Super-compact CrTiN conductive corrosion-resistant ceramic coating and preparation method thereof

Abstract

The invention relates to the technical field of hydrogen fuel cells, and discloses a super-compact CrTi N conductive corrosion-resistant ceramic coating and a preparation method thereof. The invention discloses a preparation method of a super-compact CrTiN conductive corrosion-resistant ceramic coating. The preparation method comprises the following steps of 1, metal substrate pretreatment, 2, coating deposition pretreatment, 3, pure Ti transition layer deposition and 4, CrT iN coating deposition. According to the super-compact CrTiN conductive corrosion-resistant ceramic coating provided by the invention, the surface contact resistance can reach 3.62 m omega.cm < 2 >, and the super-compact CrTiN conductive corrosion-resistant ceramic coating shows good conductivity; the corrosion current density can reach 6.8 mu A.cm <-2 >, the corrosion potential can reach-0.18 V, and good corrosion resistance is shown; the contact angle can reach 115.86 degrees, and good hydrophobicity is shown.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen fuel cells, and in particular to an ultra-dense CrTiN conductive corrosion-resistant ceramic coating and a preparation method thereof. Background Art

[0002] CrTiN coating is an alloyed coating deposited on the substrate surface through ion plating technology. It has the advantages of high bonding strength, good corrosion resistance and good conductivity. It is widely used in the fields of surface decoration and corrosion resistance of metal materials.

[0003] However, in practical applications in hydrogen fuel cells, some existing CrTiN coatings exhibit certain deficiencies in electrical conductivity, corrosion resistance, and structural stability, limiting their application in hydrogen fuel cell technology. Consequently, developing an ultra-dense CrTiN conductive, corrosion-resistant ceramic coating with excellent electrical conductivity and corrosion resistance, as well as structural stability, has become a pressing technical challenge for those skilled in the art. Summary of the Invention

[0004] The purpose of the present invention is to provide an ultra-dense CrTiN conductive corrosion-resistant ceramic coating and a preparation method thereof, wherein the ultra-dense CrTiN conductive corrosion-resistant ceramic coating has both excellent conductive and corrosion-resistant properties and a stable structure.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] One of the technical solutions of the present invention:

[0007] A method for preparing an ultra-dense CrTiN conductive corrosion-resistant ceramic coating comprises the following steps:

[0008] 1. Metal substrate pretreatment

[0009] The metal substrate is placed in a degreasing agent and ultrasonically degreased. The metal substrate is then placed in deionized water, anhydrous ethanol, and acetone in sequence and ultrasonically cleaned. Finally, the metal substrate is blown dry.

[0010] 2. Pre-treatment of coating deposition

[0011] The metal substrate pretreated in step 1) is placed in a magnetron sputtering vacuum chamber equipped with a Ti target and a Cr target, and fixed on a workpiece holder, and the metal substrate is plasma cleaned;

[0012] 3. Deposition of pure Ti transition layer

[0013] Using a Ti target as a sputtering source and argon as a working gas, an ion plating process is used to deposit a pure Ti transition layer on the surface of the metal substrate after the pre-treatment of the coating deposition in step 2);

[0014] 4. Deposition of CrTiN coating

[0015] Using Ti target and Cr target as sputtering sources, argon and nitrogen as working gases, an ion plating process is used to deposit a layer of CrTiN coating on the surface of the pure Ti transition layer obtained in step 3) to obtain the ultra-dense CrTiN conductive corrosion-resistant ceramic coating.

[0016] Furthermore, in step 1, the metal substrate is stainless steel or aluminum alloy.

[0017] Furthermore, in step 1, the duration of the ultrasonic fat removal is 8 minutes.

[0018] Furthermore, in step 1, the duration of the ultrasonic cleaning is 5 minutes.

[0019] Furthermore, in step 2, the working conditions of the plasma cleaning are: the distance between the metal substrate and the target is 90 mm, the workpiece holder speed is 8-10 r / min, and the pressure in the chamber is ≤5.0×10 -3 Pa, Ti target current is 0.3A, Cr target current is 0.1A, metal substrate bias is -100V to -400V, plasma cleaning time is 20min, and plasma cleaning temperature is 200 to 350℃.

[0020] Furthermore, in step 3, the working conditions of the ion plating process are: the workpiece holder rotation speed is 8 to 10 r / min, the chamber pressure is 0.1 to 0.5 Pa, the Ti target current is 1.8 to 2 A, the metal substrate bias is -120 V to -90 V, the deposition time is 6 to 10 min, and the deposition temperature is 200 to 350°C.

