CN115356288A - Micro-nano optical fiber gas sensor based on in-situ growth polymer and preparation method - Google Patents
Micro-nano optical fiber gas sensor based on in-situ growth polymer and preparation method Download PDFInfo
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- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/0229—Optical fibres with cladding with or without a coating characterised by nanostructures, i.e. structures of size less than 100 nm, e.g. quantum dots
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Abstract
The invention discloses a micro-nano optical fiber gas sensor based on in-situ growth polymers and a preparation method thereof, wherein the method comprises the following steps: the input optical fiber and the optical fiber grating area probe are connected in sequence; the probe part of the fiber grating area is etched, and the surface of the probe of the fiber grating area is covered with a PANI film which is formed by in-situ growth on the surface of the probe of the fiber grating area; the PANI film can adsorb set gas in the environment to reduce the conductivity of the set gas, so that the shift of the central wavelength of a reflection spectrum in the fiber grating is caused, and the detection of the concentration of the set gas is realized. According to the invention, the refractive index sensitivity characteristic of the micro-nano optical fiber and the gas-sensitive characteristic of the PANI are organically combined, the PANI film grows in situ on the surface of the optical fiber grid region, and the obtained sensor has high sensitivity, fast response/recovery time and good stability; can be used in the testing of gas, liquid composition or concentration.
Description
Technical Field
The invention relates to the technical field of optical fiber sensing, in particular to a micro-nano optical fiber gas sensor based on an in-situ grown polymer and a preparation method thereof.
Background
The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.
With the rapid development of modern industry, the discharge amount of various industrial waste gases is increasing, and a large amount of toxic gases and flammable and explosive gases are contained, so that the environment is polluted, and the human health is also harmed. The power battery of the new energy vehicle and the energy storage battery of the energy storage power station also generate various toxic gases and combustible and explosive gases after damage and before spontaneous combustion, and if the toxic gases and the combustible and explosive gases can be detected and treated properly in time, spontaneous combustion and even explosion accidents of the batteries can be avoided.
Wherein ammonia gas (NH) 3 ) Is a typical colorless and irritant toxic and harmful gas, and is a common air pollutant. Meanwhile, ammonia gas with a certain concentration can cause harm to human health. When one is at 25ppm NH 3 8h, even 35ppm NH under the environment 3 At medium time of 15min, NH 3 Can cause serious injury to eyes and respiratory tract of people. Therefore, the NH in the pollution source or the atmospheric environment can be timely and accurately monitored and controlled 3 And the concentration of toxic and harmful gases has great significance for environmental protection and human health.
The traditional electrochemical gas sensor has higher sensitivity and precision, but has poor anti-interference performance and high use temperature; the spectrum absorption type gas sensor has the advantages of large volume and high cost, and is difficult to realize in-situ online monitoring in high-dust, high-humidity and vibration environments.
Compared with the traditional sensor, the optical fiber gas sensor has the advantages of strong anti-interference performance, high selectivity, reusability, low working temperature, high response speed, capability of monitoring gas on line in situ in real time and the like. The fiber grating gas sensor is one of the widely studied fiber grating gas sensors, and utilizes the contact between gas and the gas sensitive material on the surface of the fiber grating area to induce the transmission spectrum or reflection spectrum of the fiber grating to change to some extent, so as to realize the sensing of gas. The fiber grating mainly comprises: short Period Fiber gratings, i.e., fiber Bragg Gratings (FBGs) and Long Period Fiber Gratings (LPFGs).
Compare in LPFG sensor, FBG sensor's interference killing feature is stronger, and the performance is more stable, but the fibre core of the FBG of commercialization is wrapped up by thick cladding, can't direct and external environment contact, consequently can't be based on the principle that optical refractive index changes and directly be used for gaseous detection.
Therefore, most of the current researches on biochemical sensing are carried out by using LPFG sensors, and many difficulties still need to be overcome for researches on detecting trace gases and changes thereof by using FBG sensors.
