Integrated spraying and pulling combined detection system

Abstract

The invention relates to an integrated spraying and pulling combined detection system, which comprises a spray pen, a microscopic imaging module, an electric XYZ displacement table, a laser module, a spectrometer module and an industrial control computer, and is characterized in that the microscopic imaging module comprises an objective lens, a dichroscope, a tube lens, a light splitting plain film and an imaging camera which are sequentially arranged in the same vertical direction from bottom to top; the electric XYZ displacement table bears a to-be-tested sample to enable the to-be-tested sample to move below a nozzle of the airbrush and below the objective lens, laser emitted by the laser module irradiates the to-be-tested sample through the dichroscope and the objective lens, and the spectrograph module collects spectral signals of a to-be-tested object conducted through the objective lens, the dichroscope, the tube lens and the light splitting plain film. The device has the beneficial effects that the electric XYZ displacement table is adopted to bear the to-be-tested sample, so that the to-be-tested sample moves below the nozzle of the airbrush and the objective lens, the manual transfer link of the to-be-tested sample is eliminated, manual positioning errors are avoided, and the positioning time of the to-be-tested sample after transfer is saved.

Description

Technical Field

[0001] This invention relates to the field of Raman spectroscopy, and more particularly to an integrated spraying and Raman spectroscopy combined detection system. Background Technology

[0002] Trace detection of minute particles (such as microplastics in environmental water samples, contaminants in food, and biomarkers in biological samples) is crucial for environmental monitoring, food safety, and clinical diagnosis. Among current mainstream detection technologies, surface-enhanced Raman spectroscopy (SERS) has attracted widespread attention due to its label-free and highly specific advantages. However, its application relies on the compatibility of the SERS substrate and the Raman detection equipment, and existing technologies face three major challenges:

[0003] 1. Separation of substrate preparation and detection equipment, resulting in cumbersome and inefficient operation: Traditional surface-enhanced Raman spectroscopy substrates need to be prepared on specialized equipment (such as spray coating machines and deposition machines) through methods such as photolithography, electrochemical synthesis, and physical / chemical vapor deposition. After preparation, the sample needs to be manually transferred to the Raman spectrometer for detection. The entire process involves multiple devices and multiple manual operations, with a single detection taking more than 30 minutes, which cannot meet the needs of high-throughput on-site detection.

[0004] 2. Poor repeatability of detection and reliance on manual operation: During the substrate preparation stage, spraying / deposition parameters (such as distance, pressure, and concentration) need to be manually adjusted, which can easily lead to uneven substrate coverage; during the detection stage, the sample needs to be moved manually to find the detection point, resulting in low positioning accuracy (usually error > 10 μm), which leads to the relative standard deviation (RSD) of the same batch of samples generally being > 15%, making it impossible to guarantee the stability of the detection results.

[0005] 3. Weak trace signal capture capability and insufficient sensitivity: Traditional Raman spectrometers mostly use linear array detectors, which can only acquire signals in one dimension. When detecting low concentrations (e.g., <10 ppm), the sensitivity is insufficient. -8 When dealing with tiny particles (M), the signal is easily overwhelmed by noise; and existing systems have not optimized the optical path for "substrate enhancement-signal collection", which further reduces the detection capability of trace substances. Summary of the Invention

[0006] The purpose of this invention is to overcome the above-mentioned problems in the prior art and provide an integrated spraying and pulling detection system.

[0007] To achieve the above-mentioned technical objectives and effects, the present invention is implemented through the following technical solution:

[0008] An integrated spraying and dragnet combined inspection system includes:

[0009] An airbrush is used to spray paint onto a sample to be tested.

[0010] The microscopic imaging module includes an objective lens, a dichroic mirror, a tube lens, a beam splitter, and an imaging camera arranged in the same vertical direction from bottom to top.

[0011] An electric XYZ displacement stage, which carries the sample to be tested and moves the sample below the nozzle and the objective lens of the spray gun.

[0012] A laser module, wherein the laser emitted by the laser module is irradiated onto the sample to be tested through a dichroic mirror and an objective lens;

[0013] The spectrometer module acquires the spectral signal of the test object transmitted through the objective lens, dichroic mirror, tube lens, and spectrophotometer.

[0014] An industrial control computer is communicatively connected to an imaging camera, an electric XYZ displacement stage, a laser module, and a spectrometer module.

