High-hardness glaze as well as preparation method and application thereof

Abstract

The invention discloses a high-hardness glaze as well as a preparation method and application thereof, and belongs to the field of architectural ceramics. The high-hardness glaze comprises the following raw materials in parts by weight: 12-14 parts of medium aluminum frit, 16-18 parts of high aluminum frit, 16-18 parts of potassium feldspar, 18-20 parts of albite, 3-5 parts of wollastonite, 1-3 parts of calcined talc, 5-7 parts of calcined zinc oxide, 4-6 parts of emery powder, 1-3 parts of calcined alumina, 2-4 parts of dolomite, 1-3 parts of barium carbonate, 3-5 parts of calcined kaolin, 5-7 parts of kaolin and 34-36 parts of printing paste. 44-46 parts of stamp-pad ink and 4-6 parts of water; a glaze layer prepared from the high-hardness glaze has high hardness and scratch resistance, is wide in application environment, and has good color development and good wear resistance.

Description

Technical Field

[0001] The invention belongs to the field of building ceramics, and particularly relates to a high-hardness glaze and a preparation method and application thereof. Background Art

[0002] Currently, dark-colored ceramic tiles have significant shortcomings in hardness and scratch resistance. While suitable for indoor use, these tiles are easily damaged and cannot meet the long-term demands of high-traffic locations such as airports and high-speed rail stations. In these high-traffic public areas, the surfaces are susceptible to rolling pressure from heavy objects or luggage, as well as scratches from hard objects, resulting in scratches and cracks.

[0003] In order to improve the scratch resistance of ceramic tile products, the industry will add high-hardness materials (such as sapphire crystal ingots) to increase the hardness of the glaze layer, or introduce modified materials into the protective glaze to increase the melt viscosity and thus increase the bonding strength to increase the glaze hardness.

[0004] However, adding high-hardness materials will significantly increase the cost of the glaze and its scope of application is small; after introducing modified materials, the crystals precipitated in the protective glaze will increase, resulting in glaze opacity and affecting the aesthetics of the glazed tile surface; at the same time, the hardness improvement is limited, so a new glaze is needed to prepare a high-hardness glaze layer. Summary of the Invention

[0005] In order to overcome the deficiencies of the prior art, the present invention provides a high-hardness glaze and a preparation method and application thereof; the glaze layer prepared from the high-hardness glaze of the present invention has high hardness and scratch resistance and is widely applicable.

[0006] The technical solution adopted by the present invention to solve its technical problem is:

[0007] A high-hardness glaze, comprising the following raw materials in parts by weight:

[0008] 12-14 parts of medium aluminum frit, 16-18 parts of high aluminum frit, 16-18 parts of potassium feldspar, 18-20 parts of sodium feldspar, 3-5 parts of wollastonite, 1-3 parts of calcined talc, 5-7 parts of calcined zinc oxide, 4-6 parts of corundum powder, 1-3 parts of calcined alumina, 2-4 parts of dolomite, 1-3 parts of barium carbonate, 3-5 parts of calcined kaolin, 5-7 parts of kaolin, 34-36 parts of printing paste, 44-46 parts of printing ink, 4-6 parts of water;

[0009] The aluminum frit comprises the following raw materials in weight percentage: 30-35% quartz, 12-15% kaolin, 20-24% potassium feldspar, 3-6% sodium feldspar, 11-16% calcite, 3-5% dolomite, 7-10% barium carbonate, 4-7% zinc oxide, and 2-4% soda ash;

[0010] The high-alumina frit comprises the following raw materials in percentage by weight: 10-15% quartz, 38-42% kaolin, 18-23% potassium feldspar, 12-16% calcite, 4-7% dolomite, 1-5% aluminum oxide, 1-3% zinc oxide, 1-3% borax and 4-7% calcium carbonate.

[0011] Preferably, the high hardness glaze comprises the following raw materials in parts by weight:

[0012] 13 parts of medium aluminum frit, 17 parts of high aluminum frit, 17 parts of potassium feldspar, 19 parts of sodium feldspar, 4 parts of wollastonite, 2 parts of calcined talc, 6 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined alumina, 3 parts of dolomite, 2 parts of barium carbonate, 4 parts of calcined kaolin, 6 parts of kaolin, 35 parts of printing paste, 45 parts of printing ink, 5 parts of water;

[0013] Preferably, the alumina frit comprises the following raw materials in weight percentage: 33% quartz, 12% kaolin, 20% potassium feldspar, 5% sodium feldspar, 11% calcite, 4% dolomite, 7% barium carbonate, 5% zinc oxide, and 3% soda ash;

[0014] Preferably, the components of the aluminum frit are as follows by weight: SiO2 50.8%, Al2O3 17.6%, K2O2.9%, Na2O 3.2%, CaO 8.9%, MgO 1.4%, BaO 7.7%, ZnO 4.9%, and other balances;

[0015] Preferably, the high-alumina frit comprises the following raw materials in weight percentage: quartz 10%, kaolin 40%, potassium feldspar 20%, calcite 15%, dolomite 5%, industrial alumina 2%, zinc oxide 2%, borax 2%, and calcium carbonate 4%;

[0016] Preferably, the components of the high-alumina frit are as follows by weight: SiO2 43.6%, Al2O3 30.11%, K2O 2.8%, CaO 18.8%, MgO 2.0%, ZnO 2.0%, and other balances.

