An intelligent preparation method for anti-corrosion ceramics

Abstract

The present application relates to the technical field of ceramic preparation, and specifically to an intelligent preparation method for an anti-corrosion ceramic, the method comprising: pouring deionized water into a stirred reactor, sequentially adding fluorozirconic acid, nitric acid, ethanol; chromium trioxide; zirconium nitrate and sodium fluoride; reducing agent; ammonium molybdate and complexing agent; silane coupling agent and stirring to obtain an anti-corrosion ceramic. The present application aims to analyze whether chromium trioxide has reacted completely based on the two aspects of color change and temperature change, and then adjust the amount of ethanol added, control the stirring time, ensure the conversion of hexavalent chromium to trivalent chromium, and enhance the corrosion resistance of the film layer.

Description

Technical Field

[0001] The present application relates to the technical field of ceramic preparation, and in particular to an intelligent preparation method of an anti-corrosion ceramic. Background Art

[0002] The ceramic agent is mainly composed of zirconium salts, which can transform the metal surface at room temperature to form a dense monomolecular water-repellent film, enhance the bonding between the metal surface and the coating, and improve the anti-corrosion performance of the coating. Compared with the traditional phosphating process, the ceramic process has the characteristics of cost saving, simplified process, and room temperature treatment. The finished ceramic agent is usually made of zirconium salts and silane coupling agents. The chemical bonding between the finished ceramic agent and the metal surface is weak, and the film-forming quality is poor. Rusty metals may still rust and become dusty after ceramic treatment.

[0003] In the current ceramic preparation process, chromium trioxide and ethanol are reacted to introduce trivalent chromium to enhance the corrosion resistance of the film. However, the hexavalent chromium in chromium trioxide has a serious impact on the human body and the environment. The amount of ethanol added needs to be strictly controlled to ensure that the hexavalent chromium is completely converted into trivalent chromium. In the ceramic preparation process, the color change of the reaction between chromium trioxide and ethanol during stirring may not accurately reflect the actual consumption of chromium trioxide, which makes it difficult to judge when to stop stirring. Summary of the invention

[0004] In view of the above, it is necessary to provide an intelligent preparation method of an anti-corrosion ceramic agent to solve the above problems.

[0005] An embodiment of the present application provides an intelligent preparation method of an anti-corrosion ceramic agent, the method comprising:

[0006] S1: Obtain raw materials: fluorozirconic acid, nitric acid, ethanol, chromium trioxide, zirconium nitrate, sodium fluoride, reducing agent, ammonium molybdate, complexing agent, silane coupling agent and deionized water;

[0007] S2: Pour deionized water into a stirred reactor, add fluorozirconic acid, nitric acid, and ethanol, and stir for the first time;

[0008] S3: adding chromium trioxide into the stirred reactor and stirring for the second time until the chromium trioxide reacts completely, and stopping the second stirring;

[0009] The method for judging whether the chromium trioxide reaction is complete is:

[0010] S301: Acquire RGB images of the stirring reaction at each time after adding chromium trioxide and a stirring thermal imaging image;

[0011] S302: Evenly divide the stirring reaction RGB image at each moment to obtain a plurality of reaction regions; compare the chromaticity of all color channels of each reaction region at each moment with the standard reaction image, and combine the edge features and gradient features in the corresponding reaction region to obtain the chromaticity sufficiency of each reaction region at each moment;

[0012] S303: comprehensively analyzing the overall temperature changes of all reaction areas in the stirring thermal imaging image at consecutive moments and combining the change trend of the chromaticity sufficiency to obtain the possibility of reaction termination at each moment;

[0013] S304: Based on the possibility of reaction termination at each moment and the degree of chromaticity sufficiency of all regions at each moment, determining whether to stop the second stirring;

[0014] S4: pouring zirconium nitrate and sodium fluoride into the stirred reactor and stirring for the third time;

[0015] S5: adding a reducing agent into the stirred reactor to perform a fourth stirring;

[0016] S6: adding ammonium molybdate and complexing agent and stirring for the fifth time;

[0017] S7: Adding silane coupling agent to the stirred reactor and stirring for the last time to obtain an anti-corrosion ceramic agent.

[0018] The raw materials and their mass fractions are: fluorozirconic acid (8-14), nitric acid (3-6), ethanol (1-8), chromium trioxide (0.5-4), zirconium nitrate (3.5-7), sodium fluoride (0.5-1.5), reducing agent (4-7), ammonium molybdate (4-6), complexing agent (4.5-8), silane coupling agent (1-4), and the balance is deionized water.

[0019] The first stirring operation is as follows: the first stirring speed is 30 to 40 rpm and the time is 15 to 30 minutes.

