CN114836724A

CN114836724A - Preparation method of super-hydrophobic corrosion-resistant aluminum alloy for biomedical use

Info

Publication number: CN114836724A
Application number: CN202210399508.8A
Authority: CN
Inventors: 漆雷廷
Original assignee: Individual
Current assignee: Individual
Priority date: 2021-03-05
Filing date: 2021-03-05
Publication date: 2022-08-02
Also published as: CN113046689B; CN113046689A

Abstract

The invention discloses a preparation method of a super-hydrophobic corrosion-resistant aluminum alloy for biomedical use, wherein the aluminum alloy comprises an alloy matrix, and a titanium nitride layer, a hydrophobic layer and a polydopamine layer are sequentially arranged on the surface of the alloy matrix from inside to outside; during preparation, an aluminum alloy matrix is cleaned firstly, and the aluminum alloy matrix is cleaned in a metal cleaning agent, acetone and ethanol solution so as to ensure that the surface of the aluminum alloy can be effectively coated with a subsequent coating; the alloy substrate is sequentially provided with the titanium nitride layer, the hydrophobic layer and the polydopamine layer from inside to outside, the titanium nitride layer is firstly sputtered and processed on the surface of the aluminum alloy substrate through magnetron sputtering during preparation, the titanium nitride film is a superhard coating and has high hardness, high wear resistance, low friction coefficient and good chemical stability, and the titanium nitride layer is sputtered and processed on the surface of the aluminum alloy, so that the wear resistance of the aluminum alloy can be effectively improved. The method has the advantages of reasonable process design and simple operation, and the prepared aluminum alloy has excellent wear resistance.

Description

Preparation method of super-hydrophobic corrosion-resistant aluminum alloy for biomedical use

Technical Field

The invention relates to the technical field of aluminum alloy, in particular to a preparation method of super-hydrophobic corrosion-resistant aluminum alloy for biomedical use.

Background

The aluminum alloy is one of light metal materials, and has high strength, good casting performance, good plastic processing performance, good electric conduction performance, good heat conduction performance, good corrosion resistance and good weldability, can be used as a structural material, and can be used in the directions of aerospace, aviation and the like; in the biomedical field, the aluminum alloy is widely applied.

At present, because the corrosion resistance of aluminum alloy is poor, the development of aluminum alloy in the field of biomedical science is limited, and therefore, researches on the improvement of the corrosion resistance of aluminum alloy emerge endlessly, common treatment methods include electroplating, chemical plating treatment, anodic oxidation treatment, organic polymer coating, chemical conversion treatment and the like, but the processes are complex, and the actual effect still cannot meet the requirements of people.

Based on the situation, we disclose a super-hydrophobic corrosion-resistant aluminum alloy for biomedical use and a preparation method thereof, so as to solve the problem.

Disclosure of Invention

The invention aims to provide a preparation method of a super-hydrophobic corrosion-resistant aluminum alloy for biomedical use, which aims to solve the problems in the background technology.

In order to solve the technical problems, the invention provides the following technical scheme:

the super-hydrophobic corrosion-resistant aluminum alloy for the biomedical treatment comprises an alloy matrix, wherein a titanium nitride layer, a hydrophobic layer and a polydopamine layer are sequentially arranged on the surface of the alloy matrix from inside to outside.

According to an optimized scheme, the hydrophobic layer is a hydrophobically modified layered compound, and the layered compound is mainly prepared by reacting magnesium nitrate hexahydrate, an ammonium nitrate solution and ammonia water.

According to an optimized scheme, the surface of the polydopamine layer is subjected to hydrophobic modification treatment through octadecyl trimethoxy silane.

