CN113307496B - Luminescent glaze ceramic material and preparation method and application thereof - Google Patents
Luminescent glaze ceramic material and preparation method and application thereof Download PDFInfo
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- CN113307496B CN113307496B CN202110662204.1A CN202110662204A CN113307496B CN 113307496 B CN113307496 B CN 113307496B CN 202110662204 A CN202110662204 A CN 202110662204A CN 113307496 B CN113307496 B CN 113307496B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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Abstract
The invention provides a luminescent glaze ceramic material and a preparation method and application thereof, wherein the luminescent glaze ceramic material comprises the following components: base glaze and hairA light component; the component of the base glaze comprises B 2 O 3 、TiO 2 、TeO 2 、ZnO、Na 2 O 2 、Al 2 O 3 And Bi 2 O 5 (ii) a The luminescent component comprises Tb 4 O 7 And Eu 2 O 3 . The luminous glaze ceramic material has a luminous effect and long afterglow time, can meet more diversified customer requirements, or is suitable for occasions such as escape signs and the like; the preparation method improves the stability and the afterglow time of the product by adding the pre-sintering step.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a luminous glaze ceramic material and a preparation method and application thereof.
Background
The luminous glaze can still continuously emit light after an external light source is removed. At present, the luminescent ceramic is mainly prepared by firing luminescent glaze which takes metal sulfide or rare earth doped aluminate as a substrate at a low and medium temperature. But the environmental adaptability is poor, the use condition is harsh, and the low-temperature sintered rare earth doped silicate luminescent ceramic product meets the requirements of the industry and has larger market space for the characteristics of different luminescent glazes. The long-afterglow luminous glaze consists of luminous powder, base glaze, additive and other components. When the luminescent ceramic glaze is synthesized by a microwave method by selecting the medium-low temperature base glaze frits suitable for the silicate long afterglow luminescent color, the higher the microwave sintering temperature is, the longer the microwave heat preservation time is, the more seriously the long afterglow luminescent material is damaged by high temperature melting, and when the content of the long afterglow luminescent powder is too low, the luminescent powder density in the luminescent ceramic glaze is low, so that the luminescent performance of the luminescent ceramic glaze is poor. When the content of the long-afterglow luminescent powder is too high, the glaze surface is rough and bubbles appear, so that the quality of the luminescent ceramic glaze surface is poor.
CN112159109A discloses a long afterglow luminescent ceramic glaze synthesized by microwave method and its preparation method, which comprises (1) pulverizing blank, adding deionized water into the powder, granulating, and aging for 12 h; after the blank is dried, pressing and forming; drying and sintering the formed blank to obtain the blank. (2) Weighing frit raw materials according to a frit formula, ball-milling and uniformly mixing the frit raw materials, placing the mixture into an alumina crucible, heating the mixture to a molten state in a high-temperature muffle furnace, quickly pouring the mixture into cold water for quenching to obtain a glassy frit, and drying, crushing, ball-milling and sieving the glassy frit to obtain frit powder; (3) preparing ceramic luminescent glaze by adopting a wet ball milling process, wherein the ceramic luminescent glaze comprises the following components in parts by weight: long afterglow luminescent powder, the fused block powder obtained in the step (2) and an additive; glazing the blank body by a glaze dipping method, drying and firing the glazed blank body, and cooling along with a furnace to obtain the luminescent ceramic glaze.
CN1235936A discloses a photoluminescent glaze and a method for producing the same by using a dopeAlkaline earth metal aluminates of the earth element, e.g. SrAl 2 O 4 :Eu 2+ The photoluminescent glaze prepared by substituting sulfide such as ZnS improves the afterglow time to a certain extent, but still has the problems of short afterglow time and poor glaze stability.
