Lithium containing glass with high oxidized iron content and specified redox ratio
11754764 · 2023-09-12
Assignee
Inventors
- George B. Goodwin (Cranberry Township, PA, US)
- Mehran Arbab (Pittsburgh, PA, US)
- Caroline S. Harris (Pittsburgh, PA)
- Larry J. Shelestak (Bairdford, PA, US)
Cpc classification
Y02P40/57
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B32B17/10045
PERFORMING OPERATIONS; TRANSPORTING
B32B17/10119
PERFORMING OPERATIONS; TRANSPORTING
C03C2204/00
CHEMISTRY; METALLURGY
B32B17/10064
PERFORMING OPERATIONS; TRANSPORTING
C03C3/083
CHEMISTRY; METALLURGY
F41H5/0407
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
C03C10/0027
CHEMISTRY; METALLURGY
C03B5/173
CHEMISTRY; METALLURGY
C03C21/002
CHEMISTRY; METALLURGY
International classification
C03B5/173
CHEMISTRY; METALLURGY
C03C1/00
CHEMISTRY; METALLURGY
C03C3/083
CHEMISTRY; METALLURGY
C03C4/08
CHEMISTRY; METALLURGY
F41H5/04
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Abstract
A low infrared absorbing lithium glass includes FeO in the range of 0.0005-0.015 wt %, more preferably 0.001-0.010 wt %, and a redox ratio in the range of 0.005-0.15, more preferably in the range of 0.005-010. The glass can be chemically tempered and used to provide a ballistic viewing cover for night vision goggles or scope. A method is provided to change a glass making process from making a high infrared absorbing lithium glass having FeO in the range of 0.02 to 0.04 wt % and a redox ratio in the range of 0.2 to 0.4 to the low infrared absorbing lithium glass by adding additional oxidizers to the batch materials. A second method is provided to change a glass making process from making a low infrared absorbing lithium glass to the high infrared absorbing lithium glass by adding additional reducers to the batch material. In one embodiment of the invention the oxidizer is CeO.sub.2. An embodiment of the invention covers a glass made according to the method.
Claims
1. A low infrared absorbing (LIRA) glass composition comprising: TABLE-US-00007 Component Range SiO.sub.2 60-63 wt % Na.sub.2O 10-12 wt % Li.sub.2O 4-5.5 wt % Al.sub.2O.sub.3 17-19 wt % ZrO.sub.2 2-5 wt % (Al.sub.2O.sub.3 + ZrO.sub.2) 21.5-24 wt % FeO 0.0005-0.015 wt % Fe.sub.2O.sub.3 (total iron) 50-1200 ppm; an oxidizer selected from the group of cerium oxide in the range of greater than 0 to 0.50 wt % and/or manganese oxide in the range of greater than 0 to 0.75 wt %; less than 5 wt % of additional glass forming materials and glass modifiers or colorants, selected from the group of MgO, CaO, MnO, TiO.sub.2, Sb.sub.2O.sub.3, As.sub.2O.sub.3, K.sub.2O, PbO, SO.sub.3, colorants and mixtures thereof; and a redox ratio in the range of 0.005-0.15, wherein glass formed from the glass composition and having a thickness of 0.223 inch (5.7 millimeters) has: a visible transmission over a wavelength range of 380 to 780 nm of equal to or greater than 88%; an infrared transmission over a wavelength range of 800 to 2100 nm of equal to or greater than 80%; and an infrared viewing transmission over the wavelength range of 400 to 920 nm of equal to or greater than 80%.
2. The glass composition according to claim 1, wherein the glass composition comprises cerium oxide in the range of 0.02 to 0.45 wt %.
3. The glass composition according to claim 1, comprising FeO in the range of 0.001-0.010 wt %.
4. The glass composition according to claim 1, wherein the redox ratio is in the range of 0.005-0.10.
5. An aircraft windshield formed from the glass composition according to claim 1.
6. A device for viewing radiated infrared energy, the device comprising: a housing having at least one passageway, the passageway having a first open end and a second open end, a lens system for viewing radiated infrared energy, a chemically tempered ballistic glass lens mounted adjacent to one end of the passageway, the ballistic glass lens comprising a first surface, an opposite second surface and a glass segment between the first and the second surfaces of the ballistic glass lens, and the glass segment formed from the glass composition according to claim 1.
