CN115125493B - Metal corrosion-resistant coating on surface of carbon steel and preparation method thereof - Google Patents
Metal corrosion-resistant coating on surface of carbon steel and preparation method thereof Download PDFInfo
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- CN115125493B CN115125493B CN202110314610.9A CN202110314610A CN115125493B CN 115125493 B CN115125493 B CN 115125493B CN 202110314610 A CN202110314610 A CN 202110314610A CN 115125493 B CN115125493 B CN 115125493B
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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
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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
- C23C14/0021—Reactive sputtering or evaporation
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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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
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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
- C23C14/06—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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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 common carbon steel surface TiAlN corrosion-resistant metal coating and a preparation method thereof. According to the TiAlN coating prepared on the basis of the PVD method, the TiAlN coating can be well attached to the surface of the carbon steel to form a corrosion-resistant coating, and experimental tests show that the corrosion-resistant effect of chloride ions of the coating is very obvious, and 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 combination property with the metal matrix, and can protect the carbon steel for a longer time compared with other coatings.
Description
Technical Field
The invention belongs to the field of metal surface treatment technology and corrosion electrochemistry, in particular relates to a carbon steel surface metal corrosion-resistant coating and a preparation method thereof, and particularly relates to a common carbon steel surface TiAlN corrosion-resistant metal coating and a preparation method thereof.
Background
The common carbon steel represented by Q235 and Q345 is widely applied to industries such as machinery, construction, traffic and the like, and the corrosion resistance of the material is relatively low due to low alloy content, and the corrosion resistance can be effectively improved and the corrosion life can be greatly prolonged by preparing the corrosion-resistant coating on the surface of the material. The Ti-Al-N coating is a novel coating material, has the advantages of higher hardness, higher oxidation temperature, higher hot hardness, strong adhesive force, small friction coefficient and small heat conductivity, and particularly has obvious effect of improving the corrosion resistance of materials such as carbon steel, cast iron and the like when being covered on iron alloy materials in a high-temperature corrosion environment. Therefore, the TiAlN coating has wide popularization prospect in the field of metal corrosion.
After the last century the study of TiAlN coatings has been published, one has paid great attention to its high temperature oxidation resistance and better service characteristics, and has successfully used various PVD methods to prepare TiAlN coatings, because the characteristics of TiAlN coatings described in the previous articles are different from one another. The hardness and oxidation temperature of TiAlN coating are high, and the properties of the multi-layered coating and the nano TiAlN coating are continuously improved. TiAlN has good chemical stability, strong oxidation and wear resistance, the hardness is (3400-3600 HV), the wear resistance is only slightly lower than that of a diamond-like film, and the TiAlN is a recommended hard coating in the international tool industry. When the aluminum content is 50% or more, it is A1TiN for distinction from TiAlN. The corrosion resistance of the A1TiN coating has a close relation with the content of aluminum, and when the content of the aluminum is increased as a metal of a sacrificial anode in electrochemistry, the corrosion resistance of the coating is also greatly improved.
At present, two main methods exist for preparing TiAlN coating on the surface of ferroalloy material: the invention mainly adopts a PVD method to prepare a TiAlN coating on the surface of carbon steel, wherein the PVD method comprises a reactive ion deposition method and a reactive sputtering method, and most factories adopt the former method. The reactive ion deposition method uses a metal matrix as a cathode. The metal vapor is used as anode, the metal is vaporized by means of electron gun, the metal vapor and the introduced reaction gas are ionized under the action of electric field, and the metal vapor and the introduced reaction gas are accelerated to move towards cathode, collide with each other to form coating on the workpiece. PVD has the following advantages over CVD:
(1) In the case of plain carbon steel, the smelting temperature is higher than the coating temperature, so that the hardness of the carbon steel used as a matrix is not 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 appearance of the coated product is not affected.
