CN110158035B - Metal-metal nitride multilayer coating resistant to high-temperature marine environment corrosion and preparation method thereof - Google Patents
Metal-metal nitride multilayer coating resistant to high-temperature marine environment corrosion and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of titanium alloy high-temperature protective coatings, in particular to a metal-metal nitride multilayer coating resistant to high-temperature marine environment corrosion and a preparation method thereof. The multilayer coating is formed by alternately depositing Ti sublayers and TiN sublayers on a substrate, the TiN layers are close to the substrate and the uppermost layer, and the substrate is Ti6Al4V titanium alloy; in the multilayer coating, the thickness of each TiN sublayer is 1.7-2.0 μm, and the total number of Ti sublayers is 0.1-1.0 μm and is an odd number in 13-21 layers. The preparation of the multilayer coating comprises: cleaning a substrate and alternately depositing TiN sublayers and Ti sublayers. The invention prepares the thick Ti/TiN multilayer coating with different sub-layer proportions on the titanium alloy substrate, the coating has good bonding strength with the substrate and higher thickness, and the high-temperature corrosion resistance of the titanium alloy substrate is improved by increasing the diffusion path of a corrosion medium and reducing the structural defects.
Description
The technical field is as follows:
the invention relates to the field of titanium alloy high-temperature protective coatings, in particular to a metal-metal nitride multilayer coating resistant to high-temperature marine environment corrosion and a preparation method thereof.
Background art:
the titanium alloy has low density and high strength, and is a key material of an aircraft engine compressor. But as the material of the compressor blade in medium and high temperature service, it has the following disadvantages: firstly, the hardness is lower, the erosion resistance is poorer, and secondly, the high-temperature corrosion resistance is insufficient. In particular for aircraft engines used in marine environments, the titanium alloy parts of the compressor of which are subjected to medium or high temperature Cl-The corrosion rate of the synergistic corrosion of O, water vapor and the like is far higher than the oxidation rate of pure air, and a thick brittle oxygen dissolving layer is generated on the sub-surface of the alloy at a lower temperature, so that the mechanical property of the alloy is obviously reduced.
The metal nitride coating has excellent erosion resistance and high-temperature corrosion resistance, shows good application prospect in the aspect of titanium alloy protection, and is particularly suitable for titanium alloy parts of the aircraft compressor serving in the marine environment. However, when the coating is exposed to a corrosive environment for a long time at a higher temperature, local accelerated corrosion of the coating occurs, and causes severe corrosion of an underlying substrate, and defects such as pinholes and molten drops in the coating are often the source of induced accelerated corrosion.
Increasing the thickness of the coating improves the corrosion resistance of the coating. However, as a ceramic coating, the high internal stress and intrinsic brittleness of the nitride coating cause the bonding properties of the coating to the substrate to decrease with increasing thickness, with a significant increase in the tendency of a single layer nitride coating to flake off at thicknesses in excess of 7 μm; moreover, when the coating is in service in a high-temperature environment, the coefficient of thermal expansion of the coating and the matrix which are not matched leads to larger tensile stress in the coating, the coating is easy to crack, the corrosion resistance is deteriorated, and the long-term protection performance of the coating is difficult to ensure.
Compared with a single-layer nitride coating, the metal-nitride multilayer coating has lower internal stress and good bonding strength with a matrix, and simultaneously has high mechanical property and corrosion resistance. Studies have shown (surf. coat. technol.258(2014) 102-: migration of corrosive media in defects such as droplet pinholes is inhibited or the number of through defects is reduced.
The Ti/TiN multilayer coating has the advantages of low internal stress, good coating/matrix bonding strength, high mechanical property and the like, and the reports of corrosion of the thick Ti/TiN multilayer coating in high-temperature marine environment at home and abroad are less.
The invention content is as follows:
the invention aims to provide a metal-metal nitride multilayer coating resistant to high-temperature marine environment corrosion and a preparation method thereof, which can solve the problem of high-temperature corrosion of titanium alloy and provide a thought for high-temperature protection of parts of an aircraft engine.
The technical scheme of the invention is as follows:
the multilayer metal-metal nitride coating resistant to high-temperature marine environment corrosion is formed by alternately depositing Ti sublayers and TiN sublayers on a substrate, wherein TiN layers are arranged close to the substrate and on the uppermost layer.
The thickness of each TiN sublayer is 1.7-2.0 mu m, the thickness of each Ti sublayer is 0.1-1.0 mu m, and the total number of layers of the metal/metal nitride multilayer coating is an odd number of 13-21 layers.
The matrix of the metal-metal nitride multilayer coating resistant to high-temperature marine environment corrosion is Ti6Al 4V.
The preparation method of the metal-metal nitride multilayer coating resistant to high-temperature marine environment corrosion specifically comprises the following steps:
(1) substrate cleaning
Grinding and polishing a Ti6Al4V titanium alloy substrate, putting the titanium alloy substrate into a solution in which acetone and ethanol are mixed according to a volume ratio of 1: 2-4, cleaning the titanium alloy substrate for 10-15 min by using 15-20 kHz ultrasonic waves, taking out the titanium alloy substrate and drying the titanium alloy substrate by blowing; hanging the processed sample on a sample rack, putting the sample on an ion plating vacuum chamber, closing a chamber door, and performing ion bombardment cleaning by using ion plating equipment;
(2) alternately depositing TiN sub-layers and Ti sub-layers
After the ion bombardment cleaning in the step (1) is finished, cutting off Ar and introducing N2Applying pulse negative bias to Ti6Al4V Ti alloy substrate to open cathode Ti, starting deposition of a TiN sublayer by target current; then depositing a Ti sublayer, keeping the current of the Ti target constant, and turning off N2Introducing Ar, adjusting the negative bias value of the Ti6Al4V titanium alloy matrix, and performing Ti sublayer deposition; in the subsequent deposition process, TiN sublayers and Ti sublayers are alternately deposited in sequence; and after the last Ti sublayer is deposited, depositing a TiN layer as the outermost layer.
