Nanometer sub-optical raw stone super wear-resistant diamond glaze, ceramic tile and preparation method thereof

Abstract

The present application relates to the field of building ceramic materials, and particularly discloses a kind of nano sub-light original stone super wear-resistant diamond glaze, ceramic tile and preparation method thereof, the diamond glaze includes the following chemical composition: SiO246.00~55.00%, Al2O310.00~18.00%, K2O+Na2O=5.00~9.30%, CaO+MgO+SrO+ZnO+BaO=19.00~35.00%, ZrO22.00~6.50%, SiO2 / Al2O3=3.5~4.5, K2O / Na2O=1.1~3.0;The diamond glaze coexists nano zirconium oxide grain, zirconium silicate grain and zirconium-containing silicate M grain.The present application also discloses a kind of nano sub-light original stone super wear-resistant ceramic tile and preparation method thereof correspondingly.Adopting the present application, high hardness, good wear resistance, good stain resistance, ideal color development can be realized simultaneously, with good sub-light effect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of building ceramic materials, and in particular to a nano-subtle original stone super wear-resistant diamond glaze and ceramic tile and a preparation method thereof. BACKGROUND

[0002] Subtle bricks advocate a healthy atmosphere without light pollution, and according to the law of spatial refraction, the reflection of ceramic tiles is controlled at a subtle level of 6-10°, so that the light and shade of space are moderate, and a comfortable light sensing state is created for the eyes, avoiding fatigue hazards, thus giving the product special texture and special artistic charm and being favored by users. Different scenes, different people have different feelings, cognition and preferences for light. The present application aims to provide a glaze with good 6-10° subtle effect and comprehensive performance.

[0003] Prior art 1 is Chinese patent document CN111807704A, which discloses a subtle glaze applied to sanitary ceramics, comprising the following raw materials by weight: 25-27 parts of potassium feldspar, 17-20 parts of quartz, 1-3 parts of zinc oxide, 8-12 parts of dolomite, 5-8 parts of wollastonite, 5-8 parts of kaolin, 6-8 parts of alumina, 7-9 parts of zirconium silicate, 1-4 parts of frit, 6-9 parts of barium carbonate, 5-9 parts of calcined talc and 0.5-1.5 parts of lithium carbonate. The chemical composition of the glaze paste includes the following components by mass percentage: 50.0-58.0% SiO2, 15.0-17.0% Al2O3, 1.0-2.5% ZnO, 6.0-9.0% CaO, 3.0-4.5% MgO, 4.0-6.5% BaO, 4.5-6.0% ZrO2, 3.0-4.0% K2O, 0.5-1.0% Na2O, 0.2-0.6% Li2O. Prior art 1 introduces a certain amount of lithium carbonate to achieve fluxing, reduce the melting temperature of the raw materials, facilitate the mutual fusion of the raw materials, and improve the viscosity of the frit through lithium carbonate to reduce the viscosity of the subtle glaze, so that the flow performance of the subtle glaze is improved in high temperature, which is beneficial to the flow of the crystals separated from the subtle glaze, making the crystal arrangement more uniform and orderly, facilitating the control of glaze flatness and improving the firing efficiency of sanitary ceramics.

[0004] However, prior art 1 can only solve the problem of glaze flatness of subtle glaze, but cannot solve the problem of wear resistance and hardness of the glaze. However, during the production and use of subtle glaze products, defects such as wear, scratches and easy dirt are prone to occur. Moreover, due to the presence of Li2O in comparative document 1, the melting temperature of the raw materials is reduced, which facilitates the control of glaze flatness, but due to the too low melting temperature, the glaze will melt too early and close the pores too early during the firing process, resulting in defects such as bubbling of the glaze surface or formation of pimples on the surface. If there are bubbles in the glaze or pimples on the glaze surface, the wear resistance of the glaze will decrease. SUMMARY

[0005] The technical problem solved by the present application is to provide a nano-matt original stone super wear-resistant diamond glaze, which has high hardness, good wear resistance, good stain resistance and good matt effect.

[0006] The technical problem solved by the present application is also to provide a nano-matt original stone super wear-resistant diamond glaze tile and a preparation method thereof, which has high hardness, good wear resistance, good stain resistance, ideal color development, good matt effect and pattern true effect.

[0007] To achieve the above technical effects, the present application provides a nano-matt original stone super wear-resistant diamond glaze, which comprises the following chemical composition in percentage by weight:

[0008] SiO2 46.00-55.00%, Al2O3 10.00-18.00%, K2O+Na2O=5.00-9.30%, CaO+MgO+SrO+ZnO+BaO=19.00-35.00%, ZrO22.00-6.50%, SiO2 / Al2O3=3.5-4.5, K2O / Na2O=1.1-3.0, loss on ignition 0.50-3.00%;

[0009] The diamond glaze coexists with nano-zirconium oxide grains, zirconium silicate grains and zirconium-containing silicate M grains, and M represents any one or a combination of barium, calcium, magnesium, strontium and zinc.

[0010] As an improvement of the above scheme, the particle size of the nano-zirconium oxide grains is 400-1000 nanometers, the particle size of the zirconium silicate grains is 3-10 micrometers, and the particle size of the zirconium-containing silicate M grains is 5-20 micrometers.

[0011] As an improvement of the above scheme, the particle size of the nano-zirconium oxide grains is 550-850 nanometers, the particle size of the zirconium silicate grains is 4-8 micrometers, and the particle size of the zirconium-containing silicate M grains is 7-10 micrometers.

[0012] As an improvement of the above scheme, the nano-matt original stone super wear-resistant diamond glaze has a glossiness of 6-10 degrees.

[0013] As an improvement of the above scheme, the raw materials of the nano-matt original stone super wear-resistant diamond glaze mainly include, in parts by weight, zirconium-containing frit 80-95, zirconium silicate powder 0.1-10, zirconium oxide 0.1-10, kaolin 1-20 and additives 0.1-5.

