CN104726102A - Fluorescent anti-counterfeiting material and preparation method thereof - Google Patents
Fluorescent anti-counterfeiting material and preparation method thereof Download PDFInfo
- Publication number
- CN104726102A CN104726102A CN201510113516.1A CN201510113516A CN104726102A CN 104726102 A CN104726102 A CN 104726102A CN 201510113516 A CN201510113516 A CN 201510113516A CN 104726102 A CN104726102 A CN 104726102A
- Authority
- CN
- China
- Prior art keywords
- nano
- solution
- preparation
- fluorescence
- quantum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Luminescent Compositions (AREA)
- Cosmetics (AREA)
Abstract
The invention relates to a fluorescent anti-counterfeiting material and a preparation method thereof and belongs to the technical field of preparation of biological materials. The preparation method of the fluorescent anti-counterfeiting material comprises the following steps: preparing a nano fluorescent material by adopting a hydrothermal synthesis method, firstly regulating pH of cadmium acetate solution to be alkaline, then sequentially adding mercaptoacetic acid, tellurium-ion-containing solution and potassium borohydride while stirring, after stirring is carried out for a period of time, heating a system until the system is boiled, performing sustained reaction, centrifuging, washing until supernate is free of fluorescence under ultraviolet radiation, and carrying out freeze drying on separated precipitates; treating the dried precipitates, and further compounding with a carrier material with stable properties, so that the fluorescent anti-counterfeiting material is obtained, wherein the used carrier material is nano calcium carbonate. The fluorescent anti-counterfeiting material is easy to prepare, high in repeatability and available and is stable in fluorescent property, easy to identify and convenient for detection; and the fluorescent anti-counterfeiting material has an important application prospect in the fields of commodity anti-counterfeiting due to unique properties.
Description
Technical field
The present invention relates to and a kind ofly can be used for fluorescence falsification preventing material of food, medicine and daily necessities etc. and preparation method thereof, belong to biomaterials art preparation field.
Background technology
Along with the continuous progress of society, the development of industrial or agricultural, different, a feast for the eyes commodity of class, while promotion commodity economy high speed development, also meet the needs of the living standard that people improve constantly.But also dragons and snakes jumbled together enters circulation market for tedious adulterant.Therefore, false proof, knowledge puppet is exactly always the problem being subject to people's most attention.The false proof new technique got up as development in recent years of chemistry, has and manufactures simply, and it is convenient to identify, cost is lower, good confidentiality, and reliability is high, has vast potential for future development.Fluorescence falsification preventing technology is as the one of chemical anti-counterfeiting technology, utilize material to launch fluorescence under the UV-irradiation of certain wavelength, and reach the method for distinguishing true from false, when this kind of material is used for false proof, wide in variety, luminous abundant, can be made multi color pattern, itself is colourless or look shallow, good stability, with low cost, identify simple.This just makes fluorescence falsification preventing technology become an important development direction of field of anti-counterfeit technology.
Fluorescent nano material is as one of important composition of fluorescence falsification preventing material, have at present about various fluorescent material and preparation method thereof middle-weight rare earths class fluorescent material and organic fluorescence materials more, close yttrium europium Eu (Y) (TTA) 3phen ultraviolet fluorescence powder with o-phenanthroline acetyl trifluoroacetone made corresponding fluoresent printing ink as the Tian Jun of Applied Chemistry Inst., Jiangxi Prov. Academy of Sciences, monarch respect group, but it possesses red light, color is relatively single; Chinese invention patent CN 104073255 A discloses a kind of silicic acid zirconates blue colour fluorescent powder and preparation method thereof, but this fluorescent material exists complicated process of preparation, requires the problems such as high, can not meet the requirement of anti-fake material to preparation condition.
Summary of the invention
The object of the invention is the material preparation trouble overcoming current existence, identify difficulty, the problems such as easy imitation, there is provided a kind of fluorescence falsification preventing material, this fluorescence labelling thing not only stable performance, and under general ultraviolet light irradiation, namely there is comparatively hyperfluorescenceZeng Yongminggaoyingguang, and fluorescence color abundant species, not easily imitate, be easy to identification, thus realize false proof object.Its concrete technical scheme is as follows:
A kind of nano-quantum point fluorescence falsification preventing material, this material is mainly containing fluorescence quantum and solid support material, and described solid support material is nano-calcium carbonate, and nano-calcium carbonate diameter is about 1 μm, and calcium carbonate crystal formation is mainly calcite.
