CN108003861A - Hydrophobic modified fluorescent powder and preparation method and application thereof - Google Patents
Hydrophobic modified fluorescent powder and preparation method and application thereof Download PDFInfo
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- CN108003861A CN108003861A CN201711165725.6A CN201711165725A CN108003861A CN 108003861 A CN108003861 A CN 108003861A CN 201711165725 A CN201711165725 A CN 201711165725A CN 108003861 A CN108003861 A CN 108003861A
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- 239000000843 powder Substances 0.000 title claims abstract description 205
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000002209 hydrophobic effect Effects 0.000 title abstract description 53
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 25
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 22
- 238000000197 pyrolysis Methods 0.000 claims abstract description 17
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 12
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000012670 alkaline solution Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000004381 surface treatment Methods 0.000 claims abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 67
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 37
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 29
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 21
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910018557 Si O Inorganic materials 0.000 claims description 5
- 229910004412 SrSi2 Inorganic materials 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 5
- 229910004706 CaSi2 Inorganic materials 0.000 claims description 4
- 229910018540 Si C Inorganic materials 0.000 claims description 4
- 229910007991 Si-N Inorganic materials 0.000 claims description 4
- 229910006294 Si—N Inorganic materials 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 239000000700 radioactive tracer Substances 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- -1 nitride compound Chemical class 0.000 abstract description 16
- 239000011247 coating layer Substances 0.000 abstract 1
- 238000012986 modification Methods 0.000 description 35
- 238000012360 testing method Methods 0.000 description 33
- 230000008859 change Effects 0.000 description 25
- 230000004048 modification Effects 0.000 description 21
- 239000007788 liquid Substances 0.000 description 16
- 238000010586 diagram Methods 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 13
- 238000012430 stability testing Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 229920001296 polysiloxane Polymers 0.000 description 11
- 229910004709 CaSi Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229910004122 SrSi Inorganic materials 0.000 description 9
- 230000003595 spectral effect Effects 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 150000004645 aluminates Chemical class 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical group [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000005915 ammonolysis reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000001846 repelling effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- 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
- C09K11/0883—Arsenides; Nitrides; Phosphides
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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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7734—Aluminates
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B47/00—Survey of boreholes or wells
- E21B47/10—Locating fluid leaks, intrusions or movements
- E21B47/11—Locating fluid leaks, intrusions or movements using tracers; using radioactivity
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
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- H01L33/502—Wavelength conversion materials
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Abstract
The invention provides a hydrophobic modified fluorescent powder and a preparation method and application thereof. The preparation method of the hydrophobic modified fluorescent powder comprises the following steps: the method comprises the following steps: placing the fluorescent powder in an acid solution or an alkaline solution for surface treatment to obtain surface-treated fluorescent powder; step two: mixing the surface-treated fluorescent powder with chlorosilane and an organic solvent, and stirring until the organic solvent is completely volatilized to obtain a mixture; step three: and putting the mixture in an ammonia atmosphere for pyrolysis treatment to obtain the hydrophobic modified fluorescent powder. The hydrophobic modified fluorescent powder forms a coating layer with proper thickness on the surface of the silicon-based (oxy) nitride compound fluorescent powder, and can improve the stability and the hydrophobicity of the silicon-based (oxy) nitride compound fluorescent powder in a high-temperature and high-humidity environment.
Description
Technical field
The invention belongs to luminescent material technical field, and in particular to a kind of hydrophobically modified fluorescent powder and preparation method thereof is with answering
With.
Background technology
The solid-state lighting of LED has been obtained due to its high luminous efficiency, low energy consumption, long-life, high reliability
It is widely applied very much.Fluorescent powder is one of necessary condition of solid-state lighting, usually, will be changed by fluorescent powder under blue chip
To greenish-yellow red wave band.Fluorescent powder in solid-state lighting use must have suitable luminescence band, high quantum efficiency, low
Hot-quenching is gone out and the advantage such as high reliability.
However, during the use of fluorescent powder, the problem of being commonly encountered be exactly it is hot and humid caused by light decay problem, and then
Influence the service life of fluorescent powder.For example it is known that thiogallate (SrGaS4:) and sulfide (CaS Eu:Eu and
SrS:Eu it is) unstable fluorescent powder, certainly, aluminate and silicate, or even silicon substrate (oxygen) nitrogen compound also face so
The problem of.
High temperature (high humidity) the fluorescent quenching mechanism of silicon substrate (oxygen) nitrogen compound is explained in many researchs, is passed through
Surface modification makes its material have a water resisting property to have obtained very extensive research.For example, using pyrophosphoric acid surface modification in aluminate
MAl2O4:Eu2+,Dy3+Phosphor surface forms one layer of MAl2B2O7(M=Sr, Ca, Ba) makes it have water-resistance.It is in addition, miscellaneous
Cycle compound, β-second diketone and multilayer carboxylic acid are each applied among aluminate water resistant sex modification.However, pass through water-resistance
Stability of the fluorescent powder under hot and humid environment is improved after modification to be but rarely reported.
Heat caused by hot and humid declines generally and has following two reasons：The hydrolysis of lattice and the oxidation of the centre of luminescence.In table
Face forms suitable inorganic layer and is beneficial to the erosion that protection fluorescent powder protects it from steam.However, most of inoranic membrane (examples
Such as, pyrophosphate, silicate and aluminate) it is hydrophilic material, material can be caused by forming this inoranic membrane on fluorescent material surface
Material is easier adsorbed water molecule, thus the erosion for being easier to be subject to water and make the decay of luminescence of fluorescent material, and then influence it and make
Use the service life.Blocked up inorganic layer can influence the intrinsic of fluorescent material and shine again.Therefore, the surface hydrophobic decorative layer of fluorescent material
Thickness will be adapted to, and it is still had a water resisting property in high temperature.
Therefore, a kind of fluorescent powder of new surface hydrophobicity modification is researched and developed, can be protected under hot and humid environment
It is a problem for being badly in need of solving instantly to hold good stability of photoluminescence.