[0014] As an improvement of the above scheme, the chemical composition of the zircon-containing frit comprises: SiO248.00-58.00%, Al2O38.00-18.00%, K2O+Na2O=6.00-10.00%, CaO+MgO+SrO+ZnO+BaO=20.00-33.00%, ZrO23.50-5.50%.

[0015] As an improvement of the above scheme, the nano-sublight primary stone super wear-resistant diamond glaze is sintered under the following conditions: sintering cycle is 50-220 minutes; the highest sintering temperature is 1180-1210°C, and the holding time at the highest sintering temperature is 5-20 minutes.

[0016] The time required for cooling from the highest sintering temperature to 950-1050°C is 38-45 minutes.

[0017] On the other hand, the present application also provides a nano-sublight primary stone super wear-resistant ceramic tile, comprising a ceramic tile body and a diamond glaze layer provided on the ceramic tile body, wherein the diamond glaze layer is made of the above nano-sublight primary stone super wear-resistant diamond glaze.

[0018] As an improvement of the above scheme, the thickness of the diamond glaze layer is 9-13 microns.

[0019] As an improvement of the above scheme, the chemical composition of the ceramic tile body in terms of weight percentage comprises: SiO265-70%, Al2O319-21%, CaO+MgO=0.35-0.8%, K2O+Na2O=4.5-5.5%, and loss on ignition 4.5-5.5%.

[0020] In another aspect, the present application also provides a preparation method of a nano-sublight primary stone super wear-resistant diamond glaze ceramic tile, comprising:

[0021] A. preparing a slurry of the nano-sublight primary stone super wear-resistant diamond glaze;

[0022] B. applying a base glaze on the ceramic tile body, and then applying the nano-sublight primary stone super wear-resistant diamond glaze to obtain a diamond glaze layer, drying, and sintering in a kiln.

[0023] As an improvement of the above scheme, step A comprises:

[0024] The raw materials of the zircon-containing frit are uniformly mixed, and then are added into a frit furnace to be melted into a glass liquid, and then are poured into water to be quenched to obtain the zircon-containing frit;

[0025] The raw materials are added into a ball mill according to the chemical composition of the nano-sublight primary stone super wear-resistant diamond glaze, and are ball milled to obtain a glaze slurry;

[0026] The glaze slurry is ground to obtain a nano glaze slurry with an average particle size controlled to be ≤1000 nanometers.

[0027] As an improvement of the above-mentioned scheme, the raw materials of the nano-subdull raw stone super wear-resistant diamond glaze are mainly as follows in weight parts:

[0028] Zirconium-containing clinker 80-95 parts, zirconium silicate powder 0.1-10 parts, zirconia 0.1-10 parts, kaolin 1-20 parts, and auxiliary agent 0.1-5 parts.

[0029] As an improvement of the above-mentioned scheme, in step B, the thickness of the diamond glaze layer is 9-13 microns.

[0030] The firing period is 50-220 minutes.

[0031] The maximum firing temperature is 1180-1210℃, and the holding time at the maximum firing temperature is 5-20 minutes.

[0032] The time required for cooling from the maximum firing temperature to 950-1050℃ is 38-45 minutes.

[0033] The implementation of the present application has the following beneficial effects:

[0034] Firstly, the nano-subdull raw stone super wear-resistant diamond glaze has the following chemical composition: SiO2 46.00-55.00%, Al2O3 10.00-18.00%, K2O+Na2O=5.00-9.30%, CaO+MgO+SrO+ZnO+BaO=19.00-35.00%, ZrO2 2.00-6.50%, SiO2 / Al2O3=3.5-4.5, and K2O / Na2O=1.1-3.0. The above-mentioned chemical composition is fired to make zirconia, zirconium silicate grains and zirconium silicate M grains precipitate in the glaze layer at the same time, and the abnormal growth of the grains is controlled, so that nano-zirconia grains, zirconium silicate grains and zirconium silicate M grains coexist in the glaze. The particle size of the zirconia grains is in the nano level, and the particle size of the zirconium silicate grains and the zirconium silicate M grains is in the micron level.

[0035] Furthermore, the total amount of the divalent metal oxides is large, which increases the crystallization tendency and crystallization capacity of the glaze, and barium carbonate is also added to the clinker glaze. The introduction of barium further increases the crystallization tendency and crystallization capacity of the glaze. Therefore, the diamond glaze has high hardness, good wear resistance, good stain resistance and good subdull effect.

[0036] Further, the present application reduces the firing temperature and prolongs the time required for cooling from the maximum firing temperature to 950-1050℃, which helps to protect the zirconia and zirconium silicate crystal nucleus from being easily dissolved, and the number of the grains precipitated in the glaze is more, which is also helpful to the growth of the grains.

[0037] Secondly, the nano semi-light natural stone super wear-resistant ceramic tile of the present application comprises a ceramic tile body and a diamond glaze layer arranged on the ceramic tile body, and the diamond glaze layer is made of the nano semi-light natural stone super wear-resistant diamond glaze described above. The nano semi-light natural stone super wear-resistant diamond glaze contains nano zirconium oxide grains, zirconium silicate grains and zirconium silicate M grains, so that the glaze layer formed by the nano semi-light natural stone super wear-resistant diamond glaze is very thin, and visible light can easily penetrate through the glaze layer, which is beneficial to the clear presentation of the pattern layer under the glaze layer and good color development effect.

[0038] Furthermore, the present application has excellent hardness, wear resistance and stain resistance by containing a sufficient amount of high-hardness grains (zirconium oxide, zirconium silicate and zirconium silicate M) in the glaze and controlling the particle size of the zirconium oxide grains, zirconium silicate grains and zirconium silicate M grains.

[0039] Thirdly, the preparation method of the nano semi-light natural stone super wear-resistant ceramic tile of the present application has simple process, controllable cost and strong implementability, and is convenient for industrialized popularization and application. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1 is a flow chart of the preparation method of the nano semi-light natural stone super wear-resistant diamond glaze ceramic tile of the present application. DETAILED DESCRIPTION

[0041] In order to make the purpose, technical scheme and advantages of the present application clearer, the present application will be further described in detail below with reference to the drawings.

