CN112362635A - Remote material detection device based on ultraviolet Raman spectrum analysis - Google Patents
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- 238000001514 detection method Methods 0.000 title claims abstract description 90
- 238000001237 Raman spectrum Methods 0.000 title claims abstract description 60
- 238000004458 analytical method Methods 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000000523 sample Substances 0.000 claims abstract description 31
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 230000003595 spectral effect Effects 0.000 claims abstract description 21
- 238000001228 spectrum Methods 0.000 claims abstract description 21
- 238000010183 spectrum analysis Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 28
- 238000003860 storage Methods 0.000 claims description 9
- 238000005057 refrigeration Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 238000005139 ultra-violet Raman spectroscopy Methods 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 abstract description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 14
- 230000005284 excitation Effects 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 1
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- 230000023004 detection of visible light Effects 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002594 fluoroscopy Methods 0.000 description 1
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- 238000003384 imaging method Methods 0.000 description 1
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- 230000010349 pulsation Effects 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—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
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Abstract
The invention provides a remote material detection device based on ultraviolet Raman spectrum analysis, which relates to the field of laser detection and comprises the following components: the remote detection probe comprises an ultraviolet collimating lens and an ultraviolet objective lens which are coaxially arranged; the ultraviolet laser is used for continuously emitting ultraviolet laser beams, transmitting the ultraviolet laser beams to the remote detection probe through the ultraviolet light path component, and converging and irradiating a detection target through the ultraviolet collimating lens; the remote detection probe continuously receives the target scattered light through the ultraviolet objective lens and sends the target scattered light to an ultraviolet spectrometer through the ultraviolet light path component, and the ultraviolet spectrometer filters and performs spectral analysis on the target scattered light to obtain a target spectral curve and obtains a Raman spectrum by capturing the target spectral curve; and the analysis device is used for comparing the Raman spectrum with a plurality of known material spectrum data in a multidimensional way to obtain a material component analysis result. The invention uses the ultraviolet pulse quasi-continuous emitting laser to increase the emitting distance of the laser, realizes the remote non-contact detection, and reduces the influence of stray light on the detection precision by matching with the light filtering component.
Description
Technical Field
The invention relates to the field of laser detection, in particular to a remote substance detection device based on ultraviolet Raman spectrum analysis.
Background
There are many instruments capable of analyzing the composition of a substance, but there are few instruments capable of remotely detecting and analyzing substances of several meters, and particularly, a detection means capable of remotely analyzing substances without contact on site is still scarce. The reason is discussed, because the mass spectrometer is accurate but heavy except for the laser Raman spectrometer in the existing commonly used substance analysis instrument, a sample to be detected is placed into a detection end after preparation and is subjected to mass spectrometry under a vacuum magnetic field by virtue of ionization, and remote detection cannot be realized; various infrared spectrometers also need to put the prepared test object into an instrument to test the characteristic infrared spectrum consisting of infrared absorption peaks under infrared radiation, and are difficult to perform fine detection on a target object at a distance; gas chromatography needs to collect the volatile gas of the articles and send the volatile gas into an instrument to measure the running speed of gas molecules in a capillary, and is not suitable for analyzing various articles at a distance; the ion mobility spectrometer can carry out high-sensitivity analysis on the mobility characteristic value of gas molecules or wiped sample molecules under an electric field of ions of the gas molecules or the wiped sample molecules, but is difficult to carry out remote non-contact detection; the femtosecond laser THz spectrum substance analysis can realize the analysis of the components of the articles within tens of centimeters, but the manufacturing cost is very high and the remote detection is difficult; other polymer fluorescence quenching detection, X-ray fluoroscopy or back scattering detection, dielectric detection, surface acoustic wave detection, chemical reaction detection and the like can not detect which substance component is the target object in a long distance and without contact.
