阅读说明：本技术 一种耐火耐磨瓷砖及其制备方法 (Fire-resistant and wear-resistant ceramic tile and preparation method thereof ) 是由 刘浩 于 2021-09-11 设计创作，主要内容包括：本发明公开了一种耐火耐磨瓷砖及其制备方法,涉及新材料技术领域。本发明先将钙长石、钠长石、透长石、高岭土和膨润土按比例混合、干燥、压制,制成砖坯；再制备改性水滑石和二氧化钛纳米纤维；将改性水滑石和二氧化钛纳米纤维混合制得二氧化钛纳米纤维-改性水滑石复合材料；将二氧化钛纳米纤维-改性水滑石复合材料与高岭土、硼砂、碳化硅一起混合、粉碎、搅拌制成釉浆；砖坯上釉后烧结制得一种耐火耐磨瓷砖。本发明制备的瓷砖具备优良的耐磨性能,且在具有一定的保温隔热性能同时有良好的抗压强度。(The invention discloses a refractory wear-resistant ceramic tile and a preparation method thereof, and relates to the technical field of new materials. Firstly, mixing anorthite, albite, sanile, kaolin and bentonite according to a certain proportion, drying and pressing to obtain a green brick; then preparing modified hydrotalcite and titanium dioxide nano-fibers; mixing the modified hydrotalcite and the titanium dioxide nanofiber to prepare a titanium dioxide nanofiber-modified hydrotalcite composite material; mixing, crushing and stirring the titanium dioxide nanofiber-modified hydrotalcite composite material, kaolin, borax and silicon carbide to prepare glaze slurry; the green brick is glazed and sintered to obtain the refractory and wear-resistant ceramic tile. The ceramic tile prepared by the invention has excellent wear resistance, certain heat preservation and heat insulation performance and good compressive strength.)

1. The refractory wear-resistant ceramic tile is characterized by mainly comprising 150-200 parts by weight of tile body ingredients and 30-40 parts by weight of glaze surface ingredients;

the brick ingredients comprise anorthite, albite, sanidine, kaolin and bentonite;

the glaze surface ingredients comprise kaolin, borax, silicon carbide, modified hydrotalcite and wear-resistant fibers.

2. The refractory wear-resistant tile according to claim 1, wherein the modified hydrotalcite is prepared by mixing magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate and sodium dihydrogen phosphate.

3. The refractory wear-resistant tile according to claim 2, wherein the wear-resistant fibers are titanium dioxide nanofibers prepared by mixing titanium dioxide and potassium hydroxide.

4. The fire-resistant and wear-resistant ceramic tile according to claim 3, which mainly comprises the following components in parts by weight: 180 parts of brick ingredients and 40 parts of glaze ingredients;

the brick body batching includes: 80 parts of albite, 40 parts of anorthite, 30 parts of sanidine, 20 parts of kaolin and 10 parts of bentonite;

the glaze comprises the following ingredients: 20 parts of kaolin, 2 parts of borax, 8 parts of silicon carbide, 5 parts of modified hydrotalcite and 5 parts of wear-resistant fiber.

5. The preparation method of the fire-resistant and wear-resistant ceramic tile is characterized by mainly comprising the following preparation steps:

(1) mixing, drying and pressing the ingredients of the brick body to prepare a green brick;

(2) preparing modified hydrotalcite;

(3) preparing titanium dioxide nano fibers;

(3) preparing all glaze ingredients into glaze slip;

(4) and glazing the adobes and sintering to obtain the refractory and wear-resistant ceramic tile.

6. The method for preparing the fire-resistant and wear-resistant ceramic tile according to claim 5, which mainly comprises the following preparation steps:

(1) mixing albite, anorthite, sanidine, kaolin and bentonite according to the mass ratio of 8: 4: 3: 2: 1, putting the mixture into a grinder to be ground to obtain a ground material; sieving the crushed materials, and mixing with deionized water according to a mass ratio of 4: 1, putting the mixture into a ball mill, grinding the mixture uniformly to obtain slurry, cooling the slurry to room temperature, putting the slurry into a high-temperature sterilizer for drying, putting the dried slurry into a spray drying tower, sending hot air with the temperature of 560 ℃ by using a hot air furnace to obtain dried particles, and putting the dried particles into a mould for compression molding to obtain a green brick; the thickness of the green brick is 5-8 mm.

(2) Magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate and deionized water in a mass ratio of 1: 1: 1: 20, uniformly mixing to obtain a mixed salt solution A; sodium hydroxide, sodium carbonate and deionized water are mixed according to the mass ratio of 2: 1: 20, uniformly mixing to obtain a mixed salt solution B; dropping the mixed salt solution A into the mixed salt solution B at the speed of 12ml/min, wherein the mass ratio of the mixed salt solution A to the mixed salt solution B is 2: 1, heating in an oil bath at 50 ℃ in the dropping process and magnetically stirring at the speed of 300 rpm; after the dropwise addition, adjusting the pH value of the system to 10-11 by using 1mol/L sodium hydroxide solution, and keeping the temperature at 50 ℃ for standing for 30 minutes to obtain a suspension; centrifuging the suspension for 50 minutes at the rotating speed of 2500rpm, re-dispersing the precipitate obtained by filtering in deionized water with the mass of 10 times that of the precipitate, and uniformly mixing to obtain a dispersion liquid; transferring the dispersion liquid to a hydrothermal reaction kettle, carrying out hydrothermal reaction at the temperature of 120 ℃ for 24 hours, naturally cooling a product obtained by the reaction to room temperature, carrying out suction filtration twice, washing a solid obtained by the suction filtration 3 times by using deionized water, and drying in a vacuum drying oven at the temperature of 60 ℃ for 24 hours to obtain zinc-magnesium-aluminum ternary hydrotalcite; zinc-magnesium-aluminum ternary hydrotalcite and deionized water are mixed according to the mass ratio of 3: 20, mixing to obtain hydrotalcite dispersion liquid; dropwise adding a sodium dihydrogen phosphate solution with the mass fraction of 98% into the hydrotalcite dispersion liquid at the speed of 15ml/min to obtain a mixed solution, wherein the mass ratio of the sodium dihydrogen phosphate solution to the hydrotalcite dispersion liquid is 1: 5; adjusting the pH value of the system to 4-5 by using 1mol/L dilute nitric acid solution, stirring the mixed solution at the rotation speed of 200rpm at 98 ℃ for refluxing for 12 hours, cooling to room temperature, washing the solid obtained by suction filtration by using deionized water until the washing liquid is neutral, and performing vacuum drying at 60 ℃ for 12 hours to obtain modified hydrotalcite;

