Alloy-resin-based hydrophobic membrane pre-implanted with organic phosphine compound and preparation method of alloy-resin-based hydrophobic membrane

Abstract

The invention provides an alloy-resin-based hydrophobic membrane pre-implanted with an organic phosphine compound and a preparation method thereof.The preparation method comprises the following steps that aluminum alloy serves as an anode, a platinum electrode or a graphite electrode serves as a cathode, an electrolyte is adopted, anodic oxidation is conducted, and an anodized aluminum alloy substrate is obtained; the preparation method comprises the following steps: dissolving resin and hydrophobic alumina nanoparticles in a solvent to obtain a resin-based hydrophobic precursor solution, dropwise adding the precursor solution on the surface of an aluminum alloy substrate, standing, coating, and heating to obtain the hydrophobic coating. According to the hydrophobic membrane, the interface of an aluminum alloy substrate and the super-hydrophobic membrane is strengthened by pre-implanting an organic phosphine compound, organic phosphine compound molecules are implanted into the surfaces of aluminum alloy holes, and a plurality of phosphonic acid groups of the molecules and aluminum ions form a high-bond-energy stable annular chelate through polydentate coordination. And anchoring the organic phosphonic acid molecules on the surface of the aluminum alloy substrate.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of materials, and particularly relates to an alloy-resin-based hydrophobic film pre-implanted with an organic phosphine compound and a preparation method thereof. BACKGROUND

[0002] Coating an ultrahydrophobic film on the surface of an aluminum alloy can endow the surface of the aluminum alloy material with remarkable advantages such as self-cleaning, corrosion resistance, anti-icing, and anti-bioattachment, thereby effectively prolonging the service life of the aluminum alloy material and ensuring the stable exertion of the mechanical properties of the aluminum alloy material during service. The methods for coating an ultrahydrophobic film on the surface of an aluminum alloy that have been reported so far include spraying, blade coating, dip-coating, electroplating, physical / chemical vapor deposition, laser cladding, and sol-gel methods. The above-mentioned related methods have been proven to be effective for obtaining the hydrophobicity of the film surface, but the ultrahydrophobic films currently available generally have insufficient mechanical properties and chemical stability. The surface film has excellent hydrophobicity in the initial stage of service, but the hydrophobicity gradually decreases during service. SUMMARY

[0003] In view of this, the present application aims to overcome the defects in the prior art and provides an alloy-resin-based hydrophobic film pre-implanted with an organic phosphine compound and a preparation method thereof.

[0004] To achieve the above-mentioned object, the technical solution of the present application is as follows: The present application provides an electrolyte, which comprises an organic phosphine compound, cerous oxalate, and oxalic acid. The molar concentration of the cerous oxalate in the electrolyte is 0.01-0.05 M, and the molar concentration of the organic phosphine compound in the electrolyte is 0.1-0.4 M.

[0005] Further, the organic phosphine compound is at least one of an organic phosphonic acid or an organic phosphonic acid salt; the organic phosphonic acid is at least one of aminotri(methylene)phosphonic acid, ethylenediamine tetra(methylene)phosphonic acid, or diethylenetriamine penta(methylene)phosphonic acid; and the organic phosphonic acid salt is at least one of aminotri(methylene)phosphonic acid sodium, ethylenediamine tetra(methylene)phosphonic acid sodium, or diethylenetriamine penta(methylene)phosphonic acid sodium.

[0006] The present application also provides a preparation method of an alloy-resin-based hydrophobic film pre-implanted with an organic phosphine compound, which comprises the following steps: (1) an aluminum alloy is used as an anode, a platinum electrode or a graphite electrode is used as a cathode, and the electrolyte according to claim 1 or 2 is used to perform anodic oxidation, thereby obtaining an anodized aluminum alloy substrate; (2) a resin and hydrophobic alumina nanoparticles are dissolved in a solvent to obtain a resin-based hydrophobic precursor solution, the precursor solution is added dropwise to the surface of the aluminum alloy substrate, and then coating is performed after standing, and the alloy-resin-based hydrophobic coating pre-implanted with an organic phosphine compound is obtained after heating.

