CN117682766A - Spot art colored glaze ceramic plate combining half-number glaze and preparation method thereof - Google Patents
Spot art colored glaze ceramic plate combining half-number glaze and preparation method thereof Download PDFInfo
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- CN117682766A CN117682766A CN202410153778.XA CN202410153778A CN117682766A CN 117682766 A CN117682766 A CN 117682766A CN 202410153778 A CN202410153778 A CN 202410153778A CN 117682766 A CN117682766 A CN 117682766A
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- 238000002360 preparation method Methods 0.000 title abstract description 18
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- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 68
- 239000011787 zinc oxide Substances 0.000 claims description 34
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- 239000000843 powder Substances 0.000 claims description 25
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- 238000001035 drying Methods 0.000 claims description 12
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 12
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- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims description 7
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- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 8
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- 239000000976 ink Substances 0.000 description 33
- 239000000292 calcium oxide Substances 0.000 description 22
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- 239000011734 sodium Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
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- HNDYULRADYGBDU-UHFFFAOYSA-N 8-methylnonyl benzoate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1 HNDYULRADYGBDU-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 239000002518 antifoaming agent Substances 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
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 238000004031 devitrification Methods 0.000 description 1
- SZLIWAKTUJFFNX-UHFFFAOYSA-N dihydrocitronellol benzoate Natural products CC(C)CCCC(C)CCOC(=O)C1=CC=CC=C1 SZLIWAKTUJFFNX-UHFFFAOYSA-N 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- XTIIITNXEHRMQL-UHFFFAOYSA-N tripotassium methoxy(trioxido)silane Chemical compound [K+].[K+].[K+].CO[Si]([O-])([O-])[O-] XTIIITNXEHRMQL-UHFFFAOYSA-N 0.000 description 1
- PSUYMGPLEJLSPA-UHFFFAOYSA-N vanadium zirconium Chemical compound [V].[V].[Zr] PSUYMGPLEJLSPA-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Glass Compositions (AREA)
Abstract
The invention relates to a half-number glaze combined spot art colored glaze ceramic plate and a preparation method thereof, belonging to the technical field of building ceramic plate preparation. Aiming at the problems that the color of the ceramic plate brick surface prepared by adopting the existing ink-jet technology is not bright enough and the decorative effect is single, the invention provides the zinc-titanium crystallization artistic color overglaze taking copper oxide and cobalt oxide as synergistic color-developing agents and the color scattered colored spot glaze containing ammonium metavanadate.
Description
Technical Field
The invention belongs to the field of building ceramic plate preparation, and particularly relates to a spot art colored glaze ceramic plate combined with half-number glaze and a preparation method thereof.
Background
In recent years, the application market of ceramic thin plates is becoming wider, and not only used as background walls, curtain walls and the like, but also a plurality of home or household appliances are increasingly combined with the ceramic thin plates. The ceramic sheet has high requirements on equipment, and most ceramic sheets on the market are in the presence of inkjet products or solid-color bricks. However, since the color of the ink-jet or ordinary coloring material is relatively single and not bright enough, it is difficult to achieve the effect texture of the mold on the sheet glaze before the appearance of the digital glaze, and particularly, it is more difficult to achieve the effect on the 3mm thin brick.
For this reason, it is becoming particularly important to develop a ceramic sheet having a color artistic grain effect and a mold texture effect.
Disclosure of Invention
Aiming at the problems of insufficient color of the brick surface and single decorative effect when the ceramic plate is prepared by adopting the existing ink-jet technology, the invention provides a spot art colored glaze ceramic plate combined with half-number glaze and a preparation method thereof. The effect produced by overlapping the glazes with different effects is more natural, and the texture produced by combining the digital engraving ink is more vivid.
In a first aspect, the present invention provides a method for preparing a half-size glaze-bonded spot art colored glazed ceramic board, the method comprising: firstly, digital glaze or engraving ink is printed on the surface of the green brick in an inkjet mode; then, applying a colored overglaze on the surface of the green brick after the digital glaze is printed or the ink is engraved by ink jet; then, the surface of the green brick after the colored overglaze is applied is painted with colored dispersion colored spot glaze; then, applying digital protective glaze on the surface of the green brick after applying the colored scattered pattern spot glaze; finally, drying and firing the adobe subjected to the digital protective glaze application to obtain the spot artistic colored glaze ceramic plate combined with the half-number glaze;
the raw materials of the color overglaze comprise: 25-40% of frit, 5-10% of quartz, 10-15% of calcite, 5-10% of calcined zinc oxide, 5-8% of black mud, 6-10% of zirconium silicate, 5-10% of calcined talcum, 5-10% of glass powder, 10-20% of microcrystalline powder and 0.5-2.5% of first pigment; the chemical composition of the frit comprises: in mass percent, IL:0.3 to 0.5 percent; na (Na) 2 O：5～6%；SiO 2 ：50～65%；Al 2 O 3 ：10～18%；CaO：10～15%；K 2 O：1.0～3.5%；MgO：1.0～3.0%；ZnO：0.5～8%；ZrO 2 ：0.2～0.5%；BaO：0.5～3%；
The color scattered flower spot glaze comprises the following raw materials: the weight percentage of the composite material is 25 to 40 percent of potassium feldspar, 10 to 15 percent of quartz, 25 to 45 percent of microcrystalline powder, 5 to 10 percent of zinc oxide, 5 to 10 percent of titanium oxide, 3 to 5 percent of zirconium silicate, 3 to 5 percent of ammonium metavanadate and 0.2 to 2 percent of second pigment.
