• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    Ceramic glazing with a warm feeling similar to wood. The present invention refers, in a first aspect, to a ceramic glaze that, due to its microstructural characteristics, provides a sensation of warmth to the touch, which is similar to that of wood and whose main application is directed towards the tile manufacturing sector. ceramics, especially for use as flooring for interior surfaces, combining the warmth and aesthetics of wood with the durability and easy-cleaning characteristics of porcelain stoneware, and can be used in the field of varnishes, enamels or frits used in the ceramic flooring, tile and cladding industry. The present invention, in a second aspect, refers to the use of ceramic glazing as flooring for interior surfaces. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2843267A1
    申请号:ES202030020
    申请日:2020-01-15
    公开日:2021-07-16
    发明作者:Beltran Marcos Jovani；Monsonis Javier Garcia
    申请人:Coloronda S L；
    IPC主号:
    专利说明:

    [0002] Ceramic glaze with a warm feeling similar to wood
    [0004] FIELD OF THE INVENTION
    [0006] The present invention, as indicated in its title, refers, in a first aspect, to a ceramic glaze that, due to its microstructural characteristics, provides a sensation to the touch of warmth, similar to that of wood. The present invention has its main application in the field of manufacturing ceramic tiles, especially for use as flooring for interior surfaces, combining the warmth and aesthetics of wood with the durability and easy-cleaning characteristics of porcelain stoneware. being able to be framed in the sector of varnishes, enamels or frits used in the industry of pavements, tiles and ceramic coatings.
    [0008] Likewise, in a second aspect, the invention refers to the use of ceramic glazing as flooring for interior surfaces.
    [0010] STATE OF THE ART
    [0012] The term ceramic glaze is applied to the thin layer of glass on a ceramic body resulting from the process of application and subsequent fusion at high temperature of a mass of raw materials for the purpose of protection, decoration and / or functionalization of the final ceramic product.
    [0014] The production process for a ceramic glaze is relatively simple. It starts with a series of different raw materials, which normally include frits, water-insoluble vitreous compounds that are obtained by melting and subsequent rapid cooling of controlled mixtures of raw materials. Once the raw materials have been dosed, they are wet grinding, generally using ball mills. After this process, a suspension, which must be rheologically conditioned for its subsequent application and fusion at high temperature in order to obtain the ceramic glaze.
    [0016] Ceramic glazes are generally formed by an amorphous network, dispersed without long-range order, the main network former being SiO2, in its anionic form (SiO44-). Other network formers can also be present, such as B2O3 and / or AhO3, in addition to various modifiers such as Na2O, K2O, MgO or CaO.
    [0018] The composition of the glaze, the specific heat, as well as the density presented by the glass network, will mainly depend on the sensation of greater or less warmth when in contact with the human skin of a glaze. The sensation of cold or heat perceived when being in contact with another surface is a consequence of the displacement of thermal energy from the warmer material to the colder material.
    [0020] This transfer of thermal energy in insulating materials, such as glazing, is determined by the transmission of phonons through the material between zones with different temperatures, which in turn will determine the value of thermal conductivity. These phonons, quanta of elastic wave energy or vibration of the interatomic lattice, are diffused by vibrations of the crystal lattice, so that ordered materials, such as crystalline ceramics that have a long-range order, have higher conductivity values. thermal compared to ceramic glasses, which have a highly disordered structure.
    [0022] Proof of this are the thermal conductivity values exhibited by marble, between 2080 - 2940 Wm-1K-1, compared to the 0.96 Wm-1K-1 value of a standard glaze. These values of thermal conductivity of marble or other similar materials are derived from their high crystalline ordering, being classified as cold materials from the point of view of thermal warmth. However, other types of materials such as wood, with thermal conductivity values of around 0.17 Wm-1K-1 for an oak wood, are considered as warm ( Engineering ToolBox, ( 2003). Thermal Conductivity of common Materials and Gases ( online) .Available at: https://www.engineeringtoolbox.com/thermal-conductivity-d_429.html [09/13/2019]) .
    [0024] In this sense, this value of thermal conductivity exhibited by wood is given by its microstructure, formed by a set of elongated and parallel fibers of bonded cellulose, among which there is a high porosity, presenting in This results in an intermediate value of thermal conductivity between that of its solid components and that of the air contained in the pores. Although it is true that there are numerous studies that establish a direct relationship between thermal conductivity values and the sensation of warmth to the touch of a material, other parameters that are also determining must be taken into account, such as thermal effusivity and surface contact ( Y. Obata, K. Takeuchi, Y. Furuta, K. Kanayana. Research on better use of Wood for sustainable development: Quantitative evaluation of good tactile warmth of wood, Energy. 30, 1317-1328, 2005).
