CN112661409A - Blue light-emitting organic-inorganic composite phosphate glass and preparation method and application thereof - Google Patents
Blue light-emitting organic-inorganic composite phosphate glass and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides organic-inorganic composite phosphate glass capable of emitting blue light, a preparation method and application thereof, and belongs to the technical field of organic-inorganic composite luminescent materials. The invention adopts the discharge plasma sintering method to prepare the organic-inorganic composite phosphate glass and controls the degradation temperature T of the organic phosphorus micromolecule luminescent materialdGlass transition temperature T with the phosphate glassgDifference value T ofg‑TdThe temperature is less than or equal to 10 ℃, and organic phosphorus micromolecules can be ensured to enter a glass network structure when the solid-liquid phase of the glass is converted, and the structure of the organic phosphorus micromolecules is not damaged, so that the prepared organic-inorganic composite luminescent phosphate glass has the luminescent brightnessStrong strength, good thermal stability, good chemical stability and the like. The preparation method has the advantages of simple process, convenience, rapidness, greenness, no pollution and the like.
Description
Technical Field
The invention relates to the technical field of organic-inorganic composite luminescent materials, in particular to organic-inorganic composite phosphate glass capable of emitting blue light and a preparation method and application thereof.
Background
With the development of modern science and technology, the requirements of people on the material performance are increasingly diversified, a single material is difficult to meet various requirements, and the organic-inorganic composite material is becoming a new important development direction with extremely rich vitality. Among them, the organic-inorganic composite luminescent glass has wide applications in the fields of illumination, photovoltaics and display.
The traditional organic-inorganic luminescent glass is mainly realized by a sol-gel method, the dispersion degree of the composite material prepared by the sol-gel method can reach the level of nanometer or molecule, but the research on the aspects of the synthesis method, the structure and the performance of the prepared material and the like is not mature theoretically and technically, the material system is limited, various problems exist in the practical use, and the variety of the developed material is limited.
In addition, the sol-gel method usually adopts a plurality of precursor hydrolysis reactions, so that inorganic ions are agglomerated, the production cost is high, the industrial production is not facilitated, the hydrolysis is easy to generate the emission of toxic substances, and the green production is not facilitated. Moreover, the sol-gel method for preparing the organic-inorganic luminescent glass generally comprises the steps of firstly preparing the aerogel and then carrying out high-temperature heat treatment to finally form the glass, however, the organic luminescent substances exist in the organic-inorganic composite aerogel, the temperature of the heat treatment process is low, the aerogel is not completely converted into the glass, and the chemical stability and the thermal stability of the aerogel are poorer than those of the glass.
Disclosure of Invention
The invention aims to provide blue light-emitting organic-inorganic composite phosphate glass and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of organic-inorganic composite phosphate glass capable of emitting blue light, which comprises the following steps:
mixing Li2SO4、Li2O and P2O5Mixing and sintering to obtain phosphate glass;
sequentially crushing and grinding the phosphate glass to obtain phosphate glass powder;
carrying out ball milling mixing on the phosphate glass powder, the organic phosphorus micromolecule luminescent material and a solvent, drying the obtained mixed material, and carrying out discharge plasma sintering on the obtained mixed powder to obtain organic-inorganic composite phosphate glass emitting blue light;
degradation temperature T of the organic phosphorus micromolecule luminescent materialdGlass transition temperature T with the phosphate glassgDifference value T ofg-Td≤10℃。
Preferably, the Li2SO4、Li2O and P2O5The molar ratio of (20-30): 35-45): 35.
Preferably, the particle size of the phosphate glass powder is less than or equal to 100 mu m.
Preferably, the degradation temperature T of the organic phosphorus small molecule luminescent materiald≥300℃。
Preferably, the organic phosphorus small molecule luminescent material comprises
Preferably, the ball milling and mixing time is 24-48 h.
Preferably, the mass ratio of the phosphate glass powder to the organic phosphorus small-molecule luminescent material is (10)3～104):1。
Preferably, the discharge plasma sintering process comprises setting an initial pressure to be 3KN, maintaining the pressure for 6-8 min, heating to a sintering temperature, keeping the temperature for 2-5 min, increasing the pressure to 5KN, maintaining the pressure for 3-6 min, and reducing the pressure to 3 KN; the sintering temperature T and the glass transition temperature T of the phosphate glassgIs satisfied with | T-Tg|≤10℃。
The invention provides blue light-emitting organic-inorganic composite phosphate glass prepared by the preparation method in the technical scheme, which comprises a phosphate glass matrix and an organic emitter doped in the phosphate glass matrix, wherein the organic emitter is an organic phosphorus micromolecule luminescent material.
