CN112010679A - Co-firing method-based luminescent ceramic tile preparation process and luminescent ceramic tile prepared by same - Google Patents
Co-firing method-based luminescent ceramic tile preparation process and luminescent ceramic tile prepared by same Download PDFInfo
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- CN112010679A CN112010679A CN202011175208.9A CN202011175208A CN112010679A CN 112010679 A CN112010679 A CN 112010679A CN 202011175208 A CN202011175208 A CN 202011175208A CN 112010679 A CN112010679 A CN 112010679A
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- C04B33/00—Clay-wares
- C04B33/32—Burning methods
- C04B33/34—Burning methods combined with glazing
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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Abstract
The invention relates to the technical field of ceramics, and discloses a luminous ceramic tile based on a co-firing preparation process and a preparation process thereof. The method comprises the steps of pre-sintering the light-emitting particles and preparing a finished product: the pre-sintering step of the light-emitting particles comprises the following steps: s1) preparing luminescent slurry; s2) placing the luminescent slurry into an electric furnace, and pre-burning and removing impurities at the temperature of 600-700 ℃ to prepare luminescent particles; the preparation steps of the finished product comprise: p1) spreading a first viscous material on the surface of the blank to form a lower viscous layer on the blank; p2) applying the luminescent particles to form a luminescent layer on the green body; p3) applying transparent glaze to form a transparent glaze layer on the blank; p4) placing the blank into a kiln to be sintered at 1100-1250 ℃ to prepare the luminescent ceramic tile. The luminescent layer can avoid the erosion and damage of liquid phase in the transparent glaze to luminescent powder particles in a fired molten state, and the prepared ceramic product has high luminous brightness and long luminous service life.
Description
Technical Field
The invention relates to the technical field of ceramics, and discloses a co-firing method-based luminescent ceramic tile preparation process and a luminescent ceramic tile prepared by the same.
Background
With the continuous improvement of living standard, people have higher and higher requirements on the building ceramics, and the practicability, the decoration and the functionality of the building ceramics are more and more emphasized. The luminous ceramic tile is characterized in that afterglow luminous powder is introduced into the ceramic, so that the ceramic has the characteristic of continuous luminescence under the dark condition after absorbing external energy.
The luminous ceramic tile can be widely applied to various public places and can be used as a light source or guide under the condition of power failure or emergency.
In the luminescent ceramic tile in the prior art, luminescent powder with luminescent efficacy sintered at high temperature is added into glaze during batching, and then is sintered together with a glaze layer at high temperature, and flux in raw materials erodes luminescent powder particles in a molten state of sintering together with the glaze layer; the luminescent powder is corroded by high-temperature sintering for the second time, the luminescent performance is reduced, the original equivalent luminescent efficacy is not achieved, the afterglow time is short, and the luminescent service life of the prepared product is short.
In addition, the synthesis temperature of the luminescent powder is generally above 1300 ℃, so that the luminescent powder has high fire resistance, is not easy to be melted in a glaze layer, and causes uneven glaze surface.
Disclosure of Invention
The invention provides a co-firing method-based luminescent ceramic tile preparation process and a luminescent ceramic tile prepared by the same.
To achieve the purpose, the invention adopts the following technical scheme
A luminescent ceramic tile preparation process based on a co-firing method comprises a luminescent particle pre-firing step and a finished product preparation step:
the pre-sintering step of the light-emitting particles comprises the following steps:
s1) weighing carbonate, a first oxide, a second oxide and a fluxing agent respectively according to the proportion, adding alcohol, grinding and mixing uniformly to obtain luminous slurry;
s2) placing the luminescent slurry into an electric furnace, and pre-burning and removing impurities at the temperature of 600-700 ℃ to prepare luminescent particles;
the preparation steps of the finished product comprise:
p1) spreading a first viscous material on the surface of the blank to form a lower viscous layer on the blank;
p2) distributing the luminescent particles on the surface of the lower adhesive layer to form a luminescent layer on the green body;
p3) applying transparent glaze on the surface of the luminescent layer to form a transparent glaze layer on the green body;
p4) placing the blank into a kiln to be sintered at 1100-1250 ℃ to prepare the luminescent ceramic tile;
the carbonate, the first oxide, the second oxide and the flux are activated to be a light-emitting material by solid-phase sintering at 1100 ℃ or higher.
