CN115650769B - Frosted thin ceramic plate with ultra-flat glaze and fine texture and preparation method thereof - Google Patents
Frosted thin ceramic plate with ultra-flat glaze and fine texture and preparation method thereof Download PDFInfo
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- CN115650769B CN115650769B CN202211377164.7A CN202211377164A CN115650769B CN 115650769 B CN115650769 B CN 115650769B CN 202211377164 A CN202211377164 A CN 202211377164A CN 115650769 B CN115650769 B CN 115650769B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0023—Digital printing methods characterised by the inks used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- 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
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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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Abstract
The invention discloses a frosted thin ceramic plate with ultra-flat glaze and fine texture and a preparation method thereof. The preparation method comprises the following steps: forming a microstructure containing protrusions by ink jet printing ink on the surface of the blank; applying ground coat on the surface of the green body after ink is printed by ink jet; ink-jet printing a design pattern on the surface of the green body after the primer is applied; applying protective glaze on the surface of the green body after the design pattern is printed by ink jet; and drying and firing the green body after the protective glaze is applied to obtain the frosted thin ceramic plate with the ultra-flat glaze and fine texture.
Description
Technical Field
The invention relates to a frosted thin ceramic plate with ultra-flat glaze and fine texture and a preparation method thereof, belonging to the technical field of building ceramic production and manufacturing.
Background
Ceramic plates are favored by many designers because of their lightweight, thin, durable, and decorative properties. The ceramic plate is widely used in the decoration fields of wardrobe, panel and the like. However, the popularization and application of the ceramic plate also put higher requirements on the performance and preparation of the ceramic plate. In the production and manufacture of the existing thin ceramic plate, the traditional glazing process has high requirements on the green body strength. In order to reduce edge cracking and breakage of the ceramic plate, moisture brought by glazing must be strictly controlled, and rotted bricks caused by strength attenuation due to excessive moisture are prevented. The glaze decoration of the thin ceramic plate mainly comprises half-number glazing and full-number glazing. The half digital glazing adopts the traditional mode of spraying glaze and adding digital glaze, and the glaze layer is thinner and is difficult to fill up the concave-convex part on the surface of the green body due to the limit of glazing quantity, so the flatness of the glaze surface of the half digital glazing is greatly dependent on the inherent flatness of the surface of the green brick after compression molding. The full-code glazing is completely digital glaze, and no water spraying glaze is adopted, so that the flatness of the glaze surface is completely dependent on the inherent surface of the blank. Therefore, it is an object of the present invention to provide a thin ceramic plate with a rough surface, which has a smooth texture and an ultra-flat glaze, while ensuring the quality of the ceramic plate.
Disclosure of Invention
According to the frosted thin ceramic plate with the ultra-flat glaze and fine texture and the preparation method thereof, low-gray oily ink is printed on the surface of a green body in an inkjet mode to form a fine microstructure with protrusions on the surface of a coarse green body, in addition, the raised ink points forming the microstructure and the ground glaze drops applied subsequently have large interfacial tension, the moisture of the glaze is kept in the form of countless small glaze drops on the surface of the brick in the process of being absorbed by the green body, and finally, the frosted glaze effect of the protrusions of the microstructure is densely and evenly distributed after firing.
In a first aspect, the invention provides a method for preparing a frosted thin ceramic plate with ultra-flat glaze and fine texture. The preparation method comprises the following steps:
forming a microstructure containing protrusions by ink jet printing ink on the surface of the blank;
applying ground coat on the surface of the green body after ink is printed by ink jet;
ink-jet printing a design pattern on the surface of the green body after the primer is applied;
applying protective glaze on the surface of the green body after the design pattern is printed by ink jet;
and drying and firing the green body after the protective glaze is applied to obtain the frosted thin ceramic plate with the ultra-flat glaze and fine texture.
Preferably, the ink is white ink.
Preferably, the ink jet printing ink has a gray scale of 5 to 20%.
