CN105372208B - A kind of photonic crystal fiber methane transducer based on sensitive membrane coating - Google Patents
A kind of photonic crystal fiber methane transducer based on sensitive membrane coating Download PDFInfo
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Abstract
The invention belongs to technical field of optical fiber sensing, more particularly to a kind of photonic crystal fiber methane transducer based on sensitive membrane coating, by wideband light source, single mode optical fiber, three-dB coupler, photonic crystal fiber, reflecting mirror, index-matching fluid and spectroanalysis instrument composition, two ports of three-dB coupler side pass through single mode optical fiber respectively and connect with wideband light source and spectroanalysis instrument, two ports one of the other side pass through single mode optical fiber and photon crystal optical fiber fusion splicing, another leads to index-matching fluid by single mode optical fiber, the other end of photonic crystal fiber connects reflecting mirror by single mode optical fiber, form reflective MZI interference circuit；Photonic crystal fiber covering outer application cage molecule sensitive membrane, the sonde configuration that photonic crystal fiber methane transducer is constituted together with photonic crystal fiber and reflecting mirror with the single mode optical fiber of photon crystal optical fiber fusion splicing, coated with cage molecule sensitive membrane can make Photonic Crystal Fiber Sensor realize remote distributed real-time monitoring.
Description
Technical field
The invention belongs to technical field of optical fiber sensing, and in particular to a kind of photonic crystal fiber first based on sensitive membrane coating
Alkane sensor.
Background technique
Rich coal resources in China is coal production big country in the world, while being also that the most ground of mine disaster occurs in the world
One of area, coal production faces the Safety production questions of very severe, and hinders significant risk source --- the gas of safety in production
Disaster is then the major hidden danger of the dead group's wound of group.Gas is a kind of pernicious gas being adsorbed in coal body and surrounding rock stratum, and methane
It is mine gas main component, accounts for about 83~89%.The generation of gas accident brings about great losses to the country and people's property,
Safety of Coal Mine Production is drastically influenced, it is imperative that control gas accident occurs.Wherein, most effective means are monitoring methane gas
For effectively preventing gas accident methane content status information change in mine occurs and grasps in real time for bulk concentration, monitoring result
Change situation, evaluation gas control effect, improvement China's coal-mine safety production environment to have a very important significance.As detection
Firedamp sensor is directly related to coal mine safety monitoring system reliability and sensitivity, plays decisive action to monitoring.Mesh
Before, have based on the different types of methane transducer such as semiconductor, thermocatalytic, the interference of light, infrared absorption, electrochemical process, but all
Remote distributed real-time monitoring can not be carried out, brings significant limitations to gas monitor work, therefore, studying a kind of safety can
It leans on, highly sensitive distributed methane concentration remote detecting system, there are great economic results in society.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of photonic crystal fiber methane sensings based on sensitive membrane coating
Device, by photonic crystal fiber covering outer application cage molecule sensitive membrane, to the concentration of its methane with better photosensitivity
Change can make sensitive membrane refractive index change, and then change the effective refractive index of photonic crystal fiber airport covering, make to do
It relates to spectrum phase difference to change, wave crest or trough drift about, and realize methane concentration detection；And by reflective MZI interference light
Pass enters photonic crystal fiber, forms long tail type sonde configuration, is the functionization and distributed group of Photonic Crystal Fiber Sensor
Net provides new thinking.
The invention is realized in this way a kind of photonic crystal fiber methane transducer based on sensitive membrane coating, by broadband
Light source, single mode optical fiber, three-dB coupler, photonic crystal fiber, reflecting mirror, index-matching fluid and spectroanalysis instrument composition, 3dB
Two ports of coupler side pass through single mode optical fiber respectively and connect with wideband light source and spectroanalysis instrument, and three-dB coupler is another
By single mode optical fiber and photon crystal optical fiber fusion splicing, another leads to refractive index by single mode optical fiber for two ports one of side
With liquid, the other end of photonic crystal fiber connects reflecting mirror by single mode optical fiber；
The photonic crystal fiber cladding surface coats methane sensitive membrane, the single-mode optics with the photon crystal optical fiber fusion splicing
The fine, photonic crystal fiber coated with cage molecule sensitive membrane and reflecting mirror constitute the photonic crystal fiber methane sensing together
The sonde configuration of device.
