Fluorescent glaze, fluorescent glaze layer, preparation method of fluorescent glaze layer and ceramic product

Abstract

The invention relates to fluorescent glaze, a fluorescent glaze layer, a preparation method of the fluorescent glaze layer and a ceramic product. The fluorescent glaze comprises a luminescent material and a ceramic material; the ceramic material is prepared from the following components in percentage by mass: 34 percent to 39 percent of ZnO, 30 percent to 33 percent of SiO2, 8.73 percent to 10.15 percent of Na2O, 3.22 percent to 6.1 percent of Al2O3, 3.82 percent to 5.15 percent of CaO, 3.62 percent to 4.95 percent of BaO, 1.26 percent to 1.65 percent of ZrO2, 1.4 percent to 3.05 percent of K2O, 1.35 percent to 5.8 percent of B2O3 and 1 percent to 3.65 percent of MgO. The fluorescent glaze can absorb light, store energy and emit light, and has a striking effect; and meanwhile, the adhesive force with a ceramic matrix is relatively good, and the service life of a ceramic product can be effectively prolonged by applying the coating to the surface of the ceramic matrix and firing the ceramic product with a luminous surface.

Description

Technical Field

[0001] The present application relates to the technical field of glazes, and particularly to a fluorescent glaze, a fluorescent glaze layer, a preparation method thereof, and a ceramic product. Background Art

[0002] With the continuous improvement of living standards, people have higher and higher requirements for ceramic products. They not only pursue their practicality but also attach more and more importance to their decorative and functional properties. Luminescent ceramics refer to ceramic materials that can emit visible light under certain conditions. The preparation method includes applying a luminescent glaze on the surface of a ceramic substrate and firing it into a ceramic product with surface luminescence. However, the service life of traditional luminescent ceramic products is relatively short.

[0003] Therefore, it is necessary to improve the traditional technology. Summary of the Invention

[0004] Based on this, the present application provides a fluorescent glaze, a fluorescent glaze layer, a preparation method thereof, and a ceramic product with good adhesion and effectively improved service life.

[0005] The technical solutions for the present application to solve the above technical problems are as follows.

[0006] In the first aspect of the present application, a fluorescent glaze is provided, which includes a luminescent material and a ceramic material;

[0007] Calculated by mass percentage of the ceramic material, the ceramic material includes the following components: ZnO 34% - 39%, SiO2 30% - 33%, Na2O 8.73% - 10.15%, Al2O3 3.22% - 6.1%, CaO 3.82% - 5.15%, BaO 3.62% - 4.95%, ZrO2 1.26% - 1.65%, K2O 1.4% - 3.05%, B2O3 1.35% - 5.8%, and MgO 1% - 3.65%.

[0008] In some embodiments, in the fluorescent glaze, calculated by mass percentage of the ceramic material, the ceramic material includes the following components: ZnO 36% - 39%, SiO2 30% - 32%, Na2O 8.73% - 9.6%, Al2O3 4% - 6.1%, CaO 4.5% - 5.15%, BaO 4% - 4.95%, ZrO2 1.5% - 1.65%, K2O 1.40% - 2.8%, B2O3 1.35% - 4%, and MgO 1% - 3%.

[0009] In some embodiments, in the fluorescent glaze, in the ceramic material, the mass ratio of ZnO to SiO2 is 1.1 - 1.3:1.

[0010] In some of these embodiments, in the fluorescent glaze, the mass ratio of the luminescent material to the ceramic material is 1 to 5:1.

[0011] In some of these embodiments, in the fluorescent glaze, by mass parts, the fluorescent glaze comprises 6 to 8 parts of a luminescent material and 2 to 5 parts of a ceramic material.

[0012] In some of these embodiments, in the fluorescent glaze, the luminescent material comprises a long-afterglow material; optionally, the long-afterglow material comprises at least one of strontium aluminate long-afterglow material and strontium magnesium silicate long-afterglow material.

[0013] In some of these embodiments, in the fluorescent glaze, the particle size of the luminescent material is 80 to 250 mesh.

[0014] In some of these embodiments, in the fluorescent glaze, the particle size of the ceramic material is ≥400 mesh.

[0015] In some of these embodiments, in the fluorescent glaze, the fluorescent glaze further comprises at least one of a diluent, a varnish, and a curing agent.

[0016] In some of these embodiments, in the fluorescent glaze, the diluent comprises at least one of an alcohol diluent, a ketone diluent, and an ester diluent.

[0017] In some of these embodiments, in the fluorescent glaze, the mass ratio of the diluent to the ceramic material is 1 to 5:1.

[0018] In some of these embodiments, in the fluorescent glaze, the mass ratio of the varnish to the ceramic material is 0.5 to 2:1.

[0019] In some of these embodiments, in the fluorescent glaze, the curing agent comprises at least one of an acrylate curing agent and an epoxy resin curing agent.

[0020] In some of these embodiments, in the fluorescent glaze, the mass ratio of the curing agent to the ceramic material is 0.05 to 0.2:1.

