CN105953067A - Hydrogen cylinder with leak detection function - Google Patents
Hydrogen cylinder with leak detection function Download PDFInfo
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- CN105953067A CN105953067A CN201610257951.6A CN201610257951A CN105953067A CN 105953067 A CN105953067 A CN 105953067A CN 201610257951 A CN201610257951 A CN 201610257951A CN 105953067 A CN105953067 A CN 105953067A
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- Prior art keywords
- gas
- air
- discoloration
- face
- glass substrate
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Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C13/00—Details of vessels or of the filling or discharging of vessels
- F17C13/002—Details of vessels or of the filling or discharging of vessels for vessels under pressure
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01M—TESTING STATIC OR DYNAMIC BALANCE OF MACHINES OR STRUCTURES; TESTING OF STRUCTURES OR APPARATUS, NOT OTHERWISE PROVIDED FOR
- G01M3/00—Investigating fluid-tightness of structures
- G01M3/02—Investigating fluid-tightness of structures by using fluid or vacuum
- G01M3/04—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
- G01N21/783—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour for analysing gases
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2201/00—Vessel construction, in particular geometry, arrangement or size
- F17C2201/05—Size
- F17C2201/056—Small (<1 m3)
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2221/00—Handled fluid, in particular type of fluid
- F17C2221/01—Pure fluids
- F17C2221/012—Hydrogen
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2270/00—Applications
- F17C2270/05—Applications for industrial use
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention relates to a hydrogen cylinder with leak detection function. A gaschromic gas sensor is installed on the outside surface of the hydrogen cylinder, and the gaschromic gas sensor incudes a sensing unit, a heating unit, and a data reading unit. The heating unit and the data reading unit are connected with a tungsten oxide gas-sensing film of the sensing unit, and the heating unit is used as a heating source of the tungsten oxide gas-sensing film when the film works. The sensing unit is a double-layer structure with a hollow structure in the middle part. The hydrogen cylinder can realize visual detection of the hydrogen based on the gas-sensing property and gaschromic property of the WO3 nano material, has short response time, high sensitivity, and convenient usage, is easy to operate, and can reach the objective of detecting the hydrogen leakage accurately and timely.
Description
Technical field
The application relates to electric inspection process field, is specifically related to a kind of hydrogen cylinder carrying leak detection function.
Background technology
Hydrogen is the lightest gas, and its density is the least, only the 2/29 of air.Simultaneously
Hydrogen is the main raw material of industry, is also most important industrial gases and special gas, petrochemical industry,
Electronics industry, metallurgical industry, food processing, float glass, Minute Organic Synthesis, Aero-Space etc.
Aspect has a wide range of applications.The storing of hydrogen at present mainly has gaseous state storing, liquid storing, metallic hydrogen
Compound storing etc..
Hydrogen cylinder is the container storing hydrogen, the most green steel cylinder.Owing to hydrogen is that one is inflammable easily
Quick-fried hazardous gas, the detection to its property revealed is its guarantee used safely.
Summary of the invention
For overcoming problem present in correlation technique, the application provides a kind of leak detection function that carries
Hydrogen cylinder.
First aspect according to the embodiment of the present application, it is provided that a kind of hydrogen carrying leak detection function
Bottle, described hydrogen cylinder outer surface is provided with gas-discoloration gas sensor, and described gas-discoloration gas passes
Sensor is based on WO3Gas sensitive and WO3Gas-discoloration material；Described gas-discoloration gas sensor
Including sensing unit, heating unit and data-reading unit；Described heating unit and data-reading unit
It is connected with the tungsten oxide air-sensitive film of sensing unit；Described heating unit is as tungsten oxide air-sensitive film work
Heating source when making；Data-reading unit processes the conductivity variations signal of tungsten oxide air-sensitive film with aobvious
Show the concentration value of object gas；Described sensing unit is the double-decker of hollow structure, forms bilayer knot
A face structure and the B face structure of structure are staggered relatively, distance 500 μm, A face structure and B face structure
The periphery of handing-over uses colloid to seal；Described A face include quartz glass substrate, interdigital electrode layer and
WO3Air-sensitive film layer, WO3Air-sensitive film layer is doping SnO2WO3Thin film, it is possible to achieve right
NO2The detection of gas, described B face includes quartz glass substrate and WO3Gas-discoloration layer, WO3
Gas-discoloration layer is WO3Nano wire film doping ZnTPP-2-NO2, utilize the gas-discoloration principle can
To realize the Visual retrieval to hydrogen；It is additionally provided with 2 for object gas in the structure of described B face
The air-vent penetrated.In A face, described SnO2Granularity less than 30nm, described WO3Air-sensitive
Thin film layer thickness is 700nm；In B face, described WO3Nanowire length about 1 μm, diameter about 60
nm。
Second aspect according to the embodiment of the present application, it is provided that a kind of hydrogen cylinder carrying leak detection function
Preparation method, it is preferable that the making of the sensing unit of described gas-discoloration gas sensor include with
Lower step:
S1, preparation A face structure, including following enforcement step: (1) takes certain size (4cm × 4cm)
Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2)
Spin coating one layer photoetching glue in quartz glass substrate, thickness 1 μm, under interdigital electrode mask covers
Exposure 6s, cleans with deionized water after being then passed through development 50s, uses magnetically controlled sputter method plating one
Cr film thick for layer 300nm, as interdigital electrode layer, then removes photoresist；(3) by quartz glass
Glass substrate is put in magnetic control sputtering device, is evacuated to 5 × 10-4Below Pa, is passed through Ar and O2Mixing
Gas, regulates Ar:O2Ratio is 5:1, and operating pressure is 2.4Pa, is purity 99.96% at target
Metal W target magnetic control sputtering 28min, target is the metal tin target magnetron sputtering 2min of purity 98%,
Obtain the SnO that adulterates2WO3Thin film, i.e. WO3Air-sensitive film layer；
S2, preparation B face structure, including following enforcement step: (1) takes same size (4cm × 4cm)
Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water, NaOH aqueous solution, go from
Sub-water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate to be dissolved in 200ml water,
Add excess concentrated hydrochloric acid obtain active tungstic acid precipitation, is filtered, then with deionized water cleaning until
Can't detect chloride ion, then active tungstic acid precipitation is dissolved in hydrogen peroxide, prepares colloidal sol, spin coating
In quartz glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) tungsten is taken
Acid sodium powder 4.12g is dissolved in 60ml deionized water, and regulating its pH with 3M HCl solution is 2.0,
Be subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, quartz glass substrate is lain in from
In sub-water, after stirring 1 hour, pour in rustless steel hydrothermal reaction kettle, be heated to 150 DEG C in an oven
Keep 10h, then take out quartz glass substrate and spend ionized water cleaning；(4) chloroform is selected
For solvent, take 3.8g ZnTPP-2-NO2It is configured to the solution of 5.0mg/ml, supersound process 20min,
Make solution uniform, by dripping glue mode by made solution drop coating at quartz glass substrate surface, set rotation
Painting speed is 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate at vacuum drying oven
In be dried 12h at 60 DEG C, obtain the ZnTPP-2-NO that adulterates2WO3Nano wire film, i.e. WO3
Gas-discoloration layer；
S3, assembling: by staggered relatively to the A face completed, B face structure, distance 500 μm, A
The periphery of face structure and the handing-over of B face structure uses colloid to seal, and obtains described gas-discoloration gas sensing
The sensing unit of device.
