CN112980029A - Oxygen sensing film and manufacturing method thereof - Google Patents
Oxygen sensing film and manufacturing method thereof Download PDFInfo
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- CN112980029A CN112980029A CN202110174099.7A CN202110174099A CN112980029A CN 112980029 A CN112980029 A CN 112980029A CN 202110174099 A CN202110174099 A CN 202110174099A CN 112980029 A CN112980029 A CN 112980029A
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- light
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 93
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The application relates to an oxygen sensing membrane, including printing opacity protective layer, fluorescent layer and shading ventilative layer, the fluorescent layer sets up in one side of shading ventilative layer, and the fluorescent layer is covered to the printing opacity protective layer, and the fluorescent layer includes polymer base member and the compound phosphor powder of embedding dispersion in polymer base member, and compound phosphor powder obtains through loading fluorescence indicator in printing opacity nano-particle and oxygen permeability printing opacity polymer. Also relates to a manufacturing method of the oxygen sensing film. In the oxygen sensing membrane of this application, the great specific surface area of printing opacity nano-particle can improve the fluorescence efficiency of oxygen sensing membrane, it makes fluorescence indicator dispersion even to add oxygen permeability printing opacity polymer, the stability of indicator is good, the printing opacity protective layer can prevent that fluorescence indicator from revealing and do not disturb the fluorescence signal transmission in addition, the ventilative layer of shading guarantees the interference of the other light signals of separation and pollutant when oxygen transmission, preparation technology can be simplified to complete three layer construction, be favorable to improving the measurement uniformity of oxygen sensing membrane.
Description
Technical Field
The application relates to the technical field of oxygen concentration detection, in particular to an oxygen sensing film and a manufacturing method thereof.
Background
The photochemical oxygen sensor based on the fluorescence quenching principle detects gaseous oxygen or dissolved oxygen by detecting the quenching attenuation condition of fluorescence intensity, the core component of the photochemical oxygen sensor is an oxygen sensing film, the oxygen sensing film mainly contains an indicator and a solid matrix, the fluorescence efficiency of the oxygen sensing film and the stability of the indicator have important influence on the performance of the sensor, and meanwhile, the preparation process of the oxygen sensing film also needs to ensure the consistency of the measurement performance. Therefore, it is necessary to provide an oxygen sensing membrane having high fluorescence efficiency, good stability of the indicator, and simple manufacturing process.
Disclosure of Invention
In view of the above technical problems, the present application provides an oxygen sensing membrane and a method for manufacturing the same, which have high fluorescence efficiency, good stability of the indicator, and a simple preparation process.
In order to solve the technical problem, the application provides an oxygen sensing membrane, which comprises a light-transmitting protective layer, a fluorescent layer and a light-shading breathable layer, wherein the fluorescent layer is arranged on one side of the light-shading breathable layer, the light-transmitting protective layer covers the fluorescent layer, the fluorescent layer comprises a polymer matrix and composite fluorescent powder embedded and dispersed in the polymer matrix, and the composite fluorescent powder is obtained by loading a fluorescent indicator in light-transmitting nano particles and an oxygen-permeable light-transmitting polymer.
Optionally, the mass ratio of the oxygen-permeable light-transmitting polymer to the light-transmitting nanoparticles is 1: 0.5-1: 3, and the mass of the fluorescent indicator is 1% -5% of the total mass of the oxygen-permeable light-transmitting polymer and the light-transmitting nanoparticles.
Optionally, the light-transmitting nanoparticles are hydrophobic gas-phase nano-silica, the particle size is 7-40nm, and the specific surface area is 100-2(ii)/g; and/or the oxygen-permeable light-transmitting polymer is particles or powder of at least one of polystyrene and ethyl cellulose.
Optionally, the light-transmitting protective layer is a transparent polymer sheet made of organic glass, polyvinyl chloride or polyester; and/or the polymer matrix is composite organic silicon rubber.
The present application also provides a method of making an oxygen sensing membrane, comprising:
a. providing a light-shielding breathable layer;
b. forming a fluorescent layer on the shading breathable layer, wherein the fluorescent layer comprises a polymer matrix and composite fluorescent powder embedded and dispersed in the polymer matrix, and the composite fluorescent powder is obtained by loading a fluorescent indicator in light-transmitting nano particles and an oxygen-permeable light-transmitting polymer;
c. forming a light-transmitting protective layer on the fluorescent layer;
d. an oxygen sensor film was obtained.
Optionally, step a, comprises:
mixing and stirring a shading material, fluororesin powder, an inorganic filler, organic silicon rubber and a curing agent;
and coating the mixture on a substrate for curing to obtain the shading and ventilating layer.
Optionally, step b, comprises:
b1. providing the composite fluorescent powder and a precursor of the polymer matrix, wherein the precursor of the polymer matrix is a precursor of composite organic silicon rubber;
b2. dispersing the composite fluorescent powder in a first organic solvent to obtain a mixed solution;
b3. mixing the mixed solution with a precursor of the polymer matrix to obtain a reaction solution;
b4. and coating the reaction solution on the shading and ventilating layer for curing.
Optionally, step b1, comprising:
dispersing a fluorescent indicator in a second organic solvent;
adding the oxygen-permeable light-transmitting polymer and the light-transmitting nano particles into the second organic solvent dispersed with the fluorescent indicator, and mixing;
removing the second organic solvent to isolate composite fluorescent particles;
and grinding the composite fluorescent particles to obtain the composite fluorescent powder.
Optionally, the mass ratio of the oxygen-permeable light-transmitting polymer to the light-transmitting nanoparticles is 1: 0.5-1: 3, and the addition amount of the fluorescent indicator is 1% -5% of the total mass of the oxygen-permeable light-transmitting polymer and the light-transmitting nanoparticles; and/or the oxygen-permeable light-transmitting polymer is particles or powder of at least one of polystyrene and ethyl cellulose.
Optionally, step c, comprises:
after the reaction solution is coated on the shading breathable layer, covering a transparent polymer sheet on the coating of the reaction solution to serve as the light-transmitting protective layer;
and curing the coating of the reaction solution to form the light-transmitting protective layer fixed on the fluorescent layer.