[0020] The chromaticity sufficiency of each reaction area at each moment is obtained as follows:

[0021] Obtain a standard reaction RGB image, and use the chromaticity mean of the standard reaction RGB image on the R channel, G channel, and B channel to form a standard chromaticity vector;

[0022] The chromaticity mean of each reaction area in the stirring reaction RGB image at each moment in the three color channels is used to form the chromaticity vector of each reaction area at each moment; according to the difference between the chromaticity vector of each reaction area in the stirring reaction RGB image at each moment and the standard chromaticity vector, the chromaticity difference value of each reaction area at each moment is obtained;

[0023] Perform edge detection on each reaction area of ​​the stirring reaction RGB image at each moment, and obtain the chromaticity sufficiency of each reaction area at each moment according to the gradient value of the edge pixel point and the chromaticity difference value;

[0024] The chromaticity sufficiency is positively correlated with the fusion result of the gradient values ​​of all edge pixels in the corresponding reaction area, and negatively correlated with the chromaticity difference value.

[0025] The method for obtaining the reaction termination probability at each moment is specifically as follows:

[0026] Calculate the average temperature of all pixels in the corresponding stirring thermal imaging image of each reaction area at each moment; take each moment and a preset number of nearest moments before it as the neighborhood moment set of each moment;

[0027] The slope of the temperature mean of the nth reaction area at the tth time in the neighborhood is recorded as , the slope of the chromaticity sufficiency corresponding to the neighborhood time set of the nth reaction area at the tth time is recorded as , the possibility of reaction termination at the tth moment The formula form is: ;in, represents the normalized function; N represents the total number of reaction areas at the tth moment; Indicates that the adjustment parameter is preset to be greater than zero.

[0028] Wherein, the specific steps of determining whether to stop the second stirring are:

[0029] When the possibility of reaction termination at each moment and for a set number of consecutive moments is greater than a preset termination threshold, and the average value of the chromaticity sufficiency in all reaction areas at each moment is greater than or equal to the preset reaction threshold, the second stirring is stopped;

[0030] When the possibility of reaction termination at each moment and for a set number of consecutive moments is greater than a preset termination threshold, and the average value of the chromaticity sufficiency in all reaction areas at each moment is less than a preset reaction threshold, ethanol is added and stirring is continued;

[0031] Otherwise, continue stirring.

[0032] The third stirring is performed at a temperature of 55° C., a speed of 70 to 80 rpm, and a time of 20 to 30 minutes.

[0033] The reducing agent in S5 is specifically hydroxylamine hydrochloride, and the speed of the fourth stirring is controlled to be 50-60 rpm for 15-30 minutes.

[0034] Wherein, the complexing agent in S6 is specifically tartaric acid, and the speed of the fifth stirring is controlled to be 70-80 rpm for 40-50 minutes.

[0035] The silane coupling agent in S7 is specifically γ-aminopropyltriethoxysilane, and the speed of the last stirring is 50 to 60 rpm, and the stirred reactor is stirred for 30 to 50 minutes.

[0036] This application has at least the following beneficial effects:

[0037] The present application first obtains RGB images and thermal images during the reaction of chromium trioxide and ethanol; based on the color changes of the reactions of the two and the characteristics of the liquid after the reaction is complete, the chromaticity sufficiency is constructed, which has the beneficial effect of eliminating the interference of the color of the paddle stirring blade on the image chromaticity analysis when the mixed solution of chromium trioxide and ethanol is clear in the later stage of the reaction, which is easy to cause a large difference in the standard chromaticity of the reaction area, affecting the accurate assessment of the trivalent chromium content in the stirred reactor; based on the exothermic characteristics of the chromium trioxide reduction reaction, combined with the trend of temperature changes and chromaticity changes in the stirred reactor in adjacent moments, the possibility of reaction termination is constructed to avoid the problem that in the later stage of the reaction of chromium trioxide and ethanol, due to the significant reduction in the concentration of raw materials and the strong fluidity of the mixed solution, it is difficult to judge whether there is still tertiary chromium generated by the image chromaticity change alone, thereby improving the accuracy of the stirred reactor to control the stirring stop and the amount of ethanol re-dosing, ensuring that the hexavalent chromium is completely converted into trivalent chromium, and enhancing the corrosion resistance of the film layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 A flow chart of an intelligent preparation method of an anti-corrosion ceramic agent provided in this application;

[0039] Figure 2 Schematic diagram of the paddle stirring blade in the reaction area provided in this application;

[0040] Figure 3 A schematic diagram of the change in chromaticity sufficiency in the early stage of the reaction of chromium trioxide and ethanol provided in this application;

[0041] Figure 4 A schematic diagram of the change in chromaticity sufficiency in the late stage of the reaction of chromium trioxide and ethanol provided in this application;

[0042] Figure 5 A schematic diagram of the chromaticity change sequence of the nth reaction area provided in the present application in the early stage of the reaction of chromium trioxide and ethanol;

[0043] Figure 6 A schematic diagram of the chromaticity change sequence of the nth reaction area provided in the present application at the later stage of the reaction of chromium trioxide and ethanol;

[0044] Figure 7This is a flow chart for determining whether the chromium trioxide reaction is complete. DETAILED DESCRIPTION

[0045] In the description of the embodiments of the present application, words such as "exemplary", "or", "for example" and the like are used to indicate examples, illustrations or descriptions. Any embodiment or design described as "exemplary" or "for example" in the embodiments of the present application should not be interpreted as being more preferred or more advantageous than other embodiments or designs. Specifically, the use of words such as "exemplary", "or", "for example" and the like is intended to present related concepts in a concrete manner.

