CN111289482A - Preparation method of fluorinated modified fluorescence dissolved oxygen sensing film and coating for preparing protective layer - Google Patents
Preparation method of fluorinated modified fluorescence dissolved oxygen sensing film and coating for preparing protective layer Download PDFInfo
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Abstract
The invention provides a preparation method of a fluorinated modified fluorescence dissolved oxygen sensing film and a coating for preparing a protective layer. The preparation method comprises the following steps: mixing fluorine-containing siloxane, tetraethyl silicate, deionized water and absolute ethyl alcohol, and reacting under certain conditions to obtain a fluorinated modified sol-gel matrix; preparing an ethanol solution of an oxygen quenching fluorescent indicator, mixing the ethanol solution with the fluorinated modified sol-gel matrix, and carrying out ultrasonic stirring in the dark to obtain a fluorescent sol solution; aging the substrate in a dark environment at room temperature, and spin-coating the aged sol solution on the surface of the pretreated substrate by using a spin coater to obtain the fluorinated modified fluorescent dissolved oxygen sensing film. The preparation method can improve the sensitivity of the membrane, reduce the response time and simultaneously avoid the membrane from cracking. The invention provides a coating for preparing a fluorescent dissolved oxygen sensing film protective layer, which is prepared by mixing methyl phenyl silicone resin, oil black and/or silicone and a curing agent. The protective layer can improve the long-term stability of the film.
Description
(I) technical field
The invention relates to the technical field of optical dissolved oxygen sensor membranes, in particular to a preparation method of a fluorinated modified fluorescent dissolved oxygen sensing membrane and a coating for preparing a protective layer of the fluorescent dissolved oxygen sensing membrane.
(II) background of the invention
The content of dissolved oxygen in water is one of the important indexes representing the cleanliness of water. The determination of the dissolved oxygen content in water is of great significance to the fields of industrial production, environmental monitoring, medical treatment and health, aquaculture and the like. The dissolved oxygen is measured by an iodometric method, an electrochemical method, and an optical dissolved oxygen sensor method. The iodometry is a pure chemical method, mainly comprises the steps of carrying out oxidation-reduction reaction on dissolved oxygen in water and a certain reducing substance, and then converting the consumption of a reducing agent to obtain the oxygen concentration, but has the defects of complex operation, long time and incapability of real-time online measurement. The electrochemical method, also called an electrode method, detects the content of dissolved oxygen by the magnitude of current generated by the redox reaction of oxygen on an electrode, but also has the problems that a membrane is easy to damage, electrolyte is frequently replaced, the maintenance process is complicated and the like.
The optical dissolved oxygen sensor method based on the fluorescence quenching principle has the advantages of no oxygen consumption, no need of a reference electrode, high measurement accuracy, high sensitivity, no electromagnetic interference and the like, and can meet the requirements of real-time online monitoring. The fluorescence quenching principle refers to the phenomenon that the fluorescence intensity and the service life of fluorescent molecules are reduced due to the action of fluorescent substances and extinguishing agent molecules, and common fluorescence extinguishing agents comprise halogen ions, heavy metal ions, oxygen molecules, nitro compounds, diazo compounds, carboxyl compounds, carbonyl compounds and the like. Oxygen is a natural quencher for some fluorescent substances, and the oxygen quenching process is proved to be dynamic quenching, and the principle is that the oxygen and the fluorescent substance in an excited state undergo energy transfer after collision, so that the fluorescence intensity is weakened, but the oxygen and the fluorescent substance are separated immediately after collision, and the fluorescent molecules are not subjected to chemical change, so that the quenching of the oxygen on the fluorescent molecules is reversible. The dynamic quenching process conforms to the Stern-Volmer equation, and the quenching degree of the fluorescent substance is positively correlated with the oxygen concentration.