(3) The coating has high purity and good compactness, the coating and the matrix can be well combined, and the coating characteristics have little influence on the matrix material;
(4) The surface of the coating is smooth and even, and no abnormal structure appears at corners and circular arcs, so that even and smooth coatings can be obtained on metal matrixes with different surface states;
(5) No decarburization phase is generated. The condition that the coating is easy to crack caused by corrosion of chlorine and hydrogen embrittlement deformation in a CVD method is avoided, and the density of the coating is also larger;
(6) The working process is clean, pollution-free and nuisanceless.
The surface layer of carbon steel is covered with one or more layers of metal compound (hard coating such as Ti-N, T-C, ti-Al-N, etc.) or nonmetallic compound (soft coating such as M O S 2 ，WS 2 Pure graphite, etc.), so that the overall properties of the metal are greatly improved over the service life; because the metal compound which is difficult to melt has the characteristics of higher hardness, better wear resistance, high temperature resistance and the like, when a sample is placed in a corrosive medium after the surface layer of carbon steel is covered with a hard coating, the coating can be used as a physical barrier at the moment to effectively prevent harmful ions in the solution from reaching the surface of a metal matrix to cause corrosion, and the barrier has the characteristics of high temperature resistance and wear resistanceThus, the wear resistance and the high temperature resistance of the carbon steel are improved to a certain extent.
Disclosure of Invention
The invention is based on the technology for preparing the TiAlN coating on the surface of the carbon steel, and aims to effectively improve the corrosion resistance of the carbon steel.
The technical scheme of the invention is as follows:
a preparation method of a metal corrosion-resistant coating on the surface of carbon steel 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, vertically fixing the test piece on a two-dimensional rotating rod of a rotating frame, keeping the test piece parallel to the surface of a target, and keeping the distance between the test piece and the target at 170-190 mm; fine dust on the surface of the sample is lightly blown off, a vacuum chamber door is closed, a rotating stand is started, and the rotation speed of a central shaft of a motor of the rotating stand is regulated to be 2-7 r/min;
(2) Firstly, vacuumizing to the pressure of 650 Pa-1000 Pa in the coating vacuum chamber, and then continuously vacuumizing to the pressure of 1.5 Pa-3.5 Pa in the chamber;
(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 heating preset temperature of a sample is 300-380 ℃; preserving heat for 20-35 min after reaching the temperature, wherein the indoor pressure is 5.5X10 -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 argon flow in the range of 100-280 sccm for 20-30 min, and at the moment, keeping the pressure in the vacuum chamber at about 2-2.5 Pa;
(4) Continuously introducing argon gas of 120-160 sccm, respectively starting two rows of nine Cr targets to deposit a Cr priming layer, controlling the arc striking electrode to contact with the targets in a very short time through a small cylinder, then quickly separating the targets, obviously observing blue arc ablation in front of the targets after successful arcing, spraying the targets under the action of an arc power supply, forming a low-voltage and high-current passage by the material and the arc striking electrode, wherein the argon gas flow 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 depositing a CrN priming layer, wherein the duration is 15-20 min, reducing the negative bias voltage to 100-150V, and respectively setting the flow of the nitrogen and the argon to 200-400 sccm and 10-20 sccm, wherein the flow of the argon is kept unchanged at the moment, and the flow of the nitrogen is finely adjusted according to the indoor pressure to ensure that the pressure in the vacuum chamber is kept at 1.0Pa;
(5) Closing an argon electromagnetic throttle valve, only introducing nitrogen, wherein the flow is 700-900 sccm, the Cr target and the Ti-Al alloy target are fully opened, the throttle valve opening is 20-25%, the negative bias voltage is reduced to 80-100V, the deposition of a CrN and TiAlN transition layer is started, and the pressure in a vacuum chamber is kept at 1.5-4.0 Pa; closing the Cr target, only keeping two columns of Ti-Al alloy targets to work, reducing the nitrogen flow, about 520-650 sccm, keeping the pressure in the vacuum chamber at 1.5-2 Pa, keeping the negative bias unchanged, 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, in step (1), the compressed air cleaned by the air gun is used to blow fine dust on the surface of the sample.