The preparation method of the metal-metal nitride multilayer coating resistant to high-temperature marine environment corrosion comprises the step (1) of vacuumizing to the vacuum degree of 7 multiplied by 10 before ion bombardment cleaning-3～10×10-3Pa, introducing Ar to maintain the vacuum degree at 0.2-0.5 Pa, applying a negative bias voltage of 850-950V to the Ti6Al4V titanium alloy substrate, and performing ion bombardment cleaning for 3-10 min at a duty ratio of 30-60%.
In the preparation method of the metal-metal nitride multilayer coating resistant to high-temperature marine environment corrosion, in the step (2), the purity of a Ti target is more than 99.99wt%, the diameter is 80-120 mm, the height is 50-60 mm, and the volume purity of argon and nitrogen is more than 99.99%.
The preparation method of the metal-metal nitride multilayer coating resistant to high-temperature marine environment corrosion comprises the following steps of (2) depositing TiN sublayers: ti target current of 60-80A, N2The pressure intensity is 1.4-2.0 Pa, the negative bias value is 550-600V, the deposition time is 18-21 min, the duty ratio is 20-30%, and the atomic ratio of Ti to N in the TiN layer is 1: 1.
The preparation method of the metal-metal nitride multilayer coating resistant to high-temperature marine environment corrosion comprises the following steps of (2) depositing Ti sublayers: the Ti target current is 60-80A, the Ar pressure is 0.2-0.5 Pa, the negative bias value is 50-100V, the deposition time is 2-21 min, and the duty ratio is 20-30%.
According to the preparation method of the metal-metal nitride multilayer coating resistant to high-temperature marine environment corrosion, in the deposition processes of the steps (1) to (2), the distance between a Ti target and a Ti6Al4V titanium alloy substrate is 17-22 cm, and a sample frame rotates at the speed of 3-6 rpm.
According to the preparation method of the metal-metal nitride multilayer coating resistant to high-temperature marine environment corrosion, in the coating deposition process, the temperature of a Ti6Al4V titanium alloy matrix is 300 +/-20 ℃.
The design idea of the invention is as follows:
the invention prepares the thick Ti/TiN multilayer coating with different sub-layer proportions on the titanium alloy substrate, the coating has good bonding strength with the substrate and higher thickness, and the high-temperature corrosion resistance of the titanium alloy substrate is improved by increasing the diffusion path of a corrosion medium and reducing the structural defects.
The invention has the advantages and beneficial effects that:
1. according to the invention, the metal Ti layer is periodically introduced to adsorb the internal stress of the nitride layer and effectively reduce the stress of the multilayer coating, so that the thick Ti/TiN multilayer coating with good film-substrate bonding strength can be obtained.
2. The thick Ti/TiN multilayer coating prepared by the invention prolongs the time of a corrosive medium reaching a matrix through the high thickness of the coating, and improves the high-temperature corrosion resistance of the matrix. The introduced Ti layer is of an equiaxed crystal structure, and breaks through a continuous columnar crystal structure of the TiN layer, so that the formation of penetrating defects such as cracks, micropores and crystal boundaries is inhibited, corrosive media can be prevented from reaching the titanium alloy matrix along the penetrating defects, and the coating can exert long-acting high-temperature corrosion protection.
3. The invention adopts the common ion plating vapor deposition means, has simple and convenient preparation process and is convenient for realizing industrial production and application.
4. The metal/metal nitride multilayer coating has good high-temperature marine environment corrosion resistance, and when the thickness of the Ti sublayer is 0.1 mu m, the high-temperature marine environment corrosion resistance is optimal.
Description of the drawings:
FIG. 1 is a scanning electron micrograph of the surface (a) and cross-section (b) of the Ti/TiN multilayer coating prepared in example 1.
FIG. 2 is a scanning electron micrograph of the surface (a) and cross-section (b) of the Ti/TiN multilayer coating prepared in example 1 after corrosion.
FIG. 3 is a scanning electron micrograph of the surface (a) and cross-section (b) of the Ti/TiN multilayer coating prepared in example 5.
FIG. 4 is a scanning electron micrograph of a surface (a) and a cross-section (b) of the Ti/TiN multilayer coating prepared in example 5 after corrosion.
FIG. 5 is a scanning electron micrograph of the surface (a) and cross-section (b) of the Ti/TiN multilayer coating prepared in example 6.
FIG. 6 is a scanning electron micrograph of a surface (a) and a cross-section (b) of the Ti/TiN multilayer coating prepared in example 6 after corrosion.
FIG. 7 is the scanning electron micrograph of the surface (a) and the cross section (b) of the TiN monolayer coating prepared by the comparative example.
FIG. 8 is the SEM photographs of the surface (a) and cross-section (b) of the TiN monolayer coating prepared by the comparative example after corrosion.
FIG. 9 is a graph of the corrosion gain of Ti/TiN multilayer coatings obtained in examples 1, 5, 10 and comparative example. In the figure, the abscissa t represents the oxidation time (h) and the ordinate Δ m/s represents the oxidation weight gain (mg/cm)2)。
FIG. 10 is a graph of the results of X-ray diffraction (XRD) after etching of Ti/TiN multilayer coatings obtained in examples 1, 5 and 10 and a comparative example.
The specific implementation mode is as follows:
in the specific implementation process, the preparation, characterization and measurement instrument used for preparing the metal/metal nitride multilayer coating resistant to high-temperature marine environment corrosion is as follows:
ion plating equipment, model DH-4, Shenyang North space vacuum technology, Inc.;
scanning electron microscope, model Philips FEI-aspect F, Spanish Philips Inc.;
x-ray diffractometers, D/MAX-RA X-ray energy spectrometers (XRD), japan physics machines;
high temperature corrosion thermogravimetric analyzer, model VERSA THERMHM, institute of metals of academy of sciences of china.
