A modified device and method applied to nano-silica antifouling coating agent

Abstract

The application discloses a modified device and method applied to nano-silica antifouling coating agents, the modified device comprises a plasma activation module, an ion beam assisted deposition module, an ultrasonic cavitation module, a vacuum adsorption module and a low-temperature curing unit; the modified method comprises the following steps of S1, plasma pretreatment: under a mixed gas atmosphere, Ar + beam is used for bombarding the surface of nano-silica; S2, in-situ synergistic grafting modification: a silane coupling agent KH-570, a perfluorooctyl triethoxysilane and an ionic liquid modifier are mixed, ultrasonic dispersion is performed for 30 min, and then vacuum adsorption is performed to direct film formation; S3, ion beam assisted deposition of a conductive layer: ITO conductive layers and fluorocarbon shell layers are alternately deposited in a vacuum cavity; S4, low-temperature curing: O ‑ beam triggers fluorocarbon bond rearrangement, UV-LED irradiation and far infrared heating to 75 DEG C, the crosslinking density is greater than or equal to 85%, and the prepared nano-silica antifouling coating agent has excellent antistatic property, transmittance and wear resistance, and higher adhesion.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of nanomaterials, and particularly to a modification device and method applied to a nano-silica antifouling coating agent. BACKGROUND

[0002] Nano-silica material has important value in high-end application fields such as ship antifouling coatings and marine equipment protection due to its high specific surface area, excellent chemical stability and functional modification potential. Studies have shown that the antifouling performance of the coating can be significantly improved by grafting antifouling active ingredients on the surface or constructing super-hydrophobic micro-nano structures. However, the current modification process and engineering application of nano-silica still have many technical challenges, which restrict its large-scale promotion.

[0003] In terms of modification process, the traditional method has significant limitations. The conventional process represented by the sol-gel method relies on mechanical stirring for mixing, which makes it difficult to achieve uniform action of nanoparticles and modifiers, often leading to local over-concentration of antifouling components or agglomeration. For example, some literature reports that the direct mixing process causes a decrease in the mechanical properties of the coating due to the compatibility defects of the antifouling agent and the resin matrix; while another type of self-repairing functional coating prolongs the service life, but the release rate of the antifouling agent lacks a control mechanism, making it difficult to maintain long-term protection effect. Existing modification equipment mostly uses multi-step reaction processes, such as discrete operations of modification followed by compounding, which not only have complicated processes but also have high energy consumption. In a typical case, a hydrophilic modification process requires multiple rounds of chemical reactions combined with ultrasonic treatment, which has high equipment investment cost and is difficult to realize continuous production; another type of temperature-sensitive modification system is extremely strict in reaction condition control, and has a low process fault tolerance.

[0004] The bottleneck of chemical regulation of material surface is also worth noting. The insufficient activation of the hydroxyl groups on the surface of nano-silica directly limits the grafting density of antifouling groups. In related studies, the contact angle of the material modified by polymethyl hydrogen siloxane is small, and no synergistic antibacterial function is introduced; the acrylic modification system has a strong corrosion of monomer, and there is a risk of premature termination during the reaction process, so the actual grafting efficiency is much lower than the theoretical expectation. Although some innovative attempts improve the dispersibility through the synergistic effect of multi-component siloxane, they do not integrate active antifouling functional groups, and still need subsequent secondary loading of antifouling substances. Another study improves the weather resistance by doping phytic acid, but does not develop a special modification device, resulting in insufficient interfacial bonding strength between the nano-particles and the coating matrix.

[0005] In the engineering application dimension, although the existing nano-silica antifouling coating agent has advantages such as high light transmittance, super-hydrophobicity and weather resistance in the fields of building glass and photovoltaic panels, it still faces key technical obstacles in large-scale application. The traditional sol-gel coating is prone to interface failure under the action of temperature difference cycle, mechanical stress or chemical corrosion, and its service life is usually less than half a year. The current mainstream modification technology relies on vacuum sputtering or PECVD process, which requires high temperature of more than 300 DEG C and complex vacuum equipment, resulting in a coating cost of up to 20 US dollars per square meter, and it is difficult to adapt to curved glass and other special-shaped substrates. In terms of function, conventional coatings mainly focus on single hydrophobic performance, and lack comprehensive protection capability against ultraviolet degradation, oil penetration and salt mist synergistic corrosion, and are prone to accelerated failure in marine climate conditions. SUMMARY

[0006] The application provides a modification device and method for a nano-silica antifouling coating agent, which solves the above technical problems.

