CN113372002B - Zirconium white frit, white ground glaze, and preparation method and application thereof - Google Patents
Zirconium white frit, white ground glaze, and preparation method and application thereof Download PDFInfo
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- CN113372002B CN113372002B CN202110634294.3A CN202110634294A CN113372002B CN 113372002 B CN113372002 B CN 113372002B CN 202110634294 A CN202110634294 A CN 202110634294A CN 113372002 B CN113372002 B CN 113372002B
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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
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
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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
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- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
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Abstract
Disclosure of the inventionA zirconium white frit, a white ground glaze, and preparation methods and applications thereof are provided, which relate to the technical field of building materials. The zirconium white frit comprises the following components in percentage by weight: 12 to 20 percent of zircon sand, 1 to 4 percent of calcined alumina, 15 to 25 percent of quartz, 25 to 32 percent of potassium feldspar, 1 to 6 percent of calcite, 8 to 15 percent of dolomite, 1 to 7 percent of apatite, 10 to 15 percent of calcined zinc oxide and 3 to 10 percent of tin oxide; the zirconium white frit comprises the following chemical components in percentage by weight: siO 2 2 41～45％、SnO 2 4～6％、Al 2 O 3 5～7％、Fe 2 O 3 0.01～0.05％、TiO 2 0.01～0.05％、CaO 5.5～8％、MgO 2.5～4％、K 2 O 2～4％、Na 2 O 0.5～1.5％、ZnO 9～14％、P 2 O 5 1～2％、ZrO 2 9-12% and IL 6-9%. The whiteness of the zirconium white frit prepared by the formula can reach 85 degrees, and the white ground coat prepared by the formula also has good flatness and whiteness.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a zirconium white frit, a white ground glaze, and a preparation method and application thereof.
Background
For producing the ceramic tile with white background color, the whiter the ground glaze is, the higher the product grade is, for example, high-grade marble ceramic tiles such as kara white, snow white and the like need the whiteness of the background color to be more than 80. Zirconium silicate is added into glaze as an opacifier, so that the whiteness of the glaze can be obviously improved, but the expansion coefficient of zirconium silicate is small, the glaze surface is easy to be uneven, the addition amount of zirconium silicate in the ground glaze of most marble ceramic tiles is 15-20%, the whiteness is generally about 65 degrees, the use amount of zirconium silicate is continuously increased, the increase of the whiteness is not obvious, the flatness of the ceramic tiles cannot reach the standard, and the cost is increased; improvements are needed for performance effectiveness or economic efficiency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a zirconium white frit and a white ground glaze with higher whiteness and lower cost, and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a zirconium white frit comprises the following components in percentage by weight: 12 to 20 percent of zircon sand, 1 to 4 percent of calcined alumina, 15 to 25 percent of quartz, 25 to 32 percent of potassium feldspar, 1 to 6 percent of calcite, 8 to 15 percent of dolomite, 1 to 7 percent of apatite, 10 to 15 percent of calcined zinc oxide and 3 to 10 percent of tin oxide;
the zirconium white frit comprises the following chemical components in percentage by weight: siO 2 2 41～45％、SnO 2 4～6％、Al 2 O 3 5～7％、Fe 2 O 3 0.01～0.05％、TiO 2 0.01～0.05％、CaO 5.5～8％、MgO 2.5～4％、K 2 O 2～4％、Na 2 O 0.5～1.5％、ZnO 9～14％、P 2 O 5 1～2％、ZrO 2 9 to 12 percent and IL 6 to 9 percent.
The zircon sand selected by the invention can improve the whiteness of the clinker, the opalescence of the clinker can be increased by introducing the apatite and the tin oxide, in addition, the viscosity of the aggregate is reduced by solvent materials of potassium feldspar, calcite and dolomite, the chemical activity of zinc oxide is improved, and the zinc oxide reacts with magnesium oxide and aluminum oxide to synthesize magnesium-zinc-aluminum spinel, and the materials can cooperate to increase the whiteness of the zircon white clinker and achieve the aim of normal discharging.
Preferably, the zirconium white frit comprises the following components in percentage by weight: 13 to 18 percent of zircon sand, 1 to 4 percent of calcined alumina, 19 to 22 percent of quartz, 28 to 32 percent of potassium feldspar, 1 to 5 percent of calcite, 8 to 12 percent of dolomite, 1 to 7 percent of apatite, 10 to 13 percent of calcined zinc oxide and 3 to 6 percent of tin oxide.