[0042] The present application provides a nano semi-light natural stone super wear-resistant diamond glaze, which comprises the following chemical components in percentage by weight: SiO2 46.00-55.00%, Al2O3 10.00-18.00%, K2O+Na2O=5.00-9.30%, CaO+MgO+SrO+ZnO+BaO=19.00-35.00%, ZrO22.00-6.50%, SiO2 / Al2O3=3.5-4.5, K2O / Na2O=1.1-3.0, and the loss on ignition is 0.50-3.00%.

[0043] Preferably, the nano semi-light natural stone super wear-resistant diamond glaze comprises the following chemical components in percentage by weight:

[0044] SiO2 48.00-53.00%, Al2O3 11.00-16.00%, K2O+Na2O=6.00-8.30%, CaO+MgO+SrO+ZnO+BaO=20.00-31.00%, ZrO23.00-5.50%, SiO2 / Al2O3=3.5-4.2, K2O / Na2O=1.2-2.8, and the loss on ignition is 1-2%.

[0045] More preferably, the nano-matt original super wear-resistant diamond glaze comprises the following chemical composition in percentage by weight: SiO2 49.00-52.00%, Al2O3 12.00-15.00%, K2O+Na2O=6.00-8.00%, CaO+MgO+SrO+ZnO+BaO=22.00-28.00%, ZrO2 3.00-5.0%, SiO2 / Al2O3=3.8-4.2, K2O / Na2O=1.2-2.5, and loss on ignition is 1-2%.

[0046] In the present application, SiO2 is 46.00-55.00%, Al2O3 is 10.00-18.00%, and by controlling the ratio of SiO2 / Al2O3, the nano-zirconium oxide grains, zirconium silicate grains and zirconium-containing zirconium silicate M grains can be prevented from being dissolved by too much flux, and at the same time, enough silicon source is provided for the precipitation and growth of zirconium silicate and zirconium-containing zirconium silicate M. However, when SiO2 / Al2O3 is greater than 4.5, too much silicon and too little aluminum will precipitate too much zirconium silicate and zirconium-containing zirconium silicate M, resulting in reduced transparency of the glaze. When SiO2 / Al2O3 is less than 3.5, the matt effect cannot be guaranteed.

[0047] In addition, by controlling the ratio of K2O / Na2O, more potassium than sodium is provided, and since the fluxing property of sodium is greater than that of potassium, the nano-zirconium oxide grains, zirconium silicate grains and zirconium-containing zirconium silicate M grains can be prevented from being dissolved by too much flux. However, when K2O / Na2O is greater than 3, the temperature of the glaze is too high due to too much potassium, and the glaze is prone to burning.

[0048] The diamond glaze coexists with nano-zirconium oxide grains, zirconium silicate grains and zirconium-containing zirconium silicate M grains, and M represents any one or a combination of barium, calcium, magnesium, strontium and zinc. Among them, the particle size of the zirconium oxide grains is in the nanometer level, and the particle size of the zirconium silicate grains and the zirconium-containing zirconium silicate M grains is preferably in the micron level.

[0049] The present application controls the abnormal growth and size of the grains by reasonably adjusting the composition of the diamond glaze, so that zirconium oxide grains, zirconium silicate grains and zirconium silicate M grains are precipitated in the glaze at the same time, and the coexisting grains in the glaze are nano-zirconium oxide grains, micron zirconium silicate grains and micron zirconium-containing zirconium silicate M grains. The above-mentioned three kinds of grains with different particle sizes make the glaze layer formed by them very thin, and visible light can easily pass through, which is beneficial to the clear presentation of the pattern layer below the glaze layer, and the color rendering effect is good. Moreover, the present application coexists with a sufficient number of high-hardness grains (zirconium oxide, zirconium silicate and zirconium silicate M), and the particle sizes of the zirconium oxide grains, the zirconium silicate grains and the zirconium-containing zirconium silicate M grains are controlled, so that the diamond glaze has excellent hardness, wear resistance and stain resistance at the same time.

[0050] Compared with soft light bricks and bright light bricks, the glossiness of the matte bricks is 6-10 degrees. The present application adjusts the formula composition, increases the total amount of divalent metal oxides, increases the crystallization tendency and crystallization capacity of the glaze, and also adds barium carbonate to the frit glaze. Due to the introduction of barium, the crystallization tendency and crystallization capacity of the glaze are further increased, so that the glossiness is maintained in a lower range, and a good matte effect is obtained.

[0051] In addition, the crystallization capacity of the glaze can be further increased by reducing the firing temperature and prolonging the time required for cooling from the highest firing temperature to 950-1050°C, so that more and larger grains are precipitated in the glaze, thereby maintaining the glossiness to 6-10 degrees.

[0052] It should be noted that the coexisting nano zirconium oxide grains, zirconium silicate grains and zirconium-containing silicate M grains in the diamond glaze can basically meet the requirements of hardness, wear resistance, stain resistance and color performance of the diamond glaze with matte effect as long as the particle size of the zirconium oxide grains is nanoscale, and the particle size of the zirconium silicate grains and the zirconium-containing silicate M grains is micrometer scale. The nano zirconium oxide grains are uniformly dispersed in the network framework formed by the micrometer zirconium silicate grains and the micrometer zirconium-containing silicate M grains and the base glaze. In this way, the zirconium-containing silicate M grains strengthen the base glaze surface, the zirconium silicate grains strengthen the glaze surface framework formed by the zirconium silicate M grains and the base glaze, and the nano zirconium oxide grains finally disperse and strengthen the network framework glaze layer formed by the micrometer zirconium silicate grains, the zirconium-containing silicate M grains and the base glaze. This step-by-step strengthening and toughening mechanism thus leads to a significant improvement in the overall hardness and wear resistance of the glaze layer.

[0053] Further preferably, the particle size of the nano zirconium oxide grains is 400-1000 nanometers, the particle size of the zirconium silicate grains is 3-10 micrometers, and the particle size of the zirconium-containing silicate M grains is 5-20 micrometers, which can make the hardness, wear resistance, stain resistance and color performance of the glaze layer achieve ideal effects.