[0007] The application provides a modification device for a nano-silica antifouling coating agent, which comprises a plasma activation module, wherein an atmospheric pressure dielectric barrier discharge plasma generator, an argon / oxygen mixed gas source and a Raman spectrum sensor are arranged in the module, and the module is used for dynamically adjusting plasma power density and gas ratio by a multivariate PID algorithm to stabilize the hydroxyl density.

[0008] Further, the device further comprises an ion beam assisted deposition module and an ultrasonic cavitation module, wherein a double-plasma ion source, a magnetic filter device and an ITO target material are arranged in the ion beam assisted deposition module, the ion beam assisted deposition module is used for alternately depositing a conductive layer and a fluorocarbon modifier in a vacuum cavity, and the deposition rate is controlled to be 0.5 nm / s; and a high-frequency ultrasonic transducer and a piezoelectric pressure sensor are arranged in the ultrasonic cavitation module, and the ultrasonic cavitation module is used for automatically increasing the rotating speed to 320 rpm and adjusting the inclination angle to 50 DEG according to the nano-particle D50 particle size feedback signal when D50> 50 nm is detected.

[0009] Further, the device further comprises a vacuum adsorption module and a low-temperature curing unit, wherein a laser interferometer and a vacuum gradient controller are arranged in the vacuum adsorption module, the vacuum adsorption module is used for maintaining the coating thickness by linkage control of adsorption time and pressure gradient; and a far-infrared radiation heating device, a thermal imager and a UV-LED array are arranged in the low-temperature curing unit, and the low-temperature curing unit is used for adjusting the radiation intensity according to the coating thickness distribution data.

[0010] The application provides a modification method using the modification device for a nano-silica antifouling coating agent, which comprises the following steps: S1. Plasma pretreatment: under an argon / oxygen mixed gas atmosphere, 50 eV Ar+ Beam bombardment on the surface of nanosilica for 5 minutes, when the Raman spectrum detects that the hydroxyl density is <8.0 OH / nm 2 The processing time is prolonged;

[0011] S2. In-situ synergistic grafting modification: a modifier is prepared by mixing silane coupling agent KH-570, perfluorooctyltriethoxysilane and 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide salt, and then ultrasonic dispersion for 30 min, followed by vacuum adsorption and directional film formation;

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

[0013] S4. Low-temperature curing: 100 eV O-beam current is used to trigger fluorocarbon bond rearrangement, UV-LED irradiation for 5 min and far infrared heating to 75°C for curing.

[0014] Further, the components of the modifier are 5 parts by weight of KH-570, 3 parts by weight of perfluorooctyltriethoxysilane and 0.5 parts by weight of 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide salt.

[0015] Further, in the step S3: the ITO target sputtering power is 200 W, and the oxygen partial pressure is 0.3 Pa; a vertical through structure is formed by combining a static electric field of 1 kV / cm and an ion beam incident angle of 30°.

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

[0017] Further, the step S4 low-temperature curing process also adopts a multivariable PID algorithm-cure, which is: Wherein, u cure (t) is the output signal of controlling the low-temperature curing process, adjusting the far-infrared radiation intensity and UV-LED light intensity; K'' p , K'' i , K'' d are proportional, integral and differential gain coefficients, used for the collaborative control of the film thickness, temperature and ultraviolet light intensity; e thick (t) is the film thickness deviation, the difference between the target thickness (20±0.5nm) and the actual detection value, e temp is the temperature fluctuation (target 75±2℃), 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 uniformity of curing; is the rate of change of the curing speed (such as the web line speed 3m / min), inhibiting the process fluctuation; by adjusting the radiation intensity through thermal imaging data partition, the curing energy consumption is reduced by 30%, while ensuring the crosslinking density≥85%.

[0018] Further, the total formula of the multivariable PID algorithm is:

[0019] Wherein, u(t) is the global control output, 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 dynamic gain coefficient, reflecting the proportional, integral, and derivative weight of the real-time response of the system; e(t) is a 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, eliminating long-term deviation; is the rate of change of the comprehensive error, predicting the dynamic characteristics of the system and suppressing oscillation; all formulas realize dynamic control through real-time feedback (such as Raman spectroscopy, pressure sensor, thermal imager), ensuring the performance of the coating.

