CN111533455A - Wear-resistant antifouling glazed brick glaze and preparation method thereof - Google Patents
Wear-resistant antifouling glazed brick glaze and preparation method thereof Download PDFInfo
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- CN111533455A CN111533455A CN202010648870.5A CN202010648870A CN111533455A CN 111533455 A CN111533455 A CN 111533455A CN 202010648870 A CN202010648870 A CN 202010648870A CN 111533455 A CN111533455 A CN 111533455A
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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
- C03C8/02—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
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
Abstract
The invention discloses a wear-resistant antifouling glazed brick glaze and a preparation method thereof, wherein the wear-resistant antifouling glazed brick glaze comprises raw glaze powder, No. 1 clinker powder and No. 2 clinker powder; the raw glaze powder comprises the following raw materials in percentage by weight: 8-12% of kaolin, 10-18% of calcined kaolin, 12-20% of quartz, 12-20% of dolomite, 8-15% of calcined talc, 1-5% of wollastonite, 8-15% of nepheline, 5-10% of zinc oxide, 0-5% of calcite and 6-12% of strontium carbonate; the raw materials of the No. 1 clinker powder comprise kaolin, calcined talc and fluorite, and the raw materials of the No. 2 clinker powder comprise zinc oxide, strontium carbonate and borax. The wear-resistant antifouling polished glaze brick glaze material contains a large number of cordierite microcrystals, and the cordierite microcrystals have the characteristics of transparency, high hardness and the like, can enhance the wear resistance and the antiskid effect of a glaze layer, and can solve the contradiction between the transparency and the wear resistance of the glaze layer.
Description
Technical Field
The invention relates to the technical field of architectural ceramics, in particular to a wear-resistant antifouling glaze-polished tile glaze and a preparation method thereof.
Background
The glazed brick prepared from the glaze with low wear resistance is easy to grind, the product with poor wear resistance has long service time, the reduction of glossiness is obvious, the surface is dull, and the appearance is seriously affected. At present, it has become a consensus in the industry to improve the wear resistance of the glaze by increasing the hardness of the glaze, and the prior art mainly increases the hardness and mechanical wear resistance of the glaze by increasing the crosslinking degree of the glaze layer glass structure.
For example, by introducing superfine corundum micropowder into glaze, the content of alumina in the glaze is increased, the hardness of the glaze is increased, and the wear resistance of the glaze is improved to a certain extent. However, in practical applications, it has been found that alumina, although increasing the hardness of the glaze, also reduces the transparency of the glaze, and that the incorporation of corundum crystals in excess in the glaze increases the overall porosity, resulting in a reduction in the antifouling properties of the glaze.
In addition, the content of the magnesium oxide in the glaze is increased, so that the magnesium oxide generates a crystal phase due to the fluxing action, and the wear resistance of the glaze is enhanced. However, the magnesium oxide component will reduce the refractive index of the glass phase, reducing the transparency of the glaze.
Disclosure of Invention
The invention aims to provide a wear-resistant antifouling glazed brick glaze and a preparation method thereof, and aims to solve the problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a wear-resistant antifouling glazed brick glaze, which comprises raw glaze powder, No. 1 fusion cake powder and No. 2 fusion cake powder;
the raw glaze powder comprises the following raw materials in percentage by weight: 8-12% of kaolin, 10-18% of calcined kaolin, 12-20% of quartz, 12-20% of dolomite, 8-15% of calcined talc, 1-5% of wollastonite, 8-15% of nepheline, 5-10% of zinc oxide, 0-5% of calcite and 6-12% of strontium carbonate;
the raw materials of the No. 1 clinker powder comprise kaolin, calcined talc and fluorite, and the raw materials of the No. 2 clinker powder comprise zinc oxide, strontium carbonate and borax.
In the wear-resistant antifouling glazed brick glaze, the No. 1 clinker powder is calculated according to the weight percentage of the total raw materials of the No. 1 clinker powder, wherein the addition amount of kaolin is 60-68%, the addition amount of burning talc is 20-26%, and the addition amount of fluorite is 2-6%;
the No. 2 clinker powder is calculated according to the weight percentage of the total raw materials of the No. 2 clinker powder, wherein the addition amount of zinc oxide is 3-8%, the addition amount of strontium carbonate is 6-12%, and the addition amount of borax is 1-3%.
In the wear-resistant antifouling glazed brick glaze, the sunlight direct transmittance of the No. 2 fusion cake powder is 22.5-24%, the Mohs hardness is 4 grade, and the firing temperature range is 1150-1260 ℃.
In the wear-resistant antifouling glazed brick glaze, the No. 1 fusion block powder comprises the following raw materials in percentage by weight: 60-68% of kaolin, 20-26% of calcined talc, 1-5% of quartz, 2-6% of fluorite and 1-3% of borax;
the No. 2 clinker powder comprises the following raw materials in percentage by weight: 32-38% of kaolin, 2-8% of calcined alumina, 15-20% of quartz, 10-15% of calcined talc, 2-8% of wollastonite, 3-8% of zinc oxide, 2-8% of calcite, 6-12% of strontium carbonate and 1-3% of borax.
In the wear-resistant antifouling glazed brick glaze, the weight ratio of the raw glaze powder to the No. 1 fusion block powder to the No. 2 fusion block powder is (5-6): (1-2) and (2-4).
The invention also provides a preparation method of the wear-resistant antifouling glaze-polished brick glaze, which comprises the following steps:
preparing No. 1 fusion cake powder: mixing the raw materials of the No. 1 fusion cake powder according to the proportion and preparing the mixture into powder; firing the raw materials at high temperature, discharging, cooling with water to obtain No. 1 clinker powder, powdering, sieving and drying the prepared No. 1 clinker powder, and taking 100-mesh screen underflow for later use;
preparing No. 2 fusion cake powder: mixing the raw materials of the No. 2 clinker powder according to the proportion and preparing the mixture into powder; firing the raw materials at high temperature, discharging, cooling with water to obtain No. 2 clinker powder, pulverizing the prepared No. 2 clinker powder, sieving, drying, and taking 100-mesh screen underflow for later use;
preparing raw glaze powder: uniformly mixing the raw glaze powder raw materials according to the proportion;
mixing the fusion cake powder with the raw glaze powder: and (3) adding water into the No. 1 fusion cake powder, the No. 2 fusion cake powder and the raw glaze powder prepared in the steps according to the proportion, ball-milling for 8-10 h to obtain glaze slurry, controlling the fineness to be 325 meshes, and ageing for more than 48h to obtain the wear-resistant antifouling glazed brick glaze.
In the preparation method of the wear-resistant antifouling glazed brick glaze, the high-temperature firing temperature curves in the steps of preparing the No. 1 clinker powder and preparing the No. 2 clinker powder are the same.
In the preparation method of the wear-resistant antifouling glazed brick glaze, the temperature curve of the high-temperature firing comprises the following steps:
(1) heating to 300 deg.C from normal temperature, and taking 90 min;
(2) heating from 300 deg.C to 1100 deg.C, and taking 90 min;
(3) heating from 1100 deg.C to 1520 deg.C, and taking 60 min;
(4) preserving the temperature at 1520 ℃ for 30 min;
(5) reducing the temperature from 1520 ℃ to 900 ℃ and consuming 90 min.
Has the advantages that:
(1) no. 1 fused mass powder containing a large amount of cordierite microcrystals is added into a formula system, and the cordierite microcrystals have the characteristics of transparency, high hardness and the like. Therefore, the number 1 clinker powder is mixed with the raw glaze powder, so that the number of cordierite microcrystals in the glaze layer can be increased, and the wear resistance and the anti-skid effect of the glaze layer are enhanced.
(2) No. 2 clinker powder is also added into the formula system, and the No. 2 clinker powder has the characteristics of high sunlight direct transmittance and low glaze firing temperature range, the firing temperature range of the wear-resistant antifouling glazed brick glaze can be adjusted in the formula system, the firing temperature range of the wear-resistant antifouling glazed brick glaze can be controlled by controlling the proportion of the No. 2 clinker powder in the wear-resistant antifouling glazed brick glaze, so that the quantity and size of separated cordierite crystals can be adjusted, and the contradiction between the transparency and wear resistance of a glaze layer can be solved.
(3) The wear-resistant antifouling glazed brick glaze has high matching degree between the expansion coefficient and the blank, the hardness of the glazed brick prepared from the glaze is improved, the Mohs hardness can reach 5 grade, the wear resistance is improved, the wear resistance can reach 4 grade (6000 revolutions), and the condition that the surface of the ceramic tile is scratched is effectively reduced. Since the No. 1 and No. 2 clinker powders need to be fired in the preparation process, crystal water, gas oxides and volatile substances in the raw materials of the No. 1 and No. 2 clinker powders volatilize and leave in the firing process; therefore, when the abrasion-resistant antifouling glazed tile glaze is melted and vitrified, the No. 1 clinker powder and the No. 2 clinker powder are compact glass bodies, pores on the glaze surface are few after cooling, pollutants are difficult to accumulate on the glaze surface, the antifouling performance is improved, and the antifouling grade of the glazed tile prepared from the glaze can reach 5 grades.
Drawings
The drawings are further illustrative of the invention and the content of the drawings does not constitute any limitation of the invention.
FIG. 1 is a microscopic view of the present invention in which example 13, example 17, example 18 and comparative example are shown.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
The invention provides a wear-resistant antifouling glazed brick glaze, which comprises raw glaze powder, No. 1 fusion cake powder and No. 2 fusion cake powder;
the raw glaze powder comprises the following raw materials in percentage by weight: 8-12% of kaolin, 10-18% of calcined kaolin, 12-20% of quartz, 12-20% of dolomite, 8-15% of calcined talc, 1-5% of wollastonite, 8-15% of nepheline, 5-10% of zinc oxide, 0-5% of calcite and 6-12% of strontium carbonate;
the raw materials of the No. 1 clinker powder comprise kaolin, calcined talc and fluorite, and the raw materials of the No. 2 clinker powder comprise zinc oxide, strontium carbonate and borax.
Kaolin, calcined kaolin and calcined talc in the raw glaze powder are all used as providers of silicon, aluminum and magnesium elements in a cordierite crystal structure; in addition, kaolin and calcined kaolin are also compounded with wollastonite to provide silicon, aluminum and calcium elements; moreover, dolomite also provides the elements magnesium and calcium. Fully melting the mixture into Si-Al-Mg-Ca molten glass under the high temperature condition, and fully crystallizing cordierite microcrystal and anorthite microcrystal.
In the firing process, the surface of the glaze layer is crystallized on the basis of the glass body, and cordierite microcrystals and anorthite microcrystals are separated out, and the cordierite crystals have the characteristics of transparency, high hardness and the like and simultaneously have good mechanical properties. Therefore, the cordierite crystal can enhance the hardness of the glaze, avoid the glaze from being rubbed by hard objects, obviously increase the wear resistance of the glaze, and the glaze layer has high transparency and good color development.
Because the surface of the crystal has a certain shape, the transparent crystal forms micron-scale or nano-scale protrusions on the surface of the glaze layer, so that the surface appearance of the glaze layer is changed, the friction coefficient of the glaze surface can be increased, and the anti-skid property of the glaze surface is enhanced. Because the size of the bulge is small, dirt is not easy to collect, and the glaze surface still has good easy-to-clean performance.
Because the raw glaze powder contains relatively high aluminum content, the addition of nepheline is beneficial to widening the sintering temperature range and reducing the quality defects such as deformation and the like.
The No. 1 fusion cake powder is high-temperature fusion cake powder with high hardness and high wear resistance. The raw materials of the No. 1 clinker powder comprise kaolin and calcined talc, and the kaolin and the calcined talc are fully reacted under the high-temperature condition, so that a large number of cordierite microcrystals can be crystallized, and the hardness and the wear resistance of the No. 1 clinker powder are obviously improved. The number 1 clinker powder and the raw glaze powder are mixed for use, so that the number of cordierite microcrystals in a glaze layer can be increased, the hardness of the glaze is further enhanced, and the wear resistance of the glaze is improved.
The No. 1 clinker powder also contains fluorite, and the main component of the fluorite is calcium fluoride; the fluorine element in the calcium fluoride is utilized to respectively generate SiF with silicon and aluminum elements under the high temperature condition4、AlF3(ii) a Under high temperature conditions, a small amount of SiF4And AlF3Volatilizing to increase the expansion coefficient of No. 1 clinker powder, thereby ensuring that the wear-resistant and antifouling throwing-resistant powderThe expansion coefficient of the glaze of the glazed brick is matched with that of the blank, so that the problem of serious deformation of the fired glaze due to the unmatched expansion coefficients of the glaze and the blank is solved. Meanwhile, the calcium fluoride has the function of reducing the high-temperature viscosity of the clinker, so that the No. 1 clinker powder can be completely discharged from the heating equipment, and the yield of the No. 1 clinker powder is improved.
The No. 2 clinker powder has high direct sunlight transmittance and low sintering temperature range. The raw materials of the No. 2 clinker powder comprise fluxing agents such as zinc oxide, strontium carbonate, borax and the like, wherein the zinc oxide and the strontium carbonate play roles in improving the glossiness of a glaze surface and fluxing; and the borax plays a role in reducing the viscosity of a melt and increasing the luster of the glaze. The direct sunlight transmittance of the glaze can reflect the light transmittance and the transparency. The addition of the No. 2 clinker powder can improve the transparency of the glaze, and also has the function of adjusting the firing temperature range of the glaze, and the quantity and size of cordierite crystals precipitated in a glaze layer can be adjusted by adjusting the firing temperature range of the glaze, so that the aims of enhancing the wear resistance and hardness of the glaze are fulfilled.
Specifically, the No. 1 clinker powder is calculated according to the weight percentage of the total raw materials of the No. 1 clinker powder, wherein the addition amount of the kaolin is 60-68%, the addition amount of the burning talc is 20-26%, and the addition amount of the fluorite is 2-6%; the No. 2 clinker powder is calculated according to the weight percentage of the total raw materials of the No. 2 clinker powder, wherein the addition amount of zinc oxide is 3-8%, the addition amount of strontium carbonate is 6-12%, and the addition amount of borax is 1-3%. Under the condition that the No. 1 clinker powder meets the requirement of matching with the expansion coefficient of a blank body, the weight ratio of kaolin to calcined talc is (60-68%): (20 to 26%), the amount of cordierite crystallites precipitated is the greatest at this ratio. The addition amount of fluorite is 2-6%, and in the actual operation, SiO in No. 1 clinker powder2Is about 1.51%, AL2O3The volatilization amount of (2) was 0.42%.
Specifically, the sunlight direct transmittance of the No. 2 clinker powder is 22.5-24%, the Mohs hardness is 4 grade, and the firing temperature range is 1150-1260 ℃. The direct sunlight transmission ratio of the No. 2 fusion cake powder is high, and the sintering temperature range is low, so that the wear-resistant antifouling glazed brick glaze can separate out cordierite crystals at a stable crystallization temperature, and the cordierite crystals in a glaze layer of the wear-resistant antifouling glazed brick glaze are increased.
Specifically, the No. 1 clinker powder comprises the following raw materials in percentage by weight: 60-68% of kaolin, 20-26% of calcined talc, 1-5% of quartz, 2-6% of fluorite and 1-3% of borax;
the No. 2 clinker powder comprises the following raw materials in percentage by weight: 32-38% of kaolin, 2-8% of calcined alumina, 15-20% of quartz, 10-15% of calcined talc, 2-8% of wollastonite, 3-8% of zinc oxide, 2-8% of calcite, 6-12% of strontium carbonate and 1-3% of borax.
In a preferred embodiment, the No. 1 clinker powder comprises the following raw materials in percentage by weight: 60-68% of kaolin, 20-26% of calcined talc, 1-5% of quartz, 2-6% of fluorite and 1-3% of borax; the No. 2 clinker powder comprises the following raw materials in percentage by weight: 32-38% of kaolin, 2-8% of calcined alumina, 15-20% of quartz, 10-15% of calcined talc, 2-8% of wollastonite, 3-8% of zinc oxide, 2-8% of calcite, 6-12% of strontium carbonate and 1-3% of borax. The borax can obviously reduce the sintering temperature and improve the light transmittance, but the borax can be decomposed into boron oxide and water at high temperature, and the water is changed into water vapor at high temperature, so that bubbles are generated, the probability of pores on the glaze surface is increased, pollutants are easy to accumulate on the pores, and the antifouling performance of the wear-resistant antifouling glaze-polishing brick glaze material is further reduced.
Preferably, the weight ratio of the raw glaze powder to the No. 1 fusion cake powder to the No. 2 fusion cake powder is (5-6): (1-2) and (2-4). The formula structures of the raw glaze powder, the No. 1 fusion cake powder and the No. 2 fusion cake powder are cordierite systems, wherein the raw glaze powder plays a role in adjusting the color development of the wear-resistant and antifouling glazed brick glaze and maintaining the stability of the performance of glaze slurry in the wear-resistant and antifouling glazed brick glaze. The No. 1 fusion block powder can obviously improve the hardness and the wear resistance of the wear-resistant antifouling glazed brick glaze. The No. 2 clinker powder has the characteristics of high sunlight direct transmission ratio and low firing temperature range, plays a role in adjusting the firing temperature range of the glaze, and can adjust the firing temperature range of the glaze by changing the content of the No. 2 clinker powder, so that the quantity and size of cordierite crystals precipitated in a glaze layer are adjusted, and the purposes of enhancing the wear resistance and hardness of the glaze are achieved.
The weight ratio of the raw glaze powder to the No. 1 fusion cake powder to the No. 2 fusion cake powder is (5-6): (1-2) and (2-4), the wear-resistant antifouling glazed brick glaze has better performances of hardness, wear resistance, antifouling property and the like. In the most preferred embodiment, the weight ratio of the raw glaze powder to the No. 1 frit powder to the No. 2 frit powder is 5:1: 4.
The invention also provides a preparation method of the wear-resistant antifouling glaze-polished brick glaze, which comprises the following steps:
preparing No. 1 fusion cake powder: mixing the raw materials of the No. 1 fusion cake powder according to the proportion and preparing the mixture into powder; firing the raw materials at high temperature, discharging, cooling with water to obtain No. 1 clinker powder, powdering, sieving and drying the prepared No. 1 clinker powder, and taking 100-mesh screen underflow for later use;
preparing No. 2 fusion cake powder: mixing the raw materials of the No. 2 clinker powder according to the proportion and preparing the mixture into powder; firing the raw materials at high temperature, discharging, cooling with water to obtain No. 2 clinker powder, pulverizing the prepared No. 2 clinker powder, sieving, drying, and taking 100-mesh screen underflow for later use;
preparing raw glaze powder: uniformly mixing the raw glaze powder raw materials according to the proportion;
mixing the fusion cake powder with the raw glaze powder: and (3) adding water into the No. 1 fusion cake powder, the No. 2 fusion cake powder and the raw glaze powder prepared in the steps according to the proportion, ball-milling for 8-10 h to obtain glaze slurry, controlling the fineness to be 325 meshes, and ageing for more than 48h to obtain the wear-resistant antifouling glazed brick glaze.
In the preparation method, as the No. 1 clinker powder contains borax and fluorite, bubbles are produced under the high-temperature condition in the sintering process of the No. 1 clinker powder; similarly, the No. 2 clinker powder contains borax, so that bubbles are produced under a high-temperature condition in the process of firing the No. 2 clinker powder; the method comprises the steps of firing No. 1 frit powder and No. 2 frit powder in advance, mixing the fired frit powder with raw glaze powder, discharging gas generated under a high-temperature condition when preparing No. 1 frit powder and No. 2 frit powder, reducing the probability of air holes on a glaze surface of wear-resistant and antifouling glazed brick glaze, and avoiding the problem that pollutants are accumulated on the air holes and are difficult to remove, thereby improving the antifouling capacity of the glaze surface.
Further, the temperature curves of high-temperature firing in the step of preparing the No. 1 clinker powder and the step of preparing the No. 2 clinker powder are the same. The formula structures of the No. 1 clinker powder and the No. 2 clinker powder are the same as a cordierite system, so that the temperature curves of high-temperature firing are the same.
Still further, the temperature profile of the high temperature firing includes:
(1) heating to 300 deg.C from normal temperature, and taking 90 min;
(2) heating from 300 deg.C to 1100 deg.C, and taking 90 min;
(3) heating from 1100 deg.C to 1520 deg.C, and taking 60 min;
(4) preserving the temperature at 1520 ℃ for 30 min;
(5) reducing the temperature from 1520 ℃ to 900 ℃ and consuming 90 min.
The temperature of the clinker in the firing process is from normal temperature to 1520 ℃ which takes 240 minutes, and in the process, the crystal water, gas oxide and volatile substances in the minerals are volatilized under the high-temperature condition; and then, the thermal insulation is fully carried out at 1520 ℃ so that the cordierite crystal structure is more stable, and the abrasion resistance of the frit is improved.
And (3) performance testing:
1. mohs hardness determination: and (4) stably placing the polished tile sample on a hard support with the facing upwards. The surface of a sample is scribed by selecting standard ores with different Mohs values from small to large, the surface of the sample is scribed uniformly and vertically by applying force through a new ore cutting edge, the force application needs to be moderate, and the cutting edge of the standard ore cannot be broken by excessive force application to form double-line or multi-line scribing traces. The lowest hardness value which just can generate obvious scratches is taken as the test result, and the lowest value of all the test values of the test sample is taken as the test result.
2. And (3) determining the wear resistance: 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.
3. And (3) static friction coefficient measurement: the static friction coefficient of the surface of the ceramic tile is determined by a dry method and a wet method by using a pulling slide block method in GB/T4100-2015 ceramic tile standard appendix M 'method for determining the static friction coefficient of the surface of glazed ceramic tiles and unglazed ceramic tiles'.
4. And (3) antifouling rating measurement: the pollution agent for testing the pollution resistance of the ceramic tile comprises a paste pollution agent, a pollution agent capable of generating an oxidation reaction, a pollution agent capable of generating a film, olive oil and the like, wherein the pollution resistance is classified into 1-5 grades according to the difficulty of cleaning, and the higher the grade is, the better the pollution resistance is.
5. And (3) measuring the direct sunlight transmittance: the direct sunlight transmittance of the building glass is measured by using a method for measuring the direct sunlight transmittance of GB/T2680-94.
6. Determination of the light transmittance of the glaze: distributing glaze powder on the blank powder, wherein the thickness of the glaze powder is 5mm, the thickness of the blank powder is 2mm, pressing the blank powder into blocks by a press, and after sintering in a kiln, throwing off the blank to process the blocks into sheets; and measuring the direct sunlight transmittance of the building glass by using the GB/T2680-94 measuring method to obtain the light transmittance.
Example group A
The wear-resistant antifouling raw glaze powder is prepared by the following steps:
(1) weighing raw glaze powder according to the mineral composition in the table 1 for later use;
(2) mixing 100 parts of raw glaze powder, 40 parts of water, 0.2 part of sodium carboxymethylcellulose and 0.3 part of sodium tripolyphosphate according to parts by weight, carrying out ball milling for 9 hours to obtain glaze slurry, controlling the fineness to be 325 meshes and the mass fraction of the screen residue to be 1.2%, and then ageing for 49 hours to obtain wear-resistant and antifouling raw glaze powder;
(3) replacing the overglaze in the prior production process of the glazed brick with the wear-resistant and antifouling raw glaze powder, spraying overglaze, drying, sintering in a kiln, and polishing to obtain the wear-resistant glazed brick.
The wear-resistant polished glazed tile of the example group A was subjected to the above-mentioned 1 to 4 performance tests to prepare Table 2.
In the example group a, the raw glaze powder and the chemical material were used to prepare the glaze slip, and it can be seen from table 2 that the properties of the prepared abrasion-resistant polished glazed tile are poor in mohs hardness, abrasion resistance, anti-fouling grade, static friction force and the like, wherein the test results of the raw glaze powder of the example 3 in the example group a are ideal.
Example group B
The preparation of No. 1 fusion cake powder comprises the following steps:
(1) weighing raw materials according to the mineral composition of the No. 1 clinker powder in the table 3, preparing the raw materials into powder, and performing high-temperature firing according to the following temperature curve:
a) heating to 300 deg.C from normal temperature, and taking 90 min;
b) heating from 300 deg.C to 1100 deg.C, and taking 90 min;
c) heating from 1100 deg.C to 1520 deg.C, and taking 60 min;
d) preserving the temperature at 1520 ℃ for 30 min;
e) reducing the temperature from 1520 ℃ to 900 ℃ and consuming 90 min;
after high-temperature firing, discharging and cooling by water to prepare No. 1 clinker powder, powdering, sieving and drying the prepared No. 1 clinker powder, and taking 100-mesh undersize for later use;
(2) adding water into the No. 1 clinker powder, ball-milling for 10 hours to obtain glaze slurry, controlling the fineness to be 325 meshes, and aging for 48 hours to obtain wear-resistant and antifouling glaze, wherein the mass fraction of the surplus glaze is 0.8%;
(3) replacing the overglaze in the prior production process of the glazed brick with the glaze for glaze spraying, drying, sintering in a kiln, and polishing to obtain the wear-resistant glazed brick.
The use of glaze slip prepared from fusion cake powder No. 1 has three obvious disadvantages. The method comprises the following steps: 1. the glaze color difference; 2. the light transmittance of the No. 1 fusion cake powder is low, so that the glaze has low transparency and weak transparency; 3. the glaze slip is easy to precipitate and can not be stored for a long time. Therefore, the powder of No. 1 clinker is not suitable for use alone. The wear-resistant polished tiles of example group B were subjected to the performance tests and expansion coefficient tests of 1 to 4 and 6 described above to prepare table 4.
The expansion coefficient range of No. 1 melting block powder is 225 × 10-7～235×10-7The temperature per DEG C is matched with the expansion coefficient of the blank body, and the warping degree of the ceramic tile meets the national detection standard.
As is clear from Table 4, the test results of the powder of the clinker Nos. 1 in examples 6 and 8 in example group B are more preferable in the tests of Mohs hardness, abrasion resistance, stain resistance, static friction and the like.
Example set C
The preparation of No. 2 fusion cake powder comprises the following steps:
(1) weighing the raw materials according to the mineral composition of the No. 2 clinker powder in the table 5, preparing the raw materials into powder, and performing high-temperature firing according to the following temperature curve:
a) heating to 300 deg.C from normal temperature, and taking 90 min;
b) heating from 300 deg.C to 1100 deg.C, and taking 90 min;
c) heating from 1100 deg.C to 1520 deg.C, and taking 60 min;
d) preserving the temperature at 1520 ℃ for 30 min;
e) reducing the temperature from 1520 ℃ to 900 ℃ and consuming 90 min;
after high-temperature firing, discharging and cooling by water to prepare No. 2 clinker powder, powdering, sieving and drying the prepared No. 2 clinker powder, and taking 100-mesh undersize for later use;
adding water into the No. 2 clinker powder, ball-milling for 8h to obtain glaze slurry, controlling the fineness to be 325 meshes, and keeping the screen residue to be 1.2 mass percent, and then ageing for 48h to obtain wear-resistant and antifouling raw glaze powder;
(2) mixing 100 parts of No. 2 clinker powder, 40 parts of water, 0.2 part of sodium carboxymethylcellulose and 0.3 part of sodium tripolyphosphate according to parts by weight, and performing ball milling for 9 hours to obtain a glaze material;
(3) replacing the overglaze in the prior production process of the glazed brick with the glaze for glaze spraying, drying, sintering in a kiln, and polishing to obtain the wear-resistant glazed brick.
The wear-resistant polished glazed tiles of example group C were subjected to the performance tests 1-3 and 5 described above to prepare table 6.
When the No. 2 fusion cake powder and chemical materials are mixed to prepare the glaze slurry for use, the light transmittance of the glaze layer is higher, so that the glaze material has better transparency, but poorer wear resistance and hardness. In addition, the glaze slip prepared by mixing No. 2 clinker powder and chemical materials is easy to precipitate, so that the glaze slip cannot be stored for a long time, and therefore, the No. 2 clinker powder is not suitable for being used with the chemical materials independently. As can be seen from Table 6, the results of the Mohs hardness, abrasion resistance and light transmittance tests of example 11 in example group C are more desirable.
Example set D
A wear-resistant antifouling glaze material for glazed bricks is prepared by the following steps:
(1) mixing the raw glaze powder described in example 3, the number 1 clinker powder of example 6 and the number 2 clinker powder of example 11 according to the ratio of the raw glaze powder, the number 1 clinker powder and the number 2 clinker powder in Table 7;
(2) adding water into the raw materials, ball-milling for 9h to obtain glaze slurry, controlling the fineness to be 325 meshes, and aging for 49h to obtain the wear-resistant antifouling polished glaze brick glaze, wherein the mass fraction of the surplus glaze is 1.0%;
(3) replacing the overglaze in the prior production process of the glazed brick with the wear-resistant antifouling glazed brick glaze for spraying overglaze, drying, merging into a kiln for firing, and polishing to obtain the wear-resistant glazed brick.
The wear-resistant polished tiles of example group D were subjected to the above-described performance tests 1-4 and 6 to prepare table 8.
Referring to table 8, it can be seen from comparing examples 13, 16 and 20 that, when the ratio of the number 1 frit powder is unchanged, the ratio of the raw glaze powder is increased, and the ratio of the number 2 frit powder is decreased, the hardness and wear resistance of the glaze are not significantly increased, the antifouling level and anti-slip capability are also low, and the light transmittance of the glaze is also low. Combining example 15 and example 21, it can be seen that when the ratio of the No. 2 frit powder is as low as 1, the transmittance of the glaze is reduced very significantly.
Comparing examples 13 to 15 with examples 18 and 19, it can be seen that when the ratio of the number 1 frit powder is unchanged, the ratio of the raw glaze powder is reduced, and the ratio of the number 2 frit powder is increased, the abrasion resistance of the glaze is reduced, the hardness is slightly reduced, the anti-slip capability is also reduced, but the light transmittance of the glaze is higher.
It can be seen from comparison between example 16 and example 17 that, when the raw glaze powder ratio is unchanged, the ratio of the number 1 frit powder is increased, and the ratio of the number 2 frit powder is decreased, the light transmittance of the glaze is decreased, and simultaneously, the hardness and the anti-slip capability of the glaze are improved to some extent.
From the test results of the examples 13 to 21, it can be seen that the raw glaze powder, the number 1 frit powder and the number 2 frit powder have the best hardness, wear resistance, antifouling capability and anti-skid capability when the ratio of the raw glaze powder to the number 1 frit powder to the number 2 frit powder is 5:1: 4.
Comparative test
The test data for example 13, example 17, example 18 and the control in example set D were compared to prepare the following Table 9:
wherein, the raw glaze powder in the comparative example: number 1 clinker powder: the weight ratio of No. 2 fusion cake powder is 5:4: 1; the raw glaze powder comprises the raw materials of 10% of kaolin, 15% of calcined kaolin, 12% of quartz, 20% of dolomite, 5% of wollastonite, 10% of calcined talc, 10% of nepheline, 8% of zinc oxide and 10% of strontium carbonate;
the raw materials of the No. 1 clinker powder are 15% of potassium feldspar, 20% of albite, 6% of kaolin, 8% of dolomite, 10% of calcite, 5% of calcined talc, 10% of corundum, 9% of barium carbonate, 5% of quartz, 6% of wollastonite and 6% of zinc oxide;
the raw materials of the No. 2 clinker powder are 35 percent of kaolin, 25 percent of wollastonite, 10 percent of dolomite, 18 percent of quartz, 5 percent of calcined alumina, 3 percent of borax, 1 percent of zircon sand and 3 percent of zinc oxide.
Referring to fig. 1, wherein the micrograph of example 17 is portion a of fig. 1, the micrograph of example 18 is portion b of fig. 1, the micrograph of example 13 is portion c of fig. 1, and the micrograph of the comparative example is portion d of fig. 1. The firing temperature can be controlled by adjusting the proportion of No. 2 clinker powder, thereby adjusting the generation size and quantity of cordierite. Referring to fig. 1 and table 9, when the raw glaze powder: number 1 clinker powder: when the weight ratio of the No. 2 clinker powder is 5:1:4, a large amount of cordierite crystals are generated and the volume is large.