[0021] The second aspect of the present application provides a fluorescent glaze layer, comprising a luminescent material and a ceramic material;

[0022] Calculated as the mass percentage of the ceramic material, the ceramic material comprises the following components: ZnO 34% to 39%, SiO2 30% to 33%, Na2O 8.73% to 10.15%, Al2O3 3.22% to 6.1%, CaO 3.82% to 5.15%, BaO 3.62% to 4.95%, ZrO2 1.26% to 1.65%, K2O 1.4% to 3.05%, B2O3 1.35% to 5.8%, and MgO 1% to 3.65%.

[0023] The third aspect of the present application provides a method for preparing a fluorescent glaze layer, which includes the following steps:

[0024] Apply the fluorescent glaze provided in the first aspect on the substrate, and form a fluorescent glaze layer on the substrate through sintering.

[0025] In some embodiments, in the method for preparing the fluorescent glaze layer, the sintering temperature is 550°C to 800°C;

[0026] Optionally, before the sintering step, a pre-sintering step is further included: raise the temperature to 250°C to 350°C at a rate of 0.8°C / min to 1.2°C / min, keep warm for 20 min to 40 min, then raise the temperature to 450°C to 500°C at a rate of 1.3°C / min to 1.7°C / min, and then raise the temperature to the sintering temperature at a rate of 2.5°C / min to 3.5°C / min for the sintering.

[0027] The fourth aspect of the present application provides a ceramic product, which includes the fluorescent glaze layer provided in the second aspect or the fluorescent glaze layer prepared by the preparation method provided in the third aspect.

[0028] Beneficial effects:

[0029] The fluorescent glaze of the present application can absorb light, store energy and emit light, and has a striking effect; at the same time, it has good adhesion to the ceramic substrate.

[0030] Apply the fluorescent glaze of the present application on the surface of the ceramic substrate and sinter it into a ceramic product with surface luminescence, which can effectively improve the service life of the ceramic product. Description of the drawings

[0031] In order to more clearly illustrate the technical solutions in the embodiments of the present application and more completely understand the present application and its beneficial effects, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present application, and those skilled in the art can obtain other drawings based on these drawings without creative efforts.

[0032] Figure 1 The fluorescent glaze layer provided for an embodiment;

[0033] Figure 2 The fluorescent ceramic provided for Example 1. Detailed implementation manners

[0034] The present application will be further described in detail below in conjunction with the embodiments and examples. It should be understood that these embodiments and examples are only used to illustrate the present application and not to limit the scope of the present application. The purpose of providing these embodiments and examples is to make the disclosure of the present application more thoroughly and comprehensively understood.

[0035] It should also be understood that the present application can be implemented in many different forms and is not limited to the embodiments and examples described herein. Those skilled in the art can make various changes or modifications without departing from the connotation of the present application, and the equivalent forms obtained also fall within the protection scope of the present application. For example, features described or illustrated as part of one embodiment can be combined in a suitable manner with another embodiment to produce a new embodiment. In addition, in the following description, a large number of specific details are given to provide a more thorough understanding of the present application. It should be understood that the present application can be implemented without one or more of these details.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present application belongs. The terms used in the specification of the present application herein are only for the purpose of describing the embodiments and examples and are not intended to limit the present application.

[0037] Unless otherwise stated or there is a contradiction, the terms or phrases used herein have the following meanings:

[0038] In the present application, the terms "a plurality of", "multiple types", "multiple times", etc., unless otherwise specified, mean greater than or equal to 2 in number. For example, "one or more types" means one or greater than or equal to two types.

[0039] The "combinations thereof", "any combinations thereof", "any combination manners thereof", etc. used herein include all suitable combination manners of any two or more of the listed items.

[0040] In this document, the "suitable combination manners", "suitable manners", "any suitable manners", etc. described as "suitable" are subject to being able to implement the technical solutions of the present application, solve the technical problems of the present application, and achieve the expected technical effects of the present application.

[0041] In this document, "preferred", "better", "more preferable", "it is advisable" are only used to describe embodiments or examples with better effects. It should be understood that they do not constitute a limitation on the protection scope of the present application. If "preferred" appears in a technical solution in multiple places, unless otherwise specified and there is no contradiction or mutual restriction relationship, each "preferred" is independent of each other.

[0042] In this application, terms such as "further", "even further", "especially", etc. are used for descriptive purposes, indicating differences in content, but should not be construed as limiting the scope of protection of this application.

[0043] In this application, "optionally", "optional", "option" mean that it is optional, that is, it refers to any one of the two alternative options of "having" or "not having". If "optional" appears multiple times in a technical solution, without special instructions, and without contradictions or mutual restrictions, each "optional" is independent of each other.

[0044] In this application, in "the first aspect", "the second aspect", "the third aspect", "the fourth aspect", etc., the terms "first", "second", "third", "fourth", etc. are only used for descriptive purposes, and should not be construed as indicating or implying relative importance or quantity, nor should it be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth", etc. only serve the purpose of non-exhaustive enumerative description, and should be understood not to constitute a closed limitation on quantity.

[0045] In this application, among the technical features described in an open-ended manner, it includes a closed technical solution composed of the listed features, and also includes an open-ended technical solution containing the listed features.