Preferably, the chemical composition of the primer includes: in mass percent, siO 2 ：45～50％、Al 2 O 3 : 16-19%, alkaline earth metal oxide: 9.0 to 16 percent of alkali metal oxide: 4.0 to 6.0 percent of ZrO 2 ：6.0～10％、ZnO：1.0～2.0％。
Preferably, the initial melting temperature of the primer is 1080-1130 ℃.
Preferably, the ground coat is applied by spraying glaze with the specific gravity of 1.40-1.45 g/cm 3 The glazing amount is 300-400 g/m 2 。
Preferably, the protective glaze is applied by ink-jet printing digital protective glaze.
Preferably, the chemical composition of the digital protection glaze comprises: in mass percent, siO 2 ：50～55％、Al 2 O 3 ：15～18％、CaO：15～20％、MgO：0.5～1.0％、K 2 O：0.1～0.5％、Na 2 O：4.0～5.0％、ZnO：4.0～6.0％。
Preferably, the specific gravity of the digital protective glaze is 1.15-1.35 g/cm 3 The glazing amount is 5-30 g/m 2 。
In a second aspect, the invention also provides a frosted thin ceramic plate with ultra-flat glaze and fine texture obtained by the preparation method.
Drawings
FIG. 1 is a flow chart of a process for preparing a frosted thin ceramic plate with ultra-flat glaze and fine texture according to an embodiment of the present invention;
FIG. 2 is a diagram showing the effect of the tile surface of a thin ceramic slab;
FIG. 3 is a diagram showing the effect of the tile surface of a frosted thin ceramic plate with ultra-flat glaze and fine texture;
FIG. 4 is a graph of the tile surface effect of comparative example 1;
FIG. 5 is a graph of the tile surface effect of comparative example 2;
FIG. 6 is a graph of the tile surface effect of comparative example 3;
FIG. 7 is a schematic illustration of a microstructure formed by ink jet printing ink;
fig. 8 is a pixel distribution diagram of an inkjet printed document.
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.
The following is an exemplary description of a method for preparing a frosted thin ceramic plate with ultra-flat glaze and fine texture according to the present invention with reference to fig. 1.
The ceramic base (which may also be referred to as "green body powder") is compression molded to obtain a green body of the ceramic plate. The chemical composition and the raw material composition of the ceramic base material are not limited, and the ceramic base material commonly used in the field can be adopted. As an example, the chemical composition of the ceramic base may include: in mass percent, siO 2 ：62～67％、Al 2 O 3 ：20～25％、Fe 2 O 3 ：0.06～0.1％、TiO 2 ：0.1～0.5％、CaO：0.1～0.5％、MgO：0.1～1.0％、K 2 O：2.0～3.0％、Na 2 O:2.5 to 3.5 percent of the flame-out: 4.5 to 6.5 percent. The green body is obtained in the examples specifically using conventional presses or belt molding. The resulting green body had poor surface flatness and exhibited roughness.
And drying the blank. Drying in a drying kiln may be used. For example, the drying time is 30-60 min, and the moisture of the dried green body is controlled to be 0.3-0.5 wt%.
And (3) performing ink jet printing on the surface of the dried green body to form a microstructure containing protrusions. The ink may be an oily ink, such as a white ink or a matte ink, in order to form fine structures on the rough green surface of the ink. The surface structure of the green body is relatively loose, the hydrophilicity is strong, and when the ground glaze is directly applied to the surface of the green body, the moisture in the glaze can quickly permeate into the green body, and the glaze surface is quickly dried. In order to avoid the rotten bricks of the thin ceramic plates with lower thickness specifications caused by the excessive introduction of water into the ground coat, the glazing amount of the ground coat is usually smaller. The two can not realize the frosting effect that the glaze is super flat and the texture is fine and smooth by directly applying the primer on the surface of the green body.
