CN114923863B - Detection chamber with hollow tubule for detecting substance component - Google Patents
Detection chamber with hollow tubule for detecting substance component Download PDFInfo
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- CN114923863B CN114923863B CN202210581922.0A CN202210581922A CN114923863B CN 114923863 B CN114923863 B CN 114923863B CN 202210581922 A CN202210581922 A CN 202210581922A CN 114923863 B CN114923863 B CN 114923863B
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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
- G01N21/05—Flow-through cuvettes
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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
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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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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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
- G01N21/05—Flow-through cuvettes
- G01N2021/052—Tubular type; cavity type; multireflective
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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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N2021/651—Cuvettes therefore
Abstract
The invention discloses a detection chamber with a hollow tubule for detecting material components, which belongs to the technical field of environmental safety detection and comprises a detection chamber body, wherein the input end of the detection chamber body is connected with the output end of a laser, the output end of the detection chamber body is connected with a detection channel, the detection chamber body comprises a light inlet area, the hollow tubule and a light outlet area, the light inlet area is connected with the output end of the laser, the light outlet area is connected with the light inlet area through the hollow tubule, the light outlet area is also connected with the detection channel, the central axis of the hollow tubule is coincided with the central line of a laser beam emitted by the laser, the inner wall of the hollow tubule is plated with a metal film layer, an object to be detected is placed in the hollow tubule, or the object to be detected continuously flows through the hollow tubule. By applying the hollow tubule, the Raman scattered waves generated by the laser and the substance to be detected can be gathered to form a thin beam, and then the thin beam is transmitted to a subsequent detection channel, so that the intensity of a detection signal can be greatly improved, and the detection sensitivity is further greatly improved.
Description
Technical Field
The invention relates to the technical field of environmental safety detection, in particular to a detection chamber with a hollow thin tube for detecting substance components.
Background
Sensing and detecting techniques for substance components and contents or concentrations thereof are widely applied in the petrochemical industry, food industry, pharmaceutical industry, oil and gas transportation, oil and gas storage, environmental monitoring, coal mine explosion prevention, flour mill explosion prevention, cotton mill explosion prevention, customs drug detection, medical detection, prospecting and the like, so that the sensing and detecting techniques are widely regarded. Typical methods for detecting the composition of a substance and its content or concentration include chemical methods, X-ray diffraction methods, and optical methods: the chemical method is to judge whether the substance to be detected contains a certain substance by detecting the chemical characteristics, and has the defects of complex process and more time consumption; the X-ray diffraction method is to identify the material structure through a diffraction pattern so as to judge whether a sample to be detected contains a certain material component, and has the defect that the equipment is expensive; optical methods are usually used to detect the spectral characteristics of the substances to be detected, especially raman spectroscopy methods thereof, which can accurately determine the components of the substances, and are increasingly popular because each substance has a specific raman spectrum, commonly known as fingerprint spectrum.
However, in the process of generating the raman wave by the interaction of the substance to be detected and the light beam, the light intensity is low, so that the intensity of the generated raman wave is low, the defect of poor detection accuracy is easy to occur in the subsequent detection, and the detection sensitivity is reduced.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a detection chamber with a hollow thin tube for detecting substance components.
The technical scheme of the invention is as follows:
the detection chamber with the hollow tubule for detecting the substance components comprises a detection chamber body, wherein the input end of the detection chamber body is connected with the output end of a laser, and the output end of the detection chamber body is connected with a detection channel,
the inner wall of the hollow tubule is plated with a metal film layer, and an object to be detected is placed in the hollow tubule or continuously flows through the hollow tubule. .
The invention according to the above scheme is characterized in that the detection chamber body further comprises an air inlet area and an air outlet area, the air inlet area is connected with an air inlet pipe, the air outlet area is connected with an air outlet pipe, gas to be detected is filled into the air inlet area through the air inlet pipe and is filled into the air outlet area through the hollow thin pipe, and the gas in the air outlet area is discharged through the air outlet pipe.
Furthermore, the air inlet pipe and the exhaust pipe are both Z-shaped pipes.
Further, the width of the air inlet area is larger than the inner diameter of the hollow thin tube, and the width of the air inlet area is smaller than 3 times of the inner diameter of the hollow thin tube; the width of exhaust area is greater than the internal diameter of hollow tubule, just the width of exhaust area is less than 3 times of the internal diameter of hollow tubule.
The present invention according to the above aspect is characterized in that the length of the hollow tubule is 1cm to 20cm.
The invention according to the above aspect is characterized in that the metal film layer is any one of a gold film, a silver film, a copper film, an aluminum film, a tin film, and a stainless steel film.
The invention according to the above aspect is characterized in that the hollow tubule is a circular tube, an elliptical tube, or a polygonal tube.
The present invention according to the above aspect is characterized in that the diameter of the inner diameter/maximum inscribed circle of the hollow tubule is larger than the spot diameter of the light beam output by the laser, and the diameter of the inner diameter/maximum inscribed circle of the hollow tubule is smaller than 2 times the spot diameter of the light beam output by the laser.
