CN109884035B - Detection device, detection method and anti-counterfeiting detection method for sample to be detected - Google Patents
Detection device, detection method and anti-counterfeiting detection method for sample to be detected Download PDFInfo
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Abstract
The invention relates to the technical field of spectrum detection, in particular to a detection device, a detection method and an anti-counterfeiting detection method for a sample to be detected. The invention not only utilizes the characteristics of high efficiency, reliability, high temperature and the like of the inductive coupling plasma torch to the material processing, but also combines the incomparable advantages of real-time, high speed, micro-loss, full element analysis and the like of the laser breakdown spectrum detection technology, overcomes the interference of a fluorescence background, and improves the sensitivity and the signal-to-noise ratio of the detection spectrum.
Description
Technical Field
The invention relates to the technical field of spectrum detection, in particular to a detection device, a detection method and an anti-counterfeiting detection method for a sample to be detected.
Background
In recent years, the demand for detecting common sample elements is increasing, for example, heavy metal elements in water and soil are detected to monitor and control heavy metal pollution, and various elements in organic matters such as vegetables and tea are detected to evaluate the influence of the elements on the ingested human body; meanwhile, the counterfeit problem of various food and drink products and the like is getting worse, and the authenticity identification of various drinks and foods can be analyzed by detecting characteristic elements in the drinks and foods.
Conventional analytical testing of substances typically employs sampling followed by analysis by laboratory chemical reagent processing and spectroscopic instrumentation. Although the methods have high detection accuracy, the traditional method has a long detection period and cannot perform quick and instant detection, and secondary pollution is easily caused by treatment of chemical reagents in the detection process. Recently, a series of novel detection technical methods such as a hyperspectral analysis technology, an electrochemical analysis method, a biological analysis method, a terahertz analysis method and the like combined with latest research results still have the problems of complex pretreatment, incapability of rapidly obtaining results in real time, easiness in causing secondary pollution and the like.
Laser-Induced Breakdown Spectroscopy (LIBS) is a emerging spectrum detection technology in recent years, and compared with other spectrum technologies, the LIBS has incomparable advantages of simple sample pretreatment, real-time performance, rapidness, micro-loss, full-element analysis and the like, so that the LIBS is widely concerned and is widely applied to the fields of metallurgical analysis, environmental monitoring, geological exploration, online monitoring, national defense and the like. The method is used for sample monitoring, can carry out laser-induced breakdown spectroscopy analysis only by simply processing a sample or even without processing, but has the problem of low detection sensitivity, and is the key point on how to avoid background spectra without sacrificing signal spectral intensity and signal-to-noise ratio and how to effectively improve element detection sensitivity.
In addition, the traditional nanosecond laser-induced breakdown spectrum has a continuous background fluorescence spectrum caused by strong reverse bremsstrahlung, and a target signal spectrum can be covered.
Disclosure of Invention
In order to solve the technical problems, the invention provides a detection device, a detection method and an anti-counterfeiting detection method for improving the detection sensitivity of chemical components of a sample to be detected, which are based on the simple treatment of an inductively coupled plasma torch generator (ICP) on the sample, the femtosecond laser induced breakdown of the sample to be detected to form plasma and obtain the characteristic spectrum of the sample to be detected, and the sensitivity of the detection on the chemical components of the sample to be detected is improved.
The invention adopts the following technical scheme:
a detection device for improving the detection sensitivity of chemical components of a sample to be detected comprises an atomization device, an inductance coupling plasma torch generator, a femtosecond pulse laser generator and a spectrum collection module, wherein the inductance coupling plasma torch generator is used for generating a plasma torch, the plasma torch is provided with a plasma excitation area, the atomization device is used for converting a sample to be tested into aerosol and sending the aerosol into an inductively coupled plasma torch generator, the plasma excitation area is used for preprocessing the aerosol, the femtosecond pulse laser generator is used for forming a femtosecond optical filament or a plasma grating, the femtosecond optical filament or the plasma grating is focused on the preprocessed sample to be tested, the spectrum collection module is used for collecting electromagnetic wave signals emitted by the plasma and forming a characteristic spectrum of the sample to be detected.
