Desalination protection method and system for ocean effluent chinaware

Abstract

The invention relates to the technical field of cultural relic protection, and particularly discloses a desalination protection method and system for ocean effluent chinaware. The method comprises the following steps: directionally removing free salt under the protection of an ion selective membrane through pulse electrolysis, separating out deep crystallized salt in combination with multi-stage gradient depressurization permeation, and inhibiting structural damage by adopting segmented freeze drying; the system is composed of a pretreatment unit, an electrolytic desalination unit, a gradient pressure reduction unit and a drying unit, the electrolytic desalination unit is provided with an anti-oxidation circulation system, the pressure reduction unit integrates a rotating turbulent flow field and an osmotic pressure controller, and a crack monitoring module is arranged in the drying unit. Salinity data are fed back in real time through the embedded sensor network, process parameters are dynamically optimized through the central control unit, and cooperative control over high efficiency and cultural relic safety in the desalting process is achieved.

Description

Technical Field

[0001] This invention relates to the field of cultural relic protection technology, and more specifically, to a method and system for desalination and protection of marine-exposed ceramic artifacts. Background Technology

[0002] Ceramic artifacts recovered from the seabed accumulate large amounts of soluble salts (such as sodium chloride and magnesium chloride) within their pores due to prolonged submersion in the ocean environment. When these precious artifacts are retrieved, changes in temperature and humidity cause repeated crystallization and dissolution of these salts, generating immense internal stress. This leads to irreversible damage, including surface powdering, glaze peeling, and even structural collapse. Therefore, effectively removing these harmful salts is a core challenge in protecting these artifacts.

[0003] However, existing desalination and preservation technologies have significant shortcomings. Mainstream static immersion or circulating water rinsing methods are inefficient, with extremely long desalination cycles, and are unable to completely remove stubborn crystalline salts from the deep pores of ceramics, leaving residual salts as a long-term threat. While attempting to accelerate desalination with an electric field can shorten the cycle, a continuous DC electric field can trigger water electrolysis, leading to drastic fluctuations in local pH levels, severely corroding the ceramic glaze and causing new chemical damage. Furthermore, in the crucial later drying stage, the internal stress generated by uneven moisture evaporation in conventional drying techniques can easily induce or propagate microcracks, directly damaging the structural integrity of the artifact. Simultaneously, existing technologies generally lack the ability to monitor and dynamically control core parameters of the desalination process (such as internal salt concentration and stress changes), failing to optimize the desalination path based on the specific salt migration patterns within the artifact, thus compromising the preservation effect.

[0004] The prior art (publication number: CN102173866B) provides a method for desalination and protection of marine-exposed ceramic artifacts. Its main steps are: 1) removing surface deposits from the marine-exposed ceramic artifacts and allowing them to stand in an aqueous solution for desalination; 2) subjecting the marine-exposed ceramic artifacts after standing in the aqueous solution to alternating cold-hot water immersion and ultrasonic immersion; 3) when the conductivity of the immersion solution is stable and tends to 1 μS / cm, and the remaining total salt content is below 500 μg / g, the desalination endpoint has been reached. This invention utilizes a conductivity meter and ion chromatography instrument to monitor the desalination process in real time and proposes a basis for determining the desalination endpoint. Although this technology has improvements, it still suffers from the aforementioned technical defects.

[0005] This invention aims to overcome the aforementioned key shortcomings and provide a desalination protection method and system capable of efficiently, thoroughly, and safely removing internal and deep-seated salt from marine-excavated ceramic artifacts while maximizing the protection of their physical structure and surface condition (especially the glaze). Its core objective is to address the problems of low desalination efficiency, high residual risk, susceptibility to secondary damage (chemical corrosion and physical structural destruction), and insufficient process automation in existing technologies, thereby achieving scientific and reliable protection of precious underwater archaeological ceramic artifacts. While this technology represents an improvement over traditional methods, it does not solve the problem of removing deep-seated crystalline salt.

[0006] Therefore, a method and system for desalination protection of marine ceramic artifacts is proposed to address the above problems. Summary of the Invention

[0007] In order to overcome the above-mentioned defects of the prior art, embodiments of the present invention provide a method and system for desalination protection of marine ceramic artifacts to solve the problems mentioned in the background art.

[0008] To achieve the above objectives, the present invention provides the following technical solution: a method for desalination protection of marine-exposed ceramic artifacts, comprising the following steps:

[0009] (a) Multi-stage pretreatment: The ceramic is placed in a constant temperature environment of 5-15℃. First, 20-100W, 40kHz ultrasonic waves are used in conjunction with weakly alkaline deionized water with pH 7.0-7.5 to remove surface bio-attachments. Then, microfluidic technology is used to rinse the internal pores. Finally, the composition of the cleaning solution deposits is analyzed by a laser particle size analyzer.

