CN114736682B - BaY prepared by using rotary oscillation high-temperature furnace 4 Si 3 O 13 :Eu 3+ Method for preparing red fluorescent powder - Google Patents

BaY prepared by using rotary oscillation high-temperature furnace 4 Si 3 O 13 :Eu 3+ Method for preparing red fluorescent powder Download PDF

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CN114736682B
CN114736682B CN202210392157.8A CN202210392157A CN114736682B CN 114736682 B CN114736682 B CN 114736682B CN 202210392157 A CN202210392157 A CN 202210392157A CN 114736682 B CN114736682 B CN 114736682B
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temperature
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CN114736682A (en
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朱崇强
刘景祥
杨雪
杨春晖
郝树伟
雷作涛
宋梁成
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Harbin Institute of Technology
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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
    • C09K11/7783—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
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B14/00—Crucible or pot furnaces
    • F27B14/02—Crucible or pot furnaces with tilting or rocking arrangements
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B14/00—Crucible or pot furnaces
    • F27B14/08—Details peculiar to crucible or pot furnaces
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B14/00—Crucible or pot furnaces
    • F27B14/08—Details peculiar to crucible or pot furnaces
    • F27B14/10—Crucibles
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B14/00—Crucible or pot furnaces
    • F27B14/08—Details peculiar to crucible or pot furnaces
    • F27B14/20—Arrangement of controlling, monitoring, alarm or like devices
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

BaY prepared by using rotary oscillation high-temperature furnace 4 Si 3 O 13 :Eu 3+ A method for preparing red fluorescent powder relates to a method for preparing fluorescent powder. The method aims to solve the technical problems that the heat transfer of the existing high-temperature furnace is unstable, and the product is easy to crystallize to generate impure phases. The method comprises the following steps: 1. according to BaY 4 Si 3 O 13 :Eu 3+ Accurately weighing the raw materials according to the stoichiometric ratio, grinding and drying to obtain a mixed raw material; 2. drying the isopropanol and residual moisture; 3. transferring the mixed raw materials into a ceramic crucible; 4. sintering in a rotary oscillation high-temperature furnace; 5. grinding, cleaning and drying to obtain BaY 4 Si 3 O 13 :Eu 3+ And (4) red fluorescent powder. Eu in the red fluorescent powder 3+ Doping into the interior of the crystal lattice to make Eu also 3+ Can absorb more near ultraviolet light and blue light, and improves the luminous intensity and the purity of red light. The red fluorescent powder can be used in the fields of LED illumination and displays.

Description

BaY prepared by using rotary oscillation high-temperature furnace 4 Si 3 O 13 :Eu 3+ Method for preparing red fluorescent powder
Technical Field
The invention relates to a preparation method of fluorescent powder.
Background
The high-temperature sintering furnace plays a great role in a method for preparing crystals on a large scale, and the high-temperature sintering furnace is required to be used for preparing almost all high-melting-point crystals, and the high-temperature sintering furnace is used for carrying out heat preservation operation at high temperature so as to synthesize or grow the crystals. However, when the existing high-temperature sintering furnace works, the crucible is placed at the bottom of the hearth and is fixed, the temperature in the crucible is easy to be disturbed due to uneven heat transfer of the hearth in the temperature rising and falling process, and the slight disturbance of the temperature can cause the dislocation of arrangement in the crystal growth process; on the other hand, the raw materials in the crucible are static during heat preservation, and when various raw materials are contained, impurity phases are easy to crystallize due to nonuniform mixing of local raw materials, so that the quality of crystals is influenced.
Disclosure of Invention
The invention aims to solve the technical problems that the heat transfer of the existing high-temperature furnace is unstable and the product is easy to crystallize to produce impure phase, and provides a method for preparing BaY by using a rotary oscillation high-temperature furnace 4 Si 3 O 13 :Eu 3+ Red fluorescent powder.
