Preparation method and application of high-efficiency nano scale anti-fouling membrane

Abstract

The application discloses a preparation method and application of a high-efficiency nano scale-inhibiting film, and comprises the following steps: S1, preparing a film-forming solution: sequentially dissolving organic phosphonate and a metal salt corresponding to divalent or higher valence metal ions in water, uniformly stirring, and adjusting the pH value of the solution to obtain the film-forming solution; S2, pretreating a metal substrate; S3, immersing the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1 to perform soaking treatment; or coating the film-forming solution obtained in step S1 on the surface of the metal substrate after the pretreatment in step S2. The application spontaneously constructs a dense nano scale-inhibiting film on the surface of a metal material by using an organic polyamino polymethylene phosphonic acid scale inhibitor and divalent metal ions, and the preparation method of the scale-inhibiting film has the advantages of high scale inhibition efficiency, economic feasibility, easy repair and multi-substrate applicability.

Description

Technical Field

[0001] This invention belongs to the field of industrial scale prevention and material surface treatment technology, specifically relating to a method for preparing and applying a high-efficiency nanoscale inhibitory membrane. Background Technology

[0002] Mineral scaling is the nucleation and deposition process of mineral ions dissolved in water on the surface of equipment. It occurs widely in oil and gas extraction, geothermal development, industrial cooling circulating water, seawater desalination, and daily hot water systems. Scaling leads to a decrease in the effective pipe diameter and a reduction in heat transfer efficiency, and in severe cases, it can cause pipe blockage, equipment damage, and even system failure. Statistics show that global economic losses due to scaling amount to hundreds of billions of US dollars annually, accounting for approximately 0.25% of global GDP. Therefore, effectively controlling mineral scaling has always been a common technical challenge in industrial production and water treatment.

[0003] To address the hazards of scaling, various scale inhibition strategies have been developed. Traditional scale inhibition strategies mainly include mechanical treatment, the addition of liquid chemical scale inhibitors, and scale-inhibiting functional coatings or microstructures. However, current scale inhibition methods all have insurmountable drawbacks. For example, passive descaling methods such as mechanical scraping and high-pressure water jet flushing can only provide temporary relief and are often accompanied by secondary damage to the equipment substrate, production interruptions, and continuous investment of human and material resources.

[0004] Adding liquid chemical scale inhibitors to scaled water to prevent or delay the nucleation and crystal growth of inorganic scale is currently the most widely used active scale prevention technology. For example, patent document CN106396147A discloses a liquid scale inhibitor with the following raw materials: deionized water, molybdate, organophosphonate, zinc sulfate, zinc chloride, polyacrylic acid, maleic anhydride, vanadium pentoxide, sodium gluconate, sodium tungstate, and sodium p-styrene sulfonate. However, this type of liquid scale inhibitor generally suffers from drawbacks such as large usage and limited application scenarios. More importantly, in large systems such as cooling towers and deep horizontal wells, the chemical loss of the scale inhibitor during transportation can exceed 80%, with a large amount of effective components being lost before reaching the site of action. In addition, some phosphorus- and nitrogen-containing chemical scale inhibitors can easily cause serious environmental pollution problems such as eutrophication of water bodies.

[0005] Against this backdrop, directly modifying material surfaces and constructing scale-inhibiting coatings or microstructures has become a highly regarded active scale prevention strategy in recent years. For example, patent documents CN109680279A and CN119752321A provide corresponding scale-inhibiting coating structures. By functionally designing the substrate surface, the mineral adhesion process can be delayed by forming a hydration layer, air layer, or lubrication layer, thereby inhibiting scale deposition. This approach is not limited by agent delivery distance and dilution effects, enabling continuous and active scale prevention, which has advantages that traditional methods cannot achieve. However, existing surface modification schemes generally have the following limitations: (1) Existing surface modification antifouling strategies, such as polymer hydrogel coatings, superhydrophobic micro-nano structures, diamond-like nanocoatings and lubricant injection surfaces, generally rely on complex processes such as chemical vapor deposition, plasma etching or photolithography. The preparation process requires expensive equipment and raw materials, and the cost is very high, making it difficult to promote on a large scale in extensive industrial scenarios. (2) The above coatings often have strict limitations on substrate material, surface roughness and chemical composition. The same preparation process is difficult to be universally applicable to different engineering metals, and the substrate applicability is narrow. (3) In actual working conditions, once the coating is partially damaged after being subjected to particle scouring, chemical corrosion or mechanical scratching, it will permanently lose its scale inhibition function. It cannot be repaired online or regenerated on site, which constitutes a fatal defect for industrial equipment that requires long-term continuous service.