Furthermore, the inductively coupled plasma torch generator comprises a plasma torch tube and a high-frequency induction coil connected to the plasma torch tube, wherein the plasma torch tube is composed of three coaxially arranged quartz glass tubes, and the three quartz glass tubes are used for introducing working gas.
Furthermore, the femtosecond pulse laser generator comprises a pulse laser and a focusing module connected with the pulse laser, wherein the pulse width of the pulse laser emitted by the pulse laser is in femtosecond magnitude. Furthermore, the femtosecond pulse laser generator comprises a pulse laser, a beam splitting module connected with the pulse laser, a time domain synchronization module connected with the beam splitting module and a focusing module connected with the time domain synchronization module, wherein the pulse width of the pulse laser emitted by the pulse laser is in femtosecond magnitude.
Further, the spectrum collection module comprises a fluorescence collection system and a spectrometer, and the fluorescence collection system is a focusing lens or an optical 4f system.
A detection method for detecting chemical components of a sample to be detected by using the detection device comprises the following specific steps:
A. introducing working gas into the inductively coupled plasma torch generator to enable the inductively coupled plasma torch generator to generate a plasma torch;
B. loading a sample to be detected into an atomization device, converting the sample to be detected into aerosol by the atomization device, and spraying the aerosol into a plasma excitation area of a plasma torch;
C. b, the aerosol obtained in the step B is pretreated by a plasma excitation area;
D. a laser generator generates a femtosecond optical fiber or a plasma grating, the femtosecond optical fiber or the plasma grating focuses on the sample to be detected obtained through the pretreatment in the step C, atoms of the sample to be detected are excited and ionized, and plasma is formed on the surface of the sample to be detected;
E. the method comprises the steps that electromagnetic wave signals with specific wavelengths are emitted when atoms and ions in an excited state in the plasma are transited from a high energy state to a low energy state, the electromagnetic wave signals are collected and processed by a spectrum collection module, further, a characteristic spectrum of a sample to be detected is obtained, and qualitative analysis or quantitative analysis is conducted on chemical components of the sample to be detected according to the characteristic spectrum.
Wherein, in step C, the pretreatment specifically comprises: the method comprises the steps of desolventizing the aerosol, evaporating the desolventized aerosol to form a gaseous sample to be detected, carrying out atomization treatment on the gaseous sample to be detected, and carrying out primary excitation and ionization on the atomized gaseous sample to be detected.
In step E, the obtaining of the characteristic spectrum of the sample to be measured specifically includes the following steps:
e1, determining the element type of the sample to be detected according to the wavelength of the electromagnetic wave signal emitted by the plasma;
e2, performing signal intensity test on the electromagnetic wave signals, and determining the content of each element in the sample to be tested according to the signal intensity obtained by the test;
and E3, fitting the characteristic spectrum according to the wavelength and the signal intensity as parameter coordinates.
An anti-counterfeiting detection method based on a fingerprint of a sample to be detected comprises the following specific steps:
s1, sampling: taking different batches of control samples, wherein the control samples of the same batch specifically comprise a plurality of control samples of the same production place;
s2, acquiring fingerprint information: sequentially detecting the control samples of each batch according to the method of the detection method steps A-E to obtain the chemical component information of the control samples of each batch, wherein the chemical component information comprises the element types and the element contents contained in the control samples;
s2, establishing a fingerprint: selecting 3 elements with the maximum content in the comparison sample, establishing a three-dimensional coordinate system by taking the 3 elements as XYZ coordinate axes respectively, and drawing by taking the content corresponding to the 3 elements as three-dimensional coordinate points to form a fingerprint spectrum of the comparison sample of the production place;
s3, anti-counterfeiting detection and identification: selecting a sample to be detected in the same place of production as the sample to be detected, obtaining the characteristic spectrum of the sample to be detected according to the same method in the step S2, comparing the obtained characteristic spectrum with the fingerprint of the comparison sample, and identifying the sample to be detected according to the difference of the chemical component information.
