CN117538135B - Aerosol LIBS detection composite film based on nano structure and detection method - Google Patents
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- G—PHYSICS
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- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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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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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/718—Laser microanalysis, i.e. with formation of sample plasma
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Abstract
The invention relates to an aerosol LIBS detection composite film based on a nano structure and a detection method, wherein the aerosol LIBS detection composite film based on the nano structure has three layers of structures which are tightly attached and fixed with each other, and the three layers of structures are respectively as follows: the device comprises a transparent polymer film with adhesiveness, a dispersion film with nanoscale thickness and a bearing substrate, wherein the polymer film is used for carrying out adhesiveness capture on solid particles in aerosol in gas to be detected, the dispersion film is made of a material with light dispersion capability, most laser energy can be dissipated when blank gas to be detected is detected, background signals are restrained, and the bearing substrate is a carrier of the polymer film and the dispersion film. The invention can obviously eliminate the background noise during detection, lighten the adverse effect of matrix effect and effectively improve the sensitivity and stability of LIBS detection.
Description
Technical Field
The invention relates to a nanocomposite and a detection method, in particular to an aerosol LIBS detection composite film based on a nanostructure and a detection method.
Background
The aerosol in the atmosphere refers to solid or liquid particles (particle size varies from 1nm to 100 μm) suspended in the atmosphere, and has a great influence on the environment. In one aspect, aerosols may directly scatter and absorb solar radiation, thereby indirectly affecting illumination. On the other hand, aerosol particles can also serve as cloud nuclei and ice nuclei, and finally influence rainfall conditions in a region. Furthermore, aerosol particles can also adsorb a large amount of harmful substances by using their extremely high specific surface area and spread the pollution source to a far-distance area by wind power. More dangerous, aerosol particles floating in the air for a long time can also act as a medium for physicochemical reactions to generate various harmful substances, thereby causing various acute or chronic diseases of human or animals. Therefore, the real-time monitoring of the aerosol in the air is important in the fields of environmental protection, ecological prevention and control, climate prediction and the like.
Conventional gas phase elemental analysis techniques include inductively coupled plasma-atomic emission spectroscopy (Inductively Coupled Plasma-Atomic Emission Spectrometry, ICP-AES) and inductively coupled plasma-mass spectrometry (Inductively Coupled Plasma-Mass Spectrometry, ICP-MS), both of which utilize inductively coupled plasma techniques (Inductively Coupled Plasma, ICP) to ionize species in the gas phase, except for differences in the detection methods of the ends. ICP applies an electromagnetic field using a high power radio frequency source (about 2000 a W) to ionize the working gas to form a plasma. And then introducing the gas to be measured into the generated plasma so as to make the gas to be measured into plasma. The qualitative and quantitative analysis is carried out by atomic emission spectrum of the object to be detected, namely ICP-AES technology. If mass spectrometry is used to analyze the mass to charge ratio of the generated ions, the mass spectrometry is the ICP-MS technology. The two techniques have higher sensitivity and wider linear range, and are common methods for detecting the atmospheric aerosol nowadays. ICP-related instruments are generally expensive and relatively bulky (about 1m 3 ) The method has high requirements on the operation environment, and needs a large amount of working gases (about 15L/min) such as argon, helium and the like, and cannot go out of a laboratory for on-site analysis. In addition, the instrument based on ICP technology has low tolerance to air injection and is not suitable for real-time gas-phase multi-element analysis.
To solve the above problems, researchers have developed microwave plasma torch (Microwave Plasma Torch, MPT) technology. Unlike ICP technology, MPT efficiently transfers microwave energy to working gas by using a resonant cavity, improving energy utilization, reducing the volume of the instrument, and making the gas consumption less. The microwave plasma source in MPT technology has lower power (about 100W), lower gas consumption (about 0.5L/min) and volume of about 0.1m 3 And can be directly injected by air. While MPT technology has these advantages, it is difficult to further reduce the volume because the principle and inherent structure determine that it cannot be separated from the gas such as helium or argon. This limits the application range and the large-scale popularization of the technology to a certain extent.