Preferably, the ink is a white ink. The composition of the white ink is not limited, and a white ink commonly used in the art may be used. Different from other color inks, the white ink has relatively high temperature, is favorable for forming matte texture, and plays a role in promoting the visual effect of the frosted surface. In addition, as described above, the moisture content introduced by the glaze needs to be strictly controlled in the glazing process to avoid cracking of the thin ceramic plate in the process of running the glaze line through the brick, but the insufficient application amount of the primer causes uneven surface of the blank body, and the problem of poor whiteness of the brick surface is solved, so that the white ink can well make up and solve the defects.
In some embodiments, the microstructures containing protrusions are rounded protruding microstructures formed by ink droplets (see fig. 7). The round bulges formed by the ink drops and the brick surfaces which are relatively concave around the bulges form a bionic lotus leaf structure. The diameter of the circular protrusions, the distance between adjacent protrusions, and the height of the protrusions relative to the brick surface can be adaptively changed. By way of example only, the circular protrusions have a diameter of 10-200 μm, a spacing between the protrusions of 30-400 μm, and a protrusion height of 40-90 μm.
The invention forms a microstructure by ink jet printing ink and is beneficial to forming a frosted surface with ultra-flat glaze and fine texture by matching with subsequent glazing. The desired microstructure is formed, in particular, by controlling the drop size, the nozzle resolution, and the gray scale. The droplet size is preferably 12 to 65pl (picoliters). The ink drop size can avoid the low microstructure fineness of ink jet printing caused by the overlarge ink drop, and can also avoid the influence of the overlarge ink drop caused by the rapid absorption of a blank bodyAnd (3) forming a microstructure. The nozzle resolution (number of pixels per inch) affects the number of ink drops per unit area. As can be seen from fig. 8, although the pixel dot distribution of the ink jet print file of fig. 8 appears in a checkered shape, in reality, since the nozzle holes of the ink jet print are circular, the ink droplets finally printed form dots. The ink drops are distributed on the surface of the green brick according to the ink jet printing file under the action of the resolution ratio of the spray head to form the microstructure. The nozzle resolution of the present invention is preferably 300 to 600DPI. In a particular embodiment of the invention, the ink jet print file is full, the distribution of the ink drops being controlled by resolution. The gray scale of the ink jet printing ink controls the amount of ink applied. The gray scale of the ink jet printing ink may be 0 to 100%, preferably 5 to 30%. Correspondingly, the application amount of the ink is 3-20 g/m 2 . The low gray level is more favorable for obtaining a fine microstructure on the surface of a rough green body, and is also more favorable for forming a frosted surface with ultra-flat glaze and fine texture. In some embodiments, the ink-jet printing ink has a gray scale of 5 to 20%, preferably 5 to 15%. The gray level of the ink for ink-jet printing exceeds the above range, and the state of the spray head has adverse effects on the glaze effect, in particular, the defects of oblique spray, pull lines, color marks and the like are generated after glazing. When printing in a multi-channel manner, the above-described gradation refers to the sum of the gradations of the respective channels of the ink-jet printing ink. The number of channels of the ink jet printing ink can be adjusted according to actual needs. For example, two-pass printing is used, each having a gray scale of 5 to 10%.
In the prior art, white ink is usually printed in an inkjet manner to cover the blank flaws and promote inkjet color development. The invention utilizes the oily effect of the ink, and forms a fine microstructure on the surface of the blank body through the low-gray oily ink, and the fine microstructure is favorable for controlling the fine frosted texture formed on the subsequent glaze surface.
And applying a primer on the surface of the green body after the ink is printed by the ink jet. The effect of applying the base glaze is to cover the base color and flaws of the green body, promote the color development of the ink-jet pattern, form uniform small liquid drops (glaze drops) under the effect of the oily ink microstructure, and be favorable for forming fine frosted texture after firing.
The chemical composition of the primer comprises: in mass percent，SiO 2 ：45～50％、Al 2 O 3 : 16-19%, alkaline earth metal oxide: 9.0 to 16 percent of alkali metal oxide: 4.0 to 6.0 percent of ZrO 2 :6.0 to 10 percent of ZnO:1.0 to 2.0 percent. The ground glaze contains a large amount of alkaline earth metal oxides, so that the ground glaze has fine and soft texture while low glossiness is realized.