[0046] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art in the present application. The terms used in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application.

[0047] It should also be noted that the terms "first" and "second" in this application and its drawings are used to distinguish similar objects, rather than to describe a specific order or sequence. The method disclosed in the embodiments of the present application or the method shown in the flow chart includes one or more steps for implementing the method. Without departing from the scope of protection of this application, the execution order of multiple steps can be interchanged with each other, and some steps can also be deleted.

[0048] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

[0049] Example 1

[0050] Example 1 proposes an intelligent preparation method for an anti-corrosion ceramic agent, which is applied to the technical field of ceramic agent preparation. Figure 1 , the method comprises the following steps:

[0051] S1: The raw materials and their mass ratios in this embodiment are: fluorozirconic acid: nitric acid: ethanol: chromium trioxide: zirconium nitrate: sodium fluoride: reducing agent: ammonium molybdate: complexing agent: silane coupling agent: deionized water = 8:4:2:4:3.5:0.5:4:6:4.5:1:62.5.

[0052] S2: Pour deionized water into the stirred reactor, then add fluorozirconic acid, nitric acid and ethanol to perform the first stirring. In this embodiment, the first stirring speed is 30 rpm and the time is 30 minutes.

[0053] S3: adding chromium trioxide into the stirred reactor and stirring for the second time, and stopping the second stirring when the chromium trioxide reacts completely.

[0054] Chromium trioxide is put into a stirred reactor, and ethanol and chromium trioxide react in an acidic environment to generate trivalent chromium ( ), using trivalent chromium to replace hexavalent chromium ( ), greatly reducing the pollution to the environment. At the same time, the introduction of trivalent chromium can enhance the corrosion resistance of the film layer. The stirring speed was controlled at 50 rpm for the second time.

[0055] Among them, since hexavalent chromium trioxide is used in the preparation process of the ceramic agent, but the hexavalent chromium in the chromium trioxide is highly toxic and highly mobile, it will cause serious impacts on the human body and the environment. Therefore, the amount of ethanol added and the stirring stop time need to be adjusted in the ceramic agent preparation process to ensure that the chromium trioxide reacts completely.

[0056] S301: Acquire the stirring reaction RGB images and stirring thermal imaging images at each time after adding chromium trioxide.

[0057] The image acquisition device is located on the top wall of the reactor, and the image acquisition device is used to acquire images of the solution inside the stirred reactor, and simultaneously acquires the RGB image and thermal image of the stirred reaction of chromium trioxide and ethanol in an acidic environment, and the time interval for acquiring images is 10 seconds, and the two images acquired at each moment are bilaterally filtered to eliminate noise interference in the process preparation environment. It should be noted that the implementer can select appropriate methods for the time interval for acquiring images and for processing images according to actual conditions, and this application does not limit this.

[0058] S302: Evenly divide the stirring reaction RGB image at each moment to obtain a number of reaction areas; compare the chromaticity of all color channels of each reaction area at each moment with the standard reaction image, and combine the edge features and gradient features in the corresponding reaction area to obtain the chromaticity sufficiency of each reaction area at each moment.

[0059] Since the analysis of the stirring reaction RGB image at each moment is consistent, this application takes the t-th moment as an example and divides the stirring reaction RGB image into N reaction areas; the value in this embodiment is 15; the implementer can adjust the number of reaction areas according to actual conditions, and this application does not impose any restrictions on this.

[0060] When the dark red chromium trioxide ( ) When it is first put into the acidic ethanol solution, obvious red particles will appear. With stirring, the chromium trioxide gradually dissolves and makes the solution red. Then, with the oxidation process of ethanol, the chromium trioxide is reduced to trivalent chromium. The generated trivalent chromium is blue in the ethanol environment. The resulting mixture solution is dark blue and clear with uniform color.

[0061] In the stirring reaction RGB image, the closer the chromaticity of the reaction area is to the standard dark blue, the more hexavalent chromium is converted to trivalent chromium. The present application obtains an RGB image in which hexavalent chromium is converted to trivalent chromium by artificial selection as a standard reaction RGB image, and calculates the chromaticity mean of the standard reaction RGB image on the R channel, G channel, and B channel respectively to form a standard chromaticity vector. The chromaticity mean of each reaction area in the stirring reaction RGB image at each moment in the three color channels is used to form the chromaticity vector of each reaction area at each moment; the chromaticity difference value of each reaction area is obtained according to the difference between the chromaticity vector of each reaction area in the stirring reaction RGB image at each moment and the standard chromaticity vector.