The technical scheme that embodiments herein provides includes following beneficial effect:
1. configuration aspects, creative employing double membrane structure, the air-sensitive combining tungsten oxide material is special
Property and gas-discoloration characteristic, increase the range of application of device；
2. tungsten oxide air-sensitive film passes through magnetically controlled sputter method system based on Film-mode resistor sensor, thin film
Make, by controlling partial pressure of oxygen and doped stannum oxide in manufacturing process so that thin film is to NO2Selectivity
All it is greatly improved with sensitivity；
3. tungsten oxide gas chromism film is tungsten oxide nano doping tetraphenylporphyrin zinc derivative
(ZnTPP-2-NO2) material, this dopant material, as catalyst, substantially increases tungsten oxide nanometer
Line is to H2Reactivity, improve sensitivity, and achieve " smell-seeing " to hydrogen and measure.
Aspect and advantage that the application adds will part be given in the following description, and part will be from following
Description in become obvious, or recognized by the practice of the application.It should be appreciated that above
It is only exemplary and explanatory that general description and details hereinafter describe, and can not limit the application.
Accompanying drawing explanation
Accompanying drawing herein is merged in description and constitutes the part of this specification, it is shown that meet this
Inventive embodiment, and for explaining the principle of the present invention together with description.
Fig. 1 is the schematic diagram of sensing unit in the gas-discoloration gas sensor that the present invention uses.
Fig. 2 is the flow chart preparing the sensing unit in Fig. 1.
Wherein: 1-quartz glass substrate, 2-interdigital electrode layer, 3-WO3Air-sensitive film layer, 4-hollow
Structure, 5-WO3Gas-discoloration layer.
Detailed description of the invention
Here will illustrate exemplary embodiment in detail, its example represents in the accompanying drawings.Below
Description when relating to accompanying drawing, unless otherwise indicated, the same numbers in different accompanying drawings represents identical or phase
As key element.Embodiment described in following exemplary embodiment does not represent and present invention phase one
The all embodiments caused.On the contrary, they only with as appended claims describes in detail, this
The example of the consistent apparatus and method of some aspects of invention.
Following disclosure provides many different embodiments or example for realizing the difference of the application
Structure.In order to simplify disclosure herein, hereinafter parts and setting to specific examples are described.
Certainly, they are the most merely illustrative, and are not intended to limit the application.Additionally, the application is permissible
Repeat reference numerals and/or letter in different examples.This repetition is to simplify and clearly mesh
, itself it is more than the relation between various embodiment being discussed and/or arranging.Additionally, the application
The various specific technique provided and the example of material, but those of ordinary skill in the art can anticipate
Know the applicability to other techniques and/or the use of other materials.It addition, described below first is special
Levy Second Eigenvalue " on " structure can include what the first and second features were formed as directly contacting
Embodiment, it is also possible to include the embodiment that other feature is formed between the first and second features, this
Sample the first and second feature is not likely to be directly contact.
In the description of the present application, it should be noted that unless otherwise prescribed and limit, term " peace
Dress ", should be interpreted broadly " being connected ", " connection ", for example, it may be mechanical connection or electrically connect, also
Can be the connection of two element internals, can be to be joined directly together, it is also possible to indirect by intermediary
It is connected, for the ordinary skill in the art, above-mentioned term can be understood as the case may be
Concrete meaning.
Modern society, along with economic and industry development, mankind's consumption to various natural resourcess
Being continuously increased, owing to pursuing the shortcoming of economic goal and environmental consciousness, the pollution problem of environment is the tightest
Weight.Meanwhile, show gas aspect, in productive life discharge various inflammable, explosive, have
The leakage of gas in poisonous gas and environment, pollution are also that people's property safety is big with the one of personal safety
Threaten.Therefore, gas sensor technology is one of important topic of current research.Gas sensor is
A kind of can change and the device effectively monitored or device by perception surrounding target gas levels,
It is based on physical principle or chemical reaction etc., the type of gas sensor mainly has semiconductor gas
Dependent sensor, electrochemical gas sensor, catalytic combustion type gas sensor, optical profile type gas sensing
Device etc..WO3It is a kind of preferably controllable color change material, can realize visible ray and near-infrared radiation saturating
Cross continuously adjusting of rate.Amorphous WO from Deb reported first in 19693The electrochromism effect of thin film
Since Ying, find the performance such as its gas-discoloration, photochromic, thermochromism successively, meanwhile, as
Transition metal oxide, Tungstic anhydride. is to some gas, such as NO2、NO、NH3、H2、H2S etc.
All show sensitivity characteristic；Compared with electrochromic device, WO3Gas-discoloration device has system structure
Simply, the advantage such as relative inexpensiveness, therefore its gas-discoloration characteristic is combined with gas-sensitive property,
Great significance to gas sensing optics type senser element.
The operation principle of the gas sensor used in the application is: gas sensor is sensing technology
One important branch.Gas sensor can be divided into dissimilar according to structure and material etc., wherein,
The sensitive prime material that Metal Oxide Gas Sensors is used is broad stopband N-shaped metal-oxide half
Conductor, it all shows good sensitivity characteristic to multiple gases.
The sensitive mechanism of metal oxide semiconductor gas sensor is: sensitive material is made into as thin
Films etc. are beneficial to contact the structure of air, under heating state, when it is exposed in air, and sensitive material
The total surface of material is to adsorb a certain amount of oxonium ion, forms surface potential barrier and space charge layer, can make
The sheet electron concentration of sensitive material declines, and then electrical conductivity declines；When object gas is reproducibility gas
(such as CO, H during body2), this reducibility gas can adsorb on sensitive material surface, and with surface
Oxygen reacts, and makes sheet electron concentration increase, and electrical conductivity rises therewith；When object gas is oxidation
(such as NO during property gas2), the absorption on sensitive material surface of this oxidizing gas further increases
The adsorbance of oxygen so that the electrical conductivity of sensitive material declines further；I.e. the concentration of object gas with
The electrical conductivity of sensitive material has dependency, thus, by measure sensitive material electrical conductivity change thus
Measure the concentration of object gas.