The prior art discloses a preparation method of an FBG gas sensor, which adopts a preparation method of an FBG sensor with a thermal rotation coated polymer film, and the surface of an optical fiber grating area is coated with a gas-sensitive polymer film, so that the coating quality of the polymer film on the surface of the optical fiber grating area can be ensured, and the thickness of the film is uniform; however, the optical fiber sensor utilizes the volume expansion or contraction effect generated by the polymer film coated on the surface of the optical fiber gate region after adsorbing gas, so that the gate pitch of the FBG is changed to achieve the purpose of gas detection.
Disclosure of Invention
In order to solve the problems, the invention provides a micro-nano optical fiber gas sensor based on an in-situ grown polymer and a preparation method thereof, wherein the gas concentration is detected by utilizing the characteristic that the micro-nano optical fiber is sensitive to the optical refractive index of the environment; meanwhile, in order to solve the problems of low sensitivity and poor selectivity, polyaniline (PANI) is introduced as a gas sensitive material, PANI grows in situ on the surface of a grid region of the etched fiber grating and is subjected to necessary modification treatment, and meanwhile, the appropriate thickness and coating uniformity of a PANI film layer are obtained by monitoring the intensity of a reflection spectrum in the growth process of a polymer in real time so as to ensure good and stable signal intensity of the optical fiber and effectively ensure the bonding firmness of the PANI and the surface of the grid region of the fiber grating.
In some embodiments, the following technical scheme is adopted:
a micro-nano optical fiber gas sensor based on in-situ growth polymers comprises: the input optical fiber and the optical fiber grating area probe are connected in sequence; the fiber grating area probe part is subjected to etching treatment, the surface of the fiber grating area probe is covered with a PANI film, and the PANI film is formed by in-situ growth on the surface of the fiber grating area probe.
The PANI film can adsorb set gas in the environment to reduce the conductivity of the set gas, so that the shift of the central wavelength of a reflection spectrum in the fiber grating is caused, and the detection of the concentration of the set gas is realized.
As a specific example, the fiber grating region probe described above may be an FBG fiber grating region probe. According to the invention, the optical refractive index sensitivity characteristic of the micro-nano FBG optical fiber gas sensor and the gas sensitivity characteristic of PANI are organically combined, and the PANI film grows in situ on the surface of the optical fiber grating region, so that the problems of low gas sensitivity and poor selectivity of the FBG sensor are solved; meanwhile, the technical problems of thickness control and uniform coating of the polymer on the surface of the FBG fiber bragg grating and stable and firm combination with the FBG fiber bragg grating are effectively solved by the mode of in-situ growth of the PANI film.
In other embodiments, the following technical solutions are adopted:
a preparation method of a micro-nano optical fiber gas sensor based on in-situ growth polymers comprises the following steps:
etching the fiber grating region, monitoring the central wavelength of the fiber grating reflection spectrum, and soaking the grating region with deionized water to remove impurities remaining on the surface of the grating region after the central wavelength deviates a set value;
taking out the optical fiber from the deionized water, and carrying out surface treatment on the gate region; then, drying the optical fiber;
and carrying out in-situ growth of PANI on the surface of the fiber grating region.
As a further scheme, the process of performing the in-situ growth of PANI on the surface of the fiber gate region specifically comprises:
dispersing an aniline monomer in an acid solution with a set pH value to form an aniline-acid solution;
uniformly dispersing initiator ammonium persulfate in an acid solution with the same pH value as the pH value to form an ammonium persulfate-acid solution;
vertically immersing the optical fiber grating area subjected to surface treatment into the aniline-acid solution, and cooling; adding the ammonium persulfate-acid solution into the aniline-acid solution to form a reaction solution, so that aniline starts to grow on the surface of the grid region in a polymerization manner;
and simultaneously monitoring the intensity of the central wavelength of the reflection spectrum of the fiber grating, and taking out the optical fiber after the set requirement is met.
As a further scheme, after the in-situ growth is finished, the method further comprises the following steps:
immersing the optical fiber into deionized water to clean impurities remained on the surface of the gate region;
completely immersing the gate region into an ammonia solution to perform the de-doping treatment of the PANI film;
taking out the optical fiber from the ammonia water solution, immersing the optical fiber into deionized water to remove ammonia molecules remained on the surface, immersing the optical fiber into a corresponding acid solution, and regulating the pH value of the optical fiber to re-dope the PANI film; and finally, taking out the optical fiber and fully drying the optical fiber.