The invention according to the above scheme is characterized in that the output end of the detection chamber body is sequentially connected with two or more optical filters, each optical filter is connected with a corresponding photoelectric conversion tube, and the photoelectric conversion tubes are sequentially connected with an operational amplifier, an a/D converter, a signal processor and a digital display.
Furthermore, the output end of the detection chamber body is connected with the first optical filter through an output lens, and the emission output end of each optical filter is connected with the latter optical filter.
According to the scheme, the Raman scattering wave generated by the laser and the substance to be detected can be gathered to form a thin beam by applying the hollow thin tube, and then the thin beam is transmitted to a subsequent detection channel, so that the intensity of a detection signal can be greatly improved, and the detection sensitivity is greatly improved; compared with the traditional detection chamber, the invention can improve the intensity of the detection signal by 5 orders of magnitude, does not need a complex and precise spectrometer and an X-ray device, and has the advantages of low cost and high detection speed.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a side cross-sectional view of a hollow tubule in one embodiment;
FIG. 3 is a side sectional view of a hollow tubule according to another embodiment;
FIG. 4a is a schematic structural view of a hollow thin tube of a circular tube provided with a spiral fine groove/slit;
FIG. 4b is a schematic view of a hollow thin tube of a square tube with a spiral fine groove/slit;
FIG. 4c is a side view of a hollow thin tube with a linear slot/seam;
FIG. 4d is a side view of the open pores of the hollow thin tube of the circular tube or the square tube;
FIG. 5 is a schematic diagram of the present invention applied to dual Raman wave detection;
FIG. 6 is a Raman spectrum of a standard substance when the present invention is applied to dual Raman wave detection;
FIG. 7 is a schematic diagram of the present invention applied to multiple Raman wave detection;
FIG. 8 is a Raman spectrum of the first standard substance when the present invention is applied to multiple Raman wave detection.
In the figures, the various reference numbers are:
10. a laser; 101. a laser beam; 11. an optical isolator;
20. a detection chamber;
21. a detection chamber body; 22. a hollow thin tube; 221. fine grooves/slits; 222. air holes; 23. a metal film layer; 24. an air inlet pipe; 25. an exhaust pipe;
30. a light beam converter;
411. a first optical filter; 412. a first output lens; 413. a first photoelectric conversion tube; 421. a second optical filter; 422. a second output lens; 423. a second photoelectric conversion tube; 431. a third optical filter; 432. a third output lens; 433. a third photoelectric conversion tube; 4N1, an Nth optical filter; 4N2, nth output lens; 4N3, an Nth photoelectric conversion tube;
50. a wave absorber;
60. an operational amplifier;
70. an A/D converter;
80. a signal processor;
90. a digital display.
Detailed Description
The invention is further described with reference to the following figures and embodiments:
as shown in fig. 1 to 4d, in order to overcome the defects of high cost and low precision of the detection chamber in the prior art for detecting the substance component, the invention provides a detection chamber with a hollow tubule for detecting the substance component, which comprises a detection chamber body 21, wherein the input end of the detection chamber body 21 is connected with the output end of the laser 10, and the output end of the detection chamber body is connected with the detection channel. The laser 10 is used for emitting laser which is used for acting with a substance to be detected, the detection channel is used for receiving light rays which are in the detection chamber body 21 and act with the substance to be detected, and data processing is carried out to analyze the substance to be detected in the detection chamber.
In this a take detection room of hollow tubule for detecting substance composition, detection room body 21 is including advancing light zone, hollow tubule 22 and going out the light zone, advances the light zone and is connected with the output of laser instrument 10, goes out the light zone and advances the light zone to be connected via hollow tubule 22, goes out the light zone and still is connected with detection channel. The central axis of the hollow tubule 22 coincides with the central axis of the laser beam 101 emitted by the laser 10, the laser beam 101 emitted by the laser 10 enters the hollow tubule 22 through the light inlet region, and after the laser beam reacts with the substance to be detected in the hollow tubule 22, the strong raman scattering wave is generated and emitted through the light outlet region, and enters the detection channel for light collection, signal conversion, data analysis and the like, and the central axis of the hollow tubule 22 also coincides with the central axis of the optical path system of the detection channel.
Preferably, the light inlet region is provided with a light inlet transparent window, the laser beam 101 enters the light inlet region through the light inlet transparent window, the light outlet region is provided with a light outlet transparent window, and the light beam which is reacted with the substance to be detected in the hollow tubule 22 is emitted through the light outlet transparent window and enters the subsequent detection channel.
The detection chamber body 21 further comprises an air inlet area and an air outlet area, wherein the width of the air inlet area is larger than the inner diameter of the hollow tubule 22, and the width of the air inlet area is smaller than 3 times, preferably 2 times, of the inner diameter of the hollow tubule 22; the width of the exhaust area is larger than the inner diameter of the hollow tubule 22, and the width of the exhaust area is smaller than 3 times, preferably 2 times, of the inner diameter of the hollow tubule 22, and because the gas to be measured enters the hollow tubule 22 through the gas inlet pipe 24 and leaves the hollow tubule 22 through the gas outlet pipe 25, the invention can ensure that sufficient gas to be measured enters the tubule.
