Long-lasting luminescent ceramic glaze with interlayer chemical coupling and preparation method and application thereof

Abstract

The present application relates to the technical field of ceramic glaze production, in particular to long-acting luminescent ceramic glaze with interlayer chemical coupling and its preparation method and application. The glaze is a multilayer composite structure, which comprises a bottom bonding glaze layer, a core luminescent functional glaze layer and a photochromic protective surface glaze layer from inside to outside. The core layer uses an Nb2O5-containing glaze system to realize chemical coupling with the bottom layer, and uses a core-shell structure long afterglow luminescent material to realize white light adjustment; the protective surface glaze layer adopts a WO3 / TiO2 / CeO2 composite system. The present application is prepared by a two-step method of "high-temperature one-time firing + low-temperature secondary firing", and the obtained glaze has high interlayer bonding strength, strong weather resistance, long luminescent life and can adapt to environmental light, and is suitable for safety marking products in extreme environments.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramic glaze production, in particular to a long-acting luminescent ceramic glaze with interlayer chemical coupling and a preparation method and application thereof. BACKGROUND

[0002] In extreme industrial environments such as petroleum chemical industry, power system, tunnel, offshore platform, clear and durable safety signs are essential for the safety of personnel and equipment. The widely used organic luminescent paint or signboard has problems such as poor weather resistance, easy aging and powdering, short service life, and cannot meet the long-term and maintenance-free use requirements.

[0003] It is recognized that the ideal way to solve the above problems is to incorporate luminescent powder into ceramic glaze to make luminescent ceramic. However, the existing luminescent ceramic glaze still has the following technical bottlenecks: first, the commonly used SrAl2O4:Eu, Dy luminescent powder will quickly decay in strong ultraviolet light and high temperature and humidity environment, and its luminescent color is single (mainly yellow-green), which limits the application scenarios. Second, the ultraviolet absorber added to protect the luminescent powder will continuously block the ultraviolet light, resulting in low “charging” efficiency of the luminescent powder in weak light environment such as cloudy days and evenings, forming a contradiction between “protection” and “excitation”. Third, due to the difference in thermal expansion coefficient and chemical properties between multi-layer functional glazes, the interlayer bonding strength is insufficient, and cracking or peeling occurs when the temperature changes dramatically.

[0004] Therefore, there is an urgent need in the art for a new type of luminescent ceramic glaze that can adapt to environmental changes, has ultra-long service life, multi-color luminescence and extreme weather resistance. SUMMARY

[0005] In view of the deficiencies in the prior art above, the purpose of the present application is to provide a long-acting luminescent ceramic glaze with interlayer chemical coupling, which has high interlayer bonding strength, excellent heat shock resistance and corrosion resistance through interface chemical coupling design.

[0006] Another purpose of the present application is to provide a preparation method of a long-acting luminescent ceramic glaze with interlayer chemical coupling, which adopts a two-step process of “high-temperature one-time firing + low-temperature secondary firing” to provide kinetic conditions for interface chemical reaction and stress release, ensuring the integrity and functionality of the multi-layer structure.

[0007] The third purpose of the present application is to provide an application of a long-acting luminescent ceramic glaze with interlayer chemical coupling, which is used in safety sign products of petroleum chemical facilities, power facilities, tunnels, offshore platforms or ships.

[0008] The present application is implemented by adopting the following technical solutions:

[0009] The long-acting night light ceramic glaze with interlayer chemical coupling is a multi-layer composite structure arranged on a ceramic base, which comprises, from inside to outside, a bottom bonding glaze layer, a core night light functional glaze layer, and a photochromic protective surface glaze layer.

[0010] The bottom bonding glaze layer is sintered from first inorganic silicate raw materials;

[0011] The core night light functional glaze layer is sintered from second inorganic silicate raw materials, long afterglow luminescent materials, and 4-6% niobium pentoxide in total mass of the core night light functional glaze layer;

[0012] The photochromic protective surface glaze layer is sintered from third inorganic glass raw materials, nano tungsten trioxide, nano titanium dioxide, nano cerium oxide, and CaS:Eu 2+ , Tm 3+ .

[0013] The total mass ratio of the nano tungsten trioxide, nano titanium dioxide, nano cerium oxide, and CaS:Eu 2+ , Tm 3+ in the surface glaze layer is 14.5-26.5%.

[0014] The long afterglow luminescent material is a core-shell composite structure, the core of which is an alkali earth metal silicate doped with Eu 2+ and Ho 3+ , and the shell is mesoporous silica.

[0015] In the bottom bonding glaze layer, the first inorganic silicate raw materials include, by weight percentage, feldspar 38-42%; quartz 23-27%; calcite 10-14%; zinc oxide 6-9%; kaolin 8-11%; and zircon 4-6%.

[0016] The second inorganic silicate raw materials are calcium-zinc borosilicate glass frit and active silicon dioxide; and the raw materials of the core night light functional glaze layer include, by weight percentage, calcium-zinc borosilicate glass frit 68-72%; long afterglow luminescent material 15-23%; active silicon dioxide 4-6%; and niobium pentoxide 4-6%.

[0017] The raw materials of the photochromic protective surface glaze layer include, by weight percentage, phosphate glass powder 74-82%; nano tungsten trioxide 2-4%; nano titanium dioxide 8-11%; nano cerium oxide 0.5-1.5%; and CaS:Eu 2+ , Tm 3+ : 4-10%.

[0018] The preparation method of the long-acting night light ceramic glaze with interlayer chemical coupling comprises the following steps:

[0019] (1) Apply the bottom layer bonding glaze layer and the core luminescent functional glaze layer on the ceramic substrate in turn, and perform high-temperature one-time firing to obtain a luminescent glaze substrate;

[0020] (2) Apply a photochromic protective surface glaze layer on the luminescent glaze substrate, and perform low-temperature two-time firing to obtain the long-acting luminescent ceramic glaze;

[0021] The peak temperature of the high-temperature one-time firing is 1220-1240℃.

[0022] The peak temperature of the low-temperature two-time firing is 780-820℃.

[0023] The process of the high-temperature one-time firing includes: increasing the temperature from room temperature to 600℃ at a rate of 2-4℃ / min, then increasing the temperature to 900℃ at a rate of 1-2℃ / min, and finally increasing the temperature to the peak temperature at a rate of 4-6℃ / min and maintaining for 15-25min; after firing, first cooling to 950℃ at a rate of 4-6℃ / min, and then cooling to 750℃ at a rate of 1-2℃ / min.