[0010] (b) Pulsed electrolytic desalination: A square-wave pulsed DC current with a current density of 0.5-5 mA / cm² is applied to an electric field constructed using a titanium-based platinum-plated electrode. 2 Frequency 1-10Hz, duty cycle 30%-70%, electrolyte is circulating deionized water containing 0.1-0.5mmol / L ascorbic acid, and ion-selective membrane isolates the anode and cathode regions;

[0011] (c) Gradient pressure reduction: The ceramics are moved step by step in a 5-stage osmotic pressure tank, with the osmotic pressure gradually decreasing from 3.0 MPa to 0.1 MPa and the pressure difference decrease rate between adjacent stages ≤15%, and each stage is held for 12-72 hours;

[0012] (d) Segmented freeze drying: The first stage is pre-freezing at -30℃ to -35℃ and 50-100Pa; the second stage is sublimation at -15℃ to -20℃ and 60-100Pa for 2-4 hours; and the third stage is dehydration at 25-30℃ and 10-50Pa until the moisture content is ≤0.5wt%.

[0013] Furthermore, the microjet technology described in step (a) employs a conical nozzle array with an outlet diameter of 0.1-0.3 mm, a jet pressure of 0.2-0.8 MPa, a water flow direction at an angle of 15-45° to the ceramic surface, and automatically switches the jet mode every 5 minutes of cleaning.

[0014] Furthermore, in step (b), an electrolyte temperature closed-loop control system is set up. When the electrolyte temperature is detected to be >25°C, the semiconductor cooling module is activated. The fluctuation control of ±1°C is achieved through the semiconductor cooling module and the PID temperature controller. At the same time, the inner wall of the electrolytic cell is coated with a nano titanium dioxide anti-corrosion coating.

[0015] Furthermore, in step (c), the ceramic is placed on a rotating platform with a rotation speed of 0.5-2 rpm. The surface of the platform is covered with a 3-5 mm silicone damping layer, and a vortex generator is installed at the bottom of each osmotic pressure tank to create a turbulent flow field with a Reynolds number of 2000-5000.

[0016] A desalination protection system for marine-exported ceramic artifacts includes:

[0017] The pretreatment unit includes a constant temperature ultrasonic cleaning chamber, a microjet jet module, and a laser deposition analyzer;

[0018] The electrolytic desalination unit includes an adjustable-spacing titanium-based platinum-plated electrode, a square-wave pulse power supply, and a circulating filtration system with an ion-selective membrane;

[0019] The gradient depressurization unit includes a 5-stage osmotic pressure control tank and a rotating platform;

[0020] The vacuum freeze-drying unit includes a three-stage temperature control system;

[0021] The central control unit connects to the sensors in each unit and includes an optimization module, which is used to dynamically adjust the electrolysis parameters and the pressure reduction path based on salinity data.

[0022] Furthermore, during the electrolytic desalination and gradient depressurization process, micropores with a diameter ≤0.8mm are implanted in the non-glazed area of ​​the ceramic using laser micro-drilling technology. A micro fiber optic sensor array is embedded inside the body to monitor Cl- concentration, pH value, and stress changes in real time. After implantation, nano-scale silicon-based repair agent is used to seal the micropores. The linear thermal expansion coefficient of the repair body differs from that of the body body by ≤5%. The sensor data sampling frequency is ≥1 time / minute and is wirelessly transmitted to the central processor.

[0023] Furthermore, the central processing unit's built-in convolutional neural network algorithm predicts optimal process parameters based on historical desalination databases, when a local Cl- concentration gradient > 2 mg / cm³ is detected. 3The robotic arm is triggered to adjust the orientation of the ceramic and a three-dimensional salinity distribution thermogram is generated in real time. The micro fiber optic sensor has a spatial resolution of <1mm and a sampling frequency of >1 time / minute.

[0024] Furthermore, the central control unit includes a fault diagnosis module that automatically executes a protection program when any of the following situations occur: the electrolytic cell voltage fluctuation is greater than 15% for more than 10 seconds, triggering the fuse protection and switching to the backup power supply; the concentration difference between the osmotic pressure cells deviates from the set value by more than 20%, triggering the automatic solution replenishment mechanism; the temperature change rate of the drying chamber is greater than 5℃ / min, activating the emergency heat preservation program. The solution replenishment mechanism is linked to the metering pump and the concentration sensor, with a flow control accuracy of ±0.5mL / s.

[0025] Furthermore, the electrolytic desalination unit is equipped with a byproduct recovery device, a hydrogen collection hood connected to a catalytic burner is installed in the cathode area, and a chlorine absorption tower containing 5-10% sodium thiosulfate solution is installed in the anode area. Combustion heat and reaction heat are recovered and utilized through a heat exchanger.

[0026] Furthermore, the system is equipped with a material compatibility testing module, including: setting a ceramic material spectral analysis probe in the pretreatment unit to automatically match cleaning parameters; configuring a dielectric constant detector in the electrolytic desalination unit to dynamically optimize the electric field strength; and building an acoustic emission sensor in the drying unit to monitor microcrack propagation signals in real time and adjust the drying curve.

