CN111925683B - Fluorescent whitening automobile paint based on BAM EM and preparation method thereof - Google Patents

Fluorescent whitening automobile paint based on BAM EM and preparation method thereof Download PDF

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CN111925683B
CN111925683B CN202010874428.4A CN202010874428A CN111925683B CN 111925683 B CN111925683 B CN 111925683B CN 202010874428 A CN202010874428 A CN 202010874428A CN 111925683 B CN111925683 B CN 111925683B
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powder
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automobile
bam
ammonium bicarbonate
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CN111925683A (en
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王育华
濑户孝俊
周钰涵
范毓
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Lanzhou University
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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
    • 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
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7734—Aluminates
    • 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

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Abstract

The invention discloses a BAM EM-based fluorescent whitening automobile paint and a preparation method thereof, wherein the paint is prepared from automobile varnish and green with submicron scale excited by near ultravioletAnd (3) color fluorescent powder. Weighing raw materials, eu, according to stoichiometric ratio 2 O 3 Dissolving in concentrated nitric acid to obtain a first solution; dissolving the first solution and other metal compounds in deionized water to obtain a metal ion mixed solution; NH 4 HCO 3 Dissolving in deionized water to obtain ammonium bicarbonate solution; dripping the metal ion mixed solution into an ammonium bicarbonate solution, adjusting the pH value of a precipitation system, performing centrifugal separation, and drying precipitates to obtain precursor powder; mixing the precursor powder and NH 4 Cl, calcining and grinding to obtain near ultraviolet excited green fluorescent powder with submicron scale; adding the automobile varnish, and uniformly mixing to obtain the BAM EM-based fluorescent whitening automobile paint. The preparation method of the invention utilizes a coprecipitation method to prepare the submicron fluorescent powder and simultaneously ensures the brightness as much as possible.

Description

Fluorescent whitening automobile paint based on BAM EM and preparation method thereof
Technical Field
The invention belongs to the technical field of automobile paint, and relates to BAM EM-based fluorescent whitening automobile paint and a preparation method thereof.
Background
Green light has a significant whitening effect on white, while BAM (Ba) 1-x Eu x Mg 1-y Mn y Al 10 O 17 ) The fluorescent powder can emit green fluorescence under the excitation of ultraviolet or near ultraviolet light, and sunlight contains abundant ultraviolet and near ultraviolet light. Therefore, the BAM fluorescent powder can be dissolved in the automotive varnish to obtain the automotive composite paint, and the white automobile can show an obvious fluorescent whitening effect under the excitation of sunlight by matching with the white primer of the automobile, so that a very beautiful white automobile is constructed.
Disclosure of Invention
The object of the present invention is to provide a BAM EM based fluorescent whitening automotive paint that exhibits a pronounced fluorescent whitening effect under solar excitation.
Another object of the present invention is to provide a process for the preparation of the above-mentioned automotive paint with fluorescent whitening.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a BAM EM-based fluorescent whitening automobile paint is composed of an optical functional material and a carrier material, wherein the carrier material is automobile varnish, and the optical function isThe material is near ultraviolet excited green phosphor with submicron size (average grain size less than 1 micron), and the green phosphor has the chemical formula of (Ba) z Sr 1-z ) 1-x Eu x Mg 1-y Mn y Al 10 O 17 Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and z is more than 0 and less than or equal to 1; the ratio of the excitation intensity at 400nm to the maximum excitation intensity of the excitation wavelength in the range of 250-500 nm corresponding to the green emission peak is 0.4-1.
When z =1, the chemical formula of the green phosphor is Ba 1-x Eu x Mg 1-y Mn y Al 10 O 17 Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1; preferably, x is 0.25. Ltoreq. X.ltoreq.0.5 and y is 0.1. Ltoreq.y.ltoreq.0.7, at which the ratio of the excitation intensity at 400nm of the phosphor to the maximum excitation intensity of the excitation wavelength in the range of 250 to 500nm corresponding to the green emission peak is 0.6 to 1.