[0054] If the sizes of the zirconium oxide grains, the zirconium silicate grains and the zirconium-containing silicate M grains are too large, the particle size of the zirconium-containing silicate M grains is >20 μm, which can easily reduce the glossiness of the glaze layer, and at the same time, the wear resistance, stain resistance and color performance will be poor. If the sizes of the zirconium oxide grains, the zirconium silicate grains and the zirconium-containing silicate M grains are too small, the glossiness will be too high, and the hardness will also be poor.

[0055] More preferably, the particle size of the nano zirconium oxide grains is 550-850 nanometers, the particle size of the zirconium silicate grains is 4-8 micrometers, and the particle size of the zirconium-containing silicate M grains is 7-10 micrometers, which can make the hardness, wear resistance, stain resistance and color performance of the glaze layer achieve the most ideal effects.

[0056] Preferably, the thickness of the diamond glaze layer is 9-13 microns, by reducing the glaze thickness, the transparency caused by the increase of the grain size is reduced, and the pattern layer under the glaze layer is favorably displayed.

[0057] Further, the raw materials of the nano sub-light original stone super wear-resistant diamond glaze by weight are mainly as follows: zirconium-containing clinker 80-95 parts, zircon 0.1-10 parts, zirconia 0.1-10 parts, kaolin 1-20 parts, and additives 0.1-5 parts.

[0058] Preferably, the raw materials of the nano sub-light original stone super wear-resistant diamond glaze by weight are mainly as follows: zirconium-containing clinker 82-92 parts, zircon 0.1-5 parts, zirconia 0.1-5 parts, kaolin 5-15 parts, and additives 0.1-5 parts.

[0059] More preferably, the raw materials of the nano sub-light original stone super wear-resistant diamond glaze by weight are mainly as follows: zirconium-containing clinker 82-92 parts, zircon 0.5-3 parts, zirconia 0.5-3 parts, kaolin 5-15 parts, and additives 0.1-3 parts.

[0060] The ZrO2 content of the zirconium-containing clinker is 3.50-5.50%.

[0061] The additives are selected from one or a combination of water reducing agent and methyl cellulose.

[0062] The three forms of zirconium are zirconium-containing clinker, zircon and zirconia, and the states of zirconium in the three forms are different. The zirconium in the clinker is in an ionic state, the zirconium in the zircon is in a zirconite silicon-oxygen tetrahedral lattice, and the zirconium in the zirconia is in a zirconium-oxygen face-centered cubic lattice. The zirconium in the zirconium-oxygen face-centered cubic lattice can be converted into monoclinic, tetragonal and cubic systems at any time under the influence of the surrounding environment (elemental composition and proportion) and temperature. The zirconium in the zircon is relatively stable, and the zirconium in the clinker and the zirconia is prone to crystal transformation or reaction with the surrounding calcium, magnesium, zinc, barium and strontium ions.

[0063] Therefore, the composition of the diamond glaze is designed, and the firing process is matched to better control the type, content and size of the precipitated grains. Preferably, the firing period is 50-220 minutes, the highest firing temperature is 1180-1210℃, the holding time at the highest firing temperature is 5-20 minutes, the time required for cooling from the highest firing temperature to 950-1050℃ is 38-45 minutes, and the coexisting grains in the glaze are 550-850 nm zirconia grains, 4-8 micron zirconium silicate grains and 7-10 micron zirconium-containing M silicate grains.

[0064] During the reaction, because the zirconium-containing frit particles and the added zirconia and zircon are in a mixed state at the nanometer level, the added zirconia and zircon have sufficient opportunities to react with Ca, Mg, Zn, Ba, and Sr in the frit to form zirconium silicate M. When the zircon in the frit meets the added zirconia, there is an opportunity for zirconia to be precipitated. The added zirconium silicate also has an opportunity to meet the zirconium silicate precipitated in the frit and gradually grow. Therefore, the three types of grains coexist in the glaze, namely, zirconia grain, zirconium silicate grain, and zirconium-containing silicate M grain.

[0065] As one preferred embodiment of the zirconium-containing frit, the composition of the zirconium-containing frit includes: SiO2 48.00-58.00%, Al2O3 8.00-18.00%, CaO+MgO+SrO+ZnO+BaO=20.00-33.00%, K2O+Na2O=6.00-10.00%, and ZrO2 3.50-5.50%.

[0066] The preparation method of the slurry of the nano sub-light original stone super wear-resistant diamond glaze includes:

[0067] (1) uniformly mixing raw materials of the zirconium-containing frit, melting the frit into a glass liquid in a frit furnace, and then pouring into water for quenching to obtain the zirconium-containing frit;

[0068] Preferably, the raw materials of the zirconium-containing frit are selected from one or more of quartz, potassium feldspar, sodium feldspar, talc, wollastonite, dolomite, calcite, zinc oxide, strontium carbonate, barium carbonate, aluminum oxide, zirconium silicate, and zirconia.

[0069] Preferably, the melting temperature of the frit furnace is 1450-1650°C.

[0070] (2) adding the zirconium-containing frit, zircon powder, zirconia, kaolin, and additives into a ball mill according to the chemical composition of the nano sub-light original stone super wear-resistant diamond glaze to perform ball milling to obtain a glaze slurry;

[0071] It should be noted that the selection range of the added amount of the zirconium-containing frit, zircon powder, zirconia, kaolin, and additives is set with reference to the raw materials of the nano sub-light original stone super wear-resistant diamond glaze described above.

[0072] (3) nano-grinding the glaze slurry to obtain a nano glaze slurry with an average particle size controlled to be ≤1000 nanometers.

[0073] Preferably, the glaze slurry is nano-ground to obtain a nano glaze slurry with an average particle size controlled to be 550-850 nanometers.

