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CN106404741B - Enhancing Raman spectrum liquid detecting method based on dual-hollow optical fiber - Google Patents

Enhancing Raman spectrum liquid detecting method based on dual-hollow optical fiber Download PDF

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Publication number
CN106404741B
CN106404741B CN201610887801.3A CN201610887801A CN106404741B CN 106404741 B CN106404741 B CN 106404741B CN 201610887801 A CN201610887801 A CN 201610887801A CN 106404741 B CN106404741 B CN 106404741B
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hollow
core fiber
liquid
raman
laser
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CN106404741A (en
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祝连庆
张雯
姚齐峰
董明利
娄小平
何巍
骆飞
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Beijing Information Science and Technology University
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Beijing Information Science and Technology University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N21/658Raman scattering enhancement Raman, e.g. surface plasmons

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  • Health & Medical Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
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  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

The present invention provides the enhancing Raman spectrum liquid detecting methods based on dual-hollow optical fiber, this method use wavelength be 532 nanometers continuous wave laser as light source and design use inner wall plated film dual-hollow optical fiber as detecting structure, and reference fluids and testing liquid are detected simultaneously and obtain two-way spectral signal, by obtaining compositional difference and testing liquid constituent analysis between reference fluids and testing liquid with comparative analysis to two-way raman spectral signal, therefore fluid present invention detection method is wide with use scope, measurement efficiency is high and high reliability.

