CN113955942B - High-hardness glaze and preparation method thereof - Google Patents
High-hardness glaze and preparation method thereof Download PDFInfo
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- CN113955942B CN113955942B CN202111575076.3A CN202111575076A CN113955942B CN 113955942 B CN113955942 B CN 113955942B CN 202111575076 A CN202111575076 A CN 202111575076A CN 113955942 B CN113955942 B CN 113955942B
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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
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The application relates to the technical field of glaze preparation, in particular to a high-hardness glaze and a preparation method thereof. The application provides a high-hardness glaze, wherein 1-10% of sapphire single crystal ingot is added into a known glaze according to mass percentage. The high-hardness glaze provided by the invention is applied to a glazed brick product, can greatly improve the hardness of the glazed brick, and can improve the grade and service life of the product.
Description
Technical Field
The application relates to the field of glaze preparation, in particular to a high-hardness glaze and a preparation method thereof.
Background
The fully-glazed ceramic tile is obtained by polishing a layer of transparent glaze on a decorative pattern, and along with the prevalence of ink-jet printing, the decorative pattern is more and more abundant, so that the market share of the fully-glazed ceramic tile is higher and higher.
The marble is a luxurious symbol in the fields of home furnishing and decoration, and because the marble has higher price and radioactivity and is not popularized, the marble-like ceramic tile is produced as a high-end product of full-polished glaze and is popular among consumers.
The ceramic tiles are used as semi-finished products and can be delivered to consumers only by paving. On one hand, in the process of paving and decorating the ceramic tiles, the surfaces of the ceramic tiles are inevitably scraped and collided with sand, stones and various metal objects; in ordinary life, small stones, dust and other various objects on the sole belt of the shoe can also scrape and collide with the glaze layer on the surface of the ceramic tile, and on the other hand, the ceramic tile belongs to durable goods with low attention and high consumption, and consumers do not pay attention at ordinary times but pay high attention during decoration. Therefore, the requirements of various properties of the ceramic tile are high, and particularly, the ceramic tile needs to be durable as new after being used for a long time, so that the requirement of the product on good hardness and wear resistance can be met.
Many techniques for adjusting the hardness and wear resistance of fully-polished glaze products are disclosed in the prior art, for example, publication No. CN105948503A discloses that white corundum and zirconia are used as wear-resistant agents to improve the wear resistance of glaze, and the wear-resistant transparent glaze cloth has better wear resistance when applied to the surface of a blank.
The production process of polished ceramic tile is characterized by that the whole body (general body) of the blank body is made up by adopting the mode of micropowder distribution, and after having texture decorative effect, the blank body is pressed, sintered and polished, so that the hardness can be up to 6. The glazed tile production process commonly known in the industry is to apply a transparent glaze layer after green body pressing, ink jetting/printing/roller decoration and the like, because the glazed tile has rich decoration effect and is favored by the market, but the glazed tile can not reach the level of the polished tile in the aspect of hardness all the time, so that part of consumers can give up the decoration effect and select the polished tile made of porcelain. Therefore, the development of a high-hardness glaze material can promote the grade of the glazed brick and is favored by the market.
Disclosure of Invention
The application mainly aims to provide a high-hardness glaze, and a preparation method of the high-hardness glaze, and aims to solve the problem that a glazed tile in the prior art is not high in hardness.
In order to achieve the above object, the present application provides a high-hardness glaze and a method for preparing the same.
The application provides a high-hardness glaze, wherein 1-10% of sapphire single crystal ingot is added into a known glaze according to mass percentage.
Preferably, 5-8% sapphire single crystal ingot is added to a known glaze by mass percent.
