Long-lasting anti-corrosion material surfaces suitable for marine environments, their preparation methods and applications

Abstract

This invention belongs to the field of surface engineering technology, specifically relating to a long-lasting anti-corrosion material surface suitable for marine environments and its manufacturing method. The material surface comprises a tiered micro / nano structure formed by in-situ etching of a substrate surface, a silica layer filling the pores of the tiered micro / nano structure, a methylated fluid-like m-PDMS coating grafted onto the silica layer surface, and a lubricating oil filling the pores of the m-PDMS coating. This invention proposes a long-lasting anti-corrosion material surface for marine environments, which can significantly improve corrosion resistance lifespan and possesses super-lubricating properties. When applied to ship hulls, it can provide advantages for drag reduction and energy saving.

Description

Technical Field

[0001] This invention belongs to the field of surface engineering technology, and specifically relates to a method for manufacturing a long-lasting anti-corrosion material surface suitable for marine environments. Background Technology

[0002] With increasing emphasis on deep-sea resource development, seizing the initiative in deep-sea exploration is imperative. Marine engineering equipment is the foundation of marine economic development, and the development of advanced marine engineering equipment and high-tech vessels has become a key area for breakthroughs in marine development. The marine environment is characterized by high salinity, high pressure, and high corrosiveness; therefore, improving the marine corrosion resistance of deep-sea development equipment, platforms, and various types of vessels is a current research hotspot.

[0003] Currently, one of the important methods to delay marine corrosion of material surfaces is to construct superhydrophobic surfaces. However, due to the dependence of superhydrophobic surfaces on micro- and nano-structures, the effectiveness of such anti-corrosion coatings is relatively short, making them unsuitable for and unsuitable for use in deep-sea environments. Improving the long-term protective properties of superhydrophobic surfaces is a major problem that urgently needs to be solved. Summary of the Invention

[0004] To address the aforementioned technical problems, one of the objectives of this invention is to provide a long-lasting anti-corrosion material surface suitable for marine environments.

[0005] The technical solution adopted in this invention is as follows:

[0006] A long-lasting anti-corrosion material surface suitable for marine environments, the material surface comprising:

[0007] The tiered micro / nano structure is formed by in-situ etching of a substrate surface, wherein the substrate is an iron-containing substrate;

[0008] A silica layer is filled in the pores of the tiered micro-nano structure and is tightly bonded to the tiered micro-nano structure by carbon as a bridging agent.

[0009] A methylated fluid m-PDMS coating is grafted onto the surface of the silica layer;

[0010] PDMS lubricant fills the surface pores of the m-PDMS coating.

[0011] Preferably, the substrate is a stainless steel substrate.

[0012] Preferably, the tiered micro / nano structure is an array of inverted trapezoidal recesses distributed on the substrate surface, with adjacent inverted trapezoidal recesses separated by cone-shaped structures, and the distribution density of the inverted trapezoidal recesses is 400 per cm². 2The depth of the inverted trapezoidal recessed structure is 100 μm, and the silicon dioxide layer fills the inverted trapezoidal recessed structure. The surface of the silicon dioxide layer is flush with the surface of the tiered micro-nano structure.

[0013] Preferably, the lower side length of the inverted trapezoidal recessed structure is 380 μm, the bottom inclination angle of the cone is 140°, and the top width is 25 μm.

[0014] Preferably, the m-PDMS coating thickness is 7 nm, and the PDMS lubricant filling amount is 0.5 ml / cm³. 2 .

[0015] The second objective of this invention is to provide a method for preparing a long-lasting anti-corrosion material surface suitable for marine environments as described above, comprising the following steps:

[0016] S1. Using femtosecond technology, a set size of tiered micro / nano structures are etched on the substrate surface at a designed density. The tiered micro / nano structures include arrayed inverted trapezoidal recessed structures.

[0017] S2. After depositing a carbon black layer on the surface of the tiered micro-nano structure, the obtained material is placed in a sealed container for TEOS vapor deposition, and silica nanoparticles are deposited to fill the pores in the carbon black layer.

[0018] S3. After deposition, the sample is removed and placed in a tube furnace for high-temperature sintering, so that the silica nanoparticles and the tiered micro-nano structures are firmly bonded by Fe-C and Si-C.

[0019] S4. The sintered surface is cleaned with ultraviolet ozone, and then dichlorodimethylsilane is vapor-deposited. The PDMS layer is formed by spontaneous vapor-phase polymerization of dichlorodimethylsilane on the silica surface.

[0020] S5. Continue to deposit chloroform on the surface of the PDMS layer in the vapor phase, and perform methylation treatment on the PDMS layer to obtain a fluid-like m-PDMS coating;

[0021] S6. Inject PDMS lubricating oil into the surface of the fluid-like m-PDMS coating to obtain the desired long-lasting anti-corrosion material surface.

