CN116574399A - Modified silica sol for fluorescent cap, preparation and application methods thereof and oxygen-sensitive fluorescent cap - Google Patents
Modified silica sol for fluorescent cap, preparation and application methods thereof and oxygen-sensitive fluorescent cap Download PDFInfo
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- CN116574399A CN116574399A CN202310703213.XA CN202310703213A CN116574399A CN 116574399 A CN116574399 A CN 116574399A CN 202310703213 A CN202310703213 A CN 202310703213A CN 116574399 A CN116574399 A CN 116574399A
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- Prior art keywords
- silica sol
- fluorescent
- modified silica
- cap
- oxygen
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims abstract description 60
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000001301 oxygen Substances 0.000 title claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 125000005376 alkyl siloxane group Chemical group 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 20
- -1 organosiloxane modified silica sol Chemical class 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 239000003269 fluorescent indicator Substances 0.000 claims abstract description 16
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 239000003292 glue Substances 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000003446 ligand Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 229910000071 diazene Inorganic materials 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 9
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical group [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 4
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- CSUNYJDUAUTOOT-UHFFFAOYSA-K [Ru](Cl)(Cl)Cl.N1=CC=CC2=CC=C3C=CC=NC3=C12.N1=CC=CC2=CC=C3C=CC=NC3=C12.N1=CC=CC2=CC=C3C=CC=NC3=C12 Chemical compound [Ru](Cl)(Cl)Cl.N1=CC=CC2=CC=C3C=CC=NC3=C12.N1=CC=CC2=CC=C3C=CC=NC3=C12.N1=CC=CC2=CC=C3C=CC=NC3=C12 CSUNYJDUAUTOOT-UHFFFAOYSA-K 0.000 claims description 3
- 229910021418 black silicon Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 claims description 3
- IJROHELDTBDTPH-UHFFFAOYSA-N trimethoxy(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F IJROHELDTBDTPH-UHFFFAOYSA-N 0.000 claims description 3
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 claims description 2
- SKZWFYFFTOHWQP-UHFFFAOYSA-L 4,7-diphenyl-1,10-phenanthroline;ruthenium(2+);dichloride Chemical compound Cl[Ru]Cl.C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21.C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21.C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 SKZWFYFFTOHWQP-UHFFFAOYSA-L 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- DSASKEXMZLJGKF-UHFFFAOYSA-K Cl(=O)(=O)(=O)[O-].[Ru+3].C1(=CC=CC=C1)C1=CC=NC2=C3N=CC=C(C3=CC=C12)C1=CC=CC=C1.C1(=CC=CC=C1)C1=CC=NC2=C3N=CC=C(C3=CC=C12)C1=CC=CC=C1.C1(=CC=CC=C1)C1=CC=NC2=C3N=CC=C(C3=CC=C12)C1=CC=CC=C1.Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-] Chemical compound Cl(=O)(=O)(=O)[O-].[Ru+3].C1(=CC=CC=C1)C1=CC=NC2=C3N=CC=C(C3=CC=C12)C1=CC=CC=C1.C1(=CC=CC=C1)C1=CC=NC2=C3N=CC=C(C3=CC=C12)C1=CC=CC=C1.C1(=CC=CC=C1)C1=CC=NC2=C3N=CC=C(C3=CC=C12)C1=CC=CC=C1.Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-] DSASKEXMZLJGKF-UHFFFAOYSA-K 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229960003493 octyltriethoxysilane Drugs 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- UGVSZASAQKTWDI-UHFFFAOYSA-N O.OCCNC(C(C)C)=N Chemical compound O.OCCNC(C(C)C)=N UGVSZASAQKTWDI-UHFFFAOYSA-N 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 abstract description 11
- 230000004044 response Effects 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 108010025899 gelatin film Proteins 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- LECPYKYNIWHZFT-UHFFFAOYSA-K ruthenium(3+) triperchlorate Chemical group [Ru+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LECPYKYNIWHZFT-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- 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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- A—HUMAN NECESSITIES
- A42—HEADWEAR
- A42B—HATS; HEAD COVERINGS
- A42B1/00—Hats; Caps; Hoods
- A42B1/24—Hats; Caps; Hoods with means for attaching articles thereto, e.g. memorandum tablets or mirrors
- A42B1/242—Means for mounting detecting, signalling or lighting devices
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention belongs to the technical field of sensors, and particularly relates to a fluorescent dissolved oxygen sensor, and relates to a modified silica sol for a fluorescent cap, a preparation and application method thereof and an oxygen-sensitive fluorescent cap. The product developed by the invention comprises the following components: modified silica sol, free radical initiator and oxygen sensitive fluorescent indicator; wherein the modified silica sol is an organosiloxane modified silica sol; the organosiloxane comprises alkyl siloxane, fluorine-containing alkyl siloxane and silane coupling agent KH570. The modified silica sol solution has good film forming property and low waste proportion; the prepared fluorescent film has strong toughness, high response speed and good sensing consistency. The problem of poor film forming property and sensing film response consistency of the traditional silica sol liquid is solved.