[0017] Preferably, the alumina frit is prepared by sintering a raw material of alumina frit at 1250-1350°C;

[0018] Preferably, the high-aluminum frit is prepared by sintering a high-aluminum frit raw material at 1400-1500°C;

[0019] Preferably, the medium aluminum frit is a low-temperature frit, and the high aluminum frit is a high-temperature frit.

[0020] Preferably, the high-hardness glaze further comprises one or both of sodium tripolyphosphate and sodium carboxymethyl cellulose.

[0021] The method for preparing the high-hardness glaze comprises the following steps:

[0022] The raw materials of the high-hardness glaze are mixed and then ball-milled to obtain the high-hardness glaze.

[0023] Preferably, the ball milling time is 10-30 min.

[0024] A high-hardness glaze layer is obtained by firing the high-hardness glaze or the high-hardness glaze prepared by the above-mentioned preparation method.

[0025] Preferably, the sintering temperature is 1200-1250°C and the sintering time is 40-80 minutes;

[0026] Preferably, the high-hardness glaze is polished after firing, and the polishing process is as follows:

[0027] 4-6 groups of 2+ fiber polishing modules are polished simultaneously using diamond abrasives with a particle size of 70-80 microns, 4-6 groups of 2+ fiber polishing modules are polished simultaneously using diamond abrasives with a particle size of 40-50 microns, 3-5 groups of sponge brushes are used to remove surface burrs, and then 4-6 groups of 2+ fiber polishing modules are used simultaneously using diamond abrasives with a particle size of 25-35 microns, and finally rinsed with water.

[0028] Further preferably, the high-hardness glaze is polished after firing, and the polishing process is as follows:

[0029] 5 groups of 2+ fiber polishing modules are polished simultaneously using diamond abrasives with a particle size of 75 microns, 5 groups of 2+ fiber polishing modules are polished simultaneously using diamond abrasives with a particle size of 45 microns, 4 groups of sponge brushes are used to remove surface burrs, and then 5 groups of 2+ fiber polishing modules are used simultaneously using diamond abrasives with a particle size of 30 microns, and finally rinsed with water.

[0030] More preferably, the polishing speed is 15-25 m / min.

[0031] A high-hardness ceramic tile comprises a body, a bottom glaze layer and a glaze layer, wherein the glaze layer is the high-hardness glaze layer mentioned above.

[0032] The method for preparing the above-mentioned high-hardness ceramic tiles comprises the following steps:

[0033] The green body is dried, glazed, inkjet printed, high-hardness glaze printed, fired, and polished to obtain high-hardness tiles.

[0034] Preferably, the printed high hardness glaze is printed with a 80-120 mesh full-pass screen, and the glaze amount is 100-130g / m 2 .

[0035] The beneficial effects of the present invention are:

[0036] The glaze layer prepared from the high-hardness glaze of the present invention has high hardness and scratch resistance, with a Mohs hardness of 8, can resist scratches from hard objects without leaving any marks, is applicable to a wide range of environments, has good color development, and has good wear resistance. DETAILED DESCRIPTION

[0037] The present invention is further described below with reference to the embodiments.

[0038] The following will clearly and completely describe the concept, specific scheme and technical effects of the present invention in conjunction with the embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention. The various technical features in the invention can be combined interchangeably without conflicting with each other.

[0039] The following is an exemplary description of the high-hardness glaze of the present invention that can resist scratches from hard objects without leaving any marks and its application in marble tiles.

[0040] As a preferred embodiment, the high hardness glaze of the present invention comprises the following raw materials in parts by weight:

[0041] 12-14 parts of medium aluminum frit, 16-18 parts of high aluminum frit, 16-18 parts of potassium feldspar, 18-20 parts of sodium feldspar, 3-5 parts of wollastonite, 1-3 parts of calcined talc, 5-7 parts of calcined zinc oxide, 4-6 parts of corundum powder, 1-3 parts of calcined alumina, 2-4 parts of dolomite, 1-3 parts of barium carbonate, 3-5 parts of calcined kaolin, 5-7 parts of kaolin, 34-36 parts of printing paste, 44-46 parts of printing ink, 4-6 parts of water;

[0042] Among them, the raw material formula of Chalco frit is: quartz 30-35%, kaolin 12-15%, potassium feldspar 20-24%, sodium feldspar 3-6%, calcite 11-16%, dolomite 3-5%, barium carbonate 7-10%, zinc oxide 4-7%, and soda ash 2-4%.

[0043] The raw material formula of high-alumina frit is: quartz 10-15%, kaolin 38-42%, potassium feldspar 18-23%, calcite 12-16%, dolomite 4-7%, industrial alumina 1-5%, zinc oxide 1-3%, borax 1-3%, and calcium carbonate 4-7%.