For a laser Raman spectrometer, a laser beam is used for striking on an object to excite a scattering spectrum generated by vibration energy level jump absorption of a substance molecule, the scattering spectrum represents characteristic values of various substance molecules, and a laser Raman spectrum curve of the object can be obtained by capturing and taking the characteristic values by the spectrometer, so that the substance of a sample can be analyzed and detected finely. However, the laser wavelength and the detection distance of the laser raman spectrometer are directly related to the analysis effect: since the scattered spectral energy of laser excitation is only 1/10 or less of the excitation light energy, the received light energy affects the detection distance in inverse square relation, and the excitation light energy is weaker the farther the distance is; the energy of the light is related to the wavelength, the Raman scattering intensity is inversely proportional to the 4 th power of the wavelength of the excitation light, for example, the Raman spectrum intensity of laser excitation with the wavelength of 633nm is 14 times smaller than that of laser excitation with the wavelength of 325 nm; when the object molecules are irradiated by light, the object molecules can be excited to generate fluorescence, and the fluorescence can interfere with the Raman spectrum detection of visible light; the substance is excited at certain ultraviolet wavelengths of the excitation light to produce a resonance spectroscopy phenomenon, which is a scattered light with enhanced output. The early detection of laser raman spectrometer is to irradiate an object with visible light laser or near infrared laser at a short distance to obtain an excited raman spectrum, and can perform short-distance material analysis of some articles, but the interference of fluorescence to a visible light or infrared raman spectrum curve is often caused, and a sample at a long distance cannot excite an ingestible raman scattering spectrum due to too weak energy, so that the problems of low intrinsic raman scattering efficiency, fluorescence interference and the like caused by visible light and infrared light in the past are solved, and the common laser raman spectrometer is only suitable for detection and analysis beside articles.
In recent years, raman spectroscopy instruments and technologies using ultraviolet laser have appeared, which improve intrinsic raman scattering efficiency and eliminate interference of fluorescence on raman spectroscopy curves, but the detection distance of general raman spectroscopy instruments is still not long enough, and the raman spectroscopy instruments which have article detection and analysis distances up to several meters due to the factors of small ultraviolet laser energy, poor imaging quality of an ultraviolet optical system, short optical focal length of a detection probe, small aperture and the like do not appear in the market.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a remote substance detection device based on ultraviolet Raman spectrum analysis, which specifically comprises:
the remote detection probe comprises an ultraviolet collimating lens and an ultraviolet objective lens which are coaxially arranged;
the ultraviolet laser is connected with the remote detection probe through an ultraviolet light path component and is used for continuously emitting ultraviolet laser beams, and each ultraviolet laser beam is sent to the remote detection probe through the ultraviolet light path component and is converged through the ultraviolet collimating lens and then irradiates a detection target;
the ultraviolet spectrometer is connected with the remote detection probe through the ultraviolet light path component, and the remote detection probe continuously receives target scattered light generated by the detection target through the ultraviolet objective lens and sends the target scattered light to the ultraviolet spectrometer through the ultraviolet light path component;
the ultraviolet spectrometer is used for sequentially carrying out filtering processing and spectral analysis on each target scattered light to obtain a corresponding target spectral curve, and acquiring a corresponding Raman spectrum from each target spectral curve;
and the analysis device is connected with the ultraviolet spectrometer and is used for carrying out multi-dimensional comprehensive comparison on each Raman spectrum and a plurality of pre-stored known material spectrum data to obtain a material component analysis result of the detection target corresponding to each Raman spectrum.
Preferably, a laser power supply is further arranged for connecting the ultraviolet laser and used for supplying power to the ultraviolet laser.
Preferably, the ultraviolet laser is an ultraviolet pulsating quasi-continuous emission laser.
Preferably, a light filtering component is arranged on the ultraviolet spectrometer, and the ultraviolet spectrometer performs the light filtering treatment on the target scattered light through the light filtering component.
Preferably, the filtering component is an ultraviolet band-pass rayleigh cut-off filtering component, and the filtering process is to perform rayleigh filtering on the target scattered light to filter an invalid band in the target scattered light.
Preferably, an ultraviolet linear array sensor is arranged on the ultraviolet spectrometer, and the spectrometer obtains corresponding raman spectra by taking each target spectral curve through the ultraviolet linear array sensor.
Preferably, the ultraviolet linear array sensor is an ultralow temperature refrigeration linear array sensor.
Preferably, the device further comprises a frame synchronization device, which is respectively connected to the ultraviolet laser and the ultraviolet linear array sensor, and is used for controlling the time of the ultraviolet laser outputting the ultraviolet laser beam to be consistent with the time of the ultraviolet linear array sensor performing raman spectrum pickup.
Preferably, the analysis device comprises:
a receiving unit configured to receive each of the raman spectra;
the storage unit is used for storing the spectral data of the known substances;
and the analysis unit is respectively connected with the receiving unit and the storage unit and is used for performing similarity matching on each Raman spectrum and a plurality of known material spectrum data to obtain the probability that each Raman spectrum contains each known material spectrum data as a material component analysis result of the detection target.
Preferably, the system further comprises an energy device, which is respectively connected with the ultraviolet linear array sensor and the analysis device and is used for respectively supplying power to the ultraviolet linear array sensor and the analysis device.
The technical scheme has the following advantages or beneficial effects:
(1) the laser is emitted quasi-continuously by using ultraviolet pulsation, so that the emission distance of the laser is increased, the long-distance non-contact detection is realized, and the influence of stray light on the detection precision is reduced by using a light filtering component in a matching way;
(2) and performing multi-dimensional comprehensive comparison on the Raman spectrum and a plurality of known substance spectrum data through an analysis device to realize substance component analysis of the detection target corresponding to each Raman spectrum.
Drawings
FIG. 1 is a schematic diagram of a remote material detection device according to a preferred embodiment of the present invention;
FIG. 2 is a schematic diagram of an analysis device according to a preferred embodiment of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present invention is not limited to the embodiment, and other embodiments may be included in the scope of the present invention as long as the gist of the present invention is satisfied.
In a preferred embodiment of the present invention, based on the above problems in the prior art, there is provided a remote substance detecting apparatus based on uv-raman spectroscopy, as shown in fig. 1, specifically including:
the remote detection probe 3, the remote detection probe 3 includes a ultraviolet collimator 31 and an ultraviolet objective lens 32 that are coaxially arranged;
the ultraviolet laser 1 is connected with the remote detection probe 3 through an ultraviolet light path component 2 and is used for continuously emitting ultraviolet laser beams, and each ultraviolet laser beam is sent to the remote detection probe 3 through the ultraviolet light path component 2 and is converged through an ultraviolet collimating lens 31 and then irradiates a detection target;
the ultraviolet spectrometer 4 is connected with the remote detection probe 3 through the ultraviolet light path component 2, and the remote detection probe 3 continuously receives target scattered light generated by a detection target through the ultraviolet objective lens 32 and sends the target scattered light to the ultraviolet spectrometer 4 through the ultraviolet light path component 2;
the ultraviolet spectrometer 4 is used for sequentially carrying out filtering processing and spectral analysis on each target scattered light to obtain a corresponding target spectral curve, and acquiring a corresponding Raman spectrum from each target spectral curve;
and the analysis device 6 is connected with the ultraviolet spectrometer 4 and is used for carrying out multi-dimensional comprehensive comparison on each Raman spectrum and a plurality of pre-stored known material spectrum data to obtain a material component analysis result of the detection target corresponding to each Raman spectrum.
Specifically, in this embodiment, in order to implement detection and analysis of raman spectrum material components of a target object that is several meters away on site, without being affected by weak raman spectrum energy and large attenuation of long-distance optical energy, according to the inverse relationship between the energy of excitation light and the fourth power of excitation light wavelength, a low-band ultraviolet laser with high relative energy is selected as the excitation light for long-distance raman spectrum detection, and an ultraviolet pulsed quasi-continuous emission laser capable of generating intensified laser is adopted to increase the excitation power output by the ultraviolet laser, so that the peak power of the laser output is much greater than the average power, and the material raman spectrum with a certain intensity can still be excited after the large attenuation of the optical energy distance square is satisfied.
The remote detection probe 3 consists of an ultraviolet collimator lens 31 and an ultraviolet objective lens 32, the ultraviolet collimator lens 31 is positioned at one end of the remote detection probe 3 close to a detection target, and the ultraviolet objective lens 32 is positioned at one end of the remote detection probe 3 far away from the detection target; the remote detection probe 3 adopts a Raman spectrum low-loss remote detection probe, so that the laser energy loss of a light path is greatly reduced to meet the Raman spectrum excitation detection requirement of remote detection.
The remote detection probe 3 is fixed on an ultraviolet light path component 2 which guides ultraviolet laser beams to converge and emit and images the target scattered light on a window of an ultraviolet spectrometer. In this embodiment, the high-sensitivity ultraviolet spectrometer 4 capable of receiving a weak ultraviolet laser spectrum is adopted, so that the influence of fluorescence, ambient light, excitation light, stray light and dust on the target scattered light is reduced. The ultraviolet spectrometer 4 performs rayleigh filtering on the target scattered light by using an ultraviolet band-pass rayleigh cut-off filtering component 8 to filter an invalid waveband in the target scattered light. The target spectrum of the ultraviolet spectrometer 4 is taken by the ultraviolet linear array sensor 5 capable of realizing ultralow temperature refrigeration, the linear array sensor has higher sensitivity due to ultralow temperature, a weaker Raman spectrum can be shot, the photon energy of ultraviolet laser can excite the resonance spectrum line of some substance molecules, and the resonance spectrum line has high energy and is easy to read by the ultralow temperature refrigeration linear array sensor. In the technical scheme, the time for outputting the ultraviolet laser beam by the ultraviolet laser 1 is controlled to be consistent with the time for taking the Raman spectrum by the ultraviolet linear array sensor 5 through the frame synchronization device 9, so that the temperature of the ultraviolet linear array sensor 5 is ensured to be lower, the quality of taking the Raman spectrum is improved, and the precision of the device is improved.
