CN111533579B - Ultra-large thin porcelain plate with negative ion function and manufacturing method thereof - Google Patents

Ultra-large thin porcelain plate with negative ion function and manufacturing method thereof Download PDF

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CN111533579B
CN111533579B CN202010001812.3A CN202010001812A CN111533579B CN 111533579 B CN111533579 B CN 111533579B CN 202010001812 A CN202010001812 A CN 202010001812A CN 111533579 B CN111533579 B CN 111533579B
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ultra
porcelain plate
blank
thin porcelain
equal
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CN111533579A (en
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夏昌奎
余剑峰
余昌江
余爱民
樊叶利
李华云
甄燕萍
余惠
郭程长
张文民
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Deqing Nabel Ceramic Co ltd
Jiujiang Nabel Ceramic Co ltd
Hangzhou Nabel Ceramic Co ltd
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Deqing Nabel Ceramic Co ltd
Jiujiang Nabel Ceramic Co ltd
Hangzhou Nabel Ceramic Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention discloses an ultra-large thin porcelain plate with an anion function and a manufacturing method thereof, wherein the manufacturing method comprises the following steps: A. preparing blank powder for the ultra-large specification thin porcelain plate according to a conventional method; B. preparing surface paste for the ultra-large specification thin porcelain plate according to a conventional method; C. distributing blank powder and performing die-free pressing forming; D. automatic green body cutting; E. drying the blank; F. baking; G. applying surface paste; H. drying again; I. penetrating ink jet printing; J. firing; K. and (6) edging. The invention has the beneficial effects that the invention provides the ultra-large thin porcelain plate with the negative ion function and the manufacturing method thereof, solves the problems that the blank body of the thin porcelain plate is easy to damage after the traditional thin porcelain plate adopts wet-process slurry-spraying and other water-containing decoration processes, and the defects of 'water ripple', 'frame', 'slurry curtain wire-pulling' and the like appear after slurry is applied on the surface of the blank body, and endows the ultra-large thin porcelain plate with the negative ion health and environmental protection functions.

Description

Ultra-large thin porcelain plate with negative ion function and manufacturing method thereof
Technical Field
The invention relates to the technical field of building ceramics, in particular to an ultra-large thin porcelain plate with an anion function and a manufacturing method thereof.
Background
The natural stone is influenced by long-term geological motion and climate change and is mixed with associated minerals with other colors, so that high-end, natural and rich decorative effects are formed, and the natural stone is favored by people as a high-grade decorative material. However, the radioactive minerals associated with some natural stones may cause radioactive damage to human health; the natural stone affected by geological action and weathering has more defects such as impurities, cracks and the like, is easy to generate pathological changes, and has poor service performance. In addition, the natural stone is used as an unrenewable resource, is expensive and is difficult to enter common families; the transitional mining and processing of natural stones not only causes the exhaustion of rare and rare stone resources, but also seriously damages the natural ecological environment.
Under the circumstances, products such as ceramic tiles and ceramic plates mainly based on stone imitation are continuously developed on the market. According to the definition of ceramic tiles of the national standard GB/T4100-. The general specification is 0.6m × 0.6m (upper surface area 0.36 m)2) 0.8 m.times.0.8 m (upper surface area 0.64 m)2) The maximum can reach 1.2m multiplied by 1.2m (the upper surface area is 1.44 m)2）。
According to the definition of the ceramic plate of the national standard GB/T23266-2009 ceramic plate, the ceramic plate is a plate-shaped ceramic product which is made of clay and other inorganic non-metallic materials through the production processes of forming, high-temperature firing and the like, the thickness of the ceramic plate is not more than 6mm, and the upper surface area of the ceramic plate is not less than 1.62m2。
Chinese patent CN105622055A provides a method for preparing large-size ultrathin building ceramic tile blanks, which comprises the steps of mixing a plurality of raw materials according to a certain mass percentage, preparing slurry by a wet method, pressing into strips by a semi-dry pressing forming method, and sintering for 2 hours at a certain temperature to obtain the ceramic blanks. The method is to obtain a ceramic blank by drying and sintering a large-size ultrathin building ceramic tile after the ceramic blank is molded without texture decoration on the ceramic blank. Chinese patent CN101634185 discloses a large-sized porcelain tile imitating jade quality and a preparation method thereof, wherein a base material is distributed by pattern fixed point distribution, a semitransparent ceramic material and toner are applied to form a surface layer, and then the product is obtained by the working procedures of pressing, forming, drying, firing and the like. It can be found that in the prior art, the anhydrous decoration process for preparing large-size sheets is mostly adopted, the sheets are formed by cloth and semi-dry pressing, and then dried and fired, and the anhydrous decoration process for preparing large-size sheets is adopted, and the wet-process slurry is sprayed after the formed sheets are adopted, and the water-containing decoration process for re-decoration, drying and firing is not reported. Therefore, the decoration effect of the ultra-large thin porcelain plate is limited.
The anhydrous decoration process refers to a decoration process of powder/dry particle cloth decoration, full-digital non-aqueous ink jet decoration or combination thereof adopted by the ceramic blank. The water-containing decoration process is a decoration process which at least adopts one of glaze and slurry with the water content of not less than 20 percent, screen printing glaze, roller printing glaze and water-based ink for decoration in one or more working procedures of the decoration process, and can be combined with powder/dry particle cloth decoration and non-water-based ink decoration.
The thin porcelain plate produced by the technical scheme of the invention has large specification and thin thickness, is not only suitable for an anhydrous decoration process, but also suitable for a water-containing decoration process, has three-dimensional grains as decorative patterns, has vivid texture and decoration effect of natural stones, has no defects and radioactive hazards of the natural stones, can replace the natural stones and enter common families, can reduce the exploitation and processing of rare and rare stones, reduces the influence and damage on the natural environment, has the negative ion function, can improve the air quality, and has the effects of sterilization, bacteriostasis, human body health care and the like.
Disclosure of Invention
The invention aims to solve the problems that the large-specification thin porcelain plate decoration means in the prior art is limited, the decoration effect is not rich enough, and the large-specification thin porcelain plate blank is easy to have the defects of breakage, 'water ripple', 'frame', 'slurry curtain pull wire' and the like after being decorated by a water-containing decoration process, particularly wet slurry spraying decoration, endow the thin porcelain plate with the negative ion health and environmental protection function, and provide the ultra-large-specification thin porcelain plate with the negative ion function and the manufacturing method thereof. The ultra-large thin porcelain plate with the negative ion function is a plate-shaped ceramic product prepared by clay and other inorganic non-metallic materials through production processes such as molding, high-temperature firing and the like, the water absorption rate of the plate-shaped ceramic product is not higher than 0.5%, the thickness of the plate-shaped ceramic product is not more than 6mm, and the upper surface area of the plate-shaped ceramic product is not less than 1.62m2。
The invention also aims to provide an ultra-large specification thin porcelain plate product with the negative ion function manufactured by the method.
In order to achieve the invention purpose of manufacturing a super-large specification thin porcelain plate with the anion function, the technical scheme of the invention is as follows: a manufacturing method of a super-large specification thin porcelain plate with an anion function comprises the following steps:
A. preparing blank powder for the ultra-large thin porcelain plate according to a conventional method for later use;
B. preparing the surface paste for the ultra-large specification thin porcelain plate according to a conventional method for later use;
C. distributing blank powder and performing die-free press molding: b, distributing the blank powder for the ultra-large thin porcelain plate prepared in the step A according to the designed pattern texture, and forming by a die-free compression forming process to obtain the ultra-large thin porcelain plate blankThe volume weight of the molded blank is more than or equal to 1.95g/cm3；
D. Automatic green body cutting: c, automatically cutting the blank of the ultra-large thin porcelain plate which is formed by die-free pressing in the step C to obtain the required specification and size of the blank;
E. drying the blank: d, drying the ultra-large specification thin porcelain plate blank subjected to automatic blank cutting in the step D according to a conventional method;
F. baking: e, baking the ultra-large thin porcelain plate blank dried in the step E, wherein the baking temperature is 500-800 ℃, the baking period is 5-15 min, and the volume weight of the baked thin porcelain plate blank is more than or equal to 1.80g/cm3The modulus of rupture of the baked green body is more than or equal to 3.0 MPa;
G. applying surface paste for the thin porcelain plate: f, applying the surface slurry for the ultra-large thin porcelain plate prepared in the step B on the surface of the ultra-large thin porcelain plate blank baked in the step F by using an ultra-large spray plate, wherein the diameter of the end face circle of the lower end of the ultra-large spray plate is more than or equal to 2400 mm;
H. and (3) drying again: drying the blank body of the ultra-large specification thin porcelain plate after the surface paste for the ultra-large specification thin porcelain plate is applied in the step G again according to a conventional method;
I. penetrating ink jet printing: spraying penetrating ink on the ultra-large thin porcelain plate blank dried in the step H by using a digital ink-jet printer according to a designed pattern, and matching with the pattern texture of the blank, so that the surface after penetrating ink-jet printing and the blank have similar texture, the thickness of the penetrating ink-jet layer is less than or equal to 0.5mm, and the temperature of the blank before penetrating ink-jet printing is 40-70 ℃;
J. and (3) firing: placing the ultra-large specification thin porcelain plate blank subjected to the penetrating ink jet printing in the step I into a roller kiln for sintering, wherein the sintering temperature is 1150-1250 ℃, and the sintering period is 60-150 min, so as to obtain a semi-finished product of the ultra-large specification thin porcelain plate;
K. edging: edging the semi-finished product of the ultra-large thin porcelain plate by using conventional edging processing equipment to obtain the ultra-large thin porcelain plate finished product, wherein the thickness of the ultra-large thin porcelain plate finished product is less than or equal to 6mm, and the upper surface area of the ultra-large thin porcelain plate finished product is more than or equal to 1.62m2。
And B, in order to realize the negative ion function of the ultra-large specification thin ceramic plate, 1-15% of a negative ion additive is introduced into the surface slurry for the ultra-large specification thin ceramic plate in the step B.
As a further technical scheme, the negative ion additive in the step B comprises the following components in percentage by weight: SiO 22 30%~50%、B2O3 3%~14%、Al2O3 3%~14%、Fe2O3 0~3%、MnO 0.1%~2%、MgO 0.1%~5%、CaO 0.1%~1%、Na2O 0.5%~3%、Li2O 0.1%~2%、ZrO2 10%~50%、Cs20.5 to 2 percent of O and less than or equal to 5 percent of other impurities.
In order to realize the negative ion function of the ultra-large specification thin porcelain plate, a step of printing negative ion ink can be adopted between the step I and the step J.
As a further technical scheme, the negative ion ink comprises a negative ion additive, an organic solvent and a dispersing agent.
As a further technical scheme, the composition of the negative ion additive in the negative ion ink is as follows: SiO 22 30%~50%、B2O3 3%~14%、Al2O3 3%~14%、Fe2O3 0~3%、MnO 0.1%~2%、MgO 0.1%~5%、CaO 0.1%~1%、Na2O 0.5%~3%、Li2O 0.1%~2%、ZrO2 10%~50%、Cs20.5 to 2 percent of O and less than or equal to 5 percent of other impurities.