[0006] To address the above problems, this invention is proposed. Summary of the Invention

[0007] To address the aforementioned technical problems, the present invention aims to provide a method for preparing and applying a high-efficiency nanoscale inhibitory membrane. This method utilizes an organic polyamino polymethylene phosphate scale inhibitor and divalent metal ions to spontaneously construct a dense nanoscale inhibitory membrane on the surface of a metal material. The preparation method of this scale inhibitory membrane offers advantages such as high-efficiency scale inhibition, economic feasibility, ease of repair, and applicability to multiple substrates.

[0008] To achieve the above objectives, the present invention adopts the following technical solution: In a first aspect, the present invention provides a method for preparing a high-efficiency nanoscale inhibitory membrane, comprising the following steps: S1. Preparation of film-forming solution: Dissolve the organophosphonate and the metal salt corresponding to the divalent or higher valence metal ion in water in sequence, stir evenly, and adjust the pH value of the solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate; S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1 for soaking treatment; or, coat the surface of the metal substrate after the pretreatment in step S2 with the film-forming solution obtained in step S1.

[0009] As a preferred embodiment of the present invention, in step S1, the organophosphonate is selected from at least one of polyaminopolymethylene phosphonic acid compounds.

[0010] As a preferred embodiment of the present invention, the polyaminopolymethylenephosphonic acid compound is selected from at least one of the following: diethylenetriaminepentamethylenephosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, and bis-1,6-ethylenetriaminepentamethylenephosphonic acid.

[0011] As a preferred embodiment of the technical solution of the present invention, in step S1, the metal ions are selected from, but are not limited to, Zn. 2+ Co 2+ Ni 2 + Mn 2+ Cu 2+ At least one of them.

[0012] As a preferred embodiment of the present invention, the metal salt is selected from, but is not limited to, nitrates, chlorides, and acetates.

[0013] As a preferred embodiment of the present invention, in step S1, the concentration of organophosphonate is 1~10 mmol / L; the concentration of metal ions is 2~50 mmol / L.

[0014] As a preferred embodiment of the technical solution of the present invention, in step S1, the pH value of the solution is 2 to 5.

[0015] As a preferred embodiment of the technical solution of the present invention, in step S2, the pretreatment of the metal substrate includes the following steps: polishing the metal substrate and then cleaning it with anhydrous ethanol.

[0016] As a preferred embodiment of the technical solution of the present invention, in step S3, the soaking temperature is 10~90 ℃ and the soaking time is 5~60 min.

[0017] Secondly, the present invention also aims to protect the application of the above-described method for constructing scale-inhibiting membranes in various metal environments for scale inhibition.

[0018] Compared with the prior art, the present invention has the following beneficial effects: (1) The method for preparing the scale inhibitor membrane provided by the present invention is different from the existing method of dispersing the scale inhibitor in a solution (i.e., liquid scale inhibitor). The present invention creatively achieves a high-efficiency scale inhibition effect by screening the types of organophosphonates and cations to directly construct a nanoscale scale inhibitor membrane on the surface of a metal substrate. The resulting nanoscale scale inhibitor membrane is thin, requires a small amount of scale inhibitor, is easy to implement quickly, and is convenient and efficient.

[0019] (2) The method for preparing the scale inhibitor membrane provided by the present invention can achieve high-efficiency scale inhibition. In the scale inhibition test of the precipitation solution in the simulation experiment, the amount of scale per unit area on the surface of the metal material with the nano scale inhibitor membrane is reduced by 85% to 95% compared with the metal material without the nano scale inhibitor membrane.

[0020] (3) The method for preparing the scale inhibitor film provided by the present invention also has the effect of corrosion inhibition. In the electrochemical performance test, the current density is significantly reduced, and the corresponding corrosion rate is significantly reduced.

[0021] (4) The method for preparing the scale inhibitor membrane provided by the present invention has strong substrate universality. The nanoscale inhibitor membrane prepared by the present invention can be effectively formed in a variety of engineering metals such as carbon steel, stainless steel, titanium alloy, copper, and Hastelloy. When analyzing the scale inhibition effect of the materials through the above-mentioned scale inhibition performance coating precipitation experiment, the scale inhibition efficiency of most metals can reach more than 90% after covering with the nanoscale inhibitor membrane.

[0022] (5) The method for preparing the scale inhibitor membrane provided by the present invention has the advantage of easy repair. The scale inhibitor membrane constructed by the present invention can achieve short-term regeneration and repair. The scale inhibition performance of the worn sample can be restored to more than 95% of the original intact membrane performance. It has excellent rapid in-situ repair and regeneration and anti-wear repair capabilities. It can effectively adapt to the actual service scenarios of slight wear and local damage on the workpiece surface and effectively ensure the scale inhibition and protection performance of the substrate.