[0046] In this application, regarding a numerical interval (i.e., a numerical range), without special instructions, the distribution of the optional numerical values within this numerical interval is considered continuous, and includes the two numerical endpoints of this numerical interval (i.e., the minimum value and the maximum value), as well as each numerical value between these two numerical endpoints. Without special instructions, when the numerical interval only refers to the integers within this numerical interval, it includes the two endpoint integers of this numerical range, as well as each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all sub-ranges subsumed therein. The "numerical value" in this numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. The "numerical interval" allows for a broad inclusion of numerical interval types such as percentage intervals, ratio intervals, ratio value intervals, etc.

[0047] The temperature parameter in this application, without special limitations, allows both constant temperature treatment and fluctuations within a certain temperature range. It should be understood that the so-called constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within ranges such as ±5°C, ±4°C, ±3°C, ±2°C, ±1°C are allowed.

[0048] In this application, the terms "room temperature" or "normal temperature" generally refer to 4°C to 35°C, such as 20°C ± 5°C. In some embodiments of this application, "room temperature" or "normal temperature" refers to 10°C to 30°C. In some embodiments of this application, "room temperature" or "normal temperature" refers to 20°C to 30°C.

[0049] In this application, for units involving data ranges, if the unit is only attached after the right endpoint, it means that the units of the left endpoint and the right endpoint are the same. For example, 3~5 h means that the units of the left endpoint "3" and the right endpoint "5" are both h (hours).

[0050] All the documents mentioned in this application are cited as references in this application, just as if each document is cited as a reference separately. Unless it conflicts with the invention purpose and / or technical solution of this application, the cited documents involved in this application are cited for all contents and all purposes. When this application involves cited documents, the definitions of relevant technical features, terms, nouns, phrases, etc. in the cited documents are also cited together. When this application involves cited documents, the examples and preferred methods of the relevant technical features cited can also be used as references and incorporated into this application, but only to the extent that this application can be implemented. It should be understood that when the cited content conflicts with the description in this application, this application shall prevail or be modified adaptively according to the description in this application.

[0051] The mass or weight of the relevant components mentioned in the specification of the embodiments of this application not only can refer to the specific content of each component, but also can represent the mass or weight ratio relationship between the components. Therefore, as long as the content of the relevant components in the specification of the embodiments of this application is enlarged or reduced in proportion, it is within the scope disclosed in the specification of the embodiments of this application. Specifically, the mass or weight mentioned in the specification of the embodiments of this application can be units well-known in the chemical industry such as μg, mg, g, kg, etc.

[0052] An embodiment of this application provides a fluorescent glaze, which includes a luminescent material and a ceramic material;

[0053] Calculated by mass percentage of the ceramic material, the ceramic material includes the following components: ZnO 34%~39%, SiO2 30%~33%, Na2O 8.73%~10.15%, Al2O3 3.22%~6.1%, CaO 3.82%~5.15%, BaO 3.62%~4.95%, ZrO2 1.26%~1.65%, K2O 1.4%~3.05%, B2O3 1.35%~5.8% and MgO 1%~3.65%.

[0054] The fluorescent glaze of the present application can absorb light, store energy and emit light, having a striking effect; meanwhile, it has good adhesion to the ceramic matrix. In particular, it has good adhesion to the zirconia ceramic matrix and good wear resistance, and the pencil hardness is ≥3H.

[0055] Applying the fluorescent glaze of the present application on the surface of the ceramic matrix and firing it into a ceramic product with surface luminescence can effectively improve the service life of the ceramic product.

[0056] It can be understood that in some of these examples, in the fluorescent glaze, it is composed of a luminescent material and a ceramic material;

[0057] Among them, calculated by mass percentage of the ceramic material, the ceramic material includes the following components: ZnO 34% - 39%, SiO2 30% - 33%, Na2O 8.73% - 10.15%, Al2O3 3.22% - 6.1%, CaO 3.82% - 5.15%, BaO 3.62% - 4.95%, ZrO2 1.26% - 1.65%, K2O 1.4% - 3.05%, B2O3 1.35% - 5.8% and MgO 1% - 3.65%.

[0058] In other examples, in the fluorescent glaze, it includes a luminescent material and a ceramic material;

[0059] Among them, calculated by mass percentage of the ceramic material, the ceramic material is composed of the following components: ZnO 34% - 39%, SiO2 30% - 33%, Na2O 8.73% - 10.15%, Al2O3 3.22% - 6.1%, CaO 3.82% - 5.15%, BaO 3.62% - 4.95%, ZrO2 1.26% - 1.65%, K2O 1.4% - 3.05%, B2O3 1.35% - 5.8% and MgO 1% - 3.65%.

[0060] Furthermore, in the fluorescent glaze, it is composed of a luminescent material and a ceramic material;

[0061] Among them, calculated by mass percentage of the ceramic material, the ceramic material is composed of the following components: ZnO 34% - 39%, SiO2 30% - 33%, Na2O 8.73% - 10.15%, Al2O3 3.22% - 6.1%, CaO 3.82% - 5.15%, BaO 3.62% - 4.95%, ZrO2 1.26% - 1.65%, K2O 1.4% - 3.05%, B2O3 1.35% - 5.8% and MgO 1% - 3.65%.