[0044] In addition to the above raw materials, a small amount of additives such as sodium tripolyphosphate and sodium carboxymethyl cellulose can be added to the high hardness glaze to improve the glaze slurry properties of the high hardness glaze.

[0045] The above raw materials are mixed evenly and then ball-milled, and then slurried, iron-removed and sieved to obtain protective glaze slurry.

[0046] The glaze of the present invention has a high silicon and aluminum content during the firing process. On the one hand, the high silicon content will play the role of a network connector during the sintering process, generating more glass phases in the glaze layer, and the high aluminum content will also promote the formation of the mullite phase, forming a protective layer with high hardness and high wear resistance on the surface of the glaze layer. The Mohs hardness of the final glaze layer can reach level 8, which can resist scratches from hard objects without leaving any traces, protecting the surface pattern of the tile from being destroyed. At the same time, the formed glaze layer also has good transparency, meets the requirements for use in harsh environments and is suitable for mass production of tiles, with stable performance and good product quality consistency.

[0047] As a preferred embodiment, the method for preparing high-hardness marble tiles that can resist scratches from hard objects without leaving any marks of scratches comprises the following steps:

[0048] S01: Weigh 13 parts of medium aluminum frit, 17 parts of high aluminum frit, 17 parts of potassium feldspar, 19 parts of sodium feldspar, 4 parts of wollastonite, 2 parts of calcined talc, 6 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined alumina, 3 parts of dolomite, 2 parts of barium carbonate, 4 parts of calcined kaolin, 6 parts of kaolin, and add 35 parts of printing paste, 45 parts of printing ink, and 5 parts of water. After ball milling for 20 minutes, a protective glaze is prepared for use.

[0049] S02: The blank is dried, glazed, and inkjet printed before use.

[0050] Among them, the main components of the "green body" are SiO2 68%, Al2O3 20%, Fe2O3 0.5%, TiO2 0.15%, CaO0.56%, MgO 0.92%, K2O 3.3%, and Na2O 2.3%, which are pressed into bricks by a press. "Base glaze" is a conventionally produced base glaze, whose main components are SiO2 50~53%, Al2O3 20~25%, Fe2O3 0.08~0.25%, CaO 5.0~9.0%, MgO3.0~5.0%, K2O 1.0~4.0%, Na2O 1.0~3.0%, TiO2 0.05~0.15%, BaO 0.8~2.1%, ZnO0.25~1.85%, ZrO20.2%~0.5%, MnO<0.01%, P2O5<0.04%, SO3<0.005%.

[0051] S03: Print a layer of protective glaze on the body with a 100-mesh full-pass screen, with a glaze amount of 115±5g / m 2 .

[0052] S04: The bricks coated with glaze are fired to obtain kiln-out bricks.

[0053] S05: The tiles are polished using a free polishing process. This involves using five groups of 2+ fiber polishing modules simultaneously with a 75-micron diamond abrasive, followed by five groups of 2+ fiber polishing modules simultaneously with a 45-micron diamond abrasive to descaling the glaze. Four groups of sponge brushes are then used to deburr the glaze surface. Finally, five groups of 2+ fiber polishing modules simultaneously with a 30-micron diamond abrasive are used to polish the tiles, followed by rinsing with clean water. The result is a high-hardness tile that resists scratches from hard objects without leaving a mark.

[0054] The present invention uses only a single layer of screen-printed protective glaze, and the protective glaze layer is thinner than similar tiles, so the color and transparency are better. Only the glaze is considered to improve the hardness, and the hardness of the product after polishing cannot be guaranteed. The polishing process (free polishing process) provided by the present invention does not require the elastic module, grinding brush and diamond brush in the conventional polishing process. It only relies on the free diamond grinding fluid to process the surface of the glaze layer, retaining the hard structure of the glaze layer and the thin protective glaze layer will not be polished through. Therefore, the polishing process does not damage the glaze layer, so it has excellent stain resistance without waxing; the polished tiles have a good skin feel while having excellent resistance to scratches by hard objects and do not require anti-fouling wax.

[0055] The following is further described with reference to specific embodiments.

[0056] "Parts" in the following examples are parts by weight.

[0057] The raw materials of the aluminum frit in the following example are composed of the following: quartz 33%, kaolin 12%, potassium feldspar 20%, sodium feldspar 5%, calcite 11%, dolomite 4%, barium carbonate 7%, zinc oxide 5%, and soda ash 3%. It is prepared by firing in a frit furnace at 1300°C for 6 hours. The final composition is: SiO2 50.8%, Al2O3 17.6%, K2O 2.9%, Na2O 3.2%, CaO 8.9%, MgO 1.4%, BaO 7.7%, ZnO 4.9%, and the balance is other ingredients. Its Mohs hardness is 6.5.