7. A viewing window for infrared equipment comprising glass formed from the glass composition according to claim 1.
8. The viewing window of claim 7, wherein the infrared equipment comprises infrared night goggles and/or scopes.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DESCRIPTION OF THE INVENTION
(7) As used herein, spatial or directional terms such as “inner”, “outer”, “left”, “right”, “up”, “down”, “horizontal”, “vertical”, and the like, relate to the invention as it is shown in the drawing on the figures. However, it is to be understood that the invention can assume various alternative orientations and, accordingly, such terms are not to be considered as limiting. Further, all numbers expressing dimensions, physical characteristics, and so forth, used in the specification and claims are to be understood as being modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical values set forth in the following specification and claims can vary depending upon the property desired and/or sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Moreover, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range of “1 to 10” should be considered to include any and all subranges between and inclusive of the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 1 to 6.7, or 3.2 to 8.1, or 5.5 to 10. Also, as used herein, the term “mounted over” means mounted over but not necessarily in surface contact with. For example, one article or component of an article “mounted over” another article or component of an article does not preclude the presence of materials between the articles, or between components of the article, respectively.
(8) Before discussing several non-limiting embodiments of the invention, it is understood that the invention is not limited in its application to the details of the particular non-limiting embodiments shown and discussed herein since the invention is capable of other embodiments. Further, the terminology used herein to discuss the invention is for the purpose of description and is not of limitation. Still further, unless indicated otherwise, in the following discussion like numbers refer to like elements.
(9) The non-limiting embodiments of the invention are disclosed using the lithium glass compositions disclosed in USPN '755, however, the invention is not limited thereto, and the invention can be practiced to change from one Campaign making a soda-lime-silicate glass having a high oxidized iron content, e.g. but not limited to ferrous oxide in the range of 0.02 to 0.04 wt %, and a redox ratio in the range of 0.2 to 0.4, to another Campaign making a soda-lime-silicate glass having a low oxidized iron content, e.g. but not limited to ferrous oxide in the range of 0.001 to 0.010 wt %, and a redox ratio in the range of 0.005 to 0.15.
(10) As can now be appreciated, Fe.sub.2O.sub.3 and/or FeO can be added as a colorant or a property modifier. The total amount of iron present in the lithium glasses disclosed herein is expressed in terms of Fe.sub.2O.sub.3 in accordance with standard analytical practice but that does not imply that all of the iron is actually in the form of Fe.sub.2O.sub.3. Likewise, the amount of iron in the ferrous state is reported as FeO even though it may not actually be present in the glass as FeO. In order to reflect the relative amounts of ferrous and ferric iron in the glass compositions disclosed herein, the term “redox ratio” shall mean the amount of iron in the ferrous state expressed as FeO divided by the amount of total iron expressed as Fe.sub.2O.sub.3. Furthermore, unless stated otherwise, the term “total iron” in this specification shall mean total iron expressed in terms of Fe.sub.2O.sub.3 and the term “FeO” shall mean iron in the ferrous state expressed in terms of FeO.
(11) The ranges of materials or ingredients of the lithium containing glass disclosed in USPN '755 are listed in following Table 1.
(12) TABLE-US-00004 TABLE 1 Component Range Preferred Range SiO2 59-63 wt % 60-63 wt % Na2O 10-13 wt % 10-12 wt % Li2O 4-5.5 wt % 4-5.5 wt % Al2O3 15-23 wt % 17-19 wt % ZrO2 2-5 wt % 3.5-5 wt % (Al2O3 + ZrO2) 19-25 wt % 21.5-24 wt %
(13) The weight percent of all the oxides in the glass except for lithium are measured using X-Ray Fluorescence Spectroscopy (also known as “XRFS”). The weight percent of lithium oxide in the glass is measured by atomic absorption.
(14) Minor quantities (up to about 5% by weight total) of other glass forming materials and glass modifiers or colorants can be included, e.g. MgO, MnO, TiO.sub.2, Sb.sub.2O.sub.3, As.sub.2O.sub.3, K.sub.2O, PbO, ZnO and CaO, and mixtures thereof. As is appreciated by those skilled in the art, Sb.sub.2O.sub.3 and As.sub.2O.sub.3 are oxidizers for the glass sheet drawing process, but are not compatible for use in the float glass process because the reducing conditions of the float glass chamber reduces the Sb.sub.2O.sub.3 and As.sub.2O.sub.3 to antimony and arsenic metals, respectively.