The invention has the beneficial effects that: the invention creatively combines the granulation of the inductive coupling plasma torch to the substance with the femtosecond optical fiber and the plasma grating breakdown spectrum in the ultrafast optics, not only utilizes the characteristics of the inductive coupling plasma torch such as high efficiency, reliability and high temperature to the substance treatment, but also combines the incomparable advantages of the breakdown spectrum detection technology such as real time, rapidness, micro loss, full element analysis and the like, overcomes the interference of the fluorescence background, and improves the sensitivity and the signal to noise ratio of the detection spectrum; the characteristic fingerprint spectrum of the corresponding substance to be detected is obtained by innovatively providing that the element signal strength is taken as a fingerprint parameter, so that effective anti-counterfeiting detection, substance analysis and identification, component analysis and the like are possible.
Drawings
FIG. 1 is a schematic structural diagram of a detecting device according to the present invention;
FIG. 2 is a flow chart of the working principle of the present invention;
FIG. 3 is a characteristic spectrum obtained by testing a white spirit sample;
figure 4 is a characteristic spectrum obtained by testing a tea sample.
Detailed Description
In order to facilitate understanding of those skilled in the art, the present invention will be further described with reference to the following examples and drawings, which are not intended to limit the present invention.
As shown in fig. 1 to 2, a detection apparatus for improving the detection sensitivity of a chemical component of a sample to be detected includes: the device comprises an atomizing device 3, an inductance coupling plasma torch generator 2, a femtosecond pulse laser generator 1 and a spectrum collection module 4, wherein the inductance coupling plasma torch generator 2 is used for generating a plasma torch, the plasma torch is provided with a plasma excitation area, the atomizing device 3 is used for converting a sample to be detected into aerosol and sending the aerosol into the inductance coupling plasma torch generator 2, the plasma excitation area is used for preprocessing the aerosol, the femtosecond pulse laser generator 1 is used for forming a femtosecond optical wire or a plasma grating, the femtosecond optical wire or the plasma grating is focused on the preprocessed sample to be detected, so that the sample to be detected forms plasma, and the spectrum collection module 4 is used for collecting electromagnetic wave signals sent by the plasma and forming a characteristic spectrum of the sample to be detected.
The working principle of the detection device is explained below with reference to fig. 1 to 2: during detection, working gas is introduced into an inductive coupling plasma torch generator 2, so that the inductive coupling plasma torch generator 2 generates a plasma torch, a sample to be detected is sent into an atomizing device 3, the atomizing device 3 converts the sample to be detected into aerosol and sprays the aerosol obtained by conversion into the plasma torch, the aerosol is pretreated in a plasma excitation area, a femtosecond pulse laser generator 1 emits a femtosecond optical filament or a plasma grating to be focused on the pretreated sample to be detected, atoms of the sample to be detected are excited and ionized to generate plasma, a series of electromagnetic waves with different wavelengths are generated in the process that atoms and ions in an excited state in the plasma are transited from a high energy level to a low energy level, a spectrum collection module 4 is used for collecting characteristic spectra of the sample to be detected, and the characteristic spectral lines of the characteristic spectra correspond to elements in the sample to be detected one by one, by qualitative analysis or quantitative analysis of the characteristic spectrum, the chemical component analysis of the sample to be detected and the substance analysis and identification of the sample to be detected can be realized. Wherein, the pretreatment specifically comprises the following steps: the method comprises the steps of desolventizing the aerosol, evaporating the desolventized aerosol to form a gaseous sample to be detected, carrying out atomization treatment on the gaseous sample to be detected, and carrying out primary excitation and primary ionization on the atomized gaseous sample to be detected. The invention not only utilizes the characteristics of high efficiency, reliability, high temperature and the like of the inductive coupling plasma torch to the material processing, but also combines the incomparable advantages of real-time, high speed, micro loss, full element analysis and the like of the laser breakdown spectroscopy detection technology, overcomes the interference of fluorescence background, and improves the sensitivity and the signal to noise ratio of the detection spectrum.
In this embodiment, the inductively coupled plasma torch generator 2 includes a plasma torch tube and a high-frequency induction coil connected to the plasma torch tube, the plasma torch tube is composed of three coaxially disposed quartz glass tubes, and the three quartz glass tubes are used for introducing working gas.
