CN115354259A

CN115354259A - Anticorrosive and antifouling integrated iron-based amorphous composite coating and preparation method thereof

Info

Publication number: CN115354259A
Application number: CN202211013206.9A
Authority: CN
Inventors: 张�诚; 朱鹏宇; 柳林
Original assignee: Huazhong University of Science and Technology
Current assignee: Huazhong University of Science and Technology
Priority date: 2022-08-23
Filing date: 2022-08-23
Publication date: 2022-11-18

Abstract

The invention provides an iron-based amorphous composite coating with integrated anticorrosion and antifouling functions and a preparation method thereof, belonging to the field of coatings. The invention also provides a preparation method of the anti-corrosion and anti-fouling function integrated composite coating. The composite coating has the advantages of high strength, integration of anticorrosion and antifouling functions, long-acting marine organism fouling prevention capability and excellent corrosion resistance, and the preparation method is simple and easy to popularize.

Description

Anticorrosive and antifouling integrated iron-based amorphous composite coating and preparation method thereof

Technical Field

The invention belongs to the field of composite coatings, and particularly relates to an iron-based amorphous composite coating with integrated functions of corrosion prevention and pollution prevention and a preparation method thereof.

Background

The marine environment is very harsh and complex, the salinity of atmosphere and seawater is high, and the loss caused by corrosion exceeds the loss of all other disasters. Corrosion not only causes damage to marine equipment and increases maintenance costs, but also can be a hazard to property and life safety when severe. The iron-based amorphous coating serving as a novel surface antifouling material has high corrosion resistance, high wear resistance and excellent corrosion resistance, and has wide application prospect in the fields of ocean engineering, national defense, military and the like.

In addition, in marine environments, there are many organisms that cause fouling in addition to seawater corrosion. The amorphous coating has excellent corrosion resistance, but has almost no marine biofouling prevention capability. Marine fouling organisms, also known as marine fouling organisms, are animals, plants and microorganisms that grow on the surface of all facilities in the ship bottom and the sea. The marine fouling organisms are various, and the barnacles, oysters, seaweeds and the like are more harmful and common, and most of the marine fouling organisms live on the coast and in estuaries. The attachment of fouling organisms can increase the resistance of the boat, reduce the speed of the boat, increase the energy consumption, increase the cleaning times and even cause the invasion of organisms. In order to reduce the great damage of fouling organisms to materials, the development of antifouling coatings is very important.

Various antifouling coatings have been developed for use on ships, and in the last 50 th century, a revolution has occurred in the field of antifouling paints, tributyltin compounds (TBT) being found to have the most effective antifouling properties, but they also pose a huge threat to marine life, and have since been designated as global pollutants and eventually banned. Currently, copper-containing antifouling agents which are relatively less harmful to the environment are also widely used, however, the marine environment is complicated, and the application requirements cannot be completely met by only using the copper-containing antifouling agents.

Therefore, the development of the composite coating with integrated anticorrosion and antifouling functions, simple preparation process, low cost and high bonding strength has important significance for the marine field.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide an iron-based amorphous composite coating with integrated anticorrosion and antifouling functions and a preparation method thereof.

In order to achieve the purpose, the invention provides an anticorrosive and antifouling integrated iron-based amorphous composite coating, which comprises an iron-based amorphous layer, an epoxy resin intermediate layer adhered to the surface of the iron-based amorphous coating, and a polydimethylsiloxane-cuprous oxide mixed coating adhered to the surface layer of the epoxy resin intermediate layer, wherein molecular adsorption and chemical bonding effects are generated between the surface of the iron-based amorphous coating and the epoxy resin, the epoxy resin is used for improving the bonding strength between the polydimethylsiloxane-cuprous oxide mixed coating and the surface of the epoxy resin, and the cuprous oxide is used for improving the antifouling performance of the composite coating and improving the mechanical performance of the polydimethylsiloxane.

Furthermore, the thickness of the iron-based amorphous layer is 150-250 μm, the thickness of the epoxy resin intermediate layer is 100-200 μm, and the thickness of the mixed coating of polydimethylsiloxane and cuprous oxide is 300-500 μm.

Furthermore, the anti-protein adhesion rate exceeds 80 percent, the anti-algae adhesion rate exceeds 99 percent, and the shellfish byssus adhesion can be prevented.

Further, the impedance value is increased by at least one time compared with the coating formed by mixing polydimethylsiloxane and cuprous oxide alone.

According to the second aspect of the invention, there is also provided a method for preparing the integrated iron-based amorphous composite coating with corrosion and pollution prevention functions, which comprises the following steps:

s1: the metal matrix which needs to prepare the composite coating is subjected to surface treatment to obtain a clean and rough surface,

s2: depositing an iron-based amorphous layer on the clean and rough surface of the metal substrate by adopting a thermal spraying mode,

s3: polishing the iron-based amorphous layer to obtain a flat surface, cleaning the surface,

s4: and coating an epoxy resin intermediate layer on the surface of the clean iron-based amorphous layer, after the epoxy resin intermediate layer is completely cured, coating a polydimethylsiloxane and cuprous oxide mixed coating, and curing.

Further, the iron-based amorphous coating surface is polished by 60-120 meshes of sand paper and 300-500 meshes of sand paper respectively in sequence to obtain a flat and clean surface, and then the surface is ultrasonically cleaned by deionized water and absolute ethyl alcohol solution respectively and then dried.

Further, in the step S2, the thermal spraying mode is supersonic flame spraying, the spraying moving speed is 300-600 mm/S, the spraying distance is 300-350 mm, the auxiliary gas adopts hydrogen, and the powder feeding speed is 20-30 g/min.

Further, in the step S4, the mass of cuprous oxide accounts for 0.01 wt% to 1.0 wt% of the mass of the whole polydimethylsiloxane and cuprous oxide mixed coating, and the particle size of cuprous oxide is 1 μm to 5 μm.