Further, methane sensitive membrane is the sensitive membrane of cage type supramolecular materials Cryptophane A and E preparation.
Further, transmission of the light in photonic crystal fiber methane transducer forms reflective MZI optical interference circuit, transmission
Path is as follows: the wide spectrum optical that wideband light source issues is transmitted by single mode optical fiber, is divided into the equal two-way of light intensity by three-dB coupler,
It is incident in photonic crystal fiber through single mode optical fiber all the way, another way is incident in the index-matching fluid and is absorbed, incident
Light to photonic crystal fiber is reflected by a reflector via single mode optical fiber, again pass by photonic crystal fiber and with its welding
Single mode optical fiber and three-dB coupler, after being divided into two-beam, wherein a branch of be incident in spectroanalysis instrument is analyzed, another beam
Return to wideband light source.
Further, photonic crystal fiber is the pure quartzy photonic crystal fiber of single solid core.
Further, the welding process of photonic crystal fiber and single mode optical fiber is that superfusion collapses method, in photonic crystal fiber
Two endpoints at formed two point of collapse, so that the basic mode in single mode optical fiber is divided into the fibre core that two-way is coupled to photonic crystal fiber
And covering；
Light from incident direction enter first point of collapse when be divided into two-way respectively enter photonic crystal fiber fibre core and
Covering, when by another point of collapse, two-beam merges, and since two-beam meets interference condition, interferes in meeting point.
Further, wideband light source is ASE wideband light source, and output wavelength is between 1520nm~1570nm.
There are inner cavity (or holes) inside cage molecule, cooperate (complexing) effect due to existing, are very beneficial for methane point
Son is freely accessible to inside it.After methane molecule enters inner cavity, non-covalent bond phase can occur between cage molecule and methane molecule
Interaction forms molecule aggregate-supermolecule, and wherein cage molecule is receptor, and methane molecule is donor, inside cage molecule
There are occupy-place ratio between cavity volume and methane molecule volume to be measured, and methane is than non-methane gas, such as oxygen, hydrogen, dioxy
The volume for changing carbon will more greatly, and closer to optimal occupy-place ratio, also more stable, still, when methane molecule has just enter into, supermolecule is still
It plays pendulum, methane molecule will continue to make supermolecule be finally reached energy most to by the movement of the inner cavity of entad
Small structure.
Compared with the prior art, the advantages of the present invention are as follows: 1. by brand-new material cage molecule sensitive membrane and photonic crystal
Optical fiber combines, and realizes the Sensitive Detection to methane；2. reflective MZI interference circuit is introduced photonic crystal fiber, formed
Long tail type sonde configuration can make Photonic Crystal Fiber Sensor realize remote distributed real-time monitoring；3. pair photonic crystal light
The fine fusion point with single mode optical fiber collapses method using superfusion and carries out welding, and caused loss, makes list when reducing the two welding
Be incident in mode fiber in photonic crystal fiber optically coupling in airport covering, more excellent interference spectrum is formed, to first
The detection of alkane concentration is more accurate.
Detailed description of the invention
With reference to the accompanying drawing and embodiment the present invention is described in further detail:
Fig. 1 is the photonic crystal fiber methane transducer structural schematic diagram provided by the invention based on sensitive membrane coating；
Fig. 2 is photonic crystal fiber and single mode optical fiber fusion point image of microscope schematic diagram；
Fig. 3 is that optical path when light passes through single mode optical fiber and photon crystal optical fiber fusion splicing point moves towards schematic diagram；
Fig. 4 is the interference Frequency bias situation for coating the photonic crystal fiber methane transducer measurement of cage molecule A sensitive membrane
Result figure；
Fig. 5 be coat cage molecule A sensitive membrane photonic crystal fiber methane transducer measurement concentration of methane gas with
Relational graph between resonance paddy wavelength；
Fig. 6 is the interference Frequency bias situation for coating the photonic crystal fiber methane transducer measurement of cage molecule E sensitive membrane
Result figure；
Fig. 7 be coat cage molecule E sensitive membrane photonic crystal fiber methane transducer measurement concentration of methane gas with
Relational graph between resonance paddy wavelength.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, right below with reference to examples and drawings
The present invention is further elaborated, it should be understood that and specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.