Further, in the step (1), the test pieces are subjected to treatment, and each test piece is polished in 200#, 400#, 800#, 1000#, 2000# abrasive paper in sequence, and then is dried after being washed by acetone and ethanol for later use.
Further, in the step (2), a mechanical pump is used for vacuumizing to the pressure below 1000Pa in the coating vacuum chamber, then the vacuum pump is started, and vacuumizing is continued to the pressure below 3.5Pa in the chamber.
Further, in the step (3), since the negative bias voltage adopts the domestic pulse bias voltage power supply, the bias duty ratio is adjusted to be 80-90% at the highest.
Further, in the step (4), the low voltage is 12 to 20V and the high current is 30 to 80A.
Further, in the step (4), the extremely short time is 1 to 3 seconds.
Further, in the step (5), argon is continuously introduced for protection and cooling to 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 preparation process and method of the Ti-Al-N coating on the surface of the carbon steel provided by the invention preferably comprises the following steps:
1. and loading the treated test piece and the carbon steel sheet with the same material into a vacuum chamber of the multi-arc ion plating machine, vertically fixing the test piece on a two-dimensional rotating rod of a rotating frame, keeping the test piece parallel to the surface of the target, and keeping the distance between the test piece and the target between 170 and 190mm. The compressed air cleaned by the air gun lightly blows fine dust on the surface of the sample, the vacuum chamber door is closed, the rotating stand is started, the rotating speed of the shaft of the motor of the rotating stand is regulated to be 2r/min, and the rotating speed is kept unchanged so as to ensure the uniformity of the coating sample;
2. vacuumizing by a mechanical pump until the pressure in the coating vacuum chamber is lower than 1000Pa, then starting the vacuum pump, and continuously vacuumizing until the pressure in the coating vacuum chamber is lower than 3.5Pa;
3. starting a molecular pump and a front-end gate valve to pump high vacuum, and starting a heating pipe to heat at the same time, wherein the heating time is about 120min, and the heating preset temperature of a sample is 300-380 ℃; preserving heat for 20min after reaching the temperature, wherein the indoor pressure is about 5.5X10 - 3 Pa; closing a throttle valve at the front end of the molecular pump, introducing argon gas, performing ion cleaning before coating, and adding a negative bias to about 800V, wherein the negative bias adopts a domestic pulse bias power supply, so that the bias duty ratio is adjusted to be 80% at the highest, the argon gas flow is maintained in the range of 100-280 sccm for about 20min, and the pressure in the vacuum chamber is about 2-2.5 Pa at the moment;
4. continuously introducing argon gas of 120sccm, respectively starting two rows of nine Cr targets to deposit a Cr priming layer, controlling the arc striking electrode to contact with the targets in a very short time through a small cylinder, then quickly separating the targets, obviously observing blue arc ablation in front of the targets after successful arcing, spraying the targets under the action of an arc power supply, forming a low-voltage (20V) and high-current (30-80A) passage by the material and the arc striking electrode, wherein the argon gas 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 depositing a CrN priming layer, wherein the duration is about 20min, reducing the negative bias voltage to 150V, wherein the flow of the nitrogen and the argon is about 400sccm and about 10sccm respectively, at this time, the flow of the argon is kept unchanged, the flow of the nitrogen is finely adjusted according to the indoor pressure, and the pressure in the vacuum chamber is kept at 1.0Pa;
5. closing an argon electromagnetic throttle valve, only introducing nitrogen, and keeping the flow at 900sccm, fully opening a Cr target and a Ti-Al alloy target, wherein the throttle valve is 25%, reducing the negative bias to 100V, starting to deposit a CrN and TiAlN transition layer, and keeping the pressure in a vacuum chamber at about 2.5Pa; closing the Cr target, only keeping two columns of Ti-Al alloy targets to work, reducing the nitrogen flow, about 650sccm, keeping the pressure in the vacuum chamber at 2Pa, keeping the negative bias unchanged, and depositing a working layer for 100min; stopping heating, continuously introducing argon for protection and cooling to below 60 ℃, opening the furnace door, and taking out the test sample to be detected.
