A response gel-based method and system for detecting chlorine ions in water-extracted ceramic cultural relics

Abstract

This invention discloses a method and system for detecting chloride ions in submerged ceramic artifacts based on responsive gels, belonging to the field of cultural relic protection technology. The method includes: preparing a topologically adaptive paper-cutting microstructure composite gel patch; mixing functional components into a prepolymer solution and then photocuring and laser-cutting to obtain a gel patch with a micro-cutting structure; pre-treating the surface of the submerged ceramic artifact to be tested, removing surface deposits and eliminating temperature differences to obtain a clean surface; applying the topologically adaptive paper-cutting microstructure composite gel patch to the surface of the artifact; acquiring fluorescence spectra of the chloride ion responsive gel patch, calculating the ratio of characteristic emission peak intensities to obtain the chloride ion concentration fluorescence response signal; utilizing a directional electric field to drive deep chloride ion migration, overcoming the bottleneck of low passive diffusion efficiency; and combining the relative change rate of the dynamic curve to achieve objective and accurate determination of the desalination endpoint, avoiding human error.

Description

Technical Field

[0001] This invention relates to the field of cultural relic protection technology, and in particular to a method and system for detecting chloride ions in excavated ceramic cultural relics based on responsive gel. Background Technology

[0002] As an important discovery in underwater archaeology, marine ceramic artifacts carry valuable information about trade and cultural exchange along the ancient Maritime Silk Road. However, after being immersed in seawater for hundreds of years, these artifacts have accumulated a large amount of soluble salts, mainly chlorides and sulfates, in their internal porous structure and at the interface between the glaze and the body. Studies have shown that the crystallization pressure generated by the "dissolution-recrystallization" cycle of soluble salts is the main cause of glaze peeling, body cracking, and even overall powdering of marine ceramic artifacts. Therefore, desalination has become the core link in the protection of marine ceramic artifacts. The accurate determination of the desalination endpoint is the key to ensuring the desalination effect and avoiding secondary damage to the artifacts during the protection process. At present, the determination of the desalination endpoint of marine ceramic artifacts mainly relies on the regular monitoring of the ion content or conductivity in the desalination soaking solution. When the conductivity of the soaking solution drops to a certain threshold or tends to stabilize, it is determined to be the desalination endpoint.

[0003] In terms of detection accuracy and anti-interference ability, existing technologies mostly use single-intensity fluorescence or electrochemical signals for characterization, which are easily affected by factors such as light source fluctuations, ambient background light, uneven gel thickness, and thermal diffusion caused by temperature differences on the surface of cultural relics, resulting in signal drift and making it difficult to achieve accurate quantitative analysis. In addition, in terms of the evaluation of the desalination process and the determination of the endpoint, current detection methods often focus on static concentration measurement and lack an effective monitoring mechanism for the dynamic process of ion migration. They usually rely on the subjective judgment of the operator's experience and lack objective and quantitative endpoint determination standards, which can easily lead to incomplete or excessive desalination, posing potential risks to the cultural relics themselves. Summary of the Invention

[0004] In view of the aforementioned existing problems, the present invention is proposed.

[0005] Therefore, this invention provides a method for detecting chloride ions in effluent ceramic artifacts based on responsive gels. This method addresses the issue of signal drift caused by factors such as light source fluctuations, ambient background light, uneven gel thickness, and thermal diffusion due to temperature differences on the artifact surface. These factors make accurate quantitative analysis difficult. Furthermore, current detection methods often focus on static concentration measurements and lack effective monitoring mechanisms for the dynamic process of ion migration in the assessment and endpoint determination of the desalination process. They typically rely on subjective judgment based on the operator's experience, lacking objective and quantitative endpoint determination standards. This can easily lead to incomplete or excessive desalination, posing potential risks to the artifact itself.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution: In a first aspect, the present invention provides a method for detecting chloride ions in water-exposed ceramic artifacts based on responsive gel, which includes preparing a topologically adaptive paper-cutting microstructure composite gel patch, mixing functional components into a prepolymer liquid and then photocuring and laser cutting to obtain a gel patch with a micro-cut structure. The surface of the ceramic artifact to be tested is pretreated to remove surface deposits and eliminate temperature differences, resulting in a clean surface of the artifact to be tested. The topology-adaptive paper-cutting microstructure composite gel patch is applied to the surface of the artifact to be tested. The micro-cut structure is used to unfold and achieve full adhesion and static adsorption to obtain a chloride ion responsive gel patch. Fluorescence spectra of the chloride ion responsive gel patch were acquired, and the ratio of the intensity of the characteristic emission peaks was calculated to obtain the chloride ion concentration fluorescence response signal. Based on the fluorescence response signal of chloride ion concentration, electrochemical-assisted acceleration is performed, and chloride ion migration is driven by the electrodialysis effect to obtain the dynamic curve of chloride ion concentration. The desalination endpoint is determined based on the dynamic curve of chloride ion concentration. When the signal change amplitude is less than a preset threshold, a desalination completion signal is obtained. The gel patch, once desalted, was peeled off and then soaked to regenerate it, restoring the fluorescence response signal to its initial state, thus obtaining a regenerated gel patch.