[0074] Step (3) nano-grinding the glaze slurry, so that the zirconium-containing clinker particles in the reaction process and the added zirconia and zircon are in a mixed state of nanoscale, therefore, after the nano-subtle original stone super wear-resistant diamond glaze slurry is fired, the added zirconia and zircon have sufficient opportunity to react with Ca, Mg, Zn, Ba, Sr in the clinker to form zirconium silicate M. When the zircon in the clinker meets the added zirconia, there is an opportunity to precipitate zirconia. The added zirconium silicate also has an opportunity to meet the precipitated zirconium silicate in the clinker and gradually grow. Therefore, the glaze coexists with zirconia grains, zirconium silicate grains and zirconium-containing silicate M grains.

[0075] In another aspect, the present application also provides a nano-subtle original stone super wear-resistant ceramic tile, comprising a ceramic tile body and a diamond glaze layer provided on the ceramic tile body, wherein the diamond glaze layer is made of the nano-subtle original stone super wear-resistant diamond glaze described above. The technical details of the nano-subtle original stone super wear-resistant diamond glaze are the same as described above, and will not be repeated here.

[0076] Due to the coexistence of nano-zirconia grains, zirconium silicate grains and zirconium-containing silicate M grains in the diamond glaze, the glaze layer formed thereby is very thin, visible light can easily pass through, the decrease in transparency caused by the increase in grain size and particle size can be compensated, and the pattern layer below the glaze layer can be presented in a true manner, and the color development effect is good. Moreover, by having a sufficient number of high-hardness grains (zirconia, zirconium silicate, zirconium silicate M) in the glaze and controlling the particle size of the zirconia grains, zirconium silicate grains and zirconium-containing silicate M grains, the diamond glaze has excellent hardness, wear resistance and stain resistance at the same time.

[0077] Preferably, the thickness of the diamond glaze layer is 9-13 microns. By reducing the thickness of the glaze layer, the decrease in transparency caused by the increase in grain size and particle size can be compensated, and the pattern layer below the glaze layer can be presented in a true manner.

[0078] Generally speaking, if the glaze layer contains a high content of zircon, it will have a high refractive index, thereby forming an opalescent covering layer and affecting the color development of the ceramic tile. However, by controlling the thickness of the diamond glaze layer and the particle size of the coexisting grains, the present application can avoid the formation of an opalescent covering layer and ensure the color development effect.

[0079] It should be noted that the diamond glaze of the present application can be applied to ceramic bodies of various formulations and base glazes of various formulations.

[0080] In another aspect, as shown in Figure 1 the present application also provides a preparation method of a nano-subtle original stone super wear-resistant diamond glaze ceramic tile, comprising:

[0081] S101, preparing a nano-subtle original stone super wear-resistant diamond glaze;

[0082] Preferably, step S101 comprises:

[0083] Mixing the raw materials containing zirconium frit uniformly, adding into the frit furnace to melt into glass liquid, then pouring into water to quench, obtaining zirconium-containing frit;

[0084] According to the chemical composition of the nano sub-light original stone super wear-resistant diamond glaze, the raw materials are added into the ball mill for ball milling to obtain glaze slurry;

[0085] The glaze slurry is ground to obtain nano glaze slurry with an average particle size of ≤1000 nanometers.

[0086] The raw materials of the nano sub-light original stone super wear-resistant diamond glaze are selected from zirconium-containing frit, zirconium silicate, zirconia, kaolin and additives.

[0087] The raw materials of the zirconium-containing frit are selected from one or more of barium carbonate, quartz, potassium feldspar, sodium feldspar, talc, wollastonite, dolomite, calcite, zinc oxide, strontium carbonate, aluminum oxide, zirconium silicate and zirconia.

[0088] Preferably, the nano sub-light original stone super wear-resistant diamond glaze prepared in step S101 has the following chemical composition in terms of weight percentage: SiO2 46.00-55.00%, Al2O3 10.00-18.00%, K2O+Na2O=5.00-9.30%, CaO+MgO+SrO+ZnO+BaO=19.00-35.00%, ZrO22.00-6.50%, SiO2 / Al2O3=3.5-4.5, K2O / Na2O=1.1-3.0, and loss on ignition is 0.50-3.00%. The technical details of the nano sub-light original stone super wear-resistant diamond glaze are the same as described above and will not be repeated here.

[0089] S102, on the ceramic tile body, first apply the base glaze, then apply the nano sub-light original stone super wear-resistant diamond glaze to obtain a diamond glaze layer, dry and fire in the kiln.

[0090] In step S102, preferably, the firing period is 50-220 minutes, the maximum firing temperature is 1180℃-1210℃, the holding time at the maximum firing temperature is 5-20 minutes, the time required to cool from the maximum firing temperature to 950℃-1050℃ is 38-45 minutes, achieving coexistence of zirconia grains with a particle size of 550-850 nanometers, zirconium silicate grains with a particle size of 4-8 microns and zirconium-containing silicon acid M grains with a particle size of 7-10 microns in the glaze.

[0091] When the highest firing temperature is greater than 1210℃, on the one hand, the over-fired body expansion causes the body and glaze to be not adapted, and the bubbles generated by the over-fired body will cause a large number of glaze bubbles on the glaze surface; at the same time, the zirconium silicate and zirconia serving as the crystal nucleus in the glaze will be dissolved or partially dissolved, resulting in the difficulty of the above-mentioned crystal grains to precipitate, and the hardness and wear resistance of the glaze surface are poor. When the highest firing temperature is less than 1180℃, on the one hand, the body firing causes the middle layer of the body and glaze to be difficult to form; at the same time, the glaze is also fired, and the glaze firing is manifested as that the bubbles in the glaze are not completely excluded, the transparency of the glaze is poor, and the like, thereby affecting the quality of the glaze surface.