[0021] Furthermore, in step 4, the working conditions of the ion plating process are: the workpiece holder speed is 8 to 10 r / min, the chamber pressure is 0.1 to 0.5 Pa, the Ti target current is 1.8 to 2 A, the Cr target current is 0.3 A, the metal substrate bias is -60 V, the deposition time is 80 to 120 min, and the deposition temperature is 200 to 350 ° C.

[0022] The second technical solution of the present invention:

[0023] The ultra-dense CrTiN conductive corrosion-resistant ceramic coating prepared by the preparation method of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating.

[0024] The third technical solution of the present invention:

[0025] Application of the above-mentioned ultra-dense CrTiN conductive corrosion-resistant ceramic coating in hydrogen fuel cells.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The present invention provides an ultra-dense CrTiN conductive corrosion-resistant ceramic coating with a surface contact resistance of up to 3.62 mΩ·cm. 2 , showing good electrical conductivity;

[0028] The present invention provides an ultra-dense CrTiN conductive corrosion-resistant ceramic coating with a corrosion current density of up to 6.8 μA·cm -2 , the corrosion potential can reach -0.18V, showing good corrosion resistance;

[0029] The present invention provides an ultra-dense CrTiN conductive corrosion-resistant ceramic coating with a contact angle of up to 115.86°, showing good hydrophobicity, which lays the foundation for the corrosion resistance of the CrTiN coating in acidic environments.

[0030] The present invention provides a method for preparing an ultra-dense CrTiN conductive corrosion-resistant ceramic coating, which achieves the deposition of the CrTiN coating by temperature-raising magnetron sputtering. In the initial deposition stage, incident gas-phase atoms are first adsorbed by the metal substrate. As the deposition temperature increases, the thermal activation effect is significantly enhanced. Sufficient heat can promote the diffusion of Ti, Cr, and N atoms on the metal substrate, increase the collision frequency of N atoms, promote the nitridation of Ti atoms, and promote the more uniform diffusion of Cr-N ceramic phase and Cr atoms on the metal substrate. (Cr can combine with N to form a stable Cr-N ceramic phase. , thereby effectively improving the corrosion resistance of the CrTiN coating. Cr can promote the densification of the CrTiN coating, reduce the pores inside the CrTiN coating, and effectively improve the conductivity and stability of the CrTiN coating. This realizes the preparation of an ultra-dense CrTiN conductive corrosion-resistant ceramic coating that has both excellent conductive and corrosion-resistant properties and a stable structure. In addition, as the deposition temperature increases, the crystallinity of TiN will also increase. The increase in the crystallinity of TiN will increase the number of intermediate carriers in the CrTiN coating, thereby improving the conductive properties of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating.

[0031] The present invention provides a method for preparing an ultra-dense CrTiN conductive corrosion-resistant ceramic coating. Due to the increase in deposition temperature, the density of the CrTiN coating is effectively increased, and the water contact angle of the CrTiN coating is effectively improved (the temperature is increased to promote the deposition of incident gas-phase atoms into a large grain growth morphology, increase the size of surface particles, and thus effectively increase the water contact angle of the CrTiN coating). The increase in density and water contact angle is conducive to inhibiting the infiltration of corrosive solutions, thereby improving the corrosion resistance of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating.

[0032] The present invention provides a method for preparing an ultra-dense CrTiN conductive corrosion-resistant ceramic coating. By lowering the metal substrate bias voltage to -60V, the sudden temperature rise of the metal substrate caused by thermal stress is alleviated, thereby improving the adhesion between the CrTiN coating and the stainless steel substrate and the aluminum alloy substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Various other advantages and benefits will become apparent to those skilled in the art upon reading the detailed description of the preferred embodiment below. The accompanying drawings are for illustration purposes only and are not to be considered as limiting the present invention. The same reference symbols are used throughout the drawings to represent the same components. In the drawings:

[0034] Figure 1 This is a surface morphology of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating prepared in Example 8;

[0035] Figure 2 This is a cross-sectional morphology of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating prepared in Example 8;

[0036] Figure 3 This is the water contact angle of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating prepared in Example 8. DETAILED DESCRIPTION

[0037] Various exemplary embodiments of the present invention are now described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terms used in the present invention are only for describing specific embodiments and are not intended to limit the present invention.

[0038] In addition, for numerical ranges in the present invention, it is understood that each intervening value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated value or intervening value in the stated range is also included in the present invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

[0039] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0040] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be exemplary only.