Further, unstressed configuration under general visible is irradiated, and with presenting gorgeous fluorescence under 365 nm uviolizings, its fluorescence intensity is high, stable in properties.
A preparation method for above-mentioned nano-quantum point fluorescence falsification preventing material, is characterized in that: comprise the steps:
1) in cadmium acetate solution, drip sodium hydroxide solution, adjustment pH is 10.5-11.0, and the volumetric molar concentration of cadmium acetate is finally 2-10 mM/L, needs continuous stirring in dropping process; Be Cd:Te:TGA:NaBH according to each material mol ratio under making final solution state under continuous stirring
4the amount of=1:0.2:1:10 adds Thiovanic acid successively, K
2teO
3solution and sodium borohydride, whole process pH remains unchanged, K
2teO
3volumetric molar concentration is finally 0.4-2 mM/L;
2) by above-mentioned steps 1) in solution stir 15-30 min at normal temperatures after, whole system is placed in 110-180 DEG C of oil bath pan and is heated to boiling, and carry out condensing reflux, sustained reaction, start during self-boiling to calculate, every 15 min samplings, fluorescent spectrophotofluorometer F-4500 carries out qualification fluorescence intensity;
3) by step 2) in sample cooling after first add acetone, the centrifugal quantum dot of 8000-12000 rpm, re-use dehydrated alcohol repetitive scrubbing precipitation;
4) washing of precipitate in step 3) after unstressed configuration display, is isolated precipitation to supernatant liquor under ultraviolet lamp, after pellet frozen drying, normal temperature preserves the quantum dot of preparation;
5) in sericin solution (molecular weight is 1W-2W), drip calcium ions solution simultaneously and contain carbanion solution, in solution, the concentration of sericin is 2-10 g/L, constantly stirs in dropping process; Calcium ion is kept to be Ca with the ratio of the amount of substance of carbanion
2+: CO
3 2-=1:1, the volumetric molar concentration of calcium ion is 1-5 mM/L, and the volumetric molar concentration of carbanion is 1-5 mM/L.Drip completely, keep temperature-resistant continuation at the uniform velocity to stir after 2-6 hour and leave standstill, to be precipitated with supernatant layering after, removing supernatant, centrifuge washing is placed on 30 DEG C-100 DEG C oven drying 2-24 h, and normal temperature preserves the nano-calcium carbonate solid support material of preparation;
6) be fluorescence quantum with the nano-calcium carbonate solid support material prepared in step 5) according to mass ratio by the quantum dot prepared in step 4): the amount of solid support material=1-10:100 mixes, adding mass ratio is 0.1-10 deionized water doubly, stir, make material fully in conjunction with more than 2-12 h;
7) by the aqueous solution centrifuge washing in step 6) three times, after will drying being precipitated, preserve under being placed in normal temperature, obtain fluorescence falsification preventing material of the present invention.
Further, in described step 2) in every 15 min sampling observe, wherein in 15-60 min process, quantum dot be green; In 60-360 min process, quantum dot is yellow-green colour and turns yellow gradually; In 360-450 min process, quantum dot is yellow; In 450-2000 min process, quantum dot is safran and reddens gradually; 2000 more than min colors are red and deepen gradually in time.
Further, the solution of the calcium ions described in step 5), reagent used can be calcium chloride, nitrocalcite.
Further, the solution containing carbanion described in step 5), reagent used can be sodium carbonate, salt of wormwood.
Further, the spherical nano-calcium carbonate described in step 5), its crystal formation is mainly calcite phase, and diameter is about 1 μm.
Further, described nano-quantum point fluorescence falsification preventing material, when existing with viscous liquid, the maximum and stable in properties of its fluorescence intensity, reaches more than 30 days working lipe; When existing with solid state powder, fluorescence intensity reduce, but add a small amount of water furnishing thick time, be as good as before its fluorescence intensity and drying.
Accompanying drawing explanation
Fig. 1 is that the nano-calcium carbonate particles SEM that embodiment 1 obtains schemes.
Fig. 2 is the fluorescent nano particle fluorescence 3D scintigram that embodiment 1 obtains.
Fig. 3 is the utilizing emitted light spectrogram that the obtained fluorescent nano particle of embodiment 1 obtains under 285 nm excite.
