A copper ion detection solution, method, device, computer equipment and storage medium

Abstract

The application belongs to the technical field of chemical detection, and discloses a copper ion detection liquid, a method, a device, computer equipment and a storage medium.The copper ion detection liquid comprises: dilution special pure water, potassium chloride and isopropyl alcohol; and the parameters of the dilution special pure water are: conductivity < 10 mu s / cm, solid suspended substance < 5.0 mg / L and pH is 4.5-5.5.The application provides more suitable acidity, total ion strength and ion background for EDTA titration analysis of copper ion concentration by using dilution special pure water, potassium chloride and isopropyl alcohol, so that the stability and accuracy of copper ion detection can be improved.

Description

Technical Field

[0001] This invention belongs to the field of chemical detection technology and discloses a copper ion detection solution, method, apparatus, computer equipment, and storage medium. Background Technology

[0002] Niobium-titanium and niobium-tin superconducting materials are widely used in large-scale scientific research equipment such as nuclear magnetic resonance imaging (MRI), high-frequency nuclear magnetic resonance spectrometers (NMR), high magnetic field devices, mass spectrometers, and particle accelerators. During the processing of superconducting materials, copper / niobium needs to achieve a metallurgical bond, and as processing progresses, the dimensions change towards the micrometer scale. Therefore, the cleanliness of the oxygen-free copper surface before assembly is crucial. The cleanliness of the oxygen-free copper surface is ensured through controlled cleaning processes. Oxygen-free copper is cleaned with nitric acid solution; as the cleaning process continues, the concentration of copper ions in the acid gradually increases, and the corrosion efficiency of the solution gradually decreases. Accurate analysis of the copper ion concentration in the solution, guiding solution replacement, is a necessary condition and an essential requirement for ensuring the cleaning quality of the oxygen-free copper surface.

[0003] There are two main methods for analyzing copper ion concentration: atomic absorption spectrophotometry and EDTA complexometric titration. Atomic absorption spectrophotometry is highly dependent on equipment and has a complex analytical process involving solution pretreatment, resulting in a long timeframe from sampling to obtaining the detection results. EDTA complexometric titration has a relatively shorter analysis timeframe, but it places high demands on measurement conditions such as the ionic background and acidity of the solution. Therefore, there is a need to further improve the stability and accuracy of copper ion detection. Summary of the Invention

[0004] To overcome the problems of existing technologies, this invention provides a copper ion detection solution, method, apparatus, computer equipment, and storage medium. This invention provides a more suitable acidity, total ionic strength, and ionic background for EDTA titration analysis of copper ion concentration by diluting with dedicated pure water, potassium chloride, and isopropanol, thereby improving the stability and accuracy of copper ion detection.

[0005] On one hand, the present invention relates to a copper ion detection solution for detecting copper ion concentration by EDTA complexometric titration, comprising: EDTA standard solution and PAN indicator, and further comprising: dilution-specific pure water, potassium chloride, and isopropanol;

[0006] The parameters of the dilution-specific pure water are: conductivity <10μs / cm, suspended solids <5.0mg / L, and pH 4.5–5.5;

[0007] The dilution-specific pure water includes pure water and hydrochloric acid.

[0008] Furthermore, in the copper ion detection solution provided by the present invention, the amount of potassium chloride added is 2-3 g / L, and the amount of isopropanol added is 1-2 mL / L.

[0009] Furthermore, in the copper ion detection solution provided by the present invention, the concentration of the EDTA standard solution is 0.01 mol / L.

[0010] Furthermore, in the copper ion detection solution provided by the present invention, hydrochloric acid is added to pure water with a conductivity of <1μs / cm and a pH of 6.5 to 7.5 to obtain the dilution-specific pure water.

[0011] On the other hand, the present invention relates to a method for detecting copper ions, which uses the aforementioned copper ion detection solution to detect the copper ion content in the test solution.

