CN108562546A - A kind of detecting instrument and method of the miniaturization enhanced Laser Photoacoustic Spectroscopy of multiple reflections formula photoacoustic cell - Google Patents
A kind of detecting instrument and method of the miniaturization enhanced Laser Photoacoustic Spectroscopy of multiple reflections formula photoacoustic cell Download PDFInfo
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- CN108562546A CN108562546A CN201810337667.9A CN201810337667A CN108562546A CN 108562546 A CN108562546 A CN 108562546A CN 201810337667 A CN201810337667 A CN 201810337667A CN 108562546 A CN108562546 A CN 108562546A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/1702—Systems in which incident light is modified in accordance with the properties of the material investigated with opto-acoustic detection, e.g. for gases or analysing solids
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/1717—Systems in which incident light is modified in accordance with the properties of the material investigated with a modulation of one or more physical properties of the sample during the optical investigation, e.g. electro-reflectance
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/1702—Systems in which incident light is modified in accordance with the properties of the material investigated with opto-acoustic detection, e.g. for gases or analysing solids
- G01N2021/1704—Systems in which incident light is modified in accordance with the properties of the material investigated with opto-acoustic detection, e.g. for gases or analysing solids in gases
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/1717—Systems in which incident light is modified in accordance with the properties of the material investigated with a modulation of one or more physical properties of the sample during the optical investigation, e.g. electro-reflectance
- G01N2021/1725—Modulation of properties by light, e.g. photoreflectance
Abstract
A kind of detecting instrument and method of the miniaturization enhanced Laser Photoacoustic Spectroscopy of multiple reflections formula photoacoustic cell, belong to trace gas detection technical field.The instrument includes laser light source, light source driving, optics collimator, miniaturization multiple reflections formula photoacoustic cell, air intake valve, outlet valve, microphone, Signal acquiring and processing circuit and touch screen.Wavelength modulation is carried out to laser light source, on the pool wall surface of miniaturization multiple reflections formula photoacoustic cell multiple reflections radially occur for laser.The interference of the fundamental frequency photoacoustic signal generated by solid optoacoustic effect in pool wall surface multiple reflections can be eliminated using second-harmonic detection technology, realized to minimum gas without background and highly sensitive detection.Miniaturization multiple reflections formula photoacoustic cell in the present invention can be while reducing pond internal volume, in such a way that laser is in inner wall multiple reflections, the effective power of photo-acoustic excitation light is greatly improved, therefore the requirement to gas sample amount can be reduced, and the detection sensitivity and stability of system can be improved.
Description
Technical field
The invention belongs to trace gas detection technical fields, and it is enhanced sharp to be related to a kind of miniaturization multiple reflections formula photoacoustic cell
The detecting instrument and method of light optoacoustic spectroscopy.
Background technology
The advantages that high sensitivity that optoacoustic spectroscopy trace gas detection instrument has with it is with small sampling volume, in electric power
The analysis of plant failure characteristic gas, industrial production minimum discharge monitoring, calibrating gas defects inspecting, coal mine flammable explosive gas prison
It surveys and has played important function in the applications such as medicine tidal air diagnosis.