    [0026] Thermal effusivity (e) is defined as the rate at which a material absorbs heat. This property determines the temperature of the contact interface between two bodies at different temperatures. Therefore, the higher the thermal effusivity of a material, the more easily heat will spread in that material and, consequently, the thermal sensation to the touch will be cooler. It is a directly proportional measure of the thermal conductivity (k), also involving the density (p) of the material and its heat capacity (C p ), as shown in equation (1).
    [0031] Another determining factor to consider is the contact surface. The roughness of a material has a direct influence on the thermal sensation to the touch of the same, by modifying the contact area between the material and the skin. Consequently, a ceramic material with a certain surface roughness will convey a feeling of warmth to the touch that is higher than if its surface is completely smooth.
    [0033] Therefore, wood presents this sensation of warmth to the pleasant touch due to its low thermal conductivity and its high internal porosity, consequently with a low thermal effusivity. In addition, some woods present a surface roughness that favors an increase in the sensation of warmth to the touch due to the decrease in the contact surface.
    [0035] As a result of these characteristics, wood, as well as other types of polymeric materials with similar characteristics, are widely used as flooring for interiors, due both to their warmth and to their elegance and aesthetics. In On the other hand, these surfaces have a series of disadvantages compared to ceramic flooring, with durability problems arising as a result of chemical attacks, scratching, bulging due to water absorption, as well as greater difficulty in cleaning them.
    [0037] Due to the disadvantages presented by wood compared to ceramic flooring, many efforts have been and continue to be devoted to the development of ceramic glazes that combine the good warmth characteristics of wood with the durability and easy-to-clean advantages of porcelain stoneware.
    [0039] For this purpose, two well differentiated strategies have been documented: that of creating porosity in the glaze itself and that of hindering the diffusion of phonons through the glazing through the devitrification of different phases of a crystalline nature. The growth of crystalline structures within a glaze gives rise to the so-called glass-ceramic materials or ceramic glazes.
    [0041] Glass-ceramic materials can be defined as those polycrystalline materials formed by the nucleation and controlled crystallization of glasses, where the crystalline phase must be equal to or greater than 50% of the volume of the glass. In order to cause the devitrification of the crystalline structures and provide a greater sensation of warmth, one of the solutions in the state of the art has been the devitrification of feldspathic structures, such as anorthite and albite (see for example EP3075714).
    [0043] Another of the strategies known in the state of the art to provide a sensation of thermal warmth is the incorporation of porosity in the enamel itself. To this end, the state of the art describes the addition of hollow particles on the enamel surface (JP2005041741), on the enamel itself and on the support (JP2005133337) and the introduction of intermediate layers with a porous structure (JP2005139797 and JP2005139796) .
    [0045] Furthermore, the use of different oxides is also known in the art ( E. Bernardo, MD Lazzari, P. Colombo, AS Llaudis, FJ Garcia-Ten, Lightweight Porcelain Stoneware by Engineered CeÜ 2 Addition, Adv. Eng. Mater. 12, 65-70, 2010 and H. Zhou, K. Feng, C. Chen, Z. Yan, Influence of CeÜ 2 addition on the preparation of foamed glass-ceramics form high-titanium blast furnace slag, Int. J. Min. Met . Mater. 25, 689- 695, 2018), carbides ( G. Scarinci, G. Brusatin, E. Bernardo, Production Technology of Glass Foams, in: M. Scheffler, P. Colombo ( Eds.), Cellular Ceramics, Structure Manufacturing, Properties and Applications , Wiley-VCH, Weinheim, Germany, 2005), nitrides ( M. Marangoni, B. Nait-Ali, DS Smith, M. Binhussain, P. Colombo, E. Bernardo, White sintered glass-ceramic tiles with improved thermal insulation properties for building applications, J. Eur. Ceram. Soc. 37, 1117-1125, 2017) and industrial waste ( RV Silva, J. Brito, CQ Lye, RK Dhir, The role of glass waste in the production of ceramic-based products and other applications: A review, J. Clean. Prod.
    [0046] 167, 346-364, 2017) to favor the formation of internal porosity in the glaze.
    [0048] Although in all these documents and investigations the sensation of thermal warmth is improved, there is a worsening of other properties, such as mechanical resistance or water absorption in the case of its application in porcelain stoneware.
    [0050] Another of the solutions known in the state of the art is the combination of the ceramic material with an organic coating, obtaining an organic-inorganic hybrid tile (see for example the applications WO2013095308 and WO2008122677) in order to achieve the proposed objective of improving the feeling of warmth to the touch. However, the use of organic-inorganic hybrid materials has numerous disadvantages, notably decreasing properties such as durability and resistance to chemical attack compared to a ceramic product, also introducing greater complexity during the processing of said materials.
    [0052] For all the aforementioned, it would be advantageous to develop new ceramic glazes with thermal warmth properties similar to wood, without causing a deterioration in the mechanical properties and durability intrinsic to porcelain stoneware. Pursuing this objective, the control of the microstructure together with the control of the crystallinity of the glaze and the surface roughness of the material will be the simultaneous strategies to be followed in the present invention.