[0007] As a preferred embodiment of the method for detecting chloride ions in excavated ceramic artifacts based on responsive gel described in this invention, the preparation of the topologically adaptive paper-cutting microstructure composite gel patch involves mixing functional components into a prepolymer solution, followed by photocuring and laser cutting to obtain a gel patch with a micro-cut structure. The specific steps are as follows: Methacrylamide gelatin and acrylamide were used as matrix raw materials, and calixarene-modified europium complex fluorescent probes and layered double hydroxide nanoparticles were introduced as functional fillers. The components were uniformly dispersed in the solvent by high-speed stirring to form a functionalized prepolymer with shear thinning properties. The functionalized prepolymer liquid is injected into a flat mold, and an in-situ free radical polymerization reaction is initiated by ultraviolet light to crosslink and solidify the prepolymer liquid to form a self-supporting gel matrix with a three-dimensional network structure. A spiral array of micro-cuts was etched on the surface of the self-supporting gel substrate using laser micromachining technology, and a conductive polymer layer was deposited on one side of the gel substrate using a spin-coating process, thereby obtaining the topologically adaptive paper-cutting microstructure composite gel patch with topological deformation capability.

[0008] As a preferred embodiment of the chloride ion detection method for underwater ceramic artifacts based on responsive gel described in this invention, the specific steps of pre-treating the surface of the underwater ceramic artifact to be tested—removing surface deposits and eliminating temperature differences to obtain a clean surface of the artifact—are as follows: The area to be tested of the ceramic artifacts was dry-cleaned using a soft brush to remove loose calcium carbonate deposits and biological attachments on the surface. Then, the cleaned area was gently wiped with a degreased cotton swab soaked in deionized water to remove any residual dust. After cleaning, an infrared thermal imager is used to perform a full-field temperature scan on the surface of the artifact. If an abnormal temperature gradient is detected on the surface, the operation is paused until the surface temperature of the artifact reaches thermal equilibrium with the ambient temperature, thereby obtaining a clean and thermally stable surface of the artifact to be inspected.

[0009] As a preferred embodiment of the chloride ion detection method for underwater ceramic artifacts based on responsive gel described in this invention, the method involves applying the topologically adaptive paper-cutting microstructure composite gel patch to the surface of the artifact to be tested, utilizing the micro-cutting structure to achieve full adhesion and static adsorption, thereby obtaining a chloride ion responsive gel patch. The specific steps are as follows: The conductive polymer layer side of the topology adaptive paper-cutting microstructure composite gel patch is separated from the surface of the artifact to be tested, so that the micro-cutting array side is in contact with the surface of the artifact. By applying radial pressure, the spiral micro-incisions are guided to expand and extend geometrically, allowing the gel patch to conform to the complex curvature of the artifact surface and achieve seamless adhesion. When the patch is left to stand for a preset time in an adhered state, chloride ions on the surface of the artifact are actively captured by the ion exchange effect of layered double hydroxide nanoparticles in the gel network. At the same time, the calixarene-modified europium complex fluorescent probe specifically complexes with chloride ions, thereby obtaining the chloride ion-responsive gel patch whose fluorescence signal changes with the chloride ion concentration.

[0010] As a preferred embodiment of the method for detecting chloride ions in underwater ceramic artifacts based on responsive gel described in this invention, the specific steps for acquiring fluorescence spectra of the chloride ion responsive gel patch and calculating the ratio of characteristic emission peak intensities to obtain the chloride ion concentration fluorescence response signal are as follows: The chloride ion-responsive gel patch was irradiated with excitation light of a specific wavelength using a portable fluorescence spectrometer, and the intensity of the reference peak emitted by the gel patch was simultaneously acquired. and response peak intensity ; Based on the principle of host-guest chemical complexation equilibrium, a nonlinear mapping model between the fluorescence intensity ratio and chloride ion concentration was constructed. The collected reference peak intensity and response peak intensity Substitute chloride ion concentration fluorescence response signal The expression is: ; in, The fluorescence response signal represents the chloride ion concentration, characterizing the current chloride ion enrichment level within the gel. In response to the peak intensity, the emission intensity of the chloride ion complexed probe is... The reference peak intensity corresponds to the emission intensity of the free-state probe. This is the baseline response value under chlorine-free conditions. This represents the limiting response value under saturated adsorption conditions. is the dissociation constant of the probe and chloride ions. This represents the real-time concentration of chloride ions at the gel interface. The Hill coefficient is used to characterize the combined synergistic effect.

[0011] As a preferred embodiment of the method for detecting chloride ions in excavated ceramic artifacts based on responsive gel described in this invention, the steps of electrochemically assisted acceleration based on the fluorescence response signal of chloride ion concentration, driving chloride ion migration using the electrodialysis effect, and obtaining a dynamic curve of chloride ion concentration are as follows: A unidirectional pulse voltage is applied to the conductive polymer layer of the topologically adaptive paper-cutting microstructure composite gel patch to establish a directional electric field at the interface between the gel and the artifact. The electrodialysis effect is used to overcome the resistance to ion diffusion and drive the directional migration of chloride ions from the deep interior of the cultural relic to the gel layer. Combining Fick's diffusion law and electric field migration theory, a total flux calculation model for chloride ions at the gel-artifact interface is established, and the migration rate of chloride ions is calculated in real time based on the total flux calculation model. Plot the dynamic curve of chloride ion concentration reflecting the desalination process. The expression for the total flux calculation model is as follows: ; in, The total migration flux of chloride ions under electric field assistance The effective diffusion coefficient of chloride ions in the gel medium is given. This represents the concentration gradient of chloride ions along the migration path. The charge number of the chloride ion. It is Faraday's constant. The electromobility of chloride ions, This represents the real-time concentration of chloride ions. The intensity of the applied directional electric field, Let be the ideal gas constant. The absolute temperature of the environment.

