• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Ceramic material compacted with a low level of internal stresses and its use as a construction material in coatings and floors. High performance compacted ceramic material comprising between 40% -85% by weight of vitreous phase, characterized in that it has a density comprised between 2.5 and 2.75 g/cm3. This material has a high resistance to mechanics and allows it to be shaped into large tables for use as a construction material, especially in coatings, floors or kitchen countertops. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2593095A1
    申请号:ES201530796
    申请日:2015-06-05
    公开日:2016-12-05
    发明作者:José Manuel Benito López
    申请人:Cosentino Research and Development SL；
    IPC主号:
    专利说明:

    DESCRIPTION
    COMPACT CERAMIC MATERIAL WITH A LOW LEVEL OF INTERNAL VOLTAGES AND ITS USE AS A CONSTRUCTION MATERIAL IN COATINGS AND SOILS.
    Field of the invention 5
    The present invention belongs to the technical field of compacted ceramic materials for use as building materials in coverings and floors.
    Background of the invention
    The cooking stage is one of the most important stages of the manufacturing process of ceramic materials. During the cooking stage, the ceramic materials acquire the 10 mechanical properties and the final aesthetic characteristics of the product.
    In the procedures used in the state of the art, the cooking step is carried out following a temperature cycle in which the materials are heated to reach a temperature between 1,100 ° C and 1,200 ° C, followed by rapid cooling. Said cooling only slows down at 573 ° C where it is known that a change in volume occurs due to the allotropic transformation of the quartz from the alpha phase to the beta phase, which could lead to the breakage of the material due to stress generation.
    The internal stresses that occur during the firing cycle of the ceramic materials can be attributed mainly to the differences between the coefficient of expansion of the crystalline phase and the vitreous phase of the ceramic material, and to the difference in the 20 cooling rates between the surface and interior of the product. During the cooling of the cooking cycle, the temperature gradient that is generated in the thickness of the piece produces the modification of the dimensions of the crystalline phase and the vitreous phase according to its coefficient of expansion, producing internal stresses in the resulting ceramic material. 25
    In the case of the manufacture of ceramic tables of large dimensions and thin thicknesses, the internal tensions can produce the rupture of the material during the cooking cycle. In addition, when the pieces that resist the cooking cycle are subjected to drilling or cutting processes, the tensions become evident with the appearance of cracks in the material. 30

    Peter W. Olupot et al. (World Academy of Science, Engineering and technology, 2013, vol.7, p.332-338) report that some of the projects developed to reduce tensions in ceramic products are aimed at reducing or even replacing the content of quartz in the composition by other components such as ash or alumina. Peter W. Olupot et al. Show the results obtained from the modification of the cooking cycle in a sample of ceramic material 65 mm high and 76 mm wide and with a particular design. The authors did not observe changes in the mechanical properties of the materials that were maintained from 1 h to 3 h at the maximum temperature in the cooking cycle. However, the mechanical strength decreases when the ceramic material is maintained at the maximum temperature for 30 minutes. The authors do not mention changes in the properties of the materials when the cooling rate is decreased to less than 6 ° C / min.
    A. De Noni Junior et al. (A. de Noni et al., Bol.Soc.Ceram.V., 46, 4, 163-170 (2007)) disclose the influence of cooling on 80x20x7 mm ceramic specimens obtained by pressing of an industrial atomized powder. In the cooking cycle, the 15 specimens are heated at 70 ° C / min between 25-500 ° C, and at 25 ° C / min between 500 ° C and 1,190 ° C. The document shows the results obtained by varying the cooling rate of the cooking process from 1,190 ° C to 650 ± 20 ° C and in the area around the allotropic transformation of quartz (<650 ° C). The document mentions that by increasing the cooling rate, the number of residual stresses in the material increases and 20 also improves the mechanical strength of the ceramic material. However, the thermal gradients between the surface and the interior of the piece during the allotropic transformation of the quartz produce a microstructural deterioration of the piece that counteracts the increase in mechanical resistance.
    Therefore, there is a need in the state of the art for a compacted ceramic material 25 of high mechanical performance, with a low level of internal stresses that can be machined into large parts.
    OBJECT OF THE INVENTION
    The present invention provides a compacted ceramic material of high mechanical strength, where the internal stresses generated inside the material during the cooking process have been minimized. The ceramic material of the present invention can be used for the manufacture of large tables. Due to their excellent properties the compacted ceramic materials of the present invention
    They can be used as building materials in coatings, flooring or for the manufacture of kitchen countertops.