The invention adopts another technical scheme that: a preparation method of fluorescent whitening automobile paint powder specifically comprises the following steps:
1) According to the formula (Ba) z Sr 1-z ) 1-x Eu x Mg 1-y Mn y Al 10 O 17 The stoichiometric ratio of the elements in the Eu mill, and the Eu is accurately weighed 2 O 3 、Ba(NO 3 ) 2 、Sr(NO 3 ) 2 、Mg(NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O and MnCl 2 ；
2) Eu is mixed 2 O 3 Dissolving in concentrated nitric acid with the mass fraction of 65-68% to obtain a first solution;
3) Mixing the first solution with Ba (NO) 3 ) 2 、Sr(NO 3 ) 2 、Mg(NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O and MnCl 2 Adding the mixture into deionized water, adjusting the temperature of a magnetic stirrer to 35-45 ℃, controlling the rotating speed to be 400-500 r/min, heating and stirring until solid particles are completely dissolved to obtain a metal ion mixed solution;
or mixing the first solution with Ba (NO) 3 ) 2 、Mg(NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O and MnCl 2 Adding the mixture into deionized water, adjusting the temperature of a magnetic stirrer to 35-45 ℃, controlling the rotating speed to be 400-500 r/min, heating and stirring until solid particles are completely dissolved to obtain a metal ion mixed solution;
4) Reacting NH 4 HCO 3 Adding the mixture into deionized water, adjusting the temperature of a magnetic stirrer to 35-45 ℃, controlling the rotating speed to be 400-500 r/min, heating and stirring until solid particles are completely dissolved, and obtaining an ammonium bicarbonate solution with the molar volume concentration of 3 mol/L;
5) Respectively taking the metal ion mixed solution and the ammonium bicarbonate solution according to the volume ratio of 1: 1-2, dropwise adding the metal ion mixed solution into the ammonium bicarbonate solution under the condition of stirring, adding ammonia water after dropwise adding is finished, and adjusting the pH value of a precipitation system to be 9-10; after the precipitation reaction is finished, performing centrifugal separation, pouring out supernatant liquor, and drying the precipitate in a drying oven at the temperature of between 60 and 70 ℃ for 20 to 24 hours to obtain white precursor fluffy powder;
6) Taking precursor fluffy powder and NH respectively 4 Cl, and mixing uniformly to obtain mixed powder, wherein NH is contained in the mixed powder 4 The mass fraction of Cl is 0.5-2 wt%, the mixed powder is placed in a tubular furnace which is introduced into a reducing atmosphere, the temperature is raised to 1200-1450 ℃ at the temperature raising rate of 5 ℃/min, the mixed powder is calcined for 8 hours, and the product is cooled along with the furnace and ground to prepare near ultraviolet excited green fluorescent powder with submicron scale;
reducing atmosphere of 95% by volume of N 2 And 5% of H 2 Mixing the components;
7) And (3) taking the automobile varnish, and then uniformly mixing the near ultraviolet excited submicron green fluorescent powder with the mass of 10-50% of that of the automobile varnish to obtain the BAM EM-based fluorescent whitening automobile paint.
In order to further improve the brightness and crystallinity of the fluorescent whitening automobile paint, the near ultraviolet excited submicron-scale green fluorescent powder prepared in the step 4) can be annealed at 1300 ℃ for 4-8 hours to obtain the annealed green fluorescent powder; then, the automobile varnish is taken, and the annealed green fluorescent powder with the mass of 10-50% of that of the automobile varnish is uniformly mixed to obtain the BAM EM-based fluorescent whitening automobile paint.