CN103044082A discloses a luminescent glaze for enamel color porcelain, which comprises an enamel color porcelain basic glaze and a luminescent material protective glaze, wherein the luminescent material protective glaze is prepared by mixing a flux for the luminescent material protective glaze and a luminescent material and then re-firing, and a phosphorus compound and oxides of cerium, lanthanum, yttrium, zirconium and the like are introduced into the luminescent glaze to replace fluorite, so that CaF, PbO, Na and the like in the high-temperature color porcelain process are reduced 2 O and K 2 However, the composition has a problem that the composition is not suitable for use as a building material because of its narrow adaptability.
Therefore, it is necessary to develop a new luminescent ceramic glaze material to improve the stability and afterglow duration of the luminescent glaze material in the existing building materials.
Disclosure of Invention
In order to solve the technical problems, the invention provides a luminous glaze ceramic material and a preparation method and application thereof 4 O 7 And Eu 2 O 3 As a luminescent component, is added into the base glaze, and the components of the base glaze are adjusted, so as to obtain Tb 3+ And Eu 3+ The preparation method realizes the co-doping of the luminescent component and the B in the glaze material through the step of pre-sintering 2 O 3 、TeO 2 、Na 2 O 2 And Bi 2 O 5 So that Tb is better obtained 3+ And Eu 3+ The co-doped glaze solves the problems of poor stability and short afterglow time in the existing luminescent glaze.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a luminescent glaze ceramic material, the components of which comprise: a base glaze and a luminescent component;
the component of the base glaze comprises B 2 O 3 、TiO 2 、TeO 2 、ZnO、Na 2 O 2 、Al 2 O 3 And Bi 2 O 5 。
The luminescent component comprises Tb 4 O 7 And Eu 2 O 3 。
In the invention, Na is added to the basic glaze material simultaneously in the luminescent glaze ceramic material 2 O 2 And Bi 2 O 5 To be mixed with Tb in the luminescent component 4 O 7 And Eu 2 O 3 Interact to form Tb 3+ -Eu 3+ Co-doped luminescent glaze material, wherein Bi 2 O 5 The final glaze can be distributed with bismuthate crystal phase such as sodium bismuthate or sodium aluminum bismuthate, and not only Tb 3+ And Eu 3+ The bismuthate crystal phase has a more compact grid structure compared with the conventional silicate phase, so that the stability of the luminescent glaze is obviously improved; and adopt Tb 4 O 7 And Eu 2 O 3 Compared with the single doping, under the illumination condition, the luminescent component of (1) has the excitation of respective ions and Tb 3+ With Eu 3+ Under the condition of energy transfer, and through further component content adjustment, the luminous glaze materials with different luminous colors are obtained.
Preferably, the components of the base glaze comprise, in mass fraction:
B 2 O 3 the mass fraction of (b) is 10 to 15%, and may be, for example, 10%, 11%, 11.2%, 12%, 12.3%, 12.8%, 13%, 13.5%, 14%, or 15%, but is not limited to the above-mentioned values, and other values not shown in the above range are also applicable.
TiO 2 The mass fraction (b) of (c) is 10 to 12%, and may be, for example, 10%, 10.3%, 10.5%, 10.7%, 10.9%, 11.2%, 11.4%, 11.6%, 11.8%, or 12%, but is not limited to the examplesOther values not listed within this range are equally applicable.
TeO 2 The mass fraction of (b) is 5 to 22%, and may be, for example, 5%, 7%, 9%, 11%, 13%, 15%, 17%, 19%, 21%, 22%, or the like, but is not limited to the recited values, and other values not recited in the range are also applicable.
The mass fraction of ZnO is 12 to 25%, and may be, for example, 12%, 14%, 15%, 17%, 18%, 20%, 21%, 23%, 24%, or 25%, but is not limited to the values listed, and other values not listed in this range are also applicable.
Na 2 O 2 The mass fraction of (b) is 10 to 18%, and may be, for example, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, or the like, but is not limited to the recited values, and other values not recited in the range are also applicable.
Al 2 O 3 The mass fraction of (b) is 15 to 25%, and may be, for example, 15%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, or 25%, but is not limited to the recited values, and other values not recited in the range are also applicable.
Bi 2 O 5 The mass fraction of (b) is 5 to 15%, and may be, for example, 5%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15%, but is not limited to the recited values, and other values not recited in the range are also applicable.
