Preparation method of titanium-copper one-stop fluoride-free etching solution

Abstract

The invention discloses a titanium-copper one-stop fluorine-free etching solution preparation method, and relates to the technical field of etching solution preparation, and the method comprises the following steps: S1, formula design and raw material preparation; s2, mixing reaction; s3, filtering, purifying and adjusting; s4, performing performance test and optimization; and S5, packaging and storing. According to the preparation method of the titanium-copper one-stop fluoride-free etching solution, an efficient and environment-friendly metal etching solution is provided by optimizing the component selection and proportioning scheme of the fluoride-free etching solution, and the environment-friendly chemical etching solution specially designed for titanium and copper can be prepared for the titanium and copper; compared with the prior art, the preparation method has the advantages that the balance between the etching effect and the environmental protection property is realized, the production condition and the packaging mode are strictly controlled in the preparation process, so that the stability and the effectiveness of the etching liquid in the storage and use processes are ensured, the application prospect and the market potential are relatively good, and the commercialization process and the market popularization of the fluoride-free etching liquid technology are favorably promoted.

Description

Technical Field

[0001] The invention relates to the technical field of etching solution preparation, in particular to a one-stop fluorine-free etching solution preparation method for titanium and copper. Background Art

[0002] Etching liquid is a chemical agent, which is mainly used to etch away part of the surface of certain materials. It is widely used in the production of various precision parts, circuit boards, copperplate engraving and other fields. Fluorine-free etching liquid, as the name implies, is an etching liquid that does not contain fluoride during the etching process. This kind of etching liquid has gradually gained attention due to its environmental friendliness and has become an important choice to replace traditional fluorine-containing etching liquid. Fluorine-free etching liquid has significant advantages in reducing environmental pollution and protecting the ecological environment. At the same time, it can also meet the needs of precise etching of metal surfaces. With the continuous improvement of environmental awareness and the continuous advancement of technology, fluorine-free etching liquid is expected to be more widely used and promoted in the future.

[0003] However, in the prior art, although the preparation method of fluorine-free etching solution has made certain progress, there are still some defects and challenges, which are mainly reflected in the following aspects:

[0004] First, the preparation of fluorine-free etching solution requires the selection of a variety of suitable chemical components, but the selection and proportion of these components is not easy. It is necessary to consider multiple factors such as the interaction between them, the etching effect on the target metal, and the impact on the environment. Titanium and copper are the two most important metal materials in current industrial production operations. Existing fluorine-free etching solutions are usually not suitable for etching titanium and copper at the same time.

[0005] Secondly, since one of the main advantages of fluorine-free etching solution is its environmental friendliness, in order to reduce pollution to the environment, the ingredients in fluorine-free etching solution cannot be as highly corrosive as traditional fluorine-containing etching solution, which leads to problems such as slow etching speed, insufficient etching depth or unsatisfactory etching morphology.

[0006] Therefore, it is urgent to improve this shortcoming. The present invention studies and improves the existing technology and its shortcomings, and provides a one-stop fluorine-free etching solution preparation method for titanium and copper. Summary of the invention

[0007] The object of the present invention is to provide a one-stop method for preparing a fluorine-free etching solution for titanium and copper, so as to solve the problems raised in the above-mentioned background technology.

[0008] To achieve the above object, the present invention provides the following technical solution: a one-stop fluorine-free etching solution preparation method for titanium and copper, comprising the following steps:

[0009] S1. Formulation design and raw material preparation:

[0010] According to the etching characteristics of titanium and copper, and considering the influence of various chemical components on the etching speed, etching morphology, environmental protection and other aspects of titanium and copper, a fluorine-free etching solution formula that can meet the etching requirements of both is designed, and the required raw materials, including acid, oxidant, stabilizer, surfactant and water, are prepared according to the formula requirements to ensure that the purity and quality of the raw materials meet the standards to avoid affecting the etching effect;

[0011] S2, mixed reaction:

[0012] Mix the prepared raw materials according to the formula ratio, add the raw materials in stages, and strictly control the reaction conditions so that the raw materials react fully and generate the required etching solution;

[0013] S3, filtration, purification and adjustment:

[0014] The reaction mixture is filtered and purified to remove impurities and unreacted substances therein, and the pH value, concentration and other parameters of the etching solution are adjusted as needed to meet specific etching requirements;

[0015] S4. Performance testing and optimization:

[0016] Conduct performance tests on the prepared fluorine-free etching solution, and make necessary adjustments and optimizations to the formula and preparation process based on the test results;

[0017] S5. Packaging and storage:

[0018] The fluorine-free etching solution that has passed the performance test should be packaged and marked with instructions for use and safety warning information. The finished products should be stored in a cool, dry, well-ventilated place, away from direct sunlight and high temperature environment to ensure the long-term stability and effectiveness of the etching solution.

[0019] Furthermore, in step S1, the raw material preparation ratio of the fluorine-free etching solution is as follows: 5 to 20 parts of acid, 1 to 10 parts of oxidant, 0.1 to 1 part of stabilizer (plays a role in regulating and controlling the etching reaction rate and preventing the solution from decomposing or deteriorating too quickly), 0.01 to 1 part of surfactant (plays a role in reducing the surface tension of the solution, improving wettability and fluidity, and promoting the uniform distribution of the etching solution on the surface of the etched material, etc.), and 65 to 95 parts of water;

[0020] Wherein, the acid is nitric acid and the oxidant is hydrogen peroxide;

[0021] The stabilizer is selected from one of ethylenediaminetetraacetic acid and ascorbic acid (vitamin C).

[0022] Furthermore, the surfactant is selected from anionic surfactants or nonionic surfactants, and the anionic surfactants include but are not limited to sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate, and the nonionic surfactants include but are not limited to polyethylene glycol (PEG) and polyoxyethylene ether.

[0023] Furthermore, in step S2, the raw materials are added in the order and in stages as follows:

[0024] Water: Adding a certain amount of water as a solvent helps dilute the subsequent raw materials and reduce the intensity of the initial reaction;

[0025] Nitric acid (partial): Slowly add part of the nitric acid while stirring. The addition of nitric acid will cause the solution temperature to rise and the pH value to drop, so the addition speed and stirring intensity need to be controlled;

[0026] Hydrogen peroxide: After the nitric acid is completely dissolved and mixed evenly, start adding hydrogen peroxide. Hydrogen peroxide is an oxidizing agent, which works together with nitric acid to produce an etching effect. It also needs to be added slowly and stirred thoroughly.

[0027] Nitric acid (remaining): After some nitric acid and hydrogen peroxide have reacted initially, observe the reaction speed and stability and then gradually add the remaining nitric acid;

[0028] Surfactant: Surfactant is added to improve the wettability and uniformity of the etching solution. The amount of surfactant added is small and has little effect on the temperature and pH value of the system.

[0029] Furthermore, in step S2, the reaction conditions include temperature, pH value and stirring speed, and the temperature is controlled at 20-50°C, the pH value is controlled at 2-4, the stirring speed is controlled between 800-1200rpm, and during the reaction process, the stirring speed is gradually adjusted to find the optimal value.

[0030] Furthermore, in step S3, the specific implementation steps of filtration and purification are as follows:

[0031] Pretreatment: Before filtration and purification, the reaction mixture is pretreated, such as adjusting the pH value, temperature, etc., to ensure the smooth progress of subsequent steps;

[0032] Preliminary filtration: Use filter media to perform preliminary filtration on the reaction mixture to remove visible solid particles and impurities;

[0033] Adsorption purification: The etching solution that has been initially filtered is adsorbed and purified by adsorbents such as activated carbon to remove organic impurities, pigments, odorous substances, etc.

[0034] Deep purification: Select deep purification technologies such as ion exchange, ultrafiltration or reverse osmosis as needed to further remove ionic impurities, high molecular weight organic matter, etc. in the solution;

[0035] Quality testing: The purified etching solution is subjected to quality testing, including the determination of pH value, concentration, impurity content and other indicators to ensure that the product meets the requirements.