The preparation method of the invention firstly uses Ba 2+ 、Eu 2+ 、Mg 2+ 、Mn 2+ 、Al 3+ 、Sr 2+ Coprecipitation system or Ba 2+ 、Eu 2+ 、Mg 2+ 、Mn 2+ 、Al 3+ Adding NH into a coprecipitation system 4 Cl, in the calcination process to prepare the new luminescent material. NH 4 Cl is often used for the synthesis of Ba 3 MgSi 2 O 8 Eu or (Ba, sr) 2 SiO 4 A flux of an oxide phosphor such as Eu. That is, NH 4 Cl is used to reduce the particle size of the phosphor. Under the conventional process conditions, when NH 4 When the mixture of Cl (0.2-5 wt%) and the co-precipitation precursor is calcined in a reducing atmosphere at temperatures below the solid phase synthesis temperature of 1200-1450 ℃, the oxide particles formed do not aggregate, but rather are individual small particles separated from each other. Thus, NH can be considered 4 The Cl is decomposed into a gas phase during the heating for calcination, and the formed gas can avoid aggregation between the fine oxide particles.
Secondly, compared with the conventional BAM fluorescent powder, eu in the BAM fluorescent powder of the invention 2+ And Mn 2+ Is abnormally large, resulting in an extended excitation wavelength and a significant increase in excitation intensity at NUV wavelengths of 400 nm. When the ratio of x and y of Eu and Mn is changed from 0.09 and 1.3 (conventional ratio of BAM) to 0.4 and 0.58, the ratio of excitation intensity (excitation intensity at 400 nm)/(maximum excitation intensity) is changed from 16% to 67%. This technology allows micron sized BAM EM to produce beautiful green fluorescence in the sun under outdoor (including NUV) for fluorescent whitening of automotive paints. When the Mn/Eu ratio is 1.44, the ratio of emission intensity (green emission)/(blue emission + green emission) is changed from 75% to 99% when the Eu content is changed from 0.09 to 0.4. This is probably due to the fact that the Eu-Mn average distance is greatly reduced as Eu and Mn are increased, eu 2+ →Mn 2+ The phenomenon of enhanced energy transfer.
The inventionPreparation method by NH 4 Cl is taken as a fluxing agent, submicron barium magnesium aluminate base BAM fluorescent powder particles with the particle size of less than 1 mu m are obtained by adopting a coprecipitation method, and the barium magnesium aluminate base BAM fluorescent powder has high-concentration europium ion Eu 2+ (x = 0.4) and high concentration of manganese ions Mn 2+ (x = 0.58), has super-absorption to 400nm near-ultraviolet sunlight and can emit super-green fluorescence.
The invention utilizes the coprecipitation method to prepare submicron BAM EM (Ba) 1-x Eu x Mg 1-y Mn y Al 10 O 17 Phosphor, ba prepared by adding more than conventional solid phase method 1-x Eu x Mg 1-y Mn y Al 10 O 17 (x = 0.1, y = 0.1-0.2) more Eu 2+ And Mn 2+ So that Eu is 2+ →Mn 2+ The energy transfer between the crystal grains is more efficient, and the brightness is ensured as much as possible while the submicron crystal grains are prepared. Addition of NH 4 Cl as a co-solvent reduced agglomeration of BAM EM microparticles.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of the phosphors prepared in examples 1 and 2.
FIG. 2 is an SEM photograph of the phosphor prepared in example 1.
FIG. 3 is an SEM photograph of the phosphor prepared in example 2.
FIG. 4 shows the excitation and emission spectra of the phosphor prepared in example 2.
FIG. 5 is a graph comparing the excitation spectra of the phosphors prepared in examples 1 and 2.
FIG. 6 is a graph comparing the emission spectra of the phosphors prepared in examples 1 and 2.
FIG. 7 is a graph comparing the emission spectra of the phosphor prepared in example 2 with and without annealing.
FIG. 8 is an X-ray powder diffraction pattern of the phosphor obtained in example 4.
FIG. 9 shows the excitation and emission spectra of the phosphor prepared in example 4.