Preferably, the chemical composition of the colored overglaze comprises: in mass percent, IL:1.5 to 4.5 percent; siO (SiO) 2 ：45～55%；Al 2 O 3 ：10～15%；Fe 2 O 3 ：0.1～0.2%；TiO 2 ：5～8%；CaO：10～13%；MgO：2.0～4.0%；K 2 O：1.0～3.0%；Na 2 O：0.2～0.3%；CuO：0.3～1.5%；ZnO：5～11%；ZrO 2 ：8～10%；CoO：0.1～0.2%。
Preferably, the glazing mode of the colored overglaze is glaze spraying; the specific gravity of the colored overglaze is 1.40-1.45, and the glazing quantity is 620-660 g/m 2 。
Preferably, the chemical composition of the color scattered flower spot glaze comprises: in mass percent, IL:3.5～7.9%；SiO 2 ：45～60%；Al 2 O 3 ：8～12%；Fe 2 O 3 ：0.2～0.5%；TiO 2 ：5～10%；CaO：0.2～9%；MgO：1.0～1.9%；K 2 O：1.0～3.8%；Na 2 O：1.0～2.0%；ZrO 2 ：3.0～5.0%。
preferably, the glazing mode of the colored scattered flower spot glaze is throwing glaze; the specific gravity of the colored scattered flower spot glaze is 1.55-1.60, and the glazing quantity is 40-60 g/m 2 。
Preferably, the chemical composition of the digital protection glaze comprises: in mass percent, IL:1.0 to 2.5 percent; na (Na) 2 O：2.0～3.0%；SiO 2 ：45～55%；Al 2 O 3 ：10～20%；CaO：9.0～13%；K 2 O：1.0～3.0%；MgO：1.0～2.5%；ZnO：3.0～8.0%；ZrO 2 ：0.1～0.2%；BaO：3.5～6.2%。
Preferably, the firing temperature is 1210-1225 ℃; the firing time is 65 to 75 minutes.
In a second aspect, the invention provides a half-number glaze-bonded spot art colored glaze ceramic plate obtained according to the preparation method.
Advantageous effects
(1) Creative: the ceramic plate brick surface obtained by the preparation method provided by the invention can form white crystal flowers with different shapes, and is matched with overglaze with proper colors to form a rock plate product with special crystal flower effect and strong stereoscopic impression;
(2) The decorative effect is good: compared with the common ink-jet natural brick surface ceramic rock plate, the ceramic plate provided by the invention has good brick surface effect crystal flower decoration, good permeability after a polishing process, and better white crystal flower decoration effect especially matched with light gray and beige patterns;
(3) The application range is wide: the ceramic plate provided by the invention is not influenced by environmental factors, and can be widely applied to decoration of various inner walls, floors, background walls and home desktop panels;
(4) Easy cleaning: the ceramic plate provided by the invention is completely sintered, the water absorption is within 0.3 and wt%, and the ceramic plate is super-clean and bright after half polishing, has good antifouling effect and high glossiness, and is easy to clean and sanitary;
(5) Durable: the ceramic plate provided by the invention has stable performance, is little influenced by factors such as time, environment and the like, has good wear resistance, can be kept as new for a long time, has long service life, and has wide market economic benefit and application prospect.
Drawings
FIGS. 1-4 are block face effect diagrams of half-number glaze-bonded spot art colored glaze ceramic plates prepared after engraving inks with different effect texture patterns are printed on different green bricks in the embodiment 1 of the invention;
FIG. 5 is a graph showing the effect of the tile surface of the ceramic plate prepared in comparative example 1;
FIG. 6 is a graph showing the effect of the tile surface of the ceramic plate prepared in comparative example 2;
fig. 7 is a graph showing the effect of the tile surface of the ceramic plate prepared in comparative example 3.
Detailed Description
The invention is further illustrated by the following embodiments, it being understood that the following embodiments are merely illustrative of the invention and not limiting thereof. Unless otherwise specified, each percentage refers to a mass percent.
The following preparation process of the spot artistic colored glaze ceramic plate combined with half-number glaze (spray tower granulation, cloth system distribution, press molding, drying kiln drying, sweeping blank wetting, ink-jet printing digital glaze pattern, applying surface glaze, ink-jet printing pattern or not, throwing colored glaze, applying protective glaze, drying by a drying line, kiln firing, edging, polishing by a polishing line and packing) is exemplified by the preparation method of the spot artistic colored glaze ceramic plate combined with half-number glaze. The preparation method may include the following steps.
And (5) preparing green bricks. The green bricks can be prepared by using the raw materials of the green bricks of the ceramic rock plates with higher whiteness.
In some embodiments, the chemical composition of the raw materials of the green brick may include: in mass percent, IL:4.0 to 4.8 percent; siO (SiO) 2 ：60～65%；Al 2 O 3 ：20～22%；Fe 2 O 3 ：0.1～0.5%；TiO 2 ：0.05～0.3%；CaO：0.4～0.5%；MgO：0.5～1.0%；K 2 O：2.0～3.0%；Na 2 O:3.0 to 4.0 percent. Preferably, the whiteness of the raw materials of the green bricks can be controlled to be 45-50.
In some embodiments, the green brick feedstock may have a grain size distribution of: the mass percentage is more than 30 meshes: 20-25%; 30 to 80 mesh: 60-70%, and less than or equal to 6% of 80 meshes.
