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CN120002879A - A small laser irradiation grafting and cross-linking system with controllable energy level and its application method - Google Patents

A small laser irradiation grafting and cross-linking system with controllable energy level and its application method
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Publication number
CN120002879A
CN120002879ACN202510393671.7ACN202510393671ACN120002879ACN 120002879 ACN120002879 ACN 120002879ACN 202510393671 ACN202510393671 ACN 202510393671ACN 120002879 ACN120002879 ACN 120002879A
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laser
processing
grafting
crosslinking
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李丽丽
韩爽
王玉龙
李育哲
高俊国
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Harbin University of Science and Technology
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Harbin University of Science and Technology
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Abstract

The invention relates to a small-sized laser irradiation grafting and crosslinking system with controllable energy level and an application method thereof, belonging to the technical field of material processing and modification. The system consists of an adjustable laser source, a focusing optical system, a laser energy regulation and control module, a processing platform, a chemical reaction auxiliary module, a real-time monitoring and feedback system and an intelligent control system, and can accurately control the wavelength, the power and the pulse width of laser to realize micron-level processing precision. Compared with the traditional chemical grafting method, the thermal induced crosslinking method and the plasma treatment method, the invention has the remarkable advantages of non-contact processing, low energy consumption, high precision, environmental protection and the like. The system supports efficient grafting and crosslinking of various materials (such as polymers, metals and ceramics), remarkably improves the processing efficiency and the material performance, and provides an innovative solution for material functionalization and green manufacturing.

Description

Energy-level-controllable small laser irradiation grafting and crosslinking system and application method thereof
Technical Field
The invention belongs to the technical field of material processing and modification, and particularly relates to a small-sized laser irradiation grafting and crosslinking system with controllable energy level and an application method thereof.
Background
The material surface modification technology is widely applied to the fields of polymer functional materials, biomedical devices, microelectronic devices and the like, and can effectively improve the surface properties of the materials through grafting or crosslinking means, such as enhancing the interface binding force, improving the wear resistance and corrosion resistance, introducing specific functional groups and the like. Wherein, grafting and crosslinking modification technology has become an important method for functionalization of polymer materials. However, the existing material grafting and crosslinking techniques still have many disadvantages.
The surface grafting and crosslinking methods commonly used at present include a chemical grafting method, a heat-induced crosslinking method, a plasma treatment method and a laser irradiation method. Chemical grafting methods generally rely on peroxide-based chemical initiators, which, while highly reactive, often lead to degradation of the polymer backbone with concomitant residues of byproducts, affecting the purity and performance stability of the material. Although the heat-induced crosslinking method is mature in process, the heat-induced crosslinking method needs to be carried out in a high-temperature environment, so that the heat-oxygen aging of the material is easy to be initiated, the local crosslinking degree difference is large due to uneven temperature distribution, and the common deviation can reach +/-30%. The plasma treatment method can realize the modification of the nano scale of the material surface, but the equipment power consumption is higher, the operation is complex, the modification effect maintenance time is shorter, and the modification effect maintenance time is generally less than 72 hours. In addition, the existing laser irradiation grafting and crosslinking technology has the characteristics of non-contact and fine processing, but still faces the problem of insufficient laser energy level regulation precision, and is easy to cause the phenomena of material ablation, uneven grafting and the like, so that the processing stability is poor and the product consistency is insufficient.
Most of the traditional material grafting and crosslinking systems have huge structures and low system integration level, and are difficult to meet the requirements of small-batch processing or field application in a laboratory. The technologies have generally higher energy consumption, large environmental load and insufficient green environmental protection, and limit the further application of the technologies in fine processing of high-performance materials.
In summary, the existing material surface grafting and crosslinking techniques still have a number of bottlenecks in terms of reaction condition controllability, energy consumption management, equipment volume and adaptability. Therefore, development of a novel grafting and crosslinking system with controllable energy level, miniaturized system, strong adaptability and high processing precision is needed to meet the requirements of high-polymer material functionalization and high-efficiency and environment-friendly processing of various composite materials.
Disclosure of Invention
Aiming at the problems of high material degradation risk, poor process controllability, large environmental load and the like in the traditional grafting and crosslinking technology, the invention provides a small-sized laser irradiation grafting and crosslinking system with controllable energy level. The system realizes innovation breakthrough through the following technical scheme:
The adjustable laser source adopts a semiconductor laser, the wavelength range is 355nm to 1064nm, the power adjustment range is 0.1W to 10W, the pulse frequency is 1Hz to 1kHz, and the adjustable laser source is provided with a built-in temperature control unit, so that the stability and controllability of laser output are ensured.