Further, the specific process for coating the epoxy resin intermediate layer comprises the following steps:

firstly, taking epoxy resin and an epoxy resin curing agent according to the proportion of 10: (0.5-1.5), uniformly stirring, coating the mixture on the surface of an iron-based amorphous coating, and curing for 2 +/-0.5 h at the temperature of 80 +/-5 ℃.

Further, the specific process for coating the polydimethylsiloxane and cuprous oxide mixed coating comprises the following steps:

firstly, taking a polydimethylsiloxane main agent, adding micron-sized cuprous oxide into the polydimethylsiloxane main agent to obtain a mixture, performing ultrasonic dispersion on the mixture for 3 to 4 minutes, repeating the ultrasonic dispersion for four to seven times,

then, adding a polydimethylsiloxane curing agent into the ultrasonically dispersed polydimethylsiloxane main agent, wherein the mass ratio of the main agent to the polydimethylsiloxane curing agent is 10: (0.5-1.5), stirring until the mixture is uniformly mixed,

and finally, coating the mixed polydimethylsiloxane on the surface of the epoxy resin intermediate layer which is completely cured, and curing for 2h +/-0.5 h at the temperature of 80 +/-5 ℃.

Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:

according to the invention, the epoxy resin intermediate layer is added, and the mixed coating formed by polydimethylsiloxane and cuprous oxide is combined on the iron-based amorphous surface, wherein the polydimethylsiloxane is a classical hydrophobic fouling release type antifouling coating, and the preparation method has the advantages of simple preparation process, good antifouling effect and low cost. The micron-sized cuprous oxide compounded in the polydimethylsiloxane has the broad-spectrum sterilization effect, relatively small environmental pollution and low cost. The addition of the epoxy resin intermediate layer can greatly improve the bonding strength between the iron-based amorphous coating and the polydimethylsiloxane layer. The iron-based amorphous coating is a novel surface antifouling material and has high corrosion resistance and high wear resistance. The composite coating has the characteristics of high substrate universality and strong corrosion resistance, has strong surface antifouling capability, and can effectively prevent marine organisms from attaching. The iron-based amorphous coating adopted by the invention can be prepared in a large area and has excellent corrosion resistance.

The preparation method is simple, the technological process is reliable, the preparation cost is low, and the preparation method can be used for mass production and large-area preparation.

Drawings

FIG. 1 is a schematic structural diagram and a schematic principle diagram of an anticorrosive and antifouling function integrated iron-based amorphous composite coating of the invention.

FIG. 2 is a schematic flow chart of the preparation process of the anti-corrosion and anti-fouling functional integrated composite coating according to the embodiment of the invention.

Fig. 3 is a schematic flow chart of the preparation of the mixed coating of polydimethylsiloxane and cuprous oxide according to the example of the present invention.

FIG. 4 (a) is a schematic view of supersonic flame spraying of Fe-based amorphous coating according to the embodiment of the present invention.

Fig. 4 (b) is a cross-sectional optical microscope photograph of the composite coating of an embodiment of the present invention.

Fig. 5 (a) is a scanning electron micrograph of micron-sized cuprous oxide according to example of the present invention.

Fig. 5 (b) is an XRD pattern of micron-sized cuprous oxide used in the example of the present invention.

FIG. 6 is an XRD pattern of the Fe-based amorphous coating obtained by supersonic flame spraying according to an embodiment of the invention.

FIG. 7 is a graph comparing the bonding strength of one example of the present invention and a comparative example.

FIG. 8 is a fluorescent photomicrograph of one embodiment of the invention.

FIG. 9 is a graph showing the results of EIS tests of an example of the present invention and a comparative example.

FIG. 10 is a graph comparing the results of the anti-protein adhesion test of one example of the present invention with the comparative example.

FIG. 11 (a) is a graph comparing the number of secreted surface mussel byssus strips for one example of the invention and a comparative example.

FIG. 11 (b) is a graph comparing the attachment strength of the surface mussel foot silk discs of one embodiment of the invention with the comparative example.

FIG. 12 is a graph comparing the results of the anti-algae adhesion test of one example of the present invention with the comparative example.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.

The iron-based amorphous coating serving as a novel surface antifouling material has high corrosion resistance, high wear resistance and excellent corrosion resistance, and has wide application prospect in the fields of ocean engineering, national defense, military and the like.

Polydimethylsiloxane (PDMS), which is the most widely used hydrophobic organosilicon polymer material, has the chemical formula (C) ₂ H ₆ OSi) _n . The main chain of the polydimethylsiloxane is formed by silicon-oxygen bonds, and has the characteristics of high chemical stability, high elastic limit, high transparency, good biocompatibility, low surface energy and the like. The silicon rubber is formed by crosslinking and polymerizing organic groups on silicon atoms of a silicon-oxygen main chain, and has good low-temperature resistance and excellent high-temperature resistance. In the field of marine antifouling, polydimethylsiloxane exhibits a certain flexibility in mechanical strength and is relatively easy to change into a configuration with lower surface energy, so that the polydimethylsiloxane is called a low surface energy material and is a typical application material of a fouling release coating. The polydimethylsiloxane reduces the surface energy of the polydimethylsiloxane to reduce the adhesion of fouling organisms in the sea on the surface so as to play a role in preventing fouling.

If the polydimethylsiloxane and the iron-based amorphous alloy can be combined to prepare the composite coating, the advantages of the polydimethylsiloxane and the iron-based amorphous alloy can be combined to obtain the comprehensive coating with integrated anticorrosion and antifouling functions. Although the polydimethylsiloxane coating is stable in property and has better marine antifouling performance, the polydimethylsiloxane coating has the problems of poor bonding force with an iron-based amorphous coating substrate, weak edge and easiness in stripping from the substrate material, so that the antifouling life and the antifouling effect are greatly reduced. In short, in the aspect of marine corrosion and fouling prevention of the iron-based amorphous coating and the polydimethylsiloxane coating, the problems of poor combination of the coating and a substrate, failure of the coating due to easy peeling in the service process, difficult practical application and the like exist in the related technology.