Further preferably, the zirconium white frit comprises the following components in percentage by weight: 13 to 16 percent of zircon sand, 1 to 3 percent of calcined alumina, 19 to 22 percent of quartz, 28 to 32 percent of potash feldspar, 1 to 5 percent of calcite, 8 to 12 percent of dolomite, 3 to 6 percent of apatite, 11 to 13 percent of calcined zinc oxide and 3 to 6 percent of tin oxide.
The content of each component has great influence on the whiteness of the prepared zirconium white clinker, and when the content of each component meets the proportion, the whiteness of the prepared zirconium white clinker can reach more than 80 degrees.
In addition, the invention also discloses a preparation method of the zirconium white frit, which comprises the following steps: uniformly mixing the raw materials, and calcining under the calcining conditions: heating from room temperature to 270-330 ℃ at the speed of 3-5 ℃/min, heating to 1000-1200 ℃ at the speed of 8-10 ℃/min, heating to 1500-1600 ℃ at the speed of 5-8 ℃/min, cooling to 1350-1450 ℃ at the speed of 10-15 ℃/min, preserving heat for 20-40 min, cooling with water, drying, crushing and screening the cooled fusion cake to obtain the zirconium white fusion cake.
Meanwhile, the invention also discloses a white ground glaze which comprises the zirconium white frit.
Preferably, the white base coat further comprises calcined kaolin, wollastonite, and nepheline.
Preferably, the white ground coat comprises the following components in percentage by weight: 30-40% of zirconium white frit, 18-25% of calcined kaolin, 2-10% of wollastonite and 35-42% of nepheline; the white ground coat comprises the following chemical components in percentage by weight: siO 2 2 48～53％、SnO 2 1～2％、Al 2 O 3 19～23％、Fe 2 O 3 0.01～0.05％、TiO 2 0.01～0.05％、CaO 4～6％、MgO 1～2％、K 2 O 2～4％、Na 2 O 3～6％、ZnO 3～6％、P 2 O 5 0.3～0.8％、ZrO 2 3-5% and IL 3-6%.
Further preferably, the white ground coat comprises the following components in percentage by weight: 30-40% of zirconium white frit, 18-25% of calcined kaolin, 2-8% of wollastonite and 38-42% of nepheline. The applicant of the invention proves through a plurality of experiments that when the content of each component meets the proportion, the whiteness of the prepared white ground coat is higher than 75 degrees.
Meanwhile, the invention also discloses a preparation method of the white ground glaze, which comprises the following steps: uniformly mixing zirconium white frit, calcined kaolin, wollastonite, nepheline, water and stamp-pad ink, ball-milling for 3-6 h to obtain glaze slip, screen-printing the glaze slip on the ceramic tile ground glaze, and drying to obtain white ground glaze.
Preferably, the weight ratio of the water to the stamp-pad ink is 1.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the zircon sand, the calcined alumina, the quartz, the potash feldspar, the calcite, the dolomite, the apatite, the calcined zinc oxide and the tin oxide are selected for compounding, so that the prepared zircon white frit has higher whiteness, and meanwhile, compared with the method of singly using the zircon sand, the cost is greatly saved. In addition, the prepared zirconium white frit is compounded with the calcined kaolin, the wollastonite and the nepheline, so that the prepared white ground glaze has good flatness, and meanwhile, the whiteness of the ground glaze can reach more than 70 degrees. The white glaze can play a role in whitening the ground glaze by printing the surface of the common ground glaze for 2 times through a screen printing process, is simple to operate, low in use cost and suitable for industrial application.
Drawings
FIG. 1 is a graph showing the temperature profile of the fired zirconium white frits of examples 1 to 8.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
Examples 1 to 8
The formulations of the examples of zirconium white frits of the present invention, examples 1 to 8, are shown in table 1, and the preparation methods are as follows: uniformly mixing zircon sand, calcined alumina, quartz, potash feldspar, calcite, dolomite, apatite, calcined zinc oxide and tin oxide according to a proportion, and then calcining, wherein the calcining condition is shown as figure 1, firstly raising the temperature to 300 ℃ within 90min, then raising the temperature to 1100 ℃ within 90min, then raising the temperature to 1530 ℃ within 60min, then rapidly reducing the temperature (10 min) to 1400 ℃, preserving the temperature for 30min, then cooling by water, drying, crushing and screening the cooled clinker, thus obtaining the zircon white clinker.
