EP1899097A2 - Materialien zur beschichtung keramischer körper, verfahren zu deren herstellung, verwendung davon und diese materialien enthaltende keramische artikel - Google Patents

Materialien zur beschichtung keramischer körper, verfahren zu deren herstellung, verwendung davon und diese materialien enthaltende keramische artikel

Info

Publication number
EP1899097A2
EP1899097A2 EP06777447A EP06777447A EP1899097A2 EP 1899097 A2 EP1899097 A2 EP 1899097A2 EP 06777447 A EP06777447 A EP 06777447A EP 06777447 A EP06777447 A EP 06777447A EP 1899097 A2 EP1899097 A2 EP 1899097A2
Authority
EP
European Patent Office
Prior art keywords
materials
ceramic
fired
metal powders
powders
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06777447A
Other languages
English (en)
French (fr)
Inventor
Marco Bitossi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Colorobbia Italia SpA
Original Assignee
Colorobbia Italia SpA
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 Colorobbia Italia SpA filed Critical Colorobbia Italia SpA
Publication of EP1899097A2 publication Critical patent/EP1899097A2/de
Withdrawn legal-status Critical Current

Links

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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • 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
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • 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
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0425—Copper-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/086—Cooling after atomisation
    • B22F2009/0876—Cooling after atomisation by gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • the invention relates to ceramic materials to be used as coating films for ceramic articles produced with double-fired, porous single-fired, single-fired, porcelain stoneware, third- and fourth-fire technologies.
  • a ceramic body composed of clay, feldspar and quartz and other raw materials depending on the type of article, which is then coated with films of materials of particular interest which, through firing, offer the final product suitable aesthetic and technical characteristics for commercial purposes.
  • the aforesaid materials are applied with various techniques, such as disc application, bell waterfall, dry application (during the phase to press the support or subsequently), screen printing, silicone roller technique and others.
  • some of the aforesaid materials offer the final article an appearance similar to metals, enhancing the characteristics of surface shine typical of metals. Nonetheless, these materials always associate marked shine with other aesthetic characteristics which in any case offer a visual appearance typical of ceramic materials. In particular, a certain degree of surface glassiness typical of brilliant enamels can always be noted. Even in the case of non-brilliant surfaces a texture typical of mat or semi-mat ceramic enamels can nonetheless always be noted. These last-mentioned characteristics mean that, even to the less expert eye, the ceramic tile coated with the relevant materials currently in use can immediately be distinguished from a metal surface, such as steel, copper or other true metals.
  • metal lustres applied in the
  • materials for coating ceramic bodies are intended as: enamels, crystal glazes, frits, frit granules, ceramic paints, atomized, sintered, pelletized and granulated materials, enamels and crystal glazes for screen printing or silicone roller application, enamels and crystal glazes for dry application before, during and after pressing of the support, supplied dry and/or in a medium, in a wide range of grain sizes and suitable for all specific cases.
  • Materials for coating ceramic bodies according to the present invention are composed of metal powders with an extremely high metal content and an extremely low oxide content.
  • Atomized powders produced by cooling the melted alloy in a flow of nitrogen or argon are particularly preferred, as their content of oxides is practically zero and because this technique allows the production of spherical particles which proves more efficient for the wanted result then the particles obtained by water cooling which show and irregular flake shape.
  • the powders used according to the present application consists of a mixture of particles of different diameter, normally comprised between 50 and 150 micron.
  • the fraction of particles having dimension higher then 100 micron is comprised between 20 - 40 % wt on the total of the powder, this embodiment allows the formation in the final product of aesthetic effects (so called "peacock tail” effects) which are particularly appreciated.
  • metal powders useful according to the invention can have the following composition percentages indicated in weight in relation to the total weight of the powder: iron based alloys: Fe 50 - 90%; Cr 4 - 35%; Ni 4 - 11 nickel based alloys: Ni 75 - 96%, Cr 6 - 15%, Fe 1 - 4; cobalt based alloys: Co 50 - 68%; Cr 20 - 30%, Ni 2 - 25% copper based alloys: Cu 75 - 92%; Ni 1 - 5%; Fe 1 - 3 %
  • said powders can also contain, for example, B, Si, C, W, Mo, Mn, Al, Ni,
  • metal powders used in the present application are: Fe 67% Cr 17%, Ni 12%, Mo 2,5% Mn 1 ,5%
  • the metal powders above can be applied dry to the surface of the ceramic body creating the desired decoration by means of a suitable mechanical system.
  • the ceramic body will be subjected to the usual drying and firing operations at the temperatures and for the times and cycles normally required.
  • the powders can be mixed with common materials conventionally used in ceramics, such as frits, feldspars, kaolins, clays, zirconium silicates, alumina-silica minerals containing alkaline and/or alkaline earth elements, metal oxides, ceramic pigments and others normally used to prepare materials for coating ceramic bodies as defined above according to the invention, preferably prepared separately before mixing.
