A method for preparing an oxide film on a metal material surface

Abstract

The application discloses a kind of preform methods of metal material surface oxide film, it is related to nuclear power energy technical field, including the following steps: cleaning the particle dust on the surface of metal material;Cleaning the grease on the surface of metal material;Add oxide film preform liquid to the metal material and preform, form oxide film on the surface of metal material;The preform liquid includes depleted zinc acetate, preform temperature is 250 DEG C~320 DEG C, preform pressure is 14.0MPa~16.5MPa.The dust particle and grease etc. on the surface of metal material are removed first, then preform using preform liquid, and with depleted zinc acetate as preform liquid, control preform temperature and preform pressure, form oxide film on the surface of metal material, not only make the preform process of oxide film simple, but also effectively solve the problem of poor preform effect of traditional oxide film preform process, with good anticorrosion effect, and corrosion rate is low, so that the protection effect of the oxide film to equipment is better.

Description

Technical Field

[0001] This invention relates to the field of nuclear power energy technology, and specifically to a method for pre-forming an oxide film on the surface of a metal material. Background Technology

[0002] Nuclear power plant construction is a long process with large upfront investments. Once completed, equipment maintenance and material replacements are extremely costly, making material and equipment replacement nearly impossible in many cases. In such situations, adjusting water chemistry is sought to avoid or mitigate equipment failures due to corrosion and excessive radiation during shutdowns. Finding effective measures to suppress corrosion of primary circuit structural materials during service is currently a key research focus, hot topic, and challenging area in the field of primary circuit system material corrosion research.

[0003] Existing technologies also disclose some techniques for forming an oxide film on a metal surface to prevent corrosion. For example, the published patent CN106381460B discloses a method for preventing corrosion of magnesium and its alloys and the application of a MgCO3 layer as an anti-corrosion layer. CO2 gas is plasmaized to improve its reactivity, so that it reacts with the loose and porous MgO film formed by the natural oxidation of magnesium in the air at room temperature to form a MgCO3 protective layer, thereby improving the corrosion resistance of magnesium and its alloys.

[0004] The published patent CN112267089B discloses a corrosion prevention method for aluminum alloys with ultra-fine microstructure. It utilizes the characteristic that a dense oxide film can be formed on the surface of aluminum alloys with uniform and fine microstructure and grain size below 100nm. By controlling the process conditions of grinding, polishing and static placement, a self-passivating film is formed on the surface of the aluminum alloy, thereby playing a role in corrosion prevention.

[0005] Patent CN116516330A discloses a passivation treatment system and method for the inner surfaces of equipment in the secondary loop of a nuclear power plant. The method includes: Step 1: preparing a hydrazine passivation solution in a hydrazine metering tank; Step 2: restoring the condensate polishing system to full flow treatment; Step 3: controlling the hydrazine concentration in the feedwater by adding a hydrazine metering pump; Step 4: completing the passivation treatment of the inner surfaces of the secondary loop system and equipment. This invention, by increasing the hydrazine concentration in the secondary loop, can efficiently and safely passivate the surfaces of pipelines and equipment in the secondary loop system, thereby quickly repairing the passivation film and achieving the technical effect of reducing the corrosion rate of the equipment.

[0006] To effectively reduce the corrosion of primary circuit structural materials during service, a suitable oxide film prefabrication technology is also needed. This technology forms a dense oxide film before the primary circuit system is officially put into operation, effectively inhibiting corrosion during later operation and thus mitigating primary circuit corrosion and reducing the radiation dose field outside the reactor core. However, existing metal corrosion protection methods (such as those disclosed in the three patent documents mentioned above) all suffer from complex processes and poor oxide film formation. Summary of the Invention

[0007] Given the current problems of complex processes and poor oxide film formation in preparing anti-corrosion oxide films on metal surfaces, the present invention aims to provide a pre-preparation method for oxide films on metal surfaces. This pre-preparation method is simple to operate. By adding a suitable pre-preparant, the oxide film is pre-prepared under specific temperature and pressure conditions, which effectively simplifies the pre-preparation steps and obtains a denser oxide film through a simpler method. This oxide film can effectively prevent the metal material from being corroded in subsequent high-temperature and high-pressure environments.