One of the innovation points of the invention is that a vacuum multi-arc ion plating technology is used, and plating is carried out on the surface of the carbon steel material for the first time. Namely 1, adopting a vacuum multi-arc ion plating technology. 2. The TiAlN metal coating is applied to the surface of the carbon steel for the first time.
The invention uses a Multi-Arc ion plating technology, which is a key point for realizing 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 technology core is a novel film plating technology which uses cold cathode self-sustaining vacuum Arc discharge in an evaporation source. Because the cathode target is directly evaporated, a molten pool and a cathode arc are not generated in the system (the process steps are reduced), and the control of the plating layer composition and the morphology is completed by regulating and controlling the evaporation source to serve as a cathode target component.
The beneficial technical effects of the invention are as follows:
according to the metal corrosion-resistant coating on the surface of the carbon steel and the preparation method, the TiAlN coating prepared based on the PVD method can be well adhered to the surface of the carbon steel to form the corrosion-resistant coating, and experimental tests show that the corrosion-resistant effect of the coating is very obvious (the data in Table 1 prove that the smaller the corrosion current is, the worse the corrosion resistance is), 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 combination property with the metal matrix, and can protect the carbon steel for a longer time compared with other coatings.
Drawings
FIG. 1 is a schematic diagram of a multi-arc ion plating machine;
wherein: 1-target arc source, 2-arc source target source, 3-working bias power supply motor, 4-auxiliary heating device, 5-sample to be plated, 6-sample to be plated, 7-reaction gas and 8-air exhaust.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the present invention further, but are not to be construed as limiting the present invention.
The multi-arc ion plating machine is produced by an Antai technology (domestic), the size phi of the target material is 100 multiplied by 20mm, the purity of a Cr target is 99.8 percent (2N 8), the components of the alloy target are AlCr (Al 67 percent, cr 33 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 for a Ti-Al-N coating on the surface of Q235 carbon steel comprise the following steps:
1. and loading the treated test piece and the Q235 carbon steel sheet of the same material into a vacuum chamber of a multi-arc ion plating machine, vertically fixing the test piece on a two-dimensional rotating rod of a rotating frame, keeping the test piece parallel to the surface of the target, and keeping the distance between the test piece and the target between 185 mm. The compressed air cleaned by the air gun lightly blows fine dust on the surface of the sample, the vacuum chamber door is closed, the rotating stand is started, the rotating speed of the shaft of the motor of the rotating stand is regulated to be 2r/min, and the rotating speed is kept unchanged so as to ensure the uniformity of the coating sample;
2. vacuumizing to 950Pa of the indoor pressure of the film plating vacuum chamber by using a mechanical pump, then starting the vacuum pump, and continuously vacuumizing to 3.5Pa of the indoor pressure;
3. opening a molecular pump and a front-end gate valve to pump high vacuum, and simultaneously opening a heating pipe to heat for about 120min, wherein the heating preset temperature of a Q235 sample is 300 ℃; preserving heat for 20min after reaching the temperature, wherein the indoor pressure is about 5.5X10 -3 Pa；
Closing a throttle valve at the front end of the molecular pump, introducing argon gas, cleaning ions before coating, and adding a negative bias to about 800V, wherein the negative bias adopts a domestic pulse bias power supply, so that the bias duty ratio is adjusted to be 80% at the highest, the argon gas flow is maintained in a range of 170sccm for about 20min, and the pressure in a vacuum chamber is about 2-2.5 Pa at the moment;
