Phosphating solution based on electric triggering and bionic template cooperative regulation and control as well as use method and application of phosphating solution

Abstract

The invention discloses a phosphating solution based on electric triggering and bionic template cooperative regulation and control as well as a use method and application thereof, and belongs to the technical field of phosphating solutions. The phosphating solution comprises the following components: 5-60 g / L of a phosphating precursor; 0.1 g / L to 10.0 g / L of a bionic template agent; 0.5 g / L to 20 g / L of a nanometer reinforcing phase; 7-65 g / L of a metal ion source; 0.1-3.0 g / L of an oxidizing agent; the pH regulator is used for regulating the pH value to 3.5 to 6.0; and the balance of deionized water. The phosphating precursor is one or more of phytic acid, amino trimethylene phosphonic acid and 1-hydroxyethylidene-1, 1-diphosphonic acid; when the phosphating solution is used, a workpiece is used as a cathode to apply an electric field. The phosphating solution is used for metal protection or metal drawing. A phosphating film formed by the phosphating solution based on electric triggering and bionic template cooperative regulation under the action of an electric field has excellent corrosion resistance, adhesive force and wear resistance, and sediment in the phosphating process is few.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of phosphating solution, and particularly relates to a phosphating solution based on synergistic regulation of electric triggering and biomimetic templates as well as a use method and application thereof. BACKGROUND

[0002] Traditional zinc-calcium phosphating technology is based on a phosphoric acid system and relies on toxic accelerators such as nitrite, which has problems such as environmental pollution, health risks and poor bath stability. Existing nitrite-free technologies (such as chlorate, molybdate systems) are mostly direct replacements and do not break out of the traditional framework of "oxidation promotion", which has limitations such as insufficient film performance, high cost or excessive sediment. At the same time, the traditional phosphating film has coarse crystallization and high porosity, which restricts the further improvement of its corrosion resistance. Therefore, there is an urgent need for a fundamentally innovative phosphating technology from the film formation mechanism, which can achieve environmental protection, high performance and process controllability at the same time. SUMMARY

[0003] In order to overcome the deficiencies of the prior art, the application provides a phosphating solution based on synergistic regulation of electric triggering and biomimetic templates as well as a use method and application thereof.

[0004] The application provides an environmentally friendly, high-performance and process-controllable new phosphating technology. The core of the application is that by combining biomimetic templates with interface orientation function, phosphorus precursors (such as phytic acid) that can undergo controlled hydrolysis at the interface under the triggering of an electric field, and optional functionalized nanoparticles, and introducing a direct current electric field as a reaction trigger, a significant synergistic effect is generated between the four in a weakly acidic environment and at the metal interface. Among them, the role of the electric field is particularly crucial: when the workpiece is used as a cathode, a local alkaline microenvironment is formed at its interface due to the hydrogen evolution reaction, which can efficiently catalyze the hydrolysis of phytic acid and other precursors and accurately release phosphate. This process simulates and strengthens the mechanism of molecular template regulation and material transport in biological mineralization, thereby forming an ultra-dense, high-performance nanocomposite phosphating film on the metal surface in situ. Through the synergistic effect of specific components and external electric field, the application realizes efficient and controllable film formation at a relatively low temperature.

[0005] The technical scheme adopted by the application to solve its technical problems is: The application provides a phosphating solution based on synergistic regulation of electric triggering and biomimetic templates, which comprises: Phosphating precursor: 5-60 g / L; Biomimetic template agent: 0.1-10.0 g / L; Nanometer reinforcing phase: 0.5-20 g / L; Metal ion source: 7-65 g / L; Oxidizing agent: 0.1-3.0 g / L; pH regulator: adjust the pH to 3.5-6.0; Deionized water: Balance; The phosphating precursor is one or more of phytic acid, aminotrimethylphosphonic acid (ATMP), and hydroxyethylidene diphosphonic acid (HEDP); The phosphating solution based on the coordinated control of electrical triggering and biomimetic template is used with the workpiece as the cathode to apply an electric field.

[0006] Preferably, the current density on the workpiece surface is 5-10 A / dm². 2 .

[0007] More preferably, the electric field is a DC voltage of 1-5V, and the distance between the workpiece and the counter electrode is 5-8cm.

[0008] Preferably, the biomimetic template agent is a polymeric compound that regulates crystal growth by complexing metal ions with functional groups.

[0009] Preferably, the biomimetic template agent is one or more of polyacrylic acid and polyaspartic acid.