[0062] It should be noted that, in this embodiment, the difference between vectors is measured by Euclidean distance.

[0063] It should be understood that the smaller the difference between the chromaticity vector of the reaction area and the standard chromaticity vector, the more likely the solution in the reaction area is to be dark blue, and the smaller the chromaticity difference value, the more hexavalent chromium is converted into trivalent chromium.

[0064] When hexavalent chromium is completely converted to trivalent chromium, the dark red solid chromium trioxide particles in the mixture solution are reacted and digested, and the mixture solution becomes clear. Since the paddle stirring blade is usually silver-gray, although the paddle stirring blade is in motion, the paddle stirring blade still has a high contrast compared with the mixture solution in the image, and the edge information of the paddle stirring blade can be obtained through the edge detection algorithm. The clearer the edge of the paddle stirring blade in the image, the greater the influence of the silver-gray paddle stirring blade on the image colorimetric analysis of the reaction area, and the more likely it is to cause a large difference in standard colorimetric, resulting in the problem of low colorimetric accuracy in analyzing the reaction results of chromium trioxide and ethanol. Among them, the schematic diagram of the paddle stirring blade in the reaction area is shown in the figure. Figure 2 As shown, 1 is a paddle-type stirring blade.

[0065] The RGB image of the stirring reaction at each moment is converted into a grayscale image and recorded as a stirring reaction grayscale image, wherein the grayscale conversion is a well-known technique and the specific process is not repeated here. Edge detection is performed on each reaction area of ​​the stirring reaction grayscale image at each moment, and the chromaticity sufficiency of each reaction area at each moment is obtained according to the gradient value of the edge pixel point and the chromaticity difference value; wherein the chromaticity sufficiency is positively correlated with the fusion result of the gradient values ​​of all edge pixel points of the corresponding reaction area and negatively correlated with the chromaticity difference value.

[0066] In this embodiment, for the stirring reaction grayscale image at the tth moment, the nth reaction area is used as the input of the Canny edge detection algorithm, each edge line of the nth reaction area is output, and the edge pixels on all edge lines are passed through the Sobel operator to calculate the gradient value of each edge pixel on the stirring reaction grayscale image; the chromaticity sufficiency of the nth reaction area is specifically: the variables are merged in the form of accumulation, that is, the cumulative sum of the gradient values ​​of all edge pixels in the nth reaction area is calculated, and the ratio of the cumulative sum of the nth reaction area to the chromaticity difference value is used as the chromaticity sufficiency of the nth reaction area; it should be noted that, in the process of calculating the ratio, in order to avoid the situation where the denominator is zero, it is necessary to add a preset value to the denominator, and the value is 0.01.

[0067] It should be understood that, when the result of fusion of the gradient value of all edge pixels in each reaction area is larger, it means that the visibility of the solution in the reaction area is higher, the solution is clearer, and the dark red chromium trioxide particles are more fully digested; when a paddle stirring blade appears in the reaction area, the overall chromaticity of the reaction area changes, so the paddle stirring blade has a more significant impact on the standard chromaticity difference; when the chromaticity difference value is smaller, it means that the degree of chromaticity reduction reaction in the reaction area of ​​the image is more sufficient, that is, the degree of chromaticity is greater.

[0068] S303: The overall temperature changes of all reaction areas in the stirring thermal imaging image at consecutive moments are integrated with the change trend of the chromaticity sufficiency to obtain the possibility of reaction termination at each moment.

[0069] In the early stage of the reaction between chromium trioxide and ethanol, the raw material concentration is high and the image chromaticity changes significantly, which can fully reflect that chromium trioxide is converted into trivalent chromium; in the later stage of the reaction between chromium trioxide and ethanol, the raw material concentration is greatly reduced, and with the rotation of the paddle stirring blade, the mixed solution has strong fluidity, and it is difficult to judge whether trivalent chromium is still generated by the image chromaticity change alone. At the same time, since the reaction between chromium trioxide and ethanol is an exothermic reaction that releases a lot of heat, when the image chromaticity change in the stirred reactor is small and the temperature change is small, the possibility of the termination of the reaction between chromium trioxide and ethanol is greater.