[0023] (6) The preparation method of the scale inhibitor membrane provided by the present invention is simple and can quickly and efficiently cover the nano scale inhibitor membrane layer in the equipment already in operation; the raw materials used are simple, the cost is controllable, and the effect is outstanding. Attached Figure Description

[0024] Figure 1 The image shows a SEM-EDS image of the metal substrate after processing in Example 13. Figure 2 XPS image of the metal substrate after processing in Example 13; Figure 3 The ATR-FTIR infrared spectrum signal at the same location on the metal substrate after treatment in Example 13 changes with immersion time; Figure 4 Figure 13 shows the ATR-FTIR spectra of the metal substrates obtained after immersion in DTPMP solution and DTPMP-Zn solution, respectively. Figure 13 on the left shows the ATR-FTIR spectra of the metal substrates after immersion in DTPMP solution and DTPMP-Zn solution. Figure 14 on the right shows the ATR-FTIR spectra of the metal substrates after immersion in Zn solution. 2+ ATR-FTIR spectra of the solution and the DTPMP-Zn solution after immersion; Figure 5 A comparison chart of scale inhibition efficiencies for different metal substrates; Figure 6 A comparison chart of scale inhibition efficiency of metal substrates under different abrasion conditions; Figure 7 The corrosion resistance test results are for the metal substrate treated in Example 13; Figure 8 Figure 1 shows the parameter optimization results during the preparation of the scale inhibitor membrane. Figure 2 shows the scale inhibition efficiency of the metal substrate after treatment with different cations and corresponding metal forms. Figure 3 shows the scale inhibition efficiency of the metal substrate after treatment at different pH values. Figures 4 and 5 show the scale inhibition efficiency of the metal substrate after treatment with different zinc ion concentrations. Figure 6 shows the scale inhibition efficiency of the metal substrate after treatment with different DTPMP concentrations. Figure 7 shows the scale inhibition efficiency of the metal substrate after treatment with different immersion times. Figure 8 shows the scale inhibition efficiency of the metal substrate after retreatment with different polishing and grinding grits. Figure 9 shows a comparison of the scale inhibition efficiency of the metal substrate after one-step and step-by-step treatment. Detailed Implementation

[0025] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0026] Unless otherwise specified, all raw and auxiliary materials used in this invention can be purchased through market channels.

[0027] This invention provides a method for preparing a high-efficiency nanoscale inhibitory membrane, comprising the following steps: S1. Preparation of film-forming solution: Dissolve the organophosphonate and the metal salt corresponding to the divalent or higher valence metal ion in water in sequence, stir evenly, and adjust the pH value of the solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate; S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1 for soaking treatment; or, coat the surface of the metal substrate after the pretreatment in step S2 with the film-forming solution obtained in step S1.

[0028] Of course, to accelerate the film formation of the film-forming solution, a step S4 can be added after step S3, that is... The metal substrate processed in step S3 is then air-dried or oven-dried. It is understood that the above steps are not mandatory, and those skilled in the art can choose flexibly.

[0029] In the above technical solution, an organophosphonate inhibitor is selected and spontaneously coordinated and cross-linked with at least one divalent or higher-valence metal ion on the surface of the metal material to form a dense nanofunctional film, which achieves scale inhibition and other effects. When either is used alone, the treated material has no scale inhibition effect.

[0030] In step S1 of some embodiments, the organophosphonate is selected from at least one of polyaminopolymethylenephosphonic acid compounds. Exemplarily, organophosphonates may include, but are not limited to, the following: diethylenetriaminepentamethylenephosphonic acid (DTPMP), aminotrimethylenephosphonic acid (ATMP), ethylenediaminetetramethylenephosphonic acid (EDTMP), hexamethylenediaminetetramethylenephosphonic acid (HDTMP), and bis-1,6-ethylenetriaminepentamethylenephosphonic acid (BHPMP); preferably, DTPMP.

[0031] In step S1 of some embodiments, the metal ion is selected from divalent or higher valence ions capable of coordinating with the above-mentioned organophosphonic acids, including but not limited to: Zn 2+ Co 2+ Ni 2+ Mn 2+ Cu 2+ At least one of the following; preferably, Zn 2+ The metal ions mentioned above can be added in the form of common metal salts, including but not limited to nitrates, chlorides, and acetates.