[0027] The technical effects and advantages of this invention are as follows:

[0028] Compared with existing technologies, this invention achieves efficient and non-destructive desalination protection through a multi-level synergistic mechanism, specifically encompassing five core functions: First, it employs pulsed electrolysis technology combined with ion-selective membrane isolation protection, utilizing a square wave electric field to directionally remove free salt ions while simultaneously adding antioxidants to maintain electrolyte stability, thus preventing secondary damage to artifacts caused by electrode corrosion (directional desalination). Second, it combines the principle of progressively decreasing osmotic pressure difference in a controllable gradient depressurization system with the turbulent field generated by a rotating platform to achieve gentle precipitation of deep-seated crystallized salts from ceramics, effectively blocking salt backflow (deep purification). Third, it uses an implanted sensor network to monitor changes in salinity and stress in the ceramic body in real time, dynamically optimizing electrolysis parameters and depressurization paths through artificial intelligence algorithms to form closed-loop control of process parameters (adaptive control). Fourth, it uses a segmented freeze-drying program to precisely control the water phase change process, and actively adjusts the drying curve using an acoustic emission crack early warning mechanism to minimize capillary stress damage (structural protection). Fifth, it integrates multi-source sensing modules such as material spectral analysis and dielectric constant detection to automatically adapt to the physicochemical properties of different ceramics, ensuring process safety and universality (system compatibility). Attached Figure Description

[0029] Figure 1This is a system framework diagram of the present invention.

[0030] Figure 2 This is a flowchart of the process of the present invention.

[0031] Figure 3 This is a schematic diagram of the intelligent control principle of the present invention. Detailed Implementation

[0032] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0033] Example 1:

[0034] As attached Figure 1-3 As shown, (1) a method for desalination protection of marine-exposed ceramic artifacts includes the following steps:

[0035] (a) Multi-stage pretreatment: The ceramic is placed in a constant temperature environment of 5-15℃. First, 20-100W, 40kHz ultrasonic waves are used in conjunction with weakly alkaline deionized water with pH 7.0-7.5 to remove surface bio-attachments. Then, microfluidic technology is used to rinse the internal pores. Finally, the composition of the cleaning solution deposits is analyzed by a laser particle size analyzer.

[0036] (b) Pulsed electrolytic desalination: A square-wave pulsed DC current with a current density of 0.5-5 mA / cm² is applied to an electric field constructed using a titanium-based platinum-plated electrode. 2 Frequency 1-10Hz, duty cycle 30%-70%, electrolyte is circulating deionized water containing 0.1-0.5mmol / L ascorbic acid, and ion-selective membrane isolates the anode and cathode regions;

[0037] (c) Gradient pressure reduction: The ceramics are moved step by step in a 5-stage osmotic pressure tank, with the osmotic pressure gradually decreasing from 3.0 MPa to 0.1 MPa and the pressure difference decrease rate between adjacent stages ≤15%, and each stage is held for 12-72 hours;

[0038] (d) Segmented freeze-drying: The first stage involves pre-freezing at -30℃ to -35℃ and 50-100Pa; the second stage involves sublimation at -15℃ to -20℃ and 60-100Pa for 2-4 hours; and the third stage involves dehydration at 25-30℃ and 10-50Pa until the water content is ≤0.5wt%. In this process, the marine-derived ceramics are first placed in a constant-temperature cleaning tank, which is maintained at 10℃±2℃. A deionized sodium bicarbonate aqueous solution with a pH of 7.2 is injected, and ultrasonic vibration at a power of 60W and a frequency of 40kHz is started for 30 minutes to remove surface marine organisms and loose sediments. Subsequently, a micro-jet module is activated to spray deionized water into the pores inside the ceramics through a ring of 0.2mm conical nozzles at a pressure of 0.5MPa and an inclination angle of 30°. The jet direction is switched every 5 minutes. After the cleaning solution is tested by a laser particle size analyzer and it shows that 90% of the sediment particles are less than 50μm, it is transferred to an electrolytic cell. A square wave pulsed electric field (current density 2 mA / cm²) was applied between titanium-based platinum-plated electrodes spaced 15 cm apart. 2 The electrolysis was performed at a frequency of 5 Hz and a duty cycle of 50%. The electrolyte was circulating deionized water containing 0.3 mmol / L ascorbic acid. An ion-selective membrane stabilized the pH of the cathode region at 6.5-7.5. After 72 hours of electrolysis, a six-axis robotic arm moved the ceramics into the first-stage 3.0 MPa osmotic pressure tank (28% sea salt simulated solution concentration). Each stage was held for 48 hours, and the pressure was gradually reduced to 0.1 MPa in the fifth stage (concentration gradient difference of 12%). Finally, a three-stage drying process was performed in a vacuum freeze-drying chamber: pre-freezing at -32℃ / 80Pa for 4 hours → sublimation at -18℃ / 60Pa for 6 hours → deep dehydration at 28℃ / 30Pa to a water content of 0.4%.

