WO2006120663A2 - Soda lime glass compositions and process for manufacturing containers from said compositions - Google Patents

Soda lime glass compositions and process for manufacturing containers from said compositions Download PDF

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Publication number
WO2006120663A2
WO2006120663A2 PCT/IE2006/000057 IE2006000057W WO2006120663A2 WO 2006120663 A2 WO2006120663 A2 WO 2006120663A2 IE 2006000057 W IE2006000057 W IE 2006000057W WO 2006120663 A2 WO2006120663 A2 WO 2006120663A2
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WO
WIPO (PCT)
Prior art keywords
weight
glass
composition
soda lime
lime glass
Prior art date
Application number
PCT/IE2006/000057
Other languages
French (fr)
Other versions
WO2006120663A3 (en
Inventor
Chris Todd
John Parkes
Sharon Crayton
Original Assignee
Heye Research And Development Limited
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Publication date
Priority claimed from IE20050313A external-priority patent/IES20050313A2/en
Application filed by Heye Research And Development Limited filed Critical Heye Research And Development Limited
Publication of WO2006120663A2 publication Critical patent/WO2006120663A2/en
Publication of WO2006120663A3 publication Critical patent/WO2006120663A3/en

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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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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
    • 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
    • C03C4/04—Compositions for glass with special properties for photosensitive 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
    • C03C4/08—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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass

Definitions

  • the present invention relates to soda lime glass compositions, specifically container glass compositions, that include rare earth elements that affect the light transmission properties of soda lime glass and to a process for manufacturing containers made from the compositions.
  • flint glass containers which absorb U.V. light and prevent degradation of the product held in the container, thereby providing an alternative to using amber glass containers.
  • the Rare Earth Elements are made up of two series of elements, namely, the Lanthanide and Actinide Series.
  • the Rare Earth Elements consist of the following elements:
  • the present invention provides soda lime glass compositions for producing glass containers having pre-determined light transmission properties, the compositions including at least one rare earth element or a compound thereof in an amount ranging from 0.3 to 10% by weight of the total composition so as to affect the light transmission properties of the glass.
  • the soda lime glass compositions of the present invention provide a container glass composition that causes a container produced therefrom to fluoresce.
  • the soda lime glass compositions of the present invention may provide a container glass composition that causes a dichroic effect in a glass container produced therefrom.
  • the soda lime glass compositions of the present invention include at least one rare earth element or a compound thereof in an amount ranging from 0.3% to 10% by weight of the total composition so as to affect the light transmission properties of the glass to provide U.V. absorbing and/or fluorescent and/or dichroic glass.
  • the at least one rare earth or compound thereof may be included in the soda lime glass composition in an amount ranging from 1.5% to 10% by weight of the total composition.
  • the at least one rare earth or compound thereof is included in an amount ranging from 2% to 10% by weight of the total composition.
  • the at least one rare earth element may be included in the form of the elemental oxide.
  • the present invention thus has the advantage that it provides glass container compositions, particularly for flint glass containers used for holding beverages or food stuffs.
  • the containers produced using the glass compositions of the present invention are substantially transparent.
  • glass containers produced from the compositions of the present invention absorb U.V. light yet are substantially transparent, having a yellow tint and protect contents of the container from damaging U.V. light.
  • the light transmission properties of the glass produced from the compositions of the present invention are affected so as to provide U.V. absorbing and/or fluorescent and/or dichroic glass.
  • Each individual rare earth element will produce a specific optical effect in the base glass. These effects can be exploited in certain applications. When used in combination, the inclusion of certain rare earth elements produce the desired effect. For instance, the addition of Praseodymium (Pr) and Neodymium (Nd) in the glass composition will result in producing strong dichroic glass.
  • Pr Praseodymium
  • Nd Neodymium
  • Cerium (Ce), Praseodymium (Pr), Neodymium (Nd) and Erbium (Er) are of particular use for influencing colour in flint glass.
  • soda lime glass compositions including rare earth elements or compounds thereof with other elements, preferably, Titanium or compounds thereof.
  • rare earth elements such as cerium
  • compounds thereof especially oxides thereof
  • Titanium or compounds thereof provides an advantageous U.V. absorbing effect.
  • the rare earth elements do not have to be pure and may include some contaminants that do not adversely affect the glass making process.
  • one or more of the following rare earth elements is included within the range indicated below so as to produce the desired U.V. protective, dichroic and/or fluorescent glasses:
  • compositions of the soda lime glass which are capable of blocking ultraviolet (U.V.) light and which fluoresce include the following components within the ranges indicated:
  • Er Erbium
  • Pr Praseodymium
  • Praseodymium (Pr) oxide is included in the range of 0.6% to 10% by weight and Erbium oxide is included in the range of 0.5% to 10% by weight.
  • compositions of soda lime glass which demonstrates dichroic properties includes the following components within the ranges indicated:
  • glass compositions of the present invention include one or more of the following group: a rare Earth element such as Cerium (Ce) or compounds thereof and Titanium (Ti) or compounds thereof.
  • a rare Earth element such as Cerium (Ce) or compounds thereof
  • Titanium (Ti) or compounds thereof Preferably, Titanium or a compound thereof, (for example, Titanium dioxide) is included in an amount of between 2.0% to 10% by weight of the total composition.
  • the glass compositions comprise cerium oxide and Titanium oxide.
  • the ingredients are included in an amount within the following ranges:
  • An alternative embodiment in accordance with the invention provides U. V. protective green glass.
  • the composition of the green glass having U. V. protective properties includes the following ingredients in the ranges indicated:
  • the components are added within the ranges shown with the sum total adding up to 100% by weight, including elemental oxides whose percentage lies under practical detection limit.
  • a rare earth element such as Cerium (Ce) together with Titanium (Ti), in the correct formulations, can produce a shift in the U.V. edge thereby reducing U.V. transmission to a minimum.
  • Specific identified wavelengths can be excluded from the glass by use of the other rare earth elements in the glass composition of the present invention, depending on the desired performance of the glass.
  • Ceria will also fluoresce into the blue region, and this may be the one of most interest, but there are requirements to control the glass chemistry.
  • Uranium also gives excellent green/yellow fluorescence in soda lime silica glasses but has issues for commercial uses because of its radioactivity. However, a lot of the citron yellow glass from the 50's and 60's is based on adding uranium to the glass.
  • the present invention also provides a process for manufacturing a soda lime glass having desired light transmission properties, the process comprising the step of including in the composition at least one rare earth element, or a compound thereof in an amount ranging from 0.3 to 10% by weight of the total composition so as to affect the light transmission properties of the glass to provide U.V. absorbing and/or fluorescent and/or dichroic glass.