Description
Technical Field
The invention belongs to the technical field of sensors. More particularly, relates to a fluorescent dissolved oxygen sensor, and relates to a modified silica sol for a fluorescent cap, a preparation and application method thereof and an oxygen-sensitive fluorescent cap.
Background
The oxygen molecules dissolved in the water body are called dissolved oxygen. The dissolved oxygen content of the water body is an important parameter for representing the water quality of the water body, and is also an important control index in aquaculture, sewage treatment, biochemical reaction, clinical medicine and life science. The field of dissolved oxygen measurement requires a quick, accurate and long-acting measuring method and a sensor to realize on-line monitoring of the dissolved oxygen of the water body. Currently, the measurement methods of dissolved oxygen mainly include an iodometry, an electrochemical electrode method and a fluorescence quenching method, wherein only the fluorescence quenching method has online monitoring capability.
The measurement principle of the fluorescence quenching dissolved oxygen sensor is based on the quenching effect of oxygen molecules on certain fluorescent substances. Under the irradiation of light radiation, the fluorescence indicator molecules absorb photons to transition to an excited state; the indicator molecules in the excited state are unstable, release part of the excitation energy in the form of light, emit fluorescence or phosphorescence, and transition themselves back to the ground state. When oxygen molecules collide with excited indicator molecules, excitation energy is transferred, and fluorescence (phosphorus) light emission of the fluorescent film indicator is reduced; the fluorescence intensity and the fluorescence lifetime are inversely related to the concentration of oxygen molecules, and the dissolved oxygen content of the water body to be measured can be obtained by measuring the fluorescence intensity or the fluorescence lifetime of the sensing film. The fluorescence quenching dissolved oxygen sensor has the advantages of no oxygen consumption, no reference electrode, no electrolyte, no electromagnetic field interference and the like, overcomes the defects of a Winkler titration method and a Clark electrode method, and becomes a main instrument for on-line monitoring of the dissolved oxygen of the water body.
The technical key of the fluorescence quenching oxygen sensor is an oxygen sensitive fluorescent film. It mainly consists of fluorescent indicator and carrier material for carrying the indicator. The carrier material is a support material for the fluorescent indicator and is also a film forming material for the oxygen sensitive fluorescent film. It should possess the following characteristics:
(1) Good mechanical properties and optical properties;
(2) Good oxygen solubility and oxygen diffusivity;
(3) Good fluorescent indicator compatibility;
(4) Good photochemical stability and no fluorescence activity.