Preferably, in step S1), the weight percentages of the carbonate and the first oxide are 92-96wt% and 4-8wt%, respectively; defining the carbonate and the first oxide as luminescent raw material A;
the weight ratio of the luminescent raw material A to the second oxide is 1: 1-1.5;
the content of the fluxing agent is 3-6wt% of the sum of the weight of the luminescent raw material A and the weight of the second oxide.
Optionally, in step S1), the carbonate is one of barium carbonate, lithium carbonate, strontium carbonate, and calcium carbonate;
the first oxide is one of dysprosium oxide, europium oxide and terbium oxide;
the second oxide is at least one of aluminum oxide, silicon oxide and magnesium oxide;
the fluxing agent comprises boric acid and/or a fluoroacid.
Specifically, in step S1), the purities of the carbonate, the first oxide, the second oxide and the flux are all analytically pure Ar grade; in step S2), the firing time is 1 to 3 hours.
Specifically, the particle size of the luminescent particles prepared in the luminescent particle pre-sintering step is 80-325 meshes.
Optionally, the step of preparing the finished product further comprises, between step P3) and step P4):
p31) spraying a second viscous material on the surface of the transparent glaze layer to form an upper adhesive layer on the green body.
Optionally, in step P1), the green body is a biscuit, an unfired green brick, or a green brick with a score grinder effect; the first viscous material is one of methyl paste, stamp-pad ink, ceramic dry particle glue and dextrin;
in step P2), the luminescent particles are applied at a thickness of 0.5 to 3.0 mm;
in the step P3), the transparent glaze is one of a transparent fritted glaze, a transparent dry-grained glaze and a transparent green glaze.
Optionally, in step P31), the second viscous material is one of methyl paste, stamp-pad ink, ceramic dry-grain glue and dextrin;
the cloth applying method in the finished product preparation step is one of screen printing, roller cloth and digital cloth.
Optionally, the step P4) further includes performing surface treatment on the fired luminescent ceramic tile, where the surface treatment includes full polishing, half polishing, soft polishing, and ultra-clean polishing.
Furthermore, the invention also provides a luminescent ceramic tile which is prepared by the preparation process of the luminescent ceramic tile based on the co-firing method.
The invention has the beneficial effects that: the luminescent ceramic tile preparation process based on the co-firing method comprises the steps of preparing the non-activated luminescent particles through solid-phase sintering at 600-700 ℃, and then firing the luminescent particles and the transparent glaze into the luminescent ceramic tile at the firing temperature of 1100-1250 ℃, wherein the prepared luminescent ceramic tile comprises a luminescent layer with a luminescent effect and a transparent glaze layer.
The luminescent particles contained in the luminescent layer are not contained in the glaze material of the transparent glaze layer, so that the particle erosion and damage of the flux in the transparent glaze to the luminescent powder in a sintered molten state can be avoided, and the luminescent ceramic tile is sintered once at a high temperature of more than 1100 ℃, so that the loss of luminescent efficacy is less, the luminescent efficiency is high, the prepared luminescent ceramic tile based on the co-firing preparation process has high luminescent brightness, longer luminescent life and longer afterglow time.
The surface of the transparent glaze layer covered on the luminous layer is smooth and flat, so that the luminous stereoscopic impression of the luminous ceramic tile based on the co-firing preparation process is further improved, the luminous ceramic tile is more glittering and translucent, the luminous layer can be protected from being damaged by friction, the durability of the luminous performance of the luminous ceramic tile based on the co-firing preparation process can be further improved, and the service life of the luminous ceramic tile is further prolonged.
The invention solves the technical problems of low luminous efficiency, short afterglow time and short luminous life of the prepared product of the luminous ceramic tile in the prior art.
Meanwhile, the technical problem that the surface of a glaze layer containing luminescent powder is not easy to be melted flat, so that the glaze surface is uneven is solved.
Detailed Description
The technical solution of the present invention is further described below in specific embodiments.
