WO2014049189A1 - Composition et procédé d'obtention de carreaux renforcés en céramique de grès porcelaine - Google Patents

Composition et procédé d'obtention de carreaux renforcés en céramique de grès porcelaine Download PDF

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WO2014049189A1
WO2014049189A1 PCT/ES2013/070667 ES2013070667W WO2014049189A1 WO 2014049189 A1 WO2014049189 A1 WO 2014049189A1 ES 2013070667 W ES2013070667 W ES 2013070667W WO 2014049189 A1 WO2014049189 A1 WO 2014049189A1
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weight
porcelain stoneware
proportion
obtaining according
expressed
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PCT/ES2013/070667
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English (en)
Spanish (es)
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José Francisco FERNÁNDEZ LOZANO
Julián JIMÉNEZ REINOSA
Enrique VELA CARRASCOSA
Fernando GARCÍA TOMAS
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Consejo Superior De Investigaciones Científicas
Vicar, S. A.
Pasek Minerales, S. A. U.
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Publication of WO2014049189A1 publication Critical patent/WO2014049189A1/fr

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    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/04—Clay; Kaolin
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    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • 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
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    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
    • C04B2235/3445—Magnesium silicates, e.g. forsterite
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    • C04B2235/3472—Alkali metal alumino-silicates other than clay, e.g. spodumene, alkali feldspars such as albite or orthoclase, micas such as muscovite, zeolites such as natrolite
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Definitions

  • the present invention belongs to the field of the preparation of formulations for the ceramic industry, in particular in applications of formulations for the production of porcelain stoneware both for the production of ceramic tiles and for ceramic products in their application in structural ceramics and ornamental ceramics. More specifically, the present invention relates to a new type of compositions and the process for obtaining ceramic porcelain stoneware products with a marked improvement in their mechanical strength.
  • Porcelain stoneware is a ceramic product that is vitrified throughout its mass and is very compact, which has as its essential characteristic a low and closed porosity. This material has excellent mechanical and chemical properties, which allow its use, for example, as flooring or cladding both indoors and outdoors. In addition, it has a high modulus of breakage (high mechanical strength) and toughness, with mechanical flexural strengths typically between 250 and 500 kg / cm 2 .
  • a porcelain-type vitrified product is characterized by having a microstructure that combines a vitreous matrix in which different crystalline phases are located.
  • the most common crystalline phases found in sintered stoneware are quartz, mullite, alumina, zircon, anortite and ganhite. While certain crystalline phases come from the starting products, others are consequences of chemical reactions that take place at high temperature during heat treatment.
  • Porcelain stoneware requires a well-known ceramic process that corresponds to a technologically mature process that consists, in broad strokes, of obtaining a homogeneous mixture of raw materials, forming the part and performing a heat treatment at temperatures above 1 100 ° C.
  • nanocrystalline mullite is formed, the proportion of alumina contributed by the raw materials used in the manufacture of porcelain stoneware, such as kaolinitic clays, quartz and feldspars, does not exceed 15% by weight and therefore the proportion of mullite is very limited .
  • the solution consisting of the incorporation of synthetic products such as AI2O3 is economically unfeasible.
  • quartz polymorphism of S1O2.
  • the presence of quartz in porcelain stoneware occurs as a result of the incorporation of said phase in the form of siliceous sands.
  • the quartz crystals also provide excellent wear resistance properties.
  • the percentage of quartz in a porcelain composition is limited by generating problems of efficient forming of parts, particularly if they are large formats.
  • the iron and magnesium minerals used are very abundant minerals in nature.
  • a first aspect of the present invention relates to a porcelain stoneware comprising silicate crystals selected from the list comprising magnesium silicates, iron silicates and magnesium and iron silicates, preferably iron and magnesium silicates, where the crystals are homogeneously distributed and have an average size of 20 nm to 1000 nm, preferably 50 to 500 nm and more preferably 80 to 200 nm.
  • a second aspect of the present invention relates to the process for obtaining porcelain stoneware as described above, comprising the steps of: a) mixing in aqueous medium of: i) at least one plastic clay in a proportion of 40% to 70% in weight,
  • a third aspect of the present invention relates to the use of porcelain stoneware as described above as a cover or decorative piece for floors, walls, facades, furniture or sanitary ware.
