WO2007006328A1 - Opacifying composition and process for the production of glass with an opal/stone effect or with a snow effect - Google Patents

Opacifying composition and process for the production of glass with an opal/stone effect or with a snow effect Download PDF

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Publication number
WO2007006328A1
WO2007006328A1 PCT/EP2005/007610 EP2005007610W WO2007006328A1 WO 2007006328 A1 WO2007006328 A1 WO 2007006328A1 EP 2005007610 W EP2005007610 W EP 2005007610W WO 2007006328 A1 WO2007006328 A1 WO 2007006328A1
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WO
WIPO (PCT)
Prior art keywords
oxides
glass
opacifying
effect
opal
Prior art date
Application number
PCT/EP2005/007610
Other languages
French (fr)
Inventor
Simone Baratta
Luigi Ferioli
Original Assignee
Bormioli Luigi S.P.A.
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
Application filed by Bormioli Luigi S.P.A. filed Critical Bormioli Luigi S.P.A.
Priority to PCT/EP2005/007610 priority Critical patent/WO2007006328A1/en
Publication of WO2007006328A1 publication Critical patent/WO2007006328A1/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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
    • C03C1/06—Opacifiers, e.g. fluorides or phosphates; Pigments to produce non-uniformly pigmented, e.g. speckled, marbled, or veined products

Definitions

  • the present invention relates to an opacifying com- position and the process for the production of glass having an opal/stone or snow effect.
  • the invention relates to the industrial field of the production of glass, containers and particularly high-quality aesthetic objects.
  • the production of opacified glass is generally effected in ovens in which a charge is inserted comprising a series of substances which, after melting and conditioning, feed the forming machines.
  • the glass thus produced and in particular opal glass envisages the introduction of fluorine compounds in the charge .
  • this element (it is known as being the most electro-negative element) makes it par- ticularly corrosive with respect to refractory material which forms the oven basin, to such an extent that frequent maintenance is required thereof, every 12/24 months, with stoppage times of the oven in the order of about 1 month, and whose costs, added to the investment costs, considerably influence the cost of the product.
  • the Applicant has now found that it is possible to obtain an opal/stone effect or a snow effect of glass destined for the production of high-quality objects, table accessories, by the introduction of an appropriate composition directly in the feeding channel to the forming machines leaving the oven, so-called "feeders", also solving the above problems of the known art.
  • the present invention therefore proposes to overcome the drawbacks, both ecological and relating to frequent renewal and maintenance of the process, and the production methods of opacified glass according to the known art, by means of an opacifying composition and a production process of glass having an opal/stone or snow effect.
  • the opacifying composition suitable for giving glass an opal/stone or snow effect comprises one or more of the following materials: Zirconium Oxides, Titanium Oxides, Tin Oxides, Calcium Oxides, Zinc Oxides, Yttrium Oxides, Erbium Oxides, anhydrous Alumina, Alumina hydrate, Calcined Dolomite, Calcium Phosphate; Derivatives of the grinding of refractory, electro-melted or sintered materials; Sands with a silica content higher than 85%.
  • the opacifying composition and process for the pro- duction of glass with an opal/stone or snow effect allows the production of glass having one of the following two effects :
  • composition and process according to the invention it is possible to produce glass articles which look similar to various hard natural stones (quartz, sapphire, turquoise, amethyst, opal, agate, onyx, lapisla- zuli) .
  • Any kind of colouring frit can, in fact, be superimposed with said composition and process, directly in the feeding channel of the forming machines (feeders) , at the outlet of the oven, obtaining a pastel shade uniformly distributed on the article or localized in strips of colour on the transparent glass.
  • the physico-chemical characteristics of the result- ing glass conform with all the regulations in force for packaging and contact with food, and the opacification, moreover, is obtained under controlled conditions which are such as not to leave any dangerous residual tension in the glass or influence the expansion coefficient, guaranteeing a product with good mechanical properties.
  • the process developed which takes place downstream of the melting, is characterized by considerable production flexibility, allowing rapid colour variations, intensity or effect on the end-product.
  • the opacification in the feeder can be applied to any type of glass regardless of the original composition of the vitrifiable mixture and melting technology.
  • the opacifying composition according to the inven- tion is introduced in the form of a semi-processed product and obtained by the mixing of the components specified below:
  • Opacifying composition this has the function of remaining in the glass during the processing phase in the form of micro-inclusions or aggregates of particles and gives the product one of the two desired effects, specifically an opal/stone effect or snow effect.
  • the opacifying composition suitable for giving glass the desired opal/stone effect or snow effect comprises one or more of the following materials: Zirconium Oxides, Titanium Oxides, Tin Oxides, Calcium Oxides, Zinc Oxides, Yttrium Oxides, Erbium Oxides, anhydrous Alumina, Alumina hydrate, Calcined Dolomite, Calcium Phosphate; Derivatives of the grinding of refractory, electro-melted or sintered materials; Sands with a silica content higher than 85%.
  • the particle-size of the above materials expressed in microns ranges from 20 to 500.
  • composition is further enhanced by the ad- dition of other materials: - disgregating material, which has the function of causing the shattering of the semi -processed grains by the violent evaporation of the crystallization water contained therein, salt hydrates of Boron and/or alumina hy- drate are preferably used.
  • - melting material which has the function of causing the melting of the silica matrix of the semi-processed grains generated by its shattering, this comprises salts and oxides of alkaline and alkaline-earth metals.
  • - structuring material which has the function of creating a glassy matrix which carries the micro-grains of opacifying material in the glass, this comprises one or more of the following products: salts and oxides of Silicon, Germanium, Phosphorous, Boron (Si, Ge, P, B) .
  • - binding materials which have the function of keeping the semi-process product compact, these comprise one or more of the following compounds: solutions of sodium silicate, products based on salts of alkaline or alkaline-earth metals in aqueous solution.
  • the weight percentages of the composition according to the present invention are selected in relation to the aesthetic result to be obtained and operating conditions used, said percentages are within the following ranges: Opacifying material from 10 to 80% Disgregating material from 5 to 50% Melting material from
  • Copper oxide frits for a blue colour, selenium frits for a pink colour, copper and chromium oxide frits for a turquoise colour, are known, for example.
  • the process according to the present invention comprises the feeding of the composition described in at least one of the feeding channels of the forming machines (feeders) .