According to an optimized scheme, the preparation method of the super-hydrophobic corrosion-resistant aluminum alloy for the biomedical use comprises the following steps:

(1) taking an alloy matrix, placing the alloy matrix in a metal cleaning agent, carrying out ultrasonic cleaning, washing the alloy matrix with deionized water, placing the alloy matrix in an acetone solution, cleaning the alloy matrix with ethanol, and drying the alloy matrix for later use;

(2) putting the cleaned alloy substrate in a vacuum chamber, vacuumizing, performing magnetron sputtering by adopting a pure titanium target in a high-purity nitrogen environment to form a titanium nitride layer on the surface of the alloy substrate;

(3) uniformly mixing magnesium nitrate hexahydrate and ammonium nitrate solution, adding ammonia water, adjusting pH, adding an alloy matrix with a titanium nitride layer, carrying out heat preservation reaction at the temperature of 200-;

(4) taking aminosilane, an anionic surfactant and an ethanol aqueous solution, mixing and stirring, heating to 65-70 ℃, adding a matrix A, adjusting pH, stirring for reaction, taking out, cleaning, drying in vacuum, then placing in a polydimethylsiloxane solution, soaking, drying, washing with deionized water, and drying to obtain a matrix B;

(5) and (2) taking dopamine hydrochloride and Tris-HCl buffer solution, stirring and mixing, adjusting pH, adding the substrate B, dipping, taking out, cleaning, vacuum drying, putting the substrate B into octadecyl trimethoxy silane solution, soaking for a period of time, taking out, washing with deionized water, and vacuum drying to obtain a finished product.

The optimized scheme comprises the following steps:

(1) placing the alloy matrix in a metal cleaning agent, ultrasonically cleaning at 40-50 ℃ for 10-20min, washing with deionized water, placing in an acetone solution, cleaning with ethanol, and drying for later use;

(2) placing the cleaned alloy substrate in a vacuum chamber, vacuumizing, and performing magnetron sputtering by adopting a pure titanium target under a high-purity nitrogen environment to form a titanium nitride layer on the surface of the alloy substrate;

(3) uniformly mixing magnesium nitrate hexahydrate and ammonium nitrate solution, adding ammonia water, adjusting the pH to 9, adding an alloy matrix with a titanium nitride layer, carrying out heat preservation reaction at 200-210 ℃, taking out, cleaning, and drying in vacuum to obtain a matrix A;

(4) taking aminosilane, an anionic surfactant and an ethanol aqueous solution, mixing and stirring for 20-30min, heating to 65-70 ℃, adding a matrix A, adjusting the pH to 10, stirring for reaction for 3-4h, taking out, cleaning, drying in vacuum, placing in a polydimethylsiloxane solution after drying, soaking for 10-20min, drying at 80-90 ℃, washing with deionized water, and drying to obtain a matrix B;

(5) taking dopamine hydrochloride and Tris-HCl buffer solution, stirring and mixing, adjusting the pH value to 8.5, adding the matrix B, dipping for 22-24h, taking out, cleaning, vacuum drying, putting the matrix B into octadecyl trimethoxy silane solution, soaking for 2-3h at the temperature of 60-70 ℃, taking out, washing with deionized water, and vacuum drying to obtain a finished product.

In the optimized scheme, in the step (4), the aminosilane is N-aminoethyl-gamma-aminopropyltrimethoxysilane, and the anionic surfactant is sodium dodecyl sulfate.

In the optimized scheme, in the step (1), the nitrogen flow is 10-15sccm during magnetron sputtering, the sputtering time is 10-15min, the titanium target power is 5kw, and the bias voltage is 150V.

In the optimized scheme, in the step (4), ultrasonic dispersion is carried out simultaneously during impregnation.

In the optimized scheme, in the step (4), the mass ratio of the aminosilane to the anionic surfactant is (3-4): 1.

in the optimized scheme, in the step (3), the reaction time is kept at 20-22 h.

Compared with the prior art, the invention has the following beneficial effects:

the invention discloses a super-hydrophobic corrosion-resistant aluminum alloy for biomedical use and a preparation method thereof, wherein an aluminum alloy matrix is cleaned firstly during preparation, and the aluminum alloy matrix is cleaned in a metal cleaning agent, acetone and ethanol solution to ensure that the surface of the aluminum alloy can be effectively coated with a subsequent coating; the alloy substrate is sequentially provided with the titanium nitride layer, the hydrophobic layer and the polydopamine layer from inside to outside, the titanium nitride layer is firstly sputtered and processed on the surface of the aluminum alloy substrate through magnetron sputtering during preparation, the titanium nitride film is a superhard coating and has high hardness, high wear resistance, low friction coefficient and good chemical stability, and the titanium nitride layer is sputtered and processed on the surface of the aluminum alloy, so that the wear resistance of the aluminum alloy can be effectively improved.

