CA2048061C - Ultraviolet absorbing green tinted glass - Google Patents
Ultraviolet absorbing green tinted glassInfo
- Publication number
- CA2048061C CA2048061C CA002048061A CA2048061A CA2048061C CA 2048061 C CA2048061 C CA 2048061C CA 002048061 A CA002048061 A CA 002048061A CA 2048061 A CA2048061 A CA 2048061A CA 2048061 C CA2048061 C CA 2048061C
- Authority
- CA
- Canada
- Prior art keywords
- glass
- percent
- transmittance
- iron
- total iron
- 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 - Fee Related
Links
- 239000011521 glass Substances 0.000 title claims abstract description 62
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- 238000002834 transmittance Methods 0.000 claims abstract description 32
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000006121 base glass Substances 0.000 claims abstract description 6
- 239000003086 colorant Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 9
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 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
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 11
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract 1
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 229910052684 Cerium Inorganic materials 0.000 description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 230000001603 reducing effect Effects 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 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
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured glass
-
- 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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass
Abstract
A green tinted, ultraviolet absorbing glass is obtained by the addition of colorant to a standard soda-lime-silica base glass composition and a colorant includes less than 0.5 weight percent of cerium oxide (CeO2), greater than 0.85 weight percent of total iron expressed as Fe2O3 and a ratio of ferric iron expressed as FeO to total iron of less than 0.275. The glass has a low ultraviolet transmittance, viz., no greater than 31 percent over the wavelength range of 300 to 390 nanometers at a reference glass thickness of 3.9 millimeters. An advantage of the glass of this invention over competing ultraviolet absorbing glass is the use of larger amounts of total iron and smaller proportions of iron in the ferrous state to obtain the low ultraviolet transmittance. In this manner, the amounts of cerium oxide which is expensive is reduced.
Description
~48~61 ~.
ULTRAVIOLET ABSORBING GREEN TINTED GLASS
BACKGROUND OF THE INVENTION
This invention relates to soda-lime-silica glass 5 particularly suitable for controlling transmittance of solar radiation in window glazing applications. The glass may be generally described as being green tinted, and ls designed to have low heat transmittance and particularly enhanced absorption in the ultraviolet wavelength range. This is desirable for the sake of reducing the 10 rate at which the sun's rays deteriorate plastics and fabrics in applications such as automobiles. A particular objective of the invention is to permit glass of this type to be made at a lower cost by reducing the amount of costly ingredients required.
Soda-lime-silica flat glass may be essentially characterized 15 by the following composition on a weight percentage basis of the total glass:
SiO268 - 75%
Na20 10 - 20 CaO 5 - 15 MgO O - 5 Other minor ingredients, including melting and refining aids such as S03, may also appear in the glass composition. Small amounts 25 of K20, BaO or B203 and other minor constituents have also sometimes been included in flat glass and may be considered optional. To this base glass are added the coloring constituents that produce the transmittance properties of the glass. The primary colorant in the category of glasses relevant to the present invention is iron, which 30 is usually present in both the Fe203 and FeO forms. As is conventional, the total amount of iron present in a glass is expressed herein as Fe203, regardless of the form actually present.
A typical green tinted automotive glass has about 0.5 percent by weight total iron, with the ratio of FeO to total iron being about 35 0.25.
Larger amounts of iron have been used in some specialty glasses intended to lower the total solar energy transmittance.
, ~
~ - 2 -204~06 1 However, merely increasing the amount of total iron does not reduce the ultraviolet transmittance to the extent desired even when the amount of iron present is sufficient to lower the luminous (visible light) transmittance to the m~ml~ acceptable for automotive 5 applications under conventional commercial melting conditions. The colorant composition and transmittance properties for examples of two commercial products of this high iron, dark green tinted type along with an example of the conventional, light green tinted glass described above are set forth below:
Light Green Dark Green Dark Green Example A ExamPle B ExamPle C
Total Iron (wt.%) 0.550 0.805 0.720 FeO/Tot. Iron0.251 0.293 0.270 lS LTA (%) 79.5 70.9 71.6 TS W (%) 48.1 36.9 36.5 TSIR (%) 36.7 22.9 29.2 TSET (%) 56.8 44.6 48.8 The transmittance data in the table above and throughout are 20 based on a glass thickness of 3.9 millimeters (0.154 inch). Luminous transmittance (LTA) is measured using C.I.E. standard illuminant "A"
over the wavelength range 380 to 770 nanometers. Total solar ultraviolet transmittance (TS W ) is measured over the wavelength range 300 to 390 nanometers. Total solar infrared transmittance 25 (TSIR) is measured over the wavelength range 800 to 2100 nanometers.
Total solar energy transmittance (TSET) represents a computed value based on measured transmittances from 300 to 2100 nanometers at 50 nanometer intervals.
Recently, a goal has been established to limit ultraviolet 30 transmittance to no more than 31 percent in some automotive glass.
At the same time, it is a requirement that glass in vision areas of automobiles have an LTA of at least 70 percent. Simply increasing the amount of iron to lower the ultraviolet transmittance would impermissibly lower the luminous transmittance as well, so an 35 alternative approach is needed. The use of cerium oxide in glass to reduce ultraviolet transmittance is disclosed in U.S. Patent No.
, -~ - 3 -2,860,059, and the following two examples are of commercial products that take this approach:
Exam~le D ExamPle E
CeO2 (wt~Yo) 1.06 0.70 Total Iron (wt.%) 0.780 0.858 FeO/Tot. Iron 0.290 0.282 LTA (%) 71.4 70.4 TS W (~) 27.8 28.3 TSIR (%) 22.8 20.6 TSET (~0) 44.6 42.9 These glasses exhibit the desired combination of low ultraviolet transmittance and high luminous transmittance, but the high cost of cerium sources substantially increases the cost of making these glasses. It would be desirable if these ob~ectives 15 could be met without incurring such hlgh raw material costs. High cerium content also produces an undesirable solarization effect, that is, the glass tends to darken upon exposure to ultraviolet radiation. For these reasons, it would be desirable to lower the amount of cerium reguired in this type of glass.
An objective of the present invention is to provide green tinted glass that has luminous transmittance of at least 70 percent and ultraviolet transmittance of no more than 31 percent (both transmittances at a reference thickness of 3.9 millimeters), without 25 requiring the use of as much costly cerium oxide as in prior compositions of this type. These properties may be achieved by the present invention with less than 0.5 percent by weight CeO2 in the glass, preferably less than 0.4 percent by weight CeO2. The optimized embodiments of the present invention contain less than 0.35 30 percent by weight CeO2. Compared to competing glasses, the glasses of the present invention are characterized by larger amounts of total iron and smaller proportions of the iron in the ferrous state. The total iron (expressed as Fe203) is 8reater than 0.85 percent by weight of the total glass composition, and the ratio of FeO/total 35 iron (ferrous iron expressed as FeO divided by the total iron expressed as Fe203) is less than 0.275.
. . . . .
DETAILED DESCRIPTION
The base glass composition is not critical to the present invention and may consist of any conventional soda-lime-silica flat glass composition, which may be characterized by the ranges set forth 5 above. Preferably, the base glass is one known by those of skill in the art to be producible in a continuous melting furnace and formed into a flat sheet by the float process. A specific example of a glass of the present invention can be seen in Example 1.
ExamDle 1 Si02 71.88 percent by weight Na20 13.47 CaO 8.91 MgO 3.66 15 A1203 0.27 K20 0.08 S03 0.15 Fe203 (total) 0.898 Ce02 0.28 Additionally, traces of impurities may be present without significant effect on the glass. Melting and fining aids such as S03 are useful during production of the glass, but their residual amounts in the glass can vary and have no significant effect on the properties of the glass product. K20 is present in this example as 25 an impurity, and its presence is not required, although it serves a function in the glass essentially equivalent to that of Na20. The ratio of ferrous iron ~expressed as FeO) to total iron (expressed as Fe203) for Example 1 was 0.245. The batch mixture of raw materials from which the glass of Example 1 was melted was as follows:
30 Sand1000 parts by weight Soda ash 324 Limestone 84 Dolomite 242 Salt cake 5 35 Rouge 12.32 Cerium carbonate (hydrate)5 75 Coal 1.55 20 4 ~ 0 6 1 The glass of Example 1 exhibited the following transmittance properties at a thickness of 3.9 millimeters:
LTA 70.8%
TS W 29.6%
TSIR 22.1%
TSET 43.7%
One of the ways to control the ratio of ferrous to total iron is by selecting the amount of coal or other reducing agent included in the batch mixture. Instead of coal, various other 10 sources of carbon are known to serve as reducing agents during melting of glass. Another means of control is by way of the ratio of air to fuel in the melting furnace. A higher air to fuel ratio produces conditions in the melting furnace that are more oxidizing, which, in turn, leads to a lower ferrous to total iron ratio.
