Negative ion ceramic ink, preparation method thereof and negative ion ceramic tile

Abstract

The application belongs to the technical field of building ceramics, and discloses a kind of negative ion ceramic ink and its preparation method, negative ion ceramic tile.The negative ion ceramic ink contains zirconium niobium-based composite material and tourmaline composite material synthesized independently at the same time, and the two composite materials synergistically act, not only solve the high temperature instability problem of traditional negative ion material, but also ionize air through rare earth energy transfer / lattice distortion polarization and spontaneous polarization, can induce a large number of negative ions, improve air purification efficiency.The application adopts the system of "bottom glaze-function ink-surface glaze", by adjusting the raw material components of bottom glaze and surface glaze, the negative ion material can efficiently and durably induce air negative ions, and the negative ion release amount under visible light conditions can reach 3090-3250 / cm 3 , which exceeds the health level of class I;The purification efficiency of formaldehyde is 93-95%, the persistent purification efficiency is 90-92%, which exceeds the requirements of class II standard.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of building ceramics, and particularly relates to a negative ion ceramic ink, a preparation method thereof and a negative ion ceramic tile. BACKGROUND

[0002] As a main building decoration material, the functionalization of ceramic tiles is an important direction for the upgrading of the industry. Among them, the negative ion ceramic tile with air purification function is concerned because it can continuously release negative ions and effectively degrade formaldehyde and purify indoor air. At present, the mainstream technology to realize the negative ion function of ceramic tiles is to add negative ion generating materials in glazes, among which natural tourmaline is the most common. However, the successful application of negative ion generating materials, especially tourmaline, in the ceramic tile system faces severe technical challenges, resulting in unstable and poor durability of existing products, which seriously restricts the industrialization development and market acceptance of the technology. The existing technology mainly has the following several bottlenecks:

[0003] First, there is a fundamental contradiction between the inherent high-temperature instability of negative ion materials and the high-temperature preparation process of ceramic tiles. Untreated tourmaline will have a cliff-like drop in negative ion release efficiency when the temperature exceeds 900℃; while the firing temperature of ceramic tiles is usually as high as 1100-1250℃. Therefore, natural tourmaline will undergo severe thermal decomposition during the firing process of ceramic tiles: the hydroxyl group (-OH) in its crystal structure will be removed, Fe 2+ will be oxidized to Fe 3+ , resulting in a serious weakening or even complete destruction of the core driving force of negative ion release (spontaneous polarization electric field).

[0004] Second, the existing technology lacks protection for negative ion materials and often introduces new defects. In order to improve the temperature resistance of tourmaline, common technical routes include oxide coating (such as SiO2) or mixing with a small amount of rare earth oxides (such as CeO2). However, these methods have obvious limitations: first, the conventional coating layer (such as amorphous SiO2) is easily eroded and dissolved in high-temperature molten glaze, and cannot provide long-term effective physical and chemical protection for the core. Second, the widely used CeO2 and other rare earth additives have limited effect on inhibiting the lattice collapse and grain boundary migration of tourmaline through valence compensation of oxygen vacancies, and they themselves are also prone to aggregation at high temperatures, resulting in poor dispersion and reduced protection effect.

[0005] Third, the mismatch between the glaze system and the functional layer leads to functional decay. Even if a small amount of negative ion materials "survive" at high temperatures, their function is also restricted by the glaze system. If the glaze components and negative ion ink do not match in terms of expansion coefficient, chemical compatibility and microstructure, etc., it will result in low negative ion release efficiency.

[0006] In summary, the existing negative ion ceramic tile technology, especially the technical scheme based on inkjet printing, is limited by the high-temperature instability of the core functional material, the inadequacy of the protection technology, and the mismatch of the glaze system, etc. core problems, resulting in the product generally existing the defects of low negative ion release amount, short functional life, unstable performance, etc. It is difficult to meet the market demand for high-performance, long-acting health building materials.

[0007] Therefore, there is an urgent need in the art to develop a new technical scheme that can fundamentally solve the failure problem of negative ion materials in the high-temperature sintering process and systematically solve the whole chain technical bottleneck from materials, ink to glaze, so as to develop high-efficiency, durable and stable negative ion ceramic tiles. SUMMARY

[0008] The present application provides a kind of negative ion ceramic ink and preparation method thereof, negative ion ceramic tile, to solve one or more technical problems existing in the prior art, at least provide a beneficial choice or create conditions.

[0009] To solve the above technical problems, the first aspect of the present application provides a preparation method of negative ion ceramic ink, comprising the following steps:

[0010] Preparation of zirconium-niobium-based composite material:

[0011] (1) mix CaCO3, Nb2O5, (NH4)2HPO4, Nd2O3 and Eu2O3 to obtain a mixed raw material; then pre-sinter the mixed raw material, grind it, and obtain a neodymium and europium co-doped niobium apatite powder;

[0012] (2) disperse the neodymium and europium co-doped niobium apatite powder in a mixed solvent of ethanol and water, heat it, and adjust the pH value to alkaline; then add a zirconium source solution and a first silicon source solution dropwise, stir them, obtain a mixed solution; filter the mixed solution, and perform a first calcination on the obtained solid powder to obtain a zirconium silicate coated neodymium and europium co-doped niobium apatite powder, i.e. the zirconium-niobium-based composite material;

[0013] Preparation of tourmaline composite material:

[0014] 1) soak the tourmaline in an ethanol solution of silane coupling agent, filter and dry it, disperse it in anhydrous ethanol to obtain a tourmaline suspension;

[0015] 2) heat and stir the tourmaline suspension, then add a mixed precursor solution containing an aluminum source and a second silicon source to obtain a mixed suspension; adjust the pH value of the mixed suspension to acidic, and perform a reaction; after the reaction is completed, filter it, and perform a second calcination on the obtained solid powder to obtain a mullite coated tourmaline powder, i.e. the tourmaline composite material;

[0016] The negative ion ceramic ink is prepared by mixing the zirconium-niobium-based composite material and the tourmaline composite material with a solvent and a dispersant.