[0039] (2) The microjet technology described in step (a) employs a conical nozzle array with an outlet diameter of 0.1-0.3 mm, a jetting pressure of 0.2-0.8 MPa, and a water flow direction at a 15-45° angle to the ceramic surface. The jetting mode automatically switches every 5 minutes of cleaning. The microjet jetting module is configured with a ring array of 36 conical nozzles, with an outlet diameter of 0.25 mm ± 0.05 mm. A high-pressure pump maintains a stable water pressure of 0.55 MPa ± 0.05 MPa. The jetting direction control system drives the nozzle support to rotate at a uniform speed of 10 rpm, creating a dynamically changing impact angle of 25°-40° between the water flow and the ceramic surface. After 5 minutes of clockwise jetting, the system automatically switches to counter-clockwise mode and adjusts the tilt angle by ± 5° to ensure sufficient dissolution of salt within the pores. The silicone damping layer is made of 3.5 mm thick food-grade silicone through molding, with a Shore hardness of 35A, effectively absorbing vibration energy during robotic arm transmission.

[0040] (3) In step (b), a closed-loop control system for electrolyte temperature is set up. When the electrolyte temperature is detected to be >25℃, the semiconductor cooling module is activated. The semiconductor cooling module and the PID temperature controller achieve ±1℃ fluctuation control. At the same time, the inner wall of the electrolytic cell is coated with a nano-titanium dioxide anti-corrosion coating. The outer wall of the electrolytic cell integrates a semiconductor cooling chip group. When the Pt100 temperature sensor detects that the electrolyte temperature has risen to 26℃, the TEC1-12706 cooling module is activated to quickly reduce the temperature to 24℃±0.5℃. A 50μm thick nano-titanium dioxide coating (grain size 20-30nm) is sprayed on the inner surface of the cell. Electrochemical impedance spectroscopy shows that the corrosion current density is reduced to 1 / 8 of that of the uncoated cell. A 0.2μm polytetrafluoroethylene filter is installed in the circulation pipeline, and 15% of the electrolyte is replaced every hour to maintain the effective concentration of ascorbic acid.

[0041] (4) In step (c), the ceramic vessel is placed on a rotating platform with a rotation speed of 0.5-2 rpm. The platform surface is covered with a 3-5 mm silicone damping layer, and a vortex generator is installed at the bottom of each osmotic pressure tank to create a turbulent flow field with a Reynolds number of 2000-5000. The rotating platform is driven by a stepper motor with a rotation speed of 1 rpm ± 0.1 rpm. Vortex generator blades (tilt angle 45°, blade height 1 / 3 of tank depth) are installed at the bottom of the platform. When the solution flows through the blades at a velocity of 0.3 m / s, a turbulent flow field with a Reynolds number of 3500 ± 500 is formed. This has been verified by a particle image velocimeter to improve the mass transfer coefficient by 23%. The osmotic pressure control tanks are connected by an overflow pipe. The concentration sensor feeds back data to the metering pump in real time, and deionized water is automatically added to keep the concentration difference between stages stable within ± 2% of the set value.

[0042] (5) A desalination protection system for marine-exposed ceramic artifacts, comprising:

[0043] The pretreatment unit includes a constant temperature ultrasonic cleaning chamber, a microjet jet module, and a laser deposition analyzer;

[0044] The electrolytic desalination unit includes an adjustable-spacing titanium-based platinum-plated electrode, a square-wave pulse power supply, and a circulating filtration system with an ion-selective membrane;

[0045] The gradient depressurization unit includes a 5-stage osmotic pressure control tank and a rotating platform;

[0046] The vacuum freeze-drying unit includes a three-stage temperature control system;

[0047] The central control unit connects to the sensors in each unit and includes an optimization module for dynamically adjusting electrolysis parameters and pressure reduction paths based on salinity data. The pretreatment unit features an 80L constant-temperature ultrasonic cleaning chamber with six built-in 40kHz transducers; the micro-jet module's high-pressure pump has a maximum pressure of 1.2MPa and an adjustable flow rate of 2-10L / min. The electrode array spacing in the electrolytic desalination unit is continuously adjustable from 5-20cm, driven by a servo motor, and the pulse power supply has a maximum output current of 50A (ripple coefficient <1%). The gradient pressure reduction unit has five stages with progressively increasing tank volumes of 20%, and the final stage is equipped with a reverse osmosis membrane to maintain low osmotic pressure. The vacuum freeze-drying chamber uses a three-stage cascade refrigeration system, with a cold trap temperature reaching -65℃. The central control unit is equipped with an Intel i7-1185G7 processor and runs a desalination control core developed based on ROS.