Comparative examples 1 to 4
Comparative examples 1 to 4 are zirconium white frits, the formulations of which are shown in table 1, and the preparation method is the same as in examples 1 to 8.
TABLE 1 (% by weight)
The chemical composition of the zirconium white frit prepared in example 1 was tested and the results were as follows:
the zirconium white frit comprises the following components in percentage by weight: siO 2 2 43.58％、SnO 2 4.95％、Al 2 O 3 6.44％、Fe 2 O 3 0.02％、TiO 2 0.01％、CaO 6.52％、MgO 3.12％、K 2 O 2.89％、Na 2 O 0.88％、ZnO 11.89％、P 2 O 5 1.2％、ZrO 2 10.26% and IL 7.65%.
Whiteness in examples 1-8 and comparative examples 1-4 was measured using a whiteness meter according to the national standard GB/T5950-2008 method for measuring whiteness of building materials and nonmetallic mineral products, and the test procedure was as follows:
1. grinding the frit powder into glaze slip by ball milling;
2. pouring common ground coat on the green brick;
3. printing zirconium white glaze twice on the ground glaze by using an 80-mesh silk screen;
4. and (5) after drying and firing, measuring the white glaze layer of the ceramic tile by using a whiteness instrument.
The test results are shown in table 2.
TABLE 2
As can be seen from table 2, the whiteness of examples 1 to 8 is higher than that of comparative examples 1 to 4, which indicates that the whiteness of the zirconium white frit is significantly improved by selecting the components and the content of the zirconium white frit.
Examples 9 to 16
The formula of the white ground coat of the embodiment of the invention is shown in the table 3, and the preparation method comprises the following steps: the white ground glaze is obtained by mixing the zirconium white frit described in example 1 with calcined kaolin, wollastonite, nepheline, water and stamp-pad ink, ball-milling for 10min, screen-printing for 2 times on a common ground glaze with a screen of 80 meshes, and drying. Wherein, the mass ratio of the water to the stamp-pad ink is 1, and the total weight of the water and the stamp-pad ink is the same as the total weight of the zirconium white clinker, the calcined kaolin, the wollastonite and the nepheline.
Comparative examples 5 to 8
Comparative examples 5 to 8 are white basecoats whose formulations are shown in Table 3, and the preparation method and whiteness test method are the same as in examples 9 to 16.
TABLE 3 (% by weight)
The chemical composition of the white base coat described in example 9 was tested, and the test results are as follows:
the white ground coat comprises the following chemical components in percentage by weight:
SiO 2 50.86％、SnO 2 1.73％、Al 2 O 3 21.58％、Fe 2 O 3 0.012％、TiO 2 0.01％、CaO 5.19％、MgO 1.19％、K 2 O 2.9％、Na 2 O 4.49％、ZnO 4.16％、P 2 O 5 0.42％、ZrO 2 3.59% and IL 3.67%.
Whiteness and flatness were measured for examples 9 to 16 and comparative examples 5 to 8. Glazed tile roughness refers to glazed tile's surface flatness, and glazed tile's surface flatness includes two aspects, specifically refers to glazed tile's central crookedness and glazed tile's limit curvature. The central curvature of the glazed tile means a central curvature with respect to a diagonal line calculated from a working dimension, and the side curvature of the glazed tile means a side curvature with respect to the working dimension. In the embodiment of the present invention, the flatness refers specifically to the central curvature of the glazed tile, +, which represents convex deformation, among the values of the central curvature of the glazed tile, +, which represents concave deformation. According to GB/T3810.2-2016 ceramic tile test method part 2: testing the flatness of the ceramic tile according to the test on the size and the surface quality; the test results are shown in table 4.