[0017] Specifically, this invention uses CaCO3, Nb2O5, (NH4)2HPO4, Nd2O3, and Eu2O3 as main raw materials to construct a Nd,Eu:Ca-Nb-PO niobium-based apatite structure using a solid-state method. This invention utilizes a "photocatalytic synergistic electrochemistry" enhancement mechanism, leveraging the large radius and high ion field of Nb2O3... 5+ Partially replaces P 5+ This introduces significant lattice distortion and stress into the crystal lattice, generating a powerful intrinsic polarization electric field, which serves as the fundamental driving force for the release of negative ions. Simultaneously, Nd... 3+ As a sensitizer, it has multiple absorption bands in the visible and infrared regions, effectively capturing light energy; Eu 3+ As an activator, Nd 3+ The captured energy can be transferred to Eu via nonradiative transitions. 3+ This Nd 3+ →Eu 3+ Energy transfer ultimately results in Eu 3+ The characteristic emission form is released. This process can intensify the disturbance of the electromagnetic field around the crystal lattice, thereby promoting its dissociation efficiency of water molecules in the air, and thus significantly increasing the negative ion yield. At the same time, zirconium silicate has good high-temperature stability and chemical inertness, and does not react with other glaze components at the firing temperature of ceramic tiles. This invention generates a zirconium silicate coating layer in situ through the sol-gel method, which not only provides a protective layer for the internal core, isolating it from the chemical erosion of the molten glaze; but also has strong bonding with the core, and its coefficient of thermal expansion is well matched with the ceramic glaze system, which can effectively avoid cracking due to stress during firing.

[0018] Tourmaline is a natural mineral crystal with spontaneous polarity, possessing permanent positive and negative electrodes at both ends; mullite is a high-temperature resistant ceramic material. This invention first uses a silane coupling agent to modify the surface of tourmaline to improve its compatibility with inorganic materials. Then, through in-situ hydrolysis and calcination using aluminum and silicon sources, a mullite shell is formed on the surface of the tourmaline, acting as a physical barrier to protect the core tourmaline from high-temperature oxidation and erosion by the molten glaze. Furthermore, the mullite can fuse with the ceramic glaze at high temperatures without negatively impacting the glaze's performance or surface quality. Simultaneously, the permanent electrostatic field generated by the tourmaline can penetrate the insulating mullite shell, forming a weak electric field outside the shell. When water molecules in the air diffuse to the glaze surface and approach the tourmaline composite material, they are polarized by the surface electric field; the polarized water molecules undergo distortion, their internal hydrogen-oxygen bonds are weakened, and ultimately break, generating H+. + and OH - H +Will be combined with the negative electrode of the tourmaline surface, or be neutralized quickly; and the negative OH - Then be rejected into the air, into the air anion.

[0019] The above-mentioned zirconium-niobium-based composite material and tourmaline composite material are used as anion materials, and solvent and dispersant are used to prepare anion ceramic ink. The microelectric field of the tourmaline composite material and the basic polarization electric field of the zirconium-niobium-based composite material jointly ionize air, and can continuously generate anions. Meanwhile, the rare earth elements in the zirconium-niobium-based composite material can improve the potential energy at both ends of the tourmaline crystal through radiation excitation, thereby promoting the function of the tourmaline to release anions. In addition, when light irradiation occurs, the rare earth energy transfer in the zirconium-niobium-based composite material will be activated, producing additional ionization effect, further improving the release yield of anions of the material, and improving the air purification efficiency.

[0020] In some embodiments of the present application, in step (1), the mixed raw materials include CaCO3 35-45 parts, Nb2O5 30-40 parts, (NH4)2HPO4 12-24 parts, Nd2O3 1-2 parts, and Eu2O3 0.5-1 part by weight.

[0021] In some embodiments of the present application, in step (1), the pre-sintering is calcination at a temperature of 1200-1250℃ for 3-4 hours.

[0022] In some embodiments of the present application, in step (1), the mixing is carried out by ball milling, the medium is anhydrous ethanol, the grinding ball is zirconium oxide ball, and the ball milling is carried out at a speed of 200-300 rpm for 5-6 hours.

[0023] In some embodiments of the present application, in step (1), the average particle size of the neodymium-europium co-doped niobium apatite powder is 100-300 nm.

[0024] In some embodiments of the present application, in step (2), the zirconium source solution is an aqueous solution of ZrOCl2·8H2O,

[0025] The first silicon source solution is an ethanolic solution of tetraethyl orthosilicate.

[0026] In some embodiments of the present application, in step (2), in the mixed solution, the mass ratio of the neodymium-europium co-doped niobium apatite powder, the zirconium source, and the first silicon source is (1-3):(1-2):1.

[0027] In some embodiments of the present application, in step (2), the first calcination is carried out at a temperature of 1100-1200℃ for 1-2 hours.

[0028] In some embodiments of the present application, in step (2), the mass-volume ratio of the neodymium and europium co-doped niobium apatite powder to the mixed solvent is (30-50) g:1 L; in the mixed solvent, the volume ratio of ethanol to water is (3-5):1.

[0029] In some embodiments of the present application, in step (2), the heating temperature is 50-70℃.

[0030] In some embodiments of the present application, in step (2), the pH value is 9-10.