[0062] It can be understood that in the ceramic material, calculated by mass percentage of the ceramic material, ZnO includes but is not limited to 34%, 34.5%, 35%, 35.5%, 36%, 36.5%, 37%, 37.5%, 38%, 38.5%, 39%; SiO2 includes but is not limited to 30%, 30.2%, 30.4%, 30.6%, 30.8%, 31%, 31.2%, 31.4%, 31.6%, 31.8%, 32%, 32.2%, 32.4%, 32.6%, 32.8%, 33%; Na2O includes but is not limited to 8.73%, 8.93%, 9.13%, 9.33%, 9.53%, 9.6%, 9.73%, 9.93%, 10%, 10.15%; Al2O3 includes but is not limited to 3.22%, 3.52%, 3.82%, 4%, 4.12%, 4.42%, 4.72%, 5.02%, 5.32%, 5.62%, 5.92%, 6.1%; CaO includes but is not limited to 3.82%, 4.02%, 4.22%, 4.42%, 4.5%, 4.62%, 4.82%, 5.02%, 5.15%; BaO includes but is not limited to 3.62%, 3.82%, 4%, 4.02%, 4.22%, 4.42%, 4.62%, 4.82%, 4.95%; ZrO2 includes but is not limited to 1.26%, 1.36%, 1.46%, 1.5%, 1.56%, 1.65%; K2O includes but is not limited to 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.05%; B2O3 includes but is not limited to 1.35%, 1.85%, 2.35%, 2.85%, 3.35%, 3.85%, 4%, 4.35%, 4.85%, 5.35%, 5.8%; MgO includes but is not limited to 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.65%; In some examples, it can be within the range formed by any two of these point values as the end values, and the same applies hereinafter.

[0063] In some of these examples, in the fluorescent glaze, calculated by mass percentage of the ceramic material, the ceramic material includes the following components: ZnO 36% - 39%, SiO2 30% - 32%, Na2O 8.73% - 9.6%, Al2O3 4% - 6.1%, CaO 4.5% - 5.15%, BaO 4% - 4.95%, ZrO2 1.5% - 1.65%, K2O 1.4% - 2.8%, B2O3 1.35% - 4% and MgO 1% - 3%.

[0064] In some of these examples, in the ceramic material of the fluorescent glaze, the mass ratio of ZnO to SiO2 is 1.1 to 1.3:1.

[0065] It can be understood that the mass ratio of ZnO to SiO2 includes but is not limited to 1.1:1, 1.12:1, 1.14:1, 1.16:1, 1.18:1, 1.2:1, 1.22:1, 1.24:1, 1.26:1, 1.28:1, 1.3:1.

[0066] Optionally, in the ceramic material of the fluorescent glaze, the mass ratio of ZnO to SiO2 is 1.15 to 1.25:1.

[0067] By further controlling the mass ratio of ZnO to SiO2, the adhesion to the ceramic matrix can be further improved.

[0068] In some of these examples, in the fluorescent glaze, the mass ratio of the luminescent material to the ceramic material is 1 to 5:1.

[0069] It can be understood that in the fluorescent glaze, the mass ratio of the luminescent material to the ceramic material includes but is not limited to 1:1, 1.5:1, 2:1, 2.33:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1.

[0070] Optionally, in the fluorescent glaze, the mass ratio of the luminescent material to the ceramic material is 2 to 3:1.

[0071] In some of these examples, in the fluorescent glaze, by mass, the fluorescent glaze includes 6 to 8 parts of the luminescent material and 2 to 5 parts of the ceramic material.

[0072] It can be understood that in the fluorescent glaze, by mass, the luminescent material includes but is not limited to 6 parts, 6.3 parts, 6.6 parts, 6.9 parts, 7.2 parts, 7.5 parts, 7.8 parts, 8 parts; the ceramic material includes but is not limited to 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts.

[0073] In some of these examples, in the fluorescent glaze, by mass, the fluorescent glaze includes 6 to 7 parts of the luminescent material and 3 to 4 parts of the ceramic material.

[0074] Optionally, by mass, the fluorescent glaze includes 7 parts of the luminescent material and 3 parts of the ceramic material.

[0075] In some of these examples, in the fluorescent glaze, the luminescent material includes a long afterglow material; optionally, the long afterglow material includes at least one of strontium aluminate long afterglow material and strontium magnesium silicate long afterglow material; further, the chemical formula of the strontium aluminate long afterglow material is SrAl2O4:Eu 2+ ,Dy 3+ .

[0076] Figure 1 The fluorescent glaze layer formed by using strontium aluminate long afterglow material as the luminescent material is sky blue.

[0077] Using strontium aluminate long afterglow material as the luminescent material, its luminescent effect is better than that of strontium magnesium silicate long afterglow material.

[0078] If the sintering temperature is too high in the air, the luminescent effect will become poor. The fluorescent glaze provided by this application can be sintered at a low temperature (550-800 °C) without affecting the night light effect of strontium aluminate.

[0079] In some examples, in the fluorescent glaze, the particle size of the luminescent material is 80-250 mesh.