As a further technical scheme, the organic solvent in the negative ion ink is one or a combination of any two or more of cyclohexane, diethylene glycol dibutyl ether, acetone and isopropyl ester.
In order to realize the negative ion function of the ultra-large specification thin porcelain plate, the negative ion coating material can be sprayed on the surface of the ultra-large specification thin porcelain plate after the step K.
As a further technical scheme, the negative ion coating material comprises a negative ion additive and a liquid dispersing agent.
As a further technical scheme, the negative ion coating material is negativeThe composition of the ionic additive was as follows: SiO 2230%~50%、B2O3 3%~14%、Al2O3 3%~14%、Fe2O3 0~3%、MnO 0.1%~2%、MgO 0.1%~5%、CaO 0.1%~1%、Na2O 0.5%~3%、Li2O 0.1%~2%、ZrO2 10%~50%、Cs20.5 to 2 percent of O and less than or equal to 5 percent of other impurities.
As a further technical scheme, the negative ion additive in the step B, the negative ion additive in the negative ion ink and the negative ion additive in the negative ion coating material are all nano cesium oxide/tourmaline powder composite materials prepared by an electrostatic spinning method, and the preparation method comprises the following steps: dissolving ethylene diamine tetraacetic acid in ethanol to prepare ethylene diamine tetraacetic acid ethanol solution; dissolving cesium nitrate in deionized water to prepare a cesium nitrate solution; dissolving citric acid in deionized water to prepare a citric acid solution; magnetically stirring citric acid solution, adding tourmaline powder while stirring, continuously stirring, adding cesium nitrate solution while stirring, then introducing the ethylene diamine tetraacetic acid ethanol solution, then dropwise adding ammonia water while stirring to adjust the pH value to 7-9 until the Tyndall phenomenon is generated, continuing stirring, 10 to 15 percent of polyvinylpyrrolidone is introduced, the uniformly stirred solution is placed in an emitting device of an electrostatic spinning machine, a medical injector is generally adopted, generating jet flow under the pushing of an injector and the action of high-voltage electric field force, receiving the nano-scale cesium oxide/tourmaline powder precursor on a collecting device, carrying out heat treatment on the collected nano-scale cesium oxide/tourmaline powder precursor at 400-600 ℃, removing contained organic matters, and finally obtaining the nano-scale cesium oxide/tourmaline powder. The measurement shows that the anion release amount of the modified anion additive is not less than 20000/cm3The release amount of negative ions is greatly improved after the nano cesium oxide and the tourmaline powder are compounded.
The formation of negative ions mainly lies in the ionization of gas molecules in the air, and the ionization is derived from the ionization action of natural minerals on the gas molecules in the air, and the tourmaline natural minerals have pyroelectricity and piezoelectricity and can cause small changes in temperature and pressureThe potential difference between the ore crystals can promote the ionization of gas molecules in the ambient air, and the separated electrons are attached to adjacent water and oxygen molecules to be converted into air negative ions; on the other hand, they are derived from natural effects such as ultraviolet rays and radioactive rays. In the prior art, radioactive minerals are generally added, and the radioactive rays emitted by the minerals can enhance the pyroelectricity and piezoelectricity of natural minerals such as tourmaline, thereby enhancing the ionization effect and further improving the negative ion release capability of the natural minerals. However, the addition of radioactive minerals can cause radioactive radiation hazard and affect human health. The photoelectric effect means that under the irradiation of light, electrons in a substance are excited by photons, the excited electrons are combined with water molecules or oxygen molecules in the air to form negative ions, whether the electrons in the substance are excited depends on the substance, if the work function of the electrons in the substance is smaller than the energy of light wavelength, the electrons can be excited, and the work function of the electrons in cesium is 3.0 × 10-19J, a metal with a very small electron work function, can excite its internal electrons by yellow light in visible light. The application creatively compounds the cesium oxide in the tourmaline powder, not only utilizes the capability of the tourmaline powder to generate negative ions, but also endows the tourmaline powder with the negative ions generated by the photoelectric effect, prepares the nano-scale cesium oxide/tourmaline powder by an electrostatic spinning method, and can obviously enhance the negative ion release capability of the powder. The compound cesium oxide in the tourmaline powder utilizes the photoelectric effect to increase the negative ion release concentration of the tourmaline powder.
As a further technical scheme, the liquid dispersant in the negative ion coating material is polyurethane-polymethyl methacrylate copolymer emulsion.
As a further technical scheme, the preparation method of the polyurethane-polymethyl methacrylate copolymer emulsion in the liquid dispersant comprises the following steps: firstly, preparing aqueous polyurethane emulsion: adding dehydrated polyether polyol and toluene diisocyanate into a four-mouth bottle provided with a thermometer, a stirrer and a reflux condenser, adding metered dimethylolpropionic acid dissolved in N-methylpyrrolidone, reacting at 60-80 ℃, adding quantitative 1, 4-butanediol and hydroxymethyl acrylamide, adding a proper amount of methyl methacrylate to reduce the viscosity of the system, cooling to 20-30 ℃, adding triethylamine to neutralize the carboxyl in the system, reacting for 20-40 min, and adding deionized water under high-speed stirring to prepare the waterborne polyurethane emulsion.
Next, a methyl methacrylate monomer emulsion was prepared: stirring a proper amount of deionized water, methyl methacrylate, an emulsifier and an initiator at room temperature until the emulsion is not layered to prepare the methyl methacrylate monomer emulsion.
Finally, preparing a polyurethane-polymethyl methacrylate copolymer emulsion: adding the prepared waterborne polyurethane emulsion into a four-mouth bottle, adding a certain amount of initiator, stirring, dropwise adding the prepared methyl methacrylate monomer emulsion at 70-100 ℃, preserving heat for 2h after dropwise adding, and naturally cooling to below 40 ℃ to obtain the polyurethane-polymethyl methacrylate copolymer emulsion.
In the above steps, the conventional control means in the prior art is adopted, unless otherwise specified.
In order to accomplish the second purpose of the invention, the ultra-large specification thin porcelain plate product with the negative ion function manufactured according to the steps is adopted.
As a further technical scheme, the volume weight uniformity of each part of the ultra-large specification thin porcelain plate blank in the step C is good, and the volume weight difference between any two parts in the same ultra-large specification thin porcelain plate blank is less than or equal to 0.1g/cm3。
And C, the volume weight is calculated according to the national standard GB/T3810.3-2016 ceramic tile test method part 3: measurement of Water absorption, apparent porosity, apparent relative density and volume weight [ ] the definition is given, and the volume weight is expressed as the quotient of the dry weight of the sample divided by the apparent volume (including pores). The performance of the invention is mainly used for measuring the densification degree of the blank body after the ultra-large specification thin porcelain plate is formed/dried and the finished product after the blank body is fired. The volume weight of the blank after the die-free press forming of the ultra-large specification thin porcelain plate has extremely important significance, and on one hand, the blank represents the ultra-large specification thin porcelain plateThe densification degree of the formed ceramic plate blank can meet the requirement of the green strength of the subsequent process, and the reaction sufficiency among the ultra-large specification thin ceramic plate blank powder particles in the firing process is ensured; on the other hand, the volume weight difference between any two parts in the same ultra-large thin porcelain plate blank is less than or equal to 0.1g/cm by adjusting the die-free compression molding process and the performance of the powder of the ultra-large thin porcelain plate blank3And the compactness of each part of the blank of the ultra-large specification thin porcelain plate is controlled to be uniform, so that the simultaneous shrinkage and densification of each part of the ultra-large specification thin porcelain plate can be realized in the drying and sintering processes, and the improvement of the flatness of the ultra-large specification thin porcelain plate after drying and sintering is facilitated.
The baking in the step F mainly has the following functions:
the method can solve the problems that the ultra-large specification thin porcelain plate blank is easy to damage and the like caused by adopting a water-containing decoration process, particularly wet slurry spraying decoration after the ultra-large specification thin porcelain plate blank is formed. The wet slurry spraying mode is generally suitable for ceramic tiles with smaller specifications (generally the specification is less than 900mm multiplied by 900 mm) or ceramic tiles with larger thickness (generally the thickness is more than 6 mm), but can not be directly applied to large-specification and even ultra-large-specification thin porcelain plates because the weight of the ultra-large-specification thin porcelain plate blank is much larger than that of the traditional-specification ceramic tiles (even thicker ceramic tiles), although the ultra-large specification thin porcelain plate blank has certain green strength after being dried, if the surface slurry is sprayed in a wet slurry spraying way, microcosmically, due to hydration, water molecules in the flour slurry penetrate into the crystal lattice frame of the powder on the surface of the blank body, mineral molecules in the powder on the surface of the blank body react with water molecules to generate solvated particles, so that the dissolving process of the powder is promoted, and the cohesive force between the powder on the surface of the blank body is reduced; macroscopically, the powder on the surface of the blank absorbs moisture and expands, the surface bonding strength of the blank is damaged, the green strength of the upper half part of the blank is sharply reduced, and a narrow strip-shaped conveying line (convenient for recycling the slurry) is adopted during slurry spraying instead of a wide belt-shaped conveying line, so that the ultra-large specification is very easy to cause to be thinThe deformation of the blank of the porcelain plate even exceeds the maximum deformation which can be borne by the blank to cause damage, particularly when the specification of the ultra-large specification thin porcelain plate is from 900mm multiplied by 1800mm (the upper surface area is 1.62 m)2) Increase to 1600mm multiplied by 5200mm (upper surface area 8.32 m)2) This effect is more pronounced. After the baking process of the step F is adopted, the ultra-large thin porcelain plate blank has certain strength, and the hydration effect can be greatly weakened, so that the blank damage is greatly reduced.
And secondly, organic matters in the blank of the ultra-large specification thin porcelain plate can be discharged, and the surface quality of the ultra-large specification thin porcelain plate prepared after sintering can be improved. The temperature of the baking process in the step F is 500-800 ℃, the temperature stage belongs to a preheating zone of a traditional kiln, various organic matters in the ultra-large thin porcelain plate blank are discharged at the stage, and if carbonate and sulfate exist, decomposition is started, and gas is discharged; intermolecular crystal water is removed, the blank shrinks, and the weight loss is rapidly increased; the water in the clay structure begins to be discharged, and at the temperature of 573 ℃ or so, the beta-quartz in the blank is transformed to alpha-quartz crystal phase and is accompanied with volume expansion. Therefore, after the baking process of the step F, when the ultra-large specification thin porcelain plate blank enters a kiln to be fired, almost no physical and chemical changes such as organic matter discharge exist, the stability of the firing performance of the ultra-large specification thin porcelain plate is facilitated, and the surface quality of the ultra-large specification thin porcelain plate prepared after firing is improved.