A luminescent ceramic tile preparation process based on a co-firing method comprises a luminescent particle pre-firing step and a finished product preparation step:
the pre-sintering step of the light-emitting particles comprises the following steps:
s1) weighing carbonate, a first oxide, a second oxide and a fluxing agent respectively according to the proportion, adding alcohol, grinding and mixing uniformly to obtain luminous slurry;
s2) placing the luminescent slurry into an electric furnace, and pre-burning and removing impurities at the temperature of 600-700 ℃ to prepare luminescent particles;
the preparation steps of the finished product comprise:
p1) spreading a first viscous material on the surface of the blank to form a lower viscous layer on the blank;
p2) distributing the luminescent particles on the surface of the lower adhesive layer to form a luminescent layer on the green body;
p3) applying transparent glaze on the surface of the luminescent layer to form a transparent glaze layer on the green body;
p4) placing the blank into a kiln to be sintered at 1100-1250 ℃ to prepare the luminescent ceramic tile;
the carbonate, the first oxide, the second oxide and the flux are activated to be a light-emitting material by solid-phase sintering at 1100 ℃ or higher.
In the luminescent ceramic tile in the prior art, luminescent powder with luminescent efficacy sintered at high temperature is added into glaze during batching, and then is sintered together with a glaze layer at high temperature, and flux in raw materials erodes luminescent powder particles in a molten state of sintering together with the glaze layer; the luminescent powder is corroded by high-temperature sintering for the second time, the luminescent performance is reduced, the original equivalent luminescent efficacy is not achieved, the afterglow time is short, and the luminescent service life of the prepared product is short.
According to the preparation process of the luminescent ceramic tile based on the co-firing method, luminescent particles without luminescent efficacy activated are prepared by removing impurities at 600-1250 ℃, and then solid-phase sintering is carried out at 1100-1250 ℃ to activate the luminescent efficacy, and the applied transparent glaze layer containing the transparent glaze is fired at the firing temperature of 1100-1250 ℃, so that the luminescent ceramic tile comprising the luminescent layer with the luminescent efficacy and the transparent glaze layer is prepared through the co-firing process.
The alcohol and the water removed during the baking of the boric acid can be removed through pre-burning, the particle size distribution of the formed luminescent particles is more concentrated, and the agglomeration phenomenon can not occur.
The luminescent particles contained in the luminescent layer are not contained in the transparent glaze, so that the particle erosion and damage of a flux in the transparent glaze to luminescent powder in a sintered molten state can be avoided, the luminescent ceramic tile is fired only once at a high temperature of more than 1100 ℃, the loss of luminescent efficacy is less, the luminescent efficiency is high, the luminescent ceramic tile prepared is high in luminescent brightness, and has longer luminescent life and longer afterglow time.
The surface of the transparent glaze layer covering the luminous layer is smooth and flat, the luminous stereoscopic impression of the prepared luminous ceramic tile can be further improved, the luminous ceramic tile is more glittering and translucent, the luminous layer can be protected from being damaged by friction, the durability of the luminous performance of the luminous ceramic tile can be further improved, and the service life of the luminous ceramic tile can be further prolonged.
Preferably, it is possible that, in step S1), the weight percentages of the carbonate and the first oxide are respectively 92-96wt% and 4-8 wt%; defining the carbonate and the first oxide as luminescent raw material A;
the weight ratio of the luminescent raw material A to the second oxide is 1: 1-1.5;
the content of the fluxing agent is 3-6wt% of the sum of the weight of the luminescent raw material A and the weight of the second oxide.
Different luminescent raw materials can be prepared by adopting carbonate and the first oxide with different components, and fluorescent luminescent effects with different colors or different color depths can be obtained after firing.
Specifically, in step S1),
the carbonate is one of barium carbonate, lithium carbonate, strontium carbonate and calcium carbonate;
the first oxide is one of dysprosium oxide, europium oxide and terbium oxide;
the second oxide is at least one of aluminum oxide, silicon oxide and magnesium oxide;
the fluxing agent comprises boric acid and/or a fluoroacid.
The alcohol is a grinding medium, and the mixing uniformity of the carbonate, the first oxide, the second oxide and the fluxing agent can be improved.
Specifically, in step S1), the purities of the carbonate, the first oxide, the second oxide, and the flux are all analytically pure Ar grade; in step S2), the firing time is 1 to 3 hours.
The purities of the carbonate, the first oxide, the second oxide and the fluxing agent are analytically pure Ar grades, so that the purity of the prepared luminescent particles can be guaranteed, and the damage of impurities to the luminescent powder when the luminescent performance is activated can be avoided.
Preferably, the particle size of the luminescent particles prepared in the luminescent particle pre-firing step is 80 to 325 mesh.