Description

Enhancing Raman spectrum liquid detecting method based on dual-hollow optical fiber
Technical field
The present invention relates to a kind of Raman spectrum liquid detecting methods, more particularly to the enhancing Raman light based on dual-hollow optical fiber Compose liquid detecting method.
Background technology
Raman spectroscopy has that analytical cycle is short, device is simple, can detect plurality of liquid simultaneously in detection side liquid face Etc. technical advantages, by as important species analysis detection means, in biomedicine, physical chemistry, material analysis, micro-nano test Equal fields are widely used.In recent years, application of the Raman spectroscopy on mars exploration also is proposed out, European space Boat office (ESA) and NASA (NASA) plan to emit ExoMars in 2018, and ramber will carry Raman spectrometer (Raman Laser Spectrometer, RLS) detects martian surface and deep layer substance;NASA plans to send out in the year two thousand twenty Raman spectrometer (The Scanning Habitable are carried in the 2020 science ramber of Mars (Mars 2020Rover) penetrated Enviro nanometers of ents with Raman&Luminescence for Organics and Chemicals, SHERLOC), it uses To detect mineral and organic compound under subtle rank.
However, Raman scattering is a kind of weak scattering, there are problems that under-sensitive in practical operation, it is more typical at present Be using multiple reflections enhancing by the way of.1974, Sandia National Laboratories of U.S. Hill etc. is reported to be dissipated for Raman The multiple reflections chamber for penetrating enhancing, it is multiple anti-using being made of two pairs of orthogonal total reflective mirrors and a pair of confocal planoconvex spotlight Chamber is penetrated, about 20 times of enhancing is obtained in the light intensity of focal point.2008, Shanghai Communications University X.Y.Li etc. devised nearly confocal drawing The gas detection limit of graceful enhancing chamber, system can be improved to tens ppm.2011, Texas ,Usa university Utsav etc. pairs Herriott chambers are improved, and Raman signal intensity enhances 83 times, and signal-to-noise ratio increases to 153 by 9.3.2014, China sea The detection limit of the prosperous equal further nearly anxious chambers of foreign university Yang De is increased to more than ten ppm.
In fact, although multiple reflections chamber can greatly improve Raman scattering intensities, multiple reflections chamber uses two height Reflectivity hysteroscope is enhanced, more demanding to optical path adjusting and system stability.Meanwhile if measurement object is transparent organic Thing liquid body, it is easy to due to focus it is inaccurate and by focal point on glass slide.
In conclusion common Raman detection method is analyzed only for single sample, and not because of Raman spectrum data library It can timely update and bring certain error, significantly reduce measurement efficiency and reliability.Therefore, it is necessary to one kind being equipped with reference The Raman spectroscopic detection method of sample analysis and high measurement efficiency and high reliability.
Invention content
The purpose of the present invention is to provide the enhancing Raman spectrum liquid detecting method based on dual-hollow optical fiber, this method packets Include following steps:
(a) reference fluids and testing liquid are injected separately into the first hollow-core fiber and the second hollow light of parallel side-by-side arrangement In fibre and it is full of first hollow-core fiber and second hollow-core fiber;
(b) it uses the continuous wave laser that wavelength is 532 nanometers as light source, is 50 by splitting ratio:50 coupler will The laser that the continuous wave laser is sent out is divided into beam of laser and the second beam laser;
(c) beam of laser and the second beam laser are respectively by the first lens and the second lens by described first Shu Jiguang and the second beam laser are focused to respectively in first hollow-core fiber and second hollow-core fiber;
(d) beam of laser and the second beam laser excite reference fluids and described as exciting light respectively Testing liquid generates Raman diffused light and is directed into first through the first collection light path lens and the second collection light path lens again respectively Photodetector and the second photodetector;
(e) first photodetector and second photodetector are respectively by the exciting light detected and institute It states Raman diffused light and is transmitted to data analysis system and analyzed;
(f) data analysis system obtains the drawing of the Raman spectrum and the testing liquid of the reference fluids through analysis Graceful spectrum is simultaneously compared, to obtain compositional difference and the realization between the testing liquid and the reference fluids Constituent analysis to the testing liquid.
Preferably, the data analysis system uses the method for subtracting baseline automatically respectively to the reference fluids Raman spectrum Subtract base with the testing liquid Raman spectrum to handle and wait for after reference fluids Raman spectrum after being optimized and optimization Survey liquid Raman spectrum.
Preferably, first hollow-core fiber and second hollow-core fiber are hollow silica fibre and share an outside Two ends of covering and the extramural cladding are fixed by scolding tin.
Preferably, the inner wall of first hollow-core fiber and second hollow-core fiber is coated with high inverse medium film.
Preferably, the high inverse medium film is plating silverskin.
Preferably, the length of the intensity of the Raman spectrum and first hollow-core fiber and second hollow-core fiber it Between variation below follow equation:
The liquid of the exciting light and the Raman diffused light in first hollow-core fiber or second hollow-core fiber Decay in e index in body, and loss factor having the same, wherein PRFor Raman scattered light intensity, PLFor excitating light strength, α is The loss factor of liquid in first hollow-core fiber or second hollow-core fiber, χ are first hollow-core fiber or described The length of second hollow-core fiber, K are the scattering section and the relevant constant of fiber numerical aperture of liquid in the hollow-core fiber.
Fluid present invention detection method is wide with use scope, measurement efficiency is high and high reliability.
It should be appreciated that aforementioned description substantially and follow-up description in detail are exemplary illustration and explanation, it should not As the limitation to the claimed content of the present invention.
Description of the drawings
With reference to the attached drawing of accompanying, the more purposes of the present invention, function and advantage are by the as follows of embodiment through the invention Description is illustrated, wherein:
Fig. 1 schematically shows the system composition schematic diagram of fluid present invention detection method;
Fig. 2 schematically shows the operational flowchart of fluid present invention detection method;
The Raman spectrogram that Fig. 3 is obtained by fluid present invention detection method;
The Raman spectrogram through subtracting base processing that Fig. 4 is obtained by fluid present invention detection method;
Fig. 5 is directed to the Raman spectrogram of different sample institutes test data for fluid present invention detection method.
Specific implementation mode
By reference to exemplary embodiment, the purpose of the present invention and function and the side for realizing these purposes and function Method will be illustrated.However, the present invention is not limited to exemplary embodiment as disclosed below;Can by different form come It is realized.The essence of specification is only to aid in the detail of the various equivalent modifications Integrated Understanding present invention.
Hereinafter, the embodiment of the present invention will be described with reference to the drawings.In the accompanying drawings, identical reference numeral represents identical Or similar component or same or like step.
What Fig. 1 and Fig. 2 respectively illustrated the enhancing Raman spectrum liquid detecting method the present invention is based on dual-hollow optical fiber is System composition Figure 100 and steps flow chart Figure 200.The system of fluid present invention detection method forms Figure 100:Continuous laser Device 101, the 102, first lens 103 of coupler (OC) and the second lens 104, the first hollow-core fiber 105 and the second hollow-core fiber 106, first light path lens 107 and the second collection light path lens 108, the first photodetector 109 and the second photodetection are collected Device 110 and data analysis system 111.
The step flow chart 200 of fluid present invention detection method includes the following steps:
(a) the first hollow-core fiber 105 and second that reference fluids and testing liquid are injected separately into parallel side-by-side arrangement is empty In core fibre 106 and it is full of 106 (step 201) of the first hollow-core fiber 105 and the second hollow-core fiber.First hollow-core fiber 105 and second hollow-core fiber 106 be hollow silica fibre and share two of an extramural cladding and the extramural cladding End is fixed by scolding tin.
The common general extramural cladding of hollow silica fibre contains layer of silica gel or epoxy resin layer keeps its soft and not easy to break It is disconnected, but layer of silica gel or epoxy resin layer are organic material layer and are soluble in organic solution, and this will bring detection organic liquid Detrimental effect.
To avoid above-mentioned adverse effect, in the present invention the first hollow-core fiber 105 and the second hollow-core fiber 106 share outside The both ends of wrap use and are fixed by scolding tin.Specifically, according to one section of alcolhol burner burn off of the length of optical fiber head, stone is allowed English is exposed and will be fixed in the scolding tin of optical fiber head insertion melting, again with 1 after cooling:The AB inorganic glues of 1 mixing are obturaged and are dried in the air It is dry, to effectively prevent the phenomenon that leaks after injection liquid.
Further reference fluids and testing liquid are noted from one end of the first hollow-core fiber 105 and the second hollow-core fiber 106 Entering while loweing the first hollow-core fiber 105 and 106 other end of the second hollow-core fiber makes liquid along the first hollow-core fiber 105 and Two hollow-core fibers 106 are flowed into up to being full of, but can not be expired very much, are stayed at the first hollow-core fiber 105 and the second hollow-core fiber 106 Between emptying, convenient for envelope optical fiber head, ensure the liquid expansion for having space buffer solution heated after sealing.
Preferably, the inner wall of the first hollow-core fiber 105 and the second hollow-core fiber 106 is coated with high inverse medium film, and the height is anti- Deielectric-coating is metal tunic, such as plates silverskin;This high inverse medium film can effectively enhance raman spectral signal intensity.
(b) it uses the continuous wave laser 101 that wavelength is 532 nanometers to be used as light source, is 50 by splitting ratio:50 coupler The laser that continuous wave laser 101 is sent out is divided into beam of laser and the second beam laser (step 202) by 102.
(c) beam of laser and the second beam laser are respectively by the first lens 103 and the second lens 104 by beam of laser (step 203) in the first hollow-core fiber 105 and second hollow-core fiber 106 is focused to respectively with the second beam laser.