As shown in fig. 2 and 3, in the first embodiment, the hollow tubule 22 is provided with an air inlet and an air outlet at both side ends thereof, and the inside of the hollow tubule 22 communicates with the air inlet region through the air inlet and communicates with the air exhaust region through the air outlet.
As shown in fig. 4a to 4d, in the second embodiment, the side wall of the hollow tubule 22 is formed with fine grooves/slits 221 and air holes 222 penetrating the side wall of the hollow tubule, and the inside of the hollow tubule 22 communicates with the air intake region and the air exhaust region through the fine grooves/slits 221 and the air holes 222, thereby forming a free passage for the flow of air inside and outside the hollow tubule 22. Specifically, the method comprises the following steps: when the narrow groove/slit 221 is provided in the side wall of the hollow narrow tube 22: the narrow groove/slit 221 may be linear parallel to the central axis of the hollow tubule 22, or may be a spiral (three-dimensional spiral) that surrounds the side wall of the hollow tubule 22, and the central axis of the spiral narrow groove/slit 221 coincides with the central axis of the hollow tubule. The slot width/slit width of the spiral fine slot/slit 221 is 0.1 to 1mm, and the pitch of the spiral line is 1 to 10mm. When the air hole 222 is provided in the side wall of the hollow tubule 22: the air holes 222 are uniformly or non-uniformly distributed on the side wall of the hollow tubule 22, the pore diameters of the air holes 222 are equal or different, all the air holes 222 are combined and distributed to form a net shape, the diameter of the air hole 222 is 0.1-1 mm, and the distance between the adjacent air holes 222 is 1-10 mm.
Preferably, the hollow tubule 22 has a length of 1cm to 20cm. The inner diameter/maximum inscribed circle of the hollow tubule 22 is larger than the spot diameter of the light beam output by the laser 10, and the inner diameter/maximum inscribed circle of the hollow tubule 22 is smaller than 2 times, preferably 1.3 times, the spot diameter of the light beam output by the laser 10. The hollow tubules 22 are circular, elliptical or polygonal (e.g., square, rectangular, pentagonal, hexagonal, heptagonal, octagonal, or other regular polygons, or non-regular polygons), and can be selected according to specific needs.
The inner wall of the hollow tubule 22 in the invention is plated with a metal film layer 23, and the reflection of light beams is realized through the metal film layer 23, so as to increase the effect between the laser and the substance to be detected. Specifically, the substance to be detected may be a solid substance to be detected, or may be a gaseous or liquid substance to be detected: when the substance to be detected is solid, the substance to be detected is placed in the hollow tubule 22; when the substance to be detected is gas/liquid, the substance to be detected continuously flows through the hollow tubule 22. In the present invention, the metal film layer 23 is any one of a gold film, a silver film, a copper film, an aluminum film, a tin film, and a stainless steel film, and is preferably a gold film.
The metal film layer 23 is plated in the hollow tubule 22, on one hand, the metal film forms a local surface plasma wave and amplifies the Raman scattering wave thousands to more than hundreds of thousands of times, on the other hand, the tubule restrains the Raman scattering wave in a one-dimensional area, so that the wave which is originally spherically dispersed is gathered in a one-dimensional linear structure, and the detection effect of the Raman scattering wave is improved by hundreds of times, therefore, the total detection effect is improved by more than hundreds of thousands of times compared with the traditional detection effect, and the invention has incomparable technical advantages, namely, extremely high detection sensitivity.
In order to match the inlet and outlet of the substance to be detected, the gas inlet area is connected with the gas inlet pipe 24, the gas outlet area is connected with the gas outlet pipe 25, the gas (or liquid and the like) to be detected is filled into the gas inlet area through the gas inlet pipe 24 and is filled into the gas outlet area through the hollow thin pipe 22, and the gas (or liquid and the like) in the gas outlet area is discharged through the gas outlet pipe 25. Preferably, the intake pipe 24 and the exhaust pipe 25 are each a zigzag pipe (zigzag pipe).
The output end of the detection chamber body 21 is provided with a beam converter 30, the output end of the detection chamber body 21 for realizing the light-gathering function is sequentially connected with two or more optical filters (including a first optical filter 411, a second optical filter 422, a third optical filter 433, 8230; and an Nth optical filter 4N 1), each optical filter is connected with a corresponding photoelectric conversion tube (including a first photoelectric conversion tube 413, a second photoelectric conversion tube 423, a third photoelectric conversion tube 433, 8230; and an Nth photoelectric conversion tube 4N 3) through a corresponding output lens (including a first output lens 412, a second output lens 422, a third output lens 432, a 8230; and an Nth output lens 4N 2), and the photoelectric conversion tubes are sequentially connected with an operational amplifier 60, an A/D converter 70, a signal processor 80 and a digital display 90. Specifically, the output end of the detection chamber body 21 is connected to the first optical filter 411 through an output lens, and the emission output end of each optical filter is connected to the next optical filter, so that the light beam is collected through the output lens.