The core component of an optical dissolved oxygen sensor is a fluorescent dissolved oxygen sensing membrane, which is typically composed of a fluorescent oxygen-sensitive indicator and a supporting matrix. The solid matrix adopted by the dissolved oxygen fluorescent film usually comprises a polymer and a sol-gel material, but the polymer is easy to generate photochemical reaction with the indicator, so that the optical stability of the polymer and the indicator is poor, and the sol-gel has good optical permeability, mechanical property and chemical stability, and meanwhile, the reaction condition of the preparation process is mild, the preparation mode is convenient, and the like, so that people pay attention to the solid matrix.
Although the sol-gel method has been widely used for preparing dissolved oxygen sensing films, the response time, long-term stability and other properties of the prepared dissolved oxygen sensing films still need to be improved, and matrix modification is an effective improvement means in this respect. The existing matrix modification methods comprise fluorination modification, doping of porous nanoparticles, gold film coating, titanium oxide serving as a precursor and the like.
The fluoridation modification of the sol-gel method is to take fluorine-containing siloxane as a precursor, obtain a fluorine-containing material through aging reaction, and further introduce fluorine atoms into the oxygen sensing film for modification to obtain a modified dissolved oxygen film with excellent performance. The fluorizated modified material is used for preparing the dissolved oxygen sensing film, and has the main advantages of improving the sensitivity of the sensing film, improving the long-term stability, avoiding the cracking of the film, reducing the photobleaching and the like.
When the fluorescent oxygen sensing film sheet is used, a protective coating needs to be coated on the outer layer of the fluorescent film layer to protect the fluorescent dissolved oxygen film layer from being polluted and damaged by water. However, the existing fluorescence dissolved oxygen sensing film which can be put into market application has the defects of long response time, fragile protective layer and poor long-term stability.
In view of the above, many researchers have made extensive studies on the preparation of dissolved oxygen sensing films and coated protective layers by modified sol-gel methods, and have proposed various preparation methods, but further improvements are required in the performance, long-term stability and response time of the coated films of the sensing films and the protective coatings.
Disclosure of the invention
The first purpose of the invention is to provide a preparation method of a fluorinated modified fluorescence dissolved oxygen sensing film, which has high efficiency and simple process, can improve the sensitivity of the oxygen sensitive fluorescent film, reduce the response time, avoid the problem of film cracking and obtain the fluorescence dissolved oxygen film with excellent performance.
It is a second object of the present invention to provide a coating material for producing a protective layer of a fluorogenic dissolved oxygen sensing film, which coating material produces a protective layer capable of improving the long-term stability of the fluorogenic dissolved oxygen sensing film with little influence on the response time of the fluorogenic dissolved oxygen sensing film.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a fluorinated modified fluorescence dissolved oxygen sensing membrane, comprising the following steps:
(1) mixing fluorine-containing siloxane, tetraethyl silicate, deionized water and absolute ethyl alcohol in a certain ratio, adjusting the pH to 0.5-4 by using hydrochloric acid as a catalyst, and sealing and magnetically stirring for 1-5 hours to obtain a fluorinated modified sol-gel matrix; preparing an ethanol solution of an oxygen quenching fluorescent indicator with the concentration of 3-40 mg/mL, mixing the ethanol solution with the fluorinated modified sol-gel matrix, and carrying out dark ultrasonic stirring for 10-50 minutes to obtain a fluorescent sol solution; aging the substrate at room temperature for 24-96 hours in a dark environment, spin-coating the aged sol solution on the surface of the pretreated substrate by using a spin coater, wherein the dosage of the aged sol solution for spin-coating is 60-300 mu L/5.76cm based on the surface area of the substrate2Then naturally airing to obtain a uniform fluoridation modified fluorescence dissolved oxygen sensing film;
wherein the volume ratio of the fluorine-containing siloxane to the ethyl alcohol solution of the tetraethyl silicate to the deionized water to the anhydrous ethyl alcohol to the oxygen-quenched fluorescent indicator is 1: 0.8-2: 0.2-1.2: 1-12: 0.2 to 1.0.