[0010] More preferably, the weight-average molecular weight of the polyacrylic acid is 1000-10000.

[0011] More preferably, the weight-average molecular weight of the polyaspartic acid is 1000-10000.

[0012] Preferably, the nano-reinforcing phase is surface-functionalized inorganic nanoparticles.

[0013] Preferably, the nano-reinforcing phase is one or more of aminated nano-silica (SiO2) and carboxylated nano-silica (SiO2).

[0014] More preferably, the particle size of the aminated nano-silica is 10-30 nm.

[0015] More preferably, the particle size of the carboxylated nano-silica is 10-30 nm.

[0016] Preferably, the metal ion source includes a primary film-forming cation source and an auxiliary film-forming cation source, wherein the concentration of the primary film-forming cation source is 5-40 g / L and the concentration of the auxiliary film-forming cation source is 2-25 g / L.

[0017] More preferably, the primary film-forming cation source is one or more of zinc nitrate and zinc oxide.

[0018] More preferably, the auxiliary film-forming cation source is one or more of calcium nitrate and nickel nitrate.

[0019] Further preferably, the concentration of the main film-forming cation source is 10-20 g / L, and the concentration of the auxiliary film-forming cation source is 2-10 g / L.

[0020] Preferably, the oxidizing agent is ammonium molybdate.

[0021] Preferably, the pH regulator is one or more of sodium hydroxide, potassium hydroxide, and ammonia.

[0022] Preferably, the phosphating solution based on the synergistic regulation of electric triggering and biomimetic templates comprises: Phosphating precursor: 10-20 g / L; Biomimetic template agent: 0.5-2 g / L; Nano-enhanced phase: 2-5 g / L; Metal ion source: 12-30 g / L; Oxidizing agent: 0.4-1 g / L; pH regulator: adjust the pH to 4-5.5; Deionized water: the balance.

[0023] The present application provides a method for using the above-mentioned phosphating solution based on the synergistic regulation of electric triggering and biomimetic templates, comprising the following steps: The workpiece is pretreated, then phosphated, and finally post-treated; The phosphating process comprises: immersing the pretreated workpiece as a cathode in the above-mentioned phosphating solution based on the synergistic regulation of electric triggering and biomimetic templates, applying a direct current voltage, and the current density on the surface of the workpiece is 5-10 A / dm 2 , and the workpiece is soaked for 30 s-1 minute at a temperature of 25-45℃.

[0024] Preferably, the phosphating solution in the phosphating process further comprises a counter electrode, and the voltage between the workpiece and the counter electrode is 1-5 V, and the distance between the workpiece and the counter electrode is 5-8 cm.

[0025] Further preferably, the counter electrode is stainless steel or graphite.

[0026] Preferably, the pretreatment comprises pickling and water washing.

[0027] Preferably, the post-treatment comprises water washing and drying.

[0028] The present application provides a method for using the above-mentioned phosphating solution based on the synergistic regulation of electric triggering and biomimetic templates or the above-mentioned phosphating solution based on the synergistic regulation of electric triggering and biomimetic templates in metal protection. A phosphating film is generated on the surface of a metal workpiece to protect the metal workpiece, comprising: rust removal (pickling) → water washing → phosphating (applying a direct current field) → water washing → drying.

[0029] The application provides the phosphating liquid based on the synergistic regulation of the electric triggering and the biomimetic template and the application of the use method of the phosphating liquid based on the synergistic regulation of the electric triggering and the biomimetic template in metal drawing. The phosphating film is generated on the surface of a metal workpiece, and then drawing is carried out, including rust removal (pickling) -> water washing -> phosphating (applying a direct current field) -> water washing -> drying -> drawing.

[0030] The application constructs a synergistic system composed of a "biomimetic template agent", a "controllable phosphorus precursor" and optional "functionalized nanoparticles", induces "molecular template self-assembly" and "in-situ nanocomposite" to occur at the metal / solution interface, and thus constructs an ultra-dense, high-adhesion and strong corrosion-resistant nanocomposite phosphating film on the metal surface in-situ under mild and environmentally friendly conditions.

[0031] The phosphating liquid based on the synergistic regulation of the electric triggering and the biomimetic template has the following advantages: (1) Environmental protection: no nitrite, mild and stable working liquid, and the residue amount is expected to be reduced by more than 90% than that in the traditional process, greatly reducing the waste residue treatment cost; (2) Enhanced corrosion resistance of the film layer; (3) Excellent comprehensive performance: the film layer has extremely strong adhesion to the substrate and excellent wear resistance; (4) Energy saving: low-temperature film forming, saving energy.