For example, the chemical composition of the primer may include: in mass percent, siO 2 ：45～50％、Al 2 O 3 ：16～19％、Fe 2 O 3 ：0.16～0.46％、TiO 2 ：0.15～0.25％、CaO：3～4％、MgO：1.0～1.5％、K 2 O：1～2％、Na 2 O：3～4％、ZrO 2 : 6-10%, znO: 1-2%, baO: 5-10%, loss of burning: 5.0 to 8.0 percent. The barium oxide contained in the ground coat is also beneficial to improving the texture and color development of the glaze.
The initial melting temperature of the ground coat is 1080-1130 ℃. Therefore, the defect of prickly heat holes caused by unsmooth exhaust of the green body due to early melting of the glaze can be prevented, and the prickly heat protective coating has better texture and antifouling performance. However, the initial melting temperature of the ground glaze is too low, and the phenomenon of mutually melting the glaze drops occurs, so that the frosted texture is lost.
The mineral composition of the primer may include: 1 to 5 percent of alumina, 5 to 8 percent of quartz sand, 2 to 5 percent of calcined talcum, 10 to 20 percent of potassium feldspar, 25 to 35 percent of albite, 1 to 5 percent of zinc oxide, 8 to 12 percent of kaolin, 6 to 12 percent of barium carbonate, 8 to 15 percent of zirconium silicate and 10 to 20 percent of high-calcium high-aluminum frit.
The chemical composition of the high-calcium high-aluminum frit comprises: in mass percent, siO 2 ：48～53％、Al 2 O 3 ：22～28％、CaO：13～18％、MgO：1.0～1.5％、K 2 O：3.0～4.0％、Na 2 O:2.0 to 3.0 percent of BaO:0.1 to 0.5 percent. As an example, the chemical composition of the high calcium high aluminum frit may include: in mass percent, siO 2 ：48～53％、Al 2 O 3 ：22～28％、Fe 2 O 3 ：0.16～0.46％、TiO 2 ：0.15～0.25％、CaO：13～18％、MgO：1.0～1.5％、K 2 O：3.0～4.0％、Na 2 O:2.0 to 3.0 percent of BaO:0.1 to 0.5 percent of the flame-out: 0.1 to 0.5 percent.
When the ground coat is prepared, the mineral composition and water of the ground coat are uniformly mixed, and ball milling is carried out to prepare D 90 Base coat paste =38±5 μm. The particle size distribution can be determined by a particle size analyzer. An inkjet leveling agent can be added into the ground glaze to prevent the local glaze shrinkage phenomenon of the glaze slurry caused by the excessive oiliness of the surface of the blank body. In some embodiments, the inkjet leveling agent accounts for 0.01-0.05% of the mass of the ground coat mineral composition.
The primer may be applied by spraying. The ground glaze is sprayed on the surface of the green body, and the glaze surface is densely distributed and has the frosting effect of a raised microstructure after firing, because larger interfacial tension exists between atomized glaze drops and raised ink points on the surface, and moisture is kept in the form of countless small glaze drops in the process of being absorbed by the green body, so that the frosting effect is finally formed. The frosting effect is also related to the onset temperature of the primer. The glaze drops and levels when the initial melting temperature of the ground glaze is too low, so that the frosting effect is lost, and the glaze surface is too rough and the frosting surface is not fine and smooth due to the too high initial melting temperature of the ground glaze.
The specific gravity of the ground coat can be 1.40-1.45 g/cm 3 The glazing amount can be 300-400 g/m 2 . The glazing amount of the ground coat is too low, the liquid drop drying speed is too high, and the uniform liquid drop form cannot be maintained. The application amount of the ground coat is too high, the green body strength is reduced, and the glazed line has more rotten bricks.
And (3) carrying out ink-jet printing on the surface of the green body after the primer is applied. The color and texture of the ink jet printed design pattern is adapted to follow the layout.
