CN111139069A - Preparation method of rare earth Sm doped barium fluoborate red fluorescent powder - Google Patents

Preparation method of rare earth Sm doped barium fluoborate red fluorescent powder Download PDF

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Publication number
CN111139069A
CN111139069A CN202010012787.9A CN202010012787A CN111139069A CN 111139069 A CN111139069 A CN 111139069A CN 202010012787 A CN202010012787 A CN 202010012787A CN 111139069 A CN111139069 A CN 111139069A
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fluorescent powder
sintering
grinding
temperature
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易昌凤
甄琳
吴佳芮
潘馨圆
杨春雨
肖梓晨
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Hubei University
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Hubei 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
    • 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
    • C09K11/7759—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing samarium
    • C09K11/7762—Halogenides
    • C09K11/7763—Halogenides with alkali or alkaline earth metals

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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention discloses a preparation method of rare earth Sm doped barium fluoborate red fluorescent powder, which comprises the following steps: 1) pre-sintering: weighing the raw material BaCO according to the proportion3、BaF2、H3BO3And Sm accounting for 0.05-15 percent of the total substance of the system2O3Grinding for 10-30 minutes, transferring the mixed powder into a crucible, putting the crucible into a high-temperature calcining furnace, and pre-sintering for 4-10 hours at the temperature of 600-1400 ℃ to obtain a pre-sintered sample; 2) preparing fluorescent powder: after cooling to room temperature, grinding for 5-7 minutes again, uniformly mixing, sintering at 800-1500 ℃ for 5-8 hours, cooling to room temperature to prepare powder, and obtaining the fluorescent powder; the step 1) and the step 2) are carried out in air. The invention optimizes the relevant preparation process of the red fluorescent powder, has environment-friendly preparation process, and the obtained fluorescent powder has more stable physicochemical property, relatively higher luminous efficiency, enhanced luminous performance, good luminous stability and luminous color rendering property and lower color temperature. The invention has wide market prospect.