[0070] Among them, the schematic diagram of the change of chromaticity sufficiency in the early stage of the reaction between chromium trioxide and ethanol is as follows: Figure 3 As shown; Schematic diagram of the change in chromaticity in the late stage of the reaction between chromium trioxide and ethanol, as shown Figure 4 As shown. Figure 3 and Figure 4 In the figure, each square corresponds to a reaction area, each reaction area corresponds to a chromaticity sufficiency, and the value in the reaction area is the chromaticity sufficiency corresponding to the reaction area; the squares at the same position on the left and right sides of the arrow represent the chromaticity sufficiency of the same reaction area at different times; Figure 3In the early stage of the reaction, the chromaticity sufficiency of the same reaction area increases significantly over time, and the corresponding image chromaticity changes significantly; Figure 4 In the later stage of the reaction, the chromaticity sufficiency of the same reaction area increases slightly over time, and the chromaticity change in the corresponding image is small.

[0071] Since the pixels at the same position in the stirring reaction RGB image and the stirring reaction thermal imaging image have the same actual physical position, the stirring thermal imaging image at each moment can also be equally divided into N reaction areas. In this embodiment, the t-th moment is taken as an example for analysis: the t-th moment and the preset number of nearest moments before it are taken as the neighborhood moment set of the t-th moment. It should be noted that when t is less than 5, the t-th moment and all previous moments are selected as the neighborhood moment set of the t-th moment.

[0072] For the neighborhood time set at the tth moment, calculate the mean temperature of all pixels in the nth reaction area in the stirring thermal imaging image at each moment, and sort them in the order of the moments to form the temperature change sequence of the nth reaction area at the tth moment. Count the chromaticity sufficiency of the nth reaction area at each moment in the neighborhood time set at the tth moment, sort them in the order of the moments, and form the chromaticity change sequence of the nth reaction area at the tth moment.

[0073] in, Figure 5 This is a schematic diagram of the chromaticity change sequence of the nth reaction area in the early stage of the reaction between chromium trioxide and ethanol. Figure 6 Schematic diagram of the chromaticity change sequence of the nth reaction area in the later stage of the reaction between chromium trioxide and ethanol. Figure 5 and Figure 6 In the chromaticity change sequence, the horizontal axis is the serial number value corresponding to the chromaticity sufficiency of the nth reaction area in the time sequence, and the vertical axis is the chromaticity sufficiency of the nth reaction area at different times; Figure 5 It reflects that in the early stage of the reaction, as time goes by, the chromaticity change sequence of the nth reaction area shows a trend of obvious increase in the degree of chromaticity sufficiency; Figure 6 This reflects that in the later stage of the reaction, as time goes by, the change in the chromaticity sufficiency in the chromaticity change sequence of the nth reaction area is not obvious.

[0074] The temperature change sequence and chromaticity change sequence of the nth reaction area at the tth moment are used as the input of the Sen slope estimation algorithm in turn, and the slope of the temperature change sequence of the nth reaction area at the tth moment is output respectively. and the slope of the chromaticity change sequence , the possibility of reaction termination at the tth moment The formula form is: ;in, represents the normalized function; N represents the total number of reaction areas at the tth moment; Indicates that the adjustment parameter is preset to be greater than zero, and the value is 0.01 to prevent the denominator from being 0.

[0075] It should be understood that when the temperature change and image chromaticity of the reaction area at adjacent moments tend to be stable, that is, The smaller the value, the less likely it is that trivalent chromium will continue to be produced in the reaction area, and the reaction between chromium trioxide and ethanol is likely to terminate. The bigger.

[0076] S304: Based on the possibility of reaction termination at each moment and in combination with the chromaticity sufficiency of all regions at each moment, it is determined whether the chromium trioxide has reacted completely.

[0077] When the possibility of reaction termination for a set number of consecutive moments is greater than the preset termination threshold, the reaction of chromium trioxide and ethanol in the stirred reactor is terminated. The set number is 3, the termination threshold is 0.95, and the implementer can adjust it by himself. The preset termination threshold is greater than 0. However, when the amount of ethanol added is small, chromium trioxide fails to react completely. At this time, the temperature change and image chromaticity will also tend to be stable, and the possibility of reaction termination is also high. Therefore, there are two situations in which the reaction is terminated:

[0078] 1) When the average value of the chromaticity sufficiency in all reaction areas at each moment is greater than or equal to the preset reaction threshold, the trivalent chromium content in the stirred reactor is high, the chromium trioxide reduction reaction is extremely sufficient, and no additional ethanol is needed, and the stirred reactor stops stirring.

[0079] 2) When the average value of the chromaticity sufficiency in all reaction areas at each moment is less than the preset reaction threshold, it indicates that the content of trivalent chromium in the stirred reactor is relatively low and the reduction reaction of chromium trioxide is incomplete; the preset reaction threshold is 0.85, which can be adjusted by the implementer, and the preset reaction threshold is greater than 0.

[0080] To ensure all All are converted into trivalent chromium, and additional ethanol needs to be added for reaction. The specific formula for the amount of ethanol to be added is: ; In the formula, is the amount of ethanol added at the tth moment, is the reaction threshold, is the mean value of the chromaticity sufficiency of all reaction areas at the tth moment, is the initial dosage of ethanol. It should be understood that when The larger the value is, the more hexavalent chromium in the stirred reactor has not been completely converted into trivalent chromium. After adding ethanol, stirring is continued until the average value of the chromaticity sufficiency in all reaction areas is greater than or equal to the reaction threshold value, and stirring of the stirred tank reactor is stopped.

