CN114414536A - Preparation method of dissolved oxygen sensitive film based on fluorescence - Google Patents
Preparation method of dissolved oxygen sensitive film based on fluorescence Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 76
- 239000001301 oxygen Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 44
- 238000004528 spin coating Methods 0.000 claims abstract description 31
- 239000004945 silicone rubber Substances 0.000 claims abstract description 26
- 239000004793 Polystyrene Substances 0.000 claims abstract description 21
- 239000003269 fluorescent indicator Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 229920002223 polystyrene Polymers 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000012528 membrane Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims description 36
- -1 (pentafluorobenzene) porphyrin Chemical compound 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 6
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 claims description 3
- KETXQNLMOUVTQB-UHFFFAOYSA-N 2,3,7,8,12,13,17,18-octaethylporphyrin;platinum Chemical compound [Pt].C=1C(C(=C2CC)CC)=NC2=CC(C(=C2CC)CC)=NC2=CC(C(=C2CC)CC)=NC2=CC2=NC=1C(CC)=C2CC KETXQNLMOUVTQB-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 15
- 238000001514 detection method Methods 0.000 abstract description 9
- 238000012423 maintenance Methods 0.000 abstract description 6
- 230000035699 permeability Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000032683 aging Effects 0.000 abstract description 2
- 230000003373 anti-fouling effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000012360 testing method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002795 fluorescence method Methods 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 238000009360 aquaculture Methods 0.000 description 2
- 244000144974 aquaculture Species 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- VFMUXPQZKOKPOF-UHFFFAOYSA-N 2,3,7,8,12,13,17,18-octaethyl-21,23-dihydroporphyrin platinum Chemical group [Pt].CCc1c(CC)c2cc3[nH]c(cc4nc(cc5[nH]c(cc1n2)c(CC)c5CC)c(CC)c4CC)c(CC)c3CC VFMUXPQZKOKPOF-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 1
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- 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"
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- 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
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- Physics & Mathematics (AREA)
- Immunology (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a preparation method of a dissolved oxygen sensitive membrane based on fluorescence, which comprises the steps of preparation of a fluorescence sol, spin coating and drying; wherein, the preparation of the fluorescent sol comprises the following steps: and fully mixing and dissolving polystyrene and toluene at room temperature to obtain a mixed solution, adding the fluorescent indicator and the silicone rubber, uniformly mixing, and stirring at room temperature in a dark place until the fluorescent indicator and the silicone rubber are completely dissolved to obtain the fluorescent sol agent. In the formula of the dissolved oxygen sensitive membrane, a certain proportion of high-permeability silicone rubber and a fluorescent indicator are added into a mixed solution of polystyrene and toluene, and the mixture is stirred at room temperature in a dark place to obtain a fluorescent sol agent; the preparation method does not need an aging step, greatly reduces the preparation time of the dissolved oxygen sensitive membrane, and the prepared sensitive membrane has certain hydrophobicity on the surface, good air permeability, can obviously improve the response time in the detection process, simultaneously has damage resistance and strong anti-fouling capability, and does not need frequent maintenance in use.
Description
Technical Field
The invention relates to the technical field of preparation of a dissolved oxygen sensor sensitive element based on a fluorescence method, in particular to a sensing method for detecting dissolved oxygen in water by a fluorescence method.
Background
Dissolved oxygen in water is molecular oxygen dissolved in air in water, and is an essential condition for the survival of aquatic organisms. The dissolved oxygen in water has two sources, one is that when the dissolved oxygen in water is not saturated, the oxygen in the atmosphere permeates into the water body; another source is the oxygen released by aquatic plants through photosynthesis. Only when the dissolved oxygen is sufficient, the normal metabolism and growth development of the aquatic animals can be maintained. Therefore, aquatic animals such as fish can only maintain normal life activities in the aquaculture water with sufficient dissolved oxygen. When the water body is polluted by organic matters and reducing substances, anaerobic bacteria in the water can be propagated to cause the water body to be deteriorated, and dissolved oxygen in the water body is reduced, so that the dissolved oxygen is not only an important index of the pollution degree of the water body, but also a comprehensive index for measuring the water quality. When the dissolved oxygen in the water body is lower than 4mg/L, the fish can be suffocated and die, and for human beings, the dissolved oxygen content in healthy drinking water is not less than 6 mg/L. Therefore, the measurement of the dissolved oxygen content in the water body has important significance for environmental monitoring and the development of the aquaculture industry.