The detection chamber with the hollow tubule for detecting the substance components and the Raman scattering waves generated by the substance to be detected are integrated into a thin light beam and transmitted to the photoelectric conversion tube, so that the propagation of the Raman scattering waves in other directions is greatly reduced, the detection signal intensity is greatly improved, and the detection sensitivity is greatly improved. Compared with the traditional detection mode, the aggregation effect improves the detection signal intensity by more than 5 orders of magnitude, and greatly improves the detection sensitivity.
Example 1
As shown in fig. 5 and 6, the present embodiment provides a dual raman wave detection system based on the detection chamber with a hollow tubule for detecting a substance component, which includes a laser 10, the detection chamber with a hollow tubule for detecting a substance component (i.e., the detection chamber 20), two output lenses, two optical filters, a wave absorber 50, two conversion lenses, two photoelectric conversion tubes, a dual-channel operational amplifier 60, an a/D converter 70, a signal processor 80, and a digital display 90. The light path part in the system is wrapped and sealed by a shell.
The laser 10 is connected with the detection chamber body 21 and is used for emitting the generated laser into the detection chamber body 21; preferably, the output end of the laser 10 is connected to the input end (i.e. the air inlet region) of the detection chamber body 21 through the optical isolator 11, and the reflected light of the detection chamber body 21 is isolated by the optical isolator 11 to avoid damage to the laser 10. The output light wavelength of the laser 10 is a certain wavelength between 300 nm and 200000nm, and is generally selected from 532nm, 780nm, 1064nm, or 1550nm. The intensity of the Raman scattering light is inversely proportional to the fourth power of the wavelength of the laser, but the fluorescence effect is reduced when the laser wavelength is longer, so that the short-wavelength laser needs to be selected for the material to be measured with weaker Raman effect, and the long-wavelength laser needs to be selected for the material to be measured with stronger Raman effect.
The output end of the detection chamber body 21 sequentially passes through the light beam converter 30 (including a first output lens and a second output lens) and then is connected with the first optical filter 411, the reflection output end of the first optical filter 411 is connected with the second optical filter 421, the output end of the second optical filter 421 is connected with the wave absorber 50, the light beam output by the detection chamber body 21 passes through the first output lens 412 and the second output lens 422 and then is focused into a parallel light beam, the first optical filter 411 outputs the optical signal of the first wavelength in the parallel light beam and sends the optical signals of the parallel light except the first wavelength to the second optical filter 421, the second optical filter 421 outputs the optical signal of the second wavelength in the input signal and sends the other light except the second wavelength in the input signal to the wave absorber 50 for absorption, so as to eliminate the interference of the non-raman light on the detection.
The output end of the first optical filter 411 is connected to the first photoelectric conversion tube 413 through the first output lens 412, and the output signal of the first optical filter 411 is collected by the first output lens 412 and then sent to the first photoelectric conversion tube 413 to be converted into a first electrical signal.
The output end of the second optical filter 421 is connected to the second photoelectric conversion tube 423 through the second output lens 422, and the output signal of the second optical filter 421 is collected by the second output lens 422 and then sent to the second photoelectric conversion tube 423 to be converted into a second electrical signal.
The output end of the first photoelectric conversion tube 413 and the output end of the second photoelectric conversion tube 423 are respectively connected to two input ends of the dual-channel operational amplifier 60, the first electrical signal is amplified by the dual-channel operational amplifier 60 to form a third electrical signal, and the second electrical signal is amplified by the dual-channel operational amplifier 60 to form a fourth electrical signal.
The output end of the dual-channel operational amplifier 60 is connected to the a/D converter 70, the signal processor 80, and the digital display 90 in sequence, the third electrical signal is converted into the first digital signal through the a/D converter 70 and is output from the first output end of the a/D converter 70, and the fourth electrical signal is converted into the second digital signal through the a/D converter 70 and is output from the second output end of the a/D converter 70.
The two digital signal input ends of the signal processor 80 are respectively connected with the first digital signal and the second digital signal output by the a/D converter 70, and after the first digital signal and the second digital signal are processed by mathematical operation by the signal processor 80, one digital signal giving the serial number of the substance component contained in the substance to be measured and the other digital signal giving the content or concentration of the corresponding component are output and finally displayed in the digital display 90.
In the above structure, the signal receiving center of the first photoelectric conversion tube 413 is located at the output end focal plane of the first output lens 412, and the signal receiving center of the second photoelectric conversion tube 423 is located at the output end focal plane of the second output lens 422, so as to obtain the highest power efficiency.