[0081] Among them, the judgment flow chart of the complete reaction of chromium trioxide is as follows: Figure 7 shown.

[0082] S4: Pour zirconium nitrate and sodium fluoride into the stirred reactor for a third stirring, and control the temperature of the stirred reactor to 55° C. to improve the dissolution efficiency. In this embodiment, the third stirring speed is 70 rpm and the time is 30 minutes.

[0083] S5: Continue to add reducing agent into the stirred reactor for the fourth stirring. In this embodiment, hydroxylamine hydrochloride is used as the reducing agent to ensure that chromium trioxide is reduced to trivalent chromium. In this embodiment, the speed of the fourth stirring is 50 rpm and the time is 30 minutes.

[0084] S6: Control the temperature of the stirred reactor to 30° C., add ammonium molybdate and a complexing agent for the fifth stirring, wherein the complexing agent in this embodiment is tartaric acid. In this embodiment, the speed of the fifth stirring is 70 rpm and the time is 50 minutes.

[0085] S7: Add silane coupling agent to the stirred reactor for the last stirring, wherein in this embodiment, γ-aminopropyl triethoxysilane (silane coupling agent KH-550) is used to prepare an anti-corrosion ceramic agent. In this embodiment, the last stirring speed is 50 rpm and the time is 50 minutes.

[0086] Example 2

[0087] Example 2 proposes an intelligent preparation method for an anti-corrosion ceramic agent, which is applied to the technical field of ceramic agent preparation. Figure 1 , the method comprises the following steps:

[0088] S1: The raw materials and their mass ratios in this embodiment are: fluorozirconic acid: nitric acid: ethanol: chromium trioxide: zirconium nitrate: sodium fluoride: reducing agent: ammonium molybdate: complexing agent: silane coupling agent: deionized water = 14:6:1:0.5:3.5:1.5:7:4:8:4:50.5.

[0089] S2: Pour deionized water into the stirred reactor, then add fluorozirconic acid, nitric acid and ethanol to perform the first stirring. In this embodiment, the speed of the first stirring is 36 rpm and the time is 24 minutes.

[0090] S3: adding chromium trioxide into the stirred reactor for a second stirring, and stopping the second stirring until the chromium trioxide reacts completely. The second stirring speed is controlled to be 55 rpm, and the same method as in Example 1 is used to determine whether the chromium trioxide reacts completely.

[0091] S4: Pour zirconium nitrate and sodium fluoride into the stirred reactor for a third stirring, and control the temperature of the stirred reactor to 55° C. to improve the dissolution efficiency. In this embodiment, the third stirring speed is 75 rpm and the time is 25 minutes.

[0092] S5: Continue to add reducing agent into the stirred reactor for the fourth stirring. In this embodiment, hydroxylamine hydrochloride is used as the reducing agent to ensure that chromium trioxide is reduced to trivalent chromium. In this embodiment, the speed of the fourth stirring is 60 rpm and the time is 15 minutes.

[0093] S6: The temperature of the stirred reactor is controlled at 30° C., and ammonium molybdate and a complexing agent are added for the fifth stirring, wherein the complexing agent in this embodiment is tartaric acid. In this embodiment, the speed of the fifth stirring is 75 rpm and the time is 48 minutes.

[0094] S7: Add silane coupling agent to the stirred reactor for the last stirring, wherein in this embodiment, γ-aminopropyl triethoxysilane (silane coupling agent KH-550) is used to prepare an anti-corrosion ceramic agent. In this embodiment, the last stirring speed is 55 rpm and the time is 45 minutes.

[0095] Example 3

[0096] Example 3 proposes an intelligent preparation method for an anti-corrosion ceramic agent, which is applied to the technical field of ceramic agent preparation. Figure 1 , the method comprises the following steps:

[0097] S1: The raw materials and their mass ratios in this embodiment are: fluorozirconic acid: nitric acid: ethanol: chromium trioxide: zirconium nitrate: sodium fluoride: reducing agent: ammonium molybdate: complexing agent: silane coupling agent: deionized water = 10:3:8:4:7:1:6:6:8:2:45.

[0098] S2: Pour deionized water into the stirred reactor, then add fluorozirconic acid, nitric acid and ethanol to perform the first stirring. In this embodiment, the first stirring speed is 40 rpm and the time is 15 minutes.

[0099] S3: adding chromium trioxide into the stirred reactor for a second stirring, and stopping the second stirring until the chromium trioxide reacts completely. The second stirring speed is controlled to be 60 rpm, and the same method as in Example 1 is used to determine whether the chromium trioxide reacts completely.