[0031] In some embodiments of the present application, in step (2), before the first calcination, the solid powder is further washed with ethanol and deionized water and dried.

[0032] In some embodiments of the present application, in step 1), the concentration of the silane coupling agent ethanol solution is 3-8 wt%.

[0033] In some embodiments of the present application, in step 1), the soaking time is 1-3 hours.

[0034] In some embodiments of the present application, in step 1), the solid content of the tourmaline suspension is 5-10 wt%.

[0035] In some embodiments of the present application, in step 2), the aluminum source is aluminum isopropoxide, and the second silicon source is tetraethyl orthosilicate; in the mixed suspension, the mass ratio of tourmaline, aluminum source and second silicon source is (6-8):(1-3):1.

[0036] In some embodiments of the present application, in step 2), the second calcination is performed at a temperature of 1000-1100℃ for 2-3 hours.

[0037] In some embodiments of the present application, in step 2), the heating and stirring are performed at a temperature of 70-90℃ for 1-2 hours at a rotation speed of 300-500 rpm.

[0038] In some embodiments of the present application, in step 2), the pH value is 4-5, which is conducive to the hydrolysis and deposition of the aluminum source and the silicon source.

[0039] In some embodiments of the present application, in step 2), before the second calcination, the solid powder is further washed with ethanol and dried.

[0040] In some embodiments of the present application, the raw material components of the negative ion ceramic ink include, by weight: zirconium-niobium composite material 10-15 parts, tourmaline composite material 10-15 parts, solvent 40-60 parts, and dispersant 5-10 parts.

[0041] In some embodiments of the present application, the solvent can be any solvent commonly used in the art, such as ethylene glycol, dipropylene glycol methyl ether acetate, acetone, or butanone, etc.

[0042] In some embodiments of the present application, the dispersant can be any dispersant commonly used in the art, such as polyhexamethylene adipate, polyhexamethylene terephthalate, or poly-m-phenylene terephthalate, etc.

[0043] In some embodiments of the present application, the raw material components of the negative ion ceramic ink further include 3-8 parts by weight of a defoaming agent, which can be any defoaming agent commonly used in the art, such as octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, etc.

[0044] The second aspect of the present application provides a negative ion ceramic ink prepared by the above preparation method, wherein the negative ion ceramic ink contains zirconium-niobium-based composite material and tourmaline composite material, and the maximum particle size of the negative ion ceramic ink is less than 1 μm.

[0045] Specifically, the negative ion ceramic ink of the present application contains both zirconium-niobium-based composite material and tourmaline composite material, which together ionize air and release negative ions through rare earth energy transfer / lattice distortion polarization and spontaneous polarization, respectively. Meanwhile, the rare earth elements in the zirconium-niobium-based composite material can increase the potential energy at both ends of the tourmaline crystal through radiation excitation, which is conducive to promoting the function of the tourmaline to release negative ions. In addition, the rare earth energy in the zirconium-niobium-based composite material can also be activated by light energy transmission, producing additional ionization effect and further improving the negative ion energy release of the material. Therefore, the negative ion ceramic ink of the present application not only has good high-temperature resistance, but also can induce a large number of negative ions and improve the air purification efficiency.

[0046] The third aspect of the present application provides a negative ion ceramic tile, which comprises, from bottom to top, a body, a bottom glaze layer, a negative ion functional layer, and a surface glaze layer, wherein the negative ion functional layer is formed by inkjet printing of the above negative ion ceramic ink.

[0047] In some embodiments of the present application, the raw material components of the bottom glaze layer include, by weight fraction: 35-40 parts of sodium feldspar, 8-12 parts of nepheline, 5-10 parts of titanium oxide, 12-18 parts of quartz, 12-18 parts of aluminum oxide, 6-12 parts of dolomite, 1-3 parts of talc, 10-15 parts of kaolin, and 3-8 parts of ball clay.

[0048] Specifically, the underglaze provides a flat and dense base for the body, covering the color of the body, and provides a low water permeability printing surface for the upper layer of negative ion ceramic ink to prevent excessive penetration. Based on this, the application adds a certain amount of titanium oxide and dolomite to the underglaze to form stable titanium sphene crystal grains during firing, effectively covering the body while reducing the permeability of the glaze, thereby improving the effective performance of the negative ion ceramic ink. At the same time, part of the ball clay is added to replace the kaolin, and the ball clay is a high plasticity clay with microcrystalline kaolinite and alpha-quartz particles as the main mineral components, which is beneficial to improve the air permeability and high temperature strength of the glaze.

[0049] In some embodiments of the application, the raw material components of the face glaze layer include, by weight: syenite 40-45 parts, quartz 8-12 parts, wollastonite 18-22 parts, dolomite 3-8 parts, zinc oxide 8-12 parts, barium carbonate 8-12 parts, kaolin 3-8 parts.

[0050] Specifically, compared with the traditional method of exposing the negative ion functional layer, the application applies a high-transparency face glaze on the surface, greatly improving the durability of the negative ion function. To ensure the effective performance of the negative ion functional layer, the face glaze layer must meet the requirements of good transparency and high temperature fluidity. High-transparency face glaze can make negative ion materials effectively act on air, and good fluidity can make the face glaze spread and cover the ink layer better, both of which are conducive to improving the efficiency of negative ion generation. Based on this, the application adjusts the silicon-aluminum ratio of the glaze raw material and uses syenite and barium carbonate as flux to improve the transparency and fluidity of the face glaze layer.

[0051] In some embodiments of the application, the thickness of the face glaze layer is less than 0.1mm. Thin face glaze layer is more conducive to the performance of the negative ion functional layer.

