Modification device and method applied to nano silicon dioxide antifouling coating agent

Abstract

The invention discloses a modification device and method applied to a nano silicon dioxide antifouling coating agent. The modification device comprises a plasma activation module, an ion beam auxiliary deposition module, an ultrasonic cavitation module, a vacuum adsorption module and a low-temperature curing unit. The modification method comprises the following steps: S1, plasma pretreatment: bombarding the surface of nano silicon dioxide by adopting an Ar < + > beam in a mixed atmosphere; s2, in-situ synergistic grafting modification: mixing a silane coupling agent KH-570, perfluorooctyltriethoxysilane and an ionic liquid modifier, carrying out ultrasonic dispersion for 30 minutes, and then carrying out vacuum adsorption and oriented film forming; s3, ion beam assisted deposition of a conductive layer: alternately depositing an ITO conductive layer and a fluorocarbon shell layer in the vacuum cavity; and S4, low-temperature curing: adopting an O-beam to trigger fluorocarbon bond rearrangement, performing UV-LED irradiation and far infrared heating to 75 DEG C, and enabling the crosslinking density to be greater than or equal to 85%, so that the prepared nano silicon dioxide antifouling coating agent has excellent antistatic property, anti-reflection property and wear resistance, and is relatively high in adhesive force.

Description

Technical Field

[0001] The present invention relates to the technical field of nanomaterials, in particular to a modification device and method for a nano-silica antifouling coating agent. Background Art

[0002] Nano-silica materials, with their high specific surface area, excellent chemical stability and potential for functional modification, have shown important value in high-end application fields such as ship antifouling coatings and marine equipment protection. Research has shown that by grafting antifouling active ingredients on the surface or constructing superhydrophobic micro-nano structures, the anti-biofouling performance of the coating can be significantly improved. However, there are still multiple technical challenges in the current modification process and engineering application of nano-silica, which restrict its large-scale promotion.

[0003] At the level of the modification process, traditional methods have significant limitations. Conventional processes represented by the sol-gel method rely on mechanical stirring for mixing, making it difficult to achieve uniform interaction between nano-particles and modifiers, often resulting in too high local concentration of antifouling components or agglomeration. For example, in the direct mixing process reported in some literature, due to the compatibility defect between the antifouling agent and the resin matrix, the mechanical properties of the coating decrease; while for another type of self-healing functional coating, although the service life is extended, there is no regulation mechanism for the release rate of the antifouling agent, making it difficult to maintain long-term protection effect. Most existing modification equipment adopts a multi-step reaction process, such as a discrete operation of modification first and then compounding, which is not only cumbersome but also energy-consuming. In a typical case, a hydrophilic modification process requires multiple rounds of chemical reactions combined with ultrasonic treatment, with high equipment investment cost and difficulty in achieving continuous production; another type of temperature-sensitive modification system has extremely strict control over reaction conditions and low process fault tolerance.

[0004] The bottleneck of surface chemical regulation of materials also deserves attention. The insufficient activation degree of hydroxyl groups on the surface of nano-silica directly limits the grafting density of antifouling groups. In related research, the contact angle of materials modified with polymethylhydrosiloxane is small, and no synergistic antibacterial function is introduced; while in the acrylic acid-based modification system, due to the strong corrosiveness of monomers, there is a risk of premature termination during the reaction, and the actual grafting efficiency is much lower than the theoretical expectation. Although some innovative attempts have improved the dispersibility through the synergistic effect of multi-component siloxanes, they have not integrated active antifouling functional groups and still need to load antifouling substances secondly. Another study improved the weather resistance through phytic acid doping, but did not develop a dedicated modification device, resulting in insufficient interfacial bonding strength between nano-particles and the coating matrix.

