CN111233327B - Low-temperature wear-resistant frit, wear-resistant glaze material using same and glazed tile - Google Patents
Low-temperature wear-resistant frit, wear-resistant glaze material using same and glazed tile Download PDFInfo
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- CN111233327B CN111233327B CN202010341015.XA CN202010341015A CN111233327B CN 111233327 B CN111233327 B CN 111233327B CN 202010341015 A CN202010341015 A CN 202010341015A CN 111233327 B CN111233327 B CN 111233327B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/06—Frit compositions, i.e. in a powdered or comminuted form containing halogen
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
Abstract
The invention discloses a low-temperature wear-resistant frit which comprises the following raw materials of wollastonite, dolomite, kaolin, alumina and a strong fluxing agent, wherein the raw materials do not contain feldspar; according to the mass percentage, the addition amount of the dolomite is more than 8%, the addition amount of the wollastonite is more than 20%, and the addition amount of the alumina is less than 12%. The low-temperature wear-resistant frit provided by the technical scheme avoids introducing feldspar in the formula, and is favorable for improving the wear resistance of the low-temperature wear-resistant frit so as to overcome the defects in the prior art. Further, the wear-resistant glaze using the low-temperature wear-resistant frit is provided, and the wear resistance of the glaze is improved by separating anorthite and mullite which are main crystal phases from the low-temperature wear-resistant frit. In addition, the glazed tile using the wear-resistant glaze material is provided, wherein the wear resistance is 2100 r at grade 4, and the wear resistance and abrasion resistance of 6000 r are 0.042-0.05 g.
Description
Technical Field
The invention relates to the field of architectural ceramics, in particular to a low-temperature wear-resistant frit, wear-resistant glaze material using the same and glazed tile.
Background
At present, the abrasion resistance of the glaze is a great problem in the industry. When the glaze is used as a ground decoration material, the wear-resistant performance of the glaze has higher requirements, otherwise, the glaze is easy to grind, so the wear-resistant performance of the existing glaze cannot meet the requirements.
In this regard, some manufacturers of architectural ceramics have attempted to incorporate frits into glazes to improve the abrasion resistance of the glazes. Generally, however, the frit used in the glaze is generally fired by introducing a large amount of feldspar and alumina raw materials to promote Al in the frit composition2O3Content, because a certain amount of active Al is required for the devitrification in glazes2O3Addition of Al to the frit formulation2O3In this case, it is desirable to increase the abrasion resistance of the glaze by precipitating a large amount of crystals from the melt.
Although the active Al of the frit is increased by introducing a large amount of feldspar as a raw material2O3In a large amount of Na2O and K2O, and Na2O and K2O exists mainly in a liquid phase during firing, so that Na is not easily precipitated2O、K2A class O crystal; further, Na2O and K2The O exists in a glass phase after being cooled, and the existence of the glass phase is not beneficial to the improvement of the wear resistance. Furthermore, it is also impossible to increase the active Al2O3 content of the frit by introducing a large amount of alumina in the frit formulation of the prior art, because the temperature and refractoriness of alumina are very high, the introduced alumina raw material is easily present as free alumina, and does not provide active Al2O3 for crystallization, and thus, the wear resistance of the glaze is not improved.
Disclosure of Invention
The invention aims to provide a low-temperature wear-resistant frit, which avoids the introduction of feldspar in the formula, is favorable for improving the wear resistance of the low-temperature wear-resistant frit and overcomes the defects in the prior art.
Another objective of the present invention is to provide a wear-resistant glaze using the low-temperature wear-resistant frit, which improves the wear resistance of the glaze by precipitating anorthite and mullite as main crystal phases in the low-temperature wear-resistant frit.
The invention also aims to provide a glazed tile using the wear-resistant glaze, wherein the wear resistance is 2100 r at 4 grades, and the wear resistance and abrasion resistance of 6000 r are 0.042-0.05 g.
In order to achieve the purpose, the invention adopts the following technical scheme:
the low-temperature wear-resistant frit comprises raw materials of wollastonite, dolomite, kaolin, alumina and a strong fluxing agent, wherein the raw materials do not contain feldspar;
according to the mass percentage, the addition amount of the dolomite is more than 8%, the addition amount of the wollastonite is more than 20%, and the addition amount of the alumina is less than 12%.
Preferably, the low-temperature wear-resistant frit comprises the following raw material components in percentage by mass: 20-30% of wollastonite, 8-12% of dolomite, 3-6% of a strong fluxing agent, 30-40% of kaolin, 10-18% of quartz, 6-12% of alumina and 3-5% of zinc oxide.
Preferably, the strong flux is a low-temperature strong flux.
Preferably, the low-temperature strong fluxing agent is any one of borax or fluorite.
Preferably, the low-temperature wear-resistant frit consists of the following raw material components in percentage by mass: 25% of wollastonite, 10% of dolomite, 3% of borax, 35% of kaolin, 18% of quartz, 6% of alumina and 3% of zinc oxide.
Preferably, the melting temperature range of the low-temperature wear-resistant frit is 950-1000 ℃.
Preferably, the decomposition temperature of the dolomite is 900-1000 ℃.
The wear-resistant glaze material using the low-temperature wear-resistant frit comprises the following raw material components in percentage by mass: 10-15% of carbonate, 30-35% of calcined talc, 25-30% of low-temperature wear-resistant frit, 3-5% of calcined zinc oxide, 8-12% of kaolin and 13-17% of calcined kaolin, and the wear-resistant glaze does not contain feldspar.
Preferably, the carbonate is any one of dolomite or calcite.
The glazed tile using the wear-resistant glaze material has the wear resistance of 4 grades of 2100 turns and the wear resistance of 6000 turns of 0.042-0.05 g.
The invention has the beneficial effects that:
the low-temperature wear-resistant frit provided by the technical scheme avoids introducing feldspar in the formula, and is favorable for improving the wear resistance of the low-temperature wear-resistant frit so as to overcome the defects in the prior art. Further, the wear-resistant glaze using the low-temperature wear-resistant frit is provided, and the wear resistance of the glaze is improved by separating anorthite and mullite which are main crystal phases from the low-temperature wear-resistant frit. In addition, the glazed tile using the wear-resistant glaze material is provided, wherein the wear resistance is 2100 r at grade 4, and the wear resistance and abrasion resistance of 6000 r are 0.042-0.05 g.
Detailed Description
The low-temperature wear-resistant frit comprises raw materials of wollastonite, dolomite, kaolin, alumina and a strong fluxing agent, wherein the raw materials do not contain feldspar;
according to the mass percentage, the addition amount of the dolomite is more than 8%, the addition amount of the wollastonite is more than 20%, and the addition amount of the alumina is less than 12%.
The technical scheme is that the low-temperature wear-resistant frit comprises raw materials of wollastonite, dolomite, kaolin, alumina and a strong fluxing agent.
In order to improve the wear resistance of the glaze with the low-temperature wear-resistant frit, the technical scheme of the invention improves the wear resistance of the glaze by separating anorthite and mullite which are main crystal phases in the glaze layer. Specifically, the low-temperature wear-resistant frit avoids introducing feldspar, and the addition amounts of dolomite and wollastonite are increased in the formula, so that the addition amount of the dolomite is more than 8%, and the addition amount of the wollastonite is more than 20%. The dolomite and the wollastonite not only exist in a liquid phase in the firing process, but also can provide CaO required by anorthite for crystallization in the firing process of the glaze, so that the glass phase of a glaze layer is reduced and the crystallization amount is increased after the glaze is fired and cooled, and the improvement of the wear resistance of the glaze with the low-temperature wear-resistant frit is facilitated. Compared with the prior art, the formula of the low-temperature wear-resistant frit in the technical scheme also reduces the introduction of alumina raw materials and increases the addition of kaolin, the addition amount of the alumina is less than 12%, and the kaolin and the alumina can provide silicon and aluminum elements required by mullite for mullite crystallization, so that the increase of the mullite crystallization content in a glaze layer is facilitated, and the wear resistance of a glaze with the low-temperature wear-resistant frit can be further improved.
Further, the strong flux and the weak flux are distinguished in that the ability to melt other substances in the glaze is strong or weak and the ability to reduce the high-temperature viscosity of the glaze is large or small, the strong flux has the ability to melt other substances in the glaze and the ability to reduce the high-temperature viscosity of the glaze is large, the weak flux has the ability to melt other substances in the glaze and the ability to reduce the high-temperature viscosity of the glaze is small. The introduction of the strong fluxing agent in the technical scheme is beneficial to reducing the melt viscosity of the low-temperature wear-resistant frit during melting, thereby being beneficial to the precipitation of crystals in the glaze and effectively ensuring the improvement of the wear resistance of the glaze layer.
In the low-temperature wear-resistant frit adopting the technical scheme, anorthite and mullite are separated out from a glaze layer by using the combination of wollastonite, dolomite, kaolin and alumina as main crystal phases to improve the wear resistance of the glaze, so that the glaze has high wear resistance controllability and good glaze effect. Meanwhile, anorthite and mullite are precipitated from the glaze layer to improve the wear resistance of the glaze, so the addition of feldspar is avoided in the formula of the low-temperature wear-resistant frit in the technical scheme, and Na is introduced into the glaze by potassium and albite2O and K2O, and Na2O and K2Compared with anorthite and mullite crystals, the introduction of O is impurity, and can inhibit the crystallization of anorthite and mullite, so that the wear resistance of the glaze surface is easily reduced.
Further, the low-temperature wear-resistant frit comprises the following raw material components in percentage by mass: 20-30% of wollastonite, 8-12% of dolomite, 3-6% of a strong fluxing agent, 30-40% of kaolin, 10-18% of quartz, 6-12% of alumina and 3-5% of zinc oxide.
8-12% of dolomite and 20-30% of wollastonite in the formula of the low-temperature wear-resistant frit are both providers of calcium elements in an anorthite crystal structure, and when the addition amount of the raw materials is too low, the providers of the calcium elements for separating anorthite crystals out of a glaze layer are insufficient; when the addition amount of the raw materials is too high, the performance of the fired glaze of the glaze with the low-temperature wear-resistant frit is easily deteriorated, and the glaze is easily whitened.
30-40% kaolin and 6-12% alumina in the formula of the low-temperature wear-resistant frit are providers of silicon and aluminum elements in cordierite crystals, anorthite crystals and mullite crystal structures, when the addition amounts of the kaolin and the alumina are too low, the silicon and aluminum elements in the glaze are insufficient, the cordierite crystals are not easy to separate out, and when the addition amounts of the kaolin and the alumina are too high, the melt viscosity of the low-temperature wear-resistant frit after melting is easy to cause to be too large, so that the separation of the crystals is not facilitated.
A small amount of strong fluxing agent is introduced into the formula, so that the reduction of the melt viscosity is facilitated, and the precipitation of crystals is facilitated. If the addition amount of the strong fluxing agent is less than 3 percent, the viscosity of the melt is not obviously reduced, and the crystal is not easy to precipitate; if the addition amount of the strong fluxing agent is higher than 6%, the increase of the glass phase after the glaze is cooled is easily caused, and the improvement of the wear resistance is not facilitated.
In a further aspect, the strong flux is a low temperature strong flux.
Low temperature fluxes are distinguished from high temperature fluxes in that the temperature at which the flux itself melts or liquefies is high or low, low temperature fluxes in that the temperature at which the flux itself melts or liquefies is low, and high temperature fluxes in that the temperature at which the flux itself melts or liquefies is high. The self-melting or liquefying temperature of the low-temperature fluxing agent is lower than 1150 ℃, the self-melting or liquefying temperature of the high-temperature fluxing agent is higher than 1150 ℃, and a small amount of low-temperature fluxing agent is introduced into the formula, so that the sintering temperature of the whole formula is favorably reduced, the viscosity of a fused mass of the low-temperature wear-resistant frit after melting is reduced, and the precipitation of crystals is favorably realized.
Furthermore, the low-temperature fluxing agent in the technical scheme is a low-temperature strong fluxing agent, so that the viscosity of the melt melted by the low-temperature wear-resistant frit can be reduced, the precipitation of crystals in the glaze is facilitated, and the improvement of the wear resistance of the glaze layer can be effectively ensured.
Further, the low-temperature strong fluxing agent is any one of borax or fluorite.
The common low-temperature strong fluxing agent comprises borax, fluorite, red lead, sodium carbonate and the like, the low-temperature strong fluxing agent in the technical scheme is preferably borax or fluorite, and B can be introduced into the formula by adding borax2O3Addition of fluorite can introduce CaF into the formula2Because the introduction of feldspar is avoided in the technical scheme, B2O3Or CaF2As the most effective strong fluxing agent, the introduction of the strong fluxing agent is beneficial to make up for the lack of Na or only little Na in the formula due to the lack of feldspar2O、K2The viscosity of the low-temperature wear-resistant frit melt is reduced under the influence of low-temperature fluxing agents such as O, so that crystals in the glaze can be precipitated, and the wear resistance of the glaze layer can be effectively improved.
Further, the low-temperature wear-resistant frit consists of the following raw material components in percentage by mass: 25% of wollastonite, 10% of dolomite, 3% of borax, 35% of kaolin, 18% of quartz, 6% of alumina and 3% of zinc oxide.
The technical scheme also provides the optimal addition proportion of the raw material components in the low-temperature wear-resistant frit, and the glazed tile prepared from the low-temperature wear-resistant frit with the addition proportion has the wear resistance of 4-level 2100 turns and has less wear resistance and wear resistance of 6000 turns.
Furthermore, the melting temperature range of the low-temperature wear-resistant frit is 950-1000 ℃.
Furthermore, the decomposition temperature of the dolomite is 900-1000 ℃.
The wear-resistant glaze material using the low-temperature wear-resistant frit comprises the following raw material components in percentage by mass: 10-15% of carbonate, 30-35% of calcined talc, 25-30% of low-temperature wear-resistant frit, 3-5% of calcined zinc oxide, 8-12% of kaolin and 13-17% of calcined kaolin, and the wear-resistant glaze does not contain feldspar.
At present, the other main influence of improving the wear resistance of the glaze is that the glaze cannot play a role in improving the wear resistance by adding the wear-resistant media such as corundum and the like into the glaze, and when the addition amount of corundum is large, the glaze defects such as rough glaze, whitening, chromatic aberration, large pores and the like are easy to occur, so that the antifouling performance of the glaze is also poor. However, when corundum is added into glaze, glaze is easy to opal, or the addition amount is very limited because the temperature of the glaze is increased by a substance with high refractoriness, so that the wear resistance of the glaze is difficult to control.
In order to improve the wear resistance of the wear-resistant glaze, the technical scheme of the invention ensures that anorthite, cordierite and mullite are separated out from the glaze layer as main crystal phases to improve the wear resistance of the glaze by adjusting the formula of the wear-resistant glaze. Specifically, the raw materials of the wear-resistant glaze provided by the technical scheme comprise carbonate, calcined talc, low-temperature wear-resistant frit, calcined zinc oxide, kaolin and calcined kaolin.
The use of carbonate in the technical scheme is beneficial to fully exhausting the low-temperature wear-resistant frit in the melting process, effectively avoids no closed air bubbles in the frit, and can prevent the fired glaze layer from having no defects such as pinholes and the like caused by the exhausting problem.
30-35% of burning talc in the formula of the wear-resistant glaze is a provider of magnesium element in a cordierite crystal structure, the content of burning talc is lower than 30% and can lead to insufficient content of MgO in the glaze, the wear-resistant performance of the glaze can not be well improved, and when the burning talc is higher than 35%, the glaze performance of the glaze with low-temperature wear-resistant frit after burning is easy to cause deterioration, the glaze is whitish and the transparency is poor.
The content of the low-temperature wear-resistant frit needs to be kept at 25-30%, sufficient raw materials can be provided for the anorthite, cordierite and mullite crystals separated out from the glaze layer by the low-temperature wear-resistant frit, if the content of the low-temperature wear-resistant frit is lower than 25%, the raw materials for the anorthite, cordierite and mullite crystals separated out from the glaze layer in the glaze are insufficient, the wear resistance of the glaze cannot be well improved, and if the content of the low-temperature wear-resistant frit is higher than 30%, the glaze defects of whitish glaze, poor transparency, poor color development and the like easily occur.
The kaolin is easy to disperse in water and difficult to precipitate, has better suspension property and viscosity, and the calcined kaolin is sintered in a kaolin calcining furnace to a certain temperature and time so as not to have the kaolin suspension property and viscosity. The kaolin of 8-12% is introduced into the formula, so that the suspension property and viscosity of the glaze slip can be guaranteed, and when the kaolin is less than 8%, the glaze slip has too high fluidity and is easy to precipitate, so that the glazing defect is easily caused. When the kaolin is higher than 12%, the viscosity of the glaze slip is too high, the fluidity is poor, air bubbles in the glaze slip cannot be discharged, and the glazing defect is easily caused. The kaolin and the calcined kaolin are introduced into the formula to be compounded together, so that the glaze slip performance of the glaze can be ensured. Further, the main component of kaolin and calcined kaolin is SiO2·AL2O3The kaolin is a main raw material for forming mullite crystals in the firing process, so that the introduction of kaolin and calcined kaolin into the formula is beneficial to the improvement of the wear resistance.
In the wear-resistant glaze material of the technical scheme, anorthite, cordierite and mullite are separated out from a glaze layer by utilizing the combination of calcined talc, low-temperature wear-resistant frit, kaolin and calcined kaolinThe abrasion resistance of the glaze is improved by the main crystal phase, and the abrasion resistance of the glaze is improved by abrasion-resistant media such as corundum in the prior art, so that the glaze has high abrasion resistance controllability and good glaze effect. Meanwhile, anorthite, cordierite and mullite are separated out from the glaze layer to improve the wear resistance of the glaze, so the feldspar is not added into the formula of the wear-resistant glaze material in the technical scheme, and the introduction of the feldspar is avoided, because the potassium and the albite can introduce Na into the glaze material2O and K2O, and Na2O and K2Compared with anorthite, cordierite and mullite crystals, the introduction of O is an impurity, and can inhibit the crystallization of anorthite, cordierite and mullite, so that the wear resistance of the glaze surface is easily reduced.
More specifically, the carbonate is any one of dolomite or calcite.
In the prior art, barium carbonate is generally adopted as carbonate in the wear-resistant formula, but in the technical scheme, the carbonate component in the glaze is increased by adding dolomite or calcite into the raw materials. This is because if barium carbonate is added into the formula, BaO will be introduced into the glaze, and the introduction of BaO will be impurities compared with anorthite, cordierite and mullite, which will inhibit the crystallization of anorthite, cordierite and mullite, and will also easily result in the decrease of the wear resistance of the glaze.
Further, as the calcite and the dolomite both exist in liquid phase in the firing process, the calcite and the dolomite can provide CaO required by anorthite for crystallization in the glaze firing process, thereby being beneficial to improving the wear resistance of the fired glaze layer.
The glazed tile using the wear-resistant glaze material is characterized in that: the wear resistance of the glazed tile is 2100 revolutions at 4 grades, and the wear resistance and the abrasion resistance of the glazed tile at 6000 revolutions are 0.042-0.05 g.
The low-temperature wear-resistant frit has a melting temperature of 950-1000 ℃ and the firing temperature of 1170-1180 ℃ of a conventional glazed tile, so that the low-temperature wear-resistant frit is more suitable for soft and bright glazed tiles with glaze gloss of 16-45 ℃.
The technical solution of the present invention is further explained by the following embodiments.
Example group 1-a method of making a glazed tile, comprising the steps of:
preparing low-temperature wear-resistant frit:
A. preparing fusion cake powder from the raw materials in the formula amount shown in the following table 1 in percentage by weight, preserving heat at the melting temperature of 1520 ℃ for 30min, discharging, and cooling by water to prepare fusion cakes;
B. the prepared clinker is powdered and sieved.
Preparing glazed tiles:
(1) adding the wear-resistant glaze raw material into a ball mill for ball milling to obtain a wear-resistant glaze; the wear-resistant glaze comprises the following raw material components in percentage by mass: 15% of dolomite, 30% of calcined talc, 27% of low-temperature wear-resistant frit, 3% of calcined zinc oxide, 10% of kaolin and 15% of calcined kaolin;
(2) applying the ground glaze cloth on a conventional ceramic tile green body; wherein, the ground coat can be prepared by the conventional formulation of the raw materials of the ground coat of the glazed tile;
(3) applying wear-resistant glaze cloth on the ceramic tile green body obtained in the step (2);
(4) drying and firing the ceramic tile green body obtained in the step (3) to form a glazed tile; wherein, the ceramic tile green body is sintered by a ceramic roller kiln under the conditions that the temperature is 1180 ℃ and the sintering time is 40 min.
The low-temperature wear-resistant frits of different raw material formulas in the above table 1 were respectively used to prepare glazed tiles, and the following performance tests were performed on the obtained glazed tiles:
1. abrasion resistance detection
GB/T3810.7-2016, part 7 of the ceramic tile testing method: the method for testing the wear resistance of the glazed surface of the glazed tile tests the wear resistance of the glazed surface of the product, and the wear resistance of the ceramic tile is evaluated by placing a grinding medium on the glazed surface and rotating the glazed surface and observing and comparing a worn sample with an unworn sample.
2. Measurement of 6000-turn abrasion resistance and wear resistance
Drying the sample plate to be tested in a drying oven at 110 ℃ to constant weight for recording the weight, placing a grinding medium on the glaze surface and rotating for 6000 turns, drying the sample plate to be tested in the drying oven at 110 ℃ to constant weight for recording the weight, calculating the weight difference before and after detection, and evaluating the wear resistance of the ceramic tile through abrasion.
The results are shown in table 2 below:
as can be seen from the results of the performance test of the example group 1, the glazed tile prepared by the above examples has good wear resistance, the wear resistance of the glazed tile reaches 2100 revolutions at level 4, and the wear resistance and abrasion of the glazed tile at 6000 revolutions is only 0.042-0.05 g.
Comparative example set 1-a process for producing a glazed tile
According to the same raw material formula and preparation method conditions in examples 1-6, only the mixture ratio of the low-temperature wear-resistant frit raw materials in the glazed tile is changed, as shown in table 3 below:
the low-temperature wear-resistant frits with different raw material formulas in table 3 are respectively used for preparing glazed tiles, and the obtained glazed tiles are subjected to wear resistance detection and 6000-turn wear resistance and abrasion measurement, and the results are shown in table 4 below:
as can be seen from the performance test results of the comparative example group 1, the raw material proportion of the low-temperature wear-resistant frit is controlled within the addition amount range of the technical scheme, so that the prepared glazed tile can obtain the optimal wear resistance, and the wear resistance and abrasion loss of 6000 revolutions can be effectively reduced.
Comparative example set 2-a process for producing a glazed tile
According to the same raw material formula and preparation method conditions in examples 1-6, only the kind of low-temperature strong fluxing agent in the low-temperature wear-resistant frit raw material is changed, as shown in the following comparative examples:
comparative example group 2-1: the low-temperature strong fluxing agent is fluorite;
comparative example groups 2-2: the low-temperature strong fluxing agent is red lead;
comparative example groups 2 to 3: the low-temperature strong fluxing agent is soda ash;
the glazed tile is prepared by the preparation method of the embodiment 1, and the obtained glazed tile is subjected to abrasion resistance detection and 6000-turn abrasion resistance and abrasion resistance measurement, and the results are shown in the following table 5:
as can be seen from the performance test results of the comparative example group 2, the introduction of feldspar in the technical scheme is avoided, so that the influence of lack of or only a very small amount of low-temperature fluxing agent due to the lack of feldspar in the formula can be compensated, the viscosity of the low-temperature wear-resistant frit melt can be reduced, the precipitation of crystals in the glaze can be facilitated, and the improvement of the wear resistance of the glaze layer can be effectively ensured.
Example group 2-a method of making a glazed tile, comprising the steps of:
preparing low-temperature wear-resistant frit:
A. preparing clinker powder from low-temperature wear-resistant clinker raw materials, preserving the heat at the melting temperature of 1520 ℃ for 30min, discharging the material, and cooling the material by water to prepare clinker; the low-temperature wear-resistant frit comprises the following raw material components in percentage by mass: 25% of wollastonite, 10% of dolomite, 3% of borax, 35% of kaolin, 18% of quartz, 6% of alumina and 3% of zinc oxide;
B. the prepared clinker is powdered and sieved.
Preparing glazed tiles:
(1) adding the wear-resistant glaze raw materials with the formula amount shown in the following table 6 into a ball mill for ball milling according to the mass percentage to obtain the wear-resistant glaze;
(2) applying the ground glaze cloth on a conventional ceramic tile green body; wherein, the ground coat can be prepared by the conventional formulation of the raw materials of the ground coat of the glazed tile;
(3) applying wear-resistant glaze cloth on the ceramic tile green body obtained in the step (2);
(4) drying and firing the ceramic tile green body obtained in the step (3) to form a glazed tile; wherein, the ceramic tile green body is sintered by a ceramic roller kiln under the conditions that the temperature is 1180 ℃ and the sintering time is 40 min.
The glazed tile is prepared by respectively adopting the low-temperature wear-resistant frits with different raw material formulas in the table 6, and the obtained glazed tile is subjected to the following wear resistance detection and 6000-turn wear resistance abrasion measurement, and the results are shown in the following table 7:
as can be seen from the results of the performance tests of example set 2, in Table 7, the glazed tile prepared by the above examples has good wear resistance, the wear resistance reaches 2100 rpm at level 4, and the wear resistance and abrasion at 6000 rpm are less than 0.05 g.
Comparative example group 3-a method for producing a glazed tile
According to the same preparation method in example group 2, the ratio of the raw materials of the abrasion-resistant glaze in the glazed tile is changed, as shown in the following table 8:
the glazed tile is prepared by respectively adopting the low-temperature wear-resistant frits with different raw material formulas in the table 8, and the obtained glazed tile is subjected to the following wear resistance detection and 6000-turn wear resistance abrasion measurement, and the results are shown in the following table 9:
as can be seen from the performance test results of comparative example group 3, although the degree of wear resistance of the glazed tile prepared by using the amount of the wear-resistant glaze in the formula according to the present technical scheme is the same as the degree of wear resistance of the glazed tile in which the amount of the wear-resistant glaze is not in the formula, 6000-turn wear resistance and wear resistance of the glazed tile prepared by using the amount of the wear-resistant glaze in the formula according to the present technical scheme are lower than 6000-turn wear resistance and wear resistance of the glazed tile in which the amount of the wear-resistant glaze is not in the formula.
Comparative example 4-a method for preparing a glazed tile, comprising the steps of:
preparing wear-resistant frit:
a. preparing clinker powder from the wear-resistant clinker raw material, preserving the heat at the melting temperature of 1520 ℃ for 30min, discharging the material and cooling the material by water to prepare clinker; the wear-resistant frit comprises the following raw material components in percentage by mass: 12% of albite, 20% of potassium feldspar, 7% of calcite, 4% of dolomite, 4% of wollastonite, 6% of zinc oxide, 9% of barium carbonate, 16% of kaolin, 10% of alumina and 12% of quartz;
b. the prepared clinker is powdered and sieved.
Preparing glazed tiles:
(1) adding the wear-resistant glaze raw material into a ball mill for ball milling to obtain a wear-resistant glaze; the wear-resistant glaze comprises the following raw material components in percentage by mass: 15% of dolomite, 30% of calcined talc, 27% of low-temperature wear-resistant frit, 3% of calcined zinc oxide, 10% of kaolin and 15% of calcined kaolin;
(2) applying the ground glaze cloth on a conventional ceramic tile green body; wherein, the ground coat can be prepared by the conventional formulation of the raw materials of the ground coat of the glazed tile;
(3) applying wear-resistant glaze cloth on the ceramic tile green body obtained in the step (2);
(4) drying and firing the ceramic tile green body obtained in the step (3) to form a glazed tile; wherein, the ceramic tile green body is sintered by a ceramic roller kiln under the conditions that the temperature is 1180 ℃ and the sintering time is 40 min.
The glazed tile is prepared according to the preparation method by adopting the wear-resistant frit of the conventional raw material formula in the prior art and the wear-resistant glaze material in the technical scheme, and the obtained glazed tile is subjected to wear resistance detection and 6000-turn wear resistance and abrasion measurement, so that the glazed tile prepared in comparative example 4 has the wear resistance of 4-grade 2100 turns and the 6000-turn wear resistance and abrasion resistance of 0.054 g. Therefore, although the wear resistance of the glazed tile prepared by using the low-temperature wear-resistant frit of the technical scheme is the same as that of the glazed tile prepared by using the conventional frit, the 6000-turn wear resistance of the glazed tile prepared by using the low-temperature wear-resistant frit of the technical scheme is less than that of the glazed tile prepared by using the conventional frit.
Comparative example 5-a method for preparing a glazed tile, comprising the steps of:
preparing low-temperature wear-resistant frit:
a. preparing clinker powder from low-temperature wear-resistant clinker raw materials, preserving the heat at the melting temperature of 1520 ℃ for 30min, discharging the material, and cooling the material by water to prepare clinker; the low-temperature wear-resistant frit comprises the following raw material components in percentage by mass: 25% of wollastonite, 10% of dolomite, 3% of borax, 35% of kaolin, 18% of quartz, 6% of alumina and 3% of zinc oxide;
b. the prepared clinker is powdered and sieved.
Preparing glazed tiles:
(1) adding the protective glaze raw material into a ball mill for ball milling to obtain a protective glaze; the protective glaze comprises the following raw material components in percentage by mass: 5% of albite, 20% of potassium feldspar, 5% of calcite, 13% of low-temperature wear-resistant frit, 78% of wollastonite, 12% of calcined talc, 3% of zinc oxide, 13% of barium carbonate, 8% of kaolin, 5% of calcined soil, 5% of corundum and 4% of quartz;
(2) applying the ground glaze cloth on a conventional ceramic tile green body; wherein, the ground coat can be prepared by the conventional formulation of the raw materials of the ground coat of the glazed tile;
(3) applying protective glaze cloth on the ceramic tile blank in the step (2);
(4) drying and firing the ceramic tile green body obtained in the step (3) to form a glazed tile; wherein, the ceramic tile green body is sintered by a ceramic roller kiln under the conditions that the temperature is 1180 ℃ and the sintering time is 40 min.
By adopting the low-temperature wear-resistant frit and the protective glaze material prepared from the conventional raw material formula in the prior art, the glazed tile is prepared according to the preparation method, and the obtained glazed tile is subjected to wear resistance detection and 6000-turn wear resistance and abrasion measurement, wherein the glazed tile prepared in comparative example 5 has the wear resistance of grade 4 and the wear resistance and abrasion of 6000-turn is 0.052 g. Therefore, although the wear resistance of the glazed tile prepared by using the wear-resistant glaze material of the technical scheme is the same as that of the glazed tile prepared by using the conventional protective glaze material, the wear resistance of the glazed tile prepared by using the wear-resistant glaze material of the technical scheme at 6000 revolutions is less than that of the glazed tile prepared by using the conventional protective glaze material at 6000 revolutions.
