CN108579633A - A kind of preparation method of rare-earth nanometer particles/polystyrene complex microsphere - Google Patents
A kind of preparation method of rare-earth nanometer particles/polystyrene complex microsphere Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of rare-earth nanometer particles/polystyrene complex microsphere.The present invention improves the carboxyl-content and roughness of Surfaces of Polystyrene Microparticles using institute's self assembly strategy layer by layer, make rare earth ion pass through coordinate bond with a large amount of carboxyl in surface to be connected, to improve the clad ratio of rare-earth nanometer particles, so that the clad ratio of rare-earth nanometer particles is 85 95%, to successfully prepare rare-earth nanometer particles/polystyrene complex microsphere of high clad ratio, the application manufacturing cost is low simultaneously, simple for process, has wide industrial applications foreground.
Description
Technical field
The invention belongs to inorganic/technical field of high-molecule composite preparation, and in particular to a kind of rare-earth nanometer particles/poly-
The preparation method of styrene composite microsphere material.
Background technology
Rare-earth nanometer particles/polystyrene composite microsphere material is a kind of important functional material, since it is with special
Optical property, in recent years it be found that extensive purposes in many fields, such as：Material science, medical imaging, medical diagnosis on disease,
Biomolecule detection etc..Currently, common preparation method is to be respectively synthesized rare-earth nanometer particles and polystyrene microsphere first, so
Functional modification is carried out to their surface afterwards, then tactful by particle and polystyrene by LBL self-assembly and click chemistry etc.
Microballoon is compound.
But current preparation method is led since rare-earth nanometer particles are easily reunited in cumbersome modification and recombination process
It causes the clad ratio of nano-particle relatively low, and fluorescence-intensity decay, is unable to reach the requirement of certain sector applications.
Invention content
In view of the above shortcomings of the prior art, inventor is through long-term technology and practical exploration, using institute's self assembly layer by layer
Strategy improves the carboxyl-content and roughness of Surfaces of Polystyrene Microparticles, and a large amount of carboxyl of rare earth ion and surface is made to pass through coordination
Key is connected, to improve the clad ratio of rare-earth nanometer particles, to successfully prepare rare-earth nanometer particles/polyphenyl of high clad ratio
Ethylene complex microsphere, while the application manufacturing cost is low, it is simple for process, there is wide industrial applications foreground.
One of the objects of the present invention is to provide a kind of preparation methods of rare-earth nanometer particles/polystyrene complex microsphere.
The second object of the present invention is to provide rare-earth nanometer particles/polystyrene that above-mentioned preparation method obtains compound micro-
Ball.
The third object of the present invention is to provide the application of above-mentioned rare-earth nanometer particles/polystyrene complex microsphere.
To achieve the above object, the present invention adopts the following technical scheme that：
The first aspect of the invention provides a kind of preparation method of rare-earth nanometer particles/polystyrene complex microsphere,
The method includes：
S1. polystyrene microsphere synthesizes：Polyvinylpyrrolidone is dissolved in the mixed solution of styrene and ethyl alcohol I, to
Surfactant, azodiisobutyronitrile is wherein added, under atmosphere of inert gases, after heating reaction a period of time, adds thereto
The mixed solution for entering methacrylic acid and ethyl alcohol II continues heating and reacts to obtain milky white solution；
S2. the modification of Surfaces of Polystyrene Microparticles：Polystyrene solid is obtained after step S1. milky white solutions are purified, it will
The polystyrene solid is scattered in ethyl alcohol, and polyethyleneimine stirring is added thereto, solid is scattered in water after purified
In, more carboxylate organic acids are added thereto, stirring obtains the polystyrene solid microballoon of surface modification carboxyl after purification；
S3. the synthesis of rare-earth nanometer particles/polystyrene complex microsphere：Rare earth salt aqueous solution is slowly added to containing step
S2. in the aqueous solution of the polystyrene solid microballoon of surface modification carboxyl obtained, heating stirring is after purification by obtained solid weight
Newly be dispersed in water, be slowly added to aqueous solution of alkali metal salt thereto, continue heating stirring purify afterwards for a period of time rare earth is received
Rice corpuscles/polystyrene complex microsphere.
