WO2014070364A1 - Inspectable black glass containers - Google Patents

Inspectable black glass containers Download PDF

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Publication number
WO2014070364A1
WO2014070364A1 PCT/US2013/063205 US2013063205W WO2014070364A1 WO 2014070364 A1 WO2014070364 A1 WO 2014070364A1 US 2013063205 W US2013063205 W US 2013063205W WO 2014070364 A1 WO2014070364 A1 WO 2014070364A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
black
container
glass container
strikable
Prior art date
Application number
PCT/US2013/063205
Other languages
French (fr)
Inventor
Roger P. Smith
Carol A. CLICK
Rebecca Mullen
Stephen Daniel BARTON
Original Assignee
Owens-Brockway Glass Container Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to PE2019001463A priority Critical patent/PE20191399A1/en
Priority to MX2015005168A priority patent/MX2015005168A/en
Application filed by Owens-Brockway Glass Container Inc. filed Critical Owens-Brockway Glass Container Inc.
Priority to ES13776688T priority patent/ES2959093T3/en
Priority to CN201380057484.7A priority patent/CN104870387B/en
Priority to NZ705706A priority patent/NZ705706A/en
Priority to SG11201502576UA priority patent/SG11201502576UA/en
Priority to RU2015120555A priority patent/RU2015120555A/en
Priority to MYPI2018002629A priority patent/MY196137A/en
Priority to AU2013338529A priority patent/AU2013338529B2/en
Priority to CA2889167A priority patent/CA2889167C/en
Priority to PL13776688.7T priority patent/PL2914556T3/en
Priority to BR112015009590-9A priority patent/BR112015009590B1/en
Priority to EP13776688.7A priority patent/EP2914556B1/en
Priority to EP23183233.8A priority patent/EP4242643A3/en
Publication of WO2014070364A1 publication Critical patent/WO2014070364A1/en
Priority to ZA2015/01778A priority patent/ZA201501778B/en
Priority to PH12015500748A priority patent/PH12015500748A1/en
Priority to AU2017202090A priority patent/AU2017202090B2/en

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/88—Investigating the presence of flaws or contamination
    • G01N21/95—Investigating the presence of flaws or contamination characterised by the material or shape of the object to be examined
    • G01N21/958—Inspecting transparent materials or objects, e.g. windscreens
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/02—Compositions for glass with special properties for coloured glass
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
    • G01J5/10—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors
    • G01J5/28—Radiation pyrometry, e.g. infrared or optical thermometry using electric radiation detectors using photoemissive or photovoltaic cells
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/88—Investigating the presence of flaws or contamination
    • G01N21/8806—Specially adapted optical and illumination features
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/88—Investigating the presence of flaws or contamination
    • G01N21/90—Investigating the presence of flaws or contamination in a container or its contents
    • G01N21/909—Investigating the presence of flaws or contamination in a container or its contents in opaque containers or opaque container parts, e.g. cans, tins, caps, labels
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/38—Concrete; Lime; Mortar; Gypsum; Bricks; Ceramics; Glass
    • G01N33/386—Glass
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/88—Investigating the presence of flaws or contamination
    • G01N21/8806—Specially adapted optical and illumination features
    • G01N2021/8845—Multiple wavelengths of illumination or detection
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]

Definitions

  • the present disclosure is directed to glass containers and, more particularly, to coloring of glass containers.
  • Glass containers are often composed of so-called soda-iime glass, also called soda-lime-silica glass. Many such containers are colored, for example, for aesthetic or functional purposes. Colored glass containers may be produced from soda-lime glass compositions which include one or more colorants. For example, blue glass containers can be made from soda-iime glass compositions which include cobalt oxide (CoO) as a colorant.
  • CoO cobalt oxide
  • U.S. Patents that illustrate colored glass compositions of this type include 3,326,702, 3,330,638, 3,345,190, 3,498,806, and 4,312,953.
  • a general object, in accordance with one aspect of the disclosure, is to provide a glass composition that may be used to produce cobalt blue glass containers that, upon heat treatment and striking, develop a visually black color. Accordingly, this glass composition and the glass containers formed therefrom may be referred to as "bkck-strikable.”
  • the glass containers may be inspected— before or after striking -by infrared inspection equipment in a glass container production line or in a container filling operation. Accordingly, these glass containers also may be referred to as "inspectable.”
  • the optical inspection of black glass containers had been thought impossible due to their low percentage of light transmission.
  • the present disclosure embodies a number of aspects that can be implemented separately from or in combination with each other.
  • a black-strikable glass container having a base glass portion and a latent colorant portion.
  • the base glass portion includes: 60-75 wt. % Si0 2 , 7-15 wt. % Na 2 0, 6-12 wt. % CaO, 0.1-3.0 wt. % A1 2 0 3 , 0.0-2.0 wt. % MgO, 0.0-2.0 wt. % K 2 0, 0.01-0.25 wt. % S0 3 , 0.01-0.25 wt. % Fe 2 0 3 , and 0.01-0.15 wt.