[0008] This invention is achieved through the following technical solution:

[0009] This application provides a method for preforming an oxide film on the surface of a metallic material, comprising the following steps:

[0010] Clean particulate dust from the surface of metal materials;

[0011] Clean grease from the surface of metal materials;

[0012] An oxide film pre-forming solution is added to the metal material to pre-form an oxide film on the surface of the metal material;

[0013] The pre-prepared solution includes lean zinc acetate, the pre-preparation temperature is 250℃~320℃, and the pre-preparation pressure is 14.0MPa~16.5MPa.

[0014] The pre-set temperature can be 250℃, 260℃, 270℃, 280℃, 290℃, 300℃, 310℃, 320℃, or any temperature value within this temperature range.

[0015] The pre-pressurization pressure can be 14.0MPa, 14.5MPa, 15.0MPa, 15.5MPa, 16.0MPa, 16.5MPa, or any pressure value within this pressure range.

[0016] In this invention, depleted zinc acetate is used as a pre-prepared solution and added to the cleaned metal material to form a uniform and dense oxide film on the metal material, which can effectively protect the metal material from corrosion in subsequent high temperature and high pressure environments.

[0017] The formation mechanism of this oxide film mainly involves zinc from depleted zinc acetate diffusing into the oxide lattice and competing with Co ions for electrons and holes in the oxide corrosion layer. Some Co undergoes structural reorganization, forming a new metal oxide layer on the equipment surface. Zinc can prevent further oxidation. 58 Co and 60 Co is incorporated into the outer layer of chromite spinel in the eight-core substrate, reducing the potential corrosion rate and thus lowering the radiation dose. Over time, this process results in a thinner oxide film with increased stability, effectively slowing the growth of free-flowing stainless steel cracks (FWSCC) and some fissures. Compared to traditional oxide film pre-preparations using hydrazine or similar agents, this oxide film is not only more uniform and dense but also does not affect the metal substrate structure or surface gloss, exhibiting strong corrosion resistance even under high temperature and pressure conditions. Therefore, the proposed method for pre-forming oxide films on metal surfaces effectively solves the problem of poor pre-forming effects in traditional oxide film pre-forming processes.

[0018] Furthermore, the concentration of the pre-prepared liquid is 10 mg / L to 80 mg / L.

[0019] The concentration of the pre-prepared solution can be 10 mg / L, 20 mg / L, 30 mg / L, 40 mg / L, 50 mg / L, 60 mg / L, 70 mg / L, 80 mg / L, or any concentration value within this range.

[0020] Furthermore, the pre-processing cycle time is 450h to 750h.

[0021] The pre-creation cycle time can be 450h, 500h, 550h, 600h, 650h, 750h, or any time value within the range of the pre-creation cycle time.

[0022] Furthermore, the metallic material includes stainless steel and nickel-based alloys.

[0023] Furthermore, the rinsing liquid used to clean particulate dust from the surface of metal materials is deionized water.

[0024] Furthermore, when cleaning particulate dust from the surface of metal materials, the rinsing temperature is 25℃~40℃.

[0025] The rinsing temperature can be 25℃, 30℃, 35℃, 40℃, or any temperature value within the range of the rinsing temperature.

[0026] Furthermore, when cleaning particulate dust from the surface of metal materials, the rinsing cycle time is 25 min to 50 min.

[0027] The rinsing cycle time can be 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, or any time value within the range of the rinsing cycle time.

[0028] Furthermore, rinsing solutions used to clean grease from metal surfaces include ethanol or ether.

[0029] Furthermore, when cleaning grease from the surface of metal materials, the rinsing temperature should be 20℃~45℃.

[0030] The rinsing temperature can be 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, or any rinsing temperature value within the range of the rinsing temperature.

[0031] Furthermore, when cleaning grease from the surface of metal materials, the rinsing cycle time is 30 to 60 minutes.

[0032] The rinsing cycle time can be 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, or any time value within the range of the rinsing cycle time.

[0033] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0034] (1) The present invention adopts the method of first removing dust particles and grease from the surface of metal materials, and then using a pre-preparation liquid to pre-prepare the metal materials. The pre-preparation liquid is depleted zinc acetate, and a certain pre-preparation temperature and pressure are controlled to form an oxide film on the surface of the metal materials. This not only simplifies the pre-preparation process of the oxide film, but also effectively solves the problem of poor pre-preparation effect of the traditional oxide film pre-preparation process. The oxide film has a good anti-corrosion effect, and the corrosion rate is low and the corrosion resistance time is long, which makes the oxide film better protect the equipment.