The femtosecond pulse laser generator 1 can also comprise a pulse laser 11, a beam splitting module 12 connected with the pulse laser 11, a time domain synchronization module 13 connected with the beam splitting module 12 and a focusing module 14 connected with the time domain synchronization module 13, specifically, the pulse laser 11 sends a beam of femtosecond pulse, the beam is split into two beams of laser with the energy ratio of 1:1 by the beam splitting module 12, the optical paths of the two beams of laser are adjusted to be the same by the time domain synchronization module 13, the two beams of laser are focused into a femtosecond optical filament by the focusing module 14, the two beams of femtosecond optical filament are crossed and interacted to form plasma with space period modulation, the electron density is improved, the plasma acts on high-temperature particle substance gas to be detected, and effective excitation is further realized, wherein the pulse width of the pulse laser sent by the pulse laser 11 is in the femtosecond magnitude. However, the structure of the present invention is not limited to this, and in particular, when in use, the femtosecond pulse laser generator 1 may further include only the pulse laser 11 and the focusing module 14 connected to the pulse laser 11, specifically, the pulse laser 11 emits a beam of femtosecond pulses, the femtosecond pulses are focused into a femtosecond optical filament by the focusing module 14, and the femtosecond optical filament acts on the sample to be measured, so that atoms of the sample to be measured are excited and ionized to form plasma.
The beam splitting module 12 is a beam splitting plate or other beam splitting optical elements, and the focusing module 14 is a focusing system formed by a single-chip or multi-chip focusing lens, so that two or more beams of synchronous optical fibers are coupled with each other at a certain angle to form a density period modulated plasma grating.
In this embodiment, the spectrum collection module 4 includes a fluorescence collection system and a spectrometer, and the fluorescence collection system is a focusing lens or an optical 4f system.
In this embodiment, a method for detecting chemical components of a sample to be detected by using the above detection apparatus includes the following steps:
A. a working gas is introduced into the induction coupled plasma torch generator 2, such that the induction coupled plasma torch generator 2 generates a plasma torch,
B. a sample to be tested is loaded into an atomizing device 3, and the atomizing device 3 converts the sample to be tested into aerosol and sprays the aerosol into a plasma excitation area of a plasma torch;
C. the plasma excitation area is used for pretreating the aerosol obtained in the step B;
D. the femtosecond pulse laser generator 1 generates a femtosecond optical filament or a plasma grating, the femtosecond optical filament or the plasma grating focuses on the sample to be detected obtained through the pretreatment in the step C, and atoms of the sample to be detected are excited and ionized, so that plasma is formed on the surface of the sample to be detected;
E. when atoms and ions in an excited state in the plasma are transited from a high energy state to a low energy state, an electromagnetic wave signal with a specific wavelength is emitted, the electromagnetic wave signal is collected and processed by the spectrum collection module 4, a characteristic spectrum of a sample to be detected is further obtained, and qualitative analysis or quantitative analysis is carried out on chemical components of the sample to be detected according to the characteristic spectrum.
The following describes the detection method of the present invention by taking a white spirit sample as a sample to be detected: firstly, working gas is introduced into three quartz glass tubes of an inductively coupled plasma torch generator, wherein the working gas can be inert gas such as argon or helium, and the like, wherein the working gas introduced into the outer tube is cooling gas and is used for protecting the quartz glass tubes and preventing the tube walls from being heated and melted; the working gas introduced into the middle tube is auxiliary gas, when the ionized gas passes through the high-frequency induction coil surrounding the top of the quartz tube, the huge heat energy and the alternating magnetic field generated by the coil cause the electrons and the ions of the ionized gas to repeatedly and violently collide with neon atoms in the ground state, and various particles move at high speed to form a plasma torch area similar to a coil, wherein the temperature is up to 6000-10000 ℃; working gas in the inner tube is carrier gas and is used for guiding aerosol to enter a plasma torch, then a liquor sample is introduced into an atomizing device 3, the atomizing device 3 converts the sample to be detected into the aerosol and sprays the aerosol into a plasma torch generator, the high-temperature plasma torch evaporates, atomizes, excites and ionizes the liquor sample to form liquor sample particle gas, pretreatment of the liquor sample is achieved, chemical treatment is carried out on the liquor sample by adopting a chemical reagent, chemical interference and matrix interference are avoided, then femtosecond pulse laser with single pulse energy of 1.6mJ and frequency of 1kHz is emitted through a pulse laser 11, beam splitting is carried out through a beam splitting module 12, then optical paths of two beams of pulse laser are adjusted to be synchronous through a time domain synchronization module 13, optical fibers are formed through a focusing lens, and space intersection is adjusted to form plasma gratings, the plasma grating acts on the white spirit sample particle gas to further excite and ionize and breakdown the white spirit sample particle gas to generate more atoms, ions and the like in higher excited states, namely plasmas are formed on the surface of the white spirit sample particle gas to improve the sensitivity of element detection, wherein the atoms and ions in the excited states in the plasmas emit electromagnetic waves with specific wavelengths when the atoms and ions in the excited states jump from high energy states to low energy states, at the moment, the collection delay and on-chip integration modes of ICCD of a used spectrometer are reasonably set, the high-resolution spectrometer is used for collecting the lateral fluorescence of the electromagnetic waves, namely the characteristic spectrum of the sample can be measured, and the qualitative analysis or quantitative analysis is carried out on the characteristic spectrum to realize the chemical component analysis of the sample to be measured, such as various trace elements (potassium, aluminum, iron, copper, lead, manganese and the like) contained in white spirit, Nickel, cadmium, etc.). Wherein, fig. 3 is a characteristic spectrum obtained by testing a white spirit sample. Particularly, the detection method is suitable for detecting substances in various states such as solid, liquid and gas, and based on the knowledge of the prior art, a person skilled in the art simply processes a solid sample to be detected into a liquid sample before detection, for example, the liquid sample of the sample to be detected is obtained through sintering, acidification and digestion treatment.
In this embodiment, in step C, the preprocessing specifically includes:
the method comprises the steps of desolventizing the aerosol, evaporating the desolventized aerosol to form a gaseous sample to be detected, carrying out atomization treatment on the gaseous sample to be detected, and carrying out primary excitation and ionization on the atomized gaseous sample to be detected.
In this embodiment, in step E, the obtaining of the characteristic spectrum of the sample to be detected specifically includes the following steps:
e1, determining the element type of the sample to be detected according to the wavelength of the electromagnetic wave signal emitted by the plasma;
e2, performing signal intensity test on the electromagnetic wave signals, and determining the content of each element in the sample to be tested according to the signal intensity obtained by the test;
and E3, fitting the characteristic spectrum according to the wavelength and the signal intensity as parameter coordinates.
In this embodiment, on the basis of having a high sensitivity detection for a chemical component of a sample to be detected, the chemical component of the sample to be detected (for example, information such as a type of an element contained therein, a signal intensity (corresponding element content) of each element, a proportional relationship between the element contents, and the like) is specific and unique for a substance to be detected, and the present invention also provides an anti-counterfeit detection method based on a fingerprint of the sample to be detected, which includes the following specific steps:
s1, sampling: taking different batches of control samples, wherein the control samples of the same batch specifically comprise a plurality of control samples of the same production place;
s2, acquiring fingerprint information: sequentially detecting the control samples of each batch according to the method of the detection method steps A-E to obtain the chemical component information of the control samples of each batch, wherein the chemical component information comprises the element types and the element contents contained in the control samples;
s2, establishing a fingerprint: selecting 3 elements with the maximum content in the comparison sample, establishing a three-dimensional coordinate system by taking the 3 elements as XYZ coordinate axes respectively, and drawing by taking the content corresponding to the 3 elements as three-dimensional coordinate points to form a fingerprint spectrum of the comparison sample of the production place;
s3, anti-counterfeiting detection and identification: selecting a sample to be detected in the same place of production as the sample to be detected, obtaining the characteristic spectrum of the sample to be detected according to the same method in the step S2, comparing the obtained characteristic spectrum with the fingerprint of the comparison sample, and identifying the sample to be detected according to the difference of the chemical component information.