Description

Preparation method of rare earth Sm doped barium fluoborate red fluorescent powder
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a preparation method of rare earth Sm doped barium fluoborate red fluorescent powder.
Background
With the development of science and technology, the problems of energy and environment are more and more emphasized, wherein the illumination field accounts for 19% of the total energy consumption, and the energy consumption in the aspect is greatly reduced along with the more and more obvious advantages of Light Emitting Diodes (LEDs) in the illumination field, so that the research on the LEDs is deep, and the application of the LEDs in the illumination field is promoted to have great significance. In addition, compared with incandescent lamps, fluorescent lamps and high-pressure gas discharge lamps, the LED is more energy-saving and environment-friendly, can reduce pollution to the environment to a great extent, and has important value on global sustainable development. Since the performance of the phosphor, which is an important component of the LED, directly affects the lifetime and illumination efficiency of the LED, the phosphor having high efficiency is continuously searched.
The rare earth Sm has rich energy levels, wherein a plurality of energy level transitions are positioned in a visible light region, and can well output red light and orange light. Sm, a common variable-valence rare earth ion, has been subjected to a series of intensive research and study by researchers over the past several decades due to its red down-conversion luminescence and its application characteristics in high-density optical storage. Sm3+Structure of ion and Eu3+Ion similarity and bright pure red luminescence can be obtained by down-conversion excitation, but Eu3+Higher price, increased cost of the phosphor, Sm3+The ion has a wide spectral range and has a high-efficiency fluorescence emitter in the ultraviolet to infrared regions. Since the room temperature spectral hole burning phenomenon based on Sm ions is reported for the first time, Sm ion doped fluorohalide mixed crystals show great potential application value in ultra-high density spectral data storage.
In previous reports, although there have been many discussions about boric acid systems, Ba-based5(BO3)3Phosphors of F have been rarely discussed. Have not yet been concerned withBa5(BO3)3Sm of F3+And (5) a research report of doped fluorescent powder. Thus, Ba of the present invention5(BO3)3F：Sm3+The fluorescent powder is a novel fluorescent powder.
At present, the most popular red fluorescent powder in the market has unstable physical and chemical properties, the preparation process is not environment-friendly, the luminous efficiency is low under the excitation light of 380-420nm, and the requirements of consumers can not be well met. In addition, the problems and disadvantages of low luminous stability and luminous efficiency of the fluorescent powder, poor luminous color rendering property of the LED, high color temperature and the like are urgently solved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides the preparation method of the rare earth Sm-doped barium fluoborate red fluorescent powder, which has the advantages of stable physical and chemical properties of products, high luminous efficiency, good luminous stability and luminous color rendering property, lower color temperature and environment-friendly preparation process.
In order to achieve the technical purpose, the preparation method of the rare earth Sm doped barium fluoborate red fluorescent powder is characterized by comprising the following steps:
1) pre-sintering: respectively weighing the raw material BaCO according to the subscript proportion of the elements in the molecular formula3、BaF2、H3BO3And Sm accounting for 0.05-15 percent of the total substance of the system2O3Grinding for 10-30 minutes, transferring the mixed powder into a crucible, putting the crucible into a high-temperature calcining furnace, and pre-sintering for 4-10 hours at the temperature of 600-1400 ℃ to obtain a pre-sintered sample;
2) preparation of the phosphor: cooling the pre-sintered sample in the step 1) to room temperature, taking out and grinding for 5-7 minutes, mixing uniformly, sintering at 800-1500 ℃ for 5-8 hours, naturally cooling to room temperature, and preparing the obtained sample into powder to obtain the fluorescent powder, namely Ba5(BO3)3F, x% Sm fluorescent powder, and the doping range is correspondingly 0.05% -15%;
the step 1) and the step 2) are carried out in air.
Preferably, the BaCO is weighed in the step (1)3Is 4.430mmol, said Sm2O3The grinding time is 20 minutes, the pre-sintering temperature is 1400 ℃, and the time is 4 hours; in the step (2), the grinding time is 7 minutes, the sintering temperature is 1200 ℃, the sintering time is 5 hours, and the obtained Ba5(BO3)3F, x% Sm fluorescent powder is Ba5(BO3)3F, 7.0 percent of Sm fluorescent powder.
Further preferably, the grinding is carried out in an agate mortar.
The beneficial effects of the invention at least comprise: the invention provides a novel energy-saving environment-friendly luminescent material taking barium fluoborate as a substrate, which can generate red fluorescence by doping trivalent samarium ions.
Drawings
FIG. 1 shows Ba obtained in example 1 of the present invention5(BO3)3XRD pattern of 1.0% Sm fluorescent powder;
FIG. 2 shows Ba obtained in example 1 of the present invention5(BO3)3F, 1.0% Sm fluorescent powder fluorescence map (248 nm);
FIG. 3 shows Ba obtained in example 1 of the present invention5(BO3)3F, 1.0% Sm fluorescent powder fluorescence map (407 nm);
FIG. 4 shows Ba obtained in example 1 of the present invention5(BO3)3F, 1.0% Sm fluorescent powder fluorescence map (607 nm);
FIG. 5 shows Ba obtained in example 2 of the present invention5(BO3)3XRD pattern of 3.0% Sm fluorescent powder;
FIG. 6 shows Ba obtained in example 2 of the present invention5(BO3)3F, 3.0% Sm fluorescent powder fluorescence map (249 nm);