  • pillain stoneware is meant a hard ceramic material, vitrified in all its mass and very compact, which presents as an essential characteristic a low and closed porosity, mechanical properties such as resistance to breakage and wear resistance, resistant to chemical attack and practically waterproof. To obtain it, it is based on a composition based on natural raw materials such as clay, quartz and feldspar.
  • silicate crystals means a homogeneous solid that has an ordered internal structure of its reticular particles, the chemical composition of which comprises SiO x groups.
  • a "plastic clay” is a clay that forms a moldable mass when mixed with water.
  • clay is meant hydrated aluminum silicates, from the decomposition of aluminum ores.
  • plastic clays kaolinite, smectite and illite clays are considered.
  • iron ore, magnesium or iron and magnesium means a solid chemical substance formed by biogeochemical processes that has a characteristic chemical composition (but variable within limits and an orderly atomic structure comprising cations of iron, magnesium or iron and magnesium respectively.
  • a “sand” or “quartzite sand” is an unconsolidated sedimentary material present in nature with a particle size between 0.2 ⁇ and 5000 ⁇ comprised mostly of crystalline particles of S1O2, generally in its polymorphic variety of quartz.
  • feldspar means a group of minerals comprising aluminum and calcium silicates such as anortite, of general formula CaAl2S ⁇ 20s, or sodium silicates such as albite of general formula NaAISi 3 0 8 , or potassium silicates such as potassium feldspar of general formula KAIS1O3O8, or mixtures of these bases.
  • baking is meant to undergo a heat treatment comprising high temperatures, preferably temperatures above 500 ° C.
  • Coating or decorative piece means a piece used in construction that allows a surface to be coated, whether horizontal or vertical, interior or exterior, straight or curved.
  • a first aspect of the present invention relates to a porcelain tile that it comprises silicate crystals selected from the list comprising magnesium silicates, iron silicates or magnesium and iron silicates, preferably iron and magnesium silicates, where the crystals are homogeneously distributed and have an average size of 20nm to 1000nm, preferably 50nm at 500 nm and more preferably from 80 nm to 200 nm.
  • the silicate crystals belong to the olivine mineral group.
  • olivine mineral group also called peridot, is a magnesium and iron nesosilicate.
  • the olivine group comprises at its ends the minerals Fayalite (iron silicate) and forsterite (magnesium silicate) as well as the intermediate compositions (iron and magnesium silicates). These minerals crystallize in the orthorhombic crystalline group.
  • the silicate crystals obtained are also characterized by being abundantly and with a good dispersion in the vitreous matrix of the porcelain stoneware. These crystals produce a mechanical reinforcement of porcelain stoneware.
  • the distribution and dispersion of said crystalline phases allows a reinforcement of the vitreous matrix and contributes to the crack deflection mechanisms.
  • These phases are achieved using raw materials with an important content in iron and magnesium cations. In the porcelain stoneware products of the prior art, these cations are avoided because they generate high expansion coefficients, which hinder the correct coupling of the enamels on said pieces and prevent the enamelling of the pieces.
  • the porcelain stoneware further comprises quartz crystals, where the quartz crystals have an average size of 0.5 m to 100 ⁇ , preferably 1 ⁇ to 40 ⁇ and more preferably 2 ⁇ to 20 ⁇ . Quartz grains are characterized by rounded edges that indicate a partial dissolution in the vitreous phase and a good integration in it. These crystals act favorably from the mechanical point of view, as they reinforce the vitreous matrix by differences in coefficients of expansion.
  • the porcelain stoneware of the present invention comprises crystallizations corresponding to crystalline quartz phases and olivine crystalline phases.
  • the porcelain stoneware further comprises indialite crystals in a proportion less than 10%, preferably less than 5% and more preferably less than 2%.
  • indialite is meant an aluminum and iron and magnesium cyclosilicate, which is a high temperature polymorph of cordierite. Cyclosilicates are silicates that have bound tetrahedra, with a Si: 0 1: 3 ratio. Its formation in a porcelain produces crystals of microcrystalline size, reduces the mechanical properties of porcelain stoneware and significantly decreases the thermal coefficient of expansion.