The sapphire single crystal ingot is colorless in appearance, is a crystal growing along a specific axial direction, can meet the requirement after being mechanically processed and can be sliced, and the ingot is high-purity alpha-Al2O3The total impurity content is less than 100mg/kg, the crystal structure is a hexagonal lattice structure and is formed by combining three oxygen atoms and two aluminum atoms in a covalent bond mode, 1-10% of sapphire single crystal ingot is added into a known glaze, so that the hardness of the glaze can be improved, the hardness of the glaze can be obviously improved mainly because unmelted sapphire single crystal particles are uniformly distributed on the surface of the glaze layer in the firing process, and the cost performance is highest when 5-8% of the unmelted sapphire single crystal particles are added, so that the hardness of the glaze can reach 6 grades.
Preferably, the known glaze is known transparent glaze, and the known transparent glaze comprises 60-82 parts of raw glaze powder and 18-30 parts of frit according to parts by weight.
Preferably, the raw glaze powder comprises the following raw materials in parts by weight: 2-5 parts of lithium porcelain stone, 25-35 parts of potassium feldspar, 5-15 parts of albite, 10-20 parts of quartz, 6-16 parts of kaolin, 6-12 parts of barium carbonate, 11-20 parts of dolomite and 3-8 parts of wollastonite.
Preferably, the fusion initiation temperature of the fusion cake is in the range of 1000-2O3：18-25%，BaO：8-12%。
Generally, the transparent glaze is positioned on the top of the glazed brick and is a surface directly contacted with the external environment, and the hardness of the transparent glaze directly influences the service life of the glazed brick, so that the hardness performance index of the transparent glaze is urgently required to be improved; therefore, 18-30 parts of frit is required to be added into a formula of the transparent glaze for fluxing, the firing temperature and the high-temperature viscosity are reduced, the firing range is widened, and the raw glaze material is glaze material prepared by directly mixing mineral raw materials without other processing technologies such as calcination, melting and the like; further preferably, the fusion initiation temperature of the frit is in the range of 1000-2O3: 18-25%, BaO: 8-12%, and further limiting the initial melting temperature of the frit to 1000-2O3: 18-25%, BaO: when the content is 8-12%, the fusion cake and dolomite are used as fluxing agents and high-temperature fluxing agents such as potassium feldspar and albite, and the generation and growth of mullite crystal phase are facilitated at high temperature. Meanwhile, the content of alumina in the transparent glaze is increased by introducing the sapphire single crystal into the known glaze polishing, and in order to ensure the high transparency and high gloss of the transparent glaze, the content of calcium and magnesium is adjusted by controlling a proper ratio of aluminum to silicon to obtain the transparent glaze with high transparency and high gloss.
Preferably, the zirconia is also included by 0.2-0.5% by mass percentage.
The zirconia is further added, and the inventor creatively discovers that the abrasive resistance of the glaze can be greatly improved under the synergistic effect of a small amount of zirconia and the sapphire single crystal, and the transparency of the glaze layer cannot be influenced.
The application also provides a preparation method of the high-hardness glaze, which comprises the following steps:
s1, mixing raw glaze powder;
s2, sintering the frits, and crushing the frits until the particle size is less than or equal to 200 meshes;
s3, crushing the sapphire single crystal ingot until the particle size is less than or equal to 325 meshes;
s4, mixing the materials obtained in the steps S1, S2 and S3 in proportion; wherein the sequence of steps S1, S2 and S3 can be changed arbitrarily.
Preferably, step S3 includes coarse breaking, intermediate breaking and then grinding with a sand mill or/and an air flow mill.
The raw glaze is prepared by directly mixing mineral raw materials, and other processing technologies such as calcination, melting and the like are not performed. Raw material particles are controlled within a certain range, the specific surface area of the particles can be ensured, the interface reaction is more sufficient, the sintering power is more sufficient, the glaze surface effect is better, the flatness and the antifouling performance of the glaze can be further improved, and because the hardness of the sapphire single crystal ingot is very high, the sapphire single crystal ingot is preferably subjected to rough crushing and intermediate crushing and then subjected to sand mill grinding and airflow grinding, so that the grinding effect is better.
