Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
  • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
  • C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
  • C04B41/5023—Glass-ceramics
• • 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
  • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
• • 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
  • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
• • 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
  • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
• • 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
  • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
  • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
  • C04B41/81—Coating or impregnation
  • C04B41/85—Coating or impregnation with inorganic materials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
  • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
  • C04B41/81—Coating or impregnation
  • C04B41/85—Coating or impregnation with inorganic materials
  • C04B41/86—Glazes; Cold glazes
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
  • C04B2111/0025—Compositions or ingredients of the compositions characterised by the crystal structure
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/80—Optical properties, e.g. transparency or reflexibility
  • C04B2111/82—Coloured materials

Definitions

• This invention relates to a base composition of oxides and the products derived from said composition, characterised in that following its application on a ceramic substrate and its subsequent firing, crystal formations of Russellite are obtained on the surface of the ceramic part that provide it with an appearance that is rich in chromatic hues, iridescent, metallic and shiny depending on the amount and size of the crystals present.
• This invention lies within the sector of the ceramic industry, specifically that of materials for flooring and ceramic wall lining obtained by single or double firing, structural ceramics, roof tiles, and sanitary and artistic ceramics.
• the surface coating of ceramic supports provides the parts with decoration or technical features that allow differentiation and diversification of the products, also providing them with great added value.
• These surface coatings are compositions that contain vitreous materials obtained from the fusion of inorganic substances (frit) and/or raw materials that after being subjected to the firing processes of the ceramic industry produce a vitreous matrix in which the different crystalline phases are dispersed.
• the crystallisation consists in the formation of crystalline structures within a glaze.
• the factors to be considered are: cooling conditions, molten ceramic viscosity, surface tension and the chemical composition of the glaze or enamel.
• the objective of this invention is to obtain a new crystalline formation that is currently unknown to the industry of ceramic coatings by compositions comprising a mixture of essential oxides, which are wolfram oxide (also called tungsten oxide) and bismuth oxide, together with other optional oxides as well as the method for obtaining them.
• essential oxides which are wolfram oxide (also called tungsten oxide) and bismuth oxide, together with other optional oxides as well as the method for obtaining them.
• Patent EP1970357 (Materials for coating ceramic bodies, preparation and use thereof and ceramic bodies comprising them), perfectly shows the state of the art and relates to a series of materials for coating ceramic bodies comprising a mixture of oxides from groups IB, VIB and VII of the periodic table and in particular wolfram oxide, cobalt oxide and copper oxide, in percentages by weight from 20 to 70% for wolfram oxide, from 2 to 30% for cobalt oxide and from 5 to 30% for copper oxide and other oxides in a percentage between 0 and 20%.
• this patent does not include bismuth oxide in the composition of the materials nor does it refer at any time to obtaining crystalline phases of bismuth wolframate (russellite).
• Patent US3480566 Liow Melting glass and Compositions containing the same discloses a composition used in the manufacture of electric circuits that requires the addition of noble metal powder and a liquid vehicle to a glass of the PbO-Bi203- B203-Si02 system in contrast to this invention, where it is not essential to use noble metals or lead oxide in the compositions.
• patent US3480566 The field of application of patent US3480566 is that of the manufacture of electric circuits. The firing temperatures and the application techniques differ from those of this invention, and nowhere does patent US3480566 refer to or intend to obtain crystals of bismuth wolframate (russellite).
• Patent US2663658 (Ornamental Crystalline glaze) describes an ornamental or decorative glaze that contains crystals that are big enough to be visible.
• crystals of one or more oxides of the third, fourth or fifth group of the periodic table are formed by oversaturation with an oxide or some of the oxides of the following elements: V, Ge, W, Ti, Zr, Ce, Cr, Se, Al, Te, in a matrix of glass-formers of the group consisting of PbO, Na20, K20, MgO, CaO, BaO, B203, ZnO, SrO and Bi203, except for silicon oxide.
• the silicon oxide has an inhibiting effect for the formation of these crystals.
• wolfram tungsten glazes
• wolfram tungsten glazes
• the proportion between the wolfram oxide and the glass-forming oxides is more than 1:1 and less than 19:1.
• compositions are applied on ceramic bodies but nowhere does it mention obtaining russellite crystals, and also the range of percent by weight in the compositions of Patent US2663658 differs from the working range of the composition presented in this invention.
• Patent US3607320 (Phototropic glass-ceramic articles containing bismuth doped calcium tungstate crystals) discloses a phototropic ceramic glass consisting in a vitreous matrix with 10 to 90% by weight of calcium wolframate crystals as a phototropic agent
• Said crystals are doped with bismuth and the vitreous matrix contains as forming elements boric oxide and silicon oxide.
• the crystalline phase present in this ceramic glass is calcium wolframate (Scheelite) and not the crystalline phase russellite, as described in this invention.