[0035] (2) The oxide film prefabrication method of the present invention makes the oxide film formed on the surface of the metal material more uniform and dense, and can effectively protect the metal material from corrosion in the subsequent high temperature and high pressure environment.

[0036] (3) Compared with traditional oxide film pre-preparation agents such as hydrazine, the oxide film of the present invention is not only more uniform and dense, but also does not affect the structure of the metal substrate and the surface brightness. It also has strong corrosion resistance even under high temperature and high pressure, effectively solving the problem of poor pre-preparation effect of traditional oxide film pre-preparation process. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments.

[0038] The "scope" disclosed in this application is defined by a lower limit and an upper limit. A given scope is defined by selecting a lower limit and an upper limit, which define the boundaries of the specific scope. A scope defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a scope. Unless otherwise specified, the terms "comprising" and "including" in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that it may also include or include other substances not listed, or it may only include or include the listed substances.

[0039] Therefore, the following detailed description of embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0040] Example 1

[0041] This embodiment provides a method for pre-forming an oxide film on the surface of a metal material, which is carried out according to the following steps:

[0042] S1. Use 30℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0043] S2. Use 30℃ ethanol to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0044] S3. Pre-form 304 stainless steel using 300℃ and 10ppm depleted zinc acetate. During the pre-formulation process, a pressure of 14.5MPa needs to be maintained, and the pre-formulation time is 450 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0045] Example 2

[0046] This embodiment provides a method for pre-forming an oxide film on the surface of a metal material, which is carried out according to the following steps:

[0047] S1. Use 35℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0048] S2. Use ethanol at 35℃ to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0049] S3. Pre-form 304 stainless steel using 290℃ and 50ppm zinc acetate depletion. During the pre-formulation process, a pressure of 15.0MPa must be maintained, and the pre-formulation time is 500 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0050] Example 3

[0051] This embodiment provides a method for pre-forming an oxide film on the surface of a metal material, which is carried out according to the following steps:

[0052] S1. Use 40℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0053] S2. Use 40℃ ethanol to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0054] S3. Pre-form 304 stainless steel using 310℃ and 70ppm zinc acetate. During the pre-formulation process, a pressure of 15.5MPa must be maintained, and the pre-formulation time is 550 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0055] Example 4

[0056] This embodiment provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Embodiment 1, the pre-forming temperature in this embodiment is 250°C, while other process conditions are the same as in Embodiment 1. The method is carried out according to the following steps:

[0057] S1. Use 35℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0058] S2. Use ethanol at 35℃ to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0059] S3. Pre-form 304 stainless steel using 250℃ and 50ppm zinc acetate depletion. During the pre-formulation process, a pressure of 15.0MPa must be maintained, and the pre-formulation time is 500 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0060] Example 5

[0061] This embodiment provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Embodiment 1, the pre-forming temperature in this embodiment is 260°C, while other process conditions are the same as in Embodiment 1. The method is carried out according to the following steps:

[0062] S1. Use 35℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0063] S2. Use ethanol at 35℃ to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0064] S3. Pre-form 304 stainless steel using 260℃ and 50ppm zinc acetate depletion. During the pre-formulation process, a pressure of 15.0MPa must be maintained, and the pre-formulation time is 500 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0065] Example 6

[0066] This embodiment provides a method for preforming an oxide film on the surface of a metal material. Unlike Embodiment 1, the preforming pressure in this embodiment is 270°C, while other process conditions are the same as in Embodiment 1. The method is carried out according to the following steps:

[0067] S1. Use 35℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0068] S2. Use ethanol at 35℃ to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0069] S3. Pre-form 304 stainless steel using 270℃ and 50ppm zinc acetate depletion. During the pre-formulation process, a pressure of 15.0MPa must be maintained, and the pre-formulation time is 500 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0070] Example 7

[0071] This embodiment provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Embodiment 1, the pre-forming temperature in this embodiment is 280°C, while other process conditions are the same as in Embodiment 1. The method is carried out according to the following steps:

[0072] S1. Use 35℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0073] S2. Use ethanol at 35℃ to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0074] S3. Pre-form 304 stainless steel using 280℃ and 50ppm zinc acetate depletion. During the pre-formulation process, a pressure of 15.0MPa must be maintained, and the pre-formulation time is 500 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0075] Example 8

