CN114044629A - Anti-slip antifouling glaze - Google Patents
Anti-slip antifouling glaze Download PDFInfo
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- CN114044629A CN114044629A CN202111415495.0A CN202111415495A CN114044629A CN 114044629 A CN114044629 A CN 114044629A CN 202111415495 A CN202111415495 A CN 202111415495A CN 114044629 A CN114044629 A CN 114044629A
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- parts
- glaze
- slip
- silicon nitride
- calcium fluoride
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Abstract
The invention provides an anti-slip and anti-fouling glaze, which comprises albite, quartz, calcium fluoride and silicon nitride as raw materials. The glaze material has excellent anti-slip performance and antifouling performance, good mechanical performance and no need of special improvement on production equipment and process.
Description
Technical Field
The invention belongs to the field of architectural ceramics, relates to a glaze, and particularly relates to an anti-slip antifouling glaze.
Background
At present, the ceramic market shows the characteristics of high-grade, artistic and personalized requirements, functional products and the like, and decorative materials with health and high taste become the mainstream of consumption. At present, the anti-skid function of the glazed tile is mainly realized through two aspects. On one hand, the firing temperature of the overglaze is adjusted, so that the firing temperature is increased, the formation of a glass phase is reduced, and the roughness of the surface is improved to realize the anti-skid function; on the other hand, the brick realizes the rough feeling of the brick surface through the dry grains, thereby realizing the anti-skid function. However, the surface of the anti-skid tile is easy to store dirt and scale due to low surface flatness and high roughness, and the overall antifouling performance of the anti-skid tile is poor. Therefore, the preparation of the anti-slip and anti-fouling ceramic becomes one of the research hotspots in the field.
CN111217527A discloses an anti-skid and anti-fouling glazed tile, which sequentially comprises a green body layer, a bottom glaze layer and a high-temperature particle layer from bottom to top; the ground glaze layer comprises the following raw material components in parts by weight: 20-23 parts of flint clay, 6-9 parts of mullite, 12-15 parts of power plant slag ash, 8-14 parts of white gangue, 20-30 parts of quartz sand, 10-15 parts of high-alumina bauxite, 12-15 parts of wollastonite, 10-12 parts of calcined talc, 6-8 parts of ball clay, 2-4 parts of black mud, 5-8 parts of montmorillonite, 10-15 parts of pyrophyllite, 5-8 parts of potassium feldspar, 12-15 parts of albite, 1-2 parts of borocalcite, 3-5 parts of high-boron glass powder and 5-8 parts of zirconium silicate. The bottom glaze layer is a reticular structure layer formed by the raw materials of the bottom glaze layer; the high-temperature particle layer comprises high-temperature frits and carborundum.
CN110395907A discloses dry particles for ceramic anti-slip glaze and a modified preparation method thereof, wherein the dry particles for ceramic anti-slip glaze comprise the following components in parts by weight: 97-98.5 parts of anti-skid dry particles and 1.5-3 parts of grinding modification auxiliary agents. The preparation method of the dry particles for glaze comprises the following steps: (1) preparing materials according to the proportion of chemical components to form mixed raw material powder; (2) adding the raw material powder into an intermittent ball mill, performing wet ball milling until D50 is less than or equal to 8 mu m, D97 is less than or equal to 30 mu m, and discharging slurry after the fineness is qualified; (3) pumping the slurry into a spray drying tower for drying and granulation to prepare granular powder with the grain diameter of less than 20 meshes and the moisture of less than 5 percent; (4) adding the grinding modification auxiliary agent into the powder, uniformly stirring and mixing, adding into an airflow grinding mill, and simultaneously grinding and drying; (5) controlling the total grain diameter range to be D97 not more than 45 mu m (dry method), and controlling the moisture content to be less than 0.5 percent, and finally obtaining the finished product of the dry grain for the anti-slip glaze.
Disclosure of Invention
In order to solve the technical problem, the application provides an anti-slip and anti-fouling glaze, the glaze has excellent anti-slip performance and anti-fouling performance at the same time, and has good mechanical properties, and no special improvement is needed for production equipment and process.
In order to achieve the technical effect, the invention adopts the following technical scheme:
the invention provides an anti-slip and anti-fouling glaze, which comprises feldspar, quartz, calcium fluoride and silicon nitride as raw materials.