In other embodiments, the following technical solutions are adopted:
for detecting NH 3 A concentration sensing system comprising: the fiber grating demodulator, the micro-nano fiber gas sensor and the computer; the input optical fiber of the micro-nano optical fiber gas sensor is connected with an optical fiber grating demodulator, and the optical fiber grating demodulator is connected with a computer.
By carrying out NH 3 When the concentration is detected, the optical signal output by the built-in light source of the fiber grating demodulator passes through the micro-nano fiber gas sensorThe input optical fiber enters a grid region, and a PANI film on the surface of the grid region adsorbs NH in the environment 3 ，NH 3 The molecules capture protons on the imine nitrogen in the PANI molecular chain to reduce the conductivity of the PANI film, so that the central wavelength of the reflection spectrum in the fiber core is shifted, and NH is calculated 3 The concentration of (c).
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention organically combines the refractive index sensitivity characteristic of the micro-nano optical fiber and the gas-sensitive characteristic of the PANI, the PANI film grows on the surface of the optical fiber grid region in situ, and the obtained sensor can detect NH with the concentration range of 1-100 ppm 3 The method has the advantages of high sensitivity, quick response/recovery time and good stability; can be used in the testing of gas, liquid composition or concentration.
(2) In the process of in-situ growth of PANI on the surface of the optical fiber gate region, the signal change of the micro-nano optical fiber grating is monitored in real time by a demodulator, and the growth speed and the appearance of the PANI are controlled by adjusting the pH value of the reaction solution, so that a porous PANI film with uniform particle size and uniform thickness can be prepared, and the PANI film is firmly combined with the surface of the optical fiber gate region and is not easy to fall off; the gas sensor with stable signal, moderate film thickness and excellent gas-sensitive performance can be obtained.
(3) The processes of dedoping and re-doping of the PANI film are to remove unreacted small molecules, oligomers and initiator molecules in the reaction process and eliminate the interference of the unreacted small molecules, oligomers and initiator molecules on the gas-sensitive performance of a sensor, and to realize reversible regulation and control on the PANI conductivity and obtain NH 3 Rapid response/reply feature.
Additional features and advantages of additional aspects of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a schematic structural diagram of a micro-nano FBG gas sensor in an embodiment of the invention;
FIG. 2 is a diagram of an embodiment of the present invention for detecting NH 3 A structural schematic diagram of a concentration sensing system;
fig. 3 is an electron microscope photograph of a micro-nano optical fiber with PANI grown in situ on the surface in an embodiment of the invention;
FIG. 4 shows micro-nano FBGNH based on surface in-situ growth PANI in the embodiment of the invention 3 Response value of sensor and NH 3 A concentration dependence;
FIG. 5 is a stability test curve for a sensor of an embodiment of the present invention over 60 days;
wherein, 1, inputting optical fiber, 2, optical fiber grating area probe, 3, optical fiber grating demodulator, 4, computer; 101. protective layer, 102 cladding, 103 core, 201 grating, 202 pani film.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Example one
As the background, the micro-nano optical fiber is self-aligned to NH 3 The present example solves this problem by coating a special ammonia-sensitive material, because the detection sensitivity of (b) is low and does not have excellent gas selectivity. The main challenges of the prior art are how to realize the optimization and processing of the diameter of the fiber grating, how to realize the optimization and modification processing of the sensitive coating material on the basis of the diameter, how to realize the thickness control and uniform coating of the sensitive coating material on the surface of the fiber grating, and how to stably and firmly combine the sensitive coating material with the fiber grating.
Based on this, in one or more embodiments, a micro-nano optical fiber gas sensor based on a polymer grown in situ on a surface is disclosed, in this embodiment, an FBG gas sensor is taken as an example (of course, other micro-nano optical fibers based on a refractive index sensitivity mechanism are also within the protection range of the present invention, and the same is true in the following examples), and with reference to fig. 1, specifically, the method includes: the input optical fiber 1 and the optical fiber grating area probe 2 are connected in sequence; the input optical fiber 1 is a single-mode optical fiber and comprises a fiber core 103, a cladding 102 and a protective layer 101 which are sequentially arranged from inside to outside; the fiber grating area probe 2 is etched, a grating 201 is arranged inside the fiber grating area probe, a PANI film 202 covers the surface of the fiber grating area probe 2, and the PANI film is formed by in-situ growth on the surface of the fiber grating area probe.