Laser induced breakdown spectroscopy (Laser induced breakdown spectroscopy, LIBS) uses a high power pulsed laser beam focused onto an object to be measured to generate a plasma for atomic spectroscopy. By recording and analyzing the atomic emission spectrum generated by the laser-induced plasma, an in-situ real-time measurement method can be provided for the direct analysis of the atmospheric aerosol. LIBS technology does not require working gas and complex sample preparation, and is simple and flexible in structure and can be used for analyzing almost all elements. The LIBS technology is therefore more promising for achieving in-situ real-time analysis and long-term continuous detection of aerosols. However, LIBS lasers have difficulty in efficiently exciting samples that are constantly moving in the gas phase due to the small focused spot size (in the order of microns), short pulse time (in the order of nanoseconds), low pulse repetition rate, and the like of the laser beam. The extremely low sample excitation efficiency makes LIBS technology less sensitive and stable for aerosol analysis.
In order to solve the problems faced by LIBS technology in aerosol detection applications, researchers have proposed a series of methods to improve LIBS aerosol detection sensitivity and signal stability. For example:
1. the physical chamber geometric constraint of the sample chamber and the accurate time sequence control of laser are utilized to increase the particle sample concentration in the local space, so that the excitation efficiency is improved.
2. Particles can be captured using a Continuous Wave (CW) laser, a technique also known as optical tweezers. The technique is understood to mean that when particles are irradiated with laser light, the particles are stably held near the focal point by the light pressure of the laser light, thereby achieving an operation on particles in a specific size range. After the particles are captured, the particles are excited using the LIBS technique to obtain an elemental signal.
3. Sample enrichment and immobilization was performed using a filtration membrane. An aerosol of ambient air is passed through an air pump and a diffusion dryer and then flows through the filter membrane at a constant flow rate. The particles of the desired size will remain on the filter and the filter is then removed for LIBS detection.
4. Enrichment is carried out by using the adhesive tape, and the enrichment method is similar to that of a filter membrane. Microparticles on atmospheric air sol were enriched at the designated location of the adhesive tape by air pump, followed by LIBS detection of the adhered particle sample.
However, the above techniques have certain drawbacks. The physical chamber geometry constraint method can effectively improve the laser hit rate, but in order to ensure that the aerosol advances along a predetermined route, additional auxiliary gas is always required to be continuously introduced. And requires a complex laser accurate control system; the optical tweezers capturing technology can realize the effective LIBS analysis of single particle components, but has the defects of high requirements on detection environment, high equipment requirements, complex structure and the like, and is not suitable for field detection; the filter membrane pre-enrichment method has a certain improvement on sensitivity, but only enriches particles in a specific size range, and is complex to operate; the adhesive tape adhesion enrichment can realize enrichment of most of particles, and the operation is simpler. However, the use of adhesive tape introduces significant background interference, resulting in a low LIBS signal-to-noise ratio and limited sensitivity rise. Therefore, the existing method is difficult to meet the real-time, rapid and sensitive elemental analysis of the aerosol in the field environment.
Disclosure of Invention
The invention provides an aerosol LIBS detection composite film based on a nano structure and a detection method thereof, which are used for meeting the real-time, rapid and sensitive element detection and analysis of aerosol in a field environment and improving the detection sensitivity and signal stability of multiple elements in the aerosol.
The aerosol LIBS detection composite film based on the nanostructure has three layers of structures which are tightly adhered and fixed with each other, and the three layers of structures are respectively as follows: the upper layer is a transparent polymer film with adhesiveness, the middle layer is a dispersion film with nanoscale thickness, and the lower layer is a bearing substrate, wherein the polymer film is used for carrying out adhesiveness capture on solid particles in aerosol in gas to be detected, the dispersion film is made of a material with light dispersing capability, most laser energy can be dissipated when blank gas to be detected is detected, and background signals are restrained, and the bearing substrate is a carrier of the polymer film and the dispersion film.