[0041] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0042] In the following embodiment, a method for preparing an ultra-dense CrTiN conductive corrosion-resistant ceramic coating comprises the following steps:

[0043] 1. Metal substrate pretreatment

[0044] The metal substrate was placed in a degreasing agent and ultrasonically degreased for 8 minutes. The metal substrate was then placed in deionized water, anhydrous ethanol, and acetone in sequence, and ultrasonically cleaned for 5 minutes each. Finally, the metal substrate was blown dry.

[0045] Wherein, the metal substrate is stainless steel or aluminum alloy;

[0046] 2. Pre-treatment of coating deposition

[0047] The metal substrate pretreated in step 1) is placed in a magnetron sputtering vacuum chamber equipped with a Ti target and a Cr target, and fixed on a workpiece holder, and the metal substrate is plasma cleaned;

[0048] The working conditions of the plasma cleaning are as follows: the distance between the metal substrate and the target is 90 mm, the rotation speed of the workpiece holder is 8-10 r / min, and the pressure in the chamber is ≤5.0×10 -3 Pa, Ti target current is 0.3A, Cr target current is 0.1A, metal substrate bias is -100V to -400V, plasma cleaning time is 20min, and plasma cleaning temperature is 200 to 350℃;

[0049] 3. Deposition of pure Ti transition layer

[0050] Using a Ti target as a sputtering source and argon as a working gas, an ion plating process is used to deposit a pure Ti transition layer on the surface of the metal substrate after the pre-treatment of the coating deposition in step 2);

[0051] The working conditions of the ion plating process are as follows: the workpiece holder speed is 8-10 r / min, the chamber pressure is 0.1-0.5 Pa, the Ti target current is 1.8-2 A, the metal substrate bias is -120 V to -90 V, the deposition time is 6-10 min, and the deposition temperature is 200-350 ° C.

[0052] 4. Deposition of CrTiN coating

[0053] Using a Ti target and a Cr target as sputtering sources and argon and nitrogen as working gases, an ion plating process is used to deposit a layer of CrTiN coating on the surface of the pure Ti transition layer obtained in step 3) to obtain the ultra-dense CrTiN conductive corrosion-resistant ceramic coating;

[0054] Among them, the working conditions of the ion plating process are: the workpiece holder speed is 8~10r / min, the chamber pressure is 0.1~0.5Pa, the Ti target current is 1.8~2A, the Cr target current is 0.3A, the metal substrate bias is -60V, the deposition time is 80~120min, and the deposition temperature is 200~350℃.

[0055] Example 1

[0056] An ultra-dense CrTiN conductive corrosion-resistant ceramic coating

[0057] 1. Metal substrate pretreatment

[0058] The metal substrate was placed in a degreasing agent and ultrasonically degreased for 8 minutes. The metal substrate was then placed in deionized water, anhydrous ethanol, and acetone in sequence, and ultrasonically cleaned for 5 minutes each. Finally, the metal substrate was blown dry.

[0059] Wherein, the metal substrate is stainless steel;

[0060] 2. Pre-treatment of coating deposition

[0061] The metal substrate pretreated in step 1) is placed in a magnetron sputtering vacuum chamber equipped with a Ti target and a Cr target, and fixed on a workpiece holder, and the metal substrate is plasma cleaned;

[0062] The working conditions of the plasma cleaning are as follows: the distance between the metal substrate and the target is 90 mm, the rotation speed of the workpiece holder is 9 r / min, and the pressure in the chamber is 5.0×10 -3 Pa, Ti target current is 0.3A, Cr target current is 0.1A, metal substrate bias is -100V to -400V, plasma cleaning time is 20min, and plasma cleaning temperature is 200℃;

[0063] 3. Deposition of pure Ti transition layer

[0064] Using a Ti target as a sputtering source and argon as a working gas, an ion plating process is used to deposit a pure Ti transition layer on the surface of the metal substrate after the pre-treatment of the coating deposition in step 2);

[0065] The working conditions of the ion plating process are as follows: workpiece holder speed of 9 r / min, chamber pressure of 0.5 Pa, Ti target current of 2 A, metal substrate bias of -120 V to -90 V, deposition time of 10 min, and deposition temperature of 200 ° C.

[0066] 4. Deposition of CrTiN coating

[0067] Using a Ti target and a Cr target as sputtering sources and argon and nitrogen as working gases, an ion plating process is used to deposit a layer of CrTiN coating on the surface of the pure Ti transition layer obtained in step 3) to obtain the ultra-dense CrTiN conductive corrosion-resistant ceramic coating;

[0068] Among them, the working conditions of the ion plating process are: the workpiece holder speed is 9r / min, the chamber pressure is 0.5Pa, the Ti target current is 2A, the Cr target current is 0.3A, the metal substrate bias is -60V, the deposition time is 80min, and the deposition temperature is 200℃.

