CN118145887A - Gao Baigao ink-jet pattern-penetrating composite process ceramic rock plate and preparation method thereof - Google Patents
Gao Baigao ink-jet pattern-penetrating composite process ceramic rock plate and preparation method thereof Download PDFInfo
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- CN118145887A CN118145887A CN202410585513.7A CN202410585513A CN118145887A CN 118145887 A CN118145887 A CN 118145887A CN 202410585513 A CN202410585513 A CN 202410585513A CN 118145887 A CN118145887 A CN 118145887A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 31
- 239000011435 rock Substances 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 21
- 230000008569 process Effects 0.000 title description 12
- 239000004744 fabric Substances 0.000 claims abstract description 57
- 230000000149 penetrating effect Effects 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000010304 firing Methods 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 238000005516 engineering process Methods 0.000 claims abstract description 11
- 238000007641 inkjet printing Methods 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 238000003825 pressing Methods 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 78
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- 239000000203 mixture Substances 0.000 claims description 67
- 239000013078 crystal Substances 0.000 claims description 54
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 50
- 239000011707 mineral Substances 0.000 claims description 50
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- 239000011521 glass Substances 0.000 claims description 25
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- 239000011787 zinc oxide Substances 0.000 claims description 18
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims description 17
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 1
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
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- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
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- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
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- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
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Landscapes
- Glass Compositions (AREA)
Abstract
The invention belongs to the field of ceramic building materials, and particularly relates to a high Bai Gaotou ink-jet pattern-penetrating composite technology ceramic rock plate and a preparation method thereof. The preparation method comprises the following steps: cloth penetrating the blank substrate to form a primer layer; the base material layer is coated with penetrating blank fabric to form a fabric layer; pressing the primer layer and the fabric layer into a blank; ink-jet printing a penetrating ink pattern on the surface of the blank; drying the blank body of which the surface is subjected to ink-jet printing of the penetrating ink pattern; and (5) sintering. The invention develops a high-whiteness high-transparency pattern-penetrated blank base material formula, combines Gao Baigao color-penetrating good-color-developing high-transparency pattern-penetrated blank face material formula, and can directly polish and produce pattern-penetrated ceramic tiles after firing without using base glaze.
Description
Technical Field
The invention belongs to the field of ceramic building materials, and particularly relates to a high Bai Gaotou ink-jet pattern-penetrating composite technology ceramic rock plate and a preparation method thereof.
Background
The introduction of the ink-bleeding ink has made inkjet polished tiles of great interest. The ink-jet pattern-penetrating technology can ensure that the polished tile can realize multiple improvements of color, texture and the like by utilizing the digital ink-jet printing technology while maintaining the inherent physical property advantage. The ceramic inkjet printing ink then advances further toward the functional ink. The existing oily color-permeation ink not only solves the problem of color development of common ink, but also can improve permeation depth and definition.
The ink-jet glazed tile has the advantages of good color development, high wear resistance and good antifouling performance, and thus has more advantages than common glazed tiles. Today, the ink-jet pattern-penetrating polished tiles enter the production application stage and gradually go to the market in large batches, but the production process is still immature, which also causes a new technological innovation of upstream ceramic enterprises. At present, the traditional tile is affected by the formula of the blank, the transparency and the color development are poor, and the green brick does not have light transmission performance, so that the application space of the ink-jet tile is limited. In addition, the whiteness deviation of the backing material and the surface material layer of the traditional dry-method pattern-penetrated tile is larger, the backing material layer and the surface material layer can be exposed when the product is subjected to chamfering and polishing, and the existing separation line influences the aesthetic feeling of the tile. And the current ink-jet pattern impregnation is limited in that the pattern impregnated blank is polished after being fired, and the pattern impregnated blank is rarely decorated by combining with other effect glazes.
Disclosure of Invention
Aiming at the problems, the invention develops a high-whiteness and high-transparency pattern-penetrated blank base material formula, combines a Gao Baigao-transparency, good-color-development and high-transparency pattern-penetrated blank surface material formula, and can directly polish and produce the pattern-penetrated ceramic tile after firing without using base glaze. In addition, in order to enrich the decoration of the product, a layer of quick-firing crystal glaze can be applied on the surface of the green body, and the ceramic polished tile with the technology of combining the ink-jet pattern infiltration with the crystal pattern is prepared by the technology of combining the high white high-permeability property with the color integration of the base material layer and the surface material layer.
In a first aspect, the invention provides a preparation method of a high Bai Gaotou ink-jet pattern-penetrating composite process ceramic rock plate. The preparation method comprises the following steps:
cloth penetrating the blank substrate to form a primer layer;
the base material layer is coated with penetrating blank fabric to form a fabric layer; the mineral composition of the permeable green body fabric comprises the following components in percentage by mass: guangxi white mud: 30-40%; gao Baigao kaolin: 10-20%; cloud water mill stone: 20-30%; water milling potassium feldspar: 10-15%; gao Baina feldspar: 10-15% of wollastonite: 5-15%, frit A:5-15%; the chemical composition of the frit A comprises the following components in percentage by mass ：IL：0.1-0.3%;SiO2：40-70%;Al2O3：15-20%;Fe2O3：0.1-0.2%;TiO2：0.05 -0.3%;CaO：3-6%;MgO：0.5-1.5%;K2O：4.0-6.0%;Na2O：2.0-5.0%;
Pressing the primer layer and the fabric layer into a blank;
ink-jet printing a penetrating ink pattern on the surface of the blank;
drying the blank body of which the surface is subjected to ink-jet printing of the penetrating ink pattern;
And (5) sintering.