The silica gel has low cost and easy obtaining of raw materials and simple synthesis process. The porous silica gel membrane prepared by the sol-gel method is a carrier material used for an early oxygen sensitive fluorescent membrane. The fluorescent film has good light transmittance and photochemical stability and good oxygen molecule penetrability, and is an unobtainable oxygen-sensitive fluorescent film carrier material. However, in the process of converting the sol film into a gel film, the mass of the sol film is greatly reduced and the volume tends to shrink due to solvent volatilization and condensation dehydration of silicon hydroxyl groups; in addition, the sol particles in the initial stage of gel are mainly associated by hydrogen bonds, the chemical bonding is rare, the sol film is easy to collapse and crack, and the rejection rate of the film preparation is high; the obtained silica gel film has large brittleness and poor mechanical property, and limits the application of the silica gel film in the field of oxygen sensitive fluorescent films.
Disclosure of Invention
The invention aims to overcome the defects of high brittleness and poor mechanical property of a used silica gel film in the existing products, so that the products are easy to crack and have high rejection rate, and provides a modified silica sol for fluorescent caps, a preparation and application method thereof and an oxygen-sensitive fluorescent cap.
The invention aims to provide a modified silica sol for a fluorescent cap.
The invention further aims to provide a preparation method of the modified silica sol for the fluorescent cap.
The invention further aims at providing an application method of the modified silica sol for the fluorescent cap.
It is another object of the present invention to provide an oxygen-sensitive fluorescent cap.
The above object of the present invention is achieved by the following technical scheme:
the modified silica sol for the fluorescent cap is characterized by comprising the following components:
modified silica sol, free radical initiator and oxygen sensitive fluorescent indicator;
wherein the modified silica sol is an organosiloxane modified silica sol; the organosiloxane comprises alkyl siloxane, fluorine-containing alkyl siloxane and silane coupling agent KH570.
The silica sol film is made of SiO 2 The solid skeleton formed by sol particles is saturated with solvent. The sol particles are connected through hydrogen bond of silicon hydroxyl, and the solvent has supporting effect on the framework. The process of converting silica sol film into silica gel film is nanometer SiO 2 The sol particles are dehydrated and condensed through surface silicon hydroxyl groups to form a continuous Si-O-Si three-dimensional network, and solvent volatilization, mass reduction, volume shrinkage and internal stress are unavoidable. SiO is connected in the gelation process 2 The Si-O-Si bridging of sol particles is easy to break due to internal stress, so that the three-dimensional network of the gel film is partially collapsed, the film forming property of the traditional silica sol solution is poor, the aging time becomes the key of preparing the silica gel film by the silica sol solution, the process window is narrow, and the sensing response variation is large.
According to the technical scheme, the silane coupling agent KH-570 with carbon-carbon unsaturated double bonds and the fluorine-containing silane are introduced into the sol, firstly, under the action of free radical initiation, nano silicon dioxide particles are linked through the coupling agent, so that the interaction force between the particles is increased, the strength of a sol film and the stability of a hole structure are improved, and the film forming property of a product and the consistency of a gel sensor film are obviously improved; the introduction of fluorosilane can show stronger affinity to silicon hydroxyl on the surface of nano silicon dioxide due to stronger electronegativity of fluorine element, so that not only can the energy transfer of residual silicon hydroxyl to the excited state indicator molecules be reduced, but also the problem that the permeation and diffusion of a silane coupling agent into the system are influenced due to stronger adsorption of the silicon hydroxyl, so that the effect of the coupling agent in the system is difficult to be uniform is solved; according to the technical scheme, the organosilane with the alkane chain segment is further introduced, so that the flexible alkyl is introduced on the silica sol, the content of the silicon hydroxyl is reduced, the toughness of the sol film is increased, and the film forming property of a product is improved.
Further, the alkyl siloxane is any one of dimethyl dimethoxy silane or dimethyl diethoxy silane.
However, when the amount of alkyl groups is large, a continuous organic phase appears in the system, and the pore structure of the gel film is not easily controlled, so that the response time of the sensor film is long, the consistency is also poor, and the problem can be properly solved by selecting either one of dimethyldialkoxysilane or dimethyldiethoxysilane having a small amount of alkyl groups.