    In a first aspect, the present invention is directed to a compacted ceramic material comprising between 45-85% by weight of the vitreous phase characterized in that it has a density between 2.3 and 3.0 g / cm3. 5
    In another aspect the invention is directed to the process for manufacturing the compacted ceramic material comprising a cooking cycle where the cooling rate from the maximum temperature reached up to 700 ° C is between 0.5 and 2 ° C / min.
    Likewise, a further aspect of the present invention relates to the use of compacted ceramic material 10 as a construction material, as well as its use in facades and cladding.
    DETAILED DESCRIPTION OF THE INVENTION
    The present invention relates to a compacted ceramic material comprising between 45-85% by weight of the vitreous phase characterized in that it has a density comprised between 2.3 and 3 g / cm3.
    In the context of the present invention, "ceramic material" is understood to be constituted by inorganic, polycrystalline, non-metallic compounds, whose fundamental characteristic is that they are consolidated in a solid state by means of heat treatments at high temperatures (cooking) and are formed by a combination of crystalline and vitreous phases. The inorganic compounds are formed by metallic and non-metallic elements joined by ionic or covalent bonds.
    The ceramic materials of the present invention are obtained from high purity raw materials, in the form of micronic particles, and by large forming pressures and consolidated in solid state at high sintering temperatures. The 25 compacted ceramic materials of the present invention, with a vitreous phase between 40% -85% by weight, are almost totally densified bodies, with almost total absence of pores, cracks and internal defects, which gives it high technical performance : high mechanical, thermal, abrasion and chemical attack resistance.
    In the context of the present invention, the term "micronic particles" refers to 30 particles that have a micrometric size in all three dimensions. In particular, the
    Micronic particles have sizes between 1 micrometer and 500 micrometers.
    In a particular embodiment of the invention, the mineral particles used in the manufacture of the ceramic materials of the invention are substances with a particle size of less than 200 micrometers, preferably less than 100 micrometers, especially preferred is a size of the order tens of microns, between 10-90 micrometers. More preferably, a particle size between 10 and 50 micrometers is used. The proportionate size of the particles refers to the average statistical size thereof. To select the size of the particles, sieves of different sizes are used. Preferably, 98% of the particles of the materials 10 used to prepare the ceramic material of the invention pass through a 45 µm sieve.
    These particles are preferably obtained by grinding the initial raw materials by wet and spray drying, all known techniques in the field of ceramics.
    In a variant of the invention, the composition by weight of the starting materials is in the following ranges:
    - Clays 20-35%
    - Kaolins: 5-15%
    - Feldspar: 50-70% with particle size less than 40 µm.
    Clays provide plasticity to the forming of the starting product. Since there are 20 mixtures of minerals that usually have particle sizes in the range of tens of micrometers, in general it is not necessary to subject them to an intensive grinding process, which allows maintaining the plastic properties of the clay. In the context of the present invention, the clays used have a high plasticity to allow a correct forming of the whole. In particular, the clays of the composition counteract the effect of the feldspar content that hinders the pressing stage.
    In another variant of the invention feldspars confer special properties to the ceramic material of the invention. In particular, feldspars act as fluxes in the cooking process and reduce porosity in the final material.
    In the present invention the size of the feldspar particles is also reduced by 30 micronized to tens of microns. By decreasing the size of the feldspar particles, the specific surface area and therefore their reactivity increases. Thanks to this
    In effect, bridges between the particles are generated, resulting in a compacted material where the pores are isolated from each other generating a closed porosity throughout the volume. In addition, the increase in particle reactivity allows the cooking temperature to be reduced from 1180 ° C to 1140 ° C avoiding pyroplastic deformation. 5
    In the context of the present invention, feldspars represent between 50% and 70% by weight of the materials, more preferably 55-60% by weight. Preferably the feldspars of the composition contain between 15 and 25% by weight of potassium feldspar over the total raw materials, and between 35-45% by weight of sodium feldspar over the total raw materials. 10
    Preferably 99.7% of the feldspar particles have a size less than or equal to 40µm.
    Sodium feldspar acts as a flux of lower viscosity, quickly generating bridges between particles. In addition, the small size of the particles and of the feldspar itself favors the union between the particles, decreasing the internal porosity of the material and resulting in an increase in the density of the material during the sintering process.
    Potassium feldspar brings greater viscosity to the flux, which helps maintain product stability and shape during the cooking process.
    Preferably the starting materials have a high purity which allows an exact control of the compositions and prevents defects in the material. For example, an undetermined content in organic materials can generate the appearance of pores and major defects during cooking, by burning them. The presence of unwanted mineral materials can affect the formation of the vitreous phase, causing internal stresses or problems of planarity or generation of residual porosity.