After gas-discoloration refers to that material arrives some gas, because the reversible chemical reaction occurred makes
Material produces the colour developing effect that the light to wavelengths characteristic absorbs, and the absorption spectrum of material can change,
Macro manifestations is the change of material color.Specific to WO3After contact hydrogen, it can with hydrogen generation
Back reaction, can form tungsten bronze structure (HxWO4), owing to this structure is blue, show as WO3
The color of thin film can be blue by original transparent color, again because the change of thin film color can make it saturating
The light intensity crossed changes, i.e. the light transmittance of thin film changes, therefore can be by measuring thin film
The concentration of determination of light transmittance hydrogen.
The application is based on WO3The gas-discoloration character of material and air-sensitive character, will by double membrane structure
It combines；On the one hand, WO3Air-sensitive film can measure NO in the case of external power supply and heating2
Concentration, on the other hand, can not heat with not powered etc. have particular/special requirement in the environment of, WO3Air-sensitive
Thin-film material shows limitation, now can pass through WO3Gas chromism film is to H2Detect.
Embodiment 1:
There is provided a kind of hydrogen cylinder carrying leak detection function, described hydrogen cylinder outer surface that gas is installed to cause
Variable color gas sensor, described gas-discoloration gas sensor is based on WO3Gas sensitive and WO3Gas
Cause off-color material；Described gas-discoloration gas sensor includes that sensing unit, heating unit and data are read
Take unit；The tungsten oxide air-sensitive film of described heating unit and data-reading unit and sensing unit is even
Connect；Heating source when described heating unit works as tungsten oxide air-sensitive film；At data-reading unit
The conductivity variations signal of reason tungsten oxide air-sensitive film is to show the concentration value of object gas.
Fig. 1 is the schematic diagram of sensing unit in the gas-discoloration gas sensor that the present invention uses.Reference
Fig. 1, this sensing unit is the double-decker of hollow structure, forms double-deck A face structure and B
Face structure is staggered relatively, distance 500 μm, and the periphery of A face structure and the handing-over of B face structure uses colloid
Seal；Described A face includes quartz glass substrate, interdigital electrode layer and WO3Air-sensitive film layer, WO3
Air-sensitive film layer is doping SnO2WO3Thin film, it is possible to achieve to NO2The detection of gas, described
B face includes quartz glass substrate and WO3Gas-discoloration layer, WO3Gas-discoloration layer is WO3Nanometer
Line film doping ZnTPP-2-NO2, utilize gas-discoloration principle can realize the inspection of the visualization to hydrogen
Survey；2 it are additionally provided with for air-vent that object gas penetrates in the structure of described B face.In A face,
Described SnO2Granularity less than 30nm, described WO3Air-sensitive film layer thickness is 700nm；B
In face, described WO3Nanowire length about 1 μm, diameter about 60nm；
Fig. 2 is according to the flow chart preparing sensing unit shown in an exemplary embodiment, such as Fig. 2 institute
Show, comprise the following steps:
S1, preparation A face structure, including following enforcement step: (1) takes certain size (4cm × 4cm)
Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2)
Spin coating one layer photoetching glue in quartz glass substrate, thickness 1 μm, under interdigital electrode mask covers
Exposure 6s, cleans with deionized water after being then passed through development 50s, uses magnetically controlled sputter method plating one
Cr film thick for layer 300nm, as interdigital electrode layer, then removes photoresist；(3) by quartz glass
Glass substrate is put in magnetic control sputtering device, is evacuated to 5 × 10-4Below Pa, is passed through Ar and O2Mixing
Gas, regulates Ar:O2Ratio is 5:1, and operating pressure is 2.4Pa, is purity 99.96% at target
Metal W target magnetic control sputtering 28min, target is the metal tin target magnetron sputtering 2min of purity 98%,
Obtain the SnO that adulterates2WO3Thin film, i.e. WO3Air-sensitive film layer；
S2, preparation B face structure, including following enforcement step: (1) takes same size (4cm × 4cm)
Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water, NaOH aqueous solution, go from
Sub-water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate to be dissolved in 200ml water,
Add excess concentrated hydrochloric acid obtain active tungstic acid precipitation, is filtered, then with deionized water cleaning until
Can't detect chloride ion, then active tungstic acid precipitation is dissolved in hydrogen peroxide, prepares colloidal sol, spin coating
In quartz glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) tungsten is taken
Acid sodium powder 4.12g is dissolved in 60ml deionized water, and regulating its pH with 3M HCl solution is 2.0,
Be subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, quartz glass substrate is lain in from
In sub-water, after stirring 1 hour, pour in rustless steel hydrothermal reaction kettle, be heated to 150 DEG C in an oven
Keep 10h, then take out quartz glass substrate and spend ionized water cleaning；(4) chloroform is selected
For solvent, take 3.8g ZnTPP-2-NO2It is configured to the solution of 5.0mg/ml, supersound process 20min,
Make solution uniform, by dripping glue mode by made solution drop coating at quartz glass substrate surface, set rotation
Painting speed is 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate at vacuum drying oven
In be dried 12h at 60 DEG C, obtain the ZnTPP-2-NO that adulterates2WO3Nano wire film, i.e. WO3
Gas-discoloration layer；
S3, assembling: by staggered relatively to the A face completed, B face structure, distance 500 μm, A
The periphery of face structure and the handing-over of B face structure uses colloid to seal, and obtains described gas-discoloration gas sensing
The sensing unit of device.
About the device in above-described embodiment, the concrete mode that wherein modules performs to operate exists
About the embodiment of the method has been described in detail, explanation will be not set forth in detail herein.
Data test:
In A face, air-sensitive test completes on Testing system of gas-sensor built, is put into by the device made
In quartz ampoule, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, after stable, logical
Enter by air and finite concentration NO2The mixed gas of configuration, keeps 30min, is again passed through pure air,
Record WO3The resistance value of air-sensitive film layer, respectively R (NO2) and R (air), define air-sensitive
Sensitivity is: S=R (NO2)/R (air), response time is defined as being passed through resistance after test gas
Change to the time required for the 80% of maximum changes in resistance.Test finds, this tungsten oxide air-sensitive film
NO in 8ppm concentration2Gas medium sensitivity is 30；Best-case Response Time is 12s；Through 100
Secondary testing fatigue, electrical response value drops to original 86%.WO3Air-sensitive film shows well
Sensitivity, response time and repeatability.