  • the at least one rare earth element is included in the form of the elemental oxide.
  • the process includes feeding the ingredients into a melting chamber of a furnace, melting the ingredients in the furnace to produce a melt consisting of molten glass, and subsequently passing the melt through a furnace throat into distribution channels for subsequent forming.
  • the process includes a refining step comprising controlling temperature gradient inside the furnace so as to control the viscosity of the melt.
  • the process includes the step of adding sulphates so as to encourage the formation of bubbles of sulphur dioxide (SO 2 ) gas which rise to the surface thereby enhancing the refining process.
  • SO 2 sulphur dioxide
  • Figure 1 is a schematic diagram of the regenerative furnace included in the apparatus used for producing the soda lime glasses in accordance with the present invention
  • FIG. 2 is a further schematic diagram of the furnace
  • Figure 3 is a schematic diagram of the forehearth of the apparatus
  • Figure 4 is a schematic diagram of the feeder of the apparatus
  • Figure 5a, b, c are schematic diagrams showing formation of different shapes of containers using a container forming apparatus
  • Figure 6 is a graphical representation of the annealing process
  • Figure 7 is a light transmission curve for fluorescent glass of the composition described in Example 1 hereinbelow;
  • Figure 8 is a light transmission curve for the glass with dichroic properties of the composition described in Example 2 hereinbelow; and Figure 9 is a light transmission curve for the glass with U.V. protective properties and having the composition of Example 3 hereinbelow.
  • the apparatus 1 includes raw material silos 2 (for clarity, only one silo is shown in the drawing).
  • the apparatus 1 also includes a regenerative furnace 3 having an entry port 4 and an exit port 5.
  • Raw materials are fed into the furnace 3 through the entry port 4 and the raw materials are melted to produce molten glass within the furnace.
  • the temperature of the molten glass is 1500 0 C in the lower half of the furnace.
  • a combustion chamber which includes firing ports 6.
  • the furnace includes a narrowed section 10, known as "the throat”.
  • the feeder is indicated generally by reference numeral 13 and consists of a plunger 130 moveable within a chamber 131.
  • the feeder 13 also includes an orifice ring 132 and a shearing mechanism consisting of two reciprocating blades 133, 134 for breaking off a measured amount of molten glass.
  • a "gob" of molten glass 15 is then delivered to the glass making apparatus for forming into a container of predetermined shape, as shown in Figures 5a, 5b and 5c.
  • the formed bottles are then annealed in an apparatus called a lehr indicated generally by reference numeral 20.
  • the bottles are passed along a conveyor line from the hot end 21 to the cold end 22 of the lehr 20.
  • the charging operation consists of the feeding of mixed batch (Sand, Soda Ash, Limestone, and Gullet etc) into the rear of the furnace melting chamber.
  • This furnace melting chamber comprises a rectangular refractory box, including the lower half which comprises the molten glass, glass bath and the upper half which comprises the combustion space.
  • the mixed batch is charged into the furnace 3 to match the rate that melted glass is being drawn off at the bottle forming apparatus.
  • the charging system is controlled to ensure a uniform batch cover across the width of the furnace 3 and also at a consistent depth.
  • the melting operation begins.
  • the melting operation takes place over the first two-thirds of the furnace 3, and the main source of heat comes from flames in the combustion space above the batch.
  • the flame temperature is higher than that of the furnace structure, the batch piles and molten glass. Heat is therefore transferred by radiation and convection, from the flames to the furnace structure, batch piles and the molten glass.
  • the main mode of heat transfer is by radiation. Below glass level, heat is transferred to the underside of the batch by radiation, conduction and convection from the molten glass.
  • Temperature distribution inside a furnace is not uniform, and therefore differences in temperature give rise to temperature gradients, which in turn encourage convection currents to be established both laterally and longitudinally in the glass bath.
  • the refining stage is concerned with the removal of bubbles from the melt.
  • gases become entrained in the batch material and also evolve from reactions in the glass melt.
  • These bubbles contain various percentages of CO 2 , SO 2 , etc although the highest percentage is usually CO 2 .
  • influence can be exerted over the molten glass viscosity since the viscosity decreases with increasing temperature. Controlled temperature gradients encourage bubbles to rise to the surface, coalescing with smaller bubbles as they rise upwardly and also combining with other bubbles thereby increasing buoyancy and rate of rise. This thermal refining process is enhanced by the addition of sulphates to the batch.
  • the molten glass is ready to be fed into the distribution channels via the furnace throat ready for temperature conditioning.
  • compositions of the present invention which would produce glass containers capable of absorbing ultraviolet (U.V.) light and which fluoresce include the following components within the ranges indicated:
  • composition for dichroic glass is as follows:
  • a further example of a composition for a dichroic glass composition is as follows:
  • An alternative embodiment in accordance with the invention provides U. V. protective green glass.
  • the formulation for the green container glass having U.V. absorbing properties which provide protection for contents of the container from degradation by U.V. lignt is as follows:
  • the components are added within the ranges shown with the sum total adding up to 100% by weight, including elemental oxides whose percentage lies under practical detection limit.
  • a further example of a composition for green U. V. protective glass is as follows:
  • the rare earth elements do not have to be pure but may have such other contaminants that are not detrimental to the glass making process. It will of course be understood that the present invention is not limited to the specific details herein described which are given by way of example only, and that various alterations and modifications may be made without departing from the scope of the invention as defined in the appended claims.

