused onto the surface of the ware at as low a temperature as possible to avoid thermal deformation of the ware. Cadmium oxide had been used in the past as a colorant in certain frits.
However, adverse toxicological effects from these systems have resulted in various prohibitions on the use of lead and cadmium in decorative glazes. It has, therefore, been necessary to formulate glass frit products with e~uivalent or improved performance characteristics but with no lead or cadmium components.
-` ~.2~
A number of such lead-free products have been disclosed. By way of illustration, U.S. 4,376,169 discloses frits which require the presence of alkali oxide, B2O3, A12O3, SiO~, F, P2O5, ZnO and TiO2 and which have critical compositional limits; U.S. 4,446,241 discloses frits which require the presence of Li2O, B2O3 and SiO2 among other oxides; U.S. 4,537,862 discloses frits which require the presence of B2O3, SiO2, ZrO2 and rare earth oxides with the weight ratio of ZrO2 to rare earth oxides being critical U.S 4,554,258 discloses frits which require the presence of ~i2O3, B2O3, SiO2 and alkali metal oxides where the alkali metal oxides are necessarily present in specified concentrations and U.S. 4,590,171 discloses frits which require the presence of Li2o, Na2O, BaO, Ba2O3, A1203, Si2~ ZrO2 and F- It is thus seen that the formulations have varied the nature and concentration of the oxide components in an attempt to provide acceptable frit formulations. While such frits are alleged to exhibit a variety of desirable properties, they still exhibit deficiencies in one or more performance areas.
Accordingly~ it is the primary object of this invention to provide lead-free glass frit compositions which exhibit a broad range of improved performance characteristics.
It is a further object to provide such frits which are low melting and are particularly resistant to acid attac~.
Various other objects and advantages of this invention will become apparent from the following descriptive material.
~2'7~
It has now been surprisingly determined that the aforementioned objectives are met by preparing lead-free glass frits which consist of Na2O, ZnO, B2O3 and SiO2 in appropriate concentration ranges. Such systems meet the primary requirement of being operative in vitreous coatings without the presence of lead and cadmium components. In addition, these formulations exhibit a broad range of desirable properties including low melting points, suffi-ciently low thermal expansion to avoid crazing when applied over soda-lime-silica glass and low water solubility to facilitate their use in water based spray mediums. Of particular significance is the excellent resistance to acid attack, such as ~hat encountered from various acid-containing liquids such as juice. As a result, these glass frit compositions are available for a broad range of glazing, enameling and decorating applications on a wide variety of g7assware and chinaware. They can also be applied in a variety of printing methods.
More specifically, the glass frit compositions of this invention consist of Broad Range(mole ~) P erred Range(mole %~
Na2o3.9 - 18.5 5.0 - 14.0 ZnO4.0 - 30.0 8.0 ~ 25~0 B2O33.9 - 17.5 6.0 - 13.0 SiO240.0 - 74.0 45.0 - 60.0 It is particularly to be noted that coatings which significantly exceed the 17.5 mole percent B2O3 concentration do not exhibit the minimum level of acid resistance required for such products~ In addition, coatings which contain less than the minimum 40.0 mole percent Si2 content are likewise deficient in acid resistance.
~2~7~8~
In addi~ion to the oxides listed above, the coatings may contain one or more of the following witho~t adversely ! effecting the performance characteristics:
mole percent K20 0- 8.0 Li2O 0- 5.0 CaO 0- 8.0 SrO 0- 8 0 BaO ~ 9 0 Bi23 0-10.0 A1203 0- 4.0 Zr2 0- 6.0 I Ti~2 0- 7.0 WO3 O- l.O
The K2O and Li2O will generally replace a portion of the Na2O content. The K2O will tend to increase the firing temperature and thermal expansion, while the Li2O will lower the firing temperature but may create some thermal stresses. The CaO, SrO and BaO can be added as partial replacement for the ZnO, such components increasing firing temperature and thermal expansion. Addi~ions of ZrO2 will improve alkali resistance, while the TiO2 will improve acid resistance.