15 Specifying the oxidizing control measures depends upon the particular operating characteristics of a particular melting furnace. In Example 1, oxidizing conditions during melting were exceptionally high, so the amount of coal included in the batch was larger than would be desired under other conditions. In some cases it may be 20 desirable to include no coal or other reducing agent in order to attain the oxidizing conditions required for the present invention.
High melting temperatures also tend to have a reducing effect on the glass, as can be seen in the relatively high ferrous to total iron ratios of Examples D and E of the prior art, which 25 indicates that those glasses probably required exceptionally high temperature melting conditions. Because of the low infrared transmittance of the category of dark green tinted, high iron containing glasses to which the present invention pertains, relatively high melting temperatures are to be expected. As a 30 result, makinB the conditions more oxidizing in accordance with the present invention may yleld ferrous to total iron ratios that are relatively low for dark green glass, but not substantially different from those for lightly tinted or clear glass. Therefore, the requirement of a ferrous to total iron ratio less than 0.26 in the 35 present invention is relatively low for this type of glass.
Examples 2 through 7 are additional embodiments of the present invention. Only the colorant portion of the compositions are set forth because the base glass portions vary only slightly.
Examp 1 eExamp 1 eExamp 1 eBxamp 1 eExamp 1 e Examp 1 e LTA 70 5 70 3 70-4 70.9 70.2 71.0 TSW 28.4 26.6 26.4 31.0 29.9 30.2 TSIR 23.9 23.3 25.1 20.9 20.1 21.5 TSET 44.3 43.9 44.9 43.4 42.6 43.7 15 Fe203 (total)0.957 0.973 1.132 0.882 0.907 0.896 Fe0/Ee203 0.222 0.222 0.161 0.261 0.254 0.243 20 Ce02 0.27 0.28 <0.01 0.29 0.31 0.31 Minimizing the amount of cerium oxide used is best for meeting the ob~ectives of reducing the cost of the glass and avoiding solarization, and Example 4 is an embodiment within the scope of the invention in which no cerium was used. However, the very low ferrous 25 to total iron ratio required when no cerium is tlsed may be difficult to attain in some melting furnaces. Therefore, it is preferred that a small amount of cerium be used to yield the desired reduction in ultraviolet transmittance without requiring an unduly low ferrous to total iron ratio. Additionally, cerium oxide is itself an oxidizing 30 agent whose presence assists in attaining the required ferrous to total iron ratio. Accordingly, the preferred embodiments disclosed above include 0.20 to 0.35 percent by weight Ce02 although some commercially operating furnaces may require up to 0.4 percent or more.
The ultraviolet tr~n~rnitt~nce herein has been reported with reference 35 to the wavelength range 295 to 395 nanometers and would be about 3% less for the wavelength range of 300 to 390 nanometers. Others may use the range 300 to 400 nanometers for measuring ultraviolet. The ~-204~30r~ 1 goal of a m~mllm ultraviolet transmittance of 31 percent for the present invention would be approximately equivalent to 38 percent if the range 300 to 400 nanometers is used.
Cerium is sometimes included in glass to "decolorize" the 5 glass. But the glass of the present invention has a distinctly green color. The color may be a matter of taste, and the specific color characteristics need not be considered critical to the present invention, but the glasses that have been made in accordance with the invention have been characterized by excitation purity greater than 1 10 percent, usually from 2 to 4 percent, and dominant wavelength from 495 to 535 nanometers.
The total solar energy transmittance (TSET) of the glass of the present invention is relatively low, thereby significantly reducing the amount of thermal energy that passes through a window 15 glazed with the glass. Although not critical to the invention, the TSET of the glasses of the present invention are generally lower than 45 percent.
The invention has been described with reference to specific embodiments, but it should be understood that variations and 20 modifications that are known to those of skill in the art may be resorted to within the scope of the invention as defined by the claims that follow.
ULTRAVIOLET ABSORBING GREEN TINTED GLASS
BACKGROUND OF THE INVENTION
This invention relates to soda-lime-silica glass 5 particularly suitable for controlling transmittance of solar radiation in window glazing applications. The glass may be generally described as being green tinted, and ls designed to have low heat transmittance and particularly enhanced absorption in the ultraviolet wavelength range. This is desirable for the sake of reducing the 10 rate at which the sun's rays deteriorate plastics and fabrics in applications such as automobiles. A particular objective of the invention is to permit glass of this type to be made at a lower cost by reducing the amount of costly ingredients required.
Soda-lime-silica flat glass may be essentially characterized 15 by the following composition on a weight percentage basis of the total glass:
SiO268 - 75%
Na20 10 - 20 CaO 5 - 15 MgO O - 5 Other minor ingredients, including melting and refining aids such as S03, may also appear in the glass composition. Small amounts 25 of K20, BaO or B203 and other minor constituents have also sometimes been included in flat glass and may be considered optional. To this base glass are added the coloring constituents that produce the transmittance properties of the glass. The primary colorant in the category of glasses relevant to the present invention is iron, which 30 is usually present in both the Fe203 and FeO forms. As is conventional, the total amount of iron present in a glass is expressed herein as Fe203, regardless of the form actually present.
A typical green tinted automotive glass has about 0.5 percent by weight total iron, with the ratio of FeO to total iron being about 35 0.25.
Larger amounts of iron have been used in some specialty glasses intended to lower the total solar energy transmittance.
, ~
~ - 2 -204~06 1 However, merely increasing the amount of total iron does not reduce the ultraviolet transmittance to the extent desired even when the amount of iron present is sufficient to lower the luminous (visible light) transmittance to the m~ml~ acceptable for automotive 5 applications under conventional commercial melting conditions. The colorant composition and transmittance properties for examples of two commercial products of this high iron, dark green tinted type along with an example of the conventional, light green tinted glass described above are set forth below:
Light Green Dark Green Dark Green Example A ExamPle B ExamPle C
Total Iron (wt.%) 0.550 0.805 0.720 FeO/Tot. Iron0.251 0.293 0.270 lS LTA (%) 79.5 70.9 71.6 TS W (%) 48.1 36.9 36.5 TSIR (%) 36.7 22.9 29.2 TSET (%) 56.8 44.6 48.8 The transmittance data in the table above and throughout are 20 based on a glass thickness of 3.9 millimeters (0.154 inch). Luminous transmittance (LTA) is measured using C.I.E. standard illuminant "A"
over the wavelength range 380 to 770 nanometers. Total solar ultraviolet transmittance (TS W ) is measured over the wavelength range 300 to 390 nanometers. Total solar infrared transmittance 25 (TSIR) is measured over the wavelength range 800 to 2100 nanometers.
Total solar energy transmittance (TSET) represents a computed value based on measured transmittances from 300 to 2100 nanometers at 50 nanometer intervals.
Recently, a goal has been established to limit ultraviolet 30 transmittance to no more than 31 percent in some automotive glass.
At the same time, it is a requirement that glass in vision areas of automobiles have an LTA of at least 70 percent. Simply increasing the amount of iron to lower the ultraviolet transmittance would impermissibly lower the luminous transmittance as well, so an 35 alternative approach is needed. The use of cerium oxide in glass to reduce ultraviolet transmittance is disclosed in U.S. Patent No.