The principle of raman wave detection in this embodiment is as follows: generally, raman scattering of a substance to be measured by laser generates raman scattering waves with a plurality of wavelengths, and during measurement, possible substance components need to be measured successively, and the substance to be measured is preset to contain a specific substance component during each measurement. The first wavelength is a first intensity Raman scattering wavelength generated by interaction of the laser and the substance to be detected and is equal to one Raman scattering wavelength of the preset component, and the second wavelength is a second strong Raman scattering wavelength or a third strong Raman scattering wavelength generated by interaction of the laser and the substance to be detected and is the Raman scattering wavelength of the preset component.
The data memory included in the signal processor 80 stores characteristic raman data of various standard substances at a certain concentration, the characteristic raman data are the raman frequency shift values of the strongest and second-strongest or third-strongest raman scattering peaks of various standard substances at a certain concentration and the corresponding raman line intensities thereof, and the concentration values of the standard substances are stored in the memory together with the raman frequency shift and raman intensity values. The raman line intensity of the standard substance is a first digital signal and a second digital signal measured by using the standard substance as a substance to be measured in the detection chamber with the hollow tubule for detecting the substance component.
In the process of detecting the substance to be detected, the substance to be detected is placed into the detection chamber body 21 or is filled and continuously flows through the detection chamber body 21, and the laser signal generated by the laser 10 passes through the detection chamber body 21, the two optical filters, the two photoelectric conversion tubes, the two-channel operational amplifier 60 and the a/D converter 70 to output a first digital signal and a second digital signal. The signal processor 80 performs data processing, and specifically includes the following steps:
1. determining whether the substance to be detected contains a certain substance component and giving a corresponding logic signal. The method specifically comprises the following steps:
a1, acquiring a first proportional value and a second proportional value.
(1) The first ratio is a ratio of the first digital signal divided by the second digital signal.
(2) The data memory of the signal processor stores a first standard intensity value and a second standard intensity value corresponding to the standard substance component, and the second proportional value is a ratio of the first standard intensity value to the second standard intensity value.
And A2, acquiring a difference value between the first proportional value and the second proportional value.
And calculating the difference value between the first proportional value and the second proportional value, namely, taking the value obtained by subtracting the second proportional value from the first proportional value as the difference value.
And A3, acquiring the deviation degree of the first proportional value and the second proportional value.
The degree of deviation is equal to the ratio of the above difference divided by the second ratio.
And A4, determining whether the substance is contained or not, and giving a corresponding logic signal.
Giving out a logic signal whether the substance to be detected contains a certain substance component according to the deviation value, specifically: if the absolute value of the deviation degree is less than or equal to 10%, the corresponding substance component is contained, and the logic signal is 1; if the absolute value of the degree of deviation is greater than 10%, it means that the corresponding material component is not contained, the logic signal is 0.
2. And if the substance component is contained in the substance to be detected, determining the concentration value of the substance component contained in the substance to be detected.
And B1, determining a scaling factor of the normalized strength.
The normalized intensity scaling factor is a ratio of a first digital signal measured from the substance to be detected to a first normalized intensity signal of the standard substance stored in the data storage.
And B2, calculating the concentration of a certain substance component contained in the substance to be detected.
And (4) calculating a standard intensity ratio coefficient multiplied by the concentration value of the standard substance stored in the data memory to obtain the concentration of a certain substance component in the substance to be detected.
The system of the invention needs to measure the possible substance components successively during measurement, the substance to be measured is preset to contain one specific substance component during each measurement, and another specific substance component is measured after the measurement is finished. That is, the first wavelength and the second wavelength are both set as the characteristic raman scattering wavelength of the preset standard substance component, that is, the passing wavelength of the first optical filter is adjusted to be correspondingly equal to the strongest raman scattering wavelength of the preset standard substance component, meanwhile, the passing wavelength of the second optical filter is adjusted to be correspondingly equal to the second-strongest or third-strongest raman scattering wavelength of the preset standard substance component, and then whether the substance to be detected contains the standard substance component is detected; and repeating the detection process to finish the detection of the components of the various substances.
In one embodiment, it is desirable to detect whether the samples A and B to be tested contain a standard substance and determine the concentration. The raman spectrum of the standard substance is shown in fig. 6. As can be seen from FIG. 6, the Raman spectrum of the standard substance had a plurality of Raman scattering peaks, and 110cm in the spectrum was taken -1 (relative intensity: 0.95) 747cm -1 (relative intensity: 0.58) as a reference.
The detection chamber with the hollow thin tube for detecting the substance components and the corresponding detection system are adopted for detection:
(1) The concentration of the standard substance was set to 10 -6 The passing wavelength of the first optical filter is adjusted to allow Raman frequency shift to 110cm -1 While the passing wavelength of the second optical filter is adjusted to allow a Raman shift of 747cm -1 High pass of the raman line.