  • the latent colorant portion includes: 0.0875-0.35 wt. % cuprous oxide (Cu 2 0), 0.06-0.5 wt. % stannous oxide (SnO), 0.006-0.05 wt. % bismuth oxide (Bi 2 0 3 ), and 0.02-0.10 wt. % carbon (C). Thereafter, a black-strikable glass container is formed from the black- strikable glass composition.
  • infrared light energy is directed onto and through the black glass container, and is received on an infrared light sensor.
  • the infrared light sensor Is responsive to infrared light energy received thereon having wavelengths in the range of 750- 1100 run.
  • FIG. 1 is a side elevation of a glass container in accordance with an exemplary embodiment of the present disclosure.
  • FIG, 2 is a graphical plot of light transmission through samples of inspectabie struck-black container glass doped with three different amounts of copper oxide ( ⁇ 3 ⁇ 40).
  • FIG. 1 illustrates an exemplary embodiment of a glass container 10 (e.g., glass bottle, jar, or the like) that may be produced in accordance with an exemplary embodiment of a presently disclosed manufacturing process, as described further herein below.
  • the glass container 10 may be referred to as "inspectabie,” meaning that the glass container 10 transmits a sufficient amount of infrared light to be inspected by infrared inspection equipment in a glass container production, line or in a container filling operation.
  • the glass container 10 may be produced by the following method. Additional exemplary conditions and procedures for composing and melting production container glass can be found in, e.g. the Handbook of Glass Manufacture by Fay V. Tooley (3rd ed., Ashlee Publishing 1984).
  • the method may include preparing a black-strikable glass composition.
  • the black-strikable glass composition may be thought of as having a base glass portion and a latent colorant portion. lie base: glass portli inbl ®. mH& im& ⁇ ⁇ io& glass materials and one or mofre blue >k*m matedals.
  • the b se glass p tl ii may incliide slsbstanriaily t same iB eria!S : present in cobalt Mm glass,
  • a presently preferre cobalt him glass may comprise the following materials in the: Mowin ranges of am» i3 ⁇ 4s b weig!it:
  • glass a comprise the following materials in substantially the stated amounts b weight:
  • the latent colorant portion of the black-strikable glass composition may include cuprous oxide (C11 2 O), stannous oxide (SnO), bismutii oxide ( ⁇ 2 ⁇ 3 ), and carbon (C), as this combination of materials has been found to enable the striking of copper (Cu) in soda-lime glass containers.
  • the molar ratio of tin oxide (SnO) to copper oxide (C3 ⁇ 4Q) in the latent colorant portion may be about one, for example, the molar ratio may be in the range of 0.9 to 1 , or in the range of about 1 to 0.9.
  • the latent colorant portion suitably may contain an excess of tin oxide (SnO).
  • the molar ratio of tin oxide (SnO) to copper oxide (C3 ⁇ 40) may be about 1.5.
  • the black-strikable glass composition may include about 0.175 vvt. % cuprous oxide (Cu 2 0), about 0,25 wt. % stannous oxide (SnO), about 0.0125 wt. % bismuth oxide ( ⁇ 2 ⁇ 3), and about 0.06 wt. % carbon (C).
  • the black-strikable glass composition may include 0.0875-0.35 wt. % cuprous oxide (03 ⁇ 40), 0.06-0.5 wt. % stannous oxide (SnO), 0.006-0.05 wt. % bismuth oxide (Bi 2 0 3 ), and 0.02-0.10 wt. % carbon (C).
  • the black-strikable glass composition may include substantially 0.175 wt. % cuprous oxide (Cu 2 0), substantially 0.25 wt. % stannous oxide (SnO), substantially 0.0125 wt. % bismuth oxide and substantially 0.06 wt. % carbon (C).
  • the term "substantially” means within manufacturing tolerances customary in the glass container manufacturing industry.
  • the remaining portion of black-strikable glass composition may include small amounts of other materials. Such materials may be additives, residual materials from euliet and/or impurities typical in the glass container manufacturing industry. Such materials may be present in trace amounts, for example, less than 0.2 wt %. In one specific example, the remaining portion of the black-strikable glass composition may include trace amounts of TiO?, BaO, and/or SrO.
  • the method also may Include forming black-strikable glass containers from the black-strikable glass composition.
  • a feeder located at a downstream end of the one or more forehearths may be used to measure ou gobs of molten glass and to deliver them to glass container-forming machines. Thereafter, the gobs may be formed into glass containers, for example, by press-and-hiow or blow-and-blow processes and by individual section machines, or in any other suitable manner by any suitable equipment.
  • the method further may include annealing the black-strikable glass containers in any suitable manner, for example, in an annealing le r.
  • the temperature therein may be between 550 and 600 degrees Celsius.
  • the temperature may be brought down gradually to a downstream portion, cool end, or exit of the lehr, for example, to a temperature therein of between 130 degrees Celsius and 65 degrees Celsius.