Preferably, the mineral composition of the frit a comprises, in mass percent: potassium feldspar: 30-50%; albite: 10-30%; quartz: 5-20%; wollastonite: 3-10%; 5-15% of water-washed kaolin.
Preferably, the mineral composition of the penetrating blank substrate comprises the following components in percentage by mass: guangxi white mud: 30-45%; gao Baigao kaolin: 10-20%; cloud water mill stone: 20-35%; water milling potassium feldspar: 10-15%; gao Baina feldspar: 10-15% of wollastonite: 5-15%.
Preferably, the preparation method further comprises: printing a blank Shi Jiejing glaze penetrating the ink pattern on the surface in an inkjet mode before firing; the crystal glaze comprises a base mineral and crystal nucleus dry grains; the basic mineral of the crystalline glaze comprises the following components in percentage by mass: frit B:25-50%; calcite: 10-15%; calcining zinc oxide: 5-10%; kaolin: 5-8%; calcined talc: 5-10%; sodium glass powder: 10-20%; titanium dioxide: 3-10%; the chemical composition of the frit B comprises the following components in percentage by mass ：SiO2：40-65%;Al2O3：5-10%;CaO：10-15%;K2O：3-6%;ZnO：5-20%;TiO2：1-4%.
Preferably, the chemical composition of the sodium glass powder comprises the following components in percentage by mass ：IL：0.1-0.9%;SiO2：30-60%;Al2O3：3-15%;Fe2O3：0.01-0.3%;TiO2：0.01-0.2%;CaO：5-15%;MgO：1-3%;K2O：0.3-3%;Na2O：3-15%.
Preferably, the crystal nucleus dry particles account for 0.1-0.3wt% of the basic mineral; the mineral composition of the crystal nucleus dry particles comprises the following components in percentage by mass: 20-40% of albite; quartz 10-20%; 2-5% of calcined talc; 3-6% of kaolin; 3-8% of titanium dioxide; 30-50% of zinc oxide; 0.5-3% of cryolite.
Preferably, the application mode of the crystal glaze is glaze spraying; the specific gravity of the crystalline glaze is 1.55-1.60 g/cm 3, and the application amount is 820-860 g/m 2.
Preferably, the firing temperature is 1215-1225 ℃ and the firing time is 65-80 minutes.
Preferably, the preparation method further comprises polishing the sintered blank.
In a second aspect, the invention provides a high Bai Gaotou inkjet-and-pattern-penetrating composite technical ceramic rock plate, which is obtained according to the preparation method of any one of the above-mentioned Gao Baigao-penetrating inkjet-and-pattern-penetrating composite technical ceramic rock plate.
The invention has the following beneficial effects:
1. Creative: and combining Gao Baigao with the blank with good color development, preparing the blank with bright color, clear pattern and good overall effect by using a pattern infiltration process, and firing to obtain the ceramic polished tile with bright color and good wear resistance. In addition, by combining with the crystallization glaze technology, white or blue crystal flowers can be formed on the brick surface, the stippling effect of patterns is enhanced, and the large plate product with strong third dimension is prepared.
2. The decorative effect is good: compared with a common ink-jet natural-surface ceramic large plate, the ceramic tile has bright color, is transparent in whole and has higher wear resistance. Meanwhile, the ceramic tile combined with the crystallization glaze process has the advantages of bright overall color, good crystal flower decoration effect, special permeability after polishing, and better white crystal flower decoration effect when being matched with light gray beige patterns.
3. The application range is wide: the invention is not affected by environmental factors, and can be widely applied to decoration of various interior walls, floors and background wall home desktop panels.
4. Easy cleaning: the rock plate is completely sintered, the water absorption is controlled within 0.3 percent, and the rock plate is polished to be super-clean and bright, has good antifouling effect and high glossiness; is easy to clean and sanitary.
5. Durable: the invention has stable performance, small time and environment influence factors, high wear resistance, long service life and wide market economic benefit, and can keep the same feeling as new feeling for a long time.
Drawings
FIG. 1 is a graph of the tile surface effect of example 1;
FIG. 2 is a graph of the tile effect of example 2;
FIG. 3 is a graph of the tile surface effect of comparative example 1;
FIG. 4 is a graph of the tile surface effect of comparative example 2;
FIG. 5 is a graph of the tile surface effect of comparative example 3;
FIG. 6 is a graph of the tile effect of comparative example 4.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof. Unless otherwise specified, each percentage refers to a mass percent.
According to the invention, the formulas of the backing materials and the facing materials of the traditional pattern-penetrated bricks are improved, particularly, the formula of the facing materials of the penetrated blank is improved, the frit with high glass phase content is introduced, a blank with high whiteness, high transparency, excellent color development and excellent physical and chemical properties is developed, and then the ink-jet pattern-penetrated composite ceramic rock plate with high Bai Gaotou ink-jet pattern-penetrated composite technology, which is bright in color, strong in stereoscopic impression and good in antifouling effect, is prepared by combining an ink-jet pattern-penetrated technology and sintering in a kiln. The method can also be used for compounding an inkjet pattern-penetrating process and a crystal glaze process to produce a crystal glaze ceramic rock plate which can be polished or not polished. The following illustrates a method for preparing a ceramic rock plate by using the Gao Baigao-pass inkjet-infiltration composite process.