[0020] Further, in the plasma pretreatment stage, when the hydroxyl density <8.0 OH / nm 2 is detected, the oxygen proportion is automatically increased to 10.5% and the treatment time is extended to 6 min.

[0021] The modified device and method for nano-silica antifouling coating agent proposed by the application have the following beneficial effects:

[0022] 1. The application relates to multiple function integration and performance improvement. The prepared nano-silica antifouling coating agent has excellent antistatic property, transmittance, wear resistance, and high adhesion. The plasma power, gas proportion, and solidification parameters are adjusted in real time by using a multivariable PID algorithm.

[0023] 2. The method steps and device of the application have synergistic effects. Plasma-ultrasonic wave synergistic activation and directional adsorption are adopted, and vacuum gradient control is used to guide the vertical arrangement of nano particles, thereby avoiding the agglomeration problem of traditional mechanical mixing.

[0024] 3. The plasma activation-ion beam deposition-vacuum adsorption-low temperature solidification process content related by the application realizes high function integration, low energy consumption manufacturing, and long-term stability of the antifouling coating agent, solves the problems of dispersion, high temperature dependence, and single function of traditional processes, and has significant application value in the fields of ship antifouling and photovoltaic panels. DETAILED DESCRIPTION

[0025] The embodiments of the application are described below through specific specific examples. Those skilled in the art can easily understand other advantages and effects of the application from the content disclosed in the specification. The application can also be implemented or applied by using different specific embodiments, and the details in the specification can be modified or changed based on different viewpoints and applications without departing from the spirit of the application.

[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 conventional methods unless otherwise specified. The test materials used in the following examples are commercially available unless otherwise specified.

[0027] Unless otherwise specified, all reagents were used as received without further purification.

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

[0029] Example 1

[0030] The present embodiment provides a modification device applied to a nano-silica antifouling coating agent, comprising:

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

[0032] The ion beam assisted deposition module includes an ion source unit: a double 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 adjustable incident angle of 15-75°. A magnetic filtering device (magnetic field strength 0.5 T) is provided to remove high-energy neutral particles and reduce coating damage; a target material system: a transparent conductive oxide ITO target material (resistivity ≤5×10 -4 Ω·cm, light transmittance ≥90%) is introduced for co-deposition with a fluorocarbon modifier to form a "nano-silica-conductive layer-fluorocarbon shell" sandwich structure; a vacuum cavity with a vacuum degree of ≤5×10 -3 Pa is provided with a quadrupole mass spectrometer to monitor the purity of the deposition atmosphere in real time to avoid impurity doping.

[0033] Ultrasonic cavitation module: integrated high-frequency ultrasonic transducer (frequency 28 kHz, power 500 W) is used to form a standing wave field with the bottom of the reaction cavity, with cavitation intensity ≥0.8 MPa, to realize the dispersion of nanoparticles and uniform coating of modifiers. Equipped with double-layer spiral stirring paddle (rotating speed 300 ± 10 rpm), paddle angle 45°, to promote the shear-collision mixing of nanoparticles and modifiers. Piezoelectric pressure sensor (accuracy ± 0.01 MPa) is used to feedback the cavitation intensity to the central processing unit, and when the detected value is <0.8 MPa, the ultrasonic frequency is automatically increased to 30 kHz.

[0034] Vacuum adsorption module: vacuum degree is -0.08 MPa, directional adsorption of plating agent and vertical arrangement of nanoparticles are realized through a porous titanium alloy substrate (pore size 5 μm), forming a dense "core-shell" structure, substrate surface roughness Ra≤0.1 μm, plating thickness 20±2 nm, uniformity deviation <5%. Real-time measurement of plating thickness (20±0.5 nm) is realized by laser interferometer (wavelength 632.8 nm), combined with vacuum degree (-0.08 MPa±1%) and substrate pore size (5 μm±0.1 μm) to optimize adsorption time (2±0.1 min).

[0035] Low-temperature curing unit: including 365 nm, intensity 50 mW / cm 2 UV-LED, using far infrared radiation heating (wavelength 3-5 μm), temperature 75±2℃, curing time 15 min, adapting to R2R production line speed 3 m / min, energy consumption reduced by 40%. R2R production line linkage: servo motor driven coiled material (line speed 3 m / min±0.05%), through tension sensor (range 0-500 N) and infrared thermometer (accuracy ±0.5℃) to realize synchronous regulation of low-temperature curing unit (75±0.5℃).