And thirdly, the decoration means and the decoration effect are enriched. The prior art mostly adopts the anhydrous decoration process of cloth, semi-dry pressing and forming into a thin porcelain plate blank, drying and firing, and adopts the water-containing decoration process of spraying wet-process slurry after the blank is formed, and then decorating, drying and firing, which is not reported. Therefore, the decoration means and decoration effect of the ultra-large specification thin porcelain plate are limited. After the baking process of the step F of the invention is adopted, the ultra-large specification thin porcelain plate blank has certain strength (the modulus of rupture is more than or equal to 3 MPa), and the method is not only suitable for the anhydrous decoration process, but also suitable for the water-containing decoration process, thereby enriching the decoration means and the decoration effect of the ultra-large specification thin porcelain plate.
And fourthly, compared with the traditional biscuit firing process, the baking process in the step F of the invention also has advantages. Bisque firing refers to a process of heat treatment of a green body at a certain temperature to make the green body have a certain mechanical strength. The biscuit firing temperature is 900-1100 ℃, the biscuit firing period is 50-100 min, and the biscuit firing temperature is high, so that the blank of the ultra-large thin porcelain plate has certain strength (the modulus of rupture is more than or equal to 10 MPa), the powder particles of the blank in the blank are rapidly gathered, air holes are extruded, the blank structure is remarkably densified, the adsorption capacity of the blank of the ultra-large thin porcelain plate after biscuit firing on wet process surface slurry is weakened, and the biscuit is not beneficial to implementation of large-amount wet process slurry spraying and other water-containing decoration processes. Compared with the prior art, the temperature of the baking process is lower, the period is shorter, the baked ultra-large thin porcelain plate blank has a certain strength (the modulus of rupture is more than or equal to 3 MPa), and the baked ultra-large thin porcelain plate blank still has strong adsorption capacity on wet-process surface slurry, and is suitable for wet-process slurry spraying and other water-containing decoration processes; on the other hand, compared with biscuit firing, the baking temperature is lower, the period is shorter, the energy consumption of the kiln is lower, the production flow is quicker and more efficient, and the production cost is obviously reduced.
The traditional wet method drenches the mode of applying cloth of thick liquid and appears "water ripple" defect easily, especially to the product of great specification, this defect is mainly because behind the product specification grow, and the thick liquids that the supporting thick liquids equipment size that drenches aggravation of mechanical shock that leads to thereupon the grow, thick liquids curtain area grow thereupon and the thick liquids that leads to distribute inhomogeneous etc. and give execution cloth inhomogeneous, and the product polishing back surface appears like the corrugate fluctuation of the waviness ripple of water face, influences surface decoration effect. Secondly, wet slurry spraying is adopted to apply the surface slurry on the ultra-large thin porcelain plate, so that the 'frame' defect is easy to occur, namely the surface slurry cannot be uniformly applied on the edge of the blank of the ultra-large thin porcelain plate due to the surface tension effect, so that the local slurry stacking is caused, and the 'frame' defect is formed. Thirdly, if the slurry is applied to the ultra-large thin porcelain plate in a wet slurry spraying manner, the slurry curtain wire drawing defect is easy to occur, because the specification of the ultra-large thin porcelain plate is obviously larger than that of the traditional ceramic tile, when the slurry is applied in a wet slurry spraying manner, the size of slurry spraying equipment is inevitably enlarged, the slurry curtain with uniform distribution and components is difficult to form on the large slurry spraying equipment by the surface slurry, and the slurry curtain wire drawing defect is likely to occur during slurry spraying due to the fact that a small amount of bulk fake particles caused by precipitation or impurities left by the slurry spraying equipment are not completely cleaned, and then the local slurry shortage defect is formed on the surface of the ultra-large thin porcelain plate blank, and the pit defect is formed after sintering.
The invention prepares the surface slurry for the ultra-large specification thin porcelain plate with reasonable rheological property by designing and adopting the ultra-large shower tray with the diameter of the end face circle of the lower end not less than 2400mm, and better solves the problems. Aiming at the defects of 'water ripple' and 'frame', the invention is described by combining the attached drawings 1 and 2, the designed oversized slurry spraying disc comprises a slurry spraying cover a and a slurry separator b, the slurry spraying cover a is composed of a slurry spraying cover main body cambered surface a1 and a slurry spraying cover end part cambered surface a2, and the slurry separator b is positioned at the upper center of the slurry spraying cover a. Compared with the traditional shower tray, the oversized shower tray is mainly designed and improved from three aspects: firstly, the diameter d of the end face circle at the lower end of the slurry spraying cover a is not less than 2400mm, so that the size requirement of an oversized thin porcelain plate blank with an anion function on a spraying disc for applying surface slurry can be fully met; secondly, the arc radius R1 of the arc surface a1 of the slurry pouring cover body is designed to be 4300-5000 mm, the arc radius R2 of the arc surface a2 of the end part of the slurry pouring cover is designed to be 180-240 mm, the arc surface of the slurry pouring cover body is perfectly connected with the arc surface of the end part of the slurry pouring cover through the design of the arc radii of the arc surface a1 of the slurry pouring cover body and the arc surface a2 of the end part of the slurry pouring cover, a tangent line L1 is shared by the connection part, the included angle between a tangent line L1 at the intersection point of the arc surface of the slurry pouring cover body and the arc surface of the end part of the slurry pouring cover and a horizontal line L2 is adjusted, the included angle alpha of the two tangent lines is 10-20 degrees, when the slurry for the ultra-large thin porcelain plate is overflowed to the upper surface of the slurry pouring cover a through the slurry distributor b, the pressure of the slurry overflowing to the slurry pouring cover a is very uniform and the internal bubbles of the slurry are eliminated, and the slurry overflows to the end part of the slurry pouring cover a2 at a uniform speed when the slurry is transited to the arc surface a2 through the arc surface a1 of the slurry pouring cover body on the slurry pouring cover b, finally, wet slurry spraying is carried out on the ultra-large thin porcelain plate blank through the edge of the cambered surface a2 at the end part of the slurry spraying cover; thirdly, the width c of the cambered surface a2 at the end part of the slurry spraying cover is designed to be 80-120 mm, compared with the width of the cambered surface at the end part of the traditional slurry spraying cover which is a tray, the width of the cambered surface at the end part of the slurry spraying cover is wider, the slurry for the ultra-large thin porcelain plate is more smooth when passing through the cambered surface at the end part of the slurry spraying cover, and the slurry spraying speed on the surface of the ultra-large thin porcelain plate blank is easier to control. By combining the design improvements of the three aspects, the invention well solves the defects of 'water ripple' and 'frame'. Aiming at the defect of 'slurry curtain wire drawing', the invention strictly controls the working procedures of iron removal, sieving, storage and the like of the surface slurry for the ultra-large specification thin porcelain plate by optimizing the technological parameters of the surface slurry for the ultra-large specification thin porcelain plate, such as flow rate, specific gravity, viscosity and the like, and frequently cleans related slurry applying equipment such as an ultra-large spray disc, a slurry barrel and the like, thereby finally well solving the problem of 'slurry curtain wire drawing'.
The temperature of the blank before penetrating and ink jetting in the step I needs to be controlled between 40 ℃ and 70 ℃, because the penetrating and ink jetting decoration process is adopted, the used penetrating ink is ionic solvent type ceramic ink, compared with the traditional pigment type ceramic ink, the penetrating ink has certain penetrating performance, and needs to be matched with the blank of the ultra-large specification thin porcelain plate in order to form the decoration texture with stable color development and rich layers, wherein the temperature of the blank before penetrating ink jet printing is an important factor, the temperature of the blank before penetrating ink jet printing is too low, the drying rate of penetrating ink in a surface slurry layer is easy to reduce, the penetrating ink just sprayed and printed on the surface of the surface paste layer is in a flowing state, so that the penetration depth of the penetrating ink in the surface paste layer is easily limited, and the penetrating ink is easy to irregularly diffuse on the surface of the surface paste layer to cause the fuzzy texture and the chromatic aberration of the surface of the finished product of the ultra-large thin porcelain plate; however, if the temperature of the blank body before penetrating ink jet printing is too high, organic matters in penetrating ink are rapidly heated and evaporated when the penetrating ink contacts the surface of the surface slurry layer, and the penetrating capacity of the penetrating ink and the penetrating depth in the blank body of the ultra-large specification thin porcelain plate are influenced. According to the invention, innovative labor is utilized to determine that when the temperature of the blank body before penetrating ink jet printing is 40-70 ℃, the color development of penetrating ink is facilitated, and the decorative pattern with stable color development, rich layers and fine texture is formed.
The firing system in the step J needs to be correspondingly adjusted according to the produced ultra-large specification thin porcelain plate, particularly, after the thickness of the ultra-large specification thin porcelain plate is further reduced, in the temperature rise stage of the firing process, because the temperatures of all sections of the kiln are different, and the specification of the ultra-large specification thin porcelain plate is very large, when the ultra-large specification thin porcelain plate is conveyed and heated in a wide kiln by using a roller rod, a large longitudinal temperature difference is easily formed in the advancing direction of the ultra-large specification thin porcelain plate, namely, the temperature of the part of the same ultra-large specification thin porcelain plate close to the advancing direction of the ultra-large specification thin porcelain plate is higher, the temperature of the part of the same ultra-large specification thin porcelain plate relative to the advancing direction of the ultra-large specification thin porcelain plate is lower, and the temperature of the plate is just opposite in the temperature reduction stage, so that a large longitudinal temperature difference is formed on the same ultra-large specification thin porcelain plate, the invention realizes the measures of balanced temperature rise/reduction, adjustment of air pressure and excess air coefficient in the kiln and the like by properly prolonging the temperature rise transition region and the temperature reduction transition region, namely, by a temperature rise system from the preheating zone to the burning zone and a temperature reduction system from the burning zone to the cooling zone, and can well improve the shrinkage uniformity and the flatness after burning of the ultra-large thin porcelain plate.
In the cooling stage of the firing process, if the internal stress of the ultra-large thin porcelain plate exists, local cracking caused by nonuniform stress release of the ultra-large thin porcelain plate is very easy to cause, so that the opening of a quenching air pipe in a kiln quenching area cannot be over-extended, the quenching openings of the upper layer and the lower layer of a roller rod are approximately consistent, the temperature difference between the upper layer and the lower layer of the roller rod is reduced, and the stress generated by inconsistent internal and external contraction in the cooling process of a blank body is reduced, so that the defects of wind cracking and the like of the product are avoided. Finally, the temperature difference between the upper layer and the lower layer of the roller rod can be controlled within 50-100 ℃, and the problem of cooling and cracking of the ultra-large thin porcelain plate is effectively solved.
As a further technical scheme, the linear thermal expansion coefficient of the blank layer of the semi-finished product of the ultra-large thin porcelain plate in the step J is 6.5 multiplied by 10-6~8×10-6The linear thermal expansion coefficient of the surface paste layer is 6 x 10 DEG C-6~7.5×10-6/℃。
As a further technical scheme, in the step J, the water absorption rate of the ultra-large thin porcelain plate semi-finished product is less than or equal to 0.5 percent, the failure strength is more than or equal to 800N, the modulus of rupture is more than or equal to 48MPa, and the volume weight is more than or equal to 2.25g/cm3。
As a further technical scheme, the thickness of the penetrating ink-jet printing layer in the step I is 0.1-0.5 mm.