The remote material detection in the technical scheme is a continuous process, so that the detection and analysis process is to analyze the Raman spectrum in a period of time. The raman spectrum captured by the ultraviolet line sensor 5 is transmitted to the analyzer 6 for detection and analysis, and in order to accurately obtain target scattered light excited by a target by irradiating the remote detection target with intensified laser without contact and pretreatment, the analyzer 6 makes full use of the spectral data of the known substance in the storage unit 62 as an element for performing multidimensional comparison with the raman spectrum, and the analyzer 6 performs similarity matching between the spectral data of the known substance in the storage unit 62 and the raman spectrum to obtain a probability that each raman spectrum includes the spectral data of the known substance as a substance component analysis result of the detection target.
In the preferred embodiment of the present invention, a laser power supply 7 is further provided to connect the uv laser 1 for supplying power to the uv laser 1.
Specifically, in this embodiment, the ultraviolet laser 1 is driven by providing the laser power supply 7 to supply power to the ultraviolet laser 1.
In a preferred embodiment of the present invention, the ultraviolet laser 1 is an ultraviolet pulsed quasi-continuous emission laser.
Specifically, in this embodiment, the ultraviolet pulsed quasi-continuous emission laser is used, so that the laser output peak power of the ultraviolet pulsed quasi-continuous emission laser is much larger than the average power of the ordinary ultraviolet laser 1, so that the optical energy can still excite the raman spectrum of the substance with a certain intensity after being greatly attenuated.
In the preferred embodiment of the present invention, a filter assembly 8 is disposed on the ultraviolet spectrometer 4, and the ultraviolet spectrometer 4 filters the target scattered light through the filter assembly 8.
In a preferred embodiment of the present invention, the filtering component 8 is an ultraviolet band-pass rayleigh cut-off filtering component, and the filtering process is to perform rayleigh filtering on the target scattered light to filter out invalid bands in the target scattered light.
Specifically, in this embodiment, the filtering component 8 employs an ultraviolet band-pass rayleigh cut-off component, the filtering component 8 performs rayleigh filtering processing on the target scattered light transmitted to the ultraviolet spectrometer 4, and the reflected laser, the background light and the excited fluorescence of the target scattered light are all cut off outside the wavelength of the band-pass filtered light by an ultraviolet band-pass super-steep cut-off filter in the ultraviolet band-pass rayleigh cut-off component, and enter the narrow slit window of the ultraviolet spectrometer 4 only through the raman spectrum band to be detected.
In a preferred embodiment of the present invention, an ultraviolet linear sensor 5 is disposed on the ultraviolet spectrometer 4, and the spectrometer obtains corresponding raman spectra by capturing each target spectral curve through the ultraviolet linear sensor 5.
In a preferred embodiment of the present invention, the ultraviolet linear array sensor 5 is an ultra-low temperature refrigeration linear array sensor.
Specifically, in this embodiment, the ultra-low temperature refrigeration linear array sensor is used for capturing the raman spectrum, the sensitivity of the linear array sensor is higher due to the ultra-low temperature, a weaker raman spectrum can be captured, the photon energy of the ultraviolet laser can excite the resonance line of some substance molecules, and the resonance line has large energy and is easy to be read by the ultra-low temperature refrigeration linear array sensor.
In a preferred embodiment of the present invention, the present invention further comprises a frame synchronization device 9, which is respectively connected to the ultraviolet laser 1 and the ultraviolet line sensor 5, and is configured to control a time when the ultraviolet laser 1 outputs the ultraviolet laser beam to be consistent with a time when the ultraviolet line sensor 5 performs raman spectrum capture.
Specifically, in this embodiment, the frame synchronization device 9 is arranged to control the time of the ultraviolet laser 1 outputting the ultraviolet laser beam to be consistent with the time of the ultraviolet array sensor 5 performing raman spectrum pickup, so as to ensure that the temperature of the ultraviolet array sensor 5 is low, improve the quality of the raman spectrum pickup, and improve the device precision.