[0007] Further, the current density of the anodic oxidation step in step (1) is 70-180 mA•cm -2 , and the oxidation time is 15-25 min.

[0008] Further, the solid-liquid ratio of the resin, the hydrophobic alumina nanoparticles and the solvent in step (2) is 0.1-0.2 g: 0.02-0.05 g: 1 mL.

[0009] Further, the resin is PMMA; and the solvent is ethyl acetate.

[0010] Further, the standing time in step (2) is 10-20 s.

[0011] Further, the coating amount in the coating step in step (2) is 35-40 microliters / square centimeter; the coating step in step (2) is performed by using a spin coating method or a blade coating method; the spin coating speed of the spin coating method is 1000-3000 revolutions / minute, and the spin coating time is 30-60 seconds.

[0012] Further, the heating temperature in step (2) is 150-180℃, and the heating time is 15-30 minutes.

[0013] The application further provides an alloy-resin-based hydrophobic film pre-implanted with the organic phosphine compound prepared by the preparation method.

[0014] The organic phosphine compound, the organic phosphonic acid molecule and the cerium oxalate synergistic optimization agent introduced in the anodic oxidation process can pre-implant the organic phosphine compound molecules on the surface of the aluminum alloy substrate and optimize the pore structure of the aluminum alloy substrate. The multiple phosphonic acid groups in the organic phosphine compound molecules form a high-bond-energy stable ring chelate with aluminum ions through multi-dentate coordination, and the cerium ions ionized from the cerium oxalate as a synergistic optimization agent can form a stable phosphine-oxygen-cerium coordination bond with the phosphonic acid groups. This coordination can enhance the bonding strength of the phosphonic acid groups and the aluminum ions, and can also more tightly connect the phosphonic acid groups and the aluminum substrate through a bridging effect, forming a three-dimensional network structure of phosphonic acid-cerium ion-aluminum substrate. The oxalate in the cerium oxalate has good compatibility with the oxalic acid matrix solution in the electrolyte, and can also optimize the pore structure of the anodized aluminum alloy, so as to realize the anchoring of the organic phosphine compound molecules on the surface of the aluminum alloy substrate, and the non-polar organic chain, the remaining hydroxyl group or the polar group at the other end interact with the molecular chains in the resin through hydrogen bonds or van der Waals forces, forming an interfacial reinforcement.

[0015] Compared with the prior art, the application has the following advantages: The alloy-resin base hydrophobic film pre-implanted with organic phosphine compound of the present application realizes the reinforcement of the interface between the aluminum alloy base and the super-hydrophobic film by pre-implanting organic phosphine molecules, optimizes the pore structure of the aluminum alloy base, implants the organic phosphine molecules on the surface of the aluminum alloy pores, the multiple phosphonic acid groups of the organic phosphine molecules form high-energy stable ring chelates with aluminum ions through multi-dentate coordination, anchor the organic phosphine molecules on the surface of the aluminum alloy base, and the non-polar organic chain, the remaining hydroxyl group or the polar group at the other end interacts with the molecular chain of the resin base hydrophobic film, such as ester group, through hydrogen bond or van der Waals force, to form an interface reinforcement; based on the above multi-dentate chelation and the like, the organic phosphine molecules introduced in the anodization process and the cerous oxalate synergistic optimization agent not only optimize the pore structure of the aluminum alloy, but also strengthen the interface connection between the base and the resin base hydrophobic film. Thus, the resin base hydrophobic film with strong mechanical and chemical durability on the surface of the aluminum alloy is assembled.