Meanwhile, because the titanium nitride layer is formed by magnetron sputtering, a plurality of pores and holes exist among particles of the processed titanium nitride layer, and a corrosive medium cannot be completely prevented from entering the titanium nitride layer in actual use, so that an excellent corrosion resistant effect is achieved; therefore, after the titanium nitride layer is prepared, the hydrophobic layer is prepared, the main material of the hydrophobic layer is a magnesium-aluminum sheet hydrotalcite-like structure and is mainly prepared by reaction processing of magnesium nitrate hexahydrate, ammonium nitrate solution and ammonia water, the generation of the material can not only fill gaps and holes existing in magnetron sputtering and improve the compactness of the titanium nitride layer, but also the whole hydrophobic layer is of a sheet layer structure, and when an aluminum alloy substrate is corroded, the diffusion path of a corrosion medium can be effectively prolonged through the design of the sheet layer structure, and the diffusion of the corrosion medium is hindered; meanwhile, the magnesium-aluminum sheet hydrotalcite-like structure is subjected to amination treatment and then is grafted with the hydrophobic medium, when a corrosive medium enters the hydrophobic layer, the coating is in a hydrophobic state, so that the permeation behavior of the corrosive medium entering a lower layer crack is hindered, and the corrosion resistance of the aluminum alloy can be effectively improved by combining the structure of the magnesium-aluminum sheet hydrotalcite-like structure.

On the basis of the structure, because certain gaps exist in the titanium nitride layer and the hydrophobic layer, the poly-dopamine layer is designed on the hydrophobic layer, the surface of the alloy substrate is sealed through the poly-dopamine layer, and the alloy without the poly-dopamine layer has obvious and excellent corrosion resistance; meanwhile, the polydopamine layer has higher adhesion performance and can serve as a double-sided adhesive tape in operation, and the arrangement of the polydopamine layer can further improve the adhesion of a hydrophobic layer and a titanium nitride layer on the surface of the aluminum alloy, so that the corrosion resistance and the wear resistance of the aluminum alloy are ensured.

After the polydopamine layer is prepared, octadecyltrimethoxysilane hydrophobic modification treatment is carried out outside the polydopamine layer, so that the polydopamine layer has super-hydrophobic property, and the corrosion resistance of an aluminum alloy matrix is further improved; meanwhile, due to the arrangement of the hydrophobic layer and the titanium nitride layer, the surface of the aluminum alloy is in a rough state, so that the adhesive force of the polydopamine layer can be improved, and the hydrophobic modification of the subsequent octadecyl trimethoxy silane is effectively facilitated to construct a hydrophobic interface.

The application discloses super-hydrophobic corrosion-resistant aluminum alloy for biomedical use and a preparation method thereof, the process design is reasonable, the operation is simple, the prepared aluminum alloy has excellent wear resistance, the surface of the aluminum alloy is in a super-hydrophobic state, the aluminum alloy has excellent corrosion resistance, and the aluminum alloy can be widely applied to the technical field of biomedical use and has higher practicability.

Detailed Description

The technical solutions in the examples of the present invention will be described clearly and completely below, and it is obvious that the described examples are only a part of examples of the present invention, but not all examples. All other examples, which can be obtained by a person skilled in the art without making any creative effort based on the examples in the present invention, belong to the protection scope of the present invention.