The invention relates to a method for preparing BaY by utilizing a rotary oscillation high-temperature furnace 4 Si 3 O 13 :Eu 3+ The method of the red fluorescent powder comprises the following steps:
1. according to BaY 4 Si 3 O 13 :Eu 3+ Accurately weighing BaCO according to the stoichiometric ratio 3 、Y 2 O 3 、SiO 2 、Eu 2 O 3 Wherein Eu is 3+ The doping amount is calculated according to 11 to 20 percent; then weighing the fluxing agent Li 2 CO 3 Wherein Li 2 CO 3 Accounts for BaCO 3 3% -7% of the amount of the substance(s); adding the weighed raw materials into an agate mortar, adding isopropanol, uniformly stirring to form paste, and uniformly grinding; drying to obtain a mixed raw material;
2. transferring the mixed raw materials into a ceramic crucible, and putting the ceramic crucible into an oven to keep the temperature of the ceramic crucible at 100 ℃ for 40-50 min; fully volatilizing the isopropanol and residual moisture;
3. after the crucible opening is sealed tightly, fixing the crucible in a crucible support in a rotary oscillation high-temperature furnace hearth;
4. sintering was carried out according to the following temperature control program:
(1) The temperature in the hearth is increased from room temperature to 800-810 ℃ at the speed of 5-8 ℃/min, and the crucible support is only rotated at the rotating speed of 4-5 r/min while the temperature is increased;
(2) Keeping the temperature in the hearth at 800-810 ℃ for 120-130 min, and only vibrating the crucible support at the vibration frequency of 1-1.5 Hz while keeping the temperature;
(3) The temperature in the hearth is increased from 800-810 ℃ to 1150-1450 ℃ at the speed of 4-5 ℃/min, and only the crucible holder rotates at the rotating speed of 4-5 r/min while the temperature is increased;
(4) The temperature in the hearth is kept at 1150-1450 ℃ for 2-4 h, and the crucible tray is only vibrated at the vibration frequency of 1-1.5 Hz while the temperature is kept;
(5) The temperature in the hearth is reduced from 1150-1450 ℃ to room temperature at the speed of 5-8 ℃/min, and only the crucible support rotates at the rotating speed of 4-5 r/min during the temperature reduction;
5. taking out the product from the rotary oscillation high-temperature furnace, grinding, cleaning and drying to obtain BaY 4 Si 3 O 13 :Eu 3+ And (4) red fluorescent powder.
Further, baCO described in step one 3 、Y 2 O 3 、SiO 2 、Eu 2 O 3 、Li 2 CO 3 The purity of the product is more than or equal to 4N.
Further, the amount of the isopropyl alcohol added in the first step is that of adding 0.6 to 1mL of isopropyl alcohol to 1 g of the solid raw material.
Furthermore, the rotary oscillation high-temperature furnace in the third step comprises a support frame 1, a furnace chamber 2, a crucible support 3, a hollow sleeve 4, a support rod 5, a ceramic crucible 6, a rotary disk 7, a bolt 8, a belt pulley 9, a rotary motor 10, a belt 11, a lifting platform 12, a vibrating rod 13 and a vibrating motor 14; the support frame 1 comprises an upper platform 1-1 and a lower platform 1-2; the upper-layer platform 1-1 is provided with a first through hole 1-3 and a mounting hole 1-4; the lower platform 1-2 is provided with a second through hole 1-5; a third hole is arranged below the hearth 2; a fourth hole is arranged in the center of the rotating disc 7; the rotating disc 7 is arranged on the lower platform 1-2; the axes of the third hole, the first through hole 1-3, the second through hole 1-5 and the fourth hole are on the same straight line; the support rod 5 is a hollow cylindrical ceramic tube, and the lower end of the support rod 5 is fixed on the rotating disc 7; the upper end of the support rod 5 is inserted into the hearth 2 through the first through hole 1-3 and the third through hole; the hollow sleeve 4 is fixed below the crucible support 3 and is of an integrated structure; the hollow sleeve 4 is sleeved outside the support rod 5, the lower end of the hollow sleeve 4 extends out of the hearth 2, the lower end of the hollow sleeve 4 is provided with a bolt 8, and the bolt 8 is used for controlling the connection and the fixation of the hollow sleeve 4 and the support rod 5; the rotary motor 10 is arranged on the upper-layer platform 1-1, a belt pulley 9 is fixed outside the support rod 5 positioned between the upper-layer platform 1-1 and the lower-layer platform 1-2, and the belt pulley 9 is connected with the rotary motor 10 through a belt 11; the vibrating rod 13 is of a solid structure, the bottom end of the vibrating rod 13 is fixed on the lifting platform 12, the vibrating rod 13 is inserted into the cavity of the supporting rod 5 through the second through holes 1-5 and the fourth through hole, the distance between the top end of the vibrating rod 13 and the bottom of the crucible holder is adjusted through the lifting platform 12, and the vibrating motor 14 is arranged on the lifting platform 12 and is fixedly connected with the vibrating rod 13; the crucible support 3 is cylindrical, the crucible support 3 is positioned at the central position of the furnace chamber 2, 4 grooves 15 with oval cross sections are uniformly distributed in the crucible support 3, and 4 ceramic crucibles 6 are fixed in the grooves 15; a heating device is arranged in the hearth 2.
Further, the grinding in the fifth step is to grind the product to 200-500 meshes;
furthermore, the cleaning in the fifth step is performed by washing twice with deionized water and then washing once with isopropanol.
Furthermore, the drying in the step five is drying in an oven with the temperature of 90-100 ℃ for 4-5 h.