As shown in Figure 1, showing for the photonic crystal fiber methane transducer structure provided by the invention based on sensitive membrane coating
It is intended to, including wideband light source 1, single mode optical fiber 2, three-dB coupler 3, photonic crystal fiber 4, reflecting mirror 5,6 and of index-matching fluid
Spectroanalysis instrument 7 forms, and two ports of 3 side of three-dB coupler pass through single mode optical fiber 2 and wideband light source 1 and spectrum point respectively
Analyzer 7 connects, and two ports one of 3 other side of three-dB coupler are another by single mode optical fiber 2 and 4 welding of photonic crystal fiber
A to lead to index-matching fluid 6 by single mode optical fiber 2, the other end of photonic crystal fiber 4 connects reflecting mirror by single mode optical fiber
5；4 covering outer application cage molecule sensitive membrane of photonic crystal fiber, single mode optical fiber 2, coating with 4 welding of photonic crystal fiber
There are the photonic crystal fiber 4 of cage molecule sensitive membrane and reflecting mirror 5 to constitute the probe of photonic crystal fiber methane transducer together
Structure.
The preparation and coating of cage molecule sensitive membrane:
The process of cage molecule of the present invention is made a living into reference to following equation:
The sensitive film preparation of cage molecule A and E weigh the powder 0.1g of the cage molecule A or E that prepare first, prepare
Cage molecule A or E are respectively put into and wherein dissolve by the tetrahydrofuran of 6ml, prepare silicone rubber K1000 solution, will prepare
Good Cage molecules solution is dissolved in wherein, is then added in solution curing agent K11, by the polymer-coated prepared to light
Then the cladding surface of photonic crystal fiber carries out baking at 80 DEG C~100 DEG C and accelerates solidification, the time is about 1 hour, can
It is repeatedly coated, increases sensitive film thickness, to improve the sensibility to methane.
The welding of photonic crystal fiber and single mode optical fiber: due to single mode optical fiber and during photon crystal optical fiber fusion splicing not
, there is very big loss, and the end face of two optical fiber is easy to produce gap and generates Fabry-Perot interference, to MZI in easily alignment
Interference generates interference, therefore collapses method using superfusion and carry out welding to the two, is photonic crystal fiber and single mode optical fiber with reference to Fig. 2
Fusion point image of microscope schematic diagram, Fig. 3 are optical path trend when light passes through single mode optical fiber and photon crystal optical fiber fusion splicing point, can
Know and is divided into fibre core and covering that two-way respectively enters photonic crystal fiber when light enters first point of collapse from incident direction, warp
When crossing another point of collapse, two-beam merges.
Detection of the photonic crystal fiber methane transducer to methane sensitivity: detection is adjusted with liquefied methane and liquid nitrogen
The concentration of methane, taking methane concentration respectively is 0%, 1%, 2%, 3%, 4%, and 5% is successively sensed with methane provided by the invention
Device measures.The sonde configuration of photonic crystal fiber methane transducer of the present invention is placed in the gas for having configured concentration, by
The light that wideband light source issues is divided into two beams by three-dB coupler, a branch of to be incident in photonic crystal fiber through single mode optical fiber, separately
A branch of be incident in index-matching fluid through single mode optical fiber is absorbed, two between single mode fibre and photonic crystal fiber welding
Point fusion point collapses completely, and expands waist diameter, forms two convex cones, and collapsing length is 206.53 μm, and cone waist width is
151.78 μm, when light beam passes through first collapse position, the core model of single mode optical fiber is divided into two-way and is respectively coupled to photon crystalline substance
Transmission in the fibre core and cladding mode of body optical fiber reaches second collapse position and assembles, interferes, be then followed by and be coupled to single mode
The fibre core of optical fiber, then reflected by silvered mirror, light beam backtracking is finally passed through again through the process of beam splitting, coupling
Three-dB coupler light splitting, is incident on ASE light source and spectrometer respectively, wherein the light beam for being incident on ASE light source is isolated, reaches light
The interference spectrum of the light beam of spectrometer can be shown by it and acquire related data.