Embodiment
In order to make the present invention's easy to understand more, set forth the present invention further below in conjunction with drawings and Examples.These embodiments only for illustration of and be not used in and limit the scope of the invention, NM specific experiment method in the following example, experimental technique carries out routinely usually.
Embodiment 1:
1) measuring concentration is that cadmium acetate solution 50 mL of 4 mM/L is placed in round-bottomed flask, and regulates pH between 10.5-11.0 by 1 M/L NaOH solution and carry out Keep agitation, reacts 5 min; Add 18 ulTGA, and regulate pH between 10.5-11.0 by NaOH solution, react 5 min; Measure the K that concentration is 0.8 mM/L again
2teO
3solution 50 mL and 80 ㎎ NaBH
4add among system, maintain pH between 10.5-11.0, sustained reaction 5 min.
2) round-bottomed flask is placed in oil bath pan, regulates temperature to be 170 DEG C and carry out condensing reflux reaction; 45 min carry out sampling the fluorescence quantum sample obtaining green.
3) first use acetone sedimentation by after above-mentioned sample cooling, rear dehydrated alcohol centrifuge washing, to supernatant liquor unstressed configuration under ultraviolet lamp, isolates precipitation, after precipitation being put into Freeze Drying Equipment lyophilize, preserves stand-by.
4) configure 10 g/L silk gum solution 200 ml, measure 2 mM/L CaCl respectively
2solution and 2 mM/L Na
2cO
3each 10 ml of solution; Under nature pH, two solution are joined in silk gum solution with the speed of 20/min simultaneously, in whole process, keeps temperature, pH, rotating speed constant;
5) drip completely, stopped reaction after continuation stirring 2 h, centrifugal three minutes of 8000 rpm/min, wash 3 times respectively with deionized water and dehydrated alcohol after abandoning supernatant liquor, are placed in 50 DEG C of oven dry 24 h and obtain nano-calcium carbonate calcium powder.
6) be that 1:100 in the solution mix with nano-calcium carbonate according to mass ratio by quantum dot, slight concussion makes it combine fully in 24 hours, centrifugally washes away unconjugated fluorescence quantum and namely obtains fluorescence falsification preventing material.
Embodiment 2:
1) measuring concentration is that cadmium acetate solution 50 mL of 2 mM/L is placed in round-bottomed flask, and regulates pH between 10.5-11.0 by 1 M/L NaOH solution and carry out Keep agitation, reacts 5 min; Add 9 ulTGA, and regulate pH between 10.5-11.0 by NaOH solution, react 5 min; Measure the K that concentration is 0.4 mM/L again
2teO
3solution 50 mL and 40 ㎎ NaBH
4add among system, maintain pH between 10.5-11.0, sustained reaction 5 min.
2) round-bottomed flask is placed in oil bath pan, regulates temperature to be 120 DEG C and carry out condensing reflux reaction; 400 min carry out sampling the fluorescence quantum sample obtaining yellow.
3) first use acetone sedimentation by after above-mentioned sample cooling, rear dehydrated alcohol centrifuge washing, to supernatant liquor unstressed configuration under ultraviolet lamp, isolates precipitation, after precipitation being put into Freeze Drying Equipment lyophilize, preserves stand-by.
4) configure 2 g/L silk gum solution 200 ml, measure 1 mM/L CaCl respectively
2solution and 1 mM/L Na
2cO
3each 20 ml of solution; Under nature pH, two solution are joined in silk gum solution with the speed of 20/min simultaneously, in whole process, keeps temperature, pH, rotating speed constant;
5) drip completely, stopped reaction after continuation stirring 2 h, centrifugal three minutes of 8000 rpm/min, wash 3 times respectively with deionized water and dehydrated alcohol after abandoning supernatant liquor, are placed in 50 DEG C of oven dry 24 h and obtain nano-calcium carbonate calcium powder.
6) be that 5:100 in the solution mix with nano-calcium carbonate according to mass ratio by quantum dot, slight concussion makes it combine fully in 24 hours, centrifugally washes away unconjugated fluorescence quantum and namely obtains fluorescence falsification preventing material.
