Highly wear-resistant and scratch-resistant frosted glaze slip, preparation method and ceramic

Abstract

The invention relates to a high-wear-resistance and scratch-resistance frosted glaze slip, a preparation method and a ceramic, and the high-wear-resistance and scratch-resistance frosted glaze slip is applied to a ceramic green body to be fired to form a high-wear-resistance and scratch-resistance frosted glaze ceramic. Comprising the following components: 4.7-10 parts of frit, 29-42 parts of potassium feldspar, 6-12 parts of kaolin, 10-17 parts of modified kaolin, 14-22 parts of first quartz sand, 14-22 parts of a fluxing agent, 7-11 parts of a thermal expansion stabilizer, 6.3-10 parts of a metal powder additive, 6-8 parts of an opacifier and 1-3 parts of a coloring agent. According to the frosted glaze, the surface gloss is considered, the wear resistance and the scratch resistance are remarkably improved, and the compactness is greatly improved, so that the anti-pollution performance can be improved, the problems that the traditional frosted glaze is poor in wear resistance and is easy to scratch when being used in a daily severe environment are solved, and the comprehensive performance is improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramic glaze, more particularly to a high-wear-resistance and high-scratch-resistance frosted glaze paste, a preparation method and a ceramic. BACKGROUND

[0002] With the development of the times, the aesthetic tastes of consumers are increasingly diversified, and people's requirements for daily-use porcelain are not limited to appreciation, but also pursue all-round experience: it must have aesthetic value, practical function and physical durability at the same time.

[0003] The traditional frosted glaze has a significant shortcoming: its microscopically uneven surface brings soft luster while also makes it particularly easy to hide dirt, resulting in poor stain resistance and poor wear resistance and scratch resistance, which is often far inferior to bright glaze with a dense and smooth surface. This shortcoming is more obvious in harsh environments that require frequent use and cleaning (such as kitchen countertops, dining tables, floors, and public spaces).

[0004] Therefore, there is an urgent need for a high-wear-resistance and high-scratch-resistance frosted glaze paste, a preparation method and a ceramic. SUMMARY

[0005] In order to solve the above technical problems, the present application provides a high-wear-resistance and high-scratch-resistance frosted glaze paste, a preparation method and a ceramic, and the specific technical scheme is as follows: The present application provides a high-wear-resistance and high-scratch-resistance frosted glaze paste for applying to a ceramic body to be fired to form a high-wear-resistance and high-scratch-resistance frosted glaze ceramic, which is prepared from the following components in parts by weight: frit 4.7-10 parts, potassium feldspar 29-42 parts, kaolin 6-12 parts, modified kaolin 10-17 parts, first quartz sand 14-22 parts, fluxing agent 14-22 parts, thermal expansion stabilizer 7-11 parts, metal powder additive 6.3-10 parts, opacifying agent 6-8 parts, and coloring agent 1-3 parts.

[0006] Preferably: The modified kaolin comprises calcined kaolin; The fluxing agent comprises calcite; The thermal expansion stabilizer comprises calcined talc; The metal powder additive comprises aluminum powder; The opacifying agent is selected from zirconium silicate or yttrium-stabilized zirconium oxide; The coloring agent is selected from at least one of vanadium zirconium yellow, zirconium iron red, and brilliant black.

[0007] Preferably, the first quartz sand is modified by the following steps: S1, crushing: crushing the quartz into blocks with a diameter <5 cm; S2, pre-burning: put the bulk quartz into the kiln for pre-burning, and heat to 750~800℃ at a speed of 3~5℃ / min, and keep the temperature for 2~4 hours to obtain pre-burned quartz; S3, grinding: use crushing and grinding equipment to process the pre-burned quartz into fine powder; S4, grading: grade by air flow classifier, and separate the target product with D50 of 30~50um; The metal powder additive further comprises an aluminum-silicon alloy powder component, and the aluminum-silicon alloy powder component comprises aluminum-silicon alloy powder and boron carbide micro powder, and the content of the boron carbide micro powder is 5%~23.8% of the aluminum-silicon alloy powder component.

[0008] Preferably, The application provides a preparation method for preparing the high-wear-resistance and high-scratch-resistance frosted glaze. S10, weighing raw materials: the frit, potassium feldspar, kaolin, calcined kaolin, first quartz sand, calcite, calcined talc, aluminum powder, opacifier and colorant are weighed according to the weight parts; S20, mixing: mix all the raw materials to obtain the glaze; S30, ball milling: put the glaze into a ball mill, and wet mill for 15~20min to obtain the slurry; S40, sieving: sieve the slurry through a 200-mesh screen and remove iron, and control the water content of the slurry by adding water or evaporation concentration to be 40%~50% to obtain the glaze slurry.