According to the invention, the components of the base glaze are adjusted to the above range, and the components interact with each other, so that a field environment can be better provided for the luminescent components, and the stability and afterglow time of the luminescent glaze are improved.
Preferably, the mass ratio of the luminescent component to the base glaze is 0.08 to 0.12:1, for example, 0.08:1, 0.09:1, 0.1:1, 0.11:1, or 0.12:1, but not limited to the above-mentioned values, and other values not listed in this range are also applicable.
Preferably, Tb in the luminescent component 4 O 7 And Eu 2 O 3 The mass ratio of (A) to (B) is 1 to 3:1, and may be, for example, 1:1, 1.3:1,1.5:1, 1.7:1, 1.9:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1 or 3:1, etc., but are not limited to the recited values, and other values not recited within this range are equally applicable.
Preferably, Tb in the luminescent component 4 O 7 With Bi in the base glaze 2 O 5 The mass ratio of (b) is 0.5 to 0.8:1, and may be, for example, 0.5:1, 0.52:1, 0.53:1, 0.55:1, 0.6:1, 0.68:1, 0.7:1, 0.71:1, 0.75:1 or 0.8:1, but is not limited to the above-mentioned values, and other values not shown in the above range are also applicable.
In the invention, the mass ratio of Tb in the luminescent component to Bi in the base glaze is controlled within the range of the proportion, which is more favorable for Tb 3+ The doping in the bismuthate crystal phase ensures the luminous property and the stability of the luminous glaze.
Preferably, Eu is present in the luminescent component 2 O 3 With base glaze B 2 O 3 And Bi 2 O 5 The mass ratio of the sum is 0.1 to 0.22:1, and may be, for example, 0.1:1, 0.14:1, 0.18:1, 0.19:1, 0.20:1 or 0.22:1, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable.
In the invention, the mass ratio of Eu in the luminescent component to the sum of B and Bi in the base glaze is controlled within the proportion range, so that the content of borate and bismuthate in the product can be controlled, and Eu is more favorable for 3+ Uniformly doped into the bismuthate crystal phase instead of being distributed in the crystal lattice of the borate, thereby ensuring that Eu is ensured 3+ And Tb 3+ The luminous effect and the afterglow time of the luminous glaze are improved by the mutually matched luminous characteristics.
Preferably, B in the base glaze 2 O 3 With Na 2 O 2 The mass ratio of (b) is 0.5 to 1.5:1, and may be, for example, 0.5:1, 0.52:1, 0.54:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.2:1 or 1.5:1, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the present invention, Na is ensured 2 O 2 Mass ratio of (B) 2 O 3 So as to provide sodium element for the formation of bismuthate and effectively ensure the crystalFormation of lattice defects, promotion of Eu 3+ And Tb 3+ And (4) co-doping.
The invention finds the Eu more suitable for the Eu by comprehensively selecting each component and blending the key components 3+ And Tb 3+ The composition of the codoped basic glaze obviously improves the afterglow time and the product stability of the luminescent glaze.
In a second aspect, the present invention provides a process for the preparation of a luminescent glaze ceramic material according to the first aspect, comprising the steps of:
(1) mixed luminescent component, B 2 O 3 、TeO 2 、Na 2 O 2 And Bi 2 O 5 Sequentially carrying out first ball milling and presintering at 650-750 ℃ to obtain a first mixture;
(2) mixing the first mixture and TiO 2 ZnO and Al 2 O 3 And carrying out second ball milling and sintering in sequence to obtain the luminescent glaze ceramic material.
The preparation method of the invention is that the luminescent component and the B are firstly prepared 2 O 3 、TeO 2 、Na 2 O 2 And Bi 2 O 5 The pre-sintering is carried out at the temperature of 650-750 ℃, so that the material is in a near-molten state, and the crystal phase of the oxide begins to have defects, thereby being more beneficial to luminescent components and B 2 O 3 And Bi 2 O 5 On the other hand, Tb is made to be advanced 3+ With Eu 3+ Occupies the lattice points in the subsequent formation of borate and bismuthate, reduces the occupation of Zn and Ti on the lattice points, and obviously improves the stability of the luminescent glaze material.