In this embodiment, a fiber bragg grating is used, the fiber diameter is 250 μm, the gate region diameter (after removing the polyimide or polyamide protective layer on the surface) is 125 μm, the fiber core diameter is about 8-9 μm, and the length of each gate region is 3-10 mm.
The diameter of the probe in the fiber grating area is 4-12 mu m, and the surface of the probe is covered with a PANI film; the thickness of the PANI film is 0.1-2 μm, and the PANI film is formed by in-situ growth on the surface of the probe in the fiber grating area.
The PANI membrane can adsorb set gas (such as NH) in the environment 3 ) The conductivity of the gas is reduced, so that the central wavelength of a reflection spectrum in the fiber grating is shifted, and the detection of the set gas concentration is realized.
The thickness of the PANI film is related to the in-situ growth time, the in-situ growth time is determined by the intensity of a reflection spectrum in the fiber grating, and the in-situ growth is controlled to be finished when the intensity of the reflection spectrum is attenuated to a set range.
In some embodiments, further comprising: the device comprises a substrate for fixing a fiber grating area probe, wherein two ends of the fiber grating area probe are fixed on the substrate. The substrate for fixing the grid region can be used for fixing the etched grid region, and adverse effects on PANI in-situ growth and gas-sensitive test process caused by unstable fluctuation in the subsequent operation process are avoided.
PANI is widely used in the field of gas sensing because of its good chemical and environmental stability, low price, simple synthesis, controllable conductivity, and unique doping method. In the embodiment, PANI is introduced as a sensitive material, the refractive index sensitive property of the micro-nano optical fiber and the gas sensitive property of the PANI are organically combined, and a PANI film grows in situ on the surface of the optical fiber grid region, so that the problem that the FBG sensor is not sensitive to gas detection is solved; meanwhile, the technical problems of thickness control and uniform coating of the polymer on the surface of the fiber grating and stable and firm combination with the fiber grating are effectively solved by the in-situ growth mode of the PANI film.
The micro-nano FBG gas sensor based on the surface in-situ growth polymer has high detection precision, high sensitivity and excellent stability, and can be used for testing components or concentrations of gas and liquid, such as: can realize the reaction to NH 3 、H 2 S、N 2 And detecting the concentration of gas such as O and the like.
Example two
In one or more embodiments, a method for preparing a micro-nano optical fiber gas sensor based on a surface in-situ growth polymer is disclosed, which also takes an FBG gas sensor as an example, and specifically comprises the following steps:
step (1): connecting an optical fiber with a demodulator, etching the optical fiber grating region by using hydrofluoric acid (HF) solution, taking out the optical fiber when the blue shift of the central wavelength of the optical fiber grating reflection spectrum is monitored to be 1.2-1.8 nm, and cleaning the surface of the grating region for multiple times by using deionized water to remove residual HF molecules on the surface of the grating region;
step (2): taking out the optical fiber from the deionized water, and carrying out surface treatment on the gate region; the surface treatment method can be selected from ammonia water-hydrogen peroxide (NH) 3 ·H 2 O-H 2 O 2 ) The aqueous solution of (2) can be soaked, or can be soaked by adopting a silane coupling agent solution;
wherein NH 3 ·H 2 O-H 2 O 2 The aqueous solution is prepared by dissolving NH 3 ·H 2 O、H 2 O 2 Preparing a solution with deionized water according to a certain volume ratio; the silane coupling agent can be selected from vinyl silane and amino silaneOr a methacryloxy silane type coupling agent.
And (3): placing the optical fiber subjected to surface treatment in a drying box for drying treatment, wherein the temperature of the drying box is controlled to be 60-120 ℃;
and (4): and carrying out in-situ growth of PANI on the surface of the fiber grating region.