[0022] Preferably, the filling amount of the PDMS lubricating oil is 0.5 ml / cm³. 2 The viscosity of the lubricating oil is 1000 cp.

[0023] Preferably, in the carbon black layer, the carbon black fills the inverted trapezoidal recessed structure, and the surface height of the carbon black layer is greater than or equal to the surface height of the tiered micro / nano structure.

[0024] Preferably, in step S2, the TEOS vapor deposition operation is as follows: 2 ml of TEOS and 30 wt% ammonia are placed in a vacuum-drying container, the internal pressure is adjusted to 2 kPa, and chemical vapor deposition is started. The deposition time is 24 h, so that the silica nanoparticles completely fill the pores of the carbon black layer in the inverted trapezoidal structure.

[0025] Preferably, in step S3, the high-temperature sintering temperature is 1200℃ and the sintering time is 2 hours. After sintering, the carbon black layer vaporizes and disappears, and the excess silica layer on the surface of the tiered micro-nano structure is scraped off, exposing the outline of the tiered micro-nano structure.

[0026] Preferably, the ultraviolet ozone activation time is 10 minutes.

[0027] Preferably, during the dichlorodimethylsilane vapor deposition process, the relative humidity is controlled at 45%, the temperature is 25°C, and the thickness of the deposited PDMS layer is 5 nm.

[0028] Preferably, during the trichloromethane vapor deposition process, the relative humidity of the environment is controlled at 30% and the temperature is 40°C, and a methylated fluid m-PDMS coating with a thickness of 7 nm is deposited.

[0029] Preferably, after the PDMS lubricant is filled, the substrate is tilted at 45° in any direction and left for 24 hours to ensure that the oil is completely filled, and finally the excess PDMS lubricant on the surface is removed.

[0030] The third objective of this invention is to provide the application of the above-mentioned long-lasting anti-corrosion material surface suitable for marine environments in the preparation of anti-corrosion coatings for marine engineering equipment.

[0031] The present invention also provides a corrosion-resistant component, wherein the surface of the corrosion-resistant component is provided with a long-lasting corrosion-resistant material surface suitable for marine environments as described above.

[0032] The beneficial effects of this invention are as follows:

[0033] 1) This invention proposes a long-lasting anti-corrosion material surface for marine environments. This material surface can significantly improve the corrosion resistance life in marine environments and has super-slip properties. When applied to ship hulls, it can provide advantages for reducing ship drag and saving energy.

[0034] 2) An inverted trapezoidal micron structure is etched using femtosecond lasers, then filled with carbon black-silica filler and sintered to achieve bonding, thereby enhancing the adhesion between the silica filler and the substrate. After surface hydroxylation using UV ozone cleaning, spontaneous vapor-phase polymerization of dichlorodimethylsilane (DCDMS) is performed on the silica surface to form PDMS. Then, methylation of PDMA is performed using chloroform, ultimately forming a liquid-like m-PDMS coating on the filler body. The pores within the m-PDMS are further filled with lubricating oil. Due to the extremely high capillary pressure within the pores, the lubricating oil is stably bound within the pores, preventing leakage. This ultimately forms an ultra-lubricating and ultra-wear-resistant surface material suitable for marine environments and corrosion resistance.

[0035] 3) Currently, marine antifouling and anticorrosion coatings mainly rely on physical adhesion or physical interaction forces to bond with the substrate. In the complex marine solution environment, these physical effects are greatly weakened, leading to coating detachment and product failure. In this invention, the surface of the silica nanoparticles filling the structure is connected to the surface of the iron-containing substrate through carbon as an intermediate bridge. Under high-temperature calcination, Fe-C and Si-C chemical bonds are formed respectively, tightly bonding the silica to the stainless steel surface, achieving the requirement of excellent surface stability in seawater. Attached Figure Description

[0036] Figure 1 The surface of the material prepared according to the present invention;

[0037] Figure 2 This is a schematic diagram of an inverted trapezoidal concave structure. In the diagram, h represents the depth of the inverted trapezoidal concave structure, w represents the width of the top of the cone, l represents the length of the upper side of the inverted trapezoidal concave structure, and α represents the inclination angle of the bottom of the cone.

[0038] Figure 3 These are the results of a seawater immersion experiment.

[0039] Figure 4 The results verify the super-slip properties of the material surface. Detailed Implementation

[0040] Unless otherwise stated, the terms used herein have the meanings commonly understood by those skilled in the art.