Further, the fluorine-containing alkyl siloxane is selected from any one or more of trifluoropropyl trimethoxysilane, trifluoropropyl triethoxysilane, nonafluorohexyl trimethoxysilane and tridecafluoron-octyl triethoxysilane.
Further, the free radical initiator is selected from any one or more of azo diiso Ding Mi hydrochloride, azo diiso Ding Mi hydrochloride, azo diisobutylamidine hydrochloride, azo bis (N-2-hydroxyethyl-methylpropionamidine) hydrate and azo dicarboxyethyl imidazoline propane hydrochloride.
Further, the oxygen-sensitive fluorescent indicator is a ruthenium (II) -diimine tri-ligand complex; the diimine ligand of the tri-ligand complex is one or more than two of 4, 7-diphenyl-1, 10-phenanthroline, 1, 10-phenanthroline or 2,2' -bipyridine; the anions for balancing the positive charges of divalent ruthenium in the ruthenium (II) -diimine tri-ligand complex are one or more ions selected from chloride ions, perchlorate ions and hexafluorophosphate ions; the ruthenium (II) -diimine tri-ligand complex comprises any one of tris (4, 7-diphenyl-1, 10-phenanthroline) ruthenium dichloride, tris (4, 7-diphenyl-1, 10-phenanthroline) ruthenium perchlorate and tris (1, 10-phenanthroline) ruthenium chloride.
The aqueous azo free radical initiator can be dissolved in alcohol and aqueous solution, has low activation temperature, requires lower excitation energy than ultraviolet radiation, and does not damage an indicator conjugated system; the azo free radical has low oxidation potential and is compatible with the ruthenium (II) fluorescent indicator. The aqueous azo free radical initiator can enable the unsaturated silica sol fluorescent film to be rapidly crosslinked at a lower temperature, so that the purposes of improving the film forming property of the silica sol liquid and the consistency of the gel fluorescent film are achieved.
The preparation method of the modified silica sol for the fluorescent cap comprises the following specific preparation steps:
according to the mole parts, 8-10 parts of tetraethoxysilane, 0.5-1.5 parts of fluorine-containing alkyl siloxane, 1-2 parts of silane coupling agent KH-570, 4-5 parts of alkyl siloxane, 32-45 parts of deionized water and 10-14 parts of absolute ethyl alcohol are sequentially taken;
uniformly mixing tetraethoxysilane and a silane coupling agent KH-570 to obtain a mixed solution;
firstly, uniformly mixing all absolute ethyl alcohol and 60% deionized water, regulating the pH to 1-2 by hydrochloric acid, heating to 60-62 ℃, adding fluorine-containing alkyl siloxane and alkyl siloxane in a stirring state, carrying out heat preservation stirring reaction for 10-15min, dropwise adding the mixed solution in the heat preservation stirring state, and then dropwise adding the rest 40% deionized water in the mixed solution; after the deionized water is added dropwise, continuing to perform heat preservation and stirring reaction for 80-100min, and cooling to room temperature;
standing for 8-24h at room temperature to obtain an aging liquid, dissolving a water-based azo free radical initiator accounting for 0.1-3% of the mass of the aging liquid and an oxygen-sensitive fluorescent indicator accounting for 0.01-0.3% of the mass of the aging liquid into the aging liquid, and stirring and dispersing uniformly.