[0024] The process of the low-temperature two-time firing includes: increasing the temperature from room temperature to 500℃ at a rate of 4-6℃ / min, then increasing the temperature to 700℃ at a rate of 1-3℃ / min, and finally increasing the temperature to the peak temperature at a rate of 7-9℃ / min and maintaining for 5-10min; after firing, first cooling to 550℃ at a rate of 1-3℃ / min.

[0025] The long-acting luminescent ceramic glaze with interlayer chemical coupling is applied to safety sign products of petroleum and chemical facilities, power facilities, tunnels, offshore platforms or ships.

[0026] Specifically, the preparation method of the long-acting luminescent ceramic glaze with interlayer chemical coupling is as follows:

[0027] Raw material pretreatment:

[0028] Quartz: calcined at 980-1020℃ for 1.5-2.5h, then water quenched and ball milled to D50<10μm.

[0029] Zinc oxide: calcined at 750-850℃ for 1-1.5h.

[0030] Niobium pentoxide: calcined at 800-900℃ for 1.5-2.5h, and then ball milled to D50<3μm.

[0031] Nanopowder (WO3, TiO2): mixed with 3-5% of polyacrylammonium dispersant and 25-30% of ethyl cellulose carrier by weight, and ultrasonically treated for 20-40min.

[0032] CaS:Eu 2+ , Tm 3+Surface coating pretreatment:

[0033] Ball milling: CaS:Eu 2+ , Tm 3+ The powder is ball milled to D50 < 2 μm.

[0034] Coating: The ball-milled CaS powder is dispersed in a mixed solution of ethanol and water, 1-2% of TEOS by mass of CaS and a catalytic amount of ammonia water (0.5-1.5% of ammonia water by mass of CaS powder, ammonia water concentration: 25%) are added, and the mixture is stirred and reacted at 40-60°C for 4-6 hours.

[0035] Post-treatment: After the reaction is completed, centrifugation, washing, and drying at 80°C are performed, and finally, heat treatment at 400°C for 1 hour in an inert atmosphere (N2) is performed to form CaS@SiO2 composite powder having a dense nanometer SiO2 protective layer.

[0036] Preparation of core-shell composite long afterglow luminescent material, comprising the following steps:

[0037] a. Core synthesis (Ba 1.95 Sr 0.05 SiO4:Eu 0.01 ,Ho 0.02 )

[0038] Batching and ball milling: The ingredients are weighed according to the stoichiometric ratio, 1-3 wt% H3BO3 is added as a fluxing agent, and high-energy ball milling is performed for 10-14 hours in anhydrous ethanol as the medium.

[0039] Pre-burning: After drying, pre-burning is performed at 1130-1170°C for 2-4 hours in a weak reducing atmosphere (95% N2+5% H2).

[0040] Final burning: After 5-7 hours of re-milling, sintering is performed at 1230-1270°C for 3-5 hours in the same atmosphere.

[0041] Annealing: Precise annealing is performed at a rate of -4~-6°C / min from the peak temperature to 800°C, and at a rate of -1~-2°C / min from 800°C to 300°C, and then the furnace is cooled down.

[0042] b. Core-shell structure construction (Core@mSiO2)

[0043] Coating: The core powder is dispersed in a solution containing ethanol, water, and 0.1-0.2 wt% CTAB.

[0044] Reaction: TEOS and ammonia water are slowly added dropwise, and the mixture is stirred and reacted at 35-45°C for 5-7 hours.

[0045] Post-treatment: After centrifugation, washing, and drying, calcinate in air at 520-580℃ for 3-5 hours.

[0046] Finished product: Collect the powder and dry it under vacuum at 60℃.

[0047] Glaze preparation and sintering process

[0048] Glaze preparation:

[0049] The base glaze layer and the core luminescent functional glaze layer slurry are weighed according to the formula, and deionized water (solid content 58-65%) and 0.2-0.5wt% sodium tripolyphosphate dispersant are added. The mixture is ball-milled for 16-24 hours until a fineness D90 < 25μm is achieved. The specific gravity exiting the mill is controlled at 1.40-1.50 g / cm³. 3 .

[0050] Photochromic protective glaze paste: The powder and organic carrier are mixed at a weight ratio of 1:1.1-1.3 and ground 4-6 times with a three-roll mill until the fineness is <20μm. The organic carrier is a mixture of 8% ethyl cellulose, 85% terpineol and 7% dibutyl phthalate.

[0051] Glazing and sintering process

[0052] Substrate preparation: Clean and dry the ceramic plate.

[0053] Glazing 1 (bottom layer combined with glaze): Spray glaze, wet film thickness 0.2-0.4mm, dry at room temperature for 1-3 hours.

[0054] Glazing 2 (core luminous functional glaze layer): Spray glaze, wet film thickness 0.3-0.5mm, dry at room temperature for 3-5 hours.

[0055] High-temperature single-stage firing (bottom layer + core layer):

[0056] Sintering curve:

[0057] Room temperature→600℃(2-4℃ / min);

[0058] 600℃→900℃(1-2℃ / min);

[0059] 900℃→1220-1240℃(4-6℃ / min);

[0060] Hold at peak temperature for 15-25 minutes.

[0061] Annealing profile:

[0062] Peak temperature → 950℃ (4~6℃ / min);

[0063] 950℃→750℃(1~2℃ / min);

[0064] 750℃→300℃(2~4℃ / min);

[0065] 300℃ → room temperature (cooled with the furnace).

[0066] Glazing 3 (photochromic protective glaze layer): screen printing, control the dry film thickness to 20-40μm, dry at 70-90℃ for 20-40min.

[0067] Low-temperature secondary firing (glaze layer):

[0068] Sintering curve:

[0069] Room temperature → 500℃ (4-6℃ / min, glue removal);

[0070] 500℃→700℃ (1-3℃ / min, secondary coupling platform);

[0071] 700℃→780-820℃(7-9℃ / min);

[0072] Hold at peak temperature for 5-10 minutes.

[0073] Annealing profile:

[0074] Peak temperature → 550℃ (1~3℃ / min, stress relief zone);

[0075] 550℃→300℃(3~5℃ / min);

[0076] 300℃ → room temperature (cooled with the furnace).