And as a further technical scheme, after the edge grinding treatment in the step K, cutting a finished product to obtain the required specification and size of the finished product.
As a further technical scheme, after the edge grinding treatment in the step K, a polishing process is adopted for treatment. The surface of the thin porcelain plate prepared by the method is subjected to required polishing treatment by changing the material quality and the polishing process parameters of the grinding block, so that a finished product of the ultra-large thin porcelain plate with a bright surface and a negative ion function can be obtained, and the glossiness is more than or equal to 55 gloss units; or obtaining a finished product of the ultra-large specification thin porcelain plate with the soft surface and the anion function, wherein the glossiness is 15-30 gloss units; or obtaining a finished product of the ultra-large specification thin porcelain plate with the matte surface and the anion function, wherein the glossiness is 5-15 gloss units.
The ultra-large specification thin porcelain plate with the anion function manufactured by the invention has the following beneficial effects:
compared with the prior art which mostly adopts an anhydrous decoration process, the baking process is innovatively introduced into the manufacturing method of the ultra-large specification thin porcelain plate, so that the problems that the ultra-large specification thin porcelain plate blank is easy to damage and the like caused by adopting wet-process slurry spraying and other water-containing decoration processes after the ultra-large specification thin porcelain plate blank is formed can be solved.
Compared with the existing decoration means and decoration effect of the thin porcelain plate, the invention innovatively introduces the baking process in the manufacturing method of the ultra-large thin porcelain plate, obviously improves the strength of the blank body of the ultra-large thin porcelain plate, and is suitable for the waterless decoration process and the water-containing decoration process, so that the decoration means and decoration effect are more abundant.
Compared with the traditional biscuit firing process, on one hand, the firing process disclosed by the invention has the advantages that the temperature is lower, the period is shorter, the fired ultra-large specification thin porcelain plate biscuit has certain strength and strong adsorption capacity to wet-process surface slurry, and is suitable for a wet-process slurry spraying decoration process, and the temperature of the biscuit firing process is relatively higher, the period is longer, so that the adsorption capacity of the ultra-large specification thin porcelain plate biscuit to the wet-process surface slurry after biscuit firing is greatly weakened, and the implementation of wet-process slurry spraying and other water-containing decoration processes is not facilitated; on the other hand, the baking temperature is lower, the period is shorter, the energy consumption of the kiln is lower, the production flow is quicker and more efficient, and the production cost is obviously reduced.
Compared with the traditional wet-process surface paste applying mode, the invention prepares the surface paste for the ultra-large specification thin porcelain plate with reasonable rheological property by designing and adopting the ultra-large spray disc with the end face circle diameter of not less than 2400mm, better solves the defects of 'water ripple' and 'frame', strictly controls the working procedures of iron removal, sieving, storage and the like of the surface paste for the ultra-large specification thin porcelain plate, cleans related paste applying equipment such as the ultra-large spray disc, a paste barrel and the like by optimizing the process parameters such as the flow rate, the specific gravity, the viscosity and the like of the surface paste for the ultra-large specification thin porcelain plate, and better solves the problem of 'paste curtain wire pulling'.
The invention realizes the balanced temperature rise/reduction by properly prolonging the temperature rise transition area and the temperature reduction transition area, namely, the temperature rise system from the preheating zone to the firing zone and the temperature reduction system from the firing zone to the cooling zone, and measures such as adjusting the excess coefficient of air pressure in the kiln can reduce the large longitudinal temperature difference of the ultra-large specification thin porcelain plate in the firing process of the kiln, and well improve the shrinkage uniformity and the flatness after firing of the ultra-large specification thin porcelain plate. Through the valve opening of the quenching air pipe in the quenching area of the kiln and the valve opening of the hot air pumping opening in the quenching area, the temperature difference between the upper layer and the lower layer of the roller rod is controlled within 50-100 ℃, and the problem of cooling and cracking of the ultra-large thin porcelain plate is effectively solved.
According to the invention, by introducing the anion additive into the surface slurry for the ultra-large thin porcelain plate, or printing the anion ink or spraying the anion coating material, the ultra-large thin porcelain plate is endowed with excellent anion health and environmental protection functions, and can inhibit bacteria and mildew, purify air, promote metabolism of a human body and improve the immunity of the human body. The average negative ion release amount of the super-large specification thin porcelain plate surface is more than or equal to 1500/cm3Measuring the average release amount of more than or equal to 1000 anions/cm at a position 1m away from the surface of the ultra-large specification thin porcelain plate3The standard concentration of the negative ions of the fresh air specified by the world health organization is achieved: not less than 1000-1500/cm in air3。
Drawings
FIG. 1 is a side view of the oversized shower tray of the present invention;
the slurry pouring device comprises a slurry pouring cover, b slurry separator, c slurry pouring cover end arc surface width, d slurry pouring cover lower end surface circle diameter, R1 slurry pouring cover main body arc surface arc radius, R2 slurry pouring cover end arc radius, L1 slurry pouring cover main body arc surface and slurry pouring cover end arc surface intersection point tangent line, L2 horizontal line, alpha slurry pouring cover main body arc surface and slurry pouring cover end arc surface intersection point tangent line L1 and horizontal line L2 included angle.
FIG. 2 is a view of the ultra large shower tray slurry cover of the present invention;
wherein a1 is the cambered surface of the main body of the slurry pouring cover, and a2 is the cambered surface of the end part of the slurry pouring cover.
Detailed Description
Specific embodiments are given below in conjunction with fig. 1.
Example 1
A. Preparing blank powder for the ultra-large thin porcelain plate according to a conventional method for later use;
B. preparing a surface paste for the ultra-large specification thin porcelain plate according to a conventional method, wherein the surface paste contains 5% of a negative ion additive for later use;
the negative ion additive comprises the following components: SiO 22 50%、B2O3 8%、Al2O3 3%、Fe2O3 2%、MnO 1%、MgO 3%、CaO 0.1%、Na2O 2%、Li2O 1%、ZrO2 28%、Cs20.5 percent of O and less than or equal to 5 percent of other impurities;
the preparation method of the anion additive comprises the following steps: dissolving ethylene diamine tetraacetic acid in ethanol to prepare ethylene diamine tetraacetic acid ethanol solution; dissolving cesium nitrate in deionized water to prepare a cesium nitrate solution; dissolving citric acid in deionized water to prepare a citric acid solution; magnetically stirring a citric acid solution, adding tourmaline powder while stirring, continuously stirring, adding a cesium nitrate solution while stirring, then introducing an ethylene diamine tetraacetic acid ethanol solution, then dropwise adding ammonia water while stirring to adjust the pH value to 7 until a Tyndall phenomenon is generated, continuously stirring, introducing 10% polyvinylpyrrolidone, placing the uniformly stirred solution in an emitting device in an electrostatic spinning machine, generally adopting a medical injector, generating jet flow under the action of the pushing of the injector and high-voltage electric field force, receiving a nano-scale cesium oxide/tourmaline powder precursor on a collecting device, carrying out heat treatment on the collected nano-scale cesium oxide/tourmaline powder precursor at 400 ℃, removing contained organic matters, and finally obtaining nano-scale cesium oxide/tourmaline powder;
C. distributing blank powder and performing die-free press molding: b, distributing the blank powder for the ultra-large thin porcelain plate prepared in the step A according to the designed pattern texture, and forming by a die-free compression forming process to obtain the ultra-large thin porcelain plate blank, wherein the bulk weight of the formed blank is 1.95g/cm3；
D. Automatic green body cutting: c, automatically cutting the blank of the ultra-large thin porcelain plate which is formed by die-free pressing in the step C to obtain the required specification and size of the blank;
E. drying the blank: d, drying the ultra-large specification thin porcelain plate blank subjected to automatic blank cutting in the step D according to a conventional method, wherein the drying temperature is 150 ℃;
F. baking: e, baking the ultra-large thin porcelain plate blank dried in the step E, wherein the baking temperature is 700 ℃, the baking period is 10min, and the volume weight of the baked ultra-large thin porcelain plate blank is 1.80g/cm3The modulus of rupture of the baked blank is 3.0 MPa;
G. applying cloth sizing: b, distributing the surface slurry for the ultra-large thin porcelain plate prepared in the step B on the surface of the ultra-large thin porcelain plate blank baked in the step F by using an ultra-large spray disc, wherein the diameter d of the end face circle of the lower end of the ultra-large spray disc is 2400mm, the arc radius R1 of the arc surface a1 of the slurry spray cover body of the ultra-large spray disc is 4300mm, the arc radius R2 of the arc surface a2 of the end part of the slurry spray cover is 240mm, the included angle alpha between the tangent line L1 at the intersection point of the arc surface of the slurry spray cover body and the arc surface of the end part of the slurry spray cover and the horizontal line L2 is 20 degrees, and the width c of the arc surface a2 at the end part of the slurry spray cover is 80 mm;
H. and (3) drying again: drying the blank body of the ultra-large thin porcelain plate subjected to the surface sizing for the ultra-large thin porcelain plate applied in the step G again according to a conventional method, wherein the drying temperature is 180 ℃;
I. penetrating ink jet printing: spraying penetrating ink on the ultra-large thin porcelain plate blank dried again in the step H by using a digital ink-jet printer according to a designed pattern, and matching with the pattern texture of the blank, so that the surface after penetrating ink-jet printing and the blank have similar texture and texture, the thickness of the penetrating ink-jet layer is 0.4mm, and the temperature of the blank before penetrating ink-jet printing is 40 ℃;
J. and (3) firing: placing the blank of the ultra-large specification thin porcelain plate subjected to ink jet printing in a roller kiln, and sintering by using a conventional thin porcelain plate sintering temperature system, a conventional pressure system and a conventional atmosphere system, wherein the sintering temperature is 1200 ℃, and the sintering period is 100min to obtain a semi-finished product of the ultra-large specification thin porcelain plate, and the linear thermal expansion coefficient of the blank layer of the semi-finished product of the ultra-large specification thin porcelain plate is 6.5 multiplied by 10-6The linear thermal expansion coefficient of the surface paste layer is 6 x 10 DEG C-6/℃The water absorption of the ultra-large thin porcelain plate semi-finished product is 0.3 percent, the failure strength is 815N, the breaking modulus is 48MPa, and the volume weight is 2.25g/cm3；
K. Edging: edging the semi-finished product of the ultra-large thin porcelain plate by using conventional edging processing equipment to obtain the finished product of the ultra-large thin porcelain plate with the negative ion function, wherein the specification of the finished product is 1.6m multiplied by 4.8m (the upper surface area is 7.68 m)2) 6mm in thickness, and the average negative ion release amount of the super-large thin porcelain plate surface is 1500/cm3。
Example 2
A. Preparing blank powder for the ultra-large thin porcelain plate according to a conventional method for later use;
B. preparing the surface paste for the ultra-large specification thin porcelain plate according to a conventional method for later use;
C. distributing blank powder and performing die-free press molding: b, distributing the blank powder for the ultra-large thin porcelain plate prepared in the step A according to the designed pattern texture, and forming by a die-free compression forming process to obtain the ultra-large thin porcelain plate blank, wherein the bulk weight of the formed blank is 2.10g/cm3；
D. Automatic green body cutting: c, automatically cutting the blank of the ultra-large thin porcelain plate which is formed by die-free pressing in the step C to obtain the required specification and size of the blank;