Abstract

The present invention relates to an opacifying composition and the process for the production of glass with an opal/stone effect or with a snow effect, the opacifying composition suitable for giving the glass an opal/stone effect or a snow effect comprises one or more of the following materials: Zirconium Oxides, Titanium Oxides, Tin Oxides, Calcium Oxides, Zinc Oxides, Yttrium Oxides, Erbium oxides, anhydrous Alumina, Alumina hydrate, Calcined Dolomite, Calcium Phosphate; Derivatives of the grinding of refractory, electro-melted or sintered materials; Sands with a silica content higher than 85%.

Description

OPACIFYING COMPOSITION AND PROCESS FOR THE PRODUCTION OF GLASS WITH AN OPAL/STONE EFFECT OR WITH A SNOW EFFECT.
The present invention relates to an opacifying com- position and the process for the production of glass having an opal/stone or snow effect.
In particular, the invention relates to the industrial field of the production of glass, containers and particularly high-quality aesthetic objects. In the glass industry, the production of opacified glass is generally effected in ovens in which a charge is inserted comprising a series of substances which, after melting and conditioning, feed the forming machines.
Investments for the production of the melting ovens are in themselves considerable.
Furthermore, the glass thus produced and in particular opal glass, envisages the introduction of fluorine compounds in the charge .
The aggressiveness of this element (it is known as being the most electro-negative element) makes it par- ticularly corrosive with respect to refractory material which forms the oven basin, to such an extent that frequent maintenance is required thereof, every 12/24 months, with stoppage times of the oven in the order of about 1 month, and whose costs, added to the investment costs, considerably influence the cost of the product.
From an environmental point of view, the emission of vapours of compounds deriving from the oven, are also particularly toxic and require complex abatement equip- ment .
Furthermore, in the production of normal transparent glass or coloured glass having a so-called "snow" effect, the known art envisages the formation of bubbles inside the glassy mass to provide this effect. The formation of bubbles, however, which can reach the surface of the product, can create micro-fractures and generally structurally weaken the object, and is also dangerous (cutting) when using the object.
The Applicant has now found that it is possible to obtain an opal/stone effect or a snow effect of glass destined for the production of high-quality objects, table accessories, by the introduction of an appropriate composition directly in the feeding channel to the forming machines leaving the oven, so-called "feeders", also solving the above problems of the known art. The present invention therefore proposes to overcome the drawbacks, both ecological and relating to frequent renewal and maintenance of the process, and the production methods of opacified glass according to the known art, by means of an opacifying composition and a production process of glass having an opal/stone or snow effect.
In particular, the opacifying composition suitable for giving glass an opal/stone or snow effect comprises one or more of the following materials: Zirconium Oxides, Titanium Oxides, Tin Oxides, Calcium Oxides, Zinc Oxides, Yttrium Oxides, Erbium Oxides, anhydrous Alumina, Alumina hydrate, Calcined Dolomite, Calcium Phosphate; Derivatives of the grinding of refractory, electro-melted or sintered materials; Sands with a silica content higher than 85%.
These and other objectives and advantages according to the present invention are achieved by means of an opacifying composition and a process for the production of glass having an opal/stone or snow effect according to what is specified in claim 1.
Further characteristics form the object of the dependent claims .
The characteristics and advantages of the opacifying composition and process for the production of glass with an opal/stone or snow effect according to the present invention will appear more evident from the following illustrative and non-limiting description.
The opacifying composition and process for the pro- duction of glass with an opal/stone or snow effect allows the production of glass having one of the following two effects :
- opaque glass with a uniform distribution on the whole surface of the article produced, deriving from the pres- ence of white or yellowish micro-inclusions, spherically- shaped or irregular with a normalized diameter ranging from 20 to 500 microns.
- glass in which aggregates of particles are present inside the glassy matrix, which form white or yellowish flakes having a dimension ranging from 50 to 1000 microns, present in a concentration higher than 50 flakes/cm3 of glass .