Further, in the step S1.,
The ethyl alcohol I and ethyl alcohol II is absolute ethyl alcohol；
The surfactant is logical for Qula；Further preferably Qula leads to X-305；
The anhydrous second of the styrene, absolute ethyl alcohol I, polyvinylpyrrolidone, azodiisobutyronitrile, methacrylic acid sum
Alcohol II mass ratioes are 6：34：1：0.2-0.3：0.12-0.24：16；Preferably, the mass ratio is 6：34：1：0.25：0.12-
0.24：16；Wherein, polyvinylpyrrolidonemolecules molecules amount is preferably 55000；
It is added before methacrylic acid and ethyl alcohol II, heating reaction temperature is 70 DEG C, reaction time 2-4h, and methyl is added
After acrylic acid and ethyl alcohol II, heating reaction temperature is 70 DEG C, reaction time 20-22h；
Further, in the step S2.,
The mass ratio of polystyrene solid and polyethyleneimine is 5-10：1；
The molar ratio of more carboxylate organic acids and polyethyleneimine is 5-10：1；
Wherein, the molecular weight of polyethyleneimine is 600 or 1800；
More carboxylate organic acids are citric acid, D-malic acid, L MALIC ACID or DL-malic acid；
Mixing time is 4-6h；
Further, in the step S3.,
Rare-earth salts is 1 with the carboxyl molar ratio in more carboxylate organic acids in step S2.：1；
The molar ratio of rare-earth salts and alkali metal salt is 1：1-3.5；
Wherein, rare-earth salts is terbium chloride, Europium chloride, terbium nitrate or europium nitrate；
Alkali metal salt is sodium fluoride, potassium fluoride, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate；
Heating stirring temperature is 40-60 DEG C, time 4-6h；It is 40-60 DEG C to continue heating stirring temperature, time 1-
2h；
Heretofore described purifying refers to the process of taking out solid product from solvent, including wash, centrifuge；
The second aspect of the invention, disclosing above-mentioned preparation method, that rare-earth nanometer particles/polystyrene is prepared is multiple
Microballoon is closed, the clad ratio of rare-earth nanometer particles is 85-95%；
The third aspect of the invention, disclose above-mentioned rare-earth nanometer particles/polystyrene complex microsphere material science,
Application in medical imaging, medical diagnosis on disease or biomolecule detection.
Beneficial effects of the present invention：
(1) present invention is low with toxicity in preparing polystyrene microsphere, and the strong methacrylic acid of hydrophobicity is that copolymerization is single
Body, while adding surfactant Qula in the reaction system and leading to X-305, the dispersibility of entire reaction system is enhanced, is dropped
Low reaction temperatures save production cost；
(2) carboxylic group combined with rare earth in the application has from more carboxyls introduced after LBL self-assembly
Machine acid, the present invention introduce more carboxylate organic acids using the strategy of LBL self-assembly, and not only sour dosage increases, but also selects
Organic acid can contain multiple carboxyls so that the carboxyl-content of final microsphere surface increases substantially, to be conducive to improve
The clad ratio of nano-particle, while the application manufacturing cost is low, it is simple for process, there is wide industrial applications foreground and reality
Application prospect.
Description of the drawings
Fig. 1 is rare-earth nanometer particles of the present invention/polystyrene complex microsphere preparation principle figure.
Specific implementation mode
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific implementation mode, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or combination thereof.
As previously described, because in the prior art, rare-earth nanometer particles are easily reunited in cumbersome modification and recombination process, are led
It causes the clad ratio of nano-particle relatively low, and fluorescence-intensity decay, is unable to reach the requirement of certain sector applications.