[0012] Furthermore, the copper ion detection method provided by the present invention includes: diluting the test solution (strongly acidic, pH≤0.5) to a pH of 2.2-4.0 with the dilution-specific pure water, and then sequentially adding the potassium chloride and the isopropanol, stirring and mixing evenly during the sequential addition process to obtain the diluted test solution;

[0013] Then the PAN indicator is added, and the diluted test solution changes from light blue to pinkish-purple;

[0014] Add the EDTA standard solution dropwise until the color of the diluted test solution changes from pinkish-purple to light yellowish-green, then stop adding the solution.

[0015] The concentration of copper ions in the test solution is determined based on the volume of the test solution, the dilution ratio of the test solution, the amount of EDTA standard solution added, and the concentration of the EDTA standard solution.

[0016] On the other hand, the present invention relates to a copper ion detection device, comprising:

[0017] A storage structure is provided for storing at least one of EDTA standard solution, PAN indicator, dilution-specific pure water, potassium chloride, and isopropanol; the parameters of the dilution-specific pure water are: conductivity <10μs / cm, suspended solids <5.0mg / L, and pH 4.5-5.5; the dilution-specific pure water includes pure water and hydrochloric acid.

[0018] The reaction structure is used for the reaction of the test solution with the EDTA standard solution; before the test solution reacts with the EDTA standard solution, the test solution is diluted with the special dilution pure water to a pH of 2.2-4.0, and then potassium chloride, isopropanol, and PAN indicator are added;

[0019] An injection structure for adding the EDTA standard solution dropwise to the reaction structure;

[0020] A color recognition structure is used to identify color changes in the liquid within the reaction structure;

[0021] The detection structure is used to determine the concentration of copper ions in the test solution based on the volume of the test solution, the dilution ratio of the test solution, the amount of EDTA standard solution added, and the concentration of the EDTA standard solution.

[0022] Furthermore, in the copper ion detection device provided by the present invention, the injection structure adds the EDTA standard solution at a rate of 0.1 to 0.3 mL / s.

[0023] On the other hand, the present invention relates to a computer device comprising: a processor and a memory, wherein the memory stores at least one piece of program code, the at least one piece of program code being loaded and executed by the processor to perform the operations performed in the copper ion detection method described above.

[0024] On the other hand, the present invention relates to a computer-readable storage medium storing at least one piece of program code, which is loaded and executed by a processor to implement the operations performed in the copper ion detection method described above.

[0025] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects or advantages:

[0026] (1) The main contribution of this invention is that by diluting special pure water, potassium chloride and isopropanol, it provides a more suitable acidity, total ionic strength and ionic background for EDTA titration analysis of copper ion concentration, which can improve the stability and accuracy of copper ion detection.

[0027] (2) EDTA complexometric titration analysis has high requirements for titration conditions and solution ion background (total ion concentration and conductivity). Experiments in this invention show that EDTA complexometric titration requires a suitable pH range of 2.2–4.0. Since oxygen-free copper cleaning uses nitric acid solution, the test solution is highly acidic, with a pH much less than 1, necessitating pH adjustment. Direct dilution with pure water is problematic because the high stability of pure water makes it difficult to homogenize the microscopic distribution and interactions of ions in the solution, resulting in significant polarization of different ions, which is detrimental to EDTA complexometric titration. This invention provides dedicated pure water for dilution, which improves the cleanliness of the diluted test solution and enhances its activity and ion migration capacity.

[0028] (3) When the test solution is diluted by a large ratio, the total ionic strength and conductivity of the solution are greatly reduced, making it difficult to achieve the stability and accuracy of EDTA complexometric titration. After a large dilution, the activity coefficient of copper ions changes significantly, and the reduction ratio of copper ion concentration in the actual solution is not proportional to the dilution ratio, making it difficult to accurately determine the copper ion concentration. This invention improves the measurement accuracy, stability, and sensitivity of the titration endpoint by adding potassium chloride and isopropanol. Potassium chloride is a strong electrolyte, which stabilizes the ionic strength in the solution, increases the conductivity of the solution, and creates the reaction conditions for the complexing agent to fully complex with copper ions. At the same time, the chloride and potassium ions in potassium chloride do not interfere with the titration reaction, thereby improving the accuracy and stability of complexometric titration. Meanwhile, the addition of the organic component isopropanol to the solution can reduce the polarity of the solution and improve the sensitivity of complexometric titration. Attached Figure Description

[0029] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. 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.