In the invention, the substrate can be glass, organic glass, quartz glass, a cover glass or acrylic. The pretreatment method of the base material comprises the following steps: soaking the mixture in NaOH solution for 12-48h, soaking in absolute ethyl alcohol and deionized water, finally washing with deionized water, and drying for later use.
In the present invention, the fluorine-containing siloxane may be at least one of trimethoxy (3,3, 3-trifluoropropyl) silane, trifluoropropylmethylcyclotrisiloxane, and 2,4,6, 8-tetramethyl-2, 4,6, 8-tetrakis (3,3, 3-trifluoropropyl) cyclotetrasiloxane.
In the present invention, the oxygen-quenching fluorescent indicator may be at least one of tris (2, 2-bipyridyl) ruthenium dichloride, octaethylplatinum porphyrin, tris (4, 7-biphenyl-1, 10-phenanthroline) ruthenium dichloride and tris (5-amino-1, 10-phenanthroline) ruthenium dichloride, preferably at least one of tris (2, 2-bipyridyl) ruthenium dichloride, tris (4, 7-biphenyl-1, 10-phenanthroline) ruthenium dichloride and tris (5-amino-1, 10-phenanthroline) ruthenium dichloride, and most preferably tris (4, 7-biphenyl-1, 10-phenanthroline) ruthenium dichloride. The concentration of the ethanol solution of the oxygen-quenched fluorescent indicator is preferably 6-30 mg/mL, more preferably 12-24 mg/mL, and most preferably 24 mg/mL.
In step (1) of the present invention, the volume ratio of the fluorine-containing siloxane to the ethanol solution of tetraethyl silicate to the ethanol solution of the oxygen-quenched fluorescent indicator is preferably 1: 1.0-1.6: 0.4-1.0: 1-5: 0.4 to 0.8, particularly preferably 1: 1.1: 0.4: 2: 0.8.
in the step (1) of the invention, the aging time is preferably 48 hours, and the obtained fluorescent dissolved oxygen film has high sensitivity and smooth and non-cracked surface.
In the step (1), the amount of the aged sol solution for spin coating is preferably 100-250 μ L/5.76cm based on the surface area of the substrate2Most preferably 200. mu.L/5.76 cm2。
In a particularly preferred step (1) of the present invention, the oxygen-quenched fluorescent indicator is tris (4, 7-biphenyl-1, 10-phenanthroline) ruthenium dichloride, and the concentration of the ethanol solution of the oxygen-quenched fluorescent indicator is 24 mg/mL; the aging time was 48 hours, and the amount of the aged sol solution used for spin coating was 200. mu.L/5.76 cm based on the surface area of the substrate2。
In order to improve the long-term stability of the fluorinated modified fluorolytic oxygen sensing membrane, the preparation method preferably further comprises the steps of:
(2) mixing methyl phenyl silicone resin and the substance A in proportion, fully stirring and dissolving, adding a curing agent, and continuously stirring uniformly to prepare a black layer coating liquid; spin-coating the black layer coating liquid on the outer layer of the fluorinated modified fluorescent dissolved oxygen sensing film obtained in the step (1) by using a spin coater to obtain a fluorinated modified fluorescent dissolved oxygen sensing film coated with a protective layer; the substance A is oil black and/or silicone;
wherein the mass ratio of the methyl phenyl silicone resin to the substance A and the curing agent is 1: 3% -20%: 1 to 10 percent.
In step (2) of the present invention, the curing agent may be a resin curing agent, which can cure the resin.
In step (2) of the present invention, the mass ratio of the methylphenyl silicone resin to the substance a and the curing agent is preferably 1: 5% -10%: 2 to 5 percent.
In step (2) of the present invention, the substance a is preferably silicone, which can significantly reduce the response time of the oxygen sensing film.
In a second aspect, the invention provides a coating for preparing a fluorescence dissolving oxygen sensing film protective layer, which is prepared from methyl phenyl silicone resin, a substance A and a curing agent according to a mass ratio of 1: 3% -20%: 1 to 10 percent of the total weight of the composition; the substance A is oil black and/or silicone.
Preferably, the curing agent is a resin curing agent.
Preferably, the mass ratio of the methyl phenyl silicone resin to the substance A and the curing agent is 1: 5% -10%: 2 to 5 percent.
Preferably, the substance A is silicone.
When the coating is prepared, the methyl phenyl silicone resin and the substance A are mixed in proportion, and after the methyl phenyl silicone resin and the substance A are fully stirred and dissolved, the curing agent is added and continuously stirred uniformly, so that the coating liquid is obtained.
Compared with the prior art, the invention has the technical advantages that:
(1) the invention adopts the fluorinated organic modified sol-gel method to prepare the fluorescent dissolved oxygen membrane, the process is simple and efficient, and the fluorinated organic modification enhances the affinity of the sol-gel matrix to oxygen, thereby increasing the diffusion coefficient of oxygen in the matrix, further improving the sensitivity of the dissolved oxygen sensing membrane and reducing the response time; and the hydrophobicity of the sensing membrane can be improved, so that the problems of hole collapse caused by wet gel shrinkage are solved, membrane cracking is avoided, and the fluorinated modified fluorescent dissolved oxygen membrane with excellent performance is obtained.
(2) The ruthenium complex is used as the oxygen quenching fluorescent indicator, so that the sensitivity and the response time of the fluorescent dissolved oxygen film can be improved.
(3) The protective layer with specific composition is used for protecting the fluorescent film layer from light, so that the fluorescent film layer can be protected from being damaged and polluted by water, the fluorescent dissolved oxygen film has strong pollution resistance and damage resistance, and the long-term stability of the dissolved oxygen sensing film is further improved; while not affecting or even improving the response time of the fluorescent dissolved oxygen membrane.
(IV) description of the drawings
FIG. 1 is a scanning electron micrograph of a fluorinated organically modified fluorodissolved oxygen sensor film prepared according to example 5;
FIG. 2 is a dynamic response curve of the fluorescent dissolved oxygen film coated with a black protective layer in example 15;
FIG. 3 is a dynamic response curve of the fluorinated organically modified fluorescent film in the oxygen-free water and the aerobic water in comparative example 1;
FIG. 4 is a dynamic response curve of the fluorine-free organically modified fluorescent film of comparative example 1 in oxygen-free water and oxygen-free water.
(V) detailed description of the preferred embodiments
The invention is further described below with reference to specific examples.
The transparent substrate used in all examples was a cover glass, the specification of which was 24mm × 24mm, and the pretreatment methods were: soaking in 0.1M NaOH solution for 24 hr, soaking in anhydrous ethanol and deionized water, washing with deionized water, and oven drying.
The invention adopts a dissolved oxygen sensor developed by Hangzhou Mimeji and science and technology Limited company based on a fluorescence quenching method to test the voltage response signal values of the prepared fluorescent dissolved oxygen sensing film in the oxygen-free water and the oxygen-free water under different process conditions, and obtains a corresponding response curve. Wherein the sensitivity is the ratio of the non-oxygen water voltage signal to the oxygen water voltage signal; the time required from the oxygen-free aqueous solution to the time at which the response of the aerobic aqueous solution reaches 95% of the steady-state value is defined as the response time. The specific determination method comprises the following steps: assembling the prepared fluorescent film on an oxygen sensor probe, and placing the sensor probe into oxygen-free water (saturated NaSO)3Solution), after the signal is stable, 10 data are read, and then the solution is quickly put into aerobic water (deionized water) to continue reading the data.
Example 1:
the preparation method of the fluorinated organic modified fluorescence dissolved oxygen sensing film comprises the following specific steps:
1.24ml of trimethoxy (3,3, 3-trifluoropropyl) silane and 1.36ml of tetraethyl silicate were added to a clear screw-top flask, followed by further addition of 0.48ml of deionized water and 2.50ml of absolute ethanol, followed by adjustment of the pH to 1.3 with 0.1mol/L hydrochloric acid as catalyst. Covering, sealing and magnetically stirring for 1.2 hours, adding 1.0mL of tris (4, 7-biphenyl-1, 10-phenanthroline) dichlororuthenium ethanol solution with the concentration of the indicator being 6mg/mL, ultrasonically stirring for 20 minutes, and aging for 24 hours at normal temperature in a light-tight environment. And finally, spin-coating 60 microliters of fluorescent sol solution on the surface of the pretreated transparent substrate by using a spin coater, and naturally drying to obtain the fluorinated modified dissolved oxygen sensing film.
Examples 2 to 6:
examples 2 to 6 refer to the method of example 1, except that the concentrations of the ethanol solutions of the fluorescent indicators were 3mg/mL (example 2), 12mg/mL (example 3), 18mg/mL (example 4), 24mg/mL (example 5) and 30mg/mL (example 6) in this order, and the experimental results showed that increasing the concentration of the fluorescent indicator in a certain range was advantageous for enhancing the oxygen quenching effect and increasing the sensitivity of the fluorescence-dissolved oxygen sensor membrane, but the self-quenching phenomenon also existed between indicator molecules and the increase in the concentration of the indicator also enhanced the self-quenching phenomenon, which resulted in a decrease in the sensitivity of the fluorescence membrane, and thus the concentration of the fluorescent indicator was controlled, and the oxygen sensor membranes prepared in examples 1 to 6 had sensitivities of 2.8, 2.5, 3.3, 3.5, 3.7 and 2.6, respectively, and the results showed that when the concentration of the indicator was 24mg/mL, the fluorescence dissolved oxygen sensing film has higher sensitivity.
Examples 7 to 9:
examples 7 to 9 refer to the method of example 5, except that the aging time of the fluorescent sol solution was 48 hours (example 7), 72 hours (example 8), and 96 hours (example 9), in this order, it was found that cracking occurred on the surface of the dissolved oxygen film at the aging time of 96 hours, and the experimental results showed that the sensitivity of the sensor film gradually increased with the increase of the aging time, but the film cracked due to the increase of the internal stress with the increase of the thickness of the film with the increase of the aging time, and thus the aging time of the sol solution was controlled, and the results showed that the sensitivity of the obtained fluorescent dissolved oxygen film was higher, 3.8, and the surface was smooth and not cracked when the aging time was 48 hours (example 7).
Example 10:
example 10 referring to the method of example 7, except that the volume amounts of the spin-coated fluorescent sol solution were 100 microliters, 150 microliters, 200 microliters, 250 microliters, and 300 microliters, respectively, experimental results showed that the sensitivity of the fluorescent film gradually increased with the increase of the volume amount, i.e., the film thickness, within a certain spin-coating volume amount range, but the film thickness exceeded a certain range, which resulted in the cracking of the film. The sensitivity of the films prepared with the volume amounts of 100 microliter, 150 microliter, 200 microliter, 250 microliter and 300 microliter is 3.9, 4.2, 4.5, 4.1 and 3.7 respectively, and the results show that the sensitivity of the fluorescent film prepared with the spin-coated fluorescent sol solution with the volume amount of 200 microliter is higher and the diaphragm is not cracked.
Example 11:
example 11 referring to the method of example 7, except that the oxygen-quenched fluorescent indicator was tris (2, 2-bipyridine) ruthenium dichloride, octaethylplatinum porphyrin, tris (5-amino-1, 10 phenanthroline) ruthenium dichloride in this order, the experimental results showed that the sensitivity of the fluorescent film was 2.6 and the response time was 85s when the fluorescent indicator was octaethylplatinum porphyrin; when the fluorescent indicators are tris (2, 2-bipyridyl) ruthenium dichloride and tris (5-amino-1, 10-phenanthroline) ruthenium dichloride, the sensitivity of the fluorescent film is 3.0 and 3.3 respectively, and the response time is 71s and 57s respectively. The results show that the oxygen sensing membrane performs better in terms of sensitivity and response time when the ruthenium complex is used as a fluorescent indicator.