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited thereto.
Example 1
In this embodiment, the metal/metal nitride multilayer coating resistant to corrosion in a high-temperature marine environment is formed by alternately depositing Ti sublayers and TiN sublayers on a Ti6Al4V substrate, both the substrate and the uppermost layer are TiN layers, each TiN sublayer has a thickness of 2.0 μm, each Ti sublayer has a thickness of 0.1 μm, and the total number of layers is 17.
The preparation method of the metal/metal nitride multilayer coating resistant to high-temperature marine environment corrosion specifically comprises the following steps:
(1) cleaning of substrates
Firstly, grinding and polishing a Ti6Al4V titanium alloy (Ti-6% Al-4% V, mass fraction) substrate, and then adding acetone and ethanol according to a volume ratio of 1:2, cleaning the mixed solution by using 15-20 kHz ultrasonic waves for 10-15 min, taking out and drying the cleaned solution; then, ion bombardment cleaning is carried out by using ion plating equipment, the processed Ti6Al4V titanium alloy base body is hung on a sample rack and placed into an ion plating vacuum chamber, the chamber door is closed, and vacuum pumping is carried out until the vacuum degree is 7.0 multiplied by 10-3And after Pa, introducing Ar, maintaining the vacuum degree at 0.5Pa, applying a negative bias voltage value of 950V to the substrate, and performing ion bombardment cleaning on the substrate for 3min at a duty ratio of 30%.
(2) Alternately depositing TiN sub-layers and Ti sub-layers
After the ion bombardment cleaning in the step (1) is finished, cutting off Ar and introducing N2Maintaining the vacuum degree and the air pressure at 1.4Pa, controlling the pulse negative bias value of the matrix at 600V, opening the current of a cathode Ti target, setting the current as 60A, starting the deposition of a TiN sublayer, setting the time as 18.5min and the duty ratio as 20%, keeping the sample holder rotating, keeping the speed at 3rpm, and keeping the Ti: N ratio in the obtained sublayer as 1:1 (atomic ratio); then depositing a Ti sublayer, keeping the Ti target current 70A unchanged, and turning off N2Ar is introduced, the gas pressure is controlled to be about 0.2Pa, the negative bias value of the substrate is changed to 100V, the deposition time is controlled to be 2min, the duty ratio is set to be 20 percent, and the sample holder keeps the autorotation speed of 5 rpm. In the subsequent deposition process, TiN sublayers and Ti sublayers are alternately deposited in sequence; and after the last Ti sublayer is deposited, depositing a TiN layer as the outermost layer. The heating temperature of the matrix is 300 +/-20 ℃, the distance between the cathode target and the Ti6Al4V titanium alloy matrix is 17cm, the purity of the Ti target is 99.99wt%, and the diameter and the height of the Ti target are 80mm and 55 mm.
As shown in FIGS. 1(a) - (b), the morphology of the deposited multilayer coating is observed, a small amount of molten drops with small sizes exist on the surface of the coating, the bright white is a Ti sublayer, the dark gray is a TiN sublayer, the structure is uniform and compact, and the multilayer coating is bonded with a Ti6Al4V matrixThe method is good, and no cracking or layering phenomenon is found. After being corroded for 100 hours at 450 ℃, the total weight of corrosion weight gain is small, and the weight gain is gradually increased in the corrosion process (figure 9). As shown in FIGS. 2(a) - (b), the surface is complete after corrosion, and a layer of uniform, continuous and stable r-TiO is generated on the surface2(FIG. 10), the coating was internally intact and stable, indicating that the coating of this example has good corrosion resistance.
Example 2
In this embodiment, the metal/metal nitride multilayer coating resistant to corrosion in a high-temperature marine environment is formed by alternately depositing Ti sublayers and TiN sublayers on a Ti6Al4V substrate, both the substrate and the uppermost layer are TiN layers, each TiN sublayer has a thickness of 2.0 μm, each Ti sublayer has a thickness of 0.2 μm, and the total number of layers is 15.
The preparation method of the metal/metal nitride multilayer coating resistant to high-temperature marine environment corrosion specifically comprises the following steps:
(1) cleaning of substrates
Firstly, grinding and polishing a Ti6Al4V titanium alloy (Ti-6% Al-4% V, mass fraction) substrate, and then adding acetone and ethanol according to a volume ratio of 1: 2.5, cleaning the mixed solution for 10-15 min by using 15-20 kHz ultrasonic waves, taking out and drying the cleaned solution; then, ion bombardment cleaning is carried out by using ion plating equipment, the processed Ti6Al4V titanium alloy base body is hung on a sample rack and placed into an ion plating vacuum chamber, the chamber door is closed, and vacuum pumping is carried out until the vacuum degree is 8.5 multiplied by 10-3And after Pa, introducing Ar, maintaining the vacuum degree at 0.5Pa, applying a negative bias voltage value of 950V to the substrate, and performing ion bombardment cleaning on the substrate for 5min at a duty ratio of 40%.
(2) Alternately depositing TiN sub-layers and Ti sub-layers
After the ion bombardment cleaning in the step (1) is finished, cutting off Ar and introducing N2Maintaining the vacuum degree and the air pressure at 1.5Pa, controlling the matrix pulse negative bias value at 580V, opening the cathode Ti target current, setting the current to be 65A, starting the deposition of a TiN sublayer, setting the duty ratio to be 25 percent, keeping the sample frame rotating at the speed of 4rpm, and keeping the element ratio Ti to N in the obtained sublayer to be 1 to 1 (atomic ratio); then depositing a Ti sublayer, keeping the Ti target current 65A constant, and turning off N2Introducing Ar, controlling the air pressure atAbout 0.3Pa, the negative bias value of the substrate is changed to 80V, the deposition time is controlled to be 2.5min, the duty ratio is set to be 25 percent, and the sample holder keeps the autorotation speed of 4 rpm. In the subsequent deposition process, TiN sublayers and Ti sublayers are alternately deposited in sequence; and after the last Ti sublayer is deposited, depositing a TiN layer as the outermost layer. The heating temperature of the matrix is 300 +/-20 ℃, the distance between the cathode target and the Ti6Al4V titanium alloy matrix is 18cm, the purity of the Ti target is 99.99wt%, and the diameter and the height of the Ti target are 90mm and 55 mm.