The invention provides application of the blue light-emitting organic-inorganic composite phosphate glass in the fields of illumination, photovoltaics and display.
The invention provides a preparation method of organic-inorganic composite phosphate glass capable of emitting blue light, which comprises the following steps: mixing Li2SO4、Li2O and P2O5Mixing and sintering to obtain phosphate glass; sequentially crushing and grinding the phosphate glass to obtain phosphate glass powder; carrying out ball milling mixing on the phosphate glass powder, the organic phosphorus micromolecule luminescent material and a solvent, drying the obtained mixed material, and carrying out discharge plasma sintering on the obtained mixed powder to obtain organic-inorganic composite phosphate glass emitting blue light; degradation temperature T of the organic phosphorus micromolecule luminescent materialdGlass transition temperature T with the phosphate glassgDifference value T ofg-Td≤10℃。
The invention adopts the discharge plasma sintering method to prepare the organic-inorganic composite phosphate glass and controls the degradation of the organic phosphorus micromolecule luminescent materialTemperature TdGlass transition temperature T with the phosphate glassgDifference value T ofg-TdThe organic phosphorus micromolecules can enter a glass network structure when the solid-liquid phase of the glass is converted, and the structure of the organic phosphorus micromolecules is not damaged, so that the prepared organic-inorganic composite luminescent phosphate glass has the excellent characteristics of strong luminous brightness, good thermal stability, good chemical stability and the like.
The preparation method has the advantages of simple process, convenience, rapidness, greenness, no pollution and the like.
Drawings
FIG. 1 is a flow chart of a process for preparing a blue light-emitting organic-inorganic composite phosphate glass according to the present invention;
FIG. 2 is a digital photograph of a blue light-emitting organic-inorganic composite phosphate glass prepared in example 1 under irradiation of an ultraviolet lamp;
FIG. 3 is an emission spectrum of a blue light-emitting organic-inorganic composite phosphate glass prepared in example 1.
Detailed Description
As shown in fig. 1, the present invention provides a method for preparing a blue light-emitting organic-inorganic composite phosphate glass, comprising the steps of:
mixing Li2SO4、Li2O and P2O5Mixing and sintering to obtain phosphate glass;
sequentially crushing and grinding the phosphate glass to obtain phosphate glass powder;
and carrying out ball milling and mixing on the phosphate glass powder, the organic phosphorus micromolecule luminescent material and the solvent, drying the obtained mixed material, and carrying out discharge plasma sintering on the obtained mixed powder to obtain the blue light-emitting organic-inorganic composite phosphate glass.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
In the invention, Li2SO4、Li2O and P2O5Mixing and sintering to obtain the phosphate glass. In the present inventionIn the specification, the Li2SO4、Li2O and P2O5The molar ratio of (A) to (B) is preferably (20-30): (35-45): 35, more preferably (22-28): 36-42): 35, and still more preferably (24-26): 38-40): 35.
In the present invention, the Li2SO4、Li2O and P2O5The mixing process is preferably carried out in an agate mortar. After the mixing is completed, the obtained material is placed in a quartz crucible, and the quartz crucible is placed in a muffle furnace for sintering. In the invention, the sintering temperature is preferably 800-1000 ℃, and the time is preferably 30 min.
After the sintering is completed, the present invention preferably pours the obtained molten glass onto a steel plate at room temperature to obtain a phosphate glass block.
After the phosphate glass is obtained, the phosphate glass is sequentially crushed and ground to obtain the phosphate glass powder. In the present invention, the particle size of the phosphate glass frit is preferably 100 μm or less, and the present invention does not specifically limit the specific process of the crushing and grinding, and the phosphate glass frit having the above particle size can be obtained according to a process well known in the art.
After the phosphate glass powder is obtained, the phosphate glass powder, the organic phosphorus micromolecule luminescent material and the solvent are mixed by ball milling, the obtained mixed material is dried, and the obtained mixed powder is subjected to discharge plasma sintering to obtain the blue light emitting organic-inorganic composite phosphate glass. In the invention, the degradation temperature T of the organic phosphorus small-molecule luminescent materialdPreferably more than or equal to 300 ℃, and the degradation temperature T of the organic phosphorus micromolecule luminescent materialdGlass transition temperature T with the phosphate glassgDifference value T ofg-TdPreferably ≦ 10 deg.C.
In the present invention, the organic phosphorus small molecule luminescent material preferably comprises
In the present invention, the organic Phosphorus small molecule luminescent material is preferably prepared according to the prior art (Matthew P.Duffy, phosphor-Based phosphors: Emitters for OLEDs, phosphors, sulfurs, and Silicon,190:845-853,2015), and the organic Phosphorus small molecule luminescent material of the present invention is compound 2a and compound 2b described on page 850 of the prior art.
In the present invention, the mass ratio of the phosphate glass powder to the organic phosphorus small-molecule light-emitting material is preferably (10)3～104) 1, more preferably (3000-8000): 1, and still more preferably (5000-6000): 1.
In the present invention, the solvent is preferably acetone; the process of ball milling and mixing the phosphate glass powder, the organic phosphorus micromolecule luminescent material and the solvent is preferably to dissolve the organic phosphorus micromolecule luminescent material in the solvent, add the phosphate glass powder into the obtained solution, and ball milling and mixing the obtained mixed material. In the invention, the time for ball milling and mixing is preferably 24-48 h, and more preferably 30-36 h; the rotation speed of the ball milling mixing is not specially limited, and the ball milling mixing can be carried out according to the process well known in the field; the ball-milling mixing is preferably carried out in a vessel with smooth ZrO balls, preferably 10mm in particle size.
After the ball milling and mixing are completed, the obtained liquid is preferably poured into a porcelain plate, drying and standing is carried out for 2-4 hours, and after the solvent is evaporated, uniformly mixed powder is scraped from the porcelain plate. In the invention, the drying is preferably carried out in an oven, the drying temperature is preferably 60-150 ℃, and the drying time is preferably 2-4 h, and more preferably 2.5-3.5 h.
After the drying is finished, the mixed powder is placed in a crucible with conductivity, and then is placed in a spark plasma sintering furnace for spark plasma sintering. In the present invention, the crucible having conductivity is preferably a graphite crucible. In the invention, the initial pressure is set to be 3KN, the pressure is maintained for 6-8 min, the temperature is raised to the sintering temperature, the temperature is maintained for 2-5 min, the pressure is raised to 5KN, the pressure is maintained for 3-6 min, and the pressure is reduced to 3KN in the discharge plasma sintering process; glass of the sintering temperature T and the phosphate glassGlass transition temperature TgIs satisfied with | T-TgThe absolute value is less than or equal to 10 ℃. In the invention, the heating rate is preferably 60-100 ℃/min. The invention adopts the spark plasma sintering, the plasma generated by the pulse current and the pressurization in the sintering process are beneficial to reducing the sintering temperature of the powder, and the spark plasma sintering has the characteristics of low voltage and high current, so that a glass phase can be formed between the raw material powder, and further the composite glass is obtained.
After the spark plasma sintering is finished, the temperature is preferably cooled to room temperature by water cooling, a sample is taken out, and the organic-inorganic composite phosphate glass emitting blue light is obtained after grinding and polishing treatment. In the invention, the cooling rate is preferably 15-25 ℃/min, and more preferably 10 ℃/min; the process of the grinding and polishing treatment is not particularly limited in the present invention, and may be performed according to a process well known in the art.
The invention provides blue light-emitting organic-inorganic composite phosphate glass prepared by the preparation method in the technical scheme, which comprises a phosphate glass matrix and an organic emitter doped in the phosphate glass matrix, wherein the organic emitter is an organic phosphorus micromolecule luminescent material. In the invention, the doping amount of the organic emitter in the phosphate glass matrix is preferably 0.01-0.1%, more preferably 0.03-0.08%, and even more preferably 0.05-0.06%.
The invention provides application of the blue light-emitting organic-inorganic composite phosphate glass in the fields of illumination, photovoltaics and display. The method of the present invention is not particularly limited, and the method may be applied according to a method known in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examplesUses organic phosphorus micromolecule luminescent material as
Degradation temperature TdThe temperature was 300 ℃.
Example 1
Weighing 20g of glass raw materials, wherein the glass raw material Li2SO4、Li2O and P2O5In a molar ratio of 20:45: 35; putting the glass raw materials into an agate mortar, uniformly mixing, pouring into a quartz crucible, putting the quartz crucible into a muffle furnace, and sintering at 800 ℃ for 30 min; the resulting glass melt was poured onto a steel plate at room temperature to obtain a phosphate glass block (glass transition temperature T)gAt 297 ℃ Tg-Td<10℃)；
Crushing and grinding the phosphate glass to obtain phosphate glass powder (the particle size is less than or equal to 100 mu m);
dissolving 5mg of organic phosphorus micromolecules in acetone, adding 5000mg of phosphate glass powder into the obtained solution, putting the obtained mixed solution into a container with smooth ZrO balls (the particle size is 10mm), carrying out ball milling and mixing for 48 hours, pouring the obtained mixed liquid into a ceramic dish, putting the ceramic dish into an oven at 80 ℃, standing for 3 hours, after all the solvents are evaporated, scraping the uniformly mixed powder from a porcelain plate, weighing 5g of the uniformly mixed powder, putting the powder into a graphite crucible, placing in a discharge plasma sintering furnace, setting the initial pressure to 3KN, maintaining the pressure for 6min, heating to 295 deg.C at a rate of 60 deg.C/min, keeping the temperature for 5min, increasing pressure to 5KN, maintaining the pressure for 4min, reducing pressure to 3KN, and then cooling to room temperature at the speed of 15 ℃/min by water cooling, taking out a sample, and grinding and polishing to obtain the blue light-emitting organic-inorganic composite phosphate glass.
Example 2
Weighing 20g of glass raw materials, wherein the glass raw material Li2SO4、Li2O and P2O5In a molar ratio of 25:40: 35; putting the glass raw materials into an agate mortar, uniformly mixing, pouring into a quartz crucible, putting the quartz crucible into a muffle furnace, and sintering at 800 ℃ for 30 min; pouring the obtained glass liquid on a steel plate at room temperature to obtain blocky phosphorusAcid salt glass (glass transition temperature T)gAt 295 ℃ and Tg-Td<10℃)；
Crushing and grinding the phosphate glass to obtain phosphate glass powder (the particle size is less than or equal to 100 mu m);
dissolving 4mg of organic phosphorus micromolecules in acetone, adding 5000mg of phosphate glass powder into the obtained solution, putting the obtained mixed solution into a container with smooth ZrO balls (the particle size is 10mm), carrying out ball milling and mixing for 48 hours, pouring the obtained mixed liquid into a ceramic dish, putting the ceramic dish into an oven at 80 ℃, standing for 2 hours, after all the solvents are evaporated, scraping the uniformly mixed powder from a porcelain plate, weighing 5g of the uniformly mixed powder, putting the powder into a graphite crucible, placing in a discharge plasma sintering furnace, setting the initial pressure to be 3KN, maintaining the pressure for 7min, heating to 295 deg.C at a rate of 70 deg.C/min, keeping the temperature for 5min, increasing pressure to 5KN, maintaining the pressure for 4min, reducing pressure to 3KN, and then cooling to room temperature at the speed of 15 ℃/min by water cooling, taking out a sample, and grinding and polishing to obtain the blue light-emitting organic-inorganic composite phosphate glass.
Example 3
Weighing 20g of glass raw materials, wherein the glass raw material Li2SO4、Li2O and P2O5In a molar ratio of 30:35: 35; putting the glass raw materials into an agate mortar, uniformly mixing, pouring into a quartz crucible, putting the quartz crucible into a muffle furnace, and sintering at 800 ℃ for 30 min; the resulting glass melt was poured onto a steel plate at room temperature to obtain a phosphate glass block (glass transition temperature T)gAt 293 ℃ Tg-Td<10℃)；
Crushing and grinding the phosphate glass to obtain phosphate glass powder (the particle size is less than or equal to 100 mu m);
dissolving 3mg of organic phosphorus micromolecules in acetone, adding 5000mg of phosphate glass powder into the obtained solution, putting the obtained mixed solution into a container with smooth ZrO balls (the particle size is 10mm), carrying out ball milling and mixing for 48 hours, pouring the obtained mixed liquid into a ceramic dish, putting the ceramic dish into an oven at 80 ℃, standing for 3 hours, after all the solvents are evaporated, scraping the uniformly mixed powder from a porcelain plate, weighing 5g of the uniformly mixed powder, putting the powder into a graphite crucible, placing in a discharge plasma sintering furnace, setting the initial pressure to be 3KN, maintaining the pressure for 7min, heating to 295 deg.C at a rate of 70 deg.C/min, keeping the temperature for 5min, increasing pressure to 5KN, maintaining the pressure for 4min, reducing pressure to 3KN, and then cooling to room temperature at the speed of 20 ℃/min by water cooling, taking out a sample, and grinding and polishing to obtain the blue light-emitting organic-inorganic composite phosphate glass.