[0069] Example 2

[0070] An ultra-dense CrTiN conductive corrosion-resistant ceramic coating

[0071] 1. Metal substrate pretreatment

[0072] The metal substrate was placed in a degreasing agent and ultrasonically degreased for 8 minutes. The metal substrate was then placed in deionized water, anhydrous ethanol, and acetone in sequence, and ultrasonically cleaned for 5 minutes each. Finally, the metal substrate was blown dry.

[0073] Wherein, the metal substrate is aluminum alloy;

[0074] 2. Pre-treatment of coating deposition

[0075] The metal substrate pretreated in step 1) is placed in a magnetron sputtering vacuum chamber equipped with a Ti target and a Cr target, and fixed on a workpiece holder, and the metal substrate is plasma cleaned;

[0076] The working conditions of the plasma cleaning are as follows: the distance between the metal substrate and the target is 90 mm, the rotation speed of the workpiece holder is 9 r / min, and the pressure in the chamber is 5.0×10 -3 Pa, Ti target current is 0.3A, Cr target current is 0.1A, metal substrate bias is -100V to -400V, plasma cleaning time is 20min, and plasma cleaning temperature is 200℃;

[0077] 3. Deposition of pure Ti transition layer

[0078] Using a Ti target as a sputtering source and argon as a working gas, an ion plating process is used to deposit a pure Ti transition layer on the surface of the metal substrate after the pre-treatment of the coating deposition in step 2);

[0079] The working conditions of the ion plating process are as follows: workpiece holder speed of 9 r / min, chamber pressure of 0.5 Pa, Ti target current of 2 A, metal substrate bias of -120 V to -90 V, deposition time of 10 min, and deposition temperature of 200 ° C.

[0080] 4. Deposition of CrTiN coating

[0081] Using a Ti target and a Cr target as sputtering sources and argon and nitrogen as working gases, an ion plating process is used to deposit a layer of CrTiN coating on the surface of the pure Ti transition layer obtained in step 3) to obtain the ultra-dense CrTiN conductive corrosion-resistant ceramic coating;

[0082] Among them, the working conditions of the ion plating process are: the workpiece holder speed is 9r / min, the chamber pressure is 0.5Pa, the Ti target current is 2A, the Cr target current is 0.3A, the metal substrate bias is -60V, the deposition time is 80min, and the deposition temperature is 200℃.

[0083] Example 3

[0084] An ultra-dense CrTiN conductive corrosion-resistant ceramic coating

[0085] 1. Metal substrate pretreatment

[0086] The metal substrate was placed in a degreasing agent and ultrasonically degreased for 8 minutes. The metal substrate was then placed in deionized water, anhydrous ethanol, and acetone in sequence, and ultrasonically cleaned for 5 minutes each. Finally, the metal substrate was blown dry.

[0087] Wherein, the metal substrate is stainless steel;

[0088] 2. Pre-treatment of coating deposition

[0089] The metal substrate pretreated in step 1) is placed in a magnetron sputtering vacuum chamber equipped with a Ti target and a Cr target, and fixed on a workpiece holder, and the metal substrate is plasma cleaned;

[0090] The working conditions of the plasma cleaning are as follows: the distance between the metal substrate and the target is 90 mm, the rotation speed of the workpiece holder is 9 r / min, and the pressure in the chamber is 5.0×10 -3 Pa, Ti target current is 0.3A, Cr target current is 0.1A, metal substrate bias is -100V to -400V, plasma cleaning time is 20min, and plasma cleaning temperature is 250℃;

[0091] 3. Deposition of pure Ti transition layer

[0092] Using a Ti target as a sputtering source and argon as a working gas, an ion plating process is used to deposit a pure Ti transition layer on the surface of the metal substrate after the pre-treatment of the coating deposition in step 2);

[0093] The working conditions of the ion plating process are as follows: workpiece holder rotation speed of 9 r / min, chamber pressure of 0.5 Pa, Ti target current of 2 A, metal substrate bias voltage of -120 V to -90 V, deposition time of 10 min, and deposition temperature of 250°C.