[0100] S4: Pour zirconium nitrate and sodium fluoride into the stirred reactor for a third stirring, and control the temperature of the stirred reactor to 55° C. to improve the dissolution efficiency. In this embodiment, the third stirring speed is 80 rpm and the time is 20 minutes.

[0101] S5: Continue to add reducing agent into the stirred reactor for the fourth stirring. In this embodiment, hydroxylamine hydrochloride is used as the reducing agent to ensure that chromium trioxide is reduced to trivalent chromium. In this embodiment, the speed of the fourth stirring is 60 rpm and the time is 30 minutes.

[0102] S6: Control the temperature of the stirred reactor to 30° C., add ammonium molybdate and a complexing agent to carry out the fifth stirring, wherein the complexing agent in this embodiment is tartaric acid. In this embodiment, the speed of the fifth stirring is 80 rpm and the time is 40 minutes.

[0103] S7: Add silane coupling agent to the stirred reactor for the last stirring, wherein in this embodiment, γ-aminopropyl triethoxysilane (silane coupling agent KH-550) is used to prepare an anti-corrosion ceramic agent. In this embodiment, the last stirring speed is 60 rpm and the time is 30 minutes.

[0104] The present application provides an intelligent preparation method for an anti-corrosion ceramic agent, the method comprising: firstly obtaining an RGB image and a thermal imaging image during the reaction of chromium trioxide and ethanol; constructing a chromaticity sufficiency based on the color change of the reaction of the two and the characteristics of the liquid after the reaction is complete, wherein the beneficial effect is to eliminate the interference of the color of the paddle stirring blade on the image chromaticity analysis when the mixture solution of chromium trioxide and ethanol is clear in the late stage of the reaction, which easily leads to a large standard chromaticity difference in the reaction area, affecting the accurate evaluation of the trivalent chromium content in the stirred reactor; based on the exothermic characteristics of the chromium trioxide reduction reaction, combined with the trend of temperature change and chromaticity change in the stirred reactor at adjacent moments, the possibility of reaction termination is constructed, and the problem of being difficult to judge whether there is still tertiary chromium generated by the image chromaticity change alone is avoided in the late stage of the reaction of chromium trioxide and ethanol due to the significant reduction in the raw material concentration and the strong fluidity of the mixture solution. The stirring reactor is further improved in terms of the accuracy of controlling the stirring stop and the amount of ethanol re-dosing, ensuring that the hexavalent chromium is completely converted into trivalent chromium, and enhancing the corrosion resistance of the film layer.

[0105] The flowchart and block diagram in the accompanying drawings show the possible architecture, function and operation of the system, method and computer program product according to the embodiment of the present application. In this regard, each box in the flowchart or block diagram can represent a module, a program segment or a part of the code, and the module, the program segment or a part of the code contains one or more executable instructions for realizing the specified logical function. In some alternative implementations, the function marked in the box can also occur in a different order from the order marked in the accompanying drawings. For example, two continuous boxes can actually be executed substantially in parallel, and they can sometimes be executed in the opposite order, which can depend on the functions involved. In the description corresponding to the flowchart and the block diagram in the accompanying drawings, the operations or steps corresponding to different boxes can also occur in a different order from the order disclosed in the description, and sometimes there is no specific order between different operations or steps. For example, two continuous operations or steps can actually be executed substantially in parallel, and they can sometimes be executed in the opposite order, which can depend on the functions involved. Each block in the block diagrams and / or flowcharts, and combinations of blocks in the block diagrams and / or flowcharts, may be implemented by a dedicated hardware-based system that performs the specified functions or actions, or may be implemented by a combination of dedicated hardware and computer instructions.

[0106] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application, and should all be included in the protection scope of the present application.

Claims

1. An intelligent preparation method of an anti-corrosion ceramic agent, characterized in that: The method comprises the following steps: S1: Obtain raw materials: fluorozirconic acid, nitric acid, ethanol, chromium trioxide, zirconium nitrate, sodium fluoride, reducing agent, ammonium molybdate, complexing agent, silane coupling agent and deionized water; S2: Pour deionized water into a stirred reactor, add fluorozirconic acid, nitric acid, and ethanol, and stir for the first time; S3: adding chromium trioxide into the stirred reactor and stirring for the second time until the chromium trioxide reacts completely, and stopping the second stirring; The method for judging whether the chromium trioxide reaction is complete is: S301: Acquire RGB images of the stirring reaction at each time after adding chromium trioxide and a stirring thermal imaging image; S302: Evenly divide the stirring reaction RGB image at each moment to obtain a plurality of reaction regions; compare the chromaticity of all color channels of each reaction region at each moment with the standard reaction image, and combine the edge features and gradient features in the corresponding reaction region to obtain the chromaticity sufficiency of each reaction region at each moment; S303: comprehensively analyzing the overall temperature changes of all reaction areas in the stirring thermal imaging image at consecutive moments and combining the change trend of the chromaticity sufficiency to obtain the possibility of reaction termination at each moment; S304: Based on the possibility of reaction termination at each moment and the degree of chromaticity sufficiency of all regions at each moment, determining whether to stop the second stirring; S4: pouring zirconium nitrate and sodium fluoride into the stirred reactor and stirring for the third time; S5: adding a reducing agent into the stirred reactor to perform a fourth stirring; S6: adding ammonium molybdate and complexing agent and stirring for the fifth time; S7: Adding silane coupling agent to the stirred reactor and stirring for the last time to obtain an anti-corrosion ceramic agent.