[0005] In the dimension of engineering applications, although existing nano-silica antifouling coating agents exhibit advantages such as high light transmittance, superhydrophobicity, and weather resistance in fields like architectural glass and photovoltaic panels, large-scale applications still face key technical barriers. Traditional sol-gel coatings are prone to interface failure under the action of temperature difference cycles, mechanical stress, or chemical corrosion, and their service life is usually less than half a year. Current mainstream modification technologies rely on vacuum sputtering or PECVD processes, requiring temperatures above 300 °C and complex vacuum equipment, resulting in a single-piece coating cost as high as $20 per square meter and being difficult to adapt to special-shaped substrates such as curved glass. Functionally, conventional coatings mostly focus on single hydrophobic performance and lack comprehensive protection capabilities against ultraviolet degradation, oil penetration, and synergistic salt spray erosion, and are prone to accelerated failure under marine climate conditions. Summary of the Invention

[0006] To achieve the above object, the present invention provides a modification device and method for nano-silica antifouling coating agents, solving the above technical problems.

[0007] The present invention provides a modification device for nano-silica antifouling coating agents, including a plasma activation module. An atmospheric pressure dielectric barrier discharge plasma generator, an argon / oxygen mixed gas source, and a Raman spectroscopy sensor are arranged in the module. The module is used to dynamically adjust the plasma power density and gas ratio through a multivariable PID algorithm to stabilize the hydroxyl density.

[0008] Furthermore, it also includes an ion beam assisted deposition module and an ultrasonic cavitation module. A dual plasma ion source, a magnetic filtering device, and an ITO target are arranged in the ion beam assisted deposition module. The ion beam assisted deposition module is used to alternately deposit a conductive layer and a fluorocarbon modifier in a vacuum chamber, and the deposition rate is controlled at 0.5 nm / s. A high-frequency ultrasonic transducer and a piezoelectric pressure sensor are arranged in the ultrasonic cavitation module. The ultrasonic cavitation module is used to automatically increase the rotation speed to 320 rpm and adjust the inclination angle to 50° when detecting that D50 > 50 nm according to the feedback signal of the D50 particle size of nanoparticles.

[0009] Furthermore, it also includes a vacuum adsorption module and a low-temperature curing unit. A laser interferometer and a vacuum gradient controller are arranged in the vacuum adsorption module. The vacuum adsorption module is used to maintain the coating thickness through the linkage control of adsorption time and pressure gradient. A far-infrared radiation heating device, a thermal imager, and a UV-LED array are arranged in the low-temperature curing unit. The low-temperature curing unit is used to adjust the radiation intensity in zones according to the coating thickness distribution data.

[0010] The present invention provides a modification method using the modification device for nano-silica antifouling coating agents, including the following steps: S1. Plasma pretreatment: Under an argon / oxygen mixed atmosphere, using 50 eV Ar+ The beam bombards the surface of nano-silica for 5 minutes. When the hydroxyl density detected by Raman spectroscopy is < 8.0 OH / nm 2 the treatment time is extended;

[0011] S2. In-situ synergistic grafting modification: A modifier is prepared by mixing silane coupling agent KH-570, perfluorooctyltriethoxysilane and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide. After ultrasonic dispersion for 30 min, it is vacuum adsorbed and oriented to form a film;

[0012] S3. Ion beam assisted deposition of a conductive layer: An ITO conductive layer and a fluorocarbon shell layer are alternately deposited in a vacuum chamber;

[0013] S4. Low-temperature curing: A 100 eV O- beam is used to trigger the rearrangement of fluorocarbon bonds, irradiated with UV-LED for 5 min and heated to 75 °C by far-infrared for curing.

[0014] Furthermore, by weight, the components of the modifier are 5 parts by weight of KH-570, 3 parts by weight of perfluorooctyltriethoxysilane and 0.5 part by weight of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.

[0015] Furthermore, in step S3: the sputtering power of the ITO target is 200 W and the oxygen partial pressure is 0.3 Pa; combined with an electrostatic field of 1 kV / cm and an ion beam incident angle of 30°, a vertically penetrating structure is formed.