[0036] Furthermore, the filter medium used in the preliminary filtration operation is five layers of microporous filter membranes with different filter pore sizes, and the filter pore sizes are 5 microns, 3 microns, 1 micron, 0.8 microns, and 0.45 microns, respectively.

[0037] Furthermore, the deep purification technology specifically includes:

[0038] Ion exchange: By utilizing the selective adsorption of ion exchange resins, cations (such as hydrogen ions, calcium ions) or anions (such as chloride ions, nitrate ions) in the solution are replaced to achieve the purpose of purification; in the preparation of etching solution, it is used to remove inorganic salts and other ionic impurities produced during the reaction process;

[0039] Ultrafiltration: A purification technology based on membrane separation, which uses ultrafiltration membranes with pore sizes ranging from a few nanometers to tens of nanometers to intercept macromolecular substances and particles; in the preparation of etching solutions, it is used to remove high molecular weight organic matter, proteins, colloids and other impurities, while allowing low molecular weight solvents and solutes to pass through;

[0040] Reverse osmosis: A membrane separation technology under high pressure to remove almost all impurities in water, such as soluble salts, colloids, bacteria, viruses, etc.; in the preparation of etching solution, it is used to further improve the purity of etching solution.

[0041] Furthermore, in step S4, an etching test is performed using a standard sample or an actual workpiece, and all data during the experiment are recorded to test the following properties of the fluorine-free etching solution:

[0042] Etching rate: The etching rate is evaluated by measuring the size change or weight loss of the sample before and after etching. Specifically, sampling is performed at several time points to obtain a curve of etching rate changing with time.

[0043] Etching morphology: Use a microscope or scanning electron microscope to observe the surface morphology of the sample after etching, and evaluate the uniformity, clarity and side wall roughness of the etching lines;

[0044] Environmental protection: The waste liquid generated during the etching process is collected and sent to a professional organization for environmental index testing. The test items include heavy metal content, organic matter content, pH value, etc. At the same time, it is evaluated whether the etching solution is volatile, flammable or has other potential environmental risks during use and storage.

[0045] The present invention provides a one-stop fluorine-free etching solution preparation method for titanium and copper, which has the following beneficial effects:

[0046] The present invention proposes an efficient and environmentally friendly metal etching solution by optimizing the component selection and ratio scheme of the fluorine-free etching solution. The present invention can prepare an environmentally friendly chemical etching solution specially designed for titanium and copper for the two metals. The environmentally friendly chemical etching solution can effectively etch titanium and copper at the same time without containing fluoride, meeting the needs of micro-machining, electronic manufacturing and other fields for high-precision and high-quality metal etching, achieving a balance between etching effect and environmental protection, and strictly controlling the production conditions and packaging methods during the preparation process to ensure the stability and effectiveness of the etching solution during storage and use. The present invention has good application prospects and market potential, and is helpful to promote the commercialization process and market promotion of the fluorine-free etching solution technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 A schematic flow chart of the steps of the one-stop fluorine-free etching solution preparation method for titanium and copper of the present invention;

[0048] Figure 2 Schematic diagram for comparing experimental results of the one-stop fluorine-free etching solution preparation method for titanium and copper of the present invention. DETAILED DESCRIPTION

[0049] The following embodiments of the present invention are described in further detail in conjunction with the accompanying drawings and examples. The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0050] Embodiment 1

[0051] like Figure 1 As shown, a one-stop fluorine-free etching solution preparation method for titanium and copper comprises the following steps:

[0052] S1. Formulation design and raw material preparation:

[0053] According to the etching characteristics of titanium and copper, considering the influence of various chemical components on the etching speed, etching morphology, environmental protection and other aspects of titanium and copper, a fluorine-free etching solution formula that can simultaneously meet the etching requirements of both is designed, and the required raw materials are prepared according to the formula requirements. In this embodiment, the raw material preparation ratio of the fluorine-free etching solution is as follows: 15 parts of nitric acid, 5 parts of hydrogen peroxide, 0.5 parts of ethylenediaminetetraacetic acid, 0.25 parts of sodium lauryl sulfate, and 85 parts of water, ensuring that the purity and quality of the raw materials meet the standards to avoid affecting the etching effect;

[0054] S2, mixed reaction:

[0055] The prepared raw materials are mixed according to the formula ratio, and the raw materials are added in stages, and the reaction conditions are strictly controlled to allow the raw materials to fully react and generate the required etching solution; the order of adding the raw materials and the staged addition are as follows:

[0056] Water: First, a certain amount of water is added as a solvent, which helps to dilute the subsequent raw materials and reduce the intensity of the initial reaction;

[0057] Nitric acid (partial): Slowly add part of the nitric acid while stirring. The addition of nitric acid will cause the solution temperature to rise and the pH value to drop, so the addition speed and stirring intensity need to be controlled;

[0058] Hydrogen peroxide: After the nitric acid is completely dissolved and mixed evenly, start adding hydrogen peroxide. Hydrogen peroxide is an oxidizing agent, which works together with nitric acid to produce an etching effect. It also needs to be added slowly and stirred thoroughly.

[0059] Nitric acid (remaining): After some nitric acid and hydrogen peroxide have reacted initially, observe the reaction speed and stability and then gradually add the remaining nitric acid;

[0060] Surfactant: Finally, surfactant is added to improve the wettability and uniformity of the etching solution. The amount of surfactant added is small and has little effect on the temperature and pH value of the system;

[0061] The reaction conditions include temperature, pH value and stirring speed, and the temperature is controlled at 40±5°C, the pH value is controlled at 3±0.5, and the stirring speed is controlled at 1000 rpm. During the reaction, the stirring speed is gradually adjusted to find the optimal value;

[0062] S3, filtration, purification and adjustment:

[0063] The reaction mixture is filtered and purified to remove impurities and unreacted substances therein. The specific implementation steps of filtering and purification are as follows:

[0064] Pretreatment: Before filtration and purification, the reaction mixture is pretreated, such as adjusting the pH value, temperature, etc., to ensure the smooth progress of subsequent steps;

[0065] Preliminary filtration: Use a filter medium to perform preliminary filtration on the reaction mixture to remove visible solid particles and impurities; the filter medium used in the preliminary filtration operation is five layers of microporous filter membranes with different filtration pore sizes, and the filtration pore sizes are 5 microns, 3 microns, 1 micron, 0.8 microns, and 0.45 microns, respectively;

[0066] Adsorption purification: The etching solution that has been initially filtered is adsorbed and purified by adsorbents such as activated carbon to remove organic impurities, pigments, odorous substances, etc.

[0067] Deep purification: Select deep purification technologies such as ion exchange, ultrafiltration or reverse osmosis as needed to further remove ionic impurities, high molecular weight organic matter, etc. in the solution;

[0068] Quality testing: Conduct quality testing on the purified etching solution, including the determination of pH value, concentration, impurity content and other indicators to ensure that the product meets the requirements;

[0069] Among them, deep purification technology specifically includes:

[0070] Ion exchange: By utilizing the selective adsorption of ion exchange resins, cations (such as hydrogen ions) or anions (such as nitrate ions) in the solution are replaced to achieve the purpose of purification; in this embodiment, it is used to remove inorganic salts and other ionic impurities generated during the reaction;

[0071] Ultrafiltration: A purification technology based on membrane separation, which uses ultrafiltration membranes with pore sizes ranging from a few nanometers to tens of nanometers to intercept macromolecular substances and particles; in this embodiment, it is used to remove high molecular weight organic matter, proteins, colloids and other impurities, while allowing low molecular weight solvents and solutes to pass through;

[0072] Reverse osmosis: A membrane separation technique under high pressure to remove almost all impurities in water, such as soluble salts, colloids, bacteria, viruses, etc.; in this embodiment, it is used to further improve the purity of the etching solution;

[0073] S4. Performance testing and optimization:

[0074] The prepared fluorine-free etching solution was subjected to a performance test. In this embodiment, a standard sample was used to perform an etching test, and all data during the experiment were recorded to test the following properties of the fluorine-free etching solution:

[0075] Etching rate: The etching rate is evaluated by measuring the size change or weight loss of the sample before and after etching. Specifically, sampling is performed at several time points to obtain a curve of etching rate changing with time.