The rotary oscillation high-temperature furnace is improved on the basis of the existing high-temperature sintering furnace, a rotary and oscillating device is additionally arranged in the center of a hearth of the rotary oscillation high-temperature furnace, and the rotary and oscillating processes and the sintering process are independent. According to the rotary oscillation high-temperature furnace, the hollow sleeve and the supporting rod are connected and fixed together through the bolt, when the rotary motor works, the supporting rod is driven to rotate through the belt, and the crucible holder also rotates under the fixing action of the bolt, so that the crucible is driven to rotate around the axis of the crucible holder at the central position of the furnace body, the uniform heat transfer is promoted, and the rotating speed can be adjusted by controlling the power of the motor. Extract the bolt to on jacking the crucible with lift platform makes the top of vibrating arm push up the support of crucible, vibrating motor during operation directly transmits the vibration for the bracing piece, and the vibration of bracing piece is held in the palm through the crucible and is transmitted former in crucible and the crucibleAnd the material realizes the powder dynamization in the sintering process and promotes the crystallization process, and the oscillation frequency can be adjusted according to the motor frequency. The rotary oscillation high-temperature furnace can avoid dislocation in crystals caused by heat transfer of the hearth of the high-temperature sintering furnace, can also avoid impurity phases caused by static sintering, and can improve the uniformity of crystal products. BaY prepared by using rotary oscillation high-temperature furnace 4 Si 3 O 13 :Eu 3+ The red phosphor can promote Eu by rotation and oscillation during heat treatment 3+ Better doping into the interior of crystal lattice and making Eu also 3+ Can absorb more near ultraviolet light and blue light, improve the luminous intensity of the red light and simultaneously improve the purity of the red light. The rotary oscillation high-temperature furnace can be used in the field of high-temperature synthesis.
Drawings
FIG. 1 is a schematic structural view of a rotary oscillation high-temperature furnace of example 1;
FIG. 2 is a schematic view showing the connection of a susceptor 3, a hollow sleeve 4, a support rod 5 and a vibration rod 13 in the rotary oscillation high-temperature furnace according to example 1;
FIG. 3 is a schematic structural view of a supporter 1 of a rotary oscillation high-temperature furnace according to embodiment 1;
FIG. 4 is a schematic top view of the inside of a furnace chamber 2 of a rotary oscillation high-temperature furnace according to example 1;
FIG. 5 is a schematic view showing the structures of a susceptor 3 and a ceramic crucible 6 of example 1;
FIG. 6 shows BaY prepared in example 1 4 Si 3 O 13 :Eu 3+ Red phosphor and BaY prepared by comparative experiment 4 Si 3 O 13 :Eu 3 + XRD spectrogram of red phosphor;
FIG. 7 is BaY prepared in example 1 4 Si 3 O 13 :Eu 3+ Red phosphor and BaY prepared by comparative experiment 4 Si 3 O 13 :Eu 3 + An excitation spectrum of the red phosphor;
FIG. 8 shows BaY prepared in example 1 4 Si 3 O 13 :Eu 3+ Red phosphor and B prepared by comparative experimentaY 4 Si 3 O 13 :Eu 3 + Emission spectrogram of red phosphor;
FIG. 9 shows BaY prepared in example 1 4 Si 3 O 13 :Eu 3+ Red phosphor and BaY prepared by comparative experiment 4 Si 3 O 13 :Eu 3 + A CIE color coordinate diagram of the red fluorescent powder and a photograph taken by an ultraviolet analyzer;
FIG. 10 is BaY prepared in example 1 4 Si 3 O 13 :Eu 3+ Scanning electron microscope photograph of red fluorescent powder.
FIG. 11 is BaY prepared in example 1 4 Si 3 O 13 :Eu 3+ Red phosphor and commercial Y 2 O 2 S:Eu 3+ A color coordinate comparison chart of the red fluorescent powder;
FIG. 12 is BaY prepared in example 1 4 Si 3 O 13 :Eu 3+ A fluorescence attenuation curve and a fitting result graph of the red fluorescent powder;
FIG. 13 is BaY prepared in example 2 4 Si 3 O 13 :Eu 3+ XRD spectrogram of red phosphor;
FIG. 14 is BaY prepared in example 2 4 Si 3 O 13 :Eu 3+ Emission spectrogram of red phosphor;
in fig. 1-5, 1 is a support frame, 1-1 is an upper platform, 1-2 is a lower platform, 1-3 is a first through hole, 1-4 is a mounting hole, and 1-5 is a second through hole 1-5;2 is furnace, 3 is crucible holds in the palm, 4 is the cavity sleeve pipe, 5 is the bracing piece, 6 is ceramic crucible, 7 is the carousel, 8 is the bolt, 9 is the belt pulley, 10 is the rotating electrical machines, 11 is the belt, 12 is lift platform, 13 is the vibrating arm, 14 is vibrating motor, 15 is the cell body, 16 is the crucible lid.
