CN111380805A - Photoacoustic cell with adjustable resonant frequency and adjusting method - Google Patents
Photoacoustic cell with adjustable resonant frequency and adjusting method Download PDFInfo
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- CN111380805A CN111380805A CN202010004566.7A CN202010004566A CN111380805A CN 111380805 A CN111380805 A CN 111380805A CN 202010004566 A CN202010004566 A CN 202010004566A CN 111380805 A CN111380805 A CN 111380805A
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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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/03—Cuvette constructions
- G01N21/0332—Cuvette constructions with temperature control
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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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/03—Cuvette constructions
- G01N21/0303—Optical path conditioning in cuvettes, e.g. windows; adapted optical elements or systems; path modifying or adjustment
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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
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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
- 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
Abstract
The invention discloses a photoacoustic cell with adjustable resonant frequency and an adjusting method, and belongs to the technical field of gas detection. The photoacoustic cell provided by the invention is arranged in a constant temperature box and comprises a first buffer chamber, a second buffer chamber, a resonant cavity, a first optical window, a second optical window, a first movable structure and a second movable structure; the first light window and the second light window are respectively positioned at the outer sides of the first buffer chamber and the second buffer chamber. The invention improves the originally fixed buffer chamber and resonant cavity into the movable structure capable of adjusting the structural parameters by utilizing the piezoelectric ceramics, improves the adjusting capability of the resonant frequency and the reliability and flexibility of the whole photoacoustic cell in the resonant working state, and the photoacoustic cell is arranged in the constant temperature box, thereby not only eliminating the interference caused by the change of the external temperature and the pressure intensity and avoiding the instability of the resonant frequency in the resonant working process caused by the external interference, but also adjusting the resonant frequency of the photoacoustic cell by changing the temperature and improving the working stability and the signal-to-noise ratio of the detection system.
Description
Technical Field
The invention belongs to the technical field of gas detection, and particularly relates to a photoacoustic cell with adjustable resonant frequency and an adjusting method.
Background
Photoacoustic spectroscopy is a spectroscopic technique based on the photoacoustic effect. In the photoacoustic effect, gas molecules absorb infrared light with specific wavelength and are excited to a high-energy state, the molecules in the high-energy state convert the absorbed light energy into heat energy in a non-radiative transition mode and then return to a low-energy state, then the incident light is subjected to frequency modulation, the heat energy can present periodic variation the same as the modulation frequency to generate sound waves, and sound signals are detected through a microphone and the final concentration of the gas is obtained through calculation.
The core components influencing the sensitivity of the photoacoustic spectroscopy gas detection system mainly comprise a light source, a photoacoustic cell and a microphone, and the measurement sensitivity of the whole photoacoustic system can be influenced by the line width of a laser light source, the equivalent noise power of the microphone and the like. The photoacoustic cell is used as a generating source of photoacoustic signals and is a core part of a photoacoustic spectrum measuring system, and whether the design of the photoacoustic cell reasonably and directly influences the sensitivity of detecting sound pressure signals. The resonant photoacoustic cell has the advantages of high response speed, strong resonance amplification effect, high gas detection sensitivity and the like, but the resonant photoacoustic cell is relatively complex in structure and is easy to have resonance frequency drift due to temperature, pressure and the like. A larger photoacoustic signal can be obtained only when the modulation frequency of the laser light source is aligned with the resonant frequency of the photoacoustic cell, the signal-to-noise ratio obtained by the microphone is sharply attenuated once the resonant frequency is shifted, and especially for the photoacoustic cell with a larger quality factor, the amplitude of the photoacoustic signal is greatly influenced by the shift of the resonant frequency.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a photoacoustic cell with adjustable resonant frequency and an adjusting method, which can adjust the working frequency to the standard resonant frequency and aim to solve the problem of reduced gas concentration detection capability caused by the resonant frequency drift of the photoacoustic cell.
In order to achieve the above object, the present invention provides a photoacoustic cell with adjustable resonant frequency, which is disposed inside a thermostat and comprises a first buffer chamber, a second buffer chamber, a resonant cavity, a first optical window, a second optical window, a first movable structure and a second movable structure;
the first light window and the second light window are respectively positioned at the outer sides of the first buffer chamber and the second buffer chamber;
a first piezoelectric ceramic is adhered to the outer side of the first optical window and can displace under the action of the first piezoelectric ceramic; a second piezoelectric ceramic is adhered to the outer side of the second optical window and can displace under the action of the second piezoelectric ceramic;
the first movable structure and the second movable structure are arranged on two sides of the resonant cavity, and the materials of the first movable structure and the second movable structure are the same as those of the resonant cavity;
a third piezoelectric ceramic is arranged between the first movable structure and the resonant cavity, one side of the third piezoelectric ceramic, which is close to the resonant cavity, is fixed, and the other side of the third piezoelectric ceramic is adhered to the first movable structure, so that the first movable structure can be driven to move; and a fourth piezoelectric ceramic is arranged between the second movable structure and the resonant cavity, one side of the fourth piezoelectric ceramic, which is close to the resonant cavity, is fixed, and the other side of the fourth piezoelectric ceramic, which is adhered to the second movable structure, can drive the second movable structure to move.
