CN109659070A - A kind of flexible conductive film and its application with gas sensitization performance - Google Patents
A kind of flexible conductive film and its application with gas sensitization performance Download PDFInfo
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- CN109659070A CN109659070A CN201811608197.1A CN201811608197A CN109659070A CN 109659070 A CN109659070 A CN 109659070A CN 201811608197 A CN201811608197 A CN 201811608197A CN 109659070 A CN109659070 A CN 109659070A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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Abstract
The invention discloses a kind of flexible conductive films and its application with gas sensitization performance for belonging to gas sensing technical field of material.The flexible conductive film is that two-dimension nano materials are stacked into tridimensional network in PET film substrate, and conductive polymer material is attached to the laminated film formed on tridimensional network；Two-dimension nano materials are one of molybdenum trioxide, tungstic acid, cobaltosic oxide, tin oxide, zinc oxide or a variety of, and shape is laminar, rodlike, needle-shaped, linear or hollow tubular；Conductive polymer material is protonation polyaniline, polypyrrole or polythiophene.Flexible conductive film provided by the invention can the gas concentration at room temperature to triethylamine, ethylenediamine, ammonia, ethyl alcohol, acetone, nitrogen dioxide detect, overcome the high temperature monitoring defect of inorganic nano material.
Description
Technical field
The invention belongs to gas sensing technical field of material, in particular to a kind of flexibility with gas sensitization performance
Conductive film and its application.
Background technique
Environmental pollution and food safety are related to public vital interests, thus learning gas sensing material to air quality and
Food quality is monitored necessary.Inorganic nano material is the material for being applied to gas sensing field earliest, but it is needed
High temperature test condition, limit its flammable explosive gas environment, high integrated circuit, in terms of application.
In the industrial production, triethylamine and ammonia are a kind of toxic and harmful gas of petrochemical industry release, and harmful to human is strong
Health.In terms of food, when meat and fishes and shrimps seafood product corruption, can discharge the nitrogenous gas such as triethylamine, ethylenediamine, ammonia, high
The food of the nitrogenous gas such as concentration triethylamine, ethylenediamine, ammonia directly endangers the safe diet of consumer.
Summary of the invention
The purpose of the present invention is to provide a kind of flexible conductive film and its application with gas sensitization performance, specific skill
Art scheme is as follows:
A kind of flexible conductive film with gas sensitization performance is that two-dimension nano materials are stacked into PET film substrate
Tridimensional network, conductive polymer material are attached to the laminated film formed on tridimensional network；
The two-dimension nano materials are one of molybdenum trioxide, tungstic acid, cobaltosic oxide, tin oxide, zinc oxide
Or it is a variety of, shape is laminar, rodlike, needle-shaped, linear or hollow tubular.
The conductive polymer material is protonation polyaniline, polypyrrole or polythiophene.
The two-dimension nano materials are preferably laminar molybdenum trioxide, rodlike tungstic acid, needle-shaped cobaltosic oxide, threadiness
Tin oxide, linear tin oxide zinc oxide composites or hollow tubular tin oxide.
The flake molybdenum trioxide 1~30nm of thickness, 20~100nm of width, length 500nm~5 μm；
2~50nm of the rodlike tungstic acid diameter, length 500nm~3 μm；
Needle-shaped cobaltosic oxide length 200nm~4 μm；
The threadiness tin oxide, linear tin oxide zinc oxide composites 50~100nm of diameter, length are greater than 1 μm；
The hollow tubular tin oxide 1~10nm of wall thickness, length are greater than 1 μm.
The PET film area is less than 1cm2, thickness is less than 0.15mm.
The load capacity of two-dimension nano materials is 0.05~15mg/cm in the PET film substrate2。
The weight ratio of the conductive polymer material and the two-dimension nano materials is 1:10~10:1.
The conductive polymer material is under the action of catalyst ammonium persulfate or ferric trichloride with metal oxide acidity
Active site is that attachment point aggregation growth is that scabbard form or array of protrusions are attached to the two-dimension nano materials surface.
The application of the flexible conductive film with gas sensitization performance is that the flexible conductive film is used at room temperature
In the gas concentration of detection triethylamine, ethylenediamine, ammonia, ethyl alcohol, acetone, nitrogen dioxide.
The triethylamine, ethylenediamine, ammonia, ethyl alcohol, acetone, nitrogen dioxide gas concentration Monitoring lower-cut≤1ppm.
The electrical response value of the flexible conductive film and detected gas triethylamine, ethylenediamine, ammonia, ethyl alcohol, acetone,
The gas concentration of nitrogen dioxide is linearly related；Linear relevant gas concentration is preferably 0ppm~100ppm；Linear phase
The gas concentration of pass is more preferably 0.5ppm~100ppm.