    [0054] SUMMARY OF THE INVENTION
    [0056] The present invention addresses the problem of developing a ceramic glaze for porcelain stoneware that provides a sensation of warmth to the touch similar to that of wood and also maintain the properties of mechanical strength, resistance to chemical attack and water absorption characteristic of porcelain stoneware.
    [0058] The solution provided in the present invention is based on obtaining a ceramic glaze with high internal porosity, as well as a certain surface roughness. The crystallization of different ordered crystalline phases, together with the formation of a high internal porosity within the glaze, produce a drastic decrease in the thermal conductivity of the material, due to the difficulty of the phonons to diffuse through the glass-ceramic network. which is directly related to the decrease in thermal effusivity values, as mentioned above. If these characteristics are added to the possibility of reducing the contact surface between ceramic glazing and human skin by creating surface roughness, the sensation of warmth exhibited by ceramic glazing will potentially resemble that exhibited by wood, with optimal characteristics for use as flooring on interior surfaces.
    [0060] BRIEF DESCRIPTION OF THE FIGURES
    [0062] Figure 1: Optical microscopy of a cross section of a piece made up of a ceramic support, layers of slip and the ceramic glaze of the invention heat-treated at high temperature, observing the high internal porosity of the ceramic glaze.
    [0064] Figure 2: X-ray powder diffractogram of the ceramic glaze of the invention fired at high temperature. The crystallization of the H phases are observed: Hyalofana; S: Sanidine and C: Cerium oxide.
    [0066] Figure 3: Scanning electron microscopy micrographs of the ceramic glaze of the invention: a) Micrograph of the surface, where the crystallizations of the crystal structures observed by X-ray diffraction, the hyalophane ( H), sanidine (S) and cerium oxide (C). b) Micrograph of the cross section, observing the high internal porosity of the material, showing bubbles between 10 and 300 ^ m in diameter. Crystal structures were identified by X-ray energy scattering microanalysis.
    [0067] Figure 4: Optical microscopy of a cross section of a piece made up of a ceramic support, the ceramic glaze of the invention and a cover with less porosity of the ceramic glaze of the invention, heat treated at high temperature.
    [0069] Figure 5: X-ray powder diffractogram of a conventional product cooked at high temperature. The crystallization of phases B are observed: Baddeliyite; By: Bywtownita and H: Hialofana.
    [0071] Figure 6: Scanning electron microscopy micrographs of the surface: a) of the ceramic glaze of the invention and b) of a product. In the glass-ceramic material of the invention, the crystallizations of hyalophane (H) and sanidine (S) are observed within the glaze (V). On the other hand, the observed crystallizations of baddeliyite (B), bytownite (By) and hyalofana (H) in the glaze of the conventional matte (V), are of notably smaller sizes than those presented by the glass-ceramic of the invention. Crystal structures were identified by X-ray energy scattering microanalysis.
    [0073] Figure 7: Comparison of the internal porosity of a) a ceramic glaze of the invention and b) the conventional product described in Example 2. The images show the difference in internal porosity between both materials.
    [0075] Figure 8: Topographic map of surface roughness for the ceramic glaze of the invention.
    [0077] Figure 9: Topographic map of surface roughness for a conventional granulated product.
    [0079] Figure 10: X-ray powder diffractogram of the glass-ceramic coating of the invention fired at high temperature. The crystallization of the H phases are observed: Hyalofana; S: Sanidine.
    [0080] Figure 11: Optical microscopies of the cross section of a) a piece made up of a ceramic support, ceramic glaze of the invention and glass-ceramic coating, b) conventional enamel on a slipped piece, heat treated at high temperature.
    [0082] Figure 12: Scanning electron microscopy micrograph of the cross-section of the glass-ceramic enamel of the invention with a glass-ceramic coating after heat treatment at high temperature
    [0084] DETAILED DESCRIPTION OF THE INVENTION
    [0086] The invention provides a ceramic glaze with a sensation of thermal warmth similar to that of wood, with a thermal conductivity of between 0.2 to 0.6 Wm-1K-1 and an effusivity of between 330 to 1000 Ws1 / 2 / m2K , which comprises a crystalline phase consisting of sanidine microcrystals (KAlSi3O8), hyalophane microcrystals ((K, Ba) [Al (Si, Al) Si2O8]) and CeO2 microcrystals, where the microcrystals have a rectangular morphology, a glassy phase in a percentage lower than 37% by weight with respect to the total weight of the ceramic glaze and an internal porosity-forming component in a percentage between 2 and 12.5% by weight with respect to the total weight of the ceramic glaze.