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. Other embodiments of the invention will occur to those skilled in the art without the exercise of inventive faculty based on the explanations herein, and such equivalent modifications or substitutions are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (8)
1. The utility model provides a wear-resisting antifouling glaze material of throwing glazed brick which characterized in that: comprises raw glaze powder, No. 1 fusion cake powder and No. 2 fusion cake powder;
the raw glaze powder comprises the following raw materials in percentage by weight: 8-12% of kaolin, 10-18% of calcined kaolin, 12-20% of quartz, 12-20% of dolomite, 8-15% of calcined talc, 1-5% of wollastonite, 8-15% of nepheline, 5-10% of zinc oxide, 0-5% of calcite and 6-12% of strontium carbonate;
the raw materials of the No. 1 clinker powder comprise kaolin, calcined talc and fluorite, and the raw materials of the No. 2 clinker powder comprise zinc oxide, strontium carbonate and borax.
2. The glaze for wear-resistant antifouling glazed brick as claimed in claim 1, wherein: the No. 1 clinker powder is calculated according to the weight percentage of the total raw materials of the No. 1 clinker powder, wherein the addition amount of the kaolin is 60-68%, the addition amount of the burning talc is 20-26%, and the addition amount of the fluorite is 2-6%;
the No. 2 clinker powder is calculated according to the weight percentage of the total raw materials of the No. 2 clinker powder, wherein the addition amount of zinc oxide is 3-8%, the addition amount of strontium carbonate is 6-12%, and the addition amount of borax is 1-3%.
3. The glaze for wear-resistant antifouling glazed brick as claimed in claim 2, wherein: the No. 1 fusion cake powder comprises the following raw materials in percentage by weight: 60-68% of kaolin, 20-26% of calcined talc, 1-5% of quartz, 2-6% of fluorite and 1-3% of borax;
the No. 2 clinker powder comprises the following raw materials in percentage by weight: 32-38% of kaolin, 2-8% of calcined alumina, 15-20% of quartz, 10-15% of calcined talc, 2-8% of wollastonite, 3-8% of zinc oxide, 2-8% of calcite, 6-12% of strontium carbonate and 1-3% of borax.
4. The glaze for wear-resistant antifouling glazed brick as claimed in claim 1, wherein: the sunlight direct transmittance of the No. 2 fusion cake powder is 22.5-24%, the Mohs hardness is 4 grade, and the sintering temperature range is 1150-1260 ℃.
5. The glaze for wear-resistant antifouling glazed brick as claimed in claim 1, wherein: the weight ratio of the raw glaze powder to the No. 1 fusion cake powder to the No. 2 fusion cake powder is (5-6): (1-2) and (2-4).
6. A preparation method of wear-resistant antifouling glazed brick glaze is characterized by comprising the following steps: the method for preparing the wear-resistant antifouling glaze-polished tile glaze material as claimed in any one of claims 1 to 5, comprising the following steps:
preparing No. 1 fusion cake powder: mixing the raw materials of the No. 1 fusion cake powder according to the proportion and preparing the mixture into powder; firing the raw materials at high temperature, discharging, cooling with water to obtain No. 1 clinker powder, powdering, sieving and drying the prepared No. 1 clinker powder, and taking 100-mesh screen underflow for later use;
preparing No. 2 fusion cake powder: mixing the raw materials of the No. 2 clinker powder according to the proportion and preparing the mixture into powder; firing the raw materials at high temperature, discharging, cooling with water to obtain No. 2 clinker powder, pulverizing the prepared No. 2 clinker powder, sieving, drying, and taking 100-mesh screen underflow for later use;
preparing raw glaze powder: uniformly mixing the raw glaze powder raw materials according to the proportion;
mixing the fusion cake powder with the raw glaze powder: and (3) adding water into the No. 1 fusion cake powder, the No. 2 fusion cake powder and the raw glaze powder prepared in the steps according to the proportion, ball-milling for 8-10 h to obtain glaze slurry, controlling the fineness to be 325 meshes, and ageing for more than 48h to obtain the wear-resistant antifouling glazed brick glaze.
7. The method for preparing a wear-resistant antifouling glaze-polished tile glaze according to claim 6, wherein the method comprises the following steps: the temperature curves of high-temperature firing in the steps of preparing the No. 1 fusion cake powder and preparing the No. 2 fusion cake powder are the same.
8. The method for preparing a wear-resistant antifouling glaze-polished tile glaze according to claim 7, wherein the method comprises the following steps: the temperature profile of the high-temperature firing comprises:
(1) heating to 300 deg.C from normal temperature, and taking 90 min;
(2) heating from 300 deg.C to 1100 deg.C, and taking 90 min;
(3) heating from 1100 deg.C to 1520 deg.C, and taking 60 min;
(4) preserving the temperature at 1520 ℃ for 30 min;
(5) reducing the temperature from 1520 ℃ to 900 ℃ and consuming 90 min.
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