And applying protective glaze on the surface of the green body after the design pattern is printed by ink jet to adjust the gloss of the glaze and protect the ink jet pattern. The mode of applying the protective glaze can be one of ink-jet printing digital protective glaze, spraying common protective glaze and spraying common protective glaze. The digital protective glaze is preferably printed by ink-jet printing, so that the moisture content introduced by glazing can be further reduced, and the strength of the ceramic plate is promoted to be improved.
Chemical composition of the digital protective glazeComprising the following steps: in mass percent, siO 2 ：50～55％、Al 2 O 3 ：15～18％、CaO：15～20％、MgO：0.5～1.0％、K 2 O：0.1～0.5％、Na 2 O:4.0 to 5.0 percent of ZnO:4.0 to 6.0 percent. As an example, the chemical composition of the digital protective glaze may include: in mass percent, siO 2 ：50～55％、Al 2 O 3 ：15～18％、Fe 2 O 3 ：0.05～0.15％、TiO 2 ：0.01～0.05％、CaO：15～20％、MgO：0.5～1.0％、K 2 O：0.1～0.5％、Na 2 O:4.0 to 5.0 percent of ZnO:4.0 to 6.0 percent of burning loss: 1.0 to 3.0 percent.
The glazing amount of the digital protective glaze can be adjusted according to the glossiness. In some embodiments, the specific gravity of the digital protective glaze is 1.15-1.35 g/cm 3 The glazing amount is 5-30 g/m 2 . The digital protection glaze has less glazing quantity, is convenient for adjusting the glossiness of the glaze surface, and can not influence the frosting effect generated on the brick surface. For example, the frosted thin ceramic plate with ultra-flat glaze and fine texture has a glaze gloss of 8-15 degrees.
And drying and firing the green body after the protective glaze is applied. The highest firing temperature can be 1180-1220 ℃. The firing period may be 60 to 100 minutes. For example, the maximum firing temperature is 1220 ℃.
And (5) edging and grading. Packaging and warehousing.
According to the frosted thin ceramic plate with the ultra-flat glaze and fine texture and the preparation method thereof, low-gray oily ink is printed on the surface of a green body in an inkjet mode to form a raised fine microstructure on the surface of a coarse green body, in addition, large interfacial tension exists between raised ink points forming the microstructure and ground glaze drops applied subsequently, the moisture of the glaze is kept in the form of countless small glaze drops on the surface of the brick in the process of being absorbed by the green body, and finally, the frosted glaze effect of the raised microstructure is densely and uniformly distributed after firing. As an example, the thickness of the thin ceramic plate may be 2 to 4mm. In some embodiments, the thin ceramic plate has a gauge of 1200-3200 mm by 600-1600 mm by 2.8-3.5 mm in length.