[0016] Furthermore, the plasma pretreatment process in step S1 also includes a multivariable PID-p algorithm and a multivariable PID-g algorithm. The formula of the multivariable PID-p algorithm is where, u power (t) is the output signal for controlling the plasma power, used to dynamically adjust the power density of the plasma generator, K p , K i and K d are the proportional, integral, and differential gain coefficients, corresponding to the adjustment weights of the current error, cumulative error, and error change trend respectively; e OH (t) is the hydroxyl density error, that is, the deviation between the target hydroxyl density (such as 8.2 OH / nm 2 ) and the actual Raman spectroscopy detection value; e radical (t) is the free radical concentration deviation, the difference between the actual free radical concentration and the target threshold (such as ≥ 10 15 / cm 3 ); ∫e OH (t)dt is the cumulative amount of hydroxyl density error over time, used to eliminate long-term steady-state deviation; is the change rate of the free radical concentration deviation, predicting the trend and suppressing the temperature overshoot; the formula of the multivariable PID-g algorithm is where, u gas (t) is the output signal for controlling the gas mixing ratio, used to adjust the oxygen proportion in the argon / oxygen mixed gas source; K' p and K' i are the proportional and integral gain coefficients, dynamically adjusting the response intensity of the oxygen proportion error; is the oxygen proportion fluctuation, that is, the deviation between the target oxygen proportion (such as 10%) and the actual detected value; is the cumulative integral of the oxygen proportion error, correcting the steady-state error of the gas proportion control.

[0017] Furthermore, the low-temperature curing process in step S4 also adopts the multivariable PID algorithm-cure, and the multivariable PID algorithm-cure is: where, u cure (t) is the output signal for controlling the low-temperature curing process, adjusting the far-infrared radiation intensity and the UV-LED light intensity; K″ p and K″ i and K″ d are the proportional, integral, and differential gain coefficients, used for the coordinated control of the coating thickness, temperature, and ultraviolet light intensity; e thick (t) is the coating thickness deviation, the difference between the target thickness (20±0.5nm) and the actual detected value, e temp is the temperature fluctuation (target 75±2°C), e UV is the ultraviolet light intensity error (target 50mW / cm 2 ), ∫(e temp +e UV )dt is the cumulative integral of the temperature and ultraviolet error, ensuring the curing uniformity; is the change rate of the curing speed (such as the coil line speed of 3m / min), suppressing the process fluctuation; adjusting the radiation intensity by partitioning the thermal imaging data, reducing the curing energy consumption by 30%, and ensuring the crosslinking density ≥85% at the same time.

[0018] Furthermore, the general formula of the multivariable PID algorithm is:

[0019] where, u(t) is the global control output quantity, used to comprehensively adjust the plasma power, ultrasonic frequency, vacuum pressure and other actuators; K p (t), K i (t), K d(t) is a dynamically adjusted gain coefficient, reflecting the proportional, integral, and differential weights of the system's real-time response; e(t) is the comprehensive error signal, including: hydroxyl density error (main error), grafting rate deviation (target ≥ 95%), and vacuum adsorption uniformity deviation (target < 1%); ∫e(t)dt is the cumulative integral of all errors to eliminate long-term deviations. is the rate of change of the comprehensive error, predicting the dynamic characteristics of the system and suppressing oscillations; all formulas achieve dynamic control through real-time feedback (such as Raman spectroscopy, pressure sensors, thermal imagers) to ensure coating performance.

[0020] Furthermore, in the plasma pretreatment stage, it also includes when the detected hydroxyl density < 8.0 OH / nm 2 automatically increase the oxygen ratio to 10.5% and extend the treatment time to 6 min.

[0021] A modification device and method for a nano-silica antifouling coating agent proposed by the present invention have the following beneficial effects:

[0022] 1. This application involves multi-functional integration and performance improvement. The prepared nano-silica antifouling coating agent has excellent antistatic properties, light transmittance enhancement, abrasion resistance, and high adhesion. The plasma power, gas ratio, and curing parameters are adjusted in real time using a multi-variable PID algorithm.

[0023] 2. The method steps and devices of this application cooperate synergistically. Plasma-ultrasonic synergistic activation, directional adsorption, and vacuum gradient control are used to guide the vertical arrangement of nanoparticles, avoiding the agglomeration problem of traditional mechanical mixing.

