Method for preparing hydrogen-corrosion-resistant chloride-ion-abrasion-resistant passive film layer based on CO2 one-step in-situ oxygen-carbonization and application of hydrogen-corrosion-resistant chloride-ion-abrasion-resistant passive film layer

Abstract

The invention discloses a method for preparing a hydrogen-corrosion-resistant chloride-ion-abrasion-resistant passive film layer based on CO2 one-step in-situ oxygen-carbonization and application, and belongs to the technical field of metal corrosion and protection. The method comprises the following steps of: decontaminating, grinding, polishing and drying Ti, Cr, Zr, Al or an alloy base material thereof, putting the Ti, Cr, Zr, Al or the alloy base material thereof into a reaction cavity, taking CO2 gas as an oxygen-carbonization main component, and optionally combining the CO2 gas with air or a solid oxygen supply body NiO to form an oxygen-carbonization system; and the CO2 gauge pressure is controlled to be 0-8.0 MPa, the temperature is 250-750 DEG C, heat preservation is conducted for 3-8 h, and a passive film layer is generated on the surface of the base material through the one-step in-situ oxygen-carbonization reaction. The film layer has excellent hydrogen corrosion resistance and chloride ion abrasion resistance, the preparation method is green and environment-friendly, the preparation process is simple and efficient, and the technology is mature and reliable.

Description

Technical Field

[0001] This invention belongs to the field of metal corrosion and protection technology, and in particular relates to a method and application for preparing a hydrogen corrosion resistant and chloride ion abrasion resistant passivation film based on one-step in-situ oxygen-carbonization of CO2. Background Technology

[0002] Carbon dioxide is a corrosive gas. In high-temperature (usually exceeding 500°C) and anhydrous environments, carbon dioxide gas causes a high-temperature gas-solid phase oxidation and carbonization corrosion reaction on metallic materials, forming an oxygen / carbon film. The reaction first involves the decomposition and oxidation of CO2, and then the carbonization reaction where CO gas can penetrate through defects in the oxide film (such as grain boundaries) to the metal / oxide film interface. For example, CO reacts with chromium (Cr) and iron (Fe) in the alloy to form carbides.

[0003] Ti-containing metals, when exposed to a high-temperature CO2 environment, can form TiO2 / TiC, which has both hydrogen-blocking and hydrogen-absorbing functions. x or TiO2 / TiC x / TiN composite hydrogen-absorbing and chloride-resistant passivation film.

[0004] Traditional TiO2 / TiC x The main methods for preparing composite hydrogen-blocking / chloride-resistant passivation films include chemical vapor deposition, physical vapor deposition, ion implantation, and high-temperature self-propagating methods. All prepared coatings exhibit excellent hydrogen permeation resistance. For example, Checchetto et al. prepared a TiN-TiC bilayer coating on a stainless steel substrate using ion beam-assisted deposition, achieving a hydrogen permeation reduction factor that was four orders of magnitude lower than that of stainless steel. Our research group prepared TiO2 / TiC using ion implantation and ultra-low oxygen partial pressure oxidation. x In the composite coating, the TiC (hydrogen absorber) content increased from 8.9% to 39.4% (Ti2p), while the TiO2 (hydrogen barrier) content decreased from 75.7% to 28.1% (Ti2p). After C ion implantation, the impedance and phase angle of the sample were significantly improved (Lu ZX, Zhou QY, Ling YH, et al. Preparation and hydrogenpenetration performance of TiO2 / TiCx composite coatings, 2020, 45, 14048-14061). However, these methods all suffer from problems to varying degrees, such as complex preparation methods or the need for advanced, large-scale instruments, which hinder their further application. Therefore, it is necessary to develop technologies that are more conducive to practical applications and further promote simple and practical advanced technologies to practical use.

[0005] Therefore, to further address the issue of its practical application, this application employs an in-situ oxygen-carbonization "one-step" process under controlled carbon dioxide atmosphere pressure to simply, efficiently, and reliably prepare new hydrogen corrosion-resistant and chloride ion abrasion-resistant passivation films. The implementation and development of this technology not only benefits the theoretical research and development of hydrogen energy storage and transportation (hydrogen blocking, hydrogen absorption, and hydrogen release) and chloride ion abrasion-resistant coatings, as well as the development and application of materials, but also promotes the practical application and widespread adoption of hydrogen corrosion-resistant and chloride ion abrasion-resistant coatings. Reports on the preparation of hydrogen corrosion-resistant, chloride ion abrasion-resistant, and decorative coatings based on "one-step" in-situ oxidation with CO2 are rare. This invention not only enables the resource utilization of CO2, reducing carbon emissions, and transforming corrosive CO2 at high temperatures into high-value-added utilization, enhancing product value and extending material lifespan, but also opens up a new avenue for high-value utilization of waste. This forward-looking and practically significant technology powerfully promotes the progress of materials surface engineering and carbon neutrality technology. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a method for preparing a hydrogen corrosion resistant and chloride ion erosion resistant passivation film by one-step in-situ oxygen-carbonization using high-purity CO2 as the single or main oxygen-carbonization medium. This method enables the in-situ generation of passivation film with excellent hydrogen corrosion resistance and chloride ion erosion resistance on the surface of Ti, Cr, Zr, Al and their alloys. Moreover, the method is green and environmentally friendly, and the preparation process is simple and efficient.

[0007] The present invention solves the above-mentioned technical problems through the following technical solution:

[0008] A method for preparing a hydrogen corrosion-resistant and chloride ion erosion-resistant passivation film based on one-step in-situ oxygen-carbonization using CO2 includes the following steps:

[0009] S1. The surface of the pure metal or its alloy substrate is sequentially cleaned, ground, polished and dried;

[0010] S2. The substrate treated in step S1 is placed in a reaction chamber, with CO2 gas as the main component of oxygen-carbonization, and optionally combined with air or solid oxygen donor NiO to form an oxygen-carbonization system. The CO2 gauge pressure is controlled at 0-8.0 MPa, the temperature at 250-750℃, and the temperature is maintained for 3-8 hours. Through a one-step in-situ oxygen-carbonization reaction, a hydrogen corrosion resistant and chloride ion abrasion resistant passivation film is generated on the surface of the substrate.

[0011] Furthermore, the metal is one or more of Ti, Cr, Zr, and Al.

[0012] Furthermore, the volume purity of the CO2 gas is ≥99.999%.

[0013] Furthermore, when the oxygen-carbonization system is a CO2 + air system, the volume fraction of CO2 is greater than 0% and less than 100%, with the remainder being air.

[0014] Furthermore, when the oxygen-carbonation system is a CO2 + NiO solid system, the NiO dosage is 1.0-3.0 g / 100 cm³. 3 The cavity volume is placed inside the sample boat, and oxygen is supplied through gas-phase diffusion.

[0015] Furthermore, when the oxygen-carbonation system is a CO2 + air + NiO system, the volume fraction of CO2 is greater than 0% and less than 100%, the balance is air, and the amount of NiO added is 1.0-3.0 g / 100 cm³. 3 Cavity volume.

[0016] Furthermore, the thickness of the hydrogen corrosion resistant and chloride ion abrasion resistant passivation film is 21-462 nm.

[0017] The hydrogen corrosion resistant and chloride ion abrasion resistant passivation film prepared by the method of the present invention is also within the protection scope of the present invention.

[0018] The application of the hydrogen corrosion-resistant and chloride ion abrasion-resistant passivation film prepared by the method of the present invention in the protection of hydrogen-related equipment and components, marine facilities and equipment, carbon dioxide generator sets, hydrogen energy storage and transportation devices or metal components in chlorine-containing working conditions is also within the scope of protection of the present invention.

[0019] The present invention has the following beneficial effects:

[0020] Process innovation: For the first time, the "corrosiveness" of high-purity CO2's high-temperature oxidation-carbonization is transformed into a film-forming driving force. Under conditions of 0-8.0 MPa (gauge pressure) and 250-750℃, a hydrogen corrosion-resistant and chloride ion abrasion-resistant passivation film layer is generated in situ in one step, without the need for vacuum, ion source or multi-stage post-treatment, resulting in a significant reduction in equipment investment and operating costs.