[0015] The laser module includes a laser, a first transmissive collimating lens, and a filter. The first transmissive collimating lens and the filter are located between the laser emission port of the laser and the dichroic mirror, and the filter is located between the first transmissive collimating lens and the dichroic mirror.

[0016] The spectrometer module includes an area array camera spectrometer, a second transmission collimating lens, and a high-pass filter. The high-pass filter and the second collimating lens are located between the beam splitter and the area array camera spectrometer, and the high-pass filter is located between the beam splitter and the second transmission collimating lens.

[0017] The area array camera spectrometer is equipped with an adjustable slit, a reflective collimating mirror, a blazed grating, a focusing mirror, and a thermoelectrically cooled CCD arranged in sequence according to an M-shaped optical path.

[0018] The thermoelectrically cooled CCD has 1024×256 pixels.

[0019] The objective lens is equipped with a white LED light to illuminate the sample to be tested.

[0020] The spray gun is either a gravity-feed spray gun or a pressure-feed spray gun.

[0021] The air inlet of the airbrush is connected to a pressure regulating valve for adjusting the air pressure via an air supply pipe, and the air inlet of the pressure regulating valve is connected to an air source via the air supply pipe.

[0022] The beneficial effects of this invention are:

[0023] The electric XYZ displacement stage is used to carry the sample to be tested, so that the sample can be moved under the nozzle of the spray gun and under the objective lens. This eliminates the manual transfer of the sample, avoids manual positioning errors, and saves the positioning time of the sample after transfer. The time for a single test is reduced from more than 30 minutes to less than 10 minutes, and the testing efficiency is improved by 3 times.

[0024] The paint was applied using an airbrush. Since the airbrush was already installed and fixed, and the airbrush spraying parameters were set correctly, the RSD of the substrate coverage uniformity was less than 3%. Combined with the signal accumulation of the thermoelectrically cooled CCD of the area array camera spectrometer, the RSD of the test result was less than 5%.

[0025] The thermoelectrically cooled CCD of an area array camera spectrometer can reduce dark current noise, and the accumulation of multi-row pixel signals of the thermoelectrically cooled CCD of an area array camera spectrometer can improve the signal-to-noise ratio by 8-10 times. Attached Figure Description

[0026] The accompanying drawings, which are included to provide a further understanding of the invention and form part of this application, illustrate exemplary embodiments of the invention and, together with their description, serve to explain the invention and do not constitute an undue limitation thereof. In the drawings:

[0027] Figure 1 This is a schematic diagram of the structure in this invention;

[0028] The following are the labels in the diagram: 1. Airbrush; 2. Objective lens; 3. Dichroic mirror; 4. Tubular lens; 5. Beam splitter; 6. Imaging camera; 7. Laser; 8. First transmission collimating lens; 9. Filter; 10. High-pass filter; 11. Second transmission collimating lens; 12. Area array camera spectrometer; 12. Adjustable slit; 121. Reflective collimating lens; 122. Blazed grating; 123. Focusing lens; 124. Thermoelectric cooled CCD; 125. Industrial control computer; 13. White LED light; 14. Electric XYZ stage; 15. Detailed Implementation

[0029] The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0030] like Figure 1 As shown, an integrated spraying and pulling detection system includes a spray gun 1 for spraying paint onto the sample to be tested, a microscopic imaging module, an electric XYZ displacement stage 15, a laser module, a spectrometer module, and an industrial control computer 13.

[0031] The height difference between the spray gun 1 and the sample to be tested is controlled between 5-20mm.

[0032] Airbrush 1 is either a gravity-feed airbrush or a pressure-feed airbrush. The gravity-feed airbrush has a nozzle diameter of 0.2 mm and a spraying pressure adjustment range of 0-3 bar, making it suitable for spraying concentrations of 1-10 wt% and for silver nanomaterials. The pressure-feed airbrush has a nozzle diameter of 0.3 mm and a spraying pressure adjustment range of 0-5 bar, making it suitable for spraying high-viscosity coatings, such as gold nanomaterials.

[0033] The air inlet of the airbrush 1 is connected to a pressure regulating valve for adjusting the air pressure through an air supply pipe. The air inlet of the pressure regulating valve is connected to the air source through the air supply pipe.