[0012] As a preferred embodiment of the method for detecting chloride ions in effluent ceramic artifacts based on responsive gel described in this invention, the following steps are taken: Desalination endpoint determination is performed based on the dynamic curve of chloride ion concentration; when the signal change amplitude is less than a preset threshold, a desalination completion signal is obtained. The fluorescence response signal value at the current moment is obtained by sampling the dynamic curve of chloride ion concentration at equal time intervals. and the fluorescence response signal value at the previous sampling time. ; The relative rate of change of fluorescence response signal within two adjacent sampling periods is calculated as the basis for determining whether desalination has reached equilibrium. When the relative rate of change calculated multiple times is lower than the convergence threshold, the process of releasing chloride ions inside the cultural relic is determined to be over, and the desalination completion signal is generated. The expression for the relative rate of change is: ; in, This represents the rate of change in the desalination rate, used to quantify the convergence of the desalination process. This represents the fluorescence response signal value at the current moment. This represents the fluorescence response signal value at the previous sampling time.

[0013] Secondly, the present invention provides a chloride ion detection system for water-exposed ceramic artifacts based on responsive gel, comprising a gel preparation module, a surface pretreatment module, an adhesive adsorption module, a signal acquisition module, an electrochemical acceleration module, an endpoint determination module, and an adhesive patch regeneration module. The gel preparation module is used to prepare topology-adaptive paper-cutting microstructure composite gel patches. Functional components are mixed into a prepolymer liquid and then photocured and laser-cut to obtain gel patches with micro-cut structures. The surface pretreatment module is used to pretreat the surface of the ceramic artifact to be tested by water, remove surface deposits and eliminate temperature differences, so as to obtain a clean surface of the artifact to be tested. The adhesive adsorption module is used to apply the topology adaptive paper-cutting microstructure composite gel patch to the surface of the artifact to be tested, and to achieve full adhesion and static adsorption by using the micro-cut structure to obtain a chloride ion responsive gel patch. The signal acquisition module is used to acquire fluorescence spectra of the chloride ion responsive gel patch, calculate the ratio of characteristic emission peak intensities, and obtain the chloride ion concentration fluorescence response signal. The electrochemical acceleration module is used to perform electrochemical-assisted acceleration based on the fluorescence response signal of chloride ion concentration, and to drive chloride ion migration using the electrodialysis effect to obtain a dynamic curve of chloride ion concentration. The endpoint determination module is used to determine the desalination endpoint based on the chloride ion concentration dynamic curve. When the signal change amplitude is less than a preset threshold, a desalination completion signal is obtained. The patch regeneration module is used to peel off the gel patch that has been determined to have completed desalination and soak it for regeneration, so that the fluorescence response signal is restored to the initial state, and a regenerated gel patch is obtained.

[0014] Thirdly, the present invention provides a computer device including a memory and a processor, wherein the memory stores a computer program, wherein: when the computer program is executed by the processor, it implements any step of the method for detecting chloride ions in water-exposed ceramic artifacts based on responsive gel as described in the first aspect of the present invention.

[0015] Fourthly, the present invention provides a computer-readable storage medium having a computer program stored thereon, wherein: when the computer program is executed by a processor, it implements any step of the method for detecting chloride ions in water-exposed ceramic artifacts based on responsive gel as described in the first aspect of the present invention.

[0016] The beneficial effects of this invention are as follows: By preparing a topologically adaptive paper-cutting microstructure composite gel patch with a spiral micro-notch array, seamless full-fitting of the complex curved surface of the submerged ceramic artifacts is achieved by utilizing its geometric nonlinear deformation mechanism. Combined with the calixarene-modified europium complex fluorescent probe and layered double hydroxide nanoparticles in the functional components, the interference of temperature difference on ion migration is eliminated during application through mild surface pretreatment and thermal balance control. An electrochemical-assisted acceleration mechanism is introduced, and the deep chloride ion migration is driven by a directional electric field, breaking through the bottleneck of low passive diffusion efficiency. Furthermore, the objective and accurate determination of the desalination endpoint is achieved by combining the relative change rate of the dynamic curve, avoiding human error. Attached Figure Description

[0017] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the following description of the embodiments will be briefly introduced. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 This is a flowchart of the first embodiment of the chloride ion detection method for water-exposed ceramic artifacts based on responsive gel.

[0019] Figure 2 This is a schematic diagram of the chloride ion detection system for water-exposed ceramic artifacts based on responsive gel, according to the first embodiment.

[0020] Figure 3 This is a flowchart illustrating the preparation process of the chloride ion detection method for marine-exposed ceramic artifacts based on responsive gel, as described in the second embodiment. Figure 4 This is a schematic diagram illustrating the principle of the chloride ion detection method for marine-exposed ceramic artifacts based on responsive gel, as described in the second embodiment. Figure 5 A shows the TEM image and particle size distribution of N-CDs from the second embodiment. Figure 5 B shows the TEM image and particle size distribution of Ag@N-CDs from the second embodiment; Figure 6 XPS test results for N-CDs and Ag@N-CDs in the second embodiment (A: total spectrum, BE: fine spectrum of N,S-CDs, FJ: fine spectrum of Ag@N,S-CDs). Figure 7 Fluorescence spectra of N-CDs and Ag@N-CDs after the addition of chloride ions in the second embodiment; Figure 8 The fluorescence spectra of N-CDs at different concentrations in the second embodiment; Figure 9 A represents the fluorescence spectra of N-CDs from the second embodiment after adding different concentrations of Ag+. Figure 9 B is a graph showing the relationship between the fluorescence intensity ratio and concentration in the second embodiment; Figure 10 Fluorescence spectra of Ag@N-CDs in the second embodiment after adding different concentrations of Cl-; Figure 11 This is a practical application of Ag@N-CDs on the surfaces of two types of marine-excavated ceramic artifacts, as shown in the second embodiment. Detailed Implementation

[0021] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0022] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0023] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0024] Example 1, referring to Figures 1-2This is the first embodiment of the present invention, which provides a method for detecting chloride ions in excreted ceramic artifacts based on responsive gels, comprising the following steps: S1. Prepare a topology-adaptive paper-cutting microstructure composite gel patch by mixing functional components into a prepolymer solution and then photocuring and laser cutting to obtain a gel patch with a micro-cut structure.