  • the proportion of Mg expressed as a percentage by weight of the equivalent oxide with respect to the total weight, is 8% to 22%, preferably 10% to 20% and more preferably 12 % to 16%
  • the proportion of Fe expressed as a percentage by weight of the equivalent oxide with respect to the total weight, is from 2% to 15%, preferably from 3% to 10% and more preferably from 4 % to 6%
  • the porcelain stoneware further comprises Si proportions, expressed as a percentage by weight of the oxide equivalent to the total, is 40% to 70%, preferably 45% to 62% and more preferably from 50% to 56%.
  • the porcelain stoneware also comprises proportions of Al, expressed as a percentage by weight of the oxide equivalent to the total, is 5% to 22%, preferably 8% to 20% and more preferably from 12% to 18%.
  • the porcelain stoneware further comprises Na, K and Ca in proportions of less than 5% expressed as a percentage by weight of the respective equivalent oxides with respect to the total weight.
  • the porcelain stoneware further comprises other minor compounds in a proportion less than 1% by weight with respect to the total composition.
  • the present invention allows to adapt the formulation for the development of porcelain stoneware compositions with different expansion coefficients and different sintering temperatures.
  • crystallizations that can be incorporated into porcelain stoneware are zircon crystals, corundum, spinels, garnets.
  • the effect of these other crystallizations is mainly related to the chromatic modification of the porcelain stoneware of the present invention.
  • the methods of chromatic modification of the porcelain stoneware by crystallized particles compatible with the vitreous phase of the porcelain stoneware are well described in the state of the art.
  • the Porcelain stoneware density is at least 2.4 g / cm 3 , preferably at least 2.5 g / cm 3 .
  • sintered materials have closed porosity and a water adsorption coefficient of less than 0.5%.
  • the coefficient of thermal expansion in the range 50-300 ° C is less than 70x10 "7o C " 1 , preferably less than 60x10 "7o C " 1 .
  • the expansion coefficient is maintained at adequate values due to the nature and size of the phases formed.
  • the porcelain stoneware products of the present invention have a good mechanical strength, with modules of mechanical flexural strength of at least 800 kg / cm 2 and preferably of at least 1000 kg / cm 2 .
  • the mechanical impact resistance determined by means of the restitution coefficient by means of ISO 10545-5: 1996 in the porcelain stoneware samples of the present invention reaches values of 0.80 and preferably 0.85 which are advantageous against the coefficients. of restitution for porcelain stoneware materials in the state of the art, which are less than 0.70. A higher coefficient of restitution implies greater impact resistance.
  • the porcelain stoneware further comprises a slip layer.
  • a slip layer is meant a layer that covers the exposed face of the piece of porcelain stoneware, preferably composed of light clays, and whose purpose is to make the surface of the porcelain stoneware opaque and whiten, thus solving the limitations that may arise from the surface coloring of the porcelain stoneware of the present invention.
  • the porcelain stoneware further comprises an enamel layer.
  • "Enamel” means a vitreous material that is applied to decorate and color the piece of porcelain stoneware. Enamel is the result of the melting of powdered glass through a heating process. In the enamelling process the support is covered by a layer of enamel that can be decorated with ceramic pigments. This layer of Enamel can be applied on porcelain stoneware surfaces previously coated or not by a layer of engobe. This eliminates the limitations that could be derived from the color of the pieces for surface decoration processes.
  • a second aspect of the present invention relates to the process for obtaining porcelain stoneware as described above, comprising the steps of: a) mixing in aqueous medium of: i) at least one plastic clay in a proportion of 40% at 70% by weight,
  • the plastic clay comprises phyllosilicates.
  • clays for white pastes are clay minerals associated with the types of ball clay or China clay, of an illicit-kaolinitic or kaolinitic nature.
  • Clays for white pasta are characterized by the contribution of alumina of the composition and for having a low content in iron cations.
  • Clays for red pasta are clay minerals of an illicit-chlorite or illitic-kaolinite nature. Clays for red pasta have important contents of iron cations that give them the characteristic reddish color.
  • Philosilicates are preferably of an illitic-kaolinitic or kaolinitic nature. Or illitic-chlorite.
  • the quartzitic sand or sand comprises crystalline quartz particles.