[0076] This embodiment provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Embodiment 1, the pre-forming pressure in this embodiment is 14.0 MPa, while other process conditions are the same as in Embodiment 1. The method is carried out according to the following steps:

[0077] S1. Use 35℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0078] S2. Use ethanol at 35℃ to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0079] S3. Pre-form 304 stainless steel using 300℃ and 50ppm zinc acetate. During the pre-formulation process, a pressure of 14.0MPa must be maintained, and the pre-formulation time is 500 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0080] Example 9

[0081] This embodiment provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Embodiment 1, the pre-forming pressure in this embodiment is 16.0 MPa, while other process conditions are the same as in Embodiment 1. The method is carried out according to the following steps:

[0082] S1. Use 35℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0083] S2. Use ethanol at 35℃ to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0084] S3. Pre-form 304 stainless steel using 300℃ and 50ppm zinc acetate. During the pre-formulation process, a pressure of 16.0MPa must be maintained, and the pre-formulation time is 500 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0085] Example 10

[0086] This embodiment provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Embodiment 1, the pre-forming pressure in this embodiment is 16.5 MPa, while other process conditions are the same as in Embodiment 1. The method is carried out according to the following steps:

[0087] S1. Use 35℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0088] S2. Use ethanol at 35℃ to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0089] S3. Pre-form 304 stainless steel using 300℃ and 50ppm zinc acetate. During the pre-formulation process, a pressure of 16.5MPa must be maintained, and the pre-formulation time is 500 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0090] Example 11

[0091] This embodiment provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Embodiment 1, the concentration of the pre-forming solution in this embodiment is 20 ppm, while other process conditions are the same as in Embodiment 1. The method is carried out according to the following steps:

[0092] S1. Use 30℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0093] S2. Use 30℃ ethanol to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0094] S3. Pre-form 304 stainless steel using 300℃ and 20ppm zinc acetate. During the pre-formulation process, a pressure of 14.5MPa needs to be maintained, and the pre-formulation time is 450 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, and a pre-formed oxide film is formed on the 304 stainless steel.

[0095] Example 12

[0096] This embodiment provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Embodiment 1, the concentration of the pre-forming solution in this embodiment is 30 ppm, while other process conditions are the same as in Embodiment 1. The method is carried out according to the following steps:

[0097] S1. Use 30℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0098] S2. Use 30℃ ethanol to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0099] S3. Pre-form 304 stainless steel using 300℃ and 30ppm zinc acetate. During the pre-formulation process, a pressure of 14.5MPa needs to be maintained, and the pre-formulation time is 450 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, and a pre-formed oxide film is formed on the 304 stainless steel.

[0100] Example 13

[0101] This embodiment provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Embodiment 1, the concentration of the pre-forming solution in this embodiment is 40 ppm, while other process conditions are the same as in Embodiment 1. The method is carried out according to the following steps:

[0102] S1. Use 30℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0103] S2. Use 30℃ ethanol to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0104] S3. Pre-form 304 stainless steel using 300℃ and 40ppm zinc acetate depletion. During the pre-formulation process, a pressure of 14.5MPa needs to be maintained, and the pre-formulation time is 450 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0105] Example 14

[0106] This embodiment provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Embodiment 1, the concentration of the pre-forming solution in this embodiment is 60 ppm, while other process conditions are the same as in Embodiment 1. The method is carried out according to the following steps:

[0107] S1. Use 30℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0108] S2. Use 30℃ ethanol to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0109] S3. Pre-form 304 stainless steel using 300℃ and 60ppm zinc acetate. During the pre-formulation process, a pressure of 14.5MPa needs to be maintained, and the pre-formulation time is 450 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, and a pre-formed oxide film is formed on the 304 stainless steel.

[0110] Example 15

[0111] This embodiment provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Embodiment 1, the concentration of the pre-forming solution in this embodiment is 80 ppm, while other process conditions are the same as in Embodiment 1. The method is carried out according to the following steps:

[0112] S1. Use 30℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0113] S2. Use 30℃ ethanol to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0114] S3. Pre-form 304 stainless steel using 300℃ and 80ppm zinc acetate. During the pre-formulation process, a pressure of 14.5MPa needs to be maintained, and the pre-formulation time is 450 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, and a pre-formed oxide film is formed on the 304 stainless steel.