In B face, use spectrophotometer to variable concentrations H2WO in atmosphere3Gas-discoloration layer is carried out
Light transmittance is tested, and defines T0For not leading to H2Time sample light transmittance, T is for being passed through finite concentration H2
Time sample light transmittance, relative light transmission:, be passed through H2When concentration is 5000ppm, the most thoroughly
Light rate with wavelength change, minimum 4%, be 59.7% to the maximum, and through about 10min, relatively
Light transmittance tends towards stability, it is seen that be passed through with tested gas, and tungsten oxide gas-discoloration layer light transmittance declines,
Showing as thin film color and transparent become blue from original, response time is short, shows good gas mutagens
Color performance.
Test finds, this hydrogen cylinder is provided with gas-discoloration gas sensor, utilizes gas-discoloration principle
Can realize the Visual retrieval to hydrogen, and response time is short, highly sensitive, color change interval is relatively
Greatly, it is achieved that beyond thought effect, there is certain actual application value.
Embodiment 2:
There is provided a kind of hydrogen cylinder carrying leak detection function, described hydrogen cylinder outer surface that gas is installed to cause
Variable color gas sensor, described gas-discoloration gas sensor is based on WO3Gas sensitive and WO3Gas
Cause off-color material；Described gas-discoloration gas sensor includes that sensing unit, heating unit and data are read
Take unit；The tungsten oxide air-sensitive film of described heating unit and data-reading unit and sensing unit is even
Connect；Heating source when described heating unit works as tungsten oxide air-sensitive film；At data-reading unit
The conductivity variations signal of reason tungsten oxide air-sensitive film is to show the concentration value of object gas.
Fig. 1 is the schematic diagram of sensing unit in the gas-discoloration gas sensor that the present invention uses.Reference
Fig. 1, this sensing unit is the double-decker of hollow structure, forms double-deck A face structure and B
Face structure is staggered relatively, distance 500 μm, and the periphery of A face structure and the handing-over of B face structure uses colloid
Seal；Described A face includes quartz glass substrate, interdigital electrode layer and WO3Air-sensitive film layer, WO3
Air-sensitive film layer is doping SnO2WO3Thin film, it is possible to achieve to NO2The detection of gas, described
B face includes quartz glass substrate and WO3Gas-discoloration layer, WO3Gas-discoloration layer is WO3Nanometer
Line film doping ZnTPP-2-NO2, utilize gas-discoloration principle can realize the inspection of the visualization to hydrogen
Survey；2 it are additionally provided with for air-vent that object gas penetrates in the structure of described B face.In A face,
Described SnO2Granularity less than 55nm, described WO3Air-sensitive film layer thickness is 500nm；B
In face, described WO3Nanowire length about 1 μm, diameter about 60nm；
Fig. 2 is according to the flow chart preparing sensing unit shown in an exemplary embodiment, such as Fig. 2 institute
Show, comprise the following steps:
S1, preparation A face structure, including following enforcement step: (1) takes certain size (4cm × 4cm)
Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2)
Spin coating one layer photoetching glue in quartz glass substrate, thickness 1 μm, under interdigital electrode mask covers
Exposure 6s, cleans with deionized water after being then passed through development 50s, uses magnetically controlled sputter method plating one
Cr film thick for layer 300nm, as interdigital electrode layer, then removes photoresist；(3) by quartz glass
Glass substrate is put in magnetic control sputtering device, is evacuated to 5 × 10-4Below Pa, is passed through Ar and O2Mixing
Gas, regulates Ar:O2Ratio is 5:1, and operating pressure is 2.4Pa, is purity 99.96% at target
Metal W target magnetic control sputtering 28min, target is the metal tin target magnetron sputtering 2min of purity 98%,
Obtain the SnO that adulterates2WO3Thin film, i.e. WO3Air-sensitive film layer；
S2, preparation B face structure, including following enforcement step: (1) takes same size (4cm × 4cm)
Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water, NaOH aqueous solution, go from
Sub-water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate to be dissolved in 200ml water,
Add excess concentrated hydrochloric acid obtain active tungstic acid precipitation, is filtered, then with deionized water cleaning until
Can't detect chloride ion, then active tungstic acid precipitation is dissolved in hydrogen peroxide, prepares colloidal sol, spin coating
In quartz glass substrate, 330 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) tungsten is taken
Acid sodium powder 4.12g is dissolved in 60ml deionized water, and regulating its pH with 3M HCl solution is 2.0,
Be subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, quartz glass substrate is lain in from
In sub-water, after stirring 1 hour, pour in rustless steel hydrothermal reaction kettle, be heated to 150 DEG C in an oven
Keep 10h, then take out quartz glass substrate and spend ionized water cleaning；(4) chloroform is selected
For solvent, take 3.8g ZnTPP-2-NO2It is configured to the solution of 5.4mg/ml, supersound process 20min,
Make solution uniform, by dripping glue mode by made solution drop coating at quartz glass substrate surface, set rotation
Painting speed is 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate at vacuum drying oven
In be dried 12h at 60 DEG C, obtain the ZnTPP-2-NO that adulterates2WO3Nano wire film, i.e. WO3
Gas-discoloration layer；
S3, assembling: by staggered relatively to the A face completed, B face structure, distance 500 μm, A
The periphery of face structure and the handing-over of B face structure uses colloid to seal, and obtains described gas-discoloration gas sensing
The sensing unit of device.
About the device in above-described embodiment, the concrete mode that wherein modules performs to operate exists
About the embodiment of the method has been described in detail, explanation will be not set forth in detail herein.
Data test:
In A face, air-sensitive test completes on Testing system of gas-sensor built, is put into by the device made
In quartz ampoule, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, after stable, logical
Enter by air and finite concentration NO2The mixed gas of configuration, keeps 30min, is again passed through pure air,
Record WO3The resistance value of air-sensitive film layer, respectively R (NO2) and R (air), define air-sensitive
Sensitivity is: S=R (NO2)/R (air), response time is defined as being passed through resistance after test gas
Change to the time required for the 80% of maximum changes in resistance.Test finds, this tungsten oxide air-sensitive film
NO in 8ppm concentration2Gas medium sensitivity is 30；Best-case Response Time is 15s；Through 100
Secondary testing fatigue, electrical response value drops to original 86%.WO3Air-sensitive film shows well
Sensitivity, response time and repeatability.