The present invention will be further illustrated by the following 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 frosted thin ceramic plate with the ultra-flat glaze and fine texture comprises the following steps:
step 1, dry-pressing a ceramic base material to form a green body;
step 2, drying the blank for 30-60 min, wherein the moisture of the dried blank is 0.3-0.5wt%;
step 3, forming a fine microstructure on the dried blank surface by double-channel ink-jet printing white ink, wherein the gray scale of the double channels is 5-10% respectively; the microstructure is a circular bulge microstructure formed by ink drops, the size of the ink drops is 12-65 pl, and the resolution of a nozzle is 300-600 DPI;
step 4, applying base enamel on the surface of the blank body after the white ink is printed by ink jet; the chemical composition of the primer comprises: in mass percent, siO 2 ：45～50％、Al 2 O 3 ：16～19％、Fe 2 O 3 ：0.16～0.46％、TiO 2 ：0.15～0.25％、CaO：3.0～4.0％、MgO：1.0～1.5％、K 2 O：1.0～2.0％、Na 2 O：3.0～4.0％、ZrO 2 :6.0 to 10 percent of ZnO:1.0 to 2.0 percent of BaO:5.0 to 10 percent of the flame retardant: 5.0 to 8.0 percent; the specific gravity of the ground coat is 1.40-1.45 g/cm 3 The glazing amount is 300-400 g/m 2 ；
Step 5, ink-jet printing patterns on the surface of the green body after the primer is applied;
step 6, ink-jet printing digital protective glaze on the surface of the blank body after the pattern is ink-jet printed; the chemical composition of the digital protective glaze comprises: in mass percent, siO 2 ：50～55％、Al 2 O 3 ：15～18％、Fe 2 O 3 ：0.05～0.15％、TiO 2 ：0.01～0.05％、CaO：15～20％、MgO：0.5～1.0％、K 2 O：0.1～0.5％、Na 2 O:4.0 to 5.0 percent of ZnO:4.0 to 6.0 percent of burning loss: 1.0 to 3.0 percent; the specific gravity of the digital protective glaze is 1.15-1.35 g/cm 3 The glazing amount is 5-30 g/m 2 ；
Step 7, drying and sintering the green body subjected to the ink-jet printing of the digital protective glaze, wherein the maximum sintering temperature is 1220 ℃, and the sintering period is 60-100 minutes;
step 8, edging and grading; packaging and warehousing.
Fig. 2 is a graph of the effect of the green body obtained by directly firing the green body in step 2, and the surface flatness of the green body is poor. Fig. 3 is a diagram showing the effect of the tile surface of the frosted thin ceramic plate with ultra-flat glaze and fine texture. Fig. 2 and 3 have a visually distinct difference.
Comparative example 1
The preparation method of the thin ceramic plate comprises the following steps:
step 1, dry-pressing a ceramic base material to form a green body;
step 2, drying the blank for 30-60 min, wherein the moisture of the dried blank is 0.3-0.5wt%;
step 3, applying ground enamel on the surface of the dried green body; the chemical composition of the primer comprises: in mass percent, siO 2 ：45～50％、Al 2 O 3 ：16～19％、Fe 2 O 3 ：0.16～0.46％、TiO 2 ：0.15～0.25％、CaO：3.0～4.0％、MgO：1.0～1.5％、K 2 O：1.0～2.0％、Na 2 O：3.0～4.0％、ZrO 2 :6.0 to 10 percent of ZnO:1.0 to 2.0 percent of BaO:5.0 to 10 percent of the flame retardant: 5.0 to 8.0 percent; the specific gravity of the ground coat is 1.40-1.45 g/cm 3 The glazing amount is 300-400 g/m 2 ；
Step 4, ink-jet printing patterns on the surface of the green body after the primer is applied;
step 5, ink-jet printing digital protective glaze on the surface of the blank body after the pattern is ink-jet printed; chemical composition package of the digital protective glazeThe method comprises the following steps: in mass percent, siO 2 ：50～55％、Al 2 O 3 ：15～18％、Fe 2 O 3 ：0.05～0.15％、TiO 2 ：0.01～0.05％、CaO：15～20％、MgO：0.5～1.0％、K 2 O：0.1～0.5％、Na 2 O:4.0 to 5.0 percent of ZnO:4.0 to 6.0 percent of burning loss: 1.0 to 3.0 percent; the specific gravity of the digital protective glaze is 1.15-1.35 g/cm 3 The glazing amount is 5-30 g/m 2 ；
Step 6, drying and sintering the green body subjected to the ink-jet printing of the digital protective glaze, wherein the maximum sintering temperature is 1220 ℃, and the sintering period is 60-100 minutes;
step 7, edging and grading; packaging and warehousing.
As shown in fig. 4, the surface of the brick after firing has no frosted texture, because the step of ink-jet printing of oily ink is omitted, the application amount of the primer is low, the moisture in the primer quickly permeates into the green body, the ejected glaze falls on the surface of the brick blank to be immediately dried by water, and the surface of the brick cannot be kept in the shape of small liquid drops, so that projections with frosted texture can be obtained by firing.