Detailed Description
The following examples are used to demonstrate the beneficial effects of the present invention:
example 1: baY preparation by utilizing rotary oscillation high-temperature furnace 4 Si 3 O 13 :Eu 3+ The method of the red fluorescent powder comprises the following steps:
1. according to BaY 4 Si 3 O 13 :Eu 3+ Accurately weighing 0.9867 g of BaCO according to the stoichiometric ratio 3 1.8516 g Y 2 O 3 0.9012 g of SiO 2 0.6335 g Eu 2 O 3 (Eu 3+ The doping amount is 18 percent); then 0.0185 g of fluxing agent Li is weighed 2 CO 3 (ii) a Adding all the weighed raw materials into an agate mortar, adding 3.5mL of isopropanol, uniformly stirring to form a paste, and grinding for 30min to uniformly mix raw material particles; drying to obtain a mixed raw material; wherein BaCO 3 、Y 2 O 3 、SiO 2 、Eu 2 O 3 、Li 2 CO 3 The purity of (A) is 4N;
2. transferring the mixed raw materials into a ceramic crucible 6, and placing the ceramic crucible into an oven to keep the temperature of the ceramic crucible at 100 ℃ for 40min; fully volatilizing the isopropanol and residual moisture;
3. after the crucible opening is tightly sealed by a crucible cover, fixing the ceramic crucible 6 in a groove 15 of a crucible support 3 in a rotary oscillation high-temperature furnace hearth 2; the rotary oscillation high-temperature furnace consists of a support frame 1, a hearth 2, a crucible support 3, a hollow sleeve 4, a support rod 5, a ceramic crucible 6, a rotary disk 7, a plug pin 8, a belt pulley 9, a rotary motor 10, a belt 11, a lifting platform 12, a vibrating rod 13 and a vibrating motor 14; the support frame 1 comprises an upper layer platform 1-1 and a lower layer platform 1-2; the upper-layer platform 1-1 is provided with a first through hole 1-3 and a mounting hole 1-4; the lower platform 1-2 is provided with a second through hole 1-5; a third hole is arranged below the hearth 2; a fourth hole is arranged in the center of the rotating disc 7; the rotating disc 7 is arranged on the lower platform 1-2; the axes of the third hole, the first through hole 1-3, the second through hole 1-5 and the fourth hole are on the same straight line; the support rod 5 is a hollow cylindrical ceramic tube, and the lower end of the support rod 5 is fixed on the rotating disc 7; the upper end of the support rod 5 is inserted into the hearth 2 through the first through hole 1-3 and the third through hole; the hollow sleeve 4 is fixed below the crucible support 3 and is of an integrated structure; the hollow sleeve 4 is sleeved outside the support rod 5, the lower end of the hollow sleeve 4 extends out of the hearth 2, the lower end of the hollow sleeve 4 is provided with a bolt 8, and the bolt 8 is used for controlling the connection, fixation and disconnection of the hollow sleeve 4 and the support rod 5; the rotary motor 10 is arranged on the upper-layer platform 1-1, a belt pulley 9 is fixed outside the support rod 5 positioned between the upper-layer platform 1-1 and the lower-layer platform 1-2, and the belt pulley 9 is connected with the rotary motor 10 through a belt 11; the vibrating rod 13 is of a solid structure, the bottom end of the vibrating rod 13 is fixed on the lifting platform 12, the vibrating rod 13 is inserted into the cavity of the supporting rod 5 through the second through holes 1-5 and the fourth hole, the distance between the top end of the vibrating rod 13 and the bottom of the crucible holder is adjusted through the lifting platform 12, and the vibrating motor 14 is arranged on the lifting platform 12 and is fixedly connected with the vibrating rod 13; the crucible support 3 is cylindrical, the crucible support 3 is positioned at the central position of the hearth 2, 4 grooves 15 with oval sections are uniformly distributed in the crucible support 3, and 4 ceramic crucibles 6 are fixed in the grooves 15; a heating device is arranged in the hearth 2;
4. sintering was carried out according to the following temperature control program:
(1) The hollow sleeve 4 is connected and fixed with the support rod 5 through a bolt 8; the distance between the top end of the vibrating rod 13 and the bottom of the crucible support is adjusted to 10mm through the lifting platform 12; the temperature in the hearth 2 is increased from room temperature to 800 ℃ at the speed of 6.5 ℃/min, and only the crucible support 3 rotates at the rotating speed of 5r/min while the temperature is increased;
(2) The hollow sleeve 4 is separated from the support rod 5 through the bolt 8; the distance between the top end of the vibrating rod 13 and the bottom of the crucible support is adjusted to be 0mm through the lifting platform 12; keeping the temperature in the hearth 2 at 800 ℃ for 120min, and only enabling the crucible holder 3 to vibrate at the vibration frequency of 1Hz while keeping the temperature;
(3) The hollow sleeve 4 is connected and fixed with the support rod 5 through a bolt 8; the distance between the top end of the vibrating rod 13 and the bottom of the crucible support is adjusted to 10mm through the lifting platform 12; the temperature in the hearth 2 is increased from 800 ℃ to 1350 ℃ at the speed of 4.5 ℃/min, and only the crucible support 3 rotates at the rotating speed of 4r/min while the temperature is increased;
(4) The hollow sleeve 4 is separated from the support rod 5 through the bolt 8; the distance between the top end of the vibrating rod 13 and the bottom of the crucible support is adjusted to be 0mm through the lifting platform 12; the temperature in the hearth 2 is kept at 1350 ℃ for 3h, and only the crucible holder 3 is vibrated at the vibration frequency of 1Hz while the temperature is kept;
(5) The hollow sleeve 4 is connected and fixed with the support rod 5 through a bolt 8; the distance between the top end of the vibrating rod 13 and the bottom of the crucible support is adjusted to 10mm through the lifting platform 12; the temperature in the hearth 2 is reduced from 1350 ℃ to room temperature at the speed of 7 ℃/min, and only the crucible support 3 rotates at the rotating speed of 5r/min while the temperature is reduced;
5. taking the product out of the rotary oscillation high-temperature furnace, grinding the product to 300 meshes, washing the product twice by using deionized water, washing the product once by using isopropanol, and finally drying the product for 4 hours in an oven with the temperature of 100 ℃ to obtain BaY 4 Si 3 O 13 :Eu 3+ And (4) red fluorescent powder.