[0052] The above technical solutions of the application have at least the following technical effects or advantages compared with the prior art:

[0053] (1) The application uses solid phase method to synthesize Nd, Eu: Ca-Nb-P-O niobium-based apatite structure, and uses Nb 5+ to partially replace P 5+ , which introduces huge lattice distortion and stress in the crystal lattice, thereby generating a strong intrinsic polarization electric field as the fundamental driving force for the release of negative ions. At the same time, Nd 3+ can capture light energy and transfer it to Eu 3 through non-radiative transition. + , and finally releases it in the form of characteristic emission of Eu 3+ . In addition, a zirconium silicate coating layer is generated in situ by sol-gel method, which isolates the chemical corrosion of molten glaze, thereby greatly improving the yield of negative ions.

[0054] (2) The invention first adopts silane coupling agent to modify the surface of tourmaline, then utilizes in-situ hydrolysis of aluminum source and silicon source, and calcines to form a layer of mullite shell on the surface of tourmaline, as physical isolation, which protects the core tourmaline from high temperature oxidation and the erosion of fused glaze. And the permanent electrostatic field generated by tourmaline can penetrate the insulating mullite shell, forming a weak electric field outside the shell, thereby inducing the generation of negative ions in the air.

[0055] (3) The negative ion ceramic ink of the invention contains self-synthesized zirconium-niobium-based composite material and tourmaline composite material at the same time, and the two composite materials synergistically act, not only solving the high temperature instability problem of traditional negative ion materials, but also ionizing air through rare earth energy transfer / lattice distortion polarization and spontaneous polarization, and can induce a large number of negative ions, improving the air purification efficiency.

[0056] (4) The invention adopts "base glaze - functional ink - surface glaze" system, and by adjusting the raw material components of base glaze and surface glaze, the negative ion material can efficiently and durably induce air negative ions, and realizes that the negative ion release amount can reach 3090-3250 / cm 3 under visible light conditions, exceeding the I level health grade; the formaldehyde purification efficiency is 93-95%, the persistent purification efficiency is 90-92%, exceeding the requirements of class II standard. DETAILED DESCRIPTION

[0057] The invention will be described in detail below with reference to examples, so as to facilitate the understanding of the invention by the person skilled in the art. It is necessary to particularly point out here that the examples are only used to further illustrate the invention, and cannot be understood as limiting the protection scope of the invention. The person skilled in the art, according to the above invention content, makes non-essential improvements and adjustments to the invention, which should still belong to the protection scope of the invention. At the same time, the raw materials mentioned below are not described in detail, which are all market products; the process steps or preparation methods not mentioned in detail are all known process steps or preparation methods to the person skilled in the art.

[0058] Example 1

[0059] A preparation method of a negative ion ceramic ink, comprising the following steps:

[0060] (1) Preparation of zirconium-niobium-based composite material:

[0061] Take CaCO3 35 parts, Nb2O5 30 parts, (NH4)2HPO4 12 parts, Nd2O3 1 part, Eu2O3 0.5 parts by weight, put into a nylon ball mill jar, zirconia ball as grinding ball, anhydrous ethanol as medium, ball mill at 300 rpm for 6 hours; then dry the slurry after ball milling at 80℃ for 12 hours, then grind the dried powder in an agate mortar, calcine at 1250℃ in air atmosphere for 3 hours, cool in the furnace; finally grind the calcined powder to obtain neodymium and europium co-doped niobium apatite powder.

[0062] Disperse the neodymium and europium co-doped niobium apatite powder in a mixed solvent of ethanol and water in a volume ratio of 4:1 (the mass-volume ratio of neodymium and europium co-doped niobium apatite powder to mixed solvent is 400 g:1 L), ultrasonic dispersion for 30 min; heat in water bath to 60℃, stir at 500 rpm, adjust the pH value to 9 with ammonia water; then add dropwise the aqueous solution of ZrOCl2·8H2O and the ethanol solution of tetraethyl orthosilicate, continue to stir for 12 hours to obtain a mixed solution (the mass ratio of neodymium and europium co-doped niobium apatite powder, ZrOCl2·8H2O and tetraethyl orthosilicate is 1:2:1); then filter the mixed solution, wash the obtained solid powder with ethanol and deionized water for 3 times, dry at 110℃ for 12 hours; finally calcine at 1150℃ for 1.5 hours to obtain zirconium silicate coated neodymium and europium co-doped niobium apatite powder, i.e. zirconium niobium based composite material.

[0063] (2) Preparation of tourmaline composite material:

[0064] Soak the tourmaline in a 5wt% ethanol solution of silane coupling agent KH-550 for 2 hours, filter and dry, then disperse in anhydrous ethanol, ultrasonic for 1 hour to obtain a tourmaline suspension with a solid content of 5wt%.

[0065] Heat and stir the tourmaline suspension in a water bath at 80℃, then add a mixed precursor solution containing aluminum isopropoxide and tetraethyl orthosilicate to obtain a mixed suspension (the mass ratio of tourmaline, aluminum source and second silicon source is 6:2:1); adjust the pH value of the mixed suspension to 4 and react for 6 hours; after the reaction is completed, filter, then wash the obtained solid powder with ethanol three times and dry at 100℃ for 12 hours; finally calcine at 1050℃ for 2.5 hours to obtain mullite coated tourmaline powder, i.e. tourmaline composite material.

