CN114956573A - Waxy glaze, waxy 3D ceramic tile and preparation method thereof - Google Patents
Waxy glaze, waxy 3D ceramic tile and preparation method thereof Download PDFInfo
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- CN114956573A CN114956573A CN202210914169.2A CN202210914169A CN114956573A CN 114956573 A CN114956573 A CN 114956573A CN 202210914169 A CN202210914169 A CN 202210914169A CN 114956573 A CN114956573 A CN 114956573A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
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- 239000006229 carbon black Substances 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 46
- 239000002689 soil Substances 0.000 claims description 40
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 32
- 238000010304 firing Methods 0.000 claims description 28
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- 238000007639 printing Methods 0.000 claims description 23
- 239000011787 zinc oxide Substances 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 19
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- 239000005995 Aluminium silicate Substances 0.000 claims description 16
- 235000012211 aluminium silicate Nutrition 0.000 claims description 16
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 229910052903 pyrophyllite Inorganic materials 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
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- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 229910021538 borax Inorganic materials 0.000 claims description 9
- 239000011449 brick Substances 0.000 claims description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 9
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 229920000178 Acrylic resin Polymers 0.000 claims description 8
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 229910052642 spodumene Inorganic materials 0.000 claims description 8
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 8
- 239000000454 talc Substances 0.000 claims description 8
- 229910052623 talc Inorganic materials 0.000 claims description 8
- 239000010456 wollastonite Substances 0.000 claims description 8
- 229910052882 wollastonite Inorganic materials 0.000 claims description 8
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000010459 dolomite Substances 0.000 claims description 7
- 229910000514 dolomite Inorganic materials 0.000 claims description 7
- 239000000375 suspending agent Substances 0.000 claims description 7
- 238000007641 inkjet printing Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 230000001846 repelling effect Effects 0.000 claims description 3
- 238000002834 transmittance Methods 0.000 abstract description 13
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- 239000013078 crystal Substances 0.000 description 10
- 238000005507 spraying Methods 0.000 description 9
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- 238000012360 testing method Methods 0.000 description 7
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- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
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- 229920000609 methyl cellulose Polymers 0.000 description 3
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- 239000011148 porous material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 2
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- 241001270131 Agaricus moelleri Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- -1 borate ions Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
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- 229910010293 ceramic material Inorganic materials 0.000 description 1
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- 239000002537 cosmetic Substances 0.000 description 1
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- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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Images
Classifications
-
- 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
- C03C8/22—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions containing two or more distinct frits having different compositions
-
- 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
-
- 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
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Structural Engineering (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a waxy glaze, a waxy 3D ceramic tile and a preparation method thereof, and relates to the technical field of ceramics, wherein the waxy glaze comprises the following components in parts by weight: 40-50 parts of first frit and 30-40 parts of second frit; according to the mass percentage, the preparation raw material of the first frit contains 7.5-12% of white carbon black, and the preparation raw material of the second frit contains 4.6-7.6% of nano alumina and 5.5-9.5% of white carbon black. The waxy glaze is a matte glaze, the frit is used as the main component, the porosity of the fired glaze can be reduced, the transparency of the glaze is greatly improved, and the frit can still have good light transmittance under the condition that the glaze is thick, and meanwhile, the frit can improve the fineness and the softness of the glaze, so that the glaze has the waxy texture like jade.
Description
Technical Field
The invention relates to the technical field of ceramics, in particular to a waxy glaze, a waxy 3D ceramic tile and a preparation method thereof.
Background
With the popularity of matte products in recent years, the development of the matte ceramic tiles is more rapid, and the matte products are deeply loved by consumers with soft light sensation. At present, most of matte glaze products have gloss of 8-15 degrees, and although the light sense is soft, the defects of rough texture and dark light sense generally exist, and the prior art does not have the hand feeling of the matte glaze ceramic tile surface like jade.
In addition, the matte glaze material in the prior art mainly utilizes a mode of separating out crystals during firing of divalent oxides to generate a matte effect, the matte effect is obvious when the glaze surface is thin, but the thick and heavy feeling is poor, however, when the glaze surface is thick and has the thick and heavy feeling, the transparency of the glaze surface is greatly weakened due to crystallization of the glaze surface and the existence of porosity in the glaze surface.
It is seen that improvements and enhancements to the prior art are needed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a waxy glaze, a waxy 3D ceramic tile and a preparation method thereof, and aims to overcome the technical defect of poor permeability of the waxy glaze in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the waxy glaze comprises the following components in parts by weight: 40-50 parts of first frit and 30-40 parts of second frit; according to the mass percentage, the preparation raw material of the first frit contains 7.5-12% of white carbon black, and the preparation raw material of the second frit contains 4.6-7.6% of nano alumina and 5.5-9.5% of white carbon black.
In the waxy glaze, the preparation raw materials of the first frit comprise, by weight: 15-18 parts of kaolin, 6-8 parts of zinc oxide, 3-6 parts of sodium borate, 25-36 parts of pyrophyllite, 8-12 parts of white carbon black, 5-8 parts of strontium carbonate, 10-13 parts of sodium carbonate, 12-15 parts of barium carbonate and 3-5 parts of wollastonite.
In the waxy glaze, the second frit comprises the following raw materials in parts by weight: 20-25 parts of kaolin, 5-8 parts of nano alumina, 10-15 parts of potassium carbonate, 5-8 parts of sodium carbonate, 10-15 parts of spodumene, 6-10 parts of white carbon black, 4-7 parts of talc and 30-36 parts of pyrophyllite.
In the waxy glaze, the preparation raw materials of the waxy glaze further comprise: 8-12 parts of air knife soil, 3-5 parts of zinc oxide and 5-8 parts of dolomite.
A waxy 3D ceramic tile comprises a tile blank layer, a makeup soil layer, a surface glaze layer, a pattern layer and a waxy glaze layer which are sequentially stacked, wherein sunken textures are further arranged in the surface glaze layer, the pattern layer and the waxy glaze layer, and the waxy glaze layer is prepared from the waxy glaze material.