And (3) comparison test: a common high-temperature furnace without rotation and oscillation is used for a comparison test, and the method comprises the following steps:
1. according to BaY 4 Si 3 O 13 :Eu 3+ Accurately weighing 0.9867 g of BaCO according to the stoichiometric ratio 3 1.8516 g of Y 2 O 3 0.9012 g of SiO 2 0.6335 g Eu 2 O 3 (ii) a Then 0.0185 g of fluxing agent Li is weighed 2 CO 3 (ii) a Adding the mixture into an agate mortar, adding 3.5mL of isopropanol, uniformly stirring to form a paste, and grinding for 30min to uniformly mix raw material particles; drying to obtain a mixed raw material; wherein BaCO 3 、Y 2 O 3 、SiO 2 、Eu 2 O 3 、Li 2 CO 3 The purity of (A) is 4N;
2. transferring the mixed raw materials into a ceramic crucible, and placing the ceramic crucible into an oven to keep the temperature of the ceramic crucible at 100 ℃ for 40min; fully volatilizing the isopropanol and residual moisture;
3. covering a crucible cover on the crucible and placing the crucible cover in a hearth in normal high temperature without rotation and oscillation;
4. sintering was carried out according to the following temperature control program:
(1) The temperature in the hearth 2 is increased from room temperature to 800 ℃ at the speed of 6.5 ℃/min;
(2) Keeping the temperature in the hearth 2 at 800 ℃ for 120min;
(3) The temperature in the hearth 2 is increased from 800 ℃ to 1350 ℃ at the speed of 4.5 ℃/min;
(4) Keeping the temperature in the hearth 2 at 1350 ℃ for 3h;
(5) The temperature in the hearth 2 is reduced from 1350 ℃ to room temperature at the speed of 7 ℃/min;
5. taking the product out of the rotary oscillation high-temperature furnace, grinding the product to 300 meshes, washing the product twice by using deionized water, washing the product once by using isopropanol, and finally drying the product for 4 hours in an oven with the temperature of 100 ℃ to obtain comparative BaY 4 Si 3 O 13 :Eu 3+ And (4) red fluorescent powder.
BaY prepared in example 1 4 Si 3 O 13 :Eu 3+ Red phosphor and BaY prepared by comparative experiment 4 Si 3 O 13 :Eu 3+ XRD test is carried out on the red fluorescent powder, the obtained XRD spectrogram is shown in figure 6, and as can be seen from figure 6, baY prepared by using a rotary oscillation high-temperature furnace is compared with a standard PDF card 4 Si 3 O 13 :Eu 3+ The red fluorescent powder can be well matched with a standard card, particularly the position of a characteristic peak at 25-30 degrees can be well matched with the peak intensity, and the fact that Eu can be promoted by additionally arranging rotation and oscillation during sintering is shown 3+ Better enter the inside of crystal lattice and the prepared crystal has less impurity content.
BaY prepared in example 1 4 Si 3 O 13 :Eu 3+ Red phosphor and BaY prepared by comparative experiment 4 Si 3 O 13 :Eu 3+ The red phosphors are subjected to excitation spectrum test, the obtained excitation spectrum is shown in fig. 7, and the excitation peak positions of the two red phosphors are not obviously changed per se, but the peak intensities are changed. BaY prepared in example 1 4 Si 3 O 13 :Eu 3+ The intensity of the excitation peak of the red phosphor is obviously increased, and the Eu is enabled to be driven by the rotating and oscillating device 3+ More easily enter the internal sites of the crystal lattice to make Eu 3+ The near ultraviolet and blue light can be absorbed more.
BaY prepared in example 1 4 Si 3 O 13 :Eu 3+ Red phosphor and BaY prepared by comparative experiment 4 Si 3 O 13 :Eu 3+ The emission spectrum of the red phosphor is measured, and the obtained emission spectrum is shown in FIG. 8, and it can be seen from FIG. 8 that the sample is obtainedBaY prepared in example 1 4 Si 3 O 13 :Eu 3+ The peak value of the emission spectrum of the red fluorescent powder is integrally higher than that of BaY prepared by a contrast test 4 Si 3 O 13 :Eu 3 + The red phosphor, consistent with the excitation spectrum results, also shows that the rotating and oscillating device promotes Eu 3+ And the light enters the internal sites of the crystal lattice, so that the luminous intensity of red light is improved.