Aiming at the problem that polydimethylsiloxane is easy to peel off from the surface of an iron-based amorphous coating substrate, the main ideas are as follows: and (1) modifying chemical components. Groups which are easily combined with the surface of the metal substrate (such as hydrophilic groups which can be combined with hydroxyl groups on the metal surface) are grafted in the polydimethylsiloxane segment. Or a binder component is doped, and the binding force of the coating can be directly and effectively increased by binding the binder component with the surface of the metal matrix. However, the method may have an influence on the hydrophobicity of the coating, so that the antifouling property of the coating is reduced to a certain extent; and (2) adding an intermediate layer. The transition intermediate layer which can be well combined with the iron-based amorphous coating and the polydimethylsiloxane is added, and a chemical bond is formed between the transition intermediate layer and the coating, so that the bonding force between the polydimethylsiloxane antifouling coating and the iron-based amorphous coating is indirectly increased. The method can improve the binding force and simultaneously can keep the property of the coating; and (3) modifying the surface morphology of the iron-based amorphous coating. On the premise of not changing the chemical composition of the matrix, the final iron-based amorphous coating with certain surface mechanical properties, roughness and surface morphology is obtained by mechanical treatment or machining, including sand blasting, grinding and surface texture pattern preparation methods, so that better bonding conditions of polydimethylsiloxane on the surface of the iron-based amorphous coating are provided.

In addition, copper antifouling agents are widely used antifouling agents, and mainly include divalent copper ions which act on marine fouling organisms. The copper ion has broad-spectrum bactericidal performance, the copper antifouling agent of the coating generates monovalent copper ion chloride through the action with chloride ions in seawater, a liquid film is formed on the surface, and the monovalent copper ion is further oxidized to generate divalent copper ion to play an antifouling role. The antifouling property of copper ions is achieved mainly by causing damage to the inner membrane of cells and destruction of DNA. In the invention, the copper antifouling agent is added into the polydimethylsiloxane, so that the antifouling property of the coating can be further improved.

According to the invention, the problem of poor interfacial bonding force between the iron-based amorphous coating and the polydimethylsiloxane coating is solved by adding the epoxy resin intermediate layer.

The invention provides an integrated polydimethylsiloxane iron-based amorphous coating with an anti-corrosion and anti-fouling function, which comprises an iron-based amorphous coating, an epoxy resin intermediate layer adhered to the surface of the iron-based amorphous coating, and a polydimethylsiloxane and cuprous oxide mixed coating used as a surface layer, wherein the surface of the iron-based amorphous coating and the epoxy resin have the functions of molecular adsorption and chemical bonding and have strong bonding. The epoxy resin is used as an intermediate layer for improving the bonding of the polydimethylsiloxane coating on the surface, and the bonding force is improved by times. Cuprous oxide can be used as an antifouling agent to improve the antifouling performance of the polydimethylsiloxane coating and can also improve the mechanical performance of the polydimethylsiloxane coating.

Fig. 1 is a schematic diagram of the structure and principle of the corrosion-resistant and antifouling integrated iron-based amorphous composite coating, and it can be seen from the diagram that the composite coating is attached to a metal substrate on which the composite coating is to be prepared, the iron-based amorphous coating is thermally sprayed on the metal substrate, then is subjected to sand paper polishing and ultrasonic cleaning, an epoxy resin intermediate layer is coated on the surface of the iron-based amorphous coating, and after the epoxy resin intermediate layer is cured, a polydimethylsiloxane-cuprous oxide mixed coating is coated, and a polydimethylsiloxane-cuprous oxide mixed coating is formed after curing. The component of the iron-based amorphous coating is FeCoCrMoCBY, and the metal matrix in the embodiment is brass alloy. The thickness of the iron-based amorphous layer is 150-250 μm, the thickness of the epoxy resin layer is 100-200 μm, and the thickness of the polydimethylsiloxane layer is 300-500 μm. As can be seen from fig. 1, the antifouling and anticorrosion mechanisms of the composite coating of the present invention are as follows: the polydimethylsiloxane has the characteristic of low modulus, the marine fouling organisms have weak adhesion on the surface of the polydimethylsiloxane, and are easy to clean and remove by the shearing force of water flow and a mechanical method, and the cuprous oxide serving as a common antifouling agent has a broad-spectrum bactericidal effect, is dissolved and oxidized to generate divalent copper ions playing an antifouling role, can damage the cell membrane of bacteria, and has a biofilm inhibiting effect, so that the composite coating has good antifouling performance. And the atomic arrangement of the iron-based amorphous coating is in a long-range disordered state, and the iron-based amorphous coating has a stable amorphous phase, and has excellent corrosion resistance in a splashing area with alternation of dry and wet and higher salt spray concentration due to the generation of an amorphous uniform structure and a surface passivation film. The reasons for the firm combination and the difficult falling of the composite coating are as follows: the addition of the epoxy resin intermediate layer enables the combination of the polydimethylsiloxane and the iron-based amorphous coating to be changed from Van der Waals force to the combination of molecular bonds, the coating of the epoxy resin on the iron-based amorphous coating enables epoxy groups in the epoxy resin and hydroxyl groups on the iron-based amorphous coating to form the combination of hydrogen bonds, and terminal hydroxyl groups of a macromonomer in the polydimethylsiloxane main agent can also react with the epoxy groups to form covalent bonds, so that the combination of the polydimethylsiloxane and the iron-based amorphous coating is firmer and is not easy to fall off.

