CN114671677A - Energy-saving high-hardness ceramic tile and production process thereof - Google Patents

Energy-saving high-hardness ceramic tile and production process thereof Download PDF

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CN114671677A
CN114671677A CN202210376762.6A CN202210376762A CN114671677A CN 114671677 A CN114671677 A CN 114671677A CN 202210376762 A CN202210376762 A CN 202210376762A CN 114671677 A CN114671677 A CN 114671677A
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ceramic tile
hardness
energy
parts
glaze
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CN114671677B (en
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刘高辉
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Hebei Xinbo'er Porcelain Co ltd
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Hebei Xinbo'er Porcelain Co ltd
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Abstract

The application relates to the technical field of ceramic tiles, and particularly discloses an energy-saving high-hardness ceramic tile and a production process thereof. The energy-saving high-hardness ceramic tile comprises a ceramic tile blank body and glaze, wherein the ceramic tile blank body comprises the following raw materials in percentage by weight: 25-35% of potassium feldspar powder, 25-35% of sodium feldspar powder, 10-15% of bentonite, 2-4% of calcined high-alumina powder, 8-10% of washing mud, 10-15% of quartz powder and 0.3-0.7% of composite reinforcing agent; the composite reinforcing agent comprises 3-5 parts by weight of polyvinyl butyral and 1-3 parts by weight of calcium lignosulfonate. The highest Mohs hardness, the highest breaking modulus, the highest breaking strength and the highest wear resistance of the ceramic tile are 5-grade, 56.1MPa, 1980N and 4-grade 6000 turns respectively, so that the hardness of the ceramic tile is improved; and the stain resistance grade is 4 grades, and the stain resistance is higher while the hardness is improved.

Description

Energy-saving high-hardness ceramic tile and production process thereof
Technical Field
The application relates to the technical field of ceramic tiles, in particular to an energy-saving high-hardness ceramic tile and a production process thereof.
Background
The ceramic tile is an acid and alkali resistant porcelain building decoration material which is prepared by grinding, mixing, pressing, glazing and sintering refractory metal oxides and semimetal oxides. Ceramic tiles can be divided into glazed tiles, full body tiles, polished tiles and vitrified tiles according to the process. The glazed tile is a ceramic tile obtained by firing a ceramic tile blank at a high temperature and a high pressure after glazing, and has low water absorption and rich color patterns, so that the glazed tile is widely used for wall and ground decoration.
In the related technology, the glazed tile is prepared from kaolin, feldspar powder, wollastonite, quartz and talcum powder as raw materials, the prepared glazed tile is poor in hardness, scratches are prone to occurring in the using process, the service life is affected, the glazed tile is prone to being damaged in the transportation and installation processes, and the cost is greatly increased.
Disclosure of Invention
In order to improve the hardness of the ceramic tile, the application provides an energy-saving high-hardness ceramic tile and a production process thereof.
In a first aspect, the present application provides an energy-saving high-hardness ceramic tile, which adopts the following technical scheme:
the energy-saving high-hardness ceramic tile comprises a ceramic tile blank body and glaze, wherein the ceramic tile blank body comprises the following raw materials in percentage by weight: 25-35% of potassium feldspar powder, 25-35% of sodium feldspar powder, 10-15% of bentonite, 2-4% of calcined high-alumina powder, 8-10% of washing mud, 10-15% of quartz powder and 0.3-0.7% of composite reinforcing agent; the composite reinforcing agent comprises 3-5 parts by weight of polyvinyl butyral and 1-3 parts by weight of calcium lignosulfonate.
By adopting the technical scheme, the main chemical component of the potassium feldspar powder is calcium oxide which is a flux raw material and a barren raw material, the sintering temperature in the green body is reduced, the drying time of the green body can be shortened, and the shrinkage and deformation of the green body during drying are reduced. In addition, the potassium feldspar powder is melted into feldspar glass at high temperature, gaps among the green body particles are filled, the green body is compact due to the bonding of the particles, the transparency can be improved, and the mechanical strength of the green body can be improved. In addition, the potassium feldspar powder is beneficial to the generation of a glass phase when the blank is calcined at a high temperature, so that the ceramic degree of the ceramic tile is improved, the porosity of the blank is reduced, and the hardness of the ceramic tile is improved.
The albite powder is sodium-containing aluminosilicate rock-selecting mineral, has high alumina content and low iron content, can be used as a raw material for rendering albite barren before the ceramic tile blank is fired, can reduce drying shrinkage and deformation of the ceramic tile blank, improves drying performance, shortens drying time, can be used as a flux to be filled in the blank during firing, enables the blank to be compact and reduces gaps, further improves the compactness of the ceramic tile, and improves the hardness of the ceramic tile.
The addition of the bentonite increases the plasticity and the strength of the blank, greatly increases the lubricating effect and is beneficial to ball milling; in addition, the suspension property and the stability of the bentonite are greatly enhanced, the porcelain is fine and smooth, and has collision resistance and certain mechanical strength.
The main component of the calcined high-alumina powder is alumina, the aluminum content is high, and the aluminum content in the ceramic tile blank is improved, so that the hardness of the ceramic tile is improved. The washing mud is also called washing kaolin, and has higher cohesive force, plasticity and good sintering performance. The quartz powder is a non-metallic mineral substance, is hard and wear-resistant in material and stable in chemical property, and the main mineral component is silicon dioxide, so that the plasticity of the tile pug can be adjusted, the shrinkage can be reduced during drying, the drying time can be shortened, the blank body can be prevented from deforming, the blank body can be prevented from bending and deforming during firing, the blank body combining capacity can be increased, and the hardness of the tile can be improved.
The addition of the composite reinforcing agent has the effects of mutual winding and crosslinking among molecular long chains at high temperature, so that ceramic raw material particles are more tightly bonded together, and the particles are prevented from displacing under the stress condition, thereby playing a role in reinforcement, and the composite reinforcing agent has the characteristics of good dispersity and fluidity, small using amount and remarkable reinforcing effect, and particularly can remarkably improve the strength of a green body before drying and reduce the damage of the green body; the ceramic tile has certain drying and water retention uniformity, and the reinforcing agent is carbonized and burned out when the sintering temperature reaches 400-600 ℃, so that the flowing property of slurry and the final property of the ceramic tile are not adversely affected.
The polyvinyl butyral is a novel high-molecular adhesive, has higher impact performance, and improves the hardness of a ceramic tile blank; the calcium lignosulfonate is a multi-component high-molecular polymer anionic surfactant, has high dispersibility and cohesiveness, can reduce the carbon content in a ceramic tile blank, and improves the fluidity of slurry and the sintering speed of the blank, thereby improving the hardness of the ceramic tile blank.
Preferably, the method comprises the following steps: the ceramic tile blank comprises the following raw materials in percentage by weight: 28-32% of potassium feldspar powder, 28-32% of sodium feldspar powder, 12-14% of bentonite, 2.5-3.5% of calcined high-alumina powder, 8.5-9.5% of water washing mud, 12-14% of quartz powder and 0.15-0.25% of composite reinforcing agent.
Preferably, the method comprises the following steps: the composite reinforcing agent also comprises the following raw materials in parts by weight: 1-3 parts of sodium humate, 2-4 parts of sodium carboxymethyl starch and 1-3 parts of polyvinyl alcohol.
By adopting the technical scheme, the sodium humate has the properties of ion exchange, adsorption, complexation and the like and excellent permeability and dispersibility, can effectively disperse metal oxides, forms a protective film with stable chemical properties on the surface of metal, can increase the plasticity, the fluidity and the suspension of the tile pug, can also increase the drying degree of a blank body, increases the adhesion between the blank body and glaze, and improves the hardness of the tile.
The sodium carboxymethyl starch has the advantages of improving the water retention rate and the cohesion, being beneficial to enhancing and moisturizing the ceramic tile blank and reducing the cracking of the ceramic tile. The polyvinyl alcohol has the characteristics of improving the crack resistance and the bending toughness of the ceramic tile and can further improve the hardness of the ceramic tile.
Preferably, the method comprises the following steps: the composite reinforcing agent is prepared by the following operation steps: the raw materials of the composite reinforcing agent are uniformly mixed and ball-milled to the particle size of 300-500 meshes, so as to obtain the spherical composite reinforcing agent.
By adopting the technical scheme, the composite reinforcing agent is mixed, the particle size of the composite reinforcing agent is controlled to be 300-500 meshes, the composite reinforcing agent has larger specific surface area, and the surface effect of the composite reinforcing agent is improved, so that the reinforcing effect of the composite reinforcing agent in a ceramic tile blank is further improved.
Preferably, the method comprises the following steps: the glaze comprises the following raw materials in parts by weight: 5-10 parts of nano silicon dioxide, 10-20 parts of spodumene, 4-8 parts of corundum micro powder, 3-10 parts of superfine zirconium silicate, 5-10 parts of nano zinc oxide and 1-2 parts of sodium hexametaphosphate.
By adopting the technical scheme, the nano silicon dioxide is mutually combined into an irregular network in a tetrahedral form to form a network forming body, the proportion of the network forming body in the glaze surface can be increased by adding the nano silicon dioxide, the melting temperature of the glaze material is increased, the glossiness and hardness of the ceramic tile are improved, the firing temperature is reduced, good acid and alkali resistance is kept, and the thermal expansion coefficient of the glaze material is reduced.
The addition of spodumene can reduce the sintering temperature, reduce the melt viscosity, improve the high-temperature fluidity and the glass transition strength, enhance the strength and the smoothness and the flatness of the glaze surface, reduce the thermal expansion coefficient, overcome the cracks of the glaze surface, improve the thermal stability of the glaze surface and simultaneously improve the hundred degrees and the glossiness of the glaze surface. The doping of the corundum micro powder can improve the aluminum content in the glaze, adjust the silicon-aluminum content to ensure that the net structure of the glaze is tightly connected, and improve the hardness of the glaze, thereby improving the overall hardness of the ceramic tile. The chemical stability of the superfine zirconium silicate is good, the blank glaze binding performance of ceramics can be obviously improved, and the glaze strength of ceramic tiles is improved; the addition of the nano zinc oxide reduces the viscosity of the glaze, has surface effect, small-size effect and quantum effect, has larger surface energy, enhances the surface activity, improves the Vickers hardness of the glazed surface of the ceramic tile and reduces the sintering temperature. The sodium hexametaphosphate can further improve the dispersibility of the nano silicon dioxide and the nano zinc oxide in a glaze system.
Preferably, the method comprises the following steps: the glaze is prepared by the following operation steps: mixing the raw materials of the glaze, uniformly stirring, centrifuging, drying, and grinding to 50-70 meshes to obtain the glaze.
By adopting the technical scheme, after the glaze raw materials are uniformly mixed, the particle size is controlled, the pinhole defects of the glaze surface are reduced, and the glaze layer strength is improved, so that the hardness of the ceramic tile is improved.
Preferably, the method comprises the following steps: the raw materials of the ceramic tile blank also comprise 2-6% of superfine silicon carbide and 0.02-0.04% of polyethyleneimine.
By adopting the technical scheme, the superfine silicon carbide has high purity, high reaction activity and good chemical uniformity, and the density of the ceramic tile blank can be further improved by adding the superfine silicon carbide, so that the hardness of the ceramic tile is improved; the polyethyleneimine is added as a dispersant, can generate multi-branch spherical molecules in aqueous solution, and the amino group of the polyethyleneimine can be dissociated in the aqueous solution to enable the charge of the polyethyleneimine and the charge on the surface of the superfine silicon carbide to form a double electron layer, so that steric hindrance and electrostatic repulsion are generated, and the dispersibility of the superfine silicon carbide in the raw materials of the ceramic tile blank can be improved, thereby further improving the hardness of the ceramic tile blank.
In a second aspect, the present application provides a method for preparing an energy-saving high-hardness ceramic tile, which is specifically realized by the following technical scheme:
a preparation method of an energy-saving high-hardness ceramic tile comprises the following operation steps:
mixing the ceramic tile except the glaze and the surface treating agent, ball milling, deironing and sieving, ageing and homogenizing, spray drying, pulverizing, press forming and drying to obtain a dry ceramic tile blank;
preparing glaze;
and (3) applying glaze spraying cloth on the surface of the dry blank of the ceramic tile, calcining at the temperature of 1100-1120 ℃, cooling, uniformly coating a surface treating agent on the surface of the ceramic tile, drying, and polishing the surface of the ceramic tile until the glossiness is more than 85 ℃ to obtain the energy-saving high-hardness ceramic tile.
By adopting the technical scheme, the ceramic tile is calcined by adopting a low-temperature quick-firing mode, the calcining temperature of the ceramic tile is reduced to 1100-1120 ℃, the calcining speed is high, the calcining time is only 13-15 ℃, the tightness of the ceramic tile in the sintering process is improved, and the mechanical performance of the ceramic tile is improved while the hardness of the ceramic tile is improved. And the calcining temperature and the calcining time are reduced, and the energy consumption is saved.
Preferably, the method comprises the following steps: the cooling process comprises an extremely cold period and a slow cold period, wherein the temperature of the extremely cold period is from the calcining temperature to 500 ℃, the temperature of the slow cold period is from 500 to 300 ℃, and the cooling rates of the calcining temperature falling to the extremely cold and the extremely cold falling to the slow cold are respectively 200 ℃/min and 50 ℃/min
By adopting the technical scheme, the cooling after the calcination passes through the extreme cold period and the slow cold period, the cooling rates of 200 ℃/min and 50 ℃/min for respectively reducing the calcination temperature to the extreme cold and reducing the extreme cold to the slow cold are controlled, the flatness of the ceramic tile is further improved, and the hardness of the ceramic tile is improved.
In summary, the present application includes at least one of the following beneficial technical effects:
(1) this application makes mohs' hardness, modulus of rupture, breaking strength and the abrasion resistance of ceramic tile be 4 grades, 48.6MPa, 1910N, 4 grades 3300 commentaries on classics respectively through each raw materials kind and the volume of mixing of control ceramic tile, has improved the hardness of ceramic tile.
(2) This application makes the modulus of rupture, breaking strength and the abrasion resistance of ceramic tile be 50.9MPa, 1930N, 4 grades 3600 commentaries on classics respectively through control ceramic tile glaze raw materials kind and mixing volume, has further improved the hardness of ceramic tile.
(3) According to the ceramic tile blank composite reinforcing agent, the raw materials such as the sodium carboxymethyl starch are added into the raw materials of the ceramic tile blank composite reinforcing agent, so that the breaking modulus, the breaking strength and the abrasion resistance of the ceramic tile are respectively 50.9MPa, 1930N and 3600 turns at 4 levels, and the hardness of the ceramic tile is improved.
(4) The ceramic tile is characterized in that the calcined ceramic tile is cooled through an extremely cold period and a slow cold period in the preparation process of the ceramic tile, the temperature of the extremely cold period is from the calcining temperature to 500 ℃, the temperature of the slow cold period is from 500 ℃ to 300 ℃, the cooling rates of the calcining temperature falling to the extremely cold state and the extremely cold falling to the slow cold state are respectively 200 ℃/min and 50 ℃/min, and the hardness of the ceramic tile is further improved.
Detailed Description
The present application will be described in further detail with reference to specific examples.
The following raw materials are all commercially available products, and are all sufficient for disclosure of the raw materials in the present application, and should not be construed as limiting the source of the raw materials. The method specifically comprises the following steps: potassium feldspar powder with the grain size of 100 meshes; the particle size of the albite powder is 325 meshes; bentonite with the grain size of 200 meshes; calcining high-alumina powder with the particle size of 325 meshes; washing the mud with water, wherein the grain size is 1250 meshes; quartz powder with particle size of 0.1-0.5 mm; calcium lignosulfonate, the lignin content of which is 65%; sodium humate with an effective substance content of 99%; sodium carboxymethyl starch with an effective substance content of 99%; polyvinyl alcohol with the grain diameter of 160 meshes; nano silicon dioxide with the particle size of 20 nm; spodumene with a particle size of 80 mesh; corundum micropowder with the grain diameter of 600 meshes; superfine zirconium silicate with the grain diameter of 1.8 mu m; nano zinc oxide with the particle size of 10 nm; superfine silicon carbide with the grain diameter of 8 mu m; polyvinyl alcohol, type GS-polyvinyl alcohol; polyethyleneimine, molecular weight 2 ten thousand.
The following are examples of the preparation of the composite reinforcer
Preparation example 1
The composite reinforcing agent of preparation example 1 was prepared by the following procedure:
according to the mixing amount shown in the table 1, the polyvinyl butyral and the calcium lignosulfonate are uniformly mixed and ball-milled until the particle size is 400 meshes, so that the composite reinforcing agent is obtained.
Preparation examples 2 to 5
The preparation methods and the types of the raw materials of the composite reinforcers of the preparation examples 2 to 5 are completely the same as those of the preparation example 1, except that the mixing amounts of the raw materials are different, and the detailed description is shown in table 1.
TABLE 1 PREPARATION EXAMPLES 1-5 blending amounts of respective raw materials of composite reinforcing agent
(unit: kg)
Figure BDA0003590099660000051
Preparation examples 6 to 8
The preparation methods and the types of the raw materials of the composite reinforcers of the preparation examples 6 to 8 are completely the same as those of the preparation example 4, except that the mixing amounts of the raw materials are different, and the detailed description is shown in table 2.
TABLE 2 preparation examples 6-8 blending amounts of respective raw materials of composite reinforcing agent
(unit: kg)
Raw materials Preparation example 6 Preparation example 7 Preparation example 8
Polyvinyl butyral 4 4 4
Lignosulfonic acid sodium salt 2 2 2
Humic acid sodium salt 2 2 2
Sodium carboxymethyl starch 2 3 4
Polyvinyl alcohol 2 2 2
Example 1
The energy-saving high-hardness ceramic tile of example 1 was obtained by the following procedure:
according to the mixing amount shown in the table 3, potassium feldspar powder, sodium feldspar powder, bentonite, calcined high-alumina powder, washing mud, quartz powder and the reinforcing agent prepared in the preparation example 1 are uniformly mixed, ball-milled, iron-removed and sieved, aged and homogenized, spray-dried, pulverized, pressed and molded, and dried to obtain a ceramic tile blank;
and (3) applying glaze spraying cloth on the surface of the dry tile blank, calcining at 13 ℃ at 1100 ℃, and cooling at a cooling rate of 50 ℃/min to obtain the energy-saving high-hardness tile.
The glaze material can obviously improve the blank glaze binding performance of the ceramic, and improve the glaze strength of the ceramic tile, the type 633.
Example 2
The energy-saving high-hardness ceramic tile of example 2 is obtained by the following operation steps:
according to the mixing amount shown in the table 3, potassium feldspar powder, sodium feldspar powder, bentonite, calcined high-alumina powder, washing mud, quartz powder and the reinforcing agent prepared in the preparation example 1 are uniformly mixed, ball-milled, iron-removed and sieved, aged and homogenized, spray-dried, pulverized, pressed and molded, and dried to obtain a ceramic tile blank;
according to the mixing amount shown in the table 4, uniformly mixing nano silicon dioxide, spodumene, corundum micro powder, superfine zirconium silicate, nano zinc oxide and sodium hexametaphosphate, centrifuging, drying, and grinding to 60 meshes to obtain a glaze material;
and (3) applying glaze spraying cloth on the surface of the dry blank of the ceramic tile, calcining at the temperature of 1100 ℃, cooling at the cooling rate of 50 ℃/min to obtain the energy-saving high-hardness ceramic tile.
Examples 3 to 6
The energy-saving high-hardness ceramic tiles of examples 3 to 6 have the same preparation method and the same types of raw materials as those of example 2, except that the mixing amounts of the raw materials are different, and are specifically shown in tables 3 and 4.
Table 3 examples 1-6 blending amounts of each raw material for energy-saving high-hardness tile green body
(unit: kg)
Raw materials Examples 1 to 2 Example 3 Example 4 Example 5 Example 6
Potassium feldspar powder 32.7 31.7 30.7 31.5 31.3
Albite powder 30 30 30 30 30
Bentonite clay 13 13 13 13 13
Calcining high-alumina powder 2 3 4 3 3
Washing mud 9 9 9 9 9
Quartz powder 13 13 13 13 13
Composite reinforcing agent 0.3 0.3 0.3 0.5 0.7
Table 4 examples 2-6 blending amounts of each raw material of glaze for energy-saving high-hardness ceramic tile
(unit: kg)
Figure BDA0003590099660000061
Examples 7 to 10
The energy-saving high-hardness ceramic tiles of examples 7 to 10 were prepared in the same manner and in the same types as those of example 5, except that the amounts of the respective raw materials of the glaze were different, as shown in table 5.
TABLE 5 EXAMPLES 7-10 blending amounts of respective raw materials for glaze for energy-saving high-hardness ceramic tiles
(unit: kg)
Figure BDA0003590099660000062
Figure BDA0003590099660000071
Examples 11 to 13
The energy-saving high-hardness ceramic tiles of examples 11 to 13 were prepared by the same method and same raw material types as those of example 9, except that the raw materials of the ceramic tile blank further included ultra-fine silicon carbide and polyethyleneimine, and the specific amounts thereof are shown in table 6.
TABLE 6 EXAMPLES 11-13 blending amounts of respective raw materials for green body of energy-saving high-hardness ceramic tile
(unit: kg)
Raw materials Example 11 Example 12 Example 13
Potassium feldspar powder 29.47 27.45 25.47
Albite powder 30 30 30
Bentonite clay 13 13 13
Calcining high-alumina powder 3 3 3
Washing mud 9 9 9
Quartz powder 13 13 13
Composite reinforcing agent 0.5 0.5 0.5
Superfine silicon carbide 2 4 6
Polyethylene imine 0.03 0.03 0.03
Examples 14 to 20
The energy-saving high-hardness tiles of examples 14 to 20 were prepared in the same manner as in example 12, except that the composite reinforcing agent prepared in preparation examples 2 to 8 was used as the raw material of the energy-saving high-hardness tiles, and the types and amounts of the other raw materials were the same as those of example 12.
Example 21
The energy-saving high-hardness ceramic tile in example 21 is completely the same as that in example 19 in terms of the kind and the amount of the raw materials, except that the cooling process is carried out in an extremely cold stage and a slow cold stage, wherein the temperature in the extremely cold stage is from the calcination temperature to 900 ℃, the temperature in the slow cold stage is from 900 to 200 ℃, the cooling rates of the calcination temperature falling to the extremely cold stage and the extremely cold falling to the slow cold stage are respectively 150 ℃/min and 70 ℃/min, and the cooling process from 200 ℃ to complete cooling is natural cooling, and the rest of the preparation method is completely the same as that in example 19.
Comparative example 1
The energy-saving high-hardness tile of comparative example 1 was prepared exactly in the same manner as in example 1 except that: the potassium feldspar powder in the raw materials of the energy-saving high-hardness ceramic tile blank is replaced by the same amount of quartz powder, and the other raw materials and the mixing amount are the same as those in the embodiment 1.
Comparative example 2
The energy-saving high-hardness tile of comparative example 2 was prepared exactly in the same manner as in example 1, except that: calcined high-alumina powder is not added in the raw materials of the energy-saving high-hardness ceramic tile blank, and the consumption of the potassium feldspar powder is 34.7 kg; the other raw materials and the mixing amount are the same as those in example 1.
Comparative example 3
The energy-saving high-hardness tile of comparative example 3 was prepared exactly in the same manner as in example 1, except that: the composite reinforcing agent in the raw materials of the energy-saving high-hardness ceramic tile blank is replaced by 2kg of sodium lignosulfonate in equal amount, and the other raw materials and the mixing amount are the same as those in the example 1.
Performance detection
The following test standards or methods were used to test the performance of the various examples 1-21 and comparative examples 1-3, respectively, and the results are detailed in Table 7.
Mohs scale of hardness: the ceramic tile is stably placed on a hard support, the glaze surface faces upwards, standard ores with different Mohs values are selected from small to large to scratch the surface of the ceramic tile, a new ore cutting edge is used for applying force to uniformly and vertically scratch the surface of a sample, and the lowest hardness value which just can generate obvious scratches is used as a detection result.
Modulus of rupture: the modulus of rupture is measured by GB/T3810.4-2006 section 4 of ceramic tile test method, determination of modulus of rupture and breaking strength.
Breaking strength: the destructive strength of the ceramic tile is measured by GB/T3810.4-2006 ceramic tile test method part 4, determination of modulus of rupture and destructive strength.
Abrasion resistance: GB/T3810.7-2016 ceramic tile test method part 7: determination of abrasion resistance of glazed brick the abrasion resistance of the tile was tested.
Stain resistance rating: the degree of stain resistance of the tiles was determined using GB/T3810.14-2016 ceramic tile test method part 14: determination of stain resistance.
TABLE 7 Performance test results for different energy-saving high-hardness tiles
Figure BDA0003590099660000081
Figure BDA0003590099660000091
The detection results in table 7 show that the mohs hardness, the modulus of rupture, the breaking strength and the wear resistance of the energy-saving high-hardness ceramic tile obtained by the method are respectively 5-grade, 56.1MPa, 1980N and 4-grade 6000 turns at the highest, so that the hardness of the ceramic tile is improved; and the stain resistance grade is 4 grades, and the stain resistance is higher while the hardness is improved.
In examples 1 to 6, the modulus of rupture, the breaking strength and the abrasion resistance of the energy-saving high-hardness tile in example 5 are respectively 48.6MPa, 1910N and 4-grade 3300 revolutions, which are higher than those of the tiles in examples 1 to 4 and example 6, and the abrasion resistance of the tile is improved. The result shows that the mixing amount of the calcined high-alumina powder and the composite reinforcing agent in the example 5 is more appropriate, and may relate to the fact that the main component of the calcined high-alumina powder is alumina, the content of aluminum is higher, the content of aluminum in a tile blank is increased, the composite reinforcing agent is used for more tightly bonding ceramic raw material particles together, and the particles are prevented from generating displacement under a stress condition.
In examples 7 to 10, the energy-saving high-hardness ceramic tile of example 9 had a modulus of rupture, a breaking strength and a wear resistance of 50.9MPa, 1930N and 3600 revolutions at level 4, which were all higher than those of the ceramic tiles of examples 7 to 8 and example 10, and the hardness of the ceramic tile was improved; the result shows that the superfine zirconium silicate and the nano zinc oxide in the glaze of the ceramic tile raw material in the example 9 are more appropriate in doping amount, and may be related to that the superfine zirconium silicate can obviously improve the blank glaze binding performance of the ceramic, improve the tile glaze strength, and reduce the glaze viscosity due to the addition of the nano zinc oxide, and the ceramic tile has the surface effect, the small-size effect and the quantum effect, has larger surface energy, and enhances the surface activity.
In examples 11 to 13, the energy-saving high-hardness ceramic tile of example 12 had a modulus of rupture and a breaking strength of 51.7MPa and 1930N, respectively, which were higher than those of the ceramic tiles of examples 11 and 13, and increased the hardness of the ceramic tile, indicating that the addition of ultrafine silicon carbide and polyethyleneimine to the raw material of the ceramic tile blank further increased the hardness of the ceramic tile, probably related to the addition of ultrafine silicon carbide to further increase the density of the ceramic tile blank, and polyethyleneimine to further increase the dispersibility of the ultrafine silicon carbide in the raw material of the ceramic tile blank.
In examples 14 to 17, the mohs hardness, the modulus of rupture, the breaking strength, and the abrasion resistance of the energy-saving high-hardness tile of example 16 were respectively 5, 50.9MPa, 1930N, and 3600 r at 4, which were all higher than those of the tiles of examples 14 to 15 and example 17, and the hardness of the tile was improved, indicating that the mixing amounts of the composite reinforcing agents polyvinyl butyral and sodium lignosulfonate in the tile blank raw material were more appropriate, and may be related to the polyvinyl butyral having higher impact performance and the calcium lignosulfonate having higher dispersibility and cohesiveness, reducing the carbon content in the tile blank and improving the fluidity of the slurry.
In examples 18 to 20, the energy-saving high-hardness ceramic tile of example 19 had a modulus of rupture, a breaking strength, and a wear resistance of 50.9MPa, 1930N, 3600 r at 4 th level, which were all higher than those of the energy-saving high-hardness ceramic tiles of examples 18 and 20, and increased the hardness of the ceramic tile, indicating that the amount of sodium carboxymethyl starch in the raw material of the composite reinforcing agent for ceramic tile green bodies was more suitable, and may be related to the enhancement of the ceramic tile green bodies by having improved water retention and cohesion with sodium carboxymethyl starch.