, -~ - 3 -2,860,059, and the following two examples are of commercial products that take this approach:
Exam~le D ExamPle E
CeO2 (wt~Yo) 1.06 0.70 Total Iron (wt.%) 0.780 0.858 FeO/Tot. Iron 0.290 0.282 LTA (%) 71.4 70.4 TS W (~) 27.8 28.3 TSIR (%) 22.8 20.6 TSET (~0) 44.6 42.9 These glasses exhibit the desired combination of low ultraviolet transmittance and high luminous transmittance, but the high cost of cerium sources substantially increases the cost of making these glasses. It would be desirable if these ob~ectives 15 could be met without incurring such hlgh raw material costs. High cerium content also produces an undesirable solarization effect, that is, the glass tends to darken upon exposure to ultraviolet radiation. For these reasons, it would be desirable to lower the amount of cerium reguired in this type of glass.
An objective of the present invention is to provide green tinted glass that has luminous transmittance of at least 70 percent and ultraviolet transmittance of no more than 31 percent (both transmittances at a reference thickness of 3.9 millimeters), without 25 requiring the use of as much costly cerium oxide as in prior compositions of this type. These properties may be achieved by the present invention with less than 0.5 percent by weight CeO2 in the glass, preferably less than 0.4 percent by weight CeO2. The optimized embodiments of the present invention contain less than 0.35 30 percent by weight CeO2. Compared to competing glasses, the glasses of the present invention are characterized by larger amounts of total iron and smaller proportions of the iron in the ferrous state. The total iron (expressed as Fe203) is 8reater than 0.85 percent by weight of the total glass composition, and the ratio of FeO/total 35 iron (ferrous iron expressed as FeO divided by the total iron expressed as Fe203) is less than 0.275.
. . . . .
DETAILED DESCRIPTION
The base glass composition is not critical to the present invention and may consist of any conventional soda-lime-silica flat glass composition, which may be characterized by the ranges set forth 5 above. Preferably, the base glass is one known by those of skill in the art to be producible in a continuous melting furnace and formed into a flat sheet by the float process. A specific example of a glass of the present invention can be seen in Example 1.
ExamDle 1 Si02 71.88 percent by weight Na20 13.47 CaO 8.91 MgO 3.66 15 A1203 0.27 K20 0.08 S03 0.15 Fe203 (total) 0.898 Ce02 0.28 Additionally, traces of impurities may be present without significant effect on the glass. Melting and fining aids such as S03 are useful during production of the glass, but their residual amounts in the glass can vary and have no significant effect on the properties of the glass product. K20 is present in this example as 25 an impurity, and its presence is not required, although it serves a function in the glass essentially equivalent to that of Na20. The ratio of ferrous iron ~expressed as FeO) to total iron (expressed as Fe203) for Example 1 was 0.245. The batch mixture of raw materials from which the glass of Example 1 was melted was as follows:
30 Sand1000 parts by weight Soda ash 324 Limestone 84 Dolomite 242 Salt cake 5 35 Rouge 12.32 Cerium carbonate (hydrate)5 75 Coal 1.55 20 4 ~ 0 6 1 The glass of Example 1 exhibited the following transmittance properties at a thickness of 3.9 millimeters:
LTA 70.8%
TS W 29.6%
TSIR 22.1%
TSET 43.7%
One of the ways to control the ratio of ferrous to total iron is by selecting the amount of coal or other reducing agent included in the batch mixture. Instead of coal, various other 10 sources of carbon are known to serve as reducing agents during melting of glass. Another means of control is by way of the ratio of air to fuel in the melting furnace. A higher air to fuel ratio produces conditions in the melting furnace that are more oxidizing, which, in turn, leads to a lower ferrous to total iron ratio.
15 Specifying the oxidizing control measures depends upon the particular operating characteristics of a particular melting furnace. In Example 1, oxidizing conditions during melting were exceptionally high, so the amount of coal included in the batch was larger than would be desired under other conditions. In some cases it may be 20 desirable to include no coal or other reducing agent in order to attain the oxidizing conditions required for the present invention.
High melting temperatures also tend to have a reducing effect on the glass, as can be seen in the relatively high ferrous to total iron ratios of Examples D and E of the prior art, which 25 indicates that those glasses probably required exceptionally high temperature melting conditions. Because of the low infrared transmittance of the category of dark green tinted, high iron containing glasses to which the present invention pertains, relatively high melting temperatures are to be expected. As a 30 result, makinB the conditions more oxidizing in accordance with the present invention may yleld ferrous to total iron ratios that are relatively low for dark green glass, but not substantially different from those for lightly tinted or clear glass. Therefore, the requirement of a ferrous to total iron ratio less than 0.26 in the 35 present invention is relatively low for this type of glass.
Examples 2 through 7 are additional embodiments of the present invention. Only the colorant portion of the compositions are set forth because the base glass portions vary only slightly.
Examp 1 eExamp 1 eExamp 1 eBxamp 1 eExamp 1 e Examp 1 e LTA 70 5 70 3 70-4 70.9 70.2 71.0 TSW 28.4 26.6 26.4 31.0 29.9 30.2 TSIR 23.9 23.3 25.1 20.9 20.1 21.5 TSET 44.3 43.9 44.9 43.4 42.6 43.7 15 Fe203 (total)0.957 0.973 1.132 0.882 0.907 0.896 Fe0/Ee203 0.222 0.222 0.161 0.261 0.254 0.243 20 Ce02 0.27 0.28 <0.01 0.29 0.31 0.31 Minimizing the amount of cerium oxide used is best for meeting the ob~ectives of reducing the cost of the glass and avoiding solarization, and Example 4 is an embodiment within the scope of the invention in which no cerium was used. However, the very low ferrous 25 to total iron ratio required when no cerium is tlsed may be difficult to attain in some melting furnaces. Therefore, it is preferred that a small amount of cerium be used to yield the desired reduction in ultraviolet transmittance without requiring an unduly low ferrous to total iron ratio. Additionally, cerium oxide is itself an oxidizing 30 agent whose presence assists in attaining the required ferrous to total iron ratio. Accordingly, the preferred embodiments disclosed above include 0.20 to 0.35 percent by weight Ce02 although some commercially operating furnaces may require up to 0.4 percent or more.
The ultraviolet tr~n~rnitt~nce herein has been reported with reference 35 to the wavelength range 295 to 395 nanometers and would be about 3% less for the wavelength range of 300 to 390 nanometers. Others may use the range 300 to 400 nanometers for measuring ultraviolet. The ~-204~30r~ 1 goal of a m~mllm ultraviolet transmittance of 31 percent for the present invention would be approximately equivalent to 38 percent if the range 300 to 400 nanometers is used.
Cerium is sometimes included in glass to "decolorize" the 5 glass. But the glass of the present invention has a distinctly green color. The color may be a matter of taste, and the specific color characteristics need not be considered critical to the present invention, but the glasses that have been made in accordance with the invention have been characterized by excitation purity greater than 1 10 percent, usually from 2 to 4 percent, and dominant wavelength from 495 to 535 nanometers.
The total solar energy transmittance (TSET) of the glass of the present invention is relatively low, thereby significantly reducing the amount of thermal energy that passes through a window 15 glazed with the glass. Although not critical to the invention, the TSET of the glasses of the present invention are generally lower than 45 percent.
The invention has been described with reference to specific embodiments, but it should be understood that variations and 20 modifications that are known to those of skill in the art may be resorted to within the scope of the invention as defined by the claims that follow.
Claims (5)
1. A green tinted, ultraviolet absorbing glass having a base glass compositioncomprising:
SiO2 68 - 75 weight%
Na2O 10 - 20 CaO 5 - 15 MgO 0 - 5 Al2O3 0 - 5 and a colorant portion consisting essentially of:
CeO2 Less than 0.5 weight %
Total iron (as Fe2O3) Greater than 0.85 weight %
FeO/total iron Less than 0.275 weight percent exhibiting ultraviolet transmittance no greater than 31 percent (300 to 390 nanometers) at a reference thickness of 3.9 millimeters.
