CN111518550A - Functional filler with gelling and long-afterglow luminescent characteristics and preparation method and application thereof - Google Patents
Functional filler with gelling and long-afterglow luminescent characteristics and preparation method and application thereof Download PDFInfo
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- 239000012767 functional filler Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 66
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000005084 Strontium aluminate Substances 0.000 claims abstract description 15
- VAWSWDPVUFTPQO-UHFFFAOYSA-N calcium strontium Chemical compound [Ca].[Sr] VAWSWDPVUFTPQO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims description 42
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 40
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 40
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 25
- 150000002910 rare earth metals Chemical class 0.000 claims description 24
- 239000012190 activator Substances 0.000 claims description 23
- 238000000227 grinding Methods 0.000 claims description 22
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 14
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 13
- 238000004020 luminiscence type Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- 150000004683 dihydrates Chemical class 0.000 claims description 9
- 229910052602 gypsum Inorganic materials 0.000 claims description 9
- 239000010440 gypsum Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000001879 gelation Methods 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000005054 agglomeration Methods 0.000 claims description 6
- 230000002776 aggregation Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910003669 SrAl2O4 Inorganic materials 0.000 claims description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 2
- 229910001650 dmitryivanovite Inorganic materials 0.000 claims description 2
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001707 krotite Inorganic materials 0.000 claims description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 37
- -1 rare earth ion Chemical class 0.000 abstract description 9
- 150000004645 aluminates Chemical class 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 6
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 abstract description 4
- 230000036571 hydration Effects 0.000 abstract description 3
- 238000006703 hydration reaction Methods 0.000 abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- 239000000945 filler Substances 0.000 description 23
- 229920002635 polyurethane Polymers 0.000 description 19
- 239000004814 polyurethane Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 description 11
- 239000011707 mineral Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 238000007580 dry-mixing Methods 0.000 description 8
- 238000003746 solid phase reaction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
- C09K11/641—Chalcogenides
- C09K11/643—Chalcogenides with alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7792—Aluminates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Abstract
The invention relates to the technical field of fluorescent luminescent material preparation, in particular to a functional filler with gelling and long-afterglow luminescent characteristics, and a preparation method and application thereof. The functional filler is a rare earth ion doped excited alkaline earth aluminate luminescent material, and compared with other fluorescent materials, the solid-phase synthesis method has the advantages of high fluorescence intensity, long afterglow time, stable chemical property and good weather resistance. Meanwhile, the luminescent material is endowed with new gelling characteristics, the defect that the traditional aluminate fluorescent material is easy to absorb moisture and lose fluorescence performance is overcome, because the strontium calcium sulphoaluminate phase has the characteristic of being very easy to hydrate, the moisture entering the material is consumed, and the hydration products of the strontium calcium sulphoaluminate phase are alumina gel, strontium sulfate and the like and can wrap the surface of the material to prevent the further contact between the moisture and the strontium aluminate. Meanwhile, when products such as coatings are prepared, the excellent gel property can effectively enhance the mechanical property of the products.
Description
Technical Field
The invention relates to the technical field of fluorescent luminescent material preparation, in particular to a functional filler with gelling and long-afterglow luminescent characteristics, and a preparation method and application thereof.
Background
The information disclosed in this background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
The existing fluorescent materials are divided into organic fluorescent materials and inorganic fluorescent materials. The organic fluorescent material has the limitations of complex preparation process, difficult processing, easy quenching, weak fluorescence and the like. The inorganic fluorescent material is represented by rare earth ion doped excited alkaline earth aluminate luminescent material, which has excellent fluorescence performance, but is easy to deliquesce, resulting in the loss of the fluorescence characteristic. The existing method for solving the problem that the inorganic fluorescent material is easy to deliquesce and lose efficacy is to coat a layer of protective film on the surface of the fluorescent material by a surface coating technology after fluorescent powder with excellent performance is obtained, so as to block the contact between moisture and the fluorescent material. However, the method has the disadvantages of complex process flow, high cost and high requirement on the coating process.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a functional filler with both gelling and long-afterglow luminescent properties, and a preparation method and application thereof. The functional filler is the alkaline earth aluminate long-afterglow fluorescent material with stable fluorescence performance obtained by redesigning the phase composition of the material, optimizing the performance of the material and adjusting the preparation process of the material on the basis of the traditional alkaline earth aluminate fluorescent material, and solves the defect that the traditional inorganic fluorescent material is easy to absorb water and deliquesce to cause the fluorescence performance to be invalid.