In view of this, the present invention provides a kind of preparation method of rare-earth nanometer particles/polystyrene complex microsphere, the side
Method includes：
S1. polystyrene microsphere synthesizes：Polyvinylpyrrolidone is dissolved in the mixed solution of styrene and ethyl alcohol I, to
Surfactant, azodiisobutyronitrile is wherein added, under atmosphere of inert gases, after heating reaction a period of time, adds thereto
The mixed solution for entering methacrylic acid and ethyl alcohol II continues heating and reacts to obtain milky white solution；
S2. the modification of Surfaces of Polystyrene Microparticles：Polystyrene solid is obtained after step S1. milky white solutions are purified, it will
The polystyrene solid is scattered in ethyl alcohol, and polyethyleneimine stirring is added thereto, solid is scattered in water after purified
In, more carboxylate organic acids are added thereto, stirring obtains the polystyrene solid microballoon of surface modification carboxyl after purification；
S3. the synthesis of rare-earth nanometer particles/polystyrene complex microsphere：Rare earth salt aqueous solution is slowly added to containing step
S2. in the aqueous solution of the polystyrene solid microballoon of surface modification carboxyl obtained, heating stirring is after purification by obtained solid weight
Newly be dispersed in water, be slowly added to aqueous solution of alkali metal salt thereto, continue heating stirring purify afterwards for a period of time rare earth is received
Rice corpuscles/polystyrene complex microsphere.
In the still another embodiment of the present invention, the step S1.,
The ethyl alcohol I and ethyl alcohol II is absolute ethyl alcohol；
The surfactant is logical for Qula；Further preferably Qula leads to X-305；
The anhydrous second of the styrene, absolute ethyl alcohol I, polyvinylpyrrolidone, azodiisobutyronitrile, methacrylic acid sum
Alcohol II mass ratioes are 6：34：1：0.2-0.3：0.12-0.24：16；Preferably, the mass ratio is 6：34：1：0.25：0.12-
0.24：16；Wherein, polyvinylpyrrolidonemolecules molecules amount is preferably 55000；
It is added before methacrylic acid and ethyl alcohol II, heating reaction temperature is 70 DEG C, reaction time 2-4h, and methyl is added
After acrylic acid and ethyl alcohol II, heating reaction temperature is 70 DEG C, reaction time 20-22h；
In the still another embodiment of the present invention, in the step S2.,
The mass ratio of polystyrene solid and polyethyleneimine is 5-10：1；
The molar ratio of more carboxylate organic acids and polyethyleneimine is 5-10：1；
Wherein, the molecular weight of polyethyleneimine is 600 or 1800；
More carboxylate organic acids are citric acid, D-malic acid, L MALIC ACID or DL-malic acid；
Mixing time is 4-6h；
In the still another embodiment of the present invention, in the step S3.,
Rare-earth salts is 1 with the carboxyl molar ratio in more carboxylate organic acids in step S2.：1；
The molar ratio of rare-earth salts and alkali metal salt is 1：1-3.5；
Wherein, rare-earth salts is terbium chloride, Europium chloride, terbium nitrate or europium nitrate；
Alkali metal salt is sodium fluoride, potassium fluoride, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate；
Heating stirring temperature is 40-60 DEG C, time 4-6h；It is 40-60 DEG C to continue heating stirring temperature, time 1-
2h；
Heretofore described purifying refers to the process of taking out solid product from solvent, including wash, centrifuge；
In the still another embodiment of the present invention, above-mentioned preparation method is provided, rare-earth nanometer particles/polyphenyl is prepared
The clad ratio of ethylene complex microsphere, rare-earth nanometer particles is 85-95%；
In the still another embodiment of the present invention, above-mentioned rare-earth nanometer particles/polystyrene complex microsphere is provided in material
Application in material science, medical imaging, medical diagnosis on disease or biomolecule detection.
Explanation is further explained to the present invention by the following examples, but is not construed as limiting the invention.
Embodiment one
1, polystyrene microsphere synthesizes
(1) 6g styrene is placed in 250mL three neck round bottom；
(2) 34g absolute ethyl alcohols are added, are uniformly mixed；
(3) polyvinylpyrrolidone that 1g molecular weight is 55000 is added, stirring to solid is dissolved；
(4) 0.35g Qulas are instilled and leads to X-305, be uniformly mixed；
(5) it is added in 0.25g azodiisobutyronitriles to mixed solution, stirs evenly；
(6) nitrogen is passed through under liquid level after adding 1 hour；
(7) 70 DEG C are heated to, under nitrogen atmosphere protection, continues stirring 2 hours；
(8) mixed solution of 0.24g methacrylic acids and 16g absolute ethyl alcohols is added；
(9) continue heating stirring 20 hours；
(10) after reaction stops, with alternately washing centrifugation 5 times of second alcohol and water, unreacted reactant is removed, surface is obtained
The polystyrene microsphere of carboxyl-content 4%；
2, the modification on polystyrene complex microsphere surface
(1) solid (1g) after being centrifuged in step 1 is taken, is dispersed in 10mL absolute ethyl alcohols；
(2) polyethyleneimine (0.2g, 0.33mmol) that molecular weight is 600 is added, stirs 4 hours at room temperature, with water and
Absolute ethyl alcohol alternately washs, and obtained solid is dispersed in 10mL water by centrifugation；
(3) citric acid (0.32g, 1.67mmol) is added, stirs 4 hours at room temperature, centrifugation 5 times is washed with water；
3, the synthesis of rare-earth nanometer particles/polystyrene complex microsphere
(1) microballoon for obtaining step 2 is distributed in 10mL water；
(2) the Europium chloride aqueous solution of 5mL 1mol/L is slowly added dropwise, is heated to 50 DEG C, stirs 4 hours, centrifugation is washed with water
For several times；
(3) sodium dihydrogen phosphate of 5.2mL 1mol/L is slowly added dropwise, continues heating stirring 2 hours；
(4) after having reacted, centrifugation 5 times, clad ratio 90% is washed with water.
Embodiment two
1, polystyrene microsphere synthesizes
(1) 6g styrene is placed in 250mL three neck round bottom；
(2) 34g absolute ethyl alcohols are added, are uniformly mixed；
(3) polyvinylpyrrolidone that 1g molecular weight is 55000 is added, stirring to solid is dissolved；
(4) 0.35g Qulas are instilled and leads to X-305, be uniformly mixed；
(5) it is added in 0.25g azodiisobutyronitriles to mixed solution, stirs evenly；
(6) nitrogen is passed through under liquid level after adding 1 hour；
(7) 70 DEG C are heated to, under nitrogen atmosphere protection, continues stirring 2 hours；
(8) mixed solution of 0.24g methacrylic acids and 16g absolute ethyl alcohols is added；
(9) continue heating stirring 22 hours；
(10) after reaction stops, with alternately washing centrifugation 5 times of second alcohol and water, unreacted reactant is removed, surface is obtained
The polystyrene microsphere of carboxyl-content 4%；
2, the modification on polystyrene complex microsphere surface
(1) solid (1g) after being centrifuged in step 1 is taken, is dispersed in 10mL absolute ethyl alcohols；
(2) polyethyleneimine (0.2g, 0.33mmol) that molecular weight is 600 is added, stirs 4 hours at room temperature, with water and
Absolute ethyl alcohol alternately washs, and obtained solid is dispersed in 10mL water by centrifugation；
(3) DL-malic acid (0.22g, 1.67mmol) is added, stirs 4 hours at room temperature, centrifugation 5 times is washed with water；
3, the synthesis of rare-earth nanometer particles/polystyrene complex microsphere
(1) microballoon for obtaining step 2 is distributed in 10mL water；
(2) the Europium chloride aqueous solution of 3.4mL 1mol/L is slowly added dropwise, is heated to 50 DEG C, stirs 4 hours, be washed with water from
Calculation；
(3) sodium dihydrogen phosphate of 3.6mL 1mol/L is slowly added dropwise, continues heating stirring 2 hours；
(4) after having reacted, centrifugation 5 times, clad ratio 85% is washed with water.