The method for preparing the integrated polydimethylsiloxane iron-based amorphous coating with the functions of corrosion prevention and stain resistance comprises the following steps:

s1: carrying out surface treatment on the metal matrix to obtain a clean and rough surface;

s2: and depositing an iron-based amorphous layer on the clean and rough surface of the metal matrix by adopting a thermal spraying mode. The hot spraying mode in the step S2 is supersonic flame spraying, the spraying moving speed is 300-600 mm/S, the spraying distance is 300-350 mm, the auxiliary gas adopts hydrogen, and the powder feeding speed is 20-30g/min;

s3: and (3) polishing the iron-based amorphous coating by using sand paper to obtain a flat surface, and then respectively ultrasonically cleaning by using deionized water and ethanol. In the step S3, the surface of the iron-based amorphous coating is respectively and sequentially polished by 80-mesh sand paper and 400-mesh sand paper to obtain a flat and clean surface, then the surface is respectively ultrasonically cleaned for 10 minutes by deionized water and absolute ethyl alcohol solution, and then the surface is dried by a blower;

s4: and (4) coating an epoxy resin intermediate layer on the surface of the iron-based amorphous coating obtained in the step (S3), and coating a polydimethylsiloxane coating dispersed with cuprous oxide with a certain mass fraction again after the iron-based amorphous coating is completely cured. In the composite coating of polydimethylsiloxane and cuprous oxide, the content of micron-sized cuprous oxide is 0-1.0 wt.%. The grain size of the cuprous oxide is 1-5 μm, the type of the polydimethylsiloxane is 184, and the type of the epoxy resin is 9903. In the step, the process for preparing the epoxy resin intermediate layer and the polydimethylsiloxane-cuprous oxide composite coating comprises the following steps:

firstly, mixing an epoxy resin main agent and a curing agent according to the mass ratio of 10 (0.5-1.5), stirring for 10min by using magnetic force until the mixture is uniform, then coating the mixture on the surface of the iron-based amorphous coating treated by the S3 treatment method, curing for 2h +/-0.5 h at the temperature of 80 +/-5 ℃,

then, taking a certain amount of polydimethylsiloxane main agent, adding micron-sized cuprous oxide into the polydimethylsiloxane main agent according to a certain mass ratio, and performing ultrasonic dispersion on the mixture for multiple times, wherein the specific process of the ultrasonic dispersion for one time is as follows: ultrasonic dispersion is carried out on the polydimethylsiloxane main agent added with the micron cuprous oxide for 3 to 4 minutes, the process is repeated for four to seven times,

then, a certain amount of curing agent is added into the ultrasonically dispersed polydimethylsiloxane main agent according to the mass ratio of the main agent to the curing agent 10 (0.5-1.5), magnetic stirring is carried out for 10min until the materials are uniformly mixed,

In engineering practice, a preparation method of an anticorrosive and antifouling function integrated polydimethylsiloxane iron-based amorphous coating is shown in fig. 2, and fig. 2 is a schematic flow chart of the preparation process of the anticorrosive and antifouling function integrated composite coating, and the preparation method can comprise the following steps:

firstly, carrying out surface polishing and sand blasting treatment on a metal matrix;

depositing an iron-based amorphous coating on the surface of the metal matrix after polishing and sand blasting by adopting thermal spraying;

polishing the surface of the iron-based amorphous coating by using sand paper, and then ultrasonically cleaning for multiple times;

coating a layer of epoxy resin intermediate layer on the surface of the treated iron-based amorphous coating, and curing;

and fifthly, adding micron-sized cuprous oxide particles into the polydimethylsiloxane, uniformly mixing to obtain a polydimethylsiloxane-cuprous oxide mixed coating, coating the polydimethylsiloxane-cuprous oxide mixed coating on the cured epoxy resin intermediate layer, and forming a composite coating on the metal substrate.

Fig. 3 is a schematic flow chart of the preparation of the polydimethylsiloxane and cuprous oxide composite coating. The method comprises the following specific steps:

taking a certain amount of polydimethylsiloxane main agent, adding micron-sized cuprous oxide in a certain mass ratio, and performing ultrasonic dispersion on the mixture for multiple times. The specific process of the primary ultrasonic dispersion comprises the following steps: ultrasonic dispersion is carried out on the polydimethylsiloxane main agent added with the micron cuprous oxide for 3 to 4 minutes, the process is repeated for 4 to 7 times,

and step two, adding a certain amount of curing agent into the ultrasonically dispersed polydimethylsiloxane main agent according to the mass ratio of the main agent to the curing agent 10 of 1, and stirring for 10min by using magnetic force until the materials are uniformly mixed to obtain the polydimethylsiloxane prepolymer.

The following examples are given for further details.

Example 1

(1) Pretreatment

The method comprises the steps of polishing a metal matrix by using 80-mesh abrasive paper, uniformly blasting sand on the surface of a metal matrix sample by using a sand blasting machine to form a uniform rough surface on the surface of the sample, then sequentially performing ultrasonic cleaning by using absolute ethyl alcohol and deionized water, removing oil and dirt, and finally performing vacuum drying.

(2) Supersonic flame spraying

Supersonic flame spraying is adopted to prepare the iron-based amorphous coating on the metal substrate, the spraying moving speed is 400mm/s, the spraying distance is 145mm, the stepping distance is 3mm, the auxiliary gas adopts hydrogen, and the powder feeding speed is 30g/min. And (4) observing the appearance of the section of the sprayed iron-based amorphous coating by using an optical microscope. Fig. 4 (a) is a schematic diagram of a supersonic flame spraying iron-based amorphous coating, and fig. 4 (b) is a cross-sectional optical micrograph of a composite coating, and it can be seen from the figure that the thickness of the iron-based amorphous coating is 166 micrometers, the iron-based amorphous coating has obvious texture deposited layer by layer, the thickness of an epoxy resin intermediate layer is 118 micrometers, and the thickness of a mixed coating of polydimethylsiloxane and cuprous oxide is 309 micrometers.