    [0088] The ceramic glaze of the invention presents, within the glaze, devitrifications of microcrystals of feldspathic crystalline structures of hyalophane ((K, Ba) [Al (Si, Al) Si2O8]) and sanidine (KAlSi3O8). Both crystal structures have a monoclinic C2 / m symmetry. Furthermore, in the ceramic glaze crystalline structures are also present from the raw materials mixed with the frit, with the presence of CeO2 with a cubic crystalline structure Fm / 3m. The presence of crystalline structures was confirmed by X-ray energy dispersion microanalysis. The percentage of glass phase in the glass-ceramic material is in a proportion less than 37% of the total weight of the material (see Figures 2 and 3).
    [0090] The presence of three different crystalline structures of micrometric sizes separated from each other by the vitreous phase significantly hinders the diffusion of phonons through the material (see figure 6). In addition, the presence of barium cations (of high ionic radius) in the crystalline structure of hyalophone generates a structure highly disordered crystalline, also hindering the diffusion of phonons through the material.
    [0092] The ceramic glaze has a high internal porosity, with micrometric size bubbles between 10 and 300 µm in diameter (see Figures 1 and 3b). The air contained in the pores created within the glazing of the invention causes a decrease in the thermal conductivity of the material, hindering the diffusion of phonons (thermal diffusion in air occurs by convection, as opposed to diffusion through vibrations of the interatomic network in a glaze). As a direct consequence of the increase in internal porosity and the consequent decrease in thermal conductivity, the value of thermal effusivity will also be considerably decreased according to equation 1.
    [0094] In the present invention, the internal porosity-forming component is capable of creating porosity within the glaze. In a preferred embodiment, said internal porosity-forming component is selected from the group consisting of Si3N4, PrO2, SiC, Nd2O3 or combinations thereof.
    [0096] The ceramic glaze of the present invention has an average surface roughness (ra) of between 3 and 10 µm, this having a direct influence on the thermal sensation to the touch by modifying the contact area between the material and the skin.
    [0098] For the preparation of the ceramic glaze of the invention, between 80% and 20% by weight of the frit described in table 1 and between 80% and 20% of the different raw materials selected from silicon oxide, silicate zirconium, aluminum oxide, zinc oxide, silicon nitride, calcium carbonate, cerium oxide, mullite, kaolin, sodium feldspar, wollastonite, nepheline, praseodymium oxide, barium oxide, boron oxide, magnesium carbonate, clay, strontium carbonate, silicon carbide and industrial residues, preferably between 30% and 70% frit and 30 and 70% raw materials, are wet ground together with the necessary additives, these being carboxymethylcellulose and sodium tripolyphosphate , in amounts of between 0% and 2% with respect to the aqueous suspension, also including the necessary preservative. The resulting suspension is rheologically conditioned and applied on a previously dipped porcelain stoneware support, for subsequent heat treatment at high temperature, obtaining a thin layer of the glass-ceramic material.
    [0099] Table 1: Composition of the frit -% by weight with respect to the total weight of the frit
    [0104] Density and viscosity are the most relevant quantities for enamel suspensions. The values that these parameters must possess will depend directly on the specific enamel application system to be used in each particular case, but in any case they must be such as to ensure the obtaining of a consolidated layer of dry enamel with adequate characteristics.
    [0106] In the present invention, the resulting suspension preferably has density values between 1.85 and 1.95 g / cm3.
    [0108] The heat treatment is carried out in industrial firing cycles lasting between 30-90 minutes and temperatures of 1150 ° C and 1220 ° C. The ceramic glaze resulting from this heat treatment presents the percentage by weight, with respect to the final product, expressed in terms of the following equivalent oxides, shown in the following table 2.
    [0109] Table 2: Percentage by weight of equivalent oxides in the ceramic glaze resulting from the heat treatment
    [0114] In a preferred embodiment, the percentage by weight with respect to the final product, expressed in terms of equivalent oxides of SIO2, is between 40% and 55%.
    [0116] In a preferred embodiment, the percentage by weight with respect to the final material, expressed in terms of equivalent oxides of BaO, is between 0% and 15%.
    [0118] In another preferred embodiment, the percentage by weight with respect to the final material, expressed in terms of equivalent oxides of AhO3, is between 10% and 20%.
    [0120] Preferably, the percentage by weight with respect to the final material, expressed in terms of equivalent oxides of CaO, is between 5% and 15%.
    [0122] Preferably, the percentage by weight with respect to the final material, expressed in terms of equivalent oxides of ZrO, is between 0% and 7.5%.
    [0123] In another preferred embodiment, the percentage by weight with respect to the final material, expressed in terms of equivalent oxides of CeO2, is between 0% and 10%.
    [0125] In still another preferred embodiment, the percentage by weight with respect to the final material, expressed in terms of equivalent oxides of PrO2, is between 0% and 2.5%.
    [0127] In the present invention, the application of the ceramic glaze was carried out on an enamelling line, using an enamelling bell, although it is capable of being applied by other techniques known in the field of the ceramic industry. In the hood, the enamel is pumped from the container that contains it to a reservoir above the hood. Said deposit drops the suspension by gravity on the surface of the hood, forming a continuous curtain. The enamel application was carried out on a porcelain stoneware support, previously dipped. Preferably, the thickness of the glass-ceramic enamel is in the range of 300-600 µm (Figure 1).