Selecting a base material with better whiteness according to the requirements of the rock plate blank. The chemical composition of the primer (penetrating blank primer) comprises the following components in percentage by mass ：IL：2.0-4.5%;SiO2：60-80%;Al2O3：10-20%;Fe2O3：0.1-0.3%;TiO2：0.05-0.3%;CaO：0.3-1.5%;MgO：0.3-1.5%;K2O：2.0-4.0%;Na2O：1.0-3.0%.
Preferably, the mineral with high whiteness and good transparency is used for preparing the infiltration green body base material. As an example, the mineral composition of the infiltrated green body primer comprises, in mass percent: guangxi white mud: 30-45%; gao Baigao kaolin: 10-20%; cloud water mill stone: 20-35%; water milling potassium feldspar: 10-15%; gao Baina feldspar: 10-15% of wollastonite: 5-15%. As an example, the chemical composition of the guangxi white mud, which includes ：IL：3.0-5.5%;SiO2：60-70%;Al2O3：15-23%;Fe2O3：0.1-0.3%;TiO2：0.05-0.2%;CaO：0.2-0.5%;MgO：0.2-0.5%;K2O：2.0-4.0%;Na2O：1.0-2.0%. in mass percent as an example, and the chemical composition of the cloud-float terrazzo, which includes ：IL：0.5-1.0%;SiO2：70-80%;Al2O3：10-15%;Fe2O3：0.1-0.3%;TiO2：0.05-0.2%;CaO：0.1-0.3%;MgO：0.2-0.5%;K2O：3.0-5.0%;Na2O：4.0-6.0%. in mass percent, has good light transmission properties. In some embodiments, the whiteness of the infiltrated green body bed charge is 75.6 degrees.
The raw materials of the penetrating blank substrate comprise other auxiliary agents besides mineral compositions. The auxiliary agent comprises a toughening agent, a reinforcing agent, a diluent and water glass. The toughening agent can be 1-2wt% of the composition of the base material mineral of the green body. The reinforcing agent can be 0.3-1wt% of the mineral composition of the blank substrate. The diluent may be 0.3-1wt% of the green body primer mineral composition. For example, the diluent is one of water glass and/or sodium tripolyphosphate. Water glass was specifically used in the examples. The water glass can be 0.3-1wt% of the composition of the base material mineral of the blank body.
Weighing the raw materials according to the raw material composition of the penetrating blank substrate, adding water, ball-milling uniformly, and granulating by a spray tower. The grain composition of the penetrating blank substrate comprises the following components in percentage by mass: 30 mesh or more: 20-30%;30 to 80 mesh: 60-70%; below 80 meshes less than or equal to 10 percent. Wherein, above 30 mesh refers to the part which stays on the 30 mesh screen, and below 80 mesh refers to the part which passes through the 80 mesh screen. The green body bottom material with the grain composition can ensure the forming performance of green bricks. The moisture content of the blank substrate is preferably controlled to be 8.5+/-3 wt%.
And selecting a fabric with better whiteness according to the requirements of the rock plate blank body. The chemical composition of the fabric (penetrating blank fabric) comprises the following components in percentage by mass ：IL：2.0-3.5%;SiO2：60-80%;Al2O3：10-20%;Fe2O3：0.05-0.2%;TiO2：0.05-0.3%;CaO：0.5-1.5%;MgO：0.5-1.5%;K2O：3.0-4.0%;Na2O：2.0-3.0%.
Preferably, the permeable green body fabric is prepared from minerals with high whiteness and good transparency. The existing high-whiteness fabric is mainly a high-calcium high-alumina system, has certain whiteness but is unfavorable for red and yellow color development of penetrating ink, so that the effects of high whiteness and bright color development cannot be simultaneously realized, and the penetrating blank fabric is specially designed. As an example, the mineral composition of the infiltrated green body fabric comprises, in mass percent: guangxi white mud: 30-40%; gao Baigao kaolin: 10-20%; cloud water mill stone: 20-30%; water milling potassium feldspar: 10-15%; gao Baina feldspar: 10-15% of wollastonite: 5-15%, frit A:5-15%. The frit is introduced into the green body, so that the content of the glass phase in the green body is increased, the green body is sintered, the density of the green body is improved, and the porosity is reduced. If the frit A is not introduced into the infiltrated blank fabric, the blank has low sintering degree, small bulk density, high glass phase content and large porosity, and is unfavorable for light transmission of the blank.
The chemical composition of the frit A comprises ：IL：0.1-0.3%;SiO2：40-70%;Al2O3：15-20%;Fe2O3：0.1-0.2%;TiO2：0.05-0.3%;CaO：3-6%;MgO：0.5-1.5%;K2O：4.0-6.0%;Na2O：2.0-5.0%. of using the frit A in the permeable green body fabric in percentage by mass, so that the sintering of the green body is facilitated, the density and the glass phase content of the green body are improved, the light transmission is facilitated, and the frit of the low-calcium low-magnesium high-potassium system is more beneficial to the color development of the permeable ink in the permeable fabric. However, the high calcium high magnesium high zinc system frit is not conducive to penetration of inks, especially reddish yellow coloration.