In this step, the specific process of in-situ growth of PANI is as follows:
step (4-1): dispersing an aniline monomer in an acid solution with a certain pH value to form an aniline-acid solution; wherein the acid solution can be one of inorganic acid or organic acid, such as hydrochloric acid, sulfuric acid or camphorsulfonic acid.
Step (4-2): and dispersing initiator ammonium persulfate in an acid solution with the same pH value as the pH value, and uniformly stirring to form an ammonium persulfate-acid solution.
Step (4-3): vertically immersing the surface-treated optical fiber grid region into the aniline-acid solution, placing the optical fiber grid region into an ice water bath (0-5 ℃) for cooling, and then dropwise and slowly adding the ammonium persulfate-acid solution into the aniline-acid solution to enable aniline to start to grow on the surface of the grid region in a polymerization manner;
step (4-4): the intensity of the central wavelength of the optical fiber grating region reflection spectrum output by the demodulator on the computer is observed, and when the intensity is reduced to a certain range, the optical fiber is taken out.
In this embodiment, the thickness of the PANI film grown on the surface of the fiber gate region is related to the growth time, and the longer the in-situ growth time is, the thicker the film is. However, the PANI film in this embodiment is not too thick, which easily causes the signal intensity of the optical fiber to be attenuated too much to be detected. Therefore, the time for finishing the growth of the polymer film needs to be controlled by monitoring the signal intensity change condition in the growth process in real time and attenuating the signal intensity to a certain range, that is, the film thickness meeting the signal intensity range of the optical fiber is more suitable.
After the in-situ growth process is completed, the acid doping and re-doping treatment of the PANI is carried out, and the specific process is as follows:
taking out the optical fiber after the PANI surface growth is completed, and soaking the optical fiber into deionized water to clean the unreacted aniline monomer, oligomer, initiator and other impurities remained on the surface of the gate region; then completely immersing the gate region into an ammonia water solution for a period of time, and carrying out the dedoping treatment of the PANI film; finally, taking out the optical fiber from the ammonia water solution, immersing the optical fiber into deionized water to remove ammonia molecules remained on the surface, immersing the optical fiber into a corresponding acid solution for a period of time, and regulating the pH value of the optical fiber to re-dope the PANI film; after completion, the fiber was taken out and transferred to a drying oven, and sufficiently dried.
In the embodiment, the processes of dedoping and re-doping the PANI film are used for removing unreacted aniline monomers, oligomers and residual initiator molecules in the reaction process, eliminating the interference of the aniline monomers and oligomers on the gas-sensitive performance of the sensor and obtaining the sensor with stable performance; on the other hand, in order to realize the reversible regulation and control of PANI conductivity, NH is obtained 3 Rapid response/reply feature.
The production method of this example will be specifically described below in various embodiments.
1. Hydrochloric acid doped PANI micro-nano optical fiber NH 3 The preparation process of the sensor is taken as an example, and the preparation method of the embodiment is specifically described.
In this embodiment, a 40wt% HF solution is first used to etch the gate region of the FBG, and when the etching is performed until the central wavelength of the reflection spectrum of the gate region is blue-shifted by 1.2nm, the optical fiber is taken out and the surface of the gate region is cleaned with deionized water for multiple times, and an SEM photograph of the etched bare optical fiber is shown in (a) in fig. 3. Then soaking the fiber grating region in NH 3 ·H 2 O-H 2 O 2 In an aqueous solution (ratio NH) 3 ·H 2 O：H 2 O 2 ：H 2 O =1:1: 5) After 3h, the fiber was taken out and dried in a drying oven at 40 ℃ for 2h. And (3) placing the dried optical fiber gate region in an aniline-hydrochloric acid solution, wherein the pH value of the solution is 0.3, the concentration of aniline is 0.1mol/L, after the whole optical fiber gate region is placed in an ice water bath for cooling for 30min, slowly dropwise adding an ammonium persulfate-hydrochloric acid solution (0.025 mol/L) into the aniline-hydrochloric acid solution, and starting the in-situ growth of PANI on the surface of the optical fiber gate region. Is composed ofAnd then, connecting the optical fiber to a demodulator, monitoring the intensity change of the reflection spectrum in real time on a software user interface of a computer, taking out the optical fiber until the intensity of the reflection spectrum is reduced to-25 dB, and immersing the optical fiber in deionized water to clean impurity molecules remained on the surface. And then soaking the optical fiber grating region in 1% ammonia water solution for 30min, taking out the optical fiber grating region, cleaning with deionized water, soaking in hydrochloric acid solution with the same pH value for 30min for re-doping, taking out the optical fiber after the re-doping, and drying in a drying oven at 40 ℃ for 2h. As shown in fig. 3 (b), the SEM photograph of the fiber gate region with PANI grown on the surface thereof obtained in this example shows that a PANI film is uniformly grown on the surface of the fiber gate region, and the PANI film has uniform particle size, uniform thickness, and multiple pores, and is firmly bonded to the fiber gate region without a defect of peeling.