The invention has the benefit that
(1) flexible conductive film provided by the invention is using PET film as substrate, so that can be suitably used for can for flexible conductive film
Wearing and small electronic equipment；Two-dimension nano materials are coated on PET film surface, intertexture is stacked as tridimensional network, not only
Skeleton is provided for conducting polymer apposition growth, increases the surface area that gas sensitive is exposed to air, is provided more for gas absorption
Multidigit point improves material Gas-sensing measurment；And conducting polymer is improved due to being influenced to detect by higher temperature structure collapses
Sensitive highest Applicable temperature.The addition of conductive polymer material, which makes flexible conductive film at room temperature, has gas sensitization performance.
(2) flexible conductive film provided by the invention can at room temperature to triethylamine, ethylenediamine, ammonia, ethyl alcohol, acetone,
The concentration of the gases such as nitrogen dioxide is detected, and the high temperature monitoring defect of inorganic nano material is overcome；Three are detected at room temperature
Ethamine, ethylenediamine, ammonia, ethyl alcohol, acetone, nitrogen dioxide gas concentration when, electrical response value and detected gas concentration
It is in a linear relationship, it is easy to detect；
(3) flexible conductive film provided by the invention is to triethylamine, ethylenediamine, ammonia, ethyl alcohol, acetone, titanium dioxide nitrogen
Minimal detectable concentration≤1ppm of body can be applied to the inspection of the seafoods product freshness such as field of food detection such as meat, fishes and shrimps
It surveys, can be used for the early warning detection of the toxic and harmful gas of petrochemical industry release, to ensure safe diet and human health.
Detailed description of the invention
Attached drawing 1 is flexible conductive film structural schematic diagram of the present invention；
Attached drawing 2 is 1 flexible conductive film scanning electron microscope (SEM) photograph of embodiment；
Attached drawing 3 is the correlation of embodiment 1 flexible conductive film electrical response value and Triethylamine gas concentration；
Attached drawing 4 is that 2 flexible conductive film of embodiment is tested at room temperature to 100ppm triethylamine, ethylenediamine, ammonia, second
The response of alcohol, acetone；
Attached drawing 5 is 3 flexible conductive film of embodiment at room temperature to the response of various concentration ammonia；
Attached drawing 6 is 4 gained polythiophene flexible conductive film electron microscope of embodiment；
Attached drawing 7 is 4 polythiophene flexible conductive film of embodiment at room temperature to the response of various concentration nitrogen dioxide.
Specific embodiment
The present invention provides a kind of flexible conductive film and its application with gas sensitization performance, with reference to the accompanying drawing and
The present invention is described further for embodiment.
Attached drawing 1 is flexible conductive film structural schematic diagram of the present invention, and curved bars are conducting polymer, and rodlike figure is two
Dimension nano material, cube figure are PET film.
Embodiment 1
It is 0.49cm by surface area is cut into a thickness of the PET film of 0.1mm2Square film, applied atop 3~
4mg flake molybdenum trioxide, molybdenum trioxide preferred size are 5~10nm of molybdenum trioxide thickness, 20~50nm of width, length 3~5
μm, aniline is mixed with molybdenum trioxide with weight ratio 1:10,1:3,10:1, in an acidic solution under the catalysis of ammonium persulfate, benzene
The acidic active sites polymerization that amine depends on molybdenum trioxide surface generates protonation polyaniline, and flexible conductive film, gained is made
Flexible conductive film electron microscope in Fig. 2 respectively as schemed shown in a, b, c.
Gained flexible conductive film is tested to the triethylamine concentration within the scope of 0ppm~100ppm at room temperature, triethylamine
It is 1.2 that minimum monitoring concentration, which is 0.5ppm its response, and in 1ppm, response is that 2.8 (response is that flexible conductive film exists
The ratio of resistance and the resistance in measurement atmosphere in air), response and three second of the gained flexible conductive film to triethylamine
The linear correlation of the concentration of amine, fit correlation are y=2.65+0.193x (R2=0.997), specific as shown in Figure 3.Pass through prison
Flexible conductive film resistance variations are surveyed to monitor triethylamine concentration in environment and change, to learn whether meat seafood products become
Matter.
Embodiment 2
It is 0.49cm by surface area is cut into a thickness of the PET film of 0.1mm2Square film, in applied atop 0.5
The rodlike tungstic acid of~1.5mg, 10~20nm of tungstic acid preferred size diameter, 1.5~2 μm of length, aniline and tungstic acid
With weight ratio 1:2 mixing, in an acidic solution under the catalysis of ammonium persulfate, aniline depends on tungstic acid surface aggregate into matter
Flexible conductive film is made in sonization polyaniline.
Gained flexible conductive film is tested at room temperature to 100ppm triethylamine, ethylenediamine, ammonia, ethyl alcohol, acetone
Response, test result such as Fig. 4.
Embodiment 3
Selecting the PET film with a thickness of 0.1mm to be cut into surface area is 0.49cm2Square film, in applied atop
0.5~1.5mg, 1~10nm of wall thickness, length are greater than 1 μm of hollow tubular tin oxide, by pyrroles and tin oxide with weight ratio 1:2
Mixing, in an acidic solution under the catalysis of ammonium persulfate, pyrroles polymerize to form polypyrrole in hollow tubular tin oxide surface, system
Obtain flexible conductive film.