In B face, use spectrophotometer to variable concentrations H2WO in atmosphere3Gas-discoloration layer is carried out
Light transmittance is tested, and defines T0For not leading to H2Time sample light transmittance, T is for being passed through finite concentration H2
Time sample light transmittance, relative light transmission:, be passed through H2When concentration is 5000ppm, the most thoroughly
Light rate with wavelength change, minimum 7%, be 65% to the maximum, and through about 10min, the most thoroughly
Light rate tends towards stability, it is seen that be passed through with tested gas, and tungsten oxide gas-discoloration layer light transmittance declines, table
Now transparent being become blue for thin film color from original, response time is short, shows good gas-discoloration
Performance.
Test finds, this hydrogen cylinder is provided with gas-discoloration gas sensor, utilizes gas-discoloration principle
Can realize the Visual retrieval to hydrogen, and response time is short, highly sensitive, color change interval is relatively
Greatly, it is achieved that beyond thought effect, there is certain actual application value.
Embodiment 3:
There is provided a kind of hydrogen cylinder carrying leak detection function, described hydrogen cylinder outer surface that gas is installed to cause
Variable color gas sensor, described gas-discoloration gas sensor is based on WO3Gas sensitive and WO3Gas
Cause off-color material；Described gas-discoloration gas sensor includes that sensing unit, heating unit and data are read
Take unit；The tungsten oxide air-sensitive film of described heating unit and data-reading unit and sensing unit is even
Connect；Heating source when described heating unit works as tungsten oxide air-sensitive film；At data-reading unit
The conductivity variations signal of reason tungsten oxide air-sensitive film is to show the concentration value of object gas.
Fig. 1 is the schematic diagram of sensing unit in the gas-discoloration gas sensor that the present invention uses.Reference
Fig. 1, this sensing unit is the double-decker of hollow structure, forms double-deck A face structure and B
Face structure is staggered relatively, distance 500 μm, and the periphery of A face structure and the handing-over of B face structure uses colloid
Seal；Described A face includes quartz glass substrate, interdigital electrode layer and WO3Air-sensitive film layer, WO3
Air-sensitive film layer is doping SnO2WO3Thin film, it is possible to achieve to NO2The detection of gas, described
B face includes quartz glass substrate and WO3Gas-discoloration layer, WO3Gas-discoloration layer is WO3Nanometer
Line film doping ZnTPP-2-NO2, utilize gas-discoloration principle can realize the inspection of the visualization to hydrogen
Survey；2 it are additionally provided with for air-vent that object gas penetrates in the structure of described B face.In A face,
Described SnO2Granularity less than 50nm, described WO3Air-sensitive film layer thickness is 500nm；B
In face, described WO3Nanowire length about 1 μm, diameter about 60nm；
Fig. 2 is according to the flow chart preparing sensing unit shown in an exemplary embodiment, such as Fig. 2 institute
Show, comprise the following steps:
S1, preparation A face structure, including following enforcement step: (1) takes certain size (4cm × 4cm)
Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2)
Spin coating one layer photoetching glue in quartz glass substrate, thickness 1.5 μm, cover at interdigital electrode mask
Lower exposure 6s, cleans with deionized water after being then passed through development 50s, uses magnetically controlled sputter method plating
One layer of Cr film thick for 300nm, as interdigital electrode layer, then removes photoresist；(3) by quartz
Substrate of glass is put in magnetic control sputtering device, is evacuated to 5 × 10-4Below Pa, is passed through Ar and O2Mixed
Close gas, regulate Ar:O2Ratio is 5:1, and operating pressure is 2.4Pa, is purity 99.96% at target
Metal W target magnetic control sputtering 28min, target is the metal tin target magnetron sputtering 2min of purity 98%,
Obtain the SnO that adulterates2WO3Thin film, i.e. WO3Air-sensitive film layer；
S2, preparation B face structure, including following enforcement step: (1) takes same size (4cm × 4cm)
Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water, NaOH aqueous solution, go from
Sub-water ultrasonic cleaning, the time is 20min；(2) take 22g sodium tungstate to be dissolved in 200ml water,
Add excess concentrated hydrochloric acid obtain active tungstic acid precipitation, is filtered, then with deionized water cleaning until
Can't detect chloride ion, then active tungstic acid precipitation is dissolved in hydrogen peroxide, prepares colloidal sol, spin coating
In quartz glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) tungsten is taken
Acid sodium powder 4.12g is dissolved in 60ml deionized water, and regulating its pH with 3M HCl solution is 2.0,
Be subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, quartz glass substrate is lain in from
In sub-water, after stirring 1 hour, pour in rustless steel hydrothermal reaction kettle, be heated to 150 DEG C in an oven
Keep 10h, then take out quartz glass substrate and spend ionized water cleaning；(4) chloroform is selected
For solvent, take 3.8g ZnTPP-2-NO2It is configured to the solution of 5.0mg/ml, supersound process 20min,
Make solution uniform, by dripping glue mode by made solution drop coating at quartz glass substrate surface, set rotation
Painting speed is 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate at vacuum drying oven
In be dried 12h at 60 DEG C, obtain the ZnTPP-2-NO that adulterates2WO3Nano wire film, i.e. WO3
Gas-discoloration layer；
S3, assembling: by staggered relatively to the A face completed, B face structure, distance 500 μm, A
The periphery of face structure and the handing-over of B face structure uses colloid to seal, and obtains described gas-discoloration gas sensing
The sensing unit of device.
About the device in above-described embodiment, the concrete mode that wherein modules performs to operate exists
About the embodiment of the method has been described in detail, explanation will be not set forth in detail herein.
Data test:
In A face, air-sensitive test completes on Testing system of gas-sensor built, is put into by the device made
In quartz ampoule, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, after stable, logical
Enter by air and finite concentration NO2The mixed gas of configuration, keeps 30min, is again passed through pure air,
Record WO3The resistance value of air-sensitive film layer, respectively R (NO2) and R (air), define air-sensitive
Sensitivity is: S=R (NO2)/R (air), response time is defined as being passed through resistance after test gas
Change to the time required for the 80% of maximum changes in resistance.Test finds, this tungsten oxide air-sensitive film
NO in 8ppm concentration2Gas medium sensitivity is 30；Best-case Response Time is 15s；Through 100
Secondary testing fatigue, electrical response value drops to original 86%.WO3Air-sensitive film shows well
Sensitivity, response time and repeatability.