[0032] In step S1 of some embodiments, the concentration of organophosphonate is 1~10 mmol / L; the concentration of metal ion is 2~50 mmol / L. It is understood that the concentration of organophosphonate can be any value selected from 1 mmol / L, 2 mmol / L, 3 mmol / L, 4 mmol / L, 5 mmol / L, 6 mmol / L, 7 mmol / L, 8 mmol / L, 9 mmol / L, 10 mmol / L, or any specific value within the above range; preferably, the concentration of organophosphonate is 5~8 mmol / L; similarly, the concentration of metal ions can be 2 mmol / L, 3 mmol / L, 4 mmol / L, 5 mmol / L, 6 mmol / L, 7 mmol / L, 8 mmol / L, 9 mmol / L, 10 mmol / L, 11 mmol / L, 12 mmol / L, 13 mmol / L, 14 mmol / L, 15 mmol / L, 16 mmol / L, 17 mmol / L, 18 mmol / L, 19 mmol / L, 20 mmol / L, 21 mmol / L, 22 mmol / L, 23 mmol / L, 23 mmol / L, 24 mmol / L, 25 mmol / L, 26 mmol / L, 27 mmol / L, 18 mmol / L, 19 mmol / L, 20 mmol / L, 21 mmol / L, 22 mmol / L, 23 mmol / L, 24 mmol / L, 25 mmol / L, 26 mmol / L, 27 mmol / L, 28 mmol / L, 2 ... The concentration of the metal ion is one of the following values: 24 mmol / L, 25 mmol / L, 26 mmol / L, 27 mmol / L, 28 mmol / L, 29 mmol / L, 30 mmol / L, 31 mmol / L, 32 mmol / L, 33 mmol / L, 34 mmol / L, 35 mmol / L, 36 mmol / L, 37 mmol / L, 38 mmol / L, 39 mmol / L, 40 mmol / L, 41 mmol / L, 42 mmol / L, 43 mmol / L, 44 mmol / L, 45 mmol / L, 46 mmol / L, 47 mmol / L, 48 mmol / L, 49 mmol / L, and 50 mmol / L, or any specific value within the above range; preferably, the concentration of the metal ion is 5 to 20 mmol / L. In practical applications, the molar ratio of metal ions to organophosphonates is controlled at 1 to 10:1; more preferably, the molar ratio is controlled at 2 to 3:1.

[0033] In step S1 of some embodiments, the pH value of the solution is 2-5; preferably, the pH value of the solution is 2.4-4.0. In actual adjustment, common solutions such as sodium hydroxide solution can be used.

[0034] In step S2 of some embodiments, the pretreatment of the metal substrate includes the following steps: grinding the metal substrate and then cleaning it with anhydrous ethanol. The metal substrate is selected from ferrous metals, non-ferrous metals and their alloys, including but not limited to carbon steel, stainless steel, titanium and titanium alloys, copper and copper alloys, nickel-based alloys (such as Hastelloy), etc.; the metal substrate is ground using a grinding machine or sandpaper, and the grinding grit can be in the range of 240 grit to 1000 grit; cleaning can be performed with anhydrous ethanol, and ultrasonic cleaning can be used as an aid during the cleaning process to remove surface oil and impurities.

[0035] In step S3 of some embodiments, the film-forming solution can form an antiscaling film on the surface of the metal substrate by immersion or coating. Immersion can be carried out by static immersion, stirred immersion, repeated immersion, etc.; the immersion temperature is 10~90 ℃, and the immersion time is 5~60 min; preferably, the immersion temperature is 20~60 ℃; more preferably, static immersion is selected and the immersion is carried out at room temperature. When the antiscaling film is constructed by coating, one or more of the following methods can be used: spraying, brushing, spin coating, roller coating, and spray cycle. The above processes can be carried out using existing mature methods, and the specific implementation method is not limited in this invention.

[0036] When using an immersion method for treatment, after the metal substrate is removed from the film-forming solution, it can be washed to remove any loose deposits remaining on the surface. The washing can be done first with purified water, followed by anhydrous ethanol.

[0037] The scale inhibitor membrane constructed based on the above method has a thickness of about 1~20 nm, and it is generally considered to have a scale inhibitory effect when the thickness is ≥1 nm.

[0038] The method provided by the present invention will be further described in detail below through specific implementation methods.