[0048] (6) During the electrolytic desalination and gradient depressurization process, micropores with a diameter ≤0.8mm are implanted in the non-glazed area of ​​the ceramic using laser micro-drilling technology. A micro-fiber sensor array is embedded inside the ceramic body to monitor Cl- concentration, pH value, and stress changes in real time. After implantation, the micropores are sealed with a nano-scale silicon-based repair agent. The difference between the linear thermal expansion coefficient of the repair body and the ceramic body is ≤5%. The sensor data sampling frequency is ≥1 time / minute and is wirelessly transmitted to the central processing unit. Among them, the Cl- sensing end is coated with an AgCl sensitive film, and the measurement range is 0-10 mg / cm³. 3 Accuracy ±0.15mg / cm 3 The pH sensor integrates a bromocresol purple indicator, analyzing pH values ​​via reflectance spectroscopy with a resolution of 0.05. The stress sensor employs an FBG grating, achieving a strain measurement sensitivity of 1.2 pm / με. Data is transmitted to the central processor every 30 seconds via ZigBee. When a local Cl- concentration gradient >1.8 mg / cm² is detected... 3 At that time, the robotic arm is triggered to redirect the area to a high-flow-rate zone.

[0049] (7) The convolutional neural network algorithm built into the central processing unit predicts the optimal process parameters based on the historical desalination database. When a local Cl- concentration gradient > 2 mg / cm³ is detected... 3 The robotic arm is triggered to adjust the orientation of the ceramic piece and generates a three-dimensional salinity distribution thermogram in real time. The miniature fiber optic sensor has a spatial resolution of <1mm and a sampling frequency of >1 time / minute. The convolutional neural network of the central processing unit uses VGG-16 architecture, and the input layer receives spatiotemporal sequence data from the sensor array (time step 10 minutes, spatial resolution 1mm). 3 This method extracts salt migration features through three convolutional layers, and the output layer predicts the optimal depressurization path. The training data includes 200 historical desalination cases, and the correlation coefficient R between the prediction results and actual desalination efficiency is [value missing]. 2=0.93. The three-dimensional salinity thermogram was reconstructed using the Marching Cubes algorithm, with red warning areas (Cl- > 4 mg / cm³). 3 Automatically marks coordinates and optimizes the robotic arm's motion trajectory.

[0050] (8) The central control unit includes a fault diagnosis module, which automatically executes a protection program when any of the following situations occur: Electrolytic cell voltage fluctuation > 15% for more than 10 seconds, triggering fuse protection and switching to backup power; concentration difference between osmotic pressure cells deviating from the set value > 20%, triggering the automatic solution replenishment mechanism; temperature change rate in the drying chamber > 5℃ / min, activating the emergency insulation program. The solution replenishment mechanism is linked to a metering pump and a concentration sensor, with a flow control accuracy of ±0.5mL / s. The fault diagnosis module has a preset three-level response mechanism: when the voltage sensor detects a fluctuation amplitude > 15%, the main circuit is cut off and the 24V DC backup power is switched within 0.5 seconds; when the concentration difference exceeds the limit, the peristaltic pump is triggered to replenish the solution at a flow rate of 5mL / s; when the temperature change in the drying chamber exceeds the limit, the liquid nitrogen injection valve opens instantaneously to form an air film insulation layer. Historical fault data is stored in an SQL database, and the failure probability of each unit is calculated and the maintenance cycle is optimized using a Bayesian network.

[0051] (9) The electrolytic desalination unit is equipped with a byproduct recovery device. A hydrogen collection hood connected to a catalytic burner is installed in the cathode area, and a chlorine absorption tower containing a 5-10% sodium thiosulfate solution is installed in the anode area. Combustion heat and reaction heat are recovered and utilized through a heat exchanger. The hydrogen collection hood in the cathode area is an inverted conical titanium alloy structure, with a platinum / palladium catalytic burner (operating temperature 350℃) connected to the top. Combustion heat is conducted to a preheating tank via heat pipes, raising the inlet water temperature to 40℃. The chlorine absorption tower in the anode area is filled with a 10% sodium thiosulfate solution, achieving a chlorine removal rate >99.9%. The waste liquid is recycled after electrolytic regeneration. The heat exchanger adopts a plate-fin structure, with a measured heat recovery efficiency of 68%.

[0052] (10) The system is equipped with a material compatibility test module, including: setting a ceramic material spectrum analysis probe in the pretreatment unit to automatically match the cleaning parameters, configuring a dielectric constant detector in the electro-deionization unit to dynamically optimize the electric field strength, and installing an acoustic emission sensor in the drying unit to monitor the microcrack propagation signal in real time and adjust the drying curve. Among them, the material spectrum analysis probe integrates a near-infrared spectrometer (wavelength range 900 - 1700nm), and identifies the type of pottery through a PLS regression model (such as the characteristic absorption peak of celadon at 1382nm); the dielectric constant detector is based on the principle of parallel plate capacitance (plate spacing 2mm), and automatically adjusts the electric field strength to 70% of the critical breakdown voltage at a measurement frequency of 1MHz; the acoustic emission sensor (sensitivity 80dB) captures high-frequency crack signals > 40kHz in real time during the drying stage. When the event count rate > 50 times / minute, the drying program automatically switches to the protection curve (heating rate ≤ 1℃ / h). After being processed by this system, the salt back-permeation rate of the ceramics < 5% (test sample N = 50). The accelerated aging test shows that no microcracks appear in the implanted repair area after 100 temperature and humidity cycles.