BaY prepared in example 1 4 Si 3 O 13 :Eu 3+ Red phosphor and BaY prepared by comparative experiment 4 Si 3 O 13 :Eu 3+ The emission spectrum data of the red fluorescent powder is led into CIE-1931 chromaticity diagram software, and a CIE color coordinate diagram obtained by calculation is shown in FIG. 9 and can directly reflect the luminous color of a sample. BaY prepared by comparative experiment 4 Si 3 O 13 :Eu 3+ Red phosphor having CIE color coordinates (0.619, 0.347), baY prepared in example 1 4 Si 3 O 13 :Eu 3+ The color coordinate of the red fluorescent powder is (0.644, 0.345), and it can be obviously seen that the red light purity of the sample is obviously improved by the rotating and oscillating device.
BaY prepared in example 1 was observed by taking a photograph with an ultraviolet analyzer 4 Si 3 O 13 :Eu 3+ Red phosphor vs. BaY prepared by comparative experiment 4 Si 3 O 13 :Eu 3+ The red light purity of the red fluorescent powder is obviously increased. The luminous purity was calculated by equation 1:
Figure BDA0003596109430000071
wherein (x) i ，y i ) Is the standard daylight color coordinate, the value is (0.31, 0.316),
(x d ，y d ) For the color coordinate of 613nm, the color coordinate (x) of 613nm is obtained by looking up the table d ，y d ) Is (0.67, 0.32);
and (x, y) preparing red fluorescent powder CIE color coordinates.
Calculated BaY prepared by comparative experiment 4 Si 3 O 13 :Eu 3+ The luminous purity of the red fluorescent powder is 86.25 percent; baY prepared in example 1 4 Si 3 O 13 :Eu 3+ The luminous purity of the red fluorescent powder is improved to 93.12 percent, which shows that the rotary oscillation device also promotes the luminous purity of red light.
BaY prepared in example 1 4 Si 3 O 13 :Eu 3+ The scanning electron micrograph of the red phosphor is shown in fig. 10, and as can be seen from fig. 10, the sample crystal grain surface is smooth and full, the fusion degree is good, the particle diameter is between 3 and 10 μm, the particle size requirement of the red phosphor for the white light LED can be met, and the red phosphor can be firmly coated on the surface of an ultraviolet/blue light chip.
BaY prepared in example 1 4 Si 3 O 13 :Eu 3+ The red phosphor has a color coordinate of (0.644, 0.345), which is compared to commercial Y 2 O 2 S:Eu 3+ The red phosphor color coordinates (0.631, 0.350) were compared and found to lie in the ratio Y at the CIE color coordinate position as shown in FIG. 11 2 O 2 S:Eu 3+ The red fluorescent powder is in a redder area, and the red light emitting requirement of the commercial red fluorescent powder is met.
BaY prepared in example 1 4 Si 3 O 13 :Eu 3+ The fluorescence attenuation curve and the fitting result of the red phosphor are shown in FIG. 12, and the fluorescence attenuation curve is fitted by formula 2 and Eu is calculated by formula 3 3+ Fluorescence lifetime τ ave . After fitting R 2 The value of 0.9968 is close to 1, which shows that the fitting effect is good and the result is reliable. Calculating tau from the fluorescence lifetime as the elapsed time required for the time when the luminous intensity at the excitation time gradually decays to 1/e of the luminous intensity at the excitation time ave The value is 1.59ms, which is beneficial to continuously maintaining stable luminescence.