To sum up, this application technical scheme has following beneficial effect: the invention provides a high-hardness glaze which is applied to a glazed brick product and can greatly improve the hardness of the glazed brick, the grade of the product and the service life of the product.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The application provides a preparation method of a high-hardness glaze, which comprises the following steps:
s1, mixing raw glaze powder;
the raw glaze powder in the embodiment can be a known glaze formula, can also be a preferable known transparent glaze formula, and can also be more preferable raw glaze powder obtained by mixing 2-5 parts of lithium porcelain stone, 25-35 parts of potassium feldspar, 5-15 parts of albite, 10-20 parts of quartz, 6-16 parts of kaolin, 6-12 parts of barium carbonate, 11-20 parts of dolomite and 3-8 parts of wollastonite.
S2, sintering the frits, and crushing the frits until the particle size is less than or equal to 200 meshes;
the frit formula in the embodiment can be a frit formula required by a known glaze, can also be a frit formula required by a preferred known transparent glaze, and can further preferably have an initial melting range of 1000-2O3: 18-25%, BaO: 8-12% of frit formula, the frits of the technical scheme are purchased from Shandong Zibo frit company, and the step is not needed for the known glaze which does not need to add the frits.
S3, crushing the sapphire single crystal ingot until the particle size is less than or equal to 325 meshes;
the sapphire single crystal ingot purchased in the embodiment of the technical scheme is coarsely crushed by a jaw crusher, the particle size of the sapphire single crystal ingot is controlled to be 325 meshes or below by a sand mill and/or an air flow mill after the sapphire single crystal ingot is coarsely crushed by a double-roller crusher, wherein the particle size is smaller than or equal to 325 meshes, the sieving is performed by adopting a 325-mesh sieve, and the screen residue is smaller than 0.1%.
S4, mixing the materials obtained in the steps S1, S2 and S3 in proportion; wherein the sequence of steps S1, S2 and S3 can be changed arbitrarily.
The glaze that will obtain is according to the preparation of conventional imitative marble glazed brick production technology and is obtained marble ceramic tile product, and the marble ceramic tile is prepared to the same technology that adopts same production line in all embodiments of this application, detects and the effect observation to the product, and performance detection and effect characterization method are as follows:
and (3) performance detection:
1. mohs hardness: the sample was placed smoothly on a rigid support with the facing up. 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 value that just produced a distinct scratch was used as the test result and the lowest of all the test values of the test specimen was used as the test result.
2. Wear resistance rating: GB/T3810.7-2016, part 7 of the ceramic tile testing method: the abrasion resistance of the glaze of the product is tested by the testing method in the determination of the abrasion resistance of the surface of the glazed tile, and the abrasion resistance of the ceramic tile is evaluated by placing a grinding medium on the glaze and rotating the glaze and observing and comparing a worn sample and an unworn sample.
3. Gloss: obtained by testing with a gloss measuring instrument.
4. Antifouling performance: GB/T3810.14-2016 ceramic tile test method part 14: the stain resistance of the glazed surface of the product is tested by the measuring method in the stain resistance measuring method, the thoroughly cleaned brick surface is dried to constant weight, then a staining agent is dripped on the brick surface, the results of comparing the brick surface and the action of each staining agent are graded, the 5 th grade corresponds to the most easy removal of the specified staining agent from the brick surface, and the 1 st grade corresponds to the condition that any one of the test steps can not remove the staining agent on the brick surface without damaging the brick surface.
And (3) effect characterization:
1. and (3) hardness characterization: the higher the hardness value, the better the product quality, characterized by the Mohs hardness value.
2. Wear resistance: the wear-resistant performance is better when the grade number is higher, and the wear-resistant performance is better when the revolution number is higher at the same grade.
3. Antifouling property: corresponding grade numbers are obtained through antifouling performance tests, and the higher the grade is, the better the antifouling effect is
4. And (3) decorative effect: through the permeability of naked eye observation glaze, synthesize the penetrating sense and the glossiness of glaze, can divide into 5 grades with decorative effect, the higher glaze decorative effect that is the better of rank.
5. And (3) glaze surface defects: whether surface defects such as pinholes and concave glaze exist or not is observed by naked eyes, the smoothness of the glaze surface can be divided into 5 grades, and the higher the grade is, the fewer the defects of the glaze surface are.