[0115] Example 16

[0116] This embodiment provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Embodiment 1, the metal material in this embodiment is a nickel-based alloy. Other process conditions are the same as in Embodiment 1, and the method is carried out according to the following steps:

[0117] S1. Use 30℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0118] S2. Use 30℃ ethanol to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0119] S3. The nickel-based alloy is pre-formed using 300℃ and 10ppm zinc acetate. The pressure needs to be maintained at 14.5MPa during the pre-formation process, and the pre-formation time is 450 hours. After the pre-formation is completed, the pre-formed liquid is discharged, and a pre-formed oxide film is formed on the nickel-based alloy.

[0120] Comparative Example 1

[0121] This comparative example provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Example 1, the pre-forming temperature in this comparative example is 230°C, while other process conditions are the same as in Example 1, and the method is carried out according to the following steps:

[0122] S1. Use 35℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0123] S2. Use ethanol at 35℃ to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0124] S3. Pre-form 304 stainless steel using 230℃ and 50ppm zinc acetate depletion. During the pre-formulation process, a pressure of 15.0MPa must be maintained, and the pre-formulation time is 500 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0125] Comparative Example 2

[0126] This comparative example provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Example 1, the pre-forming temperature in this comparative example is 330°C, while other process conditions are the same as in Example 1, and the method is carried out according to the following steps:

[0127] S1. Use 35℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0128] S2. Use ethanol at 35℃ to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0129] S3. Pre-form 304 stainless steel using 330℃ and 50ppm zinc acetate depletion. During the pre-formulation process, a pressure of 15.0MPa must be maintained, and the pre-formulation time is 500 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0130] Comparative Example 3

[0131] This comparative example provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Example 1, the pre-forming pressure in this comparative example is 13.0 MPa, while other process conditions are the same as in Example 1, and the following steps are followed:

[0132] S1. Use 35℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0133] S2. Use ethanol at 35℃ to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0134] S3. Pre-form 304 stainless steel using 300℃ and 50ppm zinc acetate. During the pre-formulation process, a pressure of 13.0MPa must be maintained, and the pre-formulation time is 500 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0135] Comparative Example 4

[0136] This comparative example provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Example 1, the pre-forming pressure in this comparative example is 17.0 MPa, while other process conditions are the same as in Example 1, and the following steps are followed:

[0137] S1. Use 35℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0138] S2. Use ethanol at 35℃ to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0139] S3. Pre-form 304 stainless steel using 300℃ and 50ppm zinc acetate. During the pre-formulation process, a pressure of 17.0MPa must be maintained, and the pre-formulation time is 500 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0140] Comparative Example 5

[0141] This comparative example provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Example 1, the concentration of the pre-forming solution in this comparative example is 8 ppm, while other process conditions are the same as in Example 1, and the following steps are followed:

[0142] S1. Use 35℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0143] S2. Use ethanol at 35℃ to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0144] S3. Pre-form 304 stainless steel using 300℃ and 8ppm zinc acetate. During the pre-formulation process, a pressure of 14.5MPa must be maintained, and the pre-formulation time is 500 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0145] Comparative Example 6

[0146] This comparative example provides a method for pre-forming an oxide film on the surface of a metal material. Unlike Example 1, the concentration of the pre-forming solution in this comparative example is 85 ppm, while other process conditions are the same as in Example 1, and the following steps are followed:

[0147] S1. Use 35℃ deionized water to circulate and rinse the particulate dust on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0148] S2. Use ethanol at 35℃ to circulate and rinse the grease and other substances on the surface of the metal material for 30 minutes. After rinsing, the rinsing solution is discharged normally.

[0149] S3. Pre-form 304 stainless steel using 300℃ and 85ppm zinc acetate. During the pre-formulation process, a pressure of 14.5MPa must be maintained, and the pre-formulation time is 500 hours. After the pre-formulation is completed, the pre-formulation solution is discharged, at which point a pre-formed oxide film is formed on the 304 stainless steel.

[0150] Comparative Example 7

[0151] This comparative example uses the method disclosed in the prior art (patent CN116516330A) to form a passivation film on the surface of 304 stainless steel. The specific method is as follows:

[0152] Step 1: Prepare the hydrazine passivation solution in the hydrazine metering tank;

[0153] Step 2: Restore the condensate polishing system to full flow treatment;

[0154] Step 3: Control the hydrazine concentration in the feed water to 10 ppm using a hydrazine metering pump;

[0155] Step 4: Use the hydrazine solution to pre-form 304 stainless steel. During the pre-forming process, a pressure of 14.5 MPa needs to be maintained, and the pre-forming time is 450 hours. After the pre-forming is completed, the pre-forming solution is discharged. At this time, a pre-formed oxide film is formed on the 304 stainless steel.