In the waxy 3D tile, the texture is prepared by repelling the glaze layer and the waxy glaze layer with a mold ink, wherein the mold ink comprises, in mass percent: 38-48% of waxy glaze, 20-30% of acrylic resin, 20-30% of ethyl acetate, 3-6% of dispersing agent, 0.1-0.2% of suspending agent, 0.2-0.3% of defoaming agent, 0.3-0.6% of flatting agent and 0.15% of pH value regulator.
In the waxy 3D ceramic tile, the chemical composition of the overglaze layer comprises the following components in percentage by mass: SiO 2 2 50～55%、Al 2 O 3 23～28%、CaO 1.5～3.1%、MgO 2.5～3.0%、K 2 O 3.5～4.5%、Na 2 O2.1-4.1%, ZnO 4.5-6.5%, and the balance of ignition loss and trace impurities.
In the waxy 3D ceramic tile, the chemical composition of the makeup soil layer comprises the following components in percentage by mass: al (Al) 2 O 3 26～32%、SiO 2 55～60%、CaO 1.5～2.3%、MgO 1.3～2.4%、K 2 O 3.5～4.6%、Na 2 O3.8-4.6%, and trace impurities and ignition loss in balance.
A preparation method of the waxy 3D tile as described above, wherein the preparation method comprises the following steps in sequence:
sequentially forming a brick blank layer and a makeup soil layer;
depositing first mould ink on the surface of the makeup soil layer, and forming a glaze layer on the surface of the first mould ink;
and forming a pattern layer on the surface of the overglaze layer, depositing second mould ink on the surface of the pattern layer, forming a waxy glaze layer on the surface of the second mould ink, and sintering to obtain the waxy 3D ceramic tile.
In the preparation method of the waxy 3D ceramic tile, the method for depositing the first mould ink and the method for depositing the second mould ink are both ink-jet printing methods, and the printing gray scale is 40-100%; in the firing step, the firing temperature is 1180-1300 ℃, and the firing time is 40-60 minutes.
Has the advantages that:
the invention provides a waxy glaze which is a matte glaze, the main component of the waxy glaze is a frit, organic matters and carbonates in each component are decomposed and discharged in advance due to the fact that the frit is calcined in advance, when the frit is calcined together with a blank, the porosity of pores in the glaze is greatly reduced, the transparency of the glaze can be greatly improved, and the frit still has good light transmittance under the condition that the thickness of the glaze is thick.
The invention also provides a waxy 3D ceramic tile, which comprises a tile blank layer, a makeup soil layer, a surface glaze layer, a pattern layer and a waxy glaze layer, wherein through depositing hydrophobic mold ink on the makeup soil layer and the pattern layer, sunken textures can be formed in the surface glaze layer, the pattern layer and the waxy glaze layer, so that the ceramic tile has a 3D stereoscopic effect. Meanwhile, the waxy glaze layer is prepared from waxy glaze materials, accumulation is formed through the repulsion action of mold ink, the waxy glaze materials can improve the fineness of the ceramic tile, the accumulated position has a heavy feeling, and meanwhile, the waxy glaze layer has good permeability, so that the pattern layer can be well displayed and simultaneously has a waxy texture like jade.
The invention also provides a preparation method of the waxy 3D ceramic tile, which can repel the hydrophilic overglaze layer and the waxy glaze by printing the hydrophobic mold ink on the makeup soil layer and the pattern layer so as to form sunken textures, and the waxy glaze layer positioned on the uppermost surface has fine texture and good light transmission, so that the waxy effect can be formed while the 3D effect is achieved, and the ornamental value of the ceramic tile is greatly improved.
Drawings
Fig. 1 is a schematic structural diagram of a waxy 3D tile provided by the present invention.
FIG. 2 is a pictorial representation of the tile of example 5.
Fig. 3 is a pictorial representation of the tile of example 6.
Figure 4 is a pictorial representation of the tile of example 7.
Fig. 5 is a pictorial view of the tile of example 8.
Fig. 6 is a pictorial representation of the tile of comparative example 1.
Fig. 7 is a pictorial representation of the tile of comparative example 2.
Fig. 8 is a pictorial representation of a tile according to comparative example 3.
Fig. 9 is a pictorial representation of a tile according to comparative example 4.
Fig. 10 is a pictorial representation of a tile according to comparative example 5.
Fig. 11 is a pictorial representation of a tile according to comparative example 6.
Fig. 12 is a pictorial representation of a tile according to comparative example 7.
Fig. 13 is a pictorial representation of a tile according to comparative example 8.
Figure 14 is an enlarged view, at 150 x magnification, of a portion of the tile described in comparative example 1.
Figure 15 an enlargement of a part of the tile according to example 5, magnified 150 times.
Figure 16 is an SEM image of the tile described in example 5.
In the drawings, the reference numbers: 1-blank, 2-cosmetic soil layer, 3-surface glaze layer, 4-pattern layer, 5-wax glaze layer and 6-texture.
Detailed Description
The invention provides a waxy glaze, a waxy 3D ceramic tile and a preparation method thereof, and the invention is further detailed by the following embodiments in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a waxy glaze, which comprises the following components: 40-50 parts of first frit and 30-40 parts of second frit; according to the mass percentage, the preparation raw material of the first frit contains 7.5-12% of white carbon black, and the preparation raw material of the second frit contains 4.6-7.6% of nano alumina and 5.5-9.5% of white carbon black. The waxy glaze is a matte glaze, the main component of the waxy glaze is a frit, and the frit needs to be calcined at high temperature for melting during preparation, so that organic matters, carbonate and structural water in the components can be discharged in the process of high-temperature calcination for melting, the porosity is reduced (as shown in fig. 15, pores are very few after the waxy glaze is fired), the transparency and the fine greasy feeling of the glaze are greatly increased, the glaze still has good light transmittance under the condition of thick thickness, and the technical problem that the existing glaze is easy to lose transparency when the thickness is too thick is solved.
Moreover, 7.5-12 wt% of white carbon black is added in the raw material for preparing the first frit, 4.6-7.6 wt% of nano alumina and 5.5-9.5 wt% of white carbon black are added in the raw material for preparing the second frit, and the white carbon black and the nano alumina have very small particle sizes and good dispersibility, so that in the frit preparation process, the white carbon black and the nano alumina can fully react with oxides in the raw materials to form a glass phase or a crystal (as shown in fig. 16, a great amount of glass phase and crystal can be observed to be formed after the waxy glaze is fired through an SEM (scanning electron microscope) diagram), so that the waxy glaze taking the first frit and the second frit as main raw materials has fine texture and is warm and moist like jade.