In a first aspect of the present invention, a functional filler having both gelling and long-afterglow luminescent properties is provided.
In a second aspect of the present invention, a method for preparing a functional filler having both gelling and long-afterglow luminescent properties is provided.
The third aspect of the invention is to provide an application of the functional filler with both gelling and long-afterglow luminescent properties.
In order to achieve the purpose, the invention adopts the technical scheme that:
firstly, the invention discloses a functional filler with gelling and long afterglow luminescence characteristics, which mainly comprises a strontium calcium sulphoaluminate phase and a strontium aluminate phase, wherein the chemical formula of the strontium calcium sulphoaluminate phase is Ca3SrAl6SO16The chemical formula of the strontium aluminate phase is SrAl2O4：xEu2+，yRE3+；0≤x≤0.03，0≤y≤0.075。
Further, the molar ratio of the strontium calcium sulphoaluminate phase to the strontium aluminate phase is 1: 9-9: 1; preferably 5: 4.
Further, the RE3+Is a co-activator, including but not limited to Y3+、Nd3+、Dy3+、Tb3+And the like.
Further, the functional filler also comprises CaAl2O4、Ca12Al14O33And the like. The filler is a multifunctional filler composed of multiple phases, wherein the phase 1 is Ca3SrAl6SO16It has excellent gelling properties; the phase 2 is a strontium aluminate phase, so that the filler has long afterglow luminescence characteristics, and the existence of the phase 1 has a good protection effect on a fluorescent phase, so that the phenomenon that the fluorescent property disappears due to the reaction of the strontium aluminate phase and water when the filler is prepared into a coating can be avoided.
The invention further discloses a preparation method of the functional filler with the gelling and long-afterglow luminescent properties, which comprises the following steps:
(1) grinding: calcium carbonate, alumina, calcium sulfate, strontium carbonate and rare earth excitant are respectively ground.
(2) Preparing a premix:
taking strontium carbonate and aluminum oxide, then adding a rare earth activator, and uniformly mixing; adding polyurethane acrylic acid (PUA) or polyurethane crotonate (PUB) heated to liquid state into the uniformly mixed raw materials, crushing after cooling and agglomeration, and then grinding to obtain a first premix;
and uniformly mixing calcium carbonate, strontium carbonate, dihydrate gypsum and alumina to obtain a second premix.
(3) Preparing a blend material: uniformly mixing the first premix and the second premix, adding a medium for wet mixing, continuously mixing, taking out the uniformly mixed material after the mixing is finished, and drying the uniformly mixed material to obtain a blended material;
(4) and (3) calcining: the blend is subjected to sectional calcination under the reducing atmosphere condition: and after the first-stage calcination is finished, heating for the second-stage calcination, and grinding the product after the calcination to obtain the functional filler.
Further, in the step (1), the raw materials are in the following proportions: 6-24 parts of calcium carbonate, 37-38 parts of alumina, 6-20 parts of calcium sulfate dihydrate, 19-48 parts of strontium carbonate, 0.5-3 parts of rare earth activator and 2 parts of PUA or PUB.
Further, in step (1), the rare earth activator includes, but is not limited to, Eu2O3、Tb2O3、Nd2O3And the like.
Further, in the step (2), strontium carbonate and aluminum oxide are weighed according to an equal molar ratio, and a rare earth activator accounting for 0.5-3% of the mass of the strontium carbonate is added.