E. drying the blank: d, drying the ultra-large specification thin porcelain plate blank subjected to automatic blank cutting in the step D according to a conventional method, wherein the drying temperature is 180 ℃;
F. baking: e, baking the ultra-large thin porcelain plate blank dried in the step E, wherein the baking temperature is 800 ℃, the baking period is 5min, and the volume weight of the baked ultra-large thin porcelain plate blank is 1.90g/cm3The modulus of rupture of the baked blank is 4.0 MPa;
G. applying cloth sizing: b, applying the surface slurry for the ultra-large thin porcelain plate prepared in the step B on the surface of the ultra-large thin porcelain plate blank baked in the step F by using an ultra-large tray, wherein the diameter d of the end face circle of the lower end of the ultra-large tray is 2700mm, the arc radius R1 of the arc surface a1 of the slurry spraying cover body of the ultra-large tray is 5000mm, the arc radius R2 of the arc surface a2 of the end part of the slurry spraying cover is 180mm, the included angle alpha between the tangent line L1 at the intersection point of the arc surface of the slurry spraying cover body and the arc surface of the end part of the slurry spraying cover and a horizontal line L2 is 17 degrees, and the width c of the arc surface a2 c of the end part of the slurry spraying cover is 100 mm;
H. and (3) drying again: drying the ultra-large thin porcelain plate blank subjected to surface sizing for the thin porcelain plate in the step G again according to a conventional method, wherein the drying temperature is 200 ℃;
I. penetrating ink jet printing: spraying penetrating ink on the ultra-large thin porcelain plate blank dried again in the step H by using a digital ink-jet printer according to a designed pattern, and matching with the pattern texture of the blank, so that the surface after penetrating ink-jet printing and the blank have similar texture and texture, the thickness of the penetrating ink-jet layer is 0.5mm, and the temperature of the blank before penetrating ink-jet printing is 70 ℃;
J. printing negative ion ink: spraying negative ion ink on the ultra-large specification thin porcelain plate blank after penetrating and spraying ink in the step I by adopting a digital ink-jet printer according to a designed pattern;
the negative ion ink comprises a negative ion additive, diethylene glycol dibutyl ether and a dispersing agent;
the negative ion additive comprises the following components: SiO 22 30%、B2O3 14%、Al2O3 14%、Fe2O3 1%、MnO 2%、MgO 5%、CaO 0.2%、Na2O 0.5%、Li2O 0.1%、ZrO2 30%、Cs2O2 percent and the rest impurities are less than or equal to 5 percent;
the preparation method of the anion additive comprises the following steps: dissolving ethylene diamine tetraacetic acid in ethanol to prepare ethylene diamine tetraacetic acid ethanol solution; dissolving cesium nitrate in deionized water to prepare a cesium nitrate solution; dissolving citric acid in deionized water to prepare a citric acid solution; magnetically stirring a citric acid solution, adding tourmaline powder while stirring, continuously stirring, adding a cesium nitrate solution while stirring, then introducing an ethylene diamine tetraacetic acid ethanol solution, then dropwise adding ammonia water while stirring to adjust the pH value to 8 until a Tyndall phenomenon is generated, continuously stirring, introducing 15% polyvinylpyrrolidone, placing the uniformly stirred solution in an emitting device in an electrostatic spinning machine, generally adopting a medical injector, generating jet flow under the action of the pushing of the injector and high-voltage electric field force, receiving a nano-scale cesium oxide/tourmaline powder precursor on a collecting device, carrying out heat treatment on the collected nano-scale cesium oxide/tourmaline powder precursor at 500 ℃, removing contained organic matters, and finally obtaining nano-scale cesium oxide/tourmaline powder;
K. and (3) firing: placing the blank of the ultra-large thin porcelain plate printed with the negative ion ink in the step J into a roller kiln, and sintering by using a conventional thin porcelain plate sintering temperature system, a conventional pressure system and a conventional atmosphere system, wherein the sintering temperature is 1250 ℃, and the sintering period is 60min to obtain a semi-finished product of the ultra-large thin porcelain plate, and the linear thermal expansion coefficient of the blank layer of the semi-finished product of the ultra-large thin porcelain plate is 8 multiplied by 10-6The coefficient of linear thermal expansion of the surface paste layer was 7.5X 10 at/. degree.C-6/° C, the water absorption of the ultra-large specification thin porcelain plate semi-finished product is 0.1 percent, the failure strength is 1010N, the breaking modulus is 55MPa, and the volume weight is 2.36g/cm3；
L, edging: and D, utilizing conventional edging processing equipment to carry out edging treatment on the semi-finished product of the ultra-large specification thin porcelain plate prepared in the step K to prepare the finished product of the ultra-large specification thin porcelain plate with the negative ion function, wherein the specification of the finished product is 1.6m multiplied by 3.2m (the upper surface area is 5.12 m)2) The thickness is 5.5mm, and the average negative ion release amount of the super-large thin porcelain plate is 2500/cm3。
Example 3
A. Preparing blank powder for the ultra-large thin porcelain plate according to a conventional method for later use;
B. preparing the surface paste for the ultra-large specification thin porcelain plate according to a conventional method for later use;
C. distributing blank powder and performing die-free press molding: b, distributing the blank powder for the ultra-large thin porcelain plate prepared in the step A according to the designed pattern texture, and forming by a die-free compression forming process to obtain the ultra-large thin porcelain plateA blank body, the bulk weight of the formed blank body is 2.00g/cm3；
D. Automatic green body cutting: c, automatically cutting the blank of the ultra-large thin porcelain plate which is formed by die-free pressing in the step C to obtain the required specification and size of the blank;
E. drying the blank: d, drying the ultra-large specification thin porcelain plate blank subjected to automatic blank cutting in the step D according to a conventional method, wherein the drying temperature is 200 ℃;
F. baking: e, baking the ultra-large thin porcelain plate blank dried in the step E, wherein the baking temperature is 500 ℃, the baking period is 15min, and the volume weight of the baked ultra-large thin porcelain plate blank is 1.87g/cm3The modulus of rupture of the baked blank is 3.5 MPa;
G. applying cloth sizing: b, applying the surface slurry for the ultra-large thin porcelain plate prepared in the step B on the surface of the ultra-large thin porcelain plate blank baked in the step F by using an ultra-large tray, wherein the diameter d of the end face circle of the lower end of the ultra-large tray is 2450mm, the arc radius R1 of the arc surface a1 of the slurry spraying cover body of the ultra-large tray is 4800mm, the arc radius R2 of the arc surface a2 of the end part of the slurry spraying cover is 220mm, the included angle alpha between the tangent line L1 at the intersection point of the arc surface of the slurry spraying cover body and the arc surface of the end part of the slurry spraying cover and a horizontal line L2 is 10 degrees, and the width c of the arc surface a2 at the end part of the slurry spraying cover is 120 mm;
H. and (3) drying again: drying the blank body of the ultra-large thin porcelain plate subjected to the surface sizing for the ultra-large thin porcelain plate applied in the step G again according to a conventional method, wherein the drying temperature is 150 ℃;
I. penetrating ink jet printing: spraying penetrating ink on the ultra-large thin porcelain plate blank dried again in the step H by using a digital ink-jet printer according to a designed pattern, and matching with the pattern texture of the blank, so that the surface after penetrating ink-jet printing and the blank have similar texture and texture, the thickness of the penetrating ink-jet layer is 0.3mm, and the temperature of the blank before penetrating ink-jet printing is 55 ℃;
J. printing negative ion ink: spraying negative ion ink on the ultra-large specification thin porcelain plate blank after penetrating and spraying ink in the step I by adopting a digital ink-jet printer according to a designed pattern;
the negative ion ink comprises a negative ion additive, cyclohexane, isopropyl ester and a dispersing agent;
the negative ion additive comprises the following components: SiO 22 40%、B2O3 3%、Al2O3 7%、MnO 0.1%、MgO 0.1%、CaO 1%、Na2O 3%、Li2O 2%、ZrO2 43%、Cs2O1 percent and the rest impurities are less than or equal to 5 percent;
the preparation method of the anion additive comprises the following steps: dissolving ethylene diamine tetraacetic acid in ethanol to prepare ethylene diamine tetraacetic acid ethanol solution; dissolving cesium nitrate in deionized water to prepare a cesium nitrate solution; dissolving citric acid in deionized water to prepare a citric acid solution; magnetically stirring a citric acid solution, adding tourmaline powder while stirring, continuously stirring, adding a cesium nitrate solution while stirring, introducing an ethylene diamine tetraacetic acid ethanol solution, then dropwise adding ammonia water while stirring to adjust the pH value to 9 until a Tyndall phenomenon is generated, continuously stirring, introducing 12% polyvinylpyrrolidone, placing the uniformly stirred solution in an emitting device in an electrostatic spinning machine, generally adopting a medical injector, generating jet flow under the action of the pushing of the injector and high-pressure electric field force, receiving a nano-scale cesium oxide/tourmaline powder precursor on a collecting device, carrying out heat treatment on the collected nano-scale cesium oxide/tourmaline powder precursor at 600 ℃, removing contained organic matters, and finally obtaining nano-scale cesium oxide/tourmaline powder;
K. and (3) firing: placing the blank of the ultra-large thin porcelain plate printed with the negative ion ink in the step J into a roller kiln, and sintering by using a conventional thin porcelain plate sintering temperature system, a conventional pressure system and a conventional atmosphere system, wherein the sintering temperature is 1150 ℃, the sintering period is 150min, so as to obtain a semi-finished product of the ultra-large thin porcelain plate, and the linear thermal expansion coefficient of the blank layer of the semi-finished product of the ultra-large thin porcelain plate is 7.8 multiplied by 10-6/° C, the coefficient of linear thermal expansion of the surface paste layer was 7.4 × 10-6/° C, the water absorption rate of the ultra-large specification thin porcelain plate semi-finished product is 0.07 percent, the breaking strength is 1216N, the breaking modulus is 50MPa, and the volume weight is 2.39g/cm3；
L, edging and polishing: and D, utilizing conventional edging and polishing processing equipment to carry out edging and polishing treatment on the semi-finished product of the ultra-large specification thin porcelain plate prepared in the step K to prepare the ultra-large specification thin porcelain plate finished product with a bright surface effect on the surface and a negative ion function, wherein the specification of the ultra-large specification thin porcelain plate finished product is 0.9m multiplied by 1.8m (the upper surface area is 1.62 m)2) 5.8mm in thickness and 95 gloss units in glossiness, and the average negative ion release amount of the super-large thin porcelain plate surface is 3000/cm3。
Example 4
A. Preparing blank powder for the ultra-large thin porcelain plate according to a conventional method for later use;
B. preparing the surface paste for the ultra-large specification thin porcelain plate according to a conventional method for later use;
C. distributing blank powder and performing die-free press molding: b, distributing the blank powder for the ultra-large thin porcelain plate prepared in the step A according to the designed pattern texture, and forming by a die-free compression forming process to obtain the ultra-large thin porcelain plate blank, wherein the bulk weight of the formed blank is 2.05g/cm3；
D. Automatic green body cutting: c, automatically cutting the blank of the ultra-large thin porcelain plate which is formed by die-free pressing in the step C to obtain the required specification and size of the blank;
E. drying the blank: d, drying the ultra-large specification thin porcelain plate blank subjected to automatic blank cutting in the step D according to a conventional method, wherein the drying temperature is 220 ℃;
F. baking: e, baking the ultra-large thin porcelain plate blank dried in the step E, wherein the baking temperature is 650 ℃, the baking period is 8min, and the volume weight of the baked ultra-large thin porcelain plate blank is 1.85g/cm3The modulus of rupture of the baked blank is 3.3 MPa;
G. applying cloth sizing: b, applying the surface slurry for the ultra-large thin porcelain plate prepared in the step B on the surface of the ultra-large thin porcelain plate blank baked in the step F by using an ultra-large spray pan, wherein the diameter d of the end face circle of the lower end of the ultra-large spray pan is 2600mm, the arc radius R1 of the arc surface a1 of the slurry spray cover main body of the ultra-large spray pan is 4500mm, the arc radius R2 of the arc surface a2 of the end part of the slurry spray cover is 200mm, the included angle alpha between the tangent line L1 at the intersection point of the arc surface of the slurry spray cover main body and the arc surface of the end part of the slurry spray cover and a horizontal line L2 is 13 degrees, and the width c of the arc surface a2 of the end part of the slurry spray cover is 90 mm;