Embodiment three
1, polystyrene microsphere synthesizes
(1) 6g styrene is placed in 250mL three neck round bottom；
(2) 34g absolute ethyl alcohols are added, are uniformly mixed；
(3) polyvinylpyrrolidone that 1g molecular weight is 55000 is added, stirring to solid is dissolved；
(4) 0.35g Qulas are instilled and leads to X-305, be uniformly mixed；
(5) it is added in 0.25g azodiisobutyronitriles to mixed solution, stirs evenly；
(6) nitrogen is passed through under liquid level after adding 1 hour；
(7) 70 DEG C are heated to, under nitrogen atmosphere protection, continues stirring 2 hours；
(8) mixed solution of 0.24g methacrylic acids and 16g absolute ethyl alcohols is added；
(9) continue heating stirring 20 hours；
(10) after reaction stops, with alternately washing centrifugation 5 times of second alcohol and water, unreacted reactant is removed, surface is obtained
The polystyrene microsphere of carboxyl-content 4%；
2, the modification on polystyrene complex microsphere surface
(1) solid (1g) after being centrifuged in step 1 is taken, is dispersed in 10mL absolute ethyl alcohols；
(2) polyethyleneimine (0.2g, 0.11mmol) that molecular weight is 1800 is added, stirs 4 hours at room temperature, with water and
Absolute ethyl alcohol alternately washs, and obtained solid is dispersed in 10mL water by centrifugation；
(3) citric acid (0.17g, 0.88mmol) is added, stirs 4 hours at room temperature, centrifugation 5 times is washed with water；
3, the synthesis of rare-earth nanometer particles/polystyrene complex microsphere
(1) microballoon for obtaining step 2 is distributed in 10mL water；
(2) the Europium chloride aqueous solution of 2.6mL 1mol/L is slowly added dropwise, is heated to 50 DEG C, stirs 4 hours, be washed with water from
Calculation；
(3) sodium dihydrogen phosphate of 2.8mL 1mol/L is slowly added dropwise, continues heating stirring 2 hours；
(4) after having reacted, centrifugation 5 times, clad ratio 95% is washed with water.
Example IV
1, polystyrene microsphere synthesizes
(1) 6g styrene is placed in 250mL three neck round bottom；
(2) 34g absolute ethyl alcohols are added, are uniformly mixed；
(3) polyvinylpyrrolidone that 1g molecular weight is 55000 is added, stirring to solid is dissolved；
(4) 0.35g Qulas are instilled and leads to X-305, be uniformly mixed；
(5) it is added in 0.25g azodiisobutyronitriles to mixed solution, stirs evenly；
(6) nitrogen is passed through under liquid level after adding 1 hour；
(7) 70 DEG C are heated to, under nitrogen atmosphere protection, continues stirring 2 hours；
(8) mixed solution of 0.24g methacrylic acids and 16g absolute ethyl alcohols is added；
(9) continue heating stirring 20 hours；
(10) after reaction stops, with alternately washing centrifugation 5 times of second alcohol and water, unreacted reactant is removed, surface is obtained
The polystyrene microsphere of carboxyl-content 4%；
2, the modification on polystyrene complex microsphere surface
(1) solid (1g) after being centrifuged in step 1 is taken, is dispersed in 10mL absolute ethyl alcohols；
(2) polyethyleneimine (0.2g, 0.11mmol) that molecular weight is 1800 is added, stirs 4 hours at room temperature, with water and
Absolute ethyl alcohol alternately washs, and obtained solid is dispersed in 10mL water by centrifugation；
(3) DL-malic acid (0.14g, 1mmol) is added, stirs 4 hours at room temperature, centrifugation 5 times is washed with water；
3, the synthesis of rare-earth nanometer particles/polystyrene complex microsphere
(1) microballoon for obtaining step 2 is distributed in 10mL water；
(2) the Europium chloride aqueous solution of 2mL 1mol/L is slowly added dropwise, is heated to 50 DEG C, stirs 4 hours, centrifugation is washed with water
For several times；
(3) Fluorinse of 6.5mL 1mol/L is slowly added dropwise, continues heating stirring 1 hour；
(4) after having reacted, centrifugation 5 times, clad ratio 90% is washed with water.
The foregoing is merely the preferred embodiments of the application, are not intended to limit this application, for the skill of this field
For art personnel, the application can have various modifications and variations.Within the spirit and principles of this application, any made by repair
Change, equivalent replacement, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of preparation method of rare-earth nanometer particles/polystyrene complex microsphere, which is characterized in that including：
S1. polystyrene microsphere synthesizes：Polyvinylpyrrolidone is dissolved in the mixed solution of styrene and ethyl alcohol I, thereto
Surfactant, azodiisobutyronitrile is added, under atmosphere of inert gases, after heating reaction a period of time, first is added thereto
The mixed solution of base acrylic acid and ethyl alcohol II continues heating and reacts to obtain milky white solution；
S2. the modification of Surfaces of Polystyrene Microparticles：Polystyrene solid is obtained after step S1. milky white solutions are purified, it will be described
Polystyrene solid is scattered in ethyl alcohol, and polyethyleneimine stirring is added thereto, is dispersed in water solid after purified, to
More carboxylate organic acids are wherein added, stirring obtains the polystyrene solid microballoon of surface modification carboxyl after purification；
S3. the synthesis of rare-earth nanometer particles/polystyrene complex microsphere：Rare earth salt aqueous solution is slowly added to containing step S2.