(d) beam of laser and the second beam laser are excited as exciting light respectively positioned at the first hollow-core fiber 105 and described Reference fluids and testing liquid in second hollow-core fiber 106 generate Raman diffused light (step 203) and are received again through first respectively Light harvesting Reuter mirror 107 and second collects light path lens 108 and is directed into the first photodetector 109 and the second photodetector 110.
(e) the first photodetector 109 and the second photodetector 110 pass the exciting light detected and Raman diffused light It transports to data analysis system 111 and is analyzed (step 204).
(f) data analysis system 111 through analysis obtain reference fluids Raman spectrum and testing liquid Raman spectrum simultaneously It is compared, to obtain the compositional difference between testing liquid and reference fluids and realize the constituent analysis to testing liquid (step 205).Data analysis system 111 collects two-way raman spectral signal, by comparing reference fluids and testing liquid Raman spectrum, you can complete the analysis of the liquid component in the first hollow-core fiber 105 and the second hollow-core fiber 106, realization pair The detection of liquid component.
Preferably, data analysis system 111 to reference fluids Raman spectrum and is waited for respectively using subtracting the method for baseline automatically Survey liquid Raman spectrum subtract the reference fluids Raman spectrum after base handle and optimize and it is preferred after testing liquid drawing Graceful spectrum.
Fig. 3 shows that certain tests obtained Raman spectrum, from can clearly distinguish O in liquid in Fig. 32And N2's Raman spectral signal, this shows that exciting light excites the Raman spectrum of liquid really.Incident exciting light also excites first simultaneously Hollow-core fiber 105 and 106 inner wall of the second hollow-core fiber simultaneously generate fluorescence, inclined to be lifted entire spectral background and generation baseline From phenomenon.In order to reduce influence of the fluorescence background to measured data, using subtracting the data processing method of baseline automatically to spectrum number According to base processing subtract, fluorescence background is eliminated as much as possible, baseline deviation is eliminated to the lifting effect of measurement data, to Raman spectral signal after to optimization.As shown in figure 4, the Raman spectrum data after over-subtraction base optimization processing not only remains light The position at spectrum signature peak, but also lifting effect of the fluorescence background to measurement data is significantly reduced, to improve spectrum Comparativity, intuitive and detection accuracy.
Fig. 5 shows the embodiment judged testing liquid according to measured data, wherein sample A and B be two kinds not Same liquid, and A is pure water and as known reference fluids, the Raman line of liquid A constitutes the main looks with reference to Raman spectrum.
The Raman spectrum test curve of two kinds of liquid is it is found that liquid B and liquid A have similar Raman in comparison diagram 5 Spectral line, but the intensity value of the two characteristic peak is different, and the Raman signatures peak value of liquid B is less than the peak value of liquid A.By testing liquid Raman spectrum be compared analysis with the Raman spectrum of known reference liquid, on the one hand can directly sentence from the pattern of Raman line Break the difference between sample and known reference liquid;On the other hand, can also judge in sample from the size of characteristic peaks Number containing trace mineral ingredient.It can effectively be reduced due to standard spectral data library cannot timely update by comparative analysis The error brought, greatly improves measurement efficiency and reliability.
Assuming that being in e in the liquid of exciting light and Raman diffused light in the first hollow-core fiber 105 and the second hollow-core fiber 106 Exponential damping, and loss factor having the same, then in backscattering geometry, Raman scattered light intensity and first hollow Variation between optical fiber 105 and the length of second hollow-core fiber 106 also follows following equation:
Wherein PRFor Raman scattered light intensity, PLFor excitating light strength, α is first hollow-core fiber 105 or described second The loss factor of liquid in hollow-core fiber 106, χ are the length of first hollow-core fiber 105 or second hollow-core fiber 106 Degree, K are the scattering section and fiber numerical aperture of liquid in first hollow-core fiber 105 or second hollow-core fiber 106 Relevant constant.
In conclusion the present invention is based on the enhancing Raman spectrum liquid detecting methods of dual-hollow optical fiber to use dual-hollow optical fiber Structure carries out Raman spectroscopic detection to reference fluids and testing liquid simultaneously, and to the two-way raman spectral signal of acquisition use than Obtain compositional difference and constituent analysis compared with analysis, thus fluid present invention detection method has that use scope is wide, measurement efficiency it is high with And high reliability.
The attached drawing is only schematical and draws not in scale.Although have been combined preferred embodiment to the present invention into Description is gone, it is to be understood that protection scope of the present invention is not limited to embodiment as described herein.
Explanation in conjunction with the present invention disclosed here and practice, the other embodiment of the present invention is for those skilled in the art It all will be readily apparent and understand.Illustrate and embodiment is regarded only as being exemplary, true scope of the invention and purport are equal It is defined in the claims.

Claims (5)

1. the enhancing Raman spectrum liquid detecting method based on dual-hollow optical fiber, this method comprises the following steps:
(a) reference fluids and testing liquid are injected separately into the first hollow-core fiber and the second hollow-core fiber of parallel side-by-side arrangement And it is full of first hollow-core fiber and second hollow-core fiber;
(b) it uses the continuous wave laser that wavelength is 532 nanometers as light source, is 50 by splitting ratio:50 coupler will be described The laser that continuous wave laser is sent out is divided into beam of laser and the second beam laser;
(c) beam of laser and the second beam laser are respectively swashed first beam by the first lens and the second lens Light and the second beam laser are focused to respectively in first hollow-core fiber and second hollow-core fiber;
(d) beam of laser and the second beam laser excite reference fluids and described to be measured as exciting light respectively Liquid generates Raman diffused light and is directed into the first photoelectricity through the first collection light path lens and the second collection light path lens again respectively Detector and the second photodetector;
(e) first photodetector and second photodetector are respectively by the exciting light detected and the drawing Graceful transmission of stray light to data analysis system is analyzed;
(f) data analysis system obtains the Raman light of the Raman spectrum and the testing liquid of the reference fluids through analysis It composes and is compared, waited for described to obtain the compositional difference between the testing liquid and the reference fluids and realize The constituent analysis of liquid is surveyed,
Wherein, the change between the intensity of the Raman spectrum and first hollow-core fiber and the length of second hollow-core fiber Equation is followed below changing:
In the liquid of the exciting light and the Raman diffused light in first hollow-core fiber or second hollow-core fiber Decay in e index, and loss factor having the same, wherein PRFor Raman scattered light intensity, PLFor excitating light strength, α is described The loss factor of liquid in first hollow-core fiber or second hollow-core fiber, χ are first hollow-core fiber or described second The length of hollow-core fiber, K are the scattering section and the relevant constant of fiber numerical aperture of liquid in the hollow-core fiber.
2. liquid detecting method according to claim 1, it is characterised in that:The data analysis system uses subtracts base automatically The method of line subtract base to the reference fluids Raman spectrum and the testing liquid Raman spectrum respectively and handles and obtain excellent The testing liquid Raman spectrum after reference fluids Raman spectrum and optimization after change.
3. liquid detecting method according to claim 2, it is characterised in that:First hollow-core fiber and second sky Core fibre is hollow silica fibre and two ends of a shared extramural cladding and the extramural cladding are fixed by scolding tin.
4. liquid detecting method according to claim 3, it is characterised in that:First hollow-core fiber and second sky The inner wall of core fibre is coated with high inverse medium film.
5. liquid detecting method according to claim 4, it is characterised in that:The high inverse medium film is plating silverskin.
CN201610887801.3A 2016-10-11 2016-10-11 Enhancing Raman spectrum liquid detecting method based on dual-hollow optical fiber Active CN106404741B (en)

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CN106923781A (en) * 2017-03-28 2017-07-07 戎创前沿科技(北京)有限公司 A kind of Raman Gastroscope Diagnosis instrument
CN113552110A (en) * 2021-07-16 2021-10-26 中国民航大学 Raman spectrum-based dynamic early warning system and method for thermal runaway of lithium ion battery

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JPH0756041A (en) * 1993-08-20 1995-03-03 Sumitomo Electric Ind Ltd Dual core optical fiber and temperature measuring instrument using the same
US6900890B1 (en) * 2003-11-17 2005-05-31 The Boeing Company Fiber Raman sensor for remote chemical detection
US7343074B1 (en) * 2007-02-27 2008-03-11 Corning Incorporated Optical waveguide environmental sensor and method of manufacture
US7595882B1 (en) * 2008-04-14 2009-09-29 Geneal Electric Company Hollow-core waveguide-based raman systems and methods
CN102116684B (en) * 2011-01-21 2012-09-05 中国计量学院 Self-correcting fully-distributed optical fiber Raman scattering sensor
CN103472049A (en) * 2013-06-25 2013-12-25 复旦大学 Organophosphorus detection method based on hollow-core fiber
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CN104677291A (en) * 2015-03-08 2015-06-03 哈尔滨工业大学 Double-core fiber bragg grating probe micro-scale measuring device and method based on linear cavity optical fiber laser

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