    [0129] The enamel can be applied directly on the ceramic support without the use of a slip. Additionally, the glass-ceramic enamel may present a thin coating of the same glass-ceramic nature and composition described in table 2 with less internal porosity, in order to provide greater surface protection (figure 4). Said glass-ceramic coating is capable of being applied by means of the "airless" technique.
    [0131] The porcelain stoneware support on which the ceramic glaze of the invention was applied was fired in an industrial roller kiln, preferably in firing cycles lasting between 30 and 90 minutes with maximum temperatures between 1150 and 1220 ° C, as mentioned above.
    [0133] The maximum temperature acquired in the thermal processing used for the firing of the porcelain stoneware piece and the formation of the ceramic glaze layer is decisive, the degree of internal porosity of the material of the present invention depending critically on both parameters, as well as the surface roughness.
    [0134] The ceramic glaze of the present invention, applied on a standard porcelain stoneware support, has values of mechanical resistance to bending of between 30 and 40 N / mm2.
    [0136] The ceramic glaze of the present invention does not show abrasive wear up to 600 revolutions, being consequently class 2.
    [0138] The ceramic glaze of the present invention does not have water absorption.
    [0140] The ceramic glaze of the present invention exhibits resistance to chemical attack and staining.
    [0142] In another aspect, the invention refers to the use of the ceramic glaze of the invention as a coating on porcelain stoneware supports for paving interior surfaces.
    [0144] Likewise, the ceramic glaze deposited on a ceramic support, preferably previously covered with a layer of slip, can also be used as both thermal and acoustic insulation material.
    [0146] In another aspect of the invention, the ceramic glaze can be applied directly on the ceramic support, avoiding the use of a slip layer, additionally presenting a thin coating of the same non-porous glass-ceramic material or with less porosity.
    [0148] The ceramic glaze of the invention, deposited on a ceramic support, preferably previously covered with a layer of slip, can optionally be decorated using inkjet printing technology , simulating the aesthetics of wood, for the flooring. of interior surfaces. In this particular case, the porcelain stoneware piece may also present relief
    [0150] EXAMPLES
    [0152] Example 1: Comparison between the ceramic glaze of the invention and a conventional porcelain glaze. Characteristics and properties.
    [0153] For the elaboration of the ceramic glazes, initially the weighing of the raw materials was carried out. Table 3 below shows the components for both the ceramic glaze of the invention and for a conventional porcelain glaze.
    [0155] Table 3: Raw materials used to obtain the ceramic glaze of the invention and a conventional enamel
    [0160] The percentages by weight of equivalent oxides of frits A and frit B are shown in the following table 4:
    [0162] Table 4: Percentage by weight of equivalent oxides of the frits used
    [0167] Subsequently, the raw materials were wet grinding in an alumina ball mill, with 75% solids content and 25% water for 18 minutes. The resulting suspensions were characterized by showing rejections between 1 and 2% in a 45 µm mesh. The slips were rheologically conditioned and applied with a hood on a piece of porcelain stoneware previously dipped. The application weight was around 670 g / m2. The rheological conditioning of the viscosity was carried out using a 4mm Ford cup, adjusting the viscosities of both glazes for around 50 seconds.
    [0169] The pieces obtained were baked in a single-channel roller oven in a cycle of 50 minutes at a maximum temperature of 1185 ° C for 7 minutes.
    [0170] The following table 5 shows the percentage by weight of equivalent oxides for the ceramic glaze of the invention and for the conventional enamel after its heat treatment at high temperature.
    [0172] Table 5: Percentage by weight of equivalent ceramic glazed oxides of the invention and for conventional enamel
    [0177] Figures 2 and 5 show the powder X-ray diffractions of the glass-ceramic material of the invention and of the conventional enamel, respectively, after heat treatment at 1185 ° C for 7 minutes.
    [0179] For the ceramic glaze of the invention, the crystallization of feldspathic structures of hyalophane and sanidine is observed in addition to the crystallization of cerium oxide. The percentages of crystalline phase versus vitreous phase are 63% and 37% respectively (see figure 2).
    [0181] For conventional enamel, the crystallization of different structures is observed, such as baddeliyite (ZrO2), bytownite (AlSi2O8) and hyalophane ((K, Ba) [Al (Si, Al) Si2O8]). The percentages of crystalline phase versus glass phase are 61% and 38%, respectively (see figure 4).
    [0183] In the micrographs made for both the ceramic glaze of the invention and for the conventional glaze, the different crystalline structures detected by X-ray analysis are confirmed. The sizes of the crystalline structures present in the glaze are slightly higher in the ceramic glaze of the invention (figure 6).
    [0185] Therefore, the crystal structures were confirmed by X-ray energy scattering microanalysis in both cases.