[0094] 4. Deposition of CrTiN coating

[0095] Using a Ti target and a Cr target as sputtering sources and argon and nitrogen as working gases, an ion plating process is used to deposit a layer of CrTiN coating on the surface of the pure Ti transition layer obtained in step 3) to obtain the ultra-dense CrTiN conductive corrosion-resistant ceramic coating;

[0096] Among them, the working conditions of the ion plating process are: the workpiece holder speed is 9r / min, the chamber pressure is 0.5Pa, the Ti target current is 2A, the Cr target current is 0.3A, the metal substrate bias is -60V, the deposition time is 80min, and the deposition temperature is 250℃.

[0097] Example 4

[0098] An ultra-dense CrTiN conductive corrosion-resistant ceramic coating

[0099] 1. Metal substrate pretreatment

[0100] The metal substrate was placed in a degreasing agent and ultrasonically degreased for 8 minutes. The metal substrate was then placed in deionized water, anhydrous ethanol, and acetone in sequence, and ultrasonically cleaned for 5 minutes each. Finally, the metal substrate was blown dry.

[0101] Wherein, the metal substrate is aluminum alloy;

[0102] 2. Pre-treatment of coating deposition

[0103] The metal substrate pretreated in step 1) is placed in a magnetron sputtering vacuum chamber equipped with a Ti target and a Cr target, and fixed on a workpiece holder, and the metal substrate is plasma cleaned;

[0104] The working conditions of the plasma cleaning are as follows: the distance between the metal substrate and the target is 90 mm, the rotation speed of the workpiece holder is 9 r / min, and the pressure in the chamber is 5.0×10 -3Pa, Ti target current is 0.3A, Cr target current is 0.1A, metal substrate bias is -100V to -400V, plasma cleaning time is 20min, and plasma cleaning temperature is 250℃;

[0105] 3. Deposition of pure Ti transition layer

[0106] Using a Ti target as a sputtering source and argon as a working gas, an ion plating process is used to deposit a pure Ti transition layer on the surface of the metal substrate after the pre-treatment of the coating deposition in step 2);

[0107] The working conditions of the ion plating process are as follows: workpiece holder rotation speed of 9 r / min, chamber pressure of 0.5 Pa, Ti target current of 2 A, metal substrate bias voltage of -120 V to -90 V, deposition time of 10 min, and deposition temperature of 250°C.

[0108] 4. Deposition of CrTiN coating

[0109] Using a Ti target and a Cr target as sputtering sources and argon and nitrogen as working gases, an ion plating process is used to deposit a layer of CrTiN coating on the surface of the pure Ti transition layer obtained in step 3) to obtain the ultra-dense CrTiN conductive corrosion-resistant ceramic coating;

[0110] Among them, the working conditions of the ion plating process are: the workpiece holder speed is 9r / min, the chamber pressure is 0.5Pa, the Ti target current is 2A, the Cr target current is 0.3A, the metal substrate bias is -60V, the deposition time is 80min, and the deposition temperature is 250℃.

[0111] Example 5

[0112] An ultra-dense CrTiN conductive corrosion-resistant ceramic coating

[0113] 1. Metal substrate pretreatment

[0114] The metal substrate was placed in a degreasing agent and ultrasonically degreased for 8 minutes. The metal substrate was then placed in deionized water, anhydrous ethanol, and acetone in sequence, and ultrasonically cleaned for 5 minutes each. Finally, the metal substrate was blown dry.

[0115] Wherein, the metal substrate is stainless steel;

[0116] 2. Pre-treatment of coating deposition

[0117] The metal substrate pretreated in step 1) is placed in a magnetron sputtering vacuum chamber equipped with a Ti target and a Cr target, and fixed on a workpiece holder, and the metal substrate is plasma cleaned;

[0118] The working conditions of the plasma cleaning are as follows: the distance between the metal substrate and the target is 90 mm, the rotation speed of the workpiece holder is 9 r / min, and the pressure in the chamber is 5.0×10 -3 Pa, Ti target current is 0.3A, Cr target current is 0.1A, metal substrate bias is -100V to -400V, plasma cleaning time is 20min, and plasma cleaning temperature is 300℃;

[0119] 3. Deposition of pure Ti transition layer

[0120] Using a Ti target as a sputtering source and argon as a working gas, an ion plating process is used to deposit a pure Ti transition layer on the surface of the metal substrate after the pre-treatment of the coating deposition in step 2);

[0121] The working conditions of the ion plating process are as follows: workpiece holder speed of 9 r / min, chamber pressure of 0.5 Pa, Ti target current of 2 A, metal substrate bias of -120 V to -90 V, deposition time of 10 min, and deposition temperature of 300 ° C.