As an example, the mineral composition of the frit a comprises, in mass percent: potassium feldspar: 30-50%; albite: 10-30%; quartz: 5-20%; wollastonite: 3-10%; 5-15% of water-washed kaolin.
Weighing the raw materials according to the mineral composition of the frit A, melting for 3-8 hours at 1350-1450 ℃ to obtain glass liquid, and then water quenching and crushing the glass liquid to obtain the frit A. The mesh number of the frit A may be 60-150 mesh.
The permeable green body fabric has certain light transmittance, and the transparency can reach more than 10-35%. In some embodiments, the whiteness of the infiltrated body fabric is 78.5 degrees. The raw materials of the permeable green body fabric comprise other auxiliary agents besides mineral compositions. The auxiliary agent comprises a permeation assisting agent, a red assisting agent, a yellowing assisting agent, a toughening agent, a reinforcing agent, a diluting agent and water glass. The permeation promoter can be 1-2wt% of the mineral composition of the green body fabric. The permeation aid used in the examples was purchased from XYTHO CHECTRIC Co., ltd., model number XTH-1830. The red assisting agent can be 0.3-1wt% of the mineral composition of the green body fabric. The red aid may be nano-silica. The yellowing promoter can be 0.3-1wt% of the mineral composition of the green body fabric. For example, the yellowing aid may be titanium dioxide. The toughening agent can be 1-2wt% of the mineral composition of the green body fabric. The reinforcing agent can be 0.3-1wt% of the mineral composition of the green body fabric. The diluent can be 0.3-1wt% of the mineral composition of the green body fabric. The water glass can be 0.3-1wt% of the mineral composition of the green body fabric.
Weighing the raw materials according to the raw material composition of the permeable green body fabric, adding water, ball-milling uniformly, and granulating by a spray tower. The grain composition of the permeable green body fabric comprises the following components in percentage by mass: 30 mesh or more: 20-30%;30 to 80 mesh: 60-70%; below 80 meshes less than or equal to 10 percent. Wherein, above 30 mesh refers to the part which stays on the 30 mesh screen, and below 80 mesh refers to the part which passes through the 80 mesh screen. The permeable green body fabric with the grain composition can ensure the forming performance of green bricks. The moisture content of the permeable green body fabric is preferably controlled to be 8.5+/-3 wt%.
In order to fully promote the color development of the penetrating ink and promote the color development of the blank body, the penetrating blank body fabric is designed, excessive calcium and sodium are not easy to introduce, and the high potassium and high silicon are more favorable for forming a glass phase and improving the color development of the blank body, namely the novel penetrating blank body fabric with high whiteness and bright color is specially designed, and meanwhile, the penetration and color development of the ink are more favorable through the addition of a color aid and the like.
And (3) distributing the penetrating blank substrate and the penetrating blank fabric by adopting a distribution system. A layer of penetrating blank substrate can be firstly laid to form a primer layer. For example, the primer layer may have a thickness of about 8-9mm. And then the base material layer is coated with penetrating blank fabric to form a fabric layer. For example, the thickness of the facing layer is about 2-3mm.
Note that spreading the frit a directly onto the infiltrated green body face material does not achieve the desired Gao Baigao infiltration function. The addition of the frit is more favorable for sintering the green body, improving the content of glass phase in the green body and reducing the porosity, and the components in the frit are required to be fused with other raw materials of the permeable fabric to be more favorable for improving the whiteness, color development and light transmittance of the green body.
And forming into a green body by using a press. For example, the press pressure is 122000KN and the number of molding times is 1.65 times/min. And (5) putting the green body into a drying kiln for drying. And after the drying is finished, sweeping and wetting the green body after the green body is discharged from the drying kiln. The blanks can be polished by a blank polishing machine before entering the drying kiln.
And (3) ink-jet printing the penetrating ink pattern on the surface of the blank body. Inkjet printing may be performed by an inkjet printer. Commercially available penetrating inks can be used.
Homemade penetrating inks may also be used. For example, the penetrating ink is mainly formulated of a metal salt, a stabilizer, and a polar solvent. Wherein, the mass content of the metal salt is 10-25%, the mass content of the stabilizer is 15-35%, and the mass content of the polar solvent is 40-65%. For example, the metal salt is a chloride salt including, but not limited to, ferric chloride, cobalt chloride, nickel chloride, cupric chloride, chromium chloride, and the like. For example, the stabilizers include, but are not limited to, neodecanoic acid, sodium isooctanoate, and the like. For example, the polar solvent is an alcohol ether solvent including, but not limited to, ethylene glycol butyl ether, ethylene glycol hexyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol dimethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tripropylene glycol butyl ether, tripropylene glycol methyl ether, diethylene glycol dibutyl ether, diethylene glycol hexyl ether, propylene glycol phenyl ether, and the like.
Drying the blank with the surface being subjected to ink-jet printing of the penetrating ink pattern. Drying may be performed using a drying line.
And (5) sintering. And (5) entering a kiln for sintering. The highest firing temperature can be 1215-1225 ℃ and the firing time can be 65-80 minutes.
Edging. Edging by an edging machine.
