CN117347344A - A laser Raman gas detection device and method - Google Patents
A laser Raman gas detection device and method Download PDFInfo
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- CN117347344A CN117347344A CN202311193764.2A CN202311193764A CN117347344A CN 117347344 A CN117347344 A CN 117347344A CN 202311193764 A CN202311193764 A CN 202311193764A CN 117347344 A CN117347344 A CN 117347344A
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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
- 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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Abstract
The application provides a laser Raman gas detection device and a method, wherein the device comprises a light source assembly, a reflecting cavity and a spectrum analysis assembly, wherein the light source assembly provides incident lasers with different light paths into the reflecting cavity; the inner surface of the reflecting cavity surrounds an air chamber for accommodating the gas to be detected, the inner surface is configured to be provided with a plurality of reflecting positions, and the incident laser light of different light paths is circularly reflected in the air chamber through the plurality of reflecting positions respectively; the spectrum analysis assembly comprises a spectrometer for collecting spherical Raman scattered light generated by the reaction of laser and gas to be detected so as to provide Raman spectrum signals. The laser Raman gas detection device can realize real-time high-precision detection of various mixed gases, and has the advantages of simple structure, high sensitivity, high response speed and electromagnetic interference resistance.
Description
Technical Field
The application relates to the technical field of gas detection, in particular to a laser Raman gas detection device and method.
Background
Trace multicomponent gas detection has wide demands in social production, such as power transformer fault characteristic gas detection, gas insulated metal-enclosed switchgear fault characteristic gas detection, lithium iron phosphate energy storage battery thermal runaway gas separation, natural gas component on-line monitoring, seawater dissolved gas monitoring, food management and the like.
Currently, commonly used multi-component gas detection methods include gas chromatography, electrochemical sensor methods, semiconductor sensor methods, infrared absorption spectroscopy, photoacoustic spectroscopy, and photothermal spectroscopy. The gas chromatography has high detection sensitivity and better selectivity, but has the problem that the chromatographic column is easy to age and causes performance degradation, and maintenance and calibration must be carried out regularly; the electrochemical sensor method and the semiconductor sensor method have high detection sensitivity and high response speed, but relatively serious cross interference exists among different gas components, and the sensing material is easy to age and has unsatisfactory long-term stability; infrared absorption spectroscopy, photoacoustic spectroscopy, and photothermal spectroscopy have high detection sensitivity, but it is difficult to detect low-concentration homonuclear diatomic gases such as hydrogen, oxygen, nitrogen, and the like.
In summary, the existing multi-component gas detection methods cannot realize high-precision detection of trace multi-component gas.
Disclosure of Invention
In view of the above, the application provides a laser Raman gas detection device and a method, which solve the technical problem that the existing multi-component gas detection method cannot realize high-precision detection of trace multi-component gas, and the laser Raman gas detection device not only can realize real-time high-precision detection of various mixed gases, but also has the advantages of simple structure, high sensitivity, high response speed and electromagnetic interference resistance.
In a first aspect, embodiments of the present application provide a laser raman gas detection apparatus, including a light source assembly, a reflective cavity, and a spectral analysis assembly, wherein:
the light source component provides incident laser with different light paths into the reflecting cavity;
the inner surface of the reflecting cavity surrounds an air chamber for accommodating the gas to be detected, the inner surface is configured to be provided with a plurality of reflecting positions, and the incident laser light of different light paths is circularly reflected in the air chamber through the plurality of reflecting positions respectively;
the spectrum analysis assembly comprises a spectrometer for collecting spherical Raman scattered light generated by the reaction of laser and gas to be detected so as to provide Raman spectrum signals.
In one possible implementation, the light source assembly includes two sets of helium-neon lasers and a focusing lens; the focusing lens is fixed on the reflecting cavity and is arranged opposite to the two groups of helium-neon lasers;
the two groups of helium-neon lasers respectively emit two parallel helium-neon lasers with the wavelength of 632.8 nm;
the focusing lens is used for focusing laser into the air chamber.
In one possible implementation, the focusing lens is circular and is fixed to the reflective cavity by a support.
In one possible implementation, when the inner surface of the reflective cavity is configured as a sphere, the focal length of the focusing lens does not exceed half the radius of the sphere.
In one possible implementation, the reflective cavity is coated with a reflective film on its inner surface, the reflective film having a reflectivity of greater than 98%.
In one possible implementation, the reflective cavity is further provided with a closable air outlet and a closable air outlet, and the positions of the air inlet and the air outlet are arranged to avoid the light path in the air chamber.
In one possible implementation, the spectrometer includes a filter, a monochromator, and a sensor, wherein the filter has a transmittance of greater than 99% for spherical raman scattered light and no more than 5% for other light.
In one possible implementation, the spectral analysis assembly further comprises: and the electronic equipment is used for acquiring the Raman spectrum signals output by the spectrometer and generating a Raman spectrum chart, and separating out various gas types and corresponding concentration values in the mixed gas by utilizing the Raman spectrum chart.
In a second aspect, an embodiment of the present application provides a laser raman gas detection method, including:
providing incident laser light of different light paths for the gas to be detected in the reflecting cavity, wherein the inner surface of the reflecting cavity is configured to have a plurality of reflecting positions;
and collecting spherical Raman scattered light generated by the reaction of the laser circularly reflected by the plurality of reflection positions and the gas to be detected so as to provide Raman spectrum signals.
In one possible implementation, the method further comprises:
and acquiring the Raman spectrum signals, generating a Raman spectrum chart, and utilizing the Raman spectrum chart to separate out each gas type and corresponding concentration value in the mixed gas.
The laser Raman gas detection device can realize real-time high-precision detection of various mixed gases, and has the advantages of simple structure, high sensitivity, high response speed and electromagnetic interference resistance.
Drawings
Fig. 1 is a functional block diagram of a laser raman gas detection apparatus according to an embodiment of the present application;
fig. 2 is a schematic structural diagram of a specific implementation of a laser raman gas detection apparatus according to an embodiment of the present application;
FIG. 3 is a schematic diagram of the relationship between the focal length of a focusing lens and the radius of a spherical shell according to an embodiment of the present application;
fig. 4 is a flowchart of a laser raman gas detection method according to an embodiment of the present application;
fig. 5 is a schematic diagram of an electronic device according to an embodiment of the present application.
The attached drawings are identified:
1: a light source; 2: a support; 3-1: an air inlet; 3-2: an air outlet;
4: a focusing lens; 5: a spherical shell; 6: a reflective film;
7: a spherical air chamber; 8: a spectrometer; 9: an electronic device.
Detailed Description
Various aspects and features of the present application are described herein with reference to the accompanying drawings.
It should be understood that various modifications may be made to the embodiments of the application herein. Therefore, the above description should not be taken as limiting, but merely as exemplification of the embodiments. Other modifications within the scope and spirit of this application will occur to those skilled in the art.
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the application and, together with a general description of the application given above and the detailed description of the embodiments given below, serve to explain the principles of the application.
These and other characteristics of the present application will become apparent from the following description of a preferred form of embodiment, given as a non-limiting example, with reference to the accompanying drawings.
It is also to be understood that, although the present application has been described with reference to some specific examples, those skilled in the art can certainly realize many other equivalent forms of the present application.
The foregoing and other aspects, features, and advantages of the present application will become more apparent in light of the following detailed description when taken in conjunction with the accompanying drawings.
Specific embodiments of the present application will be described hereinafter with reference to the accompanying drawings; however, it is to be understood that the disclosed embodiments are merely exemplary of the application, which can be embodied in various forms. Well-known and/or repeated functions and constructions are not described in detail to avoid obscuring the application with unnecessary or excessive detail. Therefore, specific structural and functional details disclosed herein are not intended to be limiting, but merely serve as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present application in virtually any appropriately detailed structure.