The invention discovers that the temperature environment of 650-750 ℃ is very critical, can provide a near-molten state, is difficult to directly form bismuthate and borate, and is further used with TiO 2 ZnO and Al 2 O 3 Sufficient mixing provides conditions to maintain the properties of the base glaze.
Preferably, the pre-sintering time in step (1) is 2 to 4 hours, such as 2 hours, 2.3 hours, 2.5 hours, 2.7 hours, 2.9 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours or 4 hours, but not limited to the recited values, and other values not recited in the range are also applicable.
The present invention has no special limitation on the particle size range of the luminescent component of the material, and any particle size range which can be used for preparing luminescent glaze ceramic materials and is well known to those skilled in the art can be adopted.
Preferably, the time of the first ball milling is 3 to 8 hours, for example, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, or 8 hours, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the sintering in step (2) comprises temperature programmed sintering.
Preferably, the temperature rise rate of the temperature-programmed sintering is 1 to 10 ℃/min, and for example, 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, or 10 ℃/min, etc., but not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the final temperature of the temperature programmed sintering is 1400 to 1500 ℃, and may be 1400 ℃, 1412 ℃, 1423 ℃, 1434 ℃, 1445 ℃, 1456 ℃, 1467 ℃, 1478 ℃, 1489 ℃ or 1500 ℃, for example, but not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the temperature is maintained at the final temperature for 1.5 to 2.5 hours, for example, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, 2.0 hours, 2.1 hours, 2.2 hours, 2.4 hours, or 2.5 hours, but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the time of the second ball milling is 3 to 8 hours, for example, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, or 8 hours, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the preparation method comprises the following steps:
(1) mixed luminescent component, B 2 O 3 、TeO 2 、Na 2 O 2 And Bi 2 O 5 Sequentially carrying out first ball milling and presintering at 650-750 DEG CObtaining a first mixture after 2-4 hours;
(2) mixing the first mixture and TiO 2 ZnO and Al 2 O 3 And sequentially carrying out second ball milling, heating to 1400-1500 ℃ at a speed of 1-10 ℃/min, and carrying out heat preservation for 1.5-2.5 h to obtain the luminescent glaze ceramic material.
In a third aspect, the present invention provides the use of the luminescent glaze ceramic material of the first aspect in a luminescent building material or a luminescent building sign.
The luminescent glaze ceramic material provided by the invention has long afterglow time and high stability, can be suitable for building environment, and is an excellent luminescent building material or material for luminescent building signs.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the luminescent glaze ceramic material provided by the invention has a luminescent effect, has long afterglow time which is more than or equal to 12 hours, and can meet more diversified customer requirements under the optimized condition, wherein the afterglow time is more than or equal to 30 hours;
(2) according to the preparation method of the luminous glaze ceramic material, the stability and the afterglow time of the product are improved by adding the pre-sintering step;
(3) the luminescent glaze ceramic material provided by the invention has long afterglow time and high stability, and can be well applied to the fields of noctilucent marks, road building marks and the like or occasions such as escape marks and the like.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
First, an embodiment
Example 1
The embodiment provides a luminescent glaze ceramic material, which comprises the following components in parts by weight: a base glaze and a luminescent component;
the basic glaze comprises the following components in percentage by mass:
the luminescent component comprises Tb 4 O 7 And Eu 2 O 3 Tb in the luminescent component 4 O 7 And Eu 2 O 3 The mass ratio of the luminescent component to the base glaze is 2:1, and the mass ratio of the luminescent component to the base glaze is 0.09: 1.