[0066] (3) Preparation of anion ceramic ink:

[0067] The zirconium niobium-based composite material 10 parts, the tourmaline composite material 10 parts, the ethylene glycol 40 parts, the polyhexamethylene adipic acid 5 parts, and the octylphenol polyoxyethylene ether 3 parts are weighed by weight parts. Then the zirconium niobium-based composite material and the tourmaline composite material are placed in a nylon ball mill tank, zirconium oxide balls are used as grinding balls, anhydrous ethanol is used as a medium, and ball milling is performed at a speed of 400 rpm for 8 hours, so that the maximum particle size of the slurry is less than 1 μm; the slurry after ball milling is dried at 80°C for 12 hours to prepare a composite negative ion powder; finally, the composite negative ion powder is added with ethylene glycol, polyhexamethylene adipic acid, and octylphenol polyoxyethylene ether, and stirred at a speed of 200 rpm for 1 hour to make it fully dispersed, thereby preparing the negative ion ceramic ink of the embodiment.

[0068] A preparation method of a negative ion ceramic tile, comprising the following steps:

[0069] (1) The preparation raw materials of the bottom glaze layer are weighed by weight parts: 35 parts of sodium feldspar, 8 parts of nepheline, 5 parts of titanium oxide, 12 parts of quartz, 12 parts of aluminum oxide, 6 parts of dolomite, 1 part of talc, 10 parts of kaolin, and 3 parts of ball clay; water is added for ball milling (the mass ratio of material to water is 100:40), and a bottom glaze with a fineness of 0.4wt% on a 325 mesh sieve is prepared.

[0070] (2) The preparation raw materials of the surface glaze layer are weighed by weight parts: 40 parts of nepheline syenite, 8 parts of quartz, 18 parts of wollastonite, 3 parts of dolomite, 8 parts of zinc oxide, 8 parts of barium carbonate, and 3 parts of kaolin; water is added for ball milling (the mass ratio of material to water is 100:40), and a surface glaze with a fineness of 0.4wt% on a 325 mesh sieve is prepared.

[0071] (3) The bottom glaze, the negative ion ceramic ink, and the surface glaze are sequentially applied to the surface of the body to form a bottom glaze layer, a negative ion functional layer, and a surface glaze layer (with a thickness of less than 1 mm), which are dried and fired at 1150°C for 60 minutes to prepare the negative ion ceramic tile of the embodiment.

[0072] Example 2

[0073] A preparation method of a negative ion ceramic ink, comprising the following steps:

[0074] (1) Preparation of a zirconium niobium-based composite material:

[0075] Take CaCO3 40 parts, Nb2O5 35 parts, (NH4)2HPO4 18 parts, Nd2O3 1 part, Eu2O3 1 part by weight, put into nylon ball mill jar, zirconia ball as grinding ball, anhydrous ethanol as medium, 300 rpm speed ball milling for 6 hours; then the slurry after ball milling is dried at 80℃ for 12 hours, then the dried powder is ground in agate mortar, calcined at 1250℃ in air atmosphere for 3 hours, and cooled in the furnace; finally, the calcined powder is ground to obtain, and the neodymium and europium co-doped niobium apatite powder is prepared.

[0076] The neodymium and europium co-doped niobium apatite powder is dispersed in a mixed solvent of ethanol and water in a volume ratio of 4:1 (the mass-volume ratio of neodymium and europium co-doped niobium apatite powder to mixed solvent is 400 g:1 L), and ultrasonic dispersion is performed for 30 min; the water bath is heated to 60℃, and stirring is performed at a speed of 500 rpm, and the pH value is adjusted to 10 with ammonia water; then ZrOCl2·8H2O aqueous solution and tetraethyl orthosilicate ethanol solution are added dropwise, and stirring is continued for 12 hours to obtain a mixed solution (the mass ratio of neodymium and europium co-doped niobium apatite powder, ZrOCl2·8H2O and tetraethyl orthosilicate is 2:1:1); the mixed solution is filtered again, and the solid powder obtained is washed with ethanol and deionized water for 3 times, and dried at 110℃ for 12 hours; finally, it is calcined at 1150℃ for 2 hours to obtain zirconium silicate coated neodymium and europium co-doped niobium apatite powder, i.e. zirconium niobium based composite material.

[0077] (2) Preparation of tourmaline composite material:

[0078] The tourmaline is soaked in 5wt% silane coupling agent KH-550 ethanol solution for 2 hours, filtered, dried, and then dispersed in anhydrous ethanol, ultrasonic for 1 hour to obtain a tourmaline suspension with a solid content of 8wt%.

[0079] The tourmaline suspension is heated and stirred in a water bath at 80℃, and then a mixed precursor solution containing aluminum isopropoxide and tetraethyl orthosilicate is added to obtain a mixed suspension (the mass ratio of tourmaline, aluminum source and second silicon source is 7:2:1); the pH value of the mixed suspension is adjusted to 5, and the reaction is carried out for 6 hours; after the reaction is completed, the solid powder is filtered, washed with ethanol for 3 times, and dried at 100℃ for 12 hours; finally, it is calcined at 1050℃ for 3 hours to obtain a mullite coated tourmaline powder, i.e. tourmaline composite material.

[0080] (3) Preparation of anion ceramic ink:

[0081] The zirconium niobium-based composite material 12 parts, the tourmaline composite material 12 parts, the ethylene glycol 50 parts, the polyhexamethylene adipic acid 8 parts, and the octylphenol polyoxyethylene ether 6 parts are weighed by weight parts. Then the zirconium niobium-based composite material and the tourmaline composite material are placed in a nylon ball mill jar, zirconium oxide balls are used as grinding balls, anhydrous ethanol is used as medium, and ball milling is carried out at a speed of 400 rpm for 8 hours, so that the maximum particle size of the slurry is less than 1 μm; the slurry after ball milling is dried at 80℃ for 12 hours to prepare the composite negative ion powder; finally, the ethylene glycol, the polyhexamethylene adipic acid, and the octylphenol polyoxyethylene ether are added to the composite negative ion powder, and stirring is carried out at a speed of 200 rpm for 1 hour to make it fully dispersed, so that the negative ion ceramic ink of the embodiment is prepared.

[0082] A preparation method of a negative ion ceramic tile, comprising the following steps:

[0083] (1) The preparation raw materials of the bottom glaze layer are weighed by weight parts: 38 parts of sodium feldspar, 10 parts of nepheline, 8 parts of titanium oxide, 15 parts of quartz, 15 parts of alumina, 10 parts of dolomite, 2 parts of talc, and 12 parts of kaolin, and 5 parts of ball clay; water is added for ball milling (the mass ratio of material to water is 100:40), and the bottom glaze with a fineness of 0.4wt% on a 325 mesh sieve is prepared.

[0084] (2) The preparation raw materials of the surface glaze layer are weighed by weight parts: 42 parts of nepheline syenite, 10 parts of quartz, 20 parts of wollastonite, 5 parts of dolomite, 10 parts of zinc oxide, 10 parts of barium carbonate, and 5 parts of kaolin; water is added for ball milling (the mass ratio of material to water is 100:40), and the surface glaze with a fineness of 0.4wt% on a 325 mesh sieve is prepared.

[0085] (3) The bottom glaze, the negative ion ceramic ink, and the surface glaze are applied on the surface of the body in sequence to form the bottom glaze layer, the negative ion functional layer, and the surface glaze layer (the thickness is less than 1 mm), and the negative ion ceramic tile of the embodiment is prepared after drying and firing at 1180℃ for 55 minutes.

[0086] Example 3

[0087] A preparation method of a negative ion ceramic ink, comprising the following steps:

[0088] (1) Preparation of the zirconium niobium-based composite material:

[0089] Take 45 parts of CaCO3, 40 parts of Nb2O5, 24 parts of (NH4)2HPO4, 2 parts of Nd2O3, and 1 part of Eu2O3 by weight, put them into a nylon ball mill jar, use zirconia balls as grinding balls, and anhydrous ethanol as medium, ball mill at 300 rpm for 6 hours; then dry the slurry after ball milling at 80℃ for 12 hours, grind the dried powder in an agate mortar, and calcine it at 1250℃ in air atmosphere for 3 hours with furnace cooling; finally, grind the calcined powder to obtain neodymium and europium co-doped niobium apatite powder.

[0090] Disperse the neodymium and europium co-doped niobium apatite powder in a mixed solvent of ethanol and water with a volume ratio of 4:1 (the mass-volume ratio of neodymium and europium co-doped niobium apatite powder to mixed solvent is 400 g:1 L), and ultrasonic disperse for 30 min; heat in water bath to 60℃, stir at 500 rpm, adjust the pH value to 10 with ammonia water; then add dropwise the aqueous solution of ZrOCl2·8H2O and the ethanol solution of tetraethyl orthosilicate, continue to stir for 12 hours to obtain a mixed solution (the mass ratio of neodymium and europium co-doped niobium apatite powder, ZrOCl2·8H2O and tetraethyl orthosilicate is 3:2:1); filter the mixed solution, wash the obtained solid powder with ethanol and deionized water for 3 times, and dry at 110℃ for 12 hours; finally, calcine at 1150℃ for 2 hours to obtain zirconium silicate coated neodymium and europium co-doped niobium apatite powder, i.e. zirconium niobium-based composite material.

[0091] (2) Preparation of tourmaline composite material:

[0092] Soak the tourmaline in 5wt% silane coupling agent KH-550 ethanol solution for 2 hours, filter and dry, then disperse in anhydrous ethanol, ultrasonic for 1 hour to obtain a tourmaline suspension with a solid content of 8wt%.

[0093] Heat and stir the tourmaline suspension in water bath at 80℃, then add the mixed precursor solution containing aluminum isopropyl alcohol and tetraethyl orthosilicate to obtain a mixed suspension (the mass ratio of tourmaline, aluminum source and second silicon source is 8:3:1); adjust the pH value of the mixed suspension to 4-5, and react for 6 hours; after the reaction is completed, filter, then wash the obtained solid powder with ethanol for 3 times, dry at 100℃ for 12 hours; finally, calcine at 1050℃ for 3 hours to obtain mullite coated tourmaline powder, i.e. tourmaline composite material.

[0094] (3) Preparation of anion ceramic ink:

[0095] The zirconium niobium-based composite material 15 parts, the tourmaline composite material 15 parts, the ethylene glycol 60 parts, the polyhexamethylene adipic acid 10 parts, and the octylphenol polyoxyethylene ether 8 parts are weighed by weight parts. Then the zirconium niobium-based composite material and the tourmaline composite material are placed in a nylon ball mill jar, with zirconium oxide balls as grinding balls, anhydrous ethanol as medium, and ball milling at 400 rpm for 8 hours, so that the maximum particle size of the slurry is less than 1 μm; then the ball-milled slurry is dried at 80℃ for 12 hours to prepare the composite negative ion powder; finally, the composite negative ion powder is added with ethylene glycol, polyhexamethylene adipic acid and octylphenol polyoxyethylene ether, and stirred at 200 rpm for 1 hour to make it fully dispersed, to prepare the negative ion ceramic ink of the embodiment.

[0096] A preparation method of a negative ion ceramic tile, comprising the following steps:

[0097] (1) The preparation raw materials of the bottom glaze layer are weighed by weight parts: sodium feldspar 40 parts, nepheline 12 parts, titanium oxide 10 parts, quartz 18 parts, alumina 18 parts, dolomite 12 parts, talc 3 parts, kaolin 15 parts, and ball clay 8 parts; water is added for ball milling (the mass ratio of material to water is 100:40) to prepare the bottom glaze with a fineness of 0.4wt% on a 325 mesh screen.