[0032] The application has the following beneficial effects: The phosphating liquid based on the synergistic regulation of the electric triggering and the biomimetic template forms a phosphating film under the action of an electric field, and the phosphating film has excellent corrosion resistance, adhesion and wear resistance, and the phosphating process has less residue. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 SEM images of the phosphating films of Examples 1-2 and Comparative Examples 1-4; Figure 2 Element distribution graph and total spectrum graph of EDS detection of the phosphating film of Example 1; Figure 3 Element distribution graph and total spectrum graph of EDS detection of the phosphating film of Comparative Example 4; Figure 4 Spectrum graph of anion detection of the phosphating film of Example 1. DETAILED DESCRIPTION

[0034] The application will be further described below in combination with examples.

[0035] The following will clearly and completely describe the concept, specific solutions, and technical effects of the present invention with reference to embodiments, so as to fully understand the purpose, features, and effects of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention. The various technical features in the present invention can be combined interactively without contradicting each other.

[0036] This invention provides a phosphating solution based on the synergistic regulation of electrical triggering and biomimetic templates: The phosphating solution contains the following key components, and its pH value is adjusted to a weakly acidic range of 3.5-6.0; A. Phosphating precursor: A substance that can undergo controlled hydrolysis to release phosphate ions in an alkaline microenvironment induced by an electric field.

[0037] Preferred type: Phytic acid (PA), which has high and controllable hydrolysis efficiency in the alkaline microenvironment of the cathode interface; one or two of aminotrimethylphosphonic acid (ATMP) or hydroxyethylidene diphosphonic acid (HEDP) can also be selected.

[0038] The concentration is 5-60 g / L.

[0039] B. Bionic template agents: These are polymeric compounds that regulate crystal growth by complexing metal ions with functional groups.

[0040] Preferred types: one of low molecular weight polyacrylic acid (PAA, Mw: 1000-10000) or polyaspartic acid (PASP, Mw: 1000-10000).

[0041] The concentration is 0.1-10.0 g / L.

[0042] C. Nano-reinforced phase: consists of surface-functionalized inorganic nanoparticles.

[0043] Preferred type: Aminated or carboxylated nano-silica (SiO2), with a particle size of 10-30 nm.

[0044] The concentration is 0.5-20 g / L.

[0045] D. Metal ion source: Main film-forming cation source: provides Zn 2+ It can be selected from zinc nitrate, zinc oxide, etc., with a concentration of 5-40g / L.

[0046] Auxiliary film-forming cation source: provides Ca 2+ Ni 2+ The reagents can be selected from calcium nitrate, nickel nitrate, etc., with a concentration of 2-25 g / L.

[0047] E. Auxiliary ingredients: Oxidizing agent: Ammonium molybdate, concentration 0.1-3.0 g / L.

[0048] pH adjuster: Sodium hydroxide or ammonia, used to adjust and stabilize pH.

[0049] Solvent: Deionized water, balance.

[0050] This invention provides a method for using the above-mentioned phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template: a. Pretreatment: The workpiece is pickled and washed with water to ensure a clean surface; b. Phosphating treatment: Immerse the workpiece as the cathode in the above phosphating solution, apply a DC voltage of 1-5V, and keep the distance between the workpiece and the counter electrode at 5-8cm (current density on the workpiece surface is 5-10 A / dm). 2 (), at a temperature of 25-45℃, let stand and soak for 30 seconds to 1 minute; c. Post-processing: Remove the workpiece, wash it with water, and dry it to obtain the phosphating film on the surface.

[0051] This invention provides an application of the above-mentioned phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template in metal drawing: Rust removal (pickling) → water washing → phosphating (applying DC electric field) → water washing → drying → drawing.

[0052] The working mechanism of the phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template in this invention is as follows: The first step is activation: the biomimetic template agent is preferentially adsorbed on the clean metal surface to form an ordered molecular template layer.

[0053] The second step is electrically triggered interface hydrolysis: a DC electric field (1-5V) is applied to the working fluid, with the workpiece acting as the cathode (the current density on the workpiece surface is 5-10 A / dm²). 2 At the cathode interface, an electrochemical reaction generates a locally highly alkaline microenvironment. This environment can efficiently catalyze the controlled hydrolysis of phosphorus precursor molecules such as phytic acid that are enriched there, releasing phosphate ions precisely and slowly, thus achieving "on-demand phosphorus supply" and greatly reducing sludge at the source.