(3) mixing titanium dioxide particles and a sodium hydroxide solution with the concentration of 10mol/L according to the mass ratio of 1: 30, and uniformly stirring to obtain a titanium dioxide suspension; putting the titanium dioxide suspension into a reaction kettle, reacting for 12 hours at the temperature of 200 ℃, and washing products obtained by the reaction with hydrochloric acid, water and alcohol in sequence until washing liquor is neutral; centrifuging the washed neutral reaction product at the rotating speed of 2500rpm for 50 minutes, and carrying out vacuum drying on the filtered solid at the temperature of 60 ℃ for 24 hours to obtain titanium dioxide nano fibers;

(4) uniformly mixing titanium dioxide nanofibers and modified hydrotalcite to obtain a titanium dioxide nanofiber-modified hydrotalcite composite material; mixing titanium dioxide nanofiber-modified hydrotalcite composite material, kaolin, borax and silicon carbide according to the mass ratio of 5: 10: 1: 4 mixing and putting the mixture into a grinder to be ground to the fineness of 200 meshes to obtain ground materials; mixing the crushed material and deionized water according to a mass ratio of 4: 1, mixing, stirring at 1800rpm for 8 hours to obtain glaze slip;

(5) and coating the glaze slip on the surface of the green brick, placing the glazed green brick into a kiln for high-temperature sintering, and naturally cooling to room temperature after sintering to obtain the refractory wear-resistant ceramic tile.

7. The method for preparing a fire-resistant and wear-resistant ceramic tile according to claim 6, wherein the pulverization conditions in the step (1) are 1500rpm pulverization for 30 seconds; sieving with 200 mesh sieve; grinding for 2 minutes at a grinding speed of 60 r/min; the conditions of the high-temperature sterilizing agent are 125 ℃ and 15 minutes; the conditions of spray drying were 500 ℃; the pressure of the press forming is 500kg/cm²The temperature is 40-50 ℃.

8. The method for preparing the fire-resistant and wear-resistant ceramic tile according to claim 6, wherein the mixing method of the titanium dioxide nanofibers and the modified hydrotalcite in the step (4) is as follows: titanium dioxide nano fibers, modified hydrotalcite and deionized water are mixed according to the mass ratio of 1: 1: 20, mixing, and stirring at the rotating speed of 300-500 rpm for 1 hour to obtain a mixed solution; and transferring the mixed solution into a reaction kettle, reacting for 6 hours at the temperature of 180 ℃, filtering a reaction product to obtain a solid, and vacuum-drying for 12 hours at the temperature of 60 ℃ to obtain the titanium dioxide nanofiber-modified hydrotalcite composite material.

9. The preparation method of the fire-resistant and wear-resistant ceramic tile as claimed in claim 6, wherein the thickness of the glaze in the step (5) is 0.5-1 mm; the sintering process is as follows: heating to 300-450 ℃ at the speed of 5-6 ℃/min, preserving heat for 20-30 minutes, heating to 600-800 ℃ at the speed of 8-12 ℃/min, preserving heat for 20-30 minutes, heating to 950-1250 ℃ at the heating speed of 8-12 ℃/min, preserving heat, sintering for 1-5 hours, discharging, and cooling to room temperature to obtain the refractory and wear-resistant ceramic tile.

Technical Field

The invention relates to the technical field of new materials, in particular to a fireproof and wear-resistant ceramic tile and a preparation method thereof.

Background

The ceramic tile is an acid and alkali resistant porcelain or stone building or decorating material formed by grinding, mixing, pressing, glazing and sintering refractory metal oxide and semimetal oxide. The raw materials are mostly mixed by clay, quartz, etc. With the rapid development of the building tile industry in China, the performance requirements of people on tiles are higher and higher. The ceramic tile in the current market has the defect of poor wear resistance, is easy to swell in the using process and has very serious friction loss, the service life of the ceramic tile is greatly shortened, and the market demand can not be met.

The wear resistance of the ceramic tile directly determines the service life of the ceramic tile, the floor tile on the market generally has the characteristic of smooth surface, but hard objects are easily scratched when being wiped on the floor tile, the wear resistance is insufficient, scratches and stars are invented after the floor tile is used for a period of time, dirt is easily stored, the surface of the ceramic tile is not bright as before, and consumers have to replace the ceramic tile for the second time, so that secondary loss of economy and manpower is caused. Therefore, the development of the high-wear-resistance ceramic tile product can not only improve the user experience, but also achieve the effect of saving resources.