With the composition and process according to the invention, it is possible to produce glass articles which look similar to various hard natural stones (quartz, sapphire, turquoise, amethyst, opal, agate, onyx, lapisla- zuli) .
Any kind of colouring frit can, in fact, be superimposed with said composition and process, directly in the feeding channel of the forming machines (feeders) , at the outlet of the oven, obtaining a pastel shade uniformly distributed on the article or localized in strips of colour on the transparent glass.
The physico-chemical characteristics of the result- ing glass conform with all the regulations in force for packaging and contact with food, and the opacification, moreover, is obtained under controlled conditions which are such as not to leave any dangerous residual tension in the glass or influence the expansion coefficient, guaranteeing a product with good mechanical properties.
The process developed, which takes place downstream of the melting, is characterized by considerable production flexibility, allowing rapid colour variations, intensity or effect on the end-product. The opacification in the feeder can be applied to any type of glass regardless of the original composition of the vitrifiable mixture and melting technology.
During the opacification process in the feeder, there are no emissions of polluting or harmful vapours or powders for the process operators.
The aesthetic effect obtained with this process can be applied to a wide range of articles, regardless of their design or forming process: - Table accessories: glasses, goblets, decanters, bot- ties, plates, trays. - Household items: vases, objects for bathroom lines.
- Bijouterie: charms, pendants.
- Perfumery: bottles for perfumes and .cosmetics .
The opacifying composition according to the inven- tion is introduced in the form of a semi-processed product and obtained by the mixing of the components specified below:
Opacifying composition: this has the function of remaining in the glass during the processing phase in the form of micro-inclusions or aggregates of particles and gives the product one of the two desired effects, specifically an opal/stone effect or snow effect.
The opacifying composition suitable for giving glass the desired opal/stone effect or snow effect, comprises one or more of the following materials: Zirconium Oxides, Titanium Oxides, Tin Oxides, Calcium Oxides, Zinc Oxides, Yttrium Oxides, Erbium Oxides, anhydrous Alumina, Alumina hydrate, Calcined Dolomite, Calcium Phosphate; Derivatives of the grinding of refractory, electro-melted or sintered materials; Sands with a silica content higher than 85%.
The particle-size of the above materials expressed in microns ranges from 20 to 500.
The above composition is further enhanced by the ad- dition of other materials: - disgregating material, which has the function of causing the shattering of the semi -processed grains by the violent evaporation of the crystallization water contained therein, salt hydrates of Boron and/or alumina hy- drate are preferably used.
- melting material, which has the function of causing the melting of the silica matrix of the semi-processed grains generated by its shattering, this comprises salts and oxides of alkaline and alkaline-earth metals. - structuring material, which has the function of creating a glassy matrix which carries the micro-grains of opacifying material in the glass, this comprises one or more of the following products: salts and oxides of Silicon, Germanium, Phosphorous, Boron (Si, Ge, P, B) . - binding materials, which have the function of keeping the semi-process product compact, these comprise one or more of the following compounds: solutions of sodium silicate, products based on salts of alkaline or alkaline-earth metals in aqueous solution. The weight percentages of the composition according to the present invention are selected in relation to the aesthetic result to be obtained and operating conditions used, said percentages are within the following ranges: Opacifying material from 10 to 80% Disgregating material from 5 to 50% Melting material from 5 to 50%
Structuring material from 5 to 50% Binding material from 0 to 30%
Humidity from 0 to 15%. In the feeding phase to the forming machines, suitable colouring frits can also be added to obtain coloured glass with an opal/stone effect or with a snow effect.
Copper oxide frits for a blue colour, selenium frits for a pink colour, copper and chromium oxide frits for a turquoise colour, are known, for example.
The process according to the present invention comprises the feeding of the composition described in at least one of the feeding channels of the forming machines (feeders) .