The specification may use the word "in one embodiment," "in another embodiment," "in yet another embodiment," or "in other embodiments," which may each refer to one or more of the same or different embodiments as per the application.
First, the design concept of the embodiment of the present application will be briefly described.
Currently, commonly used multi-component gas detection methods include gas chromatography, electrochemical sensor methods, semiconductor sensor methods, infrared absorption spectroscopy, photoacoustic spectroscopy, and photothermal spectroscopy. The gas chromatography has high detection sensitivity and better selectivity, but has the problem that the chromatographic column is easy to age and causes performance degradation, and maintenance and calibration must be carried out regularly; the electrochemical sensor method and the semiconductor sensor method have high detection sensitivity and high response speed, but relatively serious cross interference exists among different gas components, and the sensing material is easy to age and has unsatisfactory long-term stability; infrared absorption spectroscopy, photoacoustic spectroscopy, and photothermal spectroscopy have high detection sensitivity, but it is difficult to detect low-concentration homonuclear diatomic gases such as hydrogen, oxygen, nitrogen, and the like.
Raman spectroscopy is based on the raman scattering effect of matter when the frequency is v 0 When the incident laser of (1) passes through the gas to be measured, the incident laser excites molecules of the gas to be measured (excluding monoatomic gas) to generate a frequency v 0 +v R Is a spherical raman scattered light of (c). The different gases all have a specific Raman frequency shift v R The intensity of the raman scattered light is linearly related to the concentration of the gas, so that by detecting the raman shift and the intensity of the raman scattered light, a plurality of different substances can be simultaneously qualitatively and quantitatively analyzed. In practical applications, since the intensity of the vibration raman peak of the gas is much higher than the intensity of the corresponding rotation peak, the quantitative and qualitative analysis of the gas is generally performed based on the vibration raman peak of each gas.
Compared with the traditional detection method, the Raman spectrum is used for detecting the multi-component mixed gas, and has the following advantages: all gas components other than monoatomic gases can be detected; single wavelength lasers can achieve simultaneous measurement of multiple component mixed gases.
However, since the gas scattering cross section is extremely low, the raman signal is weak, the trace gas is difficult to measure by the conventional spontaneous raman spectroscopy technology, and the detection lower limit of each gas component is different under the same detection system and detection condition.
Aiming at the problem that the existing multi-component gas detection method cannot realize high-precision detection of trace multi-component gas, the application designs a gas detection device which can realize real-time high-precision measurement of various gases and has the advantages of high sensitivity, high response speed, simple structure and electromagnetic interference resistance based on a gas Raman enhancement technology.
In order to increase the raman scattering detection sensitivity, cavity enhancement and fiber-enhanced raman spectroscopy techniques may be employed. The cavity enhancement improves the Raman signal intensity by improving the excitation light intensity and the action path of laser and gas, and mainly comprises multiple reflection cavity enhancement, F-P cavity enhancement and laser cavity enhancement. The optical fiber enhancement improves the Raman signal intensity by improving the collection efficiency of spherical Raman scattered light, and mainly comprises silver-plated capillary enhancement and hollow optical fiber enhancement.
The application adopts a spherical air cavity enhancement mode to improve the Raman scattering detection sensitivity. Based on the Raman scattering effect, real-time online measurement of various gas types and concentrations is realized. The spherical air cavity enhancement mode can enable the number of times of circulating reflection of laser in the cavity to be more, and the enhancement efficiency of the corresponding laser is higher.
In addition, this application adopts focus lens to change incident laser propagation direction to set up focus lens focus, make laser avoid air inlet and gas outlet etc. in spherical air chamber, adopt two laser incidence simultaneously, further improve the reinforcing efficiency of laser.
After the application scenario and the design idea of the embodiment of the present application are introduced, the technical solution provided by the embodiment of the present application is described below.
As shown in fig. 1, an embodiment of the present application provides a laser raman gas detection apparatus, which includes a light source assembly 101, a reflection cavity 102, and a spectrum analysis assembly 103, wherein:
the light source component 101 provides incident laser light with different light paths into the reflecting cavity;
the inner surface of the reflecting cavity 102 encloses a gas chamber for accommodating gas to be detected, the inner surface is configured to have a plurality of reflecting positions, and the incident laser light of different light paths is circularly reflected in the gas chamber through the plurality of reflecting positions respectively; wherein the gas to be detected is mixed gas;
the spectrum analysis assembly 103 comprises a spectrometer for collecting spherical raman scattered light generated by the reaction of laser light and gas to be detected to provide a raman spectrum signal.
Specifically, the light source assembly comprises two groups of helium-neon lasers and a focusing lens; the focusing lens is fixed on the reflecting cavity and is arranged opposite to the two groups of helium-neon lasers;
the two groups of helium-neon lasers respectively emit two parallel helium-neon lasers with the wavelength of 632.8 nm;
the focusing lens is used for focusing laser into the air chamber.
Preferably, the focusing lens is circular and is fixed on the reflecting cavity through a supporting piece.
When the inner surface of the reflective cavity is configured as a sphere, the focal length of the focusing lens does not exceed half the radius of the sphere.
Preferably, the inner surface of the reflecting cavity is plated with a reflecting film, and the reflectivity of the reflecting film is more than 98%.
As a possible implementation, the reflective cavity is further provided with a closable air outlet and a closable air outlet, and the positions of the air inlet and the air outlet are arranged to avoid the light path in the air chamber.
Specifically, the spectrometer comprises an optical filter, a monochromator and a sensor, wherein the optical filter has a transmittance of more than 99% for spherical Raman scattered light and a transmittance of not more than 5% for other light.
As a possible implementation manner, the spectrum analysis component further comprises: and the electronic equipment is used for acquiring the Raman spectrum signals output by the spectrometer and generating a Raman spectrum chart, and separating out various gas types and corresponding concentration values in the mixed gas by utilizing the Raman spectrum chart.
FIG. 2 provides a block diagram of one embodiment of a laser Raman gas detection apparatus, comprising: a light source 1, a spherical air chamber 7, a focusing lens 4, a spectrometer 8 and an electronic device 9, wherein the spherical air chamber 7 comprises a spherical shell 5, and the focusing lens 4 is arranged on the spherical shell 5 and opposite to the light source 1; the spherical shell 5 is provided with a closable air inlet 3-1 and a closable air outlet 3-2; the spectrometer 8 is arranged on the spherical shell 5 at a position opposite to the focusing lens 4;
the light source comprises two groups of helium-neon lasers, and two parallel helium-neon lasers with the wavelength of 632.8nm are respectively generated. The focusing lens focuses two laser beams into the spherical air chamber. The focusing lens is of a circular structure and is mounted on the spherical housing by a support 2 (shown in fig. 2), the focal length of the focusing lens being F.
As shown in FIG. 3, in order to ensure that the reflection angle θ is large enough to enable the first reflected light to be far away from the air inlet or the air outlet, and avoid the attenuation of the intensity of the excitation light caused by the fact that laser is prematurely contacted with the air inlet or the air outlet, the focal length F of the focusing lens does not exceed half the radius R of the spherical shell, namely F is less than or equal to R/2, wherein R is the average value of the inner diameter and the outer diameter of the spherical shell.
The inner wall of the spherical shell is plated with a reflective film 6 (as shown in fig. 2), and the reflectivity of the reflective film is more than 98%. Thereby allowing low loss, cyclic reflection transmission of the laser light within the gas cell.
The air inlet and the air outlet are respectively arranged at two sides of the focusing lens.
The electronic device 9 is used for acquiring the raman spectrum signal output by the spectrometer and generating a raman spectrum chart, and separating out each gas type and corresponding concentration value in the mixed gas by utilizing the raman spectrum chart.