Comparative example 1
(1) The preparation method of the fluorinated organic modified fluorescence dissolved oxygen sensing film comprises the following specific steps:
1.24ml of fluorosilicone trimethoxy (3,3, 3-trifluoropropyl) silane and 1.36ml of tetraethyl silicate were added to a clear screw-top flask, followed by further addition of 0.48ml of deionized water and 2.50ml of absolute ethanol, followed by adjustment of the pH to 1.3 with 0.1mol/L hydrochloric acid as a catalyst. Covering, sealing and magnetically stirring for 1.2 hours, adding 1.0mL of tris (4, 7-biphenyl-1, 10-phenanthroline) dichlororuthenium ethanol solution with the concentration of the indicator being 24mg/mL, ultrasonically stirring for 20 minutes, and aging for 48 hours at normal temperature in a light-tight environment. And finally, spin-coating 200 microliters of fluorescent sol solution on the surface of the pretreated transparent substrate by using a spin coater, and naturally drying to obtain the fluorinated modified dissolved oxygen sensing film.
(2) The preparation method of the fluorine-free organic modified fluorescence dissolved oxygen sensing film comprises the following specific steps:
(2) the method is the same as the method (1), except that the siloxane is fluorosilicone-methyl trimethoxy silane, and the fluorine-free organic modified fluorescence dissolved oxygen sensing film is prepared.
The fluorine-containing and fluorine-free modified films are prepared, the surfaces of the fluorinated modified films are smooth and do not crack, signal values of the fluorescent films prepared under the conditions of fluorine and fluorine-free in oxygen-free water and oxygen-free water are tested by using a dissolved oxygen sensor based on a fluorescence quenching method, and the obtained response curves are shown in figures 3 and 4.
Example 12:
the preparation method of the fluorescent oxygen sensing film coated with the protective layer comprises the following specific steps:
the methyl phenyl silicone resin, methyl silicone resin, acrylic resin and resin curing agent used in the experimental process were purchased from Shanghai Bohua chemical Co., Ltd, and the oil black was purchased from Rui New pigment Co., Ltd, Dongguan.
Mixing 20.0g of methyl phenyl silicone resin and 1.2g of oil black, stirring by a stirrer for 1 hour to dissolve, adding 0.4g of resin curing agent, and magnetically stirring uniformly to obtain a black layer coating liquid; the black layer coating liquid was spin-coated on the outer layer of the fluorescent film (response time 42.75s) prepared in example 10 in a volume amount of 200 microliters by using a spin coater, and the fluorescent dissolved oxygen film coated with the black light-shielding layer was obtained as a protective coating. The fluorescent dissolved oxygen film coated with the protective layer has strong pollution resistance and damage resistance, and the long-term stability of the dissolved oxygen sensing film is improved.
Examples 13 to 14:
examples 13-14 the method of example 12 was followed except that the silicone resin was a methyl silicone resin (example 13) and an acrylic resin (example 14), to obtain a black light-shielding layer-coated fluorescent film. The response times of the fluorescent films coated with the black layers prepared in examples 12 to 14 were found to be 42s, 114s and 142s, respectively, by controlling the substrates of the black layers, and the results showed that the substrates were methyl phenyl silicone resin, which had a small effect on the response times of the fluorescent films.
Example 15:
example 15 the process of example 12 was referenced except that the oil black was replaced with carbon black, aqueous ink, oil ink and silicone, respectively. The signal values of the fluorescent films coated with black layers and prepared under different black shading layer materials are tested by using a dissolved oxygen sensor based on a fluorescence quenching method under the conditions of no-oxygen water and oxygen water, response curves are obtained, the performance of the fluorescent films obtained by using carbon black, water-based ink and oil-based ink is poor, the response time of the fluorescent films obtained by using a silicone material is shorter and is 14s, and the response curve graph is shown in figure 2.
Comparative example 2
(1) The preparation method of the fluorinated organic modified fluorescence dissolved oxygen sensing film comprises the following specific steps:
1.24ml of trimethoxy (3,3, 3-trifluoropropyl) silane and 1.36ml of tetraethyl silicate were added to a clear screw-top flask, followed by further addition of 0.48ml of deionized water and 2.50ml of absolute ethanol, followed by adjustment of the pH to 1.3 with 0.1mol/L hydrochloric acid as catalyst. Covering, sealing and magnetically stirring for 1.2 hours, adding 1.0mL of tris (4, 7-biphenyl-1, 10-phenanthroline) dichlororuthenium ethanol solution with the concentration of the indicator being 24mg/mL, ultrasonically stirring for 20 minutes, and aging for 48 hours at normal temperature in a light-tight environment. And finally, spin-coating 200 microliters of fluorescent sol solution on the surface of the pretreated transparent substrate by using a spin coater, and naturally drying to obtain the fluorinated modified dissolved oxygen sensing film.
(2) The preparation method of the fluorescence dissolved oxygen sensing film coated with the black protective layer comprises the following specific steps:
mixing 20.0g of methyl phenyl silicone resin and 1.2g of silicone, stirring by a stirrer for 1 hour to dissolve, adding 0.4g of resin curing agent, and magnetically stirring uniformly to obtain a black layer coating liquid; and (3) coating the black layer coating liquid on the outer layer of the fluorescent dissolved oxygen film prepared in the step (1) in a spinning manner by using a spin coater to obtain the fluorescent dissolved oxygen sensing film coated with the black protective layer.
The signal values of the fluorinated modified dissolved oxygen film and the dissolved oxygen film coated with the black protective layer in the oxygen-free water and the oxygen-containing water are tested by using a dissolved oxygen sensor based on a fluorescence quenching method to obtain a response curve, and the experimental result shows that the response time of the dissolved oxygen film coated with the black layer is shorter and is 14 s.
And (3) testing the heat resistance and the long-term stability of the fluorinated modified dissolved oxygen film (1 layer film) obtained in the step (1) and the dissolved oxygen film (2 layer film) coated with the black layer obtained in the step (2) in a water bath at 40 ℃, and testing the films in oxygen-free water and aerobic water by using a dissolved oxygen sensor based on a fluorescence quenching method every 24 hours to obtain a voltage signal value. Continuously testing for 1 month, and finding that the signal values of the 1-layer film and the 2-layer film in the anaerobic water and the aerobic water are basically unchanged; continuously testing for 3 months, and finding that the signal value of the 1 layer of membrane in the anaerobic water is reduced by 2 percent, the signal value in the aerobic water is basically kept unchanged, and the signal value of the 2 layer of membrane in the anaerobic water and the aerobic water is basically unchanged; continuously testing for 6 months, and finding that the signal value of the 1 layer of film in the anaerobic water and the aerobic water is reduced, and the signal value of the 2 layer of film in the anaerobic water and the aerobic water is basically kept unchanged; after 1 year of continuous test, the signal value of the film 1 in the anaerobic water and the aerobic water is reduced, the signal value of the film 2 in the anaerobic water is reduced by 5 percent, and the signal value in the aerobic water is basically kept unchanged. The experimental results show that 2-layer films (dissolved oxygen films coated with black protective layer) show good heat resistance and long-term stability in tests for up to 1 year.