However, since both the first frit and the second frit are ridge-like materials, they are easily precipitated in the glaze slip. In contrast, 8-12 parts of air knife soil is added into the waxy glaze, and the air knife soil has good suspension property, so that the sedimentation of ridge materials can be avoided, and the stability of glaze slip is improved. However, refractory alumina and silica are introduced into the added air-knife soil, so that the firing temperature of the glaze is increased, and 3-5 parts of zinc oxide and 5-8 parts of dolomite are further added into the waxy glaze as fluxing agents to reduce the firing temperature of the glaze.
In one embodiment, the first frit is prepared from the following raw materials in parts by weight: 15-18 parts of kaolin, 6-8 parts of zinc oxide, 3-6 parts of sodium borate, 25-36 parts of pyrophyllite, 8-12 parts of white carbon black, 5-8 parts of strontium carbonate, 10-13 parts of sodium carbonate, 12-15 parts of barium carbonate and 3-5 parts of wollastonite. Wherein the kaolin is used to provide Al forming the main skeleton 2 O 3 And SiO 2 Providing a basis for forming various crystals; the zinc oxide, the barium carbonate, the strontium carbonate and the wollastonite can respectively provide divalent oxides of ZnO, BaO, SrO and CaO, have a fluxing function and can be used as a high-temperature fluxing agent; the sodium borate and the sodium carbonate provide a monovalent oxide Na 2 O is used as a low-temperature fusing agent, and meanwhile, the sodium borate can also provide borate ions, so that the wear resistance of the glaze is improved; the white carbon black belongs to nano-scale SiO 2 The quartz glaze with smaller grain size has higher dispersity compared with quartz with larger grain size, can fully react with divalent oxides to form a glass phase with fine texture, has good light transmittance, solves the problem of rough hand feeling after firing the quartz with common grain size, and ensures that the glaze surface has fine and smooth hand feeling like jade; the pyrophyllite can provide Al in the form of silicate 2 O 3 And SiO 2 Compared to SiO in the form of an independent oxide 2 And Al 2 O 3 After being fired, the pyrophyllite can be fully combined with flux to form a crystalline phase, thereby solving the problem that SiO exists in the form of oxide 2 And Al 2 O 3 The fineness of the handfeel of the glaze is easy to reduce.
In one embodiment, the second frit is prepared from the following raw materials in parts by weight: 20-25 parts of kaolin, 5-8 parts of nano alumina, 10-15 parts of potassium carbonate, 5-8 parts of sodium carbonate, 10-15 parts of spodumene, 6-10 parts of white carbon black, 4-7 parts of talc and 30-36 parts of pyrophylliteAnd (4) portions are obtained. Wherein the kaolin and pyrophyllite function as the first frit; the potassium carbonate, sodium carbonate and spodumene can respectively provide monovalent low-temperature oxide flux K 2 O、Na 2 O、Li 2 O, and can form a melting effect with gradient temperature change, so that all components are fully melted to form a glass phase or crystal, and the existence of free quartz is avoided; the particle size of the nano alumina is in a nano level, the nano alumina is very fine, and has the characteristics of good dispersibility and large specific surface area, in the firing process, the nano alumina can react with an oxide solvent to form a zinc-aluminum spinel crystal, and the zinc-aluminum spinel crystal has soft glossiness and exquisite texture, so that the waxy glaze has the effect of being moist like jade; the talc may increase the smoothness of the glaze.
Furthermore, the raw materials of the first frit contain more divalent oxide fluxing agents, and the raw materials of the second frit contain more monovalent oxide fluxing agents, so that the firing temperatures of the first frit and the second frit are different, and therefore when the adding proportion of the first frit and the second frit is different, waxy glazes with different firing temperatures can be obtained, the range of adjustable firing temperatures of the waxy glazes is wide, and the adaptability is better.
The frit comprises a first frit and a second frit, and is prepared by calcining at high temperature, melting and cooling, wherein the first frit and the second frit are prepared from special raw materials, and the special raw materials enable the frit to have fine texture and transparent texture after being calcined at high temperature, so that glaze added with the first frit and the second frit has soft glossiness, fine texture and good light transmittance, and can meet the dual requirements of consumers on the heavy feeling and the transparent feeling.
The invention also provides a waxy 3D ceramic tile, as shown in figure 1, the waxy 3D ceramic tile comprises a tile blank layer 1, a make-up soil layer 2, a surface glaze layer 3, a pattern layer 4 and a waxy glaze layer 5, and the surface glaze layer, the pattern layer and the waxy glaze layer are also provided with sunken grains 6, and the sunken grains are obtained by the repulsion of mold ink for ink-jet printing on the surface glaze layer and the waxy glaze layer. The waxy glaze layer is prepared from the waxy glaze material which is prepared into aqueous waxy glaze slip. The mould ink adopts an organic solvent as a solvent, is an oily ink, can generate repulsion action on aqueous waxy glaze slip and surface glaze layer glaze slip, and can enable the waxy glaze layer to be accumulated on two sides of the sunken texture through the repulsion action, thereby not only forming better 3D stereoscopic effect, but also having better thickness, permeability and fineness, particularly the accumulated waxy glaze has a warm and moist decorative effect like jade.
It should be noted that the layered structure of the waxy 3D tile includes two kinds of recessed textures, and the two kinds of recessed textures are respectively prepared from the mold ink printed on the makeup soil layer and the mold ink printed on the pattern layer, but in an actual product, the tile with a three-dimensional effect is not limited to the layered structure, and may be: the ceramic tile comprises a tile blank layer, a makeup soil layer, a pattern layer and a waxy glaze layer, but a surface glaze layer is not arranged, and mould ink is printed on the pattern layer to form a sunken texture; it may also be: the ceramic tile comprises a tile blank layer, a makeup soil layer, a surface glaze layer, a pattern layer and a waxy glaze layer, and only the mould ink is printed on the makeup soil layer to form only one kind of sunken texture. The waxy 3D ceramic tile with the three-dimensional effect can be obtained by the structure, and the difference is only that the path and depth of the texture are different, and the three-dimensional effect is different.