The content of the invention
In view of the shortcomings that above-mentioned prior art, it is an object of the invention to provide a kind of hydrophobically modified fluorescent powder and its preparation
Method and application.The hydrophobically modified fluorescent powder forms the suitable bag of a layer thickness in silicon substrate (oxygen) nitrogen compound phosphor surface
Coating, it is possible to increase stability and hydrophobicity of silicon substrate (oxygen) the nitrogen compound fluorescent powder under hot and humid environment.
In order to reach foregoing goal of the invention, the present invention provides a kind of preparation method of hydrophobically modified fluorescent powder, it includes
Following steps：
Step 1：Fluorescent powder is placed in acid solution or alkaline solution and is surface-treated, is obtained surface treated
Fluorescent powder；
Step 2：The surface treated fluorescent powder is mixed with chlorosilane, organic solvent, is stirred to described organic molten
Agent volatilization is complete, obtains mixture；
Step 3：The mixture is placed in ammonia atmosphere and carries out pyrolysis processing, obtains hydrophobically modified fluorescent powder.
Above-mentioned preparation method, using having chlorosilane as the initial feed reacted, after ammonolysis and heat treatment,
One layer of stable nanometer clad can be formed in phosphor surface, so as to improve the hydrophobicity of phosphor surface, make dredging for acquisition
Water is modified fluorescent powder has very high stability and hydrophobicity under hot and humid environment.
After placing for a long time in atmosphere or in the long-term use, unmodified phosphor surface can aoxidize,
Silicon oxide compound is formed, causes the reduction of light-emitting phosphor intensity, the silicon oxide compound is mostly hydrophilic radical in addition, can be caused glimmering
The stability of light powder drastically declines, and preparation method of the invention avoids the formation of phosphor surface oxide layer, can make acquisition
The brightness of hydrophobically modified fluorescent powder obtain certain lifting.
According to a particular embodiment of the invention, it is preferable that described surface treated glimmering in terms of the quality of the fluorescent powder
The mixing ratio of light powder, chlorosilane and organic solvent is 1g：(5-15)ml：(10-50)ml.
According to a particular embodiment of the invention, it is preferable that the temperature of the pyrolysis processing is 100 DEG C -800 DEG C, and the time is
1h-3h。
In the step 3, the mixture is placed in ammonia atmosphere and carries out pyrolysis processing, chlorosilane can be made in ammonia
Under the conditions of gas with fluorescent powder (such as Ba2SiO4:Eu2+) the Si-O bonds on surface close, and in a heated condition in fluorescent powder table
Face forms inorganic nano clad, obtains the fluorescent powder by inorganic nano hydrophobically modified of stabilization.
According to a particular embodiment of the invention, it is preferable that the fluorescent powder includes silicon-based oxynitride fluorescent powder；
It is highly preferred that the fluorescent powder includes Ba2SiO4:Eu2+Green emitting phosphor, Sr2Si5N8:Eu2+Red fluorescence powder,
Ca2Si5N8:Eu2+Red fluorescence powder, Ba2Si5N8:Eu2+Red fluorescence powder, LaSiO2N:Ce3+Blue colour fluorescent powder, SrLiAl3N4:
Eu2+Red fluorescence powder, CaSi2O2N2:Eu2+Yellow fluorescent powder, SrSi2O2N2:Eu2+Green emitting phosphor, Ba3Si6O12N2:Eu2+It is green
Color fluorescent powder, SrSiN2:Eu2+Red fluorescence powder and La2Si6O3N8:Ce3+Any of blue colour fluorescent powder.
The preparation method of the fluorescent powder includes solid phase method and sol-gal process.With Ba2SiO4:Eu2+Exemplified by, with solid phase method
Ba processed2SiO4:Eu2+The raw material of green emitting phosphor is BaCO3、SiO2And Eu2O3, weigh in proportion after raw material by being ground
After roasted, wherein, Ba2SiO4:Eu2+Middle Eu2+Content be 6%；The Ba prepared with sol-gal process2SiO4:Eu2+Green
The raw material of fluorescent powder includes tetraethyl orthosilicate, barium carbonate and europium oxide, wherein, Ba2SiO4:Eu2+Middle Eu2+Content be
6%.
According to a particular embodiment of the invention, it is preferable that the step of surface treatment is：At room temperature, by the fluorescence
Powder is placed in acid solution or alkaline solution and handles 5-30min, is washed out drying, obtains the surface treated fluorescence
Powder.
According to a particular embodiment of the invention, it is preferable that preferably, it is molten that the acid solution includes hydrochloric acid solution, acetic acid
One or more combinations in liquid and oxalic acid solution, the molar concentration of the acid solution is 0.01-1mol/L.
According to a particular embodiment of the invention, it is preferable that it is molten that the alkaline solution includes potassium hydroxide solution, sodium hydroxide
One or more combinations in liquid, ammonium hydroxide and calcium hydroxide solution, the molar concentration of the alkaline solution is 0.01-1mol/
L。
According to a particular embodiment of the invention, it is preferable that the organic solvent includes normal heptane, hexamethylene, benzene and toluene
In one or more of combinations.
According to a particular embodiment of the invention, it is preferable that the chlorosilane includes dimethyl dichlorosilane (DMCS) and/or dimethyl two
Chlorosilane.
The preparation method of the present invention can select different reagents according to the specific surface group of fluorescent powder, such as fluorescent powder table
Surface treatment can in an acidic solution, and solvent can be toluene and benzene etc., chlorosilane include but not limited to dimethyl dichlorosilane (DMCS) and
Dimethyldichlorosilane.The preparation method techniqueflow is simple, and required raw material is cheap, and modification reaction process will not cause ring
The secondary pollution in border, possesses preferably by modifying the hydrophobically modified fluorescent powder prepared relative to unmodified fluorescence in situ powder
The features such as long-time stability, hydrophobicity and water repelling property.
The present invention also provides a kind of hydrophobically modified fluorescent powder, it is made by the preparation method of above-mentioned hydrophobically modified fluorescent powder
's.