  • Quartz is a mineral composed of silicon dioxide known as silica, Si0 2 , widely described and known in the state of the art and having a high hardness.
  • the feldspar comprises a group of tectosilicate minerals that are constituted primarily of igneous type rocks.
  • the iron ore, magnesium or both is a nesosilicate, preferably of the olivine group.
  • Said iron and magnesium minerals are preferably of magmatic origin. These minerals are part of dunites and peridotites, or are associated with pyroxene and chromite-like phases. They are also the main mineral component in gabros, basalts and kimberlites. It can also be in combination with silicates such as chlorites, talcs and brucites.
  • the proportion of Mg, expressed as a percentage by weight of the equivalent oxide with respect to the total weight is 8% to 22%, preferably 10% to 20% and more preferably 12% at 16%
  • the proportion of Fe expressed as a percentage by weight of the equivalent oxide with respect to the total weight it is from 2% to 15%, preferably from 3% to 10% and more preferably from 4% to 6%
  • the proportion of Si expressed as a percentage by weight of the equivalent oxide with respect to the total, is 40% to 70%, preferably 45% to 62% and more preferably 50 % to 56%.
  • the proportion of Al expressed as a percentage by weight of the equivalent oxide with respect to the total, is 5% to 22%, preferably 8% to 20% and more preferably 12 % to 18%.
  • K and Ca expressed as a percentage by weight of the respective oxides equivalent to the total weight of less than 5%.
  • the method further comprises a step (a1) after (a) and before (b) adding at least one additive, wherein the additive is selected from the list comprising defloculates, dispersants, defoamers, bactericides, binders, plasticizers and waxes.
  • the additive is selected from the list comprising defloculates, dispersants, defoamers, bactericides, binders, plasticizers and waxes.
  • a "deflocculant” is a chemical that prevents the aggregation of solid particles in a colloidal dispersion, such as sodium silicate.
  • a "dispersant” is an additive that is used to make a solute have distribution and dispersion in a solvent, such as tripolyphosphate, tetrasodium pyrophosphate, ammonium polyacrylate and sodium polyacrylate.
  • An “antifoam” is a substance that reduces the surface tension of the suspension and prevents the appearance of foams during mixing, such as a siloxane polyester.
  • a "bactericide” is a substance that prevents the proliferation of bacteria in the preparation of porcelain stoneware. Examples of suitable bactericidal substances are quaternary amines.
  • a "binder” is a chemical that has the ability to agglomerate or bind fragments or particles, such as acrylic emulsions suspended in water, acrylic styrene latex, a polyvinyl alcohol or a methylcellulose polymer.
  • a “plasticizer” is a resin or polymeric substance that confers plasticity to the green ceramic mass, in particular under pressure deformation, such as polyethylene glycol.
  • a wax is a malleable organic chemical compound.
  • Synthetic waxes comprise high molecular weight alkanes, such as paraffins.
  • Natural waxes are fatty acid esters with high molecular weight alcohols, such as beeswax. Binders, plasticizers and waxes are especially used when the process comprises an extruded step.
  • the method further comprises a step (a2) prior to (b) homogenization by grinding or dispersion of the product obtained in the previous stage.
  • a2 prior to (b) homogenization by grinding or dispersion of the product obtained in the previous stage.
  • conventional systems of the ceramic industry can be used, such as grinding or dispersion.
  • the average particle size of the homogenization slip of the porcelain stoneware raw materials of the present composition will be such that the d90 (average equivalent diameter at 90% of the distribution) is less than 100 ⁇ .
  • drying is carried out by spraying.
  • the step of forming parts is carried out by uniaxial pressing, isostatic pressing, or extrusion of ceramic bodies in green.
  • the homogeneous mixture of raw materials is dried by atomizing processes to obtain a distribution of agglomerates suitable for forming parts by conventional processes such as uniaxial pressing or isostatic pressing.
  • a Adequate proportion of water that is above the solid limit of the referred formulation of the present invention can be formed by extruding ceramic bodies in green.
  • the method further comprises a step (c1) subsequent to (c) and prior to (d) engobe application.
  • the method further comprises a step (c2) prior to (d) enamelling of the product resulting from the previous stage.
  • This enamelling can be done on the piece of porcelain stoneware with or without engobe.