In a preferred embodiment of the present invention, as shown in fig. 2, the analyzing device 6 includes:
a receiving unit 61 for receiving each raman spectrum;
a storage unit 62 for storing known substance spectral data;
and an analyzing unit 63, respectively connected to the receiving unit 61 and the storage unit 62, for performing similarity matching between each raman spectrum and a plurality of known substance spectral data to obtain a probability that each raman spectrum includes each known substance spectral data as a substance component analysis result of the detection target.
Specifically, in the present embodiment, the analysis unit 63 is configured to perform similarity matching between the raman spectrum received by the receiving unit 61 and a plurality of known material spectrum data in the storage unit 62, where the known material spectrum data includes some interference data: spectral line data influenced by interference of dust on the surface of the material, influence data of stray light of background light influenced by ambient light and mixture spectrum overlapping interference data are filtered out by comprehensive multidimensional similarity matching, and the probability that each Raman spectrum contains spectral data of known materials is obtained and used as a material component analysis result of a detection target.
In a preferred embodiment of the present invention, the method further comprises:
and the energy device 10 is respectively connected with the ultraviolet linear array sensor 5 and the analysis device 6 and is used for respectively supplying power to the ultraviolet linear array sensor 5 and the analysis device 6.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A remote material detection device based on ultraviolet Raman spectroscopy is characterized by specifically comprising:
the remote detection probe comprises an ultraviolet collimating lens and an ultraviolet objective lens which are coaxially arranged;
the ultraviolet laser is connected with the remote detection probe through an ultraviolet light path component and is used for continuously emitting ultraviolet laser beams, and each ultraviolet laser beam is sent to the remote detection probe through the ultraviolet light path component and is converged through the ultraviolet collimating lens and then irradiates a detection target;
the ultraviolet spectrometer is connected with the remote detection probe through the ultraviolet light path component, and the remote detection probe continuously receives target scattered light generated by the detection target through the ultraviolet objective lens and sends the target scattered light to the ultraviolet spectrometer through the ultraviolet light path component;
the ultraviolet spectrometer is used for sequentially carrying out filtering processing and spectral analysis on each target scattered light to obtain a corresponding target spectral curve, and acquiring a corresponding Raman spectrum from each target spectral curve;
and the analysis device is connected with the ultraviolet spectrometer and is used for carrying out multi-dimensional comprehensive comparison on each Raman spectrum and a plurality of pre-stored known material spectrum data to obtain a material component analysis result of the detection target corresponding to each Raman spectrum.
2. The remote material detection device of claim 1 wherein a laser power source is connected to said uv laser for powering said uv laser.
3. The remote material detection device of claim 2, wherein the ultraviolet laser is an ultraviolet pulsed quasi-continuous emission laser.
4. The remote material detection device as claimed in claim 1, wherein a filter assembly is disposed on the uv spectrometer, and the uv spectrometer performs the filtering process on the scattered light of the target through the filter assembly.
5. The remote material detection device as claimed in claim 4 wherein the filter assembly is an ultraviolet band-pass Rayleigh cut-off filter assembly, and the filtering is performed to Rayleigh filter the target scattered light to filter out invalid bands in the target scattered light.
6. The remote sensing device of claim 1, wherein an ultraviolet array sensor is disposed on the ultraviolet spectrometer, and the spectrometer captures each target spectrum curve through the ultraviolet array sensor to obtain a corresponding raman spectrum.
7. The remote material detection device as recited in claim 6, wherein the ultraviolet line sensor is an ultra-low temperature refrigeration line sensor.
8. The remote material detection device as claimed in claim 6, further comprising a frame synchronization device respectively connected to said uv laser and said uv line sensor for controlling the time of uv laser beam output from said uv laser to be consistent with the time of raman spectrum capture by said uv line sensor.
9. The remote species detection device of claim 1, wherein said analysis device comprises:
a receiving unit configured to receive each of the raman spectra;
the storage unit is used for storing the spectral data of the known substances;
and the analysis unit is respectively connected with the receiving unit and the storage unit and is used for performing similarity matching on each Raman spectrum and a plurality of known material spectrum data to obtain the probability that each Raman spectrum contains each known material spectrum data as a material component analysis result of the detection target.
10. The remote material detection device of claim 7, further comprising:
and the energy device is respectively connected with the ultraviolet linear array sensor and the analysis device and is used for respectively supplying power to the ultraviolet linear array sensor and the analysis device.
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| CN114965348A (en) * | 2022-07-27 | 2022-08-30 | 浙江数翰科技有限公司 | Spectrum analysis method and system based on sewage detection |
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