[0122] 4. Deposition of CrTiN coating

[0123] Using a Ti target and a Cr target as sputtering sources and argon and nitrogen as working gases, an ion plating process is used to deposit a layer of CrTiN coating on the surface of the pure Ti transition layer obtained in step 3) to obtain the ultra-dense CrTiN conductive corrosion-resistant ceramic coating;

[0124] Among them, the working conditions of the ion plating process are: the workpiece holder speed is 9r / min, the chamber pressure is 0.5Pa, the Ti target current is 2A, the Cr target current is 0.3A, the metal substrate bias is -60V, the deposition time is 80min, and the deposition temperature is 300℃.

[0125] Example 6

[0126] An ultra-dense CrTiN conductive corrosion-resistant ceramic coating

[0127] 1. Metal substrate pretreatment

[0128] The metal substrate was placed in a degreasing agent and ultrasonically degreased for 8 minutes. The metal substrate was then placed in deionized water, anhydrous ethanol, and acetone in sequence, and ultrasonically cleaned for 5 minutes each. Finally, the metal substrate was blown dry.

[0129] Wherein, the metal substrate is aluminum alloy;

[0130] 2. Pre-treatment of coating deposition

[0131] The metal substrate pretreated in step 1) is placed in a magnetron sputtering vacuum chamber equipped with a Ti target and a Cr target, and fixed on a workpiece holder, and the metal substrate is plasma cleaned;

[0132] The working conditions of the plasma cleaning are as follows: the distance between the metal substrate and the target is 90 mm, the rotation speed of the workpiece holder is 9 r / min, and the pressure in the chamber is 5.0×10 -3 Pa, Ti target current is 0.3A, Cr target current is 0.1A, metal substrate bias is -100V to -400V, plasma cleaning time is 20min, and plasma cleaning temperature is 300℃;

[0133] 3. Deposition of pure Ti transition layer

[0134] Using a Ti target as a sputtering source and argon as a working gas, an ion plating process is used to deposit a pure Ti transition layer on the surface of the metal substrate after the pre-treatment of the coating deposition in step 2);

[0135] The working conditions of the ion plating process are as follows: workpiece holder speed of 9 r / min, chamber pressure of 0.5 Pa, Ti target current of 2 A, metal substrate bias of -120 V to -90 V, deposition time of 10 min, and deposition temperature of 300 ° C.

[0136] 4. Deposition of CrTiN coating

[0137] Using a Ti target and a Cr target as sputtering sources and argon and nitrogen as working gases, an ion plating process is used to deposit a layer of CrTiN coating on the surface of the pure Ti transition layer obtained in step 3) to obtain the ultra-dense CrTiN conductive corrosion-resistant ceramic coating;

[0138] Among them, the working conditions of the ion plating process are: the workpiece holder speed is 9r / min, the chamber pressure is 0.5Pa, the Ti target current is 2A, the Cr target current is 0.3A, the metal substrate bias is -60V, the deposition time is 80min, and the deposition temperature is 300℃.

[0139] Example 7

[0140] An ultra-dense CrTiN conductive corrosion-resistant ceramic coating

[0141] 1. Metal substrate pretreatment

[0142] The metal substrate was placed in a degreasing agent and ultrasonically degreased for 8 minutes. The metal substrate was then placed in deionized water, anhydrous ethanol, and acetone in sequence, and ultrasonically cleaned for 5 minutes each. Finally, the metal substrate was blown dry.

[0143] Wherein, the metal substrate is stainless steel;

[0144] 2. Pre-treatment of coating deposition

[0145] The metal substrate pretreated in step 1) is placed in a magnetron sputtering vacuum chamber equipped with a Ti target and a Cr target, and fixed on a workpiece holder, and the metal substrate is plasma cleaned;

[0146] The working conditions of the plasma cleaning are as follows: the distance between the metal substrate and the target is 90 mm, the rotation speed of the workpiece holder is 9 r / min, and the pressure in the chamber is 5.0×10 -3 Pa, Ti target current is 0.3A, Cr target current is 0.1A, metal substrate bias is -100V to -400V, plasma cleaning time is 20min, and plasma cleaning temperature is 350℃;

[0147] 3. Deposition of pure Ti transition layer

[0148] Using a Ti target as a sputtering source and argon as a working gas, an ion plating process is used to deposit a pure Ti transition layer on the surface of the metal substrate after the pre-treatment of the coating deposition in step 2);

[0149] The working conditions of the ion plating process are as follows: workpiece holder speed of 9 r / min, chamber pressure of 0.5 Pa, Ti target current of 2 A, metal substrate bias of -120 V to -90 V, deposition time of 10 min, and deposition temperature of 350°C.