[0077] This invention abandons the use of single luminescent materials or structures that are unstable at high temperatures, and creatively combines a blue-green luminescent alkaline earth metal silicate core with a highly thermally stable orange-red long-afterglow material. By precisely controlling the ratio of the two, and utilizing the additive color mixing principle of light, their emission spectra are visually superimposed, thus achieving a continuous and tunable emission color from cool white to warm white. The niobium pentoxide (Nb₂O₅) introduced into the core glaze layer not only acts as a network former or modifier within the glaze layer, but more importantly, it can react with zinc ions (ZnO₂) diffused from the underlying glaze. 2+Nb2O5, zirconite and other key components are introduced to generate Nb-Zn compound and other enhanced crystal phases in situ at the interface, which transforms the traditional physical adhesion into strong chemical bonding. This makes the interlayer bonding strength of the glaze reach more than 20 MPa, and the thermal shock resistance exceeds 50 times, and the glaze can withstand long-term thermal shock and corrosion in extreme environments such as petroleum, chemical industry and ocean, and the service life is far longer than that of organic luminescent coating.

[0078] Compared with the prior art, the present application has the following advantages:

[0079] (1) By compounding the orange-red long afterglow material with high thermal stability with the blue-green light core, the present application fundamentally solves the problem that the traditional ZnS material cannot withstand high-temperature firing. The composite luminescent system can still maintain excellent luminescent performance after being fired at a high temperature of 1220-1240℃.

[0080] (2) By introducing Nb2O5, zirconite and other key components, “chemical rivet” crystal phases are generated in situ at the interlayer interface, which transforms the traditional physical adhesion into strong chemical bonding. This makes the interlayer bonding strength of the glaze reach more than 20 MPa, and the thermal shock resistance exceeds 50 times, and the glaze can withstand long-term thermal shock and corrosion in extreme environments such as petroleum, chemical industry and ocean, and the service life is far longer than that of organic luminescent coating.

[0081] (3) The two-step process of “high-temperature first firing + low-temperature second firing” is adopted, and the rising and falling temperature curves are accurately controlled to provide sufficient kinetic conditions for interface reaction, stress release and preservation of functional structure. The process parameter window is wide, the equipment requirement is moderate, and stable and controllable large-scale production can be easily realized. BRIEF DESCRIPTION OF DRAWINGS

[0082] Figure 1 The Ba 1.95 Sr 0.05 SiO4:Eu 0.01 , Ho 0.02 The emission spectrum of the luminescent powder is measured at 365nm as the monitoring wavelength.

[0083] Figure 2 The Ba 1.95 Sr 0.05SiO4:Eu 0.01 , Ho 0.02 The excitation spectrum of the luminescent powder was measured at 500 nm as the monitoring wavelength. DETAILED DESCRIPTION

[0084] In order to make the purpose, technical scheme of the present application more clear, the present application is further explained in detail as follows.

[0085] Feldspar: Xiangtan Sino-Korea Feldspar Mining Co., Ltd., Potassium feldspar, K2O content ≥ 10%, particle size D50 ≤ 15 μm;

[0086] Quartz: Jiangsu Pacific Quartz Co., Ltd., SiO2 content ≥ 99.9%, after calcination at 1000 ℃ and ball milling to D50 ≤ 8 μm;

[0087] Calcite: Guilin Jinshan New Material Co., Ltd., Heavy calcium carbonate, CaCO3 content ≥ 98.5%, particle size D50 ≤ 5 μm;

[0088] Zinc oxide: Liuzhou Zinc Products Co., Ltd., Indirect zinc oxide, ZnO content ≥ 99.5%, after calcination at 800 ℃;

[0089] Kaolin: China Kaolin Co., Ltd. (Suzhou), Calcined kaolin, Al2O3 content ≥ 40%, particle size D50 ≤ 2 μm;

[0090] Zircon: Guangdong Oriental Zircon Industry Technology Co., Ltd., Superfine zircon powder, ZrSiO4 content ≥ 99%, particle size D50 ~ 2 μm;

[0091] Calcium-zinc borosilicate glass frit: SiO2: 52%-58%; B2O3: 6%-10%; CaO: 8%-15%; ZnO: 5%-9%; Al2O3: 2%-5%; other impurities ≤ 0.5%, softening point 850 ± 10 ℃, thermal expansion coefficient (6.0 ± 0.2) × 10 -6 / K;

[0092] Active silicon dioxide: Wacker Industrial Group, AEROSIL ® 200, specific surface area 200 ± 25 m 2 / g;

[0093] Niobium pentoxide: Luoyang Luanchuan Molybdenum Industry Group Co., Ltd., Nb2O5 content ≥ 99.9%, after calcination at 850 ℃ and ball milling to D50 ≤ 3 μm;

[0094] Phosphate glass powder: P2O5: 45%-55%; ZnO: 10%-18%; Na2O: 3%-8%; CaO: 5%-12%; Al2O3: 1%-4%, softening point 650 ± 10 ℃;

[0095] Nano-WO3: Shanghai Aladdin Bio-Chem Technology Co., Ltd., particle size <50 nm, purity 99.9%;

[0096] Nano-TiO2: Degussa, P25, anatase, particle size about 21 nm;

[0097] Nano-CeO2: Shandong Guocui Functional Materials Co., Ltd., CeO2 content ≥99.9%, particle size 30-50 nm;

[0098] Long afterglow luminescent powder SrMgAl4O8:Eu 2+ Dy 3+ : Dalian Luminescence Technology Co., Ltd.

[0099] Borosilicate: Schott AG, SiO2: 81-83%, B2O3: 13-15%, Na2O / K2O: 4-5%; thermal expansion coefficient: 3.3 x 10 -6 / K (20-300°C);

[0100] V2O5: Sinopharm Chemical Reagent Co., Ltd.

[0101] CaS:Eu 2+ ,Tm 3+ : Youyan Rare Earth New Materials Co., Ltd.

[0102] Raw material pretreatment

[0103] Quartz: calcined at 1000°C for 2 h, then ball milled to D50 <10 μm after water quenching.

[0104] Zinc oxide: calcined at 800°C for 1.5 h.

[0105] Niobium pentoxide: calcined at 850°C for 2 h, then ball milled to D50 <3 μm.

[0106] Nano-powder (WO3, TiO2): mixed with 4% by weight of ammonium polyacrylate and 30% by weight of carrier (8% ethyl cellulose, 85% terpineol and 7% dibutyl phthalate) based on the weight of the powder, and ultrasonically treated for 30 min.