The deposited multilayer coating is observed in appearance, a certain amount of molten drops with different sizes exist on the surface of the coating, the bright white is a Ti sublayer, the dark gray is a TiN sublayer, the molten drop defect exists inside the coating, the multilayer coating is well combined with a Ti6Al4V matrix, and cracking and layering phenomena are not found. After 100h of corrosion at 450 ℃, the total amount of corrosion weight gain is small, and the weight gain is slow in the corrosion process (figure 9). The surface is complete after corrosion, and a layer of uniform, continuous and stable r-TiO is generated on the surface2(FIG. 10), the coating was internally intact and stable, indicating that the coating of this example has good corrosion resistance.
Example 3
In this embodiment, the metal/metal nitride multilayer coating resistant to corrosion in a high-temperature marine environment is formed by alternately depositing Ti sublayers and TiN sublayers on a Ti6Al4V substrate, both the substrate and the uppermost layer are TiN layers, each TiN sublayer has a thickness of 1.9 μm, each Ti sublayer has a thickness of 0.3 μm, and the total number of layers is 15.
The preparation method of the metal/metal nitride multilayer coating resistant to high-temperature marine environment corrosion specifically comprises the following steps:
(1) cleaning of substrates
Firstly, grinding and polishing a Ti6Al4V titanium alloy (Ti-6% Al-4% V, mass fraction) substrate, and then adding acetone and ethanol according to a volume ratio of 1: 3, cleaning the mixed solution by using 15-20 kHz ultrasonic waves for 10-15 min, taking out and drying the cleaned solution; then, ion bombardment cleaning is carried out by using ion plating equipment, the processed Ti6Al4V titanium alloy base body is hung on a sample rack and put into an ion plating vacuum chamber, the chamber door is closed, and vacuum pumping is carried out until the vacuum degree is 9.0 multiplied by 10-3After Pa, Ar is introduced and maintainedThe vacuum degree is 0.4Pa, the negative bias value applied to the substrate is 900V, the duty ratio is 50%, and the substrate is cleaned by ion bombardment for 7 min.
(2) Alternately depositing TiN sub-layers and Ti sub-layers
After the ion bombardment cleaning in the step (1) is finished, cutting off Ar and introducing N2Maintaining the vacuum degree and the air pressure at 1.6Pa, controlling the matrix pulse negative bias value at 560V, opening the cathode Ti target current, setting the current at 70A, starting the deposition of the TiN sublayer, setting the duty ratio at 25 percent, keeping the sample frame rotating, keeping the speed at 5rpm, and keeping the Ti: N in the obtained sublayer at 1:1 (atomic ratio); then depositing a Ti sublayer, keeping the Ti target current 70A unchanged, and turning off N2Ar is introduced, the gas pressure is controlled to be about 0.4Pa, the negative bias value of the substrate is changed to 70V, the deposition time is controlled to be 3.5min, the duty ratio is set to be 25 percent, and the sample holder keeps the autorotation speed of 5 rpm. In the subsequent deposition process, TiN sublayers and Ti sublayers are alternately deposited in sequence; and after the last Ti sublayer is deposited, depositing a TiN layer as the outermost layer. The heating temperature of the matrix is 300 +/-20 ℃, the distance between the cathode target and the Ti6Al4V titanium alloy matrix is 19cm, the purity of the Ti target is 99.99wt%, and the diameter and the height of the Ti target are 100mm and 55 mm.
And (3) observing the appearance of the deposited multilayer coating, wherein a certain amount of molten drops with larger sizes exist on the surface of the coating, the bright white is a Ti sublayer and the dark gray is a TiN sublayer, the molten drop defect exists inside the coating, and the multilayer coating is well combined with a Ti6Al4V matrix without cracking and layering phenomena. After 100 hours of corrosion at 450 ℃, the corrosion weight gain is increased, the weight gain is accelerated in the corrosion process, molten drops on the surface are corroded, and a layer of uniform r-TiO is generated on the surface2The coating is complete and stable inside, and shows that the coating of the embodiment has better corrosion resistance.
Example 4
In this embodiment, the metal/metal nitride multilayer coating resistant to corrosion in a high-temperature marine environment is formed by alternately depositing Ti sublayers and TiN sublayers on a Ti6Al4V substrate, both the substrate and the uppermost layer are TiN layers, each TiN sublayer has a thickness of 1.8 μm, each Ti sublayer has a thickness of 0.4 μm, and the total number of layers is 13.
The preparation method of the metal/metal nitride multilayer coating resistant to high-temperature marine environment corrosion specifically comprises the following steps:
(1) cleaning of substrates
Firstly, grinding and polishing a Ti6Al4V titanium alloy (Ti-6% Al-4% V, mass fraction) substrate, and then adding acetone and ethanol according to a volume ratio of 1: 3.5, cleaning the mixture for 10-15 min by using 15-20 kHz ultrasonic waves, taking out and drying the mixture; then, ion bombardment cleaning is carried out by using ion plating equipment, the processed Ti6Al4V titanium alloy base body is hung on a sample rack and placed into an ion plating vacuum chamber, the chamber door is closed, and vacuum pumping is carried out until the vacuum degree is 9.5 multiplied by 10-3And after Pa, introducing Ar, maintaining the vacuum degree at 0.3Pa, applying a negative bias voltage value of 850V to the substrate, and performing ion bombardment cleaning on the substrate for 10min at a duty ratio of 60%.