The application method of the modified silica sol for the fluorescent cap comprises the following specific application steps:
preparation of white silicon sol solution:
standing and aging the modified silica sol for 8-24 hours at room temperature, adding a water-based azo free radical initiator accounting for 0.1-3% of the mass of the modified silica sol for the fluorescent cap and titanium dioxide accounting for 5-8% of the mass of the modified silica sol for the fluorescent cap, and grinding and dispersing to obtain white silica sol liquid;
preparation of black silicon sol solution:
standing and aging the modified silica sol for 8-24 hours at room temperature, adding a water-based azo free radical initiator accounting for 0.1-3% of the mass of the modified silica sol for the fluorescent cap and pigment carbon black accounting for 1-2% of the mass of the modified silica sol for the fluorescent cap, and grinding and dispersing to obtain black silica sol liquid;
preparation of fluorescent caps:
sequentially coating the modified silica sol for the fluorescent cap on the surface of the lens to serve as a fluorescent glue layer, the white silica sol liquid to serve as a white glue layer and the black silica sol liquid to serve as a black glue layer;
before coating the next layer of glue solution, placing the coated lens in an oven, and baking for 20min at 45-50 ℃;
after coating all the glue solution is completed, placing the coated lens in an oven, and curing for 20min at 50 ℃; and then curing for 1 hour at 60 ℃, curing for 1 hour at 70 ℃ and curing for 2 hours at 80 ℃, cooling to 45 ℃ along with a furnace, preserving heat for 4 hours, cooling, and discharging to finish the application of the modified silica sol for the fluorescent cap.
An oxygen sensitive fluorescent cap prepared by the application method; the thickness of the fluorescent glue layer of the fluorescent cap is 10-60 mu m, the thickness of the white glue layer of the fluorescent cap is 5-30 mu m, and the thickness of the black glue layer of the fluorescent cap is 10-40 mu m.
Further, the thickness of the fluorescent glue layer of the fluorescent cap is 30-40 mu m, the thickness of the white glue layer of the fluorescent cap is 10-20 mu m, and the thickness of the black glue layer of the fluorescent cap is 15-25 mu m.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
According to the mole parts, 8 parts of tetraethoxysilane, 0.5 part of fluorine-containing alkyl siloxane, 1 part of silane coupling agent KH-570, 32 parts of deionized water, 10 parts of absolute ethyl alcohol and 4 parts of dimethyl dimethoxy silane are sequentially taken;
mixing tetraethoxysilane and a silane coupling agent KH-570, and stirring and mixing for 20min by using a stirrer at a rotating speed of 200r/min to obtain a mixed solution;
dividing deionized water into two parts, wherein one part is 60% of the total amount, and the other part is 40% of the total amount; mixing absolute ethyl alcohol and 60% deionized water, pouring the mixture into a reactor, regulating the pH to 1 by using hydrochloric acid with the mass fraction of 5%, heating to 60 ℃, adding fluoroalkyl alkoxysilane and dimethyl dimethoxy silane under the stirring state with the stirring speed of 400r/min, and continuing to perform heat preservation stirring reaction for 10min after the addition is finished; then dropwise adding the mixed solution into a reactor at a speed of 3mL/min under the condition of heat preservation and stirring, and dropwise adding the rest 40% deionized water into the reactor after the dropwise adding of the mixed solution is completed; after the deionized water is added dropwise, continuing to perform heat preservation and stirring reaction for 80min, and cooling to room temperature;
under the condition of room temperature, standing and ageing materials in a reactor for 8 hours, adding a free radical initiator accounting for 0.3 percent of the mass of the materials in the reactor and an oxygen sensitive fluorescent indicator accounting for 0.01 percent of the mass of the materials in the reactor, and then performing ultrasonic dispersion for 20 minutes under the condition that the ultrasonic frequency is 60kHz to obtain a product;
the fluorine-containing silane is selected from trifluoropropyl trimethoxysilane;
the free radical initiator is selected from azo diiso Ding Mi hydrochloride;
the ruthenium (II) -diimine tri-ligand complex is tris (4, 7-biphenyl-1, 10-phenanthroline) ruthenium dichloride.