[0098] (2) The preparation raw materials of the surface glaze layer are weighed by weight parts: nepheline syenite 45 parts, quartz 12 parts, wollastonite 22 parts, dolomite 8 parts, zinc oxide 12 parts, barium carbonate 12 parts, and kaolin 8 parts; water is added for ball milling (the mass ratio of material to water is 100:40) to prepare the surface glaze with a fineness of 0.4wt% on a 325 mesh screen.

[0099] (3) The bottom glaze, the negative ion ceramic ink, and the surface glaze are applied on the surface of the body in sequence to form the bottom glaze layer, the negative ion functional layer, and the surface glaze layer (thickness less than 1 mm), which are dried and fired at 1120℃ for 50 minutes to prepare the negative ion ceramic tile of the embodiment.

[0100] Comparative Example 1

[0101] The difference between Comparative Example 1 and Example 1 is that the negative ion ceramic ink does not contain the tourmaline composite material.

[0102] Comparative Example 2

[0103] The difference between Comparative Example 2 and Example 1 is that the wrapping layer of the tourmaline composite material in the negative ion ceramic ink is SiO2, i.e. no aluminum source is added in the preparation process of the tourmaline composite material.

[0104] Comparative Example 3

[0105] The difference between Comparative Example 3 and Example 1 is that the negative ion ceramic ink does not contain the zirconium niobium-based composite material.

[0106] Comparative Example 4

[0107] Comparative Example 4 differs from Example 1 in that the zirconium-niobium-based composite material in the negative ion ceramic ink does not contain niobium, i.e., Nb2O5 is not added in the preparation of the zirconium-niobium-based composite material.

[0108] Comparative Example 5

[0109] Comparative Example 5 differs from Example 1 in that the zirconium-niobium-based composite material in the negative ion ceramic ink does not contain neodymium, i.e., Nd2O5 is not added in the preparation of the zirconium-niobium-based composite material.

[0110] Comparative Example 6

[0111] Comparative Example 6 differs from Example 1 in that the zirconium-niobium-based composite material in the negative ion ceramic ink does not contain a zirconium silicate coating layer, i.e., it is a neodymium-europium co-doped niobium apatite powder.

[0112] Comparative Example 7

[0113] Comparative Example 7 differs from Example 1 in that the preparation raw materials of the base glaze layer are different, and Comparative Example 7 uses zinc oxide, talc and kaolin to replace titanium oxide, dolomite and ball clay in Example 1.

[0114] The raw material components of the base glaze layer of Comparative Example 7 include, by weight fraction: 35 parts of sodium feldspar, 8 parts of nepheline, 5 parts of zinc oxide, 12 parts of quartz, 12 parts of aluminum oxide, 6 parts of talc, 1 part of talc, and 13 parts of kaolin.

[0115] Comparative Example 8

[0116] Comparative Example 8 differs from Example 1 in that the preparation raw materials of the surface glaze layer are different, and Comparative Example 8 uses equal amounts of potassium feldspar and talc to replace the nepheline syenite and barium carbonate in Example 1.

[0117] The raw material components of the surface glaze layer of Comparative Example 8 include, by weight fraction: 40 parts of potassium feldspar, 8 parts of quartz, 18 parts of wollastonite, 3 parts of dolomite, 8 parts of zinc oxide, 8 parts of talc, and 3 parts of kaolin.

[0118] Performance test

[0119] According to the standards of “T / CBMCA 004-2018” and “T / CBMCA_005-2018 Negative Ion Ceramic Tile Health Grade Classification and Identification”, the negative ion release amount of the negative ion ceramic tiles prepared in Examples 1-3 and Comparative Examples 1-8 is detected; according to the building material industry implementation standard JC / T1074-2008, the purification performance and the purification efficiency of the negative ion ceramic tiles prepared in Examples 1-3 and Comparative Examples 1-8 are detected. Among them: the purification efficiency of the purification performance of formaldehyde is ≥75% for Class I and ≥80% for Class II; the negative ion is ≥2000 / cm3 , health level is I; 1200≤negative ions<2000 / cm 3 , health level is II; 500≤negative ions<1200 / cm 3 , health level is III; negative ions<500 / cm 3 , health level is IV; persistent purification efficiency≥60% is I, ≥65% is II. When testing, the negative ion release amount of the environment is 300 / cm 3 , all are detected under visible light conditions; meanwhile, the negative ion ceramic tile prepared in Example 1 is detected under dark conditions, and the results are shown in Table 1.

[0120] Table 1:

[0121]

[0122] As shown in Table 1, the negative ion release amount of the negative ion ceramic tile prepared in Examples 1-3 under visible light conditions can reach 3090-3250 / cm 3 , all of which exceed the I-level health level; the formaldehyde purification performance has a purification efficiency of 93-95%, and the persistent formaldehyde purification efficiency is 90-92%, which all exceed the requirements of the II-class standard, and has excellent negative ion induction effect and persistent formaldehyde removal effect. Meanwhile, the negative ion ceramic tile prepared in Example 1 under dark conditions without light irradiation cannot capture light energy and transfer it to Eu 3+ , so the negative ion induction effect and the persistent formaldehyde removal effect are all decreased. 3+

[0123] Compared with Example 1, Comparative Examples 1-6 respectively do not contain tourmaline composite material in the negative ion ceramic ink, adopt other tourmaline coating layers, do not contain zirconium-niobium-based composite material, the zirconium-niobium-based composite material does not contain niobium or neodymium, and does not contain zirconium silicate coating layer, all of which result in different degrees of decrease in the negative ion release amount and the formaldehyde purification efficiency of the negative ion ceramic tile. Thus, it is proved that there is a synergistic promotion effect between the tourmaline composite material and the zirconium-niobium-based composite material.