[0054] The third step, directed nucleation and growth: the released phosphate ions react with Zn in the solution. 2+ Ca 2+ Under the guidance of the biomimetic template, metal ions are arranged in an orderly manner, nucleate and grow along the template, forming fine grains.

[0055] The fourth step is nanocomposite: functionalized nanoparticles are "anchored" by a template agent and embedded in the growing phosphating film skeleton, serving as a reinforcing phase to fill pores and increase density, ultimately forming an organic-inorganic nano-interpenetrating network structure.

[0056] Example 1 A phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template, comprising: Phytic acid (50wt% aqueous solution): 30g / L; Polyacrylic acid (PAA, Mw≈3000): 1.5 g / L; Aminated nano-silica (particle size 15nm, 7631-86-9): 3g / L; Zinc nitrate: 18 g / L; Calcium nitrate: 8 g / L; Ammonium molybdate: 0.8 g / L; NaOH: Adjust pH to 4.8; Deionized water: Balance.

[0057] The above-mentioned method for preparing phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template includes the following steps: Phytic acid, polyacrylic acid, aminated nano-silica, zinc nitrate, calcium nitrate, and ammonium molybdate were added to deionized water according to the prescribed dosage. The pH was adjusted to 4.8 with NaOH to obtain a phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template.

[0058] The application of the above-mentioned phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template in metal phosphating includes the following steps: The 3.0mm diameter DT4E annealed wire is processed according to the following process; The processing steps are: rust removal (pickling) → water washing → phosphating (applying DC electric field) → water washing → drying.

[0059] The phosphating process parameters are as follows: DC voltage 3V, workpiece-to-counter electrode distance 5cm, and current density 5 A / dm³. 2 The workpiece is the cathode, the counter electrode is stainless steel, the temperature is 30℃, and the immersion time is 1 minute.

[0060] Test results: Membrane weight: 3.2 g / m³ 2 Sediment content: 0.8g / m³ 2 SEM images of the film are shown below. Figure 1 The film is extremely dense and continuous, with nanoparticles uniformly embedded.

[0061] Example 2 A phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template, comprising: HEDP (60wt% aqueous solution): 25g / L; Polyaspartic acid (PASP, Mw≈4000): 1.0 g / L; Carboxylated nano-silica (particle size 20nm, 7440-21-3): 2.5g / L; Zinc nitrate: 15g / L; Nickel nitrate: 3 g / L; Ammonium molybdate: 0.5 g / L; NaOH: Adjust pH to 5.0; Deionized water: Balance.

[0062] The above-mentioned method for preparing phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template includes the following steps: HEDP, polyaspartic acid, carboxylated nano-silica, zinc nitrate, nickel nitrate, and ammonium molybdate were added to deionized water according to the prescribed dosage. The pH was adjusted to 5.0 with NaOH to obtain a phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template.

[0063] The application of the above-mentioned phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template in metal phosphating includes the following steps: The 3.0mm diameter DT4E annealed wire is processed according to the following process; The processing steps are: rust removal (pickling) → water washing → phosphating (applying DC electric field) → water washing → drying.

[0064] The phosphating process parameters are: DC voltage 2.5V, workpiece-to-counter electrode distance 8cm, and current density 7 A / dm³. 2 The workpiece is the cathode, the counter electrode is graphite, the temperature is 40℃, and the immersion time is 30 seconds.

[0065] Test results: Membrane weight: 3.15 g / m³ 2 Sediment content: 1.0 g / m³ 2 SEM images of the film are shown below. Figure 1 The film layer is dense and uniform.

[0066] Comparative Example 1 A phosphating solution, its preparation method, and its application.

[0067] Based on Example 1, polyacrylic acid (PAA) was removed, while the remaining components and processes were the same as in Example 1.

[0068] Test results: Membrane weight 4.5 g / m 2 Sediment content: 10g / m³ 2 SEM images of the film are shown below. Figure 1The film crystals are coarse and uneven, and the nano-SiO2 exhibits significant agglomeration.

[0069] Conclusion: The lack of a template agent leads to nanoparticle aggregation and uncontrolled reaction, proving that PAA plays an indispensable role in guiding nucleation and dispersing nanoparticles.

[0070] Comparative Example 2 A phosphating solution, its preparation method, and its application.

[0071] Based on Example 1, the aminated nano-silica was removed, and the remaining components and processes were the same as in Example 1.

[0072] Objective: To verify the contribution of functionalized nanoparticles to the mechanical properties and compactness of films.