The invention captures most solid particles in aerosol by utilizing good adhesiveness of the polymer film, and realizes effective enrichment of the solid particles in aerosol. The dispersion film has good light dispersing capability, and when LIBS detection is carried out on the air white sample gas, the polymer film and the dispersion film can dissipate most of laser energy. That is, when a blank sample is analyzed, plasma on the composite film is difficult to excite by aerosol LIBS detection, so that background signals are greatly suppressed. If the gas to be measured contains aerosol solid particles, the solid particles are adhered by the polymer film and block part of the area of the dispersion film. This allows the LIBS laser to excite the aerosol solid particles in the enriched region stably and efficiently. Therefore, the invention can obviously eliminate the background noise during detection, lighten the adverse effect of matrix effect and effectively improve the sensitivity and stability of LIBS detection.
Further, the thinner the thickness of the polymer film, the more preferable the thickness is, and the thickness used in the present invention may be 50 to 500. Mu.m, for example, 50 μm, 70 μm, 100 μm, 150 μm, 180 μm, 200 μm, 300 μm, 400 μm, 450 μm, 500 μm, etc.
Preferably, the thickness of the polymer film is 50. Mu.m.
Further, the bearing substrate is a transparent structure.
The invention also provides an aerosol LIBS detection method, which comprises the following steps:
A. enriching the aerosol in the gas to be detected on the aerosol LIBS detection composite film;
B. placing an enrichment area of the aerosol LIBS detection composite film on an objective lens focus of a LIBS detection device for LIBS spectrum analysis;
C. outputting the element signals of LIBS spectrum analysis.
Further, step C includes: and a laser of the LIBS detection device emits laser beams to the aerosol LIBS detection composite film to ablate the gas to be detected, so that plasma on the aerosol LIBS detection composite film is excited to emit laser-induced plasma flame, a spectrum signal emitted by the laser-induced plasma flame is received by a spectrum receiving probe of the LIBS detection device, related data are collected by a spectrometer, and finally a required element signal is output by a computer.
Further, in the step a, the gas to be detected is conveyed by a gas pump, and aerosol in the gas to be detected is enriched on the aerosol LIBS detection composite film after passing through a gas pipeline.
The beneficial effects of the invention include:
1. the directional enrichment of the aerosol is realized, the adverse effect of LIBS background noise is obviously inhibited, and finally, the LIBS high-sensitivity and on-site real-time analysis of various elements in gas phase is realized.
2. The aerosol LIBS detection composite film is convenient to prepare, flexible to use and capable of being stored for a long time, does not need an additional complex device when being detected, does not need any reagent or gas harmful to human bodies or environment, and can meet the requirement of on-site rapid detection.
3. The LIBS signal of multiple elements in the aerosol can be obviously enhanced. On the one hand, the background noise can be drastically reduced under the same condition, so that the spectrometer can better receive the spectrum signals of the element to be detected. On the other hand, the laser energy can be efficiently transmitted to the gas to be detected, the LIBS signal strength is improved, and finally the LIBS signal-to-noise ratio is obviously improved.
4. The method realizes the simultaneous detection of various trace elements in the gas phase, and can be applied to various fields such as environmental detection, public health, climate prediction, national defense and military industry, semiconductor chips, nuclear industry and the like.
Drawings
FIG. 1 is a schematic diagram of the structure of the nanostructure-based aerosol LIBS detection composite film of the present invention.
FIG. 2 is an electron microscope image of the dispersive film of FIG. 1.
Fig. 3 is a schematic illustration of aerosol LIBS detection by a LIBS detection device.
Fig. 4 is a process schematic of the aerosol LIBS detection method of the invention.
FIG. 5a is a spectral diagram of detection of copper aerosols in air by the aerosol LIBS detection of composite films of the present invention.
Fig. 5b is a spectral diagram of detection of copper aerosols in air by conventional glass slides.
Reference numerals illustrate:
1: polymer film, 2: dispersion film, 3: a carrier substrate, 01: laser, 02: spectrometer, 03: computer, 4: mirror, 5: objective lens, 6: laser induced plasma flame, 7: aerosol LIBS detection composite film, 8: stage, 9: spectral receiving probe, 10: laser beam, 11: gas pump, 12: a gas conduit.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments. The components of the embodiments of the present application, which are generally described and illustrated in the figures herein, may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present application, as provided in the accompanying drawings, is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, are intended to be within the scope of the present application.