[0009] Preferably, In step S30, the weight ratio of the glaze, the ball milling medium and the dispersion medium in the ball mill is 1:(1.5~1.8):(0.5~0.6).

[0010] Preferably, The application provides a preparation method for high-wear-resistance and high-scratch-resistance frosted glaze ceramic, which is obtained by applying the glaze slurry as described in any one of the above on a ceramic body and firing to form high-wear-resistance and high-scratch-resistance frosted glaze ceramic. S100, preparing the ceramic body: select the body clay, shape the body after drying, and then perform bisque firing at a temperature of 800~900℃ to obtain the ceramic body; S200, glazing: use a glazing machine to spray the glaze slurry on the ceramic body; S300, drying: perform drying treatment on the ceramic body; S400, firing: put the dried ceramic body into a kiln for firing, and the high-wear-resistance and high-scratch-resistance frosted glaze ceramic is obtained after firing.

[0011] Preferably, Before step S200, a glaze spraying test is further included for adjusting the aperture and spraying angle of the nozzle of the glaze spraying machine.

[0012] Preferably, In step S400, the firing is performed by using a roller kiln, which comprises a preheating section, a firing section and a cooling section; the temperature of the preheating section is 300-950℃, the temperature of the firing section is 950-1200℃, and the temperature of the cooling section is 60-800℃; the ceramic body in the roller kiln sequentially passes through the preheating section, the firing section and the cooling section.

[0013] Preferably, In step S400, the holding temperature after the firing section is 1180-1210℃ for 10-30min.

[0014] Preferably, The application provides a high-wear-resistance and high-scratch-resistance frosted glaze ceramic prepared by the preparation method of the high-wear-resistance and high-scratch-resistance frosted glaze ceramic.

[0015] The application has the advantages that the surface gloss, wear resistance, scratch resistance, compactness, and pollution resistance are all improved, the core problems of the traditional frosted glaze, such as poor wear resistance, easy scratching, and poor pollution resistance, are solved, and the performance is comprehensively and significantly improved. DETAILED DESCRIPTION

[0016] The application is further described below in combination with examples.

[0017] The embodiment provides a high-wear-resistance and high-scratch-resistance frosted glaze slip, which is used for being applied to a ceramic body to form a high-wear-resistance and high-scratch-resistance frosted glaze ceramic, and is prepared from the following components in parts by weight: frit 4.7-10 parts, potassium feldspar 29-42 parts, kaolin 6-12 parts, modified kaolin 10-17 parts, first quartz sand 14-22 parts, fluxing agent 14-22 parts, thermal expansion stabilizer 7-11 parts, metal powder additive 6.3-10 parts, opacifier 6-8 parts, and coloring agent 1-3 parts.

[0018] The frit, the potassium feldspar and the fluxing agent cooperate to reduce the melting point of the glaze, to ensure that the raw materials are fully melted, and to avoid too high gloss or excessive dripping of the glaze surface, to ensure the matte texture and the density of the glaze layer; the kaolin and the modified kaolin are matched to improve the suspension stability and the anti-flowing property of the glaze slurry, to balance the plasticity and the stability to prevent the glaze layer from cracking; the first quartz sand is used to participate in the construction of the glaze layer skeleton with high hardness components, to significantly enhance the hardness and the wear resistance; the thermal expansion stabilizer matches the expansion coefficient of the body, to relieve the temperature change stress, to prolong the wear life by strengthening the glaze-body bonding force; the metal powder additive reacts to generate high hardness compounds and fill the pores, to greatly improve the wear and scratch resistance; the opacifier forms a uniform opalescent effect, to cover up the body defects and provide a soft base color; a small amount of coloring agent realizes uniform color on the premise of not interfering with the function, to balance the decoration and the functionality, and the components are finally matched to form the high wear and scratch-resistant matte glaze surface.

[0019] Further, The modified kaolin includes calcined kaolin; The fluxing agent includes calcite; The thermal expansion stabilizer includes calcined talc; The metal powder additive includes aluminum powder; The opacifier is selected from zirconium silicate or yttrium-stabilized zirconium oxide; The coloring agent is selected from at least one of vanadium-zirconium yellow, zirconium-iron red and bright black.