The preparation method of the luminescent glaze ceramic material comprises the following steps:
(1) mixed luminescent component, B 2 O 3 、TeO 2 、Na 2 O 2 And Bi 2 O 5 Sequentially carrying out first ball milling for 3.5h at 250r/min and presintering for 3h at 700 ℃ to obtain a first mixture;
(2) directly mixing the first mixture and TiO 2 ZnO and Al 2 O 3 And sequentially carrying out secondary ball milling for 4h at the speed of 400r/min, heating to 1300 ℃ at the speed of 6 ℃/min, and preserving heat for 2h to obtain the luminescent glaze ceramic material.
Example 2
The embodiment provides a luminescent glaze ceramic material, which comprises the following components in parts by weight: a base glaze and a luminescent component;
the basic glaze comprises the following components in percentage by mass:
the luminescent component comprises Tb 4 O 7 And Eu 2 O 3 Tb in the luminescent component 4 O 7 And Eu 2 O 3 The mass ratio of the luminescent component to the base glaze is 2:1, and the mass ratio of the luminescent component to the base glaze is 0.12: 1.
The preparation method of the luminescent glaze ceramic material comprises the following steps:
(1) mixed luminescent component, B 2 O 3 、TeO 2 、Na 2 O 2 And Bi 2 O 5 Sequentially carrying out first ball milling for 8 hours at 200r/min and presintering for 2 hours at 750 ℃ to obtain a first mixture;
(2) mixing the first mixture and TiO 2 ZnO and Al 2 O 3 And sequentially carrying out secondary ball milling for 8h at the speed of 350r/min, heating to 1400 ℃ at the speed of 10 ℃/min, and carrying out heat preservation for 2.5h to obtain the luminescent glaze ceramic material.
Example 3
The embodiment provides a luminescent glaze ceramic material, which comprises the following components in parts by weight: a base glaze and a luminescent component;
the basic glaze comprises the following components in percentage by mass:
the luminescent component comprises Tb 4 O 7 And Eu 2 O 3 Tb in the luminescent component 4 O 7 And Eu 2 O 3 The mass ratio of the luminescent component to the base glaze is 1:1, and the mass ratio of the luminescent component to the base glaze is 0.08: 1.
The preparation method of the luminescent glaze ceramic material comprises the following steps:
(1) mixed luminescent component, B 2 O 3 、TeO 2 、Na 2 O 2 And Bi 2 O 5 Sequentially carrying out first ball milling for 3h at 300r/min and presintering for 4h at 650 ℃ to obtain a first mixture;
(2) mixing the first mixture and TiO 2 ZnO and Al 2 O 3 And sequentially carrying out second ball milling for 3h at the speed of 500r/min, heating to 1500 ℃ at the speed of 1 ℃/min, and carrying out heat preservation for 1.5h to obtain the luminescent glaze ceramic material.
Example 4
This example provides a luminescent glaze ceramic material with components that are free of Tb 4 O 7 And Eu 2 O 3 The same as in example 1 except that the mass ratio of (A) to (B) was 0.5: 1.
Example 5
This example provides a luminescent glaze ceramic material with components that are free of Tb 4 O 7 And Eu 2 O 3 The mass ratio of (A) to (B) is 5:1, and the rest is the same as that of example 1.
Example 6
This example provides a luminescent glaze ceramic material with Bi removed from the components 2 O 5 20% by mass of Al 2 O 3 The procedure was as in example 1 except that 15% was replaced.
Example 7
This example provides a luminescent glaze ceramic material with Bi removed from the components 2 O 5 The mass content of (1) was 2%, and the balance was the same as in example 1 except that 13% of ZnO was replaced.
Example 8
This example provides a luminescent glaze ceramic material having a composition except B 2 O 3 The mass content of (1) was 5%, and the balance was the same as in example 1 except that ZnO was replaced with 18%.
Example 9
This example provides a luminescent glaze ceramic material, which contains components except B 2 O 3 20% by mass of Al 2 O 3 The substitution was 20%, and the rest was the same as in example 1.
Example 10
This example provides a luminescent glaze ceramic material, which is the same as that of example 1 except that the temperature of the pre-sintering in the preparation method is 600 ℃.
Example 11
This example provides a luminescent glaze ceramic material, which is the same as that of example 1 except that the temperature of pre-sintering in the preparation method is 800 ℃.