The focusing optical system comprises an aspheric quartz lens with high light transmittance and a high-reflectivity reflecting mirror with gold plated surface, wherein the reflectivity is more than 99.5%, the fluctuation of reflection efficiency in the incident angle range is less than 0.5%, the laser beam is efficiently conducted and focused on the surface of a material to be processed through the lens, the reflecting mirror and the optical fiber transmission system, and the dynamic optical path adjusting function is matched, so that the X/Y/Z axis multidimensional micro-displacement adjustment is realized, the displacement precision reaches +/-0.1 mu m, the material surface with different thickness and morphology is adapted, and the processing precision is ensured;
The laser energy regulation and control module comprises a beam splitter and a power control unit, adopts an electrically-regulated iris diaphragm and a polaroid to realize fine adjustment of laser intensity, can select single pulse, periodic pulse and continuous mode switching according to different materials and process requirements, and dynamically adjusts laser output by combining a real-time feedback system to realize efficient and stable energy control;
The processing platform adopts a three-dimensional moving platform, has a high-precision positioning function, has the moving precision of +/-1 mu m and the maximum travel of 100mm multiplied by 50mm, supports the automatic processing of samples with different sizes, and integrates a flexible fixing device and a vacuum adsorption system so as to ensure the stability of materials in the processing process and the accurate execution of processing paths;
The chemical reaction auxiliary module comprises a gas environment control system, the flow of inert gas (nitrogen and argon) and the flow of active gas (oxygen) are accurately regulated through a mass flowmeter, the flow regulation range of the nitrogen is 0.1L/min to 10L/min, the flow regulation range of the oxygen is 0.05L/min to 5L/min, the rapid switching and control of various atmosphere environments are realized by combining a gas mixing unit, the system has a gas purity real-time detection function, the purity of the reaction environment is ensured, and the reaction process is automatically alarmed and terminated when the gas purity is lower than a set threshold value;
the real-time monitoring and feedback system comprises a K-type thermocouple temperature sensor (the measuring range is-50 ℃ to 300 ℃, the error is +/-0.5 ℃), an optical fiber spectrometer (the wavelength resolution is +/-0.1 nm, the integration time is 1ms to 1000 ms) and a high-resolution CMOS camera (the resolution is 5MP, the positioning error is +/-1 mu m), the omnibearing dynamic monitoring of the temperature, the reaction progress and the surface morphology of a processing area is realized through multi-sensor data fusion, and processing parameters are fed back in real time and automatically corrected based on a Kalman filtering and image edge detection algorithm, so that the laser energy distribution and the scanning path are optimized;
The intelligent control system adopts an embedded processor architecture, integrates operation software and a human-computer interaction interface, supports parameter self-defining setting, processing path planning, data real-time recording and full-flow automatic control, has abnormal state intelligent alarm and linkage protection functions, and remarkably improves the convenience and safety of processing operation.
Further, the power adjustment precision of the adjustable laser source reaches 0.1mW, and the diversified requirements of different materials and different reaction types on the laser energy level can be met.
Further, the focusing optical system is optimized through Zemax optical simulation, so that the diameter of a laser focusing light spot is ensured to be smaller than 5 mu m, the energy density distribution uniformity is better than 90%, and the method is suitable for the surface modification requirements from submicron to nanometer.
Further, the dynamic light path adjusting function is realized through a piezoelectric ceramic micro-displacement platform, the X/Y/Z three-axis is synchronously adjusted, the repeated positioning precision is better than +/-0.05 mu m, and the laser dynamic focusing requirement of the material with the complex morphology is met.
Further, the laser energy regulation and control module supports graded energy scheduling, and the problems of material ablation and local overheating in the grafting or crosslinking process are avoided to the greatest extent.
Furthermore, the chemical reaction auxiliary module presets various typical process parameters, supports customized adjustment of the special atmosphere environment of polypropylene, metal, ceramic and composite materials, and meets diversified application scenes.
Further, the response time of the real-time monitoring and feedback system is smaller than 50ms, so that automatic correction of sub-second laser parameters can be realized, and high precision and high consistency of the processing process are ensured.
Furthermore, the intelligent control system is provided with a process optimization algorithm based on historical data and a remote control interface, supports production data cloud storage and multi-terminal synchronous management, and is suitable for various application scenes such as laboratories, factories and field services.
The invention also provides a laser irradiation grafting and crosslinking application method based on the system, which comprises the following steps:
(1) Material pretreatment, namely cleaning the surface of the material by deionized water and ultrasonic waves to ensure no impurity pollution;
(2) Preparing and coating a chemical solution, namely uniformly spraying maleic acid and a photoinitiator on the surface of a material to be treated after preparing the maleic acid and the photoinitiator according to the mass ratio to form a reaction layer with the thickness of not more than 10 mu m;
(3) Fixing and positioning, namely fixing a material on a sample stage through a processing platform, and ensuring that the surface is flat and positioned in the range of a laser irradiation focusing point;
(4) Setting parameters and starting processing, namely setting laser wavelength (355 nm to 1064 nm), power (2W to 10W), pulse frequency (1 Hz to 1 kHz) and scanning speed (1 mm/s to 10 mm/s) according to material properties;
(5) Performing irradiation treatment, namely performing laser irradiation in a nitrogen protection environment to ensure that the grafting or crosslinking reaction of the surface of the material is sufficient and uniform;
(6) Feedback optimization and real-time monitoring, namely dynamically adjusting laser parameters and scanning paths according to real-time temperature and spectrum data, and avoiding overheating or insufficient reaction;
(7) And (3) after-treatment and detection, cleaning and drying the material after the processing is finished, and evaluating the surface modification effect and the improvement of mechanical properties through SEM, FTIR, mechanical test and other methods.