    In a particular embodiment, the purity of the selected materials is greater than 90%. In a preferred embodiment, the feldspars of the composition have a purity greater than 90% by weight.
    The starting materials can have different compositions, although preferably there is a quantity of non-siliceous melting materials that allow obtaining 45-85% of the vitreous phase.
    In the present invention, "vitreous phase" is understood as the amorphous, non-crystalline phase between the crystalline phase grains. The percentage by weight of the vitreous phase is determined by usual procedures in the field of ceramics. In particular, the percentage by weight of the vitreous phase can be determined by X-ray diffraction.
    In a particular embodiment of the present invention, the compacted ceramic material of the present invention comprises between 45 and 85% by weight of the vitreous phase with respect to the total weight of the compacted ceramic material. Preferably between 45 and 75% by weight of the glass phase, more preferably between 50% and 70% by weight of the glass phase. In a preferred embodiment the glass phase content is 60% by weight with respect to the total weight of the compacted ceramic material. 10
    In the context of the present invention, the vitreous phase of the compacted ceramic material having a low viscosity during the cooking stage, closes the internal pores of the material upon solidification.
    The compacted ceramic material provided by the present invention has a density between 2.3 and 3 g / cm3. Preferably, between 2.4 and 2.7 g / cm3. More preferably, the compacted ceramic material has a density of 2.6 g / cm3. The density measurements provided in the present invention have been taken by immersion in water applying the Archimedes principle.
    In a particular embodiment, the compacted ceramic material has lateral dimensions of up to 4 x 2 m2, preferably up to 3.20 x 1.44 m2. More preferably 20 between 3 x 1 m2 and 4 x 2 m2. In a preferred embodiment, the compacted ceramic material has lateral dimensions of 3.20 x 1.44 m2.
    Preferably, the compacted ceramic material has a table shape with lateral dimensions of 3.20 x 1.44 m2.
    In another particular embodiment, the compacted ceramic material has a thickness of at least 1 cm, preferably 2 cm or 3 cm. Preferably, the compacted ceramic material has lateral dimensions of up to 4 x 2 m2 and a thickness of at least 1 cm. More preferably, the compacted ceramic material has lateral dimensions of 3.20 x 1.44 m2 and a thickness of at least 1 cm, preferably at least 2 cm, more preferably at least 3 cm. 30
    Preferably, the compacted ceramic material has a table shape with lateral dimensions of 3.20 x 1.44 m2 and a thickness of approximately 2 or 3 cm.
    In a further particular embodiment, the compacted ceramic material also has a porosity of less than 4% by volume. Preferably, the compacted ceramic material of the invention has an internal porosity comprised between 1 and 3% by volume. More preferably, the compacted ceramic material of the invention has a porosity of 2% by volume. 5
    "Porosity" means the empty space inside the ceramic material and is expressed in% by volume. The methods of measuring porosity and ceramic materials are known to those skilled in the art. Among these methods are mercury porosimetry, autoclave porosity measurements based on impregnation with water or immersion using simply the Archimedes principle. The 10 porosity measurements provided in the present invention have been taken by autoclave.
    Likewise, the present invention provides a process for manufacturing the compacted ceramic material.
    Once the starting materials are selected and reduced to the desired size, they can be stored for use at the right time. The different materials must be mixed uniformly, and at a suitable degree of humidity that allows for forming and pressing prior to cooking.
    Preferably, the material is mixed with water, or dried if it has been obtained wet, so that the amount in water is between 4% -9% by weight, preferably between 6% and 9%. twenty
    After the preparation of the mixture of particles constituting the raw material, in a variant of the invention the process includes a step of compaction by means of a continuous pressing station, which comprises means of compaction in the form of a roller and compaction tape. . If necessary after compaction, the product is cut as desired, for example in the form of a rectangular table. 25
    After compaction and cutting, the procedure includes a pressing stage at very high pressures, which generates an ultracompaction of the material prior to cooking. This stage contributes to the reduction of porosity in the final product and facilitates the sintering process. In this pressing the pressures may be greater than 400 kg / cm2, preferably greater than 450 kg / cm2. 30
    Once the product is shaped and the ultracompacted materials, a drying stage is carried out to reduce the water content without deforming the part.
    The drying stage can be done in a specific installation, which allows the dried parts to be stored before cooking, facilitating the management of the parts stock. Alternatively, drying can be done in the baking oven, as a step immediately prior to cooking.
    In the context of the present invention, the cooking of the ceramic material is carried out by applying a cooking cycle. The cooking cycle comprises heating the ceramic material to a certain temperature and subsequent cooling.
    Preferably in the cooking cycle, the ceramic material is heated to maximum temperatures between 1000 ° C and 1200 ° C, more preferably between 1000 ° C and 1180 ° C, even more preferably between 1120 ° C and 1160 ° C. In a particular embodiment, the maximum temperature reached in the cooking cycle is between 1180 ° C and 1200 ° C. At these temperatures the melting and sintering of the particles occurs but the deformation of the pieces is avoided, for example by gravity. Preferably, the residence time at the maximum cooking temperature is between 7 and 25 min. fifteen
    During the cooking stage, the vitrification and sintering process generates a viscous liquid phase that helps reduce the porosity in cooking of the product of the invention. In the heating of the cooking cycle, the formation of a viscous glass that surrounds the most refractory particles takes place, and that under the forces of surface tension created by the fine pores of the piece, tends to approximate the particles by increasing the contraction and reducing the porosity of the product. The high density of the starting product resulting from the ultracompaction processes and the selection of the particle size (preferably between 10 and 50 µm) give the product specific characteristics that make the vitrification and sintering process faster.
    In a particular embodiment, the cooking cycle to which the material is subjected has a duration of up to 9 hours. Preferably, the cooking cycle lasts between 1 and 9 hours. In particular, for thicknesses between 8-30 mm the cycle lasts between 100 and 500 min at a maximum temperature between 1170-1200 ° C.
    Therefore, one aspect of the present invention relates to the process for manufacturing the compacted ceramic material comprising a cooking cycle where the cooling rate from the maximum temperature reached up to 700 ° C is between 0.5 and 2 ° C / min. In particular, for thinner thicknesses, the cooling rate applied is slower.
    The inventors of the present invention have found that when the cooling rate is reduced compared to conventional methods, the compacted ceramic materials obtained from the cooking cycle have better mechanical properties, in particular mechanical strength.
    Without being linked to any theory, it is believed that when the cooling rate is slower, the atoms rearrange by decreasing the internal stresses caused. The resulting product has greater stability, allowing the subsequent machining of the piece and avoiding the appearance of cracks or breakage of the material.
    In a variant, the process for manufacturing the compacted ceramic material further comprises an annealing step at 750 ° C. The annealing stage favors the release of internal residual stresses within the material. In a preferred embodiment the annealing step is performed for 4 hours.
    In a particular embodiment, the process for manufacturing the compacted ceramic material further comprises a three-stage grinding phase. The three-stage grinding phase allows to obtain a homogeneous particle size. fifteen
    Conventional steps such as the addition of coloring substances, for example after the grinding stage, the formation of decorative veins using mineral powders of different colors, removal of metal particles, can be included in the process of manufacturing the ceramic material of the invention. etc.
    The product of the invention has unique mechanical properties which allows it to be manufactured in large pieces, even more than 3 meters long and 1.5 meters wide and with a thickness that can reach up to 3 cm or more if necessary.
    These properties make the compacted ceramic materials of the invention excellent in their use as a building material. The high chemical and physical resistance, and the large manufacturing dimensions allow its use in the coating of floors 25 and facades, where they are inert to the action of solar radiation, chemical agents, have high hardness and a controlled internal stress level which allows its cutting and manipulation without breaking the pieces.
    A particularly preferred application for the ceramic materials of the invention are kitchen countertops. The high chemical resistance and its hardness allow contact with 30 foods, food dyes, and beverages such as wine or coffee without generating stains and
    without affecting their properties. In addition, the possibility of manufacturing thicknesses of 3 cm or more gives the countertop an aesthetic appearance similar to that of natural stones.
    The invention will now be illustrated by examples, which should not be construed as limiting the invention, which is defined by the claims.
    Examples 5
    In the following example the following starting materials and amounts by weight were used:
    - 30% clay
    - 15% kaolin
    - 38% sodium feldspar 10
    - 17% potassium feldspar
    All starting materials have a purity greater than 90%.
    By grinding, the size of the feldspathic materials and the rest of the materials is reduced until a particle size below 45 µm is achieved.
    Subsequently, spray spray is sprayed until a product with a water content of 8% is achieved.
    The wet material is subjected to a forming and is ultra-pressed at 450 kg / cm2 until it reaches a thickness of 30 mm.
    Subsequently, it is dried by heat in a drying line until a product with a water content of 0.5% is achieved. twenty
    The dried product is subjected to a 500 min cooking cycle and a temperature of 1,200 ° C.