(15) In one non-limiting embodiment of the invention, when the lithium glass sheet having the composition of Table 1 is to be heated, e.g. but not limiting to the discussion, prior to bending and/or shaping of the sheet, the lithium glass composition contains the ingredients of Table 1 plus ferrous oxide in the range of 0.02 to 0.05 wt %, and preferably in the range of 0.03 to 0.038 wt %, and a redox ratio in the range of 0.2 to 0.4 and preferably in the range of 0.2 to 0.35 (hereinafter the preceding glass is also referred to as “high infrared absorbing lithium glass” or “HIRA lithium glass”). During the Campaign to make the HIRA lithium glass, additions of sulfates and carbon are made to the glass batch ingredients. The sulfates and carbon additions are made to increase the ferrous oxide content to maintain the molten glass within the desired redox ratio range.
(16) In another non-limiting embodiment of the invention, when the lithium containing glass having the composition of Table 1 is used as a viewing window for infrared equipment, e.g. but not limited to infrared night goggles, scopes, e.g. rifle scopes, the lithium glass composition contains the ingredients of Table 1. As noted, oxides of iron are not listed as a component, however, as is appreciated by those skilled in the art, it is expected that oxides of iron, e.g. ferrous iron will be present in the glass as a tramp material found in the batch materials, e.g. glass cullet. To the extent ferrous iron can be present, the invention contemplates that the glass of the invention will include the composition of Table 1 plus ferrous oxide in the range of 0.0005 to 0.015 wt %, and preferably in the range of 0.001 to 0.010 wt %, and a redox ratio in the range of 0.005 to 0.15 and preferably in the range of 0.005 to 0.10 (hereinafter the preceding glass is also referred to as “low infrared absorbing lithium containing glass” or “LIRA lithium glass”). It is expected that the total iron (Fe.sub.2O.sub.3) will be in the range of 50 to 200 ppm Fe.sub.2O.sub.3. During the Campaign to make the LIRA lithium glass, additions of oxidizers compatible with the selected glass making processes are added to the glass, e.g. cerium oxide, manganese oxide, antimony oxide, arsenic oxide and combinations thereof are added to the glass batch ingredients to maintain the molten glass within the redox ratio range for a LIRA lithium glass.
(17) As discussed above, the wt % of ferrous oxide is higher for the HIRA lithium glass to increase the absorption of the infrared wavelengths to decrease the heating time of the glass to reach the bending temperatures or to provide a level of solar heat control, and the wt % of the ferrous iron is lower for the LIRA lithium glass to reduce the absorption of infrared energy in the infrared viewing range and increase the percent transmittance of the infrared energy in the infrared viewing range to enhance the viewing of the infrared generating objects. For purposes of clarity, the ultraviolet wavelength range is 300 to 380 nanometers (hereinafter also referred to as “nm”); the visible wavelength range is 380 to 780 nm; and the near infrared wavelength range is 800 to 2100 nm; of the electromagnetic spectrum. The infrared viewing wavelength range is device dependent. In one non-limiting embodiment of the invention, the infrared viewing wavelength range is 400 to 920 nm of the electromagnetic spectrum. In the practice of the invention, the LIRA lithium glass preferably has a visible transmission of equal to and greater than 88%, more preferably a visible transmission of greater than 89% and most preferably a visible transmission of greater than 90%; an infrared transmission of equal to and greater than 80%, more preferably an infrared transmission of greater than 85% and most preferably an infrared transmission of equal to and greater than 90%; an infrared viewing transmission of equal to and greater than 80%, more preferably an infrared viewing transmission of greater than 85% and most preferably an infrared viewing transmission of greater than 90%.
(18) Further, In the practice of the invention, the HIRA lithium glass has a visible transmission of less than 88%; an infrared transmission of less than 75%; an infrared viewing transmission of less than 80%.
(19) The spectral properties of the LIRA lithium glass given above are reported at a thickness of 0.223 inch (5.7 millimeters). The visible transmission is determined using CIE Standard Illuminant A with a 2° observer over a wavelength range of 380 to 780 nanometers. The infrared transmittance is determined using Parry Moon air mass 2.0 direct solar irradiance data over a wavelength range of 800 to 2100 nm. The viewing transmittance is determined using the relative spectral irradiance of CIE Standard Illuminant A and the response function of the viewing device over the wavelength range 400 to 930 nm.
(20) The LIRA and HIRA lithium glasses of the invention can be made using a conventional non-vacuum refiner float glass system, e.g. but not limited to the type shown in
(21) Referring to
(22) Flames (not shown) to melt the batch materials 28 and to heat the molten glass 38 issue from burner ports 42 spaced along the sidewalls 26 (see
(23) As can be appreciated by those skilled in the art, the invention contemplates using a mixture of air and fuel gas, or a mixture of oxygen and fuel gas, to generate the flames to heat the batch materials and the molten glass. For a discussion of using oxygen and fuel gas in a glass melting furnace, reference can be made to U.S. Patent Application Publication No. 2009-0205711 A1 titled “Use of Photovoltaic for Waste Heat Recovery”, which Publication is incorporated herein by reference).