Further, in the step (2), the adding proportion of the polyurethane acrylate (PUA) or the polyurethane crotonate (PUB) is 1-5% of the mass of the strontium carbonate and the aluminum oxide. The additive is only used as a dispersing agent and a binder in a tabletting process, and has no substantial influence on the prepared product.
In step (2), the molar ratio of calcium carbonate, strontium carbonate, dihydrate gypsum and alumina in the second premix is 1-4: 1:1:3, preferably 1-2: 1:1:3 or 2-4: 1:1:3, and more preferably 2:1:1: 3. When the raw material ratio of the gelled phase in the filler is within the above range, the gelled phase obtained has good gelling properties.
Further, in the step (3), the mass ratio of the first premix to the second premix is 1: 9-9: 1. Specifically, the specific ratio can be determined according to the fluorescence intensity and the environmental water content, and the content of the first premix can be within the range of 10-90%. According to the invention, the rare earth element accounts for only 0.5-3%, so that the dispersion condition in the raw materials has an important influence on the fluorescence property of the filler, the rare earth element can be uniformly dispersed in the fluorescent phase raw materials by a pre-mixing mode, the rare earth element can enter a fluorescent phase mineral lattice in a solid phase reaction and then is mixed, the process of preparing the functional filler by the solid phase reaction through subsequent sectional calcination is facilitated, and the purpose that the functional filler has both the gelling property and the fluorescence property can be better realized.
Further, in the step (4), the reducing atmosphere consists of hydrogen and nitrogen; optionally, the volume percentage of the hydrogen is 8-14%, and more preferably 10%.
Further, in the step (4), the conditions of the first stage calcination are as follows: keeping the temperature for 2-12 h at 1360-1380 ℃.
Further, in the step (4), the conditions of the second stage calcination are as follows: keeping the temperature at 1390-1420 ℃ for 2-18 h.
Finally, the invention discloses application of the functional filler with the gelling and long-afterglow luminescent properties in the fields of fluorescent paint and the like.
The luminous principle of the functional filler is as follows: after the rare earth ions enter crystal lattices, the internal lattices are changed, and a luminous center is formed. After being excited by illumination, the outer electrons of the rare earth ions are shown to be transited from the ground state of 4f to the excited state of 5d, then the electrons on the excited state are transited to the excited state of a lower energy level in a relaxation mode (no energy radiation exists in the process), and finally the electrons are transited back to the ground state again, and the energy released by the electrons in the process can be emitted in the form of photons. Therefore, the filler has the advantages of high luminous efficiency, long afterglow time, stable chemical property, long service life, no radioactive hazard and the like.
One of the characteristics of the functional filler of the invention is as follows: the composite matching integrated design of different mineral phases and the new gelation property of the luminescent material solve the defect that the traditional aluminate fluorescent material is easy to absorb moisture and lose the fluorescence property. The strontium calcium sulphoaluminate phase has the characteristic of being very easy to hydrate, consumes moisture entering the material, and the hydration products of the strontium calcium sulphoaluminate phase are alumina gel, strontium sulfate and the like, and can wrap the surface of the material to prevent the moisture from further contacting with the strontium aluminate. Meanwhile, when products such as coatings are prepared, the excellent gel property can effectively enhance the mechanical property of the products.
The functional filler of the invention is characterized in that: the filler prepared by the calcination system enables different phases in the filler to be generated in large quantity under proper calcination conditions in the processes of sectional calcination and sectional heat preservation, and realizes the integrated calcination of the functional filler. Through the sectional calcination, the rare earth elements can be regulated and controlled to enter fluorescent minerals in a targeted manner, and the crystal growth state can be favorably regulated and controlled; and the solid-phase reaction process of the fluorescent mineral and the gelled mineral can be regulated and controlled, so that the gelling property and the fluorescence property of the filler are regulated and controlled.