2. The intelligent preparation method of an anti-corrosion ceramic agent according to claim 1, characterized in that: The raw materials and their mass fractions are: 8-14 of fluorozirconic acid, 3-6 of nitric acid, 1-8 of ethanol, 0.5-4 of chromium trioxide, 3.5-7 of zirconium nitrate, 0.5-1.5 of sodium fluoride, 4-7 of reducing agent, 4-6 of ammonium molybdate, 4.5-8 of complexing agent, 1-4 of silane coupling agent, and the balance is deionized water.

3. The intelligent preparation method of an anti-corrosion ceramic agent according to claim 1, characterized in that: The specific operation of the first stirring is: the first stirring speed is 30 to 40 revolutions per minute, and the time is 15 to 30 minutes.

4. The intelligent preparation method of an anti-corrosion ceramic agent according to claim 1, characterized in that: The chromaticity sufficiency of each reaction area at each moment is obtained as follows: Obtain a standard reaction RGB image, and use the chromaticity mean of the standard reaction RGB image on the R channel, G channel, and B channel to form a standard chromaticity vector; The chromaticity mean of each reaction area in the stirring reaction RGB image at each moment in the three color channels is used to form the chromaticity vector of each reaction area at each moment; according to the difference between the chromaticity vector of each reaction area in the stirring reaction RGB image at each moment and the standard chromaticity vector, the chromaticity difference value of each reaction area at each moment is obtained; Perform edge detection on each reaction area of ​​the stirring reaction RGB image at each moment, and obtain the chromaticity sufficiency of each reaction area at each moment according to the gradient value of the edge pixel point and the chromaticity difference value; The chromaticity sufficiency is positively correlated with the fusion result of the gradient values ​​of all edge pixels in the corresponding reaction area, and negatively correlated with the chromaticity difference value.

5. The intelligent preparation method of an anti-corrosion ceramic agent according to claim 1, characterized in that: The reaction termination probability at each moment is obtained as follows: Calculate the average temperature of all pixels in the corresponding stirring thermal imaging image of each reaction area at each moment; take each moment and a preset number of nearest moments before it as the neighborhood moment set of each moment; The slope of the temperature mean of the nth reaction area at the tth time in the neighborhood is recorded as , the slope of the chromaticity sufficiency corresponding to the neighborhood time set of the nth reaction area at the tth time is recorded as , the possibility of reaction termination at the tth moment The formula form is: ;in, represents the normalized function; N represents the total number of reaction areas at the tth moment; Indicates that the adjustment parameter is preset to be greater than zero.

6. The intelligent preparation method of an anti-corrosion ceramic agent according to claim 1, characterized in that: The specific steps of determining whether to stop the second stirring are: When the possibility of reaction termination at each moment and for a set number of consecutive moments is greater than a preset termination threshold, and the average value of the chromaticity sufficiency in all reaction areas at each moment is greater than or equal to the preset reaction threshold, the second stirring is stopped; When the possibility of reaction termination at each moment and for a set number of consecutive moments is greater than a preset termination threshold, and the average value of the chromaticity sufficiency in all reaction areas at each moment is less than a preset reaction threshold, ethanol is added and stirring is continued; Otherwise, continue stirring.

7. The intelligent preparation method of an anti-corrosion ceramic agent according to claim 1, characterized in that: The third stirring is performed at a temperature of 55° C., a speed of 70 to 80 rpm, and a time of 20 to 30 minutes.

8. The intelligent preparation method of an anti-corrosion ceramic agent according to claim 1, characterized in that: The reducing agent in S5 is specifically hydroxylamine hydrochloride, and the speed of the fourth stirring is controlled to be 50-60 rpm for 15-30 minutes.

9. The intelligent preparation method of an anti-corrosion ceramic agent according to claim 1, characterized in that: The complexing agent in S6 is specifically tartaric acid, and the speed of the fifth stirring is controlled to be 70-80 rpm for 40-50 minutes.

10. The intelligent preparation method of an anti-corrosion ceramic agent according to claim 1, characterized in that: The silane coupling agent in S7 is specifically γ-aminopropyltriethoxysilane. The speed of the last stirring is 50 to 60 rpm, and the stirred reactor is stirred for 30 to 50 minutes.

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