[0030] Figure 1 These are diagrams showing the state of the solution before and after the titration endpoint. In diagram A, the solution is pinkish-purple before the titration endpoint; in diagram B, the solution is yellow after the titration endpoint.

[0031] Figure 2 The images show the morphology of oxygen-free copper samples. In the images, A represents oxygen-free copper that has passed the cleaning quality test; B represents oxygen-free copper that has failed the cleaning quality test.

[0032] Figure 3 This is a diagram of the filter cleaning solution. In it, A represents the solids in the filter cleaning solution; B represents the liquid in the filter cleaning solution. Detailed Implementation

[0033] The technical solution of the present invention will be described below with reference to the embodiments. However, the present invention is not limited to the following embodiments.

[0034] Unless otherwise specified, the experimental and detection methods described in the following embodiments are conventional methods; unless otherwise specified, the reagents and materials are commercially available.

[0035] Example 1

[0036] This embodiment provides a detailed process for detecting the concentration of copper ions in oxygen-free copper cleaning solution.

[0037] (1) Preparation of 0.01 mol / L EDTA standard solution: Weigh 3.75 g of analytical grade EDTA using an analytical balance, dissolve it in pure water (conductivity < 1 μs / cm, pH 6.5 to 7.5), stir well, and prepare a 1000 mL solution which is then sealed in a volumetric flask.

[0038] (2) Preparation of PAN indicator solution (color development and quantitative reaction endpoint indication): Measure 200 mL of anhydrous ethanol in a beaker, weigh 0.25 g of PAN using an analytical balance, and slowly stir to dissolve in ethanol. The solution is reddish-yellow.

[0039] (3) Treatment and dilution of waste acid stock solution (i.e., oxygen-free copper cleaning solution) to meet titration conditions (pH): Filter the oxygen-free copper cleaning solution using a 50-micron PVC filter, such as... Figure 3 As shown. Figure 3 In this context, A represents the solid component in the filter cleaning solution. Figure 3 In the diagram, B represents the liquid remaining after the filter cleaning solution. This liquid is used as the test solution. The test solution is diluted 1000 times with dedicated dilution pure water, maintaining the pH of the diluted solution at 2.2–4.0. The parameters of the dedicated dilution pure water are: conductivity <10 μS / cm, suspended solids <5.0 mg / L, and pH 4.5–5.5. The dedicated dilution pure water is prepared by adding an appropriate amount of analytical grade hydrochloric acid to pure water (conductivity <1 μS / cm, pH 6.5–7.5), maintaining the pH of the dedicated dilution pure water at 4.5–5.5.

[0040] (4) Add 2.0-3.0 g / L of analytical grade potassium chloride to the diluted test solution, dissolve it completely, and then add 1.0-2.0 mL / L of isopropanol and dissolve it completely.

[0041] (5) Add 6-10 mL of the PAN indicator solution prepared in step (2) to 1000 mL of the test solution obtained in step (4). After adding, the solution changes from light blue to pinkish-purple. The solution state diagram before the titration endpoint is shown in the figure. Figure 1 As shown in A in the diagram.

[0042] (6) Slowly add EDTA and stir, recording the endpoint: Slowly add the EDTA standard solution prepared in step (1) to the solution and stir. Stop adding the solution the instant the color changes from pinkish-purple to light yellowish-green, and record the amount of EDTA added to prevent over-addition. The solution state diagram after the titration endpoint is shown below. Figure 1 As shown in B in the diagram.

[0043] (7) Calculate the copper ion concentration: The quantitative molar ratio of copper ions to EDTA is 1:1. Based on this, calculate the molar concentration of copper ions in the acid solution according to the acid volume, the molar concentration of EDTA, and the volume of EDTA consumed. The metering pump for adding EDTA solution to the solution should have a rate of 0.1 to 0.3 mL / s.

[0044] All the solutions described above were stirred using electromagnetic stirring; the stirring speed was controlled at 50–60 r / min.