Polishing. Polishing or semi-polishing is performed using a polishing line. For example, the polishing pad is a fiber pad comprising: 400 mesh 5 group, 600 mesh 3 group, 800 mesh 2 group, 1000 mesh 2 group. The glossiness of the polished rock plate can reach about 95 degrees. Of course, polishing may not be performed.
And (5) packaging.
In order to further enrich the surface decoration effect of the rock plate, a crystal glaze can be applied to a blank body with the surface ink-jet printed with the penetrating ink pattern before firing.
The crystalline glaze comprises a base mineral and crystal nucleus dry grains. The basic mineral composition of the crystalline glaze comprises the following components in percentage by mass: frit B:25-50 percent of calcite: 10-15 percent of calcined zinc oxide: 5-10 percent of kaolin: 5-8%, calcined talc: 5-10 percent of sodium glass powder: 10-20% of titanium dioxide: 3-10%. The introduction of the frit B is beneficial to the effect of promoting crystallization during rapid firing of the roller kiln, and meanwhile, the firing vector can be reduced, and the influence of the fluctuation of other raw materials with different components on crystallization stability is reduced after the frit B is prepared. If the frit B is not introduced into the crystalline glaze, crystallization is unstable, and the crystal flowers are sparse or even can not be precipitated.
The chemical composition of the frit B comprises the following components in percentage by mass ：SiO2：40-65%;Al2O3：5-10%;CaO：10-15%;K2O：3-6%;ZnO：5-20%;TiO2：1-4%.
The mineral composition of the frit B comprises the following components in percentage by mass: 30-50% of potassium feldspar; quartz 10-20%; 3-10% of wollastonite; 3-5% of calcite; 10-20% of sodium glass powder; 1-3% of titanium dioxide; 5-10% of zinc oxide. Weighing the raw materials according to the mineral composition of the frit B, melting for 3-8 hours at 1350-1450 ℃ to obtain glass liquid, and then water quenching and crushing the glass liquid to obtain the frit B. The mesh size of the frit B may be 60-150 mesh.
The chemical composition of the sodium glass powder can comprise, in mass percent ：IL：0.1-0.9%;SiO2：30-60%;Al2O3：3-15%;Fe2O3：0.01-0.3%;TiO2：0.01-0.2%;CaO：5-15%;MgO：1-3%;K2O：0.3-3%;Na2O：3-15%.
The crystal nucleus dry grain in the crystal glaze accounts for 0.1-0.3wt% of the basic mineral. The effect of introducing the crystal nucleus dry particles is that the part which is not melted in the high-temperature melting process can form crystal nuclei, the crystal flower can be formed by taking the crystal nucleus dry particles as the center in the heat preservation and cooling process, and the formed crystal is more three-dimensional and has better morphology. If crystal nucleus dry particles are not introduced, uneven crystal flower formation or smaller crystal flower formation can be caused, even no crystal flower exists, and the three-dimensional effect is poorer.
The chemical composition of the crystal nucleus dry particle can comprise the following components in percentage by mass ：K2O：1-5%;Na2O：6-8%;SiO2：20-40%;Al2O3：5-10%;ZnO：30-50%;TiO2：3.0-8.0%.
The mineral composition of the crystal nucleus dry particles comprises the following components in percentage by mass: 20-40% of albite by mass percent; quartz 10-20%; 2-5% of calcined talc; 3-6% of kaolin; 3-8% of titanium dioxide; 30-50% of zinc oxide; 0.5 to 3.0 percent of cryolite. Weighing the raw materials according to the mineral composition of the crystal nucleus dry particles, melting for 5-8 hours at 1350-1450 ℃ to obtain glass liquid, and then water-quenching and crushing the glass liquid to obtain the crystal nucleus dry particles. The mesh number of the crystal nucleus dry particles is 40-80 meshes.
The chemical composition of the crystalline glaze comprises the following components in percentage by mass ：IL：0.5-3%;SiO2：20-50%;Al2O3：5-10%;CaO：5-15%;MgO：0.5-3.0%;K2O：2.0-4.0%;Na2O：1-3%;ZnO：10-30%;TiO2：5-10%.
The crystalline glaze may be applied by means of a glaze spray. When spraying glaze, water and auxiliary agent are mixed into glaze slurry. The auxiliary agent comprises sodium carboxymethyl cellulose and sodium tripolyphosphate. By way of example, sodium carboxymethylcellulose comprises 0.1-0.5% by weight of the crystalline glaze and sodium tripolyphosphate comprises 0.1-0.5% by weight of the crystalline glaze.
The specific gravity of the crystalline glaze is 1.55-1.60g/cm 3, and the application amount is 820-860g/m 2. The specific gravity and the application amount of the crystal glaze are low, so that less crystal flowers or even no crystal flowers are separated out; the higher specific gravity and the higher application amount of the crystal glaze can cause excessive crystal flower overlapping and uneven layering sense penetration sense, and influence the decoration of the ink-jet pattern.
According to the invention, the ceramic rock plate of the Gao Baigao-transmission ink-jet pattern-penetrating composite technology can be prepared by developing a ceramic blank penetrating backing material and a fabric formula with high whiteness and high permeability and vivid ink color, directly printing the pattern-penetrating ink on the ceramic blank with high whiteness and high permeability, combining with a vivid ink-jet design pattern, and then firing and polishing at a high temperature in a kiln. In addition, the invention can also be combined with a special crystal glaze to prepare the ceramic rock plate with special crystal flower patterns through kiln firing.