[0058] The raw materials of the high-alumina frit in the following example are composed of the following: quartz 10%, kaolin 40%, potassium feldspar 20%, calcite 15%, dolomite 5%, industrial alumina 2%, zinc oxide 2%, borax 2%, and calcium carbonate 4%. It is prepared by firing in a frit furnace at 1450°C for 8 hours. The final composition is: SiO2 43.6%, Al2O3 30.11%, K2O 2.8%, CaO 18.8%, MgO 2.0%, ZnO 2.0%, and the balance is other ingredients. Its Mohs hardness is 7.5.

[0059] The main components of the "green body" in the following examples are SiO2 68%, Al2O3 20%, Fe2O3 0.5%, TiO2 0.15%, CaO 0.56%, MgO 0.92%, K2O 3.3%, Na2O 2.3%, and the balance is other components; it is pressed into a brick green by a press.

[0060] The "base glaze" in the following example is a conventionally produced base glaze, whose main components are SiO2 51.06%, Al2O3 21.19%, Fe2O3 0.22%, CaO 8.43%, MgO 3.56%, K2O 1.76%, Na2O 1.99%, TiO2 0.08%, BaO 1.92%, ZnO 0.91%, ZrO2 0.39%, MnO <0.01%, P2O5 <0.04%, SO3 <0.005%, and the balance is other components.

[0061] The printing paste in the following examples is 198# (Zhongrunlin Building Materials Technology) and the printing oil is 8008# (Zhongrunlin Building Materials Technology), and raw materials such as potassium feldspar are purchased from Pansheng Technology.

[0062] Example 1

[0063] A method for preparing high-hardness marble tiles that can resist scratches from hard objects without leaving any marks is as follows:

[0064] S01: Weigh 13 parts of medium aluminum frit, 17 parts of high aluminum frit, 17 parts of potassium feldspar, 19 parts of sodium feldspar, 4 parts of wollastonite, 2 parts of calcined talc, 6 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined alumina, 3 parts of dolomite, 2 parts of barium carbonate, 4 parts of calcined kaolin, 6 parts of kaolin, and add 35 parts of printing paste, 45 parts of printing oil, and 5 parts of water. After ball milling for 20 minutes, the fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60 to prepare protective glaze 1 for use.

[0065] S02: The blank is dried, glazed, and inkjet printed before use.

[0066] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m 2 .

[0067] S04: The bricks coated with glaze are fired to obtain kiln bricks, with a firing temperature of 1224°C and a firing time of 63 minutes.

[0068] S05: Polish the kiln bricks using a free polishing process, namely: 5 groups of 2+ fiber polishing modules simultaneously use a diamond abrasive with a particle size of 75 microns, 5 groups of 2+ fiber polishing modules simultaneously use a diamond abrasive with a particle size of 45 microns to peel the glaze layer, and then use 4 groups of sponge brushes to remove burrs on the glaze layer. Then, use 5 groups of 2+ fiber polishing modules simultaneously use a diamond abrasive with a particle size of 30 microns to polish (polishing speed of 20 m / min), and then rinse with clean water. Sample 1 is obtained.

[0069] Example 2

[0070] In Example 1, S01 is modified to be a common conventional glaze, and the polishing process in S05 is cancelled.

[0071] S01: Weigh 22 parts of sodium feldspar, 25 parts of potassium feldspar, 4 parts of zinc oxide, 13 parts of barium carbonate, 7 parts of kaolin, 15 parts of wollastonite, 6 parts of aluminum oxide, and 8 parts of calcined kaolin, and ball-mill them with 35 parts of printing paste, 45 parts of printing ink, and 5 parts of water for 20 minutes. The fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60. Protective glaze 2 is prepared and set aside.

[0072] S02: The blank is dried, glazed, and inkjet printed before use.

[0073] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m 2 .

[0074] S04: The glazed bricks are fired to obtain sample 2 at a temperature of 1224°C for 63 minutes.

[0075] Example 3

[0076] Only the aluminum frit is added to S01 in Example 1, and the polishing treatment in S05 is omitted.

[0077] S01: Weigh 30 parts of aluminum frit, 17 parts of potassium feldspar, 19 parts of sodium feldspar, 4 parts of wollastonite, 2 parts of calcined talc, 6 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined aluminum oxide, 3 parts of dolomite, 2 parts of barium carbonate, 4 parts of calcined kaolin, 6 parts of kaolin, and add 35 parts of printing paste, 45 parts of printing oil, and 5 parts of water. After ball milling for 20 minutes, the fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60 to prepare protective glaze 3 for use.

[0078] S02: The blank is dried, glazed, and inkjet printed before use.

[0079] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m 2 .

[0080] S04: The glazed bricks are fired to obtain sample 3 at a temperature of 1224°C for 63 minutes.

[0081] Example 4

[0082] In Example 1, only high-aluminum frit is added in S01, and the polishing process in S05 is cancelled.

[0083] S01: Weigh 30 parts of high-alumina frit, 17 parts of potassium feldspar, 19 parts of sodium feldspar, 4 parts of wollastonite, 2 parts of calcined talc, 6 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined alumina, 3 parts of dolomite, 2 parts of barium carbonate, 4 parts of calcined kaolin, 6 parts of kaolin, and add 35 parts of printing paste, 45 parts of printing oil, and 5 parts of water. After ball milling for 20 minutes, the fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60 to prepare protective glaze 4 for use.