(3) Surface treatment of iron-based amorphous coatings

And (3) respectively and sequentially polishing the surface of the iron-based amorphous coating by using 80-mesh and 400-mesh sand papers to obtain a flat and clean surface, respectively ultrasonically cleaning the surface for 10 minutes by using deionized water and an absolute ethyl alcohol solution, and then drying the surface by using a blower.

(4) Preparation of composite coatings

Firstly, mixing an epoxy resin main agent and a curing agent according to a mass ratio of 10. Then, taking a certain amount of polydimethylsiloxane main agent, adding 0.6wt.% of micron-sized cuprous oxide into the polydimethylsiloxane main agent, and performing ultrasonic dispersion on the mixture for multiple times, wherein the specific process of the ultrasonic dispersion for one time comprises the following steps: and (3) carrying out ultrasonic dispersion on the polydimethylsiloxane main agent added with the micron-sized cuprous oxide for 3-4 minutes. The ultrasonic dispersion was repeated 4 to 7 times. Then, adding a certain amount of curing agent into the ultrasonically dispersed polydimethylsiloxane main agent according to the mass ratio of the main agent to the curing agent of 10.

FIG. 5 (a) is a scanning electron micrograph of micron-sized cuprous oxide, showing that the cuprous oxide powder is irregular in shape and has a particle size of about 1 μm to 5 μm. Fig. 5 (b) is an XRD pattern of micron-sized cuprous oxide. As can be seen, the metal ions are reacted with Cu ₂ And comparing the O standard PDF card, wherein the diffraction peak position and the intensity are well matched, and the purity of the used cuprous oxide powder is proved to be higher.

FIG. 6 is an XRD pattern of the Fe-based amorphous coating obtained by supersonic flame spraying, and as can be seen, the Fe-based amorphous coating has a diffraction peak package at about 45 degrees, which proves that the amorphous coating is indeed deposited on the surface.

Example 2

The difference between this embodiment and embodiment 1 is that the parameters of each step are different, and the other steps are similar, specifically the differences are:

(4) Preparation of composite coatings

Taking a certain amount of polydimethylsiloxane main agent, adding 0.6wt.% of micron-sized cuprous oxide into the polydimethylsiloxane main agent, and performing ultrasonic dispersion on the mixture for multiple times, wherein the specific process of the ultrasonic dispersion for one time is as follows: and (3) carrying out ultrasonic dispersion on the polydimethylsiloxane main agent added with the micron-sized cuprous oxide for 3-4 minutes. The ultrasonic dispersion was repeated four to seven times. Then, adding a certain amount of curing agent into the ultrasonically dispersed polydimethylsiloxane main agent according to the mass ratio of the main agent to the curing agent of 10.5, stirring for 10min by using magnetic force until the mixture is uniform, finally, coating the surface of the iron-based amorphous coating subjected to surface polishing treatment, and curing for 2h at 85 ℃.

Example 3

(3) Surface treatment of iron-based amorphous coatings

Ultrasonic cleaning is carried out for 10 minutes by using deionized water and absolute ethyl alcohol solution respectively, and then the ultrasonic cleaning is dried by a blower without polishing the surface of the coating.

(4) Preparation of composite coatings

Taking a certain amount of polydimethylsiloxane main agent, adding micron-sized cuprous oxide into the polydimethylsiloxane main agent according to a certain mass ratio, and performing ultrasonic dispersion on the mixture for multiple times, wherein the specific process of the ultrasonic dispersion for one time is as follows: and (3) carrying out ultrasonic dispersion on the polydimethylsiloxane main agent added with the micron-sized cuprous oxide for 3-4 minutes, and repeating for 4-7 times. Then, adding a certain amount of curing agent into the ultrasonically dispersed polydimethylsiloxane main agent according to the mass ratio of the main agent to the curing agent of 10.

Example 4

The embodiment comprises the following steps:

s1: and sequentially polishing the surface of the iron-based amorphous coating by adopting 100-mesh sand paper and 500-mesh sand paper respectively to obtain a flat and clean surface, then respectively ultrasonically cleaning by using deionized water and absolute ethyl alcohol solution, and then drying to obtain a clean and rough surface.

S2: and depositing an iron-based amorphous layer on the clean and rough surface of the metal substrate by adopting a thermal spraying mode, wherein the thermal spraying mode in the step S2 is supersonic flame spraying, the spraying moving speed is 300mm/S, the spraying distance is 350mm, the auxiliary gas adopts hydrogen, and the powder feeding speed is 30g/min.

S3: and polishing the iron-based amorphous layer to obtain a flat surface, and then cleaning.

S4: and coating an epoxy resin intermediate layer on the surface of the clean iron-based amorphous layer, after the epoxy resin intermediate layer is completely cured, coating a polydimethylsiloxane and cuprous oxide mixed coating, and curing. In step S4, the mass of cuprous oxide is 0.01wt.% of the mass of the entire polydimethylsiloxane-cuprous oxide mixed coating, and the particle size of cuprous oxide is 1 μm. The specific process for coating the epoxy resin intermediate layer comprises the following steps:

firstly, mixing epoxy resin and an epoxy resin curing agent according to a mass ratio of 10.5, uniformly stirring, coating the mixture on the surface of an iron-based amorphous coating, and curing for 2 hours at 80 ℃.