FIG. 7 shows Ba obtained in example 2 of the present invention5(BO3)3F, 3.0% Sm fluorescent powder fluorescence map (407 nm);
FIG. 8 shows Ba obtained in example 2 of the present invention5(BO3)3F, 3.0% Sm fluorescent powder fluorescence map (607 nm);
FIG. 9 shows Ba obtained in example 3 of the present invention5(BO3)3XRD pattern of 5.0% Sm fluorescent powder;
FIG. 10 shows Ba obtained in example 3 of the present invention5(BO3)3F, 5.0% Sm fluorescent powder fluorescence map (249 nm);
FIG. 11 shows Ba obtained in example 3 of the present invention5(BO3)3F, a fluorescent map spectrogram (407nm) of 5.0% Sm fluorescent powder;
FIG. 12 shows Ba obtained in example 3 of the present invention5(BO3)3F, a fluorescent map spectrogram (607nm) of 5.0 percent Sm fluorescent powder;
FIG. 13 shows Ba obtained in example 4 of the present invention5(BO3)3XRD pattern of 7.0% Sm fluorescent powder;
FIG. 14 shows Ba obtained in example 4 of the present invention5(BO3)3F, 7.0% Sm fluorescent powder fluorescence map (249 nm);
FIG. 15 shows Ba obtained in example 4 of the present invention5(BO3)3F, 7.0% Sm fluorescent powder fluorescence map (407 nm);
FIG. 16 shows Ba obtained in example 4 of the present invention5(BO3)3F, 7.0% Sm fluorescent powder fluorescence map (599 nm);
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the following examples. It should be understood that this example is for illustrative purposes only and is not intended to limit the scope of the present invention.
The technical means adopted in the embodiment are conventional in the art, except for specific description.
Example 1
(1) According to the chemical formula Ba4.990Sm0.010(BO3)3The stoichiometric ratio of each element in F is used for preparing fluorescent powder with the total amount of 1mmol, and barium carbonate BaCO is respectively weighed34.490mmol, boric acid H3BO33.0mmol, barium fluoride BaF20.5mmol of samarium oxide Sm doped with 1.0 percent of total substances in the system2O3；
(2) Weighing the well weighed barium carbonate BaCO3Boronic acid H3BO3Barium fluoride BaF2Samarium oxide Sm2O3Grinding the mixture in an agate mortar for 10 minutes, transferring the mixed powder into a crucible, and putting the crucible into a high-temperature calcining furnace for presintering experiments, wherein the presintering temperature is 600 ℃, and the presintering time is 8 hours;
(3) after cooling to room temperature, taking out the obtained substance, putting the substance into an agate mortar again, grinding for 5 minutes, uniformly mixing, and then sintering at 800 ℃ for 8 hours;
(4) naturally cooling to room temperature, and fully grinding to obtain Ba5(BO3)31.0 percent of Sm fluorescent powder, and an XRD map is shown in figure 1, and a fluorescence map is shown in figures 2-4.
Example 2
The method of this example was as described in example 1, except that:
weighing barium carbonate BaCO in step (1)34.470mmol of samarium oxide Sm doped with 3.0 percent of total substances of the system2O3(ii) a In the step (2), the grinding time is 30 minutes, the pre-sintering temperature is 950 ℃, and the time is 4 hours; in the step (3), the grinding time is 7 minutes, the sintering temperature is 1500 ℃, and the time is 5 hours; step (4) obtaining Ba5(BO3)3F is 3.0 percent of Sm fluorescent powder, an XRD map is shown in figure 5, and a fluorescence map is shown in figures 6-8.
Example 3
The method of this example was as described in example 1, except that:
weighing barium carbonate BaCO in step (1)34.450mmol of samarium oxide Sm doped with 5.0 percent of total substances of the system2O3(ii) a In the step (2), the grinding time is 18 minutes, the pre-sintering temperature is 1400 ℃, and the time is 10 hours; the grinding time in the step (3) is 6 minutes,The sintering temperature is 1000 ℃, and the time is 7 h; step (4) obtaining Ba5(BO3)35.0 percent of Sm fluorescent powder, an XRD pattern is shown in figure 9, and a fluorescence pattern is shown in figures 10-12.
Example 4
The method of this example was as described in example 1, except that:
weighing barium carbonate BaCO in step (1)34.430mmol of samarium oxide Sm doped with 7.0 percent of total substances of the system2O3(ii) a In the step (2), the grinding time is 20 minutes, the pre-sintering temperature is 1400 ℃, and the time is 4 hours; in the step (3), the grinding time is 7 minutes, the sintering temperature is 1200 ℃, and the time is 5 hours; step (4) obtaining Ba5(BO3)37.0 percent of Sm fluorescent powder, an XRD pattern is shown in figure 13, and fluorescent patterns are shown in figures 14-16.
Example 5
The method of this example was as described in example 1, except that:
weighing barium carbonate BaCO in step (1)34.430mmol of samarium oxide Sm doped with samarium accounting for 0.05 percent of the total substance of the system2O3(ii) a In the step (2), the grinding time is 10 minutes, the pre-sintering temperature is 1400 ℃, and the time is 6 hours; in the step (3), the grinding time is 7 minutes, the sintering temperature is 800 ℃, and the time is 8 hours; step (4) obtaining Ba5(BO3)3F, 0.05 percent of Sm fluorescent powder.
Example 6
The method of this example was as described in example 1, except that:
weighing barium carbonate BaCO in step (1)34.430mmol of samarium oxide Sm doped with 15 percent of total substances of the system2O3(ii) a In the step (2), the grinding time is 10 minutes, the pre-sintering temperature is 1400 ℃, and the time is 4 hours; in the step (3), the grinding time is 5 minutes, the sintering temperature is 1000 ℃, and the time is 5 hours; step (4) obtaining Ba5(BO3)3F, 15% of Sm fluorescent powder.
As can be seen from the analysis of the XRD spectrum and the fluorescence spectrum of the embodiment, the fluorescent powder obtained by the invention has the advantages of purity, high crystallinity, good physical and chemical properties, high luminous intensity and high efficiency, and the emitted light is suitable for illumination.