[0020] The frit, the potassium feldspar and the calcite, the calcined talc cooperate to reduce the melting point of the glaze, the calcined talc adjusts the melt flowability, to ensure that the raw materials are fully melted, and to avoid too high gloss or excessive dripping of the glaze surface, to ensure the fine matte texture and the dense glaze layer; the kaolin and the modified calcined kaolin are matched, the calcined kaolin strengthens the anti-flowing property with a stable structure, to improve the suspension stability of the glaze slurry while balancing the plasticity and the stability, to effectively prevent the glaze layer from cracking; the first quartz sand is used to participate in the construction of the glaze layer skeleton with high hardness silica, to significantly enhance the hardness and the wear resistance; the calcined talc as the thermal expansion stabilizer matches the expansion coefficient of the body, to relieve the temperature change stress, to prolong the wear life by strengthening the glaze-body bonding force; the aluminum powder participates in the glaze melt reaction and crystallization to generate high hardness compounds and fill the pores of the glaze layer, to greatly improve the wear and scratch resistance; the zirconium silicate or the yttrium-stabilized zirconium oxide forms a uniform opalescent effect, to cover up the body defects and provide a soft white base color; a small amount of coloring agent such as vanadium-zirconium yellow and zirconium-iron red realizes uniform bright color on the premise of not interfering with the function, to balance the decoration and the functionality, and the components are finally matched to form the high wear and scratch-resistant matte glaze surface.

[0021] Further, The first quartz sand is modified by the following steps: S1, crushing: crushing the quartz into blocks with a diameter <5 cm; S2, pre-burning: put the bulk quartz into the kiln for pre-burning, and heat it to 750-800℃ at a speed of 3-5℃ / min, and keep it at this temperature for 2-4 hours to obtain pre-burned quartz; S3, grinding: use crushing and grinding equipment to process the pre-burned quartz into fine powder; S4, grading: grade by air flow classifier, and separate the target product with D50 of 30-50μm; The metal powder additive further comprises an aluminum-silicon alloy powder component, which comprises aluminum-silicon alloy powder and boron carbide micro powder, and the content of the boron carbide micro powder is 5%-23.8% of the aluminum-silicon alloy powder component.

[0022] Wherein, after the quartz is pre-burned at 750-800℃, the internal lattice structure is more stable, the internal stress can be eliminated, and the thermal expansion fluctuation at high temperature is reduced. The particle size of 30-50μm after crushing can be uniformly dispersed in the glaze slurry, avoiding the roughness of the glaze surface caused by too coarse particles or the influence on the skeleton support caused by too fine particles, so that the hardness distribution of the glaze layer is more uniform, the wear resistance is more significantly improved, and the aluminum-silicon alloy powder is used with boron carbide micro powder. At high temperature, boron carbide can effectively reduce the oxide film on the surface of aluminum-silicon alloy particles. During the heating process, it will react with the dense and stable aluminum oxide film on the surface of aluminum-silicon alloy particles, breaking the barrier that hinders the reaction of aluminum-silicon alloy and other components of the glaze. The melting point of the reaction product boron aluminates is low, which can form a local liquid phase between the particles, greatly promoting the diffusion of atoms / ions, creating conditions for the subsequent generation of new phases (high-hardness mullite, corundum or boron-containing hard phases), and then promoting the aluminum-silicon alloy to fully react in the glaze layer to generate high-hardness silicon-aluminum compounds, further enhancing the hardness and density of the glaze layer. Compared with single aluminum powder, the scratch resistance of the glaze surface is more significantly improved. With the improvement of density, the glaze layer is like a complete and non-porous barrier, so that pollutants can only form droplets on its surface, making it difficult for pollutants to embed and remain inside, and easier to clean and remove, thereby improving the stain resistance.

[0023] The embodiment also provides a preparation method for preparing the glaze slurry as described in any one of the above embodiments, comprising the following steps: S10, weighing raw materials: weigh the frit, potassium feldspar, kaolin, calcined kaolin, quartz, calcite, calcined talc, aluminum powder, opacifier and colorant according to the weight fraction; S20, mixing: mix all the raw materials to obtain glaze; S30, ball milling: put the glaze into a ball mill and wet mill for 15-20min to obtain a slurry; S40, sieving: sieve the slurry through a 200-mesh screen and remove iron, and control the water content of the slurry by adding water or evaporation concentration to 40%-50%, to obtain the glaze slurry.

[0024] The step S10 of weighing the raw materials according to the accurate weight is the basis for ensuring the proportion of each functional component, so as to avoid the failure of the flux system or the insufficient wear-resistant component due to the deviation of the components; the steps S20 and S30 of mixing and then wet grinding for 15-20 minutes can ensure that the raw material particles are in full contact and control the grinding fineness, and if the time is too short, the particles are coarse and the glaze surface is prone to appear mottling; if the time is too long, the particles are too fine and the matte texture is damaged; the 200-mesh screen in the step S40 can intercept the coarse particles that are not fully ground, and the iron removal treatment can remove the metal impurities mixed in the raw materials, so as to avoid the black spot defects on the glaze surface after firing, and the water content of 40%-50% is a key parameter, and if the water content is too low, the glaze paste is thick and prone to precipitation, and it is difficult to uniformly cover the glaze; if the water content is too high, the glaze paste is too thin, and the glaze layer thickness is difficult to control, which is prone to cause the matte texture to be blurred, and the water content makes the glaze paste have good fluidity and suspension, which is suitable for the subsequent glazing process.