[0041] The technical solution of the present invention will be described in more detail below with reference to embodiments:

[0042] Example 1

[0043] The preparation process for a long-lasting anti-corrosion material surface suitable for marine environments is as follows:

[0044] S1. A tiered micro / nano structure was etched onto a clean stainless steel substrate using femtosecond technology. See [link / reference] Figure 1-2The tiered micro / nano structure consists of an array of inverted trapezoidal depressions distributed on the substrate surface, with a distribution density of approximately 400 depressions / cm². 2 The depth h of the inverted trapezoidal recessed structure is 100 μm, the lower side length of the inverted trapezoidal recessed structure is 380 μm, the upper side length is about 475 μm, and adjacent inverted trapezoidal recessed structures are separated by a cone-shaped body. The bottom inclination angle of the cone-shaped body is 140°, and the top width is 25 μm.

[0045] S2. A carbon black layer is deposited on the surface of the tiered micro / nano structure. Carbon black is used to fill the inverted trapezoidal recessed structure, and the height of the carbon black layer exceeds the surface height of the tiered micro / nano structure to ensure that the recessed structure is completely filled. The obtained material is then placed in a sealed container, and 2 ml of TEOS and 30 wt% ammonia are added. The internal pressure is adjusted to 2 kPa, and chemical vapor deposition is started. The deposition time is 24 h, and the deposition allows the silica nanoparticles to completely fill the pores in the carbon black layer.

[0046] S3. After deposition, the substrate is removed and placed in a tube furnace at 1200℃ for 2 hours for high-temperature sintering, so that the silica nanoparticles and the surface of the tiered micro-nano structure are firmly bonded by Fe-C and Si-C.

[0047] After sintering, the carbon black layer vaporizes and disappears. Then, a stainless steel scraper is used to scrape off the excess silica layer on the surface of the tiered micro-nano structure until the outline of the tiered micro-nano structure is exposed.

[0048] S4. Perform ultraviolet ozone cleaning on the sintered surface for about 10 minutes to activate the silica and expose more hydroxyl groups on the surface; then, vapor-deposit dichlorodimethylsilane to form a PDMS layer by spontaneous vapor-phase polymerization of dichlorodimethylsilane on the silica surface.

[0049] During the deposition process, the relative humidity was controlled at 45%, the temperature was 25℃, and the thickness of the deposited PDMS layer was 5nm.

[0050] S5. Continue to deposit chloroform on the surface of the PDMS layer in the vapor phase, and perform methylation treatment on the PDMS layer to obtain a fluid-like m-PDMS coating;

[0051] During the deposition process, the relative humidity of the environment was controlled at 30% and the temperature was 40℃, and a methylated fluid m-PDMS coating with a thickness of 7nm was obtained.

[0052] S6. Fill the surface of the fluid-like m-PDMS coating with PDMS lubricating oil. After filling, tilt the substrate at 45° in any direction and leave it for 24 hours to ensure that the oil completely fills the pores. The filling amount is approximately 0.5 ml / cm². 2Then remove excess lubricating oil from the surface to obtain the desired long-lasting anti-corrosion material surface.

[0053] Example 2

[0054] Three 10×10cm 2 Stainless steel sheet:

[0055] 1) Original stainless steel;

[0056] 2) The armor structure is filled with stainless steel treated with a commercial superhydrophobic coating. This armor structure is an inverted trapezoidal microstructure manufactured using a template method. The parameters of the microstructure are set according to the present invention, but there are no sidewalls. Then, the microstructure is filled using the mature superhydrophobic coating product Extra ever dry from the United States.

[0057] 3) Stainless steel treated with the m-PDMS anti-corrosion coating prepared in this invention;

[0058] Each sample was immersed in 5L of seawater, sourced from the Dameisha sea area of ​​Shenzhen. The samples were removed on the 7th and 30th days after immersion for observation of surface corrosion.

[0059] See results Figure 3 It can be seen that existing commercial superhydrophobic coatings show large-area coating peeling off after 7 days of immersion in seawater. However, the tiered micro-nano structure m-PDMS coating provided by this invention, due to its stable interfacial bonding performance, does not show significant coating peeling after 30 days of immersion in seawater and still maintains excellent anti-corrosion performance.

[0060] In this invention, the formation of Fe-C and Si-C chemical bonds between the filler silica and the stainless steel substrate through a carbon layer at high temperatures is the main reason for the excellent stability in seawater. Currently, marine antifouling and anticorrosion coatings mainly rely on physical adhesion or physical interaction forces to bond with the substrate. In the complex marine solution environment, these physical effects are greatly weakened, leading to coating detachment and product failure.

[0061] In addition, due to the presence of fluid-like m-PDMS and a lubricating oil layer in the coating of the present invention (due to the extremely high capillary pressure in the pores, the lubricating oil can be stably bound in the pores and is not easy to leak), the coating obtained has excellent super-lubricating properties.

[0062] See Figure 4 The results of horizontal friction tests on different stainless steel surfaces (stainless steel with commercial superhydrophobic coating and stainless steel with m-PDMS anti-corrosion coating) by droplet (2ml) show that the tiered micro-nano structure m-PDMS coating of the present invention has extremely low lateral friction between itself and moving droplets, that is, the surface exhibits certain super-slip properties. When applied to ship hulls, it can provide advantages for reducing ship drag and saving energy.