In one embodiment, the mold ink comprises, in mass percent: 38-48% of waxy glaze, 20-30% of acrylic resin, 20-30% of ethyl acetate, 3-6% of dispersing agent, 0.1-0.2% of suspending agent, 0.2-0.3% of defoaming agent, 0.3-0.6% of flatting agent and 0.15% of pH value regulator. The waxy glaze is a fine powdery raw material, and can improve the dispersibility of the waxy glaze in ink; the acrylic resin can improve the adhesiveness of the ink; the ethyl acetate is an organic solvent and has a repelling effect on aqueous glaze slip, so that concave grains can be formed in the place where the mould ink is printed, and a 3D (three-dimensional) effect is obtained.
In one embodiment, the chemical composition of the overglaze layer comprises, in mass percent: SiO 2 2 50～55%、Al 2 O 3 23～28%、CaO 1.5～3.1%、MgO 2.5～3.0%、K 2 O 3.5～4.5%、Na 2 O2.1-4.1%, ZnO 4.5-6.5%, and the balance of a trace amount of impurities. The cover glaze layer is prepared from cover glaze layer glaze slip, the cover glaze layer glaze slip takes water as a solvent, sodium methylcellulose and sodium tripolyphosphate are added, and the water-based glaze slip is water-based glaze slip, so that the water-based glaze slip can be repelled when oily mould ink is encountered, and the water-based glaze slip is stacked on two sides of a printing texture of the mould ink to form an uneven three-dimensional effect.
In one embodiment, the chemical composition of the makeup soil layer comprises, in mass percent: al (aluminum) 2 O 3 26～32%、SiO 2 55～60%、CaO 1.5～2.3%、MgO 1.3～2.4%、K 2 O 3.5～4.6%、Na 2 O3.8-4.6%, and trace impurities and ignition loss in balance. The makeup clay is high-aluminum and high-silicon makeup clay, has excellent binding property with the green body, and can cover the color and air holes of the green body, so that the decoration effect of the brick surface is better.
Further, the die ink is printed by two times of ink-jet printing, the two times of ink-jet printing are respectively printed on the makeup soil layer and the pattern layer, and the die ink printed on the makeup soil layer can repel the glaze layer to form first concave grains; the mould ink printed on the pattern layer can repel the waxy glaze layer and also form second sunken grains. The first concave grains and the second concave grains can be overlapped or dislocated, and can be partially overlapped or dislocated. When overlapping, can obtain the line that the degree of depth is darker, when the dislocation, can form the line of different stereovision, specifically can set for according to actual need to obtain more beautiful decorative effect.
The application also discloses a preparation method of the waxy 3D ceramic tile, which comprises the following steps:
sequentially forming a brick layer and a makeup soil layer;
depositing first mould ink on the surface of the makeup soil layer, and forming a glaze layer on the surface of the first mould ink;
and forming a pattern layer on the surface of the overglaze layer, depositing second mould ink on the surface of the pattern layer, forming a waxy glaze layer on the surface of the second mould ink, and sintering to obtain the waxy 3D ceramic tile.
In one embodiment, the method of making comprises the steps of:
the method comprises the following steps: and pressing the green brick.
Step two: and drying the green body, wherein the moisture of the dried green body is controlled to be 0.3-0.5%, and the green body has enough strength, so that sufficient strength guarantee is provided for the subsequent transmission of the green brick on a glaze line.
Step three: and spraying the make-up clay glaze slip on the blank body.
Step four: the method comprises the steps of firstly printing mould ink on the makeup soil, wherein the printing texture of the mould ink can be designed in advance through a computer, and the mould ink takes hydrophobic organic matters as a solvent.
Step five: and the green brick enters glaze spraying equipment after passing through the first-time printing mould ink, and is sprayed with surface glaze layer glaze slurry. The glaze spraying equipment is a swing arm type high-pressure glaze spraying cabinet and is provided with 6 high-pressure spray guns, and the pressure of each spray gun is set to be 15-20 Bar; the cover glaze layer glaze slip is characterized in that glaze slip with the water content of 40-45% is adopted, sodium methylcellulose and sodium tripolyphosphate are added, and therefore the electrolyte is contained, so that the cover glaze layer glaze slip has large hydrophilicity, when the cover glaze layer glaze slip is in contact with a pattern printed with mold ink, the hydrophilicity and the hydrophobicity of the mold ink repel each other, so that the cover glaze layer glaze slip is repelled along lines of the ink to form sunken lines or pits, meanwhile, accumulation is formed on two sides of the lines printed with the mold ink, an uneven structure is formed, and a three-dimensional effect is achieved.
Step six: and drying the blank body sprayed with the overglaze at the drying temperature of 150-180 ℃ for 5 minutes, and shaping the overglaze as soon as possible by drying.
Step seven: and printing a color pattern on the overglaze layer by an ink-jet printer according to the pattern texture set by the computer. The specific pattern can be set according to actual requirements.
Step eight: and printing the mold ink for the second time according to the pattern set by the computer, wherein the mold ink is the same as the mold ink printed for the first time and is hydrophobic ink, and the printed pattern can be the same as or different from the pattern printed for the first time and can be specifically set according to actual requirements.
Step nine: after the mould ink is printed for the second time, wax glaze slip spraying is carried out, a swing arm type high-pressure glaze spraying cabinet is also adopted, the wax glaze slip takes water as a solvent, the water content of the wax glaze slip is 45-50%, and sodium methylcellulose and sodium tripolyphosphate are added simultaneously, so that sodium ion electrolyte exists in the wax glaze slip, and the wax glaze slip has larger hydrophilicity, so that the wax glaze slip can be repelled when meeting the mould ink for the second time, and is discharged at a place with the mould ink, and is piled at a place without the mould ink to form concave-convex lines with a three-dimensional effect.
Step ten: and (3) firing the ceramic tile in a kiln at 1180-1200 ℃ for 40-60 minutes to obtain the waxy glaze ceramic tile.