[0025] Further, In the step S30 of the glaze paste preparation method, the weight ratio of the glaze material, the ball milling medium and the dispersion medium in the ball mill is 1:(1.5-1.8):(0.5-0.6).

[0026] The ratio of the glaze material to the ball milling medium is controlled to be (0.5-1):(0.7-1.5), which can ensure that the ball milling medium can form sufficient impact and grinding force on the glaze material, so that the raw material particles are refined to the suitable size, and can avoid that too much medium leads to energy waste or that the medium is worn and mixed with impurities, and the proportion of the dispersion medium is 0.1-0.6, which can make the glaze material particles uniformly dispersed in the medium, prevent the particle agglomeration in the grinding process, and ensure the uniformity of the glaze paste components.

[0027] The embodiment also provides a preparation method of the high wear-resistant and scratch-resistant matte glaze ceramic, which is formed by applying the glaze paste prepared by any one of the above methods on a ceramic body and firing. S100, preparing a ceramic body: selecting a body clay, shaping by pulling the body, repairing the body and drying, and then performing bisque firing at a temperature of 800-900 DEG C to obtain the ceramic body; S200, spraying glaze: spraying the glaze paste on the ceramic body by using a glaze spraying machine; S300, drying: drying the ceramic body; S400, firing: loading the dried ceramic body into a kiln for firing, and obtaining the high wear-resistant and scratch-resistant matte glaze ceramic after firing.

[0028] In step S100, 800-900℃ preliminary sintering can make the body preliminary solidification, remove internal moisture and organic matter, form a stable structure, and avoid the glaze layer cracking due to excessive shrinkage of the body during subsequent glazing and firing; In step S200, the glazing machine is more uniform than manual glazing, can accurately control the thickness of the glaze layer, ensure the consistency of the sanding texture, and reduce the waste of glaze slurry; In step S300, the drying treatment after glazing can slowly remove the moisture on the surface of the glaze layer and the body, prevent the rapid evaporation of water during firing to produce bubbles, and cause pinholes or peeling on the glaze surface; The glaze slurry and the body are fully combined at high temperature, which not only plays the high wear resistance of the glaze slurry itself, but also ensures the firmness of the glaze body.

[0029] Further: The above-mentioned high wear-resistant and scratch-resistant sanding glaze ceramic preparation method further includes a glazing test before step S200, which is used to adjust the aperture and spray angle of the glazing machine nozzle.

[0030] The nozzle aperture directly affects the amount of glaze slurry sprayed and the particle distribution--too small aperture is easy to cause blockage, resulting in glaze layer missing; Too large aperture makes it difficult to control the flow of glaze slurry, which is easy to cause local glaze layer to be too thick, sanding texture to be blurred, and spray angle to determine the adhesion of glaze slurry on the surface of the body, improper angle will cause uneven glazing on the edge and corner of the body, through test adjustment parameters, the best nozzle state can be determined according to the shape, size of the body and the viscosity of the glaze slurry, to ensure the uniformity of the glaze layer thickness, the coherence of the sanding texture without breakpoints, avoid batch product defects caused by improper glazing parameters, and improve the production qualified rate.

[0031] Further: In step S400 of the above-mentioned high wear-resistant and scratch-resistant sanding glaze ceramic preparation method, roller kiln firing is adopted, the roller kiln includes preheating section, firing section and cooling section, and all are in oxidizing atmosphere; The preheating section temperature is 300-950℃, the firing section temperature is 950-1200℃, and the cooling section temperature is 60-800℃; The ceramic body in the roller kiln passes through the preheating section, firing section and cooling section in turn.

[0032] The 300-950℃ preheating section can slowly increase the temperature of the body and the glaze layer, gradually remove the residual moisture and organic matter, and avoid the glaze surface cracking caused by sudden temperature rise; The 950-1200℃ firing section is the core stage of glaze melting and reaction, this temperature range can ensure that the flux such as frit and calcite fully forms a glass body, the components such as quartz and aluminum-silicon alloy powder complete the skeleton construction and enhanced phase generation, the 60-800℃ cooling section adopts gradient cooling to avoid the internal stress of the glaze layer caused by too large temperature difference, and ensure the integrity of the glaze surface; The oxidizing atmosphere can prevent the metal components such as aluminum powder from being excessively reduced, ensure its participation in the glaze melt reaction and crystallization to generate high-hardness compounds, and ensure the stability of wear resistance.

[0033] Further: In step S400 of the method for preparing the high-wear-resistance and high-scratch-resistance frosted glaze ceramic, the firing step is followed by heat preservation at 1180-1210°C for 10-30 min.