[0024] 3. The plasma activation - ion beam deposition - vacuum adsorption - low-temperature curing process content involved in this application realizes the high-functional integration, low-energy consumption manufacturing, and long-term stability of the antifouling coating agent, solving the bottlenecks of uneven dispersion, high-temperature dependence, and single function in traditional processes, and having significant application value in the fields of ship antifouling, photovoltaic panels, etc. Specific Embodiments

[0025] The following specific examples illustrate the embodiments of the present invention. Those skilled in the art can easily understand the other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0026] Unless otherwise specified, the examples and comparative examples are parallel tests with the same components, component contents, preparation steps, and preparation parameters. The test methods in the following examples are all conventional methods unless otherwise specified; the test materials used in the following examples are all obtained from commercial channels unless otherwise specified.

[0027] Unless otherwise noted, all reagents are used as received without further purification.

[0028] In the preparation examples and examples of the present invention, unless otherwise specified, "parts" are all parts by weight, and concentration percentages are all weight concentrations unless otherwise specified.

[0029] Example 1

[0030] This example provides a modification device for a nano-silica antifouling coating agent, including:

[0031] Plasma activation module: An atmospheric pressure dielectric barrier discharge plasma generator is used, with a power density of 3.5 W / cm 2 , a frequency of 40 kHz, equipped with an argon / oxygen mixed gas source with a volume ratio of 9:1, for the activation of surface hydroxyl groups and the generation of free radicals on nano-silica. The temperature in the activation area is controlled at 40 ± 2 °C, and the treatment time is 5 min to ensure that the surface hydroxyl density is increased to 8.2 OH / nm 2 , integrated with an in-situ Raman spectroscopy sensor to real-time monitor the hydroxyl density (target value 8.2 OH / nm 2 ) and the free radical concentration (threshold ≥ 10 15 / cm 3 ). The gas flow rate (Ar / O2 ratio 9:1 ± 0.2%) and the power density (3.5 ± 0.1 W / cm 2 ) are dynamically adjusted through a multivariable PID algorithm.

[0032] The ion beam assisted deposition module includes an ion source unit: A dual plasma ion source (Ar + and O - are alternately output), with an energy range of 50 - 200 eV, a beam current density of 5 mA / cm 2 , and an incident angle adjustable from 15 - 75°. Equipped with a magnetic filtering device (magnetic field strength 0.5 T) to remove high-energy neutral particles and reduce coating damage; Target system: Introduce a transparent conductive oxide ITO target (resistivity ≤ 5 × 10 -4 Ω·cm, light transmittance ≥ 90%), and co-deposit with a fluorocarbon modifier to form a "nano-silica - conductive layer - fluorocarbon shell" sandwich structure; A vacuum chamber with a vacuum degree ≤ 5 × 10 -3 Pa, equipped with a quadrupole mass spectrometer to real-time monitor the purity of the deposition atmosphere and avoid impurity doping.

[0033] Ultrasonic cavitation module: An integrated high-frequency ultrasonic transducer (frequency 28 kHz, power 500 W) is adopted to form a standing wave field with the bottom of the reaction chamber. The cavitation intensity is ≥0.8 MPa to achieve the dispersion of nanoparticles and the uniform coating of modifiers. A double-layer spiral stirring paddle (rotation speed 300 ± 10 rpm, blade inclination angle 45°) is equipped to promote the shear-collision mixing of nanoparticles and modifiers. A piezoelectric pressure sensor (accuracy ±0.01 MPa) is used to feedback the cavitation intensity to the central processor. When the detected value < 0.8 MPa, the ultrasonic frequency is automatically increased to 30 kHz.

[0034] Vacuum adsorption module: The vacuum degree is -0.08 MPa. Through a porous titanium alloy substrate (pore diameter 5 μm), the directional adsorption of the coating agent and the vertical arrangement of nanoparticles are realized to form a dense "core-shell" structure. The surface roughness Ra of the substrate is ≤0.1 μm, the coating thickness is 20 ± 2 nm, and the uniformity deviation < 5%. The coating thickness (20 ± 0.5 nm) is measured in real time by a laser interferometer (wavelength 632.8 nm), and the adsorption time (2 ± 0.1 min) is optimized by combining the vacuum degree (-0.08 MPa ± 1%) and the substrate pore diameter (5 μm ± 0.1 μm).