At present, the detection of dissolved oxygen mainly comprises a chemical iodometry method and a dissolved oxygen meter method. The chemical iodometry method is complex in operation, needs large-scale instruments, needs professional technicians to complete detection in a laboratory, has hysteresis quality in detection results, and cannot realize real-time detection of the environmental water body. At present, a common dissolved oxygen meter mainly depends on an electrochemical method to realize rapid detection of dissolved oxygen, but the method mainly depends on an electrode as a sensitive element to carry out detection, frequent maintenance needs to be carried out on the electrode in use, and the maintenance operation is complex. Compared with a dissolved oxygen instrument developed based on electrochemistry and based on a fluorescence quenching principle, the dissolved oxygen instrument has the advantages of fast response, no need of oxygen consumption in the measurement process, no need of maintenance in the use of the dissolved oxygen sensitive membrane, stable property, long service life and convenient equipment maintenance, and is very suitable for long-term detection of the dissolved oxygen in water.
However, the research on the dissolved oxygen sensitive membrane by the fluorescence method in China is relatively late, and the prepared dissolved oxygen sensitive membrane generally has the problems of large individual difference, poor detection reproducibility, unstable membrane surface (easy to crack), long response time (poor air permeability) and the like.
Disclosure of Invention
The invention aims to solve the problems of large individual difference, poor reproducibility, unstable membrane surface, long response time and the like of a dissolved oxygen sensitive membrane of a current fluorescence method, and provides a preparation method of the dissolved oxygen sensitive membrane based on fluorescence.
The technical scheme of the invention is as follows:
the invention provides a preparation method of a fluorescence-based dissolved oxygen sensitive film, which comprises the steps of preparation of a fluorescence sol agent, spin coating and drying; wherein,
the preparation method of the fluorescent sol comprises the following steps: and fully mixing the polystyrene and the toluene at room temperature to obtain a mixed solution, adding the fluorescent indicator and the silicon rubber, uniformly mixing, and stirring at room temperature in a dark place until the fluorescent indicator and the silicon rubber are completely dissolved to obtain the fluorescent sol agent.
Further, the mass-volume ratio of the polystyrene to the toluene is 0.1-0.5mg/mL, and the concentration of the fluorescent indicator in the fluorescent sol solution is 2-6 mg/mL.
Further, the fluorescence indicator is one of platinum (II) m-tetra (pentafluorobenzene) porphyrin, platinum (II) octaethylporphyrin, tris (2, 2' -bipyridyl) ruthenium (II) complex, tris (4, 7-diphenyl-1, 10-phenanthroline) ruthenium (II) complex, tris (1, 10-phenanthroline) ruthenium (II) and tris (5-amino-1, 10-phenanthroline) ruthenium.
Further, the silicone rubber is a commercial silicone rubber, and the volume ratio of the added silicone rubber to the mixed solution of polystyrene and toluene is 1: 2-1: 4.
Further, the silicone rubber is Dragon skin-30 silicone rubber.
Further, the room temperature stirring time in the dark is 5-10 minutes.
Further, the spin coating step is to fix the substrate on a spin coater, drop the fluorescent sol agent on the surface of the substrate, and perform spin coating to form the fluorescence-dissolved oxygen-sensitive film on the substrate.
Furthermore, the substrate is made of polyethylene terephthalate or polymethyl methacrylate, and the thickness of the substrate is 1-3 mm.
Furthermore, the spin coating speed is 3000-.
Further, the drying step is that the substrate with the sensitive film after spin coating is placed in a dark environment at 70-90 ℃ for drying for 1.5-2.5h to obtain the sensitive element of the dissolved oxygen sensor.
The invention has the beneficial effects that:
in the formula of the dissolved oxygen sensitive membrane, a certain proportion of high-permeability silicone rubber and a fluorescent indicator are added into a mixed solution of polystyrene and toluene, and the mixture is stirred at room temperature in a dark place to obtain a fluorescent sol agent; the preparation method does not need an aging step, greatly reduces the preparation time of the dissolved oxygen sensitive membrane, and the prepared sensitive membrane has certain hydrophobicity on the surface, good air permeability, can obviously improve the response time in the detection process, simultaneously has damage resistance and strong anti-fouling capability, and does not need frequent maintenance in use.