In a preferred embodiment, in the preparation method of the waxy 3D tile, the printing grayscales of the first printing mold ink and the second printing mold ink are 40-100%. Through adjusting the printing gray level, the ceramic tile has proper ink jet amount to obtain lines with proper depth and improve the three-dimensional effect of the ceramic tile.
According to the preparation method of the waxy 3D ceramic tile, through printing the mould ink, concave grains can be formed on the surface of the tile by using the repulsive effect of the mould ink, the surface glaze layer and the waxy glaze, and then the 3D stereoscopic effect is achieved.
To further illustrate the waxy glaze, waxy 3D tile and method of making the same according to the present invention, the following examples are provided.
Example 1
The embodiment is a waxy glaze, which comprises the following components in parts by weight: 45 parts of first frit, 35 parts of second frit, 10 parts of air knife soil, 4 parts of zinc oxide and 6 parts of dolomite. The raw materials for preparing the first frit comprise, by weight: 16 parts of kaolin, 7 parts of zinc oxide, 5 parts of sodium borate, 30 parts of pyrophyllite, 10 parts of white carbon black, 7 parts of strontium carbonate, 11 parts of sodium carbonate, 14 parts of barium carbonate and 4 parts of wollastonite. The raw materials for preparing the second frit comprise: 23 parts of kaolin, 7 parts of nano-alumina, 12 parts of potassium carbonate, 7 parts of sodium carbonate, 12 parts of spodumene, 8 parts of white carbon black, 6 parts of talc and 33 parts of pyrophyllite. The first frit and the second frit are calcined and melted at the high temperature of 1450 ℃, and then are water quenched and ground to obtain the ceramic material.
Example 2
The embodiment is a waxy glaze, which comprises the following components in parts by weight: 40 parts of first frit, 40 parts of second frit, 8 parts of air knife soil, 5 parts of zinc oxide and 5 parts of dolomite. The raw materials for preparing the first frit comprise, by weight: 18 parts of kaolin, 6 parts of zinc oxide, 6 parts of sodium borate, 25 parts of pyrophyllite, 12 parts of white carbon black, 5 parts of strontium carbonate, 13 parts of sodium carbonate, 12 parts of barium carbonate and 5 parts of wollastonite. The raw materials for preparing the second frit comprise: 20 parts of kaolin, 8 parts of nano-alumina, 10 parts of potassium carbonate, 8 parts of sodium carbonate, 10 parts of spodumene, 10 parts of white carbon black, 4 parts of talc and 36 parts of pyrophyllite. The first frit and the second frit were prepared in the same manner as in example 1.
Example 3
The embodiment is a waxy glaze, which comprises the following components in parts by weight: 50 parts of first frit, 30 parts of second frit, 12 parts of air knife soil, 3 parts of zinc oxide and 8 parts of dolomite. The raw materials for preparing the first frit comprise, by weight: 15 parts of kaolin, 8 parts of zinc oxide, 3 parts of sodium borate, 36 parts of pyrophyllite, 8 parts of white carbon black, 8 parts of strontium carbonate, 10 parts of sodium carbonate, 15 parts of barium carbonate and 3 parts of wollastonite. The raw materials for preparing the second frit comprise: 25 parts of kaolin, 5 parts of nano-alumina, 15 parts of potassium carbonate, 5 parts of sodium carbonate, 15 parts of spodumene, 6 parts of white carbon black, 7 parts of talc and 30 parts of pyrophyllite. The first frit and the second frit were prepared in the same manner as in example 1.
Example 4
The embodiment is a waxy glaze, which comprises the following components in parts by weight: 48 parts of first frit, 38 parts of second frit, 11 parts of air knife soil, 4 parts of zinc oxide and 7 parts of dolomite. The raw materials for preparing the first frit comprise, by weight: 17 parts of kaolin, 7 parts of zinc oxide, 4 parts of sodium borate, 25 parts of pyrophyllite, 9 parts of white carbon black, 6 parts of strontium carbonate, 12 parts of sodium carbonate, 13 parts of barium carbonate and 4 parts of wollastonite. The raw materials for preparing the second frit comprise: 22 parts of kaolin, 6 parts of nano-alumina, 13 parts of potassium carbonate, 6 parts of sodium carbonate, 14 parts of spodumene, 9 parts of white carbon black, 5 parts of talc and 35 parts of pyrophyllite. The first frit and the second frit were prepared in the same manner as in example 1.
Example 5
This embodiment is a wax 3D tile, as shown in fig. 2, the tile includes: the glaze comprises a brick blank layer, a make-up soil layer, a surface glaze layer, a pattern layer and a waxy glaze layer, and further comprises a first texture layer and a second texture layer, wherein the first texture layer is arranged between the make-up soil layer and the surface glaze layer, the second texture layer is arranged between the pattern layer and the waxy glaze layer, the first texture layer is prepared through the repulsion action of mold ink printed on the make-up soil layer and the surface glaze layer, the second texture layer is prepared through the repulsion action of the mold ink printed on the pattern layer and the waxy glaze layer, the mold ink is organic solvent type ink and contains waxy glaze powder as described in example 1, the waxy glaze layer and the surface glaze layer are both made of water-based glaze slurry, and the glaze slurry of the waxy glaze layer is prepared from waxy glaze as described in example 1.
The chemical composition of the makeup soil layer comprises the following components in percentage by mass: al (Al) 2 O 3 26%、SiO 2 60%、CaO 2.3%、MgO 2.4%、K 2 O 4.6%、Na 2 4.6 percent of O, and the balance of trace impurities and ignition loss.
The chemical composition of the overglaze layer comprises the following components in percentage by mass: SiO 2 2 50%、Al 2 O 3 28%、CaO 1.5%、MgO 3.0%、K 2 O 3.5%、Na 2 4.1 percent of O, 4.5 percent of ZnO and the balance of proper amount and trace impurities.
The pattern layer is prepared by adopting conventional ceramic ink.
The waxy glaze layer was prepared from the waxy glaze described in example 1.
The mould ink comprises the following components in percentage by mass: 38% of waxy glaze, 30% of acrylic resin, 24.75% of ethyl acetate, 6% of dispersing agent, 0.2% of suspending agent, 0.3% of defoaming agent, 0.6% of leveling agent and 0.15% of pH value regulator. The waxy glaze is the waxy glaze described in example 1, and is ground into fine powder.