TABLE 4
From the test results, the comprehensive performance of the whiteness and the flatness of the examples 9 to 16 is obviously higher than that of the comparative examples 5 to 8, which shows that the prepared white ground coat can give consideration to the whiteness and the flatness and has good comprehensive performance by selecting the components and the content of the white ground coat.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (7)
1. The white ground coat is characterized by comprising the following components in percentage by weight: 30-40% of zirconium white frit, 18-25% of calcined kaolin, 2-10% of wollastonite and 35-42% of nepheline;
the white ground coat comprises the following chemical components in percentage by weight: siO 2 2 48～53％、SnO 2 1～2％、Al 2 O 3 19～23％、Fe 2 O 3 0.01～0.05％、TiO 2 0.01～0.05％、CaO4～6％、MgO 1～2％、K 2 O 2～4％、Na 2 O 3～6％、ZnO3～6％、P 2 O 5 0.3～0.8％、ZrO 2 3-5% and IL 3-6%;
the zirconium white frit comprises the following components in percentage by weight: 12 to 20 percent of zircon sand, 1 to 4 percent of calcined alumina, 15 to 25 percent of quartz, 25 to 32 percent of potash feldspar, 1 to 6 percent of calcite, 8 to 15 percent of dolomite, 1 to 7 percent of apatite, 10 to 15 percent of calcined zinc oxide and 3 to 10 percent of tin oxide;
the zirconium white frit comprises the following chemical components in percentage by weight: siO 2 2 41～45％、SnO 2 4～6％、Al 2 O 3 5～7％、Fe 2 O 3 0.01～0.05％、TiO 2 0.01～0.05％、CaO 5.5～8％、MgO2.5～4％、K 2 O 2～4％、Na 2 O 0.5～1.5％、ZnO 9～14％、P 2 O 5 1～2％、ZrO 2 9 to 12 percent and IL 6 to 9 percent.
2. The white ground glaze according to claim 1, wherein the zirconium white frit comprises the following components in percentage by weight: 13 to 18 percent of zircon sand, 1 to 4 percent of calcined alumina, 19 to 22 percent of quartz, 28 to 32 percent of potassium feldspar, 1 to 5 percent of calcite, 8 to 12 percent of dolomite, 1 to 7 percent of apatite, 10 to 13 percent of calcined zinc oxide and 3 to 6 percent of tin oxide.
3. The white ground glaze according to claim 2, wherein the zirconium white frit comprises the following components in percentage by weight: 13 to 16 percent of zircon sand, 1 to 3 percent of calcined alumina, 19 to 22 percent of quartz, 28 to 32 percent of potash feldspar, 1 to 5 percent of calcite, 8 to 12 percent of dolomite, 3 to 6 percent of apatite, 11 to 13 percent of calcined zinc oxide and 3 to 6 percent of tin oxide.
4. The white ground glaze according to claim 1, wherein the zirconium white frit is prepared by a method comprising: uniformly mixing the raw materials, and calcining under the calcining conditions: heating from room temperature to 270-330 ℃ at the speed of 3-5 ℃/min, heating to 1000-1200 ℃ at the speed of 8-10 ℃/min, heating to 1500-1600 ℃ at the speed of 5-8 ℃/min, cooling to 1350-1450 ℃ at the speed of 10-15 ℃/min, preserving heat for 20-40 min, cooling by water, drying, crushing and screening the cooled frit to obtain the zirconium white frit.
5. The white ground glaze according to claim 1, characterized by comprising the following components in percentage by weight: 30-40% of zirconium white frit, 18-25% of calcined kaolin, 2-8% of wollastonite and 38-42% of nepheline.
6. A method for preparing the white ground coat according to any one of claims 1 to 5, characterized in that the method comprises: uniformly mixing zirconium white frits, calcined kaolin, wollastonite, nepheline, water and printing ink, carrying out ball milling for 3-6 h to obtain glaze slip, carrying out screen printing on the glaze slip to the ceramic tile ground glaze, and drying to obtain white ground glaze.
7. The method of claim 6, wherein the weight ratio of the water and the stamp-pad ink is 1.
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| CN114477767A (en) * | 2022-04-06 | 2022-05-13 | 佛山市东鹏陶瓷发展有限公司 | Glaze with humidity adjusting function and preparation method of ceramic tile using glaze |
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| CN111333328B (en) * | 2020-05-21 | 2020-09-29 | 佛山市东鹏陶瓷发展有限公司 | High-wear-resistance glaze material with polished glaze and preparation method thereof |
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Effective date of registration: 20230516 Address after: 511825 Shengping Industrial Park, Feilaixia Town, Qingcheng District, Qingyuan City, Guangdong Province Patentee after: QINGYUAN JIANYI CERAMICS Co.,Ltd. Patentee after: Guangdong Jianyi (Group) Ceramics Co.,Ltd. Patentee after: Guangxi Jianyi Ceramics Co.,Ltd. Address before: 511825 Shengping Industrial Park, Feilaixia Town, Qingcheng District, Qingyuan City, Guangdong Province Patentee before: QINGYUAN JIANYI CERAMICS Co.,Ltd. |