[0025] Furthermore, methacrylamide gelatin and acrylamide are used as matrix raw materials, and calixarene-modified europium complex fluorescent probes and layered double hydroxide nanoparticles are introduced as functional fillers. The components are evenly dispersed in the solvent by high-speed stirring to form a functionalized prepolymer with shear thinning properties. Functionalized prepolymer liquid is injected into a flat mold, and in-situ free radical polymerization reaction is initiated by ultraviolet light, so that the prepolymer liquid crosslinks and solidifies to form a self-supporting gel matrix with a three-dimensional network structure. A spiral array of micro-cuts was etched on the surface of a self-supporting gel substrate using laser micromachining technology, and a conductive polymer layer was deposited on one side of the gel substrate using a spin-coating process, thereby obtaining a topologically adaptive paper-cutting microstructure composite gel patch with topological deformation capability.

[0026] It should be noted that by introducing paper-cutting microstructures, the gel patch possesses topological deformation capabilities, enabling it to adaptively conform to curved cultural relics. This solves the problem of poor adhesion of traditional planar patches to complex surfaces, thereby improving the reliability and applicability of the detection.

[0027] S2. Perform surface pretreatment on the area of ​​the ceramic artifact to be tested after it is submerged in water to remove surface deposits and eliminate temperature differences, so as to obtain a clean surface of the artifact to be tested.

[0028] Furthermore, a soft-bristled brush was used to dry clean the area of ​​the ceramic artifact to be tested, removing loose calcium carbonate deposits and biological attachments from the surface. Then, a degreased cotton swab soaked in deionized water was used to gently wipe the cleaned area to remove any residual dust. After cleaning, an infrared thermal imager is used to perform a full-field temperature scan on the surface of the artifact. If an abnormal temperature gradient is detected on the surface, the operation is paused until the surface temperature of the artifact reaches thermal equilibrium with the ambient temperature, thereby obtaining a clean and thermally stable surface of the artifact to be inspected.

[0029] It should be noted that the combination of dry cleaning and gentle wet wiping avoids potential damage to the artifacts from chemical reagents. At the same time, the use of an infrared thermal imager to monitor temperature balance eliminates the interference of temperature differences on subsequent ion migration detection, ensuring the accuracy of the detection data.

[0030] S3. Apply the topology-adaptive paper-cutting microstructure composite gel patch to the surface of the artifact to be tested, utilize the micro-cut structure to unfold and achieve full adhesion and static adsorption, and obtain a chloride ion responsive gel patch.

[0031] Furthermore, the conductive polymer layer side of the topology-adaptive paper-cutting microstructure composite gel patch is positioned away from the surface of the artifact to be tested, so that the micro-cut array side is in contact with the surface of the artifact. By applying radial pressure, the spiral micro-incisions are guided to expand and extend geometrically, allowing the gel patch to conform to the complex curvature of the artifact surface and achieve seamless adhesion. When the patch is left to stand for a preset time in a bonded state, chloride ions on the surface of the artifact are actively captured by the ion exchange of layered double hydroxide nanoparticles in the gel network. At the same time, the calixarene-modified europium complex fluorescent probe specifically complexes with chloride ions, thereby obtaining a chloride ion-responsive gel patch whose fluorescence signal changes with the chloride ion concentration.

[0032] It should be noted that by utilizing the geometric unfolding characteristics of the micro-incision structure, seamless adhesion between the gel patch and the surface of the artifact was achieved, avoiding detection blind spots caused by air bubbles and gaps. At the same time, the synergistic effect of the layered double hydroxide and the fluorescent probe enabled highly selective capture and response to chloride ions.

[0033] S4. Perform fluorescence spectral acquisition on the chloride ion responsive gel patch, calculate the ratio of characteristic emission peak intensities, and obtain the chloride ion concentration fluorescence response signal.

[0034] Furthermore, a portable fluorescence spectrometer was used to emit excitation light of a specific wavelength to irradiate a chloride ion-responsive gel patch, and the intensity of the reference peak emitted by the gel patch was simultaneously acquired. and response peak intensity ; Based on the principle of host-guest chemical complexation equilibrium, a nonlinear mapping model between the fluorescence intensity ratio and chloride ion concentration was constructed. The collected reference peak intensity and response peak intensity Substitute chloride ion concentration fluorescence response signal The expression is: ; in, The fluorescence response signal represents the chloride ion concentration, characterizing the current chloride ion enrichment level within the gel. In response to the peak intensity, the emission intensity of the chloride ion complexed probe is... The reference peak intensity corresponds to the emission intensity of the free-state probe. This is the baseline response value under chlorine-free conditions. This represents the limiting response value under saturated adsorption conditions. is the dissociation constant of the probe and chloride ions. This represents the real-time concentration of chloride ions at the gel interface. The Hill coefficient is used to characterize the combined synergistic effect.