[0016] The alloy-resin base hydrophobic film pre-implanted with organic phosphine compound of the present application significantly enhances the adhesion of the resin base hydrophobic film on the surface of the aluminum alloy base by pre-implanting organic phosphine molecules, the peeling area of the thin film is reduced from the original 6% to less than 2% through the ASTM-D3359 cross-cut adhesive tape adhesion international standard test, and the coating adhesion is improved to 5B level; after pre-implanting the organic phosphine molecules, the water contact angle on the surface of the hydrophobic film reaches 166°, and the rolling angle is as low as 2°, which is obviously better than the parameter setting of the super-hydrophobic film; after pre-implanting the organic phosphine molecules, the mechanical performance of the hydrophobic film is improved, and the chemical stability is also further improved, after being immersed in a 3.5 NaCl solution for 45 days, the static contact angle of the water droplet can still maintain 94% of the initial value, and the super-hydrophobic property can still be maintained. DETAILED DESCRIPTION

[0017] Unless otherwise defined, the technical terms used in the following examples have the same meanings as generally understood by those skilled in the art to which the present application belongs. The experimental reagents used in the following examples are all conventional biochemical reagents unless otherwise specified; and the experimental methods described are conventional methods unless otherwise specified.

[0018] The present application will be described in detail below with reference to the examples.

[0019] Example 1 An electrolyte solution comprising 0.1 M diethylene triamine penta-methylene phosphonic acid, 0.05 M cerous oxalate and 0.4 M oxalic acid.

[0020] A preparation method of an alloy-resin base hydrophobic film pre-implanted with organic phosphine compound, comprising the following steps: (1) using the above electrolyte solution, taking aluminum alloy as an anode, platinum electrode or graphite electrode as a cathode, and applying a current density of 100 mA•cm-2 anodizing for 20 min at a current density of 120 mA•cm (2) Dissolve PMMA resin and hydrophobic alumina nanoparticles in ethyl acetate to obtain a resin-based hydrophobic precursor solution (the concentration of PMMA resin in the precursor solution is 0.1 g / mL, and the concentration of hydrophobic alumina nanoparticles is 0.04 g / mL), pour the precursor solution onto the surface of the aluminum alloy substrate, and perform spin coating after standing for 20 s, the spin coating speed is 2000 rpm, the spin coating time is 45 s, and after heating at 150°C for 30 min, the alloy-resin-based hydrophobic coating pre-implanted with organic phosphonic acid is obtained. The water droplet contact angle on the surface of the hydrophobic film is 165°, and the adhesion of the superhydrophobic film is 5B grade according to the ASTM-D3359 cross-cut tape adhesion international standard test.

[0021] Example 2 An electrolyte solution comprising 0.05 M aminotrimethylene phosphonic acid, 0.05 M cerous oxalate, and 0.4 M oxalic acid.

[0022] A method for preparing an alloy-resin-based hydrophobic film pre-implanted with an organic phosphine compound, comprising the following steps: (1) Using the above electrolyte solution, anodize an aluminum alloy as an anode and a platinum electrode or a graphite electrode as a cathode at a current density of 120 mA•cm -2 for 20 min to obtain an aluminum alloy substrate; (2) Dissolve PMMA resin and hydrophobic alumina nanoparticles in ethyl acetate to obtain a resin-based hydrophobic precursor solution (the concentration of PMMA resin in the precursor solution is 0.1 g / mL, and the concentration of hydrophobic alumina nanoparticles is 0.04 g / mL), pour the precursor solution onto the surface of the aluminum alloy substrate, and perform spin coating after standing for 20 s, the spin coating speed is 2000 rpm, the spin coating time is 45 s, and after heating at 150°C for 30 min, the alloy-resin-based hydrophobic coating pre-implanted with organic phosphonic acid is obtained. The surface contact angle of the finally obtained coating is 166°, and the adhesion of the coating is 5B grade.

[0023] Example 3 An electrolyte solution comprising 0.05 M sodium ethylenediamine tetramethylene phosphonate, 0.05 M cerous oxalate, and 0.4 M oxalic acid.

[0024] A method for preparing an alloy-resin-based hydrophobic film pre-implanted with an organic phosphine compound, comprising the following steps: (1) Using the above electrolyte solution, anodize an aluminum alloy as an anode and a platinum electrode or a graphite electrode as a cathode at a current density of 150 mA•cm -2 for 10 min to obtain an aluminum alloy substrate; (2) PMMA resin and hydrophobic alumina nanoparticles were dissolved in ethyl acetate to obtain a resin-based hydrophobic precursor solution (the concentration of PMMA resin in the precursor solution was 0.1 g / mL, and the concentration of hydrophobic alumina nanoparticles was 0.04 g / mL), the precursor solution was poured on the surface of the aluminum alloy substrate, and after standing for 20 s, spin coating was performed at a rotation speed of 3000 rpm for 50 s, and after heating at 150°C for 30 min, the pre-implanted organic phosphonic acid alloy-resin-based hydrophobic coating was obtained. The surface contact angle of the finally obtained coating was 165°, and the adhesion of the coating was 5B level.