In B face, use spectrophotometer to variable concentrations H2WO in atmosphere3Gas-discoloration layer is carried out
Light transmittance is tested, and defines T0For not leading to H2Time sample light transmittance, T is for being passed through finite concentration H2
Time sample light transmittance, relative light transmission:, be passed through H2When concentration is 5000ppm, the most thoroughly
Light rate with wavelength change, minimum 6%, be 56.7% to the maximum, and through about 10min, relatively
Light transmittance tends towards stability, it is seen that be passed through with tested gas, and tungsten oxide gas-discoloration layer light transmittance declines,
Showing as thin film color and transparent become blue from original, response time is short, shows good gas mutagens
Color performance.
Test finds, this hydrogen cylinder is provided with gas-discoloration gas sensor, utilizes gas-discoloration principle
Can realize the Visual retrieval to hydrogen, and response time is short, highly sensitive, color change interval is relatively
Greatly, it is achieved that beyond thought effect, there is certain actual application value.
Embodiment 4:
There is provided a kind of hydrogen cylinder carrying leak detection function, described hydrogen cylinder outer surface that gas is installed to cause
Variable color gas sensor, described gas-discoloration gas sensor is based on WO3Gas sensitive and WO3Gas
Cause off-color material；Described gas-discoloration gas sensor includes that sensing unit, heating unit and data are read
Take unit；The tungsten oxide air-sensitive film of described heating unit and data-reading unit and sensing unit is even
Connect；Heating source when described heating unit works as tungsten oxide air-sensitive film；At data-reading unit
The conductivity variations signal of reason tungsten oxide air-sensitive film is to show the concentration value of object gas.
Fig. 1 is the schematic diagram of sensing unit in the gas-discoloration gas sensor that the present invention uses.Reference
Fig. 1, this sensing unit is the double-decker of hollow structure, forms double-deck A face structure and B
Face structure is staggered relatively, distance 500 μm, and the periphery of A face structure and the handing-over of B face structure uses colloid
Seal；Described A face includes quartz glass substrate, interdigital electrode layer and WO3Air-sensitive film layer, WO3
Air-sensitive film layer is doping SnO2WO3Thin film, it is possible to achieve to NO2The detection of gas, described
B face includes quartz glass substrate and WO3Gas-discoloration layer, WO3Gas-discoloration layer is WO3Nanometer
Line film doping ZnTPP-2-NO2, utilize gas-discoloration principle can realize the inspection of the visualization to hydrogen
Survey；2 it are additionally provided with for air-vent that object gas penetrates in the structure of described B face.In A face,
Described SnO2Granularity less than 50nm, described WO3Air-sensitive film layer thickness is 700nm；B
In face, described WO3Nanowire length about 1 μm, diameter about 50nm；
Fig. 2 is according to the flow chart preparing sensing unit shown in an exemplary embodiment, such as Fig. 2 institute
Show, comprise the following steps:
S1, preparation A face structure, including following enforcement step: (1) takes certain size (4cm × 4cm)
Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2)
Spin coating one layer photoetching glue in quartz glass substrate, thickness 1 μm, under interdigital electrode mask covers
Exposure 6s, cleans with deionized water after being then passed through development 50s, uses magnetically controlled sputter method plating one
Cr film thick for layer 300nm, as interdigital electrode layer, then removes photoresist；(3) by quartz glass
Glass substrate is put in magnetic control sputtering device, is evacuated to 5 × 10-4Below Pa, is passed through Ar and O2Mixing
Gas, regulates Ar:O2Ratio is 5:1, and operating pressure is 2.4Pa, is purity 99.96% at target
Metal W target magnetic control sputtering 28min, target is the metal tin target magnetron sputtering 2min of purity 98%,
Obtain the SnO that adulterates2WO3Thin film, i.e. WO3Air-sensitive film layer；
S2, preparation B face structure, including following enforcement step: (1) takes same size (4cm × 4cm)
Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water, NaOH aqueous solution, go from
Sub-water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate to be dissolved in 200ml water,
Add excess concentrated hydrochloric acid obtain active tungstic acid precipitation, is filtered, then with deionized water cleaning until
Can't detect chloride ion, then active tungstic acid precipitation is dissolved in hydrogen peroxide, prepares colloidal sol, spin coating
In quartz glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) tungsten is taken
Acid sodium powder 4.12g is dissolved in 60ml deionized water, and regulating its pH with 3M HCl solution is 2.0,
Be subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, quartz glass substrate is lain in from
In sub-water, after stirring 1 hour, pour in rustless steel hydrothermal reaction kettle, be heated to 150 DEG C in an oven
Keep 10h, then take out quartz glass substrate and spend ionized water cleaning；(4) chloroform is selected
For solvent, take 3.8g ZnTPP-2-NO2It is configured to the solution of 5.0mg/ml, supersound process 20min,
Make solution uniform, by dripping glue mode by made solution drop coating at quartz glass substrate surface, set rotation
Painting speed is 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate at vacuum drying oven
In be dried 12h at 60 DEG C, obtain the ZnTPP-2-NO that adulterates2WO3Nano wire film, i.e. WO3
Gas-discoloration layer；
S3, assembling: by staggered relatively to the A face completed, B face structure, distance 500 μm, A
The periphery of face structure and the handing-over of B face structure uses colloid to seal, and obtains described gas-discoloration gas sensing
The sensing unit of device.
About the device in above-described embodiment, the concrete mode that wherein modules performs to operate exists
About the embodiment of the method has been described in detail, explanation will be not set forth in detail herein.
Data test:
In A face, air-sensitive test completes on Testing system of gas-sensor built, is put into by the device made
In quartz ampoule, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, after stable, logical
Enter by air and finite concentration NO2The mixed gas of configuration, keeps 30min, is again passed through pure air,
Record WO3The resistance value of air-sensitive film layer, respectively R (NO2) and R (air), define air-sensitive
Sensitivity is: S=R (NO2)/R (air), response time is defined as being passed through resistance after test gas
Change to the time required for the 80% of maximum changes in resistance.Test finds, this tungsten oxide air-sensitive film
NO in 8ppm concentration2Gas medium sensitivity is 35；Best-case Response Time is 15s；Through 100
Secondary testing fatigue, electrical response value drops to original 86%.WO3Air-sensitive film shows well
Sensitivity, response time and repeatability.
In B face, use spectrophotometer to variable concentrations H2WO in atmosphere3Gas-discoloration layer is carried out
Light transmittance is tested, and defines T0For not leading to H2Time sample light transmittance, T is for being passed through finite concentration H2
Time sample light transmittance, relative light transmission:, be passed through H2When concentration is 5000ppm, the most thoroughly
Light rate with wavelength change, minimum 4%, be 59.7% to the maximum, and through about 10min, relatively
Light transmittance tends towards stability, it is seen that be passed through with tested gas, and tungsten oxide gas-discoloration layer light transmittance declines,
Showing as thin film color and transparent become blue from original, response time is short, shows good gas mutagens
Color performance.