Combining the tile performance test data of example 19 and example 21, it is found that the fracture modulus, the breaking strength and the wear resistance of example 21 are respectively 56.1MPa, 1980N and 6000 turns at 4, which are higher than those of the tile of example 19, and the hardness of the tile is improved, which indicates that when the tile is cooled after calcination and passes through an extremely cold period and a slow cold period, the extremely cold period temperature is from the calcination temperature to 500 ℃, the slow cold period temperature is from 500 ℃ to 300 ℃, and the cooling rates of the calcination temperature to the extremely cold and the extremely cold to the slow cold are respectively 200 ℃/min and 50 ℃/min, which is beneficial to improving the hardness of the tile and is possibly related to the cooling rate.
The performance detection data of the ceramic tiles of comparative examples 1-3 and example 1 show that the hardness of the ceramic tiles is improved to different degrees by adding the potassium feldspar powder, the calcined high-alumina powder and the composite reinforcing agent into the raw materials of the ceramic tiles.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (9)

1. The energy-saving high-hardness ceramic tile is characterized by comprising a ceramic tile blank and glaze, wherein the ceramic tile blank comprises the following raw materials in percentage by weight: 25-35% of potassium feldspar powder, 25-35% of sodium feldspar powder, 10-15% of bentonite, 2-4% of calcined high-alumina powder, 8-10% of washing mud, 10-15% of quartz powder and 0.3-0.7% of composite reinforcing agent; the composite reinforcing agent comprises 3-5 parts by weight of polyvinyl butyral and 1-3 parts by weight of calcium lignosulfonate.
2. The energy-saving high-hardness ceramic tile according to claim 1, wherein the ceramic tile blank comprises the following raw materials in percentage by weight: 28-32% of potassium feldspar powder, 28-32% of sodium feldspar powder, 12-14% of bentonite, 2.5-3.5% of calcined high-alumina powder, 8.5-9.5% of water washing mud, 12-14% of quartz powder and 0.15-0.25% of composite reinforcing agent.
3. The energy-saving high-hardness ceramic tile according to claim 1, wherein: the composite reinforcing agent also comprises the following raw materials in parts by weight: 1-3 parts of sodium humate, 2-4 parts of sodium carboxymethyl starch and 1-3 parts of polyvinyl alcohol.
4. The energy-saving high-hardness ceramic tile according to claim 3, wherein the composite reinforcing agent is prepared by the following steps: the raw materials of the composite reinforcing agent are uniformly mixed and ball-milled to the particle size of 300-500 meshes to obtain the spherical composite reinforcing agent.
5. The energy-saving high-hardness ceramic tile according to claim 1, wherein the glaze comprises the following raw materials in parts by weight: 5-10 parts of nano silicon dioxide, 10-20 parts of spodumene, 4-8 parts of corundum micro powder, 3-10 parts of superfine zirconium silicate, 5-10 parts of nano zinc oxide and 1-2 parts of sodium hexametaphosphate.
6. The energy-saving high-hardness ceramic tile according to claim 5, wherein the glaze is prepared by the following steps: mixing the raw materials of the glaze, uniformly stirring, centrifuging, drying, and grinding to 50-70 meshes to obtain the glaze.
7. The energy-saving high-hardness ceramic tile according to claim 1, wherein: the raw materials of the ceramic tile blank also comprise 2-6% of superfine silicon carbide and 0.02-0.04% of polyethyleneimine.
8. A process for producing energy-saving high-hardness ceramic tiles according to any one of claims 1 to 7, characterized by comprising the following operative steps:
preparing a ceramic tile blank, mixing the ceramic tile with the raw materials except the glaze and the surface treating agent, ball-milling, deironing, sieving, ageing, homogenizing, spray drying, pulverizing, press-forming and drying to obtain the ceramic tile blank;
preparing glaze;
and (3) applying glaze spraying cloth on the surface of the dry blank of the ceramic tile, calcining at the temperature of 1100-1130 ℃, cooling, uniformly coating a surface treating agent on the surface of the ceramic tile, drying, and polishing the surface of the ceramic tile until the glossiness is more than 85 ℃ to obtain the energy-saving high-hardness ceramic tile.
9. The process for producing energy-saving high-hardness ceramic tiles according to claim 8, wherein: and the cooling is carried out in an extremely cold period and a slow cold period, wherein the temperature of the extremely cold period is from the calcining temperature to 500 ℃, the temperature of the slow cold period is from 500 to 300 ℃, and the cooling rates of the calcining temperature falling to the extremely cold and the extremely cold falling to the slow cold are respectively 200 ℃/min and 50 ℃/min.
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