• bismuth oxide is present in the compositions at very low percentages, compared to this invention.
• Patent ES2310139 mentions obtaining a metallic finish using a vapour phase deposition technology (e.g. according to Patent EP1498402 Al) and states its limitations.
• compositions and methods for obtaining metallic effects in ceramic tiles and their applications comprise a mixture of essential oxides such as Si02, AI203, Fe203 and P205, together with other optional oxides.
• Document ES2301364 (Formulation for producing metallic effects) is characterised in that it comprises a first oxide chosen from AI203, P205, Si02, PbO and combinations thereof and Fe203 introduced as magnetite into the composition.
• a first oxide chosen from AI203, P205, Si02, PbO and combinations thereof
• Fe203 introduced as magnetite into the composition.
• Document ES2246166 (base composition of oxides for obtaining calcined pigments, method of synthesis of the pigments and use) discloses a base composition of oxides, characterised in that it comprises at least P205 in an amount comprised between 40-70% by weight, Fe203 in an amount comprised between 10-50% by weight and Document EP2000443 Al (Metallic glaze composition), which discloses the same composition as above but broadening its essential components with the introduction of Li20 between 0-30% by weight. These patents propose obtaining a calcined pigment that is subsequently added or mixed to give rise to an enamel slip.
• ES2310139 Al (Ceramic enamel with metallic gloss, method for obtaining it and application) proposes a formulation based on the use of particles of micro/nanometric size of different metals, metal oxides and alloys, mixed homogenously with ceramic frits, coal powder and other additives.
• creating a reduction atmosphere inside the furnace during the industrial firing of ceramic tiles (oxidizing firing) has limitations regarding the stability of the hues obtained.
• the objective of the present invention is to disclose a new composition as well as a method to obtain articles decorated with exceptional features, moreover, with advantages that exceed the state of the art mentioned above, such as: it has no limitations due to problems of toxicity such as with lead glazes with the addition of metals such as nickel, manganese and copper.
• This invention does not require any kind of modification in the usual production, application and firing systems used in the industry of coating ceramic bodies, with the extra savings this entails.
• This invention relates to obtaining a new crystalline formation unknown to date in the industry of coatings for ceramic bodies, the compositions for obtaining said crystalline phase, the process for obtaining the new crystalline phase and the ceramic products obtained.
• this invention relates to compositions comprising a mixture of oxides, which after being applied on ceramic bodies and fired, produce said crystalline phase, providing an appearance that is rich in chromatic hues, iridescent, metallic and glossy depending on the amount and size of the crystals present.
• the composition is applicable in general as a coating for any ceramic body, and specifically as a material for coating and decorating ceramic flooring and wall coating tiles obtained by single or double firing, structural ceramics, roof tiles and sanitary and artistic ceramics.
• the crystalline phase obtained with the composition object of the present invention is the bismuth wolframate known as russellite, with chemical formula Bi2W06.
• composition object of the invention comprises a mixture of oxides. Of these oxides, two are considered “basic or substantial” for obtaining the product, and the rest can be considered “excipients” or “non-substantial” for obtaining the product, since although they provide other features to the product, they are not essential to obtain the intended crystalline phase.
• the "basic or substantial” oxides are wolfram oxide (also called tungsten oxide) and bismuth oxide.
• these shall be chosen from amongst those commonly used in the industry of coatings for ceramic bodies, the function of which shall be to provide the composition with the necessary melting and flowability, favour the occurrence of the crystalline structure, crystal growth, modifying the viscosity and surface tension of the melt, formation of glass, etc.
• compositions object of the invention may contain all kinds of chromophore oxides, the purpose of which is to modify and enrich the colour of the final product obtained.
• manganese oxide copper oxide, cobalt oxide, chromium oxide, nickel oxide, iron oxide, vanadium oxide, etc.
• the ratio of the composition of the mixture of substantial oxides that chemically form the product, expressed in percent with respect to the total weight of the material are:
• the remaining oxides if they are present in the composition, they will preferably be within the range of between 0 and 70%.
• the materials according to this invention have the following composition:
• oxides 0- 60 % The mixture of oxides that make up the chemical composition may come from different raw materials, and the percentages of the components of the formula will be adjusted in each case in order to achieve the desired percentages of oxides.
• bismuth oxide can be introduced as an oxide, a nitrate, a carbonate, an aluminate of bismuth, wolfram oxide as an oxide, as calcium wolframate, as metal wolfram, etc.
• the starting materials or raw materials making up the chemical composition will be mixed and/or ground and/or shall be subjected to a melting or fritting process until obtaining a homogeneous product with a suitable particle size according to the chosen application methodology or technique.
• the particle size of the materials object of the invention will be determined by how they are presented as well as by the application technique used on the product.
• the materials object of the invention can come in different forms, all of which are intended to coat ceramic bodies and are widely used in the ceramic industry, such as for example: as a powder, as a suspension in an organic or inorganic medium (enamels, screen printing inks), as a frit, granulate, pelletised, sinterised, sprayed, and in any other form.