[0034] The microscopic imaging module includes, from bottom to top, an objective lens 2, a dichroic mirror 3, a tube lens 4, a beam splitter 5, and an imaging camera 6, arranged vertically in the same direction. A white LED lamp 14 is mounted on the objective lens 2 to provide illumination for the sample under test. The objective lens 2 has a magnification of 10x and a numerical aperture of 0.25. The imaging camera has a resolution of 1920×1080 and a frame rate of 30fps.

[0035] The laser emitted by the laser module is irradiated onto the sample under test through the dichroic mirror 3 and the objective lens 2. The laser module includes a laser 7, a first transmission collimating mirror 8, and a filter 9. The first transmission collimating mirror 8 and the filter 9 are located between the laser emission port of the laser 7 and the dichroic mirror 3, and the filter 9 is located between the first transmission collimating mirror 8 and the dichroic mirror 3.

[0036] The spectrometer module acquires the spectral signal of the sample transmitted through objective lens 2, dichroic mirror 3, tube lens 4, and beam splitter 5. The module includes an area array camera spectrometer 12, a second transmission collimating lens 11, and a high-pass filter 10. The high-pass filter and the second collimating lens are located between the beam splitter and the area array camera spectrometer, with the high-pass filter positioned between the beam splitter and the second transmission collimating lens. The tube lens has a focal length of 200mm, the beam splitter has a reflectivity of 50%, and the dichroic mirror allows Raman signals to pass through.

[0037] The area array camera spectrometer 12 is an M-type Czerny-Turner structure spectrometer. The area array camera spectrometer includes an adjustable slit 121, a reflective collimating mirror 122, a blazed grating 123, a focusing mirror 124, and a thermoelectrically cooled CCD 125, arranged sequentially according to the M-type optical path. The adjustable slit width is adjustable from 0.1 to 1 mm; the blazed grating has a line density of 1200 / mm and a blaze wavelength of 532 nm; the thermoelectrically cooled CCD is an Andor iDus model with a cooling temperature of -56℃, a pixel size of 13.5 μm × 13.5 μm, and a pixel count of 1024 × 256.

[0038] To improve spectral resolution, the grating with a line density of 1200 / mm² can be replaced with one with a line density of 2400 / mm² and a blaze wavelength of 532nm. This will increase the spectral resolution from 5cm² to 100nm. -1 Increased to 2cm -1 To distinguish closer Raman characteristic peaks (such as characteristic peaks of different types of microplastics), the slit width of the adjustable slit needs to be adjusted to 0.2mm simultaneously to ensure signal strength.

[0039] For different Raman characteristic peaks of different substances, either a 532nm laser or a 785nm laser can be selected. When using a 532nm laser, the linewidth is <0.2nm, the power adjustment range is 0-133.4mW, and the suitable narrowband filter is Chroma RET532 / 4X, the dichroic mirror is Chroma RT532RDC, and the high-pass filter is Chroma RET537LP. When using a 785nm laser, the linewidth is <0.3nm, the power adjustment range is 0-200mW, and the suitable narrowband filter is Chroma RET785 / 6X, the dichroic mirror is Chroma RT785RDC, and the high-pass filter is Chroma RET792LP. This is suitable for samples that are affected by fluorescence interference from 532nm lasers.

[0040] Objective lens, dichroic mirror, tube lens, beam splitter, imaging camera, first transmissive collimator, filter, second transmissive collimator, and high-pass filter are all mounted on an optical cage support to ensure coaxial optical path.

[0041] The laser output from the laser is collimated by the first transmission collimating lens and then focused onto the surface of the sample under test by passing through a filter, a dichroic mirror, and an objective lens in sequence. The backscattered Raman signal generated by the sample under test returns along the original optical path and passes through the dichroic mirror and a tube lens in sequence to reach the beam splitter. After being reflected by the beam splitter to the high-pass filter, it is collimated by the second transmission collimating lens and focused onto the slit of the area array camera spectrometer, so that the Raman signal can enter the area array camera spectrometer to collect the spectral signal.

[0042] The light from the area below the objective lens passes sequentially through the objective lens, dichroic mirror, tube lens, and beam splitter, and is then captured by the imaging camera to obtain an image of the area below the objective lens.

[0043] The combination of the microscopic imaging module, laser module, and spectrometer module allows some optical elements to be shared, reducing the number of optical elements used and saving space.

[0044] The spray gun is mounted on one side of an optical cage support via a bracket. An electric XYZ displacement stage carries the sample to be tested, allowing the sample to move below the nozzle and the objective lens of the spray gun.