Detailed Description
Example 1
According to the chemical formula Ba 0.91 Eu 0.09 Mg 0.87 Mn 0.13 Al 10 O 17 The stoichiometric ratio of each element in the composition is 0.032 g Eu 2 O 3 0.4756 g Ba (NO) 3 ) 2 0.4461 g Mg (NO) 3 ) 2 ·6H 2 O, 7.5026 g Al (NO) 3 ) 3 ·9H 2 O and 0.04278 g MnCl 2 (ii) a Eu is mixed 2 O 3 Completely dissolving in concentrated nitric acid with the mass fraction of 65% to obtain a first solution; mixing the first solution with Ba (NO) 3 ) 2 、Mg(NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O and MnCl 2 Adding into deionized water, adjusting the temperature of a magnetic stirrer to about 40 ℃, heating and stirring until solid particles are completely dissolved to obtain a metal ion mixed solution, wherein the rotating speed is 500 r/min; weigh 11.858 grams of NH 4 HCO 3 Dissolving in 100mL deionized water, adjusting the temperature of a magnetic stirrer to about 40 ℃, rotating at 500r/min, and heating and stirring until solid particles are completely dissolved to obtain an ammonium bicarbonate solution with the molar volume concentration of 3 mol/L. Respectively taking the metal ion mixed solution and the ammonium bicarbonate solution according to the volume ratio of 1:1, slowly dropwise adding the metal ion mixed solution into the ammonium bicarbonate solution while stirring the ammonium bicarbonate solution, and after dropwise adding is finished, adding a small amount of ammonia water to adjust the pH value of a precipitation system to be 9. And after the precipitation reaction is finished, performing centrifugal separation, pouring out supernatant liquid, and drying the precipitate in an oven at 60 ℃ for 24 hours to obtain white precursor powder. Respectively taking precursor powder and NH 4 Cl, and mixing uniformly to obtain mixed powder, wherein NH is contained in the mixed powder 4 The mass fraction of Cl is 1wt%, the mixed powder is transferred into a corundum crucible, and then 95% of N is introduced into the corundum crucible according to the volume ratio 2 And 5% of H 2 Heating to 1350 deg.C at a rate of 5 deg.C/min in a tubular furnace with reducing atmosphere, calcining for 8 hr, cooling, and grinding to obtain Ba 0.91 Eu 0.09 Mg 0.87 Mn 0.13 Al 10 O 17 And (4) green fluorescent powder. Taking the automobile varnish, and then taking Ba with the mass of 10 percent of the automobile varnish 0.91 Eu 0.09 Mg 0.87 Mn 0.13 Al 10 O 17 And (3) uniformly mixing the green fluorescent powder to obtain the BAM EM-based fluorescent whitening automobile paint.
Example 2
According to the chemical formula Ba 0.6 Eu 0.4 Mg 0.42 Mn 0.58 Al 10 O 17 The stoichiometric ratio of each element in the Eu is accurately measured, and the Eu is 0.1407 g 2 O 3 0.3136 g Ba (NO) 3 ) 2 0.2156 g Mg (NO) 3 ) 2 ·6H 2 O, 7.5026 g Al (NO) 3 ) 3 ·9H 2 O and 0.1459 g MnCl 2 (ii) a Ba was prepared by the method of example 1 0.6 Eu 0.4 Mg 0.42 Mn 0.58 Al 10 O 17 And (4) green fluorescent powder. Taking the automobile varnish, and taking Ba with the mass being 50% of the automobile varnish 0.6 Eu 0.4 Mg 0.42 Mn 0.58 Al 10 O 17 And (3) uniformly mixing the green fluorescent powder to obtain the BAM EM-based fluorescent whitening automobile paint.
The X-ray powder diffraction patterns of the phosphors prepared in examples 1 and 2 are shown in fig. 1. The peak values of the samples prepared in the examples are shown to be consistent with the peak values of the standard PDF card, indicating that the resulting samples are BAM and have no other peaks, indicating no impurities.
FIG. 2 is an SEM photograph of the green phosphor prepared in example 1. As can be seen from the figure, the particles are uniformly distributed, the particle size is consistent and less than 1 mu m, and no agglomeration exists, which indicates that the fluorescent powder which can be applied to the mrico-LED is successfully obtained by the preparation method.