Further, a temperature sensor is arranged in the incubator and used for detecting the temperature of the photoacoustic cell.
Further, the resonant cavity is of a first-order cylindrical resonance type.
Furthermore, the device also comprises a microphone arranged in the resonant cavity and used for detecting the sound signal generated by the resonant cavity.
Further, the lengths of the first buffer chamber and the second buffer chamber are equal, and the ratio of the lengths of the first buffer chamber and the second buffer chamber to the length of the resonant cavity is 1: 2.
The invention also provides a resonant frequency adjusting method based on the photoacoustic cell, which comprises the steps of
Measuring the real-time resonance frequency of the photoacoustic cell, and comparing the real-time resonance frequency with the standard resonance frequency: if the detection result is equal to the preset detection result, directly starting subsequent detection work; if there is a difference, the temperature or cavity length is changed;
and after the temperature or the cavity length is changed every time, measuring the real-time resonant frequency of the photoacoustic cell again, and if the real-time resonant frequency is not equal to the standard resonant frequency, continuously changing the temperature or the cavity length until the real-time resonant frequency is equal to the standard resonant frequency.
Further, the real-time resonance frequency of the photoacoustic cell is measured by a resonance sonography method.
Further, in the process of changing the cavity length, the ratio of the lengths of the first buffer chamber, the second buffer chamber and the resonant cavity is kept unchanged, wherein the ratio of the lengths of the first buffer chamber, the second buffer chamber and the resonant cavity is 1: 2.
The invention also provides a gas photoacoustic spectrum detection system which comprises the photoacoustic cell.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) the photoacoustic cell provided by the invention has the advantages that the originally fixed buffer chamber and resonant cavity are improved into the movable structure with adjustable structural parameters, so that the adjusting capability of the resonant frequency and the reliability and flexibility of the whole photoacoustic cell in a resonant working state are greatly improved;
(2) the photoacoustic cell is arranged in the constant temperature box, so that the interference caused by the change of the external temperature and the pressure can be eliminated, the instability of the resonant frequency in the resonant working process caused by the external interference is avoided, and the resonant frequency of the photoacoustic cell can be adjusted by changing the temperature;
(3) the invention uses the resonance spectrum method to measure the actual resonance frequency of the photoacoustic cell in real time, realizes the negative feedback adjustment of the resonance frequency, thereby accurately adjusting the working frequency to the standard frequency of the laser in real time and being beneficial to improving the Q value and the signal-to-noise ratio of the resonant cavity.
Drawings
FIG. 1 is a schematic diagram of a photoacoustic cell for photoacoustic spectroscopy of gases according to the present invention;
wherein the reference numerals are:
1-a laser; 2-a first piezoelectric ceramic; 3-a first optical window; 4-a first mobile structure; 5-a third piezoelectric ceramic; 6-a microphone; 7-a second mobile structure; 8-a second optical window; 9-a first buffer chamber; 10-a second buffer chamber; 11-a resonant cavity; 12-a second piezoelectric ceramic; 13-a fourth piezoelectric ceramic;
fig. 2 is a schematic diagram of a resonant frequency adjustment method of a photoacoustic cell of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in fig. 1, an embodiment of the present invention provides a photoacoustic cell for photoacoustic spectroscopy of a gas, including:
the gas inlet is used for introducing gas to be detected and the gas outlet is used for discharging the gas to be detected;
the first buffer chamber 9 and the second buffer chamber 10 are symmetrically arranged on two sides of the central axis of the photoacoustic cell, the first buffer chamber 9 is communicated with the air inlet, and the second buffer chamber 10 is communicated with the air outlet;
the resonant cavity 11 is of a first-order cylindrical resonance type and is communicated with the first buffer chamber 9 and the second buffer chamber 10;
the microphone 6 is arranged in the resonant cavity 11 and used for detecting a sound signal generated by the resonant cavity;
the first optical window 3 and the second optical window 4 are respectively arranged at the outer sides of the first buffer chamber 9 and the second buffer chamber 10, and the outer sides of the first optical window 3 and the second optical window 4 are respectively adhered with the first piezoelectric ceramics 2 and the second piezoelectric ceramics 12 and can move for a certain degree;
the deformation quantity of the first piezoelectric ceramic 2 and the second piezoelectric ceramic 12 can be changed by changing the size of the electric field, so that the distance from the optical window to the resonant cavity is changed, and the length of each buffer chamber can be adjusted;
the first movable structure 4 and the second movable structure 7 are arranged at two ends of the resonant cavity 11 and are made of the same material as the resonant cavity 11;
the third piezoelectric ceramic 5 and the fourth piezoelectric ceramic 13 are fixed on one side close to the resonant cavity, and when the deformation quantity changes, the first movable structure 4 and the second movable structure 7 are driven, so that the equivalent length of the resonant cavity is adjusted.