The green bricks can be prepared by conventional green brick making processes. For example, the raw materials of the green bricks are added with water, ball-milled and uniformly mixed, granulated into granules by a spray tower, and then the granules are distributed by a distribution system, pressed and molded by a press, and then the granules are dried in a drying kiln to prepare the green bricks. The green bricks can be polished by a green brick polishing machine before entering the drying kiln. In some embodiments, the press molding pressure may be 122000KN and the molding times may be 1.65 times/min. In order to enrich the color of the green brick, the raw materials of the green brick and the pigment can be mixed for use.
And (3) printing digital glaze or engraving ink on the surface of the green brick in an ink-jet way. Engraving ink is also known as "digital engraving ink", "deep engraving ink", "digital stripping ink", and the like. The green bricks can be wetted by sweeping the green bricks prior to ink-jet printing of the digital glaze or engraving of the ink. In some embodiments, the green brick may have a moisture content of 8.5±0.3 wt%.
In some embodiments, the composition of the engraving ink may include: the weight percentage is 35-55% of engraving agent, 30-45% of oily water repellent, 3-8% of lipid solvent, 5-9% of dispersing agent, 0.05-0.3% of anti-settling agent and 0.05-0.2% of defoaming agent. The digital engraving ink is commercially available, such as spanish Tao Lixi ink company deep engraving ink AM680.
Wherein the engraving agent can be one of inkjet engraving agents; the oily water repellent can be one of potassium methyl silicate and polymethyl triethoxysilane; the lipid solvent can be one of acetyl tributyl citrate, methyl laurate, isooctyl laurate and isodecyl benzoate; the dispersing agent can be one of HP1064, lubo Solsperse J909 and Lubo Solsperse J945 produced by Anshanhui iridescent material chemical engineering Co-Ltd; the anti-settling agent can be one of AKN-2140 and AKN-7010 produced by Qian you chemical industry Co., ltd; the defoamer may be one of the silicones.
The spot effect pattern can be promoted to be formed by printing digital glaze or engraving ink, and the regular floral pattern can be further formed after the spot effect pattern is sintered in a subsequent kiln.
In some embodiments, the carving ink application amount can be controlled to be 30-50 g/m 2 . The excessive application amount of the engraving ink can cause poor drying effect of the ink to cause stripping, deviation of engraving precision and unclear spot effect; too small an application amount of the engraving ink can result in shallower engraving depth and engraving texture, unclear texture effects, and poor speckle effects.
And applying a colored overglaze on the surface of the green brick after the digital glaze is printed or the ink is engraved by ink jet. The colored overglaze can be stripped off by the physical effect of the engraving ink to form the ground tint with the pattern effect. Specifically, the engraving ink is printed on the surface of a ceramic green brick in an inkjet mode through an inkjet printer, then colored overglaze with special effects is sprayed on the surface of the green brick, and the overglaze is enabled to form a specific spot pattern through the stripping action of the engraving ink.
It will be appreciated that other texture patterns (such as leather-, cloth-, or wood-, stone-like effect patterns) may be printed using the engraving ink in addition to the speckle pattern. Meanwhile, the stripping effect can be used for forming patterns with specific texture effects, such as sandstone or black slate patterns, of colorful overglaze with bright color.
In some embodiments, the chemical composition of the colored overglaze may include: in mass percent, IL:1.5 to 4.5 percent; siO (SiO) 2 ：45～55%；Al 2 O 3 ：10～15%；Fe 2 O 3 ：0.1～0.2%；TiO 2 ：5～8%；CaO：10～13%；MgO：2.0～4.0%；K 2 O：1.0～3.0%；Na 2 O：0.2～0.3%；CuO：0.3～1.5%；ZnO：5～11%；ZrO 2 ：8～10%；CoO：0.1～0.2%。
The colored overglaze provided by the invention takes copper oxide and cobalt oxide as synergistic color former, meanwhile, the glaze belongs to zinc-titanium crystallization artistic colored glaze, zinc oxide and titanium oxide in the formula need to be strictly controlled in a specific range, otherwise, the firing temperature and the glaze effect of the overglaze cannot meet the target requirements. When the content of zinc oxide and titanium oxide is too high, the crystallization amount is easily excessive on the glaze, so that partial dumb devitrification is caused, and the integral effect of the scattered flowers is influenced; when the content of zinc oxide and titanium oxide is too low, glaze pinholes are easy to appear, the glaze is uneven, and the pattern scattering effect is hardly seen. Meanwhile, copper oxide and cobalt oxide are used as a color former, and the addition amount of the copper oxide and the cobalt oxide needs to be maintained in a specific range, otherwise, the color of the glaze is deep and dark, and the temperature and the effect of the glaze are affected. When the content of copper oxide and cobalt oxide is too high, the surface of the glaze is deeply colored, and after the glaze contacts and reacts with colored dispersion point fancy glaze, the colored dispersion point fancy glaze is excessively colored due to mutual penetration, so that the boundary of the colored dispersion point fancy glaze is not clear; when the content of copper oxide and cobalt oxide is too low, the glaze is light in coloring, light in pattern scattering effect and unclear, and the overall decoration effect is poor.
In some embodiments, the raw material composition of the colored overglaze may include: 25-40% of frit, 5-10% of quartz, 10-15% of calcite, 5-10% of calcined zinc oxide, 5-8% of black mud, 6-10% of zirconium silicate, 5-10% of calcined talcum, 5-10% of glass powder, 10-20% of microcrystalline powder and 0.5-2.5% of first pigment.