The anti-counterfeiting detection method of the invention is explained below by taking a tea sample as a sample to be detected: firstly, taking tea samples of different producing areas, classifying a plurality of tea samples of the same producing area into a control sample of the same batch, then sintering, acidifying and digesting the tea samples to obtain a liquid sample without sediment, sequentially processing the tea samples of the same producing area according to the same steps in the embodiment to obtain a characteristic spectrum (see figure 4) of the tea samples of the same batch, then carrying out quantitative analysis on the characteristic spectrum to obtain elements and element contents contained in the tea samples, selecting three elements with the maximum element content in the tea samples as coordinate axes to establish a three-dimensional coordinate system, wherein the wavelength in the characteristic spectrum corresponds to a specific element, the signal intensity corresponding to the corresponding wavelength is the element content, and the content corresponding to the 3 elements is taken as a three-dimensional coordinate point to be plotted to form fingerprint spectrum information of the tea samples of the producing area, and then, the steps are sequentially repeated on the tea samples of the second producing area to obtain the fingerprint spectrum information of the tea samples of a plurality of producing areas, namely, the fingerprint spectrums corresponding to the tea samples are formed, the element types, the element contents and the relative proportions obtained by testing the real wine and the fake wine are different, the inconsistency is shown on the great difference of the characteristic fingerprint spectrums, namely, the fingerprint spectrums can be used as unique characteristic marks of the substances, and thus, the anti-counterfeiting detection is realized.
When tea anti-counterfeiting detection and identification are carried out, fingerprint spectrums of tea samples are quantitatively analyzed, standard curves of element contents in the tea samples in different producing areas are calculated according to a three-dimensional coordinate formula, any tea sample is selected as a sample to be detected, a characteristic spectrum of the sample to be detected is obtained by combining the detection device in the figure 1, information of the characteristic spectrum is sequentially substituted into the standard curves of the tea samples in different producing areas, errors of the standard curves of the tea samples in different batches are calculated, the tea belonging to the producing area is the tea with the smallest error, and therefore clear and reasonable identification and classification of the tea in different producing areas are achieved.
The method of the present invention is not limited to this, wherein, a leaf sample of a determined producing area can be randomly selected as a sample to be tested, the characteristic spectrum of the sample to be tested is obtained by combining the detection device in fig. 1, the obtained spectrum information is compared with the fingerprint spectrum information, specifically, the difference between the element types, the element contents and the relative proportions of the elements is compared, and counterfeit tea leaves can be effectively identified. All the technical features in the embodiment can be freely combined according to actual needs.
The above embodiments are preferred implementations of the present invention, and the present invention can be implemented in other ways without departing from the spirit of the present invention.
Claims (7)
1. A detection device for improving the detection sensitivity of chemical components in a sample to be detected is characterized in that: the device comprises an atomization device, an inductance coupling plasma torch generator, a femtosecond pulse laser generator and a spectrum collection module, wherein the inductance coupling plasma torch generator is used for generating a plasma torch, the plasma torch is provided with a plasma excitation area, the atomization device is used for converting a sample to be detected into aerosol and sending the aerosol into the inductance coupling plasma torch generator, the plasma excitation area is used for preprocessing the aerosol processed by the atomization device, the femtosecond pulse laser generator is used for forming a plasma grating, the plasma grating is focused on the sample to be detected after being preprocessed by the plasma excitation area, so that the sample to be detected forms plasma, and the spectrum collection module is used for collecting electromagnetic wave signals emitted by the plasma and forming a characteristic spectrum of the sample to be detected;
the femtosecond pulse laser generator comprises a pulse laser, a beam splitting module connected with the pulse laser, a time domain synchronization module connected with the beam splitting module and a focusing module connected with the time domain synchronization module, wherein the pulse width of the pulse laser emitted by the pulse laser is in femtosecond magnitude.
2. The detection apparatus for improving the detection sensitivity of the chemical components in the sample to be detected according to claim 1, wherein: the inductively coupled plasma torch generator comprises a plasma torch tube and a high-frequency induction coil connected to the plasma torch tube, wherein the plasma torch tube consists of three coaxially arranged quartz glass tubes, and the three quartz glass tubes are used for introducing working gas.
3. The detection apparatus for improving the detection sensitivity of the chemical components in the sample to be detected according to claim 1, wherein: the spectrum collection module comprises a fluorescence collection system and a spectrometer, and the fluorescence collection system is a focusing lens or an optical 4f system.
4. A method for detecting chemical components of a sample to be detected by using the detecting device of any one of claims 1-2, wherein the detecting method comprises the following steps:
A. introducing working gas into the inductively coupled plasma torch generator to enable the inductively coupled plasma torch generator to generate a plasma torch;
B. loading a sample to be detected into an atomization device, converting the sample to be detected into aerosol by the atomization device, and spraying the aerosol into a plasma excitation area of a plasma torch;
C. b, the aerosol obtained in the step B is pretreated by a plasma excitation area;
D. c, generating a plasma grating by using a femtosecond pulse laser generator, wherein the plasma grating is focused on the sample to be detected obtained by the pretreatment in the step C, and atoms of the sample to be detected are excited and ionized to form plasma on the surface of the sample to be detected;
E. the method comprises the steps that electromagnetic wave signals with specific wavelengths are emitted when atoms and ions in an excited state in the plasma are transited from a high energy state to a low energy state, the electromagnetic wave signals are collected and processed by a spectrum collection module, further, a characteristic spectrum of a sample to be detected is obtained, and qualitative analysis or quantitative analysis is conducted on chemical components of the sample to be detected according to the characteristic spectrum.
5. The detection method according to claim 4, characterized in that: in step C, the pretreatment specifically comprises: the method comprises the steps of desolventizing the aerosol, evaporating the desolventized aerosol to form a gaseous sample to be detected, carrying out atomization treatment on the gaseous sample to be detected, and carrying out primary excitation and ionization on the atomized gaseous sample to be detected.
6. The detection method according to claim 4, characterized in that: in step E, the obtaining of the characteristic spectrum of the sample to be detected specifically includes the following steps:
e1, determining the element type of the sample to be detected according to the wavelength of the electromagnetic wave signal emitted by the plasma;
e2, performing signal intensity test on the electromagnetic wave signals, and determining the content of each element in the sample to be tested according to the signal intensity obtained by the test;
and E3, fitting the characteristic spectrum according to the wavelength and the signal intensity as parameter coordinates.
7. An anti-counterfeiting detection method based on a fingerprint of a sample to be detected is characterized by comprising the following steps: the anti-counterfeiting detection method comprises the following specific steps:
s1, sampling: taking different batches of control samples, wherein the control samples of the same batch specifically comprise a plurality of control samples of the same production place;
s2, acquiring fingerprint information: sequentially detecting the control samples of each batch according to the steps A-E of the detection method of claim 4 to obtain the chemical component information of the control samples of each batch, wherein the chemical component information comprises the element types and the element contents contained in the control samples;
s3, establishing a fingerprint: selecting 3 elements with the maximum content in the comparison sample, establishing a three-dimensional coordinate system by taking the 3 elements as XYZ coordinate axes respectively, and drawing by taking the content corresponding to the 3 elements as three-dimensional coordinate points to form a fingerprint spectrum of the comparison sample of the production place;
s4, anti-counterfeiting detection and identification: selecting a sample to be detected in the same place of production as the sample to be detected, obtaining the characteristic spectrum of the sample to be detected according to the same method in the step S2, comparing the obtained characteristic spectrum with the fingerprint of the comparison sample, and identifying the sample to be detected according to the difference of the chemical component information.
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| CN107631999A (en) * | 2017-10-13 | 2018-01-26 | 中国科学院上海技术物理研究所 | LIBS and MS combination substance detection system under a kind of planet open environment |
| CN108663352A (en) * | 2018-03-27 | 2018-10-16 | 四川中医药高等专科学校 | A kind of discriminating of genunie medicinal materials and identification method |
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