Example 1:

a preparation method of super-hydrophobic corrosion-resistant aluminum alloy for biomedical use comprises the following steps:

(1) placing the alloy matrix in a metal cleaning agent, ultrasonically cleaning at 40 ℃ for 20min, washing with deionized water, placing in an acetone solution, cleaning with ethanol, and drying for later use;

(2) placing the cleaned alloy substrate in a vacuum chamber, vacuumizing, and performing magnetron sputtering by adopting a pure titanium target under a high-purity nitrogen environment to form a titanium nitride layer on the surface of the alloy substrate; the nitrogen flow is 10sccm during magnetron sputtering, the sputtering time is 10min, the titanium target power is 5kw, and the bias voltage is 150V;

(3) uniformly mixing magnesium nitrate hexahydrate and an ammonium nitrate solution, adding ammonia water, adjusting the pH to 9, adding an alloy matrix with a titanium nitride layer, carrying out heat preservation reaction at 200 ℃ for 22 hours, taking out, cleaning, and carrying out vacuum drying to obtain a matrix A;

(4) taking aminosilane, an anionic surfactant and an ethanol aqueous solution, mixing and stirring for 20min, heating to 65 ℃, adding a matrix A, adjusting the pH value to 10, stirring and reacting for 4h, taking out, cleaning, drying in vacuum, placing in a polydimethylsiloxane solution after drying, soaking for 10min, performing ultrasonic dispersion during soaking, drying at 80 ℃, washing with deionized water, and drying to obtain a matrix B;

(5) and (2) taking dopamine hydrochloride and Tris-HCl buffer solution, stirring and mixing, adjusting the pH value to 8.5, adding the matrix B, soaking for 22 hours, taking out, cleaning, drying in vacuum, placing in octadecyl trimethoxy silane solution, soaking for 2 hours at the temperature of 60 ℃, taking out, washing with deionized water, and drying in vacuum to obtain the finished product.

In this example, the aminosilane was N-aminoethyl- γ -aminopropyltrimethoxysilane, the anionic surfactant was sodium dodecylsulfate, and the mass ratio of aminosilane to anionic surfactant was 3: 1.

example 2:

(1) placing the alloy matrix in a metal cleaning agent, ultrasonically cleaning for 15min at 45 ℃, washing with deionized water, placing in an acetone solution, cleaning with ethanol, and drying for later use;

(2) placing the cleaned alloy substrate in a vacuum chamber, vacuumizing, and performing magnetron sputtering by adopting a pure titanium target under a high-purity nitrogen environment to form a titanium nitride layer on the surface of the alloy substrate; the nitrogen flow during magnetron sputtering is 12sccm, the sputtering time is 14min, the titanium target power is 5kw, and the bias voltage is 150V;

(3) uniformly mixing magnesium nitrate hexahydrate and an ammonium nitrate solution, adding ammonia water, adjusting the pH to 9, adding an alloy matrix with a titanium nitride layer, carrying out heat preservation reaction at 205 ℃ for 21 hours, taking out, cleaning, and carrying out vacuum drying to obtain a matrix A;

(4) taking aminosilane, an anionic surfactant and an ethanol aqueous solution, mixing and stirring for 25min, heating to 68 ℃, adding a matrix A, adjusting the pH value to 10, stirring and reacting for 3.5h, taking out, cleaning, drying in vacuum, placing in a polydimethylsiloxane solution after drying, dipping for 15min, performing ultrasonic dispersion while dipping, drying at 85 ℃, washing with deionized water, and drying to obtain a matrix B;

(5) and (2) taking dopamine hydrochloride and Tris-HCl buffer solution, stirring and mixing, adjusting the pH value to 8.5, adding the matrix B, soaking for 23h, taking out, cleaning, drying in vacuum, placing in octadecyl trimethoxy silane solution, soaking for 2.5h at 65 ℃, taking out, washing with deionized water, and drying in vacuum to obtain the finished product.

In this example, the aminosilane was N-aminoethyl- γ -aminopropyltrimethoxysilane, the anionic surfactant was sodium dodecylsulfate, and the mass ratio of aminosilane to anionic surfactant was 3.5: 1.

example 3:

(1) placing the alloy matrix in a metal cleaning agent, ultrasonically cleaning for 10min at 50 ℃, washing with deionized water, placing in an acetone solution, cleaning with ethanol, and drying for later use;