The ceramic tile prepared by the invention has excellent wear resistance, certain heat preservation and heat insulation performance and good compressive strength.

Disclosure of Invention

The invention aims to provide a refractory wear-resistant ceramic tile and a preparation method thereof, and aims to solve the problems in the prior art.

In order to solve the technical problems, the invention provides the following technical scheme: a refractory wear-resistant ceramic tile mainly comprises 150-200 parts by weight of tile body ingredients and 30-40 parts by weight of glaze surface ingredients;

the brick ingredients comprise anorthite, albite, sanidine, kaolin and bentonite;

the glaze surface ingredients comprise kaolin, borax, silicon carbide, modified hydrotalcite and wear-resistant fibers. .

Preferably, the modified hydrotalcite is prepared by mixing magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate and sodium dihydrogen phosphate.

Preferably, the wear-resistant fibers are titanium dioxide nano fibers prepared by mixing titanium dioxide and potassium hydroxide.

As optimization, the refractory wear-resistant ceramic tile mainly comprises the following components in parts by weight: 180 parts of brick ingredients and 40 parts of glaze ingredients;

the brick body batching includes: 80 parts of albite, 40 parts of anorthite, 30 parts of sanidine, 20 parts of kaolin and 10 parts of bentonite;

the glaze comprises the following ingredients: 20 parts of kaolin, 2 parts of borax, 8 parts of silicon carbide, 5 parts of modified hydrotalcite and 5 parts of wear-resistant fiber.

As optimization, the preparation method of the fire-resistant and wear-resistant ceramic tile mainly comprises the following preparation steps:

(1) mixing, drying and pressing the ingredients of the brick body to prepare a green brick;

(2) preparing modified hydrotalcite;

(3) preparing titanium dioxide nano fibers;

(3) preparing all glaze ingredients into glaze slip;

(4) and glazing the adobes and sintering to obtain the refractory and wear-resistant ceramic tile.

As optimization, the preparation method of the refractory wear-resistant ceramic tile mainly comprises the following preparation steps:

(1) mixing albite, anorthite, sanidine, kaolin and bentonite according to the mass ratio of 8: 4: 3: 2: 1, putting the mixture into a grinder to be ground to obtain a ground material; sieving the crushed materials, and mixing with deionized water according to a mass ratio of 4: 1, putting the mixture into a ball mill, grinding the mixture uniformly to obtain slurry, cooling the slurry to room temperature, putting the slurry into a high-temperature sterilizer for drying, putting the dried slurry into a spray drying tower, sending hot air with the temperature of 560 ℃ by using a hot air furnace to obtain dried particles, and putting the dried particles into a mould for compression molding to obtain a green brick; the thickness of the green brick is 5-8 mm.

(2) Magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate and deionized water in a mass ratio of 1: 1: 1: 20, uniformly mixing to obtain a mixed salt solution A; sodium hydroxide, sodium carbonate and deionized water are mixed according to the mass ratio of 2: 1: 20, uniformly mixing to obtain a mixed salt solution B; dropping the mixed salt solution A into the mixed salt solution B at the speed of 12ml/min, wherein the mass ratio of the mixed salt solution A to the mixed salt solution B is 2: 1, heating in an oil bath at 50 ℃ in the dropping process and magnetically stirring at the speed of 300 rpm; after the dropwise addition, adjusting the pH value of the system to 10-11 by using 1mol/L sodium hydroxide solution, and keeping the temperature at 50 ℃ for standing for 30 minutes to obtain a suspension; centrifuging the suspension for 50 minutes at the rotating speed of 2500rpm, re-dispersing the precipitate obtained by filtering in deionized water with the mass of 10 times that of the precipitate, and uniformly mixing to obtain a dispersion liquid; transferring the dispersion liquid to a hydrothermal reaction kettle, carrying out hydrothermal reaction at the temperature of 120 ℃ for 24 hours, naturally cooling a product obtained by the reaction to room temperature, carrying out suction filtration twice, washing a solid obtained by the suction filtration 3 times by using deionized water, and drying in a vacuum drying oven at the temperature of 60 ℃ for 24 hours to obtain zinc-magnesium-aluminum ternary hydrotalcite; zinc-magnesium-aluminum ternary hydrotalcite and deionized water are mixed according to the mass ratio of 3: 20, mixing to obtain hydrotalcite dispersion liquid; dropwise adding a sodium dihydrogen phosphate solution with the mass fraction of 98% into the hydrotalcite dispersion liquid at the speed of 15ml/min to obtain a mixed solution, wherein the mass ratio of the sodium dihydrogen phosphate solution to the hydrotalcite dispersion liquid is 1: 5; adjusting the pH value of the system to 4-5 by using 1mol/L dilute nitric acid solution, stirring the mixed solution at the rotation speed of 200rpm at 98 ℃ for refluxing for 12 hours, cooling to room temperature, washing the solid obtained by suction filtration by using deionized water until the washing liquid is neutral, and performing vacuum drying at 60 ℃ for 12 hours to obtain modified hydrotalcite;

(3) mixing titanium dioxide particles and a sodium hydroxide solution with the concentration of 10mol/L according to the mass ratio of 1: 30, and uniformly stirring to obtain a titanium dioxide suspension; putting the titanium dioxide suspension into a reaction kettle, reacting for 12 hours at the temperature of 200 ℃, and washing products obtained by the reaction with hydrochloric acid, water and alcohol in sequence until washing liquor is neutral; centrifuging the washed neutral reaction product at the rotating speed of 2500rpm for 50 minutes, and carrying out vacuum drying on the filtered solid at the temperature of 60 ℃ for 24 hours to obtain titanium dioxide nano fibers;

(4) uniformly mixing titanium dioxide nanofibers and modified hydrotalcite to obtain a titanium dioxide nanofiber-modified hydrotalcite composite material; mixing titanium dioxide nanofiber-modified hydrotalcite composite material, kaolin, borax and silicon carbide according to the mass ratio of 5: 10: 1: 4 mixing and putting the mixture into a grinder to be ground to the fineness of 200 meshes to obtain ground materials; mixing the crushed material and deionized water according to a mass ratio of 4: 1, mixing, stirring at 1800rpm for 8 hours to obtain glaze slip;

(5) and coating the glaze slip on the surface of the green brick, placing the glazed green brick into a kiln for high-temperature sintering, and naturally cooling to room temperature after sintering to obtain the refractory wear-resistant ceramic tile.

As optimization, the crushing condition of the step (1) is 1500rpm for 30 seconds; sieving with 200 mesh sieve; grinding for 2 minutes at a grinding speed of 60 r/min; the conditions of the high-temperature sterilizing agent are 125 ℃ and 15 minutes; the conditions of spray drying were 500 ℃; the pressure of the press forming is 500kg/cm²The temperature is 40-50 ℃.

As an optimization, the mixing method of the titanium dioxide nanofibers and the modified hydrotalcite in the step (4) comprises the following steps: titanium dioxide nano fibers, modified hydrotalcite and deionized water are mixed according to the mass ratio of 1: 1: 20, mixing, and stirring at the rotating speed of 300-500 rpm for 1 hour to obtain a mixed solution; and transferring the mixed solution into a reaction kettle, reacting for 6 hours at the temperature of 180 ℃, filtering a reaction product to obtain a solid, and vacuum-drying for 12 hours at the temperature of 60 ℃ to obtain the titanium dioxide nanofiber-modified hydrotalcite composite material.

Optimizing, wherein the thickness of the glaze surface in the step (5) is 0.5-1 mm; the sintering process is as follows: heating to 300-450 ℃ at the speed of 5-6 ℃/min, preserving heat for 20-30 minutes, heating to 600-800 ℃ at the speed of 8-12 ℃/min, preserving heat for 20-30 minutes, heating to 950-1250 ℃ at the heating speed of 8-12 ℃/min, preserving heat, sintering for 1-5 hours, discharging, and cooling to room temperature to obtain the refractory and wear-resistant ceramic tile.

Compared with the prior art, the invention has the following beneficial effects:

the invention uses clay, powdery quartz, feldspar and borocalcite as brick making raw materials when preparing the fire-resistant and wear-resistant ceramic tile, and the surface of the brick is glazed after the brick is prepared into a green brick, and then the ceramic tile is prepared by high-temperature sintering; the glaze slip is prepared from borax, silicon carbide, modified zinc-magnesium-aluminum ternary hydrotalcite and titanium dioxide nano-fibers.

Firstly, mixing titanium dioxide nano fibers and zinc-magnesium-aluminum ternary hydrotalcite, wherein the titanium dioxide nano fibers are deposited and attached to the surface of the hydrotalcite, and the hydrotalcite contains a large number of hydrophilic groups and carries the titanium dioxide nano fibers to be uniformly dispersed in silica sol; the silicon carbide in the glaze slip reacts with oxygen in the sintering process to generate carbon monoxide and carbon dioxide gas, so that a large number of air holes are generated on the glaze surface of the ceramic tile, and the heat insulation and heat preservation performance of the ceramic tile is enhanced; the ceramic tile is characterized in that the ceramic tile is heated along with the temperature rise and is sintered in a sealing mode, gas in air holes escapes outwards, pressure is increased, hydrotalcite with a lamellar structure is vertically flushed to the surfaces of the air holes under the action of the pressure, the hydrotalcite is enabled to carry titanium dioxide nano fibers and is vertically arranged on the surfaces of the air holes, the temperature rise of the hydrotalcite is continued, the titanium dioxide fibers are reserved at the air holes and serve as supports of the air holes, the strength of the ceramic tile is enhanced, the ceramic tile is enabled to have a large number of air holes on the surface, the thermal insulation performance is enhanced, meanwhile, the strength of the ceramic tile cannot be reduced due to the existence of the multiple holes, and the non-smooth microscopic morphology is formed on the surface of the ceramic tile due to the vertical arrangement of the titanium dioxide fibers at the air holes, so that the wear resistance of the ceramic tile is enhanced.

Secondly, interlayer anions of the zinc-magnesium-aluminum ternary hydrotalcite are substituted by hydrogen phosphate ions, and the hydrotalcite is decomposed and then reacts with phosphoric acid to generate an aluminum dihydrogen phosphate-based binder which can bind the titanium dioxide nanofibers with the surface of the ceramic tile; when the temperature rises, the zinc-magnesium-aluminum ternary hydrotalcite generates a large amount of zinc oxide, the zinc oxide reacts with phosphoric acid in a system to generate a zinc salt complex, the polarization capability is extremely strong, the curing of the aluminum dihydrogen phosphate-based binder can be promoted, the binding power is stronger, and the binding power between the titanium dioxide nanofibers and the surface of the ceramic tile is further enhanced; meanwhile, the liquid phase in the system is increased due to the addition of the borax, the silicon carbide reaction is more sufficient, the internal pressure of air holes is increased, part of air holes are broken and bonded with each other, a part of air holes are filled with the binder in the system, the hole wall is thickened, the volume of the glaze surface is shrunk, the volume density is increased, and the strength of the ceramic tile is enhanced.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In order to more clearly illustrate the method provided by the present invention, the following examples are provided to illustrate the method for testing each index of the refractory and wear-resistant ceramic tile manufactured in the following examples as follows:

wear resistance: according to the standard GB/T3810.7, the tile samples prepared in the examples and the comparative examples are cut into the size of 100mm x 100mm, and after cleaning, the tile samples are placed in a drying oven to be dried, the temperature is set to be 110 ℃, the mass of the tile samples is weighed after cooling, then the grinding medium is placed on the surface of the samples prepared in the examples and the comparative examples to be rotated, the number of rotations is set to be ten thousand rotations, the ceramic samples are taken out and dried, and then the mass weighing is carried out again, and the smaller the mass difference of the two weighing is, the better the wear resistance of the prepared products is.

Compression resistance: according to the standard GB/T4100, the products obtained in each example and comparative example are cut off to the periphery with the width of about 10mm, 5 samples with the size of 100mm multiplied by 100mm are respectively cut on each product, the samples are cleaned by ethanol, placed in an oven at 50 ℃ for drying for 4 hours, and placed in a dryer for cooling to the room temperature; the sample was placed on a test machine at 10000kg/m²The sample is pressed until the sample is sufficiently crushed, the total pressure required to crush the sample is recorded, and the maximum load pressure per unit area of the sample is calculated, the greater the maximum load pressure value is, the better the compressive strength of the product is.

Example 1

A refractory wear-resistant ceramic tile mainly comprises the following components in parts by weight: 180 parts of brick ingredients and 40 parts of glaze ingredients;

the brick body batching includes: 80 parts of albite, 40 parts of anorthite, 30 parts of sanidine, 20 parts of kaolin and 10 parts of bentonite;

the glaze comprises the following ingredients: 20 parts of kaolin, 2 parts of borax, 8 parts of silicon carbide, 5 parts of modified hydrotalcite and 5 parts of wear-resistant fiber.

The preparation method of the fire-resistant and wear-resistant ceramic tile mainly comprises the following preparation steps:

(1) mixing albite, anorthite, sanidine, kaolin and bentonite according to the mass ratio of 8: 4: 3: 2: 1, putting the mixture into a grinder to be ground to obtain a ground material; sieving the crushed materials, and mixing with deionized water according to a mass ratio of 4: 1, putting the mixture into a ball mill, grinding the mixture uniformly to obtain slurry, cooling the slurry to room temperature, putting the slurry into a high-temperature sterilizer for drying, putting the dried slurry into a spray drying tower, sending hot air with the temperature of 560 ℃ by using a hot air furnace to obtain dried particles, and putting the dried particles into a mould for compression molding to obtain a green brick; the thickness of the green brick is 8 mm.

(2) Magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate and deionized water in a mass ratio of 1: 1: 1: 20, uniformly mixing to obtain a mixed salt solution A; sodium hydroxide, sodium carbonate and deionized water are mixed according to the mass ratio of 2: 1: 20, uniformly mixing to obtain a mixed salt solution B; dropping the mixed salt solution A into the mixed salt solution B at the speed of 12ml/min, wherein the mass ratio of the mixed salt solution A to the mixed salt solution B is 2: 1, heating in an oil bath at 50 ℃ in the dropping process and magnetically stirring at the speed of 300 rpm; after the dropwise addition, adjusting the pH value of the system to 10 by using 1mol/L sodium hydroxide solution, and keeping the temperature at 50 ℃ for standing for 30 minutes to obtain a suspension; centrifuging the suspension for 50 minutes at the rotating speed of 2500rpm, re-dispersing the precipitate obtained by filtering in deionized water with the mass of 10 times that of the precipitate, and uniformly mixing to obtain a dispersion liquid; transferring the dispersion liquid to a hydrothermal reaction kettle, carrying out hydrothermal reaction at the temperature of 120 ℃ for 24 hours, naturally cooling a product obtained by the reaction to room temperature, carrying out suction filtration twice, washing a solid obtained by the suction filtration 3 times by using deionized water, and drying in a vacuum drying oven at the temperature of 60 ℃ for 24 hours to obtain zinc-magnesium-aluminum ternary hydrotalcite; zinc-magnesium-aluminum ternary hydrotalcite and deionized water are mixed according to the mass ratio of 3: 20, mixing to obtain hydrotalcite dispersion liquid; dropwise adding a sodium dihydrogen phosphate solution with the mass fraction of 98% into the hydrotalcite dispersion liquid at the speed of 15ml/min to obtain a mixed solution, wherein the mass ratio of the sodium dihydrogen phosphate solution to the hydrotalcite dispersion liquid is 1: 5; adjusting the pH value of the system to 4 by using 1mol/L dilute nitric acid solution, stirring the mixed solution at the rotating speed of 200rpm at 98 ℃ for refluxing for 12 hours, cooling to room temperature, washing the solid obtained by suction filtration by using deionized water until the washing liquid is neutral, and performing vacuum drying at 60 ℃ for 12 hours to obtain modified hydrotalcite;

(3) mixing titanium dioxide particles and a sodium hydroxide solution with the concentration of 10mol/L according to the mass ratio of 1: 30, and uniformly stirring to obtain a titanium dioxide suspension; putting the titanium dioxide suspension into a reaction kettle, reacting for 12 hours at the temperature of 200 ℃, and washing products obtained by the reaction with hydrochloric acid, water and alcohol in sequence until washing liquor is neutral; centrifuging the washed neutral reaction product at the rotating speed of 2500rpm for 50 minutes, and carrying out vacuum drying on the filtered solid at the temperature of 60 ℃ for 24 hours to obtain titanium dioxide nano fibers;

(4) uniformly mixing titanium dioxide nanofibers and modified hydrotalcite to obtain a titanium dioxide nanofiber-modified hydrotalcite composite material; mixing titanium dioxide nanofiber-modified hydrotalcite composite material, kaolin, borax and silicon carbide according to the mass ratio of 5: 10: 1: 4 mixing and putting the mixture into a grinder to be ground to the fineness of 200 meshes to obtain ground materials; mixing the crushed material and deionized water according to a mass ratio of 4: 1, mixing, stirring at 1800rpm for 8 hours to obtain glaze slip;

(5) and coating the glaze slip on the surface of the green brick, placing the glazed green brick into a kiln for high-temperature sintering, and naturally cooling to room temperature after sintering to obtain the refractory wear-resistant ceramic tile.

As optimization, the crushing condition of the step (1) is 1500rpm for 30 seconds; sieving with 200 mesh sieve; grinding for 2 minutes at a grinding speed of 60 r/min; the conditions of the high-temperature sterilizing agent are 125 ℃ and 15 minutes; the conditions of spray drying were 500 ℃; the pressure of the press forming is 500kg/cm²The temperature is 40-50 ℃.

As an optimization, the mixing method of the titanium dioxide nanofibers and the modified hydrotalcite in the step (4) comprises the following steps: titanium dioxide nano fibers, modified hydrotalcite and deionized water are mixed according to the mass ratio of 1: 1: 20, mixing, and stirring at the rotating speed of 300rpm for 1 hour to obtain a mixed solution; and transferring the mixed solution into a reaction kettle, reacting for 6 hours at the temperature of 180 ℃, filtering a reaction product to obtain a solid, and vacuum-drying for 12 hours at the temperature of 60 ℃ to obtain the titanium dioxide nanofiber-modified hydrotalcite composite material.

Optimally, the glaze surface in the step (5) is 1mm in thickness; the sintering process is as follows: heating to 400 ℃ at the speed of 5 ℃/min, preserving heat for 30 minutes, heating to 800 ℃ at the speed of 10 ℃/min, preserving heat for 30 minutes, heating to 1250 ℃ at the speed of 10 ℃/min, preserving heat, sintering for 5 hours, discharging, and cooling to room temperature to obtain the refractory wear-resistant ceramic tile.

Example 2

A refractory wear-resistant ceramic tile mainly comprises the following components in parts by weight: 180 parts of brick ingredients and 40 parts of glaze ingredients;

the brick body batching includes: 80 parts of albite, 40 parts of anorthite, 30 parts of sanidine, 20 parts of kaolin and 10 parts of bentonite;

the glaze comprises the following ingredients: 20 parts of kaolin, 2 parts of borax, 8 parts of silicon carbide and 10 parts of wear-resistant fibers.

The preparation method of the fire-resistant and wear-resistant ceramic tile mainly comprises the following preparation steps:

(1) mixing albite, anorthite, sanidine, kaolin and bentonite according to the mass ratio of 8: 4: 3: 2: 1, putting the mixture into a grinder to be ground to obtain a ground material; sieving the crushed materials, and mixing with deionized water according to a mass ratio of 4: 1, putting the mixture into a ball mill, grinding the mixture uniformly to obtain slurry, cooling the slurry to room temperature, putting the slurry into a high-temperature sterilizer for drying, putting the dried slurry into a spray drying tower, sending hot air with the temperature of 560 ℃ by using a hot air furnace to obtain dried particles, and putting the dried particles into a mould for compression molding to obtain a green brick; the thickness of the green brick is 8 mm.

(3) Mixing titanium dioxide particles and a sodium hydroxide solution with the concentration of 10mol/L according to the mass ratio of 1: 30, and uniformly stirring to obtain a titanium dioxide suspension; putting the titanium dioxide suspension into a reaction kettle, reacting for 12 hours at the temperature of 200 ℃, and washing products obtained by the reaction with hydrochloric acid, water and alcohol in sequence until washing liquor is neutral; centrifuging the washed neutral reaction product at the rotating speed of 2500rpm for 50 minutes, and carrying out vacuum drying on the filtered solid at the temperature of 60 ℃ for 24 hours to obtain titanium dioxide nano fibers;

(4) titanium dioxide nano fibers, kaolin, borax and silicon carbide are mixed according to the mass ratio of 5: 10: 1: 4 mixing and putting the mixture into a grinder to be ground to the fineness of 200 meshes to obtain ground materials; mixing the crushed material and deionized water according to a mass ratio of 4: 1, mixing, stirring at 1800rpm for 8 hours to obtain glaze slip;

(5) and coating the glaze slip on the surface of the green brick, placing the glazed green brick into a kiln for high-temperature sintering, and naturally cooling to room temperature after sintering to obtain the refractory wear-resistant ceramic tile.

As optimization, the crushing condition of the step (1) is 1500rpm for 30 seconds; sieving with 200 mesh sieve; grinding for 2 minutes at a grinding speed of 60 r/min; the conditions of the high-temperature sterilizing agent are 125 ℃ and 15 minutes; the conditions of spray drying were 500 ℃; the pressure of the press forming is 500kg/cm²The temperature was 50 ℃.