Based on the technical scheme, the energy-level-controllable small laser irradiation grafting and crosslinking system of the embodiment of the invention realizes high-precision and dynamic adjustment of laser energy, irradiation paths and reaction environments by integrating the adjustable laser source, the focusing optical system and the dynamic energy adjustment and real-time feedback control module, and remarkably improves the controllability and processing quality of the material grafting and crosslinking process. The invention effectively solves the problems of rough regulation and control of laser energy level, lack of real-time feedback control in the processing process, large equipment volume, high environmental load and the like in the prior art.
The miniaturized design of the invention makes the system suitable for various application scenes such as laboratory environment, small-scale production, field processing and the like, and improves the flexibility and universality of the laser grafting and crosslinking technology. The system realizes compatibility treatment on various materials such as polymers, metals, ceramics and the like through the laser output capability of multiple wavelengths and a wide power range, and provides an efficient solution for surface modification of different material systems.
In addition, the green environment-friendly process flow is adopted, so that the problems of chemical reagent residue and environmental pollution in the traditional chemical method are avoided, the energy consumption in the laser processing process is low, the overall energy efficiency ratio is improved by more than 30%, and the green manufacturing concept is met. Through intelligent control and automatic management, the invention also obviously reduces the operation threshold and the dependence on manpower, and improves the process stability and the product consistency.
Compared with the prior art, the invention has the following beneficial effects:
1. The laser energy has strong controllability, and can realize accurate material modification at the micrometer or nanometer level by combining a high-precision focusing optical system, and the minimum processing area can be less than 1 mu m. The laser pulse mode optimizes the processing rate, the grafting and crosslinking time is obviously shortened, and the efficiency is improved by more than 50 percent compared with the traditional chemical method. By means of the three-dimensional moving platform and the automatic path control function, uniform laser distribution in a processing area is ensured, and the consistency of processing effects is high.
2. The system adopts modularized and lightweight design, greatly reduces the volume and weight of the whole equipment, and is suitable for laboratories, scientific researches and industrial sites. The equipment is simple to install, can be rapidly deployed, supports mobile and portable applications, and meets the requirements of multiple scenes.
3. Environmental protection and low cost, avoids the dependence on catalysts, solvents and other chemical reagents in the traditional chemical reaction by a non-contact laser processing technology, and reduces environmental pollution and waste treatment cost. The laser source has high energy utilization rate and low power requirement, and the overall energy consumption is reduced by more than 30 percent, thereby conforming to the green manufacturing concept.
4. The system can accurately process polymers (such as PP, PVDF and the like), composite materials, metals and flexible electronic materials and adapt to the physical and chemical characteristics of different materials. The adjustable design of laser wavelength, power and pulse width can meet the grafting and crosslinking requirements of various materials, and has extremely high applicability.
5. And the intelligent and automatic processing state is monitored in real time through a temperature sensor, a spectrum analysis module and a high-definition camera, and laser parameters are dynamically optimized according to feedback, so that the processing quality is ensured. The intelligent control system realizes full-flow automation from parameter setting and processing path planning to data recording, greatly reduces manual intervention and improves operation convenience.
6. The material has obviously improved performance, high laser-induced chemical reaction efficiency, controllable grafting and crosslinking degree and obviously improved mechanical strength, heat resistance, chemical resistance and other performances. By adjusting laser parameters, various grafting and crosslinking effects can be realized, and the diversified requirements of the material in high polymer composite materials, electronic devices and biomedical materials are met.
7. The method has wide application scene, and is suitable for small-batch sample preparation and performance test in the fields of material science, chemical engineering and biomedicine. Has important application value in precision manufacture, flexible electronics, functional coating and high-performance composite material production. The portability design enables material surface repair or functionalization at the industrial site.
In summary, the invention provides the energy-level-controllable small-sized laser irradiation grafting and crosslinking system with high precision, low energy consumption, environmental protection and strong adaptability and the application method thereof, which provides a brand new technical path for the surface modification of the high polymer material, the preparation of the high-performance composite material and the manufacturing of precision devices, and has remarkable application prospect and popularization value.
Drawings
FIG. 1 is a block diagram of an overall system arrangement of the present invention;
FIG. 2 is a schematic diagram of the irradiation system of the present invention;
FIG. 3 is a schematic view of a laser irradiator of the present invention;
FIG. 4 is a diagram of a laser applicator interface design of the present invention;
FIG. 5 is a graph showing the energy wave pattern produced by the laser irradiator of the present invention;
FIG. 6 is a graph of the optical lens profile characterization and optical test of the present invention.