(2) placing the cleaned alloy substrate in a vacuum chamber, vacuumizing, and performing magnetron sputtering by adopting a pure titanium target under a high-purity nitrogen environment to form a titanium nitride layer on the surface of the alloy substrate; during magnetron sputtering, the nitrogen flow is 15sccm, the sputtering time is 15min, the titanium target power is 5kw, and the bias voltage is 150V;

(3) uniformly mixing magnesium nitrate hexahydrate and an ammonium nitrate solution, adding ammonia water, adjusting the pH to 9, adding an alloy matrix with a titanium nitride layer, carrying out heat preservation reaction at 210 ℃ for 20 hours, taking out, cleaning, and carrying out vacuum drying to obtain a matrix A;

(4) taking aminosilane, an anionic surfactant and an ethanol aqueous solution, mixing and stirring for 30min, heating to 70 ℃, adding a matrix A, adjusting the pH value to 10, stirring and reacting for 3h, taking out, cleaning, drying in vacuum, placing in a polydimethylsiloxane solution after drying, dipping for 20min, performing ultrasonic dispersion during dipping, drying at 90 ℃, washing with deionized water, and drying to obtain a matrix B;

(5) and (2) taking dopamine hydrochloride and Tris-HCl buffer solution, stirring and mixing, adjusting the pH value to 8.5, adding the matrix B, soaking for 24 hours, taking out, cleaning, drying in vacuum, placing in octadecyl trimethoxy silane solution, soaking for 2 hours at 70 ℃, taking out, washing with deionized water, and drying in vacuum to obtain the finished product.

In this example, the aminosilane is N-aminoethyl- γ -aminopropyltrimethoxysilane, the anionic surfactant is sodium dodecylsulfate, and the mass ratio of aminosilane to anionic surfactant is 4: 1.

comparative example 1:

(5) and (3) taking dopamine hydrochloride and Tris-HCl buffer solution, stirring and mixing, adjusting the pH value to 8.5, adding the matrix B, soaking for 23h, taking out, cleaning, and drying in vacuum to obtain a finished product.

comparative example 1 did not have the hydrophobic modification treatment on the surface of the polydopamine layer, and the remaining process parameters and component contents were in accordance with example 2.

Comparative example 2:

(4) taking aminosilane, an anionic surfactant and an ethanol aqueous solution, mixing and stirring for 25min, heating to 68 ℃, adding a matrix A, adjusting the pH value to 10, stirring and reacting for 3.5h, taking out, cleaning, drying in vacuum, placing in a polydimethylsiloxane solution after drying, dipping for 15min, performing ultrasonic dispersion while dipping, drying at 85 ℃, washing with deionized water, and drying to obtain a finished product.

comparative example 2 no polydopamine layer was prepared, the remaining process parameters and component contents being in accordance with example 2.

Comparative example 3:

(1) taking an alloy matrix, placing the alloy matrix in a metal cleaning agent, ultrasonically cleaning for 15min at 45 ℃, washing with deionized water, placing the alloy matrix in an acetone solution, cleaning with ethanol, and drying for later use;

(2) uniformly mixing magnesium nitrate hexahydrate and an ammonium nitrate solution, adding ammonia water, adjusting the pH to 9, adding an alloy matrix, carrying out heat preservation reaction at 205 ℃ for 21 hours, taking out, cleaning, and carrying out vacuum drying to obtain a matrix A;

(3) taking aminosilane, an anionic surfactant and an ethanol aqueous solution, mixing and stirring for 25min, heating to 68 ℃, adding a matrix A, adjusting the pH value to 10, stirring and reacting for 3.5h, taking out, cleaning, drying in vacuum, placing in a polydimethylsiloxane solution after drying, dipping for 15min, performing ultrasonic dispersion while dipping, drying at 85 ℃, washing with deionized water, and drying to obtain a matrix B;

(4) and (2) taking dopamine hydrochloride and Tris-HCl buffer solution, stirring and mixing, adjusting the pH value to 8.5, adding the matrix B, soaking for 23h, taking out, cleaning, drying in vacuum, placing in octadecyl trimethoxy silane solution, soaking for 2.5h at 65 ℃, taking out, washing with deionized water, and drying in vacuum to obtain the finished product.

comparative example 3 did not process the titanium nitride layer and the remaining process parameters and component levels were consistent with example 2.