Embodiment 3:
1) measuring concentration is that cadmium acetate solution 50 mL of 10 mM/L is placed in round-bottomed flask, and regulates pH between 10.5-11.0 by 1 M/L NaOH solution and carry out Keep agitation, reacts 5 min; Add 45 ulTGA, and regulate pH between 10.5-11.0 by NaOH solution, react 5 min; Measure the K that concentration is 2 mM/L again
2teO
3solution 50 mL and 200 ㎎ NaBH
4add among system, maintain pH between 10.5-11.0, sustained reaction 5 min.
2) round-bottomed flask is placed in oil bath pan, regulates temperature to be 180 DEG C and carry out condensing reflux reaction; 2000 min carry out sampling the fluorescence quantum sample obtaining redness.
3) first use acetone sedimentation by after above-mentioned sample cooling, rear dehydrated alcohol centrifuge washing, to supernatant liquor unstressed configuration under ultraviolet lamp, isolates precipitation, after precipitation being put into Freeze Drying Equipment lyophilize, preserves stand-by.
4) configure 5 g/L silk gum solution 200 ml, measure 5 mM/L CaCl respectively
2solution and 5 mM/L Na
2cO
3each 10 ml of solution; Under nature pH, two solution are joined in silk gum solution with the speed of 20/min simultaneously, in whole process, keeps temperature, pH, rotating speed constant;
5) drip completely, stopped reaction after continuation stirring 2 h, centrifugal three minutes of 8000 rpm/min, wash 3 times respectively with deionized water and dehydrated alcohol after abandoning supernatant liquor, are placed in 50 DEG C of oven dry 24 h and obtain nano-calcium carbonate calcium powder.
6) be that 10:100 in the solution mix with nano-calcium carbonate according to mass ratio by quantum dot, slight concussion makes it combine fully in 24 hours, centrifugally washes away unconjugated fluorescence quantum and namely obtains fluorescence falsification preventing material.
Claims (8)
1. a nano-quantum point fluorescence falsification preventing material, is characterized in that, this material is mainly containing fluorescence quantum and solid support material, and described solid support material is nano-calcium carbonate, and nano-calcium carbonate diameter is about 1 μm, and calcium carbonate crystal formation is mainly calcite.
2. nano-quantum point fluorescence falsification preventing material according to claim 1, is characterized in that, unstressed configuration under general visible is irradiated, and with presenting gorgeous fluorescence under 365 nm uviolizings, its fluorescence intensity is high, stable in properties.
3. a preparation method for the nano-quantum point fluorescence falsification preventing material described in claim 1 or 2, is characterized in that: comprise the steps:
In cadmium acetate solution, drip sodium hydroxide solution, adjustment pH is 10.5-11.0, and the volumetric molar concentration of cadmium acetate is finally 2-10 mM/L, needs continuous stirring in dropping process; Be Cd:Te:TGA:NaBH according to each material mol ratio under making final solution state under continuous stirring
4the amount of=1:0.2:1:10 adds Thiovanic acid successively, K
2teO
3solution and sodium borohydride, whole process pH remains unchanged, K
2teO
3volumetric molar concentration is finally 0.4-2 mM/L;
By above-mentioned steps 1) in solution stir 15-30 min at normal temperatures after, whole system is placed in 110-180 DEG C of oil bath pan and is heated to boiling, and carry out condensing reflux, sustained reaction, start during self-boiling to calculate, every 15 min samplings, fluorescent spectrophotofluorometer F-4500 carries out qualification fluorescence intensity;
By step 2) in sample cooling after first add acetone, the centrifugal quantum dot of 8000-12000 rpm, re-use dehydrated alcohol repetitive scrubbing precipitation;
Washing of precipitate in step 3) after unstressed configuration display, is isolated precipitation to supernatant liquor under ultraviolet lamp, and after pellet frozen drying, normal temperature preserves the quantum dot of preparation;
In sericin solution (molecular weight is 1W-2W), drip calcium ions solution simultaneously and contain carbanion solution, in solution, the concentration of sericin is 2-10 g/L, constantly stirs in dropping process; Calcium ion is kept to be Ca with the ratio of the amount of substance of carbanion
2+: CO
3 2-=1:1, the volumetric molar concentration of calcium ion is 1-5 mM/L, and the volumetric molar concentration of carbanion is 1-5 mM/L;
Drip completely, keep temperature-resistant continuation at the uniform velocity to stir after 2-6 hour and leave standstill, to be precipitated with supernatant layering after, removing supernatant, centrifuge washing is placed on 30 DEG C-100 DEG C oven drying 2-24 h, and normal temperature preserves the nano-calcium carbonate solid support material of preparation;
Be fluorescence quantum with the nano-calcium carbonate solid support material prepared in step 5) according to mass ratio by the quantum dot prepared in step 4): the amount of solid support material=1-10:100 mixes, adding mass ratio is 0.1-10 deionized water doubly, stir, make material fully in conjunction with more than 2-12 h;
By the aqueous solution centrifuge washing in step 6) three times, after will drying being precipitated, preserve under being placed in normal temperature, obtain fluorescence falsification preventing material of the present invention.