[0035] Low-temperature curing unit: It includes a UV-LED with a wavelength of 365 nm and an intensity of 50 mW / cm 2 Far-infrared radiation heating (wavelength 3 - 5 μm) is adopted, the temperature is 75 ± 2 °C, the curing time is 15 min, it is adapted to the line speed of the R2R production line of 3 m / min, and the energy consumption is reduced by 40%. R2R production line linkage: The servo motor drives the coil (line speed 3 m / min ± 0.05%). Through a tension sensor (range 0 - 500 N) and an infrared thermometer (accuracy ±0.5 °C), the synchronous regulation of the low-temperature curing unit (75 ± 0.5 °C) is realized.

[0036] Example 2

[0037] This example provides a method for applying a nano-silica antifouling coating agent, including the following specific steps:

[0038] S1. Plasma pretreatment: At an argon flow rate of 8 L / min, an oxygen proportion of 10%, a treatment time of 5 min, use a 50 eV Ar + beam current to bombard the surface of nano-silica for 30 seconds, and dynamically adjust the total treatment time according to the real-time feedback of the hydroxyl density. The beam current density is 3 mA / cm 2 , selectively etch weakly bound hydroxyl groups to form high-density anchoring sites, and the hydroxyl density on the surface of nano-silica is increased to 8.2 OH / nm 2 , if the hydroxyl density detected by Raman spectroscopy < 8.0 OH / nm 2, the oxygen ratio is automatically increased to 10.5% and the treatment time is extended to 6 min. The temperature control uses a fuzzy PID algorithm to ensure that the temperature in the activation zone is stable at 40 ± 0.2 °C, with an overshoot of <0.1 °C.

[0039] S2. In-situ synergistic grafting modification: Mix 5 parts by weight of silane coupling agent KH-570, 3 parts by weight of fluorocarbon chain monomer perfluorooctyltriethoxysilane, and 0.5 part by weight of ionic liquid modifier 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, and dissolve them in an ethanol / water mixed solvent with a volume ratio of 7:3. The total concentration of the modifier is 15 wt%, the solid content of nano-silica is 20 wt%, and the ultrasonic dispersion time is 30 min. The ultrasonic cavitation intensity is linked to the stirring speed. When the particle size distribution D50 of the nanoparticles > 50 nm, start the double-layer spiral stirring paddle, increase the speed to 320 rpm, and adjust the inclination angle to 50°. Vacuum adsorption pressure gradient control: Through the feedback of the pressure sensor, maintain -0.08 MPa in the initial adsorption stage (0 - 30 s), adjust to -0.06 MPa in the middle stage (30 - 90 s), and reduce to -0.04 MPa in the final stage (90 - 120 s) to reduce bubble residues.

[0040] S3. Vacuum adsorption and orientation film formation: Synchronously start the deposition of the IBAD conductive layer during the adsorption stage. The sputtering power of the ITO target is 200 W, the oxygen partial pressure is 0.3 Pa, the deposition rate is 0.5 nm / s, and the thickness of the conductive layer is 10 nm (surface resistance ≤ 10 6 Ω / sq, light transmittance loss < 0.5%). Combine the electrostatic field (1 kV / cm) with the ion beam current (incident angle 30°) to guide the nano-silica and the conductive layer to be oriented and arranged to form a vertically penetrating structure (electron mobility is increased to 10 -2 cm 2 / V·s). The vacuum pressure is -0.08 MPa, and the adsorption time is 2 min. During the vacuum adsorption stage, alternately deposit the conductive layer and the fluorocarbon layer, and realize the interfacial chemical bonding (interfacial binding energy ≥ 1.5 J / m 2 ) through the regulation of the ion beam current energy gradient (50 → 200 eV). A vertically arranged "core-shell" structure (the core layer is silica, and the shell layer is a fluorocarbon chain-siloxane composite layer) is formed on the substrate surface.