  • the glass containers may be annealed, preferably between 550 and 600 degrees Celsius for 30 to 90 minutes, more preferably between 525 and 575 degrees Celsius for 45 to 75 minutes, and most preferably at substantially 550 degrees Celsius for one hour.
  • the method also may include raising the temperature of the black-strikable giass containers above the highest temperature at which they are amiealed (i.e., the highest annealing temperature) to strike black coloration into the glass containers. Accordingly, this temperature- raising step may be referred to as "striking,"
  • the striking or temperature-raising step may include, for example, heat-treating the glass containers between 600 and 680 degrees Celsius for 10 to 90 minutes to produce black glass containers.
  • the temperature-raising step may include heat- treating the black-strikable glass containers between 630 and 650 degrees Celsius for 30 to 40 minutes.
  • the temperature raising or striking step may be carried out after the annealing step.
  • a furnace or secondary lehr may be used, in line or off line downstream of the annealing lehr.
  • the temperature of the glass containers may be raised in the furnace or secondary lehr to a temperature and for a lime suitable to strike black into the glass containers. Thereafter, the temperature of the black glass containers may be brought down gradually, for example, according to an annealing schedule to avoid fracture or failure of the containers.
  • the temperature raising or striking step may be carried out between the time the annealing step begins and the time the annealing step ends.
  • a separate furnace may be used off line adjacent to the annealing lehr, in another example, the annealing lehr may be operated in accordance with a modified heating profile.
  • the modified heating profile may include a typical annealing temperature profile modified to include temperatures and times suitable to strike black into the glass containers before, during, or after annealing.
  • the black-strikable glass containers may, in some respects, have a container glass composition that is different from the black-strikable glass composition.
  • the amount of sulfur trioxide (SO 3 ) retained in the glass containers may be substantially less than the amount of sulfur trioxide (SO 3 ) in the black-strikable glass composition.
  • the actual amount of sulfur trioxide (SO 3 ) retained in the glass containers will vary depending on the amount of carbon (C) in the black-strikable glass composition. In suitable embodiments, the amount of sulfur trioxide (SO 3 ) retained in the glass containers will be in the range of 0.01 to 0.22 wt. %.
  • the more carbon (C) in the black-strikable glass composition the less sulfur trioxide (SO 3 ) will be retained in die glass containers.
  • the latent colorant materials of C3 ⁇ 40, SnO, and B12O3 may be largely retained in the container glass composition.
  • about 75-100% of the Cu 2 0, SnO, and B12Q3 in the black-strikable glass composition may be retained in the container glass composition.
  • a struck-black glass container produced in accordance with this disclosure may have a wall thickness of greater than 0.040 inches (i.e., greater than about 1 mm). At this wall thickness, the glass container transmits a minimal amount of light at wavelengths between 390 mil and 700 nm and, thus, appears visually black to the human eye in natural lighting conditions (e.g.. indirect sunlight) at arm's length.
  • a struck-black glass container produced in accordance with this disclosure may transmit light in an amount less than 10 % at wavelengths between 390 nm and 675 nm.
  • a struck-black glass container produced in accordance with, this disclosure transmits infrared light in the near-infrared region of the electromagnetic spectrum (e.g., from about 750 nm to 1 100 nm) and, thus, may be inspected by infrared inspection equipment in a glass container production line or in a container filling operation.
  • a struck-black glass container produced in accordance with this disclosure may transmit light in an amount between about 30 % and about 65 % at wavelengths between 750 nm and 850 nm.
  • a struck-black glass container produced in accordance with this disclosure may transmit light in an amount of at least 40 % at a wavelength of 750 nm.
  • Glass containers produced in accordance with this disclosure may be inspected- either before or after striking— to detect for commercial variations in the glass.
  • Such commercial variations may include, for example, dimensional anomalies in the sidewalls, heels, bottoms, shoulders, and/or necks of the glass containers, as well as inhomogeneities in the glass itself that affect the optical properties of the glass containers.
  • Some of these commercial variations may be within commercially acceptable standards or thresholds, while other variations may be outside of such standards or thresholds, and thus may be unacceptable.
  • a suitable apparatus for detection of commercial variations in a glass container produced in accordance with ibis disclosure includes a light source, a Sight receiver, and an information processor,
  • the light source may include a lamp or a laser capable of emitting infrared light in the near-infrared region of the electromagnetic spectrum (e.g., from about 750 mil to 1100 nm)
  • the light receiver may include a laser optic sensor responsive to light energy at wavelengths in the range of about 750 nm to 1 100 nm.
  • a glass container produced in accordance with this disclosure may be inspected by directing light energy from an infrared, light source through the glass container and onto a light sensor.
  • infrared light in the near-infrared region of the electromagnetic spectrum may be directed through the glass container and onto the light sensor.
  • inf ared light at wavelengths in the range of about 750-850 nm may be directed through the glass container and onto the light sensor, h response, the light sensor may provide electrical signals to an information processor, which may analyze the electrical signals to determine whether the glass container is commercially acceptable or unacceptable.