H. and (3) drying again: drying the blank body of the ultra-large thin porcelain plate subjected to the surface paste for the ultra-large thin porcelain plate applied in the step G again according to a conventional method, wherein the drying temperature is 170 ℃;
I. penetrating ink jet printing: spraying penetrating ink on the ultra-large thin porcelain plate blank dried in the step H by using a digital ink-jet printer according to a designed pattern, and matching with the pattern texture of the blank, so that the surface after penetrating ink-jet printing and the blank have similar texture and texture, the thickness of the penetrating ink-jet layer is 0.35mm, and the temperature of the blank before penetrating ink-jet printing is 60 ℃;
J. and (3) firing: placing the blank of the ultra-large thin porcelain plate subjected to ink jet printing in a roller kiln, and sintering by using a conventional thin porcelain plate sintering temperature system, a conventional pressure system and a conventional atmosphere system at 1180 ℃ for 120min to obtain a semi-finished product of the ultra-large thin porcelain plate, wherein the linear thermal expansion coefficient of the blank layer of the semi-finished product of the ultra-large thin porcelain plate is 7.6 multiplied by 10-6The coefficient of linear thermal expansion of the surface paste layer was 7.3X 10/. degree.C-6/° C, the water absorption rate of the ultra-large specification thin porcelain plate semi-finished product is 0.25%, the breaking strength is 880N, the breaking modulus is 60MPa, and the volume weight is 2.31g/cm3；
K. Edging and polishing: utilizing conventional edging and polishing processing equipment to carry out edging and polishing treatment on the ultra-large specification thin porcelain plate semi-finished product;
l, spraying a negative ion coating material: spraying a negative ion coating material on the surface of the ultra-large specification thin porcelain plate subjected to edge grinding and polishing in the step K to prepare a finished ultra-large specification thin porcelain plate product with a matte effect on the surface and a negative ion function, wherein the specification of the finished product is 1.6m multiplied by 5.2m (the upper surface area is 8.32 m)2) The thickness is 4.5mm, and the glossiness is 8 gloss units; on the surface of super-large thin porcelain plateThe average negative ion release amount is 5000/cm3。
The negative ion coating material comprises a negative ion additive and polyurethane-polymethyl methacrylate copolymer emulsion;
the negative ion additive comprises the following components: SiO 22 35%、B2O3 11%、Al2O3 12%、Fe2O3 3%、MnO 1.5%、MgO 2%、CaO 0.5%、Na2O 1%、Li2O 1.5%、ZrO2 31%、Cs21.5 percent of O and less than or equal to 5 percent of other impurities;
the preparation method of the anion additive comprises the following steps: dissolving ethylene diamine tetraacetic acid in ethanol to prepare ethylene diamine tetraacetic acid ethanol solution; dissolving cesium nitrate in deionized water to prepare a cesium nitrate solution; dissolving citric acid in deionized water to prepare a citric acid solution; magnetically stirring a citric acid solution, adding tourmaline powder while stirring, continuously stirring, adding a cesium nitrate solution while stirring, then introducing an ethylene diamine tetraacetic acid ethanol solution, then dropwise adding ammonia water while stirring to adjust the pH value to 8 until a Tyndall phenomenon is generated, continuously stirring, introducing 13% polyvinylpyrrolidone, placing the uniformly stirred solution in an emitting device in an electrostatic spinning machine, generally adopting a medical injector, generating jet flow under the action of the pushing of the injector and high-voltage electric field force, receiving a nano-scale cesium oxide/tourmaline powder precursor on a collecting device, carrying out heat treatment on the collected nano-scale cesium oxide/tourmaline powder precursor at 550 ℃, removing contained organic matters, and finally obtaining nano-scale cesium oxide/tourmaline powder;
the preparation method of the polyurethane-polymethyl methacrylate copolymer emulsion comprises the following steps: firstly, preparing aqueous polyurethane emulsion: adding dehydrated polyether polyol and toluene diisocyanate into a four-mouth bottle provided with a thermometer, a stirrer and a reflux condenser, adding metered dimethylolpropionic acid dissolved in N-methylpyrrolidone, reacting at 60 ℃, adding quantitative 1, 4-butanediol and hydroxymethyl acrylamide, adding a proper amount of methyl methacrylate to reduce the viscosity of the system, cooling to 20 ℃, adding triethylamine to neutralize the carboxyl in the system, reacting for 20min, and adding deionized water under high-speed stirring to prepare an aqueous polyurethane emulsion;
next, a methyl methacrylate monomer emulsion was prepared: stirring a proper amount of deionized water, methyl methacrylate, an emulsifier and an initiator together at room temperature until the emulsion is not layered to prepare methyl methacrylate monomer emulsion;
finally, preparing a polyurethane-polymethyl methacrylate copolymer emulsion: adding the prepared waterborne polyurethane emulsion into a four-mouth bottle, adding a certain amount of initiator, stirring, dropwise adding the prepared methyl methacrylate monomer emulsion at 700 ℃, preserving heat for 2 hours after dropwise adding, and naturally cooling to 35 ℃ to obtain the polyurethane-polymethyl methacrylate copolymer emulsion.
Example 5
A. Preparing blank powder for the ultra-large thin porcelain plate according to a conventional method for later use;
B. preparing the surface paste for the ultra-large specification thin porcelain plate according to a conventional method for later use;
C. distributing blank powder and performing die-free press molding: b, distributing the blank powder for the ultra-large thin porcelain plate prepared in the step A according to the designed pattern texture, and forming by a die-free compression forming process to obtain the ultra-large thin porcelain plate blank, wherein the bulk weight of the formed blank is 1.98g/cm3；
D. Automatic green body cutting: c, automatically cutting the blank of the ultra-large thin porcelain plate which is formed by die-free pressing in the step C to obtain the required specification and size of the blank;
E. drying the blank: d, drying the ultra-large specification thin porcelain plate blank subjected to automatic blank cutting in the step D according to a conventional method, wherein the drying temperature is 175 ℃;
F. baking: e, baking the ultra-large thin porcelain plate blank dried in the step E, wherein the baking temperature is 750 ℃, the baking period is 11min, and the volume weight of the baked ultra-large thin porcelain plate blank is 1.83g/cm3The modulus of rupture of the baked blank is 5.1 MPa;
G. applying cloth sizing: b, distributing the surface slurry for the ultra-large thin porcelain plate prepared in the step B on the surface of the ultra-large thin porcelain plate blank baked in the step F by using an ultra-large spray tray, wherein the diameter d of the end face circle of the lower end of the ultra-large spray tray is 2550mm, the arc radius R1 of the arc surface a1 of the slurry spray cover body of the ultra-large spray tray is 4700mm, the arc radius R2 of the arc surface a2 of the end part of the slurry spray cover is 210mm, the included angle alpha between the tangent line L1 at the intersection point of the arc surface of the slurry spray cover body and the arc surface of the end part of the slurry spray cover and a horizontal line L2 is 15 degrees, and the width c of the arc surface a2 at the end part of the slurry spray cover is 110 mm;
H. and (3) drying again: drying the blank body of the ultra-large thin porcelain plate subjected to the surface sizing for the ultra-large thin porcelain plate applied in the step G again according to a conventional method, wherein the drying temperature is 190 ℃;
I. penetrating ink jet printing: spraying penetrating ink on the ultra-large thin porcelain plate blank dried in the step H by using a digital ink-jet printer according to a designed pattern, and matching with the pattern texture of the blank, so that the surface after penetrating ink-jet printing and the blank have similar texture and texture, the thickness of the penetrating ink-jet layer is 0.1mm, and the temperature of the blank before penetrating ink-jet printing is 65 ℃;
J. and (3) firing: placing the blank of the ultra-large specification thin porcelain plate subjected to ink jet printing in a roller kiln, and sintering by using a conventional thin porcelain plate sintering temperature system, a conventional pressure system and a conventional atmosphere system, wherein the sintering temperature is 1220 ℃, and the sintering period is 80min, so as to obtain a semi-finished product of the ultra-large specification thin porcelain plate, wherein the linear thermal expansion coefficient of the blank layer of the semi-finished product of the ultra-large specification thin porcelain plate is 7.2 multiplied by 10-6/° C, the coefficient of linear thermal expansion of the surface paste layer was 6.9 × 10-6The water absorption of the ultra-large thin porcelain plate semi-finished product is 0.09 percent at the temperature of/° C, the failure strength is 930N, the breaking modulus is 63MPa, and the volume weight is 2.37g/cm3；
K. Edging and polishing: utilizing conventional edging and polishing processing equipment to carry out edging and polishing treatment on the ultra-large specification thin porcelain plate semi-finished product;
l, spraying a negative ion coating material: spraying a negative ion coating material on the surface of the ultra-large specification thin porcelain plate subjected to edge grinding and polishing in the step K to obtain the thin porcelain plate with the soft surfaceThe finished product of the ultra-large specification thin porcelain plate with the negative ion function has the specification of 1.6m multiplied by 4.0m (the upper surface area is 6.40 m)2) The thickness is 3mm, the glossiness is 20 gloss units, and the average negative ion release amount of the super-large thin porcelain plate surface is 4000/cm3；
The negative ion coating material comprises a negative ion additive and polyurethane-polymethyl methacrylate copolymer emulsion;
the negative ion additive comprises the following components: SiO 22 45%、B2O3 5%、Al2O3 6%、Fe2O3 0.8%、MnO 0.7%、MgO 2.5%、CaO 0.3%、Na2O 1.7%、Li2O 0.9%、ZrO2 33%、Cs21.3 percent of O and less than or equal to 5 percent of other impurities;
the preparation method of the anion additive comprises the following steps: dissolving ethylene diamine tetraacetic acid in ethanol to prepare ethylene diamine tetraacetic acid ethanol solution; dissolving cesium nitrate in deionized water to prepare a cesium nitrate solution; dissolving citric acid in deionized water to prepare a citric acid solution; magnetically stirring a citric acid solution, adding tourmaline powder while stirring, continuously stirring, adding a cesium nitrate solution while stirring, then introducing an ethylene diamine tetraacetic acid ethanol solution, then dropwise adding ammonia water while stirring to adjust the pH value to 9 until a Tyndall phenomenon is generated, continuously stirring, introducing 14% polyvinylpyrrolidone, placing the uniformly stirred solution in an emitting device in an electrostatic spinning machine, generally adopting a medical injector, generating jet flow under the action of the pushing of the injector and high-pressure electric field force, receiving a nano-scale cesium oxide/tourmaline powder precursor on a collecting device, carrying out heat treatment on the collected nano-scale cesium oxide/tourmaline powder precursor at 450 ℃, removing contained organic matters, and finally obtaining nano-scale cesium oxide/tourmaline powder;
the preparation method of the polyurethane-polymethyl methacrylate copolymer emulsion comprises the following steps: firstly, preparing aqueous polyurethane emulsion, adding dehydrated polyether polyol and toluene diisocyanate into a four-mouth bottle provided with a thermometer, a stirrer and a reflux condenser, adding metered dimethylolpropionic acid dissolved in N-methyl pyrrolidone, reacting at 80 ℃, adding quantitative 1, 4-butanediol and hydroxymethyl acrylamide, adding a proper amount of methyl methacrylate to reduce the viscosity of the system, cooling to 30 ℃, adding triethylamine to neutralize the carboxyl in the system, reacting for 40min, and adding deionized water under high-speed stirring to prepare the aqueous polyurethane emulsion;
next, a methyl methacrylate monomer emulsion was prepared: stirring a proper amount of deionized water, methyl methacrylate, an emulsifier and an initiator together at room temperature until the emulsion is not layered to prepare methyl methacrylate monomer emulsion;
finally, preparing a polyurethane-polymethyl methacrylate copolymer emulsion: adding the prepared waterborne polyurethane emulsion into a four-mouth bottle, adding a certain amount of initiator, stirring, dropwise adding the prepared methyl methacrylate monomer emulsion at 100 ℃, preserving heat for 2 hours after dropwise adding, and naturally cooling to 30 ℃ to obtain the polyurethane-polymethyl methacrylate copolymer emulsion.
Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the present invention.

Claims (9)

1. A manufacturing method of a super-large specification thin porcelain plate with an anion function is characterized by comprising the following steps:
A. preparing blank powder for the ultra-large thin porcelain plate according to a conventional method for later use;
B. preparing the surface paste for the ultra-large specification thin porcelain plate according to a conventional method for later use;
C. distributing blank powder and performing die-free press molding: b, distributing the blank powder for the ultra-large thin porcelain plate prepared in the step A according to the designed pattern texture, and forming by a die-free compression forming process to obtain the ultra-large thin porcelain plate blank, wherein the bulk weight of the formed blank is more than or equal to 1.95g/cm3(ii) a Between any two parts of the blank of the ultra-large thin porcelain plateThe difference of volume weight is less than or equal to 0.1g/cm3；
D. Automatic green body cutting: c, automatically cutting the blank of the ultra-large thin porcelain plate which is formed by die-free pressing in the step C to obtain the required specification and size of the blank;
E. drying the blank: d, drying the ultra-large specification thin porcelain plate blank subjected to automatic blank cutting in the step D according to a conventional method;
F. baking: e, baking the ultra-large thin porcelain plate blank dried in the step E, wherein the baking temperature is 500-800 ℃, the baking period is 5-15 min, and the volume weight of the baked ultra-large thin porcelain plate blank is more than or equal to 1.80g/cm3The modulus of rupture of the baked green body is more than or equal to 3.0 MPa;
G. applying cloth sizing: f, applying the surface slurry for the ultra-large thin porcelain plate prepared in the step B on the surface of the ultra-large thin porcelain plate blank baked in the step F by using an ultra-large spray plate, wherein the diameter of the end face circle of the lower end of the ultra-large spray plate is more than or equal to 2400 mm; the arc radius of the arc surface of the slurry spraying cover main body of the oversized spraying disc is 4300-5000 mm, and the arc radius of the arc surface of the end part of the slurry spraying cover is 180-240 mm; the included angle between the tangent line at the intersection of the arc surface of the pulp spraying cover main body of the oversized spraying disc and the arc surface of the end part of the pulp spraying cover and the horizontal line is 10-20 degrees; the width of the arc surface at the end part of the slurry spraying cover of the oversized spraying disc is 80-120 mm;
H. and (3) drying again: drying the blank body of the ultra-large specification thin porcelain plate after the surface paste for the ultra-large specification thin porcelain plate is applied in the step G again according to a conventional method;
I. penetrating ink jet printing: spraying penetrating ink on the ultra-large thin porcelain plate blank dried again in the step H by using a digital ink-jet printer according to a designed pattern, matching with the pattern texture of the blank, so that the surface after penetrating ink-jet printing and the blank have similar texture and texture, and the temperature of the blank before penetrating ink-jet printing is 40-70 ℃;
J. and (3) firing: placing the ultra-large specification thin porcelain plate blank subjected to ink jet printing in the step I into a roller kiln for sintering, wherein the sintering temperature is 1150-1250 ℃, and the sintering period is 60-150 min, so as to obtain a semi-finished product of the ultra-large specification thin porcelain plate;
K. edging: carrying out edging treatment on the ultra-large specification thin porcelain plate semi-finished product by using conventional edging processing equipment; the finished product of the ultra-large specification thin porcelain plate with the negative ion function is prepared, the thickness of the finished product is less than or equal to 6mm, and the upper surface area of the finished product is more than or equal to 1.62m2；
The surface slurry for the ultra-large specification thin porcelain plate in the step B comprises 1-15% of negative ion additive;
the anion additive comprises the following components in percentage by weight: SiO 22 30％～50％、B2O3 3％～14％、Al2O33％～14％、Fe2O3 0～3％、MnO 0.1％～2％、MgO 0.1％～5％、CaO 0.1％～1％、Na2O 0.5％～3％、Li2O 0.1％～2％、ZrO2 10％～50％、Cs20.5 to 2 percent of O and less than or equal to 5 percent of other impurities;
the anion additive is a nano cesium oxide/tourmaline powder composite material prepared by adopting an electrostatic spinning method, and the preparation method comprises the following steps: dissolving ethylene diamine tetraacetic acid in ethanol to prepare ethylene diamine tetraacetic acid ethanol solution; dissolving cesium nitrate in deionized water to prepare a cesium nitrate solution; dissolving citric acid in deionized water to prepare a citric acid solution; magnetically stirring a citric acid solution, adding tourmaline powder while stirring, continuously stirring, adding a cesium nitrate solution while stirring, then introducing an ethylene diamine tetraacetic acid ethanol solution, then dropwise adding ammonia water while stirring to adjust the pH value until a Tyndall phenomenon is generated, continuously stirring, introducing a 10% -15% polyvinylpyrrolidone solution, placing the uniformly stirred solution in an emitting device of an electrostatic spinning machine, generally adopting a medical injector, generating jet flow under the action of the pushing of the injector and high-pressure electric field force, receiving a nano-scale cesium oxide/tourmaline powder precursor on a collecting device, carrying out heat treatment on the collected nano-scale cesium oxide/tourmaline powder precursor at 400-600 ℃, removing contained organic matters, and finally obtaining nano-scale cesium oxide/tourmaline powder;
step J, the ultra-large specification thin porcelain plateThe water absorption of the semi-finished product is less than or equal to 0.5 percent, the failure strength is more than or equal to 800N, the breaking modulus is more than or equal to 48MPa, and the volume weight is more than or equal to 2.25g/cm3The linear thermal expansion coefficient of the green body layer is 6.5 x 10-6～8×10-6The linear thermal expansion coefficient of the surface paste layer is 6 x 10 DEG C-6～7.5×10-6/℃。
2. A manufacturing method of a super-large specification thin porcelain plate with an anion function is characterized by comprising the following steps:
A. preparing blank powder for the ultra-large thin porcelain plate according to a conventional method for later use;
B. preparing the surface paste for the ultra-large specification thin porcelain plate according to a conventional method for later use;
C. distributing blank powder and performing die-free press molding: b, distributing the blank powder for the ultra-large thin porcelain plate prepared in the step A according to the designed pattern texture, and forming by a die-free compression forming process to obtain the ultra-large thin porcelain plate blank, wherein the bulk weight of the formed blank is more than or equal to 1.95g/cm3(ii) a The volume weight difference between any two parts of the blank of the ultra-large thin porcelain plate is less than or equal to 0.1g/cm3；
D. Automatic green body cutting: c, automatically cutting the blank of the ultra-large thin porcelain plate which is formed by die-free pressing in the step C to obtain the required specification and size of the blank;
E. drying the blank: d, drying the ultra-large specification thin porcelain plate blank subjected to automatic blank cutting in the step D according to a conventional method;
F. baking: e, baking the ultra-large thin porcelain plate blank dried in the step E, wherein the baking temperature is 500-800 ℃, the baking period is 5-15 min, and the volume weight of the baked ultra-large thin porcelain plate blank is more than or equal to 1.80g/cm3The modulus of rupture of the baked green body is more than or equal to 3.0 MPa;
G. applying cloth sizing: f, applying the surface slurry for the ultra-large thin porcelain plate prepared in the step B on the surface of the ultra-large thin porcelain plate blank baked in the step F by using an ultra-large spray plate, wherein the diameter of the end face circle of the lower end of the ultra-large spray plate is more than or equal to 2400 mm; the arc radius of the arc surface of the slurry spraying cover main body of the oversized spraying disc is 4300-5000 mm, and the arc radius of the arc surface of the end part of the slurry spraying cover is 180-240 mm; the included angle between the tangent line at the intersection of the arc surface of the pulp spraying cover main body of the oversized spraying disc and the arc surface of the end part of the pulp spraying cover and the horizontal line is 10-20 degrees; the width of the arc surface at the end part of the slurry spraying cover of the oversized spraying disc is 80-120 mm;
H. and (3) drying again: drying the blank body of the ultra-large specification thin porcelain plate after the surface paste for the ultra-large specification thin porcelain plate is applied in the step G again according to a conventional method;
I. penetrating ink jet printing: spraying penetrating ink on the ultra-large thin porcelain plate blank dried again in the step H by using a digital ink-jet printer according to a designed pattern, matching with the pattern texture of the blank, so that the surface after penetrating ink-jet printing and the blank have similar texture and texture, and the temperature of the blank before penetrating ink-jet printing is 40-70 ℃;
J. and (3) firing: placing the ultra-large specification thin porcelain plate blank subjected to ink jet printing in the step I into a roller kiln for sintering, wherein the sintering temperature is 1150-1250 ℃, and the sintering period is 60-150 min, so as to obtain a semi-finished product of the ultra-large specification thin porcelain plate;
K. edging: the semi-finished product of the ultra-large specification thin porcelain plate is subjected to edging treatment by utilizing conventional edging processing equipment to prepare the ultra-large specification thin porcelain plate finished product with the negative ion function, the thickness of the finished product is less than or equal to 6mm, and the upper surface area of the finished product is more than or equal to 1.62m2；
The step I and the step J also comprise a step of ink-jet printing of negative ion ink, wherein the negative ion ink is sprayed on the ultra-large thin porcelain plate blank body after the ink-jet printing of the pattern is permeated in the step I by adopting a digital ink-jet printer according to a designed pattern;
the negative ion ink comprises a negative ion additive, an organic solvent and a dispersant;
the anion additive comprises the following components in percentage by weight: SiO 22 30％～50％、B2O3 3％～14％、Al2O33％～14％、Fe2O3 0～3％、MnO 0.1％～2％、MgO 0.1％～5％、CaO 0.1％～1％、Na2O 0.5％～3％、Li2O 0.1％～2％、ZrO2 10％～50％、Cs20.5 to 2 percent of O and less than or equal to 5 percent of other impurities;
the anion additive is a nano cesium oxide/tourmaline powder composite material prepared by adopting an electrostatic spinning method, and the preparation method comprises the following steps: dissolving ethylene diamine tetraacetic acid in ethanol to prepare ethylene diamine tetraacetic acid ethanol solution; dissolving cesium nitrate in deionized water to prepare a cesium nitrate solution; dissolving citric acid in deionized water to prepare a citric acid solution; magnetically stirring a citric acid solution, adding tourmaline powder while stirring, continuously stirring, adding a cesium nitrate solution while stirring, then introducing an ethylene diamine tetraacetic acid ethanol solution, then dropwise adding ammonia water while stirring to adjust the pH value until a Tyndall phenomenon is generated, continuously stirring, introducing a 10% -15% polyvinylpyrrolidone solution, placing the uniformly stirred solution in an emitting device of an electrostatic spinning machine, generally adopting a medical injector, generating jet flow under the action of the pushing of the injector and high-pressure electric field force, receiving a nano-scale cesium oxide/tourmaline powder precursor on a collecting device, carrying out heat treatment on the collected nano-scale cesium oxide/tourmaline powder precursor at 400-600 ℃, removing contained organic matters, and finally obtaining nano-scale cesium oxide/tourmaline powder;
step J, the water absorption rate of the ultra-large thin porcelain plate semi-finished product is less than or equal to 0.5%, the failure strength is greater than or equal to 800N, the breaking modulus is greater than or equal to 48MPa, and the volume weight is greater than or equal to 2.25g/cm3The linear thermal expansion coefficient of the green body layer is 6.5 x 10-6～8×10-6The linear thermal expansion coefficient of the surface paste layer is 6 x 10 DEG C-6～7.5×10-6/℃。
3. A manufacturing method of a super-large specification thin porcelain plate with an anion function is characterized by comprising the following steps:
A. preparing blank powder for the ultra-large thin porcelain plate according to a conventional method for later use;
B. preparing the surface paste for the ultra-large specification thin porcelain plate according to a conventional method for later use;
C. distributing blank powder and performing die-free press molding: b, distributing the blank powder for the ultra-large thin porcelain plate prepared in the step A according to the designed pattern texture, and forming by a die-free compression forming process to obtain the ultra-large thin porcelain plate blank, wherein the bulk weight of the formed blank is more than or equal to 1.95g/cm3(ii) a The volume weight difference between any two parts of the blank of the ultra-large thin porcelain plate is less than or equal to 0.1g/cm3；
D. Automatic green body cutting: c, automatically cutting the blank of the ultra-large thin porcelain plate which is formed by die-free pressing in the step C to obtain the required specification and size of the blank;
E. drying the blank: d, drying the ultra-large specification thin porcelain plate blank subjected to automatic blank cutting in the step D according to a conventional method;
F. baking: e, baking the ultra-large thin porcelain plate blank dried in the step E, wherein the baking temperature is 500-800 ℃, the baking period is 5-15 min, and the volume weight of the baked ultra-large thin porcelain plate blank is more than or equal to 1.80g/cm3The modulus of rupture of the baked green body is more than or equal to 3.0 MPa;
G. applying cloth sizing: f, applying the surface slurry for the ultra-large thin porcelain plate prepared in the step B on the surface of the ultra-large thin porcelain plate blank baked in the step F by using an ultra-large spray plate, wherein the diameter of the end face circle of the lower end of the ultra-large spray plate is more than or equal to 2400 mm; the arc radius of the arc surface of the slurry spraying cover main body of the oversized spraying disc is 4300-5000 mm, and the arc radius of the arc surface of the end part of the slurry spraying cover is 180-240 mm; the included angle between the tangent line at the intersection of the arc surface of the pulp spraying cover main body of the oversized spraying disc and the arc surface of the end part of the pulp spraying cover and the horizontal line is 10-20 degrees; the width of the arc surface at the end part of the slurry spraying cover of the oversized spraying disc is 80-120 mm;
H. and (3) drying again: drying the blank body of the ultra-large specification thin porcelain plate after the surface paste for the ultra-large specification thin porcelain plate is applied in the step G again according to a conventional method;
I. penetrating ink jet printing: spraying penetrating ink on the ultra-large thin porcelain plate blank dried again in the step H by using a digital ink-jet printer according to a designed pattern, matching with the blank pattern, enabling the surface after ink-jet printing to have similar texture and texture with the blank, and enabling the temperature of the blank before penetrating ink-jet printing to be 40-70 ℃;
J. and (3) firing: placing the ultra-large specification thin porcelain plate blank subjected to the penetrating ink jet printing in the step I into a roller kiln for sintering, wherein the sintering temperature is 1150-1250 ℃, and the sintering period is 60-150 min, so as to obtain a semi-finished product of the ultra-large specification thin porcelain plate;
K. edging: the semi-finished product of the ultra-large thin porcelain plate is subjected to edging treatment by utilizing conventional edging processing equipment to prepare the ultra-large thin porcelain plate, the thickness of the ultra-large thin porcelain plate is less than or equal to 6mm, and the upper surface area of the ultra-large thin porcelain plate is more than or equal to 1.62m2；
L, spraying a negative ion coating material: spraying a negative ion coating material on the surface of the ultra-large specification thin porcelain plate edge-ground in the step K, and curing the negative ion coating material to obtain an ultra-large specification thin porcelain plate finished product with a negative ion function;
the negative ion coating material in the step L comprises a negative ion additive and a liquid dispersant;
the anion additive comprises the following components in percentage by weight: SiO 22 30％～50％、B2O3 3％～14％、Al2O33％～14％、Fe2O3 0～3％、MnO 0.1％～2％、MgO 0.1％～5％、CaO 0.1％～1％、Na2O 0.5％～3％、Li2O 0.1％～2％、ZrO2 10％～50％、Cs20.5 to 2 percent of O and less than or equal to 5 percent of other impurities;
the anion additive is a nano cesium oxide/tourmaline powder composite material prepared by adopting an electrostatic spinning method, and the preparation method comprises the following steps: dissolving ethylene diamine tetraacetic acid in ethanol to prepare ethylene diamine tetraacetic acid ethanol solution; dissolving cesium nitrate in deionized water to prepare a cesium nitrate solution; dissolving citric acid in deionized water to prepare a citric acid solution; magnetically stirring a citric acid solution, adding tourmaline powder while stirring, continuously stirring, adding a cesium nitrate solution while stirring, then introducing an ethylene diamine tetraacetic acid ethanol solution, then dropwise adding ammonia water while stirring to adjust the pH value until a Tyndall phenomenon is generated, continuously stirring, introducing a 10% -15% polyvinylpyrrolidone solution, placing the uniformly stirred solution in an emitting device of an electrostatic spinning machine, generally adopting a medical injector, generating jet flow under the action of the pushing of the injector and high-pressure electric field force, receiving a nano-scale cesium oxide/tourmaline powder precursor on a collecting device, carrying out heat treatment on the collected nano-scale cesium oxide/tourmaline powder precursor at 400-600 ℃, removing contained organic matters, and finally obtaining nano-scale cesium oxide/tourmaline powder;
the liquid dispersant is polyurethane-polymethyl methacrylate copolymer emulsion;
step J, the water absorption rate of the ultra-large thin porcelain plate semi-finished product is less than or equal to 0.5%, the failure strength is greater than or equal to 800N, the breaking modulus is greater than or equal to 48MPa, and the volume weight is greater than or equal to 2.25g/cm3The linear thermal expansion coefficient of the green body layer is 6.5 x 10-6～8×10-6The linear thermal expansion coefficient of the surface paste layer is 6 x 10 DEG C-6～7.5×10-6/℃。
4. The method for manufacturing an ultra-large-sized thin porcelain plate having a negative ion function as claimed in claim 1, claim 2 or claim 3, wherein: and D, after the edging treatment in the step K, cutting a finished product to obtain the required specification and size of the finished product.
5. The method for manufacturing an ultra-large-sized thin porcelain plate having a negative ion function as claimed in claim 1, claim 2 or claim 3, wherein: and D, after the edging treatment in the step K, adopting a polishing process for treatment.
6. The method for manufacturing an ultra-large specification thin porcelain plate with an anion function as claimed in claim 5, wherein: after the polishing process is adopted for treatment, the finished product of the ultra-large specification thin porcelain plate with the bright surface and the negative ion function is prepared, and the glossiness is more than or equal to 55 gloss units.
7. The method for manufacturing an ultra-large specification thin porcelain plate with an anion function as claimed in claim 5, wherein: after the polishing process is adopted for treatment, the finished product of the ultra-large thin porcelain plate with the soft surface and the anion function is prepared, and the glossiness is 15-30 gloss units.
8. The method for manufacturing an ultra-large specification thin porcelain plate with an anion function as claimed in claim 5, wherein: after the polishing process is adopted for treatment, the finished product of the ultra-large specification thin porcelain plate with the matte surface and the negative ion function is prepared, and the glossiness is 5-15 gloss units.
9. The ultra-large thin porcelain plate product with an anion function manufactured by the method for manufacturing the ultra-large thin porcelain plate with an anion function according to any one of claims 1 to 8.
CN202010001812.3A 2020-01-02 2020-01-02 Ultra-large thin porcelain plate with negative ion function and manufacturing method thereof Active CN111533579B (en)

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