Ba prepared in example 2 0.6 Eu 0.4 Mg 0.42 Mn 0.58 Al 10 O 17 SEM image of the phosphor, as shown in FIG. 3. It can be seen from the figure that the particles are uniformly distributed, have consistent particle size smaller than 1 μm, and are not agglomerated, indicating that the fluorescent powder which can be applied to the mrico-LED is successfully obtained.
The excitation and emission spectra of the phosphor prepared in example 2 are shown in FIG. 4. As can be seen from FIG. 4, under the excitation conditions of the wavelengths of 381nm and 400nm, the phosphor can obtain a green emission peak with an emission peak of 518nm, which indicates that the excitation peak is a broad peak of 350nm to 400 nm. Also, the fluorescent powder prepared by the preparation method is green fluorescent powder.
The excitation spectra of the green phosphors obtained in example 1 and example 2 are compared and shown in FIG. 5. As can be seen from the figure, the emission peak of the sample is red-shifted by adding a large amount of Eu and Mn ions, and the excitation peak of the sample is shifted to 400nm, so that the sample can be combined with a near ultraviolet chip.
The emission spectra of the green phosphors prepared in examples 1 and 2 are shown in FIG. 6, compared with each other, when excited at a wavelength of 400 nm. As can be seen from the figure, the emission intensity of the phosphor prepared in example 2 is significantly improved by adding a large amount of Eu and Mn ions.
Example 3
Ba was prepared as in example 2 0.6 Eu 0.4 Mg 0.42 Mn 0.58 Al 10 O 17 And (4) green fluorescent powder. Then, the green phosphor was annealed at 1300 ℃ for 8 hours to obtain annealed Ba 0.6 Eu 0.4 Mg 0.42 Mn 0.58 Al 10 O 17 And (4) green fluorescent powder. Taking the automobile varnish, and then taking Ba with the mass of 30 percent of the automobile varnish 0.6 Eu 0.4 Mg 0.42 Mn 0.58 Al 10 O 17 And (3) uniformly mixing the green fluorescent powder to obtain the BAM EM-based fluorescent whitening automobile paint.
Annealed Ba from example 3 0.6 Eu 0.4 Mg 0.42 Mn 0.58 Al 10 O 17 Green phosphor and Ba prepared in example 2 0.6 Eu 0.4 Mg 0.42 Mn 0.58 Al 10 O 17 The emission spectrum of the green phosphor is plotted as shown in fig. 7. It can be seen from fig. 7 that the brightness of the phosphor prepared in example 3 is significantly improved, which illustrates that the brightness of the phosphor is greatly increased by the annealing process.
Example 4
According to the chemical formula Ba 0.89 Sr 0.02 Eu 0.09 Mg 0.87 Mn 0.13 Al 10 O 17 The stoichiometric ratio of each element in the composition is 0.032 g Eu 2 O 3 0.4651 g Ba (NO) 3 ) 2 0.0046 g of Sr (NO) 3 ) 2 0.4461 g Mg (NO) 3 ) 2 ·6H 2 O, 7.5026 g Al (NO) 3 ) 3 ·9H 2 O and 0.04278 g MnCl 2 (ii) a Eu is mixed 2 O 3 Completely dissolving in concentrated nitric acid with the mass fraction of 65% to obtain a first solution; mixing the first solution with Ba (NO) 3 ) 2 、Sr(NO 3 ) 2 、Mg(NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O and MnCl 2 Adding into deionized water, adjusting the temperature of a magnetic stirrer to about 40 ℃, heating and stirring until solid particles are completely dissolved to obtain a metal ion mixed solution, wherein the rotating speed is 500 r/min; weigh 11.858 g NH 4 HCO 3 Dissolving in 100mL deionized water, adjusting the temperature of a magnetic stirrer to about 40 ℃, rotating at 500r/min, and heating and stirring until solid particles are completely dissolved to obtain an ammonium bicarbonate solution with the molar volume concentration of 3 mol/L. Respectively taking the metal ion mixed solution and the ammonium bicarbonate solution according to the volume ratio of 1: 2, slowly dripping the metal ion mixed solution into the ammonium bicarbonate solution while stirring the ammonium bicarbonate solution, and after dripping is finished, adding a small amount of ammonia water to adjust the pH value of a precipitation system to be 9. And after the