  • a black-strikable glass composition may be used to produce cobalt blue glass containers and optionally black glass containers by the process of "striking.' '
  • the glass containers produced according to the present disclosure may be inspected- -before or after striking by infrared inspection equipment in a glass container production line or in a container filling operation.
  • a batch of raw materials was prepared and used to produce 300g of molten glass.
  • the batch of raw materials included the necessary raw materials to produce a black-strikable glass composition.
  • the necessary amount of each raw material for the batch was weighted out in accordance with standard batch caiculation practice common in the glass industry. Thereafter, the raw materials were crushed and ground using a mortar and pestle to break up agglomerate material, and then mixed together using a mixer for about ten minutes.
  • a crucible was pre-heated in a furnace at 1350 degrees Celsius for about ten minutes. The crucible was removed from the furnace and the entire batch of raw materials was added to the crucible. The crucible was again placed in the furnace, and the temperature of the furnace was increased to form a glass melt having a temperature of about 1450 degrees Celsius. The glass melt was held at that temperature for about 3.5 hours.
  • the molten glass was poured into splat quenched patties.
  • Some of the patties were placed in an annealing oven at 550 degrees Celsius, and some of the patties were left unannealed.
  • the patties which were placed in the annealing oven were annealed at a temperature of about 550 degrees Celsius for about 10 to 20 minutes, and then a door of the annealing oven was cracked open until the annealing oven temperature decreased to a temperature of about 300 degrees Celsius. Thereafter, the annealing oven temperature was set to 20 degrees Celsius to let the glass cool down to room temperature overnight.
  • the black-strikable glass patties were heat treated at oven temperatures of 550, 600, and 650 degrees Celsius for durations of 15 to 90 minutes. At 600 and 650 degrees Celsius, the samples struck black by 30 minutes.
  • FIG. 2 illustrates three plots of Transmission (%) vs. Wavelength (run) through samples of cobalt blue glass doped with suitable amounts of the disclosed latent colorant- materials. However, each of the samples was doped with a different amount of copper oxide (Cu 2 0). The three plots illustrate samples doped with 0.12 wt. % Cu 2 0 (dash dot), 0.15 wt. % Cu 2 () (dashed), and 0.1 75 wt. % C3 ⁇ 40 (solid), respectively.
  • struck-black samples exhibit 0% to 5% transmission at wavelengths between 200 nm and 390 nm (ultraviolet light), 0% to 10% transmission at wavelengths between 390 nm and 675 nm (visible light), and 30% to 65% transmission at wavelengths between 750 nm and 850 nm (infrared light). Therefore, a struck-black glass container formed b doping a cobalt blue glass with suitable amounts of the disclosed latent colorant materials transmits a sufficient amount of infrared light so as to be inspected by infrared inspection equipment.

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Abstract

A soda-lime-silica glass container (10) related methods of manufacturing. A black-strikable glass composition having a base glass portion and a latent colorant portion is prepared. The base glass portion Includes soda-lime-silica glass materials and one or more blue colorant materials, and the latent colorant portion includes cuprous oxide (Cu2O), stannous oxide (SnO), bismuth oxide (Bi2O3), and carbon (C). Glass containers may be formed from, the back-strikable glass composition, and these glass containers may be heated to a temperature greater than 600 degrees Celsius to strike black therein. The glass containers formed from the black - strikable glass composition may be inspected before or after striking--by infrared inspection equipment.

Description

INSPECT ABLE BLACK GLASS CONTAINERS
The present disclosure is directed to glass containers and, more particularly, to coloring of glass containers.
Background ami Summary of the Disclosure
Glass containers are often composed of so-called soda-iime glass, also called soda-lime-silica glass. Many such containers are colored, for example, for aesthetic or functional purposes. Colored glass containers may be produced from soda-lime glass compositions which include one or more colorants. For example, blue glass containers can be made from soda-iime glass compositions which include cobalt oxide (CoO) as a colorant U.S. Patents that illustrate colored glass compositions of this type include 3,326,702, 3,330,638, 3,345,190, 3,498,806, and 4,312,953.
Some colorants in soda-lime glass do not immediately impart color to the glass. Instead, color may need to be developed in the colorant-containing glass by a heat-treatment process known as "striking." In this process, glass containers are formed from a glass composition which contains "latent" colorants. Thereafter, the glass containers are heated to a temperature slightly above normal annealing temperatures so that the latent colorants in the glass interact or "strike" to impart color to the glass. U.S. Patents that illustrate this method of coloring glass containers include 2,672,423, 3,513,003, and/or 3,627,548.
A general object, in accordance with one aspect of the disclosure, is to provide a glass composition that may be used to produce cobalt blue glass containers that, upon heat treatment and striking, develop a visually black color. Accordingly, this glass composition and the glass containers formed therefrom may be referred to as "bkck-strikable." The glass containers may be inspected— before or after striking -by infrared inspection equipment in a glass container production line or in a container filling operation. Accordingly, these glass containers also may be referred to as "inspectable." Until now, the optical inspection of black glass containers had been thought impossible due to their low percentage of light transmission.