[0092] The highest firing temperature needs to be cooled to 950-1050℃ for 38-45 minutes, and 950-1050℃ is the temperature range in which the three crystal grains of zirconia, zirconium silicate and zirconium silicate M are nucleated and grown together in the glaze of the system. When the temperature range time is less than 38 minutes, the three crystal grains of zirconia, zirconium silicate and zirconium silicate M are less nucleated, and the number of the three crystal grains is prone to be too small. The hardness and wear resistance of the glaze surface are difficult to reach the ideal value. Moreover, the desired matte effect cannot be achieved. When the temperature range time is greater than 45 minutes, the three crystal grains of zirconia, zirconium silicate and zirconium silicate M are prone to be too much nucleated, and the crystal grains are prone to be too large, the glaze surface is increased in opalescence and decreased in transparency.

[0093] More preferably, the firing cycle is 60-160 minutes, the highest firing temperature is 1180-1200℃, the holding time of the highest firing temperature is 10-20 minutes, and the time needed for cooling from the highest firing temperature to 980-1020℃ is 40-45 minutes.

[0094] In the reaction process, since the zirconium-containing clinker particles and the added zirconia and zircon are in a mixed state at the nanoscale, the added zirconia and zircon have sufficient opportunity to react with Ca, Mg, Ba, Zn and Sr in the clinker to form zirconium silicate M. When the zircon in the clinker meets the added zirconia, there is an opportunity to precipitate zirconia. The added zirconium silicate also has an opportunity to meet the precipitated zirconium silicate in the clinker and gradually grow. Therefore, the three crystal grains of zirconia, zirconium silicate and zirconium silicate M coexist in the glaze.

[0095] Preferably, the thickness of the diamond glaze layer formed by sintering is 9-13 microns. By reducing the thickness of the glaze layer, the reduction in transparency caused by the increase in crystal grains and particle size is compensated, which is beneficial to the true display of the pattern layer under the glaze layer.

[0096] Generally speaking, if the glaze layer contains a high content of zirconium, it will have a high refractive index, thereby forming a cloudy covering layer and affecting the color of the ceramic tile. However, by controlling the thickness of the diamond glaze layer and the particle size of the coexisting crystal grains, the formation of the cloudy covering layer can be avoided, and the color effect can be ensured.

[0097] It should be noted that after applying a base glaze, inkjet-printed pattern, and nano-matte raw stone ultra-wear-resistant diamond glaze to the body layer in sequence, the present invention can also perform inkjet-printed pattern layer again and apply top glaze to form a top glaze layer.

[0098] After firing in the kiln in step S102, the edges of the fired semi-finished product are ground to obtain the finished nano-matte raw stone ultra-wear-resistant diamond glaze ceramic tile.

[0099] The present invention will be further illustrated below with specific embodiments.

[0100] Example 1

[0101] A. Preparation of nano-matte raw stone ultra-wear-resistant diamond glaze, including:

[0102] The raw materials containing zirconium frit are mixed evenly, added to a frit furnace and melted into glass liquid, then poured into water for quenching to obtain zirconium frit;

[0103] According to the above chemical composition of nano-matte raw stone super wear-resistant diamond glaze, 89 kg of zircon frit, 10 kg of kaolin, 0.5 kg of zircon powder, 0.5 kg of zirconium oxide, 0.5 kg of water-reducing agent, and 0.1 kg of methylcellulose were added to a ball mill and ball milled to obtain glaze slurry.

[0104] The glaze slurry was nano-ground to obtain a nano-matte raw stone ultra-wear-resistant diamond glaze with an average particle size controlled at 550-850 nanometers.

[0105] B. Apply a base glaze to the ceramic tile body, then apply the nano-matte raw stone ultra-wear-resistant diamond glaze to obtain a diamond glaze layer. Dry the glaze and fire it in a kiln. The firing conditions are: a firing cycle of 65 minutes, a maximum firing temperature of 1210℃, a holding time of 6 minutes at the maximum firing temperature, and a cooling time of 38 minutes from the maximum firing temperature to 1050℃.

[0106] After firing, the nano-matte raw stone ultra-wear-resistant diamond glaze comprises the following chemical composition by weight percentage:

[0107] The composition of SiO2 is 53.25%, Al2O3 is 13.21%, K2O+Na2O=6.3%, CaO+MgO+SrO+ZnO+BaO=19.8%, ZrO2 is 6.28%, SiO2 / Al2O3=4.03, K2O / Na2O=1.15, and the loss on ignition is 1.16%.

[0108] The glaze slurry contains zirconium oxide grains with a particle size of 550–850 nanometers, zirconium silicate grains with a particle size of 4–8 micrometers, and zirconium silicate M grains with a particle size of 7–10 micrometers, wherein M represents any one or a combination of barium, calcium, magnesium, strontium, and zinc.

[0109] Example 2

[0110] A. Preparing nano sub-light original stone super wear-resistant diamond glaze, comprising:

[0111] Mixing raw materials containing zirconium frit uniformly, adding into a frit furnace to melt into a glass liquid, then pouring into water to quench, obtaining zirconium frit;

[0112] According to the chemical composition of the above nano sub-light original stone super wear-resistant diamond glaze, 90.5 kg of zirconium frit, 8 kg of kaolin, 0.5 kg of zirconium silicate powder, 1 kg of zirconium oxide, 0.5 kg of water reducing agent and 0.1 kg of methyl cellulose are added into a ball mill for ball milling, obtaining glaze slurry;

[0113] The glaze slurry is nano ground to obtain nano sub-light original stone super wear-resistant diamond glaze with an average particle size of 550-850 nm;

[0114] B. On the ceramic tile body, first apply a base glaze, then apply the nano sub-light original stone super wear-resistant diamond glaze, obtain a diamond glaze layer, dry and enter the kiln for firing. The firing conditions are: firing period of 75 minutes, maximum firing temperature of 1200℃, holding time at the maximum firing temperature of 8 minutes; the time required for cooling from the maximum firing temperature to 1000℃ is 40 minutes.

[0115] After firing, the nano sub-light original stone super wear-resistant diamond glaze comprises the following chemical composition in percentage by weight:

[0116] SiO2 54.27%, Al2O3 13.47%, CaO+MgO+SrO+ZnO+BaO=19.88%, K2O+Na2O=5.5%, ZrO24.78%, SiO2 / Al2O3=4.03, K2O / Na2O=1.50, loss on ignition of 2.10%.