4. the preparation method of nano-quantum point fluorescence falsification preventing material according to claim 3, is characterized in that, in described step 2) in every 15 min sampling observe, wherein in 15-60 min process, quantum dot be green; In 60-360 min process, quantum dot is yellow-green colour and turns yellow gradually; In 360-450 min process, quantum dot is yellow; In 450-2000 min process, quantum dot is safran and reddens gradually; 2000 more than min colors are red and deepen gradually in time.
5. the preparation method of nano-quantum point fluorescence falsification preventing material according to claim 3, is characterized in that, the solution of the calcium ions described in step 5), and reagent used can be calcium chloride, nitrocalcite.
6. the preparation method of nano-quantum point fluorescence falsification preventing material according to claim 3, is characterized in that, the solution containing carbanion described in step 5), reagent used can be sodium carbonate, salt of wormwood.
7. the preparation method of nano-quantum point fluorescence falsification preventing material according to claim 3, it is characterized in that, the spherical nano-calcium carbonate described in step 5), its crystal formation is mainly calcite phase, and diameter is about 1 μm.
8. according to the nano-quantum point fluorescence falsification preventing material one of claim 1-3 Suo Shu, it is characterized in that, when existing with viscous liquid, the maximum and stable in properties of its fluorescence intensity, reaches more than 30 days working lipe; When existing with solid state powder, fluorescence intensity reduce, but add a small amount of water furnishing thick time, be as good as before its fluorescence intensity and drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510113516.1A CN104726102B (en) | 2015-03-16 | 2015-03-16 | Fluorescence falsification preventing material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510113516.1A CN104726102B (en) | 2015-03-16 | 2015-03-16 | Fluorescence falsification preventing material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104726102A true CN104726102A (en) | 2015-06-24 |
| CN104726102B CN104726102B (en) | 2016-08-17 |
Family
ID=53450536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510113516.1A Active CN104726102B (en) | 2015-03-16 | 2015-03-16 | Fluorescence falsification preventing material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104726102B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107423798A (en) * | 2017-08-09 | 2017-12-01 | 上海朗研光电科技有限公司 | Fluorescent two-dimensional code anti-counterfeiting mark method based on nano particle |
| CN111337465A (en) * | 2020-03-06 | 2020-06-26 | 齐鲁工业大学 | Solid-state fluorescence anti-counterfeiting method based on reversible response of amine steam |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007120762A2 (en) * | 2006-04-14 | 2007-10-25 | Cambrios Technologies Corporation | Fluorescent particles bound to multifunctional scaffolds and their uses |
| CN101085870A (en) * | 2007-06-06 | 2007-12-12 | 浙江理工大学 | Sericin/calcium carbonate nano composite material and preparation method thereof |
| US20100062194A1 (en) * | 2008-09-04 | 2010-03-11 | Xiao-Dong Sun | Anti-counterfeiting methods and devices using substantially transparent fluorescent materials |
| CN102693679A (en) * | 2012-05-30 | 2012-09-26 | 广东普加福光电科技有限公司 | Anti-counterfeiting identification method by aid of quantum points |
| CN102912675A (en) * | 2012-10-15 | 2013-02-06 | 保定钞票纸业有限公司 | Quantum dot fluorescent anti-counterfeiting paper and manufacturing method thereof |
| CN103669111A (en) * | 2013-12-24 | 2014-03-26 | 长沙理工大学 | Preparation method of fluorescent semiconductor nanocrystalline security paper |
-
2015
- 2015-03-16 CN CN201510113516.1A patent/CN104726102B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007120762A2 (en) * | 2006-04-14 | 2007-10-25 | Cambrios Technologies Corporation | Fluorescent particles bound to multifunctional scaffolds and their uses |
| CN101085870A (en) * | 2007-06-06 | 2007-12-12 | 浙江理工大学 | Sericin/calcium carbonate nano composite material and preparation method thereof |
| US20100062194A1 (en) * | 2008-09-04 | 2010-03-11 | Xiao-Dong Sun | Anti-counterfeiting methods and devices using substantially transparent fluorescent materials |