Example 2
According to the mole parts, sequentially taking 9 parts of tetraethoxysilane, 1.2 parts of fluorine-containing alkyl siloxane, 1.5 parts of silane coupling agent KH-570, 40 parts of deionized water, 11 parts of absolute ethyl alcohol and 4.5 parts of dimethyl dimethoxy silane;
mixing tetraethoxysilane and a silane coupling agent KH-570, and stirring and mixing for 25min by using a stirrer at a rotating speed of 300r/min to obtain a mixed solution;
dividing deionized water into two parts, wherein one part is 60% of the total amount, and the other part is 40% of the total amount; mixing absolute ethyl alcohol and 60% deionized water, pouring the mixture into a reactor, regulating the pH to 1.5 by using hydrochloric acid with the mass fraction of 5%, heating to 61 ℃, adding fluoroalkyl alkoxysilane and dimethyl diethoxysilane in a stirring state with the stirring speed of 500r/min, and continuing to perform heat preservation stirring reaction for 12min after the addition is finished; then dropwise adding the mixed solution into a reactor at the speed of 4mL/min under the condition of heat preservation and stirring, and dropwise adding the rest 40% deionized water into the reactor after the dropwise adding of the mixed solution is completed; after the deionized water is added dropwise, continuing to perform heat preservation and stirring reaction for 90min, and cooling to room temperature;
under the condition of room temperature, standing and ageing materials in a reactor for 12 hours, adding a free radical initiator accounting for 1.0 percent of the materials in the reactor and an oxygen sensitive fluorescent indicator accounting for 0.1 percent of the materials in the reactor, and then performing ultrasonic dispersion for 25 minutes under the condition that the ultrasonic frequency is 70kHz to obtain a product;
the fluorine-containing silane is selected from trifluoropropyl triethoxysilane;
the free radical initiator is selected from azo diiso Ding Mi-line sulfate;
the oxygen-sensitive fluorescent indicator is ruthenium perchlorate tris (4, 7-diphenyl-1, 10-o-phenanthroline).
Example 3
According to the mole parts, sequentially taking 10 parts of tetraethoxysilane, 1.5 parts of fluorine-containing alkyl siloxane, 2 parts of silane coupling agent KH-570, 45 parts of deionized water, 12 parts of absolute ethyl alcohol and 5 parts of dimethyl dimethoxy silane;
mixing tetraethoxysilane and a silane coupling agent KH-570, and stirring and mixing for 30min by using a stirrer at a rotating speed of 400r/min to obtain a mixed solution;
dividing deionized water into two parts, wherein one part is 60% of the total amount, and the other part is 40% of the total amount; mixing absolute ethyl alcohol and 60% deionized water, pouring the mixture into a reactor, regulating the pH to 2 by using hydrochloric acid with the mass fraction of 5%, heating to 62 ℃, adding fluoroalkyl alkoxysilane and dimethyl dimethoxy silane under the stirring state of stirring rotation speed of 600r/min, and continuing to perform heat preservation stirring reaction for 15min after the addition is finished; then dropwise adding the mixed solution into a reactor at a speed of 5mL/min under the condition of heat preservation and stirring, and dropwise adding the rest 40% deionized water into the reactor after the dropwise adding of the mixed solution is completed; after the deionized water is added dropwise, continuing to perform heat preservation and stirring reaction for 100min, and cooling to room temperature;
under the condition of room temperature, standing and ageing the materials in the reactor for 24 hours, adding a free radical initiator accounting for 3.0 percent of the mass of the materials in the reactor and an oxygen sensitive fluorescent indicator accounting for 0.3 percent of the mass of the materials in the reactor, and then performing ultrasonic dispersion for 30 minutes under the condition that the ultrasonic frequency is 80kHz to obtain a product;
the fluorine-containing silane is selected from nonafluorohexyl trimethoxysilane;
the free radical initiator is selected from azobisisobutyronium chloride;
the oxygen-sensitive fluorescent indicator is ruthenium (II) -diimine tri-ligand complex including ruthenium tri (1, 10-phenanthroline) chloride.
Example 4
The difference between this embodiment and embodiment 1 is that: no dimethyldimethoxysilane was added and the rest of the conditions remained unchanged.
Example 5
The difference between this embodiment and embodiment 1 is that: an equimolar amount of decamethyl cyclopentasiloxane was used instead of dimethyl dimethoxy silane, the remaining conditions remained unchanged.