Comparative example 4:

(4) and (2) taking dopamine hydrochloride and Tris-HCl buffer solution, stirring and mixing, adjusting the pH value to 8.5, adding the matrix A, soaking for 23h, taking out, cleaning, drying in vacuum, placing in octadecyl trimethoxy silane solution, soaking for 2.5h at 65 ℃, taking out, washing with deionized water, and drying in vacuum to obtain the finished product.

In comparative example 4, the hydrophobic layer was not hydrophobized, and the remaining process parameters and component contents were in accordance with example 2.

Comparative example 5:

(5) taking dopamine hydrochloride and Tris-HCl buffer solution, stirring and mixing, adjusting the pH value to 8.5, adding the matrix B, soaking for 23 hours, taking out, cleaning, drying in vacuum, placing in octadecyl trimethoxy silane solution, soaking for 2.5 hours at 65 ℃, taking out, washing with deionized water, and drying in vacuum to obtain the finished product.

comparative example 5 did not have a hydrophobic layer process and the remaining process parameters and component levels were consistent with example 2.

Detection experiment:

1. the alloy matrixes prepared in examples 1-3 and comparative examples 1-5 are tested for salt corrosion resistance according to GBT1771-2007 determination of neutral salt spray resistance of colored paint and varnish, and the tested samples are graded according to GB/T6461-2002 to characterize corrosion resistance.

2. The alloy substrates prepared in examples 1-3 were taken, surface contact angle measurements were made and data recorded.

3. The alloy substrates prepared in examples 1 to 3 and comparative examples 1 to 5 were subjected to a frictional wear test using a zirconia grinding ball having a diameter of 4mm and a load of 3N at a speed of 200 revolutions per minute for 3600 s. And after the friction and wear experiment, observing the appearance of the grinding mark by using a super-depth-of-field microscope.

Item

Example 1

Example 2

Example 3

Comparative example 1

Comparative example 2

Comparative example 3

Comparative example 4

Comparative example 5

Corrosion resistance grade

9

8

6

9

8

7

Surface contact Corner

158°

160°

159°

/

Wear-resistant test Test for

The grinding scar is shallow and wide Is small in degree

Grinding scar is relatively Shallow and wide Is small in degree

The grinding mark is shallow, so that the grinding mark is shallow, has small width

Grinding scar and obvious width In example 2

The grinding marks and the widths are obviously between those of the examples 2. Between comparative examples 3

And (4) conclusion: the application discloses super-hydrophobic corrosion-resistant aluminum alloy for biomedical use and a preparation method thereof, the process design is reasonable, the operation is simple, the prepared aluminum alloy has excellent wear resistance, the surface of the aluminum alloy is in a super-hydrophobic state, the aluminum alloy has excellent corrosion resistance, and the aluminum alloy can be widely applied to the technical field of biomedical use and has higher practicability.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing examples, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention as defined in the following claims. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A preparation method of super-hydrophobic corrosion-resistant aluminum alloy for biomedical use is characterized by comprising the following steps: the method comprises the following steps:

(2) placing the cleaned alloy substrate in a vacuum chamber, vacuumizing, and performing magnetron sputtering by adopting a pure titanium target under a high-purity nitrogen environment to form a titanium nitride layer on the surface of the alloy substrate; the nitrogen flow is 12sccm during magnetron sputtering, the sputtering time is 14min, the titanium target power is 5kw, and the bias voltage is 150V;

(5) taking dopamine hydrochloride and Tris-HCl buffer solution, stirring and mixing, adjusting the pH value to 8.5, adding a matrix B, soaking for 23h, taking out, cleaning, vacuum drying, placing in octadecyl trimethoxy silane solution, soaking for 2.5h at 65 ℃, taking out, washing with deionized water, and vacuum drying to obtain a finished product;

the amino silane is N-aminoethyl-gamma-aminopropyltrimethoxysilane, the anionic surfactant is sodium dodecyl sulfate, and the mass ratio of the amino silane to the anionic surfactant is 3.5: 1.