Detailed Description
The invention relates to a small-sized laser irradiation grafting and crosslinking system with controllable energy level, which aims to realize high-precision and high-efficiency modification of the surface of a material by a laser irradiation technology. The following describes the embodiments of the present invention in detail with reference to the drawings and table contents.
1. Examples:
(1) System composition and working principle
The system mainly comprises an adjustable laser source, a focusing optical system, a laser energy regulating and controlling module, a processing platform, a chemical reaction auxiliary module, a real-time monitoring and feedback system and an intelligent control system. As shown in fig. 1, the system realizes the full-flow automatic control of laser irradiation grafting and crosslinking through a modularized design.
1. Adjustable laser source
The system adopts a semiconductor laser with a wide wavelength range as a laser source, covers 355nm to 1064nm wave bands, has a power adjustment range of 0.1W to 10W and has a pulse frequency of 1Hz to 1kHz. The laser is internally provided with a high-precision temperature control unit, and the laser cavity is maintained in an optimal working state through temperature control, so that the stability of laser wavelength and power output is ensured.
The laser guides the laser beam into the focusing optical system through an optical fiber or a free space transmission mode, so that the stability and the energy consistency of a laser output path are ensured. To achieve efficient integration of the system with external control devices, power supply systems, and safety interlock mechanisms, the laser applicator is provided with a variety of standardized interfaces (as shown in fig. 4), including a remote interlock socket, a USB socket, a universal input/output port, and a power supply voltage socket.
Fig. 3 is a schematic diagram of a laser irradiator of the present invention, showing the overall structural layout of the laser source and the detailed position distribution of each functional interface. Through the interface design, remote monitoring, data communication, laser start-stop control and equipment running state feedback can be realized, and the convenience and the system integration level of equipment operation are improved.
In addition, the technical parameters of the laser irradiator of the system are shown in table 1:
Table 1 laser irradiator parameters
Note that SM means single mode fiber, PM means polarization maintaining fiber, MM means multimode fiber, and the system flexibly configures fiber output modes according to processing requirements. Different wavelength and power configurations can flexibly cope with the processing requirements of various materials such as polymers, metals, ceramics and the like. The digital modulation is up to 150MHz, the high-speed modulation process is adapted, and the pulse laser control capability is enhanced.
2. Focusing optical system
The focusing optical system adopts an aspheric quartz lens with high light transmittance (focal length 50mm, numerical aperture NA=0.6) and a high-reflectivity reflecting mirror with gold-plated surface (reflectivity > 99.5%), and focuses the laser beam on the surface of the material to be processed through the lens, the reflecting mirror and the optical fiber transmission system.
The high-transmittance lens group and the reflecting mirror which contain the anti-reflection coating and have single lens transmittance of more than 99.8 percent and the overall light path efficiency of more than 95 percent are adopted, so that the light loss is reduced to the greatest extent. The dynamic light path adjusting function is realized by driving the micro-displacement platform through piezoelectric ceramics, the X/Y/Z axis displacement precision is +/-0.1 mu m, the repeated positioning precision is +/-0.05 mu m, and the real-time calibration of the focus position offset is supported. The light path calibration algorithm is based on CCD image feedback, and the light path deviation is automatically corrected by a Gaussian spot centroid positioning method (positioning error + -0.5 mu m). The zoom range of the adjustable focus lens is +/-10 mm, the stepping motor is driven, the step precision is 0.1 mu m, and flexible processing of materials with different thicknesses is supported. The optical path design is verified by Zemax optical simulation, the diameter of a focusing light spot is less than 5 mu m, and the uniformity of energy density distribution is more than 90%.
As shown in fig. 6, the optical lens morphology characterization and the optical test show that the focusing light spot diameter is <5 μm, and the uniformity of the energy density distribution is >90%. The dynamic light path adjusting function is realized by driving the micro-displacement platform through piezoelectric ceramics, the X/Y/Z axis displacement precision is +/-0.1 mu m, the repeated positioning precision is +/-0.05 mu m, and the real-time calibration of the focus position offset is supported.
3. Laser energy regulation and control module
The laser energy regulation and control module comprises a beam splitter and a power control unit and supports single pulse, periodic pulse and continuous mode switching. The beam splitter is used for separating the main beam and the reference beam, and energy control accuracy is guaranteed. The power control unit may adjust the laser intensity by electrically modulating an iris, a polarizer, etc. As shown in fig. 5, the energy wave generated by the laser irradiator realizes multi-level processing through dynamic energy regulation.
4. Processing platform
The processing platform is a three-dimensional moving platform, the moving precision is +/-1 mu m, the maximum travel is 100mm multiplied by 50mm, and a high-precision positioning system is provided. The platform is connected by a computer or control system to ensure movement according to a predetermined path and speed. As shown in fig. 2, a schematic structural diagram of the irradiation system illustrates the cooperative working of the processing platform and the laser beam.