The waxy 3D ceramic tile is prepared by the following method: pressing a green brick, drying, spraying the makeup soil, printing mould ink for the first time, spraying overglaze, drying, printing patterns, printing mould ink for the second time, spraying wax glaze and firing. The printing gray levels of the first printing mould ink and the second printing mould ink are 60%, the firing temperature in the firing step is 1180 ℃, and the firing time is 60 minutes.
Example 6
This example is a waxy 3D tile, as shown in fig. 3, the layered structure of which is the same as that of example 5, except that: (1) the waxy glaze used was the waxy glaze described in example 2;
(2) the chemical composition of the makeup soil layer comprises the following components in percentage by mass: al (aluminum) 2 O 3 32%、SiO 2 55%、CaO 1.5%、MgO 1.3%、K 2 O 3.5%、Na 2 3.8 percent of O, and the balance of trace impurities and ignition loss;
(3) the chemical composition of the overglaze layer comprises the following components in percentage by mass: SiO 2 2 55%、Al 2 O 3 23%、CaO 3.1%、MgO 2.5%、K 2 O 4.5%、Na 2 O2.1%, ZnO 6.5%, and the balance of reduced and trace impurities;
(4) the mould ink comprises the following components in percentage by mass: 48% of waxy glaze, 20% of acrylic resin, 28.25% of ethyl acetate, 3% of dispersing agent, 0.1% of suspending agent, 0.2% of defoaming agent, 0.3% of leveling agent and 0.15% of pH value regulator. The waxy glaze is the waxy glaze described in example 2, and is ground into fine powder.
The waxy 3D tile described in example 6 was prepared the same as in example 5, except that: the printing gray scale of the die ink is 40%, the firing temperature in the firing step is 1200 ℃, and the firing time is 40 minutes.
Example 7
This example is a waxy 3D tile, as shown in fig. 4, the layered structure of which is the same as that of example 5, except that: (1) the waxy glaze used was the waxy glaze described in example 3;
(2) the chemical composition of the makeup soil layer comprises the following components in percentage by mass: al (Al) 2 O 3 28%、SiO 2 58%、CaO 2%、MgO 2%、K 2 O 4%、Na 2 O4 percent, and the balance of trace impurities and ignition loss;
(3) the chemical composition of the overglaze layer comprises the following components in percentage by mass: SiO 2 2 53%、Al 2 O 3 26%、CaO 2.5%、MgO 2.8%、K 2 O 4.0%、Na 2 3.1 percent of O, 5.5 percent of ZnO and the balance of proper amount and trace impurities;
(3) the mould ink comprises the following components in percentage by mass: 47.85% of waxy glaze, 26% of acrylic resin, 20% of ethyl acetate, 5% of dispersing agent, 0.2% of suspending agent, 0.3% of defoaming agent, 0.5% of leveling agent and 0.15% of pH value regulator. The waxy glaze is the waxy glaze described in example 3, and is ground into fine powder.
The waxy 3D tile described in example 7 was prepared the same as in example 5, except that: the printing gray level of the die ink is 80%, the firing temperature in the firing step is 1190 ℃, and the firing time is 50 minutes.
Example 8
This example is a waxy 3D tile, as shown in fig. 5, the layered structure of which is the same as that of example 5 except that: (1) the waxy glaze used was the waxy glaze described in example 4;
(2) the chemical composition of the makeup soil layer comprises the following components in percentage by mass: al (Al) 2 O 3 30%、SiO 2 56%、CaO 2.3%、MgO 1.5%、K 2 O 4.2%、Na 2 4.4 percent of O, and the balance of trace impurities and ignition loss;
(3) the chemical composition of the overglaze layer comprises the following components in percentage by mass: SiO 2 2 55%、Al 2 O 3 25%、CaO 3.0%、MgO 3.0%、K 2 O 4.2%、Na 2 3.8 percent of O, 5.0 percent of ZnO and the balance of proper amount and trace impurities;
(4) the mould ink comprises the following components in percentage by mass: waxy glaze 44%, acrylic resin 20.95%, ethyl acetate 30%, dispersing agent 4%, suspending agent 0.2%, defoaming agent 0.3%, leveling agent 0.4%, and pH value regulator 0.15%. The waxy glaze is the waxy glaze described in example 4, and is ground into fine powder.
The waxy 3D tile described in example 8 was prepared the same as in example 5, except that: the printing gray level of the die ink is 100%, the firing temperature in the firing step is 1190 ℃, and the firing time is 45 minutes.
Comparative example 1
The comparison is a glaze and a ceramic tile.
A glaze, the basic composition of which is the same as that of example 1, except that the white carbon black in the first frit was replaced with quartz powder having a larger particle size in equal amounts.
A ceramic tile, prepared according to the method for preparing a ceramic tile described in example 5, which is different from example 5 in that the glaze described in example 5 is replaced with the glaze described in comparative example 1, and the other components and the preparation method are not changed, and the ceramic tile is obtained as shown in fig. 6.
Comparative example 2
The comparison is a glaze and a ceramic tile.
A glaze, the basic composition of which is the same as that of example 1, except that the white carbon black in the second frit was replaced with quartz powder having a larger particle size in equal amounts.
A ceramic tile, prepared according to the method for preparing a ceramic tile described in example 5, which is different from example 5 in that the glaze described in example 5 is replaced with the glaze described in comparative example 2, and the other components and the preparation method are not changed, and the ceramic tile is obtained as shown in fig. 7.
Comparative example 3
The comparison is a glaze and a ceramic tile.
A glaze, the essential ingredients of which are the same as in example 1, except that the nano-alumina in the second frit was replaced equally with alumina powder having a particle size of 325 mesh.
A ceramic tile, produced according to the method for producing a ceramic tile described in example 5, which is different from example 5 in that the glaze described in example 5 is replaced with the glaze described in comparative example 3, and the other components and the production method are not changed, and the ceramic tile is obtained as shown in fig. 8.
Comparative example 4
The comparison is a glaze and a ceramic tile.