Claims (3)

1. A preparation method of rare earth Sm doped barium fluoborate red fluorescent powder is characterized by comprising the following steps:
1) pre-sintering: respectively weighing the raw material BaCO according to the subscript proportion of the elements in the molecular formula3、BaF2、H3BO3And Sm accounting for 0.05-15 percent of the total substance of the system2O3Grinding for 10-30 minutes, transferring the mixed powder into a crucible, putting the crucible into a high-temperature calcining furnace, and pre-sintering for 4-10 hours at the temperature of 600-1400 ℃ to obtain a pre-sintered sample;
2) preparation of the phosphor: cooling the pre-sintered sample in the step 1) to room temperature, taking out and grinding for 5-7 minutes, mixing uniformly, sintering at 800-1500 ℃ for 5-8 hours, naturally cooling to room temperature, and preparing the obtained sample into powder to obtain the fluorescent powder, namely Ba5(BO3)3F, x% Sm fluorescent powder, and the doping range is correspondingly 0.05% -15%;
the step 1) and the step 2) are carried out in air.
2. The method of claim 1, wherein the rare earth Sm is doped with barium fluoborate red phosphor, the method comprises: weighing BaCO in the step (1)34.430mmol of Sm2O3The grinding time is 20 minutes, the pre-sintering temperature is 1400 ℃, and the time is 4 hours; in the step (2), the grinding time is 7 minutes, the sintering temperature is 1200 ℃, the sintering time is 5 hours, and the obtained Ba5(BO3)3F, x% Sm fluorescent powder is Ba5(BO3)3F, 7.0 percent of Sm fluorescent powder.
3. The method of claim 2, wherein the rare earth Sm is doped with barium fluoborate red phosphor comprises: the grinding is carried out in an agate mortar.
CN202010012787.9A 2020-01-07 2020-01-07 Preparation method of rare earth Sm doped barium fluoborate red fluorescent powder Pending CN111139069A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115231824A (en) * 2021-04-22 2022-10-25 天津工业大学 Rare earth element Tm doped fluoborate luminescent glass and preparation method thereof

Citations (2)

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Publication number Priority date Publication date Assignee Title
CN101514489A (en) * 2008-02-22 2009-08-26 中国科学院理化技术研究所 Fluoborate containing rare earth ions, crystal, growth method and application of crystal
CN102140347A (en) * 2010-01-28 2011-08-03 海洋王照明科技股份有限公司 Borofluoride white light emitting material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101514489A (en) * 2008-02-22 2009-08-26 中国科学院理化技术研究所 Fluoborate containing rare earth ions, crystal, growth method and application of crystal
CN102140347A (en) * 2010-01-28 2011-08-03 海洋王照明科技股份有限公司 Borofluoride white light emitting material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUHAN ZHU ET AL.: "Anomalous 5D0-7FJ photoluminescence properties and the random site occupancy of Eu3+ in Sr5(BO3)3F", 《CERAMICS INTERNATIONAL》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115231824A (en) * 2021-04-22 2022-10-25 天津工业大学 Rare earth element Tm doped fluoborate luminescent glass and preparation method thereof
CN115231824B (en) * 2021-04-22 2023-12-01 天津工业大学 Rare earth element Tm doped fluoborate luminescent glass and preparation method thereof

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Application publication date: 20200512