• the mixture of the starting materials is performed by melting them at high temperatures and then allowing them to cool.
• the granules of frit obtained are ground using suitable techniques that are known in the ceramic industry until achieving the desired particle size.
• This milling can be performed both as dry milling (producing fine grain, pellets, etc.) or by wet milling together with suitable vehicles and admixtures, producing a suspension or enamel that will be applied onto the ceramic support using any of the techniques used in the ceramic industry, which support will finally be fired.
• composition object of the invention can also be achieved at ambient temperature, without requiring fritting, or introducing part of the components of the composition as frit.
• suspensions or enamels will be obtained by mixing, homogenising and grinding the starting materials in a suspension medium and will then be applied onto the ceramic support using any of the techniques mentioned above, which will then finally be fired.
• the vehicle or dispersing medium is usually water, and the admixtures are those commonly used to guarantee their good application, suspension agents, plasticisers, glues, kaolin, bentonite, etc.
• suspensions or enamels can be sprayed, producing sprayed granules that will then be applied on the ceramic supports before, during or after the pressing step of the ceramic body.
• the ceramic body or support will then be fired.
• suspensions or enamels can be dried, micronized and mixed with suitable vehicles to provide screen printing inks.
• the vehicles or dispersion media are usually organic vehicles, in order to provide the screen printing inks with suitable properties of density, viscosity, wettability, drying, etc.
• the firing step will depend on the ceramic body to be coated, without any specific adjustments required either in the temperatures or firing times of the cycles usually used.
• a coating will be obtained in which there will be russellite crystals, providing the ceramic part with an appearance that is rich in chromatic hues, iridescent, metallic and glossy, depending on the amount and size of crystals present.
• the materials of this invention can also be applied in a single or in several layers, combining different proportions or colours or overlaying different applications on the same ceramic part, producing variations in the appearance, colour and texture of the part and allowing a great variety and diversity of aesthetic results.
• these materials can be applied and combined with other materials intended to coat ceramic bodies, slips, enamels, granulates and/or other serigraphy of common use in the industry.
• Example 1 For a greater understanding of this invention, we describe an embodiment thereof as Example 1, also including other examples with other embodiments. Please note that these should not be considered as a limitation or restriction of the scope of this invention.
• Bismuth oxide, clay, wolfram oxide and CMC glue were mixed together.
• the mixture was introduced into a ball mill with enough water to obtain a suspension with a density of more than 2200 g/l and enough time to obtain a residue of less than 3% in 45 micron mesh.
• the tile was allowed to dry and once dry it was subjected to a firing cycle in an industrial furnace at 1200°C for 65 minutes.
• the resulting ceramic part had an iridescent coating.
• the crystalline phases present in said coating were identified by x-ray diffraction using a Bruker D8-Discover unit. Interpretation of the diffractogram indicates the presence of a very oriented crystalline phase, concluding that it is russellite, syn with composition v-Bi2W06 and ICDD card (International Centre for Diffraction Data) 39-0256.
• the aqueous suspension obtained was homogenised by grinding until obtaining a residue over a 45 micron mesh of less than 0.5%. The mixture was then dried at 115°C in a laboratory oven.
• micronised mixture 100 g were weighed and 35 g were added of a screen printing vehicle formed by a mixture of synthetic polymers.
• the printed floor tile was allowed to dry and was subjected to a firing cycle in an industrial furnace at 1135°C for 50 minutes.
• the resulting ceramic part had a metallised and iridescent coating with blue and greenish hues.
• This mixture was introduced into a melting furnace for 45 minutes at 14005C.
• the resulting frit was then cooled in water and dried using a standard technique, using a laboratory oven, for example, at 100-120 9 C, or using a drying lamp.
• the dry mixture was ground and a granulometric selection was performed using sieves with different mesh sizes.
• the pellets or fine grain obtained was applied onto a part of porcelain stonewear using fine grain glue as an adhesive agent.
• the floor tile was then dried and subjected to a firing cycle in an industrial furnace at 1200?C for 80 minutes.
• the resulting ceramic part had an iridescent and glossy coating.
• This mixture was introduced into a melting furnace for 45 minutes at 10002C.
• the resulting frit was then cooled in water and dried using a standard technique, using a laboratory oven, for example, at 100-120 9 C, or using a drying lamp.
• the mixture was introduced into a ball mill with enough water to obtain a suspension with a density of more than 2200 g/l and enough time to obtain a residue of less than 1.5% in a 45 micron mesh.
• the mixture was then atomised in a laboratory atomiser.
• the atomised granules obtained were then subjected to granulometric selection using sieves with different mesh sizes.
• the resulting ceramic floor tile had a coating with a metallic and iridescent appearance in a red-brown colour.

Landscapes

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

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=43528446

Family Applications (1)

Country Status (3)

Cited By (13)

Families Citing this family (2)

Citations (24)

Family Cites Families (1)

• 2009
  • 2009-11-13 ES ES200902211A patent/ES2360781B1/es not_active Expired - Fee Related
• 2010
  • 2010-11-02 WO PCT/EP2010/006661 patent/WO2011057730A1/en active Application Filing
  • 2010-11-02 EP EP10781604A patent/EP2499106A1/en not_active Withdrawn

Patent Citations (25)

Non-Patent Citations (11)

Also Published As

Similar Documents

Legal Events