2. NH of micro-nano FBG (fiber Bragg Grating) doped with PANI (polyaniline) by hydrochloric acid 3 The preparation process of the sensor is taken as an example, and the preparation method of the embodiment is specifically described.
In this embodiment, a 24wt% HF solution is first used to etch the grating region of the FBG, and when the etching is performed until the central wavelength of the reflection spectrum of the grating region is blue-shifted by 1.4nm, the optical fiber is taken out and the surface of the grating region of the optical fiber is repeatedly cleaned with deionized water. Then soaking the fiber grating region in an aqueous solution of KH550 (gamma-aminopropyltriethoxysilane) for 2h, then taking out the fiber and placing the fiber in a drying oven to dry for 2h at 80 ℃. And (3) placing the dried optical fiber gate region in an aniline-hydrochloric acid solution, wherein the pH value of the solution is 0, the concentration of aniline is 0.1mol/L, placing the whole in an ice-water bath for cooling for 30min, slowly dropwise adding an ammonium persulfate-hydrochloric acid solution (0.05 mol/L) into the aniline-hydrochloric acid solution, and starting the in-situ growth of PANI on the surface of the optical fiber gate region. Meanwhile, the optical fiber is connected to a demodulator, the intensity change of the reflection spectrum is monitored in real time on a software user interface of a computer, the optical fiber is taken out until the intensity of the reflection spectrum is reduced to-30 dB, and the optical fiber is immersed in deionized water to clean impurity molecules remained on the surface. And then soaking the optical fiber grating region in 1% ammonia water solution for 30min, taking out the optical fiber grating region, cleaning the optical fiber grating region with deionized water, soaking the optical fiber grating region in hydrochloric acid solution with the same pH value for 60min for re-doping, taking out the optical fiber after the completion, and drying the optical fiber in a drying oven at 40 ℃ for 3h. As shown in fig. 3 (c), the SEM photograph of the fiber gate region with PANI grown on the surface thereof prepared in this example shows that a PANI film is uniformly grown on the surface of the fiber gate region, and the PANI film has a uniform particle size and a thickness greater than that of the fiber gate region in example 1, and is tightly bonded to the fiber gate region without a defect of peeling.
The gas-sensitive performance of the sensor prepared according to the technical scheme is tested, and the sensor is respectively placed in NH with the content of 10ppm, 20ppm, 50ppm and 100ppm 3 After the central wavelength of the reflection spectrum of the fiber grating region displayed on the user interface of the computer software is stable, the offset value of the closed container is calculated to obtain the wavelength offset and NH shown in FIG. 4 3 The concentration relationship curve shows that the sensor prepared by the embodiment is used for measuring NH in the range of 10-100 ppm 3 Has better response.
3. NH of micro-nano FBG (fiber Bragg Grating) doped with PANI (polyaniline) by camphorsulfonic acid 3 The preparation process of the sensor is taken as an example, and the preparation method of the embodiment is specifically described.