[0053] Example 2: Multi-source data joint modeling scenario

[0054] Step 1: Constant temperature ultrasonic cleaning

[0055] Put the salvaged ceramics into a stainless steel cleaning tank, and pre-inject a weakly alkaline solution (composition: 0.1mol / L sodium bicarbonate + deionized water) with a temperature maintained at 10℃ (allowing a ±2℃ fluctuation) into the tank. Start a 40kHz ultrasonic generator, set the power to 60W, and continuously oscillate for 30 minutes. During this process, the ultrasonic cavitation effect will strip the attached marine organisms such as corals and shells on the surface. After completion, drain the dirty liquid, and use an endoscope to check that there are no visible attachments on the inner wall as qualified.

[0056] Step 2: Micro-jet pore flushing

[0057] Transfer the ceramics to a rotating loading platform, and start 36 conical spray guns (spray nozzle diameter 0.25mm) distributed in a ring. The high-pressure pump sprays deionized water at a pressure of 0.5MPa, and the water flow direction impacts the pores at a 30° angle with the surface of the ceramics. The workbench automatically rotates counterclockwise by 90° every 5 minutes to ensure that the water flow covers all angles. After flushing for 20 minutes, take the discharged liquid and detect it with a laser particle size analyzer - if the proportion of particles with a particle size > 50μm detected exceeds 10%, repeat the flushing until it meets the standard.

[0058] Step 3: Electrolytic cell installation and parameter setting

[0059] Hang the ceramic piece in the center of the electrolytic cell, and adjust the titanium electrodes (1 μm thick platinum coating) on ​​both sides to a distance of 15 cm. Pour a deionized water solution containing 0.3 mmol / L ascorbic acid (vitamin C) into the cell, ensuring the ceramic piece is completely submerged. Set the pulse power supply parameters:

[0060] The current is calculated based on the surface area of ​​the ceramic (example: 200 cm²). 2 (Surface area corresponds to 400mA current).

[0061] The pulse frequency is fixed at 5 cycles per second (5Hz).

[0062] The power-on time in each power-on cycle is 50% (i.e., power on for 0.1 seconds followed by power off for 0.1 seconds).

[0063] Step 4: Real-time temperature control

[0064] The temperature monitoring system (PT100 sensor) is activated. When the electrolyte temperature reaches 25.5℃, the thermoelectric cooler automatically starts. The cooling power is dynamically adjusted based on the difference between the actual temperature and the target temperature (25℃).

[0065] For every 1°C increase in temperature difference, the basic cooling capacity increases by 120W.

[0066] If the temperature difference persists, an additional 15W of compensation power will be added every minute to control the temperature fluctuation within ±0.5℃, thus preventing high temperatures from accelerating chemical reactions and damaging cultural relics.

[0067] Step 5: Gradient depressurization desalination operation

[0068] ① Primary permeation tank treatment: The ceramic vessel is moved into a 3.0 MPa salinity tank (28% artificial seawater solution) using a robotic arm, and the stage is started to rotate at a speed of 1 revolution per minute. At the same time, the bottom vortex generator (blade tilt angle 45°) is turned on to create turbulence in the liquid and enhance salt precipitation.

[0069] ② Concentration Monitoring and Transfer: A fiber optic sensor implanted in the ceramic matrix measures the internal chloride ion concentration every 30 seconds. When the decrease rate of the measured value is <0.1 mg / cm³ for three consecutive measurements... 3 At a rate of / h (approximately 48 hours), the robotic arm automatically moves it to the next stage 2.64MPa concentration tank (interstage pressure difference 12%).

[0070] ③ Cyclic processing: Repeat the above process until the fifth stage 0.1MPa tank, and record the salinity changes at each point throughout the process by the central controller.

[0071] Step 6: Dynamic Optimization with Artificial Intelligence

[0072] The central processing unit's neural network continuously analyzes sensor data:

[0073] 1. Press the ceramic piece 1cm apart. 3 The grid is divided into three-dimensional coordinates.

[0074] 2. Record the salinity value of each grid every 10 minutes to form a spatiotemporal matrix.

[0075] 3. Identify areas of salt retention using a feature recognition layer (e.g., identify areas with higher salinity at the spout).

[0076] 4. Output control commands:

[0077] Adjust the robotic arm to align the high-salt zone with the direction of strong turbulence.

[0078] Extend the current dwell time in the slot (up to a maximum of 72 hours).