[0041] S4. Low-temperature rapid curing: Use a 100 eV O-beam to bombard the surface of the fluorocarbon chain, and the beam current density is 2 mA / cm 2 , trigger the rearrangement and cross-linking of the C-F bond, compress the thickness of the fluorocarbon shell layer from 2 nm to 1.5 nm (the refractive index drops from 1.38 to 1.25), and increase the light transmittance rate to 3.2%. Use 365 nm and an intensity of 50 mW / cm 2Irradiate with UV-LED for 5 min to trigger the siloxane condensation reaction, heat to 75 °C with far-infrared radiation, and the curing time is 15 min. Based on the thermal imaging data and the coating thickness distribution, the far-infrared radiation intensity, UV-LED light intensity, and coil line speed are dynamically adjusted in zones through a multivariable PID algorithm to ensure that the curing crosslink density ≥ 85% and the energy consumption is reduced by 30%.

[0042] The multivariable PID algorithm involved in the above embodiments is as follows: dynamically adjust the plasma power and ultrasonic frequency according to real-time sensor data to ensure that the hydroxyl density error < 2% and the cavitation intensity fluctuation < 5%; combining the chemical parameters (mass ratio of silane coupling agent / fluorocarbon chain monomer, solvent volume ratio, concentration) and physical parameters (vacuum pressure gradient, standing wave field frequency) collected by the above Raman spectroscopy sensor and vacuum pressure sensor, the total multivariable PID algorithm is as follows: Among them, u(t) is the global control output quantity, which is used to comprehensively adjust the plasma power, ultrasonic frequency, vacuum pressure and other actuators; K p (t), K i (t), K d (t) are dynamically adjusted gain coefficients, which reflect the proportional, integral, and differential weights of the real-time response of the system. K p (t) takes 0.5 - 2.0, K i takes 0.05 - 0.3, K d takes 0.2 - 1.0; e(t) is the comprehensive error signal, including: hydroxyl density error (main error), grafting rate deviation (target ≥ 95%), vacuum adsorption uniformity deviation (target < 1%); ∫e(t)dt is the cumulative integral of all errors to eliminate long-term deviations; is the change rate of the comprehensive error, which predicts the dynamic characteristics of the system and suppresses oscillations; all formulas achieve dynamic control through real-time feedback (such as Raman spectroscopy, pressure sensors, thermal imagers) to ensure the coating performance.

[0043] In Example 2, the formula of the multivariable PID-p algorithm in S1 plasma pretreatment is Among them, u power (t) is the output signal for controlling the plasma power, which is used to dynamically adjust the power density of the plasma generator. K p , K i and K d are the proportional, integral, and differential gain coefficients, respectively corresponding to the adjustment weights of the current error, cumulative error, and error change trend. K p takes 0.8 - 1.5, K i takes 0.05 - 0.15, K d takes 0.1 - 0.3; e OH(t) is the hydroxyl density error, that is, the deviation between the target hydroxyl density (such as 8.2 OH / nm 2 ) and the actual Raman spectroscopy detection value; e radical (t) is the free radical concentration deviation, the difference between the actual free radical concentration and the target threshold (such as ≥10 15 / cm 3 ); ∫e OH (t)dt is the cumulative amount of hydroxyl density error over time, used to eliminate long-term steady-state deviation; is the change rate of the free radical concentration deviation, predicting the trend and suppressing temperature overshoot; The multi-variable PID-g algorithm formula is where, u gas (t) is the output signal for controlling the gas mixing ratio, used to adjust the oxygen proportion in the argon / oxygen mixed gas source; K' p , K' i are the proportional and integral gain coefficients, dynamically adjusting the response intensity of the oxygen proportion error, K' p takes 0.3 - 0.8, K' i takes 0.1 - 0.2; is the oxygen proportion fluctuation, that is, the deviation between the target oxygen proportion (such as 10%) and the actual detection value; is the cumulative integral of the oxygen proportion error, correcting the steady-state error of the gas proportion control.