Wherein the initial melting temperature of the frit can be 1070-1120 ℃. The addition of the frit can play a role in improving glaze gloss and improving fluidity of the high Wen Shiyou.
In some embodiments, the frit may have a chemical composition comprising: in mass percent, IL:0.3 to 0.5 percent; na (Na) 2 O：5～6%；SiO 2 ：50～65%；Al 2 O 3 ：10～18%；CaO：10～15%；K 2 O：1.0～3.5%；MgO：1.0～3.0%；ZnO：0.5～8%；ZrO 2 :0.2 to 0.5 percent; baO:0.5 to 3 percent. Among them, calcium oxide and sodium oxide are key to make the glaze vitrification degree high. The content of sodium oxide and calcium oxide is too highThe glass phase of the glaze is increased, excessive alkali metal can also promote the further reduction of the temperature of the glaze and the high-temperature viscosity of the glaze, and the defects of over-firing holes and the like can be caused by the lower high-temperature viscosity of the glaze.
In some embodiments, the frit may have a raw material composition comprising: 30-45% of albite, 10-20% of potassium feldspar, 8-15% of calcite, 3-5% of wollastonite, 3-5% of calcined talcum, 10-15% of quartz, 2-3% of barium carbonate, 1-3% of zinc oxide and 3-5% of borax.
The black mud is clay raw material, and the plasticity of the overglaze can be promoted to be improved by adding the black mud. In some embodiments, the chemical composition of the black mud may include: in mass percent, IL:6.5 to 8.5 percent; siO (SiO) 2 ：58～63%；Al 2 O 3 ：21～28%；Fe 2 O 3 ：0.3～0.5%；TiO 2 ：0.2～0.5%；CaO：0.2～0.5%；MgO：0.5～1.0%；K 2 O：1.0～3.0%；Na 2 O：0.5～2.0%。
The glass powder is added to promote the reduction of the viscosity of the glaze, increase the vitrification degree of the glaze surface and improve the transparent feeling of the glaze surface. In some embodiments, the glass frit may have a chemical composition comprising: in mass percent, IL:0.1 to 0.3 percent; siO (SiO) 2 ：55～65%；Al 2 O 3 ：5～10%；TiO 2 ：0.1～0.2%；CaO：6～12%；MgO：0.1～0.3%；Na 2 O：10～15%。
The microcrystalline powder is added to promote slight crystallization of the glaze and increase the gloss of the glaze. In some embodiments, the chemical composition of the microcrystalline powder may include: in mass percent, IL:5 to 8.5 percent; siO (SiO) 2 ：20～35%；Al 2 O 3 ：8～10%；Fe 2 O 3 ：0.1～0.2%；TiO 2 ：0.2～5%；CaO：15～35%；MgO：0.5～2%；K 2 O：2.0～3.0%；Na 2 O：1.5～3.7%；ZnO：10～24%。
The color development of the glaze layer can be promoted by adding a first coloring material. In some embodiments, the first colorant may be at least one of copper oxide, cobalt blue, vanadium zirconium blue.
In the raw materials of the color overglaze, the microcrystalline powder, the calcined zinc oxide and the frit are required to be maintained in a proper proportion range so as to ensure that crystallization forms a good glaze effect. The content of the microcrystalline powder is too high, which can lead to the increase of the content of calcium and magnesium, and the lower temperature of the glaze surface can cause the defects of brown eye foaming and the like; the content of the microcrystalline powder is too low, so that the glaze is burned, crystallization is not obvious, the color of the glaze is not bright enough, the fluidity is poor, and spots are not natural enough. Too high content of calcined zinc oxide can lead to partial sub-glaze, excessive crystallization, insufficient natural glaze color and poor pattern scattering effect; the too low content of calcined zinc oxide can cause the crystallization of the glaze surface to be not obvious, the color effect of the glaze surface to be poor and the pattern scattering effect to be not obvious. The too high frit content can cause low temperature of the glaze, so that the defects of the glaze bubbles are easy to generate, crystallization is not obvious, and the effect of scattering flowers is poor; too low a frit content can result in poor glaze fluidity, less luster and poor efflorescence effect.
In some embodiments, the colored overglaze may be applied in a cabinet-type glaze.
Weighing the color overglaze raw material, sodium tripolyphosphate and methyl, adding water, and performing ball milling to obtain color overglaze slurry; different ball milling time can be set according to fineness requirements of the overglaze slip. In some embodiments, the fineness of the colored overglaze slip may be controlled to pass through a 200 mesh screen with a screen residue of 0.2 to 0.8wt%. By controlling the fineness of the glaze slip, the proper sintering temperature can be ensured under the condition of ensuring the quality of the glaze, and the performance and the sintering temperature of the glaze slip can be influenced by too low or too high glaze slip fineness.
In some embodiments, the specific gravity of the colored overglaze can be controlled to be 1.40-1.45, and the glazing amount can be controlled to be 620-660 g/m 2 . The proper glazing quantity can better cover the green bricks, and meanwhile, the green bricks can be ensured to be sintered at the normal temperature of the kiln. Excessive glazing amount is easy to cause raw firing, and the glaze has poor flatness and poor fluidity; when the glazing amount is too low, the defects of sintering on the glaze surface, such as prickly heat on the glaze surface, and the like, are easily caused. In addition, the overglaze with proper dosage can also ensure that the overglaze is stripped to form the ground pattern with pattern effect through the physical effect of the digital engraving ink.