According to a particular embodiment of the invention, it is preferable that surface hydrophobicity angle >=112 ° of the hydrophobically modified fluorescent powder.Into
The hot and humid test of row finds that in 100 DEG C of water heating kettles, the fluorescent powder by modification can keep the intact of phase, not have at the same time
Light drops, but fluorescent powder in situ can then be undergone phase transition under similarity condition, lose the characteristics of luminescence, thus proves glimmering after modification
Light powder still has good stability in hot and humid condition of high voltage.
According to a particular embodiment of the invention, it is preferable that the hydrophobically modified phosphor surface coats one layer by Si-O,
The inorganic covalent structure nano particles layer that Si-C and Si-N covalent bonds are formed by connecting；The inorganic covalent structure nano particles layer
Thickness is 20nm-40nm.The nano particle clad mainly by Si-O, Si-C and Si-N covalent bonds be formed by connecting strong three
Inorganic network structure is tieed up, which is tightly coated on phosphor surface, substantially increases the hydrophobicity of phosphor surface, because
This, which has more preferable long-time stability and service life.
The present invention also provides a kind of light-emitting device, the light-emitting device includes illuminating source and above-mentioned hydrophobically modified fluorescence
Powder.
According to a particular embodiment of the invention, it is preferable that the light-emitting device includes white LED lamp.
The present invention also provides above-mentioned hydrophobically modified fluorescent powder on oil field in shale gas exploitation as Interwell tracer should
With.
The hydrophobically modified fluorescent powder is injected at thousands of meters of underground in terms of the exploitation of shale gas, in Different Strata temperature, pressure
, can retention property stabilization in the case of power and salinity.In anti-drain, according to the change of light-emitting phosphor intensity, with reference to other
Geologic information, can obtain strata pressure, and anti-row leads, the information such as shale gas yield.
Compared with prior art, the invention has the advantages that：
(1) preparation method of hydrophobically modified fluorescent powder provided by the invention, by the use of have chlorosilane as reaction initial original
Material, after ammonolysis and heat treatment, forms one layer in phosphor surface and is formed by connecting by Si-O, Si-C and Si-N covalent bonds
Three-D inorganic network structure decorative layer, so as to improve the hydrophobicity of phosphor surface, more has the hydrophobically modified fluorescent powder of acquisition
There are more preferable long-time stability and service life；
(2) preparation method provided by the invention receiving in phosphor surface one layer of 20-40nm size tightly coated of formation
Rice grain, effectively prevent the formation of phosphor surface oxide layer, can obtain the brightness of the hydrophobically modified fluorescent powder of acquisition
Certain lifting；And the hydrophobically modified fluorescent powder is compared with unmodified fluorescence in situ powder, in thermostabilization, chemical stability
Tool has great advantage；
(3) hydrophobically modified fluorescent powder provided by the invention tightly coats receiving for one layer of 20-40nm size in phosphor surface
Rice grain decorative layer, therefore, it is special which possesses more preferable long-time stability, hydrophobicity and water repelling property etc.
Point；
(4) surface of hydrophobically modified fluorescent powder provided by the invention can be very good compatibility with organic matter, can be with
The uniformity of fluorescent powder during encapsulation LED is improved well, can be widely used in LEDs fluorescent powders；It is in addition, of the invention
The hydrophobically modified fluorescent powder of offer is good with stability, environmental protection, high luminous efficiency and other features, can excite the long wave inorganic
Fluorescent powder is used as tracer on oil field in shale gas exploitation.
(5) preparation method provided by the invention, instrument majority can voluntarily be processed and built needed for modification, fluorescent powder modification
Effect is good, and practicality is high, and possesses good stability for a long time, can having as the disagreeableness organic fluorescent dye of environment
Substitute is imitated, is used as the indicator of inter-well tracer test in shale gas exploitation on oil field, which has potential practical
Development prospect, and practical application is without causing secondary pollution.
Brief description of the drawings
Fig. 1 is Ba in embodiment 12SiO4:Eu2+XRD comparison diagrams before and after green emitting phosphor hydrophobically modified；
Fig. 2 is Ba in embodiment 12SiO4:Eu2+The hydrophobic angle test comparison of green emitting phosphor hydrophobically modified front and rear surfaces
Figure；
Fig. 3 is Ba in embodiment 12SiO4:Eu2+Heat stability testing comparison diagram before and after green emitting phosphor hydrophobically modified；
Fig. 4 is Ca in embodiment 22Si5N8:Eu2+XRD diagram after red fluorescence powder hydrophobically modified；
Fig. 5 is Ca in embodiment 22Si5N8:Eu2+Hydrophobic angle test chart after red fluorescence powder hydrophobically modified；
Fig. 6 is Ba in embodiment 32Si5N8:Eu2+XRD diagram after red fluorescence powder hydrophobically modified；
Fig. 7 is Ba in embodiment 32Si5N8:Eu2+Hydrophobic angle test chart after red fluorescence powder hydrophobically modified；
Fig. 8 is Sr in embodiment 42Si5N8:Eu2+XRD diagram after red fluorescence powder hydrophobically modified；
Fig. 9 is Sr in embodiment 42Si5N8:Eu2+Hydrophobic angle test chart after red fluorescence powder hydrophobically modified；
Figure 10 is LaSiO in embodiment 52N:Ce3+XRD diagram after blue colour fluorescent powder hydrophobically modified；
Figure 11 is LaSiO in embodiment 52N:Ce3+Hydrophobic angle test chart after blue colour fluorescent powder hydrophobically modified；
Figure 12 is SrLiAl in embodiment 63N4:Eu2+XRD diagram after red fluorescence powder hydrophobically modified；
Figure 13 is SrLiAl in embodiment 63N4:Eu2+Hydrophobic angle test chart after red fluorescence powder hydrophobically modified；
Figure 14 is CaSi in embodiment 72O2N2:Eu2+XRD diagram after yellow fluorescent powder hydrophobically modified；
Figure 15 is CaSi in embodiment 72O2N2:Eu2+Hydrophobic angle test chart after yellow fluorescent powder hydrophobically modified；
Figure 16 is SrSi in embodiment 82O2N2:Eu2+XRD diagram after green emitting phosphor hydrophobically modified；
Figure 17 is SrSi in embodiment 82O2N2:Eu2+Hydrophobic angle test chart after green emitting phosphor hydrophobically modified；
Figure 18 is Ba in embodiment 93Si6O12N2:Eu2+XRD diagram after green emitting phosphor hydrophobically modified；
Figure 19 is Ba in embodiment 93Si6O12N2:Eu2+Hydrophobic angle test chart after green emitting phosphor hydrophobically modified；
Figure 20 is SrSiN in embodiment 102:Eu2+XRD diagram after red fluorescence powder hydrophobically modified；
Figure 21 is SrSiN in embodiment 102:Eu2+Hydrophobic angle test chart after red fluorescence powder hydrophobically modified；
Figure 22 is La in embodiment 112Si6O3N8:Ce3+XRD diagram after blue colour fluorescent powder hydrophobically modified；
Figure 23 is La in embodiment 112Si6O3N8:Ce3+Hydrophobic angle test chart after blue colour fluorescent powder hydrophobically modified.