  • the enamelling process of the pieces with a layer of ceramic enamel gives the ceramic tile technical and aesthetic properties such as: impermeability, easy cleaning, gloss, surface texture, mechanical and chemical resistance, as well as extensive decoration possibilities.
  • the cooking of step (d) is carried out in an industrial cycle, preferably in monocoction in a fast-cooking single-layer gas oven.
  • the cooking temperature of step (d) is between 980 ° C and 1280 ° C, even more preferably between 1 100 ° C and 1200 ° C.
  • the proportions and temperature range are adjusted based on the alkali and alkaline earth earth cation content of the composition.
  • the modification of the composition of the porcelain stoneware of the present invention depending on the proportions of components used thus represents an advantage since it allows adjusting the temperature range in which densified materials are obtained.
  • This procedure is advantageous since it allows to obtain ceramic products in processes with different cooking temperatures.
  • An additional advantage of the procedure is that it allows adapting to the availability of different local raw materials, limiting dependence on Imported raw materials.
  • the cooking of step (d) comprises rapid sintering cycles with residence times at the maximum temperature of the cycles of between 1 and 30 minutes, preferably between 2 and 20 minutes and even more preferably between 3 and 10 minutes. Excellent results have been obtained when the residence time at the maximum temperature is 6 minutes.
  • sintering cycle is meant the thermal cycle that the formulation undergoes so that the necessary phases of the porcelain stoneware are formed.
  • the "residence time at maximum temperature” is the time that the formulation is subjected to the maximum temperature of the cycle. This maximum temperature is between 980 ° C and 1280 ° C, preferably between 1 100 ° C and 1200 ° C.
  • the total time of the thermal cooking cycle lasts between 30 and 100 minutes, preferably between 40 and 80 minutes and even more preferably between 45 and 60 minutes. Cooking is preferably carried out under oxidizing atmosphere.
  • a third aspect of the present invention relates to the use of porcelain stoneware as described above as a covering or decorative piece in floors, walls, facades, furniture, sanitary ware. Due to the high mechanical strength of the porcelain stoneware products of the invention, in a preferred embodiment of the third aspect of the present invention, the part is large format.
  • the term "large format" in the context of the invention means formats with surfaces greater than 0.20 m 2 , preferably formats greater than 0.30 m 2 .
  • FIG. one X-ray powder diffractogram of the sample of Example 1.
  • C Quartz
  • F Forsterite
  • E Soapstone
  • M Mullite
  • H Hercinite
  • I Intensity
  • A Angle 2 ⁇ (degrees).
  • FIG. 2 X-ray powder diffractogram of the sample of Example 3.
  • C Quartz, F: Forsterite, E: Soapstone, M: Mullite, H: Hercinite; I: Intensity; A: Angle 2 ⁇ (degrees)
  • FIG. 3 Scanning Electron Microscopy (SEM) micrograph of the polished surface and chemically attacked with hydrofluoric acid corresponding to the sample of Example 1.
  • FIG. 4 SEM micrograph of the polished and chemically attacked surface corresponding to the sample of example 1. Detail of the submicron crystalline phases.
  • Example 1 Formulation and procedure for obtaining a porcelain stoneware tile with reinforced mechanical properties.
  • dunite magnesium iron silicate
  • quartz quartz
  • composition expressed as a percentage in oxide equivalent to the total is:
  • the above formulation was homogenized in aqueous medium at a concentration of 60% by weight solids content.
  • To this mixture was added 0.2% by weight of a sodium tripolyphosphate type dispersant and 0.05% by weight of an Additive type preservative.
  • the mixture was homogenized by milling in alumina ball mill to constitute a stable suspension. The grinding carried out allows a mixture of raw materials with a size such that the slippery residue when passing through a sieve of 63 ⁇ is less than 3% by weight.
  • This suspension was spray dried to obtain an agglomerate with a size distribution between 100-600 ⁇ .
  • the residual moisture of the atomized agglomerates was in a range of 4-7% by weight.
  • the agglomerates were formed in a tile by using a uniaxial press that used a pressing pressure of 250 kg / cm 2 .
  • the pressed green tiles were dried in an oven to remove the corresponding humidity.