The green brick surface after the colored overglaze is applied is selectively ink-jet printed with a pattern. For example, inkjet printing or non-printing of the inkjet pattern may be selected according to the actual tile surface decorative effect.
And applying color dispersion fancy point glaze on the surface of the green brick after applying the color overglaze. The natural gradual change effect of the patterns can be realized by applying the colored scattered pattern spot glaze, and the fusion reaction of the patterns and the overglaze is promoted.
In some embodiments, the raw material composition of the color loose-flowered glaze may include: the weight percentage of the composite material is 25 to 40 percent of potassium feldspar, 10 to 15 percent of quartz, 25 to 45 percent of microcrystalline powder, 5 to 10 percent of zinc oxide, 5 to 10 percent of titanium oxide, 3 to 5 percent of zirconium silicate, 3 to 5 percent of ammonium metavanadate and 0.2 to 2 percent of second pigment.
The addition of the microcrystalline powder can promote the crystallization of the glaze to form a semi-transparent effect. At the same time, the use of titanium oxide and zirconium silicate in a specific ratio is beneficial to the semi-permeable effect of the glaze.
The ammonium metavanadate volatilizes in the glaze firing process to form patterns on the glaze surface, and the addition amount of the ammonium metavanadate needs to be strictly controlled. The more the addition amount is, the more the addition amount volatilizes during high-temperature decomposition, so that the scattered flowers on the brick surface are blurred, the boundary is not clear, and a good scattered flower effect cannot be formed; too little adding amount can also cause unobvious flower scattering effect, and the lace boundary is blurred and unclear.
The addition of a second colorant can promote the coloration of the glaze. In some embodiments, the second colorant may be at least one of spinel colorants, copper oxide, cobalt oxide, iron oxide, manganese oxide, and preferably one of blue-green spinel colorants. The addition of the second pigment is not excessive, so that the glaze can achieve a specific color effect, and the addition of the second pigment is excessive, so that the glaze is easy to be dark in color and not bright enough.
In some embodiments, the chemical composition of the color loose-flowered glaze may include: in mass percent, IL:3.5 to 7.9 percent; siO (SiO) 2 ：45～60%；Al 2 O 3 ：8～12%；Fe 2 O 3 ：0.2～0.5%；TiO 2 ：5～10%；CaO：0.2～9%；MgO：1.0～1.9%；K 2 O：1.0～3.8%；Na 2 O：1.0～2.0%；ZrO 2 ：3.0～5.0%。
Wherein, a small amount of titanium oxide can play a role in fluxing on one hand, and on the other hand, the opacifying effect of the titanium oxide can promote the pattern scattering effect of the glaze. The titanium oxide content is too low, which can lead to poor glaze effect, matt luster, transparent luster and heavy coloration; if the titanium oxide content is too high, phase separation is likely to occur, the glaze is bluish white, and the fluidity is deviated, and the overall pattern scattering effect is poor. At the same time, titanium oxide can be combined with coloring oxide to generate color, and too little amount can lead to color shift and poor vividness, and too much amount can lead to light color and poor gorgeous.
In some embodiments, the color-scattering spot glaze may be applied in the manner of a spray gun spot. The special effect of the glaze surface can be ensured by controlling the size and the weight of the glaze point in the application process. Wherein, the diameter of the glaze point can be 2-5 mm, and the weight can be 0.2-0.8 g. If the glaze point is too small, the weight of the glaze is light, the scattered flowers are small, and the diffusion range is small; when the glaze point is too large, the whole gray level of the glaze point is insufficient, the diffusion effect is poor, the boundary is unclear, and the pattern scattering effect of the brick surface is not natural enough.
In some embodiments, the specific gravity of the colored loose-flowered spot glaze can be controlled to be 1.55-1.60, and the glazing quantity can be 40-60 g/m 2 . Excessive application amount can cause more pattern cross overlapping, and cause boundary fusion blurring and unclear; too little application can result in small and shallow patterns that are not aesthetically pleasing.
And applying digital protective glaze on the surface of the green brick after applying the colored scattered pattern spot glaze. The intermediate protective layer can be promoted to be formed by applying the protective glaze, so that the wear resistance and the antifouling property of the product are improved.
In some embodiments, the digital protective glaze chemistry may include: in mass percent, IL:1.0 to 2.5 percent; na (Na) 2 O：2.0～3.0%；SiO 2 ：45～55%；Al 2 O 3 ：10～20%；CaO：9.0～13%；K 2 O：1.0～3.0%；MgO：1.0～2.5%；ZnO：3.0～8.0%；ZrO 2 ：0.1～0.2%；BaO：3.5～6.2%。
The colored scattered flower spot glaze and the protective glaze are fused at high temperature to form an intermediate protective layer, the scattered flower effect is covered, and the product is more wear-resistant and more antifouling in use.
In some embodiments, the raw material composition of the digital protective glaze may include: the weight percentage of the alloy is 35-45% of potassium feldspar, 15-25% of quartz, 3-5% of wollastonite, 5-8% of calcined talcum, 8-15% of barium carbonate and 3-5% of zinc oxide.