5. Chemical reaction auxiliary module
The chemical reaction auxiliary module integrates a gas environment control system, and realizes the dynamic proportioning of nitrogen (N2), oxygen (O2) or argon (Ar) through a high-precision mass flowmeter, so that the gas components of the reaction environment are ensured to be accurately controllable. The system is provided with a gas purity detection module, the gas purity is monitored in real time, and when the gas purity is detected to be lower than a set threshold (such as 99.99%), an alarm is automatically triggered and the reaction is terminated, so that the safety and the reliability of an experiment are ensured. Furthermore, the system presets gas patterns for different materials, such as:
and the polypropylene grafting is carried out in a pure nitrogen environment, the flow is set to be 5L/min, and the interference of oxygen on the grafting reaction is avoided.
And (3) oxidizing the metal surface, namely adopting mixed gas of oxygen and nitrogen, wherein the flow ratio is O22L/min+N2 L/min, and optimizing the oxidation reaction effect.
And (3) ceramic activation, namely adopting a pure argon environment, setting the flow to 8L/min, and ensuring the efficient activation of the ceramic surface.
Through nimble gas ratio and preset mode, the processing demand of multiple material can be satisfied to chemical reaction auxiliary module, is showing the accuracy and the efficiency that promote the reaction.
The gas environment control system provides protection for inert gases (such as nitrogen and argon) and prevents interference of oxygen on the reaction. The system adopts a mass flowmeter to carry out closed-loop feedback control, the nitrogen flow adjustment range is 0.1-10L/min, the control precision is +/-0.05L/min, the oxygen flow adjustment range is 0.05-5L/min, and the precision is +/-0.03L/min. The system can introduce oxygen to promote the occurrence of certain oxidation reactions, and realize the dynamic proportioning of N2/O2 through a gas mixing unit (for example, the nitrogen accounts for more than or equal to 95% in the reduction reaction and the oxygen accounts for 5-50% in the oxidation reaction). For different materials, the system is preset with gas modes of polypropylene grafting (N2 flow 5L/min), metal surface oxidation (O2 flow 2L/min+N2 L/min) and ceramic activation (Ar flow 8L/min). In addition, a gas purity detection module (detection precision is +/-0.1%) is built in the system, and when the gas purity is lower than 99.99%, the reaction is automatically alarmed and terminated.
6. Real-time monitoring and feedback system
The device comprises a K-type thermocouple temperature sensor (measuring range-50-300 ℃ and error +/-0.5 ℃), an optical fiber spectrometer with wavelength resolution +/-0.1 nm and integration time of 1-1000ms, and an image analysis module consisting of a CMOS camera (resolution 5MP and positioning error +/-1 mu m). The system is used for monitoring the temperature, the reaction state and the surface morphology of a processing area in real time and dynamically optimizing laser parameters. The data processing algorithm adopts Kalman filtering (multi-sensor data fusion error < 1%) and Canny edge detection algorithm (pixel level error +/-0.5 px), and the feedback response time is <50ms, so that the dynamic optimization of the processing process is realized.
7. Intelligent control system
The intelligent control system is based on an embedded processor, integrates a software interface and provides parameter setting, data recording and automatic control functions of the processing process. The system monitors the processing state in real time through the temperature sensor, the spectrum analysis module and the high-definition camera, and dynamically optimizes the laser parameters according to feedback.
The working principle of the system is as follows:
A laser beam (selected for suitable wavelength, power and pulse width) is first emitted by a tunable laser source by laser irradiation, suitable for the target material. The laser beam is precisely focused on the surface of the material by a focusing optical system to form a processing area with high energy density. And then under the high-energy irradiation of laser, the molecules on the surface of the material are excited, and the excited molecules and reactants are combined to form a grafted structure or form a crosslinked structure through high-energy collision. And then, moving the sample according to the set track through the processing platform to ensure that the laser completes uniform processing in the designated area. The three-dimensional movement function allows the grafting and crosslinking process to be implemented in multiple levels or complex shapes. And then, carrying out real-time monitoring and feedback adjustment on the data. The temperature of the processing area is detected by a temperature sensor, so that material degradation caused by overheating is prevented. The spectrum analysis module monitors the chemical reaction state in real time, and ensures that grafting and crosslinking are fully completed. The system dynamically adjusts laser power, pulse width or path according to the feedback data, and ensures processing precision and stability. And after finishing processing, carrying out quality assessment on the surface morphology and performance data recorded by the monitoring system. And a complete data report of the processing process is generated, so that the subsequent process optimization and mass production reference are facilitated.
Through the composition and the working principle, the invention realizes the efficient, accurate and environment-friendly material grafting and crosslinking processing process, and is suitable for various application scenes and material types.
2. Examples of specific applications
(1) Material preparation
1. Polypropylene (PP) film-a commercially available polypropylene film was selected to have a thickness of 0.1mm and cut to a size of 30mm x 30mm suitable for the experimental or production requirements.
2. The purity of the maleic acid which is selected from maleic acid with proper specification is more than or equal to 99.5 percent.