[0034] The heat preservation at 1180-1210°C for 10-30 min can make the internal reaction of the glaze layer more complete, eliminate micro-bubbles, promote uniform diffusion of components, and improve the compactness of the glaze layer.

[0035] The embodiment also provides a high-wear-resistance and high-scratch-resistance frosted glaze ceramic formed by firing a glaze slurry as described in any one of the preceding embodiments on a ceramic body.

[0036] In the glaze slurry, the functional components synergistically act at high temperatures to form a skeleton constructed by quartz and a compact glaze layer with aluminum powder-derived compounds as reinforcing phases, which endows the ceramic with high hardness and wear-resistance and scratch-resistance; the melt fluidity controlled by calcined talc and calcite ensures a fine and uniform frosted texture; the opacifier such as zirconium silicate and the specific colorant make the ceramic have good hiding power and decorative properties; compared with ordinary frosted glaze ceramic, the glaze layer of the ceramic has higher compactness, the wear-resistance is improved, the glaze color is stable, the texture is consistent, and the ceramic can meet the use requirements of various scenes such as tableware and floor tiles.

[0037] Example 1 The first quartz sand, which is a key material for the skeleton of the glaze layer, is subjected to modification treatment: after the natural quartz ore is crushed by a jaw crusher into blocks with a diameter of <5 cm, the blocks are loaded into a high-temperature kiln, heated at a rate of 4°C / min to 780°C, and heat preserved for 3 hours. This pre-burning process can effectively eliminate the internal stress of the quartz and stabilize the crystal lattice structure. Then the pre-burned quartz is ground into fine powder by a Raymond mill, and finally the target product with a D50 value of 40±2 μm is accurately separated by an air classifier, obtaining modified first quartz sand with stable structure and suitable particle size.

[0038] First, all raw materials are subjected to strict quality inspection: the frit is screened to confirm uniform particle size without caking; the powdery raw materials such as potassium feldspar powder and kaolin are dried at 105°C to detect that the moisture content is less than 0.5%; the modified quartz sand is detected by a laser particle size analyzer to confirm that the D50 value is stable in the range of 40±2 μm; the aluminum powder is sealed and kept shiny without oxidation; the zirconium silicate and vanadium zirconium yellow are uniform in color without contamination. According to the formula, the frit 66 g, potassium feldspar 330 g, kaolin 85 g, calcined kaolin 122.5 g, modified first quartz sand 170 g, calcite 169.5 g, calcined talc 85 g, aluminum powder 75.5 g, zirconium silicate 66 g, and vanadium zirconium yellow 19 g are accurately weighed, and the total amount of raw materials is 1000 g, which meets the preparation requirements of 10 pieces of 150 mm×150 mm test pieces.

[0039] The preparation process adopts a hierarchical mixing process. The raw materials are sequentially poured into a three-dimensional motion mixer according to specific gravity, and mixed at a speed of 120 r / min. Then, the mixture is transferred into a ball mill for ball milling, 1200 g of zirconium oxide balls and 420 g of wet grinding are added, and the mixture is ground for 2 hours. After ball milling, the slurry is filtered through a 200-mesh vibrating screen and then treated with magnetic iron removal for three times. The initial water content is 48.5%, and after standing and precipitation control, it stabilizes at 46.8%. The observed glaze slurry presents a uniform milky appearance with suitable fluidity.

[0040] Ten 150mmx150mm test pieces were selected for semi-porcelain blank slip casting, and after 850°C biscuit firing, the blank body with stable strength was obtained. Before glazing, the blank body surface was cleaned with an air spray gun, 42 g of glaze slurry was added to the automatic glazing system, and the automatic glazing system was used to implement cross-spraying of the preset amount of glaze slurry under a pressure of 0.4 MPa. The glazed body was naturally dried in an environment of 25°C and 55% humidity for 12 hours, and then transferred to a roller kiln for firing. The firing process strictly controls the temperature curve: the temperature is uniformly increased to 950°C at a rate of 4°C / min to remove water, the temperature is continuously increased to 1185°C and then maintained for 25 minutes, and finally cooled to room temperature at a rate of 3°C / min, maintaining an oxidizing atmosphere throughout the process. The ten samples after firing all present a uniform beige matte finish.