[0035] It should be noted that the use of the bimodal ratio method for signal acquisition effectively eliminates interference from external factors such as ambient light and light source fluctuations, improving the stability and repeatability of the detection. At the same time, the nonlinear mapping model enables precise quantification of chloride ion concentration.

[0036] S5. Electrochemical-assisted acceleration is performed based on the fluorescence response signal of chloride ion concentration, and chloride ion migration is driven by the electrodialysis effect to obtain the dynamic curve of chloride ion concentration.

[0037] Furthermore, a unidirectional pulse voltage was applied to the conductive polymer layer of the topology-adaptive paper-cutting microstructure composite gel patch to establish a directional electric field at the interface between the gel and the artifact. The electrodialysis effect is used to overcome the resistance to ion diffusion and drive the directional migration of chloride ions from the deep interior of the cultural relic to the gel layer. Combining Fick's diffusion law and electric field migration theory, a total flux calculation model for chloride ions at the gel-artifact interface was established, and the migration rate of chloride ions was calculated in real time based on the total flux calculation model. Plot the dynamic curve of chloride ion concentration reflecting the desalination process. The expression for the total flux calculation model is as follows: ; in, The total migration flux of chloride ions under electric field assistance The effective diffusion coefficient of chloride ions in the gel medium is given. This represents the concentration gradient of chloride ions along the migration path. The charge number of the chloride ion. It is Faraday's constant. The electromobility of chloride ions, This represents the real-time concentration of chloride ions. The intensity of the applied directional electric field, Let be the ideal gas constant. The absolute temperature of the environment.

[0038] It should be noted that by accelerating chloride ion migration with electrochemical assistance, the desalination detection cycle is shortened and the detection efficiency is improved. At the same time, combined with the diffusion-migration coupling model, dynamic monitoring and quantitative characterization of the desalination process are realized.

[0039] S6. Desalination endpoint is determined based on the dynamic curve of chloride ion concentration. When the signal change amplitude is less than the preset threshold, a desalination completion signal is obtained.

[0040] Furthermore, the dynamic curve of chloride ion concentration is sampled at equal time intervals to obtain the fluorescence response signal value at the current moment. and the fluorescence response signal value at the previous sampling time. ; The relative rate of change of fluorescence response signal within two adjacent sampling periods is calculated as the basis for determining whether desalination has reached equilibrium. When the relative rate of change calculated multiple times is lower than the convergence threshold, the process of releasing chloride ions inside the cultural relic is determined to be over, and a desalination completion signal is generated. The expression for the relative rate of change is: ; in, This represents the rate of change in the desalination rate, used to quantify the convergence of the desalination process. This represents the fluorescence response signal value at the current moment. This represents the fluorescence response signal value at the previous sampling time.

[0041] It should be noted that the endpoint determination method based on relative change rate avoids the subjectivity of human judgment, achieves objective and accurate determination of the desalination endpoint, prevents over-desalination or under-desalination, and ensures the safety and effectiveness of cultural relic desalination treatment.

[0042] S7. Peel off the gel patch that has been determined to be desalted and soak it to regenerate it, so that the fluorescence response signal is restored to the initial state, and a regenerated gel patch is obtained.

[0043] Furthermore, after the desalination is completed, the gel patch is peeled off from the surface of the artifact and placed in a regeneration container filled with deionized water for immersion treatment. The immersion time is 45-90 minutes, and the deionized water is changed every 15 minutes to promote the dissociation and diffusion of chloride ions. The intensity of the response peaks of the gel patch was monitored using a fluorescence spectrometer during the regeneration process. Compared with reference peak intensity When the ratio of the two values ​​recovers to more than 95% of the initial baseline value, the regeneration is considered complete. The gel patch is then removed, dried, and sealed for reuse.

[0044] It should be noted that the reuse of gel patches through soaking regeneration reduces detection costs, while the fluorescence signal can be restored to its initial state, ensuring that the detection performance of the regenerated patch is comparable to that of the fresh patch, which has good economic efficiency and sustainability.

[0045] This embodiment also provides a chloride ion detection system for underwater ceramic artifacts based on responsive gel, including: a gel preparation module, a surface pretreatment module, an adhesive adsorption module, a signal acquisition module, an electrochemical acceleration module, an endpoint determination module, and an adhesive patch regeneration module; The gel preparation module is used to prepare topology-adaptive paper-cutting microstructure composite gel patches. Functional components are mixed into a prepolymer solution and then photocured and laser-cut to obtain gel patches with micro-cut structures. The surface pretreatment module is used to pretreat the surface of the ceramic artifacts to be tested after they come out of the water, remove surface deposits and eliminate temperature differences, so as to obtain a clean surface of the artifacts to be tested. The adhesive adsorption module is used to apply the topology-adaptive paper-cutting microstructure composite gel patch to the surface of the cultural relic to be tested. It utilizes the micro-cutting structure to achieve full adhesion and static adsorption, resulting in a chloride ion responsive gel patch. The signal acquisition module is used to acquire fluorescence spectra of chloride ion responsive gel patches, calculate the ratio of characteristic emission peak intensities, and obtain the chloride ion concentration fluorescence response signal. The electrochemical acceleration module is used for electrochemical-assisted acceleration based on the fluorescence response signal of chloride ion concentration. It utilizes the electrodialysis effect to drive chloride ion migration and obtains a dynamic curve of chloride ion concentration. The endpoint determination module is used to determine the desalination endpoint based on the dynamic curve of chloride ion concentration. When the signal change amplitude is less than the preset threshold, a desalination completion signal is obtained. The patch regeneration module is used to peel off the gel patch that has been determined to be desalted and soak it for regeneration, so that the fluorescence response signal is restored to the initial state, and a regenerated gel patch is obtained.

