United States Patent (19)
`Jones et al.
`
`III IIII IIH|||||
`USO05346867A
`11)
`Patent Number:
`5,346,867
`(45.
`Date of Patent:
`Sep. 13, 1994
`
`54 NEUTRAL GRAY ABSORBING GLASS
`COMPRISING MANGANESE OXDE FOR
`SELENIUM RETENTION DURING
`PROCESSING
`75 Inventors: James W. Jones, Toledo, Ohio;
`Edward N. Boulos, Troy, Mich.
`73 Assignee: Ford Motor Company, Dearborn,
`Mich.
`21 Appl. No.: 168,347
`22 Filed:
`Dec. 17, 1993
`51
`Int. Cl. .............................................. CO3C 3/087
`52 U.S. C. ......................................... 501/71; 501/70
`58 Field of Search .................................... 501/70, 71
`56)
`References Cited
`U.S. PATENT DOCUMENTS
`Re. 25,312 1/1963 Duncan et al. ....................... 50/71
`2,394,493 2/1946 Schoendaub ....
`... 501/71 X
`3,296,004 1/1967 Duncan ................................. 501/71
`3,300,323 1/1967 Plumat et al........
`... 501/70
`3,351,475 11/1967 Hagedornet al...
`... 501/71
`3,723,142 3/1973 Kato et al. ..........
`... 501/71
`3,844,796 10/1974 Jasinski ...........
`... 501/70
`3,904,425 9/1975 Young et al. ...
`... 501/7
`3,915,722 10/1975 Schaller ..........
`... 501/57
`3,928,050 12/1975 Jasinski ...
`... 501/71
`4,104,076 8/1978 Pons ............
`... 501/66
`4,235,634 11/1980 Boyd et al...
`... 501/70
`4,339,541 7/1982 Dela Ruye......
`... 501/71
`4,792,536 12/1988 Pecoraro et al. ...
`... 501/70
`4,873,206 10/1989 Jones ...................
`... 501/71
`5,023,210 6/1991 Krumwiede et al. ................. 501/71
`
`
`
`5,030,593 7/1991 Heithoff ................................ 501/72
`5,212,122 5/1993 Pannhorst et al. .
`... 50/69
`5,264,400 1 1/1993 Nakayuchi et al. ....
`... 501/71
`5,308,805 5/1994 Baker et al. ........................... 501/71
`FOREIGN PATENT DOCUMENTS
`2082647 12/1971 France .................................. 501/70
`104.1579 9/1981 Japan .......
`... 501/71
`0739013 6/1980 U.S.S.R...
`... 501/71
`0739014 6/1980 U.S.S.R. ................................ 501/71
`OTHER PUBLICATIONS
`Chemical Approach To Glass, Milos B. Volf, Glass
`Science and Technology, 7; Elsevier-1984 (No Month).
`Primary Examiner-Mark L. Bell
`Assistant Examiner-David R. Sample
`Attorney, Agent, or Firm-Lorraine S. Melotik; Roger
`L. May
`ABSTRACT
`(57)
`A neutral gray, heat absorbing soda-lime-silica glass
`having at 4 mm. control thickness a light transmittance
`using illuminant A of 10.0% to 55.0%, ultra violet trans
`mittance less than 25.0%, and infra red transmittance is
`less than about 50.0% produced with colorants consist
`ing of 0.90 to 1.90 percent by weight total iron oxide as
`Fe2O3, 0.002 to 0.025 percent Co, 0.0010 to 0.0060 per
`cent Se, 0.10 to 1.0 percent MnO2, and 0 to 1.0 percent
`TiO2. The flat glass products having such a composition
`is particularly suitable for use as a privacy glass or Sun
`roof product in trucks and automobiles.
`
`14 Claims, No Drawings
`
`O-I Glass, Inc.
`Exhibit 1035
`Page 001
`
`

`

`1.
`
`NEUTRAL GRAY ABSORBNG GLASS
`COMPRISING MANGANESE OXDE FOR
`SELENUM RETENTON DURING PROCESSING
`
`5,346,867
`2
`5,023,210 to Krumwiede et al. discloses the use of
`chrome oxide in combination with iron oxide, cobalt
`oxide and selenium to achieve a dark gray glass without
`nickel. It does not include MnO2.