According to photoacoustic spectroscopy principle, the sensitivity of gas concentration measurement is proportional to the effective power of photo-acoustic excitation light source,
Therefore, it is the key that highly sensitive optoacoustic spectroscopy gas detection technology to improve effective power.In order to improve having for photo-acoustic excitation light
Power is imitated, can be realized by directly increasing the output power of light source and using two ways such as multiple reflections formula photoacoustic cells.With
The output power of the continuous development for laser technique, the laser light source for optoacoustic spectroscopy substantially improves, and is easier to reach watt
Magnitude.Document Hao L, Qiang S, Wu G, et al.Cylindrical mirror multipass Lissajous
system for laser photoacoustic spectroscopy[J].Review of scientific
instruments,2002,73(5):2079-2085 and Tanaka K, Miyamura K, Akishima K, et
al.Sensitive measurements of trace gas of formaldehyde using a mid-infrared
laser spectrometer with a compact multi-pass cell[J].Infrared Physics&
Technology,2016,79:1-5 devises the multi-way absorption cell based on double mirror, is used for optoacoustic spectroscopy trace gas physical examination
It surveys.In traditional acoustical signal processing system based on fundamental frequency light, since multiple reflections cause the solid light that mirror surface generates
The background of system can be significantly increased in acoustical signal, and the same frequency background of higher amplitude is superimposed upon on photoacoustic signal to be measured, reduces micro-
Measure the sensitivity of gas detection.It can be eliminated because of pool wall, window and anti-using wavelength-modulation technique and second-harmonic detection technology
Fundamental frequency interference caused by face absorbs is penetrated, is realized to photoacoustic signal without background detections.Currently, what is used in optoacoustic spectroscopy is multiple anti-
Penetrating formula absorption cell has larger volume, and job stability is not high.However, electric device fault characteristic gases analysis and
The application fields such as coal mine flammable explosive gas off-line monitoring are less due to gas sample amount, it is desirable that chamber volume is small as possible, but smaller
Photoacoustic pressure wave damps caused by photoacoustic cell sectional area makes hot damping time reduce, and then reduce optoacoustic spectroscopy minimum gas
The sensitivity of detecting system.Thus, a kind of highly sensitive Laser Photoacoustic Spectroscopy trace gas physical examination based on miniaturization photoacoustic cell of design
Surveying instrument has important application value.
Invention content
It is an object of the invention to propose a kind of enhanced Laser Photoacoustic Spectroscopy instrument of miniaturization multiple reflections formula photoacoustic cell,
While being intended to reduce the internal volume of photoacoustic cell, the effective power of photo-acoustic excitation light is greatly improved by multiple reflections mode,
The fundamental frequency light acoustic jamming that reflecting surface is eliminated using wavelength modulation second-harmonic detection method, is improved to the sensitive of trace gas detection
Degree expands the space of bigger for optoacoustic spectroscopy instrument in the application in trace gas detection field.
Technical scheme of the present invention：
A kind of detecting instrument of the miniaturization enhanced Laser Photoacoustic Spectroscopy of multiple reflections formula photoacoustic cell, including laser light source 1,
Light source driving 2, optics collimator 3, miniaturization multiple reflections formula photoacoustic cell 4, air intake valve 5, outlet valve 6, microphone 7, letter
Number acquisition with processing circuit 8 and touch screen 9；Light source driving 2 receives the modulated signal of 8 generation of Signal acquiring and processing circuit to swashing
Radiant 1 is modulated, and the laser that laser light source 1 is sent out is incident on miniaturization multiple reflections formula photoacoustic cell through optics collimator 3
4；Minimize multiple reflections formula photoacoustic cell 4 and be equipped with air intake valve 5 and outlet valve 6, entrance for controlling under test gas and
Discharge；Microphone 7 is mounted on miniaturization multiple reflections formula photoacoustic cell 4, for detecting in miniaturization multiple reflections formula photoacoustic cell 4
The photoacoustic signal of generation；The signal input part of Signal acquiring and processing circuit 8 is connected with microphone 7, and acquisition microphone 7 detects
Digital Signal Processing is carried out after photoacoustic signal；Touch screen 9 is connected with Signal acquiring and processing circuit 8, is acquired for setting signal
The photoacoustic signal measured value exported with the running parameter of processing circuit 8 and to Signal acquiring and processing circuit 8 is shown.