A glaze, the essential ingredients of which are the same as in example 1, except that the amount of white carbon black added in the first frit is 4 parts by weight.
A ceramic tile, produced according to the method for producing a ceramic tile described in example 5, which is different from example 5 in that the glaze described in example 5 is replaced with the glaze described in comparative example 4, and the other components and the production method are not changed, and the ceramic tile is obtained as shown in fig. 9.
Comparative example 5
The comparison is a glaze and a ceramic tile.
A glaze, the essential ingredients of which are the same as in example 1, except that the white carbon black is added in an amount of 14 parts by weight in the first frit.
A ceramic tile, produced according to the method for producing a ceramic tile described in example 5, which is different from example 5 in that the glaze described in example 5 is replaced with the glaze described in comparative example 5, and the other components and the production method are not changed, and the ceramic tile is obtained as shown in fig. 10.
Comparative example 6
The comparison is a glaze and a ceramic tile.
A glaze, the essential components of which are the same as in example 1, except that the second frit comprises, in parts by weight, 10 parts of nano-alumina and 12 parts of white carbon black
A ceramic tile, produced according to the method for producing a ceramic tile described in example 5, which is different from example 5 in that the glaze described in example 5 is replaced with the glaze described in comparative example 6, and the other components and the production method are not changed, and the ceramic tile is obtained as shown in fig. 11.
Comparative example 7
The comparison is a glaze and a ceramic tile.
A glaze, the essential ingredients of which are the same as in example 1, except that the second frit comprises, in parts by weight, 3 parts of nano-alumina and 3 parts of white carbon black
A ceramic tile, produced according to the method for producing a ceramic tile described in example 5, which is different from example 5 in that the glaze described in example 5 is replaced with the glaze described in comparative example 7, and the other components and the production method are not changed, and the ceramic tile is obtained as shown in fig. 12.
Comparative example 8
The comparison is a glaze and a ceramic tile.
A glaze, the essential ingredients of which are the same as in example 1, except that the second frit comprises, in parts by weight, 2 parts of nano-alumina and 15 parts of white carbon black
A ceramic tile, produced according to the method for producing a ceramic tile described in example 5, which is different from example 5 in that the glaze described in example 5 is replaced with the glaze described in comparative example 8, and the other components and the production method are not changed, and the ceramic tile is obtained as shown in fig. 13.
It should be noted that the patterns of the pattern layers in examples 4 to 5 and comparative examples 1 to 8 may be the same or different, and the texture structures of the first texture layer and the second texture layer in each example and each comparative example may be the same or different, and may be specifically selected according to actual needs.
Performance testing
The glazes prepared in examples 1 to 4 and comparative examples 1 to 8 were subjected to a light transmission test and a gloss test, wherein the light transmission test was performed by using a spectrophotometer, and specifically, the light transmission test comprises the following steps: first, the glaze materials described in examples 1 to 4 and comparative examples 1 to 8 were prepared into square samples having a thickness of 5mm and a length × width of 5cm × 5cm, and then, the transmittance thereof was measured by a spectrophotometer, and the specific results are shown in table 1. The gloss measurement is carried out according to the international standard ISO-2813 or the national standard GB/T9754, and is carried out by a WGG60-Y series gloss meter, and the specific test result is shown in Table 1.
Table 1 results of performance testing
As can be seen from table 1, the glazes of examples 1 to 4 have excellent light transmittance at the same thickness, and thus have good permeability even when the thickness of the glaze layer is relatively large, so that the pattern of the pattern layer can be fully demonstrated. Meanwhile, the glossiness of the examples 1 to 4 is lower than that of the comparative examples 1 to 6 and 8, so that the matte effect is better, and the lubricous wax texture can be formed. The light transmittance and gloss of comparative examples 1 to 8 were inferior to those of examples 1 to 8 (except for comparative example 7), and the light transmittance of comparative example 7 was inferior although it was also a matte effect. This is because the waxy glaze in examples 1 to 4 contains white carbon black and nano alumina having very small particle size, has good dispersibility, and can fully react with oxides to form a fine glass phase or crystal (as shown in fig. 16, from the SEM image of the surface layer of the waxy glaze, it can be seen that the crystal on the surface is fine and fine, and is distributed in the glass phase, and the small porosity and the dense crystal phase and glass phase structure of the glaze are the main reasons for the fine and transparent texture of the glaze), and further has softness and fine texture, and forms a waxy feeling like jade. Meanwhile, the tiles prepared in example 5 and comparative example 1 were observed with a magnifying glass (magnification 150 times), and the observation results are shown in fig. 14 and fig. 15, fig. 14 is an enlarged view of comparative example 1, and fig. 15 is an enlarged view of example 5, and it can be seen from fig. 15 that the number of bubbles is small and the light transmittance is better in example 5, and that the number of bubbles is large and the light transmittance is poor in fig. 14, and thus, the glaze described in the present application forms fewer pores and the light transmittance is better.
Apparent comparison
Observing figures 2-13, comparing glaze materials of examples 5-8 and comparative examples 1-8 to obtain the apparent structure of the ceramic tile, finding that the surface of the ceramic tile of examples 4-8 has textures with different depths, 3D stereoscopic effect, clear and visible patterns and obvious stereoscopic effect, the thickness of the waxy glaze layer on the surface is 0.1-0.35 mm, the ceramic tile is thick and heavy, good in permeability, fine and smooth and has jade texture. The tiles prepared by the glaze materials of comparative examples 1 to 8 have textures with different depths, but have insufficient stereoscopic impression, because the surface glaze materials of the tiles of comparative examples 1 to 8 are different from the waxy glaze materials, the reaction products are different at the same sintering temperature as that of example 5, and the sintering degrees are different, so that the depths of the formed sunken textures are different, the surface gloss is different, and the heavy texture, the texture and the jade texture are poor. Therefore, the content of the white carbon black in the first frit raw material and the content of the nano aluminum oxide and the white carbon black in the second frit raw material are key factors influencing the texture and the light transmittance of the glaze wax, too much or too little or no addition of the white carbon black can influence the appearance of the glaze wax effect, and the wax effect can be obtained only by the glaze with specific components and proportions. And the waxy glaze can improve the apparent effect of the ceramic tile, and has better permeability and fineness while obtaining the sense of thickness, thereby improving the ornamental value of the ceramic tile.