(24) The glass batch materials 28 moving downstream from the batch feeding end or doghouse end wall 46 are melted in the melting section 48 of the furnace 20, and the molten glass 38 moves through waist 54 (see
(25) As can now be appreciated by those skilled in the art, when changing from a Campaign making HIRA lithium glass to a Campaign making LIRA lithium glass, the ferrous iron in the molten HIRA lithium glass contained in the furnace 20 (see
(26) In the practice of the invention, the change from molten HIRA lithium glass to molten LIRA lithium glass can be made in 3 to 4 days using an oxidizing agent. In one non-limiting embodiment of the invention, cerium oxide (CeO.sub.2) and/or manganese oxide (MnO.sub.2) is/are used to oxidize the ferrous iron to the ferric iron because, as discussed above, they are compatible with the glass making process shown in
(27) More particularly, samples of the glass shown in Table 2 (also referred to as “Control Sample”); samples of the glass shown in Table 1 with additions of CeO.sub.2 (also referred to as “Cerium Samples”), and samples of the glass shown in Table 1 with additions of MnO.sub.2 (also referred to as “Manganese Samples”), were made. Samples 1-5 are the Cerium Samples having varying amounts of cerium oxide, and Samples 6 and 7 are the Manganese Samples having varying amounts of manganese oxide.
(28) TABLE-US-00005 TABLE 2 SAMPLE Control 1 2 3 4 5 6 7 Component (wt %) CeO2 0 0.165 0.245 0.270 0.375 0.437 0 0 MnO2 0 0 0 0 0 0 0.175 0.325 FeO 0.017 0.007 0.004 0.002 0.001 0.001 0.012 0.007 FeO/Fe2O3 0.189 0.083 0.044 0.020 0.019 0.009 0.132 0.072
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(30) In the practice of the invention, cerium oxide in the range of greater than 0 to 0.50 wt % can be used; in the range of 0.02 to 0.45 wt % is preferred, and in the range of 0.04 to 0.40 wt % is more preferred. Other ranges for cerium oxide include but are not limited to 0.01 to 0.15 wt %; 0.02 to 0.10 wt % and 0.03 to 0.07 wt %. Manganese oxide in the range of greater than 0 to 0.75 wt % can be used, in the range of 0.02 to 0.50 wt % is preferred, and in the amount of 0.04 to 0.45 wt % is more preferred. As can be appreciated, a mixture of CeO.sub.2 and MnO.sub.2 can be used in the practice of the invention to oxidize the ferrous iron. Generally for the given range of MnO.sub.2, one part of CeO.sub.2 replaces 1.10 to 1.50 parts of MnO.sub.2, and for the given range of CeO.sub.2, 1.10 to 1.5 parts of MnO.sub.2 replaces one part of CeO.sub.2. Glasses of lower total iron content can use lower amounts of cerium oxide or manganese oxide. The amount of cerium oxide or manganese oxide in this specification shall mean total cerium or manganese, respectively, expressed in terms of CeO.sub.2 or MnO.sub.2, even though these components may not actually be present in the glass as CeO.sub.2 or MnO.sub.2.
(31) In the following non-limiting embodiment of the invention, Campaign A is active to make HIRA lithium glass. Campaign A is designated to end and Campaign B started to make LIRA lithium glass. The composition of the HIRA lithium glass being made and the composition of the LIRA lithium glass to be made are shown in TABLE 3.