Comparative example 1
The difference between this comparative example and example 1 is that: the silane coupling agent KH-550 with equal mass is adopted to replace the silane coupling agent KH-570, and the rest conditions are kept unchanged.
Comparative example 2
The difference between this comparative example and example 1 is that: no trifluoropropyl trimethoxysilane was added and the remaining conditions remained unchanged.
Comparative example 3
The difference between this comparative example and example 1 is that: no free radical initiator was added and the remaining conditions remained unchanged.
The products obtained in examples 1 to 5 and comparative examples 1 to 3 were subjected to performance tests, and specific test methods and test results are as follows:
respectively taking 10g of each example or comparative example product, respectively stirring with 0.5g of titanium dioxide, and grinding and dispersing for 10min to obtain white silicon sol solution;
respectively taking 10g of each example or comparative example product, respectively stirring with 0.1g of carbon black powder, and grinding and dispersing for 10min to obtain black silicon sol solution;
taking a lens with a cleaned surface, coating the product of a corresponding example or a comparative example on the outer surface, treating the lens in a 50 ℃ oven for 20min, coating white silica sol on the surface of the dried coating, treating the coated surface in the 50 ℃ oven for 20min, coating black silica sol on the surface of the dried coating, treating the coated surface in the 50 ℃ oven for 20min, sequentially curing the coated surface in the oven at 60 ℃ for 1 h, curing the coated surface at 70 ℃ for 1 h and curing the coated surface at 80 ℃ for 2h, and cooling the coated surface to 45 ℃ along with a furnace and preserving the heat for 4 h. The fluorescent cap was removed from the oven and visually inspected. The fluorescent cap was left at room temperature for more than 48 hours, and fluorescence and sensing properties of the fluorescent cap were measured using a KY-III oximeter. The detection results are shown in Table 1.
Table 1: product performance test results
Compared with the prior art, the technical scheme has the advantages of good film forming property of the silica sol liquid and high yield of the gel film; the prepared oxygen-sensitive fluorescent cap has high response speed and good consistency.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. The modified silica sol for the fluorescent cap is characterized by comprising the following components:
modified silica sol, a water-based azo free radical initiator and an oxygen-sensitive fluorescent indicator;
wherein the modified silica sol is an organosiloxane modified silica sol; the organosiloxane comprises alkyl siloxane, fluorine-containing alkyl siloxane and silane coupling agent KH570.
2. The modified silica sol for a fluorescent cap according to claim 1, wherein the alkylsiloxane is either dimethyldimethoxysilane or dimethyldiethoxysilane.
3. The modified silica sol for fluorescent caps according to claim 1, wherein the fluorine-containing alkyl siloxane is selected from any one or more of trifluoropropyl trimethoxysilane, trifluoropropyl triethoxysilane, nonafluorohexyl trimethoxysilane, tridecafluoron-octyl triethoxysilane.
4. The modified silica sol for fluorescent caps according to claim 1, wherein the aqueous azo free radical initiator is selected from any one or more of azobisiso Ding Mi hydrochloride, azobisiso Ding Mi hydrochloride, azobisisobutylamidine hydrochloride, azobis (N-2-hydroxyethyl-methylpropionamidine) hydrate, and azobis carboxyethylimidazoline propane hydrochloride.
5. The modified silica sol for fluorescent caps of claim 1, wherein the oxygen-sensitive fluorescent indicator is a ruthenium (II) -diimine tri-ligand complex; the diimine ligand of the tri-ligand complex is one or more than two of 4, 7-diphenyl-1, 10-phenanthroline, 1, 10-phenanthroline or 2,2' -bipyridine; the anions for balancing the positive charges of divalent ruthenium in the ruthenium (II) -diimine tri-ligand complex are one or more ions selected from chloride ions, perchlorate ions and hexafluorophosphate ions; the ruthenium (II) -diimine tri-ligand complex comprises any one of tris (4, 7-diphenyl-1, 10-phenanthroline) ruthenium dichloride, tris (4, 7-diphenyl-1, 10-phenanthroline) ruthenium perchlorate and tris (1, 10-phenanthroline) ruthenium chloride.