The present disclosure embodies a number of aspects that can be implemented separately from or in combination with each other.
In accordance with an aspect of the disclosure, there is provided a method of making a black-strikable glass container. In this method, a black-strikable glass composition is prepared having a base glass portion and a latent colorant portion. The base glass portion includes: 60-75 wt. % Si02, 7-15 wt. % Na20, 6-12 wt. % CaO, 0.1-3.0 wt. % A1203, 0.0-2.0 wt. % MgO, 0.0-2.0 wt. % K20, 0.01-0.25 wt. % S03, 0.01-0.25 wt. % Fe203, and 0.01-0.15 wt. % CoO. The latent colorant portion includes: 0.0875-0.35 wt. % cuprous oxide (Cu20), 0.06-0.5 wt. % stannous oxide (SnO), 0.006-0.05 wt. % bismuth oxide (Bi203), and 0.02-0.10 wt. % carbon (C). Thereafter, a black-strikable glass container is formed from the black- strikable glass composition.
In accordance with another aspect of the disclosure, there is provided a method of inspecting a black glass container for commercial variations that affect optical characteristics of the glass container, in this method, infrared light energy is directed onto and through the black glass container, and is received on an infrared light sensor. The infrared light sensor Is responsive to infrared light energy received thereon having wavelengths in the range of 750- 1100 run. The disclosure, together with additional objects, features, advantages and aspects thereof, will be best understood from the following description, the appended claims and the accompanying drawings, in which:
FIG. 1 is a side elevation of a glass container in accordance with an exemplary embodiment of the present disclosure; and
FIG, 2 is a graphical plot of light transmission through samples of inspectabie struck-black container glass doped with three different amounts of copper oxide (Ο¾0).
Detaikd Description of Preferred Embodiments
FIG. 1 illustrates an exemplary embodiment of a glass container 10 (e.g., glass bottle, jar, or the like) that may be produced in accordance with an exemplary embodiment of a presently disclosed manufacturing process, as described further herein below. The glass container 10 may be referred to as "inspectabie," meaning that the glass container 10 transmits a sufficient amount of infrared light to be inspected by infrared inspection equipment in a glass container production, line or in a container filling operation.
The glass container 10 may be produced by the following method. Additional exemplary conditions and procedures for composing and melting production container glass can be found in, e.g. the Handbook of Glass Manufacture by Fay V. Tooley (3rd ed., Ashlee Publishing 1984).
The method may include preparing a black-strikable glass composition. The black-strikable glass composition may be thought of as having a base glass portion and a latent colorant portion. lie base: glass portli inbl ®. mH& im&~ \io& glass materials and one or mofre blue >k*m matedals. For ex n k;, the b se: glass p tl ii may incliide slsbstanriaily t same iB eria!S: present in cobalt Mm glass,
The term "sofealt blue glass1' m employed in its conveofenat sens m glass technolog as rferring to a glass ;havimg Mm eoi a o&Ce. ., blue glass). A presently preferre cobalt him glass may comprise the following materials in the: Mowin ranges of am» i¾s b weig!it:
60-75% SlO¾:
7-15%
6-12% CaO
0F~3.O Ah;C¾
O W* gO
O.ft--2,0% ¾
0,01-0.25%
0,01 --0.25%
0.01 0.15% Coi
More artietiiariy, and by way of ejcampl only, a preseatSy preferred eobali blue; glass a comprise the following materials in substantially the stated amounts b weight:
Figure imgf000006_0001
13% Na2<>
11% CaO:
1.6% Al2i¾:
0.5% MgO 0.4% K20
0.15% S03
0.10% Fe203
0.06% CoO.
The latent colorant portion of the black-strikable glass composition may include cuprous oxide (C112O), stannous oxide (SnO), bismutii oxide (ΒΪ2Ο3), and carbon (C), as this combination of materials has been found to enable the striking of copper (Cu) in soda-lime glass containers.
The molar ratio of tin oxide (SnO) to copper oxide (C¾Q) in the latent colorant portion may be about one, for example, the molar ratio may be in the range of 0.9 to 1 , or in the range of about 1 to 0.9. However, the latent colorant portion suitably may contain an excess of tin oxide (SnO). For example, when a excess of tin oxide (SnO) is present in the latent colorant- portion, the molar ratio of tin oxide (SnO) to copper oxide (C¾0) may be about 1.5.
In one embodiment, the black-strikable glass composition may include about 0.175 vvt. % cuprous oxide (Cu20), about 0,25 wt. % stannous oxide (SnO), about 0.0125 wt. % bismuth oxide (ΒΪ2Ο3), and about 0.06 wt. % carbon (C). For example, the black-strikable glass composition may include 0.0875-0.35 wt. % cuprous oxide (0¾0), 0.06-0.5 wt. % stannous oxide (SnO), 0.006-0.05 wt. % bismuth oxide (Bi203), and 0.02-0.10 wt. % carbon (C). In another embodiment, the black-strikable glass composition may include substantially 0.175 wt. % cuprous oxide (Cu20), substantially 0.25 wt. % stannous oxide (SnO), substantially 0.0125 wt. % bismuth oxide
Figure imgf000007_0001
and substantially 0.06 wt. % carbon (C). As used herein the term "substantially" means within manufacturing tolerances customary in the glass container manufacturing industry. The remaining portion of black-strikable glass composition may include small amounts of other materials. Such materials may be additives, residual materials from euliet and/or impurities typical in the glass container manufacturing industry. Such materials may be present in trace amounts, for example, less than 0.2 wt %. In one specific example, the remaining portion of the black-strikable glass composition may include trace amounts of TiO?, BaO, and/or SrO.
The method also may Include forming black-strikable glass containers from the black-strikable glass composition. A feeder located at a downstream end of the one or more forehearths may be used to measure ou gobs of molten glass and to deliver them to glass container-forming machines. Thereafter, the gobs may be formed into glass containers, for example, by press-and-hiow or blow-and-blow processes and by individual section machines, or in any other suitable manner by any suitable equipment.
The method further may include annealing the black-strikable glass containers in any suitable manner, for example, in an annealing le r. At an entry, hot end, or upstream portion of the annealing lehr, the temperature therein may be between 550 and 600 degrees Celsius. Through the lehr, the temperature may be brought down gradually to a downstream portion, cool end, or exit of the lehr, for example, to a temperature therein of between 130 degrees Celsius and 65 degrees Celsius. In any event, the glass containers may be annealed, preferably between 550 and 600 degrees Celsius for 30 to 90 minutes, more preferably between 525 and 575 degrees Celsius for 45 to 75 minutes, and most preferably at substantially 550 degrees Celsius for one hour.
The method also may include raising the temperature of the black-strikable giass containers above the highest temperature at which they are amiealed (i.e., the highest annealing temperature) to strike black coloration into the glass containers. Accordingly, this temperature- raising step may be referred to as "striking,"
The striking or temperature-raising step may include, for example, heat-treating the glass containers between 600 and 680 degrees Celsius for 10 to 90 minutes to produce black glass containers. In a more specific example, the temperature-raising step may include heat- treating the black-strikable glass containers between 630 and 650 degrees Celsius for 30 to 40 minutes.
In one embodiment, the temperature raising or striking step may be carried out after the annealing step. For example, a furnace or secondary lehr may be used, in line or off line downstream of the annealing lehr. The temperature of the glass containers may be raised in the furnace or secondary lehr to a temperature and for a lime suitable to strike black into the glass containers. Thereafter, the temperature of the black glass containers may be brought down gradually, for example, according to an annealing schedule to avoid fracture or failure of the containers.
in another embodiment, the temperature raising or striking step may be carried out between the time the annealing step begins and the time the annealing step ends. In one example, a separate furnace may be used off line adjacent to the annealing lehr, in another example, the annealing lehr may be operated in accordance with a modified heating profile. For instance, the modified heating profile may include a typical annealing temperature profile modified to include temperatures and times suitable to strike black into the glass containers before, during, or after annealing.
The black-strikable glass containers may, in some respects, have a container glass composition that is different from the black-strikable glass composition. For example, the amount of sulfur trioxide (SO3) retained in the glass containers may be substantially less than the amount of sulfur trioxide (SO3) in the black-strikable glass composition. The actual amount of sulfur trioxide (SO3) retained in the glass containers will vary depending on the amount of carbon (C) in the black-strikable glass composition. In suitable embodiments, the amount of sulfur trioxide (SO3) retained in the glass containers will be in the range of 0.01 to 0.22 wt. %. In general, the more carbon (C) in the black-strikable glass composition, the less sulfur trioxide (SO3) will be retained in die glass containers. As another example, the latent colorant materials of C¾0, SnO, and B12O3 may be largely retained in the container glass composition. For example, about 75-100% of the Cu20, SnO, and B12Q3 in the black-strikable glass composition may be retained in the container glass composition.
A struck-black glass container produced in accordance with this disclosure may have a wall thickness of greater than 0.040 inches (i.e., greater than about 1 mm). At this wall thickness, the glass container transmits a minimal amount of light at wavelengths between 390 mil and 700 nm and, thus, appears visually black to the human eye in natural lighting conditions (e.g.. indirect sunlight) at arm's length. For example, a struck-black glass container produced in accordance with this disclosure may transmit light in an amount less than 10 % at wavelengths between 390 nm and 675 nm.
At the same time, a struck-black glass container produced in accordance with, this disclosure transmits infrared light in the near-infrared region of the electromagnetic spectrum (e.g., from about 750 nm to 1 100 nm) and, thus, may be inspected by infrared inspection equipment in a glass container production line or in a container filling operation. For example, a struck-black glass container produced in accordance with this disclosure may transmit light in an amount between about 30 % and about 65 % at wavelengths between 750 nm and 850 nm. in one specific example, a struck-black glass container produced in accordance with this disclosure may transmit light in an amount of at least 40 % at a wavelength of 750 nm.
Glass containers produced in accordance with this disclosure may be inspected- either before or after striking— to detect for commercial variations in the glass. Such commercial variations may include, for example, dimensional anomalies in the sidewalls, heels, bottoms, shoulders, and/or necks of the glass containers, as well as inhomogeneities in the glass itself that affect the optical properties of the glass containers. Some of these commercial variations may be within commercially acceptable standards or thresholds, while other variations may be outside of such standards or thresholds, and thus may be unacceptable.
A suitable apparatus for detection of commercial variations in a glass container produced in accordance with ibis disclosure includes a light source, a Sight receiver, and an information processor, The light source may include a lamp or a laser capable of emitting infrared light in the near-infrared region of the electromagnetic spectrum (e.g., from about 750 mil to 1100 nm), and the light receiver may include a laser optic sensor responsive to light energy at wavelengths in the range of about 750 nm to 1 100 nm.
A glass container produced in accordance with this disclosure may be inspected by directing light energy from an infrared, light source through the glass container and onto a light sensor. In one embodiment, infrared light in the near-infrared region of the electromagnetic spectrum may be directed through the glass container and onto the light sensor. In another embodiment, inf ared light at wavelengths in the range of about 750-850 nm may be directed through the glass container and onto the light sensor, h response, the light sensor may provide electrical signals to an information processor, which may analyze the electrical signals to determine whether the glass container is commercially acceptable or unacceptable. Before the present discovery, no known commercially available black glass containers were believed to be capable of inspection using an infrared light source.
According to the present disclosure, a black-strikable glass composition is provided that may be used to produce cobalt blue glass containers and optionally black glass containers by the process of "striking.'' In addition, the glass containers produced according to the present disclosure may be inspected- -before or after striking by infrared inspection equipment in a glass container production line or in a container filling operation.
Several glass test samples were prepared in a laboratory environment and color was observed in each sample.
EXAMPLE 1
In the following example, a batch of raw materials was prepared and used to produce 300g of molten glass. The batch of raw materials included the necessary raw materials to produce a black-strikable glass composition. The necessary amount of each raw material for the batch was weighted out in accordance with standard batch caiculation practice common in the glass industry. Thereafter, the raw materials were crushed and ground using a mortar and pestle to break up agglomerate material, and then mixed together using a mixer for about ten minutes. While mixing, a crucible was pre-heated in a furnace at 1350 degrees Celsius for about ten minutes. The crucible was removed from the furnace and the entire batch of raw materials was added to the crucible. The crucible was again placed in the furnace, and the temperature of the furnace was increased to form a glass melt having a temperature of about 1450 degrees Celsius. The glass melt was held at that temperature for about 3.5 hours.
Thereafter, the molten glass was poured into splat quenched patties. Some of the patties were placed in an annealing oven at 550 degrees Celsius, and some of the patties were left unannealed. The patties which were placed in the annealing oven were annealed at a temperature of about 550 degrees Celsius for about 10 to 20 minutes, and then a door of the annealing oven was cracked open until the annealing oven temperature decreased to a temperature of about 300 degrees Celsius. Thereafter, the annealing oven temperature was set to 20 degrees Celsius to let the glass cool down to room temperature overnight.
After the black-strikable glass patties were annealed, they were heat treated at oven temperatures of 550, 600, and 650 degrees Celsius for durations of 15 to 90 minutes. At 600 and 650 degrees Celsius, the samples struck black by 30 minutes.
FIG. 2 illustrates three plots of Transmission (%) vs. Wavelength (run) through samples of cobalt blue glass doped with suitable amounts of the disclosed latent colorant- materials. However, each of the samples was doped with a different amount of copper oxide (Cu20). The three plots illustrate samples doped with 0.12 wt. % Cu20 (dash dot), 0.15 wt. % Cu2() (dashed), and 0.1 75 wt. % C¾0 (solid), respectively. As shown, these struck-black samples exhibit 0% to 5% transmission at wavelengths between 200 nm and 390 nm (ultraviolet light), 0% to 10% transmission at wavelengths between 390 nm and 675 nm (visible light), and 30% to 65% transmission at wavelengths between 750 nm and 850 nm (infrared light). Therefore, a struck-black glass container formed b doping a cobalt blue glass with suitable amounts of the disclosed latent colorant materials transmits a sufficient amount of infrared light so as to be inspected by infrared inspection equipment.
There thus has been disclosed suitable methods of producing a black-strikable glass composition and black-strikable glass containers that fully satisfy all of the objects and aims previously set forth. The disclosure has been presented in conjunction with several exemplary embodiments, and additional modifications and variations have been discussed. Other modifications and variations readily will suggest themselves to persons of ordinary skill the art in view of the foregoing discussion,.

Claims

1.
A met od sf niaking
Figure imgf000015_0001
glass container (lO), th&fcaetfeod including the steps of:
preparing a Maefc-smkafole glass composition, having a base glass portion and . latent colorant portion, taeis the base glass portion includes: 60-75 wt %: Sii¾, 7-15 wt. ¾ Na ¾ (5-12 w % CaO, 0.1 3.0 wt. ¼ AMK 0.0-2 0 wt. % MgO, 0.0-2.0 wt % KjC), 0.01 - 0.25 , % S<>3, 0.01 -0,25 wt. % i¾Oi> and O.Oh-OJ S wt.. % CoO and the latest - colorant portion includes Ml.&-0 wt. % enprons: oxide (¾<¾, 0.0 -0.5 ¾¾. % stannous oxide (SnOX 0.006-0.05 wt. bismuth oxide f& O$> and 0.02-0.1 i. % carbon (<¾ and
forming the black-sirikabl glass container from the black-sirikable glass composition,
7.
The method set finth in claim I hicludmg the additional siep of:
raising the tesnpemiure of the biaek-strikable g ss . container above 600 degrees Cefeins to strike Mack -eoloraO ri into the glas container,
3,
The method set forth in .claitft 3 wherein: the: temperature of the hiaek-strikab!e: glass container is raised for 10 to 90 r naies to strike black coloration into the glass container..
4.
The■■■method set forth, m e!airrs. 1 nc udin the additional step Q!V
raisfog the lemrieratare o the., biaek-sirikah!s glass container t a temper tu e between 30 md 65ί¾ degrees Celsius to strike blaefc coiar&don into th glass container.
Th method ssst forth, hi claim, wherefo. the tempe tur of the
Figure imgf000016_0001
¾l.ass container Is raised .l¾r:30 to 40 minutes to strike Mack coloration into the glass container.
A glass o jiiaiacF (19} produced by th method set forth, in claim 1; having, bine coloration.
A glass container (10) produced bv the raeihod set forth m claim 2 having Mack coloration.
s.
A tnet od oi inspecting a black glass continer (10) lor commercial, variations mat
Figure imgf000017_0001
ste s ¾>i
directing infrared light en r y OatO the black glass contalne-t; and receiving ¾h¾re light energy from the Mad lass co¾ainer om inferred light sensor,, the infrare .'light sensor 'being responsive to . J ared Iigbt; energy havin ¾¾:vel ng ihs ¼ the tmmM'TSQ. «m ΐο II 00 nm.
The method as set iorth in claim 8, whereto, the infrared fight sensor is a laser optic sensor and is responsive to intrared liglit energy having w¾veleitgths in th¾; range of 750 ran to 850 ran.
10.
The t ei&od set forth, in c tn S including the additional steps of; prrmdlpg e!ectrieai signal ftom the nfared light se s r to an jniorffiadon processor in response to infrared light energy received fens the black glass container; and
aaal v inii the etecirieal siana!s at the information, processor to deieimiae whether o mmoreial v ri tions in t e black glass container are acceptable or imaceeptaMe.
PCT/US2013/063205 2012-11-01 2013-10-03 Inspectable black glass containers WO2014070364A1 (en)

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EP13776688.7A EP2914556B1 (en) 2012-11-01 2013-10-03 Inspectable black glass containers
MYPI2018002629A MY196137A (en) 2012-11-01 2013-10-03 Inspectable Black Glass Containers
ES13776688T ES2959093T3 (en) 2012-11-01 2013-10-03 Inspectable black glass containers
CN201380057484.7A CN104870387B (en) 2012-11-01 2013-10-03 Checkable dark glass vessel
NZ705706A NZ705706A (en) 2012-11-01 2013-10-03 Inspectable black glass containers
SG11201502576UA SG11201502576UA (en) 2012-11-01 2013-10-03 Inspectable black glass containers
RU2015120555A RU2015120555A (en) 2012-11-01 2013-10-03 BLACK GLASS CONTAINERS AVAILABLE FOR INSPECTION
PE2019001463A PE20191399A1 (en) 2012-11-01 2013-10-03 INSPECTABLE BLACK GLASS CONTAINERS
AU2013338529A AU2013338529B2 (en) 2012-11-01 2013-10-03 Inspectable black glass containers
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CA2889167A CA2889167C (en) 2012-11-01 2013-10-03 Inspectable black glass containers
BR112015009590-9A BR112015009590B1 (en) 2012-11-01 2013-10-03 Method for making glass containers, black glass container, plurality of black glass containers, and method of inspecting the black glass container
MX2015005168A MX2015005168A (en) 2012-11-01 2013-10-03 Inspectable black glass containers.
EP23183233.8A EP4242643A3 (en) 2012-11-01 2013-10-03 Inspectable black glass containers
ZA2015/01778A ZA201501778B (en) 2012-11-01 2015-03-16 Inspectable black glass containers
PH12015500748A PH12015500748A1 (en) 2012-11-01 2015-04-06 Inspectable black glass containers
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