[0084] S02: The blank is dried, glazed, and inkjet printed before use.

[0085] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m 2 .

[0086] S04: The glazed bricks are fired to obtain sample 4 at a firing temperature of 1224°C for 63 minutes.

[0087] Example 5

[0088] The contents of the two frits in S01 in Example 1 were modified, and the polishing treatment in S05 was cancelled.

[0089] S01: Weigh 15 parts of medium aluminum frit, 15 parts of high aluminum frit, 17 parts of potassium feldspar, 19 parts of sodium feldspar, 4 parts of wollastonite, 2 parts of calcined talc, 6 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined alumina, 3 parts of dolomite, 2 parts of barium carbonate, 4 parts of calcined kaolin, 6 parts of kaolin, and add 35 parts of printing paste, 45 parts of printing oil, and 5 parts of water. After ball milling for 20 minutes, the fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60 to prepare protective glaze 5 for use.

[0090] S02: The blank is dried, glazed, and inkjet printed before use.

[0091] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m 2 .

[0092] S04: The glazed bricks are fired to obtain sample 5 at a firing temperature of 1224° C. for 63 minutes.

[0093] Example 6

[0094] The polishing process S05 in Example 1 is eliminated.

[0095] S01: Weigh 13 parts of medium aluminum frit, 17 parts of high aluminum frit, 17 parts of potassium feldspar, 19 parts of sodium feldspar, 4 parts of wollastonite, 2 parts of calcined talc, 6 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined alumina, 3 parts of dolomite, 2 parts of barium carbonate, 4 parts of calcined kaolin, 6 parts of kaolin, and add 35 parts of printing paste, 45 parts of printing oil, and 5 parts of water. After ball milling for 20 minutes, the fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60 to prepare protective glaze 1 for use.

[0096] S02: The blank is dried, glazed, and inkjet printed before use.

[0097] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m 2 .

[0098] S04: The glazed bricks are fired to obtain sample 6 at a firing temperature of 1224° C. for 63 minutes.

[0099] Example 7

[0100] The polishing process in S05 in Example 1 is modified.

[0101] S01: Weigh 13 parts of medium aluminum frit, 17 parts of high aluminum frit, 17 parts of potassium feldspar, 19 parts of sodium feldspar, 4 parts of wollastonite, 2 parts of calcined talc, 6 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined alumina, 3 parts of dolomite, 2 parts of barium carbonate, 4 parts of calcined kaolin, 6 parts of kaolin, and add 35 parts of printing paste, 45 parts of printing oil, and 5 parts of water. After ball milling for 20 minutes, the fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60 to prepare protective glaze 1 for use.

[0102] S02: The blank is dried, glazed, and inkjet printed before use.

[0103] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m 2 .

[0104] S04: The bricks coated with glaze are fired to obtain kiln bricks, with a firing temperature of 1224°C and a firing time of 63 minutes.

[0105] S05: Sample 7 was prepared by using only 5 groups of 2+ fiber polishing modules and a diamond polishing liquid with a particle size of 30 μm for polishing (polishing speed of 20 m / min).

[0106] Example 8

[0107] Modify the polishing process in S05 in Example 1:

[0108] S01: Weigh 13 parts of medium aluminum frit, 17 parts of high aluminum frit, 17 parts of potassium feldspar, 19 parts of sodium feldspar, 4 parts of wollastonite, 2 parts of calcined talc, 6 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined alumina, 3 parts of dolomite, 2 parts of barium carbonate, 4 parts of calcined kaolin, 6 parts of kaolin, and add 35 parts of printing paste, 45 parts of printing oil, and 5 parts of water. After ball milling for 20 minutes, the fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60 to prepare protective glaze 1 for use.

[0109] S02: The blank is dried, glazed, and inkjet printed before use.

[0110] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m 2 .

[0111] S04: The bricks coated with glaze are fired to obtain kiln bricks, with a firing temperature of 1224°C and a firing time of 63 minutes.

[0112] S05: Sample 8 was obtained after polishing (polishing speed of 20 m / min) using 15 groups of 6000 mesh elastic grinding blocks, 5 groups of 400 mesh elastic grinding blocks, 6 groups of 1000 mesh elastic grinding blocks, 4 groups of 1500 mesh elastic grinding blocks, 10 groups of 240 mesh elastic grinding blocks, 10 groups of 800 mesh elastic grinding blocks, 1 group of 1500 mesh elastic grinding blocks, 4 groups of 2000 mesh elastic grinding blocks, and 5 groups of 300 mesh elastic grinding blocks.

[0113] Comparative Example 1

[0114] The frit component in S01 of Example 1 is eliminated, and the polishing treatment in S05 is eliminated.