As shown in fig. 1, the aerosol LIBS detection composite film based on the nanostructure has three layers of structures tightly adhered and fixed to each other, which are respectively: the upper layer is a transparent polymer film 1 with adhesiveness, the middle layer is a dispersion film 2 with nanoscale thickness, and the lower layer is a bearing substrate 3, wherein the polymer film is used for carrying out adhesiveness capture on solid particles in aerosol in gas to be detected, the dispersion film 2 is made of a material with light dispersing capability, most laser energy can be dissipated when blank gas to be detected is detected, and background signals are restrained, and the bearing substrate 3 is a bearing body of the polymer film 1 and the dispersion film 2.
The main characteristics of the polymer film 1 are excellent adhesiveness, good light transmittance, thinness enough and less element interference. In this example, the polymer film 1 was an acrylic polymer film having a thickness of 50. Mu.m, and having an adhesive. In addition, other organic or inorganic transparent adhesive tapes or adhesive films including organic polymers, inorganic polymers, nanomaterials, ionic liquids, etc., such as polytetrafluoroethylene, PET materials, etc., are also possible. The adhesive can be a silica gel adhesive, a polyacrylate adhesive, a polyurethane adhesive, a polytetrafluoroethylene adhesive, a rubber adhesive, a phenolic resin adhesive, a biological protein adhesive or the like.
The nano-scale thickness of the dispersion film 2 should be ensured to have a certain thickness and no element component to be measured so as to prevent the structure from being completely destroyed by the laser and to generate interference signals. Fig. 2 shows an electron microscope image of a dispersive film 2 of nanoscale thickness. The dispersion film 2 is preferably made of a material with strong light dispersion capability, such as photonic crystal, grating, periodic nanostructure, iris, laser film, optical disk, optical film, etc. In this embodiment, the dispersive film 2 is a photonic crystal iris.
The carrier substrate 3 is simply used as a carrier of the polymer film 1 and the dispersion film 2, and various transparent materials with certain strength, such as glass, quartz, acrylic and the like, can be selected. At the same time, the carrier substrate 3 should also ensure a material with good temperature stability, otherwise deformation may occur at high temperature of the laser, resulting in uneven detection surface and affecting the detection result. Glass is chosen as the carrier substrate 3 in this embodiment.
In another embodiment, as shown in fig. 3 and 4, the aerosol LIBS detection method of the present invention comprises the steps of:
A. an aerosol LIBS test composite film 7 comprising a polymer film 1, a dispersion film 2 and a carrier substrate 3 was produced in the above-described structure and materials. The gas pump 11 is started to convey the gas to be detected, and after the gas to be detected passes through the gas pipeline 12, the aerosol in the gas to be detected is enriched on the high polymer film 1 of the aerosol LIBS detection composite film 7;
B. placing the enrichment area of the aerosol LIBS detection composite film 7 on a stage 8 of a LIBS detection device, focusing on a focus of an objective lens 5, and performing LIBS spectrum analysis;
C. the computer 03 of the LIBS detection device controls the laser 01 to emit a laser beam 10, the laser beam 10 is focused by the reflector 4 and the objective lens 5, and then the aerosol LIBS is ablated to detect the gas to be detected on the composite film 7, so that the plasma on the aerosol LIBS detection composite film 7 is excited to emit laser-induced plasma flame 6, a spectrum signal emitted by the laser-induced plasma flame 6 is received by the spectrum receiving probe 9 of the LIBS detection device, the spectrometer 02 collects related data, and finally the computer 03 outputs a required element signal.