The specific process for coating the polydimethylsiloxane and cuprous oxide mixed coating comprises the following steps:

firstly, taking a polydimethylsiloxane main agent, adding micron-sized cuprous oxide into the polydimethylsiloxane main agent to obtain a mixture, performing ultrasonic dispersion on the mixture for 3 to 4 minutes, repeating the ultrasonic dispersion for four times,

then adding a polydimethylsiloxane curing agent into the ultrasonically dispersed polydimethylsiloxane main agent, wherein the mass ratio of the main agent to the polydimethylsiloxane curing agent is 10.5, stirring until the main agent and the polydimethylsiloxane curing agent are uniformly mixed,

and finally, coating the mixed polydimethylsiloxane on the surface of the epoxy resin intermediate layer which is completely cured, and curing for 1.5h at the temperature of 80 ℃.

In the embodiment, the thickness of the iron-based amorphous layer is 150-160 μm, the thickness of the epoxy resin intermediate layer is 100-110 μm, and the thickness of the mixed coating of polydimethylsiloxane and cuprous oxide is 300-350 μm. The protein adhesion resistant rate is over 80 percent, the algae adhesion resistant rate is over 99 percent, the shellfish byssus adhesion can be prevented, and the impedance value of the coating is doubled compared with that of a single polydimethylsiloxane-cuprous oxide mixed coating.

Example 5

The steps included in this example are the same as those in example 4, except that the specific parameters are different, wherein:

s1: 60-mesh sand paper and 300-mesh sand paper are respectively adopted to polish the surface of the iron-based amorphous coating.

S2: the spraying moving speed is 600mm/s, the spraying distance is 300mm, the auxiliary gas adopts hydrogen, and the powder feeding speed is 20g/min.

S4: in step S4, the mass of cuprous oxide accounts for 1.0 wt% of the mass of the whole polydimethylsiloxane and cuprous oxide mixed coating, and the particle size of the cuprous oxide is 5 μm. The specific process for coating the epoxy resin intermediate layer comprises the following steps:

firstly, mixing epoxy resin and an epoxy resin curing agent according to a mass ratio of 10:1.5, uniformly stirring, coating the mixture on the surface of an iron-based amorphous coating, and curing for 2.5 hours at 85 ℃.

firstly, taking a polydimethylsiloxane main agent, adding micron-sized cuprous oxide into the polydimethylsiloxane main agent to obtain a mixture, performing ultrasonic dispersion on the mixture for 4 minutes, and repeating the ultrasonic dispersion for seven times, wherein the mass ratio of the polydimethylsiloxane main agent to the polydimethylsiloxane curing agent is 10:1.5, stirring until the mixture is uniformly mixed, and finally, coating the mixed polydimethylsiloxane on the surface of the epoxy resin intermediate layer which is completely cured, and curing for 2 hours at the temperature of 80 ℃.

In the embodiment, the thickness of the iron-based amorphous layer is 240-250 μm, the thickness of the epoxy resin intermediate layer is 190-200 μm, and the thickness of the mixed coating of polydimethylsiloxane and cuprous oxide is 450-500 μm. The anti-protein adhesion rate is over 80 percent, the anti-algae adhesion rate is over 99 percent, and the shellfish byssus adhesion can be prevented. The impedance value is doubled compared with the single polydimethylsiloxane and cuprous oxide mixed coating.

Example 6

s1: and respectively polishing the surface of the iron-based amorphous coating by using 80-mesh sand paper and 400-mesh sand paper in sequence.

S2: the spraying moving speed is 450mm/s, the spraying distance is 320mm, the auxiliary gas adopts hydrogen, and the powder feeding speed is 25g/min.

S4: in step S4, the mass of cuprous oxide accounts for 0.6 wt% of the mass of the whole polydimethylsiloxane and cuprous oxide mixed coating, and the particle size of the cuprous oxide is 3 μm. The specific process for coating the epoxy resin intermediate layer comprises the following steps:

firstly, mixing epoxy resin and an epoxy resin curing agent according to the mass ratio of 10.

firstly, taking a polydimethylsiloxane main agent, adding micron-sized cuprous oxide into the polydimethylsiloxane main agent to obtain a mixture, performing ultrasonic dispersion on the mixture for 3 to 4 minutes, repeating the ultrasonic dispersion for six times,

then adding a polydimethylsiloxane curing agent into the ultrasonically dispersed polydimethylsiloxane main agent, wherein the mass ratio of the main agent to the polydimethylsiloxane curing agent is 10 to 1, stirring until the main agent and the polydimethylsiloxane curing agent are uniformly mixed,

and finally, coating the mixed polydimethylsiloxane on the surface of the epoxy resin intermediate layer which is completely cured, and curing for 2.3h at the temperature of 81 ℃.

In the embodiment, the thickness of the iron-based amorphous layer is 200-210 μm, the thickness of the epoxy resin intermediate layer is 150-160 μm, and the thickness of the mixed coating of polydimethylsiloxane and cuprous oxide is 400-420 μm. The anti-protein adhesion rate is over 80 percent, the anti-algae adhesion rate is over 99 percent, and the shellfish byssus adhesion can be prevented. The impedance value is doubled compared with the single polydimethylsiloxane and cuprous oxide mixed coating.

Example 7

s1: 120-mesh sand paper and 360-mesh sand paper are respectively adopted to polish the surface of the iron-based amorphous coating.

S2: the spraying moving speed is 420mm/s, the spraying distance is 340mm, the auxiliary gas adopts hydrogen, and the powder feeding speed is 28g/min.

S4: the mass of cuprous oxide accounts for 0.4wt.% of the mass of the whole polydimethylsiloxane-cuprous oxide mixed coating, and the particle size of cuprous oxide is 3 μm. The specific process for coating the epoxy resin intermediate layer comprises the following steps:

firstly, taking a polydimethylsiloxane main agent, adding micron-sized cuprous oxide into the polydimethylsiloxane main agent to obtain a mixture, performing ultrasonic dispersion on the mixture for 3-4 minutes, repeating the ultrasonic dispersion for seven times,

then adding a polydimethylsiloxane curing agent into the ultrasonically dispersed polydimethylsiloxane main agent, wherein the mass ratio of the main agent to the polydimethylsiloxane curing agent is 10:1.5, stirring until the main agent and the polydimethylsiloxane curing agent are uniformly mixed,

and finally, coating the mixed polydimethylsiloxane on the surface of the completely cured epoxy resin intermediate layer, and curing for 2 hours at the temperature of 80 ℃.