Embodiment
In order to which technical characteristic, purpose and the beneficial effect of the present invention is more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
Embodiment 1
Present embodiments provide a kind of Ba by hydrophobically modified2SiO4:Eu2+Green emitting phosphor, it is by following step
Suddenly prepare：
Weigh 1g Ba2SiO4:Eu2+Green emitting phosphor, fluorescent powder is placed in ammonia spirit and handles 10min, is washed out
It is dry；
By the Ba after AMMONIA TREATMENT2SiO4:Eu2+Green emitting phosphor adds in 25mL normal heptanes and forms mixed solution, upwards
To state and 5mL dimethyl dichlorosilane (DMCS)s and 5ml dimethyldichlorosilanes are added in mixed solution, stir 30 minutes, normal heptane volatilizees completely,
Obtain blend sample；
The blend sample is put into horizontal pipe stove and is led to after ammonia 5min when pyrolysis 2 is small at a temperature of 500 DEG C, then
Cooling obtains the mixture of residual fraction liquid polysiloxane, which is filtered, drying and processing, you can must pass through hydrophobic change
The Ba of property2SiO4:Eu2+Green emitting phosphor.
To the Ba before and after the present embodiment hydrophobically modified2SiO4:Eu2+Green emitting phosphor carries out X-ray diffraction and hydrophobic angle
Contrast experiment, as a result as depicted in figs. 1 and 2.
Ba before the present embodiment modification2SiO4:Eu2+The XRD diagram of green emitting phosphor is as shown in fig. 1A, it can be seen that repaiies
Ba before decorations2SiO4:Eu2+Green emitting phosphor has good crystallinity；Modification Ba after modification2SiO4:Eu2+Green emitting phosphor
As shown in fig. ib, diffraction peak does not change XRD diagram, illustrates the method for modifying of the present embodiment to Ba2SiO4:Eu2+Green
The crystalline phase of fluorescent powder will not have an impact in itself.
Ba before the present embodiment modification2SiO4:Eu2+The hydrophobic angle test chart of green emitting phosphor is dredged as shown in a in Fig. 2
Nearly 0 degree of water corner connection, it is seen that the Ba before modification2SiO4:Eu2+Green emitting phosphor is total hydrophilic；Ba after modification2SiO4:Eu2+
The hydrophobic angle test chart of green emitting phosphor is as shown in the b in Fig. 2, and hydrophobic angle is 116 degree, it is seen that the method for modifying of the present embodiment exists
Ba2SiO4:Eu2+Green emitting phosphor surface forms hydrophobic structure, has achieveed the purpose that hydrophobically modified.
To the Ba before and after the present embodiment hydrophobically modified2SiO4:Eu2+Green emitting phosphor carries out heat stability testing experiment.Will
Modified Ba2SiO4:Eu2+Then green emitting phosphor is tested before and after its hydro-thermal when hydro-thermal (100 DEG C) 48 is small in water heating kettle
Spectral intensity change, and with the Ba before modification2SiO4:Eu2+Spectral intensity change contrast before and after green emitting phosphor hydro-thermal, test
The results are shown in Figure 3, wherein the Ba before modification2SiO4:Eu2+Green emitting phosphor is after 100 DEG C of hydro-thermal 48h, and spectral intensity is drastically
Reduce；And pass through the Ba of hydrophobically modified2SiO4:Eu2+Under green emitting phosphor spectral intensity after 100 DEG C of hydro-thermal 48h is only slight
Drop, shows good heat endurance.
Embodiment 2
Present embodiments provide a kind of Ca by hydrophobically modified2Si5N8:Eu2+Red fluorescence powder, it is by following step
Suddenly prepare：
Weigh 1g Ca2Si5N8:Eu2+Red fluorescence powder, fluorescent powder is placed in oxalic acid aqueous solution and handles 15min, Ran Houxi
Wash drying；
Ca after oxalic acid aqueous solution is handled2Si5N8:Eu2+It is molten that red fluorescence powder adds formation mixing in 15mL hexamethylenes
Liquid, 5mL dimethyl dichlorosilane (DMCS)s are added into above-mentioned mixed solution, are stirred 30 minutes, hexamethylene volatilizees completely, obtains mixture sample
Product；
The blend sample is put into horizontal pipe stove and is led to after ammonia 5min when pyrolysis 2 is small at a temperature of 500 DEG C, then
Cooling obtains the mixture of residual fraction liquid polysiloxane, which is filtered, drying and processing, you can must pass through hydrophobic change
The Ca of property2Si5N8:Eu2+Red fluorescence powder.
To the Ca after the present embodiment hydrophobically modified2Si5N8:Eu2+Red fluorescence powder carries out the reality of X-ray diffraction and contact angle
Test, as a result as shown in Figure 4 and Figure 5.