SiO2 68 - 75 weight%
Na2O 10 - 20 CaO 5 - 15 MgO 0 - 5 Al2O3 0 - 5 and a colorant portion consisting essentially of:
CeO2 Less than 0.5 weight %
Total iron (as Fe2O3) Greater than 0.85 weight %
FeO/total iron Less than 0.275 weight percent exhibiting ultraviolet transmittance no greater than 31 percent (300 to 390 nanometers) at a reference thickness of 3.9 millimeters.
2. The glass of claim 1 wherein the glass contains less than 0.4 percent by weight CeO2.
3. The glass of claim 1 wherein the glass exhibits luminous transmittance (illuminant A) of at least 70 percent at a thickness of 3.9 millimeters.
4. The glass of claim 1 wherein the glass exhibits a dominant wavelength from 495 to 535 nanometers.
5. The glass of claim 1 wherein the glass exhibits a total solar energy transmittance less than 45 percent at a reference thickness of 3.9 millimeters.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/559,915 | 1990-07-30 | ||
| US07/559,915 US5240886A (en) | 1990-07-30 | 1990-07-30 | Ultraviolet absorbing, green tinted glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2048061A1 CA2048061A1 (en) | 1992-01-31 |
| CA2048061C true CA2048061C (en) | 1996-04-23 |
Family
ID=24235580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002048061A Expired - Fee Related CA2048061C (en) | 1990-07-30 | 1991-07-29 | Ultraviolet absorbing green tinted glass |
Country Status (13)
| Country | Link |
|---|---|
| US (2) | US5240886A (en) |
| EP (1) | EP0469446B1 (en) |
| JP (1) | JPH08716B2 (en) |
| KR (1) | KR940002024B1 (en) |
| AT (1) | ATE135670T1 (en) |
| AU (1) | AU623303B2 (en) |
| BR (1) | BR9103240A (en) |
| CA (1) | CA2048061C (en) |
| DE (1) | DE69118042T2 (en) |
| DK (1) | DK0469446T3 (en) |
| ES (1) | ES2087187T3 (en) |
| GR (1) | GR3020136T3 (en) |
| MX (1) | MX173588B (en) |
Families Citing this family (191)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2634753B1 (en) * | 1988-07-27 | 1992-08-21 | Saint Gobain Vitrage | GLAZING WITH ELECTRICALLY CONDUCTIVE LAYER OBTAINED BY PYROLYSIS OF POWDERED COMPOUNDS, USEFUL AS A WINDSCREEN FOR A MOTOR VEHICLE |
| US5593929A (en) * | 1990-07-30 | 1997-01-14 | Ppg Industries, Inc. | Ultraviolet absorbing green tinted glass |
| FR2682101B1 (en) * | 1991-10-03 | 1994-10-21 | Saint Gobain Vitrage Int | COLORED GLASS COMPOSITION FOR MAKING WINDOWS. |
| US5470356A (en) * | 1991-10-11 | 1995-11-28 | Meszaros; Laszlo A. | Sulfur dye compositions and their production |
| JP2528579B2 (en) * | 1991-12-27 | 1996-08-28 | セントラル硝子株式会社 | Frit glass with high iron content and high reduction rate, and ultraviolet / infrared absorbing green glass using it |
| US5214008A (en) * | 1992-04-17 | 1993-05-25 | Guardian Industries Corp. | High visible, low UV and low IR transmittance green glass composition |
| FR2699526B1 (en) * | 1992-12-23 | 1995-02-03 | Saint Gobain Vitrage Int | Glass compositions intended for the manufacture of glazing. |
| US5830814A (en) * | 1992-12-23 | 1998-11-03 | Saint-Gobain Vitrage | Glass compositions for the manufacture of glazings |
| FR2699527B1 (en) * | 1992-12-23 | 1995-02-03 | Saint Gobain Vitrage Int | Glass compositions intended for the manufacture of glazing. |
| GB9302186D0 (en) * | 1993-02-04 | 1993-03-24 | Pilkington Plc | Neutral coloured glasses |
| US5350972A (en) * | 1993-05-25 | 1994-09-27 | General Electric Company | UV absorbing lamp glass |
| FR2710050B1 (en) * | 1993-09-17 | 1995-11-10 | Saint Gobain Vitrage Int | Glass composition intended for the manufacture of glazing. |
| JP3368953B2 (en) * | 1993-11-12 | 2003-01-20 | 旭硝子株式会社 | UV absorbing colored glass |
| FR2731696B1 (en) * | 1995-03-16 | 1997-04-25 | Saint Gobain Vitrage | GLASS SHEETS FOR THE MANUFACTURE OF GLAZING |
| FR2721599B1 (en) * | 1994-06-23 | 1996-08-09 | Saint Gobain Vitrage | Glass composition intended for the manufacture of glazing. |
| US5792559A (en) | 1994-07-05 | 1998-08-11 | Ppg Industries, Inc. | Composite transparency |
| US6030911A (en) * | 1994-07-22 | 2000-02-29 | Vitro Flotado, S.A. De C.V. | Green thermo-absorbent glass |
| US5553440A (en) * | 1994-10-20 | 1996-09-10 | Ppg Industries, Inc. | Multi-sheet glazing unit and method of making same |
| US5644894A (en) * | 1994-10-20 | 1997-07-08 | Ppg Industries, Inc. | Multi-sheet glazing unit and method of making same |
| AU696443B2 (en) * | 1994-10-26 | 1998-09-10 | Asahi Glass Company Limited | Glass having low solar radiation and ultraviolet ray transmittance |
| EP0790961B1 (en) * | 1994-11-11 | 1999-04-14 | Heineken Technical Services B.V. | Uv radiation-absorbing packing |
| DE69600538T2 (en) * | 1995-06-02 | 1999-01-28 | Nippon Sheet Glass Co Ltd | Ultraviolet and infrared radiation absorbing glass |
| JP3899531B2 (en) * | 1995-06-16 | 2007-03-28 | 日本板硝子株式会社 | UV infrared absorbing glass |
| US5776846A (en) * | 1996-03-01 | 1998-07-07 | Nippon Sheet Glass Co., Ltd. | Ultraviolet- and infrared-absorbing glass |
| US5747398A (en) * | 1995-12-11 | 1998-05-05 | Libbey-Owens-Ford Co. | Neutral colored glass compositions |
| GB9601780D0 (en) * | 1996-01-30 | 1996-04-03 | Pilkington Plc | A method of making glass |
| US5780372A (en) * | 1996-02-21 | 1998-07-14 | Libbey-Owens-Ford Co. | Colored glass compositions |
| US5830812A (en) * | 1996-04-01 | 1998-11-03 | Ppg Industries, Inc. | Infrared and ultraviolet radiation absorbing green glass composition |
| JPH1045425A (en) * | 1996-05-28 | 1998-02-17 | Nippon Sheet Glass Co Ltd | Ultraviolet-ray and infrared-ray absorbing glass |
| US6612133B2 (en) | 1996-06-07 | 2003-09-02 | Nippon Sheet Glass Co., Ltd. | Method for shifting absorption peak wavelength of infrared radiation absorbing glass |
| GB2315487A (en) * | 1996-06-17 | 1998-02-04 | Pilkington Plc | Ultraviolet and infra-red absorbing glass |
| US5813191A (en) | 1996-08-29 | 1998-09-29 | Ppg Industries, Inc. | Spacer frame for an insulating unit having strengthened sidewalls to resist torsional twist |
| GB2320022A (en) * | 1996-12-07 | 1998-06-10 | Pilkington Plc | Green solar control glass |
| US5776845A (en) * | 1996-12-09 | 1998-07-07 | Ford Motor Company | High transmittance green glass with improved UV absorption |
| JPH10182183A (en) * | 1996-12-19 | 1998-07-07 | Nippon Sheet Glass Co Ltd | Low ultraviolet and infrared transmission glass |
| US7096692B2 (en) * | 1997-03-14 | 2006-08-29 | Ppg Industries Ohio, Inc. | Visible-light-responsive photoactive coating, coated article, and method of making same |
| US20020155299A1 (en) | 1997-03-14 | 2002-10-24 | Harris Caroline S. | Photo-induced hydrophilic article and method of making same |
| US20030039843A1 (en) * | 1997-03-14 | 2003-02-27 | Christopher Johnson | Photoactive coating, coated article, and method of making same |