(2) Alternately depositing TiN sub-layers and Ti sub-layers
After the ion bombardment cleaning in the step (1) is finished, cutting off Ar and introducing N2Maintaining the vacuum degree and the air pressure at 1.7Pa, controlling the matrix pulse negative bias value at 560V, opening the cathode Ti target current, setting the current at 75A, starting the deposition of the TiN sublayer, setting the duty ratio at 30 percent, keeping the sample frame rotating, keeping the speed at 6rpm, and keeping the Ti: N in the obtained sublayer at 1:1 (atomic ratio); then deposit Ti sublayer, keep Ti target current 75A unchanged, close N2Ar is introduced, the gas pressure is controlled to be about 0.35Pa, the negative bias value of the substrate is changed to 60V, the deposition time is controlled to be 4min, the duty ratio is set to be 30 percent, and the sample holder keeps the autorotation speed of 6 rpm. In the subsequent deposition process, TiN sublayers and Ti sublayers are alternately deposited in sequence; and after the last Ti sublayer is deposited, depositing a TiN layer as the outermost layer. The heating temperature of the matrix is 300 +/-20 ℃, the distance between the cathode target and the Ti6Al4V titanium alloy matrix is 20cm, the purity of the Ti target is 99.99wt%, and the diameter and the height of the Ti target are 110mm and 55 mm.
And (3) observing the appearance of the deposited multilayer coating, wherein a large number of molten drops with large sizes exist on the surface of the coating, the bright white is a Ti sublayer and the dark gray is a TiN sublayer, the molten drop defect exists inside the coating, and the multilayer coating is well combined with a Ti6Al4V matrix without cracking and layering phenomena. After etching at 450 ℃ for 100h, the etching was observedThe weight gain is increased, the weight gain is accelerated in the corrosion process, molten drops on the surface are corroded, and r-TiO is generated on the surface2The corrosion layer, corrosion occurs locally inside the coating, and the corrosion resistance of the coating of this embodiment is reduced.
Example 5
In this embodiment, the metal/metal nitride multilayer coating resistant to corrosion in a high-temperature marine environment is formed by alternately depositing Ti sublayers and TiN sublayers on a Ti6Al4V substrate, both the substrate and the uppermost layer are TiN layers, each TiN sublayer has a thickness of 1.8 μm, each Ti sublayer has a thickness of 0.5 μm, and the total number of layers is 17.
The preparation method of the metal/metal nitride multilayer coating resistant to high-temperature marine environment corrosion specifically comprises the following steps:
(1) cleaning of substrates
Firstly, grinding and polishing a Ti6Al4V titanium alloy (Ti-6% Al-4% V, mass fraction) substrate, and then adding acetone and ethanol according to a volume ratio of 1: 4, cleaning the mixture for 10-15 min by using 15-20 kHz ultrasonic waves, taking out and drying the mixture; then, ion bombardment cleaning is carried out by using ion plating equipment, the processed Ti6Al4V titanium alloy base body is hung on a sample rack and placed into an ion plating vacuum chamber, the chamber door is closed, and vacuum pumping is carried out until the vacuum degree is 1 multiplied by 10-2And after Pa, introducing Ar, maintaining the vacuum degree at 0.3Pa, applying a negative bias voltage value of 900V to the substrate, and performing ion bombardment cleaning on the substrate for 3min at a duty ratio of 60%.
(2) Alternately depositing TiN sub-layers and Ti sub-layers
After the ion bombardment cleaning in the step (1) is finished, cutting off Ar and introducing N2Maintaining the vacuum degree and the air pressure at 1.8Pa, controlling the matrix pulse negative bias value at 550V, opening the cathode Ti target current, setting the current to be 80A, starting the deposition of a TiN sublayer, setting the duty ratio to be 20 percent, keeping the sample frame rotating, keeping the speed at 5rpm, and keeping Ti: N in the obtained sublayer to be 1:1 (atomic ratio); then depositing a Ti sublayer, keeping the Ti target current 80A unchanged, and turning off N2Ar is introduced, the gas pressure is controlled to be about 0.4Pa, the negative bias value of the substrate is changed to 50V, the deposition time is controlled to be 5min, the duty ratio is set to be 20 percent, and the sample holder keeps the autorotation speed of 5 rpm. TiN sublayer and Ti during subsequent depositionSub-layers are sequentially and alternately deposited; and after the last Ti sublayer is deposited, depositing a TiN layer as the outermost layer. The heating temperature of the substrate is 300 ℃, the distance between the cathode target and the Ti6Al4V titanium alloy substrate is 21cm, the purity of the Ti target is 99.99wt%, and the diameter and the height of the Ti target are 120mm and 50 mm.
As shown in fig. 3(a) - (b), when the deposited multilayer coating is observed in shape, a large number of molten drops with large sizes exist on the surface of the coating, bright white is a Ti sublayer, dark gray is a TiN sublayer, a large-size molten drop defect exists inside the coating, and the multilayer coating is well combined with a Ti6Al4V matrix, and no cracking or delamination phenomenon is found. As shown in figures 4(a) - (b), after being corroded for 100 hours at 450 ℃, the corrosion weight gain is increased, the weight gain is accelerated in the corrosion process, large molten drops on the surface are cracked and peeled off after being corroded to form a corrosion pit, and r-TiO is generated on the surface2A corrosion layer (fig. 10), in which severe internal corrosion locally occurs inside the coating, and the corrosion resistance of the coating is poor.