[0107] Surface coating pretreatment of CaS:Eu 2+ ,Tm 3+ :

[0108] Ball milling: CaS:Eu 2+ ,Tm 3+ powder (source: e.g., Beijing Zhongke Rare Earth New Materials Co., Ltd.) is ball milled to D50 <2 μm.

[0109] Coating: The milled CaS powder was dispersed in a mixture of ethanol and water, 2% of TEOS (relative to the mass of CaS) and a catalytic amount of ammonia (1% of the mass of CaS powder, ammonia concentration: 25%) were added, and the mixture was stirred at 50°C for 5 hours.

[0110] Post-processing: After the reaction was completed, centrifugation, washing, and drying at 80°C were performed, and finally, heat treatment at 400°C for 1 hour in an inert atmosphere (N2) was performed to form CaS@SiO2 composite powder with a dense nanometer SiO2 protective layer.

[0111] The firing atmosphere of the examples and comparative examples was a weak reducing atmosphere (N2 protection).

[0112] Example 1

[0113] The preparation of the core-shell composite structure long afterglow luminescent material included the following steps:

[0114] a. Core synthesis (Ba 1.95 Sr 0.05 SiO4: Eu 0.01 , Ho 0.02 )

[0115] Batching and ball milling: The ingredients were weighed according to the stoichiometric ratio, 1wt% H3BO3 was added as a fluxing agent, and high-energy ball milling was performed for 10h in anhydrous ethanol as the medium.

[0116] Pre-burning: After drying, pre-burning was performed at 1130°C for 2h in a weak reducing atmosphere (95% N2+5% H2).

[0117] Final burning: After 5h of re-milling, sintering was performed at 1230°C for 3h in the same atmosphere.

[0118] Annealing: Precise annealing was performed at a rate of 4°C / min from the peak temperature to 800°C, and at a rate of 1°C / min from 800°C to 300°C, followed by furnace cooling. Ba 1.95 Sr 0.05 SiO4: Eu 0.01 , Ho 0.02 The luminescent powder had an excitation spectrum measured at 500nm as the monitoring wavelength, as shown in Figure 2 .

[0119] b. Core-shell structure construction (Core@mSiO2)

[0120] Coating: The core luminescent powder was dispersed in a solution containing ethanol, water, and 0.1wt% CTAB.

[0121] Reaction: TEOS and ammonia were slowly added dropwise, and the mixture was stirred at 35°C for 5h.

[0122] Post treatment: centrifugation, washing, drying, calcination in air at 520℃ for 3h.

[0123] Finished product: collect the powder, vacuum drying at 60℃ to get the product.

[0124] The adding amount and ratio of each raw material are shown in Table 1.

[0125] The preparation method of the long-acting night light ceramic glaze with interlayer chemical coupling comprises the following steps:

[0126] (1) applying a bottom bonding glaze layer and a core night light functional glaze layer on a ceramic substrate in sequence, and performing high-temperature one-time firing to obtain a night light glaze substrate;

[0127] The glaze slurries of the bottom bonding glaze layer and the core night light functional glaze layer are respectively weighed according to the formula, deionized water (solid content 58%) and 0.2wt% dispersant are added, and ball milling is performed for 16h until the fineness D90 is less than 25μm. The out-mill specific gravity is controlled at 1.40g / cm 3 .

[0128] The photochromic protective surface glaze layer paste: the powder and the organic carrier are mixed in a weight ratio of 1:1.1, and are ground by a three-roll grinder for 4 times until the fineness is less than 20μm. The organic carrier is a mixture composed of 8% ethyl cellulose, 85% terpineol and 7% dibutyl phthalate.

[0129] Glazing and sintering process

[0130] Substrate preparation: clean and dry the ceramic plate.

[0131] Glazing 1 (bottom bonding glaze layer): spray glazing, wet film thickness 0.2mm, room temperature drying for 1h.

[0132] Glazing 2 (core night light functional glaze layer): spray glazing, wet film thickness 0.3mm, room temperature drying for 3h.

[0133] The process of high-temperature one-time firing includes: increasing the temperature from room temperature to 600℃ at a rate of 2℃ / min, then increasing the temperature to 900℃ at a rate of 1℃ / min, and finally increasing the temperature to the peak temperature at a rate of 4℃ / min and keeping for 15min; after firing, first cooling to 950℃ at a rate of 4℃ / min, and then cooling to 750℃ at a rate of 1℃ / min.

[0134] (2) applying a photochromic protective surface glaze layer on the night light glaze substrate, and performing low-temperature two-time firing to obtain the long-acting night light ceramic glaze;

[0135] Glazing 3 (photochromic protective surface glaze layer): screen printing, control the dry film thickness to be 20μm, and dry at 70℃ for 20min.

[0136] The low-temperature secondary sintering process includes: heating from room temperature to 500°C at 4°C / min, then heating to 700°C at 1°C / min, and finally heating to the peak temperature at 7°C / min and keeping for 5 min; after sintering, cooling to 550°C at 1°C / min.

[0137] The peak temperature of the high-temperature primary sintering is 1220°C, and the peak temperature of the low-temperature secondary sintering is 780°C.

[0138] Example 2

[0139] The core-shell composite structure long afterglow luminescent material preparation includes the following steps:

[0140] a. Core synthesis (Ba 1.95 Sr 0.05 SiO4: Eu 0.01 , Ho 0.02 )

[0141] Dosing and ball milling: weigh according to the stoichiometric ratio, add 3wt% H3BO3 as flux, use anhydrous ethanol as medium, and high-energy ball mill for 14h.

[0142] Pre-sintering: after drying, pre-sinter at 1170°C for 4h under weak reducing atmosphere (95% N2+5% H2).

[0143] Final sintering: after ball milling for 7h again, sinter at 1270°C for 5h under the same atmosphere.

[0144] Annealing: perform precise annealing, from the peak temperature to 800°C at a rate of 6°C / min; from 800°C to 300°C at a rate of 2°C / min; and then cool with the furnace. Ba 1.95 Sr 0.05 SiO4: Eu 0.01 , Ho 0.02 The excitation spectrum of the luminescent powder measured at 500nm as the monitoring wavelength is shown in Figure 2 .

[0145] b. Core-shell structure construction (Core@mSiO2)

[0146] Coating: disperse the core luminescent powder in a solution containing ethanol, water and 0.2wt% CTAB.

[0147] Reaction: slowly add TEOS and ammonia, and stir at 45°C for 7h.

[0148] Post-treatment: after centrifugation, washing and drying, calcine in air at 580°C for 5h.