[0039] Example 1 A method for preparing a high-efficiency nanoscale inhibitory membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriamine pentamethylphosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 5 mmol / L and 10 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the carbon steel C1018 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0040] Example 2 A method for preparing a high-efficiency nanoscale inhibitory membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriamine pentamethylphosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 5 mmol / L and 10 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the SS316 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0041] Example 3 A method for preparing a high-efficiency nanoscale inhibitory membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriamine pentamethylphosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 5 mmol / L and 10 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the copper substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0042] Example 4 A method for preparing a high-efficiency nanoscale inhibitory membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriaminepentimidephosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 3.5 mmol / L and 7 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the SS316 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0043] Example 5 A method for preparing a high-efficiency nanoscale inhibitory membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriaminepentimidephosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 3.5 mmol / L and 7 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 4.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the SS316 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0044] Example 6 A method for preparing a high-efficiency nanoscale inhibitory membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriaminepentimidephosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 3.5 mmol / L and 7 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 2.5 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the carbon steel C1018 to 240 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0045] Example 7 A method for preparing a high-efficiency nanoscale inhibitory membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriaminepentimidephosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 5 mmol / L and 25 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the carbon steel C1018 substrate to 400 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0046] Example 8 A method for preparing a high-efficiency nanoscale inhibitory membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriaminepentimidephosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 1 mmol / L and 2 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the SS316 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0047] Example 9 A method for preparing a high-efficiency nanoscale inhibitory membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriaminepentimidephosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 3.5 mmol / L and 7 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the SS316 substrate to 80 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 minutes. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0048] Example 10 A method for preparing a high-efficiency nanoscale inhibitory membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriaminepentimidephosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 3.5 mmol / L and 7 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the SS316 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 5 minutes. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0049] Example 11 A method for preparing a high-efficiency nanoscale inhibitory membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriamine pentamethylphosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 5 mmol / L and 10 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the SS316 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 60 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0050] Example 12 A method for preparing a high-efficiency nanoscale inhibitory membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriaminepentimidephosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 3.5 mmol / L and 7 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the SS316 substrate to 1000 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0051] Example 13 A method for preparing a high-efficiency nanoscale inhibitory membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriaminepentimidephosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 3.5 mmol / L and 7 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the C1018 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0052] Comparative Example 1 A method for preparing a nanoscale antiscaling membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriamine pentamethylphosphonic acid (DTPMP) was dissolved in water at a concentration of 5 mmol / L. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the carbon steel C1018 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0053] Comparative Example 2 A method for preparing a nanoscale antiscaling membrane includes the following steps: S1. Preparation of film-forming solution: Dissolve zinc chloride in water at a concentration of 5 mmol / L, stir well, and adjust the pH of the solution to about 3.0 with sodium hydroxide solution to obtain the film-forming solution; S2. Pretreatment of the metal substrate: After sanding the carbon steel C1018 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0054] Comparative Example 3 A method for preparing a nanoscale antiscaling membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriaminepentimidephosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 0.1 mmol / L and 0.2 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the carbon steel C1018 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0055] Comparative Example 4 A method for preparing a nanoscale antiscaling membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriaminepentimidephosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 3.5 mmol / L and 7 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 6.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the SS316 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0056] Comparative Example 5 A method for preparing a nanoscale antiscaling membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriaminepentimidephosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 3.5 mmol / L and 7 mmol / L, respectively. After stirring evenly, the pH of the solution was approximately 1.72, thus obtaining the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the carbon steel C1018 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0057] Comparative Example 6 A method for preparing a nanoscale antiscaling membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriaminepentimidephosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 3.5 mmol / L and 7 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the carbon steel C1018 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 0.5 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0058] Comparative Example 7 A method for preparing a nanoscale antiscaling membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriamine pentamethylphosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 5 mmol / L and 50 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the carbon steel C1018 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 minutes. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0059] Comparative Example 8 A method for preparing a nanoscale antiscaling membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriaminepentimidephosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 0.5 mmol / L and 1 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the SS316 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 minutes. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0060] Comparative Example 9 A method for preparing a nanoscale antiscaling membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriaminepentimidephosphonic acid (DTPMP) and zinc chloride were dissolved in water at concentrations of 3.5 mmol / L and 7 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 4.5 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the carbon steel C1018 substrate to 240 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 minutes. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0061] Comparative Example 10 A method for preparing a nanoscale antiscaling membrane includes the following steps: S1. Pretreatment of the metal substrate: After sanding the carbon steel C1018 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S2. The metal substrate after the pretreatment in step S1 is first immersed (2 min) in a 3.5 mmol / L aqueous solution of diethylenetriamine pentamethylphosphonic acid, and then immersed (2 min) in a 7 mmol / L aqueous solution of zinc chloride. The process is repeated alternately for a total immersion time of 10 min. S3. After removing the metal substrate processed in step S2 from the solution, rinse it with pure water and anhydrous ethanol, and then let it air dry.

