United States Patent Office
`
`3,498,806
`Patented Mar. 3, 1970
`
`1.
`
`3,498,806
`GLASS COMPOSITIONS AND PROCESS
`Friedrich W. Hammer, John Jasinski, and Joseph R.
`Monks, Jr., Toledo, Ohio, assignors to Owens
`Illinois, Inc., a corporation of Ohio
`No Drawing. Filed Sept. 7, 1965, Ser. No. 485,539
`Int. C. C03c 1/10, 3/04, 3/24
`U.S. C. 106 52
`15 Claims
`
`O
`
`ABSTRACT OF THE DISCLOSURE
`Highly colored glasses of generally blue or green col
`oration including such colors as Dark Maryland Blue,
`Scotch Green, Champagne Green, Cuttysark. Green and
`the like are produced from molten colorless or amber
`colored flint glasses by the direct addition to the molten
`glass in the forehearth region of a glass melting furnace
`of a powdered colorant composed of about 90 percent
`or more by weight of powdered cobalt oxide and op
`20
`stionally included powdered zinc oxide, alkali and alkaline
`earth silicate, borate and phosphate wetting agents.
`
`5
`
`25
`
`35
`
`40
`
`2
`Further, smaller amounts of colorant are required by
`the forehearth colorant technique than by the full melter
`process. Thus, in the full melter process the colorant
`along with the remainder of the batch is subjected to ex
`tremely high temperatures in the melting and refining
`Zones and these high temperatures produce substantial
`losses of the volatile colorant materials during the ex
`tended melting and refining operations. Temperatures in
`the forehearth are substantially lower than in the melting
`and refining zones, and thus losses by volatilization are
`less likely to occur by the forehearth colorant process.
`Also by operating in accordance with the forehearth
`addition technique, conditions of firing in the melter and
`refining zones, rate of batch addition to the melter, and
`other factors can be stabilized and thereby converted into
`constants for improved operation and ease of control.
`Thus careful adjustment and stabilization of tank condi
`tions leads to the production of consistently high quality
`products. The tank conditions, once. stabilized, remain so,
`This greatly improves the operation over the old full tank
`color operation where a color change caused all of these
`factors to be upset.
`Further advancement to the art
`The forehearth colorant process, although providing a
`substantial advance to the art still leaves much to be de
`sired from an economy point of view. Thus, it requires the
`preparation of a frit glass. This is melted in a separate,
`special furnace at very high temperatures using selected
`materials and high ratios of colorant. The liquid frit is
`poured into water after formation to reduce it to granular
`form. After this is carefully dried, it is then added to a
`forehearth in carefully metered amounts to produce a
`colored end product or composite glass from the fore
`hearth.
`Frit making and handling and processing are thus ex
`pensive and add to capital investment by the extra furnace
`required, by the special furnace operator, close control,
`etc.
`Nevertheless, by the forehearth technique several ap
`proaches have been taken with success because of the
`economic advantages over the full melter process. These
`are as follows:
`(a) Using a colorless base glass and adding a colorant
`enriched frit;
`(b) Using a colored base glass and enhancing the color
`by adding more colorant by means of a frit containing
`the same colorants.
`But no one has been able to advance the art to the
`ultimate by putting colorant into the forehearth in the
`form of unprocessed powdered oxide, without having to
`go through the frit process, to produce colored end prod
`uct glass. In fact, the prior art states that this cannot be
`done. For example, in U.S. Patent 2,916,387 it is stated
`at col. 2, lines 14 and following:
`"Direct addition of a colorant material such as a
`colorant metal oxide to the glass in the pool is ineffective,
`because the oxide does not liquify or dissolve sufficiently
`rapidly to produce a uniform mixture in the time and
`space available.'
`This patent further states the defects that have been
`encountered with forehearth colorant addition using frits.
`Thus, the patent continues:
`"Compositions comprising a solid glass solution of a
`colorant, on the other hand, are generally insufficiently
`concentrated to be effective.
`"For use in commercial practice, it is necessary that
`the colorant material be sufficiently concentrated so that
`only a relative small volume need be added to the molten
`glass to attain the requisite depth of coloration. Introduc
`tion of a large volume of a solid substance will produce
`
`This invention relates to the manufacture of colored
`glasses and more particularly to the manufacture of col
`ored glasses by an improved forehearth powdered colorant
`addition technique.
`Further, this invention relates to novel glass composi
`tions made by adding a powdered colorant to flint and
`30
`amber glasses.
`Accordingly, broadly the invention relates to the pro
`duction of colored glasses from either colorless or colored
`base glasses by powdered colorant addition.
`Still further, the invention relates to novel colored
`glasses possessing high ultraviolet-absorbing properties,
`but meeting commercial standards established for several
`grades of blue and green colors.
`BACKGROUND FOR THE INVENTION:
`EVOLUTION OF GLASS MAKING
`Full melter operation
`In the earlier art of making colored glass, it was the
`practice to add the colorant material to the melter along
`with other batch materials. Since a glass tank contains
`100 tons or more of molten glass in process in order to
`provide an economical operation, substantial economic
`problems of loss of both glass and product occurred dur
`ing a changeover from one color to another. This prac
`tice of course meant that only one color of glass could
`be produced by the furnace at one time and in addition
`to being inflexible as regards color change, it required an
`extremely large capital investment for a single color.
`Forehearth colorant process
`More recently the practice of adding an enriched col
`orant frit glass to the forehearth has been developed.
`This practice provides important advantages over the full
`tank method for producing colored glass. Thus, by the
`forehearth colorant method, as many colors can be pro
`duced simultaneously from a single tank as there are fore
`hearths associated with the tank. Thus, short runs of a
`single color can be made profitably as distinguished from
`the prior full melter operation.
`65
`Further flexibility is provided by the fact that in a
`given forehearth a transition from one color to another .
`can be made in the manner of a few hours as contrasted
`to a matter of several days to change a full melter from
`one color to another.
`Both time economies and reduced loss of glass are
`readily apparent.
`
`45
`
`50
`
`55
`
`80
`
`70
`
`O-I Glass, Inc.
`Exhibit 1032
`Page 001
`
`

`

`3,498,806
`4.
`3
`The following specific examples are theoretical soda
`a disadvantageous decrease in the temperature of the
`lima-flint batch analyses of colorless base. glasses into
`molten glass. For proper operation of the forming ma
`which the high colorant cobalt oxide of the present in
`chinery, the molten glass must be maintained within rela
`vention can be combined to produce composite glasses
`tively narrow temperature limits. The heat source pro
`vided to maintain the glass temperature in the forehearth,
`of blue color.
`Specific base glass No. I
`however, is of limited capacity. If substantial amounts of
`a solid substance such as a colorant composition are in
`Percent by weight
`Constituent:
`troduced into the glass in the forehearth, these heat
`SiO2 ---------------------------
`72.01
`sources are insufficient to compensate for the consequent
`Al2O3 --------------------------
`1.74
`drop in temperature. The forming machinery then fails
`to operate properly.' .
`TiO2 --------------------------
`.029
`It is accordingly an important object to provide a proc
`CaO ---------------------------
`11.38
`ess for adding powdered colorant directly to the fore
`MgO --------------------------
`1.15
`hearth, without the necessity of having to go through
`RaO (Na2O-i-K2O) --------------
`13.65
`the expensive process of frit glass forming.
`Selenium ----------------------- .00025-.00030
`A further object is to provide novel glasses having
`Specific base glass No. II
`unexpectedly high ultraviolet ray absorbing properties.
`Percent by weight
`Constituent:
`BRIEF INTRODUCTION TO THE INVENTION
`SiO2 ---------------------------------- 71.45
`The various aspects of this invention are as follows:
`Alaos --------------------------------- 1.32
`(1) The broadest aspect comprises the addition of a
`Fe2O3 -------------------------------- .037
`selected highly soluble colorant oxide per se to glass in
`a forehearth. A particularly useful application of this
`TiO2 --------------------------------- .013
`CaO ---------------------------------- 8.32
`aspect of the invention involves the use of an amber base
`glass - for unexpected color effects in the composite
`25
`glasses so produced.
`This embodiment also encompasses the use of a pow
`dered solubilizer for the powdered colorant oxide to un
`expectedly reduce dusting as the powdered materials are
`immediately wetted upon contact with the molten mass
`30
`in the forehearth.
`(2) A further important aspect is the novel glass com
`positions produced by the present invention.
`The addition of highly soluble colorant powder
`By this invention, a selected oxide has been found to
`mix unexpectedly well into molten glass in the fore
`hearth and produce uniformly colored ware. Further,
`this selected oxide has been found to produce unex
`pectedly good colors of unexpectedly high density in
`40
`the ware.
`The colorant oxide utilized in accordance with the in
`vention is cobalt oxide and in its broadest aspect, no
`processing of the cobalt oxide is necessary for use.
`Within the extended scope of the invention, selected
`solubilizers or, in effect, high temperature-sensitive wet
`45
`ting agents can be admixed with the colorant oxide pow
`der. The function of these materials is to increase the
`wetting and solution rate of the colorant cobalt oxide,
`making it possible to put the cobalt oxide into the fore
`hearth glass at an unexpectedly high rate.
`USE OF THE PRESENT INVENTION
`Before discussing the specific manner in which the
`present invention is practiced, a description of suitable
`base glasses will be provided to serve as appropriate
`background upon which the invention can be superim
`posed.
`Preparation of base glasses
`Colorless flints.
`Base flint glasses of the colorless variety that can be
`used in practicing the present invention may have an
`analysis of oxides encompassed within the ranges set out
`below. Generally it will be found that glasses falling
`within this broad compositional range are soda-lime-flint
`glasses commonly used for the manufacture of colorless
`containers such as milk bottles and the like.
`Base flint glass compositions
`Percent by weight
`Constituent:
`SiO2 --------- - - - - - - - - - - - - - - - - - -
`60-75
`Al2O3 -------------------------
`.3-14
`CaO and MgO ------------------
`6-15
`Na2O --------------------------
`7-18
`K2O ---------------------------
`0-5
`BaO ---------------------------
`O-5
`Se (selenium) ----------------- 00025-00035
`
`R2O (Na2O--K2O) --------------------- 13.28
`Selenium ---------------------- .00025-00035
`The conditions and procedure for making the above
`base glasses are found in Table IX B-11, p. 245, "Hand
`book of Glass Manufacture,' Tooley, Odgen Publishing
`Company, New York, N.Y., 1953.
`In accordance with the broad principles of the in
`vention, cobalt oxide can be added to substantially any
`oxidized glass. Accordingly, the exemplary soda-lime
`flint glasses described above are not to be considered
`limiting on the scope of the invention. They are sug
`gested as appropriate for commercial container pro
`duction.
`Flint-based ambers.-Amber glasses based on flint com
`positions also can be used in practicing the present in
`vention. These may have oxide contents encompassed
`within the ranges set out below. Generally it will be
`found that glasses falling within these compositional
`ranges are amber colored as commonly used for produc
`ing beverage and food containers. These glasses exhibit
`high absorption capacity for ultraviolet rays, i.e. on the
`order of 500 mu or less, and thus prevent light destruc
`tion of the food and beverage content placed within
`containers made therefrom.
`Base amber glasses
`Percent by weight
`Constituent:
`SiO2 ------------------------------
`60-78
`Alaos -----------------------------
`1-18
`CaO ------------------------------
`7-18
`MgO ------------------------------
`0-9
`
`Na2O - - - - -
`
`- - - - - - - -
`
`-
`
`-
`
`- - - - -
`
`-
`
`-
`
`- - - - - un rur
`
`K2O ------------------------------
`Liao ------------------------------
`BaO ------------------------------
`
`R2O (NaO--KO--Li2O) - w w
`
`w w
`
`w w - - wa w Air
`
`Fe2O3 - - - -
`
`- - - - - - - - -
`
`-
`
`- - - - - - -
`
`-
`
`- - - - - -
`
`.04-.5
`
`Sulfides ---------------------------- .004-050
`Composite glass production
`In the production of glass containers, a base glass
`is prepared in a melting tank of several hundred tons
`capacity. The batch ingredients are added at one end of
`the melting zone and after fusion, flow to the fining
`zone. The glass is issued out of the fining zone by being
`run through one or a plurality of forehearths. Each
`forehearth feeds a container manufacturing machine.
`In the forehearth colorant process a frit is metered
`into the molten glass at the point where the glass flows
`from the fining zone into the forehearth. This is done
`
`FeO3 - - - - - - - - - - - - -
`
`are r - - - - - -
`
`-
`
`- - -
`
`039
`
`10
`
`5
`
`20
`
`MgO ------'as a ruro r ree
`
`a a awm man as as car - - - - as a - an 5.58
`
`50
`
`55
`
`60
`
`65
`
`70
`
`75
`
`7-16
`
`0-5
`0-3
`0-3
`
`7-24
`
`O-I Glass, Inc.
`Exhibit 1032
`Page 002
`
`

`

`3,498,806
`5
`6
`The composite glass had the following theoretical
`by a suitable vibration feeder and hopper apparatus
`analysis based on the batch.
`as known in the art.
`Also, refractory stirrers are used to mix the colorant
`Percent by weight
`Constituent:
`into the glass and produce uniformly homogenized color
`SiO2 ---------------------------------- 72.01
`all through the glass so that ware of even color through
`Al2O3 --------------------------------- 1.74
`out will be produced.
`All of the foregoing techniques are known in the art
`TiO2 ---------------------------------- .029
`as typified by the Hagedorn Patent No. 3,024,121 dated
`CaO ---------------------------------- 11.38
`Mar. 6, 1962.
`MgO ---------------------------------- 1.15
`Generally the melting and fining zones of glass melt
`RO (NaO-i-KO) --------------------- 13.65
`ing furnaces are maintained at substantially higher tem
`Selenium ----------------------- .00025.00030
`peratures than the forehearth. Thus, melting and fining
`CoO ----------------------------------
`.2
`temperatures in the range of 2850-3000 F. are com
`In the above composition, iron was present as a minor
`monly used. These temperatures cause bubbles of oc
`impurity in the sand and TiO2 was present as a minor
`cluded gas to be driven out of the melt and this pre
`impurity in the AlaC3.
`vents seeds from being formed in the finished ware.
`Temperatures in the forehearth however must be re
`EXAMPLE II
`duced substantially to the forming temperature of the
`Colorless flint plus cobalt oxide
`glass so that the glass will be sufficiently viscous to
`form properly in the container blowing machine. If
`In this example, commercial cobalt oxide was also
`it is too hot, the viscosity will be too low to form a
`added to a flint glass within the formulation range set
`proper gob, and this will prevent formation of a proper
`forth above to provide about .2 percent cobalt oxide in
`the composite glass. The addition of the cobalt oxide was
`parison, and this in turn will prevent formation of a
`made at forehearth operating temperatures. The color ob
`properly blown container.
`Forehearth temperatures therefore are generally in the
`tained was Dark Maryland Blue.
`The composite glass had the following theoretical
`range of 2350 F. down to about the forming tempera
`ture of the glass or about 1900 to 2000 F.
`analysis based on the batch.
`Constituent:
`Percent by weight
`It is at least these lower temperatures, or at this
`point however, that the forehearth addition process of
`SiO2 ---------------------------------- 71.45
`the prior art have often encountered substantial dif
`Al2O3 --------------------------------- 1.32
`ficulties. Thus the frit glasses often have such high
`softening and liquidus temperatures that they do not melt
`readily and do not mix thoroughly at forehearth tempera
`tures. In fact in some chromium frit glasses, actual crystals
`of chromium have been found in the final ware due to
`the improper admixing and melting of the high chromium
`frit with the base glass.
`However, by the present invention cobalt oxide has
`been found to mix and fuse very readily at forehearth
`40
`temperatures. The stirring means and mixing baffles of
`the prior art can be used to produce homogeneous ad
`mixture of the cobalt oxide powder into the base glass
`to produce uniformly colored composite glass Ware.
`Within the scope of the present invention, no particu
`lar mesh size is required of the cobalt oxide. As stated
`above, unprocessed cobalt oxide can be utilized. Within
`the broad scope of the invention however mesh sizes
`in the range of -8 to 400 can be employed with mesh
`sizes of about --50 to 200 mesh being generally pre
`ferred.
`The only limitation on the cobalt oxide-is of course
`that it should be free of high melting refractory-type im
`purities.
`Rates of addition
`In accordance with the present invention, rates of
`addition for the cobalt oxide will be in the broad range
`from about .001 to about .25 percent by Weight based
`on the composite glass. Rates in the range from about
`.01 to about .25 percent by weight are generally pre
`60
`ferred inasmuch as the outstanding blue as well as the
`outstanding green glasses produced fall within these ad
`dition levels.
`The following examples illustrate some of the several
`actual runs made in accordance with the present inven
`
`Fe2O3 . .
`
`.
`
`.
`
`. .
`
`.
`
`. .
`
`.
`
`. was - - a sy as
`
`an awm a mim was ap me w a wrw a
`
`O39
`
`FeO as - was ex was wers way m maia aa ma as m mm aw &ro url wrv - m at
`
`037
`
`TiO2 ---------------------------------- 013
`CaO ---------------------------------- 8.32
`MgO ---------------------------------- 5.58
`R2O ---------------------------------- 13.28
`Selenium ----------------------- .00025-00035
`CoO ----------------------------------
`.2
`Examples I and II represent colored glasses that can
`be made from colorless flint base glasses and cobalt oxide.
`Within the scope of the invention, composite glasses based
`on colorless flints are to be encompassed which fall within
`the following compositional ranges:
`Constituent:
`Percent by weight
`SiO2 -------------------------------- 60-75
`Al2O3 -------------------------------
`.3-10
`CaO plus MgO------------------------
`6-15
`Na2O ------------------------------- 12-18
`K2O --------------------------------
`0-5
`BaO --------------------------------
`0-5
`Selenium ----------------------- .00025.00035
`CoO -------------------------------- 005-25
`EXAMPLE III
`Amber colored flint plus cobalt oxide
`In this example, commercial cobalt oxide was added
`to amber glass at forehearth operating temperatures to
`provide .1% cobalt oxide in the composite glass. The
`color obtained was Scotch Green. This is an unexpected
`color change and apparently arises from the blending of
`the blue of the cobalt oxide with the amber color pro
`duced by the iron sulfide.
`The composite glass had the following theoretical
`analysis based on batch:
`Constituent:
`Percent by weight
`SiO2 ---------------------------------- 71.97
`AlaO3 --------------------------------- 1.884
`
`Fe2O3
`
`sw. .
`
`.
`
`.
`
`. . as as a saw - - - - - an a mass or m mart me rr r
`
`042
`
`CaO ---------------------------------- 11.47
`MgO ----------------------------------
`.11
`Na2O --------------------------------- 14.08
`K2O ---------------------------------- 381
`Lithium ------------------------------- .001
`Sulfides -------------------------------- 014
`CoO ----------------------------------
`.1
`
`O
`
`5
`
`20
`
`25
`
`30
`
`35
`
`50
`
`65.
`
`tion.
`
`M
`
`- - - - - -
`
`-
`
`,
`
`EXAMPLE I
`Colorless flint base glass plugs cobalt oxide
`In this example, commercial cobalt oxide was added
`to a colorless flint glass within the broad formulation
`range set forth above to provide about 0.2% of cobalt
`oxide in the composite glass. The addition was made at
`forehearth operating temperatures. The color obtained
`was Dark Maryland Blue.
`
`70
`
`75
`
`O-I Glass, Inc.
`Exhibit 1032
`Page 003
`
`

`

`KO no am or n
`
`e
`
`s m as
`
`no was prep as c - - - -e ow. - .
`
`.
`
`.
`
`. .
`
`0-5
`
`O
`
`20
`
`3,498,806
`8
`7
`accordance with this aspect of the invention; therefore
`Example III represents a single colored glass made
`the amount of solubilizer has little if any effect on the
`from an amber flint base glass and cobalt oxide. Within
`final glass composition and its properties.
`the scope of the invention, composite glasses based on
`amber base glass are to be encompassed which fall within
`Reduction of off-gases
`the following compositional ranges:
`Due to the fact that the cobalt oxide is not a reducing
`Constituent:
`Percent by weight
`agent, off-gasing is reduced as compared to the prior art.
`SiO2 -------------------------------
`60-78
`In the prior art, when a reducing agent is added to the
`Alaos ------------------------------
`1-18
`forehearth, carbon dioxide and other gases that are re
`CaO -------------------------------
`7-18
`leased remain in the glass as tiny bubbles because fore
`MgO ------------------------------
`0-9
`hearth temperatures are not high enough to fine the glass.
`Na2O ------------------------------
`7-16
`These tiny bubbles are called seeds and blisters in the
`finished ware. These are minimized when operating in
`Liao-------------------------------
`0-3
`accordance with the principles of the present invention.
`R20 -------------------------------
`7-24
`It has been found that any physically occluded gases
`BaO -------------------------------
`0-2
`in the powdered additives are driven off by the tempera
`Fe2O3 ------------------------------
`.04-.5
`ture existent in the forehearth as the additive is laid upon
`Sulfides ---------------------------- .004-050
`the surface of the molten glass. This provides a further
`CoO ------------------------------- .005 .25
`unexpected advantage in accordance with the present in
`The foregoing examples prove the operability of the
`vention.
`present invention and illustrate at least part of the range
`Achievement of greens from amber
`of colors and color control possible by applying the prin
`By introducing cobalt oxide into an amber glass in
`ciples of the invention.
`accordance with this invention, dark greens can be readily
`Solubilizers for the colorant powder
`achieved. These greens include Champagne Green, Cutty
`Sark Green and other very dark greens. This is unique
`As pointed out above, this invention also encompasses
`in view of the fact that cobalt is a normally blue-produc
`the addition of a powdered solubilizer in combination
`with the powdered colorant oxide to produce an unexpect
`ing oxide.
`edly rapid rate of colorant addition. This unexpectedly en
`Extended scope of invention
`hances the rate of cobalt oxide assimilation by the base
`The foregoing disclosure has been directed to the use
`glass and reduces dusting.
`of cobalt oxide as an additive because of the unique char
`Thus, in accordance with this aspect of the invention,
`acteristics of this material. However, within the scope
`Solubilizers selected from the group of alkali and alkaline
`of the invention, certain extensions are encompassed.
`earth borates, alkali and alkaline earth silicates, and alkali
`Thus zinc ovide and zinc oxide-bearing frits can be com
`and alkaline earth phosphates can be used. Specific mate
`bined with the cobalt oxide at various concentrations to
`rials include sodium silicate, sodium borate and sodium
`furnish extended color ranges in greenish yellows, yellow
`phosphate, all in powder form. When such a composite
`greens, and greens and blues.
`powder mixture is introduced into the forehearth of a
`When using cobalt oxide alone with an amber glass,
`glass melting furnace, the heat of the forehearth imme
`the amber color is fixed and the color modification comes
`diately causes the solubilizer to be reduced to a molten
`about by blending the amber color with the blue provided
`40
`condition in surrounding, wetting relationship to the
`by cobalt oxide. With the addition of zinc oxide, however,
`colorant cobalt oxide powder. This immediately wets the
`the base amber is also varied. This comes about by the
`cobalt oxide and instantly starts the fusion and admixture
`fact that some of the iron sulfide forming the amber color
`of the cobalt oxide into the molten base glass. By the use
`is exchanged to form zinc sulfide which is colorless. This
`of suitable stirring equipment, the color is distributed
`reduces the intensity of the amber color. Then, the addi
`homogeneously throughout the molten base glass and ware
`tion of the blue of the cobalt oxide provides a great many
`of uniform color is readily accomplished.
`more possible shades of green.
`As an extension of this aspect of the invention, an
`For example, Champagne Green can be made from a
`alkali metal monoxide can be added in small amounts to
`normal amber by using zinc oxide along with the cobalt
`facilitate the wetting of the cobalt oxide colorant.
`oxide. By so operating, the zinc oxide takes out some of
`the amber and the cobalt oxide blue blends with the re
`The amount of solubilizer
`sulant, lesser intensity amber to provide Champagne
`It has been found that an amount of solubilizer based
`Green.
`on the amount of cobalt oxide in the range from about
`The foregoing principles are substantiated by the re
`.2 to about 10 percent by weight provides a highly useful
`sults of several runs which are summarized in the follow
`additive composition.
`ing tables.
`Losses by volatilization are very slight by operating in
`
`50
`
`55
`
`Run
`No.
`
`
`
`Percent Percent. Percent
`Fe2O3
`S.
`CoO
`182
`... 028
`O
`... 182
`... 028
`.10
`.82
`028
`. 12
`
`Percent
`Dominant
`wave- Percent bright
`length
`ness Note
`purity
`579.8
`86.6
`36.
`Standard amber.
`566.2
`49.3
`5.5 Very darkgreen.
`570.3
`617
`8.2
`Do.
`
`(The above runs illustrate the colors produced by the present invention by adding vary
`ing amounts of CoO to standard amber. Greens are produced.)
`Dominant
`Percent
`wave- Percent bright
`length
`ness Note
`purity
`576.0
`46.6
`68.9 Light amber.
`572, 6
`32.
`50.1 Greenish yellow.
`565.2
`16,
`36.6 Green.
`514.4
`3.
`27.9 Blue.
`486.3
`15.
`21.1
`Do,
`
`Percent Percent Percent
`Fe2O3
`S
`CoO
`033
`012
`O
`.033
`... 012
`.02
`033
`... 012
`.04
`.033
`012
`06
`033
`012
`.08
`
`Run
`No.
`500------
`501------
`502-----.
`503------
`504------
`
`(The above runs illustrate the unexpected effects obtainable by first modifying a stand
`ard amber to reduce the amount of iron sulfide color, and then adding CoO. The colors
`vary from greenish yellow through blue as the percent of CoO is increased.)
`
`O-I Glass, Inc.
`Exhibit 1032
`Page 004
`
`

`

`9
`
`3,498,806
`
`10
`
`20
`
`Percent
`Dominant
`wave- Percent bright
`Percent Percent Percent
`length
`ness Note
`purity
`Fe2O3
`S
`COO
`Run No.
`578.
`75.8
`50.2 Light amber.
`30
`020
`O
`525------------
`575.8
`6.6
`36.9 Greenish yellow.
`30
`.020
`.02
`526.-----------
`573.4
`58.6
`27, 3 Yellowgreen.
`130
`020
`.04
`527------------
`570.3
`47.5
`19, 5 Green,
`130
`O20
`06
`528------------
`566.5
`35.6
`15. 3 Approaches champagne green.
`30
`,020
`08
`529------------
`(The above runs illustrate further applications of the principles enumerated in the foregoing description. This
`level of amber color and CoO highlight the yellows and greens that can be produced.)
`Percent by weight
`It is to be understood that the foregoing description
`Oxide:
`is subject to reasonable extensions and that the inven-
`Sulfides -------------------------- 004-050
`tion is capable of being practiced and carried out in vari- 15
`CoO ----------------------------- 005-25
`ous ways. The phraseology or terminology employed is
`6. In a process for producing colored glass, the steps of:
`for the purpose of description and not of limitation.
`forming a molten body of refined glass from a batch of
`What is claimed is:
`glass-forming materials in the glass melting and re
`1. A shaped body of colored glass having the composi-
`fining zones of a melter at elevated temperatures,
`tion:
`flowing the refined glass from the melter into a fore
`Oxide:
`Percent by weight
`hearth,
`in the forehearth directly adding powdered colorant to
`SiO2 -------------------------------- 72.01
`AlaOa ------------------------------- 1.74
`the refined glass, the powdered colorant being com
`Fe2O3 --------------------- so se v
`as a
`rp
`.039
`posed essentially of cobalt oxide in admixture with
`TiO2 -------------------------------- .029 25
`dry powdered, high-temperature responsive wetting
`CaO -------------------------------- 11.38
`agent and being added in sufficient amount to add co
`MgO -------------------------------- 1.15
`balt oxide to the refined glass in an amount ranging
`R2O (Na2O--K2O) ------------------- 13.65
`from about .001 to about .25 percent based on the
`Selenium ------------ --------- .00025-00030
`(weight of the glass,
`CoO --------------------------------
`.2 30
`mixing the cobalt oxide into the glass to produce
`2. A shaped body of colored glass having the composi-
`homogeneous color throughout the glass,
`then issuing the molten glass from the forehearth and
`tion:
`Oxide:
`Percent by weight
`forming an article from the glass.
`SiO2 ----------------------88 or
`a Aa as
`as w 71.45
`7. In a process as defined in claim 6, wherein the
`Alsos ----------------------aw was it was ose
`1.32 35 powdered colorant oxide consists of at least 90 percent
`Fe2O3 ------------------------------- 037
`by weight of cobalt oxide powder admixed with a minor
`TiO2 -------------------------------- .013
`amount of a material selected from the group of materials
`CaO -------------------------------- 8.32
`consisting of alkali and alkaline earth silicates, alkali and
`MgO -------------------------------- 5.58
`alkaline earth borates and alkali and alkline earth phos
`R2O -------------------------------- 13.28 40 phates.
`Selenium -------------- ------- .00025-00035
`8. In a process of producing colored glass, the steps of
`CoO ---------------------------- - - - -
`.2
`melting a glass having a composition within the range:
`3. A glass having a composition within the range:
`Constituent:
`Percent by weight
`Oxide:
`Percent by weight
`SiO2 ------------------------------- 60-75
`SiO2 -------------------------------- 60-75
`Al2O3 ------------------------------- .3-14
`
`CaO--MgO
`
`-
`
`-
`
`-
`
`- -
`
`Al2O3 ------------------------------ 3-10 45
`
`CaO +MgO -------------------------- 6-15
`Nago ------------------------------- 12-18
`K2O --------------- -----------------
`0-5
`BaO -------------------------------- 0-5
`Selenium --------------------- .00025-00035 50
`CoO ------------------------------. 005-25
`4. A glass having the composition:
`Oxide:
`Percent by weight
`SiO2 -------------------------------- 71.97
`Al2O3 ------------------------------- 1.884 55
`Fe2O3 ------------------------------- .042
`CaO -------------------------------- 11.47
`MgO --------------------------------
`.11
`Na2O ------------------------------- 14.08
`K2O -------------------------------- .381 60
`Lithium ----------------------------- .00
`Sulfide ------------------------------ .014
`CoO --------------------------------
`.1
`5. A glass having a composition within the range:
`Oxide:
`Percent by weight 65
`SiO2 -----------------------------
`60-78
`Al2O3 ----------------------------
`1-18
`CaO -----------------------------
`7-18
`MgO ----------------------------
`0-9
`Na2O ----------------------------
`7-1670
`K2O -----------------------------
`O-5
`LigO ----------------------------
`O-3
`RO -----------------------------
`7-24
`BaO -----------------------------
`0-2
`Fe2O3 ----------------------------
`.04-.5 75
`
`-
`
`-
`
`-
`
`-
`
`-
`
`- - - -
`
`-