[0117] Zirconium oxide grains with a coexisting particle size of 550-850 nm, zirconium silicate grains with a particle size of 4-8 microns and zirconium-containing silicon acid M grains with a particle size of 7-10 microns coexist in the glaze slurry, wherein M represents any one or a combination of barium, calcium, magnesium, strontium and zinc.

[0118] Example 3

[0119] A. Preparing nano sub-light original stone super wear-resistant diamond glaze, comprising:

[0120] Mixing raw materials containing zirconium frit uniformly, adding into a frit furnace to melt into a glass liquid, then pouring into water to quench, obtaining zirconium frit;

[0121] According to the chemical composition of the nano sub-light natural stone super wear-resistant diamond glaze, zircon-containing clinker 91.5 kg, kaolin 7 kg, zirconium powder 1 kg, zirconia 0.5 kg, water reducing agent 0.5 kg, and methyl cellulose 0.1 kg are added into the ball mill for ball milling to obtain a glaze slurry;

[0122] The glaze slurry is nano-ground to obtain a nano sub-light natural stone super wear-resistant diamond glaze with an average particle size controlled to be 550-850 nm;

[0123] B. On the ceramic tile body, first apply a base glaze, then apply the nano sub-light natural stone super wear-resistant diamond glaze to obtain a diamond glaze layer, dry, and fire in a kiln. The firing conditions are: a firing period of 78 minutes, a maximum firing temperature of 1205℃, a holding time at the maximum firing temperature of 10 minutes, and a cooling time from the maximum firing temperature to 950℃ of 45 minutes.

[0124] The nano sub-light natural stone super wear-resistant diamond glaze comprises the following chemical composition in percentage by weight:

[0125] SiO2 54.66%, Al2O3 12.15%, CaO+MgO+SrO+ZnO+BaO=24.1%, K2O+Na2O=5.02%, ZrO2 3.17%, SiO2 / Al2O3=4.50, K2O / Na2O=2.0, and a loss on ignition of 0.9%.

[0126] The glaze slurry contains zirconia grains with a particle size of 550-850 nm, zirconium silicate grains with a particle size of 4-8 microns, and zirconium-containing silicon acid M grains with a particle size of 7-10 microns, wherein M represents any one or a combination of barium, calcium, magnesium, strontium, and zinc.

[0127] Example 4

[0128] A. Preparing a nano sub-light natural stone super wear-resistant diamond glaze, comprising:

[0129] Mixing the raw materials containing zirconium clinker uniformly, melting into a glass liquid in a clinker furnace, and then pouring into water for quenching to obtain zirconium-containing clinker;

[0130] According to the chemical composition of the nano sub-light natural stone super wear-resistant diamond glaze, zircon-containing clinker 91.5 kg, kaolin 7 kg, zirconium powder 1 kg, zirconia 0.5 kg, water reducing agent 0.5 kg, and methyl cellulose 0.1 kg are added into the ball mill for ball milling to obtain a glaze slurry;

[0131] The glaze slurry is nano-ground to obtain a nano sub-light natural stone super wear-resistant diamond glaze with an average particle size controlled to be 550-850 nm;

[0132] B. Apply the nano sub-light original stone super wear-resistant diamond glaze on the tile body, and then apply the bottom glaze to obtain a diamond glaze layer, dry, and enter the kiln for firing. The firing conditions are: a firing period of 85 minutes, a maximum firing temperature of 1210°C, a holding time at the maximum firing temperature of 15 minutes, and a time required for cooling from the maximum firing temperature to 980°C of 40 minutes.

[0133] After firing, the nano sub-light original stone super wear-resistant diamond glaze comprises the following chemical composition in percentage by weight:

[0134] SiO253.00%, Al2O3 12.24%, CaO+MgO+SrO+ZnO+BaO=24.41%, K2O+Na2O=5.78%, ZrO23.53%, SiO2 / Al2O3=4.33, K2O / Na2O=2.2, and a loss on ignition of 1.04%.

[0135] The zirconia crystal grains with a particle size of 550-850 nanometers, the zirconium silicate crystal grains with a particle size of 4-8 micrometers, and the zirconium-containing M silicate crystal grains with a particle size of 7-10 micrometers coexist in the glaze slurry, and the M represents any one or a combination of barium, calcium, magnesium, strontium, and zinc.

[0136] Example 5

[0137] A. Preparing the nano sub-light original stone super wear-resistant diamond glaze, comprising:

[0138] Mixing the raw materials containing zirconium frit uniformly, melting the frit into a glass liquid in a frit furnace, and then pouring into water for quenching to obtain a zirconium-containing frit;

[0139] According to the chemical composition of the nano sub-light original stone super wear-resistant diamond glaze, 84 kg of zirconium-containing frit, 14 kg of kaolin, 1 kg of zirconite powder, 1 kg of zirconia, 0.5 kg of water reducing agent, and 0.1 kg of methyl cellulose are added to a ball mill for ball milling to obtain a glaze slurry;

[0140] The glaze slurry is nano-ground to obtain a nano sub-light original stone super wear-resistant diamond glaze with an average particle size controlled to be 550-850 nanometers;

[0141] B. Apply the nano sub-light original stone super wear-resistant diamond glaze on the bottom glaze, with a thickness controlled to be 10 micrometers, dry, and enter the kiln for firing. The firing conditions are: a firing period of 120 minutes, a maximum firing temperature of 1190°C, a holding time at the maximum firing temperature of 15 minutes, and a time required for cooling from the maximum firing temperature to 1000°C of 45 minutes.

[0142] After firing, the nano sub-light original stone super wear-resistant diamond glaze comprises the following chemical composition in percentage by weight:

[0143] SiO2 54.65%, Al2O3 13.29%, CaO+MgO+SrO+ZnO+BaO=19.25%, K2O+Na2O=5.96%, ZrO2 5.13%, SiO2 / Al2O3=4.11, K2O / Na2O=1.8, loss on ignition 1.72%.