[0076] Etching morphology: Use a microscope or scanning electron microscope to observe the surface morphology of the sample after etching, and evaluate the uniformity, clarity and side wall roughness of the etching lines;

[0077] Environmental protection: The waste liquid generated during the etching process is collected and sent to a professional organization for environmental index testing. The test items include heavy metal content, organic matter content, pH value, etc. At the same time, it is evaluated whether the etching solution is volatile, flammable or has other potential environmental risks during use and storage;

[0078] After the performance test, the formula and preparation process are adjusted and optimized as necessary according to the test results to obtain a fluorine-free etching solution product that passes the performance test;

[0079] S5. Packaging and storage:

[0080] The fluorine-free etching solution that has passed the performance test should be packaged and marked with instructions for use and safety warning information. The finished products should be stored in a cool, dry, well-ventilated place, away from direct sunlight and high temperature environment to ensure the long-term stability and effectiveness of the etching solution.

[0081] Experimental testing

[0082] In order to more clearly illustrate the content of the present invention, the fluorine-free etching solution prepared in Example 1 was tested for performance with a commercially available fluorine-containing etching solution (i.e., 3M Novec 7500 electronic fluorinated solution from the United States, produced by 3M Company of the United States or its authorized manufacturer) and a commercially available fluorine-free etching solution (i.e., DMK331 etching solution, produced by Shenzhen Yunmin Instrument Co., Ltd.). The specific test items were the etching effect of the etching solution on titanium and copper materials, and the total amount of harmful gases (or substances) released; wherein, the test for titanium material etching was based on GB / T15085-2013, and the test for copper material etching was based on GB / T10125-1997. The results are as follows: Figure 2 As shown;

[0083] Combination Figure 2 It can be seen that the fluorine-free etching solution prepared in Example 1 can have a good etching effect on both titanium and copper materials, and the release of harmful gases (or substances) is significantly lower than that of commercially available fluorine-containing etching solutions and fluorine-free etching solutions, which solves the problem of the difficulty in balancing the etching performance and environmental protection of traditional fluorine-free etching solutions.

[0084] The embodiments of the present invention are given for the purpose of illustration and description, and are not intended to be exhaustive or to limit the invention to the disclosed forms. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments are selected and described in order to better illustrate the principles and practical applications of the present invention and to enable those of ordinary skill in the art to understand the present invention and thereby design various embodiments with various modifications suitable for specific uses.

Claims

1. A one-stop method for preparing a fluorine-free etching solution for titanium and copper, characterized in that: The following steps are involved: S1. Formulation design and raw material preparation: According to the etching characteristics of titanium and copper, a fluorine-free etching solution formula that can meet the etching requirements of both is designed, and the required raw materials, including acid, oxidant, stabilizer, surfactant and water, are prepared according to the formula requirements; S2, mixed reaction: Mix the prepared raw materials according to the formula ratio, add the raw materials in stages, and strictly control the reaction conditions so that the raw materials react fully and generate the required etching solution; S3, filtration, purification and adjustment: The reaction mixture is filtered and purified to remove impurities and unreacted substances therein, and the parameters of the etching solution are adjusted as needed to meet specific etching requirements; S4. Performance testing and optimization: Conduct performance tests on the prepared fluorine-free etching solution, and make necessary adjustments and optimizations to the formula and preparation process based on the test results; S5. Packaging and storage: The fluorine-free etching solution that has passed the performance test should be packaged, with instructions for use and safety warning information marked, and the finished products should be stored in a cool, dry and well-ventilated place.

2. The method for preparing a one-stop fluorine-free etching solution for titanium and copper according to claim 1, characterized in that: In the step S1, the raw material preparation ratio of the fluorine-free etching solution is as follows: 5-20 parts of acid, 1-10 parts of oxidant, 0.1-1 parts of stabilizer, 0.01-1 parts of surfactant, and 65-95 parts of water; Wherein, the acid is nitric acid and the oxidant is hydrogen peroxide; The stabilizer is selected from ethylenediaminetetraacetic acid and ascorbic acid.