[0062] Comparative Example 11 A method for preparing a nanoscale antiscaling membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriamine pentamethylphosphonic acid (DTPMP) and calcium chloride were dissolved in water at concentrations of 5 mmol / L and 10 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the carbon steel C1018 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0063] Comparative Example 12 A method for preparing a nanoscale antiscaling membrane includes the following steps: S1. Preparation of film-forming solution: Diethylenetriamine pentamethylphosphonic acid (DTPMP) and barium chloride were dissolved in water at concentrations of 5 mmol / L and 10 mmol / L, respectively. After stirring evenly, the pH of the solution was adjusted to about 3.0 with sodium hydroxide solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate: After sanding the carbon steel C1018 substrate to 600 grit with sandpaper, ultrasonic cleaning is performed using anhydrous ethanol. S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1, and perform static immersion treatment at room temperature for 10 min. S4. After removing the metal substrate processed in step S3 from the solution, rinse it with pure water and anhydrous ethanol, and then air dry it.

[0064] The performance of the treated metal substrates in the examples and comparative examples was tested, and the test methods and results are as follows.

[0065] (1) Scale inhibition efficiency test Prepare the treated metal substrates from the examples and comparative examples, as well as the corresponding untreated blank substrates of the same size and specifications. Use the hanging plate method to evaluate the scale inhibition performance of the nanoscale inhibitory membrane. The substrates are suspended and fixed to the iron stand by thin wires. The suspension height of all the hanging plates and the distance between them and the center of the beaker are uniform to ensure that the flow field and temperature field of the experimental system are uniform and to eliminate experimental errors.

[0066] Add scaling solution (Ca) to the beaker 2+ = 30.0 mmol / L, CO3 2- = 10.0 mmol / L, HCO3 - = 60 mmol / L, NaCl = 1 mol / L, pH = 8.59, calcium carbonate saturation index SI calcite = 2.92, 25 ℃), place the stirring magnet in the solution, set the stirring speed to 500 r / min, completely immerse the carbon steel plate in the solution, start the precipitation experiment and start timing.

[0067] After reacting for 2 hours, the tablets were removed and rinsed quickly with ultrapure water and anhydrous ethanol to remove residual solution and impurities from the surface. They were then placed in a dry environment at room temperature to air dry before testing.

[0068] A microbalance with a detection limit of 0.01 mg was used to weigh the samples coated with the nanoscale inhibitory film and the blank sample before and after the experiment to obtain the change in scale deposition mass. To ensure testing accuracy, a gravimetric method combined with inductively coupled plasma optical emission spectrometry (ICP-OES) was used to accurately measure the amount of calcium carbonate scale. Each group of air-dried samples was immersed in a 2% dilute nitric acid solution to completely dissolve the surface calcium carbonate scale. After dilution and filtration pretreatment, the calcium ion concentration in the solution was detected using ICP-OES and converted into calcium carbonate mass.

[0069] Scale inhibition efficiency ( η The calculation method is as follows: In the formula This refers to the amount of calcium carbonate deposited on the coated tablets after treatment with a nanoscale antiscaling membrane. This represents the amount of calcium carbonate deposited on the blank substrate.

[0070] (2) Corrosion resistance test The corrosion protection performance of the nanoscale inhibitory membrane was evaluated by measuring the linear sweep voltammetry (LSV) curves of the samples using a three-electrode system at room temperature using an electrochemical workstation. The test medium was a 3.5 wt% NaCl aqueous solution. In the test system, the treated / untreated metal substrates were used as the working electrode, a platinum electrode as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A linear sweep rate of 10 mV / s was set, and polarization curves were measured for each group of samples to obtain the characteristic parameters of the Tafel polarization curves. The corrosion current density was obtained by fitting the polarization curves. The corrosion inhibition efficiency of metal substrates treated with nanoscale antiscaling films and the corrosion rate of untreated metal substrates were calculated respectively.

[0071] The formula for calculating the annual corrosion rate (CR, mm / year) of a metal substrate is as follows: In the formula Corrosion current density (A / cm) 2 ); The unit conversion constant is 3272. This represents the relative atomic mass of the metal substrate; for example, the relative atomic mass of C1018 carbon steel is 55.85 g / mol. The oxidation state of the metal is the oxidation state. This refers to the density of the metallic substrate; for example, the density of C1018 carbon steel is 7.87 g / cm³. 3 .

[0072] The formula for calculating corrosion inhibition efficiency is as follows: In the formula The corrosion current density of the metal substrate treated with a nanoscale antiscaling film; This represents the corrosion current density of the untreated metal substrate.