[0080] It can be understood that the particle size of the luminescent material includes but is not limited to 80 mesh, 90 mesh, 100 mesh, 110 mesh, 120 mesh, 130 mesh, 140 mesh, 150 mesh, 160 mesh, 170 mesh, 180 mesh, 190 mesh, 200 mesh, 210 mesh, 220 mesh, 230 mesh, 240 mesh, 250 mesh.

[0081] In some examples, in the fluorescent glaze, the particle size of the ceramic material ≥ 400 mesh.

[0082] The particle size of the ceramic material ≥ 400 mesh means that the ceramic material can pass through a 400-mesh sieve.

[0083] Furthermore, the particle size of the ceramic material is 400-800 mesh.

[0084] By controlling the particle sizes of the luminescent material and the ceramic material, the distribution of the luminescent material and the ceramic material in the fluorescent glaze can be promoted to be uniform, agglomeration can be avoided, the smoothness of the fluorescent glaze layer obtained by sintering the fluorescent glaze can be effectively improved, and there are no visible pores on the surface; if the particles of the luminescent material are too thick, the surface will be rough and there will be too many pits after sintering.

[0085] In some examples, in the fluorescent glaze, the fluorescent glaze further includes at least one of a diluent, a varnish, and a curing agent.

[0086] In some examples, in the fluorescent glaze, the fluorescent glaze further includes a diluent, a varnish, and a curing agent.

[0087] In some examples, in the fluorescent glaze, the diluent includes at least one of an alcohol diluent, a ketone diluent, and an ester diluent.

[0088] Optionally, the alcohol diluent includes at least one of ethanol, n-propanol, isopropanol, and ethylene glycol.

[0089] Optionally, the ketone diluent includes at least one of methyl ethyl ketone, acetone, and methyl ethyl ketone.

[0090] Optionally, the ester diluent includes at least one of ethyl acetate and dimethyl carbonate.

[0091] In some examples, in the fluorescent glaze, the mass ratio of the diluent to the ceramic material is 1 to 5:1.

[0092] It can be understood that the mass ratio of the diluent to the ceramic material includes but is not limited to 1:1, 1.5:1, 2:1, 2.33:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1.

[0093] It can be understood that the present application does not limit the type of varnish, which can be obtained commercially. In some examples, the varnish includes acrylic resin and ethyl acetate; further, the varnish also includes an antifoaming agent.

[0094] In some examples, in the fluorescent glaze, the mass ratio of the varnish to the ceramic material is 0.5 to 2:1.

[0095] It can be understood that the mass ratio of the varnish to the ceramic material includes but is not limited to 0.5:1, 0.7:1, 0.9:1, 1.1:1, 1.3:1, 1.5:1, 1.7:1, 1.9:1, 2:1.

[0096] In some examples, in the fluorescent glaze, the curing agent includes at least one of acrylate curing agents and epoxy resin curing agents.

[0097] It can be understood that the acrylate curing agents include but are not limited to at least one of acrylates, methacrylates, and hydroxymethacrylates, etc.

[0098] In some examples, in the fluorescent glaze, the mass ratio of the curing agent to the ceramic material is 0.05 to 0.2:1.

[0099] It can be understood that the mass ratio of the curing agent to the ceramic material includes but is not limited to 0.05:1, 0.07:1, 0.09:1, 0.11:1, 0.13:1, 0.15:1, 0.17:1, 0.19:1, 0.2:1.

[0100] In some examples, in the fluorescent glaze, by mass, the fluorescent glaze includes 6 to 8 parts of a luminescent material, 2 to 5 parts of a ceramic material, 6 to 8 parts of a diluent, 1 to 2 parts of a varnish, and 0.1 to 0.2 parts of a curing agent.

[0101] In some examples, in the fluorescent glaze, by mass, the fluorescent glaze includes 7 parts of a luminescent material, 3 parts of a ceramic material, 7 parts of a diluent, 2 parts of a varnish, and 0.2 parts of a curing agent.

[0102] In some of these examples, by mass parts, the fluorescent glaze consists of the following components: 6 - 8 parts of luminescent material, 2 - 5 parts of ceramic material, 6 - 8 parts of diluent, 1 - 2 parts of varnish, and 0.1 - 0.2 parts of curing agent.

[0103] In some of these examples, by mass parts, the fluorescent glaze consists of the following components: 7 parts of luminescent material, 3 parts of ceramic material, 7 parts of diluent, 2 parts of varnish, and 0.2 parts of curing agent.

[0104] The fluorescent glaze provided by this application does not contain lead or radioactive components, has safe ingredients, is harmless to the human body, and meets the rohs detection standard; it can emit light after absorbing light energy; after the fluorescence duration exceeds 2 hours, the fluorescence gradually fades, and the fluorescence completely disappears after about 45 h - 50 h, at which time it is necessary to absorb light energy again.

[0105] One embodiment of this application provides a preparation method of a fluorescent glaze, including the following steps:

[0106] Provide raw materials according to the components of the above - mentioned fluorescent glaze, and mix the raw materials to prepare the fluorescent glaze.

[0107] In some of these examples, in the preparation method of the fluorescent glaze, it includes, but is not limited to, mixing evenly by means of stirring.

[0108] Further, after the mixing step, it further includes a step of defoaming the mixed slurry.