3. The photoinitiator is Ammonium Persulfate (APS) with the required purity not less than 98 percent.
4. Deionized water for dissolving maleic acid and photoinitiator.
5. Sample pretreatment, namely dissolving 10g of maleic acid in 90mL of deionized water to prepare a maleic acid solution with the mass fraction of 10 wt.%. Ammonium persulfate photoinitiator (1% of the mass of maleic acid) was added and stirred well until completely dissolved.
6. And fixing and installing the sample, namely fixing the material sample on a processing platform, and ensuring that the sample is stable and does not move in the laser irradiation process. The fixing method comprises the use of a mechanical clamp or suction cup.
7. And (3) optical detection of the material, namely detecting the light transmittance of the material by using a spectrometer before laser processing, and selecting the material suitable for the laser wavelength so as to improve the absorption efficiency of laser energy.
(2) Device connection and debug
1. The output of the laser needs to be connected to a focusing optical system (e.g. lens, mirror, etc.) via an adapter to ensure accurate transmission of the laser beam to the material to be processed.
2. The laser light is transmitted to the focusing lens through an optical fiber or free space. Ensure that the optical fiber connection is not loose, and adjust the insertion angle of the optical fiber to ensure that the laser beam is transmitted along a correct path.
3. The three-dimensional platform needs to be connected to a computer or control system to ensure that it can move in accordance with a predetermined path and speed. And the driving motor, the power supply and the sensor system of the platform are connected, so that the moving precision and the stability of the platform are ensured. And the temperature control platform is connected, the temperature range and the control precision are adjusted, and the temperature of the sample is ensured to be stabilized near a set value in the processing process.
4. And a high-definition camera or an infrared camera is arranged and used for monitoring the surface state of the sample in the laser processing process in real time. And the reaction condition of the sample surface is obtained in real time through image processing software, so that the uniformity and consistency of processing are ensured. The CCD camera is used for collecting focused light spot images, a centroid positioning algorithm is used for calculating light spot offset, and the piezoelectric ceramic platform is driven to compensate position deviation within a range of +/-0.5 mu m.
5. Before the laser is started, the target temperature is set to 25 ℃ through a PID control algorithm, and laser output calibration is performed after the temperature control unit is stabilized within the range of +/-0.1 ℃.
6. And setting feedback mechanisms of parameters such as temperature, power and the like, and automatically adjusting laser parameters or processing paths when the system detects abnormal processing conditions, so as to ensure that the processing process is always in an optimal state.
(3) Experimental operation
1. And placing the cleaned PP sample on an experimental platform to ensure that the sample is fixed and positioned in a laser irradiation area.
2. And the maleic acid solution is uniformly coated on the surface of the PP film by using a micro spraying system, so that the surface of the sample is ensured to be completely covered with the MA solution, and partial areas are prevented from being missed. The coating thickness is controlled within 10 μm. Standing for 10 minutes after coating ensures that the solution forms a uniform film on the PP surface.
3. The laser is started, the laser system is started, the laser power is set to be 5W, the wavelength is 355nm (matched with the absorption peak of maleic anhydride), the pulse frequency is 50Hz, and the pulse width is 10ns-1ms.
4. Under the protection of nitrogen (flow 5L/min, purity 99.99%), the surface of the sample is scanned by laser with scanning speed of 5mm/s and irradiation time of 3 minutes.
5. When the laser beam irradiates, the three-dimensional platform moves steadily according to the set path and speed, so that the laser irradiates the surface of the PP sample uniformly.
6. After the laser irradiation was completed, the sample was gently wiped with deionized water to remove unreacted maleic acid and initiator residues.
7. The sample was placed in a vacuum oven and dried for 30 minutes at a set temperature of 40 ℃.
(4) Performance assessment
1. The surface morphology of the PP sample after laser irradiation was observed using a Scanning Electron Microscope (SEM). The microstructure change of the PP sample surface is analyzed to determine whether the grafting reaction was successful.
2. The surface topography before and after the treatment was compared to see if a new structure was formed or the surface roughness was changed.
3. The sample surface chemical changes were analyzed using fourier transform infrared spectroscopy (FTIR). FTIR spectra before and after grafting were compared to see if a MA characteristic peak (e.g., absorption peak of a functional group such as c= O, C =c) appeared, thereby verifying the occurrence of grafting reaction.
4. The mechanical properties of the grafted PP samples are evaluated by tensile test, hardness test and other methods. The grafting reaction generally increases the surface strength, abrasion resistance, and tensile strength of the material.
5. Samples were tested for thermal stability using thermogravimetric analysis (TGA) and Differential Scanning Calorimetry (DSC). The grafting reaction can improve the thermal stability of PP, and the thermal degradation temperature and thermal degradation characteristics of the sample are analyzed in the test process.
6. The degree of grafting was determined using a solubility test (e.g., dissolved in an appropriate solvent) or other quantitative method to verify the effect of PP grafted MA under laser irradiation.