precipitation reaction is finished, performing centrifugal separation, pouring out supernatant liquid, and drying the precipitate in an oven at the temperature of 60 ℃ for 24 hours to obtain white precursor powder. Respectively taking precursor powder and NH 4 Cl, and mixing uniformly to obtain mixed powder, wherein NH is contained in the mixed powder 4 The mass fraction of Cl was 1wt%. The mixed powder was transferred to a corundum crucible and then charged with 95% by volume of N 2 And 5% of H 2 Heating to 1350 deg.C at a rate of 5 deg.C/min in a tube furnace with reducing atmosphere, calcining for 8 hr, cooling, and grinding to obtain Ba 0.89 Sr 0.02 Eu 0.09 Mg 0.87 Mn 0.13 Al 10 O 17 And (4) green fluorescent powder. Taking the automobile varnish, and then taking Ba with the mass being 40% of the automobile varnish 0.89 Sr 0.02 Eu 0.09 Mg 0.87 Mn 0.13 Al 10 O 17 And (3) uniformly mixing the green fluorescent powder to obtain the BAM EM-based fluorescent whitening automobile paint.
From fig. 8, it can be seen that the xrd diffraction pattern of the phosphor prepared in example 4 is consistent with that of the standard card, indicating that the sample obtained in example 4 is BAM, and has no other impurity peaks, indicating no impurities. It can be seen from FIG. 9 that the emission position of the phosphor prepared in example 4 is 513nm, which is not much different from the emission spectrum position of the phosphor prepared in example 1. The broad peak of the excitation peak of the phosphor prepared in example 4 is 350nm to 400 nm. Also, the fluorescent powder prepared by the preparation method is green fluorescent powder.
Example 5
According to the chemical formula Ba 0.75 Eu 0.25 Mg 0.3 Mn 0.7 Al 10 O 17 The stoichiometric ratio of the elements in the Eu mill, and the Eu is accurately weighed 2 O 3 、Ba(NO 3 ) 2 、Mg(NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O and MnCl 2 (ii) a Eu is mixed 2 O 3 Completely dissolving in concentrated nitric acid with mass fraction of 68% to obtain a first solution; mixing the first solution with Ba (NO) 3 ) 2 、Sr(NO 3 ) 2 、Mg(NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O and MnCl 2 Adding into deionized water, adjusting the temperature of a magnetic stirrer to about 40 ℃, heating and stirring until solid particles are completely dissolved to obtain a metal ion mixed solution, wherein the rotating speed is 400 r/min; reacting NH 4 HCO 3 Dissolving in deionized water, adjusting the temperature of a magnetic stirrer to about 40 ℃, rotating at a speed of 400r/min, and heating and stirring until solid particles are completely dissolved to obtain an ammonium bicarbonate solution with a molar volume concentration of 3 mol/L. Respectively taking the metal ion mixed solution and the ammonium bicarbonate solution according to the volume ratio of 1: 1.5, slowly dropwise adding the metal ion mixed solution into the ammonium bicarbonate solution while stirring the ammonium bicarbonate solution, and after dropwise adding is finished, adding a small amount of ammonia water to adjust the pH value of a precipitation system to 10. After the precipitation reaction is finished, centrifugal separation is carried out, supernatant liquor is poured off, and the precipitate is placed in a drying oven at 70 ℃ to be dried for 20 hours to obtainWhite precursor powder. Respectively taking precursor powder and NH 4 Cl, and mixing uniformly to obtain mixed powder, wherein NH is contained in the mixed powder 4 The mass fraction of Cl was 1wt%. The mixed powder was transferred to a corundum crucible and then charged with 95% by volume of N 2 And 5% of H 2 Heating to 1200 ℃ at a heating rate of 5 ℃/min in a tube furnace forming a reducing atmosphere, calcining for 8h, cooling along with the furnace, grinding the product to obtain Ba 0.75 Eu 0.25 Mg 0.3 Mn 0.7 Al 10 O 17 And (4) green fluorescent powder. BAM EM based optically brightened automotive paint was then prepared as in example 1.