[0036] Example 2

[0037] The embodiment provides a method applied to a nano-silica antifouling plating agent, which comprises the following specific steps:

[0038] S1, plasma pretreatment: 50 eV Ar + beam is used to bombard the surface of nano-silica for 30 seconds, the total treatment time is dynamically adjusted in real time according to the hydroxyl density, the beam density is 3 mA / cm 2 , the weakly combined hydroxyl is selectively etched to form high-density anchoring sites, the hydroxyl density of the surface of nano-silica is increased to 8.2 OH / nm 2 , and if the Raman spectrum detects that the hydroxyl density is <8.0 OH / nm 2If so, 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 activation zone temperature is stable at 40±0.2℃, with an overshoot of <0.1℃.

[0039] S2, in-situ synergistic graft modification: 5 parts by weight of silane coupling agent KH-570, 3 parts by weight of fluorocarbon chain monomer perfluorooctyltriethoxysilane and 0.5 parts by weight of ionic liquid modifier 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide salt are mixed and dissolved in a volume ratio of 7:3 of ethanol / water mixed solvent. The total concentration of the modifier is 15wt%, the solid content of the nanosilica is 20wt%, and the ultrasonic dispersion time is 30 min. The ultrasonic cavitation intensity is linked with the stirring speed, when the nanoparticle size distribution D50>50 nm, the double-layer spiral stirring paddle is started, the speed is increased to 320 rpm, the inclination angle is adjusted to 50°, and the vacuum adsorption pressure gradient control: through the feedback of the pressure sensor, in the initial adsorption stage (0-30 s), it is maintained at-0.08 MPa, in the middle stage (30-90 s), it is adjusted to-0.06 MPa, and in the final stage (90-120 s), it is reduced to-0.04 MPa, reducing bubble residue.

[0040] S3, vacuum adsorption directional film formation: IBAD conductive layer deposition is started synchronously in the adsorption stage, the ITO target sputtering power is 200 W, the oxygen partial pressure is 0.3 Pa, the deposition rate is 0.5 nm / s, and the conductive layer thickness is 10 nm (surface resistance≤10 6 Ω / sq, light transmittance loss <0.5%), combined with electrostatic field (1 kV / cm) and ion beam current (incident angle 30°), guiding the directional arrangement of nanosilica and conductive layer to form a vertical through structure (electron mobility increased to 10 -2 cm 2 / V·s), the vacuum pressure is-0.08 MPa, the adsorption time is 2 min, and the conductive layer and fluorocarbon layer are alternately deposited synchronously in the vacuum adsorption stage, and the interface chemical bonding is realized through ion beam current energy gradient regulation (50→200 eV) (interface bonding energy≥1.5 J / m 2 ), and the substrate surface forms a vertical arrangement of "core-shell" structure (core layer is silica, shell layer is fluorocarbon chain-siloxane composite layer).

[0041] S4, low-temperature rapid curing: 100 eV beam current is used to bombard the fluorocarbon chain surface, the beam current density is 2 mA / cm 2 , triggering C-F bond rearrangement and crosslinking, making the fluorocarbon shell layer thickness from 2 nm compressed to 1.5 nm (refractive index from 1.38 to 1.25), and the antireflection rate increased to 3.2%, with 365 nm, intensity 50 mW / cm 2UV-LED irradiation for 5 min, triggered siloxane condensation reaction, heated to 75℃ by far infrared radiation, curing time 15 min. Based on thermal imaging data and coating thickness distribution, the intensity of far infrared radiation, UV-LED light intensity and web line speed are dynamically adjusted by multivariate PID algorithm to ensure that the crosslinking density is ≥85% and the energy consumption is reduced by 30%.

[0042] The multivariate PID algorithm involved in the above examples is: dynamically adjusting the plasma power and ultrasonic frequency according to real-time sensor data to ensure that the hydroxyl density error is <2% and the cavitation intensity fluctuation is <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 spectrum sensor and vacuum pressure sensor, the multivariate PID total algorithm is: Wherein, u(t) is the global control output, used to comprehensively adjust the execution mechanisms such as plasma power, ultrasonic frequency, vacuum pressure; K p (t), K i (t), K d (t) is the gain coefficient adjusted dynamically, reflecting the proportional, integral and differential weights of the real-time response of the system, K p (t) is taken as 0.5-2.0, K i is taken as 0.05-0.3, K d is taken as 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, eliminating long-term deviation; is the rate of change of the comprehensive error, predicting the dynamic characteristics of the system and suppressing oscillation; all formulas realize dynamic control through real-time feedback (such as Raman spectrum, pressure sensor, thermal imager) to ensure the performance of the coating.