Test finds, this hydrogen cylinder is provided with gas-discoloration gas sensor, utilizes gas-discoloration principle
Can realize the Visual retrieval to hydrogen, and response time is short, highly sensitive, color change interval is relatively
Greatly, it is achieved that beyond thought effect, there is certain actual application value.
Embodiment 5:
There is provided a kind of hydrogen cylinder carrying leak detection function, described hydrogen cylinder outer surface that gas is installed to cause
Variable color gas sensor, described gas-discoloration gas sensor is based on WO3Gas sensitive and WO3Gas
Cause off-color material；Described gas-discoloration gas sensor includes that sensing unit, heating unit and data are read
Take unit；The tungsten oxide air-sensitive film of described heating unit and data-reading unit and sensing unit is even
Connect；Heating source when described heating unit works as tungsten oxide air-sensitive film；At data-reading unit
The conductivity variations signal of reason tungsten oxide air-sensitive film is to show the concentration value of object gas.
Fig. 1 is the schematic diagram of sensing unit in the gas-discoloration gas sensor that the present invention uses.Reference
Fig. 1, this sensing unit is the double-decker of hollow structure, forms double-deck A face structure and B
Face structure is staggered relatively, distance 500 μm, and the periphery of A face structure and the handing-over of B face structure uses colloid
Seal；Described A face includes quartz glass substrate, interdigital electrode layer and WO3Air-sensitive film layer, WO3
Air-sensitive film layer is doping SnO2WO3Thin film, it is possible to achieve to NO2The detection of gas, described
B face includes quartz glass substrate and WO3Gas-discoloration layer, WO3Gas-discoloration layer is WO3Nanometer
Line film doping ZnTPP-2-NO2, utilize gas-discoloration principle can realize the inspection of the visualization to hydrogen
Survey；2 it are additionally provided with for air-vent that object gas penetrates in the structure of described B face.In A face,
Described SnO2Granularity less than 50nm, described WO3Air-sensitive film layer thickness is 400nm；B
In face, described WO3Nanowire length about 1 μm, diameter about 30nm；
Fig. 2 is according to the flow chart preparing sensing unit shown in an exemplary embodiment, such as Fig. 2 institute
Show, comprise the following steps:
S1, preparation A face structure, including following enforcement step: (1) takes certain size (4cm × 4cm)
Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2)
Spin coating one layer photoetching glue in quartz glass substrate, thickness 1 μm, under interdigital electrode mask covers
Exposure 6s, cleans with deionized water after being then passed through development 50s, uses magnetically controlled sputter method plating one
Cr film thick for layer 300nm, as interdigital electrode layer, then removes photoresist；(3) by quartz glass
Glass substrate is put in magnetic control sputtering device, is evacuated to 5 × 10-4Below Pa, is passed through Ar and O2Mixing
Gas, regulates Ar:O2Ratio is 5:1, and operating pressure is 2.4Pa, is purity 99.96% at target
Metal W target magnetic control sputtering 28min, target is the metal tin target magnetron sputtering 2min of purity 98%,
Obtain the SnO that adulterates2WO3Thin film, i.e. WO3Air-sensitive film layer；
S2, preparation B face structure, including following enforcement step: (1) takes same size (4cm × 4cm)
Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water, NaOH aqueous solution, go from
Sub-water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate to be dissolved in 200ml water,
Add excess concentrated hydrochloric acid obtain active tungstic acid precipitation, is filtered, then with deionized water cleaning until
Can't detect chloride ion, then active tungstic acid precipitation is dissolved in hydrogen peroxide, prepares colloidal sol, spin coating
In quartz glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) tungsten is taken
Acid sodium powder 4.12g is dissolved in 60ml deionized water, and regulating its pH with 3M HCl solution is 2.0,
Be subsequently adding 2.5g (0.3M) ammonium sulfate as controlling agent, quartz glass substrate is lain in from
In sub-water, after stirring 1 hour, pour in rustless steel hydrothermal reaction kettle, be heated to 150 DEG C in an oven
Keep 10h, then take out quartz glass substrate and spend ionized water cleaning；(4) chloroform is selected
For solvent, take 3.8g ZnTPP-2-NO2It is configured to the solution of 5.6mg/ml, supersound process 20min,
Make solution uniform, by dripping glue mode by made solution drop coating at quartz glass substrate surface, set rotation
Painting speed is 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate at vacuum drying oven
In be dried 12h at 60 DEG C, obtain the ZnTPP-2-NO that adulterates2WO3Nano wire film, i.e. WO3
Gas-discoloration layer；
S3, assembling: by staggered relatively to the A face completed, B face structure, distance 500 μm, A
The periphery of face structure and the handing-over of B face structure uses colloid to seal, and obtains described gas-discoloration gas sensing
The sensing unit of device.
About the device in above-described embodiment, the concrete mode that wherein modules performs to operate exists
About the embodiment of the method has been described in detail, explanation will be not set forth in detail herein.
Data test:
In A face, air-sensitive test completes on Testing system of gas-sensor built, is put into by the device made
In quartz ampoule, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, after stable, logical
Enter by air and finite concentration NO2The mixed gas of configuration, keeps 30min, is again passed through pure air,
Record WO3The resistance value of air-sensitive film layer, respectively R (NO2) and R (air), define air-sensitive
Sensitivity is: S=R (NO2)/R (air), response time is defined as being passed through resistance after test gas
Change to the time required for the 80% of maximum changes in resistance.Test finds, this tungsten oxide air-sensitive film
NO in 8ppm concentration2Gas medium sensitivity is 30；Best-case Response Time is 15s；Through 100
Secondary testing fatigue, electrical response value drops to original 83%.WO3Air-sensitive film shows well
Sensitivity, response time and repeatability.
In B face, use spectrophotometer to variable concentrations H2WO in atmosphere3Gas-discoloration layer is carried out
Light transmittance is tested, and defines T0For not leading to H2Time sample light transmittance, T is for being passed through finite concentration H2
Time sample light transmittance, relative light transmission:, be passed through H2When concentration is 5000ppm, the most thoroughly
Light rate with wavelength change, minimum 4%, be 59.7% to the maximum, and through about 10min, relatively
Light transmittance tends towards stability, it is seen that be passed through with tested gas, and tungsten oxide gas-discoloration layer light transmittance declines,
Showing as thin film color and transparent become blue from original, response time is short, shows good gas mutagens
Color performance.