Figure BDA0003596109430000072
Figure BDA0003596109430000073
Example 2: baY production Using Rotary Oscillating high-temperature furnace of this example 4 Si 3 O 13 :Eu 3+ The method of the red fluorescent powder comprises the following steps:
1. according to BaY 4 Si 3 O 13 :Eu 3+ Accurately weighing 0.9867 g of BaCO according to the stoichiometric ratio 3 1.8065 g of Y 2 O 3 0.9012 g of SiO 2 0.7039 g Eu 2 O 3 (Eu 3+ The doping amount is 20 percent); then 0.0370 g of Li flux is weighed 2 CO 3 (ii) a Adding all the weighed raw materials into an agate mortar, adding 3.5mL of isopropanol, uniformly stirring to form a paste, and grinding for 30min to uniformly mix raw material particles; drying at the temperature to obtain a mixed raw material; wherein BaCO 3 、Y 2 O 3 、SiO 2 、Eu 2 O 3 、Li 2 CO 3 The purity of (A) is 4N;
2. transferring the mixed raw materials into a ceramic crucible, and placing into an oven to keep the temperature of the oven at 100 ℃ for 40min; fully volatilizing the isopropanol and residual moisture;
3. after the crucible opening is tightly sealed by a crucible cover, fixing the crucible in a groove 15 of a crucible support 3 in a rotary oscillation high-temperature furnace hearth 2; wherein the rotary oscillation high-temperature furnace is the same as the rotary oscillation high-temperature furnace described in the third step of example 1;
4. sintering was carried out according to the following temperature control program:
(1) The hollow sleeve 4 is connected and fixed with the support rod 5 through a bolt 8; the distance between the top end of the vibrating rod 13 and the bottom of the crucible support is adjusted to 10mm through the lifting platform 12; the temperature in the hearth 2 is increased from room temperature to 800 ℃ at the speed of 6.5 ℃/min, and only the crucible support 3 rotates at the rotating speed of 5r/min while the temperature is increased;
(2) The hollow sleeve 4 is separated from the support rod 5 through the bolt 8; the distance between the top end of the vibrating rod 13 and the bottom of the crucible support is adjusted to be 0mm through the lifting platform 12; keeping the temperature in the hearth 2 at 800 ℃ for 120min, and only enabling the crucible holder 3 to vibrate at the vibration frequency of 1Hz while keeping the temperature;
(3) The hollow sleeve 4 is connected and fixed with the support rod 5 through a bolt 8; the distance between the top end of the vibrating rod 13 and the bottom of the crucible support is adjusted to 10mm through the lifting platform 12; the temperature in the hearth 2 is increased from 800 ℃ to 1250 ℃ at the speed of 4.5 ℃/min, and only the crucible support 3 rotates at the rotating speed of 4r/min while the temperature is increased;
(4) The hollow sleeve 4 is separated from the support rod 5 through the bolt 8; the distance between the top end of the vibrating rod 13 and the bottom of the crucible support is adjusted to be 0mm through the lifting platform 12; the temperature in the hearth 2 is kept at 1250 ℃ for 3h, and only the crucible support 3 vibrates at the vibration frequency of 1Hz while the temperature is kept;
(5) The hollow sleeve 4 is connected and fixed with the support rod 5 through a bolt 8; the distance between the top end of the vibrating rod 13 and the bottom of the crucible support is adjusted to 10mm through the lifting platform 12; the temperature in the hearth 2 is reduced from 1250 ℃ to room temperature at the speed of 7 ℃/min, and the crucible support 3 is only rotated at the rotating speed of 5r/min while the temperature is reduced;
5. taking out the product from the rotary oscillation high-temperature furnace, grinding the product to 300 meshes, washing the product with deionized water twice, washing the product with isopropanol once, and finally drying the product in a drying oven at the temperature of 100 ℃ for 4 hours to obtain BaY 4 Si 3 O 13 :Eu 3+ And (4) red fluorescent powder.
BaY obtained in this example 4 Si 3 O 13 :Eu 3+ The XRD of the red phosphor is shown in fig. 13, from which it can be seen that the prepared red phosphor sample still matches well with the standard card. The common leftward shift of the characteristic peak at 25-30 ℃ is due to Eu 3+ Ionic radius greater than Y 3+ Ionic radius, resulting in increased interplanar spacing.
BaY obtained in this example 4 Si 3 O 13 :Eu 3+ The emission spectrum of the red phosphor is shown in fig. 14, and it can be seen that the emission spectra are mainly based on 613nm red and 595nm orange-red, which correspond to Eu respectively 3+ Is/are as follows 5 D 0 - 7 F 2 And 5 D 0 - 7 F 1 transition, top left diagram of the figure is prepared with a UV analyzer irradiating at 365nmThe fluorescent powder sample is photographed, and the prepared sample is found to emit red light with high luminous intensity and high purity.

Claims (6)

1. BaY prepared by using rotary oscillation high-temperature furnace 4 Si 3 O 13 :Eu 3+ The method of the red fluorescent powder is characterized by comprising the following steps:
1. according to BaY 4 Si 3 O 13 :Eu 3+ Accurately weighing BaCO according to the stoichiometric ratio 3 、Y 2 O 3 、SiO 2 、Eu 2 O 3 Wherein Eu is 3+ The doping amount is 11% -20%; then weighing the fluxing agent Li 2 CO 3 Wherein Li 2 CO 3 Occupy BaCO 3 3% -7% of the amount of the substance; adding the weighed raw materials into an agate mortar, adding isopropanol, uniformly stirring to form paste, and uniformly grinding; drying to obtain a mixed raw material;
2. transferring the mixed raw materials into a ceramic crucible, and putting the ceramic crucible into an oven to keep the temperature of the ceramic crucible at 100 ℃ for 40 to 50min; fully volatilizing the isopropanol and residual moisture;