[0041] Then, the ten samples (numbered S-01 to S-10) that passed the firing were subjected to systematic testing. Six samples were taken, and each sample was accurately cut into two equal areas along the diagonal, one for wear resistance testing (Area A) and the other for scratch resistance testing (Area B). All samples were equilibrated in a standard environment (temperature 23±2°C, humidity 50±5%) for 24 hours before testing. Then, the B areas of the six samples were subjected to scratch resistance testing in sequence using an automatic scratch tester. The constant load method was used, a diamond spherical stylus was used to perform horizontal scratch testing at a constant load of 12N, and the test steps were as follows: first, check the status of the automatic scratch tester: confirm that the diamond spherical stylus is not worn, deformed, and the needle tip curvature meets the test requirements; the equipment is placed horizontally, the scratch track is not jammed or offset, then a sample is fixed on the equipment workbench to ensure that the sample is flat and not loose, the B area is directly opposite the scratch path of the stylus, the scratch mode is set to "horizontal straight line scratch", the scratch length is set to 50mm, then the stylus height is adjusted to ensure that the stylus is vertically in contact with the surface of the B area of the sample without any inclination angle, then the equipment is started, and the B area of the sample is subjected to 1 horizontal scratch according to the set parameters. After the sample test is completed, the equipment is turned off, the sample is removed, and the same conditions are used to test the B areas of the remaining samples in sequence according to the above steps. After testing each sample, check the stylus status (no wear, no foreign matter attached), and after testing is completed, use a 50x microscope to evaluate the scratch state. The test results are shown in Table 1-1.

[0042] The abrasion resistance of the A area of the six samples was then tested in turn on the abrasion tester. The abrasion resistance test was performed after the scratch resistance test to avoid the heat generated by the abrasion resistance test affecting the scratch resistance test. The abrasion resistance test procedure was as follows: first, the initial mass of the six samples was measured and recorded, the workbench was confirmed to be level, the polishing track was confirmed to be free of jamming, and the grinding wheel mounting seat was confirmed to be secure; then, six brand-new and uniform grinding wheels (meeting the test requirements) were prepared for standby, and then one sample was fixed on the workbench, ensuring that the A area was directly opposite the polishing path of the grinding wheel, the sample was flat and not loose, the equipment was started, and 50 revolutions of pre-polishing were performed: during the pre-polishing process, the contact surface fit was observed to ensure that the grinding wheel was in full contact with the A area and the stable friction interface, and after pre-polishing was completed, the equipment was stopped, and then the equipment was started again to perform the first 250 revolutions of polishing, and after completion, the equipment was stopped, the surface of the A area and the polishing debris on the workbench were cleaned with a soft brush (to avoid affecting the subsequent polishing effect), and the above process was repeated to complete the second 250 revolutions (cumulative 500 revolutions), the third 250 revolutions (cumulative 750 revolutions), and the fourth 250 revolutions (cumulative 1000 revolutions) of polishing, and the equipment was stopped and the debris was cleaned after each 250 revolutions, and the A area was kept clean throughout the process. After 1000 revolutions of polishing were completed, the equipment was turned off, the sample was removed, and the sample was allowed to stand for 10 minutes in a dry environment at room temperature (to stabilize the sample state), the mass of the sample after testing was measured and recorded on a balance, the used grinding wheel was removed, a brand-new grinding wheel was installed, and the above process was repeated to test the abrasion resistance of the A area of the remaining samples, with a new grinding wheel used for each sample, and the parameters were kept consistent throughout the process. The test results are shown in Tables 1-2.

[0043] The remaining four samples were subjected to density testing, and the test procedure was as follows: the dry mass of each of the four samples was measured and recorded, and then sufficient distilled water was added to the boiling equipment, and the water temperature was raised to boiling. The weighed sample was completely immersed in boiling water, and the samples were kept apart to avoid touching each other or colliding with the container wall. The water was maintained at a boiling state for 2 hours, and distilled water was added during this period to ensure that the sample was always completely immersed in boiling water. After boiling was completed, heating was stopped, and the sample was allowed to cool naturally with the water to room temperature. The cooled sample was removed, and the surface was gently wiped with a wet gauze (without squeezing the internal water of the sample). The saturated mass was immediately measured and recorded on a balance, and the water absorption rate was calculated according to (water absorption rate = (saturated mass - dry mass) / dry mass x 100%). The test results are shown in Table 1-3.

[0044] Example 2 Before the experiment, first of all, all raw materials were strictly quality inspection: aluminum silicon alloy powder should keep silver gray metal luster and no oxidation, boron carbide powder required uniform particle size distribution without caking, other raw material inspection standard same as example 1.

[0045] For the first quartz sand as the key material of the glaze layer skeleton, modification treatment was carried out: the natural quartz ore was crushed to <5cm diameter by jaw crusher, then loaded into high temperature kiln to heat up to 780℃ at a rate of 4℃ / min and keep for 3 hours, this pre-burning process can effectively eliminate the internal stress of quartz, stabilize the lattice structure; then the pre-burned quartz was ground into fine powder by Raymond mill, and finally the target product with D50 of 40±2μm was accurately separated by air classifier, obtaining modified first quartz sand with stable structure and suitable particle size.