The present invention will be described in more detail by way of examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
The preparation method of the Gao Baigao ceramic rock plate by the inkjet infiltration composite process comprises the following steps:
Step 1, firstly, distributing a layer of penetrating blank base material to form a base material layer. The chemical components of the penetrating blank substrate in percentage by mass comprise ：IL：3.5%;SiO2：72.2%;Al2O3：16.5%;Fe2O3：0.2%;TiO2：0.1%;CaO：1.3%;MgO：1.2%;K2O：3%;Na2O：2%. the mineral components of the penetrating blank substrate in percentage by mass: guangxi white mud: 40%; gao Baigao kaolin: 15%; cloud water mill stone powder: 20% of a base; water milling potassium feldspar: 10%; gao Baina feldspar: 10%, wollastonite: 5%. The penetrating blank bottom material also comprises a toughening agent accounting for 1wt% of the penetrating blank bottom material mineral, a reinforcing agent accounting for 0.6wt% of the penetrating blank bottom material mineral, a diluting agent accounting for 0.6wt% of the penetrating blank bottom material mineral, and water glass accounting for 0.7wt% of the penetrating blank bottom material mineral. The primer layer had a thickness of about 9mm.
And 2, distributing the permeable blank fabric on the primer layer to form a fabric layer. The chemical components of the infiltrated body fabric comprise ：IL：2.9%;SiO2：71%;Al2O3：17.5%;Fe2O3：0.1%;TiO2：0.15%;CaO：1.15%;MgO：1.2%;K2O：3.5%;Na2O：2.5%., and the mineral composition of the infiltrated body fabric comprises the following components in percentage by mass: guangxi white mud: 30%; gao Baigao kaolin: 15%; cloud water mill stone: 20% of a base; water milling potassium feldspar: 15%; gao Baina feldspar: 10%, wollastonite: 5%, frit A:5%. The permeable green body fabric also comprises 1.5wt% of a permeation assisting agent, 0.6wt% of a red assisting agent, 0.6wt% of a yellowing assisting agent, 1.5wt% of a toughening agent, 0.6wt% of a reinforcing agent, 0.6wt% of a diluting agent and 0.6wt% of water glass. Wherein the chemical composition of the frit A comprises ：IL：0.25%;SiO2：66%;Al2O3：17%;Fe2O3：0.1%;TiO2：0.15%;CaO：5.3%;MgO：1.2%;K2O：5.5%;Na2O：4.5%. of the mineral composition of the frit A in percentage by mass: potassium feldspar: 45%; albite: 25%; quartz: 15%; wollastonite: 8%; 7% of water-washed kaolin. The whiteness of the infiltrated body fabric is about 78.5 degrees. The thickness of the facestock layer was about 3mm a.
And 3, forming the primer layer and the fabric layer into a green body by using a press.
And 4, putting the green body into a drying kiln for drying. And after the drying is finished, sweeping and wetting the green body discharged from the drying kiln.
And 5, after the green body is taken out of the drying kiln, printing a penetrating ink pattern on the surface of the green body in an inkjet mode.
And 6, drying the green body and then sintering in a kiln. The maximum firing temperature was 1225℃and the firing time was 75 minutes.
And 7, polishing. The polishing abrasive block is a fiber abrasive block comprising: 400 mesh 5 group, 600 mesh 3 group, 800 mesh 2 group, 1000 mesh 2 group.
From fig. 1, it can be seen that the product has bright color and strong stereoscopic impression. The glossiness of the polished rock plate reaches about 95 degrees.
Example 2
The preparation method of the Gao Baigao ceramic rock plate by the inkjet infiltration composite process comprises the following steps:
step 1, firstly, distributing a layer of penetrating blank base material to form a base material layer. The raw material composition and chemical composition of the infiltrated green body bed charge were the same as in example 1.
And 2, distributing the permeable blank fabric on the primer layer to form a fabric layer. The raw material composition and chemical composition of the infiltrated green fabric were the same as in example 1.
And 3, forming the primer layer and the fabric layer into a green body by using a press.
And 4, putting the green body into a drying kiln for drying. And after the drying is finished, sweeping and wetting the green body discharged from the drying kiln.
And 5, after the green body is taken out of the drying kiln, printing a penetrating ink pattern on the surface of the green body in an inkjet mode.
And 6, spraying crystalline glaze on the surface of the green body. The basic mineral of the crystalline glaze comprises the following components in percentage by mass: frit B:45%; calcite: 13%; calcining zinc oxide: 10%; kaolin: 7%; calcined talc: 7%; sodium glass powder: 15%; titanium dioxide: 3%. The chemical composition of the frit B comprises the following components in percentage by mass: siO 2：55%;Al2O3：7%;CaO：12%;K2O：4.5%;ZnO：18%;TiO2: 3.5%. The chemical composition of the sodium glass powder comprises ：IL：0.88%;SiO2：58%;Al2O3：12%;Fe2O3：0.01%;TiO2：0.01%;CaO：12%;MgO：1.5%;K2O：2.6%;Na2O：13%. crystal nucleus dry particles accounting for 0.2 weight percent of the crystal glaze basic mineral in percentage by mass. The chemical composition of the crystal nucleus dry particle comprises the following components in percentage by mass: k 2O：3%、Na2O：7%;SiO2：38%;Al2O3：9%;ZnO：38%;TiO2: 5%. The mineral composition of the crystal nucleus dry particles comprises the following components in percentage by mass: 30% of albite; 15% of quartz; 3% of calcined talc; 4.5% of kaolin; titanium dioxide 5.5%; zinc oxide 40%; 2% of cryolite. The specific gravity of the crystalline glaze was 1.58 g/cm 3 and the applied amount was 850g/m 2.