(2) Measured Raman frequency shift of 110cm -1 Has an absolute intensity of 1.52X 10 -2 Raman shift 747cm -1 Has an absolute intensity of 0.928X 10 -2 。
(3) The detection chamber with the hollow thin tube for detecting the substance components and the corresponding detection system are adopted to measure a sample A to be detected, the passing wavelengths of the two filters are the same as the setting of the measurement standard substance, and the Raman frequency shift of the sample A to be detected is measured to be 110cm -1 Has an absolute intensity of 1.064X 10 -6 Raman frequency shift 747cm -1 Has an absolute intensity of 0.632 × 10 -6 。
(4) Calculating a first ratio value of 1.52/0.928=1.638 and a second ratio value of 1.064/0.632=1.684; further, the degree of deviation of the second proportional value from the first proportional value can be calculated to be (1.684-1.638)/1.638 =0.0281, that is, the degree of deviation =2.81%.
(5) The absolute value of the deviation degree is less than 10%, namely, the standard substance component is contained in the sample to be detected.
(6) Calculating the content of standard substance components in the sample to be detected as follows: (1.064X 10) -6 /0.95×10 -2 )×10 -6 ＝1.12×10 -10 。
(7) Repeating the steps (3) to (6), and judging whether the sample B to be detected contains the substance:
measuring to obtain the Raman frequency shift of 110cm of the sample B to be measured -1 Has an absolute intensity of 1.961X 10 -6 Raman frequency shift 747cm -1 Has an absolute intensity of 0.822X 10 -6 . Accordingly, the second ratio at this time is 1.961/0.822=2.386, and the degree of deviation of the second ratio from the first ratio of the reference material at this time is (2.386-1.638)/1.638 =0.4567, that is, the degree of deviation is 45.67%.
That is, the absolute value of the deviation is greater than 10%, which indicates that the sample B to be measured does not contain the standard substance component, that is, the content is 0.
Example 2
As shown in fig. 7 and 8, the present embodiment provides a multiple raman wave detection system based on the detection chamber with a hollow capillary tube for detecting a substance component described above, which is different from embodiment 1 in that a plurality of (N) optical filters, conversion lenses, and photoelectric conversion tubes are provided, and the operational amplifier 60 is a multi-channel (N-channel) operational amplifier, and each optical filter is connected to a corresponding conversion lens and photoelectric conversion tube.
In addition, the first optical filter 411 of the N optical filters inputs the optical signal with the first wavelength in the parallel light beam into the first output lens 412 for being collected, and then the optical signal is sent into the first photoelectric conversion tube 413 to be converted into a first electric signal, and the first optical filter 411 also sends the optical signal out of the first wavelength in the parallel light beam into the second optical filter 421; the second optical filter 421 inputs the optical signal with the second wavelength in the received optical beam to the second output lens 422 for being collected, and then sends the optical signal into the second photoelectric conversion tube 423 to be converted into a second electrical signal, and the second optical filter 421 also sends the optical signal out of the second wavelength in the received optical signal to the third optical filter 431; and so on, until the nth optical filter 4N1 inputs the optical signal with the nth wavelength in the received optical signal into the nth output lens 4N2 for focusing, and then sends the optical signal into the nth photoelectric conversion tube 4N3 for converting into the nth electrical signal, the nth optical filter 4N1 also sends the optical signal out of the nth wavelength in the optical beam into the wave absorber 50, so as to eliminate the interference of the non-raman light on the detection.
In the above structure, the signal receiving center of the X-th photoelectric conversion tube is located on the focal plane of the output end of the X-th conversion lens to obtain the highest power efficiency, where X takes a value of 1 to N.
The principle of raman wave detection in this embodiment is as follows: raman scattering of a substance to be detected on laser generally generates Raman scattering waves with multiple wavelengths, wherein the 1 st to m wavelength is the wavelength of high-intensity Raman scattering waves generated by interaction of the laser and the substance to be detected; the (m + 1) -N wavelength is the wavelength at which the laser and the substance to be detected do not generate Raman scattered waves when interacting; during measurement, the possible substance components need to be measured successively, and the substance to be detected is preset to contain a specific substance component during each measurement.
The signal processor is an N-channel signal processor and comprises a data memory, and the data memory stores characteristic Raman data of various standard substances under certain concentration, wherein the characteristic Raman data are Raman frequency shift values of Raman scattering peaks with 1 st to m intensities of various standard substances under certain concentration and corresponding Raman spectral line intensities thereof, and the m-to-N non-Raman scattering frequencies and intensities of the standard substances; the concentration value of the standard substance is also stored in the memory; the Raman spectrum line intensity of the standard substance is a digital signal corresponding to 1-m strong Raman scattering and a digital signal corresponding to (m + 1) -N non-Raman scattering, which are measured by using the standard substance as a substance to be measured and utilizing the detector based on the inner wall metal-plated film slotted tubule and the multiple Raman waves, and is defined as a1 st standard intensity signal, a2 nd standard intensity signal \8230, and an Nth standard intensity signal.