Claims

1. An opacifying composition for the production of glass having an opal/stone effect or snow effect, charac- terized in that it comprises one or more of the following materials: Zirconium Oxides, Titanium Oxides, Tin Oxides, Calcium Oxides, Zinc Oxides, Yttrium Oxides, Erbium Oxides, anhydrous Alumina, Alumina hydrate, Calcined Dolomite, Calcium Phosphate; Derivatives of the grinding of refractory, electro-melted or sintered materials; Sands with a silica content higher than 85%.
2. The opacifying composition according to claim 1, wherein said materials have a particle-size expressed in microns ranging from 20 to 500.
3. The opacifying composition according to claim 1, wherein said composition also comprises salt hydrates of Boron and/or alumina hydrate .
4. The opacifying composition according to claim 1, wherein said composition also comprises salts and oxides of alkaline and alkaline-earth metals.
5. The opacifying composition according to claim 1, wherein said composition also comprises one or more of the following products: salts and oxides of Silicon, Germanium, Phosphorous, Boron.
6. The opacifying composition according to claim 1, wherein said composition also comprises one or more of the following compounds: solutions of sodium silicate, products based on salts of alkaline or alkaline-earth metals in aqueous solution.
7. The opacifying composition according to claim 6, wherein said composition is produced in the following weight percentages :
Opacifying material from 10 to 80%
Disgregating material from 5 to 50% Melting material from 5 to 50%
Structuring material from 5 to 50% Binding material from 0 to 30%
Humidity from 0 to 15%.
8. Table accessories, glasses, goblets, decanters, bot- ties,, plates, trays; household items, vases, bathroom articles; bijouterie, charms, pendants, bottles for perfumes and cosmetics produced with opacified glass according to claims 1 to 7.
9. A process for the production of glass having an opal/stone effect or a snow effect characterized in that it comprises a feeding phase of a composition according to any of the claims from 1 to 7 into the feeding channel of the forming machine .
10. The process according to claim 9, wherein opal/stone glass is produced, with a uniform distribution on the whole surface of the article produced, deriving from the presence of white or yellowish micro-inclusions, spherically-shaped or irregular with a normalized diameter ranging from 20 to 500 microns.
11. The process according to claim 9, wherein glass with a snow effect is produced, wherein aggregates of particles are present inside the glassy matrix, forming white or yellowish flakes having a dimension ranging from 50 to 1000 microns, present with a concentration higher than 50 flakes/cm3 of glass.
PCT/EP2005/007610 2005-07-11 2005-07-11 Opacifying composition and process for the production of glass with an opal/stone effect or with a snow effect WO2007006328A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2005/007610 WO2007006328A1 (en) 2005-07-11 2005-07-11 Opacifying composition and process for the production of glass with an opal/stone effect or with a snow effect