The oxygen sensing membrane comprises a light-transmitting protective layer, a fluorescent layer and a light-shading breathable layer, wherein the fluorescent layer is arranged on one side of the light-shading breathable layer, the light-transmitting protective layer covers the fluorescent layer, the fluorescent layer comprises a polymer matrix and composite fluorescent powder embedded and dispersed in the polymer matrix, and the composite fluorescent powder is obtained by loading a fluorescent indicator in light-transmitting nano particles and an oxygen-permeable light-transmitting polymer. In the oxygen sensing membrane of this application, the great specific surface area of printing opacity nano-particle can improve the fluorescence efficiency of oxygen sensing membrane, it makes fluorescence indicator dispersion even to add oxygen permeability printing opacity polymer, the stability of indicator is good, the printing opacity protective layer can prevent that fluorescence indicator from revealing and do not disturb the fluorescence signal transmission in addition, the ventilative layer of shading guarantees the interference of the other light signals of separation and pollutant when oxygen transmission, preparation technology can be simplified to complete three layer construction, be favorable to improving the measurement uniformity of oxygen sensing membrane.
The method for manufacturing the oxygen sensing film comprises the steps of providing a shading breathable layer; forming a fluorescent layer on the shading breathable layer, wherein the fluorescent layer comprises a polymer matrix and composite fluorescent powder embedded and dispersed in the polymer matrix, and the composite fluorescent powder is obtained by loading a fluorescent indicator in light-transmitting nano-particles and an oxygen-permeable light-transmitting polymer; forming a light-transmitting protective layer on the fluorescent layer; an oxygen sensor film was obtained. By the method, the prepared oxygen sensing film has a complete three-layer structure, the preparation process is simple, and the measurement consistency of the oxygen sensing film is improved.
Drawings
Fig. 1 is a schematic view showing the structure of an oxygen sensing film according to a first embodiment;
fig. 2 is a schematic flow chart showing a method for manufacturing an oxygen sensor film according to a second embodiment.
Detailed Description
The following description of the embodiments of the present application is provided for illustrative purposes, and other advantages and capabilities of the present application will become apparent to those skilled in the art from the present disclosure.
In the following description, reference is made to the accompanying drawings that describe several embodiments of the application. It is to be understood that other embodiments may be utilized and that mechanical, structural, electrical, and operational changes may be made without departing from the spirit and scope of the present application. The following detailed description is not to be taken in a limiting sense, and the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Although the terms first, second, etc. may be used herein to describe various elements in some instances, these elements should not be limited by these terms. These terms are only used to distinguish one element from another.
Also, as used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context indicates otherwise. It will be further understood that the terms "comprises," "comprising," "includes" and/or "including," when used in this specification, specify the presence of stated features, steps, operations, elements, components, items, species, and/or groups, but do not preclude the presence, or addition of one or more other features, steps, operations, elements, components, species, and/or groups thereof. The terms "or" and/or "as used herein are to be construed as inclusive or meaning any one or any combination. Thus, "A, B or C" or "A, B and/or C" means "any of the following: a; b; c; a and B; a and C; b and C; A. b and C ". An exception to this definition will occur only when a combination of elements, functions, steps or operations are inherently mutually exclusive in some way.
First embodiment
Fig. 1 is a schematic view showing the structure of an oxygen sensing film according to a first embodiment. As shown in fig. 1, the oxygen sensing membrane of the present embodiment includes a light-transmitting protective layer 13, a fluorescent layer 12 and a light-shielding air-permeable layer 11, wherein the fluorescent layer 12 is disposed on one side of the light-shielding air-permeable layer 11, and the light-transmitting protective layer 13 covers the fluorescent layer 12.
The light-shielding breathable layer 11 is used for ensuring that oxygen is transmitted to the fluorescent layer 12, and simultaneously can block the interference of other optical signals and pollutants. The shading breathable layer 11 comprises shading materials, fluororesin powder, inorganic filler and organic silicon rubber, the shading materials are preferably carbon black, the dyeing shading effect is achieved, the fluororesin powder is acid-base resistant, corrosion resistant and good in temperature stability, the shading breathable layer 11 can be loosened and porous, the mechanical strength is increased, and the inorganic filler can increase the toughness and rigidity of the shading breathable layer 11. The shading material, fluororesin powder, inorganic filler, organic silicon rubber and curing agent of the organic silicon rubber are mixed and stirred uniformly to obtain a mixture, the mixture is coated on a substrate by spin coating or screen printing, the coating thickness is 0.05-0.1 mm, and then the mixture is cured for more than 48 hours to obtain the shading breathable layer 11. Preferably, the mass ratio of the organic silicon rubber to the curing agent is 1: 0.1-1: 1; the mass fraction of the carbon black is 1-5%; the fluororesin powder is one of superfine polytetrafluoroethylene powder and polyvinylidene fluoride powder, and the mass fraction of the fluororesin powder is 1-5%; the inorganic filler is one of white carbon black, nano calcium carbonate powder or quartz powder, and the mass fraction is 0.5-3%.
The phosphor layer 12 includes a polymer matrix and a composite phosphor embedded and dispersed in the polymer matrix. Preferably, the polymer matrix is a composite silicone rubber, the precursor of the composite silicone rubber comprises hydroxyl-terminated polydimethylsiloxane (molecular weight 500-20000) and tetraethoxysilane, and the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the tetraethoxysilane is 0.5:1-4:1, and the ratio can enable the obtained fluorescent layer 12 to have better mechanical properties. Because siloxane molecular chains are relatively flexible, the glass transition temperature of the siloxane molecular chains is far lower than the room temperature, the silicon rubber has larger free volume and good oxygen molecule penetrability under the room temperature condition, and in addition, the silicon rubber and the oxygen molecule also have good affinity, so the silicon rubber has more excellent air permeability and good oxygen permeability compared with other high polymer materials, and the oxygen sensing film has quicker response time and stable oxygen measurement performance. In addition, the silicone rubber has good film forming properties, so that the fluorescent layer 12 can be prepared using a commonly used film forming process.