[0046] This embodiment also provides a computer device applicable to the chloride ion detection method for underwater ceramic artifacts based on responsive gel, comprising: a memory and a processor; the memory is used to store computer-executable instructions, and the processor is used to execute the computer-executable instructions to realize the chloride ion detection method for underwater ceramic artifacts based on responsive gel as proposed in the above embodiment.

[0047] The computer device can be a terminal, comprising a processor, memory, communication interface, display screen, and input devices connected via a system bus. The processor provides computing and control capabilities. The memory includes non-volatile storage media and internal memory. The non-volatile storage media stores the operating system and computer programs. The internal memory provides an environment for the operation of the operating system and computer programs stored in the non-volatile storage media. The communication interface is used for wired or wireless communication with external terminals; wireless communication can be achieved through Wi-Fi, carrier networks, NFC (Near Field Communication), or other technologies. The display screen can be an LCD screen or an e-ink screen. The input devices can be a touch layer covering the display screen, buttons, a trackball, or a touchpad on the computer device's casing, or an external keyboard, touchpad, or mouse.

[0048] This embodiment also provides a storage medium storing a computer program that, when executed by a processor, implements the method for detecting chloride ions in excreted ceramic artifacts based on responsive gels as proposed in the above embodiments. The storage medium can be implemented by any type of volatile or non-volatile storage device or a combination thereof, such as Static Random Access Memory (SRAM), Electrically Erasable Programmable Read-Only Memory (EEPROM), Erasable Programmable Read Only Memory (EPROM), Programmable Red-Only Memory (PROM), Read-Only Memory (ROM), magnetic storage, flash memory, magnetic disk, or optical disk.

[0049] In summary, this invention achieves seamless full adhesion to the complex curved surfaces of submerged ceramic artifacts by preparing a topologically adaptive paper-cutting microstructure composite gel patch with a spiral micro-notch array and utilizing its geometric nonlinear deformation mechanism. Combined with calixarene-modified europium complex fluorescent probes and layered double hydroxide nanoparticles in the functional components, the invention eliminates the interference of temperature difference on ion migration during application through mild surface pretreatment and thermal balance control. An electrochemical-assisted acceleration mechanism is introduced, using a directional electric field to drive deep chloride ion migration, overcoming the bottleneck of low passive diffusion efficiency. Furthermore, the invention achieves objective and accurate determination of the desalination endpoint by combining the relative change rate of the dynamic curve, avoiding human error.

[0050] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

[0051] Example 2, refer to Figures 3-11 This is the second embodiment of the present invention, which provides a method and system for detecting chloride ions in marine-exposed ceramic artifacts based on responsive gels, specifically including the following steps: Step 1: Preparation of N-CDs: 2.0000 g ammonium citrate and 0.1000 g thiourea were dissolved in 20.00 mL deionized water and stirred magnetically for 15 min. The mixture was then transferred to a reaction vessel and reacted at 200°C for 4 h to obtain a brownish-black solution. The solution emitted strong blue fluorescence under ultraviolet light. The solution was then dialyzed at 1000 Da for 24 h, with the dialysate being replaced every 2 h. After that, the solution was filtered through a 0.22 μm filter membrane and freeze-dried to obtain a black N-CDs powder sample.

[0052] Step 2: Preparation of Ag@N-CDs: The dried N-CDs powder sample was prepared into a 5 g / L solution, and an equal volume of 0.25 mol / L AgNO3 solution was added to quench it. After stirring evenly, the solution was allowed to stand for 1 h. The supernatant was then filtered and freeze-dried to obtain Ag@N-CDs powder sample.

[0053] Step 3: Gel preparation: Agarose gel was prepared according to the ratio of 1.5g agarose, 20g glycerol and 28.5g water, with Ag@N-CDs accounting for 0.5wt.%. First, the agarose, glycerol and water were stirred at 95°C to form a homogeneous sol. After cooling to 70°C, the Ag@N-CDs solution was added and stirred until homogeneous. The mixture was then poured into a preheated mold and cooled to set. Finally, it was refrigerated at 4°C to mature, resulting in a gel that exhibited extremely weak blue fluorescence under ultraviolet light.

[0054] Step 4: Testing the standard curve: Standard solutions containing different concentrations of chloride ions were prepared and added to a prepared 100 mg / L Ag@N-CDs solution. As the chloride ion concentration increased, the fluorescence intensity of Ag@N-CDs gradually increased, resulting in a series of fluorescence spectrum standard curves for different chloride ion concentrations.

[0055] 1 ml of standard chloride ion solutions of different concentrations were added to the gel and reacted for 5 min. The gel was then tested under a fluorescence spectrophotometer to obtain the fluorescence intensity curves of the gel corresponding to different chloride ion concentrations.

[0056] Step 5: Applying the gel: Apply Ag@N-CDs gel to the surface of the sample to be tested, add 1 ml of deionized water, wait 5 minutes, and then send the gel sample into a fluorescence spectrophotometer for testing. Compare the result with a standard curve to obtain the chloride ion content in the sample.

[0057] Compared with existing technologies, it has the following beneficial effects.

[0058] The chloride ion detection gel prepared by Ag@N-CDs in this invention has high sensitivity to Cl- in marine ceramic artifacts. When different ions (Na+, Mg2+, Ca2+, K+, NO3-, SO42-) are present at the same time, only Cl- can effectively enhance the fluorescence of Ag@N-CDs. This shows that the detection gel can accurately detect Cl- in marine ceramic artifacts and has high sensitivity and anti-interference ability.

[0059] When the chloride ion detection gel is used to detect the sample, it is detected by a fluorescence spectrophotometer. The greater the fluorescence intensity, the higher the chloride ion concentration.

[0060] Compared with conventional chloride ion detection methods, the detection gel can characterize the chloride ion concentration in the sample, the detection results are not affected by individual differences in human color perception, and it is non-destructive to the sample being tested, which is in line with the basic principles of cultural relic protection.

[0061] The testers can determine the chloride ion content inside the sample simply by comparing it with the standard concentration curve.

Claims

1. A method for detecting chloride ions in excreted ceramic artifacts based on responsive gels, characterized in that: include: To prepare a topology-adaptive paper-cutting microstructure composite gel patch, functional components were mixed into a prepolymer solution and then photocured and laser-cut to obtain a gel patch with a micro-cut structure. The surface of the ceramic artifact to be tested is pretreated to remove surface deposits and eliminate temperature differences, resulting in a clean surface of the artifact to be tested. The topology-adaptive paper-cutting microstructure composite gel patch is applied to the surface of the artifact to be tested. The micro-cut structure is used to unfold and achieve full adhesion and static adsorption to obtain a chloride ion responsive gel patch. Fluorescence spectra of the chloride ion responsive gel patch were acquired, and the ratio of the intensity of the characteristic emission peaks was calculated to obtain the chloride ion concentration fluorescence response signal. Based on the fluorescence response signal of chloride ion concentration, electrochemical-assisted acceleration is performed, and chloride ion migration is driven by the electrodialysis effect to obtain the dynamic curve of chloride ion concentration. The desalination endpoint is determined based on the dynamic curve of chloride ion concentration. When the signal change amplitude is less than a preset threshold, a desalination completion signal is obtained. The gel patch, once desalted, was peeled off and then soaked to regenerate it, restoring the fluorescence response signal to its initial state, thus obtaining a regenerated gel patch.

2. The method for detecting chloride ions in water-exposed ceramic artifacts based on responsive gel as described in claim 1, characterized in that: The preparation of the topology-adaptive paper-cutting microstructure composite gel patch involves mixing functional components into a prepolymer solution, followed by photocuring and laser cutting to obtain a gel patch with a micro-cut structure. The specific steps are as follows: Methacrylamide gelatin and acrylamide were used as matrix raw materials, and calixarene-modified europium complex fluorescent probes and layered double hydroxide nanoparticles were introduced as functional fillers. The components were uniformly dispersed in the solvent by high-speed stirring to form a functionalized prepolymer with shear thinning properties. The functionalized prepolymer liquid is injected into a flat mold, and an in-situ free radical polymerization reaction is initiated by ultraviolet light to crosslink and solidify the prepolymer liquid to form a self-supporting gel matrix with a three-dimensional network structure. A spiral array of micro-cuts was etched on the surface of the self-supporting gel substrate using laser micromachining technology, and a conductive polymer layer was deposited on one side of the gel substrate using a spin-coating process, thereby obtaining the topologically adaptive paper-cutting microstructure composite gel patch with topological deformation capability.

3. The method for detecting chloride ions in excreted ceramic artifacts based on responsive gel as described in claim 2, characterized in that: The surface pretreatment of the area to be tested of the unearthed ceramic artifact, which removes surface deposits and eliminates temperature differences, to obtain a clean surface of the artifact, involves the following steps: The area to be tested of the ceramic artifacts was dry-cleaned using a soft brush to remove loose calcium carbonate deposits and biological attachments on the surface. Then, the cleaned area was gently wiped with a degreased cotton swab soaked in deionized water to remove any residual dust. After cleaning, an infrared thermal imager is used to perform a full-field temperature scan on the surface of the artifact. If an abnormal temperature gradient is detected on the surface, the operation is paused until the surface temperature of the artifact reaches thermal equilibrium with the ambient temperature, thereby obtaining a clean and thermally stable surface of the artifact to be inspected.

4. The method for detecting chloride ions in water-exposed ceramic artifacts based on responsive gel as described in claim 3, characterized in that: The process involves applying the topology-adaptive paper-cutting microstructure composite gel patch to the surface of the artifact to be tested, utilizing the micro-incision structure to achieve full adhesion and static adsorption, resulting in a chloride ion-responsive gel patch. The specific steps are as follows: The conductive polymer layer side of the topology adaptive paper-cutting microstructure composite gel patch is separated from the surface of the artifact to be tested, so that the micro-cutting array side is in contact with the surface of the artifact. By applying radial pressure, the spiral micro-incisions are guided to expand and extend geometrically, allowing the gel patch to conform to the complex curvature of the artifact surface and achieve seamless adhesion. When the patch is left to stand for a preset time in an adhered state, chloride ions on the surface of the artifact are actively captured by the ion exchange effect of layered double hydroxide nanoparticles in the gel network. At the same time, the calixarene-modified europium complex fluorescent probe specifically complexes with chloride ions, thereby obtaining the chloride ion-responsive gel patch whose fluorescence signal changes with the chloride ion concentration.

5. The method for detecting chloride ions in water-exposed ceramic artifacts based on responsive gel as described in claim 4, characterized in that: The specific steps for acquiring fluorescence spectra of the chloride ion-responsive gel patch and calculating the ratio of characteristic emission peak intensities to obtain the chloride ion concentration fluorescence response signal are as follows: The chloride ion-responsive gel patch was irradiated with excitation light of a specific wavelength using a portable fluorescence spectrometer, and the intensity of the reference peak emitted by the gel patch was simultaneously acquired. and response peak intensity ; Based on the principle of host-guest chemical complexation equilibrium, a nonlinear mapping model between the fluorescence intensity ratio and chloride ion concentration was constructed. The collected reference peak intensity and response peak intensity Substitute chloride ion concentration fluorescence response signal The expression is: ; in, The fluorescence response signal represents the chloride ion concentration, characterizing the current chloride ion enrichment level within the gel. In response to the peak intensity, the emission intensity of the probe in the chloride ion complex state corresponds to... The reference peak intensity corresponds to the emission intensity of the free-state probe. This is the baseline response value under chlorine-free conditions. This represents the limiting response value under saturated adsorption conditions. is the dissociation constant of the probe and chloride ions. This represents the real-time concentration of chloride ions at the gel interface. The Hill coefficient is used to characterize the combined synergistic effect.

6. The method for detecting chloride ions in excreted ceramic artifacts based on responsive gel as described in claim 5, characterized in that: The electrochemical-assisted acceleration based on the chloride ion concentration fluorescence response signal, and the chloride ion migration driven by the electrodialysis effect, to obtain the chloride ion concentration dynamic curve, are specifically performed as follows: A unidirectional pulse voltage is applied to the conductive polymer layer of the topologically adaptive paper-cutting microstructure composite gel patch to establish a directional electric field at the interface between the gel and the artifact. The electrodialysis effect is used to overcome the resistance to ion diffusion and drive the directional migration of chloride ions from the deep interior of the cultural relic to the gel layer. Combining Fick's diffusion law and electric field migration theory, a total flux calculation model for chloride ions at the gel-artifact interface is established, and the migration rate of chloride ions is calculated in real time based on the total flux calculation model. Plot a dynamic curve of chloride ion concentration reflecting the desalination process. The expression for the total flux calculation model is as follows: ; in, The total migration flux of chloride ions under electric field assistance The effective diffusion coefficient of chloride ions in the gel medium is given. This represents the concentration gradient of chloride ions along the migration path. The charge number of the chloride ion. It is Faraday's constant. The electromobility of chloride ions, This represents the real-time concentration of chloride ions. The applied directional electric field strength, Let be the ideal gas constant. The absolute temperature of the environment.

7. The method for detecting chloride ions in water-exposed ceramic artifacts based on responsive gel as described in claim 6, characterized in that: The desalination endpoint is determined based on the dynamic curve of chloride ion concentration. When the signal change amplitude is less than a preset threshold, a desalination completion signal is obtained. The specific steps are as follows: The fluorescence response signal value at the current moment is obtained by sampling the dynamic curve of chloride ion concentration at equal time intervals. and the fluorescence response signal value at the previous sampling time. ; The relative rate of change of fluorescence response signal within two adjacent sampling periods is calculated as the basis for determining whether desalination has reached equilibrium. When the relative rate of change calculated multiple times is lower than the convergence threshold, the process of releasing chloride ions inside the cultural relic is determined to be over, and the desalination completion signal is generated. The expression for the relative rate of change is: ; in, This represents the rate of change in the desalination rate, used to quantify the convergence of the desalination process. This represents the fluorescence response signal value at the current moment. This represents the fluorescence response signal value at the previous sampling time.

8. A chloride ion detection system for underwater ceramic artifacts based on responsive gel, based on the chloride ion detection method for underwater ceramic artifacts based on responsive gel according to any one of claims 1 to 7, characterized in that: It includes a gel preparation module, a surface pretreatment module, an adhesive adsorption module, a signal acquisition module, an electrochemical acceleration module, an endpoint determination module, and an adhesive patch regeneration module; The gel preparation module is used to prepare topology-adaptive paper-cutting microstructure composite gel patches. Functional components are mixed into a prepolymer liquid and then photocured and laser-cut to obtain gel patches with micro-cut structures. The surface pretreatment module is used to pretreat the surface of the ceramic artifact to be tested by water, remove surface deposits and eliminate temperature differences, so as to obtain a clean surface of the artifact to be tested. The adhesive adsorption module is used to apply the topology adaptive paper-cutting microstructure composite gel patch to the surface of the artifact to be tested, and to achieve full adhesion and static adsorption by using the micro-cut structure to obtain a chloride ion responsive gel patch. The signal acquisition module is used to acquire fluorescence spectra of the chloride ion responsive gel patch, calculate the ratio of characteristic emission peak intensities, and obtain the chloride ion concentration fluorescence response signal. The electrochemical acceleration module is used to perform electrochemical-assisted acceleration based on the fluorescence response signal of chloride ion concentration, and to drive chloride ion migration using the electrodialysis effect to obtain a dynamic curve of chloride ion concentration. The endpoint determination module is used to determine the desalination endpoint based on the chloride ion concentration dynamic curve. When the signal change amplitude is less than a preset threshold, a desalination completion signal is obtained. The patch regeneration module is used to peel off the gel patch that has been determined to have completed desalination and soak it for regeneration, so that the fluorescence response signal is restored to the initial state, and a regenerated gel patch is obtained.

9. A computer device comprising a memory and a processor, wherein the memory stores a computer program, characterized in that: When the processor executes the computer program, it implements the steps of the method for detecting chloride ions in underwater ceramic artifacts based on responsive gel as described in any one of claims 1 to 7.

10. A computer-readable storage medium having a computer program stored thereon, characterized in that: When the computer program is executed by the processor, it implements the steps of the method for detecting chloride ions in water-exposed ceramic artifacts based on responsive gel as described in any one of claims 1 to 7.

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