As seen from Figure 4, with Ca before modified2Si5N8:Eu2+Red fluorescence powder is compared, after the present embodiment hydrophobically modified
Ca2Si5N8:Eu2+The XRD diffraction peaks of red fluorescence powder do not change, and illustrate the method for modifying of the present embodiment to Ca2Si5N8:
Eu2+The crystalline phase of red fluorescence powder will not have an impact in itself.
As seen from Figure 5, the Ca after the present embodiment hydrophobically modified2Si5N8:Eu2+The hydrophobic angle test of red fluorescence powder,
Contact angle is 118 degree, forms hydrophobic structure, has achieveed the purpose that hydrophobically modified.
To the Ca after the present embodiment hydrophobically modified2Si5N8:Eu2+Red fluorescence powder has carried out heat stability testing, its spectrum
Intensity slightly decreases after 100 DEG C of hydro-thermal 48h, shows good heat endurance.
Embodiment 3
Present embodiments provide a kind of Ba by hydrophobically modified2Si5N8:Eu2+Red fluorescence powder, it is by following step
Suddenly prepare：
Weigh 1g Ba2Si5N8:Eu2+Red fluorescence powder, is placed in ammonia spirit and handles 15min, is washed out drying；
By the Ba after AMMONIA TREATMENT2Si5N8:Eu2+Red fluorescence powder adds in 25mL benzene and forms mixed solution, is mixed to above-mentioned
Close and 3mL dimethyl dichlorosilane (DMCS)s and 3ml dimethyldichlorosilanes are added in solution, stir 30 minutes, benzene volatilizees completely, is mixed
Thing sample；
The blend sample is put into horizontal pipe stove and is led to after ammonia 5min when pyrolysis 2 is small at a temperature of 400 DEG C, then
Cooling obtains the mixture of residual fraction liquid polysiloxane, which is filtered, drying and processing, you can must pass through hydrophobic change
The Ba of property2Si5N8:Eu2+Red fluorescence powder.
To the Ba after the present embodiment hydrophobically modified2Si5N8:Eu2+Red fluorescence powder carries out the reality of X-ray diffraction and contact angle
Test, as a result as shown in Figure 6 and Figure 7.
As seen from Figure 6, with Ba before modified2Si5N8:Eu2+Red fluorescence powder is compared, after the present embodiment hydrophobically modified
Ba2Si5N8:Eu2+The XRD diffraction peaks of red fluorescence powder do not change, and illustrate the method for modifying of the present embodiment to Ba2Si5N8:
Eu2+The crystalline phase of red fluorescence powder will not have an impact in itself.
As seen from Figure 7, the Ba after the present embodiment hydrophobically modified2Si5N8:Eu2+The hydrophobic angle test of red fluorescence powder,
Contact angle is 118 degree, forms hydrophobic structure, has achieveed the purpose that hydrophobically modified.
The Ba of modification to the present embodiment2Si5N8:Eu2+Red fluorescence powder has carried out heat stability testing, its spectral intensity
Slightly decreased after 100 DEG C of hydro-thermal 48h, show good heat endurance.
Embodiment 4
Present embodiments provide a kind of Sr by hydrophobically modified2Si5N8:Eu2+Red fluorescence powder, it is by following step
Suddenly prepare：
Weigh 0.5g Sr2Si5N8:Eu2+Red fluorescence powder, is placed in ammonia spirit and handles 15min, is washed out drying；
It is added in 25ml normal heptanes and forms mixed solution, 4ml dimethyldichlorosilanes are added into above-mentioned mixed solution, stirs 30 points
Clock；Normal heptane volatilizees completely, obtains blend sample；
The blend sample is put into horizontal pipe stove and is led to after ammonia 5min when pyrolysis 2 is small at a temperature of 600 DEG C, then
Cooling obtains the mixture of residual fraction liquid polysiloxane, which is filtered, drying and processing, you can must pass through hydrophobic change
The Sr of property2Si5N8:Eu2+Red fluorescence powder.
To the Sr after the present embodiment hydrophobically modified2Si5N8:Eu2+Red fluorescence powder carries out the reality of X-ray diffraction and contact angle
Test, as a result as shown in Figure 8 and Figure 9.
As seen from Figure 8, with Sr before modified2Si5N8:Eu2+Red fluorescence powder is compared, after the present embodiment hydrophobically modified
Modification Sr2Si5N8:Eu2+The XRD diffraction peaks of red fluorescence powder do not change, and illustrate the method for modifying pair of the present embodiment
Sr2Si5N8:Eu2+The crystalline phase of red fluorescence powder will not have an impact in itself.
As seen from Figure 9, the Sr after the present embodiment hydrophobically modified2Si5N8:Eu2+The hydrophobic angle test of red fluorescence powder,
Contact angle is 114 degree, forms hydrophobic structure, has achieveed the purpose that hydrophobically modified.
To the Sr after the hydrophobically modified of the present embodiment2Si5N8:Eu2+Red fluorescence powder has carried out heat stability testing, its light
Spectral intensity slightly decreases after 100 DEG C of hydro-thermal 48h, shows good heat endurance.
Embodiment 5
Present embodiments provide a kind of LaSiO by hydrophobically modified2N:Ce3+Blue colour fluorescent powder, it is by following step
Suddenly prepare：
Weigh 0.5g LaSiO2N:Ce3+Blue colour fluorescent powder, is placed in oxalic acid aqueous solution and handles 15min, is washed out doing
It is dry；It is then added in 25ml normal heptanes, adds 3ml dimethyl dichlorosilane (DMCS)s, stirs 30 minutes, normal heptane volatilizees completely, obtains
To blend sample；
The blend sample is put into horizontal pipe stove and is led to after ammonia 5min when pyrolysis 2 is small at a temperature of 300 DEG C, then
Cooling obtains the mixture of residual fraction liquid polysiloxane, which is filtered, drying and processing, you can must pass through hydrophobic change
The LaSiO of property2N:Ce3+Blue colour fluorescent powder.