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  • 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)

Abstract

The invention relates to soda lime glass compositions for producing glass containers having pre-determined light transmission properties, the composition including at least one rare earth element or a compound thereof in an amount ranging from 0.3 to 10% by weight of the total composition so as to affect the light transmission properties of the glass to provide U.V. absorbing and/or fluorescent and/or dichroic glass. The invention also relates to a process for manufacturing soda lime glass containers using the above compositions.

Description

SODA LIME GLASS COMPOSITIONS AND PROCESS FOR MANUFACTURING CONTAINERS FROM SAID COMPOSITIONS
The present invention relates to soda lime glass compositions, specifically container glass compositions, that include rare earth elements that affect the light transmission properties of soda lime glass and to a process for manufacturing containers made from the compositions.
Glass packaged products which are light sensitive have traditionally been sold in amber glass containers. This was done so that ultraviolet (U.V.) light is absorbed through the glass and degradation of the product under the action of ultraviolet light was therefore avoided. Most beverages and many foodstuffs are prone to U.V. degradation resulting in loss of colour, affected taste and a greatly shortened shelf life.
Accordingly, it is an aim of the present invention to provide clear or coloured flint glass, particularly flint glass containers, which absorb U.V. light and prevent degradation of the product held in the container, thereby providing an alternative to using amber glass containers.
Applicants have found that rare earth elements when included in an appropriate amount in flint and green glass lead to production of glasses which block U.V. light. Applicants have also found that inclusion of certain rare earth element(s) in pre-determined amount(s) also cause a fluorescent effect in clear flint glass.
The Rare Earth Elements (REE) are made up of two series of elements, namely, the Lanthanide and Actinide Series.
The Rare Earth Elements consist of the following elements:
Lanthanide Series Actinide Series
• Lanthanum (La) • Actinium (Ac)
• Cerium (Ce) • Thorium (Th)
• Praseodymium (Pr) • Protactinium (Pa)
• Neodymium (Nd) • Uranium (U)
• Promethium (Pm) • Neptunium (Np) • Samarium (Sm) • Plutonium (Pu)
• Europium (Eu) • Americium (Am)
• Gadolinium (Gd) • Curium (Cm)
• Terbium (Tb) • Berkelium (Bk)
• Dysprosium (Dy) • Californium (Cf)
• Holmium (Ho) • Einsteinium (Es)
• Erbium (Er) • Fermium (Fm)
• Thulium (Tm) • Mendelevium (Md)
• Ytterbium (Yb) • Nobelium (No)
• Lutetium (Lu) • Lawrencium (Lw)
Accordingly, the present invention provides soda lime glass compositions for producing glass containers having pre-determined light transmission properties, the compositions including at least one rare earth element or a compound thereof in an amount ranging from 0.3 to 10% by weight of the total composition so as to affect the light transmission properties of the glass.
Ideally, the soda lime glass compositions of the present invention provide a container glass composition that causes a container produced therefrom to fluoresce.
Alternatively, the soda lime glass compositions of the present invention may provide a container glass composition that causes a dichroic effect in a glass container produced therefrom.
Preferably, the soda lime glass compositions of the present invention include at least one rare earth element or a compound thereof in an amount ranging from 0.3% to 10% by weight of the total composition so as to affect the light transmission properties of the glass to provide U.V. absorbing and/or fluorescent and/or dichroic glass.
Advantageously, the at least one rare earth or compound thereof may be included in the soda lime glass composition in an amount ranging from 1.5% to 10% by weight of the total composition.
Preferably, the at least one rare earth or compound thereof is included in an amount ranging from 2% to 10% by weight of the total composition. The at least one rare earth element may be included in the form of the elemental oxide.
The present invention thus has the advantage that it provides glass container compositions, particularly for flint glass containers used for holding beverages or food stuffs. Preferably, the containers produced using the glass compositions of the present invention are substantially transparent.
Thus, glass containers produced from the compositions of the present invention absorb U.V. light yet are substantially transparent, having a yellow tint and protect contents of the container from damaging U.V. light.
Advantageously, the light transmission properties of the glass produced from the compositions of the present invention, are affected so as to provide U.V. absorbing and/or fluorescent and/or dichroic glass.
Each individual rare earth element (REE) will produce a specific optical effect in the base glass. These effects can be exploited in certain applications. When used in combination, the inclusion of certain rare earth elements produce the desired effect. For instance, the addition of Praseodymium (Pr) and Neodymium (Nd) in the glass composition will result in producing strong dichroic glass.
Advantageously, Cerium (Ce), Praseodymium (Pr), Neodymium (Nd) and Erbium (Er) are of particular use for influencing colour in flint glass.
In another aspect of the invention, there is provided soda lime glass compositions including rare earth elements or compounds thereof with other elements, preferably, Titanium or compounds thereof. The combination of rare earth elements (such as cerium) or compounds thereof, (especially oxides thereof) with Titanium or compounds thereof provides an advantageous U.V. absorbing effect.
The rare earth elements do not have to be pure and may include some contaminants that do not adversely affect the glass making process.