[0149] Finished product: collect the powder and vacuum dry at 60°C to obtain the product.

[0150] The adding amount and ratio of each raw material are shown in Table 1.

[0151] The preparation method of the long-acting night light ceramic glaze with interlayer chemical coupling comprises the following steps:

[0152] (1) sequentially applying a bottom layer bonding glaze layer and a core night light functional glaze layer on a ceramic substrate, and performing high-temperature one-time firing to obtain a night light glaze substrate;

[0153] The bottom layer bonding glaze layer and the core night light functional glaze layer glaze paste are respectively weighed according to the formula, deionized water (65% solid content) and 0.5wt% dispersant are added, and ball milling is performed for 24h until the fineness D90 is less than 25μm. The out-mill specific gravity is controlled at 1.50g / cm 3 .

[0154] The photochromic protective surface glaze layer paste: the powder and the organic carrier are mixed at a weight ratio of 1:1.3, and are ground by a three-roll grinder for 6 times until the fineness is less than 20μm. The organic carrier is a mixture composed of 8% ethyl cellulose, 85% terpineol and 7% dibutyl phthalate.

[0155] Glazing and sintering process

[0156] Substrate preparation: ceramic plate cleaning and drying.

[0157] Glazing 1 (bottom layer bonding glaze layer): spraying glazing, wet film thickness 0.4mm, room temperature drying for 3h.

[0158] Glazing 2 (core night light functional glaze layer): spraying glazing, wet film thickness 0.5mm, room temperature drying for 5h.

[0159] The process of high-temperature one-time firing includes: increasing the temperature from room temperature to 600℃ at a rate of 4℃ / min, then increasing the temperature to 900℃ at a rate of 2℃ / min, and finally increasing the temperature to the peak temperature at a rate of 6℃ / min and keeping for 25min; after firing, first cooling to 950℃ at a rate of 6℃ / min, and then cooling to 750℃ at a rate of 2℃ / min.

[0160] (2) applying a photochromic protective surface glaze layer on the night light glaze substrate, and performing low-temperature two-time firing to obtain the long-acting night light ceramic glaze;

[0161] Glazing 3 (photochromic protective surface glaze layer): screen printing, controlling the dry film thickness to be 40μm, and drying at 90℃ for 40min.

[0162] The process of low-temperature two-time firing includes: increasing the temperature from room temperature to 500℃ at a rate of 6℃ / min, then increasing the temperature to 700℃ at a rate of 3℃ / min, and finally increasing the temperature to the peak temperature at a rate of 9℃ / min and keeping for 10min; after firing, first cooling to 550℃ at a rate of 3℃ / min.

[0163] The peak temperature of the high-temperature first firing is 1240°C; and the peak temperature of the low-temperature second firing is 820°C.

[0164] Example 3

[0165] The core-shell composite structure long afterglow luminescent material is prepared by the following steps:

[0166] a. Core synthesis (Ba 1.95 Sr 0.05 SiO4: Eu 0.01 , Ho 0.02 )

[0167] Dosing and ball milling: the raw materials are weighed according to the stoichiometric ratio, 2wt% H3BO3 is added as a fluxing agent, anhydrous ethanol is used as a medium, and high-energy ball milling is performed for 12h.

[0168] Pre-burning: after drying, pre-burning is performed at 1150°C for 3h under a weak reducing atmosphere (95% N2+5% H2).

[0169] Final firing: after 6h of re-milling, sintering is performed at 1250°C for 4h under the same atmosphere.

[0170] Annealing: precise annealing is performed from the peak temperature to 800°C at a rate of 5°C / min, from 800°C to 300°C at a rate of 2°C / min, and then the furnace is cooled down. The Ba 1.95 Sr 0.05 SiO4: Eu 0.01 , Ho 0.02 The excitation spectrum of the luminescent powder measured at 500nm as a monitoring wavelength is shown in Figure 2 . The emission spectrum measured at 365nm as a monitoring wavelength is shown in Figure 1 .

[0171] b. Core-shell structure construction (Core@mSiO2)

[0172] Coating: the core luminescent powder is dispersed in a solution containing ethanol, water and 0.2wt% CTAB.

[0173] Reaction: TEOS and ammonia are slowly added dropwise, and the reaction is stirred at 40°C for 6h.

[0174] Post-treatment: after centrifugation, washing and drying, calcination is performed in air at 550°C for 4h.

[0175] Finished product: the powder is collected and vacuum dried at 60°C to obtain the product.

[0176] The addition amount and ratio of each raw material are shown in Table 1.

[0177] The preparation method of the long-acting luminescent ceramic glaze material with interlayer chemical coupling comprises the following steps:

[0178] (1) applying a bottom bonding glaze layer and a core luminescent functional glaze layer on a ceramic substrate in sequence, and performing high-temperature one-time firing to obtain a luminescent glaze substrate;

[0179] The bottom bonding glaze layer and the core luminescent functional glaze layer glaze paste are respectively weighed according to the formula, deionized water (solid content 60%) and 0.3wt% dispersant are added, and ball milling is performed for 20h until the fineness D90<25μm. The out-mill specific gravity is controlled at 1.45g / cm 3 .

[0180] The photochromic protective surface glaze layer paste: the powder and the organic carrier are mixed in a weight ratio of 1:1.2, and are ground by a three-roll grinder for 5 times until the fineness <20μm. The organic carrier is a mixture composed of 8% ethyl cellulose, 85% terpineol and 7% dibutyl phthalate.

[0181] Glazing and sintering process

[0182] Substrate preparation: clean and dry the ceramic plate.

[0183] Glazing 1 (bottom bonding glaze layer): spray glazing, wet film thickness 0.3mm, room temperature drying for 2h.

[0184] Glazing 2 (core luminescent functional glaze layer): spray glazing, wet film thickness 0.4mm, room temperature drying for 4h.

[0185] The process of high-temperature one-time firing includes: increasing the temperature from room temperature to 600℃ at a rate of 3℃ / min, then increasing the temperature to 900℃ at a rate of 2℃ / min, and finally increasing the temperature to the peak temperature at a rate of 5℃ / min and maintaining for 20min; after firing, first cooling to 950℃ at a rate of 5℃ / min, and then cooling to 750℃ at a rate of 2℃ / min.

[0186] (2) applying a photochromic protective surface glaze layer on the luminescent glaze substrate, and performing low-temperature two-time firing to obtain the long-acting luminescent ceramic glaze;

[0187] Glazing 3 (photochromic protective surface glaze layer): screen printing, control the dry film thickness to be 30μm, and dry at 80℃ for 30min.