According to the invention, calcium fluoride and silicon nitride are added into a conventional glaze formula, and as the softening point of the silicon nitride is about 1800 ℃ and higher than the firing temperature of the ceramic tile, silicon nitride particles can be uniformly distributed in a melt in the firing process, and the roughness of the surface of dry particle glaze is improved by the grain size distribution of the silicon nitride and quartz particles, so that the anti-skid property is improved.
In a preferred embodiment of the present invention, the calcium fluoride is present in an amount of 5.0 to 10.0 parts by weight, for example, 5.5 parts, 6.0 parts, 6.5 parts, 7.0 parts, 7.5 parts, 8.0 parts, 8.5 parts, 9.0 parts or 9.5 parts, but the amount is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the silicon nitride is present in an amount of 2.0 to 5.0 parts by weight, for example, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, or 4.5 parts, but the amount is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the albite is 14.0 to 16.0 parts by weight, for example, 14.2 parts, 14.5 parts, 14.8 parts, 15.0 parts, 15.2 parts, 15.5 parts, or 15.8 parts, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the quartz is present in an amount of 10.0 to 13.0 parts by weight, such as 10.5 parts, 11.0 parts, 11.5 parts, 12.0 parts, or 12.5 parts, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
As a preferred technical scheme of the present invention, the glaze comprises the following raw materials: albite, quartz, barium carbonate, calcined talc, kaolin, wollastonite, calcined clay, zinc oxide, calcium fluoride, silicon nitride, and white corundum.
According to a preferable technical scheme of the invention, the glaze comprises the following raw materials in parts by weight: 14.0 to 16.0 parts of albite, 10.0 to 13.0 parts of quartz, 10.0 to 13.0 parts of barium carbonate, 6.0 to 9.0 parts of calcined talc, 5.0 to 7.0 parts of kaolin, 30.0 to 33.0 parts of wollastonite, 2.0 to 5.0 parts of calcined clay, 6.0 to 9.0 parts of zinc oxide, 5.0 to 10.0 parts of calcium fluoride, 2.0 to 5.0 parts of silicon nitride and 1.0 to 3.0 parts of white corundum.
The amount of barium carbonate may be 10.5 parts, 11.0 parts, 11.5 parts, 12.0 parts, 12.5 parts, etc., the amount of talc may be 6.5 parts, 7.0 parts, 7.5 parts, 8.0 parts, 8.5 parts, etc., the amount of kaolin may be 5.2 parts, 5.5 parts, 5.8 parts, 6.0 parts, 6.2 parts, 6.5 parts, or 6.8 parts, etc., the amount of wollastonite may be 30.5 parts, 31.0 parts, 31.5 parts, 32.0 parts, or 32.5 parts, etc., the amount of calcined clay may be 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, or 4.5 parts, etc., the amount of zinc oxide may be 6.5 parts, 7.0 parts, 7.5 parts, 8.0 parts, or 8.5 parts, etc., the amount of corundum may be 1.2 parts, 1.5 parts, 1.0, 2.5 parts, 2, or other numerical values are not limited to these.
According to a preferable technical scheme of the invention, the glaze comprises the following raw materials in parts by weight: 14.5 to 15.5 parts of albite, 11.0 to 12.0 parts of quartz, 11.0 to 12.0 parts of barium carbonate, 7.0 to 8.0 parts of calcined talc, 5.5 to 6.5 parts of kaolin, 31.0 to 32.0 parts of wollastonite, 3.0 to 4.0 parts of calcined clay, 7.0 to 8.0 parts of zinc oxide, 6.0 to 8.0 parts of calcium fluoride, 3.0 to 4.0 parts of silicon nitride and 1.5 to 2.5 parts of white corundum.
In a preferred embodiment of the present invention, the raw material of the glaze further includes 30 to 50 parts of water, such as 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, or 48 parts, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
As a preferable technical solution of the present invention, the preparation method of the glaze includes sequentially performing a first calcination treatment, a second calcination treatment, a first cooling, and a second cooling on a raw material.
In a preferred embodiment of the present invention, the temperature of the first calcination treatment is 1100 to 1350 ℃, for example, 1150 ℃, 1200 ℃, 1250 ℃, or 1300 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the temperature of the second calcination treatment is 1400 to 1500 ℃, such as 1410 ℃, 1420 ℃, 1430 ℃, 1440 ℃, 1450 ℃, 1460 ℃, 1470 ℃, 1480 ℃ or 1490 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the first cooling is performed by standing at 1300-1350 ℃ for 5-10 min, wherein the temperature may be 1310 ℃, 1320 ℃, 1330 ℃ or 1340 ℃, and the time may be 6min, 7min, 8min or 9min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the second cooling is furnace cooling.
According to the invention, the process is optimized, the firing is divided into two steps, the first step is to carry out heat treatment on the raw materials at 1100-1350 ℃, the second step is to carry out firing at 1400-1500 ℃, and the cooling stage is also divided into two steps, wherein the raw materials are firstly kept stand at about 1300 ℃ for 5-10 min and then cooled along with the furnace. The reason is that the melting point of calcium fluoride is 1360 ℃, the raw material is firstly made into a melt at the temperature lower than the melting point of calcium fluoride, so that the calcium fluoride is uniformly distributed in the melt, the calcium fluoride is dissolved by heating, the calcium fluoride is firstly cooled and crystallized in the cooling stage, and because silicon nitride is not dissolved, part of the calcium fluoride can be attached to the silicon nitride surface in the cooling and crystallizing process, so that the silicon nitride surface is modified, the silicon nitride surface has fluorine atoms and silicon atoms, the silicon nitride particle surface has hydrophobic and oleophobic performances at the same time, and the waterproof and antifouling purposes are achieved.
Compared with the prior art, the invention has at least the following beneficial effects:
the application provides an anti-skidding and anti-fouling glaze, through the improvement to the formula to and the corresponding improvement of going on the preparation method, the two mutually supports, makes the glaze has excellent anti-skidding performance and anti-fouling performance concurrently simultaneously, and has good mechanical properties, need not special improvement to production facility and technology.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an anti-slip and anti-fouling glaze, which comprises the following raw materials in parts by weight: 14.0 parts of albite, 10.0 parts of quartz, 10.0 parts of barium carbonate, 6.0 parts of calcined talc, 5.0 parts of kaolin, 30.0 parts of wollastonite, 2.0 parts of calcined clay, 6.0 parts of zinc oxide, 5.0 parts of calcium fluoride, 2.0 parts of silicon nitride and 1.0 part of white corundum.
Example 2
The embodiment provides an anti-slip and anti-fouling glaze, which comprises the following raw materials in parts by weight: 16.0 parts of albite, 13.0 parts of quartz, 13.0 parts of barium carbonate, 9.0 parts of calcined talc, 7.0 parts of kaolin, 33.0 parts of wollastonite, 5.0 parts of calcined clay, 9.0 parts of zinc oxide, 10.0 parts of calcium fluoride, 5.0 parts of silicon nitride and 3.0 parts of white corundum.
Example 3
The embodiment provides an anti-slip and anti-fouling glaze, which comprises the following raw materials in parts by weight: 14.5 parts of albite, 11.0-parts of quartz, 11.0 parts of barium carbonate, 7.0 parts of calcined talc, 5.5 parts of kaolin, 31.0 parts of wollastonite, 3.0 parts of calcined clay, 7.0 parts of zinc oxide, 6.0 parts of calcium fluoride, 3.0 parts of silicon nitride and 1.5 parts of white corundum.
Example 4
The embodiment provides an anti-slip and anti-fouling glaze, which comprises the following raw materials in parts by weight: 15.5 parts of feldspar, 12.0 parts of quartz, 12.0 parts of barium carbonate, 8.0 parts of calcined talc, 6.5 parts of kaolin, 32.0 parts of wollastonite, 4.0 parts of calcined clay, 8.0 parts of zinc oxide, 8.0 parts of calcium fluoride, 4.0 parts of silicon nitride and 2.5 parts of corundum.
Example 5
The embodiment provides an anti-slip and anti-fouling glaze, which comprises the following raw materials in parts by weight: the glaze comprises the following raw materials in parts by weight: 14.8 parts of albite, 11.5 parts of quartz, 11.3 parts of barium carbonate, 7.5 parts of calcined talc, 5.7 parts of kaolin, 31.5 parts of wollastonite, 3.2 parts of calcined clay, 7.7 parts of zinc oxide, 7.3 parts of calcium fluoride, 3.6 parts of silicon nitride and 1.8 parts of white corundum.
Comparative example 1
This comparative example was carried out under the same conditions as in example 5 except that calcium fluoride was not added.
Comparative example 2
This comparative example was carried out under the same conditions as in example 5 except that no silicon nitride was added.
The glazes provided in examples 1 to 5 according to the invention and comparative examples 1 to 2 were prepared on green bodies for subsequent performance testing. The used green body comprises 3.0 parts of water abrasive, 20.0 parts of kaolin, 38.5 parts of water milled sand, 3.0 parts of ultrawhite ball clay, 2.5 parts of calcined talc, 15.0 parts of Gongtian sand, 9.5 parts of high-temperature sand, 1.2 parts of bentonite and 1.5 parts of peng mud. The thickness of the blank body is 5mm, and the thickness of the glaze layer is 1 mm.
The manufacturing process parameters of the blank are as follows:
a powder preparation process: mud proportion: 1.69-1.71 g/ml
Ball milling fineness: 0.8 to 1.0% (250 mesh screen)
Particle grading: 30 mesh (including 30 mesh): 5 to 20 percent
30-60 meshes (30 meshes excluded, 60 meshes inclusive): not less than 64%
60-80 meshes (60 meshes excluded, 80 meshes inclusive): less than or equal to 12 percent
Below 80 mesh (80 mesh excluded): less than or equal to 6 percent
Moisture content of powder: 7.0 to 7.5 percent
The molding process comprises the following steps: a press machine type: PH3000
Molding pressure: 360bar
And (3) pressing period: 5.4 times/min (600X 600mm specification)
And (3) a drying process: drying temperature: 140 deg.C
Drying time: 60min
Drying the green body: less than or equal to 0.5 percent.
The manufacturing process parameters of the protective glaze powder and the dry grain glaze powder are as follows:
water spraying amount on the surface of the green brick: 5 ~ 10 g/dish (tray size 200X 600mm, same below)
Dry particle glaze specific gravity: 1.55-1.58; throwing glaze weight: 16 +/-2 g/disc;
after glazing is finished, the obtained green body is fired, and the firing process can be as follows:
and (3) firing in a kiln: a roller kiln;
firing temperature: 1300 ℃ and 1400 ℃;
and (3) firing period: 50min (first temperature section 20min, second temperature section 30min)
And (3) cooling: standing at 1350 deg.C for 10min, and cooling with the furnace.
Comparative example 3
The comparative example was conducted under the same conditions as in example 5 except that the sintering was conducted at 1300 ℃ for 50 min.
Comparative example 4
The comparative example was carried out under the same conditions as in example 5 except that only one-stage sintering was carried out at 1400 ℃ for 50 min.
Comparative example 5
The comparative example was carried out under the same conditions as in example 5 except that furnace cooling was carried out directly after completion of the sintering.
The anti-bending strength of the rock plate is tested by using an SKZ anti-bending and anti-compression detector, the friction coefficient of the glaze is tested by using GB/T4100-2015, the wet slip resistance value of the glaze is tested by using GB/T35153-2017, and the antifouling grade of the glaze is tested by using GB/T3810.14-2016. The results are shown in Table 1.
TABLE 1
| Flexural strength/N/cm | Coefficient of friction | Slip resistance value | Antifouling rating | |
| Example 1 | 11.4 | 0.75 | 45 | 5 |
| Example 2 | 12.2 | 0.82 | 52 | 5 |
| Example 3 | 11.8 | 0.76 | 47 | 5 |
| Example 4 | 12.0 | 0.80 | 51 | 5 |
| Example 5 | 11.7 | 0.78 | 49 | 5 |
| Comparative example 1 | 11.7 | 0.66 | 40 | 4 |
| Comparative example 2 | 11.6 | 0.75 | 47 | 4 |
| Comparative example 3 | 11.5 | 0.76 | 48 | 4 |
| Comparative example 4 | 11.8 | 0.62 | 33 | 5 |
| Comparative example 5 | 11.7 | 0.76 | 47 | 4 |
The test results in table 1 show that the glazes provided in examples 1 to 5 of the present invention have excellent anti-slip and anti-fouling properties, a friction coefficient of 0.75 or more, a slip resistance value of greater than 45, an anti-fouling rating of 5, and excellent mechanical properties. Compared with example 5, the comparative example 1 and the comparative example 2 respectively do not add calcium fluoride and silicon nitride, which leads to overall reduction of the anti-slip and anti-fouling performance of the glaze. Comparative examples 3 to 5 were adjusted in the sintering process as compared with example 5, and the glaze produced was also reduced in performance as compared with example 5.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The anti-slip antifouling glaze is characterized in that raw materials of the glaze comprise albite, quartz, calcium fluoride and silicon nitride.
2. The glaze of claim 1 wherein the amount of calcium fluoride is 5.0 to 10.0 parts by weight.
3. The glaze of claim 1 or 2, wherein the silicon nitride is present in an amount of 2.0 to 5.0 parts by weight.
4. The non-slip and anti-fouling glaze material as claimed in any one of claims 1 to 3, wherein the albite is present in an amount of 14.0 to 16.0 parts by weight;
preferably, the weight part of the quartz is 10.0-13.0 parts.
5. The non-slip and anti-fouling glaze according to any one of claims 1 to 4, wherein the glaze comprises the following raw materials: albite, quartz, barium carbonate, calcined talc, kaolin, wollastonite, calcined clay, zinc oxide, calcium fluoride, silicon nitride, and white corundum.
6. The glaze of claim 5, wherein the glaze comprises the following raw materials in parts by weight: 14.0 to 16.0 parts of albite, 10.0 to 13.0 parts of quartz, 10.0 to 13.0 parts of barium carbonate, 6.0 to 9.0 parts of calcined talc, 5.0 to 7.0 parts of kaolin, 30.0 to 33.0 parts of wollastonite, 2.0 to 5.0 parts of calcined clay, 6.0 to 9.0 parts of zinc oxide, 5.0 to 10.0 parts of calcium fluoride, 2.0 to 5.0 parts of silicon nitride and 1.0 to 3.0 parts of white corundum.
7. The glaze of claim 5, wherein the glaze comprises the following raw materials in parts by weight: 14.5 to 15.5 parts of albite, 11.0 to 12.0 parts of quartz, 11.0 to 12.0 parts of barium carbonate, 7.0 to 8.0 parts of calcined talc, 5.5 to 6.5 parts of kaolin, 31.0 to 32.0 parts of wollastonite, 3.0 to 4.0 parts of calcined clay, 7.0 to 8.0 parts of zinc oxide, 6.0 to 8.0 parts of calcium fluoride, 3.0 to 4.0 parts of silicon nitride and 1.5 to 2.5 parts of white corundum.
8. The anti-slip and anti-fouling glaze material as claimed in any one of claims 1 to 7, wherein the glaze material further comprises 30 to 50 parts of water.
9. The glaze of any one of claims 1 to 8, wherein the glaze is prepared by subjecting a raw material to a first calcination treatment, a second calcination treatment, a first cooling and a second cooling in this order.
10. The non-slip and anti-fouling glaze material as claimed in any one of claims 1 to 9, wherein the temperature of the first calcination treatment is 1100 to 1350 ℃;
preferably, the temperature of the second calcining treatment is 1400-1500 ℃;
preferably, the first cooling is standing for 5-10 min at 1300-1350 ℃;
preferably, the second cooling is furnace cooling.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108249763A (en) * | 2018-02-05 | 2018-07-06 | 广东省陶瓷研究所 | A kind of wear-resisting antiskid ceramics and preparation method thereof |
| CN109095769A (en) * | 2018-09-13 | 2018-12-28 | 佛山市登羽科技有限公司 | A kind of unglazed glaze and the preparation method and application thereof |
| CN112521010A (en) * | 2020-12-23 | 2021-03-19 | 江西亚航科技有限公司 | Ceramic glaze with stable performance and preparation method thereof |
| CN112939463A (en) * | 2021-04-07 | 2021-06-11 | 亚细亚建筑材料股份有限公司 | Anti-slip antifouling glaze |
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2021
- 2021-11-25 CN CN202111415495.0A patent/CN114044629B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108249763A (en) * | 2018-02-05 | 2018-07-06 | 广东省陶瓷研究所 | A kind of wear-resisting antiskid ceramics and preparation method thereof |
| CN109095769A (en) * | 2018-09-13 | 2018-12-28 | 佛山市登羽科技有限公司 | A kind of unglazed glaze and the preparation method and application thereof |
| CN112521010A (en) * | 2020-12-23 | 2021-03-19 | 江西亚航科技有限公司 | Ceramic glaze with stable performance and preparation method thereof |
| CN112939463A (en) * | 2021-04-07 | 2021-06-11 | 亚细亚建筑材料股份有限公司 | Anti-slip antifouling glaze |
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