[0073] (3) Easy repair performance To simulate the working conditions in which the workpiece surface suffers different degrees of abrasion, scratches and failure of the nanoscale inhibitory film, sandpaper of different grits was used to polish the surface of the formed nanoscale inhibitory film to construct wear samples with different roughness and damage levels, simulating the film damage defects caused by long-term scouring and abrasion of the workpiece.

[0074] The carbon steel workpiece damaged by grinding was then immersed again in the film-forming solution and left to stand at room temperature for 10 minutes. Utilizing the material's in-situ film-forming properties, the damaged and abraded areas can spontaneously induce the regrowth and deposition of a nano-scale inhibitory functional layer, regenerating a complete and dense nano-scale inhibitory film layer in situ at the damaged location, achieving rapid self-repair of nano-scale inhibitory film defects. The repaired sample was then subjected to the aforementioned static plate scale inhibition experiment again.

[0075] See Figure 1 As shown, phosphorus (P) and zinc (Zn) characteristic elements can be detected on the surface of the modified C1018 substrate, proving that the zinc-phosphorus functional components were successfully loaded onto the surface of the metal substrate, and preliminarily confirming the effective preparation of the nanoscale inhibitory membrane.

[0076] See Figure 2 As shown, a P 2p characteristic peak was detected at 133.5 eV and a Zn 2p characteristic peak was detected at 1022.3 eV, proving the successful formation of PO-Zn coordination bonds in the system and indicating the formation of a DTPMP-Zn nanoscale inhibitory film on the substrate surface. Simultaneously, due to the shielding effect of the surface nanoscale inhibitory film, the Fe 2p characteristic signal intensity corresponding to the substrate decreased by 35%-50%, and the binding energy underwent a positive shift, further verifying the complete coverage effect of the nanoscale inhibitory film on the metal substrate.

[0077] See Figure 3 As shown, the formation process of the nanoscale antiscaling membrane was dynamically monitored using attenuated total reflectance infrared spectroscopy (ATR-FTIR), with spectral data acquired every minute. The test results show that DTPMP molecules are at approximately 1230 cm⁻¹. -1 The P=O stretching vibration peak at [location] gradually weakens and breaks down during the film formation process, while [value] at ~1085 cm⁻¹ [value] [value]. -1 The characteristic absorption peak of PO-(Me) formed by the coordination of DTPMP and Zn gradually appeared, dynamically confirming the formation process of DTPMP-Zn nanoscale inhibitory film on the steel substrate surface.

[0078] See Figure 4 Referring to the corresponding DTPMP and zinc ion concentrations in Example 13, the CO181 substrate was treated using the processing method of the example to obtain... Figure 4 The processing results are shown in Figure a. Figure a shows the ATR-FTIR spectra of C1018 carbon steel after immersion in DTPMP solution for 0, 1, 2, 3, 4, 30, 45, and 60 minutes, respectively; Figure b shows the ATR-FTIR spectra of C1018 carbon steel after immersion in Zn... 2+ ATR-FTIR spectra after immersion in the solution for 0, 1, 2, 3, 4, 30, 45, and 60 minutes, respectively. The spectrum of the DTPMP-Zn nanoscale inhibitor film formed after immersion for 30 minutes is included in each figure for comparison. It can be seen from the figures that only when DTPMP and Zn... 2+ They must both exist in solution to form a nanoscale inhibitory membrane.

[0079] See Figure 5 Based on the processing method of Example 13, different metal substrates can be processed to obtain the scale inhibition membrane construction method provided by the present invention, which is applicable to different substrate types, has a high overall scale inhibition efficiency, and is widely applicable.

[0080] See Figure 6 Based on the processing method of Example 13, the processed metal substrate was polished with different mesh sizes, and the scale inhibition efficiency was measured again after reprocessing. For specific processing procedures, please refer to the test method in the aforementioned section on easy-to-repair performance. The "untreated" aspect in the figure refers to polishing without subsequent soaking treatment. As can be seen from the figure, the scale inhibition membrane construction method provided by this invention has good easy-to-repair properties.

[0081] See Figure 7 As can be seen, the current density of the C1018 substrate decreased significantly after treatment, indicating that the material treated with the nanoscale inhibitor film also has corrosion resistance.