Comparative example 2
The preparation method of the thin ceramic plate comprises the following steps:
step 1, dry-pressing a ceramic base material to form a green body;
step 2, drying the blank for 30-60 min, wherein the moisture of the dried blank is 0.3-0.5wt%;
step 3, forming a microstructure by performing two-channel ink-jet printing on the dried blank surface, wherein the gray scale of the two channels is 15% respectively; the ink drop size is 12-65 pl; the resolution of the spray head is 300-600 DPI;
step 4, applying base enamel on the surface of the blank body after the white ink is printed by ink jet; the chemical composition of the primer comprises: in mass percent, siO 2 ：45～50％、Al 2 O 3 ：16～19％、Fe 2 O 3 ：0.16～0.46％、TiO 2 ：0.15～0.25％、CaO：3.0～4.0％、MgO：1.0～1.5％、K 2 O：1.0～2.0％、Na 2 O：3.0～4.0％、ZrO 2 ：6.0～10％、ZnO：1.0～2.0％BaO:5.0 to 10 percent of the flame retardant: 5.0 to 8.0 percent; the specific gravity of the ground coat is 1.40-1.45 g/cm 3 The glazing amount is 300-400 g/m 2 ；
Step 5, ink-jet printing patterns on the surface of the green body after the primer is applied;
step 6, ink-jet printing digital protective glaze on the surface of the blank body after the pattern is ink-jet printed; the chemical composition of the digital protective glaze comprises: in mass percent, siO 2 ：50～55％、Al 2 O 3 ：15～18％、Fe 2 O 3 ：0.05～0.15％、TiO 2 ：0.01～0.05％、CaO：15～20％、MgO：0.5～1.0％、K 2 O：0.1～0.5％、Na 2 O:4.0 to 5.0 percent of ZnO:4.0 to 6.0 percent of burning loss: 1.0 to 3.0 percent; the specific gravity of the digital protective glaze is 1.15-1.35 g/cm 3 The glazing amount is 5-30 g/m 2 ；
Step 7, drying and sintering the green body subjected to the ink-jet printing of the digital protective glaze, wherein the maximum sintering temperature is 1220 ℃, and the sintering period is 60-100 minutes;
step 8, edging and grading; packaging and warehousing.
As shown in FIG. 5, the glaze effect after firing is poor, and the state of the spray head mainly reacts on the brick surface directly. This is because the droplets of ink are uniformly distributed on the green brick surface according to the nozzle resolution to form the microstructure. The microstructure protrusions of this comparative example were relatively reduced and the ink droplets began to blend with each other. When the gray level of the ink for ink-jet printing exceeds a specific range, the state of the spray head has a larger influence on the glaze effect, and the defects of oblique spray of the spray head, stay wires, color marks and the like can be seen on the brick surface after the glazed brick surface is subjected to the test after the ink with high gray level is printed.