To the LaSiO after the present embodiment hydrophobically modified2N:Ce3+Blue colour fluorescent powder carries out the reality of X-ray diffraction and contact angle
Test, as a result as shown in Figure 10 and Figure 11.
As seen from Figure 10, with LaSiO before modified2N:Ce3+Blue colour fluorescent powder is compared, changing after the present embodiment modification
Property LaSiO2N:Ce3+The XRD diffraction peaks of blue colour fluorescent powder do not change, and illustrate the method for modifying of the present embodiment to LaSiO2N:
Ce3+The crystalline phase of blue colour fluorescent powder will not have an impact in itself.
As seen from Figure 11, the LaSiO after the present embodiment modification2N:Ce3+The hydrophobic angle test of blue colour fluorescent powder, contact
Angle is 115 degree, forms hydrophobic structure, has achieveed the purpose that hydrophobically modified.
To the LaSiO after the present embodiment hydrophobically modified2N:Ce3+Blue colour fluorescent powder has carried out heat stability testing, its spectrum
Intensity slightly decreases after 100 DEG C of hydro-thermal 48h, shows good heat endurance.
Embodiment 6
Present embodiments provide a kind of SrLiAl by hydrophobically modified3N4:Eu2+Red fluorescence powder, it is by following
Prepared by step：
Weigh 1g SrLiAl3N4:Eu2+Red fluorescence powder, is placed in ammonia spirit and handles 10min, is washed out drying；
It is then added in 20ml normal heptanes and forms mixed solution, 2ml dimethyldichlorosilanes and 1ml is added into above-mentioned mixed solution
Dimethyl dichlorosilane (DMCS), stir 30 minutes；Normal heptane volatilizees completely, obtains blend sample；
The blend sample is put into horizontal pipe stove and is led to after ammonia 5min when pyrolysis 2 is small at a temperature of 600 DEG C, then
Cooling obtains the mixture of residual fraction liquid polysiloxane, which is filtered, drying and processing, you can must pass through hydrophobic change
The SrLiAl of property3N4:Eu2+Red fluorescence powder.
To the SrLiAl after the present embodiment hydrophobically modified3N4:Eu2+Red fluorescence powder carries out X-ray diffraction and contact angle
Experiment, as a result as shown in Figure 12 and Figure 13.
As seen from Figure 12, with SrLiAl before modified3N4:Eu2+Red fluorescence powder is compared, after the present embodiment modification
Modified SrLiAl3N4:Eu2+The XRD diffraction peaks of red fluorescence powder do not change, and illustrate the method for modifying pair of the present embodiment
SrLiAl3N4:Eu2+The crystalline phase of red fluorescence powder will not have an impact in itself.
As seen from Figure 13, the SrLiAl after the present embodiment modification3N4:Eu2+The hydrophobic angle test of red fluorescence powder, connects
Feeler is 106 degree, forms hydrophobic structure, has achieveed the purpose that hydrophobically modified.
To the SrLiAl after the present embodiment hydrophobically modified3N4:Eu2+Red fluorescence powder has carried out heat stability testing, its light
Spectral intensity slightly decreases after 100 DEG C of hydro-thermal 48h, shows good heat endurance.
Embodiment 7
Present embodiments provide a kind of CaSi by hydrophobically modified2O2N2:Eu2+Yellow fluorescent powder, it is by following step
Suddenly prepare：
Weigh 1g CaSi2O2N2:Eu2+Yellow fluorescent powder, is placed in oxalic acid solution and handles 15min, is washed out drying；
CaSi after oxalic acid aqueous solution is handled2O2N2:Eu2+Yellow fluorescent powder, which is added in 25ml hexamethylenes, forms mixing
Solution, 5ml dimethyl dichlorosilane (DMCS)s and 5ml dimethyldichlorosilanes are added into above-mentioned mixed solution, are stirred 30 minutes；Hexamethylene
Volatilization completely, obtains blend sample；
The blend sample is put into horizontal pipe stove and is led to after ammonia 5min when pyrolysis 2 is small at a temperature of 600 DEG C, then
Cooling obtains the mixture of residual fraction liquid polysiloxane, which is filtered, drying and processing, you can must pass through hydrophobic change
The CaSi of property2O2N2:Eu2+Yellow fluorescent powder.
To the CaSi after the present embodiment hydrophobically modified2O2N2:Eu2+Yellow fluorescent powder carries out the reality of X-ray diffraction and contact angle
Test, as a result as shown in Figure 14 and Figure 15.
As seen from Figure 14, with CaSi before modified2O2N2:Eu2+Yellow fluorescent powder is compared, the present embodiment hydrophobically modified
CaSi afterwards2O2N2:Eu2+The XRD diffraction peaks of yellow fluorescent powder do not change, and illustrate the present embodiment method of modifying pair
CaSi2O2N2:Eu2+The crystalline phase of yellow fluorescent powder will not have an impact in itself.
As seen from Figure 15, the CaSi after the present embodiment modification2O2N2:Eu2+The hydrophobic angle test of yellow fluorescent powder, connects
Feeler is 117 degree, forms hydrophobic structure, has achieveed the purpose that hydrophobically modified.
To the CaSi after the present embodiment hydrophobically modified2O2N2:Eu2+Yellow fluorescent powder has carried out heat stability testing, its spectrum
Intensity slightly decreases after 100 DEG C of hydro-thermal 48h, shows good heat endurance.
Embodiment 8
Present embodiments provide a kind of SrSi by hydrophobically modified2O2N2:Eu2+Green emitting phosphor, it is by following step
Suddenly prepare：
Weigh 0.8g SrSi2O2N2:Eu2+Green emitting phosphor, is placed in oxalic acid solution and handles 15min, is washed out drying；
SrSi after oxalic acid aqueous solution is handled2O2N2:Eu2+Green emitting phosphor, which is added in 25ml hexamethylenes, forms mixing
Solution, 5ml dimethyl dichlorosilane (DMCS)s and 5ml dimethyldichlorosilanes are added into above-mentioned mixed solution, are stirred 30 minutes；Hexamethylene
Volatilization completely, obtains blend sample；
The blend sample is put into horizontal pipe stove and is led to after ammonia 5min when pyrolysis 2 is small at a temperature of 600 DEG C, then
Cooling obtains the mixture of residual fraction liquid polysiloxane, which is filtered, drying and processing, you can must pass through hydrophobic change
The SrSi of property2O2N2:Eu2+Green emitting phosphor.