| CN102693679A (en) * | 2012-05-30 | 2012-09-26 | 广东普加福光电科技有限公司 | Anti-counterfeiting identification method by aid of quantum points |
| CN102912675A (en) * | 2012-10-15 | 2013-02-06 | 保定钞票纸业有限公司 | Quantum dot fluorescent anti-counterfeiting paper and manufacturing method thereof |
| CN103669111A (en) * | 2013-12-24 | 2014-03-26 | 长沙理工大学 | Preparation method of fluorescent semiconductor nanocrystalline security paper |
Non-Patent Citations (2)
| Title |
|---|
| LING HU ET AL.: "Fabrication of fluorescent microparticles by doping water-soluble CdTe nanocrystals into calcium carbonate for monitoring intracellular uptake", 《COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS》 * |
| 白雪莲，等: "多路发光CdxZn1-xSe量子点的制备及防伪功能设计", 《高等学校化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107423798A (en) * | 2017-08-09 | 2017-12-01 | 上海朗研光电科技有限公司 | Fluorescent two-dimensional code anti-counterfeiting mark method based on nano particle |
| CN111337465A (en) * | 2020-03-06 | 2020-06-26 | 齐鲁工业大学 | Solid-state fluorescence anti-counterfeiting method based on reversible response of amine steam |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104726102B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106497551B (en) | A kind of pure organic room temperature phosphorimetry material of high-performance and its preparation method and application | |
| US20210079297A1 (en) | Homogeneous persistent luminescence nanocrystals and methods of preparation and application thereof | |
| CN106350057B (en) | A kind of preparation method of fluorescence nano hybrid particle | |
| CN102080271B (en) | Two-photon fluorescence biological silk material and preparation method thereof | |
| CN102071027B (en) | Water-soluble rare-earth terbium ion-doped cerium fluoride nanocrystallines and preparation method thereof | |
| CN102517003A (en) | Hydro-thermal preparation method for novel near infrared water-soluble copper-indium-sulfur three-element quantum dots | |
| CN108485097A (en) | The micro- plastics and preparation method of a kind of long-persistence luminous nanometer particle to mark and application | |
| CN109504366A (en) | A kind of rare-earth complex cladding nano-hollow SiO2With cladded type rare-earth complex and preparation method thereof | |
| CN104726102A (en) | Fluorescent anti-counterfeiting material and preparation method thereof | |
| CN110408390A (en) | A kind of cerium enhancing wheat bran is carbon source red fluorescence carbon quantum dot preparation method | |
| CN106554772B (en) | A kind of preparation method of rare earth luminescent fiber | |
| CN110951479A (en) | Preparation method of PEG (polyethylene glycol) coated porous rare earth phosphate fluorescent nano material | |
| CN108485656B (en) | X-ray imaging material | |
| CN104789223A (en) | Novel method for preparing fluorescence LaVO4:Eu nanoflower and application thereof | |
| CN109776586A (en) | A kind of piece of crystal form be organic-rare-earth complex, luminescent fibre and preparation method thereof | |
| CN109181696A (en) | A kind of red long-persistence nano-luminescent materials | |
| CN103696018B (en) | A kind of novel fluorescence crystalline material sulfosalicylic acid ammonium and its preparation and purposes | |
| CN108048078B (en) | Fluorescent dual-response hollow mesoporous material and preparation method and application thereof | |
| CN103979513B (en) | A kind of cocoon-like TbPO with good luminous performance4powder body and preparation method thereof | |
| CN103074061A (en) | Synthetic method of rare earth nanometer nuclear shell spherical particle luminescent material | |
| CN102618252B (en) | Fluorescently-labeled hydroxyapatite hollow microsphere and preparation method thereof | |
| CN102676166A (en) | Water-soluble rare earth ion doped zirconium dioxide nano fluorescence labeling material and preparation method thereof | |
| CN102995154A (en) | Preparation method of rare earth fluorescence micro-nano fiber array | |
| CN105110371B (en) | A kind of many pattern metavanadate powder body and preparation method thereof | |
| CN110804433A (en) | Preparation method of chitosan-coated rare earth phosphate fluorescent nano material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |