CN115125493A - Carbon steel surface metal corrosion-resistant coating and preparation method thereof - Google Patents

Carbon steel surface metal corrosion-resistant coating and preparation method thereof Download PDF

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CN115125493A
CN115125493A CN202110314610.9A CN202110314610A CN115125493A CN 115125493 A CN115125493 A CN 115125493A CN 202110314610 A CN202110314610 A CN 202110314610A CN 115125493 A CN115125493 A CN 115125493A
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carbon steel
coating
argon
pressure
vacuum chamber
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CN115125493B (en
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李育霖
周庆军
刘明亮
李超
吴玮巍
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Baoshan Iron and Steel Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
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Abstract

The invention belongs to the field of metal surface treatment technology and corrosion electrochemistry, relates to a carbon steel surface metal corrosion-resistant coating and a preparation method thereof, and particularly relates to a plain carbon steel surface TiAlN corrosion-resistant metal coating and a preparation method thereof. The TiAlN coating prepared based on the PVD method can be well attached to the surface of carbon steel to form a corrosion-resistant coating, and experimental tests show that the chloride ion corrosion resistance effect of the coating is very obvious, so that the corrosion resistance of the carbon steel in a marine environment can be greatly improved; in addition, the TiAlN coating has higher hardness and better bonding property with a metal matrix, and can also play a role in protecting the carbon steel for a longer time compared with other coatings.

Description

Carbon steel surface metal corrosion-resistant coating and preparation method thereof
Technical Field
The invention belongs to the field of metal surface treatment technology and corrosion electrochemistry, and particularly relates to a carbon steel surface metal corrosion-resistant coating and a preparation method thereof, and particularly relates to a plain carbon steel surface TiAlN corrosion-resistant metal coating and a preparation method thereof.
Background
The plain carbon steel represented by Q235 and Q345 is widely applied to industries such as machinery, construction, traffic and the like, and the material has low self corrosion resistance due to low alloy content, so that the corrosion resistance can be effectively improved by preparing the corrosion-resistant coating on the surface of the material, and the corrosion life is greatly prolonged. The Ti-Al-N coating is a novel coating material, has the advantages of higher hardness, higher oxidation temperature, higher thermal hardness, strong adhesive force, small friction coefficient and small thermal conductivity, and particularly has obvious effect of improving the corrosion resistance of materials such as carbon steel, cast iron and the like when the coating is used for covering iron alloy materials in a high-temperature corrosion environment. Therefore, the TiAlN coating has wide popularization prospect in the field of metal corrosion.
Since the last century after the publication of research literature of TiAlN coatings, the high temperature oxidation resistance and better service characteristics of the TiAlN coatings have been very much noticed, and various PVD methods have been successfully used to prepare TiAlN coatings, because the TiAlN coatings described in the previous article have different properties due to the different preparation methods of the TiAlN coatings. The hardness and the oxidation temperature of the TiAlN coating are higher, and the performances of the multi-layer coating and the nano TiAlN coating are continuously improved. TiAlN has good chemical stability and strong oxidation and wear resistance, the hardness is 3400-3600 HV, the wear resistance is only a little lower than that of a diamond-like carbon film, and the TiAlN hard coating is a hard coating recommended by the international tool industry. When the aluminum content is more than 50%, it is A1TiN for distinction from TiAlN. The corrosion resistance of the A1TiN coating is closely related to the aluminum content, and when the aluminum is used as a metal of a sacrificial anode in electrochemistry and the content of the aluminum is increased, the corrosion resistance of the coating is also greatly improved.
At present, two methods are mainly used for preparing the TiAlN coating on the surface of the iron alloy material: the invention relates to a Chemical Vapor Deposition (CVD) method and a Physical Vapor Deposition (PVD) method, wherein the PVD method is mainly adopted for preparing a TiAlN coating on the surface of carbon steel, the PVD method is composed of two methods, namely a reactive ion deposition method and a reactive sputtering method, and the former method is adopted in most factories. The reactive ion deposition method uses a metal substrate as a cathode. The metal is vaporized by the electron gun, and the metal vapor and the introduced reaction gas are ionized under the action of the electric field and accelerated to move to the cathode, and the metal vapor and the introduced reaction gas collide with each other to form a coating on the workpiece. Compared with the CVD method, PVD has the following advantages:
(1) for plain carbon steel, the smelting temperature is higher than the coating temperature, so that the hardness of the carbon steel serving as a substrate cannot be damaged, and heat treatment is not needed after the coating;
(2) the actual thickness of the coating is only a few micrometers (up to 5 micrometers), so that the coating cost can be greatly saved, and the attractive appearance of a coated product is not influenced.
(3) The coating has high purity and good compactness, the coating and the matrix can be well combined, and the characteristics of the coating have little influence on the material of the matrix;
(4) the surface of the coating is smooth and uniform, and no abnormal structure appears at corners and circular arcs, so that uniform and smooth coatings can be obtained on metal substrates with different surface states;
(5) no decarbonized phase is produced. The situation that the coating is easy to crack due to corrosion of chlorine and hydrogen embrittlement deformation in a CVD method is avoided, and the density of the coating is higher;
(6) the working process is clean, pollution-free and nuisanceless.
Coating carbon steel with one or more layers of particularly desirable refractory metal compounds (hard coatings, e.g., Ti-N, T-C, Ti-Al-N, etc.) or non-metallic compounds (soft coatings, e.g., MOS) 2 ，WS 2 Pure graphite, etc.) so that the overall characteristics and service time of the metal are greatly improved; because the hard-to-melt metal compound has the characteristics of higher hardness, better wear resistance, high temperature resistance and the like, after a hard coating is covered on the surface layer of the carbon steel, when the sample is placed in a corrosive medium, the coating can be used as a physical barrier to effectively prevent harmful ions in a solution from reaching a metal matrixThe surface of the steel plate is rusted, and the barrier has the characteristics of high temperature resistance and wear resistance, so that the wear resistance and high temperature resistance of the carbon steel are improved to a certain extent.
Disclosure of Invention
The invention is based on the technology of preparing TiAlN coating on the surface of carbon steel, aims to effectively improve the corrosion resistance of the carbon steel, has the advantages of high temperature resistance, good chemical stability, less surface defects of the coating, thin thickness of the coating and the like, can well protect the carbon steel substrate from being corroded by corrosive media, and can protect the carbon steel substrate for a longer time due to the fact that the coating has higher hardness and is not easy to fall off.
The technical scheme of the invention is as follows:
a preparation method of a carbon steel surface metal corrosion-resistant coating comprises the following steps:
(1) loading a test piece and a carbon steel sheet made of the same material into a vacuum chamber of a multi-arc ion plating machine, wherein the test piece is vertically fixed on a two-dimensional rotating rod of a rotating frame, the test piece is kept parallel to the surface of a target material, and the distance between the test piece and the target material is kept between 170 and 190 mm; blowing off fine dust on the surface of the sample, closing a vacuum chamber door, starting the rotating frame, and adjusting the rotating speed of a central shaft of a motor of the rotating frame to be 2-7 r/min;
(2) firstly, vacuumizing until the pressure in a coating vacuum chamber is below 650-1000 Pa, and then continuously vacuumizing until the pressure in the chamber is below 1.5-3.5 Pa;
(3) starting a molecular pump and a front-end gate valve to pump high vacuum, and simultaneously starting a heating pipe to heat for 90-120 min, wherein the preset heating temperature of the sample is 300-380 ℃; keeping the temperature for 20-35 min after reaching the temperature, wherein the indoor pressure is 5.5 multiplied by 10 -3 ～8×10 -3 Pa; closing a throttle valve at the front end of the molecular pump, introducing argon, performing ion cleaning before coating, adding negative bias to 700-800V, maintaining the flow of the argon in the range of 100-280 sccm for 20-30 min, and keeping the pressure in the vacuum chamber at about 2-2.5 Pa;
(4) continuously introducing 120-160 sccm argon, respectively starting two rows of nine Cr targets to deposit Cr bottoming layers, controlling the arc striking electrodes and the targets to be in contact for a very short time through a small cylinder and then quickly separating, after arc striking is successful, obviously observing blue arc light ablation in front of the targets, spraying under the action of an arc power supply, and forming a low-voltage and high-current passage by the materials and the arc striking electrodes, wherein the flow of the argon is 120-160 sccm, the time lasts for 6-10 min, the pressure in a vacuum chamber is 2.0-4.0 Pa, and the negative bias is 600-750V; introducing nitrogen and trace argon to start to deposit a CrN priming layer, lasting for 15-20 min, reducing negative bias to 100-150V, wherein the flow rates of the nitrogen and the argon are respectively 200-400 sccm and 10-20 sccm, the flow rate of the argon is kept unchanged, the flow rate of the nitrogen is finely adjusted according to the indoor pressure, and the pressure in the vacuum chamber is kept at 1.0 Pa;
(5) closing an argon electromagnetic throttle valve, only introducing nitrogen with the flow of 700-900 sccm, fully opening the Cr target and the Ti-Al alloy target, wherein the opening of the throttle valve is 20-25%, the negative bias is reduced to 80-100V, and beginning to deposit a CrN and TiAlN transition layer, wherein the pressure in the vacuum chamber is kept at 1.5-4.0 Pa; closing the Cr target, only leaving two lines of Ti-Al alloy targets to work, reducing the nitrogen flow by about 520-650 sccm, keeping the pressure in the vacuum chamber at 1.5-2 Pa, keeping the negative bias constant, and depositing a working layer for 100-150 min; stopping heating, continuously introducing argon for protection and cooling, opening the furnace door, and taking out the test sample to be detected.
Further, fine dust on the surface of the sample is lightly blown by compressed air cleaned by an air gun in the step (1).
Further, the test pieces are processed in the step (1), each test piece is sequentially polished by 200#, 400#, 800#, 1000#, 2000# sandpaper, and is dried after being cleaned by acetone and ethanol for later use.
Further, in the step (2), a mechanical pump is used for vacuumizing until the pressure in the coating vacuum chamber is below 1000Pa, then the vacuum pump is started, and the vacuum pumping is continued until the pressure in the chamber is below 3.5 Pa.
Further, in the step (3), since the negative bias adopts a domestic pulse bias power supply, the bias duty ratio is adjusted to 80-90% at most.
Further, in the step (4), the low voltage is 12-20V, and the high current is 30-80A.
Further, in the step (4), the extremely short time is 1-3 s.
Further, in the step (5), argon is continuously introduced for protection and the temperature is cooled to be below 60 ℃.
The invention also provides the carbon steel surface metal corrosion-resistant coating prepared by the preparation method of the carbon steel surface metal corrosion-resistant coating.
The invention provides a preparation process and a method of a Ti-Al-N coating on the surface of carbon steel, preferably comprising the following steps:
1. and (3) loading the processed test piece and the carbon steel sheet made of the same material into a vacuum chamber of a multi-arc ion coating machine, wherein the test piece is vertically fixed on a two-dimensional rotating rod of a rotating frame, the test piece is kept parallel to the surface of the target material, and the distance between the test piece and the target material is kept between 170 and 190 mm. Slightly blowing fine dust on the surface of the sample by using clean compressed air of an air gun, closing a vacuum chamber door, starting the rotating frame, and adjusting the rotating speed of a shaft in a motor of the rotating frame to be 2r/min and keeping the rotating speed unchanged to ensure the uniformity of the coated sample;
2. vacuumizing by using a mechanical pump until the pressure in the coating vacuum chamber is below 1000Pa, then starting the vacuum pump, and continuously vacuumizing until the pressure in the chamber is below 3.5 Pa;
3. starting a molecular pump and a front end gate valve to pump high vacuum, and simultaneously starting a heating pipe to heat for about 120min, wherein the preset heating temperature of the sample is 300-380 ℃; keeping the temperature for 20min after reaching the temperature, wherein the indoor pressure is about 5.5 multiplied by 10 - 3 Pa; closing a throttle valve at the front end of the molecular pump, introducing argon, performing ion cleaning before coating, adding negative bias to about 800V, adjusting the bias duty ratio to be 80% at the highest because the negative bias adopts a domestic pulse bias power supply, maintaining the argon flow in the range of 100-280 sccm for about 20min, and keeping the pressure in the vacuum chamber to be about 2-2.5 Pa;
4. continuously introducing 120sccm argon, respectively starting two lines of nine Cr targets to deposit Cr bottoming layers, controlling the arc striking electrodes and the target materials to be in contact for a very short time through a small cylinder and then quickly separating, after arc striking is successful, obviously observing blue arc light ablation in front of the target materials, spraying under the action of an arc power supply, and forming an obvious spraying flow by using the materials and the arc striking electrodes, wherein a low-voltage (20V) and high-current (30-80A) passage is formed by using the materials and the arc striking electrodes, the argon flow is 120sccm, the time lasts for 6min, the pressure in a vacuum chamber is 2.0Pa, and the negative bias is 750V; introducing nitrogen and trace argon to start to deposit a CrN priming layer, wherein the duration is about 20min, reducing the negative bias to 150V, the flow rates of the nitrogen and the argon are respectively about 400sccm and 10sccm, the flow rate of the argon is kept unchanged, and the flow rate of the nitrogen is finely adjusted according to the indoor pressure to ensure that the pressure in the vacuum chamber is kept at 1.0 Pa;
5. closing an argon electromagnetic throttle valve, only introducing nitrogen with the flow of 900sccm, fully opening a Cr target and a Ti-Al alloy target, reducing the opening of the throttle valve to 25 percent, reducing the negative bias to 100V, and beginning to deposit a CrN and TiAlN transition layer, wherein the pressure in the vacuum chamber is kept at about 2.5 Pa; closing the Cr target, only leaving two lines of Ti-Al alloy targets to work, reducing the nitrogen flow, keeping the pressure in the vacuum chamber to be 2Pa, keeping the negative bias constant, and depositing a working layer for 100 min; stopping heating, continuously introducing argon for protection and cooling, cooling to below 60 ℃, opening a furnace door, and taking out a test sample to be detected.
One of the innovation points of the invention is that the vacuum multi-arc ion plating technology is used, and the surface of the material, namely carbon steel, is plated for the first time. Namely 1, a vacuum multi-arc ion plating technology is adopted. 2. The TiAlN metal coating is applied to the surface of the carbon steel for the first time.
The invention uses the Multi-Arc ion plating technology, which is a key point for realizing the good combination of TiAlN coating, AlCrN coating and carbon steel, and the Multi-Arc ion plating technology (M-AIP) is also called Arc ion plating or vacuum Arc evaporation plating, and the technical core is a new coating technology for using cold cathode self-sustaining vacuum lake light discharge in an evaporation source. Because the cathode target is directly evaporated, the system has no molten pool and cathode arc (reduces the process steps), and controls the coating composition and morphology by regulating the evaporation source as the cathode target component.
The invention has the beneficial technical effects that:
according to the carbon steel surface metal corrosion-resistant coating and the preparation method, the TiAlN coating prepared based on the PVD method can be well attached to the carbon steel surface to form the corrosion-resistant coating, and experimental tests show that the chloride ion corrosion-resistant effect of the coating is very obvious (the data in Table 1 prove that the corrosion resistance is worse when the corrosion current is smaller), and the corrosion resistance of the carbon steel in the marine environment can be greatly improved; in addition, the TiAlN coating has higher hardness and better bonding property with a metal matrix, and can protect the carbon steel for a longer time compared with other coatings.
Drawings
FIG. 1 is a schematic structural view of a multi-arc ion plating machine;
wherein: 1-a target arc source, 2-an arc source target source, 3-a working bias power supply motor, 4-an auxiliary heating device, 5-a plated sample, 6-the plated sample, 7-a reaction gas and 8-air extraction.
Detailed Description
For better understanding of the present invention, the following examples are provided to further illustrate the present invention, but the present invention is not limited to the following examples.
The multi-arc ion film plating machine is produced by the Antai technology (made in China), the size of a target material is phi 100 multiplied by 20mm, the purity of a Cr target is 99.8 percent (2N8), the components of an alloy target are AlCr (Al67 percent, Cr33 percent) and TiAl (50 percent ), and the purities of protective gas argon and working gas nitrogen are 99.999 percent.
Example 1
A preparation process and a method of a Ti-Al-N coating on the surface of Q235 carbon steel comprise the following processes and steps:
1. and (3) loading the processed test piece and a Q235 carbon steel sheet made of the same material into a vacuum chamber of a multi-arc ion coating machine, wherein the test piece is vertically fixed on a two-dimensional rotating rod of a rotating frame, the test piece is kept parallel to the surface of the target material, and the distance between the test piece and the target material is kept between 185 mm. Slightly blowing fine dust on the surface of the sample by using clean compressed air of an air gun, closing a vacuum chamber door, starting the rotating frame, and adjusting the rotating speed of a shaft in a motor of the rotating frame to be 2r/min and keeping the rotating speed unchanged to ensure the uniformity of the coated sample;
2. vacuumizing by using a mechanical pump until the pressure in the coating vacuum chamber is 950Pa, then starting the vacuum pump, and continuously vacuumizing until the pressure in the chamber is 3.5 Pa;
3. starting a molecular pump and a front end gate valve to pump high vacuum, and simultaneously starting a heating pipe to heat, wherein the heating time is about 120min, and the preset heating temperature of the Q235 sample is 300 ℃; keeping the temperature for 20min after reaching the temperature, wherein the indoor pressure is about 5.5 multiplied by 10 - 3 Pa; closing a throttle valve at the front end of the molecular pump, introducing argon, performing ion cleaning before coating, adding negative bias to about 800V, adjusting the bias duty ratio to be 80% at the highest because the negative bias adopts a domestic pulse bias power supply, maintaining the flow of the argon in the range of 170sccm for about 20min, and keeping the pressure in the vacuum chamber at about 2-2.5 Pa;
4. continuously introducing 120sccm argon, respectively starting two rows of nine Cr targets to deposit a Cr bottoming layer, quickly separating an arc ignition electrode from a target material after the arc ignition electrode is controlled by a small cylinder to be in extremely short-time contact, after the arc ignition is successful, obviously observing blue arc ablation in front of the target material, spraying under the action of an arc power supply to form an obvious spraying flow, forming a low-voltage (20V) and high-current (55A) passage by the material and the arc ignition electrode, wherein the flow of the argon is 120sccm, the time lasts for 6min, the pressure in a vacuum chamber is 2.0Pa, and the negative bias is 750V; introducing nitrogen and trace argon to start to deposit a CrN priming layer, wherein the duration is about 20min, reducing the negative bias to 150V, the flow rates of the nitrogen and the argon are respectively about 400sccm and 10sccm, the flow rate of the argon is kept unchanged, and the flow rate of the nitrogen is finely adjusted according to the indoor pressure to ensure that the pressure in the vacuum chamber is kept at 1.0 Pa;
5. closing an argon electromagnetic throttle valve, only introducing nitrogen with the flow of 900sccm, fully opening a Cr target and a Ti-Al alloy target, reducing the opening of the throttle valve to 25 percent, reducing the negative bias to 100V, and beginning to deposit a CrN and TIAlN transition layer, wherein the pressure in the vacuum chamber is kept at about 2.5 Pa; closing the Cr target, only leaving two lines of Ti-Al alloy targets to work, reducing the nitrogen flow, keeping the pressure in the vacuum chamber to be 2Pa, keeping the negative bias constant, and depositing a working layer for 100 min; stopping heating, continuously introducing argon for protection and cooling, cooling to below 60 ℃, opening a furnace door, and taking out a test sample to be detected.
In the experiment, Q235 carbon steel is selected as a metal matrix coating sample, TiAlN coating samples prepared at different temperatures on the surface of the sample are made into a standard electrode of 10 multiplied by 10mm, 3.5 wt.% NaCl solution is used as corrosive liquid, the heating preset temperature of the Q235 sample is 300 ℃, and other conditions are unchanged; the experimental conditions were static and the experimental temperature was 25 ℃. The electrochemical test adopts a potentiodynamic polarization curve to test, polarization curves of coating samples with equal area sizes are respectively tested under the same condition, a reference electrode is a Saturated Calomel Electrode (SCE), the scanning interval is-0.35-0.25V, and the scanning speed is 1 mV/s.
Example 2
In the experiment, Q235 carbon steel is selected as a metal matrix coating sample, TiAlN coating samples prepared at different temperatures on the surface of the sample are made into a standard electrode of 10 x 10mm, 3.5 wt.% NaCl solution is used as corrosive liquid, the heating preset temperature of the Q235 sample is 320 ℃, and other conditions are not changed; the experimental conditions were static and the experimental temperature was 25 ℃. The electrochemical test adopts a potentiodynamic polarization curve to test, polarization curves of coating samples with equal area sizes are respectively tested under the same condition, a reference electrode is a Saturated Calomel Electrode (SCE), the scanning interval is-0.35-0.25V, and the scanning speed is 1 mV/s.
Example 3
In the experiment, Q235 carbon steel is selected as a metal matrix coating sample, TiAlN coating samples prepared at different temperatures on the surface of the sample are made into a standard electrode of 10 multiplied by 10mm, 3.5 wt.% NaCl solution is used as corrosive liquid, the heating preset temperature of the Q235 sample is 340 ℃, and other conditions are unchanged; the experimental conditions were static and the experimental temperature was 25 ℃. The electrochemical test adopts a potentiodynamic polarization curve to test, polarization curves of coating samples with equal area sizes are respectively tested under the same condition, a reference electrode is a Saturated Calomel Electrode (SCE), the scanning interval is-0.35-0.25V, and the scanning speed is 1 mV/s.
Example 4
A preparation process and a method of a Ti-Al-N coating on the surface of Q235 carbon steel comprise the following processes and steps:
1. and (3) loading the processed test piece and a Q235 carbon steel sheet made of the same material into a vacuum chamber of a multi-arc ion coating machine, wherein the test piece is vertically fixed on a two-dimensional rotating rod of a rotating frame, the test piece is kept parallel to the surface of the target material, and the distance between the test piece and the target material is kept between 180 mm. Slightly blowing fine dust on the surface of the sample by using clean compressed air of an air gun, closing a vacuum chamber door, starting the rotating frame, and adjusting the rotating speed of a shaft in a motor of the rotating frame to be 3r/min and keeping the rotating speed unchanged to ensure the uniformity of the coated sample;
2. vacuumizing by using a mechanical pump until the pressure in the coating vacuum chamber is 800Pa, then starting the vacuum pump, and continuously vacuumizing until the pressure in the chamber is 3.5 Pa;
3. starting a molecular pump and a front-end gate valve to pump high vacuum, and simultaneously starting a heating pipe to heat, wherein the heating time is about 120min, and the preset heating temperature of a Q235 sample is 350 ℃; keeping the temperature for 15min after reaching the temperature, wherein the indoor pressure is about 5.5 multiplied by 10 - 3 Pa; closing a throttle valve at the front end of the molecular pump, introducing argon, performing ion cleaning before coating, adding negative bias to about 800V, adjusting the bias duty ratio to be 80% at the highest because the negative bias adopts a domestic pulse bias power supply, maintaining the flow of the argon in the range of 170sccm for about 20min, and keeping the pressure in the vacuum chamber at about 2-2.5 Pa;
4. continuously introducing 120sccm argon, respectively starting two lines of nine Cr targets to deposit Cr priming layers, controlling the arc striking electrodes and the target materials to be in contact for a very short time through a small cylinder and then quickly separating, after arc striking is successful, obviously observing blue arc ablation in front of the target materials, spraying under the action of an arc power supply, and forming an obvious spraying flow by using the materials and the arc striking electrodes to form a low-voltage (25V) and high-current (60A) passage, wherein the flow of the argon is 120sccm, the time lasts for 6min, the pressure in a vacuum chamber is 2.0Pa, and the negative bias is 750V; introducing nitrogen and trace argon to start depositing a CrN primer layer, keeping the time for about 20min, reducing the negative bias to 150V, wherein the flow rates of the nitrogen and the argon are about 400sccm and 10sccm respectively, the flow rate of the argon is kept unchanged, and the flow rate of the nitrogen is finely adjusted according to the pressure in the chamber to ensure that the pressure in the vacuum chamber is kept at 1.0 Pa;
5. closing an argon electromagnetic throttle valve, only introducing nitrogen with the flow of 900sccm, fully opening a Cr target and a Ti-Al alloy target, reducing the opening of the throttle valve to 25 percent, reducing the negative bias to 100V, and beginning to deposit a CrN and TIAlN transition layer, wherein the pressure in the vacuum chamber is kept at about 2.5 Pa; closing the Cr target, only leaving two lines of Ti-Al alloy targets to work, reducing the nitrogen flow, keeping the pressure in the vacuum chamber to be 2Pa, keeping the negative bias constant, and depositing a working layer for 100 min; stopping heating, continuously introducing argon for protection and cooling, cooling to below 60 ℃, opening a furnace door, and taking out a test sample to be detected.
In the experiment, Q235 carbon steel is selected as a metal matrix coating sample, TiAlN coating samples prepared at different temperatures on the surface of the sample are made into a standard electrode of 10 x 10mm, 3.5 wt.% NaCl solution is used as corrosive liquid, the heating preset temperature of the Q235 sample is 350 ℃, and other conditions are not changed; the experimental conditions were static and the experimental temperature was 25 ℃. The electrochemical test adopts a potentiodynamic polarization curve to test, polarization curves of coating samples with equal area sizes are respectively tested under the same condition, a reference electrode is a Saturated Calomel Electrode (SCE), the scanning interval is-0.35-0.25V, and the scanning speed is 1 mV/s.
Example 5
In the experiment, Q345 carbon steel is selected as a metal matrix coating sample, TiAlN coating samples prepared at different temperatures on the surface of the sample are made into a standard electrode of 10 multiplied by 10mm, 3.5 wt.% NaCl solution is used as a corrosive liquid, the heating preset temperature of the Q345 sample is 360 ℃, and other conditions are unchanged; the experimental conditions were static and the experimental temperature was 25 ℃. The electrochemical test adopts a potentiodynamic polarization curve to test, polarization curves of coating samples with equal area sizes are respectively tested under the same condition, a reference electrode is a Saturated Calomel Electrode (SCE), the scanning interval is-0.35-0.25V, and the scanning speed is 1 mV/s.
Example 6
In the experiment, Q345 carbon steel is selected as a metal matrix coating sample, TiAlN coating samples prepared at different temperatures on the surface of the sample are made into a standard electrode of 10 multiplied by 10mm, 3.5 wt.% NaCl solution is used as a corrosive liquid, the heating preset temperature of the Q345 sample is 380 ℃, and other conditions are unchanged; the experimental conditions were static and the experimental temperature was 25 ℃. The electrochemical test adopts a potentiodynamic polarization curve to test, polarization curves of coating samples with equal area sizes are respectively tested under the same condition, a reference electrode is a Saturated Calomel Electrode (SCE), the scanning interval is-0.35 to-0.25V, and the scanning speed is 1 mV/s.
TABLE 1 Properties of the samples treated in the examples
Figure RE-GDA0003210911860000081
Figure RE-GDA0003210911860000091
Of course, those skilled in the art should recognize that the above-described embodiments are illustrative only, and not limiting, and that changes and modifications can be made within the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. A preparation method of a carbon steel surface metal corrosion-resistant coating is characterized by comprising the following steps:
(1) loading the test piece and the carbon steel sheet made of the same material into a vacuum chamber of a multi-arc ion coating machine, closing a door of the vacuum chamber, starting a rotating frame, and adjusting the rotating speed of a central shaft of a motor of the rotating frame to be 2-7 r/min;
(2) firstly, vacuumizing until the pressure in a coating vacuum chamber is below 650-1000 Pa, and then continuously vacuumizing until the pressure in the chamber is below 1.5-3.5 Pa;
(3) starting a molecular pump and a front-end gate valve to pump high vacuum, and simultaneously starting a heating pipe to heat for 90-120 min, wherein the preset heating temperature of the sample is 300-380 ℃; keeping the temperature for 20-35 min after reaching the temperature, wherein the indoor pressure is 5.5 multiplied by 10 -3 ～8×10 -3 Pa; closing a throttle valve at the front end of the molecular pump, introducing argon, performing ion cleaning before coating, adding negative bias to 700-800V, maintaining the flow of the argon in the range of 100-280 sccm for 20-30 min, and keeping the pressure in the vacuum chamber at about 2-2.5 Pa;
(4) continuously introducing 120-160 sccm argon, respectively starting two rows of nine Cr targets to deposit Cr bottoming layers, controlling the arc ignition electrodes to be in contact with the targets in a very short time through a small cylinder and then quickly separating the arc ignition electrodes from the targets, forming a low-voltage and high-current passage by the materials and the arc ignition electrodes, wherein the flow of the argon is 120-160 sccm, the time lasts for 6-10 min, the pressure in the vacuum chamber is 2.0-4.0 Pa, and the negative bias is 600-750V; introducing nitrogen and trace argon to start depositing a CrN bottoming layer, lasting for 15-20 min, reducing the negative bias to 100-150V, wherein the flow rates of the nitrogen and the argon are 200-400 sccm and 10-20 sccm respectively, the flow rate of the argon is kept unchanged, the flow rate of the nitrogen is finely adjusted according to the pressure in the chamber, and the pressure in the vacuum chamber is kept at 1.0 Pa;
(5) closing an argon electromagnetic throttle valve, only introducing nitrogen with the flow of 700-900 sccm, fully opening the Cr target and the Ti-Al alloy target, wherein the opening of the throttle valve is 20-25%, the negative bias is reduced to 80-100V, and beginning to deposit a CrN and TiAlN transition layer, wherein the pressure in the vacuum chamber is kept at 1.5-4.0 Pa; closing the Cr target, only leaving two lines of Ti-Al alloy targets to work, reducing the nitrogen flow by about 520-650 sccm, keeping the pressure in the vacuum chamber at 1.5-2 Pa, keeping the negative bias constant, and depositing a working layer for 100-150 min; stopping heating, continuously introducing argon for protection and cooling, opening the furnace door, and taking out the test sample to be detected.
2. The method for preparing a carbon steel surface metal corrosion-resistant coating according to claim 1, wherein in the step (1) in a vacuum chamber of a multi-arc ion plating machine, the test piece is vertically fixed on a two-dimensional rotating rod of a rotating frame, the test piece is kept parallel to the surface of the target, and the distance between the test piece and the target is kept between 170 mm and 190 mm.
3. The method for preparing a carbon steel surface metal corrosion-resistant coating according to claim 1, wherein fine dust on the surface of the sample is lightly blown by compressed air cleaned by an air gun in the step (1), and then the door of the vacuum chamber is closed.
4. The method for preparing a carbon steel surface metal corrosion-resistant coating according to claim 1, wherein the test pieces are processed in step (1), each test piece is sequentially ground by 200#, 400#, 800#, 1000#, 2000# sandpaper, cleaned by acetone and ethanol and dried for later use.
5. The method for preparing the metal corrosion-resistant coating on the surface of the carbon steel as claimed in claim 1, wherein in the step (2), the vacuum is pumped by a mechanical pump until the pressure in the coating vacuum chamber is below 1000Pa, and then the vacuum pump is started to continue the vacuum pumping until the pressure in the chamber is below 3.5 Pa.
6. The method for preparing a carbon steel surface metal corrosion-resistant coating according to claim 1, wherein in the step (3), since the negative bias adopts a domestic pulse bias power supply, the bias duty ratio is adjusted to be at most 80-90%.
7. The method for preparing the metal corrosion-resistant coating on the surface of the carbon steel as claimed in claim 1, wherein in the step (4), the low voltage is 12-20V, and the high current is 30-80A.
8. The method for preparing the metal corrosion-resistant coating on the surface of the carbon steel as recited in claim 1, wherein in the step (4), the extremely short time is 1-3 s.
9. The method for preparing the metal corrosion-resistant coating on the surface of the carbon steel as claimed in claim 1, wherein in the step (5), argon is continuously introduced for protection and the temperature is cooled to be below 60 ℃.
10. A carbon steel surface metal corrosion-resistant coating prepared by the method for preparing the carbon steel surface metal corrosion-resistant coating according to any one of claims 1 to 9.
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