According to the invention, the thickness of the sensitive films is effectively controlled by modulating different rotating speeds by using a spin coating technology, so that the thickness difference between each sensitive film is effectively reduced, the surface of the prepared sensitive film has good uniformity, and the measurement precision of the dissolved oxygen sensor after the sensitive films are replaced in the working process is ensured.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
Fig. 1 shows a schematic diagram of a response time test curve.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. While the preferred embodiments of the present invention are shown in the drawings, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein.
Example 1
S1, preparation of the fluorescent sol: fully mixing and dissolving polystyrene and toluene at room temperature for 10min to obtain a mixed solution, adding the fluorescent indicator and the silicone rubber, uniformly mixing, and stirring at room temperature in a dark place for 5min until the fluorescent sol is completely dissolved to obtain a fluorescent sol agent;
wherein: the mass-volume ratio of the polystyrene to the toluene is 0.1mg/mL, and the concentration of the fluorescent indicator in the fluorescent sol solution is 2 mg/mL; the fluorescence indicator is platinum (II) m-tetra (pentafluorobenzene) porphyrin; the silicon rubber is Dragon skin-30 silicon rubber (brand: Smooth-On), and the volume ratio of the added silicon rubber to the mixed solution of polystyrene and toluene is 1: 4;
s2, the spin coating step is that the substrate is fixed on a spin coating machine, the fluorescent sol agent is dripped on the surface of the substrate for spin coating, and a fluorescence method dissolved oxygen sensitive film is formed on the substrate; the substrate is made of polyethylene terephthalate, and the thickness of the substrate is 1 mm; the spin coating speed is 4000r/s, and the time is 40 s;
and S3, drying, namely, placing the substrate with the sensitive film in a dark environment at 70 ℃ for drying for 1.5h to obtain the sensitive element of the dissolved oxygen sensor.
Example 2
A preparation method of a fluorescence-based dissolved oxygen sensitive film comprises the steps of preparation of a fluorescence sol agent, spin coating and drying; wherein,
s1, preparing the fluorescent sol: fully mixing and dissolving polystyrene and toluene at room temperature for 15min to obtain a mixed solution, adding the fluorescent indicator and the silicone rubber, uniformly mixing, and stirring at room temperature in a dark place for 10min until the fluorescent indicator and the silicone rubber are completely dissolved to obtain a fluorescent sol agent;
wherein: the mass-volume ratio of the polystyrene to the toluene is 0.5mg/mL, and the concentration of the fluorescent indicator in the fluorescent sol solution is 6 mg/mL; the fluorescence indicator is octaethylporphyrin platinum (II); the silicon rubber is Dragon skin-30 silicon rubber (brand: Smooth-On), and the volume ratio of the added silicon rubber to the mixed solution of polystyrene and toluene is 1: 2;
s2, the spin coating step is that the substrate is fixed on a spin coating machine, the fluorescent sol agent is dripped on the surface of the substrate for spin coating, and a fluorescence method dissolved oxygen sensitive film is formed on the substrate; the substrate is made of polyethylene terephthalate, and the thickness of the substrate is 2 mm; the spin-coating rotating speed is 3000r/s, and the time is 60 s;
and S3, drying, namely, placing the substrate with the sensitive film in a dark environment at 90 ℃ for drying for 2.5 hours to obtain the sensitive element of the dissolved oxygen sensor.