`SUMMARY OF THE INVENTION
`The present invention is a soda-lime-silica glass com
`position that is heat absorbing with a neutral gray color
`and improved selenium retention. The composition in
`its broadest embodiment comprises 68 to 75% SiO2, 10
`to 18% Na2O, 5 to 15% CaO, 0 to 10% MgO, 0 to 5%
`Al2O3, and 0 to 5% K2O, where CaO + MgO is 6 to
`15% and Na2O --K2O is 10 to 20%, with traces of
`melting and refining aids, if any, and colorants consist
`ing essentially of 0.90 to 1.90 wt.% total iron oxide as
`Fe2O3; 0.002 to 0,025 wt.% cobalt as Co; 0.0010 to
`0.0060 wt.% selenium as Se; 0.10 to 1.0 wt.% manga
`nese oxide as MnO2; and 0.0 to 10% titanium oxide as
`TiO2.
`Glass products made according to embodiments of
`the invention have the following spectral properties at 4
`mm thickness: 100 to 55.0% light transmittance using
`illuminant A (LTA), less than 25.0% ultra violet trans
`mittance, and less than 50.0% infra red transmittance.
`Preferably, the composition has a dominant wavelength
`between about 470 and 590 nanometers. Generally, as
`the quantities of the colorants increase, the 20 transmit
`tance will go down. Similarly, generally as the glass
`thickness increases for a given glass composition, the
`transmittance of the thicker glass will decrease.
`We have unexpectedly discovered that introducing
`manganese oxide in the batch increases the retention of
`selenium in the glass product over and above that ob
`tained by incorporating nitrates. While the major func
`tion of the manganese oxide is to increase the selenium
`retention, there is some absorption by manganese oxide
`in the same portion of the visible spectrum as the sele
`nium component, hence incorporation of manganese
`oxide also further enhances the grey color. Thus, less of
`the costly selenium is necessary to be present in the
`composition since the manganese oxide in effect also
`acts to provide the grey color. Desirably, the glass
`composition of this invention has a gray color which is
`obtained without the addition of nickel.
`DETAILED DESCRIPTION OF THE
`INVENTION
`Flat soda-lime-silica glass, used in the automotive and
`architectural industries and conveniently made by the
`float glass process, is generally characterized by the
`following basic composition shown in Table I, the
`amounts of the components being based on a weight
`percentage of the total glass composition:
`TABLE I
`Oxide Component
`SiO2
`Al2O3
`CaO.
`MgO
`Na2O
`K2O
`
`Weight %
`68 to 75
`0 to 5
`5 to 15
`0 to 10
`10 to 18
`0 to 5
`
`The neutral gray glass composition of the present
`invention employs this basic soda-line-silica glass com
`position wherein, additionally, CaO + MgO is 6 to 15%
`and Na2O + K2O is 10 to 20%. Preferably SO3 is 0.10
`to 0.30 wt.%, more preferably 0.14 to 0.25 wt.%. In
`
`BACKGROUND OF THE INVENTION
`This invention is directed to a heat absorbing, neutral
`gray colored glass composition. More particularly, it
`comprises soda-lime-silica glass whose coloring compo
`10
`nents consist essentially of iron oxide, cobalt, selenium,
`manganese dioxide, and optionally titanium dioxide.
`Glass having a neutral gray color and properties such
`as low infra red transmittance and low total solar en
`ergy transmittance which reduce the heat gain in the
`15
`interior of an enclosure is highly desired in the automo
`tive field. The neutral gray color is chosen for the sake
`of coordinating with a wide range of automotive paint
`colors. To be particularly useful in the automotive field,
`the glass composition should be one that is compatible
`with flat glass manufacturing methods. A glass compo
`20
`sition having these properties would be highly desir
`able, particularly for automotive privacy and sun roof
`applications.
`Some other heat absorbing gray glass compositions
`contain selenium as an essential coloring component.
`25
`For example, U.S. Pat. No. 4,873,206 to Jones discloses
`a gray glass composition which includes as the color
`ants only iron, cobalt, and selenium. Selenium is a rela
`tively low melting component with a melting point of
`217 C. and a boiling point of 685 C. which typically
`30
`leads to a volatilization of 85% or more of the selenium
`from the glass batch during glass melting and process
`ing. Selenium is a very expensive material and hence its
`emission during glass melting is less than desirable. This
`high level of volatilization takes place even though
`35
`glass manufacturers typically use sodium or potassium
`nitrates in the glass composition in an attempt to retain
`more of the selenium in the glass product.
`The present invention overcomes problems associ
`ated with selenium vaporization by incorporating man
`ganese oxide into a grey glass composition along with
`the selenium. We have unexpectedly found that incor
`porating the manganese oxide into a selenium contain
`ing glass composition aids in selenium retention during
`melt processing.