[0046] After the pretreatment of raw materials, the batch 66g, potassium feldspar 330g, kaolin 85g, calcined kaolin 122.5g, modified first quartz sand 170g, calcite 169.5g, calcined talc 85g, aluminum silicon alloy powder 69.5g, boron carbide powder 6g, zirconium silicate 66g, vanadium zirconium yellow 19g were accurately weighed according to the optimized formula, and the total amount of raw materials was 1000g. During the preparation process, the raw materials were put into the three-dimensional motion mixer in order of specific gravity and mixed at a speed of 120r / min, then transferred into the ball mill, 1200g zirconia balls and 420g water were added for wet grinding for 2 hours to ensure that the aluminum silicon alloy powder and boron carbide powder were fully dispersed. The slurry after ball milling was filtered through a 200 mesh vibrating screen and then treated with magnetic iron removal for three times, the initial moisture content was 49.2%, and after standing and precipitation control, it was stabilized at 46.8%, finally the glaze slurry with uniform cream and good flowability was obtained.

[0047] Ten pieces of 150mm×150mm test pieces were selected for semi-porcelain blank slip casting, and the blank body with stable strength was obtained after 850℃ biscuit firing. Before glazing, the surface of the blank body was cleaned with an air spray gun, 42g of glaze slurry was added to the automatic glazing system, and the automatic glazing system was used to implement cross spraying of the preset amount of glaze slurry at a pressure of 0.4MPa. The glazed blank body was naturally dried for 12 hours in an environment of 25℃ and 55% humidity, and then transferred into a roller kiln for firing. The firing process strictly controlled the temperature rising curve: the water was removed at a uniform rate of 4℃ / min to 950℃, then the temperature was continued to rise to 1185℃ and kept for 25 minutes, finally cooled to room temperature at a rate of 3℃ / min, and the whole process was kept in an oxidizing atmosphere. The ten samples after firing all showed uniform beige matte texture.

[0048] Ten samples (No. S-11 to S-20) that passed the firing test were subjected to systematic tests. Six samples (No. S-11 to S-16) were each cut along the diagonal into two equal areas, one for abrasion resistance testing (Area A) and the other for scratch resistance testing (Area B). All samples were equilibrated in a standard environment (temperature 23±2°C, humidity 50±5%) for 24 hours before testing. Scratch resistance and abrasion resistance tests were then conducted in the same manner and under the same conditions as in Example 1.

[0049] The results of the scratch resistance tests are shown in Table 2-1.

[0050] The results of the abrasion resistance tests are shown in Table 2-2.

[0051] The remaining four samples were subjected to density tests in the same manner and under the same conditions as in Example 1, and the results are shown in Table 2-3.

[0052] Comparative Example First, all raw materials were subjected to a basic quality check, and a comparative verification was conducted using a conventional ground glaze formulation and a conventional process. According to the conventional formulation, 84 g of frit, 423 g of potassium feldspar, 210 g of kaolin, 168 g of ordinary quartz sand, 126 g of calcite, 42 g of talc, 63 g of zircon silicate, and 19 g of vanadium zircon yellow were accurately weighed, for a total of 1000 g of raw materials, to meet the requirements for the preparation of 10 pieces of 150 mm x 150 mm test pieces. The ordinary quartz sand was not subjected to a pre-burning modification process.

[0053] Glaze slips were prepared in the same manner and by the same procedure as in Example 2, and 10 pieces of 150 mm x 150 mm test pieces were formed by slip casting using the same semi-porcelain body. The test pieces were subjected to a 850°C biscuit firing, and 10 samples were prepared in the same manner and by the same procedure as in Example 2.

[0054] Six samples (No. C-01 to C-10) that passed the firing test were subjected to systematic tests. Six samples (No. C-01 to C-06) were each cut along the diagonal into two equal areas, one for abrasion resistance testing (Area A) and the other for scratch resistance testing (Area B). All samples were equilibrated in a standard environment (temperature 23±2°C, humidity 50±5%) for 24 hours before testing. Scratch resistance and abrasion resistance tests were then conducted in the same manner and under the same conditions as in Example 1.

[0055] The results of the scratch resistance tests are shown in Table 4-1.

[0056] The results of the abrasion resistance tests are shown in Table 4-2.

[0057] The remaining 4 samples were tested for density in the same procedure and conditions as Example 1, and the results are shown in Table 4-3.

[0058] From the comparison of the test data of Examples 1-2 and the comparative examples, it can be seen that the average mass loss in the examples is the lowest, which is increased by about 222% compared with the comparative examples, the wear resistance and scratch resistance of Examples 1-2 are significantly improved, the water absorption rate in the examples is the lowest 0.008%, while the water absorption rate in the comparative examples is the lowest 0.471%, and the density is greatly improved at the same time.

[0059] The embodiments of the present application are described in detail above, but the present application is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the purpose of the present application.