Example 6
According to the chemical formula Ba 0.5 Eu 0.5 Mg 0.6 Mn 0.4 Al 10 O 17 The stoichiometric ratio of the elements in the Eu mill, and the Eu is accurately weighed 2 O 3 、Ba(NO 3 ) 2 、Mg(NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O and MnCl 2 (ii) a Eu is mixed 2 O 3 Completely dissolving in concentrated nitric acid with the mass fraction of 68% to obtain a first solution; mixing the first solution with Ba (NO) 3 ) 2 、Sr(NO 3 ) 2 、Mg(NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O and MnCl 2 Adding into deionized water, adjusting the temperature of a magnetic stirrer to about 40 ℃, heating and stirring until solid particles are completely dissolved to obtain a metal ion mixed solution, wherein the rotating speed is 450 r/min; reacting NH 4 HCO 3 Dissolving in deionized water, adjusting the temperature of a magnetic stirrer to about 40 ℃, rotating at a speed of 450r/min, and heating and stirring until solid particles are completely dissolved to obtain an ammonium bicarbonate solution with a molar volume concentration of 3 mol/L. Respectively taking the metal ion mixed solution and the ammonium bicarbonate solution according to the volume ratio of 1:1, slowly dripping the metal ion mixed solution into the ammonium bicarbonate solution while stirring the ammonium bicarbonate solution, and after dripping is finished, adding a small amount of ammonia water to adjust the pH value of a precipitation system to 9.5. After the precipitation reaction is finished, centrifugal separation is carried out, supernatant liquor is poured off, and the precipitate is placed in a drying oven at 65 ℃ to be dried for 22 hours to obtain white precursor powder. Respectively taking precursor powder and NH 4 Cl, and mixing uniformly to obtain mixed powder, wherein NH is contained in the mixed powder 4 The mass fraction of Cl was 1wt%. The mixed powder was transferred to a corundum crucible and then charged with 95% by volume of N 2 And 5% of H 2 Heating to 1450 deg.C at a rate of 5 deg.C/min in a tubular furnace with reducing atmosphere, calcining for 8 hr, cooling, and grinding to obtain Ba 0.5 Eu 0.5 Mg 0.6 Mn 0.4 Al 10 O 17 And (4) green fluorescent powder. BAM EM-based optically brightened automotive paint was then prepared as in example 2.
Example 7
According to the chemical formula Ba 0.625 Eu 0.375 Mg 0.9 Mn 0.1 Al 10 O 17 The stoichiometric ratio of each element in the Eu powder is accurately weighed 2 O 3 、Ba(NO 3 ) 2 、Mg(NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O and MnCl 2 (ii) a Eu is added 2 O 3 Completely dissolving in concentrated nitric acid with the mass fraction of 66% to obtain a first solution; mixing the first solution with Ba (NO) 3 ) 2 、Sr(NO 3 ) 2 、Mg(NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O and MnCl 2 The mixture was added to deionized water, and a white precursor powder was obtained in the same manner as in example 1. Respectively taking precursor powder and NH 4 Cl, and mixing uniformly to obtain mixed powder, wherein NH is contained in the mixed powder 4 The mass fraction of Cl was 1wt%. Ba was obtained in the same manner as in example 1 0.625 Eu 0.375 Mg 0.9 Mn 0.1 Al 10 O 17 And (4) green fluorescent powder. BAM EM-based optically brightened automotive paint was then prepared as in example 3.