The photoacoustic cell is arranged in an incubator (not shown in the figure) and used for adjusting the temperature of the photoacoustic cell, and the resistance heating pipe in the incubator enables the temperature in the incubator to rise in a heat dissipation mode.
A temperature sensor is also arranged in the constant temperature box and used for detecting the temperature of the photoacoustic cell; the temperature value detected by the temperature sensor is fed back to the temperature controller, if the temperature is lower than the set value, the heating is continued, and when the temperature reaches the set value, the heating is stopped to maintain the constant temperature.
Preferably, the ratio of the length of each buffer chamber to the length of the resonant cavity is 2: 1 and the ratio of its cross-sectional diameter to the cross-sectional diameter of the resonant cavity is 3: 1.
Preferably, the length of the resonant cavity 11 is 100mm, and the cross-sectional diameter is 10 mm; the first buffer chamber 9 and the second buffer chamber 10 are each 50mm in length.
The working principle of the device is described as follows: the resonant frequency of the photoacoustic cell is influenced by the structure and environmental parameters, such as processing precision, environmental temperature, pressure and other factors, and the working frequency of the photoacoustic cell can drift. Thus, the operating frequency of the photoacoustic cell can be adjusted to the standard resonant frequency by changing these relevant parameters.
For a cylindrical cavity, there is a resonant frequency formula (1)
Wherein q represents the number of longitudinal modes, Leffα where R is the radius of the cylindrical cavity, v is the speed of sound, for an equivalent cavity lengthmnIs the nth root of the mth order bessel function. Selecting a normal mode, wherein the longitudinal characteristic values, the angular characteristic values and the radial characteristic values are respectively 1, 0 and 0, and obtaining a formula (2) by a normal frequency formula:
where v is the speed of sound, LeffThe equivalent cavity length indicates that the resonant frequency of the photoacoustic cell is influenced by the sound velocity and the effective cavity length.
Wherein the formula of the sound velocity is (3)
Wherein gamma is the ratio of the constant pressure heat capacity to the constant volume heat capacity, and is a function of temperature, M is the relative molar mass, T is the temperature, and R is the molar gas constant. Because the main gas component in the cell is nitrogen, gamma is a fixed value, and R is a fixed value, the working frequency of the resonant cavity can be changed by changing the gas temperature T.
And the formula of the effective cavity length is (4)
L is the length of the resonant cavity, R is the radius of the resonant cavity, and the resonant frequency of the resonant cavity is changed by selecting to change the length of the resonant cavity because the resonant cavity is a cylinder and the radius is inconvenient to change.
The invention also provides a resonant frequency adjusting method based on the photoacoustic cell. As shown in fig. 2, the resonant frequency (i.e., the standard resonant frequency) of the photoacoustic cell is assumed to be 1000HZ, and the laser light source is modulated at this frequency. Under the influence of a certain temperature, the resonance frequency tends to drift, and the following method steps can be taken:
measuring real-time resonance frequency by using a resonance sonography method, comparing the value with the standard resonance frequency of 1000Hz, and directly starting subsequent detection work if the value is equal to the standard resonance frequency of 1000 Hz; if the difference exists, the temperature or the cavity length is changed to regulate and control the resonant frequency;
after the temperature or the cavity length is finely adjusted each time, the resonant frequency of the photoacoustic cell can be measured in real time by a resonant acoustic spectrum method, and if the resonant frequency is still not equal to 1000Hz, the micro temperature or the cavity length is continuously changed until the measured frequency is equal to the standard resonant frequency.
The above negative feedback regulation process is based on fine control of changes in cavity length and temperature. Assuming that the adjustment accuracy of the temperature is 0.5K, the adjustment accuracy of the resonant frequency is about 0.08% as obtained by the above equations (1) and (2); assuming that the adjustment accuracy of the cavity length is 0.02mm, the adjustment accuracy of the resonance frequency obtained by the foregoing formula (1) is about 0.02%. Therefore, if the drift degree of the resonant frequency is low, the cavity length can be preferentially adjusted; in addition, the above analysis also shows that the temperature adjustment range is larger, so if the resonant frequency drift degree is high, the temperature can be changed for coarse adjustment, and then the cavity length can be changed for fine adjustment.