Claims

1. A high-wear, scratch-resistant, matte glaze paste, characterized in that, The high wear-resistant and scratch-resistant frosted enamel ceramic is prepared by applying the high wear-resistant and scratch-resistant frosted enamel slurry on a ceramic body, and the high wear-resistant and scratch-resistant frosted enamel slurry is prepared by mixing the following components by weight: 4.7-10 parts of frit, 29-42 parts of potassium feldspar, 6-12 parts of kaolin, 10-17 parts of modified kaolin, 14-22 parts of first quartz sand, 14-22 parts of flux, 7-11 parts of thermal expansion stabilizer, 6.3-10 parts of metal powder additive, 6-8 parts of opacifier, and 1-3 parts of colorant.

2. The high wear-resistant and scratch-resistant frosted enamel slurry according to claim 1, characterized in that: The modified kaolin comprises calcined kaolin; The flux comprises calcite; The thermal expansion stabilizer comprises calcined talc; The metal powder additive comprises aluminum powder; The opacifier is selected from zirconium silicate or yttrium-stabilized zirconium oxide; The colorant is selected from at least one of vanadium zirconium yellow, zirconium iron red, and brilliant black.

3. The high-wear, scratch-resistant, matte glaze of claim 1 or 2, wherein, The first quartz sand is modified by the following steps: S1, crushing: crushing the quartz into blocks with a diameter of <5 cm; S2, pre-burning: placing the block quartz into a kiln for pre-burning, heating at a speed of 3-5 ℃ / min to 750-800 ℃, and keeping the temperature for 2-4 hours to obtain pre-burned quartz; S3, grinding: using crushing and grinding equipment to process the pre-burned quartz into fine powder; S4, grading: grading by using an air flow classifier to separate the target product with a D50 of 30-50 μm; The metal powder additive further comprises an aluminum-silicon alloy powder component, and the aluminum-silicon alloy powder component comprises aluminum-silicon alloy powder and boron carbide micro powder, and the content of the boron carbide micro powder is 5%-23.8% of the aluminum-silicon alloy powder component.

4. A method of manufacture characterised by, The high wear-resistant and scratch-resistant frosted enamel slurry is prepared by the following steps: S10, weighing raw materials: weighing the frit, potassium feldspar, kaolin, calcined kaolin, first quartz sand, calcite, calcined talc, aluminum powder, opacifier, and colorant by weight; S20, mixing: mixing all the raw materials to obtain the enamel; S30, ball milling: adding the enamel into a ball mill for wet milling for 15-20 min to obtain the slurry; S40, sieving: sieving the slurry through a 200-mesh screen and removing iron, and using the method of adding water or evaporation concentration to control the water content of the slurry to be 40%-50% to obtain the enamel slurry.

5. The preparation method according to claim 4, characterized in that, In step S30, the weight ratio of the enamel, ball milling medium, and dispersion medium in the ball mill is 1:(1.5-1.8):(0.5-0.6).

6. A method for preparing high wear-resistant and scratch-resistant frosted enamel ceramic, which comprises the following steps: applying the enamel slurry according to any one of claims 1-3 on a ceramic body to prepare high wear-resistant and scratch-resistant frosted enamel ceramic by firing. S100, preparing a ceramic body: selecting body clay, shaping by pulling, repairing and drying, and then bisque firing at a temperature of 800-900 ℃ to obtain the ceramic body; S200, spraying enamel: spraying the enamel slurry on the ceramic body by using an enamel spraying machine; S300, drying: drying the ceramic body; S400, firing: firing the dried ceramic body in a kiln to obtain the high wear-resistant and scratch-resistant frosted enamel ceramic.

7. The method for preparing a high-wear, scratch-resistant, matte, glazed ceramic according to claim 6, characterized in that, Before step S200, a glaze spraying test is further included for adjusting the aperture and spraying angle of the spraying nozzle of the glaze spraying machine.

8. The method of making a high-wear, scratch-resistant, matte, glazed ceramic according to claim 6, wherein, In step S400, the firing is performed by using a roller kiln, which comprises a preheating section, a firing section and a cooling section; the temperature of the preheating section is 300-950℃, the temperature of the firing section is 950-1200℃, and the temperature of the cooling section is 60-800℃; the ceramic body in the roller kiln sequentially passes through the preheating section, the firing section and the cooling section.

9. The method for preparing a high-wear, scratch-resistant, matte, glazed ceramic according to claim 8, characterized in that, In step S400, the temperature of the firing section is 1180-1210℃, and the holding time is 10-30min.

10. A high-wear, scratch-resistant, matte-glazed ceramic, characterized in that, The high-wear-resistance and high-scratch-resistance frosted glaze ceramic is prepared by the method of any one of claims 6-9.

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