[0044] In Example 2, the multi-variable PID algorithm - cure in S4 is: where, u cure (t) is the output signal for controlling the low-temperature curing process, adjusting the far-infrared radiation intensity and UV-LED light intensity; K″ p , K″ i , K″ d are the proportional, integral, and differential gain coefficients, used for the coordinated control of the coating thickness, temperature, and ultraviolet light intensity, K″ p takes 1.2 - 1.5, K″ i takes 0.2 - 0.5, K″ d takes 0.5 - 1.0; e thick (t) is the coating thickness deviation, the difference between the target thickness (20 ± 0.5 nm) and the actual detection value, e temp is the temperature fluctuation (target 75 ± 2 °C), e UV is the ultraviolet light intensity error (target 50 mW / cm 2 ), ∫(e temp + e UV )dt is the cumulative integral of the temperature and ultraviolet errors, ensuring curing uniformity; It is the change rate of the curing speed (such as the coil line speed of 3 m / min) to suppress process fluctuations; the radiation intensity is adjusted by partitioning the thermal imaging data, reducing the curing energy consumption by 30% while ensuring that the crosslinking density ≥ 85%

[0045] Comparative Example 1

[0046] The difference from Example 1 is that it lacks the ion beam assisted deposition (IBAD) module, and the others are the same.

[0047] Comparative Example 2

[0048] The difference from Example 1 is that it lacks the adaptive PID control algorithm and is adjusted manually, and the others are the same.

[0049] Comparative Example 3

[0050] The difference from Example 1 is that it lacks the ionic liquid modifier 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide with equal weight parts, and the others are the same.

[0051] Performance Test

[0052] 1. Tests such as resistance and antireflection rate: Crosslinking density test is carried out according to ASTM D2765; at a temperature of 23 °C and a humidity of 50%, resistivity tests are carried out on the examples and comparative examples according to ASTM D257. Using a four-probe resistance meter, a 100 V DC voltage is applied to measure the resistance value and calculate the surface resistivity; the examples and comparative examples are coated on a sample glass to prepare a coated substrate, and tested according to ISO 13696. Using a UV-visible spectrophotometer, the transmittance of the coated substrate is tested in the wavelength range of 400 - 800 nm; the water contact angle tests are carried out on the examples and comparative examples according to GB / T 30693. Using a contact angle measuring instrument, 2 μL of deionized water is dropped on the coated surface, and the droplet profile is fitted by the Young-Laplace equation to calculate the static contact angle; the adhesion tests are carried out on the examples and comparative examples according to ASTM D3359. Using the cross-cut method (hundred-grid test): 1 mm × 1 mm squares are scratched on the coated surface with a blade, and after sticking a 3M tape, it is quickly peeled off to observe the peeling ratio of the coating; the abrasion resistance tests are carried out on the examples and comparative examples according to ASTM D4060. Using a Taber linear abrasion tester, equipped with a CS-10 grinding wheel, applying a 500 g load, cycling and rubbing the coated surface, and recording the number of friction times when the coating is damaged. The results are shown in Table 1.

[0053] Table 1

[0054]

[0055]

[0056] The specific embodiments of the present invention have been described in detail above, but they are only examples, and the present invention is not limited to the specific embodiments described above. For those skilled in the art, any equivalent modifications and substitutions made to the present invention are also within the scope of the present invention. Therefore, all equivalent transformations and modifications made without departing from the spirit and scope of the present invention should be covered within the scope of the present invention.

Claims

1. A modification device for a nano-silica antifouling coating agent, characterized in that It includes a plasma activation module, in which an atmospheric pressure dielectric barrier discharge plasma generator, an argon / oxygen mixed gas source, and a Raman spectroscopy sensor are provided. The module is used to dynamically adjust the plasma power density and gas ratio through a multivariable PID algorithm to stabilize the hydroxyl density.

2. The modification device according to claim 1, characterized in that, It also includes an ion beam assisted deposition module and an ultrasonic cavitation module. In the ion beam assisted deposition module, a dual plasma ion source, a magnetic filtering device, and an ITO target are provided. The ion beam assisted deposition module is used to alternately deposit a conductive layer and a fluorocarbon modifier in a vacuum chamber, and the deposition rate is controlled at 0.5 nm / s. In the ultrasonic cavitation module, a high-frequency ultrasonic transducer and a piezoelectric pressure sensor are provided. The ultrasonic cavitation module is used to automatically increase the rotation speed to 320 rpm and adjust the inclination angle to 50° when it detects that D50 > 50 nm according to the feedback signal of the D50 particle size of the nanoparticles.