[0021] Hydrogen absorption-resistance synergy: Hydrogen permeation reduction factor ≥1.024E-14, with the highest low-frequency impedance of 1.43E7 and the largest phase angle of 87.52 in 0.1 M Na2SO4.

[0022] Chlorine-resistant - Abrasion: Self-corrosion current density as low as 4.3 × 10⁻⁶ -10 A cm -2 The minimum wear depth of 3.5% NaCl solution is 0.12 μm, and the wear rate decreases by more than 1-2 orders of magnitude.

[0023] Green and universally applicable: Using high-purity CO2, an industrial byproduct, as the main medium, it produces no halogens and no heavy metals. The same process is applicable to Ti, Cr, Zr, Al and their alloys. It can be directly used for on-site or factory prefabrication of corrosion protection for hydrogen-related equipment and components, marine facilities and equipment, carbon dioxide generator sets, hydrogen energy storage and transportation devices and chlorine-containing metal components, and has the conditions for large-scale promotion. Attached Figure Description

[0024] Figure 1 This is a TEM image of the hydrogen corrosion resistant and chloride ion abrasion resistant passivation film prepared in Example 3. Detailed Implementation

[0025] A method for preparing a hydrogen corrosion-resistant and chloride ion-resistant passivation film based on one-step in-situ oxygen-carbonization using CO2, comprising the following steps:

[0026] (1) Cut the substrates of Examples 1-14 into pieces with dimensions of 15×15×1.5 mm. 3 The samples were ultrasonically cleaned with acetone and ethanol (15 minutes each) sequentially to remove contaminants; then they were ground sequentially with SiC sandpaper (400 mesh, 800 mesh, 1500 mesh, 3000 mesh, 5000 mesh, 7000 mesh and 8000 mesh), polished sequentially with 2.5 μm and 0.5 μm silica polishing slurries, rinsed with deionized water and anhydrous ethanol and dried for later use.

[0027] (2) Place the substrate treated in step (1) in a tubular atmosphere furnace, and adjust the atmosphere, pressure, temperature and firing time according to the process parameters of Examples 1-14 below to obtain hydrogen corrosion resistant and chloride ion abrasion resistant passivation film under different process parameters.

[0028] Example 1:

[0029] The raw materials and process parameters for preparing the hydrogen corrosion resistant and chloride ion abrasion resistant passivation film are shown in the table below. The hydrogen corrosion resistance and chloride ion abrasion resistance of the film are as follows:

[0030]

[0031] Example 2:

[0032] The raw materials and process parameters for preparing the hydrogen corrosion resistant and chloride ion abrasion resistant passivation film are shown in the table below. The hydrogen corrosion resistance and chloride ion abrasion resistance of the film are as follows:

[0033]

[0034] Example 3:

[0035] The raw materials and process parameters for preparing the hydrogen corrosion resistant and chloride ion abrasion resistant passivation film are shown in the table below. The hydrogen corrosion resistance and chloride ion abrasion resistance of the film are as follows:

[0036]

[0037] Figure 1 The image shows a TEM image of the passivation film obtained in Example 3, which shows that the film is continuous and uniform with a thickness of approximately 462 nm.

[0038] Example 4:

[0039] The raw materials and process parameters for preparing the hydrogen corrosion resistant and chloride ion abrasion resistant passivation film are shown in the table below. The hydrogen corrosion resistance and chloride ion abrasion resistance of the film are as follows:

[0040]

[0041] Example 5:

[0042] The raw materials and process parameters for preparing the hydrogen corrosion resistant and chloride ion abrasion resistant passivation film are shown in the table below. The hydrogen corrosion resistance and chloride ion abrasion resistance of the film are as follows:

[0043]

[0044] Example 6:

[0045] The raw materials and process parameters for preparing the hydrogen corrosion resistant and chloride ion abrasion resistant passivation film are shown in the table below. The hydrogen corrosion resistance and chloride ion abrasion resistance of the film are as follows:

[0046]

[0047] Example 7:

[0048] The raw materials and process parameters for preparing the hydrogen corrosion resistant and chloride ion abrasion resistant passivation film are shown in the table below. The hydrogen corrosion resistance and chloride ion abrasion resistance of the film are as follows:

[0049]

[0050] Example 8:

[0051] The raw materials and process parameters for preparing the hydrogen corrosion resistant and chloride ion abrasion resistant passivation film are shown in the table below. The hydrogen corrosion resistance and chloride ion abrasion resistance of the film are as follows:

[0052]

[0053] Example 9:

[0054] The raw materials and process parameters for preparing the hydrogen corrosion-resistant and chloride ion abrasion-resistant passivation film are shown in the table below. The hydrogen corrosion resistance and chloride ion abrasion resistance properties of the film are as follows:

[0055]

[0056] Example 10:

[0057] The raw materials and process parameters for preparing the hydrogen corrosion-resistant and chloride ion abrasion-resistant passivation film are shown in the table below. The hydrogen corrosion resistance and chloride ion abrasion resistance properties of the film are as follows:

[0058]

[0059] Example 11:

[0060] The raw materials and process parameters for preparing the hydrogen corrosion-resistant and chloride ion abrasion-resistant passivation film are shown in the table below. The hydrogen corrosion resistance and chloride ion abrasion resistance properties of the film are as follows:

[0061]

[0062] Example 12:

[0063] The raw materials and process parameters for preparing the hydrogen corrosion resistant and chloride ion abrasion resistant passivation film are shown in the table below. The hydrogen corrosion resistance and chloride ion abrasion resistance of the film are as follows:

[0064]

[0065] Example 13:

[0066] The raw materials and process parameters for preparing the hydrogen corrosion resistant and chloride ion abrasion resistant passivation film are shown in the table below. The hydrogen corrosion resistance and chloride ion abrasion resistance of the film are as follows:

[0067]

[0068] Example 14:

[0069] The raw materials and process parameters for preparing the hydrogen corrosion resistant and chloride ion abrasion resistant passivation film are shown in the table below. The hydrogen corrosion resistance and chloride ion abrasion resistance of the film are as follows:

[0070]

Claims

1. A method for preparing a passivation film layer resistant to hydrogen etching and chlorine ion abrasion by one-step in-situ oxygen-carbonization based on CO2, characterized in that, The method comprises the following steps: S1. sequentially performing decontamination, grinding, polishing and drying on the surface of a pure metal or alloy substrate; S2. placing the substrate treated in step S1 in a reaction chamber, forming an oxygen-carbonization system with CO2 gas as the main component of oxygen-carbonization and optionally combined with air or solid oxygen supplier NiO, controlling the CO2 surface pressure to be 0-8.0 MPa, the temperature to be 250-750℃, and the holding time to be 3-8 h, and generating a hydrogen-etching-resistant and chlorine-ion-erosion-resistant passivation film layer on the surface of the substrate through one-step in-situ oxygen-carbonization reaction.

2. The method of claim 1, wherein, The metal is one or more than two of Ti, Cr, Zr and Al.

3. The method of claim 1, wherein, The volume purity of the CO2 gas is ≥99.999%.

4. The method of claim 1, wherein, When the oxygen-carbonization system is a CO2+air system, the volume fraction of CO2 is greater than 0% and less than 100%, and the rest is air.

5. The method of claim 1, wherein, When the oxygen-carbon system is CO2+NiO solid system, the amount of NiO is 1.0-3.0 g / 100 cm 3 The cavity volume, placed in the sample boat, is supplied with oxygen by gas-phase diffusion.

6. The method of claim 1, wherein, When the oxygen-carbon system is CO2+air+NiO system, the volume fraction of CO2 is greater than 0% and less than 100%, the balance is air, and the amount of NiO added is 1.0-3.0 g / 100 cm 3 Cavity volume.

7. The method of claim 1, wherein, The thickness of the hydrogen-etching-resistant and chlorine-ion-erosion-resistant passivation film layer is 21-462 nm.

8. The hydrogen-etching-resistant and chlorine-ion-erosion-resistant passivation film layer prepared by the method in any one of claims 1-7.

9. The application of the hydrogen-etching-resistant and chlorine-ion-erosion-resistant passivation film layer prepared by the method in any one of claims 1-7 in the protection and decoration of hydrogen-related equipment and components, marine facilities and equipment, carbon dioxide power generating units, hydrogen energy storage and transportation devices, or metal components in chlorine-containing working conditions.

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