The luminescent particle is prepared by sintering the carbonate, the first oxide, the second oxide and a fluxing agent in powder form to form the luminescent particle with the particle size distribution of 80-325 meshes.
Optionally, the step of preparing the finished product further comprises, between step P3) and step P4):
p31) spraying a second viscous material on the surface of the transparent glaze layer to form an upper adhesive layer on the green body.
The luminescent particles are distributed on the viscous lower adhesive layer, and the transparent glaze is covered on the luminescent particles, so that the luminescent particles are protected in the firing process, and the phenomenon that the luminescent particles which do not form a liquid phase are stripped and fall off in the firing process, so that the prepared luminescent ceramic tile loses the luminescent efficacy is avoided.
Step P31) of spraying a second viscous material on the surface of the transparent glaze layer to fix the transparent glaze better, especially when the transparent glaze layer is selected from transparent dry glaze, and further fix the luminescent particles.
According to the technical scheme of the luminescent ceramic tile in the prior art, luminescent powder is adopted and mixed with frit of transparent glaze or glaze powder for sintering, the luminescent powder is wrapped by raw materials of overglaze, and the luminescent powder is melted in the sintering process to form a solid solution, so that the luminescent powder is corroded, and the luminescent performance of the luminescent ceramic tile is influenced.
The luminescent particles adopted by the invention are luminescent particle crystals with inactivated luminescent effect formed by pre-burning and are respectively distributed with the transparent glaze, so that the phenomenon of melting erosion cannot be generated, and the prepared ceramic product has good luminescent efficiency and high brightness.
Preferably, in step P1), the green body is a biscuit tile, an unfired green tile or a green tile with a score mill effect; the first viscous material is one of methyl paste, stamp-pad ink, ceramic dry particle glue and dextrin;
in step P2), the luminescent particles are applied at a thickness of 0.5 to 3.0 mm;
in the step P3), the transparent glaze is one of a transparent fritted glaze, a transparent dry-grained glaze and a transparent green glaze.
The luminous particles are distributed with the thickness of 0.5-3.0mm, and the luminous layer with the thickness of 0.2-1.5mm is formed after sintering, so that the luminous particle has good luminous efficiency.
If the thickness of the cloth is less than 0.5mm, the thickness of the formed luminescent layer is too thin, and the luminescent brightness is insufficient; if the thickness of the cloth is more than 3.0mm, the bonding force between the overglaze on the luminous layer and the bottom green brick is weakened, and the overglaze layer is easy to peel and loosen.
Optionally, in step P31), the second viscous material is one of methyl paste, stamp-pad ink, ceramic dry-grain glue and dextrin;
the cloth applying method in the finished product preparation step is one of screen printing, roller cloth and digital cloth.
The co-firing preparation process of the luminous ceramic tile has a good application range, the lower adhesive layer and the upper adhesive layer can be made of various conventional materials only by being suitable for the same firing temperature range, and the conventional transparent glaze can be transparent frits, transparent dry particles and/or transparent glaze powder.
Preferably, the step P4) further includes performing surface treatment on the fired luminescent ceramic tile, wherein the surface treatment includes full polishing, half polishing, soft polishing and ultra-clean polishing.
The surface treatment can be carried out on the luminous ceramic tile after firing according to the requirement, and the surface treatment mode comprises but is not limited to treatment processes of full polishing, half polishing, soft polishing, super-clean polishing and the like.
Therefore, the co-firing preparation process of the luminescent ceramic tile has strong universality, and the prepared luminescent ceramic tile can be suitable for different use places and has a good application range.
The invention also provides a luminescent ceramic tile which is prepared by the preparation process of the luminescent ceramic tile based on the co-firing method.
According to the co-firing preparation process of the luminescent ceramic tile, luminescent particles contained in raw materials are luminescent particles with an inactivated luminescent effect and are prepared by removing impurities at 600-700 ℃; and then solid-phase sintering is carried out at 1100-1250 ℃ to activate the luminous efficacy, and the applied transparent glaze layer containing the transparent glaze is also sintered together at the sintering temperature of 1100-1250 ℃, so that the luminous ceramic tile comprising the luminous layer with the luminous efficacy and the transparent glaze layer is prepared through the co-sintering process.
The prepared luminescent ceramic tile has high luminescent brightness and longer luminescent life.