Test finds, this hydrogen cylinder is provided with gas-discoloration gas sensor, utilizes gas-discoloration principle
Can realize the Visual retrieval to hydrogen, and response time is short, highly sensitive, color change interval is relatively
Greatly, it is achieved that beyond thought effect, there is certain actual application value.
Those skilled in the art, after considering description and putting into practice invention disclosed herein, will readily occur to
Other embodiments of the present invention.The application is intended to any modification of the present invention, purposes or fits
Answering property changes, and these modification, purposes or adaptations are followed the general principle of the present invention and wrap
Include the undocumented common knowledge in the art of the application or conventional techniques means.Description and reality
Executing example and be considered only as exemplary, true scope and spirit of the invention are referred to by claim below
Go out.
It should be appreciated that the invention is not limited in essence described above and illustrated in the accompanying drawings
Really structure, and various modifications and changes can carried out without departing from the scope.The scope of the present invention is only
Limited by appended claim.
Claims (2)
1. the hydrogen cylinder carrying leak detection function, it is characterised in that described hydrogen cylinder appearance
Face is provided with gas-discoloration gas sensor, and described gas-discoloration gas sensor is based on WO3Air-sensitive
Material and WO3Gas-discoloration material；Described gas-discoloration gas sensor includes sensing unit, adds
Hot cell and data-reading unit；The oxidation of described heating unit and data-reading unit and sensing unit
Tungsten air-sensitive film connects；Heating source when described heating unit works as tungsten oxide air-sensitive film；Number
According to reading the conductivity variations signal of cell processing tungsten oxide air-sensitive film to show the dense of object gas
Angle value；Described sensing unit is the double-decker of hollow structure, formed double-deck A face structure and
B face structure is staggered relatively, distance 500 μm, and the periphery of A face structure and the handing-over of B face structure uses
Colloid seals；Described A face includes quartz glass substrate, interdigital electrode layer and WO3Air-sensitive film layer,
WO3Air-sensitive film layer is doping SnO2WO3Thin film, it is possible to achieve to NO2The detection of gas,
Described B face includes quartz glass substrate and WO3Gas-discoloration layer, WO3Gas-discoloration layer is WO3
Nano wire film doping ZnTPP-2-NO2, utilize that gas-discoloration principle can realize hydrogen is visual
Change detection；2 it are additionally provided with for air-vent that object gas penetrates in the structure of described B face；A face
In, described SnO2Granularity less than 30nm, described WO3Air-sensitive film layer thickness is 700nm；
In B face, described WO3Nanowire length about 1 μm, diameter about 60nm.
2. the preparation a kind of hydrogen cylinder carrying leak detection function described in claim 1, its feature
Being, wherein, the making of the sensing unit of described gas-discoloration gas sensor comprises the following steps:
S1, preparation A face structure, including following enforcement step:
(1) take the quartz glass substrate of certain size (4cm × 4cm), sequentially pass through acetone, second
Alcohol, deionized water ultrasonic cleaning 20min；
(2) spin coating one layer photoetching glue in quartz glass substrate, thickness 1 μm, cover in interdigital electrode
Masterplate exposes 6s under covering, and cleans with deionized water after being then passed through development 50s, uses magnetic control to spatter
Cr film thick for shooting method one layer of 300nm of plating, as interdigital electrode layer, then removes photoresist；
(3) quartz glass substrate is put in magnetic control sputtering device, be evacuated to 5 × 10-4Below Pa,
It is passed through Ar and O2Mixed gas, regulate Ar:O2Ratio is 5:1, and operating pressure is 2.4Pa,
Target is the metal W target magnetic control sputtering 28min of purity 99.96%, and target is the gold of purity 98%
Belong to stannum target magnetic control sputtering 2min, obtain the SnO that adulterates2WO3Thin film, i.e. WO3Air-sensitive film layer；
S2, preparation B face structure, including following enforcement step:
(1) take the quartz glass substrate of same size (4cm × 4cm), sequentially pass through acetone, second
Alcohol, deionized water, NaOH aqueous solution, deionized water ultrasonic cleaning, the time is 20min；
(2) taking 20g sodium tungstate to be dissolved in 200ml water, the concentrated hydrochloric acid adding excess obtains Porous Tungsten
Acid precipitation, is filtered, then cleans until can't detect chloride ion with deionized water, then by activity
Wolframic acid precipitation is dissolved in hydrogen peroxide, prepares colloidal sol, is spun in quartz glass substrate, at 350 DEG C
Reason 1h obtains Seed Layer, and thickness is 20nm；
(3) take sodium tungstate powder 4.12g and be dissolved in 60ml deionized water, regulate with 3M HCl solution
Its pH is 2.0, is subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, by quartz glass substrate
The end, keeps flat in deionized water, after stirring 1 hour, pours in rustless steel hydrothermal reaction kettle, at baking oven
In be heated to 150 DEG C keep 10h, then take out quartz glass substrate spend ionized water clean；
(4) selecting chloroform is solvent, takes 3.8g ZnTPP-2-NO2It is configured to 5.0mg/ml's
Solution, supersound process 20min, make solution uniform, by dripping glue mode by made solution drop coating at stone
English glass basic surface, sets spin speed as 3400rpm, and spin-coating time is 70s, finally by stone
English substrate of glass is dried 12h in vacuum drying oven at 60 DEG C, obtain the ZnTPP-2-NO that adulterates2's
WO3Nano wire film, i.e. WO3Gas-discoloration layer；
S3, assembling: by staggered relatively to the A face completed, B face structure, distance 500 μm, A
The periphery of face structure and the handing-over of B face structure uses colloid to seal, and obtains described gas-discoloration gas sensing
The sensing unit of device.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105717109A (en) * | 2016-04-21 | 2016-06-29 | 林业城 | Hydrogen gas sensor based on gasochromic function |
| CN105823776A (en) * | 2016-04-21 | 2016-08-03 | 林业城 | Liquefied petroleum gas steam gasification device with high-sensitivity detection function |
| CN105911053A (en) * | 2016-04-21 | 2016-08-31 | 林业城 | Sensing device being able to realize visualization function |
| CN105928933A (en) * | 2016-04-21 | 2016-09-07 | 林业城 | Smell-seeing hydrogen generator |
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| CN111174986A (en) * | 2019-12-30 | 2020-05-19 | 清华大学 | Pipeline leakage detection method and hydrogen pipeline |
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| CN114877242A (en) * | 2021-02-05 | 2022-08-09 | 新启时代(北京)材料科技有限公司 | Gas cylinder with hydrogen leakage monitoring function and hydrogen leakage monitoring method |
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