The composite fluorescent powder is obtained by loading a fluorescent indicator in the light-transmitting nano-particles and the oxygen-permeable light-transmitting polymer. Firstly, placing a certain amount of fluorescent indicator in an organic solvent, and ultrasonically dispersing for 20 min; then, adding a certain proportion of oxygen-permeable light-transmitting polymer and light-transmitting nano particles into an organic solvent dispersed with a fluorescent indicator, mixing and stirring uniformly, and then ultrasonically dispersing the mixed solution for 1 h; then, standing until the organic solvent is volatilized, and separating out the composite fluorescent particles; and finally, grinding the composite fluorescent particles to obtain the composite fluorescent powder. Optionally, the fluorescence indicator is one of PtOEP, PtOEPK or PtTFPP platinum porphyrin complexes, and the organic solvent used for dispersing the fluorescence indicator is toluene, xylene, ethylbenzene, dichloromethane, chloroform, tetrahydrofuran or N, N-dimethylformamide. Preferably, the light-transmitting nanoparticles are hydrophobic gas-phase nano-silica, the particle size is 7-40nm, the specific surface area is 100-2The particle diameter of the gas phase nano silicon dioxide is smaller, the specific surface area is large, and the fluorescence efficiency of the sensing film can be improvedMeanwhile, the gas-phase nano silicon dioxide is not easy to aggregate in the polymer and is dispersed more uniformly, and colorless transparent, semitransparent or white nano particles such as silicon micro powder, nano silicon micro powder or nano boron nitride can be selected during actual realization; the oxygen-permeable light-transmitting polymer is particles or powder of at least one of polystyrene and ethyl cellulose, the oxygen permeability of the polystyrene and the ethyl cellulose is high, and the oxygen-permeable light-transmitting polymer is matched with the light-transmitting nano particles for use, so that the fluorescent indicator is favorably dispersed uniformly, and the stability of the composite fluorescent powder is improved; the mass ratio of the oxygen-permeable light-transmitting polymer to the light-transmitting nanoparticles is 1: 0.5-1: 3, the mass of the fluorescent indicator is 1% -5% of the total mass of the oxygen-permeable light-transmitting polymer and the light-transmitting nanoparticles, the fluorescent indicator is uniformly dispersed and is not easy to generate self-quenching phenomenon, the fluorescent efficiency is ensured, the quenching ratio of the oxygen sensing film is 2-3, the quenching ratio can be adjusted by adjusting the ratio of the oxygen-permeable light-transmitting polymer to the light-transmitting nanoparticles, a proper measurement range is obtained, and meanwhile, the fluorescent layer 12 with high fluorescent efficiency and stable indicator is obtained.
After the preparation of the composite fluorescent powder and the precursor of the polymer matrix is finished, weighing a certain amount of the composite fluorescent powder, adding the composite fluorescent powder into an organic solvent, and performing ultrasonic dispersion for 1 hour to obtain a mixed solution; mixing the mixed solution with a precursor of a polymer matrix, and refluxing for 6 hours at 90 ℃ to obtain a reaction solution; and (3) uniformly coating a proper amount of reaction solution on the prepared shading breathable layer 11 for curing preparation. Optionally, the organic solvent used for dispersing the composite phosphor is toluene, xylene, ethylbenzene, dichloromethane, chloroform, tetrahydrofuran or N, N-dimethylformamide. Wherein, the organic solvent used for dispersing the fluorescent indicator and the organic solvent used for dispersing the composite fluorescent powder can be the same or different.
The light-transmitting protective layer 13 serves to prevent leakage of the fluorescent indicator in the fluorescent layer 12 while not interfering with transmission of the fluorescent signal. Preferably, the light-transmitting protective layer 13 is a transparent polymer sheet made of organic glass, polyvinyl chloride or polyester. Before use, the transparent polymer sheet is soaked in 0.1mol/L sodium hydroxide solution for 12 hours, washed by ethanol or distilled water, soaked in 1% silane coupling agent KH550 solution for 2 hours, taken out, washed by distilled water and dried for later use. In practice, after the reaction solution for forming the fluorescent layer 12 is coated on the light-shielding gas-permeable layer 11, a transparent polymer sheet is coated on the coating of the reaction solution to form the light-transmitting protective layer 13, and then vacuum-cured at 60 ℃ for 24 hours to form the light-transmitting protective layer 13 fixed on the fluorescent layer 12. By using the light-transmitting protective layer 13 with a complete structure, the oxygen sensing membrane can be breathable, waterproof and anti-pollution, and the service life of the oxygen sensing membrane is greatly prolonged while the fluorescent indicator is protected.
In practical implementation, the thickness of the fluorescent layer 12 is preferably 20-100 μm to ensure oxygen permeation and light transmission, the light-shielding and air-permeable layer 11 is preferably 50-100 μm to ensure air permeability and as thin as possible, and the thickness of the light-permeable protective layer 13 is not particularly required, and the whole thickness of the oxygen sensing film is only required to be less than 0.5mm, so that the oxygen sensing film can be cut into any shape of film to be applied to manufacturing a small oxygen measuring device.
The oxygen sensing membrane comprises a light-transmitting protective layer, a fluorescent layer and a light-shading breathable layer, wherein the fluorescent layer is arranged on one side of the light-shading breathable layer, the light-transmitting protective layer covers the fluorescent layer, the fluorescent layer comprises a polymer matrix and composite fluorescent powder embedded and dispersed in the polymer matrix, and the composite fluorescent powder is obtained by loading a fluorescent indicator in light-transmitting nano particles and an oxygen-permeable light-transmitting polymer. In the oxygen sensing membrane of this application, the great specific surface area of printing opacity nano-particle can improve the fluorescence efficiency of oxygen sensing membrane, it makes fluorescence indicator dispersion even to add oxygen permeability printing opacity polymer, the stability of indicator is good, the printing opacity protective layer can prevent that fluorescence indicator from revealing and do not disturb the fluorescence signal transmission in addition, the ventilative layer of shading guarantees the interference of the other light signals of separation and pollutant when oxygen transmission, preparation technology can be simplified to complete three layer construction, be favorable to improving the measurement uniformity of oxygen sensing membrane.