`45
`In addition, contrary to the suggestion of Jones in the
`patent listed above, including manganese oxide in the
`present invention composition along with the iron oxide
`did not lead to increased solarization. Solarization is the
`result of reactions that occur in glass when exposed to
`UV radiation such as that in sunlight. One such reaction
`is the shift of Fet-3 towards Fe+2. Solarization causes
`the iron to move from the oxidized species to the re
`duced species which also causes an undesirable color
`shift in the glass product. This problem of solarization is
`also discussed by Milos B. Volfin Chemical Approach to
`Glass, Elsevier Science Publishing Co., Inc., 1984, p.
`343. "Manganese as a decolorizer has the disadvantage
`of creating solarization and of being sensitive to the
`furnace atmosphere.”
`Generally, gray colored heat absorbing glasses relied,
`in the past, on the inclusion of nickel oxide as an active
`coloring agent. Nickel compounds, however, are
`known to react with other materials in soda-line-silica
`glass and form nickel sulfide "stones' in the glass. These
`65
`stones are usually small, thereby avoiding detection
`methods, but can produce an unacceptably high rate of
`breakage during tempering of the glass. U.S. Pat. No.
`
`SO
`
`55
`
`O-I Glass, Inc.
`Exhibit 1035
`Page 002
`
`

`

`10
`
`30
`
`5,346,867
`3
`4
`addition, the neutral gray glass composition consists
`Titanium dioxide may optionally be used in the pres
`essentially of the following coloring components: iron
`ent invention neutral gray glass composition to enhance
`oxide; cobalt oxide; selenium; manganese oxide; and
`achievement of a particular range of dominant wave
`optionally titanium dioxide as summarized above,
`length to the glass composition. Gray glasses of this
`The total iron oxide as Fe2O3 is present in the inven
`invention are preferably those with an excitation purity
`tion composition in quantities of 0.9 to 1.90 weight %.
`of less than about 5.5%. It is important that the present
`All weight percents disclosed herein are based on the
`invention glass product be a neutral gray, more specifi
`total weight of the invention glass composition. Typi
`cally being agreen gray; preferably the dominant wave
`cally, this ingredient is added into the batch ingredients
`length with illuminant C is between 470 and 590 nano
`meters (nm), more preferably between 480 and 570 nm,
`in oxide form, e.g., Fe2O3. The iron oxide incorporated
`most preferably between 487.5 and 558 nm, using the
`in the composition lowers both the ultra violet and the
`infra red transmittance of the glass products. More
`C.I.E. convention with a 2 observer. Titanium dioxide
`is very useful in shifting the dominant wavelength
`particularly, the iron oxide performs two functions in
`within the range of 470 to 590 nanometers. Titanium
`this glass system: (1) the oxidized form of iron oxide
`dioxide also absorbs in the ultra violet range of the
`(Fe2O3) absorbs in the ultra violet portion of the spec
`15
`spectral curve and helps to lower the ultra violet trans
`trum providing low ultra violet transmittance, and (2)
`mittance of glass in this invention.
`the reduced form of iron oxide (Fe0) absorbs in the
`We have found that glasses within the broadest scope
`infrared portion of the spectrum and the resultant glass
`of this invention have the following spectral properties
`thus has a lowered infrared transmittance. Both absorb
`when measured at a control thickness of 4.0 millime
`20
`ing functions of the iron oxide are especially valuable
`ters: light transmittance with illuminant A (LTA) be
`when the glass product is used in automobiles. When
`tween 10.0% and 55.0%, ultra violet transmittance of
`heat is absorbed by the glass, the load on air condition
`less than 25.0%, preferably less than about 10.0% when
`ers is initially reduced and there is less total heat in the
`the glass has less than 35.0% LTA, and infra red trans
`vehicle to cool.
`mittance is less than about 50.0%. As would be apparent
`25
`Cobalt, which is typically added to the batch ingredi
`to those skilled in the art in view of the present disclo
`ents as an oxide thereof, is present as a coloring compo
`sure, the glass composition of this invention may also be
`nent in the invention glass composition in an amount of
`made into glass at other thicknesses. Generally, al
`0.002 to 0,025 wt.% as Co, the cobalt functioning to
`though not meant to be so limited, the thickness for the
`absorb light from about 580 to 680 nanometers in the
`glass product would be within the range of 2.0 to 12.0
`visible portion of the spectrum. Selenium, which is
`millimeters which is typical of glass produced by the
`typically added to the batch ingredients as a metal, is
`float process.
`present as a coloring component in an amount of 0.0010
`Table II discloses the amounts of raw material batch
`to 0.0060 wt.% Se, the selenium functioning to absorb
`ingredients which are preferably used to form embodi
`light from about 430 to 540 nanometers of the visible
`ments of neutral gray glass compositions according to
`35
`spectrum. It is necessary to balance the amount of ab
`the present invention.
`sorption from selenium with that of cobalt to achieve a
`neutral gray appearance.
`TABLE II
`Manganese oxide is present in the grey glass inven
`BATCH MATERIAL
`RANGE MASS (LBS)
`tion composition in an amount of 0.10 to 1.0 wt % based
`Sand
`1000
`on MnO2. Manganese oxide can be added to the batch
`Soda Ash
`290 to 320
`glass components in a variety of forms, e.g., MnO2,
`Dolomite
`215 to 260
`Limestone
`75 to 90
`MnO4, MnO, etc. In the glass composition, it is gener
`Salt Cake
`6 to 24
`ally present in the Mn+2 and Mn+3 state, although it
`Rouge (97% Fe2O3)
`17 to 23
`may additionally be present in other states such as
`Titanium Dioxide
`0 to 5
`45
`Mnt. There are two functions that manganese oxide
`Sodium Nitrate
`3 to 20
`Manganese Dioxide
`2 to 8
`performs in the present invention composition: (1) one
`Carbocite (70% C)
`0.1 to 1.5
`form of manganese in the glass absorbs in the same area
`Cobalt Oxide (Co3O4)
`0.30 to 0.36
`as selenium so that it replaces a portion of the selenium,
`Selenium
`0.20 to 0.70
`and (2) manganese oxide acts as an oxidizer and helps to
`50
`retain a larger proportion of selenium from the batch.
`Typically, in compositions without manganese oxide, a
`large amount of selenium (about 85-90%) which is very
`costly volatilizes from the batch even when using so
`dium or potassium nitrates as oxidizers. Therefore, our
`55
`finding that manganese oxide is extremely beneficial in
`retaining a higher proportion in the final glass product
`of the selenium added into the batch (~300% increased
`selenium retention) was unexpected and is a critical
`point of this invention. As discussed above and in more
`detail below, unexpectedly we have also found that
`contrary to prior teachings, including manganese oxide
`along with iron oxide in the glass composition did not
`cause any appreciable solarization (discoloring) after
`exposure to ultra-violet light. We have discovered that
`employing manganese oxide along with iron oxide in
`amounts as specified in this invention composition, al
`lows the solarization phenomena to be minimized.
`
`As would be appreciated by those skilled in the art,
`processing aids are generally added to the glass batch
`during the melting and processing, e.g., to maintain the
`proper balance of redox conditions or as fining agents.
`For example, carbocite (anthracite coal) when added to
`the glass composition has the effect of reducing a por
`tion of the Fe2O3 to Fe0 to achieve lower infra red
`transmittance. Sodium and/or potassium nitrate are
`used in glass batches of the invention to maintain oxidiz
`ing conditions early in the melting process which aids in
`selenium retention. Nitrates have been used by others to
`improve selenium retention. Careful balance must be
`maintained between the reducing conditions from the
`carbocite and the oxidizing conditions from the nitrates
`and manganese dioxide used to improve selenium reten
`tion in the glass, because the oxidizers also act upon the
`iron oxide to shift the redox from FeO toward Fe2O3
`while carbocite shifts the iron oxide equilibrium in the
`
`65
`
`O-I Glass, Inc.
`Exhibit 1035
`Page 003
`
`

`

`6
`TABLE III-continued
`Example Example Example Example
`2
`3
`4
`21.0
`22.3
`19.0
`
`17.1
`
`% Selenium Retained
`
`10
`
`5
`
`Present invention compositions of Examples 1-4
`show amounts of retained selenium of between 17.1 and
`22.3%. In contrast, comparative Examples 5-8 below,
`not according to this invention (i.e., not including
`MnO2) show amounts of retained selenium of only be
`tween 6.2 and 7.8%. These examples show an almost
`300% increase in selenium retention when manganese
`dioxide is employed along with the selenium as in the
`present invention compositions.
`TABLE IV
`Example Example Example Example
`5
`6
`7
`8
`100.00
`100.00
`100.00
`100.00
`3141
`31.4
`31.41
`3.41
`7.25
`7.25
`7.25
`7.25
`25.83
`25.83
`25.83
`25.83
`1.096
`1.0960
`1.0960
`1.0958
`0.587
`0.5234
`0.5220
`0.5188
`2.1078
`1.8144
`2.1105
`2.105.
`0.0912
`0.0913
`0.0912
`0.097
`0.065
`0.0144
`0.0317
`0.0389
`0.0286
`0.0414
`0.0963
`0.1116
`8
`10
`22
`28
`
`Sand
`Soda Ash
`Limestone
`Dolomite
`Salt Cake
`Sodium Nitrate
`Rouge
`Carbocite
`Cobalt Oxide
`Selenium
`ppm Selenium
`in Glass
`% Selenium Retained
`
`5,346,867
`5
`opposite direction. As disclosed above, we have discov
`ered that employing manganese oxide along with iron
`oxide in the amounts specified for the invention compo
`sition, allows the solarization phenomena to be mini
`mized. The quantities of salt cake, carbocite and sodium
`nitrate preferably used in the batch ingredients to
`achieve the desired ratio between the two iron oxides in
`the final composition also helps to retard solarization in
`the invention glass. More preferably, the lbs. of batch
`materials: salt cake; sodium nitrate; carbocite is 8-18;
`5-15; 0.3-1.0, and most preferably are: 8-12; 5-10;
`0.3-1.0, respectively per 1000 lbs. of sand. These dis
`closed most preferred amounts of the three batch mate
`rials is associated with a final glass product preferably
`having 0.15-0.60 wt.% MnO2 and 1.2-1.6 wt.% total
`iron as Fe2O3 in the final glass composition.
`In order to show the unexpected effects of manganese
`dioxide on improving selenium retention in our glass
`composition, eightgrey glass compositions were made
`as described below in Tables III and IV. Neutral gray
`glass compositions made according to embodiments of
`this invention were detailed as Examples 1-4. For com
`parison, similar glass compositions except without man
`ganese dioxide were made as detailed as Examples 5-8.
`25
`All of these glasses were made by the following proce
`dure. The batches were weighed (typically 170 grams
`total) on a laboratory balance and mixed within a glass
`jar for 10 minutes each using a laboratory shaker. Each
`mixed batch was placed into a platinum-rhodium cruci
`30
`ble which was about 2' tall with about a 2.5' inside
`diameter and 4.5 ml. of water was mechanically mixed
`into the raw batch. Crucibles were placed into a natural
`gas/air furnace pre-heated to 2600 F. with 3 to 5 other
`crucibles. Furnace temperature recovers to 2600 F. in
`35
`about 30 minutes. After two hours melting, each cruci
`ble was removed in turn, glass in the crucible was fritted
`by quenching in cold water, and the fragments were
`mixed in the crucible and all crucibles were returned to
`the furnace. Furnace temperature was brought back to
`2600' F. and the fritting procedure was repeated as in
`the step above once the operating temperature was
`attained, about 45 minutes. All glass samples were
`melted for another 3 hours and each sample was poured
`into a 2.5" inside diameter graphite mold to shape the
`45
`glass samples for subsequent grinding and polishing. All
`samples were placed into an annealing furnace, brought
`up to 1050 F., held for 4 hours, then allowed to slowly
`cool to room temperature in about 16 hours. Samples
`were ground and polished and spectral properties were
`50
`measured on each sample; spectral properties were
`calibrated to a control thickness of 4 mm. Samples were
`then chemically analyzed via X-ray fluorescence or
`other tests conducted as needed.
`TABLE III
`Example Example Example Example
`2
`3
`4
`100.00
`100.00
`100.00
`31.41
`31.4
`31.41
`7.25
`7.25
`7.25
`25.83
`25.83
`25.83
`1.0960
`1.0969
`1.0969
`0.5192
`0.5233
`0.5236
`2.1103
`1.9683
`2.1061
`0.0914
`0.0916
`0.0907
`0.0313
`0.0370
`0.0392
`0.8107
`1.3750
`0.5315
`0.0490
`0.0430
`0.0577
`75
`70
`80
`
`7.8
`
`6.5
`
`6.2
`
`6.2
`
`Table V below lists the preferred ranges of resultant
`oxide constituents of our new glass composition. Fol
`lowing the table are the spectral properties of such
`preferred glass compositions according to the inven
`tion.
`
`TABLE V
`Weight %
`Oxide Component
`71 to 74
`SiO2
`0.15 to 0.25
`Al2O3
`1.20 to 1.60
`Fe2O3
`8.40 to 8.70
`CaO
`3.5 to 4.00
`MgO
`13.00 to 13.80
`Na2O
`O to 0.0
`K2O
`0.00 to 0.35
`TiO2
`0.15 to 0.6
`MnO2
`0.14 to 0.25
`SO3
`0.0160 to 0.0185
`Co (metal)
`0.0020 to 0.0040
`Se (metal)
`Preferred Glass Property Ranges (4 mm. thick glass sheet)
`Visible Transmission (Ill. A):
`16-20%
`Ultraviolet Transmission:
`5-10%
`Infrared Transmission:
`10-18%
`Total Solar Transmission:
`12-20%
`Dominant Wavelength:
`470-590 nm.
`Excitation Purity:
`0.0-5.5%
`Fe0/Total Iron Oxide as Fe2O3 Ratio:
`0.8-0.26
`
`Examples of the amounts of raw materials used to
`make various preferred embodiments of neutral gray
`glass compositions according to the present invention
`were set out in Table VI below. The table also details
`the spectral properties of the resulting glasses:
`TABLE VI
`Example Example Example Example Example
`9
`10
`11
`12
`13
`100.00
`0000
`100.00
`100.00
`100.00
`31.4
`3.41.
`31.41
`31.41
`31.41
`7.25
`7.25
`7.25
`7.25
`7.25
`
`Sand
`Soda Ash
`Limestone
`
`Sand
`Soda Ash
`Limestone
`Dolomite
`Salt Cake
`Sodium Nitrate
`Rouge
`Carbocite
`Cobalt Oxide
`Manganese Dioxide
`Selenium
`ppm Selenium
`in Glass
`
`100.00
`31.41
`7.25
`25.83
`1.0956
`0.5215
`1.8133
`0.0916
`0.0142
`0.5304
`0.0209
`26
`
`55
`
`60
`
`65
`
`O-I Glass, Inc.
`Exhibit 1035
`Page 004
`
`

`

`5,346,867
`
`7
`TABLE VI-continued
`Example Example Example Example Example
`9.
`10
`1.
`2
`13
`25.83
`25.83
`25.83
`25.83
`25.83
`1.0966
`1.0959
`1.0960
`10960
`1.0961
`0.5198
`0.5200
`0.5205
`0.5207
`0.5204
`
`Dolomite
`Salt Cake
`Sodium
`Nitrate
`2,0996
`Rouge
`O.O913
`Carbocite
`0.0300
`Cobalt
`Oxide
`Magse 0.1384
`Oxce
`Selenium
`0.0550
`Titanium
`0.0
`Dioxide
`18.3
`% LTA
`7.5
`% UV
`15.7
`% R
`16.7
`% TSET
`Rant 559.8
`length
`Excitation
`Purity, %
`
`3.3
`
`2.1008
`0.0910
`0.0308
`0.2705
`0.0411
`0.0
`
`2.1012
`0.0915
`0.0298
`02800
`0.0418
`0.0
`
`2010
`0.0914
`0.0305
`02802
`0.0415
`0.0
`
`18.8
`7.4
`15.6
`16.8
`S14.3
`
`17.9
`6.6
`15.2
`16.1
`463.7
`
`19.8
`8.2
`15.0
`16.9
`493.9
`
`19:
`6.0
`13.1
`15.5
`505.5
`
`1.3
`
`5.1
`
`3.8
`
`3.2
`
`8
`TABLE VII-continued
`Exposed 3
`Months
`Original
`Wavelength
`5 melt-0.4% MnO2 Wavelength
`558.4
`557.0
`% Excitation 2 Excitation -0.3
`Example 14-lab
`melt-no Mn nor Ti Purity 5.7
`Purity 5.4
`Example 15-lab
`% Excitation 2 Excitation -0.3
`2.1142
`melt-0.2% TiO2
`Purity 2.9
`Purity 2.6
`0.0913
`0.0305 10 Example 16-lab
`% Excitation 26 Excitation
`melt-0.2% MnO2 Purity 5.1
`Purity 5.7
`0,5601
`Example 17-lab
`9% Excitation 9% Excitation
`lit-0.4% M
`Purity 3.9
`Purity 3.9
`0.0281
`melt-0.4% MnO2
`rity
`urity
`0.560
`
`Difference
`
`-0.6
`0.0
`
`The scope of this invention includes not only glasses
`with
`ittance b O her gl
`with low transmittance, but other glasses that have a
`relatively high LTA which are heat absorbing and have
`a neutral gray green color. Exemplary of such glasses
`are those detailed in examples 18 and 19 in Table VIII
`20 below:
`
`TABLE VIII
`Example 19
`Example 18
`199
`19.
`725
`i25
`25.83
`25.83
`1.0961
`1.0960
`: 9:
`0.0912
`0.0913
`0.0057
`0.0095
`0.2779
`0.2779
`0.0280
`0.0210
`53.2
`48.7
`23.9
`23.4
`.4
`26.6
`3.