[0156] The corrosion resistance of the oxide films pre-formed on the surface of metallic materials using the methods described in Examples 1 to 16 and Comparative Examples 1 to 7 was tested. The results were obtained using the uniform corrosion immersion test method (JB / T7901-2001) and are shown in Table 1 below.

[0157] Table 1. Corrosion resistance test data of oxide films prepared by different methods.

[0158]

[0159]

[0160] As can be seen from the test data in the table, after 96 hours of testing using the uniform corrosion immersion test method (JB / T7901-2001), the corrosion resistance of the oxide film pre-prepared using the method of this invention is significantly higher than that of the oxide film pre-prepared using the method in the comparative example. Furthermore, the comparison revealed that the concentration of the pre-preparation solution, the temperature during pre-preparation, and the pressure during pre-preparation all affect the corrosion resistance of the oxide film. The oxide film pre-prepared using the pre-preparation solution concentration, temperature, and pressure specified in this invention exhibits higher corrosion resistance than the comparative example, proving that the oxide film pre-prepared using the pre-preparation method of this application has better corrosion resistance. Moreover, the pre-preparation process is simple and effectively solves the problem of poor pre-preparation effect in traditional oxide film pre-preparation processes, resulting in better protection of the equipment. Simultaneously, compared with traditional oxide film pre-preparations using hydrazine and other similar agents, the oxide film prepared using the pre-preparation method of this application is not only more uniform and dense but also does not affect the metal substrate structure and surface gloss, exhibiting strong corrosion resistance even under high temperature and high pressure environments.

[0161] The foregoing description illustrates and describes preferred embodiments of the present invention. As previously stated, it should be understood that the present invention is not limited to the forms disclosed herein and should not be construed as excluding other embodiments. It can be used in various other combinations, modifications, and environments, and can be altered within the scope of the inventive concept described herein through the foregoing teachings or techniques or knowledge in related fields. Any modifications and variations made by those skilled in the art that do not depart from the spirit and scope of the present invention should be within the protection scope of the appended claims.

Claims

1. A method for pre-forming an oxide film on the surface of a metallic material, characterized in that, Includes the following steps: Clean particulate dust from the surface of metal materials; Clean grease from the surface of metal materials; Adding an oxide film pretreatment solution to the metal material pretreatment process forms an oxide film on the surface of the metal material. This oxide film can prevent... It combines with chromite spinel; The pre-prepared solution includes lean zinc acetate, the pre-preparation temperature is 250℃~320℃, and the pre-preparation pressure is 14.0MPa~16.5MPa; The concentration of the pre-prepared solution is 10 mg / L to 80 mg / L; The pre-processing cycle time is 450 h ~ 750 h.

2. The method for pre-forming an oxide film on the surface of a metal material according to claim 1, characterized in that, The metallic materials include stainless steel and nickel-based alloys.

3. The method for pre-forming an oxide film on the surface of a metal material according to claim 1, characterized in that, The rinsing liquid used to clean particulate dust from the surface of metal materials is deionized water.

4. The method for pre-forming an oxide film on the surface of a metal material according to claim 3, characterized in that, When cleaning particulate dust from the surface of metal materials, the rinsing temperature should be 25℃~40℃.

5. A method for pre-forming an oxide film on the surface of a metallic material according to claim 3 or 4, characterized in that, When cleaning particulate dust from the surface of metal materials, the rinsing cycle time is 25 min to 50 min.

6. The method for pre-forming an oxide film on the surface of a metal material according to claim 1, characterized in that, Rinsing solutions used to clean grease from metal surfaces include ethanol or ether.

7. The method for pre-forming an oxide film on the surface of a metal material according to claim 6, characterized in that, When cleaning grease from the surface of metal materials, the rinsing temperature should be 20℃~45℃.

8. A method for pre-forming an oxide film on the surface of a metallic material according to claim 6 or 7, characterized in that, When cleaning grease from the surface of metal materials, the rinsing cycle time is 30 to 60 minutes.

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