Fig. 4,5 are the experimental result for carrying out experiment measurement using the sensing probe for being coated with cage molecule A sensitive membrane and obtaining
Figure, as shown in figure 4, when concentration of methane gas is 0% as we know from the figure, resonance paddy wavelength is interference Frequency bias situation
1556.24nm, when concentration of methane gas is 1%, resonance paddy wavelength is 1556.24nm, when concentration of methane gas is 2%, resonance
Paddy wavelength is 1555.32nm, and when concentration of methane gas is 3%, resonance paddy wavelength is 1554.12nm, concentration of methane gas 4%
When, resonance paddy wavelength is 1553.08nm, and when concentration of methane gas is 5%, resonance paddy wavelength is 1551.96nm, thus obtains figure
Relationship between 5 concentration of methane gas and resonance paddy wavelength, it is known that the drift of resonance paddy wavelength linearly reduces with methane concentration
Trend, right Linear Quasi is 0.999, and within the scope of 0%~5% concentration of methane gas, measurement sensitivity of the invention reaches
106.63nm/ percentage.
Fig. 6,7 are the experimental result for carrying out experiment measurement using the sensing probe for being coated with cage molecule E sensitive membrane and obtaining
Figure, interference Frequency bias situation are as shown in Figure 6, it is known that when concentration of methane gas is 0%, resonance paddy wavelength is 1563.65nm, methane
When gas concentration is 1%, resonance paddy wavelength is 1561.85nm, and when concentration of methane gas is 2%, resonance paddy wavelength is
1560.42nm, when concentration of methane gas is 3%, resonance paddy wavelength is 1559.12nm, when concentration of methane gas is 4%, resonance
Paddy wavelength is 1557.96nm, and when concentration of methane gas is 5%, resonance paddy wavelength is 1557.15nm, thus obtains Fig. 7 methane gas
Relationship between bulk concentration and resonance paddy wavelength, it is known that the trend that the drift of resonance paddy wavelength linearly reduces with methane concentration,
Right Linear Quasi is 0.9853, and within the scope of 0%~5% concentration of methane gas, it is dense that wave length shift sensitivity reaches 129.91nm/
Spend percentage；Compared with the photonic crystal fiber methane transducer made of the cage molecule A sensitive membrane, the first of cage molecule E is coated
Alkane transducer sensitivity has a certain upgrade, and reason may be related with chamber size in sensitive membrane quality of forming film and cage molecule.
Claims (5)
1. a kind of photonic crystal fiber methane transducer based on sensitive membrane coating, which is characterized in that by wideband light source, single-mode optics
Fibre, three-dB coupler, photonic crystal fiber, reflecting mirror, index-matching fluid and spectroanalysis instrument composition, the three-dB coupler one
Two ports of side pass through the single mode optical fiber respectively and connect with the wideband light source and spectroanalysis instrument, the three-dB coupler
By single mode optical fiber and photon crystal optical fiber fusion splicing, another leads to refraction by single mode optical fiber for two ports one of the other side
The other end of rate matching fluid, the photonic crystal fiber connects reflecting mirror by single mode optical fiber；
The photonic crystal fiber cladding surface coats methane sensitive membrane, with the single mode optical fiber of the photon crystal optical fiber fusion splicing,
Photonic crystal fiber and reflecting mirror coated with methane sensitive membrane constitute the spy of the photonic crystal fiber methane transducer together
Header structure；
The methane sensitive membrane is the sensitive membrane of cage type supramolecular materials Cryptophane A and E preparation；
The preparation of the methane sensitive membrane, coating method are as follows:
The powder 0.1g for weighing cage type supramolecular materials Cryptophane A and E first, prepares the tetrahydrofuran of 6ml, by cage type
Supramolecular materials Cryptophane A and E, which are respectively put into, wherein to be dissolved, and is prepared silicone rubber K1000 solution, will be prepared
Cage molecules solution be dissolved in wherein, then curing agent K11 is added in solution, by the polymer-coated prepared to photon
Then the cladding surface of crystal optical fibre carries out baking at 80 DEG C~100 DEG C and accelerates solidification, the time is 1 hour, is repeatedly carried out
Coating increases sensitive film thickness, to improve the sensibility to methane.