  • the dried tile was heat treated at a temperature of 1 140 ° C in an oxidizing atmosphere in a fast-cooking monostrate oven in a 50-minute cycle. Maintenance time at maximum temperature was 6 minutes As a result, a porcelain stoneware support with the following physical properties was obtained:
  • Porcelain stoneware is also characterized by presenting the following crystalline phases identified by X-ray Diffraction (XRD) (Fig. 1):
  • These particles are characterized by having a grain size of less than 500 nm and being dispersed in the vitreous matrix to form the microstructure of the porcelain stoneware reinforced by the presence of submicron crystalline phases.
  • Example 2 Formulation and procedure for obtaining a porcelain stoneware tile with reinforced mechanical properties.
  • the same formulation as in example 1 and the same drying and forming was used.
  • the dry tile was heat treated at a temperature of 1,160 ° C in an oxidizing atmosphere in a fast-firing monolayer oven in a 50-minute cycle.
  • the maintenance time at maximum temperature was 6 minutes.
  • a porcelain stoneware support with the following physical properties was obtained:
  • Example 3 Formulation and procedure for obtaining a porcelain stoneware tile with reinforced mechanical properties.
  • dunite magnesium iron silicate
  • composition expressed as a percentage in oxide equivalent to the total is:
  • the porcelain stoneware material was processed following the procedure described in example 1 (maximum temperature 1 140 ° C). As a result, a porcelain stoneware support with the following physical properties was obtained:
  • Porcelain stoneware is also characterized by presenting the following crystalline phases identified by X-ray Diffraction (XRD) (Fig. 2):
  • Example 4 Formulation and procedure for obtaining a porcelain stoneware tile with reinforced mechanical properties.
  • composition expressed as a percentage in oxide equivalent to the total is:
  • the porcelain stoneware material was processed following the procedure described in example 1 (maximum temperature 1 140 ° C). As a result, a porcelain stoneware support with the following physical properties was obtained: density 2.42 g / cm "
  • Porcelain stoneware is also characterized by presenting the following crystalline phases identified by X-ray Diffraction (XRD):

Abstract

La présente invention concerne un grès porcelaine qui comprend des cristaux de silicates choisis parmi la liste qui comprend les silicates de magnésium, les silicates de fer ou les silicates de magnésium et de fer, les cristaux étant répartis de manière homogène et possédant une taille moyenne allant de 20 nm à 1000 nm, de préférence de 50 à 500 nm. De même, cette invention concerne le procédé d'obtention desdits produits de grès porcelaine.
PCT/ES2013/070667 2012-09-25 2013-09-25 Composition et procédé d'obtention de carreaux renforcés en céramique de grès porcelaine WO2014049189A1 (fr)

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN110678432A (zh) * 2017-05-05 2020-01-10 活性矿物国际有限公司 完全或部分替代陶瓷中球粘土的组合物及其制备方法和用途
KR20200005556A (ko) * 2017-05-05 2020-01-15 엑티브 미네랄스 인터내셔널 엘엘씨 세라믹에서 볼 클레이를 완전히 또는 부분적으로 대체하기 위한 조성물, 그의 제조 방법, 및 그의 용도 (composition to completely or partially replace ball clay in ceramics, method of making, and use thereof)
EP3619181A4 (fr) * 2017-05-05 2021-01-20 Active Minerals International, LLC Composition pour remplacer totalement ou partiellement l'argile plastique dans des céramiques, procédé de fabrication et utilisation associée
US11198646B2 (en) 2017-05-05 2021-12-14 Active Minerals International, Llc Composition to completely or partially replace ball clay in ceramics, method of making, and use thereof
CN110678432B (zh) * 2017-05-05 2022-06-07 活性矿物国际有限公司 完全或部分替代陶瓷中球粘土的组合物及其制备方法和用途
US11708307B2 (en) 2017-05-05 2023-07-25 Active Minerals International, Llc Composition to completely or partially replace ball clay in ceramics, method of making, and use thereof
KR102616059B1 (ko) 2017-05-05 2023-12-19 엑티브 미네랄스 인터내셔널 엘엘씨 세라믹에서 볼 클레이를 완전히 또는 부분적으로 대체하기 위한 조성물, 그의 제조 방법, 및 그의 용도 (composition to completely or partially replace ball clay in ceramics, method of making, and use thereof)

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