The formulation compositions and temperatures in the above examples are ranges of values, inclusive of the endpoints and any values within the ranges, are implementable, and some examples are described below as specific point values.
Example 1
A preparation method of high-hardness glaze comprises the following steps:
s1, mixing raw glaze powder;
the common base coat formula commonly used by the company is adopted, and specifically comprises the following components: the weight parts of the raw materials are as follows: potassium feldspar: 35 parts, nepheline: 15 parts, quartz: 20 parts of calcined alumina: 12 parts, kaolin: 8 parts, calcined talc: 3 parts of calcined kaolin: 7 parts.
S2, crushing the sapphire single crystal ingot until the particle size is less than or equal to 325 meshes;
in the embodiment, the coarse crushing is carried out by a jaw crusher, and the particle size is controlled to be less than or equal to 325 meshes by a sand mill after the intermediate crushing is carried out by a double-roller crusher.
And S3, mixing 95 parts by mass of the raw glaze powder obtained in the step S1 and 5 parts by mass of the sapphire single crystal ingot obtained in the step 2 to obtain the high-hardness glaze.
And (3) carrying out the same firing system on the marble polished tile blank to obtain a tile product, and carrying out Mohs hardness test on the tile product.
Example 2
A preparation method of high-hardness glaze comprises the following steps:
s1, mixing raw glaze powder;
the common known common transparent glaze polishing formula commonly used by the company is adopted, and specifically comprises the following steps: according to the mass parts, the potassium feldspar: 40 parts, quartz: 12 parts, kaolin: 6 parts of wollastonite: 5 parts, calcined zinc: 5 parts, barium carbonate: 8 parts of dolomite: 10 parts, talc: 3.5 parts of calcined alumina: and 2 parts.
S2, crushing the sapphire single crystal ingot until the particle size is less than or equal to 325 meshes;
in the embodiment, the coarse crushing is carried out by a jaw crusher, and the particle size is controlled to be less than or equal to 325 meshes by a sand mill after the intermediate crushing is carried out by a double-roller crusher.
And S3, mixing 95 parts by mass of the raw glaze powder obtained in the step S1 and 5 parts by mass of the sapphire single crystal ingot obtained in the step 2 to obtain the high-hardness glaze.
And preparing the obtained glaze according to the same conventional marble-imitated glazed brick production process to obtain a marble tile product, and detecting and observing the product and the effect.
Example 3
A preparation method of high-hardness glaze comprises the following steps:
s1, mixing raw glaze powder;
the common known common transparent glaze polishing formula commonly used by the company is adopted, and specifically comprises the following steps: according to the mass parts, the potassium feldspar: 40 parts, quartz: 12 parts, kaolin: 6 parts of wollastonite: 5 parts, calcined zinc: 5 parts, barium carbonate: 8 parts of dolomite: 10 parts, talc: 3.5 parts of calcined alumina: 2 parts of flux block: 10.5 parts.
S2, sintering the frits, and crushing the frits until the particle size is less than or equal to 200 meshes;
in this example, a clinker with a particle size of not more than 200 meshes from Shandong Zibo clinker company is purchased, and the initial melting temperature is: 1150 ℃.
S3, crushing the sapphire single crystal ingot until the particle size is less than or equal to 325 meshes;
in the embodiment, the coarse crushing is carried out by a jaw crusher, and the particle size is controlled to be less than or equal to 325 meshes by a sand mill after the intermediate crushing is carried out by a double-roller crusher.
S4, mixing 71 parts by mass of the raw glaze powder obtained in the step S1 and 24 parts by mass of the frit obtained in the step 2; and 5 parts of sapphire single crystal ingot obtained in the step 3 are mixed to obtain the high-hardness glaze.
And preparing the obtained glaze according to the same conventional marble-imitated glazed brick production process to obtain a marble tile product, and detecting and observing the product and the effect.