Example 3
A preparation method of a fluorescence-based dissolved oxygen sensitive film comprises the steps of preparation of a fluorescence sol agent, spin coating and drying; wherein,
s1, preparing the fluorescent sol: fully mixing and dissolving polystyrene and toluene at room temperature for 15min to obtain a mixed solution, adding the fluorescent indicator and the silicone rubber, uniformly mixing, and stirring at room temperature in a dark place for 5min until the fluorescent sol is completely dissolved to obtain a fluorescent sol agent;
wherein: the mass-volume ratio of the polystyrene to the toluene is 0.15mg/mL, and the concentration of the fluorescent indicator in the fluorescent sol solution is 2.5 mg/mL; the fluorescent indicator is tris (5-amino-1, 10-phenanthroline) ruthenium; the silicon rubber is Dragon skin-30 silicon rubber (brand: Smooth-On), and the volume ratio of the added silicon rubber to the mixed solution of polystyrene and toluene is 1: 3;
s2, the spin coating step is that the substrate is fixed on a spin coating machine, the fluorescent sol agent is dripped on the surface of the substrate for spin coating, and a fluorescence method dissolved oxygen sensitive film is formed on the substrate; the substrate is made of polyethylene terephthalate, and the thickness of the substrate is 2 mm; the spin-coating rotating speed is 3000r/s, and the time is 60 s;
and S3, drying, namely, placing the substrate with the sensitive film in a dark environment at 80 ℃ for drying for 1.5h to obtain the sensitive element of the dissolved oxygen sensor.
Example 4
A preparation method of a fluorescence-based dissolved oxygen sensitive film comprises the steps of preparation of a fluorescence sol agent, spin coating and drying; wherein,
s1, preparing the fluorescent sol: fully mixing and dissolving polystyrene and toluene at room temperature for 15min to obtain a mixed solution, adding the fluorescent indicator and the silicone rubber, uniformly mixing, and stirring at room temperature in a dark place for 5min until the fluorescent sol is completely dissolved to obtain a fluorescent sol agent;
wherein: the mass-volume ratio of the polystyrene to the toluene is 0.15mg/mL, and the concentration of the fluorescent indicator in the fluorescent sol solution is 2.5 mg/mL; the fluorescent indicator is tris (5-amino-1, 10-phenanthroline) ruthenium; the silicon rubber is Dragon skin-30 silicon rubber (brand: Smooth-On), and the volume ratio of the added silicon rubber to the mixed solution of polystyrene and toluene is 1: 3;
s2, the spin coating step is that the substrate is fixed on a spin coating machine, the fluorescent sol agent is dripped on the surface of the substrate for spin coating, and a fluorescence method dissolved oxygen sensitive film is formed on the substrate; the substrate is made of polyethylene terephthalate, and the thickness of the substrate is 2 mm; the spin-coating rotating speed is 3000r/s, and the time is 60 s;
and S3, drying, namely, placing the substrate with the sensitive film in a dark environment at 80 ℃ for drying for 1.5h to obtain the sensitive element of the dissolved oxygen sensor.
Comparative example 1
In the preparation step, the operation was completely identical to that of example 1, except that no silicone rubber was added to S1.
Comparative example 2
In the preparation step, the operation was completely identical to that of example 2, except that no silicone rubber was added to S1.
Comparative example 3
In the preparation step, the operation was completely identical to that of example 3, except that no silicone rubber was added to S1.
Comparative example 4
In the preparation step, the operation was completely identical to that of example 4 except that the adhesive added in S1 was a nitck UV curing adhesive.
Test example 1
Response time comparison tests were performed on the elements of the dissolved oxygen-sensitive membranes prepared in examples 1 to 3 of the present invention and the elements of the dissolved oxygen-sensitive membranes of comparative example 1 (no silicone rubber was added and the remaining preparation steps were the same as in example 1), comparative example 2 (no silicone rubber was added and the remaining preparation steps were the same as in example 2), and comparative example 3 (no silicone rubber was added and the remaining preparation steps were the same as in example 3), respectively.
The invention performs the test according to JJG291-2018 & ltdissolved oxygen determinator verification procedure & gt, the sensor carried in the test process is HACH LDO-II, and a constant temperature environment required by the test is created through a DCW-0506 low-temperature constant temperature bath. According to the 'dissolved oxygen tester verification protocol', the time consumed when the indication value of the sensor reaches 10% of the original value when the dissolved oxygen sensitive film is switched between saturated dissolved oxygen water and anaerobic water environment is measured at a constant temperature and recorded as the response time of the dissolved oxygen fluorescent film. The performance test results are shown in table 1:
table 1 results of performance testing
As can be seen from table 1, the dissolved oxygen fluorescent film prepared after adding the silicone rubber has an improved air permeability and a significantly improved response time.