[0188] The process of low-temperature two-time firing includes: increasing the temperature from room temperature to 500℃ at a rate of 5℃ / min, then increasing the temperature to 700℃ at a rate of 2℃ / min, and finally increasing the temperature to the peak temperature at a rate of 8℃ / min and maintaining for 8min; after firing, first cooling to 550℃ at a rate of 2℃ / min.

[0189] The peak temperature of the high-temperature one-time firing is 1230℃; and the peak temperature of the low-temperature two-time firing is 800℃.

[0190] Example 4

[0191] A core-shell composite structure long afterglow luminescent material preparation, comprising the following steps:

[0192] a. Core synthesis (Ba 1.95 Sr 0.05 SiO4: Eu 0.01 , Ho 0.02 )

[0193] Batching and ball milling: weigh according to the stoichiometric ratio, add 1wt% H3BO3 as flux, take anhydrous ethanol as medium, and high-energy ball mill for 14h.

[0194] Pre-burning: after drying, pre-burn at 1170℃ for 2h under weak reducing atmosphere (95% N2+5% H2).

[0195] Final burning: after ball milling for 7h again, sinter at 1270℃ for 3h under the same atmosphere.

[0196] Annealing: perform precise annealing, from peak temperature to 800℃ at a rate of 6℃ / min; from 800℃ to 300℃ at a rate of 2℃ / min; and then cool down with the furnace.

[0197] b. Core-shell structure construction (Core@mSiO2)

[0198] Coating: disperse the core powder in a solution containing ethanol, water and 0.2wt% CTAB.

[0199] Reaction: slowly add TEOS and ammonia water, and stir at 45℃ for 5h.

[0200] Post-processing: after centrifugation, washing and drying, calcine at 580℃ in air for 3h.

[0201] Finished product: collect the powder and vacuum dry at 60℃ to obtain the product.

[0202] The addition amount and ratio of each raw material are shown in Table 1.

[0203] A preparation method of long-acting noctilucent ceramic glaze with interlayer chemical coupling, comprising the following steps:

[0204] (1) sequentially apply a bottom layer bonding glaze layer and a core noctilucent functional glaze layer on a ceramic substrate, and perform high-temperature one-time firing to obtain a noctilucent glaze substrate;

[0205] Bottom layer bonding glaze layer and core noctilucent functional glaze layer glaze slurry: respectively weigh according to the formula, add deionized water (solid content 65%) and 0.5wt% dispersant, and ball mill for 24h until the fineness D90<25μm. The out-mill specific gravity is controlled at 1.50g / cm 3 .

[0206] Photochromic protective glaze layer paste: the powder and the organic carrier are mixed in a weight ratio of 1:1.3, and are ground by a three-roll grinder for 4 times until the fineness is <20 μm. The organic carrier is a mixture composed of 8% ethyl cellulose, 85% terpineol and 7% dibutyl phthalate.

[0207] Glazing and sintering process

[0208] Substrate preparation: clean and dry the ceramic plate.

[0209] Glazing 1 (bottom bonding glaze layer): spray glazing, wet film thickness 0.4 mm, dry at room temperature for 1 h.

[0210] Glazing 2 (core luminescent functional glaze layer): spray glazing, wet film thickness 0.5 mm, dry at room temperature for 3 h.

[0211] The high-temperature first sintering process includes: heating from room temperature to 600℃ at a rate of 4℃ / min, then heating to 900℃ at a rate of 2℃ / min, and finally heating to the peak temperature at a rate of 6℃ / min and keeping for 25 min; after sintering, cooling to 950℃ at a rate of 6℃ / min, and then cooling to 750℃ at a rate of 2℃ / min.

[0212] (2) applying a photochromic protective glaze layer on the luminescent glaze substrate, and obtaining the long-acting luminescent ceramic glaze through low-temperature second sintering;

[0213] Glazing 3 (photochromic protective glaze layer): screen printing, control the dry film thickness to be 40 μm, and dry at 90℃ for 20 min.

[0214] The low-temperature second sintering process includes: heating from room temperature to 500℃ at a rate of 6℃ / min, then heating to 700℃ at a rate of 3℃ / min, and finally heating to the peak temperature at a rate of 9℃ / min and keeping for 10 min; after sintering, cooling to 550℃ at a rate of 3℃ / min.

[0215] The peak temperature of the high-temperature first sintering is 1240℃, and the peak temperature of the low-temperature second sintering is 820℃.

[0216] Example 5

[0217] The preparation of the core-shell composite long-afterglow luminescent material includes the following steps:

[0218] a. core synthesis (Ba 1.95 Sr 0.05 SiO4: Eu 0.01 , Ho 0.02 )

[0219] Batching and ball milling: weigh according to the stoichiometric ratio, add 1wt% H3BO3 as fluxing agent, use anhydrous ethanol as medium, and high-energy ball mill for 10 h.

[0220] Pre-burn: After drying, pre-burn at 1130℃ for 4h under weak reducing atmosphere (95%N2+5%H2).

[0221] Final burn: After ball-milling for another 5h, sinter at 1230℃ for 5h under the same atmosphere.

[0222] Annealing: Perform precise annealing from peak temperature to 800℃ at a rate of 6℃ / min; 800℃ to 300℃ at a rate of 2℃ / min; then cool down with furnace.

[0223] b. Core@mSiO2

[0224] Coating: Disperse the core powder in a solution containing ethanol, water and 0.1wt% CTAB.

[0225] Reaction: Slowly add TEOS and ammonia water, and stir at 35℃ for 5-7h.

[0226] Post-treatment: After centrifugation, washing and drying, calcine at 520℃ in air for 5h.

[0227] Finished product: Collect the powder and vacuum dry at 60℃ to obtain the product.

[0228] The addition amount and ratio of each raw material are shown in Table 1.

[0229] The preparation method of the long-acting luminescent ceramic glaze with interlayer chemical coupling comprises the following steps:

[0230] (1) Apply a bottom bonding glaze layer and a core luminescent functional glaze layer on a ceramic substrate in sequence, and perform high-temperature one-time firing to obtain a luminescent glaze substrate;

[0231] The bottom bonding glaze layer and the core luminescent functional glaze layer are respectively weighed according to the formula, deionized water (solid content 58%) and 0.2wt% dispersant are added, and ball milling is performed for 16h until the fineness D90<25μm. The out-mill specific gravity is controlled at 1.40g / cm 3 .