[0115] S01: Weigh 24 parts of potassium feldspar, 27 parts of sodium feldspar, 6 parts of wollastonite, 3 parts of calcined talc, 8 parts of calcined zinc oxide, 7 parts of corundum powder, 3 parts of calcined aluminum oxide, 4 parts of dolomite, 3 parts of barium carbonate, 6 parts of calcined kaolin, and 9 parts of kaolin, and ball-mill them with 35 parts of printing paste, 45 parts of printing oil, and 5 parts of water for 20 minutes. The fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60. Comparative protective glaze 1 is prepared for use.

[0116] S02: The blank is dried, glazed, and inkjet printed before use.

[0117] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m2 .

[0118] S04: The glazed bricks were fired to obtain a comparative sample 1 at a firing temperature of 1224°C for 63 minutes.

[0119] Comparative Example 2

[0120] The frit in S01 of Example 1 was introduced into the glaze formulation as a raw material, and the polishing treatment in S05 was omitted.

[0121] S01: Weigh 23 parts of potassium feldspar, 20 parts of sodium feldspar, 4 parts of wollastonite, 2 parts of calcined talc, 7 parts of calcined zinc oxide, 6 parts of corundum powder, 2 parts of calcined alumina, 4 parts of dolomite, 3 parts of barium carbonate, 4 parts of calcined kaolin, 14 parts of kaolin, 6 parts of quartz, and 4 parts of calcite, and ball-mill them with 35 parts of printing paste, 45 parts of printing oil, and 5 parts of water for 20 minutes. The fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60. Comparative protective glaze 2 is prepared for use.

[0122] S02: The blank is dried, glazed, and inkjet printed before use.

[0123] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m 2 .

[0124] S04: The bricks coated with glaze were fired to obtain comparative sample 2, with a firing temperature of 1224°C and a firing time of 63 minutes.

[0125] Comparative Example 3

[0126] The contents of the two frits in S01 in Example 1 were modified, and the polishing treatment in S05 was cancelled.

[0127] S01: Weigh 15 parts of medium aluminum frit, 20 parts of high aluminum frit, 17 parts of potassium feldspar, 19 parts of sodium feldspar, 3 parts of wollastonite, 2 parts of calcined talc, 4 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined alumina, 3 parts of dolomite, 2 parts of barium carbonate, 4 parts of calcined kaolin, and 4 parts of kaolin, and ball mill them with 35 parts of printing paste, 45 parts of printing oil, and 5 parts of water for 20 minutes. The fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60. Comparative protective glaze 3 is prepared for use.

[0128] S02: The blank is dried, glazed, and inkjet printed before use.

[0129] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m 2 .

[0130] S04: The glazed bricks were fired to obtain comparative sample 3 at a firing temperature of 1224°C for 63 minutes.

[0131] Comparative Example 4

[0132] The contents of the two frits in S01 in Example 1 were modified, and the polishing treatment in S05 was cancelled.

[0133] S01: Weigh 20 parts of medium aluminum frit, 20 parts of high aluminum frit, 17 parts of potassium feldspar, 17 parts of sodium feldspar, 3 parts of wollastonite, 2 parts of calcined talc, 3 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined alumina, 2 parts of dolomite, 2 parts of barium carbonate, 3 parts of calcined kaolin, 4 parts of kaolin, and add 35 parts of printing paste, 45 parts of printing oil, and 5 parts of water. After ball milling for 20 minutes, the fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60. Comparative protective glaze 4 is prepared for use.

[0134] S02: The blank is dried, glazed, and inkjet printed before use.

[0135] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m 2 .

[0136] S04: The glazed bricks were fired to obtain a comparative sample 4 at a firing temperature of 1224° C. for 63 minutes.

[0137] Comparative Example 5

[0138] The contents of the two frits in S01 in Example 1 were modified, and the polishing treatment in S05 was cancelled.

[0139] S01: Weigh 10 parts of medium aluminum frit, 20 parts of high aluminum frit, 17 parts of potassium feldspar, 19 parts of sodium feldspar, 4 parts of wollastonite, 2 parts of calcined talc, 6 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined alumina, 3 parts of dolomite, 2 parts of barium carbonate, 4 parts of calcined kaolin, 6 parts of kaolin, and add 35 parts of printing paste, 45 parts of printing oil, and 5 parts of water. After ball milling for 20 minutes, the fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60. Comparative protective glaze 5 is prepared for use.

[0140] S02: The blank is dried, glazed, and inkjet printed before use.

[0141] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m 2 .

[0142] S04: The glazed bricks were fired to obtain a comparative sample 5 at a firing temperature of 1224° C. for 63 minutes.

[0143] Comparative Example 6

[0144] The polishing process in S05 in Example 1 is modified.

[0145] S01: Weigh 13 parts of medium aluminum frit, 17 parts of high aluminum frit, 17 parts of potassium feldspar, 19 parts of sodium feldspar, 4 parts of wollastonite, 2 parts of calcined talc, 6 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined alumina, 3 parts of dolomite, 2 parts of barium carbonate, 4 parts of calcined kaolin, 6 parts of kaolin, and add 35 parts of printing paste, 45 parts of printing oil, and 5 parts of water. After ball milling for 20 minutes, the fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60 to prepare protective glaze 1 for use.