Comparative example 1
This comparative example provides a ceramic material which is the same as in example 1 except that no luminescent component is added.
The comparative example did not give a luminescent ceramic material
Comparative example 2
This comparative example provides a ceramic material to which Eu was not added 2 O 3 Otherwise, the same procedure as in example 1 was repeated.
Comparative example 3
This comparative example provides a ceramic material to which Tb was not added 4 O 7 Otherwise, the same procedure as in example 1 was repeated.
Comparative example 4
This comparative example provides a ceramic material in which Bi is removed 2 O 5 Replacement by P 2 O 5 Otherwise, the same procedure as in example 1 was repeated.
Comparative example 5
This comparative example provides a ceramic material in which B is removed 2 O 3 Replacement by SiO 2 Otherwise, the same procedure as in example 1 was repeated.
The luminescent frits of the above examples and comparative examples were tested for luminescence at room temperature by a FL-7000 type fluorescence spectrometer manufactured by hitachi corporation, and the ceramic material was coated on a slide glass, irradiated with an artificial fluorescent lamp for 5 hours, and then placed in a dark environment to observe the continuous luminescence time, as shown in table 1.
The test results of the above examples and comparative examples are shown in table 1.
TABLE 1
In conclusion, the luminous glaze ceramic material provided by the invention has a luminous effect, has long afterglow time which is more than or equal to 12 hours, has afterglow time of more than or equal to 30 hours and high afterglow intensity under the optimal condition, can meet more diversified customer requirements, or is suitable for escape signs and other occasions.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (7)
1. A luminescent glaze ceramic material is characterized by comprising the following components: a base glaze and a luminescent component;
the component of the base glaze comprises B 2 O 3 、TiO 2 、TeO 2 、ZnO、Na 2 O 2 、Al 2 O 3 And Bi 2 O 5 ；
The luminescent component comprises Tb 4 O 7 And Eu 2 O 3 ；
The basic glaze comprises the following components in percentage by mass:
B 2 O 3 10~15%；
TiO 2 10~12%；
TeO 2 5~22%；
ZnO 12~25%；
Na 2 O 2 10~18%；
Al 2 O 3 15~25%；
Bi 2 O 5 5~15%；
in the base glaze B 2 O 3 With Na 2 O 2 The mass ratio of (A) to (B) is 0.5-1.5: 1;
the mass ratio of the luminescent component to the base glaze is 0.08-0.12: 1;
tb in the luminescent component 4 O 7 And Eu 2 O 3 The mass ratio of (A) to (B) is 1-3: 1;
tb in the luminescent component 4 O 7 With Bi in the base glaze 2 O 5 The mass ratio of (A) to (B) is 0.5-0.8: 1;
eu in the luminescent component 2 O 3 With base glaze B 2 O 3 And Bi 2 O 5 The mass ratio of the sum of the two is 0.1-0.22: 1.
2. A method for preparing a luminescent glaze ceramic material as claimed in claim 1, wherein the method comprises the following steps:
(1) mixed luminescent component, B 2 O 3 、TeO 2 、Na 2 O 2 And Bi 2 O 5 Sequentially carrying out first ball milling and presintering at 650-750 ℃ to obtain a first mixture;
(2) mixing the first mixture and TiO 2 ZnO and Al 2 O 3 And carrying out second ball milling and sintering in sequence to obtain the luminescent glaze ceramic material.
3. The preparation method according to claim 2, wherein the pre-sintering time in the step (1) is 2-4 h.
4. The method according to claim 2, wherein the sintering in step (2) comprises temperature-programmed sintering.
5. The method according to claim 4, wherein the temperature-programmed sintering is performed at a temperature-raising rate of 1 to 10 ℃/min.
6. The method according to claim 4, wherein the final temperature of the temperature programmed sintering is 1400 to 1500 ℃.
7. Use of a luminescent glaze ceramic material as claimed in claim 1, characterized in that it is used in luminescent building materials or luminescent building signs.
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