Example 4
S1, mixing raw glaze powder;
the raw glaze powder is prepared by mixing the following raw materials in parts by weight: 5 parts of lithium porcelain stone, 30 parts of potassium feldspar, 15 parts of albite, 10 parts of quartz, 6 parts of kaolin, 10 parts of barium carbonate, 16 parts of dolomite and 8 parts of wollastonite.
S2, sintering the frits, and crushing the frits until the particle size is less than or equal to 200 meshes;
in this example, a clinker with a particle size of not more than 200 meshes from Shandong Zibo clinker company is purchased, and the initial melting temperature is: detecting the chemical composition of the material at 1000 ℃, wherein the chemical composition comprises SiO in percentage by mass2：49.2%，Al2O3：18%，Fe2O3+TiO2：0.6%，CaO：12%，MgO：1.6%，K2O+Na2O：6.6%，BaO：12%。
S3, crushing the sapphire single crystal ingot until the particle size is less than or equal to 325 meshes;
in the embodiment, the coarse crushing is carried out by a jaw crusher, and the particle size is controlled to be less than or equal to 325 meshes by an airflow mill after the intermediate crushing is carried out by a double-roller crusher.
S4, counting by mass, 81 parts of the raw glaze powder obtained in the step S1 and 18 parts of the frit obtained in the step 2; and mixing with 1 part of the sapphire single crystal ingot obtained in the step 3 to obtain the high-hardness glaze.
And preparing the obtained glaze according to the same conventional marble-imitated glazed brick production process to obtain a marble tile product, and detecting and observing the product and the effect.
Example 5
S1, mixing raw glaze powder;
the raw glaze powder is prepared by mixing the following raw materials in parts by weight: 2 parts of lithium porcelain stone, 25 parts of potassium feldspar, 8 parts of albite, 20 parts of quartz, 10 parts of kaolin, 12 parts of barium carbonate, 20 parts of dolomite and 3 parts of wollastonite.
S2, sintering the frits, and crushing the frits until the particle size is less than or equal to 200 meshes;
in this example, a clinker with a particle size of not more than 200 meshes from Shandong Zibo clinker company is purchased, and the initial melting temperature is: 1050 ℃, and the chemical composition of the alloy comprises Al according to mass percent2O3：20%，BaO：12%。
S3, crushing the sapphire single crystal ingot until the particle size is less than or equal to 325 meshes;
in the embodiment, the coarse crushing is carried out by a jaw crusher, and the particle size is controlled to be less than or equal to 325 meshes by an airflow mill after the intermediate crushing is carried out by a double-roller crusher.
S4, mixing 62.8 parts by mass of the raw glaze powder obtained in the step S1 and 27 parts by mass of the frit obtained in the step 2; and (3) mixing 10 parts of the sapphire single crystal ingot and 0.2 part of zirconia powder to obtain the high-hardness glaze.
And preparing the obtained glaze according to the same conventional marble-imitated glazed brick production process to obtain a marble tile product, and detecting and observing the product and the effect.
Example 6
S1, mixing raw glaze powder;
the raw glaze powder is prepared by mixing the following raw materials in parts by weight: 4 parts of lithium porcelain stone, 28 parts of potassium feldspar, 10 parts of albite, 15 parts of quartz, 12 parts of kaolin, 8 parts of barium carbonate, 17 parts of dolomite and 6 parts of wollastonite.
S2, sintering the frits, and crushing the frits until the particle size is less than or equal to 200 meshes;
in this example, a clinker with a particle size of not more than 200 meshes from Shandong Zibo clinker company is purchased, and the initial melting temperature is: at 1050 ℃, detecting chemical compositions of the nano-particles by mass percent, wherein the chemical compositions comprise SiO2：47.1%，Al2O3：22%，Fe2O3+TiO2：0.74%，CaO：11%，MgO：1.2%，K2O+Na2O：5.86%，BaO：10%，ZnO：2.1%。
S3, crushing the sapphire single crystal ingot until the particle size is less than or equal to 325 meshes;
in the embodiment, the coarse crushing is carried out by a jaw crusher, and the particle size is controlled to be less than or equal to 325 meshes by a sand mill after the intermediate crushing is carried out by a double-roller crusher.