Claims (10)
1. A preparation method of a fluorinated modified fluorescence dissolved oxygen sensing film comprises the following steps:
(1) mixing fluorine-containing siloxane, tetraethyl silicate, deionized water and absolute ethyl alcohol in a certain ratio, adjusting the pH to 0.5-4 by using hydrochloric acid as a catalyst, and sealing and magnetically stirring for 1-5 hours to obtain a fluorinated modified sol-gel matrix; preparing an ethanol solution of an oxygen quenching fluorescent indicator with the concentration of 3-40 mg/mL, mixing the ethanol solution with the fluorinated modified sol-gel matrix, and carrying out dark ultrasonic stirring for 10-50 minutes to obtain a fluorescent sol solution; aging the substrate at room temperature for 24-96 hours in a dark environment, spin-coating the aged sol solution on the surface of the pretreated substrate by using a spin coater, wherein the dosage of the aged sol solution for spin-coating is 60-300 mu L/5.76cm based on the surface area of the substrate2Then naturally airing to obtain a uniform fluoridation modified fluorescence dissolved oxygen sensing film;
wherein the volume ratio of the fluorine-containing siloxane to the ethyl alcohol solution of the tetraethyl silicate to the deionized water to the anhydrous ethyl alcohol to the oxygen-quenched fluorescent indicator is 1: 0.8-2: 0.2-1.2: 1-12: 0.2 to 1.0.
2. The method of claim 1, wherein: the preparation method further comprises the following steps:
(2) mixing methyl phenyl silicone resin and the substance A in proportion, fully stirring and dissolving, adding a curing agent, and continuously stirring uniformly to prepare a black layer coating liquid; spin-coating the black layer coating liquid on the outer layer of the fluorinated modified fluorescent dissolved oxygen sensing film obtained in the step (1) by using a spin coater to obtain a fluorinated modified fluorescent dissolved oxygen sensing film coated with a protective layer; the substance A is oil black and/or silicone;
wherein the mass ratio of the methyl phenyl silicone resin to the substance A and the curing agent is 1: 3% -20%: 1 to 10 percent.
3. The method of claim 1 or 2, wherein: the fluorine-containing siloxane is at least one of trimethoxy (3,3, 3-trifluoropropyl) silane, trifluoropropylmethylcyclotrisiloxane and 2,4,6, 8-tetramethyl-2, 4,6, 8-tetra (3,3, 3-trifluoropropyl) cyclotetrasiloxane;
the oxygen quenching fluorescent indicator is at least one of tris (2, 2-bipyridyl) ruthenium dichloride, octaethylplatinum porphyrin, tris (4, 7-biphenyl-1, 10-phenanthroline) ruthenium dichloride and tris (5-amino-1, 10-phenanthroline) ruthenium dichloride, and preferably at least one of tris (2, 2-bipyridyl) ruthenium dichloride, tris (4, 7-biphenyl-1, 10-phenanthroline) ruthenium dichloride and tris (5-amino-1, 10-phenanthroline) ruthenium dichloride.
4. The method of claim 1 or 2, wherein: the concentration of the ethanol solution of the oxygen-quenched fluorescent indicator is 6-30 mg/mL, preferably 12-24 mg/mL, and most preferably 24 mg/mL.
5. The method of claim 1 or 2, wherein: in the step (1), the aging time is 48 hours.
6. The method of claim 1, wherein: in the step (1), the amount of the aged sol solution for spin coating is 100-250 μ L/5.76cm based on the surface area of the substrate2Most preferably 200. mu.L/5.76 cm2。
7. The method of claim 1, wherein: in the step (1), the oxygen-quenched fluorescent indicator is tris (4, 7-biphenyl-1, 10-phenanthroline) ruthenium dichloride, and the concentration of an ethanol solution of the oxygen-quenched fluorescent indicator is 24 mg/mL; the aging time was 48 hours, and the amount of the aged sol solution used for spin coating was 200. mu.L/5.76 cm based on the surface area of the substrate2。
8. A coating for preparing a fluorescent dissolved oxygen sensing film protective layer is prepared from methyl phenyl silicone resin, a substance A and a curing agent according to a mass ratio of 1: 3% -20%: 1 to 10 percent of the total weight of the composition; the substance A is oil black and/or silicone.
9. The coating of claim 8, wherein: the curing agent is a resin curing agent.
10. The coating of claim 8 or 9, wherein: the mass ratio of the methyl phenyl silicone resin to the substance A to the curing agent is 1: 5% -10%: 2 to 5 percent.
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