| JPH10265239A (en) * | 1997-03-26 | 1998-10-06 | Nippon Sheet Glass Co Ltd | Ultraviolet ray and infrared ray absorption glass |
| US5851940A (en) * | 1997-07-11 | 1998-12-22 | Ford Motor Company | Blue glass with improved UV and IR absorption |
| US5807417A (en) * | 1997-07-11 | 1998-09-15 | Ford Motor Company | Nitrate-free method for manufacturing a blue glass composition |
| AU725178B2 (en) | 1997-10-20 | 2000-10-05 | Ppg Industries Ohio, Inc. | Infrared and ultraviolet radiation absorbing blue glass composition |
| US6115989A (en) * | 1998-01-30 | 2000-09-12 | Ppg Industries Ohio, Inc. | Multi-sheet glazing unit and method of making same |
| US6250026B1 (en) | 1998-01-30 | 2001-06-26 | Ppg Industries Ohio, Inc. | Multi-sheet glazing unit having a single spacer frame and method of making same |
| JP2002501999A (en) | 1998-01-30 | 2002-01-22 | ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド | Multilayer sheet glass unit and method for forming the same |
| US6289641B1 (en) | 1998-01-30 | 2001-09-18 | Ppg Industries Ohio, Inc. | Glazing unit having three or more spaced sheets and a single spacer frame and method of making same |
| US6886297B1 (en) | 1998-07-23 | 2005-05-03 | Ppg Industries Ohio, Inc. | Insulating unitless window sash |
| US6797388B1 (en) | 1999-03-18 | 2004-09-28 | Ppg Industries Ohio, Inc. | Methods of making low haze coatings and the coatings and coated articles made thereby |
| US6335086B1 (en) | 1999-05-03 | 2002-01-01 | Guardian Industries Corporation | Hydrophobic coating including DLC on substrate |
| US6461731B1 (en) | 1999-05-03 | 2002-10-08 | Guardian Industries Corp. | Solar management coating system including protective DLC |
| US6368664B1 (en) | 1999-05-03 | 2002-04-09 | Guardian Industries Corp. | Method of ion beam milling substrate prior to depositing diamond like carbon layer thereon |
| US6261693B1 (en) | 1999-05-03 | 2001-07-17 | Guardian Industries Corporation | Highly tetrahedral amorphous carbon coating on glass |
| US6447891B1 (en) | 1999-05-03 | 2002-09-10 | Guardian Industries Corp. | Low-E coating system including protective DLC |
| US6312808B1 (en) | 1999-05-03 | 2001-11-06 | Guardian Industries Corporation | Hydrophobic coating with DLC & FAS on substrate |
| US6277480B1 (en) | 1999-05-03 | 2001-08-21 | Guardian Industries Corporation | Coated article including a DLC inclusive layer(s) and a layer(s) deposited using siloxane gas, and corresponding method |
| US6280834B1 (en) | 1999-05-03 | 2001-08-28 | Guardian Industries Corporation | Hydrophobic coating including DLC and/or FAS on substrate |
| US6475573B1 (en) | 1999-05-03 | 2002-11-05 | Guardian Industries Corp. | Method of depositing DLC inclusive coating on substrate |
| US6582799B1 (en) | 1999-06-02 | 2003-06-24 | Ppg Industries Ohio, Inc. | Laminated transparency |
| US6849328B1 (en) | 1999-07-02 | 2005-02-01 | Ppg Industries Ohio, Inc. | Light-transmitting and/or coated article with removable protective coating and methods of making the same |
| MXPA02004955A (en) | 1999-11-24 | 2002-09-18 | Ppg Ind Ohio Inc | Low shading coefficient and low emissivity coatings and coated articles. |
| US20020136905A1 (en) | 1999-11-24 | 2002-09-26 | Medwick Paul A. | Low shading coefficient and low emissivity coatings and coated articles |
| US6350712B1 (en) | 2000-01-26 | 2002-02-26 | Vitro Corporativo, S.A. De C.V. | Solar control glass composition |
| CA2398368C (en) | 2000-02-11 | 2005-04-19 | Ppg Industries Ohio, Inc. | Vehicle antenna |
| AU2001243473A1 (en) * | 2000-03-07 | 2001-09-17 | American Express Travel Related Services Company, Inc. | System for facilitating a transaction |
| US7361404B2 (en) | 2000-05-10 | 2008-04-22 | Ppg Industries Ohio, Inc. | Coated article with removable protective coating and related methods |
| US7323249B2 (en) * | 2000-08-31 | 2008-01-29 | Ppg Industries Ohio, Inc. | Methods of obtaining photoactive coatings and/or anatase crystalline phase of titanium oxides and articles made thereby |
| US6677063B2 (en) | 2000-08-31 | 2004-01-13 | Ppg Industries Ohio, Inc. | Methods of obtaining photoactive coatings and/or anatase crystalline phase of titanium oxides and articles made thereby |
| US7431547B2 (en) * | 2000-10-04 | 2008-10-07 | Ppg Industries Ohio, Inc. | Corner restraint for securing articles on a shipping and/or storage rack |
| US20020172775A1 (en) * | 2000-10-24 | 2002-11-21 | Harry Buhay | Method of making coated articles and coated articles made thereby |
| US7311961B2 (en) * | 2000-10-24 | 2007-12-25 | Ppg Industries Ohio, Inc. | Method of making coated articles and coated articles made thereby |
| DE10063180A1 (en) * | 2000-12-18 | 2002-06-27 | Bayer Ag | Device for generating light signals |
| US20020120916A1 (en) * | 2001-01-16 | 2002-08-29 | Snider Albert Monroe | Head-up display system utilizing fluorescent material |
| US7200211B1 (en) | 2004-10-12 | 2007-04-03 | Palmsource, Inc. | Method and system for providing information for identifying callers based on a partial number |
| US6632760B2 (en) | 2001-10-03 | 2003-10-14 | Visteon Global Technologies, Inc. | Chrome-free green privacy glass composition with improved ultra violet absorption |
| US7232615B2 (en) * | 2001-10-22 | 2007-06-19 | Ppg Industries Ohio, Inc. | Coating stack comprising a layer of barrier coating |
| US6962759B2 (en) * | 2001-10-22 | 2005-11-08 | Ppg Industries Ohio, Inc. | Method of making coated articles having an oxygen barrier coating and coated articles made thereby |
| US6730389B2 (en) | 2001-10-25 | 2004-05-04 | Ppg Industries Ohio, Inc. | Coated substrate having a frequency selective surface |
| US6596660B1 (en) | 2001-10-26 | 2003-07-22 | Visteon Global Technologies, Inc. | Amber-free reduced blue glass composition |
| US6610622B1 (en) | 2002-01-28 | 2003-08-26 | Guardian Industries Corp. | Clear glass composition |
| US7169722B2 (en) * | 2002-01-28 | 2007-01-30 | Guardian Industries Corp. | Clear glass composition with high visible transmittance |
| US7037869B2 (en) | 2002-01-28 | 2006-05-02 | Guardian Industries Corp. | Clear glass composition |
| US7144837B2 (en) * | 2002-01-28 | 2006-12-05 | Guardian Industries Corp. | Clear glass composition with high visible transmittance |
| DE60336634D1 (en) * | 2002-02-11 | 2011-05-19 | Ppg Ind Ohio Inc | SUN PROTECTION COATING |
| CZ306231B6 (en) * | 2002-04-25 | 2016-09-07 | Ppg Ind Ohio | Coated articles having a protective coating and cathode targets for making the coated articles |
| CA2484181C (en) * | 2002-05-03 | 2010-02-23 | Ppg Industries Ohio, Inc. | Substrate having thermal management coating for an insulating glass unit |
| US7588829B2 (en) * | 2002-05-31 | 2009-09-15 | Ppg Industries Ohio, Inc. | Article having an aesthetic coating |
| US6849566B2 (en) * | 2002-07-19 | 2005-02-01 | Ppg Industries Ohio, Inc. | Blue-green grass |
| US6791065B2 (en) | 2002-07-24 | 2004-09-14 | Ppg Industries Ohio, Inc. | Edge sealing of a laminated transparency |
| US6791066B2 (en) | 2002-07-24 | 2004-09-14 | Ppg Industries Ohio, Inc. | Eliminating hot spots at end portions of bus bars of a heatable transparency having an electrically conductive member |
| US20040112411A1 (en) * | 2002-09-10 | 2004-06-17 | Boykin Cheri M. | Method and apparatus for cleaning a photoactive and/or hydrophilic surface |
| US7223523B2 (en) * | 2002-09-18 | 2007-05-29 | Ppg Industries Ohio, Inc. | Demonstration kit and method for enhancing and/or demonstrating photoactive properties |
| US6995339B2 (en) * | 2002-09-18 | 2006-02-07 | Ppg Industries Ohio, Inc. | Heatable wiper rest area for a transparency |
| US7132625B2 (en) | 2002-10-03 | 2006-11-07 | Ppg Industries Ohio, Inc. | Heatable article having a configured heating member |
| US7094716B2 (en) * | 2002-10-04 | 2006-08-22 | Automotive Components Holdings, Llc | Green glass composition |
| JP2004123495A (en) | 2002-10-07 | 2004-04-22 | Nippon Sheet Glass Co Ltd | Ultraviolet and infrared absorption colored glass plate |
| US6811884B2 (en) * | 2002-12-24 | 2004-11-02 | Ppg Industries Ohio, Inc. | Water repellant surface treatment and treated articles |
| US7105220B2 (en) * | 2003-01-29 | 2006-09-12 | Ppg Industries Ohio, Inc. | Coated article having a sealed layered edge to impede corrosion of a coating at the edge and method of making same |
| EP1611265B1 (en) * | 2003-03-28 | 2017-05-03 | Vitro, S.A.B. de C.V. | Substrates coated with mixtures of titanium and aluminum materials |
| US20040202890A1 (en) | 2003-04-08 | 2004-10-14 | Kutilek Luke A. | Methods of making crystalline titania coatings |
| US6891517B2 (en) * | 2003-04-08 | 2005-05-10 | Ppg Industries Ohio, Inc. | Conductive frequency selective surface utilizing arc and line elements |
| CN100528784C (en) * | 2003-05-30 | 2009-08-19 | Ppg工业俄亥俄公司 | Appliance with coated transparency |
| US7998602B2 (en) * | 2003-05-30 | 2011-08-16 | Ppg Industries Ohio, Inc. | Appliance with coated transparency |
| US7739851B2 (en) * | 2003-06-23 | 2010-06-22 | Ppg Industries Ohio, Inc. | Plastic spacer stock, plastic spacer frame and multi-sheet unit, and method of making same |
| US7827761B2 (en) | 2003-06-23 | 2010-11-09 | Ppg Industries Ohio, Inc. | Plastic spacer stock, plastic spacer frame and multi-sheet unit, and method of making same |
| US7856791B2 (en) * | 2003-06-23 | 2010-12-28 | Ppg Industries Ohio, Inc. | Plastic spacer stock, plastic spacer frame and multi-sheet unit, and method of making same |
| US7765769B2 (en) * | 2003-06-23 | 2010-08-03 | Ppg Industries Ohio, Inc. | Integrated window sash with lattice frame and retainer clip |
| US7950194B2 (en) | 2003-06-23 | 2011-05-31 | Ppg Industries Ohio, Inc. | Plastic spacer stock, plastic spacer frame and multi-sheet unit, and method of making same |
| US7588653B2 (en) * | 2003-06-23 | 2009-09-15 | Ppg Industries Ohio, Inc. | Method of making an integrated window sash |
| US7997037B2 (en) * | 2003-06-23 | 2011-08-16 | Ppg Industries Ohio, Inc. | Integrated window sash with groove for desiccant material |
| CN1867749B (en) * | 2003-06-23 | 2011-10-05 | Ppg工业俄亥俄公司 | Integrated window sash and methods of making an integrated window sash |
| US6995102B2 (en) * | 2003-07-16 | 2006-02-07 | Visteon Global Technologies, Inc. | Infrared absorbing blue glass composition |
| US7159756B2 (en) * | 2003-08-29 | 2007-01-09 | Ppg Industries Ohio, Inc. | Method of soldering and solder compositions |
| US7150820B2 (en) * | 2003-09-22 | 2006-12-19 | Semitool, Inc. | Thiourea- and cyanide-free bath and process for electrolytic etching of gold |
| JP5086541B2 (en) * | 2003-12-26 | 2012-11-28 | 日本板硝子株式会社 | Near-infrared absorbing green glass composition and laminated glass using the same |
| US20050208319A1 (en) * | 2004-03-22 | 2005-09-22 | Finley James J | Methods for forming an electrodeposited coating over a coated substrate and articles made thereby |
| US20050238923A1 (en) * | 2004-04-27 | 2005-10-27 | Thiel James P | Hybrid coating stack |
| US9051211B2 (en) * | 2004-04-27 | 2015-06-09 | Ppg Industries Ohio, Inc. | Effects of methods of manufacturing sputtering targets on characteristics of coatings |
| US8500965B2 (en) * | 2004-05-06 | 2013-08-06 | Ppg Industries Ohio, Inc. | MSVD coating process |
| US20060186104A1 (en) * | 2005-02-22 | 2006-08-24 | Winter John A | Fluid deposition of electrically conductive strips and articles having solid electrically conductive strips obtained therefrom |
| US7223940B2 (en) * | 2005-02-22 | 2007-05-29 | Ppg Industries Ohio, Inc. | Heatable windshield |
| JP5000097B2 (en) * | 2005-03-22 | 2012-08-15 | 日本板硝子株式会社 | Infrared absorbing green glass composition |
| US7359764B2 (en) * | 2005-05-16 | 2008-04-15 | Ppg Industries Ohio, Inc. | On-line/off-line scoring bridge |
| US7335421B2 (en) * | 2005-07-20 | 2008-02-26 | Ppg Industries Ohio, Inc. | Heatable windshield |
| US7678722B2 (en) * | 2005-07-29 | 2010-03-16 | Ppg Industries Ohio, Inc. | Green glass composition |
| JP5317704B2 (en) * | 2006-01-12 | 2013-10-16 | ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド | Display panel having function of redirecting light introduced by laser |
| US8629610B2 (en) * | 2006-01-12 | 2014-01-14 | Ppg Industries Ohio, Inc. | Display panel |
| GB0602943D0 (en) * | 2006-02-14 | 2006-03-22 | Pilkington Automotive Ltd | Vehicle glazing |
| US7909928B2 (en) * | 2006-03-24 | 2011-03-22 | The Regents Of The University Of Michigan | Reactive coatings for regioselective surface modification |
| US20070264479A1 (en) * | 2006-05-09 | 2007-11-15 | Thiel James P | Aesthetic transparency |
| US7947148B2 (en) * | 2006-06-01 | 2011-05-24 | The Regents Of The University Of Michigan | Dry adhesion bonding |
| US20080081148A1 (en) * | 2006-09-13 | 2008-04-03 | Kenneth Bond | Panel having a frame bonded thereto |
| US7736750B2 (en) | 2006-12-14 | 2010-06-15 | Ppg Industries Ohio, Inc. | Coated non-metallic sheet having a brushed metal appearance, and coatings for and method of making same |
| US8399047B2 (en) * | 2007-03-22 | 2013-03-19 | The Regents Of The Univeristy Of Michigan | Multifunctional CVD coatings |
| JP5351881B2 (en) * | 2007-03-28 | 2013-11-27 | ピルキントン グループ リミテッド | Glass composition |
| US8686319B2 (en) * | 2007-05-09 | 2014-04-01 | Ppg Industries Ohio, Inc. | Vehicle transparency heated with alternating current |
| US20080280147A1 (en) * | 2007-05-09 | 2008-11-13 | Thiel James P | Vehicle transparency |
| US8728634B2 (en) * | 2007-06-13 | 2014-05-20 | Ppg Industries Ohio, Inc. | Appliance transparency |
| US7954284B2 (en) | 2007-08-30 | 2011-06-07 | Ppg Industries Ohio, Inc. | Retainer clip for grid simulating muntins |
| US7748185B2 (en) | 2007-08-30 | 2010-07-06 | Ppg Industries Ohio, Inc. | Muntin grids for transparencies and transparencies having muntin grids |
| US8658289B2 (en) * | 2007-11-16 | 2014-02-25 | Ppg Industries Ohio, Inc. | Electromagnetic radiation shielding device |
| US8905460B2 (en) | 2008-02-25 | 2014-12-09 | Ppg Industries Ohio, Inc. | Ballistic transparency |
| US8628820B2 (en) * | 2008-03-11 | 2014-01-14 | Ppg Industries Ohio, Inc. | Reflective article and method of making a reflective article |
| GB0810525D0 (en) * | 2008-06-09 | 2008-07-09 | Pilkington Group Ltd | Solar unit glass plate composition |
| US8085460B2 (en) * | 2008-08-28 | 2011-12-27 | Ppg Industries Ohio, Inc | Electrochromic device |
| US8049949B2 (en) * | 2008-08-29 | 2011-11-01 | Ppg Industries Ohio, Inc. | Multi-layer electrode for high contrast electrochromic devices |
| US7907322B2 (en) * | 2008-10-23 | 2011-03-15 | Ppg Industries Ohio, Inc. | Electrochromic device |
| WO2010059507A1 (en) | 2008-11-19 | 2010-05-27 | Ppg Industries Ohio, Inc. | Undercoating layers providing improved topcoat functionality |
| US7998586B2 (en) | 2008-11-19 | 2011-08-16 | Ppg Industries Ohio, Inc. | Undercoating layers providing improved topcoat functionality |
| US20100124642A1 (en) * | 2008-11-19 | 2010-05-20 | Ppg Industries Ohio, Inc. | Undercoating layers providing improved conductive topcoat functionality |
| US8133599B2 (en) * | 2008-11-19 | 2012-03-13 | Ppg Industries Ohio, Inc | Undercoating layers providing improved photoactive topcoat functionality |
| UA103676C2 (en) * | 2009-05-08 | 2013-11-11 | Ппґ Індастріз Огайо, Інк. | Sun-protective coating with high solar heat gain coefficient |
| ES2668200T3 (en) * | 2009-07-21 | 2018-05-17 | Ppg Industries Ohio, Inc. | Improved busbar system for aircraft transparencies |
| US9366783B2 (en) | 2009-12-21 | 2016-06-14 | Ppg Industries Ohio, Inc. | Silicon thin film solar cell having improved underlayer coating |
| US20110146768A1 (en) | 2009-12-21 | 2011-06-23 | Ppg Industries Ohio, Inc. | Silicon thin film solar cell having improved underlayer coating |
| US9224892B2 (en) * | 2009-12-21 | 2015-12-29 | Ppg Industries Ohio, Inc. | Silicon thin film solar cell having improved haze and methods of making the same |
| US9932267B2 (en) | 2010-03-29 | 2018-04-03 | Vitro, S.A.B. De C.V. | Solar control coatings with discontinuous metal layer |
| US10654748B2 (en) | 2010-03-29 | 2020-05-19 | Vitro Flat Glass Llc | Solar control coatings providing increased absorption or tint |
| US10654747B2 (en) | 2010-03-29 | 2020-05-19 | Vitro Flat Glass Llc | Solar control coatings with subcritical copper |
| JP2012009616A (en) * | 2010-06-24 | 2012-01-12 | Asahi Glass Co Ltd | Lens for light emitting device |
| US9397240B2 (en) | 2010-12-09 | 2016-07-19 | Ppg Industries Ohio, Inc. | Corrosion resistant solar mirror |
| US9758426B2 (en) | 2011-06-29 | 2017-09-12 | Vitro, S.A.B. De C.V. | Reflective article having a sacrificial cathodic layer |
| CN104080748A (en) | 2012-01-27 | 2014-10-01 | 旭硝子株式会社 | Colored glass plate and manufacturing method thereof |
| WO2013111879A1 (en) | 2012-01-27 | 2013-08-01 | 旭硝子株式会社 | Colored glass plate and manufacturing method thereof |
| JP5999112B2 (en) | 2012-01-27 | 2016-09-28 | 旭硝子株式会社 | Colored glass plate and method for producing the same |
| US20140113120A1 (en) | 2012-10-19 | 2014-04-24 | Ppg Industries Ohio, Inc. | Anti-color banding topcoat for coated articles |
| US20140311573A1 (en) | 2013-03-12 | 2014-10-23 | Ppg Industries Ohio, Inc. | Solar Cell With Selectively Doped Conductive Oxide Layer And Method Of Making The Same |
| US20140261664A1 (en) | 2013-03-12 | 2014-09-18 | Ppg Industries Ohio, Inc. | Photovoltaic Cell Having An Antireflective Coating |
| US11292920B2 (en) | 2015-06-10 | 2022-04-05 | Ppg Industries Ohio, Inc. | Water repellant surface treatment for aircraft transparencies and methods of treating aircraft transparencies |
| US10942302B2 (en) | 2015-09-16 | 2021-03-09 | Vitro Flat Glass Llc | Solar mirrors and methods of making solar mirrors having improved properties |
| US9573841B1 (en) | 2015-10-06 | 2017-02-21 | Vidrio Plano De Mexico, S.A. De C. V. | UV absorbent green solar control glass composition |
| US10591652B2 (en) * | 2015-11-20 | 2020-03-17 | Schott Gemtron Corp. | Multi-layer coated glass substrate |
| BR112019002188B1 (en) | 2016-08-03 | 2022-11-22 | Schott Gemtron Corp | OVEN HAVING A DIELECTRICLY COATED GLASS SUBSTRATE THAT ABSORBES ELECTROMAGNETIC RADIATION AND EMITS THERMAL RADIATION |
| US11220455B2 (en) | 2017-08-04 | 2022-01-11 | Vitro Flat Glass Llc | Flash annealing of silver coatings |
| US20190041550A1 (en) | 2017-08-04 | 2019-02-07 | Vitro Flat Glass Llc | Flash Annealing of Transparent Conductive Oxide and Semiconductor Coatings |
| US10829408B2 (en) | 2017-12-13 | 2020-11-10 | Corning Incorporated | Glass-ceramics and methods of making the same |
| US11078718B2 (en) | 2018-02-05 | 2021-08-03 | Vitro Flat Glass Llc | Solar control coatings with quadruple metallic layers |
| BR112020016379A2 (en) | 2018-02-15 | 2021-01-19 | Vitro Flat Glass Llc | COATED ARTICLE HAVING A PROTECTIVE COATING CONTAINING SILICON NITRIDE AND / OR SILICON OXINITRIDE |
| US10830933B2 (en) | 2018-06-12 | 2020-11-10 | Guardian Glass, LLC | Matrix-embedded metamaterial coating, coated article having matrix-embedded metamaterial coating, and/or method of making the same |
| US10562812B2 (en) | 2018-06-12 | 2020-02-18 | Guardian Glass, LLC | Coated article having metamaterial-inclusive layer, coating having metamaterial-inclusive layer, and/or method of making the same |
| TWI776067B (en) | 2018-06-29 | 2022-09-01 | 美商維托平面玻璃有限責任公司 | Burn-off protective coating |
| US20200308045A1 (en) | 2019-03-28 | 2020-10-01 | Vitro Flat Glass Llc | Article Having a High Visible Light Reflectance and a Neutral Color |
| US11602767B2 (en) | 2019-06-28 | 2023-03-14 | Vitro Flat Glass Llc | Substrate having a burnable coating mask |
| CA3167821A1 (en) | 2020-02-14 | 2021-08-19 | Zhixun MA | Low sheet resistance coating |
| US11859439B2 (en) | 2020-04-15 | 2024-01-02 | Vitro Flat Glass Llc | Low thermal conducting spacer assembly for an insulating glazing unit |
| MX2023004370A (en) | 2020-10-14 | 2023-05-03 | Vitro Flat Glass Llc | Seal for electrochromic device. |
| WO2023064111A1 (en) | 2021-10-11 | 2023-04-20 | Vitro Flat Glass Llc | Heat-treatable coating having reduced haze |