[0025] Comparative Example 1 The difference from Example 1 is only that the electrolyte includes 0.1 M diethylene triamine pentamethylene phosphonic acid and 0.4 M oxalic acid, and the surface contact angle of the assembled hydrophobic coating is 161°, and the adhesion is 4B level.

[0026] Comparative Example 2 The difference from Example 1 is only that the electrolyte includes 0.1 M diethylene triamine pentamethylene phosphonic acid, 0.05 M cerous oxalate, and the surface contact angle of the assembled hydrophobic coating is 158°, and the adhesion is 4B level.

[0027] Comparative Example 3 The difference from Example 1 is only that the electrolyte includes 0.1 M phosphoric acid, 0.05 M cerous oxalate and 0.4 M oxalic acid, and the surface contact angle of the assembled hydrophobic coating is 160°, and the adhesion is 4B level.

[0028] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. An electrolyte, characterized by: The electrolyte comprises an organic phosphine compound, cerium oxalate and oxalic acid, the molar concentration of the cerium oxalate in the electrolyte is 0.01-0.05 M, and the molar concentration of the organic phosphine compound in the electrolyte is 0.1-0.4 M.

2. The electrolyte according to claim 1, characterized in that: The organic phosphine compound is at least one of an organic phosphonic acid or an organic phosphonic acid salt; the organic phosphonic acid is at least one of aminotrimethylene phosphonic acid, ethylenediamine tetramethylene phosphonic acid or diethylenetriamine pentamethylene phosphonic acid; and the organic phosphonic acid salt is at least one of aminotrimethylene phosphonic acid sodium, ethylenediamine tetramethylene phosphonic acid sodium or diethylenetriamine pentamethylene phosphonic acid sodium.

3. A method for preparing an alloy-resin based hydrophobic membrane pre-implanted with an organophosphorous compound, characterized by: The method comprises the following steps: (1) anodizing an aluminum alloy as an anode, a platinum electrode or a graphite electrode as a cathode, and the electrolyte of claim 1 or 2 to obtain an anodized aluminum alloy substrate; (2) dissolving a resin and hydrophobic alumina nanoparticles in a solvent to obtain a resin-based hydrophobic precursor solution, dropping the precursor solution on the surface of the aluminum alloy substrate, and coating after standing, and then heating to obtain the alloy-resin-based hydrophobic coating pre-implanted with the organic phosphine compound.

4. The method of claim 3, wherein the method is characterized by: The current density of the anodic oxidation step in step (1) is 70-180 mA•cm -2 , and the oxidation time is 15-25 min.

5. The method of claim 3, wherein the method is characterized by: The solid-liquid ratio of the resin, hydrophobic alumina nanoparticles and solvent in step (2) is 0.1-0.2 g:0.02-0.05 g:1 mL.

6. The method of claim 5, wherein the method is characterized by: The resin is PMMA, and the solvent is ethyl acetate.

7. The method of claim 3, wherein the method is characterized by: The standing time in step (2) is 10-20 s.

8. The method of claim 3, wherein the method is characterized by: The coating amount in the coating step of step (2) is 35-40 microliters per square centimeter; the coating step of step (2) is coated by spin coating or blade coating; the spin coating speed of the spin coating method is 1000-3000 revolutions per minute, and the spin coating time is 30-60 seconds.

9. The method of claim 3, wherein the method is characterized by: The heating temperature in step (2) is 150-180℃, and the heating time is 15-30 minutes.

10. An alloy-resin-based hydrophobic film pre-implanted with an organic phosphine compound prepared by the preparation method of any one of claims 1-9.