The N digital signal input terminals of the N-channel signal processor are respectively connected to the first to N-th digital signals output from the N-channel a/D converter 70, and after the N digital signals are subjected to mathematical operation by the signal processor, one digital signal giving the component number of the standard substance contained in the substance to be measured and the other digital signal giving the amount or concentration of the corresponding standard substance are output and finally displayed in the digital display 90. The signal processor performs data processing, and specifically comprises the following steps:
1. determining whether the substance to be detected contains a certain substance component and giving a corresponding logic signal. The method specifically comprises the following steps:
and A1, acquiring N ratios and N reference ratios.
(1) Dividing the first digital signal to the Nth digital signal by the first digital signal respectively to obtain N ratios, wherein the first ratio is 1;
(2) The data memory of the signal processor stores a first standard intensity value to an Nth standard intensity value corresponding to the standard substance component, and the first standard intensity value to the Nth standard intensity value are divided by the first standard intensity value respectively to obtain N reference ratios, wherein the first reference ratio is 1.
And A2, acquiring N-1 deviation values.
And calculating the difference between the obtained X-th ratio and the X-th reference value (namely subtracting the X-th reference ratio from the obtained X-th ratio), and dividing the difference by the X-th reference ratio to obtain the X-th deviation, wherein X takes 2-N.
And A3, determining whether the substance is contained or not, and giving a corresponding logic signal.
Giving out a logic signal whether the substance to be detected contains a certain substance component according to the deviation value, specifically: if the maximum value of the absolute value of the X deviation degree is less than or equal to 10 percent, the corresponding substance component is contained, and the logic signal is 1; and if the maximum value of the absolute value of the X-th deviation degree is more than 10%, the corresponding material component is not contained, the logic signal is 0 at the moment, and X takes a value of 2-N.
2. And if the substance component is contained in the substance to be detected, determining the concentration value of the substance component contained in the substance to be detected.
And B1, determining a scaling factor of the intensity of the benchmarks.
And calculating the ratio of the first digital signal to the first standard intensity signal of the standard substance stored in the data memory, and defining the ratio as a standard intensity proportionality coefficient.
And B2, calculating the concentration of a certain substance component contained in the substance to be detected.
And (4) calculating the standard intensity proportionality coefficient multiplied by the concentration value of the standard substance stored in the data memory to obtain the concentration of a certain substance component contained in the substance to be detected.
In a specific detection operation, the substance to be detected is preset to contain a specific substance component every time of detection, that is, the first wavelength to the mth wavelength are set as the characteristic raman scattering wavelength of the preset component, the (m + 1) th wavelength to the nth wavelength are non-raman scattering wavelengths, that is, the passing wavelengths of the first optical filter to the mth optical filter in the N optical filters are adjusted to be correspondingly equal to the 1 st raman scattering wavelength to the m raman scattering wavelength of the preset component, and the passing wavelengths of the m +1 th optical filter to the nth optical filter are adjusted to be correspondingly equal to the m +1 th non-raman scattering wavelength to the nth non-raman scattering wavelength of the preset component, and then whether the specific substance component is contained or not is detected.
In one embodiment, it is desirable to detect whether a sample to be tested contains a certain standard substance A and determine the concentration. The raman spectrum of the standard substance a is shown in fig. 8. As can be seen from FIG. 8, the Raman spectrum of the standard substance had a plurality of Raman scattering peaks, and 1003cm in the spectrum was taken -1 (relative intensity: 0.96) 140cm -1 (relative intensity: 0.70) as the 1 st to 2 nd reference lines of the reference substance A, and 400cm was taken -1 (relative intensity: 0.027), 600cm -1 (relative intensity: 0.019) and 800cm -1 Three non-Raman scattering spectral lines (relative intensity: 0.016) are taken as reference spectral lines.
The detection chamber with the hollow thin tube for detecting the substance components and the corresponding detection system are adopted for detection:
(1) The concentration of the standard substance was set to 2%, and the pass wavelength of the first of the five optical filters was adjusted to allow a Raman shift of 1003cm -1 Raman spectrum ofHigh pass, the pass wavelength of the second optical filter is adjusted to allow Raman shift to 140cm -1 The Raman spectral line of the optical fiber is high-pass, and the third optical filter, the fourth optical filter and the fifth optical filter are respectively adjusted to the non-Raman scattering wavelength of 400cm -1 、600cm -1 、800cm -1 High pass through the spectral line of (a).
(2) Measured Raman spectral line 1003cm -1 Has an absolute intensity of 1.92x10 -2 Raman spectrum line 140cm -1 Has an absolute intensity of 1.40X 10 -2 non-Raman spectrum line 400cm -1 、600cm -1 、800cm -1 Has an absolute intensity of 0.54X 10 -3 、0.38×10 -3 、0.32×10 -3 。
(3) The first to fifth reference ratios of the standard substance a were calculated to be 1, 0.7292, 0.0281, 0.0198, and 0.0167, respectively.