In this example, the thickness of the iron-based amorphous layer is 250 μm, the thickness of the epoxy resin intermediate layer is 200 μm, and the thickness of the mixed coating of polydimethylsiloxane and cuprous oxide is 400 μm. The anti-protein adhesion rate is over 80 percent, the anti-algae adhesion rate is over 99 percent, and the shellfish byssus adhesion can be prevented. The impedance value is doubled compared with the single polydimethylsiloxane and cuprous oxide mixed coating.

Comparative example

The comparative examples of the present invention have nine, as shown in table 1 below. In nine comparative examples, tests of iron-based amorphous coatings with different cuprous oxide contents and polydimethylsiloxane hybrid coatings without polishing and brass alloys without iron-based amorphous coatings with 0.6wt.% cuprous oxide were given.

TABLE 1 coating information for specific examples and comparative examples

The bonding strength test of the composite coating example and the comparative example prepared by the above method is performed, and the result is shown in fig. 7, fig. 7 is a graph comparing the bonding strength of the example and the comparative example of the present invention, and in the comparative example 1, the bonding force between the polydimethylsiloxane coating (comparative example 1) without micron-sized cuprous oxide and the iron-based amorphous coating is the lowest, and is 19.57N/cm ² . It can be seen from comparative examples 2 to 6 that the addition of micron-sized cuprous oxide can improve the bonding force of the polydimethylsiloxane coating on the surface of the iron-based amorphous coating, and the bonding force is increased and then reduced with the increase of the content of cuprous oxide, and reaches the highest value at the content of 0.6 wt.%. Compared with the comparative example 4 with the highest bonding force, the epoxy resin intermediate layer is added in the example 1, so that the bonding force is doubled and is increased by 100.63N/cm ² Lifting to 217.20N/cm ² Compared with the traditional hydrogel antifouling coating, the binding force of the coating is a bright point. By adding the epoxy resin interlayer, the polydimethylsiloxane antifouling coating and the iron-based amorphous layer are well connected. The epoxy resin can be solidified and firmly bonded on the surface of the iron-based amorphous alloy, and the chain segment of the polydimethylsiloxane can also be chemically bonded with the functional group on the surface of the epoxy resin, so that the bonding force of the coating is greatly improved compared with the condition of only relying on Van der Waals force.

FIG. 8 is a fluorescent photomicrograph of one embodiment of the present invention in which cuprous oxide is excited to a bluish-violet color under green fluorescence as shown in FIG. 8, indicating that cuprous oxide is uniformly dispersed in the coating. The cuprous oxide is added and dispersed, so that the dispersion strengthening effect is achieved, and the strength of the polydimethylsiloxane coating is improved. The mixed coating has the advantages of simple process, low cost, relatively friendly environment and suitability for industrial mass production, so the coating has wide application prospect in the field of marine antifouling.

The corrosion resistance of example 2 and comparative example 8 was compared using the ac impedance technique, and the results are shown in fig. 9, and fig. 9 is a graph showing the results of the EIS test of one example of the present invention and the comparative example, from which it can be seen that the arc radius of the impedance is largeThe small is in positive correlation with the impedance, namely the larger the radius is, the larger the impedance value is, the better the corrosion resistance is. As can be seen from FIG. 9, the impedance value in example 2 was 4.216X 10 ⁸ Ω·cm ² Comparative example 8 has an impedance value of 2.277X 10 ⁸ Ω·cm ² . The corrosion resistance of the composite coating is improved by adding the iron-based amorphous coating, and compared with the condition that the polydimethylsiloxane composite coating is directly coated on a brass alloy substrate, the corrosion resistance is doubled.

The results of the Bovine Serum Albumin (BSA) adhesion rate test conducted on the composite coating examples and comparative examples are shown in FIG. 10. FIG. 10 is a graph comparing the results of the anti-protein adhesion tests of one example of the present invention with those of the comparative example, and it can be seen from FIG. 10 that the samples coated with the polydimethylsiloxane composite coating (comparative example 1, comparative example 2, comparative example 3, example 2, comparative example 5 and comparative example 6) all had higher protein adhesion than the sample of the bare iron-based amorphous coating without the polydimethylsiloxane composite coating (comparative example 9), indicating that the polydimethylsiloxane composite coating can effectively resist the adhesion of bovine serum albumin. And the pure polydimethylsiloxane coating (comparative example 1) has an anti-adhesion rate of 80.39%, while comparative example 3, example 2 and comparative example 5, in which the micro-sized cuprous oxide content is 0.4wt.%,0.6wt.% and 0.8wt.%, have higher anti-adhesion rates, respectively 84.06%,83.90% and 85.49%, which are higher than 80%, meet the requirement of excellent antifouling performance. However, the anti-adhesion ratio of comparative example 6 was rather decreased to 77.68%, because: as the cuprous oxide content increases, the coating strength increases and the young's modulus decreases, partially diminishing the coating's resistance to protein adhesion.