[0144] Zirconia grains with a particle size of 550-850 nm, zirconium silicate grains with a particle size of 4-8 microns and zirconium-containing M-silicate grains with a particle size of 7-10 microns coexist in the glaze slurry, wherein M represents any one or a combination of barium, calcium, magnesium, strontium and zinc.

[0145] The tiles described in Examples 1-5 were subjected to technical tests, and the results are as follows:

[0146]

[0147] As can be seen from the above, the gloss of the tiles of Examples 1-5 is controlled within 6-10 degrees, achieving good matte effect; the hardness is high, with a Mohs hardness of 7-8; the wear resistance is good, with a wear resistance grade of 4, 9000-12000 revolutions; and the stain resistance is good, with 9 times of invisible traces basically achieved using a blue oil-based marker.

[0148] It should be noted that the detection of wear resistance is based on GB / T3810.7.

[0149] The above describes preferred embodiments of the present application, and it should be noted that, for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements are also considered to be within the scope of protection of the present application.

Claims

1. A nanometre sub-optical protogem ultra-hard diamond glaze, characterised in that, The chemical composition includes the following in percentage by weight: SiO2 46.00~55.00%, Al2O3 10.00~18.00%, K2O+Na2O=5.00~9.30%, CaO+MgO+SrO+ZnO+BaO =19.00~35.00%, ZrO22.00~6.50%, SiO2 / Al2O3=3.5~4.5, K2O / Na2O=1.1~3.0, loss on ignition 0.50~3.00%; The diamond glaze coexists with nano zirconium oxide grains, zirconium silicate grains and zirconium-containing M-silicate grains, wherein M represents any one or combination of barium, calcium, magnesium, strontium and zinc; The particle size of the nano zirconium oxide grains is 400~1000 nanometers, the particle size of the zirconium silicate grains is 3~10 micrometers, and the particle size of the zirconium-containing M-silicate grains is 5~20 micrometers; The nano sub-light primary stone super wear-resistant diamond glaze is fired under the following conditions: firing period is 50~220 minutes; the highest firing temperature is 1180℃~1210℃, and the holding time at the highest firing temperature is 5~20 minutes; The time required for cooling from the highest firing temperature to 950℃~1050℃ is 38~45 minutes.

2. The nano-metamict superhard diamond glaze of claim 1, wherein, The particle size of the nano zirconium oxide grains is 550~850 nanometers, the particle size of the zirconium silicate grains is 4~8 micrometers, and the particle size of the zirconium-containing M-silicate grains is 7~10 micrometers.

3. The nano-metamict superhard diamond glaze of claim 1, wherein, The nano sub-light primary stone super wear-resistant diamond glaze has a glossiness of 6~10 degrees.

4. The nano-metamict superhard diamond glaze of claim 1, wherein, The raw materials of the nano sub-light primary stone super wear-resistant diamond glaze mainly include, in parts by weight: Zirconium-containing frit 80-95 parts, zirconium silicate powder 0.1-10 parts, zirconium oxide 0.1-10 parts, kaolin 1-20 parts, and additives 0.1-5 parts.

5. The nano-metamict superhard diamond glaze of claim 4, wherein, The chemical composition of the zirconium-containing frit includes: SiO2 48.00~58.00%, Al2O3 8.00~18.00%, CaO+MgO+SrO+ZnO+BaO=20.00~33.00%, K2O+Na2O=6.00~10.00%, and ZrO23.50~5.50%.

6. A nano-metahalogeno hyperwearable ceramic tile, characterized by, The ceramic tile includes a tile body and a diamond glaze layer provided on the tile body, wherein the diamond glaze layer is made of the nano sub-light primary stone super wear-resistant diamond glaze according to any one of claims 1-5.

7. The nano-metamorphic super wear-resistant tile according to claim 6, characterized in that, The thickness of the diamond glaze layer is 9~13 micrometers.

8. The nano-metamorphic super wear-resistant tile according to claim 6, characterized in that, The chemical composition of the tile body includes the following in percentage by weight: SiO2 65~70%, Al2O3 19~21%, CaO+MgO=0.35~0.8%, K2O+Na2O=4.5~5.5%, and loss on ignition 4.5~5.5%.

9. A method of preparing a nanometre sub-optical protogem ultra- wear resistant diamond enameled tile, characterized by, It includes: A. preparing the slurry of the nano sub-light primary stone super wear-resistant diamond glaze according to any one of claims 1-5; B. applying a base glaze on the tile body, then applying the nano sub-light primary stone super wear-resistant diamond glaze to obtain a diamond glaze layer, drying, and firing in a kiln.

10. The preparation method of the nano-matte raw stone ultra-wear-resistant diamond glaze ceramic tile as described in claim 9, characterized in that, Step A includes: Mixing the raw materials of the zirconium-containing frit uniformly, melting the frit in a frit furnace to form a glass liquid, then pouring the glass liquid into water for quenching to obtain the zirconium-containing frit. The chemical composition of the nano sub-light raw stone super wear-resistant diamond glaze according to any one of claims 1-5, raw materials are added into a ball mill for ball milling to obtain a glaze slurry; The glaze slurry is ground to obtain a nano glaze slurry with an average particle size controlled to be ≤1000 nanometers.

11. The preparation method of the nano-matte raw stone ultra-wear-resistant diamond glaze ceramic tile as described in claim 10, characterized in that, The raw materials of the nano sub-light raw stone super wear-resistant diamond glaze are mainly as follows in weight parts: Zirconium-containing frit 80-95 parts, zirconite powder 0.1-10 parts, zirconia 0.1-10 parts, kaolin 1-20 parts, and auxiliary agent 0.1-5 parts.

12. The preparation method of the nano-matte raw stone ultra-wear-resistant diamond glaze ceramic tile as described in claim 9, characterized in that, In step B, the thickness of the diamond glaze layer is 9-13 microns; The firing period is 50-220 minutes; The highest firing temperature is 1180-1210°C, and the holding time at the highest firing temperature is 5-20 minutes; The time required for cooling from the highest firing temperature to 950-1050°C is 38-45 minutes.

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