In this embodiment, a 24wt% HF solution is first used to etch the grating region of the FBG, and when the etching is performed until the central wavelength of the reflection spectrum of the grating region is blue-shifted by 1.4nm, the optical fiber is taken out and the surface of the grating region of the optical fiber is repeatedly cleaned with deionized water. Then soaking the fiber grating region in NH 3 ·H 2 O-H 2 O 2 Aqueous solution (ratio NH) 3 ·H 2 O：H 2 O 2 ：H 2 O =1:1: 5) After 3h, the fiber was taken out and dried in a drying oven at 40 ℃ for 2h. And (3) placing the dried optical fiber gate region into an aniline-camphorsulfonic acid solution, wherein the pH value of the solution is 0.3, the concentration of aniline is 0.1mol/L, integrally placing the optical fiber gate region into an ice-water bath for cooling for 30min, and then slowly dropwise adding an ammonium persulfate-camphorsulfonic acid solution (0.05 mol/L) into the aniline-camphorsulfonic acid solution to start the in-situ growth of PANI on the surface of the optical fiber gate region. Meanwhile, the optical fiber is connected to a demodulator, the intensity change of the light reflection spectrum is monitored in real time on a software user interface of a computer, the optical fiber is taken out until the intensity of the reflection spectrum is reduced to-30 dB, and the optical fiber is immersed in deionized water to clean impurity molecules remained on the surface. Then the optical fiber is connectedSoaking the grid region in 1% ammonia water solution for 30min, taking out the optical fiber grid region, cleaning with deionized water, soaking in camphorsulfonic acid solution with the same pH value for 60min for re-doping, taking out the optical fiber after the re-doping, and drying in a drying oven at 40 deg.C for 3h. As shown in fig. 3 (d), the SEM photograph of the fiber gate region with PANI grown on the surface thereof prepared in this example shows that a PANI film is uniformly grown on the surface of the fiber gate region, and the PANI film has a uniform particle size and a thickness greater than that of the fiber gate region in example 1, and is tightly bonded to the fiber gate region without a defect of peeling.
The gas-sensitive stability of the sensor prepared according to the technical scheme is tested, and the sensor is placed in 100ppm of NH every 5 days 3 The response test was performed once and the wavelength deviation value was recorded in the closed container of (1), and a total of 12 tests for 60 days were performed, and the stability curve of the sensor as shown in fig. 5 was obtained, and it can be seen that the sensor prepared in this example has excellent stability.
EXAMPLE III
In one or more embodiments, a method for detecting NH is disclosed 3 The embodiment of the concentration sensing system is NH of a micro-nano FBG 3 The sensor is described as an example, and with reference to fig. 2, specifically includes: fiber grating demodulator 3, NH of micro-nano FBG in the first embodiment 3 A sensor and computer 4; NH of micro-nano FBG 3 The input optical fiber 1 of the sensor is connected with the fiber grating demodulator 3, and the fiber grating demodulator 3 is connected with the computer 4.
NH of micro-nano FBG in this embodiment 3 The sensor can be prepared as described in example two.
When detecting gas, the sensor is placed in a certain concentration of NH 3 In the environment; NH in PANI film adsorption environment on surface of optical fiber gate region 3 ，NH 3 The molecules capture protons on the imine nitrogen in the PANI molecular chain to reduce the conductivity of the PANI film, so that the effective refractive index of the PANI/micro-nano fiber grating composite waveguide is changed, the central wavelength of the fiber core reflection spectrum is finally shifted, and N in the environment can be obtained through software calculation in a computerH 3 The concentration of (c).
This embodiment is based on little nanofiber NH of surface normal position growth PANI 3 Sensor, acid doped PANI vs NH 3 Has reversible adsorption/desorption characteristics, and can obviously improve the NH detection of the sensor 3 Sensitivity of the molecule and effective reduction of response/recovery time; adsorption/desorption of NH by PANI 3 The conductivity and dielectric constant of the PANI film are changed, so that the refractive index of the PANI film is changed, the effective refractive index of the PANI/micro-nano optical fiber composite waveguide is further changed, and the effect of different NH concentrations is realized 3 Detection of (3).
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive changes in the technical solutions of the present invention.
Claims (10)
1. A micro-nano optical fiber gas sensor based on in-situ growth polymer is characterized by comprising: the input optical fiber and the optical fiber grating area probe are connected in sequence; the probe part of the fiber grating area is etched, and the surface of the probe of the fiber grating area is covered with a PANI film which is formed by in-situ growth on the surface of the probe of the fiber grating area;
the PANI film can adsorb set gas in the environment to reduce the conductivity of the set gas, so that the shift of the central wavelength of a reflection spectrum in the fiber grating is caused, and the detection of the concentration of the set gas is realized.