    [0187] The ceramic glaze of the invention has a high internal porosity, compared to conventional enamel (see figure 7).
    [0189] Table 6 below summarizes the main properties of the ceramic glaze of the invention in comparison with those of conventional enamel.
    [0191] Table 6: Properties of the ceramic glaze of the invention compared to those of conventional enamel
    [0196] The percentage of glass and crystalline phase is obtained from the X-ray diffractogram, by subtracting the crystalline phase from the total spectrum in the range of 20 = 20 70. These measurements were carried out on a Bruker D2 phaser.
    [0198] Scanning electron microscopies and microanalyses were performed on a JEOL 7001F EDX-WDX Oxford, INCA 350 / Wave 200 equipment.
    [0200] The surface roughness determination test was carried out using a HOMMELWERKE T8000 roughness tester, using a diamond point stylus with a 90 ° curvature and a radius of 5 ^ m.
    [0202] Thermal conductivity and effusivity measurements were performed using a C-Therm Technologies MATHIS TCi thermal conductivity analyzer, according to ASTM D7984-S.
    [0204] The determination of the resistance to surface abrasion has been carried out according to the UNE-EN ISO 10545-7: 1996 standard.
    [0206] The determination of the flexural strength has been carried out according to the UNE-EN ISO 10545-4: 2015 standard.
    [0208] The determination of resistance to chemical attack has been carried out according to the UNE-EN ISO 10545-13: 2017 standard.
    [0210] The determination of resistance to stains has been carried out according to the UNE-EN ISO 10545-14: 2015 standard.
    [0211] The determination of water absorption has been carried out according to the UNE-EN ISO 10545-3: 2018 standard.
    [0213] The ceramic glaze of the present invention has thermal conductivity and effusivity values much lower than those presented by a similar conventional material.
    [0215] Example 2: Comparison of the ceramic glaze of the invention versus a conventional glaze in a blind experiment
    [0217] In order to evaluate the sensation of warmth experienced when in contact with the ceramic glaze of the invention, a blind experiment was carried out with the two products described in example 1. For this, 30 people were chosen (15 men and 15 women ) aged between 19 and 63 years. The 2 porcelain stoneware pieces, one covered with the ceramic glaze of the invention and the other with the conventional glaze, were placed in a room heated at 18 ° C for 6 hours. After this time, considering the 2 pieces in thermal equilibrium, each individual separately took off his shoes and stepped on each of the pieces for 15 seconds, always with the same foot. Subsequently, the individual determined which of the 2 pieces gave him a greater sense of warmth.
    [0219] Of the 30 individuals who carried out the experiment, a total of 30 determined that the porcelain stoneware support coated with the ceramic glaze of the invention provided a greater sensation of warmth. Therefore, 100% of the individuals considered that the porcelain stoneware support with the ceramic glaze of the invention presented a greater sensation of warmth, ahead of the porcelain stoneware piece covered with conventional enamel.
    [0221] Example 3: Comparison of the roughness of the ceramic glaze of the invention against a conventional granulated porcelain glaze in a blind experiment
    [0223] In order to determine the direct influence of roughness on the thermal sensation to the touch, the ceramic glaze of the invention and the conventional glaze described in example 1 were compared by means of a blind experiment, applying on this Lastly, a grit coating in order to create roughness. To do this, the process detailed in Example 1 was followed, applying prior to cooking by means of the technique called "airless", a quantity of granules of around 15 grams. The suspension of granules consisted of 20% frit and a 80% organic vehicle The frit used as granules had a particle size between 0.2 and 0.045 mm and the following percentage by weight of equivalent oxides:
    [0225] Table 7: Percentage by weight of equivalent oxides of the frit used as coating grit in order to create roughness
    [0230] A ceramic material with a certain surface roughness will convey a feeling of warmth to the touch that is higher than in the case of a totally smooth surface. Figures 7 and 8 show the topographic maps at the same scale for the ceramic glaze of the invention and the conventional glaze with the grit coating, respectively. A greater roughness can be observed for the conventional glaze with grit than for the ceramic glaze of the invention. The values of thermal conductivity, thermal effusivity and surface roughness of both materials are shown in the following table 8.
    [0232] Table 8: Properties of the ceramic glaze of the invention compared with granulated conventional glass-ceramic enamel
    [0237] In order to verify the influence of surface roughness on the sensation of thermal warmth transmitted to contact, a blind experiment was carried out. Analogously to Example 2, a blind experiment was carried out following the same guidelines. In this case, the sensation of warmth perceived by 30 individuals (15 women and 15 men) when stepping on a piece of porcelain stoneware coated with the ceramic glaze of the invention and another piece of porcelain stoneware coated with a conventional glaze with grain coating was evaluated. .
    [0239] Of the 30 individuals who carried out the experiment, a total of 30 determined that the porcelain stoneware support coated with the ceramic glaze of the invention presented a greater sensation of warmth. Therefore, 100% of the individuals considered that the porcelain stoneware support with the ceramic glaze of the invention presented a greater sensation of warmth.