| CN114180832B (en) * | 2021-11-29 | 2023-09-29 | 中国建筑材料科学研究总院有限公司 | Ultraviolet radiation resistant intermediate wave transparent infrared glass and preparation method and application thereof |
| US20230312407A1 (en) | 2022-03-31 | 2023-10-05 | Vitro Flat Glass Llc | Article Coated by a Multi-Layer Coating Stack |
| WO2023239778A1 (en) | 2022-06-07 | 2023-12-14 | Vitro Flat Glass Llc | Asymmetric patterned reflective coating |
| WO2024059091A1 (en) | 2022-09-14 | 2024-03-21 | Vitro Flat Glass Llc | Magnetron sputtering vapor deposition coating composition comprising light absorptive materials |
| WO2024059124A1 (en) | 2022-09-14 | 2024-03-21 | Vitro Flat Glass Llc | Reflective coating |
Family Cites Families (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1726635A (en) * | 1929-09-03 | of corning | ||
| US2524719A (en) * | 1946-11-26 | 1950-10-03 | American Optical Corp | Glass composition |
| US2582453A (en) * | 1948-07-02 | 1952-01-15 | American Optical Corp | Absorbing glass and method of making same |
| US2655452A (en) * | 1950-05-13 | 1953-10-13 | American Optical Corp | Glasses, compositions, thereof, articles embodying said glasses, and method of making and using the same |
| US2860059A (en) * | 1953-09-03 | 1958-11-11 | Libbey Owens Ford Glass Co | Ultra-violet light absorbing glass |
| BE551558A (en) * | 1955-10-28 | |||
| US3359125A (en) * | 1963-04-17 | 1967-12-19 | Owens Illinois Inc | Radiation indicating glass |
| US3294556A (en) * | 1963-07-19 | 1966-12-27 | Corning Glass Works | Tan ophthalmic glass |
| LU46426A1 (en) * | 1964-06-29 | 1972-01-01 | ||
| GB1163482A (en) * | 1966-08-02 | 1969-09-04 | Jeleniogorska Wytwornia Optycz | Glass Sun-Filters of High Ultra-Violet and Infra-Red Absorbing Capacity and the method for manufacturing them |
| US3967040A (en) * | 1971-10-01 | 1976-06-29 | Glaverbel-Mecaniver | Production of colored glass bodies |
| SU734152A1 (en) * | 1978-03-06 | 1980-05-15 | Чернятинский стекольный завод | Glass |
| SU748912A1 (en) * | 1978-04-07 | 1980-07-15 | Рижский Ордена Ленина Государственный Электротехнический Завод Вэф Им. В.И.Ленина | Selector device |
| US4792536A (en) * | 1987-06-29 | 1988-12-20 | Ppg Industries, Inc. | Transparent infrared absorbing glass and method of making |
| US4873206A (en) * | 1988-07-05 | 1989-10-10 | Ppg Industries, Inc. | Dark, neutral, gray, nickel-free glass composition |
| IE63124B1 (en) * | 1989-11-16 | 1995-03-22 | Libbey Owens Ford Co | Infrared and ultraviolet radiation absorbing green glass composition |
| US5077133A (en) * | 1990-06-21 | 1991-12-31 | Libbey-Owens-Ford Co. | Infrared and ultraviolet radiation absorbing green glass composition |
| MY104796A (en) * | 1990-01-30 | 1994-05-31 | Geoffery Evans | Batch composition for making infrared and ultraviolet radiation absorbing green glass. |
| EP0488110B1 (en) * | 1990-11-26 | 1996-06-26 | Central Glass Company, Limited | Infrared and ultraviolet ray absorbing glass |
| DE4111702C1 (en) * | 1991-04-10 | 1992-10-08 | Flachglas Ag, 8510 Fuerth, De | |
| EP0527487B1 (en) * | 1991-08-14 | 1996-11-13 | Central Glass Company, Limited | Blue-colored infrared and ultraviolet radiation absorbing glass and method of producing same |
| US5234871A (en) * | 1991-11-27 | 1993-08-10 | Schott Glass Technologies, Inc. | Vanadium- and copper-containing glasses for use as filters for light sources intended for use with night vision devices |
| JP2528579B2 (en) * | 1991-12-27 | 1996-08-28 | セントラル硝子株式会社 | Frit glass with high iron content and high reduction rate, and ultraviolet / infrared absorbing green glass using it |
-
1990
- 1990-07-30 US US07/559,915 patent/US5240886A/en not_active Expired - Lifetime
-
1991
- 1991-07-17 MX MX9100255A patent/MX173588B/en unknown
- 1991-07-24 ES ES91112391T patent/ES2087187T3/en not_active Expired - Lifetime
- 1991-07-24 DK DK91112391.7T patent/DK0469446T3/en active
- 1991-07-24 EP EP91112391A patent/EP0469446B1/en not_active Revoked
- 1991-07-24 AT AT91112391T patent/ATE135670T1/en not_active IP Right Cessation
- 1991-07-24 DE DE69118042T patent/DE69118042T2/en not_active Revoked
- 1991-07-29 KR KR1019910013000A patent/KR940002024B1/en not_active IP Right Cessation
- 1991-07-29 AU AU81404/91A patent/AU623303B2/en not_active Ceased
- 1991-07-29 JP JP3188843A patent/JPH08716B2/en not_active Expired - Fee Related
- 1991-07-29 CA CA002048061A patent/CA2048061C/en not_active Expired - Fee Related
- 1991-07-29 BR BR919103240A patent/BR9103240A/en not_active IP Right Cessation
-
1992
- 1992-03-26 US US07/857,903 patent/US5385872A/en not_active Expired - Lifetime
-
1996
- 1996-05-31 GR GR960401516T patent/GR3020136T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| US5385872A (en) | 1995-01-31 |
| DE69118042D1 (en) | 1996-04-25 |
| BR9103240A (en) | 1992-02-18 |
| CA2048061A1 (en) | 1992-01-31 |
| ES2087187T3 (en) | 1996-07-16 |
| JPH04231347A (en) | 1992-08-20 |
| EP0469446B1 (en) | 1996-03-20 |
| ATE135670T1 (en) | 1996-04-15 |
| DK0469446T3 (en) | 1996-07-22 |
| KR940002024B1 (en) | 1994-03-14 |
| JPH08716B2 (en) | 1996-01-10 |
| US5240886A (en) | 1993-08-31 |
| DE69118042T2 (en) | 1996-11-21 |
| GR3020136T3 (en) | 1996-08-31 |
| AU623303B2 (en) | 1992-05-07 |
| MX173588B (en) | 1994-03-16 |
| AU8140491A (en) | 1992-02-06 |
| EP0469446A1 (en) | 1992-02-05 |
| KR920002483A (en) | 1992-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2048061C (en) | Ultraviolet absorbing green tinted glass | |
| US5478783A (en) | Glass compositions | |
| CA2029987C (en) | Infrared and ultraviolet radiation absorbing green glass composition | |
| CA2109059C (en) | Ultraviolet absorbing green tinted glass | |
| US5023210A (en) | Neutral gray, low transmittance, nickel-free glass | |
| US5364820A (en) | Neutral gray-colored infrared and ultraviolet radiation absorbing glass | |
| CA2139334C (en) | Neutral, low transmittance glass | |
| US5830812A (en) | Infrared and ultraviolet radiation absorbing green glass composition | |
| US5077133A (en) | Infrared and ultraviolet radiation absorbing green glass composition | |
| US5380685A (en) | Bronze-colored infrared and ultraviolet radiation absorbing glass | |
| US5320986A (en) | Green-colored infrared and ultraviolet radiation absorbing glass and method of producing same | |
| USRE37514E1 (en) | Dark gray colored glass | |
| EP0648195B1 (en) | Glass composition | |
| JPH0541574B2 (en) | ||
| US6998362B2 (en) | Glass compositions | |
| CA2209122A1 (en) | Green privacy glass | |
| MXPA97002323A (en) | Composition of absorbent green glass of infrared and ultraviol radiation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |