USRE25456E - Ultraviolet light absorbing glass - Google Patents

Ultraviolet light absorbing glass Download PDF

Info

Publication number
USRE25456E
USRE25456E US25456DE USRE25456E US RE25456 E USRE25456 E US RE25456E US 25456D E US25456D E US 25456DE US RE25456 E USRE25456 E US RE25456E
Authority
US
United States
Prior art keywords
glass
chromium oxide
ultraviolet
millimicrons
hexavalent
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
Application number
Publication date
Application granted granted Critical
Publication of USRE25456E publication Critical patent/USRE25456E/en
Expired legal-status Critical Current

Links

Images

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
    • C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/10—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce uniformly-coloured transparent products
    • 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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container 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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium

Definitions

  • the present invention relates to glasses which absorb ultraviolet radiation and short-wave radiation within the visible spectrum and more particularly to compositions of such glasses.
  • the invention is of utility in the manufacture of glass bottles, jars and other containers used for the packaging of food, beverage, and pharmaceutical products which are detrimentally affected by undesirable photochemical effects produced by such radiation.
  • the deterioration in the taste of beer, wine, ale and orange-flavored soft drinks, the development of rancidity in cooling oils and the loss of vitamin C content of milk are examples of such undesirable photochemical reactions.
  • These reactions are caused by exposing the foodstuffs to ultraviolet radiation and also to some extent to short-wave radiation within the visible spectrum.
  • the ultraviolet region of the electromagnetic spectrum is that region near the visible spectrum including wave lengths from 20 to 380 millimicrons which are longer than X-rays and shorter than visible light rays.
  • the ultraviolet portion of the spectrum is termed anything below 400 millimicrons while the visible range comprises from about 400 to 700 millimicrons.
  • a light-resistant container is one which is opaque or designed to prevent photochemical deterioration of the contents beyond the oflicial limits. of strength, quality or purity under customary conditions of handling, storage, shipment or sale.
  • the light-resistant container as defined therein shall be composed of a substance which in a thickness of two millimeters shall not transmit more than 10 percent of the incident radiation of any wave length between 2900 and 4500 Angstrom units (290 and 450 millimicrons).
  • amber glass is Re. 25,456 Patented Oct. 8, 1963 used for some packaging such as beverage and pharmaceutical products where visibility of the contents is desired either for purposes of display or inspection, or for the detection of foreign particles, or for other purposes.
  • the visibility through such amber glass is comparatively low.
  • amber glass does not possess characteristics of transmitting a high level of visible light.
  • Another object of this invention is to provide glass compositions having green coloration which possess characteristics of high ultraviolet ray absorption and visible ray transmittance.
  • Another object of this invention is to provide lighttransimtting green glasses having widely varied common base compositions, the glasses including a prescribed amount of hexavalent chromium to impart a high degree of ultraviolet ray absorption to the glass.
  • a further object of this invention is to provide yellow green or green glasses suitable for bottling beverages or containing foods which are commonly retained in emerald green glass and which new glasses will withstand increased exposure to sunlight and/ or fluorescent light without dctoriation of desirable properties of contained products.
  • green glass having a color appearance similar to emerald green, a visibility equal to that of emerald green and much greater than that of amber, permitting the examination of contents retained in containers made of such glass and having light protection" vastly exceeding that of emerald green glass and similar to that of amber.
  • Emerald green glass such as employed in bottling certain carbonated beverages generally is regarded as having C.I.E. colorimetric values consisting of the following for a typical 10.0mm. specimen; 34.4% brightness, 66.4% purity and 555 millimicrons dominant wave length.
  • Amber glass generally has distinctively different values which typically fora 2.0 mm. specimen are: 48.0% brightness, 78.8% purity and 579 millimicrons dominant wave length.
  • the ultraviolet absorption achieved by the present invention is due to the presence of hexavalent chromium in the glass also containing a minimal amount of iron as commercially melted. It is not necessary in practicing the present invention that any particular amount of iron be included in the composition. However, as is known in producing commercial melts of common glasses small amounts of iron are inherently present as a contaminant being carried into the glass with some of its major constituents such as silica sand.
  • hexavalent chromium may be produced by employing alkali metal or alkaline earth chromate or dichromates in the batch composition. It has also been found that any other chromium containing glass-forming material might be similarly employed as the source of the chromium.
  • An alkaline nitrate such as potassium nitrate (KNO or sodium nitrate (NaNO is employed in the batch to produce a prescribed amount of oxidant depending upon the particular composition and melting conditions to secure the hexavalent chromium in the end product. It is necessary in preparing the composition that both the chromium containing glass-forming material and the oxidant such as an alkaline nitrate be used together to ensure that at least a portion of the chromium either remains or is converted to the hexavalent state on melting and fining.
  • KNO potassium nitrate
  • NaNO sodium nitrate
  • the chromium is added to the glass batch preferably either as potassium dichromate (Kgcl'zoq) or sodium dichromate fNa cr O lH o) although other chromates or chromites may similarly be employed.
  • the potassium dichromate which is stable in air offers certain advantages in the production of the subject glasses over sodium dichromate which is deliquescent.
  • chromates or dichromates or mixtures thereof are utilized as the chromium containing material, at least a portion of the chromium is retained in the hexavalent state during melting and is also so retained in the final glass product.
  • the chromium containing materials employed in the glass batch may be comprised of chromium in its highest state of valence in the form of chromates and/or dichromates for securing the hexavalent chromium. In this case a major portion of the hexavalent chromium is reduced to the trivalent state in the melting furnace while a minor amount is retained in the hexavalent state in the final glass product.
  • the chromium containing material may consist of a mixture of chromate or dichromate and chromite, Wherein the heat-reacted product of the chromium containing materials consists of part hexavalent chromium oxide (CrO and part trivalent chromium oxide (Cr O).
  • the chromium containing material may be comprised entirely of trivalent chromium as in the case of utilizing iron chromite (FeO.Cr O as a batch constituent.
  • an oxidant such as the alkaline nitrate is placed in the glass batch and oxidizing conditions within the melting furnace are utilized to convert at least a portion of the trivalent chromium oxide (Cr O into hexavalent chromium oxide (CrO).
  • the hexavalent chromium is a powerful absorber of ultraviolet radiation and a less powerful absorber of visible radiation. Furthermore, it is practical to secure either by oxidation or retention of only a small portion of the chromium in the hexavalent state an amount of approximately 0.05% being adequate to absorb nearly 85% of the ultraviolet radiation and all radiations below about 440 millimicrons.
  • the hexavalent chromium produces a slightly yellowing tendency in the glass which may be desirable for producing a yellow green glass for example.
  • the addition of a small amount of copper oxide (CuO) tending to produce a bluish color will complement this yellowing tendency so that the glass resembles or closely approaches an emerald green color.
  • hexavalent chromium which is produced in a given glass composition such as emerald green, for example, is largely due to the atmosphere over the raw glass melt and the components of the batch utilized in the melting process. Control over the melting and thus the valence state of the chromium may be obtained by supplying oxygen into the batch from an oxygen bubbler disposed in the melting chamber for maintaining a slightly oxidizing atmosphere over the raw glass as melted.
  • One form of apparatus and method for producing the subject ultraviolet absorbing green glass has been disclosed in the copending patent application of Joseph C. Hamilton, Serial No.
  • the oxygen-bubbler was demonstrated to be effective in controlling the state of oxidation of the chromium, and the ultraviolet transmission.
  • the glass showed 3 /2% transmission at 400 millimicrons, while at a bubbler rate of .35 cubic foot per hour, the transmission at 400 millimicrons was only .5 In the first case, the excess air in the refiner was 2% whereas in the second case it was 10%.
  • the melting temperatures range from 2700 F. to 2875 F. and the refining or conditioning shall appear a slightly deeper shade of green glass. Glass No.
  • m n is S A O o o greater, even though the total Cr O content has been 7L8 71.3 709 7045 lowered.
  • the high alumina content is due primarily to 1.02 1.74 2.55 0.1-0.0 the utilization of high A1 0 sand, known in the trade as 12 32 iii 61? Del Monte Sand," having the following typical analvsis: 0.02 0.02 0." 0*! 15.5 10.1 11. 0 10 -20 Percmt y 8 0.304 0.410 ages 3- g o 79 ""0701 "0:05" 5.22 0.1-0? A1 0 11.9 0.001 0. 003 0. 000 .000070 p o (]7 mo 0.11 0.07 0.045 0.
  • Table IV illustrates a comparison of so-called ultra- The R 0 in the analyses represents constituents such sor glasses A through E inclusive as compared as A1 0 and other related metallic oxides which are comwith conventional emerald green and amber glasses.
  • Curves of the percent transmittance through a two millimeter specimen of wave lengths in the range of from 300 to 500 millimicrons are shown on the accompanying graph.
  • 400 millimicrons considered to be generally the line of distinction between ultraviolet and visible violet rays, it can be readily observed that emerald green glass is capable of absorbing only a small amount of ultraviolet below about 320 millirnicrons and that it transmits a very large portion of the ultraviolet between 320 and 440 millimicrons.
  • Amber glass on the other hand which is very dense and approaches opaqueness in any appreciable thickness absorbs nearly all of the ultraviolet and also a considerable amount of the visible wave lengths between 400 and 500 millimicrons as can be seen by the curve for amber on the bottom of the graph.
  • the subject ultrasorb glass melts wherein the hexavalent chromium oxide[s] (CrO percentages range from 0.005 to 0.065% by weight.
  • the minimum amount of hexavalent chromium of 0.005% transmits only a small portion of the total ultraviolet and it may also be observed that the relative amount of ultraviolet transmission is directly correlative to the relative amount of hexavalent chromium oxide present in the glass. It can also be seen how the subject glasses achieve very appreciable absorption of the ultraviolet with a high rate of transmission of the visible light in the range of from 440 millimicrons and above.
  • the properties of the Ultrasorb absorbing green glasses which have been found to be particularly desirable are the following:
  • the ultraviolet absorbing property is essentially due to hexavalent chromium in the glass which is obtained by using an oxidizing atmosphere in the melter, chromates or dichromates or chromite as the source of chromium, and niter or saltpeter as an oxidant in the batch.
  • the new glasses may contain by weight 6075% SiO 0.ll0.0% R 0 of which the major portion is A1 0 6- 12% Ca(); 06% MgO; 01% BaO; 21% alkali metal oxides; 0-5% B 0 0.020-0.20% Fe O and chromium oxide present in both the trivalent and hexavalent states usually in a total amount of less than 0.5%. It has been found preferable to employ a total chromium oxide content of 0.1-0.3% with about 0.0050.070% CrO to secure in an economical manner the very considerable absorption of ultraviolet rays.
  • the glass may contain by weight 70 to 75% SiO
  • a higher magnesium oxide content glass may be produced by using a magnesium containing component in the batch such as dolometic limestone rather than lime.
  • Comparativcly low silica-high alumina glasses having excellent absorption characteristics can be prepared from high A1 0 content sands.
  • modified borosilicate glasses by employing from about 1-5% B 0 in the glass.
  • the copper oxide (CuO) may be included in an amount of less than 0.2% by weight.
  • the ultraviolet radiation absorbing emerald green glass composition of this invention comprises essentially a sodalime-silica gloss containing at least 0.1% A1 0 such as 0.1 to 3.0% Al O less than 0.3% Fe o and about 0.10 to 0.30% total chromium oxides present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (C10 the latter chromium xide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition and said composition having C.I.E.
  • the ultraviolet radiation absorbing emerald green glass composition of this invention comprises essentially by weight 70 to 810 said percentage of A1203, 6 to 12% 010; 0 to 6% MgO; 0 to 1% BaO; O to 5% B 0 10 to 21% alkali metal oxides; including less than about 0.3% Fe O and less than about 0.3% total chromium oxides present as both trivalent chromium oxide (Cr 0 and hexavalent chromium oxide (CrO the latter ranging from about 0.005 to 0.070%; said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
  • compositions of the present invention can be summarized as follows:
  • the C.I.E. colorimetric values are based upon the I. Chromaticity Diagram C.I.E. refers to the First International Commission of Illumination and the diagram from which the values are taken defines color in terms of mixtures of theoretical colored lights
  • the C.I.E. system makes possible the exact specification of colors by means of a color map."
  • the C.I.E system of color notation specifies the color of glasses in terms of brightness, purity and dominant wave length. Brightness which is usually expressed in terms of percentage is the amount of visual response to a normal observer to the radiation emergent from a transparent object relative to the response in this observer to the radiation incident upon the object. Thus, brightness may be briefly termed the lightness of color of an object.
  • Purity which is also normally expressed in terms of percentage is a measure of the monochromaticness of a color with monochromatic light having purity of By diluting the monochromatic radiation with white light made up of all wave lengths, We thereby dilute the color and reduce purity.
  • An ultraviolet radiation absorbing green glass composition comprising essentially by weight 60 to 75% S10 0.1 to 9.5% A1 6 to 12% C210; 0 to 6% MgO; 0 to 1% B210; 0 to 13 0 to 21% alkali metal oxides; including less than about 0.3% E2 0 and less than about 0.3% total chromium oxides present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the latter ranging from about 0.005 to 0.070%] [2.
  • An ultraviolet radiation absorbing green glass composition comprising essentially by weight 60 to 75 SiO 0.1 to 9.5% A1 0 6 to 12% C210; 0 to 6% MgO; 0 to 1% BaO; 0 to 5% B 0 10 to 21% alkali metal oxides; 0.02 to 0.20% Fe O and about 0.10 to 0.30 total chromium oxides including about 0.005 to 0.070% hexavalent chromium oxide, said composition having C.I.E. colorimetricvalues for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant Wave length] [3.
  • An ultraviolet radiation absorbing green glass composition consisting essentially of the following ingredients:
  • An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing at least 0.1% Al O less than 0.3% Fe 0 and about 0.10 to 0.30% total chromium oxides expressed as Cr O and present as both trivalent chromium oxide (Cr 0 and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
  • An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing at least 0.1% AI O 0.02 to 0.20% Fe O and about 0.10 to 0.30% total chromium oxides expressed as C7 0 and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (Gro the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
  • An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing at least 0.1% A1 0 less than 0.3% Fe O C00 in an amount less than 0.01% and about 0.10 to 0.30% total chromium oxides expressed as Cr O and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% 10 brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
  • An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing at least 0.1% A1 0 0.02 to 0.20% Fe O C00 in an amount less than 0.01% and about 0.10 to 0.30% total chromium oxides expressed as Cr O and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
  • An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing at least 0.1% A1 0 less than 0.3% Fe O CuO in an amount less than 0.2% and about 0.10 to 0.30% total chromium oxides expressed as Cr O; and present as both trivalent chromium oxide (Cr o and hexavalent chromium oxide (C10 the hexavalem chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% bright ness 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
  • An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing at least 0.1% Al O 0.02 to 0.20% Fe O CuO in an amount less than 0.2% and about 0.10 to 0.30% total chromium oxides expressed as (V 0 and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
  • the glass composition of claim 10 wherein the CuO content is about 0.08%.
  • An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing 0.1 to 3.0% Al O less titan 0.3% Fe o and about 0.10 to 0.30% total chromium oxides expressed as Cr O and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
  • An ultraviolet radiation absorbing emerald green glass composition consisting essentially of soda-lime-silica glass containing 0.1 to 3.0% Al O 0.02 to 0.20% E2 0 and about 0.10 to 0.30% total chromium oxides expressed as Cr O and present as both trivalent chromium oxide (C and hexavalent chromium oxide (C10 the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
  • An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing 0.1 to 3.0% AI O less than 0.3% Fe 0 C00 in an amount less than 0.01% and about 0.10 to 0.30% total chromium oxides expressed as Cr O and present as both trivalent chromium oxide (C7 0 and lzexavalent chromium oxide (Cr the hcxavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.1.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
  • An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing 0.1 to 3.0% Al 0 less than 0.3% Fe O CuO in an amount less than 0.2% and about 0.10 to 0.30% total chromium oxides expressed as Cr O and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
  • An ultraviolet radiation absorbing emerald green glass composition consisting essentially by weight of 70 to 75% S10 0.1 to 3.0% A1 0 6 to 12% CaO, 0 to 6% MgO, 0 to 1% 13:10. 0 to B 0 to 21% alkali metal oxides, less than 0.3% Fe O and about 0.10 to 0.30% total chromium oxides, expressed as Cr 0 and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (Cro the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
  • An ultraviolet radiation absorbing emerald green glass composition consisting essentially by weight of 70 to 75% SiO 0.1 to 3.0% Al O 6 to 12% CaO, 0 to 6% MgO, 0 to 1% BaO, 0 to 5% B 0 10 to 21% alkali metal oxides, 0.02 to 0.20% Fe O 0.002 to 0.008% C00 and about 0.10 to 0.30% total chromium oxides, expressed as Cr O and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, to 87% purity and 554 to 565 millimicrons dominant wave length.
  • An ultraviolet radiation absorbing emerald green glass composition consisting essentially by weight of to S10 0.1 to 3.0% A1 0, 6 to 12% CaO, O to 6% MgO, 0 to 1% BaO, 0 to 5% B 0 10 to 21% alkali metal oxides, 0.02 to 0.20% ee o CuO in an amount less than 0.2% and about 0.10 to 0.30% total chromium oxides, expressed as Cr O and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52 brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Description

Oct. 8, 1963 TRANSMITTANCE, 7,, THROUGH 2w. 8 O
F. R. BACON ETAL Re. 25,456
ULTRAVIOLET LIGHT ABSORBING GLASS Original Filed July 11, 1960 ULTRAVIOLET ABSORBING GREEN GLASS IN COMPARISON WITH EMERALD GREEN AMBER WAVELENGTH IN MILLIMICRONS INVENTORS FR BACON 4 CA] BILL/AN A TTORNEVS United States Patent 25,456 ULTRAVIOLET LIGHT ABSORBING GLASS Frank R. Bacon, Toledo, Ohio, and Carroll J. Billian,
Bcthpage, N.Y., assignors to Owens-Illinois Glass Company, a corporation of Ohio Original No. 2,974,052, dated Mar. 7, 1961, Ser. No. 42,014, July 11, 1960. Application for reissue Mar. 6, 1962, Ser. No. 179,283
Matter enclosed in heavy brackets [II appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
16 Claims. (Cl. 106-52) The present invention relates to glasses which absorb ultraviolet radiation and short-wave radiation within the visible spectrum and more particularly to compositions of such glasses.
The invention is of utility in the manufacture of glass bottles, jars and other containers used for the packaging of food, beverage, and pharmaceutical products which are detrimentally affected by undesirable photochemical effects produced by such radiation.
In the case of comcstible products marketed in glass bottles or other containers, the deterioration in the taste of beer, wine, ale and orange-flavored soft drinks, the development of rancidity in cooling oils and the loss of vitamin C content of milk are examples of such undesirable photochemical reactions. These reactions are caused by exposing the foodstuffs to ultraviolet radiation and also to some extent to short-wave radiation within the visible spectrum. The ultraviolet region of the electromagnetic spectrum is that region near the visible spectrum including wave lengths from 20 to 380 millimicrons which are longer than X-rays and shorter than visible light rays. Generally, the ultraviolet portion of the spectrum is termed anything below 400 millimicrons while the visible range comprises from about 400 to 700 millimicrons.
It is known that ultraviolet radiation is most productive of the enumerated undesirable photochemical effects. In order to eliminate at least in part some of the abovementioned objectionable photochemical effects, amber glass has been utilized heretofore to absorb at least a portion of the ultraviolet radiation of the atmosphere. The amber glass has served to furnish some degree of light protection" to the contained products. The term light protection is commonly applied to glasses adapted to protect against ultraviolet as well as visible radiation and, as used herein, this and like terms are intended to apply to protection against all such radiation which produces undesirable photochemical effects.
As defined in US. Pharmacopoeia, volume 12, pages 6 and 7, a light-resistant container is one which is opaque or designed to prevent photochemical deterioration of the contents beyond the oflicial limits. of strength, quality or purity under customary conditions of handling, storage, shipment or sale. The light-resistant container as defined therein shall be composed of a substance which in a thickness of two millimeters shall not transmit more than 10 percent of the incident radiation of any wave length between 2900 and 4500 Angstrom units (290 and 450 millimicrons).
A desirable feature of glass bottles and other glass containers is their transparency permitting the packaged products to be visually inspected. In order to provide protection against photochemical effects amber glass is Re. 25,456 Patented Oct. 8, 1963 used for some packaging such as beverage and pharmaceutical products where visibility of the contents is desired either for purposes of display or inspection, or for the detection of foreign particles, or for other purposes. However, the visibility through such amber glass is comparatively low. Thus, amber glass does not possess characteristics of transmitting a high level of visible light.
The instant application is a continuation-in-part of our prior application Serial No. 771,031, filed October 31, 1958, and now abandoned, which in turn, is a continuation-in-part of application Serial No. 659,179, filed May 14, 1957, and now abandoned, both of said prior applications being assigned to the assignee of the present invent-ion.
Accordingly, it is an object of the present invention to provide a glass of much better visibility and which at the same time gives adequate light protection equal to or greater than that of amber glass.
Another object of this invention is to provide glass compositions having green coloration which possess characteristics of high ultraviolet ray absorption and visible ray transmittance.
Another object of this invention is to provide lighttransimtting green glasses having widely varied common base compositions, the glasses including a prescribed amount of hexavalent chromium to impart a high degree of ultraviolet ray absorption to the glass.
A further object of this invention is to provide yellow green or green glasses suitable for bottling beverages or containing foods which are commonly retained in emerald green glass and which new glasses will withstand increased exposure to sunlight and/ or fluorescent light without dctoriation of desirable properties of contained products.
The specific nature of this invention, as well as other objects and advantages thereof, will become apparent to those skilled in the art from the following detailed description taken in conjunction with the annexed sheet of drawings on which, by way of preferred example only, are illustrated the preferred embodiments of this invention.
The accompanying drawing illustrates in comparative form light protection properties of several standard and ultraviolet absorbing glasses as specific embodiments of the present invention.
in accordance with the present invention there is produced green glass having a color appearance similar to emerald green, a visibility equal to that of emerald green and much greater than that of amber, permitting the examination of contents retained in containers made of such glass and having light protection" vastly exceeding that of emerald green glass and similar to that of amber. Emerald green glass such as employed in bottling certain carbonated beverages generally is regarded as having C.I.E. colorimetric values consisting of the following for a typical 10.0mm. specimen; 34.4% brightness, 66.4% purity and 555 millimicrons dominant wave length. Amber glass generally has distinctively different values which typically fora 2.0 mm. specimen are: 48.0% brightness, 78.8% purity and 579 millimicrons dominant wave length.
The ultraviolet absorption achieved by the present invention is due to the presence of hexavalent chromium in the glass also containing a minimal amount of iron as commercially melted. It is not necessary in practicing the present invention that any particular amount of iron be included in the composition. However, as is known in producing commercial melts of common glasses small amounts of iron are inherently present as a contaminant being carried into the glass with some of its major constituents such as silica sand.
Commercial glasses made in accordance with this invention are prepared by controlling both the batch constituents of the glass as prepared and the melting and fining conditions under which they are melted. This is obtained by an oxidizing atmosphere in the melter and/or the use of oxidizing agents in the glass batch as melted. The hexavalent chromium may be produced by employing alkali metal or alkaline earth chromate or dichromates in the batch composition. It has also been found that any other chromium containing glass-forming material might be similarly employed as the source of the chromium. An alkaline nitrate such as potassium nitrate (KNO or sodium nitrate (NaNO is employed in the batch to produce a prescribed amount of oxidant depending upon the particular composition and melting conditions to secure the hexavalent chromium in the end product. It is necessary in preparing the composition that both the chromium containing glass-forming material and the oxidant such as an alkaline nitrate be used together to ensure that at least a portion of the chromium either remains or is converted to the hexavalent state on melting and fining.
The chromium is added to the glass batch preferably either as potassium dichromate (Kgcl'zoq) or sodium dichromate fNa cr O lH o) although other chromates or chromites may similarly be employed. The potassium dichromate which is stable in air offers certain advantages in the production of the subject glasses over sodium dichromate which is deliquescent. In melting and refining of the glass batch wherein chromates or dichromates or mixtures thereof are utilized as the chromium containing material, at least a portion of the chromium is retained in the hexavalent state during melting and is also so retained in the final glass product.
The chromium containing materials employed in the glass batch may be comprised of chromium in its highest state of valence in the form of chromates and/or dichromates for securing the hexavalent chromium. In this case a major portion of the hexavalent chromium is reduced to the trivalent state in the melting furnace while a minor amount is retained in the hexavalent state in the final glass product.
In another procedure for practicing the present invention the chromium containing material may consist of a mixture of chromate or dichromate and chromite, Wherein the heat-reacted product of the chromium containing materials consists of part hexavalent chromium oxide (CrO and part trivalent chromium oxide (Cr O In still another procedure the chromium containing material may be comprised entirely of trivalent chromium as in the case of utilizing iron chromite (FeO.Cr O as a batch constituent. In this case an oxidant such as the alkaline nitrate is placed in the glass batch and oxidizing conditions within the melting furnace are utilized to convert at least a portion of the trivalent chromium oxide (Cr O into hexavalent chromium oxide (CrO The hexavalent chromium is a powerful absorber of ultraviolet radiation and a less powerful absorber of visible radiation. Furthermore, it is practical to secure either by oxidation or retention of only a small portion of the chromium in the hexavalent state an amount of approximately 0.05% being adequate to absorb nearly 85% of the ultraviolet radiation and all radiations below about 440 millimicrons. The hexavalent chromium produces a slightly yellowing tendency in the glass which may be desirable for producing a yellow green glass for example. However, the addition of a small amount of copper oxide (CuO) tending to produce a bluish color will complement this yellowing tendency so that the glass resembles or closely approaches an emerald green color.
The conditions which have been pointed out above for obtaining an ultraviolet absorption glass as an end product are greatly affected by the melting and refining conditions of the glass. These conditions obviously vary considerably during the operation of a commercial open hearth type furnace such as universally used in the manufacture of glass bottles, jars, or other containers. The normal operating variations frequently result in a lack of satisfactory control of the state of oxidation of the chromium present in the glass and it is imperative that either the melting and fining conditions or the batch constituents or both be carefully controlled to secure a desired level of hexavalent chromium oxide in the final product.
The existence and amount of hexavalent chromium which is produced in a given glass composition such as emerald green, for example, is largely due to the atmosphere over the raw glass melt and the components of the batch utilized in the melting process. Control over the melting and thus the valence state of the chromium may be obtained by supplying oxygen into the batch from an oxygen bubbler disposed in the melting chamber for maintaining a slightly oxidizing atmosphere over the raw glass as melted. One form of apparatus and method for producing the subject ultraviolet absorbing green glass has been disclosed in the copending patent application of Joseph C. Hamilton, Serial No. 713,857, filed February 7, [1957,] 1958, and now abandoned, entitled Method of Producing Ultraviolet Absorbing Green Glass, which application is assigned to the same assignee as the present application. As pointed out in the referred to application conditions for obtaining ultraviolet radiation absorption glass in the melter are strongly affected by the melting conditions both as to atmosphere and constituents. Melting conditions vary considerably during the operation of a commercial open hearth furnace such as universally used in continuous tank manufacturing of molten glass of consistent quality for forming and end use demands in making bottles, jars or other containers. The referred to application of Hamilton provides method and means of eliminating melting variations and furnishes control over the hexavalent chromium oxide in the glass melt by an oxygen bubbler introducing oxygen into the glass during the melting.
As exemplary of the process disclosed in the aboveidentified application of Hamilton, tests have been run with glasses made within the composition range herein disclosed to determine the effect of the amount of hexavalent added chromium necessary to obtain complete absorption through a A inch thick sample of glass and the effect of maintaining oxidizing conditions on the transmission of allowable light. The results of these tests show that transmissions at a wave length of 400 millimicrons vary from 4% to 6% when using 03% chromium oxide (expressed as Cr O added as K Cr with 25 lbs. of niter per ton of sand and an oxygen-bubbler rate of .35 cubic feet per hour with refiner atmospheres ranging from neutral to 6% air. Transmission when .06% chromium oxide is used under the same conditions is not detectable (less than 0.1% transmission), or is reduced below any predetermined value.
With .04% chromium oxide (added as dichromate), the oxygen-bubbler was demonstrated to be effective in controlling the state of oxidation of the chromium, and the ultraviolet transmission. At a bubbler rate of .1 cubic foot per hour, the glass showed 3 /2% transmission at 400 millimicrons, while at a bubbler rate of .35 cubic foot per hour, the transmission at 400 millimicrons was only .5 In the first case, the excess air in the refiner was 2% whereas in the second case it was 10%.
These test results are examples taken from a series thereof in which it was found that the variations in the rate of oxygen bubbling easily attainable in practice were sufficient to compensate for the variations in oxidizing or reducing conditions normally encountered in open hearth melting furnaces.
In the melting of such compositions, whether or not bubblers are used, the melting temperatures range from 2700 F. to 2875 F. and the refining or conditioning duce a slightly deeper shade of green glass. Glass No.
temperatures range from 2000 F. to 2500 F. 3 contains 2.3% boric oxide (B furnishing an ex- Examples of glass batches which may be used in pracample of a modified borosilicate glass which also proticing our invention are as follows: vides ultraviolet absorption characteristics in having hexavalent chromium present. TABLE 1 Other examples of suitable glass compositions which may be utilized are those having the following theoretical Components No.1 No.2 No.3 analyses (in percentage by weight).
TABLE III Components i No. 4 i No. 5 N0. 6 N0. 7
70. 2 68. 0 00. 7 03. 4 3.2 5.0 7.0 0.5 Fluorspar i g 6 Potassium Diehrornate 0: 2 (1: 1 I): 1 0: l 14. 5 14. s 15. 0 15. 0 1.0 2.0 2.0 2.4 0.137 0.137 0.137 0.107 0. 0050 0. 0050 0. 0000 0. 0050 Chemical analyses of the glass product produced from the above glass batches are as follows:
TABLE .11 It will be noted that the alumina (A1 0 content of such glasses are substantially larger than those of Examples 1-3 above. Also, the total R 0 analysis is Chem 1A al'e 0.1 01.2 N.3 1?
m n is S A O o o greater, even though the total Cr O content has been 7L8 71.3 709 7045 lowered. The high alumina content is due primarily to 1.02 1.74 2.55 0.1-0.0 the utilization of high A1 0 sand, known in the trade as 12 32 iii 61? Del Monte Sand," having the following typical analvsis: 0.02 0.02 0." 0*! 15.5 10.1 11. 0 10 -20 Percmt y 8 0.304 0.410 ages 3- g o 79 ""0701 "0:05" 5.22 0.1-0? A1 0 11.9 0.001 0. 003 0. 000 .000070 p o (]7 mo 0.11 0.07 0.045 0. 040 0.045 moan) CaO 1.7 Na O 3.3 .0 0 10 .0 0 100 000 100 0 0 0 2 n 23 Table IV illustrates a comparison of so-called ultra- The R 0 in the analyses represents constituents such sor glasses A through E inclusive as compared as A1 0 and other related metallic oxides which are comwith conventional emerald green and amber glasses. The
monly grouped together under this heading for analytical standard emerald green and amber do not ordinarily purposes. It will be noted that the three glasses Nos. 1, contain any hexavalent chromium (CrO and only the 2 and 3 each contain a total chromium oxide content emerald green contains trivalent chromium (Cr O in an expressed as Cr O of about 0.22% and about one-third amount of 0.21% in the indicated analysis of a typical of the chromium oxide is present in the hexavalent state melt. Each of the Ultrasorb glasses may be observed in an amount of about 0.061% to secure ultraviolet abto contain varied amounts of hexavalent chrominm sorption. Glass No. 2 contains 0.7% CuO to mask the (CrO with each having relative ultraviolet ray absorpyellowing tendency of the hexavalent chromium to protion power.
TABLE IV Ultrasorb" Emerald Amber Green A B 0 D E CLLE. (IOLORIMETRIC VALUES Thickness of specimen in mm. 10 2.0 i 10 10 l 10 i 10 10 Percent Br. 34. 4 48. 0 24. 5 51.0 26. 0 30. 8 27.0 Percent Pnrfi 60. 4 78.8 87.1) 85. 5 71.8 67.0 62. 5 D.W.L. (111,0) 555 579 655 564 558 558 555 1 Percent brightness. 3 Percent purity. 3 Dominant Wave length (millimtcrons).
Curves of the percent transmittance through a two millimeter specimen of wave lengths in the range of from 300 to 500 millimicrons are shown on the accompanying graph. With 400 millimicrons considered to be generally the line of distinction between ultraviolet and visible violet rays, it can be readily observed that emerald green glass is capable of absorbing only a small amount of ultraviolet below about 320 millirnicrons and that it transmits a very large portion of the ultraviolet between 320 and 440 millimicrons. Amber glass on the other hand which is very dense and approaches opaqueness in any appreciable thickness absorbs nearly all of the ultraviolet and also a considerable amount of the visible wave lengths between 400 and 500 millimicrons as can be seen by the curve for amber on the bottom of the graph.
In between these extremes reside the subject ultrasorb glass melts wherein the hexavalent chromium oxide[s] (CrO percentages range from 0.005 to 0.065% by weight. The minimum amount of hexavalent chromium of 0.005% transmits only a small portion of the total ultraviolet and it may also be observed that the relative amount of ultraviolet transmission is directly correlative to the relative amount of hexavalent chromium oxide present in the glass. It can also be seen how the subject glasses achieve very appreciable absorption of the ultraviolet with a high rate of transmission of the visible light in the range of from 440 millimicrons and above.
The properties of the Ultrasorb absorbing green glasses which have been found to be particularly desirable are the following:
(a) The visibility similar to that of emerald green and much greater than that of amber glass.
(b) Light protection vastly exceeding that of emerald green and similar to that of amber.
(c) Batch costs only slightly exceeding that of emerald green on the basis of per ton of glass made.
(d) The ultraviolet absorbing property is essentially due to hexavalent chromium in the glass which is obtained by using an oxidizing atmosphere in the melter, chromates or dichromates or chromite as the source of chromium, and niter or saltpeter as an oxidant in the batch.
(e) A total chromium oxide content of less than 0.5% by weight and generally from about 0.1 to 0.3% total chromium oxides of which about 0.005 to 0.070% exists as hexavalent chromium oxide (CrO provides a glass having very substantial ultraviolet absorbing features. Utilizing less than 0.2% and preferably about 0.08% copper oxide (CuO) in the glass produces a near emerald green color. When the copper is omitted the glass has a more yellowish green hue due to the yellow-orangish tendency of the hexavalent chromium, the trivalent chromium oxide (Cr producing the green. Cobalt oxide (C00) may also be used to eliminate the yellowish cast to produce an emerald green. The cobalt oxide may be present in an amount less than 0.01% CoO preferably ranging from 0.002 to 0.008% C00 and about 0.004% C00 for near emerald green glasses containing 0.008 to 0.030% CrO for example.
The new glasses may contain by weight 6075% SiO 0.ll0.0% R 0 of which the major portion is A1 0 6- 12% Ca(); 06% MgO; 01% BaO; 21% alkali metal oxides; 0-5% B 0 0.020-0.20% Fe O and chromium oxide present in both the trivalent and hexavalent states usually in a total amount of less than 0.5%. It has been found preferable to employ a total chromium oxide content of 0.1-0.3% with about 0.0050.070% CrO to secure in an economical manner the very considerable absorption of ultraviolet rays. When the new glasses of the present invention contain between 0.1 and 3.0% Al 0 the glass may contain by weight 70 to 75% SiO A higher magnesium oxide content glass may be produced by using a magnesium containing component in the batch such as dolometic limestone rather than lime. Comparativcly low silica-high alumina glasses having excellent absorption characteristics can be prepared from high A1 0 content sands. Furthermore, it is possible to produce modified borosilicate glasses by employing from about 1-5% B 0 in the glass. In order to produce the green glass having a coloration near emerald green the copper oxide (CuO) may be included in an amount of less than 0.2% by weight. In melting the subject glasses it is necessary to maintain an oxidizing atmosphere in the melter with preferably a small amount of niter or saltpeter in the batch suflicient to oxidize a portion of the Cr O to the hexavalent state C10 The ultraviolet radiation absorbing emerald green glass composition of this invention comprises essentially a sodalime-silica gloss containing at least 0.1% A1 0 such as 0.1 to 3.0% Al O less than 0.3% Fe o and about 0.10 to 0.30% total chromium oxides present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (C10 the latter chromium xide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition and said composition having C.I.E. colorimetric values for I 0 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length. Thus, when 0.] to 3.0% A1 0 is present, the ultraviolet radiation absorbing emerald green glass composition of this invention comprises essentially by weight 70 to 810 said percentage of A1203, 6 to 12% 010; 0 to 6% MgO; 0 to 1% BaO; O to 5% B 0 10 to 21% alkali metal oxides; including less than about 0.3% Fe O and less than about 0.3% total chromium oxides present as both trivalent chromium oxide (Cr 0 and hexavalent chromium oxide (CrO the latter ranging from about 0.005 to 0.070%; said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
The preferred compositions of the present invention can be summarized as follows:
TABLE V Components: Percent by weight SiO 60-75 R 0 (total) 0.1-10.0 N 0 0.1-9.5 F3203 CaO 6-12 13:10 Ol.0 B 0 0-5 MgO 0-6 N320 K 0 0-1 Cr 0 (total) 0.1-0.3 cro 0.005-0.070 C00 0.002-0.008
The C.I.E. colorimetric values are based upon the I. Chromaticity Diagram C.I.E. refers to the First International Commission of Illumination and the diagram from which the values are taken defines color in terms of mixtures of theoretical colored lights The C.I.E. system makes possible the exact specification of colors by means of a color map." The C.I.E system of color notation specifies the color of glasses in terms of brightness, purity and dominant wave length. Brightness which is usually expressed in terms of percentage is the amount of visual response to a normal observer to the radiation emergent from a transparent object relative to the response in this observer to the radiation incident upon the object. Thus, brightness may be briefly termed the lightness of color of an object. Purity which is also normally expressed in terms of percentage is a measure of the monochromaticness of a color with monochromatic light having purity of By diluting the monochromatic radiation with white light made up of all wave lengths, We thereby dilute the color and reduce purity. "Dominant Wave Length, usually expressed in millimicrons (m is the wave length of monochromatic light appearing to the eye to have the same hue as the mixed light actually encountered.
Various modifications may be resorted to within the spirit and scope of the appended claims.
[1. An ultraviolet radiation absorbing green glass composition comprising essentially by weight 60 to 75% S10 0.1 to 9.5% A1 6 to 12% C210; 0 to 6% MgO; 0 to 1% B210; 0 to 13 0 to 21% alkali metal oxides; including less than about 0.3% E2 0 and less than about 0.3% total chromium oxides present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the latter ranging from about 0.005 to 0.070%] [2. An ultraviolet radiation absorbing green glass composition comprising essentially by weight 60 to 75 SiO 0.1 to 9.5% A1 0 6 to 12% C210; 0 to 6% MgO; 0 to 1% BaO; 0 to 5% B 0 10 to 21% alkali metal oxides; 0.02 to 0.20% Fe O and about 0.10 to 0.30 total chromium oxides including about 0.005 to 0.070% hexavalent chromium oxide, said composition having C.I.E. colorimetricvalues for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant Wave length] [3. An ultraviolet radiation absorbing green glass composition consisting essentially of the following ingredients:
Ingredients: Percent by Weight 510 6075 R 0 (total) 0.1-10.0 A1 0 0.1 9.5 Fe O 0.0204120 CaO 6-12 1330 O1.0 B 0 0 s MgO 0-6 Na O 10-20 K 0 O1 Cr O (total) 0.1O.3 cro 0.00;:0070 COO 0.0020.008]
4. An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing at least 0.1% Al O less than 0.3% Fe 0 and about 0.10 to 0.30% total chromium oxides expressed as Cr O and present as both trivalent chromium oxide (Cr 0 and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
5. An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing at least 0.1% AI O 0.02 to 0.20% Fe O and about 0.10 to 0.30% total chromium oxides expressed as C7 0 and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (Gro the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
6. An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing at least 0.1% A1 0 less than 0.3% Fe O C00 in an amount less than 0.01% and about 0.10 to 0.30% total chromium oxides expressed as Cr O and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% 10 brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
7. An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing at least 0.1% A1 0 0.02 to 0.20% Fe O C00 in an amount less than 0.01% and about 0.10 to 0.30% total chromium oxides expressed as Cr O and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
8. The glass composition of claim 7 wherein the C00 content is from 0.002 to 0.008%.
9. An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing at least 0.1% A1 0 less than 0.3% Fe O CuO in an amount less than 0.2% and about 0.10 to 0.30% total chromium oxides expressed as Cr O; and present as both trivalent chromium oxide (Cr o and hexavalent chromium oxide (C10 the hexavalem chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% bright ness 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
10. An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing at least 0.1% Al O 0.02 to 0.20% Fe O CuO in an amount less than 0.2% and about 0.10 to 0.30% total chromium oxides expressed as (V 0 and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
1]. The glass composition of claim 10 wherein the CuO content is about 0.08%.
12. An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing 0.1 to 3.0% Al O less titan 0.3% Fe o and about 0.10 to 0.30% total chromium oxides expressed as Cr O and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
13. An ultraviolet radiation absorbing emerald green glass composition consisting essentially of soda-lime-silica glass containing 0.1 to 3.0% Al O 0.02 to 0.20% E2 0 and about 0.10 to 0.30% total chromium oxides expressed as Cr O and present as both trivalent chromium oxide (C and hexavalent chromium oxide (C10 the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
14. An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing 0.1 to 3.0% AI O less than 0.3% Fe 0 C00 in an amount less than 0.01% and about 0.10 to 0.30% total chromium oxides expressed as Cr O and present as both trivalent chromium oxide (C7 0 and lzexavalent chromium oxide (Cr the hcxavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.1.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
15. The glass composition of claim 14 wherein the C00 content is from 0.002 to 0.008%.
16. An ultraviolet radiation absorbing emerald green glass composition consisting essentially of a soda-limesilica glass containing 0.1 to 3.0% Al 0 less than 0.3% Fe O CuO in an amount less than 0.2% and about 0.10 to 0.30% total chromium oxides expressed as Cr O and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said percentages being by weight of said glass composition, and said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
17. An ultraviolet radiation absorbing emerald green glass composition consisting essentially by weight of 70 to 75% S10 0.1 to 3.0% A1 0 6 to 12% CaO, 0 to 6% MgO, 0 to 1% 13:10. 0 to B 0 to 21% alkali metal oxides, less than 0.3% Fe O and about 0.10 to 0.30% total chromium oxides, expressed as Cr 0 and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (Cro the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
18. An ultraviolet radiation absorbing emerald green glass composition consisting essentially by weight of 70 to 75% SiO 0.1 to 3.0% Al O 6 to 12% CaO, 0 to 6% MgO, 0 to 1% BaO, 0 to 5% B 0 10 to 21% alkali metal oxides, 0.02 to 0.20% Fe O 0.002 to 0.008% C00 and about 0.10 to 0.30% total chromium oxides, expressed as Cr O and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52% brightness, to 87% purity and 554 to 565 millimicrons dominant wave length.
19. An ultraviolet radiation absorbing emerald green glass composition consisting essentially by weight of to S10 0.1 to 3.0% A1 0, 6 to 12% CaO, O to 6% MgO, 0 to 1% BaO, 0 to 5% B 0 10 to 21% alkali metal oxides, 0.02 to 0.20% ee o CuO in an amount less than 0.2% and about 0.10 to 0.30% total chromium oxides, expressed as Cr O and present as both trivalent chromium oxide (Cr O and hexavalent chromium oxide (CrO the hexavalent chromium oxide ranging from about 0.005 to 0.070%, said composition having C.I.E. colorimetric values for 10 mm. thickness of about 25 to 52 brightness, 60 to 87% purity and 554 to 565 millimicrons dominant wave length.
References Cited in the file of this patent or the original patent UNITED STATES PATENTS Armistead Jan. 11, 1955 OTHER REFERENCES
US25456D Ultraviolet light absorbing glass Expired USRE25456E (en)

Publications (1)

Publication Number Publication Date
USRE25456E true USRE25456E (en) 1963-10-08

Family

ID=2094335

Family Applications (1)

Application Number Title Priority Date Filing Date
US25456D Expired USRE25456E (en) Ultraviolet light absorbing glass

Country Status (1)

Country Link
US (1) USRE25456E (en)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3291621A (en) * 1963-05-31 1966-12-13 Owens Illinois Inc Ultraviolet light-absorbing glass
US3332790A (en) * 1964-02-06 1967-07-25 Penberthy Harvey Larry Ultraviolet absorbing green glass
US3351474A (en) * 1963-12-16 1967-11-07 Owens Illinois Inc Glass compositions resistant to discoloration, method of making and articles produced therefrom
US3364041A (en) * 1965-11-24 1968-01-16 Owens Illinois Inc Glass composition and method
US3364042A (en) * 1965-12-20 1968-01-16 Owens Illinois Inc Glass composition and method
US20140272215A1 (en) * 2011-10-25 2014-09-18 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US9145329B2 (en) 2011-10-25 2015-09-29 Corning Incorporated Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability
US9517966B2 (en) 2011-10-25 2016-12-13 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US9603775B2 (en) 2013-04-24 2017-03-28 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9700486B2 (en) 2013-04-24 2017-07-11 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9700485B2 (en) 2013-04-24 2017-07-11 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707153B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707154B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707155B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9713572B2 (en) 2013-04-24 2017-07-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9717649B2 (en) 2013-04-24 2017-08-01 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9717648B2 (en) 2013-04-24 2017-08-01 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9839579B2 (en) 2013-04-24 2017-12-12 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9849066B2 (en) 2013-04-24 2017-12-26 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US10273049B2 (en) 2012-06-28 2019-04-30 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
US10413481B2 (en) 2011-10-25 2019-09-17 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3291621A (en) * 1963-05-31 1966-12-13 Owens Illinois Inc Ultraviolet light-absorbing glass
US3351474A (en) * 1963-12-16 1967-11-07 Owens Illinois Inc Glass compositions resistant to discoloration, method of making and articles produced therefrom
US3332790A (en) * 1964-02-06 1967-07-25 Penberthy Harvey Larry Ultraviolet absorbing green glass
US3364041A (en) * 1965-11-24 1968-01-16 Owens Illinois Inc Glass composition and method
US3364042A (en) * 1965-12-20 1968-01-16 Owens Illinois Inc Glass composition and method
US11707409B2 (en) 2011-10-25 2023-07-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US11168017B2 (en) 2011-10-25 2021-11-09 Corning Incorporated Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability
US9340447B2 (en) 2011-10-25 2016-05-17 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US9517966B2 (en) 2011-10-25 2016-12-13 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US20140272215A1 (en) * 2011-10-25 2014-09-18 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US9617183B2 (en) * 2011-10-25 2017-04-11 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US9624125B2 (en) 2011-10-25 2017-04-18 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US10413481B2 (en) 2011-10-25 2019-09-17 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US11707408B2 (en) 2011-10-25 2023-07-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US11707410B2 (en) 2011-10-25 2023-07-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US11325855B2 (en) 2011-10-25 2022-05-10 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US9145329B2 (en) 2011-10-25 2015-09-29 Corning Incorporated Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability
US10597322B2 (en) 2011-10-25 2020-03-24 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US10577274B2 (en) 2011-10-25 2020-03-03 Corning Incorporated Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability
US9718721B2 (en) 2011-10-25 2017-08-01 Corning Incorporated Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability
US10441505B2 (en) 2011-10-25 2019-10-15 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US10413483B2 (en) 2011-10-25 2019-09-17 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US10413482B2 (en) 2011-10-25 2019-09-17 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US10196298B2 (en) 2011-10-25 2019-02-05 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US10273048B2 (en) 2012-06-07 2019-04-30 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
US10273049B2 (en) 2012-06-28 2019-04-30 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
US9603775B2 (en) 2013-04-24 2017-03-28 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9849066B2 (en) 2013-04-24 2017-12-26 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9839579B2 (en) 2013-04-24 2017-12-12 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9717648B2 (en) 2013-04-24 2017-08-01 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9717649B2 (en) 2013-04-24 2017-08-01 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9713572B2 (en) 2013-04-24 2017-07-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707155B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707154B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707153B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9700485B2 (en) 2013-04-24 2017-07-11 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9700486B2 (en) 2013-04-24 2017-07-11 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients

Similar Documents

Publication Publication Date Title
USRE25456E (en) Ultraviolet light absorbing glass
AU755014B2 (en) Ultraviolet-absorbing, colorless, transparent soda-lime silica glass
EP0648195B1 (en) Glass composition
CA1149826A (en) Tinted glass
US5077133A (en) Infrared and ultraviolet radiation absorbing green glass composition
AU2005210070B2 (en) Silico-sodo-calcic glass composition
EP1281686B1 (en) Ultraviolet ray-absorbing, colorless and transparent soda-lime-silica glass
JPH09110464A (en) Very deeply grey soda lime glass
US2974052A (en) Ultraviolet light absorbing glass
US2923636A (en) Glass-making frit and method
US3291621A (en) Ultraviolet light-absorbing glass
US3482955A (en) Glass decolorizing with manganese enriched alkali borate glass
EP0976691B1 (en) Ultraviolet ray absorbing glass
EP0259132B1 (en) Glasses for containers; processes for the production of same; and containers comprising said glasses
US3332790A (en) Ultraviolet absorbing green glass
WO2002066388A1 (en) Ultraviolet ray absorbing colorless transparent soda-lime-silica glass, method for production thereof and glass container comprising said glass
JPH0230637A (en) Glass bottle displaying deterioration of contents
EP0832044B1 (en) Uv radiation absorbing package
RU2725313C1 (en) Composition of sodium-calcium-silicate glass
JPH11116270A (en) Ultraviolet-ray absorbing colorless transparent soda lime-silica glass, its production and glass bottle obtained by molding same
EP0347945B1 (en) Yellow-green glass absorbing the whole range of the ultraviolet radiation