A kind of detection method of the miniaturization enhanced Laser Photoacoustic Spectroscopy of multiple reflections formula photoacoustic cell, is as follows：
First, after Signal acquiring and processing circuit 8 receives the control instruction that touch screen 9 inputs, air intake valve 5 is opened, is made
Running parameter is arranged full of miniaturization multiple reflections formula photoacoustic cell 4 under test gas；The output of Signal acquiring and processing circuit 8
Modulated signal is formed by stacking by the sinusoidal signal and sawtooth signal of fixed frequency, and modulated signal changes after being input to light source driving 2
Become the operating current of laser, realizes modulation and scanning to optical maser wavelength；The laser that laser light source 1 is sent out is through optics collimator
3 are incident on miniaturization multiple reflections formula photoacoustic cell 4, and laser is minimizing the pool wall surface of multiple reflections formula photoacoustic cell 4 radially
Direction is reflected；After minimizing the under test gas molecule absorption luminous energy in multiple reflections formula photoacoustic cell 4, moieties are energized
To excitation state, ground state is returned to after radiationless transition, the energy of molecule is converted to the periodicity of gas in the form of translation energy
Temperature change makes to generate photoacoustic signal in miniaturization multiple reflections formula photoacoustic cell 4；Microphone 7 converts the photoacoustic signal of detection
To be input to the signal input part of Signal acquiring and processing circuit 8 after electric signal, by the peak for extracting second harmonic photoacoustic signal
Value, is finally inversed by the concentration of minimum gas to be measured, finally shows measured value on the touchscreen, opens outlet valve 6 and gas is discharged.
The laser light source 1 is tunable wave length laser light source.
The miniaturization multiple reflections formula photoacoustic cell 4 is radial reflective photoacoustic cell, and laser is on round pool wall surface edge
Radial direction multiple reflections.
Second harmonic signal detector is equipped in the Signal acquiring and processing circuit 8.
The principle of the present invention is as follows：Wavelength modulation is carried out to laser light source, the photo-acoustic excitation light of transmitting is multiple in miniaturization
Multiple reflections radially occur for the round pool wall surface of reflective photoacoustic cell, and the effective power of photo-acoustic excitation light is made to have number
The raising of magnitude can increase substantially trace gas since the intensity of photoacoustic signal and the effective power of exciting light are directly proportional
The sensitivity that physical examination is surveyed.Incident angle by changing photo-acoustic excitation light is reflection time of the changeable light on round pool wall surface
Number.In addition, the fundamental frequency generated by solid optoacoustic effect in pool wall surface multiple reflections can be eliminated using second-harmonic detection technology
The interference of photoacoustic signal is realized to minimum gas without background detections, and then can further improve detection sensitivity.
Beneficial effects of the present invention：Minimizing multiple reflections formula photoacoustic cell can be while reducing pond internal volume, by swashing
Light greatly improves the effective power of photo-acoustic excitation light, therefore can reduce and be wanted to gas sample amount in the mode of inner wall multiple reflections
It asks, and the detection sensitivity of system can be improved.Compared to traditional axial multiple reflections formula absorption cell, light reflection can be increased considerably
Number, and then realize the enhancing of photoacoustic signal；And two independent speculums are not necessarily to, the stability of light path is improved.This hair
It is bright to provide a kind of technical solution of great competitiveness for trace gas detection.
Description of the drawings
Fig. 1 is the structural schematic diagram of the present invention.
Fig. 2 is the light path design figure for minimizing multiple reflections formula photoacoustic cell.
Fig. 3 is the second harmonic photoacoustic signal of the minimum gas of apparatus measures.
Fig. 4 is the second harmonic photoacoustic signal of apparatus measures under nitrogen background.
Fig. 5 is the relationship of the peak value and gas concentration of the second harmonic photoacoustic signal of apparatus measures.
In figure：1 laser light source；2 light sources drive；3 optics collimators；4 miniaturization multiple reflections formula photoacoustic cells；5 intake valves
Door 5；6 outlet valves；7 microphones；8 Signal acquiring and processing circuits；9 touch screens.
Specific implementation mode
Describe the specific implementation mode of the present invention in detail below in conjunction with technical solution and attached drawing.
A kind of enhanced Laser Photoacoustic Spectroscopy instrument of miniaturization multiple reflections formula photoacoustic cell, including laser light source 1, light source drive
Dynamic 2, optics collimator 3, miniaturization multiple reflections formula photoacoustic cell 4, air intake valve 5, outlet valve 6, microphone 7, signal acquisition
With processing circuit 8 and touch screen 9.
The running parameter of Signal acquiring and processing circuit 8 is configured by touch screen 9；Signal acquiring and processing circuit
8 output modulated signal is formed by stacking by the sinusoidal signal and sawtooth signal of fixed frequency, and modulated signal is input to light source drive
The operating current for changing laser after dynamic 2, realizes the modulation and scanning to optical maser wavelength；The laser that laser light source 1 is sent out is through light
It learns collimator 3 and is incident on miniaturization multiple reflections formula photoacoustic cell 4, pool wall table of the laser in miniaturization multiple reflections formula photoacoustic cell 4
Multiple reflections radially occur for face；It minimizes multiple reflections formula photoacoustic cell 4 and is equipped with air intake valve 5 and outlet valve 6, use
In the inlet and outlet of control under test gas；After minimizing the under test gas molecule absorption luminous energy in multiple reflections formula photoacoustic cell 4,
Moieties are excited to excitation state, and ground state is returned to after radiationless transition, and the energy of molecule is converted in the form of translation energy
Change for the periodic temperature of gas, makes to generate photoacoustic signal in miniaturization multiple reflections formula photoacoustic cell 4；Microphone 7 will detect
Photoacoustic signal be converted to the signal input part that Signal acquiring and processing circuit 8 is input to after electric signal, it is secondary humorous by extracting
The peak value of glistening light of waves acoustical signal is finally inversed by the concentration of minimum gas to be measured, finally shows measured value on the touchscreen.
Wherein, laser light source 1 is the narrow linewidth Distributed Feedback Laser or VCSEL lasers of tunable wave length, and centre wavelength is about
For 1532nm.Round pool wall surface inside miniaturization multiple reflections formula photoacoustic cell 4 be polished with gold-plated processing, laser can be made
Radially generating compared with multiple reflections.Signal acquiring and processing circuit 8 is good digital lock-in amplifier, can be to second harmonic light
Acoustical signal carries out high s/n ratio extraction.
Fig. 2 is the light path design figure for minimizing multiple reflections formula photoacoustic cell.Collimation laser round pool wall surface radially
Multiple reflections are reflected in direction, and the incident angle by changing photo-acoustic excitation light is the order of reflection of changeable light.
Fig. 3 is the second harmonic photoacoustic signal of the trace acetylene gas of apparatus measures.1ppm acetylene gas is passed through in photoacoustic cell
Body extracts wavelength using phase lock amplifying technology and modulates second harmonic photoacoustic signal.
Fig. 4 is the second harmonic photoacoustic signal of apparatus measures under nitrogen background.Output signal fluctuates above or below 0V, show into
The fundamental frequency photoacoustic signal that laser is generated in pool wall surface multiple reflections by solid optoacoustic effect is penetrated almost not have trace gas detection
There is interference.
Fig. 5 is the relationship of the peak value and gas concentration of the second harmonic photoacoustic signal of apparatus measures.Between the two have compared with
Good linear relationship is, it can be achieved that the high-precision to minimum gas detects.
The foregoing is merely the preferred embodiment of the present invention, are not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.Any modification made by all within the spirits and principles of the present invention,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of detecting instrument of the miniaturization enhanced Laser Photoacoustic Spectroscopy of multiple reflections formula photoacoustic cell, which is characterized in that the instrument
Device includes laser light source (1), light source driving (2), optics collimator (3), miniaturization multiple reflections formula photoacoustic cell (4), intake valve
Door (5), outlet valve (6), microphone (7), Signal acquiring and processing circuit (8) and touch screen (9)；Light source drives (2) to receive
The modulated signal that Signal acquiring and processing circuit (8) generates is modulated laser light source (1), and what laser light source (1) was sent out swashs
Light is incident on miniaturization multiple reflections formula photoacoustic cell (4) through optics collimator (3)；It minimizes on multiple reflections formula photoacoustic cell (4)
Equipped with air intake valve (5) and outlet valve (6), the inlet and outlet for controlling under test gas；Microphone (7) is mounted on small-sized
Change on multiple reflections formula photoacoustic cell (4), for detecting the photoacoustic signal generated in miniaturization multiple reflections formula photoacoustic cell (4)；Letter
Number acquisition is connected with the signal input part of processing circuit (8) with microphone (7), after the photoacoustic signal that acquisition microphone (7) detects
Carry out Digital Signal Processing；Touch screen (9) is connected with Signal acquiring and processing circuit (8), acquires and handles for setting signal
The running parameter of circuit (8) simultaneously shows the photoacoustic signal measured value of Signal acquiring and processing circuit (8) output.
2. a kind of detection method of the miniaturization enhanced Laser Photoacoustic Spectroscopy of multiple reflections formula photoacoustic cell, which is characterized in that specific
Steps are as follows：
First, after Signal acquiring and processing circuit (8) receives the control instruction that touch screen (9) inputs, air intake valve (5) is opened,
Make under test gas full of miniaturization multiple reflections formula photoacoustic cell (4), and running parameter is set；Signal acquiring and processing circuit (8)
Output modulated signal be formed by stacking by the sinusoidal signal and sawtooth signal of fixed frequency, modulated signal be input to light source driving
(2) operating current for changing laser afterwards, realizes the modulation and scanning to optical maser wavelength；The laser warp that laser light source (1) is sent out
Optics collimator (3) is incident on miniaturization multiple reflections formula photoacoustic cell (4), and laser is in miniaturization multiple reflections formula photoacoustic cell (4)
Pool wall surface radially reflect；It minimizes multiple reflections formula photoacoustic cell (4) and is equipped with air intake valve (5) and outlet
Valve (6), the inlet and outlet for controlling under test gas；Minimize the under test gas point in multiple reflections formula photoacoustic cell (4)
After son absorbs luminous energy, moieties are excited to excitation state, ground state are returned to after radiationless transition, the energy of molecule is to be translatable
The form of energy is converted to the periodic temperature variation of gas, makes to generate photoacoustic signal in miniaturization multiple reflections formula photoacoustic cell (4)；
Microphone (7), which is converted to the photoacoustic signal of detection, to be input to the signal of Signal acquiring and processing circuit (8) after electric signal and inputs
End is finally inversed by the concentration of minimum gas to be measured, finally shows on the touchscreen by extracting the peak value of second harmonic photoacoustic signal
Measured value opens outlet valve (6) and gas is discharged.
3. a kind of detection side of miniaturization enhanced Laser Photoacoustic Spectroscopy of multiple reflections formula photoacoustic cell according to claim 2
Method, which is characterized in that the laser light source (1) is tunable wave length laser light source.
4. a kind of inspection of miniaturization enhanced Laser Photoacoustic Spectroscopy of multiple reflections formula photoacoustic cell according to claim 2 or 3
Survey method, which is characterized in that the miniaturization multiple reflections formula photoacoustic cell (4) is radial reflective photoacoustic cell, and laser is in circle
Shape pool wall surface is radially reflected.
5. a kind of inspection of miniaturization enhanced Laser Photoacoustic Spectroscopy of multiple reflections formula photoacoustic cell according to claim 2 or 3
Survey method, which is characterized in that second harmonic signal detector is equipped in the Signal acquiring and processing circuit (8).
6. a kind of detection side of miniaturization enhanced Laser Photoacoustic Spectroscopy of multiple reflections formula photoacoustic cell according to claim 4
Method, which is characterized in that second harmonic signal detector is equipped in the Signal acquiring and processing circuit (8).
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Cited By (5)
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| CN110095413A (en) * | 2019-05-21 | 2019-08-06 | 安徽理工大学 | A kind of modular construction photoacoustic cell suitable for Laser Photoacoustic Spectroscopy detection |
| CN111896475A (en) * | 2020-07-29 | 2020-11-06 | 东北大学秦皇岛分校 | Light path range-extending type photoacoustic cell for photoacoustic spectrum trace gas detection |
| CN112683806A (en) * | 2020-12-08 | 2021-04-20 | 大连理工大学 | Method for realizing sensitivity enhancement of photoacoustic system and polishing-free photoacoustic cell by using acetate fiber membrane |
| CN114047136A (en) * | 2021-11-09 | 2022-02-15 | 大连理工大学 | High-sensitivity combined light source type photoacoustic spectroscopy multi-component gas detection system and method |
| CN115201116A (en) * | 2022-09-15 | 2022-10-18 | 中国科学院合肥物质科学研究院 | Low-noise differential type Helmholtz photoacoustic spectrum detection device and method |
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Application publication date: 20180921 |