Comparative example 6-a method for preparing a glazed tile, comprising the steps of:
preparing a frit:
a. preparing clinker powder from the clinker raw material, preserving the temperature for 30min at the melting temperature of 1520 ℃, discharging the material and cooling the material by water to prepare the clinker; the frit comprises the following raw material components in percentage by mass: 12% of albite, 20% of potassium feldspar, 7% of calcite, 4% of dolomite, 4% of wollastonite, 6% of zinc oxide, 9% of barium carbonate, 16% of kaolin, 10% of alumina and 12% of quartz;
b. the prepared clinker is powdered and sieved.
Preparing glazed tiles:
(1) adding the protective glaze raw material into a ball mill for ball milling to obtain a protective glaze; the protective glaze comprises the following raw material components in percentage by mass: 5% of albite, 20% of potassium feldspar, 5% of calcite, 13% of frit, 78% of wollastonite, 12% of calcined talc, 3% of zinc oxide, 13% of barium carbonate, 8% of kaolin, 5% of calcined soil, 5% of corundum and 4% of quartz;
(2) applying the ground glaze cloth on a conventional ceramic tile green body; wherein, the ground coat can be prepared by the conventional formulation of the raw materials of the ground coat of the glazed tile;
(3) applying protective glaze cloth on the ceramic tile blank in the step (2);
(4) drying and firing the ceramic tile green body obtained in the step (3) to form a glazed tile; wherein, the ceramic tile green body is sintered by a ceramic roller kiln under the conditions that the temperature is 1180 ℃ and the sintering time is 40 min.
The glazed tile is prepared by adopting the frit and the protective glaze of the conventional raw material formula in the prior art according to the preparation method, and the obtained glazed tile is subjected to wear resistance detection and 6000-turn wear resistance and wear resistance measurement, so that the glazed tile prepared in comparative example 6 has the wear resistance of 3-grade 750 turns and the wear resistance and wear resistance of 6000-turn is 0.114 g. Therefore, the wear resistance of the glazed tile prepared by the prior art is lower than that of the glazed tile prepared by the technical scheme, and the 6000-turn wear resistance of the glazed tile prepared by the technical scheme is much lower than that of the glazed tile prepared by the prior art.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (6)
1. A low-temperature wear-resistant frit is characterized in that: the low-temperature wear-resistant frit comprises wollastonite, dolomite, kaolin, alumina and a strong fluxing agent, and feldspar is not contained in the raw materials;
the low-temperature wear-resistant frit consists of the following raw material components in percentage by mass: 25% of wollastonite, 10% of dolomite, 3% of borax, 35% of kaolin, 18% of quartz, 6% of alumina and 3% of zinc oxide.
2. The low temperature wear resistant frit of claim 1, wherein: the melting temperature range of the low-temperature wear-resistant frit is 950-1000 ℃.
3. The low temperature wear resistant frit of claim 1, wherein: the decomposition temperature of the dolomite is 900-1000 ℃.
4. The low-temperature wear-resistant frit according to any one of claims 1 to 3, wherein the wear-resistant frit comprises the following raw materials in percentage by mass: 10-15% of carbonate, 30-35% of calcined talc, 25-30% of low-temperature wear-resistant frit, 3-5% of calcined zinc oxide, 8-12% of kaolin and 13-17% of calcined kaolin, and the wear-resistant glaze does not contain feldspar.
5. The abrasion-resistant glaze according to claim 4, wherein: the carbonate is any one of dolomite or calcite.
6. A glazed tile using the wear-resistant glaze material as claimed in any one of claims 4 to 5, wherein: the wear resistance of the glazed tile is 2100 revolutions at 4 grades, and the wear resistance and the abrasion resistance of the glazed tile at 6000 revolutions are 0.042-0.05 g.
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| CN111732340B (en) * | 2020-08-11 | 2021-03-02 | 佛山市东鹏陶瓷发展有限公司 | Wear-resistant glaze for glazed brick and preparation method thereof |
| CN111925235A (en) * | 2020-09-28 | 2020-11-13 | 佛山市东鹏陶瓷发展有限公司 | Angle-dependent different-color underglaze color ceramic tile and preparation process thereof |
| CN111925121A (en) * | 2020-09-28 | 2020-11-13 | 佛山市东鹏陶瓷发展有限公司 | Ultralow-temperature frit without fusing pearlescent pigment, preparation method thereof and ceramic glaze |
| CN115159850B (en) * | 2022-08-26 | 2023-08-08 | 佛山市东鹏陶瓷有限公司 | Low-cost wear-resistant glazed brick glaze and preparation method thereof, and glazed brick |
| CN115385575B (en) * | 2022-08-26 | 2023-08-29 | 佛山市东鹏陶瓷有限公司 | Super wear-resistant glazed brick glaze and preparation method thereof, glazed brick and preparation method thereof |
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