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2005/007610 WO2007006328A1 (en) 2005-07-11 2005-07-11 Opacifying composition and process for the production of glass with an opal/stone effect or with a snow effect

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017146662A1 (en) * 2016-02-26 2017-08-31 Turkiye Sise Ve Cam Fabrikalari A.S. Borosilicate glass with snow visual effect and the production method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58208149A (en) * 1982-05-28 1983-12-03 Nippon Furitsuto Kk Opaline frit for dry casting
US4427429A (en) * 1981-04-15 1984-01-24 Riihimaen Lasi Oy Method for the opalization of glass
JPS60131844A (en) * 1983-12-20 1985-07-13 Ishizuka Glass Ltd Manufacture of opal glass
JPS61174143A (en) * 1985-01-26 1986-08-05 Ishizuka Glass Ltd Production of opal white glass
SU1330094A1 (en) * 1985-12-13 1987-08-15 Государственный научно-исследовательский институт стекла Glass composition
EP0402007A1 (en) * 1989-05-31 1990-12-12 Johnson Matthey Public Limited Company Glass composition for use in glazes
JPH03235871A (en) * 1990-02-09 1991-10-21 Shinagawa Refract Co Ltd Artificial glass stone

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4427429A (en) * 1981-04-15 1984-01-24 Riihimaen Lasi Oy Method for the opalization of glass
JPS58208149A (en) * 1982-05-28 1983-12-03 Nippon Furitsuto Kk Opaline frit for dry casting
JPS60131844A (en) * 1983-12-20 1985-07-13 Ishizuka Glass Ltd Manufacture of opal glass
JPS61174143A (en) * 1985-01-26 1986-08-05 Ishizuka Glass Ltd Production of opal white glass
SU1330094A1 (en) * 1985-12-13 1987-08-15 Государственный научно-исследовательский институт стекла Glass composition
EP0402007A1 (en) * 1989-05-31 1990-12-12 Johnson Matthey Public Limited Company Glass composition for use in glazes
JPH03235871A (en) * 1990-02-09 1991-10-21 Shinagawa Refract Co Ltd Artificial glass stone

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 198812, Derwent World Patents Index; Class L01, AN 1988-082698, XP002365491 *
PATENT ABSTRACTS OF JAPAN vol. 008, no. 052 (C - 213) 9 March 1984 (1984-03-09) *
PATENT ABSTRACTS OF JAPAN vol. 009, no. 287 (C - 314) 14 November 1985 (1985-11-14) *
PATENT ABSTRACTS OF JAPAN vol. 010, no. 383 (C - 393) 23 December 1986 (1986-12-23) *
PATENT ABSTRACTS OF JAPAN vol. 016, no. 021 (M - 1201) 20 January 1992 (1992-01-20) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017146662A1 (en) * 2016-02-26 2017-08-31 Turkiye Sise Ve Cam Fabrikalari A.S. Borosilicate glass with snow visual effect and the production method thereof

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