2. the photonic crystal fiber methane transducer according to claim 1 based on sensitive membrane coating, which is characterized in that light
Transmission in the photonic crystal fiber methane transducer forms reflective MZI optical interference circuit, and transmission path is as follows: the width
The wide spectrum optical issued with light source is transmitted by single mode optical fiber, is divided into the equal two-way of light intensity by three-dB coupler, all the way through single-mode optics
Fibre is incident in photonic crystal fiber, and another way is incident in the index-matching fluid and is absorbed, and is incident on photonic crystal light
Fine light is reflected by a reflector via single mode optical fiber, again passes by the photonic crystal fiber and the single mode optical fiber with its welding
And three-dB coupler, after being divided into two-beam, wherein a branch of be incident in the spectroanalysis instrument is analyzed, another beam is returned
Wideband light source.
3. the photonic crystal fiber methane transducer according to claim 1 based on sensitive membrane coating, which is characterized in that institute
Photonic crystal fiber is stated as the pure quartzy photonic crystal fiber of single solid core.
4. the photonic crystal fiber methane transducer according to claim 1 based on sensitive membrane coating, which is characterized in that institute
It states the welding process of photonic crystal fiber and single mode optical fiber and collapses method for superfusion, at two endpoints of the photonic crystal fiber
Two point of collapse are formed, the basic mode in the single mode optical fiber is made to be divided into fibre core and covering that two-way is coupled to photonic crystal fiber；
Light from incident direction enter first point of collapse when be divided into two-way respectively enter the photonic crystal fiber fibre core and
Covering, when by another point of collapse, two-beam merges, and since two-beam meets interference condition, interferes in meeting point.
5. the photonic crystal fiber methane transducer according to claim 1 based on sensitive membrane coating, which is characterized in that institute
Stating wideband light source is ASE wideband light source, and output wavelength is between 1520nm~1570nm.
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| CN105973807A (en) * | 2016-06-01 | 2016-09-28 | 浙江工商大学 | Optical fiber sensing probe for detecting gas and liquid |
| CN106198409B (en) * | 2016-07-26 | 2018-08-21 | 重庆大学 | A kind of gas concentration many reference amounts detection device |
| CN110132894B (en) * | 2019-05-16 | 2022-09-09 | 中国矿业大学 | Temperature-compensated photonic crystal fiber methane sensing device |
| CN114136923A (en) * | 2021-11-29 | 2022-03-04 | 华北电力大学 | Online measurement system for dissolved methane in transformer oil |
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| CN102183485B (en) * | 2010-12-17 | 2012-12-19 | 重庆大学 | Methane sensing device based on long-period fiber grating |
| CN102169209A (en) * | 2011-05-19 | 2011-08-31 | 北京工业大学 | Method for low loss welding and end face treatment of photonic crystal optical fiber |
| CN102359943B (en) * | 2011-06-23 | 2013-06-12 | 天津大学 | Photonic crystal fibre-optical air chamber active cavity absorption-type gas detection device |
| CN102288563A (en) * | 2011-07-21 | 2011-12-21 | 天津大学 | Active cavity absorption acetylene concentration detection system and method thereof |
| CN102788768A (en) * | 2012-07-10 | 2012-11-21 | 东北大学 | Method for measuring liquid refractive index based on novel reflection-type fiber loop mirror |
| CN104568841B (en) * | 2014-12-18 | 2017-02-08 | 重庆大学 | Photonic crystal optical fiber methane sensing device based on modular interference |
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