[0043] The multivariate PID-p algorithm formula in S1 plasma pretreatment in Example 2 is Wherein, u power (t) is the output signal for controlling plasma power, used to dynamically adjust the power density of the plasma generator, K p , K i and K d are proportional, integral and differential gain coefficients, respectively corresponding to the adjustment weight of the current error, cumulative error and error trend, K p is taken as 0.8-1.5, K i is taken as 0.05-0.15, K d is taken as 0.1-0.3; e OH(t) is the hydroxyl density error, i.e. the deviation of the target hydroxyl density (e.g. 8.2 OH / nm 2 ) from the actual Raman spectrum detection value; e radical (t) is the free radical concentration deviation, the difference between the actual free radical concentration and the target threshold (e.g. ≥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 rate of change of free radical concentration deviation, predicting trends and suppressing 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 of the argon / oxygen mixed gas source; K' p , K' i are the proportional and integral gain coefficients, dynamically adjusting the response strength of the oxygen proportion error, K' p takes 0.3-0.8, K' i takes 0.1-0.2; is the oxygen proportion fluctuation, i.e. the deviation of the target oxygen proportion (e.g. 10%) from the actual detection value; is the cumulative integral of the oxygen proportion error, correcting the steady-state error of gas proportion control.

[0044] The multivariable PID algorithm-cure in Example 2 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 film thickness, temperature, and UV 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 film 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 UV light intensity error (target 50 mW / cm 2 ), ∫(e temp +e UV )dt is the cumulative integral of the temperature and UV errors, ensuring curing uniformity; To reduce the rate of change of the curing speed (e.g. 3 m / min of the web line speed), to suppress process fluctuation; to adjust the radiation intensity by thermal imaging data partitioning, to reduce the curing energy consumption by 30% while ensuring the crosslinking density ≥ 85%

[0045] Comparative Example 1

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

[0047] Comparative Example 2

[0048] The difference from Example 1 is that the adaptive PID control algorithm is absent, and the adjustment control is performed manually, and the others are the same.

[0049] Comparative Example 3

[0050] The difference from Example 1 is that the equal weight part of the ionic liquid modifier 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonylimide salt is absent, and the others are the same.

[0051] Performance Test

[0052] 1. Resistance, transmittance, etc. test: crosslinking density test according to ASTM D2765; resistance rate test according to ASTM D257 at temperature 23℃, humidity 50% for the examples and comparative examples, using four-probe resistance meter, applying 100V direct current voltage, measuring resistance value and calculating surface resistance rate; preparing the coated glass sample into a coated substrate for the examples and comparative examples, testing according to ISO 13696, using ultraviolet-visible spectrophotometer, testing the transmittance of the coated substrate in the wavelength range of 400-800nm; water contact angle test according to GB / T 30693 for the examples and comparative examples, using contact angle measuring instrument, dropping 2μL deionized water on the coated surface, fitting the droplet profile by Young-Laplace equation, calculating the static contact angle; adhesion test according to ASTM D3359 for the examples and comparative examples, using cross-cut method (cross-hatch test): drawing a 1mm×1mm square on the coated surface with a blade, then quickly peeling off the 3M tape, observing the proportion of the coating falling off; abrasion resistance test according to ASTM D4060 for the examples and comparative examples, using Taber linear abrasion tester, configuring CS-10 grinding wheel, applying 500g load, circulating the coated surface, recording the number of friction times when the coating is damaged, and the results are shown in Table 1.

[0053] Table 1

[0054]

[0055]

[0056] The above detailed description of the application is only as an example, and the application is not limited to the above described specific embodiments. Any equivalent modifications and substitutions made by those skilled in the art to the application are also within the scope of the application. Therefore, equivalent transformations and modifications made without departing from the spirit and scope of the application should be covered within the scope of the application.