3. Experimental results and data analysis
Based on experimental data, table 2 shows a comparison of experimental results of the system of the present invention compared to conventional chemical methods:
Table 2 comparative experimental data table
Index (I)Traditional chemical methodsThe invention is thatAmplitude of lift
Grafting percentage (%)65±588±335%
Reaction time (min)120893%
Energy consumption (kWh/kg)2.50.388%
According to the comparative experimental data table of Table 2, the grafting rate of the invention is 88+/-3%, which is improved by 35% compared with 65+/-5% of the traditional chemical method. The reaction time is shortened from 120 minutes to 8 minutes, and the efficiency is improved by 93 percent. The energy consumption is reduced from 2.5kWh/kg to 0.3kWh/kg, and 88% is reduced.
4. Optimizing ranges of process parameters for different materials
The system sets specific process parameters for different types of materials, as shown in table 3:
TABLE 3 optimization ranges of process parameters for different materials
As shown in Table 3, the optimization range of the technological parameters for different materials shows that the system can meet the grafting and crosslinking requirements of polymers, metals, composite materials and ceramics, and has extremely high applicability.
By integrating the experimental data and the process parameter optimization results of tables 2 and 3, the energy level controllable small-sized laser irradiation grafting and crosslinking system provided by the invention shows remarkable process advantages in various material application fields. The system adopts a miniaturized design, combines low energy consumption and high-precision control, and can efficiently treat the surface modification and functional development of high-performance products such as high-polymer composite materials, electronic devices, medical materials and the like. Compared with the traditional process, the system realizes remarkable improvement in grafting rate, reaction time and energy consumption, for example, the grafting rate is improved from 65+/-5% to 88+/-3% in the traditional chemical method, the reaction time is shortened from 120 minutes to 8 minutes, and the energy consumption is reduced from 2.5kWh/kg to 0.3kWh/kg. In addition, the system obviously reduces the energy consumption and pollution risk in the grafting and crosslinking process through a green environment-friendly process, and provides an innovative solution for realizing green manufacturing of materials.
The invention successfully solves the multiple technical problems of the traditional grafting and crosslinking technology in the aspects of reaction control, environmental adaptability, efficiency, material compatibility, processing precision, equipment volume and the like by the small laser irradiation grafting and crosslinking system with controllable energy level. Through accurate energy control, modularized design and intelligent feedback mechanism, the system obviously improves the efficiency, the accuracy and the environmental friendliness of material grafting and crosslinking processing. For example, the system supports the processing of a variety of materials, such as polymers (PP, PVDF, etc.), metals (stainless steel), composites (CFRP), and ceramics (Al2O3), and enables high precision processing by dynamic parameter tuning, with processing areas as small as 1 μm or less. The system provides a green, efficient and accurate solution for the development of high-polymer material functionalization and high-performance composite materials, and promotes the development of material modification technology to a more intelligent and environment-friendly direction.

Claims (10)

Translated fromChinese
1.一种能级可控的小型激光辐照接枝和交联系统,其特征在于,包括:1. A small laser irradiation grafting and cross-linking system with controllable energy level, characterized by comprising:可调激光源,所述可调激光源为半导体激光器,波长范围为355nm至1064nm,功率调节范围为0.1W至10W,脉冲频率为1Hz至1kHz,配备内置温控单元;An adjustable laser source, which is a semiconductor laser with a wavelength range of 355nm to 1064nm, a power adjustment range of 0.1W to 10W, a pulse frequency of 1Hz to 1kHz, and a built-in temperature control unit;聚焦光学系统,所述聚焦光学系统包括非球面设计的高透光率石英透镜和表面镀金的高反射率反射镜,通过透镜、反射镜及光纤传输系统将激光束聚焦于待处理材料表面,具备动态光路调整功能;A focusing optical system, which includes a high-transmittance quartz lens with an aspherical design and a high-reflectivity reflector with a gold-plated surface. The laser beam is focused on the surface of the material to be processed through the lens, the reflector and the optical fiber transmission system, and has a dynamic optical path adjustment function;激光能量调控模块,所述激光能量调控模块包括光束分离器和功率控制单元,支持单脉冲、周期性脉冲及连续模式切换;A laser energy control module, which includes a beam splitter and a power control unit, and