[0232] The photochromic protective face glaze layer paste: the powder and the organic carrier are mixed in a weight ratio of 1:1.1-1.3, and are ground by a three-roll grinder for 4 times until the fineness is <20μm. The organic carrier is a mixture composed of 8% ethyl cellulose, 85% terpineol and 7% dibutyl phthalate.

[0233] Glazing and sintering process

[0234] Substrate preparation: clean and dry the ceramic plate.

[0235] Glazing 1 (bottom bonding glaze layer): spray glazing, wet film thickness 0.2mm, dry at room temperature for 1h.

[0236] Glazing 2 (core luminescent functional glaze layer): spray glazing, wet film thickness 0.3 mm, room temperature drying for 5 h.

[0237] The high-temperature first firing process includes: increasing the temperature from room temperature to 600℃ at a rate of 2℃ / min, then increasing the temperature to 900℃ at a rate of 1℃ / min, and finally increasing the temperature to the peak temperature at a rate of 4℃ / min and maintaining for 15 min; after firing, first cooling to 950℃ at a rate of 4℃ / min, and then cooling to 750℃ at a rate of 1℃ / min.

[0238] (2) applying a photochromic protective surface glaze layer on the luminescent glaze substrate, and obtaining the long-acting luminescent ceramic glaze through low-temperature second firing;

[0239] Glazing 3 (photochromic protective surface glaze layer): screen printing, control dry film thickness 20 μm, 90℃ drying for 40 min.

[0240] The low-temperature second firing process includes: increasing the temperature from room temperature to 500℃ at a rate of 4℃ / min, then increasing the temperature to 700℃ at a rate of 1℃ / min, and finally increasing the temperature to the peak temperature at a rate of 7℃ / min and maintaining for 10 min; after firing, first cooling to 550℃ at a rate of 1℃ / min.

[0241] The peak temperature of the high-temperature first firing is 1220℃; and the peak temperature of the low-temperature second firing is 780℃.

[0242] Comparative Example 1

[0243] The difference from Example 3 is that Nb2O5 is replaced by the same mass of Al2O3.

[0244] Comparative Example 2

[0245] The difference from Example 3 is that the phosphate glass powder is replaced by the same mass of borosilicate.

[0246] Comparative Example 3

[0247] The difference from Example 3 is that zircon is replaced by the same mass of Al2O3.

[0248] Comparative Example 4

[0249] The difference from Example 3 is that WO3 is replaced by the same mass of V2O5.

[0250] Comparative Example 5

[0251] The difference from Example 3 is that CeO2 is not added.

[0252] Comparative Example 6

[0253] The difference from Example 3 is that Ba1.95 Sr 0.05 SiO4:Eu 0.01 ,Ho 0.02 The noctilucent powder is used for glaze spraying firing.

[0254] Comparative Example 7

[0255] The difference from Example 3 is that the core-shell composite long afterglow luminescent material is replaced by long afterglow noctilucent powder SrMgAl4O8:Eu 2+ Dy 3+ .

[0256] Comparative Example 8

[0257] The difference from Example 3 is that the peak temperature of high-temperature primary sintering is set to 850-1000℃.

[0258] The peak temperature of low-temperature secondary sintering is set to 720-750℃.

[0259] Comparative Example 9

[0260] The difference from Example 3 is that after high-temperature primary sintering, room temperature natural cooling is adopted, and after low-temperature secondary sintering, room temperature natural cooling is also adopted.

[0261] The test data of Examples 1-5 are shown in Table 2.

[0262] The test data of Comparative Examples 1-9 are shown in Table 3.

[0263] Table 1: Raw material ratio table used in Examples 1-5

[0264]

[0265] Table 2: Test data of Examples 1-5

[0266]

[0267] Interlayer bonding strength test:

[0268] According to GB / T31541-2015 “Fine Ceramic Interface Bonding Strength Test Method”, the specific steps are as follows:

[0269] Sample preparation:

[0270] Ceramic matrix (50mm×50mm×5mm) + glaze layer (thickness 0.3-0.5mm) after complete sintering process.

[0271] Cut out 10mm×10mm×5mm small samples with a diamond cutting machine, ensuring the integrity of the glaze layer.

[0272] Test method:

[0273] Scratch test: Critical load (Lc) at which the glaze layer peeled off was recorded using nanoindenter (Anton Paar UNHT) with a loading rate of 50 N / min.

[0274] Tensile test: The sample was bonded to stainless steel grips using epoxy resin (Araldite 2015), 90° peel test (speed 1 mm / min), the maximum peel strength was recorded.

[0275] Medium / strong UV transmittance test: According to GB / T 2680-2021 "Building Glass - Determination of the visible and solar transmittance and related properties - Test methods":

[0276] Instrument: Double-beam spectrophotometer (bandwidth ≤ 2 nm, integrating sphere);

[0277] Wavelength: 280 nm - 400 nm (UVA + UVB), step 5 nm;

[0278] Sample: Glaze layer single-side polished, thickness 30 μm ± 2 μm, substrate is quartz plate;

[0279] Irradiation pretreatment: 500 h UVA-340 aging according to GB / T 16422.2-2022, then measure the transmittance retention rate;

[0280] Give the average value of T(365 nm), T(280-400 nm) and the difference before and after aging.

[0281] This method is consistent with the borosilicate glass UV transmittance test conditions.

[0282] Outdoor charging efficiency test: Use a solar simulator (xenon lamp, spectrum matching AM1.5G, irradiance 1000 W / m 2 ). The sample is irradiated under the simulator for 10 minutes, then quickly moved into a dark room, the initial brightness (mcd / m 2 ) is measured using a luminance meter (Konica Minolta LS-110) and the decay curve is recorded. Charging efficiency calculation: initial brightness divided by irradiation time (min), unit mcd / m 2 ·min. Sample preparation: complete glaze coating on ceramic substrate, test after firing.

[0283] Afterglow time test: GB / T 24982-2020 "Glass Surface Luminescence Performance Test Method" is used with the following supplements:

[0284] Excitation source: xenon lamp + AM1.5G filter, irradiance 1000 lx, irradiation 10 min;

[0285] Detector: luminance meter (CIE127-2007 standard visual function correction);

[0286] Ambient: 25°C, RH 50%, Dark room background ≤ 0.01 mcd m -2 ;

[0287] Determination: Record 1 min, 10 min, 60 min luminance, fit bi-exponential decay to get τ1, τ2;

[0288] Thermal history correction: The sample was tested after artificial aging at 200°C for 24h to simulate long-term heating in the outdoors.