S4, counting by mass, 70 parts of the raw glaze powder obtained in the step S1 and 24 parts of the frit obtained in the step 2; and 3, mixing 5.6 parts of the sapphire single crystal ingot and 0.4 part of zirconia powder to obtain the high-hardness glaze.
And preparing the obtained glaze according to the same conventional marble-imitated glazed brick production process to obtain a marble tile product, and detecting and observing the product and the effect.
Example 7
S1, mixing raw glaze powder;
the raw glaze powder is prepared by mixing the following raw materials in parts by weight: 3 parts of lithium porcelain stone, 35 parts of potassium feldspar, 8 parts of albite, 14 parts of quartz, 16 parts of kaolin, 6 parts of barium carbonate, 11 parts of dolomite and 7 parts of wollastonite.
S2, sintering the frits, and crushing the frits until the particle size is less than or equal to 200 meshes;
in this example, a clinker with a particle size of not more than 200 meshes from Shandong Zibo clinker company is purchased, and the initial melting temperature is: 1100 ℃, the chemical composition of which comprises Al according to mass percent2O3：25%，BaO：8%。
S3, crushing the sapphire single crystal ingot until the particle size is less than or equal to 325 meshes;
in the embodiment, the coarse crushing is carried out by a jaw crusher, and the particle size is controlled to be less than or equal to 325 meshes by a sand mill after the intermediate crushing is carried out by a double-roller crusher.
S4, mixing 75 parts by mass of the raw glaze powder obtained in the step S1 and 20 parts by mass of the frit obtained in the step 2; and 4.5 parts of the sapphire single crystal ingot obtained in the step 3 and 0.5 part of zirconia powder are mixed to obtain the high-hardness glaze.
And preparing the obtained glaze according to the same conventional marble-imitated glazed brick production process to obtain a marble tile product, and detecting and observing the product and the effect.
The glaze and the ceramic tile prepared in the above examples 1 to 7 were subjected to performance testing, and in addition, products of ordinary marble tiles on the market were purchased for comparison in this scheme, and the specific performance testing and effect comparison results are shown in the following table:
as can be seen from the table above, the hardness of the glaze prepared by the method can reach more than 5, so that the hardness of the glaze can be obviously improved by adding the sapphire single crystal ingot.
Comparative example 1
The conditions in this comparative example were the same as those in example 6 except that the amount of the added sapphire single crystal was 0.5 parts in step S4.
Comparative example 2
The conditions in this comparative example were the same as those in example 6 except that the amount of the added sapphire single crystal was 8 parts in step S4.
Comparative example 3
The conditions in this comparative example were the same as those in example 6 except that the amount of the added sapphire single crystal was 12 parts in step S4.
Comparative example 4
The conditions in this comparative example were the same as those in example 6, except that in the crushing of the sapphire single crystal ingot in step S3, the particle size was made to be 10 mesh or less by only rough crushing with a jaw crusher, that is, the remaining fraction after crushing and passing through a 10 mesh sieve was 0.1% or less.
Comparative example 5
The conditions in this comparative example were the same as those in example 6, except that the sapphire single crystal ingot was crushed in step S3 by rough crushing with a jaw crusher, and the particle size was made 100 mesh or less by middle crushing with a twin roll crusher, i.e., the fraction of the crushed sapphire single crystal ingot passing through a 100 mesh sieve was 0.1% or less.
Comparative example 6
The conditions in this comparative example were the same as those in example 6, except that the sapphire single crystal ingot was crushed in step S3 by crushing it roughly with a jaw crusher, crushing it by a roll crusher and then controlling the particle size to 500 mesh or less with a sand mill, i.e., the fraction of 500 mesh after crushing was 0.1% or less.