4. continuously introducing argon gas of 120sccm, respectively starting two rows of nine Cr targets to deposit a Cr priming layer, controlling the arc striking electrode to contact with the targets in a very short time through a small cylinder, then quickly separating the targets, obviously observing blue arc ablation in front of the targets after successful arcing, spraying the targets under the action of an arc power supply, forming a low-voltage (20V) and high-current (55A) passage by the material and the arc striking electrode, wherein the argon gas 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 depositing a CrN priming layer, wherein the duration is about 20min, reducing the negative bias voltage to 150V, wherein the flow of the nitrogen and the argon is about 400sccm and about 10sccm respectively, at this time, the flow of the argon is kept unchanged, the flow of the nitrogen is finely adjusted according to the indoor pressure, and the pressure in the vacuum chamber is kept at 1.0Pa;
5. closing an argon electromagnetic throttle valve, only introducing nitrogen, wherein the flow is 900sccm, fully opening a Cr target and a Ti-Al alloy target, the throttle valve opening is 25%, the negative bias is reduced to 100V, depositing a CrN and TIANN transition layer is started, and the pressure in a vacuum chamber is kept at about 2.5Pa; closing the Cr target, only keeping two columns of Ti-Al alloy targets to work, reducing the nitrogen flow, about 650sccm, keeping the pressure in the vacuum chamber at 2Pa, keeping the negative bias unchanged, and depositing a working layer for 100min; stopping heating, continuously introducing argon for protection and cooling to below 60 ℃, opening the furnace door, and taking out the 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 prepared into a 10X 10mm standard electrode, 3.5wt.% 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 stationary and the experimental temperature was 25 ℃. The electrochemical test adopts electrokinetic polarization curve to test, respectively measures the polarization curve of the coating sample with equal area under the same condition, the reference electrode is Saturated Calomel Electrode (SCE), the scanning interval is-0.35-0.25V, and the scanning rate is 1mV/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 prepared into a 10X 10mm standard electrode, 3.5wt.% NaCl solution is used as corrosive liquid, the heating preset temperature of the Q235 sample is 320 ℃, and other conditions are unchanged; the experimental conditions were stationary and the experimental temperature was 25 ℃. The electrochemical test adopts electrokinetic polarization curve to test, respectively measures the polarization curve of the coating sample with equal area under the same condition, the reference electrode is Saturated Calomel Electrode (SCE), the scanning interval is-0.35-0.25V, and the scanning rate is 1mV/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 prepared into a 10X 10mm standard electrode, 3.5wt.% 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 stationary and the experimental temperature was 25 ℃. The electrochemical test adopts electrokinetic polarization curve to test, respectively measures the polarization curve of the coating sample with equal area under the same condition, the reference electrode is Saturated Calomel Electrode (SCE), the scanning interval is-0.35-0.25V, and the scanning rate is 1mV/s.
Example 4
A preparation process and a method for a Ti-Al-N coating on the surface of Q235 carbon steel comprise the following steps:
1. and loading the treated test piece and the Q235 carbon steel sheet of the same material into a vacuum chamber of a multi-arc ion plating machine, vertically fixing the test piece on a two-dimensional rotating rod of a rotating frame, keeping the test piece parallel to the surface of the target, and keeping the distance between the test piece and the target between 180 mm. The compressed air cleaned by the air gun lightly blows fine dust on the surface of the sample, the vacuum chamber door is closed, the rotating stand is started, the rotating speed of the shaft of the motor of the rotating stand is regulated to be 3r/min, and the rotating speed is kept unchanged so as to ensure the uniformity of the coating sample;
2. vacuumizing to the pressure of 800Pa in the coating vacuum chamber by using a mechanical pump, then starting the vacuum pump, and continuously vacuumizing to the pressure of 3.5Pa in the chamber;
3. opening a molecular pump and a front-end gate valve to pump high vacuum, and simultaneously opening a heating pipe to heat for about 120min, wherein the heating preset temperature of a Q235 sample is 350 ℃; preserving heat for 15min after reaching the temperature, wherein the indoor pressure is about 5.5X10 -3 Pa；
Closing a throttle valve at the front end of the molecular pump, introducing argon gas, cleaning ions before coating, and adding a negative bias to about 800V, wherein the negative bias adopts a domestic pulse bias power supply, so that the bias duty ratio is adjusted to be 80% at the highest, the argon gas flow is maintained in a range of 170sccm for about 20min, and the pressure in a vacuum chamber is about 2-2.5 Pa at the moment;
4. continuously introducing argon gas of 120sccm, respectively starting two rows of nine Cr targets to deposit a Cr priming layer, controlling the arc striking electrode to contact with the targets in a very short time through a small cylinder, then quickly separating the targets, obviously observing blue arc ablation in front of the targets after successful arcing, spraying the targets under the action of an arc power supply, forming a low-voltage (25V) and high-current (60A) passage by the material and the arc striking electrode, wherein the argon gas 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 depositing a CrN priming layer, wherein the duration is about 20min, reducing the negative bias voltage to 150V, wherein the flow of the nitrogen and the argon is about 400sccm and about 10sccm respectively, at this time, the flow of the argon is kept unchanged, the flow of the nitrogen is finely adjusted according to the indoor pressure, and the pressure in the vacuum chamber is kept at 1.0Pa;
5. closing an argon electromagnetic throttle valve, only introducing nitrogen, wherein the flow is 900sccm, fully opening a Cr target and a Ti-Al alloy target, the throttle valve opening is 25%, the negative bias is reduced to 100V, depositing a CrN and TIANN transition layer is started, and the pressure in a vacuum chamber is kept at about 2.5Pa; closing the Cr target, only keeping two columns of Ti-Al alloy targets to work, reducing the nitrogen flow, about 650sccm, keeping the pressure in the vacuum chamber at 2Pa, keeping the negative bias unchanged, and depositing a working layer for 100min; stopping heating, continuously introducing argon for protection and cooling to below 60 ℃, opening the furnace door, and taking out the 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 prepared into a 10X 10mm standard electrode, 3.5wt.% NaCl solution is used as corrosive liquid, the heating preset temperature of the Q235 sample is 350 ℃, and other conditions are unchanged; the experimental conditions were stationary and the experimental temperature was 25 ℃. The electrochemical test adopts electrokinetic polarization curve to test, respectively measures the polarization curve of the coating sample with equal area under the same condition, the reference electrode is Saturated Calomel Electrode (SCE), the scanning interval is-0.35-0.25V, and the scanning rate is 1mV/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 metal matrix coating sample are prepared into a 10X 10mm standard electrode, 3.5wt.% NaCl solution is used as corrosive liquid, the heating preset temperature of the Q345 sample is 360 ℃, and other conditions are unchanged; the experimental conditions were stationary and the experimental temperature was 25 ℃. The electrochemical test adopts electrokinetic polarization curve to test, respectively measures the polarization curve of the coating sample with equal area under the same condition, the reference electrode is Saturated Calomel Electrode (SCE), the scanning interval is-0.35-0.25V, and the scanning rate is 1mV/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 metal matrix coating sample are prepared into a 10X 10mm standard electrode, 3.5wt.% NaCl solution is used as corrosive liquid, the heating preset temperature of the Q345 sample is 380 ℃, and other conditions are unchanged; the experimental conditions were stationary and the experimental temperature was 25 ℃. The electrochemical test adopts electrokinetic polarization curves to test, respectively measures the polarization curves of the coating samples with the same area and size under the same condition, wherein the reference electrode is a Saturated Calomel Electrode (SCE), the scanning interval is-0.35 to-0.25V, and the scanning rate is 1mV/s.
Table 1 properties of each sample after treatment in each example
It will of course be appreciated by those skilled in the art that the above-described embodiments are provided for illustration only and not as limitations of the present invention, and that variations and modifications of the above-described embodiments will fall within the scope of the appended claims.
Claims (10)
1. The preparation method of the metal corrosion-resistant coating on the surface of the carbon steel is characterized by comprising the following steps of:
(1) Loading the test piece and the carbon steel sheet made of the same material into a vacuum chamber of a multi-arc ion plating machine, closing a door of the vacuum chamber, starting a rotating frame, and adjusting the rotation speed of a central shaft of a motor of the rotating frame to be 2-7 r/min;
(2) Firstly vacuumizing to a pressure below 650 Pa-1000 Pa in a coating vacuum chamber, and then continuously vacuumizing to a pressure below 1.5 Pa-3.5 Pa in the chamber;
(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 heating preset temperature of a sample is 300-380 ℃; preserving heat for 20-35 min after reaching the temperature, wherein the indoor pressure is 5.5X10 -3 ~8×10 -3 Pa; closing a throttle valve at the front end of the molecular pump, introducing argon, performing ion cleaning before coating, increasing the negative bias to 700-800V, maintaining the argon flow in the range of 100-280 sccm for 20-30 min, and at the moment, keeping the pressure in the vacuum chamber at 2-2.5 Pa;
(4) Continuously introducing argon gas of 120-160 sccm, respectively starting two rows of nine Cr targets to deposit a Cr priming layer, controlling the arc striking electrode and the targets to be contacted in a short time through a small cylinder, and then quickly separating the arc striking electrode from the targets, wherein the materials and the arc striking electrode form a low-voltage and high-current passage, the flow rate of the argon gas is 120-160 sccm, the duration is 6-10 min, the pressure in a vacuum chamber is 2.0-4.0 Pa, and the negative bias voltage is 600-750V; introducing nitrogen and trace argon to start depositing a CrN priming layer, wherein the duration is 15-20 min, reducing the negative bias voltage to 100-150V, and respectively setting the flow of the nitrogen and the argon to 200-400 sccm and 10-20 sccm, wherein the flow of the argon is kept unchanged at the moment, and the flow of the nitrogen is finely adjusted according to the indoor pressure to ensure that the pressure in the vacuum chamber is kept at 1.0Pa;
(5) Closing an argon electromagnetic throttle valve, only introducing nitrogen, wherein the flow is 700-900 sccm, fully opening a Cr target and a Ti-Al alloy target, the throttle valve opening is 20-25%, the negative bias is reduced to 80-100V, depositing a CrN and TiAlN transition layer is started, and the pressure in a vacuum chamber is kept at 1.5-4.0 Pa; closing the Cr target, only keeping two rows of Ti-Al alloy targets to work, reducing the nitrogen flow by 520-650 sccm, keeping the pressure in the vacuum chamber at 1.5-2 Pa, keeping the negative bias unchanged, 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 the metal corrosion-resistant coating on the surface of the carbon steel according to claim 1, wherein in the step (1), in a vacuum chamber of a multi-arc ion plating machine, a 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, and the distance between the test piece and the target is kept at 170-190 mm.
3. The method for producing a metallic corrosion resistant coating on a carbon steel surface according to claim 1, wherein in step (1), fine dust on the surface of the sample is lightly blown by compressed air cleaned by an air gun, and then the vacuum chamber door is closed.
4. The method for preparing a metal corrosion resistant coating on a carbon steel surface according to claim 1, wherein in the step (1), the test pieces are subjected to treatment, each test piece is polished in sequence at 200#, 400#, 800#, 1000#, 2000# sand paper, and the test pieces are dried after being washed with acetone and ethanol for later use.
5. The method for preparing the metal corrosion resistant coating on the surface of the carbon steel according to claim 1, wherein in the step (2), a mechanical pump is used for vacuumizing to the pressure below 1000Pa in a vacuum chamber of the coating film, then the vacuum pump is started, and vacuumizing is continued to the pressure below 3.5Pa in the vacuum chamber.
6. The method for preparing a metal corrosion resistant coating on a carbon steel surface according to claim 1, wherein in the step (3), a domestic pulse bias power supply is adopted for the negative bias, so that the bias duty ratio is adjusted to be at most 80-90%.
7. The method for preparing a metal corrosion resistant coating on a carbon steel surface according to claim 1, wherein in the step (4), the low voltage is 12-20 v, and the high current is 30-80 a.
8. The method for preparing a metal corrosion resistant coating on a carbon steel surface according to claim 1, wherein in the step (4), the extremely short time is 1-3 s.
9. The method for preparing a metal corrosion resistant coating on a carbon steel surface according to claim 1, wherein argon is continuously introduced into the carbon steel surface in the step (5) for protection and cooling to below 60 ℃.
10. A carbon steel surface metal corrosion resistant coating prepared by the method for preparing a carbon steel surface metal corrosion resistant coating according to any one of claims 1 to 9.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009279690A (en) * | 2008-05-21 | 2009-12-03 | Hitachi Tool Engineering Ltd | Manufacturing method of coated cutting tool |
| CN102294484A (en) * | 2010-06-22 | 2011-12-28 | 宝山钢铁股份有限公司 | Method for manufacturing 18-8 type austenite stainless steel-carbon steel coated steel plate |
| CN106702330A (en) * | 2015-11-12 | 2017-05-24 | 中国科学院金属研究所 | Carbon steel or stainless steel surface micro-arc oxidation ceramic coating based on aluminized coating, and preparation method thereof |
| CN107338409A (en) * | 2017-07-26 | 2017-11-10 | 东北大学 | Controllable magnetic field arc ion plating prepares the process of nitrogen base hard coat |
| JP2018051714A (en) * | 2016-09-30 | 2018-04-05 | 三菱マテリアル株式会社 | Surface-coated cutting tool having excellent chipping resistance and wear resistance |
| CN110344001A (en) * | 2019-08-16 | 2019-10-18 | 青岛滨海学院 | A kind of carbon steel surface corrosion-resistant erosion graded metal coating and preparation method thereof |
| CN110592535A (en) * | 2019-08-16 | 2019-12-20 | 青岛滨海学院 | Carbon steel surface abrasion-resistant high-temperature protective coating and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020166606A1 (en) * | 2001-03-12 | 2002-11-14 | Russell Caminiti | Method of coating a metal substrate |
-
2021
- 2021-03-24 CN CN202110314610.9A patent/CN115125493B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009279690A (en) * | 2008-05-21 | 2009-12-03 | Hitachi Tool Engineering Ltd | Manufacturing method of coated cutting tool |
| CN102294484A (en) * | 2010-06-22 | 2011-12-28 | 宝山钢铁股份有限公司 | Method for manufacturing 18-8 type austenite stainless steel-carbon steel coated steel plate |
| CN106702330A (en) * | 2015-11-12 | 2017-05-24 | 中国科学院金属研究所 | Carbon steel or stainless steel surface micro-arc oxidation ceramic coating based on aluminized coating, and preparation method thereof |
| JP2018051714A (en) * | 2016-09-30 | 2018-04-05 | 三菱マテリアル株式会社 | Surface-coated cutting tool having excellent chipping resistance and wear resistance |
| CN107338409A (en) * | 2017-07-26 | 2017-11-10 | 东北大学 | Controllable magnetic field arc ion plating prepares the process of nitrogen base hard coat |
| CN110344001A (en) * | 2019-08-16 | 2019-10-18 | 青岛滨海学院 | A kind of carbon steel surface corrosion-resistant erosion graded metal coating and preparation method thereof |
| CN110592535A (en) * | 2019-08-16 | 2019-12-20 | 青岛滨海学院 | Carbon steel surface abrasion-resistant high-temperature protective coating and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 40Cr 表面多弧离子镀 TiAlN/TiN 复合膜层的工艺及性能研究;蒋涛;《中国优秀硕士学位论文全文数据库工程科技I辑》;B022-125 * |
| Influence of Substrate of the Carbon Contents and Coating Thickness on Scratch and Wear Resistance of AlCrN Films;Chandrashekhar Ambiger et al;《Materials Science and Metallurgy Engineering》;第3卷(第1期);第1-7页 * |
| Influence of vacuum annealing on structures and mechanical properties of AleTieN films deposited by multi-arc ion plating;Mingxi Li et al;《Current Applied Physics》;第1470-1476页 * |
| Investigations of mechanical and tribological properties of CrAlNqC thin coatings deposited on cutting tools;E. Lugscheider et al;《Surface and Coatings Technology》;第681–686页 * |
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