(4) The detection chamber with the hollow thin tube for detecting the substance components and the corresponding detection system are adopted to measure whether the sample to be detected contains the standard substance A and the content thereof. The passing wavelengths of the three filters are the same as the arrangement of the standard substance A, and the measured sample also has two Raman scattering spectral lines and three non-Raman spectral lines, namely 1003cm -1 (Absolute intensity: 1.652X 10-6) 140cm -1 (Absolute intensity: 1.213X 10-6) 400cm -1 (Absolute intensity: 4.622X 10) -8 )、600cm -1 (Absolute Strength: 3.273X 10) -8 )、800cm -1 (Absolute intensity: 2.768X 10) -6 )。
(5) From this, the first to fifth ratios 1, 0.7343, 0.02798, 0.01981, 0.01676 can be calculated; according to the foregoing first to fifth reference ratios for the standard substance a: 1. 0.7292, 0.0281, 0.0198, and 0.0167, and the degrees of deviation from the second reference ratio to the fifth reference ratio with respect to the standard substance a were calculated to be 0.0070, -0.0043, 0.0005, and 0.0036, respectively, and thus the maximum value of the absolute values of these two degrees of deviation was calculated to be 0.0070=0.7%.
(6) Since the maximum value of the absolute values of the two degrees of deviation is 0.7% <10%, it indicates that the sample to be tested contains the component A of the standard substance.
(7) Calculating the content of standard substance components in the sample to be detected as follows: (1.652X 10) -6 /0.82×10 -2 )x2％＝4.029×10 -6 。
Finally, the sample to be detected contains the standard substance component A, and the content of the standard substance component A is 4.029 multiplied by 10 -6 。
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
The invention is described above with reference to the accompanying drawings, which are illustrative, and it is obvious that the implementation of the invention is not limited in the above manner, and it is within the scope of the invention to adopt various modifications of the inventive method concept and technical solution, or to apply the inventive concept and technical solution to other fields without modification.
Claims (8)
1. The detection chamber with the hollow tubule for detecting the substance components comprises a detection chamber body, wherein the input end of the detection chamber body is connected with the output end of a laser, and the output end of the detection chamber body is connected with a detection channel;
the inner wall of the hollow tubule is plated with a metal film layer, and an object to be detected is placed in the hollow tubule or continuously flows through the hollow tubule;
the detection chamber body further comprises an air inlet area and an air outlet area, the air inlet area is connected with an air inlet pipe, the air outlet area is connected with an air outlet pipe, an object to be detected is filled into the air inlet area through the air inlet pipe and is filled into the air outlet area through the hollow thin pipe, air in the air outlet area is exhausted through the air outlet pipe, the width of the air inlet area is larger than the inner diameter of the hollow thin pipe, and the width of the air inlet area is smaller than 3 times of the inner diameter of the hollow thin pipe; the width of the exhaust area is larger than the inner diameter of the hollow tubule, and the width of the exhaust area is smaller than 3 times of the inner diameter of the hollow tubule;
the side wall of the hollow thin tube is provided with a thin groove or a thin slit or an air hole which penetrates through the side wall of the hollow thin tube, and the inside of the hollow thin tube is communicated with the air inlet area and the air exhaust area through the thin groove/the thin slit or the air hole to form a free passage for the air to flow inside and outside the hollow thin tube;
laser beams emitted by the laser enter the hollow thin tube through the light inlet area, generate strong Raman scattering waves after the laser beams react with a substance to be detected in the hollow thin tube, emit the strong Raman scattering waves through the light outlet area, and enter the detection channel to perform light collection, signal conversion and data analysis.
2. The detection chamber with the hollow tubule for detecting the component of the substance according to claim 1, wherein the intake pipe and the exhaust pipe are both Z-shaped pipes.
3. The detection chamber with a hollow tubule for detecting a substance component according to claim 1, wherein the hollow tubule has a length of 1cm to 20cm.
4. The detection chamber with the hollow tubule for detecting the substance component according to claim 1, wherein the metal film layer is any one of a gold film, a silver film, a copper film, an aluminum film, a tin film, or a stainless steel film.
5. The detection chamber with a hollow tubule for detecting a substance component according to claim 1, wherein the hollow tubule is a circular tube, an elliptical tube, or a polygonal tube.
6. The detection chamber with a hollow tubule for detecting a substance component according to claim 1, wherein an inner diameter or a maximum inscribed circle of the hollow tubule has a diameter larger than a spot diameter of a beam output from the laser, and the inner diameter or the maximum inscribed circle of the hollow tubule has a diameter smaller than 2 times the spot diameter of the beam output from the laser.
7. The detection chamber with the hollow capillary for detecting the component of a substance according to claim 1, wherein two or more optical filters are connected to an output end of the detection chamber body in this order, each of the optical filters is connected to a corresponding photoelectric conversion tube, and the photoelectric conversion tube is connected to an operational amplifier, an a/D converter, a signal processor, and a digital display in this order.
8. The detection chamber with the hollow tubule for detecting the component of the substance according to claim 7, wherein an output end of the detection chamber body is connected to a first one of the optical filters through an output lens, and an emission output end of each of the optical filters is connected to a subsequent one of the optical filters.
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