Claims

1. A modified device applied to a nano-silica anti-fouling coating agent, characterized in that, The application discloses a plasma activation module, an atmospheric pressure dielectric barrier discharge plasma generator, an argon / oxygen mixed gas source and a Raman spectrum sensor are arranged in the module, and the module is used for dynamically adjusting plasma power density and gas proportion through a multivariate PID algorithm, so that the hydroxyl density is stabilized. The application further discloses an ion beam assisted deposition module and an ultrasonic cavitation module, a double-plasma ion source, a magnetic filtering device and an ITO target material are arranged in the ion beam assisted deposition module, the ion beam assisted deposition module is used for alternately depositing a conductive layer and a fluorocarbon modifier in a vacuum cavity, and the deposition rate is controlled to be 0.5 nm / s; a high-frequency ultrasonic transducer and a piezoelectric pressure sensor are arranged in the ultrasonic cavitation module, and the ultrasonic cavitation module is used for automatically increasing the rotating speed to 320 rpm and adjusting the inclination angle to 50° according to a nanoparticle D50 particle size feedback signal when it is detected that D50>50 nm. The application further discloses 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 for maintaining the film thickness through adsorption time and pressure gradient linkage control, and the low-temperature curing unit is provided with a far-infrared radiation heating device, a thermal imager and a UV-LED array, and the low-temperature curing unit is used for adjusting the radiation intensity according to film thickness distribution data in different regions.

2. A modification method using the modification device for nano-silica anti-fouling coating agent according to claim 1, characterized in that, The modification method comprises the following steps: S1. Plasma pretreatment: 50 eV Ar beam bombardment of the nanosilica surface for 5 minutes under an argon / oxygen gas mixture + The treatment time was extended when the Raman spectrum detected a hydroxyl density < 8.0 OH / nm 2 2 S2. In-situ synergistic graft modification: a modifier is prepared by mixing silane coupling agent KH-570, perfluorooctyltriethoxysilane and 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt, ultrasonic dispersion is carried out for 30 min, and then directional film formation is carried out through vacuum adsorption; S3. Ion beam assisted deposition of a conductive layer: ITO conductive layers and fluorocarbon shell layers are alternately deposited in a vacuum cavity; S4. Low-temperature curing: fluorocarbon bond rearrangement is triggered by using 100eV O-beam current, UV-LED irradiation is carried out for 5 min, and far-infrared heating is carried out to 75 DEG C for curing.

3. The modification method according to claim 2, characterized in that, The components of the modifier are 5 parts by weight of KH-570, 3 parts by weight of perfluorooctyltriethoxysilane and 0.5 parts by weight of 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt.

4. The modification method according to claim 2, wherein In the step S3, the ITO target material sputtering power is 200 W, and the oxygen partial pressure is 0.3 Pa; a vertical through structure is formed by combining a 1kV / cm electrostatic field and a 30° ion beam incident angle.

5. The modification method of claim 2, wherein, The step S1 plasma pretreatment process further comprises a multivariable PID-p algorithm and a multivariable PID-g algorithm, the multivariable PID-p algorithm is formula Wherein, u power (t) is an output signal for controlling plasma power, K p , K i and K d are proportional, integral and differential gain coefficients; e OH (t) is a hydroxyl density error; e radical (t) is a free radical concentration deviation; ∫e OH (t)dt is a cumulative amount of hydroxyl density error over time; is a change rate of free radical concentration deviation; the multivariable PID-g algorithm is formula Wherein, u gas (t) is an output signal for controlling gas mixing ratio; K' p , K' i are proportional and integral gain coefficients; is oxygen proportion fluctuation; is a cumulative integral of oxygen proportion error.

6. The modification method according to claim 5, wherein The low-temperature curing process in step S4 also employs a multivariate PID algorithm -cure, which is... Among them, u cure (t) represents the output signal controlling the low-temperature curing process; K" p 、K″i、K" d For proportional, integral, and differential gain coefficients; e thick (t) represents the coating thickness deviation, e temp For temperature fluctuations, e UV For ultraviolet light intensity error, ∫(e temp +e UV )dt is the cumulative integral of temperature and UV error; This represents the rate of change of curing speed.

7. The modification method of claim 5, wherein, The total formula of the multivariable PID algorithm is: Wherein, u(t) is the global control output; K p (t), K i (t), K d (t) is the gain coefficient of dynamic adjustment; e(t) is the integrated error signal; ∫e(t)dt is the cumulative integral of all errors; is the change rate of the integrated error.

8. The modification method of claim 2, wherein, Also included in the plasma pre-treatment phase is the automatic increase of the oxygen proportion to 10.5% and the extension of the treatment time to 6 min when a hydroxyl density < 8.0 OH / nm 2 is detected.

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