Compared with the prior art, the invention has the following beneficial effects:
(1) the gelling phase of the filler is strontium calcium sulphoaluminate phase, and has the characteristic of extremely easy reaction with water, so hydration products such as alumina gel, ettringite and the like can be formed by consuming water, and the gelling phase is protected. According to the invention, the fluorescence property of the material is optimized according to the adjustment of the mineral structure of the fluorescent filler, the material is endowed with excellent gelation property, the defect that the traditional fluorescent filler is easy to deliquesce and lose efficacy in the phase composition direction of the mineral is solved, and the practical application value of the fluorescent filler is improved.
(2) The preparation process of the invention can simply and effectively synthesize the alkaline earth aluminate long-afterglow fluorescent filler with high fluorescence intensity, long afterglow time, high chemical stability and weather resistance and good gelation property.
(3) According to the invention, by optimizing and improving the synthesis process of the material and adopting a solid-phase synthesis method, the fluorescent material with high fluorescence intensity, long afterglow time, stable chemical property and good weather resistance is obtained; the process of the invention has the characteristics of high efficiency and less pollution.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is an XRD test pattern of the functional filler prepared in the first embodiment of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Term interpretation section: (1) gelling property: the performance of the cementing material is that under the physical and chemical action, the slurry can be changed into firm stone-like body, and can be cemented with other materials to make into composite solid with a certain mechanical strength. (2) Long afterglow luminescence characteristics: is a characteristic of long persistence luminescent materials, which refers to the property of a material that can absorb energy and continue to emit light after excitation has ceased. (3) Functional filler: refers to a filler that is filled in other objects to impart some special functionality thereto. The functional filler prepared by the invention is a functional material with both gelation and long afterglow luminescence characteristics.
As described above, the existing rare earth ion doped excited alkaline earth aluminate luminescent material has the problem that deliquescence is easy to occur to cause the loss of the fluorescence characteristic, but the method for solving the problem through the surface coating technology has the defects of complex process flow, high cost, high requirement on the coating technology and the like. Therefore, the invention provides a functional filler with both gelling and long-afterglow luminescent properties and a preparation method thereof; the invention will now be further described with reference to the drawings and detailed description.
First embodiment
A preparation method of a functional filler with gelling and long afterglow luminescence characteristics comprises the following steps:
(1) weighing raw materials: weighing 24 parts of calcium carbonate, 37 parts of alumina, 20 parts of calcium sulfate dihydrate, 19 parts of strontium carbonate and a rare earth activator (Eu) according to parts by weight2O3)0.5 part of PUA and 0.5 part of PUA.
(2) Grinding: and (2) respectively grinding the calcium carbonate, the alumina, the strontium carbonate, the calcium sulfate dihydrate and the rare earth activator in the step (1) in an agate mortar until the calcium carbonate, the alumina, the strontium carbonate, the calcium sulfate dihydrate and the rare earth activator pass through a 200-mesh sieve.
(3) Preparing a premix: firstly, 1.9 parts and 1.3 parts of strontium carbonate and aluminum oxide are respectively weighed on an analytical balance according to the molar ratio of 1:1, and a rare earth activator accounting for 2 mass percent of the strontium carbonate and the aluminum oxide is added and uniformly mixed. Heating PUA (polyurethane) with the mass of 2% of that of strontium carbonate and alumina to liquid state, adding the heated PUA into the uniformly mixed raw materials, crushing a product obtained after cooling and agglomeration, then placing the product into a planetary ball mill, grinding the product for 180min at the rotating speed of 200rad/min, enabling the material to pass through a 200-mesh sieve, and uniformly dispersing the material to obtain a first premix for later use; calcium carbonate, strontium carbonate, dihydrate gypsum, alumina 23.5 parts, alumina 17.4 parts, alumina 19.8 parts and alumina 36 parts are respectively weighed according to the mol ratio of 2:1:1:3, and are dry-mixed in a planetary mixer at the rotating speed of 200rad/min for 60min to obtain a second premix for later use.