    The resulting product has a density between 2.4-2.7 g / cm3.
    权利要求:
    Claims (15)
    [1]
    1. Compacted ceramic material comprising between 45-85% by weight of the vitreous phase characterized in that it has a density between 2.3 and 3 g / cm3.
    [2]
    2. Compacted ceramic material according to claim 1 with lateral dimensions of up to 4 x 2 m2, preferably approximately 3.20 x 1.44 m2. 5
    [3]
    3. Compacted ceramic material according to any one of claims 1 and 2 with a thickness of at least 1 cm, preferably about 2 cm or 3 cm.
    [4]
    4. Compacted ceramic material according to any one of claims 1 to 3 which also has a porosity of less than 4% by volume.
    [5]
    5. Process for manufacturing the compacted ceramic material according to claims 1 to 4 comprising a cooking cycle where the cooling rate from the maximum temperature reached up to 700 ° C is between 0.5 and 2 ° C / min.
    [6]
    6. A process for manufacturing the compacted ceramic material according to claim 5 wherein the maximum temperature reached in the cooking cycle is between 1180 ° C and 1200 ° C.
    [7]
    7. Procedure for the manufacture of the compacted ceramic material according to claims 5 and 6 wherein the cooking cycle to which the material is subjected has a duration of up to 9 hours.
    [8]
    8. Process for manufacturing the compacted ceramic material according to claim 5 which further comprises an annealing step at 750 ° C.
    [9]
    9. Compacted ceramic material obtainable according to the procedure defined in any of claims 5 to 8, characterized in that it has a density between 2.3 and 3 g / cm3.
    [10]
    10. Use of the compacted ceramic material according to any one of claims 1 to 4 and 9 as construction material.
    [11]
    11. Use of the construction material according to claim 10 in facades and cladding.
    [12]
    12. A construction material comprising a compacted ceramic material according to any one of claims 1-4.

    [13]
    13. A construction material according to claim 12 for coating floors, walls or facades. 5

    [14]
    14. A construction material according to claim 12 for kitchen countertop.

    [15]
    15. A construction material according to claim 12, as kitchen countertop with a length greater than 3 meters. 10
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    同族专利:
    公开号 | 公开日
    WO2016193501A1|2016-12-08|
    EP3303721B1|2019-01-23|
    ES2593095B1|2017-09-22|
    ES2716120T3|2019-06-10|
    EP3303721A1|2018-04-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP2450326A2|2006-09-29|2012-05-09|Ceramext, LLC|Process for hot-forging synthetic ceramic|
    EP2455353A1|2010-11-19|2012-05-23|Imerys Services|Multilayer ceramic structures|EP3421202A1|2017-06-30|2019-01-02|Manufacturas Siles, S.L.|Method of making a sink from flat, low-porosity, compact porcelain ceramic material slabs|
    ES2823061A1|2019-11-04|2021-05-05|Sucofade S L|PROCEDURE FOR THE REALIZATION OF STRAIGHT OR CURVED FURNITURE FROM FLAT PLATES OF PORCELAIN MATERIAL |ES2442465B1|2012-07-11|2014-08-11|Cosentino Research And Development, S.L.|Procedure for manufacturing solid surfaces for construction|EP3459919A1|2017-09-26|2019-03-27|Flooring Industries Limited, SARL|Ceramic material and slab comprising a ceramic material|
    法律状态:
    2017-09-22| FG2A| Definitive protection|Ref document number: 2593095 Country of ref document: ES Kind code of ref document: B1 Effective date: 20170922 |
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201530796A|ES2593095B1|2015-06-05|2015-06-05|COMPACT CERAMIC MATERIAL WITH A LOW LEVEL OF INTERNAL VOLTAGES AND ITS USE AS A CONSTRUCTION MATERIAL IN COATINGS AND SOILS|ES201530796A| ES2593095B1|2015-06-05|2015-06-05|COMPACT CERAMIC MATERIAL WITH A LOW LEVEL OF INTERNAL VOLTAGES AND ITS USE AS A CONSTRUCTION MATERIAL IN COATINGS AND SOILS|
    PCT/EP2016/062805| WO2016193501A1|2015-06-05|2016-06-06|Reducing internal stresses in ceramic materials|
    EP16729224.2A| EP3303721B1|2015-06-05|2016-06-06|Reducing internal stresses in ceramic materials|
    ES16729224T| ES2716120T3|2015-06-05|2016-06-06|Reduction of internal stresses in ceramic materials|
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