2. The in-situ growth polymer-based micro-nano optical fiber gas sensor according to claim 1, further comprising: the device comprises a substrate for fixing a fiber grating area probe, wherein two ends of the fiber grating area probe are fixed on the substrate.
3. The in-situ grown polymer-based micro-nano optical fiber gas sensor according to claim 1, wherein the thickness of the PANI film is related to in-situ growth time, the in-situ growth time is determined by the intensity of a reflection spectrum in a fiber grating, and the in-situ growth is controlled to be finished when the intensity of the reflection spectrum is attenuated to a set range.
4. A preparation method of a micro-nano optical fiber gas sensor based on in-situ growth polymers is characterized by comprising the following steps:
etching the fiber grating region, monitoring the central wavelength of the fiber grating reflection spectrum, and soaking the grating region with deionized water to remove impurities remaining on the surface of the grating region after the central wavelength deviates a set value;
taking out the optical fiber from the deionized water, and carrying out surface treatment on the gate region; then, drying the optical fiber;
and carrying out in-situ growth of PANI on the surface of the fiber grating region.
5. The method for preparing a micro-nano optical fiber gas sensor based on in-situ growth polymer according to claim 4, wherein the process of in-situ growth of PANI on the surface of the fiber grating region specifically comprises:
dispersing an aniline monomer in an acid solution with a set pH value to form an aniline-acid solution;
uniformly dispersing initiator ammonium persulfate in an acid solution with the same pH value as the pH value to form an ammonium persulfate-acid solution;
vertically immersing the surface-treated optical fiber grating region into the aniline-acid solution, and cooling; adding the ammonium persulfate-acid solution into the aniline-acid solution to form a reaction solution, so that aniline starts to grow on the surface of the grid region in a polymerization manner;
and simultaneously monitoring the intensity of the central wavelength of the reflection spectrum of the fiber grating, and taking out the optical fiber after the set requirement is met.
6. The preparation method of the micro-nano optical fiber gas sensor based on the in-situ grown polymer according to claim 4, wherein after the in-situ growth is finished, the method further comprises the following steps:
immersing the optical fiber into deionized water to clean impurities remained on the surface of the gate region;
completely immersing the gate region into an ammonia solution to perform the dedoping treatment of the PANI film;
taking out the optical fiber from the ammonia water solution, immersing the optical fiber into deionized water to remove ammonia molecules remained on the surface, immersing the optical fiber into a corresponding acid solution, and regulating the pH value of the optical fiber to re-dope the PANI film; and finally, taking out the optical fiber and fully drying the optical fiber.
7. The preparation method of the micro-nano optical fiber gas sensor based on the in-situ grown polymer according to claim 4, wherein the surface treatment is performed on the gate region, and specifically comprises the following steps:
soaking with ammonia water-hydrogen peroxide solution or silane coupling agent solution.
8. The preparation method of the micro-nano optical fiber gas sensor based on the in-situ grown polymer according to claim 7, wherein the aqueous solution of ammonia water-hydrogen peroxide is prepared by adding NH 3 ·H 2 O、H 2 O 2 And deionized water according to a set volume ratio;
the silane coupling agent is vinyl silane, amino silane or methacryloxy silane type coupling agent.
9. For detecting NH 3 A concentration sensing system, comprising: a fiber grating demodulator, the micro-nano fiber gas sensor of any one of claims 1 to 3 and a computer; the input optical fiber of the micro-nano optical fiber gas sensor is connected with an optical fiber grating demodulator, and the optical fiber grating demodulator is connected with a computer.
10. A method for detecting NH as claimed in claim 9 3 Concentration sensing system, characterized in that NH is carried out 3 When the concentration is detected, the optical signal output by the fiber grating demodulator passes through the micro-nano fiber grating sensorInputting the optical fiber into the gate region, and adsorbing NH in the environment by PANI film on the surface of the gate region 3 ，NH 3 The molecules capture protons on the imine nitrogen in the PANI molecular chain to reduce the conductivity of the PANI membrane, so that the central wavelength of the reflection spectrum in the fiber grating is shifted, and NH is calculated 3 The concentration of (2).
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