3. The one-stop fluorine-free etching solution preparation method for titanium copper according to claim 2, characterized in that: The surfactant is selected from anionic surfactants or nonionic surfactants, and the anionic surfactants include but are not limited to sodium dodecyl sulfate and sodium dodecylbenzene sulfonate, and the nonionic surfactants include but are not limited to polyethylene glycol and polyoxyethylene ether.

4. The one-stop fluorine-free etching solution preparation method for titanium copper according to claim 1, characterized in that: In step S2, the raw materials are added in the order and in stages as follows: Water: Add a certain amount of water as a solvent; Nitric acid: While stirring, slowly add some nitric acid; Hydrogen Peroxide: After the nitric acid is completely dissolved and mixed, begin adding the hydrogen peroxide; Nitric acid: After some nitric acid and hydrogen peroxide react initially, observe the reaction speed and stability before gradually adding the remaining nitric acid; Surfactant: Surfactants are added to improve the wettability and uniformity of the etching solution.

5. The method for preparing a one-stop fluorine-free etching solution for titanium and copper according to claim 1, characterized in that: In step S2, the reaction conditions include temperature, pH value and stirring speed, and the temperature is controlled at 20-50°C, the pH value is controlled at 2-4, and the stirring speed is controlled between 800-1200rpm. During the reaction, the stirring speed is gradually adjusted to find the optimal value.

6. The method for preparing a one-stop fluorine-free etching solution for titanium and copper according to claim 1, characterized in that: In step S3, the specific implementation steps of filtration and purification are as follows: Pretreatment: Pretreatment of the reaction mixture prior to filtration and purification; Preliminary filtration: Use filter media to perform preliminary filtration on the reaction mixture to remove visible solid particles and impurities; Adsorption purification: The etching solution that has been initially filtered is adsorbed and purified by activated carbon to remove organic impurities, pigments, and odorous substances; Deep purification: Select deep purification technology as needed to further remove ionic impurities and high molecular weight organic matter in the solution; Quality testing: The purified etching solution is subjected to quality testing, including the determination of pH value, concentration, and impurity content.

7. The method for preparing a one-stop fluorine-free etching solution for titanium and copper according to claim 6, characterized in that: The filter medium used in the preliminary filtration operation is five layers of microporous filter membranes with different filter pore sizes, and the filter pore sizes are 5 microns, 3 microns, 1 micron, 0.8 microns, and 0.45 microns, respectively.

8. The method for preparing a one-stop fluorine-free etching solution for titanium and copper according to claim 6, characterized in that: The deep purification technology specifically includes: Ion exchange: By utilizing the selective adsorption of ion exchange resins, cations or anions in the solution are replaced to achieve the purpose of purification; in the preparation of etching solutions, it is used to remove inorganic salts and other ionic impurities produced during the reaction process; Ultrafiltration: A purification technology based on membrane separation, which uses ultrafiltration membranes with pore sizes ranging from a few nanometers to tens of nanometers to intercept macromolecular substances and particles; in the preparation of etching solutions, it is used to remove high molecular weight impurities while allowing low molecular weight solvents and solutes to pass through; Reverse Osmosis: A membrane separation technology under high pressure to remove all impurities in water, including soluble salts, colloids, bacteria, and viruses; in the preparation of etching solutions, it is used to further improve the purity of the etching solution.

9. The method for preparing a one-stop fluorine-free etching solution for titanium and copper according to claim 1, characterized in that: In step S4, an etching test is performed using a standard sample or an actual workpiece, and all data during the experiment are recorded to test the following properties of the fluorine-free etching solution: Etching rate: The etching rate is evaluated by measuring the size change or weight loss of the sample before and after etching. Specifically, sampling is performed at several time points to obtain a curve of etching rate changing with time. Etching morphology: Use a microscope or scanning electron microscope to observe the surface morphology of the sample after etching, and evaluate indicators such as the uniformity, clarity and side wall roughness of the etching lines; Environmental protection: The waste liquid generated during the etching process is collected and sent to a professional organization for environmental index testing. The test items include heavy metal content, organic matter content, pH value, and at the same time, it is evaluated whether the etching solution is volatile, flammable, or has other potential environmental risks during use and storage.

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