[0045] Example 2

[0046] This embodiment provides a comparative experiment on the detection method of copper ion concentration in oxygen-free copper cleaning solution.

[0047] The liquid remaining after filtering the solids from the oxygen-free copper cleaning solution was taken as the test solution. The pH of test solution 1 was 0.1, the pH of test solution 2 was 0.3, and the pH of test solution 3 was 0.5.

[0048] The parameters for dilution-specific pure water 1 are: conductivity 9.2 μs / cm, suspended solids 4.8 mg / L, pH 4.5. The parameters for dilution-specific pure water 2 are: conductivity 7.9 μs / cm, suspended solids 3.9 mg / L, pH 5. The parameters for dilution-specific pure water 3 are: conductivity 6.8 μs / cm, suspended solids 3.3 mg / L, pH 5.5.

[0049] The experiment was conducted following the steps provided in Example 1.

[0050] Experimental Group 1: Diluted with dedicated dilution water 1, with 2 g / L potassium chloride and 1 mL / L isopropanol added. Experimental Group 2: Diluted with dedicated dilution water 2, with 2.5 g / L potassium chloride and 1.5 mL / L isopropanol added. Experimental Group 3: Diluted with dedicated dilution water 3, with 3 g / L potassium chloride and 2 mL / L isopropanol added. Control Group 1: Same as Experimental Group 1, except potassium chloride was not added. Control Group 2: Same as Experimental Group 1, except isopropanol was not added. Control Group 3: Same as Experimental Group 1, except neither potassium chloride nor isopropanol was added. Control Group 4: Same as Experimental Group 1, except diluted with pure water (conductivity < 1 μS / cm, pH 7). Test solutions 1, 2, and 3 were tested using the method for determining nickel and copper ion content in electroless copper plating solutions for electromagnetic shielding films (GB / T 27581-2011), with undiluted solutions analyzed by EDTA complexometric titration. Copper ion concentration in test solutions 1, 2, and 3 was simultaneously determined using atomic absorption spectrophotometry as a standard. Each experiment was repeated three times, and the specific results are shown in Table 1.

[0051] Table 1. Detection results of copper ion concentration in oxygen-free copper cleaning solution

[0052]

[0053]

[0054] As shown in test groups 1 to 3 of Table 1, the detection method for copper ion concentration in the oxygen-free copper cleaning solution provided by this invention has an error within the allowable and controllable range of 10% compared to the result determined by atomic absorption spectrophotometry. As shown in the EDTA complexometric titration group of Table 1, the copper ion activity coefficient changes significantly after a large dilution ratio. The reduction ratio of copper ion concentration in the actual solution is not proportional to the dilution ratio, making it difficult to accurately determine the copper ion concentration. As shown in comparison groups 1 to 3 of Table 1, the absence of potassium chloride and / or isopropanol leads to significant errors in the measurement results. As shown in comparison group 4 of Table 1, the conductivity and pH of diluted pure water both affect the measurement results.

[0055] Example 3

[0056] This embodiment provides an experimental method for detecting the concentration of copper ions in oxygen-free copper cleaning solution.

[0057] Oxygen-free copper samples with and without acceptable cleaning quality were taken and subjected to surface scanning electron microscopy morphology analysis. Simultaneously, the acid solution used for cleaning the samples was analyzed by EDTA complexometric titration according to the invention's proposed method. The results showed that with continued use of the acid solution, the corrosion efficacy expressed by the morphological characteristics of the oxygen-free copper decreased to some extent. Figure 2 ; Figure 2 In the diagram, A represents the morphology of an oxygen-free copper sample that has passed the cleaning quality assessment (copper ion concentration of 13 g / L). Figure 2 B in the diagram represents a scan of an oxygen-free copper sample that failed the cleaning quality test (copper ion concentration 18 g / L). The morphology shows that the sample cleaned with a solution of substandard quality and high copper ion concentration exhibited low corrosion efficiency. Based on concentration and morphology analysis, a large dataset showing the correlation between copper ion concentration and sample morphology was compiled. From this correlation, a solution replacement standard of 15 g / L was derived.