Performance testing
1) The blue light-emitting organic-inorganic composite phosphate glass prepared in example 1 was placed in a muffle furnace at 300 ℃ for thermal stability test, and after 24 hours, the light-emitting property was observed, and the result is shown in fig. 2; as can be seen from FIG. 2, the prepared blue light-emitting organic-inorganic composite phosphate glass can still observe strong blue light emission under the irradiation of an ultraviolet lamp, which shows that the prepared blue light-emitting organic-inorganic composite phosphate glass has excellent thermal stability.
2) The blue light-emitting organic-inorganic composite phosphate glass prepared in example 1 was subjected to emission spectrum test under 365nm light excitation, and the result is shown in fig. 3; as can be seen from FIG. 3, the blue light-emitting organic-inorganic composite phosphate glass can emit blue light having a central wavelength of about 500 nm.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of blue light-emitting organic-inorganic composite phosphate glass comprises the following steps:
mixing Li2SO4、Li2O and P2O5Mixing and sintering to obtain phosphate glass;
sequentially crushing and grinding the phosphate glass to obtain phosphate glass powder;
carrying out ball milling mixing on the phosphate glass powder, the organic phosphorus micromolecule luminescent material and a solvent, drying the obtained mixed material, and carrying out discharge plasma sintering on the obtained mixed powder to obtain organic-inorganic composite phosphate glass emitting blue light;
degradation temperature T of the organic phosphorus micromolecule luminescent materialdGlass transition temperature T with the phosphate glassgDifference value T ofg-Td≤10℃。
2. The production method according to claim 1, wherein the Li is2SO4、Li2O and P2O5The molar ratio of (20-30): 35-45): 35.
3. The method according to claim 1, wherein the particle size of the phosphate glass frit is 100 μm or less.
4. The preparation method according to claim 1, wherein the degradation temperature T of the organic phosphorus small molecule luminescent materiald≥300℃。
5. The preparation method according to claim 1 or 4, wherein the organophosphorus small molecule luminescent material comprises
6. The preparation method of claim 1, wherein the ball milling and mixing time is 24-48 h.
7. The preparation method according to claim 1, wherein the mass ratio of the phosphate glass powder to the organic phosphorus small molecule luminescent material is (10)3～104):1。
8. The method according to claim 1, wherein the spark plasma sintering is performed by setting an initial periodKeeping the pressure at 3KN for 6-8 min, heating to the sintering temperature, keeping the temperature for 2-5 min, increasing the pressure to 5KN, keeping the pressure for 3-6 min, and reducing the pressure to 3 KN; the sintering temperature T and the glass transition temperature T of the phosphate glassgIs satisfied with | T-Tg|≤10℃。
9. The blue light-emitting organic-inorganic composite phosphate glass prepared by the preparation method of any one of claims 1 to 8 comprises a phosphate glass matrix and an organic emitter doped in the phosphate glass matrix, wherein the organic emitter is an organic phosphorus small-molecule luminescent material.
10. Use of the blue light emitting organic-inorganic composite phosphate glass according to claim 9 in the fields of lighting, photovoltaics and displays.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730975A (en) * | 2012-06-20 | 2012-10-17 | 武汉理工大学 | Glass-ceramic and preparation method thereof |
| CN102745893A (en) * | 2012-06-20 | 2012-10-24 | 武汉理工大学 | Composite phosphor luminescent glass and preparation method for same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730975A (en) * | 2012-06-20 | 2012-10-17 | 武汉理工大学 | Glass-ceramic and preparation method thereof |
| CN102745893A (en) * | 2012-06-20 | 2012-10-24 | 武汉理工大学 | Composite phosphor luminescent glass and preparation method for same |
Non-Patent Citations (3)
| Title |
|---|
| A.TIMAR-GABOR 等: "Thermoluminescence and optically stimulated luminescence properties of the 0.5P2O5-xBaO-(0.5-x)Li2O glass systems" * |
| CLAIRE FAVE 等: "First Example of Organophoshorus-Containing Materials for Light-Emitting Diodes" * |
| MUNIA GANGULI 等: "studies of ternary LiSO4-Li2O-P2O5 glasses" * |
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