The glaze and the ceramic tile prepared by the comparative examples 1 to 6 are subjected to performance detection, and specific performance detection and effect comparison results are shown in the following table:
as can be seen from the above table, the influence of the addition amount of the sapphire single crystal ingot on the performance, when the addition amount is too small, the effect of increasing hardness is not shown, when the addition amount of the sapphire single crystal ingot is 8% and 12%, the effect of increasing hardness is basically consistent, and on the contrary, when 12% of the sapphire single crystal ingot is added, the flatness of the glaze surface is deteriorated, so that the introduction of 5-8% of the sapphire single crystal ingot into the transparent glaze is optimal; when the particles of the sapphire single crystal ingot are larger than 200 mesh, although the hardness of the glaze is improved, the flatness of the glaze is deteriorated, and even when the particles of the sapphire single crystal ingot reach a fineness of 500 mesh, the effect is substantially the same as that of 325 mesh, and therefore, it is preferable to control the particle size of the sapphire single crystal ingot to 325 mesh from the viewpoint of flatness of the glaze and cost.
Comparative example 7
The conditions in this comparative example are the same as those in example 6, except that the frit is selected in step S2, and the frit of this example is obtained by purchasing a frit having a particle size of not more than 200 meshes from Shandong Zibo frit company, and the initial melting temperature is: 1050 ℃, and the chemical composition of the alloy comprises Al according to mass percent2O3：10%，BaO：10%。
Comparative example 8
The conditions in this comparative example are the same as those in example 6, except that the frit is selected in step S2, and the frit of this example is obtained by purchasing a frit having a particle size of not more than 200 meshes from Shandong Zibo frit company, and the initial melting temperature is: 1050 ℃, and the chemical composition of the alloy comprises Al according to mass percent2O3：30%，BaO：10%。
Comparative example 9
The conditions in this comparative example are the same as those in example 6, except that the frit is selected in step S2, and the frit of this example is obtained by purchasing a frit having a particle size of not more than 200 meshes from Shandong Zibo frit company, and the initial melting temperature is: 1050 ℃, and the chemical composition of the alloy comprises Al according to mass percent2O3：22%，BaO：3%。
Comparative example 10
The conditions in this comparative example are the same as those in example 6, except that the frit is selected in step S2, and the frit of this example is obtained by purchasing a frit having a particle size of not more than 200 meshes from Shandong Zibo frit company, and the initial melting temperature is: 1050 ℃, and the chemical composition of the alloy comprises Al according to mass percent2O3：22%，BaO：17%。
The glaze and the ceramic tile prepared by the comparative examples 7 to 10 are subjected to performance detection, and specific performance detection and effect comparison results are shown in the following table:
from the above table, it can be seen that the content of alumina and barium oxide in the frit has a great influence on the surface defects, decorative effect and antifouling property of the glaze, and when the content of alumina in the introduced frit is small, the surface of the glaze is uneven and has open pores; when the content of the introduced fusion cake alumina is too high, more closed holes exist, the glaze surface is high in temperature, the permeability of the glaze surface is poor, and the decorative effect is reduced; when the content of the introduced frit barium oxide is low, the high-temperature viscosity is low, the color development is poor, when the content of the introduced frit barium oxide is too high, the glaze surface is easy to wrinkle, the skinned glaze surface has high defects, and the glaze can meet the requirements of the defects of the ceramic tile glaze surface, the decoration effect and the antifouling property only when the frit contains a proper amount.
Comparative example 11
The conditions in this comparative example were the same as those in example 6 except that step S3 was not performed, and neither sapphire single crystal ingot nor zirconia was added in step S4.
Comparative example 12
The conditions in this comparative example were the same as those in example 6 except that no zirconia was added in step S4.
Comparative example 13
Conditions in this comparative example were the same as those in example 6 except that step S3 was not performed and no sapphire single crystal ingot was added in step S4.
Comparative example 14
The conditions in this comparative example were the same as those in example 6 except that step S3 was not performed, and the sapphire single crystal ingot was not added in step S4 and the amount of added zirconia was 2 parts.