Example 6
In this embodiment, the metal/metal nitride multilayer coating resistant to corrosion in a high-temperature marine environment is formed by alternately depositing Ti sublayers and TiN sublayers on a Ti6Al4V substrate, both the substrate and the uppermost layer are TiN layers, each TiN sublayer is 1.7 μm thick, each Ti sublayer is 1.0 μm thick, and the total number of layers is 15.
The preparation method of the metal/metal nitride multilayer coating resistant to high-temperature marine environment corrosion specifically comprises the following steps:
(1) cleaning of substrates
Firstly, grinding and polishing a Ti6Al4V titanium alloy (Ti-6% Al-4% V, mass fraction) substrate, and then adding acetone and ethanol according to a volume ratio of 1:2, cleaning the mixed solution by using 15-20 kHz ultrasonic waves for 10-15 min, taking out and drying the cleaned solution; then, ion bombardment cleaning is carried out by using ion plating equipment, the processed Ti6Al4V titanium alloy base body is hung on a sample rack and placed into an ion plating vacuum chamber, the chamber door is closed, and vacuum pumping is carried out until the vacuum degree is 1 multiplied by 10-2And after Pa, introducing Ar, maintaining the vacuum degree at 0.2Pa, applying a negative bias voltage value of 950V to the substrate, and performing ion bombardment cleaning on the substrate for 5min at a duty ratio of 50%.
(2) Alternately depositing TiN sub-layers and Ti sub-layers
After the ion bombardment cleaning in the step (1) is finished, cutting off Ar and introducing N2Maintaining the vacuum degree and the air pressure at 2.0Pa, controlling the matrix pulse negative bias value at 600V, opening the cathode Ti target current, setting the current to be 70A, starting the deposition of a TiN sublayer, setting the duty ratio to be 30 percent, keeping the sample frame rotating, keeping the speed at 5rpm, and keeping the Ti: N ratio in the obtained sublayer to be 1:1 (atomic ratio); then depositing a Ti sublayer, keeping the Ti target current 70A unchanged, and turning off N2Ar is introduced, the gas pressure is controlled to be about 0.5Pa, the negative bias value of the substrate is changed to 50V, the deposition time is controlled to be 11min, the duty ratio is set to be 30 percent, and the sample holder keeps the autorotation speed of 5 rpm. In the subsequent deposition process, TiN sublayers and Ti sublayers are alternately deposited in sequence; and after the last Ti sublayer is deposited, depositing a TiN layer as the outermost layer. The heating temperature of the matrix is 300 +/-20 ℃, the distance between the cathode target and the Ti6Al4V titanium alloy matrix is 22cm, the purity of the Ti target is 99.99wt%, and the diameter and the height of the Ti target are 100mm and 55 mm.
As shown in fig. 5(a) - (b), the deposited multilayer coating is observed in appearance, molten drops with the largest number and size exist on the surface of the coating, the bright white color is a Ti sublayer, the dark gray color is a TiN sublayer, the molten drop defect with larger size exists inside the coating, the size of partial molten drops exceeds the thickness of the TiN sublayer, the multilayer coating is well combined with a Ti6Al4V substrate, and cracking and delamination phenomena are not found. As shown in FIGS. 6(a) - (b), after 100h of corrosion at 450 ℃, the weight increase of the corrosion is the largest, the weight increase is accelerated in the corrosion process, the molten drops on the surface are peeled off after being corroded to form a corrosion pit with a larger diameter, and r-TiO is generated on the surface2And (4) a corrosion layer (figure 10), wherein the inner part of the coating is locally seriously corroded internally, and a convex oxide is formed after molten drop corrosion, so that the corrosion resistance of the coating is the worst.
Example 7
In this embodiment, the metal/metal nitride multilayer coating resistant to corrosion in a high-temperature marine environment is formed by alternately depositing Ti sublayers and TiN sublayers on a Ti6Al4V substrate, both the substrate and the uppermost layer are TiN layers, each TiN sublayer has a thickness of 1.6 μm, each Ti sublayer has a thickness of 0.7 μm, and the total number of layers is 15.
The preparation method of the metal/metal nitride multilayer coating resistant to high-temperature marine environment corrosion specifically comprises the following steps:
(1) cleaning of substrates
Firstly, grinding and polishing a Ti6Al4V titanium alloy (Ti-6% Al-4% V, mass fraction) substrate, and then adding acetone and ethanol according to a volume ratio of 1: 4, cleaning the mixture for 10-15 min by using 15-20 kHz ultrasonic waves, taking out and drying the mixture; then, ion bombardment cleaning is carried out by using ion plating equipment, the processed Ti6Al4V titanium alloy base body is hung on a sample rack and placed into an ion plating vacuum chamber, the chamber door is closed, and vacuum pumping is carried out until the vacuum degree is 1 multiplied by 10-2And after Pa, introducing Ar, maintaining the vacuum degree at 0.3Pa, applying a negative bias voltage value of 950V to the substrate, and performing ion bombardment cleaning on the substrate for 5min at a duty ratio of 50%.
(2) Alternately depositing TiN sub-layers and Ti sub-layers
After the ion bombardment cleaning in the step (1) is finished, cutting off Ar and introducing N2Maintaining the vacuum degree and the air pressure at 2.0Pa, controlling the matrix pulse negative bias value at 600V, opening the cathode Ti target current, setting the current at 70A, starting the deposition of the TiN sublayer, setting the duty ratio at 20 percent for 18min, keeping the sample rack rotating, keeping the speed at 5rpm, and keeping the Ti: N ratio in the obtained sublayer to be 1:1 (atomic ratio); then depositing a Ti sublayer, keeping the Ti target current 70A unchanged, and turning off N2Ar is introduced, the gas pressure is controlled to be about 0.4Pa, the negative bias value of the substrate is changed to 50V, the deposition time is controlled to be 14min, the duty ratio is set to be 20 percent, and the sample holder keeps the autorotation speed of 5 rpm. In the subsequent deposition process, TiN sublayers and Ti sublayers are alternately deposited in sequence; and after the last Ti sublayer is deposited, depositing a TiN layer as the outermost layer. The heating temperature of the matrix is 300 ℃, the distance between the cathode target and the Ti6Al4V titanium alloy matrix is 21cm, the purity of the Ti target is 99.99wt%, and the diameter and the height of the Ti target are 80mm and 50 mm.