The following is a conventional flint soda lime glass composition, to which rare earth elements or elemental oxides are added: SiO2 68 - 74% by weight
AI2O3 0.5 - 3.0% by weight
CaO 8.0 - 12.0% by weight
MgO 1.0 - 5.0% by weight Na2O 10.0 - 15.0% by weight
K2O 0.0 - 3.0% by weight
Fe2O3 0.0 - 0.5% by weight
SO3 0.01 - 0.6% by weight.
Advantageously, one or more of the following rare earth elements is included within the range indicated below so as to produce the desired U.V. protective, dichroic and/or fluorescent glasses:
Nd2O3 0.3 - 10.0% by weight CeO2 0.3 - 10.0% by weight
Pr2O3 0.3 - 10.0% by weight
Er2O3 0.3 - 10.0% by weight.
Preferably, the compositions of the soda lime glass which are capable of blocking ultraviolet (U.V.) light and which fluoresce include the following components within the ranges indicated:
SiO2 68 - 74% by weight
AI2O3 0.5 - 3.0% by weight CaO 8.0 - 12.0% by weight
MgO 1.0 - 5.0% by weight
Na2O 10.0 - 15.0% by weight
K2O 0.0 - 3.0% by weight
Fe2O3 0.0 - 0.5% by weight SO3 0.01 - 0.6% by weight
Pr2O3 0.5 - 10.0% by weight
Er2O3 0.4 - 10.0% by weight. The glass compositions of the invention containing the rare earth elements, Erbium (Er) and Praseodymium (Pr) in the form of their oxides, Er2O3 and Pr2O3, respectively, fluoresce a green/yellow colour under a U.V. light source.
Preferably, Praseodymium (Pr) oxide is included in the range of 0.6% to 10% by weight and Erbium oxide is included in the range of 0.5% to 10% by weight.
In an alternative embodiment of the glass in accordance with the invention, the compositions of soda lime glass which demonstrates dichroic properties includes the following components within the ranges indicated:
SiO2 68 - 74% by weight
AI2O3 0.5 - 3.0% by weight
CaO 8.0 - 12.0% by weight MgO 1.0 - 5.0% by weight
Na2O 10.0 - 15.0% by weight
K2O 0.0 - 3.0% by weight
Fe2O3 0.0 - 0.5% by weight
SO3 0.01 - 0.6% by weight Pr2O3 4.0 - 10.0% by weight
Nd2O3 3.0 - 10.0% by weight.
In an alternative embodiment, glass compositions of the present invention include one or more of the following group: a rare Earth element such as Cerium (Ce) or compounds thereof and Titanium (Ti) or compounds thereof. Preferably, Titanium or a compound thereof, (for example, Titanium dioxide) is included in an amount of between 2.0% to 10% by weight of the total composition.
Conveniently, the glass compositions comprise cerium oxide and Titanium oxide. Most preferably, the ingredients are included in an amount within the following ranges:
SiO2 68 - 74% by weight
AI2O3 0.5 - 3.0% by weight
CaO 8.0 - 12.0% by weight MgO 1.0 - 5.0% by weight
Na2O 10.0 - 15.0% by weight K2O 0.0 - 3.0% by weight
Fe2O3 0.0 - 0.5% by weight
SO3 0.01 - 0.6% by weight
CeO2 2.0 - 10.0% by weight TiO2 2.0 - 10.0% by weight.
An alternative embodiment in accordance with the invention provides U. V. protective green glass. The composition of the green glass having U. V. protective properties includes the following ingredients in the ranges indicated:
SiO2 68 - 74% by weight
AI2O3 0.5 - 3.0% by weight
CaO 8.0 - 12.0% by weight
MgO 1.0 - 5.0% by weight Na2O 10.0 - 15.0% by weight
K2O 0.0 - 3.0% by weight
Fe2O3 0.0 - 0.5% by weight
SO3 0.01 - 0.6% by weight
Cr2O3 0.0 - 1.0% by weight CeO2 2.0 - 10.0% by weight
TiO2 2.0 - 10.0% by weight.
The components are added within the ranges shown with the sum total adding up to 100% by weight, including elemental oxides whose percentage lies under practical detection limit.
The inclusion of a rare earth element such as Cerium (Ce) together with Titanium (Ti), in the correct formulations, can produce a shift in the U.V. edge thereby reducing U.V. transmission to a minimum. Specific identified wavelengths can be excluded from the glass by use of the other rare earth elements in the glass composition of the present invention, depending on the desired performance of the glass.
Advantageously, the following fluorescences are possible: (a) Inclusion of praseodymium (Pr) in the soda lime glass composition gives a number of results depending on the light source, white light will give yellow green fluorescence, and U.V. or green/yellow light is reported to give orange fluorescence,
(b) Neodymium (Nd) fluoresces red yellow in soda lime glasses,
(c) Europium (Eu) will fluoresce either a brilliant red or a weaker green depending on the chemistry of the glass,
(d) Samarium (Sm) will also cause the glass to fluoresce giving pink/orange light but the total iron content of the glass needs to be low to prevent the effect being 'quenched'.
(e) Ceria will also fluoresce into the blue region, and this may be the one of most interest, but there are requirements to control the glass chemistry.
(f) Uranium also gives excellent green/yellow fluorescence in soda lime silica glasses but has issues for commercial uses because of its radioactivity. However, a lot of the citron yellow glass from the 50's and 60's is based on adding uranium to the glass.
The present invention also provides a process for manufacturing a soda lime glass having desired light transmission properties, the process comprising the step of including in the composition at least one rare earth element, or a compound thereof in an amount ranging from 0.3 to 10% by weight of the total composition so as to affect the light transmission properties of the glass to provide U.V. absorbing and/or fluorescent and/or dichroic glass.
Preferably, the at least one rare earth element is included in the form of the elemental oxide.
Conveniently, the process includes feeding the ingredients into a melting chamber of a furnace, melting the ingredients in the furnace to produce a melt consisting of molten glass, and subsequently passing the melt through a furnace throat into distribution channels for subsequent forming.
Ideally, the process includes a refining step comprising controlling temperature gradient inside the furnace so as to control the viscosity of the melt.