[0045] The electric XYZ displacement stage has a stroke of 300mm×100mm×100mm and a positioning accuracy of ±1μm.

[0046] The industrial control computer is communicatively connected to the imaging camera, the motorized XYZ stage, the laser module, and the spectrometer module. Specifically, the motor drivers of the imaging camera and the motorized XYZ stage, as well as the thermoelectrically cooled CCD, communicate with the industrial control computer via USB interfaces, while the laser's power controller communicates with the industrial control computer via an RS485 interface.

[0047] The industrial control computer has at least an Intel i5 processor CPU and at least 16GB of memory. It also includes imaging processing software for the imaging camera, spectral processing software for the area array camera spectrometer, and customized control software developed based on LabVIEW.

[0048] The customized control software includes a parameter setting module, a collaborative control module, a data processing module, and a result output module. The parameter setting module can set the laser power, integration time, and displacement platform position. The collaborative control module synchronously controls the positioning, spraying, excitation, and detection steps. The data processing module performs baseline correction, smoothing, characteristic peak identification, and material matching. The result output module generates a test report and spectrum.

[0049] During spraying and testing, for solid samples, the sample cell is generally placed on the moving platform of the electric XYZ displacement stage, and then the sample is placed in the sample cell; for liquid samples, a 100μL microflow cell is generally placed on the moving platform of the electric XYZ displacement stage, and then the sample is fed into the microflow cell by a peristaltic pump.

[0050] The paint was applied using an airbrush. Since the airbrush was properly installed and the spraying parameters were set correctly, the RSD of the substrate coverage uniformity was <3%. Combined with the signal accumulation from the thermoelectrically cooled CCD of the area array camera spectrometer, the RSD of the detection result was <5%. (The last part, "10," appears to be an unrelated fragment and is omitted from the translation.) -9 Taking M crystal violet as an example, the characteristic peak intensity RSD of 5 repeated detections was 4.2%, which is significantly better than the 15% of the traditional technology.

[0051] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection, an electrical connection, or a connection that allows communication between them; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components, unless otherwise explicitly limited. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0052] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. An integrated spraying and joint detection system, characterized in that, include: An airbrush is used to spray paint onto a sample to be tested. The microscopic imaging module includes an objective lens, a dichroic mirror, a tube lens, a beam splitter, and an imaging camera arranged in the same vertical direction from bottom to top. An electric XYZ displacement stage, which carries the sample to be tested and moves the sample below the nozzle and the objective lens of the spray gun. A laser module, wherein the laser emitted by the laser module is irradiated onto the sample to be tested through a dichroic mirror and an objective lens; The spectrometer module acquires the spectral signal of the test object transmitted through the objective lens, dichroic mirror, tube lens, and spectrophotometer. An industrial control computer is communicatively connected to an imaging camera, an electric XYZ displacement stage, a laser module, and a spectrometer module.

2. The detection system according to claim 1, characterized in that: The laser module includes a laser, a first transmissive collimating lens, and a filter. The first transmissive collimating lens and the filter are located between the laser emission port of the laser and the dichroic mirror, and the filter is located between the first transmissive collimating lens and the dichroic mirror.

3. The detection system according to claim 1, characterized in that: The spectrometer module includes an area array camera spectrometer, a second transmission collimating lens, and a high-pass filter. The high-pass filter and the second collimating lens are located between the beam splitter and the area array camera spectrometer, and the high-pass filter is located between the beam splitter and the second transmission collimating lens.

4. The detection system according to claim 3, characterized in that: The area array camera spectrometer is equipped with an adjustable slit, a reflective collimating mirror, a blazed grating, a focusing mirror, and a thermoelectrically cooled CCD arranged in sequence according to an M-shaped optical path.

5. The detection system according to claim 4, characterized in that: The thermoelectrically cooled CCD has 1024×256 pixels.

6. The detection system according to claim 1, characterized in that: The objective lens is equipped with a white LED light to illuminate the sample to be tested.

7. The detection system according to claim 1, characterized in that: The airbrush is either a gravity-feed airbrush or a pressure-feed airbrush.

8. The detection system according to claim 1, characterized in that: The air inlet of the airbrush is connected to a pressure regulating valve for adjusting the air pressure via an air supply pipe. The air inlet of the pressure regulating valve is connected to an air source via the air supply pipe.

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