[0079] Adjust the next step down gradient (e.g., change it from 12% to 10%).

[0080] Step 7: Freeze-drying stage control

[0081] First stage (pre-freezing): The ceramics are placed in a -32℃ freezer chamber and evacuated to 80Pa. This process is maintained for 4 hours to allow the moisture in the pores to freeze completely. The uniform temperature of the entire piece is then confirmed using an infrared thermal imager.

[0082] Second stage (sublimation): The temperature is increased to -18°C at a rate of 1°C per hour, and the pressure is adjusted to 60Pa. During this stage, the solid ice directly vaporizes. When the humidity sensor detects a sudden increase in humidity, the dehumidifier is activated. If the acoustic emission sensor detects high-frequency sound waves >40kHz (indicating the formation of microcracks), the heating rate is immediately reduced to 0.5°C / h.

[0083] Third stage (deep dehydration): Continue to increase the temperature to 28℃ at a rate of 2℃ / h, and reduce the pressure to 30Pa. When the weighing system detects a mass change of <0.1g for 2 consecutive hours (corresponding to a moisture content of 0.4%), terminate the drying process.

[0084] Step 8: By-product recycling and processing

[0085] The gases produced during electrolysis are treated separately:

[0086] Hydrogen recovery: The gas in the cathode area is collected by a titanium alloy cover and introduced into a 350℃ platinum-palladium catalyst reaction chamber, where it combines with oxygen to generate water vapor. The heat energy is recovered through copper heat pipes for preheating the inlet water.

[0087] Chlorine neutralization: A sodium thiosulfate solution (10% concentration) is introduced into the anode area, and the reaction produces non-toxic sodium sulfate and hydrochloric acid. The waste liquid is decomposed and reused by an electrolytic regeneration device.

[0088] Step 9: System Self-Check and Maintenance

[0089] After completing the processing of a single cultural relic, the following procedure will be followed (the following data has been tested):

[0090] 1. Membrane performance testing: Measure the ion-selective membrane resistance > 50 Ω·cm 2 Replace the film regularly.

[0091] 2. Mechanical calibration: Use a laser rangefinder to verify the electrode spacing error (must be < ±0.5mm).

[0092] 3. Data Update: Enter the desalination parameters and results into the database and train the neural network model.

[0093] 4. Safety test: Simulate voltage fluctuations to trigger fuse protection; response time must be <0.5 seconds.

[0094] Example 3: Comparison of Structural Damage Control Effects (Accelerated Aging Test)

[0095]

[0096] Example 4: Comparison of Process Stability (Fluctuation Range of Key Parameters)

[0097]

[0098] Example 5: Comparison of desalination efficiency (residual salt content / desalination cycle)

[0099]

[0100] Finally, the following points should be noted: First, in the description of this application, it should be noted that, unless otherwise specified and limited, the terms "installation", "connection", and "linkage" should be interpreted broadly, and can be mechanical or electrical connections, or internal connections between two components, or direct connections. "Up", "down", "left", "right", etc. are only used to indicate relative positional relationships. When the absolute position of the described object changes, the relative positional relationship may change.

[0101] Secondly: The accompanying drawings of the embodiments disclosed in this invention only involve the structures involved in the embodiments disclosed in this invention. Other structures can refer to the general design. In the absence of conflict, the same embodiment and different embodiments of this invention can be combined with each other.

[0102] In conclusion, the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for desalination protection of marine-exposed ceramic artifacts, characterized in that... Includes the following steps: (a) Multi-stage pretreatment: The ceramic is placed in a constant temperature environment of 5-15℃. First, 20-100W, 40kHz ultrasonic waves are used in conjunction with weakly alkaline deionized water with pH 7.0-7.5 to remove surface bio-attachments. Then, microfluidic technology is used to rinse the internal pores. Finally, the composition of the cleaning solution deposits is analyzed by a laser particle size analyzer. (b) Pulsed electrolytic desalination: A square-wave pulsed DC current with a current density of 0.5-5 mA / cm² is applied to an electric field constructed using a titanium-based platinum-plated electrode. 2 Frequency 1-10Hz, duty cycle 30%-70%, electrolyte is circulating deionized water containing 0.1-0.5mmol / L ascorbic acid, and ion-selective membrane isolates the anode and cathode regions; (c) Gradient pressure reduction: The ceramics are moved step by step in a 5-stage osmotic pressure tank, with the osmotic pressure gradually decreasing from 3.0 MPa to 0.1 MPa and the pressure difference decrease rate between adjacent stages ≤15%, and each stage is held for 12-72 hours; (d) Segmented freeze drying: The first stage is pre-freezing at -30℃ to -35℃ and 50-100Pa; the second stage is sublimation at -15℃ to -20℃ and 60-100Pa for 2-4 hours; and the third stage is dehydration at 25-30℃ and 10-50Pa until the moisture content is ≤0.5wt%. (d) Segmented freeze drying: The first stage is to pre-freeze the crystals at -30℃ to -35℃ and 50-100Pa. The second stage is to raise the temperature to -15℃ to -20℃ and maintain it for 2-4 hours to enhance water sublimation. The third stage is to deeply dehydrate at 25-30℃ and 10-50Pa until the water content is ≤0.5%.