The invention is based on BAM EM (BaMgAl) 10 O 17 Eu, mn (space group: P63/mmc)) is composed of two parts, namely, an optical functional material and a carrier material. The optical functional material is near ultraviolet excited green fluorescent powder BaMgAl10O17 Eu 2+ ，Mn 2+ For near ultraviolet sunlightHas super-strong absorption and can emit super-strong green fluorescence under the excitation of sunlight. The green phosphor has ultra-high europium ion Eu 2+ And Mn 2+ Concentration, and has a micron scale. When preparing the green phosphor, NH is used 4 Cl is a fluxing agent, the particle size of the fluorescent powder is smaller than 1 mu m under the condition of keeping the brightness, the fluorescent powder is in a submicron scale, and the fluorescent whitening automobile paint can be obtained by dissolving the fluorescent powder into automobile varnish without traces. The fluorescent whitening automobile paint can emit green fluorescence under the irradiation of sunlight, and can embody remarkable fluorescent whitening effect by being matched with white primer of an automobile, thereby constructing a very beautiful white automobile.

Claims (1)

1. A method for preparing a fluorescent whitening automobile paint based on BAM EM is characterized in that the paint is prepared according to the chemical formula Ba 0.6 Eu 0.4 Mg 0.42 Mn 0.58 Al 10 O 17 The stoichiometric ratio of each element in the Eu white-iron powder is accurately weighed, and 0.1407 g of Eu is weighed 2 O 3 0.3136 g Ba (NO) 3 ) 2 0.2156 g Mg (NO) 3 ) 2 ·6H 2 O, 7.5026 g Al (NO) 3 ) 3 ·9H 2 O and 0.1459 g MnCl 2 (ii) a Eu is added 2 O 3 Completely dissolving in concentrated nitric acid with the mass fraction of 65% to obtain a first solution; mixing the first solution with Ba (NO) 3 ) 2 、Mg(NO 3 ) 2 ·6H 2 O、Al(NO 3 ) 3 ·9H 2 O and MnCl 2 Adding into deionized water, adjusting the temperature of a magnetic stirrer to about 40 ℃, heating and stirring until solid particles are completely dissolved to obtain a metal ion mixed solution, wherein the rotating speed is 500 r/min; weigh 11.858 g NH 4 HCO 3 Dissolving in 100mL of deionized water, adjusting the temperature of a magnetic stirrer to about 40 ℃, rotating at a speed of 500r/min, and heating and stirring until solid particles are completely dissolved to obtain an ammonium bicarbonate solution with a molar volume concentration of 3 mol/L; according to the volume ratio of 1:1, respectively taking a metal ion mixed solution and an ammonium bicarbonate solution, slowly dripping the metal ion mixed solution into the ammonium bicarbonate solution while stirring the ammonium bicarbonate solution, and after finishing dripping, adding a small amount of ammonia water to adjust the pH value of a precipitation system to 9; after the precipitation reaction is finished, centrifugal separation is carried out,pouring out the supernatant, and drying the precipitate in a drying oven at 60 ℃ for 24 hours to obtain white precursor powder; respectively taking precursor powder and NH 4 Cl, and mixing uniformly to obtain mixed powder, wherein NH is contained in the mixed powder 4 The mass fraction of Cl is lwt percent, the mixed powder is transferred into a corundum crucible and then is put into a corundum crucible, and 95 percent of N is introduced according to the volume ratio 2 And 5% of H 2 Heating to 1350 ℃ at the heating rate of 5 ℃/min in a tubular furnace forming reducing atmosphere, calcining for 8h, cooling along with the furnace, grinding the product, taking the automobile varnish, and taking Ba accounting for 50% of the mass of the automobile varnish 0.6 Eu 0.4 Mg 0.42 Mn 0.58 Al 10 O 17 Uniformly mixing green fluorescent powder to prepare the BAM EM-based fluorescent whitening automobile paint;
and annealing the prepared near ultraviolet excited submicron green fluorescent powder at 1300 ℃ for 4 to 8 hours to obtain the annealed green fluorescent powder.
CN202010874428.4A 2020-08-27 2020-08-27 Fluorescent whitening automobile paint based on BAM EM and preparation method thereof Active CN111925683B (en)

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CN108410452B (en) * 2017-02-09 2021-03-19 有研稀土新材料股份有限公司 Light-emitting material composition and light-emitting device
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