(32) TABLE-US-00006 TABLE 3 HIRA LIRA Lithium glass Lithium glass Component Campaign A Campaign B SiO2 59-63 wt % 60-63 wt % Na2O 10-13 wt % 10-12 wt % Li2O 4-5.5 wt % 4-5.5 wt % Al2O3 15-23 wt % 17-19 wt % ZrO2 2-5 wt % 3.5-5 wt % (Al2O3 + ZrO2) 19-25 wt % 21.5-24 wt % FeO 0.02-0.05 wt % 0.001-0.010 wt % FeO/Fe2O3 0.2-0.4 0.005-0.10 CeO2 0.00 0.02-0.45 wt% Fe2O3 (total iron) 800-1200 ppm 50-1200 ppm
(33) During the running of Campaign A, the HIRA lithium glass batch materials are fed into the furnace 20 (see
(34) In one embodiment of the invention, cerium carbonate is added to the batch materials to provide the cerium oxide in the glass. To make the LIRA lithium glass of TABLE 3 cerium carbonate in the range of 0.033-0.75 wt % is added to the batch materials. With the initial LIRA lithium glass batch materials (the first thirty six hour period of Campaign B), cerium carbonate in the range of 0.066-1.50 wt % is added to the batch materials. At the end of the initial thirty six hour period of Campaign B, the cerium carbonate is reduced to a range of 0.033-0.75 wt % to run Campaign B to make the LIRA lithium glass of TABLE 3. The additional cerium carbonate during the first thirty six hour period of Campaign B is made to oxidize the ferrous iron in the melting section 26 and in the refining section 56 of the furnace 20. At the end of the initial thirty six hour period, the glass batch materials for the LIRA lithium glass are moved into the melting section 46 of the furnace 20 as discussed above.
(35) In another non-limiting embodiment of the invention, if a glass being made has sufficient UV absorber, e.g. cerium oxide, after the thirty-six hour pulse, no further additions of cerium carbonate are necessary if sufficiently low iron batch, e.g. but not limiting to the invention batch having less than 0.0005 wt % is used to make the glass not having a UV absorber.
(36) The invention is not limited to the number or the length of the pulses, or the wt % of the cerium oxide in the pulses. In the practice of the invention, the wt % of cerium oxide in the pulse is usually 2 to 3 times the wt % of cerium oxide in the LIRA lithium glass batch, and the number of pulses is usually one or two. The time period of each pulse can be varied as needed. The above procedure directed to the use of CeO.sub.2 to oxidize the ferrous iron when changing from Campaign A to Campaign B is applicable to the practice of the invention using MnO.sub.2, or a mixture of CeO.sub.2 and MnO.sub.2, to change from Campaign A making HIRA lithium glass to Campaign B making LIRA lithium glass. Although the procedure is the same, the wt % of MnO.sub.2, and of the mixture of CeO.sub.2 and MnO.sub.2 is increased because the cerium oxide is a more effective oxidizer than manganese oxide.
(37) The invention is not limited to the additions of the oxidizers, e.g. but not limited to CeO.sub.2, MnO.sub.2, and mixtures of CeO.sub.2 and MnO.sub.2 to the batch materials, and the invention contemplates adding the additional oxidizer to the molten glass in the refiner 56 or to the molten glass in the melter 36 at a position upstream from the waist 54.
(38) In another non-limiting embodiment of the invention, a campaign making LIRA lithium glass is changed to a campaign making HIRA lithium glass by making additions of a reducing agent to reduce the ferric iron to ferrous iron. Reducing agents that can be used in the practice of the invention include, but are not limited to carbon, carbon containing materials, e.g. but not limited to graphite, sucrose (C.sub.12H.sub.22O.sub.11), coal, silicon metal and tin oxide (SnO.sub.2). Additional non-limiting embodiments of the invention include, but are not limited to changing campaigns for making different types of soda-lime silicate glasses or any other types of glasses, e.g. going from a HIRA or LIRA lithium glass to a soda-lime silicate glass, or visa versa.
(39) The use of the HIRA lithium glass, and the LIRA lithium glass, of the invention made during Campaigns A and B is not limiting to the invention and can be processed for use in windows for land, air, space, above water and below water, vehicles; transparencies for commercial and residential windows, covers for solar collectors, and for ballistic viewing windows. The HIRA lithium glass is generally used for viewing windows using a source that provides visible light, and is generally not recommended for viewing infrared energy from objects, e.g. the use of HIRA lithium glasses is not recommended for night goggles. For night vision equipment, the LIRA lithium glass is recommended to protect the lens system of the night vision equipment, e.g. but not limited to night vision goggles and night vision scopes. More particularly and with reference to
(40) With reference to
(41) In the practice of the non-limiting embodiments of the invention, the LIRA and HIRA lithium glasses can be uncoated or coated with any type of coating, e.g. but not limited to an environmental coating to selectively pass predetermined wavelength ranges of light and energy, a photocatalytic film or water-reducing film, or a transparent conducting oxide e.g. of the types disclosed in U.S. Pat. Nos. 5,873,203 and 5,469,657, which patents are incorporated herein by reference.
(42) The invention is not limited to the embodiments of the invention presented and discussed above which are presented for illustration purposes only, and the scope of the invention is only limited by the scope of the following claims and any additional claims that are added to applications having direct or indirect linage to this application.