And 7, drying the green body and then sintering in a kiln. The maximum firing temperature was 1220℃and the firing time was 75 minutes.
And 8, polishing. The polishing abrasive block is a fiber abrasive block comprising: 400 mesh 5 group, 600 mesh 3 group, 800 mesh 2 group, 1000 mesh 2 group.
From fig. 2, it can be seen that the product has bright color and strong stereoscopic impression, and blue crystal flowers are interspersed in the product, so that the ceramic tile is more characterized.
Comparative example 1
Comparative example 1 is substantially identical to the solution of example 1, with the main difference that: comparative example 1 used a conventional high whiteness primer and a conventional high whiteness facing. The high white primer comprises the following raw materials in percentage by mass: 30% of Guangxi stone powder; mixing white sand 6%; 5% of southern ball clay; washing kaolin 13%, potassium feldspar powder 43%; pyrophyllite 3%. The chemical composition of the high-whiteness primer comprises ：IL：3.85%;SiO2：69.5%;Al2O3：19.7%;Fe2O3：0.1%;TiO2：0.15%;K2O：5.2%;Na2O：1.5%. raw materials of the high-whiteness primer in percentage by mass: 25% of Guangxi stone powder; mixing white sand 6%; 5% of southern ball clay; 13% of water-washed kaolin and 46% of potassium feldspar powder; 3% of pyrophyllite and 2% of wollastonite. The chemical composition of the high-whiteness fabric comprises IL：4.65%;SiO2：68.6%;Al2O3：19.2%;Fe2O3：0.1%;TiO2：0.15%;CaO：0.6%;K2O：5.5%;Na2O：1.2%. Guangxi stone powder by mass percent, ：IL：2.98%;SiO2：67.5%;Al2O3：17.7%;Fe2O3：0.2%;TiO2：0.15%;K2O：1.8%;Na2O：8.5%;CaO：0.92%;MgO：0.25%. and white sand by mass percent, ：IL：2.18%;SiO2：75.9%;Al2O3：14.7%;Fe2O3：0.1%;TiO2：0.05%;K2O：3.2%;Na2O：3.5%;CaO：0.22%;MgO：0.15%. southwest ball clay by mass percent ：IL：11.08%;SiO2：51.5%;Al2O3：32.7%;Fe2O3：0.4%;TiO2：0.15%;K2O：2.7%;Na2O：1.3%;CaO：0.12%;MgO：0.05%.
From fig. 3, it can be seen that the color development of the conventional base material and the conventional face material is weaker, and particularly yellow and red are not basically developed, and the overall vividness is deviated.
Comparative example 2
Comparative example 2 is substantially identical to the solution of example 2, with the main difference that: the crystal glaze adopts tungsten crystal glaze. The tungsten-based crystal glaze comprises the following raw materials in percentage by mass: 23% of potassium feldspar; 10% of albite; quartz 10%; sodium glass powder: 22%; kaolin 5%; tungsten oxide 30%. The sodium glass frit was the same as that used in example 2. The chemical composition of the tungsten-based crystalline glaze comprises the following components in percentage by mass ：IL：2.58%;SiO2：46.6%;Al2O3：11.5%;Fe2O3：0.1%;TiO2：0.02%;CaO：3.5%;K2O：3.5%;Na2O：3.2%;WO2：29.0%.
As can be seen from fig. 4, the tungsten-based crystalline glaze has poor transparency, high coverage to the blank, and poor combination with the inkjet pattern, so that a good decorative effect is not achieved, and the glaze surface with the tungsten-based crystalline glaze has obvious defects of more pores and poor transparency after polishing.
Comparative example 3
Comparative example 3 is essentially identical to the solution of example 1, with the main difference that: the frit used in the facing of comparative example 3 was different. The frit used in comparative example 3 had a chemical composition comprising in mass percent IL：0.2%;SiO2：48.7%;Al2O3：21%;Fe2O3：0.1%;TiO2：0.2%;CaO：13%;MgO：12%;K2O：1.5%;Na2O：3.3%.
As can be seen from fig. 5, the frit used had a rough glaze, a high gloss and a weak color development, especially a red-yellow deviation.
Comparative example 4
Comparative example 4 is substantially identical to the solution of example 2, with the main difference that: the crystalline glaze adopts zirconium-zinc crystalline glaze. The zirconium-zinc system crystal glaze comprises the following raw materials in percentage by mass: 40% of potassium feldspar; 15% of quartz; sodium glass powder: 10%; kaolin 5%; 10% of calcite; 2% of calcined talc; zinc oxide: 8%; zircon 10%. The sodium glass frit was the same as that used in example 2. The chemical composition of the zirconium-based crystalline glaze comprises the following components in percentage by mass ：IL：6.58%;SiO2：51.5%;Al2O3：13.5%;Fe2O3：0.01%;TiO2：0.01%;CaO：5.2%;K2O：5.0%;Na2O：3.1%;ZnO：8%;ZrO2：7.1%.