Examples and comparative examples
1. A luminescent ceramic tile preparation process based on a co-firing method comprises a luminescent particle pre-firing step and a finished product preparation step:
the pre-sintering step of the light-emitting particles comprises the following steps:
s1) weighing carbonate, a first oxide, a second oxide and a fluxing agent respectively according to the proportion, adding alcohol, grinding and mixing uniformly to obtain luminous slurry;
s2) placing the luminescent slurry into an electric furnace, and pre-burning and removing impurities at the temperature of 600-700 ℃ to prepare luminescent particles;
the preparation steps of the finished product comprise:
p1) spreading a first viscous material on the surface of the blank to form a lower viscous layer on the blank;
p2) distributing the luminescent particles on the surface of the lower adhesive layer to form a luminescent layer on the green body;
p3) applying transparent glaze on the surface of the luminescent layer to form a transparent glaze layer on the green body;
p4) placing the blank into a kiln to be sintered at 1100-1250 ℃ to prepare the luminescent ceramic tile;
the carbonate, the first oxide, the second oxide and the flux are activated to be a light-emitting material by solid-phase sintering at 1100 ℃ or higher.
In step S1), the weight percentages of the carbonate and the first oxide are 92-96wt% and 4-8wt%, respectively; defining the carbonate and the first oxide as luminescent raw material A;
the weight ratio of the luminescent raw material A to the second oxide is 1: 1-1.5;
the content of the fluxing agent is 3-6wt% of the sum of the weight of the luminescent raw material A and the weight of the second oxide.
In step S1), the carbonate is one of barium carbonate, lithium carbonate, strontium carbonate, and calcium carbonate;
the first oxide is one of dysprosium oxide, europium oxide and terbium oxide;
the second oxide is at least one of aluminum oxide, silicon oxide and magnesium oxide;
the fluxing agent comprises boric acid and/or a fluoroacid.
In step S1), the purity of the carbonate, the first oxide, the second oxide, and the flux are all analytically pure Ar grade; in step S2), the firing time is 1 to 3 hours.
The particle size of the luminescent particles prepared in the luminescent particle pre-sintering step is 80-325 meshes.
The finished product preparation step further comprises, between step P3) and step P4):
p31) spraying a second viscous material on the surface of the transparent glaze layer to form an upper adhesive layer on the green body.
In step P1), the green body is a biscuit, an unfired green brick, or a green brick with a score grinder effect; the first viscous material is one of methyl paste, stamp-pad ink, ceramic dry particle glue and dextrin;
in step P2), the luminescent particles are applied at a thickness of 0.5 to 3.0 mm;
in the step P3), the transparent glaze is one of a transparent fritted glaze, a transparent dry-grained glaze and a transparent green glaze.
In the step P31), the second viscous material is one of methyl paste, stamp-pad ink, ceramic dry-particle glue and dextrin;
the cloth applying method in the finished product preparation step is one of screen printing, roller cloth and digital cloth.
The step P4) further comprises the step of carrying out surface treatment on the fired luminescent ceramic tile, wherein the surface treatment comprises full polishing, half polishing, soft polishing and super-clean polishing.
3. Each of the examples and comparative examples is a luminescent ceramic tile produced according to the co-firing method-based luminescent ceramic tile production process described above.
4. The contents and ratios of the specific raw material components and the parameters in each example are shown in Table 1, and the contents and ratios of the specific raw material components and the parameters in each ratio are shown in Table 2.
5. Checking whether the appearance effect of the luminescent ceramic tile prepared by each example and each comparative example is qualified or not, and the Mohs hardness, and comparing the luminescent effect and the brightness of each example and each comparative example; the test results of the examples and the substrate are shown in Table 1, and the test results of the comparative examples are shown in Table 2.
The following analysis of the conditions and test results according to the above respective examples and comparative examples
1. The detection results of the examples 1 to 4 are analyzed, so that the luminous ceramic tiles prepared in the examples 1 to 4 are transparent and smooth in appearance, have good luminous brightness and different colors, have the Mohs hardness of HM5, and are qualified in detection conclusion; therefore, the co-firing preparation process of the luminescent ceramic tile is effective, the prepared luminescent ceramic tile has better brightness and effect, and compared with the luminescent ceramic tile in the prior art, the luminescent ceramic tile has better over-brightness and surface smoothness, and is wear-resistant and long in service life.