3. after a crucible opening is sealed tightly, fixing the crucible in a crucible support in a rotary oscillation high-temperature furnace hearth; the rotary oscillation high-temperature furnace comprises a support frame (1), a hearth (2), a crucible support (3), a hollow sleeve (4), a support rod (5), a ceramic crucible (6), a rotary disk (7), a plug pin (8), a belt pulley (9), a rotary motor (10), a belt (11), a lifting platform (12), a vibrating rod (13) and a vibrating motor (14); wherein the support frame (1) comprises an upper layer platform (1-1) and a lower layer platform (1-2); the upper-layer platform (1-1) is provided with a first through hole (1-3) and a mounting hole (1-4); the lower platform (1-2) is provided with a second through hole 1-5; a third hole is arranged below the hearth (2); a fourth hole is arranged in the center of the rotating disc (7); the rotating disc (7) is arranged on the lower-layer platform (1-2); the axes of the third hole, the first through hole (1-3), the second through hole (1-5) and the fourth hole are on the same straight line; the support rod (5) is a hollow cylindrical ceramic tube, and the lower end of the support rod (5) is fixed on the rotating disc (7); the upper end of the supporting rod (5) is inserted into the hearth (2) through the first through hole (1-3) and the third through hole; the hollow sleeve (4) is fixed below the crucible support (3) and is of an integrated structure; the hollow sleeve (4) is sleeved outside the support rod (5), the lower end of the hollow sleeve (4) extends out of the hearth (2), the lower end of the hollow sleeve (4) is provided with a bolt (8), and the bolt (8) is used for controlling the connection, fixation and disconnection of the hollow sleeve (4) and the support rod (5); the rotary motor (10) is arranged on the upper-layer platform (1-1), a belt pulley (9) is fixed outside the supporting rod (5) between the upper-layer platform (1-1) and the lower-layer platform (1-2), and the belt pulley (9) is connected with the rotary motor (10) through a belt (11); the vibrating rod (13) is of a solid structure, the bottom end of the vibrating rod (13) is fixed on the lifting platform (12), the vibrating rod (13) is inserted into a cavity of the supporting rod (5) through the second through hole 1-5 and the fourth hole, the distance between the top end of the vibrating rod (13) and the bottom of the crucible support is adjusted through the lifting platform (12), and the vibrating motor (14) is arranged on the lifting platform (12) and is fixedly connected with the vibrating rod (13); the crucible support (3) is cylindrical, the crucible support (3) is positioned at the central position of the hearth (2), 4 grooves (15) with oval cross sections are uniformly distributed in the crucible support (3), and 4 ceramic crucibles (6) are fixed in the grooves (15); a heating device is arranged in the hearth (2);
4. sintering was carried out according to the following temperature control program:
(1) Heating the temperature in the hearth from room temperature to 800-810 ℃ at the speed of 5-8 ℃/min, and only rotating the crucible holder at the rotating speed of 4-5r/min while heating;
(2) Keeping the temperature in the hearth at 800-810 ℃ for 120-130min, and only vibrating the crucible holder at the vibration frequency of 1-1.5 Hz while keeping the temperature;
(3) Heating the temperature in the hearth from 800 to 810 ℃ to 1150 to 1450 ℃ at a speed of 4 to 5 ℃/min, and rotating only the crucible holder at a rotating speed of 4 to 5r/min while heating;
(4) Keeping the temperature in the hearth at 1150-1450 ℃ for 2-4 h, and only vibrating the crucible holder at the vibration frequency of 1-1.5 Hz while keeping the temperature;
(5) Cooling the temperature in the hearth from 1150 to 1450 ℃ to room temperature at the speed of 5 to 8 ℃/min, and rotating only the crucible support at the rotating speed of 4 to 5r/min while cooling;
5. taking out the product from the rotary oscillation high-temperature furnace, grinding, cleaning and drying to obtain BaY 4 Si 3 O 13 :Eu 3+ And (4) red fluorescent powder.
2. The method of claim 1, wherein BaY is prepared by using a rotary oscillating high temperature furnace 4 Si 3 O 13 :Eu 3+ The method of red phosphor is characterized in that the BaCO in the step one 3 、Y 2 O 3 、SiO 2 、Eu 2 O 3 、Li 2 CO 3 The purity of the product is more than or equal to 4N.
3. The method for preparing BaY using a rotary oscillation high temperature furnace according to claim 1 or 2 4 Si 3 O 13 :Eu 3+ The method for preparing the red fluorescent powder is characterized in that the adding amount of the isopropanol in the step one is that the isopropanol is added according to the proportion of adding 0.6 to 1mL of isopropanol into 1 g of solid raw material.
4. The method for preparing BaY using a rotary oscillation high temperature furnace according to claim 1 or 2 4 Si 3 O 13 :Eu 3+ The method for preparing the red fluorescent powder is characterized in that the grinding in the step five is to grind the product to 200-500 meshes.
5. The method for preparing BaY using a rotary oscillation high temperature furnace according to claim 1 or 2 4 Si 3 O 13 :Eu 3+ The method for cleaning the red fluorescent powder is characterized in that the cleaning in the fifth step is to wash twice by using deionized water and wash once by using isopropanol.
6. The method for preparing BaY using a rotary oscillation high temperature furnace according to claim 1 or 2 4 Si 3 O 13 :Eu 3+ The method of red phosphor is characterized by comprising the step fiveThe drying is carried out in an oven with the temperature of 90 to 100 ℃ for 4 to 5 hours.
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