Optimally, the glaze surface in the step (5) is 1mm in thickness; the sintering process is as follows: heating to 400 ℃ at the speed of 5 ℃/min, preserving heat for 30 minutes, heating to 800 ℃ at the speed of 10 ℃/min, preserving heat for 30 minutes, heating to 1250 ℃ at the speed of 10 ℃/min, preserving heat, sintering for 5 hours, discharging, and cooling to room temperature to obtain the refractory wear-resistant ceramic tile.

Example 3

A refractory wear-resistant ceramic tile mainly comprises the following components in parts by weight: 180 parts of brick ingredients and 40 parts of glaze ingredients;

the brick body batching includes: 80 parts of albite, 40 parts of anorthite, 30 parts of sanidine, 20 parts of kaolin and 10 parts of bentonite;

the glaze comprises the following ingredients: 20 parts of kaolin, 2 parts of borax, 8 parts of silicon carbide and 10 parts of modified hydrotalcite.

The preparation method of the fire-resistant and wear-resistant ceramic tile mainly comprises the following preparation steps:

(1) mixing albite, anorthite, sanidine, kaolin and bentonite according to the mass ratio of 8: 4: 3: 2: 1, putting the mixture into a grinder to be ground to obtain a ground material; sieving the crushed materials, and mixing with deionized water according to a mass ratio of 4: 1, putting the mixture into a ball mill, grinding the mixture uniformly to obtain slurry, cooling the slurry to room temperature, putting the slurry into a high-temperature sterilizer for drying, putting the dried slurry into a spray drying tower, sending hot air with the temperature of 560 ℃ by using a hot air furnace to obtain dried particles, and putting the dried particles into a mould for compression molding to obtain a green brick; the thickness of the green brick is 8 mm.

(2) Magnesium chloride hexahydrate, zinc chloride, aluminum chloride hexahydrate and deionized water in a mass ratio of 1: 1: 1: 20, uniformly mixing to obtain a mixed salt solution A; sodium hydroxide, sodium carbonate and deionized water are mixed according to the mass ratio of 2: 1: 20, uniformly mixing to obtain a mixed salt solution B; dropping the mixed salt solution A into the mixed salt solution B at the speed of 12ml/min, wherein the mass ratio of the mixed salt solution A to the mixed salt solution B is 2: 1, heating in an oil bath at 50 ℃ in the dropping process and magnetically stirring at the speed of 300 rpm; after the dropwise addition, adjusting the pH value of the system to 10 by using 1mol/L sodium hydroxide solution, and keeping the temperature at 50 ℃ for standing for 30 minutes to obtain a suspension; centrifuging the suspension for 50 minutes at the rotating speed of 2500rpm, re-dispersing the precipitate obtained by filtering in deionized water with the mass of 10 times that of the precipitate, and uniformly mixing to obtain a dispersion liquid; transferring the dispersion liquid to a hydrothermal reaction kettle, carrying out hydrothermal reaction at the temperature of 120 ℃ for 24 hours, naturally cooling a product obtained by the reaction to room temperature, carrying out suction filtration twice, washing a solid obtained by the suction filtration 3 times by using deionized water, and drying in a vacuum drying oven at the temperature of 60 ℃ for 24 hours to obtain zinc-magnesium-aluminum ternary hydrotalcite; zinc-magnesium-aluminum ternary hydrotalcite and deionized water are mixed according to the mass ratio of 3: 20, mixing to obtain hydrotalcite dispersion liquid; dropwise adding a sodium dihydrogen phosphate solution with the mass fraction of 98% into the hydrotalcite dispersion liquid at the speed of 15ml/min to obtain a mixed solution, wherein the mass ratio of the sodium dihydrogen phosphate solution to the hydrotalcite dispersion liquid is 1: 5; adjusting the pH value of the system to 4 by using 1mol/L dilute nitric acid solution, stirring the mixed solution at the rotating speed of 200rpm at 98 ℃ for refluxing for 12 hours, cooling to room temperature, washing the solid obtained by suction filtration by using deionized water until the washing liquid is neutral, and performing vacuum drying at 60 ℃ for 12 hours to obtain modified hydrotalcite;

(4) modified hydrotalcite, kaolin, borax and silicon carbide are mixed according to the mass ratio of 5: 10: 1: 4 mixing and putting the mixture into a grinder to be ground to the fineness of 200 meshes to obtain ground materials; mixing the crushed material and deionized water according to a mass ratio of 4: 1, mixing, stirring at 1800rpm for 8 hours to obtain glaze slip;

(5) and coating the glaze slip on the surface of the green brick, placing the glazed green brick into a kiln for high-temperature sintering, and naturally cooling to room temperature after sintering to obtain the refractory wear-resistant ceramic tile.

As optimization, the crushing condition of the step (1) is 1500rpm for 30 seconds; sieving with 200 mesh sieve; grinding for 2 minutes at a grinding speed of 60 r/min; the conditions of the high-temperature sterilizing agent are 125 ℃ and 15 minutes; the conditions of spray drying were 500 ℃; the pressure of the press forming is 500kg/cm²The temperature was 50 ℃.

Optimally, the glaze surface in the step (5) is 1mm in thickness; the sintering process is as follows: heating to 400 ℃ at the speed of 5 ℃/min, preserving heat for 30 minutes, heating to 800 ℃ at the speed of 10 ℃/min, preserving heat for 30 minutes, heating to 1250 ℃ at the speed of 10 ℃/min, preserving heat, sintering for 5 hours, discharging, and cooling to room temperature to obtain the refractory wear-resistant ceramic tile.

Comparative example

A refractory wear-resistant ceramic tile mainly comprises the following components in parts by weight: 180 parts of brick ingredients and 40 parts of glaze ingredients;

the brick body batching includes: 80 parts of albite, 40 parts of anorthite, 30 parts of sanidine, 20 parts of kaolin and 10 parts of bentonite;

the glaze comprises the following ingredients: 20 parts of kaolin, 4 parts of borax and 16 parts of silicon carbide.

The preparation method of the fire-resistant and wear-resistant ceramic tile mainly comprises the following preparation steps:

(1) mixing albite, anorthite, sanidine, kaolin and bentonite according to the mass ratio of 8: 4: 3: 2: 1, putting the mixture into a grinder to be ground to obtain a ground material; sieving the crushed materials, and mixing with deionized water according to a mass ratio of 4: 1, putting the mixture into a ball mill, grinding the mixture uniformly to obtain slurry, cooling the slurry to room temperature, putting the slurry into a high-temperature sterilizer for drying, putting the dried slurry into a spray drying tower, sending hot air with the temperature of 560 ℃ by using a hot air furnace to obtain dried particles, and putting the dried particles into a mould for compression molding to obtain a green brick; the thickness of the green brick is 8 mm.

(2) Mixing kaolin, borax and silicon carbide according to the mass ratio of 5: 1: 4 mixing and putting the mixture into a grinder to be ground to the fineness of 200 meshes to obtain ground materials; mixing the crushed material and deionized water according to a mass ratio of 4: 1, mixing, stirring at 1800rpm for 8 hours to obtain glaze slip;

(3) and coating the glaze slip on the surface of the green brick, placing the glazed green brick into a kiln for high-temperature sintering, and naturally cooling to room temperature after sintering to obtain the refractory wear-resistant ceramic tile.

As optimization, the crushing condition of the step (1) is 1500rpm for 30 seconds; sieving with 200 mesh sieve; grinding for 2 minutes at a grinding speed of 60 r/min; the conditions of the high-temperature sterilizing agent are 125 ℃ and 15 minutes; the conditions of spray drying were 500 ℃; the pressure of the press forming is 500kg/cm²The temperature was 50 ℃.

Optimally, the glaze surface in the step (5) is 1mm in thickness; the sintering process is as follows: heating to 400 ℃ at the speed of 5 ℃/min, preserving heat for 30 minutes, heating to 800 ℃ at the speed of 10 ℃/min, preserving heat for 30 minutes, heating to 1250 ℃ at the speed of 10 ℃/min, preserving heat, sintering for 5 hours, discharging, and cooling to room temperature to obtain the refractory wear-resistant ceramic tile.

Examples of effects

Table 1 below shows the results of performance analysis of the fire-resistant and abrasion-resistant tiles using examples 1 to 3 of the present invention and comparative examples.

TABLE 1

	Example 1	Example 2	Example 3	Comparative example
					Poor quality (g)	0.12	0.16	0.21	0.37
Specific maximum bearing pressure (kg/cm)2)	1700	1200	1350	950

From the comparison of the experimental data of the embodiment 1 and the comparative example, it can be found that silicon carbide in the glaze slip reacts with oxygen in the sintering process to generate carbon monoxide and carbon dioxide gas, so that a large number of air holes are generated on the glaze surface of the ceramic tile, the gas in the air holes escapes outwards along with the rise of temperature, the pressure is increased, the hydrotalcite with the lamellar structure is vertically flushed to the surfaces of the air holes under the action of the pressure, so that the hydrotalcite carries titanium dioxide nanofibers and is vertically arranged on the surfaces of the air holes, the temperature of the hydrotalcite is continuously increased, the hydrotalcite is decomposed, and the titanium dioxide fibers are retained at the air holes and serve as supports of the air holes, so that the compressive strength of the ceramic tile is enhanced; after the hydrotalcite is disintegrated, the hydrotalcite reacts with phosphoric acid to generate aluminum dihydrogen phosphate-based binder, the zinc-magnesium-aluminum ternary hydrotalcite is continuously decomposed to generate a large amount of zinc oxide, and zinc oxide reacts with phosphoric acid in a system to generate a zinc salt complex, so that the curing of the aluminum dihydrogen phosphate-based binder is promoted, the binding power is stronger, the binding capacity of the titanium dioxide nanofibers and the surface of the ceramic tile is further enhanced, the titanium dioxide fibers are uniformly and firmly combined on the glaze surface and present a non-smooth microscopic surface, and the wear resistance of the ceramic tile is enhanced; from the comparison of the experimental data of the embodiment 1 and the embodiment 2, it can be found that the titanium dioxide nanofibers are vertically arranged on the surfaces of the air holes by adding the hydrotalcite to serve as the supports of the air holes, so that the compressive strength of the ceramic tile is enhanced, and the hydrotalcite is decomposed to generate a binder, so that the titanium dioxide fibers are uniformly and firmly combined on the glaze surface and present a non-smooth microscopic surface, and the wear resistance of the ceramic tile is enhanced; compared with the experimental data of the embodiment 1 and the embodiment 3, the titanium dioxide nano fibers are vertically arranged on the surfaces of the air holes through the hydrotalcite and are used as the supports of the air holes, so that the compressive strength of the ceramic tile is enhanced, and the glaze surface of the titanium dioxide fiber presents a non-smooth microscopic surface, so that the wear resistance of the ceramic tile is enhanced.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.