[0146] S02: The blank is dried, glazed, and inkjet printed before use.

[0147] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m 2 .

[0148] S04: The bricks coated with glaze are fired to obtain kiln bricks, with a firing temperature of 1224°C and a firing time of 63 minutes.

[0149] S05: Comparative sample 6 was obtained by polishing with 5 groups of 2+ fiber polishing modules using a diamond polishing liquid with a particle size of 75 microns and 5 groups of 2+ fiber polishing modules using a diamond polishing liquid with a particle size of 45 microns (polishing speed of 20 m / min).

[0150] Comparative Example 7

[0151] Modify the polishing process in S05 in Example 1:

[0152] S01: Weigh 13 parts of medium aluminum frit, 17 parts of high aluminum frit, 17 parts of potassium feldspar, 19 parts of sodium feldspar, 4 parts of wollastonite, 2 parts of calcined talc, 6 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined alumina, 3 parts of dolomite, 2 parts of barium carbonate, 4 parts of calcined kaolin, 6 parts of kaolin, and add 35 parts of printing paste, 45 parts of printing oil, and 5 parts of water. After ball milling for 20 minutes, the fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60 to prepare protective glaze 1 for use.

[0153] S02: The blank is dried, glazed, and inkjet printed before use.

[0154] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m 2 .

[0155] S04: The bricks coated with glaze are fired to obtain kiln bricks, with a firing temperature of 1224°C and a firing time of 63 minutes.

[0156] S05: The glaze layer was peeled using 5 sets of 1000-mesh abrasive brushes, 5 sets of 400-mesh abrasive brushes, and 5 sets of 1500-mesh abrasive brushes. The glaze surface was then deburred using 4 sets of sponge brushes. The surface was then polished using 5 sets of 2+ fiber polishing modules and diamond abrasive fluid with a particle size of 30 microns (polishing speed of 20 m / min) to produce comparison sample 7.

[0157] Comparative Example 8

[0158] The contents of the two frits in S01 in Example 1 were modified, and the polishing treatment in S05 was cancelled.

[0159] S01: Weigh 10 parts of medium aluminum frit, 15 parts of high aluminum frit, 18 parts of potassium feldspar, 19 parts of sodium feldspar, 6 parts of wollastonite, 4 parts of calcined talc, 6 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined alumina, 3 parts of dolomite, 2 parts of barium carbonate, 4 parts of calcined kaolin, 6 parts of kaolin, and add 35 parts of printing paste, 45 parts of printing oil, and 5 parts of water. After ball milling for 20 minutes, the fineness is 0.1-0.3 (325 mesh sieve) and the specific gravity is between 1.58 and 1.60. Comparative protective glaze 8 is prepared for use.

[0160] S02: The blank is dried, glazed, and inkjet printed before use.

[0161] S03: Print a layer of protective glaze 1 on the body using a 100-mesh full-pass screen. The glaze amount is 115±5g / m 2 .

[0162] S04: The glazed bricks were fired to obtain a comparative sample 8 at a firing temperature of 1224° C. for 63 minutes.

[0163] The properties of samples 1-8 prepared in Examples 1-8 are shown in Table 1, and the properties of comparative samples 1-8 prepared in Comparative Examples 1-8 are shown in Table 2.

[0164] Table 1

[0165]

[0166]

[0167] Table 2

[0168]

[0169] From Table 1 and Table 2 we can see that:

[0170] (1) The glaze layer prepared by the protective glaze 1 in Example 1 has the highest hardness, with a Mohs hardness of 8. The glaze layer of Example 2 using ordinary conventional glaze has a lower hardness. The glaze layers of Comparative Example 1 without adding frit, Comparative Example 2 introducing frit in the form of raw materials, Example 3 adding only medium aluminum frit, and Example 4 adding only high aluminum frit have lower hardness. The glaze layers of Example 5 increasing the proportion of medium aluminum frit and Comparative Example 5 increasing the proportion of high aluminum frit have lower hardness. The glaze layers of Comparative Examples 3 and Comparative Examples 4 increasing the total amount of frit have lower hardness. The glaze layers of Comparative Example 8 reducing the total amount of frit have lower hardness. It can be seen that adding medium aluminum frit and high aluminum frit in appropriate proportions and amounts can obtain a glaze layer with higher hardness.

[0171] (2) The glaze layer prepared by protective glaze 1 in Example 6 was not polished, had low gloss and poor skin feel. The glossiness of Example 7 and Comparative Example 6 was still low after polishing. The polishing methods of Example 1 and Comparative Example 7 produced high gloss and a smooth skin feel after polishing. The conventional polishing process used in Example 8 produced high gloss and a smooth skin feel after polishing, but the hardness of the glaze layer was significantly reduced, making it easily damaged.

[0172] The above is a specific description of the preferred implementation of the present invention, but the invention is not limited to the embodiments. Those skilled in the art can make various equivalent modifications or substitutions without violating the spirit of the present invention. These equivalent modifications or substitutions are all included in the scope defined by the claims of this application.