Comparative example 15
The conditions in this comparative example were the same as those in example 3 except that step S3 was omitted, and 2 parts of zirconia was added without adding the sapphire single crystal ingot in step S4.
The glaze and the ceramic tile prepared by the comparative examples 11 to 15 are subjected to performance detection, and specific performance detection and effect comparison results are shown in the following table:
as can be seen from the results of the above examples, comparative example 11, in which neither sapphire single crystal ingot nor zirconia was added, was reduced in wear resistance by one more grade, and comparative example 12, in which no zirconia was added, was reduced in wear resistance by one more grade; comparative example 13 is a glaze formulation in which sapphire single crystal boule was not added, the abrasion resistance was reduced by one more grade, comparative example 15 is a comparative example of example 3, 2 parts of zirconia was added to the sapphire single crystal without increasing the sapphire single crystal on the basis of example 3, the abrasion resistance was improved as compared with example 3, and it was found that the abrasion resistance of the glaze was improved by the sapphire alone, the improvement range is not obvious, the zirconia can effectively improve the wear resistance of the glaze, but the improvement range is limited by adding a small amount of zirconia, and the glaze is easy to opacify by adding too much zirconia, so that the transparency of the glaze is poor, the decorative effect is not ideal, when the sapphire single crystal ingot and the zirconia act synergistically, the wear resistance of the glaze surface can be greatly improved only by trace zirconia, meanwhile, the permeability of the glaze surface can not be influenced, and the good decorative effect of the glaze surface can be kept, so that the dosage of the zirconium oxide can be effectively reduced by adding the sapphire single crystal ingot.
The above description is only a preferred embodiment of the present application, and not intended to limit the scope of the present application, and all modifications and equivalents of the technical solutions that can be directly or indirectly applied to other related fields without departing from the spirit of the present application are intended to be included in the scope of the present application.
Claims (9)
1. The high-hardness glaze is characterized in that 5.6-8% of sapphire single crystal ingot is added into a known glaze according to mass percentage, and the particle size of the sapphire single crystal ingot is less than or equal to 325 meshes.
2. The high-hardness glaze according to claim 1, wherein the known glaze is a known transparent glaze, and the known transparent glaze comprises 60-82 parts by weight of raw glaze powder and 18-30 parts by weight of frit.
3. The high-hardness glaze according to claim 2, wherein the raw glaze powder comprises the following raw materials in parts by mass: 2-5 parts of lithium porcelain stone, 25-35 parts of potassium feldspar, 5-15 parts of albite, 10-20 parts of quartz, 6-16 parts of kaolin, 6-12 parts of barium carbonate, 11-20 parts of dolomite and 3-8 parts of wollastonite.
4. The high-hardness glaze according to claim 2, wherein said frit has an onset melting temperature in the range of 1000 ℃ to 1100 ℃ and a chemical composition comprising Al in mass percent2O3：18-25%，BaO：8-12%。
5. The high-hardness glaze according to claim 1 further comprising 0.2 to 0.5% by mass of zirconium oxide.
6. The high-hardness glaze according to claim 3 further comprising 0.2 to 0.5% by mass of zirconium oxide.
7. The high-hardness glaze according to claim 4 further comprising 0.2 to 0.5% by mass of zirconium oxide.
8. A method for preparing a high-hardness glaze according to claim 2, comprising the steps of:
s1, mixing raw glaze powder;
s2, sintering the frits, and crushing the frits until the particle size is less than or equal to 200 meshes;
s3, crushing the sapphire single crystal ingot until the particle size is less than or equal to 325 meshes;
s4, mixing the materials obtained in the steps S1, S2 and S3 in proportion; wherein the sequence of steps S1, S2 and S3 can be changed arbitrarily.
9. The method of claim 8, wherein the step S3 includes coarse breaking, intermediate breaking and then grinding with a sand mill or/and an air stream mill.
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| CN114656151A (en) * | 2022-05-26 | 2022-06-24 | 佛山市东鹏陶瓷发展有限公司 | Polished tile wear-resistant glaze and preparation method thereof |
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