In some embodiments, the digital protective glaze may be applied in a full-scale inkjet printing mode. Preferably, the specific gravity of the digital protective glaze can be controlled to be 1.13-1.21, and the glaze spraying amount can be controlled to be 30-40 g/m 2 . Too much glazing amount can lead to high temperature of the glaze and poor penetration; too little glazing will result in limited protection of the glaze.
Drying, sintering, edging and polishing. And drying the adobe subjected to digital protective glaze application, and then placing the adobe into a kiln for high-temperature firing to obtain the half-number glaze combined spot art colored glaze ceramic plate.
In some embodiments, the high firing temperature may be 1210-1225 ℃, preferably 1215 ℃; the time for the high temperature firing may be 65 to 75 minutes.
The high-temperature sintering time is too short or the sintering temperature is too low, which is not beneficial to the full melt flow of the glaze at high temperature, the matte glaze surface and the uneven pattern scattering effect; the overfiring of the glaze surface can be caused by overlong high-temperature firing time or overhigh firing temperature, and the defects of frosting, prickly heat and the like of the glaze surface can be caused.
The polishing mode can adopt a polishing line half polishing process. Preferably, the fiber grinding blocks of 800 meshes 1 group and 1000 meshes 2 group are adopted for combined half-polishing; the glossiness of the polished brick surface is controlled to be 80-105 degrees, preferably 85 degrees.
The preparation method provided by the invention is to print patterns with spot effect on the existing thin plate green bricks with the thickness of less than 5.5 mm by using digital glaze, then apply a layer of colorful overglaze with bright color, form specific patterns by using the stripping effect of the digital glaze, finally spray the colorful scattered spot glaze on the surface of the ceramic tile by using a spot glaze throwing cabinet, and prepare the spot artistic colored glaze ceramic tile with bright color, strong stereoscopic impression and good antifouling effect by kiln firing.
The half-number-glaze-combined spot art colored glaze ceramic plate obtained by the preparation method provided by the invention has extremely strong weather resistance and color stability, and can be used for indoor decoration.
The present invention will be described in more detail by way of examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
The preparation method of the half digital glaze combined spot art colored glaze ceramic plate provided by the embodiment comprises the following steps:
1. a plurality of green bricks are prepared.
2. And (3) printing engraving ink on the surfaces of different green bricks in an ink jet way, so that a plurality of green bricks respectively form texture patterns with different effects.
3. And applying color overglaze on the surfaces of the green bricks after the engraving ink is printed by the ink jet. The chemical composition of the colored overglaze comprises: in mass percent, IL:2.5%; siO (SiO) 2 ：49.5%；Al 2 O 3 ：12%；Fe 2 O 3 ：0.1%；TiO 2 ：6%；CaO：10%；MgO：3.1%；K 2 O：2.5%；Na 2 O：0.2%；CuO：1.0%；ZnO：5%；ZrO 2 :8%; coO:0.1%; the raw materials of the overglaze comprise: the glass frit comprises, by mass, 25% of frit, 8% of quartz, 12% of calcite, 8% of calcined zinc oxide, 7% of black mud, 8% of zirconium silicate, 6% of calcined talcum, 9.5% of glass powder, 15% of microcrystalline powder and 1.5% of first pigment; the chemical composition of the frit comprises: in mass percent, IL:0.5%; na (Na) 2 O：5.0%；SiO 2 ：51.5%；Al 2 O 3 ：10%；CaO：15%；K 2 O：3.5%；MgO：3.0%；ZnO：8%；ZrO 2 :0.5%; baO:3.0%; the chemical composition of the microcrystalline powder comprises: in mass percent, IL:5.4%; siO (SiO) 2 ：35%；Al 2 O 3 ：8.0%；Fe 2 O 3 ：0.2%；TiO 2 ：4.6%；CaO：15%；MgO：2.0%；K 2 O：2.5%；Na 2 O:3.3%; znO:24%; applying the colored overglaze in a glaze spraying manner of a glaze cabinet; the fineness of the overglaze is that the overglaze passes through a 200-mesh screen, and the screen residue is 0.2wt%; the specific gravity of the overglaze is 1.43, and the glazing quantity is 630g/m 2 。
4. And (3) carrying out ink-jet printing on the surfaces of the green bricks after the colored overglaze is applied.
5. And (3) applying color dispersion fancy point glaze on the surfaces of the green bricks after the patterns are printed by ink jet. The color dispersion fancy glaze comprises the following raw materials: 30% of potassium feldspar, 10% of quartz, 41% of microcrystalline powder, 5.5% of zinc oxide, 6.0% of titanium oxide, 3.0% of zirconium silicate, 3.5% of ammonium metavanadate and 1% of a second pigment; the chemical composition of the color dispersion fancy glaze comprises: in mass percent, IL:7.9%; siO (SiO) 2 ：55%；Al 2 O 3 ：8.5%；Fe 2 O 3 ：0.2%；TiO 2 ：8.9%；CaO：9.0%；MgO：1.9%；K 2 O：3.8%；Na 2 O：1.8%；ZrO 2 :3.0%; applying by adopting a spray gun throwing point mode; specific gravity of 1.55, and glaze spraying amount of 55g/m 2 。
6. And applying digital protective glaze on the surfaces of the green bricks after the colored scattered pattern spot glaze is applied. The chemical composition of the digital protective glaze comprises: in mass percent, IL:2.3%; na (Na) 2 O：2.7%；SiO 2 ：53%；Al 2 O 3 ：16.5%；CaO：9.3%；K 2 O：2.7%；MgO：2.2%；ZnO：5.0%；ZrO 2 :0.1%; baO:6.2%; applying in a full-page printing mode of an ink-jet machine; specific gravity of 1.21, and glaze spraying amount of 35g/m 2 。
7. Drying, firing, edging and polishing to obtain the spot artistic colored glaze ceramic plate combined with half-number glaze. The sintering temperature is 1215 ℃ and the sintering time is 70 minutes; and (3) carrying out combined half polishing by adopting 800-mesh 1-group and 1000-mesh 2-group fiber grinding blocks, and controlling the glossiness of the brick surface to be 85 degrees after polishing.
Fig. 1 to 4 are block face effect diagrams of half-number glaze-combined spot art colored glaze ceramic plates prepared by printing engraving ink of different effect texture patterns on different green bricks in the embodiment 1 of the invention. From the figure, the ceramic plate with different brick surface texture effects prepared in the embodiment 1 has natural and vivid brick surface scattering effect, natural transition of pattern and line changes, excellent decorative effect and better artistic effect.
Comparative example 1
The preparation method of the ceramic plate provided in this comparative example is mainly different from that of example 1 in that: in step 3, the chemical composition of the colored overglaze comprises: in mass percent, IL:3.5%; siO (SiO) 2 ：46.5%；Al 2 O 3 ：11.3%；Fe 2 O 3 ：0.2%；TiO 2 ：7.5%；CaO：10.5%；MgO：2.3%；K 2 O：3.2%；Na 2 O：2.0%；CuO：2.0%；ZnO：7.5%；ZrO 2 :3.0%; coO:0.5%; the raw materials of the overglaze comprise: the glass frit comprises, by mass, 20% of frit, 12% of quartz, 15% of calcite, 8% of calcined zinc oxide, 7% of black mud, 3.5% of zirconium silicate, 5% of calcined talcum, 12% of glass powder, 15% of microcrystalline powder and 2.5% of first pigment.
The comparative example has the problems of over high content of copper oxide and cobalt oxide in the chemical composition of the colored overglaze, and the like, so that the overglaze has lower melting temperature and darker oxide coloration.
Fig. 5 is a graph showing the effect of the tile surface of the ceramic plate prepared in comparative example 1. As can be seen from the figure, the ceramic plate prepared in comparative example 1 has the defects of unclear scattered flower boundary, glaze bubble bottom and the like.
Comparative example 2
The preparation method of the ceramic plate provided in this comparative example is mainly different from that of example 1 in that: in the step 5, the raw materials of the color scattered flower spot glaze comprise: 30% of potassium feldspar, 10% of quartz, 38% of microcrystalline powder, 5.5% of zinc oxide, 6.0% of titanium oxide, 3.0% of zirconium silicate, 6.5% of ammonium metavanadate and 1.0% of a second pigment; colour scattered flower spot glazeThe chemical composition comprises: in mass percent, IL:8.9%; siO (SiO) 2 ：55%；Al 2 O 3 ：8.6%；Fe 2 O 3 ：0.2%；TiO 2 ：8.7%；CaO：9.0%；MgO：1.9%；K 2 O：3.0%；Na 2 O：1.7%；ZrO 2 ：3.0%。
Fig. 6 is a graph showing the effect of the tile surface of the ceramic plate prepared in comparative example 2. As can be seen from the graph, the color scattered pattern spot glaze adopted in the comparative example has too much ammonium metavanadate addition, so that the surface of the prepared ceramic plate brick is scattered with blurred patterns, the boundary is not clear, and a good scattered pattern effect cannot be formed.
Comparative example 3
The preparation method of the ceramic plate provided in this comparative example is mainly different from that of example 1 in that: in step 3, the chemical composition of the colored overglaze comprises: in mass percent, IL:3.5%; siO (SiO) 2 ：36.5%；Al 2 O 3 ：7.3%；Fe 2 O 3 ：0.2%；TiO 2 ：6.5%；CaO：10.5%；MgO：2.3%；K 2 O：2.2%；Na 2 O：1.7%；CuO：1.0%；ZnO：26%；ZrO 2 :2.0%; coO:0.3%; the raw materials of the color overglaze comprise: 16% of frit, 10% of quartz, 14% of calcite, 23% of calcined zinc oxide, 7% of black mud, 2% of zirconium silicate, 5% of calcined talcum, 11.7% of glass powder, 10% of microcrystalline powder and 1.3% of first pigment.
Fig. 7 is a graph showing the effect of the tile surface of the ceramic plate prepared in comparative example 3. As can be seen from the graph, the defects of frosting, matt glaze luster and the like exist on the brick surface of the prepared ceramic plate due to unreasonable arrangement of the color overglaze formula adopted in the comparative example.
The technical principle of the present invention is described above in connection with the specific embodiments. The description is made for the purpose of illustrating the general principles of the invention and should not be taken in any way as limiting the scope of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of this specification without undue burden.
Claims (8)
1. A method for preparing a half-number glaze combined spot art colored glaze ceramic plate, which is characterized by comprising the following steps: firstly, digital glaze or engraving ink is printed on the surface of the green brick in an inkjet mode; then, applying a colored overglaze on the surface of the green brick after the digital glaze is printed or the ink is engraved by ink jet; then, the surface of the green brick after the colored overglaze is applied is painted with colored dispersion colored spot glaze; then, applying digital protective glaze on the surface of the green brick after applying the colored scattered pattern spot glaze; finally, drying and firing the adobe subjected to the digital protective glaze application to obtain the spot artistic colored glaze ceramic plate combined with the half-number glaze;
the raw materials of the color overglaze comprise: 25-40% of frit, 5-10% of quartz, 10-15% of calcite, 5-10% of calcined zinc oxide, 5-8% of black mud, 6-10% of zirconium silicate, 5-10% of calcined talcum, 5-10% of glass powder, 10-20% of microcrystalline powder and 0.5-2.5% of first pigment; the chemical composition of the frit comprises: in mass percent, IL:0.3 to 0.5 percent; na (Na) 2 O：5～6%；SiO 2 ：50～65%；Al 2 O 3 ：10～18%；CaO：10～15%；K 2 O：1.0～3.5%；MgO：1.0～3.0%；ZnO：0.5～8%；ZrO 2 ：0.2～0.5%；BaO：0.5～3%；
The color scattered flower spot glaze comprises the following raw materials: the weight percentage of the composite material is 25 to 40 percent of potassium feldspar, 10 to 15 percent of quartz, 25 to 45 percent of microcrystalline powder, 5 to 10 percent of zinc oxide, 5 to 10 percent of titanium oxide, 3 to 5 percent of zirconium silicate, 3 to 5 percent of ammonium metavanadate and 0.2 to 2 percent of second pigment.
2. The method of manufacturing according to claim 1, wherein the chemical composition of the colored overglaze comprises: in mass percent, IL:1.5 to 4.5 percent; siO (SiO) 2 ：45～55%；Al 2 O 3 ：10～15%；Fe 2 O 3 ：0.1～0.2%；TiO 2 ：5～8%；CaO：10～13%；MgO：2.0～4.0%；K 2 O：1.0～3.0%；Na 2 O：0.2～0.3%；CuO：0.3～1.5%；ZnO：5～11%；ZrO 2 ：8～10%；CoO：0.1～0.2%。
3. The method of claim 1, wherein the color overglaze is applied by spraying; the specific gravity of the colored overglaze is 1.40-1.45, and the glazing quantity is 620-660 g/m 2 。
4. The method of claim 1, wherein the chemical composition of the color loose-flowered glaze comprises: in mass percent, IL:3.5 to 7.9 percent; siO (SiO) 2 ：45～60%；Al 2 O 3 ：8～12%；Fe 2 O 3 ：0.2～0.5%；TiO 2 ：5～10%；CaO：0.2～9%；MgO：1.0～1.9%；K 2 O：1.0～3.8%；Na 2 O：1.0～2.0%；ZrO 2 ：3.0～5.0%。
5. The method for preparing the colored loose-colored spot glaze according to claim 1, wherein the glazing mode is throwing glaze; the specific gravity of the colored scattered flower spot glaze is 1.55-1.60, and the glazing quantity is 40-60 g/m 2 。
6. The method according to claim 1, wherein the chemical composition of the digital protective glaze comprises: in mass percent, IL:1.0 to 2.5 percent; na (Na) 2 O：2.0～3.0%；SiO 2 ：45～55%；Al 2 O 3 ：10～20%；CaO：9.0～13%；K 2 O：1.0～3.0%；MgO：1.0～2.5%；ZnO：3.0～8.0%；ZrO 2 ：0.1～0.2%；BaO：3.5～6.2%。
7. The method according to claim 1, wherein the firing temperature is 1210 to 1225 ℃; the firing time is 65 to 75 minutes.
8. A half-size glaze-bonded spot art colored glaze ceramic board obtained according to the method of manufacture of claim 1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753465A (en) * | 2016-01-24 | 2016-07-13 | 伍剑峰 | Method of making ceramic super-flat mirror art mural and product made thereby |
| WO2017185195A1 (en) * | 2016-04-25 | 2017-11-02 | 广东宏宇新型材料有限公司 | Resource-saving glazed tile with pearlescent and colour-variable effect on surface and preparation method therefor |
| CN113305993A (en) * | 2021-06-24 | 2021-08-27 | 广东协进陶瓷有限公司 | Engraved mercerized glazed tile and production method thereof |
| WO2021189822A1 (en) * | 2020-03-23 | 2021-09-30 | 广东欧文莱陶瓷有限公司 | Fine carving ceramic tile and production process thereof |
| CN113896569A (en) * | 2021-09-26 | 2022-01-07 | 江西唯美陶瓷有限公司 | Ceramic rock plate with multicolor light-transmitting three-dimensional effect and manufacturing method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753465A (en) * | 2016-01-24 | 2016-07-13 | 伍剑峰 | Method of making ceramic super-flat mirror art mural and product made thereby |
| WO2017185195A1 (en) * | 2016-04-25 | 2017-11-02 | 广东宏宇新型材料有限公司 | Resource-saving glazed tile with pearlescent and colour-variable effect on surface and preparation method therefor |
| WO2021189822A1 (en) * | 2020-03-23 | 2021-09-30 | 广东欧文莱陶瓷有限公司 | Fine carving ceramic tile and production process thereof |
| CN113305993A (en) * | 2021-06-24 | 2021-08-27 | 广东协进陶瓷有限公司 | Engraved mercerized glazed tile and production method thereof |
| CN113896569A (en) * | 2021-09-26 | 2022-01-07 | 江西唯美陶瓷有限公司 | Ceramic rock plate with multicolor light-transmitting three-dimensional effect and manufacturing method thereof |
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| CN117682766B (en) | 2024-05-17 |
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