The deposited multilayer coating is observed in appearance, a large number of molten drops with large sizes exist on the surface of the coating, the bright white color is a Ti sublayer, the dark gray color is a TiN sublayer, the molten drop defect with large sizes exists inside the coating, the size of partial molten drops exceeds the thickness of the TiN sublayer, and the multilayer coating is well combined with a Ti6Al4V matrix and is not goodCracking and delamination phenomena were observed. After 100 hours of corrosion at 450 ℃, the corrosion weight gain is increased, the weight gain is accelerated in the corrosion process, molten drops on the surface are peeled off after being corroded to form a corrosion pit, and r-TiO is generated on the surface2And the corrosion layer is locally subjected to relatively serious internal corrosion inside the coating, and the coating is locally peeled off after molten drop corrosion, so that the corrosion resistance of the coating is relatively poor.
Comparative example
In this comparative example, a TiN single layer coating was prepared, specifically including the steps of:
(1) cleaning of substrates
Firstly, grinding and polishing a Ti6Al4V titanium alloy (Ti-6% Al-4% V, mass fraction) substrate, and then adding acetone and ethanol according to a volume ratio of 1:2, cleaning the mixed solution by using 15-20 kHz ultrasonic waves for 10-15 min, taking out and drying the cleaned solution; then, ion bombardment cleaning is carried out by using ion plating equipment, the processed Ti6Al4V titanium alloy base body is hung on a sample rack and placed into an ion plating vacuum chamber, the chamber door is closed, and vacuum pumping is carried out until the vacuum degree is 1 multiplied by 10-2And after Pa, introducing Ar, maintaining the vacuum degree at 0.3Pa, applying a negative bias voltage value of 1000V to the substrate, and performing ion bombardment cleaning on the substrate for 3min at a duty ratio of 60%.
(2) Deposition of TiN
After the ion bombardment cleaning in the step (1) is finished, cutting off Ar and introducing N2Maintaining the vacuum degree and the gas pressure at 2.0Pa, controlling the pulse negative bias value of the matrix at 600V, opening the cathode Ti target current, setting the current at 70A, the deposition time at 200min, setting the duty ratio at 25%, keeping the sample holder rotating, keeping the speed at 5rpm, and keeping the ratio of Ti to N to 1 (atomic ratio) in the obtained coating.
As shown in fig. 7(a) - (b), the deposited multilayer coating is observed in morphology, the number of the coating surface is uniform, the number of molten drops is minimum, the size is minimum, the internal structure of the coating is uniform and compact through section observation, the coating is well combined with a Ti6Al4V matrix, and cracking and delamination phenomena are not found. As shown in fig. 8(a) - (b), the weight increase during corrosion was found to be the least after 100h of corrosion at 450 ℃ and the slowest during corrosion (fig. 9). The surface is even after corrosion, no obvious peeling is found, and r-TiO is generated on the surface2Corrosion layer (fig. 10), no internal corrosion was found locally inside the coating,the coating exhibits good corrosion resistance.
Claims (3)
1. A preparation method of a metal-metal nitride multilayer coating resistant to high-temperature marine environmental corrosion is characterized in that the metal/metal nitride multilayer coating resistant to high-temperature marine environmental corrosion is formed by alternately depositing Ti sublayers and TiN sublayers on a Ti6Al4V titanium alloy substrate, the TiN layers are close to the substrate and the uppermost layer, the thickness of each TiN sublayer is 2.0 mu m, the thickness of each Ti sublayer is 0.1 mu m, and the total number of layers is 17;
the preparation method of the metal/metal nitride multilayer coating resistant to high-temperature marine environment corrosion specifically comprises the following steps:
(1) cleaning of substrates
Firstly, grinding and polishing a Ti6Al4V titanium alloy matrix, and then adding acetone and ethanol according to a volume ratio of 1:2, cleaning the mixed solution by using 15-20 kHz ultrasonic waves for 10-15 min, taking out and drying the cleaned solution; then, ion bombardment cleaning is carried out by using ion plating equipment, the processed Ti6Al4V titanium alloy base body is hung on a sample rack and placed into an ion plating vacuum chamber, the chamber door is closed, and vacuum pumping is carried out until the vacuum degree is 7.0 multiplied by 10-3After Pa, introducing Ar, maintaining the vacuum degree at 0.5Pa, applying a negative bias value of 950V to the substrate, and performing ion bombardment cleaning on the substrate for 3min at a duty ratio of 30%;
(2) alternately depositing TiN sub-layers and Ti sub-layers
After the ion bombardment cleaning in the step (1) is finished, cutting off Ar and introducing N2Maintaining the vacuum degree and the air pressure at 1.4Pa, controlling the pulse negative bias value of the matrix at 600V, opening the current of a cathode Ti target, setting the current as 60A, starting the deposition of a TiN sublayer, setting the time as 18.5min and the duty ratio as 20 percent, keeping the sample holder rotating, keeping the speed at 3rpm, and keeping the atomic ratio of Ti to N in the obtained sublayer =1: 1; then depositing a Ti sublayer, keeping the Ti target current 70A unchanged, and turning off N2Introducing Ar, controlling the gas pressure to be about 0.2Pa, changing the negative bias value of the substrate to be 100V, controlling the deposition time to be 2min, setting the duty ratio to be 20%, and keeping the autorotation speed of 5rpm of the sample holder; in the subsequent deposition process, TiN sublayers and Ti sublayers are alternately deposited in sequence; after the final Ti sublayer is depositedThen, depositing a TiN layer as the outermost layer; the heating temperature of the matrix is 300 +/-20 ℃, the distance between the cathode target and the Ti6Al4V titanium alloy matrix is 17cm, the purity of the Ti target is 99.99wt%, and the diameter and the height of the Ti target are 80mm and 55 mm.