It should be understood that equivalents and modifications of the technical solution and inventive concept thereof may occur to those skilled in the art, and all such modifications and alterations should fall within the scope of the appended claims.
Claims (10)
1. The waxy glaze is characterized by comprising the following components in parts by weight: 40-50 parts of first frit and 30-40 parts of second frit; according to the mass percentage, the preparation raw material of the first frit contains 7.5-12% of white carbon black, and the preparation raw material of the second frit contains 4.6-7.6% of nano alumina and 5.5-9.5% of white carbon black.
2. The waxy glaze according to claim 1, wherein the first frit is prepared from the following raw materials in parts by weight: 15-18 parts of kaolin, 6-8 parts of zinc oxide, 3-6 parts of sodium borate, 25-36 parts of pyrophyllite, 8-12 parts of white carbon black, 5-8 parts of strontium carbonate, 10-13 parts of sodium carbonate, 12-15 parts of barium carbonate and 3-5 parts of wollastonite.
3. The waxy glaze according to claim 1, wherein the second frit is prepared from the following raw materials in parts by weight: 20-25 parts of kaolin, 5-8 parts of nano alumina, 10-15 parts of potassium carbonate, 5-8 parts of sodium carbonate, 10-15 parts of spodumene, 6-10 parts of white carbon black, 4-7 parts of talc and 30-36 parts of pyrophyllite.
4. The waxy glaze according to claim 1, wherein said waxy glaze further comprises, in parts by weight: 8-12 parts of air knife soil, 3-5 parts of zinc oxide and 5-8 parts of dolomite.
5. A waxy 3D ceramic tile, which is characterized by comprising a tile blank layer, a makeup soil layer, a surface glaze layer, a pattern layer and a waxy glaze layer which are sequentially stacked, wherein the surface glaze layer, the pattern layer and the waxy glaze layer are also provided with sunken textures, and the waxy glaze layer is prepared from the waxy glaze material as claimed in any one of claims 1 to 4.
6. The waxy 3D tile according to claim 5, wherein the texture is produced by the repelling effect of a mold ink on the glaze layer and the waxy glaze layer, the mold ink comprising, in mass percent: 38-48% of waxy glaze, 20-30% of acrylic resin, 20-30% of ethyl acetate, 3-6% of dispersing agent, 0.1-0.2% of suspending agent, 0.2-0.3% of defoaming agent, 0.3-0.6% of flatting agent and 0.15% of pH value regulator.
7. The waxy 3D tile according to claim 5, wherein the chemical composition of the overglaze layer comprises, in mass percent: SiO 2 2 50～55%、Al 2 O 3 23～28%、CaO 1.5～3.1%、MgO 2.5～3.0%、K 2 O 3.5～4.5%、Na 2 O2.1-4.1%, ZnO 4.5-6.5%, and the balance of ignition loss and trace impurities.
8. The waxy 3D tile according to claim 5,the chemical composition of the makeup soil layer comprises the following components in percentage by mass: al (aluminum) 2 O 3 26～32%、SiO 2 55～60%、CaO 1.5～2.3%、MgO 1.3～2.4%、K 2 O 3.5～4.6%、Na 2 O3.8-4.6%, and trace impurities and ignition loss in balance.
9. A method of making the waxy 3D tile according to any of claims 5-8, comprising the steps of:
sequentially forming a brick blank layer and a makeup soil layer;
depositing first mould ink on the surface of the makeup soil layer, and forming a glaze layer on the surface of the first mould ink;
and forming a pattern layer on the surface of the overglaze layer, depositing second mould ink on the surface of the pattern layer, forming a waxy glaze layer on the surface of the second mould ink, and sintering to obtain the waxy 3D ceramic tile.
10. The preparation method of the waxy 3D ceramic tile according to claim 9, wherein the method for depositing the first mold ink and the method for depositing the second mold ink are both inkjet printing methods, and the printing gray levels are 40-100%; in the firing step, the firing temperature is 1180-1300 ℃, and the firing time is 40-60 minutes.
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| CN116375506A (en) * | 2023-06-06 | 2023-07-04 | 新明珠集团股份有限公司 | Antibacterial glazed ceramic tile with silver decorative effect and preparation method thereof |
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| CN119684038A (en) * | 2024-12-09 | 2025-03-25 | 佛山市金竹林新型材料科技有限公司 | A kind of original jade ice pattern marble tile and preparation method thereof |
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| CN116621612B (en) * | 2023-07-26 | 2023-10-17 | 佛山市三水新明珠建陶工业有限公司 | Composition for preparing ceramic overglaze, ceramic brick with mold texture, and preparation method and application thereof |
| CN119684038A (en) * | 2024-12-09 | 2025-03-25 | 佛山市金竹林新型材料科技有限公司 | A kind of original jade ice pattern marble tile and preparation method thereof |
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Address after: 528061 1st floor, No.18 taobo Avenue, Huaxia Ceramics Expo City, Nanzhuang Town, Chancheng District, Foshan City, Guangdong Province Patentee after: New Pearl Group Co.,Ltd. Patentee after: FOSHAN SANSHUI NEW PEARL CONSTRUCTION CERAMICS INDUSTRIAL Co.,Ltd. Patentee after: New Pearl (Guangdong) New Materials Co.,Ltd. Patentee after: Jiangxi Xinmingzhu Building Materials Co.,Ltd. Patentee after: Hubei new Ming Zhu Green Building Materials Technology Co.,Ltd. Address before: 528061 1st floor, No.18 taobo Avenue, Huaxia Ceramics Expo City, Nanzhuang Town, Chancheng District, Foshan City, Guangdong Province Patentee before: New Pearl Group Co.,Ltd. Patentee before: FOSHAN SANSHUI NEW PEARL CONSTRUCTION CERAMICS INDUSTRIAL Co.,Ltd. Patentee before: GUANGDONG SUMMIT CERAMICS Co.,Ltd. Patentee before: Jiangxi Xinmingzhu Building Materials Co.,Ltd. Patentee before: Hubei new Ming Zhu Green Building Materials Technology Co.,Ltd. |
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