2. Comparative examples 1 and 2 were analyzed in comparison with example 3, the difference between comparative examples 1 and 2 being: the positions of the luminous particles are different; the luminescent particles of the comparative examples 1 and 2 are respectively mixed in the transparent glaze and the first viscous material of the lower viscous layer for application, so that the luminescent particles of the comparative example 1 are melted and eroded by the raw materials in the glaze, the surface is uneven due to the exposure of the luminescent particles, the luminescent brightness of the luminescent ceramic tile of the comparative example 1 is low, and the detection conclusion is unqualified; the luminescent particles of the comparative example 2 are doped and dispersed by the first viscous substance in the lower adhesive layer, the purity and solid-phase sintering of the luminescent material of the comparative example 2 are influenced, the luminescent efficiency is obviously reduced, and the detection conclusion is unqualified; therefore, the luminous particles are distributed between the transparent glaze and the lower adhesive layer, and the luminous efficiency of the luminous particles is not affected.
3. Comparative examples 3 and 4 were analyzed in comparison with example 3, the differences between comparative examples 3 and 4 being: the luminescent particles of comparative examples 3 and 4 were applied at different thicknesses of 0.3mm and 3.5mm, respectively; out of the range of 0.5-3.0 mm; the luminescent particles distributed in the comparative example 3 are too few and insufficient in thickness, so that the luminescent brightness of the comparative example 3 is very low, the performance requirement of the luminescent brightness cannot be met, and the detection conclusion of the comparative example 3 is unqualified; the luminous particles of the comparative example 4 are distributed in too high thickness, so that the overglaze of the fired luminous ceramic tile of the comparative example 4 is stripped and loosened, and the detection conclusion of the comparative example 4 is unqualified; therefore, the thickness of the luminescent particles is preferably in the range of 0.5-3.0 mm.
4. Comparative examples 5 and 6 were analyzed in comparison with example 3, and comparative examples 5 and 6 differ in that: the firing temperatures in step P4) of comparative examples 5 and 6 were different, 1050 ℃ and 1320 ℃, respectively; the firing temperature in step P4) of comparative example 5 is lower than 1100 ℃, resulting in the unrooking of the glaze of comparative example 5, and the transparency and the light emission luminance not satisfying the use requirements; the firing temperature in step P4) of comparative example 6 exceeds 1300 ℃, causing the transparent glaze of comparative example 6 to melt too much and flow at the temperature of 1300 ℃, resulting in the glaze of the luminescent ceramic tile of comparative example 6 showing an open glaze bottom, and causing the luminescent particles to melt and erode from the raw material of the glaze layer because the temperature exceeds 1300 ℃, resulting in the reduction of the luminescent brightness of comparative example 6; the detection result of the comparative example 6 is unqualified; therefore, it is preferable that the firing temperature in step P4) is set to a value in the range of 1100-1250 ℃.
In summary, in the luminescent ceramic tile prepared based on the co-firing preparation process, the luminescent particles with the inactivated luminescent efficacy contained in the raw materials are prepared by removing impurities at the temperature of 600-1250 ℃, and then are subjected to solid-phase sintering at the temperature of 1100-1250 ℃ to activate the luminescent efficacy, and the applied transparent glaze layer containing the transparent glaze is also sintered at the sintering temperature of 1100-1250 ℃, so that the luminescent ceramic tile comprising the luminescent layer with the luminescent efficacy and the transparent glaze layer is prepared through the co-firing process.
The luminescent particles contained in the luminescent layer are not contained in the transparent glaze, so that the particle erosion and damage of a flux in the transparent glaze to luminescent powder in a fired molten state can be avoided, the luminescent ceramic tile is fired only once at a high temperature of more than 1100 ℃, the loss of luminescent efficacy is less, the luminescent efficiency is high, the prepared luminescent ceramic tile based on the co-firing preparation process has high luminescent brightness, better hardness, wear resistance and prolonged service life.
The surface of the transparent glaze layer covered on the luminous layer is smooth and flat, so that the luminous stereoscopic impression of the luminous ceramic tile based on the co-firing preparation process is further improved, the luminous ceramic tile is more glittering and translucent, the luminous layer can be protected from being damaged by friction, the durability of the luminous performance of the luminous ceramic tile based on the co-firing preparation process can be further improved, and the service life of the luminous ceramic tile is further prolonged.
The luminescent particles adopt the first oxides with different components, and after the first oxides, the carbonate and the second oxides are prepared and fired, fluorescent luminescent effects with different colors and different color depths can be obtained.