`34.8
`554.5
`512.1
`4.3
`1.8
`
`Ash
`s
`Limestone
`Dolomite
`Salt Cake
`Sir Nitrate
`8-ite
`Cobalt Oxide
`Manganese Dioxide
`Selenium
`% LTA
`% UV
`R
`: TSET
`Dominant Wavelength
`Excitation Purity, %
`
`As used throughout the disclosure of this invention
`and in Table VI above, 2 LTA is defined to be the 96 25
`luminous transmittance measured under CIE standard
`illuminant A. As used herein, the % UV is the % ultra
`violet transmittance as measured between 280 and 400
`nanometers while the 96 IR is the 76 infrared transmit-
`tance measured over the range of 720 to 2120 nanome- 30
`ters. The % TSET is the % total solar energy transmit-
`tance as defined in U.S. Pat. No. 4792 536 by the equa-
`tion:
`0.
`
`% TSET=0.44% LTA.--0.53% IR-0.03% UV
`
`35
`
`The dominant wavelength and % excitation purity
`are measured using CIE standard illuminant C.
`As discussed herein, glasses containing manganese
`and iron oxides have been known to solarize or discolor 40
`when exposed to a strong ultra violet light source. For
`example, the Jones patent discussed above teaches that
`glass containing iron oxide and MnO2 is undesirable
`because the MnO2 causes a brown coloration after UV
`exposure. In contrast, the glasses of the present inven
`45
`tion having the particular set of redox conditions within
`the scope of this invention, and specifically disclosed in
`detail above, have been found not to experience any
`appreciable solarization. Table VII below shows this.
`Embodiments of the invention glass according to this 50
`invention exhibit only a modest change of the color
`after an accelerated 3 month exposure in an Atlas,
`Model Ci65 Weather-ometer using a Xenon UV lamp.
`This 3 month exposure in the Atlas Weather-ometer is
`considered equivalent to over 4 years exposure to the 55
`sun in Arizona.
`
`Original
`Dominant
`Example 14-lab
`melt-no Mn nor Ti Wavelength
`483.0
`Dominant
`Wavelength
`493.2
`Dominant
`Example 16-lab
`melt-0.2% MnO2 Wavelength
`568.6
`Dominant
`
`Example 15-lab
`melt-0.2% TiO2
`
`Example 17-lab
`
`TABLE VII
`Exposed 3
`Months
`Dominant
`Wavelength
`483.2
`Dominant
`Wavelength
`494.2
`Dominant
`Wavelength
`570.2
`Dominant
`
`Difference
`--0.2
`
`6O
`
`-- 1.0
`
`--.6
`
`-- 1.4
`
`65
`
`Table VIII above demonstrates glasses made within the
`scope of this invention which shows the sensitivity of
`the balance that must be maintained between the cobalt
`and the selenium. A small increase in cobalt and less
`selenium moves the dominant wavelength of Example
`18 toward agreen color as in Example 19; the excitation
`purity also is lowered from the cobalt and selenium
`adjustments made in Example 18 to Example 19.
`We claim:
`1. A heat absorbing, neutral gray colored glass con
`position having a base glass composition comprising by
`weight: 68 to 75% SiO2, 10 to 18% Na2O, 5 to 15%
`CaO, 0 to 10% MgO, 0 to 5% Al2O3, and 0 to 5% K2O,
`where CaO + MgO is 6 to 15% and Na2O -- K2O is 10
`to 20%, and colorants consisting essentially of 0.90 to
`1.90 wt.% total iron oxide as Fe2O3; 0.002 to 0.025 wt.
`% cobalt as Co; 0.0010 to 0.0060 wt.% selenium as Se;
`0.10 to 1.0 wt.% manganese oxide as MnO2; and 0.0 to
`1.0% titanium oxide as TiO2; the glass at 4 mm. control
`thickness having light transmittance using illuminant A
`of 10.0% to 55.0%, ultra violet transmittance less than
`25.0%, and infra red transmittance is less than about
`50.0%.
`2. The neutral grey glass composition according to
`claim 1, wherein the dominant wavelength is between
`470 and 590 nanometers.
`3. The neutral grey glass composition according to
`claim 1, wherein SO3 is present in the composition in an
`amount about 0.01 to 0.03 wt.%.
`
`O-I Glass, Inc.
`Exhibit 1035
`Page 005
`
`

`

`5,346,867
`9
`10
`4. A heat absorbing, neutral gray colored glass com
`prises 0.15-0.60 MnO2 and 1.2-1.6 wt.% total iron as
`position having a base glass composition comprising: 71
`Fe2O3.
`10. A heat absorbing, neutral gray colored glass com
`to 74% SiO2, 13 to 13.80% Na2O, 8.4 to 8.7% CaO, 3.5
`position having a base glass composition comprising by
`to 4% MgO, 0.15 to 0.25% Al2O3, and 0 to 0.1% K2O,
`weight: 68 to 75% SiO2, 10 to 18% Na2O, 5 to 15%
`where CaO + MgO is 6 to 15% and Na2O +K2O is 10
`CaO, 0 to 10% MgO, 0 to 5% Al2O3, and 0 to 5% K2O,
`to 20%, and colorants consisting essentially of 1.20 to
`where CaO + MgO is 6 to 15% and Na2O + K2O is 10
`1.60 wt.% total iron oxide as Fe2O3; 0.0160 to 0.0185
`to 20%, and colorants consisting essentially of: 0.90 to
`wt.% cobalt as Co; 0.0020 to 0.0040 wt % selenium as
`1.90 wt.% total iron oxide as Fe2O3; 0.002 to 0.025 wt.
`Se; 0.15 to 0.60 wt.% manganese oxide as MnO2; and
`% cobalt as Co; 0.0010 to 0.0060 wt.% selenium as Se;
`0.0 to 0.35 wt.% titanium oxide as TiO2, the glass at 4
`0.10 to 1.0 wt.% manganese oxide as MnO2; and 0.0 to
`mm. control thickness having light transmittance using
`1.0% titanium oxide as TiO2; the glass at 4 mm. control
`illuminant A between 16.0% and 20.0%, ultra violet
`thickness having light transmittance using illuminant A
`transmittance between 5 and 10%, infra red transmit
`of 10.0% to 55.0%, ultra violet transmittance less than
`tance between 10 and 18%, and a dominant wavelength
`25.0%, and infra red transmittance is less than about
`50.0%; and being made from batch materials compris
`between about 470 and 590 nanometers.
`ing sand, soda ash, dolomite, limestone, salt cake, rouge,
`5. The neutral grey glass composition according to
`sodium nitrate, a manganese containing compound,
`claim 4, wherein its excitation purity is less than about
`carbocite, a cobalt containing compound, and selenium.
`5.5%.
`11. The neutral grey glass composition according to
`20
`6. The neutral grey glass composition according to
`claim 10, wherein based on 1000 lbs. of said sand in said
`claim 3, wherein the FeC/total iron oxide as Fe2O3 is
`batch ingredients used to make said composition, said
`between 0.18 and 0.26.
`ingredients comprise 6-24 lbs. salt cake; 3-20 lbs. so
`7. The neutral grey glass composition according to
`dium nitrate; and 0.1-1.5 lbs carbocite.
`12. The neutral grey glass composition according to
`claim 1, wherein based on 1000 lbs. of sand used in batch
`25
`ingredients to make said composition, other batching re
`claim 11, wherein said ingredients comprise 8-18 lbs.
`dients comprise: 6-24 lbs. salt cake; 3-20 lbs. sodium
`salt cake; 5-15 lbs. sodium nitrate; and 0.3-1.0 lbs. car
`bocite.
`nitrate; and 0.1-1.5 lbs. carbocite.
`13. The neutral grey glass composition according to
`8. The neutral grey glass composition according to
`claim 12, wherein said ingredients comprise 8-12 lbs.
`claim 6, wherein said batch ingredients comprise 8-18
`salt cake; 5-10 lbs. sodium nitrate, 0.3-1.0 lbs. carbocite;
`lbs. salt cake; 5-15 lbs. sodium nitrate; and 0.3-1.0 lbs
`and said neutral grey glass composition comprises
`carbocite.
`0.15-0.60 MnO2 and 1.2-1.6 wt.% total iron as Fe2O3.
`9. The neutral grey glass composition according to
`14. A glazing for automotive or architectural use
`claim 8, wherein said batch ingredients comprise 8-12
`prepared from the neutral grey glass composition of
`35
`lbs. salt cake; 5-10 lbs. sodium nitrate; 0.3-1.0 lbs. car
`claim 1.
`bocite; and said neutral grey glass composition com
`
`10
`
`15
`
`30
`
`sk
`
`k
`
`ck
`
`k
`
`sk
`
`45
`
`50
`
`55
`
`65
`
`O-I Glass, Inc.
`Exhibit 1035
`Page 006
`
`