6. A method for preparing the modified silica sol for fluorescent caps according to any one of claims 1 to 5, comprising the specific preparation steps of:
according to the mole parts, 8-10 parts of tetraethoxysilane, 0.5-1.5 parts of fluorine-containing alkyl siloxane, 1-2 parts of silane coupling agent KH-570, 4-5 parts of alkyl siloxane, 32-45 parts of deionized water and 10-14 parts of absolute ethyl alcohol are sequentially taken;
uniformly mixing tetraethoxysilane and a silane coupling agent KH-570 to obtain a mixed solution;
firstly, uniformly mixing all absolute ethyl alcohol and 60% deionized water, regulating the pH to 1-2 by hydrochloric acid, heating to 60-62 ℃, adding fluorine-containing alkyl siloxane and alkyl siloxane in a stirring state, carrying out heat preservation stirring reaction for 10-15min, dropwise adding the mixed solution in the heat preservation stirring state, and then dropwise adding the rest 40% deionized water in the mixed solution; after the deionized water is added dropwise, continuing to perform heat preservation and stirring reaction for 80-100min, and cooling to room temperature;
standing for 8-24h at room temperature to obtain an aging liquid, dissolving a water-based azo free radical initiator accounting for 0.1-3% of the mass of the aging liquid and an oxygen-sensitive fluorescent indicator accounting for 0.01-0.3% of the mass of the aging liquid into the aging liquid, and stirring and dispersing uniformly.
7. A method of using the modified silica sol for fluorescent caps according to any one of claims 1 to 5, comprising the specific steps of:
preparation of white silicon sol solution:
standing and aging the modified silica sol for 8-24 hours at room temperature, adding a water-based azo free radical initiator accounting for 0.1-3% of the mass of the modified silica sol and titanium dioxide accounting for 5-8% of the mass of the modified silica sol, and grinding and dispersing to obtain white silica sol liquid;
preparation of black silicon sol solution:
standing and aging the modified silica sol for 8-24 hours at room temperature, adding a water-based azo free radical initiator accounting for 0.1-3% of the mass of the modified silica sol and pigment carbon black accounting for 1-2% of the mass of the modified silica sol, and grinding and dispersing to obtain black silica sol solution;
preparation of fluorescent caps:
sequentially coating the modified silica sol for the fluorescent cap on the surface of the lens to serve as a fluorescent glue layer, the white silica sol liquid to serve as a white glue layer and the black silica sol liquid to serve as a black glue layer;
before coating the next layer of glue solution, placing the coated lens in an oven, and baking for 20min at 45-50 ℃;
after coating all the glue solution is completed, placing the coated lens in an oven, and curing for 20min at 50 ℃; and then curing for 1 hour at 60 ℃, curing for 1 hour at 70 ℃ and curing for 2 hours at 80 ℃, cooling to 45 ℃ along with a furnace, preserving heat for 4 hours, cooling, and discharging to finish the application of the modified silica sol for the fluorescent cap.
8. An oxygen-sensitive fluorescent cap, characterized in that: is prepared by the application method of claim 7; the thickness of the fluorescent glue layer of the fluorescent cap is 10-60 mu m, the thickness of the white glue layer of the fluorescent cap is 5-30 mu m, and the thickness of the black glue layer of the fluorescent cap is 10-40 mu m.
9. An oxygen-sensitive fluorescent cap according to claim 8, wherein: the thickness of the fluorescent glue layer of the fluorescent cap is 30-40 mu m, the thickness of the white glue layer of the fluorescent cap is 10-20 mu m, and the thickness of the black glue layer of the fluorescent cap is 15-25 mu m.
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| CN117589735A (en) * | 2023-11-21 | 2024-02-23 | 广东隆宇传感科技有限公司 | Oxygen-sensitive fluorescent cap, dissolved oxygen sensor and preparation method of oxygen-sensitive fluorescent cap |
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