Claims

1. A high hardness glaze, characterized in that: In parts by weight, it includes the following raw materials: 12-14 parts of medium aluminum frit, 16-18 parts of high aluminum frit, 16-18 parts of potassium feldspar, 18-20 parts of sodium feldspar, 3-5 parts of wollastonite, 1-3 parts of calcined talc, 5-7 parts of calcined zinc oxide, 4-6 parts of corundum powder, 1-3 parts of calcined alumina, 2-4 parts of dolomite, 1-3 parts of barium carbonate, 3-5 parts of calcined kaolin, 5-7 parts of kaolin, 34-36 parts of printing paste, 44-46 parts of printing ink, 4-6 parts of water; The aluminum frit comprises the following raw materials in weight percentage: 30-35% quartz, 12-15% kaolin, 20-24% potassium feldspar, 3-6% sodium feldspar, 11-16% calcite, 3-5% dolomite, 7-10% barium carbonate, 4-7% zinc oxide, and 2-4% soda ash; The high-alumina frit comprises the following raw materials in percentage by weight: 10-15% quartz, 38-42% kaolin, 18-23% potassium feldspar, 12-16% calcite, 4-7% dolomite, 1-5% aluminum oxide, 1-3% zinc oxide, 1-3% borax and 4-7% calcium carbonate.

2. The high-hardness glaze according to claim 1, characterized in that: The high hardness glaze comprises the following raw materials in parts by weight: 13 parts of medium aluminum frit, 17 parts of high aluminum frit, 17 parts of potassium feldspar, 19 parts of sodium feldspar, 4 parts of wollastonite, 2 parts of calcined talc, 6 parts of calcined zinc oxide, 5 parts of corundum powder, 2 parts of calcined alumina, 3 parts of dolomite, 2 parts of barium carbonate, 4 parts of calcined kaolin, 6 parts of kaolin, 35 parts of printing paste, 45 parts of printing ink, 5 parts of water; The aluminum frit comprises the following raw materials in weight percentage: 33% quartz, 12% kaolin, 20% potassium feldspar, 5% sodium feldspar, 11% calcite, 4% dolomite, 7% barium carbonate, 5% zinc oxide, and 3% soda ash; The components of the aluminum frit are as follows by weight: SiO2 50.8%, Al2O3 17.6%, K2O 2.9%, Na2O3.2%, CaO 8.9%, MgO 1.4%, BaO 7.7%, ZnO 4.9%, and other balances; The high-alumina frit comprises the following raw materials in weight percentage: quartz 10%, kaolin 40%, potassium feldspar 20%, calcite 15%, dolomite 5%, industrial alumina 2%, zinc oxide 2%, borax 2%, and calcium carbonate 4%; The components of the high-alumina frit are as follows by weight: SiO2 43.6%, Al2O3 30.11%, K2O 2.8%, CaO 18.8%, MgO 2.0%, ZnO 2.0%, and other balances.

3. The high hardness glaze according to claim 1, characterized in that: The aluminum frit is prepared by sintering the aluminum frit raw material at 1250-1350°C; The high-aluminum frit is prepared by sintering high-aluminum frit raw materials at 1400-1500° C. The high-hardness glaze further comprises one or both of sodium tripolyphosphate and sodium carboxymethyl cellulose.

4. The method for preparing the high-hardness glaze according to any one of claims 1 to 3, characterized in that: The following steps are involved: The raw materials of the high-hardness glaze are mixed and then ball-milled to obtain the high-hardness glaze.

5. The preparation method according to claim 4, characterized in that The ball milling time is 10-30 minutes.

6. A high hardness glaze layer, characterized in that: The glaze is obtained by firing the high-hardness glaze according to any one of claims 1 to 3 or the high-hardness glaze prepared by the preparation method according to any one of claims 4 to 5.

7. The high-hardness glaze layer according to claim 6, characterized in that: The sintering temperature is 1200-1250°C and the sintering time is 40-80 minutes; The high-hardness glaze is polished after firing, and the polishing process is as follows: 4-6 groups of 2+ fiber polishing modules are polished simultaneously using diamond abrasives with a particle size of 70-80 microns, 4-6 groups of 2+ fiber polishing modules are polished simultaneously using diamond abrasives with a particle size of 40-50 microns, 3-5 groups of sponge brushes are used to remove surface burrs, and then 4-6 groups of 2+ fiber polishing modules are used simultaneously using diamond abrasives with a particle size of 25-35 microns, and finally rinsed with water.

8. A high hardness ceramic tile, characterized in that: The invention comprises a body, a bottom glaze layer and a glaze layer, wherein the glaze layer is the high-hardness glaze layer according to any one of claims 6 to 7.

9. The method for preparing high-hardness ceramic tiles according to claim 8, characterized in that: The following steps are involved: The green body is dried, glazed, inkjet printed, high-hardness glaze printed, fired, and polished to obtain high-hardness tiles.

10. The preparation method according to claim 9, characterized in that The printed high hardness glaze is printed with 80-120 mesh full-pass screen, and the glaze amount is 100-130g / m 2 .

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