(3) Preparing a blend material: and (3) uniformly mixing the first premix and the second premix in the previous step, adding the mixture into a polytetrafluoroethylene ball milling tank, firstly performing dry mixing for 40min at 100rad/min, adding an alcohol medium after uniform mixing, performing dry mixing for 2h at the rotating speed of 200rad/min, uniformly mixing the materials, taking out the uniformly mixed materials, and drying in an oven at 60 ℃ to obtain a mixed material.
(4) Tabletting and forming: the blend of the previous step was pressed at 10MPa to a square sheet sample of 4mm by 4mm and 3mm thickness.
(5) And (3) calcining: the sample after the compression molding is put into a high-temperature furnace for sectional calcination, and the atmosphere in the high-temperature furnace is a reducing atmosphere (10% H by volume)2+90％N2). The sectional calcining process comprises the following steps: calcining at the temperature rise rate of 2 ℃/min from room temperature, keeping the temperature at 1360 ℃ for 10h, then continuously heating to the temperature rise rate of 5 ℃/min, continuously calcining, keeping the temperature at 1390 ℃ for 14h, fully performing each solid phase reaction of the minerals, completely developing crystal grains, taking out a sample after the calcination is finished, and grinding to obtain the functional filler.
Second embodiment
A preparation method of a functional filler with gelling and long afterglow luminescence characteristics comprises the following steps:
(1) weighing raw materials: weighing 7 parts of calcium carbonate, 10 parts of alumina, 6 parts of calcium sulfate dihydrate, 49 parts of strontium carbonate and a rare earth activator (Eu in a mass ratio of 1: 1)2O3And Tb2O3)1 part and 2 parts of PUA.
(2) Grinding: and (2) respectively grinding the calcium carbonate, the alumina, the strontium carbonate, the calcium sulfate dihydrate and the rare earth activator in the step (1) in an agate mortar until the calcium carbonate, the alumina, the strontium carbonate, the calcium sulfate dihydrate and the rare earth activator pass through a 200-mesh sieve.
(3) Preparing a premix: firstly, 43.4 parts of strontium carbonate and 30 parts of aluminum oxide are respectively weighed on an analytical balance according to the molar ratio of 1:1, and a rare earth activator accounting for 1% of the mass of the strontium carbonate and the aluminum oxide is added and uniformly mixed. Heating the PUA with the mass of 1% of strontium carbonate and alumina to liquid state, adding the heated PUA into the uniformly mixed raw materials, crushing the product after cooling and agglomeration, then placing the product into a planetary ball mill for grinding for 150min at the rotating speed of 50rad/min, enabling the material to pass through a 200-mesh sieve, and uniformly dispersing to obtain a first premix for later use; calcium carbonate, strontium carbonate, dihydrate gypsum, 6.5 parts of alumina, 4.8 parts of alumina, 10 parts of dihydrate gypsum and 5.5 parts of alumina are weighed according to the molar ratio of 2:1:1:3, and dry-mixed for 120min in a planetary mixer at the rotating speed of 100rad/min to obtain a second premix for later use.
(3) Preparing a blend material: and (3) uniformly mixing the first premix and the second premix in the previous step, adding the first premix and the second premix into a polytetrafluoroethylene ball milling tank, then performing dry mixing for 20min at a speed of 250rad/min, adding an alcohol medium after uniform mixing, performing dry mixing for 3h at a speed of 100rad/min again, uniformly mixing the materials, taking out the uniformly mixed materials, and drying in an oven at a temperature of 50 ℃ to obtain a mixed material.
(4) Tabletting and forming: the blend of the previous step was pressed at 15MPa to a square sheet sample of 4mm by 4mm and 3mm thickness.