[0063] The above are merely preferred embodiments of the present invention and are not intended to limit the scope of the invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A long-lasting anti-corrosion material surface suitable for marine environments, characterized in that, The material surface includes: The tiered micro / nano structure is formed by in-situ etching of a substrate surface, wherein the substrate is an iron-containing substrate; A silica layer is filled in the pores of the tiered micro-nano structure and is tightly bonded to the tiered micro-nano structure by carbon as a bridging agent. A methylated fluid m-PDMS coating is grafted onto the surface of the silica layer; PDMS lubricating oil fills the surface pores of the m-PDMS coating; The method for preparing the surface of the material includes the following steps: S1. Using femtosecond technology, a set size of tiered micro / nano structures are etched on the substrate surface at a designed density. The tiered micro / nano structures include arrayed inverted trapezoidal recessed structures. S2. After depositing a carbon black layer on the surface of the tiered micro-nano structure, the obtained material is placed in a sealed container for TEOS vapor deposition, and silica nanoparticles are deposited to fill the pores in the carbon black layer. S3. After deposition, the sample is removed and placed in a tube furnace for high-temperature sintering, so that the silica nanoparticles and the tiered micro-nano structures are firmly bonded by Fe-C and Si-C. S4. The sintered surface is cleaned with ultraviolet ozone, and then dichlorodimethylsilane is vapor-deposited. The PDMS layer is formed by spontaneous vapor-phase polymerization of dichlorodimethylsilane on the silica surface. S5. Continue to deposit chloroform on the surface of the PDMS layer in the vapor phase, and perform methylation treatment on the PDMS layer to obtain a fluid-like m-PDMS coating; S6. Inject PDMS lubricating oil into the surface of the fluid-like m-PDMS coating to obtain the desired long-lasting anti-corrosion material surface.

2. The surface of a long-lasting anti-corrosion material suitable for marine environments as described in claim 1, characterized in that, The tiered micro / nano structure is an array of inverted trapezoidal recesses distributed on the substrate surface. Adjacent inverted trapezoidal recesses are separated by cone-shaped structures, and the distribution density of the inverted trapezoidal recesses is 400 per cm². 2 The depth of the inverted trapezoidal recessed structure is 100 μm, and the silicon dioxide layer fills the inverted trapezoidal recessed structure. The surface of the silicon dioxide layer is flush with the surface of the tiered micro-nano structure.

3. The surface of a long-lasting anti-corrosion material suitable for marine environments as described in claim 2, characterized in that, The lower side of the inverted trapezoidal recessed structure is 380 μm long, the bottom inclination angle of the cone is 140°, and the top width is 25 μm.

4. The surface of a long-lasting anti-corrosion material suitable for marine environments as described in claim 1, characterized in that, The m-PDMS coating thickness is 7 nm, and the PDMS lubricant filling amount is 0.5 ml / cm². 2 .

5. The surface of a long-lasting anti-corrosion material suitable for marine environments as described in claim 1, characterized in that, In the carbon black layer, carbon black fills the inverted trapezoidal recessed structure, and the surface height of the carbon black layer is greater than or equal to the surface height of the tiered micro / nano structure.

6. The surface of a long-lasting anti-corrosion material suitable for marine environments as described in claim 1, characterized in that, In step S2, the TEOS vapor deposition operation is as follows: 2 ml of TEOS and 30 wt% ammonia water are placed in a vacuum drying container, the internal pressure is adjusted to 2 kPa, and chemical vapor deposition is started. The deposition time is 24 h, so that the silica nanoparticles completely fill the pores of the carbon black layer in the inverted trapezoidal concave structure.

7. The surface of a long-lasting anti-corrosion material suitable for marine environments as described in claim 1, characterized in that, In step S3, the high-temperature sintering temperature is 1200℃ and the sintering time is 2 hours. After sintering, the carbon black layer vaporizes and disappears, and the excess silica layer on the surface of the tiered micro-nano structure is scraped off, exposing the outline of the tiered micro-nano structure.

8. The long-lasting anti-corrosion material surface suitable for marine environments as described in claim 1, characterized in that, During the dichlorodimethylsilane vapor deposition process, the relative humidity was controlled at 45% and the temperature at 25°C, and the thickness of the deposited PDMS layer was 5 nm. During the trichloromethane vapor deposition process, the relative humidity was controlled at 30% and the temperature at 40°C, and a methylated fluid m-PDMS coating with a thickness of 7 nm was obtained.

9. The application of the long-lasting anti-corrosion material surface suitable for marine environments as described in any one of claims 1-4 in the preparation of anti-corrosion coatings for marine engineering equipment.

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