The invention captures most solid particles in aerosol by utilizing good adhesiveness of the polymer film, and realizes effective enrichment of the solid particles in aerosol. The dispersion film has good light dispersing capability, and when LIBS detection is carried out on the air white sample gas, the polymer film and the dispersion film can dissipate most of laser energy. That is, when a blank sample is analyzed, plasma on the composite film is difficult to excite by aerosol LIBS detection, so that background signals are greatly suppressed. If the gas to be measured contains aerosol solid particles, the solid particles are adhered by the polymer film and block part of the area of the dispersion film. This allows the LIBS laser to excite the aerosol solid particles in the enriched region stably and efficiently. Therefore, the invention can obviously eliminate the background noise during detection, lighten the adverse effect of matrix effect and effectively improve the sensitivity and stability of LIBS detection.
As shown in fig. 5a and 5b, the detection sensitivity (intensity) of the copper aerosol in the air is compared by the method of the invention and the traditional glass slide, 324.75 and nm are atomic emission lines of copper element, and the intensity and the content of the element are positively correlated. As can be seen from fig. 5a, the present invention shows a significant advantage of the detection of aerosol elements in air compared with the control group (slide glass) of fig. 5b without the dispersion film 2 and the polymer film 1 at a wavelength of 324.75 and nm, thereby significantly showing the superiority of the present invention compared with the conventional detection method.
The aerosol LIBS detection composite film constructed by the invention has universality and universality, the embodiment only takes LIBS as an analysis means to be displayed as an effect, and the method can be further expanded to other analysis technologies such as fluorescence spectrum, raman spectrum, infrared spectrum, ultraviolet spectrum, mass spectrum, terahertz spectrum, X-ray induced fluorescence, laser induced plasma, microwave induced plasma, radio frequency induced plasma, dielectric barrier discharge plasma and the like. In addition, the essence of the detection method of the invention is also within the protection scope of the invention after other solid phase and liquid phase are converted into gas phase.
The foregoing examples merely represent specific embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, it is possible to make related modifications and improvements without departing from the technical idea of the present application, which are all included in the protection scope of the present application.
Claims (7)
1. The aerosol LIBS detection composite film based on the nanostructure is characterized in that: has three layers of structures tightly attached and fixed with each other, and is respectively: the upper layer is a transparent polymer film (1) with adhesiveness, the middle layer is a dispersion film (2) with nanoscale thickness, and the lower layer is a bearing substrate (3), wherein the polymer film is used for carrying out adhesiveness capture on solid particles in aerosol in gas to be detected, the dispersion film (2) is a material with light dispersing capability, most laser energy can be dissipated when blank gas to be detected is detected, background signals are restrained, and the bearing substrate (3) is a bearing body of the polymer film (1) and the dispersion film (2).
2. The nanostructure-based aerosol LIBS assay composite film according to claim 1 characterized by: the thickness of the polymer film (1) is 50-500 mu m.
3. The nanostructure-based aerosol LIBS assay composite film according to claim 2 wherein: the thickness of the polymer film (1) is 50 μm.
4. The nanostructure-based aerosol LIBS assay composite film according to claim 1 characterized by: the bearing substrate (3) is a transparent structure capable of bearing the strength of the high polymer film (1) and the dispersion film (2).
5. The aerosol LIBS detection method is characterized by comprising the following steps of: the method comprises the following steps:
A. enriching the aerosol in the gas to be detected onto the aerosol LIBS detection composite film according to any one of claims 1 to 4;
B. placing an enrichment area of the aerosol LIBS detection composite film on an objective lens focus of a LIBS detection device for LIBS spectrum analysis;
C. outputting the element signals of LIBS spectrum analysis.
6. The aerosol LIBS assay method according to claim 5 wherein: the step C comprises the following steps: and a laser of the LIBS detection device emits laser beams to the aerosol LIBS detection composite film to ablate the gas to be detected, so that plasma on the aerosol LIBS detection composite film is excited to emit laser-induced plasma flame, a spectrum signal emitted by the laser-induced plasma flame is received by a spectrum receiving probe of the LIBS detection device, related data are collected by a spectrometer, and finally a required element signal is output by a computer.
7. The aerosol LIBS assay method according to claim 5 wherein: and (C) conveying the gas to be detected in the step (A) through a gas pump, and enriching the aerosol in the gas to be detected to the aerosol LIBS detection composite film after passing through a gas pipeline.
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