To the SrSi after the present embodiment hydrophobically modified2O2N2:Eu2+Green emitting phosphor carries out the reality of X-ray diffraction and contact angle
Test, as a result as shown in Figure 16 and Figure 17.
As seen from Figure 16, with SrSi before modified2O2N2:Eu2+Green emitting phosphor is compared, after the present embodiment modification
Modified SrSi2O2N2:Eu2+The XRD diffraction peaks of green emitting phosphor do not change, and illustrate this method of modifying to SrSi2O2N2:Eu2+
The crystalline phase of green emitting phosphor will not have an impact in itself.
As seen from Figure 17, the SrSi after the present embodiment modification2O2N2:Eu2+The hydrophobic angle test of green emitting phosphor, connects
Feeler is 120 degree, forms hydrophobic structure, has achieveed the purpose that hydrophobically modified.
To the SrSi after the present embodiment hydrophobically modified2O2N2:Eu2+Green emitting phosphor has carried out heat stability testing, its spectrum
Intensity slightly decreases after 100 DEG C of hydro-thermal 48h, shows good heat endurance.
Embodiment 9
Present embodiments provide a kind of Ba by hydrophobically modified3Si6O12N2:Eu2+Green emitting phosphor, it is by following
Prepared by step：
Weigh 0.5g Ba3Si6O12N2:Eu2+Green emitting phosphor, is placed in hydrochloric acid solution and handles 15min, is washed out doing
It is dry；
Ba after hydrochloric acid solution is handled3Si6O12N2:Eu2+It is molten that green emitting phosphor adds formation mixing in 25mL hexamethylenes
Liquid, 5ml dimethyl dichlorosilane (DMCS)s and 5ml dimethyldichlorosilanes are added into above-mentioned mixed solution, are stirred 30 minutes；Hexamethylene is complete
Full volatilization, obtains blend sample；
The blend sample is put into horizontal pipe stove and is led to after ammonia 5min when pyrolysis 2 is small at a temperature of 600 DEG C, then
Cooling obtains the mixture of residual fraction liquid polysiloxane, which is filtered, drying and processing, you can must pass through hydrophobic change
The Ba of property3Si6O12N2:Eu2+Green emitting phosphor.
To the Ba after the present embodiment hydrophobically modified3Si6O12N2:Eu2+Green emitting phosphor carries out X-ray diffraction and contact angle
Experiment, as a result as shown in Figure 18 and Figure 19.
As seen from Figure 18, with Ba before modified3Si6O12N2:Eu2+Green emitting phosphor is compared, after the present embodiment modification
Modification Ba3Si6O12N2:Eu2+The XRD diffraction peaks of green emitting phosphor do not change, and illustrate this method of modifying pair
Ba3Si6O12N2:Eu2+The crystalline phase of green emitting phosphor will not have an impact in itself.
As seen from Figure 19, the Ba after the present embodiment modification3Si6O12N2:Eu2+The hydrophobic angle test of green emitting phosphor,
Contact angle is 122 degree, forms hydrophobic structure, has achieveed the purpose that hydrophobically modified.
To the Ba after the present embodiment hydrophobically modified3Si6O12N2:Eu2+Green emitting phosphor has carried out heat stability testing, its light
Spectral intensity slightly decreases after 100 DEG C of hydro-thermal 48h, shows good heat endurance.
Embodiment 10
Present embodiments provide a kind of SrSiN by hydrophobically modified2:Eu2+Red fluorescence powder, itself through the following steps that
Prepare：
Weigh 0.5g SrSiN2:Eu2+Red fluorescence powder, is placed in hydrochloric acid solution and handles 15min, is washed out drying；
SrSiN after hydrochloric acid solution is handled2:Eu2+Red fluorescence powder adds in 25mL normal heptanes and forms mixed solution, to
5ml dimethyl dichlorosilane (DMCS)s and 5ml dimethyldichlorosilanes are added in above-mentioned mixed solution, is stirred 30 minutes；Normal heptane is waved completely
Hair, obtains blend sample；
The blend sample is put into horizontal pipe stove and is led to after ammonia 5min when pyrolysis 2 is small at a temperature of 600 DEG C, then
Cooling obtains the mixture of residual fraction liquid polysiloxane, which is filtered, drying and processing, you can must pass through hydrophobic change
The SrSiN of property2:Eu2+Red fluorescence powder.
To the SrSiN after the present embodiment hydrophobically modified2:Eu2+Red fluorescence powder carries out the reality of X-ray diffraction and contact angle
Test, as a result as shown in Figure 20 and Figure 21.
As seen from Figure 20, with SrSiN before modified2:Eu2+Red fluorescence powder is compared, changing after the present embodiment modification
Property SrSiN2:Eu2+The XRD diffraction peaks of red fluorescence powder do not change, and illustrate the present embodiment method of modifying to SrSiN2:Eu2+
The crystalline phase of red fluorescence powder will not have an impact in itself.
As seen from Figure 21, the SrSiN after the present embodiment modification2:Eu2+The hydrophobic angle test of red fluorescence powder, contact
Angle is 120 degree, forms hydrophobic structure, has achieveed the purpose that hydrophobically modified.
The SrSiN of modification to the present embodiment2:Eu2+Red fluorescence powder has carried out heat stability testing, its spectral intensity exists
Slightly decreased after 100 DEG C of hydro-thermal 48h, show good heat endurance.