[0109] It can be understood that defoaming the mixed slurry can remove the air introduced during the stirring process and avoid the presence of bubbles on the surface of the slurry; further, the slurry can be placed in a stirring defoaming machine to evacuate the air; further, evacuate the air for 1 - 2 minutes; the vacuum time should not be too long, otherwise the diluent in the slurry is easily extracted.

[0110] One embodiment of this application provides a fluorescent glaze layer, including a luminescent material and a ceramic material;

[0111] Calculated by mass percentage of the ceramic material, the ceramic material includes the following components: 34% - 39% of ZnO, 30% - 33% of SiO2, 8.73% - 10.15% of Na2O, 3.22% - 6.1% of Al2O3, 3.82% - 5.15% of CaO, 3.62% - 4.95% of BaO, 1.26% - 1.65% of ZrO2, 1.4% - 3.05% of K2O, 1.35% - 5.8% of B2O3, and 1% - 3.65% of MgO.

[0112] One embodiment of this application provides a preparation method of a fluorescent glaze layer, including the following steps:

[0113] The fluorescent glaze provided in the first aspect is disposed on a substrate, and a fluorescent glaze layer is formed on the substrate through sintering.

[0114] In some examples, in the method for preparing the fluorescent glaze layer, the sintering temperature is 550°C to 800°C.

[0115] It can be understood that the sintering temperature includes but is not limited to 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 680°C, 690°C, 700°C, 710°C, 720°C, 730°C, 740°C, 750°C, 760°C, 770°C, 780°C, 790°C, 800°C.

[0116] In some examples, in the method for preparing the fluorescent glaze layer, before the sintering step, it further includes a pre-sintering step: rising to a first temperature of 250°C to 350°C at a first rate of 0.8°C / min to 1.2°C / min, performing a first heat preservation for 20 min to 40 min, then rising to a second temperature of 450°C to 500°C at a second rate of 1.3°C / min to 1.7°C / min, and then rising to the sintering temperature (550°C to 800°C) at a third rate of 2.5°C / min to 3.5°C / min for sintering; further, rising to the sintering temperature for sintering for 1 min to 5 min.

[0117] It can be understood that the first rate includes but is not limited to 0.8°C / min, 0.9°C / min, 1.0°C / min, 1.1°C / min, 1.2°C / min; the first temperature includes but is not limited to 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C; the time of the first heat preservation includes but is not limited to 20 min, 22 min, 24 min, 26 min, 28 min, 30 min, 32 min, 34 min, 36 min, 38 min, 40 min; the second rate includes but is not limited to 1.3°C / min, 1.4°C / min, 1.5°C / min, 1.6°C / min, 1.7°C / min; the second temperature includes but is not limited to 450°C, 460°C, 470°C, 480°C, 490°C, 500°C; the third rate includes but is not limited to 2.5°C / min, 2.6°C / min, 2.7°C / min, 2.8°C / min, 2.9°C / min, 3.0°C / min, 3.1°C / min, 3.2°C / min, 3.3°C / min, 3.4°C / min, 3.5°C / min; the sintering time includes but is not limited to 1 min, 2 min, 3 min, 4 min, 5 min.

[0118] In some of these examples, in the method for preparing the fluorescent glaze layer, the pre-sintering and sintering steps include: rising to a first temperature at a first rate of 1 °C / min, performing a first heat preservation, then rising to a second temperature at a second rate of 1.5 °C / min, and then rising to the sintering temperature at a third rate of 3 °C / min for sintering.

[0119] In some of these examples, in the method for preparing the fluorescent glaze layer, after the fluorescent glaze material is disposed on the substrate and before the sintering step, it further includes a step of semi-curing the fluorescent glaze material layer disposed on the substrate.

[0120] In some of these examples, in the method for preparing the fluorescent glaze layer, the temperature of the semi-curing is 40 °C to 60 °C.

[0121] It can be understood that the temperature of the semi-curing includes but is not limited to 40 °C, 45 °C, 50 °C, 55 °C, 60 °C.

[0122] An embodiment of the present application provides a ceramic article, including the above-mentioned fluorescent glaze layer or the fluorescent glaze layer prepared by the above-mentioned preparation method.

[0123] The ceramic article of the present application includes the above-mentioned fluorescent glaze layer or the fluorescent glaze layer prepared by the above-mentioned preparation method, and thus has at least the same advantages as the above-mentioned fluorescent glaze layer or the fluorescent glaze layer prepared by the above-mentioned preparation method, and has a long service life.

[0124] It can be understood that the ceramic articles include but are not limited to building decoration articles, safety signs, electronic display elements such as display screens and indicator lights, biological fluorescent probes, ceramic handicrafts, sculptures, murals, the wearable field, etc.

[0125] The following will further describe the present application in detail in conjunction with specific embodiments, but the embodiments of the present application are not limited thereto.

[0126] Example 1

[0127] (1) Fluorescent glaze material components: strontium aluminate (particle size of 80 - 250 mesh) 7 g, ceramic powder 3 g, (ester-based) diluent 7 g, varnish 2 g, (epoxy resin-based) curing agent 0.2 g; wherein, the mass ratio of the luminescent material to the ceramic material is about 2.33:1; the composition of the ceramic powder: 38.6% ZnO, 31.5% SiO2, 8.87% Na2O, 5.55% Al2O3, 4.92% CaO, 4.75% BaO, 1.65% ZrO2, 1.4% K2O, 1.41% B2O3, 1.35% MgO; the mass ratio of ZnO to SiO2 is about 1.23:1. Sieve the ceramic powder through a 400-mesh sieve, then mix it with strontium aluminate, diluent, varnish, and curing agent and stir evenly, and place the obtained fluorescent slurry in a stirring degassing machine to evacuate for 2 minutes to obtain the fluorescent glaze material.

[0128] (2) Upper fluorescent glaze slurry: The barrel tube sucks the fluorescent glaze prepared in step (1) and extrudes it into the font gaps of the bezel laser engraving. Then, use a flat piece to scrape the surface flat and place it in an oven to dry at 45°C for about 30 minutes until the glaze is semi-dry. Then, use a flat piece to scrape off the excess slurry. There should be no glaze on the surface except for the fonts to be filled. Then, bake at 50°C for 15 minutes and then sinter. The final sintering temperature is 800°C. Specifically: Raise the temperature to 300°C at a rate of 1°C / min, hold for 30 minutes, raise the temperature to 500°C at a rate of 1.5°C / min, raise the temperature to 800°C at a rate of 3°C / min, and hold for 2 minutes to obtain the fluorescent ceramic; as Figure 2 shown.

[0129] Example 2

[0130] (1) Components of the fluorescent glaze: 7 g of strontium aluminate (particle size 80 - 250 mesh), 3 g of ceramic powder, 7 g of (ester-based) diluent, 2 g of varnish, 0.2 g of (epoxy resin-based) curing agent; among them, the mass ratio of the luminescent material to the ceramic material is about 2.33:1; Composition of the ceramic powder: 36.3% ZnO, 30.5% SiO2, 9.52% Na2O, 4.1% Al2O3, 4.95% CaO, 4.95% BaO, 1.65% ZrO2, 2.52% K2O, 3.01% B2O3, 2.52% MgO; The mass ratio of ZnO to SiO2 is about 1.19:1. Sieve the ceramic powder through a 400-mesh sieve, then mix it with strontium aluminate, diluent, varnish, and curing agent and stir evenly. Place the obtained fluorescent slurry in a stirring degassing machine and evacuate for 2 minutes to obtain the fluorescent glaze.

[0131] (2) Upper fluorescent glaze slurry: The barrel tube sucks the fluorescent glaze prepared in step (1) and extrudes it into the font gaps of the bezel laser engraving. Then, use a flat piece to scrape the surface flat and place it in an oven to dry at 45°C for about 30 minutes until the glaze is semi-dry. Then, use a flat piece to scrape off the excess slurry. There should be no glaze on the surface except for the fonts to be filled. Then, bake at 50°C for 15 minutes and then sinter. The final sintering temperature is 550°C. Specifically: Raise the temperature to 300°C at a rate of 1°C / min, hold for 30 minutes, raise the temperature to 500°C at a rate of 1.5°C / min, raise the temperature to 550°C at a rate of 3°C / min, and hold for 2 minutes to obtain the fluorescent ceramic.

[0132] Example 3

[0133] Basically the same as Example 1, except that the mass ratios of ZnO and SiO2 in the ceramic powder composition are different. The ceramic powder composition is as follows: 39% ZnO, 30% SiO2, 8.87% Na2O, 5.55% Al2O3, 4.92% CaO, 4.75% BaO, 1.65% ZrO2, 2.5% K2O, 1.41% B2O3, 1.35% MgO; the mass ratio of ZnO to SiO2 is about 1.3:1.

[0134] Example 4

[0135] Basically the same as Example 1, except that in the fluorescent glaze composition, there are 5 g of strontium aluminate and 5 g of ceramic powder, and the rest remains unchanged; the mass ratio of the luminescent material to the ceramic material is about 1:1.

[0136] Example 5

[0137] Basically the same as Example 1, except that in step (2), after drying at 50°C for 15 min, it is heated to 800°C at a rate of 3°C / min and held for 2 min to obtain the fluorescent ceramic.

[0138] Comparative Example 1

[0139] Basically the same as Example 1, except that in the ceramic powder composition, ZnO is replaced with an equal mass of TiO2; the ceramic powder composition is as follows: 38.6% TiO2, 31.5% SiO2, 8.87% Na2O, 5.55% Al2O3, 4.92% CaO, 4.75% BaO, 1.65% ZrO2, 1.4% K2O, 1.41% B2O3, 1.35% MgO.

[0140] Comparative Example 2

[0141] Basically the same as Example 1, except that the mass ratios of ZnO and SiO2 in the ceramic powder composition are different. The ceramic powder composition is as follows: 20.1% ZnO, 50% SiO2, 8.87% Na2O, 5.55% Al2O3, 4.92% CaO, 4.75% BaO, 1.65% ZrO2, 1.4% K2O, 1.41% B2O3, 1.35% MgO; the mass ratio of ZnO to SiO2 is about 0.402:1.

[0142] The fluorescent ceramics prepared in each example and comparative example were subjected to a boiling water cross-cut test, and the results are shown in Table 1.