(5) And (3) calcining: the sample after the compression molding is put into a high-temperature furnace for sectional calcination, and the atmosphere in the high-temperature furnace is a reducing atmosphere (10% H by volume)2+90％N2). The sectional calcining process comprises the following steps: calcining at the temperature rising rate of 10 ℃/min from room temperature, keeping the temperature at 1360 ℃ for 12h, then continuing to heat to the temperature rising rate of 6 ℃/min for continuing calcining, keeping the temperature at 1400 ℃ for 18h to ensure that each solid phase reaction of the minerals is fully carried out and the crystal grains are completely developed, taking out a sample after the calcining is finished, and grinding to obtain the functional filler.
Third embodiment
A preparation method of a functional filler with gelling and long afterglow luminescence characteristics comprises the following steps:
(1) weighing raw materials: weighing 19 parts of calcium carbonate, 38 parts of alumina, 16 parts of calcium sulfate dihydrate, 28 parts of strontium carbonate and a rare earth activator (Nd) according to parts by weight2O3)0.5 part and 2 parts of PUB.
(2) Grinding: and (2) respectively grinding the calcium carbonate, the alumina, the strontium carbonate, the calcium sulfate dihydrate and the rare earth activator in the step (1) in an agate mortar until the calcium carbonate, the alumina, the strontium carbonate, the calcium sulfate dihydrate and the rare earth activator pass through a 200-mesh sieve.
(3) Preparing a premix: firstly, 13.8 parts and 9.5 parts of strontium carbonate and aluminum oxide are respectively weighed on an analytical balance according to the molar ratio of 1:1, and a rare earth activator accounting for 2 mass percent of the strontium carbonate is added and uniformly mixed. Heating the strontium carbonate and PUB accounting for 5% of the mass of the aluminum oxide to be liquid, adding the liquid into the uniformly mixed raw materials, crushing a product obtained after cooling and agglomeration, then placing the product into a planetary ball mill, grinding the product for 30min at the rotating speed of 300rad/min, enabling the material to pass through a 200-mesh sieve, and uniformly dispersing the material to obtain a first premix for later use; calcium carbonate, strontium carbonate, dihydrate gypsum, 18.7 parts of alumina, 13.8 parts of alumina, 28.5 parts of dihydrate gypsum and 15.7 parts of alumina are respectively weighed according to the molar ratio of 4:1:1:3, and are dry-mixed for 20min in a planetary mixer at the rotating speed of 300rad/min to obtain a second premix for later use.
(3) Preparing a blend material: and (3) uniformly mixing the first premix and the second premix in the previous step, adding the first premix and the second premix into a polytetrafluoroethylene ball milling tank, then performing dry mixing for 60min at 200rad/min, adding an alcohol medium after uniform mixing, performing dry mixing for 1h at the rotating speed of 350rad/min again, uniformly mixing the materials, taking out the uniformly mixed materials, and drying in an oven at 40 ℃ to obtain a mixed material.
(4) Tabletting and forming: the blend of the previous step was pressed at 15MPa to a square sheet sample of 4mm by 4mm and 2mm thickness.
(5) And (3) calcining: the sample after the compression molding is put into a high-temperature furnace for sectional calcination, and the atmosphere in the high-temperature furnace is a reducing atmosphere (10% H by volume)2+90％N2). The sectional calcining process comprises the following steps: calcining at the heating rate of 2 ℃/min from room temperature, keeping the temperature at 1380 ℃ for 2h, then continuously heating to the heating rate of 2-6 ℃/min, continuously calcining, keeping the temperature at 1420 ℃ for 2h to ensure that each solid phase reaction of the minerals is fully carried out and the crystal grains are completely developed, taking out a sample after the calcining is finished, and grinding to obtain the functional filler.
Fourth embodiment
A preparation method of a functional filler with gelling and long afterglow luminescence characteristics comprises the following steps:
(1) weighing raw materials: weighing 41 parts of alumina, 60 parts of strontium carbonate and a rare earth activator (Eu) according to parts by weight2O3)2 parts of PUA and 2 parts of PUA.