[0058] Cleaning solutions from different stages of the oxygen-free copper cleaning process were analyzed and compared using atomic absorption spectrophotometry and the complexometric titration method of this invention. The error was within the allowable and controllable range of 10%. Furthermore, the method of this invention can be systematically calibrated to analyze errors based on the error characteristics.

[0059] As described above, the basic principles, main features, and advantages of the present invention have been well described. The above embodiments and specifications are merely descriptions of preferred embodiments of the present invention, and the present invention is not limited to the above embodiments. Various changes and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the spirit and scope of the present invention should fall within the protection scope defined by the present invention.

Claims

1. A copper ion detection solution for use in EDTA complexometric titration to detect copper ion concentration, comprising: The EDTA standard solution and PAN indicator are characterized by further comprising: dilution-specific pure water, potassium chloride, and isopropanol; The parameters of the dilution-specific pure water are: conductivity <10μs / cm, suspended solids <5.0mg / L, and pH 4.5~5.5; The dilution-specific pure water comprises pure water and hydrochloric acid. Hydrochloric acid is added to pure water with a conductivity of <1μs / cm and a pH of 6.5~7.5 to prepare the dilution-specific pure water. The amount of potassium chloride added is 2-3 g / L, and the amount of isopropanol added is 1-2 mL / L.

2. The copper ion detection solution according to claim 1, characterized in that, The concentration of the EDTA standard solution is 0.01 mol / L.

3. A method for detecting copper ions, characterized in that, The copper ion content in the test solution is detected using the copper ion detection solution according to any one of claims 1 to 2.

4. The copper ion detection method according to claim 3, characterized in that, include: The test solution is diluted to a pH of 2.2-4.0 using the dilution-specific pure water, and then the potassium chloride and isopropanol are added and mixed evenly to obtain the diluted test solution. Then the PAN indicator is added, and the diluted test solution changes from light blue to pinkish-purple; Add the EDTA standard solution dropwise until the color of the diluted test solution changes from pinkish-purple to light yellowish-green, then stop adding the solution. The concentration of copper ions in the test solution is determined based on the volume of the test solution, the dilution ratio of the test solution, the amount of EDTA standard solution added, and the concentration of the EDTA standard solution.

5. A copper ion detection device, characterized in that, The copper ion detection device includes: A storage structure is provided for storing at least one of EDTA standard solution, PAN indicator, dilution-specific pure water, potassium chloride, and isopropanol. The dilution-specific pure water has the following parameters: conductivity < 10 μS / cm, suspended solids < 5.0 mg / L, and pH 4.5–5.

5. The dilution-specific pure water comprises pure water and hydrochloric acid, prepared by adding hydrochloric acid to pure water with conductivity < 1 μS / cm and pH 6.5–7.

5. The amount of potassium chloride added is 2–3 g / L, and the amount of isopropanol added is 1–2 mL / L. The reaction structure is used for the reaction of the test solution with the EDTA standard solution; before the test solution reacts with the EDTA standard solution, the test solution is diluted with the special dilution pure water to a pH of 2.2~4.0, and then potassium chloride, isopropanol, and PAN indicator are added; An injection structure for adding the EDTA standard solution dropwise to the reaction structure; A color recognition structure is used to identify color changes in the liquid within the reaction structure; The detection structure is used to determine the concentration of copper ions in the test solution based on the volume of the test solution, the dilution ratio of the test solution, the amount of EDTA standard solution added, and the concentration of the EDTA standard solution.

6. The copper ion detection device according to claim 5, characterized in that, The injection structure adds the EDTA standard solution at a rate of 0.1~0.3 mL / s.

7. A computer device, characterized in that, The computer device includes a processor and a memory, wherein the memory stores at least one piece of program code, which is loaded and executed by the processor to perform the operations performed in the copper ion detection method according to any one of claims 3 to 4.

8. A computer-readable storage medium, characterized in that, The computer-readable storage medium stores at least one piece of program code, which is loaded and executed by a processor to perform the operations performed in the copper ion detection method as described in any one of claims 3 to 4.

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