supports single pulse, periodic pulse and continuous mode switching;加工平台,所述加工平台为三维移动台,具备高精度定位功能,移动精度为±1μm,最大行程为100mm×100mm×50mm;The processing platform is a three-dimensional moving platform with high-precision positioning function, a moving accuracy of ±1μm, and a maximum travel of 100mm×100mm×50mm;化学反应辅助模块,所述模块包括气体环境控制系统,通过质量流量计实现氮气、氧气或氩气的动态配比,具备气体纯度检测和报警功能;A chemical reaction auxiliary module, which includes a gas environment control system, realizes dynamic proportioning of nitrogen, oxygen or argon through a mass flow meter, and has gas purity detection and alarm functions;实时监控与反馈系统,所述系统包括K型热电偶温度传感器、光纤光谱仪和图像分析模块,用于实时监测加工区域温度、反应状态及表面形貌;A real-time monitoring and feedback system, comprising a K-type thermocouple temperature sensor, a fiber optic spectrometer and an image analysis module, for real-time monitoring of the temperature, reaction state and surface morphology of the processing area;智能控制系统,基于嵌入式处理器,集成软件界面,具备参数设定、数据记录和加工过程自动化控制功能。The intelligent control system is based on an embedded processor and integrated software interface, and has the functions of parameter setting, data recording and automatic control of the processing process.2.根据权利要求1所述的系统,其特征在于,所述可调激光源的功率调节精度为0.1mW。2. The system according to claim 1, characterized in that the power adjustment accuracy of the adjustable laser source is 0.1 mW.3.根据权利要求1所述的系统,其特征在于,所述聚焦光学系统的非球面石英透镜焦距为50mm,数值孔径为0.6。3. The system according to claim 1 is characterized in that the aspherical quartz lens of the focusing optical system has a focal length of 50 mm and a numerical aperture of 0.6.4.根据权利要求1所述的系统,其特征在于,所述动态光路调整功能通过压电陶瓷驱动微位移平台实现,X/Y/Z轴位移精度为±0.1μm,重复定位精度为±0.05μm。4. The system according to claim 1 is characterized in that the dynamic optical path adjustment function is realized by a piezoelectric ceramic driven micro-displacement platform, the X/Y/Z axis displacement accuracy is ±0.1μm, and the repeatability positioning accuracy is ±0.05μm.5.根据权利要求1所述的系统,其特征在于,所述光路校准算法基于CCD图像反馈,通过高斯光斑质心定位法自动修正光路偏差,定位误差为±0.5μm。5. The system according to claim 1 is characterized in that the optical path calibration algorithm is based on CCD image feedback and automatically corrects the optical path deviation through Gaussian spot centroid positioning method, and the positioning error is ±0.5μm.6.根据权利要求1所述的系统,其特征在于,所述化学反应辅助模块通过质量流量计实现氮气流量调节范围为0.1L/min至10L/min,氧气流量调节范围为0.05L/min至5L/min。6. The system according to claim 1 is characterized in that the chemical reaction auxiliary module realizes a nitrogen flow adjustment range of 0.1 L/min to 10 L/min and an oxygen flow adjustment range of 0.05 L/min to 5 L/min through a mass flow meter.7.根据权利要求1所述的系统,其特征在于,所述实时监控与反馈系统的光纤光谱仪波长分辨率为±0.1nm,积分时间为1ms至1000ms。7. The system according to claim 1, characterized in that the wavelength resolution of the fiber optic spectrometer of the real-time monitoring and feedback system is ±0.1nm, and the integration time is 1ms to 1000ms.8.根据权利要求1所述的系统,其特征在于,所述图像分析模块采用CMOS相机,分辨率为5MP,定位误差为±1μm。8. The system according to claim 1, characterized in that the image analysis module adopts a CMOS camera with a resolution of 5MP and a positioning error of ±1μm.9.根据权利要求1所述的系统,其特征在于,所述智能控制系统具备自动报警功能,当检测到气体纯度低于99.99%或加工异常时,自动停止系统运行。9. The system according to claim 1 is characterized in that the intelligent control system has an automatic alarm function, and when it is detected that the gas purity is lower than 99.99% or the processing is abnormal, the system operation is automatically stopped.10.一种基于如权利要求1至9任一项所述的能级可控的小型激光辐照接枝和交联系统的应用方法,其特征在于,包括以下步骤:10. An application method based on the energy level controllable small laser irradiation grafting and cross-linking system according to any one of claims 1 to 9, characterized in that it comprises the following steps:S1、材料预处理,将聚丙烯薄膜表面涂覆马来酸和光敏引发剂溶液;S1, material pretreatment, coating the surface of the polypropylene film with maleic acid and photoinitiator solution;S2、固定待处理材料于加工平台上,确保稳定性;S2. Fix the material to be processed on the processing platform to ensure stability;S3、启动激光系统,设定激光波长、功率和脉冲频率,控制扫描速度;S3, start the laser system, set the laser wavelength, power and pulse frequency, and control the scanning speed;S4、在氮气保护环境下,通过激光辐照实现材料表面接枝或交联;S4. Under nitrogen protection environment, the surface of the material is grafted or cross-linked by laser irradiation;S5、通过实时监测反馈系统,动态调整激光参数,确保加工精度;S5. Through real-time monitoring and feedback system, dynamically adjust laser parameters to ensure processing accuracy;S6、完成辐照后,清洗并干燥材料,进行表面性能检测和评估。S6. After irradiation, clean and dry the material, and conduct surface performance testing and evaluation.
CN202510393671.7A2025-03-312025-03-31 A small laser irradiation grafting and cross-linking system with controllable energy level and its application methodPendingCN120002879A (en)

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