[0082] See Figure 8 Figure a compares the results of parameter optimization for the preparation of nanoscale antiscaling films in the examples and comparative examples. Red represents C1018 carbon steel, and blue represents SS316 stainless steel. When the metal substrate is C1018, the treatment method is based on Example 13 with corresponding adjustments; when the metal substrate is SS316, the treatment method is based on Example 4 with corresponding adjustments. Figure a shows the divalent cation (Ca) used to form the DTPMP-metal complex nanoscale antiscaling film. 2+ Mg 2+ Ba 2+ 、Sr 2+ Zn 2+ ) and anions (Cl - NO3 - CH3COO - Screening of DTPMP at a fixed concentration (5 mM, Zn); Figure b shows the screening at a fixed concentration (DTPMP = 5 mM, Zn). 2+ The effect of pH on the formation of nanoscale inhibitory films in the range of 1.72–6.00 at a DTPMP concentration of 10 mM; Figure cd shows the effect of pH on the formation of nanoscale inhibitory films at a fixed DTPMP concentration of 5 mM. 2+ The effect of concentration on the formation of nanoscale antiscaling films; Figure e shows the effect of concentration on the formation of nanoscale antiscaling films with fixed Zn. 2+ The effect of DTPMP concentration on the formation of nanoscale inhibitory films at a DTPMP molar ratio of 2:1; Figure f shows the effect of soaking time on the formation of nanoscale inhibitory films (DTPMP = 3.5 mM, Zn 2+ = 7 mM, pH = 3.00); Figure g shows the scale inhibition efficiency after recoating on C1018 substrates polished with different grits; Figure h shows the one-step method of Example 13 (on a DTPMP=3.5 mM, Zn 2+ (Immersion in 7 mM, pH 3.00 solution for 10 minutes) and Comparative Example 10 stepwise method (alternating immersion in 3.5 mM DTPMP and 7 mM Zn) 2+A comparison of nanoscale inhibitory membrane preparation schemes (2 minutes each time, repeated for a total time of 10 minutes) was conducted. The figure shows that zinc ions provide the best treatment effect, with zinc chloride salts exhibiting the highest scale inhibition efficiency. The scale inhibition efficiency is optimal when the solution pH is around 3.0. Direct immersion significantly improves scale inhibition efficiency compared to distributed immersion.

[0083] Table 1 summarizes the scale inhibition efficiency results of various embodiments and comparative examples in this invention. As can be seen from the table, the scale inhibition membrane constructed by the method provided by this invention has a scale inhibition efficiency of up to 99% or higher.

[0084] Table 1. Scale inhibition efficiency results of the examples and comparative examples The applicant declares that the present invention is illustrated by the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of individual raw materials in the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a high-efficiency nanoscale inhibitory membrane, characterized in that, Includes the following steps: S1. Preparation of film-forming solution: Dissolve the organophosphonate and the metal salt corresponding to the divalent or higher valence metal ion in water in sequence, stir evenly, and adjust the pH value of the solution to obtain the film-forming solution. S2. Pretreatment of the metal substrate; S3. Immerse the metal substrate after the pretreatment in step S2 in the film-forming solution obtained in step S1 for soaking treatment. Alternatively, the film-forming solution obtained in step S1 can be coated onto the surface of the metal substrate after pretreatment in step S2.

2. The method for preparing a high-efficiency nanoscale inhibitory membrane according to claim 1, characterized in that, In step S1, the organophosphonate is selected from at least one of polyaminopolymethylene phosphonic acid compounds.

3. The method for preparing a high-efficiency nanoscale inhibitory membrane according to claim 2, characterized in that, The polyaminopolymethylene phosphonic acid compounds are selected from at least one of the following: diethylenetriaminepentamethylenephosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, and bis-1,6-ethylenetriaminepentamethylenephosphonic acid.

4. The method for preparing a high-efficiency nanoscale inhibitory membrane according to claim 1, characterized in that, In step S1, the metal ions are selected from, but are not limited to, Zn. 2+ Co 2+ Ni 2+ Mn 2+ Cu 2+ At least one of them.

5. The method for preparing a high-efficiency nanoscale inhibitory membrane according to claim 4, characterized in that, The metal salt is selected from, but is not limited to, nitrates, chlorides, and acetates.

6. The method for preparing a high-efficiency nanoscale inhibitory membrane according to claim 1, characterized in that, In step S1, the concentration of organophosphonate is 1~10 mmol / L; the concentration of metal ion is 2~50 mmol / L.

7. The method for preparing a high-efficiency nanoscale inhibitory membrane according to claim 1, characterized in that, In step S1, the pH value of the solution is 2 to 5.

8. The method for preparing a high-efficiency nanoscale inhibitory membrane according to claim 1, characterized in that, In step S2, the pretreatment of the metal substrate includes the following steps: polishing the metal substrate and then cleaning it with anhydrous ethanol.

9. The method for preparing a high-efficiency nanoscale inhibitory membrane according to claim 1, characterized in that, In step S3, the soaking temperature is 10~90 ℃ and the soaking time is 5~60 min.

10. The application of the method according to any one of claims 1 to 9 in metal scale inhibition.

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