In the aqueous solution of the polystyrene solid microballoon of surface modification carboxyl obtained, heating stirring after purification divides obtained solid again
It dissipates in water, is slowly added to aqueous solution of alkali metal salt thereto, continue heating stirring and purify to obtain rare earth nano grain afterwards for a period of time
Son/polystyrene complex microsphere.
2. preparation method as described in claim 1, which is characterized in that in the step S1.,
Ethyl alcohol I and ethyl alcohol II is absolute ethyl alcohol；
Surfactant is logical for Qula；Preferably Qula leads to X-305.
3. preparation method as described in claim 1, which is characterized in that in the step S1.,
The absolute ethyl alcohol II mass of styrene, absolute ethyl alcohol I, polyvinylpyrrolidone, azodiisobutyronitrile, methacrylic acid sum
Than being 6：34：1：0.2-0.3：0.12-0.24：16；Preferably, the mass ratio is 6：34：1：0.25：0.12-0.24：16；
Wherein, polyvinylpyrrolidonemolecules molecules amount is preferably 55000.
4. preparation method as described in claim 1, which is characterized in that in the step S1.,
It is added before methacrylic acid and ethyl alcohol II, heating reaction temperature is 70 DEG C, reaction time 2-4h, and metering system is added
Acid is with after ethyl alcohol II, and heating reaction temperature is 70 DEG C, reaction time 20-22h.
5. preparation method as described in claim 1, which is characterized in that in the step S2.,
The mass ratio of polystyrene solid and polyethyleneimine is 5-10：1；
The molar ratio of more carboxylate organic acids and polyethyleneimine is 5-10：1；
Wherein, the molecular weight of polyethyleneimine is 600 or 1800；
More carboxylate organic acids are citric acid, D-malic acid, L MALIC ACID or DL-malic acid.
6. preparation method as described in claim 1, which is characterized in that in the step S2.,
Mixing time is 4-6h.
7. preparation method as described in claim 1, which is characterized in that in the step S3.,
Rare-earth salts is 1 with the carboxyl molar ratio in more carboxylate organic acids in step S2.：1；
The molar ratio of rare-earth salts and alkali metal salt is 1：1-3.5；
Wherein, rare-earth salts is terbium chloride, Europium chloride, terbium nitrate or europium nitrate；
Alkali metal salt is sodium fluoride, potassium fluoride, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate.
8. preparation method as described in claim 1, which is characterized in that in the step S3.,
Heating stirring temperature is 40-60 DEG C, time 4-6h；It is 40-60 DEG C to continue heating stirring temperature, time 1-2h.
9. rare-earth nanometer particles/polystyrene complex microsphere is prepared in any one of the claim 1-8 preparation methods, special
Sign is that the clad ratio of rare-earth nanometer particles is 85-95%.
10. rare-earth nanometer particles described in claim 9/polystyrene complex microsphere is in material science, medical imaging, medical diagnosis on disease
Or the application in biomolecule detection.
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| CN110244044A (en) * | 2019-06-13 | 2019-09-17 | 苏州百源基因技术有限公司 | A kind of rare-earths dyeing magnetic bead and its preparation and application |
| CN112250779A (en) * | 2020-10-27 | 2021-01-22 | 深圳市裕同包装科技股份有限公司 | Photochromic microspheres, preparation method and application |
| CN116478694A (en) * | 2023-04-23 | 2023-07-25 | 天津大学 | Preparation and array method of polystyrene encapsulated nanocrystalline composite luminescent material |
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| CN116478694A (en) * | 2023-04-23 | 2023-07-25 | 天津大学 | Preparation and array method of polystyrene encapsulated nanocrystalline composite luminescent material |
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