Test example 2
The response time comparison test was performed on the element of the dissolved oxygen-sensitive membrane prepared in example 2 of the present invention and the element of the dissolved oxygen-sensitive membrane to which the ordinary silicone rubber was not added. Test methods test example 1 was referred to, and the test curves are shown in FIG. 1.
As can be seen from the response time test curve of fig. 1, the response speed and stability of the dissolved oxygen fluorescent film prepared by adding the silicone rubber are significantly improved compared with the dissolved oxygen fluorescent film without adding the silicone rubber.
Test example 3
Response time comparative tests were conducted on the dissolved oxygen sensitive film element prepared in example 4 of the present invention and the dissolved oxygen sensitive film element prepared by adding the noteck UV curing paste. Test methods test example 1 was referred to, and the test results are shown in table 2.
As can be seen from Table 2, the dissolved oxygen fluorescent films prepared by adding different adhesives have influence on the response time. Compared with other adhesives, the dissolved oxygen fluorescent film prepared from the Dragon skin-30 silicon rubber selected in the patent has good air permeability and quick response time.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A preparation method of a dissolved oxygen sensitive film based on fluorescence is characterized by comprising the following steps: the method comprises the steps of preparation of the fluorescent sol, spin coating and drying; wherein,
the preparation method of the fluorescent sol comprises the following steps: and fully mixing the polystyrene and the toluene at room temperature to obtain a mixed solution, adding the fluorescent indicator and the silicon rubber, uniformly mixing, and stirring at room temperature in a dark place until the fluorescent indicator and the silicon rubber are completely dissolved to obtain the fluorescent sol agent.
2. The method for preparing a dissolved oxygen-sensitive film based on fluorescence according to claim 1, wherein: the mass-volume ratio of the polystyrene to the toluene is 0.1-0.5mg/mL, and the concentration of the fluorescent indicator in the fluorescent sol solution is 2-6 mg/mL.
3. The method for preparing a dissolved oxygen-sensitive film based on fluorescence according to claim 1, wherein: the fluorescence indicator is one of platinum (II) -m-tetra (pentafluorobenzene) porphyrin, platinum (II) octaethylporphyrin, tris (2, 2' -bipyridyl) ruthenium (II) complex, tris (4, 7-diphenyl-1, 10-phenanthroline) ruthenium (II) complex, tris (1, 10-phenanthroline) ruthenium (II) and tris (5-amino-1, 10-phenanthroline) ruthenium.
4. The method for preparing a dissolved oxygen-sensitive film based on fluorescence according to claim 1, wherein: the volume ratio of the mixed solution of the silicon rubber, the polystyrene and the toluene is 1: 2-1: 4.
5. The method for preparing a dissolved oxygen-sensitive film based on fluorescence according to claim 4, wherein: the silicone rubber is Dragon skin-30 silicone rubber.
6. The method for preparing a dissolved oxygen-sensitive film based on fluorescence according to claim 1, wherein: the stirring time at room temperature in the dark is 5-10 minutes.
7. The method for preparing a dissolved oxygen-sensitive film based on fluorescence according to claim 1, wherein: the spin coating step is to fix the substrate on a spin coater, drop the fluorescent sol agent on the surface of the substrate, perform spin coating, and form the fluorescent dissolved oxygen sensitive film on the substrate.
8. The method for preparing a dissolved oxygen-sensitive membrane based on fluorescence according to claim 7, wherein: the substrate is made of polyethylene glycol terephthalate or polymethyl methacrylate, and the thickness of the substrate is 1-3 mm.
9. The method for preparing a dissolved oxygen-sensitive film based on fluorescence according to claim 7, characterized in that: the spin coating speed is 3000-.
10. The method for preparing a dissolved oxygen-sensitive film based on fluorescence according to claim 1, characterized in that: and the drying step is that the substrate with the sensitive film after spin coating is placed at 70-90 ℃ and dried for 1.5-2.5h in a dark place, and the sensitive element of the dissolved oxygen sensor is obtained.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS608736A (en) * | 1983-06-09 | 1985-01-17 | ウオルフガング・バ−ニコル | Luminescent layer used for device for measuring oxygen concentration in gas, etc. |
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