[0143] Table 1

[0144]

[0145] As can be seen from Table 1, compared with the comparative example, in the examples, the luminescent material is combined with a ceramic material formed by ZnO, SiO2, Na2O, Al2O3, CaO, BaO, ZrO2, K2O, B2O3 and MgO in appropriate proportions. The obtained fluorescent ceramics have higher adhesion and better wear resistance, effectively improving the service life. Among them, there are visible pores on the surface of the fluorescent ceramics prepared in Example 5. The fluorescent ceramics prepared in Examples 1 to 4 have better smoothness, no visible pores on the surface, and the appearance and wear resistance are better than those in Example 5.

[0146] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope recorded in this specification.

[0147] The above-described embodiments only represent several implementation manners of the present application, which are convenient for understanding the technical solutions of the present application specifically and in detail, but should not be construed as a limitation on the protection scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several deformations and improvements can be made, and these all belong to the protection scope of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the protection scope of the appended claims of the present application. Therefore, the protection scope of the patent of the present application should be subject to the content of the appended claims, and the specification can be used to explain the content of the claims.

Claims

1. A fluorescent glaze, characterized in that, It includes a luminescent material and a ceramic material; Based on the mass percentage of the ceramic material, the ceramic material includes the following components: ZnO 34% - 39%, SiO2 30% - 33%, Na2O 8.73% - 10.15%, Al2O3 3.22% - 6.1%, CaO 3.82% - 5.15%, BaO 3.62% - 4.95%, ZrO2 1.26% - 1.65%, K2O 1.4% - 3.05%, B2O3 1.35% - 5.8%, and MgO 1% - 3.65%.

2. The fluorescent glaze according to claim 1, wherein Based on the mass percentage of the ceramic material, the ceramic material includes the following components: ZnO 36% - 39%, SiO2 30% - 32%, Na2O 8.8% - 9.6%, Al2O3 4% - 6.1%, CaO 4.5% - 5.15%, BaO 4% - 4.95%, ZrO2 1.5% - 1.65%, K2O 1.4% - 2.8%, B2O3 1.35% - 4%, and MgO 1% - 3%.

3. The fluorescent glaze according to claim 1, characterized in that, In the ceramic material, the mass ratio of ZnO to SiO2 is 1.1 - 1.3:1; And / or, the mass ratio of the luminescent material to the ceramic material is 1 - 5:1; Optionally, by mass parts, the fluorescent glaze includes 6 - 8 parts of the luminescent material and 2 - 5 parts of the ceramic material.

4. The fluorescent glaze according to any one of claims 1 to 3, characterized in that, The fluorescent glaze satisfies at least one of the following characteristics: (1) The luminescent material includes a long - persistent phosphor; Optionally, the long - persistent phosphor includes at least one of strontium aluminate long - persistent phosphor and strontium magnesium silicate long - persistent phosphor; (2) The particle size of the luminescent material is 80 - 250 mesh; (3) The particle size of the ceramic material is ≥400 mesh.

5. The fluorescent glaze according to any one of claims 1 to 3, characterized in that, The fluorescent glaze further includes at least one of a diluent, a varnish, and a curing agent.

6. The fluorescent glaze according to claim 5, wherein The fluorescent glaze satisfies at least one of the following characteristics: (1) The diluent includes at least one of an alcohol diluent, a ketone diluent, and an ester diluent; (2) The mass ratio of the diluent to the ceramic material is 1 - 5:1; (3) The mass ratio of the varnish to the ceramic material is 0.5 - 2:1; (4) The curing agent includes at least one of an acrylate curing agent and an epoxy resin curing agent; (5) The mass ratio of the curing agent to the ceramic material is 0.05 - 0.2:

1.

7. A fluorescent glaze layer, characterized in that, It includes a luminescent material and a ceramic material; Based on the mass percentage of the ceramic material, the ceramic material includes the following components: ZnO 34% - 39%, SiO2 30% - 33%, Na2O 8.73% - 10.15%, Al2O3 3.22% - 6.1%, CaO 3.82% - 5.15%, BaO 3.62% - 4.95%, ZrO2 1.26% - 1.65%, K2O 1.4% - 3.05%, B2O3 1.35% - 5.8%, and MgO 1% - 3.65%.

8. A method for preparing a fluorescent glaze layer, characterized in that, It includes the following steps: Apply the fluorescent glaze according to any one of claims 1 - 6 on a substrate, and form a fluorescent glaze layer on the substrate through sintering.

9. The preparation method of the fluorescent glaze layer according to claim 8, characterized in that, The sintering temperature is 550°C to 800°C; Optionally, before the sintering step, a pre-sintering step is further included: heating to 250°C to 350°C at a rate of 0.8°C / min to 1.2°C / min, holding for 20 min to 40 min, then heating to 450°C to 500°C at a rate of 1.3°C / min to 1.7°C / min, and then heating to the sintering temperature at a rate of 2.5°C / min to 3.5°C / min for the sintering.

10. A ceramic product, characterized in that, It includes the fluorescent glaze layer as described in claim 7 or the fluorescent glaze layer prepared by the preparation method as described in any one of claims 8 to 9.

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