2. The method for desalination protection of marine-exposed ceramic artifacts according to claim 1, characterized in that: The microjet technology described in step (a) uses a conical nozzle array with an outlet diameter of 0.1-0.3 mm, a jet pressure of 0.2-0.8 MPa, a water flow direction at an angle of 15-45° to the ceramic surface, and automatically switches the jet mode every 5 minutes of cleaning.

3. The method for desalination protection of marine-exposed ceramic artifacts according to claim 1, characterized in that: In step (b), an electrolyte temperature closed-loop control system is set up. When the electrolyte temperature is detected to be >25°C, the semiconductor cooling module is activated. The fluctuation control of ±1°C is achieved through the semiconductor cooling module and the PID temperature controller. At the same time, the inner wall of the electrolytic cell is coated with a nano titanium dioxide anti-corrosion coating.

4. The method for desalination protection of marine-exposed ceramic artifacts according to claim 1, characterized in that: In step (c), the ceramic is placed on a rotating platform with a rotation speed of 0.5-2 rpm. The surface of the platform is covered with a 3-5 mm silicone damping layer, and a vortex generator is installed at the bottom of each osmotic pressure tank to create a turbulent flow field with a Reynolds number of 2000-5000.

5. A desalination protection system for marine-exported ceramic artifacts, characterized in that... include: The pretreatment unit includes a constant temperature ultrasonic cleaning chamber, a microjet jet module, and a laser deposition analyzer; The electrolytic desalination unit includes an adjustable-spacing titanium-based platinum-plated electrode, a square-wave pulse power supply, and a circulating filtration system with an ion-selective membrane; The gradient depressurization unit includes a 5-stage osmotic pressure control tank and a rotating platform; The vacuum freeze-drying unit includes a three-stage temperature control system; The central control unit connects to the sensors in each unit and includes an optimization module, which is used to dynamically adjust the electrolysis parameters and the pressure reduction path based on salinity data.

6. The desalination protection system for marine-exported ceramic artifacts according to claim 5, characterized in that: During the electrolytic desalination and gradient depressurization process, micropores with a diameter of ≤0.8mm are implanted in the non-glazed area of ​​the ceramic using laser micro-drilling technology. A micro fiber optic sensor array is embedded inside the body to monitor Cl- concentration, pH value and stress changes in real time. After implantation, nanoscale silicon-based repair agent is used to seal the micropores. The linear thermal expansion coefficient of the repair body differs from that of the body body by ≤5%. The sensor data sampling frequency is ≥1 time / minute and is wirelessly transmitted to the central processor.

7. A desalination protection system for marine-exported ceramic artifacts according to claim 5, characterized in that: The central processing unit's built-in convolutional neural network algorithm predicts optimal process parameters based on a historical desalination database. This algorithm works when a local Cl- concentration gradient > 2 mg / cm³ is detected. 3 The robotic arm is triggered to adjust the orientation of the ceramic and a three-dimensional salinity distribution thermogram is generated in real time. The micro fiber optic sensor has a spatial resolution of <1mm and a sampling frequency of >1 time / minute.

8. A desalination protection system for marine-exported ceramic artifacts according to claim 5, characterized in that: The central control unit includes a fault diagnosis module that automatically executes a protection program when any of the following situations occur: the electrolytic cell voltage fluctuation is greater than 15% for more than 10 seconds, triggering the fuse protection and switching to the backup power supply; the concentration difference between the osmotic pressure cells deviates from the set value by more than 20%, triggering the automatic solution replenishment mechanism; the temperature change rate of the drying chamber is greater than 5℃ / min, activating the emergency heat preservation program. The solution replenishment mechanism is linked to the metering pump and the concentration sensor, with a flow control accuracy of ±0.5mL / s.

9. A desalination protection system for marine-exit ceramic artifacts according to claim 5, characterized in that: The electrolytic desalination unit is equipped with a byproduct recovery device. The cathode area is equipped with a hydrogen collection hood connected to a catalytic burner, and the anode area is equipped with a chlorine absorption tower containing 5-10% sodium thiosulfate solution. Combustion heat and reaction heat are recovered and utilized through a heat exchanger.

10. A desalination protection system for marine-exported ceramic artifacts according to claim 5, characterized in that: The system is equipped with a material compatibility testing module, including: a ceramic material spectral analysis probe in the pretreatment unit to automatically match cleaning parameters; a dielectric constant detector in the electrolytic desalination unit to dynamically optimize the electric field strength; and an acoustic emission sensor in the drying unit to monitor microcrack propagation signals in real time and adjust the drying curve.

Images