    [0241] Example 4: Comparison of the ceramic glaze of the invention versus a piece of solid wood laminate flooring. Characteristics and properties
    [0242] The ceramic glaze of the invention described in example 1 is compared in this example with a piece of solid wood laminate flooring, widely used as flooring on interior surfaces. The following table summarizes the main properties for the ceramic glaze of the invention, compared to those of a solid wood flooring.
    [0244] Table 9: Properties of the ceramic glaze of the invention compared to those of a solid wood laminate flooring
    [0249] The ceramic glaze of the invention presents values of thermal conductivity and effusivity very close to those of wooden flooring, in addition to a greater surface roughness.
    [0251] The ceramic glaze of the invention has characteristics of resistance to abrasion, chemical attack, as well as optimal water absorption for use on interior surfaces.
    [0253] Consequently, the ceramic glaze of the invention combines the thermal conductivity and effusivity characteristics typical of wood with the characteristics of resistance, durability and easy cleaning intrinsic to porcelain stoneware.
    [0254] Example 5: Comparison of the ceramic glaze of the invention versus a solid wood laminate flooring using a blind experiment
    [0256] In order to compare the sensation of warmth when in contact with the ceramic glaze of the invention with that of a wooden floating floor, a blind experiment was carried out with the materials described in the previous example. For this, 30 people (15 men and 15 women) aged between 19 and 63 years were chosen. Analogously to Example 3, a porcelain stoneware piece with the ceramic glaze of the invention and a solid wood laminate piece were placed in a room heated at 18 ° C for 6 hours. After this time, considering the pieces in thermal equilibrium, each individual separately took off his shoes and stepped on each of the pieces for 15 seconds, always using the same foot. Subsequently, each individual determined which of the 2 pieces gave them a greater sense of warmth.
    [0258] Of the 30 individuals who carried out the experiment, a total of 26 determined that the porcelain stoneware support covered with the ceramic glaze of the invention provided a greater sensation of warmth. In contrast, only 4 people considered that the solid wood flooring presented a greater sensation of warmth when in contact with the skin. Therefore, 86.6% of the individuals considered that the porcelain stoneware support with the ceramic glaze of the invention presented greater warmth compared to the solid wood flooring.
    [0260] Example 6: Comparison between the ceramic glaze of the invention with a glass-ceramic coating and a conventional porcelain glaze. Characteristics and properties.
    [0262] A thin glass-ceramic coating is applied to the ceramic glaze of the invention described in Example 1, in order to enhance its mechanical resistance. For the preparation of the glass-ceramic coating, frit A described in example 1 was used, as well as different raw materials.
    [0264] The following table shows the dosed components to obtain the glass-ceramic coating.
    [0265] Table 10: Dosed components to obtain the coating
    [0266] glass ceramic.
    [0271] Subsequently, the wet grinding of the raw materials was carried out in an alumina ball mill, with 75% solids content and 25% water for 18 minutes. The resulting suspension was characterized by rejection between 1 and 2% on a 45 µm mesh. The slip was rheologically conditioned and applied using the "airíess" technique on a piece of porcelain stoneware previously glazed with the glass-ceramic of the invention. The application grammage of the was around 0.1 g / cm2 and the application density was adjusted around 1.50 g / cm3. The deposited layer was about 0.5 µm thick (Figure 1).
    [0273] The following table shows the percentage by weight of equivalent oxides for the glass-ceramic coating after its heat treatment at high temperature.
    [0275] Table 11: Percentage by weight of equivalent oxides for the glass-ceramic coating after its heat treatment at high temperature.
    [0280] Figure 10 shows the powder X-ray diffraction of the glass-ceramic coating, after heat treatment at 1185 ° C for 7 minutes.
    [0282] The diffractogram shows the crystallization of feldspathic microstructures such as sanidine (KAlSi3O8 and hyalophane ((K, Ba) [Al (Si, Al) Si2O8]). The percentages of crystalline phase and glass phase are 68, 5% and 31.5 respectively.
    [0284] The ceramic glaze of the invention with the glass-ceramic coating has a high internal porosity, compared to conventional enamel (Figure 11).
    [0286] The ceramic glaze of the invention has a spherical internal porosity of sizes between 100 and 20 µm in diameter (Figure 12).
    [0288] The following table summarizes the main properties of the ceramic glaze of the invention with the coating compared to those of conventional enamel.
    [0289] Table 12: Comparison of the main properties of the ceramic glaze with the coating of the invention with that of a conventional glaze
    [0294] The percentage of glass and crystalline phase is obtained from the X-ray diffractogram, by subtracting the crystalline phase from the total spectrum in the range of 20 = 20 70. These measurements were carried out on a Bruker D2 phaser.
    [0296] Scanning electron microscopies and microanalyses were performed on a JEOL 7001F EDX-WDX Oxford, INCA 350 / Wave 200 equipment.
    [0298] The surface roughness determination test was carried out using a HOMMELWERKE T8000 roughness tester, using a diamond point stylus with a 90 ° curvature and a radius of 5 ^ m.
    [0300] Thermal conductivity and effusivity measurements were performed using a C-Therm Technologies MATHIS TCi thermal conductivity analyzer, according to ASTM D7984-S.
    [0301] The determination of the resistance to surface abrasion has been carried out according to the UNE-EN ISO 10545-7: 1996 standard.
    [0303] The determination of the flexural strength has been carried out according to the UNE-EN ISO 10545-4: 2015 standard.
    [0305] The determination of resistance to chemical attack has been carried out according to the UNE-EN ISO 10545-13: 2017 standard.
    [0307] The determination of resistance to stains has been carried out according to the UNE-EN ISO 10545-14: 2015 standard.
    [0309] The determination of the impact resistance has been carried out according to the UNE-EN ISO 10545-5: 1998 standard.
    [0311] The determination of water absorption has been carried out according to the UNE-EN ISO 10545-3: 2018 standard.
    [0313] The ceramic glaze of the present invention has values of thermal conductivity and effusivity that are much lower than those presented by a similar conventional material, presenting the mechanical resistance properties intrinsic to porcelain stoneware.
    权利要求:
    Claims (8)
    [1]
    1. Ceramic glazing with a sensation of thermal warmth similar to that of wood, with a thermal conductivity of between 0.2 to 0.6 Wm-1K-1 and an effusivity of between 330 to 1000 Ws1 / 2 / m2K, characterized because it comprises a crystalline phase consisting of microcrystals of sanidine (KAlSi3O8), microcrystals of hyalophane ((K, Ba) [Al (Si, Al) Si2O8]) and microcrystals of CeO2, where the microcrystals have a rectangular morphology, a glassy phase in a percentage less than 37% by weight with respect to the total weight of the ceramic glaze and an internal porosity-forming component in a percentage between 2 and 12.5% by weight with respect to the total weight of the ceramic glaze.
    [2]
    2. Ceramic glaze according to claim 1, characterized in that the internal porosity-forming component is selected from the group consisting of Si3N4, PrO2, SiC, Nd2O3 or combinations thereof.
    [3]
    3. Ceramic glaze according to claim 1 or 2, characterized in that it has internal porosity with bubbles of micrometric sizes between 10 and 300 µm in diameter.
    [4]
    4. Ceramic glaze according to any of the preceding claims, characterized by an average surface roughness (ra) of between 3 and 10 µm.
    [5]
    5. Ceramic glaze according to any of the preceding claims, characterized in that, after heat treatment in industrial firing cycles lasting between 30 - 90 minutes and temperatures of 1150 ° C and 1220 ° C, it presents the following percentage by weight, with respect to the final product, expressed in terms of the following equivalent oxides:
    Between 30% and 60% SiO2,
    Between 0% and 25% BaO,
    Between 5% and 20% of AhO3,
    Between 3% and 20% CaO,
    Between 0% and 10% Na2O,
    Between 1% and 5% K2O,
    Between 0% and 10% ZrO,
    Between 0% and 5% of B2O3
    Between 0% and 6% ZnO,
    Between 0% and 2% MgO,
    Between 0% and 5% PrO2,
    Between 0% and 20% CeO2,
    Between 0% and 2% of PbO,
    Between 0% and 1% of P2O5,
    Between 0% and 5% SrO.
    [6]
    6. Use of a ceramic glaze according to any of the preceding claims, as a coating on porcelain stoneware supports for paving interior surfaces.
    [7]
    7. Use of a ceramic glaze according to any of the preceding claims, for a non-porous glass-ceramic glaze coating, as a porous glaze coating, notably improving the glaze's mechanical resistance to impact.
    [8]
    8. Use of a ceramic glaze according to any of the preceding claims, as a coating on porcelain stoneware supports, preferably the stoneware support previously coated with a layer of slip, as a thermal and acoustic insulation material.
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    同族专利:
    公开号 | 公开日
    ES2843267B2|2021-11-24|
    WO2021144490A1|2021-07-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20110111944A1|2009-11-06|2011-05-12|Huzhou Ta Hsiang Glass Products Co., Ltd.,|MgO-A12O3-SiO2-Based Crystallizable Glass and Crystallized Glass, and Manufacturing Method Thereof|
    CN108178514A|2018-01-19|2018-06-19|佛山科学技术学院|A kind of building ceramic tiles gentle eye protection matting glaze and its preparation process|
    CN108863079A|2018-08-02|2018-11-23|德化县如瓷生活文化有限公司|A kind of hacking dumb light ceramic whiteware and preparation method thereof|
    CN109399932A|2018-12-25|2019-03-01|佛山科学技术学院|A kind of ceramic glaze and ceramics|
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