Comparative example 3
The preparation method of the thin ceramic plate comprises the following steps:
step 1, dry-pressing a ceramic base material to form a green body;
step 2, drying the blank for 30-60 min, wherein the moisture of the dried blank is 0.3-0.5wt%;
step 3, forming a fine microstructure on the dried blank surface by double-channel ink-jet printing white ink, wherein the gray scale of the double channels is 5-10% respectively; a circular convex microstructure formed by ink drops, wherein the size of the ink drops is 12-65 pl; the resolution of the spray head is 300-600 DPI;
step 4, applying base enamel on the surface of the blank body after the white ink is printed by ink jet; the chemical composition of the primer comprises: in mass percent, siO 2 ：45～50％、Al 2 O 3 ：10～12％、Fe 2 O 3 ：0.16～0.46％、TiO 2 ：0.15～0.25％、CaO：6.0～8.0％、MgO：3.0～5.0％、K 2 O：3.0～4.0％、Na 2 O：1.0～2.0％、ZrO 2 : 6-10%, znO:1.0 to 2.0 percent of BaO:5.0 to 10 percent of the flame retardant: 5.0 to 8.0 percent; the specific gravity of the ground coat is 1.40-1.45 g/cm 3 The glazing quantity is 300-400 g/m 2 ；
Step 5, ink-jet printing patterns on the surface of the green body after the primer is applied;
step 6, ink-jet printing digital protective glaze on the surface of the blank body after the pattern is ink-jet printed; the chemical composition of the digital protective glaze comprises: in mass percent, siO 2 ：50～55％、Al 2 O 3 ：15～18％、Fe 2 O 3 ：0.05～0.15％、TiO 2 ：0.01～0.05％、CaO：15～20％、MgO：0.5～1.0％、K 2 O：0.1～0.5％、Na 2 O:4.0 to 5.0 percent of ZnO:4.0 to 6.0 percent of burning loss: 1.0 to 3.0 percent; the specific gravity of the digital protective glaze is 1.15-1.35 g/cm 3 The glazing amount is 5-30 g/m 2 ；
Step 7, drying and sintering the green body subjected to the ink-jet printing of the digital protective glaze, wherein the maximum sintering temperature is 1220 ℃, and the sintering period is 60-100 minutes;
step 8, edging and grading; packaging and warehousing.
As shown in fig. 6, the baked brick surface is melted and has no frosted texture, because the initial melting temperature of the ground glaze is low, so that the glaze surface is completely melted and has no frosted texture formed by the glaze drops.
Claims (8)
1. The preparation method of the frosted thin ceramic plate with the ultra-flat glaze and fine texture is characterized by comprising the following steps of:
forming a microstructure containing circular protrusions on the surface of the green body by ink-jet printing of oily ink, wherein the diameter of the circular protrusions is 10-200 mu m, the distance between the protrusions is 30-400 mu m, the height of the protrusions is 40-90 mu m, and the gray level of the ink-jet printing of the oily ink is 5-30%;
applying a primer on the surface of the green body after the oil ink is printed by ink jet, wherein the particle size distribution of the primer glaze slurry particles is D 90 =38±5 μm, the chemical composition of the primer comprises: in mass percent, siO 2 ：45～50%、Al 2 O 3 : 16-19%, alkaline earth metal oxide: 9.0 to 16 percent of alkali metal oxide: 4.0 to 6.0 percent of ZrO 2 :6.0 to 10 percent of ZnO:1.0 to 2.0 percent, wherein the initial melting temperature of the ground coat is 1080 to 1130 ℃;
ink-jet printing a design pattern on the surface of the green body after the primer is applied;
applying protective glaze on the surface of the green body after the design pattern is printed by ink jet;
and drying and firing the green body after the protective glaze is applied to obtain the frosted thin ceramic plate with the ultra-flat glaze and fine texture.
2. The method of claim 1, wherein the oily ink is a white ink.
3. The method of claim 1, wherein the ink jet printing oily ink has a gray scale of 5 to 20%.
4. The method according to claim 1, wherein the primer is applied by spraying a glaze with a specific gravity of 1.40-1.45 g/cm 3 The glazing amount is 300-400 g/m 2 。
5. The method of claim 1, wherein the protective glaze is applied by ink-jet printing a digital protective glaze.
6. The preparation method according to claim 5, characterized in thatThe chemical composition of the digital protective glaze comprises: in mass percent, siO 2 ：50～55%、Al 2 O 3 ：15～18%、CaO：15～20%、MgO：0.5～1.0%、K 2 O：0.1～0.5%、Na 2 O：4.0～5.0%、ZnO：4.0～6.0%。
7. The method according to claim 5, wherein the specific gravity of the digital protective glaze is 1.15-1.35 g/cm 3 The glazing amount is 5-30 g/m 2 。
8. The frosted thin ceramic plate with ultra-flat glaze and fine texture obtained by the preparation method according to claim 1.
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| CN106915197B (en) * | 2017-01-23 | 2020-06-12 | 蒙娜丽莎集团股份有限公司 | Preparation method of stacked ceramic plate decorative picture |
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