The luminescent particles are pre-sintered to form crystals of the non-activated luminescent particles, and the crystals and the transparent glaze are respectively applied, so that the phenomenon of melt erosion is avoided, and the prepared ceramic product has good luminous efficiency and high brightness.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A luminescent ceramic tile preparation process based on a co-firing method is characterized by comprising a luminescent particle pre-firing step and a finished product preparation step:
the pre-sintering step of the light-emitting particles comprises the following steps:
s1) weighing carbonate, a first oxide, a second oxide and a fluxing agent respectively according to the proportion, adding alcohol, grinding and mixing uniformly to obtain luminous slurry;
s2) placing the luminescent slurry into an electric furnace, and pre-burning and removing impurities at the temperature of 600-700 ℃ to prepare luminescent particles;
the preparation steps of the finished product comprise:
p1) spreading a first viscous material on the surface of the blank to form a lower viscous layer on the blank;
p2) distributing the luminescent particles on the surface of the lower adhesive layer to form a luminescent layer on the green body;
p3) applying transparent glaze on the surface of the luminescent layer to form a transparent glaze layer on the green body;
p4) placing the blank into a kiln to be sintered at 1100-1250 ℃ to prepare the luminescent ceramic tile;
the carbonate, the first oxide, the second oxide and the flux are activated to be a light-emitting material by solid-phase sintering at 1100 ℃ or higher.
2. The co-firing method-based luminescent ceramic tile preparation process of claim 1, wherein in step S1), the weight percentages of the carbonate and the first oxide are 92-96wt% and 4-8wt%, respectively; defining the carbonate and the first oxide as luminescent raw material A;
the weight ratio of the luminescent raw material A to the second oxide is 1: 1-1.5;
the content of the fluxing agent is 3-6wt% of the sum of the weight of the luminescent raw material A and the weight of the second oxide.
3. The co-firing method-based luminescent ceramic tile preparation process of claim 1, wherein in step S1), the carbonate is one of barium carbonate, lithium carbonate, strontium carbonate and calcium carbonate;
the first oxide is one of dysprosium oxide, europium oxide and terbium oxide;
the second oxide is at least one of aluminum oxide, silicon oxide and magnesium oxide;
the fluxing agent comprises boric acid and/or a fluoroacid.
4. The co-firing method-based luminescent ceramic tile production process of claim 1, wherein in step S1), the purity of the carbonate, the first oxide, the second oxide and the flux are all analytically pure Ar grade; in step S2), the firing time is 1 to 3 hours.
5. The co-firing method-based luminescent ceramic tile production process of claim 1, wherein the luminescent particles obtained from the luminescent particle pre-firing step have a particle size of 80-325 mesh.
6. The co-firing method-based luminescent ceramic tile production process of claim 1,
the finished product preparation step further comprises, between step P3) and step P4):
p31) spraying a second viscous material on the surface of the transparent glaze layer to form an upper adhesive layer on the green body.
7. The process for preparing a luminescent ceramic tile based on the co-firing method as claimed in claim 1, wherein in step P1), the green body is a biscuit, an unfired green brick, or a green brick with a score-grinding effect; the first viscous material is one of methyl paste, stamp-pad ink, ceramic dry particle glue and dextrin;
in step P2), the luminescent particles are applied at a thickness of 0.5 to 3.0 mm;
in the step P3), the transparent glaze is one of a transparent fritted glaze, a transparent dry-grained glaze and a transparent green glaze.
8. The co-firing method-based luminescent ceramic tile production process of claim 6,
in the step P31), the second viscous material is one of methyl paste, stamp-pad ink, ceramic dry-particle glue and dextrin;
the cloth applying method in the finished product preparation step is one of screen printing, roller cloth and digital cloth.
9. The co-firing method-based luminescent ceramic tile production process as claimed in claim 1, wherein the step P4) further comprises performing surface treatment on the fired luminescent ceramic tile, wherein the surface treatment comprises full polishing, half polishing, soft polishing and ultra-clean polishing.
10. A luminescent ceramic tile, characterized by being produced according to the co-firing method-based luminescent ceramic tile production process of any one of claims 1-9.
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| CN113087503A (en) * | 2021-04-02 | 2021-07-09 | 佛山市东鹏陶瓷有限公司 | Once-fired luminescent ceramic tile and preparation method thereof |
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