[0124] Compared with Example 1, Comparative Examples 7-8 respectively have different raw material components of the bottom glaze layer and the surface glaze layer, which also result in the decrease in the negative ion release amount and the formaldehyde purification efficiency of the negative ion ceramic tile. Thus, it is illustrated that the bottom glaze and the surface glaze of the application play a key role in the performance of the negative ion ceramic ink.

[0125] ​For those skilled in the art of the present application, without departing from the concept of the present application, can make several simple deductions or substitutions, without having to go through the creative labor. Therefore, the simple improvements made by the person skilled in the art according to the disclosure of the present application, should be within the scope of protection of the present application. The above examples are the preferred embodiments of the present application, any similar process and equivalent changes made, should belong to the protection scope of the present application.

Claims

1. A method for preparing negative ion ceramic ink, characterized in that, Includes the following steps: Preparation of zirconium-niobium based composite materials: (1) CaCO3, Nb2O5, (NH4)2HPO4, Nd2O3 and Eu2O3 are mixed to obtain a mixed raw material; then the mixed raw material is pre-calcined and ground to obtain Nd2O3-Eu2O3 co-doped niobium apatite powder; (2) The neodymium-europium co-doped niobium apatite powder is dispersed in a mixed solvent of ethanol and water, heated, and the pH value is adjusted to alkaline. Then, zirconium source solution and first silicon source solution are added dropwise and stirred to obtain a mixed solution; the mixed solution is then filtered, and the obtained solid powder is calcined for the first time to obtain zirconium silicate-coated neodymium-europium co-doped niobium apatite powder, namely the zirconium-niobium based composite material. Preparation of tourmaline composite materials: 1) Tourmaline was soaked in an ethanol solution of silane coupling agent, filtered, dried, and then dispersed in anhydrous ethanol to obtain a tourmaline suspension. 2) The tourmaline suspension is heated and stirred, and then a mixed precursor solution containing an aluminum source and a second silicon source is added to obtain a mixed suspension; The pH of the mixed suspension was adjusted to acidic, and the reaction was carried out. After the reaction was completed, the mixture was filtered, and the resulting solid powder was calcined a second time to obtain mullite-encapsulated tourmaline powder, which is the tourmaline composite material. The negative ion ceramic ink is prepared by mixing the zirconium-niobium-based composite material and the tourmaline composite material with a solvent and a dispersant.

2. The method for preparing negative ion ceramic ink according to claim 1, characterized in that, In step (1), the mixed raw materials include, by weight, 35-45 parts of CaCO3, 30-40 parts of Nb2O5, 12-24 parts of (NH4)2HPO4, 1-2 parts of Nd2O3, and 0.5-1 parts of Eu2O3; the pre-calcination is carried out at a temperature of 1200-1250℃ for 3-4 hours.

3. The method for preparing negative ion ceramic ink according to claim 1 or 2, characterized in that, In step (2), the zirconium source solution is an aqueous solution of ZrOCl2·8H2O, and the first silicon source solution is an ethanol solution of tetraethyl orthosilicate; in the mixed solution, the mass ratio of neodymium-europium co-doped niobiapatite powder, zirconium source and first silicon source is (1-3):(1-2):1; the first calcination is carried out at 1100-1200℃ for 1-2 hours.

4. The method for preparing negative ion ceramic ink according to claim 1, characterized in that, In step 1), the concentration of the ethanol solution of the silane coupling agent is 3-8 wt%; the soaking time is 1-3 hours; and the solid content of the tourmaline suspension is 5-10 wt%.

5. The method for preparing negative ion ceramic ink according to claim 1 or 4, characterized in that, In step 2), the aluminum source is aluminum isopropoxide and the second silicon source is tetraethyl orthosilicate; in the mixed suspension, the mass ratio of tourmaline, aluminum source and second silicon source is (6-8):(1-3):1; the second calcination is carried out at 1000-1100℃ for 2-3 hours.

6. The method for preparing negative ion ceramic ink according to claim 1, characterized in that, The raw material components of the negative ion ceramic ink, by weight, include: 10-15 parts of zirconium-niobium based composite material, 10-15 parts of tourmaline composite material, 40-60 parts of solvent, and 5-10 parts of dispersant.

7. A negative ion ceramic ink, characterized in that, The negative ion ceramic ink is prepared by the preparation method according to any one of claims 1-6, and the maximum particle size of the negative ion ceramic ink is less than 1 μm.

8. A negative ion ceramic brick, characterized in that, From bottom to top, it includes a body, a base glaze layer, a negative ion functional layer and a top glaze layer, wherein the negative ion functional layer is inkjet printed by the negative ion ceramic ink described in claim 7; The raw material components of the base glaze layer include, by weight: 35-40 parts of albite, 8-12 parts of nepheline, 5-10 parts of titanium dioxide, 12-18 parts of quartz, 12-18 parts of alumina, 6-12 parts of dolomite, 1-3 parts of talc, 10-15 parts of kaolin, and 3-8 parts of clay. The raw material components of the surface glaze layer include, by weight: 40-45 parts of nepheline syenite, 8-12 parts of quartz, 18-22 parts of wollastonite, 3-8 parts of dolomite, 8-12 parts of zinc oxide, 8-12 parts of barium carbonate, and 3-8 parts of kaolin.

Images