Embodiment 11
Present embodiments provide a kind of La by hydrophobically modified2Si6O3N8:Ce3+Blue colour fluorescent powder, it is by following
Prepared by step：
Weigh 0.5g La2Si6O3N8:Ce3+Blue colour fluorescent powder, is placed in hydrochloric acid solution and handles 5min, is washed out drying；
La after hydrochloric acid solution is handled2Si6O3N8:Ce3+It is molten that blue colour fluorescent powder adds formation mixing in 25mL normal heptanes
Liquid, 5ml dimethyl dichlorosilane (DMCS)s and 5ml dimethyldichlorosilanes are added into above-mentioned mixed solution, are stirred 30 minutes；Normal heptane is complete
Full volatilization, obtains blend sample；
The blend sample is put into horizontal pipe stove and is led to after ammonia 5min when pyrolysis 2 is small at a temperature of 600 DEG C, then
Cooling obtains the mixture of residual fraction liquid polysiloxane, which is filtered, drying and processing, you can must pass through hydrophobic change
The La of property2Si6O3N8:Ce3+Blue colour fluorescent powder.
To the La after the present embodiment hydrophobically modified2Si6O3N8:Ce3+Blue colour fluorescent powder carries out X-ray diffraction and contact angle
Experiment, as a result as shown in Figure 22 and Figure 23.
As seen from Figure 22, with La before modified2Si6O3N8:Ce3+Blue colour fluorescent powder is compared, after the present embodiment modification
Modified La2Si6O3N8:Ce3+The XRD diffraction peaks of blue colour fluorescent powder do not change, and illustrate the present embodiment method of modifying pair
La2Si6O3N8:Ce3+The crystalline phase of blue colour fluorescent powder will not have an impact in itself.
As seen from Figure 23, the La after the present embodiment modification2Si6O3N8:Ce3+The hydrophobic angle test of blue colour fluorescent powder, connects
Feeler is 120 degree, forms hydrophobic structure, has achieveed the purpose that hydrophobically modified.
The La of modification to the present embodiment2Si6O3N8:Ce3+Blue colour fluorescent powder has carried out heat stability testing, its spectrum is strong
Degree slightly decreases after 100 DEG C of hydro-thermal 48h, shows good heat endurance.
Claims (10)
1. a kind of preparation method of hydrophobically modified fluorescent powder, it comprises the following steps：
Step 1：Fluorescent powder is placed in acid solution or alkaline solution and is surface-treated, obtains surface treated fluorescence
Powder；
Step 2：The surface treated fluorescent powder is mixed with chlorosilane, organic solvent, stirs to the organic solvent and waves
Distribute entirely, obtain mixture；
Step 3：The mixture is placed in ammonia atmosphere and carries out pyrolysis processing, obtains hydrophobically modified fluorescent powder.
2. the preparation method of hydrophobically modified fluorescent powder according to claim 1, it is characterised in that：With the matter of the fluorescent powder
Gauge, the mixing ratio of the surface treated fluorescent powder, chlorosilane and organic solvent is 1g：(5-15)ml：(10-50)ml.
3. the preparation method of hydrophobically modified fluorescent powder according to claim 1, it is characterised in that：The temperature of the pyrolysis processing
Spend for 100 DEG C -800 DEG C, time 1h-3h.
4. the preparation method of hydrophobically modified fluorescent powder according to claim 1, it is characterised in that：The fluorescent powder includes silicon
Base oxynitride fluorescent powder；
Preferably, the fluorescent powder includes Ba2SiO4:Eu2+Green emitting phosphor, Sr2Si5N8:Eu2+Red fluorescence powder, Ca2Si5N8:
Eu2+Red fluorescence powder, Ba2Si5N8:Eu2+Red fluorescence powder, LaSiO2N:Ce3+Blue colour fluorescent powder, SrLiAl3N4:Eu2+It is red glimmering
Light powder, CaSi2O2N2:Eu2+Yellow fluorescent powder, SrSi2O2N2:Eu2+Green emitting phosphor, Ba3Si6O12N2:Eu2+Green emitting phosphor,
SrSiN2:Eu2+Red fluorescence powder and La2Si6O3N8:Ce3+Any of blue colour fluorescent powder.
5. the preparation method of hydrophobically modified fluorescent powder according to claim 1, it is characterised in that：The step of the surface treatment
Suddenly it is：
At room temperature, the fluorescent powder is placed in acid solution or alkaline solution and handles 5-30min, be washed out drying, obtained
The surface treated fluorescent powder；
Preferably, the acid solution includes one or more combinations in hydrochloric acid solution, acetum and oxalic acid solution, institute
The molar concentration for stating acid solution is 0.01-1mol/L；
Preferably, the alkaline solution includes one in potassium hydroxide solution, sodium hydroxide solution, ammonium hydroxide and calcium hydroxide solution
Kind or a variety of combinations, the molar concentration of the alkaline solution is 0.01-1mol/L.
6. the preparation method of hydrophobically modified fluorescent powder according to claim 1, it is characterised in that：The organic solvent includes
One or more of combinations in normal heptane, hexamethylene, benzene and toluene；
Preferably, the chlorosilane includes dimethyl dichlorosilane (DMCS) and/or dimethyldichlorosilane.
7. hydrophobically modified fluorescent powder made from the preparation method of any one of the claim 1-6 hydrophobically modified fluorescent powders.
8. hydrophobically modified fluorescent powder according to claim 7, it is characterised in that：Dredge on the surface of the hydrophobically modified fluorescent powder
Water angle >=112 °；
Preferably, the hydrophobically modified phosphor surface coats one layer of nothing being formed by connecting by Si-O, Si-C and Si-N covalent bonds
Machine covalent structure nano-particle layer；The thickness of the inorganic covalent structure nano particles layer is 20nm-40nm.
A kind of 9. light-emitting device, it is characterised in that：The light-emitting device includes dredging described in illuminating source and claim 7 or 8
Water is modified fluorescent powder；
Preferably, the light-emitting device includes white LED lamp.
10. the hydrophobically modified fluorescent powder of claim 7 or 8 on oil field in shale gas exploitation as Interwell tracer should
With.
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