Gained flexible conductive film is tested into ammonia concentration data such as Fig. 5 at room temperature, by monitoring flexible conductive film
To monitor, ammonia concentration changes resistance variations in environment in petrochemical production process.
Embodiment 4
It is 0.49cm by surface area is cut into a thickness of the PET film of 0.1mm2Square film, in applied atop 0.5
The rodlike tungstic acid of~1.5mg, 10~20nm of tungstic acid preferred size diameter, 1.5~2 μm of length, thiophene and tungstic acid
With weight ratio 1:2 mixing, thiophene depends on tungstic acid surface-active site and aggregates into polythiophene under the catalysis of ferric trichloride,
Flexible conductive film, electron microscopic picture such as Fig. 6 is made；Gained flexible conductive film is tested into the response to nitrogen dioxide at room temperature
Value, test result such as Fig. 7.
Claims (10)
1. a kind of flexible conductive film with gas sensitization performance, which is characterized in that the flexible conductive film is two wieners
Rice material is stacked into tridimensional network in PET film substrate, and conductive polymer material is attached to shape on tridimensional network
At laminated film；
The two-dimension nano materials are one of molybdenum trioxide, tungstic acid, cobaltosic oxide, tin oxide, zinc oxide or more
Kind, shape is laminar, rodlike, needle-shaped, linear or hollow tubular；
The conductive polymer material is protonation polyaniline, polypyrrole or polythiophene.
2. the flexible conductive film according to claim 1 with gas sensitization performance, which is characterized in that two wiener
Rice material is laminar molybdenum trioxide, rodlike tungstic acid, needle-shaped cobaltosic oxide, linear tin oxide, linear tin oxide oxidation
Zinc complexes or hollow tubular tin oxide.
3. the flexible conductive film according to claim 2 with gas sensitization performance, which is characterized in that the flake
Molybdenum trioxide 1~30nm of thickness, 20~100nm of width, length 500nm~5 μm；
2~50nm of the rodlike tungstic acid diameter, length 500nm~3 μm；
Needle-shaped cobaltosic oxide length 200nm~4 μm；
The threadiness tin oxide, linear tin oxide zinc oxide composites 50~100nm of diameter, length are greater than 1 μm；
The hollow tubular tin oxide 1~10nm of wall thickness, length are greater than 1 μm.
4. the flexible conductive film according to claim 1 with gas sensitization performance, which is characterized in that the PET is thin
Membrane area is less than 1cm2, thickness is less than 0.15mm.
5. the flexible conductive film according to claim 1 with gas sensitization performance, which is characterized in that the PET is thin
The load capacity of two-dimension nano materials is 0.05~15mg/cm in film substrate2。
6. the flexible conductive film according to claim 1 with gas sensitization performance, which is characterized in that described conductive high
The weight ratio of molecular material and the two-dimension nano materials is 1:10~10:1.
7. the flexible conductive film according to claim 1 with gas sensitization performance, which is characterized in that described conductive high
Molecular material is poly- by attachment point of metal oxide acidic active sites under the action of catalyst ammonium persulfate or ferric trichloride
The a length of scabbard form of symphysis or array of protrusions are attached to the two-dimension nano materials surface.
8. the application of the flexible conductive film described in any one of claim 1~7 with gas sensitization performance, which is characterized in that
It is dense that the flexible conductive film is used to detect at room temperature triethylamine, ethylenediamine, ammonia, ethyl alcohol, acetone, the gas of nitrogen dioxide
Degree.
9. application according to claim 8, which is characterized in that the triethylamine, ethylenediamine, ammonia, ethyl alcohol, acetone, two
Gas concentration Monitoring lower-cut≤1ppm of nitrogen oxide.
10. application according to claim 8, which is characterized in that the electrical response value of the flexible conductive film and tested
It is linearly related to survey gas triethylamine, ethylenediamine, ammonia, ethyl alcohol, acetone, the gas concentration of nitrogen dioxide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111254708A (en) * | 2020-03-20 | 2020-06-09 | 西北工业大学 | CNTs/polyaniline-based flexible ammonia gas sensing material and preparation method thereof |
| CN113720884A (en) * | 2020-05-25 | 2021-11-30 | 中国石油化工股份有限公司 | Wearable conductive film sensor and preparation method and application thereof |
| CN114858869A (en) * | 2022-04-28 | 2022-08-05 | 吉林大学 | ZnIn based on sulfur-rich vacancy 2 S 4 Triethylamine gas sensor of nanoflower sensitive material and preparation method thereof |
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| CN114858869A (en) * | 2022-04-28 | 2022-08-05 | 吉林大学 | ZnIn based on sulfur-rich vacancy 2 S 4 Triethylamine gas sensor of nanoflower sensitive material and preparation method thereof |
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Application publication date: 20190419 |