The results of the mussel adhesion test of the examples and comparative examples of composite coating are shown in fig. 11 (a) and 11 (b). FIG. 11 (a) is a graph comparing the number of secreted surface mussel byssus strips for one example of the invention and a comparative example. FIG. 11 (b) is a graph comparing the attachment strength of a surface mussel foot silk disc of an embodiment of the invention with a comparative example. As shown in fig. 11 (a), in example 3 and comparative example 7, the mussels secreted 67 and 154 filament discs (byssus discs), respectively, of elastomeric protein on the coating surface, indicating that mussels were more prone to selectively attach to iron-based amorphous coating surfaces without the protection of the polydimethylsiloxane coating. As shown in fig. 11 (b), in example 3 and comparative example 7, the adhesion strength of the mussel on the foot wire disc attached to the coating surface is 13kPa and 259kPa, respectively, the adhesion strength of the foot wire disc on the surface of the polydimethylsiloxane and cuprous oxide composite coating is only 1/20 of that of the iron-based amorphous coating, and the foot wire disc is very easy to detach from the coating surface, which indicates that the polydimethylsiloxane composite coating has good mussel adhesion resistance and meets the requirement of excellent antifouling performance.

The results of the anti-algae adhesion test of the composite coating example and the comparative example are shown in fig. 12, fig. 12 is a graph comparing the results of the anti-algae adhesion test of one example of the present invention and the comparative example, and the examples and the comparative example were immersed in the algae solution of nitzschia closterium in a constant temperature and humidity incubator for 30 days, and the adhesion area of diatom on the coating was counted by observing with a fluorescence microscope to calculate the anti-algae adhesion rate. As can be seen from fig. 12, after 30 days, the algae adhesion resistant rates of the polydimethylsiloxane coatings (comparative example 1, comparative example 2, comparative example 3, example 2, comparative example 5 and comparative example 6) with different micron-sized cuprous oxide contents were all above 99%, while the algae adhesion resistant rate of the sample (comparative example 9) without the exposed iron-based amorphous coating of the polydimethylsiloxane composite coating was relatively low at 97.49%, which met the requirement of excellent antifouling performance.

In an embodiment of the present invention, the polydimethylsiloxane type is 184, for example, and the epoxy type is 9903, for example.

It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims

1. The iron-based amorphous composite coating with the integrated functions of corrosion prevention and pollution prevention is characterized by comprising an iron-based amorphous layer, an epoxy resin intermediate layer adhered to the surface of the iron-based amorphous coating and a polydimethylsiloxane-cuprous oxide mixed coating adhered to the surface layer of the epoxy resin intermediate layer, wherein molecular adsorption and chemical bonding effects are generated between the surface of the iron-based amorphous coating and the epoxy resin, the epoxy resin is used for improving the bonding strength of the polydimethylsiloxane-cuprous oxide mixed coating and the surface of the epoxy resin, and the cuprous oxide is used for improving the pollution prevention performance of the composite coating and improving the mechanical performance of the polydimethylsiloxane.

2. The integrated anticorrosive and antifouling iron-based amorphous composite coating as claimed in claim 1, wherein the thickness of the iron-based amorphous layer is 150 μm to 250 μm, the thickness of the epoxy resin intermediate layer is 100 μm to 200 μm, and the thickness of the mixed coating of polydimethylsiloxane and cuprous oxide is 300 μm to 500 μm.

3. The corrosion-prevention and antifouling integrated iron-based amorphous composite coating as claimed in claim 2, wherein the protein adhesion resistance rate is over 80%, the algae adhesion resistance rate is over 99%, and shellfish byssus adhesion can be prevented.

4. The corrosion and dirt prevention integrated iron-based amorphous composite coating as claimed in claim 3, wherein the impedance value is increased by at least one time compared with the coating of the polydimethylsiloxane and the cuprous oxide alone.

5. The method for preparing the corrosion-prevention and pollution-prevention integrated iron-based amorphous composite coating according to any one of claims 1 to 4, which is characterized by comprising the following steps of:

s1: the surface treatment is carried out on the metal matrix which needs to prepare the composite coating to obtain a clean and rough surface,

6. The method for preparing the iron-based amorphous composite coating with integrated functions of corrosion prevention and stain prevention according to claim 5, wherein the iron-based amorphous coating surface is polished by 60-120-mesh sand paper and 300-500-mesh sand paper respectively to obtain a flat and clean surface, and then is subjected to ultrasonic cleaning by deionized water and absolute ethyl alcohol solution respectively, and then is dried.

7. The method for preparing an iron-based amorphous composite coating with integrated corrosion and stain resistance functions according to claim 5, wherein the thermal spraying in the step S2 is supersonic flame spraying, the spraying moving speed is 300-600 mm/S, the spraying distance is 300-350 mm, the auxiliary gas is hydrogen, and the powder feeding speed is 20-30 g/min.

8. The method for preparing an iron-based amorphous composite coating with integrated anticorrosion and antifouling functions as claimed in claim 6 or 7, wherein in step S4, the mass of cuprous oxide accounts for 0.01-1.0 wt% of the total mass of the polydimethylsiloxane-cuprous oxide mixed coating, and the particle size of the cuprous oxide is 1-5 μm.

9. The method for preparing the integrated iron-based amorphous composite coating with the functions of corrosion prevention and pollution prevention according to claim 8, wherein the specific process for coating the epoxy resin intermediate layer comprises the following steps:

firstly, mixing epoxy resin and an epoxy resin curing agent according to the mass ratio of 10 (0.5-1.5), uniformly stirring, coating the mixture on the surface of an iron-based amorphous coating, and curing for 2h +/-0.5 h at the temperature of 80 +/-5 ℃.

10. The method for preparing the iron-based amorphous composite coating with integrated corrosion and stain resistance functions according to claim 9, wherein the specific process for coating the polydimethylsiloxane-cuprous oxide mixed coating comprises the following steps:

then adding polydimethylsiloxane curing agent into the polydimethylsiloxane main agent which is dispersed by ultrasonic, wherein the mass ratio of the polydimethylsiloxane main agent to the polydimethylsiloxane curing agent is 10 (0.5-1.5), stirring until the polydimethylsiloxane main agent and the polydimethylsiloxane curing agent are uniformly mixed,