Preferably, the process includes the step of adding sulphates so as to encourage the formation of bubbles of sulphur dioxide (SO2) gas which rise to the surface thereby enhancing the refining process.
The present invention will now be described more particularly with reference to the accompanying drawings.
In the drawings:
Figure 1 is a schematic diagram of the regenerative furnace included in the apparatus used for producing the soda lime glasses in accordance with the present invention;
Figure 2 is a further schematic diagram of the furnace;
Figure 3 is a schematic diagram of the forehearth of the apparatus;
Figure 4 is a schematic diagram of the feeder of the apparatus;
Figure 5a, b, c are schematic diagrams showing formation of different shapes of containers using a container forming apparatus;
Figure 6 is a graphical representation of the annealing process;
Figure 7 is a light transmission curve for fluorescent glass of the composition described in Example 1 hereinbelow;
Figure 8 is a light transmission curve for the glass with dichroic properties of the composition described in Example 2 hereinbelow; and Figure 9 is a light transmission curve for the glass with U.V. protective properties and having the composition of Example 3 hereinbelow.
The apparatus used for manufacturing the glass in accordance with the present invention will now be described:
Referring now to Figure 1 , the apparatus for manufacturing containers made of the compositions of the invention is indicated generally by the reference numeral 1. The apparatus 1 includes raw material silos 2 (for clarity, only one silo is shown in the drawing). The apparatus 1 also includes a regenerative furnace 3 having an entry port 4 and an exit port 5. Raw materials are fed into the furnace 3 through the entry port 4 and the raw materials are melted to produce molten glass within the furnace. The temperature of the molten glass is 15000C in the lower half of the furnace. In the upper half of the furnace there is a combustion chamber which includes firing ports 6.. The furnace includes a narrowed section 10, known as "the throat". Molten glass flows through the throat 10 to the working end 11 of the furnace and from there, the molten glass flows out the exit port 5 to one of three forehearths 12 (only one is showing in the drawings). The forehearth 12 delivers the molten glass to each of a number of feeders 13 (only one of which is shown in the drawings) each feeder then delivers the molten glass to a bottle making apparatus. In Figure 4, the feeder is indicated generally by reference numeral 13 and consists of a plunger 130 moveable within a chamber 131. The feeder 13 also includes an orifice ring 132 and a shearing mechanism consisting of two reciprocating blades 133, 134 for breaking off a measured amount of molten glass. This measured amount is referred to as a "gob" of molten glass 15. The "gob" of molten glass 15 is then delivered to the glass making apparatus for forming into a container of predetermined shape, as shown in Figures 5a, 5b and 5c. After being formed in the glass making apparatus in the manner shown in Figures 5a, 5b or 5c the formed bottles are then annealed in an apparatus called a lehr indicated generally by reference numeral 20. The bottles are passed along a conveyor line from the hot end 21 to the cold end 22 of the lehr 20.
Having described the apparatus used, the composition of the soda lime glasses of the invention and the process for production of the soda lime glasses will now be described in the following Examples: EXAMPLE 1
A composition for the U.V. protective an<
SiO2 70.76% by weight
AI2O3 1.25% by weight
CaO 11.70% by weight
MgO 1.12% by weight
Na2O 13.50% by weight
K2O 0.35% by weight
Fe2O3 0.08% by weight
SO3 0.14% by weight
Pr2O3 0.6% by weight
CeO 0.1% by weight.
The light transmission curve for the glass of this composition compared with that of known flint glass is shown in Figure 7.
The Glass Manufacturing Process
The process for manufacturing flint glass containers having U.V. and fluorescent properties is as follows:
When describing the glass manufacturing process for manufacturing containers it is useful to describe the process in four stages, namely, charging, melting, refining and homogenising.
1. Charging:
The charging operation consists of the feeding of mixed batch (Sand, Soda Ash, Limestone, and Gullet etc) into the rear of the furnace melting chamber. This furnace melting chamber comprises a rectangular refractory box, including the lower half which comprises the molten glass, glass bath and the upper half which comprises the combustion space. The mixed batch is charged into the furnace 3 to match the rate that melted glass is being drawn off at the bottle forming apparatus. The charging system is controlled to ensure a uniform batch cover across the width of the furnace 3 and also at a consistent depth.
2. Melting:
Once the mixed batch has been charged into the furnace, the melting operation begins. In the regenerative furnace, the melting operation takes place over the first two-thirds of the furnace 3, and the main source of heat comes from flames in the combustion space above the batch. The flame temperature is higher than that of the furnace structure, the batch piles and molten glass. Heat is therefore transferred by radiation and convection, from the flames to the furnace structure, batch piles and the molten glass.
The main mode of heat transfer is by radiation. Below glass level, heat is transferred to the underside of the batch by radiation, conduction and convection from the molten glass.
Temperature distribution inside a furnace is not uniform, and therefore differences in temperature give rise to temperature gradients, which in turn encourage convection currents to be established both laterally and longitudinally in the glass bath.
Along with the application of heat and the physical mixing of glass and batch by convection, there are also a number of chemical reactions taking place. As the batch temperature rises, the following reactions take place.
> Evaporation of free water from the materials
> Formulation and loss of gasses such as CO2, SO2 etc
> Formulation of liquids from the melting and reactions of individual batch materials.
The melting phase of the process is said to be complete when the molten glass is free of any unmelted material. 3. Refining:
The refining stage is concerned with the removal of bubbles from the melt. During the stages of charging and melting, gases become entrained in the batch material and also evolve from reactions in the glass melt. These bubbles contain various percentages of CO2, SO2, etc although the highest percentage is usually CO2. By controlling the temperature gradients inside the furnace, influence can be exerted over the molten glass viscosity since the viscosity decreases with increasing temperature. Controlled temperature gradients encourage bubbles to rise to the surface, coalescing with smaller bubbles as they rise upwardly and also combining with other bubbles thereby increasing buoyancy and rate of rise. This thermal refining process is enhanced by the addition of sulphates to the batch. As the sulphates decompose later in the melting process, bubbles of sulphur dioxide gas rise to the surface, collecting smaller bubbles, making the bubbles grow in size and resulting in the bubbles rising rise to the surface quicker, whilst some will be absorbed into the molten glass.
4. Homogenising:
At this stage the molten glass is ready to be fed into the distribution channels via the furnace throat ready for temperature conditioning.
EXAMPLE 1a
An example of the compositions of the present invention which would produce glass containers capable of absorbing ultraviolet (U.V.) light and which fluoresce include the following components within the ranges indicated:
SiO2 68 - 74% by weight
AI2O3 0.5 - 3.0% by weight CaO 8.0 - 12.0% by weight
MgO 1.0 - 5.0% by weight
Na2O 10.0 - 15.0% by weight
K2O 0.0 - 3.0% by weight
Fe2O3 0.0 - 0.5% by weight SO3 0.01 - 0.6% by weight Pr2O3 0.6% by weight
Er2O3 0.5% by weight.
EXAMPLE Ib A further example of a composition for fluorescent glass is
SiO2 71 % by weight
AI2O3 1 % by weight CaO 11 % by weight
MgO 2% by weight
Na2O 13% by weight
K2O 0.8% by weight
Fe2O3 0.03% by weight SO3 0.07% by weight
Pr2O3 0.6% by weight
Er2O3 0.5% by weight.
EXAMPLE 2
An example of a composition for dichroic glass is as follows:
SiO2 68.00% by weight
AI2O3 1.15% by weight
CaO 10.80% by weight
MgO 1.03% by weight
Na2O 12.46% by weight
K2O 0.32% by weight
Fe2O3 0.07% by weight
SO3 0.13% by weight
Pr2O3 3.30% by weight
Nd2O3 4.40% by weight.
The light transmission curve for the glass of this composition compared with that of known flint glass is shown in Figure 8. EXAMPLE 2a
A further example of a composition for a dichroic glass composition is as follows:
SiO2 69% by weight
AI2O3 0.6% by weight
CaO 10% by weight
MgO 1.8% by weight
Na2O 10% by weight
K2O 0.8% by weight
Fe2O3 0.03% by weight
SO3 0.07% by weight
Pr2O3 4.4% by weight
Nd2O3 3.3% by weight.
The process for production of the dichroic glass of the compositions indicated in Examples 2 and 2a is the same as that already described above in Example 1.
EXAMPLE 3
An example of a glass container composition which provides container glass with U.V. absorbing properties so that contents of the container are protected from degradation by U.V. light is as follows:
SiO2 68 - 74% by weight
AI2O3 0.5 - 3.0% by weight
CaO 8.0 - 12.0% by weight
MgO 1.0 - 5.0% by weight
Na2O 10.0 - 15.0% by weight K2O 0.0 - 3.0% by weight
Fe2O3 0.0 - 0.5% by weight
SO3 0.01 - 0.6% by weight
CeO2 2.0 - 10.0% by weight
TiO2 2.0 - 10.0% by weight. The light transmission curve for the glass of the composition of Example 3 compared with that of known flint glass is shown in Figure 9.
The process for production of this glass composition is the same as that described in Example 1.
EXAMPLE 3a
A further example with the ingredients within the ranges given in Example 3 is as follows:
SiO2 70% by weight
AI2O3 1 % by weight
CaO 9% by weight
MgO 2% by weight
Na2O 12% by weight
K2O 1.9% by weight
Fe2O3 0.03% by weight
SO3 0.07% by weight
CEO2 2% by weight
TiO2 2% by weight.
The process for production of this glass composition is the same as that described in Example 1.
EXAMPLE 4
An alternative embodiment in accordance with the invention provides U. V. protective green glass. The formulation for the green container glass having U.V. absorbing properties which provide protection for contents of the container from degradation by U.V. lignt is as follows:
SiO2 68 - 74% by weight
AI2O3 0.5 - 3.0% by weight CaO 8.0 - 12.0% by weight MgO 1.0 - 5.0% by weight
Na2O 10.0 - 15.0% by weight
K2O 0.0 - 3.0% by weight
Fe2O3 0.0 - 0.5% by weight SO3 0.01 - 0.6% by weight
Cr2O3 0.0 - 1.0% by weight
CeO2 2.0 - 10.0% by weight
TiO2 2.0 - 10.0% by weight.
The components are added within the ranges shown with the sum total adding up to 100% by weight, including elemental oxides whose percentage lies under practical detection limit.
The process for production of the glass compositions of Examples 4 and 4a is the same as that described in Example 1.
EXAMPLE 4a
A further example of a composition for green U. V. protective glass is as follows:
SiO2 70% by weight
AI2O3 0.7% by weight
CaO 9% by weight
MgO 2% by weight
Na2O 12% by weight
K2O 1.4% by weight
Fe2O3 0.03% by weight
SO3 0.07% by weight
Cr2O3 0.8% by weight
CeO2 2% by weight
TiO2 2% by weight.
In all the Examples, the rare earth elements do not have to be pure but may have such other contaminants that are not detrimental to the glass making process. It will of course be understood that the present invention is not limited to the specific details herein described which are given by way of example only, and that various alterations and modifications may be made without departing from the scope of the invention as defined in the appended claims.

Claims

CLAIMS:
1. A soda lime glass composition for producing containers having pre-determined light transmission properties, the composition including at least one rare earth element or compound thereof in an amount ranging from about 0.3% to about 10% by weight of the total composition so as to affect the light transmission properties of the glass.
2. A soda lime glass composition as claimed in Claim 1 which provides a container glass composition that causes a glass container produced therefrom to fluoresce.
3. A soda lime glass composition as claimed in Claim 1 which provides a container glass composition that causes a dichroic effect in a glass container produced therefrom.
4. A soda lime glass composition as claimed in Claim 1 , the composition including at least one rare earth element or a compound thereof in an amount ranging from 0.3% to 10% by weight of the total composition so as to affect the light transmission properties of the glass to provide U.V. absorbing and/or fluorescent and/or dichroic glass.
5. A soda lime glass composition as claimed in Claim 4 wherein the at least one rare earth or compound thereof is included in an amount ranging from 1.5% to 10% by weight of the total composition.
6. A soda lime glass composition as claimed in Claim 4 wherein the at least one rare earth or compound thereof is included in an amount ranging from 2% to 10% by weight of the total composition.
7. A soda lime glass composition as claimed in Claim 1 wherein the at least one rare earth element is included in the form of the elemental oxide.
8. A soda lime glass composition as claimed in any one of the preceding claims wherein the rare earth element comprises one or more of the following group: Cerium (Ce), Praseodymium (Pr), Neodymium (Nd) and Erbium (Er).
9. A soda lime glass composition as claimed in Claim 1 wherein the composition also includes other elements or compounds thereof of said elements, preferably, Titanium or compounds thereof.
10. A container glass composition as claimed in any one of the Claims 1 to 9, wherein one or more of the following rare earth elemental oxides are included within the range indicated below so as to produce the desired U.V. protective, dichroic and/or fluorescent glasses:
Nd2O3 0.3 - 10.0% by weight CeO2 0.3 - 10.0% by weight
Pr2O3 0.3 - 10.0% by weight
Er2O3 0.3 - 10.0% by weight.
11. A glass composition as claimed in any one of the preceding claims, wherein the composition includes the following components within the ranges indicated:
SiO2 68 - 74% by weight
AI2O3 0.5 - 3.0% by weight
CaO 8.0 - 12.0% by weight MgO 1.0 - 5.0% by weight
Na2O 10.0 - 15.0% by weight
K2O 0.0 - 3.0% by weight
Fe2O3 0.0 - 0.5% by weight
SO3 0.01 - 0.6% by weight Pr2O3 0.5 - 10.0% by weight
Er2O3 0.4 - 10.0% by weight.
12. A glass composition as claimed in any one of the preceding claims, wherein the composition includes the following components within the following ranges:
SiO2 68 - 74% by weight
AI2O3 0.5 - 3.0% by weight
CaO 8.0 - 12.0% by weight
MgO 1.0 - 5.0% by weight Na2O 10.0 - 15.0% by weight K2O 0.0 - 3.0% by weight
Fe2O3 0.0 - 0.5% by weight
SO3 0.01 - 0.6% by weight
Pr2O3 4.0 - 10.0% by weight Nd2O3 3.0 - 10.0% by weight.
13. A soda lime glass composition as claimed in any one of the preceding claims wherein the composition includes one or more of the following group: Cerium (Ce) or compounds thereof and Titanium (Ti) or compounds thereof.
14. A soda lime glass composition as claimed in Claim 13 wherein Titanium or a compound thereof, is included in an amount of between 2.0% and 10% by weight of the total composition.
15. A soda lime glass composition as claimed in Claim 13 wherein the composition includes the following ingredients in an amount within the ranges indicated:
SiO2 68 - 74% by weight
AI2O3 0.5 - 3.0% by weight CaO 8.0 - 12.0% by weight
MgO 1.0 - 5.0% by weight
Na2O 10.0 - 15.0% by weight
K2O 0.0 - 3.0% by weight
Fe2O3 0.0 - 0.5% by weight SO3 0.01 - 0.6% by weight
CeO2 2.0 - 10.0% by weight
TiO2 2.0 - 10.0% by weight.
16. A soda lime glass composition as claimed in Claim 1 wherein the composition includes the following ingredients in an amount within the ranges indicated:
SiO2 68 - 74% by weight
Al2O3 0.5 - 3.0% by weight
CaO 8.0 - 12.0% by weight MgO 1.0 - 5.0% by weight Na2O 10.0 - 15.0% by weight
K2O 0.0 - 3.0% by weight
Fe2O3 0.0 - 0.5% by weight
SO3 0.01 - 0.6% by weight Cr2O3 0.0 - 1.0% by weight
CeO2 2.0 - 10.0% by weight
TiO2 2.0 - 10.0% by weight.
17. A glass container manufactured from a composition as claimed in Claim 1.
18. A container as claimed in Claimi 7, that absorbs U.V. light yet is still substantially transparent and protects contents of the container from degradation due to U.V. light.
19. A container as claimed in Claim 18 wherein the container has a yellow tint.
20. A process for manufacturing soda lime glass having desired light transmission properties, the process comprising the step of including in the composition at least one rare earth element, or a compound thereof in an amount ranging from about 0.3 to about 10% by weight of the total composition so as to affect the light transmission properties of the glass.
21. A process as claimed in Claim 20 wherein the properties of the light transmission glass are affected so as to provide U.V. absorbing and/or fluorescent and/or dichroic glass and preferably wherein the process is a container glass manufacturing process.
22. A process as claimed in Claims 20 and 21 , wherein the at least one rare earth element is included in the form of the elemental oxide.
23. A process as claimed in any one of Claims 20 to 22, wherein the process includes the following steps:
(a) feeding the ingredients into a melting chamber of a furnace;
(b) melting the ingredients in the furnace to produce a melt consisting of molten glass; and (c) subsequently passing the melt through a furnace throat into distribution channels for subsequent forming.
24. A process as claimed in Claim 23, wherein between steps (b) and (c), the process includes a refining step comprising controlling temperature gradient inside the furnace so as to control the viscosity of the melt.
25. A process as claimed in Claim 24, further including the step of adding sulphates so as to encourage the formation of bubbles of sulphur dioxide (SO2) gas which rise to the surface, thereby enhancing the refining process.
PCT/IE2006/000057 2005-05-13 2006-05-11 Soda lime glass compositions and process for manufacturing containers from said compositions WO2006120663A2 (en)

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IE20050313A IES20050313A2 (en) 2005-05-13 2005-05-13 Soda lime glass compositions and process for manafacturing containers made from said compositions
GB0517777A GB2426005A (en) 2005-05-13 2005-09-01 Soda lime compositions and process for manufacturing containers from said compositions
GB0517777.9 2005-09-01

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WO2009150382A2 (en) * 2008-06-12 2009-12-17 Saint-Gobain Emballage Object made of hollow glass
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AU2009259115B2 (en) * 2008-06-12 2014-10-30 Saint-Gobain Emballage Object made of hollow glass
CN102363553A (en) * 2010-06-09 2012-02-29 肖特公开股份有限公司 Method for producing clear glass or clear drawn glass by utilizing special refining process
CN102363553B (en) * 2010-06-09 2015-11-25 肖特公开股份有限公司 Apply the method that specific defecation method prepares transparent glass or transparent drawn glass
CN104445932A (en) * 2014-12-10 2015-03-25 中国建材国际工程集团有限公司 Pink alumina silicate glass
CN104445932B (en) * 2014-12-10 2022-06-03 中国建材国际工程集团有限公司 Pink aluminosilicate glass
WO2017180811A1 (en) * 2016-04-14 2017-10-19 Corning Incorporated Multichroic glasses with praseodymium and neodymium
US11535549B2 (en) 2016-04-14 2022-12-27 Corning Incorporated Multichroic glasses with praseodymium and neodymium

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