2. A preparation method of a metal-metal nitride multilayer coating resistant to high-temperature marine environmental corrosion is characterized in that the metal/metal nitride multilayer coating resistant to high-temperature marine environmental corrosion is formed by alternately depositing Ti sublayers and TiN sublayers on a Ti6Al4V titanium alloy substrate, the TiN layers are close to the substrate and the uppermost layer, the thickness of each TiN sublayer is 2.0 mu m, the thickness of each Ti sublayer is 0.2 mu m, and the total number of layers is 15;
the preparation method of the metal/metal nitride multilayer coating resistant to high-temperature marine environment corrosion specifically comprises the following steps:
(1) cleaning of substrates
Firstly, grinding and polishing a Ti6Al4V titanium alloy matrix, and then adding acetone and ethanol according to a volume ratio of 1: 2.5, cleaning the mixed solution for 10-15 min by using 15-20 kHz ultrasonic waves, taking out and drying the cleaned solution; then, ion bombardment cleaning is carried out by using ion plating equipment, the processed Ti6Al4V titanium alloy base body is hung on a sample rack and placed into an ion plating vacuum chamber, the chamber door is closed, and vacuum pumping is carried out until the vacuum degree is 8.5 multiplied by 10-3After Pa, introducing Ar, maintaining the vacuum degree at 0.5Pa, applying negative bias voltage of 950V to the substrate, and performing ion bombardment cleaning on the substrate for 5min at a duty ratio of 40%;
(2) alternately depositing TiN sub-layers and Ti sub-layers
After the ion bombardment cleaning in the step (1) is finished, cutting off Ar and introducing N2Maintaining the vacuum degree and the air pressure at 1.5Pa, controlling the matrix pulse negative bias value at 580V, opening the cathode Ti target current, setting the current to be 65A, starting the deposition of a TiN sublayer, setting the duty ratio to be 25 percent, keeping the sample frame rotating, keeping the speed at 4rpm, and keeping the atomic ratio of Ti to N in the obtained sublayer =1: 1; then depositing a Ti sublayer, keeping the Ti target current 65A constant, and turning off N2Introducing Ar, controlling the gas pressure to be about 0.3Pa, changing the negative bias value of the substrate to 80V, controlling the deposition time to be 2.5min, setting the duty ratio to be 25 percent,the sample holder maintains a spinning speed of 4 rpm; in the subsequent deposition process, TiN sublayers and Ti sublayers are alternately deposited in sequence; after the last Ti sublayer is deposited, depositing a TiN layer as the outermost layer; the heating temperature of the matrix is 300 +/-20 ℃, the distance between the cathode target and the Ti6Al4V titanium alloy matrix is 18cm, the purity of the Ti target is 99.99wt%, and the diameter and the height of the Ti target are 90mm and 55 mm.
3. A preparation method of a metal-metal nitride multilayer coating resistant to high-temperature marine environmental corrosion is characterized in that the metal/metal nitride multilayer coating resistant to high-temperature marine environmental corrosion is formed by alternately depositing Ti sublayers and TiN sublayers on a Ti6Al4V titanium alloy substrate, the TiN layers are close to the substrate and the uppermost layer, the thickness of each TiN sublayer is 1.9 mu m, the thickness of each Ti sublayer is 0.3 mu m, and the total number of layers is 15;
the preparation method of the metal/metal nitride multilayer coating resistant to high-temperature marine environment corrosion specifically comprises the following steps:
(1) cleaning of substrates
Firstly, grinding and polishing a Ti6Al4V titanium alloy matrix, and then adding acetone and ethanol according to a volume ratio of 1: 3, cleaning the mixed solution by using 15-20 kHz ultrasonic waves for 10-15 min, taking out and drying the cleaned solution; then, ion bombardment cleaning is carried out by using ion plating equipment, the processed Ti6Al4V titanium alloy base body is hung on a sample rack and put into an ion plating vacuum chamber, the chamber door is closed, and vacuum pumping is carried out until the vacuum degree is 9.0 multiplied by 10-3After Pa, introducing Ar, maintaining the vacuum degree at 0.4Pa, applying a negative bias voltage value of 900V to the substrate, and performing ion bombardment cleaning on the substrate for 7min at a duty ratio of 50%;
(2) alternately depositing TiN sub-layers and Ti sub-layers
After the ion bombardment cleaning in the step (1) is finished, cutting off Ar and introducing N2Maintaining the vacuum degree and the air pressure at 1.6Pa, controlling the matrix pulse negative bias value at 560V, opening the cathode Ti target current, setting the current as 70A, starting the deposition of the TiN sublayer, setting the duty ratio as 25 percent, keeping the sample frame rotating, keeping the speed at 5rpm, and keeping the atomic ratio of Ti to N in the obtained sublayer =1: 1; then depositing a Ti sublayer, keeping the Ti target current 70A unchanged, and turning off N2Introducing Ar, controlling the gas pressure to be about 0.4Pa, changing the negative bias value of the substrate to 70V, controlling the deposition time to be 3.5min, setting the duty ratio to be 25%, and keeping the autorotation speed of 5rpm of the sample holder; in the subsequent deposition process, TiN sublayers and Ti sublayers are alternately deposited in sequence; after the last Ti sublayer is deposited, depositing a TiN layer as the outermost layer; the heating temperature of the matrix is 300 +/-20 ℃, the distance between the cathode target and the Ti6Al4V titanium alloy matrix is 19cm, the purity of the Ti target is 99.99wt%, and the diameter and the height of the Ti target are 100mm and 55 mm.
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