For the change of the temperature, the working temperature of the resonant cavity can be adjusted by adjusting the set temperature of the thermostat, so that the resonant frequency is adjusted; in the process of changing the cavity length, when the third piezoelectric ceramic 5 and the fourth piezoelectric ceramic 13 make the first movable structure 4 and the second movable structure 7 move by Δ L respectively, so as to change the equivalent cavity length by 2 Δ L, in order to keep the length ratio of each buffer chamber to the resonant cavity 11 constant at 1: 2, the first optical window 3 and the second optical window 8 need to be moved by 2 Δ L respectively through the first piezoelectric ceramic 2 and the second piezoelectric ceramic 12, so that the length of each buffer chamber changes by Δ L. The Δ L of each change should be as small as possible to improve the accuracy of the negative feedback adjustment process.
The resonant frequency of the photoacoustic cell is measured in real time using a resonant acoustic spectroscopy in the above adjustment method. Resonance spectroscopy is the study of the resonant frequency of elastic objects excited by incident sound waves. Under the excitation of a sweep signal sound source, certain natural frequencies of the elastic material are obviously excited, and the elastic objects have different resonance frequencies due to different physical properties. When the physical properties of the object are not changed, the resonance frequency is also not changed, so that the resonance frequency of the elastic target object can be measured by adopting a resonance sonography method.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A photoacoustic cell with adjustable resonant frequency is characterized by being arranged in a constant temperature box and comprising a first buffer chamber (9), a second buffer chamber (10), a resonant cavity (11), a first optical window (3), a second optical window (8), a first movable structure (4) and a second movable structure (7);
the first optical window (3) and the second optical window (8) are respectively positioned outside the first buffer chamber (9) and the second buffer chamber (10);
a first piezoelectric ceramic is adhered to the outer side of the first optical window (3) and can displace under the action of the first piezoelectric ceramic; a second piezoelectric ceramic is adhered to the outer side of the second optical window (8) and can displace under the action of the second piezoelectric ceramic;
the first movable structure (4) and the second movable structure (7) are arranged on two sides of the resonant cavity (11), and the materials of the first movable structure and the second movable structure are the same as those of the resonant cavity (11);
a third piezoelectric ceramic is arranged between the first movable structure (4) and the resonant cavity (11), one side of the third piezoelectric ceramic close to the resonant cavity is fixed, and the other side of the third piezoelectric ceramic is adhered to the first movable structure (4) and can drive the first movable structure (4) to move; a fourth piezoelectric ceramic is arranged between the second movable structure (7) and the resonant cavity (11), one side of the fourth piezoelectric ceramic, which is close to the resonant cavity, is fixed, and the other side of the fourth piezoelectric ceramic is adhered to the second movable structure (7), so that the second movable structure (7) can be driven to move.
2. The photoacoustic cell of claim 1 wherein a temperature sensor is further disposed within the incubator to detect the temperature of the photoacoustic cell.
3. A photo acoustic cell as claimed in claim 2, characterized in that the resonant cavity (11) is of the first order cylindrical resonance type.
4. A photo acoustic cell as claimed in claim 3, further comprising a microphone (6) arranged in the resonant cavity (11) for detecting acoustic signals generated by the resonant cavity.
5. A photo acoustic cell as claimed in claim 3, characterized in that the length of the first buffer chamber (9) and the second buffer chamber (10) are equal, and the ratio to the length of the resonant cavity (11) is 1: 2.
6. A method for adjusting the resonant frequency of a photoacoustic cell according to any one of claims 1 to 5, comprising
Measuring the real-time resonance frequency of the photoacoustic cell, and comparing the real-time resonance frequency with the standard resonance frequency: if the detection result is equal to the preset detection result, directly starting subsequent detection work; if there is a difference, the temperature or cavity length is changed;
and after the temperature or the cavity length is changed every time, measuring the real-time resonant frequency of the photoacoustic cell again, and if the real-time resonant frequency is not equal to the standard resonant frequency, continuously changing the temperature or the cavity length until the real-time resonant frequency is equal to the standard resonant frequency.
7. The method of claim 6, wherein the real-time resonant frequency of the photoacoustic cell is measured using resonant sonography.
8. The method of claim 7, wherein the ratio of the lengths of the first and second buffer chambers to the length of the resonator is maintained constant at 1: 2.
9. A gas photoacoustic spectroscopy detection system comprising the photoacoustic cell of any one of claims 1-5.
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| CN113109268A (en) * | 2021-05-25 | 2021-07-13 | 武汉理工大学 | Photoacoustic spectroscopy enhancement device and method for gas detection using same |
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