3. The modification device according to claim 1, characterized in that, It also includes a vacuum adsorption module and a low-temperature curing unit. In the vacuum adsorption module, a laser interferometer and a vacuum gradient controller are provided. The vacuum adsorption module is used to maintain the coating thickness through the linkage control of the adsorption time and the pressure gradient. In the low-temperature curing unit, a far-infrared radiation heating device, a thermal imager, and a UV-LED array are provided. The low-temperature curing unit is used to adjust the radiation intensity in zones according to the coating thickness distribution data.

4. A modification method for the modification device of the nano-silica antifouling coating agent described in claim 1, characterized in that, The modification method includes the following steps: S1. Plasma pretreatment: Under an argon / oxygen mixed atmosphere, bombard the surface of nano-silica with a 50 eV Ar + beam for 5 minutes. When the hydroxyl density detected by Raman spectroscopy is < 8.0 OH / nm 2 , extend the treatment time; S2. In-situ synergistic grafting modification: Mix a silane coupling agent KH-570, perfluorooctyltriethoxysilane, and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide to form a modifier. After ultrasonic dispersion for 30 min, vacuum adsorption and orientation are carried out to form a film. S3. Ion beam assisted deposition of a conductive layer: Alternately deposit an ITO conductive layer and a fluorocarbon shell layer in a vacuum chamber. S4. Low-temperature curing: Use a 100 eV O - beam current to trigger the rearrangement of fluorocarbon bonds, irradiate with UV-LED for 5 min and heat to 75 °C with far-infrared for curing.

5. The modification method according to claim 4, wherein, The component of the modifier is 5 parts by weight of KH-570, 3 parts by weight of perfluorooctyltriethoxysilane, and 0.5 parts by weight of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide by weight.

6. The modification method according to claim 4, wherein In the step S3: The sputtering power of the ITO target is 200 W, and the oxygen partial pressure is 0.3 Pa. Combining with an electrostatic field of 1 kV / cm and an ion beam incident angle of 30°, a vertically penetrating structure is formed.

7. The modification method according to claim 4, wherein The plasma pretreatment process in step S1 further includes a multivariable PID-p algorithm and a multivariable PID-g algorithm. The formula for the multivariable PID-p algorithm is where u power (t) is the output signal for controlling the plasma power, K p , K i and K d are the proportional, integral, and derivative gain coefficients; e OH (t) is the hydroxyl density error; e radical (t) is the radical concentration deviation; ∫e OH (t)dt is the cumulative amount of the hydroxyl density error over time; is the rate of change of the radical concentration deviation. The formula for the multivariable PID-g algorithm is where u gas (t) is the output signal for controlling the gas mixing ratio; K' p , K' i are the proportional and integral gain coefficients; is the oxygen proportion fluctuation; is the cumulative integral of the oxygen proportion error.

8. The modification method according to claim 7, characterized in that The low-temperature curing process in step S4 also adopts a multivariable PID algorithm - cure, and the multivariable PID algorithm - cure is where u cure (t) is the output signal for controlling the low-temperature curing process; K" p , K" i , K" d are the proportional, integral, and differential gain coefficients; e thick (t) is the coating thickness deviation, e temp is the temperature fluctuation, e UV is the ultraviolet light intensity error, ∫(e temp +e UV )dt is the cumulative integral of the temperature and ultraviolet error; is the change rate of the curing speed.

9. The modification method according to claim 7, wherein The general formula of the multi-variable PID algorithm is as follows: where u(t) is the global control output; K p (t), K i (t), K d (t) are dynamically adjusted gain coefficients; e(t) is the comprehensive error signal; ∫e(t)dt is the cumulative integral of all errors; is the change rate of the comprehensive error.

10. The modification method according to claim 4, wherein, During the plasma pretreatment stage, it also includes automatically increasing the oxygen ratio to 10.5% and extending the treatment time to 6 min when the detected hydroxyl density < 8.0 OH / nm 2 is detected.

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