[0073] Test results: Membrane weight 3.8 g / m 2 Sediment content: 2.8g / m³ 2 SEM images of the film are shown below. Figure 1 The membrane structure is loose and contains visible pores.

[0074] Conclusion: The absence of nanoparticles significantly reduced the compactness, hardness, and wear resistance of the film, demonstrating their crucial reinforcing effect.

[0075] Comparative Example 3 A phosphating solution, its preparation method, and its application.

[0076] Based on Example 1, phytic acid was replaced with zinc dihydrogen phosphate with the same phosphorus content (i.e., no phytic acid was added, but 20.1 g / L of zinc dihydrogen phosphate (containing dihydrate crystals) was added), and the remaining components and processes were the same as in Example 1.

[0077] Test results: Membrane weight 5.6 g / m 2 Sediment content: 15.3 g / m³ 2 SEM images of the film are shown below. Figure 1 The film layer has uneven crystal structure and a lot of sediment.

[0078] Comparative Example 4 A phosphating solution, its preparation method, and its application.

[0079] The composition and preparation method of the phosphating solution are the same as in Example 1.

[0080] Objective: To verify the indispensability of electrical triggering in promoting phytic acid hydrolysis and reducing sludge.

[0081] The application of the above-mentioned phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template in metal phosphating includes the following steps: The 3.0mm diameter DT4E annealed wire is processed according to the following process; The processing steps are as follows: rust removal (pickling) → water washing → phosphating (immersion, without applying DC voltage) → water washing → drying.

[0082] The phosphating process parameters are: temperature 30℃, soaking time 5 minutes.

[0083] Test results: Membrane weight: 1.5 g / m³ 2 Sediment content: 5.8 g / m³ 2 SEM images of the film are shown below. Figure 1 The membrane layer is incomplete.

[0084] Conclusion: Without an applied electric field, phytic acid hydrolysis is slow, resulting in extremely low film formation efficiency, a significant increase in sludge, and poor film protection performance. This comparison strongly demonstrates the core role of the electrically triggered mechanism in achieving the high-performance effect of this invention.

[0085] Phosphating film performance testing: To ensure the accuracy and comparability of the test results, the performance tests of the phosphating films described in the examples and comparative examples were performed using the following national standard (GB / T) methods or industry-standard methods: (1) Corrosion resistance test Testing Standard: GB / T 10125-2021 "Artificial Atmosphere Corrosion Test - Salt Spray Test" Method Summary: A neutral salt spray test (NSS) was used. The phosphated sample was placed in a salt spray chamber and continuously sprayed with a 5% sodium chloride solution at (35±2)℃. The time elapsed from the start of the test until the first red corrosion product appeared on the surface of the phosphated film was recorded as the basis for evaluating corrosion resistance (unit: hours).

[0086] (2) Adhesion test Testing standard: GB / T 9286-2021 "Paints and Varnishes - Cross-cut Test" Method Summary: Using a specialized crisscross cutter, cut a grid of squares with a spacing of 1mm or 2mm onto the surface of the phosphated film, cutting down to the metal substrate. Then, gently brush away any debris with a soft brush, and firmly adhere the specialized adhesive tape to the grid by hand, then quickly peel it off. Rate the area of ​​film detachment from the substrate according to a standard chart. Grade 0 is the best, indicating completely smooth cut edges with no detachment.

[0087] (3) Abrasion resistance test Testing Standard: GB / T 1768-2006 "Determination of Abrasion Resistance of Paints and Varnishes - Rotary Rubber Grinding Wheel Method" Method Summary: A Taber abrasion tester is used. The phosphated sample is fixed on a turntable, and a specified load (e.g., 1 kg) is applied to the sample surface using a specific friction wheel (e.g., CS-10 rubber wheel), causing the sample to rotate a certain number of revolutions (e.g., 1000 revolutions). After the test, the mass loss of the sample is measured using a precision balance, and the abrasion resistance of the film is characterized by the weight loss value (mg). The lower the weight loss, the better the abrasion resistance.

[0088] The test results are shown in Table 1 below: Table 1:

[0089] It can be seen that the phosphating films of Examples 1-2 have excellent corrosion resistance, adhesion, and wear resistance, and there is little sediment during the phosphating process.

[0090] Phosphating film composition analysis: EDS and anion detection were performed on the phosphating films described in Example 1 and Comparative Example 4.

[0091] (1) The elemental distribution map and total number spectrum of the phosphating film detected by EDS in Example 1 are shown in the figure. Figure 2 The data is shown in Table 2.