[0150] 4. Deposition of CrTiN coating

[0151] Using a Ti target and a Cr target as sputtering sources and argon and nitrogen as working gases, an ion plating process is used to deposit a layer of CrTiN coating on the surface of the pure Ti transition layer obtained in step 3) to obtain the ultra-dense CrTiN conductive corrosion-resistant ceramic coating;

[0152] Among them, the working conditions of the ion plating process are: the workpiece holder speed is 9r / min, the chamber pressure is 0.5Pa, the Ti target current is 2A, the Cr target current is 0.3A, the metal substrate bias is -60V, the deposition time is 80min, and the deposition temperature is 350℃.

[0153] Example 8

[0154] An ultra-dense CrTiN conductive corrosion-resistant ceramic coating

[0155] 1. Metal substrate pretreatment

[0156] The metal substrate was placed in a degreasing agent and ultrasonically degreased for 8 minutes. The metal substrate was then placed in deionized water, anhydrous ethanol, and acetone in sequence, and ultrasonically cleaned for 5 minutes each. Finally, the metal substrate was blown dry.

[0157] Wherein, the metal substrate is aluminum alloy;

[0158] 2. Pre-treatment of coating deposition

[0159] The metal substrate pretreated in step 1) is placed in a magnetron sputtering vacuum chamber equipped with a Ti target and a Cr target, and fixed on a workpiece holder, and the metal substrate is plasma cleaned;

[0160] The working conditions of the plasma cleaning are as follows: the distance between the metal substrate and the target is 90 mm, the rotation speed of the workpiece holder is 9 r / min, and the pressure in the chamber is 5.0×10 -3 Pa, Ti target current is 0.3A, Cr target current is 0.1A, metal substrate bias is -100V to -400V, plasma cleaning time is 20min, and plasma cleaning temperature is 350℃;

[0161] 3. Deposition of pure Ti transition layer

[0162] Using a Ti target as a sputtering source and argon as a working gas, an ion plating process is used to deposit a pure Ti transition layer on the surface of the metal substrate after the pre-treatment of the coating deposition in step 2);

[0163] The working conditions of the ion plating process are as follows: workpiece holder speed of 9 r / min, chamber pressure of 0.5 Pa, Ti target current of 2 A, metal substrate bias of -120 V to -90 V, deposition time of 10 min, and deposition temperature of 350°C.

[0164] 4. Deposition of CrTiN coating

[0165] Using a Ti target and a Cr target as sputtering sources and argon and nitrogen as working gases, an ion plating process is used to deposit a layer of CrTiN coating on the surface of the pure Ti transition layer obtained in step 3) to obtain the ultra-dense CrTiN conductive corrosion-resistant ceramic coating;

[0166] Among them, the working conditions of the ion plating process are: the workpiece holder speed is 9r / min, the chamber pressure is 0.5Pa, the Ti target current is 2A, the Cr target current is 0.3A, the metal substrate bias is -60V, the deposition time is 80min, and the deposition temperature is 350℃.

[0167] The surface contact resistance, corrosion current density, corrosion potential and water contact angle of the ultra-dense CrTiN conductive corrosion-resistant ceramic coatings prepared in Examples 1 to 8 were tested, and the test results are shown in Table 1.

[0168] Table 1 Test results

[0169]

[0170] Note: The water contact angles of the coatings prepared at different deposition temperatures are measured uniformly based on the coatings on Si substrates.

[0171] As shown in Table 1, the surface contact resistance of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating provided by the present invention can reach 3.62 mΩ·cm. 2 , showing good electrical conductivity;

[0172] From the data in Table 1, it can be seen that the corrosion current density of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating provided by the present invention can reach 6.8μA·cm -2 , the corrosion potential can reach -0.18V, showing good corrosion resistance;

[0173] As can be seen from the data in Table 1, the ultra-dense CrTiN conductive corrosion-resistant ceramic coating provided by the present invention has a contact angle of up to 115.86°, showing good hydrophobicity, which lays a foundation for the corrosion resistance of the CrTiN coating in an acidic environment.

[0174] The surface morphology of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating prepared in Example 8 is shown in FIG. Figure 1 As shown;

[0175] Depend on Figure 1 It can be seen that the surface of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating prepared in Example 8 presents a typical triangular pyramidal particle accumulation with a particle size of about 20 nm. The larger particle size effectively improves the water contact angle of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating, thereby effectively improving the conductivity and corrosion resistance of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating.