(2) Grinding: and (2) respectively grinding the alumina, the strontium carbonate and the rare earth excitant in the step (1) in an agate mortar until the mixture is sieved by a 200-mesh sieve.
(3) Preparing a premix: firstly, 59.2 parts and 40.8 parts of strontium carbonate and alumina are respectively weighed on an analytical balance according to the molar ratio of 1:1, and a rare earth activator accounting for 3% of the mass of the strontium carbonate is added and uniformly mixed. Heating the PUA with the mass of 2% of that of the strontium carbonate and the alumina to liquid state, then adding the heated PUA into the uniformly mixed raw materials, crushing the product obtained after cooling and agglomeration, then placing the product into a planetary ball mill for grinding for 180min at the rotating speed of 200rad/min, enabling the material to pass through a 200-mesh sieve, and uniformly dispersing the material for later use.
(4) Preparing a blend material: and adding the premix in the previous step into a polytetrafluoroethylene ball milling tank, then dry-mixing for 40min at a speed of 100rad/min, adding an alcohol medium after uniform mixing, dry-mixing for 2h at a speed of 200rad/min, uniformly mixing the materials, taking out the uniformly mixed materials, and drying in an oven at a temperature of 60 ℃ to obtain the blend.
(5) Tabletting and forming: the blend of the previous step was pressed at 10MPa to a square sheet sample of 4mm by 4mm and 3mm thickness.
(6) And (3) calcining: the sample after the compression molding is put into a high-temperature furnace for sectional calcination, and the atmosphere in the high-temperature furnace is a reducing atmosphere (10% H by volume)2+90％N2). The sectional calcining process comprises the following steps: calcining at the heating rate of 2 ℃/min from room temperature, preserving heat at 1360 ℃ for 10h to fully perform each solid phase reaction of the minerals, ensuring complete crystal grain development, taking out a sample after calcining is finished, and grinding to obtain the fluorescent filler.
And (3) performance testing:
(1) FIG. 1 is an XRD test chart of the functional filler prepared in the first example, and it can be seen that a gel phase strontium calcium sulphoaluminate (Ca) exists in the filler3SrAl6SO16) Fluorescent phase strontium aluminate (SrAl)2O4：Eu2+，RE3+) And a small amount of Ca12Al14O33Miscellaneous phases, which prove that the filler of the invention mainly consists of a gelled phase and a fluorescent phase. Meanwhile, the volume ratio of the strontium calcium sulphoaluminate phase to the strontium aluminate phase in the functional filler is calculated to be 1: 9.
(2) The first and fourth examples were tested for fluorescence performance after freeze-thaw cycling of the filler and the results are shown in table 1. The method specifically comprises the following steps: the functional filler obtained in the first embodiment and the functional filler obtained in the fourth embodiment are ground and added into a polyacrylic acid coating, and after the coating is painted, the ultraviolet analyzer ZF-5 tests show that the coating obtained by adding the filler in the first embodiment still has a fluorescence phenomenon after being painted; the reason why the fluorescence intensity of the paint obtained by adding the filler of the fourth embodiment is obviously reduced after painting and the fluorescence phenomenon disappears after 24 hours is that: the moisture of the polyacrylic acid coating reacts with the fluorescent filler in the fourth embodiment, so that the fluorescent property of the polyacrylic acid coating is lost; the functional filler in the first embodiment can protect the fluorescent phase due to the existence of the gel phase, so that the fluorescent phenomenon still exists after 24 hours.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and not intended to limit the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of them. Therefore, any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The functional filler with both gelling and long-afterglow luminescent characteristics is characterized by mainly comprising a strontium calcium sulphoaluminate phase and a strontium aluminate phase, wherein the chemical formula of the strontium calcium sulphoaluminate phase is Ca3SrAl6SO16Strontium aluminate phaseHas the chemical formula of SrAl2O4：xEu2+，yRE3+；0≤x≤0.03，0≤y≤0.075。
2. The functional filler with both gelation and long afterglow luminescence properties of claim 1, wherein the RE is3 +Comprising Y3+、Nd3+、Dy3+、Tb3+Any one of them.