As can be seen from fig. 6, the tile surface is full of white crystals with star points, the crystal shape is single, the transmission deviation is poor compared with the crystal decoration effect of example 2.
Claims (10)
1. The preparation method of the high Bai Gaotou ink-jet pattern-penetrating composite technology ceramic rock plate is characterized by comprising the following steps of:
cloth penetrating the blank substrate to form a primer layer;
the base material layer is coated with penetrating blank fabric to form a fabric layer; the mineral composition of the permeable green body fabric comprises the following components in percentage by mass: guangxi white mud: 30-40%; gao Baigao kaolin: 10-20%; cloud water mill stone: 20-30%; water milling potassium feldspar: 10-15%; gao Baina feldspar: 10-15% of wollastonite: 5-15%, frit A:5-15%; the chemical composition of the frit A comprises the following components in percentage by mass ：IL：0.1-0.3%;SiO2：40-70%;Al2O3：15-20%;Fe2O3：0.1-0.2%;TiO2：0.05 -0.3%;CaO：3-6%;MgO：0.5-1.5%;K2O：4.0-6.0%;Na2O：2.0-5.0%;
Pressing the primer layer and the fabric layer into a blank;
ink-jet printing a penetrating ink pattern on the surface of the blank;
drying the blank body of which the surface is subjected to ink-jet printing of the penetrating ink pattern;
And (5) sintering.
2. The method of claim 1, wherein the mineral composition of the frit a comprises, in mass percent: potassium feldspar: 30-50%; albite: 10-30%; quartz: 5-20%; wollastonite: 3-10%; 5-15% of water-washed kaolin.
3. The method of claim 1, wherein the mineral composition of the infiltrated green body matrix comprises, in mass percent: guangxi white mud: 30-45%; gao Baigao kaolin: 10-20%; cloud water mill stone: 20-35%; water milling potassium feldspar: 10-15%; gao Baina feldspar: 10-15% of wollastonite: 5-15%.
4. The method of manufacturing according to claim 1, characterized in that the method of manufacturing further comprises: printing a blank Shi Jiejing glaze penetrating the ink pattern on the surface in an inkjet mode before firing; the crystal glaze comprises a base mineral and crystal nucleus dry grains; the basic mineral of the crystalline glaze comprises the following components in percentage by mass: frit B:25-50%; calcite: 10-15%; calcining zinc oxide: 5-10%; kaolin: 5-8%; calcined talc: 5-10%; sodium glass powder: 10-20%; titanium dioxide: 3-10%; the chemical composition of the frit B comprises the following components in percentage by mass ：SiO2：40-65%;Al2O3：5-10%;CaO：10-15%;K2O：3-6%;ZnO：5-20%;TiO2：1-4%.
5. The method according to claim 4, wherein the chemical composition of the soda glass powder comprises, in mass percent ：IL：0.1-0.9%;SiO2：30-60%;Al2O3：3-15%;Fe2O3：0.01-0.3%;TiO2：0.01-0.2%;CaO：5-15%;MgO：1-3%;K2O：0.3-3%;Na2O：3-15%.
6. The method according to claim 4, wherein the crystal nucleus dry particles account for 0.1 to 0.3wt% of the base mineral; the mineral composition of the crystal nucleus dry particles comprises the following components in percentage by mass: 20-40% of albite; quartz 10-20%; 2-5% of calcined talc; 3-6% of kaolin; 3-8% of titanium dioxide; 30-50% of zinc oxide; 0.5-3% of cryolite.
7. The method according to claim 4, wherein the crystalline glaze is applied by spraying; the specific gravity of the crystalline glaze is 1.55-1.60 g/cm 3, and the application amount is 820-860 g/m 2.
8. The method according to claim 1, wherein the firing temperature is 1215 to 1225 ℃ and the firing time is 65 to 80 minutes.
9. The method of manufacturing according to claim 1, further comprising polishing the fired green body.
10. Gao Baigao-penetration inkjet-penetration-patterning composite ceramic rock plate, characterized in that the Gao Baigao-penetration inkjet-penetration-patterning composite ceramic rock plate is obtained according to the preparation method of any one of claims 1 to 9.
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| US20230257297A1 (en) * | 2022-02-16 | 2023-08-17 | Guangdong Deer New Materials Co., Ltd. | Super-wear-resistant diamond glaze, ceramic tile and preparation method thereof |
| CN117142765A (en) * | 2023-08-09 | 2023-12-01 | 佛山市美添功能材料有限公司 | Low-zirconium ultra-white ceramic overglaze, glazed brick and preparation method thereof |
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| CN113979787A (en) * | 2021-11-05 | 2022-01-28 | 蒙娜丽莎集团股份有限公司 | High-wear-resistance pattern-penetrated polished porcelain tile and preparation method thereof |
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| US20230257297A1 (en) * | 2022-02-16 | 2023-08-17 | Guangdong Deer New Materials Co., Ltd. | Super-wear-resistant diamond glaze, ceramic tile and preparation method thereof |
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