[0176] The cross-sectional morphology of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating prepared in Example 8 is shown in FIG. Figure 2 As shown;

[0177] Depend on Figure 2 It can be seen that the ultra-dense CrTiN conductive corrosion-resistant ceramic coating prepared in Example 8 has a large number of fine burr columnar crystals on both sides, with uniform grain size and few defects, which effectively improves the conductivity and corrosion resistance of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating.

[0178] The water contact angle of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating prepared in Example 8 is as follows: Figure 3 As shown;

[0179] Depend on Figure 3 It can be seen that the water contact angle of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating prepared in Example 8 is as high as 115.86°, showing good hydrophobicity, which lays a foundation for the corrosion resistance of the CrTiN coating in an acidic environment.

[0180] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in the field should understand that the specific implementation methods of the present invention can still be modified or replaced by equivalents. Any modification or equivalent replacement that does not depart from the spirit and scope of the present invention should be covered by the scope of protection of the claims of the present invention.

Claims

1. A method for preparing an ultra-dense CrTiN conductive corrosion-resistant ceramic coating, characterized in that: The following steps are involved:

1. Metal substrate pretreatment The metal substrate is placed in a degreasing agent and ultrasonically degreased. The metal substrate is then placed in deionized water, anhydrous ethanol, and acetone in sequence and ultrasonically cleaned. Finally, the metal substrate is blown dry.

2. Pre-treatment of coating deposition The metal substrate pretreated in step 1) is placed in a magnetron sputtering vacuum chamber equipped with a Ti target and a Cr target, and fixed on a workpiece holder, and the metal substrate is plasma cleaned; 3. Deposition of pure Ti transition layer Using a Ti target as a sputtering source and argon as a working gas, an ion plating process is used to deposit a pure Ti transition layer on the surface of the metal substrate after the pre-treatment of the coating deposition in step 2); 4. Deposition of CrTiN coating Using Ti target and Cr target as sputtering sources, argon and nitrogen as working gases, an ion plating process is used to deposit a layer of CrTiN coating on the surface of the pure Ti transition layer obtained in step 3) to obtain the ultra-dense CrTiN conductive corrosion-resistant ceramic coating.

2. The method for preparing an ultra-dense CrTiN conductive corrosion-resistant ceramic coating according to claim 1, characterized in that: In step 1, the metal substrate is stainless steel or aluminum alloy.

3. The method for preparing an ultra-dense CrTiN conductive corrosion-resistant ceramic coating according to claim 1, characterized in that: In step 1, the duration of the ultrasonic fat removal is 8 minutes.

4. The method for preparing an ultra-dense CrTiN conductive corrosion-resistant ceramic coating according to claim 1, characterized in that: In step 1, the duration of the ultrasonic cleaning is 5 minutes.

5. The method for preparing an ultra-dense CrTiN conductive corrosion-resistant ceramic coating according to claim 1, characterized in that: In step 2, the working conditions of the plasma cleaning are: the distance between the metal substrate and the target is 90 mm, the workpiece holder speed is 8-10 r / min, and the pressure in the chamber is ≤5.0×10 -3 Pa, Ti target current is 0.3A, Cr target current is 0.1A, metal substrate bias is -100V to -400V, plasma cleaning time is 20min, and plasma cleaning temperature is 200 to 350℃.

6. The method for preparing an ultra-dense CrTiN conductive corrosion-resistant ceramic coating according to claim 1, characterized in that: In step 3, the working conditions of the ion plating process are: the workpiece holder speed is 8 to 10 r / min, the chamber pressure is 0.1 to 0.5 Pa, the Ti target current is 1.8 to 2 A, the metal substrate bias is -120 V to -90 V, the deposition time is 6 to 10 min, and the deposition temperature is 200 to 350 ° C.

7. The method for preparing an ultra-dense CrTiN conductive corrosion-resistant ceramic coating according to claim 1, characterized in that: In step 4, the working conditions of the ion plating process are: the workpiece holder speed is 8-10 r / min, the chamber pressure is 0.1-0.5 Pa, the Ti target current is 1.8-2 A, the Cr target current is 0.3 A, the metal substrate bias is -60 V, the deposition time is 80-120 min, and the deposition temperature is 200-350 ° C.

8. An ultra-dense CrTiN conductive corrosion-resistant ceramic coating prepared by the method for preparing an ultra-dense CrTiN conductive corrosion-resistant ceramic coating according to any one of claims 1 to 7.

9. Use of the ultra-dense CrTiN conductive corrosion-resistant ceramic coating according to claim 8 in a hydrogen fuel cell.

Images