[0092] The elemental distribution map and total number spectrum of the phosphating film in Comparative Example 4, obtained by EDS analysis, are shown below. Figure 3 The data is shown in Table 3.

[0093] Table 2:

[0094] Table 3:

[0095] It can be seen that the phosphating film of Comparative Example 4 does not contain P element, while the phosphating film of Example 1 contains P element and has a high oxygen element content. It is speculated that the phosphating film of Example 1 may contain phosphate ions.

[0096] (2) The anion detection spectrum of the phosphating membrane in Example 1 is shown in the figure. Figure 4 The data is shown in Table 4.

[0097] Table 4:

[0098] It can be seen that the phosphating film of Example 1 contains phosphate.

[0099] In summary, the phosphating solution of this invention, based on the synergistic regulation of electrical triggering and biomimetic template, decomposes phytic acid into phosphate under the action of an electric field, forming a dense phosphating film with other components. This film exhibits excellent corrosion resistance, adhesion, and wear resistance, and produces less sediment during the phosphating process.

[0100] The above is a detailed description of the preferred embodiments of the present invention. However, the present invention is not limited to the embodiments described. Those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of the present invention. All such equivalent modifications or substitutions are included within the scope defined by the claims of the present invention.

Claims

1. A phosphating solution based on the synergistic regulation of electrical triggering and biomimetic templates, characterized in that, include: Phosphating precursor: 5-60 g / L; Bionic template agent: 0.1-10.0 g / L; Nano-reinforced phase: 0.5-20 g / L; Metal ion source: 7-65 g / L; Oxidizing agent: 0.1-3.0 g / L; pH adjuster: Adjust pH to 3.5-6.0; Deionized water: Balance; The phosphating precursor is one or more of phytic acid, aminotrimethylphosphonic acid and hydroxyethylidene diphosphonic acid; The phosphating solution based on the coordinated control of electrical triggering and biomimetic template is used with the workpiece as the cathode to apply an electric field.

2. The phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template according to claim 1, characterized in that, The current density on the surface of the workpiece is 5-10 A / dm. 2 ; The biomimetic template agent is one or more of polyacrylic acid and polyaspartic acid.

3. The phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template according to claim 2, characterized in that, The weight-average molecular weight of the polyacrylic acid is 1000-10000; The weight-average molecular weight of the polyaspartic acid is 1000-10000.

4. The phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template according to claim 1, characterized in that, The nano-reinforcing phase is one or more of aminated nano-silica and carboxylated nano-silica.

5. The phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template according to claim 4, characterized in that, The aminated nano-silica has a particle size of 10-30 nm; The carboxylated nano-silica has a particle size of 10-30 nm.

6. The phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template according to claim 1, characterized in that, The metal ion source includes a main film-forming cation source and an auxiliary film-forming cation source, with the concentration of the main film-forming cation source being 5-40 g / L and the concentration of the auxiliary film-forming cation source being 2-25 g / L. The oxidant is ammonium molybdate; The pH adjuster is one or more of sodium hydroxide, potassium hydroxide, and ammonia water.

7. The phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template according to claim 6, characterized in that, The primary film-forming cation source is one or more of zinc nitrate and zinc oxide; The auxiliary film-forming cation source is one or more of calcium nitrate and nickel nitrate.

8. The method of using the phosphating solution based on the synergistic regulation of electrical triggering and biomimetic templates as described in any one of claims 1-7, characterized in that, Includes the following steps: The workpiece undergoes pretreatment, followed by phosphating, and finally posttreatment. The phosphating treatment includes: immersing the pretreated workpiece as a cathode into the phosphating solution based on the synergistic regulation of electrical triggering and biomimetic templates, applying a DC voltage, and setting the current density on the workpiece surface to 5-10 A / dm². 2 Soak at a temperature of 25-45℃ for 30 seconds to 1 minute.

9. The method for using the phosphating solution based on the synergistic regulation of electrical triggering and biomimetic templates according to claim 8, characterized in that, The phosphating solution used in the phosphating treatment also includes a counter electrode. The voltage between the workpiece and the counter electrode is 1-5V, and the distance between the workpiece and the counter electrode is 5-8cm. The pretreatment includes acid washing and water washing; The post-processing includes washing and drying.

10. The application of the phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template as described in any one of claims 1-7, or the method of using the phosphating solution based on the synergistic regulation of electrical triggering and biomimetic template as described in any one of claims 8-9, in metal protection or metal drawing.

Images