3. The functional filler with both gelling and long-afterglow luminescent properties as claimed in claim 1, wherein the molar ratio of the strontium calcium sulphoaluminate phase to the strontium aluminate phase is 1:9 to 9: 1; preferably 5: 4.
4. The functional filler with both gelling and long-afterglow luminescent properties as claimed in any one of claims 1 to 3, wherein the functional filler further comprises CaAl2O4Phase, Ca12Al14O33At least one of the phases.
5. A preparation method of a functional filler with both gelation and long afterglow luminescence characteristics is characterized by comprising the following steps:
(1) respectively grinding calcium carbonate, alumina, calcium sulfate, strontium carbonate and a rare earth activator;
(2) mixing strontium carbonate and aluminum oxide, adding or compounding with RE excitant and mixing; adding the PUA or PUB heated to the liquid state into the uniformly mixed raw materials, crushing after cooling and agglomeration, and then grinding to obtain a first premix;
uniformly mixing calcium carbonate, strontium carbonate, dihydrate gypsum and alumina to obtain a second premix;
(3) uniformly mixing the first premix and the second premix, adding a medium for wet mixing, continuously mixing, taking out the uniformly mixed material after the mixing is finished, and drying the uniformly mixed material to obtain a blended material;
(4) the blend is subjected to sectional calcination under the reducing atmosphere condition: and after the first-stage calcination is finished, heating for carrying out second-stage calcination, and grinding the product after the calcination, thereby obtaining the catalyst.
6. The method for preparing the functional filler with both gelation and long afterglow luminescence properties as claimed in claim 5, wherein in step (1), 6 to 24 parts by weight of calcium carbonate, 37 to 40 parts by weight of alumina, 6 to 20 parts by weight of calcium sulfate dihydrate, 19 to 48 parts by weight of strontium carbonate, 0.5 to 3 parts by weight of rare earth activator, and 2 parts by weight of PUA or PUB;
or, in the step (2), weighing strontium carbonate and aluminum oxide according to an equal molar ratio;
or in the step (2), the addition proportion of the rare earth activator accounts for 0.5-3% of the mass of the strontium aluminate.
7. The method for preparing the functional filler with both gelling and long-afterglow luminescent properties as claimed in claim 5, wherein in the step (2), the adding proportion of the PUA or PUB is 1-5%;
or in the step (2), the molar ratio of calcium carbonate, strontium carbonate, dihydrate gypsum and alumina in the second premix is 1-4: 1:1:3, preferably 1-2: 1:1:3 or 2-4: 1:1:3, and more preferably 2:1:1: 3.
8. The preparation method of the functional filler with both gelling and long-afterglow luminescent properties as claimed in claim 5, wherein in the step (3), the mass ratio of the first premix to the second premix is 1: 9-9: 1;
alternatively, in the step (4), the conditions of the first-stage calcination are as follows: preserving heat for 2-12 h at 1360-1380 ℃;
alternatively, in the step (4), the conditions of the second stage calcination are as follows: keeping the temperature at 1390-1420 ℃ for 2-18 h.
9. The method for preparing the functional filler with both gelation and long afterglow luminescence properties according to any one of claims 5 to 8, wherein in step (1), the rare earth activator comprises Eu2O3、Tb2O3、Nd2O3One or more of;
or, in the step (4), the reducing atmosphere consists of hydrogen and nitrogen; preferably, the volume percentage of the hydrogen is 8-14%, and more preferably, the volume percentage of the hydrogen is 10%.
10. Use of the functional filler having both gelling and long-afterglow luminescent properties as defined in any of claims 1 to 4 and/or the functional filler prepared by the method as defined in any of claims 5 to 9 in fluorescent coatings.
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