Second embodiment
Fig. 2 is a schematic flow chart showing a method for manufacturing an oxygen sensor film according to a second embodiment. As shown in fig. 2, the method for manufacturing an oxygen sensing film of the present embodiment includes the following steps:
Wherein, the ventilative layer of shading is used for guaranteeing oxygen to the fluorescent layer transmission, can obstruct the interference of other light signals and pollutant simultaneously. The shading breathable layer comprises shading materials, fluororesin powder, inorganic filler and organic silicon rubber, the shading materials are preferably carbon black, the dyeing shading effect is achieved, the fluororesin powder is acid-base resistant, corrosion resistant and good in temperature stability, the shading breathable layer can be loosened and porous, the mechanical strength is increased, and the inorganic filler can increase the toughness and rigidity of the shading breathable layer. The shading material, fluororesin powder, inorganic filler, organic silicon rubber and curing agent of the organic silicon rubber are mixed and stirred uniformly to obtain a mixture, the mixture is coated on a substrate by spin coating or screen printing, the coating thickness is 0.05-0.1 mm, and then the mixture is cured for more than 48 hours to obtain the shading breathable layer. Preferably, the mass ratio of the organic silicon rubber to the curing agent is 1: 0.1-1: 1; the mass fraction of the carbon black is 1-5%; the fluororesin powder is one of superfine polytetrafluoroethylene powder and polyvinylidene fluoride powder, and the mass fraction of the fluororesin powder is 1-5%; the inorganic filler is one of white carbon black, nano calcium carbonate powder or quartz powder, and the mass fraction is 0.5-3%.
And 220, forming a fluorescent layer on the shading breathable layer, wherein the fluorescent layer comprises a polymer matrix and composite fluorescent powder embedded and dispersed in the polymer matrix, and the composite fluorescent powder is obtained by loading a fluorescent indicator in the transparent nano-particles and the oxygen-permeable transparent polymer.
Preferably, the polymer matrix is a composite organic silicon rubber, the precursor of the composite organic silicon rubber comprises hydroxyl-terminated polydimethylsiloxane (molecular weight 500-20000) and tetraethoxysilane, the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the tetraethoxysilane is 0.5:1-4:1, and the ratio can enable the obtained fluorescent layer to have better mechanical properties. Because siloxane molecular chains are relatively flexible, the glass transition temperature of the siloxane molecular chains is far lower than the room temperature, the silicon rubber has larger free volume and good oxygen molecule penetrability under the room temperature condition, and in addition, the silicon rubber and the oxygen molecule also have good affinity, so the silicon rubber has more excellent air permeability and good oxygen permeability compared with other high polymer materials, and the oxygen sensing film has quicker response time and stable oxygen measurement performance. In addition, the silicon rubber has good film forming property, so that the fluorescent layer can be prepared by using a common film forming process.
When the composite fluorescent powder is prepared, a certain amount of fluorescent indicator is placed in an organic solvent, and ultrasonic dispersion is carried out for 20 min; then, adding a certain proportion of oxygen-permeable light-transmitting polymer and light-transmitting nano particles into an organic solvent dispersed with a fluorescent indicator, mixing and stirring uniformly, and then ultrasonically dispersing the mixed solution for 1 h; then, standing until the organic solvent is volatilized, and separating out the composite fluorescent particles; and finally, grinding the composite fluorescent particles to obtain the composite fluorescent powder. Optionally, the fluorescence indicator is one of PtOEP, PtOEPK or PtTFPP platinum porphyrin complexes, and the organic solvent used for dispersing the fluorescence indicator is toluene, xylene, ethylbenzene, dichloromethane, chloroform, tetrahydrofuran or N, N-dimethylformamide. Preferably, the light-transmitting nanoparticles are hydrophobic gas-phase nano-silica, the particle size is 7-40nm, the specific surface area is 100-2The gas-phase nano-silica has smaller particle size and large specific surface area, can improve the fluorescence efficiency of the sensing film, is not easy to gather in a polymer, is more uniform to disperse, and can also be colorless, transparent, semitransparent or white nano-particles such as silicon micro-powder, nano-silicon micro-powder or nano-boron nitride and the like during actual realization; the oxygen-permeable light-transmitting polymer is particles or powder of at least one of polystyrene and ethyl cellulose, the oxygen permeability of the polystyrene and the ethyl cellulose is high, and the oxygen-permeable light-transmitting polymer is matched with the light-transmitting nano particles for use, so that the fluorescent indicator is favorably dispersed uniformly, and the stability of the composite fluorescent powder is improved; the mass ratio of the oxygen-permeable light-transmitting polymer to the light-transmitting nanoparticles is 1: 0.5-1: 3, the mass of the fluorescent indicator is 1% -5% of the total mass of the oxygen-permeable light-transmitting polymer and the light-transmitting nanoparticles, the fluorescent indicator is uniformly dispersed and is not easy to generate self-quenching phenomenon, the fluorescent efficiency is ensured, the quenching ratio of the oxygen sensing film is 2-3, the quenching ratio can be adjusted by adjusting the ratio of the oxygen-permeable light-transmitting polymer to the light-transmitting nanoparticles, a proper measurement range is obtained, and meanwhile, a fluorescent layer with high fluorescent efficiency and stable indicator is obtained.
After the preparation of the composite fluorescent powder and the precursor of the polymer matrix is finished, weighing a certain amount of the composite fluorescent powder, adding the composite fluorescent powder into an organic solvent, and performing ultrasonic dispersion for 1 hour to obtain a mixed solution; mixing the mixed solution with a precursor of a polymer matrix, and refluxing for 6 hours at 90 ℃ to obtain a reaction solution; and (3) uniformly coating a proper amount of reaction solution on the prepared shading breathable layer for curing preparation. Optionally, the organic solvent used for dispersing the composite phosphor is toluene, xylene, ethylbenzene, dichloromethane, chloroform, tetrahydrofuran or N, N-dimethylformamide. Wherein, the organic solvent used for dispersing the fluorescent indicator and the organic solvent used for dispersing the composite fluorescent powder can be the same or different.
Wherein the light-transmitting protective layer is used for preventing the fluorescent indicator from leaking and simultaneously not interfering the transmission of the fluorescent signal. Preferably, the light-transmitting protective layer is a transparent polymer sheet made of organic glass, polyvinyl chloride or polyester. Before use, the transparent polymer sheet is soaked in 0.1mol/L sodium hydroxide solution for 12 hours, washed by ethanol or distilled water, soaked in 1% silane coupling agent KH550 solution for 2 hours, taken out, washed by distilled water and dried for later use. In practical implementation, after the reaction solution for forming the fluorescent layer is coated on the shading breathable layer, the transparent polymer sheet is covered on the coating of the reaction solution to be used as a light-transmitting protective layer, and then vacuum curing is carried out at 60 ℃ for 24 hours to form the light-transmitting protective layer fixed on the fluorescent layer. By using the light-transmitting protective layer with the complete structure, the oxygen sensing film can be breathable, waterproof and anti-pollution, and the service life of the oxygen sensing film is greatly prolonged while the fluorescent indicator is protected.
In practical implementation, the thickness of the fluorescent layer is preferably 20-100 μm to ensure oxygen permeation and light transmission, the light-shielding breathable layer ensures ventilation and is as thin as possible, the preferred thickness is 50-100 μm, the thickness of the light-transmitting protective layer has no special requirement, and the whole thickness of the oxygen sensing film is only required to be smaller than 0.5mm, so that the oxygen sensing film can be cut into any shape of film to be applied to manufacturing of a small oxygen measuring device.
The following describes different processes that can be achieved by the manufacturing method of the present embodiment.
The process 1 comprises the following steps:
preparing a shading breathable layer: mixing and stirring the carbon black, the superfine polytetrafluoroethylene powder, the precipitated white carbon black, the transparent organic silicon rubber and the curing agent of the transparent organic silicon rubber uniformly, coating the mixture on a glass plate by adopting spin coating or screen printing, wherein the thickness of a coating film is 0.05mm, and curing the black silicon rubber coating for more than 48 hours at room temperature to form a film. The mass ratio of the transparent organic silicon rubber to the curing agent is 1:0.1, and the mass fraction of the carbon black is 1%; the mass fraction of the superfine polytetrafluoroethylene powder is 1 percent; the mass fraction of the precipitated white carbon black is 1 percent.
Preparing the composite fluorescent powder: placing a certain amount of fluorescence indicator PtOEP in chloroform, and ultrasonically dispersing for 20 min; adding polystyrene and nano silicon dioxide filler in a certain proportion into trichloromethane, mixing and stirring uniformly, and then ultrasonically dispersing the mixed solution for 1 h; and standing until the organic solvent is volatilized, and grinding the composite fluorescent particles to obtain the composite fluorescent powder. The mass ratio of the polystyrene to the nano-silica filler is 1:0.5, the nano-silica is in a hydrophobic gas phase type, and the specific surface area is 260m2(ii)/g; the addition amount of the fluorescent indicator is 1 percent of the total mass of the polystyrene and the nano silica filler.
Precursor of polymer matrix: the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the tetraethoxysilane is 0.5: 1.
Preparation of a fluorescent layer: weighing a certain amount of composite fluorescent powder, adding the composite fluorescent powder into trichloromethane, and ultrasonically dispersing for 1h to obtain a mixed solution; mixing the mixed solution with a precursor of a polymer matrix, and refluxing for 6 hours at 90 ℃ to obtain a reaction solution; and (3) uniformly coating a proper amount of reaction solution on the prepared shading breathable layer, covering the fluorescent layer with a transparent polymer sheet, and carrying out vacuum curing at 60 ℃ for 24 hours. The fluorescent indicator accounts for 1% of the total mass of the polymer matrix, and the adding amount of the fluorescent powder is calculated according to the mass percentage.
The light-transmitting protective layer is an organic glass sheet, and is soaked in 0.1mol/L sodium hydroxide solution for 12 hours before use, washed by ethanol or distilled water, soaked in 1% silane coupling agent KH550 solution for 2 hours, taken out, washed by distilled water and dried for later use.
And (2) a process:
preparing a shading breathable layer: mixing and stirring carbon black, superfine polyvinylidene fluoride powder, nano calcium carbonate powder, transparent organic silicon rubber and a curing agent of the transparent organic silicon rubber uniformly, coating the mixture on a glass plate by adopting spin coating or screen printing, wherein the thickness of a coating film is 0.05mm, and forming a film after the black silicon rubber coating is cured for more than 48 hours at room temperature; the mass ratio of the transparent organic silicon rubber to the curing agent is 1:0.1, and the mass fraction of the carbon black is 1%; the mass fraction of the superfine polyvinylidene fluoride powder is 1 percent; the mass fraction of the nano calcium carbonate powder is 1 percent.
Preparing the composite fluorescent powder: placing a certain amount of fluorescence indicator PtOEPK in xylene, and ultrasonically dispersing for 20 min; adding polystyrene and nano silicon dioxide filler in a certain proportion into dimethylbenzene, mixing and stirring uniformly, and then ultrasonically dispersing the mixed solution for 1 h; and standing until the organic solvent is volatilized, and grinding the composite fluorescent particles to obtain the composite fluorescent powder. The mass ratio of the polystyrene to the nano-silica filler is 1:1, the nano-silica is in a hydrophobic gas phase type, and the specific surface area is 260m2(ii)/g; the addition amount of the fluorescent indicator is 1 percent of the total mass of the polystyrene and the nano silica filler.
Precursor of polymer matrix: the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the tetraethoxysilane is 1: 1.
Preparation of a fluorescent layer: weighing a certain amount of composite fluorescent powder, adding the composite fluorescent powder into dimethylbenzene, and ultrasonically dispersing for 1h to obtain a mixed solution; and mixing the mixed solution with a precursor of a polymer matrix, and refluxing for 6 hours at 90 ℃ to obtain a reaction solution. And (3) uniformly coating a proper amount of reaction solution on the prepared shading breathable layer, covering the fluorescent layer with a transparent polymer sheet, and carrying out vacuum curing at 60 ℃ for 24 hours. The fluorescent indicator accounts for 1% of the total mass of the polymer matrix, and the adding amount of the fluorescent powder is calculated according to the weight percentage.
The light-transmitting protective layer is a polyester sheet, and is soaked in 0.1mol/L sodium hydroxide solution for 12 hours before use, washed by ethanol or distilled water, soaked in 1% silane coupling agent KH550 solution for 2 hours, taken out, washed by distilled water and dried for later use.
And (3) a process:
preparing a shading breathable layer: mixing and stirring carbon black, superfine polyvinylidene fluoride powder, nano calcium carbonate powder, transparent organic silicon rubber and a curing agent of the transparent organic silicon rubber uniformly, coating the mixture on a glass plate by adopting spin coating or screen printing, wherein the thickness of a coating film is 0.05mm, and forming a film after the black silicon rubber coating is cured for more than 48 hours at room temperature; the mass ratio of the transparent organic silicon rubber to the curing agent is 1:0.1, and the mass fraction of the carbon black is 1%; the mass fraction of the superfine polyvinylidene fluoride powder is 1 percent; the mass fraction of the nano calcium carbonate powder is 1 percent.
Preparing the composite fluorescent powder: placing a certain amount of a fluorescence indicator PtTFPP in xylene, and ultrasonically dispersing for 20 min; adding polystyrene and nano silicon dioxide filler in a certain proportion into the solution, placing the solution into dimethylbenzene, mixing and stirring the mixture evenly, and then carrying out ultrasonic dispersion on the mixed solution for 1 hour; and standing until the organic solvent is volatilized, and grinding the composite fluorescent particles to obtain the composite fluorescent powder. The mass ratio of the polystyrene to the nano-silica filler is 1:2, the nano-silica is in a hydrophobic gas phase type, and the specific surface area is 260m2(ii)/g; the addition amount of the fluorescent indicator is 1 percent of the total mass of the polystyrene and the nano silica filler.
Precursor of polymer matrix: the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the tetraethoxysilane is 2: 1.
Preparation of a fluorescent layer: weighing a certain amount of composite fluorescent powder, adding the composite fluorescent powder into dimethylbenzene, and ultrasonically dispersing for 1h to obtain a mixed solution; and mixing the mixed solution with a precursor of a polymer matrix, and refluxing for 6 hours at 90 ℃ to obtain a reaction solution. And (3) uniformly coating a proper amount of reaction solution on the prepared shading breathable layer, covering the fluorescent layer with a transparent polymer sheet, and carrying out vacuum curing at 60 ℃ for 24 hours. The fluorescent indicator accounts for 1% of the total mass of the polymer matrix, and the adding amount of the fluorescent powder is calculated according to the weight percentage.
The light-transmitting protective layer is a polyester sheet, and is soaked in 0.1mol/L sodium hydroxide solution for 12 hours before use, washed by ethanol or distilled water, soaked in 1% silane coupling agent KH550 solution for 2 hours, taken out, washed by distilled water and dried for later use.
And (4) a process:
preparing a shading breathable layer: mixing and stirring carbon black, superfine polyvinylidene fluoride powder, nano calcium carbonate powder, transparent organic silicon rubber and a curing agent of the transparent organic silicon rubber uniformly, coating the mixture on a glass plate by adopting spin coating or screen printing, wherein the thickness of a coating film is 0.05mm, and forming a film after the black silicon rubber coating is cured for more than 48 hours at room temperature; the mass ratio of the transparent organic silicon rubber to the curing agent is 1:0.1, and the mass fraction of the carbon black is 1%; the mass fraction of the superfine polyvinylidene fluoride powder is 1 percent; the mass fraction of the nano calcium carbonate powder is 1 percent.
Preparing the composite fluorescent powder: placing a certain amount of fluorescence indicator PtOEP in xylene, and ultrasonically dispersing for 20 min; adding polystyrene and nano silicon dioxide filler in a certain proportion into the solution, placing the solution into dimethylbenzene, mixing and stirring the mixture evenly, and then carrying out ultrasonic dispersion on the mixed solution for 1 hour; and standing until the organic solvent is volatilized, and grinding the composite fluorescent particles to obtain the composite fluorescent powder. The mass ratio of the polystyrene to the nano-silica filler is 1:2, the nano-silica is in a hydrophobic gas phase type, and the specific surface area is 100m2(ii)/g; the addition amount of the fluorescent indicator is 1 percent of the total mass of the polystyrene and the nano silica filler.
Precursor of polymer matrix: the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the tetraethoxysilane is 2: 1.
Preparation of a fluorescent layer: weighing a certain amount of composite fluorescent powder, adding the composite fluorescent powder into dimethylbenzene, and ultrasonically dispersing for 1h to obtain a mixed solution; and mixing the mixed solution with a precursor of a polymer matrix, and refluxing for 6 hours at 90 ℃ to obtain a reaction solution. And (3) uniformly coating a proper amount of reaction solution on the prepared shading breathable layer, covering the fluorescent layer with a transparent polymer sheet, and carrying out vacuum curing at 60 ℃ for 24 hours. The fluorescent indicator accounts for 1% of the total mass of the polymer matrix, and the adding amount of the fluorescent powder is calculated according to the weight percentage.
The light-transmitting protective layer is a polyester sheet, and is soaked in 0.1mol/L sodium hydroxide solution for 12 hours before use, washed by ethanol or distilled water, soaked in 1% silane coupling agent KH550 solution for 2 hours, taken out, washed by distilled water and dried for later use.
And (5) a process:
preparing a shading breathable layer: mixing and stirring carbon black, superfine polytetrafluoroethylene powder, quartz powder, transparent organic silicon rubber and a curing agent of the transparent organic silicon rubber uniformly, coating the mixture on a glass plate by adopting spin coating or screen printing, wherein the thickness of a coating film is 0.05mm, and curing the black silicon rubber coating for more than 48 hours at room temperature to form a film; the mass ratio of the transparent organic silicon rubber to the curing agent is 1:0.1, and the mass fraction of the carbon black is 1%; the mass fraction of the superfine polytetrafluoroethylene powder is 1 percent; the mass fraction of the quartz powder is 1%.