  • ceramics such as frits, feldspars, kaolins, clays, zirconium silicates, alumina-silica minerals containing alkaline and/or alkaline earth elements, metal oxides, ceramic pigments and others normally used to prepare materials for coating ceramic bodies as defined above according to the invention, preferably prepared separately before mixing.
  • the aforesaid mixes are prepared adding metal powders to other materials conventionally used in ceramics as indicated above in a dry mixer or other machine suitable for the type of material to be mixed, to obtain homogenization.
  • the mix thus obtained is applied to the ceramic body, if necessary with the aid of the usual media (i.e. polyethylene glycol or water) and this is then fired at the normal temperatures and for the times and cycles required.
  • the ceramic article can be smoothed and polished with suitable tools, as already known in the art for products coated with conventional materials, or also uncoated products.
  • the cooling phase of the fired article can be performed in furnaces with a flow of nitrogen or argon to reduce any surface oxidation processes which can occur during said cooling phase.
  • the powders are mixed with the other conventional materials mentioned above in high percentages which reach values ranging from 35% to 85% in weight in relation to the total weight of the mixture, so that the percentage of metals Fe, Cu or Co present in the semi-finished product ready for ceramic use is very high.
  • Example 1 The purpose of adding the other ceramic raw materials mentioned is to make these new materials vitrifiable in the correct way and compatible with heat treatment subsequent to application to the support of the article, to obtain films provided with functional performances suitable for the use. This requirement, not always necessary, makes it possible also to use the components indicated above as is, when the firing temperatures, such as for porcelain stoneware, are sufficiently high to allow softening and adhesion to the support.
  • the metallic characteristics visible after firing are provided by the aforesaid metal powders.
  • METAL ENAMEL 1 100 parts of metal enamel thus obtained (METAL ENAMEL 1) are added to 50 parts in weight of commercial screen printing medium (polyethylene glycol or the like).
  • the homogenized suspension is ready for application which is performed on porcelain stoneware support in the following way:
  • the tiles obtained are dried and then fired in a single-layer roller kiln for porcelain stoneware with a maximum temperature of 1200 0 C and overall time cycle of 50 minutes.
  • METALLIC ENAMEL 2 100 parts of enamel thus obtained (METALLIC ENAMEL 2) are added to 50 parts in weight of commercial screen printing medium (polyethylene glycol or the like). The homogenized suspension is ready for application which is performed on porcelain stoneware support in the following way:
  • the tiles obtained are dried and then fired in a single-layer roller kiln for single- firing with a maximum temperature of 118O 0 C and overall time cycle of 40 minutes.
  • the tiles obtained are dried and then fired in a single-layer roller kiln for porcelain stoneware with a maximum temperature of 1200 0 C and overall time cycle of 50 minutes.
  • the metal powder FE23C manufactured by Cogne Acciai Speciali SpA is applied dry, creating a design through a suitable mechanical system on the surface of the pre-pressed or soft mixture upstream of final pressing of the tile.
  • the tiles obtained are dried and then fired in a single-layer roller kiln for porcelain stoneware with a maximum temperature of 1200 0 C and overall time cycle of 50 minutes.
  • the high percentage of iron present on the surface confirms the metallic effect.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Compositions Of Oxide Ceramics (AREA)
EP06777447A 2005-06-23 2006-06-23 Materialien zur beschichtung keramischer körper, verfahren zu deren herstellung, verwendung davon und diese materialien enthaltende keramische artikel Withdrawn EP1899097A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT000142A ITFI20050142A1 (it) 2005-06-23 2005-06-23 Materiali per la ricopertura di corpi ceramici, processi per la loro preparazione loro uso e manufatti ceramici che li comprendono
PCT/EP2006/063509 WO2006136610A2 (en) 2005-06-23 2006-06-23 Materials for coating ceramic bodies, processes for the preparation thereof, use thereof and ceramic articles including these materials

Publications (1)

Publication Number Publication Date
EP1899097A2 true EP1899097A2 (de) 2008-03-19

Family

ID=35712576

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06777447A Withdrawn EP1899097A2 (de) 2005-06-23 2006-06-23 Materialien zur beschichtung keramischer körper, verfahren zu deren herstellung, verwendung davon und diese materialien enthaltende keramische artikel

Country Status (3)

Country Link
EP (1) EP1899097A2 (de)
IT (1) ITFI20050142A1 (de)
WO (1) WO2006136610A2 (de)

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ITFI20070061A1 (it) 2007-03-14 2008-09-15 Colorobbia Italia Spa Materiali per la ricopertura di corpi ceramici, loro preparazione ed uso e corpi ceramici che li comprendono.
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ITFI20070139A1 (it) 2007-06-22 2008-12-23 Colorobbia Italiana Spa Materiale per la ricopertura di corpi ceramici, loro preparazione ed uso e corpi ceramici che li comprendono.
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Also Published As

Publication number Publication date
ITFI20050142A1 (it) 2006-12-24
WO2006136610A2 (en) 2006-12-28
WO2006136610A3 (en) 2007-07-12

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