[0289] This method has been used for long afterglow glass enamel product certification, compatible with ISO 17331:2022.

[0290] Table 3: Test data of Comparative Examples 1-9

[0291]

[0292] Note: The test method of comparative examples is consistent with examples.

[0293] From the test data in Tables 2-3, it can be seen that Example 3 performs best or close to best in all core performance indicators such as interlayer bonding strength, thermal shock resistance, response, outdoor charging efficiency, afterglow time, and weather resistance. The interlayer bonding strength and thermal shock resistance of Comparative Example 1 decrease sharply, verifying the indispensability of Nb2O5 as a key coupling agent to form a “chemical rivet” through reaction with the bottom layer ions to improve the mechanical strength of the multi-layer structure. The interlayer bonding and thermal shock resistance of Comparative Example 2 decrease, and the response slows down, proving that phosphate glass has better compatibility with the upper and lower layers and can form a more stable phosphorus-silicate transition layer. Comparative Example 3 performs worst, especially in bonding strength and thermal shock resistance, proving that Zr 4+is the core element of forming high-strength interface crystal phase. Comparative Example 4 has only a decrease of UV transmittance to 45%, and the response effect is poor, which proves that WO3 is a better photochromic functional material than V2O5 in this system. In Comparative Example 5, the medium UV transmittance and outdoor charging efficiency are significantly lower than those of Example 3, but the strong UV protection ability and long service life are comparable to those of Example 3. This proves that CeO2 significantly improves the charging efficiency in daily environment. The initial brightness, afterglow time and weather resistance of Comparative Example 6 are significantly worse than those of Example 3, which proves the great advantage of core-shell structure in improving the luminescent performance and protecting the night light powder. Comparative Example 7 proves the multifunctionality brought by special structure design. The overall performance of Comparative Example 8 declines, which proves that the specific firing system of "high-temperature first + low-temperature second" is the key process to ensure the coupling of functions and interfaces of each layer. The bonding strength and weather resistance of Comparative Example 9 are the worst, which proves that the precise annealing system is essential for releasing internal stress and obtaining stable products. Through systematic design of examples and comparative examples and comparison of data, the present application realizes the chemical coupling and response optimization between layers by introducing Nb2O5, phosphate glass, zirconite, CeO2 and other key components. The core-shell night light powder is the core to realize high performance and color adjustment; the two-step firing method and its precise temperature control are the guarantee to realize the above formula and structure design intention.

Claims

1. A long-lasting luminescent ceramic glaze with interlayer chemical coupling, characterized in that, It is a multi-layer composite structure arranged on a ceramic base, which comprises, from inside to outside, in order: a bottom bonding glaze layer sintered from first inorganic silicate raw materials; a core night light functional glaze layer sintered from second inorganic silicate raw materials, long afterglow luminescent materials and 4-6% niobium pentoxide in total mass of the core night light functional glaze layer; The photochromic protective enamel layer is formed by sintering third inorganic glass raw materials, nano tungsten trioxide, nano titanium dioxide, nano cerium oxide and CaS:Eu 2+ , Tm 3+ ​ The long afterglow luminescent material is a core-shell composite structure, the core is an alkaline earth metal silicate doped with Eu 2+ and Ho 3+ , and the shell is mesoporous silica.

2. The long-lasting luminescent ceramic glaze of claim 1, wherein, The first inorganic silicate raw materials in the bottom bonding glaze layer include, by weight percentage: feldspar 38-42%; quartz 23-27%; calcite 10-14%; zinc oxide 6-9%; kaolin 8-11%; zircon 4-6%.

3. The long-lasting luminescent ceramic glaze with interlayer chemical coupling according to claim 1, characterized in that, The second inorganic silicate raw materials are calcium-zinc borosilicate glass frit and active silicon dioxide; the raw materials of the core night light functional glaze layer include, by weight percentage: calcium-zinc borosilicate glass frit 68-72%; long afterglow luminescent materials 15-23%; active silicon dioxide 4-6%; niobium pentoxide 4-6%.

4. The long-lasting luminescent ceramic glaze of claim 1, wherein, The raw material of the photochromic protective enamel layer comprises, by weight percentage, 74-82% of phosphate glass powder, 2-4% of nano tungsten trioxide, 8-11% of nano titanium dioxide, 0.5-1.5% of nano cerium oxide, and 0.5-1.5% of CaS:Eu 2+ , Tm 3+ : 4-10%.

5. A method of preparing the long-lasting luminescent ceramic glaze chemically coupled between layers according to any one of claims 1 to 4, characterized by, The method comprises the following steps: (1) applying the bottom bonding glaze layer and the core night light functional glaze layer on the ceramic base in order, and performing high-temperature one-time firing to obtain a night light glaze base; (2) applying a photochromic protective face glaze layer on the night light glaze base, and performing low-temperature two-time firing to obtain the long-acting night light ceramic glaze; The peak temperature of the high-temperature one-time firing is 1220-1240℃. The peak temperature of the low-temperature two-time firing is 780-820℃.

6. The method of claim 5, wherein the long-lasting luminescent ceramic enamel chemically coupled between layers is prepared by the steps of: The process of the high-temperature one-time firing comprises: heating from room temperature to 600℃ at a rate of 2-4℃ / min, then heating to 900℃ at a rate of 1-2℃ / min, and finally heating to the peak temperature at a rate of 4-6℃ / min and maintaining for 15-25min; after firing, cooling to 950℃ at a rate of 4-6℃ / min, and then cooling to 750℃ at a rate of 1-2℃ / min.

7. The method for preparing long-lasting luminescent ceramic glaze with interlayer chemical coupling according to claim 5, characterized in that, The process of the low-temperature two-time firing comprises: heating from room temperature to 500℃ at a rate of 4-6℃ / min, then heating to 700℃ at a rate of 1-3℃ / min, and finally heating to the peak temperature at a rate of 7-9℃ / min and maintaining for 5-10min; after firing, cooling at a rate of 1-3℃ / min.

8. Use of the long-lasting luminescent ceramic glaze chemically coupled between layers according to any one of claims 1 to 4, characterized in that, The long-acting night light ceramic glaze is used in safety marking products for petroleum and chemical facilities, power facilities, tunnels, offshore platforms or ships.

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