Based on the same inventive concept, as shown in fig. 4, the present application provides a laser raman gas detection method, which includes:
step 201: providing incident laser light of different light paths for the gas to be detected in the reflecting cavity, wherein the inner surface of the reflecting cavity is configured to have a plurality of reflecting positions;
step 202: and collecting spherical Raman scattered light generated by the reaction of the laser circularly reflected by the plurality of reflection positions and the gas to be detected so as to provide Raman spectrum signals.
Furthermore, the method comprises the following steps:
and acquiring a Raman spectrum signal output by the spectrometer, generating a Raman spectrum chart, and utilizing the Raman spectrum chart to separate out each gas type and corresponding concentration value in the mixed gas.
As shown in fig. 5, the electronic device includes: a memory and a processor, the memory storing an executable program, the processor executing the executable program to implement: and acquiring a Raman spectrum signal output by the spectrometer, generating a Raman spectrum chart, and utilizing the Raman spectrum chart to separate out each gas type and corresponding concentration value in the mixed gas.
The processor may be a general purpose processor, a digital signal processor, an application-specific integrated circuit (ASIC), a programmable logic device (programmable logic device, PLD), or a combination thereof. The PLD may be a complex programmable logic device (complex programmable logic device, CPLD), a field-programmable gate array (field-programmable gate array, FPGA), general-purpose array logic (generic array logic, GAL) or any combination thereof. The general purpose processor may be a microprocessor or any conventional processor or the like.
The memory may include volatile memory in a computer-readable medium, random Access Memory (RAM) and/or nonvolatile memory, such as Read Only Memory (ROM) or flash memory (flash RAM). Memory is an example of a computer-readable medium.
The present embodiments also provide a storage medium carrying one or more computer programs which, when executed by a processor, implement: and acquiring a Raman spectrum signal output by the spectrometer, generating a Raman spectrum chart, and utilizing the Raman spectrum chart to separate out each gas type and corresponding concentration value in the mixed gas.
The storage medium in the present embodiment may be contained in an electronic device/system; or may exist alone without being assembled into an electronic device/system. The storage medium carries one or more programs that when executed implement methods according to embodiments of the present application.
According to embodiments of the present application, the computer-readable storage medium may be a non-volatile computer-readable storage medium, which may include, for example, but is not limited to: a portable computer diskette, a hard disk, a Random Access Memory (RAM), a read-only memory (ROM), an erasable programmable read-only memory (EPROM or flash memory), a portable compact disc read-only memory (CD-ROM), an optical storage device, a magnetic storage device, or any suitable combination of the foregoing. In the context of this document, a computer readable storage medium may be any tangible medium that can contain, or store a program for use by or in connection with an instruction execution system, apparatus, or device.
Furthermore, although the operations of the methods of the present application are depicted in the drawings in a particular order, this is not required to or suggested that these operations must be performed in this particular order or that all of the illustrated operations must be performed in order to achieve desirable results. Additionally or alternatively, certain steps may be omitted, multiple steps combined into one step to perform, and/or one step decomposed into multiple steps to perform.
While preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the application.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
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| CN202311193764.2A CN117347344A (en) | 2023-09-15 | 2023-09-15 | A laser Raman gas detection device and method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119916511A (en) * | 2025-01-24 | 2025-05-02 | 暨南大学 | A heat-insensitive multi-reflection cavity for enhanced gas Raman spectroscopy |
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2023
- 2023-09-15 CN CN202311193764.2A patent/CN117347344A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119916511A (en) * | 2025-01-24 | 2025-05-02 | 暨南大学 | A heat-insensitive multi-reflection cavity for enhanced gas Raman spectroscopy |
| CN119916511B (en) * | 2025-01-24 | 2026-03-03 | 暨南大学 | A thermally insensitive multi-reflection cavity for enhancing gas Raman spectroscopy |
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