Preparing the composite fluorescent powder: placing a certain amount of fluorescence indicator PtOEP in tetrahydrofuran chloroform, and ultrasonically dispersing for 20 min; adding ethyl cellulose and nano silicon dioxide filler in a certain proportion into the solution, placing the solution into tetrahydrofuran trichloromethane, mixing and stirring the mixture evenly, and then ultrasonically dispersing the mixed solution for 1 hour; and standing until the organic solvent is volatilized, and grinding the composite fluorescent particles to obtain the composite fluorescent powder. The mass ratio of the ethyl cellulose to the nano-silica filler is 1:2, the nano-silica is in a hydrophobic gas phase type, and the specific surface area is 260m2(ii)/g; the addition amount of the fluorescent indicator is 1 percent of the total mass of the ethyl cellulose and the nano silica filler.
Precursor of polymer matrix: the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the tetraethoxysilane is 2: 1.
Preparation of a fluorescent layer: weighing a certain amount of composite fluorescent powder, adding the composite fluorescent powder into tetrahydrofuran trichloromethane, and ultrasonically dispersing for 1h to obtain a mixed solution; and mixing the mixed solution with a precursor of a polymer matrix, and refluxing for 6 hours at 90 ℃ to obtain a reaction solution. And (3) uniformly coating a proper amount of reaction solution on the prepared shading breathable layer, covering the fluorescent layer with a transparent polymer sheet, and carrying out vacuum curing at 60 ℃ for 24 hours. The fluorescent indicator accounts for 1% of the total mass of the polymer matrix, and the adding amount of the fluorescent powder is calculated according to the weight percentage.
The light-transmitting protective layer is a polyvinyl chloride sheet, and is soaked in 0.1mol/L sodium hydroxide solution for 12 hours before use, washed by ethanol or distilled water, soaked in 1% silane coupling agent KH550 solution for 2 hours, taken out, washed by distilled water and dried for later use.
And (6) a process:
preparing a shading breathable layer: mixing and stirring carbon black, superfine polytetrafluoroethylene powder, nano calcium carbonate powder, transparent organic silicon rubber and a curing agent of the transparent organic silicon rubber uniformly, coating the mixture on a glass plate by adopting spin coating or screen printing, wherein the thickness of a coating film is 0.05mm, and curing the black silicon rubber coating for more than 48 hours at room temperature to form a film; the mass ratio of the transparent organic silicon rubber to the curing agent is 1:0.1, and the mass fraction of the carbon black is 1%; the mass fraction of the superfine polytetrafluoroethylene powder is 1 percent; the mass fraction of the nano calcium carbonate powder is 1 percent.
Preparing the composite fluorescent powder: placing a certain amount of fluorescence indicator PtOEP in ethylbenzene, and ultrasonically dispersing for 20 min; adding polystyrene and nano silicon dioxide filler in a certain proportion into the solution, placing the solution into ethylbenzene, mixing and stirring the mixture evenly, and then carrying out ultrasonic dispersion on the mixed solution for 1 hour; and standing until the organic solvent is volatilized, and grinding the composite fluorescent particles to obtain the composite fluorescent powder. The mass ratio of the polystyrene to the nano-silica filler is 1:3, the nano-silica is in a hydrophobic gas phase type, and the specific surface area is 260m2(ii)/g; the addition amount of the fluorescent indicator is 1 percent of the total mass of the polystyrene and the nano silica filler.
Precursor of polymer matrix: the mass ratio of the hydroxyl-terminated polydimethylsiloxane to the tetraethoxysilane is 3: 1.
The preparation method of the fluorescent layer comprises the following steps: weighing a certain amount of composite fluorescent powder, adding the composite fluorescent powder into ethylbenzene, and performing ultrasonic dispersion for 1 hour to obtain a mixed solution; and mixing the mixed solution with a precursor of a polymer matrix, and refluxing for 6 hours at 90 ℃ to obtain a reaction solution. And (3) uniformly coating a proper amount of reaction solution on the prepared shading breathable layer, covering the fluorescent layer with a transparent polymer sheet, and carrying out vacuum curing at 60 ℃ for 24 hours. The fluorescent indicator accounts for 1% of the total mass of the polymer matrix, and the adding amount of the fluorescent powder is calculated according to the weight percentage.
The light-transmitting protective layer is an organic glass sheet, and is soaked in 0.1mol/L sodium hydroxide solution for 12 hours before use, washed by ethanol or distilled water, soaked in 1% silane coupling agent KH550 solution for 2 hours, taken out, washed by distilled water and dried for later use.
The oxygen sensor film prepared by the above process was placed on an oxygen sensor, and the fluorescence intensity, appearance of the phosphor layer and measurement results of the fluorescence intensity were measured in air and vacuum, respectively, as shown in table 1. The larger specific surface area of the nano silicon dioxide particles can load more fluorescent indicators, and after the nano silicon dioxide particles are combined with the oxygen permeable polymer, the nano particles loaded with the fluorescent indicators are uniformly dispersed in the silicon rubber matrix, so that the fluorescence efficiency of the oxygen sensing film can be improved, and the fluorescence intensity is higher.
TABLE 1 measurement results of appearance and fluorescence intensity of fluorescent layer
| Fluorescence intensity in air/mV | Fluorescence intensity/mV in vacuum | Ratio of fluorescence intensities | Appearance of fluorescent layer | |
| Process 1 | 25 | 75 | 3 | Hard and translucent texture |
| Process 2 | 28 | 80 | 2.85 | Flexible and translucent texture |
| Process 3 | 30 | 88 | 2.93 | Flexible and transparent texture |
| Process 4 | 24 | 78 | 3.25 | Flexible and transparent texture |
| Process 5 | 35 | 95 | 2.71 | Flexible and transparent texture |
| Process 6 | 35 | 89 | 2.54 | The adhesive is not completely cured and is transparent |
The method for manufacturing the oxygen sensing film comprises the steps of providing a shading breathable layer; forming a fluorescent layer on the shading breathable layer, wherein the fluorescent layer comprises a polymer matrix and composite fluorescent powder embedded and dispersed in the polymer matrix, and the composite fluorescent powder is obtained by loading a fluorescent indicator in light-transmitting nano-particles and an oxygen-permeable light-transmitting polymer; forming a light-transmitting protective layer on the fluorescent layer; an oxygen sensor film was obtained. By the method, the prepared oxygen sensing film has a complete three-layer structure, the preparation process is simple, the measurement consistency of the oxygen sensing film is favorably improved, complex equipment is not needed, the raw materials are simple and easy to obtain, and the manufacturing cost is low.
The above embodiments are merely illustrative of the principles and utilities of the present application and are not intended to limit the application. Any person skilled in the art can modify or change the above-described embodiments without departing from the spirit and scope of the present application. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical concepts disclosed in the present application shall be covered by the claims of the present application.
Claims (10)
1. The oxygen sensing membrane is characterized by comprising a light-transmitting protective layer, a fluorescent layer and a light-shading breathable layer, wherein the fluorescent layer is arranged on one side of the light-shading breathable layer, the light-transmitting protective layer covers the fluorescent layer, the fluorescent layer comprises a polymer matrix and composite fluorescent powder embedded and dispersed in the polymer matrix, and the composite fluorescent powder is obtained by loading a fluorescent indicator in light-transmitting nano particles and an oxygen-permeable light-transmitting polymer.
2. The oxygen sensing film of claim 1, wherein the mass ratio of the oxygen permeable light-transmitting polymer to the light-transmitting nanoparticles is 1: 0.5-1: 3, and the mass of the fluorescent indicator is 1-5% of the total mass of the oxygen permeable light-transmitting polymer and the light-transmitting nanoparticles.
3. The oxygen sensing film as claimed in claim 1, wherein the light-transmitting nanoparticles are hydrophobic fumed silica with a particle size of 7-40nm and a specific surface area of 100-260m2(ii)/g; and/or the oxygen-permeable light-transmitting polymer is particles or powder of at least one of polystyrene and ethyl cellulose.
4. The oxygen sensing film of claim 1, wherein the light-transmissive protective layer is a transparent polymer sheet of plexiglass, polyvinyl chloride or polyester; and/or the polymer matrix is composite organic silicon rubber.
5. A method of making an oxygen sensing membrane, comprising:
a. providing a light-shielding breathable layer;
b. forming a fluorescent layer on the shading breathable layer, wherein the fluorescent layer comprises a polymer matrix and composite fluorescent powder embedded and dispersed in the polymer matrix, and the composite fluorescent powder is obtained by loading a fluorescent indicator in light-transmitting nano particles and an oxygen-permeable light-transmitting polymer;
c. forming a light-transmitting protective layer on the fluorescent layer;
d. an oxygen sensor film was obtained.
6. The method of manufacturing an oxygen sensing membrane according to claim 5, wherein the step a comprises:
mixing and stirring a shading material, fluororesin powder, an inorganic filler, a curing agent and organic silicon rubber;
and coating the mixture on a substrate for curing to obtain the shading and ventilating layer.
7. The method of manufacturing an oxygen sensing membrane according to claim 5, wherein step b comprises:
b1. providing the composite fluorescent powder and a precursor of the polymer matrix, wherein the precursor of the polymer matrix is a precursor of composite organic silicon rubber;
b2. dispersing the composite fluorescent powder in a first organic solvent to obtain a mixed solution;
b3. mixing the mixed solution with a precursor of the polymer matrix to obtain a reaction solution;
b4. and coating the reaction solution on the shading and ventilating layer for curing.
8. The method of making an oxygen sensing membrane of claim 7, wherein step b1 comprises:
dispersing a fluorescent indicator in a second organic solvent;
adding the oxygen-permeable light-transmitting polymer and the light-transmitting nano particles into the second organic solvent dispersed with the fluorescent indicator, and mixing;
removing the second organic solvent to isolate composite fluorescent particles;
and grinding the composite fluorescent particles to obtain the composite fluorescent powder.
9. The method for manufacturing the oxygen sensing film according to claim 5 or 8, wherein the mass ratio of the oxygen-permeable light-transmitting polymer to the light-transmitting nanoparticles is 1: 0.5-1: 3, and the addition amount of the fluorescent indicator is 1-5% of the total mass of the oxygen-permeable light-transmitting polymer and the light-transmitting nanoparticles; and/or the oxygen-permeable light-transmitting polymer is particles or powder of at least one of polystyrene and ethyl cellulose.
10. The method of manufacturing an oxygen sensing membrane according to claim 7, wherein step c comprises:
after the reaction solution is coated on the shading breathable layer, covering a transparent polymer sheet on the coating of the reaction solution to serve as the light-transmitting protective layer;
and curing the coating of the reaction solution to form the light-transmitting protective layer fixed on the fluorescent layer.
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| CN113607708A (en) * | 2021-08-06 | 2021-11-05 | 常州罗盘星检测科技有限公司 | Method for preparing oxygen sensitive membrane of dissolved oxygen sensor by loading fluorescent indicator and application |
| CN114264637A (en) * | 2021-12-21 | 2022-04-01 | 杭州浸格科技有限公司 | Dissolved oxygen real-time online monitoring sensor device, control method and use method |
| CN115595141A (en) * | 2022-09-30 | 2023-01-13 | 浙江清华柔性电子技术研究院（Cn） | Method for manufacturing oxygen sensor fluorescent film, oxygen sensor fluorescent film and oxygen sensor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113607708A (en) * | 2021-08-06 | 2021-11-05 | 常州罗盘星检测科技有限公司 | Method for preparing oxygen sensitive membrane of dissolved oxygen sensor by loading fluorescent indicator and application |
| CN114264637A (en) * | 2021-12-21 | 2022-04-01 | 杭州浸格科技有限公司 | Dissolved oxygen real-time online monitoring sensor device, control method and use method |
| CN115595141A (en) * | 2022-09-30 | 2023-01-13 | 浙江清华柔性电子技术研究院（Cn） | Method for manufacturing oxygen sensor fluorescent film, oxygen sensor fluorescent film and oxygen sensor |
| CN115805388A (en) * | 2022-12-10 | 2023-03-17 | 郑州机械研究所有限公司 | Flux-cored brazing filler metal with visible flux core and preparation method thereof |
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