The glass frits can be prepared by mixing together the oxide producing materials, such materials being well known to those skilled in the art, charging the raw material mix into a glass melting furnace at temperatures of 1000-1200C to produce the fused glass and then fritting the glass as by pouring into water or passing through water-cooled rolls. If required, the frit can be ground into powder by conventional grinding techniquesO The 12~L8~a'7 resulting products generally haYe melting points in the range of 450 to 600C and coefficients of thermal expansion in the range of 70 to 90 X 10-7 per C.
1, The frits of the present inventlon are particularly useful for vitrifiable glass decorating colors, but they may also be used in related applications such as coatings on ceramic substrates. For example, to use these materials as a glass decorating color, a slip made up of the frit of the present invention, titanium dioxide and an alcohol-water mixture is prepared. This slip is then applied to the exterior of a glass jar or a light bulb (e.g. by spraying) and the coated surface is then fired at 680C for three minutes. The result is a smooth vitreous coating which will resist attack from a variety of acidic and alkaline materials. It is also to be noted that colorants and pigments can be dissolved and/or suspended in the frits to yield colored glazes and enamels.
The following examples further illustrate the embodiments of this invention. In these examples, known techniques are utilized to mix the appropriate raw batch glass compositions, to melt them at generally about 1200C
for about 45 minutes and then to frit the compositions.
Testing is conducted by adding 4.0 grams of the glass frit to 1.0 gram of a pine oil-based medium and screen printing the resulting dispersion onto glass slides at a wet thickness of 2 mils~ The slides are fired at several temperatures to determine "Gloss Temperature", i.e. the lowest temperature which enables the glass powder to flow sufficiently to form a smooth transparent coating.
.
Acid resistance is evaluated first by utilizing ASTM
C724-81 and then by immersing the coated glass slides in 4%
~ acetic acid for a period of 24 hours. Coatin~s rated "A"
I in the first test and coatings which are not etched or only marginally etched in the second test are deemed to be acid resistant.
Typical frit formula~ions of this invention and one control ~ormulation and their attendant performance characteristics are noted in the following table.
Ingredient _ Formulation(mole %) Na2O 12.1 11.4 12.1 11.4 11.4 5.7 13.2 ZnO 18.2 17.2 13.7 17.1 8.6 17.2 13.2 B2O3 12.2 11~4 12.1 17.1 17.1 17.1 21.0 SiO2 54.5 51.4 54.6 51.5 51.4 51.4 47.4 TiO2 3.0 2.9 3.0 2.9 2.9 2.9 3.9 Li2o ~ ~ 4.5 K2O - - - - - 5.7 Bi23 _ 5.7 BaO - - - - 8.6 F2 - - - - - - 1.3 Gloss Temp(C) 650 607 621 650 677 650 621 Acid Rating A A A A A A C
not not not sl. sl. sl. coating 4~ Acetic Acid etched etched etched etch etch etch removed These results thus indicate the excellent performance benefits of the instant systems, particularly in ~he area of acid resi~stance. In addition, the results of control Formulation A illustrate the adverse effects obtained by I utilizing B203 in excess of the prescribed amounts.
¦ A similar composition can be prepared using, on a mole percent basis, 13.1% Na20, 19.7% ZnO, 8.2% B203 and 59.0~ SiO2, with the expectation of comparable performance characteristics.
Summarizing, this invention is seen to provide lead-free glass frit compositions exhibiting excellent performance characteristics particularly in the area of acid resistance. Variations may be made in procedures, proportions and materials without departing from the scope of the invention as defined by the following claims.
Claims (9)
1. A lead-free glass frit composition consisting essentially of the following components in the indicated molar percent amounts:
Na20 3.9 - 18.5 ZnO 4.0 - 30.0 B2O3 3.9 - 17.5 SiO2 40.0 - 74.0 K2O 0 - 8.0 Li2O 0 - 5.0 CaO 0 - 8.0 SrO 0 - 8.0 BaO 0 - 9.0 Bi2O3 0 - 10.0 A12O3 0 - 4.0 ZrO2 0 - 6.0 TiO2 0 - 7.0 WO3 0 - 1.0
Na20 3.9 - 18.5 ZnO 4.0 - 30.0 B2O3 3.9 - 17.5 SiO2 40.0 - 74.0 K2O 0 - 8.0 Li2O 0 - 5.0 CaO 0 - 8.0 SrO 0 - 8.0 BaO 0 - 9.0 Bi2O3 0 - 10.0 A12O3 0 - 4.0 ZrO2 0 - 6.0 TiO2 0 - 7.0 WO3 0 - 1.0
2. The composition of claim 1 wherein the indicated components are present in the indicated molar percent amounts:
Na2O 5.0 - 14.0 ZnO 8.0 - 25.0 B2O3 6.0 - 13.0 SiO2 45.0 - 60.0
Na2O 5.0 - 14.0 ZnO 8.0 - 25.0 B2O3 6.0 - 13.0 SiO2 45.0 - 60.0
3. The composition of claim 1 consisting essentially of the following components in the indicated mole percent amounts.
Na2O 12.1 ZnO 18.2 B2O3 12.2 SiO2 54.5 TiO2 3.0
Na2O 12.1 ZnO 18.2 B2O3 12.2 SiO2 54.5 TiO2 3.0
4. The composition of claim 1 consisting essentially of the following components in the indicated mole percent amounts:
Na2O 11.4 ZnO 17.2 B2O3 11.4 SiO2 51.4 TiO2 2.9 Bi2O3 5.7
Na2O 11.4 ZnO 17.2 B2O3 11.4 SiO2 51.4 TiO2 2.9 Bi2O3 5.7
5. The composition of claim 1 consisting essentially of the following components in the indicated mole percent amounts:
Na2O 12.1 ZnO 13.7 B2O3 12.1 SiO2 54.6 TiO2 3.0 Li2O 4.5
Na2O 12.1 ZnO 13.7 B2O3 12.1 SiO2 54.6 TiO2 3.0 Li2O 4.5
6. The composition of claim 1 consisting essentially of the following components in the indicated mole percent amounts:
Na2O 11.4 ZnO 17.1 B2O3 17.1 SiO2 51.5 TiO2 2.9
Na2O 11.4 ZnO 17.1 B2O3 17.1 SiO2 51.5 TiO2 2.9
7. The composition of claim 1 consisting essentially of the following components in the indicated mole percent amounts:
Na2O 11.4 ZnO 8.6 B2O3 17.1 SiO2 51.4 TiO2 2.9 BaO 8.6
Na2O 11.4 ZnO 8.6 B2O3 17.1 SiO2 51.4 TiO2 2.9 BaO 8.6
8. The composition of claim 1 consisting essentially of the following components in the indicated mole percent amounts:
Na2O 5.7 ZnO 17.2 B2O3 17.1 SiO2 51.4 TiO2 2.9 K2O 5.7
Na2O 5.7 ZnO 17.2 B2O3 17.1 SiO2 51.4 TiO2 2.9 K2O 5.7
9. A process for preparing a lead-free glass frit composition comprising the steps of (a) combining raw materials in amounts such that the glass frit will consist essentially of mole percent Na2O 3.9 - 18.5 ZnO 4.0 - 30.0 B2O3 3.9 - 17.5 SiO2 40.0 - 74.0 K2O 0 - 8.0 Li2O 0 - 5.0 CaO 0 - 8.0 SrO 0 - 8.0 BaO 0 - 9.0 Bi2O3 0 - 10.0 Al2O3 0 - 4.0 ZrO2 0 - 6.0 TiO2 0 - 7.0 WO3 0 - 1.0 (b) melting the raw material at a temperature of from 1000 to 1200°C; and (c) forming a frit from the molten mass.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US92607286A | 1986-11-03 | 1986-11-03 | |
| US926,072 | 1986-11-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1274857A true CA1274857A (en) | 1990-10-02 |
Family
ID=25452706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000550627A Expired - Lifetime CA1274857A (en) | 1986-11-03 | 1987-10-30 | Lead-free glass frit compositions |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0267154B2 (en) |
| JP (1) | JP2505828B2 (en) |
| KR (1) | KR950006202B1 (en) |
| BR (1) | BR8705807A (en) |
| CA (1) | CA1274857A (en) |
| DE (1) | DE3769435D1 (en) |
| ES (1) | ES2022449T5 (en) |
| MX (1) | MX9121A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0631995A1 (en) | 1993-06-24 | 1995-01-04 | Dentsply GmbH | Dental prosthesis |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4814298A (en) * | 1987-10-26 | 1989-03-21 | Corning Glass Works | Lead-free glasses for glaze materials |
| GB9008386D0 (en) * | 1990-04-12 | 1990-06-13 | Cookson Group Plc | Glass frit compositions |
| GB9027063D0 (en) * | 1990-12-13 | 1991-02-06 | British Ceramic Res Ltd | Improved glaze |
| GB9108257D0 (en) * | 1991-04-17 | 1991-06-05 | Cookson Group Plc | Glaze compositions |
| IT1251175B (en) * | 1991-08-13 | 1995-05-04 | Bayer Italia Spa | FRITS FOR CERAMIC SHOWCASES WITHOUT LEAD, CADMIUM AND BARIUM |
| DE4201286C2 (en) * | 1992-01-20 | 1994-11-24 | Schott Glaswerke | Use of lead and cadmium-free glass compositions for glazing, enameling and decorating and their composition |
| FR2687997B1 (en) * | 1992-03-02 | 1996-07-05 | Degussa Prod Ceramiques | GLASS SINTERS CONTAINING ZINC, FREE OF LEAD AND CADMIUM - PROCESS OF MANUFACTURE AND USE. |
| US5204291A (en) * | 1992-04-17 | 1993-04-20 | Corning Incorporated | Transparent lead-free glazes |
| ATE161523T1 (en) * | 1992-07-01 | 1998-01-15 | Proceram | LEAD-FREE, TRANSPARENT, GLASS-CERAMIC COMPOSITIONS AND ITEMS MADE THEREFROM |
| US5401287A (en) * | 1993-08-19 | 1995-03-28 | Ppg Industries, Inc. | Reduction of nickel sulfide stones in a glass melting operation |
| US5346651A (en) * | 1993-08-31 | 1994-09-13 | Cerdec Corporation | Silver containing conductive coatings |
| US5447891A (en) * | 1993-09-29 | 1995-09-05 | Ferro Corporation | Lead-free glaze or enamel for use on ceramic bodies |
| FR2712881B1 (en) * | 1993-11-25 | 1996-05-15 | Cerdec France Sa | Composition of glass frits free of lead and cadmium, in particular for the manufacture of enamels for the enameling of windshields and / or panoramic roofs. |
| GB9401818D0 (en) * | 1994-01-31 | 1994-03-23 | Cookson Group Plc | Glass compositions |
| 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 |
| US5439852A (en) * | 1994-08-01 | 1995-08-08 | E. I. Du Pont De Nemours And Company | Cadmium-free and lead-free thick film conductor composition |
| DE19502653A1 (en) * | 1995-01-28 | 1996-08-01 | Cerdec Ag | Lead-free glass composition and its use |
| DE19506123C2 (en) * | 1995-02-22 | 1997-01-09 | Cerdec Ag | Lead-free glass frit, process for its manufacture and its use |
| DE19512847C1 (en) * | 1995-04-06 | 1996-11-07 | Schott Glaswerke | Lead- and cadmium-free glass compsn. |
| FR2732960B1 (en) * | 1995-04-14 | 1997-06-20 | Eurokera | NO LEAD-FREE ENAMELS FOR THE DECORATION OF LOW-EXPANSION VITROCERAMICS |
| US5559059A (en) * | 1995-05-22 | 1996-09-24 | Cerdec Corporation | Lead-free glass frits for ceramics enamels |
| KR100262623B1 (en) * | 1998-03-18 | 2001-01-15 | 이한용 | Glass composition for producing heat insulating foam glass and method for preparing foam glass using the glass composition |
| EP1138641A1 (en) | 2000-03-30 | 2001-10-04 | Schott Glas | Lead-free bismuth silicate glasses and their uses |
| KR100632001B1 (en) * | 2005-07-29 | 2006-10-09 | 삼성전기주식회사 | Glass compositions for low temperature sintering, glass frit, dielectric compositions and multilayer ceramic condenser using the same |
| US8772189B2 (en) * | 2011-05-04 | 2014-07-08 | Ferro Corporation | Glass frit compositions for enamels |
| CN103996424A (en) * | 2014-04-16 | 2014-08-20 | 池州市华硕电子科技有限公司 | Wear-resistant printed circuit board silver slurry and preparation method thereof |
| JP6686410B2 (en) * | 2015-12-14 | 2020-04-22 | 日本電気硝子株式会社 | Crystallized glass substrate with glass powder, composite powder and painting layer |
| WO2020223178A1 (en) * | 2019-04-30 | 2020-11-05 | Corning Incorporated | Chemically durable, lithium-free glass compositions |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2799590A (en) * | 1954-05-21 | 1957-07-16 | Corning Glass Works | Glass |
| NL6412848A (en) * | 1963-11-12 | 1965-05-13 | ||
| US4312951A (en) * | 1979-09-07 | 1982-01-26 | Mobay Chemical Corporation | Low-melting, lead-free ceramic frits |
| DE3045249A1 (en) * | 1980-12-01 | 1982-07-01 | Eisenwerke Fried. Wilh. Düker GmbH & Co, 8782 Karlstadt | METHOD FOR APPLYING A RESISTANT PROTECTIVE ENAMEL COVER TO DUCTILE MOLDED BODY |
| US4417913A (en) * | 1981-10-26 | 1983-11-29 | Motorola, Inc. | Lower temperature glass and hermetic seal means and method |
-
1987
- 1987-10-26 KR KR1019870011891A patent/KR950006202B1/en not_active IP Right Cessation
- 1987-10-29 ES ES87810619T patent/ES2022449T5/en not_active Expired - Lifetime
- 1987-10-29 EP EP87810619A patent/EP0267154B2/en not_active Expired - Lifetime
- 1987-10-29 DE DE8787810619T patent/DE3769435D1/en not_active Expired - Lifetime
- 1987-10-30 BR BR8705807A patent/BR8705807A/en not_active IP Right Cessation
- 1987-10-30 CA CA000550627A patent/CA1274857A/en not_active Expired - Lifetime
- 1987-11-02 JP JP62275893A patent/JP2505828B2/en not_active Expired - Fee Related
- 1987-11-03 MX MX912187A patent/MX9121A/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0631995A1 (en) | 1993-06-24 | 1995-01-04 | Dentsply GmbH | Dental prosthesis |
| US5849068A (en) * | 1993-06-24 | 1998-12-15 | Dentsply G.M.B.H. | Dental prosthesis |
| US6126732A (en) * | 1993-06-24 | 2000-10-03 | Dentsply Detrey Gmbh | Dental prosthesis |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63117927A (en) | 1988-05-21 |
| EP0267154B2 (en) | 1994-05-11 |
| EP0267154A1 (en) | 1988-05-11 |
| KR880006135A (en) | 1988-07-21 |
| MX9121A (en) | 1993-12-01 |
| DE3769435D1 (en) | 1991-05-23 |
| EP0267154B1 (en) | 1991-04-17 |
| ES2022449B3 (en) | 1991-12-01 |
| KR950006202B1 (en) | 1995-06-12 |
| BR8705807A (en) | 1988-06-14 |
| JP2505828B2 (en) | 1996-06-12 |
| ES2022449T5 (en) | 1995-08-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed | ||
| MKEC | Expiry (correction) |
Effective date: 20121205 |